CN107442129A - A kind of hydrotreating catalyst and its preparation method and application - Google Patents
A kind of hydrotreating catalyst and its preparation method and application Download PDFInfo
- Publication number
- CN107442129A CN107442129A CN201610365746.1A CN201610365746A CN107442129A CN 107442129 A CN107442129 A CN 107442129A CN 201610365746 A CN201610365746 A CN 201610365746A CN 107442129 A CN107442129 A CN 107442129A
- Authority
- CN
- China
- Prior art keywords
- soluble
- alumina
- catalyst
- carrier
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 52
- 239000003921 oil Substances 0.000 claims abstract description 37
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 35
- 239000010703 silicon Substances 0.000 claims abstract description 35
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 27
- 239000006259 organic additive Substances 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000011282 treatment Methods 0.000 claims abstract description 4
- 238000013021 overheating Methods 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 238000007598 dipping method Methods 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 16
- 150000002894 organic compounds Chemical class 0.000 claims description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- WQABCVAJNWAXTE-UHFFFAOYSA-N dimercaprol Chemical compound OCC(S)CS WQABCVAJNWAXTE-UHFFFAOYSA-N 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 10
- 239000002671 adjuvant Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000012545 processing Methods 0.000 claims description 10
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 9
- 229910052796 boron Inorganic materials 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 239000011593 sulfur Chemical group 0.000 claims description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 229960001484 edetic acid Drugs 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 239000011777 magnesium Substances 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 229920002545 silicone oil Polymers 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229960001051 dimercaprol Drugs 0.000 claims description 6
- 238000001802 infusion Methods 0.000 claims description 6
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 5
- -1 propyl group thioether Chemical class 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- XDVOLDOITVSJGL-UHFFFAOYSA-N 3,7-dihydroxy-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound O1B(O)OB2OB(O)OB1O2 XDVOLDOITVSJGL-UHFFFAOYSA-N 0.000 claims description 4
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 239000005416 organic matter Substances 0.000 claims description 4
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 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 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 2
- OTRAYOBSWCVTIN-UHFFFAOYSA-N OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N Chemical compound OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N OTRAYOBSWCVTIN-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 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
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 229940043237 diethanolamine Drugs 0.000 claims description 2
- VLXBWPOEOIIREY-UHFFFAOYSA-N dimethyl diselenide Natural products C[Se][Se]C VLXBWPOEOIIREY-UHFFFAOYSA-N 0.000 claims description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 claims description 2
- 238000010348 incorporation Methods 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims 2
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- ZGBSOTLWHZQNLH-UHFFFAOYSA-N [Mg].S(O)(O)(=O)=O Chemical compound [Mg].S(O)(O)(=O)=O ZGBSOTLWHZQNLH-UHFFFAOYSA-N 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
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- 238000005984 hydrogenation reaction Methods 0.000 abstract description 18
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- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 79
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- 238000002803 maceration Methods 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
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- 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
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- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
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- 238000004073 vulcanization Methods 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J35/615—
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- B01J35/635—
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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- 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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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
Abstract
The present invention discloses a kind of hydrotreating catalyst and its preparation method and application, including：（1）The preparation of modified oxidized alumina-based support, the one or more in water-soluble silicon oil and soluble auxiliary agent are sequentially or simultaneously introduced into alumina-based supports, after Overheating Treatment, modified oxidized alumina-based support is made.（2）Step（1）Obtained modified oxidized alumina-based support impregnates VI B races and VIII race's active metal component, while introduces organic additive, and final hydrotreating catalyst is obtained without roasting process after drying.This method can adjust the distribution of acid centre and hydrogenation sites, make its mutually coordinated effect, improve the combination property of hydrotreating catalyst.
Description
Technical field
The present invention relates to a kind of hydrotreating catalyst and its preparation method and application, particularly one kind to be suitable to heavy end
Oil hydrogenating treatment catalyst and its preparation method and application.
Background technology
Loaded catalyst is most to be prepared using infusion process, such as various hydrogenation catalysts.Aluminum oxide is urged frequently as such
The carrier material of agent.But pure Al2O3The interaction force of active metal and carrier on surface is larger, is easily formed inactive
Species（Such as form nickel aluminate）, it is not easy complete cure and forms the II type activity phase with high hydrogenation activity.Meanwhile catalyst
The activity of surface acidity confrontation hydrogenation catalyst has considerable influence, removes the hetero atom in raw material, it is necessary to which catalyst has hydrogenolysis
Activity, this is occurred on the acid centre of catalyst, therefore, how to be weakened the strong interaction of metal and carrier, how to be made
Catalyst has suitable acidity, turns into the key of high-activity hydrogenation catalyst preparation.A lot of properties of catalyst are by carrier
Determine, thus it is one of key factor for developing catalyst to develop suitable carrier.
At present, the method being modified to alumina support is a lot, wherein introduce auxiliary agent such as silicon, phosphorus, fluorine, boron, zirconium,
Titanium, magnesium, gallium, vanadium, manganese, copper, zinc etc., it can be used for improving the property of alumina support, but due to introducing dosage, the species of auxiliary agent
It is different with mode, the property of alumina support can be made different, or even difference is very big.
