CN112958095A - Two-dimensional carrier material loaded catalyst and preparation method and application thereof - Google Patents
Two-dimensional carrier material loaded catalyst and preparation method and application thereof Download PDFInfo
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- CN112958095A CN112958095A CN202110235303.1A CN202110235303A CN112958095A CN 112958095 A CN112958095 A CN 112958095A CN 202110235303 A CN202110235303 A CN 202110235303A CN 112958095 A CN112958095 A CN 112958095A
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- graphene
- catalyst
- oxide
- carrier material
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- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- 239000012876 carrier material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 43
- 239000002131 composite material Substances 0.000 claims abstract description 31
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 30
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000011280 coal tar Substances 0.000 claims abstract description 24
- 238000005470 impregnation Methods 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 238000001338 self-assembly Methods 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000011068 loading method Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 20
- 239000011550 stock solution Substances 0.000 claims description 19
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- 229910052593 corundum Inorganic materials 0.000 claims description 14
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 14
- 239000012286 potassium permanganate Substances 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 10
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 9
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 6
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 6
- 238000004073 vulcanization Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 4
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 71
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 22
- 229910052717 sulfur Inorganic materials 0.000 abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 5
- 239000011593 sulfur Substances 0.000 abstract description 5
- 239000012535 impurity Substances 0.000 abstract description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 abstract description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 36
- 239000000203 mixture Substances 0.000 description 30
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 28
- 238000010438 heat treatment Methods 0.000 description 21
- 239000008367 deionised water Substances 0.000 description 18
- 229910021641 deionized water Inorganic materials 0.000 description 18
- 239000000243 solution Substances 0.000 description 16
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 14
- 238000000227 grinding Methods 0.000 description 13
- 239000003921 oil Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 238000011049 filling Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 229910003294 NiMo Inorganic materials 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 5
- 238000006477 desulfuration reaction Methods 0.000 description 5
- 230000023556 desulfurization Effects 0.000 description 5
- 239000000295 fuel oil Substances 0.000 description 5
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 4
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 4
- 238000007865 diluting Methods 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910001437 manganese ion Inorganic materials 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229910001414 potassium ion Inorganic materials 0.000 description 4
- -1 potassium ions Chemical class 0.000 description 4
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 4
- DEDZSLCZHWTGOR-UHFFFAOYSA-N propylcyclohexane Chemical compound CCCC1CCCCC1 DEDZSLCZHWTGOR-UHFFFAOYSA-N 0.000 description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- GNMCGMFNBARSIY-UHFFFAOYSA-N 1,2,3,4,4a,4b,5,6,7,8,8a,9,10,10a-tetradecahydrophenanthrene Chemical compound C1CCCC2C3CCCCC3CCC21 GNMCGMFNBARSIY-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 3
- PETRWTHZSKVLRE-UHFFFAOYSA-N 2-Methoxy-4-methylphenol Chemical compound COC1=CC(C)=CC=C1O PETRWTHZSKVLRE-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910009819 Ti3C2 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000000802 evaporation-induced self-assembly Methods 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910003076 TiO2-Al2O3 Inorganic materials 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000012072 active phase Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229940111121 antirheumatic drug quinolines Drugs 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005685 electric field effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
Images
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/74—Iron group metals
- B01J23/75—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
- B01J23/888—Tungsten
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- 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
-
- 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
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- 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
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
- C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
- C10G45/48—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
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- 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
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
- C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
- C10G45/48—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/50—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum or tungsten metal, or compounds thereof
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention is suitable for the technical field of hydrogenation catalysts, and provides a catalyst loaded by a two-dimensional carrier material, a preparation method and application thereof, wherein the preparation method of the catalyst comprises the following steps: preparing graphene oxide; preparing a graphene-like composite metal oxide two-dimensional carrier material by taking graphene oxide as a structure directing agent and metal precursor salt as a raw material through a solvent volatilization self-assembly method; and (3) loading active metal on the graphene-like composite metal oxide two-dimensional carrier material by adopting an isometric co-impregnation method to obtain the catalyst. The catalyst is applied to the coal tar hydrofining reaction, has high-efficiency hydrogenation and impurity removal performance, effectively removes sulfur-containing and nitrogen-containing compounds in the coal tar, has good polycyclic aromatic hydrocarbon hydrogenation saturation performance, and has good application value in the coal tar hydrofining aspect.
Description
Technical Field
The invention belongs to the technical field of hydrogenation catalysts, and particularly relates to a catalyst loaded by a two-dimensional carrier material, and a preparation method and application thereof.
Background
Coal tar is directly used as fuel, and because the content of S, N in the coal tar is high, a large amount of NOx and SOx pollutants are emitted during combustion, so that serious environmental pollution is caused, for example: acid rain, haze, etc. The deep processing treatment of the coal tar by adopting the hydro-upgrading process not only can reasonably utilize resources and reduce environmental pollution, but also improves the use value of the coal tar. The hydrorefining reaction is a reaction that occurs on a catalyst bed by hydrogenation under a high pressure condition, and the hydrogenation process includes Hydrodeoxygenation (HDO), Hydrodesulfurization (HDS), Hydrodenitrogenation (HDN), aromatic saturation, and the like. The hydrofining aims to remove sulfur, nitrogen, oxygen and metal impurities in the oil product, saturate olefin, change the composition, smell, combustibility, stability and the like of the oil product, achieve the aims of changing the property of the oil product and improving the use value, and finally prepare naphtha and high-quality fuel oil.
