CN116060140A - Method for recycling waste hydrogenation catalyst - Google Patents
Method for recycling waste hydrogenation catalyst Download PDFInfo
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- CN116060140A CN116060140A CN202111272120.3A CN202111272120A CN116060140A CN 116060140 A CN116060140 A CN 116060140A CN 202111272120 A CN202111272120 A CN 202111272120A CN 116060140 A CN116060140 A CN 116060140A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 115
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 61
- 239000002699 waste material Substances 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 53
- 238000004064 recycling Methods 0.000 title claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 45
- 229910052751 metal Inorganic materials 0.000 claims abstract description 44
- 239000002184 metal Substances 0.000 claims abstract description 43
- 239000000047 product Substances 0.000 claims abstract description 33
- 239000002253 acid Substances 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 150000001412 amines Chemical class 0.000 claims abstract description 18
- 238000010992 reflux Methods 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 238000009835 boiling Methods 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 239000012263 liquid product Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 96
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 46
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 42
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 38
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 36
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 29
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 26
- 229910052799 carbon Inorganic materials 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000000967 suction filtration Methods 0.000 claims description 24
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 21
- 229910052750 molybdenum Inorganic materials 0.000 claims description 21
- 239000011733 molybdenum Substances 0.000 claims description 20
- 229910052759 nickel Inorganic materials 0.000 claims description 16
- 239000011575 calcium Substances 0.000 claims description 15
- 229910052791 calcium Inorganic materials 0.000 claims description 15
- 229910052742 iron Inorganic materials 0.000 claims description 15
- 239000000706 filtrate Substances 0.000 claims description 14
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 13
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 11
- 239000000292 calcium oxide Substances 0.000 claims description 11
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 11
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 11
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- 239000011593 sulfur Substances 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 239000011959 amorphous silica alumina Substances 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 2
- 239000010413 mother solution Substances 0.000 claims 4
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 9
- 239000012535 impurity Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 238000005470 impregnation Methods 0.000 description 16
- 229910017318 Mo—Ni Inorganic materials 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 150000002739 metals Chemical class 0.000 description 11
- 238000001816 cooling Methods 0.000 description 7
- 229910000480 nickel oxide Inorganic materials 0.000 description 7
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 229910017313 Mo—Co Inorganic materials 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- -1 pentylene diamine Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- PZZICILSCNDOKK-UHFFFAOYSA-N propane-1,2,3-triamine Chemical compound NCC(N)CN PZZICILSCNDOKK-UHFFFAOYSA-N 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 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
- 239000006004 Quartz sand Substances 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000012050 conventional carrier Substances 0.000 description 1
- 101150108611 dct-1 gene Proteins 0.000 description 1
- 101150089388 dct-5 gene Proteins 0.000 description 1
- 101150036723 dct-6 gene Proteins 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- VLXBWPOEOIIREY-UHFFFAOYSA-N dimethyl diselenide Natural products C[Se][Se]C VLXBWPOEOIIREY-UHFFFAOYSA-N 0.000 description 1
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/12—Treating with free oxygen-containing gas
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/485—Impregnating or reimpregnating with, or deposition of metal compounds or catalytically active elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/60—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/64—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts
- B01J38/66—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts using ammonia or derivatives thereof
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a method for recycling waste hydrogenation catalysts. The method comprises the following steps: (1) roasting the waste hydrogenation catalyst in an aerobic atmosphere; mixing the roasting product with an acid solution, and heating and refluxing; (2) Adjusting the pH value of the reflux product obtained in the step (1) to 3.5-4.5 by using organic amine, and carrying out solid-liquid separation; the boiling point of the organic amine under normal pressure is more than or equal to 100 ℃; (3) And (3) taking the liquid product obtained by filtering in the step (2) as an impregnating liquid impregnating carrier, and carrying out heat treatment to obtain the regenerated hydrogenation catalyst. The method has the characteristics of simple metal recovery step and less residual impurities, and the obtained new hydrogenation catalyst has high activity, and is particularly suitable for metal recovery and reutilization of Ni (Co) -Mo series catalysts.
Description
Technical Field
The invention belongs to the field of waste catalyst recycling, and particularly relates to a method for recycling waste hydrogenation catalysts.
Background
The hydrogenation catalyst is scrapped after being used for a plurality of periods, and the common method is to extract active metals in the waste catalyst step by step and convert the active metals into metal salts or oxides. Realizing the recycling of metal. However, impurities such as iron and calcium in the waste hydrogenation catalyst affect the usability of the hydrogenation catalyst, and in the metal recovery process, the impurities generally need to be removed at a relatively high cost.
CN109837393a discloses a method for selectively recovering valuable metals from waste hydrogenation catalyst, which comprises the steps of calcining the waste hydrogenation catalyst at high temperature, pulverizing, treating with solution for three times, and selectively recovering molybdenum, nickel, vanadium and aluminum in sequence with high recovery rate. The method can recover the metals in the catalyst respectively, has complicated process, and has larger energy consumption if the metal is required to be dissolved again for preparing the hydrogenation catalyst.
CN112439462a discloses a method for recycling spent hydrogenation catalyst, which comprises: and carrying out heat treatment and grinding on the waste hydrogenation catalyst to obtain waste agent powder, separating the waste agent powder, and using the low-density waste agent powder in slurry bed catalytic hydrogenation reaction. This method does not allow complete recovery of the metals in the catalyst and the low density powder has a much poorer activity than the fresh catalyst.
