TW201741023A - Catalyst and method for hydrogenation of 1,3-cyclobutanediketone compound - Google Patents

Abstract

Catalyst for hydrogenation of 1,3-cyclobutanediketone compound is provided, which includes a support and VIIIB group transition metal loaded thereon. The support includes a first oxide powder with a surface wrapped by a second oxide. The first oxide includes silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, zinc oxide, or a combination thereof. The second oxide has a composition of MxAl(1-x)O(3-x)/2, M is alkaline earth metal, and x is 0.3 to 0.7.

Description

Catalyst and method for hydrogenating cyclobutanedione compounds

The present invention relates to hydrogenation reactions, more particularly to catalysts for their use.

Cyclobutanediol (CBDO) such as 2,2,4,4-tetramethyl-1,3-cyclobutanediol is a multifunctional intermediate widely used in the synthesis of copolymerized polyesters, for example for synthesis. A high performance polyester that can replace polycarbonate (PC). Conventional polyesters have a low glass transition temperature and are limited in applications in the medium and high temperature fields. The addition of CBDO significantly increases the glass transition temperature, weatherability, and clarity of the polyester. The polyester synthesized using CBDO has excellent physical properties similar to those of bisphenol A, such as high impact strength, excellent dimensional stability, high glass transition temperature, and no carcinogens and other toxic substances.

The process and downstream products of CBDO and its applications are mainly developed by Eastman. At present, Eastman's hydrogenation process is a high pressure hydrogenation (reaction pressure 100 bar) which hydrogenates the ketone group of tetramethylcyclobutanedione to an alcohol group. However, the higher hydrogenation temperature of this process may be more susceptible to ring-opening side reactions. If the reaction pressure is lowered but the molar ratio of hydrogen to raw material is increased to more than 300, the conversion of tetramethyl-1,3-cyclobutanedione and the selectivity of tetramethyl-1,3-cyclobutanediol can be increased. However, this reaction condition will cause a large amount of hydrogen circulation or work safety costs. In summary, the current There is a need for new methods of hydrogenating tetramethylcyclobutanedione to reduce the hydrogenation temperature and/or pressure while maintaining a high selectivity for CBDO in the product.

An embodiment of the present invention provides a catalyst for hydrogenating a cyclobutanedione compound, comprising: a carrier comprising a first oxide powder having a surface coated with a second oxide; and a Group VIIIB transition metal supported on the carrier, wherein The first oxide includes cerium oxide, aluminum oxide, zirconium oxide, titanium oxide, zinc oxide, or a combination thereof, and wherein the composition of the second oxide is M _x Al _(1-x) O _(3-x)/2 , M is an alkaline earth metal, and x is between 0.3 and 0.7.

An embodiment of the present invention provides a method for hydrogenating a cyclobutanedione compound, comprising: hydrogenating a cyclobutanedione compound with a hydrogenation catalyst to form a cyclobutanediol compound, wherein the catalyst comprises: a carrier, including a surface a first oxide powder coated with a second oxide; and a Group VIIIB transition metal supported on the support, wherein the first oxide comprises cerium oxide, aluminum oxide, zirconium oxide, titanium oxide, zinc oxide, or the like The combination, and wherein the composition of the second oxide is M _x Al _(1-x) O _(3-x)/2 , M is an alkaline earth metal, and x is between 0.3 and 0.7.

One embodiment of the present invention provides a catalyst for hydrogenating a cyclobutanedione compound, comprising: a support and a Group VIIIB transition metal supported on a support. In one embodiment, the Group VIIIB transition metal comprises ruthenium, palladium, or a combination thereof. The carrier includes a first oxide powder having a surface coated with a second oxide. The first oxide includes cerium oxide, aluminum oxide, zirconium oxide, titanium oxide, zinc oxide, or a combination thereof. In an embodiment, the first oxide may be a porous support having a specific surface area between 100 m ² /g and 300 m ² /g. In general, a larger specific surface area is more favorable for the reaction. The composition of the second oxide is M _x Al _(1-x) O _(3-x)/2 , M is an alkaline earth metal, and x is between 0.3 and 0.7. In an embodiment, x is between 0.4 and 0.6. In one embodiment, the alkaline earth metal M comprises magnesium, calcium, or a combination thereof.

