CN115109931B - Method for recycling multiple metals from tungsten-molybdenum waste residues - Google Patents
Method for recycling multiple metals from tungsten-molybdenum waste residues Download PDFInfo
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- CN115109931B CN115109931B CN202210702962.6A CN202210702962A CN115109931B CN 115109931 B CN115109931 B CN 115109931B CN 202210702962 A CN202210702962 A CN 202210702962A CN 115109931 B CN115109931 B CN 115109931B
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- tungsten
- water
- waste residue
- molybdenum
- liquid phase
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- 239000002699 waste material Substances 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 61
- MGRWKWACZDFZJT-UHFFFAOYSA-N molybdenum tungsten Chemical compound [Mo].[W] MGRWKWACZDFZJT-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 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
- 238000004064 recycling Methods 0.000 title claims abstract description 18
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 95
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 86
- 239000010937 tungsten Substances 0.000 claims abstract description 86
- 239000000463 material Substances 0.000 claims abstract description 80
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000007791 liquid phase Substances 0.000 claims abstract description 47
- 238000002156 mixing Methods 0.000 claims abstract description 38
- 239000007790 solid phase Substances 0.000 claims abstract description 37
- 239000002002 slurry Substances 0.000 claims abstract description 35
- 239000007788 liquid Substances 0.000 claims abstract description 33
- 239000000047 product Substances 0.000 claims abstract description 29
- 238000001035 drying Methods 0.000 claims abstract description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000001301 oxygen Substances 0.000 claims abstract description 24
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 24
- 238000002386 leaching Methods 0.000 claims abstract description 23
- 238000000926 separation method Methods 0.000 claims abstract description 22
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 21
- 239000010955 niobium Substances 0.000 claims abstract description 21
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 21
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000003825 pressing Methods 0.000 claims abstract description 20
- 238000005342 ion exchange Methods 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 238000004537 pulping Methods 0.000 claims abstract description 12
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 8
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 claims abstract description 7
- 150000001879 copper Chemical class 0.000 claims abstract description 4
- 150000002815 nickel Chemical class 0.000 claims abstract description 4
- 239000002244 precipitate Substances 0.000 claims abstract description 4
- 238000011084 recovery Methods 0.000 claims description 59
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 58
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 39
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 37
- 229910052802 copper Inorganic materials 0.000 claims description 37
- 239000010949 copper Substances 0.000 claims description 37
- 229910052804 chromium Inorganic materials 0.000 claims description 36
- 239000011651 chromium Substances 0.000 claims description 36
- 229910052759 nickel Inorganic materials 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 17
- 239000007800 oxidant agent Substances 0.000 claims description 14
- 239000012445 acidic reagent Substances 0.000 claims description 10
- 239000011268 mixed slurry Substances 0.000 claims description 10
- 230000001590 oxidative effect Effects 0.000 claims description 10
- 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
- 238000003723 Smelting Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 7
- 238000005086 pumping Methods 0.000 claims description 6
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 4
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 230000005484 gravity Effects 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
- 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
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 241001131927 Placea Species 0.000 claims 1
- 239000000243 solution Substances 0.000 description 32
- 239000003513 alkali Substances 0.000 description 24
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 16
- 239000003795 chemical substances by application Substances 0.000 description 15
- 229910052750 molybdenum Inorganic materials 0.000 description 15
- 239000011733 molybdenum Substances 0.000 description 15
- 239000002893 slag Substances 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000002378 acidificating effect Effects 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
- 238000000605 extraction Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 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
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 101001018064 Homo sapiens Lysosomal-trafficking regulator Proteins 0.000 description 1
- 102100033472 Lysosomal-trafficking regulator Human genes 0.000 description 1
- 235000010703 Modiola caroliniana Nutrition 0.000 description 1
- 244000038561 Modiola caroliniana Species 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- -1 acidolysis Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 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
- 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
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 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
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000009853 pyrometallurgy 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
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 230000009466 transformation Effects 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 recycling various 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 a filter residue; drying the filter residue through a drying device to obtain a dried material, crushing the dried material in a crushing device to obtain crushed materials, adding the crushed materials, water and an alkaline reagent into a slurry mixing tank to obtain slurry, adding the slurry into a high-pressure oxygen leaching device, heating and pressurizing to react to obtain a reacted material, and separating a liquid phase and a solid phase of the reacted material through a solid-liquid separation device; adding a reducing agent into the liquid phase to generate precipitate, adding water to carry out slurry mixing, and then carrying out reselection to obtain a chromium hydroxide product; ion exchange is carried out on the residual liquid phase after the reselection to obtain a tungsten product; the solid phase obtained by the separation is respectively recovered into copper salt, nickel salt, tantalum and niobium products. The method can recycle various valuable elements in the low-grade tungsten-molybdenum waste residues, and has good 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 various metals from tungsten-molybdenum waste residues.
