CN116855754A - Method for cooperatively leaching gold, silver and manganese from manganese-silver ore, high-arsenic high-sulfur gold-loaded pyrite and thiobacillus ferrooxidans - Google Patents
Method for cooperatively leaching gold, silver and manganese from manganese-silver ore, high-arsenic high-sulfur gold-loaded pyrite and thiobacillus ferrooxidans Download PDFInfo
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- 238000002386 leaching Methods 0.000 title claims abstract description 165
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 147
- 239000004332 silver Substances 0.000 title claims abstract description 147
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 144
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 132
- 239000010931 gold Substances 0.000 title claims abstract description 132
- 238000000034 method Methods 0.000 title claims abstract description 119
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 229910052683 pyrite Inorganic materials 0.000 title claims abstract description 98
- 239000011028 pyrite Substances 0.000 title claims abstract description 98
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 93
- 239000011572 manganese Substances 0.000 title claims abstract description 93
- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 80
- 239000011593 sulfur Substances 0.000 title claims abstract description 74
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 74
- GZUCQIMKDHLSEH-UHFFFAOYSA-N manganese silver Chemical compound [Mn][Ag][Ag] GZUCQIMKDHLSEH-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 241000605222 Acidithiobacillus ferrooxidans Species 0.000 title claims abstract description 32
- 230000008569 process Effects 0.000 claims abstract description 75
- PQTCMBYFWMFIGM-UHFFFAOYSA-N gold silver Chemical compound [Ag].[Au] PQTCMBYFWMFIGM-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000002893 slag Substances 0.000 claims abstract description 37
- 239000007788 liquid Substances 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 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 claims abstract description 13
- 238000006479 redox reaction Methods 0.000 claims abstract description 12
- 238000000227 grinding Methods 0.000 claims abstract description 11
- 230000003716 rejuvenation Effects 0.000 claims abstract description 9
- 238000004537 pulping Methods 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 8
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 17
- 230000003472 neutralizing effect Effects 0.000 claims description 15
- 241000093877 Acidithiobacillus sp. Species 0.000 claims description 13
- 239000012535 impurity Substances 0.000 claims description 11
- 238000005273 aeration Methods 0.000 claims description 10
- 238000011081 inoculation Methods 0.000 claims description 8
- 229940099596 manganese sulfate Drugs 0.000 claims description 8
- 239000011702 manganese sulphate Substances 0.000 claims description 8
- 235000007079 manganese sulphate Nutrition 0.000 claims description 8
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000292 calcium oxide Substances 0.000 claims description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 6
- 239000002054 inoculum Substances 0.000 claims description 6
- 239000003814 drug Substances 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 238000012258 culturing Methods 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 29
- 239000000463 material Substances 0.000 abstract description 22
- 238000005265 energy consumption Methods 0.000 abstract description 13
- 238000005272 metallurgy Methods 0.000 abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 55
- 238000006243 chemical reaction Methods 0.000 description 52
- 241000894006 Bacteria Species 0.000 description 39
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 24
- 238000007254 oxidation reaction Methods 0.000 description 24
- 230000003647 oxidation Effects 0.000 description 23
- 230000002195 synergetic effect Effects 0.000 description 20
- 229910052500 inorganic mineral Inorganic materials 0.000 description 19
- 239000011707 mineral Substances 0.000 description 19
- 235000010755 mineral Nutrition 0.000 description 19
- 238000013019 agitation Methods 0.000 description 18
- 230000001580 bacterial effect Effects 0.000 description 17
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 16
- 239000002253 acid Substances 0.000 description 14
- 230000008901 benefit Effects 0.000 description 14
- 230000000694 effects Effects 0.000 description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 13
- 229910001655 manganese mineral Inorganic materials 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000003153 chemical reaction reagent Substances 0.000 description 9
- 238000006386 neutralization reaction Methods 0.000 description 9
- 238000000746 purification Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 230000001737 promoting effect Effects 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- MMIGAXTWRKZSOT-UHFFFAOYSA-N manganese;oxosilver Chemical compound [Mn].[Ag]=O MMIGAXTWRKZSOT-UHFFFAOYSA-N 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000033116 oxidation-reduction process Effects 0.000 description 3
- 229910001739 silver mineral Inorganic materials 0.000 description 3
- 241000605118 Thiobacillus Species 0.000 description 2
- 239000001963 growth medium Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 239000009916 yin-huang Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- WNOFCXXERXPMFQ-UHFFFAOYSA-N [Mn].[Ag].[Au] Chemical compound [Mn].[Ag].[Au] WNOFCXXERXPMFQ-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 229910052598 goethite Inorganic materials 0.000 description 1
- DAFYMZZLYPHPNG-UHFFFAOYSA-N gold;thiourea Chemical compound [Au].NC(N)=S DAFYMZZLYPHPNG-UHFFFAOYSA-N 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- LFAGQMCIGQNPJG-UHFFFAOYSA-N silver cyanide Chemical compound [Ag+].N#[C-] LFAGQMCIGQNPJG-UHFFFAOYSA-N 0.000 description 1
- 229940098221 silver cyanide Drugs 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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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
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
- C12N1/20—Bacteria; Culture media therefor
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
- C12N1/20—Bacteria; Culture media therefor
- C12N1/205—Bacterial isolates
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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
-
- 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
- C22B47/00—Obtaining manganese
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12R—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES C12C - C12Q, RELATING TO MICROORGANISMS
- C12R2001/00—Microorganisms ; Processes using microorganisms
- C12R2001/01—Bacteria or Actinomycetales ; using bacteria or Actinomycetales
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Abstract
The application provides a method for cooperatively leaching gold, silver and manganese from manganese-silver ore, high-arsenic high-sulfur gold-loaded pyrite and thiobacillus ferrooxidans, and relates to the technical field of metallurgy, wherein the method comprises the following steps: step 1: crushing and finely grinding manganese-silver ore and high-arsenic high-sulfur gold-silver-loaded pyrite, fully mixing, and pulping to prepare ore pulp; step 2: inoculating thiobacillus ferrooxidans subjected to rejuvenation and expansion culture to the ore pulp, and performing biological leaching to enable manganese silver ore and pyrite in the ore pulp to rapidly undergo oxidation-reduction reaction to leach manganese, and performing solid-liquid separation on an obtained biological leaching product to obtain a manganese-rich leaching solution and leaching residues containing gold and silver; step 3: and leaching the gold and silver from the leaching slag containing the gold and silver. The full wet process provided by the application is particularly suitable for jointly treating low-grade oxidized manganese-silver ores and low-grade high-arsenic high-sulfur gold-silver-loaded pyrites, and solves the problems of low recovery rate of gold, silver and manganese, high consumption of additional materials, high process energy consumption and the like in the conventional process.
