Programme Objective Series (PROBES)

PROBES/10712007
DEVELOPMENT OF AOX STANDARDS
FOR
LARGE SCALE PULP AND PAPER
INDUSTRIES
CENTRAL POLLUTION CONTROL BOARD
MINISTRY OF ENVIRONMENT & FORESTS
Website: www.cpcb.nic.in e-mail: cpcb@nic.in
PROGRAMME OBJECTIVE SERIES
PROBES/10712007
DEVELOPMENT OF AOX STANDARDS
FOR
LARGE SCALE PULP AND PAPER
INDUSTRIES
..
~
CENTRAL POLLUTION CONTROL BOARD
MINISTRY OF ENVIRONMENT & FORESTS
e-mail: epeb@nic.in Website: www.epeb.nie.in
April 2007
CPCB, 200 Copies, 2007
Published By : Dr. B. Sengupta, Member Secretary, Central Pollution Control Board, Delhi - 32
Printing Supervision & Layout: P.K. Mahendru and Anamika Sagar.
Composing, Laser Typesetting & Cover Page Design: Suresh Chander Sharma
Printed at: DSIDC, New Delhi - 110 020.

......

a[jXeQ)
r. +no QI\3?{iCf)'!,
Wei
. M. MAUSKAR, lAS
hartman
FOREWORD
Fl<l?fUl
em "flTfC).'i)
<RUT l=j-?fT(>f[l
Central Pollution Control Board
(A Govt of India Organisation)
Ministry of Environment & Forests
Phone: 22304948/22307233
The release of the Halogenated Organic Compounds in the
environment is increasingly becoming a matter of concern due to their
carcinogenic/toxic effects. Most of these compounds are adsorbable and the
level of their presence in wastewater is assessed in terms of the parameter
'Adsorbable Organic Halides' (AOX). The formation of these compounds is
traceable to the use of Chlorine and chlorinated compounds in the various
industrial processes including the bleaching process in the pulp and paper
industries. The pulp and paper industries also being one of the major
consumers of Chlorine and its compounds, need priority attention in the
context of controlling AOX discharges in their effluents. The Central
Pollution Control board has, therefore undertaken a project for evaluation of
the various bleaching techniques used in the Pulp and Paper industries and
their relative suitability with respect to the minimum discharges of AOX in
tl:e effluents.
The present Report covers, a brief description of the pulp bleaching
process and its environmental impact, cleaner technologies for the reduction
of AOX discharges. details and findings of the studies conducted in the nine
pulp and paper units selected for this purpose, and the recommended
discharge limits for AOX.
The able execution of the project by Central Pulp & paper Research
Institute, Saharanpur, is gratefully ackno .'!edr:ed
We hope that the document would be useful to the pulp and paper
industries and all those concerned directly or indirectly with the
management of the Halogenated Organic Compounds.
c9.:- :)
(J.M. MAUS"KAR)
09 April, 2007
'Parivesh Shawan' C.B.D-cum-Oflice Complex, East Arjun Nagar, Delhi-110 032
Fax: 22304948/22307078 email: cpcb@alpha.nic.in
Website: http://www.cpcbnlc.in
Development of AOX Standards for Large Scale Pulp and Paper Industries
Project Team
Dr. B. Sengupta,
Member Secretary
MIs Central Pulp & Paper Research
Institute, Saharanpur
Mr. P. M. Ansari,
Additional Director
Dr. R. S. Mahawar,
Additional Director
Mr. H. K. Karforma,
Senior Environmental Engineer
Mr. S. K. Gupta,
Environmental Engineer
Mrs. V. Hima Jwala, Senior Research
Fellow
Overall guidance
Project execution
Project coordination
Report revision, finalization and editing
Project coordination
Project coordination and follow-up
Project coordination and follow-up
PREFACE
Bleach plant effluents from pulp & paper industries are known to exhibit toxicity to
aquatic life. The toxicity is mainly due to discharge of Halogenated Organic Compounds
formed during bleaching of pulp with chlorine based chemicals particularly molecular
chlorine. The increased environmental pressures including the control of the release of
carcinogenic compounds require the paper industries to adopt cleaner technologies
such as the Elemental Chlorine Free bleaching techniques (ECF) and Total Chlorine
Free (TCF) bleaching techniques for reduction of chlorinated organic compounds. Most
of the chlorinated organic compounds that are carcinogenic, are adsorbable and hence
the discharge of AOX needs to be controlled.
Looking into the problems and limitations of the Indian pulp & paper industries in
adoption or up-gradation of their technologies, the Central Pollution Control Board has
undertaken a project on "Development of AOX Standards for Large Scale Pulp & Paper
Industries" with an objective to assess the status of the technologies and permissible
levels of AOX in effluents in respect of the large scale pulp &paper industries.
The studies were conducted in nine selected pulp & paper industries to collect reliable
information about level of AOX generation. The studies conducted have provided useful
information on the status of the technologies and the levels of AOX discharges in the
large-scale pulp and paper industries.
1.0
2.0
2.1
2.2
2.3
2.3.1
2.3.2
2.3.3
2.4
3.0
4.0
4.1
4.2
4.3
4.4
4.5
4.6
5.0
6.0
6.1
6.2
6.2.1
6.2.2
6.2.3
6.2.4
6.2.5
6.2.6
7.0
7.1
7.2
7.3
8.0
8.1
8.2
8.3
8.4
9.0
10.0
11.0
CONTENTS
INTRODUCTION
PULP BLEACHING AND ITS ENVIRONMENTAL IMPACTS
Bleaching chemicals and Bleaching sequences
Formation of chlorinated compounds
Toxic properties of chloro-compounds
Chlorophenolics
Polychlorinated Dioxins & Furans
Carcinogenic and Mutagenic compounds
Biological effects of Bleach plant effluents
KAPPA NO. AND ITS RELATION TO PULP BLEACHING
CLEANER TECHNOLOGIES FOR AOX REDUCTION
Technologies for Kappa no. reduction
Extended Delignification
Improved Pulp Washing
Oxygen Delignification
Chlorine Dioxide substitution
Oxidative alkali extraction bleaching
NATIONAL/INTERNATIONAL LIMITS FOR AOX DISCHARGES
OBJECTIVE &SCOPE OF THE PROJECT
Criteria for Selection of industries
Methodology
Preliminary Survey of the Selected industries
Identification of Sampling Points
Analysis of samples
Evaluation of Pulp Washing Efficiency
Measurement of AOX
Measurement of Effluent flow rates
INDEPTH STUDIES IN SELECTED INDUSTRIES
Writing & Printing paper manufacturing industries
Newsprint Paper Industries
Rayon Grade Pulp Industries
GENERAL OBSERVATIONS
Writing and Printing Grade Paper Industries
Newsprint Industries
Rayon Grade Pulp Industries
Effluent Treatment Plants
CONCLUSIONS
RECOMMENDATIONS
FINALIZATION AND NOTIFICATION OF AOX STANDARDS
Page No.
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1.0 INTRODUCTION
The increasing environmental pressures and changing customer preferences in
all spheres of life has made it essential that the bleaching techniques adopted by
Indian paper industry are also critically evaluated to control and monitor the
discharges of chlorinated organics. It is already known that discharge of
chlorinated organic compounds through effluents ar.d end products from pulp &
paper industries have adverse effect on fauna ana flora. The environmental
hazards of bleach plant effluent result from the use of chlorine containing bleach
chemicals especially molecular chlorine. The developed countries specially
Scandinavian countries; Canada and USA have slowly eliminated the use of
molecular chlorine over a period of last two decades and now moving towards
total chlorine free bleaching (TCF) techniques in a phased manner. The Indian
paper industry, which primarily utilises about 20% wood, 60%nonwood and about
20% waste paper, mostly bleach the pulp by chemicals like molecular chlorine,
calcium hypochlorite which are responsible for the formation of chiaro
compounds. The quantity of chlorine required for bleaching one tonne of pulp
ranges from 50Kg - 200 Kg. The total available chlorine requirement for different
raw materials is 6-8% in case of Eucalyptus, 8-10% for Bamboo and 8-10% for
Bagasse. It is therefore essential to make an assessment of the existing AOX
levels in the effluents and technologies that are suitable for achieving the AOX
discharge limits that are acceptable in the Indian Pulp and Paper industries. The
present document covers a brief description of the pulp bleaching processes and
its environmental impacts, cleaner technologies for the reduction of AOX
discharges, details of the studies conducted for the characterization of waste
streams in large scale pulp and paper manufacturing industries, and the findings,
and the recommended discharge limits for AOX.
