عملیات فروشویی زیستی کانسنگ کم عیار کالکوپیریتی در شرایط کلریدی با استفاده از سازگاری میکروارگانیسم های بومی
محورهای موضوعی : زیست فناوری میکروبی
علی بهراد وکیل آباد
1
(استادیار، گروه سرامیک، پژوهشکده مواد، دانشگاه تحصیلات تکمیلی صنعتی و فناوری پیشرفته، کرمان،ایران)
پیمان محمدزاده جهانی
2
(استادیار گروه علوم پایه،
دانشکده پزشکی، دانشگاه علوم پزشکی بم، بم، ایران)
زهرا منافی
3
(کارشناس ارشد، واحد تحقیقات هیدرومتالورژی، مرکز تحقیق و توسعه، مجتمع مس سرچشمه،
شرکت ملی صنایع مس ایران)
کلید واژه: فروشویی زیستی, سازگاری کلریدی میکروب ها, کانسنگ کم عیار کالکوپیریتی, میکروارگانیسم های بومی,
چکیده مقاله :
سابقه و هدف: انحلال کالکوپیریت از مهمترین چالش های هیدرومتالورژی است زیرا به دلیل غیرفعال شدن سطح با رسوبات انفعالی انجام لیچینگ بسیار دشوار است. این پژوهش با هدف استفاده از ترکیب مزایای فروشویی زیستی و فروشویی کلریدی برای افزایش شاخص در بازیابی مس از منابع کم عیار کالکوپیریتی انجام گردید.مواد و روش ها: در این پژوهش، سویه های مختلف میکروارگانیسم های بومی مزوفیل، ترموفیل معتدل و مطلق از معدن سرچشمه جداسازی و به مدت 4 ماه با محیط کشت کلریدی سازگار گردید. سپس، عملیات بیولیچینگ به صورت سیستماتیک در ستون های حاوی کانسنگ کم عیار کالکوپیریتی (کمتر از 3/0 درصد مس) به منظور بررسی تاثیر کلر در فرایند بیولیچینگ اجرا شد. همچنین برای بررسی دقیق مکانیسم و فرایند تولید آنالیزهای دستگاهی جامدهای باقیمانده از لیچینگ و خوراک انجام شد.یافته ها: بر اساس آنالیزهای انجام شده (SEM، EDS، XRD) بر روی جامدات باقیمانده فروشویی زیستی، غلبه بر مشکلات ناشی از رسوبات ناخواسته طی فرایند بیولیچینگ کلریدی (2 گرم بر لیتر کلر) یکی از دلایل اصلی این نتایج تشخیص داده شد. به طوری که افزایش 23 درصدی در بازیابی با استفاده از محیط کلریدی (81 درصد با کلر و 58 درصد بدون کلر) مشاهده گردید. نتیجه گیری: کنترل رسوبات ناخواسته (غنی از آهن و گوگرد) در فرایند فروشویی زیستی کانسنگ کالکوپیریتی کم عیار، مهمترین دلیل بهبود بازیابی مس (بیش از 81 درصد مس در طول 120 روز) بود. این راندمان با تنظیم فرایند رشد و فعالیت میکروارگانیسم ها از مزوفیل ها تا ترموفیل های مطلق همراه با افزودن نمک کلریدسدیم بدست آمد.
Background & Objectives: Dissolution of chalcopyrite is one of the most important challenges of hydrometallurgy because it is difficult to leach due to its inactivation by passive precipitates like jarosites. The combination of the benefits of microbial leaching (native mesophiles, moderate thermophiles, and extreme thermophiles), and chloride leaching was the main purpose to enhance the copper recovery, especially from the low-grade chalcopyrite sources. Materials & Methods: The native microorganisms were isolated from Sarcheshmeh mine, and adapted (4 months with chloride media). Then, the bioleaching operation was systematically performed using the columns containing low chalcopyrite ore (less than 0.3% Cu) to investigate the effect of the chlorine on the bioleaching process. Different analyzes of the leaching and feed residues were used to closely examine the process and mechanisms involved (A 23% increase in recovery (81% with chlorine and 58% with no chlorine)). Results: Based on the analyses of the bio-leaching residues, overcoming the problems caused by the unwanted precipitates like jarosite during chlorinated bioprocess (2 g / l chloride) was one of the main reasons for these results which were identified using SEM, EDS analysis. And, the elemental mapping of the solid residues from microbial leaching operations proved this possible reason. Conclusion: Controlling the undesirable precipitates in the process was the most important lever to improve copper recovery (more than 81% of copper over 120 days). This was achieved by regulating the growth process and activity of microorganisms from mesophiles to extreme thermophiles with sodium chloride salt additive.