CN00110018.1 discloses a kind of hydrogenation catalyst and preparation method thereof, and the catalyst is with group VIB and VIII race
Metal is hydrogenation active component, and auxiliary agent is fluorine, while supports one kind in boron, silicon, phosphorus, magnesium, titanium, zirconium, gallium or it is mixed into and helped
Agent, its key problem in technology are prepared using coprecipitation.
CN200910236166.2 discloses a kind of preparation method of catalyst for hydrorefining pertroleum wax.This method includes：
Boehmite is weighed, adds 6%~17% silicon-containing compound and 2%~20% organic phosphorus compound solution, is being squeezed
Extruded moulding on bar machine, through drying and being calcined, the siliceous and γ-Al of phosphorus are made2O3Carrier；Silicon-containing compound is SiO2Weight is dense
The Ludox or nano silicon of degree 30%.
It is that the not calcined catalyst active component for introducing organic additive has higher point known in the art
Property is dissipated, and the interaction of the not active metal and carrier of calcined catalyst is relatively weak, therefore hydrogenation can be effectively improved
Handle reactivity.
For example, Japanese patent application 04-166231 discloses a kind of method for preparing hydrogenation catalyst, wherein carrier is used
A kind of dipping solution dipping, dipping solution include VI B races metal component, VIII race's metal component and optional phosphorus component.Carrier exists
Dry at less than 200 DEG C, contacted with polyalcohol, then dried again at less than 200 DEG C.
Japanese patent application 06-339635 discloses a kind of method, and wherein carrier is impregnated with dipping solution, dipping solution
Including organic acid, VI B races and VIII race's hydrogenation metal component and preferable phosphorus component.Carrier after dipping is done at less than 200 DEG C
It is dry.Dried impregnated carrier is contacted with organic acid or polyalcohol, and then the carrier so after processing is done at less than 200 DEG C
It is dry.
European patent application 0601722 describes a kind of method for preparing catalyst, and this method is with comprising VI B races metal group
Point, the dipping solution dipping gamma-aluminium oxide carrier of VIII race's metal component, phosphoric acid, water and diethylene glycol.The carrier of dipping exists again
Dried at 100 DEG C.Catalyst and with Kuwait's direct steaming gasoline presulfurization containing 1.15% sulphur and 3% butyl mercaptan.
It is above-mentioned not investigate the synergy of the auxiliary agent such as organic additive and Si in the prior art, and with coprecipitation or
Si auxiliary agents are added in shaping, the former can cause the auxiliary agents such as active metal and Si to enter body phase in coprecipitation process, and more
Kind material precipitates simultaneously, and identical deposition condition can not possibly be the optimal deposition condition of many kinds of substance simultaneously；And the latter is in kneading
The auxiliary agent such as Si is added during shaping, is unfavorable for that auxiliary agent is dispersed, not only the utilization rate of auxiliary agent reduces, and to the acidity of catalyst
And the equal comprehensive adjustment effect of activity is weaker, is unfavorable for the raising of catalyst combination property.
The content of the invention
For the deficiencies in the prior art, the present invention provides a kind of hydrotreating catalyst and preparation method thereof.Should
Method can adjust the distribution of acid centre and hydrogenation sites, make its mutually coordinated effect, improve hydrotreating catalyst
Combination property.
The preparation method of hydrotreating catalyst provided by the invention, including：
（1）The preparation of modified oxidized alumina-based support, by water-soluble silicon oil and soluble auxiliary agent it is one or more of successively or together
When introduce alumina-based supports, after Overheating Treatment, be made modified oxidized alumina-based support.
（2）Step（1）Obtained modified oxidized alumina-based support impregnates VI B races and VIII race's active metal component, introduces simultaneously
Organic additive, final hydrotreating catalyst is obtained without roasting process after drying.
In the inventive method, the silicone content being introduced into by water-soluble silicon oil in carrier accounts for modified oxidized aluminium base in terms of silica
The 0.1%~5.0% of vehicle weight, preferably 0.2%~3.0%, more preferably 0.2% ~ 1.5%.
In the inventive method, the content being introduced into by soluble auxiliary agent in carrier accounts for modified oxidized alumina-based support in terms of oxide
The 0.1%~10.0% of weight, preferably 0.3%~5.0%, more preferably 0.5%~2.0%.
In the inventive method, the dosage of water-soluble silicon oil and soluble auxiliary agent is introduced respectively in terms of silica and oxide
Mol ratio is 0.05 ~ 80.0, preferably 0.1 ~ 15.0, more preferably 0.3 ~ 5.0.
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：It is viscous at 25 DEG C
It is 30 ~ 100 DEG C, preferably 40 ~ 65 DEG C to spend for 200 ~ 7000mPa.s, preferably 500 ~ 5000mPa.s, cloud point.Described is water-soluble
Property silicone oil be usually to be obtained using the method for group modified silicone oil, such as polyether modified silicon oil.
