CN106669796A - Preparation method of hydro-upgrading catalyst - Google Patents
Preparation method of hydro-upgrading catalyst Download PDFInfo
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- CN106669796A CN106669796A CN201510758531.1A CN201510758531A CN106669796A CN 106669796 A CN106669796 A CN 106669796A CN 201510758531 A CN201510758531 A CN 201510758531A CN 106669796 A CN106669796 A CN 106669796A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 114
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 74
- 238000010438 heat treatment Methods 0.000 claims abstract description 44
- 150000001875 compounds Chemical class 0.000 claims abstract description 34
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 29
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 23
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000005470 impregnation Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 9
- 229920002545 silicone oil Polymers 0.000 claims abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 80
- 239000003921 oil Substances 0.000 claims description 45
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 43
- 239000002808 molecular sieve Substances 0.000 claims description 43
- 229910052710 silicon Inorganic materials 0.000 claims description 43
- 239000010703 silicon Substances 0.000 claims description 43
- 239000002253 acid Substances 0.000 claims description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 32
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 31
- 230000008569 process Effects 0.000 claims description 28
- 230000036541 health Effects 0.000 claims description 17
- 239000011148 porous material Substances 0.000 claims description 17
- 239000000377 silicon dioxide Substances 0.000 claims description 15
- 229910052681 coesite Inorganic materials 0.000 claims description 13
- 229910052906 cristobalite Inorganic materials 0.000 claims description 13
- 150000002739 metals Chemical class 0.000 claims description 13
- 229910052682 stishovite Inorganic materials 0.000 claims description 13
- 229910052905 tridymite Inorganic materials 0.000 claims description 13
- 238000007598 dipping method Methods 0.000 claims description 12
- 229910052593 corundum Inorganic materials 0.000 claims description 10
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 10
- 238000001802 infusion Methods 0.000 claims description 9
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 7
- 239000002671 adjuvant Substances 0.000 claims description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 239000004033 plastic Substances 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 238000010348 incorporation Methods 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 150000003376 silicon Chemical class 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 238000009826 distribution Methods 0.000 abstract description 4
- 230000002378 acidificating effect Effects 0.000 abstract description 3
- 238000001354 calcination Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 39
- 239000002283 diesel fuel Substances 0.000 description 23
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 9
- 239000011593 sulfur Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 7
- 238000001125 extrusion Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 6
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 230000001143 conditioned effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- HORCQSAKJDDBKB-UHFFFAOYSA-N 1-methyldibenzothiophene Chemical compound S1C2=CC=CC=C2C2=C1C=CC=C2C HORCQSAKJDDBKB-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- -1 alkyl benzothiophenes Chemical class 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical class C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 2
- 230000008570 general process Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- DGUACJDPTAAFMP-UHFFFAOYSA-N 1,9-dimethyldibenzo[2,1-b:1',2'-d]thiophene Natural products S1C2=CC=CC(C)=C2C2=C1C=CC=C2C DGUACJDPTAAFMP-UHFFFAOYSA-N 0.000 description 1
- MYAQZIAVOLKEGW-UHFFFAOYSA-N 4,6-dimethyldibenzothiophene Chemical compound S1C2=C(C)C=CC=C2C2=C1C(C)=CC=C2 MYAQZIAVOLKEGW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- HIGRAKVNKLCVCA-UHFFFAOYSA-N alumine Chemical compound C1=CC=[Al]C=C1 HIGRAKVNKLCVCA-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003138 coordinated effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 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
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7815—Zeolite Beta
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/80—Mixtures of different zeolites
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0205—Impregnation in several steps
-
- 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
-
- 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
- B01J37/08—Heat treatment
-
- 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
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
- C10G49/08—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a preparation method of a hydro-upgrading catalyst. The method comprises preparing a modified hydro-upgrading catalyst carrier, loading a hydrogenation active metal component by an impregnation method, and carrying out drying and calcining to obtain the hydro-upgrading catalyst. A preparation method of the modified hydro-upgrading catalyst carrier comprises orderly or synchronously adding water soluble silicone oil and a soluble aluminum-containing compound into a hydro-upgrading catalyst carrier and carrying out heat treatment to obtain the modified hydro-upgrading catalyst carrier. The preparation method of the hydro-upgrading catalyst can adjust distribution of an acidic center and a hydrogenation active center so that the acidic center and the hydrogenation active center coordinate with each other and thus the comprehensive performances of the catalyst are improved. The hydro-upgrading catalyst is particularly suitable as a diesel hydro-upgrading catalyst.
Description
Technical field
The present invention relates to a kind of preparation method of catalyst for hydro-upgrading, particularly for the preparation method of diesel oil hydrogenation modification catalyst.
Background technology
For cleaning diesel production, prior art mainly includes the technology such as hydrofinishing and MHUG.Hydrofinishing can reduce the sulfur content for modifying diesel oil, but limited to improving Cetane number and reduction T95 temperature capabilities.MHUG is using containing molecular sieve（Such as Y type molecular sieve, beta-molecular sieve）Catalyst for hydro-upgrading, aromatic hydrocarbons in diesel oil etc. is suitably cracked, in diesel oil is reduced while sulfur, nitrogen impurity content, improves the combination properties such as diesel cetane-number.But using current catalyst for hydro-upgrading, the combination property to improve diesel oil（Sulfur nitrogen impurity content, Cetane number, T95 temperature, arene content etc.）, it usually needs higher cracking degree, can so make diesel yield relatively low, and the yield kept by diesel oil, the combination property of diesel oil is again less than improvement well.
