CN1858276A - Method for extracting metal copper using microbe and its use - Google Patents
Method for extracting metal copper using microbe and its use Download PDFInfo
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- CN1858276A CN1858276A CNA2006100398226A CN200610039822A CN1858276A CN 1858276 A CN1858276 A CN 1858276A CN A2006100398226 A CNA2006100398226 A CN A2006100398226A CN 200610039822 A CN200610039822 A CN 200610039822A CN 1858276 A CN1858276 A CN 1858276A
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- copper
- microorganism
- nutrient solution
- metal copper
- extraction
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 88
- 239000010949 copper Substances 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 47
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 40
- 239000002184 metal Substances 0.000 title claims abstract description 40
- 239000000843 powder Substances 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 3
- 238000000605 extraction Methods 0.000 claims description 43
- 244000005700 microbiome Species 0.000 claims description 42
- 238000002386 leaching Methods 0.000 claims description 31
- 235000015097 nutrients Nutrition 0.000 claims description 31
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 23
- 241000605118 Thiobacillus Species 0.000 claims description 16
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 239000000284 extract Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 241000605008 Spirillum Species 0.000 claims description 7
- 238000005273 aeration Methods 0.000 claims description 7
- 230000001580 bacterial effect Effects 0.000 claims description 7
- 230000008021 deposition Effects 0.000 claims description 5
- 239000012467 final product Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000002791 soaking Methods 0.000 abstract description 3
- 241000894006 Bacteria Species 0.000 description 33
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 18
- 238000005516 engineering process Methods 0.000 description 10
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 229910052683 pyrite Inorganic materials 0.000 description 7
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 7
- 239000011028 pyrite Substances 0.000 description 7
- 241000605272 Acidithiobacillus thiooxidans Species 0.000 description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000009854 hydrometallurgy Methods 0.000 description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 description 6
- 239000011707 mineral Substances 0.000 description 6
- 235000010755 mineral Nutrition 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 5
- 229910052770 Uranium Inorganic materials 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 229960004643 cupric oxide Drugs 0.000 description 5
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 5
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 5
- 239000001117 sulphuric acid Substances 0.000 description 5
- 235000011149 sulphuric acid Nutrition 0.000 description 5
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 4
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000012258 culturing Methods 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 230000000813 microbial effect Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- -1 sulfuric acid amine Chemical class 0.000 description 3
- 241000193830 Bacillus <bacterium> Species 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- 241001124569 Lycaenidae Species 0.000 description 2
- 241000605268 Thiobacillus thioparus Species 0.000 description 2
- FQGMPQGXUXIOKI-UHFFFAOYSA-N [S--].[S--].[Cu++].[Zn++] Chemical compound [S--].[S--].[Cu++].[Zn++] FQGMPQGXUXIOKI-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000009395 breeding Methods 0.000 description 2
- 230000001488 breeding effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 235000014987 copper Nutrition 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910001447 ferric ion Inorganic materials 0.000 description 2
- 229910001448 ferrous ion Inorganic materials 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 229910052569 sulfide mineral Inorganic materials 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 241000521593 Acidimicrobium Species 0.000 description 1
- 241001464929 Acidithiobacillus caldus Species 0.000 description 1
- 241000605222 Acidithiobacillus ferrooxidans Species 0.000 description 1
- 241000589158 Agrobacterium Species 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 235000015076 Shorea robusta Nutrition 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 241000205091 Sulfolobus solfataricus Species 0.000 description 1
- 241001509286 Thiobacillus denitrificans Species 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000000721 bacterilogical effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052951 chalcopyrite Inorganic materials 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 238000009867 copper metallurgy Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000009615 deamination Effects 0.000 description 1
- 238000006481 deamination reaction Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000005363 electrowinning Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- LVIYYTJTOKJJOC-UHFFFAOYSA-N nickel phthalocyanine Chemical compound [Ni+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 LVIYYTJTOKJJOC-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 229940093916 potassium phosphate Drugs 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 229910052969 tetrahedrite Inorganic materials 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention discloses microbe extracting method of metal copper and its application. The method includes crushing copper connecting material into powder; soaking the powder in culture liquid containing microbe to leach out for 15-60 days; solid-liquid separating to obtain leach solution and extracting with copper extractant; reverse extracting copper from the copper extracting liquid with reverse extractant; and final electrolyzing the copper containing reverse extracting liquid to obtain metal copper. The said method may be used in extracting metal copper from printed circuit board. The method has high economic benefit and environment benefit.
