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Cobalt-based Fischer-Tropsch synthesis catalyst and its preparation method and application

A catalyst, cobalt-based fee technology, applied in the field of cobalt-based Fischer-Tropsch synthesis catalyst and its preparation, can solve the problems of catalyst active component loss, difficult reduction, lengthy process, etc., to improve catalytic activity and stability, and enhance anti-wear The effect of uniform capacity and size distribution

Active Publication Date: 2016-09-14
WUHAN KAIDI ENG TECH RES INST CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] In summary, the existing cobalt-based Fischer-Tropsch synthesis catalysts mainly have the following disadvantages: 1) The existing synthetic oil process route generally needs to go through heavy hydrocarbons, and then rehydrofining to obtain diesel oil, the process is lengthy and the energy consumption is high , the reaction product is distributed in ASF, which makes the selectivity of gasoline and diesel components in the product very low; 2) The higher the dispersion of the catalyst active phase, the catalytic activity will be improved accordingly, and the smaller the dispersion of cobalt oxide particles The higher, but the smaller the particles, the stronger the interaction with the carrier, and the less likely to be reduced. Therefore, it is difficult for existing cobalt-based Fischer-Tropsch synthesis catalysts to have both high reduction and high dispersion; 3) with the slurry bed The development of reactor synthetic oil technology has put forward higher requirements for the anti-wear performance of cobalt-based Fischer-Tropsch synthesis catalysts. The anti-wear performance of existing cobalt-based Fischer-Tropsch synthesis catalysts is not ideal enough, resulting in the loss of catalyst active components or Cracking will reduce the catalytic performance and service life, reduce the product quality and yield, and the worn catalyst will pollute the product, increasing the difficulty of refining downstream products

Method used

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  • Cobalt-based Fischer-Tropsch synthesis catalyst and its preparation method and application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031] Catalyst A: includes 2wt% active component Co, and the rest is mesoporous carbon support; the active component Co is confined in the mesoporous carbon support.

[0032] The preparation method process of catalyst A is as follows:

[0033] 1) Weigh 6g of phenol and add it to a four-neck flask, dissolve it at 40°C, then add 3.2g of 20% sodium hydroxide and stir for 15min, then add 15.53g of 37wt% formaldehyde solution to a constant pressure funnel, then added dropwise to the flask, heated to 90°C, preferably to 70-95°C, more preferably to 80-90°C, after 50 minutes of reaction, transferred the solution to the beaker, cooled to room temperature, added Adjust the pH of the solution to neutral with nitric acid, and then dry it in a vacuum oven at 40°C for 24 hours to remove the water to obtain the phenolic resin, and then add an appropriate amount of absolute ethanol solution to it to prepare a phenolic resin solution with a mass fraction of 20%. ;

[0034] 2) Weigh 8gF127 a...

Embodiment 2

[0038] Catalyst B: includes 7wt% active component Co, and the rest is mesoporous carbon support and mesoporous material shell with high mechanical strength; the active component Co is confined in the mesoporous carbon support.

[0039] The preparation method process of catalyst B is as follows:

[0040] 1) Weigh 6g of phenol and add it to a four-necked flask, dissolve it at 43°C, then add 6.4g of sodium hydroxide with a mass fraction of 20%, stir for 10min, then add 25.87g of 37wt% formaldehyde solution to a constant Press the funnel, then add it dropwise to the flask, react at 80°C for 75 minutes, transfer the solution to a beaker, cool to room temperature, add nitric acid to adjust the pH of the solution to neutral, and then dry it in a vacuum oven at 50°C After 18 hours, remove the water to obtain the phenolic resin, then weigh an appropriate amount of absolute ethanol solution and add it to form a phenolic resin solution with a mass fraction of 18-22%, preferably 20%, wher...

Embodiment 3

[0046] Catalyst C: includes 7wt% active component Co, and the rest is mesoporous carbon support and mesoporous material shell with high mechanical strength; the active component Co is confined in the mesoporous carbon support.

[0047] In the preparation method process of catalyst C, just the surfactant F127 in the step 2) of embodiment 2 is changed into the mixture of P123 and F127, and wherein P123 accounts for the mass fraction of surfactant and is 25% (surfactant can adopt P123 , one or more of F127 or F108, preferably using P123 and F127), other steps are the same as in Example 2.

[0048] The specific surface area of ​​the obtained catalyst C is 349m 2 / g, the average pore diameter is 5.0nm, the pore volume is 0.51mL / g, the thickness of the mesoporous material is 15um, and the average particle diameter is 150um.

[0049] Catalyst C is pre-reduced on a fixed bed before use, and the reducing gas is pure N 2 After the reduction is complete, the catalyst is transferred to ...

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Abstract

The invention discloses a cobalt-base Fischer-Tropsch synthesis catalyst and a preparation method and application thereof. The catalyst comprises a mesoporous carbon carrier and an active component cobalt, wherein the active component cobalt is confined in the mesoporous carbon carrier. The catalyst has specific surface area of 220-400 m<2> / g and particle diameter of 50-150 um. The preparation method employs phenolic resin solution as an organic precursor, and then a sol-gel method is employed to embed the active component Co into the mesoporous carbon carrier. The catalyst prepared by the invention before usage only requires introduction of inert gas into at a certain temperature without hydrogen reduction, so as to obtain the catalyst containing cobalt. The catalyst of the invention has the advantages of high reduction degree, high dispersity, good stability, uniform size of active component, controllable carrier aperture and high selectivity on diesel, and can meet the requirements of a slurry bed reactor on the wear resistance of the catalyst.

Description

technical field [0001] The invention relates to the field of industrial catalytic Fischer-Tropsch synthesis, in particular to a cobalt-based Fischer-Tropsch synthesis catalyst and its preparation method and application. Background technique [0002] Fischer-Tropsch synthesis means that the main component made from coal or natural gas is H 2 The reaction process of synthesizing the synthesis gas with CO and CO under the catalysis of the catalyst to synthesize hydrocarbon liquid fuel is one of the important links to realize the indirect coal liquefaction technology. Fischer-Tropsch synthesis products have the advantages of no sulfur, no nitrogen, and low aromatic content, and have more development potential in today's increasingly serious environmental pollution. The development of catalysts with high activity, high product selectivity and high stability is one of the key technologies of Fischer-Tropsch synthesis. There are many kinds of catalysts used in Fischer-Tropsch syn...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J23/75C10G2/00
Inventor 饶莎莎宋德臣刘倩倩海国良李昌元詹晓东
Owner WUHAN KAIDI ENG TECH RES INST CO LTD
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