1995 Soluble Polymer

Prog. Polym. Sci., Vol.
20, 987-1041, 1995

Copyright 0 1995 Elsevier Science Ltd
Printed in Great Britain. All rights reserved.
0079-6700/95 $29.00
Pergamon
0079-6700(95)00010-0
SOLUBLE
POLYMERS
IN WATER
PURIFICATION
BRIAN A.BOLT0
CSIRO Chemicals and Polymers, Private Bag IO, Rosebank MDC, Clayton, Victoria 3169, Australia
CONTENTS
1. Introduction
2. Natural impurities in water
2.1. Dissolved organic compounds
2.2. Insoluble impurities
2.3. Soluble inorganic matter
3. Coagulation and flocculation mechanisms
3.1. Coagulation by charge neutralization
3.2. Flocculation via polymer bridging
4. Cationic polyelectrolytes
4.1. Copolymers of quatemized dimethylaminoethyl acrylate or methacrylate
4.2. Polymers of diallyldimethylammonium
chloride
4.3. Polyelectrolytes derived from epichlorohydrin
4.4. Polyethyleneimine
4.5. Ionenes
4.6. Mannich reaction products from polyacrylamide
4.7. Polystyrene derivatives
4.8. Quatemized polyvinylpyridines
4.9. Polyvinylamine
4.10. Miscellaneous polyamines and quaternary ammonium polymers
4.11. Natural polymers
4.12. Sulphonium polymers
5. Anionic polyelectrolytes
5.1. Carboxylic acid polymers
5.2. Sulphonic acid polymers
5.3. Phosphonic acid polymers
6. Non-ionic polymers
6.1. Polyacrylamide
6.2. Poly(ethylene oxide)
7. Amphoteric polyelectrolytes
7.1. Amphoteric copolymers
7.2. Polymers containing zwitterionic units
8. Hydrophobically modified polyelectrolytes
8.1. Cationic
8.2. Anionic
8.3. Amphoteric
9. Practicalities in the use of polymeric flocculants
9.1. Makeup, selection and dosing
987
988
989
990
994
995
995
996
997
999
999
1001
1002
1002
1003
1004
1004
1005
1005
1006
1007
1008
1008
1008
1010
1011
1011
1012
1012
1012
1012
1012
1013
1015
1016
1016
to17
1017
1017
1018
988
B. A. BOLT0
9.2. Monitoring systems

9.3. Chemical analysis
9.4. Tagging of polymers
9.5. Polymer degradation
9.6. Toxicity
10. Applications of polyelectrolytes
10.1. Primary coagulation in drinking water treatment
10.2. Primary coagulation in industrial wastewater treatment
10.3. Flocculation in drinking water treatment
10.4. Advanced primary treatment of sewage
10.5. Flocculation in industrial wastewater treatment
10.6. Weighted flocculation
10.7. Sludge thickening
10.8. Mining industry applications
10.9. Metal ion removal
11. Advantages and disadvantages of using polymers
Acknowledgements
References
1018
1018
1019
1019
1020
1020
1021
1024
1025
1026
1027
1027
1028
1030
1031
1032
1033
1033
1. INTRODUCTION
This review focuses on the use of soluble polymers for the preparation of drinking
water from low quality sources and in cleaning up wastewaters of domestic or industrial origin. Potable water production normally involves physicochemical procedures,
although biological methods for nitrate removal are in use. The impurities present can
be suspended materials, in the form of clay, silica, microbial cells or algae, dissolved
and colloidal natural organic matter, and inorganics. Sewage treatment is generally
based on biological methods, both aerobic and anaerobic, although the process can be
enhanced by the addition of chemicals. Industrial effluents may also be biodegraded if
they are mainly carbonaceous, but concentration by physicochemical means is frequently desirable. Inorganic contaminants normally require the latter approach.
Physicochemical treatment covers processes such as the coagulation and flocculation of suspended solids and colloids, the adsorption of soluble materials on solid
substrates such as activated carbon and ion-exchange resins, oxidation to destroy
organic impurities and membrane technologies. The emphasis here is on the application of soluble polymers or flocculants in coagulation processes, which are followed
by a separation step in the form of sedimentation or flotation, with a final polishing by
filtration. There is some potential for the use of soluble polymers in membrane technologies as well.
Polymers have been utilized in coagulation/flocculation
processes for water purification for more than three decades. However, with a few notable exceptions in
drinking water production* and sewage sludge conditioning,3 there is not a great
deal of published information on the relationship between polymer structure and
treatment performance, that is, of ways to obtain maximum flocculation or water
exclusion, the fastest rates of both precipitation and sedimentation, the best quality
for the recovered water and the highest solids content of the final sludge. There is much
opportunity for improved polymeric flocculants that are tailor made for particular
processes.
989
SOLUBLE POLYMERS IN WATER PURIFICATION
A number of benefits arise from polymer use: the capacity of a treatment facility
may be more than doubled because the rate of solid and water phase separation is
dramatically increased as larger agglomerates are formed, the dosage of other chemicals is lowered and the volume of sludge produced is more than halved. Also, the range
of waters which can be treated is greatly widened. There are, of course, some disadvantages, with higher costs being the main concern. This presents a challenge for
future research, particularly for natural water which contains significant levels of
colour and for industrial wastewaters. Some discussion of the types of compounds
present in poor quality water supplies is appropriate; many of these have polymeric
structures.
2. NATURAL
IMPURITIES
IN WATER
The materials which occur in waterways may be dissolved as well as particulate in

nature, and can be organic or inorganic. Some of the more commonly found organic
components are shown in Fig. 1. They are formed by the biological degradation of
organic substances,4 and can consist of highly coloured compounds.
meters
1 o-6
Phytoplankton
1 o-7
1 o-8
1 o-9
10-10
t-
Cl10
cl
General colloid
range
-l
Molecular
weight
Carhohydram
Fig. 1. Particulate organic carbon (POC) and dissolved organic carbon (DOC) in natural
water (from ref. 4. Reproduced by permission of Kluwer Academic Publishers).
990
B. A. BOLT0
2.1. Dissolved Organic Compounds
Dissolved organic carbon (DOC), defined as that which will pass through a membrane having pores of 0.45 pm size, has levels in the range of 0. l-l 15 mg I-, with
575mgl- being a world average for streams.5 These pose a problem for the water
treatment industry for a number of reasons. Apart from causing colour, taste and
odour, their removal is essential to minimize the health hazard posed by the formation
of potentially carcinogenic chlorinated hydrocarbons when the final water is disinfected with chlorine - the problem of disinfection by-products. Also, DOCs interfere with the oxidation of dissolved iron and manganese to insoluble, easily removed
forms. They also foul membranes and ion-exchange resins, and exacerbate corrosion
and the deterioration of water quality in distribution systems.6
The compounds involved are amino acids, fatty acids, phenols, sterols, sugars,
hydrocarbons, urea, porphyrins and polymers. The polymers include polypeptides,
lipids, polysaccharides and humic substances. Some idea of the variation of DOC and
the amounts of various compounds present are shown in Figs 2 and 3; the variation
is seasonal as well as regional.45 Thus rivers surveyed in the United States have
varying amounts of humic substances both along a given river and from one river
to another, ranging from 0.30 to 30.0 mg 1-l. The level in June can be four times that in
December.4
Humic substances constitute about 50% of the total DOC of surface waters (Fig. 3)
but the proportion can be as high as 8O%.7 Additional problems of an aesthetic nature
arise because of their colour, and the taste and odour produced if the water is chlorinated before their removal. They are composed of many compounds that contain
Total organic carbon. mg/L

0
2c1
II
IO
25
30
35
articullatcf orgarlit cartm
Eutrophic lake
12
Marsh
Bog
Fig. 2. Approximate
concentrations
of organic carbon in some natural water sources (from
ref. 4. Reproduced
by permission of Kluwer Academic Publishers).
SOLUBLE
POLYMERS
IN WATER
991
PURIFICATION
DOC histogram
0
10
20
30
40
50
60
70
80
90
100%
Fig. 3. Dissolved organic carbon histogram for average river water with a DOC of 5 mg 1-l
(from ref. 4. Reproduced by permission of Kluwer Academic Publishers).
mainly carbon, hydrogen, oxygen, nitrogen and sulphur. There is a wide compositional
range with C, 43-62%; 0, 31-49%; N, l-7% and S, O.l-1.5%. They are dark
coloured, acidic and predominantly aromatic compounds, commonly divided into
humic acids, which are soluble in alkali but not acid, and fulvic acids, which are
soluble in both acid and base. There is a fraction that is not soluble in either acid or
alkali which is referred to as humins.
The chemical structures of the two soluble fractions are not well known, but are
believed to be similar. Many formulae have been proposed,* as shown in Fig. 4. Humic
substances are unique materials in that they
vary in their acidity, over a p& range of 3-5;
are polydisperse, with molecular weights of 300-30 000;
interact via their hydrophobic aromatic and aliphatic regions with non-polar pollutants such as pesticides and polychlorinated biphenyls;
vary in their molecular structure, having mostly phenolic and carboxylic acid functionalities, but also alcohol, quinone, ether, ester and ketone groups;
behave as negatively charged colloids or anionic polyelectrolytes at natural pH
levels, and have surface-active properties;
are often present as stable complexes with metal ions.
These variable properties influence reactivity, which changes seasonally and from
to region. The polyfunctional nature of humic acid is apparent from its titration
curve, which is less steep than that for a mixture of acetic acid and phenol, as illustrated in Fig. 5. This is a characteristic of polyelectrolyte behaviour, where groups
influence their neighbours and make additional ionization more difficult, to cause a
smearing-out of separate acidity levels.
The ratio of fulvic to humic acids present in various water resources is roughly
region
992
B. A. BOLT0
HO
HO
HO
HO
HO
COOH
;~pJJ;g-qH
cool4
cool4
OH
OH
B - Flaig, 1960
A - Fuchs, 1930
O=qH
(HO-$H)
(sugar)
0:CH
0
cooH
;&o:fl;q&
0
R-6H
C:O
(pepttde)
1982
D - Buffle, 1977
COOH
COOH
tiH
C - Stevenson,
E - Steelink,
1985
Fig. 4. Some suggested formulae for humic substances as proposed by various authors (from
ref. 8. Reproduced by permission of Plenum Press).
constant at about four (Fig. 3), but the actual amount of humic substances is very
dependent on the source, being greatest for wetlands, then streams and rivers, followed
by lakes, and least for ground water.4 The properties of fulvic and humic acids have
been summarized5 and are listed in Table 1. It can be seen that fulvic acids contain
993
PH
12 -
carboxylic
groups
10
I
2
Equivalent fraction strong base

[mol base I mol functional group]
Fig. 5. Comparison of the titration curves for an equimolar ( 10m4M) solution of acetic acid
and phenol with humic acid that contains 10m4M carboxylic acid groups (from ref. 10.
Copyright 1992 John Wiley & Sons, Inc. and reprinted with permission).
about 10% less carbon and 10% more oxygen than humic acids, and have more than
double the content of carboxylic acid groups. They have a similar preponderance of
alcohol groups, but are significantly lower in average molecular weight. Fulvic acids
are hydrophilic, whereas humic acids are more hydrophobic in character.
Humic acids are less acidic than fulvic acids, so the conjugate anions are stronger
bases, in the order humate > fulvate. Thus, heavy metal ions are bound more strongly
Table 1. Comparison
of fulvic and humic acids5
Property
Fulvic acids
Humic acids
Elemental analysis (wt%)

C
H
0
N
S
45.1
5.4
44.8
2.1
1.9
56.2
4.7
35.5
3.2
0.8
Typical groups (meq g-)

