CN113801997A - Method for recycling ammonium molybdate and molybdenum precipitation agent from low-molybdenum raffinate molybdenum - Google Patents
Method for recycling ammonium molybdate and molybdenum precipitation agent from low-molybdenum raffinate molybdenum Download PDFInfo
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- CN113801997A CN113801997A CN202010532319.4A CN202010532319A CN113801997A CN 113801997 A CN113801997 A CN 113801997A CN 202010532319 A CN202010532319 A CN 202010532319A CN 113801997 A CN113801997 A CN 113801997A
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- molybdenum
- raffinate
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- precipitation agent
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- 239000011733 molybdenum Substances 0.000 title claims abstract description 127
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 126
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000001556 precipitation Methods 0.000 title claims abstract description 35
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 title claims abstract description 34
- 235000018660 ammonium molybdate Nutrition 0.000 title claims abstract description 34
- 239000011609 ammonium molybdate Substances 0.000 title claims abstract description 34
- 229940010552 ammonium molybdate Drugs 0.000 title claims abstract description 34
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 28
- 238000004064 recycling Methods 0.000 title claims abstract description 18
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 16
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 16
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 16
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 16
- 238000002386 leaching Methods 0.000 claims abstract description 13
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 12
- 239000012535 impurity Substances 0.000 claims abstract description 10
- 238000005342 ion exchange Methods 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 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 7
- 239000002244 precipitate Substances 0.000 claims abstract description 6
- 238000003916 acid precipitation Methods 0.000 claims abstract description 4
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 4
- 238000001953 recrystallisation Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 36
- 238000000926 separation method Methods 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 11
- 229920005989 resin Polymers 0.000 claims description 11
- 239000002893 slag Substances 0.000 claims description 11
- 239000012065 filter cake Substances 0.000 claims description 10
- 150000001450 anions Chemical class 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 150000007522 mineralic acids Chemical class 0.000 claims description 8
- 238000002798 spectrophotometry method Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 150000002696 manganese Chemical class 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000012452 mother liquor Substances 0.000 claims description 6
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 238000003795 desorption Methods 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 239000003957 anion exchange resin Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000004537 pulping Methods 0.000 claims description 3
- 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 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 235000006748 manganese carbonate Nutrition 0.000 claims description 2
- 239000011656 manganese carbonate Substances 0.000 claims description 2
- 229940093474 manganese carbonate Drugs 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 2
- 150000003141 primary amines Chemical class 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 150000003335 secondary amines Chemical class 0.000 claims description 2
- 239000002002 slurry Substances 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
- 239000006228 supernatant Substances 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 150000002697 manganese compounds Chemical class 0.000 claims 2
- 239000000047 product Substances 0.000 abstract description 15
- 239000002994 raw material Substances 0.000 abstract description 6
- 230000001376 precipitating effect Effects 0.000 abstract description 5
- 239000012716 precipitator Substances 0.000 abstract 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 15
- 229910052721 tungsten Inorganic materials 0.000 description 12
- 239000010937 tungsten Substances 0.000 description 12
- 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 10
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000011572 manganese Substances 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- -1 molybdate radical ions Chemical class 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000009854 hydrometallurgy Methods 0.000 description 4
