Guidelines for Hazardous Waste Reduction Waste Reduction . _ ,. Program and Recycling Metal Finishing Printed Circuit Board Manufacturing a program of The Department of environmental Quality July 1989 ------- ------- GUIDELINES FOR WASTE REDUCTION AND RECYCLING : ' . METAL FINISHING '.'>. ELECTROPLATING PRINTED CIRCUIT BOARD MANUFACTURING Prepared by the HAZARDOUS WASTE REDUCTION PROGRAM OREGON DEPARTMENT OF ENVIRONMENTAL QUALITY First Revision July 1989 ------- ------- The ' -RiG'CN DEPARTMENT OF ; ENVIHCNT-fZ.VTAI. ..SCAlL-TTY . " -. .HAZARDOUS WASTE 'REDUCTION -PROGRAM . " . . guidelines- were prepared by the Oregon Department--of -nvi-oSJirital Quality's Hazardous'Waste Reduction Program. T orogram was established to provide technical assistance to businesses' and industries 'to reduce the -amount of hazardous walte ?ha? thev generate, deducing the amount of waste gener- at,ed helps to control" costs and protect the environment.- ^he DEQ Hazardous Waste Reduction Program works with facilities of all,sizes to come up with solutions to the problems asso- elated with the generation, storage, treatment, and disposal of hazardous waste. The program can-provide technical information on waste reduction and recycling methods for your business, .n addition, the program can provide,on-site assistance to iaen tify and implement waste reduction opportunities in your operations. ' ' _. '- _._ ... '.-'..,' The program also maintains a technical library containing information on waste reduction and recycling for a wide range of industries. Publications on specific waste reduction methods for electroplating, metal finishing, and printeoVcir-, cuit board manufacturing operations, such,as those listed in the references are available. Additional background infor- mation and worksheets for conducting- a waste reduction assess- ment are also available. To obtain information, assistance, or publications on waste reduction or recycling, please contact: DEQ Hazardous wa/ste Reduction Program 811 SW Sixth Avenue Portland,- Oregon 97204 Phone. (503) 229-5913 or Toll Free Within Oregon, 1-800-452-4011 ------- ------- TABLE OF.- CONTENTS :HAPTER r. INTRODUCTION CHAPTER 2 .'WASTE REDUCTION AND RECYCLING .METHODS '. ..' ... .' .. 5 1 GENERAL: WASTE REDUCTION METHODS .'',.; . .---. . . . 5,; " -; WASTE REDUCTION AND RECYCLING APPLICATIONS. . '. -. 9 Improved Operations and . : , .''' - ', Housekeeping Practices .- ... .. . . . . . ' 10. ' ' s ' ' ' ' ,' " " ' ' ''' .' , Drag-Out. -Reduction ^. . . . . '. . . . . . . 10 " Rihsewater Modifications . .... .... -12 /Material/Chemical Substitutions . . ';_.. . . . 13 Plating Bath Maintenance ... . ;.-. . . .-. 14 Chemical Recovery Processes . . . . .... 15 ' Metal'.Recovery Processes .'.,. . . . .-,'. '.. '. 2.0 , Sludge Management .. . . . . .-.,... 21' . Solvent Management .... ... - 21 CHAPTER 3 WASTE REDUCTION ASSESSMENTS, . . .... ... . 23 ; PLANNING AND ORGANIZATION; . ..... . . . . . .23 ASSESSMENT PHASE . . . - 24 FEASIBILITY ANALYSIS .. . . ?. . . -1 . . .' . . . ... . 31. IMPLEMENTATION OF WASTE'REDUCTION OPTIONS . . , 34 'REFERENCES ... . . . . . '. '.-'. . . . -.. ., - '....' "-. -. 3S ------- ------- CHAPTER 1 INTRODUCTION * * * * * There are several good waste reduction and recycling opportu- nities available for metal' finishing, metal' fabricating, elec- troplating, 'and printed circuit board- manufacturing operations. This-manual will help you identify methods that can be used in these operations to reduce the amount of waste generated and at the same time help you to achieve other important obj ectives such as increased profits, productivity, efficiency, and , product quality. , ' _ . ' > ' _ - : . ' - f . ^ - . . . _., - .. WHY SHOULD YOU BE INTERESTED IN WASTE REDUCTION? Many businesses are finding that waste management is becoming increasingly more burdensome in terms of time, resources, and costs, of particular concern to these businesses are such issues as: '..'/ ''". .-'.' - ' " - strict limits for.discharging process wastewaters to the -- sewer' ' - . ;.'..'''."' "" - -'.''- - costs of wastewater treatment to meet those limits - regulatory requirements for hazardous waste management: - costs of managing and disposing of hazardous wastes - liabilities associated with the management of hazardous waste " .. '_ ' . ', '' .;-,'; .-'"--. . ' " - land disposal restrictions of certain hazardous wastes Waste reduction and recycling can help you address these problems and reduce the burden of waste management on your HiVe i ness.' Waste reduction is a means of generating less waste in'your operations thereby reducing your company's efforts and resource* required for waste management. WHAT DOES WASTE REDUCTION AND RECYCLING MEAN? .waste Reduction; Waste .reduction is any activity that reduces or eliminates the generation of hazardous waste at the source, usually'within a production process. These source reduction methods include such activities as good housekeeping practices, ------- ' J- raw satenai substitutions, equipment modifications, production process changes and waste segregation. was-e Recycling; waste recycling is the recovery or reuse of what would otherwise be a waste material. Waste recycling activities include the direct use or reuse of a waste material , in"a process or the reclamation or recovery of a valuable material from a waste. These activities reduce the. amount of a waste that requires disposal. This manual addresses both waste reduction and recycling activities for metal finishing, metal fabricating, electro- plating, and printed circuit board manufacturing operations. These methods generally focus on hazardous wastes-that are a-enerated in these operations, however, these methods can also be applied to non-hazardous wastes such as wastewaters, air emissions, and solid wastes. HOW CAN MY BUSINESS BENEFIT FROM WASTE REDUCTION? Waste reduction and recycling activities can help you to: Reduce cost* associated with 'the treatment and disposal of hazardous wastes. Reduce raw material/chemical requirements which lowers operating costs. Increase production rates and improve product quality. Reduce your liability and risks associated with the management of hazardous wastes. . Improve your company's public image by taking positive steps toward, the community's waste problems. create a safer workplace by reducing exposures to hazardous wastes. « Reduce the burden of trying to comply with regulatory requirements associated with hazardous waste generation. WHAT TYPES OF INDUSTRIES CAN IMPLEMENT WASTE REDUCTION METHODS? Any business that generates hazardous waste in their opera- tions, whether it is a small business or a large corporation, can implement some method of waste reduction. This manual specifically focuses on waste reduction and recycling methods for metal finishing, metal fabricating, electroplating, and printed circuit board manufacturing operations. ------- ^r.dustrv- Overview . ....