CN114635032B - Comprehensive recycling method of waste catalyst - Google Patents
Comprehensive recycling method of waste catalyst Download PDFInfo
- Publication number
- CN114635032B CN114635032B CN202210174776.XA CN202210174776A CN114635032B CN 114635032 B CN114635032 B CN 114635032B CN 202210174776 A CN202210174776 A CN 202210174776A CN 114635032 B CN114635032 B CN 114635032B
- Authority
- CN
- China
- Prior art keywords
- filtrate
- leaching
- acid
- recovering
- filtering
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 48
- 239000002699 waste material Substances 0.000 title claims abstract description 37
- 238000004064 recycling Methods 0.000 title claims abstract description 14
- 238000002386 leaching Methods 0.000 claims abstract description 50
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000002253 acid Substances 0.000 claims abstract description 40
- 239000000706 filtrate Substances 0.000 claims abstract description 38
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 35
- 238000001914 filtration Methods 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 25
- 238000011084 recovery Methods 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000605 extraction Methods 0.000 claims abstract description 22
- 238000005342 ion exchange Methods 0.000 claims abstract description 21
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 21
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 20
- 239000010941 cobalt Substances 0.000 claims abstract description 20
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 20
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 11
- 230000001376 precipitating effect Effects 0.000 claims abstract description 11
- 239000002893 slag Substances 0.000 claims abstract description 10
- 239000012535 impurity Substances 0.000 claims abstract description 9
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims abstract description 7
- 229940044175 cobalt sulfate Drugs 0.000 claims abstract description 7
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims abstract description 7
- 238000001179 sorption measurement Methods 0.000 claims abstract description 7
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 claims abstract description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229910052573 porcelain Inorganic materials 0.000 claims abstract description 6
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 24
- 238000000926 separation method Methods 0.000 claims description 15
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 235000021110 pickles Nutrition 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 10
- 150000002739 metals Chemical class 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052721 tungsten Inorganic materials 0.000 claims description 7
- 239000010937 tungsten Substances 0.000 claims description 7
- 229910001385 heavy metal Inorganic materials 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 239000000047 product Substances 0.000 abstract description 5
- 239000002351 wastewater Substances 0.000 abstract description 5
- 238000007654 immersion Methods 0.000 abstract description 2
- NWJUARNXABNMDW-UHFFFAOYSA-N tungsten vanadium Chemical compound [W]=[V] NWJUARNXABNMDW-UHFFFAOYSA-N 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 6
- 238000007670 refining Methods 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000001110 calcium chloride Substances 0.000 description 4
- 229910001628 calcium chloride Inorganic materials 0.000 description 4
- 239000003546 flue gas Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000012716 precipitator Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- -1 ferrous metals Chemical class 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- CZIMGECIMULZMS-UHFFFAOYSA-N [W].[Na] Chemical compound [W].[Na] CZIMGECIMULZMS-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000003181 co-melting Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical group [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- KAEAMHPPLLJBKF-UHFFFAOYSA-N iron(3+) sulfide Chemical compound [S-2].[S-2].[S-2].[Fe+3].[Fe+3] KAEAMHPPLLJBKF-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000010814 metallic waste Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000002912 waste gas Substances 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B15/00—Other processes for the manufacture of iron from iron compounds
-
- 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
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
- C22B11/048—Recovery of noble metals from waste materials from spent catalysts
-
- 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
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0069—Leaching or slurrying with acids or salts thereof containing halogen
-
- 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
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/0423—Halogenated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
- C22B34/225—Obtaining vanadium from spent catalysts
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/34—Obtaining molybdenum
- C22B34/345—Obtaining molybdenum from spent catalysts
-
- 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
- C22B34/365—Obtaining tungsten from spent catalysts
-
- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geochemistry & Mineralogy (AREA)
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for comprehensively recycling a waste catalyst, which comprises the following steps: (1) taking a certain amount of waste catalyst to remove porcelain balls; (2) roasting and deoiling: (3) roasting the mixed materials; (4) water immersion: leaching with cold water for 2 hours, and filtering to obtain filter residue a and filtrate b; (5) acidifying the filtrate b to remove impurities; (6) recovering tungsten vanadium: recovering valuable metal by adopting an ion exchange adsorption method, adding acid and hydrogen peroxide to adjust the pH value to 2-3, precipitating tungstic acid, reducing vanadium, remaining in the solution, and extracting vanadium by using N235; (7) Taking the filter residue a in the step (4) for high-temperature acid leaching to obtain leaching residues and acid leaching liquid, (8) recovering noble metals; (9) recovering nickel and cobalt: filtering and crystallizing the back extraction liquid to obtain cobalt sulfate and nickel sulfate. The invention has low cost and high product purity, and no secondary slag pollution and secondary wastewater are generated, and the total recovery rate reaches more than 95 percent.
