CN109926075A - A kind of high-activity hydrogenation catalyst and preparation method thereof - Google Patents
A kind of high-activity hydrogenation catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN109926075A CN109926075A CN201711349773.0A CN201711349773A CN109926075A CN 109926075 A CN109926075 A CN 109926075A CN 201711349773 A CN201711349773 A CN 201711349773A CN 109926075 A CN109926075 A CN 109926075A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- preparation
- auxiliary agent
- diesel oil
- content
- 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 191
- 238000002360 preparation method Methods 0.000 title claims abstract description 61
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 30
- 230000000694 effects Effects 0.000 title abstract description 26
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229910052751 metal Inorganic materials 0.000 claims abstract description 52
- 239000002184 metal Substances 0.000 claims abstract description 52
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 47
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 25
- 229910052742 iron Inorganic materials 0.000 claims abstract description 18
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 17
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 150000002739 metals Chemical class 0.000 claims abstract description 11
- 230000003197 catalytic effect Effects 0.000 claims abstract description 5
- 239000002283 diesel fuel Substances 0.000 claims description 33
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 30
- 239000007864 aqueous solution Substances 0.000 claims description 25
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 15
- UPWOEMHINGJHOB-UHFFFAOYSA-N cobalt(III) oxide Inorganic materials O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 10
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 10
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 150000001869 cobalt compounds Chemical class 0.000 claims description 6
- -1 molybdate compound Chemical class 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000007790 solid phase Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- SCPWMSBAGXEGPW-UHFFFAOYSA-N dodecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OC)(OC)OC SCPWMSBAGXEGPW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- HIYNGBUQYVBFLA-UHFFFAOYSA-D cobalt(2+);dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Co+2].[Co+2].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O HIYNGBUQYVBFLA-UHFFFAOYSA-D 0.000 claims description 2
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 239000006012 monoammonium phosphate Substances 0.000 claims description 2
- 150000002816 nickel compounds Chemical class 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- BNCXNUWGWUZTCN-UHFFFAOYSA-N trichloro(dodecyl)silane Chemical compound CCCCCCCCCCCC[Si](Cl)(Cl)Cl BNCXNUWGWUZTCN-UHFFFAOYSA-N 0.000 claims description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 claims 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims 1
- 229940010552 ammonium molybdate Drugs 0.000 claims 1
- 235000018660 ammonium molybdate Nutrition 0.000 claims 1
- 239000011609 ammonium molybdate Substances 0.000 claims 1
- 239000000571 coke Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000005078 molybdenum compound Substances 0.000 claims 1
- 150000002752 molybdenum compounds Chemical class 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 229940038384 octadecane Drugs 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 3
- 238000011156 evaluation Methods 0.000 description 17
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 16
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 16
- 238000012512 characterization method Methods 0.000 description 8
- 229910000428 cobalt oxide Inorganic materials 0.000 description 8
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 8
- 238000000921 elemental analysis Methods 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 230000037396 body weight Effects 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910001593 boehmite Inorganic materials 0.000 description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- SLYCYWCVSGPDFR-UHFFFAOYSA-N octadecyltrimethoxysilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OC)(OC)OC SLYCYWCVSGPDFR-UHFFFAOYSA-N 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- RYPYGDUZKOPBEL-UHFFFAOYSA-N trichloro(hexadecyl)silane Chemical compound CCCCCCCCCCCCCCCC[Si](Cl)(Cl)Cl RYPYGDUZKOPBEL-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention provides a kind of high-activity hydrogenation catalyst and preparation method thereof, the hydrotreating catalyst includes hydrogenation metal component, auxiliary agent and carrier, hydrogenation metal component is one or more of vib metals and/or group VIII metal, Fe and P is auxiliary agent, and carrier is aluminium oxide and silica complex carrier.The present invention also provides a kind of preparation methods of above-mentioned hydrotreating catalyst.The catalyst metal components of the method for the present invention preparation are reasonably distributed, utilization rate is high, then while guarantee catalyst external surface acidity, have both reduced acid in catalyst duct, and catalyst is made to have high catalytic activity and liquid yield.
Description
Technical field
The invention belongs to PETROLEUM PROCESSING field, be related to a kind of catalysis material and preparation method thereof, more particularly to one kind plus
Hydrogen catalyst and preparation method thereof.
Background technique
As sulfur content declines year by year in fuel oil for vehicles specification, hydrodesulfurization has become processing inferior raw material production cleaning
The main path of fuel oil.The activity of Hydrobon catalyst determines the economic benefit of entire hydrodesulfurization.High activity
Hydrobon catalyst can produce the product of low-sulfur under conditions of mitigation, to extend operation cycle and save operating cost
With.
It is active component that Hydrobon catalyst, which generallys use group VIB and group VIII metal, and can be added a variety of
Auxiliary agent improves catalyst activity.Currently, the method for preparing catalyst that countries in the world generally use is exactly to use solution dipping method,
Active metal component is supported on carrier, then by drying, roasting and etc. obtain corresponding catalyst.This preparation
The catalyst activity component of method preparation is distributed on the surfaces externally and internally of catalyst carrier, the inner surface including deep inside gap
On.
CN1872962A discloses a kind of hydrotreating catalyst containing molecular sieve, and the catalyst is with aluminium oxide and Y type point
Son sieve is carrier, supported active metals component nickel, molybdenum and tungsten, i.e., first by boehmite and molecular sieve mechanical mixture, in substep
Supported active metals component can make active component evenly dispersed on carrier, keep catalyst hydrodesulfurization with higher living
Property.
