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  • P.G. Tzeferis Et Al. (1991) Bioleaching of Greek Non-Sulphide Nickel Ores Using Microorganism Assisted Leaching Process

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    P.G. Tzeferis et al. (1991). "Bioleaching of Greek non-sulphide nickel ores using microorganism assisted leaching process". In: "Forum for Applied Biotechnology", Med. Fac.Landbouww. Rijksuniv.Gent, 56(4a), 25-27 September, Belgium, pp. 1797-1802.

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    P.G. Tzeferis et al. (1991) Bioleaching of Greek Non-sulphide Nickel Ores Using Microorganism Assisted Leaching Process

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    P.G. Tzeferis et al. (1991). "Bioleaching of Greek non-sulphide nickel ores using microorganism assisted leaching process". In: "Forum for Applied Biotechnology", Med. Fac.Landbouww. Rijksuniv.Gent, 56(4a), 25-27 September, Belgium, pp. 1797-1802.

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    P.G. Tzeferis Et Al. (1991) Bioleaching of Greek Non-Sulphide Nickel Ores Using Microorganism Assisted Leaching Process

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    PETROS TZEFERIS
    P.G. Tzeferis et al. (1991). "Bioleaching of Greek non-sulphide nickel ores using microorganism assisted leaching process". In: "Forum for Applied Biotechnology", Med. Fac.Landbouww. Rijksuniv.Gent, 56(4a), 25-27 September, Belgium, pp. 1797-1802.

