CN101956071B - Biological metallurgy mineral leaching microorganism combined bacterium fluid for copper ore and method for recycling metallic copper - Google Patents
Biological metallurgy mineral leaching microorganism combined bacterium fluid for copper ore and method for recycling metallic copper Download PDFInfo
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- CN101956071B CN101956071B CN2010105266198A CN201010526619A CN101956071B CN 101956071 B CN101956071 B CN 101956071B CN 2010105266198 A CN2010105266198 A CN 2010105266198A CN 201010526619 A CN201010526619 A CN 201010526619A CN 101956071 B CN101956071 B CN 101956071B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/18—Extraction of metal compounds from ores or concentrates by wet processes with the aid of microorganisms or enzymes, e.g. bacteria or algae
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
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- 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
Abstract
The invention discloses biological metallurgy mineral leaching microorganism combined bacterium fluid for a copper ore and a method for recycling metallic copper. The method comprises the following steps that: mineral leaching microorganisms after adaptive culture, continuous amplification culture and ore pile adaptive culture are combined and used for mineral leaching, and different leaching methods are adopted aiming at the ore of different objects, which comprise a biological metallurgy processing method for lump ores, powder ores, tailings, copper smelting slags and the like; and the obtained qualified leaching solution is used to prepare two products, namely electrolytic copper by an extraction-electrodeposition method and spongy copper by a short stage displacement method. The method has the advantages of suitability for industrial production under different conditions, efficient utilization of low-grade copper ore resources and capacity of effectively protecting the ecological environment of mine areas and achieving a win-win situation of economic benefit and environmental friendliness.
Description
Technical field
The invention belongs to the biological metallurgy field, be specifically related to a kind of method of biological metallurgy leaching microbacteria composite bacterial solution and recovery copper metal thereof of copper mine stone.
Background technology
Copper is the grand strategy non-ferrous metal, is used for fields such as electric, machinofacture, national defense industry.World's copper resource mainly concentrates on states such as Chile, the U.S., Zambia.Zambia's copper mine reserves account for 6.4% of global total amount, but in the middle of the explored copper ore resource, have a considerable amount of copper mines efficiently to utilize new technology to wait exploitation owing to lacking.Especially the mine tailing stored up in a large number of Zambia country and mining barren rock resource; Need a large amount of government funds to safeguard hillock; But owing to lack otherwise effective technique, ore is stored up and has been produced a large amount of heavy metal-containing waste waters in the process, not only can't the efficient recovery heavy metal element; And bring huge destruction to the ecosystem, environment of mining area is caused serious pollution.
Biological metallurgy is that utilization is the action of microorganisms of the energy with mineral, and the oxygenolysis mineral make metals ion get into solution, further separates, extracts the new and high technology of metal.Characteristics, particularly microbial metallurgy technology such as it has that flow process is short, cost is low, environmental friendliness and low pollutions can processing low-grade, complicacy, unmanageable Mineral resources, advanced technology, production efficiency height.At present the whole world output that adopts the biological metallurgy technology to extract metallic copper has accounted for 25% of whole copper output, the U.S., Chile even arrive 30%.
Biological metallurgy technology mainly contains three kinds: dump leaching, leaching and agitation leach on the spot.The selection of different process is according to ore type and wherein has the physicochemical property of mineralogical composition to decide.The ore that relates at present mainly contains: copper mine stone, nickel cobalt ore, gold mine and uranium ore.But, also there is not the complete suitable treatment process of a cover at present to the oxidized ore of various grades and copper mine stone and the metallurgical slag and the mining barren rock of sulphide ores type.
Summary of the invention
The purpose of this invention is to provide a kind of multiple mixing effect of invading the ore deposit mikrobe of utilizing; To the oxidized ore of various grades and the copper mine stone of sulphide ores type; Comprise the biological metallurgy treatment process of lump ore, fine ore, mine tailing, acid block barren rock, copper smelting-furnace slag etc., be applicable to the suitability for industrialized production under the different condition, realized resources effective utilization; Mining area ecological environment be can effectively protect, economic benefit and eco-friendly win-win situation realized.
The biological metallurgy leaching microbacteria composite bacterial solution of a kind of copper mine stone of the present invention is that process flexibility is cultivated, and the required mikrobe of the leaching after enlarged culturing and ore storage flexibility are cultivated continuously mixes, and obtaining concentration is 1-8 * 10
6The mixed bacteria liquid of cell/mL, described mixed bacteria liquid makes up according to the cell concn proportioning of unit volume: have a liking for the ferrous thiobacillus of acid oxidase 30 ± 5.0%, have a liking for acid oxidase sulphur thiobacillus 15 ± 3.0%, iron protoxide hook end spirobacteria 30 ± 5.0%, thermophilic thiobacillus 12 ± 3.0%, sulfobacillus thermosulfidooxidans 3 ± 0.5%, metal sulfolobus 2 ± 0.5%, diligent metal coccus 3 ± 0.5%, wtih 3 ± 0.5%, ten thousand sour bacterium 2 ± 0.5%; It is described that to have a liking for the ferrous thiobacillus of acid oxidase be that 16 kinds of preserving numbers are CCTCC AB206199; CCTCC AB 206200; CCTCC AB 206201; CCTCC AB 206202; CCTCC AB 206203; CCTCC AB 206204; CCTCC AB 206205; CCTCC AB 206206; CCTCC AB 206207; CCTCCAB 206208; CCTCC AB 207053; CCTCC AB 207054; CCTCC AB 207055; CCTCC AB207056; CCTCC AB 207057; One or more of CCTCC AB 207058; Have a liking for acid oxidase sulphur thiobacillus and be 3 kinds of preserving numbers and be one or more of CCTCC AB206195, CCTCC AB 206196, CCTCC AB 206197; Iron protoxide hook end spirobacteria is that 10 kinds of preserving numbers are one or more of CCTCC AB206158, CCTCC AB 206159, CCTCCAB 206160, CCTCC AB 206161, CCTCC AB 206162, CCTCC AB 206163, CCTCC AB206164, CCTCC AB 207036, CCTCC AB 207037, CCTCC AB 207038; Thermophilic thiobacillus is that 3 kinds of preserving numbers are one or more of CCTCC AB207044, CCTCC AB 206175, CCTCC AB 206176; Sulfobacillus thermosulfidooxidans CCTCC AB207045, metal sulfolobus CCTCC AB207047, diligent metal coccus are that 3 kinds of preserving numbers are one or more of CCTCC AB207046, CCTCC AB 206191, CCTCC AB 206192; Wtih is that 14 kinds of preserving numbers are one or more of CCTCC AB206219, CCTCC AB 206220, CCTCCAB 206221, CCTCC AB 206222, CCTCC AB 206223, CCTCC AB 206224, CCTCC AB206225, CCTCC AB 206226, CCTCC AB 207065, CCTCC AB 207066, CCTCC AB 207067, CCTCC AB 207068, CCTCC AB 207069, CCTCC AB 207070; Ten thousand sour bacterium CCTCC AB207048.
