CN1398841A - Catalyst for hydrogenating 1,4-dimethyl hexahydroterephthalate to produce 1,4-dimethyl cyclohexanol and its prepn process - Google Patents
Catalyst for hydrogenating 1,4-dimethyl hexahydroterephthalate to produce 1,4-dimethyl cyclohexanol and its prepn process Download PDFInfo
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- CN1398841A CN1398841A CN 01110645 CN01110645A CN1398841A CN 1398841 A CN1398841 A CN 1398841A CN 01110645 CN01110645 CN 01110645 CN 01110645 A CN01110645 A CN 01110645A CN 1398841 A CN1398841 A CN 1398841A
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Abstract
A catalyst consists of copper oxide as main active component and cocatalyst component including zinc oxide as the first cocatalyst component and aluminia as the second cocatalyst component. To the catalyst, some compound of metal Mn and alkali earth metal may be added in addition. The catalyst is used in hydrogenating 1,4-hexahydroterephthalate to produce, 1,4-dimethyl cyclohexanol. The cocatalyst component in the catalyst improves the performance of the catalyst, and the catalyst is prepared with fewer elements in raw material, and results in simple and low cost process.
Description
The invention belongs to catalyzer, particularly a kind of 1,4 cyclohexanedicarboxylic acid dimethyl ester hydrogenation that is used for, the Catalysts and its preparation method of production 1,4 cyclohexane dimethanol.
1,4 cyclohexane dimethanol is a kind of raw material of new polyester resin.With the 1,4 cyclohexane dimethanol is the saturation type vibrin of raw material production, is used in to have many excellent characteristic on coating and the coating.At first,, make polymer chain arrange closely because 1,4 cyclohexane dimethanol has symmetrical structure, this symmetry and be arranged with closely to be beneficial to and form hydrogen bond between polymer chain, and then limited the motion of polymkeric substance, improved the hardness of polymkeric substance.Simultaneously, " chair form, the boat form " of the cyclohexane ring of para-orientation motion can provide disturbing property to coating.The high symmetry of 1,4 cyclohexane dimethanol also can make the crystallinity of vibrin improve, and the stability of powder coating, sintering resistance are improved.
1,4 cyclohexane dimethanol can be used for the production of the unsaturated polyester resin that sheet material and film use with compound.Product has satisfactory stability, electrical property and erosion resistance, is widely used in to produce film, use for electronic products resin and insulated wire etc.
The China national patent of invention, application number: 94112835.0, publication number: CN 1108234A, denomination of invention: the preparation method of cyclohexanedimethanol; The China national patent of invention, application number: 94112836.9, denomination of invention: producing the method for 1,4 cyclohexane dimethanol, all is the patent of invention of U.S. Yi Si Man in China's application, wherein about producing 1, the catalyzer of 4-cyclohexanedimethanol has been enumerated multiple ester through hydrogenation catalyzer commonly used, as PG85/1 (Cu-Cr-Mn-Ba), and DRD89/1 (Cu-Cr-Mn), DRD92/89 (Cu-Al-Mn-Cr), DRD92/92 (Cu-Zn-Mn).The listed catalysis principal feature of above-mentioned patent documentation is that copper-chromium catalyst is main, and copper-zinc catalyst is also arranged, and adds manganese, barium auxiliary agent on these catalyzer again.
The China national patent of invention, application number: 98113865.9, denomination of invention: the preparation of ethanol by hydrogenating catalyzer that is used for acetaldehyde, acetate, ethyl acetate or its mixture, be the patent of invention of Dalian Inst of Chemicophysics, Chinese Academy of Sciences in China's application, wherein done following explanation about catalyzer: the main composition of described catalyzer is a cupric oxide, carrier is an aluminum oxide, and auxiliary agent is an alkaline earth metal oxide such as CaO, MgO, BaO or copper transition metal oxide such as FeO, CoO, WO, MoO, ZnO or above-mentioned combination of oxides.
The invention provides a kind of 1,4 cyclohexanedicarboxylic acid dimethyl ester hydrogenation that is used for, produce the catalyzer of 1,4 cyclohexane dimethanol.
