UNIT 11

Structure
11.1 11.2 11.3

INDUSTRIAL EFFLUENTS

Introduction
Objectives

Industrial Effluents Pollution Parameters and Treatment Methods

Pollution Parameters Treatment Methods

Effluents from Food and Food Processing Industries Dairy Waste

Sources of Waste Methods for Reducing Wastewater Quantity Treatment of Dairy Waste

11.4

Effluents from Petrochemicals

The Petrochemicals Industry Waste Characteristics Waste Disposal Treatment

11.5

Effluents from Textiles

The Textile Industry Textile Waste Characteristics Textile Wastewater Problems Textile Waste Treatment

11.6

Effluents from Pulp and Paper Industry

The Pulp and Paper Industry Effluent from Pulp and Paper Industry Characteristics of Effluent Suspended Solids Reduction Sludge Dewatering and Disposal Methods for the Reduction of Organics Land Disposal by Irrigation and Seepage

11.7

Effluents from Tanneries

The Leather Industry Tannery Waste Characteristics Tannery Waste Treatment

11.8 11.9 11.10 11.11 11.12 11.13

Hazardous Wastes
Hazardous Waste Generation Hazardous Waste Ma nagement

Summary Terminal Questions Answers Glossary Suggested Readings

11.1

INTRODUCTION

Pollution of streams, lakes and coastal waters has emerged as a major water pollution problem. It renders these natural resources unsuitable for human consumption and even for recreational purposes like swimming, boating etc. Industrial wastes, municipal sewage and domestic wastes are the major sources of stream pollution. Agricultural activities which discharge both excessive quantities of silt and chemicals leached or washed from the soil, also contribute to water pollution. Industrial wastewater is an inevitable result of nearly all manufacturing industries. Water is used in large quantities for many purposes by industry. Only a small fraction of the water used is consumed in manufacturing process and its major portion is discharged from the plant premises. These discharges are inevitably contaminated with

Pollutants in Soil and Water

materials used in the plant. The contaminants include raw materials, unwanted substances accompanying the raw materials, manufactured products, intermediate products, by-products and other substances used in the processing. All these materials contribute to pollution of the receiving water bodies.

Objectives
After studying this unit, you should be able to: define industrial effluents and describe their physico- chemical characteristics, explain the methods of industrial effluents treatment, describe various methods of dairy waste treatment, describe sources of generation of wastewaters from petrochemical industries, understand waste disposal methods for refineries and petrochemical industries, explain sludge disposal methods used in refineries, describe characteristics of effluents from pulp and paper industry and their treatment methods, describe the salient features of tanneries and describe characteristics of its wastes, define hazardous wastes, describe its sources and their management and describe treatment and disposal of hazardous wastes.

11.2

INDUSTRIAL EFFLUENTS - POLLUTION PARAMETERS AND TREATMENT METHODS

Industrial effluents are characterized by their differences rather than their similarities. Each individual plant is an individual problem. But, there are common parameters by which pollution can be evaluated. Also, there are general treatment me thods applicable to the plants in any given industry due to their similarities. The common parameters and treatment methods need to be understood before studying the characteristics and treatment methodologies for specific industries. In this section, we will discuss the physico-chemical parameters commonly used in the study of wastewaters.

11.2.1

Pollution Parameters

Natural water is never pure and inevitably carries, in dissolved or suspended form, every material it has contacted. The presence of one or more substances at a level which does not produce objectionable characteristics is not pollution. The word "pollution" is to be applied only when impurities are present in objectionable concentrations. Quantitative evaluation of stream pollution is based on the concentration of specific impurities or identifiable groups of impurities in the stream. These concentrations are related, in turn, to the corresponding concentrations in waste waters discharged into the stream. Concentrations are usually reported in milligrams per litre (mg L1) or parts per million (ppm). Flows are usually stated in cubic meter per second (in short written as cumec). It is often desirable to express pollution in total quantity rather than in concentration. (i) Total Suspended Solid s (TSS): The total suspended solids or nonfiltrable residue is the dry weight of residue retained by filter. This is obviously the particulate matter and not the dissolved impurities; though very fine particulate matter and colloidal solids may not be reta ined on the filter. A distinction between fixed and volatile suspended matter can then be made by ignition. Coarse and floating solids are impossible to sample in a representative manner; hence they should be avoided in the sample. There is no reason to permit such wastes in an industrial or municipal effluent. They occur, of

course, in almost all the industries, like food processing plants, textile mills, and other industries, but are readily removed from the waste stream before discharge. The principal objection to total suspended solids is that they give unesthetic appearance to the stream. It is, however, no different from silt and other natural suspended matter, unless the color is unusual. Suspended matter also reduces light penetration into the stream water and hence affects oxygen regeneration by photosynthesis. (ii) Settleable Solids: The portion of total suspended matter which can be removed by quiescent settling is particularly significant. In a stream, settling tends to clarify the water, but at the expense of creating bottom deposits or sludge banks. These deposits, containing organics, decompose with formation of objectionable odours and also remove oxygen from the stream. Deliberate removal of settleable matter by sedimentation, in specially designed equipment, is one of the most useful methods of waste treatment. It is used to remove settleable matter from the raw waste and that produced from nonsettleable contaminants during the waste treatment process. Settleable matter can be determined volumetrically, using an Imhoff cone or similar vessel. It is more often determined by weight, and is the difference between total suspended solids in the water before and after laboratory settling. (iii) Total Dissolved Solids (TDS): Dissolved solids or filtrable residue, in contrast to total suspended solids, is the portion of "residue" which passes through the filter in solution or in fine suspension in the water. (iv) Turbidity: It is a measure of the effect on light, and hence on appearance of the wastewater caused by suspended and colloidal matters. It has obvious esthetic significance, both in the stream itself and in any municipal water supplies drawn from it. It may render the waters unsuitable for municipal supplies or for certain industrial uses, notably for food, beverage, and paper manufacture. (v) Oils: Oils and other floating films are highly objectionable in natural waters, for their unaesthetic qualities and for actual damage to the water-way. They retard aeration of the stream, thus killing fish. Heavy oil films have been known to trap and kill waterfowl and land wildlife. Oily films coat bridge piers and other structures, leaving unsightly deposits. They may be difficult to remove. Soluble or colloidal oils are less troublesome, except as chemical or biological action in the stream may release them as free oils. (vi) Color : Color occurs naturally in many streams, typically as a yellow or brown shade from swamp waters, or brown from iron-bearing waters. These and other colors may also be imparted by industrial effluents. Acid mine waters and natural drainage in mining regions often carry heavy iron discoloration, sometimes worsened by tannic acid and similar natural constituents of the water. Dye wastes from dyestuff manufacture, paper mills, and textile dyehouses may be spectacular and undesirable. The wastes of many industries are colored and hence objectionable to the public. Colored waters are not usable for public water supplies without treatment, which is often elaborate and expensive. They may not be usable for certain industrial waters under any circumstances. Color itself may be harmless but it is unwanted, and it may be an indication of more serious pollution such as a toxic substance. (vii) Taste : Tastes caused by pollution are significant in potable waters and in waters used for fishing. In the latter case, fish flesh often acquires and even concentrates taste -producing contaminants of the water. Many chemicals mainly phenol and its derivatives cause objectionable tastes. The medicinal taste of phenol is worsened by chlorination, used in water treatment. Phenols sometimes occur naturally, due to

Industrial Effluents

Imhoff cone is described in Unit 13 on Municipal and Domestic Wastes.

Pollutants in Soil and Water

decomposition of tannin compounds in swamp waters. Their presence in water is, however, generally blamed on industries such as coke and gas manufacture, petroleum refining, and the production of chemicals and plastics. (viii) Odor: Odour may be a characteristic of the raw waste, or it may develop in the waste or the receiving stream by decomposition of other pollutants. Odours are aesthetically offensive, even at an appreciable distance from their source. Commercial food preparation and similar operations cannot be conducted in an odourous environment. Some of the gases associated with odour may be physically damaging to structures, by causing chemical corrosion or discoloration of paint. Sulphide odours are the principal cause of complaint. (ix) Acidity, Alkalinity and pH: One of the most damaging characteristics of many industrial wastes, particularly from the inorganic industries, is their acid or alkali content. Either a high or a low pH may kill fish, cause general sterility in natural streams and inactivate the essential microorganisms in sewage treatment processes. Wastes of low pH are corrosive to steel and concrete structures in water ways or sewerage systems. The pH is maintained in wastewaters by chemical neutralisation. Adequate controls are available for this process, and the final effluent can be made suitable for discharge to either a stream or a sewer. Both acidity and alkalinity are customarily expressed in milligrams of calcium carbonate equivalent per litre. The intensity of acid or alkaline quality is expressed by the pH value, which has a more direct relationship than acidity or alkalinity to the most pollutional effects of the waste. Fish kills, for example, are caused by low pH rather than by a high concentration of titratable acidity. The measurement of pH is relatively simple, using electrometric technique. At the point of discharge, wastes should be near neutrality, us ually in pH range from 6 to 9, though it may vary with the receiving stream or sewage. (x) Chlorides: Sodium chloride brines are waste products from many industries, particularly crude petroleum production and the manufacture of soda ash and other chemicals. Concentrations of chloride up to about 500 mg L 1 are acceptable in most natural waters, with much higher quantities permissible in some, but uncontrolled discharge of brines would far surpass any reasonable limit in many streams. There is no practicable treatment to remove chlorides, so the usual solution to the problem is impoundment and carefully controlled release into streams that provide adequate dilution. Disposal to the ocean is feasible in some locations and disposal to deep underground formations in others, but chloride wastes remain one of the major unsolved problems of industries. Chlorides may be removed by reverse osmosis or electrodialysis; however, these techniques are not cost effective. (xi) Hardness: All natural waters contain some de gree of hardness, caused primarily by calcium and magnesium. Hardness, in any degree, is expensive as it causes scale formation, increases soap consumption and forms precipitates or scums. Industrial effluents that cause hardness include calcium chloride brines from many chemical industries and wastes from lime -consuming industries such as water treatment plants, pulp mills and tanneries. (xii) Surfactants: Surface-active chemicals, including the synthetic detergents cause problems in sewage treatment plants and in natural streams because of their ability to form froth. The problem has been worsened because the conventional alkyl benzene sulfonate surfactants are persistent, and refractory. Despite their organic composition, they are broken down but slowly by natural stream organisms. The detergent

Acidity or alkalinity is determined by titration to a specified pH. More commonly, the phenolphthalein and methyl orange endpoints, approximately 8.3 and 4.3, respectively, are used for their determination. These titrations indicate the quantity of neutralising material required for treatment which may preexist in the receiving stream or may be added as a part of waste treatment.

manufacturing industry is shifting to biodegradable types of detergents. Frothing may continue until the surfactant properties are destroyed in natural stream environments. Though unaesthetic , froth is not harmful and serves a useful purpose of indicating domestic pollution. (xiii) Other Solutes: Almost every chemical or substance used in industry escapes to some degree with the wastewater. These may include raw materials, intermediates, final products, by-products and processing substances. The most troublesome being sulphates, nitrates, ammonium compounds and salts of heavy metals. (xiv) Radioactivity: Radioactive wastes have great pollutional potential. Radioisotopes are becoming more widely employed for indus trial and other uses and the number of their discharge points ha s increased. They are hazardous to health because they emit high energy radiations. The danger increases when the water is consumed for drinking or for food preparation. It may worsen if the dispersed radioactive pollutants become concentrated by the chemical precipitation or the action of living organisms including microorganisms. In general, radioactivity cannot be destroyed, but radioactive wastes can be either disposed of either by dilution to a degree that is safe, or by concentrating and keeping in isolated, protected locations until they decay naturally. The choice of technique depends on the volume and concentration of the waste and other factors. (xv) Dissolved Oxygen (DO): The most generally accepted single criterion of pollution is the DO content of the stream. Under favorable nonpolluted conditions, it may approach the saturation value, or may even exceed saturation because of photosynthesis or oxygen generation in the stream. The DO saturation value depends on temperature. The reserve of available DO, for bio-oxidation of organic wastes, is not large and is easily depleted. Of course, oxygen is restored to the stream waters by photosynthesis, which is intermittent, and by absorption from the atmosphere, which is limited in rate. An overpolluted stream can thus become totally devoid of DO, a condition that is readily apparent by dead fish, bad appearance and offensive odours. If about 2 mg L 1 of DO can be maintained in all parts of the stream, nuisance conditions can be avoided. A higher concentration, perhaps 4-6 mg L1, is necessary for a healthy population. (xvi) Biochemical Oxygen Demand (BOD): The major pollutional effect of organic wastes in a stream is their consumption of DO under the influence of living microorganisms. The rate and extent of oxygen depletion is customarily evaluated by the biochemical oxygen demand (BOD) test. This is not a direct measure of organic content, but is a measure of its most significant pollutiona l characteristic, the capacity to consume oxygen. It is reported as milligrams of oxygen per litre. (xvii) Chemical Oxygen Demand (COD): The BOD test is useful in many ways but has the disadvantage that it requires long incubation time for completion (5 days at 20C or 3 days at 27C) . Organic matter in wastewater can be evaluated in a few hours by the chemical oxygen demand or COD test. This does not duplicate the BOD test; it may or may not have a consistent ratio to the BOD. There is no fully acceptable substitute for the BOD test, but the COD test has been a considerable substitute. Both tests measure organic matter and certain types of organic compounds are resistant to each of the two tests but not in the same manner. After studying the parameters, let us now study the treatment methods.

Industrial Effluents

The determination of DO requires many precautions such as avoiding changes during handling of the sample. The analysis must be performed, or at least carried to the point of chemical fixation, at the sampling site. The actual analysis involves absorption of the DO on freshly precipitated manganous hydroxide, release of an equivalent concentration of free iodine from iodide salt, and titration of the iodine with a standard sodium thiosulphate solution. Though complex, the whole procedure has been thoroughly standardized and The BOD test involves, first, a measurement of the DO initially present in a sample of water containing the waste under study. This may be a sample from the polluted stream or a batch of special water to which a known amount of waste has been added. Other samples of mixed water and waste are then incubated, in the presence of suitable microorganisms and nutrients and in an appropriate environment, usually for 5 days at 20C or 3 days at 27C. The remaining DO is then measured, the amount of DO consumed during the test is computed, and the oxygen requirements of the waste are reported as BOD. If all the DO is consumed during the incubation period, no quantitative report can be made; however, waste can be diluted to produce usable 9 data. There can be several interferences in the BOD test.

11.2.2

Treatment Methods

Pollutants in Soil and Water

Industrial wastewaters are discharged from the plant premises to some receiving water bodies which have to some degree capacity for assimilating pollution. The degree of assimilation depends on the ratio of dilution available, downstream uses of the water and characteristics of the waste. It is reasonable and proper to utilise the stream's assimilative powers to the full, short of impairing its usefulness and esthetic quality. Such reasonable use for waste transport should not be considered as pollution. A somewhat similar situation exists when industrial waste is discharged into a municipal sewer. This is often a convenient means of disposal, but it requires consideration of the possible effects. Most municipalities ban industrial wastes that are deleterious to the sewerage system, by corrosion of the sewers and plant equipment or by interference with the sewage treatment plant and process. The industrial waste contaminants may be destroyed by the sewage treatment, they may disrupt the treatment or they may simply flow unchanged through the sewerage system. In the last case, they are at least diluted by the municipal wastewater. If the assimilative capabilities of the stream or of the sewerage system are not adequate, the industrial waste should not be released in its original form. Treatment of the waste before discharge is, therefore, essential. Several treatment methodologies are available: some are related to the processes of sewage treatment while others are developed specifically for industrial wastes. These are discussed below. It is often economical to eliminate or reduce the quantity of waste at its source in the manufacturing plant prior to treatment. Several techniques exist based on engineering practices and common sense. (1) In plant Measures

The COD test is based on treating the wastewater with a known amount of dichromate, digesting at an elevated temperature to oxidise the organic matter and titrating the unconsumed dichromate with standard ferrous ammonium sulphate using ferroin indicator. The oxygen equivalent of the dichromate destroyed is reported as the COD. Chlorides are the most significant source of error, due to their reaction with dichromate however, a correction for chlorides can be made or chloride interference could be eliminated by adding mercuric sulphate to the

(i) Process Change: It is not unusual to change the manufacturing process in order to ease the pollution problem. Several instances of this kind exist and it will probably become more common as antipollution efforts continue. A related change, at great cost, has been that of the synthetic detergents i.e. from hard detergents to bio-degradable materials so that domestic laundering wastes shall be less troublesome. Now cleaner technologies are being developed to minimise pollution. (ii) Material Recovery: Raw materials and products are valuable to the manufacturer but some fraction of each tends to be lost into the waste stream. This is an economic loss and to avoid pollution, their removal also adds to the cost. There is an economic gain if such substances can be reused in manufacturing or used for some other purpose. Several substances can be recovered from waste or intercepted before they enter the waste stream. The recovery of by-products may also have merit and has been profitable to some industries. (iii) Water Reuse: Most industries use water, often in large quantities yet little or none enters the final product. The most or all of it must be discharged as a pollution-bearing waste. Water is costly, and water of quality suitable for industry becomes scarcer every year. Sometimes, with only partial purification, spent water can be reused once or several times in the manufacturing process. Spent cooling water is particularly amenable to reuse but even contaminated wastewaters have salvage value. Water unsuitable for direct reuse may be used for those purposes in which quality requirements are less strict. Final rinsing of a product may require nearly pure water, but the spent rinsewater may be usable for primary rinsing, or in a countercurrent series of rinses without intermediate purification. The concept of zero discharge has now been introduced which means complete recycle and reuse of water.

