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Electrochemical Treatment and Reuse of Nickel Plating Rinse Waters Paul T. Bolger and David C. Szlag Bord na Mona Environmental Ltd., Main Street, Newbridge, County Kildare, Ireland*

*Research performed at the National Risk Management Research Laboratory, U.S. Environmental Protection Agency, 26 W. Martin Luther King Drive, Cincinnati, OH 45268

The treatment and disposal of nickel-contaminated rinse waters places an additional cost-burden on a metal plating facility. Increasing the resource productivity within an electrolytic nickel plating process by creating a recycle loop for the “waste” components of the rinse water can reduce disposal and raw material costs. In this study, an electrowinning cel1,fitted with an anion exchange membrane, was used to recover valuable components from a simulated electrolytic nickel plating rinse water by a combination of electrodeposition and electrodialysis. The anion exchange membrane in the cell permitted a dual electrode function. Nickel metal was recovered from the rinse water at the cathode and a sul- furichydrochloric acid mixture was generated at the anode (which can be used in thepickling baths to clean metal parts). The boric acid in the rinse water could not be recovered by anion exchange due to its high acid dissociation constant. The cell worked effectively in both a batch and a continuous feed mode. The research demonstrated that this type of electrochemical cell could feasibly replace the traditional ion exchange process for treating rinse waters, and eliminate regeneration chemicaWwaste while producing useful process materiak;.

INTRODUCTION Nickel electroplating (the electrolytic deposition of

a layer of nickel on a substrate) is a versatile surface finishing process that has a wide range of decorative, engineering and electroforming applications. The nickel coatings are generally deposited from a Watts nickel solution that contains nickel sulfate, nickel chloride, and boric acid, along with organic brighten- ing agents in the case of decorative coatings. After coating, the plated parts are washed in a series of rinse water baths. These baths accumulate the “dragout” constituents of the Watts nickel bath over time and eventually require treatment. A range of technologies for treating Watts nickel rinse waters have been used, including ion exchange [ l l , electrowinning [Z, 31, evaporation [41, reverse osmosis [51, and electrodialysis [6, 71.

Many of these treatments are quite costly. For example, treatment by ion exchange requires expen- sive resins, large amounts of regenerant solution, and additional tanks, and can have a significant associated downtime if there are not dual ion exchange beds available. To reduce rinse water treatment costs, increased emphasis is being placed in metal plating shops on in-process recycling, low cost metal recovery, and pollution prevention [S-101. This research explores a simple, continuous rinse water treatment system that encompasses the aforementioned principles. The technology is essentially a combined electrowinning/electrodialysis unit that recovers nickel metal while generating a mixed inorganic acid solution that can be reused in plating shop pickling baths (See Figure 1).

The use of electrowinning to treat wastewaters contaminated with metal ions has been advanced by recent progress in electrolytic cell design, especially the development of high surface area cathodes, mak- ing it possible to recover metals to very low concentrations 121. Nickel(I1) has been successfully recovered from rinse waters by electrowinning, but the electrodeposition process tends to become inhibited by production of hydrogen ions at the anode via water electrolysis. These hydrogen ions can be neutralized by passing the electrolysis solution through a weak base anion exchange column that replaces the sulfate and chloride anions in the rinse water with hydroxide ions [31, but ion exchange adds to the overall expense of the treatment.

The pH shift could be avoided by creating a sepa- rate cathode and anode compartment in the electrowinning cell using an anion exchange membrane. In this type of cell, nickel(I1) would be plated on the cathode as usual and the excess anions (counter-ions) in the catholyte would migrate across the anion exchange membrane to the anode compartment to maintain electroneutrality. This cell would permit dual electrode use, recovering nickel metal from the rinse

Environmental Progress (V01.21, No.3) October 2002 203

Table 1. Composition of the simulated Watts nickel rinse water used in treatment studies.

Component Nickel Sulfate Chloride Boric Acid Concentration/mM 4.2 (250 ppm) 3.4 1.6 2.4

Anolyte out Watts nickel rinsewater out

f 4 -F AEM

I I I

I I Nil*

cr + ci- Nio

I 4

I & B O 3

so,% < I ' so.= I

I I

I Wntb nickel rinsewater

in (eptholyte) f

Anolyte in

Figure 1. Treatment of Watts nickel rinse water using an electrowinning/electrodialysis cell.

water at the cathode and generating an acid mixture at anode that may be used in the pickling baths to clean metal parts before plating. A flow diagram of a Watts nickel plating line is shown in Figure 2, including the likely location of an ion exchange and electrowinning treatment unit within the rinse water treatment system. Although the ion exchange unit is placed at the end of the line, to avoid overloading the resin, the electrowinning unit is placed earlier in the rinse water line, to take advantage of the higher concentrations of nickel in the first save rinse water as electrowinning operates more efficiently at higher metal concentrations. The anolyte from the electrochemical cell is occasionally bled off to the pickling bath, and the electroplated nickel is recycled back to the plating bath.