Sulfur-containing compound and aromatic hydrocarbons in diesel oil distillate, generally exist with complicated structure, such as dibenzothiophenes, alkyl benzothiophenes and methyldibenzothiophene etc., wherein be hydrogenated with more difficult removing is the thiophenes such as dibenzothiophenes, alkyl benzothiophenes and methyldibenzothiophene, especially with 4,6-
Dimethyl Dibenzothiophene（4,6- BMDBT）With
2,4,6- trimethyl dibenzothiophenes（2,4,6- BMDBT）Class formation is complicated and sulfur-containing compound that have space steric effect is most difficult to removing.Depth to be reached and ultra-deep desulfurization, it is accomplished by removing these complex structures and sterically hindered big sulfur-containing compound, and the generally more difficult removing under the harsh hydrofinishing operating condition such as High Temperature High Pressure of these sulfur-containing compounds, by being hydrocracked, diesel yield can be reduced.Therefore, in the case where keeping diesel yield higher, the impurity in diesel oil how is removed, while and the combination property of diesel oil can be improved, this is the important topic for being currently needed for studying.
Catalyst for hydro-upgrading is typically with the alumina support containing molecular sieve, at present, the method being modified to carrier is a lot, auxiliary agent such as silicon, phosphorus, fluorine, boron, zirconium, titanium, magnesium, gallium, vanadium, manganese, copper, zinc etc. are introduced wherein, can be used to improve the property of carrier, but as the consumption, the species that introduce auxiliary agent are different with mode, the property of alumina support can be made different, or even difference is very big.CN1184843A discloses a kind of catalyst for hydrocracking diesel oil, and the catalyst consists of 40～80wt% of aluminium oxide, 0～20wt% of amorphous silica-alumina, 5～30wt% of Y type molecular sieve.CN101463271A discloses a kind of catalyst for hydro-upgrading of inferior diesel and preparation method thereof, mainly using predecessor and Y type molecular sieve mixing, molding and the roasting of silica-alumina, aluminium oxide and/or aluminium oxide, the hydrogenation metal of effective dose is introduced afterwards in molding species.Above-mentioned catalyst has higher desulfurization and a denitrification activity, but the amplitude that the yield of diesel product is low, diesel-fuel cetane number is improved is little, high condensation point and the shortcomings of big density.
CN201110350790.2 discloses a kind of diesel oil hydrogenation modification catalyst and preparation method thereof.The catalyst includes the carrier and hydrogenation active metals component being made up of modified beta molecular sieve and aluminium oxide.When being used for diesel oil hydrogenation modification using the catalyst, although the condensation point of diesel oil distillate can be reduced, modification diesel-fuel cetane number is improved, but diesel yield is below 97%, it is still relatively low.
The content of the invention
For problems of the prior art, the invention provides a kind of preparation method of catalyst for hydro-upgrading.The catalyst passes through support modification, carrier is enable to provide more B-acid centers, reduce strong acid center, and the distribution of acid centre and hydrogenation sites can be adjusted, make its mutually coordinated effect, the combination property of catalyst is improved, the catalyst for hydro-upgrading is adapted to the upgrading processes of various distillates, be especially suitable for the hydro-upgrading of diesel oil distillate.
The preparation method of the catalyst for hydro-upgrading that the present invention is provided, including the preparation of modified catalyst for hydro-upgrading carrier, load hydrogenation active metals component using infusion process, drying and roasting, hydrotreating catalyst is obtained, wherein the preparation method of modified catalyst for hydro-upgrading carrier, including：Water-soluble silicon oil and solubility aluminum contained compound are sequentially or simultaneously introduced into catalyst for hydro-upgrading carrier, after heat treatment, modified catalyst for hydro-upgrading carrier is obtained.
Catalyst for hydro-upgrading carrier of the present invention, it can be the catalyst for hydro-upgrading carrier of conventional method preparation, usually with aluminium oxide and molecular sieve as key component, adjuvant component can not contained, adjuvant component can also be contained, wherein adjuvant component can be one or more in fluorine, silicon, phosphorus, titanium, zirconium, boron etc., adjuvant component content in the carrier in below 15wt%, preferred below 10wt%.Catalyst for hydro-upgrading carrier of the present invention can be prepared using kneading method, mixing plastic method etc., and the general process of kneading method is as follows, by aluminium hydroxide（Such as boehmite）With obtain after high-temperature roasting after molecular sieve mixed-forming, the condition of high-temperature roasting is as follows：In 450 DEG C～1000 DEG C roasting 1.0h～20.0h, preferably 3.0 h ~ 8.0 h.The general process of mixing plastic method is that molecular sieve is introduced during alumine hydroxide colloid is prepared, and after plastic, the alumina dry glue containing molecular sieve is obtained, and Jing molding is dried and roasting, makes carrier.The shape of carrier can make spherical, bar shaped as needed（Such as Herba Trifolii Pratentis, Herba Galii Bungei or cylindrical bars）Etc. suitable shape, conventional shaping assistant, the such as acid of extrusion aid, peptization, binding agent etc. in forming process, can be added.The property of the catalyst for hydro-upgrading carrier is as follows：Specific surface area is 200 ~ 550m2/ g, preferably 280 ~ 450m2/g；Pore volume is 0.4 ~ 1.3mL/g, preferably 0.6 ~ 1.0mL/g.
Molecular sieve of the present invention is Y type molecular sieve and/or beta-molecular sieve.On the basis of the weight of catalyst for hydro-upgrading carrier, the content of molecular sieve is 3% ~ 35%, and the content of aluminium oxide is 65% ~ 97%, and preferably the content of molecular sieve is 3% ~ 20%, and the content of aluminium oxide is 80% ~ 97%.Wherein described molecular sieve is hydrogen type molecular sieve.Wherein beta-molecular sieve preferred property is as follows：SiO2/Al2O3Mol ratio is 30 ~ 150, specific surface area 400m2/ g～750m2/ g, total pore volume 0.30mL/g～0.55mL/g, meleic acid 0.1～0.8mmol/g of amount；Y type molecular sieve preferred property is as follows：SiO2/Al2O3Mol ratio is 5 ~ 50, specific surface area 450m2/ g～800m2/ g, total pore volume 0.30mL/g～0.60mL/g, meleic acid 0.2～0.9mmol/g of amount.Beta-molecular sieve of the present invention and Y type molecular sieve can be prepared using existing method.
