德兴铜矿低品位硫化铜矿细菌浸出工艺及技术研究
摘要
我国铜矿资源以贫铜为主，大型铜矿少，500万吨铜储量的矿山只有江西德兴铜矿和西藏玉龙铜矿；目前占储量2／3以上的条件较好的铜矿山已经开采，就地质资料而言，我国还有2000万吨铜金属储量的矿山尚未开采。而我国一直是铜消耗大国，自产矿山铜精矿仅占铜消耗总量的40％左右，因此非常有必要对我国的低品位铜矿资源进行加工利用，解决我国铜工业存在的供需矛盾。
江西铜业公司德兴铜矿在露采过程中，需要剥离堆存含铜0.1-0.25％的废矿石，仅铜厂矿区就有3.26亿吨，含铜金属约57万吨，用传统的选矿-冶炼方法难以经济和有效的回收；而采用细菌浸出—萃取—电积湿法提铜工艺，则可以回收其中的20％以上，相当于我国一个中型的铜矿山。本论文依靠国家九五科技攻关项目“德兴低品位硫化铜矿细菌浸出提铜工业化试验研究”重点研究内容，结合江西铜业公司德兴铜矿细菌浸出—萃取—电积湿法提铜工厂的生产实践，针对德兴铜矿低品位铜矿石中黄铜矿占80％以上的特点，系统研究了德兴铜矿低品位铜矿细菌浸出的工业化试验、大面积高深度矿石堆浸方法的优化、大容量高效率萃取—电积设备的研制等方面的工作；开展了浸矿细菌育种的基础研究和工业化应用，通过一系列研究后，对德兴铜矿细菌浸出—萃取—电积提铜工艺进行了优化，加快了细菌浸铜速率，提高整个工艺流程的效率。
In order to enhance bacterial leaching of low grade copper ores, theoretical and application studies on copper bioleaching have been systematically carried out. And stain improvement has been engaged to optimize the technological process of bacterial dump leaching-solvent extraction-eletronwinning at Dexing Copper Mine in Jiangxi Province.
Bacterial oxidation of chalcopyrite is speeded up by FeS2, Ag and Ag2S. The dissolution of copper from the ores mainly bearing chalcopyrite is strongly accelerated by some silver-containing ore materials, while that of iron is slightly inhibited. Improved strains by conventional adaption and mutation have been applied in the industrial operation of a bacterial dump leaching-solvent extraction-electronwinning at Dexing Copper Mine so as to accelerate the bacterial leaching of copper from the ores in an attempt of promoting the efficiency of the whole technological process.
江西铜业公司德兴铜矿在露采过程中，需要剥离堆存含铜0.1-0.25％的废矿石，仅铜厂矿区就有3.26亿吨，含铜金属约57万吨，用传统的选矿-冶炼方法难以经济和有效的回收；而采用细菌浸出—萃取—电积湿法提铜工艺，则可以回收其中的20％以上，相当于我国一个中型的铜矿山。本论文依靠国家九五科技攻关项目“德兴低品位硫化铜矿细菌浸出提铜工业化试验研究”重点研究内容，结合江西铜业公司德兴铜矿细菌浸出—萃取—电积湿法提铜工厂的生产实践，针对德兴铜矿低品位铜矿石中黄铜矿占80％以上的特点，系统研究了德兴铜矿低品位铜矿细菌浸出的工业化试验、大面积高深度矿石堆浸方法的优化、大容量高效率萃取—电积设备的研制等方面的工作；开展了浸矿细菌育种的基础研究和工业化应用，通过一系列研究后，对德兴铜矿细菌浸出—萃取—电积提铜工艺进行了优化，加快了细菌浸铜速率，提高整个工艺流程的效率。
In order to enhance bacterial leaching of low grade copper ores, theoretical and application studies on copper bioleaching have been systematically carried out. And stain improvement has been engaged to optimize the technological process of bacterial dump leaching-solvent extraction-eletronwinning at Dexing Copper Mine in Jiangxi Province.