2.0 PULP BLEACHING AND ITS ENVIRONMENTAL IMPACTS
2.1 Bleaching chemicals and Bleaching sequences
The bleaching chemicals are applied in multistage sequences wherein chemicals
are mixed with pulp and allowed a period of retention for bleaching reactions to
complete. The spent chemicals and dissolved impurities are removed by washing
of pulp. The various bleaching chemicals used in pulp bleaching are given in
Table-1. The bleaching sequences can conveniently be broken into two segments
namely, Delignification Partial Sequence and Brightening Partial Sequence as
given in Table - 2. The delignification partial sequence has the principle function of
lignin removal and the brightening partial sequence increases the brightness.
Table - 1 : Chemicals Used in Pulp Bleaching
Oxidants
Chlorine
Form
Gas
Advantages
Effective, economical
delignification. Good
practical removal
.Disadvantages
Can cause loss of pulp
strength if used
improperly.
Organochlorine
formation.
Hypochlorite
Ca(OCI
2),
NaOCI Easy to make and use
solution -40 gpl
as CI
2
Can cause loss of pulp
strength if used
improperly. Cholorform
formation
Chlorinedioxide 7-10 gpl CI0
2
solution in water
Achieves high Must be made on site.
brightness without pulp I Expensive. Some
degradation. Good I organochlorine
particle removal. I formation
Oxygen Gas used with
NaOH solution
Low chemical cost.
Provides chloride-free
effluent from recovery
Used in large amounts
requires expensive
equipment. Can cause
loss of pulp strength.
-------------.- "'--". ----------_._-- ._._.-._-_._---. - " - - " ~ ' - - - " - - ' - " - ' ".- " , _.,_ _-_ ,., .._---,--"-, .-_--"_"_'.--'. -- -.-,-_.-.-_._--_._- -_ " .. - ~ - -
Hydrogen
peroxide
Ozone
Reductant
I Hydrosulfite
(for mechanical
pulps only)
Alkali Sodium
Hydroxide
2-5% solution
Gas in low
concentration in
oxygen
Solution of
Na
2
S
2
0 4 or
made onsite from
NaBH
4
solution
plus S02)
5-10% NaOH
solution
Easy to use low capital
cost
Effective, provides
chloride-free effluent
for recovery
Easy to use. Low
capital cost.
Effective and
economical
2
Expensive, poor
particle bleaching.
Decomposes readily.
Limited brightness gain
Darkens pulp
Delignification Partial
Sequences
CE
CDE
D-CE
CEO
OCE
Table ~ 2 : Bleaching Sequences
Brightening Partial
Sequences
H
o
HD
HED
HOED
OED
DEPD
C - Chlorine,
D - Chlorine dioxide,
P - Hydrogen peroxide
E -
-
H -
Extraction with sodium hydroxide
Oxygen,
Hypochlorite.
The traditional mode of delignification uses chlorine followed by extraction and
hypochlorite treatment. Oxygen is another effective delignifying agent which is
widely used to enhance the extraction stage and it is being used in advance of
chlorine in order to reduce the carryover of organic matter to bleach plant. The
hypochlorite and C102 are mainly used for brightening of pulp. CEH is the
traditional sequence used by the Indian paper industries to produce bleached
pulp. But with increasing environmental pressure to reduce or eliminate organo-
chlorine, the use of chlorine is decreasing rapidly with oxygen, peroxide and
Cl02 providing more environmentally compatible bleaching.
2.2 Formation of chlorinated compounds
The conventional kraft wood pulp bleaching which includes chlorination typically
produces 5.4-9.0 kg of chlorinated organic materials per ton of bleached pulp.
Approximately 300 different compounds in bleached pulp industries effluents
have been identified and about 200 of these are chlorinated organic compounds.
The types of chlorinated compounds found in Pulp bleaching effluents are listed
in table-3:
3
Table - 3: Chlorinated compounds found in Pulp Bleaching Effluents
Type
.-...-._--_..._.._--_.._- " "-" .._-_._- .-... __.... -.-.-.- .. ----_....-
Chlorinated acids
Chlorinated phenolics
Chlorinated aldehydes, Ketones
and lactones
Chlorinated hydrocarbons
Chlorinated others
High molecular weight materials
...._---- "-"". ' ~ - " - " " ' - - " " " ' - " - ~ - ' - - " - - " ' " , ~ , .._.._.
-- " - ..- __ -..
No. of Species Amounts
____ . _. __...0'_'.__.-- "_ . __. ~ .. _
40 upto 500g/t pulp
40 upto 100g/t pulp
45
45
20
upto 4 kg. Cllt pulp
It is well established that a series of chlarophenols are formed during bleaching
process. The nature and extent of formation of chloro-organics is determined
primarily by the residual lignin content in the pulp and the type of bleaching
chemicals employed. The discharges of chlorinated organic compounds in
paper industries effluents have long been known to exhibit acute, chronic and
some mutagenic toxicity to aquatic life. Studies conducted in developed countries
reveal that the low molecular weight chlorinated compounds are the major
contributors to toxicity and mutagenicity. Most of the chlorine is otherwise bonded
with high molecular weight organic compounds, which are stable against
biodegradation, and contributes little to toxicity and mutagenicity. However, the
past studies conducted indicate that these high molecular weight chloro
compounds might also be broken down to smaller more biologically active
compounds and can cause long-term toxic' effects to the recipients. The relative
contribution of the various chlorophenols to AOX is shown in Figure-1.
2.3 Toxic properties of chloro-compounds
2.3.1 Chlorophenolics
The Chlorinated compounds present in the alkali extraction bleach effluent are
found to be more toxic and contribute more than 90% of acute toxicity. The chloro
compounds like trichlorophenol, tri and tetra chloroguaiacols in particular may
accumulate in fish and are responsible for acute toxicity.
2.3.2 Polychlorinated Dioxins & Furans
Among the chlorinated phenolics, the dioxins & dibenzofurans are the groups of
chlorophenoles found to have toxic effects. The prominent among the dioxins
are 2,3,7,8 tetra chloro dibenzo dioxin (TCDD) and 2,3,7,8 tetra chloro dibenzo
furan (TCDF). Dioxins are highly Iypophyllic and bioaccumulative compounds.
Such compounds are formed when unchlorinated dibenzo dioxin (DBD) &
dibenzo furan (DBF) present in unbleached pulp are chlorinated in chlorination
stage. The oil based pulp industry additives particularly brown stock defoamers
4
have been identified as potential sources of such compounds. Laboratory studies
indicate a sharp increase in quantity of PCDD and PCOF when elemental
chlorine consumption is increased beyond 10-15 kg Cl2/tonne of pulp. The
dioxins are quite resistant to degradation and have an elevated potential for
bioaccumulation. The toxic effects of dioxins and the risk doses specified in
different countries/agencies are given below in table-4. TCDD has been reported
to cause cancer in rats but its effect on humans has been the centre of much
debate and is still yet to be established.
Table - 4 : Toxic Effects and Risk doses of Dioxins
.----- --.--J.---.--- ---.--..---.- ---.--.-.-- ".
Risk dose* Toxic I health effect
--------3-..--- -. -- -_._- -.-
6.4 x 10' Cancer
-.-_..
1.0 Cancer/reproductive
.---.----=2------..- ..--.....------.---..--..-..
5.7 x 10' Cancer
.._---_..__...-_.- .... _.'--- ..._----_.- ....._._--_._._._-
Agency I Country
.-
EPA
..
FDA
_.__.
* Picograms of 2,3,7,8 TCDD/kg of body weight/day
AOX 100%
I

Relatively Hydorphilic
Includes Compounds
Which can Easily Be
Hydrolysed or Metabolised
(e.g. Tricholoroacetic acid)
Relatively Lipophilic
(Fat Soluble).
Potentially Toxic.
Potentially
Bio-accumulable

Low MW Material

High MW Material
Relatively Hydrophilic (Water
Soluble). Mainly Non-aromatic,
Does not Permeate Cell Walls.
1-10% Chlorine By Weight
Low P
ow>3
Highly Lypophyllic
Bio-accumulative.