CN1339563A discloses a kind of catalyst for hydrodesulfurizationfraction fraction oil, and catalyst is with aluminium oxide or silicon-containing alumina
For carrier, using molybdenum nickel as active component, total immersion carrier is segmented using alkaline impregnation, makes on catalyst Metal Distribution more evenly,
The fraction oil hydrodesulfurizing activity of catalyst is significantly improved.
CN1289828A discloses a kind of catalyst for hydrorefining distillate oil, and catalyst is with aluminium oxide or silicon-containing alumina
Carrier adds phosphate builder using W, Mo, Ni as active component.By using segmentation total immersion technology, so that the metal point on catalyst
Cloth is more uniform, and the activity of catalyst, especially hydrodenitrogenationactivity activity are greatly improved.
CN201110446040.5 discloses a kind of preparation method of catalyst for hydrogenation of fraction oil, and Ni, Co, W/Mo are
Active component, aluminium oxide or silicon-containing alumina are carrier, and P element is auxiliary agent.Active component uses step impregnation, and catalyst has
High hydrodesulfurization activity.
Summary of the invention
Aiming at the problems existing in the prior art, it is an object of the present invention to provide a kind of hydrotreating catalyst and its preparation sides
Method, the catalyst of preparation when in use, the active high and high advantage of liquid yield.
First aspect present invention provides a kind of hydrotreating catalyst, and the hydrotreating catalyst includes hydrogenation metal group
Point, auxiliary agent and carrier, hydrogenation metal component is one or more of vib metals and/or group VIII metal, and auxiliary agent is
Fe and P, carrier be aluminium oxide and silica complex carrier, wherein Silica-coated aluminium oxide, the weight of silica
Account for the 3%~10% of carrying alumina body weight；On the basis of the weight of catalyst, the content of hydrogenation metal component is 12.0%~
25%, auxiliary agent content is 1.6%~7.6%, and the content of carrier is 67.4%~86.4%.
In hydrotreating catalyst of the present invention, vib metals are generally Mo and/or W, and group VIII metal is generally Ni
And/or Co.
In hydrotreating catalyst of the present invention, the auxiliary agent is Fe and P, on the basis of the weight of catalyst, Fe2O3Contain
Amount is 0.5%~3%, P2O5Content be 1.1%~4.6%.
In hydrotreating catalyst of the present invention, the specific surface area of the hydrogenation catalyst is 200~260m2/ g, Kong Rongwei
0.40~0.6mL/g, average pore diameter are 7.0~12.0nm.
In hydrotreating catalyst of the present invention, hydrogenation metal component is uniformly distributed on a catalyst；Auxiliary agent iron is distributed in 3/4
Content within the scope of radius to catalyst edge is 95.0wt%~98.0wt% of auxiliary agent iron total content.
In hydrotreating catalyst of the present invention, the hydrogenation metal component is preferably Mo, Co, using the weight of catalyst as base
Standard, MoO3Content is 10%~20%, Co2O3Content be 2%~5%.
Second aspect of the present invention provides a kind of preparation method of above-mentioned hydrotreating catalyst, and the preparation method includes such as
Lower content:
(1) it is prepared with compound, phosphorus-containing compound and water containing hydrogenation metal component water-soluble containing hydrogenation metal component and auxiliary agent P
Liquid；
(2) processing is modified to alumina support using auxiliary agent A, obtains catalyst precarsor A；
(3) the catalyst precarsor A that step (2) obtains is added in auxiliary agent B, is separated by solid-liquid separation after mixing, will obtained
Solid phase stood at -50 DEG C~0 DEG C, preferably -30~0 DEG C；
(4) iron containing compounds aqueous solution is added in the material that step (3) obtains, is separated by solid-liquid separation after the completion of dipping, point
Catalyst precarsor B is obtained after drying from obtained solid phase；
(5) aqueous solution that step (1) obtains is mixed with catalyst precarsor B, is urged after drying, roasting after being uniformly mixed
Agent.
In preparation method of the present invention, the compound containing hydrogenation metal component described in step (1) is containing vib metals
And/or the compound of the metal containing group VIII, the compound containing vib metals can be molybdate compound, contain tungsten
One or more of object is closed, the compound of the metal containing group VIII is one of cobalt compound, nickel compound containing
Or it is several.The compound containing hydrogenation metal component is preferably molybdate compound and cobalt compound, the molybdate compound
It can be molybdenum oxide and/or ammonium heptamolybdate；The cobalt compound is basic cobaltous carbonate and/or cobalt nitrate, the phosphorous chemical combination
Object can be one or more of phosphoric acid, ammonium dihydrogen phosphate, monoammonium phosphate.
In preparation method of the present invention, hydrogenation metal in the aqueous solution containing hydrogenation metal component and auxiliary agent P described in step (1)
The concentration of component is 0.05~0.3g/mL(in terms of hydrogenation metal oxide), the concentration of auxiliary agent P is 0.005~0.05 g/mL.
It can be prepared using the existing method in this field.
In preparation method of the present invention, alumina support described in step (2) generallys use ball-aluminium oxide, alumina support
It can be obtained by boehmite through molding, drying and roasting.The boehmite can be used conventional method and be made, such as chlorine
Change aluminium method, aluminum sulfate method, carbonizatin method etc..
