CN110252325A - Crude naphthalene selective hydrocatalyst and preparation method thereof - Google Patents
Crude naphthalene selective hydrocatalyst and preparation method thereof Download PDFInfo
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- CN110252325A CN110252325A CN201810201966.XA CN201810201966A CN110252325A CN 110252325 A CN110252325 A CN 110252325A CN 201810201966 A CN201810201966 A CN 201810201966A CN 110252325 A CN110252325 A CN 110252325A
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- catalyst
- naphthalene
- crude naphthalene
- oxide
- carbon nanotube
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- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 title claims abstract description 160
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 58
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 47
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 47
- 229910052751 metal Inorganic materials 0.000 claims abstract description 44
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000002184 metal Substances 0.000 claims abstract description 36
- 239000000470 constituent Substances 0.000 claims abstract description 20
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 19
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000011148 porous material Substances 0.000 claims abstract description 16
- 238000000465 moulding Methods 0.000 claims abstract description 11
- 238000004898 kneading Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 36
- 239000006185 dispersion Substances 0.000 claims description 32
- 239000007788 liquid Substances 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 22
- 239000004094 surface-active agent Substances 0.000 claims description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 15
- 239000013504 Triton X-100 Substances 0.000 claims description 13
- 229920004890 Triton X-100 Polymers 0.000 claims description 13
- 238000005119 centrifugation Methods 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 9
- 229910052721 tungsten Inorganic materials 0.000 claims description 9
- 239000010937 tungsten Substances 0.000 claims description 9
- 125000000524 functional group Chemical group 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 7
- 239000004744 fabric Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000002048 multi walled nanotube Substances 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000002736 nonionic surfactant Substances 0.000 claims description 6
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 5
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- ZPIRTVJRHUMMOI-UHFFFAOYSA-N octoxybenzene Chemical compound CCCCCCCCOC1=CC=CC=C1 ZPIRTVJRHUMMOI-UHFFFAOYSA-N 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 229910052738 indium Inorganic materials 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 239000002304 perfume Substances 0.000 claims 1
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 25
- 230000000694 effects Effects 0.000 abstract description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 abstract description 4
- 239000011593 sulfur Substances 0.000 abstract description 4
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical group C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 26
- 239000000047 product Substances 0.000 description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- LMIZORQOLSLQRY-UHFFFAOYSA-N benzene;naphthalene Chemical compound C1=CC=CC=C1.C1=CC=CC2=CC=CC=C21 LMIZORQOLSLQRY-UHFFFAOYSA-N 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 6
- 238000002604 ultrasonography Methods 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- -1 aromatic radical Chemical class 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- 241000219782 Sesbania Species 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- QIMMUPPBPVKWKM-UHFFFAOYSA-N 2-methylnaphthalene Chemical compound C1=CC=CC2=CC(C)=CC=C21 QIMMUPPBPVKWKM-UHFFFAOYSA-N 0.000 description 3
- 238000004438 BET method Methods 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 230000001404 mediated effect Effects 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229940011182 cobalt acetate Drugs 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
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- GLXXXIJXSRSBSJ-UHFFFAOYSA-N C1C=CC2=CC=CC=C12.[S] Chemical class C1C=CC2=CC=CC=C12.[S] GLXXXIJXSRSBSJ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- ZRXADTFMGYNRKV-UHFFFAOYSA-N [S].C1=CC=CC2=CC=CC=C21 Chemical compound [S].C1=CC=CC2=CC=CC=C21 ZRXADTFMGYNRKV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 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
- 238000004458 analytical method Methods 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 150000002469 indenes Chemical class 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 238000009736 wetting 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
- 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
- B01J23/76—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of crude naphthalene selective hydrocatalysts and preparation method thereof.The catalyst includes metal active constituent and the modified support for loading the metal active constituent, the carrier is mainly formed by carbon nanotube and aluminium oxide through kneading, molding and drying, roasting, the metal active constituent includes metal oxide, and the metal oxide includes VI B race and/or VIII race's metallic element.The hole that aperture is 8~10nm in the catalyst accounts for 0.6~0.8ml/g of 90% of total pore volume or more, Kong Rongwei, and specific surface area is 240~300m2/g.Compared with prior art, catalyst provided by the invention has the advantages that ideal pore-size distribution is concentrated, hole accommodates suitable, large specific surface area, good to sulfur-containing impurities-benzo-thiophene selective hydrogenation activity in crude naphthalene, is suitable for crude naphthalene selective hydrogenation and produces refined naphthalene.
Description
Technical field
The present invention relates to a kind of selective hydrocatalysts, specifically, being a kind of selectivity of crude naphthalene production refined naphthalene
Sulfur-containing compound selective hydrocatalyst in hydrogenation catalyst, i.e. crude naphthalene, heavy benzol naphthalene or thick naphthalene.
