CN105944717A - Catalyst for Fischer-Tropsch synthesis and preparation method and application of catalyst - Google Patents
Catalyst for Fischer-Tropsch synthesis and preparation method and application of catalyst Download PDFInfo
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- CN105944717A CN105944717A CN201610355980.6A CN201610355980A CN105944717A CN 105944717 A CN105944717 A CN 105944717A CN 201610355980 A CN201610355980 A CN 201610355980A CN 105944717 A CN105944717 A CN 105944717A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 164
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000001308 synthesis method Methods 0.000 title description 3
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 45
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 44
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 44
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 7
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 38
- 239000007789 gas Substances 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 13
- 239000000084 colloidal system Substances 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 230000003213 activating effect Effects 0.000 claims description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical group Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical group [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 4
- BMTAFVWTTFSTOG-UHFFFAOYSA-N Butylate Chemical group CCSC(=O)N(CC(C)C)CC(C)C BMTAFVWTTFSTOG-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical group [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 4
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N anhydrous n-heptane Natural products CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 32
- 239000000047 product Substances 0.000 abstract description 27
- 239000003502 gasoline Substances 0.000 abstract description 18
- 239000006227 byproduct Substances 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 description 32
- 239000002283 diesel fuel Substances 0.000 description 26
- 230000000694 effects Effects 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 238000001514 detection method Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 7
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 229910016287 MxOy Inorganic materials 0.000 description 5
- 239000006004 Quartz sand Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000013019 agitation Methods 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- 238000006073 displacement reaction Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a catalyst for Fischer-Tropsch synthesis and a preparation method and application of the catalyst. The catalyst for the Fischer-Tropsch synthesis comprises an active component and a catalyst carrier; the active component is Co; the catalyst carrier is MxOy-Al2O3, wherein M is Ru, Ce, La or Zr, x is 1 or 2, and y is 2 or 3; the content of the active component is 16 to 24 percent of the mass of the catalyst; the grain of the catalyst carrier is 4 to 10 micrometers; the specific surface area of the catalyst carrier is 210 to 320m<2>/g. When the catalyst is adopted to treat feed gas, the generation of side products such as methane can be effectively inhibited, and the products are mainly enabled to be gasoline and diesel fractions; in addition, the selectivity of senior wax can be reduced.
Description
Technical field
The invention belongs to chemical technology field, specifically, the present invention relates to a kind of catalyst for F-T synthesis and system thereof
Preparation Method and application.
Background technology
F-T synthesis is the important channel that natural gas, coal bed gas are converted into liquid fuel, to ensureing that Chinese energy safety has
Great strategic importance.Improve C5+The selectivity of hydrocarbon, the generation of the by-products such as suppression methane, is mainly grinding of F-T synthesis
Study carefully target, therefore develop low methane and high C5+Selective F-T synthetic catalyst just becomes current artificial oil technique and grinds
The focus studied carefully.The hydrocarbon products of F-T synthesis defers to typical ASF (Anderson-Schulz-Flory) regularity of distribution, products distribution
Width, only methane and macromolecule wax have higher selectivity, the most selective limit of remaining fraction: gasoline 48%, diesel oil 25%
Left and right.Therefore F-T synthesis can only obtain hydrocarbon mixture product, and poor selectivity is a marked feature of F-T synthesis.Research is opened
The target sending out F-T synthesis is to improve combined coefficient all the time, and the generation of the by-products such as suppression methane, as much as possible by hydrocarbon products collection
In in a certain fraction, therefore develop low methane and high C5+Selectivity synthesis catalyst just becomes current artificial oil technique and grinds
The focus studied carefully.
Summary of the invention
It is contemplated that one of technical problem solved the most to a certain extent in correlation technique.To this end, the one of the present invention
Purpose is to propose a kind of catalyst for F-T synthesis and its preparation method and application, uses this catalyst treatment unstripped gas
Time can effectively suppress the generation of the by-products such as methane, make product concentrate on vapour, diesel oil distillate, and advanced wax can be reduced
Selectivity.
In one aspect of the invention, the present invention proposes a kind of catalyst for F-T synthesis.Enforcement according to the present invention
Example, described catalyst includes: active component and catalyst carrier, and described active component is Co, and described catalyst carrier is
MxOy-Al2O3,
Wherein, M is Ru, Ce, La or Zr, x value 1 or 2, and y value is 2 or 3,
The content of described active component is the 16～24% of described catalyst quality,
The grain size of described catalyst carrier is 4～10 microns, and the specific surface area of described catalyst carrier is 210～320m2/g。
Thus, according to embodiments of the present invention can effectively suppress methane etc. when the catalyst treatment unstripped gas of F-T synthesis
The generation of by-product, makes product concentrate on vapour, diesel oil distillate, and can reduce the selectivity of advanced wax.
