CN111569908A - Hydrodenitrogenation catalyst and preparation method and application thereof - Google Patents
Hydrodenitrogenation catalyst and preparation method and application thereof Download PDFInfo
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- CN111569908A CN111569908A CN202010499551.2A CN202010499551A CN111569908A CN 111569908 A CN111569908 A CN 111569908A CN 202010499551 A CN202010499551 A CN 202010499551A CN 111569908 A CN111569908 A CN 111569908A
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- montmorillonite
- catalyst
- ionic liquid
- source
- hydrodenitrogenation
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- 239000003054 catalyst Substances 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 82
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 80
- 239000002608 ionic liquid Substances 0.000 claims abstract description 51
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 24
- 229910052976 metal sulfide Inorganic materials 0.000 claims abstract description 23
- 239000007900 aqueous suspension Substances 0.000 claims abstract description 18
- -1 alkyl imidazole Chemical compound 0.000 claims description 40
- 239000007788 liquid Substances 0.000 claims description 26
- 238000002425 crystallisation Methods 0.000 claims description 24
- 230000008025 crystallization Effects 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000012265 solid product Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 20
- 239000006185 dispersion Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 18
- 239000011541 reaction mixture Substances 0.000 claims description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 16
- 239000010949 copper Substances 0.000 claims description 16
- 229910052717 sulfur Inorganic materials 0.000 claims description 16
- 239000011593 sulfur Substances 0.000 claims description 16
- 239000003638 chemical reducing agent Substances 0.000 claims description 15
- 238000007598 dipping method Methods 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- 239000002736 nonionic surfactant Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 10
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 9
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- 239000012279 sodium borohydride Substances 0.000 claims description 8
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 8
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 7
- 229920000053 polysorbate 80 Polymers 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 5
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 5
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 5
- XCUPBHGRVHYPQC-UHFFFAOYSA-N sulfanylidenetungsten Chemical compound [W]=S XCUPBHGRVHYPQC-UHFFFAOYSA-N 0.000 claims description 5
- 150000001450 anions Chemical class 0.000 claims description 4
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000011148 porous material Substances 0.000 abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052799 carbon Inorganic materials 0.000 abstract description 9
- 230000008021 deposition Effects 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- 238000007306 functionalization reaction Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 230000000694 effects Effects 0.000 description 12
- 238000005984 hydrogenation reaction Methods 0.000 description 11
- 239000011734 sodium Substances 0.000 description 11
- 239000007787 solid Substances 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000013049 sediment Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- KYCQOKLOSUBEJK-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;bromide Chemical compound [Br-].CCCCN1C=C[N+](C)=C1 KYCQOKLOSUBEJK-UHFFFAOYSA-M 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 230000009849 deactivation Effects 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LVHMJHXXLZIOOJ-UHFFFAOYSA-N C(CCC)N1CN(C=C1)C.[Br] Chemical compound C(CCC)N1CN(C=C1)C.[Br] LVHMJHXXLZIOOJ-UHFFFAOYSA-N 0.000 description 2
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 2
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000002105 nanoparticle Substances 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
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000004448 titration Methods 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/049—Sulfides with chromium, molybdenum, tungsten or polonium with iron group metals or platinum group metals
-
- 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
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
-
- 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
- B01J37/0213—Preparation of the impregnating solution
-
- 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
-
- 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
Landscapes
- 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)
Abstract
The invention discloses a preparation method of a hydrodenitrogenation catalyst, which comprises the following steps: preparing montmorillonite water suspension; carrying out montmorillonite functionalization and hole expansion; the ionic liquid is used for preparing nano metal sulfide and montmorillonite composite material. The invention also discloses the catalyst prepared by the preparation method and the application of the catalyst in the residual oil hydrodenitrogenation. The invention adopts an ionic liquid chambering montmorillonite material, further adopts ionic liquid functionalized active metal, and is loaded on modified montmorillonite to be used as a residual oil hydrofining catalyst. The pore structure and the acidity distribution of the catalyst are organically matched with each other, the pore channel is smooth, the effective active surface of the catalyst is extremely high, the overall performance of the catalyst is improved, the catalyst has excellent catalytic hydrodenitrogenation performance, and carbon deposition is not easy to generate.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a hydrodenitrogenation catalyst suitable for a residual oil hydrodenitrogenation process and a preparation method and application thereof.
