CN115109931A - Method for recovering multiple metals from tungsten-molybdenum waste residue - Google Patents
Method for recovering multiple metals from tungsten-molybdenum waste residue Download PDFInfo
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- CN115109931A CN115109931A CN202210702962.6A CN202210702962A CN115109931A CN 115109931 A CN115109931 A CN 115109931A CN 202210702962 A CN202210702962 A CN 202210702962A CN 115109931 A CN115109931 A CN 115109931A
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- molybdenum
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- 239000002699 waste material Substances 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 62
- MGRWKWACZDFZJT-UHFFFAOYSA-N molybdenum tungsten Chemical compound [Mo].[W] MGRWKWACZDFZJT-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 24
- 239000002184 metal Substances 0.000 title claims abstract description 23
- 150000002739 metals Chemical class 0.000 title claims abstract description 18
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 111
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 101
- 239000010937 tungsten Substances 0.000 claims abstract description 101
- 239000000463 material Substances 0.000 claims abstract description 94
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 59
- 238000002156 mixing Methods 0.000 claims abstract description 57
- 239000007791 liquid phase Substances 0.000 claims abstract description 49
- 239000007788 liquid Substances 0.000 claims abstract description 47
- 238000000926 separation method Methods 0.000 claims abstract description 41
- 239000007790 solid phase Substances 0.000 claims abstract description 38
- 239000000047 product Substances 0.000 claims abstract description 30
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 25
- 239000011733 molybdenum Substances 0.000 claims abstract description 25
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 25
- 239000001301 oxygen Substances 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000002002 slurry Substances 0.000 claims abstract description 23
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 22
- 239000010955 niobium Substances 0.000 claims abstract description 22
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 22
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 20
- 238000003825 pressing Methods 0.000 claims abstract description 19
- 238000005342 ion exchange Methods 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 12
- 238000004537 pulping Methods 0.000 claims abstract description 12
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 claims abstract description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 7
- 150000002815 nickel Chemical class 0.000 claims abstract description 5
- 239000002244 precipitate Substances 0.000 claims abstract description 4
- 150000001879 copper Chemical class 0.000 claims abstract description 3
- 238000011084 recovery Methods 0.000 claims description 64
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 56
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 38
- 229910052802 copper Inorganic materials 0.000 claims description 38
- 239000010949 copper Substances 0.000 claims description 38
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 37
- 229910052804 chromium Inorganic materials 0.000 claims description 34
- 239000011651 chromium Substances 0.000 claims description 34
- 229910052759 nickel Inorganic materials 0.000 claims description 28
- 230000005484 gravity Effects 0.000 claims description 24
- 238000002386 leaching Methods 0.000 claims description 24
- 239000002893 slag Substances 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 16
- 239000012445 acidic reagent Substances 0.000 claims description 15
- 239000007800 oxidant agent Substances 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000011268 mixed slurry Substances 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 11
- 229920005989 resin Polymers 0.000 claims description 11
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 9
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical group [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 238000003723 Smelting Methods 0.000 claims description 8
- 238000005086 pumping Methods 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 4
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000005751 Copper oxide Substances 0.000 claims description 3
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 3
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 3
- 229910000431 copper oxide Inorganic materials 0.000 claims description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 3
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 2
- 238000002791 soaking Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 32
- 239000003513 alkali Substances 0.000 description 23
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- JPNWDVUTVSTKMV-UHFFFAOYSA-N cobalt tungsten Chemical compound [Co].[W] JPNWDVUTVSTKMV-UHFFFAOYSA-N 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 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 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- -1 nickel form copper salt Chemical class 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- SWGJCIMEBVHMTA-UHFFFAOYSA-K trisodium;6-oxido-4-sulfo-5-[(4-sulfonatonaphthalen-1-yl)diazenyl]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].C1=CC=C2C(N=NC3=C4C(=CC(=CC4=CC=C3O)S([O-])(=O)=O)S([O-])(=O)=O)=CC=C(S([O-])(=O)=O)C2=C1 SWGJCIMEBVHMTA-UHFFFAOYSA-K 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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
- 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
-
- 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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
-
- 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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet 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
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/24—Obtaining niobium or tantalum
-
- 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
- C22B34/32—Obtaining chromium
-
- 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
- C22B34/36—Obtaining tungsten
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a method for recovering multiple metals from tungsten-molybdenum waste residues, which comprises the following steps: mixing the waste residue with water, pulping, and performing filter pressing through filter pressing equipment after pulping to obtain filter residue material; drying the filter residue material by drying equipment to obtain a dried material, putting the dried material into crushing equipment for crushing to obtain a crushed material, adding the crushed material, water and an alkaline reagent into a size mixing tank to obtain a size mixing liquid, adding the size mixing liquid into high-pressure oxygen soaking equipment, heating and pressurizing for reaction to obtain a reacted material, and separating a liquid phase and a solid phase from the reacted material by solid-liquid separation equipment; adding a reducing agent into the liquid phase to generate a precipitate, adding water, mixing the slurry, and performing reselection to obtain a chromium hydroxide product; carrying out ion exchange on the rest liquid phase after reselection to obtain a tungsten product; the solid phase obtained by the separation is then respectively recycled to obtain copper salt, nickel salt, tantalum and niobium products. The method can recover various valuable elements in the low-grade tungsten and molybdenum waste residue, and has better cost performance.
Description
Technical Field
The invention relates to the field of recovery of heavy metals in residues and tailings, in particular to a method for recovering multiple metals from tungsten-molybdenum waste residues.