Total acids
RCOOH
Phenolic OH
Aliphatic OH
Quinone, ketone
OCHs
10.3
8.2
3.0
6.1
2.7
0.8
6.7
3.6
3.9
2.6
2.9
0.6
300- 10 000
700-30 000
Molecular weights
994
B. A. BOLT0
by humic acids than fulvic acids. In conventional water treatment with aluminium or
ferric salts, carried out at pH levels where the organics are present as both ionized and
free acid species, humates bind more strongly to the metal than fulvates. The greater
number of points of attachment in the case of the larger polyanions is a further factor
here. In addition, the larger non-charged and more hydrophobic humic acid molecules
adsorb more strongly to the metal hydroxide floes than the smaller fulvic acid
molecules.6310 Hence, water containing large amounts of the lower molecular weight
forms of humic substances are more difficult to treat by coagulation processes, especially if such water is low in turbidity. The lower molecular weight material is better
removed by adsorbents12 or, after oxidative degradation, by biological methods.
Thus, when an anion exchanger removes the smaller organic molecules from raw
water, the subsequent alum clarification stage is greatly facilitated. Larger floes are
formed that settle three times more rapidly, far less organics are left in the product
water, and only 25% of the original alum dose is required.t3
2.2. Insoluble Impurities
Minute particles causing turbidity and suspended particulate matter can range in
size from colloidal to 10 pm or more (see Fig. 1). They are an important component of
all natural waters and need to be taken out of potable supplies because microbes
adsorbed onto the surface of the particles can be protected from disinfection by a
coating of slime, or the particles themselves may be actual bacteria or cysts of protozoa
such as Giurdia lumbliu or Cryptosporidium. Typical levels are 2-200 mg 1-l) although
they can be as high as 200 000 mg 1-l in flooding rivers. The particles are heterogeneous
in size and chemical constitution, and mainly comprise inorganic compounds like
silica, aluminosilicates, iron and manganese oxides. They can have a substantial
organic and biological content, typically l-20%.
zL-
.4,
l.0
-0.5
*Yam Alver Partlclas

t Seawater
l YarraRiverParticles t CaCl,
AYarraRiverParticlaa * NaCl
06usthite t RedwatarCreekOOU
+ CaCla
OGoethite + Suwannee
Streaa FAt CaCl,
10
Salinity
15
20
(pptl
Fig. 6. The electrophoretic mobility of various types of particulate matter coated with humic
substances of several origins and its variation with salinity, expressed in parts per thousand
(from ref. 8. Reproduced by permission of Plenum Press).
SOLUBLE POLYMERS
IN WATER
PURIFICATION
995
The surface charge potential is an important parameter infmencing colloid stability

and adsorption behaviour. It can be monitored via particle microelectrophoresis, and
in natural systems is invariably negative, irrespective of the nature of the primary
particle.14 It decreases in magnitude as the ionic strength of the water increases.*
The charge on the particles appears to be controlled by an adsorbed layer of natural
organic matter, as well as by the salinity and the con~ntration of divalent cations in
the water, as shown in Fig. 6. Humic substances can adsorb onto the particles via
surface metal ions:
-0-Ca+
+ -OOC-R-COO-
--t -O-Ca-OOC-R-COO-
(1)
As there are other carboxylate groups on the same organic molecule which are not
bound to the metal, the overall charge on the particle is ultimately negative. The
coating of organics has a strong impact on the amount of coagulant required and
the rate of coagulation, slowing the latter down markedly at low salinities, but having
less of an effect as the salinity increases.
2.3. Soluble Inorganic Matter

Common dissolved salts are acceptable up to certain prescribed limits. There
are heavy metals in cationic and anionic forms, as well as metalloid anions, which
can be natural in origin but are more frequently a result of mining and manufacturing. A by-product of agriculture which has consequences for eutrophication
of natural waters is the presence of ammonia, nitrate and phosphate in run-off
water. Many of these contaminants are removed by physicochemical treatments.
Cationic heavy metals can be pre~pitated as the hydroxide, sulphide or carbonate.
Anionic species such as arsenate, selenate and their reduced forms are adsorbable on
metal oxides, and phosphate can be precipitated as aluminium, ferric or calcium
species.
3. COAGULATION
AND FLOCCULATION
MECHANISMS
To remove turbidity and organics from water supplies involves contending with
impurities which are negatively charged at natural pH levels, and have formed a
stabilized dispersion. The first step is to destabilize the dispersion and coagulate the
contaminants, which is generally done by the addition of positively charged species in
appropriate quantities to neutralize the charge on the impurities. A flocculation step is
then used to bring together the particles so that larger floes are produced. In water
industry parlance, the terms coagulation and flocculation are not synonymous.
Coagulation is used to describe the process whereby the original dispersion is destabilized by overcoming the forces which maintain the stability. Flocculation describes
the process whereby the destabilized particles join together to form larger agglomerates.r6 This terminology will be used throughout the present review, although it
should be realized that the two processes can take place following the addition of a
single organic polymer instead of an inorganic salt followed by a polymer.
B. A. BOLT0
996
3.1. Coagulation by Charge Neutralization
Employing hydrolysable metal salts for coagulation is a long-standing technology,

the mechanism of which has been thoroughly investigated.17 Charge neutralization
is brought about by the addition of aluminium or iron salts to form soluble hydrolysed
cations and metal hydroxide floes, the relative amounts depending on the operating
pH. In the case of aluminium, monomeric hydroxo species like A10H2+, Al(
and
Al(OH)T are formed almost instantaneously. The precipitation of A1(OH)3 commences after about one second and is ongoing.17 The dimer A12(OH)p is also produced after about one second, while in the ensuing minutes polymeric forms as large as
AMOH):,+ may be produced. Several mechanisms have been postulated for the
coagulation of humic substances and turbidity particles by aluminium ions. Thus, at
pH4-5, when the organic acids are at least 50% ionized, there is a stoichiometric
reaction to precipitate an aluminium humate:
2RCOO- + A10H2+ + (RC00)2A10H
(2)
At pH 5-6 the same reactions proceed, but through polynuclear aluminium species.
At these and higher pH levels, adsorption of the organics on aluminium hydroxide
occurs.17 It has been proposed that this occurs by the ligand exchange reaction:
RCOO- + OH-Al<
+ RCOO-Al<
+ OH-
(3)
The same reaction also takes place with the aluminium humates formed via eq. (2)
from mono- or polynuclear hydroxo forms of the aluminium cation. Normally the pH
level is about 5.5 for aluminium and slightly lower for ferric salts. The final product is
composed of aluminium hydroxide floes loaded with humics and turbidity particles.
The preponderance of the metal hydroxide cannot be taken as proof that the main
reaction is between humics and A1(OH)3, as depicted in eq. (3). The two proposed
mechanisms* for aluminium salt coagulation of humic substances are shown in Fig. 7.
Originally utilized as alum in the case of aluminium, the coagulant can also be
applied as the polynuclear cation via preformed poly(aluminium chloride) or the corresponding sulphate. The salt residual is then greatly reduced and it is found that the
Humics
Al- Humates
3+
Al (H20&
on-
-Small
------cAl-Monomers
<0-4sec
(Al OH 2+,elc.l
<I set
(ppl)
Al- Polymers
(AI,(~H);~.
n~,tot$~)
2,
-I set
(Depends
Al tOH)s tppl)
an Al~,pHl
Fig. 7. Pathways for the coagulation of humic substances by aluminium ions. The bottom
route, resulting in Al(OH)s precipitation,
is favoured by high DOC or a pH above about 6.
The other route, resulting in aluminium humate precipitation,
is favoured by low DOC and a
pH below 6 (from ref. 18. Copyright
1986 John Wiley & Sons, Inc. and reprinted with
permission).
991
usage of coagulant can be up to 30% lower. The inorganic polymeric species have a
higher positive charge and are therefore more effective in neutralizing the negative
charge on suspended clay particles and natural organic materials.20 They are more
effective for cold water and for water having high levels of organics, and can be
employed over a wider pH range than alum. However, they are more expensive.
Prepackaged combinations with various polyelectrolytes are available.
A number of coagulants are now available for water treatment, based on aluminium
and iron salts of various types, including polynuclear material either commercially
accessible or produced on site.tta2t Destabilization of the impurities in water by charge
neutralization with highly charged cationic organic polyelectrolytes is also carried out
and will be dealt with in Section 10.1.
3.2. Flocculation via Polymer Bridging
The small floes formed by coagulation can be built up into larger agglomerates by
flocculation with a polymer, with the larger particles formed in this way giving accelerated rates of sedimentation. The process involves polymer bridging, in which polyelectrolyte bound to a floe particle has looped and dangling chains which can attach to
nearby particles. This mechanism is favoured when long-chain polymers which do not
have a high level of charge are used. The nature of the surface charge on the floes
following coagulation will depend on the dose of metal salt used, but the net charge
is normally close to zero, with the number of positively and negatively charged
sites being almost equal. Often an anionic polymer will increase the size of the floes
by interaction with the positive sites on the floe surface.22 Bridging will occur when
the adsorbed chains interact with another floe in the same way, as shown
commence
Adsorption continues,
bridges shorten and
multiply
Adsorptlon and
flocculation
4 complete
Fig. 8. The bridging
flocculation model (from ref. 248. Copyright 1991 Society of Dyers and
Colourists and reprinted with permission).
B. A. BOLT0
-_
c?
I
Intar-paltkk
adsotptlon
Electrostatic attraction
brlng8 partkkr
together
**
. . I---___
:
.
:
-__
--_
_ * -00 -__-.--
Fig. 9. The charge patch agglomeration model (from ref. 248. Copyright
Dyers and Colourists and reprinted with permission).
diagrammatically
1991 Society of
in Fig. 8 and in the equation:

>Al+ + -polymer-
+ +Al< -+ >Al-polymer-Al<
(4)
According to the electrostatic charge patch model, polymer will adsorb where there
are domains of opposite char e to that on the polymer, leading to an excess of charge
associated with the polymer.2 B324When the polyelectrolyte has a high concentration of
charges, it is likely that it will adsorb onto the particles in a rather flat configuration,
leading to high-intensity patches or domains with localized excesses of the polymers
charge. Direct electrostatic attraction between the particles is hence encouraged and
domains of opposite charge in adjacent particles will combine, resulting in agglomeration as depicted in Fig. 9. The overall effect is still as in eq. (4).
Serious colloid science studies on the flocculation of particles in very clean systems
by well-defined polyelectrolytes have been carried out over the years, covering, for
example, lattices,25-27cellulose,27728silica,29-31iron oxide,30132and clays.33-35The essence
of this work is that generally there is a balance between two mechanisms: charge
neutralization with highly charged polymers and inter-particle bridging when the
polymer has a low content of ionic groups.34 There are particular issues of great
practical importance, such as effects on reaction rates3 and the size and strength of
flo~s,~~which are found to be dependent on molecular size, the degree of charge and
the ionic strength. These issues will be discussed further after the vast array of polymers available for water purification applications is reviewed.
Extensive reviews on polyelectrolytes and other polymeric flocculants, although
published some time ago, cover synthesis,37-39 applications37A3 and the range of commercial organic flocculants available.44 Flocculants are best broadly classified according to the nature of the charge they possess, that is, whether they are cationic, anionic,
zwitterionic or non-ionic. Other crucial parameters are molecular weight (MW) and
charge density (CD), with the latter generally expressed as a percentage of ionogenic
groups relative to all groups of every type for industrial products, but also as meq g-l
SOLUBLE POLYMERS
IN WATER
PURIFICATION
999
Table 2. Classification of polymeric flocculants by molecular

size and charge
Amount
MW (dalton)
CD (mol %)
High
Medium
Low
ca. lo7
105-IO6
104-lo5
50-100
ea. 25
ca. 10
for some well-defined polymers in the literature. When the exact information is not
accessible for the commercially available materials, the approximate categories of
high, medium and low will be used, as defined in Table 2.
4.
CATIONIC
POLYELECTROLYTES
There is a greater variety of molecular structures in the cationic family than in any of
the others. Generally containing quaternary ammonium groups so that the formal
positive charge is present irrespective of the pH level, cationic polymers have also been
synthesized which contain sulphonium or phosphonium groups. Weak electrolyte
versions are in use which acquire cationic properties in acidic media and are based
on polyamines containing primary, secondary or tertiary amino groups, or mixtures of
them. The preparative techniques cover polymerizations by chain growth and step
growth mechanisms, often in simple aqueous solutions, but also as water-in-oil emulsions, and the modification of existing polymers.37-39 Also, some natural products are
in practical use, either as originally substituted with active groups, or by subsequent
reaction.
4.1.
Copolymers of Quaternized Dimethylaminoethyl Acrylate or Methacrylate
Random copolymers of acrylamide and acryloyloxyethyltrimethylammonium

