CN115747529B - Molybdenum calcine treatment method - Google Patents
Molybdenum calcine treatment method Download PDFInfo
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- CN115747529B CN115747529B CN202211331700.XA CN202211331700A CN115747529B CN 115747529 B CN115747529 B CN 115747529B CN 202211331700 A CN202211331700 A CN 202211331700A CN 115747529 B CN115747529 B CN 115747529B
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- molybdate
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 99
- 239000011733 molybdenum Substances 0.000 title claims abstract description 99
- 238000000034 method Methods 0.000 title claims abstract description 70
- 238000002386 leaching Methods 0.000 claims abstract description 95
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 85
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000011591 potassium Substances 0.000 claims abstract description 81
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 81
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 48
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims abstract description 19
- 235000019341 magnesium sulphate Nutrition 0.000 claims abstract description 19
- 238000000926 separation method Methods 0.000 claims abstract description 16
- 239000002244 precipitate Substances 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims description 49
- 238000002425 crystallisation Methods 0.000 claims description 32
- 230000008025 crystallization Effects 0.000 claims description 32
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 29
- 229910052760 oxygen Inorganic materials 0.000 claims description 29
- 239000001301 oxygen Substances 0.000 claims description 29
- 239000011609 ammonium molybdate Substances 0.000 claims description 21
- 229940010552 ammonium molybdate Drugs 0.000 claims description 21
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 20
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 20
- 239000013078 crystal Substances 0.000 claims description 18
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 230000001276 controlling effect Effects 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- 230000008020 evaporation Effects 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000019270 ammonium chloride Nutrition 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000003337 fertilizer Substances 0.000 claims description 5
- -1 molybdenum ammonium potassium Chemical compound 0.000 claims description 5
- 239000012452 mother liquor Substances 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 238000003916 acid precipitation Methods 0.000 claims description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 4
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 4
- 239000003957 anion exchange resin Substances 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- FQLQNUZHYYPPBT-UHFFFAOYSA-N potassium;azane Chemical compound N.[K+] FQLQNUZHYYPPBT-UHFFFAOYSA-N 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims 1
- 238000003723 Smelting Methods 0.000 abstract description 8
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000000047 product Substances 0.000 description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 16
- 238000002441 X-ray diffraction Methods 0.000 description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- 239000002893 slag Substances 0.000 description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- 229910052698 phosphorus Inorganic materials 0.000 description 11
- 239000011574 phosphorus Substances 0.000 description 11
- 229910052710 silicon Inorganic materials 0.000 description 11
- 239000010703 silicon Substances 0.000 description 11
- 235000015393 sodium molybdate Nutrition 0.000 description 9
- 239000011684 sodium molybdate Substances 0.000 description 9
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 9
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000003795 desorption Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- XUFUCDNVOXXQQC-UHFFFAOYSA-L azane;hydroxy-(hydroxy(dioxo)molybdenio)oxy-dioxomolybdenum Chemical compound N.N.O[Mo](=O)(=O)O[Mo](O)(=O)=O XUFUCDNVOXXQQC-UHFFFAOYSA-L 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 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 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910001309 Ferromolybdenum Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 239000013461 intermediate chemical Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- MGRWKWACZDFZJT-UHFFFAOYSA-N molybdenum tungsten Chemical compound [Mo].[W] MGRWKWACZDFZJT-UHFFFAOYSA-N 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
Abstract
The invention relates to the technical field of molybdenum smelting, in particular to a treatment method of molybdenum calcine, which adopts potassium hydroxide solution to leach the molybdenum calcine to obtain potassium molybdate leaching solution; adding magnesium sulfate into the obtained potassium molybdate leaching solution for reaction, and then carrying out solid-liquid separation to obtain potassium molybdate treatment solution and MgKA precipitate; the A is PO 4 3‑ 、AsO 4 3‑ 、SiO 3 2‑ At least one of (a) and (b); controlling the pH value of the solution in the reaction stage to 8.0-10.0, adding magnesium sulfate 1.0-1.2 times the molar quantity of A in the potassium molybdate leaching solution, and reacting at 25-100 ℃. The invention also provides a scheme for obtaining the polymolybdate by polymerizing the potassium molybdate treatment solution by adjusting the pH. According to the technical scheme, the high-efficiency leaching of the molybdenum calcine and the high-selectivity separation of Mo-A can be realized, and in addition, the polymeric molybdate can be obtained based on a simple method.