EXPERIMENTAL METHODS A simulated Watts nickel rinse water was prepared

from nickel sulfate, nickel chloride, and boric acid in deionized water. The concentrations of the different components in the rinse water were based on the typ- ical concentrations of nickel, sulfate, chloride, and boric acid found in a first save rinse (See Table 1). The solution pH was approximately 4. The Watts nickel rinse water was the catholyte in the electrolysis cell and the anolyte was deionized water adjusted to pH 1.5 with concentrated sulfuric acid.

The electrolysis/electrodialysis cell was a bench- scale ElectroMPcell (Electrocell AB) with a nickel cathode and a platinized titanium anode. The high surface area cathode necessary for efficient nickel(I1) removal at low concentrations was designed in-house b inserting a segment of carbon felt (Renovare), 10 cm in area and 1.2 cm thick, into a compartment frame in which the center plastic grid had been removed.

3

When the cell was assembled the carbon felt was in direct contact with the nickel cathode plate and the Watts nickel rinse water flowed through, and across the surface of, the carbon felt. The anion exchange membrane was a low resistance Tokuyama Neosepta AM-1 membrane. The potential was controlled by a 10 volt/l5 amp power supply (Kocour Company) and the potential d rop and current across the cell was measured using a multimeter. The catholyte and anolyte solutions were recirculated around the cell by quasi-diaphragm pumps, and the flow rates were carefully regulated (1-2 1 min-l) to maintain equal hydraulic pressure on either side of the membrane and prevent water transport across the membrane. The electrolyte flow rates were based on the optimum flow velocity of a sheet-flow ED frame [111. A lower volume of anolyte (1O:l) than catholyte (30:l) was used in order to produce a more concentrated acid solution for reuse in a pickling bath.

The electrolysis treatment trials were carried out over a 12 to 24 hour period and samples were removed at selected time intervals from the anolyte and catholyte, and diluted for ion analysis. The chloride and sulfate anions were quantified on a Dionex 500 Ion Chromatograph with an ED50 conductivity detector, and a 4 mm Dionex AS11-HC anion exchange column using 15 mM NaOH as eluent under an isocratic gradient. Nickel and borate (as boron) were quantified by inductively coupled plasma spec- troscopy on a Perkin Elmer 3300 DV spectrometer.

The rinse water treatment studies were carried out in a batch and a continuous feed mode. The batch mode was utilized to determine the quantity of nickel(I1) (and anions) that could be removed from the Watts nickel rinse water by the electrochemical cell in a 24 hour period. In the continuous feed mode there was constant addition of a concentrated Watts nickel solution to the catholyte (via peristaltic pump) to sim- ulate the conditions under which an electrowinning cell would have to operate in a metal finishing line. The desired objective of operating the electrowinning cell in a continuous feed mode was to maintain the nickel(I1) ions at a constant concentration, that is, the rate of nickel(I1) removal by electrowinning equivalent to the rate of nickel(I1) addition.

RESULTS AND DISCUSSION The electrochemical thermodynamics of nickel

deposition from an aqueous solution indicate that the process is not an efficient one, as the reduction of water is thermodynamically more favorable as shown in Equations 1 and 2.

Ni2+ + 2e- + Nio I@= -0.25 V

H30i + 2e- -+ H2 + OH l? = 0.00 V (2)

204 October 2002 Environmental Progress (Vo1.21, No.3)

Table 2. The mmoles of nickel(II), sulfate, chloride and boric acid in the catholyte and anolyte before and after the 24 hour electrodeposition trial at a potential of 6 V under batch conditions.

Nickel(II) Sulfate chloride Boric Acid (mmoles) (mmoles) (moles) (mmoles)

Catholyte/O hours 126 105 51 67 Anolyte/O hours 0 208 0 0 Totau0 hours 126 313 51 67 CatholyteM4 hours 30 33 15 63 Anolyte/24 hours 5 274 31 2 Totau24 hours 35 30 7 46 65

O/O Removal from catholyte 76.2 0’0 68.5 010 70.6 010 6.0 0’0

Figure 2. Schematic of Watts nickel plating line with two possible rinse water treatment options.

