CN113800569A - Method for preparing ammonium molybdate and recovering tungsten, copper and sulfur from molybdenum-removed slag - Google Patents
Method for preparing ammonium molybdate and recovering tungsten, copper and sulfur from molybdenum-removed slag Download PDFInfo
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- CN113800569A CN113800569A CN202010527152.2A CN202010527152A CN113800569A CN 113800569 A CN113800569 A CN 113800569A CN 202010527152 A CN202010527152 A CN 202010527152A CN 113800569 A CN113800569 A CN 113800569A
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- Prior art keywords
- molybdenum
- copper
- tungsten
- ammonium
- acid
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 56
- 239000010949 copper Substances 0.000 title claims abstract description 56
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000002893 slag Substances 0.000 title claims abstract description 46
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 46
- 239000010937 tungsten Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 42
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 title claims abstract description 27
- 239000011609 ammonium molybdate Substances 0.000 title claims abstract description 26
- 235000018660 ammonium molybdate Nutrition 0.000 title claims abstract description 26
- 229940010552 ammonium molybdate Drugs 0.000 title claims abstract description 26
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 23
- 239000011593 sulfur Substances 0.000 title claims abstract description 23
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 24
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 24
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims abstract description 20
- 238000002386 leaching Methods 0.000 claims abstract description 18
- 238000005342 ion exchange Methods 0.000 claims abstract description 16
- 238000004070 electrodeposition Methods 0.000 claims abstract description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 12
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 10
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 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 claims abstract description 8
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims abstract description 7
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 6
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims abstract description 6
- 238000002425 crystallisation Methods 0.000 claims abstract description 5
- 230000008025 crystallization Effects 0.000 claims abstract description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 57
- 229910052750 molybdenum Inorganic materials 0.000 claims description 57
- 239000011733 molybdenum Substances 0.000 claims description 57
- 239000000243 solution Substances 0.000 claims description 34
- 238000001914 filtration Methods 0.000 claims description 25
- 239000000706 filtrate Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims description 13
- 239000012065 filter cake Substances 0.000 claims description 11
- 239000002244 precipitate Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 8
- 238000003795 desorption Methods 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 8
- 150000007522 mineralic acids Chemical class 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 7
- 239000003957 anion exchange resin Substances 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 5
- 238000003916 acid precipitation Methods 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 4
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims description 4
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 abstract 1
- 239000012452 mother liquor Substances 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 28
- 238000004519 manufacturing process Methods 0.000 description 10
- 238000011084 recovery Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 6
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 5
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- APCLRHPWFCQIMG-UHFFFAOYSA-N 4-(5,6-dimethoxy-1-benzothiophen-2-yl)-4-oxobutanoic acid Chemical compound C1=C(OC)C(OC)=CC2=C1SC(C(=O)CCC(O)=O)=C2 APCLRHPWFCQIMG-UHFFFAOYSA-N 0.000 description 3
- 229940125791 MSA-2 Drugs 0.000 description 3
- 108010057081 Merozoite Surface Protein 1 Proteins 0.000 description 3
- 101710162106 Merozoite surface antigen 2 Proteins 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 229910052961 molybdenite Inorganic materials 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- -1 electronics Substances 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000011684 sodium molybdate Substances 0.000 description 2
- 235000015393 sodium molybdate Nutrition 0.000 description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- 229910019934 (NH4)2MoO4 Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BIOOACNPATUQFW-UHFFFAOYSA-N calcium;dioxido(dioxo)molybdenum Chemical compound [Ca+2].[O-][Mo]([O-])(=O)=O BIOOACNPATUQFW-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
- C01G41/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C3/00—Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/008—Wet processes by an alkaline or ammoniacal leaching
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacturing & Machinery (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Mechanical Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for preparing ammonium molybdate and recovering tungsten, copper and sulfur by molybdenum-removing slag, which comprises the following main steps: the molybdenum-removed slag is subjected to high-temperature high-pressure oxidation conversion under the condition of an ammonia medium, so that the leaching rate is improved; acid-precipitating the leaching solution to obtain a mixture containing molybdic acid and tungstic acid, and dissolving the mixture with ammonia water to obtain a crude ammonium molybdate solution; removing tungsten from the ammonium molybdate solution by two steps of adsorption tungsten removal and ion exchange of the crude ammonium molybdate solution, realizing the removal of tungsten from the ammonium molybdate solution, and recovering a corresponding crude tungstic acid product; removing a small amount of divalent metal ions present in the solution by ammonium sulfide; preparing an ammonium heptamolybdate product by vacuum crystallization; the separated copper-containing solution is used for recovering metal copper by an electrodeposition method, and the mother liquor of electrodeposition is used for recovering ammonium sulfate by a triple-effect evaporator. The method has the advantages that the ammonium heptamolybdate product meeting the national standard is recovered from the molybdenum-removing slag, and simultaneously, all effective components of the molybdenum-removing slag are recovered, so that secondary recycling of all components of the molybdenum-removing slag is realized.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to the technical field of metal hydrometallurgy and resource regeneration, in particular to a method for preparing ammonium molybdate and recovering tungsten, copper and sulfur by removing molybdenum slag.
