BREF CWW Draft PDF

EUROPEAN COMMISSION
DIRECTORATE-GENERAL JRC
JOINT RESEARCH CENTRE
Institute for Prospective Technological Studies (Seville)
Technologies for Sustainable Development
European IPPC Bureau
Integrated Pollution Prevention and Control (IPPC)

Reference Document on Best Available Techniques in
Common Waste Water and Waste Gas
Treatment/Management Systems in the Chemical Sector
Draft Dated May 2000
World Trade Center, Isla de la Cartuja s/n, E-41092 Seville - Spain

Telephone: direct line (+34-95) 4488-258, switchboard 4488-318. Fax: 4488-426.
Internet: http://eippcb.jrc.es
Executive Summary
EXECUTIVE SUMMARY
KH / EIPPCB / cww_draft_1
Version May 2000
Preface
PREFACE
1.
Status of this document
Unless otherwise stated, references to the Directive in this document means the Council
Directive 96/61/EC on integrated pollution prevention and control.
This document is a working draft of the European IPPC Bureau. It is not an official publication
of the European Communities and does not necessarily reflect the position of the European
Commission.
2.
Relevant legal obligations of the IPPC Directive and the definition of BAT
In order to help the reader understand the legal context in which this document has been drafted,
some of the most relevant provisions of the IPPC Directive, including the definition of the term
best available techniques, are described in this preface. This description is inevitably
incomplete and is given for information only. It has no legal value and does not in any way alter
or prejudice the actual provisions of the Directive.
The purpose of the Directive is to achieve integrated prevention and control of pollution arising
from the activities listed in its Annex I, leading to a high level of protection of the environment
as a whole. The legal basis of the Directive relates to environmental protection. Its
implementation should also take account of other Community objectives such as the
competitiveness of the Communitys industry thereby contributing to sustainable development.
More specifically, it provides for a permitting system for certain categories of industrial
installations requiring both operators and regulators to take an integrated, overall look at the
polluting and consuming potential of the installation. The overall aim of such an integrated
approach must be to improve the management and control of industrial processes so as to ensure
a high level of protection for the environment as a whole. Central to this approach is the general
principle given in Article 3 that operators should take all appropriate preventative measures
against pollution, in particular through the application of best available techniques enabling
them to improve their environmental performance.
The term best available techniques is defined in Article 2(11) of the Directive as the most
effective and advanced stage in the development of activities and their methods of operation
which indicate the practical suitability of particular techniques for providing in principle the
basis for emission limit values designed to prevent and, where that is not practicable, generally
to reduce emissions and the impact on the environment as a whole. Article 2(11) goes on to
clarify further this definition as follows:
techniques includes both the technology used and the way in which the installation is
designed, built, maintained, operated and decommissioned;
available techniques are those developed on a scale which allows implementation in the
relevant industrial sector, under economically and technically viable conditions, taking into
consideration the costs and advantages, whether or not the techniques are used or produced
inside the Member State in question, as long as they are reasonably accessible to the
operator;
best means most effective in achieving a high general level of protection of the
environment as a whole.
Furthermore, Annex IV of the Directive contains a list of considerations to be taken into

account generally or in specific cases when determining best available techniques ... bearing in
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iii
Preface
mind the likely costs and benefits of a measure and the principles of precaution and prevention.
These considerations include the information published by the Commission pursuant to
Article 16(2).
Competent authorities responsible for issuing permits are required to take account of the general
principles set out in Article 3 when determining the conditions of the permit. These conditions
must include emission limit values, supplemented or replaced where appropriate by equivalent
parameters or technical measures. According to Article 9(4) of the Directive, these emission
limit values, equivalent parameters and technical measures must, without prejudice to
compliance with environmental quality standards, be based on the best available techniques,
without prescribing the use of any technique or specific technology, but taking into account the
technical characteristics of the installation concerned, its geographical location and the local
environmental conditions. In all circumstances, the conditions of the permit must include
provisions on the minimisation of long-distance or transboundary pollution and must ensure a
high level of protection for the environment as a whole.
Member States have the obligation, according to Article 11 of the Directive, to ensure that
competent authorities follow or are informed of developments in best available techniques.
3.
Objective of this Document
Article 16(2) of the Directive requires the Commission to organise an exchange of information
between Member States and the industries concerned on best available techniques, associated
monitoring and developments in them, and to publish the results of the exchange.
The purpose of the information exchange is given in recital 25 of the Directive, which states
that the development and exchange of information at Community level about best available
techniques will help to redress the technological imbalances in the Community, will promote
the world-wide dissemination of limit values and techniques used in the Community and will
help the Member States in the efficient implementation of this Directive.
The Commission (Environment DG) established an information exchange forum (IEF) to assist
the work under Article 16(2) and a number of technical working groups have been established
under the umbrella of the IEF. Both IEF and the technical working groups include
representation from Member States and industry as required in Article 16(2).
The aim of this series of documents is to reflect accurately the exchange of information which
has taken place as required by Article 16(2) and to provide reference information for the
permitting authority to take into account when determining permit conditions. By providing
relevant information concerning best available techniques, these documents should act as
valuable tools to drive environmental performance.
4.
Information Sources
This document represents a summary of information collected from a number of sources,

including in particular the expertise of the groups established to assist the Commission in its
work, and verified by the Commission services. All contributions are gratefully acknowledged.
5.
How to understand and use this document
The information provided in this document is intended to be used as an input to the

determination of BAT in specific cases. When determining BAT and setting BAT-based permit
conditions, account should always be taken of the overall goal to achieve a high level of
protection for the environment as a whole.
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Preface
The rest of this section describes the type of information that is provided in each section of the
document.
Chapter 1 provides a general description of waste water and waste gas, including general
information on treatment and management systems.
Chapter 2 describes the general approach to implementation of waste water and waste gas
management systems and the tools to achieve it.
Chapter 3 gives a description of treatment technologies for waste water and waste gas, including
recovery and abatement technologies, pre-treatment and end-of-pipe methods. Chapters 2 and 3
are the core of this Reference Document to provide the necessary information to come to a BAT
decision on a horizontal level.
Chapter 4 will show a BAT approach to apply to a chemical site as a whole using the
knowledge gained from chapters 2 and 3. The purpose is thus to provide general indications to
assist in the determination of BAT-based permit conditions concerning installations in chemical
industry or for the establishment of general binding rules under Article 9(8). It should be
stressed, however, that this document does not propose emission limit values for implemented
waste water and waste gas facilities. The determination of appropriate permit conditions will
involve taking account of local, site-specific factors such as the technical characteristics of the
installation concerned, its geographical location and the local environmental conditions. In the
case of existing installations, the economic and technical viability of upgrading them also needs
to be taken into account. Even the single objective of ensuring a high level of protection for the
environment as a whole will often involve making trade-off judgements between different types
of environmental impact, and these judgements will often be influenced by local considerations.
Although an attempt is made to address some of these issues, it is not possible for them to be
considered fully in this document. The techniques and levels presented in chapter 4 will
therefore not necessarily be appropriate for all cases. On the other hand, the obligation to ensure
a high level of environmental protection including the minimisation of long-distance or
transboundary pollution implies that permit conditions cannot be set on the basis of purely local
considerations. It is therefore of the utmost importance that the information contained in this
document is fully taken into account by permitting authorities.
Since the best available techniques change over time, this document will be reviewed and
updated as appropriate. All comments and suggestions should be made to the European IPPC
Bureau at the Institute for Prospective Technological Studies at the following address:
World Trade Center, Isla de la Cartuja s/n, E-41092 Seville Spain

Telephone: +34 95 4488 284
Fax: +34 95 4488 426
e-mail eippcb@jrc.es
Internet: http://eippcb.jrc.es
Version May 2000
Reference Document on Best Available Techniques in the Common Waste Water

and Waste Gas Treatment/Management Systems in the Chemical Sector
EXECUTIVE SUMMARY........................................................................................................................... i
PREFACE ...................................................................................................................................................iii
Scope.........................................................................................................................................................xiii
1
General Description ............................................................................................................................. 1
1.1
Waste Water in Chemical Industry .............................................................................................. 1
1.1.1
Characteristics ...................................................................................................................... 1
1.1.2
Waste Water Handling ......................................................................................................... 3
1.1.2.1 Process-Integrated Measures............................................................................................ 3
1.1.2.1.1 Counter Current Washing as Example for Water Saving Processes .......................... 4
1.1.2.1.2 Multiple Use and Recirculation Operations ............................................................... 4
1.1.2.1.3 Indirect Cooling with Vapour Phases......................................................................... 5
1.1.2.1.4 Waste Water-free Processes for Vacuum Generation ................................................ 5
1.1.2.1.5 Waste Water-free Processes for Exhaust Air Cleaning .............................................. 6
1.1.2.1.6 Substance Recovery or Retention from Mother Liquors or by Optimised Processes. 6
1.1.2.1.7 Use of Low-contaminated Raw Materials and Auxiliaries......................................... 7
1.1.2.2 End-of-pipe Measures ...................................................................................................... 7
1.1.2.3 Waste Water Management ............................................................................................. 10
1.2
Waste Gas in Chemical Industry................................................................................................ 13
1.2.1
Characteristics .................................................................................................................... 13
1.2.2
Waste Gas Treatment ......................................................................................................... 14
1.2.3
Waste Gas Management..................................................................................................... 17
1.3
Interdependencies between Waste Water and Waste Gas Treatment......................................... 18
2
Waste water/Waste Gas Management................................................................................................ 19
2.1
General Description of Management Systems ........................................................................... 19
2.1.1
Listing of a Quantified Inventory of all Streams................................................................ 19
2.1.1.1 General Information ....................................................................................................... 19
2.1.1.1.1 Site Information ....................................................................................................... 19
2.1.1.1.2 List of Production Plants .......................................................................................... 19
2.1.1.1.3 Information on the Production ................................................................................. 19
2.1.1.2 Stream Inventory............................................................................................................ 20
2.1.2
Setting of Internal Targets for Effluent Streams ................................................................ 20
2.1.3
Regular Review of Targets in Order to meet Anticipated Changes ................................... 20
2.1.4
Selection of the most Appropriate Emission Control Options ........................................... 20
2.1.5
Implementation of the Selected Emission Control Options ............................................... 21
2.1.6
Monitoring, Reporting and Record Keeping of Results ..................................................... 21
2.2
Management Tools..................................................................................................................... 22
2.2.1
General Management Tools ............................................................................................... 22
2.2.1.1 Environmental Management Strategy (EMS) ................................................................ 22
2.2.1.2 Setting of Internal Targets.............................................................................................. 23
2.2.1.3 Regular Review of Targets............................................................................................. 24
2.2.1.4 Cost Benefit and Risk Considerations............................................................................ 25
2.2.2
Waste Water Management Tools ....................................................................................... 25
2.2.2.1 Waste Water Register..................................................................................................... 25
2.2.2.2 Whole Effluent Assessment (WEA)............................................................................... 27
2.2.2.3 Pinch Analysis on Water and Waste Water................................................................ 27
2.2.2.4 Choice of Sewage System .............................................................................................. 29
2.2.2.4.1 Selection of Waste Water Collection and Separation/Segregation........................... 29
2.2.2.4.2 Storage or Retention Capacity for Failure Events .................................................... 31
2.2.2.4.2.1 Self-contained Buffer Devices .......................................................................... 31
2.2.2.4.2.2 Connected Buffer Devices ................................................................................ 33
2.2.2.5 Selection of Appropriate Waste Water Treatment Options ............................................ 33
2.2.3
Waste Gas Management Tools........................................................................................... 37
2.2.3.1 Waste Gas Inventory ...................................................................................................... 37
2.2.3.2 Choice of Waste Gas Collection Systems ...................................................................... 40
2.2.3.3 Selection of Appropriate Waste Gas Control Options.................................................... 40
2.2.3.4 Final Waste Gas Abatement System Design .................................................................. 44
3
Applied Treatment Technology ......................................................................................................... 47
3.1
Information presented in this Chapter ........................................................................................ 47
3.1.1
Information on Cost in this Horizontal Document ............................................................. 48
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3.1.1.1 Total Installed Costs vs Supplier Equipment Costs ........................................................48

3.1.1.2 Green Field Costs vs Retro-fitting Costs ........................................................................49
3.1.1.3 Capital Costs vs Operating Costs....................................................................................50
3.1.1.4 Initial Emission Control Costs vs Incremental Control Costs ........................................50
3.2
Waste Water Treatment ..............................................................................................................51
3.2.1
Flow Balancing...................................................................................................................53
3.2.2
Insoluble Waste Water Contaminants.................................................................................53
3.2.2.1 Gravity Separation ..........................................................................................................53
3.2.2.1.1 Sedimentation ...........................................................................................................53
3.2.2.1.2 Oil-Water Separation ................................................................................................56
3.2.2.1.2.1 American Petroleum Institute Separator (API)..................................................57
3.2.2.1.2.2 Parallel Plate Interceptor (PPI) ..........................................................................58
3.2.2.1.2.3 Corrugated Plate Interceptor (CPI) ....................................................................60
3.2.2.2 Coagulation.....................................................................................................................61
3.2.2.3 Flocculation ....................................................................................................................64
3.2.2.4 Flotation..........................................................................................................................66
3.2.2.5 Filtration .........................................................................................................................70
3.2.2.6 Pore Type Membrane Processes .....................................................................................73
3.2.2.6.1 Microfiltration (MF) .................................................................................................74
3.2.2.6.2 Ultrafiltration (UF) ...................................................................................................76
3.2.3
Soluble Non-biodegradable Waste Water Contaminants....................................................79
3.2.3.1 Precipitation....................................................................................................................79
3.2.3.2 Adsorption ......................................................................................................................81
3.2.3.2.1 Granular Activated Carbon (GAC) Adsorption........................................................82
3.2.3.2.2 Powdered Activated Carbon (PAC) Adsorption.......................................................85
3.2.3.2.3 Zeolite Adsorption....................................................................................................87
3.2.3.3 Ion Exchange ..................................................................................................................88
3.2.3.4 Diffusion Type Membrane Process ................................................................................91
3.2.3.4.1 Nanofiltration (NF)...................................................................................................91
3.2.3.4.2 Reverse Osmosis (RO) .............................................................................................94
3.2.3.5 Extraction........................................................................................................................97
3.2.3.6 Distillation/Rectification.................................................................................................99
3.2.3.7 Evaporation...................................................................................................................101
3.2.3.8 Stripping .......................................................................................................................103
3.2.3.8.1 Air Stripping ...........................................................................................................103
3.2.3.8.2 Steam Stripping ......................................................................................................106
3.2.3.9 Oxidation ......................................................................................................................108
3.2.3.9.1 Chemical Oxidation................................................................................................108
3.2.3.9.2 Wet Air Oxidation ..................................................................................................111
3.2.3.9.2.1 Low-pressure Wet Air Oxidation ....................................................................111
3.2.3.9.2.2 High-pressure Wet Air Oxidation....................................................................113
3.2.3.9.3 Waste Water Incineration .......................................................................................115
3.2.4
Soluble Biodegradable Waste Water Contaminants .........................................................117
3.2.4.1 Biological Treatment ....................................................................................................117
3.2.4.2 Nitrogen Elimination ....................................................................................................122
3.3
Rainwater Treatment ................................................................................................................126
3.3.1
Rain and Fire Water Control.............................................................................................126
3.3.2
Wet Detention Ponds ........................................................................................................126
3.3.3
Sand Filters.......................................................................................................................128
3.4
Sludge Treatment......................................................................................................................130
3.4.1
Sludge Pumping................................................................................................................131
3.4.2
Sludge Thickening............................................................................................................131
3.4.2.1 Gravity Thickening.......................................................................................................131
3.4.2.2 Centrifugal Thickening.................................................................................................134
3.4.2.3 Flotation Thickening.....................................................................................................135
3.4.2.4 Gravity Belt Thickening ...............................................................................................137
3.4.2.5 Rotary Drum Thickening ..............................................................................................138
3.4.3
Sludge De-watering ..........................................................................................................139
3.4.3.1 Sludge De-watering by Centrifugation .........................................................................139
3.4.3.2 Sludge De-watering by Belt Filter Presses ...................................................................141
3.4.3.3 Sludge De-watering by Filter Presses ...........................................................................143
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3.5
Waste Gas Treatment ............................................................................................................... 146
3.5.1
Recovery Operations and Processes for VOCs ................................................................ 148
3.5.1.1 Selective Membrane Separation ................................................................................... 148
3.5.1.2 Condensation................................................................................................................ 151
3.5.1.3 Adsorption.................................................................................................................... 158
3.5.1.4 Scrubbers for Trace Gas Removal................................................................................ 163
3.5.2
Abatement Operations and Processes for VOCs and Inorganic Gases............................. 170
3.5.2.1 Biofiltration .................................................................................................................. 170
3.5.2.2 Bioscrubbing ................................................................................................................ 173
3.5.2.3 Catalytic Filtration........................................................................................................ 175
3.5.2.4 Thermal Incineration .................................................................................................... 178
3.5.2.5 Catalytic Incineration ................................................................................................... 183
3.5.2.6 Flaring .......................................................................................................................... 186
3.5.3
Abatement Technology for Particulates ........................................................................... 191
3.5.3.1 Separator ...................................................................................................................... 191
3.5.3.2 Cyclone ........................................................................................................................ 193
3.5.3.3 Electrostatic Precipitator .............................................................................................. 195
3.5.3.4 Dust Scrubber............................................................................................................... 199
3.5.3.5 Fabric Filter.................................................................................................................. 203
3.5.3.6 Two-Stage Dust Filter .................................................................................................. 206
3.5.3.7 Ceramic Filter............................................................................................................... 208
3.5.3.8 Absolute Filter.............................................................................................................. 210
3.5.3.9 HEAF Filter.................................................................................................................. 212
3.5.3.10
Mist Filter................................................................................................................. 214
3.5.4
Abatement Operations and Processes for Gaseous Pollutants in Flue Gases ................... 215
3.5.4.1 Dry Sorbent Injection ................................................................................................... 216
3.5.4.2 Semi-dry Sorbent Injection .......................................................................................... 218
3.5.4.3 Biological Sulphur Dioxide Removal from Flue Gas................................................... 220
3.5.4.4 Selective Non-catalytic Reduction of NOx (SNCR)..................................................... 222
3.5.4.5 Selective Catalytic Reduction of NOx (SCR) ............................................................... 224
4
Best Available Techniques............................................................................................................... 227
5
Emerging Techniques ...................................................................................................................... 229
6
Conclusion and Recommendation.................................................................................................... 231
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List of tables
Table 1.1: Unit Operations and Processes and Waste Water Treatment Systems used to remove Major
Contaminants found in Waste Water ........................................................................................8
Table 1.2: Selection of Techniques for Waste Gas Emission Reduction in Relation to the Pollutant to be
removed ..................................................................................................................................15
Table 1.3: Selection of Techniques for Waste Gas Emission Reduction in Relation to Waste Gas Flow
Rate.........................................................................................................................................16
Table 1.4: Potential Emissions from Waste Water Treatment Plants .........................................................18
Table 3.1: Example for Costs of an Actual Project ....................................................................................49
Table 3.2: Removal Performance by Coagulation......................................................................................63
Table 3.3: Characteristics of Microfiltration and Ultrafiltration.................................................................73
Table 3.4: Typical Performance Characteristics of GAC Adsorbers with Feed Concentrations of about
1000 mg/l................................................................................................................................83
Table 3.5: Characteristics of Nanofiltration and Reverse Osmosis ............................................................92
Table 3.6: Removal of Pesticides Via High-pressure Wet Air Oxidation ................................................114
Table 3.7: Substantial Inhibitors to Nitrification ......................................................................................123
Table 3.8: Pollutant Removal by Wet Detention Ponds Dependent on Hydraulic Residence Time.........127
Table 3.9: Typical Metal Content in Waste Water Sludge .......................................................................130
Table 3.10: Typical Concentrations of Unthickened and Thickened Sludges for Gravity Thickeners.....133
Table 3.11: De-watering Performance of Centrifuges..............................................................................141
Table 3.12: De-watering Performance of Belt Filter Press.......................................................................143
Table 3.13: Effect of Varying Feed Concentrations on Mass of Solvent adsorbed ..................................161
Table 3.14: Types of Burner.....................................................................................................................179
Table 3.15: Filter Materials used in Fabric Filters....................................................................................204
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List of figures
Figure 1.1: General Waste Water Management Strategy........................................................................... 11
Figure 2.1: Example of a Plant-oriented EMS ........................................................................................... 23
Figure 2.2: WaterPinch - Analysis, Source and Sink Curves ................................................................. 28
Figure 2.3: Example for Water Conservation Strategy before and after WaterPinch Analysis.............. 29
Figure 2.4: Decision Diagram dealing with Waste Water Segregation and Treatment.............................. 30
Figure 2.5: Self-contained Buffer Device, Process Water included........................................................... 31
Figure 2.6: Self-contained Buffer Device, Process Water not included..................................................... 32
Figure 2.7: Connected Buffer Device, not continuously flooded............................................................... 32
Figure 2.8: Connected Buffer Device, continuously flooded..................................................................... 33
Figure 2.9: Decision Diagram for the Allocation of Waste Water Streams polluted with Organic
Substances to the Various Treatment Techniques .................................................................. 34
Figure 3.1: Schematic Overview of Waste Water Treatment in a Chemical Plant .................................... 51
Figure 3.2: Sedimentation or Settler Tank ................................................................................................. 54
Figure 3.3: Lamina or Tube Settler ............................................................................................................ 55
Figure 3.4: American Petroleum Institute Separator (API Separator)........................................................ 57
Figure 3.5: Parallel Plate Interceptor (PPI) ................................................................................................ 59
Figure 3.6: Corrugated Plate Interceptor (CPI) .......................................................................................... 60
Figure 3.7: DAF System: a) with Recycle, b) without Recycle ................................................................. 68
Figure 3.8: Conventional Downflow Multi-medium Sandfilter................................................................. 71
Figure 3.9: Pressure Filter .......................................................................................................................... 72
Figure 3.10: Typical GAC Adsorber.......................................................................................................... 83
Figure 3.11: RO Arrangement.................................................................................................................... 95
Figure 3.12: Stripping of Ammonia, Air and Steam Stripping ................................................................ 104
Figure 3.13: Mechanical-biological-chemical Waste Water Treatment Plant inclusive of Sludge
Treatment ............................................................................................................................. 118
Figure 3.14: Tower Biology, System BAYER......................................................................................... 119
Figure 3.15: Tower Biology, System HOECHST.................................................................................... 120
Figure 3.16: Nitrification/Denitrification in Series .................................................................................. 125
Figure 3.17: Nitrification/Denitrification with Denitrification pre-operated ........................................... 125
Figure 3.18: Sludge and Scum Pumps in Waste Water Treatment Plants................................................ 132
Figure 3.19: Centrifugal Sludge Thickener Applications......................................................................... 134
Figure 3.20: DAF Thickener for Waste Activated Sludge ....................................................................... 136
Figure 3.21: Belt Filter Press De-watering............................................................................................... 142
Figure 3.22: Fixed Volume Recessed Plate Filter Press .......................................................................... 144
Figure 3.23: Schematic Overview of Waste Gas Treatment in a Chemical Plant .................................... 146
Figure 3.24: Membrane Separation.......................................................................................................... 148
Figure 3.25: Typical Membrane Capillary Module.................................................................................. 149
Figure 3.26: Membrane Separation Process for Waste Gas ..................................................................... 150
Figure 3.27: Two-Stage Condensation System ........................................................................................ 153
Figure 3.28: Cryogenic Condensation Recovery System Integral with a Typical Nitrogen Blanketing
Operation.............................................................................................................................. 154
Figure 3.29: Cryogenic Recovery System under Inert Atmosphere......................................................... 154
Figure 3.30: Typical Closed-cycle Inert Gas Condensation System ........................................................ 155
Figure 3.31: Adsorption Potential of GAC with Various Organic Solvents ............................................ 159
Figure 3.32: Typical Twin-bed Adsorption Process ................................................................................ 160
Figure 3.33: Continuous Adsorption-Desorption with a Polymer Adsorbent .......................................... 160
Figure 3.34: Moving Bed Scrubber.......................................................................................................... 165
Figure 3.35: Packed Bed Scrubbers ......................................................................................................... 165
Figure 3.36: Plate Scrubber...................................................................................................................... 166
Figure 3.37: Spray Towers, (a) Counter-current, (b) Co-current ............................................................. 167
Figure 3.38: Typical Absorption/Desorption system ............................................................................... 167
Figure 3.39: Biofilter Construction .......................................................................................................... 170
Figure 3.40: Typical Biofilter Process ..................................................................................................... 172
Figure 3.41: Typical Bioscrubbing Process ............................................................................................. 174
Figure 3.42: Schematic Overview of a Catalyst Filter System................................................................. 176
Figure 3.43: Catalytic Filter Baghouse, including Sampling Trains ........................................................ 177
Figure 3.44: Basic Types of Incineration Equipment............................................................................... 179
Figure 3.45: Thermal Incineration with Pre-heating Stage ...................................................................... 180
Figure 3.46: Thermal Incineration with Steam Generation...................................................................... 181
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Figure 3.47: Catalytic Incinerator.............................................................................................................183

Figure 3.48: Injector Rod Flare ................................................................................................................188
Figure 3.49: Shielded Flare ......................................................................................................................188
Figure 3.50: Muffle Flare .........................................................................................................................189
Figure 3.51: Separator ..............................................................................................................................192
Figure 3.52: Reverse Flow Cyclone .........................................................................................................194
Figure 3.53: Straight through Cyclone .....................................................................................................194
Figure 3.54: Plate-wire Electrostatic Precipitator.....................................................................................196
Figure 3.55: Tubular Electrostatic Precipitator ........................................................................................197
Figure 3.56: Schematic Diagram of Single Stage and Two-Stage ESP....................................................197
Figure 3.57: Impingement Entrainment Scrubber ....................................................................................200
Figure 3.58: Venturi Scrubber ..................................................................................................................201
Figure 3.59: Fabric Filter..........................................................................................................................203
Figure 3.60: Two-Stage Dust Filter ..........................................................................................................206
Figure 3.61: Absolute Filter .....................................................................................................................210
Figure 3.62: HEAF Filter .........................................................................................................................212
Figure 3.63: Mist Filter.............................................................................................................................214
Figure 3.64: Dry Sorbent Injection for Sulphur Dioxide Removal (Positions of Injection) .....................216
Figure 3.65: Spray Dry Flue Gas Desulphurisation System .....................................................................218
Figure 3.66: Biological Sulphur Dioxide Removal from Flue Gas ..........................................................221
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xi
Scope
SCOPE
This Reference Document titled Common Waste Water and Waste Gas
Treatment/Management Systems in the Chemical Sector is a horizontal document, meant to
complement the BAT Reference Documents series for the chemical sector. It will not address
the performance of production processes in combination with waste water and waste gas
effluents, nor prescribe when or whether waste water/waste gas treatment is required.
The purpose of this horizontal document is to describe options for waste water/waste gas
treatment and management decision making in a general way. Achievable performance data will
be presented as illustrative examples. These examples are not meant to imply that the stated
values can be achieved with each individual application under all working conditions.
Recommendations given are normally valid in general, but they might be inappropriate with
special site-specific or production-specific circumstances.
The options for waste water and/or waste gas treatment are manifold in the chemical industry,
so this document must restrict itself to those applications that are common in the chemical
sector. This means that treatment methods only used at one site or only designed for one special
production process will not be covered by this document. They fall within the scope of
appropriate vertical documents. On the other hand, treatment operations or processes that have
not yet been applied in the chemical industry, but that are successfully in use in other sectors,
are covered when they are expected to be usefully applicable. Typically site-specific or
production-specific issues concerning waste water/waste gas treatment are generally not
covered explicitly. They are considered in a general approach to dealing with specific
conditions.
Another topic in this Reference Document is waste water/waste gas management. Since proper
management has much to do with adapting local conditions (e.g. production specifics,
legislation, local environmental situation, availability and quality of raw material and/or
auxiliaries such as water, etc.) to the economically and ecologically efficient running of an
industry site as a whole, the application of a management system is necessarily site-specific. As
with treatment systems, this document will not deal with such site-specific applications. It will,
however, describe the approach or approaches to waste water and waste gas management.
To avoid overlaps with vertical BAT Reference Documents on the chemical sector, this
horizontal document will restrict itself mostly to a detailed presentation of techniques and
systems of general applicability in the chemical sector that are relevant to the prevention or
reduction of emissions, including pre-treatment and end-of-pipe abatement. These techniques
and systems are described with regard to their impact on the environment, their costs and their
efficiency/performance. Process-integrated techniques are only touched on in a general way,
e.g. when they can be used in several processes, or when their application is generally
acknowledged.
The term impact on the environment includes, e.g.:
resource consumption such as ground water, energy, raw material, chemical substances,
etc.,
emissions to water and/or air, including noise and odour,
generation of waste,
emissions arising from events like start up/shut down.
The borderline to be drawn in this document between processes relevant to chemical

production, i.e. the scope of vertical documents, and processes relevant to emission prevention
and/or reduction, i.e. the scope of a horizontal document, is illustrated, for waste water, in
Figure I. The situation for waste gas is similar.
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xiii
Scope
Because of the complexity and diversity of waste water and waste gas originating from the
chemical industry there will be no definitive Best Available Technique for waste water and
waste gas treatment generally applicable to all chemical installations or sites. So this horizontal
Reference Document will not give a solution for the implementation of BAT for handling waste
water and waste gas in the chemical industry by naming one or several techniques. Instead it
will support guidance on reaching a BAT decision for a chemical industry site when handling
aqueous and/or gaseous releases originating from chemical installations.
Chemical
reaction
Reaction
mixture
Workup
Product
Auxiliaries,
solvents
Product
isolation
P
R
O
D
U
C
T
I
O
N
Aqueous
residue
Treatment
Waste water
Tributary
stream
treatment
R
E
D
U
C
T
I
O
N
Central
disposal
systems
Figure I: Borderline between Relevance to Production and Reduction/Prevention
xiv
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1 GENERAL DESCRIPTION
General scientific laws like chemical and/or physical equilibrium make the occurrence of waste
inevitable during chemical production processes (syntheses), so that unwanted by-products have
to be expelled. The character and scale of these emissions are highly variable and depend on the
composition of raw materials, products, intermediates, auxiliaries, process conditions, etc.
Waste occurring in chemical industry can be divided into:
waste water,
waste gas,
liquid and solid residues.
Liquid and solid residues, originating from chemical production and product handling, are to be
treated separately usually in vertical documents and are not the subject of this document.
1.1 Waste Water in Chemical Industry

1.1.1 Characteristics
From the qualitative point of view, the majority of waste water in the chemical industry does
not usually originate directly from chemical reaction steps. Though waste water can arise
directly from reactions, e.g. as condensate or reaction water, the aqueous discharges from
subsequent physico-chemical work-up of synthesis mixtures are considerably greater. Products
and/or intermediates from each synthesis or each synthesis stage are isolated and purified by
operations such as filtration, centrifugation, etc., from aqueous reaction solutions, or by workup of reaction mixtures via, e.g., extraction or distillation.
Such waste water streams or partial streams arising in direct association with chemical
syntheses process water are, for example:
mother liquors, i.e. the most highly polluted waste water streams of a synthesis, especially
the initial aqueous discharges,
washing water from purification of products,
vapour condensates,
quench water,
waste water from exhaust air/flue gas cleanup,
waste water from equipment cleaning,
waste water from vacuum generation.
Waste water partial streams from other on-site sources, such as:
scrubbing of exhaust gases from incinerations and combustions,

treatment of utility water,
bleed from boiler feed water systems (probably containing corrosion inhibitors, biocides,
scaling),
blowdown from cooling cycles,
laboratory and pilot-scale plants,
workshops,
sanitation waste water collection,
collection of rainwater from contaminated areas,
landfill leachates,
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contribute to the overall water pollution as well. So waste water generally contains as
contaminants almost every compound used or produced even intermediately in a chemical
plant.
These contaminants are, e.g.:
non-reacted starting compounds,

production residues,
auxiliaries to the extent that they are not recovered from the aqueous discharges,
intermediate compounds,
unwanted by-products.
If syntheses are carried out using organic solvents and other auxiliaries, these regularly make up
the majority of the organic pollutant load emitted to the waste water treatment facilities. On the
other hand, by-products and starting compounds are in most cases responsible for the poorly
biodegradable part of the total waste water load.
The majority of production waste water (70 90 %) consists of partial streams with a low
pollution level [cww/tm/82], e.g.:
cleaning water,
waste water from vacuum generation,
washing water from exhaust air cleanup,
waste water originating from equipment facilities such as product pumps, etc.
Partial streams such as mother liquors, initial aqueous discharges, blowdown from cleaning
cycles and vapour condensates, make up the remaining 10 30 % [cww/tm/82].
When considering pollution loads, the ratio is reversed. The more highly concentrated waste
water partial streams (10 30 % of the total waste water amount) generally contain up to 90 %
of the relevant pollutant loads [cww/tm/82].
Toxicity assessment can be used for evaluation of complex waste streams and effluent in
addition to the use of sum-parameters such as COD, AOX, or EOX. The aim is to assess the
possible hazardous character of effluent, which would be insufficiently controlled when relying
only on the chemical indications provided by those sum-parameters. On the other hand,
relatively high values for e.g. COD might be permitted under site-specific conditions, provided
that there is no toxicity involved. Toxicity assessment parameters are, e.g. fish, algae and
daphniae toxicity.
As a classification of acute toxicity based on EC and/or LC50 values the following dilution
factors are proposed [cww/tm/84]:
very strong toxic

strong toxic
toxic
minor toxic
not toxic
> 100
10 100
2 10
>12
1
Dilution factor 100 means the waste water stream has to be diluted to one hundredth of its
original concentration to enable at least 50 % of the test organisms to survive.
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1.1.2 Waste Water Handling

The different sources of waste water and its variety of pollutants and their load make a complex
system of waste water handling and treatment in its broadest possible sense inevitable for a
chemical industry site. Such a waste water handling and treatment system has to take into
account, e.g.:
process-integrated measures, such as:

- water recirculation,
- recycling of contaminants, e.g. solvents, raw reaction material or product,
- water saving and pollutant avoidance measures,
end-of-pipe measures,
integrated waste water management for the chemical site as a whole and, where possible,
integration with other schemes in the locality.
These are only a few examples among many which will be dealt with in this document.
1.1.2.1 Process-Integrated Measures

Though, strictly speaking, process-integrated measures for water conservation and prevention or
reduction of the pollutant discharge via waste water are not part of the scope of this document,
they will nevertheless be mentioned as long as they are generally applicable in chemical
production processes. They are in any case items of good management practice and for
consideration when implementing a waste water management system on a site.
Modern environmental protection is more and more shifting from end-of-pipe methods to
process-integrated or production-integrated measures. Process-integrated measures are a
source of significant environmental improvement in both new and existing plants. They are
intended to decrease or even to avoid the production of residues directly at source before
they become a discharge. Often these process improvements help to decrease costs for
additional treatment measures, as well as increase economic efficiency by increasing production
yield and/or decreasing input of raw material. Disposal costs and the limitations of end-of-pipe
treatment can influence this shift toward process-integrated measures.
Proper production-integrated environmental protection uses all possible physical, chemical
biological and engineering techniques for the prevention, reduction and recycling of residues.
Examples are:
new synthesis pathways,

use of other feedstock and process agents,
use of other fuels,
optimisation of process steps,
improved reaction procedure,
technical adaptations to the process,
improved use of catalysts and/or solvents,
optimisation of plant technology and control engineering,
recycling of auxiliaries (e.g. washing water, inert gases, solvents, catalysts),
recycling of residues immediately during the process,
use of residues as raw material for other productions (product integration within and/or
outside the location),
use of residues for energy generation.
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Obviously the development of completely new pathways for syntheses in existing plants will
remain an exception, and will be restricted to bulk products or products of high economic value.
In practice, production-integrated environmental protection will progress continuously as the
sum of many individual and maybe tiny improvements over time. Some important and
normally easily retro-fittable production-integrated measures relevant to waste water are
described below.
But, to bear in mind: this document describes the general application of process-integrated
measures and gives some examples where to implement them. It must, however, be emphasised
that, under specific circumstances, the introduction of process-integrated measures might lead to
negative impacts that over-shadow the benefits of water conservation or pollutant decrease.
Some illustrative examples are mentioned in the corresponding chapters.
1.1.2.1.1
Counter Current Washing as Example for Water Saving Processes
Conventional product washing processes are multiple extractions working batchwise by treating
the product phase with water in order to remove salts or other soluble minor components. The
amount of water used is generally many times the amount of product to be washed. At each
individual washing step there are unavoidable losses of product caused by its solubility,
emulsification and by the formation of solid layers at the phase boundary, etc.
By optimising the washing process, and/or introducing modern washing processes, such as
counter current washing, a considerable reduction of waste water (and waste) can be achieved.
A simultaneous increase of pollutant concentration might allow an easier and/or more effective
treatment, or, under special circumstances, recycling of material. The degree of optimisation
depends on the production capacity and on having frequent production runs. Counter current
washing is economic specifically for large scale plants. There it can be tailored to a particular
production process. For plants dealing with small outputs, pilot scale productions or seldom
used campaign productions, these processes usually are not viable.
1.1.2.1.2
Multiple Use and Recirculation Operations
For introducing measures concerning multiple use and recirculation operations one has to
distinguish between:
waste water originating directly from production (e.g. reaction water, distillates, washing
water, filtrates),
waste water originating from equipment cleaning (e.g. during maintenance, rinsing of
blockages or product caking, cleaning of multi-purpose equipment because of campaign or
product change).
Specific treatment steps to remove interfering constituents can improve the efficiency of a
recirculation operation. Thus, for example, neutralisation, stripping or filtration of process water
streams can enable water to be re-used, e.g. as raw water or utility water supply. The reuse of
process water (make-up water, mother liquors) is possible, when constituents such as byproducts or salts will not adversely affect the quality of downstream productions. In fact, in
multiple stage product washing, washing water streams can frequently be used as make-up
water, or as input water into a preceding washing step.
The re-use of water from washing, rinsing and equipment cleaning, has, in addition to the
reduction of waste water load, the advantage of product recovery and increase of product yield,
provided the water is recirculated into the production process itself. This requires facilities for
collection, stocking or storage of waste water, which might be a limiting factor.
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1.1.2.1.3
Indirect Cooling with Vapour Phases
The injection of water into a gaseous phase is used to cool or condense vapours. The direct
contact of water with vapour phases, however, generates large amounts of waste water polluted
by the vaporous contaminants. Introduction of surface heat exchangers instead of injection
condensers/coolers avoids the generation of polluted cooling water streams, the pollutants
remaining in the condensate. So, indirect cooling/condensing leads to water saving. To give
some idea of the potential savings it takes approximately 27 m3 of water to cool one tonne of
steam down to 35 C (the temperature generally accepted as an upper limit for discharge). With
indirect cooling this amount is run in a cooling cycle [cww/tm/82] replacing only water lost by
evaporation.
Water saving effects are decreased when entrained particles, sublimating material, crystals or
caked matter coat the heat exchange surfaces, or plug the spaces between the exchange surfaces,
so they need regular maintenance.
There are, however, processes where a conversion to indirect cooling is not appropriate
[cww/tm/82].
It can, for example, be necessary for crystallisation to stir a liquid organic phase vigorously
together with warm or hot water, and then to bring down the temperature rapidly below
solidification temperature by adding ice or cold water (temperature shock). The goal of this
procedure is to get a filterable suspension without lumps or clots.
Another example is the standard process for diazotization of amines. In this process,
temperature is kept at a constantly low level by the addition of ice, to prevent thermal
decomposition of the diazonium compound as well as its deposition on equipment, which
otherwise would mean a considerable risk of explosion.
One further example is the quenching of hot gas streams, where cold water is injected into the
gas stream to decrease its temperature so effectively and rapidly that reactions of components in
the gas stream are prevented (e.g. recombination reactions in flue gas from combustion
processes resulting in generation of PCDDs and PCDFs).
1.1.2.1.4
Waste Water-free Processes for Vacuum Generation
Owing to their almost undisturbed operation, their low maintenance requirement and their low
costs, water jet and vapour jet vacuum pumps are used universally.
Waste water-free vacuum generation can be achieved by using mechanical pumping systems in
a closed circuit procedure or by means of dry-running pumps, the closed circuit system
discharging a small amount of water as blowdown. This discharge amounts to less than 5 % of
that of the once-through system [cww/tm/82]. In some cases, waste water-free vacuum
generation can be achieved by use of the product as barrier liquid in a mechanical vacuum
pump, or by use of a gas stream out of the production process.
Whether waste water-free vacuum generation is possible has to be determined in each particular
case. In selecting the proper process, account needs to be taken of the potential problems,
particularly with respect to corrosion, tendency to caking, explosion risk, plant safety and
operational reliability. Appropriate limitations have to be considered, especially in the case of
mechanical vacuum pumps with closed cycle, such as liquid ring pumps, rotary sliding-vane
pumps or diaphragm vacuum pumps. Here, for example, vapours can decrease the lubricity of
the oil.
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Provided that gas condensation in the pump is prevented by, e.g., high gas outlet temperature,
dry-running pumps are an attractive option, when solvents are to be recovered, or when a high
vacuum is necessary. These pumps cannot be employed if the gas stream contains large
amounts of condensable, dust-forming or coating material.
1.1.2.1.5
Waste Water-free Processes for Exhaust Air Cleaning
About one third of the exhaust air cleaning systems in the chemical industry works with a
water-based scrubbing process. This captures especially inorganic compounds such as hydrogen
chloride, sulphur dioxide, nitrogen oxides, etc, as well as water-soluble organic substances.
Waste water-free technologies for exhaust air cleaning are used, in particular, when hazardous
substances or non-degradable organic substances would otherwise find access to a biological
waste water treatment plant, where they might cause disturbances or would discharge untreated
into the recipient water.
Examples of waste water-free technologies for exhaust air cleaning are [cww/tm/82]:
Exhaust air incineration that can be used as an energy source. The exhaust air streams are
collected separately and used in power stations or in other operational energy recoveries. A
precondition for this technology is a proper infrastructure. Treating the entire exhaust air
from a site by incineration is cost-intensive and has a low or negative energy yield.
Gravity separators (e.g. demisters) and bag filters are used for separating particulates.
Adsorption systems (e.g. activated carbon) are used for exhaust air streams loaded with
non-polar organic substances.
Use of organic solvents instead of water as scrubbing liquid, when organic contents are to
be removed.
1.1.2.1.6
Substance Recovery or Retention from Mother Liquors or by Optimised

Processes
Substance recovery of waste water constituents with reasonable expenditure is normally only
feasible for concentrated waste water streams. So it is usually limited to mother liquors.
Depending on the method of synthesis, mother liquors are generally aqueous solutions kept after
product separation, or washing water. Recovery might comprise, e.g.:
removal of utilisable individual compounds, such as starting materials, products, solvents,

catalysts, etc.,
material conversion with subsequent substance recovery, e.g. incineration with recovery of
chlorine as hydrochloric acid.
Substance recovery is viable for higher waste water concentrations (percentage range). If easily
removable components are concerned, e.g. volatile, solid, precipitable or extractable
compounds, recovery processes might be viable even at lower concentrations.
Substance retention by way of optimised processes encompasses the modification of process
steps as well as additional measures, such as improvement of mother liquor work-up. These
aims can also be achieved by multifunctional production integration, which affects all process
steps with influence on the waste water route.
Substance retention aside from pollutant prevention such as modification of formulation or
improvement of production yield can also be achieved by pollutant removal, e.g. adsorption or
extraction, or by conversion, e.g. oxidation or incineration.
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1.1.2.1.7
Use of Low-contaminated Raw Materials and Auxiliaries
Contaminated raw materials and/or auxiliaries can import pollutants into the production chain
and thus into the waste water system. Examples are:
metals from crude vegetable fats, or from crude sodium hydroxide,

chloro-organic compounds (AOX/EOX) from technical-grade hydrochloric acid,
contaminants of, in particular, intermediates and externally acquired precursors.
The operators ability to influence this situation is limited by:
insufficient information from suppliers,

increase of contaminant importation because of recycled materials,
transferring emission problems to other locations by work-up of the raw material.
1.1.2.2 End-of-pipe Measures

According to Metcalf & Eddy [cww/tm/4] the application of waste water treatment methods can
be divided into:
Preliminary Waste Water Treatment, which means the removal of waste water constituents
such as debris, rags and coarse suspended matter that may cause maintenance or operational
problems to the treatment operations, processes and ancillary systems.
Primary Waste Water Treatment, which means the removal of suspended solids and organic
matter with physical operations.
Secondary Waste Water Treatment, which means the removal of biodegradable organics
and suspended solids.
Tertiary or Advanced Waste Water Treatment, which means the level of treatment required
beyond secondary treatment to remove constituents of concern including nutrients, toxic
compounds, etc. The major part of pre-treatment operations or processes for segregated
waste water streams is included here.
The contaminants of major interest in industrial waste water and the unit operations, processes
or methods applicable to the removal of these contaminants are reviewed in Table 1.1
[cww/tm/4].
In the chemical industry as well as in any other industrial sector end-of-pipe measures
downstream of process-integrated measures are important contributors to the reduction of waste
water and the pollutants it carries. These end-of-pipe treatments encompass pre-treatment or
final treatment of segregated waste water streams as well as the final treatment step of collected
waste water before discharge into a recipient water. These treatment measures are manifold in
the chemical industry. Because of economic limitations - and sometimes lack of space
process-integrated measures are mainly implemented in newly built plants or production
processes, or in existing installations for a continuous output of large volume products. Existing
plants and/or processes especially when speciality chemicals and batch processes are involved
prefer decentralised end-of-pipe treatment at the point of production and/or central end-ofpipe systems.
Complex chemical production sites normally have an extensive system for the collection and
treatment of process water. Up to now the main contribution to decrease organic pollutant load
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in chemical industry has been made by centralised biological waste water treatment technology,
combined with upstream neutralisation and precipitation, where all waste water streams are
collected and finally treated together. At the outlet of optimised biological Central Waste Water
Treatment Plants (CWTP) BOD concentrations below 20 mg/l are to be found, with elimination
rates at appropriate starting concentrations of about 98 % [cww/tm/82]. The elimination
rates of COD/TOC are in the range of 60 95 %, usually between 85 95 % [cww/tm/82].
Many components are biodegradable and can be treated very efficiently in such a system.
However, attention should be paid to non-biodegradable and/or toxic components. Their
presence may reduce the efficiency or even upset the operation of the CWTP.
Contaminant
Unit Operation, Unit Process or Treatment System
Suspended solids
Screening and comminution

Grit removal
Sedimentation
Filtration
Flotation
Flocculation
Coagulation/sedimentation
Biodegradable organics
Activated-sludge variations
Intermittent sand filtration
Physical-chemical systems
Volatile organics
Air stripping
Off-gas treatment
Activated carbon adsorption
Pathogens
Chlorination
Hypochlorination
Bromine chloride
Ozonation
UV radiation
Nutrients: Nitrogen
nitrification and de-nitrification variations

Ammonia stripping
Ion exchange
Phosphorous
Metal-salt addition
Lime coagulation/sedimentation
Refractory organics
Activated carbon adsorption