Description
Technical Field
The invention relates to the technical field of metallurgy, in particular to a method for comprehensively recycling a waste catalyst.
Background
The waste SCR catalyst contains toxic oxides such as V2O5 and WO3 (or MoO 3), is mixed with heavy metal substances with dangerous characteristics such as arsenic, mercury and lead in coal-fired fly ash, risks are presented to human health and environment, the waste SCR catalyst is qualitatively used as dangerous waste in Europe, although the waste SCR denitration catalyst is not listed into dangerous waste for management by the United states EPA, the national environmental protection department pollution prevention and prevention unit can be the same with the national institute of environmental science and technology (SOS) solid waste pollution control technology in the entrusted department of solid waste and chemical management technology and the like in the institute of China, and the investigation and the approval of the waste flue gas denitration catalyst dangerous waste management license are studied to standardize the approval work of the waste flue gas denitration catalyst management license, promote the overall level of regeneration and utilization of the waste flue gas denitration catalyst, and prevent secondary pollution to the environment in the regeneration and utilization process of the waste flue gas denitration catalyst. The current research on recycling of the oil refining spent catalyst can improve the resource utilization rate and avoid the environmental pollution caused by the spent catalyst by comprehensively recycling the oil refining spent catalyst. The project further subdivides the oil refining spent catalyst into catalytic cracking, hydrotreating and catalytic reforming catalysts, and reviews the recycling technology of the three spent catalysts, thereby providing a certain reference for the development of the recycling of the Chinese petroleum spent catalyst in the direction of harmlessness and reclamation. According to the data of the national statistical bureau, the apparent consumption of Chinese petroleum in 2018 is firstly 6 hundred million tons, reaching 6.25 hundred million tons, and the equivalent increase is 0.41 hundred million tons, and the speed increase is 7%; it is expected that the domestic refinery will have a capacity of over 9 million tons per year by 2020. According to the standard measurement and calculation of the domestic oil refining industry, 0.354kg of waste catalyst is produced in each ton of crude oil refining, and 15-20 ten thousand tons of waste catalyst are produced in China each year on the basis of the waste catalyst.
The old technology (shown in figure 2) in the prior art generally adopts a noble metal waste catalyst recovery research high Wen Liu smelting method to recover noble metal, and the noble metal materials are crushed and ground to below 20 meshes according to the following steps of 1: adding a capturing agent such as Pb, pbS, cuS2 and lime according to the proportion of 0.7, controlling the S content of the mixture to be less than 5 percent, controlling the water content to be less than 15 percent, then solidifying at high pressure, air-drying, adding coke into an electric arc furnace in batches, and co-melting copper sulfide and ferric sulfide together in a weak oxidizing atmosphere at 1400-1450 ℃ to generate sulfonium, wherein the sulfonium captures noble metals. The final platinum group metal can be enriched by more than 10 times in alloy and sulfonium, and the direct yield is about 85%. The noble metal is recovered by adopting a smelting technology of a plasma furnace, the spent automobile catalyst (the carrier is cordierite 2MgO.2Al2O3.5SiO2), 10 percent of CaO is added to form CaO-Al2O3-SiO2 ternary slag phase, the melting point of the slag phase is reduced, fe3O4 is taken as a collecting raw material, coke is taken as a reducing agent, and smelting is carried out at 1500-1600 ℃, however, the recovery rate of platinum b and palladium [ b (n) is only 90 percent, and the recovery rate of rhodium l and rhodium l (n) is up to 90 percent at most.
The recovery rate of noble metal in the waste catalyst is lower than 95% by adopting high Wen Huofa, the recovery is incomplete, and meanwhile, high Wen Huofa can cause a large amount of waste gas pollution, and high Wen Huofa recovery is difficult to meet the environmental protection requirement.