The object of the present invention is achieved like this:
A kind ofly be used for 1,4-dimethyl hexahydrophthalate hydrogenation produces 1, the catalyzer of 4-cyclohexanedimethanol, it is characterized in that: this catalyzer is made up of main active ingredient and auxiliary agent, main active ingredient is a cupric oxide, auxiliary agent is to be combined by first adjuvant component and two types of adjuvant components of second adjuvant component, first adjuvant component is a zinc oxide, second adjuvant component is an aluminum oxide, main active ingredient cupric oxide weight accounts for 10-70% in total catalyst weight, the first adjuvant component zinc oxide weight accounts for 5-50% in total catalyst weight, the second adjuvant component alumina weight accounts for 1-40% in total catalyst weight.
Also can add again and contain manganese, alkaline earth metal compound, add the weight contain manganese, alkaline earth metal compound and be 5-30% in total catalyst weight.
The first adjuvant component zinc oxide weight accounts for 15-50% in total catalyst weight.
The second adjuvant component alumina weight accounts for 5-30% in total catalyst weight.
Be used for 1,4-dimethyl hexahydrophthalate hydrogenation produces 1, the method for preparing catalyst of 4-cyclohexanedimethanol is characterized in that: be with salt such as nitrate, muriate and the mixing of aluminium hydroxide water of metallic copper and all auxiliary elements, neutralize about pH=7, generate precipitation, washing, drying is used hydrogen reducing, reduction temperature is 100-500 ℃, and the recovery time is 0.5-14 hour product that obtains.
Novelty of the present invention and inventive features are:
The catalyzer that is 1,4 cyclohexanedicarboxylic acid dimethyl ester hydrogenation system 1,4 cyclohexane dimethanol among the present invention is to be different from the catalyzer described in the above-mentioned pertinent literature fully.Catalyzer of the present invention is novel ternary component catalyzer, and oxidation copper-zine oxide-aluminum oxide also can add again and contain manganese, alkaline earth metal compound.The adding of adjuvant component has improved the performance of catalyzer in the catalyzer, and uses the raw material essence few, and preparation technology is simple, and cost is low.
Fig. 1 is to use catalyzer of the present invention to carry out 1,4 cyclohexanedicarboxylic acid dimethyl ester hydrogenation, when producing 1,4 cyclohexane dimethanol, and process flow diagram.
Major equipment is as follows in the flow process: (1) 1,4 cyclohexanedicarboxylic acid dimethyl ester storage tank, (2) liquid pump, (3) vaporizer, (4) reactor, (5) water cooler, (6) separator.The concrete operations process explanation of hydrogenation is as follows: use liquid pump (2) 1 in the storage tank (1), the 4-dimethyl hexahydrophthalate is squeezed in the vaporizer (3), and mix with hydrogen, the temperature of vaporizer generally maintains 100-300 ℃, from vaporizer, come out 1, the mixed gas of 4-dimethyl hexahydrophthalate and hydrogen enters in the reactor, contact with catalyzer and hydrogenation reaction takes place, temperature of reactor generally maintains 150-350 ℃, the mixture condensation separation of coming out from reactor obtains thick product 1,4 cyclohexane dimethanol.
Further be described by the following examples: example 1.
With 65.5 gram cupric nitrates, 31.3 gram zinc nitrates and 13.1 gram aluminium hydroxides are put into the beaker that fills 500 ml distilled waters, under heated and stirred, the pH=7 that neutralizes makes it generate precipitation, and washing precipitation then was 110 ℃ of dryings 6 hours, the sheet moulding is played catalyzer in 400 ℃ of roastings 4 hours at last.In 300 ℃ of hydrogen streams, reduce before using.Example 2.
With 63.5 gram cupric nitrates, 42.4 gram zinc nitrates and 16.2 gram aluminium hydroxides are put into the beaker that fills 500 ml distilled waters, under heated and stirred, the pH=7 that neutralizes makes it generate precipitation, and washing precipitation then was 110 ℃ of dryings 6 hours, the sheet moulding is played catalyzer in 400 ℃ of roastings 4 hours at last.In 300 ℃ of hydrogen streams, reduce before using.Example 3.
65.5 gram cupric nitrates, 31.3 gram zinc nitrates, 13.1 gram aluminium hydroxides, 5.13 gram manganous nitrates and 4.4 gram nitrate of baryta are put into the beaker that fills 500 ml distilled waters, under heated and stirred, the pH=7 that neutralizes makes it generate precipitation, washing precipitation then, 110 ℃ of dryings 6 hours, the sheet moulding is played catalyzer in 400 ℃ of roastings 4 hours at last.In 300 ℃ of hydrogen streams, reduce before using.Example 4.
