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Chapter 5

ENVIRONMENTAL AUDIT

Reference: Asolekar, S. R. and Gopichandran, R. (2005). “Preventive Environmental Management – An Indian Perspective”, Foundation Books Pvt. Ltd., New Delhi (the Indian associate of Cambridge University Press, UK) We commence our discussion here on the “tools” for PEM, through to chapter 8. It is not a coincidence that the very first tool described in the “tools” segment of the book happens to be “auditing”. A variety of tools including the EIA, LCA, EMS, and inventorization are customarily used within industry and by the community to enable appropriate pro-environment choices while manufacturing, consuming, and disposing industrial products. In almost all such programmes, during the phase of investigation, the tool of “auditing” is initially employed in conjunction with the other tools (some or all – as the case may be). As discussed in earlier chapters, the Indian policy and legislative framework has a basis of systems understanding and the integrated approach has been recommended in production, consumption, and management of environment. The locus standi for the integrated approach stems from the directive principles and fundamental duties articulated in the Constitution of India, which expects the executive and citizens to endeavor to protect and improve the natural environment. Clearly, how could one ascertain protection and improvement unless one takes stock of existing practice of production, consumption, and management of resources? In other words, “auditing” environmental practices within industry or community becomes the first step towards sustainable management. It is realized lately that the auditing activity also makes sense from a cost-benefit point of view. There is a strong possibility that audit will suggest interventions that will not only save environment, but also save money and resources! In this chapter, the process of carrying out environmental audits, that can complement waste audits, applying the principles of cleaner production (CP)
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assessment through an integration of pollution prevention and waste minimization goals will be substantiated with examples. The implications of the cleaner

production strategy and mechanisms for capacity building that will enable sustain the practice; particularly considering the Indian context will be discussed. Also, the associated benefits relating to improved safety and improved indoor quality issues, improvement in product quality and resultant economic advantages, reduced cost of effluent treatment and maintenance of waste treatment facility will be highlighted. The most important benefit pertaining to the ability to lay the

foundations for a comprehensive management information system, that will guide decision-making process, will be emphasized in the following sections.

5.1

SIGNIFICANCE

OF

ENVIRONMENTAL A UDIT

AS A

T OOL

Manufacturing operations are the main source of industrial waste. Efficiencies of conversion, separation, and purification of chemicals and materials or efficiency of energy consumption in any complex process can never be 100%. As a result, wastes comprised of unutilized raw materials, impurities in raw materials, products, by-products and low-grade energy are released. In addition to the process related waste, rejected raw materials or products are other source of waste. Wastes are multi-media and multi-source in nature. Multi-media imply releases in different

forms viz., in terms of air emissions, water effluent or solid wastes. Multi-source refers to a number of sources of waste generation from the process at various stages. The environmental impact of wastes produced by industries around the globe has certainly created an increasing concern to environmentalists, industrialists, and especially the general public. Therefore, reducing waste at the sources in their respective forms is thus an integrated preventive approach and not merely an external add-on, as in the waste treatment approach which is the so-called 'End of Pipe' approach. Further to this, waste minimization essentially requires a rational and an integrated approach while using raw materials and energy in a production cycle. Hence, the production and consumption of both raw materials, and secondary material resources must be incorporated in the cycle so that any impact on environment
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does not disturb its normal function.

While there are several definitions of

environmental audit, the definition given by the CPCB has been quoted in Box 5.1. It must be remembered here that manufacturing goods and chemicals is not the only source of waste in a given industrial ecosystem. In fact a lot of waste also originates from consumption as well as disposal of the goods and chemicals. We should not forget that any economy perpetuates through the well-known cycle of production and consumption. The wheels within this cycle are of jobs and

opportunities for the individuals who get involved in the cycle of production and consumption and get rewarded with either profit or / and wages. As stated in Chapter 4, there are different kinds of “systems”. What should be included in audit-exercise depends on what is the “system” subjected to auditing. In this chapter, a great deal of emphasis is laid on industrial audits. There are two reasons for this choice. First, environmental audit is a legal requirement in India. Therefore, every process industry undertakes this exercise every year. It is for their benefit that we are describing industrial auditing in detail. Second, it is easier to understand principles and procedures of auditing relatively easily in the context of an industrial operation. The same principles essentially are utilized with

appropriate adaptations in audits of larger systems; however recognizing the fact that they are more complex and call for systematic integrated thinking. In recognition of the fact that auditing of a given industrial ecosystem must address all the stages of manufacturing, consuming, and disposing industrial products, separate discussion has been included in this book in chapters 14 and 15, wherein the issues associated with “intelligent and sustainable consumption” as well as operationalization of the so-called “Extended Producer Responsibility” have been dealt with. Finally, the Integrated Policy for Production and Consumption has been recommended for India (Chapter 17).

5.2

WHY DIFFERENT AUDITS?

In recent times the economic position of industries is apparently deteriorating due to the increasing costs of raw materials and labor, in addition to pressures of global competition and increasing environmental awareness, compelling better

compliance. Industries have to make drastic efforts to improve the situation and to
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There has been a change in this concept. unless recovered. raw materials are used in excess of the stoichiometric requirements because of the limitations on practically achievable operational efficiencies and the raw materials’ purity. Many a times. wherein all the wastes are carried to a common facility for treatment. Therefore the tendency is to be dependent on pollution control devices and then dispose the waste. liquid and solid phases. Should gaps in compliance with the regulatory requirements become obvious. which form hidden liabilities. Waste generation may vary on an hourly. In this growing complexity of problems. The management should be able to periodically review the environmental practices of the company to formulate/modify the company’s environmental policy accordingly. waste minimization and cleaner production have gained significant importance in recent years. daily and seasonal basis. Wastes from an industry include non-product discharges in gaseous. especially in case of the multiplicity of products manufactured in any given premises. In the industries. It is important to find out whether an industry is complying with environmental standards and other regulatory requirements. End-of-the-pipe waste treatment techniques.maintain production while simultaneously improving resource management and minimizing pollutants. the top management of a company or an industry may not be aware of the factual situation of their industry from an environmental angle. These excess usages of raw materials. the regulatory bodies could be apprised of these action plans and time obtained for implementation. Such unknown facts. It is also essential to periodically monitor this aspect. to the effect that. Environmental Audit Chapter 5 Page 4 . The wastewater characteristics also widely vary from stream to stream discharged from various unit operations of a particular product. especially the chemical industries. Thus the regulatory risk could be overcome and effective steps be taken for pollution control. at-source reduction. find their way to environment causing pollution. more often than not expose an industry to regulatory risks. determine the gaps and develop action plans for implementation within a reasonable time frame keeping in view the financial and other considerations of a company. the concept of waste prevention and reduction can prove to be quite effective. are proving to be ineffective and uneconomical due to the complexity of problems associated with the quantity and characteristics of wastes.

the society and the nation at large. Conventionally there are various types of audits that are carried out in the industries. pollution prevention audit. The environmental audit helps in pollution control. The objectives of environmental audit in an industry are to: Environmental Audit Chapter 5 Page 5 . total risk environmental audit. environmental management systems audit and toxics use reduction audit. The benefits of environmental audit are given in Box 5. or else the audit procedure will be subject to varying interpretations which may yield and contribute to differences in approach thereby influencing the end results. and for ‘liaison’ externally with the public and regulatory bodies. green audit. in order to reinforce confidence in them. The different types of audits in a industry can be: waste minimization audit. safety and health and conservation of natural resources and hence its overall objective can be stated as achieving sustainable development.3 PROTOCOLS AND PROCEDURES The following section on protocols and procedures of auditing has been taken verbatim from the CPCB publication entitled "Guidelines for Environmental Audit" [CPCB. respectively.1 shows the different types of environmental auditing.It is also essential that the management of a company should have a clear picture of ‘attitudes’ and ‘technical capabilities’ of their organisational set-up for protecting environment. Environmental auditing has far reaching benefits for the industry. which primarily depend on the objectives of the audit. Figure 5.2. Figure 5. and their social obligations related to environment so as to decide on the future mode of action. However for conducting environmental audit. pollution control status. Environmental auditing can be viewed as a ‘management tool’ internally. 1993]. 5. eco audit. The main objective of the environmental audit is to minimize environmental pollution and maximize economic benefits. objectives are to be defined clearly. improved production.2 and Figure 5. Public and specially the shareholders are to be made aware of the environmental status of the company.3 give step-by-step methodology recommended by CDG-SEAPO and United Nations Environment Programme and United Nations Industrial Development Organization.

Environmental Audit Chapter 5 Page 6 . vi) verify compliance with the standards and conditions prescribed by the regulatory bodies under the Water Act. iv) determine the performance of the existing waste treatment/control systems so as to modify or install additional or alternative control equipment accordingly. quantities and characteristics. their sources. v) determine the impact on the surrounding environment (groundwater. and recovery and recycling of wastes. if necessary. sensitive zone. ‘attitudinal’ view point and training. quantities and characteristics. stream.1 Audit Procedure The audit procedure broadly includes the following:  Pre-audit activities. iii) identify the possibilities of waste minimization.) due to the disposal of wastewater. emissions and solid wastes from the industry and accordingly identify suitable preventive measures. etc. agricultural area. residential area. and vii) check the effectiveness of (a) organisational set-up of the industry for decision-making and environmental management with special reference to their ‘technical’ view point.i) determine the mass balance of various materials used and the performance of various process equipment so as to identify usage of materials in excess than required. 5. their sources. and (b) environmental policy of the Company. the Air Act and the Environmental (Protection) Act. (b) determine the emissions. ii) (a) identify the areas of water usage and wastewater generation and determine the characteristics of wastewater. and (c) determine the solid wastes and hazardous wastes generated.3. to review the conversion efficiencies of process equipment and accordingly fix up norms for equipment/operation performance and minimization of the wastes.

Environmental Audit Chapter 5 Page 7 . climatic conditions. The purpose and objectives of the audit and how beneficial it would be for the industry should be made clear. 1993]. and organisational set-up and policies of the Company for environmental management. The following section discusses the procedure in detail. gaseous emissions. Resources such as the sampling and monitoring equipment and laboratory facilities for analysis should be checked for their availability at site or else arrangements should be made to access them through external sources such as private/government laboratories. or as a loan from other industries. This prior intimation to the industry helps convince the senior management and staff at various levels.4. The staff should not feel that the audit would lead to surfacing of problems and hence they would be subject to criticism by the management. wastewater generation and disposal. The information to be documented include location of the industry with surrounding land uses. Pre-audit Activities Preliminary information Pre-audit activities include various preparatory tasks. Thereafter it is important to organize an audit team and resources. of the purpose of audit and ensures their cooperation to the audit team. This would also increase employees’ awareness towards waste reduction and promote their inputs and support for the audit. The preliminary information received on the industry should be reviewed to identify main areas of concern. raw materials used. details on water utilisation. The details of these activities and the entire audit procedure are depicted in Figure 5. product manufactured. and  Post-audit activities. A typical questionnaire is given in Annexure II of the guidelines document of the CPCB [CPCB. and allocate specific tasks to team members. solid waste/hazardous waste. The programme of visit should then be intimated to the industry mentioning that the environmental audit should be considered more as a supporter than as a foe. Activities at the site.

