NL2030604A - Catalytic hydrogenation catalyst, preparation method and application thereof - Google Patents

Catalytic hydrogenation catalyst, preparation method and application thereof Download PDF

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NL2030604A
NL2030604A NL2030604A NL2030604A NL2030604A NL 2030604 A NL2030604 A NL 2030604A NL 2030604 A NL2030604 A NL 2030604A NL 2030604 A NL2030604 A NL 2030604A NL 2030604 A NL2030604 A NL 2030604A
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ruthenium
catalytic hydrogenation
catalyst
zirconium
benzoic acid
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NL2030604A
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Dutch (nl)
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NL2030604B1 (en
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Li Rongrong
Chen Xianlang
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Shaoxing Lvyi Chemical Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/36—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by hydrogenation of carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

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  • Chemical Kinetics & Catalysis (AREA)
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  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The disclosure belongs to the technical field of catalysts, and provides a catalytic hydrogenation catalyst, a preparation method and an application thereof. The disclosure provides a catalytic hydrogenation catalyst, comprising a zirconium. support and an active substance attached on the zirconium support, wherein the active substance is elemental ruthenium; the loading amount of the active substance is l—5% of the catalyst by mass. The disclosure replaces metallic elemental palladium with metallic elemental ruthenium as the catalyst to reduce cost; the catalytic hydrogenation efficiency is ensured by the combined effect of the zirconium support and elemental ruthenium, which can improve the conversion rate of benzoic acid, and the selectivity of cyclohexanecarboxylic acid in the hydrogenation reaction of benzoic acid. The conversion rate of benzoic acid achieved by the catalytic hydrogenation catalyst is 68.2—96.3%, and the selectivity of cyclohexanecarboxylic acid achieved by same is 62.4—97.5%.

Description

P1038/NLpd CATALYTIC HYDROGENATION CATALYST, PREPARATION METHOD AND
APPLICATION THEREOF
TECHNICAL FIELD The disclosure belongs to the technical field of catalysts, and in particular, to a catalytic hydrogenation catalyst, a prepa- ration method and an application thereof.
BACKGROUND ART Cyclohexanecarboxylic acid is an important chemical and medi- cal intermediate, which can be used not only for the synthesis of schistosomiasis treating medicines, anti-pregnancy medicines and photo-curing agents, but also as pesticides, vulcanized rubber solubilizers, dyes and petroleum clarifying agents; its deriva- tives, such as trans-4-isopropyl cyclohexanecarboxylic acid, can be used as the intermediate for producing a new medicine nateglinide for treating diabetes. Therefore, the research on the catalytic hydrogenation of benzoic acid for producing cyclohex- anecarboxylic acid has a relatively high application value.
A catalytic hydrogenation reaction produces products and wa- ter, and the production of other by-products can be reduced under proper conditions, which meets the requirement for green chemis- try. However, for producing cyclohexanecarboxylic acid by the cat- alytic hydrogenation of benzoic acid, a common catalyst is Pd/C catalyst, and palladium is expensive; moreover, the catalytic hy- drogenation reaction achieved by the Pd/C catalyst has strict con- ditions, which is not conductive to industrial development.
Therefore, it is urgently needed to design a catalyst with low cost and easily-controlled catalytic conditions so as to re- place Pd/C catalyst.
SUMMARY In view of this, the objective of the disclosure is to pro- vide a catalytic hydrogenation catalyst, a preparation method and an application thereof. The catalyst provided by the disclosure has low cost and easy catalytic conditions.
To achieve this objective, the disclosure provides the fol-
lowing technical solutions: The disclosure provides a catalytic hydrogenation catalyst, comprising a zirconium support and an active substance attached on the zirconium support, wherein the active substance is elemental ruthenium; the mass percentage content of the active substance in the catalytic hydrogenation catalyst is 1-5%.
Preferably, the zirconium support comprises one or more of zirconium nitride, zirconium oxide and zirconium boride.
The disclosure furthermore provides a preparation method of the catalytic hydrogenation catalyst described in the above- mentioned technical solutions, comprising the following steps: mixing the zirconium support, a ruthenium precursor and water to form a precursor dispersion; dropwise adding a reducing agent water solution in the pre- cursor dispersion for a reduction reaction so as to obtain the catalytic hydrogenation catalyst; wherein the mass ratio of the zirconium support and the ru- thenium precursor is 1000: (30.74-71.74).