Background
Tungsten-molybdenum waste residues are waste generated in non-ferrous metal smelting, the residues contain various valuable elements such as copper, nickel, chromium, tungsten, molybdenum and the like, the existing recovery method has high cost due to low content, the cost performance of recovery is low, and the residues are often stacked and discarded to become solid waste of a smelting plant.
Meanwhile, tailings generated in the separation operation in the ore dressing also contain valuable elements with more types, and like tungsten and molybdenum waste residues, the tailings are generally discarded along with industrial garbage due to low content and high recovery difficulty, and the valuable elements remained in the tailings cannot be enriched and recovered.
Tungsten and molybdenum are mixed in waste slag, which causes difficulty in separating the tungsten and the molybdenum, because the tungsten and the molybdenum cannot be effectively separated by the conventional acid leaching and alkali leaching methods, and the separation is difficult because the atomic radii, the chemical valence states and the chemical properties of the tungsten and the molybdenum in an aqueous solution are extremely similar. The existing solutions include precipitation, ion exchange, extraction, liquid membrane separation, etc., which are not suitable for the recovery of low-grade waste residue.
Patent application CNCN103103360A discloses a method for recovering metals by using APT slag, which comprises the following steps: the method for recovering copper, tungsten and molybdenum by using APT waste residue is characterized by comprising the following steps: the method comprises the following steps: a. grinding: grinding waste residue containing copper, tungsten and molybdenum generated in the production process of ammonium paratungstate to-325 meshes which is more than or equal to 90 percent; b. and (3) separating and recovering copper by alkaline leaching: b, melting the waste residue ground in the step a by using soft water with the pH value of 7.5-8.5, and filtering to separate the copper-containing residue from the tungsten-molybdenum-containing solution; then carrying out alkaline cooking leaching on the residue containing copper, wherein the alkali is NaOH, stopping adding the alkali when the alkali concentration is 35-45g/L, carrying out boiling again, keeping the temperature for 1.5-2.5h, and recycling after washing to obtain copper sulfide; c. recovering molybdenum by acid leaching and precipitation purification: adding 125-150% of vulcanizing agent which is NaHS (sodium hydrogen sulfide) in terms of Mo theoretical amount into the solution containing tungsten and molybdenum generated in the step b, boiling the solution for 2 hours after the vulcanizing agent is added, continuously stirring the solution until the solution shows rose or purple red after the vulcanizing reaction is finished, adding 3-5mol of sulfuric acid to adjust the pH value of the solution to 2.5-3, continuously boiling for 1.5-2 hours, wherein the pH value can be changed in the boiling processThe pH value is continuously measured and added with acid to adjust the pH value to generate MoS 3 The solution after precipitation was bluish black and brown MoS was observed 3 Precipitating, and filtering to obtain a product containing MoS 3 Slag and tungstic acid solution; d. tungsten recovery using ion exchange: and c, subjecting the tungstic acid solution generated in the step c to four traditional ion exchange procedures of dilution, adsorption, leaching and desorption to obtain a crude sodium tungstate solution, and subjecting the solution to the subsequent traditional procedures of artificial scheelite precipitation, acid hydrolysis, ammonium tungstate dissolution and evaporative crystallization to produce the APT. In the scheme, a large amount of alkali liquor is consumed for recovering copper through alkaline leaching, and tungsten element also exists in a system in the copper recovery process, so that tungsten loss is brought to a certain degree; and meanwhile, three metal elements of copper, tungsten and molybdenum are contained in the APT waste residue, and for the waste residue with low molybdenum content, the cost for recovering the molybdenum is overhigh and the output is lower; and if the step c is not carried out, the purity of the tungsten extracted in the subsequent step is low.
Disclosure of Invention
The invention aims to overcome the difficulty in the existing tungsten-molybdenum waste residue recovery, and provides a method for recovering multiple metals from the tungsten-molybdenum waste residue, which can solve the interference of tungsten-molybdenum separation on the whole process, complete the respective extraction of tantalum, niobium, copper, chromium, nickel and tungsten on the premise of not independently extracting molybdenum, and has higher purity of extracted products.
According to the invention, the tungsten-molybdenum waste residue is subjected to high-pressure oxygen leaching treatment to obtain a sodium tungstate solution and residue, the solution is subjected to impurity removal to obtain a pure tungstate solution, and the residue is subjected to gravity separation to obtain a mixture. Because the waste residue contains molybdenum, the tungsten is directly recovered from the waste residue, and the recovery rate of the tungsten is not high because the molybdenum interferes the extraction of the tungsten, and the high-pressure oxygen leaching method is adopted in the invention, so that the recovery rate of the tungsten is more than 95%.
In the invention, chromium is separated from tungsten-molybdenum waste slag, which is easy to cause tungsten loss, the invention adopts a reducing agent, controls the process conditions, comprises the reducing agent and water for size mixing, the proportion of the water added is that the solid-liquid mass ratio is 1:3-10, and the obtained size is reselected, so that tungsten and chromium enter a liquid phase and a solid phase respectively, thereby avoiding tungsten entrainment during chromium recovery. Furthermore, after the hydroxide of the chromium is separated, the tungsten is recovered by an ion exchange method, so that the high recovery rate of the tungsten is ensured.