- MGRWKWACZDFZJT-UHFFFAOYSA-N molybdenum tungsten Chemical compound [Mo].[W] MGRWKWACZDFZJT-UHFFFAOYSA-N 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- BIOOACNPATUQFW-UHFFFAOYSA-N calcium;dioxido(dioxo)molybdenum Chemical compound [Ca+2].[O-][Mo]([O-])(=O)=O BIOOACNPATUQFW-UHFFFAOYSA-N 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- ZXOKVTWPEIAYAB-UHFFFAOYSA-N dioxido(oxo)tungsten Chemical compound [O-][W]([O-])=O ZXOKVTWPEIAYAB-UHFFFAOYSA-N 0.000 description 2
- CDUFCUKTJFSWPL-UHFFFAOYSA-L manganese(II) sulfate tetrahydrate Chemical compound O.O.O.O.[Mn+2].[O-]S([O-])(=O)=O CDUFCUKTJFSWPL-UHFFFAOYSA-L 0.000 description 2
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound 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=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 2
- CXVCSRUYMINUSF-UHFFFAOYSA-N tetrathiomolybdate(2-) Chemical compound [S-][Mo]([S-])(=S)=S CXVCSRUYMINUSF-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910001309 Ferromolybdenum Inorganic materials 0.000 description 1
- 229910016003 MoS3 Inorganic materials 0.000 description 1
- YWKPIECJIPTMCY-UHFFFAOYSA-H [Mo+4].S(=O)(=O)([O-])[O-].[Mn+2].S(=O)(=O)([O-])[O-].S(=O)(=O)([O-])[O-] Chemical compound [Mo+4].S(=O)(=O)([O-])[O-].[Mn+2].S(=O)(=O)([O-])[O-].S(=O)(=O)([O-])[O-] YWKPIECJIPTMCY-UHFFFAOYSA-H 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000009851 ferrous metallurgy Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000005837 radical ions Chemical class 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
- C22B3/14—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions containing ammonia or ammonium salts
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/34—Obtaining molybdenum
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a method for recovering and producing ammonium molybdate from low-molybdenum raffinate molybdenum and recycling a molybdenum precipitation agent, which comprises the steps of providing a molybdenum precipitation agent for precipitating molybdate from molybdenum-containing raffinate with low molybdenum content; taking the molybdate precipitate as a raw material, and preparing an ammonium tetramolybdate product by ammonia leaching, purifying and impurity removing, ion exchange, acid precipitation, filtering and the like, and taking ammonium tetramolybdate as a raw material, and preparing an ammonium heptamolybdate product with higher added value by a recrystallization method; in the process of preparing ammonium tetramolybdate and ammonium heptamolybdate by precipitation of molybdate, the molybdenum precipitation agent is recovered in the form of manganese sulfate, and the manganese sulfate can be reused as the precipitator of molybdenum-containing raffinate for recycling. The method provided by the invention can effectively recover molybdenum in the molybdenum-containing raffinate, and can produce ammonium molybdate products meeting the national standard and recycle the precipitator, thereby realizing the environment-friendly high-value utilization of the molybdenum-containing raffinate.
Description
[ technical field ] A method for producing a semiconductor device
The invention belongs to the technical field of metal hydrometallurgy and resource regeneration, and particularly relates to a method for recycling ammonium molybdate and a molybdenum precipitation agent from low-molybdenum raffinate molybdenum.
[ background of the invention ]
Tungsten products are an important industrial resource and widely applied in the industrial field, and mainly come from various tungsten ores obtained by hydrometallurgy. China has ascertained that the storage capacity of tungsten ore resources accounts for more than 60% of the world, and the hydrometallurgical technology of producing Ammonium Paratungstate (APT) by using scheelite and wolframite as raw materials and producing various tungsten products on the basis of the APT is a main way for utilizing the tungsten resources. Scheelite and wolframite in China have the characteristic of being associated with molybdenum with different contents of metal elements, and in order to produce high-quality APT products, a tungsten-molybdenum separation process is required in a production process route of a hydrometallurgy technology. The national standard GB/T10116-2007 of China stipulates that the content of Mo in 0-grade and 1-grade products of ammonium paratungstate as impurities is not more than 2 multiplied by 10 respectively in terms of Mo/WO3 mass fraction-3And 3X 10-3. Currently, the tungsten-molybdenum separation processes developed for APT production mainly include precipitation separation, ion