In preparation method of the present invention, carrying alumina volume property described in step (2) is as follows: 0.6~0.9mL/g of Kong Rongwei,
Specific surface area is 160~320m2/ g, particle diameter 0.1mm~1.2mm.
In preparation method of the present invention, modification process described in step (2) is as follows:
(2.1) auxiliary agent A is mixed with organic solvent, obtains solution I after mixing；
(2.2) alumina support is mixed with solution I, is reacted after mixing, then through being dried to obtain catalyst precarsor
B。
In step (2.1), the auxiliary agent A is octadecyl trimethoxysilane, hexadecyl trimethoxy silane, ten
One of dialkyl group trimethoxy silane, octadecyl trichlorosilane alkane, hexadecyl trichlorosilane, dodecyltrichlorosilane
Or it is several.
In step (2.1), the organic solvent be one or more of benzene, toluene, hexamethylene, wherein auxiliary agent A with
The mass ratio of organic solvent is 1:1~1:50.
In step (2.2), the reaction temperature is 40~60 DEG C, and the reaction time is 1.0~5.0h；The drying temperature
It is 70~90 DEG C, the time is 3.0~12.0h.
In preparation method of the present invention, auxiliary agent B described in step (3) is diesel oil, and the condensation point of the diesel oil is -40~20
DEG C, preferably -40~0 DEG C, further preferably -30~0 DEG C, the diesel oil can be straight-run diesel oil, hydrogenated diesel oil, coking bavin
Oil, one of catalytic diesel oil or a variety of, it is preferred to use hydrogenated diesel oil, specifically can use commercial goods diesel oil, as 5# diesel oil,
One of 0# diesel oil, -10# diesel oil, -20# diesel oil, -35# diesel oil are a variety of, and the volume ratio of the auxiliary agent B and aluminium oxide is 1
~4:1, preferably 1~2:1.
In preparation method of the present invention, iron containing compounds described in step (4) can be in ferric nitrate, iron chloride, ferric sulfate
One or more.
In preparation method of the present invention, isolated solid phase preferably carries out high-temperature process in a nitrogen atmosphere in step (4),
Catalyst precarsor B is obtained after processing；The temperature of the high-temperature process is 300~400 DEG C, and the time is 2.0~5.0h.
In preparation method of the present invention, drying temperature described in step (5) be 60~120 DEG C, drying time be 3.0~
12.0h；The drying is carried out preferably by the way of Two stage dryer, and wherein first segment drying temperature is 60~90 DEG C, second segment
Drying temperature is 90~120 DEG C；The maturing temperature is 400~700 DEG C, and calcining time is 2.0~6.0h.
Compared with prior art, hydrotreating catalyst of the present invention and preparation method thereof has the advantages that
1, it is high with utilization rate to have the advantages that metal component is reasonably distributed for hydrotreating catalyst of the present invention, then guarantees to be catalyzed
While agent outer surface acidity, acidity in catalyst duct had both been reduced, has made catalyst that there is high catalytic activity and liquid to receive
Rate.
It 2,, not only can be with accelerating auxiliaries by introducing auxiliary agent A in the preparation method of hydrotreating catalyst of the present invention
Interaction between B and carrier, and realize the purpose being modified to alumina support simultaneously, in auxiliary agent A and auxiliary agent B
Under collective effect, it is ensured that auxiliary agent iron is as much as possible to be supported on carrier surface, ensure that catalyst external surface acidity.
3, in the preparation method of hydrotreating catalyst of the present invention, modification of the auxiliary agent A to carrier makes alumina support
On the one hand outer surface coated silica reduces the acid amount in catalyst duct, on the other hand the silica of cladding also can
The strong interaction prevented between metal component and alumina catalyst support is played, avoids active component from forming Spinel, is conducive to
The vulcanization of the active component of load further increases the activity of catalyst.
4, in the preparation method of hydrotreating catalyst of the present invention, auxiliary agent iron and alumina catalyst support interact, energy
The acidity for enough improving carrier, in this method, auxiliary agent iron is distributed in the content within the scope of 3/4 radius to catalyst edge as auxiliary agent iron
95.0wt%~98.0wt% of total content ensure that the acidity of catalyst surface while reducing acid in catalyst duct,
Make catalyst that there is high catalytic activity and liquid yield.
5, in the preparation method of hydrotreating catalyst of the present invention, the high-temperature process under nitrogen atmosphere makes carrier surface
A large amount of carbon distributions are generated, the strong interaction between metal component and carrier can be effectively prevented, generation active component is avoided to form point
Spar phase is conducive to the vulcanization of the active component of load, further increases the activity of catalyst.
Specific embodiment
Below by embodiment, the present invention is described further, and in the present invention, wt% is mass fraction.
Specific surface area, Kong Rong are measured using low temperature liquid nitrogen physisorphtion in the present invention, specifically use Merck & Co., Inc, the U.S.
The nitrogen absorption under low temperature instrument of ASAP2420 model measures；Detailed process: a small amount of sample is taken to be vacuum-treated 3 ~ 4h at 300 DEG C, most
Product is placed under the conditions of liquid nitrogen cryogenics (- 200 DEG C) afterwards and carries out nitrogen suction-desorption test.Wherein surface area is obtained according to BET equation
It arrives, pore-size distribution is obtained according to BJH model.SEM(scanning electron microscope) specifically using the JSM- of JEOL company, Japan production
The SEM(scanning electron microscope of 7500F type), it is equipped with EDAX-EDS, acceleration voltage: 20Kv, operating distance: 8mm, resolution ratio:
1nm。
Embodiment 1
(1) preparation of Mo-Co-P aqueous solution:
By 4.6g phosphoric acid H3PO4(85 wt% of concentration) is dissolved in 80mL water, and 12.4g molybdenum trioxide and 5.8g alkali formula carbon is then added
Sour cobalt is warming up to 100 DEG C and is stirred at reflux 2.0h, and constant volume is 100mL to get Mo-Co-P aqueous solution after filtering.Wherein MoO3's
Concentration is 0.12g/mL, Co2O3Concentration be 0.03g/mL, the concentration of P is 0.012g/mL.