CN112547080a discloses a method for recycling supported hydrogenation catalyst. The method comprises the steps of crushing the screened waste catalyst to below 50 microns, adding the crushed waste catalyst into a mixing and kneading process for preparing the carrier according to a certain proportion, extruding, forming, drying and roasting under an inert gas atmosphere to prepare the mixed carrier, wherein carbon on the waste catalyst weakens the interaction between metal and the carrier, and supplementing an active component impregnating solution for loading, so that the prepared catalyst has higher hydrodesulfurization activity. The method can only treat a small amount of waste catalyst, and is not suitable for treating a large amount of waste catalyst in the industrial production process.
CN112619658A discloses a method for recycling waste hydrogenation catalyst. Extracting and degreasing a waste hydrogenation catalyst, roasting to remove carbon, crushing, screening, mixing with alkali, roasting, soaking roasted waste catalyst powder with hot water, filtering to obtain filtrate and residues, and adding a polymer monomer I into the filtrate to obtain a solution I; mixing the residue with acid for reaction, filtering, and adding polymer monomer II into the filtrate to obtain solution II; and (3) carrying out parallel flow gelling reaction on the solution I and the solution II, aging, adding an initiator into the aged suspension, carrying out polymerization reaction, carrying out solid-liquid separation on materials, extruding strips for molding, and then drying and roasting to obtain the hydrogenation catalyst. The treatment method has complicated steps, generates a large amount of waste, and has high environmental cost.
Disclosure of Invention
In order to simplify the recovery steps of active metals in the waste hydrogenation catalyst, improve the recovery efficiency of metals and reduce wastes generated in the metal recovery process, the invention provides a method for recovering and reutilizing the waste hydrogenation catalyst.
The invention provides a method for recycling waste hydrogenation catalyst, which comprises the following steps:
(1) Roasting the waste hydrogenation catalyst in an aerobic atmosphere; mixing the roasting product with an acid solution, and heating and refluxing;
(2) Adjusting the pH value of the reflux product obtained in the step (1) to 3.5-4.5 by using organic amine, and carrying out solid-liquid separation; the boiling point of the organic amine under normal pressure is more than or equal to 100 ℃;
(3) And (3) taking the liquid product obtained by filtering in the step (2) as an impregnating liquid impregnating carrier, and carrying out heat treatment to obtain the regenerated hydrogenation catalyst.
According to the invention, in the step (1), the waste hydrogenation catalyst comprises the following components in percentage by mass based on the mass of the waste hydrogenation catalyst:
5% -40% of molybdenum calculated by molybdenum trioxide;
2% -10% of at least one selected from nickel and cobalt in terms of oxide;
0.01 to 1.0 percent of calcium calculated by calcium oxide;
0.01 to 3.0 percent of iron calculated by ferric oxide;
the content of S element is 3% -15%;
40% -80% of carrier.
According to the invention, in the step (1), the waste hydrogenation catalyst can also contain 2.1% -12.0% of carbon deposit.
According to the invention, the carrier in step (1) is a conventional carrier; the carrier comprises one or more of alumina, silicon oxide, amorphous silica-alumina and titanium-containing alumina.
According to the invention, the calcination temperature in step (1) is 280 to 600 ℃, preferably 320 to 550 ℃, and the calcination time is 2 to 20 hours, preferably 2 to 12 hours.
According to the invention, the carbon content in the calcined product of step (1) is 2.0wt% or less, preferably 0.6wt% or less, in terms of mass fraction.
According to the invention, the acid solution in step (1) is a mixed acid solution of phosphoric acid and sulfuric acid. Further, in the mixed acid solution, the molar concentration of phosphoric acid is 0.1 to 3.0mol/L, preferably 0.3 to 2.0mol/L, and the molar concentration of sulfuric acid is 0.05 to 1.0mol/L, preferably 0.1 to 0.6mol/L.
According to the invention, the mass ratio of the volume of the acid solution in step (1) to the calcined product obtained in step (1) is 1:1 to 4:1ml/g, preferably 1.5:1 to 3.0:1ml/g.
According to the invention, the temperature of the heating reflux in the step (1) is 80-105 ℃, preferably 95-100 ℃; the heating time is 2.0 to 12.0 hours, preferably 4.0 to 8.0 hours.
According to the invention, the pH value is regulated after the reflux product in the step (2) is cooled to 30-50 ℃. The boiling point of the organic amine is 100 ℃ or higher, preferably 100-300 ℃. Further, the organic amine comprises at least one of ethylenediamine, 1, 2-propylenediamine, 1, 3-propylenediamine, dipropylamine, dibutylamine, pentylene diamine, and 1,2, 3-propyltriamine. Preferably, the organic amine of step (2) is added in the form of an organic amine solution, wherein the mass concentration of the organic amine solution is 2% to 20%, preferably 5% to 15%.
According to the invention, the solid-liquid separation mode in the step (2) is suction filtration. Preferably, the pH-adjusted mixture is heated prior to suction filtration. The heating temperature is 50 to 100 ℃, preferably 60 to 70 ℃. The heating time is 0.5 to 4 hours, preferably 1 to 2 hours. In the suction filtration, the temperature of the suction filtrate is controlled to be 40-70 ℃, preferably 50-60 ℃. Preferably, water can be added for dilution during suction filtration. The water is used in an amount of 20 to 200% by mass, preferably 30 to 120% by mass, of the calcined product obtained in the step (1).
