CN1556230A - Method of leaching copper in copper containing pyrite using bacteria - Google Patents
Method of leaching copper in copper containing pyrite using bacteria Download PDFInfo
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- CN1556230A CN1556230A CNA2004100228264A CN200410022826A CN1556230A CN 1556230 A CN1556230 A CN 1556230A CN A2004100228264 A CNA2004100228264 A CN A2004100228264A CN 200410022826 A CN200410022826 A CN 200410022826A CN 1556230 A CN1556230 A CN 1556230A
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- 229910052683 pyrite Inorganic materials 0.000 title claims abstract description 70
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000011028 pyrite Substances 0.000 title claims abstract description 70
- 239000010949 copper Substances 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000002386 leaching Methods 0.000 title claims description 71
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 68
- 229910052802 copper Inorganic materials 0.000 title claims description 68
- 241000894006 Bacteria Species 0.000 title abstract description 22
- 230000008569 process Effects 0.000 claims abstract description 13
- 238000005507 spraying Methods 0.000 claims description 32
- 230000001580 bacterial effect Effects 0.000 claims description 25
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 17
- 230000035699 permeability Effects 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 11
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 11
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 10
- 241000605222 Acidithiobacillus ferrooxidans Species 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 8
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 6
- 239000001963 growth medium Substances 0.000 claims description 6
- 239000002054 inoculum Substances 0.000 claims description 6
- 239000005751 Copper oxide Substances 0.000 claims description 5
- 229910000431 copper oxide Inorganic materials 0.000 claims description 5
- -1 iron ions Chemical class 0.000 claims description 5
- 239000007921 spray Substances 0.000 claims description 5
- 241000605272 Acidithiobacillus thiooxidans Species 0.000 claims description 4
- 235000015097 nutrients Nutrition 0.000 claims description 4
- 238000012258 culturing Methods 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 150000001447 alkali salts Chemical class 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 230000035515 penetration Effects 0.000 claims 1
- 235000011149 sulphuric acid Nutrition 0.000 claims 1
- 239000001117 sulphuric acid Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 8
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 abstract description 7
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- PQTCMBYFWMFIGM-UHFFFAOYSA-N gold silver Chemical compound [Ag].[Au] PQTCMBYFWMFIGM-UHFFFAOYSA-N 0.000 abstract description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 10
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical compound [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 6
- 229910052951 chalcopyrite Inorganic materials 0.000 description 6
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 6
- 229910001431 copper ion Inorganic materials 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical class [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 4
- 241000193830 Bacillus <bacterium> Species 0.000 description 3
- FQGMPQGXUXIOKI-UHFFFAOYSA-N [S--].[S--].[Cu++].[Zn++] Chemical compound [S--].[S--].[Cu++].[Zn++] FQGMPQGXUXIOKI-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 229910052950 sphalerite Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052569 sulfide mineral Inorganic materials 0.000 description 3
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 3
- 241001290773 Acidiphilium acidophilum Species 0.000 description 2
- 241000589925 Leptospirillum Species 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 241000605118 Thiobacillus Species 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005188 flotation Methods 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
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000589921 Leptospirillum ferrooxidans Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 241000205098 Sulfolobus acidocaldarius Species 0.000 description 1
- 241000607598 Vibrio Species 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000001166 ammonium sulphate Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052947 chalcocite Inorganic materials 0.000 description 1
- 229910001779 copper mineral Inorganic materials 0.000 description 1
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 235000019797 dipotassium phosphate Nutrition 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
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- Manufacture And Refinement Of Metals (AREA)
Abstract
A process for extracting Cu from the Cu-contained pyrite by bacteria features that the electrochemical catalyzing action of bacteria to different sulfide ores is used sufficiently, that is, the low-potential copper sulfide is used as corrosion anode, the high-potential pyrite or gold-silver ore is used as cathode, the bacteria are used to promote the Galvanic ell effect between them, and for the residual pyrite, the special microspirobacteria are used to suppress its oxidization. Its extraction-out rate can reach more than 75% within 4 months.
Description
Technical Field
The invention relates to a leaching method of copper in copper-containing pyrite, in particular to a bacterial leaching method of copper in copper-containing pyrite.
Background
Pyrite is a mineral raw material in chemical enterprises, and is used for producing sulfur or sulfuric acid. The pyrite is generally associated with about 0.1-1.0% of copper. For chemical enterprises, copper is a harmful impurity element, the quality of pyrite is reduced, and sometimes, the pyrite is difficult to sell or reduce the price of mine enterprises due to high copper content. For non-ferrous enterprises, copper is a valuable metal, and the traditional flotation process can be adopted, so that the harm is changed into the benefit, and the waste is changed into the treasure. However, because the copper grade is low, and the copper oxide part is generally lost in the flotation tail liquid, the recovery rate is low, and the cost is high, the method is difficult to win.