Background technique
Naphthalene is important industrial chemicals, is mainly used for catalysis oxidation phthalic anhydride and dyestuff intermediate, is also used for subtracting as cement
Aqua, surfactant, plasticizer, polyester, synthetic fibers and drug etc..The naphthalene of 70% or more the country depends on coking industry,
It is very mature by coal tar production crude naphthalene technology, but the purity of crude naphthalene only has 95%, is not able to satisfy it as fine chemistry
The requirement of product raw material is required to the refined naphthalene that purity is greater than 99% by the fine chemicals that raw material produces of naphthalene.It is main in crude naphthalene
Impurity is benzothiophene, and content is about 2~3%, secondly goes back content a small amount of tetrahydronaphthalene, quinoline, beta-methylnaphthalene and ash content,
These impurity phases relatively easily remove benzothiophene, and therefore, crude naphthalene purifies refined naphthalene key processed and is to remove benzo-thiophene.
Heavy benzol naphthalene is derived from heavy benzol, and heavy benzol is the by-product generated in coal chemical industry crude benzole hydrogenation technical process.Heavy benzol naphthalene,
The method that refined naphthalene is made in crude naphthalene or thick naphthalene has physical method, chemical method and combination method.Physical method mainly has emulsion liquid membrane, crystallization
Method, rectification method；Chemical method mainly has aldehydes condensation method, acids oxidizing process and selective hydrogenation method, and wherein selective hydrogenation is domestic
Research and develop less, relative to very mature crude benzol selective hydrogenation, the selective hydrogenation of thick naphthalene still belonged in the starting stage.
In the thick naphthalene selective hydrogenation technology that Kawasaki, Japan public affairs propose, catalyst is selected from Ni-Co-Mo, aluminium/charcoal, Pt-Ni-
Mo, Pd- aluminium oxide etc. reacts at 100~300 DEG C at 0~2MPa, and sulfur content is 0.025wt% in refined naphthalene.This technology has
Part naphthalene, which is hydrogenated, generates tetrahydronaphthalene, to affect the yield of refined naphthalene.Higher refined naphthalene yield in order to obtain, selectivity
Add the refined naphthalene for also needing seven step processes that can obtain yield raising after hydrogen.
In the method that Compagnie Francise des Petroles proposes, using loaded catalyst, active component includes at least one VIIIth He
VIth race's metal, it is also an option that property contain phosphorus.Catalyst specific surface is up to 220m2/ g, and average pore size is greater than 10nm.
150~325 DEG C of selective hydrogenation temperature, 0.1~0.9MPa of pressure, before the stripping/Crystallization Procedure for entering next step
In liquid stream, the content of by-product tetrahydronaphthalene is about 3.0%, and the yield of refined naphthalene is only 97%.For the receipts for further increasing refined naphthalene
Rate is recycled back to hydrogenator entrance using tetrahydronaphthalene and combines stripping/Crystallization Procedure method.
As can be seen that problems of the prior art are the generation of tetrahydronaphthalene by-product, therefore affect refined naphthalene
Yield consumes more hydrogen though compensating for some yields to a certain extent using the method that tetrahydronaphthalene recycles
Raw material, to increase processing cost.
Summary of the invention
In order to solve the problems in the existing technology, the present invention provides a kind of crude naphthalene selective hydrogenations to produce refined naphthalene
Catalyst, with good selectivity hydrogenation activity and activity stability selective hydrocatalyst.
For realization aforementioned invention purpose, the technical solution adopted by the present invention includes:
The embodiment of the invention provides a kind of crude naphthalene selective hydrocatalysts comprising metal active constituent and load
The modified support of the metal active constituent.
Further, the described carrier is mainly formed by carbon nanotube and aluminium oxide through kneading, molding and drying, roasting.
Further, the metal active constituent includes metal oxide, the metal oxide include VI B race and/or
VIII race's metallic element.
Further, in the catalyst aperture be 8~10nm hole account for 90% of total pore volume or more, Kong Rongwei 0.6~
0.8ml/g, specific surface area are 240~300m2/g。
Further, the catalyst includes 40~90wt% modified support and 5~15wt% metal active constituent.
