CN119409230B - A kind of preparation method of ammonium heptamolybdate - Google Patents
A kind of preparation method of ammonium heptamolybdate Download PDFInfo
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- CN119409230B CN119409230B CN202510013184.3A CN202510013184A CN119409230B CN 119409230 B CN119409230 B CN 119409230B CN 202510013184 A CN202510013184 A CN 202510013184A CN 119409230 B CN119409230 B CN 119409230B
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- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title abstract description 36
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 69
- 239000011733 molybdenum Substances 0.000 claims abstract description 69
- 239000003054 catalyst Substances 0.000 claims abstract description 42
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 25
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000012141 concentrate Substances 0.000 claims abstract description 22
- 238000001816 cooling Methods 0.000 claims abstract description 14
- 238000001704 evaporation Methods 0.000 claims abstract description 11
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 238000003756 stirring Methods 0.000 claims description 31
- 239000000843 powder Substances 0.000 claims description 30
- 238000001914 filtration Methods 0.000 claims description 29
- 150000004696 coordination complex Chemical class 0.000 claims description 28
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 27
- 239000011609 ammonium molybdate Substances 0.000 claims description 27
- 229940010552 ammonium molybdate Drugs 0.000 claims description 27
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 27
- 239000000706 filtrate Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 9
- 239000001099 ammonium carbonate Substances 0.000 claims description 9
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 239000013110 organic ligand Substances 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 5
- PIPQOFRJDBZPFR-UHFFFAOYSA-N 1h-benzimidazole-5,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC2=C1NC=N2 PIPQOFRJDBZPFR-UHFFFAOYSA-N 0.000 claims description 4
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 claims description 4
- ZEVWQFWTGHFIDH-UHFFFAOYSA-N 1h-imidazole-4,5-dicarboxylic acid Chemical compound OC(=O)C=1N=CNC=1C(O)=O ZEVWQFWTGHFIDH-UHFFFAOYSA-N 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- LVPMIMZXDYBCDF-UHFFFAOYSA-N isocinchomeronic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)N=C1 LVPMIMZXDYBCDF-UHFFFAOYSA-N 0.000 claims description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- MUYSADWCWFFZKR-UHFFFAOYSA-N cinchomeronic acid Chemical compound OC(=O)C1=CC=NC=C1C(O)=O MUYSADWCWFFZKR-UHFFFAOYSA-N 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 2
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 2
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 2
- FCKJABJGVFTWPW-UHFFFAOYSA-H iron(3+);trisulfate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FCKJABJGVFTWPW-UHFFFAOYSA-H 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims 4
- 239000002002 slurry Substances 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 12
- 239000001301 oxygen Substances 0.000 abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 abstract description 12
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 8
- 150000004706 metal oxides Chemical class 0.000 abstract description 8
- 229910021529 ammonia Inorganic materials 0.000 abstract description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000002086 nanomaterial Substances 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 238000004090 dissolution Methods 0.000 abstract description 4
- 238000002386 leaching Methods 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 55
- 238000002156 mixing Methods 0.000 description 15
- 238000005303 weighing Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 230000001105 regulatory effect Effects 0.000 description 10
- 239000000084 colloidal system Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000007974 sodium acetate buffer Substances 0.000 description 4
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- UZJJFTNGFSFYTP-UHFFFAOYSA-L copper diacetate tetrahydrate Chemical compound O.O.O.O.[Cu++].CC([O-])=O.CC([O-])=O UZJJFTNGFSFYTP-UHFFFAOYSA-L 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 206010021143 Hypoxia Diseases 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229940031182 nanoparticles iron oxide Drugs 0.000 description 1
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 1
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The application relates to the technical field of ammonium heptamolybdate preparation, in particular to a preparation method of ammonium heptamolybdate. The application accelerates the dissolution of molybdenum in the molybdenum concentrate by using the high-efficiency catalyst, thereby improving the recovery rate of molybdenum. The preparation method of ammonium heptamolybdate comprises the specific steps of firstly crushing molybdenum concentrate, oxidizing low-valence molybdenum in the molybdenum concentrate into high-valence molybdenum by hydrogen peroxide under the catalysis of a catalyst, leaching, removing impurities by ammonia leaching, and finally evaporating, concentrating, cooling and crystallizing. The catalyst used in the preparation process of the ammonium heptamolybdate is a carbon-nitrogen doped metal oxide nanomaterial, has large specific surface area, is rich in oxygen vacancies and high in catalytic activity, and is beneficial to rapid oxidation and dissolution of molybdenum. In addition, a large amount of acid liquor and ammonia water are not used in the preparation process of the ammonium heptamolybdate, so that pollution is reduced.