- Industries involved in metal fabrication-, metal ^ finishing, elec*-opiating, or printed circuit board manufacturing utilize a wide range of production processes and operations. These processes' include: ". . , . surface preparation/cleaning, . ; ' -. paint stripping' ' --. ' .'',; ' . , . , . -' degreasing.' -,... ' '' -'' " . '' -' ' p ickling . : bright dipping and.chemical polishing . ; electroplating '>..-. . electroless plating . anodizing coatings (chromating, phosphating, metal coloring, 'passivating) ' , ... etching and chemical milling painting . heat treating - fabrication , - ", machining (cutting, grinding, welding, polishing, buffing) HY Thaaie Industries ' ... . These operations can generate potentially hazardous wastes listed below. The classification of .a particular waste »_s hazardous depends upon its specific characteristics and components. .spent acid or alkaline cleaning solutions spent solvents . . , , . ,_ *.u ' spent process baths: plating, etching, pickling baths sludges from process baths process rinsewaters wastewater treatment sludges paint residues and sludges still bottoms from solvent distillation systems .spent aatal working fluids (coolants, hydraulic fluids, lubricating oils, cutting oils, and quenching oils) -t HOW TO USE THIS GUIDANCE MANUAL Chapter 2 of this guidance manual describes detailed waste reduction methods that can be used to reduce or eliminate the generation of wastes from industrial processes. General-wast< reduction methods, that can be applied to.a wide range of industrial processes, are described, as well as process- specific waste reduction methods for electroplating, metal ------- finishing, and printed circuit board manufacturing operations. Chapter 2 also provides a description of the chemical and metal recovery processes including evaporation, reverse osmosis, ion exchange, electrodialysis, ultrafiltration, and electrolytic recovery. Chapter 3 describes the procedure for conducting waste reduction assessments. The assessment is a useful tool for identifying and evaluating waste reduction opportunities within a facility's operations. ------- *** *«1 ,, ; - ' .. CHAPTER' 2 WASTE .REDUCTION AND RECYCLING METHODS "r * * GENERAL WASTE REDUCTION METHODS ' -....'; Waste reduction and recycling methods are site- and process- specif ic> although a number of general- approaches, and tech- niques have been used successfully across the country to reduce many types of industrial waste. These techniques range from low or no cost methods to major 'equipment modifications requiring large capital investments. These techniques can have. ah application across a range of industries, and manufacturing processes/and can apply to hazardous as well as r.er.-hasardous wastes. These general methods include: Process and Equipment Modifications Input Material Changes Improved Operating and Housekeeping Practices Recycling Process and Equipment Modifications - ~ Redesigning or replacing equipment in order generate ' ' . less waste.- -; - - : . / '-.-',- production process to use less raw materials and/ or generate less waste. Use of automation which helps to limit inadvertent releases and off -spec product generation. Changes in operating conditions, such as flowrates, temperature r pressures, residence times. Implementing energy and water conservation programs. - -''-.*. " ,-..-," l " * ' Input Material Changes e Material substitution or replacing a. hazardous substance used in a production process with a non-hazardous or less hazardous substance. Examples include replacing a .solvent cleaner with an alkaline cleaner. -Material nurifieation involves the purification of /input or feed materials in order to avoid the introduction of inerts or impurities into the production process, When impurities are introduced, the production process must ------- eventually be purged in. order to prevent undesirable accumulation of the c6ntaminants, thus generating a waste. An example of this method is the use of deionized water for process baths and rinsewater in plating operations. ' _ Improved Operating and Housekeeping Practices . . Tmnroved material tracking and inventory practices can reduce the waste resulting from overstocking and disposal of materials with an expired shelf-life. Examples of these methods include: - purchasing and using raw materials only as needed. - keeping inventories of hazardous substances for each storage area in.the plant. - monitoring the quantities of waste resulting from expired stock. - maintaining Material Safety Data Sheets (MSDSs) for all materials in use. - labelling all containers to indicate the name and type of substance, stock number, health hazards, suggestions for handling, and first aid information. e Improved material u«aa«. handling, and Storage can reduce loss of input materials due to mishandling and improper storage. These methods include: - standardization of materials or using the minimum number of material types in your operations. This increases the potential for recycling and reduces the amount of waste requiring disposal. - improved operation and maintenance of container and drum storage arsas. . Good operating practices include: ' * providing adequate aisle spacing to facilitate container transfer and easy access for inspections. * properly labelling containers with material identification and health and safety hazards. s , * stacking containers according .to manufacturers' instructions to avoid ------- damaging -the containers from improper weight, distribution. . , . . * -segregating different hazardous substances. to prevent'.cross-contamination and-mixing of : r ,.-.' incompatibie^materials, 'and 'to facilitate . r ' . ' inventory control.- . / . . ., ' , ' ' . ;' * storing containers on-pallets or similar - 1 device to prevent, corrosion of the containers which-can result when containers come in contact with-moisture on the.floor. . *' constructing secondary containment structures, such as curbs, around storage * areas. ' . "''' . '.; . -. -," .. improved scheduling of. batch production runs to reduce the frequency of equipment and tanJc cleanings can result in less waste being generated. Reeordkeiepina and documentation-of operational proce- dures promotes the consistency of these'operations, thereby reducing the likelihood of producing unaccept- able products which must be discarded, and helps tc identify practices, that need to be improved. An operat- ing manual will assist the operators in monitoring . waste generation and identifying unplanned waste releases, and assist in responding to equipment , failures. '. - ''.-" - -.....-_ ' . , ' ' Recordkeeping should include the following items: -documentation of process procedures, control parameters, operator responsibility, and hazards . in a manual. - waste generation, waste handling and disposal ' .' COStS. .; -. . ' ;- . - . '- ''' - unplanned waste releases such as equipment . failures or spills and leaks, and costs of - cleanup. . _ :.';.''