Background
Tungsten-molybdenum waste slag is waste generated in nonferrous metal smelting, and the residue contains various valuable elements such as copper, nickel, chromium, tungsten, molybdenum and the like, and the cost of the existing recovery method is higher due to the lower content, so that the cost performance of recovery is lower, and the residue is often piled up and discarded to become solid garbage of a smelting plant.
Meanwhile, tailings generated by separation operation in mineral separation also contain more valuable elements, and the tailings are low in content and high in recovery difficulty like tungsten-molybdenum waste residues, are generally discarded along with industrial garbage, and the valuable elements remained in the tailings cannot be enriched and recovered.
The mixed existence of tungsten element and molybdenum element in waste residue makes separation of tungsten and molybdenum difficult because conventional acid leaching and alkali leaching methods cannot effectively separate tungsten from molybdenum, and the atomic radius, chemical valence state and chemical property of tungsten and molybdenum in aqueous solution are very similar, so that the separation of tungsten and molybdenum is difficult. The existing solutions include precipitation, ion exchange, extraction, liquid membrane separation, etc., which are not suitable for use in the recovery of low-grade waste residues according to the present invention.
Patent application CNCN103103360a discloses a method for recovering metals by using APT waste residues, which comprises the following steps: the method for recycling copper, tungsten and molybdenum by using APT waste residues is characterized by comprising the following steps of: the method comprises the following steps: a. grinding: grinding waste slag containing copper, tungsten and molybdenum generated in the ammonium paratungstate production process to-325 meshes of more than or equal to 90 percent; b. and (3) separating and recycling copper by alkaline leaching: c, filtering the ground waste residue in the step a by using soft water with the pH value of 7.5-8.5, and separating copper-containing slag from tungsten-molybdenum-containing solution; then the slag containing copper is boiled and leached by alkali, wherein the alkali is NaOH, when the alkali concentration is 35-45g/L, the alkali addition is stopped, and after boiling, the temperature is kept for 1.5-2.5h, and the copper sulfide is recovered after washing; c. recovering molybdenum by acid leaching and precipitation purification method: adding 125% -150% of vulcanizing agent which is NaHS based on Mo theory into the solution containing tungsten and molybdenum produced in the step b, boiling the solution for 2 hours after the vulcanizing agent is added, after the vulcanizing reaction is finished, making the solution appear rose or mauve, continuously stirring, 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 is changed in the boiling process, and continuously measuring and adding acid to adjust the pH value to produce MoS 3 The precipitated solution was blue-black and brown MoS was observed 3 Precipitation, and filtering to obtain MoS-containing extract 3 Slag and tungstic acid solution; d. recovery of tungsten using ion exchange: and c, carrying out four traditional ion exchange processes of dilution, adsorption, leaching and desorption on the tungstic acid solution produced in the step c to obtain a crude sodium tungstate solution, and carrying out the subsequent traditional processes of precipitation of artificial white tungsten, acidolysis, solution preparation of ammonium tungstate and evaporative crystallization on the solution to produce 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; meanwhile, three metal elements of copper, tungsten and molybdenum are contained in the APT waste residues, and for the waste residues with lower molybdenum content, the cost for recovering molybdenum is too high, and the yield is lower; while the purity of tungsten extracted in the subsequent step is not performed in step cLow.
Disclosure of Invention
The invention aims to overcome the difficulty in recycling the tungsten-molybdenum waste residues in the prior art, and provides a method for recycling various metals from the tungsten-molybdenum waste residues, which can solve the problem that the tungsten-molybdenum separation interferes with the whole process, and can finish the separate extraction of tantalum, niobium, copper, chromium, nickel and tungsten on the premise of not independently extracting molybdenum, and the purity of an extracted product is higher.
In the invention, the tungsten-molybdenum waste residue is subjected to high-pressure oxygen leaching treatment to obtain sodium tungstate solution and residues, the solution is subjected to impurity removal to obtain pure tungstate solution, and the residues are subjected to reselection to obtain the mixture. The method adopts a high-pressure oxygen leaching method to ensure that the recovery rate of tungsten is more than 95 percent.
The invention adopts reducing agent, controls the technological conditions including reducing agent, adding water for size mixing, the adding water proportion is 1:3-10 of solid-liquid mass ratio, the obtained size is reselected, tungsten element and chromium element enter liquid phase and solid phase respectively, thus avoiding tungsten entrainment during chromium recovery. Further, after separating the hydroxide of chromium, the tungsten is recovered by an ion exchange method, thereby ensuring the high recovery rate of tungsten.
