CN105200245A - Method for efficiently separating tungsten and molybdenum - Google Patents
Method for efficiently separating tungsten and molybdenum Download PDFInfo
- Publication number
- CN105200245A CN105200245A CN201510690665.4A CN201510690665A CN105200245A CN 105200245 A CN105200245 A CN 105200245A CN 201510690665 A CN201510690665 A CN 201510690665A CN 105200245 A CN105200245 A CN 105200245A
- Authority
- CN
- China
- Prior art keywords
- acid
- molybdenum
- tungsten
- solution
- precipitation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 128
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 120
- 239000011733 molybdenum Substances 0.000 title claims abstract description 120
- 239000010937 tungsten Substances 0.000 title claims abstract description 109
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 109
- 238000000034 method Methods 0.000 title claims abstract description 48
- 239000000243 solution Substances 0.000 claims abstract description 72
- 239000002253 acid Substances 0.000 claims abstract description 50
- 239000002244 precipitate Substances 0.000 claims abstract description 43
- 238000000926 separation method Methods 0.000 claims abstract description 19
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 11
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000605 extraction Methods 0.000 claims abstract description 7
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 7
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract 3
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 36
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 32
- 238000003916 acid precipitation Methods 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 238000001556 precipitation Methods 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 11
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 10
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 10
- 239000011609 ammonium molybdate Substances 0.000 claims description 10
- 229940010552 ammonium molybdate Drugs 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 238000005342 ion exchange Methods 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 239000000284 extract Substances 0.000 claims description 3
- 230000000717 retained effect Effects 0.000 claims 3
- 238000002156 mixing Methods 0.000 claims 2
- 239000002904 solvent Substances 0.000 claims 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 abstract description 35
- 239000000047 product Substances 0.000 abstract description 22
- MGRWKWACZDFZJT-UHFFFAOYSA-N molybdenum tungsten Chemical compound [Mo].[W] MGRWKWACZDFZJT-UHFFFAOYSA-N 0.000 abstract description 17
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 9
- 238000001914 filtration Methods 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 3
- VSOYJNRFGMJBAV-UHFFFAOYSA-N N.[Mo+4] Chemical compound N.[Mo+4] VSOYJNRFGMJBAV-UHFFFAOYSA-N 0.000 abstract 1
- 239000012535 impurity Substances 0.000 description 14
- 238000001704 evaporation Methods 0.000 description 7
- 230000008020 evaporation Effects 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- 235000015393 sodium molybdate Nutrition 0.000 description 7
- 239000011684 sodium molybdate Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 5
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 4
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical class NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- -1 thiomolybdate ion Chemical class 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 206010035148 Plague Diseases 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- CXVCSRUYMINUSF-UHFFFAOYSA-N tetrathiomolybdate(2-) Chemical compound [S-][Mo]([S-])(=S)=S CXVCSRUYMINUSF-UHFFFAOYSA-N 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
本发明涉及一种钨钼分离方法，包括：(1)先向钨钼混合溶液加入酸，形成钨酸、钼酸的混合沉淀；(2)向混合沉淀中加酸，使钼酸溶解；(3)过滤得到的钨酸沉淀用氨水溶解得到钨酸铵溶液，制得APT；(4)采用萃取剂或者离子交换树脂将含钼溶液中的钼提取出来，然后利用氨水解吸或反萃得到钼酸铵溶液，进一步制得四钼酸铵；(5)向离子交换后液或者萃余液添加适量的酸后返回至步骤(1)或(2)的混合液中。本发明所述分离方法考虑了钨钼产品的生产工艺，使分离出来的钨或钼直接用于其产品的制备，分离效果好，操作过程简单易控，易于工业化推广应用。The invention relates to a method for separating tungsten and molybdenum, comprising: (1) first adding acid to a tungsten-molybdenum mixed solution to form a mixed precipitate of tungstic acid and molybdenum acid; (2) adding acid to the mixed precipitate to dissolve the molybdenum acid; 3) The tungstic acid precipitate obtained by filtration is dissolved with ammonia water to obtain ammonium tungstate solution, and APT is obtained; (4) Molybdenum is extracted from the molybdenum-containing solution by using an extraction agent or ion exchange resin, and then desorbed or back-extracted with ammonia water to obtain molybdenum ammonium acid solution to further produce ammonium tetramolybdate; (5) return to the mixed solution of step (1) or (2) after adding an appropriate amount of acid to the ion-exchanged liquid or raffinate. The separation method of the present invention considers the production process of tungsten and molybdenum products, so that the separated tungsten or molybdenum can be directly used for the preparation of its products, the separation effect is good, the operation process is simple and easy to control, and it is easy to be popularized and applied in industrialization.
Description
技术领域technical field
本发明涉及稀有金属冶金领域，特别是钨钼冶炼过程中钨钼分离的技术方法。The invention relates to the field of rare metal metallurgy, in particular to a technical method for separating tungsten and molybdenum in the smelting process of tungsten and molybdenum.
背景技术Background technique
钨钼制品中的杂质含量严重影响其性能，对于钨制品来说最难除去的杂质元素是钼，而对于钼制品来说，钨则是最难分离的。为了提高钨钼制品的性能，钨钼的完全分离是必须的。由于镧系收缩，钨和钼具有相同的原子半径和相似的电子结构，而展现出非常相近的化学性质。因此，钨钼在自然界经常共生。目前我国钨钼资源的特点是：高钼的钨资源占全国白钨工业储量的50％左右，钼资源中高钨资源也约占1/3左右。如世界最大的柿竹园矿，Mo/WO3约为2％；河南栾川钼矿的伴生白钨储量高达62万吨(我国第二大白钨矿)，其中Mo/WO3约为10％；卢氏县夜长坪WO3储量18万吨，Mo/WO3约为30-50％；内蒙流沙山钼钨Mo/WO3约为300％。这些矿高钨、高钼，长期缺乏合适的处理工艺。为了很好的利用这些高钨高钼资源，急需开发高效的钨钼分离技术。The impurity content in tungsten and molybdenum products seriously affects its performance. For tungsten products, the most difficult impurity element is molybdenum, and for molybdenum products, tungsten is the most difficult to separate. In order to improve the performance of tungsten and molybdenum products, complete separation of tungsten and molybdenum is necessary. Due to the lanthanide contraction, tungsten and molybdenum exhibit very similar chemical properties due to the same atomic radius and similar electronic structure. Therefore, tungsten and molybdenum often coexist in nature. At present, the characteristics of my country's tungsten and molybdenum resources are: high molybdenum tungsten resources account for about 50% of the national scheelite industrial reserves, and high tungsten resources in molybdenum resources also account for about 1/3. For example, in Shizhuyuan Mine, the largest in the world, Mo/WO 3 is about 2%; the associated scheelite reserves in Henan Luanchuan Molybdenum Mine are as high as 620,000 tons (the second largest scheelite in China), of which Mo/WO 3 is about 10% ; Yechangping WO 3 reserves in Lushi County are 180,000 tons, and Mo/WO 3 is about 30-50%; Mo/WO 3 in Liushashan, Inner Mongolia is about 300%. These mines are high in tungsten and molybdenum, and have long lacked suitable treatment processes. In order to make good use of these high tungsten and high molybdenum resources, it is urgent to develop efficient tungsten and molybdenum separation technology.
