Hydroquinone hydrogenation catalyst, preparation method and hydrogenation reaction method

A technology of hydrogenation catalyst and hydroquinone, which is applied in the direction of hydrogenation preparation, molecular sieve catalyst, chemical instruments and methods, etc., can solve the problem of low yield of 1,4-cyclohexanediol, high requirements for reaction equipment, iodination Eliminate the problems of expensive shirts and other problems, and achieve the effects of simple preparation method, good catalytic effect, and low industrial cost

Inactive Publication Date: 2017-06-23
LANZHOU UNIVERSITY OF TECHNOLOGY
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AI Technical Summary

Problems solved by technology

An Huajuan et al. used Raney-Ni as a catalyst to prepare 1,4-cyclohexanediol under the condition of hydrogen pressure of 6.0 MPa. The conversion rate was 99.9%, but the hydrogen pressure was too high and the reaction conditions were harsh. Requirements for reaction equipment are too high (An Huajuan, Zhejiang Chemical Industry, 2006, 37(2):5-25)
Y. Komachil prepared 1,4-cyclohexanediol by reducing hydroquinone with thorium iodide as a reducing agent in KOH solution. Due to the high price of thorium iodide, the production cost was too high (Komaehi Y, Tetrahedron Letters, 1994, 35:4169-4172)
Wang Hongjun et al. used Ru / C as a catalyst to catalyze the hydrogenation of hydroquinone to 1,4-cyclohexanediol at a temperature of 150 °C and a hydrogen pressure of 5.0 MPa. The yield was 76.8%, but there was Disadvantages of high hydrogen pressure and harsh reaction conditions (Wang Hongjun, Molecular Catalysis, 2010, 24:315-321)
Chinese patent (CN201019100011.6) reports a method for the synthesis of hydroquinone by catalytic hydrogenation, that is, hydroquinone is hydrogenated with hydrogen in the presence of a ruthenium catalyst, in the absence of a solvent or with supercritical carbon dioxide as the reaction medium 1,4-cyclohexanediol is finally obtained in the reaction, and the reaction temperature is 60~150°C. Although this method does not use toxic and harmful organic solvents, and the reaction rate is fast, the yield of 1,4-cyclohexanediol is low , only 43.5 %

Method used

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  • Hydroquinone hydrogenation catalyst, preparation method and hydrogenation reaction method
  • Hydroquinone hydrogenation catalyst, preparation method and hydrogenation reaction method

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preparation example Construction

[0021] The preparation method of hydroquinone hydrogenation catalyst, its step is:

[0022] (1) The carrier is pre-calcined in a muffle furnace at 300-600°C for 6 hours, and then sieved for use;

[0023] (2) Prepare a solution with a concentration of 0.3-3.0 mol / L of the soluble compound of the active component Ru with distilled water, add a carrier to the prepared solution, and immerse under strong stirring for 1-5 h to obtain a solution;

[0024] (3) Make the soluble salt of component B of the additive into b solution with a concentration of 0.03~1.0 mol / L;

[0025] (4) Add the prepared b solution directly to a solution to obtain a c mixed solution, and continue aging for 2~10 h after adding;

[0026] (5) The precipitant is made into a d solution with a concentration of 0.03~2.0 mol / L;

[0027] (6) Add the prepared d solution to the c mixed solution dropwise, the reaction temperature is kept at 80 ℃ during the dropping process, and continue to age for 5~20 h after the addi...

Embodiment 1

[0051] Example 1: Weigh 0.3 g of ruthenium chloride hexahydrate and dissolve it in 60 ml of distilled water. After it is completely dissolved, add 5.5 g of HY molecular sieve and soak it at 80°C for 3 h, then dissolve 0.03 g of lanthanum oxide in 20 ml of distilled water Add the above mixed solution and continue stirring and impregnating for 3 h, then add dropwise 0.05 mol / L urea aqueous solution, continue aging for 18 h, filter and wash, then dry at 110 °C for 24 h, grind the dried catalyst to 200 mesh, The obtained catalyst was reductively activated under the following conditions: reduction with hydrogen (hydrogen pressure 0.1-3.0 MPa) at 500 °C for 3 h, and then lowered to room temperature under the protection of high-purity nitrogen. The obtained catalyst sample was recorded as 1# catalyst, and 0.5 g of catalyst 1# was taken for activity evaluation.