...-' ' , ' : , /'v ; - MSDSs... " /'/.- ;, . ' - -. '_ '" - ' - . Preventive maintenance improves the efficiency and longevity of equipment, reduces slow-downs or shutdowns from equipment failures, and reduces the likelihood of producing rejected, off-specification products. Pre- ventive maintenance should consist of regular inspec- tions and cleaning'of equipment including lubrication, ------- resting, measuring, and replacement of- worn or broken parts. _ spill anH leak prevention includes operational procedures and precautionary modifications to equipment and containment areas to minimize leaks and spills. These measures include: , . . . - installing and periodically testing overflow alarms on storage, process, and treatment tanks. - using tanks and containers according to . manufacturer instructions and only for their intended purpose. - maintaining integrity of tanks and containers. - 'implementing controlled andi supervised loading, ' unloading, and transfer of all hazardous substances. - constructing secondary containment: structures around tanks or storage areas .containing hazardous substances. - developing spill prevention plans. Waste segregation promotes recycling and recovery of waste streams and improves the treatability of a waste. Wastd types should be segregated as follows: - hazardous from non-hazardous wastes (Note: \ mixing a hazardous waste with a non-hazardous waste generally results in the entire mixture becoming a hazardous waste, which must be managed and disposed as such). - liquids from solids. - by hazardous constituent, such as chlorinated solvents from non-chlcrinatsd solvents. ^ , - waste streams containing recoverable metals from waste streams containing chelating agents. e Employee education and training is an important element. of any waste reduction and management program. Employ- ees directly involved with processes and activities that generate wastes should have an understanding, of why and . how wastes are generated, how they are managed, and costs and liabilities incurred by your company in^ generating hazardous wastes. ------- r-piove.' training should" consist of: .,. " - ' ' '- health ;and safety 'aspects of ail hazardous - ^stances being handled.. . **r oo«ration- of process equipment and waste - " llcyclinganS treatment . facilities, .. - . - procedures for handling Bleaks and spills ,; ' . -. ; '' include programs, to allocate r u r~ rMrr~-T *o the l c, waste ^reatment ', accounts and reuse_involv« . B.cl«acicn or^.=overy >* a >slu,bl. material from .. . hasardous wasta. ^ ffrryr>rTQN ^D FfryfT.T^ ftPFLKftTI^S . . '-' ' " e.... applied to metal - f abrica t ^"^ »« operations are sum- a?d printed circuit b^ »?^^Can5 evaluating waste reduction mirized below. ^"^WS^SJ emphasis should be placed options for your oPer^i°^' « cost Material handling and first on the simple, , low .or n ° «rjr_ativ-s- have been consid- process changes., After^these |^^V^dif ication and waste 1 «aste t-n and recycling metthoda includ«= , , ..laproved operations and Housekeeping Practices Drag-out Reduction Metal Recovery Processes Sludge Management solvent Management ------- J5 AND HOI The following practices are easy to implement and require little o? no capital investment: Repair all leaking tanks, pumps, valves, etc. " . inspect tank and tank liners on a re^lar basis to prevent failures that may result in bath dumps. steam coils and heat exchangers on a regular Prevent accidental contamination of steam of condensat event accenta con conate and cooling water or leakage of condensate and cooling water into the platxng bath. rinse . «» baths when not in use. * Minimise the volume of water us«d during cleanup operations . ' £3. s^uW ^ r«ov.d from th. bath wh«n not belng plated. np^fi-QUT *«-.- *.« «.v,4» nla*-*«c: solution that adheres .to the methods include: 10 ------- Modifying- properties of, the placing bach :co improve ' d-ainage of the plating' solutions ..-bade'.. into the. piatir.g' ' baths or reduce: the. concentration of dissolved metal's -r. the drag-out.; .These, methods .include: - Decreasing .bath viscosity: by reducing the -chemical concentration of 'the bath or by increasing the bath temperature. . . . ' - Decreasing bath surface tension: by adding ,non- 11 ."'.ionic wetting, agents or increasing bath ' "temperature. : , . , Lowering the withdrawal rate of parts from a bath. This method can reduce the thickness of a drag-out layer .because of surface tension effects., increasing the drain time over the plating tank. installing drain boards, drip bars, and drip tanks to capture the drag-out. The collected drag-out can be fully or partially returned to the plating- bath to make , up for evaporative losses. These devices save chemicals, reduce rinse requirements, and prevent unnecessary floor wettings. Proper racking: Carefully rack and remove parts so as .. to minimize entrapment of bath materials on surfaces and in cavities s - parts should be raekexl with major surfaces. - '; ' ' ' vertical. . - '. . ' ' . ' - parts should not: be racked directly over one another. - . ...-'. . - ... - , ' % - parts should b« oriented so that the smallest surface area of the piece leaves the bath surface " . ' last. ' ' ; "':_ i ; ;" -' :: - ' :' . : Designing parts to promote drainage, such as with no cups or shelves. . .Designing Plating racks with a minimum surface area, minimum horizontal surfaces, no pockets, and an effective orientation to promote drainage. e Using air knives with oil-free compressed air to Knock off parts and back into , the plating tanks. Using, fog and-spray rinses, parts can be spray rinsed with deionized water over the plating tanks. This method is. used when tank evaporation rates are 11 ------- sufficient to accommodate the added volume of spray water. In rack plating: Provide drain bars over the plating tank from which the rack can be hung to drain for a brief period. In barrel plating: Rotate 'the barrel over the plating tank to remove excess plating solution. i | * ' RINSEWATER MODIFICATIONS ' , Methods are available to improve rinse efficiency.and reduce the amount: of rinsewater generated. These methods include the use of one or more of the following: Still rinse or drag-out tank: A still rinse tank can be used prior to the rinse tanks with flowing water. As the concentration of the plating solutions in the still rinse tank builds up over time, the rinsewater can be returned to the bath to make up for evaporation losses. e Rinse tank mixing: The even distribution of fresh water throughout the rinse tank in addition to aeration can increase the efficiency of water use. e Water supply control valves: These are inexpensive devices to regulate the feed rate of water