The key factor in hydrogenation technology is the design of catalysts with good hydrogenation performance. The most commonly used commercial hydrogenation catalyst in coal tar hydrofinishing is Ni-promoted MoS supported on metal oxides2A bimetallic catalyst. Research on NiMoS catalysts has never been stopped for decades, and efforts have been made to improve NiMoS catalysts, mainly for the purpose of increasing catalyst activity and simplifying catalyst preparation processes.
γ-Al2O3Due to their low cost, relatively high surface area, high stability and excellent formability, are often used as commercial hydrofinishing catalyst supports. However, with ordinary gamma-Al2O3Is a carrier of the NiMoS catalyst, gamma-Al2O3Can form Mo-O-Al bonds with active metals, so that strong interaction exists between the carrier and the active metals, further limits the vulcanization of the active metals, and leads to the formation of a large amount of type I NiMoS active phases which show relatively low catalytic hydrogenation performance. Furthermore, it is becoming more and more difficult to produce fuel oil meeting strict quality standards from raw tars of increasingly lower quality using commercial hydrofinishing catalysts, and new support materials for highly efficient hydrofinishing catalysts have to be found.
Two-dimensional (2D) materials have attracted considerable attention in the field of catalysis due to their unique electronic, mechanical and chemical properties. From 2004 Geim et al (Novoseov K S, Geim a K, Morozov S V.electric field effect in atomic of carbon files [ J]Since the graphene with only one atomic layer thickness is obtained by mechanically peeling off the graphite by using an adhesive tape, many graphene-like materials are developed and prepared in succession, which rapidly drives the research of two-dimensional materials. A two-dimensional material is a material in which electrons are free to move in only two dimensions, with large lateral dimensions and only one or a few atomic layers thick in the thickness direction. Compared with the traditional catalytic material, the 2D material has larger specific surface area and abundant defect sites, and can provide more catalytic active sites. Catalytic hydrogenation performance study of Liutian column (Liutian column, alumina and MXene (Ti3C2) supported palladium catalyst [ D]Zhejiang industrial university, 2018.) with MXene (Ti), a two-dimensional material3C2) As carrier, Ti is treated by sodium hydroxide solution3C2Pd nano particles are loaded after pretreatment to obtain Pd/Ti3C2-NaOH catalyst and applying the catalyst in tests of the catalytic hydrogenation reaction of vanillin. The results show that Pd/Ti3C2the-NaOH catalyst has excellent catalytic activity and relatively better cycle stability (the substrate conversion rate and the selectivity of 4-methyl guaiacol are both more than 99 percent). Lei et al (Lei L., Wu Z., Liu H., et al. A method for the synthesis of graphene-like 2D metals and the excellent catalytic application of the hydrogenation of nitroarenes [ J].Journal of Materials Chemistry A,20189948-9961) adopts an improved evaporation-induced self-assembly (EISA) method to synthesize graphene-like CeO2Nanosheet (NS-CeO)2) Research on the load at NS-CeO2Pd cluster on (Pd/NS-CeO)2) Catalytic performance in hydrogenation of nitroaromatic. As a result, it was found that there was Pd cluster-modified CeO2The nanosheet shows excellent catalytic performance in the hydrogenation of nitroaromatic hydrocarbon under mild conditions.
A series of researches on the catalytic application of two-dimensional materials provide a new choice for the development of high-efficiency hydrofining catalysts. Therefore, the preparation of the graphene-like hydrofining catalyst based on the carbon-based material improves the hydrogenation performance of the catalyst, realizes the deep hydrogenation and impurity removal of coal tar, and is worthy of deep research.
Disclosure of Invention
The embodiment of the invention aims to provide a preparation method of a catalyst loaded by a two-dimensional carrier material, aiming at solving the problems in the background art.
The embodiment of the invention is realized in such a way that the preparation method of the catalyst loaded by the two-dimensional carrier material is characterized by comprising the following steps:
preparing graphene oxide;
preparing a graphene-like composite metal oxide two-dimensional carrier material by taking graphene oxide as a structure directing agent and metal precursor salt as a raw material through a solvent volatilization self-assembly method;
and (3) loading active metal on the graphene-like composite metal oxide two-dimensional carrier material by adopting an isometric co-impregnation method to obtain the catalyst.
Specifically, a modified Hummers method can be used to prepare highly dispersed Graphene Oxide (GO).
Further, the metal oxide is Al2O3、TiO2、CeO2Of isometal oxides or TiO2-Al2O3，CeO2-Al2O3And the like.
As a preferred embodiment of the present invention, the step of preparing graphene oxide specifically includes:
adding graphite powder and sodium nitrate into sulfuric acid, mixing, and adding potassium permanganate to react to obtain a graphene oxide stock solution;
and standing the graphene oxide stock solution, centrifuging and washing to be neutral, and freeze-drying to obtain the graphene oxide.