2-5%w/v copper mine breeze or concentrate that described ore storage flexibility cultivation is adding-0.074mm in chemical substratum are made mixed culture medium; Microorganism concn reaches 1-8 * 10 at least
7Behind the cell/mL, press 1-8 * 10 again
6Cell/mL is inoculated in the 5-10 ton ore storage, carries out ore deposit heap flexibility growth, makes it be in logarithmic phase, and microorganism concn reaches 1-8 * 10 at least
6Behind the cell/mL, press 1-8 * 10
6Cell/mL is inoculated in the 100-500 ton ore storage and cultivated 20-40 days.
Use the biological metallurgy recovery method that described leaching microbacteria composite bacterial solution carries out copper mine stone, may further comprise the steps:
(1) lump ore biological dump leaching
Lay bottom and impervious barrier, flat heap thickness is the impact plies of broken in advance good+5-40mm grade copper mine stone macrobead lump ore of 200-300mm as the stockyard on impervious barrier; Continuation with fragmentation good+the copper mine stone macrobead lump ore of 5-40mm grade carries out thin layer and builds heap, dilution heat of sulfuric acid sprays in advance, then according to 1-8 * 10
6Cell/mL inoculates described leaching microbacteria composite bacterial solution, beginning intermittent shower production operation and ventilation, and leach liquor is subsequent use;
(2) fine ore stirs the bacterium living beings drill traverse
With fragmentation good-the copper mine stone flour ore deposit and the vitriol oil of 5mm grade, contain described leaching microbacteria composite bacterial solution and join steel basin, make that microorganism concn is 1-8 * 10 in the mixing solutions
6Cell/mL; In steel basin, carry out agitation leach, leach liquor is subsequent use;
(3) mine tailing granulation biological dump leaching
At first copper mining tailing is made ball and granulate, granularity is controlled at 10-20mm, and the copper mine fine ore of laying the thick granularity of 150-200mm and be 5mm re-lays impervious barrier as bottom, and the coarse sand of flat heap 200-300mm thickness on impervious barrier is as the impact plies in stockyard; Be that the pelletizing shape copper mining tailing of 10-20mm is laid and built heap to the granularity after making ball and granulating on the impact plies then, dump leaching begins to carry out sulfuric acid early stage and sprays in advance, inoculates described leaching microbacteria composite bacterial solution then, and microorganism concn is 1-8 * 10
6Cell/mL carries out intermittent shower, and leach liquor is subsequent use;
(4) fine ore and acid block barren rock biological dump leaching
The copper content of laying granularity and be 40mm-60mm is that the copper mine of 0.09-0.3% is dug up mine acid block barren rock as bottom, and thickness is 300-400mm; Cover impervious barrier again; The thick granularity of flat heap 200-300mm is the copper mine fine ore of 5mm on impervious barrier; As the impact plies in stockyard, the ore deposit heap is carried out the paved in multi-layers mode, at first lays the acid block barren rock of the first layer copper mine; Use the mortar pump with mass concentration be 30% copper mining tailing sand pump to barren layer, make mine tailing evenly firmly be distributed in the ore bed; Re-lay second layer barren layer, again the pump CHARACTERISTICS OF TAILINGS SAND; So repeatedly, every layer heap height until the ore deposit heap is 4-6M; Dump leaching begins to carry out sulfuric acid early stage and sprays in advance, carries out described leaching microbacteria composite bacterial solution inoculation then, and microorganism concn is 1-8 * 10
6Cell/mL carries out intermittent shower, and leach liquor is subsequent use;
(5) fine ore and fine grinding copper smelting-furnace slag granulation biological dump leaching
At first the copper smelting-furnace slag is carried out fragmentation and fine grinding; Make ball with fine ore then and granulate, granularity is controlled at 20mm, and it is thick to lay 150-200mm; Granularity is that the fine ore of 5mm is as bottom; Cover impervious barrier above again, the process of flat heap 200-300mm thickness is made fine grinding smelted furnace cinder and the fine ore that ball is granulated on impervious barrier, as the impact plies in stockyard; Continue then carrying out dump leaching through fine grinding smelted furnace cinder and the fine ore of making the ball granulation, dump leaching begins to carry out sulfuric acid early stage and sprays in advance, carries out described leaching microbacteria composite bacterial solution inoculation then, and microorganism concn is 1-8 * 10
6Cell/mL carries out intermittent shower, and leach liquor is subsequent use;
(6) one or more leach liquor extraction electrodepositions that above-mentioned steps (1)-(5) obtained prepare electrolytic copper; One or more leach liquors that perhaps above-mentioned steps (1)-(5) obtained obtain copper sponge with iron powder replacement.