The main components of the waste industrial catalyst are dissolved by acid or alkali or other solvents, the filtrate is separated after impurity removal and purification, so that sulfide or metal hydroxide which is difficult to dissolve in water can be obtained, and the final product is further processed according to the requirement after drying. Spent catalysts such as noble metal catalysts, hydrodesulfurization catalysts, copper-based and nickel nie-based catalysts are generally recovered by wet methods. Electrolytic processes are also typically included in the wet process. The waste catalyst is treated by a wet method, the carrier of the waste catalyst often exists in the form of insoluble residues, if no proper treatment method is adopted, a large amount of solid waste can cause secondary pollution, and if the carrier is dissolved together with metal, the separation of the metal and the carrier can generate a large amount of waste liquid which is easy to cause secondary pollution. After the main components of the waste catalyst are dissolved, different components in the immersion liquid are separated and purified by adopting an anion-cation exchange resin adsorption method or an extraction and back extraction method, which is the key point of the study of wet recovery.
Disclosure of Invention
The invention aims to provide a method for comprehensively recycling a waste catalyst.
The technical scheme for realizing the aim of the invention is as follows: a method for comprehensively recycling waste catalyst comprises the following steps:
(1) Taking a certain amount of waste catalyst to remove porcelain balls;
(2) Roasting and deoiling: taking deoiled crushed materials, adding alkali for oxidizing roasting at the roasting temperature of 700 ℃ for 2 hours;
(3) Roasting the mixed materials;
(4) Soaking in water: leaching with cold water for 2 hours, and filtering to obtain filter residue a and filtrate b;
(5) Acidifying and impurity removing the filtrate b: adding acid into the filtrate b to adjust the pH value to 9-10, and then adding magnesium chloride to remove silicon aluminum;
(6) Recovering tungsten and vanadium: recovering valuable metal by adopting an ion exchange adsorption method, adding acid and hydrogen peroxide to adjust the pH value to 2-3, precipitating tungstic acid, reducing vanadium, keeping the vanadium in solution, extracting vanadium by using N235, and crystallizing to obtain tungsten sodium molybdate crystals;
(7) Taking the filter residue a in the step (4) for high-temperature acid leaching to obtain leaching residues and acid leaching liquid,
(8) Recovery of noble metals: iron removal and extraction are carried out on the pickle liquor, the pickle liquor adopts ion exchange separation to adsorb noble metals, and the nonferrous metals such as iron, nickel, cobalt and copper are recovered by extraction separation; filtering the raffinate after precipitation to obtain filter residue c and filtrate d, wherein the filter residue c is used for producing carbonate, and the filtrate d enters the step (4) for secondary water leaching;
(9) Recovering nickel and cobalt: filtering the back extraction liquid for crystallization, extracting and separating nickel and cobalt from the filtrate by using P507, precipitating and concentrating to obtain cobalt sulfate and nickel sulfate, and crystallizing to obtain nickel and cobalt sulfate crystals.
Preferably, the specific method of high-temperature acid leaching in the step (7) comprises the following steps: acidify with 2:1 hydrochloric acid for 4 hours at 60 ℃. Filtering to remove acid slag, and regulating pH of the filtrate to 2-3.
Preferably, the specific method for recovering noble metals in the step (8) is as follows: adding a noble metal precipitator according to the heavy metal content of 1:1.1, and filtering to obtain the noble metal mixed metal.
By adopting the technical scheme, the invention has the following beneficial effects: (1) The process adopts a full-solution process, the components in the waste catalyst are leached and recycled in a segmented way, the carriers are divided into a silica carrier and an alumina carrier according to different catalyst types, the silica carrier adopts high-temperature oxidation acid leaching after oxidation roasting, the alumina carrier adopts alkali roasting water leaching to remove aluminum, and leaching residues are subjected to low-temperature acid leaching. Acidifying alkali leaching solution to remove impurities, recovering valuable metals such as tungsten, molybdenum, vanadium and the like by ion exchange, and recovering aluminum from tail liquid. The pickle liquor adopts ion exchange separation to adsorb noble metals, and non-ferrous metals such as iron, nickel, cobalt, copper and the like are recovered by extraction separation. And (3) after the tail liquid lime is neutralized, calcium chloride is distilled and recovered, and cooling water is recycled, so that secondary slag pollution and secondary wastewater are not generated any more. The method adopts ion exchange to recycle valuable elements, has low cost and high product purity, and different products adopt different exchange resins to recycle different elements selectively. Under the condition of ensuring the leaching rate, the ion exchange resin is adopted for recovery, so that good recovery rate can be obtained, and the total recovery rate reaches more than 95%.