[ background of the invention ]
Molybdenum and tungsten belong to VIB group elements in the periodic table, are silver-white high-melting-point metals, are inactive at normal temperature and do not react with most nonmetal elements. Molybdenum and tungsten have a wide range of uses in modern industrial fields, such as steel, electronics, petroleum, chemical, medicine, etc. Molybdenum and tungsten also play different roles in some industrial fields, for example, tungsten is widely used for making various filaments and heating elements of electric furnaces, and molybdenum is an indispensable component in catalysts. With the continuous development of industrial scale, the production of molybdenum and tungsten products by using molybdenum and tungsten mineral resources is increasingly restricted by insufficient reserves in the nature, and secondary regeneration of molybdenum and tungsten is a very important way for solving the problem of insufficient mineral resources. Nowadays, technical research on secondary recycling of various molybdenum and tungsten is actively conducted.
Since molybdenum and tungsten belong to group VIB, there is a great similarity in their physical and chemical properties. In natural mineral deposits, they are often associated with each other. This results in the production of tungsten-containing and molybdenum-containing waste residues, respectively, during the industrial production of molybdenum and tungsten products. The secondary recycling of the waste residues has good resource and environmental protection significance.
Copper is one of ten large nonferrous metals, has good physical and chemical properties, and has wide application in the industrial field. Although the natural reserves of copper are relatively rich compared with molybdenum and tungsten, the copper resources are relatively deficient due to the larger industrial demand, and the copper mine reserves of China only account for 4.12 percent of the global copper reserves. The secondary resource utilization of copper plays an important role in national economic construction.
Ammonium paratungstate is an important product in industrial application of tungsten products, and is a raw material for manufacturing tungsten trioxide and metal tungsten powder. Because the tungsten product has the content of impurities in applicationVery strict limitations are imposed, and therefore, the removal of impurities is highly required in the production process of ammonium paratungstate. The impurities such as phosphorus, arsenic, silicon and the like are relatively easy to remove in the production, and the molybdenum is difficult and complicated to remove. The common methods for removing molybdenum from ammonium tungstate solution in the prior ammonium paratungstate production process comprise a selective precipitation method, an extraction method and an ion exchange method. The selective precipitation method is widely applied to the production of ammonium paratungstate due to clear principle, good effect and easy operation. The principle is that under the condition of proper temperature and pH value, ammonium sulfide is added into ammonium tungstate solution containing molybdate radical to make sulfurization reaction, and selectively MoO is added4 2-Sulfurization to MoS4 2-Then adding CuSO into the vulcanizing material4Solution is reacted to generate CuMoS with difficult solubility4Precipitating, filtering and separating to obtain a purified ammonium tungstate solution and a filter cake, namely the molybdenum-removing slag.