According to the invention, preferably, in order to adapt to the impregnation amount requirements of hydrogenation catalysts of different reactions, the impregnation liquid in the step (3) can be used as a mother liquid, and the mother liquid is adjusted so that the active metal content in the adjusted mother liquid is suitable for hydrogenation catalytic reactions. The method for adjusting the mother liquor may be a known method such as adding an active metal source or diluting with water. The active metal source is at least one of soluble salt and metal oxide of active metal. The active metal source comprises a molybdenum source and at least one selected from a nickel source and a cobalt source. Conventional auxiliaries used in impregnating solutions for hydrogenation catalysts may also be added to the impregnating solutions.
According to the present invention, it is preferable that the content of the metallic molybdenum element in the impregnation liquid obtained after the mother liquor is adjusted in the step (3) is 0.5 to 5.0mol/L, preferably 0.8 to 4.0mol/L, in terms of atoms.
According to the present invention, it is preferable that the content of metallic nickel and/or cobalt element in the impregnation liquid obtained after the mother liquor is adjusted in the step (3) is 0.2 to 2.0mol/L, preferably 0.3 to 1.5mol/L, on an atomic basis.
According to the invention, the carrier in step (3) may be selected conventionally, preferably comprising one or more of alumina, silica, amorphous silica-alumina, titania-containing alumina; in the titanium-containing alumina, the molar ratio of titanium to aluminum is 0.1 to 0.4 in terms of atoms.
According to the present invention, preferably, the specific surface area of the carrier is 150 to 500m 2 Preferably 200 to 400m 2 Per gram, the pore volume of the carrier is 0.2-1.2 cm 3 /g，0.3～1.0cm 3 And/g. The carrier can be doped with one or more of modified elements such as phosphorus, silicon, boron, fluorine, magnesium, sodium, zinc and the like. The addition amount of the modifying element is the conventional addition amount, and preferably accounts for 0.5 to 6.0 percent of the mass of the carrier.
According to the invention, the method of impregnating the support in step (3) is one of the well-known unsaturated impregnations, isovolumetric impregnations, supersaturated impregnations. The heat treatment method is at least one of drying and roasting; the atmosphere of the heat treatment may be an aerobic or anaerobic atmosphere. . The conditions of the heat treatment are as follows: the temperature of the heat treatment is 80-800 ℃, preferably 100-550 ℃, and the heat treatment time is 2-20 hours, preferably 4-15 hours.
Compared with the prior art, the invention has the following advantages:
1. in the method for recycling the waste hydrogenation catalyst, the industrial waste catalyst is roasted at low temperature, the metal in a vulcanized state is mainly converted into an oxidized state, carbon deposition covered on the surface of the catalyst can be further removed, acid solution (preferably phosphoric acid and sulfuric acid) is added into the catalyst, ca is removed, and meanwhile, a part of pore channels of a carrier are damaged, so that the metal is fully exposed; the high-temperature heating is carried out, the pH value of the solution is regulated to 3.5-4.5 by using high-boiling organic amine, the iron element is removed, meanwhile, the phosphomolybdic heteropolyacid is not hydrolyzed, the Ni (Co) -Mo impregnating solution which basically does not contain Ca and Fe ions is obtained, and the Ni (Co) -Mo impregnating solution can be used as the impregnating solution by supplementing proper metals and auxiliary agents.
2. The method can directly convert molybdenum and nickel (cobalt) metals on the waste catalyst into the impregnating solution which can be used for preparing a new hydrogenation catalyst, omits the complicated process of separating the molybdenum and the nickel (cobalt) into respective oxides (or metal salts) and then dissolving the oxides (or the metal salts) in the prior art, greatly improves the efficiency, has less residual impurities, and is particularly suitable for recycling metals of Ni (Co) -Mo series catalysts. On the other hand, in the method, the step of precipitating metal ions by using the acid solution and the step of adjusting the pH value by using the specific organic amine are combined, so that iron and calcium impurities on the waste catalyst can be efficiently removed from the impregnating solution, and the content of molybdenum metal elements is not influenced. The regenerated catalyst prepared from the recovered impregnation liquid containing the active metal is suitable for hydrogenation catalyst reaction and has high activity.
Detailed Description
The process according to the invention is described in more detail by way of examples.
In the present invention, the alumina carrier a used in the following examples was prepared as follows: taking 3000g of aluminum hydroxide dry rubber powder, 30.0g of sesbania powder, 30.0g of cellulose and 20.0g of citric acid, uniformly mixing the mixture with 2800g of nitric acid solution with the mass fraction of 2%, kneading the mixture for 20 minutes by using a kneader, extruding and molding by using a strip extruder, drying the extruded carrier at 120 ℃ for 4.0 hours under the condition that the extrusion pressure is 30.0MPa and the pore plate is 1.6mm, roasting at 600 ℃ for 4.0 hours, and obtaining the aluminum oxide carrier which is denoted as carrier A. The specific surface area of the support A was 320m 2 Per g, pore volume of 0.92cm 3 /g。
In the invention, the analysis method of the metal element in the catalyst and the solution comprises the following steps: GB/T38904-2020.
In the invention, the analysis method of the carbon content in the catalyst comprises the following steps: GB/T14265-2017.
In the invention, the calculation method of the utilization ratio S (wt%) of a certain metal in the waste catalyst comprises the following steps:
S＝(a×m1-b)/(c×m2)×100％
wherein a is the mass of the newly prepared catalyst, m1 is the mass fraction of the metal in the new catalyst, b is the mass of the metal added in the step (3), c is the mass of the waste catalyst, and m2 is the mass fraction of the metal in the waste catalyst.