This calls for the inclusion of environmental specialists. relevant waste control technologies. quality control/laboratory. The audit may take 3-10 days depending on the industry. The effectiveness of audit is a direct result of the qualifications. The number of people may vary from 4 to 8 depending on the size and complexity of the facility being audited. It is important to have well-defined and systematic procedures. laboratory/quality control. Interviews should be held with various cross-sections of the staff engaged in production. They should have the capability to examine. The team should include employees from production. environment management. The team should be sufficiently self contained and technically empowered to provide an independent view. monitoring of characteristics. without obligations to the Supervisor. technical staff for monitoring and analysis of waste samples and the ambient environment. holding discussions with the management and finally preparing the draft report. Based on a fair idea about the manufacturing process. The members should be so chosen that they would not hesitate to criticize. question. confidence. pollution control operations. etc . R&D. Activities at Site The activities at site include material balancing. evaluating performance of pollution control equipment/system. which are known and understood by all concerned. The management should be provided with a realistic assessment of environmental performance. Sometimes it is advantageous to include members from the headquarters of the industry. sample and analyze waste and interpret data. The team should understand regulatory requirements. identification of waste flows.Audit Team The audit team should be carefully selected to cover aspects of the audit. reconnaissance surveys should be made to become familiar with the layout of the plant and process operations and to understand possible impact on the surrounding Environmental Audit Chapter 5 Page 8 . their operations and process. training and proficiency of the personnel who conduct audits. so as to understand different operational mechanisms. assessing environmental quality. R & D.

mostly in a different form. dissociation. catalyst. Material Balance The entire manufacturing process of each product should be drawn into a process flow sheet representing various unit operations as blocks. the sources and quantities of generation of wastewater. wastewater and solid waste generation. Various activities to be carried out at site are discussed in detail in the following paragraphs.7 Development of Waste Flow Sheets From the material balance. The waste pretreatment. state or composition emerge.6 The quantities of inputs and outputs at each unit operation should be worked out for the entire process and data incorporated in the process flow sheet. wastewater. Also. The water balance sheet. leaks. water consumption. etc. and gaseous emissions should be worked out for each product manufactured. visits to the process plants may disclose many other discharge points due to overflows. From these flow sheets. perusal of the records of the company and the reconnaissance survey will help in developing these flow sheets. preconcentration and purification. washings. toxification. water/air. adduct formation. data sheets incorporating the raw material requirement.5. The production staff should be consulted as these people are likely to know about waste discharge points and about unplanned waste generations such as spills. A typical process flow diagram of the production of monocrotophorous pesticide is given in Figure 5. emissions. concentration. chlorination of adduct. A typical unit operation with inputs of raw materials. final treatment and disposal path should be identified.environment. A unit operation is a process where chosen materials are taken as inputs a function occurs on them and materials as output. spills and other material handing practices which are not accounted and Environmental Audit Chapter 5 Page 9 . gaseous emissions and solid waste should be identified. This process includes the unit operations of dehydration. solid waste and reusable waste in another operation is schematically shown in Figure 5. power and recycled material and outputs of products and by-products. Discussions with the staff. which shows areas of water usage and wastewater generation and their quantities is depicted in Figure 5.

the performances of the treatment facilities are to be monitored so as to check their efficiencies and to modify or install additional equipment/facility.. More than one such set of data can help generate more realistic results. agricultural etc. The surrounding environment viz. instruction. It should also cover at least one full cycle of operations. ‘Grab’ sampling means collection of sample in one pick while composite sampling requires collection of sample continuously or at predetermined frequency (1-hr. groundwater. usage of sign boards. should be taken note of and recorded. 2hr. drainage system. material handling and storage. handling of scrap and wastes. colour codes etc. The quantities and sources should be accordingly finalized and a waste flow sheet prepared. Sampling points should be identified and monitoring network established to address the above objectives. etc ) and compositing it in proportion to the flow rate observed at each sampling time. Parameters to be analyzed should be determined from the material balances of the wastes generated. Monitoring The characteristics of the wastes as generated from the sources are important to understand its use for recycle. The frequency of sampling should be fixed so as to cover variations in characteristics on an hourly and daily basis. Field Observations The entire plant should be inspected thoroughly. Samples collected should be of ‘grab’ type where characteristics do not vary significantly and of ‘composite’ type where characteristics fluctuate. streams. The method of analysis of samples should be done as per a standard procedure and by trained analysts. Also. land uses including residential. lapses/negligence in operations and attitude of operations in process and waste treatment facilities.recorded. The ‘attitude’ and ‘technical capability’ of various staff including senior management should be observed. recovery or treatment. soil. These are quite is very critical in achieving the goal of safer Environmental Audit Chapter 5 Page 10 .. safety aspects. if necessary. and ambient air quality should be monitored to determine the impact due to the industry. Aspects of site layout.

environment.3. A comparison of these requirements with the actually used in the industry gives an indication of excess usage of various raw materials. 5. The participation of the management and their acceptance of various observations and recommendations make the task of implementation meaningful. Training requirements can also be assessed based on these observations. These excesses may be presumed to be finding their way to air. The unit operations should be checked to find out the cause of excess usage of the materials and accordingly modifications made. reasons for the same should be diagnosed. water and soil thus causing pollution. a draft report should be prepared with findings and some recommendations for improvement. If the treated wastewater. Draft Report After completing the above-mentioned activities including determining material balance. The management should put forward their views. identifying waste flow. it is important to reduce these excesses. The environment manager thus can have a control over production as well as wastes generation too. The draft report should be presented to the senior management and various points should be thoroughly discussed. gaseous emissions and solid wastes do not conform to the standards prescribed by the pollution control board. Norms should then be fixed for performance of each of the unit operations. Evaluation of Waste Treatment Facilities Performance of various pretreatment and final treatment facilities should be evaluated based on the analysis reports. monitoring and analysis of various samples and field observations. and for wastes generated from each of them. Hence. Environmental Audit Chapter 5 Page 11 . The staffs responsible for production and environment are expected to scrupulously adhere to the norms.2 Post Audit Activities Synthesis of Data The requirement of various raw materials according to the mass balance of chemical equation involved in the manufacture of a product is called stoichiometric requirement.

Recommendations for the best practicable waste management systems should be formulated. alkaline. Many a times. which in reality render biological treatment ineffective. the specialist should also evolve norms for optimal utilization of resources and performance of various pollution control systems. The wastewater of similar nature could be combined and common treatment facilities provided. Environmental Audit Chapter 5 Page 12 . The members of this division and the operators of the treatment facilities should be well-trained. and pretreatment units viz. Toxic wastes should be detoxified before being treated in biological treatment plants. The designed criteria and the actual operating conditions of various treatment units should be compared and norms fixed for the operation of these units. 1993]. Similarly. neutralisation. it is observed that inorganic wastes and non-biodegradable wastes are treated in biological treatment plants. and wastewater and gaseous emissions are given in Annexure IV of the guidelines document of the CPCB [CPCB. the problems related to gaseous emissions and solid waste generation may be identified. Highly toxic wastes may be isolated and incinerated. The guidelines for environmentally safe layout are given in Annexure III and guidelines for reduction of raw materials losses.From the individual streams of wastewater. easily biodegradable. organic. not easily biodegradable and toxic streams. The wastewater should be segregated based on the characteristics. recyclable and recoverable materials should be identified and provisions made for the same. oil separator. detoxification etc . The environment division of the industry should have an environment specialist to look into matters related to pollution control and evolve norms for resource conservation/waste minimization vis-à-vis process control. Besides. at the source so as to minimise cost of final treatment. The rate of wastewater flow and polluted loads to the effluent treatment plant (ETP) should be properly regulated to keep off shock loads that affect microorganisms. All the ‘avoidable’ wastes should be completely controlled and only the ‘unavoidable’ allowed for discharge. should be provided. such as inorganic. wherever required. This would provide for efficiency and economy. acidic.

e. Priorities should be fixed and action plans with time-frame should be formulated. quality control/laboratory. is too high for investment at one instance. be sent to the top management for comments so as to include further modifications. and distillery activities. If the annual burden. This case study is pertaining to the distillery portion only and hereafter the industry will be referred to as Distillery for brevity. Follow-up Actions Follow-up actions should be under taken to check the progress of implementation of recommendations. should be implemented in phases. the distillery portion of the agro-industrial business house has made name in the national and international market because of their liquors and alcoholic beverages.To oversee the implementation of measures for pollution control and the overall management of environment. Environmental Audit Chapter 5 Page 13 . if necessary. 5. the annualized capital cost of the pollution control measures and their operating cost. and an environment specialist.4 C ASE STUDY: WATER BUDGETING FOR A DISTILLERY 5. is a prestigious group of industries in Krishipur engaged in sugar-cane crushing. The Environment Division of the industry should meet the heads of other divisions periodically to review the progress.1 About the Industry M/s Bharat Sugar Factories and Distilleries Ltd. these recommendations. Final Report The various aspects discussed above should be compiled and a final report prepared along with recommendations. Unlike many other sugar factories. i. there should be a peer group-comprising members from production. The final report may. Action Plans The recommendations should include measures for best practicable environmental management. crystallizing.4. for the implementation of all the recommendations.

and 2. Table 5. The Distillery holds consent from the State Pollution Control Board (SPCB) to manufacture four products (Table 5. Environmental Audit Chapter 5 Page 14 . scrubber water. the expansion be due to modernization. decrease or maintain at par the existing pollution load on environment.1): 5. in the field of alcohol blends and alcohol based chemicals. The purpose of this investigation was to examine.4. At the same time. steam. Krishipur. refrigeration. effluent treatment plant etc . At the site in SIDC Industrial Estate.2 shows the raw material consumption in the Distillery for both the products. The processes involved are given in Table 5. capacity utilization or change in product mix. by such expansion in fact. Due to globalization and varying market forces.2 Existing Process and Raw Materials Table 5. The industry soon attained excellent shape. this Industry (Distillery) was first established in 1973 to cater to the needs of independent India. The Distillery has provided treatment facilities. The industry is located in the basin of river Sujala. power. and the products were acclaimed superior in quality. such as water. The River Zone Policy declared by the state government allows expansion of existing industries listed as Red. the said industry is required to adjust their production schedule. and partly by changing the product mix to a certain extent. since the beginning when the first modern environmental statute was promulgated in the state.Chemical manufacturing needs a number of utilities. capacity utilization. the pollution load should decrease. Various unit operations and unit processes are involved in the production of these foodchemicals. the corporate office of the industry is environmentally conscious.3 shows different utilities in the Distillery. whether such expansion would increase. This implies expansion of the Distillery partly by way of modernization. at existing site in the two Km belt from the River provided two conditions are met. ENS and Malt.The Distillery under consideration is existing and has the necessary consent. namely 1. Food .4.

Remaining 841 kLD water is obtained through various water reclamation and recycling efforts. container washing or similar stations). internal recycle. This can be achieved through a listing of process improvement opportunities. it can be seen from Figure 5. Environmental Audit Chapter 5 Page 15 .6. The comparative budget for various inputs and outputs from different consumption stations is presented in Table 5. The detailed budget of water inputs categorized as fresh and reclaimed. floor washing.5. integrated with waste minimization options. two polluted water streams are generated from a given industry namely: “Domestic Sewage” or “Process Wastewater”. This emerges out of better resource use and helps substantially improve the economic bottomline. workers in factory-colony.5 SOME C ASE EXAMPLES ENVIRONMENTAL AUDIT OF SUCCESSFUL IMPLEMENTATION OF It is important to recognize that environmental audit as a tool helps in achieving the objectives of improving productivity. This scheme could be proposed only because an integrated view was taken while planning the entire water budget. while in some. Thus.7. Thus.8 that many depleted streams have been proposed to be put together and recycle as “II-use” or “Internal Recycle”. It is interesting to note that the proposed scheme uses only 450 kLD fresh water from SIDC. The characteristic of process wastewater is high COD loads and rather difficult streams of effluents . A few case examples of successful implementation by several firms support through waste minimization circles of the National Productivity Council.g. the water need is meager. vessel washing. New Delhi have been presented in the following.some steps of the production are quite water intensive. on one hand the spent wash created after fermentation poses a great challenge for waste managers in any distillery and on the other hand a large flow of wastewater could be rather dilute (e. second use. and internal recycling at various consumption stations in the production process has been shown in Table 5. 5. As a consequence.In an industry water is used for industrial purposes. and other losses and consumption are given in Table 5. Detailed budget of water streams generated from various consumption stations in the production process categorized as inputs to biodigester. gardening-irrigation as well as for miscellaneous applications including construction and fire fighting.

the waste minimization assessment focus helped screen aluminium scrap manually and with help of magnets. Sulfanilic acid. 2002] include the following: 1. Environmental Audit Chapter 5 The above Page 16 . This enabled an improvement in the quality of aluminium melt.17 million helped generate savings of nearly Rs. Improved heat transfer efficiency was also achieved in the process [Gireesh. 3. significantly reduced scale formation and costs associated with frequent repairs. An initial investment of approximately Rs. Cascading rinses and continuous removal of floating oils and greases from degreasing tanks helps avoid contamination of downstream baths.16 million within a year’s period [Shah. Reduction of losses of either unconverted raw materials or of isomers generated through improper reactions as part of waste streams was successfully achieved in this case. thereby reducing the treatment costs. In a firm manufacturing vinyl sulfone the process review helped identify 66 potential improvements. 2002]. contributing to a reduction of approximately 20 Kg impurities per day. 2. Appropriate energy auditing helped reduce energy losses through the adoption of sandwich type clamping of bus bars to electroplating baths replacing the traditionally used “nut & bolt” joints. which was initially not retrieved from the mother liquor was subsequently recovered. It can be seen from the above that avoidable waste streams in the form of contamination of raw materials and heat transfer retardants was categorically addressed. 2002]. called for additional before they could be implemented. resulting in the removal of iron particles and stones. This helped in yielding better quality products. temperature monitoring devices and process controls were introduced.In aluminium utensil manufacturing units. Some interesting waste minimization options identified in electroplating sector [Mahulkar. Improved housekeeping through insulated steel distribution system. Choking of burners was This intervention eliminated through filtration of furnace oil used for melting. 36 of these were found to be technically and economically feasible. Several of these however. These improvements essentially relate to avoidable wastes with a significant bearing on environmental performance as part of comprehensive environmental audit. Low concentration cyanide bath for zinc plating reduces chemical losses and pollutant concentration in wastewater.