10

(iv) Wastewater Collection: Usually the first step toward wastewater treatment is its collection from the several sources in the plant and transportation to a treatment site. Certain types of wastes should be kept separate until they reach the treatment plant or even some advanced stage of treatment e.g. acid and cyanide wastes should be segregated for the sake of safety. Strong and weak wastes, otherwise similar, are often separated for more economical treatment, perhaps to be blended after they become more or less similar in quality. On the other hand, the mixing of wastes may provide partial treatment in itself, as by partial neutralisation between acid and alkaline wastes. Mixing, too, provides equalisation or leveling of fluctuations in flow or in composition. This leads to simpler treatment or better control of discharge. In general, if treatment of discharge is facilitated by separate handling of certain wastes, separation should be maintained, but only as long as there is real benefit. (2) Particulate Removal

Industrial Effluents

The removal of particulate or suspended matter from a wastewater is an important part of its treatment because this is a less expensive operation than the chemical or biological operations needed for dissolved matter removal. The most common techniques being settling, flotation and filtration. (i) Settling : Settling or sedimentation, is the least expensive physical treatment. Several settling operations may be utilised in the processing of a given wastewater. Heavy grits are removed by passing the wastes through screens, however, finer suspended matter originally present and precipitates or sludges formed by chemical or biological treatment are removed by settling. Settling is accomplished in ordinary lagoons but more commonly special tanks are built for the purpose. An inevitable by-product of sedimentation is sludge. Removal of sludge from the settling basin may be intermittent if the quantity is small or continuous (usually by scraper mechanisms and pumps) when its volume is greater. Some heavy inorganic settled materials are solid or semisolid in nature, but most sludges are fluid slurries that require further dewatering prior to disposal. Disposal is often a problem, principally because of the land area required. Particles lighter than water of course move upward and are removed by skimmers rather than scrapers. Many oils fall under this category and are recoverable by settling and skimming. (ii) Flotation: Fine solids or particulate matter with a density less than or close to that of water are not readily removable by simple settling. Their removal can be accelerated by floating the particles with minute air bubbles. The bubbles and solids (or oils) rise to the surface and are removed by skimming. (iii) Filtration: It is generally more expensive than settling but it provides a better removal. The filtration system takes less space and has certain special applications. Sludges produced by settling can be further dewatered by filtering either on a sand bed or by mechanical equipment. Filtration of raw wastes is not a common practice because of the large volume. Treated wastes are filtered as a final treatment step if the discharge requirements are critical, as for effluents that are to be injected into porous underground formations. Screening has some mechanical similarity to filtration, and is almost universally used as an early step in industrial waste treatment. It removes coarse materials that might interfere with subsequent operations in the treatment. (3) Physical Treatment Methods
Temperature control, usually by gentle heating, is necessary in certain biological treatments such 11 as anaerobic digestion of organic sludges and the aerobic or anaerobic

The bubbles are created either by pressurizing the wastewater with air and subsequently releasing the pressure or by applying vacuum to air-saturated wastewater. Screens range from coarse bar racks with 10 or 15 cm openings to fine screens of 40 mesh or smaller. They must be kept free from solids accumulations, lest their head loss become excessively high or their throughput low.

Heat treatment of wastes is expensive and unusual. It is sometimes employed, usually on special wastes or wastes having small volume for emulsion breaking or oxidation of organic matter.

Pollutants in Soil and Water

Incineration of dewatered sludges is common in municipal sewage treatment, and may be utilised for organic indus trial wastes. It is, commonly used for disposal of trash and other solid wastes. Cooling of hot wastes may be necessary before their discharge to a stream or sewer. It is usually accomplished by spraying, cascading or simple holding. This is a problem of considerable importance in the power industry. Radioactive wastes may be stored for decay of radioactivity and above a certain minimum concentration, they require elaborate cooling equipment to dissipate the heat energy liberated spontaneously. (4) Adjustment of pH

Wastes of excessively low or high pH require neutralisation before their release. Some plants, especially in the chemical industries, create both acid and alkali wastes, for which blending provides partial neutralisation. For final pH adjustme nt, and sometimes for the whole task of neutralisation, lime, soda ash or mineral acids are used. Acidic wastes can be neutralised with various basic chemicals. Caustic soda and sodium carbonate are somewhat expensive but extremely convenient. They are widely used by small plants or for treatments where small quantities are adequate. Lime is cheaper but somewhat less convenient and is the most widely used alkaline reagent. Alkaline wastes are less problematic than acid wastes, but nevertheless often require treatment. If acidic waste streams are not available or are not adequate to neutralise alkaline wastes, sulphuric acid is commonly employed. In some industries, carbon dioxide in the form of fuel gas has been used to neutralise strong alkaline wastes. Neutralisation can be controlled by automatic instruments, and it is often desirable to record the pH of final effluent as it is discharged. Deliberate acidification waste streams or alkalisation is sometimes used as a special form of treatment e.g., oil emulsions may be broken by acidification. The pH must usually be restored close to neutrality (pH 7) before final discharge. (5) Oxidation and Reduction

The pollution characteristics of organic wastes and a few inorganic wastes can be destroyed or minimis ed by oxidation. Oxidation can be done by one or more oxidising reagents.
Aerate: To permeate or saturate a liquid with air.

Aeration is the least costly means of oxidation, but has limited effectiveness. Few industrial wastes are adequately treated by aeration alone. Aeration is necessary in some types of biological treatment, and aids chemical treatment with ferrous iron coagulants. Oxygen is more effective than air, but is rarely used because of its cost. High temperature high pressure oxidation with air is used in sewage sludge destruction and for some industrial wastes. Chlorination is the most common chemical oxidation method in industrial waste treatment. Since chlorine is costly, it should be used on concentrated rather than dilute wastes, except for final disinfection, if needed. Hypochlorite sals and chlorine dioxide t are used in special circumstances. Ozone is used for oxidising certain industrial wastes, notably phenols and cyanides. Permanganates and dichromates also have specific applications. The only significant application of chemical reduction to treat an industrial waste is in the conversion of

Chlorination: Application of chlorine to water or wastewater, generally for the purpose of disinfection, but frequently for accomplishing other biological or chemical

12

chromate wastes containing hexavalent chromium to trivalent chromium, which is more easily precipitated. (6) Chemical Precipitation

Industrial Effluents

Chemicals are often added to an industrial waste for precipitating a particular component. Metal ions, for example, are removed from solution by precipitation with alkaline reagents, and then by settling or filtration. Similarly, other components can be converted to volatile compounds by chemical treatment, and then removed in an air or gas stream. Chemical coagulation involves the precipitation of chemicals deliberately added to the wastewater in such a manner that the precipitate removes colloidal and finely divided contaminants. Iron salts, for example, are added to the waste, usually with lime, to form a precipitate of ferric hydroxide. As this precipitates, it agglomerates to large flocculant particles. On settling, they entrap fine particles that otherwise do not readily settle by themselves. This technique is used in many industries, especially for organic colloidal wastes from meat packing, canning and petroleum refining.

(7)

Other Chemical Methods

Ion exchange is used to treat certain industrial wastes, especially if the contaminants are few and noninterfering, and if the recovered material has salvage value. Dilute rinsewaters from the metal processing industries can, in this manner, be recovered for their metal values and for reusable water. Adsorption, usually by activated carbon, often removes trace concentrations of particularly troublesome contaminants. Phenolic wastes from coke production and plastic manufacture can be treated by activated carbon to remove even fractions of a milligram per litre. Some adsorbed materials are recoverable and the adsorbent regenerable. (8) Aerobic Biological Treatment

Dilute organic wastes, difficult or impossible to treat by physical or chemical methods alone, are often amenable to attack by microorganisms which may be aerobic (in the presence of dissolved oxygen) or anaerobic (in the depleted state of dissolved oxygen). Certain nutrient elements must be present, notably nitrogen and phosphorus. The organic components are destroyed by metabolic processes, ending as innocuous materials. In aerobic systems, much of the carbon is removed as carbon dioxide, the hydrogen as water, and nitrogen and sulphur as nitrate ion or nitrogen gas and sulphate ion, respectively. Some of the waste is converted to cell tissue in the microorganisms and the excess appears as sludge. Some commonly used aerobic biological processes are described below: (i) Trickling Filters: It is a well-known technique for promoting contact among an industrial waste, the microorganisms that will consume it and the oxygen needed for metabolism. This is a bed of crushed rock or other suitable medium through which the wastewater trickles and the air penetrates by natural or forced ventilation. Biological growths develop as a film on the medium, from microorganisms which are present in the wastewater or are added in the form of domestic sewage or other culture. As the microorganisms grow, the organic wastes are consumed as food and metabolised to simple and harmless compounds. Fragments of the film, containing dead and living organisms, slough off from time to time and must be removed from the effluent, usually by settling.

13

Pollutants in Soil and Water

A few organic wastes are not amenable to microbiological attack, but most compounds can, in time, develop a biological community that consumes them. Toxic materials, especially if they occur suddenly in the waste, interfere with or even kill the microorganisms, resulting in failure of the process. Equalisation of the wastewater before treatment helps to prevent such shock dosages. Nutrient elements, if not present in the waste, can be added either as chemicals or as domestic or sanitary sewage. (ii) Activated Sludge: This process brings the organic waste into contact with microorganisms in large aeration tanks, in which the bacteria grow as flocculent suspended growths. Compressed air is supplied through diffuser plates or tubes as the source of oxygen. Presettled organic waste flows continuously into the tank, for a detention and aeration period of several hours. Mixed liquor suspended solids (MLSS) overflows at the same rate and is settled. A portion of the floc is returned to the aeration unit as seed. This process often provides a smooth-running operation with excellent removal of organic matter from the waste. Many faults, however, can develop in the process. Shock loads of waste, abrupt va riations in pH, temperature, other environmental factors and the presence of toxic wastes are among the major causes of trouble. Nitrogen and phosphorus must be present; if they do not occur in the waste, sanitary sewage from the plant can be used as a source. Uniform feed and operating conditions encourage good activated sludge treatment. (iii) Lagoons: Lagoons, holding ponds or oxidation ponds provide several types of waste improvement including biological removal of organic wastes. Equalisation, sedimentation and opportunity for self-treatment inevitably occur. Chemicals can be added, if desired, for further treatment. The biological processes in a lagoon should be predominantly aerobic, for most satisfactory operation. Anaerobic conditions usually prevail in the bottom muds, but if the main part of the lagoon becomes anaerobic, bad odours and a poor degree of treatment result. Shallow lagoons and avoiding of overload are helpful in maintaining desired level of dissolved oxygen. Sodium nitrate is used as a substitute or supplement for DO but usually in emergency conditions only, to avoid odours. Lagoons are used by many industries if land is available at reasonable cost. They may be suitable as sole treatment in some plants but are better employed as final or polishing treatment of the waste before discharge. They require minimum maintenance, but some control is desirable. For good DO control, they should be shallow i.e., 1-2 m in depth and excessive plant growths should not be allowed. The banks should be kept clear of vegetation other than grasses. Any sludge build up is to be removed which is more common in inorganic settling lagoons. Lagoons are sometimes operated in series, to minimise short-circuiting of flow. (9) Anaerobic Biological Treatment

Many modific activated sludg used in both se industrial was These include with various f tapered distrib along a long ta addition of the waste, additio flocs to the bio growths, inter clarifiers, and modifications

In general, anaerobic degradation of organic matter is slower than aerobic oxidation, requiring days or weeks instead of hours. It is not practicable, therefore, to treat dilute wastes by anaerobic microorganisms because of the large tank volumes required.

In some cases, anaerobic microorganisms provide an effective treatment. The bottom layers of aerobic lagoons are usually anaerobic and may serve to decompose much organic matter even without nuisance. It is used for treating many organic wastes. Anaerobic treatment is widely used for strong wastes or waste fractions. As a rule of thumb, a 1% concentration of organic matter has been suggested as the minimum practical feed to an anaerobic process. This concentration is available in some organic industry wastes, in most organic sludges and in many solid wastes such as garbage and food wastes. Raw industrial wastes are sometimes treated by anaerobic fermentation of the whole waste in large holding tanks. The effluent is rarely suitable for discharge

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because of bad odour and high residual organics but aerobic treatment may be employed for polishing it for release. Settling tank sludges are often further processed by anaerobic digestion. The reduction in volume from raw waste to sludge makes this feasible. In digestion, much of the organic matter is gasified to methane and carbon dioxide and the residual solids or humus are not objectionable in their nature. Temperature and pH controls are desirable for optimum digestion. The solids, after 1 to 2 months digestion, can be disposed off by dewatering and incineration or other methods. (10) Ultimate Disposal The final disposal of adequately treated wastewater usually presents no special problem. It may be simply discharged into the municipal sewer or a natural water course, or into a ditch leading to the water course. Discharge to a river or lake may be through multiple outlets, to hasten the dilution. In a few instances, river water is to be pumped into the treatment plant to assure adequate dilution at the moment of discharge. Sludges are unavoidable by-products of wastewater conditioning and their disposal may present more serious problems. Sludges contain most of the pollutants removed by treatment plus the treatment chemicals. If suitable and adequate land areas are available, sludges may be disposed off by secured landfill system. Reduction in sludge volume eases its disposal and is a common practice. It includes dewatering by thickening, filtration or drying. Further reductions are accomplished by digestion of organic sludges, wet oxidation under high pressure and temperature, or incineration. Complete destruction cannot be accomplished but disposal by dumping is usually possible after volume reduction and removal of putrescibility and other obnoxious features.

Industrial Effluents

SAQ 1
What are physico-chemical parameters commonly used in the study of wastewater?

SAQ 2
Describe inplant measures to be adopted for pollution control.

SAQ 3
Briefly give various particulate removal methods.

15

Pollutants in Soil and Water

11.3

EFFLUENTS FROM FOOD AND FOOD PROCESSING INDUSTRIES DAIRY WASTES

The products processed by dairy include fluid products such as homogenised pasteurized milk for immediate consumption or nonfat dry milk powder, cheese and other less perishable products that may be stored. These products may later be used by the dairy industry or sold to the baking, candy and other industries for use as ingredients of their products. Wastes from the dairy industry resemble other food wastes but have particular problems of their susceptibility to biological attack.

11.3.1

Sources of Waste

Plants handling milk can be classified as receiving, bottling, condensing, dry milk manufacturing, ice cream manufacturing, cheese making and butter making. Other types of milk processing operations are of lesser importance. Wastewaters from dairy plants fall into three categories: industrial waste, domestic waste and spent uncontaminated waters. The last group includes water used in the refrigeration system of condensing and precooling various pasteurized products. It contains no milk solids. Industrial wastes from dairy plants consist of various dilutions of milk that enter the drainage system. These may be classified according to their source as follows: (i) Rinsewater and washwater from cans, tank trucks, equipment, product pipelines and floors (ii) Spillage, freeze-on, overflow and leakage caused by improperly maintained equipment and poor operating practices (iii) Entrainment from evaporators (iv) By-products such as buttermilk, whey, and in some cases skim milk that cannot be utilised (v) Spoiled or damaged raw or manufactured products or by-products that cannot be salvaged for other uses The volume of industrial waste discharged by a dairy plant depends mainly on the availability of water and the care exercised in managing it. A dry floor plant, using water conservation and waste saving practices, is the preferred method of operation now used in most modern plants. By employing such procedures, savings can be realised in the initial cost of water and in reduced cost of disposing of a smaller volume of waste. Let us now study about various methods which can be used to reduce the quantity of wastewater.

11.3.2

Methods for Reducing Wastewater Quantity

(i) Clear Water Segregation: Much of the water used in a milk plant remains uncontaminated after use. Condensing water and ammonia compressor jacket water from the refrigeration system and cooling water from milk coolers, vat pasteurizers,

16

and air- conditioning system fall under this category. These waters should be collected in a separate sewer and discharged directly to the receiving stream. These waters may also be reused in the plant, sometimes saving steam when used in another process requiring hot water. (ii) Waste Prevention: Loss from leakage can be prevented by care in assembly of equipment and by proper maintenance. Overflow may occur where product flows into an open or vented piece of equipment. It can be prevented by the use of float operated or electronic level controls that shut off the flow. Spillage generally results either by careless handling or improper design/layout of equipment. This loss occurs primarily where product is dumped from one vessel into another. Proper care in the dumping process eliminates most of these losses. Freeze-on may occur wherever product is in contact with a refrigerated surface, as in a cooler or an ice cream freezer. Proper controls or the use of ice water prevent freeze-on at coolers. Willful waste includes products such as whey, buttermilk and separated nonfat milk that often have little or commercial value. These high BOD products should never be allowed to enter the plant sewer system. Residual waste is found in all plants. It consists of milk products that cling to the surface of equipment or pipelines after they have been drained. It may be removed from equipment and pipelines by draining after standing for a period of time, then flushing with water and collecting the first of the rinsewater for salvage. Suc h residual products can be disposed of by pasteurizing and returning to the farm for stock feed. If care is not exercised in the operation of a vacuum pan, milk solids may become entrained into the vapour and carried over into the condenser water. This ma y be corrected by level controls and entrainment separators.

Industrial Effluents

11.3.3

Treatment of Dairy Wastes

Dairy wastes are composed almost wholly of organic matter, and, therefore, are high in oxygen demand. Milk is nature's most perfect food for bacterial and other microscopic organisms also. Dairy wastes in a stream are, therefore, consumed at a very rapid rate, causing depletion of oxygen and in some cases exhaustion resulting in evidence of serious pollution. Milk wastes also contain nitrogen and phosphorus, which are excellent plant nutrients. In disposal by irrigation, this property has value in maintenance of a ground cover crop; however, in stream the effect is detrimental. Algae and other aquatic plants are caused to grow profusely and, upon dying the dead plants add taste and odour to the water. These are often not removed by water treatment processes preparing water for domestic use. Settleable solids are not important in dairy wastes since all organic material is in colloidal or dissolved state. Little or no BOD reduction can be effected by plain sedimentation. Detention in primary settling tank causes the rapid conversion of lactose to lactic acid which precipitates the casein. The acid effluent then becomes difficult to treat in the secondary process and the casein will not digest due to the high acidity that has bactericidal qualities. Although primary sedimentation is of little value in the treatment of dairy wastes, a grit removal chamber is essential. Sand and other gritty material can damage pumps in the treatment plant and interfere with the treatment processes.

17

Pollutants in Soil and Water

Another important element in dairy waste treatment is equalisation of flow. Volume and BOD of the waste vary greatly over a 24-hour period. To apply the waste uniformly to the treatment system, a balancing tank is necessary. This tank should be of sufficient capacity to hold surges while the waste is pumped out at a uniform rate. It is essential that wastes in this tank not become septic, so air is introduced through diffusers or other means to keep the raw wastes aerobic. The treatment systems most effective for dairy wastes provide sufficient oxygen to biochemically oxidise the organic constituents. Treatment systems used extensively today are aeration or modified activated sludge, trickling filters and irrigation. Lagooning has also met with some success. (i) Aeration: The heart of aeration treatment is the aeration tank. Aerobic microorganisms are fed by organic material present in the fresh waste and are supplied with oxygen taken from air, thus providing suitable environment and conditions for their growth and reproduction. The diffused air produces constant agitation that prevents sludge from settling and brings floc particles into intimate contact with the fresh wastes entering the tank. Treatment by oxidation has two distinct phases. The assimilation phase occurs as fresh milk wastes enter the aeration tank. During this phase, the bacteria rapidly consume organic matter and require oxygen supply at a high rate for a short time. In the second or indigenous phase, the bacteria receive no new food but digest the food ingested during assimilation. This requires considerably less oxygen over a longer period of time. Since autodigestion takes place continuously even during the assimilation phase, oxygen for it must be supplied during the full time of treatment. Aeration is associated with the following problems: Foaming results by excess air applied during the indigenous phase where the demand is only 10% of the assimilation phase. Reduction of the air supply approximately 3 hours after fresh waste addition may correct this condition. Bulking may be caused by overloading because of insufficient time to complete the oxidation or insufficient air to take care of the excess organic material. An effective in-plant waste prevention program may overcome this problem. An excess ratio of carbohydrate to protein may occur in wastes from ice cream manufacture due to the added sugar. This becomes evident as a light sludge that is difficult to settle. Nitrogen supplement helps correct this problem. (ii) Tricking Filters: It is one of the first methods attempted for the treatment of dairy wastes. Early experience indicates that strong dairy wastes applied to standard rate filters causes ponding, thus making the filter inoperative. Dilution is necessary, either by the addition of cooling and other clear waters, or by use of the high rate filter with recirculation of effluent from the secondary clarifier to the plant influent. Problems with trickling filter treatment arise, usually because the lactose rapidly converts to lactic acid and reduces the pH of the holding or primary tank. This causes the casein to precipitate and also inhibits biological activity. Thus, the filters clog and natural biological film does not develop. This results in odour and poor effluent from the treatment system. Aeration of the holding tank may improve operation of the filter, eliminating ponding and odours, and improve over-all treatment plant efficiency.