It addition, the catalyst for F-T synthesis according to the above embodiment of the present invention can also have following additional technology spy
Levy:
In some embodiments of the invention, the aperture of described catalyst carrier is 4～8nm.Thus, it is possible to significantly improve this
Catalyst is to gasoline and the selectivity of diesel oil.
In some embodiments of the invention, the pore volume of described catalyst carrier is 0.4～0.7cm3/g.Thus, it is possible to enter one
Step improves this catalyst to gasoline and the selectivity of diesel oil.
In some embodiments of the invention, the M in described catalyst carrier accounts for the 0.01～0.08% of described catalyst quality.
Thus, it is possible to improve this catalyst further to gasoline and the selectivity of diesel oil.
In some embodiments of the invention, the grain diameter of described active component is 1～10nm.Thus, it is possible to carry further
This catalyst high is to gasoline and the selectivity of diesel oil.
In another aspect of the invention, the present invention proposes a kind of method preparing the catalyst for F-T synthesis.According to
Embodiments of the invention, the method includes:
(1) template and solvent, aluminum source, nitric acid, M saline solution are carried out mixed processing, in order to obtain colloid solution；
(2) described colloid solution is dried process, in order to obtain presoma；
(3) described presoma is carried out calcination process, in order to obtain MxOy-Al2O3Catalyst carrier；
(4) use equi-volume impregnating at described MxOy-Al2O3Impregnate active component Co in catalyst carrier and carry out at heat
Reason, in order to obtain Co/MxOy-Al2O3,
Wherein, M is Ru, Ce, La or Zr, x value 1 or 2, and y value is 2 or 3.
Thus, the method preparing the catalyst for F-T synthesis according to an embodiment of the invention can effectively prepare
Stating to have and have higher selective catalyst to gasoline and diesel oil, and combined coefficient is high, method is easy, it is easy to implement.
It addition, preparation according to the above embodiment of the present invention can also have the most attached for the method for the catalyst of F-T synthesis
The technical characteristic added:
In some embodiments of the invention, described template be in P123, CTAB, F127 and Polyethylene Glycol extremely
Few one.
In some embodiments of the invention, source of aluminium be selected from aluminum isopropylate., aluminium secondary butylate, aluminum nitrate, aluminum chloride and
In aluminum sulfate at least one.
In some embodiments of the invention, described solvent is in ethanol, isopropanol, ethyl acetate, ether and pentane
At least one.
In some embodiments of the invention, in step (2), described dried is to carry out under 40～80 degrees Celsius
36～72 hours.
In some embodiments of the invention, in step (3), described calcination process is to carry out under 600～800 degrees Celsius
3～6 hours.
In some embodiments of the invention, described in step (4), heat treatment is to be dried 8～12 under 80～150 degrees Celsius
Hour, then 350～600 degrees Celsius of lower roastings.
In an additional aspect of the present invention, the present invention proposes a kind of employing catalyst treatment unstripped gas for F-T synthesis
Method, wherein, in described unstripped gas, the mol ratio of hydrogen and carbon monoxide is 1.5～2.5.According to embodiments of the invention, institute
The method of stating includes:
(1) described catalyst is carried out in the reactor activating pretreatment；
(2) by the supply of described unstripped gas in described reactor with gained activating pretreatment in step (1) after catalyst connect
Touch and carry out Fischer-Tropsch synthesis, in order to obtain the reactor product containing C5～C12.
Thus, the method using the catalyst treatment unstripped gas for F-T synthesis according to embodiments of the present invention can effectively press down
The generation of the by-products such as methane processed, makes product concentrate on vapour, diesel oil distillate, and can reduce the selectivity of advanced wax, from
And the productivity of gasoline and diesel oil can be significantly improved.
It addition, employing according to the above embodiment of the present invention is all right for the method for the catalyst treatment unstripped gas of F-T synthesis
There is following additional technical characteristic:
In some embodiments of the invention, in step (1), described activating pretreatment is at ambient pressure, in hydrogen atmosphere,
Air speed is 200～1000h-1, temperature is to carry out under 230～450 degrees Celsius 6～20 hours.Thus, it is possible to improve vapour further
Oil and the productivity of diesel oil.
In some embodiments of the invention, described reactor is fixed bed reactors, fluidized-bed reactor or slurry reactor
Device.
In some embodiments of the invention, in step (2), when described reactor is fixed bed reactors, described take
The temperature of torr synthetic reaction is 230～300 degrees Celsius, and air speed is 300-2000h-1, pressure is 0.1～5.5MPa.Thus, may be used
To improve gasoline and the productivity of diesel oil further.
In some embodiments of the invention, in step (2), when described reactor is fluidized-bed reactor, described take
The temperature of torr synthetic reaction is 230～280 DEG C, and air speed is 500～3000h-1, pressure is 0.1～5.5MPa.Thus, it is possible to enter
One step improves gasoline and the productivity of diesel oil.
