Removal of Iron and Other Metal Impurities from Chromium Plating Solutions

Dr. Sergey S. Kruglikov, Nadya Kolotovkina, Tatyana Ladygina, S.S. Kruglikov Consultants, Moscow, Russia A low-cost process for the purification of conventional chromium plating solutions has been developed. It includes following stages: (1) Electrolytic transfer of pure chromic acid from contaminated plating solution diluted to a concentration of 120-150 g/l. A three-chamber cell with a cation-exchange and an anion-exchange membranes is used in this stage. (2) Removal of cationic impurities (iron, etc.) from the residual solution with low concentration of chromic acid using cation-exchange resin. (3) Purified solutions from stages (2) and (3) are added to a chromium plating tank. Conventional types of ion-exchange membranes and resins are stable in solutions used in stages (1) and (2) and there is no additional evaporation.

For more information contact: Dr. Sergey S. Kruglikov S. S. Kruglikov Consultants Moscow, Russia Phone: +7 (916) 616-9699 Fax: +7 (495) 609-2964 E-mail: skruglikov@mail.ru http://kruglikov-module.narod.ru/

Iron is a major contaminant in chromium plating solutions based on chromic acid because of chemical reaction between chromic acid and the surface of steel parts. Ferric ions formed by this reaction are not reduced at the cathode and cannot be removed by plating out. Therefore they are gradually built up in the solution. Usually plating solution is not used any more, when the concentration of ferric ions exceeds 10-15 g/l. Such solutions are sometimes treated with spent pickling solutions containing hydrochloric acid and ferrous ions acting as a reducer for hexavalent chromium. Such technology means huge losses of chromic acid and the formation of equivalent amounts of solid waste a mixture of ferric, ferrous and chromic hydroxides. Removal of iron from contaminated solutions by adding sodium hydroxide causes precipitation of insoluble iron compounds. However chromic acid is simultaneously converted into sodium chromate. There are two principally different electrochemical purification methods: 1. Removal of iron and other cationic impurities (as well as trivalent chromium) by means of electrolytic transfer from the anolyte a contaminated solution into the catholyte a diluted solution of pure chromic acid (Fig. 1)1.

O2

H2

1 2

Fe3+, Cr3+, etc. H+ 5 4 3

Fig. 1. Removal of iron and other cathionic impurities by the transfer through cation-exchange membrane. 1, anode; 2, contaminated solution; 3, cation-exchange membrane; 4, catholyte; 5, cathode. A loss of appreciable amounts of chromic acid due to its cathodic reduction and low rate of the purification process are major disadvantages of this method. The efficiency of the removal of metal ions in this process is determined by their transport numbers. Because of high concentration of chromic acid in the anolyte a major part of current is conducted by hydrogen ions. Therefore the efficiency of the purification process is very low. 2. Electrolytic transfer of chromic acid from the catholyte contaminated solution into the anolyte (Fig. 2)2. Cations do not pass through the membrane from the catholyte into the anolyte. The efficiency of the process is not high due to the cathodic reduction of a considerable part of chromic acid in the course of the electrolysis.

O2

H2

1 2

Cr3+

3
CrO42

CrO42

Fig. 2. Removal of pure chromic acid from the contaminated solution. 1, anode; 2, anion-exchange membrane; 3, cathode; The transfer of chromic acid through an anion-exchange membrane at a given value of current depends on its concentrations in the anolyte and in the catholyte. Maximum efficiency is reached, if the concentration of chromic acid in the anolyte is equal to that or is even lower than in the catholyte. Apart from that available anion-exchange membranes are not stable at concentrations of chromic acid above 140150 g/l. Therefore a contaminated plating solution should be diluted before the purification. In the course of the regeneration the anolyte should be diluted periodically in order to maintain moderate concentration difference between the catholyte and the anolyte. Finally the concentration of chromic acid in a mixture of anolytes from initial and later stages of the process may be about 100 g/l or even lower. A new method, which is a combination of (1) and (2), has been proposed recently (Fig. 3)3.

O2

H2

H+ 1 2 H2O CrO42 (Cr2O72)

Fe3+
Cr3+

H+

3 4

Fig. 3. Three-chamber cell. 1, anode; 2, anion-exchange membrane; 3, cation-exchange membrane; 4, cathode.

The electrolytic cell consists of three compartments. A new type of the catholyte is used in the combined method: diluted sulfuric acid instead of chromic acid. This change of the nature of the catholyte allows to eliminate undesirable cathodic reduction of chromic acid. Diluted contaminated plating solution is contained in the intermediate compartment. In the course of the electrolysis the concentration of chromic acid is rising up in the anolyte and is reducing in the intermediate compartment. However, there is now a risk of the transfer of sulfate ions from the catholyte into the intermediate compartment and from it into the anolyte, i.e. into a purified solution. Fortunately the experiments have shown that the transfer rate of sulfate ions is very low. The whole flow-sheet diagram of the combined process is shown in Fig. 4.