exchange separation, extraction separation, and the like. The method of precipitation separation is the earliest method for realizing industrial production, and Chinese patent CN971081113.1 invented a tungsten-molybdenum separation method based on thiomolybdate by adding (NH) into ammonium tungstate solution containing molybdenum4)2S, using tungsten, molybdenum and S2-The difference of the properties of the thioate radical ions is formed, and the molybdate radical ions in the solution are preferentially converted into thiomolybdate radical ions (MoS) under certain conditions4 2-) Then, copper ions are added into the solution, and the copper ions and thiomolybdate are used for producing insoluble compounds to realize tungsten-molybdenum separation. Chinese patent CN201810298995.2 discloses gas H2S sulfurizing, acidifying with sulfuric acid to obtain MoS3Precipitation to effect removal of molybdenum from the tungstate solution. Chinese patent CN200910043492.1 invented a method for separating tungsten and molybdenum from a mixed solution of tungstate and molybdate, in which under different acidity conditions, a precipitant is used to selectively precipitate tungstate and molybdate, thereby realizing tungsten and molybdenum separation. The precipitation molybdenum removal method has longer flow and larger tungsten loss, is suitable for treating the solution with low molybdenum content, is difficult to realize deep molybdenum removal, and removes molybdenumH will be discharged in the molybdenum process2The S gas causes environmental pollution. The ion exchange method uses weak base anion exchange resin to selectively adsorb sulfo-molybdate radical to realize deep molybdenum removal from ammonium tungstate solution (Chinese patent CN201410581400.6), or uses weak base anion resin to directly adsorb tungstate radical in the exchange solution, then uses ammonolysis exchange column to simultaneously realize purification of tungsten and preparation of ammonium tungstate solution, and prepares APT through evaporation crystallization. One of the major disadvantages of ion exchange is the large amount of waste water, which creates a problem of large waste water treatment capacity. The solvent extraction method is a more common method for separating and removing molybdenum in tungsten, and Chinese patent CN201510695363.6 realizes the separation of molybdenum from molybdenum-containing phosphotungstic acid/phosphotungstic acid solution by using an alkaline extractant. The Chinese patent CN201910101239.0 adopts TBP and sulfonated kerosene as organic phases to extract and remove molybdenum from the electro-oxidative decomposition leaching solution of the high-molybdenum scheelite, thereby obtaining better effect. The extraction process has the advantages of high metal recovery rate, good impurity removal effect, high product purity, easy quality guarantee, strong adaptability to concentrate, and the like. However, the process has more one-time investment and high requirements on production enterprises in technology. At present, large-scale manufacturers for producing ammonium paratungstate in China widely use extraction process technology.
Molybdenum is available in smaller reserves in the world relative to tungsten resources, however, molybdenum is in great demand in the fields of metallurgy and chemical industry, and particularly, molybdenum is used as a catalyst component in petrochemical industry, and the function of molybdenum cannot be replaced. Therefore, the recovery and high value utilization of molybdenum from various sources and forms has become an important technical development direction for molybdenum hydrometallurgy. As a large country for APT production in China, a large amount of process raffinate is produced every year, and contains about 2-3% of metal molybdenum. The main method for recovering molybdenum is to precipitate calcium molybdate by adding calcium salt. In the recovery process, calcium tungstate and other impurities are simultaneously separated out, and the obtained product belongs to a calcium molybdate crude product, is the same as ferromolybdenum and is generally used in the fields of ferrous metallurgy or enamel industry additives and the like. Ammonium molybdate products are widely used as raw materials in petrochemical industry and molybdenum metal industry, and the use value of calcium molybdate is obviously lower than that of ammonium molybdate.
[ summary of the invention ]
The invention aims to provide a method for recycling ammonium molybdate and a molybdenum precipitation agent in the production of low-molybdenum raffinate molybdenum, so as to solve the problem of high-value utilization of molybdenum recovery in low-molybdenum raffinate in APT production.
