Sulfur-tolerant shift methanation integrated catalyst and preparation method

A sulfur-resistant shift, catalyst technology, applied in catalyst activation/preparation, physical/chemical process catalyst, metal/metal oxide/metal hydroxide catalyst, etc., can solve problems such as retention, unindustrial application, etc. Low cost, low preparation cost, and the effect of reducing equipment investment

Active Publication Date: 2022-01-07
CHINA PETROLEUM & CHEM CORP
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] China began to develop sulfur-resistant methanation catalysts in the 1980s. Research institutes such as Dalian Institute of Chemical Physics, University of Science and Technology of China, and Shanghai Gas Research Institute developed a batch of catalysts in the 1990s, but most of them only stayed at the scale of "upgrading" experimental devices , have not been applied industrially

Method used

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  • Sulfur-tolerant shift methanation integrated catalyst and preparation method
  • Sulfur-tolerant shift methanation integrated catalyst and preparation method
  • Sulfur-tolerant shift methanation integrated catalyst and preparation method

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031] (1) 15.8g of ammonium heptamolybdate dissolved in deionized water to obtain 40mL translucent solution A.

[0032] (2) 7.8g of cobalt nitrate, 4.6g of cerium nitrate, 3g oxalic acid and dilute nitric acid were added to 1mL 15mL deionized water to obtain a solution B;

[0033] (3) containing metatitanic acid 98g, 14g 80 # calcium aluminate, 3g Tian Qing powder uniformly dry blended were added to the solution A and B, uniformly kneaded, extruded and dried naturally, to obtain a catalyst after calcination semifinished 550 ℃.

[0034] (4) The catalyst was placed in a semi-finished product in a closed reactor, to 500h -1 Into a space velocity air mixture containing 0.2% hydrogen sulfide, under the conditions of 200 ℃ and 10H is maintained, the temperature was lowered to room temperature, to obtain a finished catalyst C1. Strength, pore structure and catalytic activity data in Table 1.

Embodiment 2

[0036] (1) 18.5g of ammonium molybdate with four 50mL dissolved in deionized water to give a translucent solution A.

[0037] (2) 2.2g of cobalt nitrate, 2.5g of lanthanum nitrate, 4g of citric acid was added to 15mL deionized water to obtain a solution B;

[0038] (3) containing metatitanic acid 75.6g, 30g85 # calcium aluminate, 2g starch uniformly dry blended were added to the solution A and B, uniformly kneaded, extruded and dried naturally, to obtain a catalyst after calcination semifinished 700 ℃.

[0039] (4) The catalyst was placed in a semi-finished product in a closed reactor, to 1000h -1 Into a space velocity air mixture containing 0.1% hydrogen sulfide, under the conditions of 150 deg.] C and 15H is maintained, the temperature was lowered to room temperature, to obtain a finished catalyst C2. Strength, pore structure and catalytic activity data in Table 1.

Embodiment 3

[0041] (1) 9.8g of ammonium heptamolybdate dissolved in deionized water to obtain 35mL translucent solution A.

[0042] (2) 16.0g of cobalt nitrate, yttrium nitrate 3.68, 3g oxalic acid and 2mL of acetic acid were added to 20mL deionized water to give solution B.

[0043] (3) containing 74g of anatase, 13g75 # calcium aluminate, 6g Tian Qing powder uniformly dry blended were added to the solution A and B, uniformly kneaded, extruded and dried naturally, to obtain a catalyst after calcination semifinished 650 ℃.

[0044] (4) The catalyst was placed in a semi-finished product in a closed reactor, to 200h -1 Into a space velocity air mixture containing 0.3% hydrogen sulfide, under the conditions of 150 deg.] C and maintained for 20 h, after cooling to room temperature, to obtain a finished catalyst C3. Strength, pore structure and catalytic activity data in Table 1.

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Abstract

The invention relates to a catalyst for the sulfur-resistant shift methanation reaction of producing synthesis gas from heavy raw materials such as residual oil, heavy oil, petroleum coke, coal, etc., in particular to an integrated sulfur-resistant shift methanation catalyst and a preparation method. The sulfur-resistant shift methanation integrated catalyst includes an active component, a carrier and an auxiliary agent, and is characterized in that cobalt sulfide and molybdenum sulfide are used as active components, titanium oxide and calcium aluminate are used as carriers, and rare earth aids are used. The agent is an auxiliary agent, which is prepared by kneading method. The catalyst of the present invention is not easy to lose active components in the carrier, has good catalyst structure and activity stability, can adapt to high pressure, high space velocity, and low water-gas ratio conditions, and can carry out sulfur-tolerant shift reaction and methanation reaction at the same time, and simultaneously obtain hydrogen and The methane product has a low methanation reaction activation temperature; the preparation method has simple process and low preparation cost.

Description

Technical field [0001] The present invention relates to a catalyst resistant to sulfur heavy feedstocks to synthesis residues, heavy oils, petroleum coke, coal gas conversion methanation reaction, in particular to a sulfur-tolerant shift catalyst and a preparation method methanation integration. Background technique [0002] Currently, gasification means a small amount of hydrogen by-product of low calorific value fuel gas widely used process is to set the conversion line and non-inverting line to satisfy the demand for hydrogen gas and refinery fuel gas, but the investment in apparatus, the fuel gas heat a low value, and the fuel gas and the hydrogen demand can not be flexibly switched. If by embedding conversion stage methanation step, elimination of non conversion lines, in order to simultaneously shift and methanation reaction, after the acid gas removal purifying apparatus, the PSA is separated from the pure hydrogen, as a stripping gas byproduct heat value of the fuel gas w...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J27/051B01J37/08B01J37/20B01J35/10C10L3/08
CPCC10L3/08B01J23/002B01J27/0515B01J35/002B01J35/1019B01J35/1038B01J37/0018B01J37/20B01J2523/00B01J2523/23B01J2523/31B01J2523/3712B01J2523/47B01J2523/3706B01J2523/36
Inventor 赵庆鲁余汉涛田兆明白志敏齐焕东陈依屏李文柱
Owner CHINA PETROLEUM & CHEM CORP
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