CN109304167A - 1,4 cyclohexanedicarboxylic acid hydrogenation catalyst - Google Patents

1,4 cyclohexanedicarboxylic acid hydrogenation catalyst Download PDF

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CN109304167A
CN109304167A CN201710628273.4A CN201710628273A CN109304167A CN 109304167 A CN109304167 A CN 109304167A CN 201710628273 A CN201710628273 A CN 201710628273A CN 109304167 A CN109304167 A CN 109304167A
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catalyst
hydrogen
content
reaction
chdm
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CN109304167B (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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Abstract

The present invention relates to Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic hydrogenation catalyst, solve the problems, such as that yield is low when Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic adds hydrogen to prepare 1,4-CHDM in the prior art.By using Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic hydrogenation catalyst, including carrier, active component and co-catalyst, the carrier is active carbon, and active component includes Ru, and the co-catalyst includes the technical solution of Zn, it can be used for producing in the industrial production of 1,4-CHDM.

Description

1,4 cyclohexanedicarboxylic acid hydrogenation catalyst
Technical field
The present invention relates to Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic hydrogenation catalyst, preparation method and applications.
Background technique
1,4-CHDM (abbreviation CHDM) is the important Organic Chemicals for producing polyester resin, substitutes second by it Glycol or the polyester resin of other polynary alcohol productions have good thermal stability and thermoplasticity, can keep at a higher temperature Stable physical property and electrical property, and the product as made from this resinoid then has good chemical resistance and environment resistant. The technique of industrialized production 1,4-CHDM is mainly using dimethyl terephthalate (DMT) as raw material at present, first benzene ring hydrogenation system Standby Isosorbide-5-Nitrae-dimethyl hexahydrophthalate, then 1,4-CHDM is prepared by ester through hydrogenation reaction.Due to terephthalic acid (TPA) (PTA) price is relatively low and abundance, therefore occurs preparing Isosorbide-5-Nitrae-hexamethylene by raw material of terephthalic acid (TPA) in recent years The trend of dimethanol.Its process is generally also needed by two-step reaction, is phenyl ring selection plus hydrogen production Isosorbide-5-Nitrae-hexamethylene diformazan first Acid, then Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic repeated hydrogenation generates 1,4-CHDM.In view of the complexity of two-step process, There are Many researchers to carry out the research that terephthalic acid (TPA) one-step method adds hydrogen to prepare 1,4 cyclohexane dimethanol.Such as Mitsubishi Company discloses the work that PTA prepares CHDM in liquid-phase condition next step method in the patent JP200007596 of application in 1998 Skill.Its catalyst has selected the catalyst of the component containing Ru and Sn, preferably also contains Pt, catalyst is using active carbon as carrier.Implement Specific reaction process is disclosed in example, i.e., PTA, water and catalyst is added under argon atmosphere in autoclave, in hydrogen pressure Temperature is risen to 230 DEG C when 1MPa, then is passed through hydrogen reaction when hydrogen pressure reaches 15MPa, takes out reaction solution after reacting 4h, The yield of CHDM only has 28.3%.(the The drastic effect of platinum on such as Yoshinori Hara carbon-supported ruthenium-tin catalysts used for hydrogenation reactions of carboxylic acids.Y.Hara,K.Endou.Applied Catalysis A:General 239(2003)181–195) Hydrogenation reaction is carried out using Ru-Sn-Pt/C catalyst, although its Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic conversion ratio has reached 98%, The highest yield of 1,4-CHDM is only that the Ru-Sn-Re/C catalyst of 81.6%, US6495730 use carries out adding hydrogen Reaction, the yield of 1,4-CHDM are also only 75%.
Summary of the invention
Problem to be solved by this invention first is that 1,4 cyclohexanedicarboxylic acid existing in the prior art add hydrogen prepare 1, The low problem of 4- cyclohexanedimethanol yield provides a kind of 1,4-CHDM hydrogenation catalyst.The catalyst has 1, 4- cyclohexane cyclohexanedimethanodibasic is hydrogenated to the characteristics of 1,4 cyclohexane dimethanol high income.
Problem to be solved by this invention second is that the preparation method of catalyst described in one of above-mentioned technical problem.
Problem to be solved by this invention third is that using catalyst described in one of above-mentioned technical problem application.
One of in order to solve the above-mentioned technical problem, The technical solution adopted by the invention is as follows: Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic adds Hydrogen catalyst, including carrier, active component and co-catalyst, the carrier are active carbon, and active component includes Ru, and described help is urged Agent includes Zn.
In above-mentioned technical proposal, the active component preferably includes Re, Ru and Re and is improving 1,4-CHDM receipts There is synergistic effect in terms of rate.
In above-mentioned technical proposal, the preferably described active component of the active component further includes that Co, Ru and Co are improving Isosorbide-5-Nitrae- There is synergistic effect in terms of cyclohexanedimethanol yield.