Description
Technical Field
The application relates to the technical field of ammonium heptamolybdate preparation, in particular to a preparation method of ammonium heptamolybdate.
Background
Ammonium heptamolybdate is an important intermediate product in the molybdenum metallurgy process, is applied to preparing molybdenum powder and deep-processing products thereof, catalysts, dyes, pigments, micro-fertilizers and the like, and gradually develops to the high-tech fields of high-end material preparation, nano material synthesis, detection assay and the like along with the development of science and technology.
At present, a direct oxidizing roasting method is generally adopted in domestic production of ammonium heptamolybdate, molybdenum concentrate is firstly oxidized into industrial molybdenum oxide, the industrial molybdenum oxide is subjected to acid washing, ammonia leaching and impurity removal, ammonium tetramolybdate is precipitated and separated out, then the ammonium tetramolybdate is dissolved by ammonia water, and an ammonium heptamolybdate product is obtained through evaporation concentration and cooling crystallization. Therefore, how to further improve the preparation process of ammonium heptamolybdate, reduce environmental pollution and improve the quality of ammonium heptamolybdate is a main development direction of manufacturing enterprises.
The Chinese patent application publication No. CN112758983A discloses a preparation method of ammonium heptamolybdate, which does not adopt an ammonolysis recrystallization method of ammonium tetramolybdate, so that ammonia nitrogen wastewater pollution is reduced, but the method takes molybdenum calcine as a raw material, and the energy consumption is high in the preparation process of the molybdenum calcine, and low-valence molybdenum which is not completely oxidized is difficult to recover, so that the recovery rate of molybdenum is reduced.
In order to improve the recovery rate of molybdenum, the Chinese patent application document with the publication number of CN107601565A discloses a preparation method of ammonium molybdate, which adds hydrogen peroxide to convert low-valence molybdenum into high-valence molybdenum, so that the recovery rate of molybdenum is improved, but a large amount of organic solvents are used in the preparation process, and the post-treatment is difficult.
Disclosure of Invention
In order to reduce ammonia nitrogen pollution and improve molybdenum recovery rate, the application provides a preparation method of ammonium heptamolybdate.
A method for preparing ammonium heptamolybdate, comprising the following steps:
S1, crushing molybdenum concentrate, adding water for pulping, adding a catalyst and a hydrogen peroxide solution, uniformly mixing and stirring, adjusting the pH value to 9-11, reacting for 1-3 hours at 25-35 ℃, and filtering to obtain filtrate;
s2, introducing liquid ammonia into the filtrate, adjusting the pH value to 8.5-9, reacting for 0.5-1h at the temperature of 60-70 ℃, slowly adding ammonium carbonate while stirring, standing, and filtering to obtain an ammonium molybdate solution;
S3, evaporating and concentrating the ammonium molybdate solution until the pH value is 6-6.5, and cooling, crystallizing, filtering, washing, centrifuging and spin-drying;
the preparation method of the catalyst in the step S1 comprises the following steps:
(1) Dispersing carbon-nitrogen source organic ligand in water, adding metal active component precursor, regulating pH value to 2-6, reacting at 120-160 deg.C for 0.5-3 hr, cooling, crystallizing, grinding to obtain metal complex powder;
(2) Roasting the metal complex powder for 1-3 hours at 300-450 ℃ in nitrogen atmosphere.
