AU2016208857A1 - Cobalt-based Fischer-Tropsch synthesis catalyst and preparation method and use thereof - Google Patents
Cobalt-based Fischer-Tropsch synthesis catalyst and preparation method and use thereof Download PDFInfo
- Publication number
- AU2016208857A1 AU2016208857A1 AU2016208857A AU2016208857A AU2016208857A1 AU 2016208857 A1 AU2016208857 A1 AU 2016208857A1 AU 2016208857 A AU2016208857 A AU 2016208857A AU 2016208857 A AU2016208857 A AU 2016208857A AU 2016208857 A1 AU2016208857 A1 AU 2016208857A1
- Authority
- AU
- Australia
- Prior art keywords
- catalyst
- cobalt
- sol
- ethyl alcohol
- ai2o3
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 160
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 39
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 39
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 17
- 239000010941 cobalt Substances 0.000 title claims abstract description 17
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 71
- 239000004964 aerogel Substances 0.000 claims description 42
- 239000000499 gel Substances 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 38
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 235000019441 ethanol Nutrition 0.000 claims description 29
- 239000011148 porous material Substances 0.000 claims description 29
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- 239000002131 composite material Substances 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229960000583 acetic acid Drugs 0.000 claims description 14
- 239000012362 glacial acetic acid Substances 0.000 claims description 14
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 150000001868 cobalt Chemical class 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000002210 silicon-based material Substances 0.000 claims description 8
- 238000000352 supercritical drying Methods 0.000 claims description 8
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 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 5
- 229940011182 cobalt acetate Drugs 0.000 claims description 5
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 5
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 claims description 4
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 229930195733 hydrocarbon Natural products 0.000 description 12
- 150000002430 hydrocarbons Chemical class 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- -1 ethylene, propylene Chemical group 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/12—Silica and alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B01J35/60—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
-
- 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
Abstract
Disclosed are a cobalt-based Fischer-Tropsch synthesis catalyst and a preparation method and the use thereof. The catalyst is comprised of an active component Co and a carrier Al
Description
COBALT-BASED FISCHER-TROPSCH SYNTHESIS CATALYST AND PREPARATION
METHOD AND USE THEREOF
FIELD OF THE INVENTION
[0001] The invention belongs to the Fischer-Tropsch synthesis (F-T synthesis) field of industrial catalysis, and more particularly to a cobalt-based F-T synthesis catalyst for high diesel selectivity, method for preparing the catalyst and application ofthe catalyst.
BACKGROUND OF THE ^MENTION
[0002] F-T synthesis is a chemical process which hrrns syngas into higher hydrocarbons and is one ofthe most important methods for high-efficient toansformation and utilization of non-petooleum carbonic resources (nahrral gas, coal, residual oil, biomass, etc.). Under the influence of catalysts, syngas hrrns into a series of higher hydrocarbons which have different carbon numbers (C1-C20) and are mainly straight-chain alkanes, and some low-carbon alkenes and alcohols. Primary products are firrther processed (separation, hydrocracking or hydroisomerization) to get firel oils of certain specifications such as gasoline and diesel and chemicals such as ethylene, propylene, lubricating oil and paraffin.
[0003] Under certain reaction conditions, CO can him into C5+ hydrocarbons through catalytic hydrogenation to the greatest extent, and then convert into quality fiiel oil through hydrocracking and hydroisomerization. Metals such as Fe, Co, Ni and Ru are more ideal synthetic hydrocarbon catalysts. Among them, Ru has the highest catalytic activity and excellent product chain growth ability but the limited resource and high price ofRu limit the use ofRu as an industrial catalyst. Since Ni as a catalyst is easy to generate methane, it is a catalyst unsuited for synthesizing long-chain hydrocarbons. Therefore, F-T synthesis mostly adopts Fe and Co catalysts. Fe has a higher activity when Fe catalyzes the hydrogenation reaction of CO but Fe is easy to oxidize and form carbon deposits. In addition, Fe has a high water-gas shift reaction activity and a poor chain growth ability of synthetic hydrocarbons. Co is not sensitive to the water-gas shift reaction and has a high catalytic hydrogenation activity; the reaction rate of Co is not influenced by the partial pressure ofwater; Co is not easy to form carbon deposits and be poisonous; the selectivity of 1 generated CO2 is low; the selectivity of long-chain hydrocarbons is high; the products have less oxygen-containing compounds; Co is identified as an existing better catalyst system in synthesizing long-chain hydrocarbons. However, due to the high chain growth ability of Co, it is more difficult to realize selective synthetic products.
[0004] The dispersity of cobalt is closely related to the pore structure of catalysts. First, the conversion rate of CO ofF-Τ synthesis increases linearly as the dispersity of cobalt increases within a certain scope of cobalt dispersity. Second, due to capillary condensation, the generated heavy hydrocarbon covers the catalyst surface in the form of liquid wax and affects the dispersion ofreactants and products (in particular to a-olefin) in the pore structure of catalysts so that new polymerization is caused because a-olefin is re-absorbed by the catalyst surface. Due to the process, the product distribution deviates ftom the ASF distribution. Therefore, to adjust and control the pore structure of a carrier is an important method for adjusting and changing the product disttibution ofF-Τ synthesis to be relatively within a certain carbon number scope (for example, diesel ftaction hydrocarbons).
[0005] Chinese patent publication No. CN 1084153 discloses a method for preparing a cobalt-based catalyst for preparing higher hydrocarbons. The catalyst comprises C0/AI2O3 and a second metal which is not sensitive to carrying capacity. Although the catalyst ofthe patent has a higher catalytic activity, the product distribution ofthe catalyst still conforms to the ASF distribution. Therefore, the selectivity of gasoline and diesel in the product is very low and the wide application ofthe technique for non-petroleum lines to prepare clean liquid firel is limited.