In some embodiments of the invention, in step (2), when described reactor is paste state bed reactor, described take
The temperature of torr synthetic reaction is 230～280 degrees Celsius, and air speed is 500～3000h-1, pressure is 0.1～5.5MPa.Thus, may be used
To improve gasoline and the productivity of diesel oil further.
The additional aspect of the present invention and advantage will part be given in the following description, and part will become bright from the following description
Aobvious, or recognized by the practice of the present invention.
Accompanying drawing explanation
Above-mentioned and/or the additional aspect of the present invention and advantage will be apparent from from combining the accompanying drawings below description to embodiment
With easy to understand, wherein:
Fig. 1 is the method flow schematic diagram preparing the catalyst for F-T synthesis according to an embodiment of the invention；
Fig. 2 is that the method flow using the catalyst treatment unstripped gas for F-T synthesis according to an embodiment of the invention shows
It is intended to.
Detailed description of the invention
Embodiments of the invention are described below in detail, and the example of described embodiment is shown in the drawings, the most identical
Or similar label represents same or similar element or has the element of same or like function.Retouch below with reference to accompanying drawing
The embodiment stated is exemplary, it is intended to is used for explaining the present invention, and is not considered as limiting the invention.
In one aspect of the invention, the present invention proposes a kind of catalyst for F-T synthesis.Enforcement according to the present invention
Example, this catalyst includes: active component and catalyst carrier, and active component is Co, and catalyst carrier is MxOy-Al2O3,
Wherein, M is Ru, Ce, La or Zr, x value 1 or 2, and y value is 2 or 3, and the content of active component is catalyst
The 16～24% of quality, the crystal grain of catalyst carrier is 4～10 microns, and the specific surface area of catalyst carrier is 210～320m2/g。
Inventor finds, by Al2O3Middle doping MxOySo that MxOyCan be to Al2O3Physicochemical properties adjust
Become, and after load C o so that Co is in carrier surface high degree of dispersion, thus can effectively suppress when processing unstripped gas
The generation of the by-products such as methane, makes product concentrate on vapour, diesel oil distillate, can reduce the selectivity of advanced wax, additionally simultaneously
Use by MxOyDoping Al2O3The M formedxOy-Al2O3Catalyst carrier, can significantly improve the life-span of catalyst, and
And make gained catalyst have good mechanical stability.Concrete, MxOyCan be RuO2、CeO2、La2O3Or ZrO2。
And the too high levels of active component, Co crystal grain is reunited at catalyst surface, thus is reduced conversion ratio and vapour, the bavin of carbon monoxide
The selectivity of oil distillate, and active component content is low, Catalyst for Carbon Monoxide conversion ratio be also preferably below described under the conditions of turn
Rate；And catalyst carrier specific surface area is conducive to greatly the dispersion of active component, prevent sintering of catalyst, improve carbon monoxide
Conversion ratio, vapour, the selectivity of diesel oil distillate and the stability of catalyst, and specific surface area of catalyst is little, and active component exists
Catalyst surface is reunited, then can reduce conversion ratio and vapour, the selectivity of diesel oil distillate of carbon monoxide.
According to one embodiment of present invention, the aperture of catalyst carrier is not particularly restricted, those skilled in the art
Can select according to actual needs, according to a particular embodiment of the invention, the aperture of catalyst carrier can be
4～8nm.Inventor finds, the aperture appreciable impact Co crystallite dimension of catalyst carrier and reduction degree thereof, in aperture
Obtain the aggregation of undersized metal Co and relatively low reduction degree, have compared with macroporous catalyst relatively low activity and
Higher methane selectively, thus, uses the catalyst carrier in the application aperture to can ensure that gained catalyst has relatively
High activity and relatively low methane selectively.
According to still a further embodiment, the pore volume of catalyst carrier is not particularly restricted, those skilled in the art
Can select according to actual needs, according to a particular embodiment of the invention, the pore volume of catalyst carrier can be
0.4～0.7cm3/g.Inventor finds, the pore volume of catalyst carrier is too low, product wax that fischer-tropsch reaction generates and catalyst
Carbon distribution also can block a part of duct, thus reduces the activity of catalyst, makes catalyst slowly inactivate.
According to still another embodiment of the invention, in catalyst carrier, the content of M is not particularly restricted, art technology
Personnel can select according to actual needs, and according to a particular embodiment of the invention, the M in catalyst carrier can account for and urge
The 0.01～0.08% of agent quality.Inventor finds, auxiliary agent M can modification activities component surface, promotion from structure
Or the active center of suppression catalyst, the reduction degree changing active component Co in catalyst and dispersion, change catalyst
To carbon monoxide and the absorption of hydrogen and dissociate character and the stability to increase catalyst, reduce methane in product
Selectivity, and improve diesel oil and gasoline selective；And auxiliary agent too high levels can suppress the active center of catalyst, make to live
Property component reunite and reduce the conversion ratio of carbon monoxide, and the too low reduction degree that cannot change active component Co of auxiliary agent content and
Dispersion, it is impossible to play the effect promoting reaction.