preempting environmental protection and therefore serves as a comprehensive framework for easy implementation in industry. 2001]. Significant reduction of fugitive emission levels have been achieved in stone crushing units apart from optimizing water consumption [Ravishankar. The overall waste minimization potential that was realized with reference to the nature of the streams identified ranged from Rs. Significant waste reduction and productivity enhancement has also been identified in the cotton hosiery processing operations [Kalathiyappan. Based on the above. 2001]. through a concomitant improvement in fermentation efficiencies.three interventions that can be easily implemented also emerged out of employing the waste stream identification route as part of environmental audit emphasizing its versatility as a tool. Between 1994 and 1999. helped achieve nearly 40% reduction of spent wash quantity. which otherwise contributes to environmental loads. 2001]. High TDS and other cocktail of wastes emerge out of printing operations.to 5000/.per tonne of fabric processes through appropriate reduction in chemicals and dyestuff in the process. The auditing framework helped identify some of the most important environmentally significant hot alkaline dark colored wastewater streams emerge out of the scouring and mercerizing processes. The bleaching stage generates acidic discharges. Modification of the process. 2000]. supported by greater efficiency of raw material conversions [Kumar and Visvanathan.2000/. The importance of this tool cannot be overemphasized specially considering the fact that substantial gains in terms of reduced environmental loads can be achieved Environmental Audit Chapter 5 Page 17 . Foamy wastes tend to emerge from finishing stages. Patil [2000] reports on the significance of identifying methods of treatment and disposal of distillery spent wash. Similar economic benefits on account of reducing water consumption and separation of waste streams for suitable treatment and recovery of materials have also been reported in the sago and tapioca processing sectors [Nair. it becomes evident that the framework of environment audit serves as a very useful tool. 54 pulp and paper mills undertook assessment of improvement opportunities and in the process identified more than 1000 options for improvement in environmental performance related to reduction in water consumption and energy losses.

Environmental Audit Chapter 5 Page 18 .specially when a large cluster of firms can device interventions in relation to environmentally significant waste streams that emanate out of the processes.

assessing compliance with regulatory requirements. and      . unravels surprises and hidden liabilities due to which regulatory risk and exposure to litigation can be reduced. Foundation Books Pvt. and identifies the operations of poor performance.” CPCB (1993) Box 5.placing environmental information in the public domain. (2005).facilitating control of environmental practices by a company’s management. “Preventive Environmental Management – An Indian Perspective”. . and Gopichandran. ensures independent verification.Reference: Asolekar. Ltd. New Delhi (the Indian associate of Cambridge University Press. R. .2   Benefits of Environmental Audit determines how well the process systems and pollution control systems are performing. documented.. and .waste prevention and reduction. periodic and objective evaluation of how well the management systems are performing with the aim of: . helps in understanding the technical capabilities and attitude of the environmental organisation in a Company. policies and responsibilities. increases awareness of environmental requirements. provides up-to-date environmental data for use in plant modification. S.1 Definition of Environmental Audit “Environmental auditing is a management tool comprising a systematic. emergencies etc. identifies matters needing attention and provides timely warning to management on potential future problems. identifies potential cost savings which can be accrued through reduction in raw material consumption by way of waste minimization. R. and adoption of recycle/recovery/reduction in pollution load. UK) Box 5.

with the Company’s policy and with the environmental standards. and assists in complying with local. regional and national laws and regulations. helps to safeguard environment. CPCB [1993] .

Figure 5.8 The proposed scheme for integrated management of water streams to enhance second-use and internal recycle .

and the growth rate of chemical industry is apparently on the rise in India. In this chapter. Preventive interventions and implementation of pro-environmental initiatives and programmes have been included in this section because all of these constitute the domain of PEM. A case study has been presented to illustrate the essential steps involved in identification of potential CP interventions in a pesticide industry. and public at large have realised that problems resulting from process industries cannot be managed economically by the so-called “end-of-pipe” treatment (see Box 9.1). India happens to be among the countries in the forefront of chemical industry in the world. S. Identification of Potential Interventions Chapter 9 Page 1 . Most of the major industrial accidents and pollution. R. As one can guess. It will be useful to recall that the interventions could be at various levels. Ltd. (2005). It is in this context. The regulators or governments may impose them or they may be undertaken voluntarily by industry at the site of manufacturing or consumption. PEM is not the activity to be undertaken exclusively by the environmental engineer or any other single designated authority from senior level of management or by the shop-floor work force. UK) We begin here the discussion on interventions and programmes for PEM. Foundation Books Pvt. too. which will run from this chapter to chapter 16. There is a considerable interest in minimisation of wastes while manufacturing chemicals and engineering goods using cleaner production techniques. we first provide an overview of the concepts and practice of CP activities.Chapter 9 IDENTIFICATION OF POTENTIAL INTERVENTIONS Reference: Asolekar. and Gopichandran.. we have addressed cleaner production (CP) interventions of several kinds. are generally attributed to chemical industries. New Delhi (the Indian associate of Cambridge University Press. The manufacturers. regulatory agencies. R. “Preventive Environmental Management – An Indian Perspective”.

With new processes that cause less pollution. The UNIDO defined the complex of cleaner production using the method of correlates (see Box 9. From an economic standpoint. it helps to improve productivity and in many instances the quality of the products. apart from reducing pollution. are consumed faster than they can be regenerated. Identification of Potential Interventions Chapter 9 Page 2 . leading to better use of raw materials. and enables a firm to become more competitive.1 WHAT IS CLEANER PRODUCTION? With current trends in population growth and industrialization. In sum. while meeting the environmental expectation by adopting cleaner technologies. This requires the development and use of environmentally sound technologies. production processes. It is with this perspective. the United Nations Environmental Program (UNEP) launched the Cleaner Production Program in 1990. If sustainable development is to be achieved. Adoption of cleaner production approach has led to an increase in profit margins by as much as 40%. Natural resources. and services have to be reoriented towards new patterns in order to alleviate environmental stresses and bring better industrial productivity. It attempts to simultaneously conserve the input resources by increasing the conversion efficiencies of production. investments become productive and hence more readily accepted by industries. The other advantage of cleaner production.Finally. “Cleaner Technologies” (CT) is a term used to describe production technologies and strategies that contribute to the closure of the production-process life cycle.2). the CP approach differs from the conventional EOP approach. products. which prevent pollution and make efficient use of raw materials and produce goods as well as services (see Figure 9. This involves alternate processes and process integrated recycling. an algorithm for prioritizing options for pollution prevention has been presented. is that it provides greater control over the process involved and thus reduces the risk of accident or a breakdown. too. cleaner production represents the only recourse for all manufacturing industries.1). as stated earlier. waste byproduct utilization and environment friendly product specifications. 9. wastes and pollutants are being released faster into the environment than the capacity of ecosystems to mobilize them. With stringent regulation by government.

Now the question arises: where does one draw boundaries of the system? This can be answered only when one is clear about the objectives of the investigation. If one wants to investigate environmental effectiveness of the production practices in a given industry then the appropriate system of reference is group C. followed by consmption Group B: Production of raw materials and intermediates Group C: Production of finished goods in a process industry Group D: Consumption by community Energy and materials from A and B are feed to C. If the system under investigation is integrated from C to A and B (upstream integration) or C to D (downstream integration) or all of A to D. 2000].e. which produces finished goods.Cleaner production is thus an integrated approach and not add-on as in the case of EOP treatment. If the investigation centers around group C (i. as depicted in Figure 9. wherein relatively far less quantities of wastes are generated and the corresponding cost of waste treatment gets substantially reduced. Thus. If one wants to investigate environmental effectiveness of the production practices of the Identification of Potential Interventions Chapter 9 Page 3 By and large there could be four groups of activities . If the investigation centers around group D then the term like cleaner consumption (CC) would apply.2. then such terms as cleaner production and consumption (CP&C) would apply. The terms like CP or CT or waste minimization (WM) or recycling and recovery (R&R) or pollution prevention (PP) or PEM are some examples [Jorgensen. the overall resource utilization factor improves. When and where do we apply them? The simplest (and probably and the most accurate) answer is: all these terminologies are indeed interchangeable! Let us take a perspective of the entire system of industrial production and urban consumption – say production and consumption of an industrial product. One might wonder about the variety of terminology and concepts in PEM – often interchangeably used. leading to more profitability and competitiveness. namely: Group A: Generation of power and energy. This is in fact a prevention approach. system subjected to the study) then the terms like CP would apply.

then the intervention would be called as R&R. Similarly. if the primary objective of investigation happens to be recycling of water or recovery of solvent in a given industry. EIA. If the objective happens to be merely waste minimization then obviously the intervention will be called as WM. the extent to which data collection and interpretation would be done shall depend on the objectives of the investigation.e.2. source reduction alleviates the problems associated with handling and disposal of wastes. inventories. Good Operating Practices Identification of Potential Interventions Chapter 9 Page 4 . If the objective of investigation is to identify preventive environmental strategies pertaining to the system C+A+B. In sum. It is therefore the most desirable option for Cleaner Production (CP). upstream and downstream integration of entire system (A+B+C+D) is undertaken then it would be the EPRintervention (read chapter 15). both.1 Waste Minimization The first step in any waste minimisation program is the reduction of wastes at source. Where does this discussion lead us? The state of the art in PEM-related investigations and actions suggests that the onus is on the investigator to identify the system boundaries for investigation on one hand and define the objectives of the investigation on the other. it must be kept in mind that similar set of tools (namely: audit. 1. 9. Because little or no waste is generated. However.finished goods as well as integrate the environmental issues related to raw materials and energy inputs then the system that can apply would be groups C+A+B. then the term PEM will be utilized. Source Reduction  Recycling and Recovery 9. and recognize the fact that the system definition and the objectives of investigation are dynamically related to each other. It includes. If an analogous PEM study is undertaken where. LCA.2 C LEANER PRODUCTION TECHNIQUES There are two principal methods for achieving cleaner production:  Waste Minimization i. the terminology basically suggests the primary intention of the investigator. While the tools are not exclusive. and EMS) will be applied in all kinds of investigations.

2. Technology Changes 3. Input Material Change, and 4. Product Improvement.

Good Operating Practices
Operating practices include procedural, administrative and institutional measures that a company can use to reduce waste. Many of these measures have been used for decades by successful business for efficiency improvements and sound management practices. They can often be implemented at little cost and have high returns on investment. Good operating practices include;         Management and Personnel Involvement, Material Handling and Inventory Practices, Loss Prevention, Waste Segregation, Production Scheduling, Complete Accounting Practices, Good House Keeping, and, Preventive Maintenance.

Management and personnel involvement includes employee training, incentives and bonuses, and other programs, which encourage employees to conscientiously strive to reduce waste. For example United Phosphorous Limited has a Zero

Investment Improvement (ZII) program, as part of which regular meetings are held, to get feed back from the employees on waste minimisation. In order to promote active participation of the employees, the management awards special prizes for the persons who come up with the best suggestions. Material Handling and Inventory Practices include programs to reduce loss of input materials due to improper handling, expired shelf life, or improper storage conditions. For example, buying large quantity of materials just because the unit cost is lower will not save money if a majority of the material sits on the shelf and dries out or become unstable because of chemical decomposition.
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exceeding an expiration date, it is also useful to rotate stock periodically. Fresh material can go to the back of the shelf, with the oldest moved to the front. Loss Prevention minimizes wastes by such means as avoiding leaks and spills from equipment and preventing evaporation by keeping solvent containers closed tight. Waste Segregation practices reduce the volume of hazardous wastes by preventing the mixing of hazardous and non-hazardous waste. By judicious production

scheduling of batch runs, the frequency of equipment cleaning and the resulting waste can be reduced. Complete Accounting Practices involve allocating waste treatment and disposal costs directly to the departments or groups that generate waste, rather than charging these costs to general company overhead accounts. In doing so, the departments or groups that generate the waste become more aware of their treatment and disposal practices, thus providing a financial incentive to minimise waste. Good House Keeping Practices improve safety, delay damage to equipment, reduces breakdowns, and increases efficiency. It will also assist in discovering leaks and spills when they first occur. Preventive maintenance will also contribute greatly to waste reduction. If a tool or piece of equipment is maintained properly, it will last longer and provide more productive use of the process for which it was designed.