(e.g. Dioxin - 44% Chlorine By weight)
Fig.i. Relative contribution of Chlorophenolic Compounds to AOX
5
~ . 3 . 3 Carcinogenic and Mutagenic compounds
Bleach plant effluents contain chloroform and carbon tetra chloride which have
been classified as carcinogens. The hypo-chlorite stage is the major producer of
chloroform. The various chlorinated benzenes, phenols, epoxystearic acid and
dichloromethane present have also been classified as suspected carcinogens.
Some of the chlorinated compounds formed in Cl
2-stage
have been identified as
strong mutagens. However, a very limited information regarding the tendency of
mutagens to bioaccumulation is available.
2.4 Biological effects of Bleach plant effluents
It is well known that bleach plant effluents are toxic to fish and other organisms
mainly due to the presence of chloro-compounds. The biological effects of
chloro-compounds on fish as characterized in the laboratory studies are:
Acute toxicity:
Egg mortality
Percentage of fertilized egg.
Acute toxicity to newly hatched fry.
Late effects: Survival and stress tolerance of fry from exposed parents.
Effects on behavior: Response to rotary flow.
Physiological and Histological sublethal effects:
Growth rate
Histological changes in lever.
Occurrence of parasitic in gills of flounder
Bioaccumulation:
Effect on primary production in natural mixed phytoplankton populations.
Genotoxic effects:
Mutagenic effects
Carcinogenic effects.
3.0 KAPPA NO. AND ITS RELATION TO PULP BLEACHING
The Kappa no. is an index used by the pulp and paper industry to express the
lignin content of a pulp. Lignin is responsible for the brown coloration of paper,
and is removed by bleaching. Therefore, the lignin content must be well known,
so that only a minimum amount of bleach is used. Higher the lignin content more
is the kappa no. The pulp having high lignin content termed as hard cooked pulp
and the pulp with low lignin content is termed as soft cooked pulp. The hard
6
cooked pulp required more bleaching chemicals to attain particular brightness
compared to soft cooked pulp.
4.0 CLEANER TECHNOLOGIES FOR AOX REDUCTION
4.1 Technologies for Kappa no. reduction
Pulp & paper industries have incorporated various measures to reduce the
kappa no. and also to minimize the carry over of organic matter along with
pulp as it governs the bleach chemical demand during the bleaching process.
Some of these measures include oxygen delignification, extended deliqruflcation,
improved pulp washing, substitution of elemental chlorine with chlorine
dioxide, oxidative alkali extraction stage bleaching etc.
4.2 Extended Delignification
The pulp and paper industries normally use kraft process in batch or continuous
digesters to remove the lignin as much as possible during pulping of wood based
fibrous raw material but the process has limitation that the wood based fibrous
raw material can not be delignified to a low kappa number .Since the kappa
number is the main factor which governs the demand of chemicals for bleaching
of the pulp the process was modified to achieve maximum possible delignification
during cooking of raw materials and now most of the industries in developed
countries are employing RDH, modified continuous cooking, super batch
process etc tc reduce the kappa number of the unbleached pulp. Modified
pulping processes are energy efficient, require less chemicals for cooking of raw
materials and produce the pulp of low kappa number with better strength
properties as compared to conventional pulping processes. However, the high
capital investment and high level of operation restrict the adoption of these
technologies in Indian pulp & paper industries. Agro based pulp and paper
industries normally use soda pulping process.
4.3 Improved Pulp Washing
The pulp mill section of paper industries norrna'ly use brown stock washers for
extraction of black liquor and for washing of pulp. The washing efficiency of these
washers depend on nature and quality of fibrous raw materials. Most of the small
industries use brown stock washers for washing of pulp produced from agro
residues but the efficiency of these washers are not satisfactory as high carry
over of black liquor along with pulp was observed in agro based industries. Since
the pulp from agro residues is difficult to dewater so the industries can use the
modified washing systems such as belt filter press, double wire washer etc, to
minimize the carry over of the black liquor with pulp entering the bleachinq
section.
7
4.4 Oxygen Delignification
Oxygen delignification is a well established technology and most of the pulp mill
abroad are using this process to reduce the kappa number of pulp before
bleaching stage. Single stage oxygen pre bleaching of the pulp reduces the pulp
kappa number by 50-60 % and two stage oxygen pre-bleachinq reduces the
pulp kappa number by 80%.
The process is used in large pulp & paper industries in the developed countries.
Indian paper industries have limitations in adopting the process due to high
capital investments involved and low scale of their operation. The process needs
to develop an economically viable oxygen pressure vessel for low scale of
operation as the capacity of small scale pulp mills in the Country varies from 5-
100 ton /day or upgrade capacities of their plants for achieving viability in using
these processes.
4.5 Chlorine Dioxide Substitution
The elemental chlorine is the major source of toxic chlorinated phenolics and
dioxins compounds and contribute more than 70% of total AOX . The chlorine
dioxide, because of its high oxidation potential, decreases the formation of
chlorinated phenolics, colour, AOX, dioxins etc in addition to improved quality of
pulp. Most of the pulp mill in developed countries have substituted or replaced
elemental chlorine with chlorine dioxide. The large pulp and paper industries in
this Country have now started the use of chlorine dioxide also.
4.6 Oxidative alkali extraction bleaching
The addition of small amount of oxygen or peroxide in alkali extraction stage
improves the quality of bleach plant effluent by reducing colour & AOX. Most of
the large paper industries in India have already started the use of oxygen or
hydrogen peroxide in alkali extraction stage. The adoption of modified pulping
and bleaching processes in pulp mill developed Countries has resulted in an
increased recycling or reuse of the waste water to the internal process and
efforts are being continued to achieve zero discharge. These industries are
however required to operate the pulp mill under controlled conditions to reduce
the kappa number and also to modify their pulp washing system to minimize the
carry over of black liquor along with pulp in order to reduce the discharge of
chlorinated phenolics compounds.
5.0 NATIONAL/INTERNATIONAL LIMITS FOR AOX DISCHARGES
Most of the pulp and paper industries in developed countries have adopted new
pulping and bleaching technologies in order to reduce the generation of chloro
organics. Environmental Protection Agency (EPA) has issued the guidelines for
8
discharge of AOX, Dioxins and 12 numbers of other chlorinated organic
compounds in the effluents. In India in the year 1992, Ministry of Environment &
Forests (MoEF) has notified the discharge limits for chloro-organic compounds
as Total Organic Chlorine (TOCI) -2kg/tonne of paper for large pulp and paper
industries. The discharge limits for organo chlorine in some of the developed
countries are given in Table-5.
Table - 5: Discharge Limits Of AOX in Different Countries
COUNTRY Limits, Kg/tonne of paper MODE
--
_.-
Sweden <1.0 TOCI
Canada <1.5 AOX
. _ - ~ - _ . _ . _ - - ~
Germany <1.0 AOX
-
._._._---_._-_.
India 2.0 TOCI
--
6.0 OBJECTIVE &SCOPE OF THE PROJECT
The main objective of the study was to assess! evaluate and obtain the data on
the existing levels of AOX in the effluents from Indian pulp & paper industries
producing different grades of paper namely, writing & printing, newsprint and
rayon grade pulp using diverse raw materials, and different pulping & bleaching
processes. This scope include collection of effluent samples from the identified
sampling points to assess the levels of AOX generated & final discharge by
Indian pulp & paper industries producing a variety of end products.
6.1 Criteria for Selection of Industries
The paper industries were selected on the basis of raw materials used, bleaching
practice employed, size of the industries and the type of end products. The types
of paper industries selected for the study are:
(i) Writing & Printing grade of paper;
(ii) Rayon Grade pulp industries; and
(iii) Newsprint grade of paper.
6.2 Methodology
6'.2.1 Preliminary Survey of the Selected industries
The preliminary survey of selected pulp and paper industries was conducted
through questionnaire requesting the industries to furnish detailed information
9
related to the size of industry, usage of raw materials, bleaching process
employed, end product, existing effluent treatment facilities, disposal of treated
effluent etc. The information thus provided was verified and further updated
during the visit to selected pulp and paper industries.
