CN102580732B - Catalyst for preparing 1, 4-cyclohexanedimethanol by catalyzing dimethyl terephthalate through one-step hydrogenation and preparation method of catalyst - Google Patents
Catalyst for preparing 1, 4-cyclohexanedimethanol by catalyzing dimethyl terephthalate through one-step hydrogenation and preparation method of catalyst Download PDFInfo
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- CN102580732B CN102580732B CN 201210007690 CN201210007690A CN102580732B CN 102580732 B CN102580732 B CN 102580732B CN 201210007690 CN201210007690 CN 201210007690 CN 201210007690 A CN201210007690 A CN 201210007690A CN 102580732 B CN102580732 B CN 102580732B
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Abstract
The invention discloses a catalyst for preparing 1, 4-cyclohexanedimethanol by catalyzing dimethyl terephthalate through one-step hydrogenation and a preparation method of the catalyst, belonging to the technical field of catalyst preparation. The catalyst is a supported catalyst active ingredients of which are loaded on carriers Al2O3, wherein the active ingredients include three metals, namely, ruthenium, platinum and tin. The catalyst is prepared by adopting a co-impregnation method. According to the invention, the 1, 4-cyclohexanedimethanol is prepared by performing one-step hydrogenation on dimethyl terephthalate by only using a hydrogenation catalyst and a singe reaction solvent, and higher product yield is obtained; the separation of an intermediate product and the consumption of the solvent are avoided; and the consumption of energy and resources through the traditional process is reduced.
Description
Technical field
The invention belongs to catalyst preparation technical field, particularly a kind of Catalysts and its preparation method for the standby 1,4-CHDM of catalysis dimethyl terephthalate (DMT) one step Hydrogenation.
Background technology
1,4-CHDM is the starting monomer of manufacturing the polyester material with excellent heat stability and insulating properties, has very high industrial value.The preparation method of the 1,4-CHDM of current industrial take dimethyl terephthalate (DMT) to prepare 1,4-CHDM via benzene ring hydrogenation and ester group hydrogenation as two kinds of catalyst of prepared using.Its shortcoming is the process route complexity, needs multiple reactor and reaction dissolvent, is unfavorable for reducing the consumption of energy resources.
Summary of the invention
The present invention is directed to current 1,4-CHDM two step production technologies (adopting respectively two kinds of hydrogenation catalysts) present situation, a kind of Catalysts and its preparation method for the standby 1,4-CHDM of catalysis dimethyl terephthalate (DMT) one step Hydrogenation is provided.The present invention only adopts a kind of hydrogenation catalyst and single reaction solvent, has realized that dimethyl terephthalate (DMT) prepares 1,4-CHDM through a step hydrogenation, and has obtained higher product yield.
Catalyst for the standby 1,4-CHDM of catalysis dimethyl terephthalate (DMT) one step Hydrogenation of the present invention is loaded catalyst, and active constituent loading is at carrier A l
2o
3on; Active component is comprised of ruthenium, platinum and three kinds of metals of tin; In catalyst, the quality percentage composition of ruthenium is 1-10%, preferred 3-8%, and the quality percentage composition of platinum is 1-10%, preferred 2-8%, the quality percentage composition of tin is 3-15%, preferably 4-12%; Catalyst grain size is 40～80 orders.
The preparation of above-mentioned catalyst adopts co-impregnation, and its specific operation process is: by the RuCl of 0.025-0.20g
33H
2o, the H of 0.020-0.20g
2ptCl
66H
2the SnCl of O and 0.045-0.25g
22H
2o is dissolved in the deionized water of 1-4ml, adds the hydrochloric acid that the 0.1-0.5ml mass concentration is 20-35% to be made into mixed solution, then is 40-80 purpose carrier A l by the 0.2-1.0g granularity
2o
3add in above-mentioned mixed solution and stir, aged at room temperature 10-20h; Then at 50-70 ℃ of lower vacuum drying 8-15h; After drying in air 300-600 ℃ of lower roasting 4-10h, preferably 400-500 ℃; Then add 10-40ml water, and add 0.1-0.5 doubly to be reduced to the sodium borohydride of product of roasting quality, the recovery time is 1-3h; Finally in 40-80 ℃ of nitrogen atmosphere, dry 8-12h is standby.
Above-mentioned catalyst is applied to the standby 1,4-CHDM reaction of dimethyl terephthalate (DMT) one step Hydrogenation, and concrete reaction condition is: reaction dissolvent is oxolane, ethyl acetate or Isosorbide-5-Nitrae-epoxy six rings; The mass ratio of dimethyl terephthalate (DMT) and reaction dissolvent is 1: (15-40), and preferably 1: (20-30); The 0.02-2.0% that above-mentioned catalyst amount is the reaction system gross mass, preferably 0.05-1.0%; Reaction is carried out in hydrogen atmosphere; Course of reaction is divided two-stage process, one section reaction condition: reaction temperature is 120-200 ℃, preferably 140-190 ℃; Reaction pressure 3-7MPa, preferably 4-6.5MPa; Reaction time is 1.0-3.0h, preferably 1.5-3.5h; The second-stage reaction condition: reaction temperature is 230-280 ℃, preferably 240-270 ℃; Reaction pressure 7-9MPa, preferably 7.5-9MPa; Reaction time is 3.0-10.0h, preferably 5.0-9.0h.