[0006] Danilo L and other people (Catal. Lett, 2012, 142, 1061-1066) reported a bimetallic alloy catalyst ofFe-Co/ multi-pore silicon oxide aerogels prepared by the sol-gel process. The pore volume ofthe catalyst is larger than 2.0cnr١/g; the specific surface area ofthe catalyst is larger than 270 m2/g; and the pore diameters ofthe catalyst range ftom 16mm to 60mm. The reaction is carried out on a fixed bed. The reactivity ofthe catalyst is very high. The conversion rate of CO is up to 95%. The selectivity of low-carbon hydrocarbons C2-C4is higher.
[0007] Wang Qigang and other people (Industrial Catalysis, 2013, 21(5), 1-6) sunrnrarized various achievements of using oxide aerogels for F-T synthesis reported in foreign countries. However, the aerogels reported in the literattrre all take a single aerogel as a carrier to carry a 2 cobalt-based or iron-based catalyst. The pore diameters of the prepared aerogels are larger and the content of olefin in the obtained products is very high.
[0008] At present, there are relatively more institutions, colleges and universities studying aerogels in China. However, most ofthem shrdy a single aerogel. A few of them study composite aerogels. The aerogels are all used for photocatalysis or other materials. At present, there is no report on using aerogels for F-T synthesis in China. There are also not many reports on using aerogels for F-T synthesis overseas. Even if aerogels are used for F-T synthesis, it is a single aerogel used as a carrier and the selectivity of diesel in the product is not high.
SUMMARY OF THE INVENTION
[0009] The invention aims to provide a cobalt-based F-T synthesis catalyst with high dispersity, good heat stability and controllable carrier diameters.
[0010] The second aim ofthe invention is to provide a method for preparing the catalyst.
[0011] The third aim ofthe invention is to provide an application ofthe catalyst.
[0012] In order to solve the technical problems, the cobalt-based F-T synthesis catalyst ofthe invention comprises an active component Co and a carrier composite Al203-Si02 aerogel. If the total amount ofthe catalyst is taken as the base standard, the content ofthe Co is 2%-10 wt. % and the content ofthe composite AlOSiO? aerogel is 90%-98%. The specific surface area ofthe catalyst is 250-750 m2/g, the average pore diameter ofthe catalyst is 9-28.6 nm, and the pore volume ofthe catalyst is 2.75-4.23 mL/g.
[0013] In order to solve the second technical problem, the method for preparing the catalyst of the invention comprises the following steps: [0014] 1. preparing a AI2O3S0I: mixing an aluminum material with water, pouring a resulting mixture into ethyl alcohol, and stirring the mixhrre for 40 to 60 minutes at a constant temperahrre ranging fiom 45.C to 65.(7; standing and cooling the mixture to room temperahrre to get an ΑΙ2Ο3 sol; storing the ΑΙ2Ο3 sol in a refiigerator, a molar ratio ofthe aluminum material to the ethyl alcohol to the water being 1: (4-16): 0.6; 3 [0015] 2. preparing a Si02 sol: mixing a silicon material, water and ethyl alcohol evenly to yield a solution, adding aqueous ammonia to the solution until the pH ofthe solution is 8 to 9, and stirring the solution for 20 to 30 minutes; allowing the solution to stand to form a gel, a molar ratio ofthe silicon material to the ethyl alcohol to the water being 1: (4-6): (4-8); and [0016] 3. preparing a composite Co/AlO-SO aerogel: adding the prepared Si02 sol to the ΑΙ2Ο3 sol according to a molar rate of silicon to aluminum of 1: (1-8); stirring and adding a resulting mixed solution to a mixfore comprising glacial acetic acid, methanol and water; after the solution gels, the Al2٥3-Si02Sol is obtained; after 1 to 5 days of ageing, adding absolute ethyl alcohol to displace water in the sol; pouring out the solution in the gel every 8 hours, and then adding new absolute ethyl alcohol; repeating in this way three times, adding an ethyl alcohol solution with dissolved cobalt salt to the gel; after supercritical drying, a composite
Co/Al2٥3-Si٥2 aerogel is obtained; grinding and screening the obtained catalyst to get a 45 to 100-mesh catalyst; putting the catalyst in a Muffle firrnace and roasting the catalyst at a temperature of 400 to 500.C for 3 to 5 hours to get a target catalyst; a volume ratio ofthe glacial acetic acid to the ethyl alcohol to the water being (1-3): (20-50): (0.5-1); a ratio of a total mass of the glacial acetic acid, methanol and water to a total mass of Si٥2 and ΑΙ2Ο3 gels being (1-30): 100, and a ratio ofthe mass of Co in the cobalt salt to the total mass of Co, the Si٠2 gel and the ΑΙ2Ο3 gel being (2-10): 100.
[0017] In Step 1, the aluminum material is aluminum isopropoxide, aluminum tri-sec-butoxide or aluminum nitrate nonahydrate. The preferred aluminum material is aluminum isopropoxide or aluminum tri-sec-butoxide.
[0018] In Step 2, the silicon material is tetramethoxysilane (TMOS), tetraethyl orthosilicate (TEOS) or sodium silicate. The preferred silicon material is tetoamethoxysilane (TMOS) or tetraethyl orthosilicate (TEOS).
[0019] In Step 3, the cobalt salt is cobalt nitrate, cobalt acetate or cobalt carbonate. The preferred cobalt salt is cobalt nihate or cobalt acetate.