Background
The world petroleum resources are gradually reduced, the average consumption of diesel oil, gasoline and the like is gradually increased, the phenomena of heavy oil and poor oil of crude oil extracted from the world are gradually serious, the demand of light oil products in the social market is increased year by year, so that the technology for lightening the residual oil and the residual oil accounting for a large proportion of petroleum is more and more emphasized by people, and a large number of large petroleum companies in the world invest a large amount of manpower and material resources to develop and research the residual oil hydrogenation catalyst.
In the catalytic reaction process of residual oil hydrodenitrogenation, the hydrodenitrogenation reaction of the nitrogen-containing heterocyclic component must first completely hydrogenate and saturate the nitrogen-containing heterocyclic component, and then the nitrogen atoms can be removed. Therefore, the hydrodenitrogenation reaction requires a catalyst having a high hydrogenation activity. In addition, the hydrodenitrogenation catalyst needs to have not only good hydrogenation activity but also strong sulfur resistance.
The carrier material used by the existing residual oil hydrodenitrogenation catalyst is generally macroporous alumina and modified products thereof. CN109718751A and CN106669752A respectively disclose preparation methods of an alumina carrier for hydrodenitrogenation; CN103657736A discloses an activated carbon/alumina composite catalyst carrier and preparation and application thereof; however, the pores of the alumina carrier are mainly formed by accumulating particles, and the structural model of the alumina pores is in a network type, so that the phase change is easy to occur, and further sintering is easy to occur.
The montmorillonite crystal structure is formed by closely packing aluminum oxygen octahedrons and silicon oxygen tetrahedrons, and is mainly a three-layer structure formed by connecting two silicon oxygen tetrahedrons and one aluminum oxygen octahedron through covalent bonds, so that the arrangement of internal lattices is highly ordered. The special crystal structure makes the material have the characteristics of adsorptivity, water absorbability, cohesiveness, exchangeability, dispersibility and the like. Therefore, it can be optimized and modified, and the modified montmorillonite will have interlaminar domains, which is a very good chemical reaction site. At present, reports of using montmorillonite as a hydrogenation catalyst carrier are very rare.
Disclosure of Invention
The invention aims to provide a hydrodenitrogenation catalyst taking montmorillonite as a carrier and a preparation method thereof aiming at the requirements of the existing hydrodenitrogenation desulfurization technology.
In order to achieve the above object, the present invention provides a method for preparing a hydrodenitrogenation catalyst, comprising the steps of:
1) dispersing montmorillonite in water, standing, and removing precipitate to obtain montmorillonite water suspension;
2) adding ionic liquid and nonionic surfactant into the montmorillonite water suspension, stirring, standing, and centrifuging to obtain white solid product; drying and calcining the white solid product to obtain a montmorillonite carrier;
3) adding a metal source and a sulfur source into water, and reacting at 60-85 ℃ for 15-20h to obtain a mixed solution;
4) adding an ionic liquid and a reducing agent into the mixed solution to prepare an initial reaction mixture;
5) carrying out ultrasonic treatment on the initial reaction mixture to obtain a nano metal sulfide dispersion liquid;
6) dipping the nano metal sulfide dispersion liquid on the surface of the montmorillonite carrier by adopting an isometric dipping method, standing, and then transferring the montmorillonite carrier to a high-pressure synthesis kettle for crystallization;
7) and after crystallization is finished, separating a solid product to obtain the catalyst.
Optionally, according to the preparation method of the hydrodenitrogenation catalyst, the metal source is any two or three of a tungsten source, a nickel source and a copper source; the sulfur source is one or two of ammonium sulfide, sodium sulfide, potassium sulfide and thiourea.
Optionally, according to the preparation method of the hydrodenitrogenation catalyst, the tungsten source is a sulfur-tungsten compound, the nickel source is soluble nickel-containing sulfate or nitrate, and the copper source is soluble copper-containing sulfate or nitrate.
Alternatively, according to the preparation method of the hydrodenitrogenation catalyst of the present invention, in step 2), the ionic liquid is added in an amount of 0.5 to 5 wt% of the montmorillonite.
Optionally, according to the preparation method of the hydrodenitrogenation catalyst, in the ionic liquid, the cation is one or two of alkyl imidazole and quaternary ammonium ion, and the anion is one or more of halogen ion, tetrafluoroborate, hexafluorophosphate, borate, phosphate, carbonate and hydroxide.
Alternatively, according to the preparation method of the hydrodenitrogenation catalyst, in the step 2), the nonionic surfactant is one or two of tween 80, polyoxyethylene lauryl ether and polyoxyethylene octanol, and the molar ratio of the nonionic surfactant to the ionic liquid is 1: 1-1:5.
