Composite carrier-supported cobalt-based Fischer-Tropsch synthesis catalyst, and preparation method and application thereof

A composite carrier and Fischer-Tropsch synthesis technology, which is applied in the preparation of liquid hydrocarbon mixtures, molecular sieve catalysts, chemical instruments and methods, etc., can solve the problems of high selectivity of heavy hydrocarbons, low selectivity of methane to CO conversion, and complex catalyst preparation process problems such as low CH4 and CO2 selectivity and high CO conversion

Active Publication Date: 2015-09-02
QINGDAO INST OF BIOENERGY & BIOPROCESS TECH CHINESE ACADEMY OF SCI
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  • Abstract
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Problems solved by technology

However, some oxygen-containing compounds are easily generated on the catalyst, which affects the quality of liquid fuel, and its catalyst preparation needs to be carried out under negative pressure, and the catalyst preparation process is complicated
CN 101966463A discloses a layer of pillar montmorillonite, SiO 2 - Layered pillared montmorillonite and ZrO 2 -Pillar montmorillonite is a carrier, platinum or palladium or ruthenium noble metal promoted cobalt-based catalyst, effectively improving the C in the product 4 -C 20 selectivity, but higher methane selectivity and lower CO conversion
Suk-Hwan Kang et al. (Energy&Fuels2012, 26, 6061-6069) in the traditional Co / SiO 2 ZSM-5 was in situ synthesized on the surface of Fischer-Tropsch synthesis catalyst to increase the C 5 -C 22 Distillate oil selectivity, the preparation of the catalyst is more complex, and C 22 + Selectivity to heavy hydrocarbons is still high

Method used

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  • Composite carrier-supported cobalt-based Fischer-Tropsch synthesis catalyst, and preparation method and application thereof

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preparation example Construction

[0024] 1) Preparation of composite carrier: For example, one or more commercially purchased USY, ZSM-5, MCM-22, HY or beta zeolite molecular sieves are formulated into slurry, and then the ordered mesoporous material TiO 2 , SBA-15, SiC or ZrO 2 One or more of them are added to the slurry, and subjected to ultrasonic treatment for 0.5-10 hours, for example, ultrasonic vibration for 4 hours, to obtain the composite carrier.

[0025] 2) Introduction of additives: one or more soluble salt solutions of Ni, Mn, Zr, La, Ce, Ca or Re such as nitrate aqueous solution, for example, using the method of equal volume impregnation, equal volume impregnation to the step 1) on the composite carrier prepared, then dried and calcined. For example, dry at 100-120°C for 12-36h, such as 12h; bake at a temperature of 300-600°C for 2-8h, for example, bake at 400-600°C for 4-6h;

[0026]3) Introduction of active component cobalt: impregnating an equal volume of cobalt salt solution onto the compos...

preparation example 1

[0037] Weigh 2g of commercially purchased USY zeolite molecular sieve sieved to below 200 mesh and dissolve it in 15mL of absolute ethanol solution, stir at a constant speed with a magnetic stirrer for 2-4h to prepare a slurry, and then slowly add 18g of purchased USY zeolite to the slurry and grind to Mesoporous material ZrO below 200 mesh 2 , using a dual-frequency numerically controlled ultrasonic reactor to ultrasonically vibrate for 4 hours to form a homogeneous mixture of the two materials. Then dry it in an oven at 110°C for 12 hours and take it out. Weigh 1.3g of purchased analytically pure Ca (NO 3 ) 2 4H 2 The O powder was formulated into an aqueous solution, impregnated with an equal volume on the above-mentioned dried composite carrier, dried at 120°C for 12h, and baked in a muffle furnace at 400°C for 4h before taking it out. The analytically pure Co(NO 3 ) 2 ·6H 2 The O powder was formulated into an aqueous solution, impregnated with an equal volume on the...

preparation example 2

[0039] The process is the same as in Preparation Example 1, except that 2 g of USY zeolite molecular sieve is replaced by 2 g of ZSM-5 zeolite molecular sieve to obtain cobalt-based Fischer-Tropsch synthesis catalyst FTC2.

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Abstract

The invention relates to a composite carrier-supported cobalt-based Fischer-Tropsch synthesis catalyst, and a preparation method and an application thereof. The cobalt-based Fischer-Tropsch synthesis catalyst comprises a composite carrier prepared by using zeolite molecular sieve and an ordered meso-porous material, and an active component cobalt and an assistant which are supported on the composite carrier. The preparation method of the catalyst comprises the following steps: preparing the composite carrier composed of the zeolite molecular sieve and the ordered meso-porous material, dipping the active component cobalt and the precursor of the assistant to the composite carrier, drying, and roasting. The cobalt-based Fischer-Tropsch synthesis catalyst using the shape selection and domain restriction of the tunnels of the meso-porous material and the surface acidity of the molecular sieve maintains a high CO conversion rate and high C5-C22 distillate oil selectivity in a wide temperature range, and also has low CH4 and CO2 selectivity.

Description

technical field [0001] The invention relates to a novel cobalt-based Fischer-Tropsch synthesis catalyst, its preparation method and application in Fischer-Tropsch synthesis reaction. Background technique [0002] Fischer-Tropsch (F-T) synthesis is an important way for coal or natural gas to be indirectly converted into liquid fuels through synthesis gas. Compared with gasoline and diesel oil extracted from crude oil, the synthetic liquid fuels contain less sulfur and aromatic hydrocarbons, and are a clean energy. The traditional F-T synthesis chain growth obeys the polymerization mechanism, and the carbon number distribution of the product follows the ASF (Anderson-Schultz-Flory) distribution. Methane and heavy hydrocarbons (waxes) have high selectivity, while the remaining fractions have selectivity limits. Therefore, the products obtained by F-T synthesis are mixed hydrocarbons with a wide product distribution. want to increase gasoline and middle distillates (C 5 -C 2...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J29/14B01J29/46C10G2/00
Inventor 吴晋沪李琢吴黎阳李建青韩德志武景丽杨静
Owner QINGDAO INST OF BIOENERGY & BIOPROCESS TECH CHINESE ACADEMY OF SCI
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