In above-mentioned technical proposal, the active constituent preferably includes that Re and Co, Re and Co are improving Isosorbide-5-Nitrae-hexamethylene simultaneously There is synergistic effect in terms of dimethanol yield.
In above-mentioned technical proposal, the co-catalyst preferably includes P, Zn and P and is improving 1,4-CHDM yield There is synergistic effect with 1,4 cyclohexane dimethanol selectivity aspect is improved.
In above-mentioned technical proposal, most preferably, the active component includes Ru, Re and Co, the co-catalyst simultaneously It simultaneously include Zn and P, Ru, Re, Co, Zn and P are improving 1,4-CHDM yield and improving 1,4-CHDM Selectivity aspect has the facilitation effect being combined with each other.
In above-mentioned technical proposal, Ru content is preferably greater than 0g/L and 10g/L hereinafter, such as, but not limited in catalyst 0.01g/L、0.1g/L、0.5g/L、1g/L、1.5g/L、2g/L、2.5g/L、3g/L、3.5g/L、4g/L、5g/L、6g/L、7g/ L,8g/L,9g/L.Ru content is more preferably 0.5~6g/L in catalyst.
In above-mentioned technical proposal, Re content is preferably greater than 0g/L and 10g/L hereinafter, such as, but not limited in catalyst 0.01g/L、0.1g/L、0.5g/L、1g/L、1.5g/L、2g/L、2.5g/L、3g/L、3.5g/L、4g/L、5g/L、6g/L、7g/ L,8g/L,9g/L.Re content is more preferably 0.5~6g/L in catalyst.
In above-mentioned technical proposal, Co content is preferably greater than 0g/L and 10g/L hereinafter, such as, but not limited in catalyst 0.01g/L、0.1g/L、0.5g/L、1g/L、1.5g/L、2g/L、2.5g/L、3g/L、3.5g/L、4g/L、5g/L、6g/L、7g/ L,8g/L,9g/L.Co content is more preferably 0.5~6g/L in catalyst.
In above-mentioned technical proposal, Zn content is preferably greater than 0 and 10g/L hereinafter, such as, but not limited in catalyst 0.01g/L、0.1g/L、0.5g/L、1g/L、1.5g/L、2g/L、2.5g/L、3g/L、3.5g/L、4g/L、5g/L、6g/L、7g/ L,8g/L,9g/L.Zn content is more preferably 0.5~5g/L in catalyst.
In above-mentioned technical proposal, P content is preferably greater than 0 and 10g/L hereinafter, such as, but not limited to 0.01g/ in catalyst L、0.1g/L、0.5g/L、1g/L、1.5g/L、2g/L、2.5g/L、3g/L、3.5g/L、4g/L、5g/L、6g/L、7g/L、8g/L、 9g/L.P content is more preferably 0.5~5g/L in catalyst.
Key of the invention is the selection of active constituent and auxiliary agent, and does not have to active carbon type and the index parameter of itself Especially limitation, those skilled in the art can reasonably select.About active carbon type, such as, but not limited to active carbon can be coal Matter, fruit shell carbon as non limiting example can be coconut husk charcoal in fruit shell carbon.About the granularity of active carbon, such as, but not limited to 10~200 mesh (such as, 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.)；About the specific surface of active carbon, such as, but not limited to 0.01~1500m2/ g, within this range non-limit Property processed is exemplified as 900m2/g、1000m2/g、1100m2/g、1200m2/g、1300m2/g、1400m2/ g etc.；About active carbon Average Kong Rong, such as, but not limited to 0.1~0.7cm3/ g, non limiting example is 0.1cm within this range3/g、0.2cm3/ g、0.3cm3/g、0.4cm3/g、0.6cm3/g、0.7cm3/ g etc..Work in order to count on year-on-year basis, in the specific embodiment of the invention Property charcoal be coconut husk charcoal, granularity be 60~80 mesh, specific surface 1056m2/ g, average Kong Rongwei 0.32cm3/g。
In order to solve the above-mentioned technical problem two, The technical solution adopted by the invention is as follows: one of above-mentioned technical problem The preparation method of any one hydrogenation catalyst, includes the following steps:
A) solution of the compound of active constituent and the compound of promoter elements is mixed with active carbon；
It b) is simple substance by the active constituent element reduction in the compound of active constituent with reducing agent.
In above-mentioned technical proposal, reducing agent described in step b) is preferably hydrogen, formaldehyde, hydrazine hydrate, sodium borohydride, formic acid Or at least one of sodium formate.Specific reducing process condition can according to step b) target those skilled in the art achieved It is made the creative labor with reasonably selecting and not needing.For example, when using hydrogen nitrogen of the hydrogen volume concentration for 2~4% It is that the temperature of use is such as, but not limited to 150~300 DEG C that gaseous mixture, which carries out reduction,.
