School of Chemical Engineering

Pretreatments for membrane processes

& membranes as pretreatment
CEIC8341
Pierre Le-Clech
p.le-clech@unsw.edu.au




UNESCO Centre for Membrane Science and Technology
School of Chemical Engineering
The University of New South Wales
http://www.membrane.unsw.edu.au


Outlines
Pretreatment for MBRs

MBRs as RO pretreatment in wastewater recycling schemes

Pretreatment for desalination RO
MEMBRANE BIOREACTORS
Pretreatment of MBR why?
Pretreatment for MBR why?
Screening is the first step on any WWTP
Previous painful examples due to the lack of experience
Installation of additional sieving in MBR easily accepted
Main risk: clogging of the membrane module (especially hollow
fibre) and aerators.
Materials to remove: hairs, lint, fibrous materials and other debris

Pretreatment for MBR why?
Materials carried upwards through air bubbles rising.
Clogging usually leads to sludging. Both decrease active surface
area.
Antifouling strategies (like backwashing) not efficient to remove
clogging.
Manual cleaning is not recommended (risk of damage)
When aerator ports get affected, aeration flow patterns change,
scouring decreases and fouling increases.

Pretreatment for MBR how?
Upgrading of pretreatment necessary with retrofitting CASP into
MBR.
Conventional screening at 3-6 mm are insufficient.
Screens down to 0.8 mm could be used especially for hollow fibre
module systems.
Flat sheet modules are more tolerant to clogging (2-3 mm screening
could be enough).
For aerators: special design + periodic flushing of aerators with
water.

Pretreatment for MBR

To be considered: the increased amount of waste sludge produced
and the maintenance of the system

MBR can treat different types of sewage:
Raw
Settled
Coagulated
But always screened
Some examples:
Sidestream:
Norit X-Flow: 0.75mm
Submerged flat sheet:
Kutoba: 0.5mm
Brightwater Eng.: 6mm followed by 3mm
Toray: 0.75mm
Submerged hollow fiber:
Memcor: 2mm
Zenon: 1mm or 5mm + 0.5mm

Characteristics may change from a plant to another
Data from Judd (2006) The MBR Book

Parameters influencing screening
Size ***
Geometry (slit, hole, mesh)
Type of construction
Design (single or multi staged)









Dictated by membrane manufacturers and system suppliers
Gap size (mm)
Coarse screen 50 - 20
Middle screen 20 - 10
Fine screen 10 - 2
Coarse sieve > 1
Fine sieve < 1
Micro sieve <0.05
Sieving performances
Horizontal slit screen and mesh sieve (both with gap size of
0.75mm) have been compared:

Removal efficiency (%)






From Frechen and Schier (DESEE, University of Kassel, Germany)
SS COD N P
Slit 15 9 4 7
Mesh 25 23 11 14
Rotary drum
screen
(from Munson)
www.wecleanwater.
com/


Pretreatment as anti-fouling strategy
Coagulant/flocculent
Ferric chloride or hydroxide, aluminium sulfate
Result in particle size increase, in SMP decrease
Alum cheaper but less efficient
May even improve the permeate quality
Adsorbent
PAC (around 1.2 g/L)
Effect of the PAC saturation and resulting retention time
Polymers (cationic based from Nalco)
Could be applied to the feed (before entering the MBR Need initial
clarifier) or added into MBR directly
MBR as pretreatment
MBR-RO for wastewater treatment
High level of pretreatment required to limit RO fouling and resulting
cleaning
More frequent use of RO for wastewater recycling
Early attempts of MBR-RO from 2000-2001
Possible pretreatment by dual-membrane-processes:
CAS + MF or UF
MBR
No industrial example of MBR-RO for seawater desalination yet

Few pilot/large-scale studies
First considerations
Aqua 2000 Research Centre and Water Factory 21
MBR produced high quality effluent good enough for RO
Possible limitations with (nitrification and) denitrification
Lawrence, Adham and Barrott, 2002, Desalination

Advanced landfill leachate treatment in Korea
Retrofitting of rotating biological contractor + GAC
50 m
3
/d
Good removal of BOD (97%), and dissoved non-biodegradable organic
matters (COD: 97%, Ammonia: 96%, Nitrate: 93%)
Lower operating cost ($3/ton) compared to original system ($5/ton)
Ahn et al., 2002, Desalination

Few pilot/large-scale studies
Comparison of AS-MF-RO and MBR-RO
Lower TOC in MBR permeate
Better quality in MBR-RO
Higher flux (30%) from RO in MBR-RO
Tao et al., 2006, Water Practice and Technology
Removal of nitrate and disinfection by products (DBP) potentially not
good enough for drinking applications, although USEPA limits reached:
Nitrate level up to 3.6mgN/L (need extra denitrification step in MBR)
THM up to 40 mg/L (from MBR cleaning with chlorine, and addition of 2.25
mgCl
2
/L as RO fouling control)
Comerton et al., 2005, Water Research
Addition of GAC between MBR and RO
Gur-Reznik et al., 2008, Water Research
MBR-RO for treatment of:
Dye wastewater
Presence of salts and organic substances in MBR effluent
Water quality of RO relatively constant for recovery rates ranging from
20 to 80%
All water reuse standards met
Juang et al., 2008
Laundries wastewater
Hoinkis and Panten, 2008
Pulp and paper wastewater
Large industrial application (3-millions-Euro plant)
34000 m
2
of MBR membrane
Siemens, Germany