Aiming at the problem that the cross influence exists between the copper element and the nickel element and the chromium element, the invention takes the copper and the nickel element as a group of objects, the chromium is independently taken as a recovery object, different recovery paths are adopted for processing, the chromium mainly enters a liquid phase after high-pressure oxygen leaching, a reduction thought is adopted for the chromium, and the chromium element is reduced to form chromium hydroxide; the copper and the nickel are mainly in the solid phase, so that the separation of the copper element, the nickel element and the chromium is realized, and the copper and the nickel in the solid phase adopt an oxidation idea, so that the copper and the nickel form copper salt and nickel salt under the action of an oxidant and an acidic reagent, thereby realizing the synchronous recovery of the copper, the nickel and the chromium and also avoiding the interference on a tungsten recovery route.
Tantalum and niobium are finally recovered in the invention because the tantalum and niobium are inert in chemical property and do not react with conventional acid and alkali, and the tantalum and niobium exist in the conditioning slurry in oxide form, and the invention adopts a centrifugal device, and the centrifugal speed is above 3500r under the centrifugal condition, and the feeding speed is 2-5m 3 And/h, the tantalum and the niobium exist in oxide form and are enriched to obtain tantalum and niobium products, and the recovery rate is higher than 95%.
The specific scheme is as follows:
a method for recovering a plurality of metals from tungsten-molybdenum waste slag comprises the following steps:
the method comprises the following steps: mixing tungsten and molybdenum waste residues with water, pulping, and performing filter pressing through filter pressing equipment after pulping to obtain filter residue material;
step two: drying the filter residue material obtained in the step one by drying equipment to remove oil and water to obtain a dried material;
step three: putting the dried material obtained in the step two into crushing equipment for crushing to obtain a crushed material;
step four: adding the crushed material obtained in the step three, water and an alkaline reagent into a size mixing tank to obtain size mixing liquid;
step five: adding the slurry mixing liquid obtained in the step four into high-pressure oxygen leaching equipment, heating and pressurizing to perform reaction to obtain a reacted material;
step six: separating the reacted material obtained in the fifth step into a liquid phase and a solid phase by solid-liquid separation equipment;
step seven: adding a reducing agent into the liquid phase obtained in the sixth step to generate a precipitate, adding water for size mixing, and then performing gravity separation to obtain a chromium hydroxide product; the rest liquid phase after reselection is subjected to the next step;
step eight: carrying out ion exchange on the residual liquid phase obtained in the step seven to obtain a tungsten product;
step nine: mixing the solid phase obtained in the sixth step with an oxidant and an acidic reagent, filtering after reaction, collecting a liquid phase to obtain a solution of copper salt and nickel salt, and carrying out the next step on the filtered solid phase;
step ten: and (4) mixing the solid phase obtained in the step nine to obtain mixed slurry, pumping the mixed slurry into high-speed centrifugal equipment, controlling the feeding speed, and separating out waste residues and liquid to obtain tantalum and niobium products.
Further, the tungsten-molybdenum waste residue is tungsten smelting waste residue or valuable metal tailings, wherein the mass content of tungsten oxide is 2-10%, and the mass content of molybdenum oxide is 1-5%; preferably, the mass content of chromium oxide in the tungsten-molybdenum waste residue is greater than or equal to 1%, the mass content of copper oxide is greater than or equal to 1%, the mass content of nickel oxide is greater than or equal to 1%, the mass content of tantalum is greater than or equal to 2%, and the mass content of niobium is greater than or equal to 1%.
Further, the adding amount of water in the step one is as follows: the mass ratio of the waste residue to the water is 1: 1-5;
optionally, the temperature for drying in the second step is 200-400 ℃, and the time is 2-24 h.
Further, the granularity of the crushed particles in the third step is 50-70 meshes;
optionally, the mass ratio of the crushed materials to the water to the alkaline reagent in the fourth step is 100 (1-5): (300-400); preferably, the alkaline agent is a solid base and/or a liquid base.
Further, in the fifth step, heating and pressurizing are carried out for reaction, the heating temperature is 150-;
optionally, in the seventh step, water is added for size mixing, the proportion of the added water is 1:3-10 of solid-liquid mass ratio, and then reselection is carried out.
Further, the gravity separation is performed by adopting high-precision gravity separation equipment, and the high-precision gravity separation equipment is used for separating the hydroxide of the chromium under the centrifugal condition that the rotating speed is higher than 3500 r/min.
Optionally, in the seventh step, the reducing agent is sodium sulfide, sodium hydrosulfide or sulfur dioxide, the dosage of the reducing agent is 4-10 times of the theoretical dosage of the reducing agent required by the complete reaction of chromium, and the recovery rate of chromium is more than or equal to 95%.
Optionally, in the step eight, the ion exchange for recovering tungsten is to adsorb the liquid phase by using resin, the liquid phase contains tungstate, the tungsten element is adsorbed on the column by the resin, and then the tungsten element is replaced by the lower column by using an analytical agent to obtain an ammonium tungstate solution, wherein the recovery rate of tungsten is greater than or equal to 95%.
Further, in the ninth step, the oxidant is at least one of hydrogen peroxide, hypochlorous acid, sodium chlorate or sodium hypochlorite, and the acidic reagent is at least one of sulfuric acid, hydrochloric acid or phosphoric acid.
Further, in the ninth step, the molar ratio of the oxidizing agent to the acidic reagent is 1-2:1, the dosage of the oxidizing agent and the acidic reagent is 1-3 times of the theoretical value of complete reaction of copper and nickel, the recovery rate of copper is greater than or equal to 97%, and the recovery rate of nickel is greater than or equal to 96%.
