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Simultaneous Recovery of Nickel and Aluminium from Spent Reformer Catalyst

By Dipak J. Garole and A. D. Sawant
June 2005
The Author is Research Scholar at the Institute of Science in Mumbai, India. The Paper was
presented at the 23rd annual conference of the Indian Council of Chemist, at K.C. College,
University of Mumbai. Prof. Arun Sawant, Pro Vice Chancellor of The Mumbai University, is
the guiding teacher.
Large quantities of spent nickel catalysts are available from fertilizer, petrochemical,
vegetable oil and other industries. Disposal of spent catalyst is a problem as it falls under
category of hazardous industrial waste. The recovery of metals from these catalysts is an
important economic aspect as most of these catalysts are supported catalyst usually with
alumina / silica with varying percent of industrially important element nickel, in the reference
catalysts alone; nickel concentration varies from 2.5-20%. A spent reformer catalyst was
treated with caustic soda solution of varying concentrations at temperature 90-100°C for
different times to dissolve aluminium as sodium aluminate. The recovery of aluminium was
97.4%. The residue was digested with aqua-regia for different time period at 90-100°C. The
recovery of nickel obtained was 95-96% in the form of NiSO 4.7H2O.
Keywords: Separation; Nickel and Aluminium recovery; Spent catalyst.
Metals like Ni, Mo, Co, Rh, Pt, Pd, etc., are widely used as a catalyst in chemical and
petrochemical industries. They are generally supported on porous materials like alumina and
silica through precipitation or impregnation processes. In many of the cases, the metals are
in the form of oxides, however, in the other cases, they are reduced into active metals for
catalyzing the appropriate reactions. After periodical use of the catalysts, due to poisoning
effect of foreign material and impurities, which deposit on the surface of the catalyst, they will
become inactive. In such cases, fresh catalysts have to be substituted and the spent catalyst
will be discarded as waste material.
Disposal of such catalyst materials, which contains appreciable amounts of heavy metals, is
environmentally hazardous. Therefore, a suitable and economically viable method is required
for recovery of metals at the same time method should not pose the risk of environmental
hazards. Therefore, recovery of nickel and aluminium from such catalyst attracted the
attention of investigators.
Various processes have been developed by number of researchers. Amad et al. (1970)
studied recovery of nickel from spent hydrogenation catalyst by digestion of it with different
acids. Recovery of nickel with inorganic acid was 85-94.5%, however, with HCOOH it was
80-5% and with ACOH about 65-8%. Tiwari et al. (1972) reported dry carbonylation process
as well as wet extraction with acids for different types of nickel catalyst. The carbonylation
process recovered 90-98% of the nickel metal and NiO where as extraction with HNO 3 and
HNO3-HCl mixture recovered 65-99% of the metal and its oxide depending on the nature of
catalyst. The poor recovery by acid treatment in some cases was attributed to the higher
amount of NiAl2O4 and NiSiO3, which has higher resistance towards acid leaching. Shinohara
et al. (1976) studied leaching of spent catalyst with caustic soda solution and treating the
residue with sulfuric acid solution for recovery of nickel. Drule minela liana et al. (1979)
studied spent catalyst fused with NaOH and NaNO 3 and treated the residue with H2SO4 for
recovery of nickel. Loboiko et al. (1983) studied leaching of nickel oxide with 60-70% nitric
acid concentration at 120°C for 2-3 h. Manoliu et al. (1985) studied leaching of spent nickel
catalyst first with 50% NaOH in autoclave at 150-175°C to dissolve Al as Na-aluminate. The

The solid/ liquid ratio was kept constant at 1:2 g/mL. To the filtrate containing Ni.5 Al/Fe precipitates its hydroxide and its removed by filtration. Fe. The process conditions studied include caustic soda and aqua regia concentrations. (1988) studied spent nickel catalyst with 32% hydrochloric acid concentration at 70°C and nickel recovery was found to be 96%. Chaudhary et al. The reagents like Na 2CO3. The grayish black rings of spent catalyst were crushed and powdered. . The amount of sulfuric acid was added to it and recovery of nickel in the form of nickel sulfate crystals was found to be 95-96%. They obtained low Ni extraction efficiency (only 18%). Ganguli et al. After that the percentage of nickel and aluminium were calculated.5 by adding dilute sulfuric acid Aluminium precipitated as aluminium hydroxide was converted into its oxide. Aluminium was dissolved into sodium aluminate and pH was adjusted to 5-5. HCl. The residue left after removal of aluminium is then digested with aqua-regia at 100°C for 2 hrs and filtered.4% of the Al present in the spent catalyst were extracted using 20% caustic soda solution after 120 min. About 97. The reaction between spent catalyst and caustic soda and aqua.. Experiment Materials and Apparatus The spent reformer catalyst used in this study was provided by RCF (India). H2O2. leaching with water at 80°C and crystallization as NiCl 2 at 85% nickel yield.regia was performed in a 500-mL round bottom flask on hot plate. Sibban Singh (1993) studied leaching spent nickel catalyst with 1-3 normal nitric acid at 100°C for 1-3 h. temperature. Procedure Hundred gram of spent catalyst was added at a time to the agitated caustic soda solution (200-mL) of the required concentration. Sinka et al. and Mg was added H 2O2 and Na2CO3 and pH was adjusted to 5-5. The study investigates the leaching aluminium and nickel from spent catalyst (NiO/Al 2O3) with caustic soda and aqua regia. Molnar et al. NaOH. (1991) studied reduction roasting-sulfuric acid leaching of nickel from spent nickel catalyst. reaction temperature 80°C. (1988) reported a spent hydrocracking catalyst roasted at 390°C with NH 4Cl. The samples were analyzed for determination of metals content using spectrophotomery and atomic absorption spectroscopy (AAS). Vicol et al. Results and Discussion Effect of caustic soda concentration on extraction of aluminium The effect of caustic soda concentration on leaching of spent nickel catalyst was studied using different concentrations in the range 5-25% at a constant temperature at 80°C. (2000) studied reclamation of nickel catalyst from spent catalyst by dry reduction method. H2SO4.5-9 and nickel was recovered as nickel nitrate. Pamela et al.87 M. (1988) studied extraction of nickel from spent nickel catalyst based alumina (NiO/Al 2O3) leaching with sulfuric acid solution 90% nickel was recovered. (1993) studied leaching the low-grade spent catalyst with hydrochloric acid. The results are shown in (Fig.1). The caustic soda concentration also has a pronounced effect on the dissolution of Al 2O3. Then the pH was adjusted at 6.5 by adding NaF/HF to precipitates Mg as MgF 2 to obtained nickel sulfate solution and its precipitate which was convert carbonate by adding Na2CO3.residue treated with HNO3 (1:1) at 60°C to dissolve nickel in the solution. Al. reaction time: 2 h. (1986) studied leaching of spent catalyst with an aqueous solution of 15-23% ammonia at 60-90°C at pH 7. used were of AR grade. HNO3. The leached solution was filtered. time and solid-liquid ratio. Khanna et al. About 98% of nickel was recovered as nickel oxide under the following conditions: sulfuric acid concentration: 1. time and temperature.