[0020] In order to solve the third technical problem, when the cobalt-based F-T synthesis catalyst ofthe invention is used for F-T synthesis, the catalyst is reduced on a fixed bed reactor before use. After the catalyst cools, syngas is added for F-T synthesis. 4 [0021] The reduction conditions of the catalyst on the fixed bed are that: the gas hourly space velocity of hydrogen is 500-2000 h"\ the heating rate is l-3٥c/min, the temperahrre is 500.C, the reduction time is 4h and the reduction pressure is 0.1-1.0 MPa. The catalytic conditions ofthe catalyst on the fixed bed reactor is that: the reduction temperahrre is 240-280.C, the reduction pressure is 0.1-1 MPa, the volume ratio of Η2 to CO in the syngas is 2:1 and the gas hourly space velocity ofthe synthesis is 500-2000 h").
[0022] The invention has the advantages that: [0023] 1. The catalyst ofthe invention which is prepared by taking the composite ة10ة-203ا٨ aerogel as a cander has a three-dimensional pore system. The active component which scatters in pores evenly prevents the gathering of metal particles and is good for the dispersion ofreactants and products.
[0024] 2. The prepared catalyst ofthe invention has a large specific surface area, a large pore diameter. The active component ofthe catalyst has high dispersity and low resistance to mass transfer.
[0025] 3. The composite gel ofthe invention overcomes the disadvantage that the Si٠2 aerogel has a low effective use temperature, improves the high-temperature stability ofthe ΑΙ2Ο3 aerogel, and enhances the impregnation property ofthe sol to some extent.
[0026] 4. The prepared catalyst ofthe invention changes the toaditional ASF distribution of F-T synthesis products and the selectivity of diesel is high.
BRIEF DESCRIPTION OF THE DRAWINGS
[0027] FIG 1 is a flow chart for manufacturing a catalyst in accordance with one enrbodinrent of the invention.
BRIEF DESCRIPTION OF THE EMDODIMENTS
[0028] For firrther illustrating the invention, experiments detailing a cobalt-based Fischer-Tropsch synthesis catalyst are described hereinbelow conrbined with the drawings. It 5 should be noted that the following examples are intended to describe and not to limit the invention.
Example 1 [0029] The catalyst A comprises an active component Co and a carrier Al203-Si02 composite aerogel. The content of Co is 2%. The content of Al2٥3-Si02 is 98%. The method for preparing the catalyst A is as follow: [0030] 1. Weigh out 1.7 g deionized water and add the deionized water to 32.03 g aluminum isopropoxide. Transfer the mixture to 28.89 g ethyl alcohol. Stir the mixture at 45.C for 60 minutes. Tet the mixhrre sit until it cools to the room temperature to get the ΑΙ2Ο3 sol. Then store the ΑΙ2Ο3 sol in a reftigerator.
[0031] 2. Weigh out and evenly mix 25.38 g TMOS, 30.73 g ethyl alcohol and 12.02 g deionized water. Add aqueous ammonia to the mixture until the pH of the solution is 8, and stir the solution for 20 minutes. Let the solution sit until gel forms to get the Si٥2 sol.
[0032] 3. Weigh out and add I.18g Si٥2S0l to 8.02 g AI2O3S0I. Stir the Si٠2S0l and the ΑΙ2Ο3 sol evenly. Add the 2.76 g mixed solution of glacial acetic acid, methanol and water to the mixture ofthe Si٥2 sol and the ΑΙ2Ο3 sol. The volume ratio of glacial acetic acid to methanol to water is 1: 20: 0.5. After the solution gels, the Al2٥3-Si٥2 sol is finally obtained. After 1 day of ageing, add 40 mL absolute ethyl alcohol. Pour out the solution in the gel every 8 hours, and then add new absolute ethyl alcohol. After repeating in this way three times, add 30 mL ethyl alcohol with 0.8 g dissolved cobalt acetate teftahydrate to the gel. After supercritical drying of Tc=243٥C and Pc=6.38MPa, a composite Co/Al2٥3-Si٥2 aerogel is obtained. Grind and screen the catalyst to obtain a 40 to 100-mesh catalyst. Put the catalyst in a Muffle furnace and roast the catalyst at 400.C for 5 hours to get the catalyst A.
[0033] The specific surface area, average pore diameter and pore volume ofthe catalyst A are 250 m2/g, 28.6 nm and 4.23 mL/g respectively. 6 [0034] Before use, the catalyst is reduced on a fixed bed in advance. Before use, the catalyst is reduced by hydrogen on a fixed bed reactor. After the catalyst cools, syngas is added for F-T sythesis.
[0035] The reduction conditions of the catalyst A on the fixed bed are that: the gas hourly space velocity of hydrogen is 500 h"), the heating rate is l.c/min, the reduction temperature is 500.C, the reduction time is 4h and the reduction pressure is 0.1 MPa. The reduction conditions of the catalyst Aon the fixed bed reactor is that: the reduction temperature is 240.C, the reduction pressure is 0.1 MPa, the volume ratio of El to CO in the syngas is 2:1 and the gas hourly space velocity of the synthesis is 500 h"؛.
Example 2 [0036] The catalyst B comprises an active component Co and a carrier AlO-Si02 composite aerogel. The content of Co is 5%. The content of Al203-Si02 is 95%. The method for preparing the catalyst B is as follow: [0037] 1. Weigh out 1.7 g deionized water and add the deionized water to 38.62 g aluminum fti-sec-butoxide. Transfer the mixture to 72.22 g ethyl alcohol. Stir the mixhrre at 55.C for 55 minutes. Tet the mixhrre sit until it cools to the room temperature to get the ΑΙ2Ο3 sol. Then store the ΑΙ2Ο3 sol in a reftigerator.
[0038] 2. Weigh out and evenly mix 34.74 g TEOS, 46.09 g ethyl alcohol and 15.03 g deionized water. Add aqueous ammonia to the mixture until the pH of the solution is 9, and stir the solution for 25 minutes. Tet the solution sit until gel forms to get the Si٥2 sol.