Adopt as Fig. 1. shown in pilot plant unit carry out 1,4 cyclohexanedicarboxylic acid dimethyl ester (DMCD) hydrogenation, production 1, the test of 4-cyclohexanedimethanol (CHDM), catalyzer is selected example 1. catalyzer for use, urges than agent loadings: 3 milliliters, and reaction pressure: 6.0MPa, temperature of reaction: 240 ℃, raw material: 8.8 gram 1,4 cyclohexanedicarboxylic acid dimethyl ester/100 ml methanol, raw material input speed: 15 milliliters/hour, the H2:1.4 liter/minute, test-results is listed in example 5. in the table 1.
Adopt as Fig. 1. shown in pilot plant unit carry out 1,4-dimethyl hexahydrophthalate (DMCD) hydrogenation, the test of producing 1,4 cyclohexane dimethanol (CHDM), catalyzer is selected example 2. catalyzer for use, loaded catalyst: 3 milliliters, reaction pressure: 6.0MPa, temperature of reaction: 240 ℃, raw material: 8.8 grams 1,4-dimethyl hexahydrophthalate/100 ml methanol, the raw material input speed: 15 milliliters/hour, H
2: 1.4 liters/minute, test-results is listed in the table 1..Example 6.
Adopt as Fig. 1. shown in pilot plant unit carry out 1,4-dimethyl hexahydrophthalate (DMCD) hydrogenation, the test of producing 1,4 cyclohexane dimethanol (CHDM), catalyzer is selected example 3. catalyzer for use, loaded catalyst: 3 milliliters, reaction pressure: 6.0MPa, temperature of reaction: 240 ℃, raw material: 8.8 grams 1,4-dimethyl hexahydrophthalate/100 ml methanol, the raw material input speed: 15 milliliters/hour, H
2: 1.4 liters/minute, test-results is listed in the table 1..
Table 1. test-results
| Catalyzer | Form | DMCD transformation efficiency (%) | CHDM selectivity (%) |
| Example 1. catalyzer | 56％CuO，22.4％ZnO，2 ????2.1％Al 2O 3 | ????97.2 | ????91.4 |
| Example 2. catalyzer | 49％CuO，27％ZnO，24 ????％Al 2O 3 | ????96.2 | ????92.7 |
| Example 3. catalyzer | 50％CuO，20％ZnO，20 ????％Al 2O 3， 3.4％MnO，0.6％BaO | ????96.5 | ????91.7 |
Claims (5)
1. one kind is used for 1,4-dimethyl hexahydrophthalate hydrogenation produces 1, the catalyzer of 4-cyclohexanedimethanol, it is characterized in that: this catalyzer is made up of main active ingredient and auxiliary agent, main active ingredient is a cupric oxide, auxiliary agent is to be combined by first adjuvant component and two types of adjuvant components of second adjuvant component, first adjuvant component is a zinc oxide, second adjuvant component is an aluminum oxide, main active ingredient cupric oxide weight accounts for 10-70% in total catalyst weight, the first adjuvant component zinc oxide weight accounts for 5-50% in total catalyst weight, the second adjuvant component alumina weight accounts for 1-40% in total catalyst weight.
2. be used for 1 according to claim 1 is described, 4-dimethyl hexahydrophthalate hydrogenation produces 1, the catalyzer of 4-cyclohexanedimethanol, it is characterized in that: also can add again and contain manganese, alkaline earth metal compound, add the weight contain manganese, alkaline earth metal compound and be 5-30% in total catalyst weight.
3. according to the described catalyzer that is used for 1,4 cyclohexanedicarboxylic acid dimethyl ester hydrogenation production 1,4 cyclohexane dimethanol of claim 1, it is characterized in that: the first adjuvant component zinc oxide weight accounts for 15-50% in total catalyst weight.
4. according to the described catalyzer that is used for 1,4 cyclohexanedicarboxylic acid dimethyl ester hydrogenation production 1,4 cyclohexane dimethanol of claim 1, it is characterized in that: the second adjuvant component alumina weight accounts for 5-30% in total catalyst weight.