Tertiary ozonation
Heavy metals
Chemical precipitation
Ion exchange
Dissolved organic solids
Ion exchange
Reverse osmosis
Electrodialysis
Table 1.1: Unit Operations and Processes and Waste Water Treatment Systems used to remove
Major Contaminants found in Waste Water
The biological elimination rate of COD/TOC is mainly influenced by the content of readily
degradable and non-readily degradable substances, the latter also called recalcitrant COD or
refractive COD. Quantitative predictions on biological degradability of organic pollutants in a
CWTP are not possible without prior tests. Nevertheless, a rough estimation by rule of thumb
on biological degradability of particular waste water streams can be given:
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readily degradable are aliphatic compounds (paraffins, alcohols, carboxylic acids),

branching, ring closures and substitutions, in particular in compounds containing
heteroatoms, lead to non-readily degradable compounds,
mononuclear and binuclear aromatics (aniline, phenol, naphthalene) are subject to
biodegradation with an adapted biology,
functional groups, such as -SO3, -NO2, -Halide, at aromatics tend to loss of degradability,
increase of number of functional groups lead to decrease of degradability,
increase in water solubility of the organic compound due to hydrophilic functional groups,
such as -NO2, -NH2, -COOH and, in particular, -SO3H, leads to decreased elimination,
because the tendency of adsorption to the activated sludge as well as the adsorption capacity
of the bacteria decrease.
Before entering a CWTP chemical industry waste water normally passes through several pretreatment steps. Frequently, the waste water feed undergoes a neutralisation step, combined, if
necessary, with precipitation/sedimentation or precipitation/flocculation/sedimentation to
separate heavy metals and/or particulate organic constituents. Production residues might be used
as auxiliaries for operating the CWTP, e.g. acids or lyes for neutralisation, lime milk, iron and
aluminium compounds for precipitation/flocculation, inorganic phosphorous and nitrogen
compounds as nutrients. Those residues should not contribute significantly to environmental
pollution.
The sludge is separated, de-watered and, because of its toxic constituents, finally incinerated.
Waste water from sludge de-watering is generally recirculated to the CWTP feed, its COD
concentration being similar to that of the waste water feed.
Waste water from chemical industry might also be treated together with municipal waste water,
either in Municipal Waste Water Treatment Plants (MWTP) or in specially built plants for the
combined treatment of municipal and industrial waste water. The joint treatment is frequently
arranged in such a way that, because of its high initial organic loading and the tendency to
decreasing degradation rates in diluted waste water, the industrial waste water initially
undergoes a high performance step (e.g. tower biology), and is subsequently joined by the
municipal waste water in a second biological step.
Experience has shown that the joint treatment of municipal and chemical industry waste water
has at least at a first approach neither synergetic nor antagonistic effects [cww/tm/82]. The
disposed pollutant loads are additive. Nevertheless, an assessment of each case is
recommended, because the joint treatment may have advantages and/or disadvantages.
Advantages can be:
The operational stability of joint biological treatment can be favourably influenced by:
- improving the nutrient conditions,
- optimizing the waste water temperature and thus the degradation kinetics,
- equalizing the feed load, as long as the daily progress lines of the two waste water
streams are correspondingly structured, or can be matched to one another,
- suppressing the toxic and inhibitory effects of waste water constituents by lowering
the concentrations below the critical thresholds.
The joint treatment of waste water and sludge can, in individual cases, realise savings in
capital and operating costs.
Disadvantages can be:
Systems with mixed drainage can suffer from hydraulic overload in the event of heavy
rainfall, which might lead to increased pollutant discharge accompanied with loss of
bacteria from the activated sludge compartment of the CWTP.
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Reduced cleaning performance due to production related operation disturbances, which

leads to increased water pollution because of insufficient treatment of both municipal and
industrial waste water streams.
A good number of chemicals can, even at lower concentrations, hinder nitrification. If the
nitrification step collapses, it might take several weeks to recover and ensure sufficient
nitrogen elimination again. So, to minimise the risk for joint waste water treatment, it is
crucial to study and monitor carefully the waste water streams coming from the industrial
part for any inhibiting or disturbing factors.
Combined treatment of waste water streams from different origins bears the risk that
persistent contaminants, such as heavy metals and non-biodegradable compounds, can
escape control - ad sometimes even detection because of dilution. These contaminants
discharge without degradation into a recipient river, adsorb onto the activated sludge or are
stripped into the atmosphere during aeration. This would counteract the obligation to
prevent or control these substances at source. This disadvantage affects all treatment actions
on combined waste water streams.
Waste water from the production of inorganic chemicals is usually treated mechanically and/or
chemically before discharge into a recipient. These streams or tributary streams usually
circumvent the CWTP, because otherwise they might disturb its biological efficiency.
Another important aspect of the waste water system is the handling of rainwater and rinsing
water. In many older chemical complexes, only one sewer system is present and rainwater,
rinsing water and process water are collected in this system and directed to the waste water
treatment facilities. Especially during periods of heavy rainfall, this might lead to upsets of the
waste water treatment plant and lead to increased discharges. Modern plants usually have a
separate sewer system for the collection of rainwater. Normally, this sewer system is designed
as a first flush system. This means that the first rainwater, which may carry contamination
from roofs, roads and paved areas, is directed to a waste water treatment facility and the clean
water that follows is discharged directly to the surface water disposal system.
1.1.2.3 Waste Water Management

Waste water management describes the involvement in concept finding, planning, evaluation,
design, construction, operation and maintenance of a chemical site: i.e. a strategy to meet all
objectives connected with waste water. Waste water management encompasses, e.g.:
consideration of possible environmental impact when planning new production lines, or

planning enlargement of existing lines,
decision on implementation of process-integrated measures,
decision on production path,
decision on choice of the discharge path,
decision on implementation of central or decentralised waste water treatment,
decision on how to minimise contamination,
decision on creating an appropriate infrastructure, or to alter an existing one, for the
purposes of improving waste water quality,
evaluation of cross-media effects of the different treatment strategies.
These are only a few of the tasks efficient waste water management has to tackle. The
economical issues should not be overlooked.
Following [cww/tm/27], an overall waste water strategy should be developed by operators. It is
important for this strategy to reflect the fact that water is an increasingly valuable resource and
in some circumstances it will be possible to achieve recycling of treated effluent water for use
elsewhere on-site. The purpose of effluent treatment can be to achieve recycling or water
recovery, as well as to improve discharge quality. This overall waste water strategy has, in the
10
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final analysis, a site-specific focus, applicable only for this particular situation. But
nevertheless, the approach to achieve such a result consists mostly of general or horizontal
applications.
When planning and designing a production process, the first aim should be the prevention of
waste to be discharged as waste water. This means selecting clean technologies and clean raw
materials. If as is usually the case complete prevention of waste/waste water is not
practicable the next step is minimisation not only of volume, but also of impact caused by
hazardous substances that might be replaced in the production process. If all measures for
minimisation are taken, the next step is controlling the inevitable discharge by implementing the
most effective waste water treatment system possible, so as to minimise the total environmental
impact. The choice of the most appropriate treatment system will be based on an evaluation of:
its control efficiency,

its energy needs,
its space requirement,
the possible generation of
- (waste) gases,
- waste,
- noise,
its consumption of resources.
Another issue to take into account is the nature of the recipient water into which the industrial
site is going to discharge its waste water. It may be such as to demand special and more
stringent requirements of the effluent quality.
Planning of action is only one part of waste water management. The next and more important
step is a process of continuous improvement of a given situation, i.e. all the different stages and
steps have to be done and redone repeatedly over time. This is usually supported by company
policy on environmental issues for all their sites and by Member State legislation.
Step 1 : characterisation of individual waste

streams and total effluent
Step 2 : maximisation of preventive measures
Step 3 : identification and assessment of treatment

opportunities for each individual waste stream
Step 4 : evaluation and assessment of whole plant

treatment scenarios
Figure 1.1: General Waste Water Management Strategy
As can be seen from the short enumeration above, waste water management has a lot to do with
decision making between at least two but normally more options in light of the particular
situation. And it has of course to do with economics and competitiveness. The main
question to answer is: How can one operate a complex site and manage its water demands
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supply and discharge with the least possible impact on the environment as a whole, with the
highest economic efficiency and without any loss of product quality?
The assessment of the optimum mix of control and treatment measures for the chemical industry
involves basically a four-step management approach [cww/tm/84] as presented in Figure 1.1.
But this approach does not imply that waste water management is a once-through process,
fulfilling step 1 4. It actually involves a complex and repeating iterative process of all
steps.
Opportunities for waste water management are different for new and existing plants. In new
plants, preventive control measures and in-plant segregated waste stream treatment can be
effectively taken into account in the design stage of the plant. For existing plants, retro-fitting to
existing installations and infrastructure may involve technical and organisational constraints and
will be more expensive in general. However, the approach and principle of water management
as proposed in this chapter are basically the same for new and existing plants.
For existing plants, the starting point of a waste water management strategy will be a
compliance evaluation to determine if the current treatment measures will meet present and
potential new effluent discharge requirements. Thus for existing plants, waste generation
characterisation (step 1) involves not only the characteristics of the waste streams at source, but
of the effluent discharge as well, including toxicity testing.
Based on the knowledge of the generation of wastes of specific sources and the manufacturing
processes involved (step 1), potential methods are identified (step 2 and 3) for:
preventive (in-plant) source control measures,

in-plant treatment measures of segregated streams,
end-of-pipe treatment of combined streams.
In the identification and evaluation of treatment scenarios (step 3 and 4), individual treatment
systems are generally characterised by their ability to treat specific pollutants the target
pollutants. However, waste water streams may also contain pollutants that are not removed by
the treatment process concerned. These pollutants secondary pollutants may even inhibit the
treatment process to the extent that they render the treatment operation/process inappropriate.
This provides the basis for the main principle of waste water management. An effective waste
water management strategy is based on the principle that the introduction of pollutants into final
treatment systems not designed for their removal should be avoided or minimised.
For each individual waste water stream, step 3 of the waste water management scheme will
therefore generally include the identification and assessment of costs, removal efficiency, and
cross-media effects of the following treatment opportunities:
treatment in a combined end-of-pipe unit, including the assessment (quantification) of the

potential effects of secondary pollutants,
individual treatment of segregated streams
- in-plant,
- centrally (possibly combined) in special treatment facilities,
- end-of-pipe pre-treatment,
tertiary treatment or enhanced end-of-pipe treatment.
The optimal combination of individual in-plant treatment and combined end-of-pipe treatment
measures is evaluated in step 4 of the management scheme, by comparing selected scenarios
for:
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the overall removal efficiency, e.g. of:

- organic content (BOD, COD, TOC),
- AOX/EOX,
- toxic organic compounds,
- metals,
- nutrients (nitrogen, phosphorous),
the overall balance of cross-media effects (air, waste and energy),

the financial feasibility,
the organisational and technical feasibility.
A detailed description of waste water management systems and tools to implement them is
given in Chapter 2 of this document.
1.2 Waste Gas in Chemical Industry

1.2.1 Characteristics
Waste gas streams can roughly be divided into ducted and non-ducted, or fugitive, emissions.
Only ducted emissions can be treated. As far as fugitive emissions are concerned the objective
of waste gas management is their prevention.
The emission sources for waste gas and exhaust air in chemical industry are:
Ducted emission sources, such as:

- emissions through a collection system, diluted or not diluted by air or another
carrier gas,
- general ventilation system exhaust,
- process vents to the atmosphere, which are normally continuous or semicontinuous, such as combustion related emissions,
- purge vents, which are used only on start-up or shut-down operations,
- storage vents, e.g. tank vents, to the atmosphere,
- safety vents from the discharge of safety relief devices,
- product handling vents from transfers, loading and unloading,
- vents from captured diffuse sources, i.e. diffuse sources installed within an
enclosure or building,
- VOCs passed through an abatement system without being abated.
Multiple emissions inside a building are normally considered as diffuse emissions.
Diffuse emissions, i.e. emissions arising from direct contact of volatile components with the
atmosphere under normal operating circumstances. These can result from:
- the design of the equipment (e.g. filters, dryers, etc.),
- the operating conditions (e.g. transfer of material between containers),
- the type of operation (e.g. maintenance activities),
- a gradual release to other media (e.g. to cooling water or waste water).
Diffuse emission sources can be point, linear, surface or volume sources.
Fugitive emissions, which are a subset of diffuse emissions, such as:

- volatile components left in water,
- VOCs contained in solid or liquid waste,
- VOCs contained in the product of the facility.
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Non-ducted and non-fugitive emissions, from e.g. flares.
The usual causes for emissions of waste gas and exhaust air from a facility are:
Process emissions, which are released by the process equipment and are inherent to the
running of the plant. They can either be ducted, when released through a vent pipe, or nonducted, when released from a large surface or through openings, etc.
Emissions from storage tanks, subdivided into

- working losses, which occur when the tanks are being filled,
- breathing losses, caused by expansion of vapours when the storage temperature is
increasing (e.g. solar radiation).
Handling emissions, which are released when drums, trucks or containers are being filled.
Equipment leaks from pump and compressor seals, valves, flanges, connectors and other
piping items, or other equipment items, such as drain or vent plugs, seals, etc. These
emissions are usually fugitive emissions.
Secondary emissions, resulting from the handling or disposal of waste. Typical examples
are emissions to the atmosphere from sewers or waste water handling facilities, or
emissions in cooling towers caused by leaks of volatile products into the cooling water.
Non-routine emissions, resulting from operations other than the routine processing of the
facility, including emissions during start-up or shutdown, and during maintenance.
Accidental emissions, caused by incidents and spills of volatile products during which
vapours are released to the atmosphere.
The main air pollutants from chemical processes and energy supply are:
sulphur dioxide and other sulphur compounds,

nitrogen oxides and other nitrogen compounds,
carbon monoxide,
volatile organic compounds (VOC), which encompasses compounds with carcinogenic
potential,
particulate matter, dusts and soot which can contain heavy metal dusts and carcinogenic
compounds,
Emissions from process furnaces, steam boilers and power generating units are directly related
to the energy consumption of the process. Energy saving results in lower emissions from these
units.
1.2.2 Waste Gas Treatment

Establishing the possibilities for reducing waste gas emissions begins with a survey of the
production process and process management. In the choice of measures for emissions reduction
the following ranking is generally employed:
process-integrated measures,
end-of-pipe techniques.
Treatment of emissions to air normally takes place on-site and usually directly at the point of
generation. Transport of contaminated waste gas streams over longer distances is normally not
feasible due to the costs of transport (piping) and possible problems during transport
(condensation, corrosion, clogging etc.). Only rarely can waste gas streams with different
characteristics be treated simultaneously in one treatment unit. The main reason is that treatment
units are specifically designed for a particular waste gas composition.
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Special attention should be paid to the release of toxic and hazardous components and their
impact on the surroundings of the plant. In the chemical industry, given the toxicity and/or
hazardous characteristics of many components and the generally large volumes that are handled
and processed, external safety is an important issue.
From an environmental point of view process-integrated measures are preferred to end-of-pipe
techniques, because they ensure a source control approach. Process-integrated techniques entail:
modification of the production process,

use of different raw material,
recycling of the pollutants.
Technique
Dust separation
Separator
Cyclone
Dust scrubber
Electrostatic precipitator
(1-stage)
Electrostatic precipitator
(2-stage)
Dust filtration
Fabric filter
Catalytic filter
Ceramic filter
2-stage dust filter
Absolute filter
HEAF filter
Mist filter
Condensation
Cryocondensation
Condenser
Adsorption
Activated carbon
Regenerative adsorption
Zeolite filter
Absorption
Scrubber
Scrubber (alkaline)
Scrubber (alkaline-oxidation)
Scrubber (biogas desulphurisation)
Scrubber (acid)
Biological
Biofiltration
Bioscrubber
Oxidation
Thermal incinerator
Catalytic incinerator
Recuperative incinerator
Regenerative incinerator
Miscellaneous
Dry lime injection
Semi dry lime injection
SNCR
SCR
Membrane filtration
x
(x)
=
=
inorganic
components
in
gas and
vapour
form
organic
components
in
gas and
vapour
form
x
x
x
x
(x)
(x)
(x)
(x)
x
x
x
x
x
x
x
x
x
x
dry
matter
wet
matter
particulate
inorganic
components
particulate
organic
components
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
(x)
(x)
(x)
odour
(x)
(x)
x
(x)
x
x
x
x
x
x
x
x
x
(x)
(x)
(x)
(x)
(x)
(x)
(x)
(x)
(x)
(x)
(x)
(x)
(x)
(x)
(x)
(x)
(x)
(x)
(x)
(x)
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
(x)
x
primary application
secondary application
Table 1.2: Selection of Techniques for Waste Gas Emission Reduction in Relation to the Pollutant
to be removed
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If process-integrated measures are not possible, or do not achieve an adequate reduction, endof-pipe techniques are used. A proper selection of waste gas treatment techniques is part of a
management system, described in Chapter 2. The main selection criteria are:
characteristics of the pollutant,

flow rate of the waste gas stream.
A selection of techniques by pollutant is given in Table 1.2, and by waste gas flow rate in Table
1.3 [both cww/tm/70].
Technique
Dust separation
Separator
Cyclone
Dust scrubber
Electrostatic precipitator (1-stage)
Electrostatic precipitator (2-stage)
Dust filtration
Fabric filter
Catalytic filter
Ceramic filter
2-stage dust filter
Absolute filter
HEAF filter
Mist filter
Condensation
Cryocondensation
Condenser
Adsorption
Activated carbon
Regenerative adsorption
Zeolite filter
Absorption
Scrubber
Scrubber (alkaline)
Scrubber (alkaline-oxidation)
Scrubber (biogas desulphurisation)
Scrubber (acid)
Biological
Biofiltration
Bioscrubber
Oxidation
Thermal incinerator
Catalytic incinerator
Recuperative incinerator
Regenerative incinerator
Miscellaneous
Dry lime injection
Semi dry lime injection
SNCR
SCR
Membrane filtration
x
xx
=
=
100
[m3/hour]
1,000
[m3/hour]
10,000
[m3/hour]
100,000
[m3/hour]
x
x
x
xx
x
xx
x
x
x
xx
xx
xx
xx
xx
x
x
x
x
xx
x
x
xx
x
xx
x
x
x
xx
x
x
xx
xx
x
x
x
x
xx
x
x
x
xx
xx
x
xx
xx
x
x
x
x
x
x
x
x
x
x
x
x
x
x
xx
xx
xx
xx
xx
x
xx
xx
x
x
xx
x
x
xx
x
xx
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
xx
x
x
xx
application
most common applications
Table 1.3: Selection of Techniques for Waste Gas Emission Reduction in Relation to Waste Gas
Flow Rate
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1.2.3 Waste Gas Management

The air management strategy is part of the overall environmental management of a plant. There
are some aspects of the environmental management that are specific to air emissions, which are
discussed here.
The well-known cascading approach of prevention, process-integrated solutions and end-of-pipe
treatment generally also applies to air emissions. Special fields of attention with regard to
emission prevention are:
the raw materials and fuel composition,

the required volume of process air,
the presence of and need for inert gases in the process (e.g. nitrogen from ambient air),
the energy consumption and
the combustion conditions.
In contrast to waste water, there are substantial components of waste gas namely non-ducted
(or fugitive) gas effluent that are not susceptible to treatment. They have to be dealt with by
prevention techniques, which then become an issue for management. The management of
fugitive emissions relates to detection, quantification methods, equipment selection,
housekeeping and preventive maintenance measures. So waste gas management encompasses,
e.g.:
consideration, when planning new production lines, or planning the enlargement of existing
lines, of possible environmental impact of emission of waste gas, including fugitive
emissions,
decision on implementation of process-integrated measures, to prevent gas emissions, either
by:
- changing the production pathway,
- recirculating the gas stream or
- recovering the gaseous contaminant.
decision on choice of the discharge pathway,
decision on implementation of central or decentralised waste gas abatement,
decision on how to minimise contamination,
decision on creating an appropriate infrastructure, or to alter an existing one, for the
purposes of improving waste gas quality,
decision, so as to prevent fugitive emissions, to replace older equipment which tends to
have a high leakage rate,
decision to implement a Leak Detection and Repair (LDAR) programme.
These are just some of the tasks efficient waste gas management is confronted with. It also has
to handle atmospheric concerns on an economically viable basis.
As can be seen from this short enumeration, waste gas management as with waste water
management has a lot to do with deciding between at least two but normally more options
with regard to the circumstances of each situation. And it has of course to do with
economics and competitiveness
Planning of action is only one part of waste gas management. The next and more important step
is a process of continuous improvement of a given situation, i.e. all the different stages and
steps have to be done and redone repeatedly over time. This is usually supported by company
policy on environmental issues for all their sites, and by Member State legislation.
A detailed description of waste gas management systems and tools to implement them is given
in Chapter 2 of this document.
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1.3 Interdependencies between Waste Water and Waste Gas

Treatment
Although waste water treatment systems generally reduce the emissions to water, the operation
of these systems has its own environmental effect. Especially relevant with regard to emissions
to air from waste water treatment are those water streams which are polluted with volatile
organic compounds (VOC) and volatile inorganic compounds (e.g. ammonia, hydrogen
sulphide, etc.). Whenever these water flows are in open connection to the atmosphere, (odorous)
emissions of these components may occur. Special attention should be paid to aeration of
biological waste water treatment basins, stirring operations, open buffer tanks and settling tanks.
Air emissions may also evolve from the mixing of water flows with different temperatures or
the addition of acids or caustic for pH-adjustment. This is briefly reviewed in Table 1.4
[cww/tm/85].
Other relevant points of concern are the energy consumption and (in some cases) sludge
generation of the water treatment techniques. In many anaerobic biological waste water
treatment units, the gas generated from the treatment (biogas) is used as a fuel.
In addition to flares and incinerators, a large number of environmental and safety facilities can
be found in the chemical industry. The main purpose of these facilities is to reduce the
environmental impact and increase the safety of the plant operation. The facilities vary from
very simple measures to complicated treatment units.
In general, the overall effects of the environmental and safety facilities should be positive. That
is the reason for installing them in the first place. However, many facilities also have negative
impacts on the environment. Examples of these cross media effects are waste generated from
filters, waste water generated from scrubbers and increased energy consumption. It is very
difficult to give an indication of the break-even point, where the positive effects outweigh the
negative effects of a facility. As a rule of thumb one could say that local environmental quality
and safety should have priority. Furthermore, it is generally considered preferable for pollutants
to be in the most concentrated and controllable state. This offers the best opportunities for
recycling, further treatment or controlled disposal.
Environmental
compartment
Potential effect/emission
Air
Water
Waste
Other
Evaporation/formation of odour (e.g. H2S, NH3,

mercaptans etc.)
VOC emissions (evaporating from the water)
In principle, significant reduction of water emission
May be an extra source of emissions if rainwater is
treated together with process water and treatment system
gets overloaded
Waste water treatment sludge
The CWTP plant consumes energy. In some cases,
biogas is generated and can be used as a source of
energy.
Table 1.4: Potential Emissions from Waste Water Treatment Plants
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2 WASTE WATER/WASTE GAS MANAGEMENT

2.1 General Description of Management Systems
A proper management system of which waste water and waste gas management systems are
part is a tool to help to secure and improve environmental performance. Potential accidental
and/or fugitive emissions are normally also covered by the environmental management system.
The specific implementation of such a system at a given site depends on the environmental
impact of the activities carried out there, as well as the specific situation of the environment at
and around this site.
This horizontal document will give a general schedule to implement a management system by
first working out its characteristics, and subsequently describing the tools, instruments or
techniques that are applied to it.
All parts of Chapter 2.1 are intended to belong to both compartments, waste water and waste
gas, and are run together to avoid repetition for each medium.
2.1.1 Listing of a Quantified Inventory of all Streams

An appropriate inventory lists all sources on a site, describes the collection system, and provides
adequate characterisation of all streams.
2.1.1.1 General Information

2.1.1.1.1
Site Information
The general information listed below is needed to perform an estimation of the quantity of
effluent leaving the site and its influence on the neighbourhood. Information on:
location (map, plot plan),

size of the site (total area, built up area, drained area, covered area),
number of employees,
production units,
climate, geography, quality of soil and groundwater, neighbourhood.
2.1.1.1.2
List of Production Plants
Information for each production plant that discharges waste water and/or waste gas has to be
collected. The information comprises:
typical production plant data,

classification of production plants according to the Directive, Annex I, 4. Chemical
Industry, 4.1 4.6.
2.1.1.1.3
Information on the Production
The information comprises:
brief description of each production,

simplified process scheme,
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Chapter 2
chemical reactions (main and side reactions) and supporting operations,

operating material, intermediate and final products,
continuous or batch process or campaign operation,
sources of waste water and/or waste gas streams,
potential emergency situations (spills, leakages).
2.1.1.2 Stream Inventory

The compilation of relevant basic data on the composition and quantity of waste water and/or
waste gas streams are done in a Stream Inventory which includes each waste water and/or waste
gas stream. The streams will be listed according to the source from which they originate,
because this will be a key element in assessing their degree of contamination and the nature of
the contaminants, as well as the source reduction possibilities. Stream inventories are
management tools.
2.1.2 Setting of Internal Targets for Effluent Streams

In order to comply with the permit and further environmental restrictions that are granted for a
final discharge of waste water and/or waste gas a clear set of rules and procedures dealing with
the particular streams contributing to the final discharge is needed. Further details are described
later (Chapter 2.2.1.2 below).
2.1.3 Regular Review of Targets in Order to meet Anticipated Changes

The chemical industry and its surrounding conditions are changing constantly, e.g. according to:
quantity and quality of products,

new products,
new technologies,
new scientific knowledge,
new legal requirements,
new public perceptions and concerns,
new regional planning.
To meet these changes, a programme for continuous reduction of emissions as a management

tool has to be set up.
2.1.4 Selection of the most Appropriate Emission Control Options

Having collected all necessary information concerning emissions on a chemical site, and having
defined the environmental targets and demands made for this site, the next logical step would be
the selection of the most appropriate control options. Usually, the goal of a proper selection is to
find a cost-effective treatment method offering an optimum environmental performance. There
exist several helpful tools that are described in the special chapters for waste water and waste
gas respectively.
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2.1.5 Implementation of the Selected Emission Control Options

Once emission control measures have been selected, their implementation must be planned in
detail, regardless of whether they are of an organisational or hardware nature. Preparation
should always include at least one thorough review of the implementation plans to ensure that
the integrity of the plant is not compromised by the proposed changes. When unexpected
problems are identified during the detailed planning and/or review, the selection of the emission
control options may need to be revised.
The time required to implement emission control measures depends very much on the nature of
the measures and the type of facility where they need to be implemented:
Organisational measures, e.g. revision of operating procedures, scheduling practices, etc.,

can usually be implemented relatively quickly.
Control measures, e.g. computer control optimisation routines, may take several months to
develop and test in the operating environment.
Hardware measures, e.g. implementation of control devices, process modifications aimed at
source reduction, etc., may require from several months to several years depending upon the
size of the project and the ability to implement them in a running plant environment. This
duration includes the design of the facilities, permitting, detailed engineering, procurement
of the equipment, installation and start-up. In many cases a full plant shutdown (turnaround)
is required to make plant modifications, and in large chemical or petrochemical operations
this may happen only once every few years.
2.1.6 Monitoring, Reporting and Record Keeping of Results

Monitoring of an effluent treatment installation follows the same sort of considerations as those
addressed for a chemical production unit. Thus, the monitoring programme can be defined by
consideration of the objectives, the content (data) and the guidelines or rules used.
Objectives can be related to:

- internal or operators point of view (efficiency, quality, process optimisation, etc.),
- external requirements or considerations (authorities for compliance checking, taxes
and fees determination, the public or interested parties for information).
The content of the programme will be defined in terms of planning, preparation,

implementation, data analysis and reporting, answering such questions as:
- which parameter to examine,
- where to take samples or to monitor permanently,
- which analytical method to use,
- which resulting data (average value, peak value, etc.) to consider,
- this will lead to an enhanced knowledge of:
the untreated (raw) effluent (composition and its variation, flux and its
variation),
the treatability of an effluent, according to the field of application of each
considered treatment technique,
the running of the treatment plant (control of parameters and adjustment of
process values to any change of raw effluent),
the treated effluent (compliance with requirements reduction or elimination of
substances or ecotoxicity).
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Guidelines or rules
Knowledge of the treated effluent, just before its release into the receiving media (water or
air), is of particular importance as a key element for impact assessment. In order to improve
the credibility of the reported data, the monitoring process should be based upon:
- internally agreed procedures,
- third party certification, either for analytical results (by laboratories), or for the
whole procedure (by qualified auditors).
2.2 Management Tools

2.2.1 General Management Tools
Environmental management plays an important part in the environmental development of a
company. The following tools embody a framework for good environmental management,
aimed at the adoption of effective operational techniques.
2.2.1.1 Environmental Management Strategy (EMS)

An EMS is that part of the overall management strategy which includes the organisational
structure, responsibilities, practices, procedures, processes and resources for developing,
implementing, achieving, reviewing and monitoring the environmental policy. It governs how
business and industry manage environmental, health and safety compliance and risk. Important
elements are a commitment of the management to environmental objectives, monitoring of the
environmental performance and an effort for continuous improvement. Several standards are
available to assist this approach. Well known are ISO 14000, EMAS and Responsible Care .
The EMS is an excellent tool to improve the integrated environmental performance of a plant. It
gives management the opportunity to:
gain insight in the pollution generating mechanisms of the production processes,

make balanced decisions about environmental measures,
avoid temporary solutions and no-return investments,
act adequately and pro-actively on new environmental developments.
Management involves a cyclic process of analysis, goal formulation, execution, monitoring and
evaluation. This is also valid for environmental management. Each step in the cycle has to be
taken carefully and tools are needed to generate the necessary information and to make the right
decisions. In the following paragraphs, the general principles of the management cycle are
discussed.
As shown in Figure 2.1, a plant-oriented EMS includes the following elements:
22
Characterisation and evaluation of individual manufacturing processes to understand how

environmental pollution is generated.
Identification of options to reduce the pollution, considering in descending order of priority:
- re-think and redesign technology,
- process-integrated pollution prevention,
- end-of-pipe treatment.
Assessment of the most effective options, taking into consideration:
- environmental benefits and side-effects (cross-media aspects),
- technical, financial and organisational feasibility,
- site-specific constraints and possibilities.
Execution and monitoring
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Chapter 2
Pollution
characterisation
and evaluation
Identification
of options for
improvement
Execution and
monitoring
Assessment
of most
effective
options
Figure 2.1: Example of a Plant-oriented EMS
2.2.1.2 Setting of Internal Targets

One of the prerequisites of a proper waste water management regime is the setting of internal
targets or goals for a chemical industry site. The parameters for which internal targets will be
set should be selected according to their relevance. In order to limit the number of these
parameters, the purpose of the target setting should be kept in mind, i.e. ensuring an optimum
running of production and abatement operations, thereby minimising the impact on the
environment as a whole. It is usually not necessary to set target levels for each and every
parameter involved, but to use surrogate parameters to describe the effluent. The measurable
target levels need to be set in such a way that the permit level of the final discharge as well as
the specific local conditions can be readily met.
There are several classes of targets, one class given as general standards, another as site-specific
standards. Examples for general standards are:
commitments of the chemical industry, e.g. the Responsible Care programme with its goal
of continuously reducing emissions from manufacturing units in the chemical industry,
the requirements of Environmental Quality Objectives (EQO) or Environmental Quality
Standards (EQS) as well as technology standards and Good Manufacturing Practice
(GMP),
the general requirements for River Basins Quality (Water Framework Directive or
Member States regulations on water quality),
requirements according to company internal standards issued for all their sites, independent
of local permit demands.
Examples of site-specific standards are:
requirements of permit conditions (e.g. ensuring continuous compliance with emission limit
values),
specific limitations on the ecotoxic waste water content of any final discharge in accordance
with the limits set for the recipient river,
cost allocation of the reductions to be achieved.
When targets are being set, a plan should also be drawn up for actions to be taken when a target
level of one or more partial streams, or of the final discharge, is exceeded for a certain amount
of time. These actions have to be clearly defined and the responsibilities and competence for
these actions have to be assigned. Examples of such actions are listed below:
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Chapter 2
storage of off-spec effluent,

increase of treatment efficiency, such as:
- increase of hydraulic retention time,
- addition of reactive compounds to the waste water stream,
- addition of activated carbon,
- recycling the effluent for a second pass through the treatment plant,
early maintenance or repair to contain the increase of emission,
reduce process operation regime, or even shutdown of the unit,
provide emergency storage,
special, or even external, treatment of the effluent.
The necessary action can be a single step or a combination of several steps.

To make sense of setting targets, an appropriate monitoring system has to be installed, which
provides the operator with the necessary data to check the operations relevant to waste water
and take the appropriate actions in due time. Immediate reports from the process units and the
waste water treatment units is required in case of accident or disturbance, to make sure that
immediate action can take place to avoid an unsuitable discharge to the environment.
2.2.1.3 Regular Review of Targets

Since science and technology are subject to continuous development, the setting of operational
and environmental targets is a dynamic process, which has to undergo a regular review,
regardless of whether new legal requirements have been introduced. The goal of this regular
review is the continuous improvement of the environmental performance of the chemical site as
a whole. To achieve this permanent goal, a reduction programme should be established that
contains the following elements:
24
A periodic evaluation of environmental management practices associated with operations

and equipment, taking into account:
- environmental impacts,
- changing legislation,
- public concerns,
- implementation of ongoing improvement.
Incentives for the implementation of cost-effective actions and recognition for significant
contributions to emission reduction targets, such as:
- pricing, which means the introduction of an internal Polluter Pays Principle for
effluent discharge. The separate production units are charged internally with the
costs of the treatment facilities according to their share of pollutant input.
- internal awards (bonus payment) for operation improvement proposals by staff.
- internal competition for reducing process disturbances and accidents.
Inclusion of objectives for effluent and release prevention in design of new or modified
facilities and processes, such as:
- introduction of recycling of starting compounds or products, when modifications of
the installation are planned,
- introduction of water conservation measures, under the same conditions as above,
Preventive maintenance and appropriate control technology to minimise emissions and
losses.
Implementation of engineering and operating controls and procedures, with operating
criteria, to improve prevention, early detection and containment of spills/releases. These
procedures can be implemented either by:
- monitoring surveillance or
- ensuring prevention, early detection and/or containment of releases done by
organisation measures, using manpower, like regular control rounds, or installing
containment systems with sufficient collecting volume.
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Investigation and evaluation of spills/releases that have occurred, to identify corrective

actions that will prevent a recurrence.
Communication with employees and members of the public regarding information on
effluent, emissions, the progress in achieving reductions and future plans. This
communication should include a structured dialogue on the concern and ideas of both
employees and members of the public.
2.2.1.4 Cost Benefit and Risk Considerations

According to the definition of BAT in the Directive, a cost-benefit evaluation should be
undertaken. This cannot be done without reference to varying degrees of performance risk.
Various technical options and combinations, each one fulfilling the requirements necessary to
be considered as BAT, can be expected to have associated with them particular advantages and
drawbacks, levels of ultimate performance, and costs, dependent on how they are applied in a
special situation.
For single substance parameters one tool to evaluate different technical options and emission
scenarios is the compliance with EQS. It is feasible to predict expected emissions resulting from
the application of different options or combinations of options, and calculate how these will
fulfil EQSs for a particular installation at a particular location. The result could be an indication
for the technical option to be suitable in this special situation.
However, this possibility to select a cost-effective BAT on the basis of a consideration of risk
cannot address all parameters. Various so-called summative parameters, e.g. TOC, COD,
BOD, AOX, EOX, total effluent toxicity, etc., which are commonly used for the purpose of
end-of-pipe checking or monitoring, cannot be easily related to the main contributors
(backtracking). It is therefore necessary to accept that the evaluation of different BAT options in
terms of their ability to minimise these parameters cannot be directly based upon risk, as can be
done for single substances.
Establishing average elimination efficiencies of different BAT options and linking these to a
cost curve would most likely be the best solution. However, even for these parameters, links to
risk considerations should be made as far as is practicable [cww/tm/72].
2.2.2 Waste Water Management Tools

Effective waste water management is crucial to prevention, minimisation and treatment of
discharges to a recipient. It requires real commitment to establishing the necessary management
techniques or tools. The following sections will provide information on the main types of
management tools.
2.2.2.1 Waste Water Register

The first step in installing a waste water management system is to gather relevant basic data on
the composition and quantity of each waste water stream or partial stream. A helpful tool to do
this is the setting up of a Waste Water Register, which provides the basis for decision making
about waste water segregation, prevention or reduction strategies, as well as waste water
control.
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A waste water register consists of:
information about the chemical production process, such as:

- chemical reaction formula including starting compounds, products and by-products,
- simplified process flow-sheet of the corresponding production unit, showing
reactor, work-up and product isolation, and exactly showing the origin of the
various waste water contributions,
information about the waste water streams, such as:
- relevant data on concentration and load of important waste water components,
- flow of waste water,
- temperature,
- pH,
- conductivity,
- relevant contaminants, such as COD/TOC, Nitrogen, Phosphorous, Heavy Metals,
Halogenated Hydrocarbons
data on biodegradability such as:
- BOD-concentrations,
- results from modified Zahn-Wellens-Test,
- recalcitrant TOC loads,
- denitrification inhibition potential.
The sources of waste water are listed according to their origin. This provides indications of the
waste water contamination. Waste water origins are, e.g.:
Process water streams, i.e. streams generated in the production process, including the workup and washing processes, or water contaminated by usage within the process. Seal drum
water purges or scrubbing effluent can be considered in this category.
Discontinuous maintenance or operation streams, resulting from distinct operations such as
cleaning, tank water draw-off, etc.
Contaminated water run-off from potentially contaminated areas, which may result from
floor washing, rain or fire fighting water.
Clean water run-off from non-contaminated areas, resulting e.g. from rain.
Cooling water run-off, which potentially can be contaminated.
Utility blowdown, such as originating from cooling water, boiler, boiler feed water
generation, etc.
Chemical effluent, e.g. laboratory effluent.
Sanitary waste water or kitchen waste water.
An appropriate ranking of the distinctive waste water streams e.g. corresponding to the
characteristic and load of contaminants might serve as an attractive basis for a decision on
further release reductions. Such contaminants are:
TOC/COD,
Nitrogen, Phosphorus,
AOX/EOX, or possibly individual Halide compounds,
Heavy Metals.
On chemical sites, measures for the reduction of emissions into water are best realised for those
chemical processes where an optimum of the environmental benefit and cost ratio is achievable.
For existing installations, non-optimum elimination rates for minor waste water streams not
carrying a significant load might be permitted in special situations. This could be tolerated if
efforts were instead concentrated on streams containing significant loads, thereby reducing
overall emissions and environmental impact.
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The waste water streams at the top of the ranking list are prime candidates for a most effective
emission reduction. Indications for the necessity of a more thorough examination of waste water
partial streams are:
recalcitrant TOC > 20 kg/day,

Heavy Metals > 1 mg/l,
halogenated compounds > 10 mg/l
Nitrogen > ?
2.2.2.2 Whole Effluent Assessment (WEA)

Whole Effluent Assessment means the estimation of all potentially hazardous effects acute
and chronic toxicity, genotoxicity, persistence, bioaccumulation characteristics, etc. of
complex effluent mixtures on the ecosystem and/or individual organisms. It is a tool to identify
individual effluent sources as well as sectors or point sources that give rise to concern. The
methodology observes primarily the discharge point into the recipient water, monitoring its
hazardous potential. The assessment and control strategy follows a series of steps:
to determine which effects are estimated as hazardous, and which parameters are apt to
detect these effects,
to set targets or benchmarks for water quality, which is normally a policy decision made in
advance, or to get the voluntary commitment of all concerned,
to set targets or benchmarks for effluent quality, which is part of a regulatory process to
meet the targets set for the receiving water,
to find a detection routine for the effects in question,
to detect the effluent whether this target can be met,
to backtrack in order to find the source for the hazardous effect when the effluent target is
not met,
to identify the hazardous substance responsible for the toxic effect and find a way to control
it or prevent its appearance.
2.2.2.3 Pinch Analysis on Water and Waste Water

Pinch Analysis is a methodology of optimising the consumption of consumables in processes
and on total sites by introducing process integration techniques. It was primarily utilised as an
energy saving tool to improve the thermal efficiency in the chemical and process industry.
Recently this method has been transferred to water and waste water minimisation. There are two
major design approaches for the Pinch technology on water and waste water the approach
developed by UMIST and the one by Linnhoff March which runs under the name of
WaterPinch.
Its concept is to define and find water saving potential by, e.g. piping and control changes, and
to minimise waste water discharge by process modifications, thus enabling selective waste
water regeneration and reducing treatment costs. It is also used to design or re-design
distributed effluent treatment to lower capital costs by reducing the hydraulic load of CWTP.
The application of WaterPinch can be broken down into four steps [cww/tm/86]:
Step 1:
Drawing a flowsheet of the entire water system (supply, discharge) that shows all places
where water is used, and all points where waste water is generated.
Developing a water balance accurate to within 10 % of the amounts of the larger streams.
Defining the appropriate data for the analysis by determining water sources and water sinks.
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An according profile is presented in Figure 2.2 [cww/tm/86].

Step 2:
Selecting key contaminants or properties that prevent the direct re-use of this special waste
water stream.
Choosing design concentrations maximum allowable for sinks, and minimum practical for
sources.
Step 3:
Developing the multi-dimensional pinch analysis to determine optimum matches between
sources and sinks. Appropriate software is available for this. The procedure includes
identification of pinches and a consideration of process modifications and regeneration
options resulting in lower targets.
Step 4:
Repetition of step 3 until a practical design has been evolved.
The application of WaterPinch has succeeded in waste water savings of up to 60 %
[cww/tm/86]. Performance examples for waste water flow reduction are:
Chemicals and Fibres

Chemicals
Oil Refining
Coal Chemicals
Polymers
25 %
40 %
20 30 %
50 %
60 %
An example for water conservation strategy is given in Figure 2.3 [cww/tm/86].
Figure 2.2: WaterPinch - Analysis, Source and Sink Curves
Savings in cost are normally not restricted to the water saving costs. They can be significant if
waste water reduction can lead to the construction of a smaller CWTP, avoid expanding the
existing waste water treatment facilities or can allow the capacity expansion of production units
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without hydraulically overloading the existing CWTP. Process modification and selective water
regeneration can result in product recovery which can be economically profitable as well.
The major applications for WaterPinch and other Pinch methods are [cww/tm/86]:
to avoid production cutbacks under limited water supply conditions,

to reduce water supply costs,
to reduce capital costs of new water supply facilities (e.g. new wells, pipelines, etc),
to reduce capital costs of water treatment facilities,
to reduce waste water treatment costs,
to reduce sewer charges,
to reduce capital costs of expanding on-site waste water treatment facilities to meet
increased production loads or more stringent emission regulations,
to help comply with environmental regulations.
Figure 2.3: Example for Water Conservation Strategy before and after WaterPinch Analysis
2.2.2.4 Choice of Sewage System

2.2.2.4.1
Selection of Waste Water Collection and Separation/Segregation
Taking into account the results of the waste water register, the choice of a suitable waste water
collection system is another decisive management tool, because it helps to ensure the optimum
discharge of waste water entailing the least possible impact to the environment. Depending on
the treatment requirements, a drainage system has to be installed that answers the demands for:
rainwater drains,
cooling water drains, according to the grade of pollution,
drains for waste water suitable for direct discharge without any treatment,
drains for sanitary and kitchen waste water,
drains for process waste water according to its origin.
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Waste water from the production of organic chemicals is usually treated biologically in CWTPs,
whereas waste water from the production of inorganic chemicals undergoes mechanicalchemical treatment, if any treatment at all. So a mixing of waste water streams from organic and
inorganic production results in a dilution of both parts that makes any downstream treatment
less efficient.
Essential conditions for the successful implementation of biological waste water treatment are:
the absence of considerable concentrations of substances that might inhibit biological

degradation,
a system-dependent microbiological degradability of the waste water components,
avoidance of dilution with very low contaminated waste water streams, so that effective
concentrations allow biological degradation.
wastewater
Contaminated
y
organic
contaminants
treatment of
inorganic
contaminants
special (pre-)
treatment
y
biologically
degradable
y
Central
wastewater
treatment
receiving stream
Figure 2.4: Decision Diagram dealing with Waste Water Segregation and Treatment
Those prerequisites, as well as economic factors, demand the implementation and maintenance
of waste water separation/segregation systems. Waste water that does not need treatment e.g.
uncontaminated cooling water, or uncontaminated rainwater is segregated from waste water
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that has to undergo treatment. Another reason for waste water segregation is the reduction of
hydraulic loading for the waste water system (sewer and treatment equipment).
Waste water streams that fail to meet quality demand for treatment in the CWTP are subject to
special pre-treatment operations. So, for each waste water stream present, the following
decision process should be followed (Figure 2.4).
Part of the drainage concept is the choice of the server (or sewer) type. Most common to the
collection and transport of waste water are underground sewers, which are easier to handle,
most of all as they can be used as gravity sewers.
Under special circumstances, above-ground collectors can be an attractive option. If the
groundwater level at a site is nearly at zero, as often happens near the embankment of large
rivers or on coastal sites, there is usually no other choice. These collectors facilitate the
detection of leaks, an important issue for waste water with hazardous contents.
The ducting of waste water can be done in gravity sewers or by pressure on vacuum collectors.
2.2.2.4.2
Storage or Retention Capacity for Failure Events
Operational failures, equipment leakage, unintentional contamination of cooling water or other

disturbances in production or storage units can lead either to an increased discharge of
pollutants into the recipient via the waste water treatment plant, or to a malfunction of the
CWTP. It could be convenient to consider the buffering of waste water streams that are
contaminated in those ways. There are several devices used for this purpose. Their capacity has
to ensure that all waste water, probably including rainwater, incurred during a production failure
can be stored.
2.2.2.4.2.1
Self-contained Buffer Devices
Figure 2.5 [cww/tm/87] shows a system with two collecting devices filled alternately. Process
water is part of the sewer system. During the filling operation of one device, the content of the
other one is detected, analysed and, according to the result, released either to the waste water or
the waste disposal pathway. Each buffer device must be able to receive the entire amount of
waste water (e.g. process water, cleaning water, rainwater, etc.) arising during the interval
necessary for analysis and depletion of the other tank.
Figure 2.5: Self-contained Buffer Device, Process Water included
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Leakage can be collected in a device shown in Figure 2.6 [cww/tm/87]. In the event of a leak,
the spilled material is ducted to the buffer tank, which must be able to receive the total volume
of the waste water involved (with the exception of process water), arising during the time
necessary for analysis and depletion of the tank. Rainwater is to be taken into account as well.
Figure 2.6: Self-contained Buffer Device, Process Water not included
This device is applicable to installations, which have separated process-water and leakage
pathways, the latter probably including rainwater. Events that might have influence on the
process-water stream cannot be controlled, so the application of this buffer device might not be
preferable for chemical production installations. Its advantage is that leakage spills can be
collected as relatively concentrated solutions to enable recycling.
Figure 2.7: Connected Buffer Device, not continuously flooded
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2.2.2.4.2.2
Connected Buffer Devices
Figure 2.7 [cww/tm/87] shows a connected buffer device, disconnected when not in use. A
leakage detection system ensures the connection of the buffer tank in the event of an operational
failure. The tank must be able to receive the amount of waste water released during the time of
malfunction. The detection system must enable immediate connection to the buffer tank in the
case of an event that might influence the effluent quality. When the malfunction is repaired, the
regular waste water discharge can re-start without prior depletion of the buffer tank.
Figure 2.8 [cww/tm/87] shows a connected buffer device probably used as equalisation tank
with continuous through-flow. A leakage detection system has to ensure that the outlet is closed
in the event of operational failure. The tank must be able to receive the amount of all incoming
waste water streams, so it might be recommendable only as buffering system of partial streams.
The tank has to be depleted before the regular waste water discharge can re-start.
Figure 2.8: Connected Buffer Device, continuously flooded
2.2.2.5 Selection of Appropriate Waste Water Treatment Options

A first rough decision path as to whether a partial waste water stream needs special treatment or
pre-treatment or can be discharged into a CWTP or directly into a recipient river, is illustrated
in Figure 2.9.
To dive deeper into details: the objective of this Reference Document is to provide guidance for
both, permitting authorities and industry permit applicants, to rationalise available treatment
options. In order to provide this guidance, information on the performance of available
technique, its applicability and cost should be brought together along with the results of the
management tools.
When final waste water treatment facilities are involved, allowing sufficient time for the
selection of the most appropriate control options becomes important. Before the implementation
phase can start, due consideration has to be given to all source reduction opportunities to enable
defining an ecological and economical final effluent treatment design. In some cases, the results
of these source reduction measures will not be known until they are at least partially
implemented. Therefore the final effluent treatment design may have to be deferred till after
implementation of these source reduction options.
Available options can be evaluated and selected primarily according to:
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the characteristics of the waste water, partial streams as well as the final discharge,
the amount that needs treatment,
the targets and goals to be achieved,
the control options given for a specific case.
w astew ater
degradable
> 90%
degradable
> 70%
y
recalcitrant TO C
< 20 kg/d or < 2 t/a
n
special (pre-)
treatm ent
plants
C entral
w astew ater
treatm ent
plant
receiving stream
Figure 2.9: Decision Diagram for the Allocation of Waste Water Streams polluted with Organic
Substances to the Various Treatment Techniques
These are general items to consider when selecting treatment options. Other specific
considerations and conditions are site-specific, so that a specific determination of an appropriate
waste water treatment remains always a decision at local level, since many of the key factors
vary from site to site, e.g.:
current environmental and economic performance of the installation,

age, design, anticipated life time of the installation,
size and layout of the site,
degree of process integration within an installation and between installations,
impact on the environment as a result of an actual or foreseen emission,
remaining life time and performance of an existing pollution abatement equipment,
plant location,
availability of resources,
limitations and constraints on an installation imposed through other legislation,
results of cross-media analysis.
It is not in the scope of this horizontal Reference Document to draw conclusions about specific
waste water management on specific sites. What will be presented here is the description and
utilisation of management tools which should help in decision making. Further management
tools will be described in subchapters.
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As a result of the considerations mentioned above, the appropriate waste water handling system
will be selected according to the following options:
Source reduction.
Source reduction options should be considered first. In many instances, these will result
from process considerations described in the related vertical BREF. Suggestions for
frequently occurring causes of contamination are:
Process water usage depends on the manufacturing process used. Its contaminant
concentration depends mainly on the solubility of the process stream in water. The
following suggestions should be taken into account:
-
To segregate process water from rainwater and other water effluent, to allow re-use or
recycling, as well as to minimise the amount of water which requires treatment. The
installation of a roof over certain process areas, loading and unloading bays, etc., might
be an option to consider.
To use process water in a recycle mode, whenever it is economically feasible, with a
maximum number of recycles before its discharge (see Chapter 1.1.2.1.2 above).
To avoid direct contact cooling systems whenever it is feasible. For exceptions see
Chapter 1.1.2.1.3 above.
To review critically the need for water scrubbing systems. If they are used, it is
advisable to investigate the potential for water regeneration and re-use (see Chapter
1.1.2.1.5 above).
Water flushing and sealing systems are frequently needed for safety reasons. The water
flow to these systems should be kept to a minimum, and not be allowed to flow without
any control or restriction.
To investigate the removal of free oil to a slop oil system before its discharge to the
sewer.
To achieve an effective water/hydrocarbon separation as far as practicable in the
process equipment before discharging the water to the sewer.
To minimise the contamination generated by vacuum devices. If feasible, the use of a
process fluid instead of steam in Venturi jet devices, or of a liquid ring pump or dry
vacuum pump should be considered. Liquid ring pumps should preferably use a process
fluid as seal liquid (see Chapter 1.1.2.1.4 above).
To capture as far as possible the discharge from safety valves and thermal relief valves,
as well as bleeds from double block isolation or twin seal valves. It is not
recommendable that these discharge to areas where clean rainwater is collected.
To consider laboratory effluent collection to a slop tank.
Unintended operational releases to the sewer can generally be avoided through enhanced
operator attention. Additional instrumentation or slop collection will often be helpful to
enable operators to perform their task efficiently. Also, slop collection facilities are
recommended wherever hydrocarbon liquid releases frequently occur. To reduce
unintended operational releases, the following suggestions should be taken into account:
-
To plug or cap vents and drains whenever they are not in use.
To allow flush collection in a slop system rather than to send it to the sewer. Closed
loop sample systems or sampling valves that require no flushing (e.g. ram type
sampling valves) are preferrable. Sample bottles should be sized in such a way that
overfilling is avoided. The sampling frequency and sample should be kept to the
minimum required.
To avoid the overfilling of vessels or tanks by installation of adequate level
instrumentation or adequate procedures.
To minimise the use of hoses.
To consider collection facilities to collect hose drips.
To consider roofs over loading racks.
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To install kerbs to ensure containment of spills.