但是钨钼极其相似的化学性质导致钨钼高效分离成为困扰钨钼冶金的技术难题。到目前为止，已研究出各种各样的钨钼分离方法。(1)从钨酸盐溶液中除去钼的方法主要是在适当的条件下将钨钼溶液中的钼进行硫化，形成硫代钼酸盐。利用硫代钼酸根离子与钨酸根离子性质差异，可利用沉淀法、萃取法或离子交换法等进行分离。此类方法除了存在硫污染的问题外，还存在除钼深度不够，或不适应处理高Mo溶液，或效率不高等问题。当前从钨酸盐溶液中深度除钨的主流技术是利用含铜化合物吸附MoS4 2-分离钨钼，此技术在中国已获得广泛应用。但是，当钼钨比超过1/20，其应用效果显著变差。而胍盐沉淀法则是另外一种不需进行硫化进行钨钼分离的方法。该法是利用钨酸根及钨的同多酸根与钼酸根及钼的同多酸根性质上的差异,在酸性条件下,钨和胍盐生成沉淀而钼仍在溶液里,从而达到钨钼分离的目的。但由于仲钨酸盐的结晶问题、钨钼聚合离子的生成以及这些离子本身性质差异不大等原因限制了这种方法的工业应用。(2)上述这些方法则不能应用到从钼酸盐溶液中除去微量钨。针对从钼酸盐溶液中深度除去微量钨的这一新的钼钨分离难题，许多学者做了一些研究。有研究发现伯胺对钼和钨具有一定的分离效果。采用单级萃取操作时，除钨率能就能达到92.7％，但钼损有近5％。也有利用钨、钼聚合能力差异，采用大孔碱性阴离子交换树脂将钼酸盐溶液中微量的钨去除，除钨率可达到96％，钼损不超过4％。但是需要先调整溶液pH值并放置5～12小时才能吸附。另外，也有采用多价过渡金属的氢氧化物或者水合氧化物吸附法，通过调整溶液体系pH达到一个较好的除钨效果。However, the extremely similar chemical properties of tungsten and molybdenum make the efficient separation of tungsten and molybdenum a technical problem that plagues tungsten and molybdenum metallurgy. So far, various separation methods of tungsten and molybdenum have been studied. (1) The method of removing molybdenum from the tungstate solution is mainly to sulfide the molybdenum in the tungsten-molybdenum solution under appropriate conditions to form thiomolybdate. Utilizing the difference in properties between thiomolybdate ion and tungstate ion, it can be separated by precipitation method, extraction method or ion exchange method. In addition to the problem of sulfur pollution, this kind of method also has problems such as insufficient molybdenum removal depth, or inappropriate treatment of high Mo solution, or low efficiency. The current mainstream technology for deep removal of tungsten from tungstate solution is to use copper-containing compounds to adsorb MoS 4 2- to separate tungsten and molybdenum. This technology has been widely used in China. However, when the ratio of molybdenum to tungsten exceeds 1/20, its application effect becomes significantly worse. The guanidinium salt precipitation method is another method for separating tungsten and molybdenum without sulfidation. This method utilizes the difference in properties between tungstate and tungsten isopolyacids, molybdate and molybdenum isopolyacids. Under acidic conditions, tungsten and guanidinium salts form precipitates while molybdenum is still in solution, so as to achieve the separation of tungsten and molybdenum. Purpose. However, the industrial application of this method is limited due to the crystallization of paratungstate, the generation of tungsten and molybdenum polymer ions, and the little difference in the properties of these ions themselves. (2) The above methods cannot be applied to remove trace tungsten from molybdate solution. Aiming at the new molybdenum and tungsten separation problem of deep removal of trace tungsten from molybdate solution, many scholars have done some research. Studies have found that primary amines have a certain separation effect on molybdenum and tungsten. When using single-stage extraction operation, the tungsten removal rate can reach 92.7%, but the molybdenum loss is nearly 5%. There is also a use of the difference in the polymerization ability of tungsten and molybdenum to remove trace tungsten in the molybdate solution by using macroporous basic anion exchange resin. The tungsten removal rate can reach 96%, and the loss of molybdenum does not exceed 4%. However, it is necessary to adjust the pH value of the solution and place it for 5-12 hours before adsorption. In addition, there is also an adsorption method using hydroxides or hydrated oxides of polyvalent transition metals to achieve a better tungsten removal effect by adjusting the pH of the solution system.
以上这些方法基本上是针对微量的钨或者钼的除去，往往不能很好的处理钨钼含量都比较高的溶液，因而需要开发相应的宏量钨钼分离技术。目前也只有通过采用过渡金属盐选择性沉淀钨钼混合溶液中钨，从而达到分离钨钼的效果。虽然此方法有一定效果，但是将原本已经通过碱分解进入到溶液中的高浓度钨沉淀，后续回收这些钨还需重新再分解含钨沉淀，造成原料的不必要损耗，使整个分离钨钼的成本大大提高。The above methods are basically aimed at the removal of trace amounts of tungsten or molybdenum, and often cannot handle solutions with high tungsten and molybdenum content very well. Therefore, it is necessary to develop corresponding macro-volume tungsten and molybdenum separation technologies. At present, the effect of separating tungsten and molybdenum can only be achieved by using transition metal salts to selectively precipitate tungsten in a tungsten-molybdenum mixed solution. Although this method has a certain effect, but the high-concentration tungsten precipitates that have entered the solution through alkali decomposition, the subsequent recovery of these tungsten needs to re-decompose the tungsten-containing precipitates, resulting in unnecessary loss of raw materials, making the entire separation of tungsten and molybdenum The cost is greatly increased.