According to still another embodiment of the invention, the particle diameter of activity over catalysts component is not particularly restricted, art technology
Personnel can select according to actual needs, and according to a particular embodiment of the invention, the grain diameter of active component can be
1～10nm.Inventor find, to Fischer-Tropsch synthesis for, use the application scope grain diameter so that reactant
Molecule resistance to mass tranfer in the catalyst reduces, so that the specific surface area of catalyst is relatively large, and then ensures reactant
Can be more abundant with contacting of active specy at catalyst surface, improve the activity of catalyst.
Thus, according to embodiments of the present invention can effectively suppress methane etc. when the catalyst treatment unstripped gas of F-T synthesis
The generation of by-product, makes product concentrate on vapour, diesel oil distillate, and can reduce the selectivity of advanced wax.
In the second aspect of the invention, the present invention proposes a kind of method preparing the above-mentioned catalyst for F-T synthesis.
According to embodiments of the invention, with reference to Fig. 1, described preparation includes for the method for the catalyst of F-T synthesis:
S100: template and solvent, aluminum source, nitric acid, M saline solution are carried out mixed processing
According to embodiments of the invention, template and solvent, aluminum source, nitric acid, M saline solution are carried out mixed processing, thus
Can prepare colloid solution, wherein, M can be Ru, Ce, La or Zr.It should be noted that art technology
People mixes unit and can select the particular type of M salt according to actual needs, such as, can be its nitrate, chlorate etc..
According to one embodiment of present invention, the particular type of template is not particularly restricted, and those skilled in the art are permissible
Selecting according to actual needs, according to a particular embodiment of the invention, template can be selected from P123, CTAB, F127
With at least one in Polyethylene Glycol.
According to still a further embodiment, the particular type of solvent is not particularly restricted, and those skilled in the art are permissible
Selecting according to actual needs, according to a particular embodiment of the invention, solvent can be selected from ethanol, isopropanol, acetic acid
At least one in ethyl ester, ether and pentane.
According to still another embodiment of the invention, the particular type in aluminum source is not particularly restricted, and those skilled in the art are permissible
Select according to actual needs, according to a particular embodiment of the invention, aluminum source can be selected from aluminum isopropylate., aluminium secondary butylate,
In aluminum nitrate, aluminum chloride and aluminum sulfate at least one.
S200: colloid solution is dried process
According to embodiments of the invention, above-mentioned gained colloid solution is dried process, such that it is able to obtain presoma.Tool
Body, by dried, so that the water evaporation on colloid solution surface removes.
According to one embodiment of present invention, the condition of dried is not particularly restricted, and those skilled in the art can root
Selecting according to being actually needed, according to a particular embodiment of the invention, dried can be to carry out under 40～80 degrees Celsius
36～72 hours.
S300: presoma is carried out calcination process
According to embodiments of the invention, the presoma obtained by above-mentioned is carried out calcination process, such that it is able to prepare
MxOy-Al2O3Catalyst carrier.
According to one embodiment of present invention, the condition of calcination process is not particularly restricted, and those skilled in the art can root
Selecting according to being actually needed, according to a particular embodiment of the invention, calcination process can be to enter under 600～800 degrees Celsius
Row 3～6 hours.
S400: use equi-volume impregnating at MxOy-Al2O3Impregnate active component Co in catalyst carrier and carry out heat treatment
According to embodiments of the invention, use equi-volume impregnating M obtained by above-mentionedxOy-Al2O3Soak in catalyst carrier
Stain active component Co and carry out heat treatment, it is hereby achieved that Co/MxOy-Al2O3, wherein, x value 1 or 2, y value
It is 2 or 3.Thus, it is possible to make active component Co at MxOy-Al2O3Catalyst support surface high degree of dispersion, thus can
To significantly improve it to gasoline and the selectivity of diesel oil.Concrete, MxOyCan be RuO2、CeO2、La2O3Or ZrO2。
According to one embodiment of present invention, the condition of heat treatment is not particularly restricted, and those skilled in the art can basis
Being actually needed and select, according to a particular embodiment of the invention, heat treatment can be to be dried 8～12 under 80～150 degrees Celsius
Hour, then 350～600 degrees Celsius of lower roastings.
Thus, the method preparing the catalyst for F-T synthesis according to an embodiment of the invention can effectively prepare
Stating to have and have higher selective catalyst to gasoline and diesel oil, and combined coefficient is high, method is easy, it is easy to implement.
It is equally applicable to this preparation use for for the feature and advantage described by the catalyst of F-T synthesis it should be noted that above-mentioned
In the method for the catalyst of F-T synthesis, here is omitted.