6.2.2 Identification of Sampling Points
The sampling points selected are:
(i) Combined bleach plant effluents
(ii) Influent to ETP I Primary Clarifier
(iii) Overflow of primary clarifier, and
(iv) Final treated effluent
6.2.3 Analysis of samples
The selected pulp and paper industries were visited for indepth study. Two visits
were performed in each of the selected units for conducting the in-depth studies
in order to generate representative and realistic data based information on AOX
level in these category of pulp and paper industries. The sampling and flow
measurement were done from identified points for 24 hours composite sampling
in order to collect the representative samples. The composite samples collected
were preserved and transported for further analysis of the following parameters:
(i) pH
(ii) Suspended Solids
(iii) Chemical Oxygen Demand
(iv) Biological Oxygen Demand, and
(v) Adsorbable Organic Halides (AOX)
6.2.4 Evaluation of Pulp Washing Efficiency
The efficiency of existing pulp washing system in selected paper industries was
also evaluated by estimation of carryover of black liquor COD along with pulp
going to the bleach plant.
6.2.5 Measurement of AOX
The preserved effluent samples (composite) collected from the industries were
analysed for AOX as per DIN method - 38409H (Flask Procedure) by using DX-
20 DOHRMANN AOX analyser.
6.2.6 Measurement of Effluent flow rates
The flow rates of effluent generated were measured at different time intervals
during the sampling period by using measuring devices such as V notch,
10
rectangular notch existing in the drain channels and also by using the float
velocity method.
7.0 INDEPTH STUDIES IN SELECTED INDUSTRIES
7.1 Writing & Printing paper manufacturing industries
Unit-1
Details of the industry and findings of the study are given in Table 6
The industry is mainly based on eucalyptus, bamboo and small amount of pine
as the raw materials to produce writing & printing, and Kraft packaging grade
papers. The production of these two grades of papers was 110 tpd and 45 tpd
respectively. The Kappa no. of unbleached kraft pulp produced ranged 26-30,
and it is being used both for writing & printing grade and also for unbleached kraft
paper. For the production of writing and printing grade papers the pulp is being
bleached by CEpHH bleaching sequence to a targeted brightness level of 75%
ISO. The total AOX load generated is 3.58 Kg/t product (555 Kg/day) which is
reduced to 1.23 Kg/t product (190 kg/day) in the final effluent discharge The
over-all reduction in AOX in ETP is 65.77%.
Table - 6 : Details and findings of study in Unit-1
1.
2.
3.
4.
5.
6.
7.
8.
Installed capacity ,T / Year
Raw materials
Paper production, T/Day
a. Total
b. Kraft
c. W & P Grade
Pulping process
Kappa no. of unbleached pulp
Bleaching sequence
Bleached pulp brightness,% ISO
Characteristics of waste water
(Influent to ETP)
a. Flow, M3 IDay
b. pH
c. Suspended solids, mgll
d. Suspended solids, Kgl Day
11
- 46,000
- Bamboo, Eucalyptus, Pine
- 155
- 45
- 110
- Sulphate
- 26 - 30
- CEpHH
- 84.0
- 29290
- 7.2
- 1080
- 31633
Contd ....
e. Suspended solids, Kg/T Paper - 204
f. COD, mg/I - 1313
g. COD, Kg/Day - 38458
h. COD, Kg/ T Paper - 248
i. AOX, mg/I - 18.94
j. AOX., Kg/Day - 555
k. AOX , Kg/ T Paper - 3.58
9. Characteristics of treated waste water
a. Flow, M3 /Day - 29290
b. pH - 7.4
c. Suspended solids, mg/I - 90
d. Suspended solids, Kg/ Day
-
2636
e. Suspended solids, KglT Paper - 17
f. COD, mg/I - 269
g. COD, Kg/Day - 7879
h. COD, Kg/ T Paper - 51
i. AOX, mg/I - 6.48
j. AOX, Kg/Day - 190
k. AOX , Kg/ T Paper - 1.22
10. Efficiency of ETP
a. Reduction in SS ,% - 91.67
b. Reduction in COD,% - 79.51
c. Reduction in AOX,% - 65.78
--------------------------------------------------------------------------------------------------------
Unit-2
Details of the industry and findings of the study are given in Table 7.
The industry is manufacturing writing &printing paper, kraft paper &triplex board
from bamboo (50-60%) and mixed hardwoods (40-50%). The unbleached pulp
of Kappa 25 + 2 is used both for writing and printing grade, and also for kraft
packaging & triplex boards. The industry produces 156 tlday writing and printing
paper against a total production of 165 t/day. In case of the production of writing
and printing grade papers, the pulp is bleached by CEHH/CEHHP bleaching
sequence to a brightness level of 78% ISO. The total AOX load generated is
5.03 kg/t of paper (831 kg/day) which is reduced to 2.50 kg/t of paper production
(413 kg/day) after secondary treatment. The overall reduction in AOX in the ETP
is 50.30%.
12
Unit-3
Details of the industry and findings of the study are given in Table 8.
The industry is producing fine variety of paper from bamboo (90%) and
Eucalyptus (10%). The production of paper during sampling period was 252 tpd.
The pulp having kappa nO.20-22 is bleached by C/O EoHHO bleaching sequence
to a brightness level of 82-84% ISO. The total AOX load generated is 4.49 kg/t
paper productlon'(t tSt kg/day), which is teduced to 2.40 kg/t (603 kg/day) paper
production after secondary treatment. The overall reduction in AOX during in the
ETP is 46.72%.
Unit-4
Details of the industry and findings of the study are given in Table 9.
This industry is mainly based on bagasse, bamboo, and eucalyptus in addition to
little proportion of imported pulp. Presently the industry is producing around
63t/day rayon grade pulp, 110 t/day writing & printing paper from eucalyptus and
bamboo, and about 110t/day writing and printing paper from 90% bagasse
bleached pulp and 10% imported bleached pulp. Rayon grade pulp (kappa
no.16) is bleached by CEHD - S02 bleaching sequence to a brightness level of
87% ISO, while Eucalyptus & bamboo pulp of kappa no 18-20 is bleached by
CEHHO-S02 bleaching sequence to a brightness level of 83% ISO and bagasse
pulp of kappa 12-13 by C/OEoD bleaching sequence to brightness level of 85%
ISO. The total AOX load generated is 2.32 kg/t production (662 kg/day) which is
reduced to 1.37 kg/t production (390 kg/day) after secondary treatment and final
discharge. The overall reduction of AOX in the ETP is 41%.
Table - 7: Details and findings of study in Unit-2
1.
2.
3.
4.
5.
Installed capacity, T/ Year
Raw materials
Paper production, T / Day
a. Total
b. Kraft
c. W & P Grade
PUlping process
Kappa no of unbleached pulp
13
- 70,000
- Bamboo (50-60%)
Mixed Hardwoods(40-50%)
- 165
- 9-10
- 156
- Sulphate pulping
- 22 - 28
Contd ....
6. Bleaching sequence - CEHHp
7. Bleached pulp brightness, % ISO - 85.0
8. Characteristics of waste water
(Irifluent to ETP)
a. Flow, M3 /Day
- 44110
b. pH - 8.64
c. Suspended solids, mg/I - 3000
d. Suspended solids, Kg/ Day - 132330
e. Suspended solids, KglT Paper - 802
f. COD, mgtl - 1277
g. COD, Kg/Day - 56329
h. COD, Kg/ T Paper -
341
i. AOX, mg/I 18.83
J.
AOX, g/Day
- 831
k. AOX , Kg/ T Paper - 5.03
9. Characteristics of treated waste water
a. Flow, M3 /Day - 44110
b pH - 7.54
c. Suspended solids, mg/l - 260
d. Suspended solids, Kg/ Day - 11468
e. Suspended solids, Kg/T Paper - 70
f. COD, mgtl - 272
g. COD, Kg/Day - 11998
h. COD, Kg/ T Paper - 73
i. AOX, mg/I 9.36
j. AOX, Kg/Day 413
k. AOX , Kg/ T Paper - 2.50
10. Efficiency of ETP
a. Reduction in SS ,%
-
91.33
b. Reduction in COD, %
_.
