CN1291783C - Catalyst for producing dimethyl 1,4-cyclohexanedicarboxylate - Google Patents
Catalyst for producing dimethyl 1,4-cyclohexanedicarboxylate Download PDFInfo
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- CN1291783C CN1291783C CN 200410037338 CN200410037338A CN1291783C CN 1291783 C CN1291783 C CN 1291783C CN 200410037338 CN200410037338 CN 200410037338 CN 200410037338 A CN200410037338 A CN 200410037338A CN 1291783 C CN1291783 C CN 1291783C
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Abstract
The present invention relates to a catalyst for producing dimethyl 1, 4-cyclohexanedicarboxylate by hydrogenation of dimethyl terephthalate. A main active constituent is metal palladium, and a supporter adopts aluminium oxide; an auxiliary agent is combined by two kinds of auxiliary agents, wherein the first auxiliary agent is silicon oxide and the second auxiliary agent element is an element Ru of the VIII subgroup; the metal palladium accounts for 0.5 to 2% of the total weight of the catalyst, the silicon oxide as the first auxiliary agent accounts for 0.01 to 0.5% of the total weight of the catalyst, and the element Ru as the second auxiliary agent accounts for 0.01 to 0.5% of the total weight of the catalyst. The present invention has the characteristics of simple composition, easy preparation, low hydrogenation reaction pressure and high catalytic activity in the hydrogenation reaction, etc.; the conversion rate of the dimethyl phthalate is from 95 to 99%, and the selectivity of the dimethyl 1, 4-cyclohexanedicarboxylate is from 94 to 98%.
Description
Technical field
The present invention relates to a kind of dimethyl terephthalate (DMT) hydrogenation that is used for, produce 1, the catalyst of 4-dimethyl hexahydrophthalate.
Background technology
1, the 4-dimethyl hexahydrophthalate is preparation 1, the intermediate of 4-cyclohexanedimethanol, and with 1, the 4-cyclohexanedimethanol is the saturation type mylar that raw material is produced, and is used in to have many excellent characteristic on coating and the coating.At first, because 1, the 4-cyclohexanedimethanol has symmetrical structure, make polymer chain arrange closely, this symmetry and be arranged with closely to be beneficial to and form hydrogen bond between polymer chain, and then limited the motion of polymer, improved the hardness of polymer, simultaneously, " chair form, cage modle " motion of the cyclohexane ring that contraposition replaces can provide disturbing property to coating, 1, the high symmetry of 4-cyclohexanedimethanol also can make the crystallinity of mylar improve, and the stability of powdery paints, sintering resistance are improved.
1, the 4-cyclohexanedimethanol can be used for the production of the unsaturated polyester resin that sheet stock blown film compound uses, and product has good stable, electrical property and corrosion resistance.Be widely used in and produce film, use for electronic products resin and insulated wire etc.
As preparation 1, the intermediate of 4-cyclohexanedimethanol, 1, the 4-dimethyl hexahydrophthalate has been produced more than 30 year.US 3,334, narrated with dimethyl terephthalate (DMT) in 149 and made feedstock production 1,4-dimethyl hexahydrophthalate and 1, the method for 4-cyclohexanedimethanol.This method generates 1 at the dimethyl terephthalate (DMT) hydrogenation, needs to use high pressure for example greater than 346 crust in the process of 4-dimethyl hexahydrophthalate.Chinese invention patent application number: 94106440.9, publication number: CN 1099745A, the application of U.S. Yisiman Chemical Company, denomination of invention: rutgers hydrogenation generates the low pressure method of corresponding dimethyl hexahydrophthalate, wherein done following explanation about catalyst: described catalyst contains the palladium that is deposited on the alumina support and is selected from second kind of group VIII metallic element of nickel, platinum, ruthenium or its mixture, wherein
(1) content of palladium is the 0.1-5.0% of catalyst weight
(2) decentralization of palladium is at least 15%
(3) at least 90% palladium is positioned at catalyst surface, and its degree of depth is in 200 microns
(4) content that is selected from second kind of VIII subgroup metallic element of nickel, platinum, ruthenium or its mixture is the 0.001-1.0% (weight) of catalyst weight
(5) alumina crystal is α, θ, δ, γ, η or their mixture
The main technique condition of this method comprises the pressure of 140-250 ℃ of temperature and 5-17Mpa, and among the 18 routine embodiment in this patent specification, its operating pressure all is 12.5Mpa, and none routine operating pressure is less than 12.5Mpa.
Summary of the invention
The object of the invention is to provide a kind of dimethyl terephthalate (DMT) hydrogenation that is used for to produce 1, the catalyst of 4-dimethyl hexahydrophthalate, make it produce 1 at the dimethyl terephthalate (DMT) hydrogenation, in the process of 4-dimethyl hexahydrophthalate, operating conditions such as reaction pressure and reaction temperature be can reduce, investment and operating cost reduced.
