CN1915962A - Method for preparing 1,4 - cyclohexanedicarboxylate - Google Patents
Method for preparing 1,4 - cyclohexanedicarboxylate Download PDFInfo
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- CN1915962A CN1915962A CNA2005100288698A CN200510028869A CN1915962A CN 1915962 A CN1915962 A CN 1915962A CN A2005100288698 A CNA2005100288698 A CN A2005100288698A CN 200510028869 A CN200510028869 A CN 200510028869A CN 1915962 A CN1915962 A CN 1915962A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
This invention discloses a method for preparing dimethyl 1,4-cyclohexane dicarboxylate by hydrogenation of dimethyl terephthalate in solvent in the presence of catalyst. The solvent is water or C1-4 fatty alcohol. The catalyst (80-200 mesh) is composed of Ru (0.5-10 wt. %) as the active component, and Al2O3 as the carrier. The weight ratio of dimethyl terephthalate to the solvent is 1: (0.5-10), while that of the catalyst to dimethyl terephthalate is 1: (5-20). The reaction is performed at 120-180 deg.C under 1.0-5.0 MPa for 0.5-8.0 h. Compared with present techniques, the method has such advantages as mild hydrogenation conditions, short hydrogenation time and long catalyst service time (recycleable for more than 9 times).
Description
Technical field
The present invention relates to a kind of aromatic ester carries out the phenyl ring selective hydrogenation in the presence of catalyzer method.
Background technology
By phenyl ring being carried out selective hydrogenation is the important method that is prepared compounds by aromatics, as making the 1,4 cyclohexanedicarboxylic acid dimethyl ester by rutgers through benzene ring hydrogenation.1, the 4-dimethyl hexahydrophthalate then can produce 1 by the ester group hydrogenation again, the 4-cyclohexanedimethanol, the latter is the important Organic Chemicals of producing vibrin, the vibrin that is substituted ethylene glycol or other polyvalent alcohol production by it has good thermostability and thermoplasticity, can under higher temperature, keep stable physical properties and electrical property, obtain application more and more widely at present.
In the prior art, for the phenyl ring selective hydrogenation of aromatics is that the catalyzer of active constituent is considered to the ideal catalyzer with Pd, introduce employing Pd/C catalyzer as Japanese Patent JP2002145824, with water is that solvent prepares 1,4 cyclohexanedicarboxylic acid by the selective hydrogenation that terephthalic acid carries out phenyl ring.Hydrogenation reaction is 1 hour under the condition of 150 ℃ and hydrogen pressure 3MPa, and the terephthalic acid transformation efficiency is 99.2%, and the 1,4 cyclohexanedicarboxylic acid yield is 95.4%.But Pd is a kind of expensive rare metal, and activity of such catalysts is very unoutstanding yet.It is that active ingredient and gac are that the Ru/C catalyzer of carrier is used for such reaction that some other patent also once propose to adopt the relatively low rare metal Ru of price, and as U.S. Pat 3,027,398 and US4,654,064 are introduced.Yet relatively poor reaction preference and activity that the Ru/C catalyzer has been used for such reaction and display.
Summary of the invention
The invention provides a kind of by dimethyl terephthalate (DMT) through benzene ring hydrogenation system 1, the method of 4-dimethyl hexahydrophthalate, the technical problem that it will solve is that the catalyst activity component that adopts is not used more expensive rare metal Pd, but still require reaction to have higher product selectivity, thereby overcome the existing in prior technology defective.
Below be the technical scheme that the present invention solves the problems of the technologies described above:
A kind of preparation method of 1,4 cyclohexanedicarboxylic acid dimethyl ester, this method are raw material with the dimethyl terephthalate (DMT), comprise dimethyl terephthalate (DMT) is carried out hydrogenation reaction in solvent and in the presence of catalyzer.Solvent is taken from a kind of in water or the C1～C4 Fatty Alcohol(C12-C14 and C12-C18), and catalyzer is a loaded catalyst, and active ingredient is metal Ru, and carrier is Al
2O
3, the content of activity component metal Ru is 0.5～10wt% in the catalyzer, the granularity of catalyzer is 80～200 orders.The weight ratio of dimethyl terephthalate (DMT) and solvent is 1: (0.5～10), the weight ratio of catalyzer and dimethyl terephthalate (DMT) are 1: (5～20).Temperature of reaction is 120～180 ℃, and the reaction hydrogen pressure is 1.0～5.0MPa, and the reaction times is 0.5～8.0 hour.