The embodiment of the invention also provides the preparation methods of aforementioned industrial naphthalene selective hydrocatalyst comprising:
1) carbon nano tube dispersion liquid is prepared；
2) by aluminium oxide and the obtained carbon nano tube dispersion liquid of step 1), extruded moulding, later drying are roasted after mixing,
Obtain modified support；
3) non-ionic surface active of the functional group containing aromatic radical is added into the aqueous solution of the presoma of metal active constituent
Agent and form mixed liquor, the presoma of the metal active constituent is selected from the water solubility comprising VI B race and/or VIII race's metallic element
Compound, the metal active constituent are selected from metal oxide；
4) the obtained modified support of step 2) is impregnated in the obtained mixed liquor of step 3), is dried later, calcination process,
Obtain the selective hydrocatalyst.
Further, carbon nano tube dispersion liquid described in step 1) is made in the presence of surfactant.
Further, step 1) specifically includes:
First that the surfactant is soluble in water, solution temperature is 40~70 DEG C, and the surfactant preferably contains
The surfactant of aromatic radical functional group such as Triton X-100 Triton X-100；
The aqueous surfactant solution is added in a certain amount of carbon nanotube again (concentration is preferably 0.5~2.0wt%)
In stir evenly, it is preferred that can be used ultrasonic agitation, 5~30min of ultrasonic time, 0~5 DEG C of whipping temp；After ultrasonic agitation,
Preferably, centrifugal sedimentation can be used and remove not scattered agglomerated particles, centrifugation rate is 1500~2000r/min, when centrifugation
Between 30~60min；After centrifugation, then with the above-mentioned dispersion liquid of filter-cloth filtering, stable carbon nano tube dispersion liquid is obtained.It selects excellent
, filter cloth mesh number is 300~500 mesh.
Further, step 2) includes: that expanding agent, extrusion aid is added after mixing aluminium oxide with carbon nano tube dispersion liquid,
Extruded moulding again is dried, calcination process later；Preferably, the temperature of the drying process is 80~160 DEG C；Preferably,
The temperature of the calcination process is 400~700 DEG C, and calcining time is 1~15h；And/or the drying used in the step 3)
Temperature is 80~160 DEG C, and maturing temperature is 400~650 DEG C, and calcining time is 1~15h.
Further, any one or two kinds of VI B race or VIII race's metallic element in molybdenum, tungsten, cobalt and nickel with
On combination；Preferably, the metal oxide includes any one in molybdenum trioxide, tungstic acid, nickel oxide and cobalt oxide
Kind or two or more combinations；It is further preferred that the metal oxide is selected from molybdenum trioxide and/or tungstic acid, and
The content of metal oxide is 4~9wt% in the catalyst；It is further preferred that the metal oxide is selected from nickel oxide
And/or cobalt oxide, the content of metal oxide is 2~6wt% in the catalyst.
Further, the dosage of the carbon nanotube is 0.5~1.2wt% of modified support gross mass, especially preferably
0.6~1.0wt%.
Further, the dosage of the expanding agent is 1.0~4.0wt% of modified support gross mass.
Further, the dosage of the extrusion aid is 1.0~2.0wt% of modified support gross mass.
Further, the dosage of the step 2) surfactant is 0.5~1.0 times of carbon nanotube.
Further, the surfactant used in the step 2), step 3) is the nonionic of the functional group containing aromatic radical
Surfactant.
Further, the carbon nanotube uses short MWCNTs, and caliber is less than 8nm, and specific surface is greater than
500m2/ g, length are 0.5~2.0 μm.
The embodiment of the invention also provides the catalyst to the concrete application of crude naphthalene selective hydrogenation.
In some embodiments, the catalyst contains suitable for coking of coal industry heavy benzol naphthalene, crude naphthalene or thick naphthalene
The process of the selective hydrogenation production refined naphthalene of sulphur compound.
In some embodiments, the catalyst, which is characterized in that for crude naphthalene selective hydrogenation technique item
Part is that the volume space velocity of reaction is 0.3~1.0h-1, system response pressure hydrogen partial pressure is 4.0~6.0MPa, reaction temperature 340
~360 DEG C, hydrogen-oil ratio is 500~1000.Preferably, the volume space velocity of reaction is 0.5~0.7h-1, system response pressure hydrogen point
Pressure is 5.0MPa, and reaction temperature is 345~355 DEG C, and hydrogen-oil ratio is 600~800.