Description
Technical Field
The invention relates to the field of rare metal material preparation, in particular to a method for treating molybdenum calcine.
Background
Molybdenum is an important strategic rare metal, is widely applied to various fields of steel industry, metal pressure processing, aerospace, petrochemical industry and the like, and is listed as strategic reserve resource by a plurality of countries. China is a large country for producing and consuming molybdenum resources, and along with the continuous development of technology, the requirements of the country on molybdenum related industries are also improved to a new strategic height.
The main raw material for molybdenum smelting is molybdenum sulfide concentrate (molybdenite). The main process of molybdenum smelting is to convert molybdenum sulfide into molybdenum calcine (industrial molybdenum oxide) by adopting an oxidizing roasting method. The molybdenum calcine is mainly used as an additive in the steel industry and a raw material for producing ferromolybdenum, and is also a main raw material for producing an ammonium molybdate product. Ammonium molybdate is an important molybdenum intermediate chemical, and is used for preparing high-purity molybdenum trioxide through calcination and preparing molybdenum powder through hydrogen reduction, and is also a basic raw material of chemical products such as molybdenum catalysts, molybdenum pigments and the like.
The preparation of ammonium molybdate mainly takes molybdenum calcine which is a product of a molybdenum concentrate fire roasting process as a raw material, and is produced by a classical process route of ammonia leaching-solution purification-ammonium molybdate crystallization. For example, a plurality of enterprises such as the molybdenum industry stock company of Shaanxi Jin Dui city, the new material stock company of Siam Hua, the Luoyang Dachuan molybdenum tungsten technology, and the like still adopt classical process routes to produce the ammonium molybdate product. Since molybdenum calcine contains molybdenum dioxide, other metal compounds such as molybdates and sulfates of copper, nickel, zinc, iron, calcium and the like, residual molybdenum sulfide concentrate and the like in addition to molybdenum trioxide, dilute nitric acid pretreatment is generally required before ammonia leaching. The direct recovery rate of the ammonia leaching process of the traditional process is not high, and the required ammonia consumption is large, and the ammonia volatilizes, so that the operation environment is poor; copper and other impurities are leached out by ammonia complexation, and the subsequent impurity removal pressure is high.
For this reason, there are enterprises in recent years that develop a process for preparing ammonium dimolybdate by molybdenum calcine-alkaline leaching-ion exchange transformation-evaporative crystallization. The leaching rate of molybdenum is greatly improved by adopting sodium hydroxide to oxidize and leach molybdenum calcine in an autoclave, and the obtained sodium molybdate solution is adsorbed by ion exchange resin and convertedForm to obtain ammonium molybdate solution, na in the system + And (3) the solution enters an exchange solution to obtain an ammonium molybdate solution, and the ammonium molybdate solution is purified, evaporated and crystallized to obtain a high-purity ammonium dimolybdate product. The method has the advantages that a large amount of sodium salt wastewater produced in the process of extracting molybdenum through ion exchange needs to be specially treated; meanwhile, a large amount of ammonia water is adopted for desorption in the ion exchange transformation process, so that a large amount of ammonia nitrogen wastewater is generated in the ion exchange transformation process and the process of preparing an ammonium molybdate product from the subsequent ammonium molybdate desorption solution, and special treatment is also required.
Disclosure of Invention
In order to solve the problems of the existing molybdenum calcine treatment method, the invention aims to provide a method for treating molybdenum calcine, which aims to simplify the treatment process and improve the effect and value of wet smelting of the molybdenum calcine.
The method for treating molybdenum calcine adopts potassium hydroxide solution to leach the molybdenum calcine to obtain potassium molybdate leaching solution;
adding magnesium sulfate into the obtained potassium molybdate leaching solution for reaction, and then carrying out solid-liquid separation to obtain potassium molybdate treatment solution and MgKA precipitate;
the A is PO 4 3- 、AsO 4 3- 、SiO 3 2- At least one of (a) and (b); controlling the pH value of the solution in the reaction stage to 7.0-10.0, adding magnesium sulfate 1.0-1.2 times the molar quantity of A in the potassium molybdate leaching solution, and reacting at 25-100 ℃.