Aiming at the problem that the copper element and the nickel element have cross influence with chromium, the invention takes copper and nickel as a group of objects, takes chromium as a recovery object independently, adopts different recovery paths to process, and after high-pressure oxygen leaching, the chromium mainly enters a liquid phase, adopts a reduction thought for the chromium, and forms chromium hydroxide after the chromium element is reduced; the copper and the nickel are mainly in the solid phase, so that the separation of copper element, nickel element and chromium is realized, and the copper and the nickel in the solid phase adopt an oxidation thought, so that copper salt and nickel salt are formed under the action of an oxidant and an acidic reagent, the synchronous recovery of copper, nickel and chromium is realized, and the interference on a tungsten recovery route is avoided.
Tantalum, niobium are finally recovered in the present invention because of the fact thatThe chemical property of the alloy is inactive and does not react with conventional acid and alkali, tantalum and niobium exist in the form of oxide in the slurry, the invention adopts centrifugal equipment, the centrifugal condition is that the centrifugal speed is above 3500r, and the feeding speed is 2-5m 3 And (h) the tantalum and the niobium exist in the form of oxides and are enriched, so that tantalum and niobium products are obtained, and the recovery rate is higher than 95%.
The specific scheme is as follows:
a method for recovering multiple metals from tungsten molybdenum waste residues, comprising the following steps:
step one: mixing tungsten-molybdenum waste residues with water, pulping, and performing filter pressing through filter pressing equipment after pulping to obtain a filter residue;
step two: drying the filter residue obtained in the step one through drying equipment to remove oil and water to obtain a dried material;
step three: putting the dried material obtained in the second step into crushing equipment for crushing to obtain crushed materials;
step four: adding the crushed material, water and alkaline reagent obtained in the step three into a slurry mixing tank to obtain slurry mixing liquid;
step five: adding the slurry obtained in the step four into high-pressure oxygen leaching equipment, heating and pressurizing to react, and obtaining a reacted material;
step six: separating liquid phase and solid phase from the reacted material obtained in the fifth step through solid-liquid separation equipment;
step seven: adding a reducing agent into the liquid phase obtained in the step six to generate a precipitate, adding water to carry out size mixing, and then carrying out reselection to obtain a chromium hydroxide product; the liquid phase remained after the reselection is carried out the next step;
step eight: ion exchange is carried out on the residual liquid phase in the step seven, so that a tungsten product is obtained;
step nine: mixing the solid phase obtained in the step six 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 D, mixing the solid phase in the step nine to obtain a mixed slurry, pumping the mixed slurry into high-speed centrifugal equipment, controlling the feeding speed, and separating 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, copper oxide, nickel oxide, tantalum and niobium in the tungsten-molybdenum waste residues is greater than or equal to 1%, 2% and 1%.
Further, the water addition in the first step is as follows: the mass ratio of the waste residue to the water is 1:1-5;
optionally, the temperature of the drying in the second step is 200-400 ℃ and the time is 2-24h.
Further, in the third step, the granularity of the crushing is 50-70 meshes;
optionally, in the fourth step, the mass ratio of the broken material, the water and the alkaline agent is 100 (1-5): (300-400); preferably, the alkaline reagent is a solid base and/or a liquid base.
Further, in the step five, heating and pressurizing are carried out for reaction, the heating temperature is 150-200 ℃, the pressure is 1.0-10MPa, and the reaction time is 10-20h;
optionally, adding water for size mixing in the step seven, wherein the ratio of water to solid-liquid mass ratio is 1:3-10, and then carrying out reselection.
Further, the reselection is performed by adopting high-precision reselection equipment, and the high-precision reselection equipment separates the hydroxide of the chromium under the centrifugal condition with the rotating speed of more than 3500 r/min.
Optionally, in the seventh step, the reducing agent is sodium sulfide, sodium hydrosulfide or sulfur dioxide, the dosage 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 is used for recovering tungsten, the liquid phase is adsorbed by using resin, the liquid phase contains tungstate, tungsten element is adsorbed on a column by using the resin, then the lower column is replaced by using a resolving agent, and the ammonium tungstate solution is obtained, and the recovery rate of tungsten is more than or equal to 95%.
Further, in the step nine, 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 step nine, 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 the complete reaction of copper and nickel, the recovery rate of copper is more than or equal to 97%, and the recovery rate of nickel is more than or equal to 96%.
In the step ten, the solid phase is subjected to slurry mixing, wherein the solid-liquid ratio is 1:3-1:10, and slurry mixing is obtained; and (3) pumping the obtained size into high-speed centrifugal equipment, wherein the centrifugal speed is 3500 revolutions or more.
Further, the obtained size is pumped into high-speed centrifugal equipment, 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.
The beneficial effects are that: the invention recovers various metals from waste residue, and can realize waste recovery and reuse.
Furthermore, the invention utilizes the reselection equipment to recycle the chromium, has better chromium recycling rate, and the residual liquid after recycling the chromium is more convenient for recycling the tungsten, and the recycling rate of the tungsten is high.
