WO2023206841A1 - Procédé de séparation et d'élimination d'impuretés de tungstène et de molybdène pendant un processus de fusion de tungstène - Google Patents
Procédé de séparation et d'élimination d'impuretés de tungstène et de molybdène pendant un processus de fusion de tungstène Download PDFInfo
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- WO2023206841A1 WO2023206841A1 PCT/CN2022/108809 CN2022108809W WO2023206841A1 WO 2023206841 A1 WO2023206841 A1 WO 2023206841A1 CN 2022108809 W CN2022108809 W CN 2022108809W WO 2023206841 A1 WO2023206841 A1 WO 2023206841A1
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- WO
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- tungsten
- molybdenum
- solution
- separating
- removing impurities
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 64
- 239000010937 tungsten Substances 0.000 title claims abstract description 64
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 55
- 239000011733 molybdenum Substances 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 53
- 238000003723 Smelting Methods 0.000 title claims abstract description 20
- 239000012535 impurity Substances 0.000 title claims abstract description 20
- 238000000926 separation method Methods 0.000 title claims abstract description 14
- 241000894006 Bacteria Species 0.000 claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000005987 sulfurization reaction Methods 0.000 claims abstract description 13
- 239000002244 precipitate Substances 0.000 claims abstract description 8
- 230000002378 acidificating effect Effects 0.000 claims abstract description 4
- 238000004321 preservation Methods 0.000 claims abstract 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 31
- 230000035484 reaction time Effects 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000002054 inoculum Substances 0.000 claims description 10
- 238000009413 insulation Methods 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 150000004665 fatty acids Chemical class 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 238000005486 sulfidation Methods 0.000 claims description 4
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 abstract description 24
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 13
- 230000001603 reducing effect Effects 0.000 abstract description 13
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 abstract description 9
- -1 sulfur ions Chemical class 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000009388 chemical precipitation Methods 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract description 2
- CXVCSRUYMINUSF-UHFFFAOYSA-N tetrathiomolybdate(2-) Chemical compound [S-][Mo]([S-])(=S)=S CXVCSRUYMINUSF-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract 2
- 239000011593 sulfur Substances 0.000 abstract 2
- 229910016003 MoS3 Inorganic materials 0.000 abstract 1
- 230000036983 biotransformation Effects 0.000 abstract 1
- TVWWSIKTCILRBF-UHFFFAOYSA-N molybdenum trisulfide Chemical compound S=[Mo](=S)=S TVWWSIKTCILRBF-UHFFFAOYSA-N 0.000 abstract 1
- 239000000706 filtrate Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 238000011081 inoculation Methods 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 6
- 241001411320 Eriogonum inflatum Species 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 230000001580 bacterial effect Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 229940107700 pyruvic acid Drugs 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 208000012826 adjustment disease Diseases 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- JPNWDVUTVSTKMV-UHFFFAOYSA-N cobalt tungsten Chemical compound [Co].[W] JPNWDVUTVSTKMV-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000010310 metallurgical process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 235000006286 nutrient intake Nutrition 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/36—Obtaining tungsten
-
- 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
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/34—Obtaining molybdenum
-
- 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
Definitions
- the invention relates to the field of tungsten hydrometallurgy, specifically a method for separating tungsten and molybdenum and removing impurities during the tungsten smelting process.
- Tungsten and molybdenum are strategically important rare metals with a wide range of uses in industry. Tungsten and molybdenum both belong to Group VIB in the periodic table of elements. Due to the influence of "lanthanide shrinkage", their atomic radii, atomic structures, and chemical properties are very similar, making the separation process very difficult. In many associated tungsten and molybdenum element resources, tungsten and molybdenum exist in homogeneous and homogeneous phases. Ore dressing methods often cannot effectively separate tungsten and molybdenum elements, and metallurgical processes are usually used for separation. At present, my country's tungsten smelting enterprises basically use copper sulfide precipitation, ion exchange separation, solvent extraction separation, etc. to separate tungsten and molybdenum. However, the above processes all have shortcomings such as low molybdenum removal efficiency, high cost, and long reaction cycle.
- the purpose of the present invention is to overcome the above technical deficiencies, provide a method for separating and removing impurities from tungsten and molybdenum in the tungsten smelting process, and solve the technical problems of low molybdenum removal efficiency and long reaction cycle in the tungsten and molybdenum separation process in the prior art.
- the technical solution of the method of the present invention is:
- step (1) is 5-9.
- step (1) the pH value is adjusted by using sulfuric acid and sodium hydroxide solutions.
- step (2) the inoculum amount of sulfate-reducing bacteria is 100-10000/mL.
- the carbon source is one or more of glucose, starch, organic alcohols and fatty acids.
- step (2) the sulfidation reaction is carried out under anaerobic conditions.
- step (2) the vulcanization reaction time is 0.5 to 24 hours.
- step (3) sulfuric acid is used to adjust the pH value of solution B to 0.5-5.
- step (3) the temperature of the insulation reaction is 0-100°C.