In order to achieve the purpose, the invention provides the following technical scheme:
the application discloses a method for recycling ammonium molybdate and a molybdenum precipitation agent by recovering molybdenum from low-molybdenum raffinate, which comprises the following steps:
a) and (3) precipitation: adjusting the pH value of the low-molybdenum raffinate to 7.0-12.0 by using inorganic acid, detecting the content of molybdenum in the low-molybdenum raffinate, adding a molybdenum precipitation agent with the molar weight of 1.0-1.2 times of that of the molybdenum according to the content of the molybdenum in the low-molybdenum raffinate, stirring, and carrying out liquid-solid separation on a precipitate and a supernatant to obtain molybdenum slag, wherein the main component of the molybdenum slag is molybdate, and the molybdenum slag contains a small amount of tungstate;
b) ammonia leaching: leaching the molybdenum slag with an ammonium salt solution, adjusting the pH value to 8.5-9.0 with ammonia water, heating and keeping the temperature at 70-80 ℃, leaching for 1-5 hours, and performing solid-liquid separation after leaching to obtain a manganese salt filter cake and an ammonium molybdate solution;
c) purifying and removing impurities: keeping the ammonium molybdate solution 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 remove impurities from divalent metals in the solution, purifying for 3-5 hours, and filtering after purification to obtain filtrate;
d) acid precipitation: adding 10% of inorganic acid into the filtrate at the temperature of 40-55 ℃ until the pH value is 2.0-3.0, and performing centrifugal separation to obtain ammonium tetramolybdate and mother liquor;
e) and (3) recrystallization: putting the ammonium tetramolybdate into a reaction kettle, adjusting the pH to 6.0-7.0 by using 10% ammonia water, keeping the temperature of the crystallization kettle at 70-80 ℃, and recrystallizing to obtain ammonium heptamolybdate;
f) ion exchange: carrying out ion exchange on the mother liquor obtained in the step d) through anion resin, carrying out ion exchange on molybdate radicals on the anion resin for recovering ammonium molybdate in the mother liquor, desorbing the macroporous anion exchange resin by using ammonia water to obtain ammonium molybdate desorption solution, and returning the ammonium molybdate desorption solution to the ammonium molybdate solution in the step c);
g) and (3) molybdenum precipitation agent circulation: adding water into the manganese salt filter cake obtained in the step b), pulping, slowly adding 20% sulfuric acid, and finally enabling the acidity of the reaction system to be 3.0-5.0 in pH value to obtain manganese sulfate slurry, performing solid-liquid separation by using a filter press, and washing the solid by using clear water to obtain manganese sulfate which can be used as a molybdenum precipitation agent in the step a) for recycling.
Preferably, the molybdenum content in the low-molybdenum raffinate is detected in step a) by a spectrophotometric method.
Preferably, the inorganic acid in step a) is sulfuric acid, nitric acid or hydrochloric acid, and the molybdenum precipitation agent is a divalent compound of manganese, including but not limited to manganese sulfate, manganese chloride, manganese nitrate and manganese carbonate.
Preferably, the sulfide in step c) is ammonium sulfide, sodium sulfide or potassium sulfide.
Preferably, the inorganic acid in step d) is sulfuric acid, nitric acid or hydrochloric acid.
Preferably, the anion resin in step f) is a weakly basic anion resin, and the functional group is a primary amine, secondary amine or tertiary amine type styrene macroporous resin.
The invention has the beneficial effects that:
(1) the method for precipitating molybdate from the low-molybdenum raffinate is provided, and the molybdenum in the low-molybdenum raffinate is efficiently recovered;
(2) the method for producing ammonium molybdate by using the molybdate precipitate as the raw material is provided, and the molybdate precipitate is produced into an ammonium molybdate product meeting the national standard;
(3) provides a method for recycling the molybdenum precipitation agent of the low molybdenum raffinate, and realizes the environmental protection and high value utilization of the low molybdenum raffinate.
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 recovering and producing ammonium molybdate from molybdenum in a low-molybdenum raffinate and recycling a molybdenum precipitation agent according to the 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.
Molybdenum recovery (effect of different pH on molybdenum recovery):
example 1:
taking 10L of molybdenum raffinate, measuring the Mo content by spectrophotometric analysis to be 17.82g/L, slowly adjusting the pH to 8.0 by using 20% ammonia water at 35 ℃ under stirring, weighing 455g of manganese sulfate tetrahydrate corresponding to the Mn/Mo molar ratio of 1.1/1.0 according to the molybdenum content of the solution, preparing the manganese sulfate into a 30% manganese sulfate solution, slowly adding the manganese sulfate solution into the raffinate at the temperature of 50 ℃ and the stirring speed of 150rpm, continuously stirring for 3 hours after the addition is finished, keeping the temperature for standing and precipitating for 2 hours, filtering, and measuring the Mo and the WO in the filtrate by spectrophotometric analysis3And (3) measuring the Mo content to be 0.94g/L, wherein the filter cake is a solid phase mainly composed of manganese molybdate, and is referred to as molybdenum slag for short.