To consider adequate instrumentation to protect against overfilling of trucks.
To avoid the product loss during a water draw-off from tank bottoms.
To consider the installation of reliable interface detection instruments.
To consider the pigging of lines instead of flushing and draining, whenever applicable.
To vacuum clean spills whenever possible rather than hydrojet or steam them to the
sewer.
Not to leave water hoses to run unattended, which is good management/manufacture
practice. This is mainly a water conservation measure. Conservation of water, however,
leads to concentrated water streams that might be profitably recycled or exploited for
higher production yields. So, any means to reduce water consumption might
directionally lead to a reduction in the quantity of contaminant evacuated through the
sewer.
Turnaround and other maintenance activities often result in significant water

contamination. To minimise this requires careful planning well in advance, such as:
-
To define a dedicated equipment cleaning site, equipped with adequate facilities to

recover hydrocarbons and solid waste. Equipment cleaning should occur at this location
as far as possible (e.g. exchanger bundle cleaning).
To plan carefully the draining of equipment to avoid undesirable releases to the sewer.
To evaluate carefully the equipment cleaning needs and methods.
To define a disposal route for all cleaning effluent.
Releases resulting from equipment failure are by nature unpredictable. Preventive

maintenance for equipment and implementation of a monitoring programme are ways to
ensure that these are minimised, e.g.:
-
To avoid as far as possible pump seal failure.

To consider the installation of seal-less pumps, vibration monitoring or leak alarms on
seals.
To detect leaks to cooling water resulting from exchanger failure by periodically
checking the hydrocarbon content of the cooling water return.
To repair detected leaks as soon as possible.
To analyse frequently leaking systems to define the most suitable type of equipment,
packing, gasket, etc.
Background contamination from dirty sewer systems can be minimised by, e.g.:
-
Periodically checking sewer inspection chambers for the presence of, e.g., free
hydrocarbons. If needed, these hydrocarbons could be vacuum pumped to the slop.
Cleaning of dirty sewers, which might cause a significant level of background
contamination.
Drainage Systems
It is usually advisable to segregate drainage systems according to the kind of waste water
streams, e.g. for organically polluted waste water, for inorganically polluted waste water,
for cooling water and for rainwater. More details can be found in Chapter 2.2.2.4.1 above.
Buffer Capacity
The installation of buffer capacity is beneficial for particular waste water streams at the
production plants as well as for collected waste water streams before entering the CWTP, in
case of an operation failure. Further details in Chapter 2.2.2.4.2 above. Buffer capacity is
also important to equalise waste water streams to ensure more balanced treatment
conditions in the CWTP. Single waste water streams with, e.g., recalcitrant TOC, can be
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buffered to be dosed in a calculated manner to the CWTP. Further details can be found in
Chapter 3.2.1 below.
Treatment Methods
Treatment options to consider are:
-
pre-treatment for an individual waste water stream, e.g. a stream containing heavy
metals, or a stream that is poorly biodegradable,
final treatment for an individual waste water stream with direct discharge into the
receiving water,
treatment for distributed waste water, as pre-treatment or final treatment,
central treatment for a whole site, e.g. mechanical/biological treatment plant (biological
CWTP), or precipitation/flocculation/sedimentation plant, or central treatment for
contaminated rainwater,
no treatment for low contaminated waste water partial streams or non-contaminated
rainwater.
The various treatment operations are described in Chapter 3 below.
2.2.3 Waste Gas Management Tools

Effective waste gas management is crucial to prevention, minimisation and treatment of volatile
substances emitted to air that can have impact on the environment. Furthermore it is essential
for safety reasons, because the wrong combination and wrong treatment of gas streams lead to
explosion and considerable damage. It requires real commitment to establishing the necessary
management techniques or tools. The following sections will provide information on the main
types of management tools.
2.2.3.1 Waste Gas Inventory

Like a waste water management system, the first step for installing a waste gas management
system is to gather relevant basic data on the composition and quantity of each waste gas
stream. A helpful tool to do this is the setting up of a Waste Gas Inventory, which provides the
basis for decision making on waste gas segregation, prevention, recycling or reduction
strategies, as well as waste gas control.
A waste gas inventory consists of:
information about the chemical production process, such as

- chemical reaction formula, including starting compounds, products and byproducts,
- simplified process flow-sheet of the corresponding production unit, showing
reactor, work-up and product isolation, and showing the origin of the various waste
gas or exhausted air contributions,
information about the waste gas streams, such as
- concentration and load of components and their variability,
- flow rate and its variability,
- nature of contaminants and its variability,
- temperature,
- relevant contaminants, such as: halides, sulphur dioxides, carbon monoxide,
nitrogen oxides, particulates, heavy metals and compounds, volatile organic
compounds (VOC),
- presence of other substances, which may impact on the treatment system, such as
nitrogen, water vapour, dust, etc.
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The characterisation of each waste gas or exhausted air stream will be carried out as far as is
relevant for proper functioning of an end-of-pipe control device, or for emission reporting
purposes. The number of required parameters and the level of accuracy to which these
parameters should be known depend on the nature of the stream and its importance relative to
the total effluent.
The purpose of a waste gas inventory is to identify the most relevant emission sources and to
allow a prioritisation of the emission reduction steps to be taken. Generally speaking, this is a
four-step operation:
listing of the sources,

evaluation of the causes for emissions through each source,
quantification of the amount of emission from each source,
validation of the results through a material balance.
The emissions from some sources may result from different causes, and therefore the result of
each cause may need to be evaluated separately to quantify the emission through this source.
Furthermore, source reduction will mean concentrating on the cause of emissions rather on the
source through which it is emitted.
Emission quantification by source
Emissions can be quantified by source in a way that is adopted in the EU VOC-Directive
[cww/tm/88].
To prepare a waste gas inventory, emissions from all potential sources have to be quantified.
This can be done either by estimation, calculation or measurement according to the type of
emission and its relative importance to total VOC emissions. Some emissions are best estimated
by output source, others by cause of emissions. In particular, uncaptured emissions are very
difficult to measure. They require quantification by contributing cause.
The following are offered by way of illustration:
38
The emission from product can be estimated, when the VOC content of the product is
known. The amount of solvent contained in the product is well defined, and quantities sold
or recovered are also known.
If VOCs are contained in waste, the VOC content needs to be measured, or otherwise be
defined to calculate the quantity that could be emitted. This will also depend on the method
used for disposal of the waste.
Ducted sources of emissions to the atmosphere can be quantified by measuring the air flow
rate and VOC concentration. This measurement is, however, often relatively expensive to
make and can be complicated by access difficulties, presence of water vapour or
particulates, or other circumstances, and may represent only a snapshot of a situation which
is often variable with time. A calculation method is therefore usually preferred, where
feasible. This possibility depends on what causes the emission. For example, if a ducted
emission is produced by evaporation of a solvent in a drying operation, it is normally easier
to calculate the quantity of solvent evaporated by measuring the solvent content in the
product before drying and multiplying this by the processed quantity.
Quantities not abated in an abatement system can be calculated if the quantities sent to the
abatement system are known and the abatement efficiency is known.
Uncaptured emissions are by nature almost impossible to measure and needs to be evaluated
by considering the causes for the emissions and the related evaluation methods detailed
below.
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Emission quantification by cause

A quantification of the emissions based on their cause might often prove to be the only practical
solution, particularly for uncaptured emissions, but often also for ducted emissions. Several
methods exist to perform these calculations. It should be borne in mind that all calculation
methods provide estimates, which in some cases indicate only the order of magnitude.
Examples are:
Process emissions quantification needs to be based on a detailed understanding of the

process that is taking place. In many cases this provides a fairly accurate evaluation of the
emitted quantity, which may sometimes need to be confirmed by measurements. In
performing these calculations and measurements, care should be taken to account for the
variability that may be inherent in the process. This may be a time variability in batch
processes the amount emitted typically varies as the batch processing progresses or a
grade variability different grades of products emit different quantities. Calculations need
to reflect these, and when measurements are performed, the operating conditions during
each measurement have to be recorded carefully, and also measurements in sufficient
number have to be made to account for the full range of variability. A yearly material
balance needs to take the actual yearly production into account to reflect properly the grade
slate effect.
Storage tank emission calculations can be based on the methodology developed by the
United States Environmental Protection Agency (US EPA) [cww/tm/89]. The calculations
are cumbersome and require knowledge of some meteorological data that can be obtained
from the local Meteorological Institute. Significant storage emissions can be generated from
above ground atmospheric tanks. However, breathing losses from underground tanks or
tanks with a set pressure higher than atmospheric are significantly reduced. Working losses
depend on the number of turnovers per year (i.e. how many times the volume of the tank
was filled/emptied during the year) and are low for low turnover. If vapour balancing is
applied during tank filling, the working losses are eliminated. Therefore in many facilities
the storage emissions are low compared with the other emissions. It is advisable to evaluate
the storage losses based on material balance before embarking on detailed calculations. If
detailed calculations are required, it is strongly advised to use the TANKS computer tool
developed by the US EPA, which is a computerised version of the EPA calculation method
[cww/tm/90].
Handling emissions can be calculated assuming a vapour content of the air being exhausted
from the container being loaded corresponding to the vapour pressure of the product being
loaded at the loading temperature, multiplied by a saturation factor. The saturation factor
depends on the method of loading, and represents the degree of saturation achieved on
average in the vapour space during the loading. Saturation factors for tank trucks of BLCs
are [cww/tm/72]:
- submerged loading in a clean cargo tank: 0.5,
- submerged loading in a wet cargo tank (dedicated service): 0.6,
- splash loading: 1.45
(a factor greater than 1 represents over-saturation caused by liquid droplets being
expelled with the vapour).
Equipment leak emission calculations rely on methods developed by the US EPA and vary
from simple (based on counts of leak points and average emissions per point) to complex
(based on correlations between a measured ppm concentration at the leak interface and a
leak rate specific to the type of equipment considered). Additional description is provided in
the
US
EPA-453
Protocol
for
Equipment
Leak
Emission
Estimates
[http://www.epa.gov/ncepihom/Catalog/EPA453R95017.html]. These calculation methods
provide rough estimates of actual emissions, and usually a more sophisticated calculation
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Chapter 2
method will yield lower results. Calculations based on equipment counts are the only ones
not requiring measurements with an organic vapour analyser at each potential leak point. If
these calculations provide a satisfactory result for the purpose, no further analysis is
required. If the equipment leak emissions become significant, a Monitoring and
Maintenance programme (also called Leak Detection and Repair, or LDAR) should be
implemented, entailing measurement of each potential leak point and opportunity for repair
of leaks being discovered. This work requires skill in performing the measurements and
recording these in a database and is therefore best carried out by specialised contractors.
Non-routine emissions caused by start-up, shutdown and maintenance operations need to be

taken into account. These depend heavily on the operating methodology. No widely
accepted method to estimate these emissions exists. These can, however, become significant
in batch operations with frequent opening/closing of vessels. In these cases the best
practical approach is to set up a measurement campaign to quantify the emissions linked to
each operating step.
Accidental emissions should not occur. Since they happen, however, the related solvent loss
should be reflected in a material balance. It is recommended that these incidents be tracked
and a record kept of the estimated quantity emitted during each event.
2.2.3.2 Choice of Waste Gas Collection Systems

Waste gas collection systems are often far less extensive than waste water collection systems.
Waste gas collection systems are installed for two reasons:
as vent collection systems, routing several vents to a common abatement system,

as flaring systems, which are primarily installed to allow safe disposal of off-gas in
emergency situations.
For VOC collecting systems the most important issue is safety. There are devices that can be
installed that prevent ignition of flammable gases or minimise its effect by preventing
explosions. Such devices usually are, e.g.:
detonation arrestor,
seal drum,
water seals, etc.
The concentration in VOC collection systems must be kept below or above the explosive range,
so that the correct mixture of waste gases is a crucial point.
2.2.3.3 Selection of Appropriate Waste Gas Control Options

The current decision making process in selecting an appropriate control option for waste gas is
similar to that process for waste water, so the considerations are generally the same.
Available options for waste gas control can be evaluated and selected primarily according to:
the characteristics of the waste gas stream,

the amount of waste gas, exhaust air or flue gas needing treatment,
the targets and goals to be achieved,
the control options given for a specific case.
These are general items to consider when selecting treatment options. Other specific
considerations and conditions are site-specific, so that a specific determination of appropriate
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waste gas treatment always remains a decision at local level, since many of the key factors vary
from site to site, e.g.:
current environmental and economic performance of the installation,

age, design, anticipated life time of the installation,
size and layout of the site,
degree of process integration within an installation and between installations,
impact on the environment as a result of an actual or foreseen emission,
remaining life time and performance of an existing pollution abatement equipment,
plant location,
availability of resources,
limitations and constraints on an installation imposed through other legislation,
results of cross-media analysis.
As with waste water, this horizontal Reference Document will not draw conclusions about
specific waste gas management on specific sites. What will be presented here is the description
and utilisation of management tools, which can help in decision making. The description of
further management tools will follow.
Controlling emissions of VOCs at a cost-effective level requires investigating source reduction
opportunities first. Once all feasible source reduction possibilities have been exhausted, an endof-pipe treatment may still be required. Even then, careful planning is required to optimise the
related investment and operating costs.
When planning the modifications entailed in either source reduction or end-of-pipe treatment, it
should always be remembered that all changes can have significant safety implications,
particularly when dealing with flammable substances. Therefore it is absolutely essential that
the effect of any change on the safety of the installation be thoroughly assessed.
The selection of the most appropriate air emissions control system includes the following steps:
investigation of source reduction opportunities,

definition of the target reduction objective, based on a risk assessment and economic
evaluation,
selection of the most appropriate abatement technology.
Source Reduction
Upon investigation, further opportunities for source reduction of emissions can emerge. In most
cases the related investment is lower than for an end-of-pipe treatment. A thorough
investigation of the source reduction possibilities is therefore highly recommended. It should be
based on the causes for emissions. Therefore a good knowledge of the relative importance of
each cause will be essential for prioritisation purposes.
End-of-pipe control
When source reduction measures do not lead to sufficient emission reduction, an end-of-pipe
treatment is required. All treatment devices can handle only ducted emissions. Therefore, if
uncaptured emissions have to be abated by means other than source reduction, collection hoods
and a ventilation system are required upstream of the end-of-pipe abatement system. Installation
costs for these ventilation systems can be significant. Therefore these systems need to be
designed with cost effectiveness in mind. The investment required for the end-of-pipe treatment
itself will generally be a function of the total air flow rate to be treated, therefore efforts to
minimise this flow rate will pay off. Also, there is generally a cut-off point beyond which
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treatment of minor sources of VOC emissions cannot be justified. Finally, selecting the most
suitable treatment technology will have a significant impact on the required investment and
operating costs.
Emission collection
A collection system is required to enable end-of-pipe treatment of uncaptured emissions. These
systems usually consist of extraction hoods placed above the sources of emission, ventilation
blowers and a duct system to the abatement unit. In order to minimise the air flow rate to the
abatement unit, it is recommendable to encase the emission sources as much as possible by
means of partitions separating the sources of emission from their surroundings. This, however,
presents operability (access to equipment), safety (avoiding concentrations too close to the
lower explosion limit) and hygiene concerns (where people access is required inside the
enclosure). The enclosure needs to be designed in such a way that vapours are prevented from
escaping by ensuring sufficient air velocity through the openings (0.5 m/s minimum
recommended). The total flow rate should be sufficient to ensure dilution of vapours to a value
well below the lower explosion limit. Where this concentration is likely to be exceeded,
installation of an LEL detector inside the enclosure may be required.
In most cases, the emission abatement system will be installed on existing ducted emission
points or vent collection systems. A critical review of these existing systems is warranted before
determining the total flow rate of the abatement system. This review is required for two basic
reasons:
Actual flow rates delivered by blowers may be significantly different from the blower
design flow rate, because of pressure drop upstream and downstream of the blower. Actual
flow rates at less than 50 % of the blower design capacity are not infrequent. Therefore
basing the abatement system flow rate on the sum of design blower flow rates delivering to
the abatement unit may lead to a significantly oversized end-of-pipe treatment.
Measurement of the actual flow rates is therefore recommended. Allowance has to be made
in the final system design to account for a change in flow rates (increases or decreases),
which may be caused by the installation of the abatement unit. In the case of a decrease in
flow rate, the safety implications must be checked as well.
The existing vents or fume extraction systems may not have been designed with flow rate
minimisation in mind. Small adjustments to the design may lead to significant reductions in
flow rate and consequently significant savings on the end-of-pipe treatment cost.
Technology selection
The selection of the most appropriate abatement technology for a specific case requires
consideration of many different parameters, of which the most important are:
42
flow rate,
concentration of the contaminants,
nature of the contaminants,
presence of impurities,
concentration allowed in the exhaust air or waste gas effluent,
safety,
investment costs,
operating costs,
layout,
availability of utilities.
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From the process point of view, the flow rate and the inlet concentration are the key design
issues. However, additional to the maximum value, the degree of variability of the stream to be
treated has also to be considered.
The nature of the contaminants is of primary importance since all systems present limitations in
this respect, e.g.:
only flammable vapours can be incinerated; contaminants containing chlorine and/or

sulphur require flue gas treatment after incineration,
the efficiency of condensation depends on the vapour pressure of the contaminant at the
condensation temperature, therefore substances with higher vapour pressure are less suitable
to condensation,
only compounds with small molecules can be effectively adsorbed and desorbed; methyl
ethyl ketone (MEK) and some other products are not suitable for activated carbon
adsorption,
biofiltration of non-biodegradable compounds will not be effective,
membranes work better on specific compounds.
The value of the product being emitted will determine the incentive to recover it from the offgas, so the more valuable the product the more the use of technologies allowing recovery (e.g.
adsorption, condensation, membranes) will be preferred to destruction technologies (e.g.
incineration, biofiltration).
The presence of impurities in the off-gas will impact the design of the system. Sometimes these
impurities have to be removed in a pre-treatment step, e.g.:
water vapour, which impacts on the adsorption efficiency; the level of humidity also has an
impact on condensation systems, particularly on refrigerated or cryogenic systems, or on
filter systems,
dust, which causes trouble for adsorption or regenerative incineration where dust particulate
will plug the packing or adsorbent bed.
catalyst poisons, which will destroy the efficiency of a catalytic incinerator or a catalytic
filter.
The permitted exhaust concentration has to be considered. Most technologies are limited in
removal efficiency, and in particular condensation, absorption and biofiltration do not approach
100 % removal efficiency. This is a clear advantage of incineration systems, which reach very
high destruction efficiencies. Also adsorption systems are very efficient, as long as care is taken
to avoid saturating the adsorbent.
Safety issues are particularly important for incineration systems. Most VOC/air mixtures are
flammable at VOC concentrations above 40 g/m3 at 20 C and atmospheric pressure. In order to
avoid propagation of a flame in the inlet ducts to an incineration (flashback), one has to ensure
that the inlet concentration is always well below the lower explosion limit. A detonation arrestor
or a seal drum can be provided to prevent the risk of flashback for unexpectedly high
concentrations. Besides this, the incinerator has to be installed at a location where there is no
risk of presence of flammable vapours, and a detailed analysis is required to ensure safety of the
installation. Also systems using other technologies have to be subject to a detailed safety
review. Many systems (e.g. adsorption, membranes) will result in more concentrated streams,
possibly producing concentrations within the flammable range. For adsorption systems, bed
overheating risks have to be evaluated. Many systems include compressors or blowers which
may have safety implications. Generally, a detailed safety review of each installation is required
and it may have a significant impact on the selection of the system.
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The investment required for the system is obviously also of primary importance. When
evaluating the required investment, care should be taken to include the costs of all the required
facilities. In particular, utility supply, vent collection ducting to the abatement unit and
requirements in ancillary equipment (e.g. a seal drum for an incinerator, water treatment unit for
a condenser) may have a significant cost impact.
Although the initial investment is important, the operating costs may be even more important.
These include utility consumption, catalyst or adsorption media replacement, operations and
maintenance costs, by-product disposal, etc. When evaluating these, care should be taken to
quantify the costs associated with each stage of the operations (normal operations, regeneration,
idling). As an example, thermal oxidisers are normally fitted with refractory lining. This
refractory is sensitive to humidity and therefore has to be kept warm at all times. The amount of
fuel required to keep it warm during idling times is an important consideration for systems not
operating 24 hours per day 7 days per week. Keeping a regenerative or a flameless system at
temperature requires a fraction of the fuel needed for a simple thermal oxidiser.
Layout constraints may play an important role. Incineration systems have to be located outside
of locations where flammable vapours could be present. The installation of a system within a
hazardous area will require designing the electrical and instrumentation systems accordingly,
which may affect the cost of the unit significantly. Access requirements to the unit should be
considered as well.
Availability of utilities is yet another key aspect in the selection of the most appropriate
abatement technology. Availability of a suitable fuel is required for an incineration system, and
the fuel costs may have a big impact on the operating costs. Fixed bed adsorption systems
normally use steam for desorption; however, if steam is not available in sufficient quantity, the
design has to be adapted accordingly. Sufficient power supply is required for condensation
systems, etc.
Abatement systems are dealt with in Chapter 3.
2.2.3.4 Final Waste Gas Abatement System Design

In complex situations, where waste gas (VOCs) is expelled through multiple vents in variable
quantities, an additional decision has to be taken on whether it makes sense to collect and abate
all vents. It could be that the exclusion of a few vents would lead to significant investment
savings, even when these vents are going to be treated separately. It could then be appropriate to
quantify the impact of these vents on the system as a whole and to evaluate whether their
inclusion makes economical sense. It is, however, not always straightforward to find out which
vents should be connected to the abatement system. A methodology that can help in establishing
this is described below:
44
Listing of the flow rate and contaminant concentration for each vent. This requires field
measurements, since flow rates can differ significantly from the blower rating and
concentrations may not be known.
Screening out all source reduction ideas that can be applied to each vent and basing the
design flow rates and concentrations on the reductions that will really be applied. The
abatement system basis should be realistic, but should take reasonable source reduction
ideas into account.
Selecting a base case by including the vents which contribute most to VOC emissions and
excluding the ones which contribute only marginally. Checking that the base case is
realistic by calculating what percentage of total VOC emissions would be eliminated if
these vents were connected to an abatement system.
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Selecting the most appropriate abatement technology for this base case and asking suppliers
for quotations as a basis for a total investment estimate and adding to this base case estimate
all costs that may be relevant to the installation of the abatement unit.
Asking suppliers what the investment sensitivity is to changes in flow rate or VOC
concentration. In most cases, the investment is primarily defined by the flow rate to be
treated. If no other information is available, assuming an investment ratio equal to the 0.6th
power of the flow rate ratio provides a good basis.
Calculating the marginal investment reduction for each vent in the base case that would be
achieved by its exclusion from the base case, based on the investment sensitivity.
Calculating the marginal additional investment for each vent not included in the base case
that would be required if it were added to the base case, based on the investment sensitivity.
These calculations allow the investment required per tonne of VOC abated for each vent to
be defined. Plotting this on a graph allows the breakpoint to be defined and the vents to be
identified for which abatement would require excessive investments.
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Chapter 3
3 APPLIED TREATMENT TECHNOLOGY

This chapter describes treatment operations, processes and systems for waste water and waste
gas according to their environmental performance and impact, as well as to their economic
viability. Keeping in mind the horizontal character of this document special applications of
technologies in connection with production operations are not dealt with when their use is
restricted to this individual production. Variants of well-known technologies with only slight
variations to the general process are not mentioned separately.
The technical theory of the operations and processes dealt with in this document can easily be
found in available textbooks and therefore will not be repeated in this Reference Document. The
operations and processes dealt with are end-of-pipe and pre-treatment technologies that are
commonly used in the chemical industry. Treatments that comprise a combination of these
operations and processes are included as well. Also part of this document are technologies that
are already implemented successfully in other sectors, provided they are expected to be
applicable in the chemical sector as well. So technologies for power stations and wasteprocessing are also taken into account since large chemical sites often are equipped with their
own energy production (power, steam) and waste incineration.
The systematic overview of techniques, operations, processes and systems used in this chapter
tries to follow the path of the pollutants and to present a ranking concerning the treatment
systems in relation to their application on a chemical site. Further details can be found in
Chapters 3.2 and 3.5 below.
3.1 Information presented in this Chapter

The description of treatment operations and processes in this chapter follows a determined
pathway containing the necessary information to assist a permit writer to regulate the
implementation of BAT according to emissions to air and water for a chemical installation. The
information is also directed to an operator of chemical installations as assistance to fulfil the
BAT requirements. The fixed and formal format is chosen to make sure that for all treatment
operations and processes the same kind of information is collected and presented and a
comparison between different treatment options is feasible.
The description of treatment operations and processes is subdivided into the paragraphs:
principles,
application,
installation and design,
advantage/disadvantage,
environmental performance and impact,
monitoring,
costs.
The first paragraph, headed principles, outlines the fundamentals of a treatment technique
without going into detail. Physical and chemical theoretical background is left out deliberately.
This information can be found in a variety of good textbooks, a collection of which will be
stated in the annex. The use of chemical and mathematical formulae and equations is avoided
wherever possible without loss of information.
The second paragraph, headed application, describes how and where the technique in question
is commonly applied, with emphasis on its use in the chemical industry, but also in related
sectors, when this technique can be expected to be useful in the chemical sector as well. It
includes also the related pollutants to be treated. Combustion and waste treatment are applied in
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the chemical industry, so pollutants from these activities are also taken into consideration. Part
of this paragraph is a listing of application limits and restrictions. To emphasise again the
horizontal character of this document: process-specific and/or site-specific items might render
an application inappropriate for a particular production installation or purpose.
The third paragraph, headed installation and design, gives an overview of what equipment is
involved in this technique and how the technique is operated. This will be illustrated, e.g. by a
flow diagram. If appropriate or necessary for understanding some technical details are
presented, accompanied by a graphical sketch.
The fourth paragraph, headed advantage/disadvantage, tries to outline some problems and
benefits associated with each technique, bearing in mind that some fundamental laws of mass
and energy conservation prevent us controlling or abating anything without leaving any traces
in the environment.
The fifth paragraph headed environmental performance and impact, tries to show the effects
of the said technique. It lists the achievable emissions, or better, the performance of removing
the pollutants to control. But it also lists the impact on the environment arising from the action
of this technique, e.g. generation of sludge, waste heat, gaseous releases, noise, odour etc. The
values shown are those that can be normally expected. They will not, however, imply that these
values are achievable under all circumstances and with all applications.
The sixth paragraph, headed monitoring, describes everything that has to do with examining
the input, the output and the regular working of the technical devices.
The seventh paragraph deals with costs.
3.1.1 Information on Cost in this Horizontal Document

Costs of erecting a new emission control technology, retro-fitting existing technologies or
implementing process integrated measures, are largely dependent on site-specific and
production specific issues. Production specific and local issues are not comprised in the scope
of this document, which has to be kept in mind when evaluating cost figures. So costs quoted
here are not if not stated otherwise the costs that result from actual building or implementing
a technology into an existing infrastructure. They do not include the costs to implement an
appropriate and necessary infrastructure, either. What is more easily accessible for a horizontal
document are the supplier equipment costs relative to a waste stream or to a pollutant amount
(i.e. costs per m3 of waste water, per 1000 Nm3 of waste gas or per kg of a pollutant). The
information on costs collected in this document will evaluate the conveyed figures according to
the situation in question. Items to consider when evaluating cost data that are not normally
encompassed in this document because of their site and process specific characteristics are
explained in the following paragraphs [cww/tm/48].
3.1.1.1 Total Installed Costs vs Supplier Equipment Costs

When trying to determine the cost of emission control technologies, it is often easiest to select a
technology that appears to suit the requirements at hand, and solicit a cost quotation from a
supplier of that technology. While fast and convenient, this approach can lead to vastly
inaccurate estimates of the actual cost of the emission control technology. This occurs on an
absolute basis, like cost per tonne of emission reduced, and on a relative basis when comparing
technology options. Different technologies can often have very different distributions of
individual cost elements between the various types of costs that make up their total installed
cost.
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Operating costs must also be critically considered when developing the absolute and relative
cost comparisons of various control technologies. These can often be overlooked when taking a
hardware view of control technologies, which is often the case when considering
implementation of techniques. It is important to account for the potentially dramatically
different operating costs between technology types depending on utilities usage, labour
requirements, waste generation potential and the cost of its disposal, etc.
Supplier costs will typically include only the cost of the specific equipment that he supplies. In
many cases this is a rather small fraction of the overall materials cost for a project. Additionally,
the engineering costs associated with project design and supervision are often ignored, but can
easily equal the cost of the supplier equipment. Expenditure often not thought of when
estimating the cost of a project includes items such as the need to:
relocate existing facilities,

enlarge and/or move existing sewer lines,
perform soil investigations,
develop new as-built drawings, process and instrumentation diagrams,
modify existing piping and facilities such as blowers, pumps, etc.
An example is given in Table 3.1 [cww/tm/48] for a tail gas cleanup unit at a refinery with total
erected costs, prices from 1997 given in euros (). The direct equipment costs or supplier
costs are M 7.9, compared with the total costs of M 29.4 just 27 % of the over-all erected
costs.
Description
Equipment Costs (Vendor Costs)

Materials
Catalysts and Chemicals
7.3
0.6
Subtotal
7.9
Subtotal
8.0
1.6
2.4
12.0
Indirect Costs
Detailed Engineering
Field Supervision
Owner
Direct Costs Non Equipment
Subcontracts
Temporary Construction and Consumables
Subtotal
Total Capital
Expense
Licensing Fee
Subtotal
Final Total
8.6
0.4
9.0
28.9
0.5
0.5
29.4
Table 3.1: Example for Costs of an Actual Project
3.1.1.2 Green Field Costs vs Retro-fitting Costs

Green field installations and existing operations and units require essentially the same
technology to control specified pollutants, or to meet specified emission limit values. The
differences between these two types of installations are essentially driven by the fact that in a
green field case it is possible to ensure that all of the control technology requirements, such as:
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plot space,
utilities,
structural support,
are explicitly considered when the facility is designed. In the case of a retro-fit, the original
design choices may result in otherwise available or even preferred control technologies being of
limited applicability or possibly even infeasible. Considerations of whether a technology
constitutes an appropriate technique for a retro-fit application deal primarily with the ability of
the existing installation to meet the process, physical and structural requirements of the control
technology.
Depending on the nature of the control technology, its ability to be technically and
economically retro-fitted onto an existing facility can vary from being no more difficult than
including it in a green field design, to being essentially impossible to utilise without rebuilding
the entire existing process. This distinction in available technology being applicable to new and
existing facilities is a crucial one to include in any determinations of techniques. Where
information is available this chapter will give information about the potential retro-fittability of
a technique.
3.1.1.3 Capital Costs vs Operating Costs

Different control techniques (equipment-based controls and procedural techniques) can be very
different in terms of the distribution of costs between capital and operating expenses. Some
equipment costs while initially high are then very low in operating expense, while other very
low cost equipment approaches involve severe increases in operating costs such as labour,
utilities or expendable chemicals. It is generally easier to quantify the cost of hardware than the
full implications of the likely expenses incurred by a technique. Also equipment items will
become more costly (in current ) over time due to inflation, etc.
Concerning operating costs, labour costs play an important part, an issue that can have different
consequences on a decision in favour of or against a technique, depending on the different wage
rates in the Member States. So, if labour costs are referred to in this document, labour hours are
given when available as well.
3.1.1.4 Initial Emission Control Costs vs Incremental Control Costs

An important consideration of the cost of a technique relates to the changing cost effectiveness
that results for a given technology depending on the point of control from which one starts the
cost effectiveness calculation. Usually the costs and effectiveness given as percent of emission
reduction, or tonnes of emissions reduced of installing a technology or implementing a
technique are presented against an uncontrolled baseline operation. In such a case one calculates
the cost effectiveness easily by dividing the costs by the emission reduction achieved.
Due to real existing reasons there are many situations where certain levels of control already
exist within specific industry sites. In these cases the costs to achieve a given emission
reduction target is significantly increased over the initial cost effectiveness values for an
uncontrolled baseline operation. This needs to be accounted for in determining the cost
effectiveness of a technology or technique.
So for incremental control costs the cost effectiveness can be calculated as:
Keff = (B A)/C
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B: emission reduction for technique considered [% or mass unit]

A: emission reduction for technique already installed [% or mass unit]
C: costs for technique considered
3.2 Waste Water Treatment

Waste water and rainwater treatment in the chemical industry typically follow an order
determined by the kind of pollutants to be expected in the waste water discharge from all the
installations. An example for such an order is given in Figure 3.1.
WASTE WATER
SOLUBLES
INSOLUBLES
Gravity
Separation
Coagulation
Flocculation
Flotation
Filtration
Micro-/
Ultrafiltration
INORGANICS/
NON-BIODEGRADABLE/
POORLY BIODEGRADABLE
BIODEGRADABLE
Precipitation
Adsorption
Ion Exchange
NF/RO
Extraction
Distillation
Evaporation
Stripping
Aerobic
digestion
Anaerobic
digestion
Nitrogen
Elimination
Oxidation
Incineration
DISPOSAL
SLUDGE TREATMENT
Figure 3.1: Schematic Overview of Waste Water Treatment in a Chemical Plant
Waste water contaminants are typically either soluble or insoluble substances, so the first step in
waste water treatment will be a separation or clarification process, such as:
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Gravity Separation (Sedimentation, Oil-Water Separation),

Coagulation,
Flocculation,
Flotation,
Filtration (Filter, Membranes).
All these clarification operations are, normally, not treatment processes in their own right. They
are mainly used in combination with other operations, either as a first or a last clarification step.
As a first step they, e.g., prevent other treatment facilities from damage, clogging or fouling by
solids. As a final step they remove solids formed during a preceding treatment operation or
process. Examples will be given at another stage of this chapter.
The more or less clarified waste water will be distinguished further into a biodegradable and a
non-biodegradable part, a distinction made because central biological treatment of organic
waste water content is the usual control technology in the chemical industry. The nonbiodegradable waste water part will be segregated from the biodegradable because firstly it
might disturb the biological reaction in the CWTP and secondly it undergoes no cleaning effect
in the CWTP. The treatment of the non-biodegradable part usually takes place at the individual
production unit, before mixing this particular waste water stream with others. Treatments are
physical and/or chemical operations, such as:
Precipitation,
Adsorption,
Ion Exchange,
Membrane Filtration (Nanofiltration, Reverse Osmosis),
Extraction,
Distillation/Rectification,
Evaporation,
Stripping,
Oxidations,
Incineration.
After adequate treatment, the waste water stream will either be discharged or ducted to the
biological CWTP.
Partial waste water streams from inorganic chemical production units might be treated centrally,
if their individual contaminant content is similar in composition.
The remaining waste water part, the biodegradable section, will be transferred to a CWTP,
where biological processes transform the pollutant content into carbon dioxide and water, at
least theoretically, and a mineralised sludge. These biological processes are, e.g.:
Aerobic Digestion,
Anaerobic Digestion,
Nitrification/Denitrification.
All waste water treatment operations and processes or nearly all have one thing in common:
the production of waste, more or less solid, such as, e.g., surplus activated sludge or filtered
residue from filtration operations. This waste will be de-watered and either treated on the site or
disposed of. Several treatment facilities for sludge are described as well.
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3.2.1 Flow Balancing

In general, waste water treatment plants operate most effectively at reasonably constant
conditions, constant concerning its hydraulic load (or flow rate) as well as its contaminant load.
In practice, however, both flow rate and contaminant load can fluctuate markedly due to factors
such as:
process conditions,
use of water for washing,
ballast water treatment,
maintenance times,
rainfall, etc.
To even out the flow and load, balancing capacity may be installed upstream to the waste water
treatment facility in question. This may be either in line, or more usually, installed as a side
stream to which the flow can be diverted at peak periods or in case of production disturbances,
and run down at a controlled rate when the flow has moderated.
For process waters, tanks are used for this purpose, whereas for surface water drainage, open
lagoons or wet detention ponds may be used (see Chapter 3.3.2) [cww/tm/48].
3.2.2 Insoluble Waste Water Contaminants

Insoluble waste water contaminants are a normal phenomenon in waste water. They may consist
of inert substances such as dust from rainwater drainage or sand (as ballast in raw materials
such as lime). But they may also consist of hazardous materials such as heavy metals and their
compounds, originating from precipitation processes or production processes using catalysts.
Even dioxins can be adsorbed to solid waste water contents (e.g. catalyst of the vinyl chloride
production via oxychlorination). On the other hand, insoluble contaminants need not necessarily
be solid particulates. Liquids non-mixable with water, such as oil, substances of oily
consistency, grease or colloids belong to this category. Waste water containing insoluble
contaminants usually has to get rid of them by separation processes, which are described in the
following chapters.
3.2.2.1 Gravity Separation

3.2.2.1.1
Sedimentation
Principle
Sedimentation means the separation of suspended particles and floating material by
gravitational settling. The settled solids will be removed as sludge from the bottom, whereas
floated material will be skimmed from the water surface.
Application
Sedimentation is used to clarify waste water or rainwater from solid or floating material. It is
applicable as a one step process, a pre-treatment step or a final or intermediate clarification step.
Examples for single step processes are:
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clarifying collected rainwater in a sedimentation tank,

clarifying waste water from inert contents, such as sand, or particulates which are separable
with high efficiency.
Sedimentation as final or intermediate clarification is applied to:
separation of heavy metals, after chemical reaction, precipitation of the insoluble oxides and
flocculation; and followed by filtration,
separation of particulates which are not or only poorly separable, after flocculation or
coagulation, eventually finally followed by filtration,
removal of activated sludge in a primary, secondary or final clarifier of a CWTP.
Application limits and restrictions:
particulates must be large enough to be settleable, otherwise the addition of flocculants or

coagulants can be helpful (see chapters on Coagulation 3.2.2.2 and Flocculation
3.2.2.3 below),
volatile liquids should be avoided because of the long residence time in the separator and
the potential release of VOCs,
no limitation according to solid concentration provided the aqueous phase is still separable.
Installation and Design

To fulfil the treatment objectives, there are two types of sedimentators (or settlers) operated:
sedimentation tanks designed to provide a necessary residence time of about 1 to 2

hours, see Figure 3.2 [cww/tm/4],
lamina or tube settlers, where plates are used to enlarge the sedimentation surface, see
Figure 3.3 [cww/tm/91].
Figure 3.2: Sedimentation or Settler Tank
Storage facilities for the sedimented sludge are necessary, equipped in accordance with the
characteristics of the sludge.
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Figure 3.3: Lamina or Tube Settler
Advantage and Disadvantage

Advantages
Simplicity of the installation.
Disadvantages
Sludge to disposed of.
Unsuitable for fine material. In this case
flocculant and/or coagulant chemicals have to
be added.
Usually not a final treatment stage. A
secondary step is needed.
Environmental Performance and Impact

Since sedimentation is typically used as an intermediate or pre-treatment method, achievable
emission levels for these applications are of no great importance. Where it is used as a final
stage, e.g. as last clarification step as part of a CWTP, an emission of filterable solids of
< 10 mg/l is achievable [cww/tm/67 John et al., p.483].
Sedimented sludge and skimmed scum have to be disposed of as waste. Depending on the
origin of the separated substances, this waste might contain hazardous compounds to be treated
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accordingly. These compounds can be carbonates, fluorides, hydroxides (or oxides) of heavy
metals, phosphates, sulphates, sulphides, oily scum, etc. and under certain circumstances even
dioxins.
Input and utilities can be:
under certain circumstances flocculant and/or coagulant chemicals,

electric energy for pumps, sludge and scum removal system
The energy consumption is not known.

Sources of noise are pumps that can be enclosed and the sludge/scum removal system.
The emission of odour depends on the characteristics of the waste water stream that enters the
settler. The presence of volatile contaminants can require a closed tank or a covered basin.
Monitoring
The effluent of the sedimentation tank or of the lamina settler has to be regularly monitored in
regard to its solid content, i.e. filterable solid, settleable solid or turbidity.
Costs
The investment costs are not known
The operating costs are:
labour costs:
utilities:
consumables/residue:
total costs:
3.2.2.1.2
not known
Oil-Water Separation
Principle
Oil separation and removal can be divided into:
gravity separation of free, non-emulsified oil,

chemical treatment (emulsion breaking) and separation of emulsified oil.
Emulsion breaking chemicals are, e.g.:
polyvalent metal salts such as alum, aluminium trichloride, ferrous chloride, ferrous
sulphate,
mineral acids such as sulphuric acid, hydrochloric acid, nitric acid,
adsorbents such as pulverised clay, lime,
organic polymers such as polyamines, polyacrylates, etc.
Emulsion breaking is normally succeeded by coagulation and/or flocculation and finally by air
flotation (see Chapter 3.2.2.4 below).
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Application [cww/tm/48]
The different types of oil-water separation are applied to remove oil, grease and other nonsoluble liquids from waste water. Gravity separation is not a single step operation. It is always
combined with coagulation/flocculation after emulsion breaking and flotation, often DAF.
The collected oil has to be recovered. For this task several kinds of skimming equipment are
used, e.g.:
fixed pipe skimmers,

rotating trough skimmers,
rotating disc or drum skimmers.
3.2.2.1.2.1
American Petroleum Institute Separator (API)

An API is the simplest oil-water separator (see Figure 3.4 [cww/tm/91]), consisting of an open
rectangular basin. The standard API separators comprise an inlet section and oil-water
separation chambers. The approach channel and transition part are usually constructed in at least
two bays in order to facilitate cleaning and repair when required. Flight scrapers may be
installed to gently move the sludge to a collection pit and the oil to the skimming device.
Covers may be installed to reduce odour and emissions to air [cww/tm/48].
Figure 3.4: American Petroleum Institute Separator (API Separator)
If the buoyant liquids cannot be recycled immediately, storage facilities for the skimmed liquid
are necessary.
Advantages
Its large volume can intercept large slugs of
free oil and solids.
Disadvantages
Requires a large area.
Only comparatively large oil drops removed.

Cannot separate soluble substances.
Oil can be recovered and recycled to the
process units.
Separate emulsion breaking stage necessary.

Sludge to be disposed of.
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The main aim of the API separator is to help to improve the performance of downstream waste
water facilities by its ability to intercept large slugs of free oil and solids. The API is usually not
designed as a final treatment device.
The skimmings from the API are generally sent back to the process units, where they might be
re-used after minor cleaning operations. Otherwise they are chemical waste and have to be
adequately disposed of. The separated solids are to be disposed of as chemical waste.
Because of the possible release of volatile organic compounds the API separator should be
covered to avoid odour and health risks. Covering achieves a VOC release reduction of about
95 %. This is reported [cww/tm/48] about an API cover built in 1996.
Input and utilities are:
electric energy for oil skimming equipment (collector), and pumps

Sources of noise are the pumps, which are usually enclosed, and the oil collector.
Odour is to be expected from the buoyant oil, so that a cover is often necessary to avoid the
release of odorous substances.
Monitoring
The outlet has to be regularly monitored visually to ensure proper operation. Skimmer device
and weir have to undergo regular maintenance.
Costs
The investment costs are M 2.0 (flow rate 1200 m3/h, built in 1995) [cww/tm/48]
labour costs:
utilities:
total costs:
3.2.2.1.2.2
not known
Parallel Plate Interceptor (PPI)

A PPI is a gravity separator equipped with plates parallel to the current to promote laminar flow
and reduce the separation distance. An example is shown in Figure 3.5 [cww/tm/91]. Within a
PPI the combined surface area of the plates is significantly greater than the surface area of the
conventional API separator, resulting in a smaller ground area [cww/tm/48].
As with the API storage facilities for the skimmed liquids are necessary.
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Figure 3.5: Parallel Plate Interceptor (PPI)

Advantages
process units.
Disadvantages
High surface area with small ground area.

Plates are susceptible to fouling, so increased
maintenance requirement.
Sludge to dispose of.
The main aim of the PPI is to help to improve the performance of downstream waste water
facilities by its ability to intercept large slugs of free oil and solids. The PPI is not usually
designed as final treatment device.
The skimmings from the PPI are generally sent back to the process units, where they might be
Because of the possible release of VOCs the PPI should be covered to avoid odour and health
risks.
electric energy for oil skimming equipment and pumps

As with the API, the sources of noise are the pumping and skimming equipment. Appropriate
prevention measures have to be taken.
Because of buoyant oil, the installation might tend to release odorous substances which can
cause the requirement for covering.
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Monitoring
and oil dam have to undergo regular maintenance.
Costs
labour costs:
utilities:
total costs:
3.2.2.1.2.3
not known
Corrugated Plate Interceptor (CPI)

In the CPI, specially designed corrugated plate packs are placed counter current to the flow, as
shown in Figure 3.6 [cww/tm/91]. The effluent flows downward whereas the oil flows upward
to the surface. The CPI is particularly suitable as an installation on individual processing areas,
as close as possible to the point of waste water generation. Under these circumstances, there is
less likelihood of fouling and thus the oil might be recycled directly to the unit [cww/tm/48].
Figure 3.6: Corrugated Plate Interceptor (CPI)
Storage facilities for skimmed liquids and possibly sludge are necessary.
Advantages
process units.
Disadvantages
High surface area with small ground area.

Plates are susceptible to fouling.
Increased efficiency compared to API and PPI
by ability to remove smaller oil droplets.
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The main aim of the CPI separator is to help to improve the performance of downstream waste
water facilities by its ability to intercept large slugs of free oil and solids. The PPI usually is not
designed as a final treatment device.
The skimmings from the CPI are generally sent back to the process units, where they might be
Because of the possible release of volatile organic compounds the CPI should be covered to
avoid odour and health risks.
electric energy for oil skimming equipment, and pumps

The sources of noise are pumps and oil skimming equipment, where appropriate prevention
measures are to be taken.
Because of buoyant oil, the installation might tend to release odorous substances which can
cause the requirement of covering.
Monitoring
and oil dam have to undergo regular maintenance.
Costs
labour costs:
utilities:
total costs:
not known
3.2.2.2 Coagulation
Principle
Coagulation refers to the destabilisation of colloidal and small suspended particles (e.g. clay,
silica, iron, heavy metals, dyes, organic solids, oil in waste water), and emulsions by, e.g.,
aluminium or iron salts. Destabilisation causes the particles to settle.
Sometimes coagulation is succeeded by flocculation to induce the destabilised particles to form
large flocs that can easily be separated.
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Application
Coagulation is applied:
to increase the removal of colloids,

to condition waste water that contains colloidal components, e.g. heavy metals, or colloidal
polymers such as PVC and/or their monomers.
It is never an individual process or operation, but followed by separation operations, such as:
sedimentation of the flocs and decantation of the supernatant,

flotation, the flocs removed from the water surface by a scraper,
filtration, normally sand filtration.
exact pH range is essential during operation, because otherwise the clarification

performance might be poor,
stable emulsions cannot be broken by chemicals.