Technology Changes
Technology changes are oriented towards industrial process and equipment modifications, which will reduce waste primarily in a production setting. Technology changes may range from minor improvements that can be implemented in a matter of days at low cost to new processes with start up costs that require large capital. These changes include;     Alteration of production processes, Changes in equipment, Use of Catalyst, and, Membrane separation.
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Alteration of production process plays a very important role in pollution prevention. One good example is the Solvay process for the manufacture of soda ash. In the old process, ammonia was used, recovered and recycled while the calcium chloride solution, which was generated in the process, was discharged in the waste stream. However, in the modified version of Solvay process, ammonia is used as a raw material along with sodium chloride, and ammonium chloride is obtained as a byproduct along with soda ash. Ammonium chloride so obtained is marketed as a fertiliser. The quantity of wastes may be reduced by installing more efficient equipment or by modifying existing equipment to take advantage of better production techniques. For example, steam ejectors with barometric condensers, known for the copious amount of waste stream they generate, could be replaced by vacuum pump and surface condenser systems. Vapour emissions from storage tanks could be

reduced by having a vapour recovery system, or a flexible floating roof with a seal covering the tank. Catalysts play a major role in waste minimisation. An apt example for this would be the chlorohydrin process for producing ethylene. In the chlorohydrin process,

calcium chloride is a major waste that is formed. This problem was solved in the silver catalysed process, where direct oxidation of ethylene to ethyleneoxide takes place with carbon dioxide and water being the by-products. Catalysts have played a major role in reducing air emissions. Some examples include; the replacement of old Chambers process by contact process, and the catalytic synthesis of ammonia from nitrogen and hydrogen. Catalyst also plays a major role in hydro processing, isomerisation, catalytic cracking, and platforming. Use of membrane separation technologies could lead to optimal resource use and recovery. Membrane separation techniques are used widely for desalination,

cleaning of industrial waste, removal of salt from the effluents, recovery of valuable component from waste stream, concentration, purification and fractionating macro molecular solutions, and recycling of water. With more stringent regulations on effluent standards, a membrane separation technology is bound to find more commercial outlets in future.

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Some of the Product Improvements Product improvements are performed with the intent of reducing waste resulting from a product’s use. it helps in minimizing human errors. Some examples of product improvement are. material substitution examples are:  Linear alkylbenzenesulphonate which is biodegradable can be used instead of branched dodecylbenzenesulphonate.  Gasoline is one product that has undergone many reformulations to reduce fugitive emissions as well as emissions from combustion. On the other hand. such as some metals and polymers can be substituted in the product itself. Input material change includes material purification and material substitution. Input Material Changes Input material changes accomplish waste reduction by reducing or eliminating hazardous materials.  Dichromates. which enter a process.  Switching over from organic based cleaning system to water based cleaning system. changes in input material can help to avoid generation of hazardous wastes within a process. Identification of Potential Interventions Chapter 9 Page 8 . which are used as corrosion inhibitors in cooling water create problem of pollution.  Use of water based paints instead of solvent based paints. materials which do not require coating.  Replacement of benzidine based dyes with non-carcinogenic and nonbenzidine dyes. is an important technique for waste minimisation. In many cases. Product improvement includes product substitution and product reformulation. Also. possibilities of spillage or production of off specification materials could be eliminated by process automation. by automatically adjusting process parameters. For example.Process automation. These can be substituted by less polluting anti corrosive agents.

In some cases the waste may itself be transferred to another company for use as a raw material in its manufacturing process.9.2 Recycling and Recovery Recycling and Recovery (R&R) includes both reuse and reclamation. respectively. Reclamation is yet another form of R&R.2. the following initiatives have been taken recently to stress the government’s interest and concern for resource conservation.3 C HANGES IN INDIAN INDUSTRIES The Ministry of Environment and Forest (MoEF).  During the manufacture of phosphorous. 1. Establishment of Clean Technology Cell in the MoEF. New Delhi Govt. Apart from broadening the scope of legislation. and reused in the process. valuable materials are recovered from wastes. R&R via reuse involves either returning a waste material to the originating process as a substitute of input material. Reclamation technique differs from the reuse techniques in that the recovered material is not used by the company but is sold to another company. has laid increasing emphasis on waste minimisation. 9. Some examples of reclamation encountered in a pesticide industry are listed below:  Calcium chloride obtained as a waste stream is fused and the fused calcium chloride is sold  Ferro phosphorous slag and silicate slag from the blast furnace producing phosphorous are sold to manufacturers of iron and cement. of India.  Carbon monoxide that is produced in the production of phosphorous is used as a fuel for running the incinerator. Some of the examples of reuse encountered in United Phosphorous Limited are listed below:  Ammonia is recovered from one of the waste streams from a plant containing substantial amount of ammonium chloride. Identification of Potential Interventions Chapter 9 Page 9 . or using it in another process as an input material. the spray liquor used for the condensation of phosphorous is recycled into the spray condenser.

1 Context In India. 9. Waste Minimisation Awards to industries. 7. rapid urbanization has tended to reduce the area under cultivation. diseases and weeds. 23% of this loss is due to insects alone. India's population may cross China's population by the year 2010. 4. increase in the water cess rates etc. 5. 3. in spite of accommodating 15% of the world's population and almost 4% of the crop area of the world [CPCB. Establishment of National Cleaner Production Centre jointly with UNEP and UNIDO. subsidy. 6. There is a vast deficit between the application rate of Identification of Potential Interventions Chapter 9 Page 10 . However. India consumes less than 2% of pesticides produced worldwide. In addition.4. The indigenous pesticide production meets only 70% of the country's requirement. Pesticides have played a major role in achieving this growth. Introduction of Environmental Statement as a requirement for industries. Production of Environmental Labelling to promote green consumerism. and research related to waste minimisation. Also. surveys.2. 8. 1986].4 AN ILLUSTRATED APPROACH FOR CLEANER PRODUCTION OF PESTICIDE ACTIVE INGREDIENT 9. Establishment of a National Clean Technology Centre with support from the World Bank for waste minimisation related information dissemination and technology transfer. Supporting training programs. Reformulation of economic incentives and disincentives for example. 9. it is estimated that 30% of the Indian crop yield is lost due to rodents. there is an ever-growing demand to increase the crop productivity to meet the need of the country’s burgeoning population. food grain production has gone up by over 150% in the past three decades while crop area increase is only by 30%. Establishment of Waste Minimisation Circles to assist small and medium industries in industrial estates. insects.

Identification of Potential Interventions Chapter 9 Page 11 . 1999].16.S. and carbamate pesticides [Sawyer. The production figure stands at 80. About 25% of the farmers in India still do not use any kind of pesticide. 1994]. the market has grown by 13% and the total sales are over 400 million US$ of which 80 million US$ are accounted by exports [Dhar. and Parkin. Manufacture of pesticides in India is growing to such an extent that India is the largest manufacturer of pesticides in the third world. 1997]. However. India happens to be an important exporter of ODM. It is estimated that 1520% of the pesticide consumed in India is imported annually [Prabhu. The corresponding figure for U. use of oxydemeton-methyl (ODM). The focus of the present Cleaner Production (CP) assessment is on ODM. been introduced in the market Although a number of biopesticides have to replace toxic synthetic pesticides.chlorinated hydrocarbons. The type of pesticides used at present can be grouped into four major categories . low mammalian toxicity and fairly rapid biodegradability. new pesticides are introduced and subsequently withdrawn with a typical life cycle of about twenty years.200 mg/m2/yr [Bami. Organophosphorous pesticides are used widely on many food crops as well as commercial and residential settings.major pesticides in India and the developed countries. the average pesticide active ingredient (PAI) application rate is 57 mg/m2/yr. The chemical composition of pesticides has changed rapidly over the past few decades. is of special importance [USEPA. Research efforts are directed towards developing chemicals with high insecticidal property. On the basis of their performance and environmental impact. In India.000 tones PAI/yr. India has to even import pesticides. Since 1984. McCarty. In the context of certain cash crops such as cotton. there is a vast potential for increase in consumption and manufacture of pesticides in India.A is 250 mg/m2/yr and for Japan is as high as 1. organophosphorous pesticides continue to claim a large share in the market owing to their proven effectiveness and economic considerations. fruits like apple and vegetables like cauliflower. 1987]. These crops are important in India too. 1997].000 tones PAI/yr. due to lack of product mix. which is an organophosphorous pesticide. organophosphorous pesticides. India has an installed capacity of 1. Clearly. synthetic pyrethroids.

the wastewater has high COD as well as TDS. 1994].2 Methodology for Cleaner Production CP assessment is classically carried out in six steps namely Getting started. The focus of present study is to develop an approach. liquid and solid wastes are produced which are potentially harmful to the environment [Rodolf. an attempt has been made to identify the focus areas for cleaner production of ODM. A number of chemical reactions are involved and a wide range of gaseous. Implementing CP solutions. CP assessment was carried out for each stage of production using the following stepwise protocol. Step 1 Process study: The sequence of activities carried out in each unit operation. minimization of downstream waste generation and alternative route for product syntheses have been elaborately discussed. Hence. In this case study. Identification of Potential Interventions Chapter 9 Page 12 . 9. including resource consumption and environmental impact related to separation and purification stages while improving product specification. this methodology was modified and a four-step methodology was developed to suit the requirement. which can be utilized for other pesticides and fine chemicals manufacturing process. 1994]. the requirements and the constraints of the product manufacture. storage and transportation are taken into consideration. present.The production of ODM is highly polluting. Clearly. Relevant available information for this product was also compiled at this stage.1.4. It is however believed that the approach presented here is illustrative in nature and can be applied for other pesticides and fine chemical manufacture. role of each reactant and necessity of each process step was clearly demarcated. Finally an effort has been made to illustrate the significance of At integrated approach for continuous improvement of product specification. Characteristics of pesticide manufacturing industry wastewater are given in Table 9. Selecting CP solutions. Cleaner production measures including raw material substitution. Sustaining CP [Chandak. There is a strong need to incorporate various aspects. modification of reactor operations. Generating CP opportunities. Analyzing process steps. The toxicity level will depend upon the solubility of pesticides in water.

1999]. reactor is maintained at this temperature for the desired Identification of Potential Interventions Chapter 9 Page 13 . Step 4 Generation of CP opportunities: CP opportunities were identified which would reduce/eliminate the source and the cause of waste generation. Details of the production process are summarized below.o-dimethyl phosphorothioate ((CH3O)2POSCH2CH2SOC2H5) and the trade name is Metasystox-R [Marshall. The significant intermediates and raw materials used for the manufacture of ODM include PCl3. The required quantity of PCl3 tank is added at a controlled flowrate by maintaining reactor temperature between 40oC to 50oC. After addition of PCl3. The IUPAC nomenclature for ODM is S-2-ethyl sulphinyl ethyl o. 1977]. It is manufactured chiefly by one particular route. Each one of the four stages is a batch process. synthesis of demeton-methyl and synthesis of oxydemeton-methyl. The production process is illustrated in Figure 9. Synthesis of chlorothioalcohol CTA is manufactured from thioalcohol and PCl3.2. The first two stages are for synthesis of intermediates and the next two stages are aimed at conducting toxification reaction followed by separation of product. ethylthioethanol and methanol [CPCB. The required quantity of thioalcohol is taken in the CTA reactor. The following sections describe each of the above four steps in details. The four stages are synthesis of chlorothioalcohol. The production of ODM is carried out in four stages. output and waste parameters was done at this stage. Step 3 Identification of focus areas for CP: Detailed analysis was carried out to identify the source and the cause of waste generation.Step 2 Preparation of material balance sheet: The quantification of the major input. Process study (Step 1) The installed capacity of ODM in India is 250 TPA [CPCB. 1986].3. The application rate varies from 40-125 mg/sqm. synthesis of thiosalt. [USEPA. 1986]. The set of chemical reactions during the four stages of production of ODM has been given in Table 9.

Definite quantity of diester is added in the reactor at a controlled flowrate by maintaining temperature between 50oC to 60oC. Chlorothioalcohol batch is allowed to settle in the CTA reactor. The reaction is exothermic in nature Synthesis of demeton-methyl Reaction step: Demeton-methyl is manufactured in aqueous phase by the reaction of CTA and thiosalt formed in the earlier two stages. DM is extracted in xylene by solvent extraction where as the salts get dissolved in the water. H3PO 3 is formed as a byproduct. Separation step: The reaction batch is drained into the drowning vessel. H3PO3 and CTA physically separate out. Sodium chloride and water are formed as byproduct. After addition of diester. Thiosalt batch is cooled and then drained into the DM reactor. The mix is separated through separator. The temperature and the pH are maintained for the desired reaction time. H3PO3 layer from CTA reactor is initially added to bring down the pH of thiosalt.reaction time. H3PO3 forming the lower layer and CTA the upper layer. Sodium chloride is the byproduct formed in the reaction. temperature and pH are maintained at 40-55oC and 4-6 respectively. The required quantity of water and NaOH are taken in the thiosalt reactor. NaOH is added to the reactor to maintain the pH in the desired range. During addition. The reaction is highly exothermic in nature Manufacture of thiosalt Thiosalt is manufactured by the reaction of diester with NaOH. the reactor is maintained at this temperature for the desired reaction time. The pH of the thiosalt batch is in the high alkaline range. Upper organic layer containing high concentration of DM gets collected in one vessel and bottom aqueous layer containing traces of DM is collected in another vessel. However. The formation of DM is not exothermic in nature. CTA is then drained into the reactor. The aqueous layer contains high concentration of salt and is referred to as salt-water Identification of Potential Interventions Chapter 9 Page 14 . Thiosalt batch is highly alkaline in nature due to the presence of excess NaOH. The required quantity of xylene and water are added to it. the neutralization of H3PO3 with NaOH is highly exothermic.

