CN114635032B - 一种废催化剂综合回收利用的方法 - Google Patents
一种废催化剂综合回收利用的方法 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)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geochemistry & Mineralogy (AREA)
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
本发明公开了一种废催化剂综合回收利用的方法,包括如下步骤:(1)取一定量废催化剂去瓷球;(2)焙烧脱油:(3)混料焙烧;(4)水浸:用冷水浸出2小时,过滤,得到滤渣a和滤液b;(5)所述滤液b酸化除杂;(6)回收钨钒:采用离子交换吸附法回收有价金属,加酸和双氧水调pH值为2‑3后沉淀钨酸,钒被还原留在溶液中,用N235萃取钒;(7)取步骤(4)中的滤渣a进行高温酸浸,得到浸出渣和酸浸液,(8)回收贵金属;(9)回收镍钴:反萃液过滤结晶得硫酸钴和硫酸镍。本发明不仅成本低,产品纯度高,且不再产生二次渣污染和二次废水,总回收率达到95%以上。
Description
技术领域
本发明涉及冶金技术领域,尤其涉及一种废催化剂综合回收利用的方法。
背景技术
废弃的SCR催化剂除自身含有V2O5、WO3(或MoO3)等有毒氧化物外,还夹杂有燃煤飞灰中的砷、汞、铅等具有危险特性的重金属物质,对人体健康和环境存在风险,在欧洲被定性为危险废物,美国EPA虽然未将废SCR脱硝催化剂列入危险废物进行管理,我国环境保护部污防司近期也在委托部属固体废物与化学品管理技术中心会同中国环境科学研究院固体废物污染控制技术研究所等单位,研究起草《废烟气脱硝催化剂危险废物经营许可证审查指南》,以规范废烟气脱硝催化剂经营许可证的审批工作,提升废烟气脱硝催化剂再生、利用的整体水平,防止在废烟气脱硝催化剂的再生、利用过程中对环境造成二次污染。炼油废催化剂的回收利用现状研究,对炼油废催化剂进行综合回收利用既可以提高资源利用率,也能避免废催化剂带来的环境污染问题。本项目将炼油废催化剂进一步细分为催化裂化、加氢处理以及催化重整催化剂,分别对这三类废催化剂的回收利用技术做出综述,从而为中国石油废催化剂回收利用向无害化和资源化的方向发展提供一定的参考。据国家***数据,2018年中国石油表观消费首破6亿吨,达到6.25亿吨,同比增加0.41亿吨,增速为7%;预计到2020年,国内炼油一次加工能力将超过9亿吨。根据国内炼油行业的标准测算,每吨原油炼制将产生0.354kg废催化剂,以此为依据,每年我国将产生15-20万吨废催化剂。
现有技术的旧工艺(如图2所示)一般采用贵金属废催化剂回收研究高温锍熔炼法回收贵金属,将贵金属物料破碎研磨到20目以下,按1:0.7的比例加入Pb、PbS、CuS2等捕集剂和石灰,并控制混合料S<5%,水分<15%,然后高压固化、风干,和焦炭分批加入电弧炉中在1400~1450℃下,在弱氧化气氛中,硫化铜和硫化铁一起共融生成锍,锍将贵金属捕集。最终铂族金属在合金和锍中可以富集10倍以上,直收率约85%。采用等离子炉的熔炼技术回收贵金属,将失效汽车催化剂(载体是堇青石2MgO·2Al2O3·5SiO2),配入的10%CaO,形成CaO-Al2O3-SiO2三元渣相,降低渣相的熔点,Fe3O4为捕集原料,焦炭为还原剂,在1500~1600℃条件下进行熔炼,然而,其铂bó、钯[bǎ]的回收率只为90%,铑lǎo的回收率顶多达到90%。
采用高温火法回收废催化剂中贵金属回收率低于95%,回收不完全,同时高温火法会造成大量废气污染,高温火法回收已经难符合环保要求。