Compared with prior art, the invention has the advantages that
1, catalyst of the present invention adds short MWCNTs in modified support preparation process, makes obtained catalyst pores
Diameter is that the hole of 8~10nm accounts for 90% of total pore volume or more, this aperture is big for major impurity benzo-thiophene molecular volume in crude naphthalene
Small design.Know that benzo-thiophene molecule three-dimensional space stereochemical structure approximation regards a ball as by the calculating of quantum chemistry gaussian software,
Its diameter is about 7~10 angstroms, and naphthalene molecule is then greater than 10 angstroms.Accordingly, caliber is added to than determining short MWCNTs and is changed
In the preparation process of property alumina support (i.e. modified support), former aperture modified support is made becoming specific surface to be suitable for changing of becoming smaller
While property carrier, it is provided with the pore size distribution more concentrated.The fusing point of carbon nanotube be it is highest in known materials, roast at high temperature
It burns, will not deform and collapse.Expanding agent is added to make short MWCNTs surrounding space of the caliber less than 8nm into one
Step expands, and the ratio for making the hole of 8~10nm account for total pore volume further increases, to obtain better benzo-thiophene hydrogenation activity.This catalysis
Agent aperture reacts more benzo-thiophene molecules into catalyst inner surface, and by naphthalene molecule gear outside hole, to prevent
It carries out hydrogenation reaction and is converted into other compounds.The yield of final refined naphthalene is set to be significantly improved in this way.2, present invention catalysis
Expanding agent, extrusion aid is added using small porous aluminum oxide to be added in carbon nanotube aqueous dispersions in agent, makes through kneading, drying, roasting
Modified support, then the method for impregnating VI B race or VIII race's metal active constituent are obtained, there is catalyst of the present invention and preferably add hydrogen living
Property and activity stability, be the ethylbenzene that becomes smaller of boiling point by most of benzo-thiophene hydro-conversion, finally separated through distilling with naphthalene, made
The purity and yield of naphthalene are further improved.
3, the selective hydrogenation process conditions provided using catalyst of the present invention and invention can make benzo-thiophene carry out adding hydrogen
Reaction, and naphthalene does not originally react, and can obtain preferable desulfurization effect in this way, conducive to the raising of refined naphthalene yield.
Specific embodiment
In view of deficiency in the prior art, inventor is studied for a long period of time and is largely practiced, and is able to propose of the invention
Technical solution as follows will be further explained the technical solution, its implementation process and principle etc..
A kind of preparation method for crude naphthalene selective hydrocatalyst that the one aspect of the embodiment of the present invention provides includes:
1) carbon nano tube dispersion liquid is first prepared；
2) by aluminium oxide and the obtained carbon nano tube dispersion liquid of step 1), extruded moulding, later drying are roasted after mixing,
Obtain carrier；
3) nonionic surfactant used in step 2) is added into the aqueous solution of the presoma of metal active constituent
And mixed liquor is formed, the presoma of the metal active constituent is selected from the water solubilityization comprising VI B race and/or VIII race's metallic element
Object is closed, the metal active constituent is selected from metal oxide, later by the obtained carrier impregnation of step 2) in the mixed liquor, it
After be dried, calcination process, obtain the selective hydrocatalyst.
In some embodiments, the crude naphthalene selective hydrocatalyst by 4~9wt% VI B race metal, 2
VIII race's metal of~6wt% and modified support composition.Modified support adds carbon nanotube during the preparation process and is modified, then will live
Property component load thereon.In this catalyst, aperture is that the hole of 8~10nm accounts for 0.6~0.8ml/ of 90% of total pore volume or more, Kong Rong
G, specific surface area are 240~300m2/g。
In some embodiments, the crude naphthalene selective hydrocatalyst includes 40~90wt% carrier and 5
~15wt% metal active constituent.
In some embodiments, any one of VI B race or VIII race's metallic element in molybdenum, tungsten, cobalt and nickel
Or two or more combinations, but not limited to this.
In some embodiments, in catalyst of the invention, the metal oxide includes molybdenum trioxide, three oxidations
Any one in tungsten, nickel oxide and cobalt oxide or two or more combinations, but not limited to this.Preferably, the water solubilityization
Close object include any one or two kinds in ammonium molybdate, ammonium metatungstate, nickel nitrate, basic nickel carbonate, cobalt nitrate and cobalt acetate with
On combination, but not limited to this.
In some embodiments, the modified support is added after mixing aluminium oxide with carbon nano tube dispersion liquid
Expanding agent, extrusion aid, then extruded moulding are dried, calcination process later；Preferably, the temperature of the drying process is 80
~160 DEG C, dry 1~6h；Preferably, the temperature of the calcination process is 400~700 DEG C, and calcining time is 1~15h, especially
Preferred 3~5h.
In some embodiments, the drying temperature used in the step 3) is 80~160 DEG C, dry 1~6h；It is preferred that
, maturing temperature is 400~650 DEG C, and calcining time is 1~9h, especially preferred 3~5h.
In some embodiments, the dosage of nonionic surfactant described in step 3) be carrier gross mass 2~
10wt%.Further, the nonionic surfactant is using nonionic surfactant used in step 2), such as poly- second
Glycol octyl phenyl ether Triton X-100, but not limited to this.The effect of nonionic surfactant is added in step 3) of the present invention
It is that impregnate active metal more abundant, improves the load capacity and dispersion degree of active metal component.