In the inventive method, the 0.2%～6.0% of modified catalyst for hydro-upgrading vehicle weight, preferably 0.2%～4.0%, more preferably 0.2% ~ 1.5% is accounted in terms of silicon dioxide by the silicone content that water-soluble silicon oil is introduced in carrier.
In the inventive method, the 0.2%～8.0% of modified catalyst for hydro-upgrading vehicle weight, preferably 0.4%～5.0%, more preferably 0.5%～2.0% is accounted in terms of aluminium oxide by the aluminium content that solubility aluminum contained compound is introduced in carrier.
In the inventive method, mol ratio that the consumption of water-soluble silicon oil and solubility aluminum contained compound counted with silicon oxide and aluminium oxide respectively is introduced as 0.02 ~ 25.0, preferably 0.03 ~ 10.0, more preferably 0.08 ~ 3.0.
Water-soluble silicon oil described in the inventive method, refers to the silicone oil that can be dissolved in water, and preferred property is as follows：Viscosity when 25 DEG C is 200 ~ 7000mPa.s, and preferably 500 ~ 5000mPa.s, cloud point are 30 ~ 100 DEG C, preferably 40 ~ 65 DEG C.What described water-soluble silicon oil was usually obtained using the method for group modified silicone oil, such as polyether modified silicon oil.
In the inventive method, solubility aluminum contained compound refers to one or more in aluminum nitrate, aluminum chloride, aluminum sulfate etc..
In the inventive method, water-soluble silicon oil and solubility aluminum contained compound are sequentially or simultaneously incorporated on catalyst for hydro-upgrading carrier, first water-soluble silicon oil can be incorporated on catalyst for hydro-upgrading carrier, then again solubility aluminum contained compound is incorporated on catalyst for hydro-upgrading carrier；Or water-soluble silicon oil and solubility aluminum contained compound are incorporated on catalyst for hydro-upgrading carrier simultaneously, its incorporation way adopts infusion process, and infusion process can be incipient impregnation, or excessive dipping；Can be repeatedly dipping, or single-steeping.To improve efficiency, preferably using an incipient impregnation.
In the inventive method, described heat treatment adopts two sections of heat treatments, first paragraph is 60 DEG C～150 DEG C in temperature, preferably 90 DEG C～120 DEG C, process time is 0.5h～20.0h, preferably 1.0h～6.0h, second segment is 180 DEG C～400 DEG C in temperature, preferably 200 DEG C～350 DEG C, process time is 0.5h～20.0h, preferably 1.0h～6.0h.Heat treatment can be carried out in oxygen-containing atmosphere, and oxygen concentration is not particularly limited, such as air atmosphere etc., it is also possible to carried out in an inert atmosphere, such as nitrogen atmosphere etc..
In the inventive method, described hydrogenation active metals component is the active metal component that catalyst for hydro-upgrading is commonly used, one or more generally in vib metals and group VIII metal, wherein vib metals are preferably W and/or Mo, and group VIII metal is preferably Co and/or Ni.
Catalyst for hydro-upgrading prepared by the inventive method, on the basis of the weight of catalyst, the content of modified catalyst for hydro-upgrading carrier is 55.0wt% ~ 94.5wt%, preferably 58.0wt% ~ 90.0wt%, vib metals oxide content is 5.0wt% ~ 30.0wt%, preferably 8.0wt% ~ 30.0wt%, group VIII metal oxide content are 0.5wt% ~ 15.0 wt%, preferably 2.0 wt % ~ 12.0 wt
%。
In catalyst for hydro-upgrading preparation method of the present invention, hydrogenation active metals component is supported on carrier by infusion process, can is incipient impregnation, or excessive dipping, can is step impregnation, may also be co-impregnation, preferably equal-volume co-impregnation.Dipping method is well-known to those skilled in the art.After hydrogenation active metals component solution impregnated carrier, final catalyst is made in drying and roasting.Method for preparing catalyst is known to technical staff.Dipping solution is prepared by with the compound containing group VIB or group VIII metal, and its solution concentration can be adjusted by the consumption of each compound, and so as to prepare the catalyst of specified activity constituent content, the compound method of solution is known to those skilled in the art.With the aqueous impregnation said catalyst carrier containing active metal component, through dry and calcination stepses after dipping.The condition of the drying and roasting is conventional, and for example, baking temperature is 60 DEG C～200 DEG C, and preferably 90 DEG C～160 DEG C, drying time is 0.5h～20h, preferably 1h～6h；Sintering temperature is 300 DEG C～700 DEG C, and preferably 300 DEG C～500 DEG C, roasting time is 0.5h～20h, preferably 1h～6h.
Modified catalyst for hydro-upgrading carrier prepared by the inventive method，With a small amount of specific water-soluble silicon oil-impregnated catalyst for hydro-upgrading carrier，Which is made to load on the ad-hoc location of catalyst for hydro-upgrading carrier surface using the effect of the hydrophilic and hydrophobic group of water-soluble silicon oil，And make while or the aluminum contained compound of dipping is evenly spread to around silica group afterwards，By suitable heat treatment，The Si for being loaded、Al can more preferable coordinative role，The sial hydroxyl being more evenly distributed is formed in carrier surface ad-hoc location，On the one hand carrier surface is made to form more acid suitable acid centres，And be engaged with the former acidic site in carrier，Make the acidity and acid distribution of carrier more reasonable，Reduce strong acid content，More B-acid centers are provided，On the other hand，Be conducive to adjusting the distribution of the hydrogenation sites that the follow-up active metal using infusion process load is formed，And the cooperation of the acid centre of hydrogenation sites and carrier，So as to improve the performance of catalyst.