In the described lump ore biological dump leaching of step (1), described bottom is the coarse sand of 300-400mm thickness, and described fragmentation is good+and the copper mine stone of 5-40mm grade carries out thin layer and builds heap, and every layer height 5-7m lays the 4-6 layer; Earlier use the pH value to spray in advance, guarantee that pH of leaching solution maintains 1.7-1.9, after pH of leaching solution is stablized 48 hours, inoculate described leaching microbacteria composite bacterial solution as the dilution heat of sulfuric acid of 0.9-1.2.
The described fine ore of step (2) stirs in the bacterium living beings drill traverse, and the vitriolic mass concentration is 30-45g/L in the mixing solutions in the steel basin; Mixing speed is 40-60 rev/min; In whipping process, can also utilize air compressor machine blowing air in steel basin, leach reaction 1-3 hour.
In the described mine tailing granulation of step (3) biological dump leaching, add 2% dilute sulphuric acid when making the ball granulation, granularity is controlled at 20mm; Dump leaching begins to carry out sulfuric acid early stage and sprays in advance; Guarantee to leach environment pH value and maintain 1.7-1.9, pH value stabilization 24 hours is inoculated described leaching microbacteria composite bacterial solution.
In described fine ore of step (4) and the acid block barren rock biological dump leaching, dump leaching begins to carry out sulfuric acid early stage and sprays in advance, guarantees to leach environment PH and maintains 1.7-1.9, and environment PH is stablized and carried out said leaching microbacteria composite bacterial solution inoculation after 24 hours.
In described fine ore of step (5) and the fine grinding copper smelting-furnace slag granulation biological dump leaching; When fine ore and fine grinding copper smelting-furnace slag are granulated; At first the copper smelting-furnace slag is carried out fragmentation and fine grinding operation, make it-the 0.074mm grain size content is not less than 50%, adopt the sulfuric acid of 35-40g/L that it is made ball and granulate; Granulating, the back is unlimited placed 8-12 hour, made its face stable curing balling; Dump leaching begins to carry out sulfuric acid early stage and sprays in advance, guarantees to leach environment pH value and maintains 1.7-1.9, and environment pH value stabilization carries out described leaching microbacteria composite bacterial solution inoculation after 24 hours.
The described impervious barrier of step (1) (3) (4) (5) is the acid proof PVC geotextile of 1mm-3mm thickness.
The detailed process that the described extraction electrodeposition of step (6) prepares electrolytic copper is following: extraction adopts secondary extraction one-level to strip; Adopt Lix-984 as extraction agent; Leach liquor is at first injected extraction stoste header tank; Flow to the extraction of extraction box two-stage with the extraction agent in the organic phase header tank at 1: 1 by comparing O/A, the surplus liquid in extraction back is from flowing to circulatory pool, and the continuation of blowback ore storage utilizes leaches; Extraction load organic phases and reverse-extraction agent are after the one-level back extraction, and unloaded organic phase is returned repeated use; Extract the surplus liquid of surplus liquid and electrodeposition and carry out full cut-off road recycle; Electrodeposition adopts Ai Safa; Liquid is handled from flowing to the electric effusion circulation groove through filtering after the back extraction, after plate-type heat exchanger is warmed to 40-42 ℃, flows into Winning cell and carries out electrodeposition, and the electrodeposition lean solution is returned and made reverse-extraction agent; 7 days negative electrode work periods, the manual removal cathode copper; The anode sludge cleaned once in 1 year, took away in groove with mobile pump.
The detailed process of the described acquisition copper sponge of step (6) is following: the leach liquor original ph is adjusted between 1.5～2.0, removes Fe before the displacement
3+, control Fe
3+Concentration is not higher than 0.2g/L; The displacement terminal point is that the pH value is controlled at below 4.5; Stirring intensity is 100～150rpm/s; The normal temperature displacement, time swap 30min.
Adopt the present invention,, comprise sulphide ores and oxidized ore to various types of copper mine stones, no matter be the mining barren rock, or milltailings, comprise that the waste residue after the smelting can adopt this technology to handle, various resources are fully utilized; In addition, the biological metallurgy The Application of Technology helps the utilization of tailings pile resources effective and the efficient recovery of valency copper metal is arranged, and well protects mining area ecological environment, realizes economic benefit and eco-friendly win-win situation.
The advantage and the positively effect of invention
Key of the present invention is the copper mine stone to different objects, the mining barren rock, and milltailings, the waste residue after the smelting all adopt each adaptive technology to handle, and can obtain making full use of of resource.Adopt the biological dump leaching process recovery to reach more than 90%, the biological agitation leach technology recovery also surpasses 90%, and the leach liquor of acquisition can obtain high-quality cathodic electricity copper products through extraction electrodeposition technology, can obtain copper sponge through replacing process.
The present invention has wide promotional value and application prospect in whole world copper mine hydrometallurgy industry, can widen raw material sources, increases resource reserve, reduces production costs, and improves the level of resources utilization, prolongs mine life.
Embodiment
Further specify the present invention below in conjunction with embodiment, and unrestricted the present invention.
Carry out the biological metallurgy new technology at Zambia's Chambishi copper mine and use, composition of ores is as shown in table 1, and the analytical results that cultured microorganism group bacterial classification is formed is as shown in table 2.
The chemical multielement analysis of table 1 low grade ore, %
Table 2 unit volume mixed bacteria liquid cell concn proportioning is formed, %
Above bacterial classification is biological metallurgy microorganism resource storehouse contact purchase at China typical culture collection center (CCTCC).