Description
Technical Field
The application relates to the technical field of metallurgy, in particular to a method for cooperatively leaching gold, silver and manganese from manganese-silver ore, high-arsenic high-sulfur gold-loaded pyrite and thiobacillus ferrooxidans.
Background
The manganese-silver ore in China has low mineral resource grade, poor quality and high impurity content, so that the difficulty of the smelting process is high, the metal recovery rate is low, and the process economy is poor. Silver in manganese-silver ores is often coated in manganese oxide minerals in very small particles, so that leaching rates are generally low when gold and silver leaching agents are used for direct leaching. Aiming at low-grade manganese silver ore, scientific research work in China has proposed a two-ore one-step process, metal sulphide mineral pyrite with reducibility is adopted, manganese silver ore which takes pyrolusite and pyrolusite as main manganese-containing minerals is reduced, and oxidation-reduction reaction of manganese oxide and pyrite is promoted by adding excessive concentrated sulfuric acid at a higher reaction temperature (80-100 ℃), so that the manganese reduction leaching efficiency is improved. Because the two-ore one-step method requires harsh conditions such as high temperature, high acid and the like, the problems of large material consumption (high acid and excessive pyrite), high energy consumption, large reaction leaching slag and large neutralization slag amount (because of high acid, a large amount of neutralization reagents are needed) are caused.
The Kaolin type gold ore is a fine dip-dyeing type gold ore and is mainly characterized by high arsenic, high sulfur, low gold grade and fine embedded granularity. The Carlin type gold ore resources in China have large reserves and wide distribution, but the ore resources have poor endowment, so that pre-oxidation treatment is generally required before gold extraction. The general pre-oxidation process comprises two types of pressurized pre-oxidation and biological pre-oxidation, and the two pre-oxidation treatments have the problems of high energy consumption (the oxidation process of gold and silver-loaded sulphide minerals needs to be powered on, particularly the pressurized pre-oxidation process has higher energy consumption), difficult treatment of leaching residues and leaching solutions (the high acidity of the leaching solutions leads to complex neutralization process and high cost), large leaching residue amount, great harm to the environment caused by arsenic and the like.
Therefore, in the technical field of metallurgy, how to effectively avoid or solve the difficulties and disadvantages (low recovery rate of gold, silver and manganese, high material consumption, high process energy consumption, large slag content, easy environmental pollution and the like) of processing two materials (manganese and silver ores and high-arsenic high-sulfur loaded gold, silver and pyrite) by the conventional treatment process becomes the technical problem to be solved in the present day.
Disclosure of Invention
In order to solve the problems, in a first aspect, the application provides a method for cooperatively leaching gold, silver and pyrite with high arsenic and high sulfur, wherein the method comprises the following steps:
step 1: crushing and finely grinding manganese-silver ore and high-arsenic high-sulfur gold-silver-loaded pyrite, fully mixing, and pulping to prepare ore pulp;
step 2: inoculating rejuvenating and expanding-culturing thiobacillus ferrooxidans (Acidithiobacillus sp. Biomeek-YM-I) to the ore pulp, and performing bioleaching to enable manganese silver ore and pyrite in the ore pulp to rapidly undergo oxidation-reduction reaction to leach manganese, and performing solid-liquid separation on the obtained bioleaching product to obtain manganese-rich leaching solution and leaching slag containing gold and silver; wherein the manganese-rich leachate is used for producing manganese;
step 3: and leaching the gold and silver from the leaching slag containing the gold and silver.
Preferably, the fine grinding is used for finely grinding the manganese silver ore and the high-arsenic high-sulfur gold-silver-loaded pyrite to the concentration of-0.074 mm accounting for more than 50%.
Preferably, the mass ratio of the manganese-silver ore to the high-arsenic high-sulfur gold-silver-loaded pyrite is 5 (1-25).
Preferably, the inoculation amount of the thiobacillus ferrooxidans accounts for 1-99% of the volume of the ore pulp.
Preferably, in the bioleaching process, the concentration of the ore pulp after the inoculation of the thiobacillus ferrooxidans is 10-25%, and the pH value of the ore pulp after the inoculation of the thiobacillus ferrooxidans is controlled within the range of 0.80-2.00.
Preferably, the temperature of the bioleaching is 20-40 ℃, and the time of the bioleaching is 2-7 days.
Preferably, the stirring speed of the bioleaching is 100-600 r/min, and the aeration quantity of the stirring is 0.05m 3 /h～0.30m 3 /h。
Preferably, the step 3 includes:
firstly, calcium oxide is adopted to carry out size mixing on leaching residues containing gold and silver, and then a gold and silver leaching medicament is adopted to leach gold and silver.
Preferably, the manganese-rich leach solution is used for producing manganese, comprising:
the manganese-rich leaching solution can be used for producing manganese sulfate, electrolytic manganese or electrolytic manganese dioxide after the pretreatment process of removing impurities, purifying, neutralizing and enriching.
In a second aspect, the application provides a thiobacillus ferrooxidans, which has a preservation number of CCTCC No: m2022861 (Acidithiobacillus sp. Biometak-YM-I) is used in the method of the first aspect described above.
Compared with the prior art, the application has the following advantages:
the application provides a method for cooperatively leaching gold, silver and manganese from manganese-silver ore, high-arsenic high-sulfur gold-loaded pyrite and thiobacillus ferrooxidans, and relates to the technical field of metallurgy, wherein the method comprises the following steps: step 1: crushing and finely grinding manganese-silver ore and high-arsenic high-sulfur gold-silver-loaded pyrite, fully mixing, and pulping to prepare ore pulp; step 2: inoculating thiobacillus ferrooxidans subjected to rejuvenation and expansion culture to the ore pulp, and performing biological leaching to enable manganese silver ore and pyrite in the ore pulp to rapidly undergo oxidation-reduction reaction to leach manganese, and performing solid-liquid separation on an obtained biological leaching product to obtain a manganese-rich leaching solution and leaching residues containing gold and silver; step 3: and leaching the gold and silver from the leaching slag containing the gold and silver. The full wet process provided by the application is particularly suitable for jointly treating low-grade oxidized manganese-silver ores and low-grade high-arsenic high-sulfur gold-silver-loaded pyrites, and solves the problems of low recovery rate of gold, silver and manganese, high consumption of additional materials, high process energy consumption and the like in the conventional process.
