CN112547080A - Method for recycling supported hydrogenation catalyst - Google Patents
Method for recycling supported hydrogenation catalyst Download PDFInfo
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- CN112547080A CN112547080A CN202011575839.XA CN202011575839A CN112547080A CN 112547080 A CN112547080 A CN 112547080A CN 202011575839 A CN202011575839 A CN 202011575839A CN 112547080 A CN112547080 A CN 112547080A
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- recycling
- catalyst
- hydrogenation catalyst
- waste
- carrier
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- 239000003054 catalyst Substances 0.000 title claims abstract description 103
- 238000000034 method Methods 0.000 title claims abstract description 48
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 32
- 238000004064 recycling Methods 0.000 title claims abstract description 23
- 239000002699 waste material Substances 0.000 claims abstract description 41
- 238000001035 drying Methods 0.000 claims abstract description 23
- 238000004898 kneading Methods 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 239000011261 inert gas Substances 0.000 claims abstract description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000006259 organic additive Substances 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 239000010419 fine particle Substances 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 238000007493 shaping process Methods 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910021536 Zeolite Inorganic materials 0.000 claims description 5
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 5
- 239000002808 molecular sieve Substances 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
- 239000010457 zeolite Substances 0.000 claims description 5
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 150000002751 molybdenum Chemical class 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 238000001935 peptisation Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 238000005470 impregnation Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 7
- 239000007788 liquid Substances 0.000 abstract description 6
- 230000003993 interaction Effects 0.000 abstract description 4
- 239000000843 powder Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 3
- 238000011068 loading method Methods 0.000 abstract description 2
- 238000001125 extrusion Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 21
- 239000012299 nitrogen atmosphere Substances 0.000 description 10
- 241000219793 Trifolium Species 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 238000002791 soaking Methods 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000002283 diesel fuel Substances 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 3
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 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
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000003313 weakening effect Effects 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a method for recycling a supported hydrogenation catalyst, and belongs to the field of catalyst recycling. The deactivated hydrogenation catalyst is regenerated and sieved, and the sieved small particles and powder are treated as solid garbage, so that the environment is polluted and the resource waste is caused. In the invention, firstly, the screened waste catalyst is crushed to below 50 microns, then the crushed waste catalyst is added into a mixing and kneading process for preparing the carrier according to a certain proportion, the mixed carrier is prepared by extrusion molding, drying and roasting in an inert gas atmosphere, the carbon on the waste catalyst weakens the interaction between metal and the carrier, and the active component impregnation liquid is supplemented for loading, so that the prepared catalyst has higher hydrodesulfurization activity. The method can completely recycle the waste catalyst, and solves the problem of waste of the conventional waste catalyst as solid garbage disposal in one step.
Description
Technical Field
The invention belongs to the technical field of hydrogenation catalyst recovery, and particularly relates to a method for recycling a supported hydrogenation catalyst.
Background
Hydrogenation catalysts are the most important catalysts in petroleum processing and generally include hydrofinishing, hydrotreating and hydrocracking catalysts. The hydrogenation catalyst for industrial application is a supported hydrogenation catalyst prepared by using a VIB group metal or a VIB group and VIIIB group binary or ternary metal system as an active center, using alumina or a composite oxide obtained by doping alumina and one or more components of other metal oxides (such as titanium oxide, zirconium oxide, silicon oxide, amorphous silicon aluminum, molecular sieves, zeolite and the like) as a carrier and adopting a method of impregnation and the like. The fresh catalyst is sulfurized to generate activity, and can form type I or type II active centers according to different preparation conditions. The dispersion degree of the I-type active center is high, the interaction between the active center and the carrier is strong, the vulcanization is insufficient, and the intrinsic activity of the active center is low; the dispersion degree of the II type active center is low, the action of the active center and the carrier is weak, the sulfuration is complete, and the intrinsic activity is high. Most researchers have been working on the development of highly active type II active site hydrogenation catalysts.
The appropriate weakening of the forces between the support and the active component is one of the methods for the development of highly active hydrogenation catalysts. Generally, the introduction of an amount of carbon on the catalyst isolates the direct interaction of the active metal and the support, promoting the formation of type II active centers. For the regenerated catalyst, considering the damage of high temperature to the catalyst structure, and the migration, agglomeration and loss of active metal, the regeneration temperature is generally not higher than 500 ℃, carbon on the catalyst is not easy to burn off at the temperature, and a certain amount of carbon exists on the regenerated catalyst. After regeneration, the catalyst needs to be sieved to remove fine particles, so that the pressure drop of a reaction system is prevented from being increased due to the fact that the fine particles block a catalyst bed layer or a pipeline, and unplanned shutdown is avoided. The screened fine particles are generally used as industrial waste to be buried, and the treatment mode not only wastes resources, but also causes environmental pollution.