Coagulation needs rapid mixing, which can be achieved by:
simultaneous dosing of coagulants via multiple injection points,

preference of plug flow systems, where applicable,
flash mixer or mixing where the coagulant is added at or before the flash mixer,
static mixers or orifices.
Habitually used coagulants are [cww/tm/27]:
aluminium sulphate (alum),

ferric sulphate,
ferric chloride,
poly aluminium chloride,
poly aluminium sulphate,
cationic polymers,
anionic polymers,
non-ionic polymers.
Storage tanks for the coagulant chemicals are required, in addition to reactor, mixing and
injection devices.
When the waste water contains odorous substances the process can take place in a closed tank,
the waste gas ducted to an abatement system. The necessary equipment ducts and vents has
to be provided.
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Advantages
Enables relatively easy separation of not
readily settleable particles
Disadvantages
Additional sludge to dispose of.
Not a final treatment stage so a secondary step
is needed.
Increases clarification rate.
Special chemicals are needed entailing extra

costs.
Transfer of contaminants from waste water
into waste disposal.
Since coagulation is not used as an individual treatment method there are no emission values
to report for pollutants after a coagulation step. What can be said is that coagulation often
accompanied by flocculation usually increases the efficiency of separation processes for
particulates either originally present in the waste water stream or resulting from preceding steps.
As reported [cww/tm/51] an efficiency of more than 90 % is achievable.
The removal performance by coagulation for some important pollutants is presented in Table
3.2 [cww/tm/27].
Substance
Inorganic mercury
Cadmium and compounds
DDT (1,1,1-trichloro-2,2-bis-(pchlorophenyl)ethane)
HCB (hexachlorobenzene)
Aldrin
Dieldrin
Endrin
PCBs (polychlorinated biphenyls)
Tributyltin compounds
Trichloroethen
Perchloroethen
Removal
Performance
[%]
70
98
100
59
100
50
43
30 40
> 90
36
30
Table 3.2: Removal Performance by Coagulation
The floc, or sludge, will be disposed of as waste. Depending on the origin of the separated
substances, this waste might contain hazardous compounds which have to be treated adequately.
These compounds can be carbonates, fluorides, hydroxides (or oxides) of heavy metals,
phosphates, sulphates, sulphides, etc., oily scum and under certain circumstances even dioxins.
the coagulant chemicals, either salts or polymers, depending on the actual process,
electric energy for pumps, mixer.
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Noise is to be expected from the mixing and pumping equipment, which can be prevented or
controlled by appropriate measures. A closed tank might abate noise as well as prevent the
release of odorous substances. A contaminated gas phase can be ducted to a waste gas
abatement system.
Monitoring
The operation will be monitored to make sure that the proper amount of coagulant is added to
the mixing chamber. This is cost-effective as well as environmentally effective because it
avoids a surplus addition of chemical reagents to the waste water stream. The pH will be
recorded to make sure that correct conditions ensure reliable operation.
Costs
labour costs:
utilities:
total costs:
not known
3.2.2.3 Flocculation
Principle
The purpose of waste water flocculation is to induce suspended particles or emulsions to
agglomerate to settleable flocs. In contrast to coagulation, the flocculation process takes more
time (mostly 10 to 20 minutes), and the mixing intensity has to be appreciably smaller, because
too high a mixing velocity tears the flocs apart.
Application
Flocculation is applied:
to increase the removal of suspended solids by producing flocs large enough to settle,
to transfer emulsion droplets into large, separable globules,
to condition waste water that contains colloidal components, e.g. heavy metals or colloidal
polymers such as PVC and/or their monomers
to improve the performance of sedimentation of activated sludge in a CWTP.
It is never a stand-alone process or operation, but followed by a separation operation, such as:
sedimentation of the flocs and decanting of the supernatant,

flotation, the flocs removed from the water surface by a scraper,
filtration, normally sand filtration.
64
if metal compounds are used as flocculants, an exact pH range (either acidic or alkaline) is a
key issue, because otherwise the clarification performance might be poor,
stable emulsions cannot be broken by chemicals.
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Chapter 3

Flocculation needs gentle mixing during a longer period of time to increase the number of
particle contacts by collision. Accordingly the flocculator design is that of a mixing chamber. It
is often equipped as a baffled chamber, causing hydraulic mixing within the fluid as it flows
through the tank. Flocculator tanks, provided with paddle mixers, can be connected in series.
To ensure optimum operation it might be suitable to install an upstream oil separation or
emulsion decomposition stage, etc., to remove any substances that might interfere.
Normally used flocculants are:
air,
polyelectrolytes, cationic, anionic and non-ionic,
aluminium compounds such as alum and sodium aluminate,
iron compounds such as ferric chloride, ferric sulphate and copperas,
lime.
Partial recycling of the floc back into the flocculator can result in a better floc structure and an
optimum exploitation of flocculant.
Additional to the flocculation equipment, storage facilities for the flocculant chemicals have to
be provided. Whether the flocculation reactor or the combined flocculator/settler should be
covered depends on the waste water contaminants to be expect. With closed basins or tanks the
exhaust air has to be disposed of, e.g. by ducting it to a waste gas abatement. Adequate
equipment has to be provided for.
Advantages
Enables relatively easy separation of not
readily settleable particles
Disadvantages
Additional sludge to dispose of.
Not a final treatment stage. A secondary step
necessary.
Increases clarification rate.

Can be integrated in sedimentation tanks.
Special chemicals necessary, entailing extra

costs.
The floc can embed other contaminants that
might cause problems for disposal of the
sludge.
Transfer of contaminants from waste water
into waste disposal.

Since flocculation is never used as a sole treatment method there are no emission values to be
reported after a flocculation step. What can be said is that flocculation usually increases the
efficiency of separation processes for particulates either originally present in the waste water
stream or resulting from preceding steps. As reported [cww/tm/51], an efficiency of more than
90 % is achievable.
Flocculation of waste water that contains organic contaminants such as colloids, emulsions,
dyes and/or pathogens succeeds in a COD/TOC elimination of 30 70 % [cww/tm/82].
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The floc, or sludge, has to be disposed of as waste. Depending on the origin of the separated
substances, this waste might contain hazardous compounds which have to be treated adequately.
These compounds can be carbonates, fluorides, hydroxides (or oxides) of heavy metals,
phosphates, sulphates, sulphides, etc., oily scum and under certain circumstances even dioxins.
the flocculant chemicals, either salts or polymers, dependent on the actual process,

As with coagulation the main source for noise is the mixing and pumping equipment, which in
the case of a closed or covered tank is not a relevant issue.
If odorous substances can be expected, appropriate control measures are necessary, e.g.
covering the vessel and ducting the exhaust air to a gas abatement system.
Monitoring
The operation has to be monitored to make sure that the proper amount of flocculant is added to
the mixing chamber. This is cost-effective as well as environmentally effective because it
avoids a surplus addition of chemical reagents to the waste water stream. pH has to be recorded
to make sure that exact conditions ensure steady operation.
Costs
labour costs:
utilities:
total costs:
not known
3.2.2.4 Flotation
Principle
Flotation is a process where solid or liquid particles or particulates are separated from the waste
water phase by attaching to gas bubbles. The buoyant particles accumulate at the water surface
and are collected with skimmers [cww/tm/4].
Chemical additives, such as aluminium and ferric salts, activated silica and various organic
polymers, are commonly used to support the flotation process. Their function is to create a
surface or a structure able to absorb or entrap the air bubbles.
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Application
Flotation is used when gravity settlement is not appropriate, e.g. when:
the particulates have poor gravity settling characteristics,

the density difference between the suspended particles and water is too low,
there is a space constraint at the actual site,
oil and grease are to be removed,
recovery of material is required.
Flotation is used in petrochemical sites as a secondary treatment downstream of sedimentation

devices and prior to a biological process. Designed and operated correctly, it is capable of
separating and removing virtually all free oil from an effluent stream and can significantly
reduce the concentration of suspended solids. Flotation cannot handle gross free oil successfully
[cww/tm/48].
In chemical industry it is used, e.g. to recover product or raw material, to separate contaminants
or as the final stage of a CWTP [cww/tm/67, Neumann et al., p 327]. Examples are:
to recover silver halides from photographic chemical production,

to recover butylthion,
to recover polysilan from waste water,
to separate heavy metals from waste water streams,
to separate sludge after the final clarifier in a CWTP.
foaming detergents should be excluded,

gross free oil cannot be handled.

There are three methods of flotation, distinguished by the way air is added:
vacuum flotation, where air is dissolved at atmospheric pressure, followed by a pressure

drop to allow the formation of bubbles,
induced air flotation (IAF), where fine bubbles are drawn into the waste water via an
induction device such as a venturi or orifice plate,
dissolved air flotation (DAF), where pressurised air is dissolved into the waste water and
subsequently released to form small bubbles.
The most common flotation system is the DAF system. The waste water stream is sent to a
pressure vessel or in larger units a portion of about 30 % of the effluent is recycled to the
pressure vessel to be saturated with air. Pressures of approximately 5 7 bars are applied
[cww/tm/48]. The saturated waste water is released into the base of the main flotation tank via
an appropriately designed distribution network. Residence times can vary between 30 minutes
and several hours. Nearly all DAF units incorporate pre-treatment stages, such as flash mixing
where the flocculant or coagulant is added, followed by a calming tank where coagulation and
flocculation take place.
The design of the skimmer depends on the main tank configuration. Traditionally rotating
skimmers are used with circular tanks. Similarly configured scrapers are used to remove any
heavy sediment and oil from the bottom of the tank.
A typical dissolved-air flotation device is presented in Figure 3.7 [cww/tm/4].
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Chapter 3
Dependent on the waste water content, covering of the flotation basin might be necessary and
the exhaust air is ducted to a gas abatement device. Facilities are necessary to store the
flocculant/coagulant chemicals and the skimmed material.
Figure 3.7: DAF System: a) with Recycle, b) without Recycle

Advantages
Volume of clarification less than in gravitybased settling plants.
Disadvantages
No separation of soluble substances.
Gross free oil releases cannot be handled.
Unaffected by changes of flow rate and

temperature
Flocculant and coagulant chemicals are

needed.
Recovery of material is possible.

Clogging of valves is possible.
High separation efficiency.
Residue has to be disposed of as waste.
Higher operational costs than sedimentation.
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Known performance data are taken from [cww/tm/67, Neumann et al., p 327]:
Input:
effluent waste water:
input air saturated waste water:
compressed air consumption:
sludge discharge:
flocculant dosage:
filterable solids input:
filterable solids output:
effluent after final clarification stage of CWTP

1200 m3/h
80 135 m3/h
4.4 6.8 m3/h
20 m3/h
0.72 1.4 kg/h
20 250 mg/l
10 20 mg/l
Separation efficiency for:

TSS:
COD:
85 % (average over 200 readings)

70 % (average over 200 readings)
The separated material, if not recyclable, is disposed of as waste.

For refineries, an annual sludge production between 600 and 2400 tonnes for a unit operating at
600 m3/h is reported [cww/tm/48], but actual figures are expected to vary widely depending on
the type of effluent, the flocculant and the way the sludge is removed.
flocculant or coagulant, [cww/tm/67, Neumann et al., p 327] report a flocculant dosage of

0.72 1.4 kg/h or 0.5 1.6 ppm.
compressed air, [cww/tm/67, Neumann et al., p 327] report of 4.4 6.8 m3/h.
electric energy for pumps, mixer and compressor.
The energy consumption is 20.6 kWh/1000 m3 [cww/tm/67, Neumann et al., p 327]
Sources of noise are the pumps, mixer and compressor, which have to be equipped with
adequate shelter measures.
The release of odorous or other volatile substances if these are to be expected can be
prevented by covering the vessel or operating in a closed tank and ducting the exhaust air to a
gas abatement system.
Monitoring
To ensure reliable operation, the turbidity of the effluent has to be monitored to recognize
disturbances. The arising of foams is an important issue to detect in time. Effluent detection of
COD/TOC and TSS is obligatory.
Costs
The investment costs for the flotation system reported in [cww/tm/67, Neumann et al., p327] are
approximately kDM 5000 (plant for 1200 m3/h), inclusive capital costs, engineering design,
civil engineering works, site preparation, etc.
The investment costs for flotation in the refinery sector vary between M 1.6 and 1.8 (plants
for 300 800 m3/h) for DAF, and M 0.5 2.0 (plants for 400 820 m3/h) for IAF
[cww/tm/48]
Another source [cww/tm/92] gives:
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Flow rate
[m3/h]
Capital Costs
[M]
Annual Operating Costs

[k]
10
100
1000
10000
0.1
0.1
0.5
1.0
10
20 30
50 80
500 - 800

labour costs:
utilities:
total costs:
approximately kDM 800/year [cww/tm/67, Neumann et al., p

327] (plant with 1200 m3/h)
k 20 130/year (DAF for 300 800 m3/h) [cww/tm/48]
k 55 130/year (IAF for 400 820 m3/h) [cww/tm/48]
3.2.2.5 Filtration
Principle
Filtration describes the separation of solids from waste water effluents passing through a porous
medium. Filters typically require a cleaning operation backwashing, where the flow through
the filter is reversed, using fresh water instead. The accumulated material is washed back to the
sedimentation tank.
Application
Filtration is used frequently in waste water treatment. It is usually the final separation stage, if
low emissions of particulates are wanted. So filtration is the secondary operation for, e.g.:
separation of floc, heavy metal hydroxides etc. after sedimentation, to cope with discharge
requirements,
removal of activated sludge after the CWTP, in addition to sedimentation, to improve the
quality of biologically treated water effluent,
sludge de-watering.
colloids cannot be separated,

fine dispersed or slimy solids can bloc the filter medium.

There are several types of filter systems, e.g.
the granular-medium filter, or sand filter, which is widely used as a waste water treatment
device,
the belt filter press, which is largely used for sludge de-watering, but also for liquid/solid
separation operations,
filter presses, which usually are used for sludge de-watering, but also for liquid/solid
operations.
Sand filters consist of a granular-medium filter bed with either downward or upward flow. The
filter bed can be mono- or multi-medium. The operation can be semicontinuous filtration and
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backwashing occur sequentially or continuous filtration and backwashing operate

simultaneously. The main difference between the two operation modes is:
semicontinuously operated sand filters are run up to turbidity breakthrough, when the solid
content in the effluent starts to increase, or to limiting headloss,
continuously operated sand filters have no turbidity breakthrough or terminal headloss.
Sand filters work either by the force of gravity or an applied pressure force. Examples are given
in Figure 3.8 [cww/tm/4] for the conventional downflow multi-medium, gravity-flow filter and
in Figure 3.9 [cww/tm/4] for the pressure filter.
Belt filter press and filter press as typical sludge de-watering facilities are described in Chapter
3.4.3.2 and 3.4.3.3 below respectively.

Advantages
Disadvantages
Clogging and fouling processes are possible
with semi-continuous sandfilters.
Pollutants other than suspended solids can be

removed under certain circumstances, such as
hydrocarbons and nutrients.
Breakthrough can cause additional pollution of

the effluent.
Operation under a wide range of conditions.
Ineffective for dissolved pollutants.
Figure 3.8: Conventional Downflow Multi-medium Sandfilter
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Chapter 3
Figure 3.9: Pressure Filter

The emissions available with filtration are dependent on the pollutants. For filterable solids after
the last clarifying stage of a biological CWTP, values less than 10 mg/l are achievable.
The emissions of heavy metals after filtration as final step of precipitation,
flocculation/coagulation and sedimentation are presented in Chapter 3.2.3.1 below.
The backwashed accumulated material is recycled to the sedimentation tank or, after final
filtration behind the sludge settling basin of a CWTP, to the activated sludge basin of the
CWTP.
water for backwashing,

electric energy for pumps and mixer,
filter material probably to exchange, though this does not happen often.

The pressure drop is not known
The filtration process itself is not a relevant noise source.
The presence of odorous substances depends on the waste water content. If such substances can
be released (sand filter) closed devices might be necessary. Pressure filters and filter presses are
placed in closed vessels, exhaust air ducted to a gas abatement system.
Monitoring
To ensure reliable operation, the turbidity of the filter effluent has to be monitored to recognize
disturbances, or a breakthrough with the semi-continuous sandfilter. The pressure drop has to be
registered to be aware of clogging and barring.
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Chapter 3
Costs
The investment costs are not known.
labour costs:
utilities:
total costs:
not known
3.2.2.6 Pore Type Membrane Processes
Principle
A membrane process is the permeation of a liquid through a membrane, segregating into
permeate that passes the membrane and concentrate that is retained. Driving force of this
process is the pressure difference across the membrane.
Pore-type membranes operate like sieves. The solvent as well as particles of molecular size can
pass the pores, whereas suspended particles, colloidal particles, bacteria, viruses, and even
larger macromolecules are hold back. Porous membrane processes are microfiltration and
ultrafiltration.
Typical characteristics are shown in Table 3.3.
Parameter
Microfiltration
Ultrafiltration
Pore diameter [m]

[cww/tm/27]
0.1 - 1
0.001 0.1
Operating Pressure
[bar] [cww/tm/93]
1-4
1 10
particle size [m]
> 0.1, includes bacteria
> 0.01, includes macromolecules, viruses, colloidal particles
Separation cut-off
range [cww/tm/93]
solid/liquid: 0.1 20 m
solid/liquid: 0.005 0.1 m

solute/liquid: 10000 200000
(Molecular Weight)
Membrane type
[cww/tm/93]
symmetrical polymeric or
ceramic, 10 150 m thick
polymeric, or ceramic
asymmetric
Membrane
configuration
[cww/tm/93]
spiral-wound
hollow-fibre
tubular
ceramic
inorganic
spiral-wound
hollow-fibre
tubular
Table 3.3: Characteristics of Microfiltration and Ultrafiltration
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Chapter 3
3.2.2.6.1
Microfiltration (MF)
Application
MF is applicable when a solid free waste water is desired or hazardous contaminants such as
heavy metals after precipitation should be removed entirely.
MF can be used as a pre-treatment to remove all solids where these could cause damage or
restraint to a subsequent treatment stage, e.g. reverse osmosis, or as a preceding step to
ultrafiltration to avoid clogging or fouling at this stage.
Common MF applications include [cww/tm/93]:
degreasing processes,
metal particle recovery,
metal plating waste water treatment.
Another application of MF is the activated membrane process, where it is used as a different

option instead of the secondary clarifier after the aeration basin in a CWTP, with the advantage
of a decrease in aeration volume [cww/tm/67, Rosenwinkel et al., p. 183].
restricted capacity to retain suspended particles sized below 0.1 m,

characteristics of the membrane material, which can be vulnerable to chemical attacks.

Membranes are available in several materials and configurations. The optimum modification for
a particular application will depend on the nature of the waste water, since the different
materials have varying resistances to dissolved substances. Membrane materials for MF are, e.g.
glass fibre, polycarbonate, cellulose acetate and polyamide. The polyamide based membranes
are normally superior to cellulose acetate based membranes to remove trace organic molecules.
Usually the MF process is run cross-flow, i.e. the permeate flow is directed perpendicular to the
feed flow. The impurities remain in the feed which, reducing in volume, leaves the membrane
system as a concentrated waste stream.
Storage facilities for the concentrate should be available.

Advantages
Disadvantages
Dissolved substances and suspended particles
sized below 0.1 m are not retained
Modular systems, i.e. flexible in usage.

Clogging, plugging and fouling processes are
possible.
Compaction in the presence of softening
agents.
High prices.
Ineffective for dissolved pollutants.
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There were no performance data available.
Membrane treatment produces a residue (concentrate) of approximately 10 % of the original
feed volume, in which the target substances are present at levels approximately 10 times their
concentration in the waste water. It should be assessed if this residue can be disposed of.
With organic suspended substances the concentration increase might improve the conditions for
subsequent oxidative destruction processes. With inorganic suspended substances the
concentration stage could be used as part of a recovery process. In both cases, the permeate
water from a MF process can potentially be re-used or recycled in the industrial process, thus
reducing water input and discharge.
the membrane material,

probably antiscaling chemicals,
electric energy for pumps.
The energy consumption is directly related to the flow rate and pressure requirements. It is
generally associated with maintaining a minimum velocity of about 2 m/s across the membrane
surface.
A source of noise is the pumping equipment, which might be enclosed.
Monitoring
To ensure reliable operation, the pressure difference across the membrane has to be monitored
continuously.
Costs
A guideline for investment costs might be[cww/tm/93]:
400 1500 per m2 membrane for hollow-fibre, spirals and ceramic membranes.
Replacement membrane costs are [cww/tm/93]:
80 350 per m2 membrane for hollow-fibre, spirals and ceramic membranes.
The capital costs, including automated cleaning facilities, can be broken down approximately as
follows [cww/tm/93]:
pumps
replaceable membrane components
membrane modules (housings)
pipework, valves, framework
control system
other
30 %
20 %
10 %
20 %
15 %
5%
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Chapter 3
The operating cost [cww/tm/93] is derived from:
energy cost of maintaining the hydrostatic pressure and flow rate of the systems,
expected membrane life,
cleaning regime required,
site-specific factors, e.g. labour requirement.
They can be broken down approximately as follows [cww/tm/93]:

cleaning
energy
labour
35 50 %
12 35 %
15 20 %
15 18 %
labour costs:
utilities:
total costs:
3.2.2.6.2
not known
Ultrafiltration (UF)
Application
Compared with other membrane techniques (MF, nanofiltration or reverse osmosis), UF has a
variety of advantages, such as:
better separation efficiency than conventional filtration or sedimentation to remove

macromolecular and colloidal species,
operating at relatively low-pressures, high fluxes and mild temperatures, and therefore
particularly suitable for sensitive materials,
membranes available in many varieties of pore size, material and construction.
The main fields of application are:
removal of non-toxic degradable pollutants such as proteins and other macromolecular

compounds and toxic non-degradable components, e.g. dyes and paints, with molecular
weights greater than 1000,
separation of oil/water emulsions,
segregation of heavy metals after complexation or precipitation,
separation of components not readily degradable in sewage treatment effluents, which are
subsequently recycled to the biological stage,
pre-treatment step prior to reverse osmosis or ion exchange,
substitution of the secondary clarifier behind the aeration basin in the CWTP [cww/tm/67,
Rosenwinkel et al., p. 183].
76
restricted retaining of suspended particles sized below 0.01 m and of dissolved substances
with a molecular weight < 1000,
characteristics of the membrane material, which can be vulnerable to chemical attacks
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Chapter 3

materials have varying resistances to dissolved substances. Membrane materials for UF are
organic polymers, such as cellulose acetate, polyamide, polyimide, polycarbonate,
polyvinylchloride, polysulphone, polyethersulphone, polyacetal, copolymers of acrylonitrile and
vinyl chloride, polyelectrolyte complexes, cross-linked polyvinyl alcohol or polyacrylates. The
polyamide based membranes are normally superior to cellulose acetate based membranes to
remove trace organic molecules.
Usually the UF process is run cross-flow, i.e. the permeate flow is directed perpendicular to the
feed flow. The impurities remain in the feed which, reducing in volume, leaves the membrane
system as a concentrated waste stream.

Advantages
Disadvantages
Modular systems, so flexible in usage.

possible.
agents.
High prices.

There were no performance data available.
Membrane treatment produces a waste stream (concentrate) of approximately 10 % of the
original feed volume, in which the target substances are present at levels approximately 10
times their concentration in the waste water. It should be assessed if this residue can be disposed
of.
With organic substances the concentration increase might improve the conditions for
subsequent oxidative destruction processes. With inorganic substances the concentration stage
could be used as part of a recovery process. In both cases, the permeate water from a UF
process can potentially be re-used or recycled in the industrial process, thus reducing water
input and discharge.

probably antiscaling chemicals,
generally associated with maintaining a minimum velocity of about 2 m/s across the membrane
surface.
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Chapter 3
The energy consumption is calculated according to:
E = 50 [W/m2]/(0.5 x J [l/(m2 x h)])

with J as waste water flux [cww/tm/93]. This energy requirement does not include add-on loads
such as preliminary treatments or frequent cleaning.
A source of noise is the pumping equipment, which might be enclosed.
Monitoring
To ensure reliable operation, the pressure difference across the membrane has to be monitored
continuously.
Costs
A guideline for investment costs is[cww/tm/93]:
400 1500 per m2 membrane for hollow-fibre, spiral and ceramic membranes.
80 350 per m2 membrane for hollow-fibre, spiral and ceramic membranes.
pumps
control system
other
30 %
20 %
10 %
20 %
15 %
5%
energy cost of maintaining the hydrostatic pressure and flow rate of the system,
The operating costs can be broken down approximately as follows [cww/tm/93]:

cleaning
energy
labour
35 50 %
12 35 %
15 20 %
15 18 %
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labour costs:
utilities:
total costs:
not known
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Chapter 3
3.2.3 Soluble Non-biodegradable Waste Water Contaminants

Soluble non-biodegradable waste water contaminants can be subdivided into two classes of
compounds:
inorganic compounds such as salts or heavy metal compounds,
calcitrant, or refractive, TOC.
These are classes of compounds that are either not affected by biological treatment or tend to
disturb the biological process in a CWTP. In both cases they usually need special pre-treatment
before they can enter the CWTP. Pre-treatment operations are normally physical
separations/segregations or chemical transformations with subsequent physical separation. The
appropriate operations and processes are described in the following chapters.
3.2.3.1 Precipitation
Principle
Chemical precipitation is a process in which dissolved components react with added chemicals
to form very slightly soluble or insoluble compounds. Precipitation might be supported by
flocculant or coagulant chemicals.
The precipitate will be separated from the waste water, e.g. by sedimentation, and optionally
followed by filtration or microfiltration [cww/tm/77]. The sludge has to be disposed of.
Application
Precipitation is a process normally used to remove heavy metals, phosphate, sulphate and
fluoride from waste water. The most common precipitation chemicals are lime and dolomite.
Another source [cww/tm/77] reports a ferrous sulphate/sodium sulphide process, which is
specific to metal removal.
A common method of lime dosing is to add the lime upstream of a separation process and
remove the precipitates in the clarifier. A key issue with precipitation to achieve high removal
efficiency is an optimum adjustment of pH. The optimum pH range to remove heavy metals,
phosphate and fluoride is 9 12.
Precipitation with ferrous sulphate/sodium sulphide to remove heavy metals is operated under
neutral or alkaline conditions. Acidic pH generates hydrogen sulphide and must be avoided.
To remove phosphate from the biological CWTP, lime, aluminium or ferrous salts are added
after biological treatment. The sludge is collected in the secondary or final clarifier, then treated
and the aqueous residue recycled to the biological stage.

A precipitation system usually consists of one or two stirred mixing tanks, where the agent and
possibly other chemicals are added, and a sedimentation tank. After sedimentation, a filtration
step might complete the design, as e.g. with heavy metals, where sedimentation alone does not
cope with environmental requirements. The use of MF as a final step is reported [cww/tm/77].
Chemicals to remove phosphate are ferric chloride, aluminium sulphate, ferrous sulphate,
ferrous chloride, lime and polymers. Storage facilities for these chemicals are necessary. If lime
milk is used, the necessary devices for its preparation are part of the operation unit.
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Chapter 3

For lime:
Advantages
Prevention of increasing salt content in the
waste water.
Disadvantages
Substantial increase in the mass of sludge as
compared to metal salts.
Increase of the buffering capacity of the

CWTP.
Operating problems associated with the

handling, storage and feeding of lime
[cww/tm/4].
Improvement in sludge sedimentation.

Sludge thickening.
Maintenance problems [cww/tm/4].

Improvement of mechanical de-waterability of
sludge.
Reduction of de-watering cycle time.
For ferrous sulphate/sodium sulphide [cww/tm/77]:
Advantages
Decrease of amount of sludge (about 30 % in
volume compared to lime treatment).
Decrease of amount of chemicals used (about
40 %, compared to lime treatment).
Disadvantages
If the batch becomes acidic, generation of
hydrogen sulphide is possible.
Produces lower metal levels in treated

effluent.
No pre- or post-treatment needed.
Highly efficient at removing suspended and
dissolved metals from a waste water stream.

Achievable residual concentrations for pollutants after precipitation with lime are [cww/tm/76]:
aluminium:
copper:
chromium(III):
iron(III):
iron(II):
zinc:
lead:
nickel:
cadmium:
sulphate:
fluoride:
phosphate:
< 2 mg/l
0.07 mg/l
0.3 mg/l
< 2 mg/l
< 2 mg/l
0.01 mg/l
0.03 mg/l
0.09 mg/l
0.09 mg/l
< 400 mg/l
< 3 mg/l
< 1 mg/l
For other agents no values were available.
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The precipitants usually have to be disposed of as sludge. Often this sludge is chemical waste,
at least if heavy metals are involved, with the result that discharged activated sludge is generally
not suitable for agricultural usage. This waste may contain carbonates, fluorides, hydroxides (or
oxides) of heavy metals, phosphates, sulphates, sulphides, etc.
flocculant and/or coagulant chemicals,

precipitation agent, i.e. lime, dolomite, ferrous and ferric salts, aluminium sulphate or
polymers,
electric energy for pumps and sludge removal system

Sources of noise are pumps and sludge removal facilities. Appropriate measures for noise
control have to be taken.
If the release of volatiles and odorous substances can be expected, precipitation should be
operated in closed tanks or covered basins with ducts to gas abatement.
Monitoring
During the precipitation process the pH value and the dosage of flocculants and/or coagulants
have to be carefully adjusted.
Costs
A rough capital cost approach is [cww/tm/92]:
C = 90 + 16 x Q0.6
with Q as plant throughput in m3/h, the result given as .
The investment costs are not known.
labour costs:
utilities:
total costs:
not known
3.2.3.2 Adsorption
Principle
Adsorption is the transfer of soluble substances (solutes) from the waste water phase to a batch
of solid, highly porous, particles (the adsorbent).
For each compound to be removed, the adsorbent has a finite capacity. When this capacity is
exhausted, the adsorbent is spent and has to be replaced by fresh material. The spent adsorbent
either has to be regenerated or incinerated.
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Chapter 3
Adsorbent materials include mainly:
activated carbon,
synthetic resins,
zeolites.
3.2.3.2.1
Granular Activated Carbon (GAC) Adsorption
Application
GAC Adsorption is applied in the chemical industry to remove organic contaminants, mainly
those with refractory, toxic, coloured and/or odorous characteristics, and residual amounts of
inorganic contaminants, such as nitrogen compounds, sulphides and heavy metals. Granular
medium filters, e.g. sand filters, are commonly used upstream of the GAC adsorber to remove
the suspended solids present.
Representative applications are [cww/tm/92]:
Textiles and Dyestuffs:

Oil Refinery and Petrochemical:
Detergents, Resins, Chemicals:
Herbicides, Insecticides:
Pharmaceuticals:
Explosives:
removal of TOC, colour, dyes

removal of COD, BOD
removal of TOC, COD, xylene,
alcohols, phenols, resin intermediates,
resorcinol, nitrated aromatics, polyols
removal of chlorophenols, cresol
removal of phenol
nitrated phenol
high concentrations of suspended solids produce deposits on the adsorber, which can cause
pressure loss, flow channeling or blockages, resulting in loss of adsorption capacity,
pollutant concentration < 50000 mg/l, with adsorbent recovery [cww/tm/51],
pollutant concentration < 10000 mg/l, without adsorbent recovery [cww/tm/51],
suspended solids concentration < 20 mg/l with fixed bed adsorbers [cww/tm/4],
suspended solids concentration < 10 mg/l with moving bed adsorbers [cww/tm/51],
decreased efficiency, when compounds with low molecular weights, high polarity and high
solubility are involved,
decreased efficiency with macromolecular structures.
Typical removal characteristics of organic compounds in the order of increasing polarity are
reported in Table 3.4 [cww/tm/91].

The following adsorption systems are generally used:
82
fixed-bed adsorbers, with GAC packed in a column, up-flowed or down-flowed by the

waste water stream, placed in parallel or in series. Usually two columns are necessary for
duty and backwashing,
pulsed-bed adsorbers, with the waste water flow stopped periodically to replace the spent
GAC,
moving-bed adsorbers, with the waste water flowing upward through a steadily downward
moving GAC bed.
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Chapter 3
A typical GAC Adsorber is shown in Figure 3.10 [cww/tm/4].

Substance
Benzene
Ethylbenzene
Buthyl acetate
Ethyl acetate
Phenol
Methyl ethyl ketone (MEK)
Acetone
Pyridine
Diethanol amine
Monoethanol amine
Acetaldehyde
Formaldehyde
Isopropyl alcohol
Methyl alcohol
Removal
[%]
capacity
[mg/g]
95
84
84
51
81
47
22
47
28
7
12
9
22
4
80
19
169
100
161
94
43
95
57
15
22
18
24
7
Table 3.4: Typical Performance Characteristics of GAC Adsorbers with Feed Concentrations of
about 1000 mg/l
The adsorber device is usually built of corrosion resistant material, e.g. lined carbon-steel,
stainless steel or fibreglass-reinforced plastic.
Storage facilities for GAC are necessary.
Figure 3.10: Typical GAC Adsorber
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Chapter 3

Advantages
Good removal efficiency.
Disadvantages
Mixtures of organic compounds may cause a
significantly reduced adsorption capacity.
Enables removal of refractory and/or toxic

organic compounds.
Waste water with high solids content has to be

pre-treated.
Usually low extra space requirement.

High content of macromolecular compounds
decreases efficiency and may cause
irreversible blockage of active sites.
Systems automated.
High capital and operating costs.

Spent adsorbent has to be regenerated (high
energy consumption) or disposed of (causing
waste to be incinerated).

The efficiency of adsorption processes varies widely with waste water composition, which one
should bear in mind when references to achievable emissions or removal efficiencies are cited.
Achievable removal efficiencies are reported as [cww/tm/27]:
Inorganic mercury [feed 29 g/l]
Organic mercury [low feed]
Gamma hexachlorocyclohexane [feed 7.7 g/l]
DDT
Aldrin
Dieldrin
Atrazine [feed 0.61 g/l]
80 %
80 %
93 %
97 %
88 93 %
86 98 %
84 %
Another report gives the following data [cww/tm/82]:

Adsorbent:
waste water flow:
COD [feed 5000 mg/l]:
Phenols [feed 70 mg/l]:
AOX [feed 60 mg/l]:
GAC, moving bed adsorber,

200 m3/h
approximately 50 % removal
75 % removal
> 90 % removal.
When the adsorptive capacity of GAC has been exhausted it will be replaced and/or
regenerated. Regeneration is a high temperature process at about 800 C, so the energy costs
and consumption as well as logistics are considerable. The regeneration process of GAC
produces off-gases that contain the thermal and chemical decomposition products of the
adsorbed compounds. With each regeneration a proportion of about 10 % will be lost
[cww/tm/27] and has to be replaced by fresh GAC. This continuous renewal should be adequate
to maintain the overall quality of the GAC in the bed. The regeneration of GAC would normally
be carried out by specialist companies, which operate regeneration furnaces. These companies
will transport GAC to and from regeneration. As regeneration is relatively expensive, plants are
usually designed to give a period of at least six months between regeneration cycles.
The generation of off-gases with regeneration causes subsequent waste gas treatment, if not at
the chemical site itself, then at the site of the regenerating company, which might be considered
as a displacement of pollution from waste water to waste gas.
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If the GAC cannot be regenerated, it has to be disposed of as chemical waste and incinerated.
This might be the case if the GAC is contaminated with PCBs, dioxins, heavy metals or
dichlorobromopropane (DCBP) [cww/tm/77].
GAC used, at least the 10 % loss after each regeneration,

electric energy for pumps,

Further impact on the environment can be:
the transport of spent GAC to and from regeneration,

the regeneration operation itself at the site of a specialist company,
the energy consumption for the regeneration process,
the release of contaminants to water and/or air during this regeneration process.
Sources of noise are the pumps, which can be enclosed.
Monitoring
Input and output of the GAC adsorber device has to be monitored according to the compounds
in question. Normally a TOC measurement would be the method of choice for a breakthrough
warning.
Costs
Capital costs for GAC adsorption units, excluding installation costs but including GAC, are
given as [cww/tm/92]:
k 30
k 75
k 110
1000 kg GAC capacity

14 m3/h flow rate

60 m3/h flow rate
120 m3/h flow rate
labour costs:
utilities:
total costs:
not known
Regeneration costs of the GAC may be between 1000 and 2000 per tonne [cww/tm/92].
3.2.3.2.2
Powdered Activated Carbon (PAC) Adsorption
Application
PAC Adsorption is applied in chemical industry to remove organic contaminants, mostly those
with refractory, toxic and/or coloured characteristics. PAC is usually dosed to the waste water to
be treated as a slurry. It is removed by subsequent unit treatment processes such as
sedimentation and filtration. Or, PAC can also be added to the waste water stream at the same
point as the inorganic coagulants and removed by already existing sedimentation and filtration
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Chapter 3
devices. PAC is usually preferred where the requirement of adsorptive removal of organics is
intermittent or variable. It can be dosed individually as and when it is needed.
PAC can also be added to the aeration basin of activated sludge systems, where the
microbiological activated sludge processes are enhanced by the adsorption process.

PAC adsorbents are typically used with a mixer-settler or slurry adsorber arrangement in
combination with coagulation/flocculation agents. The PAC is added into the flocculation,
sedimentation or filtration step.
The usual equipment consists of:
bulk PAC storage tank,

PAC transfer equipment,
slurry mixing tank,
slurry dosing pump.
The adsorber devices have to be constructed of corrosion resistant material, e.g. lined carbonsteel, stainless steel or fibreglass-reinforced plastic.

Advantages
Good removal efficiency.
Disadvantages
Usually used on a once only basis.
Flexibility because of individual dosing.
Mixtures of organic compounds may cause a

significantly reduced adsorption capacity.

organic compounds.
Downstream separation processes are

necessary.
Usually low extra space requirement.

The efficiency of adsorption processes varies widely with waste water composition, which one
should bear in mind when references to achievable emissions or removal efficiencies are cited.
Gamma hexachlorocyclohexane [feed 10 g/l, dose 85 mg/l]
Aldrin [dose 20 mg/l]
Aldrin [dose 5 mg/l]
Dieldrin [dose 126 mg/l, feed 10 g/l]
Endrin [dose 70 mg/l, feed 10 g/l]
Dichlorvos
TCB [dose 20 mg/l, feed up to 200 g/l]
Fenitrothion
Azinphos-methyl
99 %
99 %
90 %
99 % [down to 0.1 g/l]
< 0.1 g/l
99 %
70 93 %
99 %
99 %
According to [cww/tm/77], PAC waste water treatment systems can treat waste water with a
COD higher than 60000 mg/l, including toxic volatile organic compounds higher than 1000
mg/l with a reduction of specific toxic organic chemicals to below the detection limit.
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The PAC is usually removed together with the slurry from sedimentation and/or filtration.
PAC,
Monitoring
Laboratory tests are needed in advance of process design to assess the required dose of PAC.
Costs
labour costs:
utilities:
total costs:
3.2.3.2.3
not known
Zeolite Adsorption
Application
Zeolite adsorption is applied to remove ammonia or heavy metals, such as cadmium, from
waste water. When the zeolite bed is spent, it will be regenerated.

A typical zeolite adsorption plant operates two adsorption beds, one in duty and the other in
regeneration mode. Besides the adsorber beds, regeneration facilities are part of the equipment.
Suitable zeolites can adsorb about 4 kg NH4-N per m3 of zeolite bed.
Storage facilities for zeolites and the regenerant chemicals are necessary.

Advantages
Good removal efficiency for ammonia.
Disadvantages
Zeolites have to be regenerated.
Process generates a stream of concentrated
ammonia waste.

Ammonia [feed 25 mg/l]
98 % [0.5 mg/l]
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Chapter 3
The process generates a stream of concentrated ammonia waste. This can be ducted to a
conventional waste water treatment plant for biological treatment. Alternatively, it can undergo
a treatment comprised of air stripping to recover ammonia from the waste stream, followed by
adsorption in dilute acid to form a fertiliser which can be sold.
zeolites, which will be regenerated,

sodium chloride for regeneration, regenerant amounts to about 10 30 bed volumes

Monitoring
Input and output of the zeolite adsorber device has to be monitored according to NH4-N or
heavy metals, to get the warning of a breakthrough.
Costs
labour costs:
utilities:
total costs:
not known
3.2.3.3 Ion Exchange
Principle
Ion Exchange is the removal of undesired or hazardous ionic constituents in waste water and
their replacement by more acceptable ions from an ion exchange resin, where they are
temporarily retained and afterwards released into a regeneration or backwashing liquid.
Application
Ion exchange is applied to remove unwanted ionic species from waste water, e.g.:
heavy metal ions cationic or anionic, e.g. Cr3+ , CrO42- or cadmium and its compounds,
with low feed concentrations,
anions such as halides, sulphates, nitrates and cyanides,
soluble, ionic organic compounds, e.g. carboxylic acids, sulphonic acids, some phenols,
amines as acid salt, quaternary amines, alkylsulphates and organic mercury can be removed.
Ion exchange is feasible as an end-of-pipe treatment, but its greatest value lies in its recovery
potential. It is commonly used as an integrated operation in waste water treatment, e.g. to
recover rinse water and process chemicals. Typical influent concentrations are between 10 and
1000 mg/l. Suspended particles in the feed should be less than 50 mg/l to prevent plugging.
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swelling of resin particles due to high ionic strength in the waste water,
thermal limits of anion resins generally in the vicinity of 60 C,
nitric acid, chromic acid, hydrogen peroxide, iron, manganese and copper can damage the
resins because of corrosiveness,
interfering of inorganic compounds, e.g. iron precipitates or organic compounds, e.g.
aromatics, can cause irreversible adsorption to the resin.

The equipment of an ion exchanger usually consists of:
a vertical cylindrical pressure vessel with corrosion-resistant linings that contains the resin,
usually as a packed column with several possible configurations,
a control valves and piping system, directing the flow of waste water and regeneration
solution to the proper locations,
a system to regenerate the resin, consisting of salt dissolving and dilution control
equipment.
An inlet distribution system is located at either the top or the bottom of the vessel and provides
even distribution of the influent waste water, to prevent hollowing out flow channels in the resin
bed. It acts also as collector for backwash water.
Ion exchangers commonly in use are macroporous granule resins with cationic or anionic
functional groups, such as:
strong acid cation exchangers (SAC), neutralising strong bases and converting neutral salts
into their corresponding acids,
weak acid cation exchangers (WAC), able to neutralise strong bases and used for
dealkalisation,
strong base anion exchangers (SBA), neutralising strong acids and converting neutral salts
into their corresponding bases,
weak base anion exchangers (WBA), neutralising strong acids and used for partial
demineralisation.
The ion exchange operation cycle comprises:
the actual ion exchange operation,

the backwash stage, including removal of accumulated particles and reclassification of the
ion exchange resin bed,
the regeneration stage, using a low volume/high concentration solution, reloading the ion
exchange resin with the respective ion, and releasing the unwanted ion species to the
regeneration solution,
the displacement, or slow rinse, with a slow water flow displacing the regeneration solution
through the bed,
the fast rinse, removing of the remaining traces of the regeneration solution, inclusive any
residual hardness, from the resin bed.
Storage facilities for the regeneration chemicals are necessary.
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Chapter 3

Advantages
In principle all ions can be removed from
aqueous liquids.
It operates on demand, relatively insensitive to
flow variations.
Disadvantages
Not feasible at high levels of total dissolved
solids, suspended particles and/or organic
compounds.
The brine resulting from regeneration has to
be treated or to be disposed of.
High efficiency possible.

Bacteria growth on the resin surface.
Recovery of valuable species is possible.
Fouling caused by precipitation or adsorption.
Water recovery possible.
Interfering of competing ions in the waste
water.
No sludge produced.
A large variety of specific resins are available.
Attrition of resin particles, due to regeneration

or mechanical impacts.
High costs.

Typical effluent ion concentrations that can be achieved are in the range of 0.1 10 mg/l with
influent concentrations of 10 1000 mg/l.
The regeneration of ion exchange resins results in a small volume of concentrated acid or salt
solution, containing the removed ions originating from the resin. This enriched liquid has to be
treated separately to remove these ions, e.g. heavy metals by precipitation.
The rinsing water from regeneration contains the same ions as the brine, but in relatively low
concentrations. Whether this part can be discharged directly or has to undergo treatment
depends on the actual concentrations.
ion exchange resin, which has to be removed after its service life has run out,
regeneration liquid, e.g. hydrochloric acid, sulphuric acid, sodium chloride, sodium
hydroxide, etc.,
backwash and rinsing water,

Monitoring
Influent and effluent of the ion exchange vessel have to be carefully monitored to recognize the
occurrence of breakthrough.
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Costs
Capital costs depend on the nature of the feed stream. For a packed height of 1 m and 1 m of
diameter costs are about k 60 (vessel, valves, resin). For each 0.5 m of diameter the costs rise
by about k 20 [cww/tm/92].
labour costs:
utilities:
total costs:
not known
3.2.3.4 Diffusion Type Membrane Process
Principle
A membrane process is the permeation of a liquid through a membrane, segregating into
permeate that passes the membrane and concentrate that is retained. Driving force of this
process is the pressure difference across the membrane.
Diffusion type membranes are (ideally) free of pores. The solvent passes the membrane layer by
way of diffusion. Diffusion type membranes can hold back all particles down to the size of
organic molecules and even ions. Provided that the feed is particle free, diffusion-type
membranes are mainly used when complete recycling of permeate and/or concentrate is desired.
Diffusion type membrane processes are nanofiltration and reverse osmosis. Their typical
characteristics are illustrated in Table 3.5.
3.2.3.4.1
Nanofiltration (NF)
Application
NF is applicable to remove larger organic molecules and multivalent ions in order to recycle
and re-use the waste water or reduce its volume and simultaneously increase the concentration
of contaminants to such an extent that other subsequent destruction processes are feasible.
restricted capacity to retain suspended particles sized below a molecular weight of 200,
characteristics of the membrane material, which can be vulnerable to chemical attacks.

materials have varying resistances to dissolved substances. Membrane materials for NF are, e.g.
cellulose acetate and polyamide. The polyamide-based membranes are normally superior to
cellulose acetate-based membranes, regarding the removal of trace organic molecules.
Usually NF processes are operated cross-flow, i.e. the permeate flow is directed perpendicular
to the feed flow. The impurities remain in the feed which, reducing in volume, leaves the
membrane system as a concentrated waste stream.
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Parameter
Nanofiltration
Reverse Osmosis
Pore diameter [m]

[cww/tm/27]
0.01 0.001
< 0.001
Operating Pressure
[bar] [cww/tm/93]
20 - 40
15 - 60
particle size [m]
particles of molecular weight

200 10000
down to ionic species
Separation Cut-off
Range [cww/tm/93]
solid/liquid: 0.001 0.01 m

solute/liquid: 200 20000
(Molecular Weight)
solid/liquid: < 0.001 m

solute/liquid: < 500 (Molecular
Weight)
Membrane Type
polymeric asymmetric or
composite
polymeric asymmetric or
composite
Membrane
Configuration
spiral-wound
tubular
spiral-wound
tubular
Table 3.5: Characteristics of Nanofiltration and Reverse Osmosis
Even under the best pre-treatment regimes and programmes, membranes will foul and
deteriorate in performance if cleaning is not ensured. So NF systems should be designed in such
a way those modules can be taken offline and cleaned mechanically or chemically.

Advantages
Disadvantages
Modular systems, i.e. flexible in usage.

Clogging, plugging and fouling processes.
agents.
High prices.

Achievable removal efficiencies reported [cww/tm/27] are:
Inorganic mercury
Organic mercury
Cadmium and its compounds
Tetrachloromethane
1,2-Dichloroethane
Trichlorobenzene
Atrazine
Perchloroethen
92
> 90 %
> 90 %
> 90 %
96 %
71 %
96 %
> 70 %
90 92 %.
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of.
could be used as part of a recovery process. In both cases, the permeate water from a membrane
process could potentially be re-used or recycled in the industrial process, thus reducing water

chemicals for membrane cleaning operations,
mainly associated with maintaining a minimum velocity of about 2 m/s across the membrane
surface.
Monitoring
To ensure reliable operation the pressure difference across the membrane has to be continuously
monitored.
Costs
A guideline for investment costs is[cww/tm/93]:
350 1100 per m2 membrane for spiral and tubular membranes.
pumps
control system
other
30 %
20 %
10 %
20 %
15 %
5%
energy cost of maintaining hydrostatic pressure and flow rate of the system,
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cleaning
energy
labour
35 50 %
12 35 %
15 20 %
15 18 %
labour costs:
utilities:
total costs:
3.2.3.4.2
not known
Reverse Osmosis (RO)
Application
RO is a process to separate water and the dissolved constituents down to ionic species through a
semipermeable membrane by inducing a pressure higher than the osmotic pressure. It is applied
when a high grade of purity is required. Examples are:
desalination,
final removal of, e.g.:
- degradable components if biological treatment is not available,
- heavy metals,
- toxic components,
segregation of pollutants with the aim of concentrating or further processing them.
These issues are often connected with the recycling of process water. RO is also used in
combination with post-treatment techniques for the permeate, e.g. ion exchange or GAC
adsorption.
concentrated solutions with an osmotic pressure so high that it either exceeds available
operating pressure or is not economically viable,
salt solutions with low solubility which tend to precipitate when the concentration
increases, incurring fouling,
solutions with contaminants tending to polymerisation, also incurring fouling,
low thermal and chemical resistance of the membrane material, which limits their
application to a restricted pH and temperature range (18 30 C).

An industrial RO plant usually consists of three separate sections:
94
the pre-treatment section where the feed is treated by chemical clarification (precipitation,
coagulation/flocculation or flotation) and subsequent filtration, or by filtration and
subsequent ultrafiltration,
the RO section where high-pressure is applied and the waste water cross-flowed across the
membrane,
the post-treatment section where the permeate is prepared for reuse or discharge, and the
concentrate brine collected for further work-up or disposal.
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A typical RO arrangement is illustrated in Figure 3.11 [cww/tm/4].

materials have varying resistances to dissolved substances. Membrane materials for RO are
organic polymers, such as cellulose acetate, polyamide, polyimide, polycarbonate,
polyvinylchloride, polysulphone, polyethersulphone, polyacetal, copolymers of acrylonitrile and
vinyl chloride, polyelectrolyte complexes, cross-linked polyvinyl alcohol or polyacrylates. The
polyamide-based membranes are normally superior to cellulose acetate-based membranes to
remove trace organic molecules.
Figure 3.11: RO Arrangement
RO units are arranged as modules either in parallel to provide the necessary hydraulic
capacity or in series to increase the degree of efficiency.
Even under the best pre-treatment regimes and programmes, membranes will foul and
deteriorate in performance if cleaning is not ensured. So NF systems should be designed in such
a way that modules can be taken off-line and cleaned mechanically or chemically.

Advantages
Disadvantages
possible.
Modular systems, so flexible in usage.