In the embodiment of the application, the synergistic promotion effect of the thiobacillus ferrooxidans on the gold-silver pyrite with high arsenic and high sulfur and the synergistic promotion effect of the thiobacillus ferrooxidans on two ores are utilized, so that noble metals (gold and silver) and manganese are efficiently recovered, the consumption of additional materials such as sulfuric acid, a neutralizing reagent and the like and energy in the reaction process is reduced, the total slag amount and the neutralizing slag amount of the reaction are reduced, the disposal cost of leached slag is further reduced, and the problems of low gold-silver manganese recovery rate, high material consumption, high process energy consumption, high slag amount, easiness in causing environmental pollution and the like are solved. The introduction of the exclusive bacteria (thiobacillus ferrooxidans) not only promotes the oxidation reaction of the high-arsenic high-sulfur gold-silver-loaded pyrite, but also applies excessive acid generated in the oxidation process to the oxidation-reduction process of the manganese-silver ore, namely, the exclusive bacteria has synergistic promotion effect on the high-arsenic high-sulfur gold-silver-loaded pyrite; and under the promotion of special bacteria, manganese silver ore and generated excessive acid and high-arsenic high-sulfur gold-silver-loaded pyrite are subjected to oxidation-reduction reaction rapidly and efficiently, namely, the special bacteria promote the reaction of the two ores, so that the package of manganese mineral in the manganese silver ore and the package of pyrite in the high-arsenic high-sulfur gold-silver-loaded pyrite on gold and silver are opened rapidly and efficiently while the reaction is carried out, the opening degree of mineral package is improved, and the efficient leaching of manganese is realized, so that the recovery rate of gold and silver in the subsequent process is further realized. In addition, the introduction of the special bacteria promotes the reaction of dissolving and producing acid of the product (reduced sulfur) after oxidation reduction, and the generated sulfuric acid is used for promoting the oxidation reduction reaction, so that the coated minerals are opened more quickly and efficiently, and the efficient leaching of manganese and gold and silver is realized.
The application provides a method for extracting gold, silver and manganese from manganese and silver ores and high-arsenic high-sulfur loaded gold, silver and pyrite by utilizing special bacteria in a synergistic way, which has the characteristics of low investment, low process energy consumption, low production cost (less additional materials, such as sulfuric acid, neutralizing agents and the like), less waste liquid and slag, short process flow, low reaction temperature and the like, can improve the utilization rate of resources, and can obtain larger economic benefit, social benefit and environmental benefit, and is particularly suitable for cooperatively treating low-grade oxidized manganese and silver ores and low-grade high-arsenic high-sulfur loaded gold, silver and pyrite.
Drawings
In order to more clearly illustrate the embodiments of the application or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of the method for cooperatively leaching gold, silver and manganese from manganese silver ores, high-arsenic high-sulfur gold-loaded pyrites;
fig. 2 is a process flow diagram of the present application.
Detailed Description
The following examples are provided for a better understanding of the present application and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the application, any product which is the same or similar to the present application, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present application.
Specific experimental steps or conditions are not noted in the examples and may be performed in accordance with the operation or conditions of conventional experimental steps described in the prior art in the field. The reagents used, as well as other instruments, are conventional reagent products available commercially, without the manufacturer's knowledge. Furthermore, the drawings are merely schematic illustrations of embodiments of the disclosure and are not necessarily drawn to scale. The same reference numerals in the drawings denote the same or similar parts, and thus a repetitive description thereof will be omitted. Some of the block diagrams shown in the figures are functional entities and do not necessarily correspond to physically or logically separate entities.
In a first aspect, referring to fig. 1, fig. 1 is a flowchart of a method for co-leaching gold, silver and manganese from manganese silver ores, high-arsenic high-sulfur loaded gold, silver and pyrite, provided by the application, the method comprises:
s101, crushing, finely grinding and fully mixing manganese-silver ore and high-arsenic high-sulfur gold-silver-loaded pyrite, and pulping to prepare ore pulp;
wherein, the manganese-silver ore mainly refers to the ore in which manganese minerals (pyrolusite and pyrolusite) exist in the form of tetravalent oxide.
S102, inoculating rejuvenating and expanding cultured thiobacillus ferrooxidans (Acidithiobacillus sp. Biomeek-YM-I) to the ore pulp, and then performing bioleaching to enable manganese silver ore and pyrite in the ore pulp to rapidly undergo oxidation-reduction reaction to leach manganese, and performing solid-liquid separation on the obtained bioleaching product to obtain manganese-rich leaching solution and leaching slag containing gold and silver; wherein the manganese-rich leach solution is used for producing a manganese product;
the classification names of the thiobacillus ferrooxidans are as follows: acidithiobacillus sp.biomeek-YM-I, accession number: china center for type culture Collection, address: the preservation date of the university of Wuhan, china is: 2022, 06, 10, deposit No.: cctccc No: m2022861.
Wherein, rejuvenation and expansion culture are specifically as follows: rejuvenating and expanding culture of special bacteria (thiobacillus ferrooxidans) to obtain bacterial liquid suitable for target minerals (manganese-silver ores and high-arsenic high-sulfur gold-silver-loaded pyrite); wherein the culture temperature is 15-40 ℃, the culture pH value is 0.80-3.50, the concentration of manganese element in the culture medium is 0-70 g/L, and the concentration of arsenic element is 0-15 g/L.