In some embodiments, it is 0.3~0.6ml/g that the alumina pore, which holds, the average value in aperture is 2~
10nm。
In some embodiments, at the time of molding, this can be selected in extrusion aid used and expanding agent to the modified support
Substance known to field, expanding agent are the 1.0~4.0wt%, preferably 3.0~4.0wt% of vehicle weight.It such as can be selected optional
Expanding agent known to the fields such as sesbania powder, starch, polyvinyl alcohol, methylcellulose further improves carrier pore structure.It helps crowded
Agent is 1.0~2.0wt% of vehicle weight.
In some embodiments, at the time of molding, the dosage of the carbon nanotube is modified support gross mass to modified support
0.5~1.2wt%, especially preferably 0.6~1.0wt%.
In some embodiments, carbon nano tube dispersion liquid can be prepared by the known method in this field.Preferably, carbon nanometer
Pipe dispersion liquid is made in the presence of surfactant by carbon nanotube；It is especially preferred, first the surfactant is dissolved in
In water, solution temperature is 40~70 DEG C, and the surfactant is preferably for example poly- second of surfactant of the functional group containing aromatic radical
Glycol octyl phenyl ether Triton X-100；The use of the surfactant of functional group containing aromatic radical, can be because of the fragrance of aromatic group
Ring is stronger to carbon nanotube adsorption, so that carbon nanotube be made to dissolve in water more evenly.Again by a certain amount of carbon nanotube
It is added in this aqueous surfactant solution (concentration is preferably 0.5~2.0wt%) and stirs evenly, it is preferred that ultrasound can be used and stir
It mixes, 5~30min of ultrasonic time；The purpose of ultrasonic agitation also for obtaining more evenly more stable carbon nano-tube solution, in order to
The foaming phenomena because of caused by the presence of surfactant is prevented, ultrasonic agitation carries out at 0~5 DEG C, and preferably with ultrasound
5min is further continued for the mode being stirred by ultrasonic, total 5~30min of ultrasonic time after stopping 3~5min；Preferably, it is heavy that centrifugation can be used
Drop removes not scattered agglomerated particles, and centrifugation rate is 1500~2000r/min, 30~60min of centrifugation time；Centrifugation terminates
Afterwards, then with the above-mentioned dispersion liquid of filter-cloth filtering, stable carbon nano tube dispersion liquid is obtained.Select it is excellent, filter cloth mesh number be 300~500
Mesh.Especially preferred, the carbon nanotube uses short MWCNTs, and caliber is less than 8nm, and specific surface is greater than 500m2/ g,
Length is 0.5~2 μm.
The embodiment of the invention also provides aforementioned catalytic agents selectively to add in coking of coal industry heavy benzol naphthalene, crude naphthalene or thick naphthalene
The process of hydrogen production refined naphthalene.In some embodiments of the invention, the volume space velocity of selective hydrogenation be 0.5~
0.7h-1, system response pressure hydrogen partial pressure is 5.0MPa, and reaction temperature is 345~355 DEG C, under the conditions of hydrogen-oil ratio is 600~800,
Major impurity is that heavy benzol naphthalene, crude naphthalene or the thick naphthalene of benzo-thiophene are reacted through one-stage selective hydrogenation, can make 99.8% or more sulphur
Indenes is converted into ethylbenzene, and naphthalene is almost without reaction, and the boiling point of ethylbenzene is significantly lower than naphthalene, therefore purity can be obtained using distillating method
With the higher refined naphthalene product of yield.Result ideal so mainly has benefited from " customized " to catalyst duct, short more
The use of wall carbon nano tube and expanding agent makes the pore-size distribution high concentration of catalyst of the present invention, only benzo-thiophene is made to enter catalyst
Inner surface is reacted, and naphthalene is foreclosed.Technical solution of the present invention is made below in conjunction with several embodiments further
It illustrates.
Following embodiment is intended to use active metal dipping solution.Illustrate to prepare dipping by taking active metal tungsten and nickel as an example
The method of solution: taking a certain amount of deionized water, and ammonium metatungstate (or ammonium molybdate), nickel nitrate (or basic carbonate are added thereto
Nickel, cobalt nitrate, cobalt acetate) crystal, after all dissolutions, standing, filtering obtains metal impregnation solution, wherein WO3Or MoO3's
Content is that the content of 10.0~25.0g/100ml, NiO or CoO are 7.0~15.0g/100ml.Metal impregnation solution is formulated as
This field mature technology, can refer to pertinent literature.