5 h.5-2. About 98% of the Ni present in the spent catalyst was extracted using 80% aqua-regia solution after 120 min. The aqua regia concentration also has a pronounced effect on the dissolution of NiO. For aluminium and Nickel respectively. Higher aqua-regia concentration in range 80-100% at constant temperature 80°C. The time has .Effect of aqua-regia concentration on extraction of nickel The plot of Ni extraction against aqua-regia concentration is presented in (Fig. The solid/liquid ratio was kept constant at 1:2 g/mL and 1/3g/mL. at a constant temperature of 80°C was carried out (Fig 3).2) The extraction of nickel was found to be quantitatively. 80% aqua.regia and time period in the range of 0. The solid/liquid ratio was kept constant at 1:3 g/mL. Effect of Time on Extraction of aluminium and nickel A spent catalyst with of 20% caustic soda.

In the temperature range of 60-100°C. The effect of Solid/ Liquid ratio on leaching efficiency and the concentration of Aluminium in the caustic soda solution S/L ratio {g/ml) Recovery (%) .timeb period and 20% caustic concentration and 80% aqua-regia concentration.significant effect on dissolution of nickel aluminium oxide. The solid/liquid ratio was found to be best for 1:2 and 1:3 g/mL for Al and Ni extractions. Solid-Liquid ratio (S/L) on extraction of aluminium and nickel The minimum S/L ratio of 1 /2 g/ml. and 98% Ni were extracted. had no adverse effect on extraction of aluminium is shown in Table 1. After 2h leaching time 97.4% and 98% of the Al and Ni present in the spent catalyst is extracted after 2h at a reaction temperature 90°C. Table 1. Effect of Temperature on Extraction of aluminium and nickel The effect of reaction temperature on Al and Ni extraction is plotted in (Fig.7% Al. was found to be sufficient for aluminium extraction and the S/L ratio increases upto 1/3 g/ml.4) for spent catalyst of 2h. About 97.

R. 4.0 ¼ 98. N.A.Fedorova.60 1/2 97. J. Sci.. Leaching of valuable metal in waste desulfurization catalyst. V. Japan kokai. Costea loan. 1972. Technology 9(2-3).the extraction efficiency negligible. 1979.. R.40 While in case of nickel the S/L ratio 1/3 g/ml. Pantaz´ev. o Shinohara. V. 1970. Yokio.. Ro 67 818. A.40 1/2. A.0 Conclusion 1.70 1/3 98. 86. Masood. M. Rom.masakaku. 1983.. Recovery of Ni from spent catalyst.0 1/2...I. Factors affecting the recovery of Ni from spent Ni-alumina and NiO-silica type catalyst.5 97. N. N. 5. B. o Tiwari.0 ½ 60.40 1/3 97. The rate of extraction of aluminium was found maximum at temperature 80°C further increase temperature no adverse effect on aluminium extraction.I. D. 76.. o Loboiko.P.. Volovikov. G. The effect of Solid/ Liquid ratio on leaching efficiency and the concentration of Nickel in the aquaregia S/L ratio {g/ml) Recovery (%) 1/1 40. Alekseenko. Could bring 98% of nickel in solution.. Golodenko. Arora. Kutovoi.I. Mitsuhasli.5 97. 227-232. Ganguli.. 2. Atroshchenko. The results are shown in Table 2. Very high recovery of aluminium obtained in very short time. Grin. The spent catalyst needs to leached with NaOH at 90-100°C to form soluble aluminium compound and it is easy to recovery of aluminium. 1976. Reference o Amhad.I. 134-8. The residue left after recovery of aluminium leaching with aqua regia at a temperature 90-100°C dissolution 2 hrs. G. Bhatty. Recovery of nickel as NiSO4. K..1/1 96. Table 2. o Drule minela liana.V. 3. 7(4). 002. (Karachi).7H2O crystals was obtained 95-96%. . M.... N.N. C. was found to be best for nickel extraction and the S/L ratio increases upto 1/4 g/ml.. Ind. Ya.

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