A microsphere catalyst for preparing lower hydrocarbons from synthetic gas and a preparing method of the catalyst

A technology for synthesis gas and low-carbon hydrocarbons, applied in catalyst activation/preparation, chemical instruments and methods, physical/chemical process catalysts, etc., can solve problems such as catalyst deactivation, easy overheating, and insufficient concentration of products, and achieve optimal Catalytic effect, good technical effect, effect of improving activity

Active Publication Date: 2016-03-30
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0034] The technical problem to be solved by the present invention is that in the prior art, since the reaction of synthesizing light hydrocarbons from synthesis gas is a strong exothermic reaction, when a fixed bed is used, it is difficult to remove heat from the reaction, and it is easy to overheat, so that the catalyst is easily deactivated; When the bed is changed, the products are not concentrated enough, and the selectivity of low-carbon hydrocarbons, especially low-carbon olefins, is not high enough. Provide a new method for producing low-carbon hydrocarbons from syngas

Method used

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  • A microsphere catalyst for preparing lower hydrocarbons from synthetic gas and a preparing method of the catalyst
  • A microsphere catalyst for preparing lower hydrocarbons from synthetic gas and a preparing method of the catalyst
  • A microsphere catalyst for preparing lower hydrocarbons from synthetic gas and a preparing method of the catalyst

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0065] Take 612.0 grams of ferric nitrate and 22.53 grams of zinc nitrate in the same container, add 1000g of water to dissolve, obtain material I, take 0.4 grams of lanthanum nitrate and add 10g of water to dissolve, obtain material II, take 0.15 grams of chromium trioxide, add 100g of water, Stir and dissolve to obtain material III.

[0066] Mix materials I, II, and III, add 312.5 grams of 40% by weight aluminum sol material under stirring, then add 50 g of a solution containing 0.1 gram of KOH, adjust the pH value of the above slurry with ammonia water to make the pH of the mixed slurry = 6.0 After fully stirring, the prepared slurry is subjected to microsphere formation in a spray dryer according to the usual method, and finally in a rotary roaster with an inner diameter of 89 mm and a length of 1700 mm (φ89×1700 mm) at 500 ° C Roasting 2.0 hours, the catalyst composition of making is:

[0067] 50 wt% Fe 100 Cr 0.1 Zn 5.0 K 0.1 La 0.1 o x +50wt%Al 2 o 3

Embodiment 2

[0069] Take 611.9 grams of ferric nitrate and 22.53 grams of zinc nitrate in the same container, add 1000g of water to dissolve, obtain material I, take 0.4 grams of lanthanum nitrate and add 10g of water to dissolve, obtain material II, take 0.15 grams of chromium trioxide, add 100g of water, Stir and dissolve to obtain material III.

[0070] Mix materials I, II, and III, add 312.5 grams of 40% by weight aluminum sol material under stirring, and then add 0.1 gram of KOH and 0.06 gram of RuCl 3 50g of the solution, adjust the pH value of the above slurry with ammonia water to make the pH=6.0 of the mixed slurry, after fully stirring, the prepared slurry is carried out into microspheres in a spray dryer according to the usual method, and finally the inner diameter is 89 mm, length is 1700 mm (φ89 * 1700 mm) rotary roaster at 500 ℃ roasting 2.0 hours, the catalyst composition of making is:

[0071] 50 wt% Fe 100 Cr 0.1 Zn 5.0 K 0.1 La 0.1 Ru 0.01 o x +50wt% Al 2 o 3

Embodiment 3

[0073] Take 611.8 grams of ferric nitrate and 22.52 grams of zinc nitrate in the same container, add 1000g of water to dissolve, obtain material I, take 0.4 grams of lanthanum nitrate and add 10g of water to dissolve, obtain material II, take 0.15 grams of chromium trioxide, add 100g of water, Stir and dissolve to obtain material III.

[0074] Mix materials I, II and III, add 312.5 grams of 40% by weight aluminum sol material under stirring, then add 0.1 gram of KOH, 0.04 gram of PdCl 2 and 0.06 g RuCl 3 50g of the solution, adjust the pH value of the above-mentioned slurry with ammonia water so that the pH=6.0 of the mixed slurry, obtain the slurry after fully stirring, carry out the microsphere molding of the prepared slurry in a spray drier according to the usual method, Inner diameter is 89 millimeters at last, and length is 2.0 hours in 500 ℃ of roastings in the rotary roaster of 1700 millimeters (φ 89 * 1700 millimeters), and the catalyst composition of making is:

[0...

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Abstract

The invention relates to a microsphere catalyst for preparing lower hydrocarbons from synthetic gas and a preparing method of the catalyst, and mainly overcomes problems in the prior art that reaction heat dissipation is difficult when fixed beds are used, and temperature runaway can easily arise so that catalysts are liable to deactivate because reactions of synthesizing the lower hydrocarbons from the synthetic gas are strongly exothermal reactions and a problem that selectivity of lower hydrocarbons especially lower olefins is low. According to a technical scheme, an iron-based fluidized bed catalyst adopting aluminium oxide as a carrier and adopting an active component comprising a composition is adopted, with the chemical formula based on an atomic ratio being shown as Fe<100>KaZnCr<c>La<d>Ox, the synthetic gas is adopted as a raw material, and the raw material is brought into contact with the iron-based fluidized bed catalyst in a fluidized bed and reacts to produce the lower hydrocarbons. The problems are overcome by adoption of the technical scheme. The catalyst can be used for industrial synthesis of the lower hydrocarbons from the synthetic gas in fluidized beds.

Description

technical field [0001] The invention relates to a catalyst for producing low-carbon hydrocarbons from microspherical synthesis gas and a preparation method thereof. Background technique [0002] The method of converting synthesis gas into hydrocarbons through catalyst action was invented by German scientists Frans Fischer and Hans Tropsch in 1923, referred to as F-T synthesis, that is, CO undergoes a heterogeneous catalytic hydrogenation reaction on a metal catalyst to produce straight-chain alkanes and alkenes. Master's mixture process. Germany carried out research and development in the 1920s and realized industrialization in 1936. After World War II, it was closed because it could not compete economically with the oil industry; South Africa has abundant coal resources, but lacks oil resources and has long-term Restricted by international social economic and political sanctions, it was forced to develop coal-to-oil industrial technology, and built the first coal-based F-T...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/86B01J37/08B01J23/89C07C11/04C07C11/06C07C11/08C07C1/04C07C9/04C07C9/06C07C9/08C07C9/10
CPCY02P20/52
Inventor 陶跃武庞颖聪宋卫林李剑锋
Owner CHINA PETROLEUM & CHEM CORP
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