REFINING AND TREATMENT OF PALLADIUMFROM SECONDARY RESOURCES

Rabatin Ľ., Vadász P., Tomášek K. Institute of Metallurgy and Materials, Faculty of Metallurgy Technical University of Košice, Slovakia Abstract Palladium extraction and refining is a complicated chemical process consisting of the repeated chemical dissolution and selective precipitation of Pd salt. There is necessary to suggest a specific process variation of every type of Pd input. Chemical technology of the treatment of palladium slime obtained from the silver electrolysis at Ag-Pd electronic scrap treatment were tested and verified in the laboratory scale by authors of this paper. Chemical reactions of the palladium dissolution, selective precipitation and reduction processes are described and their thermochemical data are discussed. The individual steps of the technological flow sheet of palladium extraction and refining is described in the second part of this work. Palladium slime is leached by aqua regia, and then palladium - chloride salt is precipitated by ammonium chloride. After annealing and reduction in hydrogen atmosphere is Pd - sponge obtained with purity of 95 wt. % Pd. After refining of this Pd sponge by repeating of the same processes were Pd sponge with purity of 99 wt. % Pd and 95 % efficiency obtained. Key words: palladium, extraction, refining, reduction

1. INTRODUCTION The first scientific tests of palladium associated with the appearance and processing of platinum go back to the year 1803 [1]. Palladium belongs to the eighth group of the periodic table and is located in the so-called light platinum triad - ruthenium, rhodium and palladium. Platinum metals in the earth's crust are very common (10-7 to 10-9 mole.%). Their scarcity is also related to their large dispersion. Palladium has a strong ability to absorb (dissolve) gases. Especially great is the absorption of hydrogen [2]. Even at moderate heating in vacuum hydrogen escapes. Palladium is still on the air, the annealing above 300 ° C, the purple colour of the surface, there is the emergence of ADT. Palladium oxide is raising the temperature (above 870 ° C) once again breaks the surface and enter into the original metal colour. Palladium is dissolved in Aqua Regia, but it also acts on the nitric acid, hydrochloric acid, respectively boiling concentrated sulphuric acid [1]. A large dispersion of platinum metals and the difficulty of obtaining them are causing their high price. Palladium is one of the metals, which are often used in the chemical and automotive industries as catalysts in electrical engineering, dentistry and jewellery. Wastes from these industries are becoming, recently significant source of palladium. Acquisition of platinum metals (from both primary and secondary raw materials) is a very complex set of chemical - analytical methods. Large consumption of reagents and a large number of repetitive operations is also reflected in the price of these metals.

In the theoretical part of the paper provides an overview of some methods of obtaining palladium and description of chemical reactions taking place in these processes. The experimental section describes the technology of obtaining palladium in the process of electrical scrap, which was conducted at the Institute of Metallurgy and Materials HF TU Košice [3]. This meal was made up of contacts, which contain Ag-Pd alloy with different contents of palladium. Palladium is concentrated in sludge during the electrolytic refining of silver. In the presented article is given technological scheme of processing Pd - sludge, to metallic palladium and its refining purity over 99% Pd. Ongoing processes we have tried to give chemical equations and the relevant thermodynamic parameters. 2. THEORETICAL PART 2.1 Dissolution Study of literature [1, 2, 4-6] showed that the palladium can be dissolved in concentrated nitric acid or in Aqua Regia, according to the following reactions: Pd (s) + 4HNO3 (l) = Pd (NO3) 2 (l) + 2NO2 (g) + 2H2O (l) (1) Arises palladium nitrate (water soluble), water and gaseous carbon dioxide. In practice, the technology being used in Aqua Regia dissolution, which is prepared by mixing one part concentrated nitric acid and three parts concentrated hydrochloric acid. Arises nitrozylu chloride and chlorine gas, and products of this reaction in an aqueous environment may be further reacted according to the following reactions: HNO3 (l) + 3HCl (l) = NOCl (g) + Cl2 (g) + 2H2O (l) (2) 2Cl2 (g) + 2H2O (l) = 4HCl (l) + O2 (g) (3) NOCl (g) + H2O (l) = HNO2 (l) + HCl (l) (4) 3HNO2 (l) + H2O (l) = HNO3 (l) + 2NO (g) + 2H2O (l) (5) NO (g) + 3NO2 (g) + H2O (l) = 2HNO3 (l) + 2NO (g) (6) Chemical reaction of dissolution of palladium in Aqua Regia can be described by the following equations: Pd (s) + 2NOCl (g) + Cl2 (g) + H2O (l) = PdCl4 (l) + 2NO (g) + H2O (l) (7) PdCl4 (l) + 2HCl (l) + H2O (l) = H2PdCl6 (l) + H2O (l) (8) H2PdCl6 (l) + H2O (l) = H2PdCl4 (l) + Cl2 (g) + H2O (l) (9) When dissolving in Aqua Regia palladium occurs paládičitého of chloride, which reacts with hydrochloric acid to form hexachloropaládičitej. This is due to elevated temperature decomposes according to reaction (9) tetrachloropaládnatú acid and chlorine gas. Equation (2) to (6) describe the reaction in progress in the preparation of Aqua Regia. These reactions occur simultaneously, the products of one reaction become the next reaction reagents. 2.2 Selective exclusion