The recycling of the spent catalyst is a constant concern. Some recovery techniques of the spent catalyst have been developed, and most techniques mainly recover metals in the spent catalyst because of high metal recovery value. Chinese patent CN200810228402.1 discloses a method for recovering molybdenum from molybdenum-containing spent catalyst, which comprises roasting and crushing the spent catalyst, mixing with alkaline substance, roasting, leaching with mixed acid solution, and precipitating with alkaline solution to recover molybdenum. CN201110432230.1 discloses a method for recovering metal tungsten and nickel from waste nickel-tungsten catalysts, which comprises the steps of carrying out high-temperature reduction roasting on the waste catalysts, carrying out extraction separation and concentration crystallization on a replacement leached solution to obtain nickel crystals, carrying out high-temperature roasting on the replacement leached filter residues, washing with hot water, and recovering tungsten by using acid. CN202010405370.9 discloses a method for recovering and preparing solid sodium metaaluminate and pseudo-boehmite from molybdenum-nickel spent catalyst. Firstly, extracting, roasting and screening the inactivated hydrogenation demetalization catalyst, then, sequentially carrying out saturated dipping treatment by using an organic acid solution and an alkali solution, and finally, filtering, drying and roasting to recover the carrier component.
The method uses a large amount of acid and alkali no matter the metal components in the waste catalyst or the carrier are recovered, multiple times of extraction is needed, the extraction process is very complicated to control, the recovery rate is low, the product purity is low, and the industrial production difficulty is high. The fine particles screened out in the regeneration process are used as industrial waste to be buried, so that resources are wasted, and environmental pollution is caused. Therefore, it is necessary to develop a method for recycling the waste hydrogenation catalyst with low cost.
Disclosure of Invention
In order to solve the problems, the invention provides a method for recycling a supported hydrogenation catalyst. The deactivated hydrogenation catalyst is regenerated and sieved, the sieved fine particles are crushed into particles with the particle size of less than 50 microns, then the particles are added into a kneading process for preparing the carrier according to a certain proportion, the particles are extruded, formed and dried, and the particles are roasted in an inert gas atmosphere to prepare a mixed carrier, the interaction between metal and the carrier is weakened by carbon in the particles, and the prepared catalyst has high hydrodesulfurization activity. The method can completely recycle the screened waste catalyst, and solves the problem of waste of the conventional screened waste catalyst as solid waste. Meanwhile, the addition amount of the organic additive is reduced, the viscosity of the impregnation liquid is reduced, the impregnation time is shortened, and the method has important industrial application value.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for recycling a supported hydrogenation catalyst comprises the following steps:
(1) crushing the screened waste catalyst: sieving the waste hydrogenation catalyst, and then crushing the sieved fine particles into particles below 50 microns; preferably to less than 10 microns.
(2) Kneading and molding: adding the screened waste catalyst particles into the primary carrier in the kneading process, uniformly mixing, adding an acid solution for peptization, extruding into strips for forming, drying, shaping and screening, and roasting in an inert gas atmosphere to prepare a blended carrier;
(3) and (3) preparing a solution from a VIB group element-containing compound, a VIII group element-containing compound and a solvent, impregnating the mixed carrier obtained in the step (2), and drying or roasting in an inert atmosphere to obtain the hydrogenation catalyst.
Furthermore, the waste catalyst used in the step (1) is a supported catalyst which takes VIB group metal or VIB and VIIIB group binary or ternary metal as an active center, and takes composite oxide obtained by doping alumina or alumina and one or more of titanium oxide, zirconium oxide, silicon oxide, amorphous silicon aluminum, molecular sieve and zeolite as a carrier.
Further, the waste catalyst used in the step (1) has a sulfur content of not more than 1.0% and a carbon content of not more than 4.0%.
Further, the adding amount of the waste catalyst particles in the step (2) is 10-50% of the mass of the primary carrier.
Further, the preliminary carrier in the step (2) comprises pseudo-boehmite, or pseudo-boehmite mixed with one or more components of titanium oxide, zirconium oxide, silicon oxide, amorphous silicon aluminum, molecular sieve, zeolite and the like.