Preferably, the particle size of the zirconium support is 10- 50 nm.
Preferably, the ruthenium precursor is ruthenium acetate, ru- thenium nitrosyl nitrate, anhydrous ruthenium chloride or rutheni- um acetylacetonate.
Preferably, the concentration of the ruthenium precursor in the precursor dispersion is 1-8 mg/mL.
Preferably, the reducing agent in the reducing agent water solution comprises one or more of sodium borohydride, potassium borohydride or hydrazine hydrate.
Preferably, the molar ratio of the reducing agent and the ru- thenium in the ruthenium precursor is (5-15):1.
The disclosure furthermore provides an application of the catalytic hydrogenation catalyst described in the above-mentioned technical solutions or prepared by the preparation method de- scribed in the above-mentioned technical solutions in the hydro- genation reaction of benzoic acid.
Preferably, the hydrogenation reaction of benzoic acid com- prises the following steps:
mixing the benzoic acid, the catalytic hydrogenation catalyst and water, and performing the hydrogenation reaction in a hydrogen atmosphere; wherein the mass ratio of the benzoic acid and catalytic hy- drogenation catalyst is (1-4):1; the hydrogenation reaction pressure is 0.5-1.5 MPa, and the temperature is 40-100°C.
The disclosure provides a catalytic hydrogenation catalyst, comprising a zirconium support and an active substance attached on the zirconium support, wherein the active substance is elemental ruthenium; the mass percentage content of the active substance in the catalytic hydrogenation catalyst is 1-5%. The disclosure re- places metallic elemental palladium with metallic elemental ruthe- nium as the catalyst to reduce cost; the catalytic hydrogenation efficiency is ensured by the combined effect of the zirconium sup- pert and elemental ruthenium, which can improve the conversion rate of benzoic acid and the selectivity of cyclohexanecarboxylic acid in the hydrogenation reaction of benzoic acid.
The disclosure furthermore provides the preparation method of the catalytic hydrogenation catalyst described in the above- mentioned technical solutions, comprising the following steps: mixing the zirconium support, the ruthenium precursor and water to form the precursor dispersion; dropwise adding the reducing agent water solution in the precursor dispersion for the reduction reac- tion so as to obtain the catalytic hydrogenation catalyst, wherein the mass ratio of the zirconium support and the ruthenium precur- sor is 1000:{(30.74-71.74). The preparation method provided by the disclosure has simple operation, wide sources for all raw materi- als, and low cost.
The disclosure furthermore provides an application of the catalytic hydrogenation catalyst described in the above-mentioned technical solutions or prepared by the preparation method de- scribed in the above-mentioned technical solutions in the hydro- genation reaction of benzoic acid. During the use of the catalytic hydrogenation catalyst of the disclosure for catalyzing the hydro- genation reaction of benzoic acid, the hydrogenation reaction pressure is 0.5-1.5 MPa, the temperature is 40-100°C, the reaction conditions can be easily controlled, the conversion rate of benzo- ic acid is high, and the selectivity of cyclohexanecarboxylic acid is high as well.
The data of the embodiments show that the conversion rate of benzoic acid achieved by the catalytic hydrogenation catalyst of the disclosure is 31.7-96.3%, and the selectivity of cyclohex- anecarboxylic acid achieved by same is 62.4-97.5%.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a TEM (Transmission Electron Microscope) picture of a catalytic hydrogenation catalyst according to embodiment 1; FIG. 2 is a TEM picture of a catalytic hydrogenation catalyst according to embodiment 2.
DETAILED DESCRIPTION OF THE EMBODIMENTS The disclosure provides a catalytic hydrogenation catalyst, comprising a zirconium support and an active substance attached on the zirconium support, wherein the active substance is elemental ruthenium; the mass percentage content of the active substance in the catalytic hydrogenation catalyst is 1-5%.
The catalytic hydrogenation catalyst provided by the disclo- sure comprises a zirconium support, and the zirconium support preferably comprises one or more of zirconium nitride, zirconium oxide and zirconium boride.
The catalytic hydrogenation catalyst provided by the disclo- sure comprises an active substance attached on the zirconium sup- port, and the active substance is elemental ruthenium; the active substance is coupled to and loaded on the surface of the zirconium support through chemical bonds formed by electronic mutual trans- fer.
