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Sulfur-tolerant pre-shift catalyst and preparation and vulcanization method thereof

A catalyst and pre-shift technology, which is applied in the direction of catalyst activation/preparation, chemical instruments and methods, heterogeneous catalyst chemical elements, etc., can solve the problems of less research and reports on sulfur-resistant pre-shift catalyst carriers, and achieve good economic benefits and Environmental benefits, outstanding activity stability, and good structural stability

Active Publication Date: 2022-03-01
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Sepiolite is widely used, but there are few studies and reports on the support of sulfur-tolerant pre-shift catalysts

Method used

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  • Sulfur-tolerant pre-shift catalyst and preparation and vulcanization method thereof
  • Sulfur-tolerant pre-shift catalyst and preparation and vulcanization method thereof
  • Sulfur-tolerant pre-shift catalyst and preparation and vulcanization method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0041] The preparation method of described sulfur-resistant pre-shift catalyst comprises the steps:

[0042] 1) Dissolve 2.4g of α-titanic acid in 60mL of dilute nitric acid solution to prepare a modified solution; add the modified solution to 120g of sepiolite and knead for 4 hours, after standing for 4 hours, dry at 100°C for 24h, roast at 420°C for 8h and pulverize To obtain modified sepiolite to less than 160 mesh;

[0043] 2) Weigh 8.5g of cobalt nitrate and 18.0g of ammonium molybdate, add 60mL of ammonia water and 3mL of ethylenediamine, heat to 70°C to obtain a clear solution A1, the measured pH value is 12, add 3g of oxalic acid and 2mL of acetic acid respectively Remove 20mL of deionized water to obtain solution B1;

[0044] 3) Crush the waste hydrogenation catalyst to 160 mesh, weigh 100g as aggregate, mix with modified sepiolite and 2.02g of metatitanic acid, add solution A1, knead evenly, then add solution B1, knead evenly, Shaped, air-dried, and then calcined a...

Embodiment 2

[0046] The preparation method of described sulfur-resistant pre-shift catalyst comprises the steps:

[0047] 1) Dissolve 4.53α-titanic acid in 80mL dilute nitric acid solution to prepare a modified solution; add the modified solution to 150g sepiolite and knead for 6 hours, let it stand for 8 hours, dry at 120°C for 16 hours, roast at 450°C for 8 hours and pulverize To obtain modified sepiolite to less than 160 mesh;

[0048] 2) Weigh 15.08g of cobalt nitrate and 49.78g of ammonium molybdate, add 100mL of ammonia water and 4mL of ethylenediamine, heat to 75°C to obtain a clear solution A2, the measured pH value is 12, add 5g of citric acid to 40mL of deionized Obtain solution B2 in water;

[0049] 3) Pulverize the waste hydrogenation catalyst to 160 mesh, weigh 100g as aggregate, mix evenly with modified sepiolite and 2.83g metatitanic acid, add solution A2, knead evenly, then add solution B2, knead evenly, and Molded, air-dried, and then calcined at 460°C for 8 hours to obt...

Embodiment 3

[0051] The preparation method of described sulfur-resistant pre-shift catalyst comprises the steps:

[0052] 1) Dissolve 7.25α-titanic acid in 100mL dilute nitric acid solution to prepare a modified solution; add the modified solution to 140g sepiolite and knead for 6 hours, let stand for 12 hours, dry at 100°C for 24 hours, roast at 420°C for 6 hours and pulverize To obtain modified sepiolite to less than 160 mesh;

[0053] 2) Weigh 20.11g of cobalt nitrate and 68.66g of ammonium molybdate, add 150mL of ammonia water and 6mL of ethylenediamine, heat to 70°C to obtain a clear solution A3, the measured pH value is 11.5, add 6g of oxalic acid and 12mL of acetic acid respectively 30mL deionized water to obtain solution B3;

[0054] 3) Crush the waste hydrogenation catalyst to 160 mesh, weigh 100g as aggregate, mix evenly with modified sepiolite, 6.5g squid powder, and 6.13g metatitanic acid, add solution A3, knead evenly, and then add solution B3, kneaded evenly, shaped, air-dr...

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Abstract

The invention belongs to the technical field of sulfur-tolerant shift, and particularly relates to a sulfur-tolerant pre-shift catalyst and a preparation and vulcanization method thereof. The catalyst takes acidi-TiO2 modified sepiolite as a carrier and loaded molybdenum and cobalt as active components, comprises the following components in percentage by weight of oxides: 3.0 to 8.0 percent of molybdenum oxide, 1.0 to 4.0 percent of titanium dioxide, 0.5 to 3.0 percent of cobalt oxide and the balance of sepiolite, and is prepared by adopting a mixing and kneading method. The catalyst is high in strength, good in structural stability, low in initial activity and good in activity stability, cobalt and molybdenum are reduced to be in a metal state and then vulcanized, deep vulcanization can be achieved, the activity stability is more prominent, and the catalyst is suitable for protecting the sulfur-tolerant shift catalyst under severe conditions of high pressure, high space velocity and high water-gas ratio; the sepiolite which is wide in source and low in cost is adopted as the raw material, the preparation process is simple, the preparation cost of the catalyst is greatly reduced, and good economic benefits and environmental protection benefits are achieved.

Description

technical field [0001] The invention belongs to the technical field of sulfur-resistant shifting, and in particular relates to a sulfur-resistant pre-shifting catalyst and its preparation and vulcanization method. Background technique [0002] The cobalt-molybdenum series sulfur-resistant wide-temperature shift catalyst is mainly used for the production of raw material gas from heavy raw materials such as heavy oil, residual oil, and coal, and is the core catalyst in the field of coal chemical industry. In recent years, with the development of the coal chemical industry and the advancement of coal chemical technology, the gasification unit process, which is the leading coal chemical industry, is also constantly introducing new ones, and the CO content in the coal gasification synthesis gas is getting higher and higher, such as Siemens GSP gasification technology in Germany The CO content of the synthesis gas reaches more than 55%, and the CO content of the synthesis gas in t...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/882B01J35/10B01J37/00B01J37/18B01J37/20C01B3/16
CPCB01J23/882B01J23/002B01J37/0018B01J37/18B01J37/20C01B3/16B01J2523/00C01B2203/0283C01B2203/1052B01J35/31B01J35/30B01J35/615B01J35/635B01J2523/47B01J2523/68B01J2523/845Y02P20/52
Inventor 姜建波白志敏王昊薛红霞王民余汉涛赵庆鲁
Owner CHINA PETROLEUM & CHEM CORP
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