In the culture process of the special bacteria, the culture medium has a certain concentration of manganese and arsenic, so that the special bacteria obtained by culture have higher tolerance to manganese and arsenic to obtain the bacterial liquid of the target mineral, and the special bacteria can be more quickly adapted to the process environment of the application (because of the manganese silver ore, the system of the application contains higher manganese ions). Wherein, 70g/L and 15g/L are respectively the maximum concentration of manganese and arsenic elements which can be tolerated by the special bacteria. If the specific bacteria are not domesticated, when the manganese concentration is higher than 5g/L or the arsenic concentration is higher, the leaching rate of valuable metals is insufficient due to the fact that the bacteria are not tolerant. The process adds manganese and arsenic elements in rejuvenation and expansion culture flow, so that the special bacteria can adapt to a target system faster and better, and the rejuvenation and expansion culture time is shortened.
Wherein the thiobacillus ferrooxidans is used for promoting the generation of sulfuric acid required in the oxidation-reduction reaction process.
Step S102 is a process of leaching manganese from the manganese silver ore (opening the package of the manganese mineral in the manganese silver ore to silver) so as to leach silver subsequently; meanwhile, the method is also a process of pre-oxidizing the high-arsenic high-sulfur gold-silver-loaded pyrite (the package of the gold and silver in the high-arsenic high-sulfur gold-loaded pyrite is opened) so as to leach the gold and silver subsequently. According to the method provided by the application, for leaching the manganese silver from the manganese silver ore, the addition amount of sulfuric acid and pyrite is small; for leaching gold and silver from high-arsenic high-sulfur gold-silver-loaded pyrite, the pre-oxidation energy consumption is low and the time is short.
In the prior art, a two-ore one-step method is based on the following reaction: mnO (MnO) 2 +FeS 2 (additionally added high amount of pyrite) +H 2 SO 4 (additionally added large amount of sulfuric acid)
→MnSO 4 +Fe 2 (SO 4 ) 3 +S
The main biochemical reactions on which the application is based are as follows:
MnO 2 (silver-containing) +FeS 2 (containing gold and silver) +H 2 SO 4 →MnSO 4 +Fe 2 (SO 4 ) 3 +H 2 O①
FeS 2 +O 2 +H 2 O→Fe 2 (SO 4 ) 3 +H 2 SO 4 (bacterial action) (2)
S+O 2 +H 2 O→H 2 SO 4 (bacterial action) (3)
In the concrete implementation, the synergistic effect of the two materials is utilized to ensure that the single material is highBiological oxidation of arsenic high-sulfur gold-silver-loaded pyrite to MnO 2 The method is synergistic with dedicated bacteria for oxidation, and utilizes the biological oxidation of dedicated bacteria for acid production, thereby promoting the oxidation of reduced sulfur, simultaneously using the generated sulfuric acid for the reduction of manganese, and having strong oxidizing property (main mineral in manganese silver ore-manganese mineral MnO 2 Manganese silver ore such as pyrolusite, pyrolusite) and pyrite FeS which is a main mineral in gold, silver and pyrite with strong reducibility (high arsenic and high sulfur loading gold, silver and pyrite 2 ) The method is characterized in that the high-arsenic high-sulfur gold-silver-loaded pyrite is subjected to oxidation-reduction reaction under certain conditions (specific bacteria, temperature, oxygen content, pH and the like), the package of manganese mineral in the manganese-silver ore on silver and the package of pyrite in the high-arsenic high-sulfur gold-silver-loaded pyrite on gold and silver are opened during the reaction, so that the leaching of manganese is realized, and the leaching of gold and silver is further realized.
The introduction of the exclusive bacteria (1) promotes the reaction (2) to make the reaction (2) more complete, and applies the excessive acid generated in the oxidation process of the high-arsenic high-sulfur loaded gold-silver pyrite to the reduction process of the manganese-silver ore (namely, the reaction (2) generates excessive acid), namely, the synergistic promotion effect of the exclusive bacteria and the high-arsenic high-sulfur loaded gold-silver pyrite; (2) Under the promotion of special bacteria, manganese and silver ores react with excessive acid (also comprising sulfuric acid generated after the dissolution of elemental sulfur) generated by high-arsenic high-sulfur loaded gold and silver pyrite and high-arsenic high-sulfur loaded gold and silver pyrite (1), so that the reaction (1) is promoted, namely, the synergistic effect of two ores and the synergistic promotion effect of the special bacteria and the two ores are promoted, and the coated minerals (the coating of manganese minerals in the manganese and silver ores and the coating of gold and silver minerals in the high-arsenic high-sulfur loaded gold and silver pyrite) are opened more rapidly and efficiently while the reaction is carried out, the opening degree of mineral coating is improved, and the efficient leaching of manganese is realized, so that the recovery rate of gold and silver in the subsequent flow is further improved; (3) The product elemental sulfur of the reaction (1) is dissolved under the promotion of special bacteria to generate sulfuric acid, and the sulfuric acid is also used for promoting the reaction (1) to be carried out, so that the coated minerals are opened more quickly and efficiently, and the efficient leaching of manganese and gold and silver is realized. Therefore, the introduction of the special bacteria can better promote the reaction (reactions (1), (2) and (3)) in the whole system, so that the elementary reaction in the reaction process is obviously changed, noble metals (gold, silver) and manganese are efficiently recovered, the consumption of additional materials such as sulfuric acid, a neutralizing reagent and the like and energy is reduced, the total slag amount and the neutralizing slag amount of the reaction are reduced, and the cost for using the neutralizing reagent is further reduced.
The full wet process provided by the application is particularly suitable for cooperatively treating low-grade oxidized manganese-silver ores and low-grade high-arsenic high-sulfur gold-silver-loaded pyrites, and solves the problems of low gold and silver recovery rate, high process energy consumption, high material consumption, large slag quantity, easiness in environmental pollution and the like of the conventional process. Therefore, the method provided by the application has the advantages of low investment, low process energy consumption, low production cost (less additional materials), less waste liquid and slag quantity, short process flow, low reaction temperature and the like, can improve the resource utilization efficiency, and can obtain greater economic benefit, social benefit and environmental benefit. Compared with the method for separately treating the manganese silver ore and separately treating the high-arsenic high-sulfur gold-silver-loaded pyrite, the method provided by the application has the advantages that the gold and silver recovery rate is greatly improved, and gold and silver in the two ores can be leached simultaneously.
S103, leaching the gold and silver from the leaching slag containing the gold and silver.