The molybdenum-removing slag mainly comprises molybdenum, copper and sulfur and contains a certain amount of tungsten, different elements in the molybdenum-removing slag are recovered, different economic values can be generated, and the comprehensive recovery of the elements is the final target. Chinese patents CN201210375776.2, CN201811366398.5, cn201810848354.x and CN201710476682.7 disclose methods for removing molybdenum slag and recovering molybdenum and copper, and the obtained products are metal molybdates, mainly sodium molybdate and calcium molybdate, and copper products in different forms. Chinese patent CN201811308570.1 discloses a method for preparing ammonium phosphotungstate from molybdenum-removing slag. Chinese patent CN201810845345.5 discloses a method for preparing iron molybdate by using molybdenum-removing slag as a raw material. Chinese patent CN201010555831.7 discloses a method for recovering tungsten from molybdenum-removing slag. In the above methods, only a part of the components of the molybdenum-removed slag are recovered, and other components may be useless waste. Chinese patents CN201811366395.1 and CN201910982680.4 disclose methods for recovering molybdenum, copper, tungsten and sulfur from molybdenum-removing slag respectively, wherein the method for recovering molybdenum, copper, tungsten and sulfur from molybdenum-removing slag comprises the steps of wet leaching the molybdenum-removing slag, the leaching degree is not high enough, the recovery rate of molybdenum is limited, and the method for recovering molybdenum, copper, tungsten and sulfur from the molybdenum-removing slag comprises the step of roasting the molybdenum-removing slag at a high temperature to generate sulfide gas pollution. Chinese patents CN201310429671.5 and CN201410529610.0 disclose methods for preparing crude ammonium molybdate by using molybdenum removal slag, wherein the method for directly leaching the molybdenum removal slag has low leaching rate, and the method for roasting the molybdenum removal slag in a resistance furnace has the problem of environmental pollution.
The method is characterized in that molybdenum ore is used as a resource to produce ammonium molybdate, the currently widely used technical route is a method for preparing molybdenum calcine by roasting molybdenum concentrate at high temperature and co-producing sulfuric acid, and the prepared molybdenum calcine can realize higher molybdenum leaching rate by ammonia leaching. In addition, a technical route for directly leaching molybdenite raw materials is provided, wherein a mixture of an oxidant, an alkaline leaching agent and the like is utilized in the route, molybdenum disulfide of molybdenite is converted into molybdate anion under the conditions of high temperature and high pressure, and meanwhile, negative divalent sulfur is converted into hexavalent sulfur to form sulfate anion. Chinese patent CN201610906901.6 discloses a method for treating molybdenite with co-production of ammonium molybdate and ammonium sulfate by oxygen pressure water leaching method.
The basic composition of the molybdenum removing slag can be expressed as CuMoS4Wherein the valence of sulfur is minus 2. The total leaching rate is not high by adopting the normal pressure condition to carry out alkaline leaching, acid leaching and ammonia leaching, and the technical route is easy to cause the waste of molybdenum and tungsten. The molybdenum oxide and the copper oxide are converted by adopting a roasting method, so that sulfur oxide gas is generated in the roasting process, and pollution is easily caused. Chinese patent No. CN201810848354.X discloses a method for preparing a sodium molybdate product by treating molybdenum removal slag under the conditions of high temperature and high pressure by using a sodium hydroxide solution as a medium and using industrial oxygen as an oxidant.
[ summary of the invention ]
The invention aims to provide a method for preparing ammonium molybdate and recovering tungsten, copper and sulfur from molybdenum-removed slag so as to fully recover various secondary resource components in the molybdenum-removed slag generated in the production of ammonium paratungstate.