Alumina-based supports of the present invention refer to using aluminum oxide as key component, can be free of adjuvant component, also may be used
So that containing adjuvant component, wherein adjuvant component can be the one or more in fluorine, silicon, phosphorus, titanium, zirconium, boron etc., and adjuvant component is in oxygen
Change the content in alumina-based support in below 30wt%, preferably below 20wt%, more preferably below 15wt%.Institute in the present invention
Alumina-based supports are aluminium hydroxide（Such as boehmite）Obtained after high-temperature roasting, the condition of high-temperature roasting
It is as follows：1.0h~20.0h, the h of preferably 3.0 h ~ 8.0 are calcined at 450 DEG C~1000 DEG C.Described alumina-based supports can be with
Prepared using conventional method, according to the needs of practical application, shaping carrier can be made, i.e., again through height after aluminium hydroxide is molded
Temperature roasting obtains alumina-based supports.Spherical, bar shaped can be made as needed for the shape of carrier（Such as clover, bunge bedstraw herb
Or cylindrical bars）Etc. suitable shape, conventional shaping assistant, such as extrusion aid, peptization acid, adhesive can be added in forming process
Deng.The property of the alumina-based supports is as follows：Specific surface area is 120 ~ 420m2/ g, preferably 220 ~ 320m2/g；Pore volume is
0.4 ~ 1.3mL/g, preferably 0.6 ~ 1.0mL/g；Pore volume shared by hole of the bore dia less than 4nm accounts for less than the 20% of total pore volume, excellent
Choosing accounts for less than 10%, more preferably less than 5%.
In the inventive method, soluble auxiliary agent refers to containing one or more of combinations in the compounds such as aluminium, zirconium, boron, magnesium.
Soluble aluminum contained compound refers to one or more of combinations in aluminum nitrate, aluminium chloride, aluminum sulfate etc..Soluble chemical combination containing zirconium
Thing refers to one or more of combinations in zirconium nitrate, zirconium chloride, zirconium oxychloride etc..Soluble boron-containing compound refers to boron
One or more of combinations in acid, ammonium pentaborate, tetraboric acid ammonium etc..Soluble magnesium-containing compound is magnesium acetate, magnesium chloride, nitre
One or more of combinations of the compounds such as sour magnesium, magnesium sulfate.
In the inventive method, water-soluble silicon oil and soluble auxiliary agent are sequentially or simultaneously incorporated on carrier, you can first by water
Dissolubility silicone oil is incorporated on carrier, and then soluble auxiliary agent is incorporated on carrier again；Or by water-soluble silicon oil and solubility
Auxiliary agent is incorporated on carrier simultaneously, and its incorporation way uses infusion process, and infusion process can be incipient impregnation or excess
Dipping；Can be multiple dipping or single-steeping.To improve efficiency, preferably using once isometric co-impregnation.
In the inventive method, using two sections of heat treatments, first paragraph is 60 DEG C~150 DEG C in temperature, excellent for described heat treatment
Elect 90 DEG C~120 DEG C as, processing time is 0.5h~20.0h, preferably 1.0h~6.0h, second segment temperature be 180 DEG C~
400 DEG C, preferably 200 DEG C~350 DEG C, processing time is 0.5h~20.0h, preferably 1.0h~6.0h.Heat treatment can be
Carried out in oxygen-containing atmosphere, oxygen concentration is not particularly limited, such as air atmosphere, can also carried out in an inert atmosphere, than
Such as nitrogen atmosphere.
Step（2）In need to introduce organic additive, organic additive is 0.01 with group VIB atomic molar ratio：1~5：1
（In terms of final catalyst content）.Organic additive is the one or more in organic compounds containing nitrogen, organic compounds containing sulfur.
Organic additive need to introduce simultaneously with group VIB and metal component of group VIII.The species of organic additive is people in the art
Known to member.
The organic compounds containing nitrogen is the organic matter including at least a covalent bond nitrogen-atoms, in organic compounds containing nitrogen
Carbon number is 1 ~ 20, specific such as ethylenediamine, triethylamine, hexamethylene diamine, preferably except the nitrogen comprising at least one covalent bond is former
It is sub outer, also including at least a hydroxyl or the organic compound of carboxy moiety, such as：Monoethanolamine, diethanol amine, triethanolamine, second
Ethylenediamine tetraacetic acid (EDTA)（EDTA）, nitrilotriacetic acid（NTA）With ring ethylenediamine tetra-acetic acid etc..
The organic compounds containing sulfur is the organic matter including at least a covalent bond sulphur atom, in organic compounds containing sulfur
Carbon number is generally 1 ~ 20.Such as mercaptan（General formula R-SH）, thioether（General formula R-S-R）, disulphide（General formula R-S-S-
R）, the R in these sulfur-containing compounds is the alkyl containing 1 ~ 10 carbon atom, such as ethyl mercaptan, second propyl group thioether, DMDS
Deng.The group substitution of one or more carboxyls, carbonyl, ester, ether, hydroxyl, sulfydryl, such as mercapto can be contained in organic compounds containing sulfur
Guanidine-acetic acid, mercaptopropionic acid, dimercaprol dimercaptopropanol etc..In addition to above-mentioned sulfur-containing compound, sulfone and sulfoxide compound can be included, such as two
Methyl sulfoxide, dimethyl sulfone etc..
