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108-Soluble Polymers in Water Purification
108-Soluble Polymers in Water Purification
BRIAN A.BOLT0
CSIRO Chemicals and Polymers, Private Bag IO, Rosebank MDC, Clayton, Victoria 3169, Australia
CONTENTS
1. Introduction 988
2. Natural impurities in water 989
2.1. Dissolved organic compounds 990
2.2. Insoluble impurities 994
2.3. Soluble inorganic matter 995
3. Coagulation and flocculation mechanisms 995
3.1. Coagulation by charge neutralization 996
3.2. Flocculation via polymer bridging 997
4. Cationic polyelectrolytes 999
4.1. Copolymers of quatemized dimethylaminoethyl acrylate or methacrylate 999
4.2. Polymers of diallyldimethylammonium chloride 1001
4.3. Polyelectrolytes derived from epichlorohydrin 1002
4.4. Polyethyleneimine 1002
4.5. Ionenes 1003
4.6. Mannich reaction products from polyacrylamide 1004
4.7. Polystyrene derivatives 1004
4.8. Quatemized polyvinylpyridines 1005
4.9. Polyvinylamine 1005
4.10. Miscellaneous polyamines and quaternary ammonium polymers 1006
4.11. Natural polymers 1007
4.12. Sulphonium polymers 1008
5. Anionic polyelectrolytes 1008
5.1. Carboxylic acid polymers 1008
5.2. Sulphonic acid polymers 1010
5.3. Phosphonic acid polymers 1011
5.4. Natural polymers 1011
6. Non-ionic polymers 1012
6.1. Polyacrylamide 1012
6.2. Poly(ethylene oxide) 1012
6.3. Natural polymers 1012
7. Amphoteric polyelectrolytes 1012
7.1. Amphoteric copolymers 1013
7.2. Polymers containing zwitterionic units 1015
8. Hydrophobically modified polyelectrolytes 1016
8.1. Cationic 1016
8.2. Anionic to17
8.3. Amphoteric 1017
9. Practicalities in the use of polymeric flocculants 1017
9.1. Makeup, selection and dosing 1018
987
988 B. A. BOLT0
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 indus-
trial 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 fre-
quently desirable. Inorganic contaminants normally require the latter approach.
Physicochemical treatment covers processes such as the coagulation and floccu-
lation 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 appli-
cation 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 tech-
nologies as well.
Polymers have been utilized in coagulation/flocculation processes for water purifi-
cation 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.
SOLUBLE POLYMERS IN WATER PURIFICATION 989
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 chemi-
cals 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 dis-
advantages, 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.
meters
Phytoplankton I
Molecular weight
t-
General colloid range
-l
Cl10 Carhohydram
cl
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
T
- 25 30 35
II IO
Eutrophic lake 12
I I
Marsh
I I
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 PURIFICATION 991
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 pol-
lutants such as pesticides and polychlorinated biphenyls;
vary in their molecular structure, having mostly phenolic and carboxylic acid func-
tionalities, 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
region 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 illu-
strated 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
992 B. A. BOLT0
HO
HO
HO
HO
HO
COOH
cool4
cool4 ;~pJJ;g-qH
OH OH
O=qH
(HO-$H)‘ (sugar)
0:CH
0 0
cooH ;&o:fl;q&
0 \ , COOH
R-6H
C:O (pepttde)
COOH
tiH
C - Stevenson, 1982 I
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
SOLUBLE POLYMERS IN WATER PURIFICATION 993
PH
12 -
carboxylic
groups
I
1-
0 1 2 3
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
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, especi-
ally 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
0 5 10 15 20
Salinity (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
Humics
Al (H20&
3+ on-
------cAl-Monomers
I -Small
I
Al- Polymers
<‘0-4sec (Al OH 2+,elc.l <I set (AI,(~H);~. n~,tot$~)
2, Al tOH)s tppl)
-I set
(Depends 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).
SOLUBLE POLYMERS IN WATER PURIFICATION 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.
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
Intar-paltkk
adsotptlon
--
_
c?
J
.--
I Electrostatic attraction
brlng8 partkkr
**
. . I---___
together
.‘ :
: -__ -
--_ _ * --
00 -__--
Fig. 9. The charge patch agglomeration model (from ref. 248. Copyright 1991 Society of
Dyers and Colourists and reprinted with permission).
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 emul-
sions, 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.
co co
I I
NH2 0
- bvie
3
la, R I H
Ib, R = Me
1000 B. A. BOLT0
II
SOLUBLE POLYMERS IN WATER PURIFICATION 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 dialkylamino-
neopentyl acrylate, where the alkyl group is methyl or ethy1.55
Me
IV
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% pro-
tonation. 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 tri-
fluoride, 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-substi-
tuted methyl, propyl and phenyl derivatives have been made,79 as has linear poly-
propyleneimine.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 bac-
teriostatic 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
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-tert-
butylcarbamate, 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% com-
pletion 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,
w NH,
n
XI
1006 B. A. BOLT0
XI1
XIII
SOLUBLE POLYMERS IN WATER PURIFICATION 1007
NH2 -
5. ANIONIC POLYELECTROLYTES
co 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 dis-
persion 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 homo-
and 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 electro-
chemical carboxylation of poly(viny1 halides) and polybutadiene.13’ So far the maxi-
mum 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 pro-
ducts 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/ ‘O_
XVI
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.
kzjf
co
n
v 00
n
I I
0 NH
--
=3
SOLUBLE POLYMERS IN WATER PURIFICATION 1011
XxIa, A q H
Xxlb, R = Me
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.