In the disclosure, the mass percentage content of the active substance in the catalytic hydrogenation catalyst is preferably
1.5-3.5%, further preferably 2.5%.
The disclosure furthermore provides a preparation method of the catalytic hydrogenation catalyst described in the above- mentioned technical solutions, comprising the following steps: mixing the zirconium support, a ruthenium precursor and water to form a precursor dispersion; dropwise adding a reducing agent water solution in the pre-
cursor dispersion for a reduction reaction so as to obtain the catalytic hydrogenation catalyst.
In the disclosure, unless otherwise specified, the raw mate- rials used by the disclosure are preferably marketable products.
5 In the disclosure, the zirconium support, the ruthenium pre- cursor and water are mixed to form the precursor dispersion.
In the disclosure, the zirconium support preferably comprises one or more of zirconium nitride, zirconium oxide and zirconium boride, further preferably zirconium nitride, zirconium oxide or zirconium boride; the particle size of the zirconium support is preferably 10-50 nm.
In the disclosure, the ruthenium precursor is preferably ru- thenium acetate, ruthenium nitrosyl nitrate, anhydrous ruthenium chloride or ruthenium acetylacetonate, further preferably anhy- drous ruthenium chloride.
In the disclosure, the water is preferably deionized water.
In the disclosure, the mass ratio of the zirconium support and the ruthenium precursor is 1000: (30.74-71.74), preferably 1000:51.24. In the disclosure, the concentration of the ruthenium precursor in the precursor dispersion is preferably 1-8 mg/mL, further preferably 3.07-7.174 mg/mL, more preferably 5.124 mg/mL.
In the disclosure, the mixing is preferably performed under a stirring condition, and the stirring rotation speed is preferably 200-800 rpm, further preferably 500 rpm; time is preferably 4-12 h, preferably 5-7 h, more preferably 6 h.
In the disclosure, the ruthenium precursor and the zirconium support are mixed thoroughly so as to provide the basis for the subsequent reduction and the uniform distribution of elemental ru- thenium obtained by reduction.
After the precursor dispersion is formed, the reducing agent water solution is dropwise added in the precursor dispersion for a reduction reaction so as to obtain the catalytic hydrogenation catalyst.
In the disclosure, the reducing agent in the reducing agent water solution preferably comprises one or more of sodium borohy- dride, potassium borohydride or hydrazine hydrate, preferably so- dium borohydride; the concentration of the reducing agent water solution is preferably 4.703 mg/mL.
In the disclosure, the molar ratio of the reducing agent and the ruthenium in the ruthenium precursor is preferably (5-15):1, further preferably (9-11):1, more preferably 10:1.
In the disclosure, the dropwise adding speed is preferably 1- s/drop, further preferably 5 s/drop.
In the disclosure, the reduction reaction temperature is preferably room temperature, that is, there is no need for addi- tional heating or additional cooling; the reduction reaction time 10 is preferably 0.5-5 h, preferably 0.8-1.3 h, more preferably 1.0 h; the reduction reaction time is clocked sine the completion of the dropwise adding of the precursor dispersion. In the disclo- sure, the reduction reaction is preferably performed under a stir- ring condition, and the stirring rotation speed is preferably 200- 800 rpm, further preferably 500 rpm.
After the reduction reaction, the disclosure furthermore com- prises the step of filtering the reduction reaction system and drying the obtained solid, wherein the drying temperature is pref- erably 40-100°C, further preferably 70-20°C, more preferably 80°C; the time is preferably 3-8 h, further preferably 5-7 h, more pref- erably 6 h; the drying method is preferably a vacuum drying meth- od; the drying is preferably performed in a vacuum drying chamber.
In the reduction reaction process described in the disclo- sure, the ruthenium ion in the ruthenium precursor is reduced by the reducing agent into elemental ruthenium that is uniformly loaded on the zirconium support.
The disclosure furthermore provides an application of the catalytic hydrogenation catalyst described in the above-mentioned technical solutions or prepared by the preparation method de- scribed in the above-mentioned technical solutions in the hydro- genation reaction of benzoic acid.
In the disclosure, the hydrogenation reaction of benzoic acid preferably comprises the following steps: mixing the benzoic acid, the catalytic hydrogenation catalyst and water, and performing the hydrogenation reaction in a hydrogen atmosphere.