Further, in the step ten, the solid phase is subjected to size mixing, wherein the solid-liquid ratio is 1:3-1:10, and size mixing slurry is obtained; and (3) pumping the obtained slurry into high-speed centrifugal equipment, wherein the centrifugal speed is more than 3500 revolutions.
Further, the obtained size mixing material is injected into a high-speed centrifugal device, and the feeding speed is controlled to be 2-5m 3 And/h, the recovery rate of tantalum and the recovery rate of niobium are more than or equal to 95 percent.
Has the advantages that: the invention recovers a plurality of metals from the waste residue, can realize the recycling of the waste, adopts high-pressure oxygen leaching reaction equipment to ensure that valuable elements can fully react, and lays a foundation for subsequent separation and enrichment.
Furthermore, the method utilizes gravity separation equipment to recover chromium, has better chromium recovery rate, is more convenient to recover tungsten from the residual liquid after chromium recovery, and has high tungsten recovery rate.
Moreover, the method adopts different recovery paths for copper, nickel and chromium, thereby not only ensuring the recovery rate of the copper, the nickel and the chromium, but also avoiding the interference on the recovery of tungsten, and having great environmental protection significance and economic value on the recovery and utilization of non-renewable resources.
Finally, the invention recovers the tantalum and niobium products in a centrifugal mode, the recovery rate of the tantalum is more than or equal to 95 percent, the recovery rate of the niobium is more than or equal to 95 percent, and the recovery effect is better.
Detailed Description
Definitions for some of the terms used in the present invention are given below, and other terms not described have definitions and meanings known in the art:
tungsten-molybdenum waste residue: the tungsten-molybdenum waste residue is tungsten smelting waste residue or valuable metal tailings, wherein the tungsten smelting waste residue can be tungsten-containing cobalt-containing slag materials generated in a wet-process or fire-process metallurgy process, such as tungsten-cobalt slag obtained by a saltpeter smelting process, tungsten-cobalt slag obtained by an oxidation smelting process, tungsten-cobalt slag obtained by a sodium carbonate roasting process, tungsten-cobalt slag obtained by an oxidation roasting alkaline leaching process, and tungsten-containing residues obtained by other processes. The valuable metal tailings can be tailings obtained by performing flotation on copper-containing ores, tungsten-containing ores and nickel-containing ores. In a specific embodiment, the mass content of tungsten oxide in the tungsten-molybdenum waste residue is 2-10%, the mass content of molybdenum oxide is 1-5%, the mass content of chromium oxide in the tungsten-molybdenum waste residue is greater than or equal to 1%, the mass content of copper oxide is greater than or equal to 1%, the mass content of nickel oxide is greater than or equal to 1%, the mass content of tantalum is greater than or equal to 2%, and the mass content of niobium is greater than or equal to 1%.
In the invention, the alkaline reagent is utilized to realize the transformation of the tungsten in the step four, thereby realizing the purpose of recovering the tungsten, and the transformed tungsten can be dissolved out in a large amount and enter a liquid phase when reacting in a high-pressure oxygen leaching device, thereby achieving the high-efficiency recovery of the tungsten.
In the invention, in the fifth step, most of tungsten enters a liquid phase through high-pressure oxygen leaching reaction so as to achieve high-efficiency recovery of the tungsten. In order to ensure the effect of the high-pressure oxygen leaching reaction, the waste residue is dried and crushed after size mixing in the steps from the first step to the third step, the difference among different batches of raw materials can be adjusted, so that the materials are more uniform, the size mixing obtained after size mixing in the step four is high in uniformity, and a foundation is laid for efficient separation and extraction of high-pressure oxygen leaching. Meanwhile, in the fifth step, the chromium element in the waste residue enters into a liquid phase, and the copper and the nickel are mainly remained in a solid phase.
In the invention, in the seventh step, a reducing agent is utilized to enable chromium to form a precipitate, and the hydroxide of the chromium is separated out under high-speed centrifugation by adopting gravity separation operation, so that the tungsten loss is reduced.
In the invention, the oxidizing agent and the acidic reagent are adopted in the ninth step, so that the copper element and the nickel element in the solid phase form salt and are recovered under the coordination of the oxidizing agent and the acidic reagent, and the extraction efficiency of the copper element and the nickel element is higher.
Preferably, in the ninth step, the molar ratio of the oxidizing agent to the acidic reagent is 1-2:1, and the amount of the oxidizing agent and the acidic reagent is 1-3 times of the theoretical value of complete reaction of copper and nickel, wherein the theoretical value calculation of the acidic reagent and the oxidizing agent is performed according to a chemical reaction equation, and if sulfuric acid is used as the acidic reagent and oxygen is used as the oxidizing agent, the chemical reaction equation is as follows:
2Cu+2H 2 SO 4 +O 2 ＝2CuSO 4 +H 2 O
2Ni+2H 2 SO 4 +O 2 ＝2NiSO 4 +H 2 O
preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available. In the following examples, "%" means weight percent, unless otherwise specified.