[0039] 3. Weigh out and add 4.71 g Si٥2 sol to 7.44 g ΑΙ2Ο3 sol. Stir the Si٥2 sol and the ΑΙ2Ο3 sol evenly. Add the 1.82 g mixed solution of glacial acetic acid, methanol and water to the mixture ofthe Si٥2 sol and the ΑΙ2Ο3 sol. The volume ratio of glacial acetic acid to methanol to water is 2:25:0.7. After the solution gels, the Al2٥3-Si٥2 sol is finally obtained. After 3 days of ageing, add 40 mL absolute ethyl alcohol. Pour out the solution in the gel every 8 hours, and then add new absolute ethyl alcohol. After repeating in this way three times, add 30 mT ethyl alcohol with 1.30 g dissolved cobalt carbonate to the gel. After supercritical drying of Tc=243٥C and Pc=6.38 MPa, a composite Co/Al203-Si02 aerogel is obtained. Grind and screen the catalyst to obtain a 40 to 7 100-mesh catalyst. Put the catalyst in a Muffle flirnace and roast the catalyst at 450.C for 4 hours to get the catalyst B.
[0040] The specific surface area, average pore diameter and pore volume of the catalyst B are 500 m2/g, 16.11 nm and 3.86 mL/g respectively.
[0041] Before use, the catalyst is reduced on a fixed bed in advance. Before use, the catalyst is reduced by hydrogen on a fixed bed reactor. After the catalyst cools, syngas is added for F-T synthesis.
[0042] The reduction conditions ofthe catalyst B on the fixed bed are that: the gas hourly space velocity of hydrogen is 1000 h"1, the heating rate is 2٥c/min, the reduction temperature is 500.C, the reduction time is 4h and the reduction pressure is 0.5 MPa. The reduction conditions ofthe catalyst B on the fixed bed reactor is that: the reduction temperature is 260.C, the reduction pressure is 0.5 MPa, and the volume ratio of 2لا to CO in the syngas is 2:1 and the gas hourly space velocity ofthe synthesis is 1000 h"'.
Example 3 [0043] The catalyst c comprises an active component Co and a carrier AlOj-SO composite aerogel. The content of Co is 10%. The content of Al203-Si02 is 90%. The method for preparing the catalyst c is as follow: [0044] 1. Weigh out 1.7 g deionized water and add the deionized water to 58.88 g aluminum nitrate nonahydrate. Transfer the mixhrre to 115.56 g ethyl alcohol. Stir the mixture at 65.C for 40 minutes. Let the mixhrre sit until it cools to the room temperature to get the ΑΙ2Ο3 sol. Then store the ΑΙ2Ο3 sol in a refrigerator.
[0045] 2. Weigh out and evenly mix 34.74 g TEOS, 61.46 g ethyl alcohol and 18.036 g deionized water. Add aqueous ammonia to the mixhrre until the pH ofthe solution is 8, and stir the solution for 30 minutes. Let the solution sit until gel forms to get the Si٥2 sol.
[0046] 3. Weigh out and add 9.42 g Si٥2 sol to 8.09 g ΑΙ2Ο3 sol. Stir the Si٥2 sol and the ΑΙ2Ο3 sol evenly. Add the 0.18 g mixed solution of glacial acetic acid, methanol and water to the mixture ofthe Si٥2 sol and the ΑΙ2Ο3 sol. The volume ratio of glacial acetic acid to methanol to water is 3:50:1.After the solution gels, the AI2O3-SOS0I is finally obtained. After 5 days of ageing, add 40 mL absolute ethyl alcohol. Pour out the solution in the gel every 8 hours, and then add new absolute ethyl alcohol. After repeating in this way three times, add 30 mL ethyl alcohol with 9.60 g dissolved cobalt nitrate hexahydrate to the gel. After supercritical drying of Tc=243٠C and Pc=6.38 MPa, a composite Co/Al203-Si02 aerogel is obtained. Grind and screen the catalyst to obtain a 40 to 100-mesh catalyst. Put the catalyst in a Muffle firmace and roast the catalyst at 500.C for 3 hours to get the catalyst c.
[0047] The specific surface area, average pore diameter and pore volume of the catalyst c are 750 m2/g, 9 nm and 2.75 mL/g respectively.
[0048] Before use, the catalyst is reduced on a fixed bed in advance. Before use, the catalyst is reduced by hydrogen on a fixed bed reactor. After the catalyst cools, syngas is added for F-T synthesis.
[0049] The reduction conditions ofthe catalyst c on the fixed bed are that: the gas hourly space velocity of hydrogen is 1500 h"', the heating rate is 3٠c/min, the reduction temperature is 500.C, the reduction time is 4h and the reduction pressure is 1 MPa. The reduction conditions ofthe catalyst c on the fixed bed reactor is that: the reduction temperature is 280.C, the reduction pressure is 1 MPa, and the volume ratio ofH2 to CO in the syngas is 2:1 and the gas hourly space velocity ofthe synthesis is 2000 h"؛.
Example 4 [0050] The catalyst D comprises an active component Co and a carrier Al203-Si02 composite aerogel. The content of Co is 5%. The content of Al203-Si02is 95%. The method for preparing the catalyst D is as follow: [0051] 1. Weigh out 1.7 g deionized water and add the deionized water to 38.62 g aluminum fti-sec-butoxide. Transfer the mixhrre to 86.66 g ethyl alcohol. Stir the mixture at 60.C for 45 minutes. Let the mixhrre sit until it cools to the room tenrperahrre to get the ΑΙ2Ο3 sol. Then store the ΑΙ2Ο3 sol in a reftigerator. 9 [0052] 2. Weigh out and evenly mix 34.74 g TEOS, 38.41 g ethyl alcohol and 18.04 g deionized water. Add aqueous ammonia to the mixture until the pH ofthe solution is 8, and stir the solution for 30 minutes. Let the solution sit until gel forms to get the Si٥2 sol.