The molybdenum calcine contains Mo, P, si and other components, and is leached together with molybdenum in the wet leaching process of the molybdenum calcine, so that the quality of molybdenum products is affected. Aiming at the problems, the invention provides a concept of coupling molybdenum calcine hydrometallurgy and MgKA precipitation reaction for the first time in the industry, however, the research and development process finds that in order to realize the brand-new smelting concept, the problems that the MgKA phase is difficult to control, crystals are difficult to form, the separation selectivity of Mo and MgKA is not ideal are required to be faced, and aiming at the technical problems faced by the brand-new concept, the invention discovers that the molybdenum calcine is leached by potassium hydroxide and then is matched with magnesium sulfate to assist the reaction and the combined control of the temperature and the pH of the reaction stage, so that the synergy can be realized unexpectedly, the leaching of the molybdenum calcine can be effectively improved, the separation selectivity and the separation efficiency of the Mo and the A can be improved, the accompanying crystallization of the Mo can be reduced, the smelting effect is improved, and the economic value of smelting is improved.
In the present invention, the leaching of potassium hydroxide and the combined control of the magnesium-containing material and the pH and temperature of the reaction are key to improving the selectivity of the smelting separation and facilitating the obtainment of a polymeric molybdate product based upon pH control.
In the invention, the leaching process comprises a first-stage normal pressure leaching process and a second-stage oxygen pressure leaching process aiming at the first-stage normal pressure leaching slag;
and combining the first-stage normal pressure leaching solution and the second-stage oxygen pressure leaching solution to obtain the potassium molybdate leaching solution.
The atmospheric leaching conditions are as follows: the KOH dosage is 2.4 to 3.0 times of the mole amount of Mo in the molybdenum calcine;
preferably, the liquid-solid ratio of the atmospheric leaching process is 4.5:1-8.5:1 (mL/g);
preferably, the reaction temperature in the atmospheric leaching process is 60-100 ℃;
preferably, the reaction time of the atmospheric leaching process is 1 to 5 hours.
Preferably, the conditions of the oxygen pressure leaching process are: the KOH dosage is 2.4 to 3.0 times of the mole amount of Mo in the molybdenum calcine;
preferably, the liquid-solid ratio of the oxygen pressure leaching process is 2:1-5:1 (mL/g);
preferably, the reaction temperature of the oxygen pressure leaching process is 160-200 ℃;
preferably, the reaction time of the oxygen pressure leaching process is 1 to 5 hours;
preferably, the oxygen partial pressure of the oxygen pressure leaching process is 1.5-1.8 Mpa.
Preferably, the reaction temperature is 60 to 80 ℃. The pH is preferably 8 to 9. It is found that under the preferred conditions, better separation selectivity of molybdenum and A can be obtained, which is beneficial to the subsequent pH polymerization to obtain the polymolybdate.
The invention also comprises a method for recycling the obtained high-quality potassium molybdate solution.
For example, in the invention, the obtained potassium molybdate treatment liquid is used for preparing molybdenum ammonium potassium double salt;
preferably, the steps for preparing the molybdenum ammonium potassium double salt by adopting the potassium molybdate solution are as follows: regulating and controlling the pH value of the potassium molybdate treatment solution to 5-7, adding ammonium sulfate into the solution, evaporating and crystallizing to 1/2-2/3 of the volume of the solution, and filtering to obtain ammonium potassium double salt crystals of molybdenum, wherein the addition amount of the ammonium salt is 0.95-1.1 times of the theoretical amount.
In the invention, the prepared potassium molybdate solution can be used for preparing ammonium molybdate;
preferably, the step of preparing ammonium molybdate from a potassium molybdate solution comprises:
controlling the pH value of the potassium molybdate treatment solution to be 6-8, then adopting strong alkaline anion exchange resin or alkaline extractant to extract molybdenum, obtaining ammonium molybdate solution after ammonia water and ammonium chloride are desorbed or back-extracted, and then adopting an evaporation crystallization mode to prepare ammonium paramolybdate; or preparing ammonium tetramolybdate by adopting an acid precipitation crystallization mode.