78.70
c. Reduction in AOX, % - 50.30
-----------------------------------------------------------------------------------------------------------
14
Table - 8: Details and findings of the study in Unit - 3
1. Installed capacity, T/ Year - 1,00,000
2. Raw materials - Bamboo (90 %)
- Eucalyptus(10 %)
3. Paper production, T/Day
a. Total - 252
b. W & P Grade - 252
4. Pulping process - Sulphate
5. Kappa no of unbleached pulp - 20
6. Bleaching sequence - C/DEoHHD
7. Bleached pulp brightness,% ISO - 84.0
8. Characteristics of waste water
(Influent to ETP)
a. Flow, M3/Di::IY - 79200
b. pH - 7.6
c. Suspended solids, mg/I - 1017
d. Suspended solids, Kg/ Day - 80546
e. Suspended solids, KglT Paper - 320
f. COD, mg/ - 1177
g. COD, Kg/Day - 93218
h. COD, Kg/ T Paper - 370
i. AOX, mg/I 14.28
j. AOX, Kg/Day 1131
k. AOX I Kg/ T Paper - 4.49
9. Characteristics of treated waste water
a. Flow, M3 /Day - 79080
b. pH - 7.1
c. Suspended solids, mg/I - 235
d. Suspended solids, Kg/ Day - 18584
e. Suspended solids, KglT Paper
- 74
f. COD, mg/I - 291
g. COD, Kg/Day - 23012
h. COD, Kg/ T Paper
-
91
i. AOX, mg/I 7.62
j. AOX, Kg/Day 603
k. AOX , Kg/ T Paper - 2.40
10. Efficiency of ETP
a. Reduction in SS ,% - 76.89
b. Reduction in COD, %
- 75.28
c. Reduction in AOX, %
- 46.68
---------------------------------------------------------------------------------------_.._-----------------
15
Table9 : Details and findings of the study in Unit-4
1. Installed capacity,TlYear:
a. Total - 1,49,900
b. W&P Grade - 36,000 (Eucalyptus &bamboo)
82,500 (bagasse)
c. Rayon pulp - 31,200 (Eucalyptus)
2. Raw material - Bamboo, Eucalyptus & bagasse
3. Paper production, T/Day:
a. Total - 285
b. W & P Grade - 222
c. Rayon pulp - 63
4. Pulping process - Sulphate(Eucalyptus & bamboo)
Soda (bagasse)
5. Kappa no of unbleached pulp - 16 (Eucalyptus, RG)
13 (bagasse, W & P)
20 (Eucalyptus & bamboo, W & P)
6. Bleaching sequence - CEHD (RG)
- CEHH D/S02(E)
- C/ DEoD ( B)
7. Bleached pulp brightness,% ISO - 86 (Eucalyptus, RG)
80 (bagasse, W & P)
83 (Eucalyptus, W & P)
8. Characteristics of waste water (Influent to ETP)
a. Flow, M3/Day - 61440
b. pH - 6.6
c. Suspended solids, mgll - 370
d. Suspended solids, Kg/ Day - 22733
e. Suspended solids,Kg/T paper - 80
f. COD, mgll - 485
g. COD, Kg/Day - 29798
h. COD, Kg/ T Paper - 105
i. AOX, mgll - 10.77
j. AOX, Kg/Day - 662
k. AOX , Kg/ T Paper - 2.32
Contd....
16
9. Characteristics of treated waste water
a. Flow , M3 /Day - 61440
b. pH - 7.3
c. Suspended solids, mg/I - 240
d. Suspended solids, Kg/ Day - 14745
e. Suspended solids, KglT Paper - 52
f. COD, mg/I - 390
g. COD, Kg/Day - 23962
h. COD, Kg/ T Paper - 84
i. AOX, mg/I - 6.35
j. AOX, Kg/Day - 390
k. AOX , Kg/ T Paper - 1.37
10. Efficiency of ETP
a. Reduction in SS ,% - 35.14
b. Reduction in COD, % - 19.59
c. Reduction in AOX, % - 41.00
Unit-5
Details of the industry and findings of the study are given in Table 10
The industry has installed capacity of 300 tonnes/day of manufacturing high
quality bleached paper varieties. The main fibrous raw materials used are bamboo
and wood. The mill has employed cleaner technologies like RDH Pulping, Oxygen
Delignification with chlorine dioxide bleaching. The CDEoPD bleaching sequence
is used for bleaching of the pulp having Kappa No 15-17. The AOX level in effluent
before treatment is 1.92 Kg/tonne of paper while after treatment in ETP its level
comes down to 1.07 Kg/tonne of paper. The over-all reduction in AOX in the ETP
is 44%.
Details of the industry and findings of the study are given in Table 11.
The paper industry has installed capacity of 53868 t/year for manufacturing writing
& printing grade of paper. The main fibrous raw materials used for manufacturing
17
of quality paper are bamboo,wood,bagasse and grasses( Sabai,khar & Kai). The
industry has two pulping street, new pulp mill is used to produce wood pulp having
kappa nO.20-21. While the existing old pulp mill with eight nos. of digestors (32 m
3
each) is used to produce pulp of kappa nO.13-15 from bagasse & grasses. The
industry is practicing both conventional bleaching (CHH) for pulp of low kappa no.
pulp & CDEDD for wood pulp. The AOX level in effluent before treatment is 4.0
Kg/tonne of paper while after treatment in ETP its level comes down to 1.84
Kg/tonne. The over-all reduction in AOX in the ETP is 54%.
7.2 Newsprint Paper Industries
Unit-7
Details of the industry and findings of the study are given in Table 12
The industry is based on bagasse, Eucalyptus and imported Chemi Mechanical
Pulp (CMP) wood. During sampling period, the production of industry was 276
tid of newsprint and 253 tid of writing and printing paper. The chemical pulp ( CP)
produced from bagasse & Eucalyptus have Kappa 8-10 & 18-22 respectively.
The bagasse & Eucalyptus chemical pulps are bleached by CEH .& CEHH
bleaching sequences to the brightness level of 75 & 85% ISO respectively. The
CMP bagasse is bleached by hydrogen peroxide to brightness level of 65% ISO.
The newsprint fibre furnish is 40% bagasse CP, 40% bagasse Chemi Mechanical
Pulp ( CMP) & 20% imported CMP of wood pulp while fibre furnish for writing &
printing paper is 75% bagasse CP & 25% hardwood CP. The total AOX load
generated based on total production of newsprint together with writing &printing
paper is 1.79 kg/t(946 kg/day) production which is reduced to 0.80 kg/t produc
tion (424 kg/day) after secondary treatment. The above AOX level of 1.79 kg/t
product is the combined AOX generated from newsprint as well as from writing
and printing grades. Out of the total production about 10-12% is the imported
CMP wood which does not require any bleaching and about 20-22% is the
bagasse CMP where the bleaching done IS very mild with hydrogen peroxide and
there is no possibility of AOX generation. The AOX generation is mainly due to
the bleaching of CP of bagasse and wood. The overall reduction in AOX in the
ETP is 55.30%.
18
Table - 10 : Details and finding of the study in Unit - 5
---------------------------------------------------------------------------------------------------------------------
Exercise Exercise Av.Values
I II
-------------------------------------------------------------------------------.-------------------------------------