And moreover, the method adopts different recovery paths for copper, nickel and chromium, so that the recovery rate of the copper, the nickel and the chromium is guaranteed, the interference on tungsten recovery is avoided, and the method has great environmental protection significance and economic value on the recovery and utilization of non-renewable resources.
Finally, the invention recovers tantalum and niobium products in a centrifugal way, the recovery rate of tantalum is more than or equal to 95%, and the recovery rate of niobium is more than or equal to 95%, thus having better recovery effect.
Detailed Description
Definitions of some of the terms used in the present invention are given below, and other unrecited terms have definitions and meanings well 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 generated in a wet method or a pyrometallurgical process, for example, tungsten-cobalt slag obtained by using a saltpeter smelting process, tungsten-cobalt slag obtained by using an oxidation smelting process, tungsten-cobalt slag obtained by using a sodium carbonate roasting process, tungsten-cobalt slag obtained by using an oxidation roasting alkaline leaching process, and tungsten-containing residues obtained by other processes. The valuable metal tailings can be tailings obtained by flotation of copper-containing ores, tungsten-containing ores and nickel-containing ores. In a specific embodiment, the tungsten and molybdenum waste residues contain 2-10% of tungsten oxide and 1-5% of molybdenum oxide, the chromium oxide in the tungsten and molybdenum waste residues contains 1% or more of chromium oxide, 1% or more of copper oxide, 1% or more of nickel oxide, 2% or more of tantalum and 1% or more of niobium.
In the invention, the step four realizes transformation of tungsten by using an alkaline reagent, thereby realizing the purpose of recovering tungsten, and the transformed tungsten can be dissolved out in a large amount and enter a liquid phase when reacting in high-pressure oxygen leaching equipment, so as to realize high-efficiency recovery of tungsten.
In the invention, the step five is to make most of tungsten enter liquid phase through high pressure oxygen leaching reaction so as to achieve high-efficiency recovery of tungsten. In order to ensure the effect of the high-pressure oxygen leaching reaction, waste residues are subjected to slurry mixing, then are dried and crushed in the first to third steps, and the difference between raw materials in different batches can be adjusted, so that the materials are more uniform, the slurry mixing obtained after the slurry mixing in the fourth step is uniform and high, and a foundation is laid for efficient separation and extraction of the high-pressure oxygen leaching. Meanwhile, in the fifth step, chromium element in the waste residue enters a liquid phase, and copper and nickel mainly remain in a solid phase.
In the invention, in the seventh step, the reducing agent is utilized to lead the chromium to form a precipitate, and the gravity separation operation is adopted to lead the hydroxide of the chromium to be separated out under high-speed centrifugation, thereby reducing the tungsten loss.
In the invention, the step nine adopts the oxidant and the acid reagent, so that the copper element and the nickel element in the solid phase form salts to be recovered under the cooperation of the oxidant and the acid reagent, and the extraction efficiency of the copper element and the nickel element is higher.
Preferably, in the step nine, the molar ratio of the oxidizing agent to the acidic agent is 1-2:1, and the amount of the oxidizing agent to the acidic agent is 1-3 times of the theoretical value of the complete reaction of copper and nickel, wherein the calculation of the theoretical values of the acidic agent and the oxidizing agent is performed according to a chemical reaction equation, taking sulfuric acid as the acidic agent and oxygen as the oxidizing agent as an example, and 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 preferred embodiments of the present invention are described below, it should be understood that the present invention may be embodied in various forms and should not be limited to the embodiments set forth herein. The specific techniques or conditions are not identified in the examples and are performed according to techniques or conditions described in the literature in this field or according to the product specifications. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention. In the examples below, "%" refers to weight percent, unless explicitly stated otherwise.
The main components of tungsten molybdenum slag used in the examples are shown in the following table:
TABLE 1 Main ingredients of waste residue and content table (mass percent)
Example 1
The method for recycling tungsten-molybdenum waste residues comprises the following steps:
step one: taking 500g of tungsten-molybdenum waste residues, adding 500g of water, pulping, and performing filter pressing on the pulpified materials through filter pressing equipment to obtain filter residue form materials; step two: drying the filter residue obtained in the step one for 24 hours at 300 ℃ through drying equipment to remove oil and water in tungsten-containing waste materials to obtain a drying material; step three: crushing the dried material obtained in the second step in crushing equipment, wherein the granularity is 60 meshes, so as to obtain crushed materials; step four: adding the crushed material, water and solid alkali obtained in the step three into a slurry mixing tank according to a certain proportion to obtain slurry, wherein the mass ratio of the crushed material to the solid alkali to the water is 100:2:300; the solid alkali is tablet alkali, step five: feeding the slurry obtained in the step four into high-pressure oxygen leaching equipment, heating to 180 ℃, reacting for 16 hours under the oxygen pressure of 2MPa, stirring at the rotation speed of 600 r/min, and obtaining a reacted material after the reaction is completed; step six: and D, separating the liquid phase and the solid phase from the reacted material obtained in the step five through solid-liquid separation equipment.