The bacterial leaching technology has the characteristics of low cost, high leaching rate and the like, and is an effective method for recovering copper in the pyrite. However, some pyrites are in the form of fine sludge with poor permeability; some pyrites contain sphalerite besides chalcopyrite, and the sphalerite often inhibits leaching of the chalcopyrite in the process of leaching copper by bacteria; in addition, because the pyrite is a main mineral and the content of the pyrite is far higher than that of a copper mineral, the pyrite is inevitably and partially oxidized at the same time in the bacterial leaching process, so that the acid yield of the solution is high, the pH value is greatly reduced, the activity of copper leaching bacteria is influenced, and the copper leaching rate is reduced; on the other hand, the reduction of sulfur is caused, and the sulfur content of the pyrite is reduced.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the bacterial leaching method which has low cost and high leaching rate, can quickly recover copper in pyrite and does not influence the sulfur content of the pyrite.
The technical principle of the bacterial leaching method for recovering copper in pyrite is as follows. The inventor researches the chemical components and phase compositions of the copper-containing pyrite and the bacterial leaching mechanism, and finds that copper sulfide generally exists in the forms of chalcopyrite, chalcocite and a small amount of copper oxide ore, and the copper sulfide minerals are distributed in the pyrite in a strip shape and a block shape, are sometimes staggered and mutually contained, have more cracks and are mostly oxidized into copper blue on the surface; chalcopyrite, zinc blende and pyrite are symbiotic, and gold particles and silver gold ores are often associated in gaps.
According to the distribution characteristics, the electrochemical catalysis of bacteria among different sulfide minerals is fully utilized, namely, low-potential copper sulfide is used as a corrosion anode, high-potential pyrite and gold and silver ores are used as cathodes, and the bacteria are utilized to promote the primary battery effect among the copper sulfide and the copper sulfide; other pyrites which do not form the primary battery effect inhibit the activity of the obligate bacteria (leptospirillum spp) of oxidized pyrite by controlling the process conditions, thereby achieving the purpose of slowing down the oxidation of the pyrite. The method comprises the following steps: before leaching by using the bacterial leaching solution, firstly leaching copper oxide in the leaching solution by using sulfuric acid with the concentration of 1-2g/L, and then catalyzingleaching of zinc blende by using leached copper ions, wherein the zinc blende is catalytically leached, so that the potential inhibition effect of the zinc blende on the leaching of chalcopyrite bacteria is eliminated earlier, and the reaction is as follows:
the crystal lattice of the zinc blende is damaged due to the substitution of metal ions, the substituted product cannot form a complete crystal lattice and is easily oxidized by high iron, the reduced ferrous iron is oxidized by bacteria to be regenerated, the whole reaction is repeated in cycles, the bacterial leaching of the zinc blende is accelerated, and meanwhile, the potential inhibition of the zinc blende on the chalcopyrite is eliminated earlier.
The invention adopts a bacterial oxidation method to leach copper in pyrite, and the strains mainly comprise some moderate-temperature strains, such as Thiobacillus ferrooxidans (Thiobacillus ferrooxidans), ferrous ferrooxidans (Ferrobacillus ferrooxidans), Thiobacillus thiooxidans (Ferrobacillus thiooxidans), Thiobacillus acidophilus (Thiobacillus acidophilus) and the like. High temperature species such as sulfolobus acidocaldarius, microluo (leptospirillum theoferrooxidans), Thiobacillus thermosulfidooxidans (Sykfibacillus thermosulfidooxidans), etc. as well as microluo (leptospirillum ferrooxidans) and Thiobacillus thiooxidans (Thiobacillus thiooxidans) should not be inoculated and the activity of its natural species should be inhibited by process conditions to prevent these bacteria from excessively oxidizing sulfur in pyrite.
The specific process of the invention is as follows:
① making into piles
The method comprises the following steps of (1) alternately stacking the fine and muddy pyrites and blocky pyrites in a layered mode, determining the layer thickness degree of the fine and muddy pyrites according to the relative resource quantity of the two types of pyrites and the maximum permeability of the fine and muddy pyrites measured before stacking, and enabling the fine and muddy pyrite layer to be as thin as possible, wherein the fine and muddy pyrite layer is generally not more than 5m, and the preferred thickness is 1-3 m; the permeability is preferably maintained at 10L/h.m2Above, the minimum should be not less than 5L/h.m2Otherwise, the spray system would be difficult to operate unless the drip system is used instead. The massive pyrite does not need to be crushed because the crystal grains are generally not large, the aggregate of the crystal grains is looser, copper sulfide is distributed among cracks in a strip shape, and the granularity cannot influence the leaching rate of bacteria on copper.
