CN109985620A - A kind of hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining and its preparation method and application - Google Patents
A kind of hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining and its preparation method and application Download PDFInfo
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- tropsch synthesis
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- 239000003054 catalyst Substances 0.000 title claims abstract description 129
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 104
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 104
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 100
- 238000007670 refining Methods 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 146
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims abstract description 89
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 44
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 46
- 239000000243 solution Substances 0.000 claims description 41
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 40
- 239000002243 precursor Substances 0.000 claims description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 28
- 239000001257 hydrogen Substances 0.000 claims description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 27
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 22
- 239000010970 precious metal Substances 0.000 claims description 19
- 241000219782 Sesbania Species 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 17
- 239000011148 porous material Substances 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 239000000428 dust Substances 0.000 claims description 13
- 238000005516 engineering process Methods 0.000 claims description 13
- 229910017604 nitric acid Inorganic materials 0.000 claims description 13
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 12
- 229910052763 palladium Inorganic materials 0.000 claims description 12
- 230000001376 precipitating effect Effects 0.000 claims description 11
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 7
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 4
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 3
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 238000007493 shaping process Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 abstract description 54
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 35
- 229910052799 carbon Inorganic materials 0.000 abstract description 35
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 31
- 230000008021 deposition Effects 0.000 abstract description 20
- 238000009826 distribution Methods 0.000 abstract description 15
- 238000004939 coking Methods 0.000 abstract description 11
- 150000001875 compounds Chemical class 0.000 abstract description 10
- 238000006356 dehydrogenation reaction Methods 0.000 abstract description 6
- 238000003541 multi-stage reaction Methods 0.000 abstract description 3
- 239000003921 oil Substances 0.000 description 104
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 22
- 238000005259 measurement Methods 0.000 description 19
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 16
- -1 polyethylene Polymers 0.000 description 16
- 239000004698 Polyethylene Substances 0.000 description 11
- 229910021529 ammonia Inorganic materials 0.000 description 11
- 229910052593 corundum Inorganic materials 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 229920000573 polyethylene Polymers 0.000 description 11
- 229910001845 yogo sapphire Inorganic materials 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 230000009467 reduction Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 239000005864 Sulphur Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 150000001993 dienes Chemical class 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000003245 coal Substances 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 230000009849 deactivation Effects 0.000 description 3
- 230000002779 inactivation Effects 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 229910003294 NiMo Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 238000009704 powder extrusion Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- C10G45/10—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 platinum group metals 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
- C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
- C10G45/40—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing platinum group metals or compounds thereof
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- 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)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention provides a kind of hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining, including noble metal and γ-Al2O3Carrier, wherein the quality of the noble metal is the γ-Al2O3The 0.2%-2.0% of carrier quality, by controlling the content of noble metal, so that catalyst is reached the balance between metallicity-acidity, enhance hydrogenating function, reducing alkene leads to the coking carbon distribution of catalyst because dehydrogenation reaction occurs, therefore, the present invention does not need stepwise reaction only with a kind of catalyst, the hydrofinishing of Fischer-Tropsch synthesis oil can be completed, and catalyst coking carbon deposition rate is low, the service life is long, can guarantee higher olefin conversion and conversion rate of oxygenated compound for a long time.
Description
Technical field
The present invention relates to hydrogenation catalyst technical fields, and in particular to a kind of hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining and its
Preparation method and application.
Background technique
As the increasingly deficient and people of petroleum resources are to environmentally friendly attention, Devoting Major Efforts To Developing coal liquefaction has become pass
The focus of note.Indirect coal liquefaction can not only make full use of coal resources abundant, and can produce a large amount of cleaning high-quality
Fuel oil, alleviate the pressure of dependence on foreign countries for oil, safeguard strategic security.The Low Temperature Fischer Tropsch synthesis of indirect coal liquefaction production
Oil is the clean fuel of a kind of " no sulphur, nitrogen-free and without aromatic hydrocarbons ", but own contains a large amount of alkene and oxygenatedchemicals, acid
Property it is stronger, if in following process without processing, not only easily corrode equipment, but also will affect the property of end product,
Therefore it needs to carry out Low Temperature Fischer Tropsch synthetic oil to add hydrogen saturation, hydrogenation deoxidation, to improve oil property.By can after hydrofinishing
Quality raw materials are provided for hydroisomerizing reaction, to obtain food grade solvent oil.
Currently, the catalyst for carrying out hydrofinishing (alkene saturation and hydrogenation deoxidation) to F- T synthesis crude oil mainly has two
Class: first is that sulphided state catalyst (such as sulphided state NiMo, CoMo and NiMoW catalyst), second is that the nickel-base catalyst of reduction-state.Sulphur
Change state catalyst and needs presulfurization just hydrogenation activity with higher and stability.After through a long time operation, the sulphur on catalyst
The sulphur that may be lost, lead to active decline, and lose is possibly into causing sulphur pollution in product.And for the nickel of reduction-state
Base catalyst due to carboxylic acid in oil from Fischer-Tropsch synthesis and metallic nickel nickel carboxylate easily generated, and causes its active component nickel to be lost, into
And catalyst is made to be easy inactivation.
Chinese patent literature CN102041067A discloses a kind of hydrofinishing process of oil from Fischer-Tropsch synthesis, deposits in hydrogen
Under, oil from Fischer-Tropsch synthesis is first contacted with diene hydrogenation saturation catalyst, is mainly saturated diene hydrogenation, then is taken off with hydrogen is added
VPO catalysts contact carries out alkene saturation and hydrogenation deoxidation reaction, obtains hydrotreated product, hydrogenation deoxidation used in this method
Catalyst is noble metal catalyst or high-nickel catalyst, and wherein the carrier of noble metal catalyst is aluminium oxide, silica and dioxy
Change one of titanium or a variety of, noble metal is platinum or palladium, and the weight content of noble metal in the catalyst is 0.5%-5.0%, is urged
The specific surface area of agent is 150-300m2/ g carries out hydrofining reaction using the noble metal catalyst, can overcome sulphided state
The shortcomings that catalyst, avoids activity decline caused by sulphur loss, and to the sulphur pollution of product, while also overcoming reduction-state
The defect of nickel-base catalyst easy in inactivation, to reach higher hydrogenation efficiency.But before using the catalyst, it is necessary to first
Make Fischer-Tropsch synthesis oil and another diene hydrogenation saturation catalyst haptoreaction, carries out alkene again after being saturated diene hydrogenation
Saturation and hydrogenation deoxidation reaction, to reduce the possibility of coking carbon distribution, avoid catalyst inactivation.