Bacterial oxidation of chalcopyrite is speeded up by FeS2, Ag and Ag2S. The dissolution of copper from the ores mainly bearing chalcopyrite is strongly accelerated by some silver-containing ore materials, while that of iron is slightly inhibited. Improved strains by conventional adaption and mutation have been applied in the industrial operation of a bacterial dump leaching-solvent extraction-electronwinning at Dexing Copper Mine so as to accelerate the bacterial leaching of copper from the ores in an attempt of promoting the efficiency of the whole technological process.
引文
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2．武汉大学、复旦大学生物系微生物教研室．微生物学(第二版)，北京：高等教育出版社，1987
3. G R Postgate. The sulfate-reducing bacterial, Cambrige Univ. Press, Cambridge, 1984
4. A R Colmer and M E Hinkle. Science, 1947, 106:253-256
5. S R Hutchins and M S Davidson. Ann. Rev. Microbiol., 1986,40:311-336
6. N A Kinsel. J. Bacteriol., 1960,80:628-632
7. A P Jr. Harrison. Ann. Rev. Microbiol., 1984,38:265-292
8. G J W Arkesteyn and J AM. De. Bont. Can. J. Microbiol., 1980,26:1057-1065
9. J A Brierley. App. Environ. Microbiol., 1978,36:523-525
10．浸矿技术编委会编．浸矿技术，北京：原子能出版社，1994
11. W E Razzell and P C Trussell. J. Bacteriol., 1963,85:595-603
12. W Rudolfs and A Helbronner. Soil Science, 1922,14:459-464
13. M E C Barros. Appl. Environ. Microbiolo., 1984,47:593-595
14. E Drobner and H Huber. Appl. Environ. Microbiolo., 1990,56:2922-2923
15. R Guay and M Silver. Can. J. Microbiol., 1975,21:281-288
16. H Huber. Arch. Microbiol., 1989,151:479-485
17. S Lutters and H H Hanert, Arch. Microbiol., 1989,151:245-251
18. M E Mackintosh. J. Gen. Microbiol., 1978,105:215-218
19. J T Pronk and J C de Bruyn. Appl. Environ. Microbiol., 1992,58:2227-2230
20. T Sugio and W Mizunashi. J. Bacteriol., 1987,169:4916-4922
21. J G Cobley and J C Cox. Microbiol. Rev. Dec., 1983,47(4):579-595
22. P L Wichlace and R F Unz. Appl. Environ. Microbiol., 1991,57:138-145
23. O H Tuovinen. Geomicrobiol. J., 1993,10:207-217
24. T M Bhatti and J M Bigham. Appl. Environ. Microbiol., 1993,59:1984-1990
25. R G L McCready and W D Gould. Microbial Mineral Recovery, New York, 1990:107-126
26. C L Brierley. Bacterial Leaching, Crit. Rev. Microbiol., 1978,6:207-262
27. S C Lorbach and J M Shively. Geomicrobiol. J., 1993,10:219-226
28. L B Sukla. Hydrometallurgy, 1995,37:387-391
29. S S Bang and K N Narayana. Hydrometallurgy, 1995,37:181-192
30. Y A Attia and M Elzeky. Hydrometallurgy, 1989,22:291-230
31. R Y Wan and J D Miller. Metall. Trans., 1985,16B:575-588
32. V K Berry and L E Murr. Scanning Electron Microscopy, 1977,1:137-146
33. A M Nielsen and J V Beck. Science, 1972,175:1124-1127
34. H Sakaguchi and A E Torma. Appl. Envion. Microbiol., 1976,31:7-16
