CN109304166B - Catalyst for hydrogenation of 1, 4-cyclohexane dicarboxylic acid - Google Patents

Catalyst for hydrogenation of 1, 4-cyclohexane dicarboxylic acid Download PDF

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CN109304166B
CN109304166B CN201710628245.2A CN201710628245A CN109304166B CN 109304166 B CN109304166 B CN 109304166B CN 201710628245 A CN201710628245 A CN 201710628245A CN 109304166 B CN109304166 B CN 109304166B
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catalyst
hydrogen
content
cyclohexanedimethanol
reaction
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CN109304166A (en
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司丹
畅延青
朱庆才
张海涛
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • 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
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/60—Platinum group metals with zinc, cadmium or mercury
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/36—Rhenium
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    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
    • 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
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
    • 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
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
    • 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
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/187—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases

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Abstract

The invention relates to a catalyst for hydrogenation of 1, 4-cyclohexanedicarboxylic acid, which solves the problem of low yield when 1, 4-cyclohexanedicarboxylic acid is hydrogenated to prepare 1, 4-cyclohexanedimethanol in the prior art. The technical scheme that the catalyst for hydrogenation of 1, 4-cyclohexanedicarboxylic acid comprises a carrier, an active component and a cocatalyst, wherein the carrier is activated carbon, the active component comprises Re, and the cocatalyst comprises Zn can be used in industrial production of 1, 4-cyclohexanedimethanol.

Description

Catalyst for hydrogenation of 1, 4-cyclohexane dicarboxylic acid
Technical Field
The invention relates to a catalyst for hydrogenation of 1, 4-cyclohexanedicarboxylic acid, a preparation method and application thereof.
Background
1, 4-cyclohexanedimethanol (CHDM for short) is an important organic chemical raw material for producing polyester resin, the polyester resin produced by using the CHDM instead of ethylene glycol or other polyols has good thermal stability and thermoplasticity, can keep stable physical property and electrical property at higher temperature, and products prepared by the resin have good chemical resistance and environmental resistance. At present, dimethyl terephthalate is mainly used as a raw material in the process of industrially producing 1, 4-cyclohexanedimethanol, dimethyl 1, 4-cyclohexanedicarboxylate is prepared by benzene ring hydrogenation, and then 1, 4-cyclohexanedimethanol is prepared by ester hydrogenation. Due to the relatively low price and abundant sources of terephthalic acid (PTA), a trend has arisen in recent years to produce 1, 4-cyclohexanedimethanol starting from terephthalic acid. The process also usually comprises two steps, namely, firstly, the benzene ring is selectively hydrogenated to produce 1, 4-cyclohexanedicarboxylic acid, and then the 1, 4-cyclohexanedicarboxylic acid is hydrogenated to produce 1, 4-cyclohexanedimethanol. Considering the complexity of the two-step process, many researchers have conducted one-step hydrogenation of terephthalic acid to 1, 4-cyclohexanedimethanol. For example, JP200007596 filed in 1998 by Mitsubishi chemical corporation in Japan discloses a process for preparing CHDM by a one-step method under liquid phase conditions with PTA. The catalyst adopts a catalyst containing Ru and Sn components, and preferably also contains Pt, and the catalyst takes active carbon as a carrier. The embodiment discloses a specific reaction process, namely adding PTA, water and a catalyst in an autoclave under the protection of argon, raising the temperature to 230 ℃ when the hydrogen pressure is 1MPa, introducing hydrogen for reaction when the hydrogen pressure reaches 15MPa, taking out the reaction liquid after 4 hours of reaction, wherein the yield of CHDM is only 28.3%. Yoshinori Hara et al (The polymeric effect of platinum on carbon-supported ruthenium-tin catalysts used for hydrogenation reactions of carboxylic acids. Y. Hara, K. endo. applied catalysts A: General 239(2003) 181-195) used in The hydrogenation reaction using Ru-Sn-Pt/C catalyst, although The conversion of 1, 4-cyclohexanedicarboxylic acid reached 98%, The maximum yield of 1, 4-cyclohexanedimethanol was only 81.6%, and The yield of 1, 4-cyclohexanedimethanol was only 75% when The hydrogenation reaction was carried out using Ru-Sn-Re/C catalyst as described in US 6495730.
Disclosure of Invention
The invention provides a catalyst for hydrogenation of 1, 4-cyclohexanedicarboxylic acid, which aims to solve the problem of low yield of 1, 4-cyclohexanedimethanol prepared by hydrogenation of 1, 4-cyclohexanedicarboxylic acid in the prior art. The catalyst has the characteristic of high yield of 1, 4-cyclohexanedimethanol generated by hydrogenation of 1, 4-cyclohexanedicarboxylic acid.
The second problem to be solved by the present invention is a method for preparing the catalyst.
The third problem to be solved by the present invention is to use the catalyst described in one of the above technical problems.
In order to solve one of the above technical problems, the technical solution adopted by the present invention is as follows: the catalyst for hydrogenation of 1, 4-cyclohexanedicarboxylic acid comprises a carrier, an active component and a cocatalyst, wherein the carrier is activated carbon, the active component comprises Re, and the cocatalyst comprises Zn.