Recovered xylene is used in the process. Required quantity of DM. and separation (whatever applicable) were studied both from chronology as well as mass balance point of view. The reaction is exothermic in nature. each unit operation was documented and activities including charging. It is important to note here that each unit operation and individual batch was followed during the production process. Excess H2O2 is destroyed with sodium bisulphite and batch is neutralized with liquor ammonia solution.The organic layer containing DM solution is vacuum distilled in the long tube evaporator (LTE) to further concentrate DM. water and sulfuric acid are taken in the DM oxidation reactor. Salt water containing traces of DM is extracted in xylene recovered from LTE in the salt-water extraction vessel.g. The batch is filtered in the filter press to remove the salts and transferred to the storage tank. The salts crystallize out in the organic phase. discharging. Finally it is detoxified with sodium hypochlorite and drained as Preparation of material balance sheet (Step 2) As described earlier. The batch is diluted with the desired solvent. the ODM manufacturing plant has several unit operations for reaction and separation of intermediates and products. There were seven activities carried out during DM Chapter 9 Page 15 Identification of Potential Interventions . The reactor is maintained at this temperature after addition of H2O2 for the desired reaction time. Figure 9. reaction. For e. cooling. pH is brought in the neutral range. Separation step: The batch is then heated to remove xylene and water. Bottom water is made alkaline by addition of NaOH and fed to column heating to recover traces of xylene and traces of DM. Salts are formed in the reactor as a result of H2O2 destruction and neutralization of sulfuric acid.. Synthesis of oxydemeton-methyl Reaction step: Oxydemeton-methyl is formed by oxidation of demeton-methyl in an acidic medium in aqueous phase. Calculated quantity of H2O2 is added at a controlled flowrate maintaining the temperature between 35oC to 45oC. heating. After separating through separator. effluent.4 was developed to study the sequence of activities during DM synthesis in stage 3. extracted xylene is recycled to the drowning vessel. stirring. First.

When these two reaction mixtures are brought together in Stage-3. This has been graphically illustrated in Figure 9. NaOH charging. In the formation of thiosalt in stage-2. and H3PO3. which are the feed materials for DM.5. besides CTA. during process study was prepared. Further. Build-up of impurities Oxy-demeton methyl (ODM) is formed in a batch process as discussed in section-3. thiosalt. where as the other reactant is the limiting reactant. water (used for dilution and byproduct). sampling and reactor maintenance. Identification of focus areas for CP (Step 3) The production process and material balance for each unit operation was assessed to identify the cause of waste generation. In the final product. material balance for typical input / output parameters emerging from stage 3. Commercial NaOH is diluted to initiate the reaction. H3PO3 (byproduct) and excess PCl3 are present. The composition of the reaction mixture prior to the formation of DM based on a thorough mass balance across the DM reactor is as given in Table 3 Identification of Potential Interventions Chapter 9 Page 16 . contains NaCl. NaOH is added in excess of the required stoichiometric quantity. the excess PCl3 reacts with water forming H3PO3 and HCl. one of the reactants is added in excess. NaCl (byproduct). NaOH addition. besides CTA and thiosalt. Various causes of waste generation as we go further down the production line are enumerated here. In the formation of CTA in stage-1. the final reaction mass. In each of the four stages. In the final product. besides the required product. and the excess NaOH are present. Salt is also present as a byproduct form the thiosalt process. acid layer charging. As a result. H3PO3 is also present as a byproduct from the CTA reactor. Na3PO3. PCl3 is used in excess of the required stoichiometric quantity and thioalcohol is the limiting reactant. Similar exercise was carried out for the other unit operations. These acids are neutralized by addition of NaOH resulting in formation of salts in the DM reactor.manufacture including thiosalt charging. CTA layer charging.

The salts and the other compounds are present in abundance (their concentration in the reaction mass is of the order of 165 g/L) when compared with the two reactants namely CTA at 148 g/L and thiosalt at 240 g/L. respectively. the DM is extracted in xylene where as the salts get dissolved in the aqueous layer. Hence. accumulation of impurity and addition of excess chemicals have and add on effect on each other as we go down the production line and this becomes a major source of waste generation. Thus. as one progresses down the production line. Under these conditions. This issue is of greater concern. This leads to lower conversion rates and hence excess chemicals have to be added which further add on to the concentration of impurity in the form of byproduct for the next process step. impurities build-up in the form of byproducts and undesirable substances. The entire quantity of PCl3 and NaOH used in the process ends up as waste. thiosalt has to be added in large excess when compare to the required stoichiometric quantity in the DM reaction. excessive use of water further dilutes the reactant concentration in DM reactor. a major fraction of organic impurity will be carried with the product in the solvent and a major Identification of Potential Interventions Chapter 9 Page 17 . PCl3 is extremely hazardous in nature. Low atom selectivity The overall equation for formation of DM combining the first three stages can be written as 1/3PCl3 +OHC2H4SC2H5 +3NaOH+(OCH3)2PSCl (OCH3)2POSC2H4SC2H5+2NaCl+H2O+1/3Na3PO3 The above equation implies that the reaction has low atom selectivity (55. Due to its explosive nature. Long separation process In the separation stage.6%). In the present separation process. as thiosalt is a secondary reactant and not a primary reactant. This indicates that the concentration of the reactants is less than the concentration of impurities and byproduct. This issue is of concern as both these chemicals are used in excess quantity. In addition.

which is quite high when compared with the solubility of the product. Repetitive addition and removal of chemicals. The solubility of DM in water is 3. The salt is not likely to affect the quality of the product. the following three issues emerge as the focus areas for Cleaner Production of oxydemeton-methyl:    Excess use of chemicals and water Excess formation of salts and their removal Cyclic synthesis and separation process Chapter 9 Page 18 Identification of Potential Interventions . The present separation process is not able to remove organic impurity. A fraction of pesticide also gets washed off with the water. initially xylene added during the solvent extraction is evaporated in LTE. which is likely to affect the functional property of the pesticide. In the entire production process there is a repeated addition/removal of chemicals. Subsequently. solvents and water as can be seen from the process flow chart. The separation process is highly energy intensive and happens to be the most polluting step of the entire production process. The aqueous layer from the separation process is difficult to treat due to high TDS and toxic compounds present in it. solvent and water Formation of DM takes place in the aqueous phase. The quantity of salts and other inorganic impurities present in 3000L of salt water is of the order of 1000 kg. The oxidation of DM to ODM takes place in aqueous acidic medium.6. This implies that the major objective of the separation process is to remove mainly the inert salts formed and the water added during various stages.3 g /L [RSC. An overview of the origin of pollution during the separation is illustrated in Figure 9. The salts formed are filtered out in the end. The required regulatory standard of the pesticide in water is of the order of 10 g /L [CPCB. From the above discussion. 1987]. The solvent is added as the final product is to be supplied in a particular solvent. The acid is neutralized and the water is evaporated after ODM formation. 1989]. DM is extracted in xylene to remove salt and water. Hence. water and acid are added to DM.fraction of inorganic impurity will be removed with water.

in certain Page 19 optimum concentration at which the reaction should proceed. The concentration of the excess reactant varies from an initial maximum value to a minimum value at the end of the reaction. Unsteady conditions prevail in the reactor with respect to concentration of reactants and products. However. It is of greater concern as thiosalt is a secondary reactant and not a primary reactant. the reaction does not proceed at an uniform rate and varies with the concentration of the reactants. one reactant is added initially to the reactor and the second reactant is added to it at a controlled flowrate. Identification of Potential Interventions Chapter 9 .ODM. The concentration of the Excess reactants (%w/w and %w/v) is not uniform and goes down with time. separation. thiosalt holds special significance. The approach adopted to resolve the issues discussed above can be grouped under six categories. reactants are added to overcome this condition. which has been taken up for detailed CP assessment. Acordingly. as it has to be added in large excess of the required stoichiometric quantity in the DM reaction. It is required due to addition of excess chemicals. The problem also has to be analyzed from the point of view of yield of product. Modification of reactor operations Modifications in CTA reactor operations: In each of the four steps of product formation. B. they are generic in nature and are likely to be encountered in the manufacture of other pesticides and fine chemicals.These problems have come to light with reference to the particular product . There is a need to simplify the separation stage either by reducing the number of steps or by totally eliminating the separation stage. which have been discussed in the following sections. formation of salts and addition of excess water. Hence. This also implies that there is no defined Also. which follow the typical three steps (toxification. The separation stage is the most problematic step as far as waste generation and energy consumption is concerned. and purification) Generation of CP opportunities (Step 4) The overall process of ODM formation has to be analyzed taking into consideration the following two points: A.

it is not possible to maintain other required conditions such as pH and temperature because of the unsteady conditions. Making modifications in reactor operations can make the reaction rate and conditions more uniform.cases. which is present in excess and not PCl3. Two possibilities emerge from this point. Due to safety reasons. The reaction is almost complete during the charging stage itself as is supported by the fact that the temperature starts falling during the reactor maintenance stage although the reaction is exothermic in nature. thioalcohol (TA) is added initially to the reactor. First point is that required excess of PCl3 is not maintained throughout the reaction. Adequate safety precautions will have to be taken to carry out this alternative. PCl3 is added in excess of the required stoichiometric quantity. As the excess quantity of PCl3 added in the CTA reaction poses severe problems down the production process. it is actually TA.g. efforts have to be put in to reduce /eliminate the quantity of PCl3 at this stage itself. at least not in the quantity in which it is added. 25%). PCl3 is added at a controlled flow rate. An excess PCl3 is added towards the end of the reaction so as to ensure complete conversion of thioalcohol. The second one is that excess PCl3 added might not be required throughout the reaction. it may not be possible to execute this option  The feedstock -thioalcohol and PCl3 can be added in stages. The reaction is instantaneous in nature and starts during the addition stage itself. In CTA formation. This indicates that excess PCl3 will move the reaction in the forward direction. as PCl3 is highly explosive in nature. The desired reaction temperature can be maintained. Initially a predetermined quantity of thioalcohol is added (for e. If PCl3 is maintained at a uniform excess concentration throughout the reaction then the yield of the product will be high and the overall excess PCl3 used in the reaction will come down. Then PCl3 can be added to it at a controlled flow rate and a defined excess value (For Identification of Potential Interventions Chapter 9 Page 20 . There are three possible alternatives to achieve this condition. as the reaction will proceed at a more uniform rate.  Excess PCl3 can be added to the reactor and thioalcohol can be added to it at a controlled flow rate. This implies that during the first few hours of the reaction.

Modifications in thiosalt reactor operations: In the formation of thiosalt. This would ensure that the reaction proceeds to completion. This would lead to reduced consumption of NaOH. Adequate provisions for heat transfer and safety will have to be made for this condition.7% (w/v) to a final value of 2. the reaction will move in the forward direction. 5. Lesser quantities of PCl3 will reduce formation of phosphonic acid and hydrochloric acid in the DM reaction step when it reacts with water. It implies that the concentration of NaOH in the reactor varies from an initial value of 23.g.  PCl3 and thioalcohol can be added simultaneously so that a uniform excess of PCl3 is maintained during the reaction. inclusive of the requirement for second stage addition of thioalcohol) is left at the end of the first stage. The quantity of water in the reactor almost remains constant at about 2000 L. Staged removal of phosphonic acid layer from the CTA reactor: As the phosphonic acid physically separates out. The next batch of thioalcohol and PCl3 can be added in the same sequence.5 kg to a final value of 58 kg. The suitability of the two type of reactors-plug flow versus continuously stirred reactors will have to be determined. NaOH is added in excess of the required quantity. reducing the reaction time. NaOH is added initially to the reactor and then diester is added to it at a controlled flow rate. The reaction starts once the diester is added to the reactor.9% Identification of Potential Interventions Chapter 9 Page 21 . This would also accelerate the reaction rate. excess PCl3 can be maintained and safety considerations are also to be taken care of. it can be removed from the reactor at regular intervals. This option suggests that a continuous reactor for this reaction will be a better choice than the batch reactor. As the concentration of the product will go down. By following this procedure. Detailed analysis will also have to be carried out to determine if any multiple/ seriesparallel reactions take place due to variation in the concentration value of the feed material. reduced salt formation and lesser quantity of heat released during the reaction.e. Detailed trials and calculations will determine the number of stages and exact quantity of PCl3 and thioalcohol to be added in each stage. The quantity of NaOH varies from an initial value of 473.