Catalyst prepared by the inventive method, the suitable catalyst for hydro-upgrading as various distillates, particularly diesel oil hydrogenation modification catalyst, during the catalyst is used for diesel oil hydrogenation modification, with deep hydrodesulfurizationof activity, and can keep improving the combination properties such as Cetane number in the case that diesel yield is higher.
Specific embodiment
In the present invention, cloud point refers to the water-soluble silicon oil solution that mass concentration is 1% is heated to after muddiness and stops heating, temperature of the lower observation aqueous solution of stirring by muddy change when limpid.
The preparation method of the modified catalyst for hydro-upgrading carrier provided according to the present invention, which can specifically adopt following steps：
1st, solubility aluminum contained compound is configured to into solution A, wherein aluminum contained compound concentration is calculated as 0.1g/100mL ~ 32g/100mL with aluminium oxide；
2nd, water-soluble silicon oil is configured to into solution B, wherein water-soluble silicon oil concentration is calculated as 0.1g/100mL ~ 20g/100mL with silicon oxide；
3rd, solubility aluminum contained compound and water-soluble silicon oil are hybridly prepared into into solution C, wherein aluminum contained compound concentration is calculated as 0.1g/100mL ~ 16g/100mL with aluminium oxide, and water-soluble silicon oil concentration is calculated as 0.1g/100mL ~ 10g/100mL with silicon oxide；
4th, water-soluble silicon oil and aluminum contained compound are guided on catalyst for hydro-upgrading carrier using a kind of at least following mode：
I, impregnate catalyst for hydro-upgrading carrier with solution C, preferably through health preserving after, then by two sections of heat treatments, obtain modified catalyst for hydro-upgrading carrier；In wherein two sections heat treatments, first paragraph is 60 DEG C～150 DEG C in temperature, preferably 90 DEG C～120 DEG C, process time is 0.5h～20.0h, preferably 1.0h～6.0h, second segment are 180 DEG C～400 DEG C, preferably 200 DEG C～350 DEG C in temperature, process time is 0.5h～20.0h, preferably 1.0h～6.0h；
II, impregnate catalyst for hydro-upgrading carrier with solution B, preferably through health preserving after, by Low Temperature Heat Treatment, then dipping solution A, preferably through health preserving after, then by two sections of heat treatments, obtain modified catalyst for hydro-upgrading carrier；Wherein Low Temperature Heat Treatment is that process time is 0.5h～20.0h, preferably 1.0h～6.0h at 60 DEG C～150 DEG C, preferably 90 DEG C～120 DEG C；In two sections of heat treatments, first paragraph is 60 DEG C～150 DEG C in temperature, preferably 90 DEG C～120 DEG C, process time is 0.5h～20.0h, preferably 1.0h～6.0h, second segment are 180 DEG C～400 DEG C, preferably 200 DEG C～350 DEG C in temperature, process time is 0.5h～20.0h, preferably 1.0h～6.0h.
In the inventive method, heat treatment can be carried out in oxygen-containing atmosphere, and oxygen concentration is not particularly limited, such as air atmosphere etc., it is also possible to carried out in an inert atmosphere, such as nitrogen atmosphere etc..
The inventive method is not specifically limited to the conditioned time after dipping solution, conditioned time is defined by can guarantee that water-soluble silicon oil and the uniform adsorption of aluminum contained compound component, those skilled in the art can be judged according to the absorption situation of the viscosity situation of solution and solution, determine conditioned time.
The technical scheme that the invention is further illustrated by the following examples, but invention should not be deemed limited in this embodiment.In the present invention, wt% is mass fraction, without specified otherwise, is air atmosphere.
In the present invention, meleic acid amount, B-acid and L acid are determined using Pyridine adsorption IR spectra method, and wherein meleic acid amount is the sum of B-acid and L acid acid amount.
In embodiment, water-soluble silicon oil A used is by the industrial organosilicon new material company production in Qingdao, SiO2Content is 15wt%, viscosity（25℃）1500 ~ 5000 mPa.s, cloud point are 47 DEG C；Water-soluble silicon oil B is produced by Laiyang is along bright Chemical Co., Ltd, SiO2Content is 9wt%, viscosity（25℃）For 500～1500mPa.s, cloud point is 45～55 DEG C；Water-soluble silicon oil C is produced by Laiyang Sheng Bang organosilicons Science and Technology Ltd.,SiO2Content is 30wt%, viscosity（25℃）For 600～5000mPa.s, cloud point is 42～46 DEG C.
In embodiment, the property of beta-molecular sieve B1 used is as follows：SiO2/Al2O3Mol ratio is 50, specific surface area 566m2/ g, total pore volume 0.45mL/g, meleic acid amount 0.42mmol/g；The property of beta-molecular sieve B2 used is as follows：SiO2/Al2O3Mol ratio is 80, specific surface area 553m2/ g, total pore volume 0.46mL/g, meleic acid amount 0.38mmol/g.The property of Y type molecular sieve Y1 used is as follows：SiO2/Al2O3Mol ratio is 15, specific surface area 633m2/ g, total pore volume 0.48mL/g, meleic acid amount 0.49mmol/g；The property of Y type molecular sieve Y2 used is as follows：SiO2/Al2O3Mol ratio is 29, specific surface area 645m2/ g, total pore volume 0.49mL/g, meleic acid amount 0.44mmol/g.