因此，基于以上分析，开发新的高效钨钼分离技术十分必要。Therefore, based on the above analysis, it is necessary to develop a new high-efficiency separation technology of tungsten and molybdenum.
发明内容Contents of the invention
本发明的目的是提供一种高效的钨钼分离方法，特别适合处理高浓度钨钼混合溶液。该方法考虑了钨钼产品的生产工艺，使分离出来的钨或钼直接用于其产品的制备，分离效果好，操作过程简单易控，易于工业化推广应用。The purpose of the present invention is to provide an efficient method for separating tungsten and molybdenum, which is especially suitable for processing high-concentration tungsten and molybdenum mixed solutions. The method considers the production process of tungsten and molybdenum products, so that the separated tungsten or molybdenum can be directly used for the preparation of the products, the separation effect is good, the operation process is simple and easy to control, and it is easy to be popularized and applied in industrialization.
为了实现上述目的，本发明采用如下技术方案：In order to achieve the above object, the present invention adopts the following technical solutions:
一种钨钼分离方法，包括如下步骤：A method for separating tungsten and molybdenum, comprising the steps of:
(1)先向钨钼混合溶液加酸至溶液pH值为1-3，反应形成钨酸、钼酸的混合沉淀，分离，洗涤；(1) Add acid to the tungsten-molybdenum mixed solution until the pH value of the solution is 1-3, react to form a mixed precipitate of tungstic acid and molybdic acid, separate and wash;
(2)向混合沉淀中继续加酸，使钼酸溶解，而钨酸继续保留在沉淀中；(2) Continue to add acid to the mixed precipitate to dissolve the molybdic acid, while the tungstic acid continues to remain in the precipitate;
(3)过滤得到的钨酸沉淀，洗涤，用氨水溶解，得到钨酸铵溶液，进一步制得APT；(3) The precipitated tungstic acid obtained by filtration is washed and dissolved with ammonia water to obtain an ammonium tungstate solution, and further prepare APT;
(4)采用萃取剂或者离子交换树脂将步骤(2)得到的含钼溶液中的钼提取出来，然后利用氨水解吸或反萃得到钼酸铵溶液，进一步制得四钼酸铵；(4) extracting the molybdenum in the molybdenum-containing solution obtained in step (2) by using an extractant or an ion exchange resin, then utilizing ammonia desorption or stripping to obtain an ammonium molybdate solution, and further preparing ammonium tetramolybdate;
(5)向离子交换后液或者萃余液添加适量的酸后返回至步骤(1)或(2)的混合液中。(5) Add an appropriate amount of acid to the ion-exchanged liquid or raffinate and return it to the mixed liquid in step (1) or (2).
上述反应历程为：先加入酸使体系pH值控制在1-3之间，钨和钼将会同时分别形成钨酸和钼酸混合沉淀。再继续加入高浓度的酸进行分解反应，可将钼酸沉淀溶解返回至溶液中，而钨酸沉淀则无论酸浓度多高都不会溶解，从而达到钼与钨的分离。The above reaction process is as follows: first add acid to control the pH value of the system between 1-3, and tungsten and molybdenum will simultaneously form tungstic acid and molybdenum acid mixed precipitation. Continue to add high-concentration acid to carry out the decomposition reaction, and the molybdenum acid precipitate can be dissolved and returned to the solution, while the tungstic acid precipitate will not dissolve no matter how high the acid concentration is, so as to achieve the separation of molybdenum and tungsten.
本发明所述分离钨钼的方法中，步骤(1)中，所述钨钼混合溶液中钨与钼的质量比为0.1～10:1，优选0.2-3.2:1，且钨和钼的浓度分别为10～300g/L。In the method for separating tungsten and molybdenum described in the present invention, in step (1), the mass ratio of tungsten to molybdenum in the tungsten-molybdenum mixed solution is 0.1-10:1, preferably 0.2-3.2:1, and the concentration of tungsten and molybdenum 10-300g/L respectively.
本发明所述分离钨钼的方法中，步骤(1)中，溶液pH值为1-2.5。In the method for separating tungsten and molybdenum of the present invention, in step (1), the pH value of the solution is 1-2.5.
本发明所述分离钨钼的方法中，步骤(1)中，反应温度为40-80℃。In the method for separating tungsten and molybdenum described in the present invention, in step (1), the reaction temperature is 40-80°C.
本发明所述分离钨钼的方法中，步骤(1)和(3)中，所述酸为硫酸，盐酸和硝酸中的一种或几种。其中，各酸的浓度为：硫酸的浓度为1～16mol/L，盐酸的浓度为1～12mol/L，硝酸浓度1～14mol/L。In the method for separating tungsten and molybdenum of the present invention, in steps (1) and (3), the acid is one or more of sulfuric acid, hydrochloric acid and nitric acid. Wherein, the concentration of each acid is as follows: the concentration of sulfuric acid is 1-16 mol/L, the concentration of hydrochloric acid is 1-12 mol/L, and the concentration of nitric acid is 1-14 mol/L.
本发明所述分离钨钼的方法中，步骤(2)中，通过控制酸的浓度和加入量使钼酸溶解进入到混合液中，而钨酸保留在沉淀中。所述酸的加入量与混合沉淀中钼酸的摩尔比为2～10：1，优选3-8.2:1。In the method for separating tungsten and molybdenum described in the present invention, in step (2), molybdic acid is dissolved into the mixed solution by controlling the concentration and amount of acid added, while tungstic acid remains in the precipitate. The molar ratio of the added amount of the acid to the molybdic acid in the mixed precipitate is 2-10:1, preferably 3-8.2:1.
本发明所述分离钨钼的方法中，步骤(2)中，酸浓度越高，钼酸的溶解效果越高；但酸浓度太高对设备的要求也相应提高，还会增加生产成本，本发明优选浓度为8-16mol/L的硫酸。In the method for separating tungsten and molybdenum described in the present invention, in step (2), the higher the acid concentration, the higher the dissolving effect of molybdic acid; but the too high acid concentration also increases the requirements for equipment accordingly, and also increases the production cost. Invention preferred concentration is the sulfuric acid of 8-16mol/L.
本发明所述分离钨钼的方法中，步骤(2)中，反应温度为65-90℃。In the method for separating tungsten and molybdenum described in the present invention, in step (2), the reaction temperature is 65-90°C.
