WO2023206841A1 - Method for separation and impurity removal of tungsten and molybdenum during tungsten smelting process - Google Patents
Method for separation and impurity removal of tungsten and molybdenum during tungsten smelting process 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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- tungsten
- molybdenum
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- 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
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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
- 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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Abstract
The present invention relates to a method for separation and impurity removal of tungsten and molybdenum during a tungsten smelting process. The method comprises the following steps: (1) adjusting the pH value of a molybdenum-containing tungstate solution to 5-10, so as to obtain a solution A; (2) adding a sulfate reducing bacterium strain and a carbon source to the solution A, and subjecting same to a sulfuration reaction, so as to obtain a solution B; and (3) adjusting the solution B until same is acidic, subjecting same to a heat preservation reaction to generate a precipitate, and filtering out the precipitate, so as to finish the separation and impurity removal of tungsten and molybdenum. In the present invention, a biotransformation technology is combined with chemical precipitation; sulfate ions are firstly reduced into sulfur ions by using sulfate reducing bacteria; the sulfur ions are then subjected to a thioation reaction with molybdate ions in a tungstate solution to form thiomolybdate; after the sulfuration process is completed, the pH is adjusted to convert MoS4 2- into a MoS3 precipitate; therefore, the purpose of efficiently removing molybdenum is achieved. Provided is a brand new technology for efficient separation of tungsten and molybdenum during a tungsten smelting process, which method can effectively remove 94% or more of molybdenum in a sodium tungstate solution.
Description
本发明涉及钨湿法冶炼领域，具体为一种钨冶炼过程中钨、钼分离除杂的方法。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.
钨和钼是重要的战略稀有金属，在工业上具有广泛的用途。钨、钼同属元素周期表中ⅥB族，由于受“镧系收缩”影响，二者的原子半径、原子结构、化学性质都极其相似，使得分离过程难度很大。许多伴生钨钼元素资源中钨钼以类质同相存在，采用选矿方法往往不能有效地将钨、钼元素分离，通常采用冶金工艺进行分离。目前我国钨冶炼企业基本采用的是硫化铜沉淀法、离子交换分离法、溶剂萃取分离法等分离钨、钼，但以上工艺均存在除钼效率低、成本高、反应周期长等缺点。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.
发明内容Contents of the invention
本发明的目的在于克服上述技术不足，提供一种钨冶炼过程中钨、钼分离除杂的方法，解决现有技术中钨钼分离工艺除钼效率低、反应周期长的技术问题。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.
为达到上述技术目的，本发明方法的技术方案是：In order to achieve the above technical objectives, the technical solution of the method of the present invention is:
包括以下步骤：Includes the following steps:
(1)调节含钼钨酸盐溶液的pH值至5～10，得到溶液A；(1) Adjust the pH value of the molybdate-tungstate-containing solution to 5 to 10 to obtain solution A;
(2)向溶液A中加入硫酸盐还原菌菌种及碳源，进行硫化反应，得到溶液B；(2) Add sulfate-reducing bacteria strains and carbon sources to solution A to perform a sulfurization reaction to obtain solution B;
(3)调节溶液B至酸性，保温反应生成沉淀，滤除沉淀，完成钨、钼分离除杂。(3) Adjust solution B to be acidic, maintain the temperature and react to form a precipitate, filter out the precipitate, and complete the separation and removal of impurities from tungsten and molybdenum.
进一步地，步骤(1)中pH值为5～9。Further, the pH value in step (1) is 5-9.
进一步地，步骤(1)中通过硫酸和氢氧化钠溶液调节pH值。Further, in step (1), the pH value is adjusted by using sulfuric acid and sodium hydroxide solutions.
进一步地，步骤(2)中，硫酸盐还原菌菌种的接种量为100～10000 个/mL。Further, in step (2), the inoculum amount of sulfate-reducing bacteria is 100-10000/mL.
进一步地，步骤(2)中，碳源为葡萄糖、淀粉、醇类有机物和脂肪酸中的一种或几种。Further, in step (2), the carbon source is one or more of glucose, starch, organic alcohols and fatty acids.
进一步地，步骤(2)中，硫化反应是在无氧条件下进行的。Further, in step (2), the sulfidation reaction is carried out under anaerobic conditions.