Further calculated quantity of NaOH can be added to maintain the concentration of NaOH in the desired range.g. the entire quantity of NaOH is added initially and water is added to dilute NaOH. This further reduces the w/w concentration of NaOH. At present. As the concentration of NaOH can be maintained within a narrower range. NaOH is consumed whereas the water remains in the reactor. Detailed calculations and trials will considerably reduce the quantity of water and sodium hydroxide added during thiosalt formation. While reducing the quantity of water. During the reaction. This indicates that either or all the three points listed below hold well. Instead of one time addition of NaOH. The reaction mass is at a temperature of 50oC -65oC. Another alternative is to add caustic at a controlled reactor to maintain the same excess concentration throughout the reaction. Water is added with the NaOH and further water is added to reduce the concentration of water from 50% (w/w) to 20%(w/w). This has Identification of Potential Interventions Chapter 9 Page 22 .  % Excess of NaOH is not maintained at a constant value in the reactor during the reaction   % Excess NaOH added initially may not be required during the reaction Desired reaction condition of %excess of NaOH concentration not defined/maintained leading to lower conversion rates Modification in sequence of addition of NaOH can reduce the quantity of NaOH and water added to the reactor. Reduction in water and salt holds special significance in reference to the one-pot process discussed later as discussed in section 7. as it is already present in the reactor to dilute NaOH. both of which are not desired. as this will impose the lower limit to the extent to which the quantity of water can be reduced in the thiosalt formation process.(w/v). The heat effects of dilution will also have to be taken into consideration. The point to be noted is that the reaction is proceeding at these varying concentrations of NaOH. Also. water is not to be added. a calculated quantity of NaOH can be added (e. diester is added leading to the formation of thiosalt and sodium chloride. The residual NaOH is neutralized by H3PO 3 in the DM forming salt and releasing heat. 100 kg) and the required quantity of water be added to reduce its concentration to 20%(w/w). the quantity of excess NaOH can also be reduced. the solubility of thiosalt in water also has to be taken into consideration. excess quantity of NaOH used may lead to hydrolysis of product and should be avoided. As the reaction proceeds. During this addition.

It would reduce hydraulic load on the detoxification plant. The probability of using it in place of process water in the thiosalt/DM process should also be looked into. the sampling time to determine DM and H2O2 concentration at the end of the reaction is 1 hr. Also. This time should be incorporated in the reaction time as reaction is under progress during sampling. As the water has high TDS. indicating that the reaction is complete. In the ODM synthesis. Reduce quantity / flowrate of H2O 2 in the ODM reactor: As indicated by mass balance for ODM synthesis. The temperature of the reactor has to be maintained at the desired reaction temperature. This would not only reduce the reaction time but also reduce the consumption of resources required in the maintenance of reactor. 1977] in the DM reactor will enhance the rate of the reaction. time taken to determine pH after two hours is 30 minutes. it is suggested that this should be accounted for in the reaction time. brine. Reuse of salt-water from separator: Salt-water can be reused in the drowning vessel. Incorporation of sampling time into reaction time: At several stages. In case of DM synthesis. the overall reaction time increases by 30 minutes. and reduce the reaction time. The overall reaction time should also be reduced as the reaction is taking place in acidic conditions. As the reaction is under progress during the sampling. there is a probable further oxidation of DM to other products as neither DM is present. Also. the number of times the water can be recycled will be limited and can be experimentally determined. sampling is done to check the concentration of the various compounds. Reduction in water will reduce the reaction volume and will reduce the heating and the cooling requirements. which can lead to hydrolysis of the product. and cooling water are used depending upon the requirement.to be cooled before being added to DM reactor. providing excess reaction time can also lead to decomposition of the products into byproducts. The sampling time is quite substantial in certain cases. Hence. nor corresponding ODM is present in the Identification of Potential Interventions Chapter 9 Page 23 . Steam. the concentration of CTA remains constant over the last two hours. Addition of catalyst in DM reactor: Addition of copper as catalyst [Marshall. as this water would be containing the excess thiosalt carryover from the DM reaction.

is discussed in section 7(One-pot process). triester is better than diester. However. which is rather elaborate. as H2O2 is added 15% in excess of the required stoichiometric quantity and only 75% of the H2O is used for oxidation of DM. 1500L of the initial 2000L of water added to the reactor is for dilution for NaOH.final reaction batch. 65% (~350 kg) of the inorganic impurities present in the DM reactor is from the thiosalt reactor. as discussed in section 5.1.5. The main source of addition of water is dilution of NaOH . Also the consumption of NaOH is 50% less. Hence. This could be possible. this happens to be the quantity of water which is required to be removed Identification of Potential Interventions Chapter 9 Page 24 . it is clear that salt is not formed when triester is used. the plant is designed to manufacture diester. which has to be diluted to 20%(w/w). 270 kg of this is NaCl which is formed as a byproduct. which would lead to simplification of the production process which. Also. as a raw material. Substituting diester by triester ((OCH3)3PS) as feed material can eliminate this problem. As discussed later in section 7. The chemical reaction for manufacture of thiosalt DM from triester is as follows: (OCH3)3PS + NaOH Reaction with diester is: 2NaOH + (OCH3)2PSCl (OCH3)2PSNaO+NaCl (OCH3)2PSNaO+ CH3OH From the above equations. it becomes an impurity leading to the addition of excess chemicals down the production line. This loss can be reduced/eliminated by reducing the quantity/ flowrate of H2O 2 addition. complicated and energy intensive is to remove these salts. Raw material substitution Substitution of diester by triester in the thiosalt formation: The main objective of separation. But reduction of salt formation at this stage. As can be seen from the material balance sheet for DM reaction in Figure 9. Problem of separation can be simplified by reducing the quantity of formation of salts itself. the salt formation and the NaOH consumption will take place during the formation of triester. Yield of upto 97% of the theoretical values are obtained when using theoretical or very small excess of hydrogen peroxide [Lane. Substitution of NaOH by KOH in the thiosalt formation: The second objective of separation is to remove excess water. Detailed techno-economic feasibility analysis will have to be carried out taking into consideration all the factors. 1957]. Also.

in the DM formation step. hence creating the need for the separation stage. this acid has to be neutralized with NaOH. the quantity of water added at this stage can be reduced by 50%. Minimization of downstream waste generation As discussed before in section 5. then it can be used at a concentration of 40%(w/w) as per the information provided during the case study. Separation of H3PO3 layer: In the present production process. The thiosalt reaction batch has to be cooled prior to the addition to DM reactor.1. Different techniques of separation have to be employed as per the nature of the byproduct. Hence.5) and the same solvent can be retained.for oxidation stage. The various CP opportunities in this category have been discussed in this section. The DM formation step in itself is not exothermic. This leads to a build up of salt in the reactor. It will lead to simplification of the production process as discussed in section 7 (One-pot process). 150 kg of the salts present in the reactor is from neutralization. This can be avoided by segregating the byproducts as we go down the production line. But the pH actually goes down to 1-2.25 US$/kg [CW. An overall cost-benefit analysis will have to be made for substitution of NaOH by KOH. The ODM concentration in the final product is also 50%(w/w). Also. But KOH is more expensive than NaOH and also stoichiometrically more quantity of KOH will be required. a limited quantity can be added to the tank to bring down the pH to the desired Identification of Potential Interventions Chapter 9 Page 25 . then it would reduce the number of steps in separation process considerably as the evaporation stage can be eliminated. additional cooling arrangements have to be made for maintaining the heat generated during neutralization reaction. the entire quantity of H3PO3 layer from the CTA reactor vessel is added to bring down the pH of thiosalt in the range of 4-6. Hence. If the oxidation is carried out in organic phase (as discussed later in section 6. If KOH is used instead of NaOH. as we go down the production line. 2000]. there is a build up of impurity in the form of byproducts. This results in addition of excess chemicals and lower yield of the product. As H3PO3 layer physically separates out in the CTA tank. The cost of KOH is 1 US $/kg where as cost of caustic lye is 0. Use of same solvent in solvent extraction as in the final product: The concentration of DM obtained after separator is 50%(w/w).

Thiosalt is added in large excess of the required stoichiometric quantity. This will greatly reduce the impurity concentration in the DM reactor. The cooling arrangements will not be required not only in the demeton-methyl process but also in the thiosalt process. The pure thiosalt solution can be added to the DM reactor. The probable reason for the excess quantity to be added is the presence of salts. Identification of Potential Interventions Chapter 9 Page 26 . water. approximately 350 kg of salt is added to the reactor from the thiosalt reactor. and NaOH. A detailed techno-economic feasibility of the available separation techniques has to be done to select the most suitable one for the process. It will reduce the build up of salt in the DM reactor. which would reduce the consumption of thiosalt also. Elimination of NaOH addition in DM tank: The desired pH for the reaction is 4-6 and when the entire quantity of H3PO3 is added from the CTA tank. It will also help in achieving the one-pot process as discussed in section 7. Elimination of NaOH is possible if the entire layer of H3PO3 is not added. Due to the presence of these compounds. Segregating thiosalt from salt and water will reduce the quantity of thiosalt added. To raise the pH. The molecular weight of thiosalt is 164 where as that of NaCl is 58. This would reduce build up of salt in the reactor. to segregate thiosalt from the other products.5 and NaOH is 40. which can interfere in the reaction. as a carryover from the earlier two stages is approximately 500 kg. The thiosalt reaction mass consists of thiosalt. Separation of thiosalt: The quantity of salts and other inorganic impurities present in the DM reactor. NaCl. As the reactants will be present in higher concentration. NaOH is added. the required additional quantity will be less. concentration of thiosalt is 68. Membrane separation techniques like ultrafiltration can be considered which separate compounds on the basis of their molecular weights. As seen in the material balance sheet for DM synthesis in figure 3. it goes below 2. Around 150-kg salt is formed in the reactor due to neutralization of phosphonic acid.range. If only solid concentration is considered. Water addition with NaOH can be avoided.3%. the concentration of thiosalt in the final reaction batch is 25% (w/w) and 29% (w/v).

4. The basic principle of extraction is difference in solubility of the compound which has to be extracted in the two-phase liquid system [McCabe and Smith. water and xylene are practically immiscible in each other and separated on the basis of gravity in the separator. which is wastage of energy. 1987]. Along with water. The reaction mass remains for a considerable amount of time (~12 hrs) in acidic medium after DM formation. Hence. Hence.1 The basic principle of separation in the separator is difference in density. DM is extracted in xylene. When the organic layer is taken to the LTE. Improvement of separation efficiency: The mass balance across the separator after drowning vessel indicates approximately 300L of water carryover with the organic layer. Xylene along with DM is lighter than water. It forms the upper layer in the separator and is separated out. the rate of hydrolysis of DM is slow in acidic medium the time is substantial. DM is completely soluble in xylene. This water has to be removed by distillation. it should form the lower layer. salt is also carried over to the organic layer collection vessel. the salt crystallizes out thus causing frequent clogging of LTE. This loss can be avoided by neutralizing the reaction mass in the drowning vessel. DM is heavier than water and is insoluble in water [RSC. This can be avoided by improving the separation efficiency. The properties of the thiol and the thion isomer is given in Table 9. Separation efficiency can be improved by:     Providing settling time in the drowning vessel Increasing settling time in the separator by reducing flowrate Increasing number of stages of the separator Addition of emulsion breaker Modification in separation technique In the present separation process. The specific gravity of xylene is 0. If Identification of Potential Interventions Chapter 9 Page 27 . Although.86 and that of DM is 1. 1976]. In this case. loss of product due to hydrolysis can be substantial.Neutralization of reaction mass in drowning vessel: The thiol and the thion isomers of DM are readily hydrolysed in alkali. The two liquids. when taken to the separator without being extracted in xylene. It is practically insoluble in water. Cleaning of LTE further generates water pollution problem.