The introducing of P can be any phosphorus-containing compound.
In order to solve the above-mentioned technical problem three, technical scheme is as follows:
Catalyst described in any one of technical solution of one of above-mentioned technical problem adds hydrogen in 1,4 cyclohexanedicarboxylic acid Synthesize the application in 1,4 cyclohexane dimethanol reaction.
Key of the invention is the selection of catalyst, for specific process and process conditions, the technology of this field Personnel can reasonably select.Such as, but not limited to:
The synthetic method of 1,4-CHDM includes the following steps: to take water as a solvent, in the above-mentioned technical solutions In the presence of described in any item hydrogenation catalysts, Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic reacts to obtain 1,4-CHDM with hydrogen.
In above-mentioned technical proposal, preferable reaction temperature is 180~250 DEG C；Reaction temperature is more preferably 200~230 DEG C.
In above-mentioned technical proposal, preferably Hydrogen Vapor Pressure is 5~12MPa；Hydrogen Vapor Pressure is preferably 8~10MPa.
In above-mentioned technical proposal, the mass ratio of Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic and water is preferably 1:(1~10), more preferably 1: (4~7).
In above-mentioned technical proposal, preferred reaction time is 1~5 hour.
When can be seen that catalyst of the present invention for the synthetic reaction from the data of specific embodiment, raw material Isosorbide-5-Nitrae- The conversion ratio of cyclohexane cyclohexanedimethanodibasic has reached 99.3%, and the selectivity of target product CHDM has also reached 96.5% namely CHDM Yield reached 95.8%, achieve preferable technical effect.
Specific embodiment
[embodiment 1]
The preparation of catalyst
By RuCl3·3H2O and ZnCl2It is dissolved in water, 1200 milliliters of maceration extract containing 6 grams of Ru and 4 gram of Zn are obtained, by the leaching Stain liquid is mixed with 1L active carbon, dipping for 24 hours, dry 6 hours at 80 DEG C, then in hydrogen nitrogen mixture (hydrogen in gaseous mixture Air volume concentration is that 3%) 250 DEG C of reduction 3h obtain finished catalyst.
ICP-AES is analyzed, and the Ru content in catalyst is 6g/L, and Zn content is 4g/L.
The synthesis of 1,4 cyclohexane dimethanol
Autoclave is added in 150g Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic and 600g water, the above-mentioned resulting catalyst of 50ml is added, opens Stirring is opened, is first passed through nitrogen displacement three times, is being passed through hydrogen displacement three times, then passing to hydrogen makes Hydrogen Vapor Pressure rise to 8.5MPa And keep stable, 230 DEG C of maintaining reaction temperature, and continuously it is passed through hydrogen reaction 3h.After reaction, catalyst is filtered out while hot, Reaction solution is analyzed respectively with liquid chromatogram and gas-chromatography, calculates the yield of CHDA conversion ratio, CHDM selectivity and CHDM.
For convenient for comparing, catalyst composition and synthetic reaction result are listed in table 1.
[embodiment 2]
The preparation of catalyst
By RuCl3·3H2O and Na2HPO4It is dissolved in water, obtains 1200 milliliters of maceration extract containing 6 grams of Ru and 4 gram of P, it will be described Maceration extract is mixed with 1L active carbon, and dipping is for 24 hours, 6 hours dry at 80 DEG C, then in hydrogen nitrogen mixture (in gaseous mixture Hydrogen volume concentration is that 3%) 250 DEG C of reduction 3h obtain finished catalyst.
ICP-AES is analyzed, and the Ru content in catalyst is 6g/L, P content 4g/L.
The synthesis of 1,4 cyclohexane dimethanol
Autoclave is added in 150g Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic and 600g water, the above-mentioned resulting catalyst of 50ml is added, opens Stirring is opened, is first passed through nitrogen displacement three times, is being passed through hydrogen displacement three times, then passing to hydrogen makes Hydrogen Vapor Pressure rise to 8.5MPa And keep stable, 230 DEG C of maintaining reaction temperature, and continuously it is passed through hydrogen reaction 3h.After reaction, catalyst is filtered out while hot, Reaction solution is analyzed respectively with liquid chromatogram and gas-chromatography, calculates the yield of CHDA conversion ratio, CHDM selectivity and CHDM.
For convenient for comparing, catalyst composition and synthetic reaction result are listed in table 1.
[embodiment 3]
The preparation of catalyst
By ReCl3·6H2O and ZnCl2It is dissolved in water, 1200 milliliters of maceration extract containing 6 grams of Re and 4 gram of Zn are obtained, by the leaching Stain liquid is mixed with 1L active carbon, dipping for 24 hours, dry 6 hours at 80 DEG C, then in hydrogen nitrogen mixture (hydrogen in gaseous mixture Air volume concentration is that 3%) 250 DEG C of reduction 3h obtain finished catalyst.