1. Installed capacity,TIY 90,000
2. Raw materials Bamboo and Hard wood
3. Writing & printing paper
production TID 281 332 307
4. Pulping process RDH (Sulphate)
5. Kappa No. of unbl.Pulp 15-17 15-17
6. Bleaching practice C/DEoPD
7. Bleached Pulp
Brightness,% ISO 86-88
8. Characteristics of combined waste water (influent to ETP)
- Flow m
3/d
26537 26878 26708 ,
-pH 8.4 7.96 8.18
- Suspended Solids,mg/l 1480 1620 1550
- Suspended Solids,kg/t paper 140 131 136
- COD,mg/l 1471 1645 1558
- COD,Kg/t paper 139 133 136
- AOX,mg/l 16.68 27.34 22.01
- AOX,kg/t paper 1.58 2.21 1.92
9. Characteristics of Primary clarifier outlet
-pH 7.30 7.44 7.37
- Suspended Solids,mg/l 160 290 225
- COD,mg/l 738 806 772
- AOX,mg/l 13.68 24.71 19.20
10. Characteristics of final discharge
-pH 7.75 7.66 7.71
- Suspended Solids,mg/l 120 180 150
- Suspended Solids,kg/t paper 11 15 13
- COD,mg/l 356 380 368
- COD,kg/t paper 34 31 33
- AOX,mg/l 11.10 13.29 12.20
- AOX,kg/t paper
1 05 1.08 1.07
11. Performance of ETP.
- Reduction in Suspended Solids,% 92 86 89
- Reduction in COD,% 76 77 77
- Reduction in AOX,%
34 51 44
12. Waste waterdischarge,m
3/t
paper 94 81 88
----------------------------------.---------------------------------------------------------------------------.-----
19
Table - 11 : Details and findings of the study in Unit - 6
Exercise
I
Exercise
II
Av.Values
------------------------------------------------------------------_._------------------_._---------------------------
1. Installed capacity,TIY 53868
2. Raw materials Wood,Bamboo, Bagasse &Grasses
3. Writing &printing paper
production,T/D 182 213 198
4. Pulping process Sulphate process
5. Kappa No. of unbl.Pulp
- Bamboo/wood 20-21
- Grasses/Bagasse 13-15
6. Bleaching practice
- Bamboo/wood C/DEDD
- Grasses/Bagasse CHH
7. Bleached Pulp Brightness. % ISO 78-86
8. Characteristics of combined waste water (influent to ETP)
- Flow m
3/d
44590 41340 42965 ,
-pH 6.7 7.4 7.05
- Suspended Solids,mgll 490 600 545
- Suspended Solids,kg/t paper 120 116 118
- COD,mg/1 687 782 735
- COD,Kg/t paper 168 152 160
- AOX,mg/1 18.17 18.30 18.24
- AOX,kg/t paper 4.45 3.55 4.00
9. Characteristics of Primary clarifier outlet
-pH 7.10 7.20 7.15
- Suspended Solids,mgll 130 140 135
- COD,mgll 503 539 521
-AOX,mg/1 14.98 12.77 13.88
10. Characteristics of final discharge
-pH 7.10 7.30 7.20
- Suspended Solids,mg/I 60 40 50
- Suspended Solids,kg/t paper 15 8 12
- COD,mg/1 144 164 154
- COD,kg/t paper 35 32 34
- AOX,mgll 8.86 7.77 8.32
- AOX,kg/t paper 2.17 1.51 1.84
11. Efficiency of ETP:
- Reduction in Suspended Solids, % 87 93 90
- Reduction in COD,% 79 79 79
- Reduction in AOX, % 51 57 54
12. Wastewater discharge,m
3/t
paper 245 194 220
- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - ~ - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - . - - - - - -
20
Table - 12 : Details and findings of the study in Unit-7
1. Installed capacity, T/ Year
a. Total - 2,00,000
b. Newsprint - 1,00,000 (Bagasse & imported wood pulp)
c. W & P Grade - 1,00,000(Eucalyptus& bagasse)
2. Raw materials - Bamboo,Eucalyptus,bagasse Imp. wood pulp
3. Paper production,T/Day:
a. Total - 529
b. Newsprint - 276
c. W & P Grade - 253
4. Pulping process - Sulphate (bagasse & Eucalyptus)
CMP(bagasse)
5. Kappa no of unbleached pulp - 20 ( Eucalyptus CP)
10 (bagasse CP)
6. Bleaching sequence - CEH(bagasse CP)
- CEHH(Euc.CP)
- P(bagasse CMP)
7. Bleached pulp brightness, - 85 ( Bagasse, CP)
% ISO - 65 (Bagasse, CMP)
- 75 (Eucalyptus, CP)
8. Characteristics of waste water (Influent to ETP)
a. Flow, M3 IDay - 69120
b. pH - 6.3
c. Suspended solids, mg/l - 740
d. Suspended solids, Kgl Day - 51149
e. Suspended solids,Kg/T paper - 97
f. COD, mg/I - 853
g. COD, Kg/Day - 58959
h. COD, Kg/ T paper - 112
i. AOX, mg/I - 13.69
j. AOX, Kg/Day - 946
k. AOX, Kg/ T paper - 1.79
21
9. Characteristics of treated waste water
10.
a. Flow, M3 /Day
b. pH
c. Suspended solids, mg/I
d. Suspended solids, Kg/ Day
e. Suspended solids,Kg/T paper
f. COD, mg/I
g. COD, Kg/Day
h. COD, Kg/ T paper
i. AOX, mg/I
j. AOX, Kg/Day
k. AOX , Kg/ T paper
Efficiency of ETP
a. Reduction in SS ,%
b. Reduction in COD,%
c. Reduction in AOX,%
Unit-8
- 68160
- 6.95
- 90
- 6134
- 12
- 181
- 12337
- 23
- 6.22
- 424
- 0.80
- 88.00
- 79.08
- 55.30
Details of the industry and findings of the study are given in Table 13.
This newsprint industry is based on hardwoods (Eucalyptus & Casurina) CMP,
CP of hardwoods and bamboo/reed (70:30) and the imported CP of softwood.
The newsprint production was 25Ot/d during sampling period. The CP produced
from hardwoods & bamboo/reed having Kappa no. around 20 is bleached by
CH/E sequence to a brightness level around 60-65% ISO. While CMP produced
from hardwoods is bleached by Hydrogen peroxide to brightness level around
55% ISO. The newsprint furnish is 70-75% CMP & 25-30% CP including
imported CPo The results indicated that generation of total AOX load is 0.53 kg/t
of newsprint (133 kg/day) which is reduced to 0.14 kg/t newsprint(36kg/d)
production after secondary treatment. The over-all reduction in AOX is about
72.79% during the treatment.
22
7.3 Rayon Grade Pulp Industries
Unit-9
Details of the industry and findings of the study are given in Table 14
This industry is mainly based on hardwoods (Eucalyptus and Casuarina) for
manufacturing about 110t /day rayon grade pulp. The unbleached pulp of kappa
no. 12.8 is bleached by CEoHEpD bleaching sequence to a brightness level of
85% ISO. The total AOX load generated is 0.69-kg/t pulp (76 kg/day), which is
reduced to 0.2 kg/t pulp (22 kg/day) after secondary treatment. The low level of
AOX generation is mainly due to low kappa of the unbleached pulp and use of
oxygen in extraction stage and chlorine dioxide in the final stage of bleaching.
The overall reduction in AOX level in the ETP is 71.05% .
8.0 GENERAL OBSERVATIONS
A summary of the findings of the generation/discharges of AOX, SS and COD in
different pulp and paper industries is given in Table 15.
8.1 Writing and Printing Grade Paper Industries
The summary results of the AOX generation and discharge in large scale writing
and printing paper industries are given in Table 16.
AOX generation in pulp & paper industries producing writing & printing grade
paper is found to be generally higher than newsprint and Rayon grade
manufacturing industries due to high Kappa no. of the pulp and excessive use of
molecular chlorine for achieving high brightness. Therefore, the generation of
AOX is comparatively higher for writing and printing paper where final brightness
is important. The levels of AOX measured in mill samples vary from 1.92 to 5.32
kg.AOX/t paper. In the industries, where chlorine dioxide and oxygen or peroxide
reinforced alkali extraction stage are used as bleaching agent, the generation of
AOX is on lower side compared to level of AOX generated using conventional
CEHH bleaching sequences.
23
Table - 13 : Details and findings of the study in Unit-8
1, Installed capacity,T/ Year - 1,00,000
2, Raw materials - Bamboo, Eucalyptus, Casurina,
Reed, &Imported wood pulp
3. Paper production, TlDay - 250
4. Pulping process - Sulphate (Eucalyptus,Casurina
bamboo and Reed)
- CMP (Eucalyptus and Casurina)
5. Kappa no of unbleached pulp - 20 (CP)
6. Bleaching sequence - CH/E(CP)
- P(CMP)
7, Bleached pulp brightness,% ISO - 63 (CP)
- 50 (CMP)
8, Characteristics of waste water (Influent to ETP)
a, Flow, M3 /Day - 27311
b. pH - 4.75
c. Suspended solids, mg/I - 540
d. Suspended solids, Kg/ Day - 14748
e, Suspended solids,Kg/T paper - 59
f. COD, mg/I - 668
g. COD, Kg/Day - 18244
h, COD, Kg/ T paper - 73
I. AOX, m g / ~ - 4.85
l AOX, Kg/Day - 133
k. AOX , Kg/ T paper - 0.53
9, Characteristics of treated waste water
a, Flow, M3 /Day - 27305
b. pH - 6.70
c. Suspended solids, mg/l - 136
d. Suspended solids, Kg/ Day - 3714
e. Suspended solids,Kg/T paper - 15
f. COD, mg/I - 353
g. COD, Kg/Day - 9639
h. COD, Kg/ T paper - 39
I. AOX, mg/I - 1.32
j. AOX, Kg/Day - 36
k. AOX , Kg/ T paper - 0.14
10 Efficiency of ETP
a. Reduction in SS ,% - 74.82
b. Reduction in COD,% - 47.16
c. Reduction in AOX,% - 72.79
--------------------------------------------------------------------------------------------------------------_.