In one embodiment, the weight ratio of the first oxide to the second oxide in the support is between 1:3 and 4:1. In one embodiment, the weight ratio of the first oxide to the second oxide in the support is between 1.5:1 and 3:1. The x (content of M) and the weight ratio of the first oxide to the second oxide in the composition of the second oxide have a certain relationship with the characteristics (pH) of the carrier. Generally, the carrier alkalinity increases as the ratio of x to the second oxide increases. A suitable ratio of x value to second oxide (i.e., M content in the carrier) results in higher reactivity and product selectivity. In one embodiment, the M salt and the aluminum salt may be first dissolved in an alkaline solution to form an M-aluminum sol gel. Then, the M-alumina sol gel and the first oxide are mixed, and after filtration, sintering and pulverization are carried out to obtain a carrier which is a first oxide having a surface coated with a second oxide (M-aluminum oxide).

In one embodiment, the weight ratio of Group VIIIB transition metal to carrier is between 1:10 and 1:200. In one embodiment, the weight ratio of Group VIIIB transition metal to carrier is between 1:10 and 1:50. If the proportion of the Group VIIIB transition metal is too high, the catalyst cost will increase. If the proportion of the Group VIIIB transition metal is too low, the cyclobutanedione compound cannot be effectively hydrogenated. In one embodiment, the carrier may further include a rare earth element, and the rare earth element is between 1% and 10% by weight of the carrier, wherein the rare earth metal comprises lanthanum, cerium, or a combination thereof.

In one embodiment, the carrier of the catalyst comprises magnesium oxide aluminum coated on the porous alumina powder (including tantalum oxide as the case may be), and the base metal is supported on the carrier.

In an embodiment, the forming agent may further be included in the carrier, and the forming agent may be exemplified by alumina sol, silica gel, titanium sol, zirconium sol. Or pitch, the role of the molding agent is to shape the catalyst carrier (such as a column).

In one embodiment of the present invention, the catalyst is mixed with hydrogen to hydrogenate a cyclobutanedione compound to form a cyclobutanediol compound. When the structure of the cyclobutanedione compound is The structure of the cyclobutanediol compound formed after hydrogenation is . When the structure of the cyclobutanedione compound is The structure of the cyclobutanediol compound formed after hydrogenation is . When the structure of the cyclobutanedione compound is The structure of the cyclobutanediol compound formed after hydrogenation is . The above R ¹ , R ² , R ³ and R ⁴ are each hydrogen, a C _1-10 alkyl group, a C _5-10 cycloalkyl group, or a C _6-10 aryl group, and each of R ⁵ and R ⁷ is a C _5-10 cycloalkyl group, each of R ⁶ and R ^{8 being} each hydrogen, a C _1-10 alkyl group, a C _5-10 cycloalkyl group, or a C _6-10 aryl group, and n and m Each is between 4 and 9. In one embodiment, the structure of the cyclobutanedione compound is And the structure of the cyclobutanediol compound is . In one embodiment, the structure of the cyclobutanedione compound is And the structure of the cyclobutanediol compound is . In one embodiment, the structure of the cyclobutanedione compound is And the structure of the cyclobutanediol compound is . In one embodiment, the structure of the cyclobutanedione compound is And the structure of the cyclobutanediol compound is . In one embodiment, the structure of the cyclobutanedione compound is And the structure of the cyclobutanediol compound is . In one embodiment, the structure of the cyclobutanedione compound is And the structure of the cyclobutanediol compound is . In addition to the above cyclobutanedione compounds, other suitable cyclobutanedione compounds may be employed to form the corresponding cyclobutanediol compounds.

In one embodiment, the hydrogen pressure of the hydrogenation process described above can be between 10 and 120 bar. In one embodiment, the hydrogen pressure of the hydrogenation process described above can range from 30 to 70 bar. In general, the rate of hydrogenation increases as the pressure of hydrogen increases, whereas if the pressure of hydrogen is too high, equipment and cost of work are increased. In one embodiment, the temperature of the hydrogenation process described above is between 50 ° C and 200 ° C. In one embodiment, the temperature of the hydrogenation process described above is between 60 ° C and 120 ° C. The rate of hydrogenation increases with increasing temperature, however, if the temperature of the hydrogenation process is too high, the proportion of by-products is increased.

The above catalyst has the following advantages in hydrogenating a cyclobutanedione compound: (1) a medium-low temperature medium pressure hydrogenation process; (2) a conversion rate of >99%; and (3) a high selectivity of the cyclobutanediol compound product. rate.