In the specific implementation, the gold and silver leaching can be realized by thoroughly opening the package due to the package. Therefore, in the application, the step S102 extracts manganese element, realizes the efficient leaching of manganese, opens the package of manganese minerals on silver and silver minerals, and creates conditions for leaching silver in the subsequent leaching residues; and performing gold and silver cyanide leaching by pulp mixing and various gold leaching agents, leaching gold and silver from the biological leaching slag, and realizing gold and silver leaching, namely step S104.
In the specific implementation, in the biological leaching process of step S102, the leaching of manganese is realized, and only the package of silver and gold and silver minerals (i.e., the package of manganese minerals in the manganese-silver ores and the package of pyrite in the high-arsenic high-sulfur loaded pyrite) is opened, and gold and silver are not leached in a biological leaching manner, but leaching of gold and silver is realized in step S103. Therefore, according to the application, for Jin Yinlai, pretreatment (pretreatment, namely, step S101-step S102) is performed by adopting a biological synergistic method, so that the subsequent gold and silver leaching process (namely, step S103) is promoted, and the gold and silver leaching is realized with high efficiency.
If the high-arsenic high-sulfur gold-loaded pyrite has no gold element (only silver is the noble metal element), the step S103 is as follows: silver is leached from leaching slag containing silver.
In the embodiment of the application, the synergistic promotion effect of the special bacteria on the high-arsenic high-sulfur gold-silver-loaded pyrite and the synergistic promotion effect of the special bacteria on the two ores are utilized, so that the noble metal (gold, silver) and manganese are efficiently recovered, the addition amount of sulfuric acid in the reaction process is reduced, the consumption of additional materials and energy is further reduced, the cost of using a neutralizing reagent is further reduced, and the total slag amount and the neutralizing slag amount of the reaction are reduced. The introduction of the exclusive bacteria (1) promotes the reaction (2) to make the reaction (2) more complete, and applies the excessive acid generated in the oxidation process of the high-arsenic high-sulfur loaded gold-silver pyrite to the reduction process of the manganese-silver ore (namely, the reaction (2) generates excessive acid), namely, the synergistic promotion effect of the exclusive bacteria and the high-arsenic high-sulfur loaded gold-silver pyrite; (2) Under the promotion of the special bacteria, the manganese-silver ore rapidly and efficiently reacts with excessive acid generated by the high-arsenic high-sulfur loaded gold-silver pyrite and the high-arsenic high-sulfur loaded gold-silver pyrite to generate redox reaction (1), so that the reaction (1) is promoted, namely, the synergistic effect of the two ores and the synergistic promotion effect of the special bacteria and the two ores are promoted, and the wrapping minerals (the wrapping of the manganese mineral in the manganese-silver ore to silver and the wrapping of the pyrite in the high-arsenic high-sulfur loaded gold-silver pyrite to gold and silver) are rapidly and efficiently opened while the reaction is generated, so that the efficient leaching of manganese is realized, the opening degree of the wrapping of the minerals is improved, and the gold and silver recovery rate of the subsequent flow is further improved; (3) The elemental sulfur generated by incomplete oxidation of the high-arsenic high-sulfur gold-silver-loaded pyrite is promoted by the special bacteria, and then sulfuric acid is generated after dissolution, and the sulfuric acid is also used for promoting the reaction (1), so that the coated minerals are opened more rapidly and efficiently, and the high-efficiency leaching of manganese and gold is realized.
The method provided by the application has the advantages of low investment, low process energy consumption, low production cost (less additional materials such as sulfuric acid, pyrite, neutralizing agents and the like), less waste liquid and slag, short process flow, low reaction temperature and the like, can improve the resource utilization efficiency, and can obtain greater economic benefit, social benefit and environmental benefit.
Compared with the method for separately treating the manganese silver ore and separately treating the high-arsenic high-sulfur gold-silver-loaded pyrite, the method provided by the application has the advantages that the gold and silver recovery rate is greatly improved, and gold and silver in the two ores can be leached simultaneously. The method provided by the application realizes the cooperative utilization of two materials, and effectively avoids or solves the technical problem when the two materials are independently processed. If the manganese-silver ore is treated independently, the package of the manganese mineral on the silver cannot be opened due to the lack of reaction conditions (pyrite and sulfuric acid), the recovery rate of manganese is low, and the recovery and utilization of valuable elements are difficult to realize. And, if the recovery of manganese minerals is to be enhanced, a large amount of sulfuric acid and reducing minerals are required; if Jin Yinhuang iron ore is treated independently, if no special strain is added, the oxidation rate of the pyrite is extremely low, the package of the gold and the silver cannot be opened, the gold and the silver cannot be recovered, if the special strain is added, the oxidation-reduction pyrite can be better, but the oxidation efficiency is still lower than that of an experimental group in which the manganese and silver ore and the strain are added simultaneously, and the package opening degree and the recovery rate of the gold and the silver are also lower.
Preferably, the fine grinding is used for finely grinding the manganese silver ore and the high-arsenic high-sulfur gold-silver-loaded pyrite to the concentration of-0.074 mm accounting for more than 50%.
Preferably, the mass ratio of the manganese-silver ore to the high-arsenic high-sulfur gold-silver-loaded pyrite is 5 (1-25).
In the specific implementation, in the mass ratio range of the manganese-silver ore and the high-arsenic high-sulfur gold-loaded pyrite, the ideal recovery rate of manganese and gold can be realized, but if the addition amount of the manganese-silver ore is too large, the recovery rate of manganese and silver in the manganese-silver ore is possibly insufficient; if the addition amount of the manganese-silver ore is too small, the recovery rate of gold and silver in the pyrite is possibly insufficient; if the adding amount of the gold-silver-loaded pyrite is too large, the recovery rate of gold and silver in the pyrite is possibly insufficient; if the addition amount of the gold-silver-loaded pyrite is too small, the recovery rate of silver in the manganese-silver ore is possibly insufficient.
Preferably, the inoculation amount of the thiobacillus ferrooxidans accounts for 1-99% of the volume of the ore pulp.
Preferably, in the bioleaching process, the concentration of the ore pulp after the inoculation of the thiobacillus ferrooxidans is 10-25%, and the pH value of the ore pulp after the inoculation of the thiobacillus ferrooxidans is controlled within the range of 0.80-2.00.
In particular, the pulp concentration is in the range of the pulp concentration required before bioleaching.
Preferably, the temperature of the bioleaching is 20-40 ℃, and the time of the bioleaching is 2-7 days.