It is described that to have a liking for the ferrous thiobacillus of acid oxidase be that 16 kinds of preserving numbers are CCTCC AB 206199; CCTCC AB 206200; CCTCC AB 206201; CCTCC AB 206202; CCTCC AB 206203; CCTCC AB 206204; CCTCCAB 206205; CCTCC AB 206206; CCTCC AB 206207; CCTCC AB 206208; CCTCC AB207053; CCTCC AB 207054; CCTCC AB 207055; CCTCC AB 207056; CCTCC AB 207057; One or more of CCTCC AB 207058; Have a liking for acid oxidase sulphur thiobacillus and be 3 kinds of preserving numbers and be one or more of CCTCC AB206195, CCTCC AB 206196, CCTCC AB 206197; Iron protoxide hook end spirobacteria is that 10 kinds of preserving numbers are one or more of CCTCC AB206158, CCTCC AB 206159, CCTCC AB 206160, CCTCC AB 206161, CCTCC AB 206162, CCTCC AB 206163, CCTCC AB 206164, CCTCC AB 207036, CCTCC AB 207037, CCTCC AB 207038; Thermophilic thiobacillus is that 3 kinds of preserving numbers are one or more of CCTCCAB207044, CCTCC AB 206175, CCTCC AB 206176; Sulfobacillus thermosulfidooxidans CCTCC AB207045, metal sulfolobus CCTCC AB207047, diligent metal coccus are that 3 kinds of preserving numbers are one or more of CCTCCAB207046, CCTCC AB 206191, CCTCC AB 206192; Wtih is that 14 kinds of preserving numbers are one or more of CCTCC AB206219, CCTCC AB 206220, CCTCC AB 206221, CCTCC AB 206222, CCTCC AB 206223, CCTCC AB 206224, CCTCC AB 206225, CCTCC AB 206226, CCTCCAB 207065, CCTCC AB 207066, CCTCC AB 207067, CCTCC AB 207068, CCTCC AB207069, CCTCC AB 207070; Ten thousand sour bacterium CCTCC AB207048.
The called after of above-mentioned bacterial strains preservation:
CCTCC AB 206199 has a liking for the ferrous thiobacillus CSU 206059 Acidithiobacillus ferrooxidans of acid oxidase
CCTCC AB 206200 has a liking for the ferrous thiobacillus CSU 206060 Acidithiobacillus ferrooxidans of acid oxidase
CCTCC AB 206201 has a liking for the ferrous thiobacillus CSU 206062 Acidithiobacillus ferrooxidans of acid oxidase
CCTCC AB 206202 has a liking for the ferrous thiobacillus CSU 206064 Acidithiobacillus ferrooxidans of acid oxidase
CCTCC AB 206203 has a liking for the ferrous thiobacillus CSU 206065 Acidithiobacillus ferrooxidans of acid oxidase
CCTCC AB 206204 has a liking for the ferrous thiobacillus CSU 206066 Acidithiobacillus ferrooxidans of acid oxidase
CCTCC AB 206205 has a liking for the ferrous thiobacillus CSU 206068 Acidithiobacillus ferrooxidans of acid oxidase
CCTCC AB 206206 has a liking for the ferrous thiobacillus CSU 206069 Acidithiobacillus ferrooxidans of acid oxidase
CCTCC AB 206207 has a liking for the ferrous thiobacillus CSU 206071 Acidithiobacillus ferrooxidans of acid oxidase
CCTCC AB 206208 has a liking for the ferrous thiobacillus CSU 206073 Acidithiobacillus ferrooxidans of acid oxidase
CCTCC AB 207053 has a liking for the ferrous thiobacillus CSU 206061 Acidithiobacillus ferrooxidans of acid oxidase
CCTCC AB 207054 has a liking for the ferrous thiobacillus CSU 206063 Acidithiobacillus ferrooxidans of acid oxidase
CCTCC AB 207055 has a liking for the ferrous thiobacillus CSU 206067 Acidithiobacillus ferrooxidans of acid oxidase
CCTCC AB 207056 has a liking for the ferrous thiobacillus CSU 206070 Acidithiobacillus ferrooxidans of acid oxidase
CCTCC AB 207057 has a liking for the ferrous thiobacillus CSU 206072 Acidithiobacillus ferrooxidans of acid oxidase
CCTCC AB 207058 has a liking for the ferrous thiobacillus CSU 206074 Acidithiobacillus ferrooxidans of acid oxidase
CCTCC AB 206195 has a liking for acid oxidase sulphur thiobacillus CSU 206051 Acidithiobacillus thiooxidans
CCTCC AB 206196 has a liking for acid oxidase sulphur thiobacillus CSU 206052 Acidithiobacillus thiooxidans
CCTCC AB206197 has a liking for acid oxidase sulphur thiobacillus CSU 206053 Acidithiobacillus thiooxidans
CCTCC AB206158 iron protoxide hook end spirobacteria CSU 206002 Leptospirillum ferrooxidans
CCTCC AB206159 iron protoxide hook end spirobacteria CSU 206003 Leptospirillum ferrooxidans
CCTCC AB206160 iron protoxide hook end spirobacteria CSU 206004 Leptospirillum ferrooxidans
CCTCC AB206161 iron protoxide hook end spirobacteria CSU 206005 Leptospirillum ferrooxidans
CCTCC AB206162 iron protoxide hook end spirobacteria CSU 206006 Leptospirillum ferrooxidans
CCTCC AB206163 iron protoxide hook end spirobacteria CSU 206008 Leptospirillum ferrooxidans
CCTCC AB206164 iron protoxide hook end spirobacteria CSU 206009 Leptospirillum ferrooxidans
CCTCC AB207036 iron protoxide hook end spirobacteria CSU 206001 Leptospirillum ferrooxidans
CCTCC AB207037 iron protoxide hook end spirobacteria CSU 206007 Leptospirillum ferrooxidans
CCTCC AB207038 iron protoxide hook end spirobacteria CSU 206010 Leptospirillum ferrooxidans
CCTCC AB207044 thermophilic thiobacillus CSU206027 Acidithiobacillus caldus
CCTCC AB206175 thermophilic thiobacillus CSU206026 Acidithiobacillus caldus
CCTCC AB206176 thermophilic thiobacillus CSU206028 Acidithiobacillus caldus
CCTCC AB207045 sulfobacillus thermosulfidooxidans CSU 206043 Sulfobacillus thermosulfidooxidans
CCTCC AB207047 metal sulfolobus CSU 206047 Sulfolobus metallicus
The diligent metal coccus of CCTCC AB207046 CSU 206045 Metallosphaera sedula
The diligent metal coccus of CCTCC AB206191 CSU 206044 Metallosphaera sedula
The diligent metal coccus of CCTCC AB206192 CSU 206046 Metallosphaera sedula
CCTCC AB206219 wtih CSU 206091 Acidiphilium sp.