Alternatively, according to the preparation method of the hydrodenitrogenation catalyst, the reducing agent is one or both of sodium borohydride and hydroxylamine hydrochloride.
Alternatively, according to the preparation method of the hydrodenitrogenation catalyst, the crystallization conditions are as follows: the crystallization temperature is 50-200 ℃, and the crystallization time is 10-120 h.
On the other hand, the invention also provides a hydrodenitrogenation catalyst obtained by the preparation method of the hydrodenitrogenation catalyst.
In another aspect, the invention also provides the application of the catalyst in the residual oil hydrodenitrogenation reaction.
The invention has the beneficial effects that:
the invention adopts an ionic liquid pore-enlarging montmorillonite material, further adopts ionic liquid functionalized active metal, and loads modified montmorillonite for a residual oil hydrofining catalyst. The prepared catalyst has the advantages that the pore structure and the acidity distribution of the catalyst are organically matched with each other by adopting the ionic liquid, the pore channel is smooth, the effective active surface of the catalyst is extremely high, the overall performance of the catalyst is improved, the catalyst has high catalytic denitrification activity, and carbon deposition is not easy to generate.
Detailed Description
The invention is further described below with reference to specific embodiments.
In one aspect, the present invention provides a method for preparing a hydrodenitrogenation catalyst, comprising the steps of:
step 1): dispersing montmorillonite in water, standing, and removing precipitate to obtain montmorillonite water suspension;
step 2): adding ionic liquid and nonionic surfactant into the montmorillonite water suspension, stirring, standing, and centrifuging to obtain white solid product; drying and calcining the white solid product to obtain a montmorillonite carrier;
step 3): adding a metal source and a sulfur source into water, and reacting at 60-85 ℃ for 15-20h to obtain a mixed solution;
step 4): adding an ionic liquid and a reducing agent into the mixed solution to prepare an initial reaction mixture;
step 5): carrying out ultrasonic treatment on the initial reaction mixture to obtain a nano metal sulfide dispersion liquid;
step 6): dipping the nano metal sulfide dispersion liquid on the surface of the montmorillonite carrier by adopting an isometric dipping method, standing, and then transferring the montmorillonite carrier to a high-pressure synthesis kettle for crystallization;
step 7): and after crystallization is finished, separating a solid product to obtain the catalyst.
In the preparation method, the ionic liquid and the nonionic surfactant are used, wherein the ionic liquid is a liquid consisting of organic cations and inorganic anions, is a novel green solvent and has a wide application prospect. Ionic liquids have many superior properties compared to traditional solvents: the product has good thermal stability, chemical stability and low volatility; the catalyst has high solubility to various organic and inorganic compounds, has double functions of a solvent and a catalyst, and can be used as a solvent for a plurality of chemical reactions or a catalyst carrier required in catalytic reactions; the polarity of the ionic liquid can be regulated, a two-phase or multi-phase system can be formed, and the ionic liquid is suitable for being used as a separation solvent or forming a new reaction separation coupling system; the ionic liquid has designability, and the property of the ionic liquid can be changed according to the types of the anions and the cations. In the application, the hydrophilic and hydrophobic properties among montmorillonite layers can be adjusted by utilizing the ionic liquid, so that the nano particles are more loosely, continuously and uniformly fixed on the surface of the montmorillonite, a loose pore structure is presented, the activity and the reaction space of nano metal sulfide are favorably increased, and the hydrogenation effect of the catalyst is improved. In addition, the ionic liquid is matched with the nonionic surfactant for use, so that the interlayer spacing and the pore volume of the montmorillonite can be increased and regulated, and the thermal stability of the montmorillonite is improved.
Specifically, in the above step 1), the concentration of the aqueous suspension of montmorillonite is 0.5 to 1.5%, preferably 1%. For example, 1.0g of purified montmorillonite is weighed, dispersed in 100mL of deionized water, stirred electrically for 5 hours, and left to stand for 12 to 24 hours. Then removing the sediment to obtain the montmorillonite water suspension with the mass fraction of 1 percent.
In the above step 2), it is preferable that the ionic liquid and the nonionic surfactant are dropwise added to the aqueous suspension of montmorillonite, and electrically stirred at 50 ℃ for 5 hours, and left to stand for aging overnight, whereby a white solid deposit is formed at the bottom of the container and a pale yellow transparent liquid is formed at the upper part. The product was obtained as a white solid by centrifugation. Washing the white product with ethanol for three times, then drying in vacuum, and finally calcining at the high temperature of 300-800 ℃ to obtain the functionalized and expanded montmorillonite carrier.
