CN111672508B - Preparation and application of catalyst for preparing 1,4-dimethyl cyclohexanedicarboxylate through dimethyl terephthalate hydrogenation - Google Patents
Preparation and application of catalyst for preparing 1,4-dimethyl cyclohexanedicarboxylate through dimethyl terephthalate hydrogenation Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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Abstract
The invention provides a preparation method and application of a catalyst for preparing 1,4-cyclohexane dimethyl phthalate through dimethyl terephthalate hydrogenation, wherein a catalyst carrier is gamma-Al 2 O 3 The main catalyst is ruthenium and tin. The invention has the advantages of simple preparation steps, mild preparation conditions, low cost and easy industrial production, and the catalyst has the characteristics of high catalytic activity and less by-products, the hydrogenation conversion rate of the dimethyl terephthalate reaches 100 percent, and the selectivity is more than 95-99.5 percent.
Description
Technical Field
The invention belongs to the field of catalyst preparation, and particularly relates to preparation and application of a catalyst for preparing 1,4-dimethyl cyclohexanedicarboxylate through dimethyl terephthalate hydrogenation.
Background
1,4-dimethyl cyclohexanedicarboxylate (DMCD) is an important organic chemical intermediate, and has wide application in the fields of polymer synthesis and modification, production of coatings and plasticizers and the like. Meanwhile, DMCD is also an intermediate for synthesizing 1,4-Cyclohexanedimethanol (CHDM). The polymer material synthesized by using CHDM as a monomer has good thermal stability, and can maintain the physical property and the electrical property at high temperature. The current synthetic route to DMCD is primarily through the hydrogenation of dimethyl phthalate (DMT),
the patent with the publication number of CN105056996B discloses a catalyst for preparing DMCD by DMT selective hydrogenation, wherein Ru is used as a main catalyst, the selectivity of DMCD is more than 98%, but the preparation process of the catalyst is complex, high-pressure hydrogen is required for reduction, and simultaneously, methanol is used as a reaction solvent, the subsequent process of separating the solvent and the product is involved, and the complexity of the process is increased. The patent with publication number CN102935365B discloses a catalyst for preparing DMCD, pd is used as a main catalyst, and a fixed bed reaction process is adopted. But the reaction temperature is high. In the process for preparing DMCD disclosed in the patent publication No. US3334149, the reaction pressure is higher, greater than 34MPa.
In summary, the main problems of the existing catalysts are complex preparation process, high reaction temperature and pressure, complex synthesis process, low yield and the like.
Disclosure of Invention
In view of the above, the invention aims to provide a preparation method and an application of a catalyst for preparing 1,4-cyclohexanedicarboxylate by hydrogenating dimethyl terephthalate, so as to solve the problems of complex preparation process, high cost, and low reaction conversion rate and selectivity of the existing catalyst.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a catalyst for preparing 1,4-cyclohexane dimethyl phthalate by hydrogenating dimethyl terephthalate comprises a carrier and a main catalyst, wherein the carrier is gamma-Al 2 O 3 The main catalyst is ruthenium and tin.
Further, ruthenium accounts for 1-5% of the total weight of the catalyst, and tin accounts for 0.1-1% of the total weight, preferably ruthenium accounts for 2.5-4% of the total weight of the catalyst, and tin accounts for 0.1-0.5% of the total weight of the catalyst.
The invention also provides a preparation method of the catalyst for preparing 1,4-dimethyl cyclohexanedicarboxylate by hydrogenating dimethyl terephthalate, which comprises the following steps:
s1, ruthenium salt with certain mass, tin salt with certain mass and gamma-Al with certain mass 2 O 3 Adding into polyol respectively to obtain ruthenium-containing polyolPolyol solution, polyol solution of tin and gamma-Al 2 O 3 The polyol dispersion of (4);
s2, adding the gamma-Al obtained in the step S1 2 O 3 The polyhydric alcohol solution of ruthenium and the polyhydric alcohol solution of tin obtained in the step S1 are slowly added into the polyhydric alcohol dispersion liquid at the same time, and after uniform mixing, the pH of the mixed solution is adjusted to 10-11 by 0.5-2mol/L of the polyhydric alcohol solution of organic base;
s3, heating the mixed solution obtained in the step S2 to 50-100 ℃, and stirring for 1-2 hours;
s4, filtering, washing and centrifuging the product obtained in the step S3, and drying at 120 ℃ for 12 hours;
and S5, crushing the product obtained in the step S4, tabletting and forming to obtain the catalyst.