Step seven: adding sodium sulfide with the molar quantity being 5 times of the theoretical value into the liquid phase obtained in the step six, adding water for size mixing, wherein the water adding proportion is 1:3 of the solid-liquid ratio, then carrying out reselection, and adopting high-precision reselection equipment, wherein chromium exists in the solid phase to obtain a hydroxide product of chromium, and the recovery rate of chromium is 95%. The liquid phase remaining after the reselection is subjected to the next step.
Step eight: the tungsten in the residual liquid phase is recovered by adopting an ion exchange method, and the specific method is as follows: and adsorbing tungsten in the sodium tungstate solution by using 201 x 7 resin, adsorbing the tungsten on an upper column, and then replacing the tungsten on a lower 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 D, collecting the solid phase obtained in the step six, and adding sulfuric acid with a theoretical value of 1.5 times and hydrogen peroxide with a theoretical value of 2 times to obtain a salt product of copper and nickel, wherein the recovery rate of copper is 97.83%, and the recovery rate of nickel is 98.59%.
Step ten: and D, mixing the solid phase in the step nine to obtain a mixed slurry, pumping the mixed slurry into high-speed centrifugal equipment, controlling the feeding speed, and separating waste residues and liquid to obtain tantalum and niobium products. Specifically, the solid-to-liquid ratio of the slurry is 1:3, and the feeding speed is controlled to be 2m 3 And/h, the centrifugal rate is 3400r, the recovery rate of tantalum is 95.17%, and the recovery rate of niobium is 95.83%.
Example 2
The method for recycling tungsten-molybdenum waste residues comprises the following steps:
step one: taking 500g of tungsten-molybdenum waste residues, adding 1000g of water, pulping, and performing filter pressing on the pulpified materials through filter pressing equipment to obtain filter residue form materials; step two: drying the filter residue obtained in the step one for 16 hours at 400 ℃ through drying equipment to remove oil and water in tungsten-containing waste materials to obtain a drying material; step three: crushing the dried material obtained in the second step in crushing equipment, wherein the granularity is 100 meshes, so as to obtain crushed materials; step four: adding the crushed material, water and solid alkali which are obtained in the step three into a slurry mixing tank according to a certain proportion, wherein the mass ratio of the crushed material to the solid alkali to the water is 100:3:400; step five: feeding the slurry obtained in the step four into high-pressure oxygen leaching equipment, reacting under certain conditions to obtain a reacted material, heating to 160 ℃, reacting for 12 hours at the rotating speed of 650 r/min under the oxygen pressure of 1.2MPa, and obtaining the reacted material after the reaction is completed; step six: and D, separating the liquid phase and the solid phase from the reacted material obtained in the step five through solid-liquid separation equipment.
Step seven: adding sodium sulfide with the molar quantity being 5 times of the theoretical value into the liquid phase obtained in the step six, adding water for size mixing, wherein the water adding proportion is 1:5 of the solid-liquid ratio, then carrying out reselection, and adopting high-precision reselection equipment, wherein chromium exists in the solid phase to obtain a hydroxide product of chromium, and the recovery rate of chromium is 95.35%. The liquid phase remaining after the reselection is subjected to the next step.
Step eight: the tungsten in the residual liquid phase is recovered by adopting an ion exchange method, and the specific method is as follows: and adsorbing tungsten in the sodium tungstate solution by using 201 x 7 resin, adsorbing the tungsten on an upper column, and then replacing the tungsten on a lower 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 D, collecting the solid phase obtained in the step six, and adding hydrochloric acid with a theoretical value of 1.6 times and sodium chlorate with a theoretical value of 2.5 times to obtain a salt product of copper and nickel, wherein the recovery rate of copper is 97.28%, and the recovery rate of nickel is 98.32%.
Step ten: mixing the solid phase in the step nine to obtain a mixed slurry, pumping the mixed slurry into high-speed centrifugal equipment, controlling the feeding speed, and separating waste residue and liquidAnd obtaining tantalum and niobium products. Specifically, the solid-to-liquid ratio of the slurry is 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
The method for recycling tungsten-molybdenum waste residues comprises the following steps:
step one: taking 500g of tungsten-molybdenum waste residues, adding 1200g of water, pulping, and performing filter pressing on the pulpified materials through filter pressing equipment to obtain filter residue form materials; step two: drying the filter residue obtained in the step one for 8 hours at 350 ℃ through drying equipment to remove oil and water in tungsten-containing waste materials to obtain a drying material; step three: crushing the dried material obtained in the second step in crushing equipment, wherein the granularity is 120 meshes, so as to obtain crushed materials; step four: adding the crushed material, water and solid alkali which are obtained in the step three into a slurry mixing tank according to a certain proportion, wherein the mass ratio of the crushed material to the solid alkali to the water is 100:2:300; step five: feeding the slurry obtained in the step four into high-pressure oxygen leaching equipment, reacting under certain conditions to obtain a reacted material, heating to 160 ℃, reacting for 16 hours at the rotating speed of 600 r/min under the oxygen pressure of 1.5MPa, and obtaining the reacted material after the reaction is completed; step six: and D, separating the liquid phase and the solid phase from the reacted material obtained in the step five through solid-liquid separation equipment.