Floc circulatin aeration tank to form clump increases transfer of oxy individual cell clumping may where the cen particle is not sufficient oxyg becomes anae necessary, the maintain a hig agitat ion in th the individual dispersed. Th exposes maxim surface and th rapid oxygen aerators, by sh tend to breaku

18

(iii) Irrigation: Where suitable land is available, disposal of dairy wastes by irrigation is feasible. It is often the most economical and least troublesome method. Transpiration, evaporation, and, to a small degree, percolation take off the water. Bacteria, naturally present in the earth, convert the organic constituents to carbon dioxide, water and other products such as nitrates. Since the bacteria are mostly of the aerobic type and require oxygen; therefore, it is necessary to provide a period of rest to allow the soil to take in air. As the liquid percolates through the soil it draws in air, making oxygen available for the aerobic process. If application of waste to the soil is continuous the available oxygen is consumed, causing anaerobiosis and accompanying malodours. To prevent this condition, irrigation piping should be moved every day or every second day. (iv) Lagooning: Stabilisation lagoons are used extensively for treatment of domestic wastes. These systems have also been used to treat combinations of dome stic and dairy wastes. Aerobic lagoons or oxidation ponds are designed to have a large surface area per unit volume. Oxygen is introduced into the liquid by natural or mechanical aeration and by photosynthesis. BOD loading is important and must be controlled so that oxygen demand of waste decomposition does not exceed the ability of the reoxygenation processes to supply the necessary oxygen. (v) Other Treatment Systems: Chemical precipitation has been used where lime is used to raise the pH, and ferrous sulphate or other coagulating chemicals to cause precipitation. The precipitate, however, removes only material in colloidal suspension and does not alter the composition of the dissolved solids. The cost of chemicals, the cost of labor to handle the chemicals, and the sludge make this process unattractive.

Industrial Effluents

ust be taken on in the gation e disposal. t are slope of soil and rop. Other include the of cloudiness e. The area gation ds on the

SAQ 4
What are sources of waste in a dairy plant?

SAQ 5
Describe in short aeration methods for the treatment of dairy waste.

11.4

EFFLUENT FROM PETROCHEMICAL INDUSTRY

Petroleum industry operations, from production to marketing, result in wastewaters of various compositions, but all are characterised by their content of oil. Other industries including metal finishing, vegetable oil production, meat production, and organic

19

Pollutants in Soil and Water

chemicals manufacture, also produce oil wastes and have utilised techniq ues developed for petroleum industry.

11.4.1

The Petrochemicals Industry

The major units of petroleum industry are; (i) production (or mining) (ii) transportation, (iii) refining and (iv) marketing. The special field of petrochemical manufacture, is also added to these in which petroleum serves as the basic raw material. The petrochemical products are innumerable comprising pharmaceuticals, polymers, fertilizers etc. (i) Production: It involves recovery of petroleum from underground sources as crude oil. Natural gas is obtained from the same or separate wells but its recovery and purification are relatively free from wastewater problems. Smaller quantities of oil are produced from oil shales, obtained by hard-rock mining, and recovered by distillation or other processes. Wastes from production operations include muds lost during drilling operations; oily losses during drilling and production and brines accompaning the crude oil. If adequate stream flow is available, brines may be disposed of by dilution, after oil removal. Discharge underground is a more common practice, and may be used to maintain pressure on the producing well. Ponding for evaporation is sometimes feasible, but may cause contamination of potable aquifers. (ii) Transportation: It includes moving crude oil from production area to refinery and distribution of finished products to market. Pollution problems arise primarily from accidents and equipment failure. Accidents can be minimised and procedures for salvaging or destroying spills should be known to all personnel involved. Water ballast in empty oil tankers can be reasonably freed from oil before discharge to waterway. Wastes from the cleaning of transportation equipment also require special treatment. (iii) Refining : The major produc ts of refining are fuels, lubricants, greases and semiraw materials for the chemical and petrochemical industries. Modernisation has improved the effectiveness of wastewater treatments. Expansion of refining capacity has also reduced over-all water usage. Water is used in refining operations primarily for indirect cooling and does not come into contact with hydrocarbons. However, water used in washing stocks and steam recovered as condensate from processing operations comprise process wastewater and is usually contaminated. (iv) Petrochemical Production: The following main processes convert petroleum hydrocarbons into raw materials for chemical industries: (a) removal of hydrogen to give unsaturated hydrocarbons (alkenes or aromatics), (b) oxidation and (c) chlorination. Wastewaters from petrochemical works comprise surface run-off, process water and cooling water. The problem of water-immiscible oils and solvents, possibly with high BOD and significant solid levels are common to both oil refineries and petrochemical works. (v) Marketing: The marketing of petroleum products may cause stream pollution by spills or other losses during transportation and by minor losses at bulk stations and individual retailers. The latter are difficult to control because of their small size, large number, wide distribution and the fact that most discharges are to municipal sewerage systems and are not easily observed. Adequate control of wastewater prevents oily

The principal r operations are by pressure an distillation, the catalytic cracki re-forming, po and alkylation such as acid tr lube stocks, sw gasoline, extra stripping are in the preparatio specifications.

20

wastes from entering the sewer, as by collecting used crankcase oil and by providing oil traps in the sewer to collect oils that enter despite the precautions taken.

Industrial Effluents

11.4.2

Waste Characteristics

ely in

Wastewaters usually contain oil which may be separable, emulsified or dissolved chemicals including acids, alkalis, sulphides, mercaptans, ammonia and phenols and suspended solids. The extent of recirculation and reuse of water in refineries depends upon its availability having satisfactory quality. Increased recirculation and reuse of water results in decrease in water intake and net effluent discharge, but paradoxically is accompanied by an increase in actual consumptive use because of the resulting evaporation. Second to cooling, the major use of water is for boiler feed. The resulting steam is used for stripping and distillation and because the steam comes in contact with petroleum products, the process condensate may be contaminated. Process wastewater is usually defined as any water or steam condensate that has been in direct contact with oil and can therefore contain oil or chemical contaminants. This includes spent caustic and acid solutions, product and crude washwater, crude desalting water condensate from steam stripping, distillation and steam cleaning or regeneration of catalysts and clays. Separable and emulsified oils are found in wastewater sources. Sulphides occur in crude desalting water and from gasoline condensate receivers at distillation and cracking units. Phenolic wastes are found in condensate waters from catalytic cracking, in gasoline washwaters following caustic treating, and from lube oil and solvent production processes utilising phenols. Many oxidisable solutes present in refinery wastewaters contribute to the over-all oxygen demand. Taste and odour in wastewaters are caused by phenolic, naphthenic, nitrogenous and organic sulphur compounds. They originate from treating operations for removal of sulphur, nitrogen, and oxygen compounds from crude and distillate products, decomposition products from distillation and catalytic cracking, barometric condenser water and crude desalting washwater.

d windage ling towers f process mosphere are ive uses. through ooling tower discharge of

y originate in ing equipment condensate pping hwater from ng and g, releases wn or startup offs from quipment cooling tower

ant wastes,

ources such as

mp gland ire fighting

11.4.3

Waste Disposal /Treatment

generally

r to the

(i) In-Plant Procedures: They are procedures which include a number of steps related to waste control. These involve specific operations and specific equipment for waste control in the most effective and least expensive manner. They are used to prevent entry to the sewer system of substances that would complicate the final waste treatment operation. Other in-plant procedures involve recovery of raw materials, intermediates and final products within a particular unit area; reuse of water in cooling towers; reuse of a chemical in a series of treatment steps in which initial use requires the highest concentration and successive uses are met by lower strength; and treatment procedures that condition a waste for discharge to the sewer or remove it from the system for special or selective disposition. Oil is usually collected from a drainage system at each refining unit, in a number of sumps conveniently located near the unit. Wastewater from the sumps is usually collected in a closed system that discharges to the refinery main sewers, from which the oil is collected in master separators.

arged to manual ystem is ollection of

21

Pollutants in Soil and Water

Cooling tower is the most important of the reuse systems which may increase the consumptive uses of water, but reduces the amount of water taken from the raw water supply. Thus, it reduces the volume of wastewater to be treated. The cooling tower operates as a closed system; hence is effective in reducing oil losses to refinery sewer. Caustic soda is used in the treatment of many crude stocks to remove hydrogen sulfide and mercaptans. Incidental to this treatment is the formation of caustic cresylates. Other stock treating operations employ caustic cresylates to accomplish sweetening. There is usually an accumulation of caustic cresylate to be discarded from the system. (ii) Stripping and Oxidation: In the distillation of crude oil and in catalytic cracking, sour condensate waters are produced which contain varying concentrations of sulphides, mercaptans, ammonia and phenolics depending upon the type of crude oil, the cracking conditions, and the amount of steam used. The most common method of treating sour condensate water is by steam stripping in a tower. Sulphides, mercaptans, and ammonia leave the tower as overhead gases, and the major part of the phenolics is drained to the sewer system in the tower bottoms. Distribution of the components between overhead and bottoms is controlled by design and manner of operation. Hydrogen sulphide and mercaptans are relatively easy to strip. Complete ammonia removal is difficult, and requires large amounts of steam. Some refiners use a combination of fuel, gas and steam for stripping these waters. Oxidation of sour water in towers is done by leading it into the bottom of the tower with sufficient air to oxidise the sulphur compounds and ammonia by exothermic reaction. Usually the sulphur compounds are oxidised to thiosulphate and the ammonia to water and nitrogen; phenolics are not affected. The degree of oxidation is controlled by the contact time provided in the tower. Oxidation to sulphate can be done by using higher pressure and extended contact time. Spent caustic solutions containing sulphides and mercaptides are also oxidised in towers; in some instances, along with the sour waters.

Steam distill stripping commonly use water soluble v components fr wastewater str process is usu out in a contin employing pla that used for f distillation. Th is pre heated b exchanger and into the distill near the top w is introduced n bottom of the wastewater wh down the colu action of gravi contact with th vapours rising bottom of the the waste pass column it lose progressively volatile consti these volatile m depleted comp volatile consti out of the was the top of the can be taken aw processing. A diagram of the

Fig 11.1: Steam Distillation Plant

(iii) Combustion: It is used to a limited extent for selected wastes. Hydrofluoric acid alkylation and spent aluminum chloride sludges are sometimes burned in special incinerators. Combustion of spent caustic solutions, including sulfide, mercaptide and cresol types has found limited application because of air pollution, corrosion of the incinerator and difficulties of handling the slag which is mostly sodium carbonate, formed in the combustion chamber.

22

In some refineries, where petrochemical manufacture is a part of the operations, spent or waste solvents are incinerated as a means of disposal. However, chlorinated hydrocarbon disposal by this means requires absorption towers for removing the hydrogen chloride formed. The small size of this operation may permit discharge of the absorbed acid to the sewer system or permit the expense of neutralisation. The burning of oily sludges and salt- bearing acid sludges in power station furnaces has been practiced in the past and is feasible where oil or coal is used as fuel. Air pollution control, however, limits this practice. (iv) Solvent Extraction: It finds limited use in an oil refinery and is sometimes used on phenol-bearing wastes such as caustic cresylates and sour water stripper bottoms. Control of the wastewater pH is required to put the phenolic material in the acid form. The cresol-bearing solvent is recovered by extraction with strong caustic solution to produce the marketable product. (v) Housekeeping : Good housekeeping includes repair of leaks, avoidance of oil discharge with the necessary elimination of water from process units, proper disposition of solids and spent chemicals, careful handling of emulsions, an awareness by all personnel that waste treatment begins at the process unit. Sampling lines should be installed in a manner to allow collection at the unit of line flushings. (vi) Terminal Treatment: Oil refineries usually employ separate sewer systems for oily water or process waste, spent cooling water, storm drainage, and sanitary sewage. Sanitary sewage is usually collected in a separate system and discharged to city sewers. If municipal facilities are not available, septic tanks are employed, with the overflow going to drainage fields. If secondary treatment is used for the refinery effluent, the overflow from sanitary sewage septic tanks is discharged to the nearest oil water sewer. (vii) Gravity Separators: Gravity separation is the final treatment step for oil refinery wastewaters. For process wastewaters or the oily water sewer system an oil-water separator designed by American Petroleum Institute and known as API separator is commonly used. A longitudinal section of API separator is shown in Fig. 11.2.

Industrial Effluents

tor is a large k designed to wastewater

e to the tewater e length of

Fig. 11.2: American Petroleum Institute (API) Separator

This is a gravity separator in which oil accumulates on the surface and heavy solids settle to the bottom. Oil skimming and bottom sludge removal are required periodically. Storm drainage and spent cooling water are frequently routed through separators of this type. Gravity separation may provide the total treatment needed for simple refineries, however, where there is a complex of operations involving lube oils and petrochemicals, additional treatment may be required. It may consist of chemical

23

Pollutants in Soil and Water

flocculation, air flotation with or without chemicals, or biological oxidation by means of trickling filters, activated sludge or ponding for an extended time. (viii) Chemical Flocculation: It cons ists of the addition of a reagent to a wastewater to form a precipitate removable by settling. Aluminium sulphate, ferric chloride and aluminium chloride are the most common reagents used. Sometimes, substances present in the wastewater, such as calcium bicarbonate and magnesium carbonate may be made to form precipitates and serve as flocculation agents. When the pH of the wastewater is controlled within the proper range, hydrated reaction products of the flocculation agents result; these relatively insoluble compounds, initially present as colloids, agglomerate as flocs . During agglomeration, they become associated with other colloidal and suspended matter. As the floc particles grow, their apparent density increases and they settle, carrying with them whatever insoluble matter may have become trapped during the growth period. Polyelectrolytes are frequently used to hasten the flocculation process. Chemical flocculation is effective in reducing the suspended matter content of wastewater including insoluble matter in a finely divided state. Oil content can be reduced to its solubility level. Some BOD is removed but the removal is limited to oxygen-demanding substances present initially as colloids or other particulates. (ix) Coalescence: Coalescence de -oilers have been developed to get away from chemical based wastewater treatment systems. The coalescer works by a physico-chemical action of drawing tiny oil droplets together, separation of discrete larger droplets within the coalescing media and production of large oil droplets which are collected at the top of the vessel. An outline of coalsecnce de -oiler is given in Fig. 11.3. The plant normally works in upflow mode.

The coalescen progressively filtered out su solids can be r washed using flushing. The preconditionin allows effectiv

Air flotation o advantage of a separation tha separation and requirements a

Fig. 11.3: Coalesence De-Oiler

(x) Air Flotation: In this process, wastewater is saturated, usually under pressure with a gas such as air and is then released to a vessel at atmospheric or reduced pressure. The supersaturation is relieved by formation of tiny bubbles which while forming and rising through the water attach themsel es to particulate matter and take it to the v surface, from where it can be skimmed. Air flotation, with or without chemicals, can yield a greatly improved effluent in appearance and oil content. It can serve as the final treatment for refinery effluent whe re oxygen demand requirements are not important. (xi) Biological Oxidation: It is used extensively for treating refinery wastewater. Both trickling filters and activated sludge have been adapted to the treatment of selected waste streams and to total effluents. Bio-oxidation ponds also are widely used. Biotreatment has been limited to selected streams which contain phenolic compounds. With the decline of water usage, refinery effluents become of poorer quality and the need for treatment is greater, even though the absolute amount of polluting materials may be less than it was when effluent volumes were greater.