5. be used for 1 according to claim 1 is described, 4-dimethyl hexahydrophthalate hydrogenation produces 1, the method for preparing catalyst of 4-cyclohexanedimethanol is characterized in that: be with salt such as nitrate, muriate and the mixing of aluminium hydroxide water of metallic copper and all auxiliary elements, neutralize about pH=7, generate precipitation, washing, drying is used hydrogen reducing, reduction temperature is 100-500 ℃, and the recovery time is 0.5-14 hour product that obtains.
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| CNB01110645XA CN1164548C (en) | 2001-04-13 | 2001-04-13 | Catalyst for hydrogenating 1,4-dimethyl hexahydroterephthalate to produce 1,4-dimethyl cyclohexanol and its prepn process |
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| CNB01110645XA CN1164548C (en) | 2001-04-13 | 2001-04-13 | Catalyst for hydrogenating 1,4-dimethyl hexahydroterephthalate to produce 1,4-dimethyl cyclohexanol and its prepn process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102381976A (en) * | 2010-09-01 | 2012-03-21 | 中国石油天然气股份有限公司 | Method for preparing 1, 4-cyclohexane dioctyl phthalate dimethyl |
| CN102381938A (en) * | 2010-09-01 | 2012-03-21 | 中国石油天然气股份有限公司 | Method for preparing 1,4-cyclohexanedimethanol |
| CN102796001A (en) * | 2011-05-25 | 2012-11-28 | 江苏恒祥化工有限责任公司 | Solvent-free preparation method of 1, 4-DMCD |
| CN102795965A (en) * | 2011-05-24 | 2012-11-28 | 江苏恒祥化工有限责任公司 | Method for synthesizing 1,4-cyclohexanedimethanol |
| CN101745396B (en) * | 2008-12-03 | 2013-05-01 | 中国科学院大连化学物理研究所 | Catalyst for preparing succinic acid dialkyl ester and preparation method thereof |
| CN104549322A (en) * | 2013-10-29 | 2015-04-29 | 中国石油天然气股份有限公司 | Catalyst for producing 1,4-cyclohexanedimethanol by hydrogenation and preparation and application thereof |
| CN104829431A (en) * | 2015-05-20 | 2015-08-12 | 南京大学连云港高新技术研究院 | Application of catalyst in improving proportion of trans-1, 4-cyclohexanedimethanol |
| CN104888789A (en) * | 2015-05-20 | 2015-09-09 | 南京大学连云港高新技术研究院 | Catalyst for preparing 1,4-cyclohexanedimethanol |
| CN104907073A (en) * | 2014-03-13 | 2015-09-16 | 中国石油化工股份有限公司 | Ester hydrogenation catalyst, preparation method and ester hydrogenation reaction method |
| CN105237341A (en) * | 2015-09-08 | 2016-01-13 | 江苏恒祥化工有限责任公司 | Preparation method of 1,4-cyclohexanedimethanol |
| CN106748704A (en) * | 2016-11-14 | 2017-05-31 | 中海油天津化工研究设计院有限公司 | A kind of method of the cyclohexanedimethanol of coproduction 1,4 and the dicarbaldehyde of cyclohexyl 1,4 |
| CN107805183A (en) * | 2017-09-30 | 2018-03-16 | 山东玉皇化工有限公司 | The method that one kettle way catalytic hydrogenation prepares 1,4 cyclohexanedimethanols |
| CN109879724A (en) * | 2019-03-26 | 2019-06-14 | 大连理工大学 | A kind of method that high dispersive rhenium-based catalyst prepares 1,4 cyclohexane dimethanol |
| CN110560072A (en) * | 2019-09-19 | 2019-12-13 | 黄河三角洲京博化工研究院有限公司 | Catalyst for producing 1, 6-hexanediol by hydrogenation of adipate and preparation method thereof |
| CN112717941A (en) * | 2019-10-14 | 2021-04-30 | 中国石油化工股份有限公司 | Ester hydrogenation catalyst, and preparation method and application thereof |
| CN114436770A (en) * | 2020-10-20 | 2022-05-06 | 中国石油化工股份有限公司 | Method for preparing cyclohexanedimethanol by hydrogenation of cyclohexanedicarboxylic acid dibasic ester |