作为本发明优选的实施方式，步骤(2)中，还可以在加入酸后再加入钨粉，使部分未溶的钼酸进一步溶解，而钨酸保留在沉淀中。或者，向混合沉淀中同时加入酸和钨粉，控制酸的浓度和加入量使钼酸溶解进入到溶液中，而钨酸保留在沉淀中。所述钨粉的加入量与钼酸沉淀的摩尔比为0.1～0.5：1。As a preferred embodiment of the present invention, in step (2), tungsten powder can also be added after adding the acid to further dissolve part of the undissolved molybdic acid, while the tungstic acid remains in the precipitate. Or, add acid and tungsten powder to the mixed precipitate at the same time, control the concentration and amount of acid so that molybdic acid dissolves into the solution, while tungstic acid remains in the precipitate. The molar ratio of the added amount of the tungsten powder to the molybdic acid precipitation is 0.1-0.5:1.
本发明所述分离钨钼的方法中，步骤(3)中，所得钨酸沉淀中钨钼质量比大幅增加，达到100～1000：1。比值越大说明钨酸中钼含量越少，分离的越彻底。同理含钼溶液中钼钨质量比也是数值越大说明钼中钨钼含量越少，分离的约彻底。In the method for separating tungsten and molybdenum described in the present invention, in step (3), the mass ratio of tungsten and molybdenum in the obtained tungstic acid precipitation is greatly increased, reaching 100-1000:1. The larger the ratio, the less molybdenum content in tungstic acid, and the more thorough the separation. Similarly, the mass ratio of molybdenum and tungsten in the molybdenum-containing solution is also larger, indicating that the content of tungsten and molybdenum in molybdenum is less, and the separation is about complete.
作为本发明优选的实施方式，所述分离钨钼的方法，包括如下步骤：As a preferred embodiment of the present invention, the method for separating tungsten and molybdenum includes the following steps:
(1)向钨钼质量比为0.1～10：1的钨/钼酸钠混合液中加酸至溶液pH值为1～3，搅拌反应，得到钨酸和钼酸的混合沉淀；(1) Add acid to the tungsten/sodium molybdate mixed solution with a tungsten-molybdenum mass ratio of 0.1-10:1 until the pH of the solution is 1-3, stir and react to obtain a mixed precipitate of tungstic acid and molybdic acid;
(2)向混合沉淀中加酸，得到含钼溶液及钨酸沉淀；其中，酸的加入量与混合沉淀中钼酸的摩尔比为2～10：1；(2) Add acid to the mixed precipitate to obtain molybdenum-containing solution and tungstic acid precipitate; wherein, the molar ratio of the amount of acid added to molybdic acid in the mixed precipitate is 2 to 10:1;
(3)将钨酸沉淀用氨水溶解得到钨酸铵溶液，经蒸发结晶得到APT；(3) Dissolve the tungstic acid precipitate with ammonia water to obtain ammonium tungstate solution, and obtain APT through evaporation and crystallization;
(4)采用萃取剂或者离子交换树脂将步骤(2)得到的含钼溶液中的钼提取出来，然后利用氨水解吸或反萃得到钼酸铵溶液，经酸沉制备得到四钼酸铵；(4) Extract the molybdenum in the molybdenum-containing solution obtained in step (2) using an extractant or an ion exchange resin, then utilize ammonia desorption or stripping to obtain an ammonium molybdate solution, and prepare ammonium tetramolybdate through acid precipitation;
(5)向离子交换后液或者萃余液添加适量的酸后返回至步骤(1)或(2)的混合液中。(5) Add an appropriate amount of acid to the ion-exchanged liquid or raffinate and return it to the mixed liquid in step (1) or (2).
本发明所述分离方法考虑了钨钼产品的生产工艺，使分离出来的钨或钼直接用于其产品的制备，分离效果好，操作过程简单易控，易于工业化推广应用。The separation method of the present invention considers the production process of tungsten and molybdenum products, so that the separated tungsten or molybdenum can be directly used for the preparation of its products, the separation effect is good, the operation process is simple and easy to control, and it is easy to be popularized and applied in industrialization.
具体实施方式Detailed ways
以下实施例用于说明本发明，但不用来限制本发明的范围。The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention.
实施例1Example 1
一种钨钼分离方法，包括如下步骤：A method for separating tungsten and molybdenum, comprising the steps of:
(1)先向钨浓度为10g/L、钨钼质量比为0.2：1的钨/钼酸钠混合溶液中加入硫酸，搅拌反应，控制反应温度为60℃和溶液pH值为2.5，反应10分钟，反应完成后经过滤洗涤得到钨酸和钼酸混合沉淀；(1) First add sulfuric acid to the tungsten/sodium molybdate mixed solution with a tungsten concentration of 10g/L and a mass ratio of tungsten to molybdenum of 0.2:1, stir and react, control the reaction temperature to 60°C and the pH value of the solution to 2.5, and react for 10 Minutes, after the reaction is completed, the mixed precipitate of tungstic acid and molybdic acid is obtained by filtering and washing;
(2)向混合沉淀中加入浓度为12mol/L的硫酸，其加入量与沉淀中钼酸的摩尔比为6：1，控制反应温度为70℃和反应时间为2小时，反应完成后经过滤洗涤得到钨钼质量比为845：1的钨酸沉淀和钼钨质量比为667:1的含钼溶液；(2) Add sulfuric acid with a concentration of 12mol/L to the mixed precipitate, the molar ratio of the added amount to the molybdic acid in the precipitate is 6:1, control the reaction temperature to 70°C and the reaction time to 2 hours, and filter after the reaction is completed Wash to obtain a tungsten acid precipitate with a tungsten-molybdenum mass ratio of 845:1 and a molybdenum-containing solution with a molybdenum-tungsten mass ratio of 667:1;
(3)将钨酸沉淀用氨水溶解得到钨酸铵溶液，经蒸发结晶得到APT，杂质含量达到国标0级产品要求；(3) Dissolve tungstic acid precipitation with ammonia water to obtain ammonium tungstate solution, and obtain APT through evaporation and crystallization, and the impurity content reaches the national standard 0-grade product requirements;
(4)采用离子交换树脂将溶液中的钼提取，负载钼树脂用氨水解吸得到钼酸铵溶液，经酸沉制备得到四钼酸铵，杂质含量达到国标0级产品要求；(4) The molybdenum in the solution is extracted by ion exchange resin, the loaded molybdenum resin is desorbed with ammonia water to obtain ammonium molybdate solution, and ammonium tetramolybdate is prepared through acid precipitation, and the impurity content reaches the national standard 0 grade product requirements;
(5)离子交换后液经补加硫酸后再返回用于沉淀钨酸和钼酸的反应。(5) After ion exchange, the solution is added with sulfuric acid and then returned to the reaction for precipitating tungstic acid and molybdic acid.
