Low-temperature sulfur-tolerant shift catalyst as well as preparation method and application thereof

A sulfur-resistant conversion and catalyst technology, which is applied in the direction of molecular sieve catalysts, chemical instruments and methods, physical/chemical process catalysts, etc., can solve the problems affecting the structural stability and catalytic activity of catalysts, poor ability to resist fluctuations in working conditions, and precipitation of alkali metals Problems such as loss or hardening, to achieve the effects of shortening residence time, reducing diffusion resistance, and concentrating pore size distribution

Active Publication Date: 2021-03-05
CHINA PETROLEUM & CHEM CORP +1
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AI-Extracted Technical Summary

Problems solved by technology

Under low-temperature shift conditions, the sulfur-resistant shift catalyst needs to have good hydration resistance and structural stability, and most of its coagents are alkali metal compounds. However, the inventors of the present disclosure have found through research that alkali metal compounds In the relatively hig...
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Method used

In this series of embodiments, adopt ammoniacal liquor to regulate pH. Can prevent the introduction of other metal ions.
The present disclosure limits the pore distribution of 5~50nm aperture to account for more than 85% purpose of total pore volume is to provide carrier hydrothermal stability, and the relative distribution of concentration aperture, thereby shortens the residence time of reactant in molecular sieve channel , reducing the diffusion resistance.
The present disclosure makes titanium-silicon molecular sieve to modify alumina carrier, and directly co...
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Abstract

The invention provides a low-temperature sulfur-tolerant shift catalyst as well as a preparation method and application thereof. A titanium silicalite molecular sieve and aluminum oxide are used as acarrier to load a catalytic active ingredient; the catalytic active ingredient is cobalt-molybdenum composite metal oxide; the titanium silicalite molecular sieve is combined with an alkali metal compound; the specific surface area of the catalyst is 200m <2>/g-250m <2>/g, and the pore distribution with the pore diameter of 5-50nm in the catalyst accounts for more than 85% of the total pore volume. The preparation method comprises the following steps of: by taking a titanium source, silicic acid alkali metal salt and aluminum salt as raw materials, carrying out a coprecipitation method and calcining to obtain a titanium silicalite molecular sieve combined with an alkali metal compound; mixing the titanium silicalite molecular sieve with aluminum oxide to form a carrier; adding molybdenum salt and cobalt salt into the carrier; and carrying out a reaction to load a cobalt-molybdenum composite metal oxide on the carrier, so as to obtain the low-temperature sulfur-tolerant shift catalyst.According to the method, after coprecipitation is performed in the coprecipitation method, and a precipitate is washed until the pH value is 7.5-8.5. The catalyst provided by the invention has relatively high structural stability and catalytic activity.

Application Domain

Technology Topic

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  • Low-temperature sulfur-tolerant shift catalyst as well as preparation method and application thereof

Examples

  • Experimental program(7)
  • Effect test(1)

Example Embodiment

[0069]Example 1
[0070]8.6 g of tetraethyl titanate was dissolved in 30 ml anhydrous alcohol, and 165 g sodium silicate and 100 ml of deionized water were added, then the pH to 10 was adjusted to the solution A with concentrated ammonia water, and 132 g of aluminum nitrate was dissolved in 250 mL deion. In the water, heated to 60 ° C, and the solution A was added while stirring, then the mixed solution was heated to 80 ° C, and the temperature was maintained at a temperature of 4 h, and the material was washed with deionized water to pH 8.0, and dried at 110 ° C, after 3 h after 600 ° C After mixed with 30 g of active alumina powder, 4G Tianjing powder, 2 g of starch, dry mix were added; 10.4 g of ammonium molybdenum was dissolved in 30 ml of deionized water, and the above powder was added, and 3 g of citric acid , 3 g of oxalic acid and 11.7 g of cobalt nitrate were dissolved in 30 ml deionized water, and combined with molding in the above kneading material, then naturally dried, 480 ° C was baked 4h, naturally, the catalyst C1 was obtained.

Example Embodiment

[0071]Example 2
[0072]2.9 g of titanate is dissolved in 20 ml of anhydrous alcohol, 71 g sodium silicate and 70 ml of deionized water were added, then the pH to 10 was adjusted to the solution A with concentrated ammonia water, and 147 g of nitrate was dissolved in 280 ml deion. In the water, heated to 60 ° C, and the solution A was added while stirring, then the mixed solution was heated to 80 ° C, and the temperature was 5 h, and the material was washed with deionized water to pH 8.0, dried at 120 ° C, 550 ° C after calcination 2h After mixing ball milling of 50 g of active alumina powder, 3G Tianjing powder, 3 g of starch, dry mixed 20 minutes; 12.4 g of ammonium molybdate dissolved in 40 ml of deionized water, add 3 g of citric acid, 1 ml of dilute nitric acid and 7.8 g of nitrate were dissolved in 30 ml deionized water, and combined with molding in the kneading material, then naturally dried, 400 ° C was baked 5h, and naturally catalyst C2 was obtained.
[0073]Among them, the dilute nitric acid is mixed for the commercially available concentrated nitric acid and deionized water to be obtained by mass ratio of 1: 5, and the concentration of the commercially available concentrated nitric acid is 68% (mass percent).

Example Embodiment

[0074]Example 3
[0075]11.4 g of tetraethyl titanate was dissolved in 45 ml anhydrous alcohol, 142 g of sodium silicate and 90 ml of deionized water were added, then the pH to 10 was adjusted with concentrated ammonia water to obtain a solution A, and 110 g of nitrate was dissolved in 190 ml to ion In the water, heated to 60 ° C, and the solution A was added while stirring, and then the mixed solution was heated to 80 ° C, and the temperature was 4 h, and the material was washed with deionized water to pH 8.0, dried at 110 ° C, after calcination at 650 ° C for 3 h After mixed with 37 g of active alumina powder, 2G fields, 4G starch, dry mix were added; 7.4 g of ammonium molybdenum was dissolved in 20 mL of deionized water, and the above powder was added, and 5 g of citric acid And 15.5 g of nitrate is dissolved in 35 ml of deionized water, and combined with molding in the above kneading material, then naturally dried, and then the catalyst C3 is obtained after 3 hours of 450 ° C.
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Description & Claims & Application Information

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