24
Table - 14: Details and findings of the study in untt- 9
1. Installed capacity, T/ Year - 1,00,000
2. Raw materials - Eucalyptus & Casurina
3. Pulp production, T/Day - 110
4. Pulping process - Sulphate
5. Kappa no of unbleached pulp - 12.8
6. Bleaching sequence - CEoHEpD(CP)
7. Bleached pulp brightness,% ISO - 84
8. Characteristics of waste water (Influent to ETP)
a. Flow, M3 /Day - 18360
b. pH - 7.70
c. Suspended solids, mg/I - 227
d. Suspended solids, Kg/ Day - 4168
e. Suspended solids,Kg/T paper - 38
f. COD, mg/I - 653
g. COD, Kg/Day - 11989
h. COD I Kg/ T paper - 109
i. AOX, mg/l - 4.14
j. AOX, Kg/Day - 76
k. AOX , Kg/ T paper - 0.69
9. Characteristics of treated waste water
a. Flow, M3 /Day - 17208
b. pH - 7.30
c. Suspended solids, mgll - 50
d. Suspended solids, Kg/ Day - 860
e. Suspended solids,KglT paper - 7.82
f. COD, mg/I - 281
g. COD, Kg/Day - 4836
h. COD, Kg/ T paper - 44
i. AOX, mg/l 1.26
j. AOX, Kg/Day 22
k. AOX Kg/ T paper - 0.20
10. Efficiency of ETP
a. Reduction in SS ,% - 79.36
b. Reduction in COD,% - 59.67
c. Reduction in AOX, % - 71.48
- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - ~ - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -
25
Table - 15 : AOX Generation in different Pulp & Paper Industries
- ---_.--_.-----_._.._--_.- _._.... _.._--_...... _ . _ - - - , - - ~ - - - - ._-"--
s. Details of Paper Mill
Unit-1 Unit-2 ueu-a Unit-4 Unit-5 Unit-6 Unit-? Unit-8 Unit-9
No
--------
1 Paper production.Tzday
a, Total 155 165 252 285 307 198 529 250 110
b. Kraft 45 10
c. W & P Grade 110 156 -- 222 307 198 253
d. Rayon pulp --
-- -- 63 -- --
-- -- 110
e. Newsprint -- -- -- -- -- -- 276 250
2. Kappa no of unbleached pulp 26-30 22-28 20 16 (RG) 15-17 20- 10(B) 20 12
21(W)
10(B) 13-15(B) 20(E)
20(E)
3. Bleaching sequence CEpHH CEHH C/OE)H CEOH COEopO COEOO CEH(B) CHE CEoHEp
HO (RG) (W) 050
2
C/DEoO CHH(B) CEHH
(B) (W)
CEHHD P(B)
(W)
4. Bleached pulp brightness, 84 85 84 86 87 82 85 63 84
%150 80
83
5. Wastewater generated m
3
/T 18 267 314 2
A C
87 217 129 109 156 ,0
paper
26
S. Details of Paper Mill
Unit-1 Unit-2 Unit-3 Unit-4 Unit-5 Unit-6 Unit-7 Unit-8 Unit-9
No
6. AOX generated KglT paper
a. W & P grade 3.58 5.03 4.49 2.32 1.92 4.0
b. Rayon pulp -- --
-- -- -- -- -- -- 0.69
c. Newsprint -- --
.-
-- -- -- 1.79 0.53
7. Total AOX at final discharge 1.22 2.50 2.40 1.37 1.07 1.84 0.80 0.14 0.20
KglT paper
8. SS removal KglT paper
8.1 SS in untreated eff!. 204 802 320 80 136 118 97 59 38
8.2 SS in treated eff!. 17.0 80.0 74.0 52.0 13 12 12.0 15.0 8.0
9. COD removal KglT paper
9.1 COD in untreated eff!. 248 341 370 105 136 160 112 73 109
9.2 COD in treated eff!. 51.0 73.0 91.0 84.0 33 34 23.0 39.0 44.0
10. Efficiency of ETP
a. Reduction in TSS, % 91.67 91.33 76.89 35.14 89 90 88.0 74.82 79.36
b. Reduction in COD, % 79.51 78.70 75.28 19.59 77 79 79.10 47.16 59.67
c. Reduction in AOX, % 65.78 50.30 46.72 41.00 44 54 55.30 72.78 71.00
Note: Unit-1; Unit-2; Unit-3; Unit -4; Unit -5; Unit -6; Unit -7; Unit -8; Unit -9
CP- Chemical pulp; CMP :- Chemi-mechanical pulp;
C - Chlorination; E- Extraction; H- Hypochlorite
P - Hydrogen peroxide 0 - Chlorine dioxide;O - Oxygen
(RG)- Rayon grade;(W) Wood,(B) Bagasse,(E) Eucalyptus
27
8.2 Newsprint Paper Industries
The summary results of the AOX generation and discharge in newsprint paper
Industries are given in Table 17.
The level of AOX generation in case of chemi-mechanical pulp(CMP) bleached
with hydrogen peroxide, is negligible. Therefore, the AOX generation kg/t
newsprint mainly depends on the proportion of CMP and CP in the pulp. The
level of AOX measured in effluent samples collected from newsprint Industries is
less than 1.0 kg AOX/t paper. The pulp furnish used in these industries contains
major portion of mechanical pulp which is bleached with Hydrogen peroxide while
chemical pulp is given a mild bleaching action with chlorine based chemicals to
achieve 60% brightness level. The low degree of brightness in newsprint paper
and use of per-oxide in bleaching resulted in low level of AOX in the effluent.
8.3 Rayon Grade Pulp Industries
The summary results of the AOX generation and discharge in large scale Rayon
Grade Pulp Industries are given in Table 18.
The kappa of unbleached in rayon grade pulp is quite low i.e 12-16 which required
less quantity of the bleaching chemicals mainly chlorine and chlorine dioxide
resulting in low level of AOX in effluent. The AOX generation level ranges
between 1.48 to 1.68 kg/t of pulp.
8.4 Effluent Treatment Plants
(i)
(ii)
(iii)
Studies conducted in the industries reveal that biological effluent treatment
plants appears to be effective in removal of chlorinated organic
compounds. The maximum reduction in AOX i.e. about 70% is observed
in newsprint and rayon grade pulp industries while in writing and printing
paper industries, the reduction in AOX varies from 41 to 55 %. The high
reduction in AOX in newsprint and rayon grade pulp industries may be
because of low level of AOX in combined waste water and other reasons
may be perhaps because of low molecular weight AOX compounds.
There is a wide variation in quantity of wastewater discharged per tonne of
paper. The wastewater quality varies from industry to industry depending
upon the raw materials used and quality of end product. The lowest figures
of 109-130 m
3
/t were observed in newsprint followed by 155 m
3
/t in rayon
grade pulp and 190-315 m
3
/t in writing and printing paper industries.
The generation and discharge of suspended solids in wastewaters also
vary from industry to industry and also from product to product. The
28
reduction in SS during external treatment (ETP) observed varies from 35
to 92%.
(iv) The generation and discharge of COD measured also vary from industry
to industry depending on end product. The reductions in COD observed
after secondary treatment varied from 47 to 80 % except in Unit-4, where
COD reduction measured was only 20 % which may be because of
unstabilization of new bagasse based pulp industries at the time of sample
collection.
(v) The industries which have accomplished the modernization of bleach plant
operation by inducting the chlorine dioxide, and oxidative alkali extraction
stage with oxygen and hydrogen peroxide certainly has the reduced AOX
discharges.
Table - 16 : AOX generation ana mscnarqe in large scale Writing & Printing paper
Industries
-_._._._-_._-"-_._--- ..... ,,--_._._-------_._--_._.._ - - - - - ~ - - - - - - -
s. Parameters Unit 1 Unit 2 Unit 3 Unit 5 Unit 6
No
- - . ~ - - _ ... --- .