进一步地，步骤(2)中，硫化反应时间为0.5～24h。Further, in step (2), the vulcanization reaction time is 0.5 to 24 hours.
进一步地，步骤(3)中，采用硫酸调节溶液B的pH值至0.5～5。Further, in step (3), sulfuric acid is used to adjust the pH value of solution B to 0.5-5.
进一步地，步骤(3)中，保温反应的温度为0～100℃。Further, in step (3), the temperature of the insulation reaction is 0-100°C.
进一步地，步骤(3)中，保温反应的时间0.5～5h。Further, in step (3), the insulation reaction time is 0.5 to 5 hours.
与现有技术相比，本发明的有益效果包括：Compared with the existing technology, the beneficial effects of the present invention include:
1、本发明利用生物转化技术与化学沉淀相结合，先利用硫酸盐还原菌将硫酸根离子还原成硫离子，硫离子再与钨酸盐溶液中的钼酸根离子硫代化反应，形成硫代钼酸盐，硫化过程完全后，调节pH，使MoS
4
2-转化为MoS
3沉淀，从而达到高效除钼的目的，提供了一种全新钨冶炼过程中钨、钼高效分离技术。
1. The present invention uses biological conversion technology combined with chemical precipitation. First, 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.
2、该方法流程短，能耗低，极大降低了钨冶炼成本，增加了企业效益；能够有效去除钨酸钠溶液中94％以上的钼。2. 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.
图1是本发明的工艺流程图。Figure 1 is a process flow diagram of the present invention.
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。In order to make the purpose, technical solutions and advantages of the present invention more clear, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described here are only used to explain the present invention and are not intended to limit the present invention.
本发明是针对类似CN201911414064.5处理结束的钨酸钠溶液做进一步处理。在实际生产应用过程中，该发明方案通常先要对钨酸钠溶液进行净化除杂，除去溶液中含有的硅磷等元素；在净化除杂过程中常采用过量的硫酸镁溶液进行除硅磷，优选1.5mol/L的稀硫酸调酸，液体中残余的过量硫酸根也为后续利用硫酸盐还原菌提供了基础条件。The present invention is aimed at further processing the sodium tungstate solution that has been processed similar to CN201911414064.5. In the actual production and application process, 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.
钨酸钠溶液中的钨钴存在形式多样，分别以WO
3、Co表达含量，本发 明采用的钨酸钠溶液分析测得WO
3：115.20g/L、Mo：0.49g/L。
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.
参见图1，本发明钨冶炼过程中钨钼分离除杂的方法，包括以下步骤：Referring to Figure 1, the method for separating and removing impurities from tungsten and molybdenum in the tungsten smelting process of the present invention includes the following steps:
(1)用稀硫酸或氢氧化钠溶液调节含钼的钨酸盐溶液至酸性；(1) Use dilute sulfuric acid or sodium hydroxide solution to adjust the molybdenum-containing tungstate solution to acidity;
(2)加入硫酸盐还原菌(SRB)菌种及足量碳源(碳源为：葡萄糖、淀粉、醇类如乙醇、丙醇等、脂肪酸如乳酸盐、丙酮酸、苹果酸等中的一种或几种混合)，添加碳源摩尔量应超过SO
4
2-离子摩尔量2倍(m
碳:m
硫酸根
-＝2:1为理论用量)，其中SO
4
2-离子摩尔量可根据前期添加的量进行计算。在无氧条件下，硫酸盐还原菌利用碳源逐步将SO
4
2-离子还原成S
2-离子，S
2-离子与钨酸盐溶液中的MoO
4
2-离子硫代化，形成硫代钼酸盐；
(2) Add sulfate reducing bacteria (SRB) strains and sufficient carbon sources (carbon sources are: glucose, starch, alcohols such as ethanol, propanol, etc., fatty acids such as lactate, pyruvic acid, malic acid, etc. One or several mixtures), the molar amount of carbon source added should exceed 2 times the molar amount of SO 4 2- ion (m carbon : m sulfate - = 2:1 is the theoretical amount), in which the molar amount of SO 4 2- ion can be Calculated based on the amount added previously. Under anaerobic conditions, 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;
(3)硫化过程完全后，继续加入稀硫酸酸化，使MoS
4
2-与酸反应形成MoS
3沉淀；过滤后即可得到纯净的钨酸盐溶液。
(3) After the sulfurization process is complete, continue to add dilute sulfuric acid for acidification, so that MoS 4 2- reacts with the acid to form MoS 3 precipitation; after filtration, a pure tungstate solution can be obtained.