The above and other objects, features, and advantages of the present invention will become more apparent and understood.

Example

Preparation Example A

First, a 1 L deionized aqueous solution containing magnesium nitrate (256 g) and aluminum nitrate (357 g) was added to a 1 L deionized water solution containing sodium hydroxide (208 g) and sodium carbonate (152 g), stirred at room temperature and aged for 18 hours to form Magnesium alumina sol gel (sol-gel). Then, 200 g of alumina powder (the powder composition of 95 wt% alumina and 5 wt% of cerium oxide) was added to the magnesium alumina sol gel, and the mixture was continuously stirred for 1 hour, followed by filtration, and the obtained filter cake was washed three times with water and then dried at 110 ° C. The dried powder (the surface coated with magnesium oxide aluminum oxide/yttria powder) is subjected to a molding step to obtain a uniform particle of 20 to 30 mesh number, which is used as a carrier for supporting the catalyst. . 20 g of the carrier was weighed, and a RuCl ₃ solution (containing 0.4 g of ruthenium) was added, stirred for 20 minutes until the dispersion was uniform, and then heated to 120 ° C for 5 hours to remove the solvent. Then, the mixture was heated to 200 ° C for 12 hours, then placed in water at 80 ° C for five times, and then dried at 120 ° C for 4 hours to obtain a carrier coated with ruthenium as the A catalyst. The weight ratio of the carrier to the ruthenium was 100:2.

Preparation Example B

20 g of alumina (Al ₂ O ₃ ) was added to a RuCl ₃ solution (containing 0.4 g of ruthenium), stirred for 20 minutes until the dispersion was uniform, and then heated to 120 ° C for 5 hours to remove the solvent. Then, after heating to 200 ° C for 12 hours, it is washed with water in 80 ° C for five times, and then dried at 120 ° C for 4 hours to obtain a surface-coated alumina carrier as a B catalyst, wherein alumina and bismuth The weight ratio is 100:2.

Preparation C

20 g of zeolite (ZSM-5, source: sud-chemie SiO ₂ /Al ₂ O ₃ = 27) was added to the RuCl ₃ solution (containing 0.4 g of hydrazine), stirred for 20 minutes until the dispersion was uniform, and then heated to 120 ° C and maintained at 5 Hours to remove solvent. After heating to 200 ° C for 12 hours, it was washed with water in 80 ° C for five times, and then dried at 120 ° C for 4 hours to obtain a zeolite-coated zeolite carrier as a C catalyst, wherein the weight ratio of zeolite to rhodium It is 100:2.

Preparation Example D

First, a 1 L deionized aqueous solution containing magnesium nitrate (256 g) and aluminum nitrate (357 g) was added to a 1 L deionized water solution containing sodium hydroxide (208 g) and sodium carbonate (152 g), stirred at room temperature and aged for 18 hours to form Magnesium alumina sol gel (sol-gel). Then, 100 g of alumina powder (the powder composition of 95 wt% alumina and 5 wt% of cerium oxide) was added to the magnesium alumina sol gel, and stirring was continued for 1 hour, followed by filtration, and the obtained filter cake was washed three times with water and then dried at 110 ° C. The dried powder (the surface coated with magnesium oxide aluminum oxide/yttria powder) is subjected to a molding step to obtain uniform particles of 20 to 30 mesh numbers, which is a carrier for supporting the catalyst. . 20 g of the carrier was weighed, a RuCl ₃ solution (containing 1.6 g of hydrazine) was added, stirred for 20 minutes until the dispersion was uniform, and then heated to 120 ° C for 5 hours to remove the solvent. After heating to 200 ° C for 12 hours, it was placed in water at 80 ° C for five times, and then dried at 120 ° C for 4 hours to obtain a carrier coated with ruthenium as a D catalyst. The weight ratio of the carrier to ruthenium was 100:8.