[0053] 3. Weigh out and add 3.14 g Si٥2S0l to 7.96 g AI2O3S0I. Stir the Si02S0l and the ΑΙ2Ο3 sol evenly. Add the 2.22 g mixed solution of glacial acetic acid, methanol and water to the mixhrre ofthe Si٥2 sol and the ΑΙ2Ο3 sol. The volume ratio of glacial acetic acid to methanol to water is 1: 15: 0.5. After the solution gels, the Al2٥3-Si٥2 sol is finally obtained. After 4 days of ageing, add 40 mL absolute ethyl alcohol. Pour out the solution in the gel every 8 hours, and then add new absolute ethyl alcohol. After repeating in this way three times, add 30 mL ethyl alcohol with 2.88 g dissolved cobalt nitrate hexahydrate to the gel. After supercritical drying of Tc=243٠C and Pc=6.38 MPa, a composite Co/Al2٥3-Si٥2 aerogel is obtained. Grind and screen the catalyst to obtain a 40 to 100-mesh catalyst. Put the catalyst in a Muffle furnace and roast the catalyst at 500.C for 3 hours to get the catalyst D.
[0054] The specific surface area, average pore diameter and pore volume ofthe catalyst D are 634 m2/g, 12.38 nm and 3.67 mL/g respectively.
[0055] Before use, the catalyst is reduced on a fixed bed in advance. Before use, the catalyst is reduced by hydrogen on a fixed bed reactor. After the catalyst cools, syngas is added for F-T synthesis.
[0056] The reduction conditions ofthe catalyst D on the fixed bed are that: the gas hourly space velocity of hydrogen is 500 h"', the heating rate is l.c/min, the reduction temperature is 500.C, the reduction time is 4h and the reduction pressure is 0.5 MPa. The reduction conditions ofthe catalyst D on the fixed bed reactor is that: the reduction temperature is 265.C, the reduction pressure is 0.69 MPa, the volume ratio of Η2 to CO in the syngas is 2: 1, and the gas hourly space velocity ofthe synthesis is 500 h"'.
Comparative Example 1 [0057] The catalyst E comprises an active component Co and a carrier ΑΙ2Ο3 aerogel. The content of Co is 5%. The content of ΑΙ2Ο3 aerogel is 95%. The method for preparing the catalyst E is as follows: 10 [0058] 1. Weigh out 1.7 g deionized water and add the deionized water to 58.88 g aluminum nitrate nonahydrate. Transfer the mixture to 86.66 g ethyl alcohol and stir the mixture at 60.C for 45 minutes. Add 18 mL propylene oxide as a network inducing agent and stir the mixhrre evenly. Let the mixhrre sit until gel forms.
[0059] 2. Put the obtained gel in a constant-temperahrre drying oven at 40.C for 48 hours of ageing. Steep the gel in 35 mL absolute ethyl alcohol at a temperahrre ofbelow 60.C for 12 hours two times. Then, steep the gel in 30 mL absolute ethyl alcohol which contains TEOS with a volume ftaction of 80% for 24 hours two times. Then, steep the gel in 30 mL absolute ethyl alcohol for 12 hours two times. Then, add a 30 mL ethyl alcohol solution with 2.07 g dissolved cobalt nitrate hexahydrate. After supercritical drying of Tc=243٠C and Pc=6.38 MPa, a C0/AI2O3 aerogel is obtained. Grind and screen the obtained catalyst to obtain a 40 to 100-mesh catalyst.
Put the catalyst in a Muffle firmace and roast the catalyst at 500.C for 3 hours to get the catalyst E.
[0060] The specific surface area, average pore diameter and pore volume of the catalyst E are 392 m2/g, 10.43 nm and 1.65 mL/g respectively.
[0061 ] Before use, the catalyst E is reduced on a fixed bed in advance. Before use, the catalyst is reduced by hydrogen on a fixed bed reactor. After the catalyst cools, syngas is added for F-T synthesis.
[0062] The reduction conditions of the catalyst E on the fixed bed are that: the gas hourly space velocity of hydrogen is 500 h"', the heating rate is l.c /min, the reduction temperature is 500.C, the reduction time is 4h and the reduction pressure is 0.5 MPa. The reduction conditions ofthe catalyst E on the fixed bed reactor is that: the reduction temperahrre is 265.C, the reduction pressure is 0.69 MPa, the volunre ratio ofH2 to CO in the syngas is 2:1 and the gas hourly space velocity ofthe synthesis is 500 h"'.
Comparative Example 2 [0063] The catalyst F comprises an active component Co and a carrier SiO؛ aerogel. The content of Co is 5%. The content of Si02 aerogel is 95%. The method for preparing the catalyst F is as follows: 11 [0064] 1. Weigh out and mix 27.66 g TEOS, 48.94 g ethy] alcohol, and 9.58 g deionized water to form a reaction mixhrre. Add oxalic acid to adjust the pH to 3-4. After 24 hours, add ammonia to adjust the pH to 8. Stir the reaction mixhrre for 30 minutes. Let the reaction mixhrre sit until gel forms.
[0065] 2. Put the obtained gel at room temperature for 48 hours of ageing. Steep the gel in 35 mL absolute ethyl alcohol for 24 hours two times. Then, add a 30 mL ethyl alcohol solution with 2.07 g dissolved cobalt niftate hexahydrate. After supercritical drying of Tc=243٠C and Pc=6.38MPa, a Co/Si٥2 aerogel is obtained. Grind and screen the obtained catalyst to obtain a 40 to 100-mesh catalyst. Put the catalyst in a Muffle furnace and roast the catalyst at 500.C for 3 hours to get the catalyst E.