In order to achieve the purpose, the invention provides the following technical scheme:
the application discloses a method for preparing ammonium molybdate and recovering tungsten, copper and sulfur by molybdenum-removing slag, which comprises the following steps:
a) high-pressure oxygen leaching: crushing, grinding and sieving the molybdenum-removed slag, adding 200-300-mesh undersize powder into an autoclave, adding ammonia water, introducing oxygen into the autoclave through a pipeline, controlling the oxygen partial pressure to be 2.3-2.7 MPa, heating the autoclave to 90-110 ℃, reacting for 8-10 hours under stirring, cooling the autoclave to 40 ℃, taking out the solution, and filtering to obtain a mixed solution containing molybdenum, tungsten, copper and sulfate radicals and filter residues;
b) acid precipitation: adjusting the pH of the mixed solution obtained in the step a) to 3.5-4.5 by using 10% inorganic acid, and performing solid-liquid separation to obtain a mixed filter cake of molybdic acid and tungstic acid and a filtrate containing copper sulfate;
c) dissolving ammonia: dissolving the mixed filter cake obtained in the step b) by using ammonia water, adjusting the pH value to 8.0-8.9, completely dissolving the precipitate, and filtering to remove a small amount of insoluble impurities to obtain a mixed solution containing molybdate radicals and tungstate radicals;
d) adsorbing and removing tungsten: adjusting the pH of the mixed solution obtained in the step c) to 9.0-10.0 under the stirring condition, and dropwise adding 2mol/L FeCl3Dissolving, adding 10% HNO3Adjusting the pH value to 6.5-7.0, stirring for 4 hours, and filtering to obtain a filtrate, wherein a filter cake is crude tungstic acid;
e) purifying: maintaining the filtrate obtained in the step d) at 85-90 ℃ and under the condition that the pH value is 8.0-10.0, adding a proper amount of sulfide to precipitate and purify the divalent metal in the solution for 3-5 hours, filtering the liquid to obtain filtrate, and discarding a filter cake;
f) ion exchange: adjusting the pH of the filtrate obtained in the step e) to 7.5-8.5 by using 10% inorganic acid, and then enabling the filtrate to pass through an ion exchange column, adsorbing tungstate radicals on the ion exchange column, and allowing molybdate radicals to flow out to obtain a post-crosslinking solution;
g) vacuum crystallization: adjusting the pH value of the post-crosslinking liquid obtained in the step f) to 6.0-7.0, keeping the temperature of a crystallization kettle at 70-80 ℃, and crystallizing under a vacuum condition to obtain ammonium heptamolybdate;
h) desorption, precipitation and filtration: desorbing the ion exchange column adsorbing tungstate radicals in the step f) by using ammonia water or a sodium hydroxide solution to obtain an ammonium tungstate or sodium tungstate solution, adjusting the pH of the ammonium tungstate or sodium tungstate solution to 3.0-4.0 by using inorganic acid, precipitating tungstic acid, and filtering to obtain crude tungstic acid;
i) electro-deposition: placing the filtrate obtained in the step b) in a double-membrane three-chamber electrolytic tank, taking copper as a cathode, performing electro-deposition on the copper at the temperature of 40 ℃, and stripping the copper on the electrode to obtain recovered copper;
j) triple-effect evaporation: evaporating the electrolyte obtained in the step i) by using a triple-effect evaporator to obtain distilled water and recovered ammonium sulfate.
Preferably, small amounts of sodium peroxide and iron catalyst are added simultaneously with the addition of ammonia water in step a).
Preferably, the inorganic acid in step b) is nitric acid, sulfuric acid or hydrochloric acid.
Preferably, the sulfide in step e) is ammonium sulfide, sodium sulfide or potassium sulfide.
Preferably, the ion exchange column in step f) is a strongly acidic styrene-based anion exchange resin exchange column or a weakly acidic styrene-based anion exchange resin exchange column.
The invention has the beneficial effects that: the invention provides a method for recovering ammonium molybdate, tungsten, copper and sulfur from molybdenum-removed slag, which realizes the full recovery of effective components in the molybdenum-removed slag:
(1) the molybdenum slag is removed through high-temperature high-pressure oxidation conversion, so that sulfur is converted into sulfate radicals, the leaching rate of effective components is improved by introducing an oxidant and a catalyst, and the emission of sulfur oxides is not generated;
(2) a small amount of tungsten in the molybdenum slag is separated and removed by adopting an ion exchange method, so that the discharge of waste water is reduced;
(3) by utilizing an electrodeposition method, the recovered copper with higher purity can be obtained for subsequent refining;
(4) the ammonium sulfate recovered by triple effect evaporation can be used as an agricultural fertilizer;
the features and advantages of the present invention will be described in detail by embodiments in conjunction with the accompanying drawings.
[ description of the drawings ]
FIG. 1 is a process flow diagram of a method for preparing ammonium molybdate and recovering tungsten, copper and sulfur from molybdenum removal slag according to the present invention;
[ detailed description ] embodiments
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the accompanying drawings and examples. It should be understood, however, that the description herein of specific embodiments is only intended to illustrate the invention and not to limit the scope of the invention. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present invention.