In embodiment, the diameter of cylindrical vector used is about 1.2mm, and length is about 3 ~ 5mm, and its physico-chemical property is as shown in table 1.
The preparation of Z1：By beta-molecular sieve B1, macroporous aluminium oxide (pore volume 1.0mL/g, specific surface area 400m2/ g), binding agent (mol ratio of nitric acid and little porous aluminum oxide is 0.3) be put into mixed grind in chaser, add water, be rolled into paste, extrusion, extrusion bar obtain carrier Z1 in 110 DEG C of dryings 4 hours then in 550 DEG C of roastings 4 hours.
The preparation of Z2：By beta-molecular sieve B1, Y type molecular sieve Y1, macroporous aluminium oxide (pore volume 1.0mL/g, specific surface area 400m2/ g), binding agent (mol ratio of nitric acid and little porous aluminum oxide is 0.3) be put into mixed grind in chaser, add water, be rolled into paste, extrusion, extrusion bar obtain carrier Z2 in 110 DEG C of dryings 4 hours then in 550 DEG C of roastings 4 hours.
The preparation of Z3：By beta-molecular sieve B2, Y type molecular sieve Y2, macroporous aluminium oxide (pore volume 1.0mL/g, specific surface area 400m2/ g), binding agent (mol ratio of nitric acid and little porous aluminum oxide is 0.3) be put into mixed grind in chaser, add water, be rolled into paste, extrusion, extrusion bar obtain carrier Z3 in 110 DEG C of dryings 4 hours then in 550 DEG C of roastings 4 hours.
The physico-chemical property of catalyst for hydro-upgrading carrier used in 1 embodiment of table
| Project | Z1 | Z2 | Z3 |
| Beta-molecular sieve content, wt% | _ | 4 | 6 |
| Y molecular sieve content, wt% | 10 | 6 | 6 |
| Aluminium oxide | Surplus | Surplus | Surplus |
| Specific surface area, m2/g | 355 | 346 | 369 |
| Pore volume, mL/g | 0.63 | 0.64 | 0.64 |
| Saturation liquid absorption, mL/100g | 72 | 73 | 73 |
Mo predecessors in the present embodiment in Mo, Ni, P impregnation liquid used are MoO3, Ni predecessors are basic nickel carbonate, and P predecessors are phosphoric acid.
Embodiment 1
Aluminum nitrate 41.5g is weighed, appropriate amount of deionized water dissolving is added, makes volume be 105mL, obtained solution A1.Water-soluble silicon oil A 30.9g are weighed, appropriate amount of deionized water dissolving is added, makes volume be 105mL, obtained solution B1.Under stirring, 35mL B1 solution is poured slowly in 35mL A1 solution, and adds appropriate amount of deionized water, made final volume be 72mL, be configured to C1 solution.
100g catalyst for hydro-upgrading carrier Z1 are taken, solution C 1 is uniformly sprayed on carrier Z1, after health preserving 10 hours, 100 DEG C of heat treatment 2h of Jing, 220 DEG C of heat treatment 2h obtain modified carrier S 1.
Take 100g catalyst for hydro-upgrading carrier Z1,1 deionized water of 35mL solution Bs is diluted to into 72mL, uniformly it is sprayed on carrier Z1, health preserving 10 hours, Jing after 100 DEG C of heat treatment 2h, 35mL A1 solution deionized waters are diluted to into 72mL again, uniformly it is sprayed on carrier Z1, after health preserving 3 hours, 100 DEG C of heat treatment 2h of Jing, 220 DEG C of heat treatment 2h, obtain modified carrier S 2.
Embodiment 2
Aluminum chloride 13.0g, water-soluble silicon oil B 20.8g are weighed, appropriate amount of deionized water dissolving is added, makes volume be 156mL, obtained solution C2.
100g catalyst for hydro-upgrading carrier Z1 are taken, 78mL solution Cs 2 are uniformly sprayed on carrier Z1, after health preserving 10 hours, 100 DEG C of heat treatment 2h of Jing, 220 DEG C of heat treatment 2h obtain modified carrier S 3.
100g catalyst for hydro-upgrading carrier Z1 are taken, 78mL solution Cs 2 are uniformly sprayed on carrier Z1, after health preserving 10 hours, in a nitrogen atmosphere, 100 DEG C of heat treatment 2h of Jing, 350 DEG C of heat treatment 2h obtain modified carrier S 4.
Embodiment 3
Aluminum nitrate 5.9g, water-soluble silicon oil C 1.7g are weighed, appropriate amount of deionized water dissolving is added, makes volume be 78mL, obtained solution C3.
100g catalyst for hydro-upgrading carrier Z2 are taken, solution C 3 is uniformly sprayed on carrier Z2, after health preserving 10 hours, 100 DEG C of heat treatment 2h of Jing, 250 DEG C of heat treatment 2h obtain modified carrier S 5.
Embodiment 4
Aluminum nitrate 35.5g, 11.5 g of water-soluble silicon oil C are weighed, appropriate amount of deionized water dissolving is added, makes volume be 78mL, obtained solution C4.
100g catalyst for hydro-upgrading carrier Z2 are taken, solution C 4 is uniformly sprayed on carrier Z2, after health preserving 10 hours, 100 DEG C of heat treatment 2h of Jing, 250 DEG C of heat treatment 2h obtain modified carrier S 6.
Embodiment 5
Aluminum nitrate 13.3g, water-soluble silicon oil C 1.7g are weighed, appropriate amount of deionized water dissolving is added, makes volume be 78mL, obtained solution C5.
100g catalyst for hydro-upgrading carrier Z3 are taken, solution C 5 is uniformly sprayed on catalyst for hydro-upgrading carrier Z3, after health preserving 10 hours, 100 DEG C of heat treatment 2h of Jing, 250 DEG C of heat treatment 2h obtain modified carrier S 7.