According to the technical scheme, firstly, under the catalysis of a catalyst, low-valence molybdenum in molybdenum concentrate is oxidized into high-valence molybdenum by hydrogen peroxide, the high-valence molybdenum enters a solution, then liquid ammonia is introduced to generate ammonium molybdate, then ammonium carbonate is added to remove impurities, and finally, the ammonium heptamolybdate is obtained through evaporation concentration, cooling crystallization, filtration, washing, centrifugation and spin-drying.
The catalyst plays an important role in the process of molybdenum dissolution. Firstly, the active component in the catalyst is metal oxide, which can continuously receive electrons and lose electrons, plays a role of electron transfer, continuously and circularly regenerates, not only maintains the activity of the catalyst, but also can support the decomposition of hydrogen peroxide to promote the oxidation of molybdenum, secondly, after carbon and nitrogen doping, the metal oxide in the catalyst can increase oxygen vacancies, so that the catalytic activity is higher, thirdly, the catalyst takes carbon and nitrogen as a matrix, the defect that the metal oxide nano material is easy to agglomerate is overcome, and higher stability is provided for the catalyst, and the catalyst is prevented from being deactivated in the long-time use process.
In addition, liquid ammonia is directly introduced in the ammonia leaching process instead of using ammonia water solution, ammonia recovery is simple, the use amount of ammonia water is greatly reduced, and accordingly ammonia nitrogen wastewater emission is reduced, and enough ammonia sources can be provided, so that ammoniation reaction can be rapidly and efficiently carried out, the generation rate of ammonium molybdate is improved, and the reaction time is shortened.
In the preparation process of the catalyst, firstly, a metal complex is synthesized by a hydrothermal method, then the metal complex is used as a precursor, and the catalyst is obtained by high-temperature roasting in a nitrogen atmosphere. Firstly, nitrogen is introduced under the high temperature condition, so that the oxygen concentration is reduced, oxygen atoms in the material are separated due to oxygen deficiency to form oxygen vacancies, secondly, carbon and nitrogen react with metal oxide under the high temperature condition, oxygen in the metal oxide is consumed to form oxygen vacancies, and thirdly, the desorption of the oxygen atoms can be increased in the acidic environment. Therefore, the catalyst obtained by the method is rich in oxygen vacancies, and the oxygen vacancies can adsorb reactant molecules, such as hydrogen peroxide molecules, so that the reactant molecules are decomposed into oxygen active species, and the oxygen active species are strong oxidants, so that molybdenum disulfide in molybdenum concentrate powder can be further attacked, the sulfur-molybdenum bond breakage of the molybdenum disulfide is promoted, the molybdenum is oxidized from a low valence state to a high valence state, the oxidation process is accelerated, and the oxidation reaction rate is improved. In addition, oxygen vacancies can also cause local electron density changes, which is beneficial to electron transfer, and not only can provide extra electrons to participate in catalytic reaction, but also can accept electrons, thereby improving the catalytic reaction rate.
Preferably, in the step S1, the mass ratio of the molybdenum concentrate powder to the catalyst to the hydrogen peroxide is 100 (0.5-2) to 15-30.
Preferably, in the step S1, the solid-to-liquid ratio of the molybdenum concentrate powder to water is 1 (3-4.5).
Preferably, the metal complex powder in step (1) is modified by a method comprising the steps of:
dissolving ferric salt in water, slowly adding sodium hydroxide while stirring, filtering, adding acetic acid into the precipitate, stirring to form colloid solution, dispersing metal complex powder into colloid solution, centrifuging, washing, and drying.
In the technical scheme, the iron oxide nano particles formed after roasting are smaller by forming the iron colloid solution, so that the specific surface area of the catalyst nano material is improved, the dispersibility is better, the agglomeration of nano iron oxide is reduced, and the catalytic activity of the catalyst is further improved. In addition, the nano ferric oxide can also be used as a metal active component to synergistically improve the catalytic activity of the catalyst.