Further, in the step S1, the mass fraction of the polyol solution of ruthenium is 1-10%, the mass fraction of the polyol solution of tin is 1-10%, and gamma-Al is 2 O 3 The polyol dispersion liquid has a mass fraction of 10 to 50%.
Further, in the step S1, the mass fraction of the polyol solution of ruthenium is 5.4%, the mass fraction of the polyol solution of tin is 1.6%, and γ -Al is added 2 O 3 The polyol dispersion was 33.3% by mass.
Further, in the step S1, the ruthenium salt is ruthenium acetate or ruthenium trichloride, the tin salt is stannous chloride, and the polyol is one or a combination of several of ethylene glycol, glycerol, 1,4-butanediol, 1,6-hexanediol, 1,2-dodecanediol, 1,2-hexadecanediol, D-sorbitol, and ribitol.
Further, in the step S2, the organic base is one or a combination of several of trimethylamine, triethylamine, diethylenetriamine and triethylenetetramine.
Further, in the step S3, the heating temperature is 70 to 90 ℃.
The invention also provides a process for preparing 1,4-cyclohexanedicarboxylate by hydrogenating dimethyl terephthalate, which comprises the following steps of using the catalyst in slurry bed to prepare 1,4-cyclohexanedicarboxylate by hydrogenating dimethyl terephthalate, using 1,4-cyclohexanedicarboxylate as a solvent, wherein the feeding mass ratio of dimethyl terephthalate to 1,4-cyclohexanedicarboxylate is 1 (0.5-2), and the feeding mass ratio of dimethyl terephthalate to the catalyst is 10: (1-5), the reaction pressure is 4-8MPa, the reaction temperature is 100-140 ℃, the reaction time is 30-200min, and the 1,4-cyclohexane dicarboxylic acid dimethyl ester is obtained by separating the catalyst after cooling.
Further, the reaction pressure is 4-6MPa, the reaction temperature is 110-130 ℃, and the reaction time is 60-120min.
Compared with the prior art, the preparation and the application of the catalyst for preparing 1,4-dimethyl cyclohexanedicarboxylate by hydrogenating dimethyl terephthalate have the following advantages:
the catalyst has the advantages of simple preparation steps, mild preparation conditions, low cost and easy industrial production; the catalyst is used for preparing DMCD by DMT hydrogenation, a slurry bed reactor is adopted for reaction, and a solvent and the catalyst do not need to be separated; the whole reaction flow has simple operation, mild reaction conditions and high reaction conversion rate and product selectivity.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail with reference to examples.
In the following examples, the process conditions for the reaction were as follows: adding the prepared catalyst, DMT and DMCD into a slurry bed reactor, wherein the feeding mass ratio of DMT to DMCD is 1, the feeding mass ratio of DMT to catalyst is 10:1, the reaction pressure is 4-8MPa; the reaction temperature is 100-140 ℃; the reaction time is 30-200min. After the reaction, the catalyst and the product were separated and sampled, and the composition of the product was analyzed by a gas chromatograph.