(2) The process is mainly characterized in that all powder is transferred into solution through alkali-melting acid leaching, valuable metals in the powder are recovered through chemical treatment means (precipitation, ion exchange and extraction), base metals are precipitated through means of neutralization precipitation and the like, waste water is distilled to recover calcium chloride, and water is recycled. The leaching pH value is controlled to be 9-10, and the precious metal is recovered by ion exchange after acidification with 1mol/L sulfuric acid to pH value of 2-3. And (5) extracting the tail liquid to recover nickel and cobalt. The process is simple and the recovery rate is high.
Drawings
In order that the invention may be more readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings, in which
FIG. 1 is a schematic flow chart of the present invention;
FIG. 2 is a flow chart of the prior art old process.
Detailed Description
Example 1
Referring to fig. 1, the method for comprehensively recycling the waste catalyst in the embodiment comprises the following steps:
(1) Taking a certain amount of waste catalyst to remove porcelain balls;
(2) Roasting and deoiling: taking deoiled crushed materials, adding alkali for oxidizing roasting at the roasting temperature of 700 ℃ for 2 hours;
(3) Roasting the mixed materials;
(4) Soaking in water: leaching with cold water for 2 hours, and filtering to obtain filter residue a and filtrate b;
(5) Acidifying and impurity removing the filtrate b: adding acid into the filtrate b to adjust the pH value to 9-10, and then adding magnesium chloride to remove silicon aluminum;
(6) Recovering tungsten and vanadium: recovering valuable metal by adopting an ion exchange adsorption method, adding acid and hydrogen peroxide to adjust the pH value to 2-3, precipitating tungstic acid, reducing vanadium, remaining in the solution, and extracting vanadium by using N235;
(7) Taking the filter residue a in the step (4) for high-temperature acid leaching to obtain leaching residues and acid leaching liquid,
(8) Recovery of noble metals: iron removal and extraction are carried out on the pickle liquor, the pickle liquor adopts ion exchange separation to adsorb noble metals, and the nonferrous metals such as iron, nickel, cobalt and copper are recovered by extraction separation; filtering the raffinate after precipitation to obtain filter residue c and filtrate d, wherein the filter residue c is used for producing carbonate, and the filtrate d enters the step (4) for secondary water leaching;
(9) Recovering nickel and cobalt: filtering and crystallizing the back extraction liquid, extracting and separating nickel and cobalt from the filtrate by using P507, and precipitating and concentrating to obtain cobalt sulfate and nickel sulfate.
The specific method of high-temperature acid leaching in the step (7) comprises the following steps: acidify with 2:1 hydrochloric acid for 4 hours at 60 ℃. Filtering to remove acid slag, and regulating pH of the filtrate to 2-3.
The specific method for recovering noble metals in the step (8) comprises the following steps: adding a noble metal precipitator according to the heavy metal content of 1:1.1, and filtering to obtain the noble metal mixed metal.
The process is mainly characterized in that all powder is transferred into solution through alkali-melting acid leaching, valuable metals in the powder are recovered through chemical treatment means (precipitation, ion exchange and extraction), base metals are precipitated through means of neutralization precipitation and the like, waste water is distilled to recover calcium chloride, and water is recycled.
The leaching pH value is controlled to be 9-10, and the precious metal is recovered by ion exchange after acidification with 1mol/L sulfuric acid to pH value of 2-3. And (5) extracting the tail liquid to recover nickel and cobalt. The process is simple and the recovery rate is high.
