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Carboxylic acid hydrogenation catalyst, preparation method and application thereof

A hydrogenation catalyst and catalyst technology, applied in the petrochemical field, can solve the problems of harsh operating conditions, low selectivity and high reaction pressure

Active Publication Date: 2016-03-30
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0011] In summary, there are some technical and commercial problems in the prior art: high catalyst cost and limited supply of raw materials for catalyst production, low space-time yield, low selectivity, high reaction pressure makes operating conditions too harsh, energy Excessive consumption

Method used

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  • Carboxylic acid hydrogenation catalyst, preparation method and application thereof
  • Carboxylic acid hydrogenation catalyst, preparation method and application thereof
  • Carboxylic acid hydrogenation catalyst, preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0048] Get 1 liter of cobalt nitrate aqueous solution of 1mol / L, add ammonium molybdate 9.5 grams and lanthanum nitrate 7.5g wherein,

[0049] Add 20wt% sodium carbonate solution for precipitation until the pH value is about 9.0, and stir for 2 hours under heating conditions to obtain the precursor I.

[0050] Add 10g of concentrated nitric acid and 6g of calcium nitrate tetrahydrate into 300ml of water, and slowly add to 500g of diluted water glass aqueous solution (with a silicon dioxide content of about 10wt%) to form a white precipitate, and use a high-power stirrer to stir the precipitate to form Slurry, these slurry substances were added to the precursor I, and the aging was continued for 1 hour under stirring conditions. After washing and filtering, and drying overnight to obtain a dry filter cake, 15 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...

Embodiment 2

[0052] Get 1 liter of cobalt nitrate aqueous solution of 1.5mol / L, add 6.0 grams of cerium nitrate and 4 grams of chromium nitrate therein, fully dissolve, under the situation of stirring, add 60 grams of titanium dioxide powders produced by Degussa Company (the model is P25 , the particle size is greater than 150 mesh), and the resulting solid-containing liquid is called solution I. 250ml of ammonium metatungstate solution (tungsten content is about 1.5wt%) dissolved in ammonia water is solution II; 20wt% sodium carbonate solution is solution III. Pour solution II into solution I for precipitation, and finally use solution III to adjust the pH value to about 6.7. Wash and filter subsequently to obtain a wet filter cake; spray 25ml of boric acid solution containing 0.1wt% in this filter cake and leave it to dry after 1 hour. The dry filter cake is calcined and decomposed and shaped to obtain the catalyst CHZ-22.

Embodiment 3

[0054] Dissolve 240g and 15g of dried cobalt nitrate and chromium nitrate respectively in 800ml of n-propanol under the condition of rising temperature, control the temperature at 50-60°C, slowly add 300g of tetraethyl orthosilicate, and prepare cobalt-containing and chromium orthosilicate. Take 100 g of the above cobalt- and chromium-containing ethyl orthosilicate and dissolve it in ethanol, add 600 ml of water and 5.0 g of concentrated nitric acid, and place it at 75° C. for 6 hours to obtain a gel. Add 20ml of silver nitrate aqueous solution (60mgAg / ml) to the above gel, stir and make a slurry, and spray dry the slurry to obtain fine microspheres. After the above-mentioned microspheres were sieved to remove particles above 300 μm, they were calcined at 400° C., and the above-mentioned powder was shaped into tablets to obtain the catalyst CHZ-23.

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Abstract

The invention relates to a carboxylic acid hydrogenation catalyst which comprises a carrier, cobalt elements, and VIB-group elements, wherein the cobalt element accounts for 15 wt%-50 wt% of the total weight of the catalyst; the VIB-group element is at least one selected from molybdenum, tungsten, and chromium, and accounts for 0.5 wt%-15 wt% of the total weight of the catalyst; the carrier is at least one selected from silica, diatomite, calcium silicate, zirconia, and titanium oxide, and accounts for 20 wt%-80 wt% of the total weight of the catalyst. The catalyst is high in activity, high in selectivity of target products, low in manufacturing cost, and mild in reaction conditions.

Description

technical field [0001] The invention belongs to the petrochemical field, and more specifically relates to a catalyst capable of hydrogenating carboxylic acid into alcohol with a high yield and its preparation method and application. Background technique [0002] The research on the hydrogenation of carboxylic acid to alcohol has a long history. As early as 1950, Ford et al applied for the method of converting carboxylic acid to alcohol by using ruthenium catalyst. However, because the cost of petroleum resources was relatively low in the last century and human beings paid less attention to sustainable development, the production of alcohols mostly adopts olefin hydration, oxidation-hydration and other technologies. After entering the 21st century, with the large-scale development of renewable systems and petroleum alternative resources (coal, natural gas, shale gas, coal bed methane), the hydrogenation of carboxylic acids to alcohols has become a more economical and sustaina...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J23/89B01J23/888C07C29/149C07C31/08C07C31/20
Inventor 黄龙王国清田保亮戴伟李宝芹杨溢唐国旗彭晖
Owner CHINA PETROLEUM & CHEM CORP
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