Preparation Example E

First, a 1 L deionized aqueous solution containing magnesium nitrate (256 g) and aluminum nitrate (357 g) was added to a 1 L deionized water solution containing sodium hydroxide (208 g) and sodium carbonate (152 g), stirred at room temperature and aged for 18 hours to form Magnesium alumina sol gel (sol-gel). Then, 100 g of alumina powder (aluminum powder having a powder composition of >99 wt%) was added to the magnesium alumina sol gel, and stirring was continued for 1 hour, followed by filtration. The obtained filter cake was washed three times with water and then dried at 110 ° C, and dried. The powder (the surface of the alumina powder coated with magnesium oxide aluminum) is subjected to a molding step to obtain a uniform particle of 20 to 30 mesh number, which is a carrier for supporting the catalyst. 20 g of the carrier was weighed, and a RuCl ₃ solution (containing 0.4 g of ruthenium) was added, stirred for 20 minutes until the dispersion was uniform, and then heated to 120 ° C for 5 hours to remove the solvent. After heating to 200 ° C for 12 hours, it was placed in water at 80 ° C for five times, and then dried at 120 ° C for 4 hours to obtain a carrier coated with ruthenium as an E catalyst. The weight ratio of the carrier to the ruthenium was 100:2.

Preparation Example F

First, a 1 L deionized aqueous solution containing magnesium nitrate (256 g) and aluminum nitrate (357 g) was added to a 1 L deionized water solution containing sodium hydroxide (208 g) and sodium carbonate (152 g), stirred at room temperature and aged for 18 hours to form Magnesium alumina sol gel (sol-gel). Then, 100 g of alumina powder (aluminum powder having a powder composition of >99 wt%) was added to the magnesium alumina sol gel, and stirring was continued for 1 hour, followed by filtration. The obtained filter cake was washed three times with water and then dried at 110 ° C, and dried. The powder (the surface of the alumina powder coated with magnesia-alumina) is subjected to a molding step to obtain uniform particles of 20 to 30 mesh numbers, which is a carrier for supporting the catalyst. 20 g of the carrier was weighed, a RuCl ₃ solution (containing 1.6 g of hydrazine) was added, stirred for 20 minutes until the dispersion was uniform, and then heated to 120 ° C for 5 hours to remove the solvent. Then, the mixture was heated to 200 ° C for 12 hours, and then placed in water at 80 ° C for five times, and then dried at 120 ° C for 4 hours to obtain a carrier having a surface coated with ruthenium as a F catalyst. The weight ratio of the carrier to the ruthenium was 100:8.

Example 1

6 ml of 20-30 mesh A catalyst was placed in a fixed bed reactor and tested in a trickle-bed mode for 4 wt% 2,2,4,4-tetramethyl-1,3 - Cyclobutanedione is subjected to a hydrogenation reaction. Reaction conditions: the solvent is ethyl acetate (Ethyl acetate, EA), the weight hourly space velocity (WHSV) of the feed is 0.24 hr ^-1 , the reaction temperature is 80 ° C, the reaction pressure is 35 kg / cm ² and hydrogen The molar ratio to 2,2,4,4-tetramethyl-1,3-cyclobutanedione was 69. The hydrogenation results were analyzed by gas chromatography (GC) as follows: the conversion of 2,2,4,4-tetramethyl-1,3-cyclobutanedione was 99.9%, and the product was 2, 2, 4, The selectivity of 4-tetramethyl-1,3-cyclobutanediol (CBDO) was 77.6%, as shown in Table 1.

Example 2

Similar to Example 1, the difference was that the reaction pressure was changed to 60 kg/cm ² and the molar ratio of hydrogen to 2,2,4,4-tetramethyl-1,3-cyclobutanedione was 69, and the other reaction parameters were the same. The hydrogenation results by GC analysis were as follows: the conversion of 2,2,4,4-tetramethyl-1,3-cyclobutanedione was 99.9%, and the selectivity of CBDO in the product was 98.4%, as shown in Table 2. Show.

Example 3

Take 6ml of 20-30mesh B catalyst in a fixed bed reactor and test in a continuous trickle-bed mode for 4wt% 2,2,4,4-tetramethyl-1,3 - Cyclobutanedione is subjected to a hydrogenation reaction. Reaction conditions: solvent is EA, feed WHSV is 0.24 hr ^-1 , reaction temperature is 80 ° C, reaction pressure is 35 kg / cm ² and hydrogen and 2,2,4,4-tetramethyl-1,3-ring The dimethylglyoximetry molar ratio was 69. The hydrogenation results by GC analysis were as follows: the conversion of 2,2,4,4-tetramethyl-1,3-cyclobutanedione was 88.6%, and the selectivity of CBDO in the product was 7.4%, as shown in Table 1. .

