CN1806913A - Catalyst for preparation of 1,4-cyclohexane dimethanol by hydrogenation of dimethyl terephthalate and preparation method thereof - Google Patents
Catalyst for preparation of 1,4-cyclohexane dimethanol by hydrogenation of dimethyl terephthalate and preparation method thereof Download PDFInfo
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- CN1806913A CN1806913A CN 200510038146 CN200510038146A CN1806913A CN 1806913 A CN1806913 A CN 1806913A CN 200510038146 CN200510038146 CN 200510038146 CN 200510038146 A CN200510038146 A CN 200510038146A CN 1806913 A CN1806913 A CN 1806913A
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Abstract
The invention relates the method for preparation of catalyst used for 1, 4-cyclohexane dimethanol with dimethyl terephthalate. The method comprises main active component, auxiliary agent and support. The method is one-step hydrogenation to produce 1, 4-cyclohexane dimethanol. Main active component is ruthenium, the first catalyst promoter is tin, and the second catalyst promoter is manganese metal.
Description
The present invention relates to a kind of dimethyl terephthalate (DMT) hydrogenation that is used for and produce 1, the catalyst of 4-cyclohexanedimethanol adopts a step hydrogenation method to produce 1, the 4-cyclohexanedimethanol.
1, catalyst characteristics of the present invention is:
This catalyst is made up of main active component, auxiliary agent and carrier three parts.
Main active component is a metal Ru;
First cocatalyst component adopts metallic tin;
Second cocatalyst component adopts manganese metal.
2, preparation method characteristic of the present invention is:
The content of metal Ru is at 0.5-5%,
The first co-catalyst tin accounts for 0.01-0.5% in total catalyst weight,
The second co-catalyst manganese accounts for 0.01-0.05% in total catalyst weight;
Catalyst base is selected aluminium oxide for use, and alumina crystal is a kind of among α, θ, δ, γ, the η or their mixture, and the area of aluminium oxide is 100m
2/ g-200m
2/ g.
With the soluble salts of metal Ru and all auxiliary elements, as nitrate, muriatic aqueous solution dipping carrier, drying, use hydrogen reducing, reduction temperature is 150-600 ℃, the recovery time is 5-15 hour.
Advantage of the present invention is:
Adopt institute of the present invention controlling catalyst, adopt a step segmentation hydrogenation preparing 1, the 4-cyclohexanedimethanol, production technology is simple, and reaction pressure obviously reduces.
Example 1: take by weighing the 12g alundum (Al, take by weighing the 0.6g manganese nitrate, be dissolved in the 15ml water, the 12g alundum (Al that the water solution impregnation weighs up.150 ℃ of oven dry, 500 ℃ of roasts 6 hours.Getting the 1ml stannous chloride aqueous solution (0.1gSn/ml) and 1.5g ruthenic chloride (RuCl3.3H2O) and 100ml water mixes.Use the good catalyst intermediate of the above-mentioned roast of this solution impregnation then, air dry, 100 ℃ of oven dry, drying is two hours in 500 ℃ of hydrogen streams.
Example 2: take by weighing the 12g alundum (Al, take by weighing the 0.6g manganese nitrate, be dissolved in the 15ml water, the 12g alundum (Al that the water solution impregnation weighs up.150 ℃ of oven dry, 500 ℃ of roasts 3 hours.Getting the 1ml stannous chloride aqueous solution (0.1gSn/ml) and 2g ruthenic chloride (RuCl3.3H2O) and 100ml water mixes.Use the good catalyst intermediate of the above-mentioned roast of this solution impregnation then, air dry, 100 ℃ of oven dry, drying is three hours in 500 ℃ of hydrogen streams.
Example 3: take by weighing the 12g alundum (Al.2g ruthenic chloride (RuCl3.3H2O), the 2ml stannous chloride aqueous solution (0.1gSn/ml) 100ml water mix, and flood this solution with the 12g alundum (Al that weighs up, air dry, 300 ℃ of roasts 2 hours.Take by weighing the 0.45g manganese nitrate and be dissolved in the 50ml water, flood this solution with the good catalyst intermediate of above-mentioned roast, 120 ℃ of oven dry, reduction is 3 hours in 400 ℃ of hydrogen streams.