The organic matter mentioned in this patent be above-claimed cpd and with other kinds of type organics of said structure one kind or
It is several.
Hydrogenation active metal component described in the inventive method is the active metal component that hydrotreating catalyst is commonly used,
One or more generally in vib metals and group VIII metal, wherein vib metals are preferably W and/or Mo,
Group VIII metal is preferably Co and/or Ni.
Hydrotreating catalyst prepared by the inventive method, on the basis of the weight of catalyst, modified oxidized alumina-based support
Content be 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
The wt % of wt%, preferably 2.0 wt % ~ 12.0.
In hydrotreating catalyst preparation method of the present invention, hydrogenation active metal component is to support carrier by infusion process
On, it can be incipient impregnation or excessive dipping, can be step impregnation or co-impregnation, be preferably isometric
Co-impregnation.Dipping method is well-known to those skilled in the art.After hydrogenation active metal component solution impregnating carrier, through dry
It is dry that final catalyst is made.Method for preparing catalyst is known to technical staff.Dipping solution is by using containing group VIB or
Prepared by the compound of VIII race's metal, its solution concentration can be adjusted by the dosage of each compound, so as to prepare specified activity
The catalyst of constituent content, the compound method of solution are known to those skilled in the art.The drying condition be it is conventional,
For example, drying temperature is 60 DEG C~200 DEG C, preferably 90 DEG C~160 DEG C, drying time is 0.5h~20h, preferably 1h~
6h。
Above-mentioned catalyst is used for hydrotreating reaction, it is characterised in that：Reaction condition is such asUnder：Reaction stagnation pressure 3.0MPa ~
18.0MPa, volume space velocity 0.2h during liquid-1~4.0h-1, hydrogen to oil volume ratio 200:1~2000:1, reaction temperature is 230 DEG C ~ 430
℃。
Modified oxidized alumina-based support used by the inventive method, with a small amount of specific water-soluble silicon oil oxide impregnation aluminium
Base carrier, the effect using the hydrophilic and hydrophobic grouping of water-soluble silicon oil make it load to the certain bits on alumina-based supports surface
Put, and make while or the adjuvant component that impregnates afterwards evenly spread to around silica group, by suitable heat treatment, bear
The Si of load and the more preferable coordinative role of adjuvant component energy, form the silicon hydroxyl being more evenly distributed in carrier surface ad-hoc location
Base, carrier surface is formed more acid suitable acid centres, and be engaged with the former acidic site of carrier surface,
Make acidity and the acid distribution of carrier more reasonable, on the other hand, by introducing organic additive, it is follow-up negative to be more beneficial for regulation
The distribution for the hydrogenation sites that the active metal of load is formed, makes the coordination of the acid centre of hydrogenation sites and carrier surface
Coordinate, so as to improve the performance of catalyst.
The hydrogenation removing impurities matter of hydrotreating catalyst prepared by the inventive method especially suitable for heavy distillate（As sulphur,
Nitrogen etc.）Catalyst, especially hydrodenitrogenationactivity activity increase rate are larger.
Embodiment
In the present invention, cloud point refers to stop after the water-soluble silicon oil solution that mass concentration is 1% is heated into muddiness
Heating, stir temperature when the lower observation aqueous solution becomes limpid by muddiness.
According to the preparation method of modified oxidized alumina-based support provided by the invention, it can specifically use following steps：
1st, soluble auxiliary agent is configured to solution A, wherein being calculated as 0.1g/100mL ~ 32g/100mL containing assistant concentration with oxide；
2nd, water-soluble silicon oil is configured to solution B, wherein water-soluble silicon oil concentration is calculated as 0.1g/100mL ~ 20g/ with silica
100mL；
3rd, soluble auxiliary agent and water-soluble silicon oil are hybridly prepared into solution C, wherein assistant concentration is calculated as 0.1g/ with oxide
100mL ~ 16g/100mL, water-soluble silicon oil concentration are calculated as 0.1g/100mL ~ 10g/100mL with silica；
4th, water-soluble silicon oil and auxiliary agent are guided in alumina-based supports using a kind of at least following mode：
I, with solution C oxide impregnation alumina-based support, after health, by two sections of heat treatments, modified oxidized alumina-based support is obtained；
Wherein two sections heat treatment in, first paragraph temperature be 60 DEG C~150 DEG C, preferably 90 DEG C~120 DEG C, processing time be 0.5h~
20.0h, preferably 1.0h~6.0h, second segment temperature be 180 DEG C~400 DEG C, preferably 200 DEG C~350 DEG C, processing time
For 0.5h~20.0h, preferably 1.0h~6.0h；
II, with solution B oxide impregnation alumina-based support, after health, by Low Temperature Heat Treatment, then dipping solution A, after health, lead to
Two sections of heat treatments are crossed, obtain modified oxidized alumina-based support；Wherein Low Temperature Heat Treatment be at 60 DEG C~150 DEG C, preferably 90 DEG C~
120 DEG C, processing time is 0.5h~20.0h, preferably 1.0h~6.0h；In two sections of heat treatments, first paragraph is 60 DEG C in temperature
~150 DEG C, preferably 90 DEG C~120 DEG C, processing time is 0.5h~20.0h, preferably 1.0h~6.0h, and second segment is in temperature
For 180 DEG C~400 DEG C, preferably 200 DEG C~350 DEG C, processing time is 0.5h~20.0h, preferably 1.0h~6.0h.