[0066] The specific surface area, average pore diameter and pore volume of the catalyst F are 652 m2/g, 15.8 nm and 2.76 mL/g respectively.
[0067] Before use, the catalyst F is reduced on a fixed bed in advance. Before use, the catalyst is reduced by hydrogen on a fixed bed reactor. After the catalyst cools, syngas is added for F-T synthesis.
[0068] The reduction conditions ofthe catalyst F on the fixed bed are that: the gas hourly space velocity of hydrogen is 500h"', the heating rate is l.c /min, the reduction temperafore is 500.C, the reduction time is 4h and the reduction pressure is 0.5MPa. The reduction conditions ofthe catalyst F on the fixed bed reactor is that: the reduction temperahrre is 265.C, the reduction pressure is 0.69 MPa, the volume ratio of Η2 to CO in the syngas is 2:1 and the gas hourly space velocity ofthe synthesis is 500 h"' [0069] The assessment results ofthe catalysts prepared in the embodiment and the comparative embodiment are shown in Table 1.
Table 1 Comparison of Reactant Conversion Rates and Product Selectivity of Catalysts A-F
Catalysts Xco/% S(Ci)/٥/٥ SCO/./. S(C5-Cs)/% S(C9-Ci8)/% S(C18 + )/% A 38.5 14.6 17.8 21.5 38.8 IT B 40.2 10.3 11.1 25.2 49.1 4.3 c 45.2 10.1 10.3 28.5 48.3 2.8 D 42.9 7.8 9.8 24.0 56.1 2.3 12 E 22.7 18.6 11.3 24.2 43.9 2.0 F 28.6 15.0 17.2 26.0 38.7 3.1 [0070] As show in Table 1, as the carrying capacity of active component increases, the conversion rates of CO in the catalysts A-C increase gradually. Maybe the larger the carrying capacity is, the higher the dispersity of active component is. The pore diameter ofthe catalyst A is larger. Although the carrying capacity is small, the resistance to mass transfer is very small, which is good for the conversion of CO. Therefore, the conversion rate of CO ofthe catalyst A can still reach 38.5%. When the carj-ying capacity is 5%, the selectivity ofthe obtained diesel ofthe catalyst is the highest. Therefore, the catalyst D is obtained by optimizing reaction conditions. The maximum selectivity ofthe diesel ofthe catalyst D reaches 56.1% because the prepared composite aerogel carrier has an irregular, internally-interconnected three-dimensional network structure, the high specific surface area and the large pore diameter are good for the dispersity of activity component and the mass transfer of reactants and products, and most active components scatter in pores ofthe aerogel so that it is not easy to lose active components.
[0071 ] Compared to the catalysts E and F which take a single aerogel as the carrier, the catalyst D which takes a composite aerogel as the carrier has a higher conversion rate of CO and a higher selectivity of diesel.
[0072] The experiment results show that the prepared catalysts of the invention have advantages that the dispersity of active components is high, it is not easy to lose the active components and the selectivity ofthe diesel ofthe catalyst is high. 13
Claims (10)
1. A cobalt-based Fischer-Tropsch synthesis catalyst, comprising: an active component Co and a carrier composite AI2O3-S1O2 aerogel; wherein, with a total weight of the catalyst as a base standard, a content of the Co is 2%-10 wt. % and a content of the composite AI2O3-S1O2 aerogel is 90%-98 wt. %; a specific surface area of the catalyst is 250-750 m /g, an average pore diameter of the catalyst is 9-28.6 nm, and a pore volume of the catalyst is 2.75-4.23 mL/g.
2. A method for preparing the cobalt-based F-T synthesis catalyst of claim 1, comprising: 1) preparing a AI2O3 sol: mixing an aluminum material with water, pouring a resulting mixture into ethyl alcohol, and stirring the mixture for 40 to 60 minutes at a constant temperature ranging from 45°C to 65°C; standing and cooling the mixture to room temperature to get an AI2O3 sol; storing the AI2O3 sol in a refrigerator, a molar ratio of the aluminum material to the ethyl alcohol to the water being 1: (4-16): 0.6; 2) preparing a Si02 sol: mixing a silicon material, water and ethyl alcohol evenly to yield a solution, adding aqueous ammonia to the solution until the pH of the solution is 8 to 9, and stirring the solution for 20 to 30 minutes; allowing the solution to stand to form a gel, a molar ratio of the silicon material to the ethyl alcohol to the water being 1: (4-6): (4-8); and 3) preparing a composite C0/AI2O3-S1O2 aerogel: adding the prepared Si02 sol to the AI2O3 sol according to a molar rate of silicon to aluminum of 1: (1-8); stirring and adding a resulting mixed solution to a mixture comprising glacial acetic acid, methanol and water; after the solution gels, the AI2O3-S1O2 sol is obtained; after 1 to 5 days of ageing, adding absolute ethyl alcohol to displace water in the sol; pouring out the solution in the gel every 8 hours, and then adding new absolute ethyl alcohol; repeating in this way three times, adding an ethyl alcohol solution with dissolved cobalt salt to the gel; after supercritical drying, a composite C0/AI2O3-S1O2 aerogel is obtained; grinding and screening the obtained catalyst to get a 45 to 100-mesh catalyst; putting the catalyst in a Muffle furnace and roasting the catalyst at a temperature of 400 to 500°C for 3 to 5 hours to get a target catalyst; a volume ratio of the glacial acetic acid to the ethyl alcohol to the water being (1-3): (20-50): (0.5-1); a ratio of a total mass of the glacial acetic acid, methanol and water to a total mass of S1O2 and AI2O3 gels being (1-30): 100, and a ratio of the mass of Co in the cobalt salt to the total mass of Co, the S1O2 gel and the AI2O3 gel being (2-10): 100.