As another preferred embodiment of the present invention, the step of preparing the graphene-like composite metal oxide two-dimensional carrier material by using graphene oxide as a structure directing agent and a metal precursor salt as a raw material and using a solvent volatilization self-assembly method specifically includes:
dispersing graphene oxide in absolute ethyl alcohol, adding metal precursor salt and aluminum isopropoxide, stirring, drying and roasting to obtain a graphene-like composite metal oxide two-dimensional carrier material;
or comprises the following steps:
dispersing graphene oxide in absolute ethyl alcohol, adding aluminum isopropoxide, stirring, drying and roasting to obtain graphene-like Al2O3；
Adding metal precursor salt into absolute ethyl alcohol for mixing to obtain an impregnation liquid;
graphene-like Al2O3Adding the graphene-like composite metal oxide into the impregnation liquid, stirring and impregnating, and then drying and roasting to obtain the graphene-like composite metal oxide two-dimensional carrier material.
In another preferred embodiment of the present invention, the metal precursor salt is at least one of tetrabutyl titanate (TBT), aluminum isopropoxide, zirconium oxychloride, cerium nitrate and zirconium nitrate.
In another preferred embodiment of the present invention, the active metal is at least one of Ni, Mo, Co, and W.
As another preferable aspect of the embodiment of the present invention, the preparation method further includes the steps of:
and tabletting and screening the catalyst, and then placing the catalyst in an atmosphere containing hydrogen sulfide and hydrogen for vulcanization treatment.
Specifically, the hydrogen sulfide content of the atmosphere of hydrogen sulfide and hydrogen is 5-15 vol%; the temperature of the vulcanization treatment is 300-400 ℃.
Another object of the embodiments of the present invention is to provide a catalyst prepared by the above preparation method.
Another object of the embodiments of the present invention is to provide an application of the above catalyst in coal tar hydrofining.
Specifically, the catalyst can be applied to coal tar Hydrodesulfurization (HDS), Hydrodenitrogenation (HDN) and aromatic hydrocarbon hydrogenation saturation.
According to the preparation method of the catalyst loaded by the two-dimensional carrier material, provided by the embodiment of the invention, graphene oxide is used as a structure directing agent, the graphene-like composite metal oxide two-dimensional carrier material with large specific surface area and abundant defect sites is prepared by a solvent volatilization self-assembly method, and then an isometric impregnation method is adopted to load active metal on the graphene-like composite metal oxide two-dimensional carrier material, so that more active sites can be provided, the adsorption of reactants is facilitated, and the catalytic hydrogenation performance of the catalyst is further improved; the catalyst is applied to the coal tar hydrofining reaction, has high-efficiency hydrogenation and impurity removal performance, effectively removes sulfur-containing and nitrogen-containing compounds in the coal tar, has good polycyclic aromatic hydrocarbon hydrogenation saturation performance, and has good application value in the coal tar hydrofining aspect.
Drawings
FIG. 1 is an SEM image of a catalyst prepared in example 2 of the present invention.
FIG. 2 is a graph of the results of the complete denitrification rate of quinoline on a NiMoS catalyst.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
This embodiment provides a method for preparing a catalyst supported on a two-dimensional support material, which is characterized by comprising the following steps:
s1, mixing 5g of graphite powder and 2.5g of NaNO3Add 130mL of concentrated H2SO4In an ice bath for 2h (reaction temperature not exceeding-5 ℃). Then 15g KMnO4(KMnO is preliminarily mixed4Grinding the particles into powder) is slowly added into the reaction system (the addition is finished within 3-4h, and the temperature of the reaction system is maintained at 5-10 ℃). The above solution was transferred to a 35 ℃ water bath (the bath kettle temperature was previously heated to 35 ℃) and 230mL of deionized water (temperature below 50 ℃) was slowly added thereto and the reaction was continued with stirring for 1 h. The temperature of the water bath is adjusted to 98 ℃, the heating is closed after the stirring reaction is carried out for 30min, and 400mL of deionized water is slowly added into the system for diluting. After the reaction, 10mL of 30 wt% hydrogen peroxide is added to remove the unreacted KMnO4And stirred for 1 h. And after the GO is prepared, filling the obtained GO stock solution into a 2L big beaker, filling deionized water, stirring for 1h, and standing. And after GO completely sinks into the bottom, removing the supernatant. After repeating the step for 5 times, centrifuging the GO stock solution to be neutral in a centrifugal washing mode to remove residual water-soluble ions (such as potassium ions, sodium ions, manganese ions, sulfate ions and the like) in the GO stock solution, and then freeze-drying the GO stock solution for later use to obtain Graphene Oxide (GO).
S2, ultrasonically dispersing a certain amount of graphene oxide in absolute ethyl alcohol for 1h, and then slowly adding a dilute ethanol solution of TBT and aluminum isopropoxide in a certain metering ratio (the ratio of the mass of the graphene oxide to the total mass of the TBT and the aluminum isopropoxide needs to be 1, TiO is required to be added, and the ratio of the mass of the graphene oxide to the total mass of the TBT and the aluminum isopropoxide is 1)2And Al2O3In a mass ratio of 1:4) and stirring for 24 hours to obtain a mixture. Then, the mixture is dried for 10 hours at 40 ℃, then dried for 10 hours in a drying oven at 60 ℃, and finally dried for 6 hours at 80 ℃ in a vacuum drying oven; then, grinding the dried solid sample into powder, roasting at 550 ℃ for 8h at the heating rate of 2 ℃/min to obtain the bulk phase type graphene-like materialThe composite metal oxide two-dimensional support material of (2). And (3) the graphene-like composite metal oxide two-dimensional carrier material obtained after roasting is named as TA-2Db, and the water absorption of the carrier material is measured and ground for later use.
