Powder Technology 103 1999.

260264

Arsenic removal through the decrepitation of colemanite ores

Fatma Arslan
a

a,)

, Cuneyt Arslan b, Mehmet S. Celik

Istanbul Technical Uniersity, Mining Faculty, Mining Engineering Department, Mineral and Coal Processing Diision, 80626 Maslak, Istanbul, Turkey b Istanbul Technical Uniersity, Chemistry and Metallurgy Faculty, Metallurgical Engineering Department, Extractie Metallurgy Diision, 80626 Maslak, Istanbul, Turkey Received 17 August 1998; received in revised form 10 December 1998; accepted 11 January 1999

Abstract Despite their high boron contents, some boron deposits in Turkiye contain considerable amountS of arsenic. Arsenic in boron minerals receives penalty in marketing and thus its removal is necessary. Since colemanite undergoes decrepitation at temperatures near its decomposition, the objective of this study was to determine the extent of arsenic removal through the decrepitation of colemanite ores with high As content. The effect of temperature, retention time, and particle size range was investigated and the degree of arsenic removal and the quality of colemanite concentrate were quantified. The results reveal that arsenic removals of 9598% with As levels as low as 0.02% in the colemanite concentrate are achieved. q 1999 Elsevier Science S.A. All rights reserved.
Keywords: Decrepitation; Boron minerals; Colemanite; Arsenic; Calcination; Beneficiation

1. Introduction Turkiye has the largest boron reserves in the world. Boron deposits are located in four regions, namely; Eskisehir-Kirka, Kutahya-Emet, Balikesir-Bigadic, and Kestelek Bursa. Some of these deposits contain considerable amount of arsenic in spite of their high boron contents. Boron ores are generally upgraded by concentration techniques including physical, chemical, and physicochemical processes. Among these processes, flotation and heat treatment are potential techniques for the removal of arsenic from the boron ores. The removal of arsenic from colemanite Ca 2 B 6 O 7 P 5H 2 O. by flotation has been studied w1,2x. One of these studies claims that 80% of the arsenic minerals was concentrated by flotation using potassium amyl xanthate as collector at a natural pH of 9.3. In another study, a colemanite concentrate with 44.4% B 2 O 3 content was recovered with 85.1% efficiency from a colemanite ore assaying 22.9% B 2 O 3 and 0.27% As. An arsenic concentrate of 15.72% As was obtained with 85.5% recovery, leaving the final colemanite concentrate with 0.05% As.

) Corresponding author. Tel.: q90-212-285-6357; Fax: q90-212-2856863; E-mail: arslan@sariyer.cc.itu.edu.tr

Hydrated boron minerals undergo reduction in their original weight after the heat treatment, due to loss of water molecules. Thermal treatment of boron minerals also results in some structural modifications, due to formation of micropores and the resultant expansion of the crystal matrix upon development of uneven distribution of stresses. Such internal stresses subsequently induce fractures and in turn, fragmentation of the crystals. When they are heated to the decomposition temperature, some minerals, such as colemanite, break to a fine powder. A similar phenomenon may also occur upon cooling. This phenomenon is called decrepitation. Clearly, one should distinguish the difference between decrepitation and calcination of volatile minerals, e.g., barite or calcite, where the original mineral is converted to the oxide form w3,4x. Decrepitation followed by air tabling is utilized at the American Borate plant near Lathrop Wells, NV, for upgrading of colemanite w5x. The possibility of decrepitation followed by wet tabling has been recently suggested as an alternative to air tabling w6x. Enhancement of boric-acid production upon decrepitation of colemanite at temperatures higher than 6008C has been reported w7x. Decrepitation properties of colemanite ore have also been studied to some extent w3,8x. These studies indicated that although most boron minerals exhibit various degrees of hydration, only colemanite appears to undergo decrepitation. Cole-

0032-5910r99r$ - see front matter q 1999 Elsevier Science S.A. All rights reserved. PII: S 0 0 3 2 - 5 9 1 0 9 9 . 0 0 0 2 0 - 0

F. Arslan et al.r Powder Technology 103 (1999) 260264 Table 1 Particle size distribution and corresponding chemical analysis of colemanite sample Particle size range mm. Amount by wt.% % B2 O3 Content y 4.76 q 3.36 y3.36 q 2.36 y2.36 q 1.68 y1.68 q 1.00 y1.00 q 0.841 y0.841 q 0.600 y0.600 Total 17.2 16.4 15.6 13.9 4.1 7.4 25.4 100.0 31.7 30.9 30.8 30.7 21.8 29.0 30.4 30.7 Distribution 17.7 16.5 15.7 13.9 4.0 7.0 25.0 100.0 % As Content 0.46 0.36 0.38 0.40 0.40 0.69 0.43 0.43 Distribution 18.4 13.8 13.8 12.9 3.8 11.9 25.4 100.0

