Article No : a11_251

Flocculants
HANS BURKERT, BASF Aktiengesellschaft, Ludwigshafen, Federal Republic
of Germany
JURGEN HARTMANN, BASF Aktiengesellschaft, Ludwigshafen, Federal Republic
of Germany

1. Introduction. . . . . . . . . . . . . . . . . . ..... . 199 3.2. Specific Ion Adsorption . . . . . . . . . ..... . 203

2. Classification of Flocculants. . . . . . ..... . 199 3.3. Polymer Charge Patch. . . . . . . . . . ..... . 203
2.1. Inorganic Flocculants. . . . . . . . . . . ..... . 199 3.4. Polymer Bridging. . . . . . . . . . . . . . ..... . 203
2.2. Natural Organic Flocculants . . . . . ..... . 200 4. Uses . . . . . . . . . . . . . . . . . . . . . . . . ..... . 204
2.3. Synthetic Organic Flocculants . . . . ..... . 200 5. Choice of Optimum Flocculant . . . ..... . 204
2.3.1. Chemical Structure . . . . . . . . . . . . . ..... . 200 6. Legal Aspects. . . . . . . . . . . . . . . . . ..... . 206
2.3.2. Production Requirements . . . . . . . . . ..... . 201 7. Economic Aspects . . . . . . . . . . . . . ..... . 207
3. Flocculation Mechanisms. . . . . . . . ..... . 203 References . . . . . . . . . . . . . . . . . . . ..... . 207
3.1. Double Layer Compression . . . . . . ..... . 203

1. Introduction sedimentation, clarification, filtration, or cen-

Flocculants are used to optimize the separation of
the solid phase from the liquid phase in aqueous
suspensions. These suspensions usually consist
of organic or inorganic particles, which are of
finely divided to colloidal consistency and are
distributed in water as a dispersion medium. With
smaller particles, the suspension is more stable,
i.e., the lower is the tendency for the particles to
agglomerate and sediment. However, addition of
a flocculant drastically increases the rate of par-
ticle sedimentation so that a clear, supernatant
liquid is obtained. The settled sludge can then be
filtered rapidly or centrifuged, resulting in a more
efficient separation.
In this article, a distinction is made between
organic and inorganic flocculants in accordance
with the international convention.
trifugation aids, according to their final use.
The ability of synthetic polymers to increase
the sedimentation rate of suspensions was first
observed in 1939 [4]. The flocculation effect
exerted by synthetic water-soluble polymers
was discovered at the beginning of the 1950s
at BASF, and at about the same time, Cyana-
mid filed a patent application for polymeric
flocculants in Canada [5]. Flocculants pro-
duced by BASF were first used successfully
in 1955 for the clarification of washing water
in German collieries [6]. Shortly afterwards,
Dow Chemical introduced their flocculants
into the United States market. Since then,
organic flocculants have steadily gained in
importance and are now used worldwide in
many branches of industry and in water-treat-
ment plants.

Inorganic Flocculants are mostly aluminum

or iron salts that form insoluble hydroxide pre-
cipitates in water. Impurities in the water are 2. Classification of Flocculants
adsorbed onto the sedimenting precipitate
flocs and are thus removed from the water. A 2.1. Inorganic Flocculants
combination of inorganic and organic flocculants
is frequently employed in the treatment of water. The most important inorganic flocculants are
the trivalent salts of aluminum and iron, as
Organic Flocculants are natural or synthetic well as activated silica, and are listed in
water-soluble polymers. They may also be called Table 1.