Referring to FIG. 1, CuMoS is a basic composition of the molybdenum-removing slag4In order to realize the total recovery of molybdenum, tungsten, copper and sulfur components, the invention adopts high-temperature high-pressure oxidation reaction to carry out oxidation conversion on the components, and in an ammonia medium, the main chemical reaction equation is as follows:
CuMoS4+8O2+8NH3+4H2O→(NH4)2MoO4+CuSO4+3(NH4)2SO4
when the reaction is complete, the products have better solubility in water, and a small amount of insoluble residues are filtered and discarded. And then carrying out systematic separation on the solution containing molybdenum, tungsten, copper and sulfur to prepare an ammonium heptamolybdate product, a crude tungstic acid product, a metal copper product and an ammonium sulfate fertilizer product, thereby realizing the complete recovery of chemical components except for molybdenum slag.
Example 1:
500g of sieved molybdenum-removing slag is added into a 2000mL autoclave, 1000mL of 10% ammonia water is added, the autoclave is closed, then oxygen is introduced into the autoclave through a pipeline, the oxygen partial pressure is controlled at 2.5MPa, the temperature of the autoclave is heated at 100 ℃, and the reaction is carried out for 8 hours under stirring. Cooling the autoclave to 40 ℃, taking out the solution, and filtering to obtain a mixed solution containing molybdenum, tungsten, copper and sulfate radicals; placing the mixed solution into a 5000mL flask, adjusting the pH to 4.0 by using 10% nitric acid for precipitation, and after solid-liquid separation, respectively obtaining molybdic acid and tungstic acid mixed precipitates and a solution containing copper sulfate; dissolving the precipitate in a 5000mL flask with 10% ammonia water, adjusting pH to 8.5, dissolving all precipitate, and filtering to remove a small amount of insoluble impurities; the pH of the obtained solution is adjusted to 9.5 under the stirring condition, and a proper amount of 2mol/L FeCl is added dropwise3Dissolving, adding 10% HNO3Adjusting pH to 6.8, stirring for 4 hr, filtering, and filteringRecovering the crude tungstic acid from the cake; adjusting the pH of the filtrate to 9.0 with 20% ammonia water, adding a small amount of ammonium sulfide, maintaining the temperature for 4 hours, cooling to 40 deg.C, and filtering; introducing the filtrate into an exchange column filled with weakly acidic styrene anion exchange resin, and receiving effluent of the exchange column; adjusting the pH of the effluent to 7.0 by using 10% ammonia water in a 1000mL flask at the stirring speed of 150rpm, heating to 75 ℃, vacuumizing by using a water circulating pump, and crystallizing to obtain an ammonium heptamolybdate product, wherein the product can meet the requirements of MSA-1 and MSA-2 products of the national standard (GB/T3460-2017) of ammonium molybdate through a national standard analysis method; by analyzing the molybdenum content of the raw material and the molybdenum content of the ammonium molybdate product, the recovery rate of molybdenum is calculated to be 93 percent; desorbing the ion exchange column by using 25% ammonia water to obtain tungstate radical desorption liquid, and adjusting the pH of the tungstate radical desorption liquid to 3.5 by using 10% nitric acid to obtain recovered crude tungstic acid; putting the solution containing the copper sulfate obtained after the acid precipitation into a double-membrane three-chamber electrolytic tank, carrying out electro-deposition on copper at the temperature of 40 ℃ by taking the copper as a cathode, and stripping the copper on an electrode to obtain a recovered copper product; putting the solution after electrodeposition into a 5000mL flask, heating to 70 ℃, vacuumizing to-0.06 MPa by using a water circulating vacuum pump, carrying out reduced pressure distillation, and recovering ammonium sulfate solid.