S3, weighing a certain amount of Ni (NO)3)2·6H2O and (NH)4)6Mo7O24·4H2Dissolving O in deionized water to prepare a proper amount of impregnation liquid. Subsequently, a predetermined amount of TA-2Db was added to the immersion liquid, and the mixture was stirred and immersed at room temperature for 12 hours or more. After impregnation, the mixture is transferred to a 120 ℃ oven for drying for 12h, and then is roasted for 4h at 550 ℃, and the heating rate is 3 ℃/min, so that the catalyst is obtained. The catalyst obtained after roasting is named as NiMo/TA-2Db, wherein, MoO3The supported amount was 15 wt%, and the atomic ratio of Ni/(Ni + Mo) was 0.3.
Example 2
This embodiment provides a method for preparing a catalyst supported on a two-dimensional support material, which is characterized by comprising the following steps:
s1, mixing 5g of graphite powder and 2.5g of NaNO3Add 130mL of concentrated H2SO4In an ice bath for 2h (reaction temperature not exceeding-5 ℃). Then 15g KMnO4(KMnO is preliminarily mixed4Grinding the particles into powder) is slowly added into the reaction system (the addition is finished within 3-4h, and the temperature of the reaction system is maintained at 5-10 ℃). The above solution was transferred to a 35 ℃ water bath (the bath kettle temperature was previously heated to 35 ℃) and 230mL of deionized water (temperature below 50 ℃) was slowly added thereto and the reaction was continued with stirring for 1 h. The temperature of the water bath is adjusted to 98 ℃, the heating is closed after the stirring reaction is carried out for 30min, and 400mL of deionized water is slowly added into the system for diluting. After the reaction, 10mL of 30 wt% hydrogen peroxide is added to remove the unreacted KMnO4And stirred for 1 h. And after the GO is prepared, filling the obtained GO stock solution into a 2L big beaker, filling deionized water, stirring for 1h, and standing. And after GO completely sinks into the bottom, removing the supernatant. Repeating the steps for 5 times, centrifuging the GO stock solution to neutrality in a centrifugal washing mode to remove residual water-soluble ions (such as potassium ions, sodium ions, manganese ions, sulfate ions and the like) in the GO stock solution, and then removing the residual water-soluble ionsAnd (4) carrying out freeze drying for later use to obtain Graphene Oxide (GO).
S2, ultrasonically dispersing a certain amount of graphene oxide in absolute ethyl alcohol for 1h, then slowly adding a certain amount of dilute ethanol solution of aluminum isopropoxide (the ratio of the mass of the graphene oxide to the mass of the aluminum isopropoxide needs to be 1), and stirring for 24h to obtain a mixture. Then, the mixture is dried for 10 hours at 40 ℃, then dried for 10 hours in a drying oven at 60 ℃, and finally dried for 6 hours at 80 ℃ in a vacuum drying oven; then, grinding the dried solid sample into powder, roasting at 550 ℃ for 8h at the heating rate of 2 ℃/min to obtain graphene-like Al2O3Is named as Al2O3-2D, measuring its water absorption and grinding for use; adding a certain amount of TBT into a proper amount of absolute ethyl alcohol to prepare an impregnation liquid, and then adding weighed roasted Al2O3-2D (with TiO requirement)2And Al2O3The mass ratio of (1: 4), stirring and dipping for more than 12h, then drying at 120 ℃ for 12h, roasting at 500 ℃ for 8h, and heating up at the rate of 3 ℃/min to obtain the supported graphene-like composite metal oxide two-dimensional carrier material (TiO)2-Al2O3Composite oxide powder), named TA-2 Ds.
S3, weighing a certain amount of Ni (NO)3)2·6H2O and (NH)4)6Mo7O24·4H2Dissolving O in deionized water to prepare a proper amount of impregnation liquid. Subsequently, a certain amount of the above TA-2Ds was added to the immersion liquid, and the mixture was immersed at room temperature for 12 hours or more with stirring. After impregnation, the mixture is transferred to a 120 ℃ oven for drying for 12h, and then is roasted for 4h at 550 ℃, and the heating rate is 3 ℃/min, so that the catalyst is obtained. The catalyst obtained after calcination is named NiMo/TA-2Ds, wherein, MoO3The supported amount was 15 wt%, and the atomic ratio of Ni/(Ni + Mo) was 0.3. In addition, the SEM image of the catalyst is shown in the attached figure 1.