Preferably, the carbon-nitrogen source organic ligand in the step (1) is one of imidazole-4, 5-dicarboxylic acid, benzimidazole-5, 6-dicarboxylic acid, pyridine-3, 4-dicarboxylic acid, pyridine-2, 6-dicarboxylic acid and pyridine-2, 5-dicarboxylic acid.
Preferably, in the step (1), the metal active component is one of copper oxide, cobalt oxide and nickel oxide.
Preferably, in the step (1), the mass ratio of the carbon-nitrogen source organic ligand to the metal active component precursor is 1 (1.2-1.8).
Preferably, the mass ratio of the ferric salt to the acetic acid is 1 (0.45-0.7).
Preferably, the mass ratio of the ferric salt to the metal complex powder is 1 (0.5-1.8).
The technical scheme of the application at least comprises the following beneficial effects:
1. According to the application, the carbon-nitrogen doped metal oxide nano material is used as a catalyst to catalyze the transition from low-valence molybdenum to high-valence molybdenum, so that the oxidation process of molybdenum is accelerated, the dissolution of molybdenum is promoted, and the recovery rate of molybdenum is improved.
2. According to the application, the metal complex powder is obtained through a hydrothermal method, and then is roasted in a nitrogen atmosphere, so that the specific surface area is increased, the number of oxygen vacancies is increased, and the catalytic activity of the catalyst is improved.
3. According to the application, the metal complex powder is dispersed in the colloidal solution of iron, and after roasting, the loaded nano iron oxide has larger specific surface area and more uniform distribution, so that the catalytic activity of the catalyst is further improved.
4. The application does not use ammonia water and a large amount of acid solution, but directly introduces liquid ammonia, the ammonia recovery is simple, the use amount of the ammonia water is greatly reduced, thereby reducing the emission of ammonia nitrogen wastewater, providing enough ammonia source, improving the formation rate of ammonium molybdate and shortening the reaction time.
Drawings
FIG. 1 is a graph showing the change in the purity of ammonium heptamolybdate and the recovery of molybdenum.
Detailed Description
The present application will be described in further detail with reference to examples.
The raw materials of the examples and comparative examples of the present application are commercially available in general except for the specific descriptions.
Examples
Example 1
The preparation method of the ammonium heptamolybdate in the embodiment comprises the following steps:
S1, weighing 100g of molybdenum concentrate (42.56% of molybdenum), crushing, adding 300g of water for size mixing, adding 0.5g of catalyst and 50g of 30% hydrogen peroxide solution, uniformly mixing and stirring, adding 1mol/L sodium hydroxide solution for regulating the pH value to 9, reacting for 3 hours at 25 ℃, and filtering to obtain filtrate;
s2, introducing liquid ammonia into the filtrate, adjusting the pH value to 8.5, reacting for 1h at the temperature of 60 ℃, slowly adding ammonium carbonate while stirring until the solution is transparent, standing and filtering to obtain an ammonium molybdate solution;
s3, evaporating and concentrating the ammonium molybdate solution until the pH value is 6, and cooling and crystallizing, filtering, washing, centrifuging and spin-drying the concentrated ammonium molybdate solution;
the preparation method of the catalyst in the embodiment comprises the following steps:
(1) 1g of imidazole-4, 5-dicarboxylic acid is weighed and dispersed in 50mL of deionized water, 1.8g of cobalt acetate tetrahydrate is added, an acetic acid-sodium acetate buffer solution is added to adjust the pH value to 2, the mixture is reacted for 3 hours at 120 ℃, and the mixture is cooled, crystallized and ground to obtain metal complex powder;
(2) And (3) roasting the metal complex powder for 3 hours at 300 ℃ in a nitrogen atmosphere.