3. The method of claim 2, wherein in 1), the aluminum material is aluminum isopropoxide, aluminum tri-sec-butoxide or aluminum nitrate nonahydrate.
4. The method of claim 2 or 3, wherein in 1), the aluminum material is aluminum isopropoxide or aluminum tri-sec-butoxide.
5. The method of claim 2 or 3, wherein in 2), the silicon material is tetramethoxysilane (TMOS), tetraethyl orthosilicate (TEOS) or sodium silicate.
6. The method of claim 5, wherein in 2), the silicon material is tetramethoxysilane (TMOS) or tetraethyl orthosilicate (TEOS).
7. The method of claim 2 or 3, wherein in 3), the cobalt salt is cobalt nitrate, cobalt acetate or cobalt carbonate.
8. The method of claim 7, wherein in 3), the cobalt salt is cobalt nitrate or cobalt acetate.
9. Use of the cobalt-based Fischer-Tropsch synthesis catalyst of claim 1 for Fischer-Tropsch synthesis, the use comprising reducing the catalyst using hydrogen in a fixed bed reactor, cooling the catalyst, and applying the catalyst for Fischer-Tropsch synthesis.
10. The use of claim 9, wherein reduction conditions of the catalyst on the fixed bed are that: a gas hourly space velocity of hydrogen is 500-2000 h'1, a heating rate is l-3°C/min, a reduction temperature is 500°C, a reduction time is 4h and a reduction pressure is 0.1-1.0 megapascal; catalytic conditions of the catalyst on the fixed bed reactor is that: a reaction temperature is 240-280°C, a reaction pressure is 0.1-1 MPa, a volume ratio of H2 to CO in syngas is 2:1 and a gas hourly space velocity of the synthesis is 500-2000 h'1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU2018282301A AU2018282301A1 (en) | 2015-01-23 | 2018-12-18 | Cobalt-Based Fischer-Tropsch Synthesis Catalyst And Preparation Method And Use Thereof |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510035042.3 | 2015-01-23 | ||
| CN201510035042.3A CN104624192B (en) | 2015-01-23 | 2015-01-23 | Cobalt-based fischer-tropsch synthesis catalyst and preparation method and application |
| PCT/CN2016/071563 WO2016116055A1 (en) | 2015-01-23 | 2016-01-21 | Cobalt-based fischer-tropsch synthesis catalyst and preparation method and use thereof |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU2018282301A Division AU2018282301A1 (en) | 2015-01-23 | 2018-12-18 | Cobalt-Based Fischer-Tropsch Synthesis Catalyst And Preparation Method And Use Thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| AU2016208857A1 true AU2016208857A1 (en) | 2017-09-07 |
Family
ID=53203715
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU2016208857A Abandoned AU2016208857A1 (en) | 2015-01-23 | 2016-01-21 | Cobalt-based Fischer-Tropsch synthesis catalyst and preparation method and use thereof |
| AU2018282301A Abandoned AU2018282301A1 (en) | 2015-01-23 | 2018-12-18 | Cobalt-Based Fischer-Tropsch Synthesis Catalyst And Preparation Method And Use Thereof |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU2018282301A Abandoned AU2018282301A1 (en) | 2015-01-23 | 2018-12-18 | Cobalt-Based Fischer-Tropsch Synthesis Catalyst And Preparation Method And Use Thereof |
Country Status (6)
| Country | Link |
|---|---|
| CN (1) | CN104624192B (en) |
| AU (2) | AU2016208857A1 (en) |
| BR (1) | BR112017015799A2 (en) |
| CA (1) | CA2974446A1 (en) |
| RU (1) | RU2661897C1 (en) |
| WO (1) | WO2016116055A1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104624192B (en) * | 2015-01-23 | 2017-04-12 | 武汉凯迪工程技术研究总院有限公司 | Cobalt-based fischer-tropsch synthesis catalyst and preparation method and application |
| CN105170153A (en) * | 2015-09-02 | 2015-12-23 | 浙江工业大学 | SiO2 aerogel supported Co-based catalyst and application thereof |
| FR3044004B1 (en) * | 2015-11-23 | 2017-12-15 | Ifp Energies Now | PROCESS FOR SYNTHESIZING HYDROCARBONS FROM SYNTHESIS GAS IN THE PRESENCE OF A CATALYST BASED ON COBALT TRAPS IN A MESOPOROUS OXIDE MATRIX OBTAINED FROM AT LEAST ONE COLLOIDAL PRECURSOR |
| FR3044005B1 (en) * | 2015-11-23 | 2017-12-15 | Ifp Energies Now | PROCESS FOR SYNTHESIZING HYDROCARBONS FROM SYNTHESIS GAS IN THE PRESENCE OF A CATALYST BASED ON COBALT TRAPS IN A MESOPOROUS OXIDE MATRIX AND OBTAINED FROM AT LEAST ONE MONOMERIC PRECURSOR |
| CN107185463B (en) * | 2017-06-26 | 2019-10-18 | 浙江工业大学 | A kind of SiO2-Al2O3The synthetic method of mixed oxide aerogel material |
| CN108435179B (en) * | 2018-05-04 | 2020-11-20 | 山东师范大学 | Preparation method of double-activity monatomic ammonia synthesis catalyst |
| CN110330899A (en) * | 2019-06-27 | 2019-10-15 | 浙江森井科技股份有限公司 | A kind of adhesive and preparation method thereof for photocatalyst |
| CN112973694A (en) * | 2019-12-12 | 2021-06-18 | 中国科学院大连化学物理研究所 | Aluminum element promoted disordered mesoporous silica-supported cobalt-based catalyst and preparation and application thereof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4717708A (en) * | 1983-12-27 | 1988-01-05 | Stauffer Chemical Company | Inorganic oxide aerogels and their preparation |