(2) preparation of catalyst:
By 73.1g alumina support (Kong Rongwei 0.70mL/g, specific surface area 300m2/ g, it is spherical, particle diameter 0.4mm~
It 0.6mm) is added in the cyclohexane solution for containing 36.7g dodecyltrimethoxysilane containing 200mL, is reacted at 50 DEG C
3.0h obtains catalyst precarsor A in 70 DEG C of dry 8h；It is then added in 200mL5# diesel oil, filters, obtain after impregnating 30min
To material be placed in 0 DEG C low-temp reaction bath in.Then the aqueous solution of 100mL ferric nitrate containing 5.1g is added, is filtered after impregnating 2h,
By obtained solid 350 DEG C of high-temperature process 4.0h in a nitrogen atmosphere, catalyst precarsor B is obtained；100mLMo-Co-P is water-soluble
It after liquid is diluted to 150mL, is added in catalyst precarsor B, after mixing in 70 DEG C of dry 4h, then heats to 110 DEG C and do
Then in 450 DEG C of roasting 3.0h catalyst is made, wherein MoO in dry 4h3Content is 12wt%, Co2O3Content is 3.0wt%, and P contains
Amount is 1.2wt%, Fe2O3Content is 1.0wt%, and the weight of silica accounts for the 10% of carrying alumina body weight.The materialization of catalyst
Property is shown in Table 1.
(3) catalyst characterization:
Elemental analysis is carried out to catalyst by SEM, molybdenum oxide and cobalt oxide are uniformly distributed on a catalyst；Iron oxide is distributed in
Content within the scope of 3/4 radius to catalyst edge is the 98.0wt% of total content.
(4) evaluation of catalyst:
Evaluating catalyst carries out on micro-reactor, carries out presulfurization to catalyst before activity rating.Evaluating catalyst condition is
6.0 MPa of Hydrogen Vapor Pressure, volume space velocity 2.0h when liquid-1, hydrogen-oil ratio 500:1,340 DEG C of reaction temperature.Activity rating raw material oiliness
Matter is shown in Table 2.Activity evaluation is shown in Table 3.
Embodiment 2
(1) preparation of Mo-Co-P aqueous solution:
By 5.7g phosphoric acid H3PO4(85 wt% of concentration) is dissolved in 80mL water, and 15.6g molybdenum trioxide and 7.2g alkali formula carbon is then added
Sour cobalt is warming up to 100 DEG C and is stirred at reflux 2.0h, and constant volume is 100mL to get Mo-Co-P aqueous solution after filtering.Wherein MoO3's
Concentration is 0.15g/mL, Co2O3Concentration be 0.038g/mL, the concentration of P is 0.015g/mL.
(2) preparation of catalyst:
By 70.1g alumina support (Kong Rongwei 0.70mL/g, specific surface area 300m2/ g, it is spherical, particle diameter 0.4mm~
It 0.6mm) is added in the cyclohexane solution for containing 33.1g hexadecyl trimethoxy silane containing 200mL, is reacted at 50 DEG C
3.0h obtains catalyst precarsor A in 70 DEG C of dry 8h；It is then added in 200mL0# diesel oil, filters, obtain after impregnating 30min
To material be placed in -10 DEG C low-temp reaction bath in.Then the aqueous solution of 100mL ferric nitrate containing 7.6g is added, impregnates mistake after 2h
Obtained solid 350 DEG C of high-temperature process 4.0h in a nitrogen atmosphere are obtained catalyst precarsor B by filter；By 100mLMo-Co-P water
It after solution is diluted to 150mL, is added in catalyst precarsor B, after mixing in 70 DEG C of dry 4h, then heats to 110 DEG C
Then in 450 DEG C of roasting 3.0h catalyst is made, wherein MoO in dry 4h3Content is 15wt%, Co2O3Content is 3.8wt%, P
Content is 1.5wt%, Fe2O3Content is 1.5wt%, and the weight of silica accounts for the 8% of carrying alumina body weight.The materialization of catalyst
Property is shown in Table 1.
(3) catalyst characterization:
SEM being crossed all, elemental analysis being carried out to catalyst, molybdenum oxide and cobalt oxide are uniformly distributed on a catalyst；Iron oxide distribution
Content within the scope of 3/4 radius to catalyst edge is the 98.0wt% of total content.
(4) evaluation of catalyst:
For evaluating catalyst with embodiment 1, Activity evaluation is shown in Table 3.
Embodiment 3
(1) preparation of Mo-Co-P aqueous solution:
By 5.7g phosphoric acid H3PO4(85 wt% of concentration) is dissolved in 80mL water, and 15.6g molybdenum trioxide and 7.2g alkali formula carbon is then added
Sour cobalt is warming up to 100 DEG C and is stirred at reflux 2.0h, and constant volume is 100mL to get Mo-Co-P aqueous solution after filtering.Wherein MoO3's
Concentration is 0.15g/mL, Co2O3Concentration be 0.038g/mL, the concentration of P is 0.015g/mL.