Example 1:
(1) 200.0g of industrially used waste hydrogenation catalyst Mo-Ni is taken and roasted in a muffle furnace at 450 ℃ for 4 hours. The obtained calcined product was designated ZC-1.
The waste hydrogenation catalyst Mo-Ni hydrotreating catalyst comprises the following components: 20.71% molybdenum, calculated as molybdenum trioxide; 4.07% nickel, calculated as nickel oxide; 0.44% calcium calculated as calcium oxide; 1.24% iron, calculated as ferric oxide; 8.22% of carbon deposit, 10.35% of sulfur and the balance of carrier alumina.
The carbon content of the roasted product is 0.52wt% in terms of mass fraction.
The solution of deionized water, phosphoric acid and sulfuric acid was prepared into 200ml, and the resulting mixed acid solution was designated as AQ-1, wherein the molar concentration of phosphoric acid was 0.4mol/L and the molar concentration of sulfuric acid was 0.2mol/L.
100.0g ZC-1 was taken, 200ml of the mixed acid solution AQ-1 was added thereto, and the mixture was heated to reflux, and the heating temperature was controlled at 100℃for 6.0 hours.
(2) After stopping heating, cooling to 40 ℃, slowly adding an ethylenediamine solution with a mass fraction of 10% to the reflux product, measuring the pH value of the solution during the period, and stopping dripping when the pH value of the solution is 4.0, wherein the mass of the added solution is 24.6g. The solution was then heated to 65℃for 1.0 hour. And (3) carrying out suction filtration at the temperature of between 50 and 60 ℃, wherein the water quantity added in the suction filtration process is 80.0g, and the obtained filtrate is denoted as FQ-1.
(3) 4.5g of molybdenum trioxide and 3.5g of nickel nitrate hexahydrate are added to the FQ-1 in the step (2), and heated to concentrate to 70.0ml, and the obtained impregnating solution is JQ-1. In the impregnating solution, the content of metallic molybdenum element is 2.23mol/L and the content of metallic nickel element is 0.86mol/L in atomic terms.
70g of alumina carrier A was taken, the JQ-1 was impregnated on the carrier A, and the catalyst obtained after drying at 120℃for 5 hours and then baking at 420℃for 4 hours was designated CT-1.
Example 2:
(1) 200.0g of industrially used waste hydrogenation catalyst Mo-Ni is taken and roasted in a muffle furnace at 450 ℃ for 4 hours. The obtained calcined product was designated ZC-2.
The waste hydrogenation catalyst Mo-Ni hydrotreating catalyst comprises the following components: 34.98% molybdenum, calculated as molybdenum trioxide; 7.85% nickel calculated as nickel oxide; 0.23% calcium calculated as calcium oxide; 0.63% iron, calculated as ferric oxide; 7.54% of carbon deposit, 16.29% of sulfur and the balance of carrier alumina.
In the roasting product of the step (1), the carbon content is 0.86 weight percent in terms of mass fraction.
The solution of deionized water, phosphoric acid and sulfuric acid was prepared into 200ml, and the obtained mixed acid solution was designated as AQ-2, wherein the molar concentration of phosphoric acid was 0.6mol/L and the molar concentration of sulfuric acid was 0.05mol/L.
100.0g ZC-2 was taken, 200ml of the mixed acid solution AQ-2 was added thereto, and the mixture was heated to reflux, and the heating temperature was controlled at 100℃for 6.0 hours.
(2) After stopping heating, cooling to 50 ℃, slowly adding 10% by mass of 1,2, 3-propanetriamine to the solution, measuring the pH value of the solution during the period, and stopping dripping when the pH value of the solution is 4.0, wherein the mass of the added solution is 33.7g. The solution was then heated to 65℃for 1.0 hour. And (3) carrying out suction filtration at the temperature of between 50 and 60 ℃, wherein the water quantity added in the suction filtration process is 80.0g, and the obtained filtrate is denoted as FQ-2.
(3) To the above FQ-2, 4.5g of molybdenum trioxide and 3.5g of nickel nitrate hexahydrate were added, and the mixture was heated and concentrated to 70.0ml, whereby the resulting impregnation liquid was designated JQ-2. Namely, in the impregnating solution, the content of metallic molybdenum element is 3.25mol/L and the content of metallic nickel element is 1.03mol/L in terms of atom.
70.0g of alumina carrier A is taken, the JQ-2 is immersed on the carrier A, and is dried for 5 hours at 120 ℃, and then is roasted for 4 hours at 420 ℃, and the obtained catalyst is CT-2.
Example 3:
(1) 200.0g of industrially used waste hydrogenation catalyst Mo-Ni is taken and roasted in a muffle furnace at 450 ℃ for 4 hours. The obtained calcined product was designated as ZC-3.
The waste hydrogenation catalyst Mo-Ni hydrotreating catalyst comprises the following components: 14.56% molybdenum, calculated as molybdenum trioxide; 3.12% nickel, calculated as nickel oxide; 0.72% calcium calculated as calcium oxide; 2.61% iron based on ferric oxide; 9.58% of carbon deposit, 7.27% of sulfur and the balance of carrier alumina.
In the roasting product of the step (1), the carbon content is 0.44 weight percent in terms of mass fraction.