chloride, formed by quaternization of dimethylaminoethyl acrylate with methyl chloride, are extensively used in the water industry. An extensive survey of this category of
polymers outlines their many applications.39 The methacrylate analogue is also commercially available. The cationic content in the copolymers (I) can be lo-100 mol%.
Note that in this structure and those that follow, the counterion has been omitted. The
preparative details have been summarized and kinetic data and reactivity ratios
co
co
NH2 0
la, R I H
Ib, R = Me
bvie
3
1000
B. A. BOLT0
obtained for continuous free radical polymerization in an inverse (water-in-oil) microsuspension. 45 The effects of pH, salt concentration, counterion type and soluble
organics were determined. Potassium persulphate or azocyanovaleric acid was used
as initiator at 45-60C.
The quaternized aminoacrylate copolymer (Ia) having a CD of 30mol% has been
used for clay flocculation studies34 and has been investigated by 13CNMR to determine
the sequential length distribution, one of the important parameters that affects solution properties.46 It was found that there was less of an alternating distribution than
would have been anticipated from the reactivity ratios, attributable to the heterogeneity of copolymers prepared at high degrees of conversion.
In copolymers with acrylamide, hydrolysis of the ester groups has been investigated
and found to be CD and pH dependent, with hydrolysis increasing as is to be expected
under more alkaline conditions:
Pol-COOCHzCH2
NMe3 + OH- + Pol-COO-
+ HOCH2CH2 NMe3
(5)
Earlier studies47 suggested that some degradation occurred even at pH 6 for polymers
having a CD of 24mol%, with a half-life of 24 h at pH 7 and 0.25 h at pH 8.5. The
polymer was stable in a pH 4 environment. There is no evidence of hydrolysis for the
acrylamide units up to pH 8.5. More recent work on ester hydrolysis on less ionic
polymers having a CD of 6 mol% gives a half-life of 22 months, presumably at neutral
pH.48 For a CD of 30 mol% the process is also very slow, especially for pure solutions,
whereas salt or pH levels above 8 causes an ease of degradation which is not observed
for the cationic homopolymer.46 The chain conformation is altered on hydrolysis by
virtue of the anionic carboxylates formed, which reduce the extension of the chain and
make the polymer less efficient in clay flocculation.48 Hydrolysis has also been shown
to produce imide substituents which reduce polymer solubility, as they can form
crosslinks.
Terpolymers based on (I) and incorporating a third monomer which is hydrophilic
have been synthesized and a version based on methoxyethyl acrylate has been tested
for sludge conditioning.49 Copolymers as in (\b but with monomers other than
acrylamide, are known: the vinylpyrrolidone,
acrylonitrile,51 and 2-methyl-5vinylpyridine52 variants of (Ib) have been prepared, and the latter two tested as
flocculants.
Similar polymerizations in aqueous solution have been studied for the somewhat
analogous amide copolymers (II), prepared from acrylamide and methacrylamidopropyltrimethylammonium
chloride.39153 They have the advantage of the cationic
II
1001
amide being a more reactive monomer, and the product being more hydrolytically
stable.54 The weakly basic tertiary amine versions of (Ia) and (II) have likewise been
explored. A variation on this theme is the use of higher esters such as dialkylaminoneopentyl acrylate, where the alkyl group is methyl or ethy1.55
4.2. Polymers of Diallyldimethylammonium Chloride
Polymerization of diallyldimethylammonium
chloride produces a water-soluble
polymer, despite the bifunctionality of the monomer. The free-radical polymerization
involves a cyclization mechanism56 to produce a five-membered ring.57 The polymer
(III) is of low to medium MW and contains pyrrolidinium units. It is commonly
known as polyDADMAC and is much used in the water industry. Polymerization
in inverse microsuspensions of the water-in-oil type has been reported.58 High-MN
copolymers have been made with acrylamide.59 The random copolymer has practical application in sludge conditioning. Graft copolymers have also been made from
polyDADMAC and acrylamide by first making a copolymer of DADMAC containing l-10 mol% acrylic acid, and esterifying it with 3-chloro-1,2-propandiol to introduce cis-diol groups. These serve as grafting sites for acrylamide in the presence of
ceric ions.62 A later approach via a copolymer with 3,4-dihydroxycyclohexylmethyl
acrylate gives higher-MW material and less homopolymer.63 Another route to highMWmaterial is by linking a copolymer of DADMAC and diallylamine hydrochloride
with polyvinylamine by reaction with epichlorohydrin.64 High-WY material can be
made by including a crosslinking agent like methylene-his-acrylamide
or glycidyl
acrylate in the polymerization with DADMAC.65 A high-WY product is claimed
by copolymerizing DADMAC and methyltriallylammonium
or tetraallylammonium
chlorides.66
Alternating copolymers of low to medium MW have been prepared from
DADMAC and sulphur dioxide, and tested for clay flocculation.67 The diethyl and
weakly basic versions of the sulphur dioxide copolymer with one or both methyl
groups replaced by hydrogen have also been prepared.
Variations of (III) in which large alkyl and other substituents are present in lieu of
one of the methyl groups are known. These include linear and branched-chain aliphatic, benzyl, piperidino and morpholino groups.68 The dodecyl derivative, as a
homopolymer or as copolymers with DADMAC or acrylamide, inhibits algal and
bacterial growth, as does the octyl derivative which has the second methyl replaced
by hydrogen.69 Similar tertiary amino polymers have been prepared which contain
decyl and hexadecyl groups.68170 A copolymer of 3-chloro-2-hydroxypropyldiallylamine hydrochloride and DADMAC has virucidal properties.71
1002
B. A. BOLT0
Me
IV
4.3. Polyelectrolytes Derived from Epichlorohydrin

Epichlorohydrin
forms polymers with ammonia and primary and secondary
amines, the preparation of which have been thoroughly reviewed.37 The reaction
with ammonia gives lightly branched polymers of low MN which are not of great
commercial interest. Primary amines such as methylamine give weakly basic products
of higher MWwhich have been used to aid solids separation in the minerals industrye3
The products have been quaternized to give useful flocculants.37 Similar polymers
made with butylamine or cyclohexylamine have been studied for humic acid
precipitation.72
The reaction of epichlorohydrin with a secondary amine such as dimethylamine
produces the low-MW linear polymer (IV) in which all the nitrogens are in the
quaternary ammonium form. Medium-MW branched polymers can be obtained by
terpolymerization with a small amount of primary amine. Diamines such as ethylenediamine are also used for this purpose. Similar flocculants have been prepared from
epichlorohydrin
and mixed amines like N, N-dimethyl- 1,3_propylenediamine
or
diethylenetriamine,
where the polymer ends up with some of its tertiary amino
groups quaternized by epichlorohydrin.37
The nucleophilic displacement of chloro groups in polyepichlorohydrin by a tertiary
amine produces a quaternary ammonium polymer having a polyether backbone.54173
Medium-WY materials can be made by using the mildest amination conditions to
avoid cleavage of the polymer backbone.74 As well as the preferred polymer (V) from
trimethylamine, weakly basic versions have been obtained with dimethylamine,
diethylamine, piperidine or diethanolamine.
4.4. Polyethylene&nine
Branched polyethyleneimine (VI) is one of the earliest known cationic flocculants,
and is often employed in treating industrial effluents. It is normally obtained by the
ring-opening polymerization of ethyleneimine with cationic initiators.37t54975It is a
weakly basic polyelectrolyte of medium MW that contains a mixture of primary,
secondary and tertiary amino groups, generally in the ratio 1: 2 : 1. Hence its cationic
character is pH-dependent, with about 40% of the amino groups protonated at pH 6,
CH,NMr,
V
SOLUBLE POLYMERS
IN WATER
PURIFICATION
1003
VI
and 60% at pH4.76 It is not easy to fully protonate the polymer because of the
polyelectrolyte effect: the buildup of charges on the chain makes the approach of
further protons more di~cult. Even at pH2 there is not much more than 75% protonation. Complexation of the polymer with heavy metal ions has received much
attention.77 Q ua ternization with dimethyl sulphate has been carried out,78 but only
polyethyleneimine itself is important in wastewater treatment.
Linear polyethyleneimine is crystalline and soluble in hot but not cold water. It has
been synthesized by the ring-opening polyme~zation of 2-oxazoline with boron trifluoride, followed by alkaline hydrolysis.79 The polymers have low MW, but a
medium-MW material can be obtained from 2-phenyl-2-oxazoline by using acidic
conditions to hydrolyse the poly(N-benzoylethyleneimine)
that is formed.* N-substituted methyl, propyl and phenyl derivatives have been made,79 as has linear polypropyleneimine.81
The linear and branched forms of polyethyleneimine offer a good opportunity for
investigating the influence of chain branching on flocculant performance, for both the
mixed polyamine and the fully quaternized forms.
4.5. lonenes
Quaternary ammonium polymers in which the nitrogen is in the main chain of the
polymer can be prepared by reacting dihalo compounds with a tertiary diaminesl or
from tertiary amines con~i~ng an w-halo group.54 Called ionenes, these polymers
have the general structure (VII), but when x and y are less than 3 no polymer is formed.
When x = y = 3 the product, designated a 3,3-ionene, has the highest CD of any in the
series. The ionenes have a charge on every unit in the polymer, so the CD in this series
needs to be defined as meqg- rather than mol%. The low-MW products have bacteriostatic properties and have been explored as flocculants for clay suspensions.82
Some 22 polymers, including 3,3-, 3,4-, 6,2-, 4,4- and 6,6-ionenes, were tested and a
dependence of performance on both MW and CD was observed, suggesting that both
charge neutralization and polymer bridging are involved.83
VII
1004
B. A. BOLT0
VI11
The symmetrical 3- or 3,3-ionene can be made by polymerizing dimethylaminopropyl chloride.84 Of medium MW, and as the ionene of highest CD, its flocculation
efficiency is the best of any ionene polymer. It should be noted that the polyelectrolyte
(IV) fits this category also, as it is a 3-ionene in which each aliphatic link is hydroxylated. A substituted 3,4-ionene containing unsaturation which offers opportunities for
grafting has been prepared from N,N,N,N-tetramethyl-1,3_propylenediamine
and
2,3&s(bromomethyl)-1 ,3-butadiene.85
4.6. Mannich Reaction Products from Polyacrylamide
By reacting polyacrylamide with formaldehyde and a secondary amine such as
dimethylamine, followed by quaternization, the polymer (VIII) is produced which is
useful as a flocculant.37 Variations on this theme include adding m-phenylenediamine
as well as dimethylamine to the reaction mixture to form a weakly basic material which
has found application in sludge conditioning.86 The quaternization has also been
carried out with epichlorohydrin.87
4.7. Polystyrene Derivatives
Polyvinylbenzyl chloride can be prepared by chloromethylating polystyrene, polymerizing vinylbenzyl chloride or chlorinating polymethylstyrene.37 Amination with
trimethylamine then produces poly(vinylbenzyltrimethylammonium
chloride),3g a
high-CD but low-MW quaternary ammonium polymer of structure (IX). A typical
polymer would have a CD of 80-85 mol%, plus 2-7% unreacted chloromethyl groups
and lo- 13% hydrolysed groups. The use of aliphatic amines where the alkyl group has
up to four carbon atoms gives superior products to those obtained from heterocyclic
amines like pyridine or N-methylpiperidine. * When amination is such that the CD is
about 60mol%, excellent clay flocculating properties are claimed. Another aspect is
the use of hydroxyalkyl tertiary amines in the amination step, to produce quaternary
ammonium polymers with one or two hydroxylalkyl groups on the nitrogen.8g
SOLUBLE POLYMERS
IN WATER PURIFICATION
1005
4.8. Quaternized Polyvinylpyridines

Some of the earliest polyelectrolytes known are based on pyridine,37 the range of
products being l-vinyl, 2- or 4-vinyl and 2-methyl-5-vinyl derivatives.39 They can be
made from the quaternized monomer or by quaternizing the polymer (not necessary in
the first-mentioned example) to produce the cationic polymer (X), which shows the
structure of the poly( 1-methyl-4-vinylpyridinium)
cation. These low-MI+, high-CD
products have been tested in the tertiary treatment of secondary sewage effluent in the
case of the I-butyl analogue, and in coagulating microbial cells in the case of the
I-benzyl derivative.
High-WV as well as high-CD polymers of the I-alkyl-2-methyL5vinylpyridinium
type have been investigated as flocculating agents for both natural water and wastewater when the alkyl group is methyl,92 and for coagulating lattices when that group is
ethy1.93
4.9. Polyvinylamine
To obtain polyvinylamine it is necessary to mask the amino group in an appropriate
monomer such as N-vinylformamide,
although N-vinylacetamide,37 N-vinyl-tertbutylcarbamate, N-vinylsuccinimide and N-vinylphthalimide94 have also been used
in less satisfactory approaches. The polymerization to polyvinylformamide can yield
high-MW material which is best hydrolysed to polyvinylamine (XI) in concentrated
alkali to give virtually 100% conversion. Acid hydrolysis proceeds to only 65% completion because of the buildup of positive charges on the chain.95
Another route is from polyacrylamide by means of the Hofmann reaction with
sodium hypochlorite, followed by strong alkali at low temperature. This is reported
to yield a 90% conversion of amide to amino groups, even with high-MWpolymer.96
Studies have shown that, with insufficient hypochlorite, 2-10% of the amide groups
are converted to carboxylate groups, while an excess of the reagent results in a l-5%
formation of urea groups.94 A recent method utilizes bromine and the monosodium
salt of ethylene glycol in that solvent, instead of hypochlorite and aqueous conditions,
NH,
XI
1006
B. A. BOLT0
XI1
followed by acid then alkaline hydrolysis to give a quantitative conversion to polyvinylamine.

