5

Flocculants

5.1 INTRODUCTION Polymers of different chemical composition are used in the mineral processing industry as flocculants, coagulants and dispersants. The number of these polymers continues to grow and applications have expanded to include selective flocculation, anti-scaling agents and binders for dust control. All these chemicals are either organic polymers or inorganic sub-stances. Because polymeric compounds can vary in electrical charge, molecular weight, three-dimensional structure and hydrophobicity, the range of compositions of functional polymers is virtually limitless. The polymers used in the above applications can be broadly defined as large molecules made up of repeating units. In the case of long-chain synthetic polymers, a reactive monomer unit is polymerized with the same or other monomer units in a sequential fashion resulting in molecular strands. The number of linked units may vary anywhere from a few to as many as hundreds of thousands. This number reflects the molecular weight of the polymer. The polymers used in flocculation, coagulation and dispersion, are either synthetic polymers (produced from polyacrylates) or natural polymers (starches, guar gums, etc.).

5.2

CLASSIFICATION OF FLOCCULANTS, COAGULANTS AND DISPERSANTS

The chemicals used for flocculation, coagulation and dispersion can be classified into two broad groups: inorganic and organic reagents. A different classification [1] is based on the action of the flocculant and is divided into the following categories: Polymers with flocculating action Polymers with dispersing actions Polymers with coagulating actions.

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5. Flocculants

5.2.1

Inorganic flocculants

Inorganic flocculants are used in applications where the source of cationic charge is required. Typical inorganic flocculants include: Calcium salts; typically lime Aluminum salts; such as sulfates or soda alum Iron salts such as ferrous sulfate and ferric chloride.

Aluminum salts have been widely used in water treatment applications as well as in those in which coagulation is required. Ferro salts are used in applications where low pH is used, namely, in hydrometallurgical processes. 5.2.2 Organic flocculants

Organic flocculants can be divided into two main groups [2]: natural and synthetic flocculants. Natural flocculants are derived from natural sources and have the general formula
CH2 C H C O H C H H C H n H O H C O

These flocculants can be derived from guar gums, hydrolyzed starch, modified polysac-charides and others. The use of these flocculants is less common for dewatering, but they are widely used for selective flocculation during the treatment of iron ores and other oxides. Synthetic flocculants are commonly used in dewatering circuits. The number and varieties of these flocculants is very large. In principle, these flocculants can be divided into three distinct classes depending on the charge of the functional group. Non-ionic polymers These polymers are exclusively derived from acrylamides by polymerization. The molecular weight of these polymers ranges from 1 to 15 million. A typical structure of a nonionic polyacrylamide is
CH2 CH n C O NH2 CH C CH C O NH2 n

5.2 Classification of Flocculants, Coagulants and Dispersants

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Other non-ionic polymers include

CH2 CH CN Polyacrylonitriles n OCH CH
2 2

and polyethylene oxide:

Polyelectrolytes Polyelectrolytes, depending on their charge (i.e. positive or negative) can be anionic or cationic. The representatives of the anionic flocculant group are: Co-polymers of acrylatesacrylamides:
CH CH
2

CH2 CH C x O O Na
y

C O NH2

The y-component can vary between 10% and 30%. Examples are the separan-type flocculant: Separan NP10 Y = 10% Separan NP20 Y = 20% Separan NP30 Y = 30%
CH2 CH C O O Na n CH3
CH2 C

C O O Na Polymethacrylates

Polyacrylates

Aerofloc 548 and 552 flocculants belong to this group.

H2C CH

CH2 CH n Polystyrene - sulfonic acid SO3H SO3H Polyvinyl - sulfonic acid n

Examples of flocculants from this group are natural polymers produced from carboxymethylcellulose, Tylose CBR400 and methylcellulose Tylose MH200, manufactured by Clariant Chemicals (formerly Hoechst Chemicals).

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5. Flocculants

Cationic polyelectrolytes are represented by polyethylene amines, polyvinyl amines and polyvinyl pyridines:
H CH2 CH2 N

CH CH
2

HCl

Polyethylene amines

NH3Cl Polyvinyl amines

H2C CH

N R

Cl n

Polyvinyl pyridines

The reaction products of the polyacrylamide and primary amines are:

HO Cl

C C NH CH2 NH2 CH2

R

Co-polymers Co-polymers are a reaction product of maleic acid and other compounds described by Wadsworth et al. [3], and include the following: Co-polymer of styrene and maleic acid:
CH2 CH C6H5 CH CH

CO2H CO2H

Co-polymer of acrylic acid and maleic acid

CH2 CH CO2H CH CO H
2

CH CO2H

Co-polymer of vinylmethyl ether and maleic acid

CH2 CH OCH3 CH CH

CO2H CO2H

5.3 General Application

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5.3

GENERAL APPLICATION

Application of the reagents described under flocculants can be broadly categorized into three major groups. These include flocculants, coagulants and dispersants. Table 5.1 lists some of the most important polymers that belong to each category. Polymeric and inorganic flocculants are employed in the mineral processing industry during the treatment of sulfides, oxides and silicates. Nowadays, they are used more and more in water treatment plants and also in waste treatment. Coagulants are chemicals that reduce the repellent charge on solids, allowing them to collide and agglomerate. In the treatment of very fine particles, such as clay, hydrometallurgical leach residue, etc., coagulants are used together with flocculants to improve settling characteristics. Dispersants in mineral processing have found a wide range of applications. In flotation of clay-containing ores, dispersants have been found to improve metallurgical results and
Table 5.1 List of the most important polymers presented in three categories Category Flocculants Chemical/polymer 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 1. 2. 3. 4. 5. 1. 2. 3. 4. 5. Polyacrylamides Acrylamide/sodium acrylate co-polymers Sodium or ammonium polyacrylates a a Acrylamide DMAEM or DMEA quat co-polymers Acrylamide DADMAC co-polymers Polyethylene oxide Guar gum Hydrolyzed starch Acrylamide/sodium 2-amps co-polymers (sulfonate) Modified polysaccharides Ferro salts Poly DADMAC DADMAC/acrylamide co-polymers Epichlorohydrin/dimethylamine condensation polymers Poly aluminum chloride Amine/formaldehyde condensation reagents Polyacrylic acid sodium or ammonium salts Methylacrylates/acrylic co-polymers Acrylate/2-amps co-polymers Polymaleic acid and sodium salts Methacrylate/acrylic co-polymers and salts Low molecular weight Low molecular weight Low molecular weight Low molecular weight Low molecular weight Class Non-ionic Anionic Anionic Cationic Cationic Non-ionic Anionic

Coagulants

Dispersants

Homopolymers of diallyl dimethyl ammonium chloride with the general formula: CH2 N H3C CH3 Cl CH2 n

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5. Flocculants

reduce reagent consumptions. Dispersants are extensively used in selective flocculation. In maintaining the stability of slurry and controlling slurry viscosity, dispersants play an important role. Many regulating reagents described in Chapter 3 also have a dispersing effect.

REFERENCES
1. Mahoney, R.P., and Roe, J.W., Polymer Usage in Mineral Beneficiation, In (P.S. Mulukutta ed)

Reagents for Better Metallurgy, SMME, 1994. 2. Blazy, P., Flocculation and Flocculants, Industrie Minerale-Metallurgie, Paris, France, 1973. 3. Wadsworth, H.E., and Cutler, I.B., Flocculation of Mineral Suspensions with Coprecipitated Polyelectrolytes, Mining Engineering, Vol.6, pp. 134142, April 1956.