Further, the adding amount of the acid solution in the step (2) is 1-10% of the total mass of the carrier; the acid solution is an inorganic acid or an organic acid, wherein the inorganic acid comprises any one of sulfuric acid, phosphoric acid, hydrochloric acid and nitric acid, the organic acid comprises any one of acetic acid, oxalic acid and citric acid, the concentration of the acid solution is preferably 3-5 wt%, and the acid solution is preferably a nitric acid solution.
Further, the drying process in the step (2) is as follows: drying for 2-4 h at room temperature, and then drying for 2-4 h in an oven at 120 ℃.
Further, the roasting conditions in the inert gas atmosphere in the step (2) are specifically as follows: the inert gas is one or more of nitrogen, argon and helium, the roasting is carried out by heating from room temperature to 400-1000 ℃ at a heating rate of 10-50 ℃/min for 4 hours, preferably, the heating rate is 10 ℃/min, and the roasting temperature is 900 ℃.
Further, the compound of the group VIB element in step (3) is preferably a nickel salt, the nickel salt includes but is not limited to one or more of nickel nitrate, nickel acetate and basic nickel carbonate, and the compound of the group VIB element is preferably a molybdenum salt, and includes but is not limited to molybdate, molybdenum trioxide and the like; preferably, the nickel salt is basic nickel carbonate and the molybdenum salt is molybdenum trioxide.
Further, the solvent in the step (3) is phosphoric acid solution or phosphoric acid solution added with organic additives, and the organic additives are one or more of ethylene glycol, diethylene glycol, glycerol and citric acid.
Has the advantages that: the invention realizes the recycling of the waste catalyst by one step, and the recycling method is simple; the method overcomes the defect that the waste catalyst is used as industrial solid waste for landfill treatment, reduces the use amount of organic additives due to residual carbon on the waste catalyst, and reduces the preparation cost of the catalyst.
Detailed Description
The preparation and use of the present invention are further described with reference to the following specific examples, but the specific embodiments described herein are only for illustrating and explaining the present invention and are not intended to limit the present invention.
Example 1
Weighing 204.0g of macroporous pseudo-boehmite, uniformly mixing with 15 g of sieved waste catalyst powder, slowly adding 5wt% of nitric acid solution in the kneading process, continuously kneading for 10 min for peptizing, extruding and molding to prepare clover strips with the diameter phi of 1.45, standing for 2 h at room temperature, drying for 2 h in a 120 ℃ oven, cooling to room temperature, shaping to obtain clover strips with the length of 3-5mm, sieving by using a 20-mesh standard sieve, placing in a muffle furnace, heating from room temperature to 900 ℃ at the speed of 10 ℃/min, roasting for 4h under the nitrogen atmosphere, and naturally cooling to room temperature to obtain the blended carrier S1.
Weighing 18 g of concentrated phosphoric acid (85 wt%), dissolving in 50 g of deionized water, mixing with 34 g of molybdenum oxide and 12 g of basic nickel carbonate, and stirring and refluxing at 90 ℃ and 300r/min until the concentrated phosphoric acid is completely dissolved to prepare impregnation liquid A.
Weighing 100 g of the mixed carrier S1, soaking the soaking solution A on the carrier in an equal volume according to the water absorption of the mixed carrier S1, drying the carrier at 120 ℃ for 4 hours, and keeping the temperature at 200 ℃ for 4 hours under a nitrogen atmosphere to obtain the catalyst C1.
Example 2
Weighing 204.0g of macroporous pseudo-boehmite, uniformly mixing with 45 g of sieved waste catalyst powder, slowly adding 5wt% of nitric acid solution in the kneading process, continuously kneading for 10 min for peptizing, extruding and molding to prepare clover strips with the diameter phi of 1.45, standing for 2 h at room temperature, drying for 2 h in a 120 ℃ oven, cooling to room temperature, shaping to obtain clover strips with the length of 3-5mm, sieving by using a 20-mesh standard sieve, placing in a muffle furnace, heating from room temperature to 900 ℃ at the speed of 10 ℃/min, roasting for 4h under the nitrogen atmosphere, and naturally cooling to room temperature to obtain the blended carrier S2.
Weighing 100 g of the mixed carrier S2, soaking the soaking solution A on the carrier in an equal volume according to the water absorption of the mixed carrier S2, drying the carrier at 120 ℃ for 4 hours, and keeping the temperature at 200 ℃ for 4 hours under a nitrogen atmosphere to obtain the catalyst C2.
