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Cobalt catalyst for preparing alcohol by highly selective hydrogenation of carboxylic acid

A hydrogenation catalyst and catalyst technology, applied in the chemical industry, can solve the problems of harsh operating conditions, low space-time yield, high reaction pressure, etc., and achieve the effects of low cost, good stability, and environmentally friendly composition

Active Publication Date: 2014-05-14
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0012] In summary, there are some technical and commercial problems in the existing carboxylic acid technical solutions: high cost of catalysts and limited supply of raw materials to produce catalysts, low space-time yield, low selectivity, and high reaction pressure make the operating conditions Too demanding, too high energy consumption

Method used

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  • Cobalt catalyst for preparing alcohol by highly selective hydrogenation of carboxylic acid
  • Cobalt catalyst for preparing alcohol by highly selective hydrogenation of carboxylic acid
  • Cobalt catalyst for preparing alcohol by highly selective hydrogenation of carboxylic acid

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0058] Get 1 liter of cobalt nitrate aqueous solution of 1mol / L, add the precipitated silica 40g (silicon dioxide (SiO 2 ) content%≥95.0, fineness (325 mesh sieve residue)%≤1.8, specific surface area is 400~600m 2 / g), the temperature was raised to 60 degrees, and 20wt% sodium carbonate aqueous solution was added under the condition of vigorous stirring until the pH value was 9.0. Gradually raise the temperature to 85° C., keep the constant temperature for 2 hours, add 3.0 g of lanthanum nitrate, continue to keep the temperature for 2 hours, cool down to room temperature, and slowly add 6.0 g of boric acid. After washing and filtering, and drying overnight to obtain a dry filter cake, 10 ml of silver nitrate solution containing 0.1 wt % was sprayed into the filter cake and then granulated. The particles were calcined and decomposed, and then pelletized to obtain the catalyst CHZ-91.

Embodiment 2

[0060] Take 1 liter of 1.2mol / L cobalt nitrate aqueous solution, add 1.0 g of silver nitrate and 10.2 g of copper nitrate to it, after fully dissolving, add concentrated ammonia water (containing NH 3 Mass percentage is about 28%) 0.6L, forming a transparent complex solution. Raise the temperature to 70°C, keep the temperature constant for 2 hours, then slowly add it into 500g of diluted water glass aqueous solution (with a silicon dioxide content of about 10wt%), and then add dropwise 100ml of calcium nitrate solution (calcium nitrate concentration 1.0 mol / L), and continue to stir at constant temperature for 12 hours, add 8 g of boric acid and gradually cool the slurry to room temperature. The above slurry was filtered, washed, and dried overnight to obtain a dry filter cake. The filter cake was roasted and decomposed, and then pelletized to obtain the catalyst CHZ-92.

Embodiment 3

[0066] The above catalyst was evaluated in a fixed-bed reactor for the hydrogenation of acetic acid to produce ethanol. The filling volume was 10ml, diluted with 1:1 quartz sand, and reduced with pure hydrogen before use. The maximum reduction temperature was 450~500°C , the specific reaction conditions and reaction results are shown in Table 1.

[0067] In this example, the acetic acid conversion rate and ethanol selectivity were calculated according to the carbon mole percentage of each component.

[0068]

[0069]

[0070] Other products are: acetaldehyde, ethane, methane, carbon monoxide, carbon dioxide, acetic aldehyde, acetone, propanol, etc.;

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Abstract

The invention relates to a catalyst at least containing cobalt and boron, and a method for preparing alcohol by carboxylic acid hydrogenation with the use of the catalyst. According to the invention, the catalyst at least comprises cobalt accounting for 10 wt%-50 wt% of the total weight of the catalyst, and boron accounting for 1.0 wt%-10 wt% of the total weight of the catalyst. With the catalyst, carboxylic acid can be converted into corresponding alcohol and ester with selectivity of more than 90% under a condition with a temperature of 220-300 DEG C and a pressure of 0.5-4.0 MPa; the catalyst is high in activity, good in stability, and low in cost; the reaction condition when the catalyst is used is not strict; and commercial operation is easy to realize.

Description

technical field [0001] The invention belongs to the field of chemical industry. Specifically, the invention relates to a cobalt-boron catalyst capable of hydrogenating carboxylic acid into alcohol with high yield and its preparation and application method. technical background [0002] The hydrogenation of carboxylic acid to produce alcohol is an important chemical reaction, such as the hydrogenation of acetic acid to produce ethanol and the hydrogenation of lactic acid to produce propylene glycol. This is due to several reasons: due to technological progress, the production cost of carboxylic acids has decreased, such as acetic acid, with the maturity of methanol carbonyl process, the production cost has decreased; or due to the change of raw materials, the production of carboxylic acids has become sustainable, Such as lactic acid, 3-hydroxypropionic acid and other biomass derivatives. [0003] The research on the hydrogenation of carboxylic acid to produce alcohol has a l...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/89C07C29/149C07C31/08C07C31/20
Inventor 黄龙王国清戴伟田保亮李宝芹杨溢唐国旗彭晖
Owner CHINA PETROLEUM & CHEM CORP
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