In the disclosure, the mass ratio of the benzoic acid and catalytic hydrogenation catalyst is preferably (1-4):1, further preferably 1.22:1; the mass ratio of the benzoic acid and water is preferably (5-50) :1000, further preferably 12.2:1000. In the disclosure, the hydrogenation reaction pressure is preferably 0.5-1.5 MPa, further preferably 1.0 MPa; the tempera- ture is preferably 40-100°C, further preferably 70-90°C, more pref- erably 80°C; the hydrogenation reaction time is preferably 0.1-2 h, further preferably 1 h. During the use of the catalytic hydrogenation catalyst of the disclosure for the hydrogenation reaction of benzoic acid, the re- action pressure and temperature are low, and the conditions are mild and can be easily controlled.
The catalytic hydrogenation catalyst, the preparation method and the application of the disclosure will be described in detail with reference to the embodiments, but these embodiments should not be understood as any limitation to the protection scope of the disclosure.
Embodiment 1 1) 1 g of zirconium oxide (of which particle size is 10-50 nm) and 51.24 mg of anhydrous ruthenium chloride are weighed and then mixed in 10 mL of water, and then the mixture is stirred at 500 rpm for 6 h to obtain a precursor dispersion.
2) 94.06 g of sodium borohydride is weighed and then dis- solved in 20 mL of water to obtain a sodium borohydride water so- lution; then, the sodium borohydride water solution is dropwise added in the precursor dispersion (at a dropwise adding speed of 5 s/drop), a reduction reaction is performed at 500 rpm for 1 h, the reaction solution is filtered, the obtained solid is dried in a vacuum at 80°C for 6 h to obtain the catalytic hydrogenation cata- lyst, wherein the mass percentage content of ruthenium in the cat- alytic hydrogenation catalyst is 2.5%.
FIG. 1 is a TEM picture of a catalytic hydrogenation catalyst according to embodiment 1. According to FIG. 1, it can be seen that the metallic ruthenium particles have small particle size and are well dispersed. 10 mg of the obtained catalytic hydrogenation catalyst, 1 mL of water and 12.2 mg of benzoic acid are mixed in a high pressure reactor to have a hydrogenation reaction under the conditions of 1 MPa and 80°C for 1 h. The results are that the conversion rate of benzoic acid is 96.3%, and the selectivity of cyclohexanecarbox- ylic acid is 97.5%.
Embodiment 2 1) 1 g of zirconium nitride (of which particle size is 10-50 nm) and 51.24 mg of anhydrous ruthenium chloride are weighed and then mixed in 10 mL of water, and then the mixture is stirred at 500 rpm for 6 h to obtain a precursor dispersion.
2) 94.06 g of sodium borohydride is weighed and then dis- solved in 20 mL of water to obtain a sodium borohydride water so- lution; then, the sodium borohydride water solution is dropwise added in the precursor dispersion (at a dropwise adding speed of 5 sg/drop), a reduction reaction is performed at 500 rpm for 1 h, the reaction solution is filtered, the obtained solid is dried in a vacuum at 80°C for 6 h to obtain the catalytic hydrogenation cata- lyst, wherein the mass percentage content of ruthenium in the cat- alytic hydrogenation catalyst is 2.5%.
FIG. 2 is a TEM picture of a catalytic hydrogenation catalyst according to the present embodiment. From the comparison between FIG. 1 and FIG. 2, it can be seen that the catalytic hydrogenation catalyst obtained by the present embodiment has poor ruthenium dispersion effect, and there is little agglomeration.
10 mg of the obtained catalytic hydrogenation catalyst, 1 mL of water and 12.2 mg of benzoic acid are mixed in a high pressure reactor to have a hydrogenation reaction under the conditions of 1 MPa and 80°C for 1 h. The results are that the conversion rate of benzoic acid is 85.8%, and the selectivity of cyclohexanecarbox- ylic acid is 90.3%.
Embodiment 3 1) 1 g of zirconium boride (of which particle size is 10-50 nm) and 51.24 mg of anhydrous ruthenium chloride are weighed and then mixed in 10 mL of water, and then the mixture is stirred at 500 rpm for 6 h to obtain a precursor dispersion.