Q ua t ernary ammonium forms of the polymer are more effective in water
clarification than alum or the epichlorohydrin-dimethylamine
polymer (IV).98
4.10. Miscellaneous Polyamines and Quaternary Ammonium Polymers
Many other approaches to the synthesis of cationic polyelectrolytes based on nitrogen compounds have been made.37?39154
Some of the products which are of use in water
treatment include polyvinylimidazoline (XII), prepared by reacting polyacrylonitrile
and ethylenediamine with thioacetamide as catalyst.99 A high-MW, high-CD polyelectrolyte is obtained which has commercial application as a flocculant, either in the
protonated form or after quaternization of the tertiary nitrogen.OOlOA variation is a
similar reaction with NJGdimethylpropylenediamine
to produce a six-membered ring
product which is useful in sludge dewatering.* Another is the reaction of polyacrylonitrile with dicyanodiamide to produce an analogous flocculant containing melamine
units, plus other functionalities like carboxylic acid, amide and nitrile.lo3 A flocculant
possessing melamine units attached to the polymer backbone by ether links has been
made by reacting poly(viny1 alcohol) with formaldehyde and melamine.lo3 The reaction of dicyanodiamide, formaldehyde and hexamethylenetetramine
is reported to
yield a polymer which gives up to 12% more suspended solids removal and up to
13% larger floes relative to polyacrylamide in the clarification of river water and of
wastewater from the textile industry.lo5
Some further examples are the formation of quaternary ammonium centres in either
the starting monomer or the final polymer, the latter being achieved by the replacement of chloro groups. Thus, vinyl chloroacetate can be aminated with trimethylamine
and polymerized to a quaternary ammonium flocculant,io6 and polychlorinated
alkanes having 13-19 carbon atoms can, on reaction with ethylenediamine and subsequent quaternization, produce a flocculant effective for turbidity and colour removal
for petroleum industry wastewater.
XIII
SOLUBLE
POLYMERS
IN WATER
NH2
PURIFICATION
1007
Poly(amido-amines) constitute a class of polymers which have many interesting

applications. One variety with potential use as a flocculant in the mineral industry
is that made from the his-acrylamide of piperidine reacted with N,N-dialkylethylenediamine to form the polymer (XIII), where R is methyl or hydroxyethyl. The flocculants perform better as the pH is lowered.
4.11. Natural Polymers
There are several naturally occurring polymers which have inherent cationic properties or can be modified to yield a cationic polyelectrolyte. The most prominent of these
is chitosan, a partially deacetylated chitin which can be considered as a 1 : 4 random
copolymer of N-acetyl-a-o-glucosamine
and a-p-glucosamine. The homopolymer of
the latter is shown as structure (XIV). The commercial product is of medium MWand
has a CD which is pH-dependent and can be as high as 80 mol%. lo9 The application of
chitosan in water purification has been extensively reviewed, with references to its
use in decolourizing dyehouse effluents, the treatment of food processing wastes, metal
ion removal and sludge conditioning. Most recently, a mixture of chitosan and bentonite has been tested for the removal of turbidity and colour from surface waters, and
found to perform as well as or better than alum or alum plus a cationic or non-ionic
polyacryamide, albeit at slightly higher cost. 11 The sludge volume is increased, but its
quality is better, and there is a reduced need for pH adjustment chemicals.
Starch, a polymer composed of a-D-glucose units, can be converted to a cationic
derivative by the reaction of the primary OH group in alkali treated starch with N-(3chloro-2-hydroxypropyl)trimethylammonium
chloride, so that the cationic site is
attached via an ether link to the polymer chain.12 The product has medium MW
and the CD can be low or medium. A medium-CD material was better in tests on
clarifying clay, raw and treated sewage suspensions, and has been used as a demulsifier
for oil in water emulsions. Graft copolymers of starch and 2-hydroxy-3-methacryloyloxypropyltrimethylammonium
chloride or mixtures of dimethylaminoethyl
methacrylate and acrylamide have been prepared and evaluated for flocculation
performance. 13,14
A number of flocculating agents have been reported which are lignin-based, prepared by modifying kraft lignin to give it cationic character.15 A Mannich reaction
product and a quaternary ammonium derivative made by chloromethylation
and
amination were less efficient than alum for the removal of colour from pulp mill
effluents.
1008
B. A. BOLT0
The reaction of tannin with formaldehyde and aminoethanol produces a weakly

basic polymer which is more effective than alum in removing turbidity and especially
colour from river water.l16
4.12. Sulphonium Polymers
Ternary sulphonium polymers are of interest in a number of applications, and some
copolymers have been tested for water treatment. However, they do not seem to have
any special advantages over the more readily available quaternary ammonium products. They are more likely to degrade, unfortunately producing odorous materials.
The sulphonium analogues of structures (I), (III) and (IX) have been prepared. Thus,
homopolymers of acryloyloxyethyldimethylsulphonium
methosulphate and its copolymers with acrylamide are obtained in high-W+ form by using acetone as the polymerization solvent, from which the polymer precipitates.117 The copolymer is
particularly suitable as a flocculant. Meth diallylsulphonium salts have likewise been
polymerized and copolymers produced. l1 r Vinylbenzyldimethylsulphonium
chloride
gives polymers which are effective as thickening agents and in the flocculation of slimes
in the mining industry. Its copolymers with acrylamide have been prepared.393120
The reaction of 2-chloromethylbutadiene
with dialkyl sulphides produces a sulphonium salt which can be polymerized to give cationic materials with flocculating properties.12* The alkylation of polythiodiethanol, a polymer of bis(hydroxyethy1) sulphide,
with 1,4-dichloro-2-butene yields branched polysulphonium compounds of low MW
and a CD above 60 mol% .122They are as effective as quaternary ammonium polymers
in clarifying clay suspensions.
Quaternary phosphonium polymers are also known3 an example being the methylphenylphosphonium
version of (III). 123Applications in the water purification industry
have not been identified.
5. ANIONIC
POLYELECTROLYTES
Polymers containing anionic groups are best categorized by their functionality. By

far the most common are those containing weakly acidic carboxylic acid groups, where
the CD will depend on pH. Also utilized are strongly acidic groups, for example,
sulphonic acid groups, which are fully ionized at normal operating pH levels.
Phosphorus analogues are also known.
5.1. Carboxylic Acid Polymers
High-Ml% carboxylic acid polymers based on polyacrylamide are extensively
employed as flocculating agents in the water and other process industries, where a
low CD is the general rule. One exception is the separation of red mud from alumina,
where a high-CD polymer performs better.373124Alumina coated with polyacrylate
may be electrostatically and sterically protected against aggregation at an optimal
dose.125 Copolymers of structure (XV) can be prepared either by copolymerization
of acrylamide and acrylic acid or its salts, or by polymerization of acrylamide followed
co
1009
co
I
I
NH,
O-
xv
by partial hydrolysis.37 The former route gives a roughly random copolymer, whereas
some clustering can occur in the alkaline hydrolysis approach. Water-in-oil emulsions
are preferred for both routes; the hydrolysis can be carried out without destabilizing
the dispersion, a step that is achieved later by the addition of an inverting agent.26 The
use of block copolymer surfactants of the ABA type in emulsion polymerizations gives
higher po$nerization
rates, higher-MW products, and better stability of the
emulsions.
The CD can be determined by potentiometric titration of the copolymers. For a
given pH, the CD is found to increase with an increase in the copolymer concentration
or the ionic strength.i2* The pK, is a function of concentration and the mole fraction
of acrylate.
Very low-MI% (generally under 10 000) polymers of high CD are used for the dispersion of scale-forming precipitates and the inhibition of crystallization of potential
deposits. 37 They are sy nthesized by homopolymerization
of acrylic or methacrylic
acids, or by extensive hydrolysis of acid precursor groups. The acrylates are used
for deposit control in cooling towers, the methacrylates being more commonly used
for the same purpose in boilers. Maleic acid polymers made from hydrolysed homoand copolymers of maleic anhydride have important applications in this area. Of a
range of polymers recently investigated, partially hydrolysed polyacrylamide was
superior in inhibiting silica scale deposition. 12
A possible new route to the preparation of acrylic acid copolymers is the electrochemical carboxylation of poly(viny1 halides) and polybutadiene.13 So far the maximum extent of carboxylation achieved is 10%. Low-M@, high-CD anionic polymers
of structure (XVI) based on acrylamidoalkanoates
have been made and tested at
pH 6.5 as coagulant aids for alum in water treatment.13r The x = 6 and x = 11 products were superior to the x = 11 methacrylo and ethacrylo analogues, and were as
effective as conventional commercial cationic polymers. The adsorption of random
and block copolymers of acrylic acid and vinyl alcohol which are of very low MW
(33 000-l 10 000) onto barium titanate particles has been measured.132 In very
k-\jf
n
co
NH
GO
@H&x/
XVI
O_
1010
B. A. BOLT0
T
n
low-CD polymers containing up to 3.4mol% carboxylate, more than three times the
amount of block copolymer is adsorbed compared to the random copolymer.
5.2. Sulphonic Acid Polymers
Poly(vinylsulphonic acid) is the simplest example of this family of fully ionized strong
electrolyte polymers. Ion binding by the polymer has been the subject of several
studies.33 The homopolymer (XVII) and its copolymers with methacrylic acid are
reported to be useful in deposit control, as are copolymers of allylsulphonic acid and
fumaric acid.37 The ion-binding properties of poly(styrenesulphonic acid) have likewise been studied;34 it has considerable commercial importance in deposit control,
especially as low-&W hydrolysed copolymers with maleic anhydride, and some use as
a flocculant. It is generally prepared by sulphonation of polystyrene, and careful
choice of the sulphonating conditions is necessary to minimize crosslinking and the
formation of insoluble gels. The best reagent appears to be a sulphur trioxide-trialkylphosphate complex, with the major product being the para isomer (XVIII).37
Several acrylate or acrylamide polymers containing sulphonate groups are commercially relevant as high-MW flocculants or low-MI+ deposit control agents.54 These
include homopolymers of sodium 2-methacryoyloxyethyl
sulphonate35 (XIX) and
sodium 2-acrylamido-2-methylpropyl
sulphonate136 (XX), and their copolymers
with acrylamide or acrylic acid. 137For the latter products, copolymer compositions of
high-&W materials have been determined by 13C NMR for a CD range of 5-75 mol%.
kzjf
co
n
n
00
NH
-=3
SOLUBLE POLYMERS
IN WATER
PURIFICATION
1011
q H
R = Me
XxIa, A
Xxlb,
The adsorption of (XX) on sodium kaolinite clay has been followed with a 14C-tagged
acrylamide copolymer and determined as a function of pH and temperature.13*
Similar useful polymeric flocculants have been made from hydroxy-substituted
species such as 3-methacryloyloxy-2-hydroxypropyl
sulphonate by starting with the
appropriate monomers,54 or by reacting polyacrylamide or copolymers of acrylamide
and acrylic acid with N-(2-hydroxy-3-sulphopropyl)amide.39
Sulphated hydroxy polymers are also known, an example being the sulphate ester
made from poly(viny1 alcohol) by reaction with chlorosulphonic acid,37 but these are
hydrolytically unstable at extreme pH levels.
5.3. Phosphonic Acid Polymers
One of the simplest phosphorus-containing
polymers is poly(vinylphosphonic acid),
shown as structure (XXIa); its polyelectrolyte behaviour has been investigated.14
Being a strong dibasic acid, it is capable of a very high CD. The polymeric phosphonates are mainly used in deposit control and as sequestering agents because of their
chelating properties. The various products available have been reviewed.37 Phosphonated polyethylene is knowns4 Poly(isopropenylphosphonic
acid) of structure OU(Ib)
is a new polymeric dispersant for iron deposit control in high-pressure industrial
boilers.141
The complicated synthesis of further acrylate and methacrylate polymers having
phosphonate groups has been reported recently.42 Phosphonomethylated
polyacrylamides suitable for water treatment are reported.43
Many sulphated polysaccharides are available as natural biopolymers or their
derivatives, some examples being heparin, dextran sulphate, mannan sulphate and
I
NH
NH
1012
B. A. BOLT0
chondroitin sulphate, but the applications are mainly medical.lU One proposed for
use in the water industry is the modified natural polymer lignin sulphonate, prepared
by sulphonating low-MWkraft pine lignin. 145Certain of these polymers are equivalent
in performance to cationic polyacrylamides for the dewatering of sewage sludge.
Potato starch contains 0.13% phosphorus in the form of phosphated hydroxy
groups, and can be considered as an anionic polyelectrolyte of extremely low CD.46
6. NON-IONIC
POLYMERS
Synthetic polymers like polyacrylamide are a relatively recent innovation in the

water industry, dating back some three decades, but some polymers of natural
origin have been used for many centuries.
6.1. Polyacrylamide
Synthetic polymers which are often quoted as non-ionic actually contain, as in the
case of polymers and copolymers made from acrylamide, some l-3% of anionic
groups arising from the hydrolysis of amide groups.43 Polyacrylamide with less than
1% hydrolysis can be prepared by careful attention to the monomer concentration,
pH, temperature and initiator, with a redox type preferred.37 The hydrolysis conditions have received detailed attention. *47
6.2. Poly(ethylene
oxide)
Polymers of low to high MW are available. They have application in mining flotation processes and drag reduction in pipeline flo~s.~~ The adsorption of triblock
copolymers containing poly(propylene oxide) on colloids is greater the more hydrophobic the copolymer.48
Those utilized include starches, galactomannans, cellulose derivatives, microbial

polysaccharides, gelatins and glues. They are used as flocculants to aid solid-liquid
separations, and vary in their structure, ME, biodegradability, and ease of dissolution.49 Their main advantages are ready acceptance on health grounds and
ease of biodegradation. Tannins have also received attention.15 Of historical interest
is the purification of drinking water with macerated seeds from the horseradish tree,15
while recently the enhanced extraction of algae from ponds with crushed red sorella
seeds has been reported.152
7. AMPHOTERIC
POLYELECTROLYTES
Amphoteric polyelectrolytes, or polyampholytes, have both anionic and cationic