Preferably, in the ionic liquid, the cation is one or two of alkyl imidazole and quaternary ammonium ion, the anion is one or more of halogen ion, tetrafluoroborate, hexafluorophosphate, borate, phosphate, carbonate and hydroxide, and the ionic liquid may be, for example, 1-propyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium bromide, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium hexafluorophosphate, etc. The nonionic surfactant is one or two of tween 80, polyoxyethylene lauryl ether and polyoxyethylene octanol.
Further preferably, in step 2), the ionic liquid is added in an amount of 0.5 to 5% by weight, i.e. 0.5 to 5% by weight, of the montmorillonite, and may be, for example, 1%, 2%, 3%, 4% by weight. The molar ratio of the nonionic surfactant to the ionic liquid is 1:1-1:5, for example, 1:1, 1:3, 1: 5.
In the step 3), the metal source is any two or three of a tungsten (W) source, a nickel (Ni) source and a copper (Cu) source; the sulfur source is one or two of ammonium sulfide, sodium sulfide, potassium sulfide and thiourea. Preferably, the tungsten source is a sulfur tungsten compound, more preferably, the sulfur tungsten compound source is a dithiotungstate and a tetrathiotungstic acidOne or two of the salts, the cation of which is Na+、K+One or two of (a); and the molar concentration of the sulfur-tungsten compound is 0.05-2 mol/l. Also preferably, the nickel source is a soluble nickel-containing sulfate or nitrate and the copper source is a soluble copper-containing sulfate or nitrate.
At present, the metal components used by the hydrogenation catalyst are mostly VIB, VIIB and VIII groups of the periodic table of elements, and the metal elements of other groups in the periodic table of elements are rarely related, in fact, copper (Cu) elements of other groups in the periodic table of elements, such as IB groups, still remain high-activity catalysts for hydrogenation of heavy residual oil, and particularly, the activity of the catalysts is greatly enhanced if the catalysts are combined with other catalysts for use. Moreover, the cost of the copper (Cu) compound used as the catalyst is greatly reduced compared with that of the molybdenum (Mo), cobalt (Co) and other series catalysts
In the catalyst, the metal active component contains at least two of the VI B, VIII and IB metal components, and the compound use of the metals not only improves the catalyst activity and increases the residual oil conversion rate, but also reduces the catalyst cost when cheap copper is used.
In addition, one or more elements with positive and negative electric properties are introduced into the catalyst, so that the catalyst has the required average electronegativity, the pore structure is changed, the activity of demetallization, N removal and S removal of the catalyst is high, and the catalyst has a good carbon deposit resistance effect.
In the step 4), the reducing agent is one or two of sodium borohydride and hydroxylamine hydrochloride. Further preferably, in this step, the molar ratio of the added ionic liquid to the reducing agent is 0.1-20:1, and may be, for example, 0.5:1, 1:1, 5:1, 10:1, 15: 1.
The residual oil hydrogenation reaction is carried out on a catalyst, belongs to heterogeneous catalytic reaction and has chemical adsorption effect. In the residual oil hydrogenation reaction, the catalyst deactivation process is divided into three periods: initial rapid deactivation by carbon deposition, intermediate slow deactivation by metal sulfides, and final rapid deactivation by catalyst pore plugging. Therefore, the acid strength of the residual oil hydrogenation catalyst must be moderate, so that the impurity removal rate of the catalyst can be ensured, the residual oil molecules are not excessively cracked, and the hydrogen consumption of a hydrogenation device is lower. In the application, the particle size distribution of the active metal can be optimized by adjusting the use amounts of the metal sources (active metals) in different ionic liquids and catalysts, the acid distribution and the metal distribution can be adjusted in a targeted manner, and the content of the active components can be increased.
In the step 5), before the ultrasonic treatment, ethanol may be added to the initial reaction mixture to disperse the mixture, so as to improve the effect of the ultrasonic treatment; the volume of ethanol added may be equal to the volume of the initial reaction mixture. And carrying out ultrasonic treatment for 3-8 minutes.
In the step 6), the nano metal sulfide dispersion liquid is dipped on the surface of the montmorillonite carrier by an isometric dipping method, then is kept stand for 5-15h at room temperature and then is transferred to a high-pressure synthesis kettle for crystallization. Preferably, the crystallization is carried out under the condition that the pH value is 5.0-11.0, the crystallization temperature is 50-200 ℃ (preferably 60-180 ℃, such as 80 ℃, 100 ℃, 120 ℃, 150 ℃, 170 ℃), and the crystallization time is 10-120h (preferably 20-100h, such as 30h, 50h, 70h, 90 h). In this step, for example, ammonia, NaOH, KOH, HCl, HNO can be used3And (3) adjusting the pH value of the reaction system of the high-pressure synthesis kettle, preferably selecting ammonia water as an alkali source and nitric acid as an acid source.