In the technical scheme, the active component preferably comprises Ru, and the Ru and the Re have a synergistic effect on the aspect of improving the yield of the 1, 4-cyclohexanedimethanol.
In the technical scheme, the active component preferably comprises Co, and Re and Co have a synergistic effect on the aspect of improving the yield of the 1, 4-cyclohexanedimethanol.
In the technical scheme, the active component preferably comprises Ru and Co at the same time, and the Ru and the Co have a synergistic effect on the aspect of improving the yield of the 1, 4-cyclohexanedimethanol.
In the technical scheme, the cocatalyst preferably comprises P, Zn and P, and the cocatalyst has a synergistic effect in the aspects of improving the yield of the 1, 4-cyclohexanedimethanol and improving the selectivity of the 1, 4-cyclohexanedimethanol.
In the above technical solution, it is most preferable that the active component simultaneously includes Ru, Re and Co, the Co-catalyst simultaneously includes Zn and P, and Ru, Re, Co, Zn and P have a combined promoting effect in increasing the yield of 1, 4-cyclohexanedimethanol and increasing the selectivity of 1, 4-cyclohexanedimethanol.
In the technical scheme, the content of Ru in the catalyst is preferably more than 0 g/L and less than or equal to 10 g/L, such as but not limited to 0.013 g/L0, 0.13 g/L1, 0.53 g/L2, 1.03 g/L3, 1.53 g/L4, 2.03 g/L5, 2.53 g/L6, 3.03 g/L7, 3.53 g/L, 4.03 g/L, 5.03 g/L, 6.03 g/L, 7.03 g/L, 8.03 g/L and 9.03 g/L, and the content of Ru in the catalyst is more preferably 0.5-6 g/L.
In the above technical solution, the Re content in the catalyst is preferably more than 0 g/L and less than 10 g/L, such as but not limited to 0.013 g/L0, 0.13 g/L1, 0.53 g/L2, 1.03 g/L3, 1.53 g/L4, 2.03 g/L5, 2.53 g/L6, 3.03 g/L7, 3.53 g/L, 4.03 g/L, 5.03 g/L, 6.03 g/L, 7.03 g/L, 8.03 g/L, 9.03 g/L, and the Re content in the catalyst is more preferably 0.5 to 6 g/L.
In the above technical solution, the Co content in the catalyst is preferably more than 0 g/L and less than 10 g/L, for example, but not limited to, 0.013 g/L0, 0.13 g/L1, 0.53 g/L2, 1.03 g/L3, 1.53 g/L4, 2.03 g/L5, 2.53 g/L6, 3.03 g/L7, 3.53 g/L, 4.03 g/L, 5.03 g/L, 6.03 g/L, 7.03 g/L, 8.03 g/L, 9.03 g/L, and the Co content in the catalyst is more preferably 0.5 to 6 g/L.
In the technical scheme, the Zn content in the catalyst is preferably more than 0 and less than 10 g/L, such as but not limited to 0.013 g/L, 0.13 g/L0, 0.53 g/L1, 1.03 g/L2, 1.53 g/L3, 2.03 g/L4, 2.53 g/L5, 3.03 g/L6, 3.53 g/L, 4.03 g/L, 5.03 g/L, 6.03 g/L, 7.03 g/L, 8.03 g/L and 9.03 g/L, and the Zn content in the catalyst is more preferably 0.5-5 g/L.
In the above technical solution, the P content in the catalyst is preferably more than 0 and 10 g/L or less, for example but not limited to 0.013 g/L, 0.13 g/L0, 0.53 g/L1, 1.03 g/L2, 1.53 g/L3, 2.03 g/L4, 2.53 g/L5, 3.03 g/L6, 3.53 g/L, 4.03 g/L, 5.03 g/L, 6.03 g/L, 7.03 g/L, 8.03 g/L, and 9.03 g/L, and the P content in the catalyst is more preferably 0.5 to 5 g/L.
The key point of the invention is the selection of active components and auxiliary agents, and the variety and index parameters of the active carbon are not particularly limited, and can be reasonably selected by a person skilled in the art. With respect to the activated carbon type, for example, but not limited to, the activated carbon may be coal, shell carbon, of which coconut shell carbon is a non-limiting example. Regarding the particle size of the activated carbon, for example, but not limited to, 10 to 200 mesh (for example, but not limited to, 20 mesh, 30 mesh, 40 mesh, 50 mesh, 60 mesh, 70 mesh, 80 mesh, 90 mesh, 100 mesh, 120 mesh, 150 mesh, 180 mesh, etc.); as for the specific surface of the activated carbon, for example, but not limited to, 0.01 to 1500m2In this range, 900m is given as a non-limiting example2/g、1000m2/g、1100m2/g、1200m2/g、1300m2/g、1400m2G,/g, etc.; as for the average pore volume of the activated carbon, for example, but not limited to, 0.1 to 0.7cm3In this range, by way of non-limiting example, 0.1cm3/g、0.2cm3/g、0.3cm3/g、0.4cm3/g、0.6cm3/g、0.7cm3G,/etc. For the sake of comparability, the activated carbon in the specific embodiment of the invention is coconut shell carbon, the granularity is 60-80 meshes, and the specific surface is 1056m2Per g, average pore volume of 0.32cm3/g。
In order to solve the second technical problem, the invention adopts the following technical scheme: a method for preparing a hydrogenation catalyst according to any one of the above technical problems, comprising the steps of:
a) mixing the solution of the compound of the active component and the compound of the cocatalyst element with the activated carbon;
b) reducing the active component elements in the compound of the active component into simple substances by using a reducing agent.