sites on the same polymer chain. The sites of opposite character may be of a strong or
weak electrolyte type, and the ratio of sites can be varied. An equal number of anionic
1013
and cationic groups results in zwitterionic structures, which may also be incorporated
in one monomeric unit to give betaine-like structures.
A unique feature of 1 : 1 amphoteric polyelectrolytes is their anti-polyelectrolyte
behaviour, in the sense that an increase in ionic strength causes an increase rather
than a decrease in the viscosity of the solution. This property is of immense significance in applications like enhanced oil recovery. Other uses are water clarification,
sludge conditioning and the adsorption of metal ions and dyes. Variations from the
1 : 1 ratio result in normal polyelectrolyte properties.
7.1. Amphoteric Copolymers
There are review articles on their synthesis, which can be by copolymerization or by
substitution in an existing polymer. 1531154
The products are random, alternating, graft
or block copolymers, depending on the method of preparation. The copolymerization
of strongly basic cationic monomers such as methacrylamidopropyltrimethylammonium
chloride1551156 or 2-(acrylamido)-2-methylpropyhrimethylammonium
chloride1571158with strongly acidic anionic monomers such as sodium 2-acrylamido2-methylpropyl sulphonate gives a product with the simple structure (XXII). Free
radical or redox initiators are effective. An inverse microsuspension method was
employed to produce a high-MWmaterial in one case.156 The copolymer composition
can be determined by 13C NMR and elemental analysis, and shows a slight tendency
towards alternation.157158 Polyampholytes with balanced stoichiometry showed an
increased water solubility and enhanced viscosity on adding salt.156
The same type of strongly basic cationic monomers in the form of acryloyloxyethyltrimethylammonium
chloride159-161 or DADMAC16* have been copolymerized with
weakly acidic anionic monomers such as those arising from acrylic or methacrylic acid
to give structures akin to (XXIII). The former are claimed to be effective in sludge
dewatering,159160as is their terpolymer with acrylamide.161 The DADMAC copolymers on the other hand are claimed to be useful flocculants, other variations for this
application being terpolymers with hydroxyalkyl acrylates,162 or the use of 3-acrylamido-3-methylbutanoic
acid as the weakly acidic monomer.164 The latter in a lowCD terpolymer with acrylamide performs well in drag reduction.157 When the acidic
monomer is maleic acid or its anhydride, the copolymer is effective in controlling scale
deposition.65 Amphoteric polymers have been made by reacting half the chloro
groups in chloromethylated
polystyrene with trimethylamine, and the remainder
with sodium phloroglucinate to yield the polymer (XXIV). Here the aim was to
1014
B. A. BOLT0
produce a flocculant which is cationic at pH 5-6 and neutral at pH 10-l 1, to ensure its
disengagement from carrier particles at the elevated PH.~~
Weakly basic cationic monomers
in the form of dimethylaminoethyl
methacrylate15367 or 2-acrylamido-2-methylpropyldimethylamine168
form polyampholytes of type (XXV) with the strongly acidic anionic monomer sodium
2-acrylamido-2-methylpropyl
sulphonate. The first of these basic monomers gives a
product useful in sludge conditioning.67 Polymers from the second have been characterized by 13C NMR and shown to have a high alternating tendency, while low- to
medium-CD terpolymers with acrylamide have enhanced viscosities compared to
high-CD polymers, the latter having half the viscosity of the lower-CD versions.6g
The combination of weakly basic and weakly acidic monomers has received much
attention. Those derived from dimethylaminoethyl
acrylate or methacrylate and
acrylic or methacrylic acid are claimed to be appropriate for sludge dewatering
since they form large strong flocs,17* and are noted to form complexes with dyes,
surfactants and cationic polyelectrolytes.71 The terpolymer with acrylamide can
also yield sludges of low water content.72 The same property is obtained when the
basic monomer is dimethylaminopropyl
acrylate.73 The terpolymer of 2-acrylamido2-methylpropyldimethylamine,
3-acrylamido-3-methylbutanoic
acid, and acrylamide
has enhanced water absorbency.74 Copolymers of 2-methyl-5-vinylpyridine
and
acrylic acid are capable of metal ion uptake.75 Block copolymers have been made
from 2-vinylpyridine
and acrylate or methacrylate
esters by living anionic
XXVI
SOLUBLE POLYMERS
IN WATER
PURIFICATION
1015
XXVII
?5
N+
coo-
xxv111
polymerization, followed by hydrolysis.53 Graft copolymers obtained from the reaction of ethyleneimine with poly(acrylic acid) are effective as sludge dehydrating
agents.176
7.2. Polymers Containing Zwitterionic Units
By reacting the his-acrylamide of piperidine with amino acids of the type
NH2(CH&COOH,
poly(amido-amines) of structure (XXVI) can be formed,108 with
x = l-3 or 5. They bind to copper ions, but disperse copper mineral particles, whereas
polymers like (XIII) with no acidic functionality and with R a methyl or hydroxyethyl
group flocculate the mineral. The carboxymethylation of chitosan, shown as (XIV),
via the reaction of hydroxy groups with chloroacetic acid yields a polymer containing
zwitterionic groups, depending on the pH level. The modified polymer has the advantage of being soluble at high PH.~~ An amphoteric polymer synthesized from polyacrylonitrile and dicyandiamide has use as a flocculant for treating industrial
effluents.78 The resulting structure (XXVII) contains 15.6mol% of carboxylic acid
groups and a similar amount of weakly basic aliphatic groups, plus 62.5 mol% of
amide groups, with the remainder being nitrile and tetrahydropyridine
units. It is
soluble in weakly acidic or alkaline media,
Extensive studies of the synthesis and properties of polymeric betaines have been
carried out.54 A typical example of a polyvinylbetaine179 is shown in (XXVIII), with
XXIX
1016
B. A. BOLT0
coca
xxx
the zwitterionic structure being dependent on pH. The polyvinylsulphobetaines

are
similar, with a sulphonate in lieu of a carboxylate group.** The main attribute of the
polymeric betaines is anti-polyel~trolyte
behaviour in terms of solubility and viscosity, with the solubility depending on the presence of salts and being strongly
influenced by the nature of the salt. The viscosity increases with increasing salt
concentration.
Synthetic poly(a~no acids) are well known,@ poly(L-aspartic acid), for example,
receiving increasing attention for its metal-adsorbing properties as applied to the
inhibition of corrosion18 and scale deposition,182 and in formulating detergents.ls3
A major point of practical interest with this polymer, shown as structure (XXIX), is its
biodegradability.84 Amino acid substituents have been used in cationic polyelectrolytes to give the polymer overall neutrality at high pH. Thus, glycine has been incorporated in structure (XXIV) instead of phloroglucinol.146
8. HYDROPH[OBICALLY
MODIFIED
POLYELECTROLYTES
Amphiphilic polymers are of interest as dispersants to help suspend solid particles in

liquids in the paint, paper, textile and other industries. They also have potential as
viscosity modifiers, and a neutral polymer like poly(N-isopropylacrylamide)
has the
additional characteristic of thermally sensitive behaviour. In hydrophobically modified polymers the rheological properties depend very much on the number of alkyl
groups per chain, and whether the groups are randomly situated or occur at the ends of
the chain.186 Some charged versions may have use as flocculants and adsorbents.
8.1. Cationic
Part amination of chloromethylated polystyrene as in (IX) gives water-soluble products when the CD is greater than 35 mol%. They will flocculate silica suspensions
used as models for raw water, and will also adsorb non-polar organic pollutants of the
polyaromatic hydrocarbon type.lp7 The two processes may occur simultaneously, with
fluorescence studies showing that adsorption involves the hydrophobic part of the
polymer and increases with an increase in the hydrophobic nature of both the polymer
and the pollutant.
Surface-active copolymers of methacryloyloxyethyltrimethylammonium
chloride
with n-butyl methacrylate have been prepared in ABA triblock form, with the
cationic blocks at the ends.*** Copolymers of the same cationic monomer with acrylamide which have an anionic surfactant ionically bonded to them have been used to
SOLUBLE POLYMERS
IN WATER
1017
PURIFICATION
xxx1
flocculate sewage.* The copolymers of dimethyldodecyl(Z-acrylamidoethyl)ammonium bromide and acrylamide shown as (XXX) have interesting solution properties.
With a CD of 5 mol% the random copolymer undergoes intramolecular hydrophobic
association, as determined by pyrene probe fluorescence, whereas block structures
promote inte~olecular
association.19o Inte~olecular
association is enhanced with
increases in the length of the hydrophobic blocks or in the number of blocks in the
polymer chain.
Terpolymers of acrylamide with acrylic acid, sodium 3-acrylamido-3-methylbutanoate

or sodium 2-acrylamido-2-methylpropyl
sulphonate which contain
0.5 mol% of n-decylacrylamide have been synthesized and characterized.g1 Hydrophobic associations in the carboxylate terpolymers are more pronounced than in the
sulphonate analogue. Products of this type may have commercial applications in many
areas, including flocculation. Surfactant-like properties are exhibited by ABA triblock
copolymers of methacrylic acid and 2-ethylhexyl methacrylate, with the charged units
again being at the ends of the chain.192
8.3. Amphoteric
Viscosity studies of terpolymers containing acrylamide, 2-methacryloyloxyethyl
sulphonate and variously substituted 2-methacryloyloxyethylalkyldimethylammonium
ions show shielding effects by hydrophobic groups.193 Heptafluorobutyl and benzyl
substituents prevent the formation of ionic clusters of the oppositely charged units,
present at up to 2-4mol%, thus causing an expansion of the polymer chain in water.
However, the rigidity of the chain can reinforce this effect, with the benzylic polymers
performing better than the fluorocarbon analogues.
9.
PRACTICALITIES
IN THE
USE
OF POLYMERIC
FLOCCULANTS
There are a number of practical topics that need particular attention when using
polyelectrolytes for water or wastewater treatment. They include specific handling
requirements in making up polymer feed, selection of polymer type and dose, methods
of controlling and monitoring the dosage, analysis of residual polymer in the purified
water, allowances for polymer degradation, and concerns over polymer toxicity.
1018
B. A. BOLT0
9.1. Makeup, Selection and Dosing