| CN114436771A (en) * | 2020-10-20 | 2022-05-06 | 中国石油化工股份有限公司 | Method for preparing cyclohexanedimethanol |
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2001
- 2001-04-13 CN CNB01110645XA patent/CN1164548C/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101745396B (en) * | 2008-12-03 | 2013-05-01 | 中国科学院大连化学物理研究所 | Catalyst for preparing succinic acid dialkyl ester and preparation method thereof |
| CN102381976A (en) * | 2010-09-01 | 2012-03-21 | 中国石油天然气股份有限公司 | Method for preparing 1, 4-cyclohexane dioctyl phthalate dimethyl |
| CN102381938A (en) * | 2010-09-01 | 2012-03-21 | 中国石油天然气股份有限公司 | Method for preparing 1,4-cyclohexanedimethanol |
| CN102381976B (en) * | 2010-09-01 | 2013-09-04 | 中国石油天然气股份有限公司 | Method for preparing 1, 4-cyclohexane dioctyl phthalate dimethyl |
| CN102381938B (en) * | 2010-09-01 | 2014-08-06 | 中国石油天然气股份有限公司 | Method for preparing 1,4-cyclohexanedimethanol |
| CN102795965A (en) * | 2011-05-24 | 2012-11-28 | 江苏恒祥化工有限责任公司 | Method for synthesizing 1,4-cyclohexanedimethanol |
| CN102796001A (en) * | 2011-05-25 | 2012-11-28 | 江苏恒祥化工有限责任公司 | Solvent-free preparation method of 1, 4-DMCD |
| CN104549322A (en) * | 2013-10-29 | 2015-04-29 | 中国石油天然气股份有限公司 | Catalyst for producing 1,4-cyclohexanedimethanol by hydrogenation and preparation and application thereof |
| CN104907073A (en) * | 2014-03-13 | 2015-09-16 | 中国石油化工股份有限公司 | Ester hydrogenation catalyst, preparation method and ester hydrogenation reaction method |
| CN104888789A (en) * | 2015-05-20 | 2015-09-09 | 南京大学连云港高新技术研究院 | Catalyst for preparing 1,4-cyclohexanedimethanol |
| CN104829431A (en) * | 2015-05-20 | 2015-08-12 | 南京大学连云港高新技术研究院 | Application of catalyst in improving proportion of trans-1, 4-cyclohexanedimethanol |
| CN104888789B (en) * | 2015-05-20 | 2017-05-17 | 南京大学连云港高新技术研究院 | Catalyst for preparing 1,4-cyclohexanedimethanol |
| CN105237341A (en) * | 2015-09-08 | 2016-01-13 | 江苏恒祥化工有限责任公司 | Preparation method of 1,4-cyclohexanedimethanol |
| CN106748704A (en) * | 2016-11-14 | 2017-05-31 | 中海油天津化工研究设计院有限公司 | A kind of method of the cyclohexanedimethanol of coproduction 1,4 and the dicarbaldehyde of cyclohexyl 1,4 |
| CN107805183A (en) * | 2017-09-30 | 2018-03-16 | 山东玉皇化工有限公司 | The method that one kettle way catalytic hydrogenation prepares 1,4 cyclohexanedimethanols |
| CN109879724A (en) * | 2019-03-26 | 2019-06-14 | 大连理工大学 | A kind of method that high dispersive rhenium-based catalyst prepares 1,4 cyclohexane dimethanol |
| CN110560072A (en) * | 2019-09-19 | 2019-12-13 | 黄河三角洲京博化工研究院有限公司 | Catalyst for producing 1, 6-hexanediol by hydrogenation of adipate and preparation method thereof |
| CN112717941A (en) * | 2019-10-14 | 2021-04-30 | 中国石油化工股份有限公司 | Ester hydrogenation catalyst, and preparation method and application thereof |
| CN112717941B (en) * | 2019-10-14 | 2023-08-29 | 中国石油化工股份有限公司 | Ester hydrogenation catalyst and preparation method and application thereof |
| CN114436770A (en) * | 2020-10-20 | 2022-05-06 | 中国石油化工股份有限公司 | Method for preparing cyclohexanedimethanol by hydrogenation of cyclohexanedicarboxylic acid dibasic ester |
| CN114436771A (en) * | 2020-10-20 | 2022-05-06 | 中国石油化工股份有限公司 | Method for preparing cyclohexanedimethanol |
| CN114436770B (en) * | 2020-10-20 | 2024-05-03 | 中国石油化工股份有限公司 | Method for preparing cyclohexanedimethanol by hydrogenation of cyclohexanedicarboxylic acid dibasic ester |
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