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Catalyst for hydrogenation of acetic acid to ethanol, preparation method and application thereof

A technology for catalyst and ethanol production, which is applied in the direction of catalyst activation/preparation, chemical instruments and methods, preparation of hydroxyl compounds, etc. It can solve the problems of increased load cost, large space velocity, and catalytic activity and stability to be improved, and achieve a reduction The effect of usage amount, improvement of catalytic activity, excellent catalytic activity and stability

Active Publication Date: 2022-03-22
CHNA ENERGY INVESTMENT CORP LTD +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

It can be seen from the patent results disclosed by Senanese that the supported Pt catalyst has certain catalytic activity in the hydrogenation process of acetic acid, but the loading of Pt and additives is still relatively high, and the loading of Pt is basically more than 1%. , but the catalytic activity and stability still need to be improved, and the preparation method is mainly based on the conventional impregnation method
[0003] In addition, CN103331158A discloses a multi-step impregnation method in which carrier modifiers, active components and auxiliary agents are loaded on carriers such as silica, activated carbon, alumina, etc., although the catalyst prepared by this method shows better Activity and stability, but the process of this scheme is complicated, the loading of active metal is about 1%, each step of impregnation needs to be dried and roasted for a long time, and the hydrogen acid is relatively large during the reaction process, and the space velocity is relatively large. The gas consumption is large, which increases the load cost of the device

Method used

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  • Catalyst for hydrogenation of acetic acid to ethanol, preparation method and application thereof
  • Catalyst for hydrogenation of acetic acid to ethanol, preparation method and application thereof
  • Catalyst for hydrogenation of acetic acid to ethanol, preparation method and application thereof

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preparation example Construction

[0040] In the second aspect, the present invention also provides the preparation method of the above-mentioned catalyst, the preparation method comprising: under the condition of ultrasound, the precursor of the active component and the first coagent The precursor is loaded on the support and / or the modified support, and then solid-liquid separation, drying and roasting are carried out in sequence; wherein, the impregnation solution used in the co-impregnation method and / or step-by-step impregnation method contains a surfactant.

[0041] In the present invention, the co-impregnation method and the step-by-step impregnation method can adopt operation steps well known to those skilled in the art. Specifically, when the co-impregnation method is used, the preparation method of the catalyst provided by the invention includes: Under ultrasonic conditions, the carrier and / or the modified carrier is immersed in the impregnating liquid, followed by solid-liquid separation, drying and r...

Embodiment 1

[0095] This example is used to illustrate the catalyst provided by the present invention and its preparation method.

[0096] (1) Preparation of modified carrier

[0097] 32.01g of magnesium nitrate was dissolved in 100mL of ethylene glycol solution, and it was added dropwise to silica sol (285.7g, containing 35% SiO 2 )-ammonia water (30mL) mixed solution, at the same time continuously add dropwise ammonia water diluted 10 times to control the pH value of the solution to maintain a weak acidity, after the dropwise addition is complete, continue to stir for 1-4h, and then let it stand for aging for 1-5h, A precipitate was obtained.

[0098] The precipitate obtained above was filtered and washed several times until the pH value of the solution was neutral, and a filter cake was obtained after filtration. Then, directly mix the obtained filter cake with 6g of scallop powder and 6g of calcium silicate, pour it into a kneader, slowly add 50mL of nitric acid solution with a conce...

Embodiment 2

[0104] This example is used to illustrate the catalyst provided by the present invention and its preparation method.

[0105] (1) Preparation of modified carrier

[0106] 100g silicon dioxide powder (BET measurement specific surface area is 320m 2 / g) directly mixes with 6g squat powder and 6g calcium silicate, pours it into the kneader, slowly adds 50mL nitric acid solution with a concentration of 7% to knead and extrude into a solid rod shape of 3mm×5mm, Dry at 120°C for 2h, and calcined at 500°C for 4h to prepare the modified carrier.

[0107] (2) Preparation of catalyst

[0108] Dissolve 1.64 g of platinum nitrate and 1.74 g of stannous oxalate in 10 mL of ethylene glycol, respectively, and mix the two solutions to form a co-impregnation solution. Furthermore, 30 mL of a 0.5 mg / mL sodium dodecylbenzenesulfonate-ethylene glycol solution was prepared. Then, after the above co-impregnation solution, sodium dodecylbenzenesulfonate-ethylene glycol solution and modified carr...

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Abstract

The invention relates to the field of catalysts, and discloses a catalyst for hydrogenating acetic acid to produce ethanol, a preparation method and application thereof. Specifically, the catalyst includes: a carrier and an active component loaded on the carrier, a first coagent, an optional second coagent and an optional carrier modifier, and the first coagent is in The surface of the carrier is eggshell-shaped distribution; wherein, based on the total weight of the catalyst, in terms of oxides, the content of the active component is 0.2-1% by weight, and the content of the first coagent is 0.5-5% by weight, the content of the second coagent is 0-20% by weight, the content of the carrier modifier is 0-20% by weight, and the content of the carrier is 54-99.7% by weight. The catalyst provided by the invention is used in the process of hydrogenation of acetic acid to produce ethanol, and the catalyst shows higher activity of hydrogenation of acetic acid, ethanol selectivity and stability.

Description

technical field [0001] The invention relates to the field of catalysts, in particular to a catalyst for hydrogenating acetic acid to produce ethanol, a preparation method and application thereof. Background technique [0002] At present, the technology of hydrogenation of acetic acid to ethanol has been commercialized by American Senanese Company in Nanjing, Jiangsu Province with an annual output of 275,000 tons. For this reason, Senanese Company has applied for a series of patents on the hydrogenation of acetic acid to ethanol, of which US7863489 is selected Platinum and tin are the active components, which are loaded on silicon oxide, calcium silicate, graphite, alumina and other carriers by impregnation. At 250 ° C, the gas space velocity is 2500 h -1 , under the condition that the pressure is 22 bar, the conversion rate of acetic acid is lower than 85%, and the ethanol selectivity exceeds 93%, but the stability of the catalyst decreases as the reaction proceeds. US76087...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J23/62B01J27/188B01J27/19B01J35/02B01J37/02B01J37/34C07C29/149C07C31/08B01J35/00
CPCC07C29/149B01J23/624B01J27/188B01J27/19B01J37/0203B01J37/343B01J35/50C07C31/08
Inventor 龙俊英田树勋陈强程继红孟祥堃胡云剑
Owner CHNA ENERGY INVESTMENT CORP LTD