In the above technical solution, the reducing agent in step b) is preferably at least one of hydrogen, formaldehyde, hydrazine hydrate, sodium borohydride, formic acid or sodium formate. The specific reduction process conditions can be chosen reasonably by the person skilled in the art according to the objectives to be achieved in step b) and without any inventive effort. For example, when the reduction is performed by using a hydrogen-nitrogen mixed gas with a hydrogen volume concentration of 2-4%, the temperature is, for example, but not limited to, 150-300 ℃. The reduction time may be, for example, 1 to 5 hours.
The introduction of P can be any phosphorus-containing compound.
In order to solve the third technical problem, the technical scheme of the invention is as follows:
the application of the catalyst in the technical scheme of one of the technical problems in the reaction of synthesizing 1, 4-cyclohexanedimethanol by hydrogenating 1, 4-cyclohexanedicarboxylic acid.
The key to the present invention is the choice of catalyst, which can be reasonably selected by one skilled in the art for the specific process and process conditions. Such as but not limited to:
the synthesis method of the 1, 4-cyclohexanedimethanol comprises the following steps: using water as a solvent, and reacting 1, 4-cyclohexanedicarboxylic acid with hydrogen in the presence of the catalyst in any one of the above technical schemes to obtain 1, 4-cyclohexanedimethanol.
In the technical scheme, the preferable reaction temperature is 180-250 ℃; the reaction temperature is more preferably 200 to 230 ℃.
In the technical scheme, the preferable hydrogen pressure is 5-12 MPa; the hydrogen pressure is preferably 8-10 MPa.
In the technical scheme, the mass ratio of the 1, 4-cyclohexanedicarboxylic acid to the water is preferably 1 (1-10), and more preferably 1 (4-7).
In the technical scheme, the preferable reaction time is 1-5 hours.
It can be seen from the data of the specific embodiment that when the catalyst of the present invention is used in the synthesis reaction, the conversion rate of the raw material 1, 4-cyclohexanedicarboxylic acid reaches 99.3%, the selectivity of the target product CHDM also reaches 96.5%, that is, the yield of CHDM reaches 95.8%, and a good technical effect is achieved.
Detailed Description
[ example 1 ]
Preparation of the catalyst
Adding RuCl3·3H2O and ZnCl2Dissolving in water to obtain 1200 ml of impregnation liquid containing 6g of Ru and 4g of Zn, mixing the impregnation liquid with 1L activated carbon, impregnating for 24h, drying at 80 ℃ for 6 h, and then reducing at 250 ℃ for 3h in hydrogen and nitrogen mixed gas (the volume concentration of hydrogen in the mixed gas is 3%) to obtain a finished catalyst.
The ICP-AES analysis showed that the catalyst had a Ru content of 6 g/L and a Zn content of 4 g/L.
Synthesis of 1, 4-cyclohexanedimethanol
Adding 150g of 1, 4-cyclohexanedicarboxylic acid and 600g of water into an autoclave, adding 50ml of the obtained catalyst, starting stirring, introducing nitrogen for three times, introducing hydrogen to increase the pressure of the hydrogen to 8.5MPa and keep the pressure stable, maintaining the reaction temperature at 230 ℃, and continuously introducing the hydrogen for reaction for 3 hours. After the reaction is finished, the catalyst is filtered off while the catalyst is hot, the reaction solution is respectively analyzed by liquid chromatography and gas chromatography, and the CHDA conversion rate, the CHDM selectivity and the CHDM yield are calculated.
For ease of comparison, the catalyst compositions and the results of the synthesis reactions are shown in Table 1.
[ example 2 ]
Preparation of the catalyst
Adding RuCl3·3H2O and Na2HPO4Dissolving in water to obtain 1200 ml of impregnation liquid containing 6g of Ru and 4g of P, mixing the impregnation liquid with 1L activated carbon, impregnating for 24h, drying at 80 ℃ for 6 h, and then reducing at 250 ℃ for 3h in hydrogen and nitrogen mixed gas (the volume concentration of hydrogen in the mixed gas is 3%) to obtain a finished catalyst.
The ICP-AES analysis showed that the catalyst had a Ru content of 6 g/L and a P content of 4 g/L.