Summary of the invention
Therefore, the technical problem to be solved in the present invention is that hydrogenation of Fischer-Tropsch synthesis oil purification in the prior art is overcome to need to adopt
It is carried out with different catalysts substep, to reduce the defect of coking carbon deposition rate, to provide a kind of use a kind of catalyst, is not needed
Hydrofining reaction can be completed in substep, and coking carbon deposition rate is low, can keep higher olefin conversion for a long time and containing oxidation
Close a kind of hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining of object conversion ratio, preparation method and its in hydrogenation of Fischer-Tropsch synthesis oil technique
Application.
For this purpose, the present invention provides a kind of hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining, including noble metal and γ-Al2O3It carries
Body, wherein the quality of the noble metal is the γ-Al2O3The 0.2%-2.0% of carrier quality.
The hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining, the noble metal are palladium or platinum.
The hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining, the γ-Al2O3The specific surface area of carrier is 350-500m2/
G, mean pore size 2.1-5.0nm.
The present invention provides the preparation methods of the hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining described in one kind, including,
S1, excess of ammonia aqueous solution and aluminum nitrate solution cocurrent are mixed, makes the pH 8-9 of final solution；By generation
After washing of precipitate, separation, nitric acid is added and is stirred, obtains precursor sol；
Structure directing agent is added in S2, Xiang Suoshu precursor sol, drying obtains γ-Al2O3Predecessor；
S3, by the γ-Al2O3Predecessor is mixed with sesbania powder, and dust technology is added, and is uniformly mixed, is roasted after shaping and drying
It burns, obtains the γ-Al2O3Carrier；
S4, soluble precious-metal salt and deionized water or acid solution are made into precious metal impregnation liquid, by the γ-Al2O3It carries
Body is impregnated in the precious metal impregnation liquid, and then drying, roasting, obtain the hydrogenation of Fischer-Tropsch synthesis oil refining catalytic
Agent.
The preparation method of the hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining, in S1 step, the temperature of the stirring is 80-
100 DEG C, the time of stirring is 2 hours or more；In S2 step, the structure directing agent is poly- for polyethylene oxide-polypropylene oxide-
Ethylene oxide (P123), with the Al ionometer in the precursor sol, Al ion and the molar ratio of the structure directing agent are
1:0.02-1.0 the temperature of the drying is 100-120 DEG C；In S3 step, the quality of the sesbania powder accounts for the γ-Al2O3Before
The 1.0-8.0% of amount of substance is driven, the temperature of the drying is 100-120 DEG C, and the temperature of the roasting is 400-600 DEG C, roasting
Time be 3-8 hours.
The preparation method of the hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining, in S4 step, the soluble precious-metal salt
For one or more of palladium chloride, palladium nitrate, palladium acetate, platinum chloride, platinum nitrate, chloroplatinic acid.
The preparation method of the hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining, in S4 step, the time of the dipping is 12-
24 hours, the temperature of the drying was 60-120 DEG C, and the time of drying is 4-12 hours, and the temperature of the roasting is 400-550
DEG C, the time of roasting is 3-8 hours.
The present invention also provides the hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining described in one kind in hydrogenation of Fischer-Tropsch synthesis oil technique
In application.
Application of the hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining in hydrogenation of Fischer-Tropsch synthesis oil technique, the Fischer-Tropsch close
At the condition of oily hydrogenation technique are as follows: pressure 2-4MPa, hydrogen/oil volume ratio 300-800, air speed 2.0-8.0h-1, reaction temperature 150-
300℃。
Technical solution of the present invention has the advantages that
1. a kind of hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining provided by the invention, including noble metal and γ-Al2O3Carrier,
In, the quality of the noble metal is the γ-Al2O3The 0.2%-2.0% of carrier quality, due to γ-Al2O3Carrier has weak
Acidity, by by noble metal and γ-Al2O3Carrier combination uses, and makes the catalyst while having metallicity and faintly acid, due to
During noble metal catalyst catalysis Fischer-Tropsch synthesis oil reaction, it can occur to add hydrogen and dehydrogenation reaction simultaneously, if dehydrogenation is anti-
It should be greater than hydrogenation reaction, then can generate coking carbon distribution, this catalyst is γ-Al by the quality of control noble metal2O3Carrier quality
0.2%-2.0% enhance hydrogenating function so that catalyst be made to reach the balance between metallicity-acidity, reduce alkene
Lead to the coking carbon distribution of catalyst because dehydrogenation reaction occurs, therefore, the present invention does not need first to carry out only with a kind of catalyst
The stepwise reaction of alkadienes saturation, can be completed the hydrofinishing of Fischer-Tropsch synthesis oil, and catalyst coking carbon deposition rate is low, the service life
It is long, it can guarantee higher olefin conversion and conversion rate of oxygenated compound for a long time；In addition, by the content of control noble metal,
On the one hand, it avoids noble-metal-supported amount too high, and the dispersion degree of noble metal is caused to be deteriorated, particle agglomeration causes under activity
Drop and cost increase, and on the other hand, also avoid because noble-metal-supported amount is too low, and cause activated centre few, and catalytic activity is small.
2. a kind of hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining provided by the invention, the noble metal is palladium or platinum, by adopting
It uses palladium or platinum as noble metal active component, catalyst activity with higher can be made, improve olefin conversion and oxygen-containing chemical combination
Object conversion ratio.
3. a kind of hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining provided by the invention, the γ-Al2O3The specific surface area of carrier
For 350-500m2/ g, mean pore size 2.1-5.0nm, since alkene saturation and hydrogenation deoxidation reaction are exothermic reaction,
Thermal discharge is big, Wen Shenggao, by using the alumina support with high specific surface area and smaller aperture due, makes noble metal active group
Divide and better disperse, the reunion of noble metal active component and sintering deactivation caused by avoiding because of high temperature exothermic improve making for catalyst
Use the service life；Due in Fischer-Tropsch synthesis oil hydro carbons and the oxygenatedchemicals overwhelming majority be chain, kinetic diameter is smaller, leads to
Crossing control pore size is 2.1-5.0nm, it is ensured that catalyst to chain hydro carbons and oxygenatedchemicals selectivity with higher,
To improve catalytic efficiency, guarantee higher olefin conversion and conversion rate of oxygenated compound.