CCTCC AB206220 wtih CSU 206093 Acidiphilium sp.
CCTCC AB206221 wtih CSU 206094 Acidiphilium sp.
CCTCC AB206222 wtih CSU 206096 Acidiphilium sp.
CCTCC AB206223 wtih CSU 206097 Acidiphilium sp.
CCTCC AB206224 wtih CSU 206099 Acidiphilium sp.
CCTCC AB206225 wtih CSU 206101 Acidiphilium sp.
CCTCC AB 206226 wtih CSU 206103 Acidiphilium sp.
CCTCC AB 207065 wtih CSU 206092 Acidiphilium sp.
CCTCC AB 207066 wtih CSU 206095 Acidiphilium sp.
CCTCC AB 207067 wtih CSU 206098 Acidiphilium sp.
CCTCC AB 207068 wtih CSU 206100 Acidiphilium sp.
CCTCC AB 207069 wtih CSU 206102 Acidiphilium sp.
CCTCC AB 207070 wtih CSU 206104 Acidiphilium sp.
2,070,480,000 sour bacterium CSU 206050 Acidianus manzaensis of CCTCC AB.
Detailed process is following:
At first will leach required mikrobe and shake bottle at 2.5L respectively and carry out flexibility and cultivate, adopt every kind of corresponding chemical substratum of mikrobe; After every kind of equal continuous passage of mikrobe five times, be inoculated into the continuous enlarged culturing device of corresponding 50L, adopt breeze and concentrate to make mixed culture medium; Microorganism concn reaches 1-8 * 10 at least
7Behind the cell/mL, inoculate in the 5-10 ton ore storage, carry out ore deposit heap flexibility growth, make it be in logarithmic phase, microorganism concn reaches 1-8 * 10 at least
6Behind the cell/mL, be inoculated in the 100-500 ton ore storage, after 20-40 days again that the leaching in the ore storage is required mikrobe in the nutrient solution that enlarges according on show to make up:
Embodiment 1
The lump ore dump leaching:
Lay bottom and impervious barrier, bottom is the coarse sand of 300-400mm granularity, and flat heap thickness is the impact plies of broken in advance good+5-40mm grade copper mine stone macrobead lump ore of 200-300mm as the stockyard on impervious barrier; Continuation with fragmentation good+the copper mine stone macrobead lump ore of 5-40mm grade carries out thin layer and builds heap, every layer height 5-7m lays the 4-6 layer; Earlier use the pH value to spray in advance, guarantee that pH of leaching solution maintains 1.7-1.9, after pH of leaching solution is stablized 48 hours, according to 1-8 * 10 as the dilution heat of sulfuric acid of 0.9-1.2
6Cell/mL inoculates above-mentioned leaching microbacteria combination, beginning intermittent shower production operation and ventilation, and dump leaching 270 days, the leaching yield of copper is 90.11%, obtaining copper ion concentration is the leach liquor of 2.51g/L.
The agitation leach of fine ore bacterium:
With fragmentation good-the copper mine stone flour ore deposit and the vitriol oil of 5mm grade, contain above-mentioned leaching microbacteria combination and join steel basin, liquid-solid volume mass ratio is 2.33L/kg, makes that microorganism concn is 1-8 * 10 in the mixing solutions
6Cell/mL; The vitriolic mass concentration is 30-45g/L in the mixing solutions in the steel basin; The steel basin volume is 50M
3, constant temperature agitation leach 2h under the room temperature, mixing speed is 60 rev/mins, and the average technic index of working continuously month is: the leaching yield of copper is 92.32%, and sulfuric acid consumption is 3.18 tons of/ton copper, and obtaining copper ion concentration is the leach liquor of 4.85g/L.Two portions leach liquor mixes and to extract-the electrodeposition process operation, obtains the negative electrode electrolytic copper of 99.995% purity in the first batch.
It is following that extraction electrodeposition prepares the electrolytic copper detailed process, and extraction adopts secondary extraction one-level to strip; Adopt Lix-984 as extraction agent; Leach liquor is at first injected extraction stoste header tank; Flow to the extraction of extraction box two-stage with the extraction agent in the organic phase header tank at 1: 1 by comparing O/A, the surplus liquid in extraction back is from flowing to circulatory pool, and the continuation of blowback ore storage utilizes leaches; Extraction load organic phases and reverse-extraction agent are after the one-level back extraction, and unloaded organic phase is returned repeated use; Extract the surplus liquid of surplus liquid and electrodeposition and carry out full cut-off road recycle; Electrodeposition adopts Ai Safa; Liquid is handled from flowing to the electric effusion circulation groove through filtering after the back extraction, after plate-type heat exchanger is warmed to 40-42 ℃, flows into Winning cell and carries out electrodeposition, and the electrodeposition lean solution is returned and made reverse-extraction agent; 7 days negative electrode work periods, the manual removal cathode copper; The anode sludge cleaned once in 1 year, took away in groove with mobile pump.
Embodiment 2
According to the operation lump ore dump leaching of embodiment 1 270 days, the leaching yield of copper was 94.23%, and obtaining copper ion concentration is the leach liquor of 3.66g/L.
Operation fine ore bacterium according to embodiment 1 stirs, and the average technic index of working continuously month is: the leaching yield of copper is 95.62%, and sulfuric acid consumption is 3.65 tons of/ton copper, and obtaining copper ion concentration is the leach liquor of 5.78g/L.Two portions leach liquor mixes and to extract-the electrodeposition process operation, obtains the negative electrode electrolytic copper of 99.995% purity in the first batch.