Example 4: adopt the small test device shown in the Figure of description to carry out the dimethyl terephthalate (DMT) hydrogenation and produce 1, the 4-cyclohexanedimethanol.Catalyst filling amount 10ml, reaction pressure 5.5-6.0MPa, reaction temperature: in a hour temperature is risen to 150 ℃, 140-150 ℃ of reaction of control temperature 1 hour, in 1 hour, temperature is risen to 250 ℃ then, 250-260 ℃ of control temperature, 8.0MPa reaction 3 hours.
Result such as following table:
| Sequence number | Catalyst | Form | The DMT conversion ratio | The CHDM selectivity |
| 1 | Example 1 | 3.73% ruthenium; 0.03%; Manganese 0.03% tin | 98.16％ | 93.60％ |
| 2 | Example 2 | 5.0% ruthenium; 0.04%; Manganese 0.03% tin | 98.25％ | 98.05％ |
| 3 | Example 3 | 5.0% ruthenium; 0.03%; Manganese 0.06% tin | 98.50％ | 97.37％ |
Description of drawings:
The Figure of description shown device is that " example 4 " carries out dimethyl terephthalate (DMT) hydrogenation production 1, the small test device of 4-cyclohexanedimethanol.
Claims (2)
1, a kind of dimethyl terephthalate (DMT) hydrogenation that is used for produces 1, and the catalyst of 4-cyclohexanedimethanol adopts a step hydrogenation method to produce 1, the 4-cyclohexanedimethanol.
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 Ru;
First cocatalyst component adopts metallic tin;
Second cocatalyst component adopts manganese metal.
2, a kind of dimethyl terephthalate (DMT) hydrogenation that is used for produces 1, and the Preparation of catalysts method of 4-cyclohexanedimethanol is characterized in that:
The content of metal Ru is at 0.5-5%,
The first co-catalyst tin accounts for 0.01-0.5% in total catalyst weight,
The second co-catalyst manganese accounts for 0.01-0.05% in total catalyst weight;
Catalyst base is selected aluminium oxide for use, and alumina crystal is a kind of among α, θ, δ, γ, the η or their mixture, and the area of aluminium oxide is 100m
2/ g-200m
2/ g.
With the soluble salts of metal Ru and all auxiliary elements, as nitrate, muriatic aqueous solution dipping carrier, drying, use hydrogen reducing, reduction temperature is 150-600 ℃, the recovery time is 5-15 hour.
Advantage of the present invention is:
Adopt institute of the present invention controlling catalyst, adopt a step segmentation hydrogenation preparing 1, the 4-cyclohexanedimethanol, production technology is simple, and reaction pressure obviously reduces.
Example 1:
Take by weighing the 12g alundum (Al, take by weighing the 0.6g manganese nitrate, be dissolved in the 15ml water, the 12g alundum (Al that the water solution impregnation weighs up.150 ℃ of oven dry, 500 ℃ of roasts 6 hours.Getting the 1ml stannous chloride aqueous solution (0.1gSn/ml) and 1.5g ruthenic chloride (RuCl3.3H2O) and 100ml water mixes.Use the good catalyst intermediate of the above-mentioned roast of this solution impregnation then, air dry, 100 ℃ of oven dry, drying is two hours in 500 ℃ of hydrogen streams.
Example 2:
Take by weighing the 12g alundum (Al, take by weighing the 0.6g manganese nitrate, be dissolved in the 15ml water, the 12g alundum (Al that the water solution impregnation weighs up.150 ℃ of oven dry, 500 ℃ of roasts 3 hours.Getting the 1ml stannous chloride aqueous solution (0.1gSn/ml) and 2g ruthenic chloride (RuCl3.3H2O) and 100ml water mixes.Use the good catalyst intermediate of the above-mentioned roast of this solution impregnation then, air dry, 100 ℃ of oven dry, drying is three hours in 500 ℃ of hydrogen streams.