In addition to the above considerations, it is preferable to stack a layer of high-grade and high-oxidation-rate pyrite with copper on top of each layer of pyrite containing copper and zinc sulfides, so that the copper ions leached by sulfuric acid can catalyze the leaching of zinc from the underlying pyrite and the potential inhibition of the pyrite by the sphalerite can be released early.
Other heap leaching requires the same general heap leaching method.
② culturing strain and preparing nutrients from its liquid extract
The strain is mainly Thiobacillus ferrooxidans, and can also be ferrous iron oxideBacillus ferrooxidans, ferrous sulfur oxide Bacillus, etc. The inoculum is preferably isolated, purified and improved, and the inoculum improvement can be carried out according to the method described in the present invention patent application No. 03124788.1, which was filed on 9/3/2003 by the present inventors. The strains with stronger pyrite oxide, such as ferrous oxide micro-spirochete bacteria and high-temperature ferrous oxide micro-spirochete bacteria, are not suitable to exist, and the bacteria with strong sulfur oxide capacity, such as sulfur oxide thiobacillus and the like, are also not suitable to be removed. The strain culture medium is prepared by adding 1-6g/L (preferably 2-4g/L) of ammonium sulfate into 5-20% (w/v) of ore pulp (preferably 10-15% ore pulp); dipotassium hydrogen phosphate 0.1-1.0g/L (preferably 0.3-0.7 g/L); the pH value is 1.0-3.0, and the optimal range is 1.7-2.5. Other nutrient media, such as magnesium sulfate, may not be added, as the mineral content is generally sufficient. The inoculum can also be cultured with 9k basic salt, but the amount of ferrous sulfate is preferably selected from 34-22 g/L.
The preparation of the leaching solution is basically the same as that of a seed bacteria culture solution, ferrous sulfate is not suitable to be added into the leaching solution, and the growth of the microspira is promoted by overhigh iron; the concentration of iron is controlled below 5g/L, preferably not more than 3 g/L; the addition amount and pH value of ammonium sulfate and dipotassium hydrogen phosphate are the same as those of the seed bacteria culture solution.
③ spray or drip
Inoculating the strain into the leaching solution according to the proportion of 0.05-5% (v/v), and immediately spraying; the liquid-solid ratio of the leaching solution to the pyrite is preferably 1: 5-100, and preferably 1: 10-50. Since the passage time and growth condition of Thiobacillus ferrooxidans are better controlled than those of Microspirillum, it will become the main bacterium for leaching and preferentially decompose copper sulphide minerals.
The first spraying is extremely important, and the maximum permeability and the maximum adsorption capacity of the pile are predicted. The specific method comprises the following steps: spraying with 1/4-1/2 spraying strength of maximum permeability, and spraying with 1/4-3/4 spraying strength of maximum permeability after the spraying amount reaches the maximum adsorption amount, preferably 1/3-2/3.
During leaching, the iron concentration of the leaching liquid is preferably controlled to be below 5g/L, and preferably not more than 3 g/L.
The spraying system should also be considered, and it should be distinguished from cold and warm wind in spring, summer, autumn and winter, rainy days, fine days and daytime at night. Generally, the spraying time is 8-10 points and 17-19 points every day, and the spraying is stopped at 10-17 points and at night; it is not suitable for spraying in rain, and can be sprayed once in short time (1-2 hr) when it rains continuously for more than 24 hr, and its intensity is preferably low, and is preferably 1/5-/4 of maximum permeability. It is not suitable for spraying when blowing strong wind. In winter, the spraying time should be shortened by 1-2 hours.
When the permeability of the ore heap is not good enough, a dripping system can be adopted.
④ recovery of copper sulfate solution
The copper ions in the leachate can be enriched by known extraction methods. When the concentration of copper ions reaches more than 1g/L, extraction is carried out in time. The extraction pregnant solution is used for producing the electric copper plate according to the traditional electrodeposition process. Theextraction tail liquid returns to the pile or enters a tail liquid pool.
