Difunctional ternary supported noble metal catalyst and application thereof

Abstract

The invention belongs to the technical field of noble metal catalysts, and particularly relates to a bifunctional ternary supported noble metal catalyst for preparing 2-hydroxy-gamma-butyrolactone through malic acid hydrogenation and application. The invention relates to a ternary supported noble metal catalyst, which has two catalytic reaction functions of hydrogenation and lactonization, the active metal of the catalyst has a higher catalytic hydrogenation function, and the molecular sieve provides favorable reaction acidic sites for lactonization. A combination of metals Re, Ru and Pt is used as an active metal component of the catalyst; wherein in percentage by weight, the zeolite molecular sieve accounts for 82-84%, and the active metal accounts for 16-18%. According to the present invention, the high activity and high selectivity noble metal catalyst has high activity and high selectivity under neutral and low temperature conditions, and the hydrogenation and the lactonization reaction are simultaneously performed in the synthesis system by using the bifunctional ternary metal catalyst and using the malic acid as the raw material so as to directly obtain the alpha-hydroxy-gamma-butyrolactone;

Description

Technical Field

[0001] The invention belongs to the technical field of precious metal catalysts, and specifically relates to a bifunctional ternary supported precious metal catalyst for preparing 2-hydroxy-gamma-butyrolactone by hydrogenating malic acid and an application thereof. Background Art

[0002] With the updating of pharmaceutical industry technology and the upgrading of product quality, the added value of pharmaceutical intermediates and the optimization of process routes are constantly improving. As a very important pharmaceutical intermediate, α-hydroxy-γ-butyrolactone is widely used in the synthesis of new drugs and material development, and its synthesis method has also received widespread attention from researchers. Malic acid, as a natural product, is commonly found in all fruits and is an excellent raw material for the preparation of α-hydroxy-γ-butyrolactone. However, malic acid itself has poor thermal stability and begins to decompose naturally at temperatures of 140-150°C. Therefore, it is difficult to synthesize α-hydroxy-γ-butyrolactone using malic acid as a raw material. At present, there are mainly the following routes for preparing α-hydroxy-γ-butyrolactone from malic acid or its derivatives: Denmark SE reported that malic acid was used as a raw material (Denmark, SE; Yang, S.-MJ Am. Chem. Soc. 2004, 126, 12432-12440), carboxyl and α-hydroxy groups were protected by acetone under the catalysis of boron trifluoride etherate, β-carboxyl groups were reduced by sodium borohydride / boron trifluoride etherate or sodium borohydride / iodine or zinc borohydride, and then α-hydroxy-γ-butyrolactone was synthesized by four steps of deprotection and lactonization under the catalysis of p-toluenesulfonic acid. The reaction process of this method is risky, and the post-treatment and distillation process are complicated and costly, which is not economical and safe in industrial production. The patent (CN112939901A) uses malic acid diester compounds as raw materials, which are reduced to 4-hydroxy-succinic acid ethyl ester under the action of hydrolase, and then reduced to 2,4-dihydroxybutyric acid by sodium borohydride, and then α-hydroxy-γ-butyrolactone is generated under the action of acid catalysis. This method uses enzyme catalysis, which is costly and has poor universality, increasing the economic burden of industrial production. Patent WO2011124578A1 reports a method for preparing α-hydroxy-γ-butyrolactone by hydrogenation of malic acid using a bimetallic Sn-Ru catalyst, with a conversion rate of 85% and a yield of 55%. The reaction conditions of this method are harsh, and the catalyst needs to be activated at 450°C, and the reaction temperature is as high as 300°C.

[0003] The above patented technology has the problems of complex process, long synthesis route, large amount of three wastes and high production cost. The purpose of the present invention is to develop a safe, green, simple, efficient and low-cost catalyst and method for preparing α-hydroxy-γ-butyrolactone. Summary of the invention

[0004] The problem to be solved by the present invention is to provide a bifunctional ternary supported precious metal catalyst for preparing 2-hydroxy-γ-butyrolactone by hydrogenating malic acid and its application in view of the problems of complex process, long synthesis route, large amount of three wastes and high production cost in the prior art.