PuPtSn/Al prepared by the present invention
2o
3loaded catalyst has realized that by dimethyl terephthalate (DMT) be the standby 1,4-CHDM of raw material one step Hydrogenation.The present invention only adopts a kind of hydrogenation catalyst and single reaction solvent, realized that dimethyl terephthalate (DMT) prepares 1 through a step hydrogenation, the 4-cyclohexanedimethanol, and obtain higher product yield, avoid the separation of intermediate product and the consumption of solvent, reduced the consumption of traditional handicraft to energy resources.
The specific embodiment:
[embodiment 1]
By 0.13g RuCl
33H
2o, 0.22g SnCl
22H
2o and 0.096g H
2ptCl
66H
2o is dissolved in the 2ml deionized water, adds hydrochloric acid that the 0.2ml mass concentration is 35% to dissolving fully, then to add the 1g granularity be 60-80 purpose Al
2o
3, aged at room temperature 20h, at 60 ℃ of dry 12h of vacuum, then in air 450 ℃ of roasting 8h; Then add 20ml water, add the 0.5g sodium borohydride to be reduced, till after 2h, obviously bubble is emitted to nothing; Finally in 70 ℃ of nitrogen atmospheres, dry 10h is standby.
Active component ruthenium, tin and the platinum of the catalyst of preparation load on carrier A l
2o
3upper, wherein the quality percentage composition of ruthenium is 5%, and the quality percentage composition of platinum is 3.2%, and the quality percentage composition of tin is 11.7%; Catalyst grain size is the 60-80 order.
[embodiment 2]
By 0.13g RuCl
33H
2o, 0.22g SnCl
22H
2o and 0.13g H
2ptCl
66H
2o is dissolved in the 2ml deionized water, adds hydrochloric acid that the 0.2ml mass concentration is 35% to dissolving fully, then to add the 1g granularity be 40-60 purpose Al
2o
3, aged at room temperature 20h, at 60 ℃ of dry 12h of vacuum, then in air 450 ℃ of roasting 8h; Then add 20ml water, add the 0.5g sodium borohydride to be reduced, till after 2h, obviously bubble is emitted to nothing; Finally in 70 ℃ of nitrogen atmospheres, dry 10h is standby.
Active component ruthenium, tin and the platinum of the catalyst of preparation load on carrier A l
2o
3upper, wherein the quality percentage composition of ruthenium is 5%, and the quality percentage composition of platinum is 4.8%, and the quality percentage composition of tin is 11.7%; Catalyst grain size is the 40-60 order.
[embodiment 3]
By 0.13g RuCl
33H
2o, 0.22g SnCl
22H
2o and 0.19g H
2ptCl
66H
2o is dissolved in the 2ml deionized water, adds hydrochloric acid that O.2ml mass concentration is 35% to dissolving fully, then to add the 1g granularity be 40-80 purpose Al
2o
3, aged at room temperature 20h, at 60 ℃ of dry 12h of vacuum, then in air 450 ℃ of roasting 8h; Then add 20ml water, add the 0.5g sodium borohydride to be reduced, till after 2h, obviously bubble is emitted to nothing; Finally in 70 ℃ of nitrogen atmospheres, dry 10h is standby.
Active component ruthenium, tin and the platinum of the catalyst of preparation load on carrier A l
2o
3upper, wherein the quality percentage composition of ruthenium is 5%, and the quality percentage composition of platinum is 7.2%, and the quality percentage composition of tin is 11.7%; Catalyst grain size is the 40-80 order.
The catalyst of above-described embodiment 1,2,3 preparations is applied to dimethyl terephthalate (DMT) one step Hydrogenation standby 1, the reaction of 4-cyclohexanedimethanol, concrete reaction condition is: using the 45g oxolane as solvent and the 1g dimethyl terephthalate (DMT) be placed in the 250ml autoclave, the catalyst that adds 0.3g embodiment 1,2 or 3 preparations, use the nitrogen replacement tertiary air after the enclosed high pressure still, then use three nitrogen of hydrogen exchange; Start heating and be stirred to 180 ℃ of reaction temperatures under hydrogen pressure 3MPa, adjust subsequently reaction pressure to 6MPa, after two hours, temperature is risen to 260 ℃, pressure is adjusted into 8.5MPa, reacts with this understanding 8 hours, stops reaction.Reaction result is as follows:
The conversion ratio that the catalyst that uses embodiment 1 to prepare carries out hydrogenation reaction is 97.1%, and target product 1,4-CHDM yield is 53.2%;
The conversion ratio that the catalyst that uses embodiment 2 to prepare carries out hydrogenation reaction is 98.2%, and target product 1,4-CHDM yield is 75.1%;
The conversion ratio that the catalyst that uses embodiment 3 to prepare carries out hydrogenation reaction is 98.2%, and target product 1,4-CHDM yield is 64.6%.