(4): 315-328.
2. Davis-Belmar C, Cautivo D, Demergasso C, Rautenbach G. Bioleaching of copper secondary sulfide ore
in the presence of chloride by means of inoculation with chloride-tolerant microbial culture. Hydrometallurgy. 2014; 150: 308-312.
3. Gao X, Yang Y, Pownceby MI, Zhong S, Chen M. A sulfur K-Edge XANES and raman study on the
effect of chloride ion on bacterial and chemical leaching of chalcopyrite at 25° C. Mining, Metallurgy
Explor. 2019; 36(2): 343-352.
4. Vakylabad AB, Schaffie M, Naseri A, Ranjbar M, Manafi Z. Optimization of staged bioleaching of lowgrade chalcopyrite ore in the presence and absence of chloride in the irrigating lixiviant: ANFIS simulation. Bioprocess Biosystems Engin. 2016; 39(7): 1081-1104.
5. Velásquez-Yévenes L, Torres D, Toro N. Leaching of chalcopyrite ore agglomerated with high chloride
concentration and high curing periods. Hydrometallurgy. 2018; 181: 215-220.
6. Zhao H, Zhang Y, Zhang X, Qian L, Sun M, Yang Y. The dissolution and passivation mechanism of
chalcopyrite in bioleaching: An overview. Minerals Engin. 2019; 136: 140-154.
7. Darezereshki E, Darban AK, Abdollahy M, Jamshidi-Zanjani A, Vakylabad AB, Mohammadnejad S.
The leachability study of iron-oxides from mine tailings in a hybrid of sulfate-chloride lixiviant. J
Environ Chem Eng. 2018; 6(4): 5167-5176.
8. Hernández PC, Dupont J, Herreros OO, Jimenez YP, Torres CM. Accelerating copper leaching from
sulfide ores in acid-nitrate-chloride media using agglomeration and curing as pretreatment. Minerals.
2019; 9(4): 250.
9. Castillo J, Sepúlveda R, Araya G, Guzmán D, Toro N, Pérez K. Leaching of white metal in a NaClH2SO4 system under environmental conditions. Minerals. 2019; 9(5): 319.
10. Hidalgo T, Kuhar L, Beinlich A, Putnis A. Kinetics and mineralogical analysis of copper dissolution
from a bornite/chalcopyrite composite sample in ferric-chloride and methanesulfonic-acid solutions.
Hydrometallurgy. 2019.
11. Khaleque HN, Kaksonen AH, Boxall NJ, Watkin EL. Chloride ion tolerance and pyrite bioleaching
capabilities of pure and mixed halotolerant, acidophilic iron-and sulfur-oxidizing cultures. Minerals
Engineering. 2018; 120: 87-93.
12. Martins FL, Patto GB, Leão VA. Chalcopyrite bioleaching in the presence of high chloride
concentrations. J Chem Technol Biotechnol. 2019.
13. Vakylabad AB, Schaffie M, Naseri A, Ranjbar M, Manafi Z. A procedure for processing of pregnant
leach solution (PLS) produced from a chalcopyrite-ore bio-heap: CuO Nano-powder fabrication.
Hydrometallurgy. 2016; 163: 24-32.
14. Robertson S, van Staden P, Seyedbagheri A. Advances in high-temperature heap leaching of
refractory copper sulphide ores. J South Afr Institute Mining Metallurgy. 2012; 112(12): 1045-1050.
15. Watling H. The bioleaching of sulphide minerals with emphasis on copper sulphides—a review.
Hydrometallurgy. 2006; 84(1-2): 81-108.
16. Vilcáez J, Inoue C. Mathematical modeling of thermophilic bioleaching of chalcopyrite. Minerals
Eng. 2009; 22(11): 951-960.