1952] Option (ii) and option (iii) is for production of thiol isomer of ODM [Schrader. Polar solvent accelerates isomerisation probably due to the fact that isomerisation takes place via ionic products [Matolcsy. Option (i) is for production of thion isomer [Schrader. Nadasy. using xylene) at present for separation of DM. 1952] (iii) (CH3O)2POCl + NaSCH2CH2SC2H5 (CH3O)2POSCH2CH2SC2H5 [Schrader. then (I) is to be followed. This would eliminate the need for elaborate solvent extraction (involving separation. Alternate chemical route for DM formation and oxidation From literature review. 1951] (ii) (CH3O)POSNa+ClCH2CH2SC2H5 (CH3O)2POSCH2CH2SC2H5 [Schrader. If the final required product is a thiol isomer then three alternatives are (1) (2) (3) Option (i) followed by isomerism at high temperature Option(ii) Option (iii) Chapter 9 Page 28 Identification of Potential Interventions . Trials will have to be conducted to select the proper method of separation. These are (i) C2H5SCH2CH2OH + (CH3O)2PSCl +K2CO 3 (CH3O)2PSOCH2CH2SC2H5 [Schrader. there are three possible routes for manufacture of DM . Each of the above alternatives is to be carried in an inert solvent such as acetone. Isomerisation is rapid at high temperature in three hours and is complete in 3 hrs at 130oC. methyl ethyl ketone. 1952]. 1951].the separation is not proper then some advanced gravitational separation technique such as centrifugation/floatation can be applied to enhance the separation efficiency. and Andrish 1988]. If the final isomer is a mix of thion and thion isomer. The thion isomer from step (i) undergoes partial thion-thiol isomerism and the technical product contains 30% of the thiol isomer.

1993] depending upon the type of crop. The corresponding salt formation is 100 kg less per mole of DM (166.33 kg for the present process and 58. If the presence of salt does not affect the quality of the product. then the product separation stage could be simplified and the waste generated during separation stage can be reduced significantly. One-stage instead of three-stage reaction can be followed. Identification of Potential Interventions Chapter 9 Page 29 . Technologies like reverse osmosis are not used for removal of salt from wastewater due to economic reasons.5. formation and oxidation of DM can take place in an inert solvent. Also. Also. from the final product. Hence. It is through the wastewater generated during separation of salts. there is no economically viable method for removal of the TDS from wastewater and it does finally find its way into the surface/ground water resources. PCl3 is not used and consumption of NaOH is 50% less. and the final product ODM is to be used as an agrochemical. the presence of salt is not likely to have any harmful effect on the crops on which it is applied. the salt addition from pesticide if left in the final product is negligible. (CH3O)2POCl is the required feed material instead of (CH3O)2PSCl.5kg for the proposed process). at present. (NH4)2SO4 which is formed after neutralization of sulphuric acid is actually a fertilizer for plants. this salt is mostly in the form of sodium chloride which is not toxic in nature. This issue becomes more important as it is the process of removal of these salts. Also. The discussion holds significance with respect to one-pot process discussed in section 7 Modification in product specification Another issue is if it is at all necessary to remove salt (which is mainly common salt). In (3). Compared to salt addition from irrigation water. and energy intensive. Also. which is most polluting. The permissible TDS An overall concentration in irrigation water is in the range of 500-5000-mg/L [CPHEEO. that toxic pesticide finds its way into surface and groundwater resources.At present (2) is being followed in the plant. comparison of (1) and (2) is given in Table 9. DM can be directly prepared from diester and thioalcohol in the presence of acid binding agent. In (1). 1-3 times a season [USEPA. 1999]. The application rates of oxydemeton-methyl vary from 42-125mgPAI/m2.

If the salt and water concentrations are minimized in the DM reactor. A point to be noted at this stage is that the final product ODM is soluble and stable in water. There are two possible strategies that have been identified to reduce the number of process steps by carrying One-pot DM formation and oxidation avoiding the separation. Identification of Potential Interventions Chapter 9 Page 30 .The presence of salt may cause problem during storage and transportation stage. the final product preparation in solvent base is also debatable. The separation step can be eliminated and both the product formation and oxidation steps can take place in aqueous phase in one reactor. solvent.3 Alternate Strategies for ODM Manufacture At present. This step is carried out to remove water and salt. Efforts should be put in to reduce the quantity of salt to the extent possible and then assess the impact of the residual salt on the final product application. Water is the preferred dilutent for ODM [Lane. As an intermediate step. Hence. Organic impurity is extracted with the product in solvent extraction. Also. A detailed review of the various advantages and disadvantages of the presence of the salt in the final product is required. 1957]. both formation and oxidation of DM take place in aqueous phase. then the DM reaction batch can be directly taken up for oxidation. There can also be a problem during the product formulation stage if it is in organic solvent. It can lead to corrosion of the storage drums. DM is extracted in solvent and this solvent is subsequently distilled off. One-Pot Aqueous Process (Option I) The DM reaction batch contains large quantities of salt and water which are to be removed prior to oxidation. “One-pot process” is the correct strategy to be adopted in the light of the problems faced by the current cyclic process. In the present production process there is a repeated addition/removal of chemicals. extraction and evaporation stages. This can be avoided by combining the two steps of DM formation and oxidation. 9.4. use of solvent such as xylene is being discouraged in many countries due to its toxic effects. and water. The two strategies developed incorporate the various CP measures discussed in section 6. This cyclic synthesis and separation process sequence is responsible for creation of a rather high pollution load and energy and raw material consumption in the plant.

The impact of the residual salt on the production process and quality will have to be assessed. The water can be removed by evaporation. It is not likely to affect the functional property of the pesticide. The process sequence for “One-pot aqueous process" is illustrated in Figure 9. The main source of these compounds. 1957]. The quantity of salt and water has to be reduced to the extent possible. The product can be sent for packaging. If the salts are not interfering in the formulation and transportation stage then it can be left in the final product. the quantity of the water and salt present in the two stages has to be balanced. It also has to be compared with the salt removal efficiency of the present separation process. their quantification and possible measures for reduction is given in Table 9. Removal of salts is optional. The salts can be removed in filter press as is being done in the current process.6 The total quantity of inorganic compounds in the output from the DM reactor is of the order of 1000 kg. DM formation can be followed by DM oxidation in one reactor.7. ODM can be subsequently diluted with the desired solvent. Sulphoxide-containing esters of phosphoric acid and thiophosphoric esters are completely soluble in water and are stable in it [Lane.7 To combine the two steps. Identification of Potential Interventions Chapter 9 Page 31 The .The quantity of water in the DM reactor and ODM reactor have been computed as given below: Total water in DM reactor Process water in thiosalt Water added with NaOH (thiosalt) Water added with NaOH (DM) Total water TOTAL WATER IN ODM REACTOR Process Water Water with H2O2 Water with other chemicals Total water = = = 200 L = 500 L 50 L 250 L = = 1550 L = = 473 L 100 L 2123 L The measures suggested to reduce the quantity of water and the possible reduction is given in Table 9.

If the dilutent is water. Removal of salts is to be done by filter press.4 Conclusions The main contents of the waste generated from the pesticide industry include byproducts. 9. which is highly explosive in nature. One-pot process in organic phase (option II) DM formation and oxidation can take place in organic phase as per chemistry discussed in section 6. this aspect can also be taken care of.8. is not used in this process. The process for one-pot-process in organic phase is illustrated in Figure 9. Hence.1. It is not desirable to apply solvents on the plants. Hence.4. The cyclic synthesis and separation process was concluded to be responsible for high pollution load and resource consumption. Removal of salts is optional as discussed in section 7. salts are not likely to affect the functional property of the pesticide   Eliminate need for removal of salt. The point to be noted here is that there is no significant effluent stream arising out of the two strategies illustrated above. PCl3. As discussed in section 6. water and addition of solvent The final product is used as an agrochemical. DM formation can be followed by oxidation in the same reactor.6. NaOH consumption is reduced by 50%. corresponding salt formed is reduced by 65% compared with salts formed in the existing process.5. the environmental costs can also be brought down considerably. the reaction should be carried out in the same solvent as is desired in the final product. Preferably. This does not include salts formed due to excess chemicals and neutralization. excess chemicals and a fraction of product which is lost as waste. The separation stage is followed to remove inert salts from the process and is not able to remove the organic Identification of Potential Interventions Chapter 9 Page 32 .preferred diluent is therefore water. If the final product is prepared in water it would have numerous advantages:  Salt can be left in the product and is not likely to interfere in storage and transportation stage.

unsteady conditions with respect to concentration of reactants/products prevail during the course of the reaction. Although this research has addressed the existing production process of ODM. The salts are not likely to affect the functional property of the pesticides. fine chemicals. It is timely to illustrate such an approach for CP of these polluting chemicals because rather little efforts are made in identifying and developing CP alternatives by way of retrofitting the existing production unit. On the basis of scientific data. experience of the plant personnel and the material balance sheets. A need is felt to avoid the separation stage.impurities. Research and development activities have to be initiated to evaluate techno-economic feasibility of employing “one-pot process” for formation of ODM. Identification of Potential Interventions Chapter 9 Page 33 . In the batch reactions. Modification in reactor operations can make reactor conditions more uniform. Alternate chemical routes can increase atom selectivity. Another major cause for waste generation is the adoption of batch. In fact. this approach can be meaningfully employed for CP of pesticides. product separation/concentration and formulation. One-pot process is the correct strategy to be adopted in light of the problems faced by the current cyclic process. pharmaceuticals. the approach illustrated in this document is not limited in its details and entirety as well as utility for ODM or PAI alone as a group of chemicals. bringing down the quantity of excess chemicals used. These excess chemicals end up as wastes. semi-batch reactions for the various stages. where as the organic impurities can do so. Chemistry of reaction with low atom selectivity and using phosphorous trichloride as raw material has been identified as the third major reason for generation of waste. the need to review the process sequence was felt. Excess chemicals are added to overcome this barrier and to maintain a minimum concentration of reactants till the end of the reaction. dye & dye intermediates which typically employ batch process and invariably go through cyclic process of product synthesis. It can however be judged to be “practical“ only after detailed research & development efforts and full-scale production trials are carried out to ascertain the impact on product stability and product specification.

There should be procedure or method to rank the different waste streams. A systematic approach to ranking pollution prevention or waste reduction projects will consist of two steps. e) ease and cost of implementing pollution prevention options. to screen the available waste streams. The first step identifies the waste streams where the highest gains from pollution prevention might be realized. a rating of 0 to 5 points can be assigned to each stream for each of following criteria. each with different technical characteristics. and f) demonstrated effectiveness of pollution prevention options. The second stage is to propose and prioritize specific pollution prevention options for the high-ranking waste streams. Now. it will highlight the number of processes and waste streams. The procedure for conducting a waste audit in an industry consisted of the following steps. 1) Subdivide the industry into processes and the processes into streams 2) Conduct a waste survey 3) Screen the waste streams and identify the high-priority streams 4) Develop pollution prevention options for the high-priority streams 5) Screen the pollution prevention options and identify the high-priority options 6) Evaluate the high-priority pollution prevention options. By conducting a waste audit in industry. Identification of Potential Interventions Chapter 9 Page 34 . and environmental impacts. c) possible regulatory impact in the future. The rating depends on the weightage of the criteria. a) waste quantity and frequency.9. d) safety and health risks to the employees and the community. b) the cost of managing existing waste.5 ALTERNATIVE APPROACHES POLLUTION PREVENTION TO PRIORITIZING OPTIONS FOR An industry can have hundreds of waste streams. treatment costs.

and 6) quantifiable results. The evaluations were converted into unitless scores from 0 to 50. the top twenty options were evaluated to provide capital cost and cost savings estimates. It can be seen that the main criteria are risk reduction. catastrophic. which defines the hierarchical structure of the ranking criteria. 2) reduction of waste volume or disposal/treatment cost. and product liability. Liability costs are made up of remedial. The three types of liability were considered to be equally important. There is another method used for screening the pollution prevention options. with higher scores indicating greater desirability. The criteria chosen for prioritizing these options is shown in Figure 9.9. capital costs. The total liability score is equal to Identification of Potential Interventions Chapter 9 Page 35 . Cost factors are comprise operating and maintenance costs. Evaluations of each criterion in Figure 9. After this preliminary screening was done. and product liabilities are 50. 3) ease of implementation. The bases used for evaluating the criteria are not always obvious. The next step was to propose pollution prevention options for these streams. catastrophic. These options were screened by assigning a rating of 0 to 5 points based on each of the following criteria: 1) pollution prevention hierarchy: source reduction favored over recycling which is further favored over waste treatment. so each liability score was assigned a weight of one third. and liability costs. 4) proven performance.The streams with highest scores were assigned the highest priority for reduction. 5) safety and health risks. 11. Sample Calculation: Consider the scores for remedial. technical characteristics.9 were made for ranking each option. and 33. and cost factors.