Synthesis of 1, 4-cyclohexanedimethanol
Adding 150g of 1, 4-cyclohexanedicarboxylic acid and 600g of water into an autoclave, adding 50ml of the obtained catalyst, starting stirring, introducing nitrogen for three times, introducing hydrogen to increase the pressure of the hydrogen to 8.5MPa and keep the pressure stable, maintaining the reaction temperature at 230 ℃, and continuously introducing the hydrogen for reaction for 3 hours. After the reaction is finished, the catalyst is filtered off while the catalyst is hot, the reaction solution is respectively analyzed by liquid chromatography and gas chromatography, and the CHDA conversion rate, the CHDM selectivity and the CHDM yield are calculated.
For ease of comparison, the catalyst compositions and the results of the synthesis reactions are shown in Table 1.
[ example 3 ]
Preparation of the catalyst
Adding Recl3·6H2O and ZnCl2Dissolving in water to obtain 1200 ml of impregnation liquid containing 6g of Re and 4g of Zn, mixing the impregnation liquid with 1L activated carbon, impregnating for 24h, drying at 80 ℃ for 6 h, and then reducing at 250 ℃ for 3h in hydrogen and nitrogen mixed gas (the volume concentration of hydrogen in the mixed gas is 3%) to obtain a finished catalyst.
The catalyst had an Re content of 6 g/L and a Zn content of 4 g/L by ICP-AES analysis.
Synthesis of 1, 4-cyclohexanedimethanol
Adding 150g of 1, 4-cyclohexanedicarboxylic acid and 600g of water into an autoclave, adding 50ml of the obtained catalyst, starting stirring, introducing nitrogen for three times, introducing hydrogen to increase the pressure of the hydrogen to 8.5MPa and keep the pressure stable, maintaining the reaction temperature at 230 ℃, and continuously introducing the hydrogen for reaction for 3 hours. After the reaction is finished, the catalyst is filtered off while the catalyst is hot, the reaction solution is respectively analyzed by liquid chromatography and gas chromatography, and the CHDA conversion rate, the CHDM selectivity and the CHDM yield are calculated.
For ease of comparison, the catalyst compositions and the results of the synthesis reactions are shown in Table 1.
[ example 4 ]
Preparation of the catalyst
Adding Recl3·6H2O and Na2HPO4Dissolving in water to obtain 1200 ml of impregnation liquid containing 6g of Re and 4g of P,and mixing the impregnation liquid with 1L activated carbon, impregnating for 24 hours, drying at 80 ℃ for 6 hours, and then reducing at 250 ℃ for 3 hours in hydrogen-nitrogen mixed gas (the volume concentration of hydrogen in the mixed gas is 3%) to obtain a finished catalyst.
The catalyst had an Re content of 6 g/L and a P content of 4 g/L by ICP-AES analysis.
Synthesis of 1, 4-cyclohexanedimethanol
Adding 150g of 1, 4-cyclohexanedicarboxylic acid and 600g of water into an autoclave, adding 50ml of the obtained catalyst, starting stirring, introducing nitrogen for three times, introducing hydrogen to increase the pressure of the hydrogen to 8.5MPa and keep the pressure stable, maintaining the reaction temperature at 230 ℃, and continuously introducing the hydrogen for reaction for 3 hours. After the reaction is finished, the catalyst is filtered off while the catalyst is hot, the reaction solution is respectively analyzed by liquid chromatography and gas chromatography, and the CHDA conversion rate, the CHDM selectivity and the CHDM yield are calculated.
For ease of comparison, the catalyst compositions and the results of the synthesis reactions are shown in Table 1.
[ example 5 ]
Preparation of the catalyst
Mixing of Co (OAc)2·4H2O and ZnCl2Dissolving in water to obtain 1200 ml of impregnation liquid containing 6g of Co and 4g of Zn, mixing the impregnation liquid with 1L activated carbon, impregnating for 24h, drying at 80 ℃ for 6 h, and reducing at 250 ℃ for 3h in hydrogen and nitrogen mixed gas (the volume concentration of hydrogen in the mixed gas is 3%) to obtain a finished catalyst.
The catalyst had a Co content of 6 g/L and a Zn content of 4 g/L by ICP-AES analysis.
Synthesis of 1, 4-cyclohexanedimethanol
Adding 150g of 1, 4-cyclohexanedicarboxylic acid and 600g of water into an autoclave, adding 50ml of the obtained catalyst, starting stirring, introducing nitrogen for three times, introducing hydrogen to increase the pressure of the hydrogen to 8.5MPa and keep the pressure stable, maintaining the reaction temperature at 230 ℃, and continuously introducing the hydrogen for reaction for 3 hours. After the reaction is finished, the catalyst is filtered off while the catalyst is hot, the reaction solution is respectively analyzed by liquid chromatography and gas chromatography, and the CHDA conversion rate, the CHDM selectivity and the CHDM yield are calculated.
For ease of comparison, the catalyst compositions and the results of the synthesis reactions are shown in Table 1.
[ example 6 ]
Preparation of the catalyst
Mixing of Co (OAc)2·4H2O and Na2HPO4Dissolving in water to obtain 1200 ml of impregnation liquid containing 6g of Co and 4g of P, mixing the impregnation liquid with 1L activated carbon, impregnating for 24h, drying at 80 ℃ for 6 h, and reducing at 250 ℃ for 3h in hydrogen and nitrogen mixed gas (the volume concentration of hydrogen in the mixed gas is 3%) to obtain a finished catalyst.