实施例2Example 2
一种钨钼分离方法，包括如下步骤：A method for separating tungsten and molybdenum, comprising the steps of:
(1)先向钨浓度为185g/L、钨钼质量比为1.2：1的钨/钼酸钠混合溶液中加入盐酸，搅拌反应，控制反应温度为70℃和溶液pH值为1，反应90分钟，反应完成后经过滤洗涤得到钨酸和钼酸混合沉淀；(1) First add hydrochloric acid to the tungsten/sodium molybdate mixed solution with a tungsten concentration of 185g/L and a tungsten-molybdenum mass ratio of 1.2:1, and stir for reaction. Minutes, after the reaction is completed, the mixed precipitate of tungstic acid and molybdic acid is obtained by filtering and washing;
(2)向混合沉淀中加入浓度为16mol/L的硫酸，其加入量与沉淀中钼酸的摩尔比为5.5：1，控制反应温度为80℃和反应时间为3小时，反应完成后经过滤洗涤得到钨钼质量比为897:1的钨酸沉淀和钼钨质量比为720:1的含钼溶液；(2) Add sulfuric acid with a concentration of 16mol/L to the mixed precipitate, the molar ratio of the added amount to molybdic acid in the precipitate is 5.5:1, control the reaction temperature to 80°C and the reaction time to 3 hours, and filter after the reaction is completed Washing to obtain a tungsten acid precipitation with a mass ratio of tungsten to molybdenum of 897:1 and a molybdenum-containing solution with a mass ratio of molybdenum to tungsten of 720:1;
(3)将钨酸沉淀用氨水溶解得到钨酸铵溶液，经蒸发结晶得到APT，杂质含量达到国标0级产品要求；(3) Dissolve tungstic acid precipitation with ammonia water to obtain ammonium tungstate solution, and obtain APT through evaporation and crystallization, and the impurity content reaches the national standard 0-grade product requirements;
(4)采用萃取剂将溶液中的钼提取，负载钼有机相用氨水解吸得到钼酸铵溶液，经酸沉制备得到四钼酸铵，杂质含量达到国标0级产品要求；(4) The molybdenum in the solution is extracted with an extractant, and the molybdenum-loaded organic phase is desorbed with ammonia water to obtain an ammonium molybdate solution, which is prepared by acid precipitation to obtain ammonium tetramolybdate, and the impurity content reaches the national standard 0-grade product requirements;
(5)萃余液经补加硫酸后再返回用于沉淀钨酸和钼酸的反应。(5) The raffinate is returned to the reaction of precipitating tungstic acid and molybdic acid after adding sulfuric acid.
实施例3Example 3
一种钨钼分离方法，包括如下步骤：A method for separating tungsten and molybdenum, comprising the steps of:
(1)先向钨浓度为215g/L、钨钼质量比为3.2：1的钨/钼酸钠混合溶液中加入盐酸搅拌反应，控制反应温度为80℃和溶液pH值为1.2，反应3小时，反应完成后经过滤洗涤得到钨酸和钼酸混合沉淀；(1) Add hydrochloric acid to the tungsten/sodium molybdate mixed solution with a tungsten concentration of 215g/L and a tungsten-molybdenum mass ratio of 3.2:1 and stir to react. Control the reaction temperature at 80°C and the pH value of the solution at 1.2, and react for 3 hours , After the reaction is completed, the mixed precipitate of tungstic acid and molybdic acid is obtained by filtering and washing;
(2)向混合沉淀中加入浓度为12mol/L的盐酸，其加入量与沉淀中钼酸的摩尔比为3：1，同时还加入钨粉，其加入量与沉淀中钼酸的摩尔比为0.5，控制反应温度为90℃和反应时间为2.5小时，反应完成后经过滤洗涤得到钨钼质量比为927:1的钨酸沉淀和钼钨质量比为823:1的含钼溶液；(2) Adding hydrochloric acid with a concentration of 12mol/L to the mixed precipitate, the molar ratio of the amount added to the molybdic acid in the precipitate is 3:1, and tungsten powder is also added at the same time, the molar ratio of the added amount to the molybdic acid in the precipitate is 0.5, control the reaction temperature to be 90°C and the reaction time to be 2.5 hours. After the reaction is completed, filter and wash to obtain a tungsten acid precipitate with a tungsten-molybdenum mass ratio of 927:1 and a molybdenum-containing solution with a molybdenum-tungsten mass ratio of 823:1;
(3)将钨酸沉淀用氨水溶解得到钨酸铵溶液，经蒸发结晶得到APT，杂质含量达到国标0级产品要求；(3) Dissolve tungstic acid precipitation with ammonia water to obtain ammonium tungstate solution, and obtain APT through evaporation and crystallization, and the impurity content reaches the national standard 0-grade product requirements;
(4)采用萃取剂将溶液中的钼提取，负载钼有机相用氨水解吸得到钼酸铵溶液，经酸沉制备得到四钼酸铵，杂质含量达到国标0级产品要求；(4) The molybdenum in the solution is extracted with an extractant, and the molybdenum-loaded organic phase is desorbed with ammonia water to obtain an ammonium molybdate solution, which is prepared by acid precipitation to obtain ammonium tetramolybdate, and the impurity content reaches the national standard 0-grade product requirements;
(5)萃余液经补加硫酸后再返回用于分解钨酸和钼酸的混合沉淀反应。(5) The raffinate is returned to the mixed precipitation reaction for decomposing tungstic acid and molybdic acid after adding sulfuric acid.