In the invention, the obtained potassium molybdate solution can be used for preparing polymerized potassium molybdate crystals;
preferably, the step of preparing polymerized potassium molybdate crystals using a potassium molybdate solution comprises:
regulating the pH value of the potassium molybdate treatment solution to 1-4 to combine the polymeric molybdate with potassium to form polymeric potassium molybdate crystals with extremely low solubility, wherein the crystallization temperature is preferably 25-80 ℃, and the crystallization time is preferably 0.5-2 h.
In the invention, the polymerization of molybdic acid root can be promoted based on the simple joint control of the pH value of the potassium molybdate solution, and the polymerized potassium molybdate crystal with extremely low solubility can be produced.
In the invention, the obtained crystallization mother liquor is used for preparing the compound fertilizer by adopting an evaporation crystallization mode after deep extraction of molybdenum.
The preferred method for treating molybdenum calcine comprises the following steps:
step (1): leaching the molybdenum calcine by adopting potassium hydroxide to obtain potassium molybdate leaching solution; the leaching process comprises the following steps: firstly, carrying out normal pressure leaching on molybdenum calcine by adopting potassium hydroxide to obtain primary leaching liquid and primary leaching slag; then, potassium hydroxide is adopted to carry out oxygen pressure leaching on the first-stage leaching slag, so as to obtain a second-stage leaching liquid and a second-stage leaching slag; and combining the first-stage leaching solution and the second-stage leaching solution to obtain the potassium molybdate leaching solution. The atmospheric leaching conditions are as follows: the KOH dosage is 2.4 to 3.0 times of the mole amount of Mo in the molybdenum calcine (1.2 to 1.5 times of the molybdenum calcine excess coefficient); the liquid-solid ratio in the normal pressure leaching process is preferably 4.5:1-8.5:1 (mL/g); the reaction temperature in the normal pressure leaching process is preferably 60-100 ℃; the reaction time in the atmospheric leaching process is preferably 1 to 5 hours. The conditions of the oxygen pressure leaching process are: the KOH dosage is 2.4 to 3.0 times of the mole amount of Mo in the molybdenum calcine; the liquid-solid ratio in the oxygen pressure leaching process is 2:1-5:1 (mL/g); the reaction temperature in the oxygen pressure leaching process is 160-200 ℃; the reaction time of the oxygen pressure leaching process is 1 to 5 hours; the oxygen partial pressure in the oxygen pressure leaching process is 1.5-1.8 Mpa.
Step (2): regulating the pH value of the obtained potassium molybdate leaching solution to 7-10, and adding magnesium sulfate for reaction; the reaction time is 1 to 5 hours at the reaction temperature of between 25 and 100 ℃. And then carrying out solid-liquid separation to obtain a potassium molybdate solution and MgKA crystals:
step (3): further preparing molybdenum ammonium potassium double salt, polymeric potassium molybdate product and ammonium molybdate product from the potassium molybdate solution prepared in the step (2);
wherein, the conditions of the process for preparing the molybdenum ammonium potassium double salt are as follows: adding sulfuric acid to regulate the pH value of the potassium molybdate treatment liquid to 5-7, adding ammonium sulfate into the solution, adding ammonium salt in an amount which is 0.95-1.1 times of the theoretical amount, evaporating and crystallizing to 1/2-2/3 of the volume of the solution, and filtering to obtain ammonium potassium double salt crystals of molybdenum.
The conditions of the process for preparing ammonium molybdate are as follows: adding sulfuric acid to adjust the pH value of the potassium molybdate treatment solution to 6-8, then adopting strong alkaline anion exchange resin or alkaline extractant to extract molybdenum, desorbing or back-extracting ammonia water and ammonium chloride to obtain ammonium molybdate solution, and then adopting an evaporation crystallization mode to prepare ammonium paramolybdate; or preparing ammonium tetramolybdate by adopting an acid precipitation crystallization mode.
The conditions of the process for preparing the polymerized potassium molybdate are as follows: adding sulfuric acid to regulate the pH value of the potassium molybdate treatment liquid to 1-4, and combining molybdate with potassium in different polymerization degrees to form polymerized potassium molybdate crystals, wherein the crystallization temperature is 25-80 ℃ and the crystallization time is 0.5-2 h.
Step (4): and preparing the compound fertilizer by using the crystallization mother liquor.