The catalyst had a Co content of 6 g/L and a P content of 4 g/L by ICP-AES analysis.
Synthesis of 1, 4-cyclohexanedimethanol
Adding 150g of 1, 4-cyclohexanedicarboxylic acid and 600g of water into an autoclave, adding 50ml of the obtained catalyst, starting stirring, introducing nitrogen for three times, introducing hydrogen to increase the pressure of the hydrogen to 8.5MPa and keep the pressure stable, maintaining the reaction temperature at 230 ℃, and continuously introducing the hydrogen for reaction for 3 hours. After the reaction is finished, the catalyst is filtered off while the catalyst is hot, the reaction solution is respectively analyzed by liquid chromatography and gas chromatography, and the CHDA conversion rate, the CHDM selectivity and the CHDM yield are calculated.
For ease of comparison, the catalyst compositions and the results of the synthesis reactions are shown in Table 1.
[ example 7 ]
Preparation of the catalyst
Adding RuCl3·3H2O、ReCl3·6H2O and ZnCl2Dissolving in water to obtain 1200 ml of impregnation liquid containing 3g of Ru, 3g of Re and 4g of Zn, mixing the impregnation liquid with 1L activated carbon, impregnating for 24h, drying at 80 ℃ for 6 h, and then reducing at 250 ℃ for 3h in hydrogen and nitrogen mixed gas (the volume concentration of hydrogen in the mixed gas is 3%) to obtain a finished catalyst.
The ICP-AES analysis showed that the catalyst had a Ru content of 3 g/L, a Re content of 3 g/L and a Zn content of 4 g/L.
Synthesis of 1, 4-cyclohexanedimethanol
Adding 150g of 1, 4-cyclohexanedicarboxylic acid and 600g of water into an autoclave, adding 50ml of the obtained catalyst, starting stirring, introducing nitrogen for three times, introducing hydrogen to increase the pressure of the hydrogen to 8.5MPa and keep the pressure stable, maintaining the reaction temperature at 230 ℃, and continuously introducing the hydrogen for reaction for 3 hours. After the reaction is finished, the catalyst is filtered off while the catalyst is hot, the reaction solution is respectively analyzed by liquid chromatography and gas chromatography, and the CHDA conversion rate, the CHDM selectivity and the CHDM yield are calculated.
For ease of comparison, the catalyst compositions and the results of the synthesis reactions are shown in Table 1.
It can be seen from the comparison of example 7 with examples 1 and 3 that Ru and Re have a synergistic effect in increasing the yield of 1, 4-cyclohexanedimethanol.
[ example 8 ]
Preparation of the catalyst
Adding RuCl3·3H2O、ReCl3·6H2O and Na2HPO4Dissolving in water to obtain 1200 ml of impregnation liquid containing 3g of Ru, 3g of Re and 4g of P, mixing the impregnation liquid with 1L activated carbon, impregnating for 24h, drying at 80 ℃ for 6 h, and then reducing at 250 ℃ for 3h in hydrogen and nitrogen mixed gas (the volume concentration of hydrogen in the mixed gas is 3%) to obtain a finished catalyst.
The ICP-AES analysis showed that the catalyst had a Ru content of 3 g/L, a Re content of 3 g/L and a P content of 4 g/L.
Synthesis of 1, 4-cyclohexanedimethanol
Adding 150g of 1, 4-cyclohexanedicarboxylic acid and 600g of water into an autoclave, adding 50ml of the obtained catalyst, starting stirring, introducing nitrogen for three times, introducing hydrogen to increase the pressure of the hydrogen to 8.5MPa and keep the pressure stable, maintaining the reaction temperature at 230 ℃, and continuously introducing the hydrogen for reaction for 3 hours. After the reaction is finished, the catalyst is filtered off while the catalyst is hot, the reaction solution is respectively analyzed by liquid chromatography and gas chromatography, and the CHDA conversion rate, the CHDM selectivity and the CHDM yield are calculated.
For ease of comparison, the catalyst compositions and the results of the synthesis reactions are shown in Table 1.
As can be seen by comparing example 8 with examples 2 and 4, Ru and Re have a synergistic effect in increasing the yield of 1, 4-cyclohexanedimethanol.
[ example 9 ]
Preparation of the catalyst
Adding Recl3·6H2O、Co(OAc)2·4H2O and ZnCl2Dissolving in water to obtain 1200 ml of impregnation liquid containing 3g of Re, 3g of Co and 4g of Zn, mixing the impregnation liquid with 1L activated carbon, impregnating for 24h, drying for 6 h at 80 ℃, and then reducing for 3h at 250 ℃ in hydrogen and nitrogen mixed gas (the volume concentration of hydrogen in the mixed gas is 3%) to obtain a finished catalyst.
The catalyst had an Re content of 3 g/L, a Co content of 3 g/L and a Zn content of 4 g/L by ICP-AES analysis.