The combinati flotation with flocculation is effective than alone. It produ same degree o chemical flocc does it faster, m some of the ef upset simple c flocculation an accomplishes

24

Selection of ty biotreatment d largely on cos available for th plant. The bio pond requires area for its ins Where area is a terrain favorab method of low in installation The pond has g capacity to wi shocks from o toxic substanc

A clear-cut basis is lacking for selection of a trickling filter or activated sludge unit for treating the total effluent from a refinery. Both units can give approximately equal performances. Installation costs are usually greater for a trickling filter but it is considered to withstand the effects of overloads and toxic materials better than activated sludge. (xii) Chemical Oxidation: It has limited use in the treatment of refinery wastes, however, it is employed in towers of spent caustic solutions containing sulphides and mercaptides and for sour condensate. The operation is carried out as a continuous process, with solution and air fed to the bottom of the tower. The reaction is exothermic and provides heat once it is started. Sulphur compounds are converted to thiosulphates. Temperature and pressure vary with composition of the waste and degree of oxidation desired. Oxidation by ozonation or chlorination is seldom used because of costs. Use of these agents on biotreated effluents offers a possible tertiary treatment in extreme conditions. This could be justified only for taste and odour compounds that are refractory to the usual biomethods. However, the taste and odour compounds are among the last components in the mixture to react with these oxidising agents. The relatively large amount of oxidant consumed in oxidising residual BOD, plus that required to establish mass action conditions needed to effect oxidation of the taste and odour constituents, makes the process prohibitively expensive. (xiii) Final Waste Water Treatment: It involves removal of residual suspended solids to achieve still lower BOD and suspended solids levels. It is commonly done by using pressure filter. The problem is more likely to lie with residual COD arising from dissolved organic compounds which resist biological treatment. These compounds are removed by using activated carbon as a tertiary treatment method. Powdered activated carbon is added to the aeration basin in the activated sludge process. The toxic organic compounds get adsorbed and are removed. (xiv) Underground Disposal: Deep well disposal is being increasingly used for selected industrial wastes. It has be en used for brine disposal in oil field regions for many years. At the refinery, wells can be employed to dispose of sour condensate streams, spent caustic solutions and spent acids. Waste solutions charged to the well must be free from suspended matter in order to avoid plugging the sidewell of the borehole. Fresh water or acid may be injected into the well initially, to establish a front or barrier between the waste and the original formation water. This prevents reactions between components of the waste and the underground water which would give precipitates and plug the formation. (xv) Dilution: It offers only limited possibilities for meeting the oxygen demands of a waste and has considerable capacity for accepting a waste containing high dissolved solids. The characteristics of the waste and the properties of the waters into which the waste is to be discharged must be carefully weighed when treatment requirements are being balanced against dilution potentialities. (xvi) Evaporation: It can be an important asset in arid regions where ponds without outlets i.e., seepage and evaporation ponds, are used. (xvii) Sludge Disposal: It is one of the most difficult problems in the treatment of refinery wastewaters. Sludges are derived directly from waste treatment and they also originate in oil processing operations. Segregation of sludges minimises difficulties and

Industrial Effluents

ds should be mpartments. asin of at least g time should n oil and mits easier it is allowed larger ponds. ogical quired, having eability and overed by a impermeable n. There ological faults the receiving

elow the depth uture potable he area. The erly cased hat upper safe from

tion may be lanting high on (HRT) posal site.

either waste processing, it sess the se operations ludges and to aracteristics.

he sources btained at als. Thus, the varies from erratic results ank bottoms ain heavy require special paring Sludge and m air flotation

25

Pollutants in Soil and Water

expenses in ultimate disposition. Sludges can be considered under the following four general types: oily , oil-free, chemical and biotreatment. (a) Oily Sludges : These are derived from oil-water separators, tank bottoms or cleanings, air flotation treatment of wastewaters, and cleaning or dredging from lagoons or oxidation ponds. They consist of slurries of oily solids in water. If final disposition is to be in some remote area, thickening may be required to minimise transportation costs. Centrifuging may be used to accomplish a higher degree of water removal, after thickening of the sludge to 10-15% oily solids to produce a satisfactory centrifuge feed. The dewatered and relatively oil-free solid can be disposed of by incineration or used as landfill. (b) Oil-free Sludges: Solids from water conditioning may consist of silt, calcium carbonate, magnesium hydroxide and minor amounts of organic matter along with precipitated treating agents. The composition varies with the water source. They should not be discharged to the oily water sewer system because they can promote emulsification and inhibit oil-water separation. These solids are thickened and dewatered by centrifuging which are then suitable for landfill. (c) Chemical Sludges: A variety of chemical sludges result from oil refining operations. Spent aluminum chloride complex, sulphuric acid alkylation sludge, calcium fluoride from HF alkylation, and acid sludge from the treating of lube oil stocks require special handling. Sludges from lube oil stock treating and sulphuric acid alkylation are treated for acid recovery in the refinery, or sold to acid manufacturers. Spent aluminum chloride complex has been disposed of by buried with crushed lime stone or hydrolying and using as a source of aluminum in chemical flocculation. Where possible, such sludge is simply drowned to avoid hydrochloric acid liberation and sent to a pit containing alkaline waste in which the aluminum hydroxide is allowed to accumulate. Calcium fluoride sludge is an end product from treating HF alkylation plant wastewater. It is removed from the final settler as a slurry, drained free from water and buried. (d) Biotreatment Sludge: Sludges from the treatment of refinery wastes by trickling filters or the activated sludge process can be digested anaerobically in the same manner as sanitary sewage sludge. Sludges from oxidation ponds and aeration basins, however, contain considerable oily matter and respond poorly to anaerobic digestion. Disposition of these sludges can be accomplished by dewatering, centrifuging and incinerating; spreading in a suitable area for complete drying or using as landfill.

SAQ 6
What are the major contaminants of wastewater from refineries and petrochemical industries?

SAQ 7
What is an API oil separator?

26

Industrial Effluents

11.5

EFFLUENT FROM TEXTILES INDUSTRY

Textile manufacturing operations are among the major industrial water users. This industry has the wastes most difficult to treat satisfactorily. Textile wastes are variable in character which makes their treatment a complex problem. In a modern textile mill, many compounds produced by other industries are used. Synthetic yarns, dyes and finishes from the chemical industries and sizes from the food-producing industries are among these substances. Some of these compounds are added onto the basic fiber and then partially or wholly washed off as pollutants. These compounds may be organic or inorganic in nature. Inorganic materials may render water unsuitable for use because of excess concentrations of soluble salts, and because insoluble salts precipitate and deposit on stream bottoms, blanketing aquatic life and even clogging streams. The organic compounds may undergo a gradual chemical or biological change which removes oxygen from the water, resulting in a septic condition characterised by odours, gases, floating solids and a generally disagreeable appearance. Metal salts may be toxic to animals, fish and other aquatic life.

11.5.1

The Textile Industry

All fibers used in the textile industry are either natural or manufactured The natural . fibers can be further subdivided into animal and vegetable fibers and the manufactured fibers are divided into regenerated and synthetic fibers. The principal fibers of commercial significance are given in Table 11.1. Table 11.1: Fibers of Commercial Significance
Natural Animal Wool Silk Hair Vegetable Cotton Flax Hemp Manufactured Regenerated Rayon Soyabean Casein Synthetic Polyamide Polyacrylic Polyester

used in couring and o longer a waste

in many mills ust" the wool, ng much of ities before begin. The then sent to a ne, and is ugh a solution ergent stored owls at about rmerly a dure to run the

(i) Animal Fibers Wool contains large quantities of dirt, grass, burrs, dried sheep perspiration and wool grease discharged from glands to protect the fiber during growth of the animal. In extreme cases, it may contain as little as 30% fiber, with 70% foreign matter, and may be as high as 45% grease. Wastes are contributed by the scouring, carbonising, bleaching, dyeing and finishing operations. The foreign matter may be removed by scouring in warm water with soap and alkali. The amount of soap present increases the BOD of the waste. Currently, soap has been

order to uint, but little s unless the recovered. f synthetic

27

Pollutants in Soil and Water

replaced by synthetic detergents with an extremely low BOD. Consequently, BOD of the discharge can be attributed almost exclusively to the raw wool itself. Wool scouring wastes would interfere with municipal sewage treatment system because of their grease content and the broken fibers. When soap and soda ash were used as the detergent materials, the liquors were treated with concentrated sulphuric acid to separate the grease. This was drawn off and purified for other uses. With synthetic detergents, this method is not always feasible and the centrifuge is frequently used to remove fibers and excess grease. Centrifuging generally produces a better quality of grease, suitable for use in cosmetics, but the recovery is about one -third of the grease present, whereas the acid-cracking method gives almost quantitative yields. Wool grease has been recovered by treating waste liquor with calcium hypochlorite, reducing the pH to about 7.5, discarding the clear liquors and treating the scum and sludge with sulphuric acid. Solvent scouring of wool has been introduced for recovering the grease and hence reducing the pollution lo ad on the stream. Scoured wool may be dyed. Wastes from a dyeing and finishing process are contributed by the spent liquors and subsequent washing of the wool after bleaching, dyeing or other finishing. It is usually not practical to separate rinsewaters from the stronger wastes. These wastes vary greatly in strength because of the amount of water used and various types of dyes and other chemicals. Waste from wool dyeing and finishing has been treated by chemical precipitation with iron or aluminum salts. Usually, it is better to use biological treatment with either the trickling filter or an aeration process. (ii) Vegetable Fibers Cotton has been the mainstay of the vegetable fiber industries and is converted to finished fibre by the following operations: (a) Slashing : Before yarn can be woven into fabric, it must be strengthened by loading with starch or other sizing substances. This operation is called "Slashing" and little liquid waste results. Substitution of sizes with low BOD values such as carboxymethyl cellulose in place of starch reduces BOD in the final effluent. (b) Scouring and Sizing: It is necessary to remove certain natural ingredients and the sizing materials from slashing operations to prepare cloth for dyeing and finishing. This may contribute about 50% of the total pollution load in textile processing. Acids and enzymes are used to hydrolyse the starch. Caustic soda, soda ash, chlorine, peroxides, silicates, sodium bisulphite, acids, detergents and penetrants are used in scouring to prepare a clean, white cloth for finishing. Scouring may contribute up to 30% of the total waste load. Natural impurities in cotton contribute about 3% of the total BOD in the final waste. (c) Bleaching: Bleaching operations use chlorine or peroxide to remove natural colouring matters which contributes about 10% to the pollution load. (d) Mercerizing: It consists of passing cloth through 20% caustic soda solution. It contributes negligible BOD but a high degree of alkalinity. (e) Dyeing: It is done in many ways and new dyes and auxiliary chemicals add to the complexity of the operation. The pollution load may be 20-40% but volume is large and there is a high degree of color.

The cloth at slashing stage is "creige," and may be sold as such. Subsequent operations are considered as finishing but include preparatory treatments.

Vat dyes are fa applied by red dyestuff to s with caustic so sodium hydros oxidising on th peroxide, chrom oxidising agent

28

Developing dy by diazotising acid and sodiu subsequently t developer. Nap are naphthols a fabric, dried, th through a deve

Industrial Effluents

These dye wastes are difficult to treat in biological processes because of high air requirements to oxidise the sulphur dye molecule and because of the toxicity of chromate. Chromium removal is, therefore, carried out using ferrous salt to bring down chromium content below 3 mg L 1 in the waste going to conventional biotreatment plants and below 10 mg L1 in that going to bio-aeration lagoons or prolonged activated sludge treatment processes. (f) Finishing : Finishing operations impart the desired feel and appearance, and better wear properties such as softness, stiffness, smoothness, slickness and luster. Chemicals used in finishing include starches and dextrins, natural and synthetic waxes, synthetic resins, ammonium and zinc chlorides, softening agents, penetrants and various special chemicals to improve service and wash-wear qualities or impart rainproofing, oil and soil repellency, and fireproofing. The waste is low in volume, with some BOD contribution from starch, gums, waxes and resins. (iii) Regenerated Fibers (a) Viscose Rayon: Viscose rayon is a manufactured textile fiber, filament, yarn, thread, or fabric, composed of regenerated cellulose. It is made by the viscose, cupra-ammonium or nitrocellulose process. Natural impurities in regenerated fibers are negligible. Viscose and other regenerated rayons dye readily with most of the dyestuffs used on cotton. Rayon is not as resistant to chemicals as is cotton, hence, drastic treatments must be avoided. High temperature decreases its resistance to acids and oxidising bleaches. (b) Acetate Rayon: Acetate rayon is a cellulose acetate fibre rather than a regenerated cellulose. It is not as absorbent as other rayons, and is more resistant to staining than regular rayon. Acetate does not usually require bleaching but if bleaching is necessary, only mild oxidising agents can be used. (iv) Synthetic Fibers They include polyamides, acrylics and polyesters. (a) Polyamides: Nylon is a polyamide. It is not affected by heat or cold. It has high abrasion resistance and is more resistant to burning than cotton, wool, rayon, or silk. It is also resistant to insects, mildew, mold, fungi and many chemicals. (b) Acrylics (Polyacrylates): They are synthetic polymers that contain acrylic units in the polymer chain. They are resistant to sunlight, weathering, industrial fumes, chemicals, insects, and bacteria. This resistance makes it more difficult to dye these fibers. (c) Polyesters: They have remarkable resistance to heat, low flammability, good shape and crease retention. They are readily processed although dyeing requires a carrier or pressure technique.
Viscose rayon is highly absorbent, and takes up water readily. The presence of water increases the penetration of reagents into the cellulose, increases the electrical conductivity, and reduces the breaking strength. Rayon should not be confused with acetate

11.5.2

Textile Waste Characteristics

The pollutional characterisitcs of textile wastes differ widely among various segments of the industry, and each type of waste presents a special treatment problem. Organic substances such as dyes, starches, and detergents in textile waste undergo chemical and biological changes which consume dissolved oxygen from the receiving stream and so destroy fish life. Such organics are to be removed to prevent septic conditions and

29

Pollutants in Soil and Water

A composite waste from an integrated cotton textile plant comprises starches, dextrins, gums, glucose, waxes, pectins, alcohols, fatty acids, acetic acid, soaps, detergents, sodium hydroxide, carbonates, sulphides, sulphates, chlorides, dyes and pigments, carboxymethyl cellulose, gelatine, dye carriers (phenols and benzoic acid), peroxides, and chlorine bleach compounds. The volume of waste per 1000 kg of finished goods ranges from 200 to 1000 M 3.

obnoxious odours, and to avoid rendering the stream waters unsuitable for municipal, industrial, agricultural and residential use. High concentrations of soluble inorganic salts may make the stream unsuitable for industrial and municipal use, and may have a corrosive effect on boats and other structures. Metals such as chromium and zinc are toxic to aquatic life, and should be removed before discharge. Colours from dyes vary and, although not toxic, are esthetically objectionable particularly in drinking and recreational waters. Certain carrier chemicals used in dyeing, such as phenols, may add tastes and odours.

11.5.3

Textile Wastewater Problems

(i) Recovery and Reuse Waste reduction, prevention, and utilisation practices reduce the quantity of materials wasted and can lead to savings in materials. Some of these in-plant measures and ways in which waste may be reduced are as follows: (a) Reduction of Waste Volume: Strong rinsewaters from dye operations may be reused to make up new baths. Weak rinses may be recycled through in-plant water treatment units. In a counterflow system, rinse-waters are circulated in the opposite direction to movement of the cloth. (b) Reduction of Process Chemicals: Chemicals may be reduced to a minimum by proper control of cloth processing e.g. by the use of redox potential to control hydrosulphite in vat dyeing. (c) Recovery and Reuse of Chemicals: Caustic soda can be recovered from mercerizing liquors and reused, as can sodium dichromate from dyeing operations. (d) Substitution of Chemicals: It is desirable to substitute chemicals with low pollutional effects for those that are more pollutional. Examples include carboxymethyl cellulose for starch in slashing, mineral acid for acetic acid which has a significant BOD, nonbiodegradable synthetic detergents for soap, and polyvinyl alcohol and polystyrenes for starch in finishing. (e) Good Housekeeping: It requires close control of all operations to avoid spillage and wastage of materials. Preparation of too large batches of solutions should be avoided so that they are not to be thrown away at the end of a run. (ii) Water Conservation Water should be used economically due to ever increasing cost and scarcity in future. Reduction of water use in processing conserves the water but the concentration of pollution increases.

In a counterflow system, rinse waters are circulated in the opposite direction to the movement of the cloth.

11.5.4

Textile Waste Treatment

Inspite of the efforts made to reduce waste strength and volume by conservation and good housekeeping, the problem of pollution still remains. The wastes may be treated in various ways and the best combination of methods differs from plant to plant. Each plant evaluates possible treatment procedures according to existing treatment, type of waste and degree of treatment needed. (A) Physical and Chemical Methods (i) Segregation: The segregation of wastes for separate and special treatment depends

30

on the following: the characteristics of individual wastes and the stream requirements. the cost of in-plant changes such as piping and sewers. the benefits gained if weak effluent can be discharged untreated to the stream. the cost of having skilled workers to minimise human errors. (ii) Lagooning and Storage: Equalisation eliminates variation in flows and pollution load, and is accomplished by storage, as in a lagoon. Proper maintenance of lagoons is necessary to avoid odours. Aeration helps to reduce odours and other pollutional characteristics. Lagooning with aeration after other biotreatment processes serves as a polishing treatment and accomplishes maximum pollution removal, usually above 95%. Oxidation ponds, with and without aeration are the most effective type of lagoon. (iii) Screening: Bar screens and rotating screens remove objectionable coarse solids from certain textile wastes containing fibers and trash. (iv) Mechanical Filtration: Coke, ash, coal, rock, and sand filters are frequently used on highly polluted wastes as a secondary treatment, to polish the effluent to a high degree of clarity and usually to a BOD below 10 mg L 1. (v) Pre-aeration and Post-aeration: Physical and chemical aeration by diffusion, spraying or cascading provides oxygen and prevents anaerobic decomposition to control malodourous gases. (vi) Neutralisation: Neutralisation of wastewater is required to adjust its pH according to the pH limits required for the receiving streams, or to adjust the waste to pH less than 10.0 for biological treatment in conventional processes. (vii) Chemical Precipitation: Good results are obtained either by chemical precipitation alone or by chemical precipitation in combination with lagooning. The cost of treatment is, however, higher than that done by biological methods. (viii) Chemical Oxidation: Certain wastewaters containing dyes and auxiliary chemicals are reducing in character. These should be segregated and oxidised with air or chlorine before they are mixed with other plant wastes for further treatment. Chlorine oxidises reducing compounds and is also used in final treatment to reduce the bacteria count. (B) Biological Oxidation Methods Biological methods for removing pollutants utilise natural processes involving bacteria and other microorganisms for oxidation of the organic wastes to produce a satisfactory effluent. Certain textile wastes free from toxic substances may be treated biologically because of their high nutrient content of nitrogen and phosphorus. (i) The trickling filter process: This removes a large part of the organic pollution, and the effluent can usually be discharged to a stream after final settling. Other approach for treating textile wastes more economically is the use of plastic media in the filters, followed by oxidation ponds for polishing. Trickling filter treatment of sewage and textile waste averages about 75% removal of BOD. More efficient operation can be obtained by recirculation of part of the treated effluent or by treating through 2 stages of filters in series. Trickling filters may also be

Industrial Effluents

In oxidation ponds, without air, the usual loading is 20 kg of BOD per acre, but may be up to 40 kg or more in polishing or posttreatment operations. With air, 3-10 days retention is required, depending on the amount of oxygen applied.

Chlorine retards biological oxidation by destroying microorganisms and should be used sparingly where further reduction in pollution is desired in stream assimilation

onal activated , the wastewater, ettling, flows ize to retain low. The s in activated

31

Pollutants in Soil and Water

used as a unique method to reduce the high alkali content of textile wastes of pH 12 or above, prior to activated sludge treatment. (ii) The activated sludge process: This treatment is very efficient and removes upto 95% of the BOD resulting in a clear, stable effluent from normal wastes. The activated sludge process is more sensitive than trickling filters to changes in pH and to shock loads. It costs less to construct and requires little space. Sludge disposal must be provided. Total oxidation, extended aeration, prolonged aeration, indigenous respiration, and other activated sludge variations with greatly increased aeration periods are be ing used more extensively in treating textile waste because of their simplicity and low construction and operating costs. The process involves aerating seeded wastes from 12 to 72 hours, until the organic matter is nearly or totally oxidised, then discharging to the stream. Primary settling and sludge digestion and disposal may be eliminated. The effluent is usually settled, however, the sludge returned to the aeration tank for further oxidation. The method of aeration is optional, and either mechanical agitation or diffused air can be used advantageously to obtain efficiency and economy. Fig. 11.4 depicts a typical prolonged bioaeration process.

The biosorption, contact aeration, step aeration, and other modified activated sludge processes have been found to be less subject to upsets, more economical, and equally efficient for treating sewage or mixtures of sewage with textile waste. Less tank space is required, and the primary settling tank is optional.

Fig. 11.4 : Prolonged Bioaeration Process

(iii) Oxidation ponding : It is perhaps the cheapest method for reducing the pollution load in textile waste, if land is available. Wastewater flows through a shallow pond, usually about 1.5 m deep if colorless, and 1 m deep if dye wastes are present, with upto 30 days retention time and a BOD loading of about 20 kg per acre per day. BOD loadings can range upto 40 kg or more if the waste has been biologically pretreated and seeded. Oxygen from air and from algae production feeds the active organisms which stabilise the organic matter. Recirculation may be used to prevent anaerobic conditions. Finally, we can say that each plant needs to study its own possible treatment methods to obtain the best treatment at the lowest cost. This involves the setting up of a pilot plant. It is desirable to consider all of the treatment methods mentioned above, particularly prolonged bioaeration and oxidation ponding processes. Trickling filters, especially the plastic type followed by polishing in oxidation ponds have been observed to be effective in the treatment of textile wastes.