And preparing the compound fertilizer by adopting an evaporation crystallization mode after deeply extracting molybdenum from the obtained crystallization mother liquor.
Advantageous effects
1. The invention provides a treatment idea of combining efficient leaching of molybdenum calcine and MgKA selective precipitation for the first time; and further through the leaching of potassium hydroxide and the subsequent magnesium sulfate auxiliary reaction and the joint control of temperature and pH, the high-selectivity separation of Mo and A can be effectively realized, the high-quality potassium molybdate treatment liquid can be obtained, and in addition, mgKA with a certain crystalline state can be obtained.
2. The characteristic that the molybdenum polymeric ions and potassium ions are combined to generate polymeric potassium molybdate with small solubility under a weak acid system is utilized, and the simple and efficient extraction of molybdenum is realized by adopting an acid precipitation crystallization mode, so that the technology for extracting molybdenum by using the traditional ion exchange or solvent extraction can be replaced;
3. the crystallization mother liquor adopts an evaporation crystallization mode to prepare the compound fertilizer, so that the effective utilization of potassium and sulfur is realized.
Drawings
FIG. 1 is an XRD pattern of the primary leaching residue obtained in example 1;
FIG. 2 is an XRD pattern of the secondary leaching residue obtained in example 1;
FIG. 3 is an XRD pattern of the dephosphorized slag obtained in example 1;
FIG. 4 is an XRD pattern of the polymerized potassium molybdate product obtained in example 1;
FIG. 5 is an XRD pattern of the ammonium tetramolybdate product obtained in example 5;
figure 6 XRD pattern of the precipitate of comparative example 3.
Detailed Description
The following examples are further described in connection with the present invention and are intended to illustrate the invention rather than to limit it.
In the following cases, the concentration of the magnesium sulfate solution is not particularly required, and is, for example, 1M.
Example 1
Step (1): molybdenum calcine (containing MoO) 3 72.15％，Cu4.06％，SiO 2 7.53％，P 2 O 5 0.13%) and 100g, adding the mixture into 450mL KOH solution with the molar quantity of Mo being 2.4 times of that of molybdenum calcine, leaching the mixture for 2 hours at 60 ℃, filtering and collecting residues, drying the residues, and obtaining the leached residues with XRD shown in figure 1 and molybdenum leaching rate of 77.6%. Then placing the leached slag in an autoclave for oxygen pressure leaching, setting the oxygen partial pressure to be 1.5Mpa, adding the leached slag into KOH solution with the molar quantity of Mo being 2.4 times of that of molybdenum calcine, and reacting for 2 hours at 160 ℃ in a liquid-solid ratio of 2:1 (mL/g). And mixing the two leaching solutions to obtain potassium molybdate leaching solution, wherein the total leaching rate of molybdenum reaches 98.8%, and XRD of the secondary leaching slag is shown in figure 2.
Step (2):
the pH of the potassium molybdate leach solution was controlled to 9.0 and a magnesium sulfate solution was added, wherein the molar amount of Mg in magnesium sulfate was 1 time the total molar amount of P/Si in the leach solution, and the reaction was stirred at 80 ℃ for 1 hour while maintaining the pH at 9.0 at all times. Then solid-liquid separation is carried out to obtain potassium molybdate treatment liquid and precipitate, and XRD of the obtained precipitate sample is shown in figure 3 after analysis and detection to obtain crystalline MgKPO 4 The phosphorus removal rate is 99.9%, the silicon removal rate is 96.5%, and the molybdenum loss rate is 0.14%.
Step (3):
and adding sulfuric acid to adjust the pH value of the potassium molybdate treatment solution to 1.5, and combining molybdate with potassium to form crystals with different polymerization degrees. Crystallization at 80 ℃ for 2h and filtration to obtain a polymerized potassium molybdate product, the molybdenum crystallization rate is 98.8%, and the XRD is shown in figure 4.
Example 2
The only difference compared to example 1 is that the pH of the reaction stage of step (2) is changed, specifically comprising the following experimental groups:
group A: the potassium molybdate leach solution was controlled to a pH of 7 in the reaction stage, and other operations and parameters were the same as in example 1.