The solution of deionized water, phosphoric acid and sulfuric acid was prepared into 200ml, and the resulting mixed acid solution was designated as AQ-3, wherein the molar concentration of phosphoric acid was 0.30mol/L and the molar concentration of sulfuric acid was 0.40mol/L.
100.0g ZC-3 was taken, 200ml of the mixed acid solution AQ-3 was added thereto, and the mixture was heated to reflux, and the heating temperature was controlled at 100℃for 6.0 hours.
(2) After stopping heating, cooling to 50 ℃, slowly adding 10% by mass of 1,2, 3-propanetriamine to the solution, measuring the pH value of the solution during the period, and stopping dripping when the pH value of the solution is 4.0, wherein the mass of the added solution is 28.8g. The solution was then heated to 65℃for 1.0 hour. And (3) carrying out suction filtration at the temperature of between 50 and 60 ℃, wherein the water quantity added in the suction filtration process is 80.0g, and the obtained filtrate is denoted as FQ-3.
(3) To the above FQ-3, 4.5g of molybdenum trioxide and 3.5g of nickel nitrate hexahydrate were added, and the mixture was heated and concentrated to 70.0ml, whereby the resulting impregnation liquid was designated JQ-3. Namely, in the impregnating solution, the content of metallic molybdenum element was 1.69mol/L and the content of metallic nickel element was 0.71mol/L in terms of atom.
70.0g of alumina carrier A is taken, the JQ-3 is immersed on the carrier A, and is dried for 5 hours at 120 ℃, and then is roasted for 4 hours at 420 ℃, and the obtained catalyst is CT-3.
Example 4:
(1) 200.0g of industrially used waste hydrogenation catalyst Mo-Co hydrogenation catalyst is taken and roasted in a muffle furnace at 450 ℃ for 4 hours. The obtained calcined product was designated as ZC-4.
The waste hydrogenation catalyst Mo-Co hydrotreating catalyst comprises the following components: 21.08% molybdenum, calculated as molybdenum trioxide; 4.23% cobalt, calculated as cobalt oxide; 0.50% calcium calculated as calcium oxide; 1.46% iron, calculated as ferric oxide; 6.84% of carbon deposit, 11.22% of sulfur and the balance of carrier alumina.
In the roasting product of the step (1), the carbon content is 0.59 weight percent in terms of mass fraction.
The solution of deionized water, phosphoric acid and sulfuric acid was prepared into 200ml, and the resulting mixed acid solution was designated as AQ-4, wherein the molar concentration of phosphoric acid was 0.40mol/L and the molar concentration of sulfuric acid was 0.20mol/L.
100.0g ZC-4 was taken, 200ml AQ-3 was added thereto, and the mixture was heated to reflux, and the heating temperature was controlled at 100℃for 6.0 hours. After stopping heating, cooling to 50 ℃, slowly adding dibutylamine with the mass fraction of 10% into the solution, measuring the pH value of the solution during the period, stopping dripping when the pH value of the solution is 3.5, and the mass of the dripped solution is 40.1g. The solution was then heated to 65℃for 1.0 hour. And (3) carrying out suction filtration at the temperature of between 50 and 60 ℃, wherein the water quantity added in the suction filtration process is 80.0g, and the obtained filtrate is denoted as FQ-4.
(3) To FQ-4, 4.5g of molybdenum trioxide and 3.5g of cobalt nitrate hexahydrate were added, and the mixture was heated and concentrated to 70.0ml, whereby the resulting impregnation liquid was designated JQ-4. Namely, in the impregnating solution, the content of metallic molybdenum element was 2.25mol/L and the content of metallic cobalt element was 0.86mol/L in terms of atom.
70.0g of alumina carrier A is taken, JQ-4 is soaked on the carrier A, the carrier A is dried for 5 hours at 120 ℃, and then the catalyst obtained after roasting for 4 hours at 420 ℃ is recorded as CT-4.
Example 5:
(1) 200.0g of industrially used waste hydrogenation catalyst Mo-Co hydrogenation catalyst is taken and roasted in a muffle furnace at 450 ℃ for 4 hours. The obtained calcined product was designated as ZC-5.
The waste hydrogenation catalyst Mo-Co hydrotreating catalyst comprises the following components: 21.08% molybdenum, calculated as molybdenum trioxide; 4.23% cobalt, calculated as cobalt oxide; 0.50% calcium calculated as calcium oxide; 1.46% iron, calculated as ferric oxide; 6.84% of carbon deposit, 11.22% of sulfur and the balance of carrier alumina.
In the roasting product of the step (1), the carbon content is 0.5 weight percent in terms of mass fraction.
The solution of deionized water, phosphoric acid and sulfuric acid was prepared into 200ml, and the obtained mixed acid solution was designated as AQ-5, wherein the molar concentration of phosphoric acid was 0.45mol/L and the molar concentration of sulfuric acid was 0.25mol/L.
100.0g ZC-5 was taken, 200ml AQ-5 was added thereto, and the mixture was heated to reflux, and the heating temperature was controlled at 100℃for 6.0 hours. After stopping heating, cooling to 50 ℃, slowly adding 10% by mass of pentylene diamine into the solution, measuring the pH value of the solution during the period, and stopping dripping when the pH value of the solution is 4.5, wherein the mass of the dripped solution is 48.2g. The solution was then heated to 65℃for 1.0 hour. And (3) carrying out suction filtration at the temperature of between 50 and 60 ℃, wherein the water quantity added in the suction filtration process is 80.0g, and the obtained filtrate is denoted as FQ-5.