Step seven: adding sodium sulfide with the molar quantity being 5 times of the theoretical value into the liquid phase obtained in the step six, adding water for size mixing, wherein the water adding proportion is 1:10 of the solid-liquid ratio, then carrying out reselection, and adopting high-precision reselection equipment, wherein chromium exists in the solid phase to obtain a hydroxide product of chromium, and the recovery rate of chromium is 93.25%. The liquid phase remaining after the reselection is subjected to the next step.
Step eight: the tungsten in the residual liquid phase is recovered by adopting an ion exchange method, and the specific method is as follows: and adsorbing tungsten in the sodium tungstate solution by using 201 x 7 resin, adsorbing the tungsten on an upper column, and then replacing the tungsten on a lower column by using a resolving agent to obtain the ammonium tungstate solution. The recovery of tungsten was tested to be 96.58%.
Step nine: and D, collecting the solid phase obtained in the step six, and adding phosphoric acid with a theoretical value of 1.7 times and hypochlorous acid with a theoretical value of 3 times to obtain a salt product of copper and nickel, wherein the recovery rate of copper is 97.35%, and the recovery rate of nickel is 96.85%.
Step ten: and D, mixing the solid phase in the step nine to obtain a mixed slurry, pumping the mixed slurry into high-speed centrifugal equipment, controlling the feeding speed, and separating waste residues and liquid to obtain tantalum and niobium products. Specifically, the solid-to-liquid ratio of the slurry is 1:7, and the feeding speed is controlled to be 5m 3 The centrifugation rate was 3800r, the recovery rate of tantalum was 95.28%, and the recovery rate of niobium was 95.33%.
Example 4
The method for recycling tungsten-molybdenum waste residues comprises the following steps:
step one: taking 500g of tungsten-molybdenum waste residues, adding 2500g of water, pulping, and performing filter pressing on the pulpified materials through filter pressing equipment to obtain filter residue form materials; step two: drying the filter residue obtained in the step one for 12 hours at 200 ℃ through drying equipment to remove oil and water in tungsten-containing waste materials to obtain a drying material; step three: crushing the dried material obtained in the second step in crushing equipment, wherein the granularity is 70 meshes, so as to obtain crushed materials; step four: adding the crushed material, water and solid alkali obtained in the step three into a slurry mixing tank according to a certain proportion to obtain slurry, wherein the mass ratio of the crushed material to the solid alkali to the water is 100:3:300; the solid base is sodium hydroxide. Step five: feeding the slurry obtained in the step four into high-pressure oxygen leaching equipment, reacting under certain conditions to obtain a reacted material, heating to 150 ℃, reacting for 16 hours under the oxygen pressure of 8MPa, stirring at the rotation speed of 500r/min, and obtaining the reacted material after the reaction is completed; step six: and D, separating the liquid phase and the solid phase from the reacted material obtained in the step five through solid-liquid separation equipment.
Step seven: adding sodium sulfide with the molar quantity being 5 times of the theoretical value into the liquid phase obtained in the step six, adding water for size mixing, wherein the water adding proportion is 1:10 of the solid-liquid ratio, then carrying out reselection, and adopting high-precision reselection equipment to ensure that chromium exists in the solid phase to obtain a chromium hydroxide product. The liquid phase remaining after the reselection is subjected to the next step.
Step eight: the tungsten in the residual liquid phase is recovered by adopting an ion exchange method, and the specific method is as follows: and adsorbing tungsten in the sodium tungstate solution by using 201 x 7 resin, adsorbing the tungsten on an upper column, and then replacing the tungsten on a lower column by using a resolving agent to obtain the ammonium tungstate solution.
Step nine: and D, collecting the solid phase obtained in the step six, and adding sulfuric acid with a theoretical value of 1 time and sodium chlorate with a theoretical value of 2 times to obtain a salt product of copper and nickel.