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    1797 Med. Fac. Landbouww. Rijksuniv. Gent, 56(4a), 1991 BIOLEACHING OF GREEK NON-SULPHIDE NICKEL ORES USING MICROORGANISM ASSISTED LEACHING PROCESS P. Tzeferis, S. Agatzini, E.T. Nerantzis A. Dudeney, D. Leak & K. Alibhai National Technical University of Athens Laboratory of Metallurgy 42 Patission street, 06 82 Athens, Greece ABSTRACT Nickel is of vital importance in many modern industrial processes. Nickel ore deposits are found either as sulphides or as laterites.The dominating importance of lateritic ores for the future supply of nickel becomes obvious when one considers that about 80% of the presently known nickel reserves are associated with lateritic types of ores and it is strongly believed that the nickel production will in the not too distant future be dominated by laterite ores. Nickel from laterites is produced both pyrometallurgically and hydrometallurgically but most of the current industrial practice is energy intensive and non-economic for low-grade ores.The aim of the present study was to develop a low energy method using microorganisms in order to recover nickel from low-grade Greek laterites, as Greece has extensive laterite domestic sources.Bioleaching experiments were carried out to study the leachabiity of various laterite ore samples by several fungal strains. All strains, prior to leaching, were adapted to nickel and laterite environment by gradual acciimatisation. Two bioleaching tecniques were developed: (a) leaching in the presence of microorganisms and (b) chemical leaching at high temperature (85°C) with a solution consisted of the metabolic products obtained from the cultivation of fungus strains at 30°C in carbohydrate media such as glucose, sucrose and molasses. It was found that up to 55-60% of the nickel was extracted using the first technique and fungi strains Po (Penicilium sp.) and Ag (Aspergillus sp.) in almost 50 days. Losses of soluble nickel in the fungal biomass were found to be 3.5% and 10.8%, respectively.The cobalt recovery achieved was around 50%. Nickel recoveries obtained by the second technique were in the range of 70-72%. Use of factory grade Greek beet molasses, after chemical pretreatment with ferrocyanide, can contribute to a considerable reduction of overall cost since their price in Greek industrial market is considerably lower than price of industrially produced sulphuric acid and at least twenty times less than price of food grade sucrose. TROD! 1ON Nickel plays an important role in modern technology since it has numerous applications. Nickel consumption growth rate is expected (1) to increase significantly until the year 2000, primarily because of its increasing use in the stainless steel industry (which is the main consumer of nickel) but also because of many new applications (e.g. in the electronic industry, modern corrosion control, building and construction industries e.t.c.).Nickel ore deposits are found either as sulphides or as laterites. It is foreseen(@) that, in the near very future, laterites will become of dominating importance for the future supply of nickel. Greece has extensive laterite deposits with a low nickel content. The development of an economical method to exploit those deposits is of great importance for the Greek metallurgical industry. Biohydrometallurgy or bacterial (fungal) metal extraction is considered a low cost and non-waste effective technology allowing a comprehensive use of mineral resources using microorganisms and/ or their metabolites (®). Biological leaching is applicable to all ore grades and to waste materials from traditional ore processing, has lower energy requirements than conventional processes (operates at ambient temperatures) and is less hazardous from environmental aspect (4). z The aim of this work was to investigate the possibilty of using microorganisms in order to extract nickel and cobalt from low-grade Greek laterites. The work was performed at the Laboratory of Metallurgy of the NTUA and part of it was carried out in the framework of cooperation with the Centre for Biotechnology and the Mineral Resources Engineering Department of the Imperial College, London. 2. MATERIALS AND METHODS -Laterite ore samples Two lateritic nickel ore samples with different chemical and mineralogical composition were employed: (a) “Litharakia” (Euboes island, Greece) low-grade ore with 0.73% Ni and (b) ‘Kastoria” (kastoria, Northern Greece) ore with relatively high nickel content 4.239%. jicroorganisms ‘The folowing organisms were employed: . a) Strains of Aspergilus sp., Ay, Az & Ag (Commonwealth Mycological institute, London, courtesy of Dr.Leak, Imperial college) b) Strains of Penicilfum sp., Po, P14, Poa & Pg (Federal Institute of Geo-Sciences and Natural Resources, Hanover, courtesy of Dr. Bosecker) ¢) Strain of Penicilium sp., F;, isolated from an actively laterising nickel ore deposit (Mantoudi, Euboea island). 4) Strains of Aspergillus sp.A, and Penicilium sp., P, obtained from a Greek collection (Technical Educational Institute, Athens) ‘All strains screened for their ability to produce organic chelating acids (mainly citric and oxalic acids) and their tolerance to nickel concentrations and low pH conditions. Moreover, adaptation of all fungus strains was proceeded in nickel concentrations up to 4000ppm and laterite content up to 10% by stepwise increasing nickel and laterite content in the culture medium. - Media The following types of media were employed: a) Czapek-Dox broth or agar (GZ- CzA), b) Modified “Shu & Johnson’ (5) sucrose based media, c) Factory grade Greek beet molasses, obtained from “Hellenic Sugar Industry S.A. (E.B2). All (a), (b), and (c) types of media were used for both fungus growth and bioleaching experiments in different carbohydrate content (3% and 15% respectively). 1799 - Chemical leaching experiments. The chemical leaching tests were carried out before microbiological leaching experiments commenced in order to determine which organic acids (produced biologically) were responsible for nickel solubilsation from laterite crystal lattice. This preliminary work was considered necessary because leaching efficiency of heterotrophs mainly depends on the production of organic metabolic compounds (organic acids, amino acids, polysaccharides) with significant metal-binding properties which are excreted from the cells to the medium(®). Various organic acids and combinations mainly between organic acids and sulphuric acid were tested in the concentration range of 0.1-0.5M. The leaching test were carried out in conical flasks containing known weights of ore and volumes: of synthetic organic: acid solutions. : -Bioleaching experiments. Bioleaching tests were carried out in flasks following two different techniques: {a) Microorganisms are cultivated in the presence of the ore. In this technique medium and inoculum are added to the ore. Prior to leaching, ore was sterilised to avoid interference from organisms present in the ore (indigenous). ee (b) Leaching with metabolic products of fungal growth after separation from the biomass (two phase procedure). Cultivation was carried out in lab. fermenters and leaching with biologically produced acid metabolites at both natural pH (final pH of the fermentation process) and even lower pH (acidified to 0.3 by means of sulphuric acid). 