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

A catalyst and ethanol production technology, which is applied in the direction of catalyst activation/preparation, chemical instruments and methods, preparation of hydroxyl compounds, etc., can solve the problems of catalytic activity and stability, high space velocity, increased load cost, etc., and achieve excellent Catalytic activity and stability, the effect of improving catalytic activity and reducing the amount of use

Active Publication Date: 2019-01-15
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 prepare ethanol, preparation method and application thereof
  • Catalyst for hydrogenation of acetic acid to prepare ethanol, preparation method and application thereof
  • Catalyst for hydrogenation of acetic acid to prepare ethanol, preparation method and application thereof

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preparation example Construction

[0040] In the second aspect, the present invention also provides a preparation method of the above catalyst, the preparation method comprising: under the condition of ultrasonic, by co-impregnation method and / or step-by-step impregnation method, the precursor of the active component and the first co-agent are mixed The precursor is loaded on the carrier and / or the modified carrier, and then solid-liquid separation, drying and calcination are carried out in sequence; wherein, the impregnation liquid used in the co-impregnation method and / or the 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 adopted, the preparation method of the catalyst provided by the present invention includes: Under the condition of ultrasonic, the carrier and / or the modified carrier a...

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] 32.01 g of magnesium nitrate was dissolved in 100 mL of ethylene glycol solution, and it was added dropwise to the silica sol (285.7 g, containing 35% SiO) through a dropping funnel under constant stirring. 2 )-ammonia water (30mL) mixed solution, at the same time, continuously add 10 times diluted ammonia water to control the pH value of the solution to maintain weak acidity. 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, the obtained filter cake was directly mixed with 6g of saffron powder and 6g of calcium silicate, poured into the kneader, slowly added dropwise with 50mL of nitric acid solution with a concentration of 7%, kneaded and extruded i...

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 of silica powder (the specific surface area measured by BET is 320m 2 / g) directly mixed with 6g of saffron powder and 6g of calcium silicate, poured it into the kneader, slowly added dropwise 50mL of nitric acid solution with a concentration of 7%, kneaded and extruded into a 3mm × 5mm solid rod shape, in The modified carrier was prepared by drying at 120°C for 2h and calcining at 500°C for 4h.

[0107] (2) Preparation of catalyst

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

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Abstract

Relating to the catalyst field, the invention discloses a catalyst for hydrogenation of acetic acid to prepare ethanol, a preparation method and application thereof. Specifically, the catalyst comprises: a carrier, and an active component, a first active assistant, an optional second active assistant and an optional carrier modifier that are loaded on the carrier. The first active assistant is ineggshell-shaped distribution on the carrier surface. Specifically, on the basis of the total weight of the catalyst and in terms of oxides, the content of the active component is 0.2-1wt%, the contentof the first active assistant is 0.5-5wt%, the content of the second active assistant is 0-20wt%, the content of the carrier modifier is 0-20wt%, and the content of the carrier is 54-99.7wt%. When used for the process of hydrogenation of acetic acid to prepare ethanol, the catalyst provided by the invention shows high acetic acid hydrogenation activity, ethanol selectivity and stability.

Description

technical field [0001] The invention relates to the field of catalysts, in particular to a catalyst for producing ethanol by hydrogenation of acetic acid and a preparation method and application thereof. Background technique [0002] At present, the technology of hydrogenation of acetic acid to ethanol has been commercialized by the American company Sennes in Nanjing, Jiangsu with an annual output of 275,000 tons. For this reason, Sennes has applied for a series of patents on the hydrogenation of acetic acid to ethanol, of which US7863489 selected Platinum and tin are active components, which are supported on silica, calcium silicate, graphite, alumina and other carriers by impregnation. At 250°C, the gas space velocity is 2500h. -1 , under the condition of 22 bar pressure, the conversion rate of acetic acid is lower than 85%, and the selectivity of ethanol exceeds 93%, but with the progress of the reaction, the stability of the catalyst decreases. US7608744 uses 10% Co as ...

Claims

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Application Information

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Patent Type & Authority Applications(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