Metal linishers are represented in the partnership by the metal linishing Association or Southern Calirornia. The project implements P2 techniques and technologies at metal liniing racilities in southern california and documenting and sharing results. Electrowinning is an electrolytic technology used to reco er metals rrom electroplating rinse waters.
Metal linishers are represented in the partnership by the metal linishing Association or Southern Calirornia. The project implements P2 techniques and technologies at metal liniing racilities in southern california and documenting and sharing results. Electrowinning is an electrolytic technology used to reco er metals rrom electroplating rinse waters.
Metal linishers are represented in the partnership by the metal linishing Association or Southern Calirornia. The project implements P2 techniques and technologies at metal liniing racilities in southern california and documenting and sharing results. Electrowinning is an electrolytic technology used to reco er metals rrom electroplating rinse waters.
Merit Partnership Pollution Prevention Project for Metal Iinishers
The Merit Partnership is a joint enture between U.S. Lni-
ronmental Protection Agency ,LPA, Region 9, state and local regulatory agencies, priate sector industries, and community representaties. The partnership was created to promote pol- lution preention ,P2,, identiry P2 technology needs, and ac- celerate P2 technology transrer within arious industries in southern Calirornia. One or these industries is metal rinish- ing, which is represented in the Merit Partnership by the Metal linishing Association or Southern Calirornia ,MlASC,. To- gether, MlASC, LPA Region9, and the Calirornia Manurac- turing Technology Center ,CMTC, established the Merit Part- nership P2 Project ror Metal linishers. This project inoles implementing P2 techniques and technologies at metal rinish- ing racilities in southern Calirornia and documenting and sharing results. Technical support ror this project is proided by Tetra Tech LM Inc. ,rormerly PRC Lnironmental Man- agement, Inc.,. The project is runded by the Lnironmental Technology Initiatie and LPA Region 9 and is implemented, in part, by CMTC through the National Institute or Stan- dards and Technology. FLFCTROWINNING TFCHNOLOGY DFSCRIPTION Llectrowinning is an electrolytic technology used to recoer metals rrom electroplating rinse waters. Although electrowin- ning has traditionally been used only ror metal recoery, its application in a well designed and controlled rinse system can signiricantly reduce rinse water use, wastewater generation, and chemical discharge. An electrowinning unit has three main components: ,1, an electrolytic cell, ,2, a rectirier, and ,3, a pump. The electro- lytic cell and rectirier are shown in ligure 1. An electrolytic cell is a tank in which cathodes and anodes are typically ar- ranged in alternating order ,see ligure2,. The cathodes and anodes are attached to their respectie bus bars, which supply the electrical potential to the unit. The electrolytic cell may include reatures to improe rinse water circulation within the cell, such as a rlow disperser or air spargers. Vhen an electrowinning unit is in operation, the electrical potential applied to the electrodes causes dissoled metals and other positiely charged ions to migrate toward and plate onto the cathodes. As metals deposit on the cathodes, the metal buildup decreases the deposition rate. Vhen the metal depo- sition rate is no longer surricient, cathodes are remoed rrom the electrolytic cell ror on-site or orr-site metal recycling. In some cases, recoered metals are pure enough to be reused in process baths. As metals are chemically reduced at the cath- odes, other rinse water components are oidized at the anodes. Ir cyanide is present, it is oidized to cyanate and then to carbon dioide and nitrogen. NOVLMBLR J997 Iigure J. Llectrowinning Rectifier and Llectrolytic Cell Iigure 2. Cross-section of Llectrowinning Unit TO STATIC RINSL OUTLLT BUS BAR CATHODL ANODL CONNLCTION TO RLCTIlILR INLLT PUMP lROM STATIC RINSL lLOV DISPLRSLR AIR SPARGLR MFTAL RFCOVFRY AND WASTFWATFR RFDUCTION USING FLFCTROWINNING TFCHNOLOGY APPLICATIONS Llectrowinning is most commonly used to recoer gold, siler, copper, cadmium, and zinc. Gold and siler are the most successrully recoered metals because or their high electropotential. Chromium is the only metal commonly used in electroplating that is not recoerable by electrowinning. Nickel recoery is possible, but the process is ery pH-sensitie as the pH must be maintained within a small range ror metal deposition to occur. Some rluoroborate-con- taining solutions, such as tin and tin-lead solutions, can corrode cer- tain anode materials. Most etchant solutions dissole metals orr the cathodes as quickly as they are de- posited. DFSIGN AND IMPLFMFNTATION CONSIDFRATIONS The design and implementation or an electrowinning unit are dependant on the