Example two:
500g of sieved molybdenum-removing slag, 1000mL of 10% ammonia water, 5g of sodium peroxide and 5g of ferric nitrate are added into a 2000mL autoclave, the autoclave is closed, then oxygen is introduced into the autoclave through a pipeline, the oxygen partial pressure is controlled at 2.5MPa, the autoclave is heated at 100 ℃, and the reaction is carried out for 8 hours under stirring. Cooling the autoclave to 40 ℃, taking out the solution, and filtering to obtain a mixed solution containing molybdenum, tungsten, copper and sulfate radicals; placing the mixed solution into a 5000mL flask, adjusting the pH to 4.0 by using 10% nitric acid for precipitation, and after solid-liquid separation, respectively obtaining molybdic acid and tungstic acid mixed precipitates and a solution containing copper sulfate; dissolving the precipitate in a 5000mL flask with 10% ammonia water, adjusting pH to 8.5, dissolving all precipitate, and filtering to remove a small amount of insoluble impurities; the pH of the obtained solution is adjusted to 9.5 under the stirring condition, and a proper amount of 2mol/L FeCl is added dropwise3Dissolving, adding 10% HNO3Adjusting the pH value to 6.8, stirring for 4 hours,filtering, and recovering crude tungstic acid from filter cakes; adjusting the pH of the filtrate to 9.0 with 20% ammonia water, adding a small amount of ammonium sulfide, maintaining the temperature for 4 hours, cooling to 40 deg.C, and filtering; introducing the filtrate into an exchange column filled with weakly acidic styrene anion exchange resin, and receiving effluent of the exchange column; adjusting the pH of the effluent to 7.0 by using 10% ammonia water in a 1000mL flask at the stirring speed of 150rpm, heating to 75 ℃, vacuumizing by using a water circulating pump, and crystallizing to obtain an ammonium heptamolybdate product, wherein the product can meet the requirements of MSA-1 and MSA-2 products of the national standard (GB/T3460-2017) of ammonium molybdate through a national standard analysis method; the recovery rate of molybdenum is calculated to be 98% by analyzing the molybdenum content of the raw material and the molybdenum content of the ammonium molybdate product; desorbing the ion exchange column by using 25% ammonia water to obtain tungstate radical desorption liquid, and adjusting the pH of the tungstate radical desorption liquid to 3.5 by using 10% nitric acid to obtain recovered crude tungstic acid; putting the solution containing the copper sulfate obtained after the acid precipitation into a double-membrane three-chamber electrolytic tank, carrying out electro-deposition on copper at the temperature of 40 ℃ by taking the copper as a cathode, and stripping the copper on an electrode to obtain a recovered copper product; putting the solution after electrodeposition into a 5000mL flask, heating to 70 ℃, vacuumizing to-0.06 MPa by using a water circulating vacuum pump, carrying out reduced pressure distillation, and recovering ammonium sulfate solid.
Example three:
500g of sieved molybdenum-removing slag, 1000mL of 10% ammonia water, 5g of sodium peroxide and 5g of ferric nitrate are added into a 2000mL autoclave, the autoclave is closed, then oxygen is introduced into the autoclave through a pipeline, the oxygen partial pressure is controlled at 2.5MPa, the autoclave is heated at 100 ℃, and the reaction is carried out for 8 hours under stirring. Cooling the autoclave to 40 ℃, taking out the solution, and filtering to obtain a mixed solution containing molybdenum, tungsten, copper and sulfate radicals; placing the mixed solution into a 5000mL flask, adjusting the pH to 4.0 by using 10% nitric acid for precipitation, and after solid-liquid separation, respectively obtaining molybdic acid and tungstic acid mixed precipitates and a solution containing copper sulfate; dissolving the precipitate in a 5000mL flask with 10% ammonia water, adjusting pH to 8.5, dissolving all precipitate, and filtering to remove a small amount of insoluble impurities; the pH of the obtained solution is adjusted to 9.5 under the stirring condition, and a proper amount of 2mol/L FeCl is added dropwise3Dissolving, adding 10% HNO3Adjusting the pH value to 6.8 and stirringStirring for 4 hours, filtering, and recovering crude tungstic acid from filter cakes; adjusting the pH of the filtrate to 9.0 with 20% ammonia water, adding a small amount of ammonium sulfide, maintaining the temperature for 4 hours, cooling to 40 deg.C, and filtering; introducing the filtrate into an exchange column filled with strongly acidic styrene anion exchange resin, and receiving effluent of the exchange column; adjusting the pH of the effluent to 7.0 by using 10% ammonia water in a 1000mL flask at the stirring speed of 150rpm, heating