CN103290223A - Comprehensive recovery method for multiple metals of waste catalyst - Google Patents
Comprehensive recovery method for multiple metals of waste catalyst Download PDFInfo
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- CN103290223A CN103290223A CN2013102044762A CN201310204476A CN103290223A CN 103290223 A CN103290223 A CN 103290223A CN 2013102044762 A CN2013102044762 A CN 2013102044762A CN 201310204476 A CN201310204476 A CN 201310204476A CN 103290223 A CN103290223 A CN 103290223A
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- vanadium
- molybdenum
- preimpregnation
- leaching
- spent catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 49
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 21
- 239000002184 metal Substances 0.000 title claims abstract description 19
- 150000002739 metals Chemical class 0.000 title claims abstract description 13
- 238000011084 recovery Methods 0.000 title claims description 12
- 239000002699 waste material Substances 0.000 title abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 37
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 37
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 31
- 239000011733 molybdenum Substances 0.000 claims abstract description 31
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000003723 Smelting Methods 0.000 claims abstract description 20
- 238000002386 leaching Methods 0.000 claims abstract description 20
- 239000002893 slag Substances 0.000 claims abstract description 19
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 18
- 239000010941 cobalt Substances 0.000 claims abstract description 18
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000605 extraction Methods 0.000 claims abstract description 12
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 10
- 239000001117 sulphuric acid Substances 0.000 claims abstract description 8
- 235000011149 sulphuric acid Nutrition 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 6
- 239000012535 impurity Substances 0.000 claims abstract description 5
- 239000010703 silicon Substances 0.000 claims abstract description 4
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 claims description 12
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 10
- 239000004411 aluminium Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003921 oil Substances 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229960001866 silicon dioxide Drugs 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 241000220317 Rosa Species 0.000 claims description 3
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 3
- 239000011609 ammonium molybdate Substances 0.000 claims description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 3
- 229940010552 ammonium molybdate Drugs 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 150000002815 nickel Chemical class 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 10
- 239000007788 liquid Substances 0.000 abstract description 7
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 abstract 1
- 230000004907 flux Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 11
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000011734 sodium Substances 0.000 description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910004261 CaF 2 Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- 235000015393 sodium molybdate Nutrition 0.000 description 2
- 239000011684 sodium molybdate Substances 0.000 description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- XACAZEWCMFHVBX-UHFFFAOYSA-N [C].[Mo] Chemical compound [C].[Mo] XACAZEWCMFHVBX-UHFFFAOYSA-N 0.000 description 1
- ANFIEGWCRSNVFS-UHFFFAOYSA-N [Na].OCl(=O)=O Chemical compound [Na].OCl(=O)=O ANFIEGWCRSNVFS-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- PTXMVOUNAHFTFC-UHFFFAOYSA-N alumane;vanadium Chemical compound [AlH3].[V] PTXMVOUNAHFTFC-UHFFFAOYSA-N 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- UIFOTCALDQIDTI-UHFFFAOYSA-N arsanylidynenickel Chemical compound [As]#[Ni] UIFOTCALDQIDTI-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005363 electrowinning Methods 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- -1 handstone Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for comprehensively recovering multiple metals of a waste catalyst. Firstly, the waste catalyst is presoaked and ground by dilute sulphuric acid, presoaked slag is cured by concentrated sulphuric acid, cured materials are leached by water or presoaking liquid, and the leaching rate of vanadium is more than 85 percent and the leaching rate of aluminum is less than 10 percent in the whole selective vanadium extraction process. After vanadium extraction, slag is subjected to pyrometallurgical smelting by adding a proper flux, so that the separation of valuable metals such as nickel, cobalt, molybdenum and the like from impurities such as aluminum, silicon and the like is realized. The nickel cobalt and the molybdenum in the pyrometallurgical smelting matte phase can be further separated through pressure acid leaching, and the molybdenum can be recovered through ammonia leaching. The process firstly adopts a selective leaching method to recover vanadium, avoids the separation of vanadium and aluminum, fully utilizes the heat value of residual organic matters in the waste catalyst in the pyrometallurgical smelting process, saves energy consumption, avoids the leaching of aluminum in the traditional process and saves the consumption of a leaching agent.
