Chromium recovery from exhausted baths generated in plating processes and its reuse in the tanning industry.

Chromium plating used for functional purposes provides an extremely hard, wear and corrosion resistant layer by means of electrolytic deposition. Typical layer thicknesses range between 2.5 and 500 µm. Chromium electroplating baths contain high concentrations of Cr(VI) with chromium trioxide (CrO(3)) as the chromium source. When because of technical or economic reasons a bath gets exhausted, a waste containing mainly chromium as dichromate as well as other heavy metals is generated. Chromium may then be purified for use in other industrial processes with different requirements. In this work, a sustainable system for using galvanic wastes as reagents in the leather tanning industry, thus reducing quantity of wastes to be treated, is presented. Metal cations present in the chromium exhausted bath were precipitated with NaOH. Then, the solution containing mainly soluble Cr(VI) was separated. By means of sodium sulphite in acidic conditions, Cr(VI) was reduced to Cr(III) as chromium (III) sulphate. From chromium (III) sulphate a basic Cr(III) sulphate may be obtained, which is one of most used compounds in the tanning industry. Cr(III) concentration in the final solution allows its reuse without concentration, but with a slight dilution.

Semi-dynamic leaching tests of nickel containing wastes stabilized/solidified with magnesium potassium phosphate cements.

Herein is presented a study on the long-term leaching behaviour of nickel containing wastes stabilized/solidified with magnesium potassium phosphate cements. Two different semi-dynamic leaching tests were carried out on monolithic materials: ANS 16.1 test with liquid-to-solid ratio (L/S) of 10 dm(3) kg(-1) and increasing renewal times, and ASTM C1308 test with liquid-to-solid ratio (L/S) of 100 dm(3) kg(-1) and constant renewal time of 1 day. ASTM C1308 provides a lower degree of saturation of the leachant with respect to the leached material. The effectiveness of magnesium potassium phosphate cements for the inertization of nickel was proved. XRD analyses showed the presence of bobierrite on the monolith's surface after the leaching test, which had not been detected prior to the leaching test. In addition, the calculated cumulative release of the main components of the stabilization matrix (Mg(2+), total P and K(+)) was represented versus time in logarithmic scale and it was determined if the leaching mechanism corresponds to diffusion. Potassium is released by diffusion, while total phosphorous and magnesium show dissolution. Magnesium release in ANS 16.1 is slowed down because of saturation of the leachant. Experimental results demonstrate the importance of L/S ratio and renewal times in semi-dynamic leaching tests.

Leaching behaviour of magnesium phosphate cements containing high quantities of heavy metals.

Stabilization/solidification (S/S) is one of the most employed techniques for treating liquid wastes containing heavy metals. Magnesium potassium phosphate cements have been used in recent years as stabilizing agents with positive results. However, little information is available about the retention of the metals by magnesium potassium phosphate cements matrices with the exception of the results of compliance tests. In this work, several pastes were prepared by reaction between low grade MgO and KH(2)PO(4) in the presence of different heavy metal nitrate solutions (containing Cd(II), Cr(III), Cu(II), Ni(II), Pb(II) or Zn(II)). In all cases, the initial metal content of the dissolution was 25 g dm(-3) and the oxide-phosphate ratio of the pastes was (50:50) in weight. Four different leaching tests were conducted on magnesium potassium phosphate cement pastes: simple batch test (EN 12457-2), equilibrium leaching test, availability test (NEN 7371) and acid neutralization capacity test (ANC). The metal leachate concentration was determined by means of ICP-MS. The stabilization of metals was successful in all cases, although the immobilizing system shows a better behaviour for Pb(II) and Cr(III) under acidic or neutral conditions.

Effect of heavy metals and water content on the strength of magnesium phosphate cements.

In this paper the mechanical properties of magnesium potassium phosphate cements used for the Stabilization/Solidification (S/S) of galvanic wastes were investigated. Surrogate wastes (metal nitrate dissolutions) were employed containing Cd, Cr(III), Cu, Ni, Pb or Zn at a concentration of 25 g dm(-3) and different water-to-solid (W/S) ratios (0.3, 0.4, 0.5 and 0.6 dm(3)kg(-1)) have been employed. Cements were prepared by mixing hard burned magnesia of about 70% purity with potassium dihydrogen phosphate. Compressive strength and tensile strength of specimens were determined. In addition the volume of permeable voids was measured. It was found that when comparing pastes that the volume of permeable voids increases and mechanical strength decreases with the increase of water-to-solid ratio (W/S). Nevertheless pastes with the same material proportions containing different metals show different mechanical strength values. The hydration products were analyzed by XRD. With the increase of water content not previously reported hydration compound was detected: bobierrite.