The inventive method is not specifically limited to the conditioned time after dipping solution, and conditioned time is to can guarantee that water-soluble silicon
The uniform adsorption of oily and contained adjuvant component is defined, and those skilled in the art can be according to the viscosity situation of solution and the absorption of solution
Situation is judged, to determine conditioned time.
The technical scheme that the invention is further illustrated by the following examples, but invention should not be deemed limited to this reality
Apply in example.In the present invention, wt% is mass fraction, no specified otherwise, is air atmosphere.
In embodiment, water-soluble silicon oil A used is produced by the industrial organosilicon new material company in Qingdao, SiO2Content is
15wt%, viscosity（25℃）1500 ~ 5000 mPa.s, cloud point are 47 DEG C；Water-soluble silicon oil B is by Laiyang Shunming Chemical Co., Ltd
Production, SiO2Content is 9wt%, viscosity（25℃）For 500~1500mPa.s, cloud point is 45~55 DEG C；Water-soluble silicon oil C is by Lay
Yang Shengbang organosilicons Science and Technology Ltd. produces, SiO2Content is 30wt%, viscosity（25℃）For 600~5000mPa.s, cloud point
For 42~46 DEG C.
The pore structure of aluminum hydroxide solid elastomer powder used is as shown in table 1 in embodiment and comparative example：
The pore structure of aluminum hydroxide solid elastomer powder used in the embodiment of table 1 and comparative example
Embodiment 1
Macropore aluminum hydroxide solid elastomer powder 3800g, SB powder 200g is taken, adds citric acid and each 160g of sesbania powder, is well mixed.Then
Diluted nitric acid aqueous solution 2900g is uniformly added into, wherein concentration of nitric acid is 3.0wt%.By material kneading 15min, then roll
20min, with diameter 1.7mm clover orifice plate extrusion.500 DEG C of roasting 4h after 120 DEG C of dry 4h.Carrier after roasting is designated as
Z。
Alumina support Z physico-chemical property is as shown in table 2：
The alumina support Z of table 2 physico-chemical property
Embodiment 2
Aluminum nitrate 33.2g is weighed, adds appropriate amount of deionized water dissolving, it is 105mL, obtained solution A1 to make volume.Weigh water solubility
Silicone oil A 19.1g, appropriate amount of deionized water dissolving is added, it is 105mL, obtained solution B1 to make volume.Under stirring, by 35mL
B1 solution is poured slowly into 35mL A1 solution, and adds appropriate amount of deionized water, and it is 77mL to make final volume, is configured to C1 solution.
Take 100g alumina support Z, by solution C 1 uniformly sprinkling on the alumina support, after health 10 hours, through 100 DEG C
2h is heat-treated, 220 DEG C of heat treatment 2h, obtains modified carrier S 1.
100g alumina support Z are taken, 35mL solution Bs 1 are diluted to 77mL with deionized water, are uniformly sprayed on carrier Z,
Health 10 hours, 75mL is diluted to deionized water after 100 DEG C are heat-treated 2h, then by 35mL A1 solution, is uniformly sprayed at this
On carrier, after health 3 hours, through 100 DEG C of heat treatment 2h, 220 DEG C of heat treatment 2h, modified carrier S 2 is obtained.
Distinguish incipient impregnation S1, S2 with the maceration extract containing Mo, Ni, P and dimercaprol dimercaptopropanol, dimercaprol dimercaptopropanol is with finally urging
The mol ratio of agent Mo contents is 0.10：After 1,120 DEG C of dry 4h, the catalyst of acquisition is designated as CAT1 and CAT2 respectively.
Embodiment 3
Weigh boric acid 1.5g, water-soluble silicon oil B 16.6g, add appropriate amount of deionized water dissolving, make volume be 77mL, obtained solution
C2。
Take 100g alumina support Z, by solution C 2 uniformly sprinkling on the alumina support, after health 10 hours, through 100 DEG C
2h is heat-treated, 220 DEG C of heat treatment 2h, obtains modified carrier S 3.
Tetraboric acid ammonium 1.6g, boric acid 1.5g, water-soluble silicon oil B 16.6g are weighed, appropriate amount of deionized water dissolving is added, makes body
Product is 77mL, obtained solution C3.
Take 100g alumina support Z, by solution C 3 uniformly sprinkling on the alumina support, after health 10 hours, in nitrogen
Under atmosphere, through 100 DEG C of heat treatment 2h, 350 DEG C of heat treatment 2h, modified carrier S 4 is obtained.