4. it is provided by the invention one kind described in hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining preparation method, including, S1, general
Excess of ammonia aqueous solution and the mixing of aluminum nitrate solution cocurrent, make the pH 8-9 of final solution；By the washing of precipitate of generation, separation
Afterwards, nitric acid is added to be stirred, obtains precursor sol；Structure directing agent is added in S2, Xiang Suoshu precursor sol, through drying
It is dry, obtain γ-Al2O3Predecessor；S3, by the γ-Al2O3Predecessor is mixed with sesbania powder, and dust technology is added, and is uniformly mixed,
It is roasted after shaping and drying, obtains the γ-Al2O3Carrier；S4, soluble precious-metal salt and deionized water or acid solution are made into
Precious metal impregnation liquid, by the γ-Al2O3Carrier is impregnated in the precious metal impregnation liquid, and then drying, roasting, obtain
It can be made by S1-S3 step with high-specific surface area, smaller aperture due, height to the hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining
γ-the Al of thermal stability2O3Carrier, high-specific surface area can be such that noble metal active component better disperses, and avoid making because of high temperature exothermic
Reunion and sintering deactivation at noble metal active component, improve the service life of catalyst, and lesser aperture can then guarantee
Catalyst improves catalytic efficiency to chain hydro carbons and oxygenatedchemicals selectivity with higher, guarantees higher alkene conversion
Rate and conversion rate of oxygenated compound, and high thermal stability then can guarantee that catalyst keeps stablizing in adding hydrogen exothermic reaction, when long
Between keep higher catalytic efficiency；In S1 step, by mixing excess of ammonia aqueous solution and aluminum nitrate solution cocurrent, with dropwise addition
Mixed phase ratio, can be made the hydrated alumina of single crystal phase, be more advantageous to plastic, to obtain the activity with high mechanical strength
γ-Al2O3Carrier improves the thermal stability of catalyst, prevents the sintering for causing catalyst because of high temperature exothermic from damaging, extension is urged
The agent service life；In S2 step, by the way that structure directing agent, the shape of controllable presoma primary particle are added into precursor sol
State makes γ-Al obtained2O3Carrier has high thermal stability and high-specific surface area；In S3 step, by by γ-Al2O3Forerunner
Object is mixed with sesbania powder extrusion aid, makes γ-Al2O3Predecessor preferably forms；In S4 step, by by γ-Al2O3Carrier leaching
Stain makes noble metal preferably be carried on γ-Al in precious metal impregnation liquid2O3On carrier, the activity of catalyst is improved.
5. the preparation method of hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining described in one kind provided by the invention, in S1 step,
The temperature of the stirring is 80-100 DEG C, and the time of stirring is 2 hours or more；In S2 step, the structure directing agent is polycyclic
Oxidative ethane-polypropylene oxide-polyethylene oxide (P123), with the Al ionometer in the precursor sol, Al ion with it is described
The molar ratio of structure directing agent is 1:0.02-1.0, and the temperature of the drying is 100-120 DEG C；In S3 step, the sesbania powder
Quality account for the γ-Al2O3The 1.0-8.0% of predecessor quality, the temperature of the drying are 100-120 DEG C, the roasting
Temperature is 400-600 DEG C, and the time of roasting is 3-8 hours, in S1 step, by the temperature and time of control stirring, makes to mix
Object preferably plastic；In S2 step, the amount of structure directing agent is added by control, can preferably regulate and control presoma primary particle
Form, γ-Al obtained2O3Carrier has high thermal stability, big specific surface area and lesser aperture；In S3 step, pass through
The amount of sesbania powder is added in control, can make γ-Al2O3Predecessor preferably forms, by controlling final drying temperature, roasting temperature
Degree and calcining time, it is ensured that form the γ-with biggish specific surface area, lesser aperture and high thermal stability
Al2O3Carrier.
6. the preparation method of hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining described in one kind provided by the invention, in S4 step,
The time of the dipping is 12-24 hours, and the temperature of the drying is 60-120 DEG C, and the time of drying is 4-12 hours, described
The temperature of roasting is 400-550 DEG C, and the time of roasting is 3-8 hours, passes through the time of control dipping, it is ensured that noble metal active
Ingredient is sufficiently submerged in γ-Al2O3Carrier, the temperature and time dried and roasted by control, can make noble metal in γ-Al2O3It carries
It is better dispersed on body, avoids reacting the sintering deactivation for leading to catalyst because of high temperature exothermic.
7. hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining described in one kind provided by the invention is in hydrogenation of Fischer-Tropsch synthesis oil technique
In application, by hydrogenation of Fischer-Tropsch synthesis oil technique use the catalyst, it is possible to reduce in hydrogenation technique, alkene because
Dehydrogenation reaction occurs and leads to the coking carbon distribution of catalyst, stepwise reaction is not required to using a kind of catalyst, Fischer-Tropsch conjunction can be completed
At the hydrofinishing of oil, and catalyst coking carbon deposition rate is low, and the service life is long, can keep higher olefin conversion and oxygen-containing for a long time
Compound ratio transformation.
8. hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining described in one kind provided by the invention is in hydrogenation of Fischer-Tropsch synthesis oil technique
In application, the condition of the hydrogenation of Fischer-Tropsch synthesis oil technique are as follows: pressure 2-4MPa, hydrogen/oil volume ratio 300-800, air speed
2.0-8.0h-1, 150-300 DEG C of reaction temperature, by controlling lower reaction temperature, the side reactions such as dehydrogenation, cracking can be reduced
It carries out, coking carbon deposition rate is reduced, by controlling other reaction conditions, it is ensured that higher alkene conversion and oxygenate conversion
Rate.
Specific embodiment
Embodiment 1
Present embodiments provide a kind of hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining, including precious metal palladium Pd and γ-Al2O3It carries
Body, wherein the quality of noble metal is γ-Al2O30.2%, the γ-Al of carrier quality2O3The specific surface area of carrier is 460m2/ g,
Mean pore size is 3.5nm.
The hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining the preparation method is as follows:
S1,75g aluminum nitrate is dissolved in 100g deionized water, the ammonia spirit and aluminum nitrate for being 2.5% by mass concentration
Solution cocurrent is added in beaker, makes the pH 8 of final solution；Obtained precipitating is washed repeatedly, filter after be dispersed in
In ionized water, make volume 200mL, 80 DEG C of stirrings are lower to be added dropwise 1mol/L nitric acid 16mL, continues stirring 4 hours, obtains 1mol/L
Precursor sol.
S2,40mL precursor sol is taken, 4.64g polyethylene oxide-propylene oxide-polyethylene oxide is added at room temperature
(P123) dry directly at 110 DEG C after being completely dissolved, obtain γ-Al2O3Predecessor.
S3, the above-mentioned γ-Al of 200g is taken2O3Predecessor is uniformly mixed with 10g sesbania powder, then adds the dust technology of 5wt%,
It forms in banded extruder, is dried through 120 DEG C after mixing, 500 DEG C roast 5 hours, and γ-Al is made2O3Carrier, specific surface area
For 460m2/g。
S4, palladium chloride is configured to the aqueous solution that mass concentration is 0.8%, according to equi-volume impregnating, by 50g γ-
Al2O3Carrier is added in the above-mentioned solution of 20ml, is impregnated 12 hours, is dried 4 hours through 120 DEG C, and 480 DEG C roast 4 hours, are made
Pd/γ-Al2O3Catalyst, the load capacity of Pd are 0.2%.