32

The treatment because of low and low main due to simplic operations. D are the usual s land located a distance of 0.5 from residenti problem of co

SAQ 8
What are the pollutants generally present in a composite cotton textile plant wastewater?

Industrial Effluents

SAQ 9
Describe lagooning and storage of textile industry effluent.

11.6

EFFLUENTS FROM PULP AND PAPER INDUSTRY

The manufacture of pulp, paper and paperboard is continuously increasing. New pulping and bleaching processes, as well as new adaptations of older ones, have contributed to fulfil increasing demands. This is particularly true of processes permitting the use of previously undesirable species of wood.

11.6.1

The Pulp and Paper Industry

The most common types of pulp produced are kraft, sulphite, neutral sulphite, semichemical, and groundwood. In addition, soda, cold soda, chemi-groundwood and other special pulps are made in limited quantities. Some textile fiber pulps such as flax, cotton rag, and jute are made in relatively small quantities for use in specialty papers. Coarse type papers are made from straw and bagasse. Paper products can generally be classified into four major categories, fine papers, coarse papers, tissues and specialties papers. Examples of fine papers are bond, book, mimeo, printing, writing and white papers in general. Coarse papers include newsprint, common wrapping and container boards as well as building products. Tissues include most of the widely used thin papers such as utility tissues, glassine and special wrapping papers. A few of the almost innumerable specialty papers are electrical insulating, cigarette, photographic, card stocks and monetary papers.

Most types of pulp produced can be bleached to various degrees of brightness for different uses. Kraft and sulphite pulps are bleached to a high degree to produce chemical cellulose.

11.6.2

Nature of Effluents 33

Pollutants in Soil and Water

The major stream pollution problems arising from from pulp and paper making are caused by suspended matters and dissolved organic substances. The former forms bottom deposits in receiving streams and la tter are inimical to aquatic life, unsightly and odouriferous on decomposition. Such deposits can also exert an appreciable demand for the dissolved oxygen contained in the overlying water. The discharge of highly dispersed solids such as fiber debris, filler and coating materials can render the stream opalescent which retards self-purification by limiting light penetration. Dissolved solids found in spent pulping liquors can have a variety of effects on streams. Wood supers deplete the dissolved oxygen and stimulate the growth of slime organisms, causing biological imbalance. Lignins and tannins, cause discoloration and resin acid soaps and mercaptans, in high concentration, are toxic to aquatic life. Problems resulting from the normal discharge of inorganic compounds such as acids and alkalies are minor. Because the major difficulties arise from organic matter, these effluents are generally classified as organic wastes. Large quantities of water are employed in the production of pulp and paper products. Water is needed for grinding wood, as a carrying agent in chemical pulping and bleaching, to bring chemicals and heat into contact with the raw material, as a pulp washing agent, as a "furnish" carrier in the paper machine system, and in wood preparation, it is employed as a conveying and washing agent and for hydraulic debarking.

The quantity of water employed varies with the physical equipment of a particular mill, the processes employed, the product produced and its availability. Both surface water and groundwater supplies are employed and most of the used water is returned to surface streams since loss through evaporation is generally less than 5% of the volume handled. The reuse of effluents is widely practiced because of savings in heat, fiber, chemicals and in water requirement itself. Where process water is treated to a high degree, the latter saving can be substantial. The reduction in effluent volume can substantially minimise the size of effluent treatment structures required. Reuse, however, can reach to a point where further recycling leads to detrimental conditions in the mill and its operation.

11.6.3

Characteristics of Effluents

(i) Wood Preparation Effluents: These effluents result from transporting, washing and debarking wood and contain both coarse and fine particles of bark, wood slivers and silt. In addition, some dissolved solids are present in them from sap washed from the wood. Their concentration depends largely on the season in which the wood was cut and on the degree of water recirculation practiced. (ii) Screening and Pulp Cleaning Waters: These contain wood debris, pulp, fines and grit. (iii) Mechanical Pulping Effluents: They contain both fine and coarse wood debris and solubles released on grinding or milling of the wood.

These result from the production of groundwood and defibrinated wood.

34

(iv) Mechanical-Chemical Pulping Effluents: These are similar to mechanical pulping effluents. In addition, they contain spent chemicals and soluble substances released by treatment of the wood with caustic soda or sodium bisulphite prior to mechanical pulping. (v) Chemical Pulping Wastes: They contain spent liquor itself, with the exceptions of kraft and soda pulp production where the spent liquor is invariably recovered and some other types of pulp production where heavy spent liquor is segregated for recovery, by-product production or separate disposal. These effluents contain low level of suspended solids. Bulk of the impurities remain in solution in the form of lignins, tannins, carbohydrates, salts of fatty acids and other organics, wood ash constituents and spent cooking chemicals. (vi) Textile Fiber Pulping Effluents: These consist of draining and washwaters obtained from the cooking and washing of jute, rags, flax, cotton linters, rope and similar materials. The cooking chemical is generally caustic in nature and in some instances a scouring step employing detergents precedes cooking. The effluents contain impurities present in the raw materials, cooking chemicals and products of cellulose hydrolysis. (vii) Deinking Wastes: Deinked pulp is produced from used papers which are cooked in caustic solutions containing dispersing agents, and are washed to remove inks, filler and coating materials prior to bleaching. Filler and coating materials, inks, sizing, fine fibers, and hydrolysis products are contained in such effluents. (viii) Paperboard Effluents: Fillers, fine fibers, sizing and coating materials are contained in the wastewaters from the used paper processes and wood juices in those obtained from defibrinating wood. (ix) Machine Waters: In general, these contain mainly fiber fines and fillers, but may also contain a considerable amount of dissolved solids from sizing materials and special additives of both organic and inorganic materials. When operating on furnishes of pulps that have not be en previously thoroughly washed the machine water can contain a considerable amount of soluble substances added in the pulping process. (x) Bleaching Wastes: All types of pulp can be bleached to improve brightness. Most of the chemicals used are oxidising agents including chlorine, chlorine dioxide, hypochlorites, peroxides and hydrosulphites. In bleaching most alkaline wood pulps, caustic soda is used to remove materials rendered extractable by the oxidising agents. Each bleaching stage is followed by a washing step to remove extracted materials and spent chemicals. Bleaching washwaters are generally colored by the presence of lignins and tannins removed from the pulp. In addition, they also contain a small amount of fiber fines and hydrolysis products. Pollution loads vary from mill to mill and even within the same mill for a number of reasons. For example, wood harvested during different seasons contains variable amounts of solubles and the degree of cooking varies for the various grades of pulp produced. When fiber is reclaimed from salvaged materials, the effluent character depends to a large degree on the type of materials employed. The BOD produced varies almost directly with the pulp yield obtained from wood. Efficient heat and chemical recovery systems, as employed in chemical pulp mills, can reduce these losses.

Industrial Effluents

These effluents are produced by the preparation of kraft, soda, sulphite, or semichemical pulps.

Some paperboards, insulating boards and roofing felts are produced from used papers, pulp made by defibrinating wood in an attrition mill, or a combination of the two materials together with some virgin fiber. In most of these processes, the bulk of the losses is contained in the machine water, although in some the furnish is washed and thickened prior to delivery to the paper machine.

11.6.4

Suspended Solids Reduction 35

Pollutants in Soil and Water

The suspended matter consists mainly of fiber, fiber debris, filling and coating materials such as clays, calcium carbonate and titanium dioxide. In most mills, the bulk of these materials are captured from the machine waters by means of screening, filtration, settling or flotation devices and are returned to the system for reuse. Their efficiency depends upon the process employed and the nature of the solids they are expected to retain. Under some conditions, highly efficient devices of this kind can retain a sufficient quantity of the suspended solids so that further removal is not necessary. The most common means for treating solids-bearing wastes in the paper industry is sedimentation, although in some plants flotation and filtration are used.

11.6.5

Sludge Dewatering and Disposal

Coagulants such as alum, activated silica and polyelectrolytes are used to render the non-settleable solids settleable. In general, sedimentation without the addition of coagulants removes 70-80% of the total suspended solids. This percentage can be lower when highly efficient savealls are employed in the mill or when dispersing agents are present. The percentage may be higher when coagulants are used in the papermaking process. Coagulants can produce a total suspended solids reduction in excess of 90% when interfering substances

The underflow from clarifiers treating pulp and paper mill effluents ranges in consistency from 2 to 12% solids depending on the nature of the solids settled out and the clarifier operation. The length, type, concentration and degree of hydration of fiber present in the waste treated can all influence the density of the underflow. Some effluents, such as those containing groundwood fines or highly hydrated glassine fiber, produce very thin underflows that are difficult to thicken and to remove from the clarifier in a concentration suitable for further dewatering and disposal. In some instances, flotation is employed to separate the more hydrous solids which generally produces thicker slurries. Underflows of under 5% solids concentration are generally moved by positive displacement or centrifugal pumps, and thicker flows are handled by screw impeller pumps. Secondary thickening is sometimes used where further dewatering prior to disposal is practiced. Some papermill sludges such as deinking sludge can be dewatered by vacuum filtration while others such as most boardmill sludges are resistant to filtration. In most plants, conditioning agents are not used, because most of the common ones are not effective in promoting dewatering. Polyelectrolytes are also used for this purpose. Drying beds are used by some mills to dewater sludge. Some of these have underdrains while others are simply impoundments in which water separating from the solids is decanted and natural drying is allowed to take place. When the sludge becomes sufficiently dense, it is dug out mechanically and transported to a disposal area. Such basins are generally built in multiple so that cleaned sections are available at all times. Land disposal is almost universally used for final disposition of paper mill sludges. In some instances, the sludge is mixed with other materials for use as fill. If the concentration of nitrogenous sizing materials is low and the sludge is sufficiently dry, this practice does not give rise to an odour problem.

Horizontal conveyor-type centrifuges are more effective for dewatering some of the more difficult sludges, such as the sludge produced by clarification of fine papermill and boardmill effluents. Vacuum filtration produces cakes varying between 20 and 30% solids. Horizontal conveyor-type centrifugals can produce cakes up to 40% solids with a recovery In some instances, because of natural terrain and the fact that either long storage is available or a high percentage of BOD reduction is not necessary, deep stabilisation basins are constructed. These also serve a dual purpose of providing storage 36 controlled discharge conforming to regulation in proportion to flow in the

11.6.6

Methods for the Reduction of Organics

(i) Stabilisation Basins: These are the most widely used for biological oxidation of pulp and paper effluents. Two types of basins used are: natural reaeration type and the mechanically aerated type. The natural reaeration basin is normally shallow and can be irregular in depth, since its design is based essentially on air-exposed water surface, particularly when a high degree of BOD reduction is required. Mechanically aerated basins have come into use in recent years for raising oxidation rates and hence shortening the storage period required. If the nutrient elements, nitrogen and phosphorus, are in short supply in a specific waste, these reductions may be diminished somewhat, but it is doubtful that addition of these elements is justified as it is with the activated sludge process.

Industrial Effluents

These basins must receive a waste substantially free from settleable solids because, if allowed to accumulate, these liquefy on decomposition and add to the BOD loading. For this reason, it is prudent to build a small entrance basin, that can be cleaned periodically, between the effluent clarification system and the major stabilizing system, to trap suspended matter overflowing the clarifier during periods of upset. Stabilisation basins have following advantages over mechanical oxidation systems: They are not subjected to process upset. They can absorb variations in loading. They require little attention. They involve little operating cost. The greatest shortcomings are the high land requirement, particularly with non-aerated basins, and the fact that color is not removed from pulping effluents. Odour, from either aerated or non-aerated stabilisation basins, is no problem when kraft mill effluents are treated. However, when certain other effluents such as boardmill waste are treated, a high degree of aeration must be provided to prevent formation of odourous gases. (ii) Trickling Filters: Many attempts have been made to apply trickling filters for waste treatment. Experiments have indicated that filters using stone media are costly and are not satisfactory for general application as they cannot provide a high degree of purification at high loading rates and they are subjected to clogging with fiber. Plastic media have been employed in trickling filters providing partial purification of pulp mill effluents since they largely eliminate the media-clogging problem and can be operated at high hydraulic loadings. These media are also used for pretreatment and cooling of hot effluents prior to the application of other methods of oxidation. (iii) Activated Sludge Treatment: This process could be applied for reduction of BOD of kraft pulping effluents to a high degree if good internal mill control of waste strength and alkalinity is practiced, and nutrients in the form of ammonia and phosphates are added. It is also effective for other wastes from the production of pulp and paper products, paperboard, roofing felt, neutral sulphite pupping, and deinking effluents. Effluents can also be treated in municipal activated sludge plants in combination with sanitary sewage. Two modifications of the basic activated sludge process are needed for the treatment of pulp and paper wastes. In the contact stabilisation system, aeration periods employed for the mixed liquor are shorter than normal and the return sludge is aerated for a substantial period. The capital cost is somewhat reduced by this modification and that a reservoir of active sludge is maintained against possible damage to the mixed liquor sludge by shock loads. The other modification is the so-called "dynamic" system in which aeration, sludge separation and sludge return are incorporated in a single unit. This arrangement promotes improved conditions, since the return sludge does not have to be pumped and is returned in fresh condition to the waste undergoing treatment. Although successful in treating most pulp and paper mill effluents and combinations thereof, the activated sludge process has following serious shortcomings: i) The capital cost is high, ranging depending on size, and exclusive of pretreatment for reduction of the suspended solids content of the waste. ii) Removal of color is not effected to a high degree when treating pulping and bleaching water.

The stabilisation basins themselves are best built in multiple to prevent short circuiting. At least two separate basins should be used, or one or more dividing walls provided if a single basin is employed. All dikes should be built properly on the basis of soil conditions and provided with core walls where necessary. Basins should be cleared of stumps, and the bottom should be compacted or sealed if this appears necessary. Inlet and outlet structures should be designed to provide for Performance tests with the plastic media indicated that the filter has potential to remove a large quantity of BOD at high application rates. The operating cost is somewhat lower than for activated sludge treatment since less power is generally required for waste recycle than for aeration. Nutrient addition is necessary for

Because there is a greater degree of sensitivity inherent in the dynamic arrangement than to the conventional process, hydraulic design capacity, particularly of the settling sections of such units 37 should be conservative.

Pollutants in Soil and Water

iii) The sludge produced compacts poorly and is extremely resistant to dewatering and hence presents a disposal problem. It is to be vacuum filtered where a large quantity of primary sludge is available to absorb it. iv) Wastes having a BOD approaching 3000 mg L-1 cannot be treated because of the oxygen exchange limitation. There is also the fact that its sensitivity to surges in waste load requires careful control. The treatment of a fraction of the total effluent by this process, followed by recombination with the remaining waste flow, stimulates further oxidation of the total waste in stabilisation basins and thus shortens the storage period required for a given degree of oxidation.

11.6.7

Land Disposal by Irrigation and Seepage

The activated sludge process is generally applied where sufficient and suitable land is not available for stabilisation basins and where the degree of oxidation of the waste needs to be high. The waste to be treated must be free from mineral acidity or caustic alkalinity. The temperature should preferably be below 110C. Requirements for added nutrient are generally somewhat less than the theoretical optimum of 1 mg L-1 nitrogen to 20 mg L-1 of BOD and 1 mg L-1 of phosphorus to 60 mg L-1 of Although well suited to reasonably level land and warm weather application, irrigation disposal exhibits some disadvantages in hilly terrain. Land disposal does not have the potential of wholesale application as a treatment method in the industry. In some instances, however, it does offer an economically attractive means of solving some of the waste disposal problems of the industry where small waste volumes

Several factors have contributed toward accepting the principles of irrigation in contrast to depending upon seepage through porous soils. Foremost is the general scarcity of soils suitable for high rate seepage installations at most mills. Unless an extremely porous soil is available, the land requirement becomes large and the distribution problem serious and costly. Vegetation, by increasing soil porosity and evaporating considerable water through transpiration, reduces greatly the land area requirement. Irrigation has both advantages and disadvantages. The mills located in agricultural areas provide the effluent to supplement existing irrigation water. The limitation does restrict use of irrigation either to relatively small mills or for disposal of specific effluents of relatively low volume. BOD loading generally must be maintained below 100 kg per acre per day to maintain the soil in aerobic condition. The pH should not be below 6.0 or above 9.0, and the sodium adsorption ratio (SAR) should be less than 8.0. There is no evidence that the disposition of salt-bearing effluents from pulp and paper making operations differs substantially from irrigation with water of similar salt content. Since the potential for groundwater contamination does exist when highly colored effluents are applied to the soil, individual site evaluation for soil type, direction of groundwater movement, and location of existing wells must be made. The operating cost of land disposal compares favorably with other methods of secondary treatment and may substantially save capital investment. Added advantages over other methods are that BOD reduction may approach 100% and performance is uniform. The pumping cost for spray irrigation systems is generally less than the power requirement of biological treatment processes.

SAQ 10
What are major stream pollution problems of pulp and paper industry?

38

Industrial Effluents

SAQ 11
How are solid bearing wastes treated?

were located streams

11.7

EFFLUENT FROM TANNERIES

or hides, anning tannery and ther to the f leather reams also ss water and nels for the waste

Raw materials used in leather manufacture comprises hides of cattle and the skins of certain other animals. These are mostly co-products or by-products of edible meats. The hides are received at the tannery from slaughter house either fresh or preserved. The tannery converts the hide into usable forms.

11.7.1

The Leather Industry

The leather industry is one of the oldest industries which has now developed as a huge technical industry. This industry really comprises many industries as each type of leather involves a different process with little standardisation. Basically there are only three or four types of tannage, but the finishing processes are more numerous. Sole, belting and saddlery leathers are tanned with infusions of barks, wood, nuts and leaves and this is known as vegetable tanning process. Shoe upper leathers may be made from calf, goat, horse or cattle hides tanned with mineral salts which constitutes the chrome tanning process. Some leathers are tanned by a combination of vegetable and chrome or in combination with the newer synthetic tanning materials. All skins and hides are voided of hair and extraneous tissues before being tanned. This is accomplished by steeping the hides in a saturated lime solution fortified with sodium sulphide or similar materials. The skins and hides are then subjected to enzyme treatment to remove the final hair debris and to control welling. Water is essential for all the above purposes. Chemical composition of the water used is most important to obtain desired quality of leather. A tanner with two plants in different locations may find it difficult to make the same quality leather in both tanneries. The only standard recognised is that of distilled water. However, hardness and othe r qualities of natural waters are controlled by treatment and the water made is satisfactory for use in tanneries. The water used in tanneries should be free from microorganisms. The presence of bacteria is controlled by the use of disinfectants. There is continuous change in the chemicals used; therefore, the effluent is not constant from year to year. The application of enzyme preparations for loosening of the hair will reduce the use of lime suspensions and the difficultly disposable sulphides. Trimming and fleshing of hides at the packing house or hide processing establishment eliminate coarse solids and reduce the quantity of smaller solids in tannery effluent. Organic solvents may also be used in place of water in the processing of vegetable tanned and mineral or chrome tanned leathers. This practice would change the tannery

Substitute tannages have also been developed, such as the syntans and synthetic tans. Some leathers are tanned with formaldehyde and while others are tanned with zirconium salts in a process similar to chrome Tanners derive their water supply from many sources or combinations of sources like, rivers, lakes, creeks, wells and municipal supplies. There is practically no reusage of water by the tanning industry. There has been a constant increase in the ratio of water to leather produce; this accounts for better control and shorter time uses of water. In place 39 of using a single soak water, the trend is to change the water 2 or 3 times for an

Pollutants in Soil and Water

waste materials. In leather finishing process, solvent - dispersed pigments are gradually replacing the aqueous-type finishes.