2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

DOI: 10.1002/14356007.a11_251
200 Flocculants
Table 1. Inorganic flocculants
Type Formula
Alum Al2(SO4)3
14 H2O
Poly(aluminum chloride) Al(OH)1.5(SO4)0.125Cl1.25
Sodium aluminate NaAlO2
Iron(III) chloride FeCl3
Iron(III) sulfate Fe2(SO4)3
Iron(III) sulfate chloride FeClSO4
Iron(II) sulfate FeSO4
7 H2O
Sodium silicate Na2SiO3
(activated silica)
2.2. Natural Organic Flocculants
The group of natural organic flocculants includes
water-soluble starch [9005-25-8] [7], guar gum,
alginates [9005-38-3], and products based on
chitin [8], glue, and gelatin [9]. Owing to their
low relative molecular masses (10 000
100 000), these flocculants are only moderately
efficient. Despite the very low cost of some of
these natural products, the cost-to-performance
ratio of synthetic flocculants is considerably
more favorable due to their very high relative
molecular masses. Consequently, natural organic
flocculants have steadily declined in importance.
Only soluble starch was able to maintain its
market position in certain fields for any length
of time, e.g., in the preparation of bauxite
(red mud flocculation [10], ! Aluminum Oxide)
and the purification of water (! Water, 4. Treat-
ment by Flocculation and Filtration). Starch was
chosen for the latter application because, unlike
synthetic organic flocculants, its use did not re-
quire legal permission. Flocculants based on nat-
ural organic polymers are now of little importance
and are not, therefore, further discussed.
2.3. Synthetic Organic Flocculants
2.3.1. Chemical Structure
The chemical structure of synthetic organic floc-
culants determines their flocculating properties.
They are water-soluble polymers which can be
Vol. 15
CAS registry
number Comments
[7784-31-8] used as a powder (17 wt % Al2O3) or 50 wt % solution
(8.5 wt % Al2O3)
[7446-70-0] obtained by partially hydrolyzing AlCl3 [7446-70-0],
used as a solution (10 wt % Al2O3)
[1302-42-7] used as a powder and solution
[7705-08-0] used as a powder (100 wt % FeCl3) or solution
(35 45 wt %)
[10028-22-5] used as a granulate
[12410-14-9] obtained by oxidation of FeSO4 with chlorine in
solution, used as a solution (30 40 wt %)
[7782-63-0] used as a crystalline powder
[1344-09-8] used as a solution
classified into nonionic polymers [11], and ionic
polymers (polyelectrolytes); the latter can be
further subdivided into anionic, cationic, and
amphoteric types [12]. Examples of flocculants
from each of these groups are given in Table 2.
Nonionic Polymers. Other nonionic homo-
polymers not cited in Table 2 can be produced
from 1-vinyl-2-pyrrolidone [88-12-0], N-vinyl-
formamide [13162-05-5], methoxyethylene
[107-25-5], etc. Poly(vinyl alcohol) [9002-
89-5] is synthesized by hydrolysis of poly(vinyl
acetate). Very high molecular mass poly(ethyl-
ene oxide) [25322-68-3] is obtained by polymer-
izing ethylene oxide over special catalysts,
e.g., alkaline-earth carbonates or aluminum
alcoholates (C1 C4) [13], [14]. Nonionic homo-
polymers are, however, of little commercial im-
portance as flocculants.
Ionic Polymers. The most important ionic
polymeric flocculants are copolymers derived
from acrylamide [79-06-1] and a charged como-
nomer [! Polyacrylamides and Poly(Acrylic
Acids)].
Anionic Polymers. Almost all anionic poly-
meric flocculants are synthesized as homopoly-
mers or acrylamide copolymers of the alkali-
metal or ammonium salts of acrylic acid [79-
10-7]. Methacrylic acid [79-41-4], maleic acid
[6915-18-0], ethylenesulfonic acid [1184-84-4],
4-styrenesulfonic acid [98-70-4], and 2-methyl-2-
[(1-oxo-2-propenyl)amino]-1-propanesulfonic
Vol. 15
Table 2. Synthetic organic flocculants
acid [15214-89-8] are also used as comonomers
in acrylamide copolymers, but are of little prac-
tical importance.
Cationic Polymers. Other water-soluble como-
nomers are used for the production of cationic
polymers in addition to those listed in Table 2,
the most important being the following: substituted
acrylamide and methacrylamide salts [1619]; N-
vinylformamide [13162-05-5] and N-vinylaceta-
mide [5202-78-8], which are polymerized and
hydrolyzed in alkaline or acidic media to viny-
lamine copolymers [593-67-9] [2023]; and salts
of N-vinylimidazole [1072-63-5], 2-vinylpyridine
[100-69-6] or 4-vinylpyridine [100-43-6].
Water-insoluble or sparingly water-soluble
comonomers can also be incorporated, provided
the resulting copolymers are still soluble in
water.
Cationic homopolymers and copolymers of
dialkyldiallylammonium chlorides, e.g., diallyl-
dimethylammonium chloride [7398-69-8], can
be produced by free-radical polymerization;
these polymers are composed of chains bearing
cyclic structures [2428]. The polyamines are
another important class of cationic flocculants