Example 2:
10L of molybdenum-containing raffinate was taken, and the Mo content measured by spectrophotometric analysis was 17.82g/L, and the pH was slowly adjusted to 12.0 with 20% ammonia water at 35 ℃ under stirring. According to the molybdenum content of the solution, 455g of manganese sulfate tetrahydrate corresponding to the Mn/Mo molar ratio of 1.1/1.0 is weighed and prepared into a 30% manganese sulfate solution, the manganese sulfate solution is slowly added into raffinate at the temperature of 50 ℃ and the stirring speed of 150rpm, stirring is continued for 3 hours after the addition is finished, and then the temperature is kept for standing and precipitating for 2 hours. Filtering, and measuring Mo and WO in the filtrate by spectrophotometric analysis3And (3) measuring the Mo content to be 1.51g/L, wherein the filter cake is a solid phase with manganese molybdate as a main component, and is called molybdenum slag for short.
Preparing an ammonium molybdate product:
referring to FIG. 1, 500g of the molybdenum slag obtained in example 1 was charged in a 5000mL flaskAdding 1500mL of clean water, heating, adding 65g of ammonium carbonate under the condition of stirring speed of 150rpm, adjusting the pH to 8.5 by using 20% ammonia water, keeping the temperature at 75-80 ℃ for ammonium leaching for 3 hours, and then cooling to 40 ℃, and completing leaching. And (4) carrying out solid-liquid separation by using a Buchner funnel to obtain a manganese salt filter cake and an ammonium molybdate solution. The resulting ammonium molybdate solution was added to a 5000mL flask, heated to 90 ℃ and pH 9.0, and 10% (NH) was added4)2About 10mL of S solution is used for precipitating and removing impurities from divalent metal ions in the solution, keeping the temperature for 4 hours for purification, and then cooling to 40 ℃. And filtering the liquid after impurity removal by using a Buchner funnel, slowly adding 10% nitric acid solution into the obtained filtrate in a 5000mL flask at the temperature of 45-50 ℃ and the stirring speed of 150rpm to carry out acid precipitation on the filtrate, keeping stirring for 2 hours, standing for 1 hour, and filtering by using the Buchner funnel, wherein the solid is an ammonium tetramolybdate product. In order to prepare ammonium heptamolybdate, 200g of ammonium tetramolybdate is added into a 1000mL flask by using the ammonium tetramolybdate as a raw material, the pH value is adjusted to 6 by using 10% ammonia water under the condition of stirring speed of 150rpm, the crystallization temperature is kept at 75 ℃, and the ammonium heptamolybdate product is recrystallized by using a water circulating pump to pump vacuum. The ammonium tetramolybdate and ammonium heptamolybdate products reach the national standard of ammonium molybdate (GB/T3460-.
And (3) molybdenum precipitation agent circulation:
referring to fig. 1, 100g of manganese salt filter cake obtained by solid-liquid separation in the ammonia leaching step is taken, 100mL of clean water is added for pulping, the temperature is kept at 50 ℃, 20% sulfuric acid is slowly added, the acidity of a reaction system is finally enabled to be pH to 4.0, stirring is continued for 2 hours, the temperature is reduced to 40 ℃, then a Buchner funnel is used for filtering and separation, and the filter cake is washed by clean water, so that a manganese sulfate molybdenum precipitation agent is prepared, and the manganese sulfate can be used as a molybdenum precipitation agent of molybdenum-containing raffinate for recycling.