Description
Technical field
The invention belongs to the microorganism hydrometallurgical technology, relate to and a kind ofly utilize microorganism therefrom to extract method of metal copper, the invention still further relates to the application of this method in the metallic copper that extracts printed-wiring board (PWB).
Background technology
Bacteriosmelt claims microbial leaching again, is the industrial a kind of novel process of hydrometallurgy in modern age.It mainly is to use molten lean ore, abandoned mine, mine tailing and Daye slag etc. of soaking of bacterium method, to reclaim some valuable non-ferrous metal and rare metal, reaches and prevents that Mineral resources run off, and maximally utilise a kind of metallurgical method of mineral reserve.
Bacteriosmelt starts from 1974, and U.S. scientist Colmer and Hinkle had isolated a strain iron protoxide bacillus (Thiobacillus ferrooxidans) from acid mine water at that time.After this Bu Linuo of the U.S. etc. separates from the mineral water of Bingham valley, the Utah State again and has obtained thiobacillus thiooxidans (T.thiooxidans) and thiobacillus ferrooxidant, with these two kinds of bacterium immersion copper sulfide ores, found that and can be dissolved out metal from ore.So far bacteriosmelt technology begins to grow up.In the U.S., this method production gained of copper system application of 10% is arranged approximately, only bacterium smelting steel method is adopted in the Bingham valley, and is annual with regard to recyclable copper 72000t.More noticeable is that uranium also can adopt the bacteriosmelt method to adopt the smelting recovery.According to reports, in area, the special lake of Ontario, Canada state Erie Australia, have at least three uranium ore companies carrying out this work.Tan Luoke company introduces the lake water that contains thiobacillus ferrooxidant and handles a large amount of lean ores, the oxide compound 7000kg of every month recyclable uranium near lake water like that.
In recent years, the research of China's bacteriosmelt and application have also had suitable development, utilize the copper metallurgy of bacteriosmelt method and reclaim uranium to have certain scale.Bacterium is controlled gold and has developed into a kind of important smelting means at present, utilizes this method can come tens kinds of valuable and rare metals such as smelting copper, lead, zinc, gold and silver, manganese, nickel, chromium, molybdenum, cobalt, bismuth, vanadium, selenium, arsenic, thallium, cadmium, gallium, uranium.
The principle of bacteriosmelt:
About bacterium principle the molten leaching of metal from ore, so far still among inquiring into.Someone finds, bacterium can be metal molten leaching from ore the indirect action of the metabolite that generates in the bacterium vital movement, or be called pure chemistry reaction leaching and say, be meant by bacteriological action to produce sulfuric acid and ferric sulfate that lixiviate goes out useful metal in the ore as solvent by sulfuric acid or ferric sulfate then.Sulfuric acid and ferrum sulfuricum oxydatum solutum are the active solvents of common use in general sulfide mineral and other mineralogical chemistry extraction (hydrometallurgy).For example thiobacillus thiooxidans and poly-thiobacillus can be oxidized to sulfuric acid to the sulphur in the ore, and thiobacillus ferrooxidant can be oxidized to ferric sulfate to ferrous sulfate.Its reaction formula is as follows:
By above-mentioned reaction, bacterium has obtained energy needed, and ferric sulfate can change into soluble compound such as iron in the ore or copper and be dissolved out from ore, and its chemical process is:
Relevant metallic sulfide through bacterium is molten soak after, collect acid-containing solution, various metals concentrated and precipitated by methods such as displacement, extraction, electrolysis or ion-exchanges.
The investigator who has thinks that the principle of bacteriosmelt is that bacterium has direct lixiviate effect to ore.They find that some nonferrous copper mines such as copper glance, tetrahedrite etc. do not need to add iron, and thiobacillus ferrooxidant can be leached copper equally significantly; That is to say that bacterium exists the ability of direct oxidation to ore, contact dissolving metal is come out by physical chemistry between bacterium and the ore.The investigator who has finds that also some can produce a kind of organism by the bacterium of organism life, and is chimeric with the metal ingredient in the ore, thereby metal is dissolved out from ore.Electron micrograph also confirms: thiobacillus thiooxidans is after assemble on sulphur crystalline surface, and etch has vestige to ore.In addition, microbial cells can produce various enzymes in mineral surface, has also supported bacterium directly to act on the theory of soaking the ore deposit.