The main components of the tungsten-molybdenum slag adopted in the examples are shown in the following table:
TABLE 1 Main composition and content of waste residue (mass percent)
Example 1
A method for recovering tungsten and molybdenum waste residues comprises the following steps:
the method comprises the following steps: taking 500g of tungsten-molybdenum waste residue, adding 500g of water, mixing slurry and pulping, and performing filter pressing on the pulped material through filter pressing equipment to obtain a filter residue form material; step two: drying the filter residue material obtained in the step one at 300 ℃ for 24h by using drying equipment to remove oil and water in the tungsten-containing waste material to obtain a dried material; step three: putting the dried material obtained in the step two into crushing equipment for crushing, wherein the granularity is 60 meshes, and obtaining a crushed material; step four: adding the crushed material obtained in the step three, water and solid alkali into a size mixing tank according to a certain proportion to obtain size mixing liquid, wherein the mass ratio of the crushed material to the solid alkali to the water is 100: 2: 300, respectively; step five, taking solid alkali as flake alkali: feeding the slurry prepared in the step four into a high-pressure oxygen leaching device, heating to 180 ℃, reacting for 16 hours at an oxygen pressure of 2MPa, and stirring at a rotating speed of 600 r/min to obtain a reacted material after the reaction is finished; step six: and D, separating the reacted material obtained in the fifth step into a liquid phase and a solid phase by using solid-liquid separation equipment.
Step seven: and adding sodium sulfide with the molar quantity 5 times of the theoretical value into the liquid phase obtained in the step six, adding water for size mixing, wherein the water adding ratio is 1:3 of the solid-to-liquid ratio, then performing gravity separation, and adopting high-precision gravity separation equipment to enable chromium to exist in the solid phase to obtain a chromium hydroxide product, wherein the recovery rate of the chromium is 95%. And (5) carrying out next step on the rest liquid phase after reselection.
Step eight: and (2) recovering tungsten in the residual liquid phase by adopting an ion exchange method, wherein the specific mode is as follows: adsorbing tungsten in the sodium tungstate solution by using 201-7 resin, adsorbing the tungsten on the column, and then replacing the tungsten on the column by using a resolving agent to obtain the ammonium tungstate solution. The recovery of tungsten was tested to be 98.5%.
Step nine: and (3) collecting the solid phase obtained in the step six, and adding sulfuric acid with the theoretical value of 1.5 times and hydrogen peroxide with the theoretical value of 2 times to obtain a copper and nickel salt product, wherein the recovery rate of copper is 97.83%, and the recovery rate of nickel is 98.59%.
Step ten: and (4) mixing the solid phase obtained in the step nine to obtain mixed slurry, pumping the mixed slurry into high-speed centrifugal equipment, controlling the feeding speed, and separating out waste residues and liquid to obtain tantalum and niobium products. Specifically, the solid-liquid ratio of the slurry is adjusted to be 1:3, and the feeding speed is controlled to be 2m 3 The centrifugation rate was 3400r, the recovery of tantalum was 95.17%, and the recovery of niobium was 95.83%.
Example 2
A method for recovering tungsten and molybdenum waste residues comprises the following steps:
the method comprises the following steps: taking 500g of tungsten-molybdenum waste residue, adding 1000g of water, mixing slurry and pulping, and performing filter pressing on the pulped material by using filter pressing equipment to obtain a filter residue form material; step two: drying the filter residue material obtained in the step one at 400 ℃ for 16h by using drying equipment to remove oil and water in the tungsten-containing waste material to obtain a dried material; step three: putting the dried material obtained in the step two into crushing equipment for crushing, wherein the granularity is 100 meshes, and obtaining a crushed material; step four: adding the crushed material obtained in the step three, water and solid alkali which is flake alkali into a size mixing tank according to a certain proportion to obtain size mixing liquid, wherein the mass ratio of the crushed material to the solid alkali to the water is 100: 3: 400, respectively; step five: feeding the slurry prepared in the step four into a high-pressure oxygen leaching device, reacting under certain conditions to obtain a reacted material, heating to 160 ℃, reacting for 12 hours at the oxygen pressure of 1.2MPa and the rotating speed of 650 r/min to obtain a reacted material after the reaction is finished; step six: and D, separating the reacted material obtained in the fifth step into a liquid phase and a solid phase by using solid-liquid separation equipment.
Step seven: and adding sodium sulfide with the molar quantity 5 times of the theoretical value into the liquid phase obtained in the step six, adding water for size mixing, wherein the water adding ratio is 1:5 of the solid-to-liquid ratio, then performing gravity separation, and adopting high-precision gravity separation equipment to enable chromium to exist in the solid phase to obtain a chromium hydroxide product, wherein the recovery rate of the chromium is 95.35%. And (5) carrying out next step on the rest liquid phase after reselection.
Step eight: and (2) recovering tungsten in the residual liquid phase by adopting an ion exchange method, wherein the specific mode is as follows: adsorbing tungsten in the sodium tungstate solution by using 201-7 resin, adsorbing the tungsten on the column, and then replacing the tungsten on the column by using a resolving agent to obtain the ammonium tungstate solution. The recovery of tungsten was tested to be 98.75%.
Step nine: and (3) collecting the solid phase obtained in the step six, and adding hydrochloric acid with the theoretical value of 1.6 times and sodium chlorate with the theoretical value of 2.5 times to obtain salt products of copper and nickel, wherein the recovery rate of copper is 97.28%, and the recovery rate of nickel is 98.32%.
Step ten: and (4) mixing the solid phase obtained in the step nine to obtain mixed slurry, pumping the mixed slurry into high-speed centrifugal equipment, controlling the feeding speed, and separating out waste residues and liquid to obtain tantalum and niobium products. Specifically, the solid-liquid ratio of the slurry is adjusted to be 1:5, and the feeding speed is controlled to be 3m 3 The centrifugation rate was 3500r, the recovery of tantalum was 95.33% and the recovery of niobium was 95.25%.
