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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.