The content of active ingredient Ru is preferably 2.0～8.0wt% in the catalyzer that uses in the above-mentioned reaction; Solvent is preferably taken from a kind of in water, methyl alcohol or the ethanol; The weight ratio of dimethyl terephthalate (DMT) and solvent is preferably 1: (1～5); The weight ratio of catalyzer and dimethyl terephthalate (DMT) is preferably 1: (10～15).
Above-mentioned temperature of reaction is preferably 130～170 ℃; The reaction hydrogen pressure is preferably 3.0～5.0MPa; Reaction times is preferably 1.0～3.0 hours.
Catalyzer generally adopts immersion process for preparing, and its process comprises that the soluble salt with Ru is dissolved in deionized water and is mixed with steeping fluid, with alkaline solution the steeping fluid pH value is adjusted to 4～10, with carrier A l
2O
3Be placed in one dipping 0.5～5.0 hour adds 5～40% formaldehyde solution then and carried out reduction reaction 0.5～3.0 hour, filter, wash the catalyzer finished product.
Above-mentioned catalyzer is preferably hydrate ruthenium trichloride at the soluble salt of the Ru described in the preparation process, and its general formula is RuCl
3XH
2O; Described alkaline solution preferably is selected from a kind of in sal volatile, ammonium bicarbonate soln, ammoniacal liquor, sodium carbonate solution, sodium hydroxide solution or the potassium hydroxide solution, and the concentration of alkaline solution is 5～40%.
The contriver found through experiments, although catalyzer active ingredient of the present invention is not used more expensive rare metal Pd, but still has shown the ideal target product selectivity, and has demonstrated better reactive behavior.Compared with prior art, hydrogenation conditions of the present invention is gentle more, and the reaction times is shorter.In addition, the work-ing life of catalyzer is longer, generally can be recycled more than 9 times.
Below will the invention will be further described by specific embodiment.
In an embodiment, yield is defined as:
Embodiment
One, Preparation of catalysts:
[embodiment 1]
With 2gRuCl
3XH
2O (about 37%Ru) is dissolved in the 325ml deionized water and is mixed with steeping fluid, is heated with stirring to 60 ℃, and the sodium hydroxide solution of adding 20% is adjusted to 8 with the steeping fluid pH value.Add 14.3g carrier A l
2O
3Powder continues to stir 10 minutes.Be cooled to room temperature and left standstill 0.5 hour, drip 9.2g 36% formaldehyde solution, stirring reaction 1 hour left standstill 0.5 hour, filtered, and with deionized water wash 4 times, promptly obtained finished catalyst, and the granularity of catalyzer is 80～200 orders.
[embodiment 2]
Change RuCl
3XH
2O and carrier A l
2O
3Consumption, add 30% ammonium bicarbonate soln the steeping fluid pH value be adjusted to 5, all the other are with embodiment 1.
[embodiment 3]
Change RuCl
3XH
2O and carrier A l
2O
3Consumption, add 20% sodium carbonate solution the steeping fluid pH value be adjusted to 8, all the other are with embodiment 1.
[embodiment 4]
Change RuCl
3XH
2O and carrier A l
2O
3Consumption, add 25% sal volatile the steeping fluid pH value be adjusted to 8, all the other are with embodiment 1.
[embodiment 5～8]
Change RuCl
3XH
2O and carrier A l
2O
3Consumption, all the other are with embodiment 1.
The Ru content of each embodiment catalyzer sees Table 1.