In the concrete implementation, the reaction temperature is low, and the energy consumption is low. In addition, in the leaching process, other new energy sources such as ultrasonic equipment and the like are not needed to be additionally arranged for improving the reaction efficiency so as to enable the reaction to be carried out. It should be noted that the temperature range is also the temperature required by the growth of the special bacteria, if the temperature reaches 60 ℃, the bacteria die, and the synergistic leaching of manganese and gold and silver by the special bacteria and the two ores cannot be realized.
Preferably, the stirring speed of the bioleaching is 100-600 r/min, and the aeration quantity of the stirring is 0.05m 3 /h～0.30m 3 /h。
In specific implementation, the concentration of ore pulp before bioleaching, the pH value of the ore pulp, the temperature and time of bioleaching, the stirring rotating speed and the aeration quantity are set to maintain the normal growth of bacteria and ensure the effective recovery of valuable metals (gold, silver) and manganese. It should be noted that the bioleaching process is a continuous stirring process.
Preferably, the step 3 includes:
firstly, calcium oxide is adopted to carry out size mixing on leaching residues containing gold and silver, and then a gold and silver leaching medicament is adopted to leach gold and silver.
In the specific implementation, the gold and silver leaching agent can be thiourea or cyanide. Furthermore, the gold and silver leaching process adopts cyanide leaching, thiourea gold leaching, thiosulfate gold leaching and various environment-friendly gold and silver leaching agents sold in the market.
Preferably, the manganese-rich leach solution is used for producing manganese, comprising:
the manganese-rich leaching solution can be used for producing manganese sulfate, electrolytic manganese or electrolytic manganese dioxide after the pretreatment process of removing impurities, purifying, neutralizing and enriching.
In the concrete implementation, the requirements on the manganese sulfate solution are different in the production process of manganese sulfate, electrolytic manganese or electrolytic manganese dioxide. The pretreatment processes such as impurity removal, purification, enrichment and the like before the leaching solution enters the next production process are determined according to the concentration of main element manganese in the leaching solution and the types and contents of impurity elements (the contents of elements in the process raw materials of manganese-silver ore and high-arsenic high-sulfur gold-silver-loaded pyrite are different, and the contents of elements in the leaching solution are different). In general, conventional processes such as iron removal processes (e.g., neutralization iron removal, extraction iron removal, goethite iron removal, etc.), copper and zinc removal purification processes (extraction, ion exchange, sulfidation precipitation, etc.), neutralization processes (lime neutralization, sodium hydroxide neutralization, etc.), enrichment processes (concentration crystallization, etc.) may be applied to the process for producing manganese.
In a second aspect, the application provides a thiobacillus ferrooxidans, which has a preservation number of CCTCC No: m2022861 (Acidithiobacillus sp. Biometak-YM-I) is used in the method of the first aspect described above.
In the embodiment of the application, the synergistic promotion effect of the thiobacillus ferrooxidans on the gold-silver pyrite with high arsenic and high sulfur and the synergistic promotion effect of the thiobacillus ferrooxidans on two ores are utilized, so that noble metals (gold, silver) and manganese are recovered efficiently, the addition amount of sulfuric acid in the reaction process is reduced, the consumption of additional materials and energy is further reduced, the cost of using a neutralizing reagent is further reduced, and the total slag amount and the neutralization slag amount of the reaction are reduced.
In order to enable those skilled in the art to better understand the present application, the following description is made with reference to a number of specific examples.
Example 1
Referring to fig. 2, fig. 2 is a process flow diagram of the present application.
Manganese silver ore (manganese content is 25.22%, silver grade is 869.90 g/t) and high-arsenic high-sulfur silver-loaded yellow with a mass ratio of 5:1.5Iron ore (iron content 46.83%, sulfur content 39.59%, arsenic content 1.22%, silver grade 61.40 g/t) is crushed and finely ground until-0.074 mm accounts for more than 50%, and then fully mixed and slurried to prepare ore pulp. Inoculating the ore pulp with Acidithiobacillus sp.biomeek-YM-I bacterial liquid, performing bioleaching (or biological agitation leaching), wherein bacterial inoculum size is 20% of the volume of the ore pulp, controlling the reaction temperature at 33 ℃ in the biological agitation leaching process, and controlling the agitation rotating speed at 160r/min, and the aeration amount in the agitation process at 0.1m 3 And (3) adding sulfuric acid solution in the leaching process to control the pH value of the whole reaction to be 1.50, carrying out solid-liquid separation on the biological leaching product obtained after the leaching is finished for 4 days to obtain leaching slag containing silver and manganese-rich leaching solution, wherein the leaching rate of manganese is 98.54%. The manganese-rich leaching solution can be used for producing manganese sulfate, electrolytic manganese or electrolytic manganese dioxide after pretreatment such as impurity removal, purification, enrichment and the like. The leaching slag containing silver adopts calcium oxide for size mixing and adopts gold and silver leaching agents for silver leaching, and the conditions of silver leaching are as follows: pulp concentration is 40%, pulp pH value is controlled to be 11.5, stirring rotation speed is 400r/min, and leaching time is 48h. The total leaching rate of silver is 97.73%.
Example 2
Manganese-silver ore (22.64% of manganese content and 801.20g/t of silver grade) and high-arsenic high-sulfur gold-carrying pyrite (31.15% of iron content, 31.21% of sulfur content and 3.15% of arsenic content) with a mass ratio of 5:3 are crushed and finely ground until the gold grade is more than 50% of-0.074 mm, and then fully mixed and slurried to prepare ore pulp. Inoculating the ore pulp with Acidithiobacillus sp.biomeek-YM-I bacterial liquid, performing biological agitation leaching, wherein bacterial inoculum size is 20% of the ore pulp volume, controlling the reaction temperature at 33 ℃ in the biological agitation leaching process, and the agitation rotating speed at 160r/min, and the aeration amount in the agitation process is 0.1m 3 And/h, adding sulfuric acid solution in the leaching process to control the pH value of the whole reaction to be 1.50, and enabling the bioleaching time to be 4 days. And (3) carrying out solid-liquid separation on the biological leaching product after leaching to obtain leaching residues containing gold and silver and a manganese-rich leaching solution, wherein the leaching rate of manganese is 96.97%. The manganese-rich leaching solution can be used for producing manganese sulfate, electrolytic manganese or electrolytic manganese dioxide after pretreatment such as impurity removal, purification, enrichment and the like. The leaching slag containing gold and silver adopts calcium oxide for size mixing and gold and silver leaching agent for gold and silver leachingThe leaching conditions are as follows: pulp concentration is 40%, pulp pH value is controlled to be 11.5, stirring rotation speed is 400r/min, and leaching time is 48h. The total leaching rate of silver is 94.33%, and the leaching rate of gold is 83.31%.