The competition of water electrolysis with nickel deposition, and the associated production of hydroxide ions, was clearly demonstrated in the initial trials on removing nickel(I1) from a Watts nickel rinse water in the Electrocell with an anion exchange membrane. The pH of the catholyte increased from pH 4 to pH 7 over a period of 2 to 3 hrs at a potential of 6 V, result- ing in the undesirable precipitation of nickel(I1) hydroxide on the cathode and membrane. In order to avoid the pH increase in the catholyte, a pH con- troller, set at an upper pH limit of 5.0, was used to introduce small quantities of acidic anolyte back to the catholyte in order to maintain the pH in the region of 4.5 to 5.0.

The amount of nickel(II1, sulfate, chloride, and boric acid in the catholyte and anolyte before and after the electrodeposition are shown in Table 2. At an electrodeposition potential of 6 V and pH between 4.5-5.0, the nickel deposit on the cathode was entirely nickel metal (gray-black), and there was no observ- able nickel(I1) hydroxide deposit (green). The data in Table 2 does indicate that there was some transport of nickel(I1) ions to the anolyte over the 24 hour period (4%), reflecting the difficulty in balancing hydraulic pressure across the membrane. When adjustments for the nickel(I1) loss to the anolyte were made, 72.2% of nickel(I1) was removed from the rinse water and elec- trodeposited on the cathode over a 24 hour period.

Both sulfate (68.6% removal) and chloride (70.6% removal) were effectively removed from the catholyte via transport across the anion exchange membrane. The electroneutrality of the catholyte was maintained, as the cumulative mmoles of anions (72 mmoles S042- and 36 mmoles Cl-> transported to the anolyte were approximately electronically equivalent to the mmoles of nickel deposited on the cathode (96 mmoles Ni2+).

The removal of ions from the catholyte and the change in concentration of anions in the anolyte over the period of the electrodeposition are shown in Figures 3 and 4, respectively. It is apparent that sulfate and chloride anions were transported across the anion exchange membrane at the same rate as nickel(I1) was removed from the solution, and only in quantities suffi- cient to maintain electroneutrality in the catholyte. The pH of the anolyte decreased from 1.5 to 1.4 during the 24 hours. In contrast to sulfate and chloride, there was minimal removal of boric acid from the catholyte, and only a slight accumulation of boric acid in the anolyte. The low removal of boric acid from the catholyte (6.0% removal) can be explained in terms of its high acid dissociation constant. The ftrst acid dissociation constant of boric acid is 9.27 [121. At a pH of 4.5 to 5.0 boric acid existed completely in the undissociated form and was unavailable for transport across the anion exchange membrane.


0 5 10 15 P 25

mmlhatr

I 0 5 10 15 20 25

TlmlhlWS

A second 12 hour rinse water treatment trial was carried out under continuous feed conditions. A peristaltic pump was set to dose a concentrated Watts nickel solution (300 mM nickel) to the catholyte at a rate of 3 mmoles of nickel per hour. The results of the trial are presented in Table 3 and in Figures 5 and 6. During the trial, it was observed that there was an increase in the nickel(I1) removal kinetics from the catholyte. This may be due to the formation of a layer of nickel metal on the carbon felt. The change in nickel(I1) removal kinetics over the period of the electrodeposition made it difficult to maintain a constant concentration for the components in the catholyte and it can be observed from Figure 5 that the concentrations of nickel, sulfate and chloride ions gradually decrease during the trial. Over a period of 12 hours, 46 mmoles of nickel(I1) (discounting for the amount of nickel transferred to the anolyte) were deposited on the cathode. This is consistent with the amount of nickel(I1) removed from the catholyte over the first 12 hours of the batch experiment.

The transfer and accumulation of sulfate and chloride in the anolyte follows a different pattern to that observed for these anions in the first 12 hours of the initial batch trial. The transfer of sulfate and chloride to the anolyte is sluggish at first, which may be a reflection of the slower removal kinetics of nickel(I1) initially, and then becomes more rapid (See Figure 6). As in the batch trial, the sulfate and chloride are only transferred to the anolyte at a rate that maintains catholyte electroneutrality. The pH of the anolyte decreased from 1.55 to 1.46 during the continuous feed treatment trial. Over the 12 hours, 20 mmoles of boric acid were added to the catholyte. At the end of the trial it was found that 18 mmoles of boric acid had accumulated in the catholyte, meaning only 2 mmoles of boric acid was removed. This corresponds to the increase of only 1 mmole of boric acid in the anolyte at the end of the trial, as shown in Figure 6.