Description
Technical field
The invention belongs to catalyzer secondary resource recovery technology field, be specifically related to a kind of method of many metals of spent catalyst comprehensive reutilization.
Background technology
Metals such as vanadium, molybdenum, tungsten are normal and be called refractory metal.Have good ductility, matter is hard, the performance of salt tolerant acid and sulfuric acid, and better than most of stainless steels in the performance of gasproof-salt-aqueous corrosion, because these metals have variable valence state, be catalyzer raw material rare in the chemical industry simultaneously.Therefore, these elements have purposes very widely in the industry of metallurgy, chemical industry, iron and steel.Along with the high speed development of China's modernization construction, the demand of this metalloid is increasing.
Nickel has ferromagnetic metallic element, and it can high polish and anticorrosive.Be mainly used in alloy (as nickel steel and nickeline) and as catalyzer (as Raney nickel, refer to being used as the catalyzer of hydrogenation especially), can be used to make currency etc., be plated in and prevent from other metals getting rusty.
Above-mentioned metal distributes at occurring in nature and all relatively disperses, and the raw ore ore grade is lower, and along with the continuous increase of produced quantity, minable ore grade is more and more lower, so cost of winning constantly increases.And a large amount of spent catalyst becomes the rare secondary resource of these metals in petroleum industry and the chemical industry.Spent catalyst is compared with the nature ore has characteristics such as of high grade, that composition is simple.The method that reclaims at present metals such as nickel, cobalt, molybdenum, vanadium from spent catalyst mainly is alkali roasting (or blank roasting) → water logging (alkali soaks) method or acid, two step of alkali lixiviation process, metallic element in the spent catalyst is converted into soluble salt enters solution, solution separates the acquisition metal of purifying again.
Application number is the Chinese patent application of CN201110147614.9, has announced a kind of nickeliferous spent catalyst recoverying and utilizing method that relates to.This method is calcined nickeliferous spent catalyst, and temperature 300-600 ℃, time 2-3 hour, the organism of removal catalyst residue; Then it is pulverized, adopt the nitric acid two-stage of concentration 1.5-4.5mol/L to leach.The nickel that this method reclaims exists with the nickel nitrate solution form.
Application number is the Chinese patent application of CN200910188100.0, announced a kind of method that from molybdenum-contained waste catalyst, reclaims metal, at first with spent catalyst oil removing, pulverizing, mix with soda ash then, roasting, water leaches after the roasting, adopts organic extractant recovery molybdenum wherein, utilizes the spent acid preparation mixed acid solution that discharges in this method, for the treatment of the solid residue after the water logging, further reclaim the metal in spent acid and the residue.This inventive method can further improve the rate of recovery of metal in the spent catalyst, and the operational condition severity reduces simultaneously, and energy consumption is low, goes for the metal recovery process of molybdenum-contained waste catalyst.
Application number is the Chinese patent application of CN200910020761.2, has announced a kind of method that reclaims molybdenum from the alumina base molybdenum-contained waste catalyst, and carry out according to the following step successively: (1) is with alumina base molybdenum-contained waste catalyst and circulating mother liquor, NaOH solution and Na
2CO
3Go into the ball mill combined grinding after the batching, calcine grog, stir stripping with adjusting liquid, dissolution fluid is implemented solid-liquid separation, gets crude liquor of sodium aluminate; (2) with after the crude liquor of sodium aluminate dilution, implement the carbonating branch and solve aluminum hydroxide slurry; Slurries get low-grade aluminium hydroxide and contain the molybdenum carbon mother liquid after separating; (3) the high concentration carbon acid sodium solution is introduced carbonating tower and implemented the carbonating decomposition; Yellow soda ash and carbonic acid gas, water are separated out the sodium bicarbonate crystallization after further reacting, and form the sodium bicarbonate slurries; The sodium bicarbonate slurries are after sedimentation and thickening, and filtering separation obtains solid sodium bicarbonate and contains the molybdenum carbonization mother liquor; (4) contain the molybdenum carbonization mother liquor through the steam heating decomposition of wetting, evaporate after the sodium bicarbonate thermolysis in the solution is converted to yellow soda ash; (5) through (1) to (4) step cycle, adjust pH value back and extract molybdenum with ion exchange method.