The effect of the molybdenum precipitation agent after circulation is as follows:
200mL of molybdenum-containing raffinate, and the Mo content of the molybdenum-containing raffinate is 17.82g/L by spectrophotometric analysis. Slowly adjusting pH to 8.0 with 20% ammonia water under stirring, weighing Mn/Mo molar ratio of 1.1/1.0 according to the molybdenum content of the solution, and recoveringRemoving water content of manganese sulfate 45.5g, preparing into 30% manganese sulfate solution, slowly adding into raffinate at 50 deg.C and stirring speed of 150rpm, stirring for 3 hr, standing for 2 hr, filtering, and measuring Mo and WO in filtrate by spectrophotometry3The content of Mo is measured to be 0.99g/L, and the filter cake is a solid phase with manganese molybdate as a main component.
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 (6)
1. A method for recycling ammonium molybdate and molybdenum precipitation agent by recovering low-molybdenum raffinate molybdenum is characterized in that: the method comprises the following steps:
a) and (3) precipitation: adjusting the pH value of the low-molybdenum raffinate to 7.0-12.0 by using inorganic acid, detecting the content of molybdenum in the low-molybdenum raffinate, adding a molybdenum precipitation agent with the molar weight of 1.0-1.2 times of that of the molybdenum according to the content of the molybdenum in the low-molybdenum raffinate, stirring, and carrying out liquid-solid separation on a precipitate and a supernatant to obtain molybdenum slag, wherein the main component of the molybdenum slag is molybdate, and the molybdenum slag contains a small amount of tungstate;
b) ammonia leaching: leaching the molybdenum slag with an ammonium salt solution, adjusting the pH value to 8.5-9.0 with ammonia water, heating and keeping the temperature at 70-80 ℃, leaching for 1-5 hours, and performing solid-liquid separation after leaching to obtain a manganese salt filter cake and an ammonium molybdate solution;
c) purifying and removing impurities: keeping the ammonium molybdate solution 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 remove impurities from divalent metals in the solution, purifying for 3-5 hours, and filtering after purification to obtain filtrate;
d) acid precipitation: adding 10% of inorganic acid into the filtrate at the temperature of 40-55 ℃ until the pH value is 2.0-3.0, and performing centrifugal separation to obtain ammonium tetramolybdate and mother liquor;
e) and (3) recrystallization: putting the ammonium tetramolybdate into a reaction kettle, adjusting the pH to 6.0-7.0 by using 10% ammonia water, keeping the temperature of the crystallization kettle at 70-80 ℃, and recrystallizing to obtain ammonium heptamolybdate;
f) ion exchange: carrying out ion exchange on the mother liquor obtained in the step d) through anion resin, carrying out ion exchange on molybdate radicals on the anion resin for recovering ammonium molybdate in the mother liquor, desorbing the macroporous anion exchange resin by using ammonia water to obtain ammonium molybdate desorption solution, and returning the ammonium molybdate desorption solution to the ammonium molybdate solution in the step c);
g) and (3) molybdenum precipitation agent circulation: adding water into the manganese salt filter cake obtained in the step b), pulping, slowly adding 20% sulfuric acid, and finally enabling the acidity of the reaction system to be 3.0-5.0 in pH value to obtain manganese sulfate slurry, performing solid-liquid separation by using a filter press, and washing the solid by using clear water to obtain manganese sulfate which can be used as a molybdenum precipitation agent in the step a) for recycling.
2. The method for recycling the ammonium molybdate and the molybdenum precipitation agent in the process of recovering and producing the low-molybdenum raffinate molybdenum as claimed in claim 1, wherein: and b) detecting the content of molybdenum in the low-molybdenum raffinate in the step a) by adopting a spectrophotometric method.
3. The method for recycling the ammonium molybdate and the molybdenum precipitation agent in the process of recovering and producing the low-molybdenum raffinate molybdenum as claimed in claim 1, wherein: the inorganic acid in the step a) is sulfuric acid, nitric acid or hydrochloric acid, and the molybdenum precipitation agent adopts a divalent manganese compound, wherein the divalent manganese compound comprises, but is not limited to, manganese sulfate, manganese chloride, manganese nitrate and manganese carbonate.
4. The method for recycling the ammonium molybdate and the molybdenum precipitation agent in the process of recovering and producing the low-molybdenum raffinate molybdenum as claimed in claim 1, wherein: the sulfide in the step c) is ammonium sulfide, sodium sulfide or potassium sulfide.