conriguration and control or the electro- plating and rinse operations ror which the unit will be used. Llectrowinning can eliminate the need ror continuously rlow- ing rinse water in a rinse system ir dragout reduction tech- niques and multiple rinse tanks are used. The most common and cost-errectie application or electrow- inning inoles installing an electrowinning unit on a stag- nant rinse tank located arter a dragout recoery tank. To main- tain a steady-state metal concentration in the stagnant rinse at or below the maimum contaminant concentration, the rate or metal deposition onto the electrowinning cathodes must be greater than or equal to the rate or dragin rrom the preceding tank. Thus the metal deposition rate is a key design parameter that ultimately arrects the capacity, size, and cost or the elec- trowinning unit. Because metal and cyanide concentrations in the stagnant rinse are lowered, subsequent rinses will be cleaner,` allowing the rinse water rlow rates in these rinses to be reduced or turned orr. In many cases, rinse water rlow is reduced to a rate equal to the eaporation rate rrom the stagnant rinse. VAXlVlZL VLTAL DLOSlTlON LATL Maimizing and controlling these rour ractors will improe electrowinning unit perrormance. Metal Concentration: To achiee high recoery rates, electrowinning should be applied to concentrated rinse waters. Thererore, electrowinning is most errectiely ap- plied to a stagnant rinse. Current Density: Metal deposition occurs at raster rates with higher current densities. Howeer, ir the current den- sity is too high, the solution surrounding the cathodes can become depleted or metals, which limits the metal deposi- tion rate. The ecess` current applied to the electrodes is wasted on conerting water into hydrogen and oygen. Mixing: Miing disrupts the metal depletion layer that would rorm in a stagnant solution, allowing the electrow- inning unit to be operated at a higher current density with a corresponding higher deposition rate. Cathode Surface Area: Metal deposition rate is propor- tional to cathode surrace area. Two main types or cathodes are aailable: ,1, rlat plate cathodes and ,2, reticulated cath- odes. llat plate cathodes are made or stainless steel, hae an errectie surrace area equal to their apparent area, and are reusable. Vhen deposited metal reaches a thickness or 3,16 to 1,4 inch, rlat plate cathodes should be remoed and cleaned. The adantage or rlat plate cathodes are their reusability and the ability to recoer metals on-site. Re- ticulated cathodes are made or metal-coated carbon ribers and hae an errectie surrace area that is ten times their apparent area. The adantage or using reticulated cathodes is their high deposition rate. Reticulated cathodes are not reusable, rully loaded cathodes are, thererore, sent orr site ror recycling. Lentually, dissoled salts that are not remoed or oidized by the electrowinning unit accumulate in the rinse water. Ir these accumulated salts start negatiely impacting rinsing quality, the rinse water tanks should be drained and rilled with clean water. Spent rinse water can be eaporated, treated, or dis- posed or orr site. CASF STUDY: FLFCTROWINNING AT ALL MFTALS All Metals Processing Company ,All Metals, is a small job shop in Burbank, Calirornia, that perrorms cadmium, bronze, and zinc electroplating and black oide coating ror aerospace and other industrial customers. All Metals employs 15 work- ers, and its racility has about 8,000 square reet or space ror plating operations. In early 1996, All Metals set a goal to reduce water use and eliminate wastewater discharge to the sewer. All Metals was motiated by high city sewer rees and pressure rrom the mu Most Successful Most Successful Most Successful Most Successful Most Successful Electrowinning Electrowinning Electrowinning Electrowinning Electrowinning Applications Applications Applications Applications Applications ! !! !! Gold ! !! !! Silver ! !! !! Copper ! !! !! Cadmium ! !! !! Zinc Helpful Hint Helpful Hint Helpful Hint Helpful Hint Helpful Hint The electrowinning unit should be operated 24 hours per day to maximize metal recovery and to maintain the lowest possible metal and cyanide (if present) concen- trations in the stagnant rinse. Operating the unit during nonproduction hours allows it to recover metals and de- stroy cyanide that accumulate during production. nicipal wastewater treatment plant ,POTV, to decrease the metal concentrations in treated wastewater. In cooperation with the Merit Partnership, All Metals agreed to pursue its goal in two phases. All Metals and the Merit Partnership de- cided to rocus their errorts on the cadmium electroplating line because it was the most rrequently used process line, dragout rrom this line contributed the largest quantities or metals to the wastewater, and All Metals had eceeded their cadmium wastewater discharge limits on seeral occasions. Phase 1 inoled ealuating oerall process erriciency and con- trol. The purpose or Phase 1 was to reduce dragout and opti- mize rinse water use to the maimum etent reasible berore selecting and purchasing recycling or recoery technologies. Process modirications made during Phase 1 are described in a preious Merit Partnership ract sheet titled Modirying Tank Layouts to Improe Process Lrriciency.