- step (3) the insulation reaction time is 0.5 to 5 hours.
- the beneficial effects of the present invention include:
- the present invention uses biological conversion technology combined with chemical precipitation.
- sulfate reducing bacteria are used to reduce sulfate ions into sulfide ions.
- the sulfide ions then react with molybdate ions in the tungstate solution to form sulfonate.
- Molybdate after the sulfurization process is complete, adjust the pH to convert MoS 4 2- into MoS 3 and precipitate, thereby achieving the purpose of efficient molybdenum removal and providing a new efficient separation technology of tungsten and molybdenum in the tungsten smelting process.
- This method has a short process and low energy consumption, which greatly reduces the cost of tungsten smelting and increases corporate benefits; it can effectively remove more than 94% of molybdenum in sodium tungstate solution.
- Figure 1 is a process flow diagram of the present invention.
- the present invention is aimed at further processing the sodium tungstate solution that has been processed similar to CN201911414064.5.
- the inventive solution usually first purifies and removes impurities from the sodium tungstate solution to remove elements such as silicon and phosphorus contained in the solution; in the process of purifying and removing impurities, excessive magnesium sulfate solution is often used to remove silicon and phosphorus. It is preferred to use 1.5 mol/L dilute sulfuric acid to adjust the acidity. The residual excess sulfate in the liquid also provides basic conditions for the subsequent use of sulfate reducing bacteria.
- Tungsten cobalt in the sodium tungstate solution exists in various forms, and the content is expressed as WO 3 and Co respectively.
- the sodium tungstate solution used in the present invention is analyzed and measured to have WO 3 : 115.20g/L and Mo: 0.49g/L.
- the method for separating and removing impurities from tungsten and molybdenum in the tungsten smelting process of the present invention includes the following steps:
- SRB sulfate reducing bacteria
- carbon sources are: glucose, starch, alcohols such as ethanol, propanol, etc., fatty acids such as lactate, pyruvic acid, malic acid, etc.
- sulfate reducing bacteria use carbon sources to gradually reduce SO 4 2- ions into S 2- ions, and S 2- ions are thiolated with MoO 4 2- ions in the tungstate solution to form sulfonate molybdate;
- the neutralization pH of the tungstate solution is: 5-10
- the inoculation amount of sulfate-reducing bacteria is 100-10000/mL
- the sulfurization reaction time is 0.5-24h
- the acid-adjusting temperature is 0-100°C
- the acidifying acid-adjusting pH is: 0.5-5
- acid adjustment reaction time is 0.5 ⁇ 5h;
- the present invention uses sulfate reducing bacteria to reduce SO 4 2- ions into S 2- ions, and the S 2- ions are sulfated with MoO 4 2- ions in the tungstate solution to form thiomolybdate.
- the sulfidation process After completion, continue to add dilute sulfuric acid to react MoS 4 2- with acid to form MoS 3 precipitation, thereby achieving the purpose of efficient molybdenum removal.
- the main reaction equation is as follows:
- CH 2 O represents organic carbon source
- the test results in Table 2 show that the type and number of bacterial groups in samples with large inoculums increases. As the culture time increases, due to nutrient consumption, metabolic waste accumulation and other reasons, the competition for nutrients among bacterial groups becomes fierce, and reduction occurs in the later stage. There was an obvious decreasing trend. Under the condition of inoculation amount of 5000/mL, carbon source and sulfate reducing bacteria had the strongest reducing effect on SO 4 2- ions. Among them, the optimal inoculation amount of sulfate-reducing bacteria ranges from 2000 to 6000/mL, and the optimal inoculum amount of sulfate-reducing bacteria ranges from 5000/mL.