ICP-AES is analyzed, and the Re content in catalyst is 6g/L, and Zn content is 4g/L.
The synthesis of 1,4 cyclohexane dimethanol
Autoclave is added in 150g Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic and 600g water, the above-mentioned resulting catalyst of 50ml is added, opens Stirring is opened, is first passed through nitrogen displacement three times, is being passed through hydrogen displacement three times, then passing to hydrogen makes Hydrogen Vapor Pressure rise to 8.5MPa And keep stable, 230 DEG C of maintaining reaction temperature, and continuously it is passed through hydrogen reaction 3h.After reaction, catalyst is filtered out while hot, Reaction solution is analyzed respectively with liquid chromatogram and gas-chromatography, calculates the yield of CHDA conversion ratio, CHDM selectivity and CHDM.
For convenient for comparing, catalyst composition and synthetic reaction result are listed in table 1.
[embodiment 4]
The preparation of catalyst
By ReCl3·6H2O and Na2HPO4It is dissolved in water, obtains 1200 milliliters of maceration extract containing 6 grams of Re and 4 gram of P, it will be described Maceration extract is mixed with 1L active carbon, and dipping is for 24 hours, 6 hours dry at 80 DEG C, then in hydrogen nitrogen mixture (in gaseous mixture Hydrogen volume concentration is that 3%) 250 DEG C of reduction 3h obtain finished catalyst.
ICP-AES is analyzed, and the Re content in catalyst is 6g/L, P content 4g/L.
The synthesis of 1,4 cyclohexane dimethanol
Autoclave is added in 150g Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic and 600g water, the above-mentioned resulting catalyst of 50ml is added, opens Stirring is opened, is first passed through nitrogen displacement three times, is being passed through hydrogen displacement three times, then passing to hydrogen makes Hydrogen Vapor Pressure rise to 8.5MPa And keep stable, 230 DEG C of maintaining reaction temperature, and continuously it is passed through hydrogen reaction 3h.After reaction, catalyst is filtered out while hot, Reaction solution is analyzed respectively with liquid chromatogram and gas-chromatography, calculates the yield of CHDA conversion ratio, CHDM selectivity and CHDM.
For convenient for comparing, catalyst composition and synthetic reaction result are listed in table 1.
[embodiment 5]
The preparation of catalyst
By Co (OAc)2·4H2O and ZnCl2It is dissolved in water, 1200 milliliters of maceration extract containing 6 grams of Co and 4 gram of Zn are obtained, by institute It states maceration extract to mix with 1L active carbon, dipping is for 24 hours, 6 hours dry at 80 DEG C, then in hydrogen nitrogen mixture (gaseous mixture Middle hydrogen volume concentration is that 3%) 250 DEG C of reduction 3h obtain finished catalyst.
ICP-AES is analyzed, and the Co content in catalyst is 6g/L, and Zn content is 4g/L.
The synthesis of 1,4 cyclohexane dimethanol
Autoclave is added in 150g Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic and 600g water, the above-mentioned resulting catalyst of 50ml is added, opens Stirring is opened, is first passed through nitrogen displacement three times, is being passed through hydrogen displacement three times, then passing to hydrogen makes Hydrogen Vapor Pressure rise to 8.5MPa And keep stable, 230 DEG C of maintaining reaction temperature, and continuously it is passed through hydrogen reaction 3h.After reaction, catalyst is filtered out while hot, Reaction solution is analyzed respectively with liquid chromatogram and gas-chromatography, calculates the yield of CHDA conversion ratio, CHDM selectivity and CHDM.
For convenient for comparing, catalyst composition and synthetic reaction result are listed in table 1.
[embodiment 6]
The preparation of catalyst
By Co (OAc)2·4H2O and Na2HPO4It is dissolved in water, 1200 milliliters of maceration extract containing 6 grams of Co and 4 gram of P are obtained, by institute It states maceration extract to mix with 1L active carbon, dipping is for 24 hours, 6 hours dry at 80 DEG C, then in hydrogen nitrogen mixture (gaseous mixture Middle hydrogen volume concentration is that 3%) 250 DEG C of reduction 3h obtain finished catalyst.
ICP-AES is analyzed, and the Co content in catalyst is 6g/L, P content 4g/L.
The synthesis of 1,4 cyclohexane dimethanol
Autoclave is added in 150g Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic and 600g water, the above-mentioned resulting catalyst of 50ml is added, opens Stirring is opened, is first passed through nitrogen displacement three times, is being passed through hydrogen displacement three times, then passing to hydrogen makes Hydrogen Vapor Pressure rise to 8.5MPa And keep stable, 230 DEG C of maintaining reaction temperature, and continuously it is passed through hydrogen reaction 3h.After reaction, catalyst is filtered out while hot, Reaction solution is analyzed respectively with liquid chromatogram and gas-chromatography, calculates the yield of CHDA conversion ratio, CHDM selectivity and CHDM.