17. Dopson M, Lövgren L, Boström D. Silicate mineral dissolution in the presence of acidophilic
microorganisms: implications for heap bioleaching. Hydrometallurgy. 2009; 96(4): 288-293.
18. Senanayake G. A review of chloride assisted copper sulfide leaching by oxygenated sulfuric acid and
mechanistic considerations. Hydrometallurgy. 2009; 98(1-2): 21-32.
19. Vakylabad AB, Schaffie M, Ranjbar M, Manafi Z, Darezereshki E. Bio-processing of copper from
combined smelter dust and flotation concentrate: A comparative study on the stirred tank and airlift
reactors. J Hazardous Materials. 2012; 241: 197-206.
20. Vakylabad AB, Ranjbar M, Manafi Z, Bakhtiari F. Tank bioleaching of copper from combined
flotation concentrate and smelter dust. Int Biodeterior Biodegrad. 2011; 65(8): 1208-1214.
21. Vakylabad AB. A comparison of bioleaching ability of mesophilic and moderately thermophilic
culture on copper bioleaching from flotation concentrate and smelter dust. Int J of Mineral
Processing. 2011; 101(1-4): 94-99.
22. Pakostova E, Grail BM, Johnson DB, editors. Column bioleaching of a saline, calcareous copper
sulfide ore. Solid State Phenomena; 2017.
23. Hawkes RB, Franzmann PD, O’hara G, Plumb JJ. Ferroplasma cupricumulans sp. nov., a novel
moderately thermophilic, acidophilic archaeon isolated from an industrial-scale chalcocite bioleach
heap. Extremophiles. 2006; 10(6): 525-530.
24. Leahy M, Davidson M, Schwarz M. A model for heap bioleaching of chalcocite with heat balance:
mesophiles and moderate thermophiles. Hydrometallurgy. 2007; 85(1): 24-41.
25. Petersen J, Dixon DG. Principles, mechanisms and dynamics of chalcocite heap bioleaching.
Microbial processing of metal sulfides: Springer; 2007. p. 193-218.
26. Xingyu L, Biao W, Bowei C, Jiankang W, Renman R, Guocheng Y. Bioleaching of chalcocite
started at different pH: Response of the microbial community to environmental stress and leaching
kinetics. Hydrometallurgy. 2010; 103(1-4): 1-6.
27. Hawkes RB, Franzmann PD, Plumb JJ. Moderate thermophiles including “Ferroplasma
cupricumulans” sp. nov. dominate an industrial-scale chalcocite heap bioleaching operation.
Hydrometallurgy. 2006; 83(1-4): 229-236.
28. Bobadilla-Fazzini RA, Pérez A, Gautier V, Jordan H, Parada P. Primary copper sulfides bioleaching
vs. chloride leaching: Advantages and drawbacks. Hydrometallurgy. 2017; 168: 26-31.
29. Lu Z, Jeffrey M, Lawson F. The effect of chloride ions on the dissolution of chalcopyrite in acidic
solutions. Hydrometallurgy. 2000; 56(2): 189-202.
30. Lu Z, Jeffrey M, Lawson F. An electrochemical study of the effect of chloride ions on the dissolution
of chalcopyrite in acidic solutions. Hydrometallurgy. 2000; 56(2): 145-155.
31. Dutrizac J. Elemental sulphur formation during the ferric chloride leaching of chalcopyrite.
Hydrometallurgy. 1990; 23(2-3): 153-176.
32. Tao H, Dongwei L. Presentation on mechanisms and applications of chalcopyrite and pyrite
bioleaching in biohydrometallurgy – a presentation. Biotechnol Report. 2014; 4: 107-119.
33. Akcil A, Ciftci H, Deveci H. Role and contribution of pure and mixed cultures of mesophiles in
bioleaching of a pyritic chalcopyrite concentrate. Minerals Eng. 2007; 20(3): 310-318.
34. Tao H, Dongwei L. Presentation on mechanisms and applications of chalcopyrite and pyrite
bioleaching in biohydrometallurgy–a presentation. Biotechnol Report. 2014; 4: 107-119.
35. Rawlings D, Tributsch H, Hansford G. Reasons why'Leptospirillum'-like species rather than
Thiobacillus ferrooxidans are the dominant iron-oxidizing bacteria in many commercial processes for
the biooxidation of pyrite and related ores. Microbiol Reading. 1999; 145(1): 5-14.