Claims (4)
1. the preparation method for the catalyst of the standby 1,4-CHDM of catalysis dimethyl terephthalate (DMT) one step Hydrogenation, is characterized in that, adopts the co-impregnation preparation, and its specific operation process is: by the RuCl of 0.025-0.20g
33H
2o, the H of 0.020-0.20g
2ptCl
66H
2the SnCl of O and 0.045-0.25g
22H
2o is dissolved in the deionized water of 1-4ml, adds the hydrochloric acid that the 0.1-0.5ml mass concentration is 20-35% to be made into mixed solution, then is 40-80 purpose carrier A l by the 0.2-1.0g granularity
2o
3add in above-mentioned mixed solution and stir, aged at room temperature 10-20h; Then at 50-70 ℃ of lower vacuum drying 8-15h; After drying in air 300-600 ℃ of lower roasting 4-10h; Then add 10-40ml water, and add 0.1-0.5 doubly to be reduced to the sodium borohydride of product of roasting quality, the recovery time is 1-3h; Finally in 40-80 ℃ of nitrogen atmosphere, dry 6-12h is standby;
The catalyst for the standby 1,4-CHDM of catalysis dimethyl terephthalate (DMT) one step Hydrogenation prepared is loaded catalyst, and active constituent loading is at carrier A l
2o
3on; Active component is comprised of ruthenium, platinum and three kinds of metals of tin; Catalyst grain size is the 40-80 order; In catalyst, the quality percentage composition of ruthenium is 3-8%, and the quality percentage composition of platinum is 2-8%, and the quality percentage composition of tin is 4-12%.
2. the catalyst dimethyl terephthalate (DMT) one step Hydrogenation that method prepares according to claim 1 standby 1, the application of 4-cyclohexanedimethanol, it is characterized in that, concrete reaction condition is: reaction dissolvent is oxolane, ethyl acetate or Isosorbide-5-Nitrae-epoxy six rings; The mass ratio of dimethyl terephthalate (DMT) and reaction dissolvent is 1:(15-40); The 0.02-2.0% that the consumption of catalyst is the reaction system gross mass; Reaction is carried out in hydrogen atmosphere; Course of reaction is divided two-stage process, one section reaction condition: reaction temperature is 120-200 ℃, reaction pressure 3-7MPa, and the reaction time is 1.0-3.0h, the second-stage reaction condition: reaction temperature is 230-280 ℃, reaction pressure 7-9MPa, the reaction time is 3.0-10.0h.
3. application according to claim 2, is characterized in that, the mass ratio of described dimethyl terephthalate (DMT) and reaction dissolvent is 1:(20-30).
4. application according to claim 2, is characterized in that, the 0.05-1.0% that the consumption of catalyst is the reaction system gross mass.
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|---|---|---|---|
| CN 201210007690 CN102580732B (en) | 2012-01-11 | 2012-01-11 | Catalyst for preparing 1, 4-cyclohexanedimethanol by catalyzing dimethyl terephthalate through one-step hydrogenation and preparation method of catalyst |
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|---|---|---|---|
| CN 201210007690 CN102580732B (en) | 2012-01-11 | 2012-01-11 | Catalyst for preparing 1, 4-cyclohexanedimethanol by catalyzing dimethyl terephthalate through one-step hydrogenation and preparation method of catalyst |
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| CN102580732B true CN102580732B (en) | 2013-12-25 |
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| CN103524304B (en) * | 2013-10-22 | 2015-02-04 | 上虞盛晖化工股份有限公司 | Preparation method of 1,4-cyclohexanedimethanol |
| US9115155B1 (en) * | 2014-03-20 | 2015-08-25 | Eastman Chemical Company | Low-pressure synthesis of cyclohexanedimethanol and derivatives |
| CN105294393A (en) * | 2015-11-05 | 2016-02-03 | 中国科学院过程工程研究所 | Method for preparing 1,4-cyclohexanedimethanol through one-pot hydrogenation |
| KR102287646B1 (en) * | 2018-12-31 | 2021-08-06 | 한화솔루션 주식회사 | Carbon-based noble metal-transition metal complex catalyst and preparation method thereof |
| CN112473663A (en) * | 2019-09-12 | 2021-03-12 | 中国科学院过程工程研究所 | Catalyst for preparing alicyclic amine from aromatic amine and preparation method and application thereof |
| KR20220110945A (en) | 2021-02-01 | 2022-08-09 | 한화솔루션 주식회사 | Preparation method of bimetal hydrogenation catalyst |
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Non-Patent Citations (2)
| Title |
|---|
| Ana B.Hungria et al..Single-Step Conversion of Dimethyl Terephthalate into Cyclohexanedimethanol with Ru5PtSn, a Trimetallic Nanoparticle Catalyst.《Angew.Chem.Int.Ed》.2006,第45卷4782-4785. |
| Single-Step Conversion of Dimethyl Terephthalate into Cyclohexanedimethanol with Ru5PtSn, a Trimetallic Nanoparticle Catalyst;Ana B.Hungria et al.;《Angew.Chem.Int.Ed》;20060623;第45卷;4782-4785 * |
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