Selective elimination of palladium from acid solution tetrachloropaládnatej be done using ammonium chloride, yielding tetrachloridpaládnato ammonium ((NH4) 2 [PdCl4]). Before it is necessary to remove the presence of sodium nitrate, and the addition of hydrochloric acid and boiling or addition of sodium chloride and hydrochloric acid [1, 2, 4-6]. Tetrachloropaladnatan ammonium compound is soluble in a given environment and therefore it is necessary to stabilize. Getting insoluble compounds of palladium is possible in two ways. The first is based on the addition of ammonia (NH3) and hydrochloric acid [4], according to reactions: H2PdCl4 (l) + 2NH4Cl (l) + H2O (l) = (NH4) 2 [PdCl4] (l) + 2HCl (l) + H2O (l) (10) (NH4) 2 [PdCl4] (l) + 4NH3 (l) + H2O (l) = [Pd (NH3) 4] Cl2 (l) + 2NH4Cl (l) + H2O (l) (11) [Pd (NH3) 4] Cl2 (l) + 2HCl (l) + H2O (l) = [Pd (NH3) 2] Cl2 (s) + 2NH4Cl (l) + H2O (l) (12) Diammin compound dichloro-palladium ([Pd (NH3) 2] Cl2) is filtered and washed with dilute hydrochloric acid. This compound is slightly soluble in cold water, which is used in the refining of palladium from the accompanying elements [4]. In the second method is tetrachloropaládnatan ammonium is oxidized with sodium chloride and hydrochloric acid [5] hexachloropaládičitan ammonium according to the equation: 2 ((NH4) 2 [PdCl4]) (l) + 2NaCl (l) + 2HCl (l) + 2NOCl (g) + 6H2O (l) = 2 ((NH4) 2 [PdCl6]) (s) + 2NaNO3 + (l) + Cl2 (g) + 5H2 (g) + H2O (l) (13) The solution falls hexachloropaládičitan compound ammonium ((NH4) 2 [PdCl6]) red, which is filtered and washed with dilute hydrochloric acid to remove the excess ammonium chloride. Thermochemical and thermodynamic data on these reactions are not available in the literature or databases available. 2.3 Reduction Metallic palladium is obtained by thermal decomposition of the dried compound (NH3) 2 [PdCl 2], respectively. (NH4) 2 [PdCl6] in a reducing atmosphere at temperatures above 870 ° C [1, 4, 5], according to the following reactions: 3 ((NH3) 2 [PdCl 2]) (s) = 3PD (s) + 4NH4Cl (s) + 2HCl (g) + N2 (g) (14) 3 ((NH4) 2 [PdCl6]) (s) = 3PD (s) + 2NH4Cl (s) + 16HCl (g) + N2 (g) (15) NH4Cl (s) = HCl (g) + NH3 (g) (16) At temperatures above 350 ° C, ammonium chloride decomposes, respectively. at 520 ° C sublimes [9]. In the literature [2] are given feedback on direct reduction of palladium from aqueous solutions such as palladium chloride. PdCl 2 (l) + CO (g) + H2O (l) = Pd (s) + CO2 (g) + 2HCl (l) (17)