The process adopts a full-solution process, the components in the waste catalyst are leached and recycled in a segmented way, the carriers are divided into a silica carrier and an alumina carrier according to different catalyst types, the silica carrier adopts high-temperature oxidation acid leaching after oxidation roasting, the alumina carrier adopts alkali roasting water leaching to remove aluminum, and leaching residues are subjected to low-temperature acid leaching. Acidifying alkali leaching solution to remove impurities, recovering valuable metals such as tungsten, molybdenum, vanadium and the like by ion exchange, and recovering aluminum from tail liquid. The pickle liquor adopts ion exchange separation to adsorb noble metals, and non-ferrous metals such as iron, nickel, cobalt, copper and the like are recovered by extraction separation. And (3) after the tail liquid lime is neutralized, calcium chloride is distilled and recovered, and cooling water is recycled, so that secondary slag pollution and secondary wastewater are not generated any more. The method adopts ion exchange to recycle valuable elements, has low cost and high product purity, and different products adopt different exchange resins to recycle different elements selectively. Under the condition of ensuring the leaching rate, the ion exchange resin is adopted for recovery, so that good recovery rate can be obtained, and the total recovery rate reaches more than 95%.
Example two
A method for comprehensively recycling a waste catalyst is characterized by comprising the following steps: the method comprises the following steps:
(1) Taking a certain amount of waste catalyst to remove porcelain balls;
(2) Roasting and deoiling: taking deoiled crushed materials, adding alkali for oxidizing roasting at the roasting temperature of 650 ℃ for 2 hours;
(3) Roasting the mixed materials;
(4) Soaking in water: leaching with cold water for 1.8 hr, and filtering to obtain residue a and filtrate b;
(5) Acidifying and impurity removing the filtrate b: adding acid into the filtrate b to adjust the pH value to 9, and then adding magnesium chloride to remove silicon aluminum;
(6) Recovering tungsten and vanadium: recovering valuable metal by adopting an ion exchange adsorption method, adding acid and hydrogen peroxide to adjust the pH value to 2-3, precipitating tungstic acid, reducing vanadium, remaining in the solution, and extracting vanadium by using N235;
(7) Taking the filter residue a in the step (4) for high-temperature acid leaching to obtain leaching residues and acid leaching liquid,
(8) Recovery of noble metals: iron removal and extraction are carried out on the pickle liquor, the pickle liquor adopts ion exchange separation to adsorb noble metals, and the nonferrous metals such as iron, nickel, cobalt and copper are recovered by extraction separation; filtering the raffinate after precipitation to obtain filter residue c and filtrate d, wherein the filter residue c is used for producing carbonate, and the filtrate d enters the step (4) for secondary water leaching;
(9) Recovering nickel and cobalt: filtering and crystallizing the back extraction liquid, extracting and separating nickel and cobalt from the filtrate by using P507, and precipitating and concentrating to obtain cobalt sulfate and nickel sulfate.
The specific method of high-temperature acid leaching in the step (7) comprises the following steps: acidify with 2:1 hydrochloric acid for 4 hours at 55 degrees. Filtering to remove acid slag, and regulating pH of the filtrate to 2-3.
The specific method for recovering noble metals in the step (8) comprises the following steps: adding a noble metal precipitator according to the heavy metal content of 0.8:1.1, and filtering to obtain the noble metal mixed metal.
The overall recovery of this example was up to 95.5%.
Example III
A method for comprehensively recycling a waste catalyst is characterized by comprising the following steps: the method comprises the following steps:
(1) Taking a certain amount of waste catalyst to remove porcelain balls;
(2) Roasting and deoiling: taking deoiled crushed materials, adding alkali for oxidizing roasting, wherein the roasting temperature is 750 ℃ and the time is 3 hours;
(3) Roasting the mixed materials;
(4) Soaking in water: leaching with cold water for 2.5 hours, and filtering to obtain filter residue a and filtrate b;
(5) Acidifying and impurity removing the filtrate b: adding acid into the filtrate b to adjust the pH value to 9-10, and then adding magnesium chloride to remove silicon aluminum;
(6) Recovering tungsten and vanadium: recovering valuable metal by adopting an ion exchange adsorption method, adding acid and hydrogen peroxide to adjust the pH value to 2-3, precipitating tungstic acid, reducing vanadium, remaining in the solution, and extracting vanadium by using N235;
(7) Taking the filter residue a in the step (4) for high-temperature acid leaching to obtain leaching residues and acid leaching liquid,
(8) Recovery of noble metals: iron removal and extraction are carried out on the pickle liquor, the pickle liquor adopts ion exchange separation to adsorb noble metals, and the nonferrous metals such as iron, nickel, cobalt and copper are recovered by extraction separation; filtering the raffinate after precipitation to obtain filter residue c and filtrate d, wherein the filter residue c is used for producing carbonate, and the filtrate d enters the step (4) for secondary water leaching;
(9) Recovering nickel and cobalt: filtering and crystallizing the back extraction liquid, extracting and separating nickel and cobalt from the filtrate by using P507, and precipitating and concentrating to obtain cobalt sulfate and nickel sulfate.