5. The method for recycling the ammonium molybdate and the molybdenum precipitation agent in the process of recovering and producing the low-molybdenum raffinate molybdenum as claimed in claim 1, wherein: the inorganic acid in the step d) is sulfuric acid, nitric acid or hydrochloric acid.
6. The method for recycling the ammonium molybdate and the molybdenum precipitation agent in the process of recovering and producing the low-molybdenum raffinate molybdenum as claimed in claim 1, wherein: the anion resin in the step f) is weak-base anion resin, and the functional group is primary amine, secondary amine or tertiary amine type styrene macroporous resin.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6113868A (en) * | 1996-07-05 | 2000-09-05 | H. C. Starck Gmbh & Co. Kg | Process for treating tungstate solutions to reduce molybdenum impurity and other impurity content |
| CN101565778A (en) * | 2009-05-22 | 2009-10-28 | 中南大学 | Method for depositing and separating tungsten and molybdenum in tungstate/molybdate mixed solution |
| WO2011150583A1 (en) * | 2010-06-04 | 2011-12-08 | 中南大学 | Method for extracting tungsten and molybdenum respectively from tungstate-molybdate mixed solution |
| CN102616857A (en) * | 2012-01-16 | 2012-08-01 | 渤海大学 | Preparation method of manganese molybdate microcrystal |
| CN102730758A (en) * | 2012-07-14 | 2012-10-17 | 河南科技大学 | Method for reducing and removing metal impurities from ammonium molybdate solution by using ion exchange resin |
| CN103265079A (en) * | 2013-06-05 | 2013-08-28 | 杭州临安慧尔钼业科技有限公司 | Method for recovering molybdenum from molybdenum containing waste acid of filament wire |
| 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 |
| CN111154991A (en) * | 2020-01-19 | 2020-05-15 | 北京工业大学 | Method for separating tungsten and molybdenum from tungsten molybdate solution |
-
2020
- 2020-06-12 CN CN202010532319.4A patent/CN113801997A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6113868A (en) * | 1996-07-05 | 2000-09-05 | H. C. Starck Gmbh & Co. Kg | Process for treating tungstate solutions to reduce molybdenum impurity and other impurity content |
| CN101565778A (en) * | 2009-05-22 | 2009-10-28 | 中南大学 | Method for depositing and separating tungsten and molybdenum in tungstate/molybdate mixed solution |
| WO2011150583A1 (en) * | 2010-06-04 | 2011-12-08 | 中南大学 | Method for extracting tungsten and molybdenum respectively from tungstate-molybdate mixed solution |
| CN102616857A (en) * | 2012-01-16 | 2012-08-01 | 渤海大学 | Preparation method of manganese molybdate microcrystal |
| CN102730758A (en) * | 2012-07-14 | 2012-10-17 | 河南科技大学 | Method for reducing and removing metal impurities from ammonium molybdate solution by using ion exchange resin |
| CN103265079A (en) * | 2013-06-05 | 2013-08-28 | 杭州临安慧尔钼业科技有限公司 | Method for recovering molybdenum from molybdenum containing waste acid of filament wire |
| 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 |
| CN111154991A (en) * | 2020-01-19 | 2020-05-15 | 北京工业大学 | Method for separating tungsten and molybdenum from tungsten molybdate solution |
Non-Patent Citations (3)
| Title |
|---|
| 刘锦锐: ""钼酸铵生产工艺流程综述"", 《云南冶金》 * |
| 孙培梅等: ""选择性沉淀法从钨酸盐溶液中除钼的工业试验"", 《中国有色金属学报》 * |
| 孙培梅等: ""钨钼分离方法的研究进展"", 《中国钼业》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116443930A (en) * | 2023-04-24 | 2023-07-18 | 安庆市月铜钼业有限公司 | Ammonium heptamolybdate production process and production system thereof |
| CN116443930B (en) * | 2023-04-24 | 2024-01-23 | 安庆市月铜钼业有限公司 | Ammonium heptamolybdate production process and production system thereof |
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