Comparative example 1
Water-soluble silicon oil A 10.3g are weighed, appropriate amount of deionized water dissolving is added, makes volume be 78mL, obtained solution B2.100g catalyst for hydro-upgrading carrier Z1 are taken, solution B 2 is uniformly sprayed on carrier Z1, after health preserving 10 hours, 100 DEG C of heat treatment 2h of Jing, 220 DEG C of heat treatment 2h obtain modified carrier DS1.
Comparative example 2
Aluminum nitrate 13.8g is weighed, appropriate amount of deionized water dissolving is added, is made volume be 78mL, is configured to A2 solution.100g catalyst for hydro-upgrading carrier Z1 are taken, solution A 2 is uniformly sprayed on carrier Z1, after health preserving 10 hours, 100 DEG C of heat treatment 2h of Jing, 220 DEG C of heat treatment 2h obtain modified carrier DS2.
Comparative example 3
Compared with the preparation method of carrier S 2 in embodiment 2, this comparative example is first to introduce aluminium salt, introduces water-soluble silicon oil afterwards, and detailed process is as follows：
Take 100g catalyst for hydro-upgrading carrier Z1,35mL A1 solution deionized waters are diluted to into 78mL, uniformly it is sprayed on carrier Z1, after health preserving 3 hours, 100 DEG C of heat treatment 2h of Jing, 1 deionized water of 35mL solution Bs is diluted to into 76mL again, uniformly it is sprayed on carrier Z1, health preserving 10 hours, Jing after 100 DEG C of heat treatment 2h, 220 DEG C of heat treatment 2h, obtain modified carrier DS3.
Table 2
Embodiment and the catalyst for hydro-upgrading support prepared by comparative example
| Bearer number | S1 | S2 | S3 | S4 | S5 | S6 | S7 |
| Introduce Al2O3Amount, wt% | 1.8 | 1.8 | 1.3 | 1.3 | 0.8 | 4.6 | 1.8 |
| Introduce SiO2Amount, wt% | 1.5 | 1.5 | 0.9 | 0.9 | 0.5 | 3.2 | 0.5 |
| Specific surface area, m2/g | 309 | 308 | 305 | 312 | 311 | 281 | 314 |
| Pore volume, mL/g | 0.61 | 0.61 | 0.62 | 0.62 | 0.63 | 0.57 | 0.63 |
| Infrared total acid, mmol/g | 0.518 | 0.498 | 0.502 | 0.525 | 0.509 | 0.487 | 0.519 |
| B-acid, mmol/g | 0.119 | 0.115 | 0.108 | 0.121 | 0.114 | 0.112 | 0.119 |
| L acid, mmol/g | 0.399 | 0.383 | 0.394 | 0.404 | 0.395 | 0.375 | 0.400 |
| Strong acid content *, % | 15.0 | 14.6 | 14.3 | 14.8 | 15.3 | 13.9 | 15.2 |
* note：In table 2, strong acid content refers to that acid amount when measuring using determination of infrared spectroscopy acid more than 450 DEG C accounts for the percent of total acid content.
Continued 2
| Bearer number | Z1 | Z2 | Z3 | DS1 | DS2 | DS3 |
| Introduce Al2O3Amount, wt% | - | - | - | - | 1.8 | 1.8 |
| Introduce SiO2Amount, wt% | - | - | - | 1.5 | - | 1.5 |
| Specific surface area, m2/g | 355 | 346 | 369 | 326 | 322 | 312 |
| Pore volume, mL/g | 0.63 | 0.64 | 0.64 | 0.62 | 0.62 | 0.61 |
| Infrared total acid, mmol/g | 0.438 | 0.449 | 0.430 | 0.469 | 0.423 | 0.455 |
| B-acid, mmol/g | 0.071 | 0.075 | 0.074 | 0.084 | 0.059 | 0.076 |
| L acid, mmol/g | 0.367 | 0.374 | 0.356 | 0.385 | 0.364 | 0.379 |
| Strong acid content *, % | 24.5 | 23.8 | 24.7 | 20.1 | 12.0 | 13.3 |
Embodiment 6 ~ 12
Take carrier strip S1, S2 in the embodiment of the present invention, S3, S4, S5, S6 and S7 respectively, with Mo, Ni, P solution difference incipient impregnation 2h after, 120 DEG C are dried 3h, 480 DEG C of roasting 2h, respectively obtain catalyst T1, T2, T3, T4, T5, T6 and T7.
Comparative example 4 ~ 8
Carrier strip DS1, DS2 and DS3 of comparative example of the present invention are taken respectively, and the carrier Z1 and Z2 used by embodiment, distinguished after incipient impregnation 2h with Mo, Ni, P solution, 120 DEG C are dried 3h, 480 DEG C of roasting 2h, respectively obtain catalyst DT1, DT2, DT3, DT4 and DT5.
The composition of 3 catalyst of table
| Catalyst is constituted | T1 | T2 | T3 | T4 | T5 | T6 | T7 |
| MoO3, wt% | 20.82 | 20.59 | 20.73 | 20.80 | 20.75 | 20.86 | 20.83 |
| NiO, wt% | 3.99 | 4.12 | 3.95 | 3.98 | 4.05 | 4.09 | 4.08 |
| P, wt% | 1.35 | 1.36 | 1.32 | 1.33 | 1.35 | 1.33 | 1.32 |
Continued 3
| Catalyst is constituted | DT1 | DT2 | DT3 | DT4 | DT5 |
| MoO3, wt% | 20.85 | 20.71 | 20.83 | 20.77 | 20.89 |
| NiO, wt% | 3.98 | 3.96 | 3.97 | 3.99 | 3.94 |
| P, wt% | 1.33 | 1.35 | 1.36 | 1.34 | 1.35 |
Embodiment 13
Henchnmrk test of the present embodiment for catalyst.