Measure 20mL Pd/ γ-Al2O3Catalyst is placed in continuous fixed bed reactors.First in 400 DEG C of hydrogen atmospheres
Middle reduction 8 hours, is then cooled to 300 DEG C, carries out hydrogenation of Fischer-Tropsch synthesis oil refining reaction.Reaction feed ratio are as follows: hydrogen/oil
(volume) than being 800, (carbon number distribution C5-C45, alkene account for 40wt% or more to Fischer-Tropsch synthesis oil, and oxygenatedchemicals accounts for
20wt% or so, acid value are about 15.4mgKOH/g) it is pumped by plunger pump.Reaction temperature is 300 DEG C, and reaction stagnation pressure is 2MPa,
WHSV=2.0h-1。
After reaction carries out 100 hours, measuring carbon deposition quantity by thermogravimetry is 1.8% (mass percent), with reference to SH/T
In 0741-2004 gasoline in hydrocarbon system's composition measuring method (multidimensional gas chromatography) and SH/T0663-1998 gasoline certain alcohols and
Ethers measuring method (gas chromatography), using gas chromatograph-mass spectrometer (GC-MS), to the F- T synthesis of reaction front and back
Oil carries out constituent content measurement, calculates the conversion ratio of olefin conversion and oxygenatedchemicals, and calculation formula is as follows: olefin conversion
The content * 100% of alkene in=(content of alkene in content-product of alkene in raw material)/raw material；The conversion of oxygenatedchemicals
The content * of oxygenatedchemicals in rate=(content of oxygenatedchemicals in content-product of oxygenatedchemicals in raw material)/raw material
100%, the result of measurement are as follows: olefin conversion 99.9wt%, conversion rate of oxygenated compound 99.0wt%.
Embodiment 2
Present embodiments provide a kind of hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining, including precious metal palladium Pd and γ-Al2O3It carries
Body, wherein the quality of noble metal is γ-Al2O30.5%, the γ-Al of carrier quality2O3The specific surface area of carrier is 350m2/ g,
Mean pore size is 5.0nm.
The hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining the preparation method is as follows:
S1,75g aluminum nitrate is dissolved in 100g deionized water, the ammonia spirit and aluminum nitrate for being 2.5% by mass concentration
Solution cocurrent is added in beaker, makes the pH 9 of final solution；Obtained precipitating is washed repeatedly, filter after be dispersed in
In ionized water, make volume 200mL, 100 DEG C of stirrings are lower to be added dropwise 1.5mol/L nitric acid 20mL, continues stirring 2 hours, obtains
The precursor sol of 1mol/L.
S2,40mL precursor sol is taken, 4.64g polyethylene oxide-propylene oxide-polyethylene oxide is added at room temperature
(P123) dry directly at 100 DEG C after being completely dissolved, obtain γ-Al2O3Predecessor.
S3, the above-mentioned γ-Al of 200g is taken2O3Predecessor is uniformly mixed with 2g sesbania powder, then adds the dust technology of 5wt%, is mixed
It forms in banded extruder after closing uniformly, is dried through 100 DEG C, 400 DEG C roast 8 hours, and γ-Al is made2O3Carrier, specific surface area are
350m2/g。
S4, palladium nitrate is configured to the aqueous solution that mass concentration is 2.4%, according to equi-volume impregnating, by 50g γ-
Al2O3Carrier is added in above-mentioned 22.5ml solution, is impregnated 15 hours, is dried 6 hours through 110 DEG C, 450 DEG C roast 6 hours, system
Obtain Pd/ γ-Al2O3Catalyst, the load capacity of Pd are 0.5%.
Measure 20mL Pd/ γ-Al2O3Catalyst is placed in continuous fixed bed reactors.First in 400 DEG C of hydrogen atmospheres
Middle reduction 8 hours, is then cooled to 280 DEG C, carries out hydrogenation of Fischer-Tropsch synthesis oil refining reaction.Reaction feed ratio are as follows: hydrogen/oil
(volume) than being 800, (carbon number distribution C5-C45, alkene account for 40wt% or more to Fischer-Tropsch synthesis oil, and oxygenatedchemicals accounts for
20wt% or so, acid value are about 15.4mgKOH/g) it is pumped by plunger pump.Reaction temperature is 280 DEG C, and reaction stagnation pressure is 2MPa,
WHSV=2.0h-1。
After reaction carries out 100 hours, method same as Example 1 is used to measure carbon deposition quantity as 1.3% (quality percentage
Number), the result of the measurement of the conversion ratio of olefin conversion and oxygenatedchemicals are as follows: olefin conversion 99.9wt%, containing oxidation
Conjunction object conversion ratio is 99.0wt%.
Embodiment 3
Present embodiments provide a kind of hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining, including precious metal palladium Pd and γ-Al2O3It carries
Body, wherein the quality of noble metal is γ-Al2O31.0%, the γ-Al of carrier quality2O3The specific surface area of carrier is 500m2/ g,
Mean pore size is 2.1nm.
The hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining the preparation method is as follows:
S1,15g aluminum nitrate is dissolved in 80g deionized water, mass concentration is molten for 2.0% ammonia spirit and aluminum nitrate
Liquid cocurrent is added in beaker, makes the pH 8 of final solution；Obtained precipitating is washed repeatedly, filter after be dispersed in from
In sub- water, make volume 200mL, 90 DEG C of stirrings are lower to be added dropwise 0.5mol/L nitric acid 12mL, continues stirring 3 hours, obtains 0.2mol/
The precursor sol of L.
S2,40mL precursor sol is taken, 9.28g polyethylene oxide-propylene oxide-polyethylene oxide is added at room temperature
(P123) dry directly at 120 DEG C after being completely dissolved, obtain γ-Al2O3Predecessor.
S3, the above-mentioned γ-Al of 200g is taken2O3Predecessor is uniformly mixed with 16g sesbania powder, then adds the dust technology of 5wt%,
It forms in banded extruder, is dried through 110 DEG C after mixing, 600 DEG C roast 3 hours, and γ-Al is made2O3Carrier, specific surface area
For 500m2/g。
S4, palladium chloride is configured to the aqueous solution that mass concentration is 3.3%, according to equi-volume impregnating, by 50g γ-
Al2O3Carrier is added in the above-mentioned solution of 25ml, is impregnated 18 hours, is dried 8 hours through 100 DEG C, and 480 DEG C roast 5 hours, are made
Pd/γ-Al2O3Catalyst, the load capacity of Pd are 1.0%.