In the step 7), the process of separating the solid product comprises the following steps: filtering, washing with deionized water and drying to obtain the product. The separation process is a conventional operation in the prior art, and specific operation steps and parameters are not described herein.
On the other hand, the invention also provides a hydrodenitrogenation catalyst obtained by the preparation method of the hydrodenitrogenation catalyst. The specific surface area of the prepared catalyst is 200-450m2The pore volume is 0.6-1.8 ml/g, and the pore diameter is 10-35 nm.
In another aspect, the invention also provides the application of the catalyst in hydrodenitrogenation reaction of inferior wax oil and residual oil. The catalyst shows excellent catalytic activity in hydrodenitrogenation, has good sulfur resistance and residual carbon resistance, and has wide application prospect in high-denitrification reaction of raw materials such as inferior wax oil, residual oil and the like.
To describe the invention in detail, the Applicant has used tungsten disulfide nickel copper/montmorillonite (WNiCuS)2Montmorillonite) as an example, the preparation method of the hydrodenitrogenation catalyst of the present application is exemplified. It should be understood that the following specific examples are illustrative of specific implementations of the invention only and are not to be construed as limiting the scope of the invention.
Example 1
1.0g of purified montmorillonite was weighed, dispersed in 100mL of deionized water, stirred electrically for 5 hours, and left to stand overnight. The sediment was removed to obtain an aqueous suspension of montmorillonite having a mass fraction of 1%.
Adding ionic liquid 1-butyl-3-methylimidazole hexafluorophosphate and surfactant Tween 80 dropwise into the 1% montmorillonite water suspension, electrically stirring for 5h at 50 ℃, and standing and aging for 12-24 h. The bottom of the vessel was a white solid deposit and the top was a pale yellow transparent liquid. The product was obtained as a white solid by centrifugation. Washing the white product with ethanol for three times, then drying in vacuum, and finally calcining at the high temperature of 300 ℃ to obtain the functionalized and chambered montmorillonite carrier. Wherein the adding amount of the 1-butyl-3-methylimidazole hexafluorophosphate is 0.5 wt% of the montmorillonite, and the molar ratio of the Tween 80 to the 1-butyl-3-methylimidazole hexafluorophosphate is 1: 1.
Adding a metal source and a sulfur source into deionized water, and reacting at 60 ℃ for 20 hours to obtain a mixed solution; wherein the metal source is sodium dithiotungstate (Na)2WO2S2) The sulfur source is ammonium sulfide, the molar ratio of the four substances (sodium dithiotungstate, nickel sulfate, copper sulfate and ammonium sulfide) is 1:1:1:1, and the total added mass is 50% of the mass of the montmorillonite. And adding the ionic liquid 1-butyl-3-methylimidazole hexafluorophosphate and the reducing agent sodium borohydride into the mixed solution again, uniformly stirring, and preparing an initial reaction mixture, wherein the molar ratio of the ionic liquid 1-butyl-3-methylimidazole hexafluorophosphate to the reducing agent sodium borohydride is 5: 1. Adding to the initial reaction mixture an equal volume of the initial reaction mixtureAnd (5) performing ultrasonic treatment on ethanol for 5min to obtain the nano metal sulfide dispersion liquid.
And (2) dipping the nano metal sulfide dispersion liquid on the surface of the montmorillonite carrier by adopting an isometric dipping method, standing and aging for 10h at room temperature, then transferring the montmorillonite carrier into a high-pressure synthesis kettle, crystallizing for 30h at 100 ℃, and adjusting the pH value of a reaction system by using NaOH and HCl during crystallization to keep the pH value of the reaction system at 7.0-8.0. After crystallization is finished, filtering to obtain a solid product, washing the solid product by deionized water, and finally drying the solid product to obtain the catalyst WNiCuS2Montmorillonite (montmorillonite).
Example 2
0.5g of purified montmorillonite was weighed, dispersed in 100mL of deionized water, stirred electrically for 5 hours, and left to stand overnight. The sediment was removed to obtain an aqueous suspension of montmorillonite having a mass fraction of 0.5%.