Group B: the potassium molybdate leach solution was controlled to a pH of 8 in the reaction stage, and other operations and parameters were the same as in example 1.
Group C: the pH of the potassium molybdate leach solution and the reaction stage were controlled to be 10, and other operations and parameters were the same as in example 1.
The P/Si removal rate and the molybdenum loss rate prepared in each group of step 2 are respectively as follows:
group A: the phosphorus removal rate is 98.6%, the silicon removal rate is 95.1%, and the molybdenum loss rate is 0.28%.
Group B: the phosphorus removal rate is 99.4%, the silicon removal rate is 96.2%, and the molybdenum loss rate is 0.11%.
Group C: the phosphorus removal rate is 98.8%, the silicon removal rate is 95.1%, and the molybdenum loss rate is 0.22%.
The pH of the potassium molybdate treatment solution is preferably controlled to 8.0 to 9.0.
Example 3
The only difference compared to example 1 is that the reaction temperature of step (2) is changed to:
group A: the temperature was 100 ℃.
Group B: the temperature was 60 ℃.
Group C: the temperature was 40 ℃.
Group D: the temperature was 25 ℃.
The P/Si removal rate and the molybdenum loss rate prepared in each group of step 2 are respectively as follows:
group A: the phosphorus removal rate is 98.9%, the silicon removal rate is 95.1%, and the molybdenum loss rate is 0.32%.
Group B: the phosphorus removal rate is 99.2%, the silicon removal rate is 95.9%, and the molybdenum loss rate is 0.18%.
Group C: the phosphorus removal rate is 98.7%, the silicon removal rate is 94.6%, and the molybdenum loss rate is 0.54%.
Group D: the phosphorus removal rate is 98.1%, the silicon removal rate is 94.4%, and the molybdenum loss rate is 0.85%.
The reaction temperature is preferably controlled to 60 to 80 ℃.
Example 4
The only difference compared to example 1 is that the polymerization pH of step (3) was changed, the experimental groups were:
group A: the pH of step (3) was 3.0 and the crystallization rate of the polymerized potassium molybdate was 98.47%.
Group B: the pH of step (3) was 4.0 and the crystallization rate of the polymerized potassium molybdate was 94.27%.
Example 5
The difference from example 1 is only that the potassium molybdate treatment liquid was prepared by using steps (1) and (2) of example 1, and then molybdenum was extracted by using a strongly basic anion exchange resin D201, with an extraction rate of 99.8%. The molybdenum-loaded resin is desorbed by ammonia water and ammonium chloride to obtain ammonium molybdate solution, and the desorption rate of molybdenum is 99.1 percent. Nitric acid is added into the ammonium molybdate solution obtained by desorption to adjust the pH of the solution to 1.5, the solution is stirred for 1h and then filtered to obtain an ammonium tetramolybdate crystal product, the crystallization rate of molybdenum is 95.6 percent, and XRD (X-ray diffraction) of the molybdenum is shown in figure 5.
Example 6
The difference from example 1 was only that the potassium molybdate treatment liquid was prepared by using the steps (1) and (2) of example 1, then sulfuric acid was added to adjust the pH of the potassium molybdate treatment liquid to 6.0, then ammonium sulfate was added to the solution in an amount of 1.1 times the theoretical amount, and the crystals were evaporated to 1/2 of the volume of the solution, and the ammonium-potassium double salt crystals of molybdenum were obtained by filtration, with a molybdenum crystallization rate of 94.1%.
Comparative example 1:
the only difference compared to example 1 is that a sodium hydroxide leaching system is used instead of a potassium hydroxide leaching system, in particular:
step (1): 100g of molybdenum calcine (same as in example 1) is added into 450mL of NaOH solution with the molar quantity of Mo being 2.4 times of that of the molybdenum calcine, leached for 2 hours at 60 ℃, and residues are filtered, collected and dried, wherein the leaching rate of the molybdenum is 77.1 percent. Then placing the leached slag in an autoclave for oxygen pressure leaching, setting the oxygen partial pressure to be 1.5Mpa, adding the leached slag into NaOH solution with the molar quantity of 2.4 times of Mo in molybdenum calcine, and reacting for 2 hours at 160 ℃ in a liquid-solid ratio of 2:1 (mL/g). Mixing the two leaching solutions to obtain sodium molybdate leaching solution, wherein the total leaching rate of molybdenum reaches 98.2 percent.