Example 4

Similar to Example 3, the difference was that the reaction pressure was changed to 60 kg/cm ² and the molar ratio of hydrogen to 2,2,4,4-tetramethyl-1,3-cyclobutanedione was 69, and the other reaction parameters were the same. The hydrogenation results by GC analysis were as follows: the conversion of 2,2,4,4-tetramethyl-1,3-cyclobutanedione was 99.9%, and the selectivity of CBDO in the product was 20.6%, as shown in Table 2. Show.

Example 5

6 ml of 20-30 mesh C catalyst was placed in a fixed bed reactor and tested in a trickle-bed mode for 4 wt% 2,2,4,4-tetramethyl-1,3 - Cyclobutanedione is subjected to a hydrogenation reaction. Reaction conditions: the solvent is EA, the WHSV of the feed is 0.24 hr ^-1 , the reaction temperature is 80 ° C, the reaction pressure is 35 kg / cm ² , and hydrogen and 2,2,4,4-tetramethyl-1,3- The cyclobutanedione molar ratio was 69. The hydrogenation results by GC analysis were as follows: the conversion of 2,2,4,4-tetramethyl-1,3-cyclobutanedione was 61.8%, and the selectivity of CBDO in the product was 1.7%, as shown in Table 1. .

Example 6

Similar to Example 5, the difference was that the reaction pressure was changed to 60 kg/cm ² and the molar ratio of hydrogen to 2,2,4,4-tetramethyl-1,3-cyclobutanedione was 69, and the other reaction parameters were the same. The hydrogenation results by GC analysis were as follows: the conversion of 2,2,4,4-tetramethyl-1,3-cyclobutanedione was 99.4%, and the selectivity of CBDO in the product was 22.7%, as shown in Table 2. Show.

As can be seen from the first table, the conversion of 2,2,4,4-tetramethyl-1,3-cyclobutanedione with self-made catalyst (including magnesium aluminum oxide) and the CBDO of the catalyst with the same enthalpy loading. The selectivity is the best and the proportion of ring-opening by-products is low, as the partially hydrogenated cyclic ketol product can be recovered via separation. The structure of the above cyclic ketol is And the ring opening by-product comprises a ring-opening ketone alcohol such as , TMPD such as , DIPK such as , DIPA such as Or a combination of the above.

It can be seen from the second table that the conversion of 2,2,4,4-tetramethyl-1,3-cyclobutanedione with self-made catalyst (including magnesium aluminum oxide) and CBDO are the same catalyst loading. The selectivity is the best and the proportion of open-loop by-products is low. As can be seen from Tables 1 and 2, increasing the hydrogen pressure increases the selectivity of CBDO. The definition of cyclic keto alcohols and ring opening by-products is as described above.

Example 7-1

6 ml of 20-30 mesh D catalyst was placed in a fixed bed reactor and tested in a trickle-bed mode for 4 wt% 2,2,4,4-tetramethyl-1,3 - Cyclobutanedione is subjected to a hydrogenation reaction. Reaction conditions: the solvent is n-butanol (n-Butanol, BuOH), the WHSV of the feed is 0.24 hr ^-1 , the liquid hourly space velocity (LHSV) of the feed is 4 hr ^-1 , and the reaction temperature is 135 ° C. The reaction pressure was 50 kg/cm ² , and the molar ratio of hydrogen to 2,2,4,4-tetramethyl-1,3-cyclobutanedione was 69. The hydrogenation results by GC analysis were as follows: the conversion of 2,2,4,4-tetramethyl-1,3-cyclobutanedione was 99.8%, and the selectivity of CBDO in the product was 10%, as shown in Table 3. .

Example 7-2

Similar to Example 7-1, the difference is that the reaction pressure is changed to 35 kg/cm ² , and the molar ratio of hydrogen to 2,2,4,4-tetramethyl-1,3-cyclobutanedione is 69, and the feed is the reduced WHSV 0.12hr ^-1, LHSV feed of reduced 2hr ^-1, and the reaction temperature dropped to 100 ℃, the other reaction parameters. The hydrogenation results by GC analysis were as follows: the conversion of 2,2,4,4-, tetramethyl-1,3-cyclobutanedione was 99.9%, and the selectivity of CBDO in the product was 77.3%, as shown in Table 3. Shown.