Microorganism in the bacteriosmelt and culture condition:
The microorganism of participation bacteriosmelt has a variety of, mainly contains following several: thiobacillus thiooxidans, thiobacillus thioparus (T.thioparus), deamination thiobacillus (T.denitrificans) and some heterotrophic bacteriums, thiobacillus ferrooxidant (as bacillus, Agrobacterium) etc.
Microorganism in the bacteriosmelt mostly is the chemosynthetic autotroph bacterium, and how acidproof they are generally, even still can survive below pH1.The bacterium energy sulfur oxide and the sulfide that have therefrom obtain energy for existence.
When cultivating metallurgical bacterium, at first should be different with the impurity situation according to ore kind and various component thereof, select suitable bacterial classification.Can make tolerance and molten the soak efficient of bacterial strain enhancing in case of necessity by the method for breeding to full genus.Secondly, preparation suitable culture base is with the required bacterium of enlarged culturing.Because metallurgical bacterium mostly is autotroph, generally need do not add the phosphorus source in the substratum, but need to add sulfuric acid amine or saltpetre, potassiumphosphate, sal epsom, ferric sulfate, sulphur etc. as N and mineral origin.The pH of substratum is advisable with 3～4.Culture temperature is 28～32 ℃.Must ventilate in the culturing process in order to breeding.Generally in culturing process, should avoid solar radiation.Someone had once designed a kind of new " 9K " substratum, and every milliliter of substratum can obtain bacterial cell 2～4 * 10
8Individual, be applied to metallurgical industry favourable condition is provided for cultivating a large amount of bacteriums.
Application number is the bacterial leaching way that application for a patent for invention that CN200410022826.4 (publication number is CN1556230A), name are called " method that bacterium is leached the copper in the cupriferous pyrite stone " discloses copper in a kind of cupriferous pyrite stone, this method is utilized the bacterium electrochemical catalysis effect between the different sulfide minerals, the copper sulfide that is low potential is as the corrosion anode, the pyrite of noble potential, kustelite be as negative electrode, utilizes bacterium to promote galvanic effect between them; Other does not constitute the pyrite of galvanic effect, then by the pyritous obligate bacterium of CONTROL PROCESS condition inhibited oxidation---little spirillum isoreactivity reaches the purpose of slowing down oxidation of pyrite.Pyrite for the coexistence of copper zinc sulfide at first leaches cupric oxide with sulfuric acid, with the leaching of the cupric ion catalysis zink sulphide that leaches, owing to zink sulphide is leached by catalysis, thereby has early eliminated the current potential restraining effect that zink sulphide leaches the chalcopyrite bacterium again.The present invention has following positively effect: under natural particle size, natural weather condition, bacterium was leached 4 months, and the leaching yield of copper can reach more than 75%; Copper zinc sulfide coexistence pyrite can realize that copper, zinc leach simultaneously, and is approaching when leaching effect exists with no zinc sulphide minerals.
The patent No. is CN02151601.4 (Granted publication number for CN1208480C), the patent of invention that name is called " a kind of method of extracting copper from the mixed type copper mine " discloses a kind ofly extracts method of metal copper from the mixed type copper deposit, it is to be raw material with copper-sulphide ores and copper oxide ore, respectively it is broken into qualified muck, bacteria heap leaching is directly used in the qualified ore deposit of cupric oxide, and screening is washed in the qualified ore deposit of cupric oxide earlier, again respectively to sludge, ore in sand form carries out agitation leach and dump leaching, leach liquor is extracted, extract a surplus liquid part and return bacteria heap leaching, the supplemental acid balance, another part is transported to agitation leach and dump leaching, as whole ore deposit reagent that soak, after this load organic phases after the extraction is carried out conventional back extraction successively, electrodeposition can obtain the high purity cathode copper.This complete wet method combined technology does not need grind grading, roasting and flue gas acid preparing, mine tailing, tailings coarse size are easily stored up, the copper-sulphide ores leaching yield reaches 80%, copper oxide ore reaches 93%, advantages such as having high-recovery, low cost, fewly drop into, be pollution-free can be and has the geographic metallurgical industry of this mixed type copper ore resource and bring new development.