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manite produces a fragmentation pattern similar to that of minerals ground in ball mills. Earlier studies on decrepitation of colemanite were performed with either pure colemanite mineral or colemanite ores. Therefore, in the light of these studies, arsenic removal during the decrepitation of colemanite ores constituted the main objective of this study. The effects of several parameters on the arsenic removal and the quality of colemanite concentrate were investigated. Results were compared with those obtained with the decrepitation of pure colemanite ores in terms of the decrepitation properties and the B 2 O 3 content.

sample box was removed and weighed immediately to determine the weight loss. Screen analysis was then performed on some samples, followed by chemical analysis. The B 2 O 3 content of colemanite samples was determined by volumetric titration using mannitol, whereas As was analyzed spectrophotometrically and by the Gutzeit method by Etibank Emet Colemanite Works. for accuracy check. Both methods gave almost the same results.

3. Results and discussions The effects of temperature, time, and particle size range on the removal of arsenic from colemanite ores along with environmental aspects are delineated below. 3.1. Effect of temperature Samples in the size range of y4.76 q 3.36 mm were subjected to the heat treatment at temperatures varying

2. Experimental 2.1. Materials Representative colemanite samples were taken from the lump-size tailings y150 mm. stockpiled out of the handsorting operation to the Emet Concentrator in Turkiye. The sample size was reduced to below 4.76 mm through a series of crushers and then screened to several size groups as shown in Table 1. The percent B 2 O 3 and As contents in corresponding size ranges are also given. The analysis shows no definitive trend between the As content and particle size ranges. As seen from the table, the original samples contained 30.7% B 2 O 3 and 0.43% As. The arsenic minerals were mainly those of orpiment As 2 S 3 . and realgar As 2 S 2 . by mineralogical examinations. It should be noted that pure hydrated colemanite and calcined anhydrous colemanite, respectively, assay 50.81% and 65.17% B2 O3. 2.2. Methods Experiments were conducted in a Heraeus muffle furnace. Tests were carried out in a 600-cm3 10 =15 =4 cm. steel box with a lid. The sample box was first brought to the desired temperature; 50 g of sample was immediately placed into the box and then returned to the furnace to start the experiment. At the end of each experiment, the

Fig. 1. Weight loss change with temperature during the decrepitation of pure colemanite and colemanite ore containing high arsenic y4.76q3.36 mm particle size range, 15 min heating time..

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Fig. 2. Variation of percent passing 0.2 mm with time for pure and colemanite ore with high arsenic content y4.76q3.36 mm particle size range..

Fig. 3. Arsenic removal from colemanite ore upon heat treatment vs. temperature 15 min heating time, y4.76q3.36 mm particle size range..

from 3008 to 5508C, for 15 min. Similar to the earlier studies conducted on decrepitation of pure colemanite from the same region w3x, weight loss and the amount of sample passing through a 0.2-mm screen were determined upon heat treatment. The results are shown together in Figs. 1 and 2. The percent weight loss increased with increasing temperature up to 5008C and leveled off above that. Studies conducted earlier indicated that the onset of dehydration of colemanite occurred at 2628C and that of decomposition at 4128C w4x. As seen from Fig. 1, the percent weight loss upon decrepitation of pure colemanite mineral showed similar trend to that obtained with the arsenical colemanite ore. However, higher percent weight losses were observed with arsenical colemanite ores as compared to the pure colemanite. This is probably due to the presence of clay minerals in the colemanite ore which experience a different weight loss pattern on heating. As shown in Fig. 2, marginal differences are observed on the fragmentation behavior of pure and arsenical colemanite upon decrepitation, as measured by the percentage passing through a 0.2-mm screen. This shows that arsenical colemanite ore displays similar fragmentation pattern with that of pure colemanite. Percent weight loss, and % B 2 O 3 and
Table 2 Decrepitation of arsenical colemanite ore at different temperatures Temperature 8C. 300 350 400 450 500 550 Weight loss %. 6.2 14.6 16.5 21.2 30.2 30.0 B2 O3 %. 33.8 37.1 38.0 40.2 45.4 45.3 As %. 0.39 0.25 0.20 0.17 0.026 0.024 As removal %. 20.0 48.2 55.3 71.0 96.1 96.4