______~ _____~ , _ 4.'_, .. _. ___ _______' " _ . ~ ~ _______,, _____. _______
1. Raw materials Bamboo, Bamboo & Bamboo & Bamboo & Bamboo,
Pine & wood Eucalpytus Wood wood
Eucalyptus (Mixed grasses &
hardwood) Bagasse
2. Pulping process Sulphate Sulphate SUlphate Sulphate Sulphate
(RDH)
3. Pulp Kappa No. 26-30 22-28 20 15-17 20-21
4. Oxygen delignification No No No Yes No
5. Bleaching sequence CEoHH CEHHP C/DEoHHD C/DEopD C/DEDDCH
H
6. Total Paper
Production, tlday
a. Writing & Printing 110 156 252 307 198
b. Others 45 10
7. Total CI
2
Applied % 10.5 16.2 9.45 4.6 9.5+14.0
8. Total Elemental CI
2,%
6.0 7.70 5.50 3.5 6.0+5.0
9. Chlorine dioxide, % 0.25 1.10 3.5
10. AOX content, mgll
a. Influent 18.94 18.83 14.28 2201 18.24
b. Effluent (Final) 6.48 9.36 7.62 12.20 8.32
11. AOX level, kg/t paper
a. Generation 5.05 5.32 4.49 1.92 4.0
b. Final Discharge 1.72 2.65 2.39 1.07 1.84
12. Reduction in AOX, % 66 50 47 44 54
13. Effluent discharge, 189 267 314 88 220
m
3
/t paper
29
Table - 17 : AOX generation and discharge in Newsprint paper Industries
Parameters
Raw materials
Kappa No.
- Chemical Pulp
- Mechanical pulp
Bleaching Sequences
Chemial Pulp
Mechanical Pulp
Unit-8
Bamboo, Eucalyptus,
Casurina, Reed and
Imp. wood pulp
20
CHE
P+P
Unit-7
Bagasse, Bamboo,
Eucalyptus and
Imp. wood pulp
20-Eucalyptus
10-Bagasse
CEH -Bagasse
CEHH-Eucalyptus
p
Total Chlorine applied, %
Total Elemental Chlorine,%
Newsprint production,t/d
Other variety(W&P),t/d
Total Flow,m
3/d
AOX,Level
-Influent,mg/I
-Effluent" "
AOX,Kg/t product
-Generation
-Final Discharge
Reduction in AOX, %
5.80
4.00
250
27311
4.85
1.32
0.53
0.14
72.79
9.50
6.00
276
253
69120#
13.69#
6.22#
1.79#
0.80#
55.20
-----------------------------------------------------------------------------------------------------------------
(#) Includes writing and printing paper grade street
30
Table - 18 : AOX generation and discharge in Rayon grade pulp Industries
--_._--_.._-----_.__. _ - - - - - - - - ~ - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - ~ - - - - - - - - - - - - - - - - -
Parameters Unit-9 Unit-4
Raw materials Eucalyptus,Casurina
Pulp Kappa No 12.8
Bleaching Sequences CEoHEpD
Total Chlorine applied, % 4.60
Eucalyptus
16.00
CEHD
5.5
Total Elemental Chlorine,%
Total pulp production, tid
Total Flow,m
3/d
AOX Level,mg/l
Influent
Effluel'lt
AOX,Kg/t pulp
-Generation
-Final Discharge
Reduction in AOX, %
2.50
110
18360
4.14
1.26
0.69
0.20
71.48
2.80
63
61440#
41.00
(#) Includes writing and printing paper grade streets from Bagasse Eucalyptus
and Bamboo.
9.0 CONCLUSIONS
(i) Most of paper industries are producing varieties of paper depending on
the market needs.
(ii) Almost all the paper industries are using diverse raw materials due to non
availability of conventional single raw material and asa consequence, the
performance of existing equipment and technology is usually below the
expected standards.
31
(iii) In most of the paper industries studied, the effluent treatment plants
(ETPs) are having treatment loads more than their designed capacity
because industries have continued with their capacity expansion
programmes perhaps without upgrading their ETPs.
(iv) The generation of AOX measured in effluents from both rayon grade pulp
& newsprint industries was below 1.0 kg AOX/t paper. The degradation of
AOX in biological treatment plant observed is more than 70% and the level
of AOX measured was further reduced below 0.50 kg/t paper in final
discharge. The higher reduction of AOX in these categories of industries
compared to writing & printing paper industries may be because of low
initial concentration of AOX in influents.
(v) The generation of AOX measured varies from 2.0 to 5.30 kg AOX/t paper.
The lower value i.e 2.0 kg was measured in relatively modern industry (
Unit-5) employing RDH pulping, oxygen delignification with chlorine
dioxide in bleaching processes. In general, the generation of AOX in
writing & printing paper industries varied from 1.92 to 5.32 kg AOX/t
paper. The degradation of AOX in biological treatment plant varies from
44 to 65 % and the level of AOX in final discharge reduced from 2.0-5.3
kg to 1.0 - 2.65 kg of AOX/t paper in these category of industries. The
variation in performance of ETP for removal of AOX may also be due to
initial high concentration of AOX in terms of mg/l due to varying quantity of
water consumed per tone of paper. The main reason of high level of AOX
may be because of use of high dosage of molecular chlorine due to high
carryover of organic matter alongwith pulp to bleaching section & also
requirement of high brightness of end product. The results of AOX
assessed indicate that the generation of AOX at source is lower in the
industries using modified pulping & bleaching processes, where the
generation of AOX is about 2.00 kg which is further reduced to 1.00 kg/t
paper in final discharge. However, some paper industries have already
started the use of chlorine dioxide & oxidative alkali extraction bleaching to
improve the quality of pulp & bleach plant effluent.
(vi) The discharge of waste water in wnting & printing paper industries
measured during study was comparatively higher & in some industries the
final discharge of effluent measured was more than 270m
3/t
paper. In
most of industries, the treated effluent is being discharged into river except
(Unit-7) where almost entire quantity of treated effluent is utilized for land
irrigation by local farmers.
32
10.0 RECOMMENDATIONS
(i) The newsprint grade paper and rayon grade pulp industries may continue
to use the existing pulping & bleaching conditions, since the final
discharge of AOX in these categories of industries is well below 1.0kg
AOX/t of product. However, in rayon grade pulp industries, the generation
& discharge of AOX levels could be further reduced to lower levels by little
substitution of molecular chlorine with chlorine dioxide without any
modification in existing operating conditions. It is observed that the
industries studied are using chlorine dioxide in final stage of bleaching,
where the generation of AOX is negligible.
(ii) The higher level of AOX appears to be only in writing and printing pulp &
paper industries especially in those which 'are using molecular chlorine or
very little chlorine dioxide is used to bleach the pulp to high brightness
level where final discharge of AOX varies from 2.40 to 2.70 kg/t of paper
while in industries using modified pulping &bleaching processes, the final
discharge of AOX varies from 1.0 to 2.0 kg/t of paper.
(iii) Attempts should be made to reduce the generation of AOX at source
through (a) controlled pulp industry operation for maintaining low kappa no
of pulp, (b) improved pulp washing technique to reduce chemical
carryover with the pulp, (c) use of Oxygen delignification process to
reduce Kappa no of pulp, (d) use of Chlorine dioxide substitution in place
of elemental chlorine, (e) use of Oxygen at alkali extraction stage, and (f)
regular monitoring of Effluent Treatment Plant for its proper operation.
11.0 FINALIZATION AND NOTIFICATION OF AOX STANDARDS
The standards of AOX recommended by the Peer & Core Committee are as
follows
SINo. Discharge limit of AOXI t o!-'pape.r Date of implementation
1. 2.0 Kg/t of paper From January 01,2002
2. 1.0 Kg/t of paper From April 01,2002
Ministry of Environment & Forests (GOI) has finalized and notified the following
standards of AOX in case of Large scale pulp & paper industries vide notification
G.S.R.546(E), dated 30.08.2005. The maximum permissible discharge limits for
AOX specified in this notification are:
(A) 1.50 Kg/t of paper produced with effect from the date of notification i.e
30.8.2005, and
(B) 1.00 Kg/t of paper produced with effect from the 1
st
day of March,2008.
----- 0 -----
33