The - Treatment - of - Arsenic - Bearing - Ores Alkaline PDF
The - Treatment - of - Arsenic - Bearing - Ores Alkaline PDF
The - Treatment - of - Arsenic - Bearing - Ores Alkaline PDF
(1)
(2)
(3)
(4)
Dissolution of elemental sulfur in sodium hydroxide is also used as a lixiviant for alkaline
sulfide leaching of arsenic. The combination of sodium hydroxide and elemental sulfur
results in the formation of species other than just sulfide (S-2). Both sodium polysulfide
(Na2SX) and sodium thiosulfate (Na2S2O3) are created along with sulfide. Figure 1
illustrates the equilibrium diagram for sulfur while Figure 2 illustrates the more
commonly encountered meta stable sulfur diagram.
The generation of these predominant meta stable species is illustrated simplistically in the
following scenario.
4So + 6NaOH 2Na2S + Na2S2O3 + 3H2O
(5)
(6)
Due to the oxidizing power of polysulfide on sodium thioantimonite, the major species in
solution is normally sodium thioarsenate (Na3AsS4). This can be viewed as follows:
Na2SX + (X-1)Na3AsS3 (X-1)Na3AsS4 + Na2S
(7)
(8)
Figure 3. Equilibrium Species Eh-pH Diagram for Sulfur and Alkaline Sulfide Gold
Currently, studies are underway on the actual kinetics and mechanism of the alkaline
sulfide system (64,65,66). A rotating electrochemical quartz crystal microbalance
(REQCM) is being utilized to study the system.
Gold leached by the alkaline sulfide system is readily recoverable by several means
including electrowinning, gaseous precipitation, chemical precipitation, cementation,
solvent extraction and ion exchange. Conventional methods of gold recovery such as
zinc or aluminum cementation are not applicable to this type of solution because of the
dangers associated with stibine or arsine gas generation. As well, the conventional
method of direct collection of gold by activated carbon does not work in these solutions
as it does for gold cyanide solutions.
A novel gold recovery practice(11) has been adopted to quantitatively and selectively
recover gold from complex alkaline sulfide solutions containing a mixture of metals such
as arsenic, tin, mercury and antimony. This is illustrated by selectively removing gold
from an alkaline sulfide leach solution containing these impurities. The assay of the
solution tested is shown in Table IV, and the assays of the final products is shown in table
V. The overall results are presented in Table VI.
Table IV. Alkaline Sulfide Leach Head Solution Assay
Volume L
0.5
Au
88.7 ppm
Sb
21.0 g/L
As
5.31 g/L
Hg
274 ppm
Sn
1.84 g/L
Au
14.4 ppm
Sb
21.1 g/L
As
5.21 g/L
Hg
274 ppm
Sn
1.89 g/L
Gold
Antimony
Arsenic
Tin
Mercury
Liquid
16.5%
100.0%
100.0%
100.0%
100.0%
Solid
83.5%
0.0%
0.0%
0.0%
0.0%
Further stages of gold recovery treatment on this solution indicate that almost 100% of
the gold can be selectively recovered from the mercury, arsenic, tin and antimony in the
solution. In addition, the substrate solids which have been employed to load the gold
consist of several cheap and readily available materials and direct processing of the
material is probably the cheapest and most effective method of refining the gold.
Also the waste alkaline sulfide solutions can be recycled for further gold leaching or
further processed with low temperature oxidation to sodium sulfate, Na2SO4. This also
oxidizes the arsenic to soluble sodium arsenate which can then be precipitated by
conventional means using iron compounds. This oxidation process has been practiced in
industry (69). The resultant sodium sulfate, after arsenic removal, is further treated by
purification and crystallization to produce high grade, marketable sodium sulfate. This
process is illustrated simplistically in the following scenario.
2 O2 + Na2S Na2SO4
(9)
(10)
(11)
(12)
Na3AsS4 + 2 O2
Na3AsO4
(13)
This versatile and environmentally benign chemical is then be sold to and utilized in
industries such as pulp and paper, glass, ceramics, detergents, textile dyes, mineral feed
supplements, bleach and photography. As such, there is no environmental or
toxicological issue in the use of alkaline sulfide gold recovery as the waste products
become value added, marketable by-products.
As well the sodium sulfate produced can be used to regenerate the sodium hydroxide
needed in the process in a manner analogous to industrial dual alkali scrubbing systems
(70). This is as follows:
2Na2SO4 + Ca(OH)2 CaSO4 + 2NaOH
(14)
The clean gypsum product can then be marketed and used in such applications as
agricultural soil amendments or as an additive in primary cement manufacture. In
addition, initial efforts are underway and have been successful in regenerating the
necessary H2SO4 and NaOH reagents from the Na2SO4 by-product. The details of this
process will be given in future publications and may be illustrated as follows:
Na2SO4 + 2H2O H2SO4 + 2NaOH
(15)
Pb,%
46.0
Pb,%
0.0
Sb,%
95.0
As,%
99.0
Zn,%
0.0
In this case, a high grade, 38% copper , concentrate with minimal arsenic was produced
for treatment by smelting. The gold in solution was recovered with the technology
portrayed earlier in the paper and the arsenic was precipitated and stabilized with iron
after oxidation of the alkaline waste solutions.