As contents together with % As removals at different temperatures are presented in Table 2. While percent weight loss and % B 2 O 3 contents increased with increasing temperature, % As content decreased with increasing temperature. Fig. 3 shows % As removal vs. temperature. Increasing the temperature from 3008 to 5508C resulted in an increase in the % As removal up to 5008C and remained almost constant above that. This is the temperature range where arsenical ores are roasted w9x. Arsenic, sulfur and many of their compounds have significant vapor pressures at the roasting temperatures of arsenical concentrates i.e., 4508 to 6508C.. Table 3 lists vapor pressures of some arsenical compounds of interest w912x. The equilibrium vapor pressures of arsenic and sulfur increase with increasing temperature and become significant under the conditions of 0.01 and 0.1 atm and 5008 and 6008C, usually employed for roasting. Arsenic sulfides, such as realgar As 2 S 2 . and orpiment As 2 S 3 . are not stable above 3078C as evident in Table 3. The arsenic sulfides present in the concentrates or in the vapor phase decompose at higher temperatures to yield elemental arsenic and sulfur vapors which easily
Table 3 Vapor pressure of certain species during roasting of arsenical sulfide concentrates w710x Species in vapor phase
a

Species in condensed phase

Equilibrium vapor pressure mm Hg. 3078C 4078C 14 5.6 1.3 77.3 10.7 5078C bp 5258C sp 6038C 158 248.5

Sulfur Arsenic a Arsenic As 4 S 4

b a b

Sulfur Arsenic Arsenopyrite Realgar Orpiment

5 0.0002 0.0002 0.62

Includes all polymers. Includes arsenic, sulfur and combined sulfides.

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Fig. 4. Phase-stability diagram for AsSO system at 3078C w9x.

Fig. 5. Arsenic removal vs. retention time at 4508C y4.76q3.36 mm particle size range..

oxidize by air w9x. Two oxidation products, As 2 O 3 and SO 2 , leave the roaster as off-gases along with nitrogen and any unused oxygen. Fig. 4, which shows the AsSO phase stability diagram at 3078C, has been drawn based on the thermodynamic data compiled from various sources w1214x. This is a typical temperature for the early stages of roasting. There is a strong driving force to oxidize both sulfur and arsenic to SO 2 and As 2 O 3 , as evident in Fig. 4. A similar phenomenon occurs during the decrepitation of colemanite ores with high arsenic content. Complete fragmentation of pure colemanite is only observed above 5008C and this is in agreement with the optimum arsenic removal temperature found both theoretically and experimentally. 3.2. Effect of retention time Decrepitation experiments using samples in the particle size range of y4.76 q 3.36 were performed at 4508C for 5 to 30 min. Experimental results are shown in Table 4. Increasing the time of heat treatment resulted in an increase in % As removal, as presented in Fig. 5. The % B 2 O 3 content of the colemanite concentrates were also increased with increasing the time of decrepitation. It is to be noted that at 4508C, even 20 min of heating time is not sufficient to reach As removals of 90% and thus, 5008C
Table 4 Results of the decrepitation experiments run at 4508C for different periods Time min. 5 15 20 30 Weight loss %. 1 23 25 26 B2 O3 %. 32.0 41.2 42.3 42.8 As %. 0.45 0.12 0.083 0.043 As removal %. 3.0 80.0 86.5 93.0

appears to be necessary for reaching As removals of over 90% at 15 min decrepitation time. 3.3. Effect of particle size Experiments performed in different particle size ranges are shown in Table 1. The results obtained under optimum conditions of 5008C and 15 min are tabulated in Table 5 and Fig. 6. As seen in Table 5, decreasing the particle size marginally affected the % As removal and % B 2 O 3 content of the colemanite concentrates. The amount of material passing through a 0.2-mm screen upon heat treatment is almost the same. This is in line with our earlier results on pure colemanite, where no dependence of particle size on fragmentation of decrepitated colemanite upon decrepitation was found w3x. 3.4. Enironmental aspects Since arsenic and most of its compounds are toxic, environmental pollution caused by arsenic emissions which leave the roasters should carefully be controlled and miniTable 5 Results of decrepitation tests run with samples of different size ranges 5008C and 15 min heating time. Particle size range mm. y4.76 to q3.36 y3.36 to q2.36 y2.36 to q1.68 y1.68 to q1.00 y1.00 to q0.841 y0.841 to q0.600 y0.600 Wt.% less Weight B 2 O 3 As %. than 0.2 mm loss %. %. 85.7 82.9 82.2 83.2 83.7 83.6 83.8 30.2 28.6 27.0 27.6 26.0 25.8 25.8 45.4 43.3 42.2 42.2 40.3 39.1 41.0 0.026 0.017 0.018 0.018 0.022 0.018 0.025 As removal %. 96.1 96.6 96.5 96.7 95.9 98.1 95.7