Application number is the Chinese patent application of CN200710303806.8, announced a kind of dissolution processing method of nickelous oxide dead catalyst, it is characterized in that its dissolution process process is sieve to be removed the nickelous oxide dead catalyst of lumpy materials such as handstone, slag, adding concentration is in the above hydrochloric acid soln of 5N/L, under 85 ℃ of-100 ℃ of temperature, stirring condition, add oxygenant chloric acid sodium or feed chlorine, the control oxidizing potential is 0.5-1.0V; Carried out solubilizing reaction 1-5 hour, and obtained green nickel chloride solution.The method of this invention, leaching and dissolution rate height do not need to carry out pyroprocessing and pressure treatment has reduced cost, have solved a production technology difficult problem.In conjunction with existing nickel electrowinning technology, the nickel in can the efficient recovery spent catalyst.
Application number is the Chinese patent application of CN200410050503.6, announced a kind of method of utilizing vanadium-containing wasting catalyst to produce Vanadium Pentoxide in FLAKES, this method is: remove a certain amount of deposition oil in the catalyzer earlier, put in the water after then it being pulverized and leach, by oxidation and add alkali and regulate pH value 8.5-9.5, at 50-60 ℃ of following extraction time 1-2 hour, recovery vanadic acid sodium and sodium molybdate solution were a leach liquor after the solid-liquid separation; Filter residue after the washing is calcined in rotary kiln, 850～900 ℃ of temperature of kiln head, and 350～400 ℃ on kiln tail makes the vanadium transformation efficiency greater than 96%; Material after the calcining is soluble in water, stirs down and leaches, and recovery vanadic acid sodium and sodium molybdate solution are the secondary leach liquor after solid-liquid separation; Merge leach liquor, remove foreign matter of phosphor again, add excessive ammonium chloride in the leach liquor after will purifying under the normal temperature, make vanadic acid sodium generate the ammonium meta-vanadate precipitation, ammonium meta-vanadate after the solid-liquid separation is put in the film-making stove, decompose the V2O5 that makes fusion at 800～850 ℃ of following ammonium vanadate, make sheet through the film-making stove and be finished product.These invention characteristics are that the sulphur in the spent catalyst is deviate from by the method for oxidation dipping, by deviating from the part oil composition in the spent catalyst, reduce the flue-gas temperature of calcining kiln kiln tail.
Aforesaid method says that on the whole resource recovery is low, and it is serious that renewable resource not easy to be recycled or that economic worth is low abandon phenomenon.
Summary of the invention
The objective of the invention is the deficiency at aforementioned technology, a kind of wide adaptability is provided, save leaching agent, the spent catalyst treatment technology of the comprehensive utilization energy.
Purpose of the present invention is achieved through the following technical solutions:
The comprehensive method that reclaims of the many metals of a kind of spent catalyst is characterized in that,
A: when the content of vanadium in the spent catalyst 0.5% when above, may further comprise the steps:
(1) dilute sulphuric acid preimpregnation: spent catalyst is placed the stirring mill, add dilute sulphuric acid, levigate, preimpregnation;
(2) slaking water logging: with preimpregnation slag vitriol oil slaking in the step (1), add fluorochemical in the maturing process as additive, promote dissociating between element, the vanadium extraction of water logging selectivity obtains the Vanadium Pentoxide in FLAKES product after the slaking;
(3) pyrometallurgical smelting: vanadium making slag in the step (2) is carried out pyrometallurgical smelting, reclaim nickel, cobalt, molybdenum, nickel, cobalt, molybdenum are gone into sulfonium, and impurity such as aluminium, silicon are gone into slag;
(4) pressurization is leached: the sulfonium phase pressurized acid leaching that obtains in the step (3), reclaim nickel, cobalt, and obtain single nickel salt, rose vitriol product;
(5) ammonia lixiviate molybdenum: adopt ammonia to soak the recovery molybdenum leached mud that obtains in the step (4), obtain the ammonium molybdate product;
B: when the content of vanadium in the spent catalyst was lower than 0.5%, spent catalyst directly entered step (3) pyrometallurgical smelting successively, (4) pressurization is leached and (5) ammonia lixiviate molybdenum.