实施例4Example 4
一种钨钼分离方法，包括如下步骤：A method for separating tungsten and molybdenum, comprising the steps of:
(1)先向钨浓度为123g/L、钨钼质量比为1：1的钨/钼酸钠混合溶液中加入盐酸，搅拌反应，控制反应温度为40℃和溶液pH值为1.8，反应6小时，反应完成后经过滤洗涤得到钨酸和钼酸混合沉淀；(1) First add hydrochloric acid to the tungsten/sodium molybdate mixed solution with a tungsten concentration of 123g/L and a mass ratio of tungsten to molybdenum of 1:1, stir and react, control the reaction temperature to 40°C and the pH value of the solution to 1.8, and react 6 hour, after the completion of the reaction, the mixed precipitate of tungstic acid and molybdic acid was obtained by filtering and washing;
(2)向混合沉淀中加入浓度为8mol/L的盐酸，其加入量与沉淀中钼酸的摩尔比为4.5：1，控制反应温度为65℃和反应时间为1.5小时，然后再加入钨粉，其加入量与沉淀中钼酸的摩尔比为0.4，控制反应温度为65℃和反应时间为2.0小时，反应完成后经过滤洗涤得到钨钼质量比为745:1的钨酸沉淀和钼钨质量比为678:1的含钼溶液；(2) Add hydrochloric acid with a concentration of 8mol/L to the mixed precipitate, the molar ratio of the added amount to molybdic acid in the precipitate is 4.5:1, control the reaction temperature to 65°C and the reaction time to 1.5 hours, and then add tungsten powder , the molar ratio of the added amount to the molybdenum acid in the precipitation is 0.4, the control reaction temperature is 65°C and the reaction time is 2.0 hours, after the reaction is completed, the tungsten acid precipitation and the molybdenum-tungsten mass ratio of 745:1 are obtained by filtering and washing. A molybdenum-containing solution with a mass ratio of 678:1;
(3)将钨酸沉淀用氨水溶解得到钨酸铵溶液，经蒸发结晶得到APT，杂质含量达到国标0级产品要求；(3) Dissolve tungstic acid precipitation with ammonia water to obtain ammonium tungstate solution, and obtain APT through evaporation and crystallization, and the impurity content reaches the national standard 0-grade product requirements;
(4)采用离子交换树脂将溶液中的钼提取，负载钼树脂用氨水解吸得到钼酸铵溶液，经酸沉制备得到四钼酸铵，杂质含量达到国标0级产品要求；(4) The molybdenum in the solution is extracted by ion exchange resin, the loaded molybdenum resin is desorbed with ammonia water to obtain ammonium molybdate solution, and ammonium tetramolybdate is prepared through acid precipitation, and the impurity content reaches the national standard 0 grade product requirements;
(5)离子交换后液经补加硫酸后再返回用于沉淀钨酸和钼酸的反应。(5) After ion exchange, the solution is added with sulfuric acid and then returned to the reaction for precipitating tungstic acid and molybdic acid.
实施例5Example 5
一种钨钼分离方法，包括如下步骤：A method for separating tungsten and molybdenum, comprising the steps of:
(1)先向温度为25℃，钨浓度为145g/L、钨钼质量比为2.0：1的钨/钼酸钠混合溶液中加入硫酸搅拌反应，控制溶液pH值为2.5，反应4小时，反应完成后经过滤洗涤得到钨酸和钼酸混合沉淀；(1) First add sulfuric acid to the tungsten/sodium molybdate mixed solution with a temperature of 25°C, a tungsten concentration of 145g/L, and a tungsten-molybdenum mass ratio of 2.0:1, and stir to react. Control the pH of the solution to 2.5, and react for 4 hours. After the reaction is completed, the mixed precipitate of tungstic acid and molybdic acid is obtained by filtering and washing;
(2)向混合沉淀中加入浓度为10mol/L的硝酸，其加入量与沉淀中钼酸的摩尔比为8.2：1，控制反应温度为75℃和反应时间为8.0小时，反应完成后经过滤洗涤得到钨钼质量比为816:1的钨酸沉淀和钼钨质量比为736:1的含钼溶液；(2) Add nitric acid with a concentration of 10mol/L to the mixed precipitate, the molar ratio of the added amount to molybdic acid in the precipitate is 8.2:1, control the reaction temperature to 75°C and the reaction time to 8.0 hours, and filter after the reaction is completed Washing to obtain a tungstic acid precipitation with a mass ratio of tungsten to molybdenum of 816:1 and a molybdenum-containing solution with a mass ratio of molybdenum to tungsten of 736:1;
(3)将钨酸沉淀用氨水溶解得到钨酸铵溶液，经蒸发结晶得到APT，杂质含量达到国标0级产品要求；(3) Dissolve tungstic acid precipitation with ammonia water to obtain ammonium tungstate solution, and obtain APT through evaporation and crystallization, and the impurity content reaches the national standard 0-grade product requirements;
(4)采用萃取剂将溶液中的钼提取，负载钼有机相用氨水解吸得到钼酸铵溶液，经酸沉制备得到四钼酸铵，杂质含量达到国标0级产品要求；(4) The molybdenum in the solution is extracted with an extractant, and the molybdenum-loaded organic phase is desorbed with ammonia water to obtain an ammonium molybdate solution, which is prepared by acid precipitation to obtain ammonium tetramolybdate, and the impurity content reaches the national standard 0-grade product requirements;
(5)萃余液经补加硫酸后再返回用于分解钨酸和钼酸混合沉淀的反应。(5) The raffinate is returned to the reaction for decomposing the mixed precipitation of tungstic acid and molybdic acid after adding sulfuric acid.