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2. This experimental study reveals that most of the arsenic present in the arsenical colemanite ores could be removed during decrepitation. While the decrepitated colemanite concentrate with very low arsenic content is suitable for use in the production of boric acid, the arseniccontaining minerals leave the furnace as As 2 O 3 and SO 2 . Air pollution emitted by this process could be eliminated by the sublimation of the off-gases yielding technical grade As 2 O 3 , sublimation of which is repeated until the desired purity is reached. References
w1x D. Boztepe, Beneficiation of B 2 O 3 by decreasing arsenic content of y3 mm ponds tailing of Emet colemanite concentrator, MS thesis, ITU Mining Faculty, 1988 in Turkish.. w2x M. Kose, S. Ertekin, M. Gunduz, M. Oztoprak, Selective recovery of colemanite and arsenic minerals from boron tailings, Proceedings of XIth Turkish Mining Congress of Turkey, 1989, pp. 407415 in Turkish with English abstract.. w3x M.S. Celik, A. Uzunoglu, F. Arslan, Powder Technol. 79 2. 1994. 167172. w4x M.S. Celik, T. Batar, Y. Akin, F. Arslan, Upgrading schemes for boron minerals through calcination, Miner. Metall. Processing J. 15 1. 1998. 5356. w5x P.R. Smith, R.A. Walters, Mining Eng., Feb. 1980, p. 199. w6x O.F. Emrullahoglu, M. Kara, R. Tolun, M.S. Celik, Powder Tech nol. 77 1993. 215. w7x T.W. Davies, S. Colak, R.M. Hooper, Powder Technol. 65 1991. 433. w8x S. Sener, G. Ozbayoglu, Separation of ulexite from colemanite by calcination, Min. Eng. 6. June 1995. 697704. w9x M.C. Jha, M.J. Kramer, Recovery of gold from arsenical ores, in: V. Kudryk, D.A. Corrigan, W.W. Liang Eds.., Precious Metals: Mining, Extraction, and Processing, TMS of AIME, 1984, pp. 337265. w10x B.A. Strathdel, L.M. Pidgeon, Thermal decomposition of vapor pressure measurements on arsenopyrite and on arsenical ores, Canadian Mining and Metallurgical Bulletin, December 1961, pp. 883 887. w11x R. Hultgren, P.D. Desai, D.T. Hawkins, M. Gleisser, K. Kelly, D.D. Wagman, Selected Values of the Thermodynamic Properties of the Elements, American Society for Metals, Metals Park, OH, 1973. w12x K.C. Mills, Thermodynamic Data for Inorganic Sulfides, Selenides and Tellurides, Butterworth, London, 1974. w13x A.D. Mah, Thermodynamic data for arsenic sulfide reactions, US Bureau of Mines Report of Investigations 8671, 1982. w14x D.R. Stull, H. Prophet, JANAF Thermochemical Tables, 2nd edn., NSRDS-NBS37, National Bureau of Standards, Washington, DC, 1971. w15x J.O. Burckle, G.H. March, R.L. Meek, Arsenic emissions and control-gold roasting operations, Environmental J. 6 1981. 443451. w16x W.H. Lederer, R.J. Fenstenheim Eds.., Arsenic, Van Nostrand-Reinhold, New York, 1983.

Fig. 6. Arsenic removal vs. particle size at 5008C for 15 min.

mized. The atmospheric emission of arsenic consists of As 2 O 3 , both as a particulate matter or as vapor present in equilibrium with air w9x. Therefore, it is important to install not only an efficient condensation system operating at low temperature, about 1008C, but also a particulate collection system. The particulate emissions could be managed by using a hot electrostatic precipitator, an air quench in a mixer-cooler and a cold baghouse either by themselves or in combination w15x. As for the solids, arsenic oxide could be purified and sold to the alloy manufacturing industry and the agricultural chemical industry w16x. Otherwise, the arsenic compounds should be stored in a sealed space.

4. Conclusions 1. Decrepitation tests were conducted on colemanite samples assaying 30.7% B 2 O 3 and 0.43% As. Effects of temperature, retention time, and particle size on the arsenic removal and the B 2 O 3 content of the concentrates were investigated. Arsenic removal was found to be independent of the particle size. Increasing the temperature resulted in an increase in the percent arsenic removal. Decrepitated colemanite concentrate contained 0.026% As which corresponded to the As removal of 96.1% at 5008C and 15 min of heating time. The corresponding B 2 O 3 grade of the concentrate varied in the range of 4045% B 2 O 3 .