To FQ-5, 4.5g of molybdenum trioxide and 3.5g of cobalt nitrate hexahydrate were added, and the mixture was heated and concentrated to 70.0ml, whereby the resulting impregnation liquid was designated JQ-5. Namely, in the impregnating solution, the content of metallic molybdenum element was 2.30mol/L and the content of metallic cobalt element was 0.87mol/L in terms of atom.
70.0ml of alumina carrier A is taken, JQ-5 is soaked on the carrier A, the carrier A is dried for 5 hours at 120 ℃, and then the catalyst obtained after roasting for 4 hours at 420 ℃ is recorded as CT-5.
Comparative example 1:
(1) 200.0g of industrially used waste hydrogenation catalyst Mo-Ni is taken and roasted in a muffle furnace at 450 ℃ for 4 hours. The obtained calcined product was designated as DZC-1.
The waste hydrogenation catalyst Mo-Ni hydrotreating catalyst comprises the following components: 20.71% molybdenum, calculated as molybdenum trioxide; 4.07% nickel, calculated as nickel oxide; 0.44% calcium calculated as calcium oxide; 1.24% iron, calculated as ferric oxide; 8.22% of carbon deposit, 10.35% of sulfur and the balance of carrier alumina.
In the roasting product of the step (1), the carbon content is 0.52 weight percent in terms of mass fraction.
100.0g of DZC-1 was taken, 200ml of deionized water was added thereto, and the mixture was heated to reflux, and the heating temperature was controlled at 100℃for 6.0 hours.
(2) After stopping heating, carrying out suction filtration at the temperature of 50-60 ℃, wherein the water quantity added in the suction filtration process is 80.0g, and the obtained filtrate is named as DFQ-1.
(3) Adding nickel and molybdenum elements into the DFQ-1 in the step (2), heating the mixture to concentrate the mixture to 70.0ml, and obtaining a dipping liquid DJQ-1, wherein the adding amount of the nickel and molybdenum elements is the same as that of the step (3) in the example 1.
70.0ml of alumina carrier A is taken, DJQ-1 is soaked on the carrier A, the carrier A is dried for 5 hours at 120 ℃, and then the carrier A is roasted for 4 hours at 420 ℃, and the obtained catalyst is named DCT-1.
Comparative example 2:
(1) 200.0g of industrially used waste hydrogenation catalyst Mo-Ni is taken and roasted in a muffle furnace at 450 ℃ for 4 hours. The obtained calcined product was designated as DZC-2.
The waste hydrogenation catalyst Mo-Ni hydrotreating catalyst comprises the following components: 20.71% molybdenum, calculated as molybdenum trioxide; 4.07% nickel, calculated as nickel oxide; 0.44% calcium calculated as calcium oxide; 1.24% iron, calculated as ferric oxide; 8.22% of carbon deposit, 10.35% of sulfur and the balance of carrier alumina.
In the roasting product of the step (1), the carbon content is 0.52 weight percent in terms of mass fraction.
200ml of a solution was prepared with deionized water and phosphoric acid, and the resulting mixed acid solution was designated as DAQ-2, wherein the molar concentration of phosphoric acid was 0.4mol/L.
100.0g of DZC-2 was taken, 200ml of DAQ-2 was added thereto, and the mixture was refluxed with heating at 100℃for 6.0 hours.
(2) After stopping heating, cooling, carrying out suction filtration at the temperature of 50-60 ℃, wherein the water quantity added in the suction filtration process is 80.0g, and the obtained filtrate is named as DFQ-2.
(3) The added amounts of nickel and molybdenum elements were the same as those in the step (3) of example 1, and the resultant impregnation was heated and concentrated to 70.0ml, and the resultant impregnation was DJQ-2.
70.0g of alumina carrier A is taken, DJQ-2 is soaked on the carrier A, the carrier A is dried for 5 hours at 120 ℃, and then baked for 4 hours at 420 ℃, and the obtained catalyst is named DCT-2.
Comparative example 3:
(1) 200.0g of industrially used waste hydrogenation catalyst Mo-Ni is taken and roasted in a muffle furnace at 450 ℃ for 10 hours. The obtained calcined product was designated as DZC-3.
The waste hydrogenation catalyst Mo-Ni hydrotreating catalyst comprises the following components: 20.71% molybdenum, calculated as molybdenum trioxide; 4.07% nickel, calculated as nickel oxide; 0.44% calcium calculated as calcium oxide; 1.24% iron, calculated as ferric oxide; 8.22% of carbon deposit, 10.35% of sulfur and the balance of carrier alumina.
In the roasting product of the step (1), the carbon content is 0.52 weight percent in terms of mass fraction.
200ml of solution was prepared with deionized water, phosphoric acid and sulfuric acid, and the resulting mixed acid solution was designated DAQ-3. Wherein the molar concentration of phosphoric acid is 0.4mol/L, and the molar concentration of sulfuric acid is 0.2mol/L.
100.0g of DZC-3 was taken, 200ml of DAQ-3 was added thereto, and the mixture was refluxed with heating at 100℃for 6.0 hours.
(2) After stopping heating, the pH of the test mixture was 1.0. And (3) carrying out suction filtration at the temperature of between 50 and 60 ℃, wherein the water quantity added in the suction filtration process is 80.0g, and the obtained filtrate is named as DFQ-3.
The added amounts of nickel and molybdenum elements were the same as those in the step (3) of example 1, and the resultant impregnation was heated and concentrated to 70.0ml, and the resultant impregnation was DJQ-3.