at an optimum level. e Spray rinsing: In this method, when the workpiece is sprayed with water, the process solution films are washed off the parts through use of'impact and diffusion forces. This method, which can reduce water usage as much as 75%, is effective on simple workpieces, such as sheets, but has limited application for odd-shaped pieces. e Fog rinsing: This method uses water and air pressure to produce a fine mist which reduces the concentration of the drag-out film. This method is effective on simple workpieces but has limited application for odd-shaped pieces. e Cascade rinsewater recycling: In this method, overflow from one rinse tank can be used as the water supply for another compatible rinsing operation. Countercurrent rinsing with multiple tanks: In this arrangement, three rinse tanks are operated in series with the water flowing- from the tank farthest away from the plating tank toward the tank closest to the plating 12 ------- - > '-ar.'k by g-ravity or pumping. The workplace is tiall-y'* inaersed in each of the .three rinse .ranks, counter-current to the rinsewater ' f low, from the, least pure rinse, tank to 'the cleanest rinse tank. . - ' Counte-rcurrent rinsing can reduce rinse flows by . : '''-"' over 95% compared to/single overflow 'rinses. - '''Disadvantages, with this arrangement include .additional space requirement's,, additional . production time', requirements,, and 'costs of > .additional rinse tanks. ' . . MATERIAL/ CHEMICAL ?TT?STTTOTTONS . ' ... '.'.- The incentive for substituting process chemicals containing nonpolluting materials has surfaced in recent years -in response to the increasing complexity of pollution control regulations. BY eliminating polluting process materials such . as hexavalent chromium or cyanide-bearing chemicals, the treatments retired to detoxify these wastes are also eliminated. This is desir- able particularly for hexavalent chromium and cyanide wastes since they require a special treatment step and equipment to detoxify - : : ' , . Material and chemical substitutes are now being gradually introduced into the marketplace by chemical manufacturers and suppliers. When evaluating and selecting chemical substitutes for a particular application, a r.'jsber of factors should b= considered, such as: ^ . ' Are substitutes available and practical? Will substitutes, solve .one -problem but create another? "'".'" - \ ''.-.'-'" ; , ...... - / .-_. ! will tighter chemical controls be required of the bath? Will product- quality and/ or production rate be affected? Will the change involve any cost increases or decreases? Some commonly used material and chemical substitutes in electroplating, metal finishing, and printed circuit board manufacturing operations are summarized below: ical Subsfeitutg* for Alkaline Cvanide Plating '' in. zinc plating, chemical substitutes include: , - ammonium or potassium chloride baths for , ' complex ing' zinc. 13 ------- - acid .sulfate, chloride, and fiuoroborate baths. In cadmium plating, chemical substitutes include: - acid baths consisting of cadmium oxide, sulfuric acid, distilled water and anionic compounds. - cadmium chloride. in copper plating, copper sulfate can be. used as a chemical substitute. In tin plating, acid tin chloride can be used as a chemical substitute. ' . Chromium Plating Baths Trivalent chromium solutions can be used in place of hexavalent chromium solutions in some situations. This reduces drag-out concentrations of chromium. Pickling solution and Brian* Dip Alternatives Sulfuric acid and hydrogen peroxide can b« used , as , substitutes for chromic acid. Cleaners Trisodiua phosphate sr asscr.ia can b* us«d a substitutes for cyanide cleaners. Coer Etehants Sulfuric peroxide can be used as a "substitute for persulfate. , . PLATING BATH MAINTENANCE Plating solutions contain valuable metals in high concen- trations as well as chemical salts. and additives, over a period of time, contaminants can build up in the plating bath and reduc* th« effectiveness of th« plating operation. For reasons of economics, th«s«. plating baths ar« rarely ever changed out or dunp«d. S«v«ral methods are available to maintain th« quality of the plating bath and include: Removing impurities from plating baths: , - Suspended solids can be removed by filtering. 14 ------- - Nickel baths'can be'purified by 'activated- carscr. . adsorption. '.. ' . ''- Carbonates in cyanide bath's can. be removed by. chemical, precipitation. ; . . - using deionized water for makeup and.- as :rinsewater. CHFMICAI, 'PROCESSES ' Chemical recovery processes' are available to reconcentrate, plating solutions from, rinsewater for reuse and to. purify spen. process solutions. These methods are summarized below. When < Evaluating a recovery process for a .particular plati.ng oper- ation, general and site-specific factors must be considered These factors include the metal being plated, drag-out rates, concentration of metals in the rinsewater, rinsewater fj£w- rates, space requirements, personnel requirements, energy requirements, and cost and payback period of the recovery system. , ' ' - ' . ' :' . . . - '''".' Evaporation! Application: In this process, rinsewater is boiled to concentrate the' plating solution. Steam from the process is.condensed and reused for rinsing. The plating solution is returned to the plating bath. This process can recover 90 to 99% of the dragged-out metals. Drag-out -recovery of 'rinsevatsrs frcr: - hot chromium baths - ambient temperature nickel baths ; - metal cyanide baths Use in conjunction with countercurrent ' rinsing. . Simple,.reliable, widely applicable process. , Relatively maintenance-free compared with other recovery processes. Disadvantages: High energy use. Requires periodic removal of impurities from the recovered plating solutions. Advantages: Reverse Osmosis: 'in this process, water is separated from dissolved metal salts by forcing the water through a - semipermea'ble membrane at high ,15 ------- Application: Advantages: pressures. A concentrated solution con- taining the. plating metals is produced and returned to the plating bath. The purified water is reused for rinsing. This process can recover up to 99% of the dragged-out metals. ' Drag-out recovery of rinsewaters from,the following plating-baths: ' - acidic nickel (Watts nickel lines) - nickel sulfamate - copper pyrophosphate - copper sulfate - nickel fiuoroborate - zinc chloride - zinc, sulf ate -cyanide baths for copper, zinc, and cadmium For use on lines with heated plating baths where evaporation is high enough to allow the concentrate to be fed directly to the plating bath. Use in eonjunction with still rinse tanks, countercurrent rinsing, or other rinsevater conservation techniques. Produces m^dina to high ccr.scr.trnticr.3 cf metal salts for reuse in the plating baths. Disadvantages: Performs efficiently on dilute rinsewaters. Nonselective in removing dissolved substances from the solution. Impurities such.as organic brighteners, wetting agents, and unwanted metals may be returned to the plating bath along with the recovered metal. To prevent fouling of the membrane, prefiltering of the rinsewater is required to remove solid particles, oxidizing materials, and oil and grease. * ' Limited application for solutions with high oxidation potential (chromic acid) or extreme pH (i.e. high pH cyanide baths) -due to destruction of membranes. 