From the outset there was some concern that chloride ion may be lost from the anolyte via oxidation to

chlorine gas at the anode. The redox potentials for chlorine and water oxidation are given in Equations 3 and 4.

2 C t - 2 e - j C12 &?=+1.35V (3 )

2H20 - 4e- -+ 02 + 4H+ &? = + 1.23 V (4)

Although the oxidation potential for water is higher than the chloride ion, the over potential for oxygen evolution can be significant especially on a platinized titanium anode and can result in chlorine evolution. Although the total amount of chloride after the trials is somewhat less than before, (8-10%) it is not clear if this is due to chloride loss via chlorine evolution, or analytical error. In this context, it is worth noting that the mmoles of sulfate present after the trials is also less before the trials and by about the same amount as the chloride ion. As the oxidation of sulfate is unlikely (Eo = 1.96) the source of the sulfate and chlorine dis- crepancy before and after the trials may be analytical.

The average nickel removal rate from the Watts nickel rinse water for the trials was 3.75 mmoles/hour. The current efficiency for the process (fraction of elec- trical charge involved in nickel(I1) deposition) can be calculated using Equation 5.

Current efficiency = (M x Z x F)/(I x T) (5)

M = Moles of nickel(I1) deposited Z = Ion charge T = Time(s) F = Faraday's number (96,500 A s mol-l) I = Current (A)

The average current during the electrolysis was 0.3 A. This gives a current efficiency for the process of 0.67, that is, 67% of the current supplied to the electrochemical cell was used to deposit nickel(I1) on the cathode. Given the inherent competition at the electrode between nickel deposition and the reduction of

206 October 2002 Environmental Progress (V01.21, No.3)

Tab 3. The mmoles of nickel(II), sulfate, chloride, and boric acid in the catholyte and anolyte before and after the 12 hour electrodeposition trial (6 V) under continuous feed conditions.

Nickel@) Sulfate chloride Boric Acid (mmoles) (mmoles) (mmoles) (mmoles)

Catholyte/O hours 132 111 54 67 Anolyte/O hours 0 210 0 0 ToWO hours 132 321 54 67 mmoles added to catholyte during trial 36 29 14 20 Catholyte/l2 hours 120 97 45 85 Anolyte/l 2 hours 2 246 19 1 ToWl2 hours 122 343 64 86

l4 1: 1

I 0 2 4 6 8 1 0 1 2 1 4 nmihoun

Figure 5. The concentration of nickel(II1, sulfate, chloride, and boric acid in the catholyte as a function of time for a 12 hour electrodeposition trial in a divided electrowinning cell with an anion exchange membrane at a potential of 6 V with continuous addition of Watts nickel solution.

4 - +sulk. +Chloride -n- Bocic add

0 2 4 6 8 10 12 14

nnnihwn

Figure 6. The change in concentration of sulfate, chloride, and boric acid in the anolyte as a function of time for a 12 hour electrodeposition trial in a divided electrowinning cell with an anion exchange membrane at a potential of 6 V with continuous addition of Watts nickel solution to the catholyte.

water (See Equations 1 and 2), this would be consid- ered a satisfactory current efficiency. The current supplied to the cell was also being used to transport anions across the cell, and to generate acid in the anolyte, so there was dual use of the electrodes from a current efficiency perspective. The energy consumption for nickel removal from the rinse water can be calculated from Equation 6 [131.

Energy consumption = (2 x F x E)/(CE x 1/3.6x10 6 ) (6)

Z = Ion charge F = Faraday’s number E = Cell potential CE = Current efficiency

At a cell potential of 6 V and a current efficiency of 0.67, the energy consumption for the process is 0.48 KW h-l mol-l which is equivalent to 8.2 KW h-l per kilogram of nickel(I1) removed. Given a utility price of $0.07 per KW h-l, the operating cost of the electrochemical cell would be $0.57 per kilogram of nickel(I1) removed. The capital cost of the electrochemical cell and the comparative cost compared to ion exchange can only be evaluated for research that is sized to production-scale, and tested in a plating shop.