实施例6Example 6
一种钨钼分离方法，包括如下步骤：A method for separating tungsten and molybdenum, comprising the steps of:
(1)先向钨浓度为106g/L、钨钼质量比为1.1：1的钨/钼酸钠混合溶液中加入盐酸搅拌反应，控制反应温度为55℃和溶液pH值为1.2，反应3小时，反应完成后经过滤洗涤得到钨酸和钼酸混合沉淀；(1) Add hydrochloric acid to the tungsten/sodium molybdate mixed solution with a tungsten concentration of 106g/L and a mass ratio of tungsten to molybdenum of 1.1:1 and stir for reaction. Control the reaction temperature at 55°C and the pH value of the solution at 1.2, and react for 3 hours , After the reaction is completed, the mixed precipitate of tungstic acid and molybdic acid is obtained by filtering and washing;
(2)向混合沉淀中加入浓度为8mol/L的硫酸，其加入量与沉淀中钼酸的摩尔比为5.3：1，同时还加入钨粉，其加入量与沉淀中钼酸的摩尔比为0.45，控制反应温度为85℃和反应时间为3.5小时，反应完成后经过滤洗涤得到钨钼质量比为983:1的钨酸沉淀和钼钨质量比为766:1的含钼溶液；(2) Adding sulfuric acid with a concentration of 8mol/L to the mixed precipitation, the molar ratio of its addition to molybdic acid in the precipitation is 5.3:1, and also adding tungsten powder at the same time, the molar ratio of its addition to molybdic acid in the precipitation is 0.45, the control reaction temperature is 85°C and the reaction time is 3.5 hours. After the reaction is completed, filter and wash to obtain a tungstic acid precipitate with a tungsten-molybdenum mass ratio of 983:1 and a molybdenum-containing solution with a molybdenum-tungsten mass ratio of 766:1;
(3)将钨酸沉淀用氨水溶解得到钨酸铵溶液，经蒸发结晶得到APT，杂质含量达到国标0级产品要求；(3) Dissolve tungstic acid precipitation with ammonia water to obtain ammonium tungstate solution, and obtain APT through evaporation and crystallization, and the impurity content reaches the national standard 0-grade product requirements;
(4)采用萃取剂将溶液中的钼提取，负载钼有机相用氨水解吸得到钼酸铵溶液，经酸沉制备得到四钼酸铵，杂质含量达到国标0级产品要求；(4) The molybdenum in the solution is extracted with an extractant, and the molybdenum-loaded organic phase is desorbed with ammonia water to obtain an ammonium molybdate solution, which is prepared by acid precipitation to obtain ammonium tetramolybdate, and the impurity content reaches the national standard 0-grade product requirements;
(5)萃余液经补加硫酸后再返回用于沉淀钨酸和钼酸的反应。(5) The raffinate is returned to the reaction of precipitating tungstic acid and molybdic acid after adding sulfuric acid.
虽然，上文中已经用一般性说明及具体实施方案对本发明作了详尽的描述，但在本发明基础上，可以对之作一些修改或改进，这对本领域技术人员而言是显而易见的。因此，在不偏离本发明精神的基础上所做的这些修改或改进，均属于本发明要求保护的范围。Although the present invention has been described in detail with general descriptions and specific embodiments above, it is obvious to those skilled in the art that some modifications or improvements can be made on the basis of the present invention. Therefore, the modifications or improvements made on the basis of not departing from the spirit of the present invention all belong to the protection scope of the present invention.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510690665.4A CN105200245A (en) | 2015-10-22 | 2015-10-22 | Method for efficiently separating tungsten and molybdenum |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510690665.4A CN105200245A (en) | 2015-10-22 | 2015-10-22 | Method for efficiently separating tungsten and molybdenum |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105200245A true CN105200245A (en) | 2015-12-30 |
Family
ID=54948198
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510690665.4A Pending CN105200245A (en) | 2015-10-22 | 2015-10-22 | Method for efficiently separating tungsten and molybdenum |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105200245A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106435224A (en) * | 2016-08-17 | 2017-02-22 | 湖南金源新材料股份有限公司 | Method for preparing ammonium paratungstate from waste containing tungsten |
| CN108751259A (en) * | 2018-08-17 | 2018-11-06 | 厦门钨业股份有限公司 | A kind of method and its device of tungsten waste production ammonium metatungstate |
| CN109988923A (en) * | 2019-03-29 | 2019-07-09 | 厦门钨业股份有限公司 | A kind of tungsten separation method |
| CN111470537A (en) * | 2020-05-07 | 2020-07-31 | 厦门钨业股份有限公司 | Ammonium molybdate recovery method and method for removing impurity tungsten in ammonium molybdate |
| CN111659535A (en) * | 2020-05-26 | 2020-09-15 | 金堆城钼业股份有限公司 | Molybdenum-tungsten separation method |
| CN111893326A (en) * | 2020-08-03 | 2020-11-06 | 中南大学 | A method for extracting tungsten by two-step acid decomposition method |
| CN112899482A (en) * | 2021-01-15 | 2021-06-04 | 厦门钨业股份有限公司 | Treatment method of molybdenum removal slag |
| CN113800565A (en) * | 2020-06-11 | 2021-12-17 | 杭州临安慧尔钼业科技有限公司 | Method for preparing high-purity ammonium heptamolybdate by photooxidation conversion of filament-melting molybdenum-containing waste acid |
| CN114959261A (en) * | 2022-04-29 | 2022-08-30 | 北京科技大学 | Method for recovering tungsten, molybdenum, nickel and cobalt from multi-metal alloy in full-wet process |
| CN119859753A (en) * | 2025-01-07 | 2025-04-22 | 宁夏宁东清大国华环境资源有限公司 | A comprehensive utilization method of waste catalyst |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3969484A (en) * | 1974-03-22 | 1976-07-13 | Nittetsu Mining Company, Ltd. | Process for recovering tungsten from alkaline leaching solution of tungsten ores |
| US4278644A (en) * | 1980-04-15 | 1981-07-14 | Cabot Corporation | Process for partitioning Mo and W from a mixed CaMoO4 -CaWO4 precipitate |
| CN101880780A (en) * | 2010-06-04 | 2010-11-10 | 中南大学 | Method for separating and extracting tungsten-molybdenum from mixed solution of tungstate-molybdate |
| CN101921916A (en) * | 2010-08-16 | 2010-12-22 | 华电电力科学研究院 | Method for recycling metal oxide from waste flue gas denitration catalyst |
| CN102162030A (en) * | 2011-03-25 | 2011-08-24 | 中南大学 | Ion-exchange separation method for tungsten and molybdenum in tungstate and molybdate mixed solution |
| CN103103358A (en) * | 2012-11-23 | 2013-05-15 | 陈泉兴 | Method for recovering metal by use of APT (ammonium paratungstate) waste slag |
| CN103160690A (en) * | 2011-12-14 | 2013-06-19 | 虹京环保有限公司 | Method for recovering metal oxide from SCR denitration waste catalyst |
-
2015
- 2015-10-22 CN CN201510690665.4A patent/CN105200245A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3969484A (en) * | 1974-03-22 | 1976-07-13 | Nittetsu Mining Company, Ltd. | Process for recovering tungsten from alkaline leaching solution of tungsten ores |