Adding ionic liquid 1-ethyl-3-methylimidazole tetrafluoroborate and surfactant laurinol polyoxyethylene ether dropwise into the 0.5% montmorillonite water suspension, electrically stirring for 5h at 50 ℃, standing and aging for 12-24 h. The bottom of the vessel was a white solid deposit and the top was a pale yellow transparent liquid. The product was obtained as a white solid by centrifugation. Washing the white product with ethanol for three times, then drying in vacuum, and finally calcining at the high temperature of 500 ℃ to obtain the functionalized and chambered montmorillonite carrier. Wherein the addition amount of the 1-ethyl-3-methylimidazole tetrafluoroborate is 2 wt% of the montmorillonite, and the molar ratio of the polyoxyethylene lauryl ether to the 1-ethyl-3-methylimidazole tetrafluoroborate is 1: 3.
Adding a metal source and a sulfur source into deionized water, and reacting at 70 ℃ for 18h to obtain a mixed solution; wherein the metal source is sodium dithiotungstate (K)2WO2S2) The sulfur source is sodium sulfide, and the molar ratio of the four substances (sodium dithiotungstate, nickel nitrate, copper sulfate and sodium sulfide) is 1:1:1: 1. Adding the ionic liquid 1-ethyl-3-methylimidazole tetrafluoroborate and the reducing agent hydroxylamine hydrochloride into the mixed solution again, stirring uniformly, and preparing an initial reaction mixture, wherein the molar ratio of the ionic liquid 1-ethyl-3-methylimidazole tetrafluoroborate to the reducing agent hydroxylamine hydrochlorideIs 0.5: 1. And adding ethanol with the same volume as the initial reaction mixture into the initial reaction mixture, and carrying out ultrasonic treatment for 5min to obtain the nano metal sulfide dispersion liquid.
And (3) dipping the nano metal sulfide dispersion liquid on the surface of the montmorillonite carrier by adopting an isometric dipping method, standing for 15h at room temperature, then transferring to a high-pressure synthesis kettle, crystallizing for 50h at 180 ℃, and adjusting the pH value of a reaction system by using NaOH and HCl during crystallization to keep the pH value of the reaction system at 7.0-8.0. After crystallization is finished, filtering to obtain a solid product, washing the solid product by deionized water, and finally drying the solid product to obtain the catalyst WNiCuS2Montmorillonite (montmorillonite).
Example 3
1.5g of purified montmorillonite was weighed, dispersed in 100mL of deionized water, stirred electrically for 5 hours, and left to stand overnight. The sediment was removed to obtain an aqueous suspension of montmorillonite having a mass fraction of 1.5%.
Adding ionic liquid 1-butyl-3-methylimidazolium bromide and surfactant Tween 80 dropwise into the 1.5% montmorillonite water suspension, stirring electrically at 50 deg.C for 5 hr, standing and aging for 12-24 hr. The bottom of the vessel was a white solid deposit and the top was a pale yellow transparent liquid. The product was obtained as a white solid by centrifugation. Washing the white product with ethanol for three times, then drying in vacuum, and finally calcining at the high temperature of 800 ℃ to obtain the functionalized and chambered montmorillonite carrier. Wherein the adding amount of the 1-butyl-3-methylimidazolium bromide is 4 wt% of the montmorillonite, and the molar ratio of the Tween 80 to the 1-butyl-3-methylimidazolium bromide is 1: 5.
Adding a metal source and a sulfur source into deionized water, and reacting at 80 ℃ for 20 hours to obtain a mixed solution; wherein the metal source is sodium dithiotungstate (K)2WO2S2) The sulfur source is ammonium sulfide, and the molar ratio of the four substances (sodium dithiotungstate, nickel sulfate, copper nitrate and ammonium sulfide) is 1:1:1: 1. Adding the ionic liquid 1-butyl-3-methylimidazole bromine salt and the reducing agent sodium borohydride into the mixed solution again, uniformly stirring the mixture to prepare an initial reaction mixture, wherein the molar ratio of the ionic liquid 1-butyl-3-methylimidazole bromine salt to the reducing agent sodium borohydrideIs 1: 1. And adding ethanol with the same volume as the initial reaction mixture into the initial reaction mixture, and carrying out ultrasonic treatment for 5min to obtain the nano metal sulfide dispersion liquid.
And (3) dipping the nano metal sulfide dispersion liquid on the surface of the montmorillonite carrier by adopting an isometric dipping method, standing for 5 hours at room temperature, then transferring to a high-pressure synthesis kettle, crystallizing for 100 hours at 20 ℃, and adjusting the pH value of a reaction system by using NaOH and HCl during crystallization to keep the pH value of the reaction system at 7.0-8.0. After crystallization is finished, filtering to obtain a solid product, washing the solid product by deionized water, and finally drying the solid product to obtain the catalyst WNiCuS2Montmorillonite (montmorillonite).