In the following examples, the catalyst was prepared as follows:
s1, mixing a certain mass of ruthenium salt, stannous chloride and a certain mass of gamma-Al 2 O 3 Respectively adding the mixture into 1,4-butanediol to obtain 1,4-butanediol solution with 5.4 mass percent of ruthenium, 1,4-butanediol solution with 1.6 mass percent of tin and gamma-Al with 33.3 mass percent 2 O 3 1,4-butanediol dispersion; the metal ruthenium accounts for 1-5% of the total weight of the catalyst, and the metal tin accounts for 0.1-1% of the total weight;
s2, adding the gamma-Al obtained in the step S1 2 O 3 Adding 1,4-butanediol solution of ruthenium and 1,4-butanediol solution of tin slowly into 1,4-butanediol dispersion liquid at the same time, mixing uniformly, and adjusting the pH of the mixed solution to 10 by using 1mol/L of diethylenetriamine/1,4-butanediol solution;
s3, heating the mixed solution obtained in the step S2 to 80 ℃, and stirring for 2 hours;
s4, filtering, washing and centrifuging the product obtained in the step S3, and drying at 120 ℃ for 12 hours;
and S5, crushing the product obtained in the step S4, tabletting and forming to obtain the catalyst.
Example 1
0.27g of ruthenium trichloride, 0.08g of stannous chloride and 10g of gamma-Al are respectively added 2 O 3 5ml, 5ml and 30ml of 1,4-butanediol are added and mixed well. To gamma-Al 2 O 3 While adding 1,4-butanediol solution of ruthenium and 1,4-butanediol solution of tin slowly into 1,4-butanediol dispersion, mixing them uniformly, and then adjusting the pH of the mixed solution to 10 with 1mol/L of diethylenetriamine/1,4-butanediol solution. Heating the mixed solution to 80 ℃, stirring for 2 hours to obtain a product, filtering, washing, centrifuging, drying for 12 hours at 120 ℃, crushing, tabletting and forming to obtain the catalyst. Reaction process conditions are as follows: the temperature is 120 ℃, the reaction pressure is 6MPa, and the reaction time is 80min. The catalyst evaluation results are shown in Table 1.
Example 2
A catalyst was prepared by following the procedure of example 1 while changing the amount of ruthenium trichloride to 0.81 g. The reaction process conditions are the same.
Example 3
A catalyst was prepared by following the procedure of example 1 while changing the amount of ruthenium trichloride to 1.35 g. The reaction process conditions are the same.
Example 4
The catalyst was prepared according to the procedure in example 1, changing the amount of ruthenium trichloride to 0.81g and the amount of stannous chloride to 0.016 g. The reaction process conditions are the same.
Example 5
The catalyst was prepared according to the procedure in example 1, changing the amount of ruthenium trichloride to 0.81g and the amount of stannous chloride to 0.032 g. The reaction process conditions are the same.
Example 6
A catalyst was prepared by following the procedure of example 1 while changing the amount of ruthenium trichloride to 0.81g and the amount of stannous chloride to 0.13 g. The reaction process conditions are the same.
Example 7
The catalyst was prepared according to the procedure of example 1, changing the amount of ruthenium trichloride to 0.81g and the amount of stannous chloride to 0.16 g. The reaction process conditions are the same.
Example 8
A catalyst was prepared by following the procedure of example 1 while changing the amount of ruthenium trichloride to 0.81 g. The reaction process conditions are as follows: the reaction temperature was changed to 100 ℃ and the rest of the process conditions were the same.
Example 9
A catalyst was prepared by following the procedure of example 1 while changing the amount of ruthenium trichloride to 0.81 g. Reaction process conditions are as follows: the reaction temperature was changed to 140 ℃ and the rest of the process conditions were the same.
Example 10
A catalyst was prepared by following the procedure of example 1 while changing the amount of ruthenium trichloride to 0.81 g. Reaction process conditions are as follows: the reaction pressure is changed to 4MPa, and the rest process conditions are the same.
Example 11
A catalyst was prepared by following the procedure of example 1 while changing the amount of ruthenium trichloride to 0.81 g. Reaction process conditions are as follows: the reaction pressure is changed to 8MPa, and the other process conditions are the same.
Example 12
A catalyst was prepared by following the procedure of example 1 while changing the amount of ruthenium trichloride to 0.81 g. The reaction process conditions are as follows: the reaction time was changed to 30min, and the rest of the process conditions were the same.