` Phase 1 modirica- tions resulted in a 50 percent dragout and rinse water reduc- tion, a 60 percent wastewater treatment chemical reduction, improed rinsing quality, and more erricient work rlow, the Phase 1 payback period was 1. years. By improing oerall process erriciency rirst, All Metals was able to more cost-errectiely apply a metal recoery technology and moe toward eliminating cadmium wastewater discharges to the POTV. lor Phase 2, electrowinning was determined to be the most reasible technology ror All Metals to reduce or eliminate wastewater discharges rrom the cadmium electroplat- ing operation. FLFCTROWINNING UNIT INSTALLATION AND OPFRATION All Metals purchased a Retec Model 6 electrowinning unit rrom U.S. lilter,Memtek, or Billerica, Massachusetts. The Model 6 holds si cathodes and has a 100-ampere capacity. The electrolytic cell and rectirier were mounted on a shelr aboe a stagnant rinse tank ,Rinse1, that rollows a spray dragout recoery tank ,see ligure 3,. Reticulated cathodes were used in the electrowinning unit. Anticipating that the electrowin- ning unit would reduce cadmium and cyanide concentrations in Rinse 1, All Metals turned orr the rinse water rlow in the subsequent counterrlow rinse and conerted it into a two-stage stagnant rinse ,Rinses 2 and3,. Rinse water was manually transrerred rrom Rinse 2 to Rinse 1 in order to make up ror eaporatie losses, rinse water in Rinse 3 rlows through a weir into Rinse 2 when clean water is added to Rinse 3. In addition, All Metals installed an electric heater on Rinse 2 to increase eaporation, thereby increasing the countercurrent rlow or clean water rrom Rinse 3. A heater could not be in- stalled on Rinse 1 because it is a plastic tank that could not tolerate higher temperatures. All Metals also installed an in- tank riltration system on Rinse 2 to remoe suspended solids rrom the rinse water. RFSULTS The electrowinning unit is operated at the All Metals racility 24 hours a day, days a week. The cathodes are replaced eery 3 months on aerage. Based on the start and rinish weights or the cathodes, about 2 kilo- grams ,4.4 pounds, or cad- mium was recoered on the si cathodes arter 2 months or operation. Spent cath- odes are picked up by a scrap metal dealer ror recy- cling. Berore the electrowinning unit was installed, rinse water rlowed through the counterrlow rinse tank at a rate or 0.5gallon per minute. Since the electrow- inning unit was installed, Electrowinning Costs Electrowinning Costs Electrowinning Costs Electrowinning Costs Electrowinning Costs Capital: Capital: Capital: Capital: Capital: Electrowinning units typically cost $5,000 to $15,000, depending on the units size and design and the type of cathodes used. Reusable, flat plate cathodes cost about $200 each, and disposable, reticulated cath- odes cost about $12 each. O&M: O&M: O&M: O&M: O&M: Labor, electrode replacement, maintenance, and energy costs are low. Iigure 3. All Metals' Cadmium Llectroplating Line CADMIUM CYANIDE PLATING RINSE NO. 2 CADMIUM BARREL PLATING SPRAY RINSE RINSE NO. 1 WALL RINSE NO. 3 HEATER ELECTROWINNER IN-TANK FILTER Helpful Hint Helpful Hint Helpful Hint Helpful Hint Helpful Hint Ideally, a heater should be installed on the rinse tank connected to the electrowinning unit. This design fea- ture concentrates the influent to the electrowinning unit, which increases the metal deposition rate. It also in- creases the countercurrent flow of rinse water from sub- sequent rinses. Benefits of Electrowinning on All Metals' Benefits of Electrowinning on All Metals' Benefits of Electrowinning on All Metals' Benefits of Electrowinning on All Metals' Benefits of Electrowinning on All Metals' Cadmium Line Cadmium Line Cadmium Line Cadmium Line Cadmium Line ! !! !! 94% water use reduction ! !! !! Elimination of cadmium-bearing wastewater ! !! !! No cadmium discharge limit violations ! !! !! Simplified wastewater discharge permit ! !! !! Decreased WWTS O&M and filter cake generation all the rinse tanks hae been operated in a stagnant mode, and the temperature or the rinse water in Rinse 2 has been main- tained at about 115 o l, resulting in the eaporation or about 15 gallons or rinse water per day. Consequently, 15 gallons or clean water per day is added to Rinse 3 in order to compensate ror the water transrerred into Rinse 2 to make up ror eapora- tie losses. Based on comparison or water use on the cadmium electroplating line berore and arter installation or the electrow- inning unit, rinse water use has been reduced by 94 percent and wastewater is no longer generated rrom the rinses. Because not all dissoled solids are remoed by the