The patent No. be CN99121385.8 (Granted publication number for CN1293259), name be called " recovery copper and mickel " patent disclosure a kind of method that from the cupric sulfide that is the ore pulp form and nickel sulfide concentrate, reclaims copper and mickel.This ore pulp is carried out bio-oxidation, cupric sulfide is become solubility copper sulfate, nickelous sulfide becomes the solubility single nickel salt.Liquid is separated with ore pulp, and solution produces the sulfuric acid content height and the low raffinate of copper sulfate content through solvent extraction agent.Use the sulphuric acid soln back extraction then.Electrowinning copper from sulphuric acid soln, a part of poor copper raffinate turns back to the bio-oxidation step.From another part raffinate, reclaim nickel.Preferred bacterium is a kind of bacterium during thiobacillus ferrooxidant, thiobacillus thiooxidans, ferricoxidans, Thiobacillus Caldus, Acidimicrobium and sulfolobus solfataricus belong at least.
The copper that the using microbe that above-mentioned document proposed extracts is the copper in the compound, and its existence form is ionic condition, does not appear in the newspapers for the technology that adopts microorganism to extract metallic copper.
Printed-wiring board (PWB) (PCB) is one of basic element of character of electronic product composition, along with rolling up of electronic product demand, has produced a large amount of abandoned printed circuit boards, and also can produce a large amount of scrap stock in the printed-wiring board (PWB) production process.At present, have that investment is big, easily produce poisonous, harmful the like waste in the process with technological methods such as mechanical treatment process, method of chemical treatment.Contain a large amount of metallic coppers in these printed-wiring board (PWB)s, these metallic coppers are wasted in a large number as important industrial raw material, but do not have effective means to recycle at present.
Summary of the invention
The objective of the invention is provides a kind of less investment, technology is simple, efficient the is high microorganism that utilizes therefrom to extract method of metal copper at the problems referred to above.
Another object of the present invention provides the application of aforesaid method in the metallic copper that extracts printed-wiring board (PWB).
The objective of the invention is to be achieved through the following technical solutions:
A kind of microorganism extraction method of metal copper of utilizing may further comprise the steps:
The pending material that a. will contain metallic copper is ground into powder;
B. the powder input is contained in the nutrient solution of microorganism, keep leaching 15-60 days;
C. separate solid and liquid after leaching, get leach liquor, extract with copper extractant; Cupric extraction liquid after the extraction is carried out back extraction copper with reverse-extraction agent;
D. the cupric strip liquor carries out electrolytic deposition, get final product metallic copper.
The described microorganism extraction method of metal copper of utilizing, wherein powder needed 40 mesh sieves.
The described microorganism extraction method of metal copper of utilizing, wherein powder is 10～300g/L with the ratio that contains the nutrient solution of microorganism.
The described microorganism extraction method of metal copper of utilizing, wherein microorganism is little spirillum of thiobacillus ferrooxidant, iron protoxide or their mixture.
The described microorganism extraction method of metal copper of utilizing, wherein the prescription of nutrient solution is:
| Composition | (NH 4) 2SO 4 | KCl | K 2HPO 4 | MgSO 4·7H 2O | Ca(NO 3) 2 | FeSO 4·7H 2O | H 2O |
| Nutrient solution B1 | 1.0～3.0g | 0.1～0.3g | 0.2～0.5g | 0.2～0.7g | 0.01～0.1g | 9g～50g | 1L |
| Nutrient solution B2 | 0.15～0.5g | 0.05～0.1g | 0.05～0.1g | 0.50～1.0g | 0.01～0.1g | 9g～40g | 1L |
The described microorganism extraction method of metal copper of utilizing, wherein the pH of nutrient solution is 1.5～2.5, uses H
2SO
4Regulate.
Describedly utilize microorganism to extract method of metal copper, contain wherein that bacterial concentration reaches 10 in the nutrient solution of microorganism
7～10
8Individual/more than the mL order of magnitude.Under the normal circumstances, the upper limit of concentration of bacterial growth is usually 10
10Individual/mL.