to 75 ℃, vacuumizing by using a water circulating pump, and crystallizing to obtain an ammonium heptamolybdate product, wherein the product can meet the requirements of MSA-1 and MSA-2 products of the national standard (GB/T3460-2017) of ammonium molybdate through a national standard analysis method; the recovery rate of molybdenum is calculated to be 95 percent by analyzing the molybdenum content of the raw material and the molybdenum content of the ammonium molybdate product; desorbing the ion exchange column by using 25% ammonia water to obtain tungstate radical desorption liquid, and adjusting the pH of the tungstate radical desorption liquid to 3.5 by using 10% nitric acid to obtain recovered crude tungstic acid; putting the solution containing the copper sulfate obtained after the acid precipitation into a double-membrane three-chamber electrolytic tank, carrying out electro-deposition on copper at the temperature of 40 ℃ by taking the copper as a cathode, and stripping the copper on an electrode to obtain a recovered copper product; putting the solution after electrodeposition into a 5000mL flask, heating to 70 ℃, vacuumizing to-0.06 MPa by using a water circulating vacuum pump, carrying out reduced pressure distillation, and recovering ammonium sulfate solid.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (5)
1. A method for preparing ammonium molybdate and recovering tungsten, copper and sulfur by molybdenum-removing slag is characterized in that: the method comprises the following steps:
a) high-pressure oxygen leaching: crushing, grinding and sieving the molybdenum-removed slag, adding 200-300-mesh undersize powder into an autoclave, adding ammonia water, introducing oxygen into the autoclave through a pipeline, controlling the oxygen partial pressure to be 2.3-2.7 MPa, heating the autoclave to 90-110 ℃, reacting for 8-10 hours under stirring, cooling the autoclave to 40 ℃, taking out the solution, and filtering to obtain a mixed solution containing molybdenum, tungsten, copper and sulfate radicals and filter residues;
b) acid precipitation: adjusting the pH of the mixed solution obtained in the step a) to 3.5-4.5 by using 10% inorganic acid, and performing solid-liquid separation to obtain a mixed filter cake of molybdic acid and tungstic acid and a filtrate containing copper sulfate;
c) dissolving ammonia: dissolving the mixed filter cake obtained in the step b) by using ammonia water, adjusting the pH value to 8.0-8.9,
dissolving the precipitate completely, and filtering to remove a small amount of insoluble impurities to obtain a mixed solution containing molybdate radicals and tungstate radicals;
d) adsorbing and removing tungsten: adjusting the pH of the mixed solution obtained in the step c) to 9.0-10.0 under the stirring condition, and dropwise adding 2mol/L FeCl3Dissolving, adding 10% HNO3Adjusting the pH value to 6.5-7.0, stirring for 4 hours, and filtering to obtain a filtrate, wherein a filter cake is crude tungstic acid;
e) purifying: maintaining the filtrate obtained in the step d) at 85-90 ℃ and under the condition that the pH value is 8.0-10.0, adding a proper amount of sulfide to precipitate and purify the divalent metal in the solution for 3-5 hours, filtering the liquid to obtain filtrate, and discarding a filter cake;
f) ion exchange: adjusting the pH of the filtrate obtained in the step e) to 7.5-8.5 by using 10% inorganic acid, and then enabling the filtrate to pass through an ion exchange column, adsorbing tungstate radicals on the ion exchange column, and allowing molybdate radicals to flow out to obtain a post-crosslinking solution;
g) vacuum crystallization: adjusting the pH value of the post-crosslinking liquid obtained in the step f) to 6.0-7.0, keeping the temperature of a crystallization kettle at 70-80 ℃, and crystallizing under a vacuum condition to obtain ammonium heptamolybdate;
h) desorption, precipitation and filtration: desorbing the ion exchange column adsorbing tungstate radicals in the step f) by using ammonia water or a sodium hydroxide solution to obtain an ammonium tungstate or sodium tungstate solution, adjusting the pH of the ammonium tungstate or sodium tungstate solution to 3.0-4.0 by using inorganic acid, precipitating tungstic acid, and filtering to obtain crude tungstic acid;
i) electro-deposition: placing the filtrate obtained in the step b) in a double-membrane three-chamber electrolytic tank, taking copper as a cathode, performing electro-deposition on the copper at the temperature of 40 ℃, and stripping the copper on the electrode to obtain recovered copper;
j) triple-effect evaporation: evaporating the electrolyte obtained in the step i) by using a triple-effect evaporator to obtain distilled water and recovered ammonium sulfate.