Step (2):
the pH of the sodium molybdate leach solution was controlled to 9.0 and a magnesium sulfate solution was added, wherein the molar amount of Mg in magnesium sulfate was 1 time the total molar amount of P/Si in the leach solution, and the reaction was stirred at 80 ℃ for 1 hour while maintaining the pH at 9.0 at all times. And then carrying out solid-liquid separation to obtain sodium molybdate treatment liquid and magnesium phosphate and magnesium silicate precipitate, wherein the phosphorus removal rate is 95.6%, the silicon removal rate is 94.3%, and the molybdenum loss rate is 0.26%.
Step (3):
the sodium molybdate treatment solution was adjusted to pH 1.5 with the addition of sulfuric acid, and no molybdate crystallization occurred.
Comparative example 2:
the only difference compared to example 1 is that the process of steps (1) and (2) is modified, in particular:
step (1): 100g of molybdenum calcine (example 1) is added into 450mL of NaOH solution with the molar quantity of Mo being 2.4 times of that of the molybdenum calcine, leached for 2 hours at 60 ℃, and residues are filtered, collected and dried, wherein the leaching rate of the molybdenum is 77.1 percent. Then placing the leached slag in an autoclave for oxygen pressure leaching, setting the oxygen partial pressure to be 1.5Mpa, adding the leached slag into NaOH solution with the molar quantity of 2.4 times of Mo in molybdenum calcine, and reacting for 2 hours at 160 ℃ in a liquid-solid ratio of 2:1 (mL/g). Mixing the two leaching solutions to obtain sodium molybdate leaching solution, wherein the total leaching rate of molybdenum reaches 98.2 percent.
Step (2):
controlling the pH of the sodium molybdate leaching solution to 9.0, adding ammonium chloride solution and NH 4 + The ratio of the added amount to the total mole of P/Si in the solution was 1:1, and then a magnesium sulfate solution was added, wherein the mole of Mg in magnesium sulfate was 1 time the total mole of P/Si in the leachate, and the reaction was stirred at 80℃for 1 hour, while maintaining the pH at 9.0 at all times. And then carrying out solid-liquid separation to obtain sodium molybdate treatment liquid.
Step (3):
and adding sulfuric acid to adjust the pH of the sodium molybdate treatment solution to 1.5, wherein molybdate crystallization does not occur, and a polymeric molybdate product is not obtained.
Comparative example 3
The only difference compared to example 1 is that the pH of the reaction stage of step (2) is controlled to be 11:
step (1): as in example 1.
Step (2):
the pH of the potassium molybdate leach solution was controlled to 11.0 and a magnesium sulfate solution was added, wherein the molar amount of Mg in magnesium sulfate was 1 time the total molar amount of P/Si in the leach solution, and the reaction was stirred at 80 ℃ for 1 hour while maintaining the pH at 11.0 at all times. And then carrying out solid-liquid separation to obtain potassium molybdate treatment liquid and precipitate, analyzing and detecting the obtained precipitate sample to obtain XRD (X-ray diffraction) as shown in figure 6, and obtaining amorphous precipitate with a phosphorus removal rate of 94.1%, a silicon removal rate of 93.4% and a molybdenum loss rate of 0.31%.
Step (3):
and adding sulfuric acid to adjust the pH value of the potassium molybdate treatment solution to 1.5, and combining molybdate with potassium to form crystals with different polymerization degrees. Crystallizing at 80 deg.c for 2 hr and filtering to obtain polymerized potassium molybdate product. The yield and quality of the product were inferior to example 1.
Comparative example 4
The only difference compared to example 1 is that the pH of the reaction stage of step (2) is controlled to be 6:
step (1): as in example 1.
Step (2):
the pH of the potassium molybdate leach solution was controlled to 6.0 and a magnesium sulfate solution was added, wherein the molar amount of Mg in magnesium sulfate was 1 time the total molar amount of P/Si in the leach solution, and the reaction was stirred at 80 ℃ for 1 hour while maintaining the pH at 6 at all times. And then carrying out solid-liquid separation to obtain potassium molybdate treatment liquid and precipitate, wherein the phosphorus removal rate is 98.2%, the silicon removal rate is 95.2%, and the molybdenum loss rate is 6.43%.