In the third aspect of the invention, the present invention proposes a kind of employing catalyst treatment unstripped gas for F-T synthesis
Method, wherein, in described unstripped gas, the mol ratio of hydrogen and carbon monoxide is 1.5～2.5.According to embodiments of the invention, ginseng
Examining Fig. 2, described employing includes for the method for the catalyst treatment unstripped gas of F-T synthesis:
S10: catalyst is carried out in the reactor activating pretreatment
According to one embodiment of present invention, the condition of activating pretreatment is not particularly restricted, and those skilled in the art are permissible
Selecting according to actual needs, according to a particular embodiment of the invention, activating pretreatment can be at ambient pressure, hydrogen gas
In atmosphere, air speed is 200～1000h-1, temperature is to carry out under 230～450 degrees Celsius 6～20 hours.Concrete, by pre-work
Change processes and metal-oxide can be reduced into corresponding metal simple-substance by reacting with hydrogen.
According to still a further embodiment, the particular type of reactor is not particularly restricted, and those skilled in the art can
To select according to actual needs, according to a particular embodiment of the invention, reactor can use fixed bed reactors, stream
Fluidized bed reactor or paste state bed reactor.
S20: carry out Fischer-Tropsch by contacting with the catalyst after gained activating pretreatment in step S10 in unstripped gas supply to reactor
Synthetic reaction
According to embodiments of the invention, by unstripped gas supply to reactor with gained activating pretreatment in step S10 after urge
Agent contact carries out Fischer-Tropsch synthesis, such that it is able to prepare the reactor product containing C5～C12.It should be noted that
If no special instructions, herein " C5～C12 reactor product " refers to the Organic substance having 5 to 12 carbon atoms in carbochain.
According to one embodiment of present invention, when reactor is fixed bed reactors, the temperature of Fischer-Tropsch synthesis is
230～300 degrees Celsius, air speed is 300-2000h-1, pressure is 0.1～5.5MPa.Thus, it is possible to improve further gasoline and
The productivity of diesel oil.
According to still a further embodiment, when reactor is fluidized-bed reactor, the temperature of Fischer-Tropsch synthesis is
230～280 DEG C, air speed is 500～3000h-1, pressure is 0.1～5.5MPa.Thus, it is possible to improve gasoline and diesel oil further
Productivity.
According to still another embodiment of the invention, when reactor is paste state bed reactor, the temperature of Fischer-Tropsch synthesis is
230～280 degrees Celsius, air speed is 500～3000h-1, pressure is 0.1～5.5MPa.Thus, it is possible to improve further gasoline and
The productivity of diesel oil.
Thus, according to embodiments of the present invention use for F-T synthesis catalyst treatment unstripped gas method by use
Unstripped gas is processed by the catalyst for F-T synthesis stated, and can effectively suppress the generation of the by-products such as methane, make product
Thing concentrates on vapour, diesel oil distillate, and can reduce the selectivity of advanced wax, such that it is able to significantly improve gasoline and diesel oil
Productivity.
Below with reference to specific embodiment, present invention is described, it should be noted that these embodiments are the most descriptive
, and limit the present invention never in any form.
Embodiment 1
Under room temperature, 16gP123 is dissolved in the ethanol of 320ml, after P123 is completely dissolved, by containing the 67% of 26.8ml
Nitric acid (mass concentration), 144mmol aluminum isopropylate. and the RuCl of 16mmol3Mixed solution join in above-mentioned solution, so
After after strong agitation 5h, by the colloid of gained at 60 DEG C of dry 48h, obtain presoma, then by gained presoma at 700 DEG C
Lower calcination 4 hours, obtains Ru2O3-Al2O3Catalyst carrier, then uses equi-volume impregnating, with Co (NO3)2·6H2O is
Co source, at Ru2O3-Al2O3Main active component Co of upper dipping, active metal Co load capacity 20wt%, after standing overnight, then
At 120 DEG C of dry 12h, 400 DEG C of roasting 2h, obtain 20wt%Co/Ru2O3-Al2O3Catalyst.
After testing, 20wt%Co/Ru2O3-Al2O3The diffraction maximum of the oxide of active metal Co, table it is not detected by catalyst
Bright Co is at Ru2O3-Al2O3High degree of dispersion in catalyst carrier, Co active component nano particle diameter is 2nm, catalyst carrier
Crystal grain be 5 μm.