其中，钨酸盐溶液中和pH：5～10，硫酸盐还原菌接种量100～10000个/mL，硫化反应时间0.5～24h，调酸温度0～100℃，酸化调酸pH:0.5～5，调酸反应时间0.5～5h；Among them, 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, and the acidifying acid-adjusting pH is: 0.5-5 , acid adjustment reaction time is 0.5~5h;
本发明是利用硫酸盐还原菌将SO
4
2-离子还原成S
2-离子，S
2-离子与钨酸盐溶液中的MoO
4
2-离子硫代化，形成硫代钼酸盐，硫化过程完全后，继续加入稀硫酸，使MoS
4
2-与酸反应形成MoS
3沉淀，从而达到高效除钼的目的。主要反应方程式如下：
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:
2H
++2CH
2O+SO
4
2-→S
2-+2H
2CO
2+H
2O
2H + +2CH 2 O+SO 4 2- →S 2- +2H 2 CO 2 +H 2 O
MoO
4
2-+4S
2-+4H
2O→MoS
4
2-(或MoO
xS
4-x
2-)+OH
-
MoO 4 2- +4S 2- +4H 2 O→MoS 4 2- (or MoO x S 4-x 2- )+OH -
式中CH
2O代表有机物碳源。
In the formula, CH 2 O represents organic carbon source.
下面通过具体的实施例对本发明做进一步详细说明。The present invention will be further described in detail below through specific examples.
实施例1 考察钨酸钠溶液pH值的影响Example 1 Investigating the influence of pH value of sodium tungstate solution
取钨酸钠溶液分析测得WO
3：115.20g/L、Mo：0.49g/L。向溶液中加入稀硫酸或氢氧化钠分别调至pH＝5、6、7、8、9；
The sodium tungstate solution was analyzed and found to be WO 3 : 115.20g/L and Mo: 0.49g/L. Add dilute sulfuric acid or sodium hydroxide to the solution to adjust pH=5, 6, 7, 8, and 9 respectively;
取中和后的钨酸钠溶液500ml至容量瓶中，SRB菌接种量5000个/mL与足量碳源，(碳源为：葡萄糖、淀粉、醇类如乙醇、丙醇等、脂肪酸如乳酸盐、丙酮酸、苹果酸等中的一种或几种混合)混合均匀后堵住瓶塞，静止存放进行硫化反应，24h后将溶液过滤，然后加入稀硫酸调节至pH＝1，升温至100℃，保温2h后降温过滤，分别测得滤液中钨和钼含量如下表1 所示。Take 500ml of the neutralized sodium tungstate solution into a volumetric flask, add an inoculum amount of SRB bacteria of 5000/mL and a sufficient amount of carbon source (carbon source is: glucose, starch, alcohols such as ethanol, propanol, etc., fatty acids such as milk (a mixture of one or more of salts, pyruvic acid, malic acid, etc.), mix evenly, plug the bottle stopper, and store it statically for vulcanization reaction. After 24 hours, filter the solution, then add dilute sulfuric acid to adjust to pH = 1, and heat to 100°C, incubate for 2 hours, then cool down and filter. The contents of tungsten and molybdenum in the filtrate are measured as shown in Table 1 below.
表1 不同钨酸钠溶液pH值环境下所得滤液中钨和钼含量Table 1 Contents of tungsten and molybdenum in the filtrate obtained under different pH values of sodium tungstate solution
| pH值pH value | WO 3含量(g/L) WO 3 content (g/L) | Mo含量(g/L)Mo content (g/L) |
| 55 | 101.32101.32 | 0.0450.045 |
| 66 | 102.42102.42 | 0.0360.036 |
| 77 | 101.52101.52 | 0.0270.027 |
| 88 | 101.79101.79 | 0.0410.041 |
| 99 | 100.65100.65 | 0.0570.057 |
表1试验结果说明，溶液偏酸或偏碱都会影响碳源与硫酸盐还原菌对SO
4
2-离子的还原作用，在中性pH＝7条件下，碳源与硫酸盐还原菌对SO
4
2-离子的还原作用最强。其中较优的范围pH＝5～9，最优条件pH＝7。
The test results in Table 1 illustrate that whether the solution is too acidic or too alkaline will affect the reduction of SO 4 2- ions by the carbon source and sulfate-reducing bacteria. Under the condition of neutral pH = 7, the carbon source and sulfate-reducing bacteria can reduce SO 4 ions . 2- ions have the strongest reducing effect. Among them, the preferable range is pH=5-9, and the optimal condition is pH=7.