The content ratio that relates among the present invention (per-cent), unless otherwise indicated beyond, be mass ratio.
Further, spent catalyst preimpregnation and levigate while carry out in grinding stirring in the step (1), and the preimpregnation liquid-solid ratio is 2-10:1, and the preimpregnation temperature is normal temperature-90 ℃, and preimpregnation acidity is 20g/L-150g/L.
Further, step (2) maturing process fluoride additive is CaF
2
Further, slaking is the 15-30% of weight of material with the acid amount in the step (2), and curing temperature 80-150 ℃, the curing time is 12h-48h, addition of C aF in the maturing process
2Add-on be the 1-10% of raw catalyst quality.
Further, step (3) is allocated silicon-dioxide and reduced iron powder in vanadium making slag before pyrometallurgical smelting.
Further, middle melting temperature range 1200-1500 ℃ of step (3), smelting time is 0.5h-2h.
The present invention compares with existing technology and has the following advantages and effect:
1. selectivity vanadium extraction by add additive in maturing process, has realized the purpose of metals such as single stage method separation vanadium and aluminium, molybdenum, nickel, cobalt.In the whole selectivity vanadium extraction process, the leaching yield of vanadium is greater than 85%, and the leaching yield of aluminium is lower than 10%, has avoided aluminium vanadium separation problem in the prior art, has saved corresponding flow process and cost.
2. if the content of vanadium in the former spent catalyst is lower, do not have the value of recycling, then selectivity vanadium extraction link can be omitted in this technology, directly enters subsequent technique, so technology of the present invention has adaptability widely.
3. pyrometallurgical smelting takes full advantage of the thermal value of the residual organic matter in the spent catalyst, has saved the energy, owing to separated aluminium and nickel, cobalt, molybdenum by the method for pyrometallurgical smelting, compares the leaching agent consumption when having avoided aluminium to be leached with traditional technology.
Description of drawings
Fig. 1 is process flow sheet of the present invention.
Embodiment
Below in conjunction with accompanying drawing the present invention is further specified.
Content according to vanadium in the spent catalyst determines whether to carry out selectivity leaching vanadium process: if content of vanadium is more than 0.5% in the spent catalyst, then carry out selectivity and leach the vanadium process, otherwise spent catalyst directly enters the pyrometallurgical smelting process.
If the content of vanadium may further comprise the steps more than 0.5% in the spent catalyst:
(1) dilute sulphuric acid preimpregnation: spent catalyst is placed the stirring mill, add dilute sulphuric acid, levigate, preimpregnation.
(2) slaking water logging: with preimpregnation slag vitriol oil slaking in the step (1), adding fluorochemical in the maturing process (can be NaF, KF, CaF
2, preferred CaF
2) as additive, promote dissociating between element.Slaking is the 15-30% of weight of material with the acid amount, and curing temperature 80-150 ℃, the curing time is 12h-48h, addition of C aF in the maturing process
2Add-on be the 1-10% of raw catalyst quality.Water logging selectivity vanadium extraction after the slaking, leach liquor obtains the Vanadium Pentoxide in FLAKES product after the metallurgical means purification and impurity removal of routine, separation.In the whole selectivity vanadium extraction process, the leaching yield of vanadium is greater than 85%, and the leaching yield of aluminium is lower than 10%.
(3) pyrometallurgical smelting: vanadium making slag in the step (2) is carried out pyrometallurgical smelting, reclaim nickel, cobalt, molybdenum, nickel, cobalt, molybdenum are gone into sulfonium, and impurity such as aluminium, silicon are gone into slag.
(4) pressurization is leached: the sulfonium phase pressurized acid leaching that obtains in the step (3), reclaim nickel, cobalt, and obtain single nickel salt, rose vitriol product.
(5) ammonia lixiviate molybdenum: adopt ammonia to soak the recovery molybdenum leached mud that obtains in the step (4), obtain the ammonium molybdate product.