Example 3
A method for recovering tungsten and molybdenum waste residues comprises the following steps:
the method comprises the following steps: taking 500g of tungsten-molybdenum waste residue, adding 1200g of water, mixing slurry and pulping, and performing filter pressing on the pulped material by using filter pressing equipment to obtain a filter residue form material; step two: drying the filter residue material obtained in the step one at 350 ℃ for 8h by using drying equipment, and removing oil and water in the tungsten-containing waste material to obtain a dried material; step three: putting the dried material obtained in the step two into crushing equipment for crushing, wherein the granularity is 120 meshes, and obtaining a crushed material; step four: adding the crushed material obtained in the step three, water and solid alkali which is flake alkali into a size mixing tank according to a certain proportion to obtain size mixing liquid, wherein the mass ratio of the crushed material to the solid alkali to the water is 100: 2: 300, respectively; step five: feeding the slurry mixing liquid obtained in the fourth step into a high-pressure oxygen leaching device, reacting under certain conditions to obtain a reacted material, heating to 160 ℃, reacting for 16 hours at the oxygen pressure of 1.5MPa and the rotating speed of 600 r/min, and obtaining a reacted material after the reaction is finished; step six: and D, separating the reacted material obtained in the fifth step into a liquid phase and a solid phase by using solid-liquid separation equipment.
Step seven: and adding sodium sulfide with the molar quantity 5 times of the theoretical value into the liquid phase obtained in the step six, adding water for size mixing, wherein the water adding ratio is 1:10 of the solid-to-liquid ratio, then performing gravity separation, and adopting high-precision gravity separation equipment to enable chromium to exist in the solid phase to obtain a chromium hydroxide product, wherein the recovery rate of the chromium is 93.25%. And (5) carrying out next step on the rest liquid phase after reselection.
Step eight: and (2) recovering tungsten in the residual liquid phase by adopting an ion exchange method, wherein the specific mode is as follows: adsorbing tungsten in the sodium tungstate solution by using 201-7 resin, adsorbing the tungsten on the column, and then replacing the tungsten on the column by using a resolving agent to obtain the ammonium tungstate solution. The recovery rate of tungsten is 96.58% through testing.
Step nine: and (4) collecting the solid phase obtained in the step six, and adding phosphoric acid with the theoretical value of 1.7 times and hypochlorous acid with the theoretical value of 3 times to obtain a salt product of copper and nickel, wherein the recovery rate of copper is 97.35 percent, and the recovery rate of nickel is 96.85 percent.
Step ten: and (4) mixing the solid phase obtained in the step nine to obtain mixed slurry, pumping the mixed slurry into high-speed centrifugal equipment, controlling the feeding speed, and separating out waste residues and liquid to obtain tantalum and niobium products. Specifically, the solid-liquid ratio of the slurry is adjusted to be 1:7, and the feeding speed is controlled to be 5m 3 The centrifugation rate was 3800r, the recovery of tantalum was 95.28% and the recovery of niobium was 95.33%.
Example 4
A method for recovering tungsten and molybdenum waste residues comprises the following steps:
the method comprises the following steps: taking 500g of tungsten-molybdenum waste residue, adding 2500g of water, mixing slurry and pulping, and performing filter pressing on the pulped material through filter pressing equipment to obtain a filter residue form material; step two: drying the filter residue material obtained in the first step at 200 ℃ for 12 hours by drying equipment, and removing oil and water in the tungsten-containing waste material to obtain a dried material; step three: putting the dried material obtained in the step two into crushing equipment for crushing, wherein the granularity is 70 meshes, and obtaining a crushed material; step four: adding the crushed material obtained in the step three, water and solid alkali into a size mixing tank according to a certain proportion to obtain size mixing liquid, wherein the mass ratio of the crushed material to the solid alkali to the water is 100: 3: 300, respectively; the solid base is sodium hydroxide. Step five: feeding the slurry prepared in the step four into a high-pressure oxygen leaching device, reacting under certain conditions to obtain a reacted material, heating to 150 ℃, reacting for 16 hours under the oxygen pressure of 8MPa, and stirring at the rotating speed of 500r/min to obtain a reacted material after the reaction is finished; step six: and D, separating the reacted material obtained in the fifth step into a liquid phase and a solid phase by using solid-liquid separation equipment.
Step seven: and adding sodium sulfide of which the molar quantity is 5 times of the theoretical value into the liquid phase obtained in the step six, adding water for size mixing, wherein the water adding ratio is 1:10 of the solid-to-liquid ratio, then performing gravity separation, and adopting high-precision gravity separation equipment to enable chromium to exist in a solid phase to obtain a chromium hydroxide product. And (5) carrying out next step on the rest liquid phase after reselection.
Step eight: and (2) recovering tungsten in the residual liquid phase by adopting an ion exchange method, wherein the specific mode is as follows: adsorbing tungsten in the sodium tungstate solution by using 201-7 resin, adsorbing the tungsten on the column, and then replacing the tungsten on the column by using a resolving agent to obtain the ammonium tungstate solution.
Step nine: and (4) collecting the solid phase obtained in the sixth step, and adding sulfuric acid with the theoretical value of 1 time and sodium chlorate with the theoretical value of 2 times to obtain the salt products of copper and nickel.