实施例2 考察SRB菌接种量的影响Example 2 Examining the influence of SRB bacterial inoculation amount
取钨酸钠溶液分析测得WO
3：115.20g/L、Mo：0.49g/L；向溶液中加入稀盐酸分别调至pH＝7；
Take the sodium tungstate solution and analyze it to find WO 3 : 115.20g/L and Mo: 0.49g/L; add dilute hydrochloric acid to the solution to adjust the pH to 7;
取中和后的钨酸钠溶液500ml至容量瓶中，SRB菌接种量分别为2000、3000、4000、5000、6000个/mL与足量碳源，混合均匀后堵住瓶塞，静止存放进行硫化反应，24h后将溶液过滤，然后加入稀硫酸调节至pH＝1，升温至100℃，保温2h后降温过滤，分别测得滤液中钨和钼含量如下表2所示。Take 500ml of the neutralized sodium tungstate solution into a volumetric flask. The SRB bacterial inoculation amounts are 2000, 3000, 4000, 5000, 6000/mL and a sufficient amount of carbon source. Mix evenly, plug the bottle stopper, and store statically. After 24 hours of sulfidation reaction, the solution was filtered, then dilute sulfuric acid was added to adjust to pH=1, the temperature was raised to 100°C, kept for 2 hours and then cooled and filtered. The tungsten and molybdenum contents in the filtrate were measured as shown in Table 2 below.
表2 不同SRB菌接种量下所得滤液中钨和钼含量Table 2 Contents of tungsten and molybdenum in the filtrate obtained under different SRB bacterial inoculation amounts
| SRB菌接种量(个/mL)SRB bacteria inoculum volume (pieces/mL) | WO 3含量(g/L) WO 3 content (g/L) | Mo含量(g/L)Mo content (g/L) |
| 20002000 | 100.21100.21 | 0.0520.052 |
| 30003000 | 101.12101.12 | 0.0480.048 |
| 40004000 | 100.75100.75 | 0.0410.041 |
| 50005000 | 101.52101.52 | 0.0270.027 |
| 60006000 | 101.78101.78 | 0.0310.031 |
表2试验结果说明，接种量大的样品中菌群类型与数量多随培养时间延长，由于营养物质消耗、代谢废物积累等原因，菌群间对营养物的争夺竞争激烈，后期还原作用就出现了明显的降低趋势，在接种量5000个/mL条件下，碳源与硫酸盐还原菌对SO
4
2-离子的还原作用最强。其中较优硫酸 盐还原菌接种量的范围2000～6000个/mL，其中最优硫酸盐还原菌接种量的范围5000个/mL。
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.
实施例3 考察不同反应时间的影响Example 3 Examining the influence of different reaction times
取钨酸钠溶液分析测得WO
3：115.20g/L、Mo：0.49g/L；向溶液中加入稀盐酸分别调至pH＝7；
Take the sodium tungstate solution and analyze it to find WO 3 : 115.20g/L and Mo: 0.49g/L; add dilute hydrochloric acid to the solution to adjust the pH to 7;
取中和后的钨酸钠溶液500mL至容量瓶中，SRB菌接种量5000个/mL与足量碳源，混合均匀后堵住瓶塞，静止存放进行硫化反应，反应时间分别为8、12、16、20、24h后将溶液过滤，然后加入稀硫酸调节至pH＝1，升温至100℃，保温2h后降温过滤，分别测得滤液中钨和钼含量如下表3所示。Take 500mL of the neutralized sodium tungstate solution into a volumetric flask, add an inoculum amount of 5000 SRB bacteria/mL and a sufficient amount of carbon source, mix evenly, plug the bottle, and store statically for sulfurization reaction. The reaction times are 8 and 12 respectively. , filter the solution after 16, 20, and 24 hours, then add dilute sulfuric acid to adjust to pH = 1, raise the temperature to 100°C, keep it for 2 hours, then lower the temperature and filter. The contents of tungsten and molybdenum in the filtrate were measured as shown in Table 3 below.
