Cobalt-molybdenum low-temperature sulfur tolerant shift catalyst and preparation method thereof

A sulfur-resistant conversion and catalyst technology, applied in chemical instruments and methods, physical/chemical process catalysts, metal/metal oxide/metal hydroxide catalysts, etc., can solve the problem of poor catalyst structure stability and activity stability, Unavoidable operation of the catalyst, reduction of the specific surface of the catalyst, etc., to achieve good economic benefits, good stability of low-temperature conversion activity, and improvement of activity stability and structural stability

Active Publication Date: 2017-04-05
CHINA PETROLEUM & CHEM CORP
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] Industrial low-slew shift catalysts often use the method of adding alkali metal additives to improve their low-temperature shift activity, but the alkali metal additives have the disadvantages of easy loss and easy hardening of the catalyst when it meets water
In addition, the industrial low-stable catalyst carrier contains alumina components. Under the condition of water vapor, the phase structure of alumina can be partially transformed into AlOOH phase. During the process of phase transformation, the pore structure of the support changes significantly. , leading to the reduction of the specific surface of the catalyst, the deterioration of the structural stability and activity stability of the catalyst, and the shortening of the service life
[0004] Although the low-slew catalyst is applied at the end of the conversion system, the operating conditions are relatively mild, but when the production load is adjusted to bring the process gas close to the dew point, the gaseous water will condense into the catalyst bed due to slight fluctuations in the pressure, and the catalyst is inevitable operating under wet conditions

Method used

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  • Cobalt-molybdenum low-temperature sulfur tolerant shift catalyst and preparation method thereof
  • Cobalt-molybdenum low-temperature sulfur tolerant shift catalyst and preparation method thereof
  • Cobalt-molybdenum low-temperature sulfur tolerant shift catalyst and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0043] Dissolve 8.9g of ammonium molybdate in 30.0mL of deionized water to obtain ammonium molybdate solution A; dissolve 11.6g of cobalt nitrate in 30.0mL of deionized water, then add 3.0g of citric acid and 3.0g of oxalic acid to the above cobalt nitrate in sequence solution, stirring and dissolving to obtain solution B containing cobalt. Dissolve 2.7g of lanthanum nitrate in 20mL of deionized water to obtain rare earth additive solution C.

[0044] Weigh 50.0g gibbsite, 8.0g nano zirconia, 30.8g activated carbon, 6g scallop powder and mix evenly, add solution A, knead evenly; then add solution B, knead, shape, dry naturally, and then use high temperature steam Calcined at 380°C for 4h, and then naturally lowered to room temperature to obtain a semi-finished catalyst. The semi-finished catalyst was impregnated with rare earth additive solution C for 3 hours, air-dried, and then fired at 380°C for 4 hours with high-temperature steam to obtain sulfur-tolerant shift catalyst C...

Embodiment 2

[0046] Dissolve 9.2g of ammonium molybdate in 30.0mL of deionized water to obtain ammonium molybdate solution A; dissolve 11.6g of cobalt nitrate in 40.0mL of deionized water, then add 3.0g of citric acid and 3.0g of oxalic acid to the above cobalt nitrate in sequence solution, stirring and dissolving to obtain solution B containing cobalt. Dissolve 2.9g of lanthanum nitrate in 30mL of deionized water to obtain rare earth additive solution C.

[0047] Weigh 51.0g gibbsite, 5.0g nano zirconia, 32.4g activated carbon, 5g scallop powder and mix evenly, add solution A, knead evenly; then add solution B, knead, shape, dry naturally, and then use high temperature steam Calcined at 375°C for 5h, and naturally lowered to room temperature to obtain a semi-finished catalyst. The semi-finished catalyst was impregnated with rare earth additive solution C for 3 hours, dried naturally, and then calcined at 380°C for 4 hours with high-temperature steam to obtain sulfur-tolerant shift cataly...

Embodiment 3

[0049] Dissolve 9.8g of ammonium molybdate in 30.0mL of deionized water to obtain ammonium molybdate solution A; dissolve 11.8g of cobalt nitrate in 30.0mL of deionized water, then add 3.0g of citric acid and 3.0g of carboxymethyl cellulose in sequence into the above-mentioned cobalt nitrate solution, boiled and stirred to dissolve to obtain cobalt-containing solution B. Dissolve 4.0 g of lanthanum nitrate in 35 mL of deionized water to obtain rare earth additive solution C.

[0050] Weigh 52.0g of gibbsite, 7.0g of nano-zirconia, 28.2g of activated carbon, and 8g of scallop powder, mix them evenly, add solution A, and knead evenly; then add solution B, knead, shape, dry naturally, and then use high-temperature steam Calcined at 375°C for 5h, and naturally lowered to room temperature to obtain a semi-finished catalyst. The semi-finished catalyst was impregnated with rare earth additive solution C for 3 hours, dried naturally, and then calcined at 380°C for 4 hours with high-t...

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Abstract

The invention relates to a cobalt-molybdenum low-temperature sulfur tolerant shift catalyst and a preparation method thereof and belongs to the technical field of carbon monoxide shifting. The catalyst comprises active ingredients, an accessory ingredient and carriers, wherein the active ingredients include a cobaltiferous compound and a molybdenum-containing compound, the accessory ingredient is a lanthanum rare earth accessory ingredient, and the carriers include boehmite, nano zirconium oxide and activated carbon. According to cobalt-molybdenum low-temperature sulfur tolerant shift catalyst, AlOOH is utilized to replace an Al2O3 ingredient commonly used in an industrial catalyst, so that the problem that a catalyst containing a gamma-Al2O3 carrier is subjected to phase transformation caused by soaking in water due to working condition changes during operation at a temperature approximate to the dew point can be avoided; the activated carbon ingredient has relatively high specific surface and adsorptive properties, is beneficial to uniform distribution of the active ingredients, and is capable of enhancing adsorptive collection of hydrogen sulfide, so that the shift activity is improved; nano zirconium oxide is capable of improving the crack resistance and tenacity of a common activated carbon carrier; the rare earth accessory ingredient can be used for improving the activity stability and structural stability of the shift catalyst; the preparation method is simple and practical and is easy in production.

Description

technical field [0001] The invention relates to a cobalt-molybdenum-based low-temperature sulfur-resistant shift catalyst and a preparation method thereof, belonging to the technical field of carbon monoxide shift. Background technique [0002] With the rapid development of the coal chemical industry and the continuous improvement of the coal gasification process, the CO content in the gasification synthesis gas is getting higher and higher, some even as high as 70%. On the other hand, the scale of coal gasification is also expanding. The conversion process and conversion catalyst put forward higher requirements. At present, for coal-to-hydrogen and synthetic ammonia production, the conversion process of "pre-transformation + two-stage medium-high temperature main conversion + low-temperature conversion" is mostly used. Among them, the low-temperature shift plays the role of minimizing the CO content at the outlet. From a thermodynamic point of view, the water-gas shift rea...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/887B01J35/10C01B3/16
CPCY02P20/52
Inventor 赵庆鲁余汉涛田兆明白志敏齐焕东王昊薛红霞姜建波
Owner CHINA PETROLEUM & CHEM CORP
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