If the content of vanadium is lower than 0.5% in the spent catalyst, then spent catalyst directly enters step (3) pyrometallurgical smelting, carries out subsequent step (4) pressurization then and leaches and step (5) ammonia lixiviate molybdenum.
Embodiment 1:
Fetch the high-nickel catalyst 1000g from certain petrochemical plant, adopt the sulfuric acid preimpregnation of liquid-solid ratio 5:1,100g/L in stirring mill, the preimpregnation slag adopts the adding vitriol oil to carry out slaking, slag acid mass ratio 4:1,106 ℃ of curing temperatures, curing time 48h.The slaking slag leaches with presoak, and extraction temperature is 80 ℃, extraction time 4h.After preimpregnation, the slaking water logging, the leaching yield of vanadium is 88.0%, and the leaching yield of aluminium is 9.3%.The leached mud that obtains is allocated silicon-dioxide and reduced iron powder into, at 1350 ℃ of following melting 2h, obtains sulfonium and slag item, and the sulfonium rate of going into of nickel, cobalt, molybdenum is respectively 90%, 89%, 82%.Sulfonium obtains nickel, cobalt, molybdenum product according to the metallurgical means of routine.
Embodiment 2:
Fetch the high cobalt spent catalyst 1000g from certain petroleum chemical enterprise, content of vanadium is very low in this catalyzer, does not have to recycle to be worth, and therefore directly carries out pyrometallurgical smelting, according to the concrete composition of catalyzer, allocate 280g silicon-dioxide into, the 420g reduced iron powder is at 1350 ℃ of following melting 2h, obtain sulfonium and slag phase, the sulfonium rate of going into of nickel, cobalt, molybdenum is respectively 94%, 95%, 79%.Sulfonium obtains nickel, cobalt, molybdenum product according to the metallurgical means of routine.
Claims (6)
1. the comprehensive method that reclaims of the many metals of spent catalyst is characterized in that,
A: when the content of vanadium in the spent catalyst 0.5% when above, may further comprise the steps:
(1) dilute sulphuric acid preimpregnation: spent catalyst is placed the stirring mill, add dilute sulphuric acid, levigate, preimpregnation;
(2) slaking water logging: with preimpregnation slag vitriol oil slaking in the step (1), add fluorochemical in the maturing process as additive, promote dissociating between element, the vanadium extraction of water logging selectivity obtains the Vanadium Pentoxide in FLAKES product after the slaking;
(3) pyrometallurgical smelting: vanadium making slag in the step (2) is carried out pyrometallurgical smelting, reclaim nickel, cobalt, molybdenum, nickel, cobalt, molybdenum are gone into sulfonium, and impurity such as aluminium, silicon are gone into slag;
(4) pressurization is leached: the sulfonium phase pressurized acid leaching that obtains in the step (3), reclaim nickel, cobalt, and obtain single nickel salt, rose vitriol product;
(5) ammonia lixiviate molybdenum: adopt ammonia to soak the recovery molybdenum leached mud that obtains in the step (4), obtain the ammonium molybdate product;
B: when the content of vanadium in the spent catalyst is lower than 0.5%, spent catalyst is directly entered step (3) pyrometallurgical smelting, enter step (4) pressurization then successively and leach and step (5) ammonia lixiviate molybdenum.
2. method according to claim 1 is characterized in that, spent catalyst preimpregnation and levigate while carry out in grinding stirring in the step (1), and the preimpregnation liquid-solid ratio is 2-10:1, and the preimpregnation temperature is normal temperature-90 ℃, and preimpregnation acidity is 20g/L-150g/L.
3. method according to claim 1 is characterized in that, fluoride additive is CaF described in the step (2)
2
4. method according to claim 3 is characterized in that, slaking is the 15-30% of weight of material with the acid amount in the step (2), and curing temperature 80-150 ℃, the curing time is 12h-48h, addition of C aF in the maturing process
2Add-on be the 1-10% of raw catalyst quality.
5. method according to claim 1 is characterized in that, step (3) is allocated silicon-dioxide and reduced iron powder in vanadium making slag before pyrometallurgical smelting.
6. method according to claim 1 is characterized in that, middle melting temperature range 1200-1500 ℃ of step (3), and smelting time is 0.5h-2h.
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