Following embodiment is intended to use carbon nano tube dispersion liquid.The preferred preparation process of carbon nanotube aqueous dispersions
It is as follows: 1) 15g Triton X-100 Triton X-100 to be dissolved in 976g water, at 40 DEG C, stirred to transparent molten
Liquid；
2) 20g short MWCNTs CNT402 (Beijing Deco Dao Jin Science and Technology Ltd. product) is added, stirring makes carbon
Nanotube is by aqueous dispersant complete wetting；
3) under ultrasound condition, keep dispersion liquid dispersion more uniform.Every stirring 5 minutes, is further continued for ultrasound after stopping 5min
Stirring, total ultrasonic time 30min；Preferably, ultrasound procedure in 0 DEG C of environment can be placed in exist into water without particulate matter.
4) after ultrasound, by above-mentioned dispersion liquid centrifugal sedimentation, not scattered agglomerated particles are removed.Centrifugation rate is
1800r/min, centrifugation time 45min；
5) centrifugation terminates, and by 500 mesh filter-cloth filterings of supernatant liquid, obtains stable carbon nano tube dispersion liquid.Drying is heavy
It forms sediment to constant weight, is denoted as 4.3g.Thermogravimetric analysis is carried out to precipitating, thermal weight loss rate when writing down 450 DEG C is about 20%, i.e., divides in precipitating
Powder content；
6) having prepared 993g content in this way is about 1.7% carbon nano tube dispersion liquid, spare.
Embodiment 1
(1) preparation of modified support
Take the small porous aluminum oxide of 100g (the common aperture alumina powder that commercially available 0.3~0.6ml/g of Kong Rongwei can be used),
After 60g foregoing carbon nanotubes dispersion liquid, 4g sesbania powder are mixed, the aqueous solution of 50ml 2g containing citric acid is added, mediated, be extruded into
After type, 100 DEG C of dry 5h, then at 600 DEG C 3h is roasted, strip carrier is made.
(2) preparation of catalyst:
A, the preparation of metal impregnation solution is as described above, takes tungsten nickel solution (WO3Content 20.0g/100ml, NiO content
For 7.0g/100ml) 40ml, Triton X-100 Triton X-100 is added, aqueous solution is made in additional amount about 6g；
B, modified support obtained in 100g step (1) is taken, the aqueous solution (wherein containing metal ion) being made into is added to
Middle dipping, and be filtered；
C, the obtained product of step 2) b is placed in baking oven, the dry 3h at 120 DEG C；
D, finally the product of drying is placed in Muffle furnace, and calcines 5h under the conditions of 550 DEG C to get the thick naphthalene of processing is arrived
The catalyst is named as A by selective hydrocatalyst.
Wherein the content of tungsten in the carrier is 8.0wt% to catalyst A, and the content of nickel in the carrier is 2.8wt%, activity
Total metal content has 10.8wt%.Using BET (specific surface tester) method, A catalyst specific surface 280m is learnt2/ g, Kong Rong
0.68ml/g.Aperture is that the hole of 8.0-10.0nm accounts for the 96% of total pore volume,.
Embodiment 2
(1) preparation of carrier
Take the small porous aluminum oxide of 100g (the common aperture alumina powder that commercially available 0.3~0.6ml/g of Kong Rongwei can be used),
After 36g carbon nano tube dispersion liquid, 3g sesbania powder are mixed, the aqueous solution of 50ml 1.5g containing citric acid is added, mediated, be extruded into
After type, 120 DEG C of dry 3h, then at 500 DEG C 4h is roasted, strip carrier is made.
(2) preparation of catalyst:
A, the preparation of metal impregnation solution is as described above, takes tungsten nickel solution (WO3Content 10.0g/100ml, NiO content
For 10.0g/100ml) 40ml, Triton X-100 Triton X-100 is added, aqueous solution is made in additional amount about 8g；
B, carrier obtained in 100g step (1) is taken, is added to dipping in the aqueous solution (wherein containing metal ion) being made into, and carry out
Filtering；
C, the obtained product of step (2) b is placed in baking oven, the dry 6h at 100 DEG C；
D, finally the product of drying is placed in Muffle furnace, and calcines 3h under the conditions of 600 DEG C to get the thick naphthalene of processing is arrived
The catalyst is named as B by selective hydrocatalyst.
Wherein the content of tungsten in the carrier is 4.0wt% to catalyst B, and the content of nickel in the carrier is 4.0wt%, activity
Total metal content has 8.0wt%.Using BET method, B catalyst specific surface 258m is known2/ g, Kong Rong 0.62ml/g.Aperture is 8.0-
The hole of 10.0nm accounts for the 93% of total pore volume.