Step (3):
as in example 1, the yields and quality of the products produced were inferior to those of example 1.
Claims (13)
1. The treatment method of the molybdenum calcine is characterized in that potassium hydroxide solution is adopted to leach the molybdenum calcine to obtain potassium molybdate leaching solution;
adding magnesium sulfate into the obtained potassium molybdate leaching solution for reaction, and then carrying out solid-liquid separation to obtain potassium molybdate treatment solution and MgKA precipitate;
the A is PO 4 3- 、AsO 4 3- 、SiO 3 2- At least one of (a) and (b); controlling the pH value of the solution in the reaction stage to 7.0-10.0, and magnesium sulfateThe addition amount of the catalyst is 1.0-1.2 times of the molar amount of A in the potassium molybdate leaching solution, and the reaction temperature is 25-100 ℃;
the atmospheric leaching conditions are as follows: the KOH dosage is 2.4-3.0 times of the mole amount of Mo in the molybdenum calcine;
the liquid-solid ratio in the normal pressure leaching process is 4.5:1-8.5:1 mL/g;
the reaction temperature in the normal pressure leaching process is 60-100 ℃;
the conditions of the oxygen pressure leaching process are: the KOH dosage is 2.4-3.0 times of the mole amount of Mo in the molybdenum calcine;
the reaction temperature in the oxygen pressure leaching process is 160-200 ℃;
the oxygen partial pressure in the oxygen pressure leaching process is 1.5-1.8 mpa;
the molybdenum ammonium potassium double salt is prepared from the obtained potassium molybdate treatment liquid, and the steps are as follows: regulating and controlling the pH value of the potassium molybdate treatment solution to 5-7, adding ammonium sulfate into the solution, wherein the addition amount of the ammonium salt is 0.95-1.1 times of the theoretical amount, evaporating and crystallizing to 1/2-2/3 of the volume of the solution, and filtering to obtain ammonium potassium double salt crystals of molybdenum.
2. The process of claim 1, wherein the leaching process comprises a first stage atmospheric leaching process and a second stage leaching process for the oxygen pressure of the first stage atmospheric leaching residue;
and combining the first-stage normal pressure leaching solution and the second-stage oxygen pressure leaching solution to obtain the potassium molybdate leaching solution.
3. The process of claim 2, wherein the reaction time of the atmospheric leaching process is 1 to 5 hours.
4. The treatment method according to claim 2, wherein the liquid-solid ratio in the oxygen pressure leaching process is 2:1-5:1 mL/g.
5. The treatment method according to claim 2, wherein the reaction time of the oxygen pressure leaching process is 1 to 5 hours.
6. The method according to claim 1, wherein the reaction time is 1 to 5 hours.
7. The method according to any one of claims 1 to 6, wherein the prepared potassium molybdate treatment solution is used for preparing ammonium molybdate.
8. The method according to claim 7, wherein the step of preparing ammonium molybdate from the potassium molybdate treatment solution comprises the steps of:
controlling the pH value of the potassium molybdate treatment solution to be 6-8, extracting molybdenum by adopting a strong alkaline anion exchange resin or an alkaline extractant, desorbing or back-extracting ammonia water and ammonium chloride to obtain an ammonium molybdate solution, and preparing ammonium paramolybdate by adopting an evaporation crystallization mode; or preparing ammonium tetramolybdate by adopting an acid precipitation crystallization mode.
9. The method according to any one of claims 1 to 6, wherein the obtained potassium molybdate treatment liquid is used for preparing polymerized potassium molybdate crystals.
10. The process of claim 9, wherein the step of preparing polymerized potassium molybdate crystals using the potassium molybdate treatment fluid comprises:
regulating the pH value of the potassium molybdate treatment solution to 1-4, and combining the polymeric molybdate with potassium to form polymeric potassium molybdate crystals.
11. The process of claim 10, wherein the crystallization temperature is 25-80 ℃.
12. The method according to claim 11, wherein the crystallization time is 0.5 to 2 hours.
13. The method according to claim 9, wherein the obtained crystallization mother liquor is used for preparing the compound fertilizer by evaporating and crystallizing after deep extraction of molybdenum.
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