35. O H Tuovinen and D P Kelly. Arch. Microbiol., 1974,98:167-181
36. D W Duncan and C C Walden. Dev. Ind. Microbiol., 1972,13:66-74
37. M P Silverman. J. Bacteriol., 1963, 10:1046-1051
38. L E Murr and V K Berry. Hydrometallury, 1976,2:11-24
39. N C Trivedi and H M Tsuchiya. Int. J. Mineral Process., 1975,2:1-11
40．北京矿冶总院编译．细菌在采矿工程中的应用，北京：冶金工业出版社，1972
41. A D Agate. World J. Microbiol., 1996,12:487-495
42. K K Dwivedy and A K Mathur. Hydrometallury, 1995,38:99-109
43．孙春宝，魏德洲。国外金属矿选矿，1996，3：35-42
44．T G Carnahan．黄金提取技术，北京：北京大学出版社，1991
45．陈驹声．微生物工程，北京：化学工业出版社，1994
46．汤树德等．微生物学通报，1983，10(5)：201-204
47．胡岳华，康自珍等．国外金属矿选矿，1997，8：42-45
48．康自珍等．黄铜矿细菌氧化机理初步研究，中南工业大学硕士论文，1997
49. G I Karavaiko and G Rossi. Biogeotechnology of Metals, Center for International Projects GKNT, Moscow, 1988
50. L E Murr. Minerals Science Engineering, 1980,12(3):121-189
51. J V Beck. Biotechnology Bioengineering, 1967,9:487-501
52. L Ahonnen and P Hiltunen. In: Fundamental and Applied Biohydrometallurgy, Elsevier, Amsterdam, 1986:13-20
53. A Basaran and O H Tuovinen, Coal Prep., 1987,5:39-55
54. M Tszos and B Volesky. Biotechnol. Bioeng.,m 1982,24:955-969
55. R W Smith. Mineral Process. Extract. Metall. Rev., 1989,4:277-299
56. F Kargl and J G Welssman. Biotechnol. Bioeng., 1984,26:604-612
57. J A Solari and G Huerta. Colloids and Surfaces, 1992, 69:159-166
58. B K Chakrabarti and P C Banerjee. Can. J. Microbiol., 1991,37:692-696
59. D L Jones and E Petters. In: Extractive Metallurgy of Copper(Vol. 2), J C Yannapulos(eds.), Metallurgy Soc. AIME, New York, 1976:633-653
60. J D Sullivan. Trans. AIME, 1942,106:515-546
61. S Venkatachalam. Mineral Engineering, 1991,4:1115-1126
62. F Habashi. Chalcopyrite:its chemistry and metallurgy, McGraw-Hill Book Co., New York, 1978
63．沈同，王镜岩等．生物化学，北京：高等教育出版社，1991
64. A Bruynesteyn and R Hackl. In: Bacterial Leaching Metals from Ores on Intern. Seminar on Dump and Inderground, G I Karavaiko (eds.), Center For Environment Projection, Moscow, 1990:10-20
65. A P Methta and L E Murr. Biotechnol. Bioeng., 1982,14:919-940
66. V K Berry and L E Murr. Hydrometallurgy, 1978, 3:309-326
67．G Milazzo and M Blank，肖科译．生物电化学：生物氧化还原反应，天津：天津科学技术出版社，1990
68. V P Skulachev. Curr. Top. Bioeng., 1971, 4:127-151
69．李缉熙，牛中奇．生物电磁学概论，西安：西安电子科技大学出版社，1990
70. S B Yunker and J M Radovich. Biorechnol. Bioeng., 1986,28:1867-1875
71. N A Kinsel and W W Umbreit. J. Bacteriol., 1964,87:1243-1246
72. J T Pronk. Geomicrobiol. J., 1993,10:153-171
73. B A Blaycock and A Nason. J. Biol. Chem., 1963,238:3453-3462
74. V I Groudeva and S N Groudev. Bulgar. Acad. Sci., 1980,33:1401-1404
75. M W H Mao and P R Dugan. FEMS Microbiol. Lett., 1980,8:121-125
76. D E Rawlings. J. Biotechnol., 1984, 158:737-738