3.RES DI 1. Among various organic acids (acetic, citric, oxalic, formic, lactic, suiphosalicylic) tested for their ability to dissolve nickel from lateritic ore samples used, most effective was citric acid including both samples. Although citric acid requires for effective leaching longer time (40-50 days) than equimolar sulphuric acid, in the case of ‘kastoria” garnieritic sample it performed better than sulphuric acid (yields of 57.5% versus 52.7% of the nickel respectively) at the same conditions (0.5M, 30°C, 10% pulp density), depended markedly on the type of mineralisation. Oxalic acid was the least effective leaching agent as far as nickel is concerned while leached much more iron than any other organic leaching agent used (63% of iron from "kastoria® and 20% from ‘Litharakia” sample). One possible explanation for this could be the following reductive process (FeO is soluble): Fej0g + CoH04 —> 2FeO + 260p + HzO Results of chemical leaching are shown in Table 1.The considerable variability in nickel recoveries achievable in chemical leaching of different samples depends on the type of mineralisation. 1802 |. GE AL ION From the above described preliminary study on the feasibility of using bioleaching to Tecover nickel from non-sulphide nickeliferous Greek ores can be concluded that samples tested ere generally amenable to bioleaching by both techniques used in laboratory scale. Maximum yields obtained were up to 72% of nickel, 50-55% of cobalt and 20-25% of iron codissolution.Yet, much remains to be done before heterotrophic leaching process will find technical and economic application and thus become profitable business. Expensive nutrient requirments have to be replaced by inexpensive molasses or other organic waste products (e.g. from paper, food and beverage industries) in order to reduce the overall cost. Use of Greek molasses, although they have a variable chemical composition and need chemical pretreatment before bioleaching to attain higher nickel yields, can contribute towards this direction of research. REF! ICE 1.J.P. Schade and M.O. Pearce (1988)."The role of nickel in modern technology’. In: Proceedings of a symposium on the extractive metalurgy of nickel and cobalt, 117th TMS Annual Meeting, Phoenix Arizona, January 25-28, 1988. 2. T.R.Scott (1976) "Recent advances in hydrometaliurgy with implications for the developing countries” In:"Economics of mineral engineering”, seminar organised by the United Nations in co-operation with the government of Turkey, Ankara, April 1976, pp. 56-89. 3. G.L.Karavaiko, G.Rossi, A.D. Agate, S.N.Groudev, Z.Z.Avakyan (1988) . Bioaeot ology of Metals, (Manual), UNEP, USSR Commission for UNEF, Centre for International Projects GKNT, Moscow, pp.321. 4. D.G. Lundgren et.al. (1986). "Chemical reactions important in Bioleaching and Bioaccumulation” In: H.L.Ehrlich and D.S.Holmes, Editors. "Workshop on biotechnology for the mining, metal-refining and fossil fuel processing industries". Biotechnol. Bioeng., Symposium No.16., John Wiley & Sons, Inc. 1986,pp.7-22. 5.P.Shu and M.J.Johnson(1948). “The interdependence of medium constituents in citric acid production by submerged fermentation”. Bacteriol, 56, pp.577-585. 6. K.Bosecker (1985). "Leaching of lateritic nickel ores with heterotrophic microorganisms" , In: proceedings of the sixth international symposium on Biohydrometalturgy, Vancouver, Canada, August 21-24, 1985. KNOWL MENT The authors are grateful to the Commission of the European Communities (CEC), Directorate General for Science, Research and Development, DG-XIl C-5, the General Secretariat of Research and Technology of Greece (f..E.T) and the General Mining and Metallurgical S.A.LARCO for financial support. Thanks are also expressed to the Hellenic Sugar Industry S.A. (E.B.Z) for molasses samples and relative information. 1801 “itis noteworthy that Ni/Fe in sample “Litharakia” is 0.05. Numbers marked in the above table indicate a decrease in the recovery owing either to biosortion of metal in fungal biomass of precipitation of organometallic compounds or hydroxides (calcium citrate, iron citrate, goethite) . 3, Leaching of “Litharakia” ore sample with metabolic products produced as & result of the cultivation of strains Pz and Ag in sucrose based media at 30°C, gave extractions of nickel up to 25% when it was carried out without any dilution with mineral acids and up to 72% when it was carried out after acidification to a pH of 0.3 by means of sulphuric acid. In both cases leaching temperature was 95°C. Although the pracess.as a whole is being mote expensive because of the cost of fermentation and consumption of mineral acids, there is also the alternative use of washed and dryed mycelium which represent @ protein-rich valuable foodstuff. ‘A simplified process flowsheet for nickel recovery from laterites using the above two- = phase technique follows: ‘SOLID-_ LIQUID MICROBIAL PROTEIN ‘SEPARATION ORGANIC ACIDS-CONTAINING NON-SULPHIDE ‘CULTURE SOLUTION NICKELIFEROUS: ORE SULPHURIC ACID TO APH OF 03 QRGANOMETALLIC OMPLI SOLID RESIDUE ein ‘SOLUTION 4. Chemical leaching of ‘Litharakia” ore sample using metabolic products of strains Pp and F 4 (most effective strains for bioleaching in molasses media) in 15% molasset media after acidification of fermented liquid to pH 0.3 with suiphuric acid, gave nickel yields of 54% and 62%, respectively. Before fermentation procedure, the beet-molasses medium was treated by adding 1.59 of potassium ferrocyanide- (K4iFe(CN)g]) which has been used extensively in the treatment of molasses for the production of citric acid by mold fermentation . Itis suggested that better resuits obtained after this pretreatment could ascribed to at least two functions of ferrocyanide. The first is to remove deleterious trace metals from the medium whereas the second is to act as a direct inhibitor of growth of the mycelium. Both functions can stimulate citric acid production. Results mentioned above (up to 62%) compared to nickel recoveries in pure sucrose media (up to 72%) and leaching with sulphuric acid (45.5%) all at the same leaching conditions (pH:0.3, temperature: 96°C, leaching time:S hours) are much more attractive in economic terms despite cost of necessary pretreatment of molasses. Greek, factory grade, untreated molasse’s price in Greek industrial market is estimated 13-14 drsikg, considerably lower than the price of industrially produced sulphuric acid and at least twenty times less than the price of food grade sucrose. 1800 TABLE 1 ee Leaching of laterite low-grade nickel ore “Litharakla” pulp density:10%, Particle size

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