Measure 20mL Pd/ γ-Al2O3Catalyst is placed in continuous fixed bed reactors.First in 400 DEG C of hydrogen atmospheres
Middle reduction 8 hours, is then cooled to 250 DEG C, carries out hydrogenation of Fischer-Tropsch synthesis oil refining reaction.Reaction feed ratio are as follows: hydrogen/oil
(volume) than being 800, (carbon number distribution C5-C45, alkene account for 40wt% or more to Fischer-Tropsch synthesis oil, and oxygenatedchemicals accounts for
20wt% or so, acid value are about 15.4mgKOH/g) it is pumped by plunger pump.Reaction temperature is 250 DEG C, and reaction stagnation pressure is 3MPa,
WHSV=4.0h-1。
After reaction carries out 100 hours, method same as Example 1 is used to measure carbon deposition quantity as 1.4% (quality percentage
Number), the result of the measurement of the conversion ratio of olefin conversion and oxygenatedchemicals are as follows: olefin conversion 99.9wt%, containing oxidation
Conjunction object conversion ratio is 99.5wt%.
Embodiment 4
Present embodiments provide a kind of hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining, including precious metal palladium Pd and γ-Al2O3It carries
Body, wherein the quality of noble metal is γ-Al2O31.5%, the γ-Al of carrier quality2O3The specific surface area of carrier is 460m2/ g,
Mean pore size is 3.5nm.
The hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining the preparation method is as follows:
S1,75g aluminum nitrate is dissolved in 100g deionized water, the ammonia spirit and aluminum nitrate for being 2.5% by mass concentration
Solution cocurrent is added in beaker, makes the pH 8 of final solution；Obtained precipitating is washed repeatedly, filter after be dispersed in
In ionized water, make volume 200mL, 80 DEG C of stirrings are lower to be added dropwise 1mol/L nitric acid 16mL, continues stirring 4 hours, obtains 1mol/L
Precursor sol.
S2,40mL precursor sol is taken, 4.64g polyethylene oxide-propylene oxide-polyethylene oxide is added at room temperature
(P123) dry directly at 110 DEG C after being completely dissolved, obtain γ-Al2O3Predecessor.
S3, the above-mentioned γ-Al of 200g is taken2O3Predecessor is uniformly mixed with 10g sesbania powder, then adds the dust technology of 5wt%,
It forms in banded extruder, is dried through 120 DEG C after mixing, 500 DEG C roast 5 hours, and γ-Al is made2O3Carrier, specific surface area
For 460m2/g。
S4, palladium acetate is configured to the aqueous solution that mass concentration is 5.0%, according to equi-volume impregnating, by 50g γ-
Al2O3Carrier is added in the above-mentioned solution of 31.5ml, is impregnated 20 hours, is dried 10 hours through 80 DEG C, 520 DEG C roast 4 hours, system
Obtain Pd/ γ-Al2O3Catalyst, the load capacity of Pd are 1.5%.
Measure 20mL Pd/ γ-Al2O3Catalyst is placed in continuous fixed bed reactors.First in 400 DEG C of hydrogen atmospheres
Middle reduction 8 hours, is then cooled to 200 DEG C, carries out hydrogenation of Fischer-Tropsch synthesis oil refining reaction.Reaction feed ratio are as follows: hydrogen/oil
(volume) than being 800, (carbon number distribution C5-C45, alkene account for 40wt% or more to Fischer-Tropsch synthesis oil, and oxygenatedchemicals accounts for
20wt% or so, acid value are about 15.4mgKOH/g) it is pumped by plunger pump.Reaction temperature is 200 DEG C, and reaction stagnation pressure is 4MPa,
WHSV=6.0h-1。
After reaction carries out 100 hours, method same as Example 1 is used to measure carbon deposition quantity as 1.5% (quality percentage
Number), the result of the measurement of the conversion ratio of olefin conversion and oxygenatedchemicals are as follows: olefin conversion 100.0wt%, containing oxidation
Conjunction object conversion ratio is 99.5wt%.
Embodiment 5
Present embodiments provide a kind of hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining, including precious metal palladium Pd and γ-Al2O3It carries
Body, wherein the quality of noble metal is γ-Al2O32.0%, the γ-Al of carrier quality2O3The specific surface area of carrier is 460m2/ g,
Mean pore size is 3.5nm.
The hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining the preparation method is as follows:
S1,75g aluminum nitrate is dissolved in 100g deionized water, the ammonia spirit and aluminum nitrate for being 2.5% by mass concentration
Solution cocurrent is added in beaker, makes the pH 8 of final solution；Obtained precipitating is washed repeatedly, filter after be dispersed in
In ionized water, make volume 200mL, 80 DEG C of stirrings are lower to be added dropwise 1mol/L nitric acid 16mL, continues stirring 4 hours, obtains 1mol/L
Precursor sol.
S2,40mL precursor sol is taken, 4.64g polyethylene oxide-propylene oxide-polyethylene oxide is added at room temperature
(P123) dry directly at 110 DEG C after being completely dissolved, obtain γ-Al2O3Predecessor.
S3, the above-mentioned γ-Al of 200g is taken2O3Predecessor is uniformly mixed with 10g sesbania powder, then adds the dust technology of 5wt%,
It forms in banded extruder, is dried through 120 DEG C after mixing, 500 DEG C roast 5 hours, and γ-Al is made2O3Carrier, specific surface area
For 460m2/g。
S4, palladium chloride is configured to the aqueous solution that mass concentration is 4.8%, according to equi-volume impregnating, by 50g γ-
Al2O3Carrier is added in the above-mentioned solution of 35ml, is impregnated 24 hours, is dried 12 hours through 60 DEG C, and 550 DEG C roast 3 hours, are made
Pd/γ-Al2O3Catalyst, the load capacity of Pd are 2.0%.
Measure 20mL Pd/ γ-Al2O3Catalyst is placed in continuous fixed bed reactors.First in 400 DEG C of hydrogen atmospheres
Middle reduction 8 hours, is then cooled to 180 DEG C, carries out hydrogenation of Fischer-Tropsch synthesis oil refining reaction.Reaction feed ratio are as follows: hydrogen/oil
(volume) than being 300, (carbon number distribution C5-C45, alkene account for 40wt% or more to Fischer-Tropsch synthesis oil, and oxygenatedchemicals accounts for
20wt% or so, acid value are about 15.4mgKOH/g) it is pumped by plunger pump.Reaction temperature is 180 DEG C, and reaction stagnation pressure is 4MPa,
WHSV=8.0h-1。
After reaction carries out 100 hours, method same as Example 1 is used to measure carbon deposition quantity as 2.0% (quality percentage
Number), the result of the measurement of the conversion ratio of olefin conversion and oxygenatedchemicals are as follows: olefin conversion 100.0wt%, containing oxidation
Conjunction object conversion ratio is 99.9wt%.