| CN1057321C (en) * | 1996-05-31 | 2000-10-11 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing heavy hydrocarbon from synthesized gas and preparation method |
| US6235677B1 (en) * | 1998-08-20 | 2001-05-22 | Conoco Inc. | Fischer-Tropsch processes using xerogel and aerogel catalysts by destabilizing aqueous colloids |
| JP4429063B2 (en) * | 2003-04-07 | 2010-03-10 | 新日本製鐵株式会社 | Catalyst for producing hydrocarbon from synthesis gas, method for producing the catalyst, and method for producing hydrocarbon |
| FR2879478B1 (en) * | 2004-12-17 | 2007-10-26 | Inst Francais Du Petrole | COBALT CATALYST FOR THE FISHER-TROPSCH SYNTHESIS |
| CN101890373B (en) * | 2009-05-19 | 2012-06-27 | 中国石油化工股份有限公司 | Silica-alumina composite carrier and method for preparing same |
| CN102233282B (en) * | 2010-04-30 | 2013-06-26 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis catalyst taking silicon oxide-aluminum oxide as carrier and application thereof |
| CN104624192B (en) * | 2015-01-23 | 2017-04-12 | 武汉凯迪工程技术研究总院有限公司 | Cobalt-based fischer-tropsch synthesis catalyst and preparation method and application |
-
2015
- 2015-01-23 CN CN201510035042.3A patent/CN104624192B/en active Active
-
2016
- 2016-01-21 WO PCT/CN2016/071563 patent/WO2016116055A1/en active Application Filing
- 2016-01-21 AU AU2016208857A patent/AU2016208857A1/en not_active Abandoned
- 2016-01-21 BR BR112017015799A patent/BR112017015799A2/en not_active Application Discontinuation
- 2016-01-21 RU RU2017129692A patent/RU2661897C1/en not_active IP Right Cessation
- 2016-01-21 CA CA2974446A patent/CA2974446A1/en not_active Abandoned
-
2018
- 2018-12-18 AU AU2018282301A patent/AU2018282301A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| BR112017015799A2 (en) | 2018-03-27 |
| CN104624192B (en) | 2017-04-12 |
| CA2974446A1 (en) | 2016-07-28 |
| WO2016116055A1 (en) | 2016-07-28 |
| AU2018282301A1 (en) | 2019-01-17 |
| CN104624192A (en) | 2015-05-20 |
| RU2661897C1 (en) | 2018-07-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU2016208857A1 (en) | Cobalt-based Fischer-Tropsch synthesis catalyst and preparation method and use thereof | |
| RU2624441C2 (en) | Cobalt nanocatalizer of fisher-tropsh synthesis, localized in porous material, and method of its obtaining | |
| Yang et al. | A double-shell capsule catalyst with core–shell-like structure for one-step exactly controlled synthesis of dimethyl ether from CO2 containing syngas | |
| CN102452878B (en) | Method for preparing low-carbon olefin by synthetic gas one-step technology | |
| CN102059118B (en) | Dual mesoporous cobalt-based catalyst as well as preparation method and application thereof | |
| CN101698152A (en) | Cobalt-based compounded catalyst and preparing method and application thereof | |
| Okabe et al. | Fischer–Tropsch synthesis over Co–SiO2 catalysts prepared by the sol–gel method | |
| CN101098752B (en) | Cobalt-based catalyst for fischer-tropsch synthesis | |
| CN103203238A (en) | Fischer-Tropsch synthesis catalyst, its preparation and application | |
| CN106607043B (en) | Ferrum-based catalyst and its preparation method and application | |
| EP4046710A1 (en) | Core-shell iron-based catalyst used for direct production of aromatic hydrocarbons from syngas, and preparation method and application therefor | |
| CN105665003A (en) | Hierarchical pore molecular sieve catalyst and preparation method thereof | |
| CN107913729B (en) | Composite catalyst and preparation method thereof | |
| CN106540674B (en) | A kind of metal-doped zirconia catalyst and preparation method thereof with catalyzing and synthesizing the application in gas catalyzed conversion | |
| CN107486226A (en) | Catalyst, the preparation method and its usage of preparation of low carbon olefines by synthetic gas | |
| CN102600864B (en) | Cobalt-based catalyst for Fischer Tropsch synthesis and preparation method thereof | |
| CN105435801B (en) | Load typed iron catalyst and its preparation method and application | |
| CN106607048B (en) | The method of fixed bed production low-carbon alkene | |
| CN102441391B (en) | Preparation method of cobalt-based catalyst for Fischer Tropsch synthesis | |
| CN106040245A (en) | Co-based catalyst as well as preparation method and application thereof | |
| CN102164670A (en) | Preparation methods for liquid hydrocarbons by fischer-tropsch synthesis through slurry reaction | |
| CN101411989A (en) | Preparation of Co-based Fischer-Tropsch synthetic catalyst using silicon based molecular sieve with mixed macropore and mesopore as vector, and uses thereof | |
| CN108654637A (en) | A kind of cobalt-base catalyst and preparation method and application and Fischer-Tropsch synthesis method | |
| CN102059119B (en) | Mesoporous-macroporous cobalt-based catalyst and preparation method and application thereof | |
| CN110295054A (en) | A method of producing mixing isoparaffin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MK5 | Application lapsed section 142(2)(e) - patent request and compl. specification not accepted |