Synthesis of 1, 4-cyclohexanedimethanol
Adding 150g of 1, 4-cyclohexanedicarboxylic acid and 600g of water into an autoclave, adding 50ml of the obtained catalyst, starting stirring, introducing nitrogen for three times, introducing hydrogen to increase the pressure of the hydrogen to 8.5MPa and keep the pressure stable, maintaining the reaction temperature at 230 ℃, and continuously introducing the hydrogen for reaction for 3 hours. After the reaction is finished, the catalyst is filtered off while the catalyst is hot, the reaction solution is respectively analyzed by liquid chromatography and gas chromatography, and the CHDA conversion rate, the CHDM selectivity and the CHDM yield are calculated.
For ease of comparison, the catalyst compositions and the results of the synthesis reactions are shown in Table 1.
It can be seen from the comparison of example 9 with examples 3 and 5 that Re and Co have a synergistic effect in increasing the yield of 1, 4-cyclohexanedimethanol.
[ example 10 ]
Preparation of the catalyst
Adding Recl3·6H2O、Co(OAc)2·4H2O and Na2Dissolving HPO4 in water to obtain 1200 ml of impregnation liquid containing 3g of Re, 3g of Co and 4g of P, mixing the impregnation liquid with 1L of activated carbon, impregnating for 24h, drying at 80 ℃ for 6 h, and then reducing at 250 ℃ for 3h in hydrogen-nitrogen mixed gas (the volume concentration of hydrogen in the mixed gas is 3%) to obtain a finished catalyst.
The catalyst had an Re content of 3 g/L, a Co content of 3 g/L and a P content of 4 g/L by ICP-AES analysis.
Synthesis of 1, 4-cyclohexanedimethanol
Adding 150g of 1, 4-cyclohexanedicarboxylic acid and 600g of water into an autoclave, adding 50ml of the obtained catalyst, starting stirring, introducing nitrogen for three times, introducing hydrogen to increase the pressure of the hydrogen to 8.5MPa and keep the pressure stable, maintaining the reaction temperature at 230 ℃, and continuously introducing the hydrogen for reaction for 3 hours. After the reaction is finished, the catalyst is filtered off while the catalyst is hot, the reaction solution is respectively analyzed by liquid chromatography and gas chromatography, and the CHDA conversion rate, the CHDM selectivity and the CHDM yield are calculated.
For ease of comparison, the catalyst compositions and the results of the synthesis reactions are shown in Table 1.
It can be seen from the comparison of example 10 with examples 4 and 6 that Re and Co have a synergistic effect in increasing the yield of 1, 4-cyclohexanedimethanol.
[ example 11 ]
Preparation of the catalyst
Adding RuCl3·3H2O、Co(OAc)2·4H2O and ZnCl2Dissolving in water to obtain 1200 ml of impregnation liquid containing 3g of Ru, 3g of Co and 4g of Zn, mixing the impregnation liquid with 1L activated carbon, impregnating for 24h, drying for 6 h at 80 ℃, and then reducing for 3h at 250 ℃ in hydrogen-nitrogen mixed gas (the volume concentration of hydrogen in the mixed gas is 3%) to obtain a finished catalyst.
By ICP-AES analysis, the content of Ru in the catalyst is 3 g/L, the content of Co in the catalyst is 3 g/L, and the content of Zn in the catalyst is 4 g/L.
Synthesis of 1, 4-cyclohexanedimethanol
Adding 150g of 1, 4-cyclohexanedicarboxylic acid and 600g of water into an autoclave, adding 50ml of the obtained catalyst, starting stirring, introducing nitrogen for three times, introducing hydrogen to increase the pressure of the hydrogen to 8.5MPa and keep the pressure stable, maintaining the reaction temperature at 230 ℃, and continuously introducing the hydrogen for reaction for 3 hours. After the reaction is finished, the catalyst is filtered off while the catalyst is hot, the reaction solution is respectively analyzed by liquid chromatography and gas chromatography, and the CHDA conversion rate, the CHDM selectivity and the CHDM yield are calculated.
For ease of comparison, the catalyst compositions and the results of the synthesis reactions are shown in Table 1.
As can be seen by comparing example 11 with examples 1 and 5, Ru and Co have a synergistic effect in increasing the yield of 1, 4-cyclohexanedimethanol.
[ example 12 ]
Preparation of the catalyst
Adding RuCl3·3H2O、Co(OAc)2·4H2O and Na2HPO4Dissolving in water to obtain 1200 ml of impregnation liquid containing 3g of Ru, 3g of Co and 4g of P, mixing the impregnation liquid with 1L activated carbon, impregnating for 24h, drying for 6 h at 80 ℃, and then reducing for 3h at 250 ℃ in hydrogen-nitrogen mixed gas (the volume concentration of hydrogen in the mixed gas is 3%) to obtain a finished catalyst.
The ICP-AES analysis showed that the catalyst had a Ru content of 3 g/L, a Co content of 3 g/L and a P content of 4 g/L.