The specific method of high-temperature acid leaching in the step (7) comprises the following steps: acidify with 2:1 hydrochloric acid for 4 hours at 70 ℃. Filtering to remove acid slag, and regulating pH of the filtrate to 2-3.
The specific method for recovering noble metals in the step (8) comprises the following steps: according to the heavy metal content, the weight ratio is 1:1.2 adding a noble metal precipitator, and filtering to obtain noble metal mixed metal.
The overall recovery of this example was up to 95.8%.
While the foregoing is directed to embodiments of the present invention, other and further details of the invention may be had by the present invention, it should be understood that the foregoing description is merely illustrative of the present invention and that no limitations are intended to the scope of the invention, except insofar as modifications, equivalents, improvements or modifications are within the spirit and principles of the invention.
Claims (1)
1. A method for comprehensively recycling a waste catalyst is characterized by comprising the following steps: the method comprises the following steps:
(1) Taking a certain amount of waste catalyst to remove porcelain balls;
(2) Roasting and deoiling: taking deoiled crushed materials, adding alkali for oxidizing roasting at 650-750 ℃ for 2-3 hours;
(3) Roasting the mixed materials;
(4) Soaking in water: leaching with cold water for 1.8-2.5 hr, and filtering to obtain residue a and filtrate b;
(5) Acidifying and impurity removing the filtrate b: adding acid into the filtrate b to adjust the pH value to 9-10, and then adding magnesium chloride to remove silicon aluminum;
(6) Recovering tungsten and vanadium: recovering valuable metal by adopting an ion exchange adsorption method, adding acid and hydrogen peroxide to adjust the pH value to 2-3, precipitating tungstic acid, reducing vanadium, remaining in the solution, and extracting vanadium by using N235;
(7) Taking the filter residue a in the step (4) for high-temperature acid leaching to obtain leaching residues and acid leaching liquid,
(8) Recovery of noble metals: iron removal and extraction are carried out on the pickle liquor, the pickle liquor adopts ion exchange separation to adsorb noble metals, and the nonferrous metals such as iron, nickel, cobalt and copper are recovered by extraction separation; filtering the raffinate after precipitation to obtain filter residue c and filtrate d, wherein the filter residue c is used for producing carbonate, and the filtrate d enters the step (4) for secondary water leaching;
(9) Recovering nickel and cobalt: filtering and crystallizing the back extraction liquid, extracting and separating nickel and cobalt from the filtrate by using P507, and precipitating and concentrating to obtain cobalt sulfate and nickel sulfate;
the specific method of high-temperature acid leaching in the step (7) comprises the following steps: acidifying with 2:1 hydrochloric acid for 4 hours at 55-70deg.C; filtering acid non-slag, and regulating pH value of filtrate to 2-3;
the specific method for recovering noble metals in the step (8) comprises the following steps: adding a noble metal precipitant according to the heavy metal content of 0.8-1:1.1-1.2, and filtering to obtain noble metal mixed metal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210174776.XA CN114635032B (en) | 2022-02-24 | 2022-02-24 | Comprehensive recycling method of waste catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210174776.XA CN114635032B (en) | 2022-02-24 | 2022-02-24 | Comprehensive recycling method of waste catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114635032A CN114635032A (en) | 2022-06-17 |
| CN114635032B true CN114635032B (en) | 2024-01-30 |
Family
ID=81948694
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210174776.XA Active CN114635032B (en) | 2022-02-24 | 2022-02-24 | Comprehensive recycling method of waste catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114635032B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999058732A1 (en) * | 1998-05-08 | 1999-11-18 | Shell Oil Company | Process to recover molybdenum and vanadium metals from spent catalyst by alkaline leaching |