16 ------- -<*«' s-x-.hanae;' The ion exchange process can be used .or, '."" ".""" -'removing contaminants from process baths or ' recovering.dissolved metals from rinsewaters. .The process can recovery 90 to 95% of the metals ', in drag-out. 'There are two types of 'ion exchange units, cation and anion. The selection- of the type of : .. ion exchange -unit to use for a particular . application will depend upon the ionic charge of the contaminant to be removed or.metal to be ; recovered. --.".-, , . .,-.'; >;> 'A cation exchange unit, contains a specific type of resin to remove positively charged ions .rom.- solution, such as metal cations. The cations removed from the solution are typically replaced by hydrogen ions that are displaced from the resin> The solution that exits the cation exchange unit has a limited potential for reuse as a rinsewater due the presence of the . hydrogen ions which make the solution acidic, After a period of time, the capacity of the resin to Remove additional metal cations becomes ' limited and the resin must be regenerated if it is to be further utilized. Regeneration of the cation exchange unit consists of passing a strong acid, sucn as sulfuric acid, througn resin bed. The solution exiting the cation exchange unit from the regeneration process contains the metal ions, which can be returned to plating bath. An anion exchange unit contains a type of resin to remove negatively-charged ions from solution, such as chromate and cyanide. Typically with anion. exchange units, hydroxide ions are ^ displaced from the resin to replace the anions removed'from the solution. The anion exchange units are regenerated with a strong base, such as sodium hydroxide. Application: Purification of spent process acids. Recovery of anodizing baths. Drag-out recovery of rinsewaters from the . . following plating baths: 17 ------- Advantages: Disadvantages; - Acid copper ' - Acid zinc - Nickel - Tin - Cobalt . - Chromium / Can remove all metal ions from a relatively dilute solution. Low capital and operating costs compared to other recovery processes . Not capable of producing a highly concentrated stream for return to the plating baths. Does not remove organic additives from a wastewater. Prefiltering of the rinsewater may be required to remove solid particles and oil which can cause fouling of the rssin. Not cost effective when drag-out rates are low. . Equipment is complex, requiring tight operation and aaintsr.anc« . Monitoring of the ion exchange unit is required to ensure that the resin capacity is not exceeded.. Resins require periodic regeneration .with strong acid or caustic. E Lec,trod i a 1 vs i s t Application: In this process water is separated from dissolved salts using a network of alternately-spaced anion-permeable and cation-permeable membranes. An electric potential is applied across the membranes to provide the driving force. This process- can recover 90 to 95% of the metals in drag-out. Regeneration of chromic acid etchant.. Drag-out recovery of rinsevaters from the following plating baths: - nickel - acid zinc 18 ------- Advantages: Disadvantages: - zinc cyanide - chromium -' . gol'd . - -~ silver Use 'in conjunction with a still rinse- tank. ' ' '.-. ' , " - . , ' ! - ' '.";' Achieves higher concentration o,f metals than reverse osmosis or ion exchange. Energy efficient. Can operate .continuously without, requiring regeneration. Requires little; space. : Nonselective in removing dissolved substances from the solution. Impurities such as organic brighteriers, wetting agents , and unwanted metals may be returned to the plating bath along with the recovered metal . Membranes are sensitive to extreme pH, flow variations, and suspended solids. Pref iitering o£ tne rinsewater may oe required to remove solid particles and oil which can cause fouling of the - resins. ..'...' ' . - , , Requires careful operation and periodic maintenance to- avoid damage to the membranes. t r a f i 11 ration: Application: In this process, a solution is filtered through an extremely fine filter to -remove . solids, emulsions, and high molecular weight organics. Regeneration of alkaline cleaners, coolants, or process baths requiring removal of particles and emulsified oils wastewater treatment process for volume reduction of spent coolants, cleaners, and rinsewaters. ------- Advantages: Disadvantages: Efficient for removing suspended solids, emulsified oils, and other hrgh molecula: weight organic compounds. Low capital and operating costs. Easy to operate and requires little maintenance. ' Limited application for recovery of dissolved metals from rinsevaters. Requires periodic backwashing to remove, captured solids. METAL RECOVERY PROCESSES E1ectrolvtic Recovery: Advantage: This process involves the electro- chemical reduction of metal ions to their elemental forms as a powder or foil. A direct current is passed through a metal-bearing solution by means of cathode plate and insoluble anodes. The cathode consists of a stainless steel or carbon fiber plate upon which the recovered metal is deposited. After the coating is sufficiently thick, the metal is peeled off and sent to a refiner or the coated stainless steel cathode is used as an anode in plating baths, serving a source of metals. Application: Oxidation of cyanide. Reduction of hexavalent chromium in wastewaters. Recovery of metals from plating and etching bath drag-out, such as gold, silver, copper, cadaium, zinc, tin, and lead. Regeneration of ammoniacal and chloride etch solutions during metal recovery. Us* in conjunction with m still.rinse tank. Not a labor-intensive operation. Low energy requirements. 20 ------- - . - . -. _ Lev energy .requirements". Disadvantages: Limited application for recovery,of ,' . ' . chromium from solutions.; . . '. .' . '. Monitoring of the solution concentration \ ' ; -is. required. _'.-.''''. SLUDGE MANAGEMENT , - ". ' ', " '.'.