For convenient for comparing, catalyst composition and synthetic reaction result are listed in table 1.
[embodiment 7]
The preparation of catalyst
By RuCl3·3H2O、ReCl3·6H2O and ZnCl2It is dissolved in water, obtains the maceration extract containing 3 grams of Ru, 3 grams of Re and 4 gram of Zn 1200 milliliters, the maceration extract is mixed with 1L active carbon, dipping is for 24 hours, 6 hours dry at 80 DEG C, then in hydrogen nitrogen 250 DEG C of reduction 3h of gaseous mixture (hydrogen volume concentration is 3% in gaseous mixture) obtain finished catalyst.
ICP-AES is analyzed, and the Ru content in catalyst is 3g/L, and Re content is 3g/L, and Zn content is 4g/L.1,4- hexamethylene The synthesis of alkane dimethanol
Autoclave is added in 150g Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic and 600g water, the above-mentioned resulting catalyst of 50ml is added, opens Stirring is opened, is first passed through nitrogen displacement three times, is being passed through hydrogen displacement three times, then passing to hydrogen makes Hydrogen Vapor Pressure rise to 8.5MPa And keep stable, 230 DEG C of maintaining reaction temperature, and continuously it is passed through hydrogen reaction 3h.After reaction, catalyst is filtered out while hot, Reaction solution is analyzed respectively with liquid chromatogram and gas-chromatography, calculates the yield of CHDA conversion ratio, CHDM selectivity and CHDM.
For convenient for comparing, catalyst composition and synthetic reaction result are listed in table 1.
By embodiment 7 and embodiment 1 and embodiment 3 on year-on-year basis as can be seen that Ru and Re is improving Isosorbide-5-Nitrae-hexamethylene diformazan There is synergistic effect in terms of alcohol yield.
[embodiment 8]
The preparation of catalyst
By RuCl3·3H2O、ReCl3·6H2O and Na2HPO4It is dissolved in water, obtains the dipping containing 3 grams of Ru, 3 grams of Re and 4 gram of P 1200 milliliters of liquid, the maceration extract is mixed with 1L active carbon, dipping is for 24 hours, 6 hours dry at 80 DEG C, then in hydrogen nitrogen 250 DEG C of reduction 3h of gas gaseous mixture (hydrogen volume concentration is 3% in gaseous mixture) obtain finished catalyst.
ICP-AES is analyzed, and the Ru content in catalyst is 3g/L, and Re content is 3g/L, P content 4g/L.1,4- hexamethylene The synthesis of alkane dimethanol
Autoclave is added in 150g Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic and 600g water, the above-mentioned resulting catalyst of 50ml is added, opens Stirring is opened, is first passed through nitrogen displacement three times, is being passed through hydrogen displacement three times, then passing to hydrogen makes Hydrogen Vapor Pressure rise to 8.5MPa And keep stable, 230 DEG C of maintaining reaction temperature, and continuously it is passed through hydrogen reaction 3h.After reaction, catalyst is filtered out while hot, Reaction solution is analyzed respectively with liquid chromatogram and gas-chromatography, calculates the yield of CHDA conversion ratio, CHDM selectivity and CHDM.
For convenient for comparing, catalyst composition and synthetic reaction result are listed in table 1.
By embodiment 8 and embodiment 2 and embodiment 4 on year-on-year basis as can be seen that Ru and Re is improving Isosorbide-5-Nitrae-hexamethylene diformazan There is synergistic effect in terms of alcohol yield.
[embodiment 9]
The preparation of catalyst
By ReCl3·6H2O、Co(OAc)2·4H2O and ZnCl2It is dissolved in water, obtains the leaching containing 3 grams of Re, 3 grams of Co and 4 gram of Zn 1200 milliliters of stain liquid, the maceration extract is mixed with 1L active carbon, dipping is for 24 hours, 6 hours dry at 80 DEG C, then in hydrogen 250 DEG C of reduction 3h of nitrogen mixture (hydrogen volume concentration is 3% in gaseous mixture) obtain finished catalyst.
ICP-AES is analyzed, and the Re content in catalyst is 3g/L, and Co content is 3g/L, and Zn content is 4g/L.1,4- hexamethylene The synthesis of alkane dimethanol
Autoclave is added in 150g Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic and 600g water, the above-mentioned resulting catalyst of 50ml is added, opens Stirring is opened, is first passed through nitrogen displacement three times, is being passed through hydrogen displacement three times, then passing to hydrogen makes Hydrogen Vapor Pressure rise to 8.5MPa And keep stable, 230 DEG C of maintaining reaction temperature, and continuously it is passed through hydrogen reaction 3h.After reaction, catalyst is filtered out while hot, Reaction solution is analyzed respectively with liquid chromatogram and gas-chromatography, calculates the yield of CHDA conversion ratio, CHDM selectivity and CHDM.