Example 4
1.0g of purified montmorillonite was weighed, dispersed in 100mL of deionized water, stirred electrically for 5 hours, and left to stand overnight. The sediment was removed to obtain an aqueous suspension of montmorillonite having a mass fraction of 1%.
Dropwise adding the ionic liquid 1-ethyl-3-methylimidazole hexafluorophosphate and surfactant octanol polyoxyethylene ether into the 1% montmorillonite aqueous suspension, electrically stirring for 5 hours at 50 ℃, and standing and aging for 12-24 hours. The bottom of the vessel was a white solid deposit and the top was a pale yellow transparent liquid. The product was obtained as a white solid by centrifugation. Washing the white product with ethanol for three times, then drying in vacuum, and finally calcining at the high temperature of 600 ℃ to obtain the functionalized and chambered montmorillonite carrier. Wherein the addition of the 1-ethyl-3-methylimidazole hexafluorophosphate is 5 wt% of the montmorillonite, and the molar ratio of the octanol polyoxyethylene ether to the 1-ethyl-3-methylimidazole hexafluorophosphate is 1: 4.
Adding a metal source and a sulfur source into deionized water, and reacting for 15 hours at 85 ℃ to obtain a mixed solution; wherein the metal source is sodium dithiotungstate (Na)2WO2S2) The sulfur source is ammonium sulfide, and the molar ratio of the four substances (sodium dithiotungstate, nickel sulfate, copper sulfate and ammonium sulfide) is 1:1:1: 1. Adding ionic liquid 1-ethyl-3-methylimidazolium hexafluorophosphate and reducing agent sodium borohydride into the mixed solution again, stirring uniformly to prepare an initial reaction mixture, wherein the ionic liquid 1-ethylThe molar ratio of the-3-methylimidazolium hexafluorophosphate salt to the reducing agent sodium borohydride is 20: 1. And adding ethanol with the same volume as the initial reactant into the initial reaction mixture, and performing ultrasonic treatment for 5min to obtain the nano metal sulfide dispersion liquid.
And (3) dipping the nano metal sulfide dispersion liquid on the surface of the montmorillonite carrier by adopting an isometric dipping method, standing for 10 hours at room temperature, then transferring to a high-pressure synthesis kettle, crystallizing for 120 hours at 60 ℃, and adjusting the pH value of a reaction system by using NaOH and HCl during crystallization to keep the pH value of the reaction system at 7.0-8.0. After crystallization is finished, filtering to obtain a solid product, washing the solid product by deionized water, and finally drying the solid product to obtain the catalyst WNiCuS2Montmorillonite (montmorillonite).
Comparative example 1
Essentially identical to the procedure for the preparation of example 1, with the difference that: in the preparation process of the functionalized and expanded montmorillonite carrier and the nano metal sulfide dispersion liquid, no ionic liquid is added as an auxiliary agent.
Comparative example 2
Essentially identical to the procedure for the preparation of example 2, with the difference that: in the preparation process of the functionalized and expanded montmorillonite carrier and the nano metal sulfide dispersion liquid, no ionic liquid is added as an auxiliary agent.
Comparative example 3
Essentially identical to the procedure for the preparation of example 3, with the difference that: in the preparation process of the functionalized and expanded montmorillonite carrier and the nano metal sulfide dispersion liquid, no ionic liquid is added as an auxiliary agent.
Comparative example 4
Essentially identical to the procedure for the preparation of example 4, with the difference that: in the preparation process of the functionalized and expanded montmorillonite carrier and the nano metal sulfide dispersion liquid, no ionic liquid is added as an auxiliary agent.
WNiCuS prepared in examples 1-4 above2WNiCuS in/montmorillonite composite catalyst2A uniform continuous monolayer was formed on the surface of the montmorillonite support. WNiCuS2The mass ratio of montmorillonite is 1-5: 10-20. Based on the total mass of the obtained catalyst, the content of W (based on the weight of the metal oxide) is 6-32Wt%, Ni content (based on the weight of the metal oxide) of 1.5-10 wt%, Cu content (based on the weight of the metal oxide) of 1.5-10 wt%, and specific surface area of 200-450m2The pore volume is 0.6-1.8 ml/g, and the pore diameter is 10-35 nm.