Example 7-3

Similar to Example 7-2, the difference was that the reaction temperature was lowered to 80 ° C, and the other reaction parameters were the same. The hydrogenation results by GC analysis were as follows: the conversion of 2,2,4,4-tetramethyl-1,3-cyclobutanedione was 99.9%, and the selectivity of CBDO in the product was 97.2%, as shown in Table 3. Show.

As can be seen from the third table, when the D catalyst having a high Ru ratio is used, lowering the hydrogenation temperature does not lower the conversion ratio of 2,2,4,4-tetramethyl-1,3-cyclobutanedione, and The selectivity of CBDO in the product can be increased.

Example 8

Similar to Example 1, the difference was that the reaction pressure was changed to 20 kg/cm ² , and the molar ratio of hydrogen to 2,2,4,4-tetramethyl-1,3-cyclobutanedione was 69, and the other reaction parameters were the same. . The hydrogenation results by GC analysis were as follows: the conversion of 2,2,4,4-tetramethyl-1,3-cyclobutanedione was 99.9%, and the selectivity of CBDO in the product was 76.3%, as shown in Table 4. Show.

As can be seen from Table 4, increasing the reaction pressure increases the selectivity of CBDO in the product. From a comparison of Tables 3 and 4, increasing the Ru content in the catalyst increases the selectivity of CBDO in the product.

Example 8-1

6 ml of 20-30 mesh E catalyst was placed in a fixed bed reactor and tested in a trickle-bed mode for 4 wt% 2,2,4,4-tetramethyl-1,3 - Cyclobutanedione is subjected to a hydrogenation reaction. Reaction conditions: solvent EA, the feed WHSV of 0.24hr ^-1, LHSV of the feed of 4hr ^-1, reaction temperature was 80 ℃, reaction pressure of 35kg / cm ^2, and the hydrogen and 2,2,4,4 The tetramethyl-1,3-cyclobutanedione molar ratio was 69. The hydrogenation results by GC analysis were as follows: the conversion of 2,2,4,4-tetramethyl-1,3-cyclobutanedione was 99.9%, and the selectivity of CBDO in the product was 99.2%, as shown in Table 5. . On the other hand, after the operation of the above continuous hydrogenation reaction for more than 135 hours, the conversion ratio of 2,2,4,4-tetramethyl-1,3-cyclobutanedione is 99.9%, and the selectivity of CBDO in the product is selected. At 99.5%, it is apparent that this catalyst has long-term stability with hydrogenation conditions.

Example 8-2

Similar to Example 8-1, the difference was that the reaction temperature was lowered to 70 ° C, and the other reaction parameters were the same. The hydrogenation results by GC analysis were as follows: the conversion of 2,2,4,4-tetramethyl-1,3-cyclobutanedione was 99.95%, the selectivity of CBDO in the product was 92.8%, and the ring-opening by-product The ratio is very low, as shown in Table 5.

Example 8-3

Similar to Example 8-1, the difference was that the reaction temperature was lowered to 60 ° C, and the other reaction parameters were the same. The hydrogenation results by GC analysis were as follows: the conversion of 2,2,4,4-tetramethyl-1,3-cyclobutanedione was 99.18%, and the selectivity of CBDO in the product was 75.2%, as shown in Table 5. Show.

Example 8-4

Similar to Example 8-1, the difference is that the reaction temperature is lowered to 60 ° C, the reaction pressure is increased to 60 kg / cm ² , and hydrogen and 2,2,4,4-tetramethyl-1,3-cyclobutanedione The ear ratio was 69 and the other reaction parameters were the same. The hydrogenation results by GC analysis were as follows: the conversion of 2,2,4,4-tetramethyl-1,3-cyclobutanedione was 99.9%, and the selectivity of CBDO in the product was 99.2%, as shown in Table 5. Show.

As can be seen from the fifth table, even a carrier containing no La exhibits a good CBDO selectivity. On the other hand, lowering the temperature will reduce the selection of CBDO in the product. The selectivity, but can be combined with higher reaction pressure at medium and low temperatures to increase the selectivity of CBDO in the product.