(2) preparation of catalyst:
By 71.9g alumina support (Kong Rongwei 0.70mL/g, specific surface area 300m2/ g, it is spherical, particle diameter 0.4mm~
It 0.6mm) is added in the cyclohexane solution for containing 20.6g hexadecyl trimethoxy silane containing 200mL, is reacted at 50 DEG C
3.0h obtains catalyst precarsor A in 70 DEG C of dry 8h；It is then added in 200mL0# diesel oil, filters, obtain after impregnating 30min
To material be placed in -10 DEG C low-temp reaction bath in.Then the aqueous solution of 100mL ferric nitrate containing 10.1g is added, impregnates mistake after 2h
Obtained solid 350 DEG C of high-temperature process 4.0h in a nitrogen atmosphere are obtained catalyst precarsor B by filter；By 100mLMo-Co-P water
It after solution is diluted to 150mL, is added in catalyst precarsor B, after mixing in 70 DEG C of dry 4h, then heats to 110 DEG C
Then in 450 DEG C of roasting 3.0h catalyst is made, wherein MoO in dry 4h3Content is 15wt%, Co2O3Content is 3.8wt%, P
Content is 1.5wt%, Fe2O3Content is 2.0wt%, and the weight of silica accounts for the 5% of carrying alumina body weight.The materialization of catalyst
Property is shown in Table 1.
(3) catalyst characterization:
Elemental analysis is carried out to catalyst by SEM, molybdenum oxide and cobalt oxide are uniformly distributed on a catalyst；Iron oxide is distributed in
Content within the scope of 3/4 radius to catalyst edge is the 97.5wt% of total content.
(4) evaluation of catalyst:
For evaluating catalyst with embodiment 1, Activity evaluation is shown in Table 3.
Embodiment 4
(1) preparation of Mo-Co-P aqueous solution:
By 6.9g phosphoric acid H3PO4(85 wt% of concentration) is dissolved in 80mL water, and 18.6g molybdenum trioxide and 8.7g alkali formula carbon is then added
Sour cobalt is warming up to 100 DEG C and is stirred at reflux 2.0h, and constant volume is 100mL to get Mo-Co-P aqueous solution after filtering.Wherein MoO3's
Concentration is 0.18g/mL, Co2O3Concentration be 0.045g/mL, the concentration of P is 0.018g/mL.
(2) preparation of catalyst:
By 68.7g alumina support (Kong Rongwei 0.70mL/g, specific surface area 300m2/ g, it is spherical, particle diameter 0.4mm~
It 0.6mm) is added in the cyclohexane solution for containing 12.3g octadecyl trimethoxysilane containing 200mL, is reacted at 50 DEG C
3.0h obtains catalyst precarsor A in 70 DEG C of dry 8h；It is then added in 200mL-10# diesel oil, is filtered after impregnating 30min,
Obtained material is placed in -20 DEG C of low-temp reaction bath.Then the aqueous solution of 100mL ferric nitrate containing 13.2g is added, after impregnating 2h
Obtained solid 350 DEG C of high-temperature process 4.0h in a nitrogen atmosphere are obtained catalyst precarsor B by filtering；By 100mLMo-Co-P
It after aqueous solution is diluted to 150mL, is added in catalyst precarsor B, after mixing in 70 DEG C of dry 4h, then heats to 110
DEG C dry 4h, then in 450 DEG C of roasting 3.0h, obtained catalyst, wherein MoO3Content is 18wt%, Co2O3Content is 4.5wt%,
P content is 1.8wt%, Fe2O3Content is 2.5wt%, and the weight of silica accounts for the 3% of carrying alumina body weight.The object of catalyst
Change property and is shown in Table 1.
(3) catalyst characterization:
Elemental analysis is carried out to catalyst by SEM, molybdenum oxide and cobalt oxide are uniformly distributed on a catalyst；Iron oxide is distributed in
Content within the scope of 3/4 radius to catalyst edge is the 97.0wt% of total content.
(4) evaluation of catalyst:
For evaluating catalyst with embodiment 1, Activity evaluation is shown in Table 3.
Embodiment 5
(1) preparation of catalyst:
In embodiment 1, will 350 DEG C of high-temperature process 4.0h in a nitrogen atmosphere, be changed in the case where relative degree of vacuum is -0.1MPa,
Catalyst is made, wherein MoO in 110 DEG C of dry 8.0h3Content is 12wt%, Co2O3Content is 3.0wt%, P content 1.2wt%,
Fe2O3Content is 1.0wt%, and the weight of silica accounts for the 10% of carrying alumina body weight.The physico-chemical property of catalyst is shown in Table 1.
(2) catalyst characterization:
Elemental analysis is carried out to catalyst by SEM, molybdenum oxide and cobalt oxide are uniformly distributed on a catalyst；Iron oxide is distributed in
Content within the scope of 3/4 radius to catalyst edge is the 98.0wt% of total content.
(3) evaluation of catalyst:
For evaluating catalyst with embodiment 1, Activity evaluation is shown in Table 3.
