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Catalyst for producing ethanol and preparation method thereof

A catalyst and a technology for producing ethanol, which are applied in chemical instruments and methods, preparation of hydroxyl compounds, preparation of organic compounds, etc., can solve the problems of limited large-scale industrial application of catalyst costs, low space-time yield of ethanol, etc., and achieve inhibition of catalyst deactivation. , Small change in activity, the effect of improving thermal stability

Active Publication Date: 2013-06-26
XIAMEN UNIV +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0008] The transition metal phosphorus compound catalyst reported by CN102631941A can selectively convert acetic acid into ethanol under milder conditions, and the yield is greater than 90%, but the space-time yield of ethanol is low
[0009] In summary, the results of the existing literature show that the noble metal catalyst system exhibits good performance in the hydrogenation reaction of glacial acetic acid, but its expensive catalyst cost limits the possibility of its large-scale industrial application

Method used

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  • Catalyst for producing ethanol and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0035] Dissolve 0.75g of nickel nitrate and 0.36g of ferric nitrate in 50mL of deionized water, add 1g of silicon dioxide, and stir for 1h with the aid of ultrasonic waves. Weigh 0.20 g of potassium borohydride and dissolve it in 5 mL of deionized water, add it into the above mixture with stirring, slowly raise the temperature to 70 °C and continue stirring for 4 h, filter and wash. The obtained solid was dispersed in 10 mL of deionized water, 7.35 mL of 0.1 g / mL aluminum nitrate solution was slowly dropped into the above suspension, stirred and evaporated to dryness at 90 °C, and then calcined at 500 °C for 4 h. The catalyst pellets were sieved to obtain 40-60 mesh solids in 5%H 2 -95%N 2 Reduction in a mixed gas atmosphere for 4 hours, the reduction temperature is 600°C, and the obtained catalyst is 10% Al 2 o 3 15%Ni-5%Fe / SiO 2 .

[0036] Using glacial acetic acid as the raw material, using a fixed-bed reaction system with a catalyst loading of 0.18g, the temperature w...

Embodiment 2

[0038] Keeping the reaction pressure, hydrogen-acid ratio, space velocity and other conditions in Example 1, the temperature was raised to 400°C at a rate of 5°C / min, and after 24 hours, the temperature was lowered back to 220°C, the conversion rate of acetic acid was 97.4%, and the selectivity of ethanol was 96.1% %, thermal stability coefficient 0.99.

Embodiment 3

[0040] Dissolve 0.50 g of nickel nitrate and 0.36 g of ferric nitrate in 30 mL of deionized water, add 1 g of silicon dioxide, and stir for 1 h with the aid of ultrasonic waves. Weigh 0.10g of sodium borohydride and dissolve it in 5mL of deionized water, add it into the above mixture under stirring, slowly raise the temperature to 70°C and continue stirring for 4h, filter and wash, and then roast at 500°C for 4h. The catalyst pellets were sieved to obtain 40-60 mesh solids in 5%H 2 -95%N 2 Reduction in a mixed gas atmosphere for 4 hours, the reduction temperature is 500°C, and the obtained catalyst is 10%Ni-5%Fe / SiO 2 .

[0041] Using glacial acetic acid as raw material, using a fixed-bed reaction system with a catalyst loading of 0.2g, raising the temperature to 220°C at a rate of 10°C / min under a hydrogen flow of 50mL / min, adjusting the hydrogen pressure to 2.0MPa, and controlling the hydrogen flow rate to 157mL / min. The liquid flow rate is 0.005mL / min, and the liquid hou...

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Abstract

The invention relates to a catalyst for producing ethanol and a preparation method thereof. The weight ratio of reactive metal to aid to a protective agent to a carrier in components of the catalyst is (5-30):(0-20):10:100, wherein the reactive metal is any one of nickel, cobalt, copper and manganese; the aid is any one of iron, molybdenum, cerium, barium, zinc and tin; the protective agent is aluminium nitrate or silica sol; and the carrier is carbon nano tube or silica. By taking glacial acetic acid hydrogenation ethanol production reaction as an example, the acetic acid conversion rate is more than 99 percent, the ethanol selectivity is more than 95 percent, the service life of the catalyst exceeds 1000 hours, and the space time yield of the ethanol is more than 1000mg / g-cat. / h under the conditions of the reaction temperature of 225 DEG C and the hydrogen pressure of 2.5MPa. According to introduction of the protective agent, the heat stability of the catalyst is greatly improved, and the series of catalysts are low in cost, simple in preparation, excellent in performance and high in stability and have good industrial application prospects.

Description

technical field [0001] The invention relates to a hydrogenation catalyst, especially a catalyst for producing ethanol from acid or ester hydrogenation and a preparation method thereof. Background technique [0002] Ethanol is a basic industrial raw material and an important organic solvent. It is mainly used in food, chemical industry, military industry, medicine and other fields. In recent years, ethanol gasoline is obtained by adding 5-20% absolute alcohol to gasoline. It is a pollution-free high-octane Valuable gasoline additives can reduce the dependence and consumption of petroleum, and are beneficial to environmental protection, becoming an important energy supplement and strategic resource for the country. The production of ethanol mainly includes biological fermentation method, ethylene hydration method, direct synthesis gas method and indirect synthesis gas method. At present, the industrial production methods of ethanol mainly include grain fermentation method and...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/755B01J23/83B01J23/78B01J23/34B01J27/185B01J23/80B01J23/72C07C31/08C07C29/149
Inventor 叶林敏袁友珠李雯婧张博吴文章吴飞明张素斌计扬黄莹李建辉
Owner XIAMEN UNIV
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