electrowin- ning unit, conductiity is monitored in Rinses 1 and 3 ,see ligure 4,. Rinse 3 is drained to dispose or the dissoled solids buildup and replenished with clean rinse water eery 6 weeks on aerage. The drained rinse water is eaporated onsite by All Metals. In addition, cyanide concentrations are periodi- cally measured in Rinse 1, these concentrations hae been signiricantly reduced by the electrowinning unit. All Metals purchased the Retec Model 6 electrowinning unit ror >,500, the electric tank heater ror >690, and the in-tank riltration system ror >50. All Metals spent an additional >250 on electrical hardware such as wiring and a ruse bo and a total or 20 labor hours ror unit installation and startup. Op- eration and maintenance ,O&M, epenses include about >20 per month ror electricity and >290 per year ror reticulated cathode purchase. Arter installation or the electrowinning unit, no increase in the number or reject parts occurred, and no aderse impacts on production were obsered. Motiated by the success or the electrowinning unit ror the cadmium operation, All Metals has installed another electrowinning unit in a copper electro- plating stagnant rinse. The estimated 8.-year payback period is relatiely high be- cause it considers only direct costs and saings. Other ben- eficial outcomes may lower the payback period. lor e- ample, the electrowinning unit takes All Metals one-step closer to its goal or zero discharge to the sewer, which will eliminate the >2,860 annual wastewater discharge ree. Also, All Metals is no longer susceptible to cadmium discharge iolations, which can result in >1,000 rines. Ior more information on this case study or the Merit Partnership, contact the following individuals: Laura Bloch ,LPA Region 9, at ,415, 44-229 John Siemak ,CMTC, at ,310, 263-309 Dan Cunningham ,MlASC, at ,818, 986-8393 Tim Roach ,All Metals, at ,818, 846-8844 Dan Hegyan ,U.S. lilter,Memtek, at ,310, 33-655 Assistance ror this ract sheet was proided by Tetra Tech LM Inc. Cost Savings Before Before Before Before Before After After After After After Savings Savings Savings Savings Savings Water Use - Cd 240 gal/day 15 gal/day $110/yr Sewer Discharge - Cd 240 gal/day 0 gal/day $480/yr WWTS O&M $11,080/yr $10,220/yr $860/yr Filter Cake Disposal 760 lb/mo 700 lb/mo $114/yr Annual Savings = $1,564/yr* Annual Savings = $1,564/yr* Annual Savings = $1,564/yr* Annual Savings = $1,564/yr* Annual Savings = $1,564/yr* Total Costs = $9,010 Total Costs = $9,010 Total Costs = $9,010 Total Costs = $9,010 Total Costs = $9,010 O&M Costs = $530/yr O&M Costs = $530/yr O&M Costs = $530/yr O&M Costs = $530/yr O&M Costs = $530/yr Payback Period = 8.7 yrs Payback Period = 8.7 yrs Payback Period = 8.7 yrs Payback Period = 8.7 yrs Payback Period = 8.7 yrs *Annual savings does not include potential reclaim value for recovered metals *Annual savings does not include potential reclaim value for recovered metals *Annual savings does not include potential reclaim value for recovered metals *Annual savings does not include potential reclaim value for recovered metals *Annual savings does not include potential reclaim value for recovered metals Iigure 4. Conductivity Measurements in Rinse J 0 5 10 15 20 25 30 35 40 4 / 2 8 5 / 5 5 / 1 3 5 / 2 0 5 / 2 8 6 / 4 6 / 1 1 7 / 7 7 / 3 1 8 / 7 8 / 1 4 8 / 2 1 8 / 2 8 9 / 5 9 / 1 2 Date - 1997 C o n d u c t i v i t y
( m S / c m ) Bath Dump Bath Dump Cathodes Dissolved Bath Dump Cathodes Dissolved Lessons Learned Lessons Learned Lessons Learned Lessons Learned Lessons Learned Cathode installation and maintenance is critical to the electrowinning units performance. All Metals experi- enced two incidents in which the cathodes dissolved into the circulating rinse water when the electrical connec- tion between the bus bar and cathodes was disrupted. The first incident occurred when three cathodes were improperly placed in the electrowinning unit. The sec- ond incident was caused by reuse of cathode connec- tors. As the connectors gradually became corroded, the electrical connection between the cathodes and bus bar was lost. All Metals now replaces the cathode All Metals now replaces the cathode All Metals now replaces the cathode All Metals now replaces the cathode All Metals now replaces the cathode connectors every time that the cathodes are replaced connectors every time that the cathodes are replaced connectors every time that the cathodes are replaced connectors every time that the cathodes are replaced connectors every time that the cathodes are replaced and periodically checks the cathodes to assure their and periodically checks the cathodes to assure their and periodically checks the cathodes to assure their and periodically checks the cathodes to assure their and periodically checks the cathodes to assure their proper connection to the bus bar. proper connection to the bus bar. proper connection to the bus bar. proper connection to the bus bar. proper connection to the bus bar.