Example 3
This embodiment provides a method for preparing a catalyst supported on a two-dimensional support material, which is characterized by comprising the following steps:
s1, mixing5g of graphite powder and 2.5g of NaNO3Add 130mL of concentrated H2SO4In an ice bath for 2h (reaction temperature not exceeding-5 ℃). Then 15g KMnO4(KMnO is preliminarily mixed4Grinding the particles into powder) is slowly added into the reaction system (the addition is finished within 3-4h, and the temperature of the reaction system is maintained at 5-10 ℃). The above solution was transferred to a 35 ℃ water bath (the bath kettle temperature was previously heated to 35 ℃) and 230mL of deionized water (temperature below 50 ℃) was slowly added thereto and the reaction was continued with stirring for 1 h. The temperature of the water bath is adjusted to 98 ℃, the heating is closed after the stirring reaction is carried out for 30min, and 400mL of deionized water is slowly added into the system for diluting. After the reaction, 10mL of 30 wt% hydrogen peroxide is added to remove the unreacted KMnO4And stirred for 1 h. And after the GO is prepared, filling the obtained GO stock solution into a 2L big beaker, filling deionized water, stirring for 1h, and standing. And after GO completely sinks into the bottom, removing the supernatant. After repeating the step for 5 times, centrifuging the GO stock solution to be neutral in a centrifugal washing mode to remove residual water-soluble ions (such as potassium ions, sodium ions, manganese ions, sulfate ions and the like) in the GO stock solution, and then freeze-drying the GO stock solution for later use to obtain Graphene Oxide (GO).
S2, ultrasonically dispersing a certain amount of graphene oxide in absolute ethyl alcohol for 1 hour, and then slowly adding a dilute ethanol solution of zirconium oxychloride and aluminum isopropoxide in a certain metering ratio (the ratio of the mass of the graphene oxide to the total mass of the zirconium oxychloride and the aluminum isopropoxide needs to be 1, ZrO is ZrO, and the like)2And Al2O3In a mass ratio of 1:4) and stirring for 24 hours to obtain a mixture. Then, the mixture is dried for 10 hours at 40 ℃, then dried for 10 hours in a drying oven at 60 ℃, and finally dried for 6 hours at 80 ℃ in a vacuum drying oven; and then, grinding the dried solid sample into powder, and roasting at 550 ℃ for 8h at the heating rate of 2 ℃/min to obtain the bulk-phase graphene-like composite metal oxide two-dimensional carrier material. The graphene-like composite metal oxide two-dimensional carrier material obtained after roasting is named ZA-2Db, and the water absorption rate of the graphene-like composite metal oxide two-dimensional carrier material is measured and ground for later use.
S3, weighing a certain amount of Ni (NO)3)2·6H2O and (NH)4)6Mo7O24·4H2Dissolving O in deionized water to prepare a proper amount of impregnation liquid. Subsequently, a predetermined amount of ZA-2Db was added to the impregnation solution, and the mixture was stirred and impregnated at room temperature for 12 hours or more. After impregnation, the mixture is transferred to a 120 ℃ oven for drying for 12h, and then is roasted for 4h at 550 ℃, and the heating rate is 3 ℃/min, so that the catalyst is obtained. The catalyst obtained after roasting is named as NiMo/ZA-2Db, wherein MoO3The supported amount was 15 wt%, and the atomic ratio of Ni/(Ni + Mo) was 0.3.
Example 4
This embodiment provides a method for preparing a catalyst supported on a two-dimensional support material, which is characterized by comprising the following steps:
s1, mixing 5g of graphite powder and 2.5g of NaNO3Add 130mL of concentrated H2SO4In an ice bath for 2h (reaction temperature not exceeding-5 ℃). Then 15g KMnO4(KMnO is preliminarily mixed4Grinding the particles into powder) is slowly added into the reaction system (the addition is finished within 3-4h, and the temperature of the reaction system is maintained at 5-10 ℃). The above solution was transferred to a 35 ℃ water bath (the bath kettle temperature was previously heated to 35 ℃) and 230mL of deionized water (temperature below 50 ℃) was slowly added thereto and the reaction was continued with stirring for 1 h. The temperature of the water bath is adjusted to 98 ℃, the heating is closed after the stirring reaction is carried out for 30min, and 400mL of deionized water is slowly added into the system for diluting. After the reaction, 10mL of 30 wt% hydrogen peroxide is added to remove the unreacted KMnO4And stirred for 1 h. And after the GO is prepared, filling the obtained GO stock solution into a 2L big beaker, filling deionized water, stirring for 1h, and standing. And after GO completely sinks into the bottom, removing the supernatant. After repeating the step for 5 times, centrifuging the GO stock solution to be neutral in a centrifugal washing mode to remove residual water-soluble ions (such as potassium ions, sodium ions, manganese ions, sulfate ions and the like) in the GO stock solution, and then freeze-drying the GO stock solution for later use to obtain Graphene Oxide (GO).