用酸或者碱或其他溶剂溶解废工业催化剂的主要成分,滤液除杂纯化后,经分离,可得难溶于水的硫化物或金属氢氧化物,干燥后按需要再进一步加工成最终产品。贵金属催化剂、加氢脱硫催化剂、铜系及镍nie系等废催化剂一般采用湿法回收。通常也把电解法包括在湿法之中。用湿法处理废催化剂,其载体往往以不溶残渣形式存在,如无适当的处理方法,这些大量固体废弃物会造成二次公害,若载体随金属一起溶解,金属和载体的分离会产生大量废液易造成二次污染。将废催化剂的主要组分溶解后,采用阴阳离子交换树脂吸附法或采用萃取、反萃取的方法将浸液中不同组分分离、提纯出来是湿法回收的研究重点。
发明内容
本发明的目的是提供一种废催化剂综合回收利用的方法。
实现本发明目的的技术方案是:一种废催化剂综合回收利用的方法,包括如下步骤:
(1)取一定量废催化剂去瓷球;
(2)焙烧脱油:取脱油粉粹料加碱氧化焙烧,焙烧温度为700度,时间为2小时;
(3)混料焙烧;
(4)水浸:用冷水浸出2小时,过滤,得到滤渣a和滤液b;
(5)所述滤液b酸化除杂:滤液b加酸调节pH值为9-10后加入氯化镁除硅铝;
(6)回收钨钒:采用离子交换吸附法回收有价金属,加酸和双氧水调pH值为2-3后沉淀钨酸,钒被还原留在溶液中,用N235萃取钒,结晶后得到钨钼酸钠结晶;
(7)取步骤(4)中的滤渣a进行高温酸浸,得到浸出渣和酸浸液,
(8)回收贵金属:酸浸液进行除铁和萃取,酸浸液采用离子交换分离吸附贵金属,萃取分离回收铁、镍、钴、铜有色金属;萃余液沉淀后进行过滤得到滤渣c和滤液d,所述滤渣c用于生产碳酸盐,滤液d进入步骤(4)中进行二次水浸;
(9)回收镍钴:反萃液过滤结晶,滤液用P507萃取分离镍钴,沉淀浓缩得硫酸钴和硫酸镍,结晶后得到硫酸镍钴结晶。
作为优选,步骤(7)中高温酸浸的具体方法为:用2:1的盐酸酸化4小时,温度60度。滤除酸不熔渣,滤液调pH2-3。
作为优选,所述步骤(8)中回收贵金属的具体方法为:根据重金属含量按1:1.1加入贵金属沉淀剂,过滤后得贵金属混合金属。
采用了上述技术方案,本发明具有以下的有益效果:(1)本工艺采用全溶工艺,将废催化剂中各组分分段浸出回收,根据不同催化剂种类载体分为二氧化硅载体和氧化铝载体,二氧化硅载体采用氧化焙烧后高温氧化酸浸,氧化铝载体采用碱焙烧水浸除铝,浸出渣低温酸浸。碱浸液酸化除杂,离子交换回收钨、钼、钒等有价金属,尾液回收铝。酸浸液采用离子交换分离吸附贵金属,萃取分离回收铁、镍、钴、铜等有色金属。尾液石灰中和后蒸馏回收氯化钙,冷却水回用,不再产生二次渣污染和二次废水。采用离子交换回收有价元素,成本低,产品纯度高,不同产品采用不同交换树脂选择性回收不同元素。在保证浸出率的情况下,采用离子交换树脂回收可以获得很好的回收率,总回收率达到95%以上。
(2)本工艺主要特点是通过碱熔酸浸将全部粉末转移至溶液当中,通过化学处理手段(沉淀、离子交换及萃取)回收其中有价金属,贱金属通过中和沉淀等手段沉渣,废水通过蒸馏回收氯化钙,水回用。浸出pH值控制在9-10,酸化用1mol/L的硫酸酸化至pH值2-3后进行离子交换回收贵金属。尾液通过萃取回收镍钴。工艺简单回收率高。
附图说明
为了使本发明的内容更容易被清楚地理解,下面根据具体实施例并结合附图,对本发明作进一步详细的说明,其中
图1为本发明的流程示意图;
图2为现有技术的旧工艺的流程对比示意图。
具体实施方式
实施例一
见图1,本实施例的废催化剂综合回收利用的方法,包括如下步骤:
(1)取一定量废催化剂去瓷球;
(2)焙烧脱油:取脱油粉粹料加碱氧化焙烧,焙烧温度为700度,时间为2小时;
(3)混料焙烧;
(4)水浸:用冷水浸出2小时,过滤,得到滤渣a和滤液b;
(5)所述滤液b酸化除杂:滤液b加酸调节pH值为9-10后加入氯化镁除硅铝;
(6)回收钨钒:采用离子交换吸附法回收有价金属,加酸和双氧水调pH值为2-3后沉淀钨酸,钒被还原留在溶液中,用N235萃取钒;
(7)取步骤(4)中的滤渣a进行高温酸浸,得到浸出渣和酸浸液,
(8)回收贵金属:酸浸液进行除铁和萃取,酸浸液采用离子交换分离吸附贵金属,萃取分离回收铁、镍、钴、铜有色金属;萃余液沉淀后进行过滤得到滤渣c和滤液d,所述滤渣c用于生产碳酸盐,滤液d进入步骤(4)中进行二次水浸;