High prices.
Low operating temperatures.
High-pressures required. Low permeate fluxes.
Possibility of fully automatic operation.
Increasing osmotic pressure during operation.
Potential for recovery of contaminants.
With time, permeability might decrease due to
compaction.
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Chapter 3

Achievable removal efficiencies reported are [cww/tm/27]:
Gamma Hexachlorocyclohexane
DDT
Aldrin
Dieldrin
Dichlorvos
Atrazine
Simazine
Trifluralin
Fenitrothion
Azinphos-methyl
Malathion
99 %
100 %
100 %
100 %
98 %
84 - 97 %
95 %
99 %
99 %
98 %
99 %

of.
could be used as part of a recovery process. In both cases, the permeate water from a membrane
process could potentially be re-used or recycled in the industrial process, thus reducing water

chemicals for membrane cleaning operations,
The energy consumption is directly related to flow rate and pressure requirements. It is mostly
associated with maintaining a minimum velocity of about 2 m/s across the membrane surface.
Monitoring
To ensure reliable operation the pressure difference across the membrane has to be continuously
monitored.
Costs
A guideline for investment costs is [cww/tm/93]:
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pumps
control system
other
30 %
20 %
10 %
20 %
15 %
5%
energy cost of maintaining the hydrostatic pressure and flow rate of the system,

cleaning
energy
labour
35 50 %
12 35 %
15 20 %
15 18 %
labour costs:
utilities:
total costs:
not known
3.2.3.5 Extraction
Principle
Extraction means transferring soluble contaminants from the waste water phase into a solvent.
Desirable properties for suitable solvents are:
low solubility and miscibility in water; examples are toluene, pentane and hexane,
greater dissolution capacity of the contaminant than water,
easy separation of solvent and waste water, e.g. because of large density difference,
easy separation of contaminants, e.g. because of low evaporation heat when distillation is
applied,
thermal stability.
Application
Solvent extraction is used with a variety of organic contaminants, when a suitable solvent is
available and if the contaminant concentration is not too low. At low concentrations extraction
is not compatible with adsorption or biological treatment. It is often used as a pre-treatment to
adsorption and/or biological treatment units.
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Examples are [cww/tm/82]:
removal of phenol (phenosolvan process),

recycling of metals, like zinc,
recycling of substances from mother liquors,
removal of phosphoric acid esters,
removal of chloro-aromatics,
pre-treatment concentrating of aromatic sulphonic acids
solvent loss entails costs and environmental impact,

solvent regeneration can be very complicated and cost intensive,
suitability of the solvent,
waste water should be almost free of suspended solids and/or emulsions.

Extraction is operated in columns where the waste water is brought into contact with the organic
solvent in different ways, e.g.:
counter current cascades,

mixer-settler contactors,
sieve plate columns,
packed columns,
spray towers,
rotating disc contactors,
centrifugal contactors, etc.
Downstream facilities are operated for liquid/liquid separation and distillation of the solvent
fraction. The remaining waste water phase normally has to get rid of the dissolved extraction
solvent, e.g. by stripping.
Storage facilities for the extraction solvent and the residue have to be provided for, equipped
with the necessary safety items to prevent emissions to air and soil.

Advantages
Under special conditions material recovery
possible.
Disadvantages
Residues have to be disposed of or incinerated.
Requires solvent recovery.

organic compounds.
Limited application because of solvent

characteristics.
Pre-treatment because of suspended solids.

No removal efficiency data yet available.
The loss of organic solvent during operation causes emissions of waste gas or of solvent residue
to waste water. The latter usually requires additional treatment, e.g. stripping, the former a
ducted removal to, e.g., incineration or adsorption.
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After solvent recovery (distillation or rectification) the bottom residue that contains the
extracted contaminants has to be disposed of as chemical waste, normally by incineration.
solvent, replacement of losses,

energy of subsequent treatment,
electric energy for pumps, mixers,
Monitoring
The input to the extraction unit has to be checked to prevent unwanted solids to enter, which
might cause disturbance to the process or destruction to the plant. Regular maintenance is
necessary in order to prevent or detect solvent losses to the environment.
Costs
labour costs:
utilities:
total costs:
not known
3.2.3.6 Distillation/Rectification
Principle
Distillation or rectification is the separation of waste water from its contaminants by
transferring them into the vapour phase. The enriched vapour phase will be condensed
afterwards.
Operating the process under vacuum conditions lowers the boiling temperature and allows the
separation of vulnerable substances.
Application
Waste water distillation or rectification has a limited application. It is often used as a process
integrated measure to recover starting material and/or product from mother liquors. As a waste
water treatment operation it is applied, e.g.:
to recover solvent after waste water extraction,

to recover solvent from waste water, e.g. separation of alcohols from methyl cellulose
production,
to treat oil emulsions.
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Chapter 3
feed concentration has to be large enough for distillation to become economically feasible,
sufficient difference between boiling temperatures of waste water and contaminants,
azeotropic mixtures need auxiliaries, or else distillation is not applicable.

Distillation and rectification are performed in columns, equipped with plates or packing
material, and a downstream condenser device. The heating is often done by direct steam
injection to avoid local overheating.
Storage facilities equipped with the necessary safety items have to be provided for distillate and
residue.

Advantages
possible.
Disadvantages
Residues have to be disposed of, usually by
incineration.

organic compounds.
High energy consumption.

Available removal efficiencies are [cww/tm/82]:
phenol in waste water
methanol in waste water
epichlorohydrin in waste water
aniline in waste water
chlorobenzene in waste water
from 5 %
from 8 %
from 0.7 %
from 0.4 %
from 0.01 %
to 0.2 %
to 0.2 %
to 0.07 %
to 0.01 %
to 0.001 %
The loss of organic solvent during the process causes emissions of waste gas to the air or
solvent residue to waste water. The latter usually requires additional treatment, e.g. stripping,
the former a ducted removal to, e.g., incineration or adsorption.
steam for heating,

energy for subsequent treatment,
electric energy for pumps, mixers,
Monitoring
The input to the distillation/rectification unit has to be checked to prevent the entrance of
unwanted solids that might cause disturbance to the process or damage to the plant. Regular
maintenance is necessary so that solvent losses to the environment do not occur or can be
detected in time.
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Costs
labour costs:
utilities:
total costs:
not known
3.2.3.7 Evaporation
Principle
Evaporation of waste water is a distillation process where water is the volatile substance,
leaving the concentrate as bottom residue to be disposed of. The aim of this operation is to
reduce the volume of waste water or to concentrate mother liquors. The volatile steam is
collected in a condenser and the condensed water is recycled.
Operating under vacuum decreases the boiling temperature and enables recycling of substances
that would otherwise decompose.
Application
Evaporation is applied when concentrated waste water streams are wanted or recommended,
e.g.:
to concentrate mother liquors in order to recycle valuable substances,

to evaporate and crystallise solids, either to recover or remove them from the waste water
effluent,
as pre-treatment in order to concentrate the waste stream before thermal exploitation, waste
water incineration or disposal as hazardous waste.
Evaporation units should be operated in such a way that the necessary thermal energy is
delivered by exploiting the waste heat of production processes [cww/tm/82].
fouling of the heat exchanger(s),

corrosion of the evaporator body and heat exchanger,
presence of foam generating substances,
presence of colloidal and suspended particles,
When material recovery is the main purpose, a pre-treatment operation is required before
evaporation can be started, Examples of pre-treatment are:
separation of insoluble, free liquid phases, e.g. oil,

chemical/physical operations to separate heavy metals and/or other solids.
Further treatment, e.g. incineration, after evaporation is required, if the concentrate is not
recycled.
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There are many types of evaporators. Their suitability depends on the individual requirements.
Examples of evaporators are:
natural-circulation evaporators, suitable for material not sensitive to heat,

short-tube vertical evaporators, suitable for liquors not corrosive or crystallising,
basket-type evaporators, same application as short-tube evaporators,
falling film evaporators, used in fertiliser industry to concentrate urea, phosphoric acid,
ammonium nitrate etc.,
agitated thin film evaporators, used for concentrating, fractionating, deodorizing and
stripping in the production of pharmaceuticals, polymers, organic and inorganic chemicals.
Evaporators are usually operated in series, where the condensation heat of one stage heats the
condensate (i.e. waste water) of the preceding stage. Operation under vacuum minimises energy
demand.
Storage facilities have to be provided for residues before their disposal (or recycling).

Advantages
possible.
Disadvantages
Residues have to be disposed of, normally by
incineration, if not suitable for recycling.

organic compounds.
Tends to fouling.
Tends to corrosion.
Reduces waste water amount.

Tends to foaming.
Reduces hazardous waste amount, volume.
High energy consumption.

Evaporation is normally a waste water free process, because the condensate will be recycled
with or without further treatment and the concentrate will be recycled or disposed of as waste,
e.g. by incineration.
steam for heating,

energy for subsequent treatment,
Monitoring
Proper maintenance of the heat exchangers is a crucial point. Encrustations, fouling and
corrosion disturb the heat transfer to the liquid and decrease the energy efficiency.
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Costs
labour costs:
utilities:
total costs:
not known
3.2.3.8 Stripping
Principles
Waste water stripping is an operation in which waste water is brought into contact with a gas
current in order to transfer volatile pollutants from the water phase to the gas phase. The
pollutants are removed from the stripping gas so it can be recycled into the process and reused.
The subsequent removal of the volatile pollutants from the gas phase can be accomplished by:
adsorption on GAC, zeolite or synthetic resins,

absorption by non-aqueous solvent and subsequent desorption,
condensation or partial condensation and subsequent further treatment,
incineration.
Generally speaking, treatment of the stripping gas is an essential process step and sometimes
more complicated than the stripping operation itself. To obtain an efficient treatment in total,
both the stripping stage and the stripping gas treatment have to be carefully adjusted to each
other.
3.2.3.8.1
Air Stripping
Application
The close contact of waste water with a current of air enables volatile components to evaporate.
Such volatile components can be:
chlorinated hydrocarbons, such as trichloroethen, perchloroethen, trichloromethane,

dichloroethane, trichloroethane,
ammonia and hydrogen sulphide, their volatility strongly dependent on temperature and pH,
organic solvents, petrol, diesel fuel, low aromatics, phenol, mercaptanes,
Air stripping can be operated with or without heating the stripping column, the latter used with
easily volatile or vulnerable compounds. The necessary heating energy is usually supplied by
exploiting process heat.
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Chapter 3

The most common methods for air stripping are:
packed tower aeration,

spray aeration,
diffused air aeration,
Further equipment is:
a buffer tank for waste water,

a pre-treatment tank for pH adjustment.
An example of air stripping of ammonia is illustrated in Figure 3.12 [cww/tm/78].
Figure 3.12: Stripping of Ammonia, Air and Steam Stripping

Advantages
High removal efficiency.
Disadvantages
Under certain conditions high capacity for
fouling (e.g. sour water strippers in refineries)
and therefore injection of anti-fouling agents
necessary
Low-pressure drop.
Low energy consumption.
Stripping gas has to be treated.

Achievable removal efficiencies are:
air stripping of ammonia, pH 11 12, waste water stream
0.5 30 m3/h, feed 20000 mg/l
with lower feed concentrations and optimum conditions
[cww/tm/82]
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50 200 mg/l
< 5 mg/l
Chapter 3
air stripping of production waste water, removal of volatiles

in central stripper, feed rate 1 m3/h, feed concentration of
2000 mg/l contaminants dichloromethane, trichloromethane,
benzene, toluene, xylene, esters, and ethers [cww/tm/82]
99 %
sour water stripping, design effluent of ammonia 150 mg/l,

design flow rate 20 m3/h [cww/tm/48]
13 mg/l
sour water stripping, design effluent of ammonia 50 mg/l,

design flow rate 32 m3/h [cww/tm/48]
35 mg/l
carbontetrachloride, packed tower aeration, air/water 5-35:1
90 98 %
1,2-dichloroethane, packed tower aeration, air/water 35:1
65 %
trichloroethen, packed tower aeration, air/water 4-30:1

spray aeration
69 92 %
90 %
perchloroethen, packed tower aeration, air/water 5:1

spray aeration
95 %
90 %
The last 4 examples reported by [cww/tm/27].

Air stripping is not an individual process. It needs downstream gas treatment. The removed
volatiles might either be recycled to a production process or incinerated. Environmental impacts
that can occur downstream are either the release of exhaust air from an incineration process or
the consumption of energy by a condensation or regeneration operation.
chemicals such as acid or caustic soda or lime, if the pH level is an issue,

anti-fouling agents,
electric energy for pumps and air vents/compressor.
Monitoring
To ensure reliable operation the pH of the waste water has to be monitored, in particular if
ammonia or hydrogen sulphide are involved.
Costs
The capital costs are:
M 4.0 for sour water stripper, design flow rate 30 m3/h,

design ammonia effluent 10 mg/l [cww/tm/48]
labour costs:
utilities:
k 21/year [cww/tm/48]
total costs:
The capital costs are:
M 5.3 for sour water stripper, design flow rate 32 m3/h,

design ammonia effluent 50 mg/l [cww/tm/48]
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Chapter 3
labour costs:
utilities:
total costs:
k 175/year (not known whether steam is used) [cww/tm/48]
3.2.3.8.2
Steam Stripping
Application
Steam stripping as an alternative to air stripping is applied to compounds that are less volatile
and/or less vulnerable. It enables the stripper to be operated under simpler separation
conditions. The potential volatile components for steam stripping are:
chlorinated hydrocarbons such as trichloroethene, perchloroethene, trichloromethane,

dichloroethane, trichloroethane,
ammonia and hydrogen sulphide, their volatility strongly dependent on temperature and pH,
organic solvents, petrol, diesel fuel, low aromatics, phenol, mercaptanes.
If ammonia or hydrogen sulphide are to be stripped, a proper pH adjustment is crucial. With

ammonia a pH > 9.5 is necessary, with hydrogen sulphide the pH range is about 2 3.
Steam is normally delivered by the steam generation equipment already existing on the site or
by exploited waste heat. If there is no existing steam generation equipment, steam stripping
might not be economically feasible.

The equipment consists of:
stripping column, operated counter flow,

feed pre-heater, recovering heat from the subsequent strip steam condenser,
condenser, air or water cooled,
downstream facilities for gas treatment (adsorption, condensation or incineration).

Advantages
High removal efficiency.
Low pressure drop.
Disadvantages
Under certain conditions high capacity for
fouling (e.g. sour water strippers in refineries)
and therefore injection of anti-fouling agents
necessary.
Steam generation costs energy.
Steam has to be separated by condensation.
Resulting stripping gas has to be treated.
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ammonia stripping [feed 1 % weight of ammonia]
[cww/tm/27]
99 % [< 50 mg/l]
steam stripping of chloromethanes [feed 6 m3/h, > 200 mg/l]

[cww/tm/82]
< 1mg/l
steam stripping of methanol [feed 3.4 m3/h, 3.6 % weight]

[cww/tm/82]
97 %
steam stripping of dichloromethane and methylal [feed 4 m3/h,

5000 mg/l dichloromethane, 30000 mg/l methylal]
[cww/tm/82]
99 %
steam stripping of aromatics [feed 400 m3/h, 500 1000 mg/l BTX]
[cww/tm/82]
> 99 %
Steam stripping is not an individual process. It needs downstream gas treatment. The removed
volatiles might either be recycled to a production process or incinerated. Environmental impacts
that can occur downstream are either the release of exhaust air from an incineration process or
the consumption of energy by a condensation or regeneration operation.
chemicals such as acid or caustic soda or lime, if the pH level is an issue,

steam, 0.3 tonne of steam per tonne waste water treated (steam stripping of ammonia)
[cww/tm/27], or 0.26 tonne of steam per tonne waste water treated (steam stripping of
methanol) [cww/tm/82]
electric energy for pumps and air vents/compressor.
Monitoring
To ensure a proper operation the pH of the waste water has to be monitored, in particular if
ammonia or hydrogen sulphide are involved.
Costs
Costs of a 50 m3/h plant [cww/tm/92]:
capital costs: k 200 300
operating costs: k 300 400 per year.
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Chapter 3
3.2.3.9 Oxidation
3.2.3.9.1
Chemical Oxidation
Principle
Chemical oxidation is the conversion of pollutants by chemical oxidation agents other than
oxygen/air or bacteria. Chemical oxidation agents are, e.g.:
chlorine,
sodium or calcium hypochlorite,
chlorine dioxide,
ozone (with or without UV irradiation),
hydrogen peroxide/UV irradiation
hydrogen peroxide/ferrous salts (Fentons agent)
Reaction products are carbon dioxide, water and hydrogen chloride, the latter when chlorinated
organic contaminants are involved. During normal operation, chemical oxidation results in a
number of products originating from decomposition of short-lived radicals. These products are
usually short-chained and easily biodegradable.
Normally chemical oxidation needs further downstream treatment facilities like a CWTP.
Application
Chemical oxidation is applied when the waste water contains contaminants that are not readily
biodegradable, might disturb the biological process in a downstream CWTP or have properties
too harmful to be released into a common sewer system. Examples for such contaminants are:
oil and grease,

phenols,
polycyclic aromatic hydrocarbons (PAHs)
organic halides,
pesticides,
cyanide,
sulphide,
heavy metal complexes.
Frequent operations in connection with chemical oxidation are:
oxidation with ozone,

oxidation with ozone/UV irradiation,
oxidation with hydrogen peroxide/UV irradiation,
oxidation with ozone, hydrogen peroxide and UV irradiation,
oxidation with chlorine, hypochlorite
Oxidation reactions with active oxygen (ozone, hydrogen peroxide), often accompanied with
UV irradiation, are used, e.g., to treat leachates from landfills or remove recalcitrant COD,
odorous components or colour pigments.
Oxidation with chlorine or sodium chlorite is used to remove organic contaminants. Quite
surprisingly, organic halides can also be drastically reduced. An example is the SOLOXProcess to eliminate (at elevated pressure and temperatures) COD/TOC and AOX of waste
water originating from epichlorohydrin production. The actual process is applied on a chemical
site where chlorine is produced and easily accessible.
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Chapter 3
when UV irradiation is involved, clear solutions are required or at least recommended,

substances that tend to fouling can decrease the efficiency,
carbonate concentration has to be low,
low ammonia content [cww/tm/27].

The design of an oxidation reactor depends on its special purpose.
Normally oxidation processes are operated at pressures of up to 5 bar [cww/tm/82]. Depending
on whether UV irradiation is acting as an accelerator, the equipment of the reactor has to
provide for the radiation source, e.g. a low-pressure mercury lamp. In such a case the reactor
usually consists of quartz tubes, transparent to UV rays, confining the waste water, and the UV
lamps outside, or the UV lamps inside the quartz tubes that are enclosed by the waste water.
If ozone is involved in the process, an ozone generator is part of the equipment, because ozone
as an unstable compound cannot be transported and has to be generated in situ. After treatment,
surplus ozone has to be eliminated. Safety requirements to handle ozone are strict.
With hydrogen peroxide as reaction agent, a GAC adsorber is necessary to eliminate surplus
agent.
Application of chlorine entails special equipment, such as titan manufactured vessels.
Additional installations should be provided that can eliminate surplus chlorine or hypochlorite
by, e.g., sulphite.
Storage facilities have to be provided for the oxidation agents, bearing in mind the hazardous
potential of these substances.

Advantages
Waste water with recalcitrant COD
concentrations over a range of some g/l down
to less than 1 g/l can be treated [cww/tm/77].
Process can be combined with any other to
achieve optimum results (GAC adsorption,
stripping, activated sludge biology).
Disadvantages
High costs.
High operational costs.
High energy consumption: ozone generation,
UV generation, pressure and heating for
chlorine oxidation.
High demands on feed quality.
Ozone has to be handled with care.
Hydrogen peroxide can be hazardous under
certain conditions.
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Reported removal efficiencies are:
SOLOX-process for epichlorohydrin
> 90 % TOC
(TOC feed about 1 g/l, AOX feed about 40 mg/l)
about 80 % AOX
[cww/tm/82] SOLOX-process is individual treatment in this case.
The major issue for chemical oxidation is to eliminate calcitrant organic contents and trouble
makers to the subsequent biological treatment. This might be accomplished by breaking these
components into short-chain ones. Bearing that in mind, the most practical source of
performance evidence might not be just the removal efficiency of the oxidation process, e.g. for
COD/TOC and/or AOX/EOX, but also the overall reduction of these contaminants achieved in
co-operation with precedent and subsequent treatment operations and processes.
Chemical oxidation with ozone and/or hydrogen peroxide does not normally create a problem
transfer from the water to the air and/or the disposal section. The use of chlorine or
hypochlorite, however, has to be validated critically for each application. Chlorine and
hypochlorite might in contrast to the example of the SOLOX-process generate chlorinated
organic compounds that are poorly degradable and/or toxic. This can also be detected when
waste water loaded with organic compounds is mixed with other streams that contain surplus
hypochlorite from preceding oxidation steps. Waste water treated by chlorine oxidation has to
be relieved from surplus chlorine or hypochlorite before it is discharged into the general sewer
system.
the oxidation agent,

chemical agents to destroy surplus oxidation agents,
electric energy for pumps and irradiation device (if UV is applied)
electric energy for ozone generation.
Monitoring
During the oxidation process a thorough monitoring of operation parameters is crucial. The
ozone concentration in air has to be checked for safety reasons ozone concentrations of
15 - 20 % in air are very unstable and tend to decomposition [cww/tm/27]. Also for safety
reasons the oxygen concentration has to be monitored. The effluent should be checked for
surplus oxidation agents.
Costs
110
labour costs:
utilities:
total costs:
not known
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Chapter 3
3.2.3.9.2
Wet Air Oxidation
Principle
Wet air oxidation is the reaction with oxygen in the aqueous phase. Reaction products are,
besides carbon dioxide and water:
hydrogen chloride from organic chlorides,

sulphate from sulphides, sulphites and rhodanide,
nitrate from nitrite,
nitrogen from hydrazine, or from ammonia, if a catalyst is used.
In relation to the applied pressure, wet air oxidation distinguishes a low-pressure and a highpressure variant.
3.2.3.9.2.1
Low-pressure Wet Air Oxidation
Application
The low-pressure variant of wet air oxidation is operated at temperatures between 50 and
200 C and pressures between 4 and 20 bar with a residence time of 0.5 to 3 hours. It is applied
to waste water containing contaminants that are either not readily biodegradable or might
disturb the biological process in a downstream CWTP, or that have properties too harmful to
release them into an ordinary sewer system. It is also used for sludge treatment. The substances
preferably considered for low-pressure wet air oxidation are, e.g.:
nitrite that is converted to nitrate in a one-step process at 30 50 C,

hydrazine that is converted to nitrogen in a one-step, homogeneously catalysed process at
50 - 120 C,
sulphite that is converted to sulphate in a two-step, homogeneously catalysed process at
120 - 140 C,
phenol and naphthene derivatives that are converted at 120 150 C,
chlorinated aromatics that are converted by catalysis at 120 190 C.
recommendable for COD concentrations between 5000 and 50000 mg/l with COD
concentrations from 10000 mg/l on being autothermal [cww/tm/82] and over 100000 mg/l
demanding dilution [cww/tm/27],
fluoride concentrations < 10 mg/l, higher concentrations to be pre-treated,
waste water to be collected and equalised before oxidation.

Equipment and design for the low-pressure wet air oxidation process are [cww/tm/51]:
the high-pressure reactor vessel, e.g.

a well mixed, vertical bubble column without mechanical mixing,
a horizontal reactor with agitated compartments in series,
a vertical underground tube reactor or deep well reactor,
a packed bed reactor with catalyst,
the high-pressure pump for waste water or sludge transportation,
the compressor for air/oxygen supply,
the gas/liquid separator,
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Chapter 3
pressure reducing valves,

the heat exchanger system with pre-heating facilities for the waste water input.
The demands on the reactor vessel material are high, so in some cases titan or titan alloys might
be necessary.

Advantages
to less than 1 g/l can be treated.
Can be combined with other treatments.
Disadvantages
High costs.
Dioxins can be destroyed or generated
[cww/tm/82].

Elimination efficiency of about 60 90 % with COD/TOC and/or AOX is reported
[cww/tm/82].
makers to subsequent biological treatment. This might be accomplished by breaking these
Under adverse conditions generation or regeneration of dioxins can occur, so residues might
need further treatment.
The effluents from this process aqueous and off-gas have to undergo downstream treatment,
e.g. biological treatment, adsorption or stripping of waste water, and gas scrubbing, biofiltration
or incineration of waste gas.
the oxidation agent, i.e. air or oxygen,

electric energy for pumps, and compressor
Monitoring
During the whole process a thorough monitoring of operation parameters such as pressure,
temperature and oxygen content will inform about faultless working.
Costs
112
labour costs:
utilities:
total costs:
not known
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3.2.3.9.2.2
High-pressure Wet Air Oxidation
Application
The high-pressure variant of wet air oxidation is run at temperatures between 150 and 340 C
and at pressures between 7 and 200 bar with a residence time of 0.5 to 3 hours. It is applied to
waste water containing contaminants that are either not readily biodegradable or might disturb
the biological process in a downstream CWTP, or that have properties too harmful to be
released into an ordinary sewer system. Waste water streams treated by this method normally
range between 5 and 100 m3/h. They usually originate from productions of organic dyes, their
aromatic intermediates and pesticides. The substances preferably considered for high-pressure
wet air oxidation are, e.g.:
organic nitro compounds that are converted to nitrogen,

organic amino compounds or aromatics containing nitrogen hetero atoms that are converted
to ammonia,
organic sulphur compounds that are converted to sulphate,
organic phosphorous compounds that are converted to phosphate,
chlorinated organic compounds that are converted to hydrochloric acid.
The main reaction products are carbon dioxide and water.

recommendable for COD concentrations between 20000 and 150000 mg/l [cww/tm/82],
concentrations over 100000 mg/l demanding dilution [cww/tm/27],
fluoride concentrations < 10 mg/l, higher concentrations to be pre-treated,
salt loads such as calcium, iron and aluminium salts have to be minimised as far as possible
[cww/tm/82],
pH range between 1 4,
waste water to be collected and equalised before oxidation, and possibly concentrated to a
COD content of > 20000 mg/l [cww/tm/82].

Equipment and design for the high-pressure wet air oxidation process are [cww/tm/51]:
the high-pressure reactor vessel, e.g.

a well mixed, vertical bubble column without mechanical mixing,
a horizontal reactor with agitated compartments in series,
a vertical underground tube reactor or deep well reactor,
a packed bed reactor with catalyst,
the high-pressure pump for waste water or sludge transportation,
the compressor for air/oxygen supply,
the gas/liquid separator,
pressure reducing valves,
the heat exchanger system with pre-heating facilities for the waste water input.
The reactor vessel material is usually titan or titan alloys, so a pH range from 1 - 4 is necessary.
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Chapter 3

Advantages
to less than 1 g/l can be treated.
Disadvantages
High costs.
Can be combined with other treatments.
Oxidation products have to be disposed of.
High elimination efficiency.
Downstream waste water treatment and

exhaust gas treatment necessary.
Exhaust gas is clean of dust, nitrogen oxides

and sulphur dioxide.
No dioxins [cww/tm/27].

Elimination efficiency of about 90 99 % for COD/TOC is reported [cww/tm/82].
Elimination efficiency for pesticides is reported in [cww/tm/27], see Table 3.6.
Compound
Aldrin
DDT
Endosulfan
Endrin
2,4-dichlorophenol
Influent [g/l]
Effluent [g/l]
500
21000
18400
3600
180
< 50
< 300
291
< 100
< 3.1
Table 3.6: Removal of Pesticides Via High-pressure Wet Air Oxidation
Subsequent treatment is necessary for the exhaust gas stream as well as for the oxidised waste
water, which means catalytic waste gas treatment for carbon oxide and low molecular
hydrocarbons, and waste water stripping followed by biological treatment.
the oxidation agent, i.e. air or oxygen,

catalyst, if used,
electric energy for pumps, and compressor
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Monitoring
During the whole process a thorough monitoring of operation parameters such as pressure,
temperature and oxygen content will inform about faultless working.
Costs
labour costs:
utilities:
total costs:
3.2.3.9.3
not known
Waste Water Incineration
Principle
Waste water incineration is the oxidation with air of organic and inorganic waste water
contaminants and the simultaneous evaporation of the aqueous part at normal pressure and a
temperature range between 730 1200 C. In chemical industry, waste water incineration is
often operated centrally or, as co-incineration, in waste combustion plants. Reaction products
are carbon dioxide, water and other inorganic compounds in relation to the contaminants of the
waste water stream.
Application
Incineration is applied to waste water containing compounds that are either not readily
biodegradable or might disturb the biological process in a downstream CWTP, or that have
properties too harmful to be released into an ordinary sewer system. Such contents are e.g.:
aqueous residues from dye production,

aqueous residues from rubber production, containing extremely large loads of salt,
aqueous extracts from pesticide productions.
Waste water streams that are incinerated generally cover a range between 2 30 m3/h with
COD concentrations between 50000 100000 mg/l, so incineration will be autothermal. Lower
concentrations require extra fuel.
Waste water of low combustion heat can be injected into rotary kilns for co-combustion with
waste.
incineration of waste water containing chlorine and/or sulphur can require flue gas
treatment,
generation of nitrogen oxides increases when combustion temperature increases,
solids and salts need separation systems to remove dust and aerosols.
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Chapter 3

Devices for waste water incineration can be constructed as ordinary combustion chamber or
fluidised bed incinerator. There is a high demand on the stability of the plant material.
Combustion chambers are often built in ceramics.
Waste water incineration can also occur in an ordinary waste combustion plant, with waste
water as an additional input. Pre-treatment might be necessary to eliminate particulates
exceeding a maximum size to prevent jet blockage.

Advantages
Waste water with high organic content will be
nearly completely removed.
Elimination of pollutants also possible with
high salt concentration.
Disadvantages
Makes sense only with high TOC
concentrations, or when there is no other
choice because of the characteristics of the
contaminants.
Low organic concentrations need auxiliary
fuel.
Waste heat can be used.
Solid waste to be disposed of.

Incineration of sulphur and/or halide
compounds might demand flue gas treatment
causing waste water.
With increasing temperature increasing
generation of nitrogen oxides.

Organic compounds are almost totally removed removal efficiency > 99 % [cww/tm/82].
co-operation with precedent and subsequent treatment operations and processes. A thorough
comparison with other oxidation processes in relation to the impact on the environment as a
whole should be drawn for each possible application.
fuel, if the TOC content is too low to support autothermal incineration,

waste gas and/or waste water treatment agents, where necessary,
electric energy for pumps, burners, secondary treatment devices,
Monitoring
During the whole process a thorough monitoring of operation parameters, such as oxygen
content, temperature, content of sulphur oxides, nitrogen oxides, hydrogen halides, dust etc. will
inform about faultless working.
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Costs
labour costs:
utilities:
total costs:
not known
3.2.4 Soluble Biodegradable Waste Water Contaminants

In the chemical industry, the major part of the waste water streams is more or less loaded with
biodegradable contaminants. For this reason, it makes sense to transfer the collected waste
water (or a part of that collection) to a central biological treatment plant. Substances that might
disturb biological degradation have been removed earlier. Biological treatment will be described
in the following chapters.
3.2.4.1 Biological Treatment
Principle
Biological treatment is an oxidation or mineralisation process with micro-organisms
bacteria as agents, using contaminants as nutrients. There are two types of micro-organisms:
aerobic organisms that need oxygen for their growth,

anaerobic organisms that do not digest oxygen.
Thus biological treatment plants are working under either aerobic or anaerobic conditions.
The effluent waste water is brought into contact with a dense population of suitable microorganisms for a time sufficient to break down the contaminants. By consuming the organic feed
from the waste water effluent, the micro-organisms grow transforming into new bacteria mass
the activated sludge. The sludge is constantly washed out of the reaction vessel and transported
to the secondary clarifier where it settles. The major part of the settled sludge is recycled to the
mixing tank to serve as biomass for the activated sludge process. Excess biological solids are
removed, de-watered and disposed of.
The degradation products of biological treatment depend on the way the process is operated.
Aerobic treatment results in carbon dioxide and water, anaerobic treatment in carbon dioxide
and methane.
Application
Biological waste water treatment is very popular in the chemical industry. Since most
production sites handle organic chemicals, biological treatment is a common and efficient tool
as an end-of-pipe technology. It is generally applied as CWTP prior to discharging the effluent
waste water into a receiving water.
Important application factors [cww/tm/27]:
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Chapter 3
treatability of the waste water with biological systems, which might require stream
segregation and pre-treatment upstream of the CWTP,
behaviour of the substances during treatment, e.g. volatility, adsorption to sludge, chemical
reactions and interactions between individual compounds during the treatment process,
decomposition,
sludge arising and disposal, with anaerobic processes yielding significantly smaller amounts
of excess sludge,
cost,
size of the CWTP.
A biological degradation process requires nutrients, such as nitrogen and phosphorous

compounds, to nourish the micro-organisms. A nutrient ratio BOD:N:P of 100:5:1 is normally
applied. Critical ratios are BOD:N of 32:1 and BOD:P of 150:1. Other nutrients are mineral
salts of potassium, sulphate etc. Chemical industry waste water is usually low in these
substances, which means that they have to be specially added before the biological treatment
starts.
The biodegradability of a waste water stream can, by rule of thumb, be estimated by its
COD/BOD ratio [cww/tm/27]:
COD/BOD > 100

COD/BOD 100 10
COD/BOD < 10
relatively undegradable waste water

moderately degradable
relatively degradable
the presence of inhibitors to aerobic processes, e.g. pesticides, polyaromatic compounds,

organic halides, arsenic, borate, cadmium, chromate, chromium(III), copper. lead,
manganese, mercury, nickel, silver, zinc and
high salt loads disturb the biological process by damaging the micro-organisms.

A typical CWTP operated in the chemical industry is shown in Figure 3.13 [cww/tm/81].
Figure 3.13: Mechanical-biological-chemical Waste Water Treatment Plant inclusive of Sludge

Treatment
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Chapter 3
Biological waste water treatment typically takes advantage of a CWTP. It is a complex process
that includes preparatory and subsequent separation operations. The different facilities are:
mixing station, where neutralisation and flocculation chemicals are added and mixed
(usually lime milk and/or mineral acids, ferrous sulphate); might be covered to prevent
releases of odorous substances,
primary clarifier, where the floc is removed; might be covered to prevent fugitive releases
of odorous substances,
aeration basin, or activated sludge basin, with nutrient feed at the entry, aeration jets and
sludge, where the biological reaction takes place; may be designed diversly; might be
covered to prevent fugitive releases of odorous substances,
alternative for anaerobic processes: closed reaction tank with gas duct (carbon dioxide and
methane),
secondary clarifier with sludge recycling and transfer to sludge treatment; might be replaced
by microfiltration,
further treatment facilities for waste water subsequent to secondary clarifier, such as
flotation,
covered basins or anaerobic reactors equipped with ducts to a waste gas abatement system
or, with methane, to an energy generation device,
waste gas abatement facilities such as GAC adsorption, incineration or flare.
Unlike MWTPs industrial CWTPs are generally not equipped with sludge digesters.
Sludge treatment will be dealt with in a separate chapter (Chapter 3.4 below) of this document.
The aeration basin, though always coping with the same biological process, can have totally
different designs, in line with its task. One example is the high performance tower biology
working in various versions at different chemical sites. This technology takes into account a
better degradation efficiency because of smaller air bubbles ascending in a large column (the
tower) of waste water and thus increasing distinctly the air/waste water contact. Two examples
are shown in Figure 3.14 and Figure 3.15 [cww/tm/81]:
Figure 3.14: Tower Biology, System BAYER
The necessary volume of basins or tanks depends on the amount of effluent discharged into the
CWTP and the residence time obligatory for appropriate biological degradation. The residence
time varies along with the biodegradability of the waste water content. One CWTP reports a
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Chapter 3
residence time in the activated sludge part of 17 hours (waste water volume 8000 m3/day, COD
input 20 tonnes/day, COD degradation 17 tonnes/day) [cww/tm/95].
Figure 3.15: Tower Biology, System HOECHST

Advantages
Cost effective treatment of organic
contaminants.
Disadvantages
Biological processes can be inhibited by
contaminants.
Environmental impact lower than with other

treatment processes.
Process is temperature dependent as the microorganisms do not work at extreme

temperatures, either too low or too high.
Large amount of waste water can be treated.

Energy efficiency is high, energy is mostly
produced by sustainable methods (metabolism
of micro-organisms with air and water).
Degradation into harmless compounds.
Generation of sludge that has to be disposed

of.
The aeration process causes stripping effects
for volatile compounds resulting in fugitive
releases.
Activated sludge processes release odorous
substances.

In the first place, the task of biological waste water treatment is to mineralise organic chemicals
to carbon dioxide and water. So the performance efficiency is usually demonstrated by its BOD
or COD/TOC degradation.
Available emissions and/or removal efficiencies are:
BOD at the effluent:
BOD degradation:
20 mg/l,
about 98 % [both cww/tm/82]
COD/TOC degradation:
60 95 % [cww/tm/82]
usually 85 95 %
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The COD/TOC degradation efficiency depends on pre-treatment measures and/or upstream

waste water segregation.
A critical environmental issue of biological treatment is the release of volatile substances, often
accompanied by odour, caused by stripping effects of air injection in the aeration basin. To
prevent these fugitive emissions, those parts of the CWTP that tend to release fugitive emissions
e.g. mixing station, primary clarifier and aeration basin might be covered. The exhausted air
is ducted to a waste gas treatment, such as GAC adsorption or incineration. With anaerobic
treatment the generation and presence of low chain carboxylic acids require operations in closed
tanks. The generated gas enriched with methane is ducted to an incineration or combustion plant
where it can be exploited for heat generation.
The sludge normally contains undegraded pollutants, such as organic halides, aromatics and
heavy metals. Because of its pollutant content the excess sludge is frequently incinerated.
Before incineration the sludge is transferred to thickening and drying, where its heat content is
increased to support autothermal incineration.
the electric energy for all the equipment such as pumps, aeration jets, vents, mixers and
sludge collector,
treatment agents such as flocculant and neutralisation chemicals, nitrogen and phosphorus
nutrients,
adsorbent for exhausted air treatment.
Monitoring
Monitoring a CWTP has two tasks, first to shelter the plant from the input of inhibitors, second
to prevent an uncontrolled discharge from the plant into the receiving water. Monitoring the
input is best done at or near the production site to take appropriate measures early enough, e.g.
by diverting the particular waste water part stream to a buffer or retention system.
The discharge of the CWTP is usually constantly monitored because of permit requirements.
The parameters to analyse are at least those limited in the permit, such as BOD, COD/TOC,
AOX/EOX, the heavy metals, etc. Further parameters to monitor that are helpful to protect the
water quality of the receiving water are the different acute toxicity parameters such as fish,
algae and daphniae toxicity. Other parameters relating to chronic toxicity or persistency should
be taken into account as part of Whole Effluent Assessment.
Costs
labour costs:
utilities:
total costs:
not known
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Chapter 3
3.2.4.2 Nitrogen Elimination
Principle
Nitrogen, or more precisely ammonium, is removed by a special biological treatment that
consists of two steps:
nitrification, where Nitrosomonas bacteria oxidise ammonium (NH4) to the intermediate

nitrite (NO2) that is, under aerobic conditions, converted to nitrate (NO3) by Nitrobacter
bacteria,
denitrification, where several genera of bacteria (e.g. Achromobacter, Aerobacter etc.)
converse nitrate to nitrogen gas under anoxic conditions.
Nitrification/denitrification is usually incorporated in central biological waste water treatment.
Application
Nitrification/denitrification is applied to waste water (streams) that contains a considerable
amount of nitrogen compounds, in particular amines and ammonium compounds. The control of
ammonium discharge is a key issue to protect the quality of surface water (e.g. rivers), because
the conversion of ammonium to ammonia, dependent on pH, results in fish toxicity.
Nitrification/denitrification is a tertiary treatment (see Chapter 1.1.2.2).
temperatures below 12 15 C restrain the growth of nitrobacter bacteria in the nitrification

step; as response the sludge residence time has to increase accordingly,
the presence of waste water contaminants that might induce inhibition of bacteria growth
and thus stop the entire nitrogen elimination process, see Table 3.7 [cww/tm/27].

Nitrification/denitrification is typically incorporated in the CWTP that, for this purpose, is
equipped with additional reaction basins or tanks (or a tank divided into denitrification and
nitrification zones). A vital factor for denitrification is the ratio of oxygenated nitrogen
(nitrate/nitrite) and BOD. A value of lower than 0.2 ensures a complete denitrification process.
There exist different modifications of nitrification/denitrification, two of them shown in Figure
3.16 and Figure 3.17 [cww/tm/81].
In the first case nitrification and denitrification are operated in series. The N/BOD ratio will be
improved by adding easily biodegradable TOC, e.g. methanol, at the entry of the denitrification
stage. An extra subsequent aeration sector is obligatory.
The second modification operates with pre-installed denitrification. At the entry to the
biological treatment the nitrate/BOD ratio is at its lowest, whereas the oxygen consumption of
the waste water is at its highest, thus offering optimum conditions for denitrification. This
modification works well in smaller denitrification basins or zones. A large part of the nitrated
waste water has to be recycled to the entry of the denitrification basin or zone.
If wanted, nitrification/denitrification can also be operated separately from the CWTP, for
example in separate tanks. This is a valuable solution when only some of the waste water needs
to be treated. The demands on the equipment are not exceedingly high.
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Compound
Thiourea
Thiosemicarbazide
sodium methyldithiocarbamate
methyl isocyanate
allyl isothiocyanate
1,1-dichloroethane
1,1-dichloroethen
1,2-trans-dichloroethen
1-naphthylamine
2,2-bipyridine
ammonia-N
benzene
benzidine dihydrochloride
benzocaine
benzylamine
tetrachloromethane
chlorobenzene
trichloromethane
dimethylgloxime
dimethylphthalate
dodecylamine
ethylendiamine
hexamethyldiamine
monoethanolamine
methylamine
methyl thiouronium sulphate
skatole
sodium dimethyldithiocarbamate
sodium cyclopentamethylenethiocarbamate
guanidine carbonate
allyl alcohol
benzyl thiouronium chloride
diguanide
allylthiourea
thioacetamide
dithio-oxamide
mercaptobenzthiazole
N-methylalanine
naphthalene
naphthylethylene diamine
dihydrochloride
nihydrin
p-aminopropiophenone
p-nitroaniline
p-nitrobenzaldehyde
Inhibition
Reduction in
Concentration
Rate
[mg/l] dissolved
[%]
1
1
1
1
1
125
75
75
15
16 / 20
200
500
20 - 100
> 100
> 100
50
100
18
> 100
100
<1
17
85
>100
<1
10
10
20
50
50
50
50
50
starting point
20
50
20
20
20 100
20 100
1
1
1
1
1
50
23
50
50
50
50
50
50
50
50
50
> 100
43
31
87
50
50
50
50
50
50
50
50
50
50
75
50
50
50
50
50
50
50
50
50
50
Table 3.7: Substantial Inhibitors to Nitrification
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Compound
p-phenylazoaniline
phenol
tannic acid
toluene
triethylamine
zinc
copper
cyanide
chromium(VI)
lead
mercury
quinoline
p-benzoquinone
tetramethylthiuramthiocarbamate
pyridine
cresols
cetyl trimethyl ammonium
tetramethylthiuram disulphide
hydrazine
8-hydroxy-quinoline
diallyl ether
carbon disulphide
dicyandiamide
strychnine hydrochloride
potassium thiocyanate
EDTA (ethylene diamine tetra
acetate)
N-methylalanine hydrochloride
cetyl pyridinium chloride
sodium azide
dichlorophen
trimethylamine hydrochloride
2,4,6-tribromophenol
methylene blue
streptomycin
Inhibition Con- Reduction in

centration
Rate
[mg/l] dissolved
[%]
72
3
> 100
350
127
0.08 0.5
0.005 0.5
0.34
0.25
0.5
1
10
10
20
50
30
50
starting point
50
20
20
20
20 100
20 100
20 100
20 100
20 100
> 100
> 100
300
350
50
50
50
50
50
50
50
50
50
50
50
50
starting point
starting point
starting point
starting point
starting point
50
50
50
550
20 100
20 100
20 100
> 100
> 100
100
400
50
50
50
50
50
50
50
Table 3.7: continued

Advantages
Effective elimination of nitrogen compounds.
Process can be integrated in the existing
biological treatment, e.g. in the CWTP.
Disadvantages
Operation sensitive to varying conditions, pH,
temperature, inhibitors, waste water contents.
Process might necessitate carbon as nutrient
feed.
Gaseous releases to air, e.g. nitrous oxide.
Process can be inhibited by contaminants.
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methanol
oxygen
Nitrification
Basin
Denitrification
Basin
Intermediate
Aeration
entry
Final
Clarifier
recycle
excess
sludge
discharge
Figure 3.16: Nitrification/Denitrification in Series

oxygen
entry
Denitrification
Basin
Nitrification
Basin
Final
Clarifier
recirculation
discharge
recycle
excess
sludge
Figure 3.17: Nitrification/Denitrification with Denitrification pre-operated

Appropriately working nitrification/denitrification reduces the content of nitrogen compounds
in waste water considerably, especially ammonium.
As part of the CWTP, nitrification/denitrification basins and equipment contribute to the release
of odorous and volatile substances. No further emissions to the environment are to be expected.
the electric energy for the additional equipment such as pumps, aeration jets, vents, mixers,
sludge collector,
treatment agents, e.g. additional carbon feed, if necessary,
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With the pre-operated denitrication process, the major part of the waste water stream that leaves
the nitrification basin or zone has to be re-ducted to biological aeration, thus requiring a great
deal of pumping energy.
The common noise sources such as pumps, jets, mixers, etc. should be considered and
appropriate measures taken, e.g. enclosure of equipment.
Monitoring
The regulations for the CWTP are also valid for monitoring the nitrification/denitrification
process. The process has to be protected from the entry of inhibiting substances and the
receiving water from uncontrolled discharges.
Costs
labour costs:
utilities:
total costs:
not known
3.3 Rainwater Treatment

3.3.1 Rain and Fire Water Control
An essential point for industrial activities is the prevention of uncontrolled effluents from the
site. Where appropriate, extra guarded discharge facilities, e.g. extra rainwater tanks or basins,
may be installed as a means of controlling the discharge of pollutants in consequence of heavy
falls of rainwater and fire fighting water. Their function is to allow retention of these waters for
inspection and examination before making a decision on whether to discharge directly to the
receiving water or to re-direct it for supplementary treatment.
Such facilities may include a first flush compartment and hold-up for rainwater to cater for the
effluent which occurs as a result of the first rain after a relatively dry period and further
compartments for subsequent rainfall.
The pumping capacity to transfer contaminated effluent from the controlled discharge facility to
further treatment should be based on the available intake capacity of the secondary treatment
facility, whilst considering the need to sufficiently empty the controlled discharge facility
before the next rain [cww/tm/48].
3.3.2 Wet Detention Ponds

Principle
A wet detention pond is a constructed pond that maintains a permanent pool of water within a
designated area, and relies on physical, biological and chemical processes to remove pollutants
from rainwater runoff. Additionally, wet detention ponds control the rainwater flow to prevent
downstream strain of the recipient. As new rainwater enters the pond, treated water is displaced
and discharged into a receiving body of water. Pollutant removal in the pond is achieved using
solid settling or sedimentation. Depending on the kind of pollutant and the hydraulic residence
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time, eutrophication might occur. From time to time it will be necessary to remove the
sediment.
Application
A wet detention pond is used to clarify and/or cleanse rainwater of pollutants. These pollutants
can include sediment, organic matter and, under certain circumstances, dissolved metals and
nutrients. It can be applied to industrial sites with contaminated surfaces such as roads, parking
spaces and roofs covered with fall-out from stacks etc., or to storage, loading and unloading
areas where leaks might be discharged together with rainwater.

The operation of wet detention ponds relies on the existence of a permanent pool of water
within the basin. A large ratio between permanent pool storage and the mean rainwater runoff
results in increased retention and treatment between two rain events, and ensures the permanent
existence of water in the pond. Normally a hydraulic residence time of two weeks is suggested
if biological removal is intended. On the other hand, two thirds of the sediment, trace metals
and nutrients are removed as the result of a settling process within 24 hours [cww/tm/77].
The water within the pond is discharged through a wet pond outlet that consists of a vertical
riser attached to a horizontal barrel that conveys the rainwater flow beneath the embankment to
a recipient. The outlet is designed to let excess water pass while maintaining a permanent pool.
Risers are typically placed in, or on the edge of, the embankment and are capped with a rubbish
rack to prevent clogging.

Advantages
For dischargers into weak recipients detention
ponds decrease the potential for downstream
flooding and streambank erosion.
Disadvantages
Removal of suspended solids, metals and

dissolved nutrients from receiving water.

Achievable pollutant removal at various hydraulic residence times (HRT) is shown in Table 3.8
[cww/tm/77].
Parameter
Total Suspended Solids (TSS)
Total Phosphorous
Soluble Nutrients
Lead
Zinc
BOD
COD
Percent Removal
varying HRT
HRT 2 weeks
50 90
30 90
40 80
80 90
50 70
70 80
40 50
20 40
20 - 40
Table 3.8: Pollutant Removal by Wet Detention Ponds Dependent on Hydraulic Residence Time
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Sedimented sludge has normally to be disposed of, probably as waste, but this rarely happens. It
might be necessary after several years, depending on the size of the pond.
Monitoring
Proper maintenance will ensure continued accurate functioning of the wet detention pond. This
includes:
clearing rubbish and debris,

conducting routine inspections of the embankment and spillway to check structural integrity
and look for signs of erosion or animal habitation,
conducting periodic repairs on the embankment, emergency spillway, inlet and outlet,
removing sediment and algae,
removing woody vegetation or trees from the embankment that could potentially weaken
the embankment,
maintaining the outfall area.
Costs
labour costs:
utilities:
total costs:
3 hours per month

no costs
not known
3.3.3 Sand Filters

Principle
A special application of sand filters is their function to treat rainwater runoff and remove
pollutants such as suspended solids, BOD, phosphorous and even some kinds of bacteria
[cww/tm/77]. Sand filters provide a highly effective instrument to remove pollutants from
rainwater while remaining flexible in application to allow for modifications in basic design
structure to accommodate site-specific criteria.
Application
The sand filter can be applied where there is not enough space to incorporate a wet detention
pond on an industrial site. It is used to treat rainwater from contaminated surfaces such as roads,
roofs, parking areas, storage areas, loading and unloading areas of an industrial site.

Sand filters for rainwater treatment are usually composed of two components, a sedimentation
chamber, where floatables and heavy sediments are removed, and a filtration chamber, where
additional pollutants are removed.
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Examples of sand filters are:
the surface sand filter basin,

the underground vault sand filter,
the double trench sand filter,
the stone reservoir trench sand filter,
the peat sand filter.