Dissolution systems which are designed to take into account the unique physical
characteristics of polymers are well documented.9496 The selection of the optimum
type and dose of polymer required is determined by jar tests, as is done for metal salt
coagulants.40>196 Typical doses are l-lOmgl_
for drinking water production, lo100 mg 1-l for wastewater treatment, and 100-1000 mg 1-l for sludge conditioning. 197
For water and sludge treatment generally, under- or overdosing of polymer can have
very significant detrimental effects. Underfeeding causes high suspended solids and
colour levels in the product water; overfeeding results in redispersion of the impurities
and carryover of polymer from the clarifier to the filter, with blinding of the latter so
that there is an increased backwash frequency and water 10~s.~~Considerable effort
has gone into ways of monitoring polymer requirements during process operation.
9.2. Monitoring Systems
Control of flocculant use by a streaming current detector (SCD) has been the most
successful method to date. The streaming current is caused by the movement of
counterions beyond the shear plane of surfaces within the sensor. The fluid motion
carrying the ions results from piston reciprocation within a closed cylinder in contact
with a sampled flo~.~~ The output from the SCD is related to the zeta potential or
electrophoretic mobility of the suspended particles. Hence it is possible to directly
follow the reduction of the negative surface charge on the particles in the water,
and to select the optimum dose which occurs when the charge is neutralized. Automated control for drinking water production is then achievable.200 The technique has
also been successfully applied to sludge conditioning, optimal sludge flocculation
being obtained at near neutral streaming current.201
Another promising method is based on measurements of fluctuations in the intensity
of light transmitted through a flowing suspension. 202In some cases quantitative information on floe size can be derived, but the main use of the technique is as a sensitive
monitor of the state of aggregation.
9.3. Chemical Analysis
It is essential to determine the ultimate fate of polymers used in the treatment
process, plus that of any impurities present in the original polymer. A number of
approaches have been studied. To confirm that all the added polymer remains
attached to particles which are removed prior to water. use, it is necessary to analyse
for polymer residues in solution. This can be done by colloid titration against a
polyelectrolyte of opposite charge, using dyes203>2or with fluorescent compounds
as indicators,205 but the method is not especially sensitive, 0.5%1 mg 1-l being the lower
limit. A variation on this theme for cationic flocculants is to measure the light absorbance at 680 nm following progressive additions of a standard solution of an o, odihydroxyazo compound, which participates in an association reaction with the polymer.206 A similar method is based on tannic acid.207
SOLUBLE
POLYMERS
IN WATER
PURIFICATION
1019
In the analysis of a high-M@, low-CD copolymer of acrylamide and sodium acrylate (XV), separation by exclusion chromatography and fragmentation by flash pyrolysis followed by GC-MS have also been employed.* A number of impurities were
present at very low levels in water treated with the commercial product, including the
monomers acrylamide and sodium acrylate, and also hydroxypropionitrile and traces
of isobu~yro~trile from the initiator. The sensitivity was lo-20 pg 1-l.
9.4. Tagging of Polymers
A number of workers have followed the course of flocculation with specially synthesized 14C-tagged polymers.20g They have been used to show that dissolved organic
matter reacts with the polymer before the turbidity particles, and that hydrolytic
degradation of polyacrylamide is negligible under normal operating conditions. 38The
final destination of a p$ymer used in a particular treatment process has been shown to
be on solid particles.
A fluores~ently labelled cationic polyacrylamide has been made by including choline
in a Hofmann reaction on polyacrylamide.210 The solution behaviour of polyelectrolytes has been extensively studied via photophysical studies of pyrene-labelled
polymers, one example being polyacrylamides substituted with 0.3 mol% of pyrenesulphonamide.211
9.5. Polymer Degradation
The hydrolysis of the ester links in the cationic polyacrylamides (I) has been discussed in Section 4.1 and shown to be pH- and CD-dependent, being more facile as the
pH is increased.4W8 As has also been mentioned, amide groups are generally much
more stable.
Oxidation of anionic polyacrylamides with ozone under disinfection conditions is
reported to produce mainly formic acid.208 Likewise, chlorine under disinfection conditions forms trihalomethanes, mostly from the monomeric material present, but the
amounts do not cause a problem because of the very low levels of the starting compounds (< lOOngl_). The level obtained from the polymer in another case was 78 /&g1-1.22PolyDADMAC forms similar amounts.23
Biodegradation of synthetic polymers is extremely slow, as most of the structures
utilized are resistant, although amide groups are susceptible,214 as are the ester links in
cationic polyacrylamides.215 The poly(acrylic acid) formed can be degraded in the
natural environment, but only material of very low MW (below 4000) seems to be
affected.216 Biodegradability
of the methacrylate chain can be facilitated by
HO-N=C
I
NH,
CO
I
NH
AH
xxx11
1020
B. A. BOLT0
incorporating N-benzyl-4-vinylpyridinium
units.217 A more biodegradable anionic
polyelectrolyte in the form of sodium polyvinyloxyacetate @XXI) has been prepared
which cleaves to produce easily degradable poly(viny1 alcoho1).218
Natural polymers based on polysaccharides and proteins are readily degraded at the
ether and amide sites, respectively.214 Where the solids recovered from wastes are of
value, as in the food processing industry, biodegradability is a useful attribute. Synthetic analogues of natural polymers which have this advantage, such as poly(aspartic
acid)219 and acrylic acid grafts on polysaccharides,220 are seen to have a future as
biodegradable scale control agents.
9.6. Toxicity
The normally used anionic and non-ionic polymers are of low toxicity generally, but
cationic types are more toxic, especially to aquatic organisms; the monomers are generally
more toxic than the polymers. 221Because of concern about contaminants, Japan and
Switzerland do not permit the use of polyelectrolytes for drinking water treatment,
and Germany and France have set stringent limits. The health significance of possible
contaminants has recently been reviewed in detai1.213Limits on the level of monomer
are strictly controlled, especially with acrylamide products, where as a general rule the
maximum allowable content of free acrylamide is 0.025%, and the residue in drinking
water in most countries is limited to 25 pg 1-l . For polyDADMAC the monomer content
limit is 5%, and a suggested maximum permitted level in reservoirs is 500 pg 1-l .222
For drinking water production the recommended maximum doses for the usual
commercial flocculants are 10 mg 1-l for quaternary ammonium polymers213>221and
0.5 mg 1-l for products based on acrylamide, while flocculants based on starch can be
used at 3-5 mg 1-l depending on the type.221 Polyethyleneimines are generally not used
in potable water treatment, and there is concern about epichlorohydrin-derived
flocculants for this purpose.213
In determining the toxicity of polymers to aquatic species there are different parameters compared to non-polymeric additives.2 2 Synthetic polymers tend not to be
readily absorbed by organisms, and their toxicity may be substantially altered by key
aquatic components.223 Cationic polymers are markedly more toxic to aquatic organisms than anionic or non-ionic polymers, being of moderate to high toxicity.224 They
are detrimental to fish because of gill blockage, which causes suffocation.197 This is
greatly reduced by the addition of solids such as clays which are normally present in
various forms in receiving waters and sediments, where they can strongly adsorb the
cationic polyelectrolyte.225 Humic acids also affect the toxicity, reducing it by an order
of magnitude at a humic acid level of 5 mg 1-i .226The cationic polymer pregtred by
polymerizing vinyl chloroacetate after its amination with trimethylamine
has a
reduced toxicity to fish, presumably because of loss of the cationic groups by cleavage
of the ester links.
10.
APPLICATIONS
The main applications
OF POLYELECTROLYTES
of organic polyelectrolytes
in the water industry
are in
1021
coagulation and flocculation, and in sludge treatment. The first two processes are
usually followed by sedimentation and filtration, although with only slightly contaminated waters the sedimentation step can be omitted. Flotation is an option instead of
sedimentation, especially for algae-laden waters or for oil- and grease-contaminated
wastes. The sludges obtained from the various separation processes have very high
water contents and must be further concentrated to minimize transportation costs;
polymers have a role in this sludge conditioning. The removal of metal ions from
solution by soluble polymers is another application, either by forming a precipitate
or by producing a much larger soluble polymer-metal complex which can be removed
via membrane technology.
10.1. Primary Coagulation in Drinking Water Treatment
Organic polymers may be used as primary coagulants as well as in the more traditional flocculation step of binding already-formed small floes into larger particles. The
polymer acts as a destabilizing agent via a charge neutralization-precipitation
mechanism, and is also an agent for floe growth as illustrated in Fig. 10. In the
production of drinking water a cationic polyelectrolyte of high CD and low to
medium MW such as polyDADMAC (III) can be used instead of a metal salt as the
primary coagulant (Section 3.1). Polymers of the epichlorohydrin-dimethylamine
type (IV), allowable in some countries, are also effective, as is polyethyleneimine
lnitidl Chemical Interaction
HumicAcid
Cationic Polymer
Destabilized Particle
F lot Formation
Destabilized Particles
Schematic
representation
Cross LinkedFlocParticle
of humic acid/PEl destabilization
Fig. 10. Diagrammatic representation of the destabilization of humic acid by a cationic