Example 5
A method for recovering tungsten and molybdenum waste residues comprises the following steps:
the method comprises the following steps: taking 500g of tungsten-molybdenum waste residue, adding 1500g of water, mixing slurry and pulping, and performing filter pressing on the pulped material by using filter pressing equipment to obtain a filter residue form material; step two: drying the filter residue material obtained in the step one at 350 ℃ for 10 hours by drying equipment to remove oil and water in the tungsten-containing waste material to obtain a dried material; step three: putting the dried material obtained in the step two into crushing equipment for crushing, wherein the granularity is 50 meshes, and obtaining a crushed material; step four: adding the crushed material obtained in the step three, water and solid alkali into a size mixing tank according to a certain proportion to obtain size mixing liquid, wherein the mass ratio of the crushed material to the solid alkali to the water is 100: 4: 400, respectively; the solid base is flake base. Step five: feeding the slurry prepared in the step four into a high-pressure oxygen leaching device, reacting under certain conditions to obtain a reacted material, heating to 200 ℃, reacting for 10 hours under the oxygen pressure of 2MPa, and stirring at the rotating speed of 600 r/min to obtain a reacted material after the reaction is finished; step six: and D, separating the reacted material obtained in the fifth step into a liquid phase and a solid phase by using solid-liquid separation equipment.
Step seven: and adding sodium sulfide with the molar quantity 3 times of the theoretical value into the liquid phase obtained in the step six, adding water for size mixing, wherein the water adding ratio is 1:5 of the solid-to-liquid ratio, then performing gravity separation, and adopting high-precision gravity separation equipment to enable chromium to exist in a solid phase to obtain a chromium hydroxide product. And (4) carrying out the next step on the rest liquid phase after reselection.
Step eight: and (2) recovering tungsten in the residual liquid phase by adopting an ion exchange method, wherein the specific mode is as follows: adsorbing tungsten in the sodium tungstate solution by using 201-7 resin, adsorbing the tungsten on the column, and then replacing the tungsten on the column by using a resolving agent to obtain the ammonium tungstate solution.
Step nine: and (5) collecting the solid phase obtained in the sixth step, and adding phosphoric acid with the theoretical value being 1 time and sodium hypochlorite with the theoretical value being 2 times to obtain salt products of copper and nickel.
Example 6
A method for recovering tungsten and molybdenum waste residues comprises the following steps:
the method comprises the following steps: taking 500g of tungsten-molybdenum waste residue, adding 1000g of water, mixing slurry and pulping, and performing filter pressing on the pulped material by using filter pressing equipment to obtain a filter residue form material; step two: drying the filter residue material obtained in the step one at 400 ℃ for 5 hours by using drying equipment to remove oil and water in the tungsten-containing waste material to obtain a dried material; step three: putting the dried material obtained in the step two into crushing equipment for crushing, wherein the granularity is 60 meshes, and obtaining a crushed material; step four: adding the crushed material obtained in the step three, water and solid alkali into a size mixing tank according to a certain proportion to obtain size mixing liquid, wherein the mass ratio of the crushed material to the liquid alkali to the water is 100: 5: 350 of (a); the liquid alkali is strong ammonia. Step five: feeding the slurry prepared in the step four into a high-pressure oxygen leaching device, reacting under certain conditions to obtain a reacted material, heating to 150 ℃, reacting for 10 hours at an oxygen pressure of 10MPa, and stirring at a rotating speed of 800 r/min to obtain a reacted material after the reaction is finished; step six: and D, separating the reacted material obtained in the fifth step into a liquid phase and a solid phase by using solid-liquid separation equipment.
Step seven: and adding sodium sulfide with the molar quantity 4 times of the theoretical value into the liquid phase obtained in the step six, adding water for size mixing, wherein the water adding ratio is 1:7 of the solid-to-liquid ratio, then performing gravity separation, and adopting high-precision gravity separation equipment to enable chromium to exist in a solid phase to obtain a chromium hydroxide product. And (5) carrying out next step on the rest liquid phase after reselection.
Step eight: and (2) recovering tungsten in the residual liquid phase by adopting an ion exchange method, wherein the specific mode is as follows: adsorbing tungsten in the sodium tungstate solution by using 201-7 resin, adsorbing the tungsten on the column, and then replacing the tungsten on the column by using a resolving agent to obtain the ammonium tungstate solution.
Step nine: and (4) collecting the solid phase obtained in the sixth step, and adding hydrochloric acid with the theoretical value of 2 times and hypochlorous acid with the theoretical value of 2 times to obtain the salt products of copper and nickel.
Comparative example 1
Referring to example 1, the oxygen partial pressure was changed to 0 in example 1, and the final tungsten recovery rate was only 63.4% without changing other conditions.
Comparative example 2
With reference to example 1, the other conditions were unchanged, and steps seven and eight were performed as follows:
step seven: and adding sodium sulfide with the molar quantity 5 times of the theoretical value into the liquid phase obtained in the sixth step, and then performing pressure filtration, wherein the recovery rate of chromium is 85.20%. And (4) carrying out the next step on the residual liquid phase after filter pressing.
Step eight: and (2) recovering tungsten in the residual liquid phase by adopting an ion exchange method, wherein the specific mode is as follows: adsorbing tungsten in the sodium tungstate solution by using 201-7 resin, adsorbing the tungsten on the column, and then replacing the tungsten on the column by using a resolving agent to obtain the ammonium tungstate solution. The recovery of tungsten was tested to be 75.35%.