36. Petersen J, Dixon D. Thermophilic heap leaching of a chalcopyrite concentrate. Minerals Eng. 2002;
15(11): 777-785.
_||_
(4): 315-328.
2. Davis-Belmar C, Cautivo D, Demergasso C, Rautenbach G. Bioleaching of copper secondary sulfide ore
in the presence of chloride by means of inoculation with chloride-tolerant microbial culture. Hydrometallurgy. 2014; 150: 308-312.
3. Gao X, Yang Y, Pownceby MI, Zhong S, Chen M. A sulfur K-Edge XANES and raman study on the
effect of chloride ion on bacterial and chemical leaching of chalcopyrite at 25° C. Mining, Metallurgy
Explor. 2019; 36(2): 343-352.
4. Vakylabad AB, Schaffie M, Naseri A, Ranjbar M, Manafi Z. Optimization of staged bioleaching of lowgrade chalcopyrite ore in the presence and absence of chloride in the irrigating lixiviant: ANFIS simulation. Bioprocess Biosystems Engin. 2016; 39(7): 1081-1104.
5. Velásquez-Yévenes L, Torres D, Toro N. Leaching of chalcopyrite ore agglomerated with high chloride
concentration and high curing periods. Hydrometallurgy. 2018; 181: 215-220.
6. Zhao H, Zhang Y, Zhang X, Qian L, Sun M, Yang Y. The dissolution and passivation mechanism of
chalcopyrite in bioleaching: An overview. Minerals Engin. 2019; 136: 140-154.
7. Darezereshki E, Darban AK, Abdollahy M, Jamshidi-Zanjani A, Vakylabad AB, Mohammadnejad S.
The leachability study of iron-oxides from mine tailings in a hybrid of sulfate-chloride lixiviant. J
Environ Chem Eng. 2018; 6(4): 5167-5176.
8. Hernández PC, Dupont J, Herreros OO, Jimenez YP, Torres CM. Accelerating copper leaching from
sulfide ores in acid-nitrate-chloride media using agglomeration and curing as pretreatment. Minerals.
2019; 9(4): 250.
9. Castillo J, Sepúlveda R, Araya G, Guzmán D, Toro N, Pérez K. Leaching of white metal in a NaClH2SO4 system under environmental conditions. Minerals. 2019; 9(5): 319.
10. Hidalgo T, Kuhar L, Beinlich A, Putnis A. Kinetics and mineralogical analysis of copper dissolution
from a bornite/chalcopyrite composite sample in ferric-chloride and methanesulfonic-acid solutions.
Hydrometallurgy. 2019.
11. Khaleque HN, Kaksonen AH, Boxall NJ, Watkin EL. Chloride ion tolerance and pyrite bioleaching
capabilities of pure and mixed halotolerant, acidophilic iron-and sulfur-oxidizing cultures. Minerals
Engineering. 2018; 120: 87-93.
12. Martins FL, Patto GB, Leão VA. Chalcopyrite bioleaching in the presence of high chloride
concentrations. J Chem Technol Biotechnol. 2019.
13. Vakylabad AB, Schaffie M, Naseri A, Ranjbar M, Manafi Z. A procedure for processing of pregnant
leach solution (PLS) produced from a chalcopyrite-ore bio-heap: CuO Nano-powder fabrication.
Hydrometallurgy. 2016; 163: 24-32.
14. Robertson S, van Staden P, Seyedbagheri A. Advances in high-temperature heap leaching of
refractory copper sulphide ores. J South Afr Institute Mining Metallurgy. 2012; 112(12): 1045-1050.
15. Watling H. The bioleaching of sulphide minerals with emphasis on copper sulphides—a review.
Hydrometallurgy. 2006; 84(1-2): 81-108.
16. Vilcáez J, Inoue C. Mathematical modeling of thermophilic bioleaching of chalcopyrite. Minerals
Eng. 2009; 22(11): 951-960.
17. Dopson M, Lövgren L, Boström D. Silicate mineral dissolution in the presence of acidophilic
microorganisms: implications for heap bioleaching. Hydrometallurgy. 2009; 96(4): 288-293.