To better illustrate the catalytic activity advantage of the nano tungsten disulfide nickel copper/montmorillonite prepared in examples 1-4 in hydrodenitrogenation of residual oil, the applicant performed hydrodenitrogenation reaction on residual oil in a high-pressure microreactor by using the catalysts prepared in examples 1-4 and comparative examples 1-4 under the following specific process conditions: the catalyst loading is 200ml, the experimental device keeps the hydrogen partial pressure at 9-15MPa, the reaction temperature is between 300 ℃ and 400 ℃, the volume ratio of hydrogen to oil is 750, and the initial nitrogen content of the residual oil is 1200 mg/kg. And the carbon deposition amount of the catalyst after running for 1000h is tested. The specific test results are shown in table 1 below.
From the test results of table 1, it can be found that the catalysts prepared in examples 1 to 4 have a denitrification rate of 95%, 93%, 95%, 98% for the residual oil, respectively, exhibit excellent catalytic activity, and are excellent in carbon deposition resistance. In comparative examples 1 to 4, the ionic liquid was not added as an auxiliary, and the catalytic performance and the carbon deposition resistance were both significantly reduced.
TABLE 1 evaluation results of catalyst Properties in examples and comparative examples
In the above test, the nitrogen content in the residual oil is carried out on an RPA-200A type microcoulometer by adopting a microcoulometric titration method, the carbon deposition amount is carried out on a NETZSCH TG 209F3 thermogravimetric analyzer by adopting a thermogravimetric analysis method, and the specific test steps are not repeated herein.
It should be noted that the above-mentioned embodiments illustrate rather than limit the invention, and that those skilled in the art will be able to design alternative embodiments without departing from the scope of the appended claims. In the claims, any reference signs placed between parentheses shall not be construed as limiting the claim. The word "comprising" does not exclude the presence of elements or steps not listed in a claim. The usage of the words first, second and third, etcetera do not indicate any ordering and these words may be interpreted as names.
Claims (10)
1. The preparation method of the hydrodenitrogenation catalyst is characterized by comprising the following steps of:
1) dispersing montmorillonite in water, standing, and removing precipitate to obtain montmorillonite water suspension;
2) adding ionic liquid and nonionic surfactant into the montmorillonite water suspension, stirring, standing, and centrifuging to obtain white solid product; drying and calcining the white solid product to obtain a montmorillonite carrier;
3) adding a metal source and a sulfur source into water, and reacting at 60-85 ℃ for 15-20h to obtain a mixed solution;
4) adding an ionic liquid and a reducing agent into the mixed solution to prepare an initial reaction mixture;
5) carrying out ultrasonic treatment on the initial reaction mixture to obtain a nano metal sulfide dispersion liquid;
6) dipping the nano metal sulfide dispersion liquid on the surface of the montmorillonite carrier by adopting an isometric dipping method, standing, and then transferring the nano metal sulfide dispersion liquid into a high-pressure synthesis kettle for crystallization;
7) and after crystallization is finished, separating a solid product to obtain the catalyst.
2. The method of claim 1, wherein the metal source is any two or three of a tungsten source, a nickel source, and a copper source; the sulfur source is one or two of ammonium sulfide, sodium sulfide, potassium sulfide and thiourea.
3. The method of claim 2, wherein the tungsten source is a sulfur tungsten compound, the nickel source is a soluble nickel-containing sulfate or nitrate, and the copper source is a soluble copper-containing sulfate or nitrate.
4. The method for producing a hydrodenitrogenation catalyst according to claim 1, wherein in step 2), the ionic liquid is added in an amount of 0.5 to 5 wt% based on the montmorillonite.
5. The method of claim 1, wherein the ionic liquid contains one or more cations selected from the group consisting of alkyl imidazole and quaternary ammonium ions, and anions selected from the group consisting of halogen ions, tetrafluoroborate, hexafluorophosphate, borate, phosphate, carbonate, and hydroxide.
6. The method for preparing the hydrodenitrogenation catalyst according to claim 1, wherein in the step 2), the nonionic surfactant is one or two of tween 80, polyoxyethylene lauryl ether and polyoxyethylene octanol, and the molar ratio of the nonionic surfactant to the ionic liquid is 1:1-1: 5.
7. The method of claim 1, wherein the reducing agent is one or both of sodium borohydride and hydroxylamine hydrochloride.
8. The method for preparing a hydrodenitrogenation catalyst according to any one of claims 1 to 7, wherein the crystallization conditions are: the crystallization temperature is 50-200 ℃, and the crystallization time is 10-120 h.
9. A hydrodenitrogenation catalyst obtained by the production method according to any one of claims 1 to 8.
10. Use of the catalyst according to claim 9 in hydrodenitrogenation reactions of resids.
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