PdCl 2 (l) + H2 (g) + H2O (l) = Pd (s) + 2HCl (l) + H2O (l) (18) Reaction (17) is used for analytical evidence to carbon monoxide gas. Table 1 Termochemical data of some Pd reduction reactions [10] The data listed in Table 1, obvious that the chemical processes of refining palladium are described in the literature lack. Thermodynamic data of palladium compounds studied in the literature [80-10] were published, and therefore it was not possible to assess the negotiability of chemical reactions, dissolution, selective elimination and reduction of palladium in those works [4 and 5]. Similarly, inadequate and sometimes are referred to several different properties of the compounds of palladium [2, 4, 5, 7 and 9]. 3. EXPERIMENTAL PART The experimental section describes the technology of obtaining palladium in the process of electrical scrap, which was developed and implemented at the Institute of Metallurgy and Materials HF TU Košice [3]. Scrap electrical contact was formed that included alloy Ag - Pd with different contents of palladium (Table 2). Palladium is concentrated in sludge during the electrolytic refining of silver. Pdprocessing technology - the sludge is divided into three phases (Fig. 1). In the first phase of palladium is dissolved in Aqua Regia, sludge, followed by selective elimination phase palladium compound and its stabilization in the last stage of the palladium complex to thermal decomposition to metallic palladium. Obtained by Pd - Fungus again dissolved in Aqua Regia, selectively eliminated and thermal decomposition, multiple repetition of these chemical processes may be obtained palladium purity over 99% Pd. Vyrafinovaná Pd - sponge is melted in a vacuum induction furnace on a metal ingot. Ongoing processes we have tried to express the chemical equations. 3.1 Stage sludge leaching palladium (palladium mushrooms) Chemical composition of starting material and products in the processing and refining of palladium is shown in Table 2 In the first stage of the process sludge palladium dissolved in hot Aqua Regia, the following conditions: Leaching (dissolution) parameters: HCl: HNO3 = 3: 1 L: S = 3: 1 Temperature: 85 to 95 ° C Leaching time: 120 min. Table 2 Chemical composition of the input and output products of the Pd treatment and refining Where: A 1 - anode slime from Ag-electrolysis [wt. %] B 1 - filtrate from Pd-slime extraction [g. l-1]

B 2 - filtrate from Pd-sponge refining [g. l-1] C 1 - Pd-sponge [wt. %] C 2 - rafinated Pd-sponge [wt. %] Fig.1 Technological flow sheet of Pd extraction and refining Sludge composition of palladium (Table 2, sample A1), it is clear that during leaching in Aqua Regia, will take place mainly chemical reactions (2) to (9) in the previous chapter, and which are just a summary equations (2) and ( 19). Given the high silver content in palladium and copper sludge, we count in the process of leaching and chemical reactions with silver and copper with Aqua Regia, equation (23) and (24). HNO3 (l) + 3HCl (l) = NOCl (g) + Cl2 (g) + 2H2O (l) (2) Pd (s) + 2NOCl (g) + Cl2 (g) + 2H2O (l) = H2PdCl4 (l) + NO (g) + NO2 (g) + H2O (l) (19) 4Ag (s) + 2NOCl (g) + Cl2 (g) + 2H2O (l) = 4AgCl (s) + NO (g) + NO2 (g) + H2 (g) + H2O (l) (20) 2Cu (s) + 2NOCl (g) + Cl2 (g) + H2O (l) = 2CuCl2 (l) + 2NO (g) + H2O (l) (21) Palladium is dissolved in hot Aqua Regia acid to form tetrachloropaládnatej (H2PdCl4), whose creation is described in chemical equation (7) to (9), in Chapter 2.1. Silver falls in the form of AgCl precipitate and copper passes into solution in the form of cupric chloride (CuCl2). Silver chloride precipitate was filtered, washed and dried. Dried silver chloride melts, the reduction with the addition of Na2CO3 and obtained metallic silver purity from 95 to 99% Ag. In the case of palladium refining hubs palladium leaching stage is replaced by a slurry by dissolving palladium mushrooms in Aqua Regia, in identical conditions. Crucially there are ongoing chemical reactions (19) and (21). 3.2 Phase selective elimination and stabilization of palladium compounds Tetrachloropaládnatá acid is selectively precipitated by ammonium chloride (NH4Cl), to form the compound palladium tetrachloride nitrate ((NH4) 2 [PdCl4]) by reaction (10). Cupric chloride reacts with ammonium nitrate to form soluble compounds Copper nitrate tetrachloride by reaction (22). CuCl2 (l) + 2NH4Cl (l) + H2O (l) = (NH4) 2 [CuCl4] (l) + H2O (l) (22) Divalent palladium compound, i.e. ammonium palladium tetrachloride is unstable and therefore the palladium is oxidized with sodium chloride and hydrochloric acid štvormocnú compound, ie hexachlorid paladičito ammonium ((NH4) 2 [PdCl6]), which is insoluble in this environment, reaction (13). The resulting red precipitate was filtered and washed with dilute hydrochloric acid (50 to 10 vol.% HCl) to reduce the copper content in the precipitate to a minimum. Pd content in the filtrate (0.3 to 0.5 gl-1) is continuously controlled, collected, thickens and campaign-treated in a separate stage of processing raw materials palladium with organic compounds or liquid extraction [1, 4, 6]. After obtaining the Palladium, the filtrate containing copper can be processed in the process of copper production.