Embodiment 3
(1) preparation of carrier
Take the small porous aluminum oxide of 100g (the common aperture alumina powder that commercially available 0.3~0.6ml/g of Kong Rongwei can be used),
After 48g carbon nano tube dispersion liquid, 3.5g sesbania powder are mixed, the aqueous solution of 50ml 1.0g containing citric acid is added, mediated, be extruded into
After type, 140 DEG C of dry 1h, then at 400 DEG C 5h is roasted, strip carrier is made.
(2) preparation of catalyst
A, the preparation of metal impregnation solution is as described above, takes tungsten nickel solution (WO3Content 15.0g/100ml, NiO content
For 12.5g/100ml) 40ml, Triton X-100 Triton X-100 is added, aqueous solution is made in additional amount about 4g；
B, carrier obtained in 100g step (1) is taken, is added to dipping in the aqueous solution (wherein containing metal ion) being made into, and carry out
Filtering；
C, the obtained product of step b2 is placed in baking oven, the dry 2h at 140 DEG C；
D, finally the product of drying is placed in Muffle furnace, and calcines 4h under the conditions of 450 DEG C to get the thick naphthalene of processing is arrived
The catalyst is named as C by selective hydrocatalyst.
Wherein the content of tungsten in the carrier is 6.0wt% to catalyst C, and the content of nickel in the carrier is 5.0wt%, activity
Total metal content has 11.0wt%.Using BET method, C catalyst specific surface 268m is known2/ g, Kong Rong 0.64ml/g.Aperture is 8.0-
The hole of 10.0nm accounts for the 95% of total pore volume.
Reference examples 1
(1) preparation of carrier: in addition to being added without carbon nanotube powder, other steps are the same as embodiment 3.
(2) preparation of catalyst: with embodiment 3.
Comparative catalyst DC is thus made, the content of tungsten, nickel in the carrier is the same as catalyst C.Using BET method,
Know this DC catalyst specific surface 156m2/ g, Kong Rong 0.49ml/g.The hole of aperture 8.0-10.0nm accounts for the 79% of total pore volume.This is urged
The obvious disperse of agent ideal pore-size distribution.From the above various embodiments as can be seen that comparing table by catalyst prepared by the method for the present invention
Area, Kong Rong and ideal 8~10nm of aperture account for total pore volume ratio and are significantly greater than the obtained catalyst of reference examples.
The raw material that the obtained A of 1-3 of the embodiment of the present invention is used to C catalyst and the obtained DC catalyst activity evaluation of reference examples
Oil is crude naphthalene, and fraction range is at 172~246 DEG C, density 1150kg/m3, 5360 μ g/g of sulfur content, wherein naphthalene content
97.0%, benzo-thiophene content 2.3% is other for compounds such as indenes and beta-methylnaphthalenes.Evaluation condition is selective hydrogenation volume
Air speed is 0.5h-1, system response hydrogen partial pressure is 5.0MPa, and reaction temperature is 350 DEG C, hydrogen-oil ratio 650.Equipped with the small of catalyst
The fixed bed hydrogenation catalyst vulcanization step that type device uses those skilled in the art to know well, after vulcanization, device operating
The Product samples that initial activity is taken when 50h after device continuously runs 3000 hours, then take Product samples, and analysis detection takes twice
Sulfur content in sample product, and contained with naphthalene and benzo-thiophene in GC-MS (combined gas chromatography mass spectrometry) analytical selective hydrogenation product
Amount, obtains data and is listed in table 1.
The activity and its stability data of the obtained catalyst A to C of 1 embodiment 1-3 of table and the obtained catalyst DC of reference examples
As can be seen from Table 1, the obtained A of 1-3 of the embodiment of the present invention~C catalyst desulfurization degree is high, is hydrogenated to tetrahydro without naphthalene
Change the side reaction of naphthalene, desulfurization degree is greater than 99.8%, hence it is evident that is better than existing such catalyst.I.e. desulphurizing activated selectivity is high, more
It is significantly that its activity stability is good.The obtained catalyst of the present invention is compared with reference examples catalyst, to crude naphthalene, heavy benzol naphthalene or slightly
Naphthalene selective hydrogenation produces refined naphthalene, and activity is high, and activity stability is good.As it can be seen that because of the selective hydrogenation activity of catalyst of the present invention
It is good, therefore to same materials, then the yield of refined naphthalene is higher than existing similar catalyst.
It should be appreciated that the technical concepts and features of above-described embodiment only to illustrate the invention, its object is to allow be familiar with this
The personage of item technology cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all
Equivalent change or modification made by Spirit Essence according to the present invention, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of crude naphthalene selective hydrocatalyst, it is characterised in that including 40~90wt% modified support and 5~15wt%
Metal active constituent, the modified support are mainly formed by carbon nanotube and aluminium oxide through kneading, molding and drying, roasting, institute
Stating metal active constituent includes metal oxide, and the metal oxide includes VI B race and/or VIII race's metallic element.Aperture is 8
~10nm.