Comparative example 1
(1) preparation of catalyst:
In embodiment 1, by 100mL Mo-Co-P aqueous solution and 50mL contain 5.1g ferric nitrate aqueous solution mix, then plus
Enter to 81.2g alumina support (Kong Rongwei 0.70mL/g, specific surface area 300m2/ g, it is spherical, particle diameter 0.4mm~
In 0.6mm), after mixing in 70 DEG C of dry 4h, 110 DEG C of dry 4h are then heated to, obtained solid is roasted at 450 DEG C
Catalyst is made, wherein MoO in 3.0 h3Content is 12wt%, Co2O3Content is 3.0wt%, P content 1.2wt%, Fe2O3Content
For 1.0wt%.The physico-chemical property of catalyst is shown in Table 1.
(2) catalyst characterization:
Elemental analysis is carried out to catalyst by SEM, molybdenum oxide, cobalt oxide and iron oxide are uniformly distributed on a catalyst.
(3) evaluation of catalyst:
For evaluating catalyst with embodiment 1, Activity evaluation is shown in Table 3.
Comparative example 2
It is substantially the same manner as Example 1, the difference is that not using auxiliary agent A dodecyltrimethoxysilane to carrying alumina
Body is modified processing.
(1) preparation of catalyst:
By 81.2g alumina support (Kong Rongwei 0.70mL/g, specific surface area 300m2/ g, it is spherical, particle diameter 0.4mm~
It 0.6mm) is added in 200mL5# diesel oil, is filtered after impregnating 30min, obtained material is placed in 0 DEG C of low-temp reaction bath.It will
The aqueous solution that 100mL contains 5.1g ferric nitrate is added in above-mentioned material, is filtered after impregnating 2h, by obtained solid in nitrogen gas
The lower 350 DEG C of high-temperature process 4.0h of atmosphere, obtain catalyst precarsor；After 100mLMo-Co-P aqueous solution is diluted to 150mL, it is added to
In catalyst precarsor, after mixing in 70 DEG C of dry 4h, 110 DEG C of dry 4h are then heated to, then roast 3.0 at 450 DEG C
Catalyst is made, wherein MoO in h3Content is 12wt%, Co2O3Content is 3.0wt%, P content 1.2wt%, Fe2O3Content is
1.0wt%.The physico-chemical property of catalyst is shown in Table 1.
(2) catalyst characterization:
Elemental analysis is carried out to catalyst by SEM, molybdenum oxide and cobalt oxide are uniformly distributed on a catalyst；Iron oxide is distributed in
Content within the scope of 3/4 radius to catalyst edge is the 97.0wt% of total content.
(3) evaluation of catalyst:
For evaluating catalyst with embodiment 1, Activity evaluation is shown in Table 3.
Modification of the auxiliary agent A to catalyst makes carrying alumina external surface coated silica, on the one hand can weaken carrier
The acidity of itself, on the other hand the silica of cladding can also play strong mutually between prevention metal component and alumina catalyst support
Effect avoids active component from forming Spinel, is conducive to the vulcanization of the active component of load, further increases the work of catalyst
Property.So compared with Example 1,2 catalyst of comparative example does not use auxiliary agent A modified, and carrying alumina external surface does not coat two
The acidity of silica, catalyst is not weakened.Therefore, the conversion ratio of catalyst and selectivity are all influenced.
Comparative example 3
It is substantially the same manner as Example 1, the difference is that auxiliary agent B is not used to handle catalyst precarsor A.
(1) preparation of catalyst:
Catalyst precarsor A is added in the aqueous solution of 100mL ferric nitrate containing 5.1g, is filtered after impregnating 2h, the solid that will be obtained
350 DEG C of high-temperature process 4.0h in a nitrogen atmosphere obtain catalyst precarsor B；100mLMo-Co-P aqueous solution is diluted to 150mL
Afterwards, it is added in catalyst precarsor B, after mixing in 70 DEG C of dry 4h, 110 DEG C of dry 4h is then heated to, then 450
DEG C roasting 3.0h, is made catalyst, wherein MoO3Content is 12wt%, Co2O3Content is 3.0wt%, P content 1.2wt%, Fe2O3
Content is 1.0wt%, and the weight of silica accounts for the 10% of carrying alumina body weight.The physico-chemical property of catalyst is shown in Table 1.
(2) catalyst characterization:
Elemental analysis is carried out to catalyst by SEM, molybdenum oxide, cobalt oxide and iron oxide are uniformly distributed on a catalyst.
(3) evaluation of catalyst:
For evaluating catalyst with embodiment 1, Activity evaluation is shown in Table 3.
The property of 1 catalyst of table
2 raw material oil nature of table
The Activity evaluation of 3 catalyst of table
Claims (27)
1. a kind of hydrotreating catalyst, the hydrotreating catalyst includes hydrogenation metal component, auxiliary agent and carrier, adds hydrogen golden
Category group is divided into one or more of vib metals and/or group VIII metal, and auxiliary agent is Fe and P, carrier be aluminium oxide and
Silica complex carrier；On the basis of the weight of catalyst, the content of hydrogenation metal component is 12.0%~25%, auxiliary agent content
It is 1.6%~7.6%, the content of carrier is 67.4%~86.4%.
2. hydrotreating catalyst described in accordance with the claim 1, it is characterised in that: vib metals are Mo and/or W, the
Group VIII metal is Ni and/or Co.
3. hydrotreating catalyst described in accordance with the claim 1, it is characterised in that: the weight of silica accounts for alumina support
The 3%~10% of weight.
4. hydrotreating catalyst described in accordance with the claim 1, it is characterised in that: the auxiliary agent is Fe and P, with catalyst
On the basis of weight, Fe2O3Content be 0.5%~3%, P2O5Content be 1.1%~4.6%.