Distinguish incipient impregnation S3 and S4 with the maceration extract containing Mo, Ni, P and nitrilotriacetic acid, nitrilotriacetic acid with it is final
The mol ratio of catalyst Mo contents is 0.2：1, through 120 DEG C of dry 4h, the catalyst of acquisition is designated as CAT3 and CAT4 respectively.
Embodiment 4
Zirconium nitrate 3.7g, water-soluble silicon oil C 2.1g are weighed, adds appropriate amount of deionized water dissolving, it is 77mL to make volume, is made molten
Liquid C4；Solution C 4 is uniformly sprayed on 100g alumina supports Z, after health 10 hours, through 100 DEG C of heat treatment 2h, 240 DEG C
3h is heat-treated, obtains modified carrier S 5.
With the maceration extract incipient impregnation S5 containing Mo, Ni, P and ethylenediamine tetra-acetic acid, ethylenediamine tetra-acetic acid is with finally urging
The mol ratio of agent Mo contents is 0.10：After 1,130 DEG C of vacuum drying 4h, the catalyst of acquisition is designated as CAT5.
Embodiment 5
Zirconium nitrate 13.5g, the g of water-soluble silicon oil C 9.2 are weighed, adds appropriate amount of deionized water dissolving, it is 77mL to make volume, is made
Solution C 5.Solution C 5 is uniformly sprayed on 100g alumina supports Z, after health 10 hours, through 100 DEG C of heat treatment 2h, 250 DEG C
2h is heat-treated, obtains modified carrier S 6.
With the maceration extract incipient impregnation S6 containing Mo, Ni, P, monoethanolamine and mercaptopropionic acid, monoethanolamine and mercaptopropionic acid mole
Than for 1：1, the mol ratio of total dosage and final catalyst Mo contents is 0.5：1,120 DEG C of dry 4h, the catalyst of acquisition are designated as
CAT6。
Comparative example 1
Macropore aluminum hydroxide solid elastomer powder 190g, SB powder 10g is taken, adds citric acid and each 8g of sesbania powder, is well mixed.Weigh water-soluble
Property silicone oil A 14.0g, tetraboric acid ammonium 2.1g, boric acid 2.2g, then add aqueous solution of nitric acid in, after stirring, obtain 155g
Acid solution, wherein concentration of nitric acid are 2.7wt%.By above-mentioned material kneading 15min, 20min is then rolled, with the three of diameter 1.7mm
Leaf grass orifice plate extrusion.500 DEG C of roasting 4h after 120 DEG C of dry 4h.Carrier after roasting is designated as DS1.
By the carrier S 3 in embodiment 3 change carrier DS1 into made of catalyst be designated as DCAT1.
Comparative example 2
After maceration extract incipient impregnation S1,120 DEG C of dry 4h containing Mo, Ni, P, the catalyst of acquisition is designated as DCAT2.
Comparative example 3
By the aqueous solution incipient impregnation carrier S 1 containing dimercaprol dimercaptopropanol, after 100 DEG C are heat-treated 2h, then incipient impregnation
Mo, Ni, P solution（The mol ratio of dimercaprol dimercaptopropanol and final catalyst Mo contents is 0.10：1）, after 120 DEG C of dry 4h, obtain
Catalyst be designated as DCAT3.
Comparative example 4
After maceration extract incipient impregnation S2,120 DEG C of dry 4h containing Mo, Ni, P, then incipient impregnation contains nitrilotriacetic acid
Solution（The mol ratio of nitrilotriacetic acid and final catalyst Mo contents is 0.20：1）, through 120 DEG C of dry 4h, the catalysis of acquisition
Agent is designated as DCAT4.
Comparative example 5
With the maceration extract incipient impregnation Z containing Mo, Ni, P and ethylenediamine tetra-acetic acid, ethylenediamine tetra-acetic acid and final catalyst Mo
The mol ratio of content is 0.10：After 1,130 DEG C of vacuum drying 4h, the catalyst of acquisition is designated as DCAT5.
