Preparation method and application of core-shell structure cobalt-base catalyst of middle distillate for synthesis gas preparation

A technology of cobalt-based catalysts and middle distillates, which is applied in the preparation of liquid hydrocarbon mixtures, physical/chemical process catalysts, metal/metal oxides/metal hydroxide catalysts, etc., to achieve high yield, good dispersion, and selectivity sex high effect

Active Publication Date: 2010-08-18
中科潞安能源技术有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the narrow pore size on the microporous H-ZSM-5

Method used

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  • Preparation method and application of core-shell structure cobalt-base catalyst of middle distillate for synthesis gas preparation
  • Preparation method and application of core-shell structure cobalt-base catalyst of middle distillate for synthesis gas preparation
  • Preparation method and application of core-shell structure cobalt-base catalyst of middle distillate for synthesis gas preparation

Examples

Experimental program
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Effect test

Embodiment 1

[0019] Dissolve 3g of cobalt nitrate and 6g of polyvinylpyrrolidone 4000 in 800mL of absolute ethanol, respectively, and transfer them to a polytetrafluoroethylene-lined reactor. React in a homogeneous reactor at 180° C. for 4 hours, and after cooling, transfer the above solution into a beaker to obtain an ethanol suspension containing cobalt tetraoxide nanoparticles. Then, 2L of absolute ethanol, 1.6L of deionized water, 150mL of ammonia water, and 6g of cetyltrimethylammonium bromide were added to the above ethanol suspension, and after stirring for a period of time, 20mL of ethyl orthosilicate was added. After reacting for a period of time, it was filtered, dried, ground, and calcined at 500°C for 6 hours to obtain a cobalt-based catalyst with a core-shell structure, which was named C-1.

[0020] Catalyst evaluation experiment In a pressurized fixed-bed reactor, pure hydrogen was used for temperature-programmed reduction at 300°C, and after cooling down, it was replaced wit...

Embodiment 2

[0022] Dissolve 7g of cobalt acetate and 14g of polyvinylpyrrolidone 10000 in 700mL of absolute ethanol, respectively, and then transfer to a polytetrafluoroethylene-lined reactor. React in a homogeneous reactor at 190° C. for 3 hours, and after cooling, transfer the above solution into a beaker to obtain an ethanol suspension containing cobalt tetroxide nanoparticles. Then add 2L of absolute ethanol, 1L of deionized water, 150mL of ammonia water, and 5g of cetyltrimethylammonium bromide to the above-mentioned ethanol suspension, and after stirring for a period of time, add 10mL of ethyl orthosilicate. After reacting for a period of time, filter, dry, grind, and bake at 400°C for 5 hours to obtain a cobalt-based catalyst with a core-shell structure, which is named C-2.

[0023] Catalyst evaluation experiment In a pressurized fixed-bed reactor, pure hydrogen was used for temperature-programmed reduction at 350°C, and after cooling down, it was replaced with synthesis gas for re...

Embodiment 3

[0025] Dissolve 13g of cobalt nitrate and 26g of polyvinylpyrrolidone 40000 in 1L of absolute ethanol, and then transfer them to a Teflon-lined reactor. React in a homogeneous reactor at 180° C. for 2 hours, and after cooling, transfer the above solution into a beaker to obtain an ethanol suspension containing cobalt tetroxide nanoparticles. Then add 1.5L of absolute ethanol, 1.5L of deionized water, 100mL of ammonia water, and 4g of cetyltrimethylammonium bromide to the above-mentioned ethanol suspension, and after stirring for a period of time, add 15mL of ethyl orthosilicate. After reacting for a period of time, filter, dry, grind, and bake at 550°C for 4 hours to obtain a cobalt-based catalyst with a core-shell structure, which is named C-3.

[0026] Catalyst evaluation experiment In a pressurized fixed-bed reactor, the pure hydrogen was used to reduce the temperature at 400°C by temperature programming, and after cooling down, it was replaced with synthesis gas for reacti...

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Abstract

The invention relates to a core-shell structure cobalt-base catalyst of a middle distillate for synthesis gas preparation, which comprises the following components in percentage by weight: 5 to 30 percent of cobalt and 70 to 95 percent of silica. The catalyst has the following physical properties: the specific surface area is 200 to 1400m<2>/g, the pore volume is 0.5 to 1.3cm<3>/g, the average pore size is 2.0 to 18nm, the cobalt crystallite dimension is 12 to 25nm, and the particle size of the core-shell structure cobalt-base catalyst is less than 100nm, and cobaltosic oxide nano particles are coated in a mesoporous silicon shell to form a core-shell structure. The invention has the advantages of simple operation, high yield, high activity and high selectivity of the middle distillate.

Description

technical field [0001] The invention belongs to the preparation and application of a synthetic oil product catalyst, in particular to a preparation method and application of a catalyst with a cobalt-based core-shell structure for producing middle distillates from syngas. Background technique [0002] Due to the rapid economic development and the depletion of oil resources, the price of crude oil has risen. Fischer-Tropsch synthesis has once again become a research hotspot. Cobalt-based catalysts are attracting extensive attention due to their low water-gas shift reaction, high reactivity, and selectivity to linear saturated hydrocarbons. However, the distribution of hydrocarbon products synthesized by cobalt-based catalysts is wide. In order to reduce the selectivity of long-chain heavy hydrocarbons and improve the selectivity of middle distillates, structure-controlled cobalt-based catalysts were designed to improve the selectivity of middle distillates. Tsubaki et al. o...

Claims

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Application Information

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IPC IPC(8): B01J23/75C10G2/00
Inventor 孙予罕解荣永李德宝侯博王俊刚
Owner 中科潞安能源技术有限公司
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