and are obtained by polycondensation. The
starting materials are alkylene dichlorides or
epichlorohydrin and ammonia, low molecular
mass alkylene polyamines, or polyaminoamides
Flocculants 201
[2933]. Polycondensation of ethyleneimine
[151-56-4] yields polyethylenimines.
Amphoteric Polymers that bear both anionic
and cationic charges are of little practical impor-
tance as flocculants.
2.3.2. Production Requirements
The raw materials used to synthesize organic
flocculants are described in Section 2.3.1.
High molecular mass polymers are required
for efficient flocculation (cf. Section 3.4). Thus,
very strict requirements are imposed on the
purity of the starting materials, especially the
monomers. Contamination by inhibitors or by
chain-transfer or cross-linking agents must be
avoided. Water is the preferred solvent because
other solvents either yield polymers of lower
molecular mass due to transfer reactions or pose
an ecological risk.
A second important prerequisite for obtaining
a high molecular mass is a polymerization tem-
perature that is as low as possible. The polymeri-
zation temperature depends largely on the
choice of initiator. Conventional free-radical
initiators, such as alkali-metal persulfates and
peroxides, are being superseded by azo initiators,
which decompose at lower temperatures, e.g.,
202 Flocculants
2,20 -azobis(2-amidinopropane)hydrochloride,
2,20 -azobis(2,4-dimethylvaleronitrile). Alterna-
tive initiators are redox catalysts (e.g., ascorbic
acid) and UV and g-radiation [3439]. Attempts
are also being made to achieve homogeneous
temperature distribution by removing the heat
produced during polymerization as efficiently as
possible from the reaction vessel, e.g., by using
evaporative cooling, special monomer feed tech-
niques in thin layers [36], [40], [41], or two-phase
systems. A method for trapping the heat of
polymerization with endothermic reactions has
also been described [42], [43].
Synthetic organic flocculants are marketed as
liquids (either solutions or emulsions) and solids.
Solutions. Polycondensation in an aqueous
solution is an important technique for producing
polyamine flocculant solutions. A polymer con-
tent of ca. 50 wt % can be attained.
When acrylamide is copolymerized in solu-
tion, the high molecular masses that are desired
result in highly viscous, gel-like solutions, which
are difficult to handle when the polymer content
exceeds 10 wt %. Special metering and solubi-
lizing equipment is required [44]. These solu-
tions are important starting materials for the
manufacture of solid flocculants.
Emulsions. Emulsion flocculants are more
important than solution flocculants and are made
by the polymerization of water-in-oil emulsions
[4550] (for details of emulsion polymerization,
! Polymerization Processes, 2. Modeling of
Processes and Reactors). A concentrated aque-
ous monomer solution is emulsified with emul-
sifiers in a dispersion phase that usually consists
of a high-boiling mixture of aliphatic hydrocar-
bons. The particle size of the emulsions is 0.1
10 mm and their viscosity is low, usually less than
1500 mPa
s. Polymerization is then started by
adding oil- or water-soluble initiators; azo in-
itiators are preferred, but the use of UV irradia-
tion has also been described [51]. Wetting agents
are added to the polymerized water-in-oil emul-
sions prior to use; the emulsions are then inverted
in water [52]. Variations on this simple batch
method dissipate the heat of polymerization more
efficiently either by evaporative cooling [53],
[54] or by special monomer feed techniques
[56], [56]. These methods yield emulsions with
a polymer content of 25 45 wt %. An even
Vol. 15
higher polymer content can be obtained by azeo-
tropic distillation of the internal aqueous phase
and some of the hydrocarbon mixtures [57].
Water-in-oil emulsions are easy to handle
despite their high polymer content and require
no drying with the attendant risk of product
damage. However, the starting materials are
more expensive and the stability of the emulsions
is limited.
Solids. Liquid products can be dried to give
powders. Drying methods include precipitation
of the polymers with low molecular mass alco-
hols or acetone in a heavy-duty mixer, drying on
rollers, spray-drying, azeotropic distillation with
inert organic solvents, and irradiation with
microwaves. Water-in-oil emulsions are not of-
ten dried because of the relatively high initial cost
of the raw materials. Solid flocculants are usually
obtained from aqueous polymer solutions. High
polymer concentrations are used to reduce drying
costs. The solutions form firm gels, which are
cut into small pieces and dried. The particle size
of the final powder is adjusted by milling and
sieving.