Example 13
A catalyst was prepared by following the procedure of example 1 while changing the amount of ruthenium trichloride to 0.81 g. Reaction process conditions are as follows: the reaction time was changed to 200min, and the rest of the process conditions were the same.
Example 14
A catalyst was prepared by following the procedure of example 1 while changing the ruthenium salt to ruthenium acetate in an amount of 0.83 g. The reaction process conditions are the same.
Comparative example 1
A catalyst was prepared by following the procedure in example 1 while changing the amount of ruthenium trichloride to 0.135 g. The reaction process conditions are the same.
Comparative example 2
A catalyst was prepared by following the procedure of example 1 while changing the amount of ruthenium trichloride to 1.62 g. The reaction process conditions are the same.
Comparative example 3
The catalyst was prepared according to the procedure in example 1, varying the amount of stannous chloride used to 0.008 g. The reaction process conditions are the same.
Comparative example 4
The catalyst was prepared according to the procedure in example 1, varying the amount of stannous chloride used to 0.32 g. The reaction process conditions are the same.
Comparative example 5
The catalyst is prepared by a traditional impregnation method. 0.81g of ruthenium trichloride, 0.08g of stannous chloride and 10g of gamma-Al are respectively added 2 O 3 Adding into 40ml water, mixing well, standing for 12h, and drying at 120 deg.C for 12h. The dried solid was calcined at 500 ℃ for 4h. Cooling, grinding into powder, putting into a tube furnace, and reducing for 4h at 180 ℃ in the atmosphere of hydrogen to obtain the catalyst. The reaction process conditions are the same.
Table 1 evaluation results of catalysts in examples
As can be seen from Table 1, when the mass fraction of Ru was 3% and the mass fraction of Sn was 0.5%, the highest conversion and selectivity of the obtained product were obtained. A decrease in the mass fraction of Ru and a decrease in the mass fraction of Sn leads to a decrease in selectivity, and a decrease in the mass fraction of Ru or an increase in the mass fraction of Sn leads to a decrease in conversion. Meanwhile, the optimal evaluation conditions of the catalyst are that the reaction temperature is 120 ℃, the reaction time is 80min, and the reaction pressure is 6MPa, under the reaction conditions, the conversion rate of DMT is 100%, and the selectivity of DMCD is 99.5%. It was found by comparative examples 1 to 4 that the selectivity of DMCD significantly decreases in the case where the mass fractions of Ru and Sn are not within the range of the claims. It was found by comparative example 5 that the performance of the catalyst of the present invention was significantly improved compared to the conventional impregnation method.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the scope of the present invention, which is intended to cover any modifications, equivalents, improvements, etc. within the spirit and scope of the present invention.
Claims (8)
1. A catalyst for preparing 1,4-cyclohexane dimethyl phthalate by hydrogenating dimethyl terephthalate is characterized in that: comprises a carrier and a main catalyst, wherein the carrier is gamma-Al 2 O 3 The main catalyst is ruthenium and tin, the ruthenium accounts for 1-5% of the total weight of the catalyst, the tin accounts for 0.1-1% of the total weight of the catalyst, and the preparation method of the catalyst for preparing 1,4-dimethyl cyclohexanedicarboxylate through dimethyl terephthalate hydrogenation specifically comprises the following steps:
s1, ruthenium salt with certain mass, tin salt with certain mass and gamma-Al with certain mass 2 O 3 Respectively adding into polyol to obtain ruthenium polyol solution, tin polyol solution and gamma-Al 2 O 3 The polyol dispersion of (1);
s2. Go to stepGamma-Al obtained in step S1 2 O 3 The polyhydric alcohol solution of ruthenium and the polyhydric alcohol solution of tin obtained in the step S1 are slowly added into the polyhydric alcohol dispersion liquid at the same time, and after uniform mixing, the pH of the mixed solution is adjusted to 10-11 by 0.5-2mol/L of the polyhydric alcohol solution of organic base;
s3, heating the mixed solution obtained in the step S2 to 50-100 ℃, and stirring for 1-2 hours;
s4, filtering, washing and centrifuging the product obtained in the step S3, and drying at 120 ℃ for 12 hours;
and S5, crushing the product obtained in the step S4, tabletting and forming to obtain the catalyst.