(9)回收镍钴:反萃液过滤结晶,滤液用P507萃取分离镍钴,沉淀浓缩得硫酸钴和硫酸镍。
步骤(7)中高温酸浸的具体方法为:用2:1的盐酸酸化4小时,温度60度。滤除酸不熔渣,滤液调pH2-3。
所述步骤(8)中回收贵金属的具体方法为:根据重金属含量按1:1.1加入贵金属沉淀剂,过滤后得贵金属混合金属。
本工艺主要特点是通过碱熔酸浸将全部粉末转移至溶液当中,通过化学处理手段(沉淀、离子交换及萃取)回收其中有价金属,贱金属通过中和沉淀等手段沉渣,废水通过蒸馏回收氯化钙,水回用。
浸出pH值控制在9-10,酸化用1mol/L的硫酸酸化至pH值2-3后进行离子交换回收贵金属。尾液通过萃取回收镍钴。工艺简单回收率高。
本工艺采用全溶工艺,将废催化剂中各组分分段浸出回收,根据不同催化剂种类载体分为二氧化硅载体和氧化铝载体,二氧化硅载体采用氧化焙烧后高温氧化酸浸,氧化铝载体采用碱焙烧水浸除铝,浸出渣低温酸浸。碱浸液酸化除杂,离子交换回收钨、钼、钒等有价金属,尾液回收铝。酸浸液采用离子交换分离吸附贵金属,萃取分离回收铁、镍、钴、铜等有色金属。尾液石灰中和后蒸馏回收氯化钙,冷却水回用,不再产生二次渣污染和二次废水。采用离子交换回收有价元素,成本低,产品纯度高,不同产品采用不同交换树脂选择性回收不同元素。在保证浸出率的情况下,采用离子交换树脂回收可以获得很好的回收率,总回收率达到95%以上。
实施例二
一种废催化剂综合回收利用的方法,其特征在于:包括如下步骤:
(1)取一定量废催化剂去瓷球;
(2)焙烧脱油:取脱油粉粹料加碱氧化焙烧,焙烧温度为650度,时间为2小时;
(3)混料焙烧;
(4)水浸:用冷水浸出1.8小时,过滤,得到滤渣a和滤液b;
(5)所述滤液b酸化除杂:滤液b加酸调节pH值为9后加入氯化镁除硅铝;
(6)回收钨钒:采用离子交换吸附法回收有价金属,加酸和双氧水调pH值为2-3后沉淀钨酸,钒被还原留在溶液中,用N235萃取钒;
(7)取步骤(4)中的滤渣a进行高温酸浸,得到浸出渣和酸浸液,
(8)回收贵金属:酸浸液进行除铁和萃取,酸浸液采用离子交换分离吸附贵金属,萃取分离回收铁、镍、钴、铜有色金属;萃余液沉淀后进行过滤得到滤渣c和滤液d,所述滤渣c用于生产碳酸盐,滤液d进入步骤(4)中进行二次水浸;
(9)回收镍钴:反萃液过滤结晶,滤液用P507萃取分离镍钴,沉淀浓缩得硫酸钴和硫酸镍。
步骤(7)中高温酸浸的具体方法为:用2:1的盐酸酸化4小时,温度55度。滤除酸不熔渣,滤液调pH2-3。
所述步骤(8)中回收贵金属的具体方法为:根据重金属含量按0.8:1.1加入贵金属沉淀剂,过滤后得贵金属混合金属。
本实施例的总回收率达到95.5%。
实施例三
一种废催化剂综合回收利用的方法,其特征在于:包括如下步骤:
(1)取一定量废催化剂去瓷球;
(2)焙烧脱油:取脱油粉粹料加碱氧化焙烧,焙烧温度为750度,时间为3小时;
(3)混料焙烧;
(4)水浸:用冷水浸出2.5小时,过滤,得到滤渣a和滤液b;
(5)所述滤液b酸化除杂:滤液b加酸调节pH值为9-10后加入氯化镁除硅铝;
(6)回收钨钒:采用离子交换吸附法回收有价金属,加酸和双氧水调pH值为2-3后沉淀钨酸,钒被还原留在溶液中,用N235萃取钒;
(7)取步骤(4)中的滤渣a进行高温酸浸,得到浸出渣和酸浸液,
(8)回收贵金属:酸浸液进行除铁和萃取,酸浸液采用离子交换分离吸附贵金属,萃取分离回收铁、镍、钴、铜有色金属;萃余液沉淀后进行过滤得到滤渣c和滤液d,所述滤渣c用于生产碳酸盐,滤液d进入步骤(4)中进行二次水浸;
(9)回收镍钴:反萃液过滤结晶,滤液用P507萃取分离镍钴,沉淀浓缩得硫酸钴和硫酸镍。
步骤(7)中高温酸浸的具体方法为:用2:1的盐酸酸化4小时,温度70度。滤除酸不熔渣,滤液调pH2-3。
所述步骤(8)中回收贵金属的具体方法为:根据重金属含量按1:1.2加入贵金属沉淀剂,过滤后得贵金属混合金属。
本实施例的总回收率达到95.8%。