An industrially important alternative for ob-
taining solid flocculants is based on polymeriza-
tion of a water-in-oil suspension [5861] (for
details of suspension polymerization, ! Poly-
merization Processes, 2. Modeling of Processes
and Reactors). The concentrated aqueous mono-
mer solution is emulsified in the presence of
special protective colloids in a hydrophobic
phase. The hydrophobic phase may be a low-
boiling aliphatic compound, an aromatic hydro-
carbon, or a halogen derivative of the latter.
Polymerization is started with water-soluble
initiators and proceeds by evaporative cooling
to produce polymer beads that contain water and
have a particle size of 0.1 0.5 mm. The water
is then removed by azeotropic distillation, the
hydrophobic phase serving as an entraining
agent. The solid product is obtained after sepa-
ration of the organic solvent, drying, and sieving.
Solid flocculants with high molecular masses
can also be prepared by precipitation polymeri-
zation in, for example, tert-butanol or its mix-
tures with water [62], [63], but this method is less
important.
The advantages of solid products are their
high flocculant concentration, which results in
lower marketing costs and increased stability.
Vol. 15
Their disadvantages are the necessity for a drying
stage, with the associated risk of product damage,
and their slow rate of dissolution. The latter
problem has been largely solved by the develop-
ment of modern dosing devices.
3. Flocculation Mechanisms
The stability of a suspension depends on the
number, size, density, and surface properties of
the solid particles (internal or dispersed phase)
and on the density of the external phase or
dispersion medium. The stability and destabili-
zation of colloids, suspensions, and emulsions
are discussed in detail elsewhere ( ! Colloids,
! Colloids, ! Colloids; ! Disperse Systems
and Dispersants, ! Disperse Systems and Dis-
persants; ! Emulsions).
In aqueous suspensions, the particle surface
has an electrical (usually negative) charge,
which, for example, in mineral solids originates
from the dissociation of protons from surface
hydroxyl groups belonging to silicate groups
[64]. If counterions (e.g., Ca2 or Mg2) are
present in the surrounding water, they accumu-
late on the surface of the suspended particles,
forming an ionic double layer [65]. The excess
negative charge at the shear surface of the double
layer (the zeta potential) can be measured with
a zeta meter. As the zeta potential increases, the
coulombic repulsion between the particles be-
comes stronger and the suspension is more stable.
Many authors distinguish between coagula-
tion and flocculation [66]. Flocculation is surfaces. Thus, positively charged polymer cen-
usually taken to mean the process in which
particles are interlinked by molecular chains with
no change in the zeta potential (anionic and
nonionic organic flocculants). Coagulation,
however, is taken to mean the electrical neutrali-
zation of suspended particles, as brought about
by iron and aluminum hydroxide.
Four models are used to explain how floccu-
lants aid particle agglomeration. However, more
than one of these mechanisms probably act
simultaneously.
3.1. Double Layer Compression
As the cation concentration in the water in-
creases, the thickness of the ionic double layer
Flocculants 203
decreases (i.e., the double layer is compressed),
thereby reducing the number of collisions be-
tween the particles and rendering the suspension
unstable [67]. This mechanism accounts to some
extent for the destabilization of suspensions by
inorganic salts, especially by monovalent ions.
3.2. Specific Ion Adsorption
The mechanism of specific ion adsorption always
applies when cations are bound chemically to the
particle surface, e.g., by forming complexes with
the surface atoms. Thus, the particle charge may
be partially or completely neutralized [68], [69].
In the latter case, the particles no longer repel
each other and the conditions for agglomeration
are optimal.
Trivalent aluminum and iron salts are exam-
ples of flocculants that function in this way. In
water they are partially or totally hydrolyzed to
form positively charged dibasic, tribasic, or poly-
meric hydroxides that adsorb onto the particle
surface and neutralize its charge according to
their degree of hydrolysis.
3.3. Polymer Charge Patch
When cationic polymers are added to a suspen-
sion, they are adsorbed to the surfaces of particles
with negative charge as described in Section 3.2.
They neutralize the negative charge, but their
charge density is higher than that of the particle
ters (polymer charge patches) are formed on the
particle surfaces and, in turn, come into contact
with the negatively charged surfaces of other