Catalyst performance evaluation experiment is carried out on 100mL small hydrogenation devices, carries out presulfurization to catalyst before performance evaluation.Evaluating catalyst condition is in reaction stagnation pressure 10.0MPa, 1.5 h of volume space velocity during liquid-1, hydrogen to oil volume ratio 800：1, reaction temperature is 365 DEG C.Henchnmrk test raw material oil nature is shown in Table 4, Evaluation results are shown in Table 5, from data in table, catalyst for hydro-upgrading is prepared with the present invention, catalyst it is desulphurizing activated apparently higher than comparative example catalyst, diesel-fuel cetane number is improved into more than 10 units under conditions of diesel yield being kept not less than 98%, and product quality has obtained good improvement.
Table
4
Raw material oil nature
| Raw oil | Catalytic diesel oil |
| Density (20 DEG C), g/cm3 | 0.9489 |
| Boiling range/DEG C | |
| IBP/ EBP | 185/372 |
| Condensation point, DEG C | 5 |
| Total sulfur, g/g | 8798 |
| 4,6-BMDBT contents, g/g | 108.9 |
| Nitrogen, g/g | 1247 |
| Cetane number | 28 |
| C, wt% | 87.75 |
| H, wt% | 11.06 |
Table
5
Catalyst performance
Evaluation result
| Catalyst is numbered | T1 | T2 | T3 | T4 | T5 | T6 | T7 |
| Diesel oil | |||||||
| Yield, wt% | 98.3 | 98.5 | 98.2 | 98.5 | 98.5 | 98.6 | 98.7 |
| Density (20 DEG C), g/cm3 | 0.8393 | 0.8392 | 0.8395 | 0.8392 | 0.8393 | 0.8391 | 0.8395 |
| T95, DEG C | 349 | 350 | 350 | 348 | 348 | 349 | 348 |
| Condensation point, DEG C | -20 | -20 | -21 | -22 | -22 | -21 | -22 |
| Cetane number | 47.8 | 47.9 | 48.0 | 48.1 | 48.0 | 47.5 | 48.2 |
| Sulfur, g/g | 8 | 7 | 8 | 7 | 7 | 7 | 7 |
Continued 5
| Catalyst is numbered | DT1 | DT2 | DT3 | DT4 | DT5 |
| Diesel oil | |||||
| Yield, wt% | 97.3 | 97.5 | 97.2 | 97.1 | 97.0 |
| Density (20 DEG C), g/cm3 | 0.8385 | 0.8408 | 0.8392 | 0.8368 | 0.8372 |
| T95, DEG C | 347 | 352 | 348 | 345 | 346 |
| Condensation point, DEG C | -20 | -18 | -19 | -22 | -23 |
| Cetane number | 45.8 | 43.2 | 44.8 | 45.0 | 45.1 |
| Sulfur, g/g | 10 | 18 | 15 | 14 | 13 |
Claims (23)
1. a kind of preparation method of catalyst for hydro-upgrading, including：The preparation of modified catalyst for hydro-upgrading carrier, loads hydrogenation active metals component, drying and roasting using infusion process, obtains catalyst for hydro-upgrading, wherein the preparation method of modified catalyst for hydro-upgrading carrier includes：Water-soluble silicon oil and solubility aluminum contained compound are sequentially or simultaneously introduced into catalyst for hydro-upgrading carrier, after heat treatment, modified catalyst for hydro-upgrading carrier is obtained.
2. in accordance with the method for claim 1, it is characterised in that：Described catalyst for hydro-upgrading carrier, be with aluminium oxide and molecular sieve as key component, with or without adjuvant component, wherein adjuvant component be fluorine, silicon, phosphorus, titanium, zirconium, one or more in boron, adjuvant component content in the carrier is in below 15wt%.
3. in accordance with the method for claim 1, it is characterised in that：The property of the catalyst for hydro-upgrading carrier is as follows：Specific surface area is 200 ~ 550m2/ g, pore volume are 0.4 ~ 1.3mL/g；It is preferably as follows：Specific surface area is 280 ~ 450m2/ g, pore volume are 0.6 ~ 1.0mL/g.
4. in accordance with the method for claim 1, it is characterised in that：Described catalyst for hydro-upgrading carrier adopts kneading method or mixing plastic method to prepare.
5. according to the method described in claim 1 or 4, it is characterised in that：Described catalyst for hydro-upgrading carrier is Jing molding and the catalyst for hydro-upgrading carrier through high-temperature roasting, and the condition of high-temperature roasting is as follows：In 450 DEG C～1000 DEG C roasting 1.0h～20.0h.
6. in accordance with the method for claim 1, it is characterised in that：On the basis of the weight of catalyst for hydro-upgrading carrier, the content of molecular sieve is 3% ~ 35%, and the content of aluminium oxide is 65% ~ 97%, and preferably the content of molecular sieve is 3% ~ 20%, and the content of aluminium oxide is 80% ~ 97%.
7. in accordance with the method for claim 1, it is characterised in that：Described molecular sieve is Y type molecular sieve and/or beta-molecular sieve.
8. in accordance with the method for claim 7, it is characterised in that：Described molecular sieve is hydrogen type molecular sieve, and wherein beta-molecular sieve property is as follows：SiO2/Al2O3Mol ratio is 30 ~ 150, specific surface area 400m2/ g～750m2/ g, total pore volume 0.30mL/g～0.55mL/g, meleic acid 0.1～0.8mmol/g of amount；Y type molecular sieve property is as follows：SiO2/Al2O3Mol ratio is 5 ~ 50, specific surface area 450m2/ g～800m2/ g, total pore volume 0.30mL/g～0.60mL/g, meleic acid 0.2～0.9mmol/g of amount.