11.7.2

Tannery Waste Characteristics

Tannery waste is mainly waterborne and has high BOD, suspended solids, soluble materials, color and odour. The discharge is highly putrefactive with foul appearance and odour. The industry is referred as one of the most polluting. The basic established principles for waste management have been implemented with slow pace due to lack of standardisation in the process. The tannery effluent contains small bits of skin tissue, soluble proteins, hair, blood, dirt or filth, manure, earth, salts of many kinds, and much lime, all mixed with sulphides, sulphydrates, amines, chrome and vegetable tanning agents, sugars, starches, oils and fats, acids, alkalies, dyes and pigments. The quantity and concentration of the contaminants preclude the possibility of direct discharge into a receiving stream. Commercial tanneries discharge their wastes after at least primary treatment, and many have secondary or even tertiary treatment systems. Tannery wastes are evaluated for their pollutional potential by tests such as BOD, total, dissolved, settleable and suspended solids, pH, basicity and free mineral acidity, color and turbidity, chlorides, sulphides, Kjeldahl nitrogen, lipids, chromium, taste and odour. Bio-chemical oxygen demand is used extensively in evaluation of tannery waste discharge and is usually very high in comparison with domestic sewage. The BOD of mixed wastes ranges from 500 to 2000 mg L1, and sometime it may be as high as 45,000 mg L1 from spent vegetable tan liquors. It is estimated that the BOD of the average tannery will amount to 7 or 8 kg for each 100 kg of hide made into leather. The tannery waste poses serious problem of organic pollution and therefore, effective measures are required for BOD reduction and control. The intermittent flow discharge is accountable for as much as 75% of the oxygen demand and when the discharge is blended and discharged at a regular rate the BOD is greatly reduced.
The ratio of litres of water to kilograms of hide processed varies greatly from plant to plant, even among those that make the same type of leather. The lower this ratio, the greater the concentration of A hide as removed from the animal will have about 65% moisture content; it will produce a leather with about 12% moisture with a yield of about 70 kg of leather for each 100 kg of hide. The total solids of a typical vegetable tannery (where sole, belting strap, case, and upholstery leathers are processed) may be as high as 7000 mg L-1. About half of this will be organic which being putrescible, accounts for the malodours associated with

Continuous op intermittent di the tannery ca material to va considerably in concentrations evaluation of t waste disposa needs to consi individual plan constituting a problem. Mos operations con processing ani leather, from t soaking and w application of

The chief source of BOD in a tannery effluent is beamhouse where hide trimming, soaking, washing, liming, and bating take place. Other areas contribute lesser amounts. The solids in tannery waste are mainly the extraneous matters and the soluble proteins of the hide. The average present-day tannery has 2000-3000 mg L1 of suspended solids before treatment. This consists of shreds of skin tissue, hair, and excess lime and chemical precipitates. The discharge of effluent with high suspended solids will cause sludge deposites in the receiving stream or sewer. In due course of time, these deposits may become considerable and require dredging or sewer cleaning. In untreated tannery discharge, the settleable solids vary from 7 to 12%. Their removal is an essential operation in the treatment of tannery wastes. The pH of a tannery waste also varies. In those plants where mixing is practiced, the acid is neutralised by the alkali which is usually in excess, and the resultant pH is alkaline i.e. from 8 to 11. The pickle liquors (sulphuric acid and sodium chloride) have a pH of 2 or less. The pH of chrome liquors ranges from 3 to 5, vegetable liquors pH vary from 3 to 6, and the pH of lime liquors which contain sulphides amines may be as high as 13. Thus, mixing of all tannery discharges into a single system is the most practical and economic method for control of BOD, solids and pH.

40

n large the hide of , the high nterferes g process. It ctice to distribute s of fats by

Turbidity is caused by many constituents in the effluent and is directly associated with the color which varies from a dirty brown to greens, blues and a milky appearance. The vegetable tans are reddish but when they come into contact with iron salts, an inky black or intermediate shades result. The wastes also contain dyes and pigments but the latter are usually in such small quantities that they influence the total color only to a minor degree. The most serious aspect of turbidity is its blocking of sunlight and its effect on aquatic life. The toxicity of tannery waste after vegetable tanning is of minor consideration. However, materials such as arsenic, chromium, high acidity or alkalinity, and sulphides are present in chrome tanning. They can cause toxicity if in high enough concentration. The salts and chemicals include sodium chloride, soda ash, sulphides with their reducing action and amines. Some of these can be toxic to aquatic life and can cause malodours. The total malodours are also contributed to by decomposition of organic matter and by hydrogen sulphide formed by contact of sulphides with acids. Nonfibrous proteins are removed when hides or skins are soaked and washed in water, depilated in saturated lime containing as much as 15% undissolved lime and bated in an enzyme liquor. These are albumins, globulins, mucoids and mucopolysaccharides, commonly referred to as the cement substances in tannery parlance and constituting the soluble proteins. These globular proteins are in various stages of denaturation. Each of the beamhouse processes contribute to the total nitrogen in the effluent. All skin proteins are capable of chemical breakdown and contribute to the turbidity, malodours and BOD of the effluent. All skins and hides contain a certain amount of lipid material. Waxy fats are added from the sebaceous glands, phospholipids from the body and the neutral fats mainly triglycerides occur as extraneous tissue beneath the hide. The fleshy fatty tissue is removed mechanically but fragments get in to the tannery waste. Sebaceous fats are mostly removed by the depilation process; neutral fats are partially removed as soaps in the lime bath and these soaps and fatty acids contribute to the effluent.

Industrial Effluents

or hide has must be this, a bath of raw oils is still wet rtially quors of the total dverse

ment of e is well tanner uses ducing it t o a e treatment the use of -active arious me fatty

11.7.3

Tannery Waste Treatment

The large volume of effluent of tannery industry defeats any economic recovery process. Leather processes are carried out empirically, with a lack of detailed technical understanding. This has resulted in a reluctance to change, and even the reuse of materials is generally avoided. Modifications such as change in materials used, proper maintenance of equipment, improved housekeeping, automation to eliminate human errors, recovery, separate disposal of materials which are pollutants and the installation of more efficient treatment systems are all significant. In considering process changes, it is important to realise that there are many different processes for each type of leather and each type of tannage. Therefore, no standard modification can be recommended or adopted. The problem is individual at each facility. Many changes including the selection of new materials have been made in view of economic and pollution aspects. Dimethylamine (DMA) sulphate has replaced the mixture of amines because the amine odour is absent until the DMA is placed in the unhairing bath. The absence of lime also yields a more desirable effluent. Another change in materials adopted by many tanners is the use of proteolytic enzymes for loosening the hair. Thus the use of lime in the unhairing system is eliminated. Both these changes reduce solids in the tannery effluent.

41

Pollutants in Soil and Water

Although equipment changes are seldom made yet they have been effective in reducing pollution. Replacement of paddle wheel pits for agitation of the stock during unhairing and bating by drums allows a nearly continuous process, without dumping of the stock after each process step. This results in a one -time use of water which has less pollutants when discharged. Better housekeeping helps to keep work places clean by daily washes which eliminates the accumulation of decaying scraps and results in a more dilute total effluent. Automation in control systems has resulted in more uniform processing and a more uniform effluent. The character of skins and hides, however, is such that in tanning much human judgment is required. One of the undesirable pollutants in tannery effluents has been the spent vegetable tan liquors. These liquors, in the past, were produced by leaching various woods, barks, leaves, and nuts with accompanying weak runoff liquors. The use of lagoons for effluent is common. Synthetic tanning materials are used in combination with natural and mineral tanning materials. The synthetic materials are expensive and are used only in small quantities; most of them are absorbed by the hide and remain as part of the leather. Primary treatment is by screening, settling basins and lagoons. Some tanners have secondary treatment plants comprising biological oxidation and settling. The methods used in other industries are also applicable to tannery waste disposal. Depending upon its location and the volume of its effluent, a tannery uses the system that is best. Lagoon and reservoir systems, with controlled volume discharge, are used by many large tanneries. A tannery has many sections producing discharges and it has been well established that combining all discharges into a holding tank, where mixing is accomplished, constitutes the best first step. This may be followed by screening, precipitation and filtration.

SAQ 12
What are the characteristics and main constituents of tannery effluents?.

SAQ 13
Why mixing of all tannery discharges into a single system provides their economical and practical treatment?

42

Industrial Effluents

11.8

HAZARDOUS WASTES

Hazardous materials have become a part of our daily lives. We use a number of chemicals, many of which are known carcinogens while others are suspected carcinogens. Some occur naturally whereas others are man-made substances produced for the benefits desired by our society. We use chemicals for many purposes. For example, about 80 percent of textiles produced annually in India are synthetic organic chemicals like polyester and nylon. The weight of organic chemical dye is from 1-8% of clothing. All fabrics are treated with a wide variety of organic chemicals to impart desired properties. Another chemical asbestos which has been extensively used in the construction and building, is also hazardous.

11.8.1

Occurrence of Hazardous Waste

tics in ackaging is tics are rise about eight of the id waste opolitan

Hazardous wastes are the inevitable by-products of an industrialised society and are present around us. The large variety and amounts of chemicals used in production leads to various types and amounts of hazardous wastes. Automobiles, televisions, furniture etc. all get their shine from manufacturing processes that produce hazardous wastes. Wastewater discharges of toxic chemicals to rivers and sewage treatment plants add enormous amounts of these substances in water. In addition to manufacturers, the common household also contributes to the pollution by hazardous wastes. Many plastic materials can generate harmful combustion products when burned. These toxic compounds comprise carbon monoxide, sulphur dioxide, nitrogen oxides, ammonia, formaldehyde, hydrogen cynide , hydrogen chloride etc. The insulating fluid used in the electrical transformer also generate toxic materials when burned, particularly if the fluid contains polychlorobiphenyls (PCBs). They are stable compounds, taking decades to decompose. PCB contamination is widespread and the chemical has been found in the soil, water, fish, human breast milk and tis sue. Hazardous wastes and hazardous materials affect everyone, directly or indirectly. But the two have important differences between them. Hazardous wastes are those substances which because of their quantity or concentration; or physical, chemical or infectious characteristics may cause, or significantly contribute to, an increase in mortality or in serious irreversible or incapacitating reversible illness; or pose a substantial present or potential hazard to human health or the environment when improperly treated, stored, transported, disposed of or otherwise managed. Hazardous waste can also be defined as any waste other than radioactive waste which by reasons of physical and/or chemicals reactive, toxic, explosives, corrosive or other characteristics causes danger to health or environment. Thus, hazardous waste is any residue that may cause significant damage to human health or environment unless adequately handled. For the purpose of identifying the Hazardous Wastes, The Ministry of Environment and Forests has amended Hazardous Wastes (Management and Handling) Rules 1989 in 2003. As per the amended rules, the Hazardous Wastes shall include:

o the family

They have ul properties nductivity ability.

43

Pollutants in Soil and Water

a)

b)

All wastes listed in Colum (3) of Schedule-I which prescribes 36 processes of various industries and the streams generating Hazardous Wastes from each of these industries. Wastes having constituents exceeding the concentrations listed in Schedule-2. Class A Class B Class C Class D Class E Concentration limit 50 mg/kg (20 constituents) Concentration limit 5,000 mg/kg (30 constituents) Concentration limit 20,000 mg/kg (17 constituents) Concentration limit 50,000 mg/kg (9 constituents) Concentration limit - Classified as Hazardous Wastes at all concentrations Flammable substances Substances which generate hazardous quantities of flammable gases on contact with water or damp air.

c)

Wastes listed in Lists A and B of Schedule 3 (Part A) is applicable only in case of import or export of Hazardous Wasted if they process any of the Hazardous Characteristics listed in Part-B of Schedule 3. Schedule 3 prescribes detailed list of wastes applicable for imports and exports, category-wise. Part-B of Schedule 3, provides list of following 14 Hazardous characteristics: i) Explosive ii) Flammable Liquids iii) Flammable Solids iv) Substances or wastes liable to spontaneous combustion v) Substances or wastes which, in contact with water emit flammable gases vi) Oxidizing vii) Organic Peroxides viii) Poisons (acute) ix) Infectious substances x) Corrosives xi) Liberation of toxic gases in contact with air or water xii) Toxic (Delayed or Chronic ) xiii) Eco-toxic xiv) Capable of yielding another material, e.g., leachate, which possesses any of the characteristics listed above.

Hazardous Waste Management Rules as amended in 2003 also include the following schedules: Schedule 4 List of non-ferrous metal wastes applicable for registration of recyclers (22 waste categories) Schedule 5 Specifications for used oil suitable for re-refining (13 parameters) Schedule 6 Specifications for waste oil suitable for recycling (5 parameters) Schedule 7 List of authorities and corresponding duties. Schedule 8 Hazardous wastes prohibited for import and export (29 wastes).

11.8.1
The presence of toxic materials is determined by using an extraction procedure which is 44 designed to simulate the leaching action that occurs in landfill.

Hazardous Waste Generation

Manufacturing industries, small business enterprises households, hospitals, research and testing laboratories and the agriculture industry are among the generators of hazardous

waste. In many cases, industries install specialised treatment facilities to handle the hazardous waste. Household solid wastes are not legally classified as hazardous, however, it creates both public health and environmental problems. Many typical household substances are pesticides, paints and paint thinners, cleaners for drains, oven and toilets bleach, metal polish and automotive products (antifreeze, batteries, motor oil, and gasoline). Many such chemicals lead to waste dumps on storage.

Industrial Effluents

xample, such as nt and exchanges covery are as waste iques. detract et of , which is e from

11.8.2

Management of Hazardous Waste

There are several alternative methods of hazardous waste management. They can be prioritized as follows: (i) Waste Reduction at source, (ii) Off-site Recycling, Recovery or Reuse, (iii) Treatment and (iv) Disposal. The first category is the most preferred; the second and third categories are considered "preferred hazardous waste management alternative s" (after the waste has been generated). The last category is the least preferred. (i) Waste Reduction at Source

Often, very little emphasis is given on waste reduction. Effort is always devoted to control pollution after the waste is generated. Waste reduction involves not only expensive plant retrofit and innovations in plant design, but also changes in the way people think and act. The inertia of current practices at all levels is

It is the most desirable hazardous waste management alternative. Thus, in designing a manufacturing process, the waste that may be produced should be critically considered along with the availability of raw materials, energy and water. As far as possible, processes which produce no waste or least troublesome waste should be adopted. Finally, treatment, storage or disposal facilities must also certify that they have a waste minimisation program. The following activities reduce waste at source:

On-site recycling of a (potential) waste . Improvements in process technology and equipment that alter the primary source of waste generation. Improvements in plant operations, e.g., better housekeeping, improved materials handling and equipment maintenance, better monitoring and automation of process equipment, and improved waste tracking or mass balance. Substituting raw materials that introduce fewer hazardous substances or smaller quantities of such substances into the production process. Redesign or reformulation of end products.

(ii) Recycling, Recovery and Waste Exchange Obviously, it is impossible to eliminate all waste generation. Therefore, as much as possible, waste should be recycled, recovered or exchanged for reuse. This is easier said than done. Certain types of waste are more difficult than others to recycle or recover usable materials from them. Recycling, recovery and exchange are gene rally more expensive than waste reduction at the source. This added expense is partly due to the added costs of storing and/or transporting the waste. In addition, there are potential health risks and legal liability associated with the possibility of spills, accidents, and other environmental releases during handling, storing, recycling, recovery and exchange. Not all wastes are contaminated and waste streams vary significantly in difficulty of recycling. The hazardous wastes can be divided into the following five types: Type I : Unused commercial chemicals in packages

45

Pollutants in Soil and Water

Type II Type III Type IV Type V

: : : :

Process wastes that are economically and technologically feasible to recycle without prior treatment Process wastes that are economically and technologically feasible to recycle if pretreated and purified Process wastes that are not presently economically and technologically feasible to recycle Wastes that are undesirable to recycle

The above classification stresses the importance of keeping wastes separate so that they can be more easily put back into the production activity. This categorisation also forces evaluation of the available techniques for treatment and recovery. (a) Recycling: It involves the use of waste streams as components in industrial and chemical processes either directly or by the partial recovery of the usable raw materials in the waste. Almost all hazardous materials are recyclable and, in many cases, the technology exists for recovery. There are several constraints on recycling hazardous waste. One is the lack of sufficient economic incentives. As long as the disposal methods remain cheaper than the cost of resource reuse, recycling in not likely to increase. Another constraint is the lack of recycling centers. Transporting waste materials to relatively distant facilities is costly and dangerous because of the possibility of spills. (b) Recovery: Various classes of inorganic and organic wastes having the greatest potential for recovery are: (i) Energy recovery from concentrated organic liquid wastes, e.g., incineration of waste organic liquids and oils (ii) Recovery of materials from concentrated organic liquid wastes, e.g., distillation and recovery of waste solvents (iii) Recovery of metals from industrial sludges and metal plating wastes, e.g., recovery of chromium, copper and nickel from spent plating batches. (c) Solvent Recovery: Solvent reclamation processes vary from solvent to solvent. Waste solvents include aliphatic, aromatic and halogenated solvents, paints, degreasing solvents, floor sealers, urethane, epoxides, urethane/epoxy strippers and furniture strippers. Deliveries of waste solvents to the treatment facility are sampled and checked for composition. Typically acceptable materialis at least 50 percent recoverable and contains less than 20 percent solids, depending on the type of solvent and the transportation costs involved. The material is separated by solvent type and loaded into receiving tanks to be batch processed. Processing is done in a solvent still, typically, a distillation unit or a thin film evaporator. Recovered solvent is accumulated in product tanks by solvent type. Most facilities sell the distillate as a reclaimed product. Some facilities have a fractionating column which can produce reconstituted or refined products approaching or equaling the specifications of the original products. (d) Oil Recovery: Waste oils include transformer oil, equipment oil, motor oil, cutting oil, soluble oil, diesel oil, gasoline, antifreeze, brake fluid and hydraulic oils. Used oil is not a hazardous waste. Most oil reclaimers operate as reclaimers of non-hazardous liquid waste only. Deliveries of waste oil are sampled to determine the percentage of recoverable waste oil and the percentage of bottom sludge and water. These undesirable constituents undermine the value of the waste oil to the reclaimer.