Catalyst F-T activity rating: in fixed bed reactor (12mm*600mm), loaded catalyst is 2g catalysis
Agent, 8g quartz sand, catalyst normal pressure, 300ml/min pure hydrogen atmosphere under in 360 DEG C reduce 10h, then naturally cool to
Less than 80 DEG C switch to unstripped gas, temperature reaction after displacement completely.Reaction condition: 240 DEG C, 500h-l, 1.5MPa, raw material
H in gas2/ CO=2 (mol ratio).Air inlet, wet is controlled by mass flowmenter through the unstripped gas of the purified treatment such as deoxidation, dehydration
It is vented after the metering of formula effusion meter.Reaction result is as shown in table 1:
Table 1 selectivity of product detection data
Embodiment 2
Under room temperature, 16gP123 is dissolved in the ethanol of 320ml, after P123 is completely dissolved, by containing the 67% of 26.8ml
Ce (the NO of nitric acid (mass concentration), 144mmol aluminum isopropylate. and 16mmol3)3Mixed solution join above-mentioned solution
In, then after strong agitation 5h, by obtained colloid at 60 DEG C of dry 48h, obtain presoma, then by gained forerunner
Body is calcination 4 hours at 700 DEG C, obtain Ce2O3-Al2O3Catalyst carrier, then uses equi-volume impregnating, with
Co(NO3)2·6H2O is Co source, at Ru2O3-Al2O3Main active component Co of upper dipping, active metal Co load capacity 20wt%,
After standing overnight, then at 120 DEG C of dry 12h, 400 DEG C of roasting 2h, obtain 20wt%Co/Ce2O3-Al2O3Catalyst.
After testing, 20wt%Co/Ce2O3-Al2O3It is not detected by the diffraction maximum of the oxide of active metal Co on catalyst, shows
Co is at Ce2O3-Al2O3Upper high degree of dispersion, Co active component nano particle diameter is 3nm, and the crystal grain of catalyst carrier is 7 μm.
Catalyst F-T activity rating: in fixed bed reactor (12mm*600mm), loaded catalyst is 2g catalysis
Agent, 8g quartz sand, catalyst normal pressure, 300ml/min pure hydrogen atmosphere under in 360 DEG C reduce 10h, naturally cool to 80 DEG C
Hereinafter switch to unstripped gas, temperature reaction after displacement completely.Reaction condition: 240 DEG C, 500h-l, 1.5MPa, in unstripped gas
H2/ CO=2 (mol ratio).Air inlet, wet type stream is controlled by mass flowmenter through the unstripped gas of the purified treatment such as deoxidation, dehydration
It is vented after gauge metering.Reaction result is as shown in table 2:
Table 2 selectivity of product detection data
Embodiment 3
Under room temperature, 16gP123 is dissolved in the ethanol of 320ml, after P123 is completely dissolved, by containing the 67% of 26.8ml
La (the NO of nitric acid (mass concentration), 144mmol aluminum isopropylate. and 16mmol3)3Mixed solution join above-mentioned solution
In, then after strong agitation 5h, by the colloid of gained at 60 DEG C of dry 48h, obtain presoma, then by gained presoma
At 700 DEG C, calcination 4 hours, obtain La2O3-Al2O3Catalyst carrier, then uses equi-volume impregnating, with
Co(NO3)2·6H2O is Co source, at La2O3-Al2O3Main active component Co of upper dipping, active metal Co load capacity 20wt%,
After standing overnight, then at 120 DEG C of dry 12h, 400 DEG C of roasting 2h, obtain 20wt%Co/La2O3-Al2O3Catalyst.
After testing, 20wt%Co/La2O3-Al2O3It is not detected by the diffraction maximum of the oxide of active metal Co on catalyst, shows
Co is at La2O3-Al2O3Upper high degree of dispersion, Co active component nano particle diameter is 5nm, and the crystal grain of catalyst carrier is 6 μm.
Catalyst F-T activity rating: in fixed bed reactor (12mm*600mm), loaded catalyst is 2g catalysis
Agent, 8g quartz sand, catalyst normal pressure, 300ml/min pure hydrogen atmosphere under in 360 DEG C reduce 10h, naturally cool to 80 DEG C
Hereinafter switch to unstripped gas, temperature reaction after displacement completely.Reaction condition: 240 DEG C, 500h-l, 1.5MPa, in unstripped gas
H2/ CO=2 (mol ratio).Air inlet, wet type stream is controlled by mass flowmenter through the unstripped gas of the purified treatment such as deoxidation, dehydration
It is vented after gauge metering.Reaction result is as shown in table 3:
Table 3 selectivity of product detection data
Embodiment 4
Under room temperature, 16gP123 is dissolved in the ethanol of 320ml, after P123 is completely dissolved, by containing the 67% of 26.8ml
Zr (the NO of nitric acid (mass concentration), 144mmol aluminum isopropylate. and 16mmol3)4Mixed solution join above-mentioned solution
In, then after strong agitation 5h, by obtained colloid at 60 DEG C of dry 48h, obtain presoma, then by obtained
Presoma is calcination 4 hours at 700 DEG C, obtain ZrO2-Al2O3Catalyst carrier, then uses equi-volume impregnating, with
Co(NO3)2·6H2O is Co source, at ZrO2-Al2O3Main active component Co of upper dipping, active metal Co load capacity 20wt%, quiet
After putting overnight, then at 120 DEG C of dry 12h, 400 DEG C of roasting 2h, obtain 20wt%Co/ZrO2-Al2O3Catalyst.