For convenient for comparing, catalyst composition and synthetic reaction result are listed in table 1.
By embodiment 9 and embodiment 3 and embodiment 5 on year-on-year basis as can be seen that Re and Co is improving Isosorbide-5-Nitrae-hexamethylene diformazan There is synergistic effect in terms of alcohol yield.
[embodiment 10]
The preparation of catalyst
By ReCl3·6H2O、Co(OAc)2·4H2O and Na2HPO4 is dissolved in water, obtains the leaching containing 3 grams of Re, 3 grams of Co and 4 gram of P 1200 milliliters of stain liquid, the maceration extract is mixed with 1L active carbon, dipping is for 24 hours, 6 hours dry at 80 DEG C, then in hydrogen 250 DEG C of reduction 3h of nitrogen mixture (hydrogen volume concentration is 3% in gaseous mixture) obtain finished catalyst.
ICP-AES is analyzed, and the Re content in catalyst is 3g/L, and Co content is 3g/L, P content 4g/L.1,4- hexamethylene The synthesis of alkane dimethanol
Autoclave is added in 150g Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic and 600g water, the above-mentioned resulting catalyst of 50ml is added, opens Stirring is opened, is first passed through nitrogen displacement three times, is being passed through hydrogen displacement three times, then passing to hydrogen makes Hydrogen Vapor Pressure rise to 8.5MPa And keep stable, 230 DEG C of maintaining reaction temperature, and continuously it is passed through hydrogen reaction 3h.After reaction, catalyst is filtered out while hot, Reaction solution is analyzed respectively with liquid chromatogram and gas-chromatography, calculates the yield of CHDA conversion ratio, CHDM selectivity and CHDM.
For convenient for comparing, catalyst composition and synthetic reaction result are listed in table 1.
By embodiment 10 and embodiment 4 and embodiment 6 on year-on-year basis as can be seen that Re and Co is improving Isosorbide-5-Nitrae-hexamethylene diformazan There is synergistic effect in terms of alcohol yield.
[embodiment 11]
The preparation of catalyst
By RuCl3·3H2O、Co(OAc)2·4H2O and ZnCl2It is dissolved in water, obtains the leaching containing 3 grams of Ru, 3 grams of Co and 4 gram of Zn 1200 milliliters of stain liquid, the maceration extract is mixed with 1L active carbon, dipping is for 24 hours, 6 hours dry at 80 DEG C, then in hydrogen 250 DEG C of reduction 3h of nitrogen mixture (hydrogen volume concentration is 3% in gaseous mixture) obtain finished catalyst.
ICP-AES is analyzed, and the Ru content in catalyst is 3g/L, and Co content is 3g/L, and Zn content is 4g/L.
The synthesis of 1,4 cyclohexane dimethanol
Autoclave is added in 150g Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic and 600g water, the above-mentioned resulting catalyst of 50ml is added, opens Stirring is opened, is first passed through nitrogen displacement three times, is being passed through hydrogen displacement three times, then passing to hydrogen makes Hydrogen Vapor Pressure rise to 8.5MPa And keep stable, 230 DEG C of maintaining reaction temperature, and continuously it is passed through hydrogen reaction 3h.After reaction, catalyst is filtered out while hot, Reaction solution is analyzed respectively with liquid chromatogram and gas-chromatography, calculates the yield of CHDA conversion ratio, CHDM selectivity and CHDM.
For convenient for comparing, catalyst composition and synthetic reaction result are listed in table 1.
By embodiment 11 and embodiment 1 and embodiment 5 on year-on-year basis as can be seen that Ru and Co is improving Isosorbide-5-Nitrae-hexamethylene diformazan There is synergistic effect in terms of alcohol yield.
[embodiment 12]
The preparation of catalyst
By RuCl3·3H2O、Co(OAc)2·4H2O and Na2HPO4It is dissolved in water, obtains the leaching containing 3 grams of Ru, 3 grams of Co and 4 gram of P 1200 milliliters of stain liquid, the maceration extract is mixed with 1L active carbon, dipping is for 24 hours, 6 hours dry at 80 DEG C, then in hydrogen 250 DEG C of reduction 3h of nitrogen mixture (hydrogen volume concentration is 3% in gaseous mixture) obtain finished catalyst.
ICP-AES is analyzed, and the Ru content in catalyst is 3g/L, and Co content is 3g/L, P content 4g/L.
The synthesis of 1,4 cyclohexane dimethanol
Autoclave is added in 150g Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic and 600g water, the above-mentioned resulting catalyst of 50ml is added, opens Stirring is opened, is first passed through nitrogen displacement three times, is being passed through hydrogen displacement three times, then passing to hydrogen makes Hydrogen Vapor Pressure rise to 8.5MPa And keep stable, 230 DEG C of maintaining reaction temperature, and continuously it is passed through hydrogen reaction 3h.After reaction, catalyst is filtered out while hot, Reaction solution is analyzed respectively with liquid chromatogram and gas-chromatography, calculates the yield of CHDA conversion ratio, CHDM selectivity and CHDM.