The invention has the following positive effects: under the conditions of natural granularity and natural weather, the leaching rate of copper can reach over 75 percent after bacteria leaching for 4 months; the coexistence of copper-zinc sulfide and pyrite can realize the simultaneous leaching of copper and zinc, and the leaching effect is similar to that of zinc-free sulfide minerals.
The benefits are as follows: the bacterial leaching of copper from copper-bearing pyrite has high benefit and little pollution. If the production cost is only 0.5 ten thousand yuan/ton (almost negligible because the amount of sulfuric acid is very small) calculated by the current copper price of 2.0 ten thousand yuan/ton, the copper per ton can be profitable by about 1.5 ten thousand yuan. In addition, because bacteria are used for leaching impurity elements such as copper, calcium, magnesium, aluminum, potassium, silicon and the like, the removed impurity amount can reach more than 7 percent of the total amount, the sulfur content of the pyrite is increased, the quality is improved, the original low-grade waste pyrite (S is less than or equal to 30 percent) can be easily sold from difficult sale, and the benefit of about 30-100 yuan per ton of pyrite can be increased for enterprises.
Detailed Description
The invention is further illustrated by the following examples.
Example 1 bacterial leaching of copper from copper-containing pyrite
(1) Piling the fine mud-shaped copper-containing pyrite and the blocky copper-containing pyrite according to the proportion of 1: 2, and layering and piling the fine mud-shaped pyrite layer with the thickness of 1.5m and the blocky pyrite layer with the thickness of 2.7 m; piling 600 tons of bacterial heap with the average copper content of about 0.4%; 38m of adsorbed water in the pile3(ii) a (2) The method mainly comprises the steps of culturing strains and preparing nutrient leaching solution, wherein the culture medium is 10% (w/v) ore pulp, 4g/L of ammonium sulfate and 0.5g/L of dipotassium phosphate are added, and the pH value is 2.0. Preparing a leaching solution; of ammonium sulphate and dipotassium hydrogen phosphateThe adding amount is respectively 5g/L and 0.4g/L, and a small amount of sulfuric acid is added to adjust the pH value to 2.0; is totally leachedIn the process, the concentration of iron ions is controlled to be below 3g/L by a sedimentation tank; (3) the volume of the spray leaching liquid is 41m3Inoculating the strain into the leaching solution according to the proportion of 2% (v/v), and immediately spraying; maximum permeability 54Lh-1m-2(ii) a The spraying intensity is controlled to be 18-27Lh-1m-2. Spraying at 8-10 am and 17-19 pm on days with temperature over 15 deg.C, and spraying at less than 15 deg.C for one hour each time.
When the copper is leached for two months, the leaching rate of the copper reaches 54 percent, and when the copper is leached for four months, the leaching rate of the copper reaches 79 percent. Except that a small amount of sulfuric acid is added when the pH of the leaching solution is adjusted, acid is basically not added in the whole leaching process, the pH is naturally kept between 2.0 and 2.5 all the time, and the phenomenon of pH reduction caused by a large amount of acid production does not occur. After copper leaching, the sulfur content in the leaching residue is improved by 1.9 percent compared with the original pyrite.
Example 2 bacterial leaching of copper and zinc from pyrite containing copper and zinc sulphides
(1) Piling up the pyrite containing copper and zinc sulfides and fine muddy pyrite with the oxidation rate of about 30 percent and the copper grade of about 0.8 percent in a layering manner according to the proportion of 1: 1; fine muddy pyrite is arranged on the upper layer, and pyrite containing copper-zinc sulfide is arranged on the lower layer, so that copper oxide on the upper layer can be leached by sulfuric acid, and leached copper ions can catalyze bacterial leaching of zinc on the lower layer, and further the bacterial leaching of copper in the copper-zinc sulfide can be accelerated; each layer is 2m thick and piled into 500 tons; (2) the strain culture and leachate nutrition preparation strain uses Thiobacillus ferrooxidans, ferrous oxide bacillus and ferrous oxide bacillus, the used culture medium is 8% (w/v) ore pulp, 5g/L ammonium sulfate, 0.2g/L dipotassium hydrogen phosphate and pH value is 1.5. Preparing a leaching solution, wherein the adding amount of ammonium sulfate and dipotassium hydrogen phosphate is 2g/L and 0.8g/L respectively, and adjusting the pH value to 1.8; controlling the concentration of iron ions to be less than 4g/L in the leaching process; (3) spraying sulfuric acid with the concentration of 1-2g/L to leach copper oxide in the zinc blende, and then catalyzing the leached copper ions to leach the zinc blende; then inoculating the strain at a ratio of 1% (v/v) to 80m3Immediately spraying the leachate; maximum permeability of 45Lh in fine-mud pyrite deposit-1m-2(ii) a The spraying intensity is controlled to be 15-20Lh-1m-2. Other spraying conditions were the same as in example 1.