Advantages
High removal efficiencies achievable.
Disadvantages
Dissolved substances are not removed, if
adsorption does not occur.
Hydrocarbons are also removed.

Can be used on small sites where a wet
detention pond is not possible due to space
limitations

With a sand filter for rainwater treatment, the following removal efficiency ranges are reported
[cww/tm/77], filter type a double trench sand filter:
Total Suspended Solids (TSS):
BOD:
TOC:
Total Kjeldahl Nitrogen (TKN):
Zinc:
Total Phosphorous (TP):
Total Nitrogen:
Nitrate Nitrogen:
80 83 %
77.5 %
65.9 %
70.6 %
81.6 %
72.3 %
47.2 %
62.7 %
Backwashed sludge has to be disposed of as waste.

Monitoring
Performance of sand filters may be sustained through frequent inspections and regular
replacement of the filter media. Accumulated rubbish and debris should be removed from the
sand filter whenever it is necessary. The performance can be increased by organising the
drainage area appropriately, for example by building roofs over loading and unloading areas or
by regularly cleaning the roads or parking areas.
Costs
The investment costs are dependent on the filter system and vary widely
labour costs:
utilities:
total costs:
3 hours per year

no costs
not known
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Chapter 3
3.4 Sludge Treatment

All treatment operations and processes described above result in a specific amount of sludge
arising from the applied treatment techniques. Amount, consistency and content of sludge
depend on the kind of waste water (i.e. pollutant content) and the method of treatment the waste
water run through. It is usually a liquid, or semisolid liquid, with solid contents between
0.25 - 12 % (weight) [cww/tm/4] and contains primarily the pollutants removed from the waste
water. Surplus activated sludge from a biological CWTP consists mostly of degradation
(mineralisation) products and bacterial tissue as well as adsorbed pollutants such as heavy
metals. Typical metal contents in untreated waste water sludge are shown in Table 3.9
[cww/tm/4].
Metal
Arsenic
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Manganese
Mercury
Molybdenum
Nickel
Selenium
Tin
Zinc
Dry Sludge
Range
[mg/kg]
1.1 230
1 3410
10 99000
11.3 2490
84 17000
1000 154000
13 26000
32 9870
0.6 56
0.1 214
2 5300
1.7 17.2
2.6 329
101 49000
Table 3.9: Typical Metal Content in Waste Water Sludge
Untreated sludge is not suitable to discharge or dispose, because of its
content of pollutants offensive to waste water, thus sludge cannot be discharged into a
receiving water,
large amount of water, thus its incineration is energetically an unattractive option.
These are some of the reasons why sludge has to go through special treatment
operations/processes, such as:
thickening,
conditioning,
de-watering,
final treatment (incineration, wet-air oxidation).
Sludge originating from waste water of the chemical industry is in general not suitable for
agricultural purposes, but this depends on Member State legislation. A critical aspect can be the
content of heavy metals, AOX/EOX and other persistent sludge components.
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3.4.1 Sludge Pumping

The characteristics of sludge e.g. its consistency require the application of special sludge
pumps. Examples of sludge pumps are:
plunger pumps, with simplex, duplex or triplex units (one, two or three plungers), capacity
2.5 3.8 l/s, obtainable with heads up to 70 m [cww/tm/4], working for all kinds of sludge
such as scum, primary sludge, sludge from chemical precipitation, return or waste activated
sludge, thickened sludge (Figure 3.18 a, [cww/tm/4]),
progressive cavity pumps, capacity up to 75 l/s, discharge heads of 137 m available
[cww/tm/4], working for scum, primary sludge, sludge from chemical precipitation, return
or waste activated sludge, thickened sludge; expensive maintenance (Figure 3.18 b,
[cww/tm/4]),
centrifugal pumps of non-clog design, to be equipped with variable speed drives, commonly
used, e.g. for scum, return or waste activated sludge (Figure 3.18 c, [cww/tm/4]),
torque-flow pumps, very effective in sludge convey when variable speed control is applied,
commonly in use for scum, primary sludge, sludge from chemical precipitation, return or
waste activated sludge, thickened sludge (Figure 3.18 d, [cww/tm/4]),
diaphragm pumps, usually with low capacity (14 l/s) and low head (15 m) [cww/tm/4],
commonly in use for scum, primary sludge, sludge from chemical precipitation, return or
waste activated sludge, thickened sludge (Figure 3.18 e, [cww/tm/4]),
high-pressure piston pumps, normally used within high-pressure applications, commonly
working for thickened sludge or sludge to be pumped over longer distances; pumps are very
expensive (Figure 3.18 f, [cww/tm/4]),
rotary lobe pumps, commonly working for primary sludge, sludge from chemical
precipitation, thickened sludge (Figure 3.18 g, [cww/tm/4]).
3.4.2 Sludge Thickening

Principle
Thickening is an operation to increase the solid content of sludge and remove a part of the water
fraction using physical applications such as:
gravity thickening,
centrifugal thickening,
flotation thickening,
gravity belt thickening,
rotary drum thickening.
The benefit of sludge thickening is a manifold (about five fold or more) decrease in volume to
facilitate subsequent treatment operations as well as decrease the necessary size and capacity of
treatment equipment.
3.4.2.1 Gravity Thickening
Application
Gravity thickening is applied to untreated primary sludge, waste activated sludge and a mixture
of both.
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Chapter 3

Gravity thickening works with similar equipment to sedimentation. Typically a circular tank is
used. Its design is shown in Figure 3.2.
Storage facilities have to be provided for the thickened sludge.
Figure 3.18: Sludge and Scum Pumps in Waste Water Treatment Plants
[(a) plunger pump, (b) progressive cavity pump, (c) centrifugal non-clog pump, (d) torque flow
pump, (e) diaphragm pump, (f) piston pump, (g) rotary lobe pump]
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Advantages
Excellent results with untreated primary
sludge.
Disadvantages
Only marginal results with large plants.
For waste activated sludge only poor solids

With small plants generally satisfactory results concentration.
with sludge concentrations between 4 and 6 %.

The thickening effect is not very high unless the sludge has undergone thermal conditioning
before. For examples see Table 3.10 [cww/tm/4]:
Sludge concentration [%]

Unthickened Thickened
Type of Sludge
primary sludge
air activated sludge
primary and air activated sludge
thermally conditioned primary sludge
thermally conditioned waste activated
sludge
thermally conditioned primary and waste
activated sludge
27
0.5 1.5
25
36
0.5 1.5
5 10
23
28
12 15
6 10
3-6
8 - 15
Table 3.10: Typical Concentrations of Unthickened and Thickened Sludges for Gravity Thickeners
electric energy for pumps, sludge and scum removal system

Sources of noise are pumps, which can be enclosed, and the sludge/scum removal system.
The emission of odour depends on the kind of sludge and its biological degradation in the
thickener. The presence of volatile contaminants may require a closed tank or a covered basin.
Monitoring
To prevent disturbances the thickening process has to be examined at least visually. Sludge
input and its consistency should be frequently monitored. The appearance of bulking sludge has
to be detected to prevent its release.
Costs
labour costs:
utilities:
total costs:
not known
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Chapter 3
3.4.2.2 Centrifugal Thickening
Application
Centrifugal thickening is applied to waste activated sludge.

The two main applications of centrifugal thickening are:
the solid bowl centrifuge,

the imperforate basket centrifuge,
both illustrated in Figure 3.19 [cww/tm/4].
Figure 3.19: Centrifugal Sludge Thickener Applications

(a) Solid Bowl Centrifuge, (b) Imperforate Basket Centrifuge
The solid bowl centrifuge works continuously, the sludge particles driven to the periphery of the
vessel. The imperforate basket centrifuge is processed batch-wise, the solids concentrating at
the wall and the centrate decanted.

Advantages
For solids that are difficult to filter.
Disadvantages
High maintenance and power costs.
Can be worked in limited space.
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No performance data available.
electric energy for pumps, sludge and scum removal system, rotation of centrifuge,
polymer addition for waste activated sludge thickening, with the solid bowl centrifuge 0 4
kg/tonne dry solid, with the basket centrifuge 1 3 kg/tonne dry solid [cww/tm/4].

Sources of noise are pumps that can be enclosed, the sludge/scum removal system and the
rotating centrifuge. Appropriate measures have to be taken for noise control.
Monitoring
To prevent disturbances the input has to be checked to prevent damage to the equipment.
Costs
labour costs:
utilities:
total costs:
not known
3.4.2.3 Flotation Thickening
Application
DAF is applied to waste activated sludge and to a mixture of untreated primary sludge and
waste activated sludge. Sludge containing metal salts has also successfully been flotated.

A DAF thickener is shown in Figure 3.20 [cww/tm/4]. The depressurised solution releases air
bubbles that carry the sludge to the top of the DAF unit from where it is removed. When low
temperatures and/or odour control are an objective, the DAF unit is normally enclosed in a
building.

Advantages
Good efficiency for waste sludge from
biological treatment processes.
Disadvantages
Vulnerable to freezing (blocking of air jets).
Release of odorous substances (stripping
effect).
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Chapter 3

electric energy for pumps, sludge and scum removal system and compressor,
polymer addition to thicken waste activated sludge, 2 5 kg/tonne dry solids [cww/tm/4].

Sources of noise are pumps which can be enclosed, the sludge/scum removal system and the
inlet of pressurised air/waste water mixture. Appropriate measures for noise control have to be
taken, e.g. enclosure of the equipment. Enclosure might be also an appropriate measure for
odour control.
Figure 3.20: DAF Thickener for Waste Activated Sludge
Monitoring
To prevent disturbances the thickening process has to be examined at least visually. To ensure
accurate working the parameters to be monitored are the sludge input and its consistency. The
addition of polymers should be monitored to ensure appropriate improvement of the flotation
process.
Costs
136
labour costs:
utilities:
total costs:
not known
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Chapter 3
3.4.2.4 Gravity Belt Thickening
Application
Gravity belt thickening is applied to waste activated sludge, particularly to solids concentrations
of less than 2 % [cww/tm/4].
Installation and Design [cww/tm/4]

The main equipment consists of a gravity belt moving over driven rollers. The conditioned
sludge is added at one end into a feed/distribution box. The sludge is ridged and furrowed by a
series of plow blades, allowing the released water to pass through the belt. Afterwards the belt
travels through a wash cycle.

Advantages
Useful for raw and digested sludge.
Disadvantages
Polymer addition required.

electric energy for pumps, drive of the belt,

polymer addition for waste activated sludge thickening, 3 7 kg/tonne dry solid
[cww/tm/4].

Sources of noise are pumps and the belt drive, thus it might be appropriate to enclose the
equipment.
Monitoring
To prevent disturbances the thickening process has to be examined at least visually.
Costs
labour costs:
utilities:
total costs:
not known
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Chapter 3
3.4.2.5 Rotary Drum Thickening
Application
Rotary drum thickening is applied to waste activated sludge.

A rotary drum-thickening unit consists of a sludge conditioning system with polymer feed and
rotating cylindrical screens. The polymer is mixed with thin sludge in the mixing and
conditioning drum. The flocculated sludge is separated from the water in the rotating screen
drums. The thickened sludge rolls out at the end of the drum, the separated water decants
through the screens [cww/tm/4].

Advantages
Low maintenance.
Disadvantages
Polymer addition necessary.
Low energy use.

Small space requirements.

A thickening range of 3 4 % has been reported for waste activated sludge [cww/tm/4].
electric energy for pumps, drum rotation drive,

polymer addition for waste activated sludge thickening.

Sources of noise are pumps and the drive of the rotary drum, thus it might be appropriate to
enclose the equipment.
Monitoring
To prevent disturbances the thickening process has to be examined at least visually. The sludge
input and its consistency should be monitored regularly.
Costs
138
labour costs:
utilities:
total costs:
not known
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Chapter 3
3.4.3 Sludge De-watering

Sludge de-watering is the removal of water from sludge to such an extent that its volume is
extensively diminished in a way that it can be handled more easily. The advantages are:
reduced sludge volume decreases transport costs when transferring sludge from one
operation unit to the next,
de-watered sludge is easier to handle and transfer because of its more solid consistency,
de-watering is an obligatory precedent to sludge incineration,
prevention of leachates when landfilled.
3.4.3.1 Sludge De-watering by Centrifugation
Principle
Two kinds of centrifuges are commonly in use:
the solid bowl centrifuge (see Figure 3.19 a),

the imperforate basket centrifuge (see Figure 3.19 b).
Application
Solid bowl centrifuges are operated with untreated primary sludge, waste activated sludge,
thermally conditioned sludge, etc. The addition of chemicals, e.g. polymers, improves the
process.
Imperforate basket centrifuges are normally operated with small biological wastewater plants,
where chemical conditioning is not essential.

Fine, non-settling particulates in the centrate will pass through the treatment system after being
returned to the influent. To avoid their discharge, the sludge residence time might be increased
(decrease of feed rate or increase of centrifuge volume) or chemical conditioning might be
utilised (increase of particle size).
Especially the generation of noise owing to the rotating centrifuges should be considered.
Usually firm foundations of the equipment are required to prevent or control noise.
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For the solid bowl centrifuge [cww/tm/4]:
Advantages
Minimal odour problems.
Disadvantages
Moderately high suspended solids content in
centrate.
Fast start-up and shut-down capabilities.

Skilled maintenance personnel required.
Easy installation.
Efficient production of dry sludge cake.
Requires grit removal and sludge grinder

upstream.
Low capital cost/capacity ratio.
High power costs.
Space requirements relatively low compared

with other de-watering systems.
For the imperforate basket centrifuge [cww/tm/4]:
Advantages
Chemical conditioning might be not required.
Disadvantages
Limited size capacity.
Minimal odour problems.
High consumption of energy per sludge unit

de-watered.
Fast startup and shutdown capabilities.

Very flexible in meeting process requirements.
Not affected by grit.
Skimming stream might produce significant

recycle load.
Highest capital cost/capacity ratio of the dewatering systems.
Excellent results for difficult sludges.

Produces lowest cake solids concentration of
the de-watering systems.
Low capital cost/capacity ratio.

Space requirements relatively low compared
with other de-watering systems.
Vibrations and noise generation.

Typical performance data of the solid bowl and the imperforate basket centrifuges are presented
in Table 3.11 [cww/tm/4]:
flocculant and/or coagulant chemicals, with dosage rates of 1 7.5 kg/tonne dry solid
[cww/tm/4],
electric energy for pumps, centrifuge.

Sources of noise are pumps and the rotating centrifuge, thus noise control is a central issue.
Sturdy foundations and soundproofing have to be provided.
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Cake
Solids
[%]
Type of Sludge
Untreated primary
Untreated primary + air activated
Waste air activated
Waste oxygen activated
thermally conditioned primary +
air activated
25-35
12-20
5-15
10-20
30-40
Solid Bowl
Solids Capture [%]
Without
With
CheChemicals
micals
75-90
55-65
60-80
60-80
75-85
> 90
> 90
> 90
> 90
> 90
Imperforate Basket
Solids Capture [%]
Cake
Without
With
Solids
CheChe[%]
micals
micals
25-30
12-14
8-14
90-95
85-90
> 95
> 90
> 90
Table 3.11: De-watering Performance of Centrifuges
Monitoring
The influent has to be checked to prevent damage by grit and oversized particles.
Costs
labour costs:
utilities:
total costs:
not known
3.4.3.2 Sludge De-watering by Belt Filter Presses
Principle
The conditioned sludge is introduced on a gravity drainage section where it thickens and the
water separates because of gravity. This operation can be assisted by vacuum, simultaneously
enhancing drainage and reducing odour. After gravity drainage, pressure is applied in a lowpressure sector, where the sludge is squeezed between opposing porous belts to release
additional water. The de-watered sludge cake is removed from the belts by means of scraper
blades [cww/tm/4].
Application
Belt filter presses are applicable to almost all types of sludge. Normally the addition of
flocculant chemicals and polymers is necessary.
sensitive to widely variable sludge characteristics.
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Chapter 3

A typical belt filter press is shown in Figure 3.21 [cww/tm/4].
The system consists of:
sludge feed pumps,

polymer feed equipment,
flocculator for sludge conditioning,
belt filter press,
sludge cake conveyor,
support systems such as washwater pumps, compressed air, etc.
Safety considerations should include good ventilation to remove gases such as hydrogen
sulphide and mechanical measures to prevent accidents because of, e.g. loose hanging filter
cloth etc.
Figure 3.21: Belt Filter Press De-watering

Advantages
Low energy requirement.
Disadvantages
Hydraulic limitations.
Low capital and operating costs.
Sludge grinder in feed required.
Easy maintenance.
Very sensitive to incoming sludge feed

characteristics.
Production of very dry cake.

Easy system shutdown.
142
Short media life compared to other dewatering devices.
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Chapter 3

Typical de-watering performances for belt filter presses are presented in Table 3.12 [cww/tm/4]:
Type of Sludge
Primary
Primary + waste acitivated
Waste activated
Thermally conditioned primary + waste activated
Feed Solids
[%]
Cake Solids
[%]
37
36
14
48
28 44
20 35
12 20
25 50
Table 3.12: De-watering Performance of Belt Filter Press
flocculant and/or coagulant chemicals,

electric energy for pumps, belt filter,
washing water.

Sources of noise are pumps and the belt filter press working. Appropriate control measures have
to be taken.
Monitoring
The influent has to be checked carefully to prevent damage because of grit and other particles.
Costs
labour costs:
utilities:
total costs:
not known
3.4.3.3 Sludge De-watering by Filter Presses
Principle
Filter presses are facilities where the solid/liquid separation takes place at high-pressure
(7 - 15 bar). The sludge is forced through a series of filter cloths where the particulates remain
as filter cake. The filtrate is recycled to the waste water treatment plant. Generally chemicals
have been added to the sludge as conditioning and flocculation agents. The filtration process
consists of the steps [cww/tm/4]:
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Chapter 3
filling the filter press,

keeping the filter press under pressure,
opening the filter press,
washing and discharging the cake,
closing the filter press.
Application
Filter presses are applied when a low content of suspended solids in the filtrate is required
and/or a high de-watering efficiency is sought.

The most common types of filter presses for sludge de-watering are:
the fixed volume recessed plate filter press (shown in Figure 3.22 [cww/tm/4]),
the variable volume recessed plate filter press.
Issues for the installation of filter press equipment are [cww/tm/4]:
adequate ventilation in the de-watering compartment, 6 to 12 air changes per hour are
recommended, depending on the temperature,
high-pressure washing systems,
an acid wash circulation system, when the sludge has been conditioned with lime,
sludge grinder upstream of the conditioning tank,
cake breakers or shredders after the filter press,
equipment to facilitate removal and maintenance of the plates.
Figure 3.22: Fixed Volume Recessed Plate Filter Press
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Chapter 3
If no immediate incineration is intended, storage facilities should be provided for the filter cake
material.

Advantages
High cake solids concentration.
Disadvantages
Batch operation.
Low suspended solids in filtrate.
High equipment, labour and utilities costs.
High solids capture.
Special requirements for support structure.

Large floor area required for equipment.
Skilled maintenance personnel required.
Limited filter cloth life.

Filter presses give the highest cake solids concentration of all de-watering facilities. Sludge
concentrations of 30 52 % (dry matter content) can be achieved.
conditioning chemicals, often lime,

electric energy for pumps,
water to wash the filter plates.

The filter cake has to be disposed of. Usually this is done by incineration, either on-site or offsite.
Monitoring
Filter cloths are sensitive to mechanical damage, thus oversized or otherwise critical solids must
not enter the filter press.
Costs
labour costs:
utilities:
total costs:
not known
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Chapter 3
3.5 Waste Gas Treatment

The categorisation for waste water treatment that follows the characteristics of pollutants would
not be similarly successful as the one for waste water treatment. With waste gas, not only the
nature of pollutants determines which treatment operation or process to apply, but also their
source of creation. Dust generated in an incineration plant or at a loading/unloading site might
need different treatment operations; or solvents evaporating as VOCs from a chemical process
or product work-up are differently treated than VOCs set free from a waste water treatment
plant or from a storage hall. Whereas some discharges might allow material recovery, others
might require abatement processes. Figure 3.23 illustrates this situation.
WASTE GAS
PRODUCTION
AND
WORKUP
R
E
C
O
V
E
R
Y
VOC
INORGANIC
GASES
DUST
Membranes
Condensation
Adsorption
Scrubbing
Biofiltration
Bioscrubbing
Incineration
Separation
Dust
Scrubbing
HANDLING
A
B
A
T
E
M
E
N
T
R
E
C
O
V
E
R
Y
VOC
INORGANIC
GASES
DUST
Adsorption
Scrubbing
Biofiltration
Bioscrubbing
Incineration
Dust
Scrubbing
Filtration
INCINERATION
A
B
A
T
E
M
E
N
T
R
E
C
O
V
E
R
Y
DUST
NOx
SOx
A
B
A
T
E
M
E
N
T
ESP
Cyclone
Filtration
Catalytic
Filtration
Sorbent
Injection
Biological
SO2 Removal
SNCR
SCR
Filtration
Figure 3.23: Schematic Overview of Waste Gas Treatment in a Chemical Plant
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Chapter 3
A plain ranking for waste gas treatment operations and processes, that encompasses both
nature of pollutants and source of creation might cause overlaps or repetitions, or even gaps,
because some technologies are applicable to several kinds of pollutants, or to several kinds of
sources. Thus this document has chosen as approach to develop the waste gas treatment
description:
recovery operations and processes for VOCs,

abatement operations and processes for VOCs and inorganic gases,
abatement technologies for particulates,
abatement operations and processes for gaseous pollutants in flue gases.
Some of the described technologies are individual operations and/or processes, others are only
used as secondary pre-treatment methods to avoid damage to the main treatment facilities or just
take the role of a pre-filter. Others can be used as both individual or secondary technology.
Examples will be given in the subsequent paragraphs.
Recovery operations and processes for VOCs are:
Selective Membrane Separation,
Condensation,
Adsorption,
Scrubbing for Trace Gas Removal,
Abatement operations and processes for VOCs and inorganic gases are:
Biofiltration,
Bioscrubbing,
Catalytic Filtration,
Thermal Incineration,
Catalytic Incineration,
Flaring,
taking into consideration adsorption as well, because it can also be used as an abatement
technology. Not all the technologies above are suitable for inorganic gases.
Abatement technologies or facilities for particulates are:
Separator,
Cyclone,
Electrostatic Precipitator,
Dust Scrubber,
Fabric Filter,
Two Stage Dust Filter,
Ceramic Filter,
Absolute Filter,
HEAF Filter,
Mist Filter.
Abatement operations and processes for gaseous pollutants in flue gases are:
Dry Sorbent Injection,

Semi-dry Sorbent Injection,
Biological Sulphur Dioxid Removal,
Selective Non-catalytic Reduction of NOx (SNCR),
Selective Catalytic Reduction of NOx (SCR).
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Most waste gas treatment technologies have one thing in common: they produce waste. This
waste can be a solid waste, to be disposed of, or liquid waste discharged as waste water that has
to be treated. This will be discussed in the relevant chapters.
3.5.1 Recovery Operations and Processes for VOCs

3.5.1.1 Selective Membrane Separation
Principle
Membrane separation takes into account the selective permeability of organic vapours when
permeating through a membrane. Organic vapours have a considerately higher permeation rate
than oxygen, nitrogen, hydrogen or carbon dioxide (10 to 100 times higher [cww/tm/74]). The
waste gas stream is compressed and passed over the membrane. The enriched permeate can be
recovered by methods such as condensation. The process is most appropriate to high vapour
concentrations. Additional treatment may be needed to achieve concentration levels low enough
to discharge [cww/tm/80].
The permeation process is schematically shown in Figure 3.24 [cww/tm/70].
gas
gas
permeate
Figure 3.24: Membrane Separation
Application
Membrane separation is usually employed to recover solvent vapours from waste gas or exhaust
air. It is applied, e.g., in the chemical industry, the petrochemical industry, refineries and the
pharmaceutical industry. Examples are [cww/tm/74]:
recovery of olefin monomers from polyolefin resin degassing streams,

recovering of vinyl chloride from PVC manufacturing,
recovery of solvent and hydrocarbon vapours from tank-filling,
recovery of hydrocarbon feedstocks from refinery vent and fuel gas streams,
recovery of hydrogen from refinery offgas.
Recoverable compounds include:
148
alkanes,
olefins,
chlorinated hydrocarbons,
aromates,
ketones,
ethers,
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esters,
alcohols,
monomers such as vinyl chloride, ethen, or propen.
waste gas flow:

temperature:
pressure:
dust content:
VOC concentration:
depends on membrane area,

ambient temperature, dependent on the membrane material,
dependent on the membrane material,
very low,
< 1000 ppm up to 90 %
The presence of dust can damage the membrane surface, thus very low dust concentrations are
considered necessary or have to be achieved before the waste gas stream can be ducted into a
membrane system.

Membrane separators are designed as modules, e.g. as capillary modules (see Figure 3.25)
[cww/tm/64], manufactured as a polymer layer.
Figure 3.25: Typical Membrane Capillary Module
A membrane separation system consists of:
the membrane modules,

a compressor,
a condenser (or another recovery unit),
vents and ducts.
A typical membrane separation process is illustrated in Figure 3.26 [cww/tm/64]. There are
several processing methods, e.g. operating condensation upstream instead of downstream.
To create the necessary pressure difference between feed and permeate sides of the membrane
(1 10 bar) the system works either by means of excess pressure on the feed side, vacuum
(about 2 mbar) on the permeate side or both [cww/tm/64].
During the rise of vapour concentration within the membrane unit, the concentration level can
climb from lower to higher than explosive limit and thus develop an explosive mixture. So steps
have to be taken to avoid this situation or to handle the risk.
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Chapter 3
Advantages/Disadvantages
Advantages
The re-use of solvent is possible.
Disadvantages
Subsequent work-up and/or treatment step
necessary.
The operation in itself is simple.

Explosion risk.
For higher capacities large membrane areas
are needed.
High cost.

An efficiency range of 90 to > 99 % for recovery of hydrocarbons, and about 99.9 % for other
VOCs is achievable, depending on the related application [cww/tm/74].

cooling liquids,
energy for compressors, pumps, fans and/or cooling devices.
Figure 3.26: Membrane Separation Process for Waste Gas
The energy consumption is approximately 250 kWh/1000 Nm3/h, including the electric energy
for the fan [cww/tm/70].
The pressure difference can be 1 10 bar across the membrane [cww/tm/64].
Some utilities may be derived from subsequent cleaning steps, such as heat exchanger for
condensing, incineration or adsorption.
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Chapter 3
Membrane separation is frequently used as a concentration step followed by a final recovery

step. Since the enrichment of VOCs in the gas phase increases the dew point of the waste gas
stream, subsequent condensation might become easier and more economical. If the enriched
waste gas stream has to be incinerated, the increase of VOC concentration decreases the
consumption of additional fuel.
VOCs from membrane separation processes are usually recycled and no residues result from the
actual membrane process. It may, however, give cause to waste in a subsequent treatment step.
Residual emissions might arise from cooling water or the treated waste gas stream. These gas
streams either are released to the atmosphere via stack or to a following waste gas treatment
step, such as adsorption, incineration etc.
Monitoring
The efficiency of the membrane separation system may be determined by monitoring the
concentration of the solvent vapours before and after the membrane system. VOCs can be
measured as total carbon, using a flame ionisation detector.
Additionally the vapour/oxygen content has to be carefully observed for safety reasons
(explosion risk).
Costs
The investment costs are approximately k 300/1000 Nm3/h for a 200 Nm3/h system
[cww/tm/70]
The operating costs are [cww/tm/70]:
labour costs:
approximately k 1.5/year (4 days per year)
utilities:
k 60/1000 Nm3/h
not known
1.5 + 60 x flow/1000 k/year
total costs:
Cost relevant parameters are the waste gas flow rate and the technical service life of the
membrane. Revenue is the recovered VOC.
System costs vary in relation to the desired recovery target, capacity and design. Payback period
in connection with high-value products can be between four months and one year [cww/tm/74].
Other VOCs might have no payback at all. Combination with another process (e.g. adsorption
or absorption) might be profitable compared with a one step separation.
3.5.1.2 Condensation
Principle
Condensation is a technique that eliminates solvent vapours from a waste gas stream by
reducing its temperature below its dew point, often employing refrigeration.
There are three methods of condensation:
coolant/refrigerant condensation,
cryogenic condensation,
closed-cycle inert gas condensation.
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Chapter 3
Coolant/refrigerant condensation is carried out by means of direct (i.e. contact between gas and
cooling liquid) or indirect cooling (i.e. cooling via heat exchanger). Direct condensation
requests an additional separation stage, thus indirect condensation is preferred. Recovery
systems vary from simple, single condensers to more complex, multi-condenser systems
designed to maximise energy and vapour recovery [cww/tm/71].
Cryogenic condensation is carried out at extremely low temperatures using cryogenic nitrogen
[cww/tm/71].
Closed-cycle inert gas condensation is designed for closed-cycle systems together with high
vapour concentrations. A fixed volume of inert gas generally nitrogen is continuously
recycled around the oven and the condensation unit. A proportion of the nitrogen/vapour
mixture is continuously drawn into the recovery module, where a series of heat exchangers cool
and condense the vapours [cww/tm/71].
Application
Condensation is employed to recover solvent vapours. Whereas conventional condensation
techniques (coolant/refrigerator condensation) are suitable for solvents with a reasonably high
vapour pressure, cryogenic condensation is able to cope with all solvents irrespective of their
individual vapour pressures [cww/tm/71].
Condensation systems are regarded as useful preliminary recovery units to reduce a high solvent
loading preceding to further recovery processes, e.g. activated carbon adsorption, but also as
viable single options for solvent recovery [cww/tm/71]. They can also be used to recover VOCs
from effluent gases of waste water stripping operations.
Application limits and restrictions [cww/tm/70]:
waste gas flow:
temperature:
pressure:
dust content:
odour:
ammonia:
DCM:
toluene:
MEK:
acetone:
methanol:
VOC:
100 - 100000 Nm3/h (conventional condensation)

up to 1000 Nm3/h (cryogenic condensation),
50 - 80 C (conventional condensation)
up to 65 C (cryogenic condensation),
atmospheric (conventional condensation)
20 mbar 6 bar (cryogenic condensation),
< 50 mg/Nm3 (non sticky),
> 100000 ou/Nm3,
200 1000 mg/Nm3,
20 1000 g/Nm3 (cryogenic condensation),
200 1000 g/Nm3 (cryogenic condensation).

Coolant/refrigerant condensation is operated with two types of heat exchangers:
152
The conventional shell-and-tube heat exchanger [cww/tm/71]

Low volatility solvents can be effectively recovered using water-cooled or air-cooled
systems. For more volatile solvents, two-stage condensation using water-cooling in the first
stage and refrigeration in the second stage may be necessary.
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Chapter 3
A two-stage system consists of:
the recuperator, using the cold purified gas stream as chilling agent,
the pre-cooler for further cooling, using chilled water or the cold purified gas stream,
the main refrigerator condenser,
the necessary vents and ducts.
A typical two-stage condensation system is illustrated in Figure 3.27 [cww/tm/71].

Another option involves partial condensation at a slightly higher temperature followed by
removal of the remaining solvent from the gas stream by another technique, such as
adsorption.
To minimise fog formation, a series of condensers can be used, as well as a demister and/or
reduction of the gas velocity throughout the condenser.
solventladen
air
Recuperator,
using cold
purified air
Pre-cooler using
chilled water or
cold purified air
purified
air
Refrigerated
Condenser
captured
solvent
Figure 3.27: Two-Stage Condensation System
Spiral heat exchanger [cww/tm/71]

This basically consists of two long strips of plate wrapped to form a pair of concentric spiral
passages. The cooling medium enters through a peripheral nozzle, spirals to the centre and
exits, via a pipe, to a nozzle on the periphery. Process vapours enter through the bottom of
the condenser and flow upwards in cross-flow.
The operation options for cryogenic condensation are [cww/tm/71]:
The vaporisation of nitrogen (heat of evaporation) is used as a coolant, the solvent vapour
condensing at the cold surface of the condenser. The evaporated nitrogen is used as a
blanket to keep the VOC concentration below 25 % of the lower explosive limit. An
example is shown in Figure 3.28 [cww/tm/71].
Cryogenic condensation is run under an inert atmosphere enabling the gas stream to contain
higher concentrations of VOCs. This is shown in Figure 3.29 [cww/tm/71].
The condensation system consists of:
the pre-condenser, using chilled water or glycol,

the main process condenser(s),
the process economiser,
the nitrogen economiser,
the nitrogen vaporiser,
the necessary vents and ducts.
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Chapter 3
Figure 3.28: Cryogenic Condensation Recovery System Integral with a Typical Nitrogen
Blanketing Operation
Figure 3.29: Cryogenic Recovery System under Inert Atmosphere
A typical closed-cycle inert gas condensation system consists of:
154
the heat exchanger, pre-cooling the gas stream,

the main condenser, mechanically refrigerated to as low as 40 C,
the solvent separator,
the nitrogen supply.
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Chapter 3
A typical system is shown in Figure 3.30 [cww/tm/71].
Figure 3.30: Typical Closed-cycle Inert Gas Condensation System
Advantages
With conventional condensation, recovery of
heat possible.
Disadvantages
Cooling water necessary, or in the case of
cryogenic condensation liquid nitrogen.
Recovery of organic solvents.
Variable efficiency with variable waste gas

flow rates and compositions.
Compact technique.
Good process handling possible. Emissions
can be calculated, at least approximately.
Not suitable for wet gas streams formation

of ice.
Very low dew points require temperatures
difficult to attain.
Freezing of surfaces may impede heat transfer.

The following performance data are achievable:
With conventional condensation [cww/tm/70]:
Odour:
Ammonia:
60 to 90 % reduction
20 60 % reduction
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Chapter 3
With cryogenic condensation [cww/tm/70]:
< 20 mg/Nm3
< 100 mg/Nm3
< 150 mg/Nm3
< 150 mg/Nm3
< 150 mg/Nm3
DCM (at 95 C):

Toluene (at 65 C):
MEK (at 75 C):
Acetone (at 86 C):
Methanol (at 60 C):
According to [cww/tm 64] solvent concentrations in waste gas streams at 60 C are achievable
as follows:
1775 mg/Nm3
275 mg/Nm3
75 mg/Nm3
8 mg/Nm3
0.75 mg/Nm3
Aceton:
Methanol:
Heptan:
Toluene:
i-Propanol:
In an installation to load barges, an average hydrocarbon recovery of 95 % is reported

[Forrester, LeBlanc, Chemical Engineering, May 1988, 145-150, cited in cww/tm/80], with
condenser temperatures varying from 45 C in winter to 26 C in summer.
The main utilities and input required for condensation systems depend on the individual system.
Basic heat exchange condenser require:
cooling liquid,
electricity for fans, pumps and refrigeration facilities.
Cryogenic condenser systems require:
liquid nitrogen,
process cooling, if applied,
cooling water, if applied,
electricity for fans and refrigeration facilities,
steam to thaw frozen condensers, if required.
Inert gas cycle condenser systems require:
nitrogen supply for the inert atmosphere, any emergency purges and/or refrigeration.
electricity for fans and refrigeration plant.
An estimated 10 kg/h of nitrogen needed for each kW of cooling required, but this depends on
plant design, solvent type, etc. A typical inert gas cycle plant may use 1 2 tonnes/day of
nitrogen [cww/tm/71].
The energy consumption is:
no information
The pressure drop is 1 - 2 mbar (conventional condensation) [cww/tm/70].

20 50 mbar (cryogenic condensation) [cww/tm/70].
Further input is moisture-free compressed air for pneumatic operations.
During condensation, condensate is formed that can be re-used, re-processed or disposed of as
liquid waste or waste water. Liquid waste might have to be disposed of as hazardous waste (e.g.
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Chapter 3
incinerated), whereas aqueous discharges might be treated in special pre-treatment systems or in

the CWTP.
There are still moderately high VOC concentrations after condensation processes, which require
further treatment (e.g. adsorption, or incineration).
Monitoring
The efficiency of the condensation system as an air cleaning system may be determined by
monitoring the concentration of the solvent vapours before and after. VOCs can be measured as
total carbon, excluding particulate matter, using a flame ionisation detector. Abatement
efficiencies for odorous emissions are determined by taking grab samples at appropriate
sampling points and subsequently analysing them by olfactometry.
Additionally, on inert gas cycle systems, oxygen analysis is carried out to ensure that an inert
atmosphere of less than 5 % oxygen is maintained for safety reasons in the oven vent
stream. If the oxygen content is too high, nitrogen is injected to restore the inert atmosphere
[cww/tm/71].
Costs
The investment costs are:
k 5/1000 Nm3/h (excluding cooling water supply, such as pump,

pipes, cooling tower) for the conventional condensation, and
k 500/1000 Nm3/h (excluding secondary techniques and nitrogen
storage) for the cryogenic condensation [cww/tm/70].
The operating costs are [cww/tm/70]:

labour costs:
1 employee day per week for the cryogenic and 2 hours per week for
the conventional condensation
utilities:
no information
nitrogen costs, cooling water costs
total costs:
variable, not known
Revenue is the recovered VOC.
Capital cost factors are [cww/tm/71]:
emission flow rate overall size of the system,

temperature reduction required equipment costs (the greater the reduction the higher the
costs)
solvent mixtures more complex separation techniques
solvent solubility the more soluble, the more complex separation techniques required.
Operating cost factors are:
emission flow rate utility requirements,

cooling load costs for the supply of cooling agent (the greater the required cooling load
the higher the costs),
solvent mixtures more energy-intensive separation techniques required,
solvent solubility the more soluble, the more energy-intensive the separation
techniques.
Basic heat exchange condensers do not generally need dedicated control systems.
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Chapter 3
Cryogenic systems use standard programmable logic controllers to control nitrogen

requirements for cooling. Automatic operation of the plant should be possible, provided alarms
are set as required and routine checks are carried out by operators during each shift.
Traditional condensation equipment can be readily retro-fitted, with the heat exchangers being
positioned nearby or on top of the relevant piece of equipment.
Cryogenic systems, which are usually only cost-effective on sites that already use nitrogen, may
be skid-mounted. Such systems, which may replace any existing nitrogen vaporisers, should be
installed near a liquid nitrogen source to minimise the length of cryogenic pipeline. Cryogenic
condensation systems can either be retro-fitted to existing plants or integrated into new plants.
Refrigerated vent condensers can be used on solvent tanks, where it is necessary to control
emissions from several closely grouped tanks. In this case, a central refrigeration compressor
can be used to supply small vent condensers on each tank.
In the case of drying ovens, inert gas cycle units are difficult to retro-fit onto existing
production plants; they are more suited to new plants. [cww/tm/71]
3.5.1.3 Adsorption
Principle [cww/tm/79]
Adsorption is a heterogeneous reaction in which gas molecules are retained on a solid surface
(adsorbent). Some adsorbents can preferentially adsorb specific chemical compounds and thus
remove them from effluent streams controlling VOCs and odours.
The three major types of adsorber systems are:
fixed bed unsteady-state adsorbers, which are the simplest and most common,
fluidised bed adsorbers, which have superior mass transfer characteristics,
continuous moving bed adsorber.
Application
Adsorption is normally used for two purposes: as abatement technology for VOCs, odours and
trace gases, and for solvent recovery, if the solvent vapours are sufficiently free from other
pollutants. The application as abatement technology is not recommended for waste gases with
very high VOC concentrations, because the consequent regeneration requirements would
adversely affect profitability.
Adsorption is also used to remove volatile compounds from the effluent gas stream of waste
water stripping operations.
158
waste gas flow:

temperature:
pressure:
hydrocarbon content:
odour:
mercury:
dioxins:
hydrogen sulphide:
100 - 100000 Nm3/h,

15 - 80 C,
1 20 atm,
10 10000 mg/Nm3, depending on lower explosion limit,
10000 200000 ou/Nm3,
1 10 mg/Nm3,
10 100 TEQ/Nm3,
10 200 mg/Nm3.
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Chapter 3
The relative humidity of the waste gas should not be too high; wet gas streams with a relative
humidity higher than 70 % are not easy to handle, whereas fully saturated gas streams are
virtually impossible to process [cww/tm/70].

An issue to consider when designing an adsorber system is the type of adsorbent required.
Typical adsorbents are, e.g. [cww/tm/71]:
granular activated carbon (GAC),

molecular sieve zeolites,
macroporous polymer particles,
silica gel,
sodium-aluminium silicates.
GAC is the most common adsorbent to remove organic vapours. It has the ability to recover
solvents from low concentrations and it is not selective towards polar molecules. The relative
adsorption potential of GAC with various VOCs is illustrated in Figure 3.31 [cww/tm/71].
When impregnating GAC with an oxidant, e.g. potassium permanganate, a significant
improvement can be achieved to remove odorous components. When impregnating GAC with
sulphur compounds, the retention of heavy metals mainly mercury is improved, whereas
potassium iodide improves the capacity to remove hydrogen sulphide [cww/tm/70].
Figure 3.31: Adsorption Potential of GAC with Various Organic Solvents
Adsorbers are often connected in series, the final adsorber playing the role of a police filter.
Most adsorber systems use adsorbents that can be regenerated. They are designed as multiple
bed adsorbers to enable adsorption and regeneration to occur simultaneously. It is generally
necessary to raise the temperature of the adsorbent bed to release the adsorbate. Steam is often
used for this purpose. After the desorption process the steam is condensed and the organic
material separated by decanting or distillation. Hot inert gas may also be used, from which the
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Chapter 3
VOC is recovered by condensation. A typical twin-bed adsorption process is shown in Figure

3.32 [cww/tm/71].
Figure 3.32: Typical Twin-bed Adsorption Process
Polymer adsorbent systems use heated air for the desorption/regeneration process. Polymer
adsorbents have the advantage of [cww/tm/71]:
durability,
being uneffected by elevated humidity,
no catalysing effects prompting the degradation of unstable solvents,
regeneration under very mild conditions,
recovery of high purity solvents.
But polymer adsorbents are about ten times more expensive than GAC [cww/tm/71]. The
continuous adsorption/desorption process with a polymer adsorbent is shown in Figure 3.32
[cww/tm/71].
Figure 3.33: Continuous Adsorption-Desorption with a Polymer Adsorbent
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Chapter 3
Advantages
Simple and robust technology.
Disadvantages
Contaminated adsorbent has to be disposed of,
if regeneration is not possible or suitable.
High saturation grade of the adsorbent.

Particulates in the waste gas stream can cause
problems.
Simple installation.
Simple maintenance.
Breakthrough can occur in mixtures before

saturation of the sorbent.
Cannot be used with wet waste gas streams.
Not suitable for high gas speeds.
Not suitable for high concentrations of VOCs.
Potentially high fire risk for GAC adsorbers.

The following emissions are achievable [cww/tm/70]:
5 100 mg/Nm3
80 95 % efficiency
< 0.05 mg/Nm3
< 0.1 ng TEQ/Nm3
80 95 % efficiency
Hydrocarbon (VOC):
Odour:
Mercury:
Dioxins:
Hydrogen sulphide:
The typical adsorption efficiency for several common solvents using GAC is shown in Table
3.13 [cww/tm/71].
Solvent
feed 1 g/Nm3
Adsorption efficiency (%)

feed 10 g/Nm3
feed 100 g/Nm3
Dichloromethane
11
31
45
Styrene
34
38
41
Tetrachloroethen
50
61
65
Toluene
32
34
37
1,1,1-Trichloroethen
33
47
55
1,1,2-Trichlorotrifluoroethane
11
29
45
Table 3.13: Effect of Varying Feed Concentrations on Mass of Solvent adsorbed
The chief utilities and input required for adsorption systems are:
steam or hot oil (to heat the desorbing inert gas), depending on the desorption method,
cooling water for condensing desorbed solvent,
the adsorbent material.
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Chapter 3
As a general rule, steam regeneration of GAC requires a steam to solvent weight ratio between
1.5:1 and 6:1. Inert gas desorption, using e.g. nitrogen, necessitates according to operating
experience 35 Nm3 of nitrogen to desorb one tonne of solvent. [cww/tm/71]. Another source
[cww/tm/64] reports of:
Steam:
Cooling Water:
Loss of GAC:
1.7 4.0 t/t solvent regained

35 60 m3/t solvent regained
0.5 1 kg/t solvent regained.
The energy consumption is 35 - 100 kWh per tonne regained solvent. [cww/tm/64]
The pressure drop is 20 - 50 mbar. [cww/tm/64]
The loaded GAC either has to be regenerated, producing waste water when carried out with
steam, or disposed of. Depending on the adsorbed pollutants, the disposal might be classified as
hazardous waste that has to be treated appropriately, e.g. by waste incineration. This might be a
key issue when contaminants such as dioxins or mercury are to be expected.
Monitoring [cww/tm/79]
The abatement efficiency of the system may be determined by monitoring the concentration of
VOC/odour before and afterwards. VOCs can be measured as total carbon (excluding
particulate matter), using a flame ionisation detector. A qualitative analysis of the emissions can
be carried out if grab samples of gas are taken at selected sampling points and are subsequently
analysed by GC/MS. Abatement efficiencies for odorous emissions are determined by taking
grab samples at appropriate sampling points and subsequently analysing them by olfactometry.
The most important measurement is the pressure drop across the dust filters and across the
adsorbent bed. Across the filters the pressure should rise steadily after renewal or cleaning. Too
rapid a rise gives warning of too high a pressure drop later on due to an abnormal dust load.
Across the bed the pressure should remain roughly constant. Any increase indicates either dust
by-passing the dust filter or adsorbent dust from granule breakdown. There should also be an
alarm for high pressure.
Costs [cww/tm/70]
The investment costs are k 5 10/1000 Nm3/h
labour costs:
utilities:
total costs:
not known
none
600 1300 per tonne GAC (inclusive of disposal)
not known
162

solvent type choice of adsorbent,
solvent adsorption efficiency and solvent concentration quantity of adsorbent required,
solvent mixtures more or less complex separation techniques
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Chapter 3
Operating cost factors are [cww/tm/71]:

solvent loading use of utilities (steam) in adsorption/desorption cycle and rate of
adsorbent degradation,
presence of impurities reducing life time of adsorbent,
ease of solvent desorption temperature for desorption,
techniques.
Provided sufficient space is available, retro-fitting an adsorption system to an existing

manufacturing process is generally straightforward. The space requirement of a continuous
adsorption/desorption unit is approximately 25 % that of a two-bed adsorber system.
Adsorption systems are typically controlled by a programmable logic controller, with new
systems based on breakthrough sequencing of the beds. When the emission level from an
operating bed reaches a pre-set level, the beds are switched over and regeneration starts. This is
energy efficient as desorption is always performed on a saturated bed.
Subject to consideration of flammable hazards, control systems can be designed to allow a
solvent concentration of up to 40 % of the lower explosive limit. This minimises both fan power
and steam consumption. If flow rates and solvent loading are variable, power requirements can
be optimised by fitting control dampers or variable speed drives for the fan. [cww/tm/71]
3.5.1.4 Scrubbers for Trace Gas Removal

Scrubbing is used as an abatement process for gases such as hydrogen halides, sulphur dioxide,
ammonia, amines and odorous substances, but also as a recovery process for organic solvents
which are readily soluble in water or characterised by a high boiling point.
Principle
Liquid scrubbing or absorption is a mass transfer between a soluble gas and a solvent in
contact with each other. Physical scrubbing is preferred for solvent recovery, whereas chemical
scrubbing is restricted to removing and abating gaseous compounds.
Water as a scrubbing liquid is suitable to absorb soluble acidic gases such as:
hydrogen chloride,
hydrogen fluoride,
silicon hexafluoride,
but also for:
ammonia,
organic components soluble in water.
Alkaline solutions are suitable for absorbing less soluble acidic gases such as:
sulphur dioxide,
hydrogen sulphide,
chlorine,
phenols.
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Chapter 3
Acid solutions are suitable for absorbing:
ammonia,
amines,
esters.
Organic solvents are suitable to absorb organic components less soluble in water.
Oxidising solutions (containing agents such as permanganate, hypochlorite, chlorine dioxide,
ozone, hydrogen peroxide, bisulphite) can be helpful to control organic odours. [cww/tm/70,
cww/tm/79]
Application
Gas scrubbing is applied in chemical industry to abate gaseous pollutants such as hydrogen
halides, halides, sulphur dioxide, ammonia, amines and organic odours in waste gas streams. It
is also used to recover solvents from waste gas streams.
waste gas flow:

temperature:
pressure:
dust content:
alcohols:
ammonia content:
amines content:
esters content:
sulphur dioxide content:
hydrogen fluoride content:
hydrogen chloride content:
nitric acid content:
phenol content:
50 - 500000 Nm3/h,
5 - 80 C,
atmospheric,
< 10 mg/Nm3,
up to 5000 mg/Nm3 ,
up to 20000 mg/Nm3, dependent on absorbent,
up to 1000 mg/Nm3, denpendent on absorbent,
over 100 mg/Nm3,
up to 10000 mg/Nm3, depending on absorbent,
up to 50000 mg/Nm3, denpending on absorbent,
up to a few g/Nm3, depending on absorbent

Various types of scrubbers are operated. The choice is dependent on the requirement of the
abatement/recovery efficiency, energy need, reagents and the properties of the waste gas stream.
Examples are, e.g.:
Fibrous Packing Scrubber

The fibrous packing scrubber consists of a chamber with gas inlet and outlet, containing
mats of fibrous packing material which are sprayed with liquid. The units may be designed
for horizontal or vertical gas flow. Typical fibre materials are glass, plastic, and steel. They
are used to remove acidic components (hydrogen fluoride, hydrogen chloride, sulphuric
acid, nitric acid) and organic/inorganic compounds from effluent gas streams.
The blockage of nozzles, plugging of fibre beds and insufficient irrigation of fibrous mats
might cause problems.
164
Moving Bed Scrubbers

Moving bed scrubbers consist of zones of mobile packing, usually plastic or glass spheres.
The vessel shell contains support grids, on which the packing material is placed, inlets and
outlets for gas scrubbing liquor and a mist eliminator. Moving bed scrubbers are applied to
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Chapter 3
remove sulphur dioxide, hydrogen fluoride and odours. A typical device is shown in Figure
3.34 [cww/tm/79].
Problems encountered with this technology are bed scaling, nozzle plugging and packing
deterioration.
Figure 3.34: Moving Bed Scrubber
Packed Bed Scrubbers

Packed bed scrubbers consist of an outer shell containing a bed of packing material on
support grids, liquid distributors, gas and liquid inlets and outlets and a mist eliminator.
Packed bed scrubbers, with appropriate reagents, have been successfully used to absorb
sulphur dioxide, other acid gases and odour. A typical example is shown in Figure 3.35
[cww/tm/79].
Figure 3.35: Packed Bed Scrubbers
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Chapter 3
Packed bed scrubbers are not suitable for particle collection because of plugging.
Consequently a separate particulate abatement device may be necessary to precede a packed
bed absorber.
Plate Scrubbers
Plate scrubbers consist of a vertical tower with several horizontal perforated (sieve) trays
stacked in it. Baffles are situated a short distance above the apertures in the plates. The
typical application for plate scrubbers is the absorption of acids, sulphur dioxide and
odours. An example is given in Figure 3.36 [cww/tm/79].
Problems encountered with this technology are scaling and plugging. Plate scrubbers are not
suitable for foaming liquids.
Figure 3.36: Plate Scrubber
Spray Towers
Spray towers (or spray scrubbers) consist of spray nozzles at the top of the tower, through
which the scrubbing liquid enters, and a gas inlet near the bottom. Generally the waste gas
stream passes up the tower countercurrent to the liquid flow. The typical application for
spray towers is to remove acid gases and odours. An example is shown in Figure 3.36
[cww/tm/79].
Plugging of spray nozzles might cause problems.
When absorbed VOCs can be recovered, an additional desorption step is necessary. The usual
method of desorption/regeneration of the organic content is steam stripping, transferring the
VOCs back to the gaseous phase. The strip gas will subsequently be condensed and collected.
The condensate will either be re-used directly in the process or segregated into its components
by, e.g. distillation. Stripping and eventually distillation are carried out with reduced pressure in
order to reduce the temperature and minimise the degradation risk of the organic compounds
[cww/tm/71].
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Chapter 3
Figure 3.37: Spray Towers, (a) Counter-current, (b) Co-current
A typical absorption/desorption system is shown in Figure 3.38 [cww/tm/71].
Figure 3.38: Typical Absorption/Desorption system
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Chapter 3
Advantages
Wide range of uses.
Disadvantages
Waste water due to replacement of scrubbing
water.
Many suppliers and applications.