2. crude naphthalene selective hydrocatalyst according to claim 1, it is characterised in that: aperture is in the catalyst
The hole of 8~10nm accounts for 0.6~0.8ml/g of 90% of total pore volume or more, Kong Rongwei, and specific surface area is 240~300m2/g。
3. crude naphthalene selective hydrocatalyst according to claim 1, it is characterised in that: VI B race or VIII race gold
Belong to any one or two or more combination of the element in molybdenum, tungsten, cobalt and nickel；Preferably, the metal oxide includes
Any one in molybdenum trioxide, tungstic acid, nickel oxide and cobalt oxide or two or more combinations；It is further preferred that institute
State metal oxide be selected from molybdenum trioxide and/or tungstic acid, and in the catalyst metal oxide content be 4~
9wt%；It is further preferred that the metal oxide is selected from nickel oxide and/or cobalt oxide, and metal oxygen in the catalyst
The content of compound is 2~6wt%.
4. crude naphthalene selective hydrocatalyst according to claim 1, it is characterised in that: the Kong Rongwei of the aluminium oxide
0.3~0.6ml/g, the average value in aperture are 2~10nm.
5. a kind of preparation method of crude naphthalene selective hydrocatalyst, characterized by comprising:
1) carbon nano tube dispersion liquid is prepared；
2) by aluminium oxide and the obtained carbon nano tube dispersion liquid of step 1), extruded moulding, dry later, roasting are obtained after mixing
Modified support；
3) into the aqueous solution of the presoma of metal active constituent be added the functional group containing aromatic radical nonionic surfactant and
Mixed liquor is formed, the presoma of the metal active constituent is selected from the water-soluble chemical combination comprising VI B race and/or VIII race's metallic element
Object, the metal active constituent are selected from metal oxide；
4) the obtained modified support of step 2) is impregnated in the obtained mixed liquor of step 3), is dried later, calcination process, obtained
The selective hydrocatalyst.
6. preparation method according to claim 5, which is characterized in that step 1) includes: by the table of the functional group containing aromatic radical
Face activating agent is soluble in water, and solution temperature is 40~70 DEG C, obtained aqueous surfactant solution is added in carbon nanotube later,
After even dispersion, the carbon nano tube dispersion liquid is formed；Preferably, the surfactant of the functional group containing aromatic radical includes poly- second
Glycol octyl phenyl ether Triton X-100；Preferably, step 1) further include: aqueous surfactant solution is added in carbon nanotube
In and be stirred by ultrasonic, 5~30min of ultrasonic time, 0~5 DEG C of whipping temp, later using centrifugal sedimentation mode remove it is undispersed
Agglomerated particles, centrifugation rate are 1500~2000r/min, and 30~60min of centrifugation time after centrifugation, then uses filter-cloth filtering
Above-mentioned dispersion liquid obtains stable carbon nano-tube dispersion liquid；Preferably, filter cloth mesh number is 300~500 mesh.
7. preparation method according to claim 5, which is characterized in that step 2) includes: by aluminium oxide and carbon nanotube point
After dispersion liquid mixing, expanding agent, extrusion aid, then extruded moulding is added, is dried later, calcination process；Preferably, the drying
The temperature of processing is 80~160 DEG C；Preferably, the temperature of the calcination process is 400~700 DEG C, and calcining time is 1~15h；
And/or the drying temperature used in the step 3) is 80~160 DEG C, maturing temperature is 400~650 DEG C, calcining time 1
~15h.
8. according to crude naphthalene selective hydrocatalyst described in claim 5 or 6, it is characterised in that: the carbon nanotube
Dosage is the 0.5~1.2wt%, especially preferably 0.6~1.0wt% of modified support gross mass；And/or the carbon nanotube
Using short MWCNTs, caliber is less than 8nm, and specific surface is greater than 500m2/ g, length are 0.5~2.0 μm.
9. according to right want 7 described in crude naphthalene selective hydrocatalyst, it is characterised in that: the dosage of the expanding agent be change
1.0~the 4.0wt%, preferably 3.0~4.0wt% of property carrier gross mass；And/or the dosage of the extrusion aid is modified carries
1.0~2.0wt% of body gross mass.
10. crude naphthalene selective hydrocatalyst according to claim 5, it is characterised in that: described containing virtue in step 3)
The dosage of the surfactant of perfume base functional group is 0.5~1.0 times of carbon nanotube mass.
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