The composition and property of the catalyst of table 3
| Composition | CAT1 | CAT2 | CAT3 | CAT4 | CAT5 | CAT6 |
| MoO3, wt% | 23.1 | 23.0 | 23.3 | 23.5 | 23.2 | 23.3 |
| NiO, wt% | 2.99 | 3.09 | 3.02 | 3.10 | 3.13 | 3.05 |
| P, wt% | 1.21 | 1.19 | 1.22 | 1.23 | 1.25 | 1.23 |
| Introduce SiO2Amount, wt% | 0.9 | 0.9 | 1.4 | 1.4 | 0.6 | 2.5 |
| Introduce amount of auxiliary, wt% | Al2O3, 1.4% | Al2O3, 1.4% | B2O3, 0.8% | B2O3, 1.6% | ZrO2, 1.0% | ZrO2, 3.5% |
| Catalyst property | ||||||
| Infrared total acid, mmol/g | 0.402 | 0.399 | 0.406 | 0.409 | 0.405 | 0.393 |
Continued 3
| Catalyst forms | DCAT1 | DCAT2 | DCAT3 | DCAT4 | DCAT5 |
| MoO3, wt% | 23.3 | 23.1 | 23.1 | 23.0 | 23.3 |
| NiO, wt% | 3.08 | 3.03 | 3.08 | 3.10 | 3.12 |
| P, wt% | 1.23 | 1.25 | 1.26 | 1.26 | 1.21 |
| Introduce SiO2Amount, wt% | 1.4 | 0.9 | 0.9 | 0.9 | - |
| Introduce amount of auxiliary, wt% | B2O3, 1.6% | Al2O3, 1.4% | Al2O3, 1.4% | Al2O3, 1.4% | - |
| Catalyst property | |||||
| Infrared total acid, mmol/g | 0.345 | 0.383 | 0.387 | 0.380 | 0.322 |
Embodiment 6
The present embodiment is catalyst CAT1 ~ CAT6 and comparative catalyst DCAT1 ~ DCAT5 active appraisal experiment.
Catalyst activity evaluation experimental is carried out on 100mL small hydrogenation devices, catalyst is carried out before activity rating pre-
Vulcanization.Evaluating catalyst condition is the h of volume space velocity 1.0 in reaction stagnation pressure 12.0MPa, liquid-1, hydrogen to oil volume ratio 800：1, instead
It is 375 DEG C to answer temperature.Active appraisal experiment is shown in Table 4 with raw material oil nature, and Activity evaluation is shown in Table 5.
The raw material oil nature of table 4
| Feedstock oil | |
| Density (20 DEG C), g/cm3 | 0.9108 |
| Sulfur content, wt% | 1.81 |
| Nitrogen content, μ g/g | 1220 |
| Boiling range, DEG C | |
| IBP/ EBP | 295/529 |
The catalyst activity evaluation result of table 5
| Catalyst | CAT1 | CAT2 | CAT3 | CAT4 | CAT5 | CAT6 |
| With respect to denitrification activity, % | 133 | 135 | 138 | 139 | 131 | 132 |
| It is relatively desulphurizing activated, % | 129 | 128 | 130 | 132 | 127 | 126 |
Continued 5
| Catalyst | DCAT1 | DCAT2 | DCAT3 | DCAT4 | DCAT5 |
| With respect to denitrification activity, % | 100 | 112 | 117 | 115 | 112 |
| It is relatively desulphurizing activated, % | 100 | 109 | 115 | 116 | 111 |
From table 5, compared with comparative example catalyst, with hydrotreating catalyst of the present invention, hydrodesulfurization and denitrification activity are equal
Improve a lot, especially the activity of hydrodenitrogeneration.
Claims (20)
- A kind of 1. preparation method of hydrotreating catalyst, it is characterised in that：Including：（1）The preparation of modified oxidized alumina-based support, by water-soluble silicon oil and soluble auxiliary agent it is one or more of successively or together When introduce alumina-based supports, after Overheating Treatment, be made modified oxidized alumina-based support；（2）Step（1）Obtained modified oxidized alumina-based support impregnates VI B races and VIII race's active metal component, while introduces organic Additive, final hydrotreating catalyst is obtained without roasting process after drying.
- 2. according to the method for claim 1, it is characterised in that：The silicone content being introduced into by water-soluble silicon oil in carrier is with dioxy SiClx meter accounts for the 0.1%~5.0% of modified oxidized alumina-based support weight, and preferably 0.2%~3.0%, more preferably 0.2%~1.5%。
- 3. according to the method for claim 1, it is characterised in that：The content being introduced into by soluble auxiliary agent in carrier is with oxide Meter accounts for the 0.1%~10.0% of modified oxidized alumina-based support weight, preferably 0.3%~5.0%, more preferably 0.5% ~2.0%.
- 4. according to the method for claim 1, it is characterised in that：Introduce the dosage difference of water-soluble silicon oil and soluble auxiliary agent Using the mol ratio that silica and oxide are counted as 0.05 ~ 80.0, preferably 0.1 ~ 15.0, more preferably 0.3 ~ 5.0.
- 5. according to the method for claim 1, it is characterised in that：Water-soluble silicon oil, refer to the silicone oil that can be dissolved in water, preferable Matter is as follows：Viscosity at 25 DEG C is 200 ~ 7000mPa.s, preferably 500 ~ 5000mPa.s, and cloud point is 30 ~ 100 DEG C, is preferably 40~65℃。
- 6. according to the method for claim 1, it is characterised in that：Alumina-based supports refer to using aluminum oxide as key component, Without adjuvant component or contain adjuvant component, wherein adjuvant component is the one or more in fluorine, silicon, phosphorus, titanium, zirconium, boron etc., is helped Content of the agent component in alumina-based supports is in below 30wt%, preferably below 20wt%, more preferably below 15wt%.
- 7. according to the method for claim 1, it is characterised in that：Alumina-based supports are aluminium hydroxide after high-temperature roasting Obtain, the condition of high-temperature roasting is as follows：1.0h~20.0h, the h of preferably 3.0 h ~ 8.0 are calcined at 450 DEG C~1000 DEG C.