Example 9-1

Take 6ml of 20-30mesh F catalyst in a fixed bed reactor and test in a continuous trickle-bed mode for 4wt% 2,2,4,4-tetramethyl-1,3 - Cyclobutanedione is subjected to a hydrogenation reaction. Reaction conditions: the solvent is EA, the WHSV of the feed is 0.24 hr ^-1 , the LHSV of the feed is 4.5 hr ^-1 , the reaction temperature is 60 ° C, the reaction pressure is 20 kg/cm ² , and the hydrogen gas is ² , ² , 4, The 4-tetramethyl-1,3-cyclobutanedione molar ratio was 69. The hydrogenation results by GC analysis were as follows: the conversion of 2,2,4,4-tetramethyl-1,3-cyclobutanedione was 99.9%, and the selectivity of CBDO in the product was 99.6%, as shown in Table 6. .

Example 9-2

Similar to Example 9-1, the difference is that the concentration of 2,2,4,4-tetramethyl-1,3-cyclobutanedione is changed to 6 wt%, the LHSV of the feed is decreased to 3 hr ^-1 , and other reactions The parameters are the same. The hydrogenation results by GC analysis were as follows: the conversion of 2,2,4,4-tetramethyl-1,3-cyclobutanedione was 99.9%, and the selectivity of CBDO in the product was 99.3%, as shown in Table 6. Show.

Example 9-3

Similar to Example 9-1, the difference was that the concentration of 2,2,4,4-tetramethyl-1,3-cyclobutanedione was changed to 8 wt%, and the LHSV of the feed was decreased to 2.25 hr ^-1 . The reaction parameters are the same. The hydrogenation results by GC analysis were as follows: the conversion of 2,2,4,4-tetramethyl-1,3-cyclobutanedione was 99.9%, and the selectivity of CBDO in the product was 99.1%, as shown in Table 6. Show.

Example 9-4

Similar to Example 9-3, the difference is that the solvent is changed to a cosolvent of EA and BuOH. (weight ratio is 0.5:0.5), other reaction parameters are the same. The hydrogenation results by GC analysis were as follows: the conversion of 2,2,4,4-tetramethyl-1,3-cyclobutanedione was 99.9%, and the selectivity of CBDO in the product was 93.8%, but the ring-opening by-product The ratio is low, as shown in Table 6.

Example 9-5

Similar to Example 9-4, the difference was that the concentration of 2,2,4,4-tetramethyl-1,3-cyclobutanedione was changed to 10% by weight, and the LHSV of the feed was decreased to 1.8 hr ^-1 . The reaction parameters are the same. The hydrogenation results by GC analysis were as follows: the conversion of 2,2,4,4-tetramethyl-1,3-cyclobutanedione was 99.9%, and the selectivity of CBDO in the product was 93.5%, but the ring-opening by-product The ratio is low, as shown in Table 6.

Example 9-6

Similar to Example 9-5, the difference was that the reaction pressure was increased to 60 kg/cm ² , and the molar ratio of hydrogen to 2,2,4,4-tetramethyl-1,3-cyclobutanedione was 69, and other reactions were observed. The parameters are the same. The hydrogenation results by GC analysis were as follows: the conversion of 2,2,4,4-tetramethyl-1,3-cyclobutanedione was 99.9%, and the selectivity of CBDO in the product was 99.5%, as shown in Table 6. Show.

Example 10

Take 7ml of 20-30mesh E catalyst in a 1/2吋 fixed bed reactor and test in a continuous trickle-bed mode for 4wt% 2,2,4,4-tetramethyl -1,3-cyclobutanedione is subjected to a hydrogenation reaction. Reaction conditions: the solvent is EA, the WHSV of the feed is 0.24 hr ^-1 , the reaction temperature is 80 ° C, the reaction pressure is 60 kg / cm ² , and hydrogen and 2,2,4,4-tetramethyl-1,3- The cyclobutanedione molar ratio is 12. The hydrogenation results by GC analysis were as follows: the conversion of 2,2,4,4-tetramethyl-1,3-cyclobutanedione was 99.9%, and the selectivity of CBDO in the product was 99.1%.

As can be seen from the sixth table, when the F catalyst having a high Ru ratio is used, lowering the hydrogenation pressure does not lower the selectivity of CBDO in the product. Alternatively, the hydrogenation process described above can be combined with different solvent combinations, reactant concentrations, and feed flow rates to increase the flexibility of the hydrogenation process.

While the invention has been described above in terms of several embodiments, it is not intended to limit the invention, and any one of ordinary skill in the art can be modified and modified without departing from the spirit and scope of the invention. Therefore, the scope of the invention is defined by the scope of the appended claims.