Thus, when pyrite material is difficult to oxidize, the recovery of the encapsulated precious metal will be lower under the same conditions.
Example 3
Referring to fig. 2, fig. 2 is a process flow diagram of the present application.
And crushing and finely grinding manganese-silver ores (the manganese content is 25.22 percent, the silver grade is 869.90 g/t) and high-arsenic high-sulfur silver-loaded pyrite (the iron content is 46.83 percent, the sulfur content is 39.59 percent, the arsenic content is 1.22 percent and the silver grade is 61.40 g/t) with mass ratios of 5:10, 5:15 and 5:20 respectively until the manganese content and the silver content are more than 50 percent, and fully mixing and pulping to prepare ore pulp. Inoculating the ore pulp with Acidithiobacillus sp.biomeek-YM-I bacterial liquid, performing biological agitation leaching, wherein bacterial inoculum size is 20% of the ore pulp volume, controlling the reaction temperature at 33 ℃ in the biological agitation leaching process, and the agitation rotating speed at 160r/min, and the aeration amount in the agitation process is 0.1m 3 And (3) supplementing sulfuric acid solution in the leaching process to control the pH value of the whole reaction to be 1.50, and carrying out solid-liquid separation on the biological leaching product obtained after the leaching is finished for 4 days to obtain leaching slag containing silver and manganese-rich leaching liquid, wherein the manganese leaching rate is 98.77%, 98.63% and 99.02% in sequence. The manganese-rich leaching solution can be used for producing manganese sulfate, electrolytic manganese or electrolytic manganese dioxide after pretreatment such as impurity removal, purification, enrichment and the like. The leaching slag containing silver adopts calcium oxide for size mixing and adopts gold and silver leaching agents for silver leaching, and the conditions of silver leaching are as follows: pulp concentration is 40%, pulp pH value is controlled to be 11.5, stirring rotation speed is 400r/min, and leaching time is 48h. The total leaching rate of silver is 94.68%, 92.54% and 91.06% in sequence.
Comparative example 1
Comparative example 1 differs from example 1 in that the Acidithiobacillus sp.biomeek-YM-I bacterial liquid was not inoculated, but that the manganese-silver ore and the excessive high-arsenic high-sulfur silver-loaded pyrite were directly mixed thoroughly (mass ratio of 2:1) and then added with excessive sulfuric acid to carry out chemical agitation leaching, the temperature during the reaction was 33 ℃, the agitation rotational speed was 160r/min, and the aeration amount during the agitation was 0.1m 3 And/h, the pH at the reaction end point is 0.81, the leaching rate of manganese is 62.19% only and the leaching rate of silver is 45.96% only after leaching for 4 days.
In this comparative example, in order to increase the leaching rate of manganese, the addition amount of high-arsenic high-sulfur silver-loaded pyrite was increased. However, in this comparative example, the silver recovery rate in pyrite was insufficient due to the lack of bacterial action.
The mechanism involved in this comparative example 1 is:
MnO 2 +FeS 2 +H 2 SO 4 →MnSO 4 +Fe 2 (SO 4 ) 3 +S
when the addition amount of sulfuric acid and pyrite is insufficient or the reaction temperature is too low, the reduction leaching rate of manganese and the reduction leaching rate are reduced; still further, the reason for the low reduction leaching rate and the low reduction leaching rate of manganese is mainly that the chemical oxidation dissolution rate of pyrite is not fast enough, the oxidation rate is not high enough, and the concentration of materials participating in the reaction is reduced, namely, the utilization rate of pyrite is low. Therefore, in comparative example 1, in order to increase the recovery rate of manganese and to enable the pyrite to be fully utilized, oxidation-reduction reaction was performed by adding an excessive amount of concentrated sulfuric acid and pyrite.
Further problems arise from the addition of excess concentrated sulfuric acid and pyrite in comparative example 1: the excessive sulfuric acid causes high acidity of the manganese-rich liquid and high concentration of heavy metal ions, so that a large amount of neutralization reagents such as lime, sodium carbonate, sodium hydroxide and the like are needed in the purification and impurity removal stage of the solution, namely, excessive use of the medicament is caused, and the cost is increased; the amount of the reaction leaching slag is large, and a large amount of pyrite remained in the leaching slag is not fully utilized and acid is produced to dissolve iron under the natural weathering effect in the piling process, so that potential harm to the environment is continuously caused; meanwhile, a large amount of neutralizing agents such as lime, sodium carbonate, sodium hydroxide and the like are used in the solution purification and impurity removal stage, so that a large amount of neutralizing slag is generated, and a large amount of solid waste and even dangerous waste are generated to be treated.
From this, it can be seen that the leaching rates of manganese and silver were higher in example 1 than in comparative example 1, which was not inoculated with the specific bacteria.
Comparative example 2
The difference between comparative example 2 and example 2 is that the co-recovery of the manganese silver oxide enriched concentrate (intermediate product of the manganese silver ore enriched by the beneficiation process) and the high-arsenic gold-bearing pyrite is not considered, but treated separately.
(1) High-arsenic high-sulfur gold-loaded pyrite independent treatment
Inoculating Acidithiobacillus sp.biomeek-YM-I bacterial liquid after pulping the high-arsenic high-sulfur gold-loaded pyrite, carrying out biological agitation leaching, wherein the bacterial inoculum size accounts for 20% of the volume of pulp after pulping, the reaction temperature in the biological leaching process is 33 ℃, the agitation speed in the biological leaching process is 160r/min, and the aeration amount in the agitation process is 0.1m 3 And (3) leaching for 4 days, and cyaniding gold leaching is carried out on the leached slag, wherein the technological conditions are as follows: pulp concentration 40%, pulp pH 11.5, stirring rotation speed 400rpm, leaching time 48h, gold leaching rate 68.16%.