Example 2
The preparation method of the ammonium heptamolybdate in the embodiment comprises the following steps:
S1, weighing 100g of molybdenum concentrate (42.56% of molybdenum), crushing, adding 450g of water for size mixing, adding 0.5g of catalyst and 50g of 30% hydrogen peroxide solution, mixing and stirring uniformly, adding 1mol/L sodium hydroxide solution for regulating the pH value to 11, reacting for 1h at 35 ℃, and filtering to obtain filtrate;
S2, introducing liquid ammonia into the filtrate, adjusting the pH value to 9, reacting for 0.5h at the temperature of 70 ℃, slowly adding ammonium carbonate while stirring until the solution is transparent, standing and filtering to obtain an ammonium molybdate solution;
s3, evaporating and concentrating the ammonium molybdate solution until the pH value is 6.5, and cooling, crystallizing, filtering, washing, centrifuging and spin-drying the concentrated ammonium molybdate solution;
the preparation method of the catalyst in the embodiment comprises the following steps:
(1) 1g of pyridine-2, 5-dicarboxylic acid is weighed and dispersed in 50mL of deionized water, 1.2g of nickel sulfate hexahydrate is added, an acetic acid-sodium acetate buffer solution is added to adjust the pH value to 6, the mixture reacts for 0.5h at 160 ℃, and cooling crystallization and grinding are carried out to obtain metal complex powder;
(2) And (3) roasting the metal complex powder for 1h at 450 ℃ in a nitrogen atmosphere.
Example 3
The preparation method of the ammonium heptamolybdate in the embodiment comprises the following steps:
s1, weighing 100g of molybdenum concentrate (42.56% of molybdenum), crushing, adding 400g of water for size mixing, adding 0.5g of catalyst and 50g of 30% hydrogen peroxide solution, mixing and stirring uniformly, adding 1mol/L sodium hydroxide solution for regulating the pH value to 10, reacting for 2 hours at the temperature of 30 ℃, and filtering to obtain filtrate;
S2, introducing liquid ammonia into the filtrate, adjusting the pH value to 8.5, reacting for 0.5h at the temperature of 65 ℃, slowly adding ammonium carbonate into the filtrate while stirring until the solution is transparent, standing and filtering to obtain an ammonium molybdate solution;
s3, evaporating and concentrating the ammonium molybdate solution until the pH value is 6.5, and cooling, crystallizing, filtering, washing, centrifuging and spin-drying the concentrated ammonium molybdate solution;
the preparation method of the catalyst in the embodiment comprises the following steps:
(1) 1g of benzimidazole-5, 6-dicarboxylic acid is weighed and dispersed in 50mL of deionized water, 1.5g of copper acetate tetrahydrate is added, the pH value is regulated to be 4 by adding acetic acid-sodium acetate buffer solution, the mixture is reacted for 1h at 135 ℃, cooled, crystallized and ground, and metal complex powder is obtained;
(2) And (3) roasting the metal complex powder for 2 hours at 400 ℃ in a nitrogen atmosphere.
Example 4
The preparation method of ammonium heptamolybdate in this example is different from that in example 3 in that:
s1, weighing 100g of molybdenum concentrate (42.56% of molybdenum), crushing, adding 400g of water for size mixing, adding 2g of catalyst and 100g of 30% hydrogen peroxide solution, mixing and stirring uniformly, adding 1mol/L sodium hydroxide solution for regulating the pH value to 10, reacting for 2 hours at 30 ℃, and filtering to obtain filtrate;
The rest of the procedure is the same as in example 3;
the catalyst described in this example was prepared in the same manner as in example 3.
Example 5
The preparation method of ammonium heptamolybdate in this example is different from that in example 3 in that:
S1, weighing 100g of molybdenum concentrate (42.56% of molybdenum), crushing, adding 400g of water for size mixing, adding 1.5g of catalyst and 75g of 30% hydrogen peroxide solution, mixing and stirring uniformly, adding 1mol/L sodium hydroxide solution for regulating the pH value to 10, reacting for 2 hours at the temperature of 30 ℃, and filtering to obtain filtrate;
The rest of the procedure is the same as in example 3;
the catalyst described in this example was prepared in the same manner as in example 3.