Example 3
Weighing 204.0g of macroporous pseudo-boehmite, uniformly mixing with 75 g of sieved waste catalyst powder, slowly adding 5wt% of nitric acid solution in the kneading process, continuously kneading for 10 min for peptizing, extruding and molding to prepare clover strips with the diameter phi of 1.45, standing for 2 h at room temperature, drying for 2 h in a 120 ℃ oven, cooling to room temperature, shaping to obtain clover strips with the length of 3-5mm, sieving by using a 20-mesh standard sieve, placing in a muffle furnace, heating from room temperature to 900 ℃ at the speed of 10 ℃/min, roasting for 4h under the nitrogen atmosphere, and naturally cooling to room temperature to obtain the blended carrier S3.
Weighing 100 g of the mixed carrier S3, soaking the soaking solution A on the carrier in an equal volume according to the water absorption of the mixed carrier S3, drying the carrier at 120 ℃ for 4 hours, and keeping the temperature at 200 ℃ for 4 hours under a nitrogen atmosphere to obtain the catalyst C3.
Example 4
Adding 15 g of ethylene glycol into the impregnation liquid A, continuously stirring and refluxing for 2 h at 90 ℃ and 300r/min, impregnating on 100 g of mixed carrier S3 in an equal volume, drying for 4h at 120 ℃, and keeping the temperature of 200 ℃ for 4h under a nitrogen atmosphere to obtain a catalyst C4.
Comparative example 1
Weighing 204.0g of macroporous pseudo-boehmite, slowly adding 5wt% of nitric acid solution in the process of kneading, continuously kneading for 10 minutes for peptizing, extruding and forming to obtain clover strips with the diameter phi of 1.45, drying for 2 hours at room temperature, drying for 2 hours in an oven at 120 ℃, cooling to room temperature, shaping to obtain clover strips with the length of 3-5mm, sieving by using a 20-mesh standard sieve, placing in a muffle furnace, raising the temperature from room temperature to 900 ℃ at the speed of 10 ℃/minute in the nitrogen atmosphere, keeping the temperature for 4 hours, and naturally cooling to room temperature to obtain the alumina carrier S4.
Soaking the soaking solution A on 100 g of alumina carrier S4 in the same volume, drying at 120 ℃ for 4h, and keeping the temperature at 200 ℃ for 4h under a nitrogen atmosphere to obtain the catalyst C5.
Comparative example 2
Adding 30 g of ethylene glycol into the impregnation liquid A, continuously stirring and refluxing for 2 h at 90 ℃ and 300r/min, impregnating on 100 g of alumina carrier S4 in an equal volume, drying for 4h at 120 ℃, and keeping the temperature constant at 200 ℃ for 4h under a nitrogen atmosphere to obtain a catalyst C6.
The carriers are respectively subjected to physicochemical property tests, and the results are shown in table 1:
TABLE 1 Carrier Properties
From examples 1 to 3, it can be seen that the specific surface area of the blending carriers S1 to S3 was from 129 m with the increase in the amount of the waste catalyst incorporated2The/g is reduced to 98 m2(ii)/g; the pore volume is in a descending trend; the average pore diameter is not obviously changed along with the increase of the doping amount and is kept at about 16 nm; the lateral pressure strength is reduced quickly to 118N/cm at higher doping amount, but meets the requirement of industrial application. The comparative example 1 is an alumina carrier without doping a waste catalyst, compared with a doped carrier, the doping of a proper amount of the waste catalyst has little influence on the specific surface area, the pore volume, the average pore diameter and the lateral pressure strength of the carrier, and shows that the doped carrier has excellent physical and chemical properties, is suitable for serving as a catalyst carrier and simultaneously solves the problem of recycling the waste catalyst.
Application example 1: diesel oil hydrorefining reaction
The hydrofining activity evaluation of C1-C6 was carried out on a fixed bed pilot plant, the loading of the catalyst was 20 mL, and the reaction conditions were: the reaction temperature is 340 ℃, the hydrogen pressure is 9 MPa, the hydrogen-oil volume ratio is 300:1, and the space velocity is 1.5 h-1. The mixed diesel oil is used as a reaction raw material, and the properties of the mixed diesel oil are shown in the following table 2.
TABLE 2 Mixed Diesel feedstock Properties
The catalyst test results are shown in table 3 below.