-" Sludges produced in process baths and as a result of ' wastewater1 treatment processes are typically hazardous wastes that .must be appropriately managed., Frequent management problems with these sludges include" the high volumes-generated that must .be handled cand costs for disposa'1. Some waste, management alternatives 'are available, to,help alleviate these problems. / Sludoe Dewaterino: :- -" ..';'' . - ,.' Several mechanical dewatering devices that reduce sludge volumes are commercially available. These devices include: Centrifuges . , Filter presses , . - . « Vacuum filters . . . Sludge dryers . treatment Chemical Selection A wide range of treatment chemicals is available for precipitating dissolved metals out of a solution. Some .of these chemicals produce less sludge-when compared to other chemicals of comparable removal efficiency. Therefore, the selection of a treatment chemical for a particular application is important for reasons of efficiency and sludge volume .production. ' V ..'',." - ' - - ., Examples of treatment chemicals that produce less sludge- include: ".'- :..': _ . _ , . ' use of caustic soda (NaOH) instead of lime (Ca(OH) 2-) ' * use cf polymers instead of ferrous sulfate and alum*. SOLVENT MANAGEMENT ..'..'-' -M ' - ; . --: --.-.. Organic solvents are widely used in metal finishing operations for cleaning, decreasing, and paint stripping. The management and disposal of spent organic solvents are becoming increas-- ingly more difficult and expensive. Some waste reduction and recycling methods for organic solvents are summarized below. ------- Material Suhstj*--"* i°-Q ' . Alternatives to using solvents include: .Alkaline cleaners High pressure hot water washings Steam cleaning . ' * ecovered and reu.sed. pece. The particles can be recovered and reu.sed. Recovery and Reuse . . Methods for reusing and recovering spent solvents include the following: ' reuse: This involves using a spent finishing applications e "ffn*;t Beveling:. Several waste management services * are available for recycling »PV°i££SbS your facility site or at an offsite location. 22 ------- ..TSR' 3 /- \ .WASTE REDUCTION: ASSESSMENTS A waste reduction' assessment is a step-by-step procedure that -an be used by a facility ' s, own employees to identify waste reduction and recycling opportunities. -The assessment can he.p . Jou.to understand the facility ' s wastes and processes ^dent, viable options for reducing wastes, and determine which options art technically and economically feasible to justify implemen- tation in your operations. The amount of effort required for a waste reduction assessment will depend upon the size and type of your business. Small facilities with only a few processes will obviously require less time" and resources for the assessment. Large facilities with mtny processes may require a team of skilled professionals to conduct a more detailed technical and economic evaluation of waste reduction options. , . considerino the wide range of waste reduction and recycling .. opSortuni?ies available for metal finishing and'.l^rbplating. opSrltions, it is likely that your business can implement waste reduction methods and end up saving money as a result.^ The following steps will provide you with some general guidance in identifying and implementing waste reduction and recycling practices in your operations. Mote that all waste streams should be considered when conducting an assessment, *uou " hazardous wastes, wastewaters, air emissions, and non-hazardous solid waste. Additional sources of information on waste reduction methods and implementation can be found in the ; .references-, i . . ' . ' . . - - ' There are several different, tasks, involved when conducting. a waste reduction assessment. These tasks include the following: Planning and Organization * Assessment Phase - e Feasibility Analysis e Implementation and Evaluation PTAMNTNG Planning and organizing waste reduction assessment are esslntiai: steps to ensure a Program's success. ^^ is conducted prior to actual assessment phase. Important elements, of this tasfc are summarized below.. 23 ------- Get a commitment and support from management. It is a _ .e to provide the time, personnel, financing, and. other resources required for developing a waste reduction program. . ' important for the management of a company to support waste reduction program. The management must be abi< Develop a formal policy statement describing the waste reduction program objectives. .Involve employees in all phases of waste reduction program development. Organize a waste reduction assessment team. - Get people who know the facility, processes, and operating procedures, and are familiar with your waste management practices, environmental "regulations, and waste reduction and recycling techniques. Get people from affected departments or groups, such as production, maintenance, environmental, safety, sales, purchasing, etc. Involve line operators and production supervisors. - Appoint, a team leader who has a strong technical background and good problem-solving and manag skills. Set goals to achieve waste reduction. Recognize potential barriers and problems that may hinder waste reduction program development. ASSESSMENT PHASE This phase involves an evaluation of the facility's operations, waste streams, and waste management practices and the identifi- cation and screening of potential waste reduction and recycling options. Important steps of this phase include the following: 1) Faeilitv Information One of the first steps of the assessment is to gather background information on production processes, operating procedures, waste streams, and current waste management activities, collecting data, will create a basis by which the assessment team can track the flow and characteristics of. the waste streams over'time. This will be useful in identifying 24 ------- i 1 4 ^B g* """" collected .. team is. better production, rates ; - . ^ process descriptions and efficiencies . condition of proce,a ea^ip*ent, such as tanXs, pu,Ps, pipes/'and valves . sourc,. or pot.nU.1' spur=« of X..X, and operating procedures . maintenance:procedures and schedule., .operating and;maintenance costs , .energy/utility usage and costs material inventory -s or o«,.r raw material costs . «t.ri»l transfer and handling procedures e storage procedure* ' .source, oi leaX, or spi^s in ***** - . condition of pipe*. P-PS- tanK,', valve,, and storage/ delivery areas . 25 ------- Data; . activities, processes, or input materials that generate waste streams physical and chemical characteristics of the each waste stream . hazardous classification of ^V^^ant^ which wastes are hazardous and which, are not.) of waste stream 'generation. (i.e. continuous or nt, such as from9periodic cleaning activities or bath dumps) ' . rates 'of generation of each waste stream and any variability in these rates Waste e current disposition of 'each waste stream (i.e. hew is it handled, treated, and disposed) . costs of managing waste streams, including treatment and disposal costs * operational procedures for waste treatment units e efficiency of waste treatment units quantity and characteristics of all treated wastes, sludges, and residues waste stream mixing (are hazardous wastes mixed with non-hazardous wastes or are potentially recyclable wastes mixed with other wastes? )^ « Reduction; , e current waste reduction and recycling methods being implemented . ' e effectiveness of those methods , sgureea gf Baekq-ramid' m formation 26 ------- --ocess flow diagrams .