After testing, 20wt%Co/ZrO2-Al2O3It is not detected by the diffraction maximum of the oxide of active metal Co on catalyst, shows
Co is at ZrO2-Al2O3Upper high degree of dispersion, Co active component nano-particle 4nm, the grain size of catalyst carrier is 5 μm.
Catalyst F-T activity rating: in fixed bed reactor (12mm*600mm), loaded catalyst is 2g catalysis
Agent, 8g quartz sand, catalyst normal pressure, 300ml/min pure hydrogen atmosphere under in 360 DEG C reduce 10h, naturally cool to 80 DEG C
Hereinafter switch to unstripped gas, temperature reaction after displacement completely.Reaction condition: 240 DEG C, 500h-l, 1.5MPa, in unstripped gas
H2/ CO=2 (mol ratio).Air inlet, wet type stream is controlled by mass flowmenter through the unstripped gas of the purified treatment such as deoxidation, dehydration
It is vented after gauge metering.Reaction result is as shown in table 4:
Table 4 selectivity of product detection data
Embodiment 5
Repeating embodiment 2, it the difference is that only: aluminum source uses aluminium secondary butylate, and its reaction result is as shown in table 5:
Table 5 selectivity of product detection data
Embodiment 6
Repeating embodiment 2, it the difference is that only: aluminum source uses aluminum nitrate, and its reaction result is as shown in table 6:
Table 6 selectivity of product detection data
Embodiment 7
Repeating embodiment 2, it the difference is that only: aluminum source uses aluminum chloride, and its reaction result is as shown in table 7:
Table 7 selectivity of product detection data
Embodiment 8
Repeating embodiment 2, it the difference is that only: aluminum source uses aluminum sulfate, and its reaction result is as shown in table 8:
Table 8 selectivity of product detection data
Embodiment 9
Catalyst uses the catalyst of embodiment 2, and reactor uses fluidized-bed reactor, and its reaction result is as shown in table 9:
Table 9 selectivity of product detection data
Embodiment 10
Catalyst uses the catalyst of embodiment 2, and reactor uses paste state bed reactor, and its reaction result is as shown in table 10:
Table 10 selectivity of product detection data
Comparative example
Under room temperature, 16gP123 is dissolved in the ethanol of 320ml, after P123 is completely dissolved, by containing the 67% of 26.8ml
Nitric acid (mass concentration) and the mixed solution of 144mmol aluminum isopropylate. join in above-mentioned solution, then in strong agitation
After 5h, by obtained colloid at 60 DEG C of dry 48h, obtain presoma, then by the calcination at 700 DEG C of gained presoma
4 hours, obtain mesoporous Al2O3, then use equi-volume impregnating, with Co (NO3)2·6H2O is Co source, mesoporous
Al2O3Main active component Co of upper dipping, active metal Co load capacity 20wt%, after standing overnight, then it is dried at 120 DEG C
12h, 400 DEG C of roasting 2h, obtain 20wt%Co/Al2O3Catalyst.
After testing, 20wt%Co/Al2O3It is not detected by the diffraction maximum of the oxide of active metal Co on catalyst, shows Co
At Ru2O3-Al2O3Upper high degree of dispersion, Co active component nano particle diameter is 8nm, and the crystal grain of catalyst carrier is 8 μm.
Catalyst F-T activity rating: in fixed bed reactor (12mm*600mm), loaded catalyst is 2g catalysis
Agent, 8g quartz sand, catalyst normal pressure, 300ml/min pure hydrogen atmosphere under in 360 DEG C reduce 10h, naturally cool to 80 DEG C
Hereinafter switch to unstripped gas, temperature reaction after displacement completely.Reaction condition: 240 DEG C, 500h-l, 1.5MPa, in unstripped gas
H2/ CO=2 (mol ratio).Air inlet, wet type stream is controlled by mass flowmenter through the unstripped gas of the purified treatment such as deoxidation, dehydration
It is vented after gauge metering.Reaction result is as shown in table 11:
Table 11 selectivity of product detection data
In the description of this specification, reference term " embodiment ", " some embodiments ", " example ", " concrete example ",
Or specific features, structure, material or the feature bag that the description of " some examples " etc. means to combine this embodiment or example describes
It is contained at least one embodiment or the example of the present invention.In this manual, to the schematic representation of above-mentioned term necessarily
It is directed to identical embodiment or example.And, the specific features of description, structure, material or feature can be arbitrary
Individual or multiple embodiment or example combine in an appropriate manner.Additionally, in the case of the most conflicting, the skill of this area
The feature of the different embodiments described in this specification or example and different embodiment or example can be combined by art personnel
And combination.
Although above it has been shown and described that embodiments of the invention, it is to be understood that above-described embodiment is exemplary,
Being not considered as limiting the invention, those of ordinary skill in the art within the scope of the invention can be to above-described embodiment
It is changed, revises, replaces and modification.