- 8. according to the method for claim 1, it is characterised in that：The property of the alumina-based supports is as follows：Specific surface area For 120 ~ 420m2/ g, preferably 220 ~ 320m2/g；Pore volume is 0.4 ~ 1.3mL/g, preferably 0.6 ~ 1.0mL/g；Bore dia is less than Pore volume shared by 4nm hole accounts for less than the 20% of total pore volume, preferably accounts for less than 10%, more preferably less than 5%.
- 9. according to the method for claim 1, it is characterised in that：Soluble auxiliary agent refers to containing compounds such as aluminium, zirconium, boron, magnesium In one or more of combinations, soluble aluminum contained compound refers to one or more of in aluminum nitrate, aluminium chloride, aluminum sulfate Combination, soluble zirconium-containing compound refer to one or more of combinations in zirconium nitrate, zirconium chloride, zirconium oxychloride, soluble Boron-containing compound refers to one or more of combinations in boric acid, ammonium pentaborate, tetraboric acid ammonium, and soluble magnesium-containing compound is second One or more of combinations in sour magnesium, magnesium chloride, magnesium nitrate, sulfuric acid magnesium compound.
- 10. according to the method for claim 1, it is characterised in that：Water-soluble silicon oil and soluble auxiliary agent sequentially or simultaneously draw Enter onto carrier, you can first water-soluble silicon oil is incorporated on carrier, then soluble auxiliary agent is incorporated on carrier again；Or Water-soluble silicon oil and soluble auxiliary agent are incorporated on carrier simultaneously, its incorporation way uses infusion process, and infusion process is isometric Dipping or excessive dipping；Repeatedly dipping or single-steeping.
- 11. according to the method for claim 1, it is characterised in that：Described heat treatment is existed using two sections of heat treatments, first paragraph Temperature is 60 DEG C~150 DEG C, and preferably 90 DEG C~120 DEG C, processing time is 0.5h~20.0h, preferably 1.0h~6.0h, the Two sections are 180 DEG C~400 DEG C in temperature, and preferably 200 DEG C~350 DEG C, processing time is 0.5h~20.0h, preferably 1.0h ~6.0h.
- 12. according to the method for claim 1, it is characterised in that：Step（2）The organic additive and group VIB of middle introducing Atomic molar ratio is 0.01：1~5：1, in terms of final catalyst content, organic additive is organic compounds containing nitrogen, sulfur-bearing has One or more in machine compound.
- 13. according to the method for claim 1, it is characterised in that：The organic compounds containing nitrogen is common including at least one The organic matter of valence link nitrogen-atoms, carbon number is 1 ~ 20 in organic compounds containing nitrogen, preferably except including at least one covalent bond Nitrogen-atoms outside, also including at least a hydroxyl or the organic compound of carboxy moiety.
- 14. according to the method for claim 1, it is characterised in that：Organic compounds containing nitrogen be ethylenediamine, triethylamine, oneself two Amine, monoethanolamine, diethanol amine, triethanolamine, ethylenediamine tetra-acetic acid, nitrilotriacetic acid, one kind in ring ethylenediamine tetra-acetic acid or It is several.
- 15. according to the method for claim 1, it is characterised in that：Carbon number is 1 ~ 20 in organic compounds containing sulfur.
- 16. according to the method for claim 1, it is characterised in that：Organic compounds containing sulfur includes mercaptan（General formula R-SH）、 Thioether（General formula R-S-R）Or disulphide（General formula R-S-S-R）, wherein R is the alkyl containing 1 ~ 10 carbon atom.
- 17. according to the method for claim 1, it is characterised in that：Organic compounds containing sulfur be ethyl mercaptan, second propyl group thioether, One or more in DMDS, TGA, mercaptopropionic acid, dimercaprol dimercaptopropanol, dimethyl sulfoxide (DMSO), dimethyl sulfone.
- 18. according to the method for claim 1, it is characterised in that：Active metal component is vib metals and group VIII One or more in metal, wherein vib metals are preferably W and/or Mo, and group VIII metal is preferably Co and/or Ni.
- A kind of 19. catalyst prepared using claim 1 to 18 either method, it is characterised in that：Using the weight of catalyst as Benchmark, the content of modified oxidized alumina-based support are 55.0wt% ~ 94.5wt%, preferably 58.0wt% ~ 90.0wt%, VI B Family metal oxide content is 5.0wt% ~ 30.0wt%, preferably 8.0wt% ~ 30.0wt%, group VIII metal oxide Content is the wt % of 0.5wt% ~ 15.0 wt%, preferably 2.0 wt % ~ 12.0.
- 20. catalyst described in claim 19 is used for hydrotreating reaction, it is characterised in that：Reaction condition is as follows：React stagnation pressure 3.0MPa ~ 18.0MPa, volume space velocity 0.2h during liquid-1~4.0h-1, hydrogen to oil volume ratio 200:1~2000:1, reaction temperature 230 ℃~430℃。
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