1 4 7

2 5 8

3 6

Fig. 4. Flow-sheet diagram of a combined method. 1, fresh water; 2, contaminated solution; 3, catholyte; 4, anode chamber; 5, intermediate compartment; 6, cathode chamber; 7, purified solution; 8, solution from the intermediate compartment with low concentrations of chromic acid and iron. Purified solution is collected in the container 7 and can be used for the replenishment of plating solutions or may be concentrated by evaporation. Certain problems are related with the efficiency of the process, when the concentration of chromic acid in the intermediate compartment becomes too low. Lower concentration of chromic acid in the intermediate compartment results in higher energy consumption and lower efficiency of the process. The use of a three-compartment cell and sulfuric acid in the catholyte allows to eliminate losses of chromic acid related with cathodic reduction. Slow transfer of metal ions into the catholyte is of no importance in this method, since purified chromic acid is accumulated in the anolyte. However, there is a problem of the utilization of the solution in the intermediate compartment which by the end of the electrolysis still contains appreciable amounts of chromic acid and ferric ions.

An alternative purification process which may be effective both technically and economically is based on the ion-exchange treatment. Unfortunately, commercially available cathion-exchange resin is stable only at moderate concentrations of chromic acid 4050 g/l. Therefore a right choice between the electrochemical and ion-exchange methods will depend on the requirements for the concentration of the purified solution, on the cost of electric energy and on the volumes of the solution to be purified per unit time. The latter factor is also an important one, since the membrane electrolysis proceeds quite slowly. Purely electrochemical process is probably most efficient for the recovery of chromic acid from reclaim tanks in chromium plating lines. Anodic and cathodic half-cells are immersed directly into the reclaim tanks (Fig. 5).

H2O

+
2

3 4 1 5

7 8

Fig. 5. Removal of chromic acid from the reclaim tank by means of two immersed electrochemical modules. 1, chromium plating tank; 2, reclaim tank; 3, anodic module; 4, anode; 5, anion-exchange membrane; 6, cation-exchange membrane; 7, cathode; 8, cathodic module. The concentration of chromic acid in the rinse water is maintained constant at low level and the input of chromic acid into next rinsing tanks is proportionally reduced. Chromic acid free of cationic impurities is concentrated in the anodic module and this concentrate is periodically added to the plating tank. This method allows to solve two problems simultaneously: the removal of iron and the recuperation of chromic acid from reclaim tanks. For large-scale chromium plating especially in decorative applications, where plating time is very short, ion-exchange is preferable because of higher energy consumption and lower rate of the purification in the electrochemical process. In other cases a combination of both processes will probably be economical. A principal arrangement of the components of the purification unit, which includes a multisectional three-chamber cell and an ion-exchange column, is shown in Fig. 6.

1 2 3
H2 O

5a 6a 7a

5b 6b 7b

5c 6c 7c

5d 6d 7d

8
Fig. 6. Principal arrangement of the components of the purification unit. 1, plating solution (250 g/l CrO3); 2, cathion-exchange column; 3, container for ferric sulfate sulfuric acid mixture + rinse water; 4, purified solution (125 g/l CrO3); 5a to 5d, anode compartments; 6a to 6d, intermediate compartments; 7a to 7d, cathode compartments; 8, catholyte preparation and utilization unit. The three-chamber cell is divided into four sections. It allows to maintain the contact of the solutions in the anode and in the intermediate compartments in a desirable manner: the concentrations of chromic acid at two sides of the anion-exchange membrane are approximately same. Rinse water from the column containing traces of chromic acid is used for the dilution of the initial plating solution, and purified chromic acid from the column 2 feeds the anode compartment 5a. At a fixed value of direct current the purification rate can be increased or decreased easily by changing volume of the solution feeding compartment 6d . If this value is increasing, the purification rate will increase, however, at the account of lower concentration of the purified solution collected in the container 4. In the opposite case at lower values of the purification rate a contribution of the ionexchange to the total process becomes smaller and the concentration of the purified solution increases.

Conclusions 1. Removal of ferric ions and other heavy metals from the solutions of chromic acid using three-compartment electrolytic cell is most efficient way in the case of reclaim tanks in chromium plating lines. 2. In small-scale decorative plating and hard-chrome applications a combination of electrochemical and ion-exchange methods seems to be most suitable. 3. Ion-exchange alone may be most suitable for high-output decorative plating lines. References 1. S.S. Kruglikov, D.Yu. Turaev, Electroplating & Surface Treatment, 10, #3, 57 (2002) 2. S.S. Kruglikov, D.Yu. Turaev, Yu.V. Tikhinova, Electroplating & Surface Treatment, 10, #1, 35 (2002) 3. S.S. Kruglikov, Proc. AESF SUR/FIN 2006, Milwaukee, p. 484