Embodiment 6
Present embodiments provide a kind of hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining, including noble metal platinum Pt and γ-Al2O3It carries
Body, wherein the quality of noble metal is γ-Al2O30.2%, the γ-Al of carrier quality2O3The specific surface area of carrier is 460m2/ g,
Mean pore size is 3.5nm.
The hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining the preparation method is as follows:
S1,75g aluminum nitrate is dissolved in 100g deionized water, the ammonia spirit and aluminum nitrate for being 2.5% by mass concentration
Solution cocurrent is added in beaker, makes the pH 8 of final solution；Obtained precipitating is washed repeatedly, filter after be dispersed in
In ionized water, make volume 200mL, 80 DEG C of stirrings are lower to be added dropwise 1mol/L nitric acid 16mL, continues stirring 4 hours, obtains 1mol/L
Precursor sol.
S2,40mL precursor sol is taken, 4.64g polyethylene oxide-propylene oxide-polyethylene oxide is added at room temperature
(P123) dry directly at 110 DEG C after being completely dissolved, obtain γ-Al2O3Predecessor.
S3, the above-mentioned γ-Al of 200g is taken2O3Predecessor is uniformly mixed with 10g sesbania powder, then adds the dust technology of 5wt%,
It forms in banded extruder, is dried through 120 DEG C after mixing, 500 DEG C roast 5 hours, and γ-Al is made2O3Carrier, specific surface area
For 460m2/g。
S4, platinum nitrate is configured to the aqueous solution that mass concentration is 0.6%, according to equi-volume impregnating, by 50g γ-
Al2O3Carrier is added in the above-mentioned solution of 30ml, is impregnated 12 hours, is dried 4 hours through 120 DEG C, and 400 DEG C roast 8 hours, are made
Pt/γ-Al2O3Catalyst, the load capacity of Pt are 0.2%.
Measure 20mL Pt/ γ-Al2O3Catalyst is placed in continuous fixed bed reactors.First in 400 DEG C of hydrogen atmospheres
Middle reduction 8 hours, is then cooled to 300 DEG C, carries out hydrogenation of Fischer-Tropsch synthesis oil refining reaction.Reaction feed ratio are as follows: hydrogen/oil
(volume) than being 800, (carbon number distribution C5-C45, alkene account for 40wt% or more to Fischer-Tropsch synthesis oil, and oxygenatedchemicals accounts for
20wt% or so, acid value are about 15.4mgKOH/g) it is pumped by plunger pump.Reaction temperature is 300 DEG C, and reaction stagnation pressure is 2MPa,
WHSV=2.0h-1。
After reaction carries out 100 hours, method same as Example 1 is used to measure carbon deposition quantity as 1.6% (quality percentage
Number), the result of the measurement of the conversion ratio of olefin conversion and oxygenatedchemicals are as follows: olefin conversion 99.9wt%, containing oxidation
Conjunction object conversion ratio is 99.0wt%.
Embodiment 7
Present embodiments provide a kind of hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining, including noble metal platinum Pt and γ-Al2O3It carries
Body, wherein the quality of noble metal is γ-Al2O30.5%, the γ-Al of carrier quality2O3The specific surface area of carrier is 460m2/ g,
Mean pore size is 3.5nm.
The hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining the preparation method is as follows:
S1,75g aluminum nitrate is dissolved in 100g deionized water, the ammonia spirit and aluminum nitrate for being 2.5% by mass concentration
Solution cocurrent is added in beaker, makes the pH 8 of final solution；Obtained precipitating is washed repeatedly, filter after be dispersed in
In ionized water, make volume 200mL, 80 DEG C of stirrings are lower to be added dropwise 1mol/L nitric acid 16mL, continues stirring 4 hours, obtains 1mol/L
Precursor sol.
S2,40mL precursor sol is taken, 4.64g polyethylene oxide-propylene oxide-polyethylene oxide is added at room temperature
(P123) dry directly at 110 DEG C after being completely dissolved, obtain γ-Al2O3Predecessor.
S3, the above-mentioned γ-Al of 200g is taken2O3Predecessor is uniformly mixed with 10g sesbania powder, then adds the dust technology of 5wt%,
It forms in banded extruder, is dried through 120 DEG C after mixing, 500 DEG C roast 5 hours, and γ-Al is made2O3Carrier, specific surface area
For 460m2/g。
S4, platinum chloride is configured to the aqueous solution that mass concentration is 1.3%, according to equi-volume impregnating, by 50g γ-
Al2O3Carrier is added in the above-mentioned solution of 32.5ml, is impregnated 15 hours, is dried 6 hours through 110 DEG C, 450 DEG C roast 6 hours, system
Obtain Pt/ γ-Al2O3Catalyst, the load capacity of Pt are 0.5%.
Measure 20mL Pt/ γ-Al2O3Catalyst is placed in continuous fixed bed reactors.First in 400 DEG C of hydrogen atmospheres
Middle reduction 8 hours, is then cooled to 280 DEG C, carries out hydrogenation of Fischer-Tropsch synthesis oil refining reaction.Reaction feed ratio are as follows: hydrogen/oil
(volume) than being 800, (carbon number distribution C5-C45, alkene account for 40wt% or more to Fischer-Tropsch synthesis oil, and oxygenatedchemicals accounts for
20wt% or so, acid value are about 15.4mgKOH/g) it is pumped by plunger pump.Reaction temperature is 280 DEG C, and reaction stagnation pressure is 2MPa,
WHSV=2.0h-1。
After reaction carries out 100 hours, method same as Example 1 is used to measure carbon deposition quantity as 0.9% (quality percentage
Number), the result of the measurement of the conversion ratio of olefin conversion and oxygenatedchemicals are as follows: olefin conversion 99.9wt%, containing oxidation
Conjunction object conversion ratio is 99.5wt%.
Embodiment 8
Present embodiments provide a kind of hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining, including noble metal platinum Pt and γ-Al2O3It carries
Body, wherein the quality of noble metal is γ-Al2O31.0%, the γ-Al of carrier quality2O3The specific surface area of carrier is 460m2/ g,
Mean pore size is 3.5nm.
The hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining the preparation method is as follows:
S1,75g aluminum nitrate is dissolved in 100g deionized water, the ammonia spirit and aluminum nitrate for being 2.5% by mass concentration
Solution cocurrent is added in beaker, makes the pH 8 of final solution；Obtained precipitating is washed repeatedly, filter after be dispersed in
In ionized water, make volume 200mL, 80 DEG C of stirrings are lower to be added dropwise 1mol/L nitric acid 16mL, continues stirring 4 hours, obtains 1mol/L
Precursor sol.