particles and also destabilize the suspension
[70], [71]. Flocculation involving relatively low
molecular mass cationic polymers (e.g., poly-
ethylenimine) is thought to proceed by this
mechanism.
3.4. Polymer Bridging
In polymer bridging, high molecular mass poly-
mer chains are adsorbed onto the particle surface
and form bridges between adjacent particles
[7275]. Adsorption occurs by electrostatic
forces, van der Waals forces, hydrogen bonding,
204 Flocculants
and chemical bonding. This model is used to
account for the flocculation produced by high
molecular mass organic flocculants. The bridg-
ing mechanisms of anionic, cationic, and non-
ionic organic flocculants are different.
Mineral (anionic) suspensions are generally
flocculated with anionic polyelectrolytes for
economic reasons (e.g., in the coal mining in-
dustry). This is only possible beause the anionic
particles are not suspended in deionized water,
but in hard water. Water hardness varies and is
primarily caused by divalent calcium and mag-
nesium ions. These positively charged ions are
adsorbed onto the negatively charged particle
surface to form an ionic double layer. The
positively charged ions face outward and allow
the anionic flocculant to approach the particle
closely enough to be adsorbed to its surface [72].
In this case, bridging is the result of a genuine
chemical bond in which the divalent cations link
the solid particles with the active groups on the
polymer chain. However, hydrogen bonding
may also play a role. Obviously, mineral sus-
pensions cannot be flocculated in very soft
water due to the absence of divalent ions.
Therefore, the suspensions must be hardened
with anhydrous lime prior to the addition of the
polymer. Alternatively, cationic flocculants can
be used.
Obviously, the probability that a polymer can
be adsorbed simultaneously onto different parti-
cles and act as a bridge between them increases
with an increase in its molecular mass. Accord-
ingly, the most effective anionic flocculants
have molecular masses of ca. (10 20)106.
Thus, sedimentation is quicker and filtration is
easier when large stable agglomerates or flocs
are formed [76].
Since cationic flocculants are positively
charged, they partially or completely neutralize
negative charge on particle surfaces, and the
polymer chains cross-link adjacent particles.
The only bridging mechanism that is available
to nonionic synthetic flocculants, e.g., polyacryl-
amide and poly(ethylene oxide), is hydrogen
bonding.
4. Uses
The fact that suspended solid particles can be
made to agglomerate to form large, rapidly
Vol. 15
settling, easily filterable flocs is exploited to
clarify suspensions and dewater the resulting
sludges. Flocculants are added to accelerate set-
tling in basins and to dewater sludge in vacuum
filters, sand filters, belt filters, filter presses, and
centrifuges. However, water purification is not
the sole application of flocculants. Each branch
of industry has its own priorities, which may be
maximum recovery of a solid matter and/or
the separation of a clear aqueous phase. Combi-
nations of organic and inorganic flocculants can,
to some extent, remove dyes and oily impurities
from effluents.
If the density of the flocs is similar to that of
the aqueous phase, they may float and not settle.
Thus, flocculants may promote flotation, but
this may be troublesome if solids of different
composition are to be separated (coal and ore
flotation) [77].
The most important uses of flocculants are
summarized in Table 3.
5. Choice of Optimum Flocculant
Flocculant manufacturers now offer comprehen-
sive ranges of anionic, cationic, and nonionic
flocculants that differ from one another in the
chemistry of their monomeric building blocks,
the nature and size of their ionic charge, and their
molecular mass [137]. It is not always easy to
predict which flocculant is most suitable to obtain
the desired sedimentation rate for a specific
application. Broadly speaking, anionic and
nonionic organic flocculants are best for neutral
suspensions that consist primarily of inorganic
solids, whereas cationic flocculants are best for
neutral suspensions containing predominantly
organic solids.
Inorganic flocculants are used mainly to clar-
ify suspensions containing a low concentration
of particulate material, e.g., in the purification of
surface water to potable water. The voluminous
hydroxide flocs adsorb both solid and dissolved
contaminants. If the flocs sediment too slowly,
the sedimentation rate can be accelerated by
adding an organic flocculant.
pH Value. The pH is important in selection
of a flocculant because it determines the degree
of dissociation of anionic and cationic polyelec-
trolytes. Complete dissociation of the flocculant
Vol. 15 Flocculants 205