2) 94.06 g of sodium borohydride is weighed and then dis-
solved in 20 mL of water to obtain a sodium borohydride water so- lution; then, the sodium borohydride water solution is dropwise added in the precursor dispersion (at a dropwise adding speed of 5 g/drop), a reduction reaction is performed at 500 rpm for 1 h, the reaction solution is filtered, the obtained solid is dried in a vacuum at 80°C for 6 h to obtain the catalytic hydrogenation cata- lyst, wherein the mass percentage content of ruthenium in the cat- alytic hydrogenation catalyst is 2.5%.
mg of the obtained catalytic hydrogenation catalyst, 1 mL 10 of water and 12.2 mg of benzoic acid are mixed in a high pressure reactor to have a hydrogenation reaction under the conditions of 1 MPa and 80°C for 1 h. The results are that the conversion rate of benzoic acid is 68.2%, and the selectivity of cyclohexanecarbox- ylic acid is 83.75.
Embodiment 4 1) 1 g of zirconium oxide (of which particle size is 10-50 nm) and 30.74mg of anhydrous ruthenium chloride are weighed and then mixed in 10 mL of water, and then the mixture is stirred at 500 rpm for 6 h to obtain a precursor dispersion.
2) 94.06 g of sodium borohydride is weighed and then dis- solved in 20 mL of water to obtain a sodium borohydride water so- lution; then, the sodium borohydride water solution is dropwise added in the precursor dispersion (at a dropwise adding speed of 5 s/drop), a reduction reaction is performed at 500 rpm for 1 h, the reaction solution is filtered, the obtained solid is dried in a vacuum at 80°C for 6 h to obtain the catalytic hydrogenation cata- lyst, wherein the mass percentage content of ruthenium in the cat- alytic hydrogenation catalyst is 1.5%.
10 mg of the obtained catalytic hydrogenation catalyst, 1 mL of water and 12.2 mg of benzoic acid are mixed in a high pressure reactor to have a hydrogenation reaction under the conditions of 1 MPa and 80°C for 1 h. The results are that the conversion rate of benzoic acid is 77.3%, and the selectivity of cyclohexanecarbox- ylic acid is 90.3%.
Embodiment 5 1) 1 g of zirconium oxide (of which particle size is 10-50 nm) and 71.74mg of anhydrous ruthenium chloride are weighed and then mixed in 10 mL of water, and then the mixture is stirred at 500 rpm for 6 h to obtain a precursor dispersion. 2) 94.06 g of sodium borohydride is weighed and then dis- solved in 20 mL of water to obtain a sodium borohydride water so- lution; then, the sodium borohydride water solution is dropwise added in the precursor dispersion (at a dropwise adding speed of 5 s/drop), a reduction reaction is performed at 500 rpm for 1 h, the reaction solution is filtered, the obtained solid is dried in a vacuum at 80°C for 6 h to obtain the catalytic hydrogenation cata- lyst, wherein the mass percentage content of ruthenium in the cat- alytic hydrogenation catalyst is 3.5%.
10 mg of the obtained catalytic hydrogenation catalyst, 1 mL of water and 12.2 mg of benzoic acid are mixed in a high pressure reactor to have a hydrogenation reaction under the conditions of 1 MPa and 80°C for 1 h.
The results are that the conversion rate of benzoic acid is
88.4%, and the selectivity of cyclohexanecarboxylic acid is 62.4%. Embodiment 6 1) 1 g of zirconium oxide (of which particle size is 10-50 nm) and 51.24 mg of anhydrous ruthenium chloride are weighed and then mixed in 10 mL of water, and then the mixture is stirred at 500 rpm for 6 h to obtain a precursor dispersion.
2) 94.06 g of sodium borohydride is weighed and then dis- solved in 20 mL of water to obtain a sodium borohydride water so- lution; then, the sodium borohydride water solution is dropwise added in the precursor dispersion (at a dropwise adding speed of 1 g/drop), a reduction reaction is performed at 500 rpm for 1 h, the reaction solution is filtered, the obtained solid is dried in a vacuum at 80°C for 6 h to obtain the catalytic hydrogenation cata- lyst, wherein the mass percentage content of ruthenium in the cat- alytic hydrogenation catalyst is 2.5%.
10 mg of the obtained catalytic hydrogenation catalyst, 1 mL of water and 12.2 mg of benzoic acid are mixed in a high pressure reactor to have a hydrogenation reaction under the conditions of 1 MPa and 80°C for 1 h. The results are that the conversion rate of benzoic acid is 85.1%, and the selectivity of cyclohexanecarbox- ylic acid is 90.1%.