3.3 Stage pyrolysis compounds paládičitej After filtration and washing, the merger of (NH4) 2 [PdCl6] dried at 200 ° C in order to remove physically and chemically bound water. The dried ammonium hexachlorid paládičito the thermal decomposition at 650 ° C in air atmosphere by reaction (23). 2 (NH4) 2 [PdCl6] (s) + O2 (g) = 2PdO (s) + 4NH3 (g) + 4HCl (g) + 4Cl2 (g) (23) Thermal decomposition is performed to complete the layout of the compound of ammonia, hydrochloric acid and chlorine, while the boats remain spade palladium oxide. In the next stage of the process to reduce the palladium oxide to metallic palladium, the flow of gas mixture: argon + hydrogen (5-10 vol.% H2) and at 1000 ° C. Palladium oxide decomposes to palladium metal powder (Pd-sponge, light gray) and water vapor as reaction (24). ADT (s) + H2 (g) + Ar (g) = Pd (s) + H2O (g) + Ar (g) (24) Table 2 shows the chemical composition of Pd-fungi (C 1), obtained from palladium sludge and composition of palladium mushrooms after one-stage refining (C 2). Purity Pd fungi increased from 95.64% to 99.75% Pd Pd. Multiple repetition of the refining process may be obtained palladium palladium purity of 99.9% Pd. 4. CONCLUSION In the presented paper presents a palladium sludge processing technology for pure palladium, which was designed and implemented at the Institute of Metallurgy and Materials HF TU Košice. Palladium sludge contained about 60% Pd 20% Ag, 18% Cu and about 2% (Zn, Ni, Mn, Fe), the sludge is infused in Aqua Regia, the solution to precipitate silver chloride, which is filtered and processed to Metallic silver. In the next stage of the solution selectively exclude hexachlorid paládičito ammonium compound, which is in the final stage of thermal decomposition process and reduces to the metal palladium. She won the palladium sponge to clean about 95% Pd, which is refined the same technology. One-product of refining of palladium purity over 99% Pd-Pd in the form of mushrooms. The effectiveness of the acquisition of Ag-Pd - Pd contacts that technology was 95%. It is clear that increasing the purity palladium causes a rise in the cost and reduces the effectiveness of obtaining Pd. If the requirements of higher purity can be chemical refining repeated until the desired purity palladium finished product. Sewage processing solutions with a low concentration of palladium is demanding both technically and economically. Used to process liquid extraction or analytical chemistry for the use of organic compounds, which adversely affect the human body [4-6]. Palladium hub can be melted in a vacuum induction furnace or in a protective atmosphere and cast into ingots. Thanks This work was addressed within the Ministry of Education grant project VEGA SR No. 1/6002/99 Literature [1] Kmeťová, D.: Metallurgy of precious and rare metals. Temporary college textbook. Editing Center at the Technical University in Kosice, 1984.

[2] Gažo, J., Kohout, J., Serátor, M., Šramko, T., Sigmund, M.: General and Inorganic Chemistry, 3rd Edition. ALFA, Bratislava, 1981 [3] Vadász, P., Rabatin, Ľ., Tomasek, K.: Recovery of silver and palladium from scrap electronics. Acta Metallurgica Slovaca, 6, 2000, 2, 125-132 [4] Maslenickij IN, Čugajev LV, Borba VF, Nikitin MB Střížkov LS: Metallurgija blagorodnych metallov. Moscow, 1987 Metallurgija [5] Hoke C.M.: Refining Precious Metal Wastes. Reprint available from Met-Chem Research, P.O. BOX 3014, Boulder, 1940, USA [6] Beamisch FE: The Analytical Chemistry of the Noble Metals. Pergamon Press, Oxford, 1966 [7] Chemical table. Translation: Mervart M., Šob J., John Wiley 1955 [8] I. Barin, O. Knacke: Thermochemical properties of inorganic substances. Springer-Verlag Berlin Heidelberg New York, Verlag Stahleisen mbh Düsseldorf 1973 [9] RH Perry, CH Chilton: Chemical Engineers' Handbook. McGraw-Hill Book Company, 5 edition, 1973 [10] A. Roine: Outokumpu HSC Chemistry for Windows, Version 3.2

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