70.0g of alumina carrier A is taken, DJQ-3 is soaked on the carrier A, the carrier A is dried for 5 hours at 120 ℃, and then baked for 4 hours at 420 ℃, and the obtained catalyst is named DCT-3.DCT-3 had a weight of 98.9g
Comparative example 4:
23.0g of molybdenum trioxide, 17.0g of nickel nitrate hexahydrate, 5.0g of phosphoric acid with the mass fraction of 85 percent, 100ml of deionized water and heating to 100 ℃ for 6 hours, evaporating and concentrating to 70.0ml, and recording the prepared solution as DJQ-4. Namely, in the impregnating solution, the content of metallic molybdenum element was 2.28mol/L and the content of metallic nickel element was 0.84mol/L in terms of atom.
70.0g of alumina carrier A is taken, DJQ-4 is soaked on the carrier A, the carrier A is dried for 5 hours at 120 ℃, and then baked for 4 hours at 420 ℃, and the obtained catalyst is named DCT-4.
Comparative example 5:
23.0g of molybdenum trioxide, 17.0g of cobalt nitrate hexahydrate, 5.0g of phosphoric acid with the mass fraction of 85 percent, 100ml of deionized water and heating to 100 ℃ for 6 hours, evaporating and concentrating to 70.0ml, and recording the prepared solution as DJQ-5. Namely, in the impregnating solution, the content of metallic molybdenum element was 2.28mol/L and the content of metallic cobalt element was 0.83mol/L in terms of atom.
70.0g of alumina carrier A is taken, DJQ-5 is soaked on the carrier A, the carrier A is dried for 5 hours at 120 ℃, and then baked for 4 hours at 420 ℃, and the obtained catalyst is named DCT-5.
Comparative example 6:
(1) 200.0g of industrially used waste hydrogenation catalyst Mo-Ni is taken and roasted in a muffle furnace at 450 ℃ for 4 hours. The obtained calcined product was designated as DZC-6.
The waste hydrogenation catalyst Mo-Ni hydrotreating catalyst comprises the following components: 20.71% molybdenum, calculated as molybdenum trioxide; 4.07% nickel, calculated as nickel oxide; 0.44% calcium calculated as calcium oxide; 1.24% iron, calculated as ferric oxide; 8.22% of carbon deposit, 10.35% of sulfur and the balance of carrier alumina.
The carbon content of the roasted product is 0.52wt% in terms of mass fraction.
200ml of solution is prepared by deionized water, phosphoric acid and sulfuric acid, and the obtained mixed acid solution is referred to as DAQ-6, wherein the molar concentration of the phosphoric acid is 0.4mol/L, and the molar concentration of the sulfuric acid is 0.2mol/L.
100.0g of DZC-6 was taken, 200ml of a mixed acid solution DAQ-6 was added thereto, and the mixture was refluxed with heating at 100℃for 6.0 hours.
(2) After stopping heating, cooling to 40 ℃, slowly adding a diethylamine solution with a mass fraction of 10% to the reflux product, measuring the pH value of the solution during the period, and stopping dripping when the pH value of the solution is 4.0. The solution was then heated to 65℃for 1.0 hour. And (3) carrying out suction filtration at the temperature of between 50 and 60 ℃, wherein the water quantity added in the suction filtration process is 80.0g, and the obtained filtrate is named as DFQ-6.
(3) Adding nickel and molybdenum elements into the DFQ-6 in the step (2), heating and concentrating to 70.0ml, wherein the obtained impregnating solution is DJQ-6, wherein the adding amount is the same as that of the step (3) in the example 1.
70g of alumina carrier A was taken, the above DJQ-6 was impregnated on the carrier A, and after drying at 120℃for 5 hours and then baking at 420℃for 4 hours, the obtained catalyst was designated DCT-6.
Table 1 shows the metal content of the final catalyst obtained in each of the above examples. Table 2 shows the metal recovery rates of the corresponding examples.
TABLE 1 Metal content in the final catalysts obtained in each case
TABLE 2 utilization of active metals in spent catalyst in various examples
| Mo，wt％ | Ni，wt％ | Co，wt％ | |
| Example 1 | 84.18 | 90.79 | - |
| Example 2 | 80.85 | 86.57 | |
| Example 3 | 86.14 | 91.39 | |
| Example 4 | 80.96 | - | 84.59 |
| Example 5 | 82.89 | - | 87.53 |
| Comparative example 1 | 20.08 | 19.22 | - |
| Comparative example 2 | 86.59 | 93.07 | - |
| Comparative example 3 | 84.62 | 90.9 | - |
| Comparative example 6 | 82.06 | 91.11 | - |
The catalysts prepared in the examples and comparative examples were subjected to experimental evaluation by screening the catalysts, mixing 20ml of 20-30 mesh particles with 20ml of quartz sand with the same mesh number at a ratio of 1:1, and then filling the mixture into a reaction tube, wherein the reaction raw material is VGO, and the properties are shown in Table 2.
Before evaluation, the catalyst was subjected to in-situ sulfiding under the following conditions: cyclohexane solution of DMDS with 5% of vulcanizing liquid, vulcanizing pressure of 6.0MPa and liquid hourly space velocity of 1.5h -1 The hydrogen-oil volume ratio is 500:1, the temperature is 230 ℃ in the first stage of vulcanization, the duration is 5.0h, the temperature is 340 ℃ in the second stage of vulcanization, and the duration is 3.0h. After the completion of the vulcanization, the temperature of the reaction tube was lowered to room temperature, and then the raw materials were switched to evaluate the reaction.