Leaching for four months, wherein the total leaching rate of the mixed pile reaches 76 percent. The leaching rates of the unmixed pyrite containing copper and zinc sulfide are 71% and 57% respectively.
Claims (10)
1. A bacterial leaching method for copper in copper-containing pyrite is characterized by comprising the following steps:
(1) making piles
Alternately stacking the fine and blocky pyrites in a layered manner, determining the layer thickness degree of the fine and blocky pyrites according to the relative resource amount of the two types of pyrites and the maximum permeability of the fine and blocky pyrites measured before stacking, wherein the thickness of the fine and blocky pyrites is less than or equal to 5m, and the permeability is more than or equal to 5L/hm2；
(2) Culturing strain and preparing nutrients from its extract
The strain comprises at least one of thiobacillus ferrooxidans, ferrobacillus ferrooxidans and thiobacillus thiooxidans, wherein a culture medium used for culture is 5-20% (w/v) ore pulp, 1-6g/L of ammonium sulfate, 0.1-1.0g/L of dipotassium hydrogen phosphate and 1.0-3.0 of pH value are added; or 9k basic salt is used, and the adding amount of ferrous sulfate is 34-22 g/L;
preparing a leaching solution, wherein the adding amount of ammonium sulfate and dipotassium hydrogen phosphate is 1-6g/L and 0.1-1.0g/L respectively, the pH value is 1.0-3.0, and the concentration of iron ions is controlled below 5g/L in the leaching process;
(3) spraying or dripping
Inoculating the strain into the leachate at a ratio of 0.05-5% (v/v), and immediately spraying or dripping; the liquid-solid ratio of the leaching solution to the pyrite is 1: 5-100;
the first spraying is carried out with the spraying strength of 1/4-1/2 with the maximum permeability of the fine mud-like pyrite layer; after the spraying amount reaches the maximum adsorption amount, spraying according to the spraying strength 1/4-3/4 of themaximum permeability of the fine mud-shaped pyrite layer; the spraying time is 8-10 points and 17-19 points per day;
(4) and recovering the copper sulfate solution.
2. The method for the bacterial leaching of copper from copper-containing pyrite according to claim 1, wherein the thickness of said fine slimy pyrite layer is 1-3m when heaped.
3. The method for bacterial leaching of copper from copper-containing pyrite according to claim 1, wherein said inoculum is Thiobacillus ferrooxidans.
4. The method for the bacterial leaching of copper from pyrite containing copper according to claim 1, 2 or 3, wherein the culture medium used for the inoculum culture is 10-15% (w/v) pulp, ammonium sulfate 2-4g/L and/or dipotassium hydrogen phosphate 0.3-0.7g/L is added; the pH value is 1.7-2.5.
5. The method for bacterial leaching of copper from a copper-containing pyrite according to claim 1, 2, or 3, wherein said leachate has an iron ion concentration of 3g/L or less, ammonium sulfate and dipotassium hydrogen phosphate are added in amounts of 2-4g/L and 0.3-0.7g/L, respectively, and a pH of 1.7-2.5.
6. A method for bacterial leaching of copper from a copper-containing pyrite according to claim 1, 2, or 3, wherein the liquor-to-solid ratio of leachate to pyrite is in the range of 1: 10 to 50.
7. A method for bacterial leaching of copper from a copper-containing pyrite according to claim 1, 2, or 3, wherein after the first spraying, the spraying is performed at a maximum penetration spray intensity of 1/3-2/3.
8. A method for bacterial leaching of copper from copper-containing pyrite according to claim 1, 2, or 3, wherein the spraying is done once on days that continuously rain for more than 24 hours, for a period of 1-2 hours, at a spray intensity of 1/5-1/4 of maximum permeability of the fine slime layer of pyrite.
9. A method as claimed in claim 1, 2 or 3, wherein the bacterial leach solution is subjected to leaching of copper oxide in the copper-containing pyrite using sulphuric acid at a concentration of 1 to 2g/L prior to leaching.
10. The bacterial leaching process of copper from pyrite containing copper according to claim 4, wherein the culture medium used for the inoculum culture is 10-15% (w/v) pulp, ammonium sulfate 2-4g/L and/or dipotassium hydrogen phosphate 0.3-0.7g/L are added; the pH value is 1.7-2.5 s.
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