表3 不同反应时间所得滤液中钨和钼含量Table 3 Contents of tungsten and molybdenum in the filtrate obtained at different reaction times
| 反应时间(h)Reaction time(h) | WO 3含量(g/L) WO 3 content (g/L) | Mo含量(g/L)Mo content (g/L) |
| 88 | 100.24100.24 | 0.0890.089 |
| 1212 | 101.38101.38 | 0.0570.057 |
| 1616 | 100.69100.69 | 0.0390.039 |
| 2020 | 101.49101.49 | 0.0280.028 |
| 24twenty four | 101.52101.52 | 0.0270.027 |
表3试验结果说明，SRB菌种配合碳源对SO
4
2-离子的还原作用随反应时间增长而增强，在反应时间达到20h条件下，碳源与硫酸盐还原菌对SO
4
2-离子的还原作用达到最大(20h后加长时间对其影响较小，综合考虑为20h最佳)。其中较优的反应时间为8～24h，最优反应时间为20h。
The test results in Table 3 show that the reducing effect of SRB bacteria on SO 4 2- ions when combined with carbon sources increases with the reaction time. When the reaction time reaches 20 hours, the carbon source and sulfate reducing bacteria reduce SO 4 2- ions. The reduction effect reaches the maximum (extension of time after 20h has little effect on it, and 20h is the best overall consideration). Among them, the preferred reaction time is 8 to 24h, and the optimal reaction time is 20h.
实施例4 考察不同调酸液pH值的影响Example 4 Examining the influence of different pH values of acid-adjusting solutions
取钨酸钠溶液分析测得WO
3：115.20g/L、Mo：0.49g/L；向溶液中加入稀盐酸分别调至pH＝7；
Take the sodium tungstate solution and analyze it to find WO 3 : 115.20g/L and Mo: 0.49g/L; add dilute hydrochloric acid to the solution to adjust the pH to 7;
取中和后的钨酸钠溶液500ml至容量瓶中，SRB菌接种量5000个/mL与足量碳源，混合均匀后堵住瓶塞，静止存放进行硫化反应，反应时间为20h后将溶液过滤，然后加入稀硫酸分别调节至pH＝0.5、1、2、3，升温至100℃，保温2h后降温过滤，分别测得滤液中钨和钼含量如下表4所示。Take 500ml of the neutralized sodium tungstate solution into a volumetric flask, add an inoculum amount of 5000 SRB bacteria/mL and a sufficient amount of carbon source, mix evenly, plug the bottle stopper, and store it statically for sulfurization reaction. After the reaction time is 20 hours, add the solution Filter, then add dilute sulfuric acid to adjust to pH = 0.5, 1, 2, and 3 respectively, raise the temperature to 100°C, keep it for 2 hours, then lower the temperature and filter, and measure the tungsten and molybdenum contents in the filtrate as shown in Table 4 below.
表4 不同调酸液pH值所得滤液中钨和钼含量Table 4 Contents of tungsten and molybdenum in filtrate obtained from different pH values of acid-adjusting solution
| 调酸液pH值Adjust pH value of acid solution | WO 3含量(g/L) WO 3 content (g/L) | Mo含量(g/L)Mo content (g/L) |
| 0.50.5 | 101.72101.72 | 0.0280.028 |
| 11 | 101.49101.49 | 0.0280.028 |
| 22 | 100.58100.58 | 0.0420.042 |
| 33 | 100.26100.26 | 0.0510.051 |
表4试验结果说明，调酸液pH升高会抑制MoS
4
2-与酸形成MoS
3沉淀反应的进行，导致除钼效率降低。在调酸液pH＝1条件下，溶液中MoS
4
2-离子完全沉淀。其中较优的反应pH范围为0.5～3，最优反应pH为1。
The test results in Table 4 show that increasing the pH of the acid-adjusting solution will inhibit the precipitation reaction of MoS 4 2- and acid to form MoS 3 , resulting in a reduction in molybdenum removal efficiency. Under the condition of pH=1 of the acid-adjusting solution, MoS 4 2- ions in the solution are completely precipitated. Among them, the preferred reaction pH range is 0.5-3, and the optimal reaction pH is 1.