For convenient for comparing, catalyst composition and synthetic reaction result are listed in table 1.
By embodiment 12 and embodiment 2 and embodiment 6 on year-on-year basis as can be seen that Ru and Co is improving Isosorbide-5-Nitrae-hexamethylene diformazan There is synergistic effect in terms of alcohol yield.
[embodiment 13]
The preparation of catalyst
By RuCl3·3H2O、ReCl3·6H2O and ZnCl2、Na2HPO4It is dissolved in water, is obtained containing 3 grams of Ru, 3 grams Re and 3 gram 1200 milliliters of maceration extract of Zn, 1 gram of P, the maceration extract is mixed with 1L active carbon, and dipping is for 24 hours, 6 hours dry at 80 DEG C, Then finished catalyst is obtained in 250 DEG C of reduction 3h of hydrogen nitrogen mixture (hydrogen volume concentration is 3% in gaseous mixture).
ICP-AES is analyzed, and the Ru content in catalyst is 3g/L, and Re content is 3g/L, and Zn content is 3g/L, and P content is 1g/L。
The synthesis of 1,4 cyclohexane dimethanol
Autoclave is added in 150g Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic and 600g water, the above-mentioned resulting catalyst of 50ml is added, opens Stirring is opened, is first passed through nitrogen displacement three times, is being passed through hydrogen displacement three times, then passing to hydrogen makes Hydrogen Vapor Pressure rise to 8.5MPa And keep stable, 230 DEG C of maintaining reaction temperature, and continuously it is passed through hydrogen reaction 3h.After reaction, catalyst is filtered out while hot, Reaction solution is analyzed respectively with liquid chromatogram and gas-chromatography, calculates the yield of CHDA conversion ratio, CHDM selectivity and CHDM.
For convenient for comparing, catalyst composition and synthetic reaction result are listed in table 1.
By embodiment 13 and embodiment 7 and embodiment 8 on year-on-year basis as can be seen that Zn and P is improving Isosorbide-5-Nitrae-hexamethylene diformazan Alcohol yield and raising 1,4 cyclohexane dimethanol selectivity aspect have synergistic effect.
[embodiment 14]
The preparation of catalyst
By ReCl3·6H2O、Co(OAc)2·4H2O and ZnCl2、Na2HPO4It is dissolved in water, is obtained containing 3 grams of Re, 3 grams of Co and 3 1200 milliliters of maceration extract of gram Zn, 1 gram of P, the maceration extract are mixed with 1L active carbon, for 24 hours, dry 6 is small at 80 DEG C for dipping When, then finished catalyst is obtained in 250 DEG C of reduction 3h of hydrogen nitrogen mixture (hydrogen volume concentration is 3% in gaseous mixture).
ICP-AES is analyzed, and the Re content in catalyst is 3g/L, and Co content is 3g/L, and Zn content is 3g/L, and P content is 1g/L。
The synthesis of 1,4 cyclohexane dimethanol
Autoclave is added in 150g Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic and 600g water, the above-mentioned resulting catalyst of 50ml is added, opens Stirring is opened, is first passed through nitrogen displacement three times, is being passed through hydrogen displacement three times, then passing to hydrogen makes Hydrogen Vapor Pressure rise to 8.5MPa And keep stable, 230 DEG C of maintaining reaction temperature, and continuously it is passed through hydrogen reaction 3h.After reaction, catalyst is filtered out while hot, Reaction solution is analyzed respectively with liquid chromatogram and gas-chromatography, calculates the yield of CHDA conversion ratio, CHDM selectivity and CHDM.
For convenient for comparing, catalyst composition and synthetic reaction result are listed in table 1.
By embodiment 14 and embodiment 9 and embodiment 10 on year-on-year basis as can be seen that Zn and P is improving Isosorbide-5-Nitrae-hexamethylene diformazan Alcohol yield and raising 1,4 cyclohexane dimethanol selectivity aspect have synergistic effect.
[embodiment 15]
The preparation of catalyst
By RuCl3·3H2O、Co(OAc)2·4H2O and ZnCl2、Na2HPO4It is dissolved in water, is obtained containing 3 grams of Ru, 3 grams of Co and 3 1200 milliliters of maceration extract of gram Zn, 1 gram of P, the maceration extract are mixed with 1L active carbon, for 24 hours, dry 6 is small at 80 DEG C for dipping When, then finished catalyst is obtained in 250 DEG C of reduction 3h of hydrogen nitrogen mixture (hydrogen volume concentration is 3% in gaseous mixture).