Example 5
The method for recycling tungsten-molybdenum waste residues comprises the following steps:
step one: taking 500g of tungsten-molybdenum waste residues, adding 1500g of water, pulping, and performing filter pressing on the pulpified materials through filter pressing equipment to obtain filter residue form materials; step two: drying the filter residue obtained in the step one for 10 hours at 350 ℃ through drying equipment to remove oil and water in tungsten-containing waste materials to obtain a drying material; step three: crushing the dried material obtained in the second step in crushing equipment, wherein the granularity is 50 meshes, so as to obtain crushed materials; step four: adding the crushed material, water and solid alkali obtained in the step three into a slurry mixing tank according to a certain proportion to obtain slurry, wherein the mass ratio of the crushed material to the solid alkali to the water is 100:4:400; the solid alkali is tablet alkali. Step five: feeding the slurry obtained in the step four into high-pressure oxygen leaching equipment, reacting under certain conditions to obtain a reacted material, heating to 200 ℃, reacting for 10 hours under the oxygen pressure of 2MPa, stirring at the rotating speed of 600 r/min, and obtaining the reacted material after the reaction is completed; step six: and D, separating the liquid phase and the solid phase from the reacted material obtained in the step five through solid-liquid separation equipment.
Step seven: adding sodium sulfide with the molar quantity being 3 times of the theoretical value into the liquid phase obtained in the step six, adding water for size mixing, wherein the water adding proportion is 1:5 of the solid-liquid ratio, then carrying out reselection, and adopting high-precision reselection equipment to ensure that chromium exists in the solid phase to obtain a chromium hydroxide product. The liquid phase remaining after the reselection is subjected to the next step.
Step eight: the tungsten in the residual liquid phase is recovered by adopting an ion exchange method, and the specific method is as follows: and adsorbing tungsten in the sodium tungstate solution by using 201 x 7 resin, adsorbing the tungsten on an upper column, and then replacing the tungsten on a lower column by using a resolving agent to obtain the ammonium tungstate solution.
Step nine: and D, collecting the solid phase obtained in the step six, and adding phosphoric acid with a theoretical value of 1 time and sodium hypochlorite with a theoretical value of 2 times to obtain a salt product of copper and nickel.
Example 6
The method for recycling tungsten-molybdenum waste residues comprises the following steps:
step one: taking 500g of tungsten-molybdenum waste residues, adding 1000g of water, pulping, and performing filter pressing on the pulpified materials through filter pressing equipment to obtain filter residue form materials; step two: drying the filter residue obtained in the step one for 5 hours at 400 ℃ through drying equipment to remove oil and water in tungsten-containing waste materials to obtain a drying material; step three: crushing the dried material obtained in the second step in crushing equipment, wherein the granularity is 60 meshes, so as to obtain crushed materials; step four: adding the crushed material, water and solid alkali obtained in the step three into a slurry mixing tank according to a certain proportion to obtain slurry, wherein the mass ratio of the crushed material to the liquid alkali to the water is 100:5:350; the liquid alkali is concentrated ammonia water. Step five: feeding the slurry obtained in the step four into high-pressure oxygen leaching equipment, reacting under certain conditions to obtain a reacted material, heating to 150 ℃, reacting for 10 hours under the oxygen pressure of 10MPa, stirring at the rotating speed of 800 r/min, and obtaining the reacted material after the reaction is completed; step six: and D, separating the liquid phase and the solid phase from the reacted material obtained in the step five through solid-liquid separation equipment.
Step seven: adding sodium sulfide with the molar quantity being 4 times of the theoretical value into the liquid phase obtained in the step six, adding water for size mixing, wherein the water adding proportion is 1:7 of the solid-liquid ratio, then carrying out reselection, and adopting high-precision reselection equipment to ensure that chromium exists in the solid phase to obtain a chromium hydroxide product. The liquid phase remaining after the reselection is subjected to the next step.
Step eight: the tungsten in the residual liquid phase is recovered by adopting an ion exchange method, and the specific method is as follows: and adsorbing tungsten in the sodium tungstate solution by using 201 x 7 resin, adsorbing the tungsten on an upper column, and then replacing the tungsten on a lower column by using a resolving agent to obtain the ammonium tungstate solution.
Step nine: and D, collecting the solid phase obtained in the step six, and adding hydrochloric acid with a theoretical value of 2 times and hypochlorous acid with a theoretical value of 2 times to obtain salt products of copper and nickel.
Comparative example 1
Referring to example 1, the other conditions were not changed, and only the oxygen partial pressure in example 1 was changed to 0, and the final tungsten recovery rate was only 63.4%.
Comparative example 2
Referring to example 1, the other conditions were unchanged, and steps seven and eight were operated as follows:
step seven: and D, adding sodium sulfide 5 times the theoretical molar quantity into the liquid phase obtained in the step six, and then performing filter pressing, wherein the recovery rate of chromium is 85.20%. And carrying out the next step on the residual liquid phase after the filter pressing.