Table 3. Uses of Flocculants

Field of application Use Flocculant type* Reference

Mining industries
Coal clarification of washwater and flotation tailings, a-PAA [78], [79]
filtration of concentrates, a-PAA [80], [81]
dewatering of tailings a-PAA, PEI, c-PAA [82], [83]
Ores clarification of flotation tailings, a-PAA [8487]
thickening and filtration of concentrates PAA, a-PAA
Potash clarification of potash solutions a-PAA [88], [89]
(hot solution and flotation processes),
dewatering of tailings PAA, PEO
Fluorite and barytes clarification of flotation tailings a-PAA [90], [91]
Kaolin thickening of kaolin slurries a-PAA [92], [93]
Salt works clarification of raw brine, sludge dewatering PAS, a-PAA [94]
Phosphate water recovery in mines, PAA, a-PAA
filtration of gypsum, a-PAA [9597]
clarification of phosphoric acid PAA
Uranium processing filtration of acidic or alkaline solutions PAA, PEO [98], [99]
Foundries and clarification of water for scrubbing gas from
metalworking blast furnaces, clarification of effluents from
sintering and pickling plants, a-PAA [100102]
purification of electrolytic solutions, PAA, a-PAA [103105]
clarification of electroplating effluents a-PAA [101]
Bauxite benification thickening of red muds (Bayer process) PAS ! Aluminum Oxide, [106]
TiO2 production clarification of black liquor, c-PAA, CCP [107]
filtration of TiO2 PAA
Paper industry retention of kaolin and PEI, c-PAA, PA [108114]
dewatering of slurries on paper machines, PEI, c-PAA, PA
pulp recovery PEI, c-PAA, PA
effluent clarification and dewatering a-PAA, c-PAA
Communal and effluent purification, IF, a-PAA [115117]
industrial water thickening of activated sewage sludge, c-PAA [118]
treatment plants flotation of activated sewage sludge, c-PAA [119]
mechanical dewatering of sewage sludge, c-PAA [120124]
phosphate precipitation IF, a-PAA [125]
Clarification of flocculation of surface water, IF, a-PAA [126128]
potable and clarification of wash water used to flush filters, a-PAA
non-potable water filter conditioning a-PAA, PEI, PA [129], [130]
Sugar processing clarification of sugar juice, dewatering of sludge a-PAA [131133]
Biotechnology dewatering of biological sludges PEI, PA, c-PAA [134136]
*
CCP cationic carbamoyl polymers; IF inorganic flocculants; PA poly(alkylene polyamines); PAA polyacrylamide;
a-PAA copolymers of acrylamide and sodium acrylate; c-PAA copolymers of acrylamide and cationic substituted (meth)acrylates,
neutralized and quaternized; PAS poly(sodium acrylate); PEO poly(ethylene oxide); PEI polyethylenimine.