| US4278644A (en) * | 1980-04-15 | 1981-07-14 | Cabot Corporation | Process for partitioning Mo and W from a mixed CaMoO4 -CaWO4 precipitate |
| CN101880780A (en) * | 2010-06-04 | 2010-11-10 | 中南大学 | Method for separating and extracting tungsten-molybdenum from mixed solution of tungstate-molybdate |
| CN101921916A (en) * | 2010-08-16 | 2010-12-22 | 华电电力科学研究院 | Method for recycling metal oxide from waste flue gas denitration catalyst |
| CN102162030A (en) * | 2011-03-25 | 2011-08-24 | 中南大学 | Ion-exchange separation method for tungsten and molybdenum in tungstate and molybdate mixed solution |
| CN103160690A (en) * | 2011-12-14 | 2013-06-19 | 虹京环保有限公司 | Method for recovering metal oxide from SCR denitration waste catalyst |
| CN103103358A (en) * | 2012-11-23 | 2013-05-15 | 陈泉兴 | Method for recovering metal by use of APT (ammonium paratungstate) waste slag |
Non-Patent Citations (2)
| Title |
|---|
| 张邦胜等: "沉淀法分离钨钼的研究进展", 《江西有色金属》 * |
| 文颖频等: "钨钼分离的研究与进展", 《湖南冶金》 * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106435224A (en) * | 2016-08-17 | 2017-02-22 | 湖南金源新材料股份有限公司 | Method for preparing ammonium paratungstate from waste containing tungsten |
| CN106435224B (en) * | 2016-08-17 | 2019-01-25 | 湖南金源新材料股份有限公司 | Method for preparing ammonium paratungstate from waste containing tungsten |
| CN108751259A (en) * | 2018-08-17 | 2018-11-06 | 厦门钨业股份有限公司 | A kind of method and its device of tungsten waste production ammonium metatungstate |
| CN109988923A (en) * | 2019-03-29 | 2019-07-09 | 厦门钨业股份有限公司 | A kind of tungsten separation method |
| CN111470537A (en) * | 2020-05-07 | 2020-07-31 | 厦门钨业股份有限公司 | Ammonium molybdate recovery method and method for removing impurity tungsten in ammonium molybdate |
| CN111659535A (en) * | 2020-05-26 | 2020-09-15 | 金堆城钼业股份有限公司 | Molybdenum-tungsten separation method |
| CN111659535B (en) * | 2020-05-26 | 2022-10-11 | 金堆城钼业股份有限公司 | Molybdenum-tungsten separation method |
| CN113800565A (en) * | 2020-06-11 | 2021-12-17 | 杭州临安慧尔钼业科技有限公司 | Method for preparing high-purity ammonium heptamolybdate by photooxidation conversion of filament-melting molybdenum-containing waste acid |
| CN111893326B (en) * | 2020-08-03 | 2021-07-20 | 中南大学 | A method for extracting tungsten by two-step acid decomposition method |
| CN111893326A (en) * | 2020-08-03 | 2020-11-06 | 中南大学 | A method for extracting tungsten by two-step acid decomposition method |
| CN112899482A (en) * | 2021-01-15 | 2021-06-04 | 厦门钨业股份有限公司 | Treatment method of molybdenum removal slag |
| CN114959261A (en) * | 2022-04-29 | 2022-08-30 | 北京科技大学 | Method for recovering tungsten, molybdenum, nickel and cobalt from multi-metal alloy in full-wet process |
| CN119859753A (en) * | 2025-01-07 | 2025-04-22 | 宁夏宁东清大国华环境资源有限公司 | A comprehensive utilization method of waste catalyst |
| CN119859753B (en) * | 2025-01-07 | 2025-11-11 | 宁夏宁东清大国华环境资源有限公司 | Comprehensive utilization method of waste catalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105200246B (en) | A kind of method for detaching tungsten | |
| CN105200245A (en) | Method for efficiently separating tungsten and molybdenum | |
| CN102212697B (en) | Tungsten slag treatment method | |
| CN103789552B (en) | Method for recovering rhenium from high-temperature alloy pickle liquor | |
| CN103290224B (en) | Recovery process for valuable metals in tungsten residues | |
| CN105349803B (en) | A kind of method from the phosphotungstic acid containing molybdenum/phosphotungstate solution separation tungsten | |
| CN106611841B (en) | A method for preparing nickel-cobalt-manganese ternary material precursor by utilizing nickel-cobalt slag material | |
| CN107162067A (en) | A kind of method that high-purity sulphuric acid nickel is reclaimed from nickeliferous old and useless battery | |
| CN103966446A (en) | Method for separating and recovering copper, nickel and iron from electroplating sludge | |
| CN105692698B (en) | The depth separation method of molybdenum, vanadium in a kind of vanadium solution containing molybdenum | |
| CN105271413B (en) | A kind of method for extracting tungsten from phosphotungstic acid/phosphotungstate solution | |
| CN105603220B (en) | A method of step by step arithmetic vanadium chromium and removing aluminium silicon from alkaline aqueous solution | |
| CN103436715B (en) | A method for extracting vanadium from stone coal | |
| CN106148737A (en) | A kind of method reclaiming association rhenium resource from sandstone-type uranium mineralization with respect ground dipping uranium extracting process adsorption tail liquid | |
| CN108545775B (en) | A method for separating tungsten and molybdenum from ammonium tungstate solution with high molybdenum content | |
| CN102781841B (en) | The preparation method of ammonium tungstate aqueous solution | |
| CN109022787B (en) | Method for extracting nickel and molybdenum from nickel-molybdenum ore acidic leaching solution | |
| CN105950877A (en) | Method for recovering vanadium in impurity removing slag by using vanadium precipitation waste water | |
| CN107519948B (en) | A kind of compound amine-based weakly basic anion exchange resin and method for recovering rhenium from arsenic sulfide slag leaching solution | |
| CN113800569B (en) | Recovery method for preparing ammonium molybdate, tungsten, copper and sulfur by molybdenum removal slag | |
| CN103451447A (en) | Method for recovering copper and cobalt from high-iron waste water treatment and residue | |
| CN113801997A (en) | Method for recycling ammonium molybdate and molybdenum precipitation agent from low-molybdenum raffinate molybdenum | |
| CN106629790B (en) | A method of separation is containing magnesium lithium in magnesium, lithium solution | |
| CN119177366B (en) | A method for separating metallic molybdenum and rhenium from a nickel-based high-temperature alloy electrochemical solution | |
| CN103602807B (en) | Treating method of removed molybdenum slag produced from tungsten smelting processes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20151230 |
|
| RJ01 | Rejection of invention patent application after publication |