77. D E Rawlings and L M Pretorius. Appl. Biochem.,1984,1:129-143
78. J C Cox and D H Boxer. Biotechnol. Appl. Biochem., 1986,8:269-275
79．邱冠周，王军．国外金属矿选矿，1998，6：29-33
80. M Drolet and P Zangga. Mol. Microbiol., 1990,4:1381-1391
81．魏以和，王军．国外金属矿选矿，1996，1：1-13
82．江西铜业公司编写。溶浸-萃取-电积资料汇编，1991
83．北京有色金属设计研究总院编写．智利-美国堆浸-萃取-电积技术考察报告，1993
2．武汉大学、复旦大学生物系微生物教研室．微生物学(第二版)，北京：高等教育出版社，1987
3. G R Postgate. The sulfate-reducing bacterial, Cambrige Univ. Press, Cambridge, 1984
4. A R Colmer and M E Hinkle. Science, 1947, 106:253-256
5. S R Hutchins and M S Davidson. Ann. Rev. Microbiol., 1986,40:311-336
6. N A Kinsel. J. Bacteriol., 1960,80:628-632
7. A P Jr. Harrison. Ann. Rev. Microbiol., 1984,38:265-292
8. G J W Arkesteyn and J AM. De. Bont. Can. J. Microbiol., 1980,26:1057-1065
9. J A Brierley. App. Environ. Microbiol., 1978,36:523-525
10．浸矿技术编委会编．浸矿技术，北京：原子能出版社，1994
11. W E Razzell and P C Trussell. J. Bacteriol., 1963,85:595-603
12. W Rudolfs and A Helbronner. Soil Science, 1922,14:459-464
13. M E C Barros. Appl. Environ. Microbiolo., 1984,47:593-595
14. E Drobner and H Huber. Appl. Environ. Microbiolo., 1990,56:2922-2923
15. R Guay and M Silver. Can. J. Microbiol., 1975,21:281-288
16. H Huber. Arch. Microbiol., 1989,151:479-485
17. S Lutters and H H Hanert, Arch. Microbiol., 1989,151:245-251
18. M E Mackintosh. J. Gen. Microbiol., 1978,105:215-218
19. J T Pronk and J C de Bruyn. Appl. Environ. Microbiol., 1992,58:2227-2230
20. T Sugio and W Mizunashi. J. Bacteriol., 1987,169:4916-4922
21. J G Cobley and J C Cox. Microbiol. Rev. Dec., 1983,47(4):579-595
22. P L Wichlace and R F Unz. Appl. Environ. Microbiol., 1991,57:138-145
23. O H Tuovinen. Geomicrobiol. J., 1993,10:207-217
24. T M Bhatti and J M Bigham. Appl. Environ. Microbiol., 1993,59:1984-1990
25. R G L McCready and W D Gould. Microbial Mineral Recovery, New York, 1990:107-126
26. C L Brierley. Bacterial Leaching, Crit. Rev. Microbiol., 1978,6:207-262
27. S C Lorbach and J M Shively. Geomicrobiol. J., 1993,10:219-226
28. L B Sukla. Hydrometallurgy, 1995,37:387-391
29. S S Bang and K N Narayana. Hydrometallurgy, 1995,37:181-192
30. Y A Attia and M Elzeky. Hydrometallurgy, 1989,22:291-230
31. R Y Wan and J D Miller. Metall. Trans., 1985,16B:575-588
32. V K Berry and L E Murr. Scanning Electron Microscopy, 1977,1:137-146
33. A M Nielsen and J V Beck. Science, 1972,175:1124-1127
34. H Sakaguchi and A E Torma. Appl. Envion. Microbiol., 1976,31:7-16
35. O H Tuovinen and D P Kelly. Arch. Microbiol., 1974,98:167-181
36. D W Duncan and C C Walden. Dev. Ind. Microbiol., 1972,13:66-74
37. M P Silverman. J. Bacteriol., 1963, 10:1046-1051
38. L E Murr and V K Berry. Hydrometallury, 1976,2:11-24
39. N C Trivedi and H M Tsuchiya. Int. J. Mineral Process., 1975,2:1-11
