Recovery and Refining of Precious Metals Alloys by OxiNitrogen Leaching

Renato Bonora , Luciano Morselli

Department of Industrial Engineering, University of Padua, Italy UNIFRONT Spin off of the University of Padua Department of Industrial Chemistry, University of Bologna, Italy Speaker: Renato Bonora

Corresponding author: Renato Bonora, [email protected]

Abstract In recent years the demand for gold and other precious metals has increased dramatically, insomuch as in the last decade gold prices have quintupled. In the contest of the lack of trust in the traditional financial market, recovery and refining of precious metals from e-waste, automotive catalysts, and scrap jewellery and waste generated by jewellery manufacture have become increasingly more important. Controlled recovery of precious metals reduces additional waste production and helps prevent the need for supplementary mining. Metal recovery and refining processes can also have adverse effects on the environment when not conducted properly, especially when the pressure of the precious metals market price makes the refining companies speed up production. Separation technology described here is the hydrometallurgical method whereby gold-bearing alloys are obtained from gold scraps and wastes. Different metal grades are refined by aqua-regia or nitric acid dissolution in the presence of oxi-nitrogen species. Keywords: Precious metals, Hydrometallurgy, Oxi-nitrogen species, Leaching.

Introduction

The research effort was carried out with the purpose of industrially implementing improvements in the hydrometallurgical leaching of low and high-gold grade alloys for pure metal production. Nitrogen gaseous species, produced during oxidative leaching of low and high-grade gold-bearing alloys, respectively by nitric acid and aqua-regia, instead of being released into the atmosphere or cleaned, have been properly oxided with pure oxygen thus generating high oxidant solutions. The on site generated nitrogen species are more powerful oxidizing agents in comparison to conventional acid leaching processes; the catalytic oxidant property of nitrogen species (nitrate and nitrite) enhances the oxidation rates at a relatively lower temperature in a slightly pressurised-leaching reactor. Consequently, the modified process has shown unmistakably important improvements in terms of reduction both of relative quantity of the reagents used in the refining process, and the reaction times. Furthermore a reduction of relative process costs has been observed, due mainly to the far less consumption of reagents, with greater benefit for environmental impact and the costs of the whole process itself.

The full-scale test performed with the regenerated solutions, in the refurbished and adapted existing plant, demonstrated important advantages in reducing the consummation of nitric acid and reducing subsequently the consummation of other reagents and waste produced. The full-scale processes and related equipment used in the research permitted treatment of about 100 kg alloy per cycle.

1.1

Background

The manufacture of gold jewellery always generates scraps and waste, whether made by traditional techniques in a workshop or by mass production in a factory, such as gold sweepings, ashes, polishing dusts, crucibles, exhausted solutions, etc. electronic-waste is also a rich source of precious metals and its recycling business is rapidly growing. Table 1 reports the typical content of gold in different scraps and wastes. All of those materials need to be recycled back to pure gold and other metals.

Table 1. Representative gold contents for scraps and waste

Most recycled materials may contain, in addition to gold, all sorts of metals, depending on scraps and waste origin, such as: Silver, Palladium and sometimes Platinum, Copper, Nickel, Aluminium, Zinc, Tin, Lead and Iron. In addition, small amounts of elements like Beryllium, Barium and others have to be considered. Precious metal extraction or recovery from scraps commonly requires a combination of comminution, hydrometallurgical, and pyrometallurgical processes to be performed on raw materials in which they are contained. When precious metals are sufficiently concentrated there are several methods used to separate them. The most common methods used in the gold refining industry are the inquartion and parting and Aqua Regia processes respectively, for low and high gold content.

2 2.1

Refining processes Inquarting and parting process

The process is used for the treatment of low gold concentration scrap, 250/1000 (%) or less. When the gold concentration is higher then 250%, the refinable material is melted with additional silver to produce the alloy containing the designed concentration (inquarting). The dilution ensures that all the base metals and silver can be dissolved in nitric acid, leaving a gold sludge (parting) on the filter. The silver leaching reaction by nitric acid can be summarized by the follow equation: 4 Ag(s) + 6HNO3(aq) = 4AgNO3(aq) + NO(g) + NO2(g) + 3 H2O(l) (1) + Copper, as well silver, is oxidized by concentrated nitric acid, to produce Cu2 ions; the nitric acid is reduced to nitrogen dioxide: Cu(s) + 4HNO3(aq) = Cu(NO3)2(aq) + 2NO2(g) + 2H2O(l) In dilute nitric acid, the reaction produces nitric oxide, NO, instead: 3Cu(s) + 8HNO3(aq) = 3Cu(NO3)2(aq) + 2NO(g) + 4H2O(l) (3) (2)

The gold sludge is washed, filtered, and dried. Any Platinum present will also be dissolved, but insoluble platinum group metals (PGMs) will remain. Aqua Regia refining is necessary if pure gold is needed. The outline of the process is given in Figure 1.