Example 3:
Take by weighing the 12g alundum (Al.2g ruthenic chloride (RuCl3.3H2O), the 2ml stannous chloride aqueous solution (0.1gSn/ml) 100ml water mix, and flood this solution with the 12g alundum (Al that weighs up, air dry, 300 ℃ of roasts 2 hours.Take by weighing the 0.45g manganese nitrate and be dissolved in the 50ml water, flood this solution with the good catalyst intermediate of above-mentioned roast, 120 ℃ of oven dry, reduction is 3 hours in 400 ℃ of hydrogen streams.
Example 4:
Adopt small test device to carry out the dimethyl terephthalate (DMT) hydrogenation and produce 1, the 4-cyclohexanedimethanol.Catalyst filling amount 10ml, reaction pressure 5.5-6.0MPa, reaction temperature: in a hour temperature is risen to 150 ℃, 140-150 ℃ of reaction of control temperature 1 hour, in 1 hour, temperature is risen to 250 ℃ then, 250-260 ℃ of control temperature, 8.0MPa reaction 3 hours.Result such as following table:
Sequence number Catalyst Form The DMT conversion ratio The CHDM selectivity
1 Example 1 3.73% ruthenium; 0.03%; Manganese 0.03% tin 98.16％ 93.60％
2 Example 2 5.0% ruthenium; 0.04%; Manganese 0.03% tin 98.25％ 98.05％
3 Example 3 5.0% ruthenium; 0.03%; Manganese 0.06% tin 98.50％ 97.37％
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200510038146 CN1806913A (en) | 2005-01-18 | 2005-01-18 | Catalyst for preparation of 1,4-cyclohexane dimethanol by hydrogenation of dimethyl terephthalate and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510038146 CN1806913A (en) | 2005-01-18 | 2005-01-18 | Catalyst for preparation of 1,4-cyclohexane dimethanol by hydrogenation of dimethyl terephthalate and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100465145C (en) * | 2007-06-01 | 2009-03-04 | 华东理工大学 | Process of preparing 1,4-cyclohexane dimethand |
| 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 |
| CN101417950B (en) * | 2008-10-27 | 2012-05-23 | 中国科学院大连化学物理研究所 | Method for preparing 1,2-cyclohexane cyclohexanedimethanol dibasic ester |
| 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 |
| CN103691432A (en) * | 2013-12-31 | 2014-04-02 | 江苏金桥盐化集团有限责任公司 | Ruthenium/aluminum oxide catalyst, as well as preparing method and application thereof |
| CN105582961A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | 1,4-cyclohexan dimethyl dicarboxylate hydrogenation catalyst |
-
2005
- 2005-01-18 CN CN 200510038146 patent/CN1806913A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100465145C (en) * | 2007-06-01 | 2009-03-04 | 华东理工大学 | Process of preparing 1,4-cyclohexane dimethand |
| CN101417950B (en) * | 2008-10-27 | 2012-05-23 | 中国科学院大连化学物理研究所 | Method for preparing 1,2-cyclohexane cyclohexanedimethanol dibasic ester |
| 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 |
| 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 |
| CN103691432A (en) * | 2013-12-31 | 2014-04-02 | 江苏金桥盐化集团有限责任公司 | Ruthenium/aluminum oxide catalyst, as well as preparing method and application thereof |
| CN103691432B (en) * | 2013-12-31 | 2016-05-25 | 江苏金桥盐化集团有限责任公司 | A kind of ruthenium/aluminium oxide catalyst, method for making and application thereof |
| CN105582961A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | 1,4-cyclohexan dimethyl dicarboxylate hydrogenation catalyst |
| CN105582961B (en) * | 2014-10-24 | 2018-04-06 | 中国石油化工股份有限公司 | 1,4 dimethyl hexahydrophthalate hydrogenation catalysts |
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