Embodiment 3
According to the operation lump ore dump leaching of embodiment 1 270 days, the leaching yield of copper was 90.25%, and obtaining copper ion concentration is the leach liquor of 2.45g/L.
Operation fine ore bacterium according to embodiment 1 stirs, and the average technic index of working continuously month is: the leaching yield of copper is 92.32%, and sulfuric acid consumption is 3.25 tons of/ton copper, and obtaining copper ion concentration is the leach liquor of 4.75g/L.Two portions leach liquor mixes a part and extracts-the electrodeposition process operation, obtains the negative electrode electrolytic copper of 99.995% purity in the first batch.Part leach liquor obtains the copper sponge of cupric 88% through replacing process.
The detailed process that obtains copper sponge is following, and the leach liquor original ph is adjusted between 1.5～2.0, removes Fe before the displacement
3+, control Fe
3+Concentration is not higher than 0.2g/L; The displacement terminal point is that the pH value is controlled at below 4.5; Stirring intensity is 100～150rpm/s; The normal temperature displacement, time swap 30min.
Embodiment 4
According to the operation lump ore dump leaching of embodiment 1 270 days, the leaching yield of copper was 91.24%, and obtaining copper ion concentration is the leach liquor of 2.68g/L.
Operation fine ore bacterium according to embodiment 1 stirs, and the average technic index of working continuously month is: the leaching yield of copper is 92.32%, and sulfuric acid consumption is 3.36 tons of/ton copper, and obtaining copper ion concentration is the leach liquor of 4.97g/L.Two portions leach liquor part is mixed and is extracted-the electrodeposition process operation, obtains the negative electrode electrolytic copper of 99.995% purity in the first batch.Part leach liquor obtains the copper sponge of cupric 88% through replacing process.
Embodiment 5
The chemical multielement analysis of table 3 copper mining barren rock, %
Table 4 copper melting waste slag chemistry multielement analysis, %
Fine ore and acid block barren rock biological dump leaching:
The copper content of laying 300-400mm is that the copper mine of 0.09-0.30% is dug up mine acid block barren rock as bottom; Cover impervious barrier again, the thick granularity of flat heap 200-300mm is the copper mine fine ore of 5mm on impervious barrier, as the impact plies in stockyard; The ore deposit heap is carried out the paved in multi-layers mode; At first lay the acid block barren rock of the first layer copper mine, use the mortar pump with mass concentration be 30% copper mining tailing sand pump to barren layer, make mine tailing evenly firmly be distributed in the ore bed; Re-lay second layer barren layer, again the pump CHARACTERISTICS OF TAILINGS SAND; So repeatedly, every layer heap height until the ore deposit heap is 4-6M; Dump leaching begins to carry out sulfuric acid early stage and sprays in advance, guarantees to leach environment PH and maintains 1.7-1.9, and environment PH is stablized and carried out above-mentioned leaching microbacteria combination inoculation after 24 hours, and microorganism concn is 1-8 * 10
6Cell/mL carries out intermittent shower, and leach liquor is subsequent use;
Fine ore and fine grinding copper smelting-furnace slag granulation biological dump leaching:
When fine ore and fine grinding copper smelting-furnace slag are granulated; At first the copper smelting-furnace slag is carried out fragmentation and fine grinding operation; Making it-the 0.074mm grain size content reaches more than 50%; Adopt the sulfuric acid of 35-40g/L right-and the 0.074mm grain size content reaches 70% above fine ore and fine grinding copper smelting-furnace slag is made the ball granulation, and the back of granulating is opened wide and was placed 8-12 hour, makes its face stable curing balling; Dump leaching begins to carry out sulfuric acid early stage and sprays in advance, guarantees to leach environment pH value and maintains 1.7-1.9, and environment pH value stabilization carries out above-mentioned leaching microbacteria combination inoculation after 24 hours, and microorganism concn is 1-8 * 10
6Cell/mL carries out intermittent shower, and leach liquor is subsequent use.
The equal dump leaching 270 days of granulating of above-mentioned fine ore and acid block barren rock, fine ore and fine grinding copper smelting-furnace slag, the leaching yield of copper is 85.24%, obtaining copper ion concentration is the leach liquor of 1.65g/L.Leach liquor mixes and to extract-the electrodeposition process operation, obtains the negative electrode electrolytic copper of 99.95% purity in the first batch.A part obtains the copper sponge of cupric 87% through replacing process.