Au ( 250%) + Ag, base metals, PGMs (Grains) Nitric Acid

Ag, base metals, Pt, Pd (Solution)

Au + Ir, Ru, Rh, Os (Sludge)

Ag, PGMs, base metals

Au + PGMs (to Aqua Regia pocess) (Sludge)

Figure 1. Outline of the inquarting and parting process.

2.2

Aqua Regia refining process

The aqua regia process is used to produce gold of up to 999.99 % purity; by this process the purity of gold obtained by inquartation can be increased. The alloy is grained to increase surface area, and aqua regia is added. The feed material, from the inquartation process, or Gold with > 250 % with silver content of

100% or less so that Aqua Regia (mixture is formed by freshly mixing concentrated nitric acid and hydrochloric acid, usually in a volume ratio of 1:3) dissolves gold into soluble gold chloride, each acid performs in a different way according to the following equations: Au(s) + 3 NO3(aq) + 6 H+(aq) Au3+(aq) + 3 NO2(g) + 3 H2O(l), and (4) 3+ Au (aq) + 4 Cl (aq) AuCl4(aq). (5) Nitric oxide can be produced rather than nitrogen dioxide according to the following reaction: Au(s) + NO3 (aq) + 4 H+(aq) Au3+(aq) + NO(g) + 2 H2O(l). (6) When the gold is completely dissolved, the insoluble silver chloride can be separated from the solution, along with the insoluble Platinum, Palladium, and other Platinum group metals. The gold can then be selectively precipitated using a number of reducing agents available, more often by sodium bisulphite, after the gold solution has been basified. Platinum group metals, Silver, and Copper will be successively separated. Inquarting and aqua regia processes both emit brown vapours of nitrogen oxide while metals are being dissolved. Fume abatement systems are generally required to reduce emission of these toxic fumes and to comply with pollution laws. The nitrogen oxide vapours, instead of being wasted, can be profitably recycled to produce the highly reactive oxy-nitrogen species solution that can be used in metal leaching. The outline of the process is given in Figure 2.

Au (> 250 %) + Ag (< 100 %) + base metals, PGMs (Grains) Aqua Regia, heat

Au, some base metals, Pt, Pd (Solution) Meta bisulphite Na2S2O5

AgCl + Ir, Ru, Rh, Os (Sludge)

Treatments to recover Ag and PGMs

Pure Au (Powder)

Pt, Pd, base metals (Solution)

Treatments to recover PGMs

Figure 2. Outline of the aqua regia process. The reaction of the nitric acid and the aqua-regia processes with the metals generates fumes of nitrogen oxide, these fumes are acrid, choking and extremely toxic and fume abatement

systems is needed to reduce emission to comply with pollution laws. Commonly, the NOxcontaining gas is sucked by standard blowers together with atmospheric air to a packed column washed by caustic solution. The alkaline resulting solution containing nitrates and nitrites periodically requires to be disposed of in accordance with law. Absorption of NOx, at the partial pressures of 300 Pa, with the addition of oxygen was experimented at 10C with water. The utilisation of the resulting acid solution in both, inquarting and parting and aqua regia processes were investigated.

2.3

Leaching with oxy-nitrogen species

The principle of precious metals leaching with oxy-nitrogen species is based on that nitrogen species (NO, NO2, etc.) being powerful oxidizing agents for metals.i The NO(g) produced in the reactions (1) shows low solubility in the aqueous leaching solutions and consequently it will be accumulated in the head space of the reactor and, due to the positive pressure in the oxidation reactor, where it can be rapidly oxidized by an oxygen rich atmosphere to produce nitrogen dioxide. Consequently, NO2 can be absorbed into the water at a high rate. In the leaching reactor NO is continuously generated and consequently the oxi-nitrogen species are continuously produced. The regeneration of the oxidant can be efficiently performed in absorption columns during leaching according to the simplified following reactions: 2NO(g) + O2(g) = 2NO2(g) 2NO2(g) = 2NO2(aq) 2NO2(aq) + 2NO2(aq) + H+ = 4NO+(aq) + 2H2O (7) (8) (9)

Under these conditions, nitrite originally presented as NO is rapidly converted into N2O4 (dimer of NO2 species)ii. It is assumed that the actual leach reaction is due to NO+ and not NO3-. Redox couple of NO+/NO in high hydrogen-ion activity solution shows an extremely high oxidation potential as shown in Table 2iii,iv,v.