Claims (10)
1. the catalyst for F-T synthesis, it is characterised in that including: active component and catalyst carrier, described work
Property component is Co, and described catalyst carrier is MxOy-Al2O3,
Wherein, M is Ru, Ce, La or Zr, x value 1 or 2, and y value is 2 or 3,
The content of described active component is the 16～24% of described catalyst quality,
The grain size of described catalyst carrier is 4～10 microns, and the specific surface area of described catalyst carrier is 210～320m2/g。
Catalyst the most according to claim 1, it is characterised in that the aperture of described catalyst carrier is 4～8nm.
Catalyst the most according to claim 1 and 2, it is characterised in that the pore volume of described catalyst carrier is
0.4～0.7cm3/g。
4. according to the catalyst according to any one of claim 1-3, it is characterised in that the M in described catalyst carrier accounts for
The 0.01～0.08% of described catalyst quality.
5. according to the catalyst according to any one of claim 1-4, it is characterised in that the grain diameter of described active component
It is 1～10nm.
6. the method for the catalyst for F-T synthesis prepared described in any one of claim 1-5, it is characterised in that
Including:
(1) template and solvent, aluminum source, nitric acid, M saline solution are carried out mixed processing, in order to obtain colloid solution；
(2) described colloid solution is dried process, in order to obtain presoma；
(3) described presoma is carried out calcination process, in order to obtain MxOy-Al2O3Catalyst carrier；
(4) use equi-volume impregnating at described MxOy-Al2O3Impregnate active component Co in catalyst carrier and carry out at heat
Reason, in order to obtain Co/MxOy-Al2O3,
Wherein, M is Ru, Ce, La or Zr, x value 1 or 2, and y value is 2 or 3.
Method the most according to claim 6, it is characterised in that described template is selected from P123, CTAB, F127
With at least one in Polyethylene Glycol；
Optional, source of aluminium be in aluminum isopropylate., aluminium secondary butylate, aluminum nitrate, aluminum chloride and aluminum sulfate at least one；
Optional, described solvent is at least one in ethanol, isopropanol, ethyl acetate, ether and pentane.
8. according to the method described in claim 6 or 7, it is characterised in that in step (2), described dried is
Carry out under 40～80 degrees Celsius 36～72 hours；
Optional, in step (3), described calcination process is to carry out under 600～800 degrees Celsius 3～6 hours；
Optional, in step (4), described heat treatment is to be dried 8～12 hours under 80～150 degrees Celsius, then exists
350～600 degrees Celsius of lower roastings.
9. the method using the catalyst treatment unstripped gas for F-T synthesis according to any one of Claims 1 to 5,
In described unstripped gas, the mol ratio of hydrogen and carbon monoxide is 1.5～2.5, it is characterised in that including:
(1) described catalyst is carried out in the reactor activating pretreatment；
(2) by the supply of described unstripped gas in described reactor with gained activating pretreatment in step (1) after catalyst connect
Touch and carry out Fischer-Tropsch synthesis, in order to obtain the reactor product containing C5～C12.
Method the most according to claim 9, it is characterised in that in step (1), described activating pretreatment be
Under normal pressure, in hydrogen atmosphere, air speed is 200～1000h-1, temperature is to carry out under 230～450 degrees Celsius 6～20 hours；
Optional, described reactor is fixed bed reactors, fluidized-bed reactor or paste state bed reactor；
Optional, in step (2), when described reactor is fixed bed reactors, the temperature of described Fischer-Tropsch synthesis
Being 230～300 degrees Celsius, air speed is 300-2000h-1, pressure is 0.1～5.5MPa；
Optional, in step (2), when described reactor is fluidized-bed reactor, the temperature of described Fischer-Tropsch synthesis
Being 230～280 DEG C, air speed is 500～3000h-1, pressure is 0.1～5.5MPa；
Optional, in step (2), when described reactor is paste state bed reactor, the temperature of described Fischer-Tropsch synthesis
Being 230～280 degrees Celsius, air speed is 500～3000h-1, pressure is 0.1～5.5MPa.
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| WO2018188532A1 (en) * | 2017-04-10 | 2018-10-18 | 武汉凯迪工程技术研究总院有限公司 | High-nitrogen crude oil hydrorefining catalyst and preparation method therefor, and preparation method for carrier thereof |
| CN109847737A (en) * | 2017-11-30 | 2019-06-07 | 中国科学院大连化学物理研究所 | A kind of preparation method of carrier nanometer catalyst |
| CN109529905A (en) * | 2018-12-21 | 2019-03-29 | 陕西师范大学 | A kind of method of the controllable modulation Fischer-Tropsch reaction product distribution of Co base catalyst |
| CN109529905B (en) * | 2018-12-21 | 2022-03-04 | 陕西师范大学 | Method for controllably modulating Fischer-Tropsch reaction product distribution by Co-based catalyst |
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