Two, by the reaction of dimethyl terephthalate (DMT) through benzene ring hydrogenation system 1,4 cyclohexanedicarboxylic acid dimethyl ester:
[embodiment 9～16]
The catalyzer that embodiment 1～8 is obtained is used for embodiment 9～16 successively, by the benzene ring hydrogenation prepared in reaction 1,4 cyclohexanedicarboxylic acid dimethyl ester of dimethyl terephthalate (DMT).Catalyzer, reaction raw materials and aqueous solvent are inserted in the autoclave in proportion, and the airtight back of autoclave is extracted air in the still out, feeds hydrogen exchange, and the control hydrogen pressure is 2MPa, progressively is heated to required temperature of reaction.Feed hydrogen to hydrogen pressure again and arrive required reaction hydrogen pressure, begin to react timing.Keep hydrogen pressure to reaction to finish.System cools, filtration catalizer, reaction solution be through gas chromatographic analysis, the counting yield yield.
The concrete reaction conditions of each embodiment sees Table 2, and reaction times and product yield see Table 3.
Table 1.
| Catalyzer Ru content (wt%) | |
| Embodiment 1 | 5 |
| Embodiment 2 | 2.5 |
| Embodiment 3 | 3.5 |
| Embodiment 4 | 4 |
| Embodiment 5 | 2 |
| Embodiment 6 | 6 |
| Embodiment 7 | 8 |
| Embodiment 8 | 8 |
Table 2.
| Solvent | Raw material/solvent (weight ratio) | Catalyst/feed (weight ratio) | Temperature of reaction (℃) | Reaction hydrogen pressure (MPa) | |
| Embodiment 9 | Methyl alcohol | 1/1 | 1/15 | 140 | 5 |
| Embodiment 10 | Methyl alcohol | 1/1 | 1/15 | 130 | 5 |
| Embodiment 11 | Methyl alcohol | 1/1 | 1/15 | 140 | 5 |
| Embodiment 12 | Ethanol | 1/1.2 | 1/15 | 150 | 5 |
| Embodiment 13 | Methyl alcohol | 1/1.5 | 1/10 | 150 | 4 |
| Embodiment 14 | Water | 1/5 | 1/10 | 170 | 3 |
| Embodiment 15 | Water | 1/4 | 1/12 | 160 | 4 |
| Embodiment 16 | Methyl alcohol | 1/1 | 1/15 | 140 | 5 |
Annotate: raw material=dimethyl terephthalate (DMT)
Table 3.
| Reaction times (hour) | 1,4 cyclohexanedicarboxylic acid dimethyl ester yield (%) | |
| Embodiment 9 | 1 | 99.5 |
| Embodiment 10 | 1.5 | 97.4 |
| Embodiment 11 | 1.2 | 98.2 |
| Embodiment 12 | 2 | 98.5 |
| Embodiment 13 | 2.5 | 95.4 |
| Embodiment 14 | 2.5 | 98.9 |
| Embodiment 15 | 2 | 96.2 |
| Embodiment 16 | 1 | 98.7 |
Claims (8)
1, a kind of 1, the preparation method of 4-dimethyl hexahydrophthalate, this method is raw material with the dimethyl terephthalate (DMT), comprise dimethyl terephthalate (DMT) is carried out hydrogenation reaction in solvent and in the presence of catalyzer, solvent is taken from a kind of in water or the C1～C4 Fatty Alcohol(C12-C14 and C12-C18), catalyzer is a loaded catalyst, and active ingredient is metal Ru, and carrier is Al
2O
3The content of activity component metal Ru is 0.5～10wt% in the catalyzer, the granularity of catalyzer is 80～200 orders, the weight ratio of dimethyl terephthalate (DMT) and solvent is 1: (0.5～10), the weight ratio of catalyzer and dimethyl terephthalate (DMT) is 1: (5～20), temperature of reaction is 120～180 ℃, and the reaction hydrogen pressure is 1.0～5.0MPa, and the reaction times is 0.5～8.0 hour.
2, the preparation method of 1,4 cyclohexanedicarboxylic acid dimethyl ester according to claim 1, the content that it is characterized in that active ingredient Ru in the described catalyzer is 2.0～8.0wt%.