TABLE 3 catalyst test results
The catalyst test results show that compared with the C5 without the waste catalyst, the hydrodesulfurization activity of the catalysts C1-C3 prepared by adding different amounts of waste catalysts is improved, the sulfur content of refined diesel oil is less than 10 ppm, the polycyclic aromatic hydrocarbon content is obviously reduced, and the hydrogenation performance of the catalyst is excellent. Compared with the catalyst C3, the catalyst C4 is supplemented with organic additive ethylene glycol, and the hydrogenation and desulfurization performance reaches the level of the fresh catalyst C6. In the waste catalyst mixed with the carrier, the recycling problem of the waste catalyst is solved, the addition amount of organic additives in the impregnation is reduced, the viscosity of the impregnation liquid is reduced, the uniform impregnation is facilitated, the production efficiency of the catalyst is improved, and the method has great industrial application value.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (10)
1. A method for recycling a supported hydrogenation catalyst is characterized by comprising the following steps: the method comprises the following steps:
(1) crushing the screened waste catalyst: sieving the waste hydrogenation catalyst, and then crushing the sieved fine particles into particles below 50 microns;
(2) kneading and molding: adding the screened waste catalyst particles into the primary carrier in the kneading process, uniformly mixing, adding an acid solution for peptization, extruding into strips for forming, drying, shaping and screening, and roasting in an inert gas atmosphere to prepare a blended carrier;
(3) and (3) preparing a solution from a VIB group element-containing compound, a VIII group element-containing compound and a solvent, impregnating the mixed carrier obtained in the step (2), and drying or roasting in an inert atmosphere to obtain the hydrogenation catalyst.
2. The method for recycling the supported hydrogenation catalyst according to claim 1, wherein the method comprises the following steps: the waste catalyst used in the step (1) is a supported catalyst which takes VIB group metal or VIB and VIIIB group binary or ternary metal as an active center, and takes composite oxide obtained by doping alumina or alumina and one or more of titanium oxide, zirconium oxide, silicon oxide, amorphous silicon-aluminum, molecular sieve and zeolite as a carrier.
3. The method for recycling the supported hydrogenation catalyst according to claim 1, wherein the method comprises the following steps: the waste catalyst used in the step (1) has a sulfur content of not more than 1.0% and a carbon content of not more than 4.0%.
4. The method for recycling the supported hydrogenation catalyst according to claim 1, wherein the method comprises the following steps: and (3) adding the waste catalyst particles in the step (2) in an amount of 10-50% of the mass of the primary carrier.
5. The method for recycling the supported hydrogenation catalyst according to claim 1, wherein the method comprises the following steps: the primary carrier in the step (2) comprises pseudo-boehmite, or the pseudo-boehmite is mixed with one or more components of titanium oxide, zirconium oxide, silicon oxide, amorphous silicon-aluminum, molecular sieve, zeolite and the like.
6. The method for recycling the supported hydrogenation catalyst according to claim 1, wherein the method comprises the following steps: the adding amount of the acid solution in the step (2) is 1-10% of the total mass of the carrier; the acid solution is inorganic acid or organic acid, wherein the inorganic acid comprises any one of sulfuric acid, phosphoric acid, hydrochloric acid and nitric acid, and the organic acid comprises any one of acetic acid, oxalic acid and citric acid.
7. The method for recycling the supported hydrogenation catalyst according to claim 1, wherein the method comprises the following steps: the drying process in the step (2) is as follows: drying for 2-4 h at room temperature, and then drying for 2-4 h in an oven at 120 ℃.
8. The method for recycling the supported hydrogenation catalyst according to claim 1, wherein the method comprises the following steps: the roasting condition in the inert gas atmosphere in the step (2) is specifically as follows: the inert gas is one or more of nitrogen, argon and helium, and the roasting is carried out by raising the temperature from room temperature to 400-1000 ℃ at a temperature raising rate of 10-50 ℃/min and maintaining for 4 hours.
9. The method for recycling the supported hydrogenation catalyst according to claim 1, wherein the method comprises the following steps: and (3) the VIB group element compound is nickel salt, and the VIB group element compound is molybdenum salt.
10. The method for recycling the supported hydrogenation catalyst according to claim 1, wherein the method comprises the following steps: and (3) the solvent is phosphoric acid solution or phosphoric acid solution added with organic additives, and the organic additives are one or a mixture of more of ethylene glycol, diethylene glycol, glycerol and citric acid.
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