以上所述的具体实施例,对本发明的目的、技术方案和有益效果进行了进一步详细说明,所应理解的是,以上所述仅为本发明的具体实施例而已,并不用于限制本发明,凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (1)
1.一种废催化剂综合回收利用的方法,其特征在于:包括如下步骤:
(1)取一定量废催化剂去瓷球;
(2)焙烧脱油:取脱油粉粹料加碱氧化焙烧,焙烧温度为650-750度,时间为2-3小时;
(3)混料焙烧;
(4)水浸:用冷水浸出1.8-2.5小时,过滤,得到滤渣a和滤液b;
(5)所述滤液b酸化除杂:滤液b加酸调节pH值为9-10后加入氯化镁除硅铝;
(6)回收钨钒:采用离子交换吸附法回收有价金属,加酸和双氧水调pH值为2-3后沉淀钨酸,钒被还原留在溶液中,用N235萃取钒;
(7)取步骤(4)中的滤渣a进行高 温酸浸,得到浸出渣和酸浸液,
(8)回收贵金属:酸浸液进行除铁和萃取,酸浸液采用离子交换分离吸附贵金属,萃取分离回收铁、镍、钴、铜有色金属;萃余液沉淀后进行过滤得到滤渣c和滤液d,所述滤渣c用于生产碳酸盐,滤液d进入步骤(4)中进行二次水浸;
(9)回收镍钴:反萃液过滤结晶,滤液用P507萃取分离镍钴,沉淀浓缩得硫酸钴和硫酸镍;
步骤(7)中高温酸浸的具体方法为:用2:1的盐酸酸化4小时,温度55-70度;滤除酸不熔渣,滤液调pH2-3;
所述步骤(8)中回收贵金属的具体方法为:根据重金属含量按0.8-1:1.1-1.2加入贵金属沉淀剂,过滤后得贵金属混合金属。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210174776.XA CN114635032B (zh) | 2022-02-24 | 2022-02-24 | 一种废催化剂综合回收利用的方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210174776.XA CN114635032B (zh) | 2022-02-24 | 2022-02-24 | 一种废催化剂综合回收利用的方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114635032A CN114635032A (zh) | 2022-06-17 |
CN114635032B true CN114635032B (zh) | 2024-01-30 |
Family
ID=81948694
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210174776.XA Active CN114635032B (zh) | 2022-02-24 | 2022-02-24 | 一种废催化剂综合回收利用的方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114635032B (zh) |
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 (zh) * | 2015-11-23 | 2016-01-27 | 刘楚玲 | 一种从废石油催化剂中回收钒和钼的方法 |
CN106498165A (zh) * | 2016-10-21 | 2017-03-15 | 北京矿冶研究总院 | 一种从废fcc催化剂中熔融氯化挥发回收镍、钒的方法 |
CN113234930A (zh) * | 2021-04-25 | 2021-08-10 | 北京科技大学 | 一种火法-湿法结合回收废石油加氢催化剂的方法 |
-
2022
- 2022-02-24 CN CN202210174776.XA patent/CN114635032B/zh 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 (zh) * | 2015-11-23 | 2016-01-27 | 刘楚玲 | 一种从废石油催化剂中回收钒和钼的方法 |