3, the preparation method of 1,4 cyclohexanedicarboxylic acid dimethyl ester according to claim 1 is characterized in that described solvent takes from a kind of in water, methyl alcohol or the ethanol.
4, the preparation method of 1,4 cyclohexanedicarboxylic acid dimethyl ester according to claim 1 and 2, the weight ratio that it is characterized in that described catalyzer and dimethyl terephthalate (DMT) is 1: (10～15).
5, according to the preparation method of claim 1 or 3 described 1,4 cyclohexanedicarboxylic acid dimethyl esters, the weight ratio that it is characterized in that described dimethyl terephthalate (DMT) and solvent is 1: (1～5).
6, the preparation method of 1,4 cyclohexanedicarboxylic acid dimethyl ester according to claim 1 is characterized in that described temperature of reaction is 130～170 ℃.
7, the preparation method of 1,4 cyclohexanedicarboxylic acid dimethyl ester according to claim 1 is characterized in that described reaction hydrogen pressure is 3.0～5.0MPa.
8, the preparation method of 1,4 cyclohexanedicarboxylic acid dimethyl ester according to claim 1 is characterized in that the described reaction times is 1.0～3.0 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2005100288698A CN1915962A (en) | 2005-08-17 | 2005-08-17 | Method for preparing 1,4 - cyclohexanedicarboxylate |
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|---|---|---|---|
| CNA2005100288698A CN1915962A (en) | 2005-08-17 | 2005-08-17 | Method for preparing 1,4 - cyclohexanedicarboxylate |
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Cited By (4)
| 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 |
| CN105056996A (en) * | 2015-08-20 | 2015-11-18 | 郑州大学 | Catalyst for selectively hydrogenating dimethyl terephthalate to prepare 1,4-cyclohexane dimethyl isophthalate and preparation method and use method of catalyst |
| CN111468112A (en) * | 2020-05-19 | 2020-07-31 | 西南化工研究设计院有限公司 | Catalyst for preparing 1, 4-cyclohexane dimethyl phthalate by selective hydrogenation of dimethyl terephthalate and preparation method thereof |
| CN113332977A (en) * | 2021-05-25 | 2021-09-03 | 哈尔滨工业大学（深圳） | Catalyst for phthalate hydrogenation catalytic reaction and preparation method and application thereof |
-
2005
- 2005-08-17 CN CNA2005100288698A patent/CN1915962A/en active Pending
Cited By (8)
| 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 |
| 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 |
| CN105056996A (en) * | 2015-08-20 | 2015-11-18 | 郑州大学 | Catalyst for selectively hydrogenating dimethyl terephthalate to prepare 1,4-cyclohexane dimethyl isophthalate and preparation method and use method of catalyst |
| CN105056996B (en) * | 2015-08-20 | 2017-05-17 | 郑州大学 | Catalyst for selectively hydrogenating dimethyl terephthalate to prepare 1,4-cyclohexane dimethyl isophthalate and preparation method and use method of catalyst |
| CN111468112A (en) * | 2020-05-19 | 2020-07-31 | 西南化工研究设计院有限公司 | Catalyst for preparing 1, 4-cyclohexane dimethyl phthalate by selective hydrogenation of dimethyl terephthalate and preparation method thereof |
| CN111468112B (en) * | 2020-05-19 | 2021-04-16 | 西南化工研究设计院有限公司 | Catalyst for preparing 1, 4-cyclohexane dimethyl phthalate by selective hydrogenation of dimethyl terephthalate and preparation method thereof |
| CN113332977A (en) * | 2021-05-25 | 2021-09-03 | 哈尔滨工业大学（深圳） | Catalyst for phthalate hydrogenation catalytic reaction and preparation method and application thereof |
| CN113332977B (en) * | 2021-05-25 | 2022-04-01 | 哈尔滨工业大学（深圳） | Catalyst for phthalate hydrogenation catalytic reaction and preparation method and application thereof |
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