实施例5 考察保温温度的影响Example 5 Examining the influence of insulation temperature
取钨酸钠溶液分析测得WO
3：115.20g/L、Mo：0.49g/L；向溶液中加入稀盐酸分别调至pH＝7；
Take the sodium tungstate solution and analyze it to find WO 3 : 115.20g/L and Mo: 0.49g/L; add dilute hydrochloric acid to the solution to adjust the pH to 7;
取中和后的钨酸钠溶液500ml至容量瓶中，SRB菌接种量5000个/mL与足量碳源，混合均匀后堵住瓶塞，静止存放进行硫化反应，反应时间为20h后将溶液过滤，然后加入稀硫酸调节至pH＝1，升温至60、70、80、90、100℃，保温2h后降温过滤，分别测得滤液中钨和钼含量如下表5所示。Take 500ml of the neutralized sodium tungstate solution into a volumetric flask, add an inoculation amount of 5000 SRB bacteria/mL and a sufficient amount of carbon source, mix evenly, plug the bottle stopper, and store it statically for sulfurization reaction. After the reaction time is 20 hours, add the solution Filter, then add dilute sulfuric acid to adjust to pH=1, raise the temperature to 60, 70, 80, 90, and 100°C, keep it for 2 hours, then lower the temperature and filter. The contents of tungsten and molybdenum in the filtrate are measured as shown in Table 5 below.
表5 不同保温温度所得滤液中钨和钼含量Table 5 Contents of tungsten and molybdenum in filtrate obtained at different holding temperatures
| 反应温度(℃)Reaction temperature (℃) | WO 3含量(g/L) WO 3 content (g/L) | Mo含量(g/L)Mo content (g/L) |
| 6060 | 102.11102.11 | 0.0620.062 |
| 7070 | 101.43101.43 | 0.0520.052 |
| 8080 | 100.88100.88 | 0.0330.033 |
| 9090 | 101.73101.73 | 0.0280.028 |
| 100100 | 101.49101.49 | 0.0280.028 |
表5试验结果说明，MoS
4
2-与酸形成MoS
3沉淀的反应随温度升高而不断增强，在保温温度达到90℃条件下，溶液中MoS
4
2-离子完全沉淀。其中较优的保温温度范围为60～100℃，最优保温温度为90℃。
The test results in Table 5 show that the reaction between MoS 4 2- and acid to form MoS 3 precipitation continues to increase as the temperature increases. When the holding temperature reaches 90°C, MoS 4 2- ions in the solution are completely precipitated. Among them, the preferable insulation temperature range is 60~100℃, and the optimal insulation temperature is 90℃.
实施例6 考察保温时间的影响Example 6 Investigating the influence of holding time
取钨酸钠溶液分析测得WO
3：115.20g/L、Mo：0.49g/L；向溶液中加入稀盐酸分别调至pH＝7；
Take the sodium tungstate solution and analyze it to find WO 3 : 115.20g/L and Mo: 0.49g/L; add dilute hydrochloric acid to the solution to adjust the pH to 7;
取中和后的钨酸钠溶液500mL至容量瓶中，SRB菌接种量5000个/mL与足量碳源，混合均匀后堵住瓶塞，静止存放进行硫化反应，反应时间为20h后将溶液过滤，然后加入稀硫酸调节至pH＝1，升温至90℃，保温0.5、 1、1.5、2、3h后降温过滤，分别测得滤液中钨和钼含量如下表6所示。Take 500mL of the neutralized sodium tungstate solution into a volumetric flask, add an inoculum amount of 5000 SRB bacteria/mL and a sufficient amount of carbon source, mix evenly, plug the bottle stopper, and store statically for sulfurization reaction. After the reaction time is 20 hours, add the solution Filter, then add dilute sulfuric acid to adjust to pH = 1, raise the temperature to 90°C, hold for 0.5, 1, 1.5, 2, and 3 hours, then cool down and filter. The tungsten and molybdenum contents in the filtrate are measured as shown in Table 6 below.