- Reaction temperature (°C) WO 3 content (g/L) Mo content (g/L) 60 102.11 0.062 70 101.43 0.052 80 100.88 0.033 90 101.73 0.028 100 101.49 0.028
- the present invention uses a combination of biological + chemical methods to develop a new method for efficient separation of tungsten and molybdenum in the tungsten smelting process; using sulfate reducing bacteria to reduce SO 4 2- ions can efficiently remove molybdenum, thereby fully recovering tungsten and molybdenum. resource.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Biotechnology (AREA)
- Microbiology (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
La présente invention concerne un procédé de séparation et d'élimination d'impuretés de tungstène et de molybdène pendant un processus de fusion de tungstène. Le procédé comprend les étapes suivantes consistant : (1) à ajuster la valeur de pH d'une solution de tungstate contenant du molybdène sur une plage de 5 à 10, de façon à obtenir une solution A; (2) à ajouter une souche de bactérie réductrice de sulfate et une source de carbone à la solution A, et à soumettre cette dernière à une réaction de sulfuration, de façon à obtenir une solution B; et (3) à ajuster la solution B jusqu'à ce qu'elle soit acide, puis à la soumettre à une réaction de conservation de chaleur pour générer un précipité, et à filtrer le précipité, de façon à terminer la séparation et l'élimination d'impuretés du tungstène et du molybdène. Dans la présente invention, une technologie de biotransformation est combinée à une précipitation chimique; des ions sulfates sont d'abord réduits en ions soufre à l'aide de bactéries réductrices de sulfate; les ions soufre sont ensuite soumis à une réaction de thiolation avec des ions molybdate dans une solution de tungstate pour former un thiomolybdate; une fois le processus de sulfuration achevé, le pH est ajusté pour convertir le MoS4 2- en un précipité de MoS3; ce qui permet d'atteindre l'objectif d'élimination efficace de molybdène. L'invention concerne une toute nouvelle technologie de séparation efficace du tungstène et du molybdène pendant un processus de fusion de tungstène, lequel procédé peut éliminer efficacement 94 % ou plus de molybdène dans une solution de tungstate de sodium.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210460653.2 | 2022-04-28 | ||
| CN202210460653.2A CN114855000B (zh) | 2022-04-28 | 2022-04-28 | 一种钨冶炼过程中钨、钼分离除杂的方法 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2023206841A1 true WO2023206841A1 (fr) | 2023-11-02 |
Family
ID=82633706
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/CN2022/108809 WO2023206841A1 (fr) | 2022-04-28 | 2022-07-29 | Procédé de séparation et d'élimination d'impuretés de tungstène et de molybdène pendant un processus de fusion de tungstène |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN114855000B (fr) |
| WO (1) | WO2023206841A1 (fr) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1251825A (zh) * | 1998-10-20 | 2000-05-03 | 中南工业大学 | 钨钼分离的硫代钼酸盐制备方法 |
| US6113868A (en) * | 1996-07-05 | 2000-09-05 | H. C. Starck Gmbh & Co. Kg | Process for treating tungstate solutions to reduce molybdenum impurity and other impurity content |
| CN101434919A (zh) * | 2007-11-13 | 2009-05-20 | 北京有色金属研究总院 | 一株硫酸盐还原菌及其以稻草为碳氮源处理酸性矿山废水的工艺 |
| CN102642930A (zh) * | 2012-03-31 | 2012-08-22 | 中国科学院成都生物研究所 | 利用电流生长的硫酸盐还原菌处理重金属废水的方法 |
| CN208218924U (zh) * | 2018-04-04 | 2018-12-11 | 江西铜鼓有色冶金化工有限责任公司 | 一种钨冶炼过程中硫化除钼的系统 |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4303623A (en) * | 1981-01-19 | 1981-12-01 | Amax Inc. | Separation of trace molybdenum from tungstate solutions |
| CN1166565C (zh) * | 2001-10-16 | 2004-09-15 | 张启修 | 含钼的钨酸钠溶液中分离钼用的硫代钼酸盐制备方法 |
| CN1289683C (zh) * | 2005-06-18 | 2006-12-13 | 山西大学 | 纳米金属硫化物的微生物制备方法 |
| CN101338662B (zh) * | 2007-09-30 | 2013-04-10 | 盎亿泰地质微生物技术（北京）有限公司 | 预防和降低含水体系中的硫化氢和提高石油采收率的方法 |
| CN101177303B (zh) * | 2007-11-02 | 2010-06-02 | 北京有色金属研究总院 | 一种从钨酸盐溶液中除钼、砷、锑、锡的方法 |
| CN105660705A (zh) * | 2015-12-30 | 2016-06-15 | 哈尔滨工业大学 | 一种复合型硫酸盐还原菌活性生态抑制剂及其应用 |
| CN113788593B (zh) * | 2021-11-15 | 2022-02-18 | 中南大学 | 一种利用硫酸盐还原菌和铅锌冶炼渣协同处理含砷废液的方法 |
-
2022
- 2022-04-28 CN CN202210460653.2A patent/CN114855000B/zh active Active
- 2022-07-29 WO PCT/CN2022/108809 patent/WO2023206841A1/fr unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6113868A (en) * | 1996-07-05 | 2000-09-05 | H. C. Starck Gmbh & Co. Kg | Process for treating tungstate solutions to reduce molybdenum impurity and other impurity content |
| CN1251825A (zh) * | 1998-10-20 | 2000-05-03 | 中南工业大学 | 钨钼分离的硫代钼酸盐制备方法 |
| CN101434919A (zh) * | 2007-11-13 | 2009-05-20 | 北京有色金属研究总院 | 一株硫酸盐还原菌及其以稻草为碳氮源处理酸性矿山废水的工艺 |
| CN102642930A (zh) * | 2012-03-31 | 2012-08-22 | 中国科学院成都生物研究所 | 利用电流生长的硫酸盐还原菌处理重金属废水的方法 |
| CN208218924U (zh) * | 2018-04-04 | 2018-12-11 | 江西铜鼓有色冶金化工有限责任公司 | 一种钨冶炼过程中硫化除钼的系统 |
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| Publication number | Publication date |
|---|---|
| CN114855000B (zh) | 2023-08-22 |
| CN114855000A (zh) | 2022-08-05 |
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