NEWater in Singapore
High grade water production
94,000 m3/d (by 3 factories)
UF-RO-UV installed in May 2000
More recently, MBR-RO has been considered in order to limit TOC
in effluent for use in electronics industry
Parameter AS-MF RO MBR RO

TOC 7 4.8-5.0
Turbidity < 0.2 < 0.2
NH4- N 1.96-5.54 1.00
TDS 573-703 557-749
RO feed (mg/L)
Parameter AS-MF RO MBR RO

TOC 0.033-0.053 0.024-0.033
Turbidity < 0.1 < 0.1
NH4- N 0.07-0.42 0.05-0.22
TDS 9.8-13.3 8.9-13.1
RO permeate (mg/L)
MBR-RO:
RO run at 22 LMH without
CIP for 5 months
AS-MF RO:
Only 17 LMH
Qin et al., 2005, J. Memb. Sci.
A couple of working examples from GE
Size
(MGD)
Comm.
date
Application Removal (mg/l)
ABR
Wietzendorf,
Germany
0.6 2003 RO water reused in
the process for
washing potato

COD 85
TKN 10
PO4-P 1.5
Chungwa
Picture Tube
III, Taiwan
1.1 2003 TFT-LCD
Manufacturing

COD 35.2
BOD 6.5

Other examples
City of Colony Key (1.5 MLD)
City of Laguna (1.9 MLD)
Treatment of concentrated raw juice before discharge (Kubota)

Energy costs
Feed Pretreatment
(kWh/m
3
)
RO system
(kWh/m
3
)
Total
(kWh/m
3
)
Surface water 0.15-0.3
Wastewater AS 0.4-0.8 0.4-0.5 0.8-1.3
Wastewater MBR 0.8-1.0 0.4-0.5 1.2-1.5
Brackish (up to 2000 ppm) 0.1-0.3 0.6-0.9 0.8-1.0
Brackish (higher salinity) 0.3 1.4 1.7
Seawater 0.3-1.0 2.0-3.0 2.3-4.0
MBR energy costs:
Microbiology (0.3 kWh/m
3
)
Fouling control - air (0.4 kWh/m
3
)
Pearce, 2008, Desalination
PRETREATMENT FOR RO
IN SEA/BRACKISH WATER
What to be removed?
Suspended solids
Soluble iron, manganese, aluminium
Calcium salt scaling
Organics
Biological fouling
Why?
Improving the OPEX of the plant
Prolonging operation between chemical cleanings
Extending membrane life
Improving water recovery
Reducing corrosion
And improving produced water quality
Technologies available
Membrane (MF-UF)
Separation and Filtration
Flotation
Clarification
Multimedia
Cartridge/Bag
Ion exchange (softening)
Chemical feed
Coagulation, flocculation
Antiscallant
Dispersant
Precipitation softening
pH correction, biocide, chlorination (+dechlorination)
Membranes
MF (0.1-0.8 micron) - alone
UF (for extra TOC removal) UF+coagulation (to form backwashable
cake)
Low recovery and high energy consumption (EC)
Very little difference between MF and NF
Separation and Filtration
Flotation/dissolved air flotation (DAF)
http://video.google.com/videoplay?docid=283743212792193130#
Oils, algae, low levels of SS that can float by attachment of air bubbles
by flocculation
Good water recovery (97%) and moderate EC
Clarification
Contaminants that can easily coagulate and/or flocculate into larger
particles
Good water recovery (97%) and low EC
Media filtration
Most common
Combined with coagulation
Good recovery (96%) and low EC (one daily backwash)
Variation in feed quality must be combined with variation in coagulation
dosing (chemicals to be slightly underdosed)



Chemical additions
Coagulation
Neutralisation of surface charge of SS and TOC for precipitation and
bind together
Coagulants: low MW cationic polymers or iron, alum
Low dose can remove almost all SS
High dose (at low pH) can remove lots of TOC)
Flocculation
Binding small SS to larger molecule
Flocculants: high MW polymers
Low dose for DAF
Flocculants are fragile, short shelf life
Chemical additions
Antiscallants
Increase solubility of soluble salts
Phosphonic (or carboxillic or maleic) acids
Phosphonic is a nutrient so
Dispersants
Prevent precipitates from coagulating
Carboxilic acid (for fine SS)
Precipitation for softening (Removal of scalants)
Increase of pH, + carbonate to precipitate calcium and magnesium and
silica


pH correction
Adjust to:
6.3 to precipitation aluminium
5.5 with metal coagulants to reduce TOC
Above 8 to increase silica solubility
And to convert available CO2
And to improve rejection of some compounds
Around 8-8.5 with oxidant to remove manganese
Chlorination/dechlorination
Chlorination to precipitate iron and manganese
Shock chlorination to remove marine growth
Or use of biocide

Dechlorination necessary to protect active layer of membrane (free
chlorine attack)
By activated carbon
Sodium bisulphite
High dose of UV

Destruction of microorganisms/bacteria liberates nutrients which
could foul and increase biofouling
Few lessons to remember:
Always consider the waste streams produced by the membrane
process (and its pre-treatment)

Tradeoff between level of pre-treatment (i.e. its costs) and the
accepted level of fouling in the main membrane process (i.e. and its
resulting O&M costs) is always difficult to optimise.

Many options available out there, with some of them now being
widely accepted by the community (but still lively discussion for
some of them)