Synthesis of 1, 4-cyclohexanedimethanol
Adding 150g of 1, 4-cyclohexanedicarboxylic acid and 600g of water into an autoclave, adding 50ml of the obtained catalyst, starting stirring, introducing nitrogen for three times, introducing hydrogen to increase the pressure of the hydrogen to 8.5MPa and keep the pressure stable, maintaining the reaction temperature at 230 ℃, and continuously introducing the hydrogen for reaction for 3 hours. After the reaction is finished, the catalyst is filtered off while the catalyst is hot, the reaction solution is respectively analyzed by liquid chromatography and gas chromatography, and the CHDA conversion rate, the CHDM selectivity and the CHDM yield are calculated.
For ease of comparison, the catalyst compositions and the results of the synthesis reactions are shown in Table 1.
As can be seen by comparing example 12 with examples 2 and 6, Ru and Co have a synergistic effect in increasing the yield of 1, 4-cyclohexanedimethanol.
[ example 13 ]
Preparation of the catalyst
Adding RuCl3·3H2O、ReCl3·6H2O and ZnCl2、Na2HPO4Dissolving in water to obtain a solution containing 3g of Ru and 3g of Re, 3g of Zn and 1200 ml of impregnation liquid of 1g of P, mixing the impregnation liquid with 1L activated carbon, impregnating for 24h, drying for 6 h at 80 ℃, and then reducing for 3h at 250 ℃ in hydrogen-nitrogen mixed gas (the volume concentration of hydrogen in the mixed gas is 3%) to obtain a finished catalyst.
By ICP-AES analysis, the catalyst had a Ru content of 3 g/L, a Re content of 3 g/L, a Zn content of 3 g/L and a P content of 1 g/L.
Synthesis of 1, 4-cyclohexanedimethanol
Adding 150g of 1, 4-cyclohexanedicarboxylic acid and 600g of water into an autoclave, adding 50ml of the obtained catalyst, starting stirring, introducing nitrogen for three times, introducing hydrogen to increase the pressure of the hydrogen to 8.5MPa and keep the pressure stable, maintaining the reaction temperature at 230 ℃, and continuously introducing the hydrogen for reaction for 3 hours. After the reaction is finished, the catalyst is filtered off while the catalyst is hot, the reaction solution is respectively analyzed by liquid chromatography and gas chromatography, and the CHDA conversion rate, the CHDM selectivity and the CHDM yield are calculated.
For ease of comparison, the catalyst compositions and the results of the synthesis reactions are shown in Table 1.
As can be seen by comparing example 13 with examples 7 and 8, Zn and P have a synergistic effect in increasing the yield of 1, 4-cyclohexanedimethanol and increasing the selectivity of 1, 4-cyclohexanedimethanol.
[ example 14 ]
Preparation of the catalyst
Adding Recl3·6H2O、Co(OAc)2·4H2O and ZnCl2、Na2HPO4Dissolving in water to obtain 1200 ml of impregnation liquid containing 3g of Re, 3g of Co, 3g of Zn and 1g of P, mixing the impregnation liquid with 1L activated carbon, impregnating for 24h, drying at 80 ℃ for 6 h, and then reducing at 250 ℃ for 3h in hydrogen-nitrogen mixed gas (the volume concentration of hydrogen in the mixed gas is 3%) to obtain a finished catalyst.
The catalyst had an Re content of 3 g/L, a Co content of 3 g/L, a Zn content of 3 g/L and a P content of 1 g/L by ICP-AES analysis.
Synthesis of 1, 4-cyclohexanedimethanol
Adding 150g of 1, 4-cyclohexanedicarboxylic acid and 600g of water into an autoclave, adding 50ml of the obtained catalyst, starting stirring, introducing nitrogen for three times, introducing hydrogen to increase the pressure of the hydrogen to 8.5MPa and keep the pressure stable, maintaining the reaction temperature at 230 ℃, and continuously introducing the hydrogen for reaction for 3 hours. After the reaction is finished, the catalyst is filtered off while the catalyst is hot, the reaction solution is respectively analyzed by liquid chromatography and gas chromatography, and the CHDA conversion rate, the CHDM selectivity and the CHDM yield are calculated.
For ease of comparison, the catalyst compositions and the results of the synthesis reactions are shown in Table 1.
It can be seen from the comparison of example 14 with examples 9 and 10 that Zn and P have a synergistic effect in increasing the yield of 1, 4-cyclohexanedimethanol and increasing the selectivity of 1, 4-cyclohexanedimethanol.
[ example 15 ]
Preparation of the catalyst
Adding RuCl3·3H2O、Co(OAc)2·4H2O and ZnCl2、Na2HPO4Dissolving in water to obtain 1200 ml of impregnation liquid containing 3g of Ru, 3g of Co, 3g of Zn and 1g of P, mixing the impregnation liquid with 1L activated carbon, impregnating for 24h, drying at 80 ℃ for 6 h, and then reducing at 250 ℃ for 3h in hydrogen-nitrogen mixed gas (the volume concentration of hydrogen in the mixed gas is 3%) to obtain a finished catalyst.
According to ICP-AES analysis, the content of Ru in the catalyst is 3 g/L, the content of Co in the catalyst is 3 g/L, the content of Zn in the catalyst is 3 g/L, and the content of P in the catalyst is 1 g/L.