S2, ultrasonically dispersing a certain amount of graphene oxide in absolute ethyl alcohol for 1h, and then slowly adding a certain amount of dilute ethanol solution of aluminum isopropoxide (the mass of the graphene oxide and the mass of the isopropanol need to be satisfied)The mass ratio of aluminum is 1), and stirring is carried out for 24 hours to obtain a mixture. Then, the mixture is dried for 10 hours at 40 ℃, then dried for 10 hours in a drying oven at 60 ℃, and finally dried for 6 hours at 80 ℃ in a vacuum drying oven; then, grinding the dried solid sample into powder, roasting at 550 ℃ for 8h at the heating rate of 2 ℃/min to obtain graphene-like Al2O3Is named as Al2O3-2D, measuring its water absorption and grinding for use; adding a certain amount of cerous nitrate into a proper amount of absolute ethyl alcohol to prepare an impregnation liquid, and then adding weighed roasted Al2O3-2D (CeO is required to be satisfied)2And Al2O3The mass ratio of (1: 4), stirring and dipping for more than 12h, then drying at 120 ℃ for 12h, roasting at 500 ℃ for 8h, and heating up at the rate of 3 ℃/min to obtain the supported graphene-like composite metal oxide two-dimensional carrier material (CeO)2-Al2O3Composite oxide powder), designated CA-2 Ds.
S3, weighing a certain amount of Ni (NO)3)2·6H2O and (NH)4)6Mo7O24·4H2Dissolving O in deionized water to prepare a proper amount of impregnation liquid. Subsequently, a predetermined amount of the above CA-2Ds is added to the immersion liquid, and the mixture is immersed at room temperature for 12 hours or more with stirring. After impregnation, the mixture is transferred to a 120 ℃ oven for drying for 12h, and then is roasted for 4h at 550 ℃, and the heating rate is 3 ℃/min, so that the catalyst is obtained. The catalyst obtained after calcination is named NiMo/CA-2Ds, wherein, MoO3The supported amount was 15 wt%, and the atomic ratio of Ni/(Ni + Mo) was 0.3.
Example 5
This embodiment provides a method for preparing a catalyst supported on a two-dimensional support material, which is characterized by comprising the following steps:
s1, ultrasonically dispersing a certain amount of the graphene oxide prepared in the above example 1 in absolute ethyl alcohol for 1 hour, then slowly adding a diluted ethanol solution of TBT and aluminum isopropoxide in a certain stoichiometric ratio (the ratio of the mass of the graphene oxide to the total mass of the TBT and the aluminum isopropoxide needs to be 0.5), and stirring for 24 hours to obtain a mixture. Then, the mixture is dried for 10 hours at 40 ℃, then dried for 10 hours in a drying oven at 60 ℃, and finally dried for 6 hours at 80 ℃ in a vacuum drying oven; and then, grinding the dried solid sample into powder, and roasting at 550 ℃ for 8h at the heating rate of 2 ℃/min to obtain the bulk-phase graphene-like composite metal oxide two-dimensional carrier material. And (3) the graphene-like composite metal oxide two-dimensional carrier material obtained after roasting is named as TA-2Db, and the water absorption of the carrier material is measured and ground for later use.
S2, weighing a certain amount of Ni (NO)3)2·6H2O and (NH)4)6W7O24·6H2Dissolving O in deionized water to prepare a proper amount of impregnation liquid. Subsequently, a predetermined amount of TA-2Db was added to the immersion liquid, and the mixture was stirred and immersed at room temperature for 12 hours or more. After impregnation, transferring the mixture to a 120 ℃ oven for drying for 12h, and then roasting the mixture at 550 ℃ for 4h at the heating rate of 3 ℃/min to obtain the catalyst, wherein MoO is3The supported amount was 20 wt%, and the atomic ratio of Ni/(Ni + W) was 0.2.
Example 6
This embodiment provides a method for preparing a catalyst supported on a two-dimensional support material, which is characterized by comprising the following steps:
s1, ultrasonically dispersing a certain amount of the solution obtained in the above example 1 in absolute ethyl alcohol for 1 hour, slowly adding a certain stoichiometric amount of a dilute ethanol solution of zirconium nitrate and aluminum isopropoxide (the ratio of the mass of graphene oxide to the total mass of aluminum isopropoxide and zirconium nitrate needs to be 2), and stirring for 24 hours to obtain a mixture. Then, the mixture is dried for 10 hours at 40 ℃, then dried for 10 hours in a drying oven at 60 ℃, and finally dried for 6 hours at 80 ℃ in a vacuum drying oven; and then, grinding the dried solid sample into powder, roasting at 550 ℃ for 8h at the heating rate of 2 ℃/min to obtain a bulk phase type graphene-like composite metal oxide two-dimensional carrier material, measuring the water absorption rate of the bulk phase type graphene-like composite metal oxide two-dimensional carrier material, and grinding for later use.
S2, weighing a certain amount of cobalt nitrate and dissolving the cobalt nitrate in deionized water to prepare a proper amount of impregnation liquid. Then, a certain amount of the graphene-like composite metal oxide two-dimensional carrier material is added into the impregnation liquid, and the mixture is stirred and impregnated for more than 12 hours at room temperature. And after impregnation, transferring the mixture to a 120 ℃ oven for drying for 12h, and then roasting the mixture at 550 ℃ for 4h at the heating rate of 3 ℃/min to obtain the catalyst, wherein the load of CoO is 10 wt%.
Application example I HDN reaction of quinoline
Preparing simulated coal tar: dissolving a certain amount of quinoline in cyclohexane to prepare a solution with the nitrogen content of 500ppm, and adding n-decane as an internal standard to obtain the simulated coal tar.