S2,40mL precursor sol is taken, 4.64g polyethylene oxide-propylene oxide-polyethylene oxide is added at room temperature
(P123) dry directly at 110 DEG C after being completely dissolved, obtain γ-Al2O3Predecessor.
S3, the above-mentioned γ-Al of 200g is taken2O3Predecessor is uniformly mixed with 10g sesbania powder, then adds the dust technology of 5wt%,
It forms in banded extruder, is dried through 120 DEG C after mixing, 500 DEG C roast 5 hours, and γ-Al is made2O3Carrier, specific surface area
For 460m2/g。
S4, chloroplatinic acid is configured to the aqueous solution that mass concentration is 3.1%, according to equi-volume impregnating, by 50g γ-
Al2O3Carrier is added in the above-mentioned solution of 34ml, is impregnated 18 hours, is dried 8 hours through 100 DEG C, and 480 DEG C roast 5 hours, are made
Pt/γ-Al2O3Catalyst, the load capacity of Pt are 1.0%.
Measure 20mL Pt/ γ-Al2O3Catalyst is placed in continuous fixed bed reactors.First in 400 DEG C of hydrogen atmospheres
Middle reduction 8 hours, is then cooled to 250 DEG C, carries out hydrogenation of Fischer-Tropsch synthesis oil refining reaction.Reaction feed ratio are as follows: hydrogen/oil
(volume) than being 800, (carbon number distribution C5-C45, alkene account for 40wt% or more to Fischer-Tropsch synthesis oil, and oxygenatedchemicals accounts for
20wt% or so, acid value are about 15.4mgKOH/g) it is pumped by plunger pump.Reaction temperature is 250 DEG C, and reaction stagnation pressure is 3MPa,
WHSV=4.0h-1。
After reaction carries out 100 hours, method same as Example 1 is used to measure carbon deposition quantity as 1.0% (quality percentage
Number), the result of the measurement of the conversion ratio of olefin conversion and oxygenatedchemicals are as follows: olefin conversion 100.0wt%, containing oxidation
Conjunction object conversion ratio is 99.5wt%.
Embodiment 9
Present embodiments provide a kind of hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining, including noble metal platinum Pt and γ-Al2O3It carries
Body, wherein the quality of noble metal is γ-Al2O31.5%, the γ-Al of carrier quality2O3The specific surface area of carrier is 460m2/ g,
Mean pore size is 3.5nm.
The hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining the preparation method is as follows:
S1,75g aluminum nitrate is dissolved in 100g deionized water, the ammonia spirit and aluminum nitrate for being 2.5% by mass concentration
Solution cocurrent is added in beaker, makes the pH 8 of final solution；Obtained precipitating is washed repeatedly, filter after be dispersed in
In ionized water, make volume 200mL, 80 DEG C of stirrings are lower to be added dropwise 1mol/L nitric acid 16mL, continues stirring 4 hours, obtains 1mol/L
Precursor sol.
S2,40mL precursor sol is taken, 4.64g polyethylene oxide-propylene oxide-polyethylene oxide is added at room temperature
(P123) dry directly at 110 DEG C after being completely dissolved, obtain γ-Al2O3Predecessor.
S3, the above-mentioned γ-Al of 200g is taken2O3Predecessor is uniformly mixed with 10g sesbania powder, then adds the dust technology of 5wt%,
It forms in banded extruder, is dried through 120 DEG C after mixing, 500 DEG C roast 5 hours, and γ-Al is made2O3Carrier, specific surface area
For 460m2/g。
S4, platinum chloride is configured to the aqueous solution that mass concentration is 4.9%, according to equi-volume impregnating, by 50g γ-
Al2O3Carrier is added in the above-mentioned solution of 26.5ml, is impregnated 20 hours, is dried 10 hours through 80 DEG C, 520 DEG C roast 4 hours, system
Obtain Pt/ γ-Al2O3Catalyst, the load capacity of Pt are 1.5%.
Measure 20mL Pt/ γ-Al2O3Catalyst is placed in continuous fixed bed reactors.First in 400 DEG C of hydrogen atmospheres
Middle reduction 8 hours, is then cooled to 180 DEG C, carries out hydrogenation of Fischer-Tropsch synthesis oil refining reaction.Reaction feed ratio are as follows: hydrogen/oil
(volume) than being 800, (carbon number distribution C5-C45, alkene account for 40wt% or more to Fischer-Tropsch synthesis oil, and oxygenatedchemicals accounts for
20wt% or so, acid value are about 15.4mgKOH/g) it is pumped by plunger pump.Reaction temperature is 180 DEG C, and reaction stagnation pressure is 4MPa,
WHSV=6.0h-1。
After reaction carries out 100 hours, method same as Example 1 is used to measure carbon deposition quantity as 1.3% (quality percentage
Number), the result of the measurement of the conversion ratio of olefin conversion and oxygenatedchemicals are as follows: olefin conversion 100.0wt%, containing oxidation
Conjunction object conversion ratio is 99.9wt%.
Embodiment 10
Present embodiments provide a kind of hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining, including noble metal platinum Pt and γ-Al2O3It carries
Body, wherein the quality of noble metal is γ-Al2O32.0%, the γ-Al of carrier quality2O3The specific surface area of carrier is 460m2/ g,
Mean pore size is 3.5nm.
The hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining the preparation method is as follows:
S1,75g aluminum nitrate is dissolved in 100g deionized water, the ammonia spirit and aluminum nitrate for being 2.5% by mass concentration
Solution cocurrent is added in beaker, makes the pH 8 of final solution；Obtained precipitating is washed repeatedly, filter after be dispersed in
In ionized water, make volume 200mL, 80 DEG C of stirrings are lower to be added dropwise 1mol/L nitric acid 16mL, continues stirring 4 hours, obtains 1mol/L
Precursor sol.
S2,40mL precursor sol is taken, 4.64g polyethylene oxide-propylene oxide-polyethylene oxide is added at room temperature
(P123) dry directly at 110 DEG C after being completely dissolved, obtain γ-Al2O3Predecessor.
S3, the above-mentioned γ-Al of 200g is taken2O3Predecessor is uniformly mixed with 10g sesbania powder, then adds the dust technology of 5wt%,
It forms in banded extruder, is dried through 120 DEG C after mixing, 500 DEG C roast 5 hours, and γ-Al is made2O3Carrier, specific surface area
For 460m2/g。
S4, platinum nitrate is configured to the aqueous solution that mass concentration is 4.8%, according to equi-volume impregnating, by 50g γ-
Al2O3Carrier is added in the above-mentioned solution of 31ml, is impregnated 24 hours, is dried 12 hours through 60 DEG C, and 550 DEG C roast 3 hours, are made
Pt/γ-Al2O3Catalyst, the load capacity of Pt are 2.0%.