Embodiment 2

[0052] Example 2: Weigh 0.3 g of ruthenium oxide and dissolve it in 60 ml of distilled water. After it is completely dissolved, add 5.5 g of NaY molecular sieve and soak it at 80°C for 1.5 h, then dissolve 0.03 g of calcium nitrate in 20 ml of distilled water, add Continue to stir and impregnate in the above mixed solution for 9 h, then add dropwise 0.03 mol / L potassium carbonate aqueous solution, continue aging for 14 h, filter and wash, then dry at 95 °C for 10 h, and then dry at 110 °C for 14 h, The dried catalyst was ground to 200 mesh, and the obtained catalyst was reductively activated under the following conditions: reducing with hydrogen (hydrogen pressure 0.1-3.0 MPa) at 480 °C for 4 h, and then cooling down to room temperature under the protection of high-purity nitrogen. The obtained catalyst sample was recorded as 2# catalyst, and 0.5 g of catalyst 2# was taken for activity evaluation.

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Abstract

The invention relates to a hydroquinone hydrogenation catalyst, a preparation method and a hydrogenation reaction method. The catalyst contains an active ingredient of Ru, an auxiliary agent La and a carrier, wherein the composition of the catalyst is shown as x percent Ru-y percent La / carrier, wherein the x percent Ru-y percent La / carrier, wherein the x percent represents the mass percentage of the Ru in the catalyst; the y percent represents the mass percentage of the La in the catalyst; the content of each ingredient of the catalyst is shown as follows: the mass percentage of Ru is 0.5 to 5 percent; the mass percentage of La is 0.2 to 2 percent; the rest is the carrier. Catalyst precursors are prepared by an immersion-precipitation method; then, the catalyst precursors are reduced in the hydrogen-containing atmosphere; the para-nitrotoluene hydrogenation Ru-La bimetal catalyst is obtained; in the reaction for preparing p-methyl-cyclohexylamine through nitrotoluene hydrogenation, the p-methyl-cyclohexylamine can be strongly adsorbed onto the catalyst; a great amount of tar can be further generated; the proceeding of the reaction is inhibited; through the addition of the La, the problem of strong adsorption of the catalyst on the p-methyl-cyclohexylamine is well solved; the tar generation quantity is reduced.

Description

technical field [0001] The invention relates to the technical field of catalytic hydrogenation, in particular to a catalyst preparation technology for synthesizing 1,4-cyclohexanediol by catalytic hydrogenation of hydroquinone. Background technique [0002] 1,4-Cyclohexanediol is mainly used to synthesize some anticancer drugs and biological controller markers, etc. It is a widely used pharmaceutical intermediate and new material monomer. At present, the production volume of this product in my country is very small, but its demand is very large, especially the high-purity cis and trans 1,4-cyclohexanediol and spectroscopically pure 1,4-cyclohexanediol are in short supply. Due to the large output and low price of petroleum phenol products, it is the simplest and most convenient way to synthesize 1,4-cyclohexanediol by catalytic hydrogenation of hydroquinone. At present, there is no catalyst that can synthesize 1,4-cyclohexanediol in a green and efficient manner. Therefore, i...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/58B01J23/63B01J29/12B01J29/44C07C29/20C07C35/14
CPCB01J29/126B01J23/58B01J23/63B01J29/44B01J2229/186C07C29/20C07C35/14
Inventor 李贵贤李红伟季东
Owner LANZHOU UNIVERSITY OF TECHNOLOGY
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