表6 不同保温时间所得滤液中钨和钼含量Table 6 Contents of tungsten and molybdenum in filtrate obtained at different holding times
| 保温时间(h)Keeping time (h) | WO 3含量(g/L) WO 3 content (g/L) | Mo含量(g/L)Mo content (g/L) |
| 0.50.5 | 100.87100.87 | 0.0710.071 |
| 11 | 101.31101.31 | 0.0620.062 |
| 1.51.5 | 100.51100.51 | 0.0390.039 |
| 22 | 101.73101.73 | 0.0280.028 |
| 33 | 101.52101.52 | 0.0280.028 |
表6试验结果说明，MoS
4
2-与酸形成MoS
3沉淀的反应随反应时间增长而不断增强，在反应时间达到2h条件下，溶液中MoS
4
2-离子完全沉淀。其中较优的反应时间范围为0.5-3h，最优保温时间为2h。
The test results in Table 6 show that the reaction between MoS 4 2- and acid to form MoS 3 precipitation continues to increase as the reaction time increases. When the reaction time reaches 2 hours, MoS 4 2- ions in the solution are completely precipitated. The optimal reaction time range is 0.5-3h, and the optimal holding time is 2h.
对比例1：离子交换分离法除钼Comparative Example 1: Molybdenum removal by ion exchange separation method
工业上应用的传统方法为强碱性阴离子交换法，取500mL钨酸钠溶液分析测得WO
3：115.20g/L、Mo：0.49g/L，首先加热钨酸钠溶液至80～90℃，向溶液中缓慢加入密度1.20～1.25g·cm
-3的Na
2S做硫化剂，控制溶液pH＝7～7.5进行硫化。将硫化完成后的溶液倒入装有树脂的交换柱中吸附，由于溶液在交换柱中流动，工作效率较低，48h后吸附完成。吸附完成后所得钨酸钠溶液中WO
3:96.53g/L，Mo:0.045g/L，钼吸附率为90.8％。
The traditional method applied in industry is the strong alkaline anion exchange method. Take 500mL of sodium tungstate solution and analyze and measure WO 3 : 115.20g/L, Mo: 0.49g/L. First, heat the sodium tungstate solution to 80~90°C. Slowly add Na 2 S with a density of 1.20 to 1.25 g·cm -3 as a vulcanizing agent into the solution, and control the pH of the solution = 7 to 7.5 for vulcanization. Pour the vulcanized solution into an exchange column filled with resin for adsorption. Since the solution flows in the exchange column, the work efficiency is low, and the adsorption is completed after 48 hours. After the adsorption is completed, the sodium tungstate solution obtained has WO 3 : 96.53g/L, Mo: 0.045g/L, and the molybdenum adsorption rate is 90.8%.
由于MoS
4
2-对强碱性阴离子交换树脂亲和力很大，通常采用氧化法使之氧化成MoO
4
2-解析。氧化过程放出大量热易使树脂变质，需降低解析速率，且解析完成后需大量的水淋洗树脂，增大钨损。由结果可知，传统离子交换法过程复杂，工作效率低，除钼率和钨保留率皆较低且产生大量废水。
Since MoS 4 2- has a great affinity for strong alkaline anion exchange resins, oxidation method is usually used to oxidize it into MoO 4 2- for analysis. The oxidation process releases a large amount of heat, which can easily cause the resin to deteriorate, requiring the analysis rate to be reduced. After the analysis is completed, a large amount of water is required to rinse the resin, which increases tungsten loss. It can be seen from the results that the traditional ion exchange method has a complicated process, low work efficiency, low molybdenum removal rate and tungsten retention rate, and generates a large amount of wastewater.
本发明利用生物+化学方式的结合，开发了一种全新的钨冶炼过程中钨、钼高效分离的方法；采用硫酸盐还原菌还原SO
4
2-离子可高效除钼，从而充分回收钨、钼资源。其中最优条件为钨酸盐溶液中和pH＝7，硫酸盐还原菌接种量5000个/mL，硫化反应时间20h，调酸温度90℃，调酸pH＝1，调酸反应时间2h，能够有效去除钨酸钠溶液中94％以上的钼。
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. Among them, the optimal conditions are tungstate solution neutralization pH=7, sulfate-reducing bacteria inoculum amount 5000/mL, sulfurization reaction time 20h, acid-adjusting temperature 90°C, acid-adjusting pH=1, acid-adjusting reaction time 2h. Effectively removes more than 94% of molybdenum in sodium tungstate solution.
以上所述本发明的具体实施方式，并不构成对本发明保护范围的限定。任何根据本发明的技术构思所做出的各种其他相应的改变与变形，均应包 含在本发明权利要求的保护范围内。The above-described specific embodiments of the present invention do not limit the scope of the present invention. Any other corresponding changes and modifications made based on the technical concept of the present invention shall be included in the protection scope of the claims of the present invention.