[0005] To achieve the above purpose, the present invention adopts the technical solution as follows:

[0006] A ternary supported noble metal catalyst has two catalytic reaction functions of hydrogenation and lactonization. The catalyst active metal has a higher catalytic hydrogenation function, and the molecular sieve provides favorable reaction acid sites for lactonization: the catalyst uses an ultra-high silicon-aluminum ratio zeolite molecular sieve as a catalyst carrier and a combination of metals Re, Ru, and Pt as a catalyst active metal component; wherein, by weight percentage, 82-84% of the zeolite molecular sieve and 16-18% of the active metal.

[0007] The specific surface area of ​​the catalyst is 200-500m 2 / g, with a total pore volume of 0.3-0.4cm 3 / g, the silicon-to-aluminum ratio (atomic ratio) is 200-400.

[0008] The metal mass ratio of the active metal is Re:Ru:Pt=2-6:1:1.

[0009] The Re metal is one or both of ammonium perrhenate and perrhenic acid, the Ru metal is one or both of ruthenium nitrate and ruthenium chloride, and the Pt metal is one or both of platinum nitrate and platinum nitrate.

[0010] The carriers are all H-type zeolite molecular sieves with a specific surface area of ​​300-800m 2 / g, pore volume is 0.3-0.6cm 3 / g.

[0011] A method for preparing the ternary supported noble metal catalyst:

[0012] 1) mixing the zeolite molecular sieve and a deionized water solution, and preparing a slurry by ultrasonic dispersion and stirring;

[0013] 2) preparing a metal salt solution, dissolving a metal salt containing Re in water, mixing the solution with the slurry obtained in step 1), stirring the solution thoroughly, removing water by rotary evaporation, and reducing the solution with high-temperature hydrogen to obtain a Re / zeolite molecular sieve;

[0014] 3) The Re / zeolite molecular sieve powder obtained in step 2) is immersed in an aqueous solution containing Ru and Pt metal salts by an equal volume method, left at room temperature, dried, and then reduced with high temperature hydrogen to obtain a catalyst Re-Ru-Pt / zeolite molecular sieve.

[0015] Further speaking

[0016] In step 1), the molecular sieve and deionized water are mixed in a mass ratio of 1:28-33, the ultrasonic time is 5-10 minutes, and the mixture is stirred and mixed;

[0017] In step 2), the mass ratio of metal Re to water in the Re metal salt aqueous solution is 1:200, and the mixture is stirred and mixed, and then the mixture is mixed with the slurry obtained in step 1) at a ratio of 0.1:1, and then the mixture is rotary evaporated at 65-75°C, and then the reduction temperature is 350-450°C in the presence of hydrogen, and the reduction time is 3-6h;

[0018] In step 3), an aqueous solution containing Ru and Pt metal salts is prepared, and the Re / zeolite molecular sieve is impregnated therein by an equal volume method, placed at room temperature for 12-24 hours, dried at 110°C for 6-10 hours, and reduced in hydrogen at a temperature of 250-350°C for 2-4 hours to obtain a catalyst Re-Ru-Pt / zeolite molecular sieve.

[0019] An application of the ternary supported bifunctional noble metal catalyst is the application of the catalyst in the preparation of 2-hydroxy-γ-butyrolactone by hydrogenation of malic acid.

[0020] The catalyst is used in the preparation of α-hydroxy-γ-butyrolactone in the hydrogenation lactonization reaction of malic acid, wherein the mass ratio of the catalyst to the reactant (malic acid) is 1:9-11.

[0021] Compared with the prior art, the patent of this invention has the following advantages:

[0022] The invention discloses a highly active and highly selective noble metal catalyst, which has high activity and selectivity under neutral and low temperature conditions, and utilizes the bifunctional ternary metal catalyst, uses malic acid as a raw material, and simultaneously performs hydrogenation and lactonization reactions in a synthesis system to directly obtain α-hydroxy-γ-butyrolactone. The method has a simple and efficient reaction process, a safe reaction process, does not generate toxic and harmful byproducts, is green and environmentally friendly, and is suitable for mass production of α-hydroxy-γ-butyrolactone; specifically:

[0023] 1. The catalyst of the present invention can obtain a high yield of the target product α-hydroxy-γ-butyrolactone under mild conditions of the reaction system, and has high reaction activity and selectivity.

[0024] 2. The catalyst of the present invention has high safety in use, the malic acid raw material used is cheap and easily available, and the production cost is low.