Claims (16)

A catalyst for hydrogenating a cyclobutanedione compound, comprising: a carrier comprising a first oxide powder having a surface coated with a second oxide; and a Group VIIIB transition metal supported on the carrier, wherein the first The monooxide comprises cerium oxide, aluminum oxide, zirconium oxide, titanium oxide, zinc oxide, or a combination thereof, and wherein the composition of the second oxide is M _x Al _(1-x) O _(3-x)/2 , M is an alkaline earth metal, and x is between 0.3 and 0.7. The catalyst for hydrogenating a cyclobutanedione compound according to claim 1, wherein the alkaline earth metal comprises magnesium, calcium, or a combination thereof. The catalyst for hydrogenating a cyclobutanedione compound according to claim 1, wherein the Group VIIIB transition metal comprises ruthenium, palladium or a combination thereof. The catalyst for hydrogenating a cyclobutanedione compound according to claim 1, wherein the weight ratio of the first oxide to the second oxide is between 1:3 and 4:1. The catalyst for hydrogenating a cyclobutanedione compound according to claim 1, wherein the weight ratio of the Group VIIIB transition metal to the carrier is between 1:10 and 1:200. The catalyst for hydrogenating a cyclobutanedione compound according to claim 1, wherein the carrier further comprises a rare earth element, and the rare earth element accounts for between 1% by weight and 10% by weight of the carrier. A method for hydrogenating a cyclobutanedione compound, comprising: hydrogenating a cyclobutanedione compound with a catalyst in combination with hydrogen to form a cyclobutanediol compound, wherein the catalyst of the hydrogenated cyclobutanedione compound comprises: a carrier comprising a first oxide powder having a surface coated with a second oxide; and a Group VIIIB transition metal supported on the support, wherein the first oxide comprises cerium oxide, aluminum oxide, zirconium oxide, oxidation Titanium, zinc oxide, or a combination thereof, and wherein the composition of the second oxide is M _x Al _(1-x) O _(3-x)/2 , M is an alkaline earth metal, and x is between 0.3 and 0.7 between. The method of hydrogenating a cyclobutanedione compound according to claim 7, wherein the alkaline earth metal comprises magnesium, calcium, or a combination thereof. The method of hydrogenating a cyclobutanedione compound according to claim 7, wherein the Group VIIIB transition metal comprises ruthenium, palladium, or a combination thereof. The method of hydrogenating a cyclobutanedione compound according to claim 7, wherein the weight ratio of the first oxide to the second oxide is between 1:3 and 4:1. The method of hydrogenating a cyclobutanedione compound according to claim 7, wherein the weight ratio of the Group VIIIB transition metal to the carrier is between 1:10 and 1:200. The method of hydrogenating a cyclobutanedione compound according to claim 7, wherein the carrier further comprises a rare earth element, and the rare earth element comprises between 1% by weight and 10% by weight of the carrier. The method for hydrogenating a cyclobutanedione compound according to claim 7, wherein the structure of the cyclobutanedione compound is: Wherein R ¹ , R ² , R ³ and R ⁴ are each hydrogen, a C _1-10 alkyl group, a C _5-10 cycloalkyl group, or a C _6-10 aryl group, and each of R ⁵ and R ⁷ is a C _5-10 cycloalkyl group, each of R ⁶ and R ^{8 being} each hydrogen, a C _1-10 alkyl group, a C _5-10 cycloalkyl group, or a C _6-10 aryl group, and n and m Each is between 4 and 9. The method of hydrogenating a cyclobutanedione compound according to claim 7, wherein the structure of the cyclobutanediol compound is: Wherein R ¹ , R ² , R ³ and R ⁴ are each hydrogen, a C _1-10 alkyl group, a C _5-10 cycloalkyl group, or a C _6-10 aryl group, and each of R ⁵ and R ⁷ is a C _5-10 cycloalkyl group, each of R ⁶ and R ^{8 being} each hydrogen, a C _1-10 alkyl group, a C _5-10 cycloalkyl group, or a C _6-10 aryl group, and n and m Each is between 4 and 9. The method of hydrogenating a cyclobutanedione compound according to claim 7, wherein the pressure of the hydrogen is between 10 and 120 bar. The method of hydrogenating a cyclobutanedione compound according to claim 7, wherein the temperature of the hydrogenated cyclobutanedione compound is between 50 ° C and 200 ° C.