Claims (10)
- 一种钨冶炼过程中钨、钼分离除杂的方法，其特征在于，包括以下步骤：A method for separating tungsten and molybdenum and removing impurities during tungsten smelting, which is characterized by including the following steps:(1)调节含钼钨酸盐溶液的pH值至5～10，得到溶液A；(1) Adjust the pH value of the molybdate-tungstate-containing solution to 5 to 10 to obtain solution A;(2)向溶液A中加入硫酸盐还原菌菌种及碳源，进行硫化反应，得到溶液B；(2) Add sulfate-reducing bacteria strains and carbon sources to solution A to perform a sulfurization reaction to obtain solution B;(3)调节溶液B至酸性，保温反应生成沉淀，滤除沉淀，完成钨、钼分离除杂。(3) Adjust solution B to be acidic, maintain the temperature and react to form a precipitate, filter out the precipitate, and complete the separation and removal of impurities from tungsten and molybdenum.
- 根据权利要求1所述的钨冶炼过程中钨、钼分离除杂的方法，其特征在于，步骤(1)中pH值为5～9。The method for separating and removing impurities from tungsten and molybdenum in the tungsten smelting process according to claim 1, characterized in that the pH value in step (1) is 5 to 9.
- 根据权利要求1所述的钨冶炼过程中钨、钼分离除杂的方法，其特征在于，步骤(1)中通过硫酸和氢氧化钠溶液调节pH值。The method for separating and removing impurities from tungsten and molybdenum in the tungsten smelting process according to claim 1, characterized in that in step (1), the pH value is adjusted by sulfuric acid and sodium hydroxide solution.
- 根据权利要求1所述的钨冶炼过程中钨、钼分离除杂的方法，其特征在于，步骤(2)中，硫酸盐还原菌菌种的接种量为100～10000个/mL。The method for separating and removing impurities from tungsten and molybdenum during tungsten smelting according to claim 1, characterized in that in step (2), the inoculum amount of sulfate-reducing bacteria is 100 to 10,000/mL.
- 根据权利要求1所述的钨冶炼过程中钨、钼分离除杂的方法，其特征在于，步骤(2)中，碳源为葡萄糖、淀粉、醇类有机物和脂肪酸中的一种或几种。The method for separating and removing impurities from tungsten and molybdenum during tungsten smelting according to claim 1, characterized in that in step (2), the carbon source is one or more of glucose, starch, organic alcohols and fatty acids.
- 根据权利要求1所述的钨冶炼过程中钨、钼分离除杂的方法，其特征在于，步骤(2)中，硫化反应是在无氧条件下进行的。The method for separating and removing impurities from tungsten and molybdenum in the tungsten smelting process according to claim 1, characterized in that in step (2), the sulfidation reaction is carried out under anaerobic conditions.
- 根据权利要求1所述的钨冶炼过程中钨、钼分离除杂的方法，其特征在于，步骤(2)中，硫化反应时间为0.5～24h。The method for separating and removing impurities from tungsten and molybdenum in the tungsten smelting process according to claim 1, characterized in that in step (2), the sulfurization reaction time is 0.5 to 24 hours.
- 根据权利要求1所述的钨冶炼过程中钨、钼分离除杂的方法，其特征在于，步骤(3)中，采用硫酸调节溶液B的pH值至0.5～5。The method for separating and removing impurities from tungsten and molybdenum in the tungsten smelting process according to claim 1, characterized in that in step (3), sulfuric acid is used to adjust the pH value of solution B to 0.5-5.
- 根据权利要求1所述的钨冶炼过程中钨、钼分离除杂的方法，其特征在于，步骤(3)中，保温反应的温度为0～100℃。The method for separating and removing impurities from tungsten and molybdenum in the tungsten smelting process according to claim 1, characterized in that in step (3), the temperature of the insulation reaction is 0 to 100°C.
- 根据权利要求1所述的钨冶炼过程中钨、钼分离除杂的方法，其特征在于，步骤(3)中，保温反应的时间0.5～5h。The method for separating and removing impurities from tungsten and molybdenum in the tungsten smelting process according to claim 1, characterized in that in step (3), the time of the heat preservation reaction is 0.5 to 5 hours.
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