This catalyst is made up of main active component, auxiliary agent and carrier three parts, and main active component is a Metal Palladium, and carrier is selected aluminium oxide for use, and the specific area of aluminium oxide is at 50m
2/ g-200m
2/ g, auxiliary agent are combined by two types of auxiliary agents, and first auxiliary agent is a silica, and second auxiliary element is from VIII subgroup element ruthenium (Ru).Metal Palladium accounts for 0.5-2% (weight) in total catalyst weight, the first auxiliary agent silica accounts for 0.01-0.5% (weight) in total catalyst weight, the second auxiliary element VIII subgroup metallic element ruthenium (Ru) accounts for 0.01-0.5% (weight) in total catalyst weight.The Preparation of catalysts method is that drying is with using behind the hydrogen reducing with the muriatic aqueous solution of Metal Palladium, second auxiliary element and an amount of Ludox dipping carrier.
Use catalyst of the present invention to carry out the dimethyl terephthalate (DMT) hydrogenation, produce 1, during the 4-dimethyl hexahydrophthalate, the temperature of blender generally maintains 100-200 ℃, the dimethyl terephthalate (DMT) solution that comes out from blender and the mixture of hydrogen enter in the reactor, contact with catalyst and hydrogenation reaction takes place, temperature of reactor generally maintains 150-350 ℃, reaction pressure: 4.0-6.0mPa, rutgers conversion ratio 95-99%, 1,4-dimethyl hexahydrophthalate selectivity 94-98%.This catalyst have form simple, preparation easily, it is low to have hydrogenation reaction pressure for hydrogenation process, characteristics such as catalytic activity height.
Description of drawings
Fig. 1. use catalyst of the present invention to carry out the dimethyl terephthalate (DMT) hydrogenation, produce 1, process flow diagram during the 4-dimethyl hexahydrophthalate.
Wherein: 1 dimethyl terephthalate (DMT) solution storage tank, 2 blenders, 3 reactors, 4 separators, 5.1,4-dimethyl hexahydrophthalate storage tank, 6 liquid pumps, 7 coolers,
The specific embodiment
Embodiment 1.
Dispose 50 milliliters and contain 1.67 gram PdCl
2, 0.01 gram RuCl
3Aqueous hydrochloric acid solution adds and contains 0.25 gram SiO
210 milliliters of Ludox, flood alundum (Al 48.745 grams of accurate weighing with this aqueous solution, air dry, 120 ℃ of oven dryings, 300 ℃ of roastings one hour.Adopt as Fig. 1. shown in pilot plant unit carry out dimethyl terephthalate (DMT) (DMT) hydrogenation, produce 1, the test of 4-dimethyl hexahydrophthalate (DMCD), capital equipment is as follows: 1 dimethyl terephthalate (DMT) solution storage tank, 2 blenders, 3 reactors, 4 separators, 5.1,4-dimethyl hexahydrophthalate storage tank, 6 liquid pumps, 7 coolers, concrete operations technology is as follows: with liquid pump (6) the dimethyl terephthalate (DMT) solution in the storage tank (1) is squeezed in the blender (2), and mixed with hydrogen, the dimethyl terephthalate (DMT) solution that comes out from blender and the mixture of hydrogen enter in the reactor (3), contact with catalyst and hydrogenation reaction takes place, the mixture that comes out from reactor obtains thick product through 1 through condenser (7) and separator (4), and the 4-dimethyl hexahydrophthalate enters 1,4-dimethyl hexahydrophthalate storage tank (5).Loaded catalyst: 5 milliliters, reaction pressure: 4.0mPa, reaction temperature: 184 ℃, raw material: 18 gram dimethyl terephthalate (DMT)/500 milliliter ethyl acetate, the raw material charging rate: 50 milliliters/hour, H
2/ DMT=100 (mol/mol), result of the test is listed in the table 1..
Embodiment 2.
Dispose 50 milliliters and contain 0.42 gram PdCl
2, 0.51 gram RuCl
3Aqueous hydrochloric acid solution adds and contains 0.005 gram SiO
210 milliliters of Ludox, flood alundum (Al 49.495 grams of accurate weighing with this aqueous solution, air dry, 120 ℃ of oven dryings, 300 ℃ of roastings one hour.
Adopt pilot plant unit to carry out dimethyl terephthalate (DMT) (DMT) hydrogenation as embodiment 1, produce 1, the test of 4-dimethyl hexahydrophthalate (DMCD), catalyst is selected example 2 catalyst for use, loaded catalyst: 5 milliliters, and reaction pressure: 6.0mPa, reaction temperature: 184 ℃, raw material: 18 gram dimethyl terephthalate (DMT)/500 milliliter ethyl acetate, the raw material charging rate: 50 milliliters/hour, H
2/ DMT=100 (mol/mol), result of the test is listed in the table 1..