Comparative example 3
Referring to example 2, the sodium chlorate addition amount in example 2 was changed to 0, the final copper recovery rate was only 55.48%, and the nickel recovery rate was only 52.68% without changing other conditions.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. A method for recovering various metals from tungsten-molybdenum waste residue is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the following steps: mixing tungsten and molybdenum waste residues with water, pulping, and performing filter pressing through filter pressing equipment after pulping to obtain filter residue material;
step two: drying the filter residue material obtained in the step one by drying equipment to remove oil and water to obtain a dried material;
step three: putting the dried material obtained in the step two into crushing equipment for crushing to obtain a crushed material;
step four: adding the crushed material obtained in the step three, water and an alkaline reagent into a size mixing tank to obtain size mixing liquid;
step five: adding the slurry mixing liquid obtained in the step four into high-pressure oxygen leaching equipment, heating and pressurizing to perform reaction to obtain a reacted material;
step six: separating the reacted material obtained in the fifth step into a liquid phase and a solid phase by solid-liquid separation equipment;
step seven: adding a reducing agent into the liquid phase obtained in the sixth step to generate a precipitate, adding water for size mixing, and performing gravity separation to obtain a chromium hydroxide product; the rest liquid phase after reselection is subjected to the next step;
step eight: carrying out ion exchange on the residual liquid phase obtained in the step seven to obtain a tungsten product;
step nine: mixing the solid phase obtained in the sixth step with an oxidant and an acidic reagent, filtering after reaction, collecting a liquid phase to obtain a solution of copper salt and nickel salt, and carrying out the next step on the filtered solid phase;
step ten: and (4) mixing the solid phase obtained in the step nine to obtain mixed slurry, pumping the mixed slurry into high-speed centrifugal equipment, controlling the feeding speed, and separating out waste residues and liquid to obtain tantalum and niobium products.
2. The method for recovering a plurality of metals from tungsten-molybdenum slag according to claim 1, wherein: the tungsten-molybdenum waste residue is tungsten smelting waste residue or valuable metal tailings, wherein the mass content of tungsten oxide is 2-10%, and the mass content of molybdenum oxide is 1-5%; preferably, the mass content of chromium oxide in the tungsten-molybdenum waste residue is greater than or equal to 1%, the mass content of copper oxide is greater than or equal to 1%, the mass content of nickel oxide is greater than or equal to 1%, the mass content of tantalum is greater than or equal to 2%, and the mass content of niobium is greater than or equal to 1%.
3. The method for recovering a plurality of metals from tungsten-molybdenum slag according to claim 1, wherein: the adding amount of water in the first step is as follows: the mass ratio of the waste residue to the water is 1: 1-5;
optionally, the temperature for drying in the second step is 200-400 ℃, and the time is 2-24 h.
4. The method for recovering a plurality of metals from tungsten-molybdenum slag according to claim 1, wherein: the granularity of the crushed particles in the third step is 50-70 meshes;
optionally, the mass ratio of the crushed materials to the water to the alkaline reagent in the fourth step is 100 (1-5): (300-400);
preferably, the alkaline agent is a solid base and/or a liquid base.
5. The method for recovering a plurality of metals from tungsten-molybdenum slag according to claim 1, wherein: heating and pressurizing to carry out reaction in the fifth step, wherein the heating temperature is 150-;
optionally, adding water for size mixing in the seventh step, wherein the proportion of the added water is 1:3-10 of the solid-liquid mass ratio, and then reselecting.
6. The method for recovering a plurality of metals from tungsten-molybdenum slag according to claim 1 or 5, wherein: the gravity separation adopts high-precision gravity separation equipment for gravity separation, and the high-precision gravity separation equipment separates hydroxide of chromium under the centrifugal condition that the rotating speed is higher than 3500 r/min;
optionally, in the seventh step, the reducing agent is sodium sulfide, sodium hydrosulfide or sulfur dioxide, the using amount of the reducing agent is 4-10 times of the theoretical amount of the reducing agent required by the complete reaction of chromium, and the recovery rate of chromium is more than or equal to 95%;
optionally, in the step eight, the ion exchange for recovering tungsten is to adsorb the liquid phase by using resin, the liquid phase contains tungstate, the tungsten element is adsorbed on the column by the resin, and then the tungsten element is replaced by the lower column by using an analytical agent to obtain an ammonium tungstate solution, wherein the recovery rate of tungsten is greater than or equal to 95%.
7. The method for recovering a plurality of metals from tungsten-molybdenum slag according to claim 1, wherein: in the ninth step, the oxidant is at least one of hydrogen peroxide, hypochlorous acid, sodium chlorate or sodium hypochlorite, and the acidic reagent is at least one of sulfuric acid, hydrochloric acid or phosphoric acid.
8. The method for recovering a plurality of metals from tungsten molybdenum slag according to claim 7, wherein: in the ninth step, the molar ratio of the oxidant to the acidic reagent is 1-2:1, the dosage of the oxidant and the acidic reagent is 1-3 times of the theoretical value of complete reaction of copper and nickel, the recovery rate of copper is more than or equal to 97 percent, and the recovery rate of nickel is more than or equal to 96 percent.
9. The method for recovering a plurality of metals from tungsten-molybdenum slag according to claim 1, wherein: step ten, mixing the solid phase to obtain mixed slurry, wherein the solid-liquid ratio is 1:3-1: 10; and (3) pumping the obtained slurry into high-speed centrifugal equipment, wherein the centrifugal speed is more than 3500 revolutions.
10. The method for recovering a plurality of metals from tungsten molybdenum slag according to claim 1 or 9, wherein: pumping the obtained slurry into high-speed centrifugal equipment, and controlling the feeding speed to be 2-5m 3 And/h, the recovery rate of tantalum and the recovery rate of niobium are more than or equal to 95 percent.
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