The described microorganism extraction method of metal copper of utilizing adopts stirring, aeration, stirring and aeration blended mode or sleep mode to leach when wherein leaching.
Describedly utilize microorganism to extract the application of method of metal copper in the metallic copper that extracts printed-wiring board (PWB).
Describedly utilize microorganism to extract method of metal copper, wherein step c, d belong to sophisticated Technology (write as Zhu village. modern copper hydrometallurgy. Beijing: metallurgical industry press, 2002).
Beneficial effect of the present invention:
It is zeroth order (metal) state that present technique leaches object copper, and the copper that extracts during available technology adopting microorganism hydrometallurgy is to exist with the form of divalence with compound, and mechanism of action, interaction medium that this has just determined microorganism hydrometallurgy in the present invention and the prior art etc. is different.Existing microorganism hydrometallurgical technology is the lattice etc. that utilizes ferric iron and microbial destruction copper compound, and there is not valent variation in copper in the leaching process, and just the insoluble compound with copper changes soluble compound into.Present technique is to utilize ferric iron and microorganism to the effect of metallic copper, makes copper change divalence into by zeroth order, thereby enters solution.In this process, ferric ion changes ferrous ion into, and ferrous ion changes ferric ion into by microbiological oxidation again, has realized the recycle of iron ion.Can realize the leaching of small amounts of iron to a large amount of copper by this circulation, reduce the usage quantity of iron ion, this also is the essential place that present technique is different from chemical corrosion method.Utilize this circulation to leach metallic copper, can reduce investment and working cost greatly.The ferrous natural oxidation is very slow under acidic conditions, and copper is very stable in non-oxidizing acid, so nutrient solution can not be realized the leaching (experimental result confirmation) of copper at all under the situation of not adding microorganism.This explanation present technique is interaction by microorganism and substratum, makes the copper leaching that circulated.
Present technique has the common feature of microorganism hydrometallurgy, compare promptly that other metallurgical technologies have less investment, cost is low, metal recovery rate is high and advantage such as pollution-free, the metallic copper leaching efficiency can reach 97%, and need not to add chemical substances such as a large amount of acid, only utilized the Circulation of ferric iron, realized that the high-level efficiency of metallic copper leaches copper.When the electron wastes problem was more and more outstanding, this method had well solved the copper resources effective and has reclaimed, and has good economic benefit and environmental benefit.
Embodiment
The invention will be further elaborated below by embodiment, but do not limit the present invention.
Embodiment 1:
(1) printed-wiring board (PWB) that will remove components and parts is ground into 40 purpose powder;
(2) the printed-wiring board (PWB) powder is dropped into cultured containing among the thiobacillus ferrooxidant nutrient solution B1 by 10g/L;
Nutrient solution B1 prescription is:
| (NH 4) 2SO 4 | KCl | K 2HPO 4 | MgSO 4·7H 2O | Ca(NO 3) 2 | FeSO 4·7H 2O | H 2O | |
| Nutrient solution B1 | 3.0g | 0.2g | 0.5g | 0.5g | 0.01g | 45.0g | 1L |
The pH of nutrient solution B1 is 2.0, uses H
2SO
4Regulate.
Culturedly contain that thiobacillus ferrooxidant concentration reaches 10 among the thiobacillus ferrooxidant nutrient solution B1
7Individual/more than the mL order of magnitude.
(3) adopt stirring and aeration hybrid mode to leach 15 days, leaching efficiency can reach 100%;
(4) solid and liquid after separation is leached are got leach liquor, carry out three grades of extractions with extraction agent P204, and leach liquor and extraction agent ratio are 1: 1;
(5) the cupric extraction liquid after will extracting carries out back extraction copper with sulphuric acid soln;
(6) the cupric strip liquor carries out electrolytic deposition, get final product highly purified metallic copper.
Embodiment 2:
(1) printed-wiring board (PWB) that will remove components and parts is ground into 80 purpose powder;
(2) the printed-wiring board (PWB) powder is dropped into cultured containing among the little spirillum nutrient solution of the iron protoxide B2 by 20g/L;
The prescription of nutrient solution B2 is:
| (NH 4) 2SO 4 | KCl | K 2HPO 4 | MgSO 4·7H 2O | Ca(NO 3) 2 | FeSO 4·7H 2O | H 2O | |
| Nutrient solution B2 | 0.2g | 0.1g | 0.1g | 0.5g | 0.01g | 10g | 1L |
The pH of nutrient solution B2 is 2.5, uses H
2SO
4Regulate.