- ' Material and heat balances for production processes and waste treatment processes ./, - _ ' -_ . -. operating manuals and process descriptions : , equipment specifications and data sheets, piping and instrument diagrams .. plot. and elevation plans '. sewer diagrams ' . ; , , . equipment layouts 'and work flow diagrams hazardous waste- manifests . emission inventories . annual hazardous waste reports envlronmentalSaudit and inspection reports- . reports ( 'or r.l««« inventoriw (SMI* Title III requirements) . product composition' and batch she«ts material application diagrams . material safety data sh««ts (MSDS) product and raw ftatarial inventory records op«rator data logs production schedules _,. d«parta«ntal cost accounting reports company environmental policy statenmnts organization charts in some situations it may b* necessary to develop flow diagrams and mS?.riaror Sass balances of th* major waste generating operations. Th«s« flow diagrams and mass glances help to identify waste sources, concentrations, and rates of .generation. . .. 2) q w**n funds time, and- personnel are limited, it may be and budget permit. Items that should be considered when prioritizing include: compliance with current and future regulations . costs of waste treatment and disposal ', - .' . 27- . . :'". ' '. - -. ------- potential environmental and. safety liability quantity of waste haza-dous properties of the waste (including toxicity, reactivity, corrosivity, and ignitability) safety hazards to employees potential for reduction, recycling, or recovery potential for removing bottlenecks in production or waste treatment potential recovery of valuable by-products available budget and expertise for the waste reduction assessment program and projects 3) SJ-te Inspection The purpose of the site Inspection is to verify background _ information, fill data gaps and resolve questions raised while collecting and reviewing data, identify additional sources of wastes? and collect information on actual operating and waste management practices. The inspection concentrates on under- standing how and why wastes are generated. For each of the selected processes or operations *««£ . evaluated, the inspection should follow the process from the point where raw materials enter the process to the point where products and wastes exit. Some general guidelines for conducting the site inspection . include the following: ' Prior to the inspection: - make a list of items that require clarification. - notify personnel involved within the process or area to be inspected. Schedule the inspection t°'coincide^with_ the particular operation of interest; if the operation is P«"?^f. or intermittent in nature (e.g. bath dumping, chemical , addition, etc.). ' . . ' . e During the inspection take notes and P^fF*** th?, t areas of interest. This helps to recall details that may be forgotten at a later date. 28 ------- Monitor the .operation at different times' during.the. shift and during thedifferent shifts, especially, if waste generation is highly dependent on human , : involvement. :t ' ;; interview the operators, maintenance personnel, shift , supervisors, and foremen in .the area's being inspected. Assess .the" operators1 and supervisors' ^awareness of the waste generation aspects of the operation and familiar- ity with the impacts their operation may,have 'on other 'operations. . ^ . Observe housekeeping aspects of the operation. Check for signs of leaks or spills. Assess the overall cleanliness -of the site. , Note any odors and fumes. Evaluate the organizational structure and level of coordination of environmental activities between various departments. . ... ''," . . Evaluate administrative, controls, such" as cost accounting procedures, material purchasing procedures, and waste collection procedures. , - 4) Generating Waste Reduction Potions After the data collection and site inspection stages of the assessment, the next step involves identifying possible waste reduction and recycling options* This step requires the expertise of the assessment team members. Much of this knowledge comes from their education and on-the-job training. Other sources of waste reduction and recycling information are listed below: '. . .. :. : , ',' . " . "';. ; e Trade associations , e Plant engineers and operators e Published literature such.as technical journals, trade journals, government reports, conference proceedings, and research reports, ; e DEQ Waste Reduction Program e Workshops, conferences, and seminars e Equipment vendors . consultants and employees from other facilities 29 ------- Waste -eduction and recycling methods for electroplating, metal finishing, and printed circuit board manufacturing operations vere discussed in Chapter 2 of this guidance manual. 5) screening apd Selecting Wasta Reduction 'Qp^ons for Further Evaluation Since detailed evaluation of technical and economic feasibility is usually costly, the proposed waste reduction options should be screened to identify those that deserve further evaluation. The screening procedure serves to eliminate suggested options that appear marginal, impractical, or inferior without a detailed and more costly feasibility study. When considering options, emphasis should be placed on process " changes and other source reduction measures, .followed by recy- cling and reuse. Many source reduction-.options involve no or low capital costs and can be easily implemented. After these alternatives have been considered, then the more expensive equipment modifications and waste recycling options should be evaluated. , The following criteria should be considered when screening and selecting options: existing technology (does the necessary technology exist to develop the option?) extent of current use in the industry i, P , , , successful performance history « cost and cost effectiveness reduction in the waste's quantity and hazardous characteristics (toxicity, flammability, reactivity, corrosivity) * reduction of treatment and disposal costs reduction in safety hazard e reduction in liability and insurance costs e "reduction of input material costs effect on product quality low capital cost low operation and maintenance costs 30 ------- c short implementation period ' . ' . , v o ease, of- implementation ' 7, ' . . . ' o other benefits , . . . : . FEASIBILITY ANALYSTS . / ' . . .: . ; ~- ' ' ,.'