For roof fitting, support structures needed.
Very high efficiency with good design.
For outdoor fitting, frost protection needed
Compact installation thanks to favourable ratio (according to climate).
between capacity and device volume.
Packing material sensitive to clogging because
Simple and robust technology.
of dust or grease.
Simple maintenance.
Only few wear-sensitive components.

The following performance data are achievable [cww/tm/70]:
alcohols:
acids (HF, HCl):
nitric acid:
chromic Acid:
ammonia:
amines:
esters:
sulphur dioxide:
hydrogen fluoride:
hydrogen chloride:
phenols:
< 95 %, emission > 100 mg/Nm3

> 99 %, emission < 10 50 mg/Nm3 (water scrubber)
> 99 %, emission < 10 50 mg/Nm3 (water scrubber)
< 0.1 1 mg/Nm3 (water scrubber)
> 99 %, emission < 1 mg/Nm3 (acid scrubber)
> 99 %, emission < 1 mg/Nm3 (acid scrubber)
> 80 % (acid scrubber)
< 40 mg/Nm3 (alkaline scrubber)
> 90 % (alkaline scrubber)
The main utilities and consumables required for absorption systems are [cww/tm/71]:
electric energy to drive the fans and pumps,

cooling water or chilled water for the condensers,
steam at about 120 C for the steam stripper,
a vacuum system.
Provided there is efficient heat exchange between stripper input and output, the heat
requirement for absorption is likely to be around 30 40 kg per 1000 Nm3/h of waste gas
[cww/tm/71].
Additionally, a work-up of the recirculating liquid is required, dependent on its degradation and
evaporation losses.
Waste water from regeneration has to be disposed of. It can be treated as waste water, re-used as
process water or concentrated to recover VOCs. Regeneration might also cause emissions to air.
The energy consumption is 0.2 0.5 kWh per 1000 Nm3/h, not including the electric energy
for the fan.
The pressure drop is 4 -8 mbar.
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The energy for distillation or steam stripping should be borne in mind.
The abatement efficiency of the scrubbing system may be determined by monitoring the
concentration of trace gases before and afterwards. Sulphur dioxide is usually monitored with
infra red analysers; wet chemical methods are used for hydrogen halides. VOCs can be
measured as total carbon, excluding particulate matter, using a flame ionisation detector. A
qualitative analysis of the emissions can be done if grab samples of gas are taken at selected
sampling points and are subsequently analysed by GC/MS. Abatement efficiencies of odorous
emissions are determined by taking grab samples at appropriate sampling points and
subsequently analysing them by olfactometry.
The pressure drop across the scrubber, the liquid/reagent flow rate and in some cases pH need to
be routinely monitored. Wet scrubbers should be inspected regularly to identify any
deterioration in the plant, such as corrosion or blockages. Access to the scrubber should be
readily available.
Costs [cww/tm/70]
The investment costs are k 2 4/1000 Nm3/h
labour costs:
utilities:
total costs:
0.5 employee-days/week
electricity 0.02 0.05/1000 Nm3/h
water and waste water
variable, not known

recovery efficiency required height of the scrubbing column,
solvent type choice of scrubbing liquid,
solvent mixtures more complex separation techniques
Operating cost factors are:

solvent absorption efficiency scrubbing liquid recirculation rate, and hence, pumping
requirements,
solvent loading rate of desorption and subsequent utility requirements, such as steam,
scrubbing liquid degradation high purge rate of spent liquid, and hence, high treatment
and/or disposal costs,
ease of solvent desorption temperature for desorption,
techniques.
Provided sufficient space is available, absorption systems can be relatively easily retro-fitted to
existing plants. Retro-fits of existing absorption systems with improved structured packings
and/or liquids can also be carried out to improve the operation of recovery equipment.
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Chapter 3
A programmable logic controller system is typically used to manage the operation of the plant
automatically. A program is available which can predict the optimum operating parameters, i.e.
circulation and steam requirement, for a given composition of the air stream. This is particularly
useful where changes in the airflow and/or the solvent concentration are likely to be significant.
Action by plant operators is minimal, provided that automatic shut-down is fitted and alarms set
up on the control system, e.g. for low liquid flow or loss of vacuum.
Maintenance requirements are likely to be low. They are mainly limited to routine checks on the
desorber vacuum system and equipment with moving parts. [cww/tm/71]
3.5.2 Abatement Operations and Processes for VOCs and Inorganic

Gases
The terms VOCs and inorganic gases comprise organic solvents and inorganic compounds
such as hydrogen halides, halides, ammonia, carbon monoxide, cyanides or their mixtures with
air. They are found in any of the gaseous discharges from production processes, storage and
handling processes, e.g. loading and unloading. The usual treatment systems are described
below. It is not thought helpful to categorise the treatment techniques as, e.g. techniques for
inorganic compounds and organic compounds, since in reality these two kinds of pollutants are
often found together, and/or the treatment systems are applicable to both.
3.5.2.1 Biofiltration
Principle
The waste gas stream is passed through a bed of peat, heather or compost where it is
biologically degraded by naturally occurring micro-organisms into carbon dioxide and water.
A Biofilter is shown in Figure 3.39 [cww/tm/79].
Figure 3.39: Biofilter Construction
Application
Biofiltration is used in the chemical and petrochemical industry as well as in sewage treatment
plants. It is an abatement technique that removes readily biodegradable components, such as
ammonia, amines, hydrocarbons, hydrogen sulphid, toluene, styrene and odorous contaminants.
Biofiltration is preferably applicable to low concentrations of pollutants easily soluble in water.
170
waste gas flow:

temperature:
100 400 Nm3/h per m2 of filter surface [cww/tm/64],

15 40 C,
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pressure:
hydrocarbon concentration:
odour concentration:
toluene concentration:
styrene concentration:
atmospheric,
200 1000 mg/Nm3,
20000 200000 ou/Nm3,
20 100 mg/Nm3,
50 500 mg/Nm3.
Compounds that contain nitrogen, sulphur or chlorine in concentrations higher than 10 20

mg/Nm3 can acidify and deactivate the biofilter, which brings about an increase of the
replacement frequency of the filter material.

Biofilters can be divided into:
soil-based biofilters,
non soil-based biofilters.
A soil-based biofilter consists of a layer of porous soil underlain by a network of pipes through
which the contaminated air is blown to the filter. Soil filters require a long residence time and
therefore tend to be large. They might be used for low gas rates.
A non soil-based biofilter consists of a layer of material, supporting a suitable microbial
population and placed above a distribution system which supplies the contaminated waste gas
stream to the filter uniformly. The gas stream is fed to the filter by electric fans.
The micro-organisms are enclosed in a fixed bed consisting of moist carriers, such as e.g.
compost or peat. The height of the filter material is between 0.5 and 2.5 m, with a maximum of
two to three layers. The specific load of the filter bed is between 100 and 400 Nm3/h per m2 of
filter surface [cww/tm/64]. The moisture balance is usually very critical (relative moisture of
about 95 % and more is required). It is regulated by moistening the filter material in
combination with a pre-connected humidifier or gas scrubber. In some cases the moisture
balance is monitored by on-line weighing of the filter material.
For application to warm waste gas streams (> 35 C) cooling is necessary, either by mixing with
air or introducing a gas scrubber or heat exchanger.
The residence time to allow an effective abatement of, e.g., odour depends on the pollutant
concentration. As a rough guide, a minimum residence time of 30 to 45 seconds should be
aimed for.
A typical biofilter process is shown in Figure 3.40 [cww/tm/64].
Advantages
Simple construction.
Disadvantages
Dried out filter beds are difficult to re-wet.
Biodegradation to carbon dioxide and water.
Relatively bulky design.
In combination with adsorption and absorption

also suitable for barely soluble components.
Poisoning and acidification of the biomass

must be avoided.
Fluctuations in the gas stream have a great
impact on performance.
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Chapter 3
Figure 3.40: Typical Biofilter Process

A degradation of 75 95 % is achievable.
Hydrocarbons:
Odour:
Toluene:
Styrene:
75 95 % (> 5 mg/Nm3)
75 95 % (> 5000 ou/Nm3)
80 95 % (> 5 mg/Nm3)
80 90 % (> 10 mg/Nm3)
Input is the filter material (root wood, bark, peat, compost or a mixtures of some or all of these)
and water to keep the necessary moisture level. The service life of the filter material depends on
its stress by acidification, poisoning and/or depletion.
Electric energy is needed for fan(s) and pumps.
The energy consumption is not known
The pressure drop is 5 20 mbar (excluding the gas ducts)
The filter material has to be disposed of from time to time. Since not all VOCs sent through the
biofilter are biodegradable, there might be loaded filter material containing hazardous
contaminants that has to be disposed of as waste (incineration). The percolate water that is
released from the filter material may contain organic residues and has to be disposed of.
Monitoring
The moisture balance has to be carefully examined because it is a critical item for the accurate
operation of biofilters.
The efficiency may be determined by assessing the inlet and outlet gases, the appropriate
method depending on the pollutants to abate.
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Costs
The investment costs are approximately k 5 20/1000 Nm3/h
labour costs:
utilities:
total costs:
1 employee-hour per week per filter and 2 employee-days per

year
5 l water per 1000 Nm3
200 per m3 of filter material (service life 0.5 5 years)
not known
Cost relevant parameters are the waste gas flow rate, the pollutant concentration in the gas
stream, the type of component in the gas stream and the required efficiency. There are no
revenues.
Operation and maintenance costs are low, because no fuel or chemicals are needed.
3.5.2.2 Bioscrubbing
Bioscrubbing combines gas absorption and biodegradation with the scrubbing water containing
a population of microbes suitable to oxidise the noxious gas components.
Application
Bioscrubbing is used in chemical and petrochemical industry as well as in sewage treatment
plants. It is an abatement technique that removes readily biodegradable components, such as
ammonia, amines, hydrocarbons, hydrogen sulphide, toluene, styrene and odorous
contaminants. Bioscrubbing is rather applicable to low concentrations of pollutants easily
soluble in water.
waste gas flow:

temperature:
pressure:
VOC concentration:
odour concentration:
ammonia concentration:
1000 3000 Nm3/h per m2 of column surface [cww/tm/64],

15 40 C,
atmospheric,
100 1000 mg/Nm3,
> 20000 ou/Nm3,
50 200 mg/Nm3.

The bioreactor design is founded on an activated sludge or a sludge-on-carrier system. The
water sludge mixture is recirculated into the reactor. The absorbed pollutants are degraded in
aerated sludge tanks. The scrubbing tower should be designed in such a way that a contact time,
depending on the contaminants, of about one second is provided.
Bioscrubbers are frequently inoculated with activated sludge from, e.g. a biological waste water
treatment plant. Depending on the composition of the waste gas the performance of the
bioscrubber will only attain the desired level after some weeks of adaptation. Inoculation with
cultures prepared in fermenters is particularly applied to contaminants that hold sulphur
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Chapter 3
(mercaptans, hydrogen sulphide, dimethyl sulphide, etc.) or chlorine (chlorinated methanes or

ethanes) [cww/tm/70].
A typical bioscrubber process is shown in Figure 3.41 [cww/tm/64].
Figure 3.41: Typical Bioscrubbing Process
Advantages
Biodegradation produces only (at least
theoretically) carbon dioxide and water.
Disadvantages
Biomass can build up, resulting in blockage of
the circulating water.
High concentrations can be abated owing to

high microbial conversion.
Poorly soluble components are more difficult

to abate.
Also suitable for high concentrations of

compounds containing sulphur, chlorine,
and/or nitrogen.
Poisoning of the biomass must be avoided.

Fluctuations, e.g. changing concentrations, in
the gas stream have a great impact on
performance.
Environmental Performance and Impact [cww/tm/70]

An average degradation of 80 95 % is achievable.
VOC:
Odour:
Ammonia:
80 90 %
70 80 %
80 95 %
Input are:
174
low doses of nutrients, such as phosphorous, potassium and trace-elements,

water in proportion to discharge and evaporation,
chemicals to amend acidification, e.g. caustic soda for pH adjustment,
electric energy for fans and pumps.
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The energy consumption is not known

The pressure drop is 2 5 mbar.
Because of biological activities in the bioscrubber, the salt concentration in the circulation water
increases and thus has to be discharged from time to time. This waste water effluent has to be
treated or disposed of in some other way.
Surplus activated sludge has to be disposed of, dependent on the contaminants or degradation
products, e.g. by incineration.
Occasionally odour might arise from the tanks storing the circulation water, so collection of
exhaust air and its subsequent ducting to a treatment facility might be obligatory.
Monitoring
Efficiency may be determined by chemical analysis or assessing the odour of inlet and outlet
gases.
Costs
labour costs:
utilities:
total costs:
day per week (variable)

not known
no information
not known
Cost relevant parameter is the waste gas flow rate. There are no revenues.
3.5.2.3 Catalytic Filtration
Principle
Catalytic filtration is the elimination of gaseous components accompanied by particulate
separation. It is comparable to the operation of fabric filters (see Chapter 3.5.3.5). The
distinction is between the filter materials, the catalytic filter being loaded with a catalyst
(titanium/vanadium system) that destroys pollutants by catalytical gas reaction. The separated
dust will be removed and disposed of separately. An example of catalytic filtration is illustrated
in Figure 3.42 [cww/tm/85].
Application
Catalytic filtration is used to separate particulates and eliminate hazardous contaminants from
the gaseous phase. The chief contaminants this technology is applied to are dioxins and furans
(PCDD and PCDF). But other contaminants such as polyaromatic hydrocarbons (PAH),
polychlorinated benzenes (PCB), VOCs and chlorinated phenols (PCP) can be eliminated as
well.
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Chapter 3
temperature range:
ammonia content:
sulphur oxides content:
moisture content:
filtration velocity:
180 260 C,
< 200 ppm,
< 50 ppm,
5 35 %,
48 84 m/h (48 84 m3/h gas per m2 membrane surface)
[information provided by GORE],
deactivation by arsenium, potassium, calcium, sulphur
Figure 3.42: Schematic Overview of a Catalyst Filter System
The temperature range is determined by the filter medium (260 C) and by condensation of
moisture or VOC (180 C), though temperatures down to 140 C have been successfully
operated [information provided by GORE]. Condensation of flue gas causes the catalyst to
drown, i.e. it will be saturated.

The catalyst filter consists of an expanded polytetrafluoroethen (ePTFE) membrane, laminated
to a catalytic felt substrate, the catalyst inserted in the needle felt. It is composed as modules in
a baghouse, shown in Figure 3.43 [cww/tm/85], in a way that it can be easily fitted to an
existing plant. The module construction enables an easy implementation into existing gas
streams for test purposes. The dust is separated via dust hopper.
Advantages
Destruction of hazardous gaseous compounds
without residues.
Disadvantages
Restricted to a temperature range between
180 - 260 C, possibly down to 140 C.
Operation with various contaminants possible.
No wet or sticky dusts as input.
Easily retro-fittable.
Catalyst can be de-activated by catalyst

poisons such as ammonia, sulphur, arsenium.
Catalyst more than 10 years active.

Dust contains dioxins and furans.
Lower operation costs.
No waste except separated dust to be disposed
of.
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Chapter 3
clean gas
bag house cleaning frequency
between 10 min. and 24 hours
particle
filter
raw gas
180 - 250C
< 120C
sampling train
gas phase
collector
particle
filter
< 120C
pump
sampling train
sampling time
3 hours
gas phase
collector
sampling time
0,25 - 3 hours
depending on
dust load
hopper
dust
pump
Figure 3.43: Catalytic Filter Baghouse, including Sampling Trains

Achievable values are [information provided by GORE]:
dioxin removal efficiency:
dust removal:
98.5 99.5 %
0.006 0.072 ng TEQ/Nm3
measurements at waste incinerators, crematories
0.3 4 mg/Nm3
The separated dust possibly mixed with precoat material is the only residue. The quantity
depends on the dust content of the gas to be treated and of its temperature (gas streams at higher
temperatures contain less particulates). The filtered dust is normally contaminated with dioxins
and furans and will be classified as hazardous waste, which has to be disposed of.
Performance and maintenance have to be monitored carefully. The mass emission to assess the
performance of the filter can be determined by monitoring the particulate concentration in the
effluent waste gas stream, using an isokinetic sampling probe or a meter based on, e.g.
UV/visible opacity, beta rays or particle impingement. The monitoring of dioxins is normally
carried out when there is reason to investigate (and doubt) the catalyst performance, because the
analytic procedure is very complex and cost intensive.
Temperature and pressure drop across the bag filter need to be routinely monitored. The latter is
used to indicate if it is necessary to begin the cleaning cycle. Bag filters should be inspected
regularly to identify any deterioration in the filter housing or filters. Hence access to the filter
should be available.
Costs
According to operational experience, the working life of the filter material and catalyst is longer
than 10 years.
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Chapter 3
The investment costs are M$ 1.0 for a waste incineration plant of a capacity of about 60000
tonnes/year.
labour costs:
utilities:
total costs:
not known
not known
not known
not known
3.5.2.4 Thermal Incineration
Thermal incineration is the oxidation process of combustible gases and odorants in a waste gas
stream, by heating a mixture of contaminants with air or oxygen at high temperatures in a
furnace. Under conditions of complete combustion, the end products are carbon dioxide, water
and nitrogen oxides. If the contaminants or the fuel contain sulphur and/or halides, sulphur
dioxide and/or hydrogen halides will also be there.
Application
Thermal incineration, as an appropriate abatement technique to control VOCs and odours, is
widely utilised in several industry sectors where these pollutants are frequently present. The
incineration of chlorine compounds usually demands distinct conditions in specifically designed
facilities.
waste gas flow:

combustion temperature:
residence time in combustion chamber:

VOC concentration:
1000 30000 Nm3/h [cww/tm/64],

800 1200 C (not applicable to organic
halides) [cww/tm/64],
0.3 2 seconds [cww/tm/64],
> 1 2 g/Nm3 (taking into consideration the
lower explosive limit).

Fundamental requirements for the total oxidation of VOCs and odorants are:
contact of the contaminants with sufficient oxygen for a long enough time at a high enough
temperature (about 200 400 C above the auto ignition temperature of the gaseous/volatile
compounds),
suppressing de-novo synthesis of dioxins/furans (when halogenated VOCs are present).
Recommended conditions are:
- residence time > 1.5 s
- temperature > 850 C
- oxygen content > 3 %
- quenching of flue gas after incinerator to rush through the recombination window
of dioxins
a sufficient degree of turbulence to ensure thorough mixing,
a special design that ensures these conditions.
To achieve these goals three basic types of incinerators are generally used, which are illustrated
in Figure 3.44 [cww/tm/79]:
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line burner,
tunnel incinerator,
jet incinerator.
Figure 3.44: Basic Types of Incineration Equipment
The design criteria for an incineration system depend mainly on the nature of the waste gas
stream, which determines the combustion conditions. Some of the most important items are:
The burners
Some important types of burners are described in Table 3.14 [cww/tm/79].
Burner
Characteristics
Distributed Burner
gives much better mixing of the fuel and combustion air and of hot
gases with the bypass air. This produces short flames and thus allows
a greater residence time. However, only clean gases and gaseous fuels
can be used. There is limited turndown (ratio between full and
minimum output) and combustion air with a high oxygen content may
be required.
Single Source Burner
is less expensive than distributed burners.
Premix Burner
provides efficient combustion, but can only take gaseous fuel and
clean air.
Diffusion Burner
can take liquid or gaseous fuel and clean or dirty air.
Vortex Burner
provides efficient combustion and a short flame, but a fan capable of

delivering 500 mm water gauge is needed, there is low turndown and
liability to fouling.
Oil Burner
gives longer flames, is more expensive, requires more maintenance,

has more limited turndown and is generally not as clean as a gas
burner.
Table 3.14: Types of Burner
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Chapter 3
The mixing section [cww/tm/79]

Good mixing can be achieved by:
- natural diffusion between turbulent streams,
- impingement of gas streams at an angle,
- changes in direction of flow, round corners or past baffles.
The combustion chamber [cww/tm/79]

Conditions for dimensioning the combustion chamber are:
- its diameter must allow turbulent flow,
- it has to be large enough to take the flame without quenching,
- its length is determined by the length of the flame plus the length needed to achieve
mixing,
- it must be resistant to temperature and corrosion,
- it must withstand frequent expansion and contraction.
Waste gas pre-treatment [cww/tm/79]

Pre-treatment necessary before entering the incinerator:
- condensing out water vapour from a wet waste gas,
- removal of solid and liquid contaminants,
- pre-heating, which reduces fuel requirements.
Heat recovery [cww/tm/79]

In the recuperative system, the effluent gas stream from the incinerator passes through a
heat exchanger, which allows heat to be transferred continuously in order to pre-heat the
incoming gas stream. This system is particularly suitable for waste gas streams of
comparatively low flow rates (< 14 Nm3/s) containing high levels of VOCs and/or odorants.
50 80 % heat recovery is generally achieved.
The regenerative system uses two sets of ceramic bed heat exchangers. One is heated by
direct contact with the exhaust gas while the other is used to pre-heat the incoming gases.
The system is operated in a way that the beds alternate between heating and cooling. This
system is particularly suitable for waste gas streams of comparatively high flow rate (up to
200 Nm3/s) containing low levels of VOCs and/or odorants. 80 95 % heat recovery is
generally achieved.
Safety equipment [cww/tm/79]

Necessary safety devices are:
- protection against flame flashback by devices, e.g. parallel plate flame arrestors,
multiple screen flame arrestors, and/or water seals,
- burner purge period on start up of the incinerator,
- shut off flows in the event of flame failure,
- limiting of peak temperatures.
Typical incineration processes are shown in Figure 3.45 and Figure 3.46 [cww/tm/64].
Figure 3.45: Thermal Incineration with Pre-heating Stage
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Figure 3.46: Thermal Incineration with Steam Generation
Advantages
High and constant performance possible.
Disadvantages
Emission of carbon dioxide and nitrogen
oxides.
Simple principle.
Risk of dioxin formation.
Reliable in operation.
Recuperative and regenerative incineration
have a high thermal efficiency, with the effect
of lower extra fuel consumption and lower
carbon dioxide emission.
Flue gas treatment necessary for VOCs

containing sulphur and/or halides.
Process integration of residual heat or steam

generation is possible.
The reaction temperature has to be kept low enough to minimise NOx formation but high
enough to achieve total combustion.

An average degradation of VOCs from 95 99 % is achievable.
Input are:
fuel, e.g. natural gas or oil, during start-up and under non-autothermal conditions. The
autothermal point for VOCs is in the range between 6 10 g/Nm3.
water, when vapour generation is combined with incineration.
electric energy for fans.
The energy consumption
no information
The pressure drop is 10 50 mbar

The emissions to the environment include carbon dioxide, traces of carbon monoxide, water and
nitrogen oxides.
When the incinerated VOCs contain sulphur and/or halides, further emissions of sulphur
dioxide and/or hydrogen halides are expected. These should be abated with suitable techniques.
When chlorinated VOCs are incinerated, the formation of dioxins can normally be expected. If
special precautions are not taken during the incineration process to exclude with certainty the
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combination/re-combination of dioxins and furans, the effluent gas stream has to go through a
special treatment.
The impact of the expelled heat and steam effluent have to be taken into account.
The combustion temperature, the level of carbon monoxide and the oxygen content of the
effluent gas stream should be monitored to control the combustion conditions.
VOC and/or odour before and after the incinerator. VOCs can be measured as total carbon,
using a flame ionisation detector. A qualitative analysis of the emissions can be done by taking
grab samples at selected sampling points and by subsequently analysing them by GC/MS.
Abatement efficiencies for odorous emissions are determined by taking grab samples at an
appropriate sampling point and subsequently analysing them by olfactometry.
Burners have to be inspected regularly and, if necessary, cleaned. If deposits build up rapidly,
preventive action needs to be taken. Effective pre-treatment may be necessary to clean the
contaminated waste gas before it enters the burner. If the deposits are due to carbon this may
indicate the use of the wrong waste gas/fuel ratio and the need to check the setting of controls.
Costs [cww/tm/70]
k 10 50/1000 Nm3/h (recuperative)
k 20 30/1000 Nm3/h (regenerative)
labour costs:
utilities:
total costs:
day per week

not known
no information
not known
Cost saving parameter is the autothermal point of the VOC content. A possible revenue is the
heat recovery.
Capital costs depend on a number of factors [cww/tm/80], e.g.:
volume of waste gases to be treated dimensions of combustion chamber,

heat content of the waste gas design of combustion equipment, auxiliary fuel
requirements,
combustion temperature materials of construction,
instrumentation,
heat recovery options,
installation requirements (indoor, outdoor, ground level, rooftop, etc.).
Kilns and boilers can be used for the incineration of VOCs, if temperature and residence time
are in the correct range. This can be an attractive option where the kiln or boiler is already on
site.
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3.5.2.5 Catalytic Incineration
Principle
Catalytic incineration is the oxidation of combustible gases and odorants, by heating a mixture
of contaminated gas and air or oxygen in the presence of a catalyst surface. Total combustion
can be achieved at remarkably lower temperatures than with thermal incineration. A typical
operational temperature range is 200 500 C [cww/tm/64]. In the case of total combustion, the
final products are carbon dioxide, water and nitrogen oxides. If the contaminants or the fuel
contain sulphur and/or halides, sulphur dioxide and/or hydrogen halides will be present as well.
Application
Catalytic incineration as an appropriate abatement technique to control VOCs and odours is
widely applied in a number of industry sectors where these pollutants are frequently present.
waste gas flow:

residence time:
catalyst loading:
VOC concentration:
100 20000 Nm3/h [cww/tm/64],

200 500 C [cww/tm/64],
0.3 0.5 seconds,
2000 20000 Nm3/h waste gas per m3 catalyst [cww/tm/64],
> 1 2 g/Nm3 (taking care of lower explosive limit)

The basic components of a catalytic incinerator are shown in Figure 3.47 [cww/tm/79]:
the burner,
the heat exchanger, to pre-heat the waste gas stream,
the catalyst.
Figure 3.47: Catalytic Incinerator
Key issues are:
The catalyst
Typical catalytic materials are:
platinum,
palladium,
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rhodium,
copper chromite,
oxides of copper, chromium, manganese, nickel, cobalt, deposited on support
material.
Operational conditions
- preferred fuel: natural gas,
- most suitable burner: distributed burner,
- chambers should be constructed of stainless steel or carbon steel,
- burner section of sufficient length to provide even flow and temperature distribution
across the catalyst surface,
- flat flow profile across the catalyst face,
- waste gas should move through the catalyst bed in plug flow with minimum
backmixing,
- typcial residence time 0.3 0.5 seconds.
Waste gas pretreatment

Pre-treatment needed before entering the incinerator:
- condensing water vapour from a wet waste gas,
- removal of solid and liquid contaminants,
- pre-heating, which reduces fuel requirements.
Heat recovery
In the recuperative system, the effluent gas stream from the incinerator passes through a
heat exchanger, which allows heat to be transferred continuously to pre-heat the incoming
gas stream. This system is particularly suitable for waste gas streams of comparatively low
flow rates (< 14 Nm3/s) containing high levels of VOCs and/or odorants. 50 80 % heat
recovery is generally achieved.
The regenerative system uses two sets of ceramic bed heat exchangers. One is heated by
direct contact with the exhaust gas while the other is used to pre-heat the incoming gases.
The system is operated in a way that the beds alternate between heating and cooling. This
system is particularly suitable for waste gas streams of comparatively high flow rate (up to
200 Nm3/s) containing low levels of VOCs and/or odorants. 80 95 % heat recovery is
generally achieved.
Safety equipment
Necessary safety devices are:
- protection against flame flashback by devices, e.g. parallel plate flame arrestors,
multiple screenflame arrestors, and/or water seals,
- burner purge period on start up of the incinerator,
- shut off flows in event of flame failure,
- limiting of peak temperatures.
The catalytic incinerator should be designed to facilitate the removal of the catalyst for cleaning
or replacement purposes.
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Advantages
More compact than thermal incinerators.
Disadvantages
oxides.
Requiring lower temperatures and less fuel

than thermal incinerators.
Little or no NOx produced from atmospheric

fixation.
All catalysts susceptible to poisoning agents,

fouling agents and activity suppressants.

Simple principle.
Recuperative and regenerative incineration
have a high thermal efficiency, with the effect
of lower extra fuel consumption and lower
carbon dioxide emission.
Process integration of residual heat or steam
generation is possible.
Catalyst poisons are: silicon, arsenic, phosphorous, selenium and their compounds.

An average degradation of VOCs from 95 99 % or < 20 50 mg/Nm3 is achievable.
The degradation of odours is in the range of 80 95 %.
Input are:
fuel, e.g. natural gas or oil, during start-up and under non-autothermal conditions. The
autothermal point for VOCs is in the range of 1 2 g/Nm3.
catalyst,
water, when vapour generation is combined with incineration.
electric energy for fans.
no information
The pressure drop is 10 50 mbar

The emissions to the environment include carbon dioxide, traces of carbon monoxide and water.
The catalyst has a working life of up to two years. It then has to be regenerated or disposed of as
chemical or even hazardous waste.
When the incinerated VOCs contain sulphur and/or halides, further emissions of sulphur
dioxide and/or hydrogen halides are to be expected. These have to be abated with suitable
techniques.
When chlorinated VOCs are incinerated, the formation of dioxins can normally be expected. If
special precautions are not taken during the incineration process to exclude with certainty the
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combination/re-combination of dioxins and furans, the effluent gas stream has to go through a
special treatment.
The impact of the expelled heat and vapour effluent have to be taken into account.
The bed temperature, pressure drop, combustion temperature and the level of carbon monoxide
and oxygen content of the effluent gas stream should be monitored to control the combustion
conditions.
VOC and/or odour before and behind the incinerator. VOCs can be measured as total carbon,
using a flame ionisation detector. A qualitative analysis of the emissions can be done by taking
grab samples at selected sampling points and by subsequently analysing them by GC/MS.
Abatement efficiencies for odorous emissions are determined by taking grab samples at an
appropriate sampling point and subsequently analysing them by olfactometry.
Burners have to be inspected regularly and, if necessary, cleaned. If deposits build up rapidly,
preventive action needs to be taken. Effective pre-treatment may be necessary to clean the
contaminated waste gas before it enters the burner. If the deposits are due to carbon this may
indicate the use of the wrong waste gas/fuel ratio and the need to check the setting of controls.
Costs [cww/tm/70]
labour costs:
utilities:
total costs:
day per week

not known
no information
not known
Cost relevant parameter is the autothermal point of the VOC content. A possible revenue is the
heat recovery.
3.5.2.6 Flaring
Principle.
Several waste gas streams are collected and ducted to a central flare system. The contaminants
are oxidised at temperatures above 800 C. In contrast to other incineration processes there is no
heat recovery and no flue gas treatment. The final products are carbon dioxide, water, nitrogen
oxides and, if compounds containing chlorine and/or sulphur are present, there is also a
considerable amount of hydrogen chloride and/or sulphur dioxide in the effluent flare gas. The
temperature necessary for flaring is reached either by autothermal incineration or added support
fuel gas.
Application
Flares are used to safely dispose of surplus combustible gases and vapours when there is no
opportunity to use or recycle them. VOCs from vents, pumps and compressors are collected and
routed to a flare system. A significant function of flares is to prevent the unwanted occurrence
of larger amounts of inflammable gases as a safety measure or under emergency conditions.
Technically, all points in a chemical plant with a potential safety release of combustible gases
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are connected to a flare system. Flares are widely used in the oil, gas and petrochemical
industry. They are not, however, regularly used as a continuous measure.
Whereas elevated flares height varying between 20 m and 120 m [cww/tm/84] are normally
used as emergency and relief gas flaring, ground flares are more often employed as routine
flaring provided that the waste gas does not contain sour gas constituents (e.g. hydrogen
sulphide). The advantage of ground flares is their low noise, radiation-free and odourless
operation and low purge gas requirements.
Elevated flares are designed for large capacities (hundreds of tonnes per hour), ground flares for
much smaller amounts (tens of tonnes per hour) [cww/tm/84].
waste gas flow:

up to 1000000 Nm3/h [cww/tm/64],
minimum 800 C [cww/tm/64],
residence time in combustion
chamber (flare equipment):
1 2 seconds [cww/tm/64],
VOC concentration:
0 100 %,
oxygen content after
incineration:
> 5 %,
velocity in the flare fast enough (up to 20 m/s) to prevent backflash.
The installation of flares might be difficult and expensive in a retro-fit situation.

Different kinds of flares are shown in Figure 3.48 3.50 [cww/tm/64].
A key issue for flaring is smoke suppression, which is typically achieved by adding sufficient
air to the flare to ensure that all carbon is converted into carbon dioxide. Air is supplied by
entrainment using a suppressant, via a series of inductors located round the flare tip, or by an air
blower. Suppressants commonly used are:
steam, supplied at up to 7 bar gauge pressure, normally used on large sites where steam is
easily available,
air, suited to applications requiring a small and relatively inexpensive installation,
high-pressure gas, which is very costly,
water, supplied at a water pressure of about 20 bar gauge, suitable where water is freely
available in large quantities.
Industry usually requires a smokeless capacity of 10 15 % for elevated flares and 100 % for
ground flares. The best smokeless capacity is known for substances with low molecular weight
and high chemical bond saturation, i.e. methane is smokeless (high smokeless capacity) and
olefins have the worst smokeless capacity.
The most commonly used flare system is the Flame Front Generator which works by igniting a
waste gas/air mixture within the ignition piping system in a way that a ball of flame travels up
the pipe to ignite the pilot. A proper design of the flame front generator should considered:
the ignition gas/air ratio,

constant composition of ignition gas,
the ignition flame speed,
design of ignition gas pipeline,
weatherproofed system,
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quality of the material,

number of pilots per flare (1 4),
pilot shields against wind, etc.,
quality of the pilot gas,
pilot gas/air mixing,
maintenance of the pilot,
monitoring and operation of the pilot.
Figure 3.48: Injector Rod Flare
Figure 3.49: Shielded Flare
The burners have to be designed to deal with the anticipated quantity of source gas so as to
prevent turbulence and air entrainment. Liquid knock-out pots must be installed upstream of the
burner, which should be equipped with liquid drains to minimise emissions of liquid droplets.
Proper safety devices and operating conditions are a prerequisite as protection against flame
flashback.
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Figure 3.50: Muffle Flare
Advantages
Stand-by equipment for emergency use.
Disadvantages
No pollutant abatement beyond the flare.
Efficient abatement system concerned with

surplus combustible and non-recyclable gases.
Smoke suppressants needed.

Coke formation may cause tip blockage.

Acid gases can cause problems.
Back burning needs to be avoided.
oxides.
Noise is an important issue.
Light nuisance for elevated flares.
High costs in case of retro-fitting

A destruction efficiency of 99.5 % is observed. Since there is no flue gas treatment installed
beyond the flare, the incineration pollutants such as sulphur dioxide, nitrogen oxides, soot and
possibly dioxins leave the flare unabated. For these reasons, ground flares are not suited for
poisonous and hazardous gases. The combination/recombination reaction to dioxins, however,
is not favoured because of the lack of a recombination window and metal surfaces acting as
catalyst.
Input are:
smoke suppressants such as steam, air, water or high-pressure gas (e.g. natural gas),
ignition gas for the ignition pilot (mostly bottled propane or butane),
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purge gas (nitrogen or fuel), to keep the system on overpressure to prevent explosive
mixtures,
pilot gas,
electric energy for fans and pumps
Flaring is connected with the emission of noise. The most significant sources that can be
attributed to noise are [cww/tm/94]:
smoke suppressant injection,

combustion process,
vents.
no information
The pressure drop is
no information
Any steam assisted flare generates noise, due to the high-pressure steam jets and injectors and
the combustion noise associated with hydrocarbons. High-pressure steam generates high
frequency noise and also improves combustion efficiency, thereby increasing energy release and
burning rate, which again results in a higher combustion noise. Combustion noise is typically
low frequency noise, comparable to the vent noise from turbulent mixing of waste gases and air.
High frequency noise is most serious to humans.
The suppression of noise is a crucial environmental issue and thus an important design aspect
that requires concern at an early stage. Noise avoidance aspects are, e.g.:
reduction or attenuation of the high frequency steamjet noise by using multiport steam
injectors, which, on the other hand, can lead to increased coke formation under low-flow
conditions; orifice design for the latter drawback is essential.
siting of the injectors in a way that the jet streams can interact and reduce the mixing noise.
increasing the efficiency of suppressant with better and more responsive forms of control.
restricting steam pressure to < 7 bar.
using a silencer around the steam injector as an acoustic shield for the injectors.
using air blown flares or enclosed ground flares.
Further impacts are:
light nuisance from elevated flares,

odour nuisance because of insufficient combustion (mostly with ground flares).
The flow rate of the smoke suppressant to the flare tip has to be checked to ensure that sufficient
suppressant is introduced, but not more than is required to prevent smoking. This can be
achieved in three different ways:
by an array of thermo-couples rated for at least 1000 C,

by a ground-based infra-red detector,
by metering flare gas flow to the ratio of suppressant flow to flare gas flow. Flow control
usually takes place with control valves or, in the case of air-blown flares, with varying fan
pitch, inlet vane pitch or blower speed.
Rapid response of the control system is essential, preferably by means of electronic

transmission of control signals between the, usually remote, flare stack and the relevant control
room. Installation of TV to monitor the flare in the control room should be considered to allow
a manual intervention of suppressant control if this should be necessary.
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Concerning the pilot, the operational monitoring equipment to apply can be, e.g.:
thermo-couples (careful of erroneous signals),

direct surveillance of the pilot flame (e.g. TV-surveillance),
infra-red monitoring (careful, water absorbs IR), sometimes modified with optical
monitoring to surmount the IR-absorption of water,
luminosity measurement,
ionisation probes,
low-pressure alarm,
flow control of the purge gas.
Costs
The investment costs are approximately M 1.3 for a 5.0 Mtonne/year refinery [cww/tm/48]
labour costs:
utilities:
total costs:
not known
not known
no information
M 3.0/year [cww/tm/48]
3.5.3 Abatement Technology for Particulates

Particulate pollutants are dust, heavy metals and their compounds, aerosols, mist and soot,
which can frequently be found in waste gas streams, flue gas streams and exhaust air streams in
the chemical industry. Dust particles and heavy metals (and/or compounds) are found in
production waste gas streams, when solids and powdery compounds are handled, formed and/or
stored, as well as in the flue gas or exhaust air streams of combustion sites, e.g. power plants or
waste incineration. Aerosols and mist appear, e.g., during reaction and work-up of production
mixtures. The common treatment systems are described below. Waste gas treatment of
particulate pollutants is usually an abatement operation. Recycling or re-use of particulates is
not the rule.
3.5.3.1 Separator
Principle
The waste gas stream is passed into a chamber where the dust, aerosols and/or droplets are
separated from the gas under the influence of gravity/mass inertia. The separation process is
supported by baffles, lamellae or metal gauze. An example is given in Figure 3.51 [cww/tm/70].
Application
A separator is usually not installed as an individual technique but as a preliminary step to
various dust filter systems, scrubbers, cooling towers etc. It is used, e.g., to prevent entrainment
of the washing liquid with the purified waste gas.
waste gas flow:

dust content:
droplets:
100 100000 Nm3/h,

no restriction,
no restriction.
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Figure 3.51: Separator

The design should ensure a good uniform speed distribution inside of the vessel. Preferential
flows have an adverse effect on efficiency. The employment of internal obstructions in the
inertia separator enables operation at higher speeds, which represents a reduction in volume of
the separator compared with the settling chamber. The drawback is the increasing pressure drop.
Advantages
No moving parts.
Disadvantages
Low removal efficiency.
Very low-pressure drop.
Not suitable when the density difference

between gas and particulates is small.
Suitable for high temperature (> 1000 C)

The feasible removal rate for contaminants is:
dust:
droplets:
10 - 90 %
approximately 100 mg/Nm3
Consumables and utilities are:
separators usually do not make use of consumables.

cleaning system for the baffles or the lamellae of inertia separators (demisters) require an
amount of water of about 100 200 l/m2 surface.
There is no energy consumption, except for the fan.

The pressure drop is < 5 mbar.
Residues are the separated dust and/or the separated droplets. As contaminated liquid or sludge
they have to undergo waste water treatment or are incinerated.
Depending on its source, the separated dust might be contaminated e.g. dust originating from
incineration might contain dioxins and/or heavy metals and their oxides. This type of dust might
be classified as hazardous waste that has to be disposed of accordingly.
Costs
The investment costs are low, and since the separator is usually integrated in other systems, a
useful figure cannot be given.
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labour costs:
utilities:
total costs:
none
none
depends on dust content and type for disposal costs
depends on dust content and type for disposal costs
Cost relevant parameters are the pressure drop and disposal of separated dust. There are no
revenues.
3.5.3.2 Cyclone
Principle
The cyclone is an inertial gas-cleaning device making use of centripetal forces for the separation
process.
Wet cyclones introduce water into the waste gas stream to increase the weight of the particulate
material. By means of this technique also fine material can be removed and the efficiency can
be increased.
Application
Cyclones are widely used and particularly suitable to collect particles of >10 m diameter.
Efficiencies of >80 % are achievable. They are frequently upstream of more expensive
technologies in the gas cleaning line in order to remove coarse material and hence reduce the
dust burden entering the chief abatement equipment or to prevent damage by coarse particles.
waste gas flow:

100 - 100000 Nm3/h,
dust content:
up to a few kg/Nm3 [cww/tm/64],
maximum operational temperature: 540 C.
The efficiency of particle collection by means of a cyclone decreases with temperature, due to
increased gas viscosity. A dust collected with 75 % efficiency at 100 C will be collected with
50 % efficiency at about 300 C.

There are two types of cyclones, the reverse flow and the straight through cyclone.
The Reverse Flow Cyclone (Figure 3.52 [cww/tm/79]), which is the most common, consists of:
a cylindrical shell with conical base,

a dust collection hopper,
an air inlet, either tangential or axial, and outlets.
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Figure 3.52: Reverse Flow Cyclone
The waste gas stream is channelled into a vortex, where centripetal forces sustain the circular
motion. The airflow carries the dust to the collection hopper. At the base of the cone the gas
flow reverses and clean gas passes back along the centre of the cyclone.
The Straight Through Cyclone (Figure 3.52 [cww/tm/79]) is equipped with fixed or moving
impellers. The inlet gas stream is channelled into a spiral. Inertia causes particles above the
critical size to travel in an expanding helix. As a result, the clean gas concentrates along the
centre axis of the cyclone and dirty gas concentrates near the wall.
Figure 3.53: Straight through Cyclone
Advantages
Disadvantages
Unsuitable for fine material and low
concentrations.
Recovery of raw material.

No moving parts.
Axial entry cyclones cannot be used with dusts

which are likely to cause excessive erosion or
clogging of the vanes in the inlet.
Several dusts become tacky as they cool.
Dust explosion is possible.
Noise.
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Dust removal up to 95 % is achievable, depending on the particle size.
Input are:
water in wet cyclones, the amount dependent on the gas temperature.

The energy consumption is 0.25 1.5 kWh/1000 Nm3/h, the electric energy for the fan is
included [cww/tm/70].
The pressure drop is up to 15 mbar [cww/tm/70].
Dust is emitted as residue and has to be disposed of. The amount depends on the dust load of
the waste gas. Depending on its source, the separated dust can be contaminated e.g. dust
originating from incineration might contain dioxins and/or heavy metals and their oxides. This
type of dust might be classified as hazardous waste that has to be disposed of accordingly.
A mass emission to assess the performance of a cyclone can be determined by monitoring the
particulate concentration in the effluent gas stream, using an isokinetic sampling probe or a
meter based on, e.g., UV/visible opacity, beta rays or particle impingement.
Maintenance requirements for cyclones are low there should be easy access to enable periodic
inspection of the cyclone for erosion or corrosion. The pressure drop across the cyclone is
routinely monitored and the dust handling system is checked for blockages.
Costs [cww/tm/70]
The investment costs are 900/1000 Nm3/h
labour costs:
utilities:
total costs:
approximately 200/year
Cost-relevant parameters are the waste gas flow and the pressure drop. Revenue is the removed
material.
3.5.3.3 Electrostatic Precipitator
The electrostatic precipitor (ESP) consists of a series of high voltage electrodes and
corresponding collector electrodes. Particles are charged and subsequently separated from the
gas stream under the influence of the electric fields generated between the electrodes. ESPs are
used to remove the small fraction of particulates.
ESPs work as Single or Two Stage ESPs.
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Application
The single stage ESP is used in large complex flue gas treatment systems, e.g. in power stations
and waste incinerations as a dust and fly ash abatement. As part of the dust, heavy metals and
their compounds are eliminated as well and disposed of together with the other particulates. It is
also suitable for separating aerosols and mists.
waste gas flow:

temperature:
pressure:
dust content:
corona power:
no restrictions [cww/tm/64],
< 500 C,
atmospheric,
< 100 g/Nm3 [cww/tm/64],
100 1000 W per Nm3/s.
The two-stage ESP is applied to remove dust and oil mists. It is an alternative to surface
filtration (HEPA-filter). The two stage ESP is common where small waste gas streams
(< 25 Nm3/s) and a high proportion of submicron particles, e.g. smoke or oil mist, are involved.

There are three types of ESPs:
plate/wire ESP, the most common type of electrostatic precipitators, suitable for high gas
flows, an example shown in Figure 3.54 [cww/tm/79],
flat plate ESP, used with low gas flows between 50 100 Nm3/s, containing particles of low
mass median diameter and high resistivity,
tubular ESP, tend to be wet and are used with wet and/or sticky particles, an example shown
in Figure 3.55 [cww/tm/79].
Figure 3.54: Plate-wire Electrostatic Precipitator
In single stage ESPs the electric field used to generate the corona discharge is also employed to
attract and hence remove the charged particles, with charging and discharging taking place in
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one appliance. In a two stage ESP, charging and removal of the particles occur in separate
electric fields, the second one being purely electrostatic.
Figure 3.55: Tubular Electrostatic Precipitator
The principal difference between single and two-stage ESP is illustrated in Figure 3.56
[cww/tm/79].
Figure 3.56: Schematic Diagram of Single Stage and Two-Stage ESP
Wet ESPs use water as intermittent or continuous flow to wash the electrodes. For wet
ESPs, re-entrainment of dust into the clean waste gas stream is not a problem. Disposal and
handling of the effluent sludge is, however, more expensive than for a dry waste material.
The basis for the ESP design is the gas flow rate and the gas speed in the filter (0.6 - 1 m/s).
ESPs occupy a lot of space with large gas volumes. Temperature and humidity affect
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significantly the resistivity of the particles. So moisture might be used to reduce the resistivity
and thus enable the collection of high resistivity particles.
Systems with elevated risks, such as explosion and fire, must be equipped with safety devices,
such as explosion hatch, sprinkler system etc.
Advantages
Separation of very small fractions is possible.
Disadvantages
Explosion risk is a vital issue.
Low-pressure drop.
The separation capacity depends on the

resistivity of dust particles.
Suitable for wet and dry matter.