Measure 20mL Pt/ γ-Al2O3Catalyst is placed in continuous fixed bed reactors.First in 400 DEG C of hydrogen atmospheres
Middle reduction 8 hours, is then cooled to 150 DEG C, carries out hydrogenation of Fischer-Tropsch synthesis oil refining reaction.Reaction feed ratio are as follows: hydrogen/oil
(volume) than being 300, (carbon number distribution C5-C45, alkene account for 40wt% or more to Fischer-Tropsch synthesis oil, and oxygenatedchemicals accounts for
20wt% or so, acid value are about 15.4mgKOH/g) it is pumped by plunger pump.Reaction temperature is 150 DEG C, and reaction stagnation pressure is 4MPa,
WHSV=2.0h-1。
After reaction carries out 100 hours, method same as Example 1 is used to measure carbon deposition quantity as 1.5% (quality percentage
Number), the result of the measurement of the conversion ratio of olefin conversion and oxygenatedchemicals are as follows: olefin conversion 100.0wt%, containing oxidation
Conjunction object conversion ratio is 99.9wt%.
Comparative example 1
This comparative example provides a kind of hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining similar to Example 5, unique difference
It is in the quality of precious metal palladium Pd is γ-Al2O3The 0.1% of carrier quality.
Using the catalyst, hydrogenation of Fischer-Tropsch synthesis oil refining reaction, reaction are carried out under conditions of same as Example 5
After 100 hours, the carbon deposition quantity of measurement is 4.0%, the result of the measurement of the conversion ratio of olefin conversion and oxygenatedchemicals are as follows: alkene
Hydrocarbon conversion rate is 85.0%, conversion rate of oxygenated compound 85.1%.
Comparative example 2
This comparative example provides a kind of hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining similar to Example 5, unique difference
It is in the quality of precious metal palladium Pd is γ-Al2O3The 5.0% of carrier quality.
Using the catalyst, hydrogenation of Fischer-Tropsch synthesis oil refining reaction, reaction are carried out under conditions of same as Example 5
After 100 hours, the carbon deposition quantity of measurement is 5.3%, the result of the measurement of the conversion ratio of olefin conversion and oxygenatedchemicals are as follows: alkene
Hydrocarbon conversion rate is 91.0%, conversion rate of oxygenated compound 90.2%.
Comparative example 3
This comparative example provides a kind of hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining similar to Example 5, unique difference
It is in γ-Al2O3The specific surface area of carrier is 200m2/ g, average pore size 7.3nm.
Using the catalyst, hydrogenation of Fischer-Tropsch synthesis oil refining reaction, reaction are carried out under conditions of same as Example 5
After 100 hours, the carbon deposition quantity of measurement is 2.2%, the result of the measurement of the conversion ratio of olefin conversion and oxygenatedchemicals are as follows: alkene
Hydrocarbon conversion rate is 89.9%, conversion rate of oxygenated compound 89.2%.
Comparative example 4
This comparative example provides a kind of hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining similar to Example 5, unique difference
It is in in preparation γ-Al2O3When carrier, in S1 step, the ammonia spirit that mass concentration is 2.5% is instilled into aluminum nitrate dropwise
In solution.
Using the catalyst, hydrogenation of Fischer-Tropsch synthesis oil refining reaction, reaction are carried out under conditions of same as Example 5
After 100 hours, the carbon deposition quantity of measurement is 2.3%, the result of the measurement of the conversion ratio of olefin conversion and oxygenatedchemicals are as follows: alkene
Hydrocarbon conversion rate is 88.9%, conversion rate of oxygenated compound 87.9%.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (9)
1. a kind of hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining, which is characterized in that including noble metal and γ-Al2O3Carrier, wherein institute
The quality for stating noble metal is the γ-Al2O3The 0.2%-2.0% of carrier quality.
2. hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining according to claim 1, which is characterized in that the noble metal be palladium or
Platinum.
3. hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining according to claim 1 or 2, which is characterized in that the γ-Al2O3It carries
The specific surface area of body is 350-500m2/ g, mean pore size 2.1-5.0nm.
4. a kind of preparation method of the described in any item hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining of claim 1-3, feature exist
In, including,
S1, excess of ammonia aqueous solution and aluminum nitrate solution cocurrent are mixed, makes the pH 8-9 of final solution；By the precipitating of generation
After washing, separation, nitric acid is added and is stirred, obtains precursor sol；
Structure directing agent is added in S2, Xiang Suoshu precursor sol, drying obtains γ-Al2O3Predecessor；
S3, by the γ-Al2O3Predecessor is mixed with sesbania powder, and dust technology is added, and is uniformly mixed, is roasted, obtain after shaping and drying
To the γ-Al2O3Carrier；
S4, soluble precious-metal salt and deionized water or acid solution are made into precious metal impregnation liquid, by the γ-Al2O3Carrier exists
It is impregnated in the precious metal impregnation liquid, then drying, roasting, obtain the hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining.
5. the preparation method of hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining according to claim 4, which is characterized in that S1 step
In, the temperature of the stirring is 80-100 DEG C, and the time of stirring is 2 hours or more；In S2 step, the structure directing agent is poly-
Oxide-polypropylene oxide-polyethylene oxide (P123), with the Al ionometer in the precursor sol, Al ion and institute
The molar ratio for stating structure directing agent is 1:0.02-1.0, and the temperature of the drying is 100-120 DEG C；In S3 step, the sesbania
The quality of powder accounts for the γ-Al2O3The 1.0-8.0% of predecessor quality, the temperature of the drying are 100-120 DEG C, the roasting
Temperature be 400-600 DEG C, time of roasting is 3-8 hours.
6. the preparation method of hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining according to claim 4 or 5, which is characterized in that S4
In step, the soluble precious-metal salt is one of palladium chloride, palladium nitrate, palladium acetate, platinum chloride, platinum nitrate, chloroplatinic acid
Or it is several.
7. according to the preparation method of the described in any item hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining of claim 4-6, feature exists
In in S4 step, the time of the dipping is 12-24 hours, and the temperature of the drying is 60-120 DEG C, and the time of drying is 4-
12 hours, the temperature of the roasting was 400-550 DEG C, and the time of roasting is 3-8 hours.
8. a kind of described in any item hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining of claim 1-3 are in hydrogenation of Fischer-Tropsch synthesis oil technique
In application.
9. hydrogenation of Fischer-Tropsch synthesis oil catalyst for refining answering in hydrogenation of Fischer-Tropsch synthesis oil technique according to claim 8
With, which is characterized in that the condition of the hydrogenation of Fischer-Tropsch synthesis oil technique are as follows: pressure 2-4MPa, hydrogen/oil volume ratio 300-800 are empty
Fast 2.0-8.0h-1, 150-300 DEG C of reaction temperature.
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