. After/identifying potential ^waste,reduction and recycling- options-, the next step is to conduct a detailed analysis of these options. The analysis of these options .includes both a technical and economic evaluation.. , Technical .Evaluation <_ - , The technical evaluation determines whether a proposed waste reduction option will work in a specific application. The following criteria should b« considered when conducting a technical evaluation: : - - -''," ' . will th« option work in this application? - How has it worked in similar applications? Will the option cr«at« less waste or just move the waste problem from one form to another? e Is the system safe for workers? . « Will product quality -fc'e' azintair.sd? ';,',,' " e Will the option adversely affect productivity? Is space available? Are the hew equipment, materials, or procedures. ; compatible with production operating procedures, work flow, and production rates? e Is additional labor required? Are utilities available or must they be installed? e How long will .production.be stopped in order to install -.the system? \"- .-..''" ; "-'' "\ ".' . .' ' ' '.' '.''".. e Is special expertise required to operate or maintain the new system? Does the vendor provide acceptable service? Does the system create other environmental problems? ' -''-...''. .3,1' ''.'. ''.-". ------- For equipment: related options: ' ' . V'si* facilities that have installed. the equipment, These visits can be arranged through equipment vendors and industry contacts. ,,, Solicit operator's comments and compare to vendor claims. .,'' conduct bench-scale or pilot demonstrations. Rental test units for bench-scale' experiments may be available from equipment vendors for use. some vendors may install equipment on a trial, basis, with acceptance and payment after a prescribed time, if the user is satisfied. ^valuation The economic evaluation is conducted using standard measures of Srofitabilitv such as payback period, return on investment, !nd net oriseAt value. Most companies have their own methods fSr S^lSHSS pSjSt. for implementation. In conducting an economic evaluation various costs and savings must be considered. Some of these factors are described below. For the purpose of evaluating a project to reduce waste . quIntitiSs, some types of costs are more significant and easily quantified. These costs include: e disposal fees transportation costs predisposal treatment costs raw material costs operating and maintenance costs When conducting the economic evaluation of waste reduction Sese^costs should be considered first .bmu.« th.y . ave a greater effect on project «cononiCVnd^h effort to estimate reliably. Other elements, such listed below, are usually secondary in their direct impact and should be included in fine-tuning the analysis. Costs; site development process equipment materials connections to utilities and services new utility and service facilities other non-process equipment construction/installation 32 ------- engineering and'consulting services , permitting '-.costs- ; . ' - .contractor's fees . -, ,. training costs - -, v , , . . ; . . ', " finance charges .-. = . ;. ,. . Coeratinq Cost? and Savings; ;, / . ' . , , -.Reduced! waste management costs . I.onsite and,offsite treatment, storage, disposal costs. ' " ..'.. - -;state generator fees . . ' - transportation costs - - . ,:. - permitting, monitoring, reporting, and recordkeeping costs " . ' ' Input material cost savings insurance and liability savings Chaha«s in cost associatad with product quality (costs lor Icrap? reworlc, and quality ^control inspections) * Changes in utility costs Changes in operating and maintenance costs for labor, burden, and benefits Changes in operating and maintenance supplies changes in overhead costs ; Changes in revenues from increased (or decreased) production . increased revenues from the sale of by-products Final and th« .& and .vaiuations. Th. r«port also affected groups be arven tne cnanc* wu review and comment ... report ShSIldcSUain a discussion of the following £, 9£*Wfe » ^^^^^ - r waste reduction options evaluated and results of the evaluation . , , , v - " .recommended options for implementation ' '. ' ' -33 ''' ' -..'". ------- . w*ethe~ the recommended technology or procedure has beer. established in the industry, with a mention of success- ful applications .how the project will be implemented required"resources, such as money, expertise, personnel, Available in-house and those resources that must be brought in from outside estimated construction period and production downtime expected performance of project . how the performance of_the project can be evaluated after it is .implemented reduction in environmental and safety liability Th. implantation of selected waste will Generally follow the procedures established by compandor implanting any new procedure, Pfocess cations, or equipment change. The assessment report to g«£ management approval and funding the selected projects. Steps involved reduction project include the following: Io help wait. a waste preparing a detailed design preparing a construction bid package lelSctinl construction staff and purchasing materials installing new equipment training personnel ; . starting operation monitoring and evaluating performance . justify the development of other waste reduction projects The waste reduction assessment program ****** options that were not pursued earlier 34 ------- REFERENCES Inforaation-'contained in -this-guidance document has been derived from the fpilowing sources:. , . . . .. Higg'ins, T. E. , CH2MHill, Evaluating Hazardous-. Waste Minimization Programs for Metal Fin.^hina Processes..- Presented at the AOI/AEA/DEQ workshop on "Responsible Hazardous Waste Management", Wilsonville, Oregon, March 24, 1987,.' ;, * -. . ' -: , . .' Lorton, G. A., and D. A. Hanlon, Jacobs Engineering .Group inc., waste Minimi 7*r1 on Assessments. prefente^L^Co California Aerospace Environmental Association Conference, Long Beach, California, February 17, 1988. -' '; ' New York State Departnent of Environmental Conservation, m-aff New York State Hazardous Waste Reduction Guidance Manual. November 1988. U.S. Environmental Protection Agency, Su.mm.arv .. .. gontrol and T-reatmenfe Technology for the Metal Finishing . Tndv!strv. Tn-.Planr- changes. Industrial Environmental Research Lab > Cincinnati; Ohio, , EPA/625/8^82-008, January ;1982. ' ..,''-..' '.,.'. :'-.''. ' U.S. Environmental Protection Agency, fleeing .. Waste Requirements for Metal Finishers. Seminar PUS Heat ion. Otfice o£ Researcn and Development, Cincinnati, Ohio, EPA/625/4-87/018 , September 1987 U.S'. Environmental Protection Agency, Wast;e .. Environmental Qualifcv with Economic Benefit?, Of f ice of Solid Waste and Emergency Response, Washington, D.C., EPA/530-SW-87-026, October 1987. U.S. Environmental Protection Agency, TftV SPA Manual f 07 v**±* Minim^M^ian opportunity Assessment , tHazardo,us wHte Enginiering Research Laboratory, Cincinnati, Ohio, EPA/5QQ/2-SS/02S, April 1988. For additional references on waste' reduction and recycling refer to OEQ's Bibliography of Hazardous Publications. ; 35 ------- ------- |