5. hydrotreating catalyst described in accordance with the claim 1, it is characterised in that: the specific surface area of the hydrogenation catalyst is
200~260m20.40~0.6mL/g of/g, Kong Rongwei, average pore diameter are 7.0~12.0nm.
6. hydrotreating catalyst described in accordance with the claim 1, it is characterised in that: hydrogenation metal component is uniform on a catalyst
Distribution；Auxiliary agent iron be distributed in 3/4 radius of catalyst to the content within the scope of catalyst outer edge be auxiliary agent iron total content
95.0wt%~98.0wt%.
7. hydrotreating catalyst described in accordance with the claim 1, it is characterised in that: the hydrogenation metal component is Mo and Co,
On the basis of the weight of catalyst, MoO3Content is 10%~20%, Co2O3Content be 2%~5%.
8. the preparation method of hydrotreating catalyst described in any claim in claim 1-7, it is characterised in that: the system
Preparation Method includes following content:
(1) it is prepared with compound, phosphorus-containing compound and water containing hydrogenation metal component water-soluble containing hydrogenation metal component and auxiliary agent P
Liquid；
(2) processing is modified to alumina support using auxiliary agent A, obtains catalyst precarsor A；
(3) the catalyst precarsor A that step (2) obtains is mixed with auxiliary agent B, is separated by solid-liquid separation after mixing, will separated
The solid phase arrived is stood at -50 DEG C~0 DEG C, preferably -30~0 DEG C；
(4) iron containing compounds aqueous solution is mixed with the material that step (3) obtains, is separated by solid-liquid separation after the completion of dipping, separated
Obtained solid phase is dried to obtain catalyst precarsor B；
(5) aqueous solution that step (1) obtains is mixed with catalyst precarsor B, is urged after drying, roasting after being uniformly mixed
Agent.
9. preparation method according to claim 8, it is characterised in that: the change containing hydrogenation metal component described in step (1)
Conjunction object is the compound containing vib metals and/or the metal containing group VIII.
10. preparation method according to claim 9, it is characterised in that: the compound containing vib metals is chemical combination containing molybdenum
One or more of object, Tungstenic compound, the compound of the metal containing group VIII are cobalt compound, in nickel compound containing
It is one or more of.
11. preparation method according to claim 8, it is characterised in that: the compound containing hydrogenation metal component be containing
Molybdenum compound and cobalt compound.
12. according to preparation method described in claim 10 or 11, it is characterised in that: molybdate compound is molybdenum oxide and/or seven
Ammonium molybdate；The cobalt compound is basic cobaltous carbonate and/or cobalt nitrate.
13. preparation method according to claim 8, it is characterised in that: the phosphorus-containing compound is phosphoric acid, biphosphate
One or more of ammonium, monoammonium phosphate.
14. preparation method according to claim 8, it is characterised in that: contain hydrogenation metal component described in step (1) and help
The concentration of hydrogenation metal component is 0.05~0.3g/mL in the aqueous solution of agent P, and the concentration of auxiliary agent P is 0.005~0.05 g/mL.
15. preparation method according to claim 8, it is characterised in that: modification process described in step (2) is such as
Under:
(2.1) auxiliary agent A is mixed with organic solvent, obtains solution I after mixing；
(2.2) alumina support is mixed with solution I, is reacted after mixing, then through being dried to obtain catalyst precarsor
B。
16. preparation method according to claim 15, it is characterised in that: auxiliary agent A described in step (2.1) is octadecane
Base trimethoxy silane, hexadecyl trimethoxy silane, dodecyltrimethoxysilane, octadecyl trichlorosilane alkane, ten
One or more of six alkyltrichlorosilanes, dodecyltrichlorosilane.
17. preparation method according to claim 15, it is characterised in that: organic solvent described in step (2.1) be benzene,
One or more of toluene, hexamethylene.
18. preparation method according to claim 15, it is characterised in that: the mass ratio of the auxiliary agent A and organic solvent is
1:1~1:50.
19. preparation method according to claim 15, it is characterised in that: reaction temperature described in step (2.2) be 40~
60 DEG C, the reaction time is 1.0~5.0h；The drying temperature is 70~90 DEG C, and the time is 3.0~12.0h.
20. preparation method according to claim 8, it is characterised in that: auxiliary agent B described in step (3) is diesel oil, described
The condensation point of diesel oil is -40~20 DEG C, preferably -40~0 DEG C, further preferably -30~0 DEG C.
21. preparation method according to claim 20, it is characterised in that: the diesel oil is straight-run diesel oil, hydrogenated diesel oil, coke
Change diesel oil, one of catalytic diesel oil or a variety of, it is preferred to use hydrogenated diesel oil.
22. preparation method according to claim 20, it is characterised in that: the diesel oil uses commercial goods diesel oil, such as 5#
One of diesel oil, 0# diesel oil, -10# diesel oil, -20# diesel oil, -35# diesel oil are a variety of.
23. preparation method according to claim 8, it is characterised in that: the auxiliary agent B and the volume ratio of aluminium oxide be 1~
4:1, preferably 1~2:1.
24. preparation method according to claim 8, it is characterised in that: iron containing compounds described in step (4) are nitric acid
One or more of iron, iron chloride, ferric sulfate.
25. preparation method according to claim 8, it is characterised in that: isolated solid phase is in nitrogen gas in step (4)
High-temperature process is carried out under atmosphere, and catalyst precarsor B is obtained after processing.
26. according to the preparation method described in claim 25, it is characterised in that: the temperature of high-temperature process is 300~400 DEG C, when
Between be 2.0~5.0h.
27. preparation method according to claim 8, it is characterised in that: drying temperature described in step (5) is 60~120
DEG C, drying time is 3.0~12.0h；The drying is carried out preferably by the way of Two stage dryer, wherein first segment drying temperature
It is 60~90 DEG C, second segment drying temperature is 90~120 DEG C；The maturing temperature is 400~700 DEG C, calcining time 2.0
~6.0h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711349773.0A CN109926075B (en) | 2017-12-15 | 2017-12-15 | High-activity hydrotreating catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711349773.0A CN109926075B (en) | 2017-12-15 | 2017-12-15 | High-activity hydrotreating catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109926075A true CN109926075A (en) | 2019-06-25 |
| CN109926075B CN109926075B (en) | 2021-08-31 |
Family
ID=66979911
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711349773.0A Active CN109926075B (en) | 2017-12-15 | 2017-12-15 | High-activity hydrotreating catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109926075B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3487011A (en) * | 1966-11-23 | 1969-12-30 | Gulf Research Development Co | Hydrodesulfurization of naphthas |
| CN1778873A (en) * | 2004-11-26 | 2006-05-31 | 中国石油天然气股份有限公司 | Inferior diesel oil hydrotreating catalyst |
| CN103769178A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Hydro-desulfurization catalyst and preparation method thereof |
| CN104588056A (en) * | 2013-11-03 | 2015-05-06 | 中国石油化工股份有限公司 | Catalyst used for preparation of dimethyl ether through dehydration of methanol and preparation method thereof |
| CN107297209A (en) * | 2016-04-16 | 2017-10-27 | 中国石油化工股份有限公司 | A kind of hydrotreating catalyst and preparation method thereof |
-
2017
- 2017-12-15 CN CN201711349773.0A patent/CN109926075B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3487011A (en) * | 1966-11-23 | 1969-12-30 | Gulf Research Development Co | Hydrodesulfurization of naphthas |
| CN1778873A (en) * | 2004-11-26 | 2006-05-31 | 中国石油天然气股份有限公司 | Inferior diesel oil hydrotreating catalyst |
| CN103769178A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Hydro-desulfurization catalyst and preparation method thereof |
| CN104588056A (en) * | 2013-11-03 | 2015-05-06 | 中国石油化工股份有限公司 | Catalyst used for preparation of dimethyl ether through dehydration of methanol and preparation method thereof |
| CN107297209A (en) * | 2016-04-16 | 2017-10-27 | 中国石油化工股份有限公司 | A kind of hydrotreating catalyst and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109926075B (en) | 2021-08-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4156859B2 (en) | Gas oil hydrotreating catalyst, method for producing the same, and gas oil hydrotreating method | |
| CN106179382B (en) | A kind of preparation method of body phase hydrotreating catalyst | |
| CN105579135B (en) | Hydrotreating catalyst, the manufacturing method of the hydrotreating catalyst of heavy hydrocarbon oil and the hydrotreating method of heavy hydrocarbon oil of heavy hydrocarbon oil | |
| CN105579134B (en) | The hydrotreating catalyst of heavy hydrocarbon oil and the hydrotreating method of heavy hydrocarbon oil | |
| US10137436B2 (en) | Hydrogenation catalyst for heavy hydrocarbon oil and hydrogenation method for heavy hydrocarbon oil | |
| CN106179474B (en) | A kind of Hydrobon catalyst and its preparation method | |
| CN106179381B (en) | The preparation method of Hydrobon catalyst | |
| WO2011023668A2 (en) | Solutions and catalysts comprising group vi metal, group viii metal, and phosphorus | |
| CN106693982B (en) | Gasoline hydrogenation catalyst and preparation method thereof | |
| CN107297209A (en) | A kind of hydrotreating catalyst and preparation method thereof | |
| CN111375396B (en) | Hydrotreating catalyst carrier, catalyst and preparation method thereof | |
| CN109304183A (en) | Handle the hydrotreating catalyst and the preparation method and application thereof of inferior oil material | |
| CN106607068B (en) | A kind of Hydrobon catalyst and preparation method thereof | |
| CN106179385B (en) | A kind of preparation method of Hydrobon catalyst | |
| CN100556994C (en) | Phosphorated diesel oil hydrofining catalyst and preparation method thereof | |
| JP4689198B2 (en) | Hydrocarbon hydrotreating catalyst, process for producing the same, and hydrotreating process for hydrocarbon oil | |
| CN109772387B (en) | Hydrotreating catalyst and preparation method thereof | |
| CN103816914A (en) | Preparation method of light distillate oil hydrodesulfurization catalyst | |
| CN107970943B (en) | Dipping solution of hydrogenation catalyst and preparation method of hydrogenation catalyst | |
| RU2732944C1 (en) | Method of producing low-sulphur diesel fuel | |
| CN106179388B (en) | A kind of preparation method of hydrotreating catalyst | |
| CN106179384B (en) | A kind of preparation method of Hydrobon catalyst | |
| CN109926075A (en) | A kind of high-activity hydrogenation catalyst and preparation method thereof | |
| CN109926072A (en) | A kind of hydrotreating catalyst and preparation method thereof | |
| CN106179377B (en) | A kind of preparation method of Hydrobon catalyst composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231009 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |