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 catalyst for adding hydrogen for Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic.The catalystHave the characteristics that 1,4 cyclohexanedicarboxylic acid is hydrogenated to 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: being used for Isosorbide-5-Nitrae-hexamethylene diformazanThe catalyst of acid plus hydrogen, including carrier, active component and co-catalyst, the carrier are active carbon, and active component includes Re, instituteStating co-catalyst includes P.
In above-mentioned technical proposal, the active component preferably includes Ru, Ru and Re and is improving 1,4-CHDM receiptsThere is synergistic effect in terms of rate.
In above-mentioned technical proposal, the active component preferably includes Co, Re and Co and is improving 1,4-CHDM receiptsThere is synergistic effect in terms of rate.
In above-mentioned technical proposal, the active constituent preferably includes that Ru and Co, Ru and Co are improving Isosorbide-5-Nitrae-hexamethylene simultaneouslyThere is synergistic effect in terms of dimethanol yield.
In above-mentioned technical proposal, the co-catalyst preferably includes Zn, Zn and P and is improving 1,4-CHDM yieldThere 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 simultaneouslyIt simultaneously include Zn and P, Ru, Re, Co, Zn and P are improving 1,4-CHDM yield and improving 1,4-CHDMSelectivity 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 catalyst0.014g/L、0.14g/L、0.54g/L、1.04g/L、1.54g/L、2.04g/L、2.54g/L、3.04g/L、3.54g/L、4.04g/L,5.04g/L,6.04g/L,7.04g/L,8.04g/L,9.04g/L.In catalyst Ru content be more preferably 0.5~6g/L。
In above-mentioned technical proposal, Re content is preferably greater than 0g/L and 10g/L hereinafter, for example but unlimited in catalyst0.014g/L、0.14g/L、0.54g/L、1.04g/L、1.54g/L、2.04g/L、2.54g/L、3.04g/L、3.54g/L、4.04g/L,5.04g/L,6.04g/L,7.04g/L,8.04g/L,9.04g/L.In catalyst Re content be more preferably 0.5~6g/L。
In above-mentioned technical proposal, Co content is preferably greater than 0g/L and 10g/L hereinafter, such as, but not limited in catalyst0.014g/L、0.14g/L、0.54g/L、1.04g/L、1.54g/L、2.04g/L、2.54g/L、3.04g/L、3.54g/L、4.04g/L,5.04g/L,6.04g/L,7.04g/L,8.04g/L,9.04g/L.In catalyst Co content be more preferably 0.5~6g/L。
In above-mentioned technical proposal, Zn content is preferably greater than 0 and 10g/L hereinafter, such as, but not limited in catalyst0.01g/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 in catalyst0.014g/L、0.14g/L、0.54g/L、1.04g/L、1.54g/L、2.04g/L、2.54g/L、3.04g/L、3.54g/L、4.04g/L,5.04g/L,6.04g/L,7.04g/L,8.04g/L,9.04g/L.P content is more preferably 0.5~5g/ in catalystL。
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 itselfEspecially limitation, those skilled in the art can reasonably select.About active carbon type, such as, but not limited to active carbon can be coalMatter, 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 to10~200 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, 150Mesh, 180 mesh etc.)；About the specific surface of active carbon, such as, but not limited to 0.01~1500m2/ g, within this range non-limitProperty processed is exemplified as 900m2/g、1000m2/g、1100m2/g、1200m2/g、1300m2/g、1400m2/ g etc.；About active carbonAverage 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 inventionProperty 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 problemThe 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 acidOr at least one of sodium formate.Specific reducing process condition can according to step b) target those skilled in the art achievedIt 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,.It is small that the time of reduction for example can be 1~5When.
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 acidSynthesize 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 fieldPersonnel 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 solutionsIn the presence of described in any item catalyst, 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 CHDMYield 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 leachingStain 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 mixtureAir 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, opensStirring 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 8.5MPaAnd 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 describedMaceration 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 mixtureHydrogen 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, opensStirring 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 8.5MPaAnd 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 leachingStain 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 mixtureAir 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, opensStirring 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 8.5MPaAnd 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 describedMaceration 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 mixtureHydrogen 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, opensStirring 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 8.5MPaAnd 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 instituteIt 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 mixtureMiddle 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, opensStirring 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 8.5MPaAnd 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 instituteIt 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 mixtureMiddle 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, opensStirring 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 8.5MPaAnd 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 Zn1200 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 nitrogen250 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.
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, opensStirring 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 8.5MPaAnd 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 diformazanThere 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 P1200 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 nitrogen250 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.
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, opensStirring 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 8.5MPaAnd 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 diformazanThere 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 Zn1200 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 hydrogen250 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.
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, opensStirring 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 8.5MPaAnd 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 diformazanThere 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 P1200 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 hydrogen250 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.
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, opensStirring 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 8.5MPaAnd 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 diformazanThere 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 Zn1200 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 hydrogen250 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, opensStirring 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 8.5MPaAnd 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 diformazanThere 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 P1200 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 hydrogen250 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, opensStirring 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 8.5MPaAnd 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 diformazanThere 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 gram1200 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 is1g/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, opensStirring 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 8.5MPaAnd 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 diformazanAlcohol 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 31200 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 dippingWhen, 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 is1g/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, opensStirring 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 8.5MPaAnd 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 diformazanAlcohol 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 31200 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 dippingWhen, 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 is1g/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, opensStirring 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 8.5MPaAnd 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 twoMethanol 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, Na2HPO4 be dissolved in water, obtain containing 2.5Gram 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 soakedStain 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 containsAmount 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, opensStirring 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 8.5MPaAnd 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-hexamethyleneDimethanol yield and raising 1,4 cyclohexane dimethanol selectivity aspect have the facilitation effect being combined with each other.
Table 1