Synthesis of 1, 4-cyclohexanedimethanol
Adding 150g of 1, 4-cyclohexanedicarboxylic acid and 600g of water into an autoclave, adding 50ml of the obtained catalyst, starting stirring, introducing nitrogen for three times, introducing hydrogen to increase the pressure of the hydrogen to 8.5MPa and keep the pressure stable, maintaining the reaction temperature at 230 ℃, and continuously introducing the hydrogen for reaction for 3 hours. After the reaction is finished, the catalyst is filtered off while the catalyst is hot, the reaction solution is respectively analyzed by liquid chromatography and gas chromatography, and the CHDA conversion rate, the CHDM selectivity and the CHDM yield are calculated.
For ease of comparison, the catalyst compositions and the results of the synthesis reactions are shown in Table 1.
It can be seen from the comparison of example 15 with examples 11 and 12 that Zn and P have a synergistic effect in increasing the yield of 1, 4-cyclohexanedimethanol and increasing the selectivity of 1, 4-cyclohexanedimethanol.
[ example 16 ]
Preparation of the catalyst
Adding RuCl3·3H2O、ReCl3·6H2O、Co(OAc)2·4H2O and ZnCl2Na2HPO4 was dissolved in water to give 1200 ml of an impregnation solution containing 2.5g of Re, 1g of Co, 3g of Zn and 1g of P, the impregnation solution was mixed with 1L of activated carbon, impregnated for 24 hours, dried at 80 ℃ for 6 hours, and then reduced at 250 ℃ for 3 hours in a hydrogen-nitrogen mixed gas (the volume concentration of hydrogen in the mixed gas is 3%) to give a finished catalyst.
By ICP-AES analysis, the content of Ru in the catalyst is 2.5 g/L, the content of Re is 2.5 g/L, the content of Co is 1 g/L, the content of Zn is 3 g/L and the content of P is 1 g/L.
Synthesis of 1, 4-cyclohexanedimethanol
Adding 150g of 1, 4-cyclohexanedicarboxylic acid and 600g of water into an autoclave, adding 50ml of the obtained catalyst, starting stirring, introducing nitrogen for three times, introducing hydrogen to increase the pressure of the hydrogen to 8.5MPa and keep the pressure stable, maintaining the reaction temperature at 230 ℃, and continuously introducing the hydrogen for reaction for 3 hours. After the reaction is finished, the catalyst is filtered off while the catalyst is hot, the reaction solution is respectively analyzed by liquid chromatography and gas chromatography, and the CHDA conversion rate, the CHDM selectivity and the CHDM yield are calculated.
For ease of comparison, the catalyst compositions and the results of the synthesis reactions are shown in Table 1.
In comparison with examples 1 to 15, it can be seen that Ru, Re, Co, Zn and P have mutually combined promoting effects in increasing the yield of 1, 4-cyclohexanedimethanol and increasing the selectivity of 1, 4-cyclohexanedimethanol.
TABLE 1
Figure BDA0001363288650000141

Claims (6)

  1. The catalyst for hydrogenation of 1, 4-cyclohexanedicarboxylic acid comprises a carrier, an active component and a cocatalyst, wherein the carrier is activated carbon, the active component comprises Re and Co, and the cocatalyst comprises Zn, wherein the Re content is more than 0 g/L and less than 10 g/L, the Co content is more than 0 g/L and less than 10 g/L, and the Zn content is more than 0 g/L and less than 10 g/L.
  2. 2. The catalyst according to claim 1, wherein the Re content of the catalyst is 0.5 to 6 g/L.
  3. 3. The catalyst according to claim 1, wherein the Zn content in the catalyst is 0.5 to 5 g/L.
  4. 4. A process for preparing a catalyst as claimed in any one of claims 1 to 3, comprising the steps of:
    a) mixing the solution of the compound of the active component and the compound of the cocatalyst element with the activated carbon;
    b) reducing the active component elements in the compound of the active component into simple substances by using a reducing agent.
  5. 5. The method according to claim 4, wherein the reducing agent in step b is at least one selected from hydrogen, formaldehyde, hydrazine hydrate, sodium borohydride, formic acid and sodium formate.
  6. 6. Use of the catalyst according to any one of claims 1 to 3 in the reaction of 1, 4-cyclohexanedimethanol through hydrogenation of 1, 4-cyclohexanedicarboxylic acid.
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Publication number Priority date Publication date Assignee Title
CN1426324A (en) * 2000-03-24 2003-06-25 巴斯福股份公司 Method for production of alcohols on rhenium-containing activatod charcoal supported catalysts
CN103769089A (en) * 2012-10-25 2014-05-07 中国石油化工股份有限公司 Catalyst preparation method, and synthesis method of catalyst and trans-1,4-cyclohexane dicarboxylic acid

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1426324A (en) * 2000-03-24 2003-06-25 巴斯福股份公司 Method for production of alcohols on rhenium-containing activatod charcoal supported catalysts
CN103769089A (en) * 2012-10-25 2014-05-07 中国石油化工股份有限公司 Catalyst preparation method, and synthesis method of catalyst and trans-1,4-cyclohexane dicarboxylic acid

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