is desired, and anionic and cationic flocculants
are, therefore, preferred for alkaline and acidic
suspensions, respectively. Nonionic polymers
are affected very little by the pH. In the case of
highly acidic suspensions, nonionic polymers are
often preferred to cationic flocculants for eco-
nomic reasons.
Flocculant Addition. At a given flocculant
addition rate, the suspension settles more slowly
if its solid content increases or if its average
particle diameter decreases [6]. However, the
amount of flocculant that is required also depends
on the strength of its ionic charge. Figure 1
illustrates the difference in behavior between a
strong and a weak anionic flocculant in a neutral
suspension.
Powder flocculants tend to clump when they
are simply added to water, and a great deal of
energy is needed to incorporate emulsions into
water. Manufacturers supply instructions with
their products and also offer simple devices for
overcoming the above-mentioned difficulties as
well as problems encountered in continuous
processes. Integrated semiautomatic and auto-
matic equipment is commercially available.
Polymeric flocculants are generally used as
0.05 0.1 wt % solutions. Inorganic flocculants
206 Flocculants
Figure 1. Relationship between the sedimentation rate of a
suspension and the quantity of flocculant added a) Weakly
anionic flocculant; b) Strongly anionic flocculant
are supplied in crystalline form or as aqueous
solutions and are used as 10 wt % solutions.
Normally 0.1 0.5 g of flocculant is added
per cubic meter of suspension in the thickener
or settling basin. When sludge is dewatered with
the aid of filters and centrifuges, 2 8 kg of
flocculant per ton of dry sludge is necessary.
Laboratory Tests. When a flocculant is
chosen, it is always helpful to carry out labora-
tory trials with a series of different flocculants
[138]. Fresh suspensions must be used. Repre-
sentative samples should be taken if the compo-
sition of the suspension varies considerably. The
manufacturers literature should be consulted
for further details. The following tests can be
used, depending on the intended application:
1. Sedimentation tests in a shaker provide infor-
mation about the sedimentation rate and
clarity of the supernatant [139]. Laboratory
results can be helpful in calculating flocculant
doses required in continuously operating
thickeners, thus eliminating long trial periods
in the initial period of use [140].
2. Filter plate tests (vacuum filtration).
3. Buchner funnel tests (filtration with and with-
out vacuum) [141], [142].
4. Pressure filter tests [143].
5. Determination of filtration rate (capillary suc-
tion time) [144], [145].Tests 2 5 provide
information about the dewatering of sludges,
Vol. 15
especially with regard to the thickness and
moisture content of the filter cake and the
filtration efficiency.
6. Determination of floc stability [143]; this test
provides information about the dewatering of
sludges in centrifuges.
7. Jar test [146]: In this test the flocculant is
added to a suspension in a jar (beaker). Slow
stirring induces the formation of voluminous
hydroxide flocs that surround the slurry. The
sedimentation and clarity of the test samples
are compared after the stirrer has been
switched off. This test is performed on slurries
containing very little sedimentable material
for which organic flocculants are generally
unsuitable.
8. Dynamic flocculation measurement with the
aid of a laser beam [147]. This method is also
used for optimizing the flocculant metering
rate in continuously operating systems.
6. Legal Aspects
The high molecular mass polymeric flocculants
are not toxic in themselves. Certain precautions
should be taken, however, because they all
contain small proportions of residual toxic