polyelectrolyte (from ref. 227. Copyright 1979 American Chemical Society and reprinted
with permission).
1022
B. A. BOLT0
Settled
UV
300
s
(
g
200
2
2
100
Cationic
12
polymer
16
dosage
20
24
(mg/L)
Fig. 11. Jar test data for the coagulation of 10 mg 1-l of humic acid at pH 6 by means of a
cationic polyelectrolyte (from ref. 18. Copyright 1986 John Wiley & Sons, Inc. and reprinted
with permission).
(VI), which is of theoretical interest only. Laboratory studies show that the negative
charge on humic substances can be eliminated by the cationic polymer polyethyleneimine,227 facilitating agglomeration. The best turbidity and colour removal
occur when the mobility or zeta potential of the particles is close to zero, or the
particles carry net zero charge (Fig. 11).18
In jar tests on synthetic and natural waters of low turbidity and moderate to high
colour, high-CD cationic polymers are effective in removing the organics responsible
for colour, and for lowering the potential to form trihalomethanes
after
The
CD
rather
than
the
MW
is
important
in
selecting
the
optimal
chlorination.228
conditions, and the initial periods of both rapid and slow mixing are critical in the
formation of flo~s.~~~These waters are ideal candidates for polymer coagulation.
Avoiding the use of an inorganic coagulant has the advantages that a smaller
amount of sludge is produced in a system less sensitive to pH, and that there is less
dissolved salt present. 40,230There is also concern that residuals from aluminium-based
coagulants may have a link with Alzheimers disease.
A settleable floe is not usually formed, but the solids can be readily removed by
filtration when strong porous floes are needed. For dilute suspensions the settling stage
normally employed in conventional treatment plants is kinetically inefficient. In direct
1023
filtration, where some time is allowed for floe growth to achieve optimum size, there is
no such sedimentation step, which makes for lower capital costs. The use of polymers
to facilitate direct filtration has been reviewed some time ago, and the effect of charge
type and MW summarized.231 The main mechanism is charge neutralization, with anionic
polymers being the least effective, although there is an improvement if calcium or magnesium cations are present. Cationic polyelectrolytes have a distinct advantage over the
metal salts which are commonly used in this procedure, because they effect charge
neutralization without the formation of additional solids in the form of metal hydroxide precipitate. Moreover, the floes from inorganic coagulants are not compressible,
so they take up much of the space in the filter medium, rapidly causing a pressure
drop.232 Polymers give the advantages of a deformable floe, extended filter runs, and
decreased sludge volume from filter backwashing. Polymer MWdoes not seem to be a
major variable. The initial mixing intensity and the mixing time are the most important
parameters in determining the particle size of the floe formed prior to filtration.231
Direct filtration is an appropriate process for obtaining potable water from a raw
water that is not heavily contaminated, as otherwise too high a dose of polymer is
needed or the polymer must be used in conjunction with metal salts. Typically, a dose
range of 0.5-5 mg 1-l of active polymer is required,** with the aim of presenting small
pin-sized floes to the top of the filters before the development of large floes, so that the
top of the filter bed is not rapidly covered to cause blocking. The floes should enter the
body of the filter and have a strong tendency to adsorb to the filter medium (usually
sand).233 The upper limits to the levels of impurities in the raw water for adequate
performance in terms of filter run length have been set at 5 nephelometric turbidity
units (NTU) and 40 platinum colour units (PCU),234 although there are many
examples of much dirtier raw waters being satisfactorily treated. Thus, water having
a seasonal variation of turbidity of 2-176 NTU has been cost-effectively treated on the
full scale with cationic polymers instead of alum in a direct filtration system.235
For waters high in organics, a substantial polymer dose is needed, but compared to
alum usage the filter run can be more than double in length, as shown in pilot plant
studies.* To achieve a head loss of 1OOcm of water at a dose of 14mg 1-l of alum
required 5.5 h. When 10 mg 1-l of a cationic polyelectrolyte was the coagulant instead
of alum, to attain the same head loss when there was no flocculation stage took 14 h. If
a flocculation time of 18.4 min was in force, the time required was extended to 24 h.
If it is found that direct filtration of waters containing large amounts of humic
substances with cationic polymers as the sole flocculant is not economic because of
the high dose required, conventional metal ion coagulants can be used with a lower
dose than is normal to minimize the amount of precipitate. This is followed by a highCD cationic polymer such as polyDADMAC (III), used in charge neutralization mode
rather than causing particle bridging to give large floes, although the floe size is still
increased.236 Such a mode of operation is in extensive use.
Another very worthy application is in increasing the capacity of a filter plant which
has been operated with inorganic coagulant by polyelectrolyte addition. Thus an
increased flow of 25% was achieved by adding 0.3 mg 1-l of cationic polymer after
ferric chloride dosing, the level of which was lowered from 12-15 to 8-9 mg 1-l .233
1024
B. A. BOLT0
This was accompanied by a longer filter cycle time of 17-20 h vs 1l-l 3 h, and an
improvement in the product water quality. The cost of the polymer was completely
recovered by the decreased outlay on ferric chloride. When alum is used, careful
control also minimizes the carryover of aluminium-containing
particles into the distribution system.237
A number of workers have discussed the turbidity limits when alum is the coagulant,
and this has been reviewed recently in a consideration of highly turbid waters, covering
a range of 5-200 NTU.238 It was noted that the alum dose required for effective
coagulation and filtration could be the limiting factor, with 12-15 mgl- suggested
as the upper limit. A combination of 7 mg 1-l of alum, 0.26mg 1-l of the high-CD
cationic polymer derived from epichlorohydrin
and dimethylamine
(IV) and
0.01 mgl- of polyacrylamide as filter aid successfully treated 21-28 NTU water.239
The concept of pretreating the medium rather than dosing polymer to the full feedwater flow has been explored, and the binding of polymers to sand noted to be ten
times more intense for cationic and non-ionic polymers than for anionic polymers.231
The polymer can be added to the backwash water for a portion of the backflow time.
There have been pilot studies of the method but it is not in common use.
Cationic polymers can coagulate freshwater algae at doses of I- 10 mg 1-l .240However, the high salinity of marine systems inhibits the process. Direct filtration experiments have demonstrated that the dose of cationic polymer must be more than that
necessary to overcome the effects of exocellular matter released by the algae, and then
good cell removal is possible.241 A high-CD polymer is preferred. Employing an
inorganic coagulant for this purpose can disrupt the cell membrane and release compounds which give rise to taste and odour in the product water.242 With blue-green
algae, toxins are produced which can be a health hazard. They can be removed by
oxidation or by adsorption on activated carbon, but these are both expensive treatment options. The amphoteric polymer (XXVII) obtained by reacting polyacrylonitrile with dicyandiamide has been shown to aggregate algal cells without killing
them.78
10.2. Primary Coagulation in Industrial Wastewater Treatment
Coagulation with organic polymers followed by sedimentation can clean up industrial effluents when the floes formed are dense enough. Those most successfully treated
are from the food industry, where chitosan (XIV) can give a 90% reduction in the
turbidity of bean processing wastewaters, allowing the reuse of some wash waters.243 It
can also reduce mesophilic bacterial spore counts by 96%. The treatment of wastes
from many food processing industries and the recovery of useful solids are included in
a major literature review on chitosan. Chitosan and polyethyleneimine (VI) are
effective in enhancing separation of cell debris by centrifugation in the processing of
biotechnical products.244
Polyethyleneimine245 and the low-CD amphoteric polymer (XXVII)78 are capable
of removing colour from paper mill effluents. Partial colour removal from dyehouse
wastes is possible with a high-CD cationic polymer, but at very high doses.246 The
amphoteric polymer (XXVII) is claimed to eliminate colour from similar wastes.178 In
1025
other examples, applying a cationic polymer with clay, which acts as both an adsorbent and a weighting agent, takes out some colour but is less effective than alum.247 In
fact, inorganic coagulants are much used in industrial effluent treatment, often in
conjunction with a polymeric flocculant, as will be dealt with in Sections 10.3 and 10.4.
Wool scouring effluents can be coagulated with polymer only, a high-MWpolymer of
slightly cationic or slightly anionic behaviour being preferred, depending on the
characteristics of the waste.248 In one example a 100 mg 1-l dose of the cationic type
reduced chemical oxygen demand (COD) and suspended solids (SS) by 50% and 57%,
respectively. The redeposition of colloidal magnetite particles during the decontamination of nuclear reactors is reduced in the presence of polyelectrolytes. Poly(acrylic
acid) was the most effective of many cationic and anionic species investigated.249
In the treatment of industrial effluents that are loaded with emulsified oil and grease,
as occurs in wool scouring or in steel mills, the organic phase sometimes prefers to float
rather than settle. High separation rates can be achieved by first coalescing the
organics and then using induced air or foam flotation.250 Large air bubbles are
formed which result in faster rise rates and lower capital costs than are achieved
with the small-bubble systems prevailing in the competing technology of dissolved
air flotation. For oil and grease emulsions an inorganic coagulant is not required, the
necessary effect being obtained with the medium-CD, high-MW copolymer of acrylamide and quaternized dimethylaminoethyl acrylate or methacrylate (I), which adequately neutralizes the negatively charged organic phase. The lack of a dependence on
MW suggests that bridging of particles by the polymer does not occur to any significant degree, and that charge neutralization is sufficient to ensure coalescence, as shown
earlier in Figs 9 and 10.
In dissolved air flotation a proportion of the treated water is recycled through a
pressurized air saturation system, and the air-saturated water is then released into the
water to be treated.196 Suitable polymers can redress any floe shearing brought about
by overly vigorous contacting of the bubbles with the particles. The solids attach
themselves to the small bubbles produced and float to the surface. Oil-in-water emulsions in food industry wastes can be broken by cationic polymers such as chitosan,
polyethyleneimine
or the copolymer of acrylamide and quaternized dimethylaminoethyl acrylate (Ia) of medium CD and high MW.251 Cationic starch of low
CD can also break emulsions of this type.252 Oils can be removed from metal processing wastewater by flotation after the addition of a cationic polymer plus an acrylamidoxime-acrylhydroxamic
acid copolymer of structure (XXXII).253 Particles in
refinery wastewaters have been destabilized with a high-CD, low-MU cationic
polymer and then agglomerated with a high-CD, very high-MW anionic polyacrylamide.254
10.3. Flocculation in Drinking Water Treatment
A major use of organic polymers in water treatment is as a coagulant aid to bridge
the coagulated particles formed when an aluminium or iron salt has been used as the
primary coagulant, in the manner described in Section 3.2. An appropriate polyelectrolyte can increase floe size: a strong dense floe of regular size is preferred. The large
1026
B. A. BOLT0
aggregates that form then settle more rapidly. The particles produced by the inorganic
salt generally have a slightly positive or slightly negative surface charge, depending on
the dose of metal salt and the pH of the system.
With floes of slightly positive character an anionic polymer of low or medium CD
and high MW is appropriate, such as the partially hydrolysed polyacrylamide (XV),
and the reaction is as in eq. (4) and Fig. 8. The use of polymers in this way results in a
substantial lowering of the alum dose required, a 40-60% reduction being possible.22t31t96Thus for a water containing 5 mg 1-l of humic acid, a dose of 75 mg 1-r
of alum will remove only 20%, but dosing 5 mg 1-l of an anionic polymer in conjunction with 10 mg 1-l of alum will give a 95% reduction.22 An excess of polymer can
cause redispersion of the impurities.227
When the coagulated solids have a slightly negative charge, a cationic polymer of
low CD and high MW, such as the copolymer of acrylamide and quaternized
dimethylaminoethyl acrylate or methacrylate (I), is effective in forming larger flo~s:~
>Al-OOCRCOO-
+ polymer+
+ -OOCRCOO-Al<
--+ >A1-00CRC00-polymer-00CRC00-A1<
(6)
Processes are now being optimized for organics removal in enhanced coagulation
systems so that the production of harmful disinfection by-products is minimized.256
These systems are also used for the elimination of particulates to the greatest possible
extent to ensure the absence of pathogenic organisms like Giardia lamblia and Cryptosporidium in the product water.257 This requires the best combination of inorganic salts
as coagulant and polymer as flocculant, the best type of polymer and the optimum
concentration ratio and process conditions.258 Sludge properties are also very dependent on the additives utilized, especially the amount of inorganic coagulant. The
emerging technology of coagulant recovery will do much to reduce the volume of
sludge for disposal.259 Separation of organic material from the recovered metal ions
is essential if performance equivalent to that of fresh coagulant is desired.
10.4. Advanced Primary Treatment of Sewage
Chemically assisted sedimentation of sewage can provide an intermediate level of
treatment to give a temporary upgrade, but it cannot meet biological secondary treatment performance of 85% biochemical oxygen demand (BOD) and SS removal. A
recent example at a plant treating 500 Mid-* of sewage has shown a substantial
improvement when ferric chloride is dosed at 50mgll for 6 h, then 15 mgl- for
the rest of the day, always with an anionic polymer such as the partially hydrolysed
polyacrylamide (XV) at 1 mg 1-l .260The removal of BOD is then 36% vs 15-20% with
no chemicals, and 55% of the SS is taken out vs 25-40% when no chemicals are added.
If lime is the coagulant, a low- or medium-CD cationic polymer of high MW is
preferred.
An analogous approach to sewage treatment makes use of a fluidized pellet bed
separator, in which coagulation with lo- 15 mg 1-l of poly(aluminium chloride) and
flocculation with 1.5 mg 1-i of a low-CD anionic polyacrylamide removes suspended
SOLUBLE
POLYMERS
IN WATER
PURIFICATION
1027
matter and forms large pellets.26 In a later variation, pelletizing is brought about with
only a cationic polymer, at a dose rate of 10-20mg1-.262 Pelletization has been
studied for drinking water preparation, but is less effective on dilute feed waters.
Partial phosphate elimination from sewage by precipitation with metal salts has
long been in use. A recent variation of the method has been the replacement of
some of the metal salt with a cationic polymer without loss of efficiency of phosphate
removal, indicating that the polymer is involved in adsorption of anionic phosphorus
species.263 In a full-scale plant the normal dose of 23 mg 1-l of ferrous sulphate was
reduced to 12 mg 1-r plus 3 mg 1-r of a high-CD cationic polymer, along with
0.2mgl- of a high-WV anionic polymer to act as a flocculant. The removal of
BOD was increased from 30% to 55% while the phosphors
uptake was left
unchanged. The sludge produced after the activated sludge step was then more readily
biodegraded because of the lower inorganics content.
Polyelectrolyte applications in industrial wastewater treatment have been reviewed

recently, many of the applications being as flocculants used in conjunction with inorganic coagulants.247 Examples include effluents from the textile, dye and milk industries. On average, the addition of a cationic polymer after alum improved turbidity
removal in sed~entation
by 69% and COD removal by 16%. The cost of using a
coagulant aid in this way was offset by savings on primary coagulant and improved
effluent quality. Similar work has been performed on bleach plant effluents from pul
mills, where a high-CD polyDADMAC has been tested after the addition of alum. 28
Some of the organics not removed with alum could be taken out with the polymer.
After coagulation and flocculation have been carried out in this way, the floes
obtained may be separated by dissolved air flotation rather than sedimentation. The
clean up of some dyehouse effluents is possible by the addition of calcium or ferric
ions, followed by a cationic polymer, with calcium being more effective.265 After
colour removal by coagulation with alum or ferric sulphate, sometimes assisted by a
high-CD, low-MW polyDADMAC, a cationic polyacrylamide of low CD but crosslinked (see Section 10.7) and of high MW assists separation by dissolved air
flotation.266 An adsorptive clay may also be added in extreme cases. Many other
examples exist, especially in the food and beverage industries, where wastes from
abattoirs, dairy products, fruit juice and brewing are routinely concentrated by Aotation. A recent development is a block copolymer containing hydrophobic and hydrophilic segments which can give savings of up to z?O%.~~~
Sedimentation may be greatly enhanced by binding impurities to a weighting agent.

In the most radical example of this technique a recyclable magnetic coagulant is
employed which has its settling rate further accelerated by applying a magnetic
field, such that the size of the clarifier needed is less than a third of that of conventional
processes. Magnetite, Fe304, can be used as a primary coagulant, and with a particle
1028
B. A. BOLT0
size of 1- 10 pm the reaction rate is four times greater than with metal salt coagulants.
It is then capable of very rapid sedimentation by passing it through a simple magnetic
field, when intense flocculation occurs.268 In the drinking water version of the process
the initial contact of magnetite with raw water at pH 6 results in rapid adsorption of
humic substances by the iron oxide surface, giving it a negative charge:
-OOCRCOO-
+ +H20-Fe<
4 -OOCRCOO-Fe<
+ H20
(7)
A cationic polymer is used to bind free negatively charged turbidity particles to

the similarly charged organic+laden magnetite.74 The loaded magnetite slurry is
passed through a permanent magnetic field on its way to the settling stage. A highCD, low- to medium-MWpolymer
of the polyDADMAC type (III) is the flocculant of
choice:
>Fe-OOCRCOO-
+ +polymer+ + -OOC-
-+ >Fe-OOCRCOO-polymer-OOC-
(8)
In the regeneration stage, carried out at pH 11 and with washing on magnetic drum
separators, the charge on the magnetite is reversed, so the like-charged impurities are
repelled from the surface as in:
>Fe-COO-polymer-OOC+ >Fe-O-
+ -COO-polymer-OOC-
+ 20H+ H20
(9)
The particles are demagnetized merely by pumping action in their transport back to
the start of the process. The concept has now been realized on the full scale at several
locations.
Another weighted system is based on sand, which is recovered from the final sludge
by cycloning and reused.269a270In the preparation of drinking water from surface water
the optimum dose of metal salt coagulant was predetermined from jar tests to be
20 mgl-.
Sand of size less than 160 pm was then injected simultaneously with an
appropriate polyelectrolyte, presumably cationic, at doses of 1.5 g 1-l and 0.15 mg 1-l
respectively, so that a dense floe formed around each sand particle. The contact times
were four times less than with traditional processes, and settling rates five times
greater. A lamellar plate settler was used for the separation stage. A full-scale plant
is now in operation,271 and application of the technique to stormwater treatment is
reported.272
Polymer-coated fibreglass has been suggested for the removal of suspended matter
The fibres, after an aminosilane conditioning, are
from water and wastewater.
coated with the reaction product of epichlorohydrin and poly(viny1 alcohol) with a
polyamideamine.
10.7. Sludge Thickening
Some degree of concentration is normally required to reduce transport costs; the
various methods available*96 are summarized in Table 3 for a water treatment plant
SOLUBLE POLYMERS
Table 3. Concentration
Sludge conditioning
method
Batch settlement
Continuous thickening
without polymer dosing
with polymer dosing
Centrifuging
Filter pressing
IN WATER
PURIFICATION
1029
of sludges from water treatment plants96