CONCLUSION It was shown that, in principle, an electrochemi-

cal cell divided by an anion exchange membrane can be used to remove nickel(II), chloride, and sulfate from Watts nickel rinse water at high current efficiencies. Boric acid will not removed from the rinse water due to its high acid dissociation constant. It is critical to maintain the water balance between the anolyte and catholyte in the cell. Dur- ing the rinse water treatment, the anolyte becomes increasingly acidic and a mixed sulfuric/hydrochlo- ric acid is generated. This acid can be used to maintain the catholyte at optimum pH for nickel deposition, and to avoid nickel(I1) hydroxide precipitation, by feeding a small amount of it back to the catholyte. Over a longer period of time, the acid may be bled off for recycle to the pre-treatment pickling baths.

There is no apparent loss of chloride ion from the anolyte via oxidation to chlorine gas at the anode. The evolution of chlorine gas would be undesirable from a health and safety, membrane life and resource perspective. With further development and scale-up, this type of electrochemical cell represents an opportunity to replace the traditional ion exchange process for treating rinse waters eliminat-


ing regeneration chemicals/waste and producing a mixed acid that could be reused in the plating process.

ACKNOWLEDGMENTS This research was supported by an appointment to

the Postgraduate Research Participation Program at the National Risk Management Research Laboratory administered at the Oak Ridge Institute for Science and Education through an interagency agreement between the US. Department of Energy and the U.S. Environmental Protection Agency.

Note: The discussion of certain technologies and men- tioning of trade names in this paper does not in any way represent an endorsement of those technologiedproducts by the U S . Environmental Protection Agency.

LITERATURE CITED 1. Cushnie, G., Pollution Prevention and Control

Technology for Plating Operations, National Cen- ter for Manufacturing Sciences, Ann Arbor, MI, 1994

2. Kniazewycz , G., “New 3-D Electrolytic Cell Advances the Concept of Waste Minimization in Plating Applications,” Proceedings of the Electro- chemical Processing Conference, Capenhurst, Cheshire, UK, April 12-15, 1999.

3. Szlag, D. and D. Djlhoff, “An Environmental and Economic Comparison of Ion Exchange and Recently Commercialized Electrochemical Tech- nologies for the Recovery of Rinse Water in a Bright Nickel Plating Facility,” Proceedings of the 2000 AESF/EPA Conference f o r Environmental Ekcellence, pp 343-351, Orlando, FL, 2000.

~~ ~ ~ ~ ~ ~ ~~~~

4. Lindsey, T.C. and P.M. Randall, “Recycling Nick- el Electroplating Rinse Waters by Low Tempera- ture Evaporation and Reverse Osmosis,” U S . EPA Technical Report, EPA/GOO/R-93/160, August 1 993.

5. Schmidt, C. and I. Erbas-White, “Watts Nickel and Rinse Water Recovery via an Advanced Reverse Osmosis System,” U.S. EPA Technical Report, EPA/600/R-93/150, 1994.

6. Markovac, V. and H.C. Heller , “Principles of Electrodialysis for Nickel Plating Rinse Water,” Plat. and Sur. Fin., 68, pp 66-69, 1981.

7. Itoi, S., I. Nakamura, and T. Kawahara, “Elec- trodialytic Recovery of Metal Finishing Waste- water,” Desalination, 32, pp 383-389, 1980.

8. Blackburn, J.W., “Electrodialysis Applications for Pollution Prevention in the Chemical Processing Industry,” J. Air & Waste Manage. Assoc., 49, pp

9. Hayashi, T., “Recycle Treatment of Wastewater from Nickel Plating,” U.S. Patent US4009101, 1975.

10. Brooks, C.S., “Nickel Metal Recovery from Metal Finishing Industry Wastes,” Proceedings of the 42nd Industrial Waste Conference, pp 847-852, 1988.

11. Davis, T.A., J.D. Genders, and D. Pletcher, “A First Course in Ion-Permeable Membranes,” The Electrochemical Consultancy, Hants, England, 155, 1997.

12. Lide, D.R., CRC Handbook of Chemistry and Physics, 48th Edition, CRC, London, UK, pp 8- 42, 1997.

13. Pletcher, D. and F.C. Walsh, Industrial Elec- trochemisty, Second Edition, Blackie Academic and Professional Publishers, Glasgow, UK, pp

934-942, August 1999.

74-75, 1990.

208 October 2002 Environmental Progress (V01.21, No.3)

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