Embodiment 3.
Dispose 50 milliliters and contain 0.84 gram PdCl
2, 0.1 gram RuCl
3Aqueous hydrochloric acid solution adds and contains 0.05 gram SiO
210 milliliters of Ludox, flood alundum (Al 49.4 grams of accurate weighing with this aqueous solution, air dry, 120 ℃ of oven dryings, 300 ℃ of roastings one hour.
Adopt the pilot plant unit of embodiment 1 to carry out dimethyl terephthalate (DMT) (DMT) hydrogenation, produce 1, the test of 4-dimethyl hexahydrophthalate (DMCD), loaded catalyst: 5 milliliters, reaction pressure: 5.0mPa, reaction temperature: 184 ℃, raw material: 18 gram dimethyl terephthalate (DMT)/500 milliliter ethyl acetate, the raw material charging rate: 50 milliliters/hour, H
2/ DMT=100 (mol/mol), result of the test is listed in the table 1..
Table 1. result of the test
| Catalyst | Form | DMT conversion ratio (%) | DMCD selectivity (%) |
| Example 1. catalyst | 2％Pd，0.01％Ru，0.5％SiO 2/Al 2O 3 | 98.26 | 94.42 |
| Example 2. catalyst | 0.5％Pd，0.5％Ru，0.01％SiO 2/Al 2O 3 | 95.52 | 97.53 |
| Example 3. catalyst | 1％Pd，0.1％Ru，0.1％SiO 2/Al 2O 3 | 96.81 | 95.68 |
Claims (3)
1. produce 1 for one kind, the catalyst of 4-dimethyl hexahydrophthalate, it is characterized in that: this catalyst is made up of main active component, auxiliary agent and carrier three parts, main active component is a Metal Palladium, carrier is selected aluminium oxide for use, auxiliary agent is to be combined by two types of auxiliary agents, first auxiliary agent is a silica, second auxiliary element is VIII subgroup element Ru, Metal Palladium accounts for 0.5-2% in total catalyst weight, the first auxiliary agent silica accounts for 0.01-0.5% in total catalyst weight, the second auxiliary element Ru accounts for 0.01-0.5% in total catalyst weight.
2. a kind of production 1 according to claim 1, the catalyst of 4-dimethyl hexahydrophthalate is characterized in that: the specific area of aluminium oxide is at 50m
2/ g-200m
2/ g.
3. according to claim 1-kind of production 1, the Preparation of catalysts method of 4-dimethyl hexahydrophthalate, it is characterized in that: the Preparation of catalysts method is with the muriatic aqueous solution of Metal Palladium, second auxiliary element and an amount of Ludox dipping carrier, drying is with obtaining behind the hydrogen reducing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410037338 CN1291783C (en) | 2004-04-29 | 2004-04-29 | Catalyst for producing dimethyl 1,4-cyclohexanedicarboxylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410037338 CN1291783C (en) | 2004-04-29 | 2004-04-29 | Catalyst for producing dimethyl 1,4-cyclohexanedicarboxylate |
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| Publication Number | Publication Date |
|---|---|
| CN1689698A CN1689698A (en) | 2005-11-02 |
| CN1291783C true CN1291783C (en) | 2006-12-27 |
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| CN 200410037338 Expired - Fee Related CN1291783C (en) | 2004-04-29 | 2004-04-29 | Catalyst for producing dimethyl 1,4-cyclohexanedicarboxylate |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012117976A1 (en) * | 2011-03-01 | 2012-09-07 | 三菱瓦斯化学株式会社 | Method for producing alicyclic carboxylic acid and catalyst used in same |
| 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 |
| CN104649864A (en) * | 2013-11-19 | 2015-05-27 | 中国石油天然气股份有限公司 | Method for producing 1,4-cyclohexanedimethanol through hydrogenation of dialkyl terephthalate |
| TWI577658B (en) | 2015-05-06 | 2017-04-11 | 中國石油化學工業開發股份有限公司 | Method for preparation of dimethyl 1,4-cyclohexanedicarboxylate and method for preparation of 1,4-cyclohexanedimethanol |
| CN106554281A (en) * | 2015-09-24 | 2017-04-05 | 中国科学院大连化学物理研究所 | A kind of method that methyl benzoate hydrogenation reaction produces cyclohexanecarboxylic acid methyl esters |
| CN111036279B (en) * | 2019-12-12 | 2023-02-10 | 西安近代化学研究所 | Preparation method of catalyst applied to hydrogenation synthesis of cyclohexane-1, 2-diisononyl phthalate by diisononyl phthalate |
| CN113429549B (en) * | 2021-07-29 | 2023-03-21 | 天津斯坦利新型材料有限公司 | Composite catalyst, preparation method and polycyclohexylene dimethylene terephthalate prepared by using composite catalyst |
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