2. The method for recovering the ammonium molybdate and the tungsten, the copper and the sulfur prepared from the molybdenum removal slag as claimed in claim 1, is characterized in that: a small amount of sodium peroxide and an iron catalyst can be added at the same time of adding ammonia water in the step a).
3. The method for recovering the ammonium molybdate and the tungsten, the copper and the sulfur prepared from the molybdenum removal slag as claimed in claim 1, is characterized in that: the inorganic acid in the step b) is nitric acid, sulfuric acid or hydrochloric acid.
4. The method for recovering the ammonium molybdate and the tungsten, the copper and the sulfur prepared from the molybdenum removal slag as claimed in claim 1, is characterized in that: the sulfide in the step e) is ammonium sulfide, sodium sulfide or potassium sulfide.
5. The method for recovering the ammonium molybdate and the tungsten, the copper and the sulfur prepared from the molybdenum removal slag as claimed in claim 1, is characterized in that: the ion exchange column in the step f) is a strongly acidic styrene anion exchange resin exchange column or a weakly acidic styrene anion exchange resin exchange column.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102296180A (en) * | 2011-09-05 | 2011-12-28 | 中南大学 | Method for separating tungsten, molybdenum and bismuth in bismuth sulfide ore concentrate |
| CN103288135A (en) * | 2013-06-05 | 2013-09-11 | 杭州临安慧尔钼业科技有限公司 | Method for recycling all chemical components in filament melting molybdenum-containing waste acid |
| CN103388160A (en) * | 2013-07-19 | 2013-11-13 | 北京科技大学 | Method for preparation of ultrafine copper powder by waste circuit board copper dissolution-electrodeposition combined method |
| CN103964558A (en) * | 2014-04-30 | 2014-08-06 | 广东大众农业科技股份有限公司 | Wastewater zero emission method during production process of ammonium tungstate/ammonium molybdate |
| CN106086480A (en) * | 2016-06-30 | 2016-11-09 | 中南大学 | A kind of processing method of Tungsten smelting molybdenum removal slag |
| CN109576734A (en) * | 2017-09-28 | 2019-04-05 | 中国科学院过程工程研究所 | A method of recycling metal from sophisticated electronic waste |
| CN110106358A (en) * | 2019-05-09 | 2019-08-09 | 厦门钨业股份有限公司 | The method of precipitation and separation tungsten from high tungsten high molybdenum tungsten acid salt solution |
-
2020
- 2020-06-11 CN CN202010527152.2A patent/CN113800569B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102296180A (en) * | 2011-09-05 | 2011-12-28 | 中南大学 | Method for separating tungsten, molybdenum and bismuth in bismuth sulfide ore concentrate |
| CN103288135A (en) * | 2013-06-05 | 2013-09-11 | 杭州临安慧尔钼业科技有限公司 | Method for recycling all chemical components in filament melting molybdenum-containing waste acid |
| CN103388160A (en) * | 2013-07-19 | 2013-11-13 | 北京科技大学 | Method for preparation of ultrafine copper powder by waste circuit board copper dissolution-electrodeposition combined method |
| CN103964558A (en) * | 2014-04-30 | 2014-08-06 | 广东大众农业科技股份有限公司 | Wastewater zero emission method during production process of ammonium tungstate/ammonium molybdate |
| CN106086480A (en) * | 2016-06-30 | 2016-11-09 | 中南大学 | A kind of processing method of Tungsten smelting molybdenum removal slag |
| CN109576734A (en) * | 2017-09-28 | 2019-04-05 | 中国科学院过程工程研究所 | A method of recycling metal from sophisticated electronic waste |
| CN110106358A (en) * | 2019-05-09 | 2019-08-09 | 厦门钨业股份有限公司 | The method of precipitation and separation tungsten from high tungsten high molybdenum tungsten acid salt solution |
Non-Patent Citations (3)
| Title |
|---|
| 简钢: "离子交换法分离废催化剂中钨钼金属氧化物的研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 邱定蕃等编: "《稀贵金属冶金新进展》", 30 April 2019, 冶金工业出版社 * |
| 黄普选等: "新生态氢氧化铁分离钨钼的工艺研究", 《吉林化工学院学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115925080A (en) * | 2022-11-23 | 2023-04-07 | 江西理工大学 | Treatment method of tungsten smelting wastewater |
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