Embodiment 7 1) 1 g of zirconium oxide (of which particle size is 10-50 nm) and 51.24 mg of anhydrous ruthenium chloride are weighed and then mixed in 10 mL of water, and then the mixture is stirred at 500 rpm for 6 h to obtain a precursor dispersion.
2) 94.06 g of sodium borohydride is weighed and then dis- solved in 10 mL of water to obtain a sodium borohydride water so- lution; then, the sodium borohydride water solution is dropwise added in the precursor dispersion (at a dropwise adding speed of 5 s/drop), a reduction reaction is performed at 500 rpm for 1 h, the reaction solution is filtered, the obtained solid is dried in a vacuum at 80°C for 6 h to obtain the catalytic hydrogenation cata- lyst, wherein the mass percentage content of ruthenium in the cat- alytic hydrogenation catalyst is 2.5%.
10 mg of the obtained catalytic hydrogenation catalyst, 1 mL of water and 12.2 mg of benzoic acid are mixed in a high pressure reactor to have a hydrogenation reaction under the conditions of 1 MPa and 80°C for 1 h. The results are that the conversion rate of benzoic acid is 73.8%, and the selectivity of cyclohexanecarbox- ylic acid is 84.1%.
Embodiment 8 1) 1 g of zirconium oxide (of which particle size is 10-50 nm) and 51.24 mg of anhydrous ruthenium chloride are weighed and then mixed in 10 mL of water, and then the mixture is stirred at 500 rpm for 6 h to obtain a precursor dispersion.
2) 94.06 g of sodium borohydride is weighed and then dis- solved in 20 mL of water to obtain a sodium borohydride water so- lution; then, the sodium borohydride water solution is dropwise added in the precursor dispersion (at a dropwise adding speed of 5 g/drop), a reduction reaction is performed at 500 rpm for 1 h, the reaction solution is filtered, the obtained solid is dried in a vacuum at 80°C for 6 h to obtain the catalytic hydrogenation cata- lyst, wherein the mass percentage content of ruthenium in the cat- alytic hydrogenation catalyst is 2.5%.
10 mg of the obtained catalytic hydrogenation catalyst, 1 mL of water and 12.2 mg of benzoic acid are mixed in a high pressure reactor to have a hydrogenation reaction under the conditions of 1 MPa and 40°C for 1 h. The results are that the conversion rate of benzoic acid is 31.7%, and the selectivity of cyclohexanecarbox- ylic acid is 90.13.
Embodiment 9 1) 1 g of zirconium oxide (of which particle size is 10-50 nm) and 51.24 mg of anhydrous ruthenium chloride are weighed and then mixed in 10 mL of water, and then the mixture is stirred at 500 rpm for 6 h to obtain a precursor dispersion.
2) 65.84mg of sodium borohydride is weighed and then dis- solved in 10 mL of water to obtain a sodium borohydride water so- lution; then, the sodium borohydride water solution is dropwise added in the precursor dispersion (at a dropwise adding speed of 5 s/drop), a reduction reaction is performed at 500 rpm for 1 h, the reaction solution is filtered, the obtained solid is dried in a vacuum at 80°C for 6 h to obtain the catalytic hydrogenation cata- lyst, wherein the mass percentage content of ruthenium in the cat- alytic hydrogenation catalyst is 2.5%.
10 mg of the obtained catalytic hydrogenation catalyst, 1 mL of water and 12.2 mg of benzoic acid are mixed in a high pressure reactor to have a hydrogenation reaction under the conditions of 1 MPa and 80°C for 1 h. The results are that the conversion rate of benzoic acid is 78.1%, and the selectivity of cyclohexanecarbox- ylic acid is 83.5%.
Embodiment 10 1) 1 g of zirconium oxide (of which particle size is 10-50 nm) and 51.24 mg of anhydrous ruthenium chloride are weighed and then mixed in 10 mL of water, and then the mixture is stirred at 500 rpm for 6 h to obtain a precursor dispersion.