Re-entrainment can be a problem due to high
gas velocities, poor rapping or poor gas flow.
Suitable for liquids, aerosols, mists
With wet cleaning, corrosion can occur in the

presence of acid components in the gas stream.
Sensitive to maintenance of the correct
geometrical alignment.

Dust emissions vary in a range between 5 75 mg/Nm3, depending on the resistivity of the
particles. Also aerosols and mists are eliminated.
Input are:
electric energy for the electric field, fans.

rinsing water for wet ESPs, which can be recycled.
The energy consumption is approximately 0.5 - 2 kWh/1000 Nm3/h [cww/tm/64].

The pressure drop is 0.5 3 mbar [cww/tm/70].
With dry ESPs, the separated dust is emitted as residue, with wet ESPs the separated dust
merges with the rinsing water, both being treated as waste water.
Depending on its source, the separated dust can be contaminated e.g. dust originating from
A mass emission to assess the performance of an ESP can be determined by monitoring the
particulate concentration in the effluent gas stream, using an isokinetic sampling probe or
meters based on, e.g. UV/visible opacity, beta rays or particle impingement. The current and
voltage across the electrostatic precipitator, the rapping rate and the temperature need to be
routinely monitored. The dust outlet from the collection hopper has to be maintained free of
blockages so that the hopper does not become overfilled and thus causing short circuiting of the
electrostatic precipitator.
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ESPs need to be regularly inspected to detect any deterioration, e.g. corrosion, of the electrodes,
insulating materials or rapping system. Hence, access to the precipitator needs to be free of
obstruction, but within safety standards.
Costs [cww/tm/70]
The investment costs are approximately k 14/1000 Nm3/h (based on 100000 Nm3/h), scale-up
factor to power of 0.6. In case of the two step ESP they are 600 - 900/1000 Nm3/h
labour costs:
utilities:
total costs:
Two stage ESP:
k 1.5/year (estimated on 1 hour per week), k 2.5/year for the

two stage ESP
approximately 100/year per 1000 Nm3/h
none
1.5 + 0.1 x flow/1000 k/year
2.5 + 0.1 x flow/1000 k/year
Cost relevant parameters are flow rate of the waste gas stream, the dust concentration and the
efficiency. There are no revenues.
3.5.3.4 Dust Scrubber
Dust scrubbing is applied to remove particulates from a gas stream by contact with a liquid,
usually water.
Application
Dust scrubbing is mainly applied to remove dust, but gaseous contaminants such as hydrogen
halides are regularly removed simultaneously.
waste gas flow:

temperature:
pressure:
dust content:
hydrogen chloride:
hydrogen fluoride:
relative humidity
up to 200000 Nm3/h,
< 150 C,
atmospheric,
< 100 g/Nm3 [cww/tm/64],
a few mg/Nm3,
a few mg/Nm3,
> 60 %.
With temperatures above 150 C, the waste gas stream should be quenched first.

Different types of dust scrubbers are operated, e.g.:
Fibrous Packing Scrubber

The fibrous packing scrubber consists of a chamber with gas inlet and outlet, containing
mats of fibrous packing material, which are sprayed with liquid. They are typically applied
to remove soluble particles, mist, gas and gaseous contaminants.
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Fibrous packing scrubbers are not suitable to collect insoluble particles, because these cause
clogging of the fibre bed.
Impingement and Entrainment Scrubbers

Impingement-entrainment scrubbers contain a mechanism to accelerate the inlet gas stream
towards a liquid surface and an entrainment separator. They are generally not suitable for
mass transfer applications, e.g. trace gas removal, but to handle high or low gas streams and
operate at lower pressure drops than venturi scrubbers.
An example is given in Figure 3.57 [cww/tm/79].
Figure 3.57: Impingement Entrainment Scrubber
Moving Bed Scrubbers

Moving bed scrubbers contain zones of mobile packing material placed on support grids,
where gas and scrubbing liquid can mix, and a mist eliminator. An example is given in
Figure 3.34 [cww/tm/79].
Bed scaling, nozzle plugging and packing deterioration can cause problems.
Plate Scrubbers
Plate scrubbers consist of a vertical tower with several horizontal perforated (sieve) trays
stacked in it. Baffles are situated at a short distance above the apertures in the plates. Gas
and liquid are operated in counter-flow. An example is given in Figure 3.36 [cww/tm/79].
Problems encountered with this technology are scaling and plugging.
Spray Towers
Spray towers (or spray scrubbers) consist of spray nozzles at the top of the tower, through
which the scrubbing liquid enters, and a gas inlet near the bottom. They are typically
applied to remove particulates and trace gases. An example is given in Figure 3.37
[cww/tm/79].
Problems encountered with this technology are plugging and corrosion on the liquid side.
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Venturi Scrubbers
The characteristic feature of a venturi scrubber is the constriction to the duct venturi throat
causing an increase in gas velocity. Liquid is introduced to the scrubber and forms a film
on the walls, which is atomised by the gas stream in the venturi throat. Alternatively, with
ejector venturi scrubbers, the liquid is sprayed into the venturi throat. Venturi scrubbers are
highly efficient particle scrubbing devices, because they are suitable down to submicron
particles. They can also be utilised to remove trace gases, particularly reactive slurries. An
example is given in Figure 3.58 [cww/tm/79].
A problem encountered with this technology is the erosion that can occur due to high throat
velocities. To prevent the emission of droplets, a demister is integrated in the scrubber.
Figure 3.58: Venturi Scrubber
Advantages
High efficiencies are feasible, even with fine
dust.
Disadvantages
Contamination of the demister may be a
problem.
Simultaneous cooling of waste gas streams

with high entrance temperature.
High-pressure drop.
Dust is collected as sludge and has generally
to be processed first before re-use, or has to be
disposed of as landfill, or otherwise.
No explosion risk.
Suitable for corrosive gases.
Small dimension compared with fabric filter or
ESP.
Also removes other i.e. gaseous
contaminants.
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The removal rate feasible for contaminants is:
dust:
hydrogen chloride:
hydrogen fluoride:
up to 99 %
90 %
90 %.
Input are:
the amount of scrubbing water, dependent on the temperature and humidity of the gas
stream. For dust removal a Water/Gas factor between 0.27 l/Nm3 for the plate scrubber and
venturi scrubber, and up to 4 13 l/Nm3 for the spray tower is observed.
electric energy for pumps and fans.
The energy consumption is approximately 1.2 6 kWh/1000 Nm3/h [cww/tm/64].

The pressure drop is 2 25 mbar in a spray tower, 20 200 mbar in a venturi scrubber
[cww/tm/64].
With wet dust removal technique a secondary installation to separate the suspension is
compulsory.
Depending on its source, the separated dust can be contaminated e.g. dust originating from
A mass emission to assess the performance of a wet scrubber can be determined by monitoring
the particulate concentration in the effluent gas stream, using an isokinetic sampling probe or a
meter based on, for example, UV/visible opacity, beta rays or particle impingement. The
pressure drop across the scrubber and the liquid/reagent flow rate need to be routinely
monitored. Wet scrubbers should be inspected regularly to identify any deterioration in the
plant, such as corrosion or blockages. There should be ready access to the scrubber.
Costs [cww/tm/70]
The investment costs are approximately k 5/1000 Nm3/h at 10000 Nm3/h, scale-up factor to
the power of 0.3. The investment costs for the water removal installation are not included.
labour costs:
utilities:
total costs:
k 2.5/year (estimated on 2 hours per week)

approximately 100/year per 1000 Nm3/h
not known
2.5 + 0.1 x flow/1000 k/year
Cost relevant parameters are the pressure drop and the liquid recirculation. There are no
revenues.
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3.5.3.5 Fabric Filter
Principle
The waste gas stream is passed into a large chamber fitted with filter material. Initially the
fabric itself acts as the filter. As dust builds up on the bag surface the filter cake takes over as
filter, thus enabling the removal of finer particle sizes. When the pressure drop reaches a certain
limit the dust cake has to be removed. An example of a fabric filter is shown in Figure 3.59
[cww/tm/79].
Figure 3.59: Fabric Filter
Application
Primarily the fabric filter is used to remove dust. In combination with injection systems
(including adsorption, semi-dry lime injection), it can also be applied to remove specific
gaseous contaminants.
gas flow:
temperature:
pressure:
dust content:
no restrictions,
< 280 C,
< 70 C for the improved compact filter,
atmospheric,
< 100 g/Nm3 [cww/tm/64]
The relative humidity of the waste gas should be kept low to avoid condensation. If fabric filters
are operated at the dew point of the flue gas, the dust becomes wet and the filtration process
ceases the fabric filter is blinding.

Fabric filters are usually manufactured as bags hindering particulate matter above a certain size
to pass through.
There are three types of fabric filter:
shaker fabric filter,

reverse flow fabric filter,
pulse jet fabric filter.
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The choice of filter material is determined by the properties of the solids to be removed and the
residual emission. Temperature and pressure determine the mechanical design of the housing.
Corrosion of filter and housing material can be a problem if the gas stream consists of acidic
components, especially at temperatures below the dew point. For appropriate filter fabrics see
Table 3.15 [cww/tm/79]. Woven fabrics are commonly used with shaker and reverse flow fabric
filters, felt ones with pulse jet fabric filters.
GENERIC NAME
Natural fibre cellulose

Polyolefine
Glass
Polyamide
aromatic polyamide
Fluorocarbon
Polybenzimidazole
Polytetrafluoroethen
Homopolymer Acrylic
Stainless Steel
CHEMICAL
RESISTANCE TO
Acids
Alkalies
poor
excellent
good
poor
fair
excellent
good
excellent
good
good
excellent
excellent
poor
excellent
very good
excellent
fair
excellent
excellent
good
OPERATING
TEMP.
(C)
80
87
260
93
204
232
537
230
140
454
MAX.
TEMP.
(C)
105
87
287
121
218
260
649
260
538
FIRE
RESISTANCE
poor
poor
good
poor
poor
poor
poor
poor
poor
good
Table 3.15: Filter Materials used in Fabric Filters
There are various versions available with respect to the cleaning system and the potential to
replace filter modules, each of them with its specific properties.
Other near relatives of the fabric filter are:
Compact filter, which is also known as Cassette Filter or Envelope Filter, and is a version
of the fabric filter. The distinction lies in the compact way in which the filter material is
fitted. The filter material is pleated, e.g. like a concertina, to obtain a far larger specific
filtration surface. The space saving, however, is partly eliminated by the lower fabric load
of this type of filter.
Improved Compact Filter, which is also known as Sintamatic, Sinter Lamellae Filter or
Spirot Tube, is another version of the fabric filter. The improved compact filter consists of
porous sintered material with pleated filter elements for the Sintamatic or Sinter Lamellae
Filter, which provides a longer service life and thereby reduced maintenance costs.
Systems with an elevated risk, such as explosion and fire, have to be equipped with safety
facilities, such as explosion hatch, sprinkler system etc. On the dirty side of the filter, there
should be an explosion relief that opens to a safe place, e.g. outside the building.
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Advantages
Dust is separated without using consumables.
The separated dust might be re-used in the
preceding process.
Residual emissions are virtually independent
of the intake concentration. Ventilated air can
be used again as intake air after filtration.
Disadvantages
Waste gas temperature has to be < 280 C,
owing to the temperature resistance of the
fabric. Special fabric can withstand higher
temperatures. The improved compact filter can
only work < 70 C.
No wet or sticky dusts allowed as input.
Fabric filters take up large space.
There is an explosion risk.
Baghouse fires possible if very hot particles
are released from furnaces or because of
pyrophoric materials.

Dust can be abated down to 10 mg/Nm3 when operating a fabric filter or a compact filter, and
below 1 mg/Nm3 when operating an improved compact filter.
Input are:
filter fabric with filtration areas between 8 10 m2 per 1000 Nm3/h waste gas,
pre-coating of the filter fabric, probably necessary for sticky or static dusts or as protection
of the filter fabric,
compressed air (3 7 bar), to clean the filter elements, with an input between 2 2.5 Nm3/h
per 1000 Nm3/h,
The energy consumption is approximately 0.2 1.2 kWh/1000 Nm3/h [cww/tm/64].

The pressure drop is 10 25 mbar [cww/tm/64].
The separated dust possibly mixed with pre-coat material is the only residue. Its quantity
depends on the dust content of the incoming gas stream. Depending on its source, the separated
dust can be contaminated e.g. dust originating from incineration might contain dioxins and/or
heavy metals and their oxides. This type of dust might be classified as hazardous waste that has
to be disposed of accordingly.
Performance and maintenance have to be carefully monitored. The mass emission to assess the
performance of a fabric filter can be determined by monitoring the particulate concentration in
the effluent waste gas stream, using an isokinetic sampling probe or a meter based on, e.g.
UV/visible opacity, beta rays or particle impingement.
Temperature and pressure drop across the fabric filter need to be routinely monitored. The latter
is used to indicate when the cleaning cycle has to start. Fabric filters should be inspected
regularly to identify any deterioration of fabric or housing. Hence access to the fabric filter
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Costs [cww/tm/70]
The working life of filter material is about 5 years for fabric filter and compact filter and 8 years
for the improved compact filter.
The investment costs are k 1.0 4.5/1000 Nm3/h, depending on the housing design
( 500 - 700/1000 Nm3/h for filter material, linear with the waste gas stream. The filter material
for the improved compact filter is more expensive 800/1000 Nm3/h but that is more than
balanced by its longer service life)
labour costs:
utilities:
total costs:
k 2.5/year (estimated on 2 hours per week)

350/year (1 hour per month) for the improved compact filter
150/year per 1000 Nm3/h
100 140/year per 1000 Nm3/h
2.5 + 0.3 x flow/1000 k/year
350 + 240 x flow/1000 /year
Cost effective parameters are the waste gas stream, the filter material and the fabric load.
Saving or revenues can be expected from recovered raw material.
3.5.3.6 Two-Stage Dust Filter
Principle
The two-stage dust filter contains metal gauze as filter material. A filter cake is built up in the
first filtration stage and the actual filtration takes place in the second stage. Depending on the
pressure drop across the filter, the second stage is cleaned and the system switches between the
two stages (step one becomes the second and vice versa). A mechanism to remove the filtered
dust is integrated in the system. The dust drops to the bottom of the chamber where it has to be
removed. An example is shown in Figure 3.60 [cww/tm/70].
Figure 3.60: Two-Stage Dust Filter
Application
Primarily the two-stage dust filter is operated to remove particulates. In combination with
injection systems (inclusive adsorption, semi-dry lime injection), it can also be used to remove
specific gaseous contaminants.
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waste gas flow:

temperature:
pressure:
dust content:
up to 75000 Nm3/h per module,

up to approximately 400 C,
atmospheric,
no restrictions.

Since metal gauze has a larger load capacity than a fabric filter, less filter area (i.e. less filter
material) is required. This advantage, however, is usually eliminated because of the two-stage
system.
facilities, such as explosion hatch, sprinkler system etc.
Advantages
High efficiency for residual emissions,
virtually independent of intake concentration.
Disadvantages
High costs, compared to fabric and compact
filter.
Ventilated air re-usable as intake air.
Frequent switching between the two

compartments.
Modular structure.
No extra filter material; steel-only design.
Filter load higher than for a fabric or compact
filter.
Valve control necessary in a dusty

environment.
Also for damp, sticky, fibrous or static dust.

The two-stage dust filter usually works highly efficiently. Dust emissions of about 1 mg/Nm3
are feasible.
Input are:
filter material:
metal gauze.
compressed air:
compressed air (3 7 bar) is needed for cleaning the filter.
The energy consumption is approximately 1.5 kWh/1000 Nm3/h, the electric energy for the fan
is included.
The pressure drop is 5 18 mbar, exclusive of that in the gas ducts.
The separated dust is the only residue. Its quantity depends on the dust content of the incoming
gas. Depending on its source, the separated dust can be contaminated e.g. dust originating
from incineration might contain dioxins and/or heavy metals and their oxides. This type of dust
might be classified as hazardous waste that has to be disposed of accordingly.
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performance of a two stage dust filter can be determined by monitoring the particulate
concentration in the effluent waste gas stream, using an isokinetic sampling probe or a meter
based on, e.g. UV/visible opacity, beta rays or particle impingement.
is used to indicate when the cleaning cycle has to start. Fabric filters should be inspected
regularly to identify any deterioration of filter material and housing. Hence access to the filter
Costs [cww/tm/70]
The investment costs are k 30/1000 Nm3/h, based on a system of 1700 Nm3/h
labour costs:
utilities:
total costs:
2000/year (estimated on 1.5 hours per week)

not known
over 2000 + 350 x flow/1000 /year
Cost effective parameter is the pressure drop. Saving or revenues can be expected from recycled
raw material.
3.5.3.7 Ceramic Filter
Principle.
Ceramic as filter material enables the filter to be operated at high temperatures without cooling
facilities for the flue gas. A mechanism to remove the filtered dust, either by compressed air or
mechanical devices, is integrated in the system. The dust drops to the bottom of the chamber
where it has to be removed.
Application
A ceramic filter is primarily used to remove dust. Because of its high temperature resistance it is
preferably operated in incinerators and gasification systems.
waste gas flow:

temperature:
pressure:
dust content:
2000 500000 Nm3/h,

< 1000 C,
atmospheric,
up to 20 g/Nm3.
When the ceramic filter is operated at low temperatures, the relative humidity of the flue gas
should be kept low to avoid condensation.

facilities, such as explosion hatch, sprinkler system etc.
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Advantages
Dust separation without input of consumables.
The separated dust may be re-used in the
preceding process.
Disadvantages
Less suitable for sticky dusts as input.
Residual emissions are virtually independent

of the intake concentration. Ventilated air can
be used again as intake air after filtration.
Temperature fluctuations when cleaning with

compressed air. Damage to the ceramic filter
material might occur.
Modular structure.
Sealing of the filter housing more critical

owing to the use of brittle ceramics.
Expensive.
Compact construction.
Suitable for high temperatures.

Dust emissions of below 1 mg/Nm3 are achievable.
Input are:
filter material:
ceramic
pre-coatings of the filter material, possibly necessary for sticky dusts.
compressed air:
3 7 bar, to clean the filter.
The energy consumption is approximately 1 kWh/1000 Nm3/h, the electric energy for the fan is
not included.
The pressure drop is 70 300 mbar, exclusive of that in the gas ducts.
The separated dust possibly mixed with pre-coat material is the only residue. The quantity
depends on the dust content of the incoming gas. Depending on its source, the separated dust
can be contaminated e.g. dust originating from incineration might contain dioxins and/or
heavy metals and their oxides, which might be classified as hazardous waste to be disposed of
adequately.
performance of a ceramic filter can be determined by monitoring the particulate concentration
in the effluent waste gas stream, using an isokinetic sampling probe or a meter based on, e.g.
The temperature and pressure drop across the filter need to be routinely monitored. The latter is
used to indicate when the cleaning cycle has to start. Ceramic filters should be inspected
regularly to identify any deterioration. Hence access to the filter should be available.
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Costs [cww/tm/70]
The service life of the filter material is about 3 5 years.
The investment costs are k 30 55/1000 Nm3/h, (approximately linear with the waste gas
stream, as investment is largely determined by the filter material).
labour costs:
utilities:
total costs:
350/year (estimated on 1 hour per month)

approximately over 150/year per 1000 Nm3/h
350 + 300 x flow/1000 /year
Cost effective parameters are the waste gas stream, the filter material and the material load.
Saving or revenues can be expected from recovered raw material.
3.5.3.8 Absolute Filter
Principle
The contaminated waste gas stream is sent into a chamber, where it is forced through a filter.
The separation is based on surface filtration, so no dust penetrates into the filter material. The
cleaned gas stream leaves the filter, the dust remains behind. The purification can be carried out
with an integrated system which is controlled by time and pressure. The separated dust can be
removed from the filter. In very small systems no cleaning mechanism is necessary. Here the
filter as cartridge will be replaced, or externally recycled. An example is shown in Figure
3.61 [cww/tm/70].
Application
The absolute filter is primarily used to remove dust from waste gas streams that are not too
large. It can be used as a second stage behind a dust filter that can cope with high dust loads.
waste gas flow:

temperature:
pressure:
dust content:
100 - 2000 Nm3/h per module,

< 350 C,
atmospheric,
< 1 mg/Nm3.
The relative humidity of the waste gas should be kept low to avoid condensation.
Figure 3.61: Absolute Filter
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Temperature and pressure determine the mechanical design of the housing, which is built of
steel, stainless steel or plastic.
specific volume:
specific weight:
approximately 0.03 m3 per 1000 Nm3/h waste gas,

approximately 0.01 tonnes per 1000 Nm3/h.
The basis for the filter dimension is the waste gas flow rate and the surface load of the filter.
Advantages
Separation of very small fractions is possible.
Disadvantages
Not suitable for wet substances.
Very high efficiency with very low residual

emission.
Not suitable for high dust loads.
Low pressure drop.

Modular structure.

Dust emissions down to < 0.1 mg/Nm3 are achievable.
Input are:
filter material:
glass fibre
The energy consumption is lower than 0.1 kWh/1000 Nm3/h, the electric energy for the fan is
included.
The pressure drop is 0.5 2.5 mbar.
The loaded filter elements have to be disposed of as waste. Each module can absorb
approximately 1 kg of dust.
performance of an absolute filter can be determined by monitoring the particulate concentration
in the effluent waste gas stream, using an isokinetic sampling probe or a meter based on, e.g.
is used to indicate when the cleaning cycle has to start. Filters should be inspected regularly to
identify any deterioration of housing and filter material. Hence access to the filter should be
available.
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Costs [cww/tm/70]
The service life of the filter material is about 1 year.
The investment costs are 60 120/1000 Nm3/h.
labour costs:
utilities:
total costs:
2500/year (estimated on 2 hours per week)

not known
60 - 120/year per 1000 Nm3/h
2500 + 60 x flow/1000 /year
Cost effective parameter is flow rate of the waste gas stream. There are no revenues.
3.5.3.9 HEAF Filter
Principle
An HEAF filter is a flat bed filter in which aerosols combine into droplets. Highly viscous
droplets remain on the filter fabric and can eventually clog the filter. When a pre-set value of
pressure difference is reached, the filter fabric has to be replaced by a new and clean filter,
which can be exchanged during continuous operation, because the filter fabric is set on a roll.
The treated waste gas leaves the treatment device via a mist filter, which has to separate the
entrained layer of viscous droplets. An example is shown in Figure 3.62 [cww/tm/70].
Figure 3.62: HEAF Filter
Application
HEAF filters are normally applied to remove aerosols such as oil, plasticisers and condensable
VOCs.
waste gas flow:

temperature:
pressure:
up to approximately 25000 Nm3/h,

not known, dependent on fabric,
atmospheric

The housing is built of steel or stainless steel, dependent on the demands.
specific volume:
specific weight:
212
2 - 7 m3 per 1000 Nm3/h waste gas,

0.16 0.5 tonnes per 1000 Nm3/h.
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Additionally a droplet separator is implemented for droplets with low viscosity. The design of
the secondary droplet separator can be a lamellar type separator (inertia separator) or a mist
filter.
Advantages
Continuous process.
Disadvantages
High-pressure drop.
Suitable for highly viscous droplets.

The removal rate for pollutants is:
Droplets emission:
aerosols:
up to 99 %
up to 99 %
Input are:
filter fabric on a roll, about 300 per 160 m roll.

electric energy for fan and pumps.
The energy consumption is lower than 0.1 kWh/1000 Nm3/h, the electric energy for the fan is
not included.
The pressure drop is 80 mbar
Residues to be disposed of are the loaded filter rolls, containing the contaminants separated as
droplets, aerosols and dust. They have to be disposed of as chemical or hazardous waste and are
usually sent to waste incineration.
Costs [cww/tm/70]
The investment costs are k 5.7 8.0/1000 Nm3/h.
labour costs:
utilities:
total costs:
approximately 3000/year (estimated on 2.5 hours per week)

not known
not known
> 3000/year
Cost effective parameters are waste gas flow rate and the pressure drop. There is no revenue.
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3.5.3.10 Mist Filter
Principle
Mist filters are operated as deep bed filtration, which takes place over the entire depth of the
filter. Solid dust particles remain in the filter until it is saturated and thus has to be cleaned by
flushing. When the mist filter is used to collect droplets and/or aerosols, it is usually selfcleaning, drained by the liquid. An example is shown in Figure 3.63 [cww/tm/70].
Figure 3.63: Mist Filter
Application
Mist filters are used to remove misty pollutants, such as droplets and aerosols. When the filter
material is cleaned in-situ, they are also applicable to solid particles soluble in liquids. Owing to
clogging, they are less suitable for solid dusts and greasy vapours.
Mist filters can be used as secondary devices.
waste gas flow:

temperature:
dust content:
aerosols:
1000 - 150000 Nm3/h per module,

< 170 C,
< 1 mg/Nm3,
a few g/Nm3.
There are no strict restrictions to soluble dusts.

Temperature and pressure determine the mechanical design of the housing, which is built of
steel or plastic.
The basis for the filter dimension is the waste gas flow rate, and the filter load.
Advantages
Selfcleaning systems for the collection of
liquids.
Disadvantages
The cleaning of the filter results in a
contaminated washing liquid.
Suitable for filtration of liquid aerosols.
High-pressure drop with solid dust particles.

Clogging risk.
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dust:
aerosols:
up to 99 %
up to 99 %
Input are:
filter material, often glass fibre or plastic, depending on the application.

washing liquid for cleaning.
The energy consumption:
not known
The pressure drop is normally up to 25 mbar, can be up to 90 mbar when applied to big loads.
Residues to be disposed of are the washing liquid, which contains filtered dust, and the loaded
filter material. The washing liquid either has to undergo waste water treatment or is disposed of
as waste, e.g. incinerated.
Costs [cww/tm/70]
The investment costs are 2.3/1000 Nm3/h (for small systems up to 2000 Nm3/h)
labour costs:
utilities:
total costs:
2500/year (estimated on 2 hours per week)

not known
250 - 600/year per 1000 Nm3/h (depending on the filter
material)
2500 + 450 x flow/1000 /year
Cost effective parameter is the pressure drop. The revenue is the recovery of the product.
3.5.4 Abatement Operations and Processes for Gaseous Pollutants in

Flue Gases
Pollutants from incineration processes are particulates, discussed in Chapter 3.5.3, and gases
such as sulphur dioxide, nitrogen oxides, hydrogen halides and, last but not least, the so-called
dioxins poly-chlorinated (or halogenated) p-dibenzo dioxins and furans. Waste gas treatment
of these gaseous pollutants is abatement technology, with the option, however, that some
abatement products can be used as raw material in other manufacturing processes, e.g. raw
hydrochloric acid, sulphur or gypsum.
Gaseous pollutants such as sulphur dioxide, hydrogen halides or dioxins can be abated
practically as a side-reaction in treatment operations mentioned above, such as dust scrubbing
or trace gas scrubbing for sulphur dioxide and hydrogen halides, or adsorption on GAC or
catalytic filtration for dioxins.
Common operations and processes for the waste gas treatment of these gaseous pollutants are
described below.
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3.5.4.1 Dry Sorbent Injection
Principle
A fine-powdered sorbent, e.g. lime, is injected into the waste gas or flue gas stream, where it
reacts with acid gases, generating a dry waste material. The sorbent can be injected at various
points, according to the temperature and conditions at which it is most reactive. The dry waste
material is removed in the particle abatement equipment, which is commonly a fabric filter (bag
filter).
The reaction products depend on the type of sorbent, the reaction temperature and the content of
excess oxygen in the flue gas. With excess oxygen, for example, the total oxidation to sulphate
occurs at temperatures above 800 C. Below this temperature a mixture of sulphate, sulphite and
sulphide is formed. The optimum temperature for the direct reaction with hydrated lime or
sodium bicarbonate is between 130 180 C.
Application
Dry sorbent injection is typically used to reduce emissions of sulphur dioxide, hydrogen
chloride and hydrogen fluoride. It is suitable for small plants or for retro-fit applications where
the capital expenditure for other systems might be very expensive.
waste gas flow:

SOx concentration:
10000 30000 Nm3/h,

none.
Figure 3.64: Dry Sorbent Injection for Sulphur Dioxide Removal (Positions of Injection)
Commonly used injection systems are:
216
furnace injection of limestone at temperatures between 1100 1250 C,

heat exchanger injection of slaked lime at temperatures of about 550 ,
post furnace injection of slaked lime at relatively high humidity at temperatures of 5 15 C
above flue gas saturation,
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post furnace injection of sodium based compounds, e.g. sodium bicarbonate, between heat
exchanger and particulate abatement device, at a temperature range between 130 180 C.
The dry sorbent injection systems are shown in Figure 3.64 [cww/tm/79].
The choice of the sorbent depends on its availability. It is in most cases a naturally occurring
material, such as limestone, dolomite or hydrated compounds derived from these raw materials.
Advantages
No extra installations are necessary, since a
dust removal system is usually installed
already.
Disadvantages
Large surplus of lime that has to be disposed
of as waste.
Low efficiency.
Very low cost system compared with others.

The added sorbent can, by interacting with fly
ash, cause fouling of heat exchanger surfaces.

Achievable values are:
SOx elimination:
HCl:
HF:
approximately 70 %
< 10 mg/Nm3
< 1 mg/Nm3
There is no extra energy consumption.

There is no extra pressure drop.
Since the sorbent injection takes place in an existing incineration plant, all utilities such as
electric energy for fans and pumps, fabric material for the dust abatement system, etc. are
already operating, independently ofthe injection operation. Thus the only input is the sorbent.
Because of the specific operational conditions, a much larger amount of sorbent is needed than
stoichiometrically calculated. With lime, for example, it is three times the theoretical quantity.
The residue is a mixture of the original sorbent and the reaction products and has to be disposed
of. Included are all pollutants that have not been destroyed during the incineration process, such
as heavy metal compounds and/or dioxins, dependent on the input of the incineration
installation. So the residual dust might be hazardous waste that has to be disposed of under
special conditions.
The performance of the dry sorbent injection system is examined by determining the sulphur
dioxide and particulate abatement efficiencies.
The pressure drop is routinely monitored across the (bag) filter. When an ESP is used, electric
current and field strength are monitored to give warning of any malfunction in the particulate
abatement device.
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Chapter 3
Costs [cww/tm/70]
There are no considerable extra investment costs.
labour costs:
utilities:
total costs:
approximately 2500/year (2 hours per week)

approximately 150/1000 Nm3/h
approximately 100 140/1000 Nm3/h plus sorbent
approximately 2500 + 300 x flow/1000 /year plus sorbent
Cost effective parameters are the waste gas flow rate, pressure drop, sulphur dioxide load. There
are no revenues.
3.5.4.2 Semi-dry Sorbent Injection
Semi-dry sorbent injectors (or spray dryers) are used to control acidic compounds (sulphur
dioxide, hydrogen chloride, hydrogen fluoride) in a flue gas stream. Droplets of reagents, e.g.
lime or sodium carbonate/bicarbonate, are contacted with the flue gas in a reaction chamber in
such a way that liquid is continuously evaporating during the reaction. The result is a dry
product, which can be collected at the base of the chamber or in the particulate abatement
device, e.g. a fabric filter (bag filter) or an ESP.
Application
Dry sorbent injection is normally used to control emissions of acidic gases in combustion plants
and incinerators.
waste gas flow:

SOx concentration:
up to 1000000 Nm3/h,
none.
Figure 3.65: Spray Dry Flue Gas Desulphurisation System
218
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Chapter 3

The total spray dryer system consists of:
the spray dryer atomiser and reaction chamber,

associated slurry/liquid equipment (lime slurries or sodium carbonate/bicarbonate
solutions),
a particulate collection device,
a particulate recycling device.
A spray dryer system, used for desulphurisation, is shown in Figure 3.65 [cww/tm/79].
There are three types of atomisers generating the droplets:
rotary atomiser,
two fluids atomiser,
spray nozzles.
The reaction chamber is a tower or a duct, the droplets and the flue gas flowing co-currently.
Advantages
Relatively simple installation.
Disadvantages
Large surplus of lime that has to be disposed
of.
Better separation performance than with dry

sorbent injection.
Cheaper than wet scrubbing.
Low separation performance.

Humidity might be a disturbance to the
secondary fabric filter (bag filter).

SOx elimination:
HCl:
HF:
> 90 % [cww/tm/79]
> 99 %, or < 10 mg/Nm3
< 1 mg/Nm3
Input are:
the sorbent; the quantity of lime required is approximately 1.5 times the theoretical quantity.
water to prepare the slurry; the amount dependent on temperature and relative humidity of
the flue gas stream. The flue gas streams are frequently cooled to just above their dew point.
no information
The pressure drop is approximately 25 mbar.

The residue is a mixture of the original sorbent and the reaction products and has to be disposed
of. Included are all pollutants that have not been destroyed during the incineration process, such
as heavy metal compounds and/or dioxins, dependent on the input of the incineration
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219
Chapter 3
installation. So the residual dust might be hazardous waste that has to be disposed of under
special conditions.
The performance of the spray dryer system is examined by determining the acidic gas
concentration and particulate abatement efficiencies.
Temperature, pressure drop and liquid/gas flow rates are routinely monitored.
Costs [cww/tm/70]
The investment costs are approximately k 11/1000 Nm3/h (based on 100000 Nm3/h).
labour costs:
utilities:
total costs:
approximately k 20/year (1 day per week)

approximately 250/1000 Nm3/h
approximately 100 140/1000 Nm3/h plus sorbent
approximately 20000 + 400 x flow/1000 /year plus sorbent
Cost effective parameters are the waste gas flow rate, pressure drop, sulphur dioxide load. There
are no revenues.
3.5.4.3 Biological Sulphur Dioxide Removal from Flue Gas
Principle
The biological sulphur dioxide removal system is a combination of a waste gas scrubber
(absorber) and a biological waste water treatment facility. In the absorber, the waste gas stream
containing sulphur dioxide is brought into contact with washing water. A mixture of sulphite
and sulphate is formed. In a subsequent anaerobic biological process, this mixture is converted
biologically into sulphide. The ensuing aerobic step converts sulphide into elemental sulphur,
which is separated and the supernatant water recycled to the scrubber.
Application
The biological technology to remove sulphur dioxide is suitable to clean flue gases of
combustion plants or waste gases of sulphuric acid production plants. Heavy metals can be
removed as well by way of this method. Omitting the first anaerobic biological degradation
step, hydrogen sulphide from biogas, ventilation air and high-pressure natural gas can also be
eliminated. The resulting product is elemental sulphur. Heavy metals are removed and
recovered as metal sulphides.
Pilot plant conditions [cww/tm/75]:
220
waste gas flow:

temperature:
pressure:
sulphur dioxide concentration:
water content:
carbon dioxide content:
nitrogen content:
oxygen content:
hydrogen chloride concentration:
6000 Nm3/h,
120 C,
atmospheric,
2000 mg/Nm3,
6.9 vol %,
12.9 vol %,
75.2 vol %,
5 vol %,
250 mg/Nm3,
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Chapter 3
25 mg/Nm3,
75 mg/Nm3.
hydrogen fluoride concentration:

Fly Ash:

The equipment to remove sulphur dioxide consists of four parts:
an absorber (spray tower), responsible for the removal of sulphur dioxide from the flue gas
stream, with water as the absorbent,
an anaerobic reactor, where sulphites and sulphates are reduced to sulphides by bacteria in
the presence of ethanol, hydrogen, starch or glucose; heavy metals are precipitated as metal
sulphides,
an aerobic reactor (gas lift loop reactor type), where sulphides are converted to elemental
sulphur by bacteria in the presence of oxygen,
a sulphur recovery unit (tilted plate separator).
The sulphur will either be de-watered in a decanter centrifuge to about 60 70 % dry solid
sulphur, with a purity of 95 %, or melted to produce liquid sulphur.
The process is illustrated in Figure 3.66.
Effluent
Bleed
Influent
A
N
A
E
R
O
B
I
C
A
B
S
O
R
B
E
R
A
E
R
O
B
I
C
Sulphur
H2 or ethanol
Air
Figure 3.66: Biological Sulphur Dioxide Removal from Flue Gas
Advantages
Recovery as elemental sulphur with purity of
at least 95 %.
Heavy metals are removed simultaneously
with the option of recycle.
Scrubbing water is used in recirculation so no
additional waste water is produced.
Disadvantages
Biomass can result in blockage of the nozzles
if not removed from the circulating water
stream.
Poisoning of the biomass must be avoided.
Additional electron donor compounds such as
ethanol, hydrogen, starch, glucose, etc are
necessary.
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221
Chapter 3

A sulphur dioxide removal efficiency of about 98 % is achievable.
Input are:
water as absorbent liquid, operated in recirculation, only evaporation and blowdown losses
to be replaced,
electron donor compounds for the anaerobic biological step (ethanol, hydrogen, starch,
glucose, etc., alternatively used),
electric energy for fans and pumps
Energy consumption:
not known
Pressure drop:
according to scrubber processes
Because of the circulation process, the salt concentration in the scrubbing water increases, so
the adsorbent has to be discharged from time to time. This water effluent has to be treated as
waste water or disposed of otherwise.
Surplus activated sludge has to be disposed of, e.g. by incineration, dependent on the waste gas
contaminants or the degradation compounds.
Heavy metal sulphides have to be disposed of, either as chemical waste, or, preferably, as raw
material for other processes. Another product is elemental sulphur that can be used as raw
material in sulphuric acid production, or it can be used as soil amendment [cww/tm/75].
Monitoring
Efficiency may be determined by chemical analysis of the inlet and outlet gases. The presence
of hydrogen sulphide has to be monitored to check leaks or explosive gas mixtures.
Costs
The investment costs are higher than for sodium hydroxide scrubbing.
labour costs:
utilities:
total costs:
not known
not known
no information
not known, but lower than for sodium hydroxide scrubbing.
Revenue is the regain of elemental sulphur and, under favourable conditions, the recycling of
heavy metals.
3.5.4.4 Selective Non-catalytic Reduction of NOx (SNCR)
Principle
Ammonia or urea is injected into the flue gas stream after combustion or incineration, reducing
nitrogen oxides to nitrogen and water. Usually a 25 % solution of ammonia is injected. When
ammonia is employed, the point of injection is in the area where the flue gases have reached a
temperature between 930 980 C, whereas urea is injected in an area where the gas
temperature is between 950 1050 C.
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Chapter 3
Application
SNCR is used to abate nitrogen oxides in combustion processes, including industrial and utility
boilers, incinerators and industrial refinery and petrochemical process furnaces.
waste gas flow:

temperature:
pressure:
NOx:
none,
930 1050 C, dependent on the reagent,
atmospheric,
a few g/Nm3,

aqueous ammonia storage tank,

the ammonia vaporiser,
a carrier gas supply, steam or compressed air,
injector nozzles.
The injection occurs inside the flue gas duct after incineration.
Advantages
Relatively simple installation.
Disadvantages
Ammonia system is critical relative to safety.
Low investment.
High temperature necessary.

Usually high ammonia slip.

NOx elimination:
50 - 80 %
Under advantageous reaction conditions an ammonia slip below 5 ppm is possible.

Input are:
ammonia, 570 kg per tonne nitrogen oxide removed,

with ammonia as reagent, steam is used to evaporate the ammonia before injection,
electric energy for pumps and fans.
no information
There is no pressure drop due to operational conditions.

Emissions from the SNCR process are mainly nitrogen and water vapour. An ammonia slip is
also observed, that can be up to 100 mg/Nm3, but under advantageous conditions is as low as
5 ppm.
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Chapter 3
Monitoring
The performance of the SNCR system can be monitored by analysing the nitrogen oxides
content before and after the treatment and the ammonia and oxygen content of the effluent gas
stream.
The temperature and pressure drop are routinely monitored.
Costs [cww/tm/70]
The investment costs are approximately k 2.3 3.9/1000 Nm3/h
labour costs:
utilities:
total costs:
not known
not known
ammonia or urea
very low
Cost effective parameter is the consumption of ammonia or urea. There are no revenues.
3.5.4.5 Selective Catalytic Reduction of NOx (SCR)
Principle
The waste gas stream is passed over a catalyst, ammonia or urea injected upstream. The
optimum mixing of these two streams over the catalyst bed is vital. Nitrogen oxides and
ammonia react to nitrogen and water. The temperature range is between 150 and 400 C
Application
SCR is operated to abate nitrogen oxides in combustion processes, including industrial and
utility boilers, incinerators and industrial refinery and petrochemical process furnaces.
waste gas flow:

temperature:
pressure:
NOx:
dust:
up to 1000000 Nm3/h,
150 400 C,
atmospheric,
a few g/Nm3,
to a few g/Nm3.

aqueous ammonia storage tank,

the ammonia vaporizer,
a carrier gas supply, steam or compressed air,
injector nozzles,
the catalyst bed.
The catalyst can be composed of vanadium, titanium, tungsten or molybdenum.

The injection occurs in the flue gas duct after incineration.
224
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Chapter 3
In the presence of sulphur dioxide, the temperature of the incoming waste gas stream should be
above dew point to avoid deposit of ammonium sulphate.
Advantages
Low operating costs.
Disadvantages
Ammonia system is critical relative to safety.
Simultaneous removal of dioxins possible.
Catalysts limited service life.

High costs of catalyst.
Usually high ammonia slip.

NOx concentration:
approximately 50 mg/Nm3
When favourable reaction conditions are applied an ammonia slip below 2 - 10 ppm is possible.
Input are:
ammonia, 370 kg per tonne of nitrogen oxide removed,

catalyst with a service life of approximately 16000 hours (about 2 years).
Energy consumption
no information
The pressure drop is 1 10 mbar (exclusive that of the duct).

With ammonia as reagent, steam is used to evaporate the ammonia before injection.
Emissions from the SNCR process are primarily nitrogen and water vapour. Additionally an
ammonia slip is observed that can be up to 100 mg/Nm3, but under favourable conditions down
to 2 ppm. Nitrous oxide can be formed as a by-product, more readily when urea is used.
The catalyst has to be disposed of as chemical waste or might be recycled.
Monitoring
The performance of the SNCR system can be monitored by analysing the nitrogen oxides
content before and after the treatment and the ammonia and oxygen content of the effluent gas
stream.
Temperature and pressure drop are routinely monitored.
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225
Chapter 3
Costs [cww/tm/70]
The investment costs are approximately k 7.5 32.0/1000 Nm3/h
labour costs:
utilities:
total costs (investment
plus operating)
not known
not known
approximately 140 per tonne NOx removed
k 1.0 5.0 per tonne NOx removed
Cost effective parameter is the consumption of ammonia or urea. There are no revenues.
Retro-fitting of SCR can require radical modifications of the existing installation and thus
demand high investment costs. This is expressed in the wide range of investment costs above.
226
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Chapter 4
4 BEST AVAILABLE TECHNIQUES
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227
Chapter 5
5 EMERGING TECHNIQUES
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229
Chapter 6
6 CONCLUSION AND RECOMMENDATION
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231
References
REFERENCES
[cww/tm/4]
Metcalf & Eddy, Inc.,
Waste Water Engineering Treatment, Disposal, and Reuse,
3rd edition, revised by Tchobanoglous, Burton,
McGraw-Hill, New York, 1991
[cww/tm/27]
Environment Agency (UK), HMSO, 1997
Technical Guidance Note A4,
Effluent Treatment Techniques
[cww/tm/48]
CONCAWE, May 1999
Document No. 99/01,
Best Available Techniques to reduce Emissions from Refineries
[cww/tm/51]
RIZA (NL), 1990
Inventory of Treatment Techniques for Industrial Waste Water
[cww/tm/64]
BASF, July 1999
Verfahrenstechniken der Abgas-/Abluftbehandlung
[cww/tm/67]
VDI-Gesellschaft Verfahrenstechnik und Chemie-ingenieurwesen, 1999
4. GVC-Abwasser-Kongress 1999, Preprints
[cww/tm/70]
Tauw, Feb 2000
InfoMil,
Dutch Notes on Waste Gas Treatment
[cww/tm/71]
ENTEC UK Ltd., 1996
Environmental Technology Best Practice Programme, Guide GG12,
Solvent Capture for Recovery and Re-use from Solvent-laden Gas Streams
[cww/tm/72]
CEFIC, Dec 1999
IPPC BAT Reference Document. Waste Water/Waste Gas Treatment. Chemical Industry
Contribution Paper on Waste Water/Waste Gas Management
[cww/tm/74]
Environmental Processes 98, Hydrocarbon Processing 71-118,
Aug 1998
[cww/tm/75]
Paques Bio Systems B.V., Apr 1997,
Jansen, Buisman,
Biological SO2 Removal from Flue Gas
Version May 2000
233
References
[cww/tm/76]
European Lime Association, 1999
Lime and Dolomite Products for the Treatment of Drinking Water, Waste Water and
Sewage Sludge
[cww/tm/77]
Naval Facilities Engineering Service Center (USA), June 1998
Joint Service Pollution Prevention Technical Library,
http://enviro.nfesc.navy.mil/p2library
[cww/tm/78]
Verfahrenstechnik, Mar 1999
Kaiser, Lehner,
Dampf- und Luftstrippung zur Rckgewinnung von Ammoniak aus Abwasser
[cww/tm/79]
Environment Agency (UK), Apr 1994
Pollution Abatement Technology for Particulate and Trace Gas Removal
[cww/tm/80]
Environment Agency (UK), Febr 1994
Pollution Abatement Technology for the Reduction of Solvent Vapour Emissions
[cww/tm/81]
P. Kunz,
Behandlung von Abwasser,
Vogel Verlag, Wrzburg, 2nd Edition 1990
[cww/tm/82]
Background Paper to Annexe 22 Waste Water Ordinance,
Germany, 2000
[cww/tm/84]
InfoMil, Feb 2000
Dutch Notes on BAT for the Large Volume Organic Chemicals Industry
[cww/tm/85]
W.L. GORE & Ass., 1999
Plinke et al.,
Catalytic Filtration Dioxin Destruction in a Filter Bag,
unpublished
[cww/tm/86]
Linnhoff et al., Aug 1998
Intelligent Networking of Process Waste Water Streams in the Chemical Industry
http://www.linnhoffmarch.com/Resources/Pinch.html
[cww/tm/87]
DVWK Regeln 134/1997,
Technische Regel wassergefhrdender Stoffe (TRwS) Abwasseranlagen als Auffangvorrichtungen
234
Version May 2000
References
[cww/tm/88]
Council Directive 1999/13/EC,
11.3.1999
[cww/tm/89]
US-EPA, 1995
AP-42 Emission Estimating Handbook, section 7.1 Storage of Organic Liquids
http://www.epa.gov./ttn/chief/ap42.html
[cww/tm/90]
US-EPA OAQPS, Dec 1999
TANKS 4.06 for Windows
http://www.epa.gov/ttnchie1/tanks.html
[cww/tm/91]
Nalco Chemical Company,
The NALCO Water Handbook,
2nd Edition,
McGraw-Hill, New York, 1988
[cww/tm/92]
ENTEC UK Ltd., 1996
Cost-effective Separation Technologies for Minimising Wastes and Effluents
[cww/tm/93]
ENTEC UK Ltd., 1997
Cost-effective Membrane Technologies for Minimising Wastes and Effluents
[cww/tm/94]
Environment Agency (UK), Nov 1993
Guidance on Effective Flaring in the Gas, Petroleum, Petrochemical and Associated
Industries
[cww/tm/95]
European Water Pollution Control, Vol 7, 1, 1997
Meyer, Hanke,
Reduction of nitrogen and phosphorous discharges from Bayers Dormagen production
site
Version May 2000
235

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EUROPEAN COMMISSION

Integrated Pollution Prevention and Control (IPPC)

World Trade Center, Isla de la Cartuja s/n, E-41092 Seville - Spain

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Status of this document

Furthermore, Annex IV of the Directive contains a list of considerations to be taken into

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Objective of this Document

This document represents a summary of information collected from a number of sources,

How to understand and use this document

The information provided in this document is intended to be used as an input to the

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World Trade Center, Isla de la Cartuja s/n, E-41092 Seville Spain

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Reference Document on Best Available Techniques in the Common Waste Water

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3.1.1.1 Total Installed Costs vs Supplier Equipment Costs ........................................................48

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Figure 3.47: Catalytic Incinerator.............................................................................................................183

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The borderline to be drawn in this document between processes relevant to chemical

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Figure I: Borderline between Relevance to Production and Reduction/Prevention

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1.1 Waste Water in Chemical Industry

scrubbing of exhaust gases from incinerations and combustions,

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non-reacted starting compounds,

very strong toxic

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1.1.2 Waste Water Handling

process-integrated measures, such as:

1.1.2.1 Process-Integrated Measures

new synthesis pathways,

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Counter Current Washing as Example for Water Saving Processes

Multiple Use and Recirculation Operations

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Indirect Cooling with Vapour Phases

Waste Water-free Processes for Vacuum Generation

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Waste Water-free Processes for Exhaust Air Cleaning

Substance Recovery or Retention from Mother Liquors or by Optimised

removal of utilisable individual compounds, such as starting materials, products, solvents,

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Use of Low-contaminated Raw Materials and Auxiliaries

metals from crude vegetable fats, or from crude sodium hydroxide,

The operators ability to influence this situation is limited by:

insufficient information from suppliers,

1.1.2.2 End-of-pipe Measures

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Unit Operation, Unit Process or Treatment System

Screening and comminution

nitrification and de-nitrification variations

Activated carbon adsorption

Dissolved organic solids

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readily degradable are aliphatic compounds (paraffins, alcohols, carboxylic acids),

Disadvantages can be:

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