Table 2 - Potentials of hydrometallurgical redox potentialvi

Redox Equation NO3 + 4H +3e = NO + 2H2O

Eh (pH = 0, H2 ref.) 0.957 V 1.202 V 1.230 V 1.358 V 1.450 V

2H +e = NO + H2O
+ -

O2 + 4H + 4e = 2H2O Cl2(g)+2e = 2Cl NO + e = NO

Table 2. Potential of hydrometallurgical oxidizers included the couple NO+/NO.

2.4

Industrial application of oxi-nitrogen leaching

The application of oxi-nitrogen oxidative leaching has been tested in a full-scale plant evaluating the main economic aspects in comparison to the conventional process. Figure 3. shows the outline of the oxi-nitrogen leaching species recovery (red) in the inquarting and parting process. The amounts of nitrogen chemicals are reported as mole of the nitric acid solution that generated them, and referred to 1 kg of alloy.

0.1 mole (as HNO3)

Gasometer HNO3 (67%) 7.2 mole P = 300 Pa T = 15C O2 2.7 mole

3.5 mole (as HNO3)

Leaching reactor 1 kg alloy Au 200% Ag 800% T = 60C

3.4 mole (as HNO3)

AgNO3 solution 7 mole (as HNO3)

Figure 3. Outline of the inquartation and parting process.

Figure 4. Shows the outline of the oxi-nitrogen species recovery (red) implemented in the Acqua Regia process. The amounts of nitrogen chemicals are reported as mole of the nitric acid solution that generated them, and referred to 1 kg of alloy.

0.6 mole (as HNO3)

P = atm T = 15C HNO3 (67%) 1.1 mole HCl (37%) 30.4 mole
O2 = 4.5mole

Leaching reactor 1 kg alloy Au 600% Ag 100 % Base metals 300% T = 60C

6.1 mole (as HNO3)

Meta bisulphite Au solution 0.4 mole (as HNO3)

Pure Au (Powder)

Figure 4. Outline of the Aqua Regia process.

The dissolution of the gold in the aqua regia process was conducted under atmospheric pressure in an open vessel equipped with a condenser to minimize loss of water.

Results

The results of the full-scale test performed with both processes are summarised in Table 3.

Table 3 The operating conditions used both in the conventional (old) and modified (new) leaching processes and the compared results.
Inquarting and parting
(Au 200%, Ag 800%)

Aqua Regia (Au 600%, Ag 100%,

Parameter Old New Variation %=-100(oldnew)/old +8 0 -32 Old

New

Variation %=-100(oldnew)/old +3 -29 -89 -50

Solubilisation yield (3h) (%) Reaction temperature (C) Nitric acid consumption (molenitric acid/kgalloy) Meta bisulphite consumption kgMeta bisulphite/kgalloy Oxygen consumption NlitreO2/kgalloy Exhausted solution production litre/kgalloy *Higher purity of gold.

90 80 10.6 -

98* 80 7.2 -

95 85 10.5 1.2

98 60 1.1 0.6

5.5

48 4.2

+100 -24

7.9

80 5.8

+100 -26

The results change with the different alloy leached.

Conclusions

Industrially proven and applied nitrogen species leaching has been utilized to treat a number of different alloys. The data reported represents the working condition practically utilised with the considered alloys. This technology offers many advantages in both processes, including primarily, sizable reduction of nitric acid used in the leaching phase and consequently a proportional reduction of the reducing agent solution, such as bisulphite in the aqua regia process for gold reduction. This very process shows a dramatic reduction in the use of nitric acid; in fact the system, related to the nitrogen compounds, is almost folly closed. Uncondensable gases are periodically discharged. The lower amount of bisulphite is mainly due to the less amounts of nitrogen compounds needed to be reduced and the residual acidity to be neutralised. The reduction in the production of wastewater was practically evaluated for both processes around 25%. The reduction of the consumption of reagents

permits low capital costs and low operating costs in the running of the processes and in the depuration of fumes and disposal of wastewater. References

Gok, Ozge. "OXIDATIVE LEACHING OF SULFIDE ORES WITH THE PARTICIPATION OF NITROGEN SPECIES-A REVIEW." Journal of Ore Dressing 12.24 (2010). ii Awad, H. H., and Stanbury, D. M., 1993, Autoxidation of NO in aqueous solution, Int. J. Chem. Kinet., V: 25, pp. 375-381. iii Peters, E. "Hydrometallurgical process innovation." Hydrometallurgy 29.1 (1992): 431-459. iv Anderson, Corby G., Leo E. Krys, and Kevin D. Harrison. "Treatment of metal bearing mineral material." U.S. Patent No. 5,096,486. 17 Mar. 1992. v Anderson, Corby G. "Alkaline sulfide recovery of gold utilizing nitrogen species catalysed pressure leaching." Hydrometallurgy 1 (2003). vi Anderson, C. G. "Applications of NSC pressure leaching." Presentation at Pressure Hydrometallurgy (2004).