2) 112.87mg of sodium borohydride is weighed and then dis- solved in 10 mL of water to obtain a sodium borohydride water so- lution; then, the sodium borohydride water solution is dropwise added in the precursor dispersion (at a dropwise adding speed of 5 s/drop}, a reduction reaction is performed at 500 rpm for 1 h, the reaction solution is filtered, the obtained solid is dried in a vacuum at 80°C for 6 h to obtain the catalytic hydrogenation cata- lyst, wherein the mass percentage content of ruthenium in the cat- alytic hydrogenation catalyst is 2.5%.
mg of the obtained catalytic hydrogenation catalyst, 1 mL of water and 12.2 mg of benzoic acid are mixed in a high pressure reactor to have a hydrogenation reaction under the conditions of 1 MPa and 80°C for 1 h. The results are that the conversion rate of benzoic acid is 69.3%, and the selectivity of cyclohexanecarbox- 10 ylic acid is 76.2%.
Comparative Example 1
30.51 mg of ruthenium nitrosyl nitrate solution (15.95 wt% of ruthenium nitrosyl nitrate in dilute nitric acid) is added into a beaker; the solution is supplemented to 10 mL by deionized water; 50 mg of zirconium oxide is added, and successively the solution is stirred uniformly. Then, the beaker is dried in a drying cham- ber at 120°C for 16 h and afterwards calcined at 200°C for 2 h. Fi- nally, in a hydrogen atmosphere with hydrogen flow rate of 31 L/h, a reduction reaction is performed in a tube furnace at 200°C for 90 min, so as to obtain the catalyst.
10 mg of the obtained catalyst, 1 mL of water and 12.2 mg of benzoic acid are mixed in a high pressure reactor to have a hydro- genation reaction under the conditions of 1 MPa and 80°C for 1 h. The results are that the conversion rate of benzoic acid is 82.8%, and the selectivity of cyclohexanecarboxylic acid is 74.2%.
Comparative Example 2 1) 1 g of alumina (of which particle size is 10-50 nm) and
51.24 mg of anhydrous ruthenium chloride are weighed and then mixed in 10 mL of water, and then the mixture is stirred at 500 rpm for 6 h to obtain a precursor dispersion.
2) 94.06 g of sodium borohydride is weighed and then dis- solved in 20 mL of water to obtain a sodium borohydride water so- lution; then, the sodium borohydride water solution is dropwise added in the precursor dispersion (at a dropwise adding speed of 5 s/drop), a reduction reaction is performed at 500 rpm for 1 h, the reaction solution is filtered, the obtained solid is dried in a vacuum at 80°C for 6 h to obtain the catalytic hydrogenation cata- lyst, wherein the mass percentage content of ruthenium in the cat- alytic hydrogenation catalyst is 2.5%.
10 mg of the obtained catalytic hydrogenation catalyst, 1 mL of water and 12.2 mg of benzoic acid are mixed in a high pressure reactor to have a hydrogenation reaction under the conditions of 1 MPa and 40°C for 1 h. The results are that the conversion rate of benzoic acid is 20.5%, and the selectivity of cyclohexanecarbox- ylic acid is 40.3%.
From the embodiments and comparative examples, it can be seen that compared with alumina support, the zirconium support used by the disclosure co-acts with ruthenium to achieve higher conversion rate of benzoic acid and higher selectivity of cyclohexanecarbox- ylic acid for the catalytic hydrogenation reaction of benzoic ac- id.
The above descriptions are only preferred embodiments of the disclosure, and it should be noted that those of ordinary skill in the art can further make several improvements and modifications without departing from the principle of the disclosure, and those improvements and modifications should be included in the protec- tion scope of the disclosure.