9. in accordance with the method for claim 1, it is characterised in that：The 0.2%～6.0% of modified catalyst for hydro-upgrading vehicle weight, preferably 0.2%～4.0%, more preferably 0.2% ~ 1.5% is accounted in terms of silicon dioxide by the silicone content that water-soluble silicon oil is introduced in carrier.
10. in accordance with the method for claim 1, it is characterised in that：The 0.2%～8.0% of modified catalyst for hydro-upgrading vehicle weight, preferably 0.4%～5.0%, more preferably 0.5%～2.0% is accounted in terms of aluminium oxide by the aluminium content that solubility aluminum contained compound is introduced in carrier.
11. in accordance with the method for claim 1, it is characterised in that：Mol ratio that the consumption of water-soluble silicon oil and solubility aluminum contained compound counted with silicon oxide and aluminium oxide respectively is introduced as 0.02 ~ 25.0, preferably 0.03 ~ 10.0, more preferably 0.08 ~ 3.0.
12. in accordance with the method for claim 1, it is characterised in that：Described water-soluble silicon oil is the silicone oil that can be dissolved in water, and property is as follows：Viscosity when 25 DEG C is 200 ~ 7000mPa.s, and preferably 500 ~ 5000mPa.s, cloud point are 30 ~ 100 DEG C, preferably 40 ~ 65 DEG C.
13. according to the method described in claim 1 or 12, it is characterised in that：Described water-soluble silicon oil is polyether modified silicon oil.
14. in accordance with the method for claim 1, it is characterised in that：Described solubility aluminum contained compound is aluminum nitrate, aluminum chloride, one or more in aluminum sulfate.
15. in accordance with the method for claim 1, it is characterised in that：The heat treatment adopts two sections of heat treatments, and first paragraph is 60 DEG C～150 DEG C in temperature, and process time is 0.5h～20.0h, and second segment is 180 DEG C～400 DEG C in temperature, and process time is 0.5h～20.0h, is preferably as follows：First paragraph is 90 DEG C～120 DEG C in temperature, and process time is 1.0h～6.0h, and second segment is 200 DEG C～350 DEG C in temperature, and process time is 1.0h～6.0h.
16. in accordance with the method for claim 1, it is characterised in that：Water-soluble silicon oil and solubility aluminum contained compound are successively incorporated on carrier, its incorporation way adopts infusion process, first water-soluble silicon oil is impregnated on carrier, Jing after health preserving, by Low Temperature Heat Treatment, then again solubility aluminum contained compound is impregnated on carrier, by two sections of heat treatments, obtains modified catalyst for hydro-upgrading carrier；Wherein Low Temperature Heat Treatment is that process time is 0.5h～20.0h at 60 DEG C～150 DEG C.
17. in accordance with the method for claim 16, it is characterised in that：In the dipping solution that solubility aluminum contained compound is made into, aluminum contained compound concentration is calculated as 0.1g/100mL ~ 32g/100mL with aluminium oxide；In the dipping solution that water-soluble silicon oil is made into, water-soluble silicon oil concentration is calculated as 0.1g/100mL ~ 20g/100mL with silicon oxide.
18. in accordance with the method for claim 1, it is characterised in that：Water-soluble silicon oil and solubility aluminum contained compound are incorporated on carrier simultaneously, its incorporation way adopts infusion process, will water-soluble silicon oil and solubility aluminum contained compound be impregnated on carrier simultaneously, Jing after health preserving, by two sections of heat treatments, modified catalyst for hydro-upgrading carrier is obtained.
19. in accordance with the method for claim 18, it is characterised in that：By in the dipping solution of solubility aluminum contained compound and water-soluble silicon oil mixed preparing, aluminum contained compound concentration is calculated as 0.1g/100mL ~ 16g/100mL with aluminium oxide, and water-soluble silicon oil concentration is calculated as 0.1g/100mL ~ 10g/100mL with silicon oxide.
20. according to the arbitrary described method of claim 16 ~ 19, it is characterised in that：Infusion process adopts an incipient impregnation.
21. according to the arbitrary described method of claim 16 ~ 19, it is characterised in that：Two sections of described heat treatments, first paragraph are 60 DEG C～150 DEG C in temperature, and process time is 0.5h～20.0h, and second segment is 180 DEG C～400 DEG C in temperature, and process time is 0.5h～20.0h, is preferably as follows：First paragraph is 90 DEG C～120 DEG C in temperature, and process time is 1.0h～6.0h, and second segment is 200 DEG C～350 DEG C in temperature, and process time is 1.0h～6.0h.
22. in accordance with the method for claim 1, it is characterised in that：Described hydrogenation active metals component is one or more in vib metals and group VIII metal, and wherein vib metals are W and/or Mo, and group VIII metal is Co and/or Ni.
23. in accordance with the method for claim 22, it is characterised in that：On the basis of the weight of catalyst, the content of modified catalyst for hydro-upgrading carrier is 55.0wt% ~ 94.5wt%, preferably 58.0wt% ~ 90.0wt%, vib metals oxide content is 5.0wt% ~ 30.0wt%, preferably 8.0wt% ~ 30.0wt%, group VIII metal oxide content is 0.5wt% ~ 15.0 wt%, preferably 2.0 wt% ~ 12.0 wt%.
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| CN111318312A (en) * | 2018-12-13 | 2020-06-23 | 中国石油化工股份有限公司 | Hydrogenation modified catalyst carrier, preparation method and application thereof |
| CN114453016A (en) * | 2020-10-21 | 2022-05-10 | 中国石油化工股份有限公司 | Preparation method of hydrotreating catalyst, hydrotreating catalyst and application |
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