monomers [148], especially acrylamide. Legal
controls apply when the flocculants are used in
the manufacture of food, in the purification of
potable water, or for the clarification of sugar
juice.
A list of the flocculants that are approved by
the EPA for water purification is printed annually
in the United States [149]. Many other countries
have their own regulations, but these regulations
differ very little from each other. Generally, the
residual monomeric acrylamide content must be
less than 0.05 wt % of the polymer content; the
amount of flocculant added to untreated water
should not exceed 1 g/m3 [150].
The United States regulations on the clarifi-
cation of sugar juice [151] are generally observed
worldwide; they stipulate that the residual acryl-
amide monomer content must account for less
than 0.05 wt % of the polymer content, and the
quantity of added flocculant must not exceed
5 g/m3. Methods for determining the residual
monomeric acrylamide content of polymers and
the residual flocculant content of treated water
have been described [150], [152].
Vol. 15
7. Economic Aspects
In 1984, the use of synthetic organic flocculants
(calculated as dry mass) in Western Europe was
Table 4. Representative worldwide producers of inorganic flocculants
Flocculant Producers
Alum Allied (USA)
Amer. Cyanamid (USA)
Boliden (Sweden)
Giulini Chemie (FRG)
Stauffer (USA)
Nikkei Kako (Japan)
Scintoma Aluminium
Smelting (Japan)
Poly(aluminum chloride) Giulini Chemie (FRG)
Sachtleben Chemie (FRG)
Sodium aluminate Giulini Chemie (FRG)
Nalco Chemical (USA)
Sachtleben Chemie (FRG)
Iron(III) chloride BASF (FRG)
Dow Chemical (USA)
Pennwalt (USA)
Solvay (Switzerland)
Iron(III) sulfate Giulini Chemie (FRG)
Iron(III) sulfate chloride Kronos Titan (FRG)
Iron(II) sulfate Kronos Titan (FRG)
Pfizer (USA)
Soci
et
e des Fabriques de
Produits Chimiques de
Thann et Mulhouse
(France)
Sodium silicate Allied (USA)
Solvay (Belgium)
Wollner-Werke (FRG)
Table 5. Primary worldwide producers of synthetic organic
flocculants
Producer Flocculant trade name
Allied Colloids (UK) Magnafloc, Percol, Zetag
Amer. Cyanamid (USA) Superfloc, Accurac
BASF (FRG) Sedipur, Polymin
Betz Laboratories (USA) Polyfloc, Betz
Calgon (USA) Calgon, Hydraid
Chemische Fabrik Praestol
Stockhausen (FRG)
Dow Chemical (USA) Separan, Purifloc
Hercules (USA) Hercofloc, Reten
Kurita Kogyo (Japan) Kurifloc
Mitsubishi Chemical (Japan) Diaclear
Nalco Chemical (USA) Nalco
R
ohm (FRG) Rohafloc
Sankyo Chemical (Japan) Sanpoly
Sanyo Chemical (Japan) Sanfloc
Soci
et
e Nationale de Floculant Floerger
(France)
Flocculants 207
ca. 15 000 t and in the United States ca. 40 000 t,
half of this being accounted for by polyacryla-
mides. Large markets also exist in Canada, South
America, Africa, Australia, and Japan.
Of the inorganic flocculants, alum
(Al2(SO4)3
18 H2O) enjoys the largest market
share. In 1978, ca. 400 000 t was used in the
United States and ca. 150 000 t in Western Eur-
ope, in both cases almost exclusively for water
treatment.
Representative worldwide producers of inor-
ganic and synthetic organic flocculants are given
in Tables 4 and 5.
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210 Flocculants Vol. 15

Further Reading H. I. Heitner: Flocculating Agents, Kirk Othmer Encyclo-

D. H. Bache, R. Gregory: Flocs in Water Treatment, IWA
Publ., London 2007.
J. Bratby: Coagulation and Flocculation in Water and Waste-
water Treatment, 2nd ed., IWA Pub., Seattle WA 2006.
S. M. Bulatovic: Handbook of Flotation Reagents, Elsevier,
Amsterdam 2007.
pedia of Chemical Technology, 5th edition, John Wiley
& Sons, Hoboken, NJ, online DOI: 10.1002/0471238961.
0612150308050920.a01.pub2.
P. A. Williams (ed.): Handbook of Industrial Water Soluble
Polymers, Blackwell Pub., Oxford 2007.