Claims (10)

CONCLUSIESCONCLUSIONS 1. Katalysator voor katalytische hydrogenering, omvattende een zirkoniumdrager en een op de zirkoniumdrager bevestigde actieve stof, waarbij de actieve stof elementair ruthenium is; waarbij het massapercentage-gehalte van de actieve stof in de katalysator voor katalytische hydrogenering 1-5 % is.A catalyst for catalytic hydrogenation comprising a zirconium support and an active substance attached to the zirconium support, the active substance being elemental ruthenium; wherein the mass percentage content of the active substance in the catalyst for catalytic hydrogenation is 1-5%. 2. Katalysator voor katalytische hydrogenering volgens conclusie 1, met het kenmerk, dat de zirkoniumdrager een of meer van zirko- niumnitride, zirkoniumoxide en zirkoniumboride omvat.Catalytic hydrogenation catalyst according to claim 1, characterized in that the zirconium support comprises one or more of zirconium nitride, zirconium oxide and zirconium boride. 3. Werkwijze voor het vervaardigen van de katalysator voor kataly- tische hydrogenering volgens conclusie 1 of 2, omvattende de vol- gende stappen: het mengen van de zirkoniumdrager, een rutheniumvoorloper en water om een voorloperdispersie te vormen; het druppelsgewijs toevoegen van een waterige oplossing van een reductiemiddel in de voorloperdispersie om een reductiereactie uit te voeren om de katalysator voor katalytische hydrogenering te verkrijgen; waarbij de massaverhouding van de zirkoniumdrager en de ruthenium- voorloper 1000: (30,74-71,74) is.A process for preparing the catalyst for catalytic hydrogenation according to claim 1 or 2, comprising the steps of: mixing the zirconium support, a ruthenium precursor and water to form a precursor dispersion; adding an aqueous solution of a reducing agent in the precursor dispersion dropwise to carry out a reduction reaction to obtain the catalyst for catalytic hydrogenation; wherein the mass ratio of the zirconium support and the ruthenium precursor is 1000: (30.74-71.74). 4. Werkwijze voor het vervaardigen volgens conclusie 3, waarbij de deeltjesgrootte van de zirkoniumdrager 10 - 50 nm is.The manufacturing method according to claim 3, wherein the particle size of the zirconium support is 10-50 nm. 5. Werkwijze voor het vervaardigen volgens conclusie 3, met het kenmerk, dat de rutheniumvoorloper rutheniumacetaat, rutheniumni- trosylnitraat, watervrij rutheniumchloride of rutheniumacetylace- tonaat is.The manufacturing process according to claim 3, characterized in that the ruthenium precursor is ruthenium acetate, ruthenium nitrosyl nitrate, anhydrous ruthenium chloride or ruthenium acetylacetonate. 6. Werkwijze voor het vervaardigen volgens conclusie 3 of 5, waar- bij de concentratie van de rutheniumvoorloper in de voorloperdis- persie 1 - 8 mg/ml is.The manufacturing process according to claim 3 or 5, wherein the concentration of the ruthenium precursor in the precursor dispersion is 1-8 mg/ml. 7. Werkwijze voor het vervaardigen volgens conclusie 3, waarbij het reductiemiddel in de waterige oplossing van het reductiemiddel een of meer van natriumboorhydride, kaliumboorhydride of hydrazi- nehydraat omvat.The manufacturing process according to claim 3, wherein the reducing agent in the aqueous solution of the reducing agent comprises one or more of sodium borohydride, potassium borohydride or hydrazine hydrate. 8. Werkwijze voor het vervaardigen volgens conclusie 7, waarbij de molaire verhouding van het reductiemiddel en het ruthenium in de rutheniumvoorloper (5-15) : 1 is.The manufacturing process according to claim 7, wherein the molar ratio of the reducing agent and the ruthenium in the ruthenium precursor is (5-15) :1. 9. Toepassing van de katalysator voor katalytische hydrogenering in overeenstemming met conclusie 1 of 2 of bereid door de berei- dingswerkwijze in overeenstemming met een van de conclusies 3 - 8 in de hydrogeneringsreactie van benzoëzuur.Use of the catalyst for catalytic hydrogenation according to claim 1 or 2 or prepared by the preparation method according to any one of claims 3 to 8 in the hydrogenation reaction of benzoic acid. 10. Toepassing in overeenstemming met conclusie 9, waarbij de hy- drogeneringsreactie van benzoëzuur de volgende stappen omvat: het mengen van het benzoëzuur, de katalysator voor katalytische hydrogenering en water, en het uitvoeren van de hydrogeneringsre- actie in een waterstofatmosfeer; waarbij de massaverhouding van het benzoëzuur en de katalysator voor katalytische hydrogenering (1-4) : 1 is; waarbij de reactiedruk bij de hydrogenering 0,5 - 1,5 MPa is en de temperatuur 40 —- 100 °C is.The use according to claim 9, wherein the hydrogenation reaction of benzoic acid comprises the steps of: mixing the benzoic acid, the catalytic hydrogenation catalyst and water, and conducting the hydrogenation reaction in a hydrogen atmosphere; wherein the mass ratio of the benzoic acid and the catalyst for catalytic hydrogenation is (1-4) : 1; wherein the reaction pressure in the hydrogenation is 0.5-1.5 MPa and the temperature is 40-100°C.
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