18. Senanayake G. A review of chloride assisted copper sulfide leaching by oxygenated sulfuric acid and
mechanistic considerations. Hydrometallurgy. 2009; 98(1-2): 21-32.
19. Vakylabad AB, Schaffie M, Ranjbar M, Manafi Z, Darezereshki E. Bio-processing of copper from
combined smelter dust and flotation concentrate: A comparative study on the stirred tank and airlift
reactors. J Hazardous Materials. 2012; 241: 197-206.
20. Vakylabad AB, Ranjbar M, Manafi Z, Bakhtiari F. Tank bioleaching of copper from combined
flotation concentrate and smelter dust. Int Biodeterior Biodegrad. 2011; 65(8): 1208-1214.
21. Vakylabad AB. A comparison of bioleaching ability of mesophilic and moderately thermophilic
culture on copper bioleaching from flotation concentrate and smelter dust. Int J of Mineral
Processing. 2011; 101(1-4): 94-99.
22. Pakostova E, Grail BM, Johnson DB, editors. Column bioleaching of a saline, calcareous copper
sulfide ore. Solid State Phenomena; 2017.
23. Hawkes RB, Franzmann PD, O’hara G, Plumb JJ. Ferroplasma cupricumulans sp. nov., a novel
moderately thermophilic, acidophilic archaeon isolated from an industrial-scale chalcocite bioleach
heap. Extremophiles. 2006; 10(6): 525-530.
24. Leahy M, Davidson M, Schwarz M. A model for heap bioleaching of chalcocite with heat balance:
mesophiles and moderate thermophiles. Hydrometallurgy. 2007; 85(1): 24-41.
25. Petersen J, Dixon DG. Principles, mechanisms and dynamics of chalcocite heap bioleaching.
Microbial processing of metal sulfides: Springer; 2007. p. 193-218.
26. Xingyu L, Biao W, Bowei C, Jiankang W, Renman R, Guocheng Y. Bioleaching of chalcocite
started at different pH: Response of the microbial community to environmental stress and leaching
kinetics. Hydrometallurgy. 2010; 103(1-4): 1-6.
27. Hawkes RB, Franzmann PD, Plumb JJ. Moderate thermophiles including “Ferroplasma
cupricumulans” sp. nov. dominate an industrial-scale chalcocite heap bioleaching operation.
Hydrometallurgy. 2006; 83(1-4): 229-236.
28. Bobadilla-Fazzini RA, Pérez A, Gautier V, Jordan H, Parada P. Primary copper sulfides bioleaching
vs. chloride leaching: Advantages and drawbacks. Hydrometallurgy. 2017; 168: 26-31.
29. Lu Z, Jeffrey M, Lawson F. The effect of chloride ions on the dissolution of chalcopyrite in acidic
solutions. Hydrometallurgy. 2000; 56(2): 189-202.
30. Lu Z, Jeffrey M, Lawson F. An electrochemical study of the effect of chloride ions on the dissolution
of chalcopyrite in acidic solutions. Hydrometallurgy. 2000; 56(2): 145-155.
31. Dutrizac J. Elemental sulphur formation during the ferric chloride leaching of chalcopyrite.
Hydrometallurgy. 1990; 23(2-3): 153-176.
32. Tao H, Dongwei L. Presentation on mechanisms and applications of chalcopyrite and pyrite
bioleaching in biohydrometallurgy – a presentation. Biotechnol Report. 2014; 4: 107-119.
33. Akcil A, Ciftci H, Deveci H. Role and contribution of pure and mixed cultures of mesophiles in
bioleaching of a pyritic chalcopyrite concentrate. Minerals Eng. 2007; 20(3): 310-318.
34. Tao H, Dongwei L. Presentation on mechanisms and applications of chalcopyrite and pyrite
bioleaching in biohydrometallurgy–a presentation. Biotechnol Report. 2014; 4: 107-119.
35. Rawlings D, Tributsch H, Hansford G. Reasons why'Leptospirillum'-like species rather than
Thiobacillus ferrooxidans are the dominant iron-oxidizing bacteria in many commercial processes for
the biooxidation of pyrite and related ores. Microbiol Reading. 1999; 145(1): 5-14.
36. Petersen J, Dixon D. Thermophilic heap leaching of a chalcopyrite concentrate. Minerals Eng. 2002;
15(11): 777-785.
