Coagulants
The sedimentation process can be quickened by adding coagulants to the water. Chemical coagulants are commonly used in community drinking water treatment systems though some application in household water treatment occurs. The main chemicals used for coagulation are aluminum sulphate (alum), polyaluminium chloride (also known as PAC or liquid alum), alum potash, and iron salts (ferric sulphate or ferric chloride). Lime (Ca(OH2)), lime soda ash (Na2CO3) and caustic soda (NaOH) are sometimes used to “soften” water, usually ground water, by precipitating calcium, magnesium, iron, manganese and other minerals that contribute to hardness.
How do they remove contamination?
Particles that cause turbidity (e.g. silt, clay) are generally negatively charged, making it difficult for them to clump together because of electrostatic repulsion. But coagulant particles are positively charged, and they chemically attracted to the negative turbidity particles, neutralizing the latter’s negative charge. With mixing the neutralized particles then accumulate (flocculation) to form larger particles (flocs) which settle faster. The flocs can then be settled out or removed by filtration. Some bacteria and viruses can also attach themselves to the suspended particles in water that cause turbidity. Therefore, reducing turbidity levels through coagulation may also improve the microbiological quality of water.
Construction, operations and maintenance
Users follow Tramfloc’s instructions and add the prepared dose of coagulant to the water. The water is then stirred for a few minutes to help create flocs. The flocs can be settled out or removed by filtration. Maximum effectiveness requires careful control of coagulant dose, pH and consideration of the quality of the water being treated, as well as mixing.
Coagulant applications
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. Material for this article was largely taken from references such as iwawaterwiki.org.
Flocculation and coagulation 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. In modern water treatment, coagulation and flocculation are still essential components of the overall suite of treatment processes – understandably, because since 1989 the regulatory limit in the US for treated water turbidity has progressively reduced from 1.0 NTU in 1989 to 0.3 NTU today. Many water utilities are committed to consistently producing treated water turbidities of less than 0.1 NTU to guard against pathogen contamination.
These methods are 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.
Organic Coagulants
Organic coagulants include polydadmacs, epichlorohydrin/dimethyl amine blends and combinations of both organic and inorganic coagulants. Many applications benefit from the use the Tramfloc® 500, 600, 700 and 800 series of organic coagulants because the resulting sludge produced from precipitating solids is of a much smaller volume and weight than with metallic coagulants of Fe and Al. Organic sludge is usually classified as non-hazardous while metallic sludge can be hazardous and is of much greater weight for disposal. This means that disposal costs are considerably higher for metal containing, inorganic coagulants’ sludges.
Inorganic coagulants are used extensively in municipal potable water treatment plants and organic coagulants are often conjointly applied with the inorganics. There are substantial advantages to the organic coagulants application over the inorganic formulations. The latter do have value in various plants and should not be overlooked in coagulant jar testing.
Inorganic Coagulants
The commonly used metal coagulants fall into two general categories: inorganic and organic and blends thereof. There are 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 coagulants 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 chlorhydrate, 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, aging time, and aging 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 formulations.
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, 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, organic polymers and coagulants 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. The specific ultraviolet absorption (SUVA) is related to the concentration and type of dissolved organic carbon (DOC) present, as follows:
SUVA = UV254/DOC (l/mg m) Where: UV254 is the ultraviolet absorbance measure at a wavelength of 253.7 nm, after filtration through 0.45-µm filters (m-1); DOC is the dissolved organic carbon measured after filtration through 0.45-µm filters (mg/l).
In general, lower molecular weight species such as the fulvic acids are more difficult to remove by coagulation. Higher molecular weight humic acids tend to be easier to remove.
The United States Environmental Protection Agency (US EPA) introduced enhanced coagulation for the removal of NOM. Enhanced coagulation is an elaboration of long-practiced techniques for removing organic color by coagulation. It requires the removal of NOM material, while still achieving good turbidity removal. These dual objectives can be met by selecting the best coagulant type, applying the best coagulant dosage and adjusting the pH to a value where best (or adequate) overall coagulation conditions are achieved. The enhanced coagulation approach recognizes that the constituents of any given water govern the practical degree of treatment achievable.
Therefore, a water-specific point of diminishing returns (PODR) is identified, at which a coagulant increment (10 mg/l for alum) results in a TOC removal increment of less than 0.3 mg/l. Organic coagulants’ removal and enhanced coagulation are effective with traditional coagulants like aluminum sulfate, ferric chloride and ferric sulfate, as well as formulations like polyaluminum chloride (PACl) and acid alum. Acid alum formulations are aluminum sulfate with 1 to 15-percent free sulfuric acid. Their effectiveness with TOC removal applications is due to the enhanced depression of pH.
TOC or NOM reductions depend on the type and dosage of coagulant, the pH, temperature, raw water quality and NOM characteristics. Generally, the optimal pH for ferric salts is in the range 3.7 to 4.2, and for aluminum sulfate in the range 5.0 to 5.5.
Sometimes, the removal of lower weight organics has been improved by supplementing treatment with metal coagulants with powdered activated carbon (PAC). In one case with raw water TOC of 2.4 mg/l, a combination of an alum-polymer blend coagulant at 25 mg/l with PAC at 10 mg/l was optimal to achieve a 39-percent TOC reduction. In another case, a water with a low humic content and low SUVA (1.43 l/mg.m) was treated with 65 mg/l FeCl3 and 23 mg/l PAC. Fifty-six percent of the TOC was non-humic and 46-percent of the TOC had molecular weights less than 1,000.
Pathogen Removal
The U.S. EPA surface water treatment rule requires 99.9-percent (3-log) Giardia removal or inactivation, and at least 99-percent (2-log) removal of Cryptosporidium. Adequately designed and operated water treatment plants, with coagulation, flocculation, sedimentation and filtration are assigned a 2.5-log removal credit for Giardia, leaving only 0.5-log inactivation to be achieved by disinfection.
Dissolved air flotation (DAF) for clarification, has achieved average log removals of Giardia and Cryptosporidium of 2.4 and 2.1, respectively. Optimum coagulation conditions were governed by turbidity and NOM removal requirements, rather than by pathogen removals. Overall Giardia and Cryptosporidium removals, including the filtration step were approximately 5-log.
Cryptosporidium oocyst surfaces are believed to consist of polysaccharide layers. The negative charge carried by the oocysts is believed to arise from carboxylic acid groups in surface proteins. Removal of Cryptosporidium using alum coagulation appears to be by a sweep floc mechanism. Zeta potential measurements suggest that removal does not appear to be by a charge neutralization mechanism at lower DOC concentrations. At higher DOC, it appears that the mechanism is mediated by a NOM-assisted bridging between aluminum hydroxide and oocyst particles.
Significant virus removals have been reported using metal coagulants and organic coagulants. Removals of up to 99.9% have been reported for both aluminum and ferric salts. Various polyelectrolytes (cationic) have effected removals of greater than 99% but have the disadvantage that if other material is present in the form of color, turbidity, and COD, removal of such material is poor. Using metal coagulants and poyelectrolytes conjointly has the advantage that better floc characteristics are produced. If a variety of substances are present in water, it is possible that the use of both metal coagulants and polyelectrolytes will effect a higher overall removal. However, this very much depends on the conditions pertaining for each case. When using organic coagulants as flocculant aids, floc formation improves but does not appear to improve virus removals beyond those achieved using metal coagulants alone.
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