And (3) vulcanization of the catalyst: first, NiMo/TA-2Db is tableted and sieved to 20-40 mesh, and then treated in a micro reaction tube furnace with 10 vol% H2S/H2Heating to 400 ℃ at the speed of 5 ℃/min under the atmosphere (55mL/min), vulcanizing for 4h, cooling to room temperature, and taking out the catalyst, wherein the name is NiMoS/TA-2D.
HDN reaction of quinoline: the HDN reaction of quinoline is carried out in an autoclave. 60mL of simulated fuel oil and 0.2g of NiMoS/TA-2Db were sequentially added to a 200mL autoclave. And (3) filling 3MPa of hydrogen into the reaction kettle at room temperature, wherein the reaction temperature is 350 ℃, the reaction time is 4h, and the rotating speed is 400 rpm. Taking a first sample when the reaction temperature is reached, and marking the first sample as 0; samples were taken every 1h thereafter and recorded as 1,2,3, 4. After the reaction is finished, the composition of the reaction product is qualitatively and quantitatively analyzed by using a full two-dimensional gas chromatography-mass spectrum/hydrogen flame ionization detector (GC × GC-MS/FID).
Calculation of the complete denitrification Rate:
in the formula, CQThe quinoline content in the original simulated oil; cpThe content of the complete denitrification product in the oil is simulated after the reaction is finished.
After 4 hours of reaction, the complete denitrification rate of quinoline is 41.81%, the denitrification rate is improved, and the generated complete denitrification products mainly comprise Propylbenzene (PB) and Propylcyclohexane (PCH).
Application example two, HDN reaction of quinoline
The preparation of simulated coal tar was the same as in example 1.
And (3) vulcanization of the catalyst: a certain amount of NiMo/TA-2Ds of 20-40 meshes is placed in a miniature reaction tube furnace at 10 vol% of H2S/H2Raising the temperature to 400 ℃ at the speed of 5 ℃/min under the atmosphere (55mL/min), vulcanizing for 4h, cooling to room temperature, and taking out the catalyst, which is named as NiMoS/TA-2 Ds.
HDN reaction of quinoline: the HDN reaction of quinoline is carried out in an autoclave. 60mL of simulated fuel oil and 0.2g of NiMoS/TA-2Ds were sequentially added to a 200mL autoclave. The initial pressure of hydrogen is 3MPa, the reaction temperature is 350 ℃, the reaction time is 4h, and the rotating speed is 400 rpm. After the reaction is finished, products are quantitatively analyzed by GC × GC-MS/FID, and the complete denitrification rate of the final quinoline reaches 74.81%.
Wherein the complete denitrification rate of quinoline on the NiMoS catalyst is shown in the attached figure 2.
HDS of application example III, DBT and HDN reaction of quinoline
Preparing simulated coal tar: and simultaneously adding a certain amount of quinoline and DBT into cyclohexane to prepare a solution with the nitrogen content and the sulfur content both being 500ppm, and adding n-decane as an internal standard to obtain the simulated coal tar.
Simultaneous HDS and HDN reactions: 60mL of simulated fuel oil and 0.2g of vulcanized NiMoS/ZA-2Db were sequentially added to a 200mL autoclave. And (3) filling 3MPa of hydrogen into the reaction kettle at room temperature, wherein the reaction temperature is 350 ℃, the heating rate is 5 ℃/min, the reaction time is 4h, and the rotating speed is 400 rpm. Samples were taken every 1 hour and the products were analyzed to calculate the desulfurization of DBT and the complete denitrification of quinoline.
Calculation of desulfurization degree:
in the formula, C0The content of DBT in the original simulated oil; ctThe DBT content in the oil was simulated for a specific time after hydrodesulfurization.
With the reaction, the desulfurization rate of DBT finally reaches 95.60%, the complete denitrification rate of quinoline reaches 63.80%, the desulfurization rate and the denitrification rate are greatly improved, and the catalyst has good hydrodesulfurization and denitrification performance.
HDS reaction of DBT, application example four
Preparing simulated coal tar: and dissolving a certain amount of DBT and n-decane in cyclohexane to obtain the simulated coal tar. Wherein the sulfur content in the simulated oil is 500ppm, and n-decane is used as an internal standard.
HDS reaction of DBT: taking 0.2g of vulcanized NiMoS/CA-2Ds catalyst, and adding the catalyst into a high-pressure reaction kettle containing 60mL of simulation oil. The initial pressure of hydrogen is 3MPa, the reaction temperature is 350 ℃, the heating rate is 5 ℃/min, the reaction time is 4h, and the rotating speed is 400 rpm. The hourly sampling was quantitatively analyzed by GC × GC-MS/FID and the desulfurization rate was calculated to be 96.10.
Application example five, phenanthrene hydrogenation saturation reaction
Preparing simulated coal tar: phenanthrene and n-decane (internal standard) are added into cyclohexane according to a certain proportion to obtain the simulation oil with the phenanthrene content of 1 wt%.