40．北京矿冶总院编译．细菌在采矿工程中的应用，北京：冶金工业出版社，1972
41. A D Agate. World J. Microbiol., 1996,12:487-495
42. K K Dwivedy and A K Mathur. Hydrometallury, 1995,38:99-109
43．孙春宝，魏德洲。国外金属矿选矿，1996，3：35-42
44．T G Carnahan．黄金提取技术，北京：北京大学出版社，1991
45．陈驹声．微生物工程，北京：化学工业出版社，1994
46．汤树德等．微生物学通报，1983，10(5)：201-204
47．胡岳华，康自珍等．国外金属矿选矿，1997，8：42-45
48．康自珍等．黄铜矿细菌氧化机理初步研究，中南工业大学硕士论文，1997
49. G I Karavaiko and G Rossi. Biogeotechnology of Metals, Center for International Projects GKNT, Moscow, 1988
50. L E Murr. Minerals Science Engineering, 1980,12(3):121-189
51. J V Beck. Biotechnology Bioengineering, 1967,9:487-501
52. L Ahonnen and P Hiltunen. In: Fundamental and Applied Biohydrometallurgy, Elsevier, Amsterdam, 1986:13-20
53. A Basaran and O H Tuovinen, Coal Prep., 1987,5:39-55
54. M Tszos and B Volesky. Biotechnol. Bioeng.,m 1982,24:955-969
55. R W Smith. Mineral Process. Extract. Metall. Rev., 1989,4:277-299
56. F Kargl and J G Welssman. Biotechnol. Bioeng., 1984,26:604-612
57. J A Solari and G Huerta. Colloids and Surfaces, 1992, 69:159-166
58. B K Chakrabarti and P C Banerjee. Can. J. Microbiol., 1991,37:692-696
59. D L Jones and E Petters. In: Extractive Metallurgy of Copper(Vol. 2), J C Yannapulos(eds.), Metallurgy Soc. AIME, New York, 1976:633-653
60. J D Sullivan. Trans. AIME, 1942,106:515-546
61. S Venkatachalam. Mineral Engineering, 1991,4:1115-1126
62. F Habashi. Chalcopyrite:its chemistry and metallurgy, McGraw-Hill Book Co., New York, 1978
63．沈同，王镜岩等．生物化学，北京：高等教育出版社，1991
64. A Bruynesteyn and R Hackl. In: Bacterial Leaching Metals from Ores on Intern. Seminar on Dump and Inderground, G I Karavaiko (eds.), Center For Environment Projection, Moscow, 1990:10-20
65. A P Methta and L E Murr. Biotechnol. Bioeng., 1982,14:919-940
66. V K Berry and L E Murr. Hydrometallurgy, 1978, 3:309-326
67．G Milazzo and M Blank，肖科译．生物电化学：生物氧化还原反应，天津：天津科学技术出版社，1990
68. V P Skulachev. Curr. Top. Bioeng., 1971, 4:127-151
69．李缉熙，牛中奇．生物电磁学概论，西安：西安电子科技大学出版社，1990
70. S B Yunker and J M Radovich. Biorechnol. Bioeng., 1986,28:1867-1875
71. N A Kinsel and W W Umbreit. J. Bacteriol., 1964,87:1243-1246
72. J T Pronk. Geomicrobiol. J., 1993,10:153-171
73. B A Blaycock and A Nason. J. Biol. Chem., 1963,238:3453-3462
74. V I Groudeva and S N Groudev. Bulgar. Acad. Sci., 1980,33:1401-1404
75. M W H Mao and P R Dugan. FEMS Microbiol. Lett., 1980,8:121-125
76. D E Rawlings. J. Biotechnol., 1984, 158:737-738
77. D E Rawlings and L M Pretorius. Appl. Biochem.,1984,1:129-143
78. J C Cox and D H Boxer. Biotechnol. Appl. Biochem., 1986,8:269-275
79．邱冠周，王军．国外金属矿选矿，1998，6：29-33
80. M Drolet and P Zangga. Mol. Microbiol., 1990,4:1381-1391
81．魏以和，王军．国外金属矿选矿，1996，1：1-13
82．江西铜业公司编写。溶浸-萃取-电积资料汇编，1991
83．北京有色金属设计研究总院编写．智利-美国堆浸-萃取-电积技术考察报告，1993