Example 6
The preparation method of ammonium heptamolybdate in this example is the same as in example 5;
The preparation method of the catalyst in the embodiment comprises the following steps of;
(1) 1g of benzimidazole-5, 6-dicarboxylic acid is weighed and dispersed in 50mL of deionized water, 1.5g of copper acetate tetrahydrate is added, the pH value is regulated to be 4 by adding acetic acid-sodium acetate buffer solution, the mixture is reacted for 1h at 135 ℃, cooled, crystallized and ground, and metal complex powder is obtained;
(2) Weighing 14g of ferric chloride hexahydrate, dissolving in 100mL of deionized water, stirring for dissolving, slowly adding 50mL of 1mol/L sodium hydroxide solution while stirring to form a precipitate, performing centrifugal separation, filtering, adding 6.3g of acetic acid into the wet precipitate, stirring for 1h to form a colloid solution, adding 7g of metal complex powder into the colloid solution, dispersing for 0.5h, performing centrifugal separation, washing and drying to obtain modified metal complex powder;
(3) And (3) roasting the modified metal complex powder for 2 hours at 400 ℃ in a nitrogen atmosphere.
Example 7
The preparation method of ammonium heptamolybdate in this example is the same as in example 6;
the preparation method of the catalyst described in this example is different from that of example 6 in that:
(2) Weighing 20g of ferric sulfate nonahydrate, dissolving in 100mL of deionized water, stirring for dissolving, slowly adding 50mL of 1mol/L sodium hydroxide solution while stirring to form a precipitate, centrifuging, filtering, adding 14g of acetic acid into the wet precipitate, stirring for 1h to form a colloid solution, adding 36g of metal complex powder into the colloid solution, dispersing for 0.5h, centrifuging, washing and drying to obtain modified metal complex powder;
The remaining steps were the same as in example 6.
Example 8
The preparation method of ammonium heptamolybdate in this example is the same as in example 6;
the preparation method of the catalyst described in this example is different from that of example 6 in that:
(2) Weighing 14g of ferric nitrate nonahydrate, dissolving in 100mL of deionized water, stirring for dissolving, slowly adding 50mL of 1mol/L sodium hydroxide solution while stirring to form a precipitate, centrifuging, filtering, adding 8.4g of acetic acid into the wet precipitate, stirring for 1h to form a colloid solution, adding 14g of metal complex powder into the colloid solution, dispersing for 0.5h, centrifuging, washing and drying to obtain modified metal complex powder;
The remaining steps were the same as in example 6.
Comparative example
Comparative example 1
The preparation method of the ammonium heptamolybdate of the comparative example comprises the following steps:
S1, weighing 100g of molybdenum concentrate (42.56% of molybdenum), crushing, adding 400g of water for size mixing, adding 50g of 30% hydrogen peroxide solution, mixing and stirring uniformly, adding 1mol/L sodium hydroxide solution for regulating the pH value to 10, reacting for 2 hours at 30 ℃, and filtering to obtain filtrate;
S2, introducing liquid ammonia into the filtrate, adjusting the pH value to 8.5, reacting for 0.5h at the temperature of 65 ℃, slowly adding ammonium carbonate into the filtrate while stirring until the solution is transparent, standing and filtering to obtain an ammonium molybdate solution;
And S3, evaporating and concentrating the ammonium molybdate solution until the pH value is 6.5, and cooling, crystallizing, filtering, washing, centrifuging and spin-drying the concentrated ammonium molybdate solution.