Concentration in
(wt% solids)
Concentration out
(wt% solids)
0.03-0.2
l-3
0.03-0.2
0.03-0.2
l-5
l-10
2-3
5-10
12-17
20-25
sludge. This application consumes more polyelectrolytes than any other. Polymers are
used to give large dense floes which result in a more rapid settling of sludges and also
clearer supernatants, which are recycled. In static settling the resulting strengthened
floes settle to a slightly larger volume, but in raked continuous thickeners they can be
compressed without being broken, thus producing a much thicker material. Polymers
can also improve dewatering characteristics during centrifugation and filtration. Typically, in centrifugation 1S-3 kg of polymer is used per tonne of dry solids.274 The high
shear forces present during centrifugation make the use of polymers essential.
For sludge treatment generally, polymers of low or medium CD and high MW such
as (I) or (XV) give the best performance, with the charge type depending on the origin
of the sludge, Thus, for a water treatment plant sludge where alum is the coagulant, the
sludge particles generally have a positive surface charge, so an anionic polymer is
appropriate, although non-ionics such as polyacrylamide are also employed. On the
other hand, for a sewage sludge from an activated sludge plant the biosolids have a
negative surface charge, so a cationic polymer is the better performer.42 Some results
which are characteristic of the two types of sludges are shown in Table 4.
The mixing or pumping of sludges can result in increased difficulty of dewatering
because of their sensitivity to shear. When a medium-CD, high-MB anionic polyacrylamide is employed on alum sludge, the dewatering response is dependent on both
the shear and the mixing time.275 The polymer requirements increase with longer
mixing times and at higher shear as a result of the disaggregation of the sludge.
More polymer is then needed to reagglomerate the particles created by excessive
mixing conditions.
The influence of the CD of cationic polymers has been explored.2761277A low CD
Table 4. Typical gravity thickener operation@
Type of sludge
Polymer used
Solids loading
(kgm - d-)
Underflow
(wt% solids)
Alum from drinking water
None
Anionic
None
Cationic
25
25
9-11
22-35
1.5-2.0
334
2.4-2.6
2.6
Activated sludge from sewage
1030
B. A. BOLT0
gives floes having a flexible structure that have good shear resistance but are not
exceptional in their filtration properties. A medium or high CD on the other hand
results in good filtration properties, but the floes are more sensitive to shear. A dual
polymer method involving a high-CD, low-MY cationic polymer and, after suitable
ageing, a high-CD, high-MWcationic polymer has been successfully used to dewater a
biological sludge, to give a final solids content of 1l-14% vs the 8-l 1% obtained by
conventional methods.278
A recent advance has been the development of high-MY cationic polyacrylamides
of type (I) by crosslinking them in a very controlled manner. Random links between
two pol
er chains are made by connecting the amide groups through a methylene
bridge. 2r The advantage of these materials is that overdosing does not cause the
restabilization of a slurry, because adsorption of the polymer onto the surface of a
particle cannot result in its occupying all of the active sites. This arises because the
polymer is much less deformable and cannot spread over the surface of the particle.
Reflocculation can take place, the overall effect being the production of a very stable
floe. When used in sludge conditioning, massive agglomeration takes place which is
initially capable of some breakdown with subsequent shear. Ultimately equilibrium is
reached and the floe structure assumes a stable state. The floe size can be 30% larger
than that obtained with the corresponding linear polymer, and the reduction in size on
applying shear about 10% instead of more than 90%. Crosslinked polymers have been
most successful in dewatering sludges via centrifugation, when a cake of higher solids
content offers significant cost savings. Other applications include dewatering via belt
presses and the sedimentation of slurries subject to high shear.
Other variations on polymer design include a high-CD copolymer made by grafting
quaternized dimethylaminoethyl
methacrylate onto the epichlorohydrin-dimethylamine polymer (IV);28o including about 2 mol% of methoxyethyl acrylate in structure
(I) to form a terpolsmer, *49making a copolymer of acrylamide and dimethylaminoneopentyl acrylate;
and polymers made from acryloyl- or methacryloylamidopropyltrialkylammonium
chloride, where the alkyl groups can be ethyl, propyl or
butyl, and one may be benzyl.281
10.8. Mining Industry Applications
Selective flocculation, selective dispersion and flotation are extensively used in
mineral beneficiation, a very specialized area for which the use of conventional and
tailored polymers has been reviewed in detai1.38j282Separation of particles containing
toxic metals can be facilitated by adding a polymer which complexes with the metal.
Thus, polyacrylamide has been used to coagulate suspended material which contains
bound Hg2+ ions.283
In the waste treatment area, the concept of weighted flocculation based on magnetite as the coagulant has been extrapolated to heavy metals recovery from acidic
tailings dams in the mining industry, where by raising the pH the nuisance metals
such as aluminium and iron can be precipitated onto the magnetite, leaving the desired
metal in the treated wastewater, which then goes to further processing. Alternatively,
all the metals can be precipitated so that the treated liquor can be safely released to
1031
waterways.284 Both the magnetite and the hydroxy metal species have positive surface
charges under the prevailing acid conditions, so an anionic polyelectrolyte is used to
facilitate binding between them:
>Fe-OH;
+ -polymer-
+ fAl(OH)2 + >Fe-polymer-A1(OH)2
A low-CD, high-MW polymer such as a part-hydrolysed

and regeneration is achieved with acid:
>Fe-polymer-A1(OH)2
+ 4H + >Fe-OH;
+ Hz0
polyacrylamide
+ H-polymer-H
(10)
is effective,
+ A13+ + H20
(11)
10.9. Metal Zon Removal

Many studies have been made of the binding of metal ions to polyelectrolytes.
Weakly acidic polymers containing carboxylic acid groups have high affinities for
many heavy metal ions, although their uptakes are strongly pH-dependent. Spectroscopic studies of Cu2+ binding to poly(methacrylic acid) are reported,285 and the
polymer has been used as a model for the binding of alkaline earth and some transition
metal ions to humic acid.286 Hydrolysed maleic acid copolymers with ethylene, propylene or isobutene will bind with Cu2+ more strongly than with Ni2+ or Ba2+,
according to spectral evidence.287 Complexes of the first two of these metals with
polyethyleneimine have been similarly explored.77
Hence, when a polymer possesses coordinating functionalities, it can sequester ions
from aqueous solutions. The phenomenon can be put to good use in the removal of
toxic metals from wastewaters. After attachment of the metal to the polymer, separation is readily achieved if precipitation occurs because of the metal ions crosslinking
the polymer chains. This happens, for example, when cellulose xanthate is used to
recover Cd2+ from plating wastewater.
Analogous systems are Cu2+ or Cr3+ precipitation with a copolymer of maleic and acrylic acids289 and Cu2+ removal with a
polymer made from dichloroethane and ammonia which has been substituted with
dithiocarbamate.290 Another variation is the extraction of Pb2+ from contaminated
soil by sequestering it with polyethyleneimine containing carboxylic acid groups, after
which the polymer is regenerated by precipitation with acid to leave the lead in
solution.291
A polymer of opposite charge may be the means of precipitation, as when polyethyleneimine is reacted with poly(acrylic acid)-bound Cu2+. Regeneration with acid
releases the metal, leaving the insoluble metal-free polymer complex behind.292
Another example is the uptake of heavy metal ions by high-CD cationic polymers
like polyDADMAC or polyethyleneimine after a pretreatment with an anionic surfactant, followed by addition of an anionic polyacrylamide.293
An alternative approach is to concentrate the soluble metal-loaded polymer
using membrane technology. Thus, Cu2+ has been bo und to the anionic polystyrene
sulfonate (XVIII) and an essentially metal-free filtrate obtained by ultrafiltration.294 It
was postulated that poly(acrylic acid) would be a better proposition, as it could take
up the copper at high pH and after concentration could be released by lowering the pH
1032
B. A. BOLT0
to 4, when the polymer would be insoluble and could be recovered for reuse. Similar
work has been done on Cu2+ abstractio n with carboxymethylcellulose, which was
superior to polystyrene sulphonate,295 and with alginic acid.296 Poly(acrylic acid)
has been used for Cu2+ and Zn2+ remova1.297 An extensive study of metals removal
from plating effluents and other metal finishing wastewaters with low-MW poly(acrylic acid) and polyethyleneimine has obtained data for Cu2+ and Zn2+, and proposed electrolysis or acid treatment and a second ultrafiltration step to regain the
original polymer for further use.298 The membranes tested had pore sizes ranging
from 12 to > 30 nm. The method is suggested as a means of extracting metals from
sea water, with results reported for further metal ions like nickel, cobalt, cadmium,
manganese and chromium.
Anions can likewise be concentrated by binding them to the cationic polymers
polyethyleneimine or polyDADMAC and separating the loaded polymer by ultrafiltration. Arsenic in various acidic and anionic forms has been removed from groundwater by this means.299 The removal of chromate ions bound to polyDADMAC by the
same method has a chromate recovery route by precipitation with reagents such as
barium chloride.300
11.
ADVANTAGES
AND
DISADVANTAGES
OF USING
POLYMERS
The benefits arising from polymer use are several: the main two are the increase in
the rate of separating the solid and water phases arising from larger agglomerate sizes,
which can mean significant capital savings because of up to a doubling of throughput;
and the dramatically decreased sludge volume, to as low as a third of what would
otherwise be obtained.
The overall advantages of polyelectrolytes can be summarized as follows:
l
l
l
l
l
l
l
l
the solid-liquid separation rate is increased;

only 10 wt% of the dose of inorganic reagent is needed;
a smaller sludge volume is produced;
extended filter runs are obtained;
a wider range of waters can be treated;
a less pH-dependent process results;
a lowered usage of other chemicals ensues;
there is a lower dissolved salt level in the product water.
There are, of course, disadvantages

benefits:
l
l
l
l
l
l
which must be balanced against the above
operating costs may be higher;

there are toxicity concerns about residual monomers in potable water supplies and
about cationic polymers and the aquatic environment;
each type of water may need its own particular polymer;
inadequate provision of chemical and technical data by manufacturers;
overdosing can restabilize a dispersion and affect other process aspects;
stored polymer solutions may biodegrade.
1033
Achieving improved performance with reduced doses of appropriate polymers is the

challenge for future research in the area. Such an aim can be met only by optimizing
the polymer structure for particular applications. There is much to be done here, since
current theories on polymer behaviour in coagulation and flocculation are still at the
broad stage, with unfortunately much of the early work having been done on poorly
characterized polymers. The theories do not allow predictions of the nature of the
eventual floe, which will have different desired properties depending on the specific
application.30 Adequate attention has not yet been given to specific interactions
between functional groups, the focus so far being on bulk electrostatic and hydrophobic effects; nor has account been taken of the detailed structure of the polymer
backbone as well as its active substituents.
ACKNOWLEDGEMENTS
Helpful suggestions from CSIRO colleagues Nevil Anderson, David Dixon, Rob
Eldridge and Luis Kolarik are gratefully acknowledged.
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1995 Soluble Polymer

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Prog. Polym. Sci., Vol.

20, 987-1041, 1995

9.2. Monitoring systems

SOLUBLE POLYMERS IN WATER PURIFICATION

The materials which occur in waterways may be dissolved as well as particulate in

2.1. Dissolved Organic Compounds

Total organic carbon. mg/L

articullatcf orgarlit cartm

SOLUBLE POLYMERS IN WATER PURIFICATION

Equivalent fraction strong base

of fulvic and humic acids5

Elemental analysis (wt%)

Typical groups (meq g-)

*Yam Alver Partlclas

The surface charge potential is an important parameter infmencing colloid stability

2.3. Soluble Inorganic Matter

3.1. Coagulation by Charge Neutralization

Employing hydrolysable metal salts for coagulation is a long-standing technology,

SOLUBLE POLYMERS IN WATER PURIFICATION

Fig. 8. The bridging

in Fig. 8 and in the equation:

Table 2. Classification of polymeric flocculants by molecular

Copolymers of Quaternized Dimethylaminoethyl Acrylate or Methacrylate

Random copolymers of acrylamide and acryloyloxyethyltrimethylammonium

NMe3 + OH- + Pol-COO-

SOLUBLE POLYMERS IN WATER PURIFICATION

4.3. Polyelectrolytes Derived from Epichlorohydrin

4.8. Quaternized Polyvinylpyridines

followed by acid then alkaline hydrolysis to give a quantitative conversion to polyvinylamine.

Poly(amido-amines) constitute a class of polymers which have many interesting

The reaction of tannin with formaldehyde and aminoethanol produces a weakly

Polymers containing anionic groups are best categorized by their functionality. By

SOLUBLE POLYMERS IN WATER PURIFICATION

Synthetic polymers like polyacrylamide are a relatively recent innovation in the

Those utilized include starches, galactomannans, cellulose derivatives, microbial

Amphoteric polyelectrolytes, or polyampholytes, have both anionic and cationic

SOLUBLE POLYMERS IN WATER PURIFICATION

the zwitterionic structure being dependent on pH. The polyvinylsulphobetaines

Amphiphilic polymers are of interest as dispersants to help suspend solid particles in

Terpolymers of acrylamide with acrylic acid, sodium 3-acrylamido-3-methylbutanoate

9.1. Makeup, Selection and Dosing

The main applications

in the water industry

SOLUBLE POLYMERS IN WATER PURIFICATION

lnitidl Chemical Interaction

Fig. 10. Diagrammatic representation of the destabilization of humic acid by a cationic

SOLUBLE POLYMERS IN WATER PURIFICATION

SOLUBLE POLYMERS IN WATER PURIFICATION

Polyelectrolyte applications in industrial wastewater treatment have been reviewed

Sedimentation may be greatly enhanced by binding impurities to a weighting agent.

A cationic polymer is used to bind free negatively charged turbidity particles to

of sludges from water treatment plants96

Table 4. Typical gravity thickener operation@

Alum from drinking water

Activated sludge from sewage

SOLUBLE POLYMERS IN WATER PURIFICATION

A low-CD, high-MW polymer such as a part-hydrolysed

10.9. Metal Zon Removal

the solid-liquid separation rate is increased;

There are, of course, disadvantages

which must be balanced against the above

operating costs may be higher;

SOLUBLE POLYMERS IN WATER PURIFICATION

Achieving improved performance with reduced doses of appropriate polymers is the