Culturedly contain that the little spirillum concentration of iron protoxide reaches 10 in the little spirillum nutrient solution of iron protoxide
8Individual/more than the mL order of magnitude.
(3) adopt stirring and aeration hybrid mode to leach 20 days, leaching efficiency can reach 98%;
(4) solid and liquid after separation is leached are got leach liquor, carry out three grades of extractions with extraction agent P204, and leach liquor and extraction agent ratio are 1: 1;
(5) the cupric extraction liquid after will extracting carries out back extraction copper with sulphuric acid soln;
(6) the cupric strip liquor carries out electrolytic deposition, get final product highly purified metallic copper.
Embodiment 3:
(1) printed-wiring board (PWB) that will remove components and parts is broken into 80 purpose powder;
(2) the printed-wiring board (PWB) powder is dropped into cultured containing among the thiobacillus ferrooxidant nutrient solution B2 by 50g/L;
The prescription of nutrient solution B2 is:
| (NH 4) 2SO 4 | KCl | K 2HPO 4 | MgSO 4·7H 2O | Ca(NO 3) 2 | FeSO 4·7H 2O | H 2O | |
| Nutrient solution B2 | 0.15g | 0.05g | 0.05g | 1.0g | 0.1g | 25g | 1L |
The pH of nutrient solution B2 is 1.5, uses H
2SO
4Regulate.
Culturedly contain that thiobacillus ferrooxidant concentration reaches 10 in the thiobacillus ferrooxidant nutrient solution
7Individual/more than the mL order of magnitude.
(3) adopt stirring and aeration hybrid mode to leach 30 days, leaching efficiency can reach 97%;
(4) solid and liquid after separation is leached are got leach liquor, carry out three grades of extractions with extraction agent P204, and leach liquor and extraction agent ratio are 1: 1;
(5) the cupric extraction liquid after will extracting carries out back extraction copper with sulphuric acid soln;
(6) the cupric strip liquor carries out electrolytic deposition, get final product highly purified metallic copper.
Embodiment 4:
Described in embodiment 3, other conditions are constant, and printed-wiring board (PWB) powder addition is 300g/L in the step 2, and extraction time kept 60 days in the step 3, keep during leaching stirring, and leaching efficiency can reach 97%.
Embodiment 5:
Described in embodiment 3, other conditions are constant, and bacterium is adopted the mixture of thiobacillus ferrooxidant and the little spirillum of iron protoxide, leaching efficiency 98%.
Reference examples:
Described in embodiment 3, do not contain bacterium in the nutrient solution, other conditions are constant, and leaching efficiency is 10%.
Claims (9)
1, a kind of microorganism extraction method of metal copper of utilizing is characterized in that may further comprise the steps:
The pending material that a. will contain metallic copper is ground into powder;
B. the powder input is contained in the nutrient solution of microorganism, keep leaching 15-60 days;
C. separate solid and liquid after leaching, get leach liquor, extract with copper extractant; Cupric extraction liquid after the extraction is carried out back extraction copper with reverse-extraction agent;
D. the cupric strip liquor carries out electrolytic deposition, get final product metallic copper.
2, the microorganism extraction method of metal copper of utilizing according to claim 1 is characterized in that powder needed 40 mesh sieves.
3, the microorganism extraction method of metal copper of utilizing according to claim 1 is characterized in that powder and the ratio that contains the nutrient solution of microorganism are 10～300g/L.
4, the microorganism extraction method of metal copper of utilizing according to claim 1 is characterized in that microorganism is little spirillum of thiobacillus ferrooxidant, iron protoxide or their mixture.
5, the microorganism extraction method of metal copper of utilizing according to claim 1 is characterized in that the prescription of nutrient solution is:
(NH
4)
2SO
4 KCl K
2HPO
4 MgSO
4·7H
2O
Ca(NO
3)
2 FeSO
4·7H
2O
H
2O
Nutrient solution B1 1.0～3.0g 0.1～0.3g 0.2～0.5g 0.2～0.7g 0.01～0.1g 9g～50g 1L
Nutrient solution B2 0.15～0.5g 0.05～0.1g 0.05～0.1g 0.50～1.0g 0.01～0.1g 9g～40g 1L
6, the microorganism extraction method of metal copper of utilizing according to claim 5 is characterized in that the pH of nutrient solution is 1.5～2.5, uses H
2SO
4Regulate.