Some of the notable sector-specific ones focus on energy conservation in iron and steel industry [UNIDO and MITI.33  11  0.4) are also elaborated [Jorgensen. 1999]. A wide range of examples of immense relevance in Indian contexts have been covered in a practical guide to cleaner production and enhanced profitability [Modak. Some additional perspectives on what CT and environmental technology stands for (Box Identification of Potential Interventions Chapter 9 Page 36 . UNEP and UNIDO. USAID. which is an integral part of cleaner production. and the Handbook of the climate change mitigation options for developing country utility and regulatory agencies [USEA.33  31 Using the same procedure the score for risk reduction. 2001] focuses exclusively on tools and techniques for identifying hotspots in industry related to identification of improvement opportunities in energy utilization. 1992]. in order of desirability. and low. 1995]. 2000]. and technical characteristics is evaluated. The Handbook of energy audits and management [Tyagi. Opportunities for introducing the diverse CP interventions have been identified and the scope for significant economic benefits has also been highlighted by them.33  33  0. and waste minimization in the synthetic textile dyeing and printing industry [NPC. the pollution prevention and abatement handbook [WB.50  0. 1998]. 9. It will be useful to note that concepts of cleaner production has drawn the attention of several agencies and experts engaged in guiding and enabling industrial development. medium. The various options are ranked as high. 1999].

S. Due to pressure from public. . and Gopichandran. Perhaps an even greater surprise was the vigorous response of the general public.. The major emphases of these regulations have been to treat the effluents before they are discharged. who until then had shown little or no interest in global environmental issues. the new and alarming issue was the discovery that harmful effects or chemicals could accumulate over a long period of time and cause problems far from the actual source. Thus this system relies entirely on the down stream control of the pollution. The inherent weakness of this approach is that it is curative in nature and is not based on more appropriate methods of preventing pollution.Reference: Asolekar. industries adopted the end-of-the-pipe (EOP) treatment technology. UK) Box 9. end-of-thepipe (EOP) approach is being viewed as a missed opportunity in converting valuable resources to final products. R. R.1 End-of-the-pipe Approaches Had Limited Success! Credits for the first serious out cry of warning regarding ecological backlashes goes to Rachel Carson for her book “Silent Spring” describing the harmful effect of DDT on the ecosystem. these methods just transfer pollution from one form to another. Foundation Books Pvt. wherein all the wastes are brought to a common place for treatment before release to the environment. The end-of-pipe method of achieving environmental compliance suffers from major drawbacks. The deficiencies in the EOP approach are being slowly tackled by new approaches to cleaner production. At that time. In addition to the high cost of treatment. In response to these regulations. the government in various countries laid rules and regulations for the control of pollution. New Delhi (the Indian associate of Cambridge University Press. With increasing constraints on the availability of resources. Ltd. “Preventive Environmental Management – An Indian Perspective”. (2005).

CP includes conserving raw material and energy.2 Definition of cleaner production Cleaner production (CP) is continuous application of integrated preventive strategy applied to process. however economically sound. change of habits and human adaptations. eliminating toxic raw materials and reducing the quantity and toxicity of all emissions and wastes. For products. the risks in terms of working conditions . UNIDO [1998] Box 9. which are new and untried. CP focuses on incorporating environmental concerns into designing and delivering goods. coupled with an unwillingness to adopt processes. acts as brakes on the dissemination of clean technologies. Lack of knowledge of environmentally sound processes. For services.3 Constraints in Adopting Cleaner Production Concern over product quality: Manufacturers and customers must be convinced that new process will produce equally high quality products. which are available. products and services to increase Eco-efficiency and reduce the risk to humans and the environment. from raw material extraction to its final disposal.Box 9. The existence of an economic climate where investment generally is limited and are subjected to high rates of interest. For processes. Moreover many of the industrial enterprises in India are small and are unable to afford costly new equipment.for instance. In addition to the technical and economic risks. . CP involves reducing the negative impacts along the life cycle of a product.

apart from changing production technologies in order to achieve lesser levels of emissions. Cleaner Technology could emerge from LCA or in the process of evolving EMSs.  Eco-technologies refers to the use of ecosystems in attempts to resolve pollution related problems. ecosystems Source: Jorgensen.Box 9.4 Different classes of technologies for environmental improvement  Environmental technologies refer to such a technology. which offers several methods to remove pollution from point sources  Cleaner Technology explores recycling of by-product or wastes. 2000 Such ecosystems could also imply designed .

300 2..000 4. Foundation Books Pvt. and Gopichandran.000 COD pH Total dissolved solids (TDS) Total suspended solids 73. Ltd. UK) Table 9. (2005).2 Stagewise reactions employed during oxydemeton-methyl production . R. 2001] Table 9. New Delhi (the Indian associate of Cambridge University Press.Reference: Asolekar. R.000 1-12 80.1 Wastewater characteristics for pesticide manufacturing unit Parameter Maximum concentration encountered (mg/L)* Typical concentration encountered (mg/L)* 13.000 4. “Preventive Environmental Management – An Indian Perspective”.800 3000 *Source: WB [1998] and CPCB (1993) #Source: Sinha.000 5-6 70.000 Typical concentration for ODM effluent (mg/L)# 30. S.

Stage. 1 Product Chlorothioalcohol(CTA) Chemical Reaction PCl3+ (Phosphorous trichloride) 3HOC2H4SC2H5 (Thioalcohol) 3 ClC2H4SC2H5+ (CTA) H3PO3 (Phosphonic acid) (OCH3)2PSNaO+NaCl (Thiosalt) (Sodium chloride) CH3O)2POSC2H4SC2H5+ NaCl (DM) (Sodium chloride) + H20 (Water) 2 Thiosalt 2NaOH +(OCH3)2 PSCl (Sodium hydroxide) (Diester) 3 Demeton-methyl (DM) (OCH3)2PSNaO +ClC2H4SC2H5 (Thiosalt) (CTA) 4 Oxydemtonmethyl(ODM) (CH3O)2POSC2H4SC2H5 + H2O2 (DM) (Hydrogen Peroxide) (CH3O)2POSC2H4SOC2H5+H2O (ODM ) (Water) [Source: Sinha. 2001] .

5 kg 100 kg 2200 L 3500 L [Source: Sinha. 1955] .002%-0.1x10 (H ) 9.25x10 (H ) 0.02% 0. 2001] Table 9.02% -2% [Source: Metcalf.5 C o 2.4 Properties of thion and thiol isomers of DM Temperature Alkali Hydrolysis Acid Hydrolysis Solubility 84.1x10 (OH ) -3 + -3 - Thiol isomer 0.5 C o Thion isomer 2.3 Composition of DM reaction mixture Compound CTA Thiosalt Salts Others Water Reaction Volume Quantity 521.814(OH-) -3 + 24.4 kg 841 kg 475.Table 9.

3 (iii) Modification in thiosalt reactor operations Substitution of NaOH by KOH Elimination of NaOH addition in DM tank Require trials. 2001] .Table 9. 2001] Table 9.8 106 160. No.33 Four Nil Required Required Nil 106 160.1 (iii) 6. 1000L 1000L 100L [Source: Sinha.2 (ii) 6. 2. 1. 6. Phase Raw material (per kg mole) in kg PCl3 Thioalcohol Diester NaOH 3.5 80 166.5 40 58. 7. 4 5. No. CP measure Possible reduction in water quantity 6.6 CP measures for reduction of water in DM reactor Opt.5 Two Copper No No Parameter Actual process Aqueous Proposed process Organic [Source: Sinha. Salt formation (kg/kgmol) Duration (hours) Catalyst Cooling for neutralization of acid H2SO4 for DM oxidation 45.5 Comparison of existing process and modified process for ODM manufacture Sl.Approx.

1 (i).1 (iii) 6.2 (i) 6.7 Quantification and possible measures for reduction of inorganic compounds in DM reactor Compound Source Quantity CP mesures Possible Reduction NaCl From thiosalt reactor 275 kg 6. 50 kg 274 kg 274 kg Requires trials Requires trials Nil 274 kg Total 148 kg [Source: Sinha.3 (iii) Byproduct in DM reactor Total Na3PO3 H3PO3 Thiosalt Neutralization of H3PO3 Reaction of excess PCl3 with water Excess thiosalt from thiosalt reactor 154 kg 6.3 (ii) Neutralization in DM reactor 54 kg 6. 2001] . (ii).3 (ii) Directly proportional to the quantity of salts reduced 245 kg 573 kg 148 kg 6.3 (i) 72 kg -----do---Approx. 6.Table 9.

2002] .  Figure 9.Cleaner Production Is a preventive environmental strategy Applied to entire production and service cycle Process:   Products:  Reduction of waste through better design Use of waster for new products    Conservation of raw material.1 Cleaner Production [Source: UNIDO. water and energy Reduction of Quantity/Toxicity of emission at source Reduction of cost and risks Evaluation of technology options Services:  Efficient environmental management in design and delivery Impact:   Improved efficiency Better environmental performance Increased competitive advantage.

Energy Raw Materials & Intermediates Producers Power Energy Materials Energy Process Industry for Finished Goods Upstream integration Production chain ends Consumption begins Products Downstream Integration Consumer Figure 9.2 Mass Exchange Schematic in the Production-Consumption Network of an Industrial Product .

2001] .PCl3 Thioalcohol CTA Reactor (Stage 1) CTA NaOH Thiolsalt (Stage 2) Thiolsalt DM reactor (stage 3) DM Drowning Vessel Reactor NaOH Water Diester Water Xylene Org.3 Process flowchart for manufacture of oxydemeton-methyl. Layer Separator Xylene Aq. Layer NaOH Alkalination Column Heating NH3 Neutralization NaOCl Detoxification To ETP Xylene/ MIBK Predrying Postdrying Solvent Dilution Filtration Salts Storage ODM Figure 9. Layer Xylene Long Tube Evaporator Water H2O2 H2SO4 NaHSO3 DM Oxidation (Stage 4) Excess H2O2 Destruction Salt Water Extraction Aq. [Source: Sinha.

2001] .Thiosalt reaction mass (i)Thiosalt Charging Time= 20 min Temperature=20-40oC Alkaline pH (ii) Acid Layer Charging Time= 10 min o o Temperature=20 -40 C Acidic pH Phosphoric layer addition (iii) NaOH addition NaOH Cooling water(Recycled) Organic layer(CTA) Time= 5 min o o Temperature= 30 50 C Acidic pH (iv) CTA layer Charging Time: 10 min Temperature: 20-50oC Acidic pH (v)NaOH addition Time=5 min o Temperature= 20-50 C NaOH (vi)Sampling For pH Time= 30 min (vii)Reactor maintenance pH=4-6 Temperature=40=60oC Periodic sampling for CTA concentration TO DROWNING VESSEL Figure 9.4 The seven-step process conducted in one reactor called as “DM reaction vessel “ is shown along with sequencing of several additions made during the course of the reaction [Source: Sinha.

[Source: Sinha. 2001] Input Raw material Org. Impurities(Small fract. Byproduct.)+ Inorg.INPUT CTA MASS: CTA: 557 Kg Others 131 kg THIOSALT REACTION MASS Thiosalt: 840 kg Others:304 kg Water : 2150 L NaOH ADDITION NaOH :90 kg Water :90 L OUTPUT DM: 964 kg CTA:35.6 kg Thiosalt : 154 kg DEMETONMETHYL REACTION VESSEL Others: 900 kg Water: 2250 L Figure 9.impurity.)+ Solvent Waste Water+ Inorg. Inorg.) (Liquid phase is carried over from the toxification stage to the separation stage) Figure 9. Org. Impurities(Large fract.5 Material Balance sheet for synthesis of demeton-methyl synthesis [Source: Sinha. impurities Inorg.6 Genesis of pollution in pesticide active ingredient manufacture. 2001] .impurities (Small frac. impurities Water TOXIFICATION REACTION Product. Impurities (Large frac. impurity. Excess raw Material Waste Venting Loss Solvent SEPARATION AND PURIFICATION PROCESS Output Product+ Org.)+ Org.)+ Product+Solvent(Small qty.

solvent Filtration of salts (Optional) Xylene Xylene Condensor Salt cake Packaging Drums of PAI in organic solvent Figure 9. 2001] .Stepwise addition of raw materials Step 1: DM Synthesis as per the process described in section 3 Step 2: Oxidation of DM by addition of H2O2 and H2SO4 Water Removal of water by evaporation Dilution of ODM concentrate Approp.7 One-pot process for ODM synthesis in aqueuous phase (Option I) [Source: Sinha.

Stepwise additon of addition of raw materials Step 1: DM synthesis as per process chemistry discussed in section 6. 2001] .5 in organic phase Step 2: DM oxidation as per section 6.8 One-pot process for ODM synthesis in organic phase (Option II) [Source: Sinha.5 in organic phase Dilution of ODM concentrate (Optional) Filtration of salts(Optional) Salt cake Packaging Drums of PAI in organic solvent Figure 9.

GOAL Identify the Most desirable Pollution Prevention Options for the Refinery Risk Reduction (Double weight) Technical Characteristics Cost Factors Resource Utilization Timeliness Release Reduction Transferability Operation and Maintenance Liability Capital Raw Material Utility Mode Quantity Remedial Catastrophic Product Figure 9. 1993] .9 Criteria Hierarchy [Source: USEPA.