| WO2008111802A1 (en) * | 2007-03-13 | 2008-09-18 | Man Joo Kim | Method of recovering valuable metals from the vrds spent catalyst |
| CN105274344A (en) * | 2015-11-23 | 2016-01-27 | 刘楚玲 | Method for recycling vanadium and molybdenum from waste petroleum catalyst |
| CN106498165A (en) * | 2016-10-21 | 2017-03-15 | 北京矿冶研究总院 | Method for recovering nickel and vanadium from waste FCC catalyst through melting, chlorination and volatilization |
| CN113234930A (en) * | 2021-04-25 | 2021-08-10 | 北京科技大学 | Method for recovering waste petroleum hydrogenation catalyst by combining pyrogenic process and wet process |
-
2022
- 2022-02-24 CN CN202210174776.XA patent/CN114635032B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999058732A1 (en) * | 1998-05-08 | 1999-11-18 | Shell Oil Company | Process to recover molybdenum and vanadium metals from spent catalyst by alkaline leaching |
| WO2008111802A1 (en) * | 2007-03-13 | 2008-09-18 | Man Joo Kim | Method of recovering valuable metals from the vrds spent catalyst |
| CN105274344A (en) * | 2015-11-23 | 2016-01-27 | 刘楚玲 | Method for recycling vanadium and molybdenum from waste petroleum catalyst |
| CN106498165A (en) * | 2016-10-21 | 2017-03-15 | 北京矿冶研究总院 | Method for recovering nickel and vanadium from waste FCC catalyst through melting, chlorination and volatilization |
| CN113234930A (en) * | 2021-04-25 | 2021-08-10 | 北京科技大学 | Method for recovering waste petroleum hydrogenation catalyst by combining pyrogenic process and wet process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114635032A (en) | 2022-06-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Hoffmann | Recovery of platinum-group metals from gabbroic rocks metals from auto catalysts | |
| US20180371578A1 (en) | Hydrometallurgical treatment process for extraction of precious, base and rare elements | |
| CN111575489B (en) | Method for pyrogenically treating waste automobile exhaust catalyst | |
| CN105400962A (en) | Method for recycling platinum group metal from waste catalysts | |
| CN102534226A (en) | Method for extracting precious metal from spent automobile catalyst by concentration smelting-wet separation process | |
| AU2011376315B2 (en) | Process for purifying zinc oxide | |
| WO2006119611A1 (en) | A process for the treatment of electric and other furnace dusts and residues containing zinc oxides and zinc ferrites | |
| CN110863108A (en) | Method for recovering platinum group metal in waste catalyst by melt extraction and vacuum distillation | |
| CN101956070A (en) | Recovery method of molybdenum concentrates | |
| CN101831542A (en) | Method for extracting metallic elements of ferrum, magnesium and calcium from molybdenum milltailings | |
| CN107557580A (en) | Method for removing copper and cadmium by zinc hydrometallurgy purification | |
| JP2013209732A (en) | Method for recovering nickel | |
| CN114635032B (en) | Comprehensive recycling method of waste catalyst | |
| CN110055425B (en) | Electroplating sludge heavy metal recycling method | |
| CN216514040U (en) | System for recovering copper, nickel, zinc, chromium and iron from electroplating sludge or other multi-metal mixture | |
| Liu et al. | Comprehensive recovery of Sn-Cu bearing residue and preparation of high purity SnO2 and CuSO4· 5H2O | |
| CN108677024B (en) | Method for recovering rare metals lanthanum cerium and zirconium from smelting slag | |
| CN113969355A (en) | Short-process preparation process for preparing zinc-cadmium alloy by using organic cobalt slag | |
| CN112267025A (en) | Method for extracting palladium from low-grade failure alumina carrier catalyst | |
| CN103011284B (en) | Method for removing impurities from crude bismuth oxide | |
| JP5521433B2 (en) | Filtration method of slurry containing colloidal silica | |
| CN115505751B (en) | Method for enriching germanium and indium from copper sulfide ore and co-producing blister copper | |
| CN102992401B (en) | Process for producing bismuth aluminate by using crude bismuth oxide | |
| RU2484154C1 (en) | Processing wastes containing nonferrous and platinum metals | |
| CN115369266B (en) | Method for removing and recycling arsenic in chlorohydrochloric acid leaching solution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |