CN107970963B - A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil - Google Patents
A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil Download PDFInfo
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- CN107970963B CN107970963B CN201610920673.8A CN201610920673A CN107970963B CN 107970963 B CN107970963 B CN 107970963B CN 201610920673 A CN201610920673 A CN 201610920673A CN 107970963 B CN107970963 B CN 107970963B
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- Prior art keywords
- desulfurization
- weight
- hydrocarbon oil
- catalyst
- oxide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 155
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 133
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 133
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 133
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 128
- 230000023556 desulfurization Effects 0.000 title claims abstract description 126
- 238000000034 method Methods 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 46
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 39
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- 239000004927 clay Substances 0.000 claims abstract description 29
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 22
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 22
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 17
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 15
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- 239000010941 cobalt Substances 0.000 claims abstract description 14
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- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 4
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 3
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- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
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- 239000012018 catalyst precursor Substances 0.000 claims description 2
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- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- IJMWOMHMDSDKGK-UHFFFAOYSA-N Isopropyl propionate Chemical compound CCC(=O)OC(C)C IJMWOMHMDSDKGK-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- CCLUHSUSTSVOPJ-UHFFFAOYSA-N propan-2-ol;tin Chemical compound [Sn].CC(C)O CCLUHSUSTSVOPJ-UHFFFAOYSA-N 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- INZDTEICWPZYJM-UHFFFAOYSA-N 1-(chloromethyl)-4-[4-(chloromethyl)phenyl]benzene Chemical compound C1=CC(CCl)=CC=C1C1=CC=C(CCl)C=C1 INZDTEICWPZYJM-UHFFFAOYSA-N 0.000 abstract description 40
- 238000005299 abrasion Methods 0.000 abstract description 13
- 239000003921 oil Substances 0.000 description 97
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 43
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- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 1
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000011363 dried mixture Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- OWYGZENDPUIOCD-UHFFFAOYSA-N niobium(5+) oxygen(2-) tantalum(5+) Chemical compound [O-2].[Ta+5].[O-2].[Nb+5] OWYGZENDPUIOCD-UHFFFAOYSA-N 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000007686 potassium Nutrition 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/66—Pore distribution
- B01J35/695—Pore distribution polymodal
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to desulfurization of hydrocarbon oil field, the method for a kind of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil is disclosed.On the basis of the total weight of the desulfurization of hydrocarbon oil catalyst, which contains: 1) at least one metal oxide selected from IIB, VB and group vib element of 10~80 weight %；2) the non-aluminum oxide of 3~35 weight %, the non-aluminum oxide are at least one of titanium dioxide, zirconium dioxide and stannic oxide；3) vanadium carbide of 5~40 weight %；4) laminated clay column of 1~20 weight %；5) metallic promoter agent of 5~30 weight %, the metallic promoter agent are selected from least one of cobalt, nickel, iron and manganese.The desulfurization of hydrocarbon oil catalyst has better stability and higher desulphurizing activated, and better abrasion resistance properties, the service life is longer.
Description
Technical field
The present invention relates to desulfurization of hydrocarbon oil fields, and in particular, to a kind of desulfurization of hydrocarbon oil catalyst and preparation method thereof and hydrocarbon
The method of oily desulfurization.
Background technique
As people are to the pay attention to day by day of environmental protection, environmental regulation is also increasingly stringent, and reduces the sulphur of gasoline and diesel oil
Content is considered as improving one of the most important measure of air quality.Most of sulphur in China's gasoline products are from hot-working
Gasoline blending component, such as catalytically cracked gasoline.Therefore the reduction of sulfur content helps to reduce the production of China's gasoline in hot-working petroleum
The sulfur content of product.The existing gasoline products standard GB 17930-2011 " motor petrol " in China was required on December 31st, 2013,
Sulfur content must drop to 50 μ g/g in gasoline products.And following gasoline product quality standard will be more stringent.At this
In the case of kind, catalytically cracked gasoline, which has to pass through deep desulfuration just, can make gasoline products meet environmentally friendly requirement.
Currently, mainly selective catalytic desulfurhydrogenation and catalytic hydrogenation adsorb two kinds of desulfurization to the process for deep desulphurization of oil product
Method.Catalytic hydrogenation absorption desulfurization is to inhale the sulfide in hydrocarbon ils in certain temperature, pressure and realizing under conditions of face hydrogen
Attached removing, it is low and not high to the purity requirement of hydrogen which has the characteristics that hydrogen consumes, so that the technology is in terms of fuel desulfuration
It has broad application prospects.
CN1355727A discloses a kind of combination of adsorbents suitable for removing sulphur from cracking gasoline and diesel fuel
Object is made of zinc oxide, silica, oxidation al and ni, and wherein for nickel substantially to restore valence state presence, amount can be from de-
Sulphur is removed in the cracking gasoline or diesel fuel stream contacted under the conditions of sulphur with the nickeliferous adsorbent composition.The composition is logical
It crosses and is granulated to form particle by the compound particles that zinc oxide, silica and aluminium oxide are formed, use nickel or nickeliferous chemical combination after dry, roasting
Object dipping, re-dry, roasting, reduction obtain.
CN1382071A discloses a kind of combination of adsorbents suitable for removing sulphur from cracking gasoline and diesel fuel
Object is made of zinc oxide, silica, aluminium oxide and cobalt, and wherein for cobalt substantially to restore valence state presence, amount can be from de-
Sulphur is removed in the cracking gasoline or diesel fuel stream contacted under the conditions of sulphur with the adsorbent composition containing cobalt.
US6150300 discloses a kind of method for preparing adsorbent, including prepares spheric granules: will (a) contain silica
Composition, the composition containing dispersion metal oxide in an aqueous medium and the composition containing zinc oxide mix shape
First mixture is not squeezed out at the first mixture and；(b) forming first mixture at spherical shape has diameter 10-
The particle of 1000mm.Wherein step (a) further includes mixing with metallic promoter agent.
CN1422177A discloses a kind of combination of adsorbents suitable for removing sulphur from cracking gasoline and diesel fuel
Object is made of zinc oxide, expanded perlite, aluminium oxide and promoter metals, wherein the promoter metals are substantially to restore
Valence state and contact under desulfurization conditions in Shi Nengcong cracking gasoline or diesel fuel stream remove sulphur amount exist.
CN1627988A discloses one kind suitable for the removing elementary sulfur from cracking gasoline and diesel fuel and vulcanization conjunction
The adsorbent composition of object, the adsorbent composition includes: zinc oxide, expanded perlite, aluminate and promoter metals,
Described in promoter metals will lead to when making cracking gasoline or diesel fuel stream and it is contacted under desulfurization conditions from cracking
The amount of desulfurization in the stream of gasoline or diesel fuel exists, and at least partly described promoter metals exist with 0 valence state.
CN1856359A discloses a kind of method for producing composition, comprising: a) mixing liquid, zinc compound, contain two
Silica material, aluminium oxide and co-catalyst, to form its mixture；B) dry mixture, to form dried mixing
Object；C) the dried mixture is calcined, to form the mixture through calcining；D) under suitable condition with reducing agent appropriate
By mixture reduction through calcining, to produce the composition and e) of the co-catalyst content in it with reduction valence state
Recycling changes composition.Co-catalyst contains selected from various metals such as nickel.
CN1871063A discloses a kind of method for producing composition, this method comprises: a) by liquid, zinc compound,
It is mixed containing earth silicon material, aluminium oxide to form its mixture；B) dry this of the mixture is mixed to form first
Through drying composite；C) described first is calcined through drying composite to form first through calcining mixt；D) by promotor knot
Close described first through within calcining mixt or on formed be promoted mixture；E) mixture and choosing are promoted described in making
It contacts from the acid of citric acid, tartaric acid and combinations thereof to be formed through contact mixture；F) by it is described through contact mixture it is dry with
Second is formed through drying composite；G) described second is calcined through drying composite to form second through calcining mixt；H) exist
Suitable reducing agent reduction described second is used wherein to promote containing reduction valence state through calcining mixt to produce under the conditions of appropriate
Into agent content composition and i) recycle the composition.
Although published adsorbent has certain desulfurization performance, with the raising of gasoline quality standard, to product
Content of sulfur in gasoline requires also constantly stringent.And such catalyst is easy to happen abrasion in use, needs to be continuously replenished
Catalyst improves operating cost.It can be seen that, it is desirable to provide it is a kind of to be urged with more high desulfurization activity and the novel of abrasion resistance properties
Agent.
Summary of the invention
The purpose of the invention is to overcome the desulphurizing activated low, structural instability of the adsorbent of the prior art and wear resistance
Can difference defect, provide the method for a kind of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil.
To achieve the goals above, the present invention provides a kind of desulfurization of hydrocarbon oil catalyst, with the total of the desulfurization of hydrocarbon oil catalyst
On the basis of weight, which contains: 1) at least one of 10~80 weight % is selected from IIB, VB and group vib element
Metal oxide；2) the non-aluminum oxide of 3~35 weight %, the non-aluminum oxide are titanium dioxide, zirconium dioxide and two
At least one of tin oxide；3) vanadium carbide of 5~40 weight %；4) laminated clay column of 1~20 weight %；5) 5~30 weight
The metallic promoter agent of % is measured, the metallic promoter agent is selected from least one of cobalt, nickel, iron and manganese.
The present invention also provides the methods for preparing desulfurization of hydrocarbon oil catalyst of the invention, comprising: (1a) is by vanadium carbide, non-aluminum
Binder, water and acidic liquid contact to form slurries, by the slurries and laminated clay column, it is at least one selected from IIB, VB and
The metal oxide of group vib element is mixed to get carrier pulp；Or non-al binder, water and acidic liquid are contacted shape by (1b)
At slurries, by the slurries and laminated clay column, at least one metal oxide, vanadium carbide selected from IIB, VB and group vib element
It is mixed to get carrier pulp；(2) carrier pulp is formed, first dry, the first roasting, obtains carrier；(3) in institute
The precursor for introducing metallic promoter agent in carrier is stated, second dry and the second roasting is then carried out, obtains catalyst precarsor；(4) will
The catalyst precarsor restores in a hydrogen atmosphere, obtains desulfurization of hydrocarbon oil catalyst.
The present invention also provides desulfurization of hydrocarbon oil catalyst made from method of the invention.
The present invention also provides a kind of methods of desulfurization of hydrocarbon oil, comprising: in a hydrogen atmosphere, by hydrocarbon oil containing surphur and the present invention
The desulfurization of hydrocarbon oil catalyst of offer carries out desulphurization reaction at 350~500 DEG C, 0.5~4MPa.
Containing the stable vanadium carbide of chemical property (VC) in the composition of desulfurization of hydrocarbon oil catalyst provided by the invention, reduce
With the dependent interaction of the metal oxides such as zinc oxide, the formation such as silicic acid zinc material, such as the embodiment 1 that Fig. 1 is shown are avoided
The characteristic peak of zinc silicate is not present in XRD spectra after the hydrothermal aging of the desulfurization of hydrocarbon oil catalyst A1 of acquisition.The present invention provides
Desulfurization of hydrocarbon oil catalyst there is better stability and higher desulphurizing activated, can be during desulfurization of hydrocarbon oil more effectively
Sulphur in hydrocarbon ils is adsorbed on desulfurization of hydrocarbon oil catalyst, the lower hydrocarbon ils of sulfur content is obtained.And hydrocarbon ils provided by the invention
Desulphurization catalyst has better abrasion resistance properties, and catalyst attrition is lower in sweetening process, and the service life is longer.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is XRD spectrum of the obtained desulfurization of hydrocarbon oil catalyst A1 of embodiment 1 before and after hydrothermal aging；
Fig. 2 is XRD spectrum of the obtained desulfurization of hydrocarbon oil catalyst B1 of comparative example 1 before and after hydrothermal aging.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of desulfurization of hydrocarbon oil catalyst, on the basis of the total weight of the desulfurization of hydrocarbon oil catalyst, the hydrocarbon ils
Desulphurization catalyst contains: 1) at least one metal oxide selected from IIB, VB and group vib element of 10~80 weight %；2)3
The non-aluminum oxide of~35 weight %, the non-aluminum oxide are at least one in titanium dioxide, zirconium dioxide and stannic oxide
Kind；3) vanadium carbide of 5~40 weight %；4) laminated clay column of 1~20 weight %；5) metallic promoter agent of 5~30 weight %, institute
It states metallic promoter agent and is selected from least one of cobalt, nickel, iron and manganese.
Preferably, on the basis of the total weight of the desulfurization of hydrocarbon oil catalyst, the total weight with the desulfurization of hydrocarbon oil catalyst is
Benchmark, the desulfurization of hydrocarbon oil catalyst contain the metal oxide of 25~70 weight %, the non-alumina of 6~25 weight %
Compound, the vanadium carbide of 10~30 weight %, the laminated clay column of 2~15 weight %, the metal promoted of 8~25 weight %
Agent.
It is highly preferred that on the basis of the total weight of the desulfurization of hydrocarbon oil catalyst, with the total weight of the desulfurization of hydrocarbon oil catalyst
On the basis of, which contains the metal oxide of 40~60 weight %, the non-aluminum of 8~15 weight %
Oxide, the vanadium carbide of 12~25 weight %, the laminated clay column of 2~10 weight %, the metal of 12~20 weight %
Promotor.
In the present invention, the content of each component in the desulfurization of hydrocarbon oil catalyst can be measured by XRD crystal phase analysis method.
According to the present invention, in the spectrogram that the desulfurization of hydrocarbon oil catalyst is obtained through XRD analysis 2 θ be 37.3 °, 43.36 °
With 63.10 ° at there are the crystal phase peaks of vanadium carbide.
Contain the vanadium carbide with face-centered cubic crystal structure in desulfurization of hydrocarbon oil catalyst provided by the invention as structure
Constituent element can be effectively prevented from since the structure vanadium carbide has very high hydrothermal stability during carrying out desulfurization of hydrocarbon oil
Such as silicic acid zinc material is formed in the composition of the catalyst, guarantees that the catalyst has better desulphurizing activated and stability.Preferably,
The desulfurization of hydrocarbon oil catalyst is not have at 22.0 °, 25.54 °, 48.9 ° and 59.4 ° in 2 θ in the XRD spectra after hydrothermal aging
Occur the characteristic peak of zinc silicate.The condition of the hydrothermal aging include: temperature be 500~700 DEG C, steam partial pressure be 10~
30kPa, processing the time be 10~for 24 hours.
According to the present invention, the laminated clay column is interstratified minerals crystal, is handed over by two kinds of single layer mineral clay component rules
For rearranging, bottom surface spacing is not less than 1.7nm.Under preferable case, what the desulfurization of hydrocarbon oil catalyst was obtained through XRD analysis
There are the characteristic peaks of the laminated clay column at 2 θ is 3.4 ° in spectrogram.Preferably, the example of the laminated clay column includes but not
It is limited at least one of rectorite, Yun Mengshi, bentonite, montmorillonite and smectite, it is preferable that the laminated clay column is tired support
Soil.
According to the present invention, at least one metal oxide selected from IIB, VB and group vib element can for zinc oxide,
At least one of cadmium oxide, vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide and tungsten oxide, it is described under preferable case
Metal oxide is at least one of zinc oxide, molybdenum oxide and vanadium oxide；It is highly preferred that the metal oxide is oxidation
Zinc.
In accordance with the present invention it is preferred that the metallic promoter agent is nickel and/or cobalt, the desulfurization of hydrocarbon oil catalyst can have
There is higher desulphurizing activated and regenerability；It can the metallic promoter agent be further preferably nickel.
In the case of, according to the invention it is preferred to, the non-aluminum oxide is aluminium oxide, titanium dioxide, zirconium dioxide and dioxy
Change at least one of tin.Preferably, the non-aluminum oxide provides viscous between each component in the desulfurization of hydrocarbon oil catalyst
Knot effect.
In the present invention, the desulfurization of hydrocarbon oil catalyst can also contain other components, as desulphurization catalyst can contain
Component, such as clay, molecular sieve, alkali metal oxide etc..Wherein the content of clay can be 1~10 weight %, molecular sieve
Content can be 5~20 weight %, and the content of alkali metal oxide is 0.1~5 weight %.
In the present invention, the clay can be selected from raw clay well-known to those skilled in the art, common clay kind
Class may be incorporated for the present invention, and the preferably described clay can be selected from kaolin, halloysite, montmorillonite, diatomite, Ai Luo
One of stone, halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite are a variety of.
In the present invention, the molecular sieve can be selected from MFI structure molecular sieve, SAPO structure molecular screen, FAU structure molecular screen
At least one of with BEA structure molecular screen.FAU structure molecular screen can for X-type molecular sieve, Y type molecular sieve, USY, REUSY,
At least one of REHY, REY, PUSY, PREHY and PREY, SiO2: Al2O3Molar ratio be (1~4): 1.BEA structural molecule
Sieve can be beta-molecular sieve, SiO2: Al2O3Molar ratio be (5~10): 1.SAPO molecular sieve is SAPO-5, SAPO-11, SAPO-
31, at least one of SAPO-34 and SAPO-20.MFI structure molecular sieve can be for ZSM-5 molecular sieve and/or using phosphorus or mistake
Cross metal-modified ZSM-5 molecular sieve；It preferably, can be at least one of ZSM-5, ZRP-1 and ZSP-3, SiO2: Al2O3
Molar ratio be (15~100): 1.
In the present invention, the alkali metal oxide can be sodium oxide molybdena and/or potassium oxide.
The present invention also provides a kind of methods for preparing desulfurization of hydrocarbon oil catalyst of the invention, comprising: (1a) by vanadium carbide,
Non- al binder, water and acidic liquid contact to form slurries, and the slurries and laminated clay column, at least one are selected from IIB, VB
Carrier pulp is mixed to get with the metal oxide of group vib element；Or (1b) contacts non-al binder, water and acidic liquid
Slurries are formed, by the slurries and laminated clay column, at least one metal oxide selected from IIB, VB and group vib element, carbonization
Vanadium is mixed to get carrier pulp；(2) carrier pulp is formed, first dry, the first roasting, obtains carrier；(3) exist
The precursor of metallic promoter agent is introduced in the carrier, is then carried out second dry and the second roasting, is obtained catalyst precarsor；(4)
The catalyst precarsor is restored under hydrogen atmosphere, obtains desulfurization of hydrocarbon oil catalyst.
According to the present invention, the vanadium carbide used selects specific structure that can provide desulfurization of hydrocarbon oil catalyst with preferably resistance to
Grind performance and desulphurizing activated.Under preferable case, vanadium carbide has face-centered cubic crystal structure, in the form of sheets or column structure.It is preferred that
Ground, the grain diameter of vanadium carbide are 2~30 μm, preferably 3~15 μm.Preferably, the specific surface area of vanadium carbide is 10m2/ g~
50m2/g；Preferably 20m2/ g~35m2/g。
In preparation method of the invention, being added for the metal oxide can be for the powder shape of the metal oxide
Formula is added, and is added in form of slurry again after water can also being added to be mixed into slurries the metal oxide.
In the present invention, at least one metal oxide selected from IIB, VB and group vib element can be zinc oxide, oxygen
At least one of cadmium, vanadium oxide, niobium oxide tantalum oxide, chromium oxide, molybdenum oxide and tungsten oxide；Preferably zinc oxide, oxidation
At least one of molybdenum and vanadium oxide；More preferably zinc oxide.
According to the present invention, as previously mentioned, the laminated clay column is rectorite, Yun Mengshi, bentonite, montmorillonite and smectite
At least one of；Preferably rectorite.
In the case of, according to the invention it is preferred to, non-al binder is selected from titanium dioxide binder, zirconium dioxide binder and two
At least one of tin oxide binder.
Preferably, the titanium dioxide binder is to hydrolyze in the acidic liquid, and in first roasting condition
Under be changed into the substance of anatase titanium dioxide.Further, the titanium dioxide binder can be selected from titanium tetrachloride, titanium
At least one of acetoacetic ester, isopropyl titanate, acetic acid titanium, hydrous titanium oxide and anatase titanium dioxide.
Preferably, the zirconium dioxide binder is to hydrolyze in the acidic liquid, and in first roasting condition
Under be changed into the substance of zirconium dioxide.Further, the zirconium dioxide binder can selected from zirconium chloride, zirconium oxychloride,
At least one of acetic acid zirconium, hydrous zirconium oxide(HZO) and amorphous zirconium dioxide.
Preferably, the stannic oxide binder is to hydrolyze in the acidic liquid, and in first roasting condition
Under be changed into the substance of stannic oxide.Further, the stannic oxide binder can be selected from tin tetrachloride, four isopropanols
At least one of tin, tin acetate, aqua oxidation tin and stannic oxide.
In the present invention, the titanium dioxide binder, zirconium dioxide binder and stannic oxide binder are molten with excess acid
Liquid contact, can hydrolyze and generate caking property colloidal solution.
According to the present invention, the acidic liquid can be acid or the aqueous solution of acid, and the acid can be selected from water-soluble
Inorganic acid and/or organic acid, the preferably described acid can be at least one of hydrochloric acid, nitric acid, phosphoric acid and acetic acid.
In the case of, according to the invention it is preferred to, the dosage of the acidic liquid makes the pH value 1~5 of the carrier pulp, excellent
It is selected as 1.5~4.
In the present invention, step (1a) and (1b) middle amount that water is added can be not specially limited, as long as can obtain described
Carrier pulp.Such as it is 5:1~10:1 that the amount of water and the weight ratio of the non-al binder, which is added,；Or the amount of water is added
Weight ratio with the weight summation of the non-al binder and vanadium carbide is 5:1~10:1.
In the present invention, it can also be added other components for preparing desulphurization catalyst in step (1a) and (1b), such as clay,
Molecular sieve, precursor of alkali metal oxide etc..Clay, molecular sieve are as previously mentioned, repeat no more.The preceding body of alkali metal oxide
Body can be to be changed into the substance of alkali metal oxide, such as alkali metal oxide, alkali under the first roasting condition of step (2)
Nitrate, alkali metal sulfates, the alkali metal phosphate of metal, such as sodium oxide molybdena, potassium oxide, sodium nitrate, nitric acid can be selected from
At least one of potassium, potassium sulfate, sodium sulphate, potassium phosphate and sodium phosphate.
In the present invention, the obtained carrier pulp can be the forms such as paste or slurries.It can be by the carrier pulp
Dry reshaping after thickening.The more preferable carrier pulp is slurry form, and it is 20~200 that granularity can be formed by spray drying
μm microballoon, reach molding purpose.For the ease of spray drying, it is dry before the carrier pulp solid content can for 10~
50 weight %, preferably 20~50 weight %.It can also include that water is added during obtaining the carrier pulp, water adds
Entering amount, there is no particular limitation, as long as obtained carrier pulp meets above-mentioned solid content.
In the present invention, the first drying means and condition in step (2) are known to those skilled in the art, such as dry
Method can be dry, dry, forced air drying.Under preferable case, the described first dry temperature can be room temperature~400
DEG C, preferably 100~350 DEG C；Described first dry time be 0.5h or more, preferably 0.5~100h, more preferably 2~
20h。
In the present invention, the first roasting condition in step (2) is also known to those skilled in the art, under preferable case,
The temperature of first roasting is 400~700 DEG C, preferably 450~650 DEG C；The time of first roasting is at least 0.5h,
Preferably 0.5~100h, more preferably 0.5~10h.
According to the present invention, for step (3) for metallic promoter agent to be added, the metallic promoter agent is as previously shown.The metal
The precursor of promotor is the substance that can be changed into the oxide of metallic promoter agent under the second roasting condition；Under preferable case,
The precursor of the metallic promoter agent can be selected from acetate, carbonate, nitrate, sulfate, the rhodanate of metallic promoter agent
At least one of with oxide.It is preferred that the precursor of the metallic promoter agent can be at least one of cobalt, nickel, iron and manganese
At least one of acetate, carbonate, nitrate, sulfate, rhodanate and oxide；The preferably vinegar of nickel and/or cobalt
At least one of hydrochlorate, carbonate, nitrate, sulfate, rhodanate and oxide；Can be preferably nickel nitrate and/or
Cobalt nitrate；More preferably at least one of the acetate of nickel, carbonate, nitrate, sulfate, rhodanate and oxide；
Particularly preferably nickel nitrate.
In the case of, according to the invention it is preferred to, the method that the precursor of metallic promoter agent is introduced on carrier is dipping or precipitating.
The dipping can be the solution or suspension impregnation carrier with the precursor of metallic promoter agent；The precipitating can be to promote metal
Solution or suspension into the precursor of agent are mixed with carrier, and ammonium hydroxide is then added by the precursor precipitation of metallic promoter agent in carrier
On.
In the case of, according to the invention it is preferred to, the described second dry temperature is 50~300 DEG C, preferably 100~250 DEG C；
Described second dry time was 0.5~8h, preferably 1~5h.
Preferably, the temperature of second roasting is 300~800 DEG C, preferably 450~750 DEG C；Second roasting
Time is 0.5h or more, preferably 1~3h.Second roasting can carry out in the presence of oxygen or oxygen-containing gas, until
Volatile materials is removed and the precursor of metallic promoter agent is converted into the oxide form of metallic promoter agent, obtains catalyst
Precursor.
According to the present invention, in step (4), the oxide of the metallic promoter agent in the catalyst precarsor is changed into metal
The catalyst precarsor can be restored under hydrogen atmosphere, deposit metallic promoter agent substantially with reduction-state by simple substance
Obtaining catalyst of the invention.The condition of the reduction is only by the oxide of the metallic promoter agent in the catalyst precarsor
It is changed into metal simple-substance, and the metal oxide in the carrier will not change.Under preferable case, the temperature of the reduction is
300~600 DEG C, preferably 400~500 DEG C；The time of the reduction is 0.5~6h, preferably 1~3h；The hydrogen gas
The content of hydrogen is 10~60 volume % in atmosphere.
In the present invention, step (4) can carry out catalyst precarsor reduction immediately after catalyst precarsor is made, can also be with
It is carried out (before being adsorbed for desulfurization) before use.Metal since metallic promoter agent is easy to oxidize, and in catalyst precarsor promotees
Exist in the form of an oxide into agent, therefore to be readily transported, catalyst precarsor is restored and carrying out desulfurization absorption by preferred steps (4)
Preceding progress.It is described to be reduced to make the metal in the oxide of metallic promoter agent substantially to exist with reduction-state, it obtains of the invention
Desulphurization catalyst.
In the case of, according to the invention it is preferred to, the non-al binder, vanadium carbide, the metal oxide, the layer column are viscous
In the desulfurization of hydrocarbon oil catalyst that the additional amount of the precursor of the native and described metallic promoter agent makes, with desulfurization of hydrocarbon oil catalysis
On the basis of the total weight of agent, the desulfurization of hydrocarbon oil catalyst contains the metal oxide of 10~80 weight %, preferably comprises
25~70 weight %, further preferably 40~60 weight %；The non-aluminum oxide containing 3~35 weight %, preferably comprises 6
~25 weight %, further preferably 8~15 weight %；Vanadium carbide containing 5~40 weight %, preferably comprises 10~30 weights
Measure %, further preferably 12~25 weight %；The laminated clay column containing 1~20 weight %, preferably comprises 2~15 weights
Measure %, further preferably 2~10 weight %；The metallic promoter agent containing 5~30 weight %, preferably comprises 8~25 weights
Measure %, further preferably 12~20 weight %.
The dosage that other components can be added in method provided by the invention, the desulfurization of hydrocarbon oil catalysis that can make
In agent, the clay containing 1~10 weight %, the molecular sieve of 5~20 weight %, the alkali metal oxide of 0.1~5 weight %.
The present invention also provides desulfurization of hydrocarbon oil catalyst made from method of the invention.
The present invention also provides a kind of methods of desulfurization of hydrocarbon oil, this method comprises: in a hydrogen atmosphere, by hydrocarbon oil containing surphur with
Desulfurization of hydrocarbon oil catalyst provided by the invention carries out desulphurization reaction at 350~500 DEG C, 0.5~4MPa；Preferably, 400~
450 DEG C, carry out desulphurization reaction under 1.0~2.0MPa.The sulphur in hydrocarbon ils is adsorbed on catalyst in the process, to obtain
The hydrocarbon ils of low sulfur content.
In the present invention, the catalyst after reaction can be reused after regeneration.The regeneration carries out under oxygen atmosphere,
Regenerated condition includes: that regenerated pressure is normal pressure, and regenerated temperature is 400~700 DEG C, preferably 500~600 DEG C.
In the present invention, the catalyst after regeneration is before re-starting desulfurization of hydrocarbon oil, it is also necessary to it is restored under hydrogen atmosphere,
The reducing condition of catalyst after regeneration includes: that temperature is 350~500 DEG C, preferably 400~450 DEG C；Pressure be 0.2~
2MPa, preferably 0.2~1.5MPa.
In the present invention, being related to pressure is gauge pressure.
In the present invention, the hydrocarbon ils includes cracking gasoline and diesel fuel, wherein " cracking gasoline " means that boiling range is 40
It is from making biggish hydrocarbon molecule be cracked into heat or catalytic process compared with small molecule DEG C to 210 DEG C of hydrocarbon or its any fraction
Product.Applicable thermal cracking process includes but is not limited to coking, thermal cracking and visbreaking etc. and combinations thereof.Applicable catalysis
The example of cracking process includes but is not limited to fluid catalystic cracking and heavy oil catalytic cracking etc. and combinations thereof.Therefore, applicable
Catalytically cracked gasoline include but is not limited to coker gasoline, pressure gasoline, visbreaker gasoil, fluid catalystic cracking gasoline and
Heavy oil cracked gasoline and combinations thereof.In some cases, in the methods of the invention be used as hydrocarbon-containifluids fluids when can before desulfurization incite somebody to action
The cracking gasoline fractionation and/or hydrotreating.The hydrocarbon that " diesel fuel " means that boiling range is 170 DEG C to 450 DEG C mixes
The liquid of object or its any fractional composition.Such hydrocarbon-containifluids fluids include but is not limited to light cycle oil, kerosene, straight-run diesel oil and add hydrogen
Handle diesel oil etc. and combinations thereof.
Term used herein " sulphur " represents any type of element sulphur such as hydrocarbon-containifluids fluids such as cracking gasoline or diesel engine combustion
The organosulfur compound being commonly present in material.Sulphur present in hydrocarbon-containifluids fluids of the present invention includes but is not limited to carbonyl sulfide (COS), two
Nitric sulfid (CS2), mercaptan or other thiophenes etc. and combinations thereof, especially include thiophene, benzothiophene, alkylthrophene,
The bigger thiophene-based chemical combination of the molecular weight being commonly present in alkyl benzothiophenes and methyldibenzothiophene and diesel fuel
Object.
Contain vanadium carbide component in the composition of desulfurization of hydrocarbon oil catalyst provided by the invention, the component is in the multiple of catalyst
It is not easy the effect of reacting with zinc oxide component in reaction and regenerative process, will not produce silicic acid zinc material urges the desulfurization of hydrocarbon oil
Agent reduces desulphurizing activated because losing zinc oxide.Catalyst of the present invention has very high desulphurizing activated, while also having obvious
Increase catalyst abrasion strength resistance property, be applicable to the reaction repeatedly and regeneration of catalytically cracked gasoline or diesel fuel
Sweetening process.
The present invention will be described in detail by way of examples below.
The desulfurization of hydrocarbon oil catalyst that embodiment and comparative example obtains uses X-ray diffractometer (Siemens company D5005 type)
XRD spectra is obtained, structure determination, Cu target, K α radiation, solid probe, tube voltage 40kV, tube current 40mA are carried out；
Vanadium carbide used in embodiment is vanadium carbide -1, vanadium carbide -2 and vanadium carbide -3, is had by Sinopec catalyst
Nanjing branch company, limit company provides, and specific structural features are shown in Table 1,
Table 1
* it is measured by laser particle analyzer (Mastersizer 2000 of Malvern company).
In the following Examples and Comparative Examples, the composition of desulfurization of hydrocarbon oil catalyst is calculated according to feeding intake.
Embodiment 1
This example demonstrates that the preparation method of desulfurization of hydrocarbon oil catalyst of the invention.
The titanium tetrachloride (Beijing Chemical Plant analyzes pure, 99 weight %) of 3.25kg is slowly added to the 5 weight % of 4.6kg
Dilute hydrochloric acid, be slowly stirred and crystalline titanium dioxide avoided to be precipitated, obtain the titanium colloidal sol pH=2.0 of pale yellow transparent；
(1) carrier is prepared.By Zinc oxide powder (Headhorse company, 99.7 weight % of purity), the 0.93kg of 4.43kg
Rectorite (catalyst asphalt in Shenli Refinery, contain butt 0.70kg), the deionized water of the vanadium carbide -1 of 2.06kg and 6.57kg it is mixed
It closes, obtains the mixed serum of zinc oxide, rectorite and vanadium carbide after stirring 30min；Then above-mentioned titanium colloidal sol is added, is stirred after mixing
It mixes 1h and obtains carrier pulp；
The carrier pulp is used into Niro Bowen Nozzle TowerTMThe spray dryer of model is done by spraying
Dry, spray drying pressure is 8.5 to 9.5MPa, and 500 DEG C of inlet temperature is hereinafter, outlet temperature is about 150 DEG C.By being spray-dried
The first 1h dry at 180 DEG C of the microballoon arrived, then roasts 1h at 635 DEG C and obtains carrier；
(2) catalyst precarsor processed.By the carrier of 3.2kg with the Nickelous nitrate hexahydrate of 3.51kg (Beijing chemical reagents corporation,
98.5 weight % of purity >) and 0.6kg deionized water solution dipping, obtained dipping object is after 180 DEG C of dry 4h, in sky
Catalyst precarsor is made in 635 DEG C of roasting 1h of gas atmosphere；
(3) it restores.By catalyst precarsor in hydrogen atmosphere reductase 12 h at 425 DEG C, obtain desulfurization of hydrocarbon oil catalyst A1.
The chemical composition of A1 are as follows: zinc oxide content is 44.3 weight %, and carbonization content of vanadium is 20.6 weight %, and rectorite contains
Amount is 7.0 weight %, and content of titanium dioxide is 10.0 weight %, and nickel content is 18.1 weight %.
Embodiment 2
This example demonstrates that the preparation method of desulfurization of hydrocarbon oil catalyst of the invention.
Titanium dioxide 1.25kg (Detitanium-ore-type, contain butt 1.17kg) is taken to be added to the deionized water and 1.0kg of 1.8kg
In the hydrochloric acid (chemistry is pure, and Beijing Chemical Plant produces) of 30 weight %, pH=1.9 is stirred to react 1h, obtains the titanium of pale yellow transparent
Colloidal sol；
By the vanadium carbide -2 of 1.50kg, 0.4kg montmorillonite (catalyst asphalt in Shenli Refinery, contain butt 0.30kg),
The Zinc oxide powder of 5.52kg and the deionized water of 10.0kg mix under stiring, obtain zinc oxide, montmorillonite and vanadium carbide
Mixed serum, above-mentioned titanium colloidal sol be then added and stirs 1h obtain carrier pulp；
Method referring to embodiment 1 carries out the spray drying forming of carrier pulp and introduces active component nickel, after reduction
To desulfurization of hydrocarbon oil catalyst A2.
The chemical composition of A2 are as follows: zinc oxide content is 55.2 weight %, and carbonization content of vanadium is 15.0 weight %, titanium dioxide
Content is 11.7 weight %, and montmorillonite content is 3.0 weight %, and nickel content is 15.1 weight %.
Embodiment 3
This example demonstrates that the preparation method of desulfurization of hydrocarbon oil catalyst of the invention.
Tetraethyl titanate 3.90kg (Aldrich analyzes pure, 99 weight %) and the deionized water of 1.6kg is taken to stir
In the case where be slowly added into 3.8kg 10 weight % nitric acid (analysis pure, Beijing Chemical Plant produce) solution in, pH=2.3,
And 1h is stirred, obtain the titanium colloidal sol of pale yellow transparent；
By the Zinc oxide powder of 4.93kg, 0.66kg rectorite (catalyst asphalt in Shenli Refinery, contain butt 0.50kg),
The deionized water mixing of the vanadium carbide -3 and 10.8kg of 1.6kg, obtains zinc oxide, class support support and vanadium carbide after stirring 30min
Then mixed serum is added titanium colloidal sol and stirs 1h and obtain carrier pulp；
The spray drying forming of carrier pulp is carried out referring to the method for embodiment 1.
Catalyst precarsor and catalyst are prepared referring to the method for embodiment 1, unlike, it is molten with nickel nitrate and cobalt nitrate
Liquid substitutes Nickelous nitrate hexahydrate impregnated carrier, introduces active component nickel and cobalt, desulfurization of hydrocarbon oil catalyst A3 is obtained after reduction.
The chemical composition of A3 are as follows: zinc oxide content is 49.3 weight %, and carbonization content of vanadium is 16.0 weight %, titanium dioxide
Content is 13.5 weight %, and rectorite content is 5.0 weight %, and nickel content is 8.1 weight %, and cobalt content is 8.1 weight %.
Embodiment 4
This example demonstrates that the preparation method of desulfurization of hydrocarbon oil catalyst of the invention.
Tetraethyl titanate 3.90kg (Aldrich analyzes pure, 99 weight %) and the deionized water of 1.6kg is taken to stir
In the case where be slowly added into 3.8kg 10 weight % nitric acid (analysis pure, Beijing Chemical Plant produce) solution in, pH=2.3,
And 1h is stirred, obtain the titanium colloidal sol of pale yellow transparent；
By the Zinc oxide powder of 4.93kg, the vanadium carbide -1 of 1.6kg, 0.66kg rectorite (catalyst asphalt in Shenli Refinery,
Deionized water mixing containing butt 0.50kg) and 8.8kg, obtains the mixing of zinc oxide, rectorite and vanadium carbide after stirring 30min
Slurries；Then titanium colloidal sol is added and stirs 1h and obtains carrier pulp；
Method referring to embodiment 1 carries out the spray drying forming of carrier pulp and introduces active component nickel, after reduction
To desulfurization of hydrocarbon oil catalyst A4.
The chemical composition of A4 are as follows: zinc oxide content is 49.3 weight %, and carbonization content of vanadium is 16.0 weight %, titanium dioxide
Content is 13.5 weight %, and rectorite content is 5.0 weight %, and nickel content is 16.2 weight %.
Embodiment 5
This example demonstrates that the preparation method of desulfurization of hydrocarbon oil catalyst of the invention.
The zirconium chloride (Beijing Chemical Plant analyzes pure, 99 weight %) of 2.60kg is slowly added to the deionization of 5.0kg
Water, and the nitric acid solution of the 5 weight % of 4.6kg is added, it is slowly stirred and zirconium oxide crystallization is avoided to be precipitated, obtain pale yellow transparent
Zirconium colloidal sol pH=2.1；
By the Zinc oxide powder (Headhorse company, 99.7 weight % of purity) of 4.43kg, 1.40kg vanadium carbide -2,
The rectorite (catalyst asphalt in Shenli Refinery contains butt 1.0kg) and the deionized water of 6.57kg of 1.32kg mixes, and stirs 30min
The mixed serum of zinc oxide, rectorite and vanadium carbide is obtained afterwards；Then above-mentioned zirconium colloidal sol is added, 1h is stirred after mixing and obtains carrier
Slurries；
Method referring to embodiment 1 carries out the spray drying forming of carrier pulp and introduces active component nickel, after reduction
To desulfurization of hydrocarbon oil catalyst A5.
The chemical composition of A5 are as follows: zinc oxide content is 44.3 weight %, and carbonization content of vanadium is 14.0 weight %, and rectorite contains
Amount is 10.0 weight %, and zirconium dioxide content is 13.6 weight %, and nickel content is 18.1 weight %.
Embodiment 6
This example demonstrates that the preparation method of desulfurization of hydrocarbon oil catalyst of the invention.
By the tin tetrachloride (SnCl of 3.21kg4·5H2O, Alfa company, 99%) it is slowly added to the deionized water of 4.6kg,
And the nitric acid solution of the 5 weight % of 4.6kg is added, it is slowly stirred and oxidation tin crystals is avoided to be precipitated, it is molten to obtain colorless and transparent tin
Glue pH=2.1；
By the Zinc oxide powder (Headhorse company, 99.7 weight % of purity) of 4.43kg, 1.40kg vanadium carbide -3,
The rectorite (catalyst asphalt in Shenli Refinery contains butt 1.0kg) and the deionized water of 6.57kg of 1.32kg mixes, and stirs 30min
The mixed serum of zinc oxide, rectorite and vanadium carbide is obtained afterwards；Then above-mentioned tin oxide sol is added, 1h is stirred after mixing and obtains carrier
Slurries；
Method referring to embodiment 1 carries out the spray drying forming of carrier pulp and introduces active component nickel, after reduction
To desulfurization of hydrocarbon oil catalyst A6.
The chemical composition of A6 are as follows: zinc oxide content is 44.3 weight %, and carbonization content of vanadium is 24.0 weight %, and rectorite contains
Amount is 10.0 weight %, and stannic oxide content is 13.6 weight %, and nickel content is 18.1 weight %.
Comparative example 1
The deionized water of the Zinc oxide powder of 4.43kg and 6.57kg are mixed, obtain zinc oxide slurries after stirring 30min；
Take the expanded perlite of boehmite 1.81kg (catalyst Nanjing branch company contains butt 1.36kg) and 2.46kg
(catalyst Nanjing branch company contains butt 2.40kg) is stirred, and deionized water 4.6kg is then added and is uniformly mixed, adds
The hydrochloric acid of the 30 weight % of 360ml makes slurries pH=2.1, is warming up to 80 DEG C of aging 2h after stirring acidification 1h, adds zinc oxide
Stirring 1h obtains carrier pulp after slurries mixing.
Method referring to embodiment 1 carries out the spray drying forming of carrier pulp and introduces active component nickel, after reduction
To desulfurization of hydrocarbon oil catalyst B1.
The chemical composition of B1 are as follows: zinc oxide content is 44.3 weight %, and expanded perlite content is 24.0 weight %, oxidation
Aluminium content is 13.6 weight %, and nickel content is 18.1 weight %.
Comparative example 2
Boehmite 1.56kg (Shandong Aluminum Plant produces, and contains butt 1.17kg) and the diatomite of 1.85kg is taken (to contain butt
It 1.80kg) is stirred, deionized water 8.2kg is then added and is uniformly mixed, the hydrochloric acid for adding the 30 weight % of 260ml makes to starch
80 DEG C of aging 2h are warming up to after liquid pH=1.9, stirring acidification 1h.The Zinc oxide powder of 5.52kg is added simultaneously after temperature reduction
Stirring 1h obtains carrier pulp.
Method referring to embodiment 1 carries out the spray drying forming of carrier pulp and introduces active component nickel, after reduction
To desulfurization of hydrocarbon oil catalyst B2.
The chemical composition of B2 are as follows: zinc oxide content is 55.2 weight %, and diatomite content is 18.0 weight %, and aluminium oxide contains
Amount is 11.7 weight %, and nickel content is 15.1 weight %.
Comparative example 3
The deionized water of the Zinc oxide powder of 4.93kg and 5.57kg are mixed, obtain zinc oxide slurries after stirring 30min；
Take diatomite (world's mine of boehmite 1.80kg (Shandong Aluminum Plant produces, and contains butt 1.35kg) and 2.16kg
Industry company contains butt 2.10kg) it is stirred, deionized water 4.6kg is then added and is uniformly mixed, adds 30 weights of 300ml
The hydrochloric acid of amount % makes slurries pH=2.5, is warming up to 80 DEG C of aging 2h after stirring acidification 1h.It is stirred after adding the mixing of zinc oxide slurries
It mixes 1h and obtains carrier pulp.
Method referring to embodiment 3 carries out the spray drying forming of carrier pulp and introduces active component nickel and cobalt, restores
After obtain desulfurization of hydrocarbon oil catalyst B3.
The chemical composition of B3 are as follows: zinc oxide content is 49.3 weight %, and diatomite content is 21.0 weight %, and aluminium oxide contains
Amount is 13.5 weight %, and nickel content is 8.1 weight %, and cobalt content is 8.1 weight %.
Comparative example 4
The deionized water of the Zinc oxide powder of 4.93kg and 5.57kg are mixed, obtain zinc oxide slurries after stirring 30min；
Taking boehmite 1.80kg (Shandong Aluminum Plant produces, and contains butt 1.35kg) and the kaolin of 2.84kg, (Suzhou is high
Ling Tu factory contains butt 2.10kg) it is stirred, deionized water 3.6kg is then added and is uniformly mixed, adds 30 weights of 300ml
The hydrochloric acid of amount % makes slurries pH=2.5, is warming up to 80 DEG C of aging 2h after stirring acidification 1h.It is stirred after adding the mixing of zinc oxide slurries
It mixes 1h and obtains carrier pulp.
Method referring to embodiment 1 carries out the spray drying forming of mixing taste and introduces active component nickel, obtains after reduction
Desulfurization of hydrocarbon oil catalyst B4.
The chemical composition of B4 are as follows: zinc oxide content is 49.3 weight %, and kaolin content is 21.0 weight %, and aluminium oxide contains
Amount is 13.5 weight %, and nickel content is 16.2 weight %.
Comparative example 5
According to the method for embodiment 1, it unlike, is prepared according to embodiment 2 in CN101774593A ordered porous
It is de- to obtain hydrocarbon ils with the vanadium carbide -1 of the ordered porous carbonitride of silicium material substitution 2.40kg of 2.40kg for carbonitride of silicium material
Sulfur catalyst B5.
The chemical composition of B5 are as follows: zinc oxide content is 44.3 weight %, and ordered porous carbonitride of silicium material content is 24.0
Weight %, alumina content are 13.6 weight %, and nickel content is 18.1 weight %.
Embodiment 7
(1) abrasion strength resistance is evaluated.Abrasion strength resistance test is carried out to desulfurization of hydrocarbon oil catalyst A1-A6 and B1-B5.Using
Straight tube wears method, and method the results are shown in Table 2 with reference to RIPP 29-90 in " petrochemical analysis method (RIPP) experimental method ".It surveys
It is smaller to try obtained numerical value, shows that abrasion strength resistance is higher.It is thin when wearing under certain condition that abrasion index is corresponding in table 2
The percentage that powder generates.
(2) desulfurization performance is evaluated.To desulfurization of hydrocarbon oil catalyst A1-A6 and B1-B5 using the micro- anti-experimental provision of fixed bed into
Row HDS evaluation experiment, by the desulfurization of hydrocarbon oil Catalyst packing of 16g in the fixed bed reactors that internal diameter is 30mm, a length of 1m.
Catalytically cracked gasoline of the raw material hydrocarbon ils for sulphur concentration 780ppm, reaction pressure 1.38MPa, hydrogen flowing quantity are
6.3L/h, gasoline flow 80mL/h, reaction temperature are 410 DEG C, and the weight space velocity of raw material hydrocarbon ils is 4h-1, carry out hydrocarbon oil containing surphur
Desulphurization reaction.
It is measured with sulfur content in product gasoline desulphurizing activated.Sulfur content passes through offline chromatogram analysis method in product gasoline,
It is measured using the GC6890-SCD instrument of An Jielun company.
In order to which accurate characterization goes out activity of the desulfurization of hydrocarbon oil catalyst in industrial actual motion, after the completion of HDS evaluation experiment
Catalyst regeneration treatment is carried out under 550 DEG C of air atmosphere.Desulfurization of hydrocarbon oil catalyst is subjected to HDS evaluation experiment, regeneration
Its activity settles out substantially after 6 circulations, indicates to urge with the sulfur content in the product gasoline after the 6th stable circulation of catalyst
The activity of agent, sulfur content and liquid yield are as shown in table 2 in product gasoline after stablizing.
Desulfurization of hydrocarbon oil catalyst A1-A6 and the B1-B5 working sulfur capacity for carrying out desulfurization of hydrocarbon oil are calculated, the results are shown in Table 4.Its
In, penetrating in working sulfur capacity refers to: fresh desulfurization of hydrocarbon oil catalyst is taken off under above-mentioned desulfurization performance evaluation condition
Reaction of Salmon-Saxl is 10 μ g/g or more until reacting sulfur content in the product hydrocarbon oil obtained, that is, defines desulfurization of hydrocarbon oil catalyst and have penetrated.
Working sulfur capacity refers to: the content of the sulphur of absorption is accumulated on the desulfurization of hydrocarbon oil catalyst having penetrated (with the total of desulfurization of hydrocarbon oil catalyst
On the basis of weight).
GB/T 503-1995 and GB/T 5487-1995 is respectively adopted to measure before reaction and gasoline after the 6th stable circulation
Motor octane number (MON) and research octane number (RON) (RON), the results are shown in Table 2.
Table 2
Note: the data in table in relation to octane number are the variable quantities of the octane number compared to feed gasoline."-" indicate compared to
The octane number of feed gasoline reduces.
1, the sulfur content of feed gasoline is 780ppm, RON 93.0, MON 82.7.
2, △ MON indicates the value added of product MON；
3, △ RON indicates the value added of product RON；
4, △ (RON+MON)/2 is the difference of product anti-knock index and raw material anti-knock index.
It can be seen that in desulfurization of hydrocarbon oil catalyst provided by the invention from the result data of table 2 containing vanadium carbide component, hydrocarbon
The sulfur content for reducing gasoline still can be well realized after carrying out multiple circulation desulfurization in oily desulphurization catalyst, illustrates the catalyst
With better desulphurizing activated and activity stability.And the abrasion index of the desulfurization of hydrocarbon oil catalyst is lower, illustrates have more
Good abrasion strength resistance, so as to so that the desulfurization of hydrocarbon oil catalyst has longer service life.Desulfurization of hydrocarbon oil in comparative example 5
Catalyst contains ordered porous carbonitride of silicium material, the vanadium carbide without containing the application, therefore abrasion index much higher than embodiment
The abrasion index of catalyst obtained illustrates that desulfurization of hydrocarbon oil catalyst provided by the invention can have better wear-resisting property.
Embodiment 8
Aging, condition are carried out to desulfurization of hydrocarbon oil catalyst A1-A6 and B1-B5 are as follows: catalyst is placed in 600 DEG C, water steaming
16h is handled under the atmosphere that gas partial pressure is 20kPa.
To before and after aging A1 and B1 carry out XRD spectra analysis, wherein XRD spectra such as Fig. 1 institute before and after A1 hydrothermal aging
Show, fresh dose there are the crystal phase peaks of vanadium carbide at 2 θ=37.3 °, 43.36 ° and 63.10 ° with aging agent；B1 hydrothermal aging
The XRD spectra of front and back is as shown in Figure 2.
Do not occur 2 θ=22.0 ° of zinc silicate, 25.54 °, 48.9 ° in Fig. 1, in the XRD spectra after A1 hydrothermal aging
With 59.4 ° of characteristic peak；In Fig. 2, occurs the features described above peak of zinc silicate in the XRD spectra after B1 hydrothermal aging.Using
Silicic acid Zn content in the XRD spectra of crystal content quantitative analysis B1-B5, the results are shown in Table 3.
The desulfurization performance that A1-A6 and B1-B5 after aging are evaluated with evaluation method same as Example 7, the results are shown in Table
3。
Desulfurization of hydrocarbon oil catalyst A1-A6 and B1-B5 after the aging working sulfur capacity for carrying out desulfurization of hydrocarbon oil is calculated, is as a result seen
Table 4.
Table 3
Note: the data in table in relation to octane number are the variable quantities of the octane number compared to feed gasoline."-" indicate compared to
The octane number of feed gasoline reduces.
1, the sulfur content of feed gasoline is 780ppm, RON 93.0, MON 82.7.
2, △ MON indicates the value added of product MON；
3, △ RON indicates the value added of product RON；
4, △ (RON+MON)/2 is the difference of product anti-knock index and raw material anti-knock index.
From the results shown in Table 3, it after ageing process, is not generated in the desulfurization of hydrocarbon oil catalyst that embodiment obtains
Zinc silicate, and the catalyst in comparative example 1-4, zinc oxide can generate zinc silicate with the material of silicon oxide-containing, to make catalyst
Desulphurizing activated reduction.
Table 4
From the results shown in Table 3, it after ageing process, is not generated in the desulfurization of hydrocarbon oil catalyst that embodiment obtains
Zinc silicate, and the catalyst in comparative example 1-4, zinc oxide can generate zinc silicate with the material of silicon oxide-containing, to make catalyst
Desulphurizing activated reduction.
The data of product gasoline can also be seen that the still available high product of method provided by the invention from table 2 and 3
Yield of gasoline, the octane number of gasoline also change less.
From table 4, it can be seen that carrying out the working sulfur capacity of gasoline desulfurization using gasoline desulphurization catalyst of the invention before aging
It is close with using the working sulfur capacity of gasoline desulphurization catalyst of comparative example, after ageing process, since the hydrocarbon ils that embodiment obtains is de-
Without generating zinc silicate in sulfur catalyst, and the catalyst in comparative example 1-4, zinc oxide can generate silicon with the material of silicon oxide-containing
Sour zinc so that the working sulfur capacity of catalyst be made to be decreased obviously, therefore desulphurizing activated is significantly reduced.
From table 4, it can be seen that carrying out the working sulfur capacity of desulfurization of hydrocarbon oil using desulfurization of hydrocarbon oil catalyst of the invention before aging
It is close with using the working sulfur capacity of desulfurization of hydrocarbon oil catalyst of comparative example；After ageing process, since the hydrocarbon ils that embodiment obtains is de-
Without generating zinc silicate in sulfur catalyst, and the catalyst in comparative example 1-4, zinc oxide can generate silicon with the material of silicon oxide-containing
Sour zinc so that the working sulfur capacity of catalyst be made to be decreased obviously, therefore desulphurizing activated is significantly reduced.
Claims (15)
1. a kind of desulfurization of hydrocarbon oil catalyst, on the basis of the total weight of the desulfurization of hydrocarbon oil catalyst, which contains
Have:
1) zinc oxide of 10~80 weight %；
2) the non-aluminum oxide of 3~35 weight %, the non-aluminum oxide are in titanium dioxide, zirconium dioxide and stannic oxide
It is at least one；
3) carbide vanadium vc of 5~40 weight %；
4) laminated clay column of 1~20 weight %；
5) metallic promoter agent of 5~30 weight %, the metallic promoter agent are selected from least one of cobalt, nickel, iron and manganese；
Wherein, carbide vanadium vc has face-centered cubic crystal structure.
2. desulfurization of hydrocarbon oil catalyst according to claim 1, wherein using the total weight of the desulfurization of hydrocarbon oil catalyst as base
Standard, the desulfurization of hydrocarbon oil catalyst contain the metal oxide of 40~60 weight %, the non-aluminum bonding of 8~15 weight %
Agent, the carbide vanadium vc of 12~25 weight %, the laminated clay column of 2~10 weight %, the metal promoted of 12~20 weight %
Agent.
3. desulfurization of hydrocarbon oil catalyst according to claim 1 or 2, wherein the desulfurization of hydrocarbon oil catalyst is obtained through XRD analysis
To spectrogram in 2 θ be 37.3 °, 43.36 ° and 63.10 ° at there are the crystal phase peaks of carbide vanadium vc.
4. a kind of method for preparing desulfurization of hydrocarbon oil catalyst described in any one of claim 1-3, comprising:
Carbide vanadium vc, non-al binder, water and acidic liquid are contacted and to form slurries by (1a), and the slurries and layer column are glued
Soil, zinc oxide；Or
(1b) contacts non-al binder, water and acidic liquid to form slurries, by the slurries and laminated clay column, zinc oxide, carbon
Change vanadium VC and is mixed to get carrier pulp；
(2) carrier pulp is formed, first dry, the first roasting, obtains carrier；
(3) precursor of metallic promoter agent is introduced in the carrier, is then carried out second dry and the second roasting, is obtained catalyst
Precursor；
(4) catalyst precarsor is restored under hydrogen atmosphere, obtains desulfurization of hydrocarbon oil catalyst；
Wherein, carbide vanadium vc has face-centered cubic crystal structure.
5. according to the method described in claim 4, wherein, carbide vanadium vc is in the form of sheets or column structure.
6. method according to claim 4 or 5, wherein the grain diameter of carbide vanadium vc is 2~30 μm；Carbide vanadium vc
Specific surface area is 10 m2The m of/g~502/g。
7. according to the method described in claim 6, wherein, the grain diameter of carbide vanadium vc is 3~15 μm.
8. according to the method described in claim 6, wherein, the specific surface area of carbide vanadium vc is 20 m2/ g~35m2/g。
9. according to the method described in claim 4, wherein, the non-al binder is selected from titanium dioxide binder, zirconium dioxide
At least one of binder and stannic oxide binder；The titanium dioxide binder is selected from titanium tetrachloride, tetraethyl titanate, titanium
At least one of isopropyl propionate, acetic acid titanium, hydrous titanium oxide and anatase titanium dioxide；The zirconium dioxide binder choosing
From at least one of zirconium chloride, zirconium oxychloride, acetic acid zirconium, hydrous zirconium oxide(HZO) and amorphous zirconium dioxide；The dioxy
Change tin binder and is selected from least one of tin tetrachloride, four isopropanol tin, tin acetate, aqua oxidation tin and stannic oxide.
10. according to the method described in claim 4, wherein, the laminated clay column is rectorite, Yun Mengshi, bentonite, montmorillonite
At least one of with smectite.
11. according to the method described in claim 4, wherein, the precursor of the metallic promoter agent is selected from the acetic acid of metallic promoter agent
At least one of salt, carbonate, nitrate, sulfate, rhodanate and oxide.
12. according to the method described in claim 4, wherein, the dosage of the acidic liquid makes the pH value 1 of the carrier pulp
~5；The acidic liquid is the aqueous solution of acid or acid, and the acid is selected from water-soluble inorganic acid and/or organic acid.
13. according to the method described in claim 4, wherein, the described first dry temperature is room temperature~400 DEG C, described first
The dry time is 0.5~8 h；The temperature of first roasting is 400~700 DEG C, and the time of first roasting is 0.5 h
More than；Described second dry temperature is 50~300 DEG C, and the described second dry time was 0.5~8 h；Second roasting
Temperature be 300~800 DEG C, it is described second roasting time be 0.5~4 h；The temperature of the reduction is 300~600 DEG C, institute
The time for stating reduction is 0.5~6h, and hydrogen content is 10~60 volume % in the hydrogen atmosphere.
14. desulfurization of hydrocarbon oil catalyst made from method described in any one of claim 4-13.
15. a kind of method of desulfurization of hydrocarbon oil, comprising: in a hydrogen atmosphere, will be any in hydrocarbon oil containing surphur and claim 1-3 and 14
Desulfurization of hydrocarbon oil catalyst described in one carries out desulphurization reaction at 350~500 DEG C, 0.5~4MPa.
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