[0025] 3. The method of the present invention has simple and efficient reaction process, safe reaction process, green and environmentally friendly, and is suitable for mass production of α-hydroxy-γ-butyrolactone. Specific embodiments

[0026] The technical features of the present invention are further described below through examples, but are not limited to the examples.

[0027] The present invention uses a zeolite molecular sieve with an ultra-high silicon-aluminum ratio as a carrier to prepare a bifunctional ternary supported noble metal catalyst. The obtained catalyst can be used in a mild reaction system with malic acid as a raw material to simultaneously carry out hydrogenation and lactonization reactions to directly obtain α-hydroxy-γ-butyrolactone. The reaction process is simple, the raw materials are cheap and easy to obtain, and the catalyst has high reaction activity and selectivity, high safety in use, and is suitable for the industrial production of α-hydroxy-γ-butyrolactone.

[0028] Example 1

[0029] 1) Take 10g of H-beta zeolite molecular sieve (industrial product) and mix it with 300g of deionized water, ultrasonicate it for 10min, transfer it into a three-necked flask and stir it for 0.5h to obtain a slurry, wherein the H-beta molecular sieve has a silicon-aluminum ratio of 200 and a specific surface area of ​​660m 2 / g, pore volume 0.38cm 3 / g.

[0030] 2) Take 2.14g of ammonium perrhenate (Re content 70%) in a beaker, dissolve it in 30g of deionized water, stir for 1h, and then mix the mixture with the slurry obtained in step 1) at a ratio of 0.1:1. After mixing, transfer it to a rotary evaporator and perform rotary evaporation to remove water at 70°C. After the water is completely removed, reduce it with hydrogen at 450°C for 3h to obtain Re / H-beta zeolite molecular sieve powder.

[0031] 3) Take the Re / H-beta powder obtained in step 2) in a beaker, weigh 1.25 g of ruthenium nitrate (Ru content 20%) and 1.25 g of platinum nitrate (Pt content 20%) respectively, mix them, and then mix them with 7.5 g of deionized water. Use the equal volume method to impregnate the metal salt aqueous solution into the Re / H-beta zeolite molecular sieve powder, leave it at room temperature for 24 h, dry it at 110°C for 6 h, reduce it with hydrogen at a temperature of 250°C and a reduction time of 4 h to obtain a Re-Ru-Pt / H-beta catalyst, named C1.

[0032] Example 2

[0033] The difference from Example 1 is that the H-beta molecular sieve has a silicon-aluminum ratio of 400 and a specific surface area of ​​620 m 2 / g, pore volume 0.35cm 3 / g, and other conditions were the same as in Example 1, to obtain a Re-Ru-Pt / H-beta catalyst, numbered C-2.

[0034] Example 3

[0035] 1) Take 10g of H-beta zeolite molecular sieve (industrial product) and mix it with 300g of deionized water, ultrasonicate it for 5min, transfer it into a three-necked flask and stir it for 0.5h to obtain a slurry, wherein the H-beta molecular sieve has a silicon-aluminum ratio of 200 and a specific surface area of ​​660m 2 / g, pore volume 0.38cm 3 / g.

[0036] 2) Take 1.43g of ammonium perrhenate (Re content 70%) in a beaker, dissolve it in 30g of deionized water, stir for 1h, and then mix the mixture with the slurry obtained in step 1) at a ratio of 0.1:1. After mixing, transfer it to a rotary evaporator and perform rotary evaporation to remove water at 70°C. After the water is completely removed, reduce it with hydrogen at 350°C for 6h to obtain Re / H-beta zeolite molecular sieve powder.

[0037] 3) Take the Re / H-beta powder from step 2) in a beaker, weigh 2.5 g of ruthenium nitrate (Ru content 20%) and 2.5 g of platinum nitrate (Pt content 20%) respectively, mix them, and then mix them with 6 g of deionized water. Use the equal volume method to impregnate the metal salt aqueous solution into the Re / H-beta zeolite molecular sieve powder, leave it at room temperature for 24 hours, dry it at 110°C for 10 hours, and use hydrogen reduction temperature of 350°C for 2 hours to obtain a Re-Ru-Pt / H-beta catalyst, named C3.

[0038] Example 4

[0039] 1) Take 10g of H-beta zeolite molecular sieve (industrial product) and mix it with 300g of deionized water, ultrasonicate it for 5min, transfer it into a three-necked flask and stir it for 0.5h to obtain a slurry, wherein the H-beta molecular sieve has a silicon-aluminum ratio of 300 and a specific surface area of ​​643m 2 / g, pore volume 0.41cm 3 / g.

[0040] 2) Take 1.9g of ammonium perrhenate (Re content 70%) in a beaker, dissolve it in 30g of deionized water, stir for 1h, and then mix the mixture with the slurry obtained in step 1) at a ratio of 0.1:1. After mixing, transfer it to a rotary evaporator and perform rotary evaporation to remove water at 70°C. After the water is completely removed, reduce it with hydrogen at 400°C for 4h to obtain Re / H-beta zeolite molecular sieve powder.

[0041] 3) Take the Re / H-beta powder of step 2) in a beaker, weigh 1.65g of ruthenium nitrate (Ru content 20%) and 1.65g of platinum nitrate (Pt content 20%) respectively, mix them, and then mix them with 7.5g of deionized water. Use the equal volume method to impregnate the metal salt aqueous solution into the Re / H-beta zeolite molecular sieve powder, leave it at room temperature for 24h, dry it at 110℃ for 10h, reduce it with hydrogen at a temperature of 300℃ and a reduction time of 3h to obtain a Re-Ru-Pt / H-beta catalyst, named C4.

[0042] Example 5

[0043] 1) Take 10g of H-ZSM-5 zeolite molecular sieve (industrial product) and mix it with 300g of deionized water, ultrasonicate it for 5min, transfer it into a three-necked flask and stir it for 0.5h to obtain a slurry, wherein the silicon-aluminum ratio of H-ZSM-5 molecular sieve is 300 and the specific surface area is 562m 2 / g, pore volume 0.39cm 3 / g.

[0044] 2) Take 1.9g of ammonium perrhenate (Re content 70%) in a beaker, dissolve it in 30g of deionized water, stir for 1h, and then mix the mixture with the slurry obtained in step 1) at a ratio of 0.1:1. After mixing, transfer it to a rotary evaporator and perform rotary evaporation to remove water at 70°C. After the water is completely removed, reduce it with hydrogen at 400°C for 4h to obtain Re / H-ZSM-5 zeolite molecular sieve.

[0045] 3) Take the Re / H-ZSM-5 zeolite molecular sieve powder of step 2) in a beaker, weigh 1.65g of ruthenium nitrate (Ru content 20%) and 1.65g of platinum nitrate (Pt content 20%) respectively, mix them, and then mix them with 7.5g of deionized water. The metal salt aqueous solution is impregnated into the Re / H-ZSM-5 zeolite molecular sieve powder by an equal volume method, left at room temperature for 24h, dried at 110°C for 10h, reduced with hydrogen at a temperature of 300°C and a reduction time of 3h to obtain a Re-Ru-Pt / H-ZSM-5 catalyst, named C5.

[0046] Comparative Example 1

[0047] The difference from Example 1 is that the active metal is only Re element, and does not contain Ru and Pt active metals. Other conditions are the same as Example 1, and the catalyst is named D-1.

[0048] Comparative Example 2

[0049] The difference from Example 1 is that the active metal does not contain Re element, but contains two active metals, Ru and Pt. Other conditions are the same as Example 1. The catalyst is named D-2.

[0050] Comparative Example 3

[0051] The difference from Example 1 is that activated carbon is used as the catalyst carrier, and other conditions are the same as Example 1. The catalyst is named D-3.

[0052] Table 1 Catalyst properties and composition data of Examples 1-5

[0053]

[0054] Table 2 Comparative Examples 1-3 Catalyst Properties and Composition Data

[0055]

[0056] The evaluation conditions are as follows:

[0057] The catalyst test was carried out in a 100 mL hydrogenation autoclave. The mass ratio of each precious metal catalyst prepared in the above embodiment to the reactant (malic acid) was 1:10, the solvent was tetrahydrofuran, the reaction temperature was 135° C., the rotation speed was 850 r / min, the hydrogen pressure was 10.0 MPa, and the reaction time was 12 h.

[0058] Conversion rate: The target product, by-products and raw materials were analyzed by liquid chromatography area normalization 100% quantification method.

[0059]

[0060] Optional:

[0061] Table 2 Evaluation data of examples and commercial catalysts

[0062]

[0063] As can be seen from Table 2, under the same evaluation conditions, the conversion rate of the catalyst of the present invention is above 75.6%, and the selectivity is above 44.2%.