Claims (3)
1. the biological metallurgy leaching microbacteria composite bacterial solution of a copper mine stone is characterized in that, is process flexibility is cultivated, and the required mikrobe of the leaching after enlarged culturing and ore storage flexibility are cultivated continuously mixes, and obtaining concentration is 1-8 * 10
6The mixed bacteria liquid of cell/mL, described mixed bacteria liquid makes up according to the cell concn proportioning of unit volume: have a liking for the ferrous thiobacillus of acid oxidase 30 ± 5.0%, have a liking for acid oxidase sulphur thiobacillus 15 ± 3.0%, iron protoxide hook end spirobacteria 30 ± 5.0%, thermophilic thiobacillus 12 ± 3.0%, sulfobacillus thermosulfidooxidans 3 ± 0.5%, metal sulfolobus 2 ± 0.5%, diligent metal coccus 3 ± 0.5%, wtih 3 ± 0.5%, ten thousand sour bacterium 2 ± 0.5%; It is described that to have a liking for the ferrous thiobacillus of acid oxidase be that 16 kinds of preserving numbers are CCTCC AB 206199; CCTCCAB 206200; CCTCC AB 206201; CCTCC AB 206202; CCTCC AB 206203; CCTCC AB 206204; CCTCC AB 206205; CCTCC AB 206206; CCTCC AB 206207; CCTCC AB 206208; CCTCC AB207053; CCTCC AB 207054; CCTCC AB 207055; CCTCC AB 207056; CCTCC AB 207057; One or more of CCTCC AB 207058; Have a liking for acid oxidase sulphur thiobacillus and be 3 kinds of preserving numbers and be one or more of CCTCC AB206195, CCTCC AB 206196, CCTCC AB 206197; Iron protoxide hook end spirobacteria is that 10 kinds of preserving numbers are one or more of CCTCC AB206158, CCTCC AB 206159, CCTCC AB 206160, CCTCC AB 206161, CCTCC AB 206162, CCTCC AB 206163, CCTCC AB 206164, CCTCC AB 207036, CCTCCAB 207037, CCTCC AB 207038; Thermophilic thiobacillus is that 3 kinds of preserving numbers are one or more of CCTCC AB207044, CCTCC AB 206175, CCTCC AB 206176; Sulfobacillus thermosulfidooxidans CCTCCAB207045, metal sulfolobus CCTCC AB207047, diligent metal coccus are that 3 kinds of preserving numbers are one or more of CCTCC AB207046, CCTCC AB 206191, CCTCC AB 206192; Wtih is that 14 kinds of preserving numbers are one or more of CCTCCAB206219, CCTCC AB 206220, CCTCC AB 206221, CCTCC AB 206222, CCTCC AB 206223, CCTCC AB 206224, CCTCC AB 206225, CCTCC AB 206226, CCTCC AB 207065, CCTCC AB207066, CCTCC AB 207067, CCTCC AB 207068, CCTCC AB 207069, CCTCC AB 207070; Ten thousand sour bacterium CCTCC AB207048;
2-5%w/v copper mine breeze or concentrate that described ore storage flexibility cultivation is adding-0.074mm in chemical substratum are made mixed culture medium; Microorganism concn reaches 1-8 * 10 at least
7Behind the cell/mL, press 1-8 * 10 again
6Cell/mL is inoculated in the 5-10 ton ore storage, carries out ore deposit heap flexibility growth, makes it be in logarithmic phase, and microorganism concn reaches 1-8 * 10 at least
6Behind the cell/mL, press 1-8 * 10
6Cell/mL is inoculated in the 100-500 ton ore storage and cultivated 20-40 days.
2. application rights requires 1 described leaching microbacteria composite bacterial solution to carry out the biological metallurgy recovery method of copper mine stone, it is characterized in that, may further comprise the steps:
(1) lump ore biological dump leaching
Lay bottom and impervious barrier, flat heap thickness is the impact plies of broken in advance good+5-40mm grade copper mine stone macrobead lump ore of 200-300mm as the stockyard on impervious barrier; Continuation with fragmentation good+the copper mine stone macrobead lump ore of 5-40mm grade carries out thin layer and builds heap, dilution heat of sulfuric acid sprays in advance, then according to 1-8 * 10
6The described leaching microbacteria composite bacterial solution of cell/mL inoculation claim 1, beginning intermittent shower production operation and ventilation, leach liquor is subsequent use;
(2) fine ore stirs the bacterium living beings drill traverse
With fragmentation good-the copper mine stone flour ore deposit and the vitriol oil of 5mm grade, contain right and require 1 described leaching microbacteria composite bacterial solution to join steel basin, make that microorganism concn is 1-8 * 10 in the mixing solutions
6Cell/mL; In steel basin, carry out agitation leach, leach liquor is subsequent use;
(3) mine tailing granulation biological dump leaching
At first copper mining tailing is made ball and granulate, granularity is controlled at 20mm, and the copper mine fine ore of laying the thick granularity of 150-200mm and be 5mm re-lays impervious barrier as bottom, and the coarse sand of flat heap 200-300mm thickness on impervious barrier is as the impact plies in stockyard; Be that the pelletizing shape copper mining tailing of 20mm is laid and built heap to the granularity after making ball and granulating on the impact plies then, dump leaching begins to carry out sulfuric acid early stage and sprays in advance, inoculates the described leaching microbacteria composite bacterial solution of claim 1 then, and microorganism concn is 1-8 * 10
6Cell/mL carries out intermittent shower, and leach liquor is subsequent use;
(4) fine ore and acid block barren rock biological dump leaching
The copper content of laying granularity and be 40mm-60mm is that the copper mine of 0.09-0.3% is dug up mine acid block barren rock as bottom, and thickness is 300-400mm; Cover impervious barrier again; The thick granularity of flat heap 200-300mm is the copper mine fine ore of 5mm on impervious barrier; As the impact plies in stockyard, the ore deposit heap is carried out the paved in multi-layers mode, at first lays the acid block barren rock of the first layer copper mine; Use the mortar pump with mass concentration be 30% copper mining tailing sand pump to barren layer, make mine tailing evenly firmly be distributed in the ore bed; Re-lay second layer barren layer, again the pump CHARACTERISTICS OF TAILINGS SAND; So repeatedly, every layer heap height until the ore deposit heap is 4-6m; Dump leaching begins to carry out sulfuric acid early stage and sprays in advance, carries out the described leaching microbacteria composite bacterial solution inoculation of claim 1 then, and microorganism concn is 1-8 * 10
6Cell/mL carries out intermittent shower, and leach liquor is subsequent use;
(5) fine ore and fine grinding copper smelting-furnace slag granulation biological dump leaching
