Coagulation and Flocculation in Water and Wastewater Treatment

Coagulation and Flocculation

Coagulation and flocculation are an essential part of drinking water treatment as well as wastewater treatment.This article provides an overview of the processes and looks at the latest thinking.Coagulation and flocculation are essential processes in various disciplines. In potable water treatment, clarification of water using coagulating agents has been practiced from ancient times. As early as 2000 BC the Egyptians used almonds smeared around vessels to clarify river water. The use of alum as a coagulant by the Romans was mentioned in around 77 AD. By 1757, alum was being used for coagulation in municipal water treatment in England.
Coagulation is also important in several wastewater treatment operations.  A common example is chemical phosphorus removal and another, in overloaded wastewater treatment plants, is the practice of chemically enhancing primary treatment to reduce suspended solids and organic loads from primary clarifiers.
The Coagulants
The commonly used metal coagulants fall into two general categories: those based on aluminum and those based on iron. The aluminum coagulants include aluminum sulfate, aluminum chloride and sodium aluminate. The iron coagulants include ferric sulfate, ferrous sulfate, ferric chloride and ferric chloride sulfate. Other chemicals used as coagulants include hydrated lime and magnesium carbonate.
The effectiveness of aluminum and iron coagulants arises principally from their ability to form multi-charged polynuclear complexes with enhanced adsorption characteristics. The nature of the complexes formed may be controlled by the pH of the system.
When metal coagulants are added to water the metal ions (Al and Fe) hydrolyze rapidly but in a somewhat uncontrolled manner, forming a series of metal hydrolysis species. The efficiency of rapid mixing, the pH, and the coagulant dosage determine which hydrolysis species is effective for treatment.
There has been considerable development of pre-hydrolyzed inorganic coagulants, based on both aluminum and iron to produce the correct hydrolysis species regardless of the process conditions during treatment. These include aluminum chlorohydrate, polyaluminum chloride, polyaluminum sulfate chloride, polyaluminum silicate chloride and forms of polyaluminum chloride with organic polymers. Iron forms include polyferric sulfate and ferric salts with polymers. There are also polymerized aluminum-iron blends.
The principal advantages of pre-polymerized inorganic coagulants are that they are able to function efficiently over wide ranges of pH and raw water temperatures. They are less sensitive to low water temperatures; lower dosages are required to achieve water treatment goals; less chemical residuals are produced; and lower chloride or sulfate residuals are produced, resulting in lower final water TDS. They also produce lower metal residuals.
Pre-polymerized inorganic coagulants are prepared with varying basicity ratios, base concentrations, base addition rates, initial metal concentrations, ageing time, and ageing temperature. Because of the highly specific nature of these products, the best formulation for a particular water is case specific, and needs to be determined by jar testing. For example, in some applications alum may outperform some of the polyaluminum chloride formulations1.
PoIymers are a large range of natural or synthetic, water soluble, macromolecular compounds that have the ability to destabilize or enhance flocculation of the constituents of a body of water.
Natural polymers have long been used as flocculants. For example, Sanskrit literature from around 2000 BC mentions the use of crushed nuts from the Nirmali tree (Strychnos potatorum) for clarifying water – a practice still alive today in parts of Tamil Nadu in Inia, where the plant is known as Therran and cultivated also for its medicinal properties. In general, the advantages of natural polymers are that they are virtually free of toxins, biodegradable in the environment and the raw products are often locally available. However, the use of synthetic polymers is more widespread. They are, in general, more effective as flocculants because of the level of control made possible during manufacture.
Important mechanisms relating to polymers during treatment include electrostatic and bridging effects.  Polymers are available in various forms including solutions, powders or beads, oil or water-based emulsions, and the Mannich types. The polymer charge density influences the configuration in solution: for a given molecular weight, increasing charge density stretches the polymer chains through increasing electrostatic repulsion between charged units, thereby increasing the viscosity of the polymer solution.
 One concern with synthetic polymers relates to potential toxicity issues, generally arising from residual unreacted monomers. However, the proportion of unreacted monomers can be controlled during manufacture, and the quantities present in treated waters are generally low.
Removal of Natural Organic Matter
Natural organic material (NOM) is usually associated with humic substances arising from the aqueous extraction of living woody substances, the solution of degradation products in decaying wood and the solution of soil organic matter. These substances are objectionable for a number of reasons: they tend to impart color to waters; they act as a vehicle for transporting toxic substances and micro-pollutants, including heavy metals and organic pollutants; and they react with chlorine to form potentially carcinogenic by-products.
The degree to which coagulation can remove organic material depends on the type of material present.
Flocs in Water Treatment