Step eight: the tungsten in the residual liquid phase is recovered by adopting an ion exchange method, and the specific method is as follows: and adsorbing tungsten in the sodium tungstate solution by using 201 x 7 resin, adsorbing the tungsten on an upper column, and then replacing the tungsten on a lower column by using a resolving agent to obtain the ammonium tungstate solution. The recovery of tungsten was 75.35% by test.
Comparative example 3
Referring to example 2, the other conditions were not changed, and only the sodium chlorate addition amount in example 2 was changed to 0, and the final copper recovery rate was only 55.48% and the nickel recovery rate was only 52.68%.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner without contradiction. The various possible combinations of the invention are not described in detail in order to avoid unnecessary repetition.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (10)
1. A method for recycling multiple metals from tungsten-molybdenum waste residues is characterized by comprising the following steps: the method comprises the following steps:
step one: mixing tungsten-molybdenum waste residues with water, pulping, and performing filter pressing through filter pressing equipment after pulping to obtain a filter residue; 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%; the mass content of chromium oxide in the tungsten-molybdenum waste residue is more than or equal to 1%, the mass content of copper oxide is more than or equal to 1%, the mass content of nickel oxide is more than or equal to 1%, the mass content of tantalum is more than or equal to 2%, and the mass content of niobium is more than or equal to 1%;
step two: drying the filter residue obtained in the step one through drying equipment to remove oil and water to obtain a dried material;
step three: putting the dried material obtained in the second step into crushing equipment for crushing to obtain crushed materials;
step four: adding the crushed material, water and alkaline reagent obtained in the step three into a slurry mixing tank to obtain slurry mixing liquid;
step five: adding the slurry obtained in the step four into high-pressure oxygen leaching equipment, heating and pressurizing to react, and obtaining a reacted material;
step six: separating liquid phase and solid phase from the reacted material obtained in the fifth step through solid-liquid separation equipment;
step seven: adding a reducing agent into the liquid phase obtained in the step six to generate a precipitate, adding water to carry out size mixing, and then carrying out reselection to obtain a chromium hydroxide product; the liquid phase remained after the reselection is carried out the next step;
step eight: ion exchange is carried out on the residual liquid phase in the step seven, so that a tungsten product is obtained;
step nine: mixing the solid phase obtained in the step six 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; in the step nine, the mol ratio of the oxidant to the acid reagent is 1-2:1, the consumption of the oxidant and the acid reagent is 1-3 times of the theoretical value of the complete reaction of copper and nickel, the recovery rate of copper is more than or equal to 97%, and the recovery rate of nickel is more than or equal to 96%;
step ten: mixing the solid phase in the step nine to obtain a mixed slurry, and pumping the mixed slurry into a high placeA rapid centrifugal device for controlling the feeding speed to be 2-5m 3 And (3) obtaining tantalum and niobium products, wherein the recovery rate of tantalum and the recovery rate of niobium are more than or equal to 95%.
2. The method for recovering multiple metals from tungsten molybdenum waste residue according to claim 1, wherein: the water addition amount in the first step is as follows: the mass ratio of the waste residue to the water is 1:1-5.
3. The method for recovering multiple metals from tungsten molybdenum waste residue according to claim 1, wherein: and in the second step, the temperature of the drying is 200-400 ℃ and the time is 2-24h.
4. The method for recovering multiple metals from tungsten molybdenum waste residue according to claim 1, wherein: the granularity of the crushing in the third step is 50-70 meshes.
5. The method for recovering multiple metals from tungsten molybdenum waste residue according to claim 4, wherein: in the fourth step, the mass ratio of the broken material, the water and the alkaline reagent is 100 (1-5): (300-400).
6. The method for recovering multiple metals from tungsten molybdenum waste residue according to claim 5, wherein: the alkaline reagent is a solid base and/or a liquid base.
7. The method for recovering multiple metals from tungsten molybdenum waste residue according to claim 1, wherein: in the fifth step, heating and pressurizing are carried out for reaction, the heating temperature is 150-200 ℃, the pressure is 1.0-10MPa, and the reaction time is 10-20h.
8. The method for recovering multiple metals from tungsten molybdenum waste residue according to claim 7, wherein: and step seven, adding water for size mixing, wherein the mass ratio of the water to the solid-liquid is 1:3-10, and then carrying out reselection.
9. The method for recovering multiple metals from tungsten molybdenum waste residue according to claim 1 or 7, wherein: the high-precision gravity separation equipment is adopted for gravity separation, and the high-precision gravity separation equipment separates the hydroxide of the chromium under the centrifugal condition with the rotating speed of 3500r/min or above.
10. The method for recovering multiple metals from tungsten molybdenum waste residue according to claim 9, wherein: in the seventh step, the reducing agent is sodium sulfide, sodium hydrosulfide or sulfur dioxide, the dosage 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%.
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