CN106498165A (zh) * | 2016-10-21 | 2017-03-15 | 北京矿冶研究总院 | 一种从废fcc催化剂中熔融氯化挥发回收镍、钒的方法 |
CN113234930A (zh) * | 2021-04-25 | 2021-08-10 | 北京科技大学 | 一种火法-湿法结合回收废石油加氢催化剂的方法 |
Also Published As
Publication number | Publication date |
---|---|
CN114635032A (zh) | 2022-06-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US10988826B2 (en) | Hydrometallurgical treatment process for extraction of precious, base and rare elements | |
Hoffmann | Recovery of platinum-group metals from gabbroic rocks metals from auto catalysts | |
CN102534226B (zh) | 熔炼富集-湿法分离工艺从失效汽车催化剂中提取贵金属的方法 | |
CN111575489B (zh) | 一种火法处理废汽车尾气催化剂的方法 | |
CN105400962A (zh) | 一种从废催化剂中回收铂族金属的方法 | |
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 (zh) | 一种熔体萃取真空蒸馏回收废旧催化剂中铂族金属的方法 | |
CN101956070A (zh) | 一种钼精矿回收方法 | |
CN101831542A (zh) | 一种从钼选矿尾矿中提取金属元素铁、镁、钙的方法 | |
CN107557580A (zh) | 一种湿法炼锌净化除铜镉的方法 | |
JP2013209732A (ja) | ニッケルの回収方法 | |
CN104152699A (zh) | 一种废Pt-Re/Al2O3石油重整催化剂综合回收的方法 | |
CN113969355A (zh) | 一种利用有机钴渣制备锌镉合金的短流程制备工艺 | |
CN114635032B (zh) | 一种废催化剂综合回收利用的方法 | |
CN110055425B (zh) | 一种电镀污泥重金属资源化方法 | |
CN216514040U (zh) | 电镀污泥或其他多金属混合物回收铜、镍、锌、铬、铁的*** | |
Liu et al. | Comprehensive recovery of Sn-Cu bearing residue and preparation of high purity SnO2 and CuSO4· 5H2O | |
CN108677024B (zh) | 一种从熔炼渣中回收稀有金属镧铈和锆的方法 | |
CN112267025A (zh) | 一种从低品位失效氧化铝载体催化剂中提取钯的方法 | |
CN103011284B (zh) | 一种粗氧化铋除杂方法 | |
JP5521433B2 (ja) | コロイド状シリカを含むスラリーのろ過方法 | |
CN102992401B (zh) | 一种用粗氧化铋生产铝酸铋的工艺 | |
US20240110259A1 (en) | Method for co-producing blister copper by enriching germanium and indium from a copper sulfide ore | |
CN115369266B (zh) | 一种氯盐酸性浸出液中砷的去除和回收的方法 |
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 |