[0064] In summary, the present invention uses ultra-high silicon-aluminum ratio zeolite molecular sieve as a catalyst carrier, and the prepared bifunctional ternary supported precious metal catalyst uses malic acid as a raw material to prepare α-hydroxy-γ-butyrolactone under mild reaction system conditions, with high reaction activity and selectivity, and simultaneously carries out hydrogenation and lactonization reactions in the reaction system to directly obtain α-hydroxy-γ-butyrolactone, with a conversion rate of more than 75.6% and a selectivity higher than 44.2%, while the catalyst conversion rate of comparative example 2 is the highest, which is only 55.2%, and the catalyst selectivity of comparative example 1 is the highest, which is only 26.9%. The technical method of the present invention has a simple reaction process, cheap and easy-to-obtain raw materials, high safety in use, and is suitable for mass production of α-hydroxy-γ-butyrolactone.

Claims

1. A ternary supported noble metal catalyst, characterized in that: The ultra-high silicon-aluminum ratio zeolite molecular sieve is used as a catalyst carrier, and a combination of metals Re, Ru and Pt is used as a catalyst active metal component; wherein, by weight percentage, the zeolite molecular sieve accounts for 82-84% and the active metal accounts for 16-18%.

2. The ternary supported noble metal catalyst according to claim 1, characterized in that: The specific surface area of ​​the catalyst is 200-500m 2 / g, with a total pore volume of 0.3-0.4cm 3 / g, the silicon-to-aluminum ratio (atomic ratio) is 200-400.

3. The ternary supported noble metal catalyst according to claim 1, characterized in that: The metal mass ratio of the active metal is Re:Ru:Pt=2-6:1:

1.

4. The ternary supported noble metal catalyst according to claim 3, characterized in that: The Re metal is one or both of ammonium perrhenate and perrhenic acid, the Ru metal is one or both of ruthenium nitrate and ruthenium chloride, and the Pt metal is one or both of platinum nitrate and platinum nitrate.

5. The ternary supported noble metal catalyst according to claim 1, characterized in that: The carriers are all H-type zeolite molecular sieves with a specific surface area of ​​300-800m 2 / g, pore volume is 0.3-0.6cm 3 / g.

6. A method for preparing the ternary supported noble metal catalyst according to claim 1, characterized in that: 1) mixing the zeolite molecular sieve and a deionized water solution, and preparing a slurry by ultrasonic dispersion and stirring; 2) preparing a metal salt solution, dissolving a metal salt containing Re in water, mixing the solution with the slurry obtained in step 1), stirring the solution thoroughly, removing water by rotary evaporation, and reducing the solution with high-temperature hydrogen to obtain a Re / zeolite molecular sieve; 3) The Re / zeolite molecular sieve powder obtained in step 2) is immersed in an aqueous solution containing Ru and Pt metal salts by an equal volume method, left at room temperature, dried, and then reduced with high temperature hydrogen to obtain a catalyst Re-Ru-Pt / zeolite molecular sieve.

7. The method for preparing the ternary supported noble metal catalyst according to claim 6, characterized in that: In step 1), the molecular sieve and deionized water are mixed in a mass ratio of 1:28-33, the ultrasonic time is 5-10 minutes, and the mixture is stirred and mixed; In step 2), the mass ratio of metal Re to water in the Re metal salt aqueous solution is 1:200, and the mixture is stirred and mixed, and then the mixture is mixed with the slurry obtained in step 1) at a ratio of 0.1:1, and then the mixture is rotary evaporated at 65-75°C, and then the reduction temperature is 350-450°C in the presence of hydrogen, and the reduction time is 3-6h; In step 3), an aqueous solution containing Ru and Pt metal salts is prepared, and the Re / zeolite molecular sieve is impregnated therein by an equal volume method, placed at room temperature for 12-24 hours, dried at 110°C for 6-10 hours, and reduced in hydrogen at a temperature of 250-350°C for 2-4 hours to obtain a catalyst Re-Ru-Pt / zeolite molecular sieve.

8. An application of the ternary supported noble metal catalyst according to claim 1, characterized in that: The catalyst is used in preparing 2-hydroxy-γ-butyrolactone by hydrogenating malic acid.

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