The waste oil i into receiving t phase separatio The oily phase to a series of tr tanks where a of indirect heat treatment is ut separate out su water. Filters a remove suspen Recovered oil to product stor Filtrates are eit accumulated in for disposal or through a dewa such as vacuum

46

(iii) Treatment It refers to activities designed to limit the hazardous characteristics (e.g., toxicity, corrosivity, flammability, reactivity), volume and complexity of the wastes before disposal. As such, treatment should be undertaken only after source reduction and recycling or recovery techniques have been exhausted. Various treatment methods often result in the separation of the liquid and solid components of the waste stream. Because these components often become more concentrated or pure, treatment enables the waste generator or recycler to recover usable component and is also considered a process step to recycling or resource recovery. This duality of function has given rise to some confusion, in the same way as waste recycling, treatment and recovery are often confused with waste reduction techniques. True waste reduction begins at the source, not after the waste has been generated. The most common types of treatment alternatives are as follows: (a) Chemical treatment: neutralisation, precipitation, ion exchange, oxidation/reduction, solidification/fixation and dechlorination. (b) Physical treatment: solid/liquid separation processes (screening, sedimentation. flotation, filtration and centrifugation); membrane separation processes (dialysis, reverse osmosis, ultrafiltration, and electrodialysis), evaporation, distillation/steam stripping, solvent extraction and adsorption. (c) Biological Treatment: activated sludge, trickling filter, aerated lagoons, waste stabilization ponds and anaerobic digestion. (d) Thermal treatment: calcination, pyrolysis, open burning, and incineration (e.g., rotary kiln fluidised bed, multiple hearth and liquid injection). (iv) Disposal

Industrial Effluents

an be classified egories he waste ocessed. For ration of and recapturing al uses y called energy . On the other ing most solids ds can be reatment" or a p because it he form and waste; the disposal. ubstances can umes and/or free liquids and g no further incineration. has been called n disposal

It refers to the discharge of waste into or onto the land or water including the ground water. Ideally, hazardous wastes should be treated (e.g. neutralised, detoxified, clarified, oxidised, or reduced in volume) Although incineration has its own limitations as a waste before disposal which can be done as follows:
management technique either for treatment or disposal, it is increasingly preferred as a means of limiting the generators' potential legal liability associated with the wastes. Because of this and other factors such as the ban on landfilling untreated hazardous wastes, the incineration process of hazardous waste management is the most preferred.

(a) Land Disposal: It is the most common method of disposing and includes open dumps, surface impoundments, sanitary landfills, "secure" chemical landfills and underground injection wells. Landfills and surface impoundments, are the least favoured method for managing hazardous wastes.

(b) Open Dumps: It is the oldest method of disposing wastes, however, it is the least acceptable form of land disposal. Wastes are litreally dumped on a designated site or unused areas such as vacant lots, streams, ravines or along roadsides. Wastes range from household garbage and dead animals to junked cars and toxic chemicals. Often, these wastes are burned, either intentionally (to reduce volume) or unintentionally (through accidents or spontaneous combustion). Open dumps pose many environmental problems. Decaying waste typically left uncovered, creates odours and attracts disease vectors, e.g., rats, birds, flies, and other insects. Rain, snow and surface waters pass through the waste and pollute ground and surface waters. Runoff from these areas can pollute streams, lakes and wetlands.

47

Pollutants in Soil and Water

Fires from dumped refuse create air pollution. An uncovered dump is unsightly, and a strong wind can litter the countryside for lo ng distances. (c) Surface Impoundments: They are sometimes called open ponds or evaporation ponds. They are also not well accepted for land disposal. Their primary purpose is either volume reduction (treatment) or outright disposal. Impounded liquids can overflow during heavy precipitation, thus contaminating the ground, Sanitary landfills are well nearby surface waters and the groundwater. Solvents in open ponds engineered, well-controlled evaporate readily and it is difficult to determine where the resulting land disposal sites for solid, toxic air emissions will end up. Further, these impoundments may non-hazardous wastes. also leak. They are a great (d) Sanitary Landfills: It is the most widely accepted alternative to open dumps and burning of garbage. Typical wastes of sanitary landfills include residential, office and industrial wastes. The waste stream may include sludge or remaining solids from sewage treatment plants, or animal, agricultural and demolition wastes. Sanitary landfills are designed to handle only non-hazardous wastes. However, some hazardous waste are mixed with the solid wastes that are landfilled. In the past, these sites received household hazardous wastes and commercial industrial wastes (likely of including hazardous wastes) in addition to household refuse. The present ground water contamination indicates that industrial (or household) hazardous wastes are the source of the problem. The same situation is likely to be present at many of the municipal solid waste landfills.
improvement over open dumps and surface impoundments. Wastes are spread and compacted in layers a few feet thick. At least once a day, the wastes are covered with a layer of earth and again compacted. This minimises the problems associated with the open dump such as odours, fires, wind-blown wastes, and vectors. Sanitary landfills can also pose potential environmental problems; they may leak, smell, generate gas (e.g. vinyl chloride and methane) and be a nuisance. They are one of the much-needed but "noxious" facilities.

The joint disposal of municipal (domestic) and industrial (including hazardous) wastes by landfill has advantage in terms of water protection compared with discrete chemical landfills. Site experience reportedly show that chemical and physico-chemical reactions within a municipal waste landfill can prevent, or at least substantially reduce, the potential hazards of the deposited wastes. Investigations at joint disposal sites have shown that municipal wastes absorb and retain oils and other organic substances such as halogenated hydrocarbons. Phenols are reversibly absorbed and significantly degraded; however, heavy metals are not solubilised. While such practice may have some benefits, it is difficult to predict the chemical reactions that would result from such unknown mixtures of wastes. It could be equally reasonable to suppose that some new hazardous chemicals may be unwittingly synthesized by the interactions of many substances that are intermingled in the landfill. It is also possible that such degradation of organics may be due to the action of bacteria or microorganisms that would be found in biological treatment. If this is the case, more controlled conditions should be provided to encourage the biological degradation of wastes. This biodegradation could be better done outside the confines of a traditional landfill. Meanwhile, it would seem prudent that hazardous waste landfills should be designed as such, rather than as ordinary sanitary landfills. (e) Hazardous Waste Landfills: Secure landfills (SLF),

The sheer number of solid waste landfills nationwide and the potential health risks associated with hazardous wastes at these sites should be of concern. The distinction between a hazardous waste landfill and a non-hazardous solid waste landfill is only a matter of degree. All landfills could eventually leak, and therefore testing of all solid waste sites for hazardous waste leakage into the air and water needs to be routinely done.

48

sometimes called secure chemical waste landfills have become the accepted repository for hazardous wastes. They are carefully constructed earthen excavations specifically designed to both contain hazardous wastes and keep them from escaping into the environment, either by leaching into the groundwater or by evaporating. Secure landfills are subject to location and operational requirements, including the monitoring of surface and groundwater, and the avoidance of flood and earthquake-prone areas, wetlands, and historic places. The SLF utilised double containment principles to prevent liquid hazardous waste (leachate) from migrating out of the landfill. Combinations of impermeable soils, clay and synthetic flexible membrane liners are used to contain wastes and leachate in the landfill. An additional layer of soil may then be added over the synthetic liner to prevent physical damage such as tears and punctures. A monitoring and leachate collection system is placed between the bottom clay layer and the synthetic liner. An additional layer of clay, synthetic liner and leachate monitoring system is placed on top of the first layer for additional protection. The leachate collection system is facilitated by troughs and pipes build into the landfill to channel the leachate to collection points. Assuming that the landfill did not accept liquid wastes, the presence of liquids in the leachate collection system alerts the operator to the possibility of a facility failure. The operator can drain the leachate and make the necessary repairs before material escapes the landfill, either through a downward route (leaching) into the groundwater directly below, or through breaks on the rim of the landfill. In addition to the monitoring and collection systems placed in the landfill, monitoring wells are also placed outside the facility to test groundwater for changes which may indicate the facility is leaking material into the environment. Air pollution monitors are also placed near the landfill to detect hazardous emissions from the facility. (f) Underground Injection: It is used for the disposal of oil field wastes. This technique is now being used for disposing of other wastes also. In underground (deepwell) injection process, wastes are injected through wells into porous limestone and sandstone formations several kilometers below the earth's surface. Critics of deepwell injection point out that a lack of precise knowledge about subsurface conditions and potential reaction of wastes within "impermeable" geologic layers preclude the use of this disposal practice. (g) Overview on Land Disposal Techniques: The land disposal techniques described above only vary in their degree of unacceptability. Land disposal of hazardous waste is not a permanent solution. Critics consider land disposal another form of storage, a transfer of wastes from one place to another. Land disposal can give a false sense of security that the waste problem has been solved. Even secure landfills will fail in time. Land disposal of wastes containing dioxins and similar compounds should not be done unless they have been treated to reduce their toxicity. The prohibition applies to such commonly used solvents as acetone, carbon tetrachloride, tri- and tetrachlorethylene, methanol, toluene and xylene. The most effective treatment available today for concentrated and dioxins wastes is high temperature incineration. Other technologies include air stripping, batch distillation, biological treatment, carbon adsorption and thin film evaporation.

Industrial Effluents

SAQ 14
Give characteristics of hazardous waste.

49

Pollutants in Soil and Water

SAQ 15
Describe activities to reduce hazardous waste at source.

SAQ 16
Write treatment alternatives for hazardous waste.

11.9

SUMMARY

Let us now summarise the main points that have been discussed in this unit. The contaminated water released from industries after its use is known as industrial effluent. Its quality is measured by physico-chemical parameters. The waste is subjected to treatment to improve its quality before discharge. Suspended matters are removed by settling, flotation and filtration. Heat treatment, cooling and temperature control are also required in some treatment process. Chemical reactions like oxidation, reduction and precipitation are the basis of chemical treatment. Aerobic and anaerobic biological treatment processes are utilised for the treatment of waste containing soluble organics. Treated effluents are discharged either into water bodies or onto land. The products processed by dairy include fluid products, nonfat dry milk powder, cheese and less perishable products. The waste water from a dairy contains excessive organics and nutrients like nitrogen and phosphorus. The treatment system for dairy waste comprises; aeration or modified activated sludge, trickling filters and application on land. Lagooning is also effective to some extent. Chemical treatment using lime and ferrous sulphate is also used, however, this method is not cost effective.

50

Refineries and petrochemical industries discharge wastewaters which are characterised by immiscible oils, solvents, high BOD and significant solid levels. Waste treatment and effluent disposal methods comprises; i) inplant procedures, ii) stripping and oxidation, iii) combustion, iv) solvent extraction, v) good house keeping, vi) terminal treatment, vii) gravity separations, viii) chemical flocculation, ix) coalescence, x) air flotation, xi) biological oxidation, xii) chemical oxidation, xiii) final wastewater treatment, xiv) underground disposal xv) dilution and xvi) evaporation and proper sludge disposal. Textile wastes from various segments differ widely in characteristics. A composite waste from an integrated cotton textile plant contains varied type of chemicals. Waste reduction, prevention and reuse practices provide saving of materials and reducing the quantity of waste discharges. Physical, chemical and biological methods are used for the treatment of waste. Physical and chemical methods comprise; i) segregation, ii) lagooning and storage, iii) screening, iv) mechanical filtration, v) preparation and post aeration, vi) neutralisation, vii) chemical precipitation and viii) chemical oxidation. Trickling filters, activated sludge and oxidation ponding are the biological oxidation methods used for treatment. Trickling filters coupled with polishing in oxidation pond is the most effective treatment method. The major pollutants of pulp and paper industry effluents are suspended matters and dissolved organic substances. The industry requires large volume of water and consequently releases huge quantities of effluent. The suspended matters consist mainly of fiber, fiber debris, filling and coating materials which are captured by means of savealls. Non-settleable solids are made settleable by the addition of coagulants and coagulant aids like polye lectrolytes. Stabilisation basins, trickling filters and activated sludge treatments are employed for the reduction of organics. Disposal of effluent on land does not offer potential of whole sale application Tannery waste is mainly waterborne and has high BOD, suspended solids, soluble materials, color and odour. The quantity and concentration of the contaminants preclude the possibility of direct discharge into a receiving stream without treatment. The pH of wastes emanating from different sections vary considerably. Mixing of all tannery discharges into a single system provides most economical and practicable solution for pH adjustment and ultimately control of BOD and solids. The effluents are subjected to primary treatment which consists of screening, settling basins and lagoons. In some cases, secondary treatment comprising biological oxidation and settling is also employed. Hazardous wastes are inevitable by-products of an industrialised society. Any residue that may cause significant damage to human health or environment is categorised as hazardous waste. A waste is classified as hazardous, if it exhibits one or more characteristics like explosive, flammable, corrosive, oxidizing, acute poison, infectious, toxic etc. The methods of hazardous waste management include waste reduction at the source, offsite recycling, recovery or reuse, treatment and disposal. Common types of treatment alternatives are chemical, physical, biological and thermal treatments. Thermal treatment using incineration technique is the most preferred technique of hazardous waste management. Treated hazardous wastes are disposed on land, however, this is not a permanent solution because this is simply a transfer of wastes from one place to another.

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11.10
1. 2. 3. 4.

TERMINAL QUESTIONS

Describe biological treatment methods for industrial effluents. Write a short note on the treatment of dairy waste. Describe methods for disposal of sludges from petrochemical industry. Explain the working of the trickling filter process for the treatment of effluent from textile industry. Write briefly a note on the use of stabilisation basins for the reduction of organics from pulp and paper effluents. Give a brief account of tannery waste treatment system. Give an outline of hazardous waste disposal.

5.

6. 7.

11.11

ANSWERS

Self-Assessment Questions
1. Physico-chemical parameters commonly used in the study of wastewater are i) total suspended solids, ii) settleable solids, iii) total dissolved solids, iv) turbidity v) oils, vi) colour, vii) taste, viii) odour, ix) acidity, x) alkalinity, xi) pH, xii) chlorides, xiii), hardness, xiv) surfactants, xv) inorganic cations and anions, xvi) radioactivity, xvii) dissolved oxygen, xviii) biochemical oxygen demand and xix) chemical oxygen demand. Inplant measures to control pollution are: i) Process change: This is done by adopting newer technologies which generate lesser pollutants. ii) Material recovery: Products and by-products are either recovered from the wastes or intercepted before they enter the waste stream. iii) Water reuse: The wastewater after treatment is used again. Sometimes, the treated wastewater is utilised for irrigation or green belt development around the industry. iv) Wastewater collection: Wastewater is collected judiciously to make the final treatment easy. Toxic wastes are collected separately. Acid and alkaline wastes are mixed together for partial neturalisation. Particulate matters are generally removed using settling, flotation and filtration techniques. In settling the wastewater is detained in a specially built tank for predetermined period. The heavier suspended particulates settle as sludge and are removed by scrapers. Particles lighter than water move upwards and are removed by skimmers. Fine particulates with density less or close to water do not settle. These particles, however, move upward by incorporating minute air bubbles in the wastes. Flotation process utilises this property. The bubble and solids or oils rise to the surface and are remove d by skimming. Filtration is done to remove the particulates from the treated effluent. Coarse particulates are removed by passing the wastes through screens.

2.

3.

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4.

They include referigeration system of condensing, precooling system for pasteurized products, rinse and washwater, spillage, leakage, overflow, unutilised byproducts and spoiled or damaged raw or manufactured products. The system comprises an aeration tank in which aerobic microorganisms are developed. The waste containing organic material is fed to the tank and fresh air containing oxygen is also supplied. Thus, conditions suitable for the growth and reproduction of microorganisms are provided which ultimately result in the reduction of organic content of the waste. They include oil which may be separable, emulsified or dissolved; chemicals including acids, alkalis, sulphides, mercaptans, ammonia and phenols and suspended solids.

Industrial Effluents

5.

6.

7. API separator is a gravity separator designed by American Petroleum Institute. It is basically a large rectangular tank designed to slow down the wastewater flow rate so that oil droplets can rise to the surface of the wastewater slowly along the length of the tank. Thus, oil accumulates on the surface and heavy solids settled down to the bottom. Oil skimming and bottom sludge scrapping are to be done periodically. 8. They include starches, dextrins, gums, glucose, waxes, pectins, alcohols, fatty acids, acetic acid, soaps, detergents, sodium hydroxide, carbonates, sulphides, sulphates, chlorides, dyes and pigments, carboxy methyl cellulose, gelatine, dye carriers (phenols and benzoic acid), peroxides and chlorine bleach. It provides equalisation to the characteristics of effluent which in turn eliminate variation in pollution load. Oxidation ponds with and without aeration are the most effective type of lagoon. Aeration, however, helps to reduce odours and pollutional characteristics.

9.

10. (i) The effluents contain suspended matters and dissolved organic substances. The former forms bottom deposits in receiving streams and the latter are inimical to aquatic life, unsightly and on decomposition produce odour problems. (ii) The discharge of highly dispersed solids such as fiber debris, filter and coating materials can render a stream opalescent which retards self -purification by limiting light penetration. (iii) Dissolved wood supers deplete the dissolved oxygen and stimulate the growth of slime organisms causing biological imbalance. (iv) Lignins and tannins cause discoloration. (v) Resin acid soaps and mercaptans in high concentration are toxic to aquatic life. 11. Solid bearing wastes comprise fiber, fiber debris and filling and coating materials such as clays filling, calcium carbonate and titanuim dioxide. These substances are removed from the effluents by save alls such as screening, filtration, settling or flotation devices and returned to the system for reuse. The most common process of treating solid waste bearing waste is sedimentation. In some cases, flotation and filtration are also used. 12. The tannery waste has high BOD, suspended solids, soluble materials, colour and odour. It contains small bits of skin tissue, soluble proteins, hair, blood, dirt or filth, manure, earth, salts and lime, all mixed with sulphides, sulphydrates, amines, chrome and vegetable tanning agents, sugar starches, oils and fats, acids, alkalies, dyes and pigments.