+ I 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
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 condi-
tions have received detailed attention. *47
7. AMPHOTERIC POLYELECTROLYTES
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 signifi-
cance 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.
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
methacrylate153”67 or 2-acrylamido-2-methylpropyldimethylamine168 form poly-
ampholytes 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 charac-
terized 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-acrylamido-
2-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
”
0
N+
I
coo-
xxv111
XXIX
1016 B. A. BOLT0
coca
xxx
8.1. Cationic
Part amination of chloromethylated polystyrene as in (IX) gives water-soluble pro-
ducts 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 acryl-
amide which have an anionic surfactant ionically bonded to them have been used to
SOLUBLE POLYMERS IN WATER PURIFICATION 1017
xxx1
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.
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
HO-N=C CO
I I
NH, NH
AH
xxx11
1020 B. A. BOLT0
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 floc-
culants for this purpose.213
In determining the toxicity of polymers to aquatic species there are different para-
meters 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 organ-
isms 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.
coagulation and flocculation, and in sludge treatment. The first two processes are
usually followed by sedimentation and filtration, although with only slightly contami-
nated 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.
1 I
HumicAcid Cationic Polymer Destabilized Particle
F lot Formation
. Settled UV
300
s
‘(
g 200
2
2 100
0 4 8 12 16 20 24
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 poly-
ethyleneimine,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
chlorination.228 The CD rather than the MW is important in selecting the optimal
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 Alzheimer’s 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
SOLUBLE POLYMERS IN WATER PURIFICATION 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 mag-
nesium 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 hydro-
xide 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 high-
CD 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 dis-
tribution 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 feed-
water 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 .240How-
ever, the high salinity of marine systems inhibits the process. Direct filtration experi-
ments 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 com-
pounds 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 treat-
ment options. The amphoteric polymer (XXVII) obtained by reacting polyacrylo-
nitrile with dicyandiamide has been shown to aggregate algal cells without killing
them.‘78
other examples, applying a cationic polymer with clay, which acts as both an adsor-
bent 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 decontami-
nation 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 acryl-
amide and quaternized dimethylaminoethyl acrylate or methacrylate (I), which ade-
quately 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 signifi-
cant 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 emul-
sions in food industry wastes can be broken by cationic polymers such as chitosan,
polyethyleneimine or the copolymer of acrylamide and quaternized dimethyl-
aminoethyl 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 process-
ing wastewater by flotation after the addition of a cationic polymer plus an acryl-
amidoxime-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 poly-
acrylamide.254
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 pos-
sible.22t31t’96Thus 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 conjunc-
tion 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:~”
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.
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:
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. Typi-
cally, 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 poly-
acrylamide 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
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-dimethyl-
amine polymer (IV);28o including about 2 mol% of methoxyethyl acrylate in structure
(I) to form a terpolsmer, *49making a copolymer of acrylamide and dimethylamino-
neopentyl acrylate; and polymers made from acryloyl- or methacryloylamido-
propyltrialkylammonium chloride, where the alkyl groups can be ethyl, propyl or
butyl, and one may be benzyl.281
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 + Hz0 (10)
A low-CD, high-MW polymer such as a part-hydrolysed polyacrylamide is effective,
and regeneration is achieved with acid:
>Fe-polymer-A1(OH)2 + 4H’ + >Fe-OH; + H-polymer-H + A13+ + H20
(11)
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 pro-
posed 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 ultrafil-
tration. Arsenic in various acidic and anionic forms has been removed from ground-
water 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
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 the solid-liquid separation rate is increased;
l only 10 wt% of the dose of inorganic reagent is needed;
l a smaller sludge volume is produced;
l extended filter runs are obtained;
l a wider range of waters can be treated;
l a less pH-dependent process results;
l a lowered usage of other chemicals ensues;
l there is a lower dissolved salt level in the product water.
There are, of course, disadvantages which must be balanced against the above
benefits:
l operating costs may be higher;
l there are toxicity concerns about residual monomers in potable water supplies and
about cationic polymers and the aquatic environment;
l each type of water may need its own particular polymer;
l inadequate provision of chemical and technical data by manufacturers;
l overdosing can restabilize a dispersion and affect other process aspects;
l stored polymer solutions may biodegrade.
SOLUBLE POLYMERS IN WATER PURIFICATION 1033
ACKNOWLEDGEMENTS
Helpful suggestions from CSIRO colleagues Nevil Anderson, David Dixon, Rob
Eldridge and Luis Kolarik are gratefully acknowledged.
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