The reaction evaluation condition is 370 ℃, the reaction pressure is 15.0MPa, and the liquid hourly space velocity is 1.0h -1 The hydrogen oil volume ratio is 1000:1, after 300 hours of reaction, the sample is sampled and analyzed, and the properties of the sample after hydrogenation reaction are shown in table 3.
TABLE 3 VGO feedstock Properties
TABLE 4 Properties of the product after hydrogenation
From the analysis and evaluation results of the metal content of the catalyst, the method of the embodiment of the invention can effectively utilize more than 80% of valuable metals such as Mo, ni, co and the like in the waste catalyst, and can effectively prevent Ca and Fe impurities from entering the solution, and the catalytic activity of the hydrogenation catalyst prepared from the impregnating solution has equivalent reaction activity under the condition of the same metal loading as that of the catalyst prepared from fresh raw materials. Compared with the comparative example, the method of the embodiment of the invention has obvious advantages on the metal utilization rate in the waste catalyst.
Claims (13)
1. A method for recycling waste hydrogenation catalyst comprises the following steps:
(1) Roasting the waste hydrogenation catalyst in an aerobic atmosphere; mixing the roasting product with an acid solution, and heating and refluxing;
(2) Adjusting the pH value of the reflux product obtained in the step (1) to 3.5-4.5 by using organic amine, and carrying out solid-liquid separation; the boiling point of the organic amine under normal pressure is more than or equal to 100 ℃;
(3) And (3) taking the liquid product obtained by filtering in the step (2) as an impregnating liquid impregnating carrier, and carrying out heat treatment to obtain the regenerated hydrogenation catalyst.
2. The process according to claim 1, wherein the organic amine in step (2) has a boiling point of 100 to 300 ℃ at normal pressure.
3. The method according to claim 1 or 2, wherein the organic amine in step (2) comprises at least one of ethylenediamine, 1, 2-propylenediamine, 1, 3-propylenediamine, dipropylamine, dibutylamine, pentylenediamine; preferably, the organic amine is added in the form of an organic amine solution, wherein the mass concentration of the organic amine solution is 2% to 20%, preferably 5% to 15%.
4. The method according to claim 1, wherein the mixture before solid-liquid separation in step (2) is heated; the heating temperature is 50-100 ℃, preferably 60-70 ℃; the heating time is 0.5 to 4 hours, preferably 1 to 2 hours.
5. The method according to claim 1, wherein the solid-liquid separation in step (2) is performed by suction filtration; in the suction filtration, the temperature of the suction filtrate is controlled to be 40-70 ℃, preferably 50-60 ℃.
6. The method according to claim 1, wherein in the step (1), the waste hydrogenation catalyst comprises, based on the mass of the catalyst:
5% -40% of molybdenum calculated by molybdenum trioxide;
2% -10% of at least one selected from nickel and cobalt in terms of oxide;
0.01 to 1.0 percent of calcium calculated by calcium oxide;
0.01 to 3.0 percent of iron calculated by ferric oxide;
the content of the sulfur element is 3% -15%;
50% -80% of carrier;
further, the carbon deposition is contained in an amount of 2.1 to 12.0 percent.
7. The method according to claim 1, wherein the carbon content in the calcined product of step (1) is 2.0wt% or less, preferably 0.6wt% or less, in terms of mass fraction.
8. The method according to claim 1, wherein the acid solution in step (1) is a mixed acid solution of phosphoric acid and sulfuric acid, wherein the molar concentration of phosphoric acid is 0.1 to 3.0mol/L, preferably 0.3 to 2.0mol/L, and the molar concentration of sulfuric acid is 0.05 to 1.0mol/L, preferably 0.1 to 0.6mol/L; and/or the mass ratio of the volume of the acid solution to the calcined product in step (1) is 1:1 to 4:1ml/g, preferably 1.5:1 to 3.0:1ml/g.
9. The process according to claim 1 or 8, wherein the temperature of the heated reflux in step (1) is 80-105 ℃, preferably 95-100 ℃; the heating time is 2.0 to 12.0 hours, preferably 4.0 to 8.0 hours.
10. The method according to claim 1, wherein the impregnating solution in step (3) is used as a mother solution, and the mother solution is adjusted so that the content of active metal in the adjusted mother solution is suitable for hydrogenation catalytic reaction, wherein the adjusting method is to add an active metal source or add water for dilution; preferably, the content of metallic molybdenum element in the impregnating solution obtained after the mother solution is regulated in the step (3) is 0.5-5.0 mol/L, preferably 0.8-4.0 mol/L in terms of atoms; the content of metallic nickel and/or cobalt element is 0.2 to 2.0mol/L, preferably 0.3 to 1.5mol/L.
11. The method of claim 1, wherein the support in step (3) comprises one or more of alumina, silica, amorphous silica alumina, and titania-containing alumina.
12. The method according to claim 1 or 11, wherein the specific surface area of the carrier in step (3) is 150 to 500m 2 Preferably 200 to 400m 2 Per gram, the pore volume of the carrier is 0.2-1.2 cm 3 /g，0.3～1.0cm 3 /g。
13. The method according to claim 1, wherein the conditions of the heat treatment in step (3) are: the temperature of the heat treatment is 80-800 ℃, preferably 100-550 ℃, and the heat treatment time is 2-20 hours, preferably 4-15 hours.
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