At first the copper smelting-furnace slag is carried out fragmentation and fine grinding; Make ball with fine ore then and granulate, granularity is controlled at 20mm, and it is thick to lay 150-200mm; Granularity is that the fine ore of 5mm is as bottom; Cover impervious barrier above again, the process of flat heap 200-300mm thickness is made fine grinding smelted furnace cinder and the fine ore that ball is granulated on impervious barrier, as the impact plies in stockyard; Continue then carrying out dump leaching through fine grinding smelted furnace cinder and the fine ore of making the ball granulation, dump leaching begins to carry out sulfuric acid early stage and sprays in advance, carries out the described leaching microbacteria composite bacterial solution inoculation of claim 1 then, and microorganism concn is 1-8 * 10
6Cell/mL carries out intermittent shower, and leach liquor is subsequent use;
(6) one or more leach liquor extraction electrodepositions that above-mentioned steps (1)-(5) obtained prepare electrolytic copper; One or more leach liquors that perhaps above-mentioned steps (1)-(5) obtained obtain copper sponge with iron powder replacement;
In the described lump ore biological dump leaching of step (1), described bottom is the coarse sand of 300-400mm thickness, and described fragmentation is good+and the copper mine stone of 5-40mm grade carries out thin layer and builds heap, and every layer height 5-7m lays the 4-6 layer; Earlier use the pH value to spray in advance, guarantee that pH of leaching solution maintains 1.7-1.9 as the dilution heat of sulfuric acid of 0.9-1.2, after pH of leaching solution is stablized 48 hours, the described leaching microbacteria composite bacterial solution of inoculation claim 1;
The described fine ore of step (2) stirs in the bacterium living beings drill traverse, and the vitriolic mass concentration is 30-45g/L in the mixing solutions in the steel basin; Mixing speed is 40-60 rev/min; In whipping process, utilize air compressor machine blowing air in steel basin, leach reaction 1-3 hour;
In the described mine tailing granulation of step (3) biological dump leaching; The dilute sulphuric acid of adding 2% when making the ball granulation; Granularity is controlled at 20mm, and dump leaching begins to carry out sulfuric acid early stage and sprays in advance, guarantees to leach environment pH value and maintains 1.7-1.9; PH value stabilization 24 hours, the described leaching microbacteria composite bacterial solution of inoculation claim 1;
In described fine ore of step (4) and the acid block barren rock biological dump leaching; Dump leaching begins to carry out sulfuric acid early stage and sprays in advance; Guarantee to leach environment PH and maintain 1.7-1.9, environment PH is stablized and is carried out the said leaching microbacteria composite bacterial solution inoculation of claim 1 after 24 hours;
In described fine ore of step (5) and the fine grinding copper smelting-furnace slag granulation biological dump leaching; When fine ore and fine grinding copper smelting-furnace slag are granulated; At first the copper smelting-furnace slag is carried out fragmentation and fine grinding operation, make it-the 0.074mm grain size content is not less than 50%, adopt the sulfuric acid of 35-40g/L that it is made ball and granulate; Granulating, the back is unlimited placed 8-12 hour, made its face stable curing balling; Dump leaching begins to carry out sulfuric acid early stage and sprays in advance, guarantees to leach environment pH value and maintains 1.7-1.9, and environment pH value stabilization carries out the described leaching microbacteria composite bacterial solution inoculation of claim 1 after 24 hours.
3. the biological metallurgy recovery method of copper mine stone according to claim 2 is characterized in that, the described impervious barrier of step (1) (3) (4) (5) is the acid proof PVC geotextile of 1mm-3mm thickness.
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| PCT/CN2011/001790 WO2012055167A1 (en) | 2010-10-31 | 2011-10-26 | Bacterial liquid of microbial combinations for biometallurgical leaching of copper ore and method for recovering metallic copper therefrom |
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| CN101956071B (en) * | 2010-10-31 | 2012-04-11 | 中南大学 | Biological metallurgy mineral leaching microorganism combined bacterium fluid for copper ore and method for recycling metallic copper |
| JP5848440B2 (en) * | 2012-04-27 | 2016-01-27 | 京セラ株式会社 | Method for recovering tungsten compounds |
| CN103014335B (en) * | 2013-01-10 | 2014-08-13 | 紫金矿业集团股份有限公司 | Process for comprehensively recovering gold and copper through combined biological dump leaching of refractory gold concentrate and copper melting slag |
| CN103396964B (en) * | 2013-08-01 | 2015-04-29 | 中南大学 | Compound bacterium community capable of efficiently leaching sulphide ore, and compounding method and application method thereof |
| CN103451437B (en) * | 2013-09-06 | 2015-07-08 | 聂源 | Recovery and utilization method of valuable metal sludge containing copper, nickel and cobalt |
| CN104745497B (en) * | 2013-12-30 | 2018-03-16 | 北京有色金属研究总院 | A kind of technique for carrying out high sulfur coal mine biological desulphurization using exclusive desulfurization Mixed Microbes |
| EA028575B1 (en) * | 2014-04-08 | 2017-12-29 | Тоо "Биопром Технолоджиес" | Consortium of mesophilic and moderately thermophilic chemolithotrophic bacteria for tank leaching of refractory sulphide-containing ores |
| CN104130963B (en) * | 2014-07-31 | 2016-09-07 | 黑龙江八一农垦大学 | One strain is addicted to acid iron-oxidizing bacteria and the purposes in copper mine leaches thereof |
| CN104152691B (en) * | 2014-08-08 | 2016-04-27 | 西北矿冶研究院 | Biological heap leaching process for stripping copper sulfide ore in open air |
| CN105154671B (en) * | 2015-07-23 | 2018-03-16 | 中南大学 | Fine particle industrial solid wastes build heap technique and its application |
| CN105821210B (en) * | 2016-05-11 | 2017-11-07 | 中南大学 | It is a kind of to build the high method containing fine tailings of heap processing based on Biofilms |
| CN106381386B (en) * | 2016-09-27 | 2018-12-25 | 章梦涛 | A kind of leaching processing method of low-grade high shale content copper mine |
| CN109777756A (en) * | 2019-02-13 | 2019-05-21 | 黑龙江八一农垦大学 | A kind of microbial inoculum and the application of simultaneous removing hydrogen sulfide and ammonia |
| CN110863117B (en) * | 2019-11-22 | 2021-05-04 | 江南大学 | Method for promoting leaching of poor chalcocite biological column |
| CN112680600B (en) * | 2020-12-17 | 2022-06-10 | 有研资源环境技术研究院(北京)有限公司 | Process for recovering copper and enriching precious metals from sponge copper slag through biological oxidation |
| CN116043014A (en) * | 2023-02-09 | 2023-05-02 | 中国科学院过程工程研究所 | Method for combined leaching of ores |
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