2. The catalyst for preparing 1,4-cyclohexanedicarboxylate by hydrogenating dimethyl terephthalate as claimed in claim 1, wherein: in the step S1, the mass fraction of the polyol solution of ruthenium is 1-10%, the mass fraction of the polyol solution of tin is 1-10%, and gamma-Al is 2 O 3 The polyol dispersion liquid has a mass fraction of 10 to 50%.
3. The catalyst for preparing 1,4-cyclohexanedicarboxylate by hydrogenating dimethyl terephthalate as claimed in claim 1, wherein: in the step S1, the mass fraction of the polyol solution of ruthenium is 5.4%, the mass fraction of the polyol solution of tin is 1.6%, and gamma-Al is added 2 O 3 The polyol dispersion was 33.3% by mass.
4. The catalyst for preparing 1,4-cyclohexanedicarboxylate by hydrogenating dimethyl terephthalate as claimed in claim 1, wherein: in the step S1, the ruthenium salt is ruthenium acetate or ruthenium trichloride, the tin salt is stannous chloride, and the polyol is one or a combination of more of ethylene glycol, glycerol, 1,4-butanediol, 1,6-hexanediol, 1,2-dodecanediol, 1,2-hexadecanediol, D-sorbitol and ribitol.
5. The catalyst for preparing 1,4-cyclohexanedicarboxylate by hydrogenating dimethyl terephthalate as claimed in claim 1, wherein: in the step S2, the organic base is one or a combination of several of trimethylamine, triethylamine, diethylenetriamine and triethylenetetramine.
6. The catalyst for preparing 1,4-cyclohexane dicarboxylic acid dimethyl ester by hydrogenation of dimethyl terephthalate as claimed in claim 1, wherein: in the step S3, the heating temperature is 70-90 ℃.
7. Use of the catalyst of claim 1 for the hydrogenation of dimethyl terephthalate to produce 1,4-dimethyl cyclohexanedicarboxylate, wherein: the specific process is that the catalyst is used for preparing 1,4-cyclohexane dimethyl dicarboxylate by hydrogenating dimethyl terephthalate in a slurry bed, 1,4-cyclohexane dimethyl dicarboxylate is used as a solvent, the feeding mass ratio of dimethyl terephthalate to 1,4-cyclohexane dimethyl dicarboxylate is 1 (0.5-2), and the feeding mass ratio of dimethyl terephthalate to catalyst is 10: (1-5), the reaction pressure is 4-8MPa, the reaction temperature is 100-140 ℃, the reaction time is 30-200min, and the 1,4-cyclohexane dicarboxylic acid dimethyl ester is obtained by separating the catalyst after cooling.
8. The catalyst of claim 7 for use in the hydrogenation of dimethyl terephthalate to produce 1,4-dimethyl cyclohexanedicarboxylate, wherein: the reaction pressure is 4-6MPa, the reaction temperature is 110-130 ℃, and the reaction time is 60-120min.
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| JP3887845B2 (en) * | 1996-06-28 | 2007-02-28 | 三菱化学株式会社 | Catalyst for hydrogenation reaction, production method thereof, and hydrogenation reaction method using the catalyst |
| CN102935365B (en) * | 2012-11-12 | 2014-12-03 | 中国石油化工股份有限公司 | Catalyst and method for preparing 1,4-cyclohexane dimethyl isophthalate |
| 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 |
| CN105536784A (en) * | 2016-01-26 | 2016-05-04 | 青岛科技大学 | Method for preparing catalyst for cyclohexanedicarboxylic acid dibasic ester preparation and application of catalyst |
| CN106984310A (en) * | 2017-03-27 | 2017-07-28 | 常州大学 | A kind of method for preparing catalyst of phthalic ester plasticizer hydrogenation and application |
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