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13. The chemical reactions in leather processing have variation from high acidity to high alkalinity. Thus, the effluent emanating from various units have different pH and organic contents. The pickle liquours have a pH of 2 or less whereas pH of lime liquours containing sulphides and amines may be as high as 13. Mixing of all effluents into a single system bring the pH almost to neutrality (pH 7). This amounts to saving in the cost of chemicals otherwise to be used for neutralisation. The mixing of all effluents, therefore, provides most practical and economic solution for the treatment of tannery waste. 14. A waste is called hazardous if it possess one or more of the characteristics like explosive, flammable, corrosive, oxidizing, acute poison, infectious , toxic etc. 15. The most desirable hazardous waste management alternative is either avoid or minimise the waste generated at source. If possible non-waste producing processes are to be adopted. Waste reduction at source means adoptation of an alternate technology which generates least quantity of waste. Five classes of activities that reduce waste at the source are: (i) on-site recycling of a potential waste, (ii) improvement in process technology and equipment that alter the primary source of waste generation, (iii) improvements in plant operations, e.g., better house keeping, improved materials handling and equipment maintenance, better monitoring and automation of process equipment, and improved waste tracking or mass balance, (iv) substituting raw materials that introduce fewer hazardous substances or smaller quantities of such substances into the production process and (v) redesign or reformulation of end products. 16. Treatment refers to activities designed to limit the hazardous characteristics, volume and complexity of the wastes before their disposal. The most common types of treatment alternatives are: (i) chemical treatment comprising neutralisation, precipitation, ion exchange, oxidation / reduction, solidification / fixation and dechlorination, (ii) physical treatment which includes solid liquid/liquid separation processes, membrane separation processes, ultrafiltration, electrodialysis, evaporation, distillation, stream stripping, solvent extraction and adsorption, (iii) biological treatment which includes activated sludge, trickling filter, aerated lagoons, waste stabilisation ponds, and anaerobic digestion, (iv) thermal treatment comprising calcination, pyrolysis, open burning and incineration. Among these processes, the incineration is the most preferred technology.

Terminal Questions
1. Industrial effluents having low concentrations of organics are often difficult to be treated by physical or chemical methods alone. But they are amenable to attack by microorganisms which may be aerobic. The growth of microorganisms requires the presence of nitrogen and phosphorus nutrients. The organic components are destroyed by metabolic processes ending as innocuous materials. In aerobic process, much of carbon is removed as carbon dioxide, the hydrogen as water, and nitrogen and sulphur as nitrate ion or nitrogen gas and sulphate ion, respectively. Some of the waste is converted to cell tissue in the microorganisms and the excess appears as sludge.

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Industrial Effluents

Trickling filters, activated sludge and lagoons are the treatment systems used for aerobic treatment of effluent. All these systems work on the principle of oxidation of organics in the presence of dissolved oxygen by microorganisms. In some cases, anaerobic microorganisms provide effective treatment. Anaerobic degradation of organic matter is slower than aerobic oxidation. In anaerobic process, the organic matter is gasified to methane and carbon dioxide. 2. The effluent of dairy waste is rich in organics present in colloidal and dissolved state. Biological oxidation is, therefore, a preferred method for its treatment. The waste is initially passed through a grit chamber to remove sand and other gritly materials. The effluent from grit cha mber is diverted to an equilisation tank. This tank has sufficient capacity to hold surges while the waste is pumped out at uniform rate. Air is introduced through diffuser in the tank so that the wastes do not become septic. The treatment systems most effective for dairy wastes should provide sufficient oxygen to bio-chemically oxidise the organic constituents. Treatment systems used extensively are aeration or modified activated sludge, trickling filters and irrigation. Lagoons are also used in some cases. Each sludge from petrochemical industry i.e. oily, oil-free, chemical and biotreatment, has its own characteristics and needs a particular method of disposal. (i) Oily sludges consist of slurries of oily solids in water and are thickened by centrifugation before disposition to some remote area or incineration. (ii) Oil free sludges are thickened and dewatered by centrifugation. The dewatered solids are disposed as landfill. (iii) Chemical sludges contain useable chemicals which are separated by specific treatment. The residues are dried and buried. (iv) Biotreatment sludge from biotreatment units are digested anaerobically. Disposition of residual sludge is accomplished by dewatering, centrifuging and incinerating. These are also disposed as landfill. 4. The wastewater from textile industry is initially sprayed over a broken medium, such as stone or plastic. The medium serves as a base for biological growth which in the presence of air drawn through the filter, attack the organic matter of the waste and use it for food. This removes a large part of the organic pollution and the effluent can usually be discharged to a stream after a final settling. Mixing of sewage with textile effluent provides about 75% removal of BOD by trickling filter. Stabilisation basins are the most widely used for biological oxidation of effluents. Two types of basins - natural reaeration and mechanical aeration types are used. The natural reaeration basin is normally shallow and stabilisation basins are also used which provide storage for controlled discharge of treated effluent. In mechanical aerated basin, air is supplied by mechanical surface aerator. The basins are supplied wastewater substantially free from settleable solids. A small entrance basin is made between effluent clarification system and the major stabilisation system to trap suspended matter over flowing. The stabilisation basins are built in multiple to prevent short circuiting. At least two separate basins are used simultaneously or one or more dividing walls are provided if a single basin is used. Microbes act on organics present in the waste and degrade them. In normal case aeration is provided from mechanical means, however, for board mill waste a high degree of aeration needs to be provided to prevent formation of odourous gas. The system requires considerable area of land which is a main short coming.

3.

5.

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Pollutants in Soil and Water

6.

The tannery wastes are given only primary treatment which includes screening, settling basins and lagoons. In some cases, secondary treatment comprising biological oxidation and settling is also needed. The treatment methods used for the effluents of other industries are also applicable to tannery waste disposal. A tannery uses a treatment that is best suited, depending upon its location and the volume of its effluent. Lagoon and reservoir systems with controlled volume discharge are used by many large tanneries. A tannery has many units producing discharges. Mixing of these discharges into a holding tank constitutes the best first step in treatment. The mixed effluent is to be treated by screening, precipitation and filtration. Disposal of hazardous waste refers to the discharge of waste into or onto the land or water. Ideally hazardous waste should be neutralised, detoxified, clarified, oxidised or reduced in volume before being disposed of. The alternatives are: land disposal, open dumps, surface impoundments, sanitary landfills, secure landfills and underground injection. Land disposal of hazardous waste is not a permanent solution but is another form of storage i.e., a transfer of wastes from one place to another. Land disposal can give a false sense of security and even secure land fills will fail in time. Land disposal of waste containing dioxins and similar compounds should not be done unless they have been treated to reduce their toxicity. The most effective treatment available today for concentrated and dioxins wastes is high temperature incineration. Other technologies for treatment include air stripping, batch distillation, biological treatment, carbon adsorption and thin film evaporation.

7.

11.12

GLOSSARY

ACIDITY - Quantitative capacity of aqueous solutions to react with hydroxl ions. Measured by titration, with a standard solution of a base to a specified end point. Usually expressed as milligrams per litre of calcium carbonate. ACTIVATED CARBON - Carbon "activated" by high temperature heating with steam or carbon dioxide, producing an internal porous particle structure. ADSORPTION - Adhesion of an extremely thin layer of molecules (gas or liquid) to the surfaces of solids (e.g., granular activated carbons) or liquids with which they are in contact. AERATE - To permeate or saturate a liquid with air. ALKALINITY - Capacity of water to neutralize acids, imparted by the water's content of carbonates, bicarbonates, hydroxides, and occasionally borates, silicates, and phosphates. Expressed in milligrams per litre of equivalent calcium carbonate. ANAEROBIC WASTE TREATMENT - Waste stabilization brought about by the action of microorganisms in the absence of air or elemental oxygen. Usually refers to waste treatment by methane fermentation. BIOCHEMICAL OXYGEN DEMAND (BOD) - Measure of the concentration of organic impurities in wastewater. The amount of oxygen required by bacteria while stabilizing organic matter under aerobic conditions, expressed in milligrams per litre, is determined entirely by the availability of material in the wastewaters to be used as biological food and by the amount of oxygen utilised by the microorganisms during oxidation.

56

BIOLOGICAL OXIDATION - Process in which living organisms in the presence of oxygen convert the organic matter contained in wastewater into a more stable or mineral form. BUFFER - Any combination of chemicals used to stabilize the pH or alkalinities of solutions. CHEMICAL COAGULANT - Destabilization and initial aggregation of colloidal and finely divided suspended matter by the addition of floc-forming chemicals like alum . CHEMICAL OXYGEN DEMAND (COD) - Measure of the oxygen-consuming capacity of inorganic and organic matter present in water or wastewater, expressed as the amount of oxygen consumed from a chemical oxidant in a specific test. It does not differentiate between stable and unstable organic matter and thus, does not necessarily correlate with biochemical oxygen demand. CHLORINATION - Application of chlorine to water or wastewater, generally for the purpose of disinfection, but frequently for accomplishing other biological or chemical results. CLARIFICATION - Any process or combination of processes to reduce the concentration of suspended matter in a liquid. COAGULATION - Process by which chemicals (coagulants) are added to an aqueous system, to render finely divided, dispersed matter with slow or negligible settling velocities into more rapidly settling aggregates. Forces that cause dispersed particles to repel each other are neutralized by the coagulants. COLLOIDAL MATTER - Dispersion of very small (1 mu to 0.5 u) particles that will not settle but may be removed by coagulation or biochemical action or membrane filtration. COMMINUTION - Process of cutting and screening solids contained in wastewater flow before it enters the pumps or other units in the treatment plant. COMPOSITE WASTEWATER SAMPLE - Combination of individual samples of water or wastewater taken at selected intervals (generally hourly or some similar specified period), to minimize the effect of the variability of the individual sample. Individual samples may have equal volume or may be roughly proportional to the flow at time of sampling. DETENTION TIME - Average period of time a fluid element is retained in a basin or tank before discharge. ELECTRICAL CONDUCTIVITY - Reciprocal of the resistance in Ohms measured between opposite faces of a centimeter cube of an aqueous solution at a specified temperature. Expressed as micromhos or micro Siemens per centimetre at 25C or specified temperature. FATS - Triglyceride esters of fatty acids. Erroneously used a synonym for grease. FLOC - Agglomeration of finely divided or colloidal particles resulting from certain chemical, physical or biological operations. GREASE - In wastewater, a group of substances, including fats, waxes, free fatty acids, calcium and magnesium soaps, minerals oils, and certain other non-fatty materials. The type of solvent and method used for extraction should be stated for quantification. GREASE SKIMMER - Device for removing floating grease or scum from the surface of wastewater in a tank. GRIT CHAMBER - Detention chamber or an enlargement of a sewer, designed to reduce the velocity of flow of the liquid, to permit the separation of minerals from organic solids by differential sedimentation.

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Pollutants in Soil and Water

HARDNESS - Characteristics of water imparted by salts of calcium, magnesium, and iron (such as bicarbonates, carbonates, sulphates, chlorides, and nitrates), which causes curdling of soap, deposition of scale in boilers, damage in some industrial processes, and sometimes objectionable taste. It may be determined by a standard laboratory procedure or computed from the amounts of calcium, magnesium, iron, aluminum, manganese, barium, strontium, and zinc, and is expressed as milligram per 1 litre of equivalent calcium carbonate. HYDRAULIC LOADING - Quantity of flow passing through a column or packed bed, expressed in the units of volume per unit time per unit area; e.g., (m3/m2.s). INDUSTRIAL WASTES - Liquid wastes from industrial processes, as distinct from domestic or sanitary wastes. INFILTRATION - Ground water that seeps into pipes, channels, or chambers through cracks, joints, or breaks. INFLUENT - Wastewater or other liquid (raw or partially treated) flowing into a reservoir, basin, treatment process, or treatment plant. INORGANIC MATTER - Chemical substances of mineral origin; not of basically carbon structure, with animal or vegetable origin. POND - 1) Shallow body of water, i.e., lagoon or lake; or 2) pond containing raw or partially treated wastewater in which aerobic or anaerobic stabilization occurs. METHYL ORANGE ALKALINITY - Measure of the total alkalinity of an aqueous suspension or solution, determined by the quantity of sulphuric acid required to bring the water pH to a value of 4.3 as indicated by the change in color of methyl orange. Expressed in milligrams CaCO3 per litre. MICROSCREENING - Form of surface filtration using specially woven wire fabrics mounted on the periphery of a revolving drum. MONITORING - 1) Measurement, sometimes continuous, of water or wastewater quality; or 2) procedure or operation of locating and measuring radioactive contamination, by means of survey instruments that can detect and measure, as does rate, ionizing radiations. NON-SETTLEABLE SOLIDS - Suspended matter that does not settle or float to the surface of water in a period of 1 hour. ORGANIC MATTER - Chemical substances of animal or vegetable origin of basically carbon structure, comprising compounds consisting of hydrocarbons and their derivatives. ORGANIC NITROGEN - Nitrogen combined in organic molecules, such as protein, amines, and amino acids. OVERFLOW RATE - One of the criteria for the design of settling tanks in treatment plants, expressed in cubic metres per day per square metre (m3/m2.d) of surface area in the settling tank. OXIDATION - Addition of oxygen to a compound. More generally, any reaction involving the loss of electrons from an atom. OXIDATION POND OR LAGOON - Basin used for retention of wastewater before final disposal, in which biological oxidation of organic materials is effected by natural or artificially accelerated transfer of oxygen to the water from air. PATHOGENIC ORGANISMS - Organisms, usually microscopic in size (e.g., bacteria and viruses), that may cause disease in the host organisms by their parasitic growth.

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pH - Reciprocal of the logarithm of the hydrogen ion concentration. T he concentration is the weight for hydrogen ions, in grams per litre of solution. Neutral water, for example, has a pH value of 7 and hydrogen ion concentration of 10 -7. PHENOLPHTHALEIN ALKALINITY - Measure of the hydroxides plus one- half the normal carbonates in aqeuous suspension. Measured by the amount of sulphuric acid required to bring the water to a pH of 8.3, as indicated by a change in colour of phenolphthalein expressed as mg/l of calcium carbonate. PHYSICAL-CHEMICAL TREATMENT (PCT) PLANT - Treatment sequence in which physical and chemical processes are used to the exclusion of explicitly biological process. POLYELECTROLYTES - Chemicals consisting of high molecular weight molecules with many reactive groups situated along the length of the chain. Polyelectrolytes react with the fine particles in the waste and assist in bringing them together into larger and heavier masses for settling. POST -CHLORINATION - Application of chlorine to the final treated wastewater or effluent following plant treatment. PRE-CHLORINATION - Chlorination at the headworks of the plant; influent chlorination prior to plant treatment. PRIMARY SETTLING TANK - First settling tank for the removal of settleable solids through which wastewater is passed in a treatment works. PRIMARY TREATMENT - 1) First (sometimes only) major treatment in a wastewater treatment works, usually sedimentation; or 2) removal of a substantial amount of suspended matter, but little or no colloidal and dissolved matter. SEWAGE - Mixture of all liquid domestic wastes including faecal matter and urine. RAW SLUDGE - Settled sludge promptly removed from sedimentation tanks before decomposition has much advanced. Frequently referred to as undigested sludge. RECIRCULATION RATE - Rate of return of part of the effluent from a treatment process to the incoming flow. RESIDUAL CHLORINE - Chlorine remaining in water or wastewater at the end of a specified contact period as combined or free chlorine. SALINITY - 1) Relative concentration of salts, such as sodium chloride, in a given water, usually expressed as mg/l of chloride (cl); or 2) measure of the concentration of dissolved mineral substances in water. SANITARY SEWER - Sewer that carries liquid and water-carried human wastes from residences, commercial buildings, industrial plants, and institutions, together with minor quantities of storm, surface, and groundwater(s) that are not admitted intentionally. Significant quantities of industrial wastewater are not carried in sanitary sewers. SCREEN - Device with openings, generally of uniform size, used to retain or remove suspended or floating solids in flowing water or wastewater and to prevent them from entering an intake or passing a given point in a conduit. The screening element may consist of parallel bars, rods, wires, grating, wire mesh, or perforated plate; the openings may be of any shape, although they are usually circular or rectangular. Also a device used to segregate granular material, such as sand, crushed rock, and soil, into various sizes.

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SECONDARY SETTLING TANK - Tank through which effluent from some prior treatment process flows for the purpose of removing settleable solids. SECONDARY WASTEWATER TREATMENT - Treatment of wastewater by biological methods after primary treatment by sedimentation. SEDIMENTATION - Process of subsidence and deposition of suspended matter carried by water, wastewater, or other liquids, by gravity. Usually accomplished by reducing the velocity of the liquid to below the point at which it can transport the suspended material. Also called settling. SELF-PURIFICATION - Natural processes occurring in a stream or other body of water resulting in the reduction of bacteria, satisfaction of the BOD, stabilization of organic constituents, replacement of depleted dissolved oxygen, and the return of the stream biota to normal. SETTLEABLE SOLIDS - Matter in wastewater that will not stay in suspension during a preselected settling period (such as 1 hour) but settles to the bottom or floats to the top. SKIMMING TANK - Tank so designed that floating matter will rise and remain on the surface of the wastewater until removed, while the liquid discharges continuously under certain walls or scum baffles. SLOUGHINGS - Trickling filter slimes that have been washed off filter media. They are generally quite high in BOD and will degrade effluent quality unless removed. SUSPENDED SOLIDS - Solids that float on the surface of, or are in suspension in, water, wastewater, or other liquids, and that are largely removable by filtering. TOT AL SOLIDS - Sum of dissolved and undissolved constituents in water or wastewater, usually expressed in milligrams per litre. TURBIDIMETER - Instrument for measurement of turbidity, in which a standard suspension is generally used for reference. TURBIDITY - Condition in water or wastewater caused by the presence of suspended matter, resulting in the scattering and absorption of light rays. Measure of fine suspended matter in liquids. Analytical quantity, usually expressed in Jackson Turbidity Units (JTU) / Nephalometric Turbidity Units (NTU).

11.13
1. 2.

SUGGESTED READINGS

Gurnham, C.F.,"Principles of Industrial Waste Treatment" Wiley, Newyork, 1955 Standard Methods for the Examination of Water and Wastewater, "19the edition, American Public Health As sociation, Washington DC (1995) U.S.Dept. Agr. Handbook No.176 "Dairy Waste Treatment by Aeration - Theory, Design, Construction and Operation," 1960 Gurnham, C.F. "Industrial Wastewater Control, Academic Press", Newyork, 1965 American Petroleum Institute, "Manual on Disposal of Refinery Wastes", Vol.I, "Wastewater Containing Oil", 7th edition 104 pp., 1963 Barnes D., Forster, C.F. and Hrudey, S.E., "Petroleum and Organic Chemicals Industries", Pitman Publishing Limited, London, 1984 U.S.Public Health Service, "An Industrial Waste Guide to the Cotton Textile Industry", 1959

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4. 5.

6.

7.

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Masselli, J.W., Masseli, N.W. and Burford, M.G. (Hall laboratory of Chemistry, Wesleyan University, Moddle town, Conn.), "Tannery Wastes: Pollution Sources and Methods of Treatment", New England Interstate Water Pollution Control Commission, 1958 Guidelines for Management and Handling of Hazardous Wastes; Ministry of Environment and Forests, Government of India, New Delhi, 1991 and Hazardous Wastes (Management and Handling) Amendment Rules, 2003.

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