ICP-AES is analyzed, and the Ru content in catalyst is 3g/L, and Co content is 3g/L, and Zn content is 3g/L, and P content is 1g/L。
The synthesis of 1,4 cyclohexane dimethanol
Autoclave is added in 150g Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic and 600g water, the above-mentioned resulting catalyst of 50ml is added, opens Stirring is opened, is first passed through nitrogen displacement three times, is being passed through hydrogen displacement three times, then passing to hydrogen makes Hydrogen Vapor Pressure rise to 8.5MPa And keep stable, 230 DEG C of maintaining reaction temperature, and continuously it is passed through hydrogen reaction 3h.After reaction, catalyst is filtered out while hot, Reaction solution is analyzed respectively with liquid chromatogram and gas-chromatography, calculates the yield of CHDA conversion ratio, CHDM selectivity and CHDM.
For convenient for comparing, catalyst composition and synthetic reaction result are listed in table 1.
By embodiment 15 and embodiment 11 and embodiment 12 on year-on-year basis as can be seen that Zn and P is improving Isosorbide-5-Nitrae-hexamethylene two Methanol yield and raising 1,4 cyclohexane dimethanol selectivity aspect have synergistic effect.
[embodiment 16]
The preparation of catalyst
By RuCl3·3H2O、ReCl3·6H2O、Co(OAc)2·4H2O and ZnCl2、Na2HPO4It is dissolved in water, is obtained containing 2.5 Gram Re, 2.5 grams of Re, 1 gram of Co and 3 gram of Zn, 1200 milliliters of maceration extract of 1 gram of P, the maceration extract is mixed with 1L active carbon, is soaked Stain is for 24 hours, 6 hours dry at 80 DEG C, then at 250 DEG C of hydrogen nitrogen mixture (hydrogen volume concentration is 3% in gaseous mixture) Reduction 3h obtains finished catalyst.
ICP-AES is analyzed, and the Ru content in catalyst is 2.5g/L, and Re content is 2.5g/L, and Co content is 1g/L, and Zn contains Amount is 3g/L, P content 1g/L.
The synthesis of 1,4 cyclohexane dimethanol
Autoclave is added in 150g Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic and 600g water, the above-mentioned resulting catalyst of 50ml is added, opens Stirring is opened, is first passed through nitrogen displacement three times, is being passed through hydrogen displacement three times, then passing to hydrogen makes Hydrogen Vapor Pressure rise to 8.5MPa And keep stable, 230 DEG C of maintaining reaction temperature, and continuously it is passed through hydrogen reaction 3h.After reaction, catalyst is filtered out while hot, Reaction solution is analyzed respectively with liquid chromatogram and gas-chromatography, calculates the yield of CHDA conversion ratio, CHDM selectivity and CHDM.
For convenient for comparing, catalyst composition and synthetic reaction result are listed in table 1.
By embodiment 16 and embodiment 1~15 on year-on-year basis as can be seen that Ru, Re, Co, Zn and P are improving Isosorbide-5-Nitrae-hexamethylene Dimethanol yield and raising 1,4 cyclohexane dimethanol selectivity aspect have the facilitation effect being combined with each other.
Table 1

Claims (8)

1.1,4- cyclohexane cyclohexanedimethanodibasic hydrogenation catalysts, including carrier, active component and co-catalyst, the carrier are activity Charcoal, active component include Ru, and the co-catalyst includes Zn.
2. hydrogenation catalyst according to claim 1, it is characterized in that in catalyst Ru content be greater than 0g/L and 10g/L with Under.
3. hydrogenation catalyst according to claim 3, it is characterized in that Ru content is 0.5~6g/L in catalyst.
4. hydrogenation catalyst according to claim 1, it is characterized in that Zn content is greater than 0 and 10g/L or less in catalyst.
5. hydrogenation catalyst according to claim 1, it is characterized in that Zn content is 0.5~5g/L in catalyst.
6. the preparation method of hydrogenation catalyst according to any one of claims 1 to 5, includes the following steps:
A) solution of the compound of active constituent and the compound of promoter elements is mixed with active carbon；
It b) is simple substance by the active constituent element reduction in the compound of active constituent with reducing agent.
7. preparation method according to claim 6, it is characterized in that reducing agent described in step b is selected from hydrogen, formaldehyde, hydration At least one of hydrazine, sodium borohydride, formic acid or sodium formate.
8. catalyst described in any one of right 1~4 is in 1,4 cyclohexanedicarboxylic acid hydrogenation synthesis 1,4 cyclohexane dimethanol Application in reaction.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN105498763A (en) * 2014-09-25 2016-04-20 中国石油化工股份有限公司 1, 4-cyclohexanedimethanol catalyst

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN105498763A (en) * 2014-09-25 2016-04-20 中国石油化工股份有限公司 1, 4-cyclohexanedimethanol catalyst

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