CO sulfur tolerant shift catalyst in cobalt-molybdenum system and preparation method

A sulfur-resistant conversion and catalyst technology, which is applied in the direction of catalyst carriers, chemical instruments and methods, physical/chemical process catalysts, etc., can solve the problems of poor stability, short service life, easy deactivation, etc., achieve outstanding results and improve activity Stability, vulcanization effect

Active Publication Date: 2013-12-18
SHANDONG QILU KELI CHEMICAL RESEARCH INSTITUTE CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] The technical problem to be solved by the present invention is to provide a novel cobalt-molybdenum-based CO sulfur-tolerant shift catalyst to solve the problem of MgAl 2 o 4 Industrial catalysts supported by spinel have problems of poor stability, easy deactivation and short service life under high CO content (≥60%) syngas shift conditions

Method used

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  • CO sulfur tolerant shift catalyst in cobalt-molybdenum system and preparation method
  • CO sulfur tolerant shift catalyst in cobalt-molybdenum system and preparation method
  • CO sulfur tolerant shift catalyst in cobalt-molybdenum system and preparation method

Examples

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Embodiment 1

[0034] Example 1: Preparation of Al-Ti-based surface layer magnesium aluminum spinel

[0035] Buy industrial product spherical alumina carrier with a specific surface of 260m 2 / g, the specific pore volume is 0.44ml / g, the strength is 96N / particle, the water absorption rate is 70%, and the bulk density is 0.60g / ml. The carrier was analyzed by X-ray diffractometer, and the main component of the carrier was γ-Al 2 o 3 . Prepare 90g TiO 2 / L TiCl 4 Acetone solution 70ml, impregnated with 100g of the above-mentioned alumina carrier, placed in the air and fully hydrolyzed, washed to no Cl - , dried at 120°C for 6h, and calcined at 550°C for 3h to obtain an aluminum-titanium composite carrier. Dissolve 100g of magnesium nitrate crystals in 50ml of water, heat to 60°C until the crystals are completely dissolved, impregnate 100g of aluminum-titanium composite carrier with this solution, dry at 120°C for 8 hours, and roast at 600°C for 3 hours to obtain the surface magnesium alum...

Embodiment 2

[0036] Example 2: Preparation of Al-Ti-based surface-layer magnesium-aluminum spinel

[0037] Use the alumina support in embodiment 1, prepare 37gTiO 2 / L TiCl 4 Acetone solution 70ml, impregnated with 100g of the above-mentioned alumina carrier, placed in the air and fully hydrolyzed, washed to no Cl - , dried at 100°C for 8h, and calcined at 500°C for 3h to obtain an aluminum-titanium composite carrier. Dissolve 300g of magnesium nitrate crystals in 60ml of water, heat to 60°C until the crystals are completely dissolved, impregnate 100g of the above-mentioned aluminum-titanium composite carrier with this solution, dry at 100°C for 10 hours, and roast at 750°C for 3 hours to obtain a surface-layer magnesium-aluminum spinel carrier. Carrier composition: TiO 2 : 2%, MgO: 20%, the balance is Al 2 o 3 ;Strength: 136N / piece; Water absorption: 50%; Number Z02.

Embodiment 3

[0038] Example 3: Preparation of Al-Ti-based surface-layer magnesium-aluminum spinel

[0039] Use the alumina carrier in embodiment 1, prepare 70gTiO 2 / L TiCl 4 Acetone solution 70ml, impregnated with 100g of the above-mentioned alumina carrier, placed in the air and fully hydrolyzed, washed to no Cl - , dried at 120°C for 10h, and calcined at 500°C for 3h to obtain an aluminum-titanium composite carrier. Dissolve 25g of magnesium nitrate crystals in 20ml of water, heat to 60°C until the crystals are completely dissolved, impregnate 100g of the above-mentioned aluminum-titanium composite carrier with this solution, dry at 80°C for 12 hours, and roast at 700°C for 3 hours to obtain a surface-layer magnesium-aluminum spinel carrier. Carrier composition: TiO 2 : 4.5%, MgO: 3%, the balance is Al 2 o 3 ;Strength: 97N / piece; Water absorption: 58%; Number Z03.

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Abstract

The invention provides a CO sulfur tolerant shift catalyst in a cobalt-molybdenum system. The CO sulfur tolerant shift catalyst comprises a carrier and active components, wherein the carrier is aluminium-titanium-based surficial magnesium-aluminium spinel; the active components are cobalt and molybdenum. The catalyst is ball-shaped. A preparation method comprises the following steps: introducing titanium on aluminium oxide to prepare the aluminium-titanium composite carrier; uniformly introducing magnesium on the aluminium-titanium composite carrier, and carrying out roasting and phase inversion to form the aluminium-titanium-based surficial magnesium-aluminium spinel; introducing the active components into the aluminium-titanium-based surficial magnesium-aluminium spinel to prepare the catalyst. The CO sulfur tolerant shift catalyst provided by the invention has the advantages that the low-temperature activity and the low-sulfur activity are good, the stability is strong, the adaptability to the demanding conversion condition of synthesized gas with high CO content (more than or equal to 60%) is stronger, the difficulties of poor stability, easy inactivity and short service life when the existing industrial catalyst is used for shifting of the synthesized gas with high CO content as a shifting or pre-shifting catalyst are solved, and the application range of the traditional CO sulfur tolerant shift catalyst is greatly expanded.

Description

technical field [0001] The invention relates to a cobalt-molybdenum-based CO sulfur-tolerant shift catalyst, in particular to a cobalt-molybdenum-based CO sulfur-tolerant shift catalyst with an aluminum-titanium-based surface layer magnesium-aluminum spinel as a carrier and a preparation method thereof. Background technique [0002] CO sulfur-tolerant shift catalysts are widely used to transform sulfur-containing and CO-containing gases generated from heavy oil, residual oil or coal to produce ammonia synthesis gas, hydrogen and carbonyl synthesis gas. Compared with the commonly used iron-chromium-based shift catalysts, it has wide operating temperature range, high shift activity, and no sulfur poisoning problem. Therefore, it has received extensive attention, and many countries have carried out research and development. At present, one of the successfully developed sulfur-tolerant shift catalysts is based on MgAl 2 o 4 Spinel is used as a carrier and does not contain alka...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/882B01J32/00B01J21/10C01B3/16
CPCY02P20/52
Inventor 谭永放田力高步良程玉春邓建利
Owner SHANDONG QILU KELI CHEMICAL RESEARCH INSTITUTE CO LTD
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