7, according to claim 1ly utilize microorganism to extract method of metal copper, it is characterized in that containing that bacterial concentration reaches 10 in the nutrient solution of microorganism
7～10
8Individual/more than the mL order of magnitude.
8, the microorganism extraction method of metal copper of utilizing according to claim 1 adopts stirring, aeration, stirring and aeration blended mode or sleep mode to leach when it is characterized in that leaching.
9, claim 1 is described utilizes microorganism to extract the application of method of metal copper in the metallic copper that extracts printed-wiring board (PWB).
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| CNB2006100398226A CN100404705C (en) | 2006-04-24 | 2006-04-24 | Method for extracting metal copper using microbe and its use |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100398226A CN100404705C (en) | 2006-04-24 | 2006-04-24 | Method for extracting metal copper using microbe and its use |
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| CN1858276A true CN1858276A (en) | 2006-11-08 |
| CN100404705C CN100404705C (en) | 2008-07-23 |
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ID=37297233
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206751A (en) * | 2011-04-29 | 2011-10-05 | 常州纺织服装职业技术学院 | Method for continuously recovering copper from printed circuit boards by microbial metabolites under action of micro electric field |
| CN102363890A (en) * | 2011-10-26 | 2012-02-29 | 广州有色金属研究院 | Method for recovering metal copper in waste circuit board |
| CN103898550A (en) * | 2014-04-14 | 2014-07-02 | 常州纺织服装职业技术学院 | Recovery method of cupper in circuit board |
| CN104328280A (en) * | 2014-10-15 | 2015-02-04 | 上海第二工业大学 | Method and equipment for recycling all metal components in waste flexible circuit board |
| CN109182751A (en) * | 2018-08-27 | 2019-01-11 | 江南大学 | A method of chalcopyrite Bioleaching is promoted based on iron sulphur metabolic regulation |
| CN109628357A (en) * | 2019-02-12 | 2019-04-16 | 黑龙江八农垦大学 | A kind of ferrous oxide complex microbial inoculum and its application |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19960132A1 (en) * | 1999-12-14 | 2001-06-21 | Alexander Beckmann | Process for the extraction of copper and other metals |
| CN1265001C (en) * | 2002-10-28 | 2006-07-19 | 北京有色金属研究总院 | New technology of leaching copper sulfide ore using copper ore acidic ore pit water containing bacteria |
-
2006
- 2006-04-24 CN CNB2006100398226A patent/CN100404705C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206751A (en) * | 2011-04-29 | 2011-10-05 | 常州纺织服装职业技术学院 | Method for continuously recovering copper from printed circuit boards by microbial metabolites under action of micro electric field |
| CN102206751B (en) * | 2011-04-29 | 2013-10-02 | 常州纺织服装职业技术学院 | Method for continuously recovering copper from printed circuit boards by microbial metabolites under action of micro electric field |
| CN102363890A (en) * | 2011-10-26 | 2012-02-29 | 广州有色金属研究院 | Method for recovering metal copper in waste circuit board |
| CN103898550A (en) * | 2014-04-14 | 2014-07-02 | 常州纺织服装职业技术学院 | Recovery method of cupper in circuit board |
| CN104328280A (en) * | 2014-10-15 | 2015-02-04 | 上海第二工业大学 | Method and equipment for recycling all metal components in waste flexible circuit board |
| CN109182751A (en) * | 2018-08-27 | 2019-01-11 | 江南大学 | A method of chalcopyrite Bioleaching is promoted based on iron sulphur metabolic regulation |
| CN109182751B (en) * | 2018-08-27 | 2019-09-03 | 江南大学 | A method of chalcopyrite Bioleaching is promoted based on iron sulphur metabolic regulation |
| CN109628357A (en) * | 2019-02-12 | 2019-04-16 | 黑龙江八农垦大学 | A kind of ferrous oxide complex microbial inoculum and its application |
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|---|---|
| CN100404705C (en) | 2008-07-23 |
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