Comparative example 2
The preparation method of the ammonium heptamolybdate of the comparative example comprises the following steps:
S1, weighing 100g of molybdenum concentrate (42.56% of molybdenum), crushing, adding 400g of water for size mixing, adding 0.5g of nano ferric oxide and 50g of 30% hydrogen peroxide solution, mixing and stirring uniformly, adding 1mol/L sodium hydroxide solution for regulating the pH value to 10, reacting for 2 hours at the temperature of 30 ℃, and filtering to obtain filtrate;
S2, introducing liquid ammonia into the filtrate, adjusting the pH value to 8.5, reacting for 0.5h at the temperature of 65 ℃, slowly adding ammonium carbonate into the filtrate while stirring until the solution is transparent, standing and filtering to obtain an ammonium molybdate solution;
And S3, evaporating and concentrating the ammonium molybdate solution until the pH value is 6.5, and cooling, crystallizing, filtering, washing, centrifuging and spin-drying the concentrated ammonium molybdate solution.
Comparative example 3
The preparation method of the ammonium heptamolybdate of the comparative example comprises the following steps:
S1, weighing 100g of molybdenum concentrate (containing 42.56% of molybdenum), crushing, adding 50g of sodium hypochlorite solution with the concentration of 30%, uniformly stirring, adding 1mol/L sodium hydroxide solution to adjust the pH value to 10, reacting for 2 hours at the temperature of 30 ℃, and filtering to obtain filtrate;
S2, introducing liquid ammonia into the filtrate, adjusting the pH value to 8.5, reacting for 0.5h at the temperature of 65 ℃, slowly adding ammonium carbonate into the filtrate while stirring until the solution is transparent, standing and filtering to obtain an ammonium molybdate solution;
And S3, evaporating and concentrating the ammonium molybdate solution until the pH value is 6.5, and cooling, crystallizing, filtering, washing, centrifuging and spin-drying the concentrated ammonium molybdate solution.
Performance test
Detection method
1. Purity of ammonium heptamolybdate
The purity of ammonium heptamolybdate obtained by the production methods of examples 1 to 8 and comparative examples 1 to 3 was examined with reference to GB/T657-2011 chemical reagent ammonium molybdate tetrahydrate (ammonium molybdate), and the measurement results are shown in FIG. 1.
2. Molybdenum recovery
Elemental analysis was used to determine the molybdenum content in the molybdenum concentrate and ammonium heptamolybdate.
Molybdenum recovery was calculated according to the formula ω=m 1φ1/m0φ0 ×100%, where ω is molybdenum recovery,%, "m 1 is ammonium heptamolybdate mass, g, # 1 is molybdenum content in ammonium heptamolybdate,%," m 0 is molybdenum concentrate mass, g, # 0 is molybdenum content in molybdenum concentrate,%, and the result is shown in fig. 1.
Analysis of results
As can be seen from FIG. 1, the purity of ammonium heptamolybdate obtained by the preparation methods of examples 1 to 8 can reach more than 95%, even more than 99%, and the recovery rate of molybdenum can reach more than 98% at the highest.
As can be seen from the data of examples 1-3 and comparative examples 1-3 in FIG. 1, the addition of the catalyst is advantageous for the improvement of molybdenum recovery, and the metal oxide is more catalytically active after carbon nitrogen doping, and the molybdenum recovery is improved.
As can be seen from the data of examples 3-5 in FIG. 1, the molybdenum recovery increases by more than 90% with increasing amounts of catalyst and hydrogen peroxide solution, but the molybdenum recovery increases less significantly after increasing to a certain level.
As can be seen from the data of examples 5-8 in FIG. 1, the incorporation of nano-iron oxide further improved the molybdenum recovery by adjusting and even reaching over 98%.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (6)
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| CN110681382A (en) * | 2019-09-18 | 2020-01-14 | 太原理工大学 | MOF-cobalt-based metal oxide catalyst for catalytic oxidation of toluene and preparation method thereof |
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| WO2013142022A1 (en) * | 2012-03-23 | 2013-09-26 | Kennecott Utah Copper Llc | Process for the conversion of molybdenite to molybdenum oxide |
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| CN110681382A (en) * | 2019-09-18 | 2020-01-14 | 太原理工大学 | MOF-cobalt-based metal oxide catalyst for catalytic oxidation of toluene and preparation method thereof |
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