Therefore, when the special bacteria (ferrous oxide thiobacillus) are only adopted to pre-oxidize the high-arsenic high-sulfur gold-loaded pyrite and further leach gold and silver, the synergistic effect between the two ores and the separate effect of the special bacteria on the two ores are not utilized, and although the biological pre-oxidation can be carried out on the high-arsenic high-sulfur gold-loaded pyrite, the oxidation efficiency is still lower than that of an experimental group (see example 2) in which the manganese and silver ores and the bacterial are added simultaneously, and the wrapping opening degree and the recovery rate of gold are also lower.
It should be noted that if the Jin Yinhuang iron ore is treated separately, if no special strain is added, the oxidation rate of pyrite is extremely low, the package of gold and silver cannot be opened, and gold and silver cannot be recovered.
(2) Separate treatment of manganese silver oxide enriched concentrate
The manganese silver oxide enriched concentrate is inoculated with Acidithiobacillus sp.biomeek-YM-I bacterial liquid after pulp mixing, biological stirring leaching is carried out, bacterial inoculum size is 20%, reaction temperature is controlled to be 33 ℃ in the biological stirring leaching process, stirring rotating speed is 160r/min, and aeration amount in the stirring process is 0.1m 3 And (3) adding sulfuric acid solution in the leaching process to control the pH value of the whole reaction to be 1.50, wherein the leaching time is 5 days, the leaching rate of manganese is only 1.48%, and the leaching process conditions of cyanide leaching silver from the leached manganese slag are as follows: the concentration of the ore pulp is 40 percent,the pH value of the ore pulp is 11.5, the stirring rotation speed is 400rpm, the leaching time is 48 hours, and the silver leaching rate is 6.14 percent.
Therefore, when the special bacteria (ferrous oxide thiobacillus) are only used for leaching manganese from the manganese silver ore, the synergistic effect between the two ores and the separate effect of the special bacteria on the two ores are not utilized, so that the wrapping of the manganese ore on the silver cannot be opened, the recovery rate of manganese is low, and the recovery and utilization of valuable elements are difficult to realize. And, more importantly, if the recovery of the metal elements of the manganese mineral is to be improved, a large amount of sulfuric acid and a reducing mineral are required.
For the purposes of simplicity of explanation, the methodologies are shown as a series of acts, but one of ordinary skill in the art will recognize that the present application is not limited by the order of acts described, as some acts may, in accordance with the present application, occur in other orders and concurrently. Further, those skilled in the art will recognize that the embodiments described in the specification are all of the preferred embodiments, and that the acts and components referred to are not necessarily required by the present application.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present disclosure. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, one skilled in the art can combine and combine the different embodiments or examples described in this specification.
The method for cooperatively leaching gold, silver and manganese from the manganese-silver ore, the high-arsenic high-sulfur loaded gold, silver and pyrite and the thiobacillus ferrooxidans are described in detail, and specific examples are applied to the description of the principle and the implementation mode of the method, and the description of the examples is only used for helping to understand the method and the core idea of the method; meanwhile, as those skilled in the art will have variations in the specific embodiments and application scope in accordance with the ideas of the present application, the present description should not be construed as limiting the present application in view of the above.
Claims (10)
1. The method for cooperatively leaching the gold, silver and manganese from the manganese-silver ore and the high-arsenic high-sulfur gold-loaded pyrite is characterized by comprising the following steps of:
step 1: crushing and finely grinding manganese-silver ore and high-arsenic high-sulfur gold-silver-loaded pyrite, fully mixing, and pulping to prepare ore pulp;
step 2: inoculating rejuvenating and expanding-culturing thiobacillus ferrooxidans (Acidithiobacillus sp. Biomeek-YM-I) to the ore pulp, and performing bioleaching to enable manganese silver ore and pyrite in the ore pulp to rapidly undergo oxidation-reduction reaction to leach manganese, and performing solid-liquid separation on the obtained bioleaching product to obtain manganese-rich leaching solution and leaching slag containing gold and silver; wherein the manganese-rich leach solution is used for producing a manganese product;
step 3: and leaching the gold and silver from the leaching slag containing the gold and silver.
2. The method of claim 1, wherein the fine grinding finely grinds the manganese silver ore and the high-arsenic high-sulfur gold-loaded pyrite to-0.074 mm accounting for more than 50%.
3. The method according to claim 1, wherein the mass ratio of the manganese-silver ore to the high-arsenic high-sulfur gold-silver pyrite is 5 (1-25).
4. The method of claim 1, wherein the inoculum size of the thiobacillus ferrooxidans is 1% to 99% of the volume of the pulp.
5. The method according to claim 1, wherein in the bioleaching process, the concentration of the pulp after inoculation of the thiobacillus ferrooxidans is 10-25%, and the pH of the pulp after inoculation of the thiobacillus ferrooxidans is controlled to be in the range of 0.80-2.00.
6. The method of claim 1, wherein the bioleaching temperature is 20 ℃ to 40 ℃ and the bioleaching time is 2 to 7 days.
7. The method according to claim 1, wherein the stirring speed of the bioleaching is 100-600 r/min, and the aeration amount of the stirring is 0.05m 3 /h～0.30m 3 /h。
8. The method according to claim 1, wherein the step 3 comprises:
firstly, calcium oxide is adopted to carry out size mixing on leaching residues containing gold and silver, and then a gold and silver leaching medicament is adopted to leach gold and silver.
9. The method of claim 1, wherein the manganese-rich leach solution is used to produce a manganese product, comprising:
the manganese-rich leaching solution can be used for producing manganese sulfate, electrolytic manganese or electrolytic manganese dioxide after the pretreatment process of removing impurities, purifying, neutralizing and enriching.
10. Thiobacillus ferrooxidans, characterized in that the thiobacillus ferrooxidans (Acidithiobacillus sp. Biomeek-YM-I) with the preservation number of CCTCC No. M2022861 is used in the method according to any one of the preceding claims 1-9.
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| CN202310804782.3A CN116855754A (en) | 2023-06-30 | 2023-06-30 | Method for cooperatively leaching gold, silver and manganese from manganese-silver ore, high-arsenic high-sulfur gold-loaded pyrite and thiobacillus ferrooxidans |
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