Phenanthrene hydrogenation saturation reaction: the hydrogenation saturation reaction of phenanthrene is carried out in a high-pressure reaction kettle. 60mL of the simulated oil and 0.2g of NiMoS/TA-2Db were sequentially added to a 200mL autoclave. And (3) charging 4MPa of hydrogen into the reaction kettle at room temperature, wherein the reaction temperature is 280 ℃, the reaction time is 4h, and the rotating speed is 400 rpm. Taking a first sample when the reaction temperature is reached, and marking the first sample as 0; samples were taken every 1h thereafter and recorded as 1,2,3, 4. After the reaction, the composition of the reaction product was analyzed qualitatively and quantitatively by GC X GC-MS/FID. After reacting for 4h, phenanthrene can be hydrogenated to generate perhydrophenanthrene on a NiMoS/TA-2Db catalyst, wherein the selectivity of perhydrophenanthrene (PHP) is 1.27%, and the conversion rate of phenanthrene can reach 62.53%.
Application example six, HDN and phenanthrene Hydrosaturation reaction of quinoline
Preparing simulated coal tar: a certain amount of quinoline, phenanthrene and n-decane was added simultaneously to cyclohexane, the nitrogen content being 500ppm, the phenanthrene content being 1 wt% and n-decane being the internal standard.
HDN and phenanthrene hydrosaturation of quinolines: 60mL of simulated oil and 0.2g of NiMoS/TA-2Ds are sequentially added into a 200mL high-pressure reaction kettle to carry out HDN and hydrogenation saturation reaction simultaneously. And (3) filling 3MPa hydrogen into the reaction kettle at room temperature, wherein the reaction temperature is 350 ℃, the reaction time is 4h, and the rotating speed is 400 rpm. After the reaction, the composition of the reaction product was analyzed qualitatively and quantitatively by GC X GC-MS/FID. The results show that the addition of phenanthrene does not affect the HDN of quinoline. On a NiMoS/TA-2Ds catalyst, quinoline HDN and phenanthrene hydrogenation saturation reaction can be carried out simultaneously, wherein the complete denitrification rate of quinoline is 72.35%, and the conversion rate of phenanthrene is 39.92%.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
The patent focuses on the preparation of the graphene-like material and the application of the graphene-like material in hydrofining, so that the preparation of the graphene oxide in the embodiment can be reduced to a certain extent, the mass ratio of the graphite powder, the sodium nitrate and the potassium permanganate does not need to be changed, and the mass ratio is kept at 5g:2.5g:15 g. In the embodiment, an embodiment of changing the mass ratio of the graphene oxide to the metal precursor salt may be added, wherein the mass ratio of the graphene oxide to the metal precursor salt is only 0.5-2.
Claims (9)
1. A preparation method of a catalyst loaded on a two-dimensional carrier material is characterized by comprising the following steps:
preparing graphene oxide;
preparing a graphene-like composite metal oxide two-dimensional carrier material by taking graphene oxide as a structure directing agent and metal precursor salt as a raw material through a solvent volatilization self-assembly method;
and (3) loading active metal on the graphene-like composite metal oxide two-dimensional carrier material by adopting an isometric co-impregnation method to obtain the catalyst.
2. The preparation method of the catalyst loaded on the two-dimensional support material according to claim 1, wherein the step of preparing the graphene oxide specifically comprises:
adding graphite powder and sodium nitrate into sulfuric acid, mixing, and adding potassium permanganate to react to obtain a graphene oxide stock solution;
and standing the graphene oxide stock solution, centrifuging and washing to be neutral, and freeze-drying to obtain the graphene oxide.
3. The method for preparing a catalyst loaded with a two-dimensional support material according to claim 1, wherein the step of preparing the graphene-like composite metal oxide two-dimensional support material by using graphene oxide as a structure directing agent and a metal precursor salt as a raw material and using a solvent volatilization self-assembly method specifically comprises:
after graphene oxide is dispersed in absolute ethyl alcohol, adding metal precursor salt and aluminum isopropoxide, stirring, drying and roasting to obtain the graphene-like composite metal oxide two-dimensional carrier material.
4. The method for preparing a catalyst loaded with a two-dimensional support material according to claim 1, wherein the step of preparing the graphene-like composite metal oxide two-dimensional support material by using graphene oxide as a structure directing agent and a metal precursor salt as a raw material and using a solvent volatilization self-assembly method specifically comprises:
dispersing graphene oxide in absolute ethyl alcohol, adding aluminum isopropoxide, stirring, drying and roasting to obtain graphene-like Al2O3；
Adding metal precursor salt into absolute ethyl alcohol for mixing to obtain an impregnation liquid;
graphene-like Al2O3Adding the graphene-like composite metal oxide into the impregnation liquid, stirring and impregnating, and then drying and roasting to obtain the graphene-like composite metal oxide two-dimensional carrier material.
5. The method of claim 1, 3 or 4, wherein the metal precursor salt is at least one of tetrabutyl titanate, aluminum isopropoxide, zirconium oxychloride, cerium nitrate and zirconium nitrate.
6. The method of claim 1, wherein the active metal is at least one of Ni, Mo, Co, W.
7. The method of claim 1, further comprising the steps of:
and tabletting and screening the catalyst, and then placing the catalyst in an atmosphere containing hydrogen sulfide and hydrogen for vulcanization treatment.
8. A catalyst prepared by the preparation method of any one of claims 1 to 7.
9. Use of the catalyst of claim 9 in coal tar hydrofinishing.
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