Summary
From the cited examples in the paper, which utilized fundamental principles of alkaline
sulfide hydrometallurgy as well as its industrially proven applications for the selective
arsenic removal, it is obvious that arsenic bearing ores, concentrates and materials can be
effectively treated.
References
1.
Anderson, C. G., Nordwick, S. M., and Krys, L.E., "Processing of Antimony at the
Sunshine Mine", Residues and Effluents - Processing and Environmental Considerations,
ed. R.G. Reddy, W. P. Imrie, P.B. Queneau (San Diego, CA: AIME-TMS, 1992), 349366.
2.
Anderson, C. G. and Krys, L. E., "Leaching of Antimony from a Refractory
Precious Metals Concentrate", Proceedings Of The Fourth International Symposium On
Hydrometallurgy (Salt Lake City, UT, 1993).
3.
Nordwick, S. M. and Anderson, C. G., "Advances In Antimony Electrowinning At
The Sunshine Mine", Proceedings Of The Fourth International Symposium On
Hydrometallurgy, (Salt Lake City, UT, 1993).
4.
Anderson, C. G., et. al., Antimony Separation Process", U.S. Patent No. 5,290,338,
March 1, 1994.
5.
6.
7.
M. Jeffrey, and C.G. Anderson, A Fundamental Study of the Alkaline Sulfide
Leaching of Gold, The European Journal of Mineral Processing and Environmental
Protection, October 2002.
8. C.G. Anderson, The Chemical Analysis of Industrial Alkaline Sulfide
Hydrometallurgical Processes, The Society of Mineral Analysts and the Canadian
Mineral Analysts Annual Meeting, Spokane, Washington, April 2002.
9. C.G. Anderson, Industrial Nitrogen Species Catalyzed Pressure Leaching and
Alkaline Sulfide Gold Recovery from Refractory Gold Concentrates, Precious Metals
2001, 25th Annual IPMI Meeting, Tucson, Arizona, June 2001.
10. C. R. Edwards, 1985 Engineering the Equity Concentrate Leach Process, In:
Complex Sulfides: Processing of Ores, Concentrates and By-Products, A.D Zunkel, et al,
eds. Proceedings of a symposium sponsored by the Metallurgical Society of AIME and
the CIMM, TMS-AIME Fall Extractive Meeting, San Diego CA, Nov. 10-13 1985, p.
197-219.
11. R.R Lunt, D.K. Modrow and G.K. Roset, Adaption of Dilute Mold Lime Dual
Alkali Scrubbing at Stillwater Mining Companys PGM Smelter, Hydrometallurgy
2003, Vancouver, B.C. October 2003.
12. Nadkarni, R.M., and Kusik, C.L., Hydrometallurgical Removal of Arsenic from
Copper Concentrates Arsenic Metallurgy Fundamentals and Applications, Edited by
R.G. Reddy, J.L. Hendrix and P.B. Queneau, Phoenix, Arizona, 1988.
13. H. Glazkov and A. L. Tseft, "Solubility of Sulfide Minerals of antimony and arsenic
in metal salts at elevated pressure", Sb. Nauch Tr. Irkutsk. Gos. Nauch-Issled. lnst._Redk.
Met^l, 9 (1961), 2Q4-B.
14. E. I. Agladze, et al., "Production of arsenic tcisulfide", Tr. Inst. Prikl. Khiro. i
Electrokliini,_Akad. Nauk_Gruz. SSg.l (1959) 125-30.
15. P. U. van Stein, "Selective Separation of Antimony from Concentrates", German Offen.
No. 2,020,656 (25 Feb. 1971).
16. W. C. Holmes, "How electrolytic antimony is made at Sunshine Plant", Ens. Mining J.
145 (3) (1944), 54-8.
17. W. C. Holmes, "Electrolytic recovery of antimony from Letrahedrite concentrates", U.
S. Patent. No. 2,331,375 (12 Oct. 1944).
18. G. F. Gnatyshenko and T. R. Polyvyanni, "Arsenic leaching from Cottrell dusts by
sodium sulfide", lav. Ahad. Naub. Kaz. SSR. Ser. Met. Qboaashch. Ogneuporov.. 3 (1961),
35-9.
19. J. Kaloc, et al., "Alkaline leaching of tetrahedrite concentrates", Hutn. Listy. Z2 (9)
(1967). 626-9.
20. I. R. Polyvyanni, et al., "Leaching arsenic from arsenic-containing dust by means of
sodium sulfide", Tr. Jlnst. Met- Oboeashck. Akad. Mauk Kaz. SSR, 6 (1963) 77-90.
21. R. M. Nadkarni, C. L. Kusik and H. P. Heissner, "Method of removing arsenic and
antimony from Copper Ore Concentrate", U. S. Patent 3, 911,073, Oct. 7, 1975.