Ester hydrogenation catalyst and method of making and use in the hydrogenation of dimethyl succinate to 1,4-butanediol

Abstract

The present application provides an ester hydrogenation catalyst, which is applied to the reaction of preparing 1,4-butanediol by hydrogenating dimethyl succinate, and the ester hydrogenation catalyst comprises a main catalyst and a carrier; the main catalyst comprises copper oxide, manganese oxide and aluminum oxide; the carrier comprises silicon oxide and zirconium oxide; the content of the copper oxide is 20-50% by weight percentage of the ester hydrogenation catalyst, the content of the manganese oxide is 5-15%, the content of the aluminum oxide is 10-25%, and the content of the carrier is 30-45%; the carrier has a large specific surface area, which is beneficial to the dispersion of active centers and improves the catalytic activity of the ester hydrogenation catalyst; there is a certain interaction between the zirconium species and the active centers, which limits the migration and agglomeration of the active centers, so that the ester hydrogenation catalyst exhibits excellent stability. The present application also provides a preparation method of the ester hydrogenation catalyst and the application of the ester hydrogenation catalyst in the preparation of 1,4-butanediol by hydrogenating dimethyl succinate.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of ester hydrogenation catalysts, in particular to an ester hydrogenation catalyst, a preparation method and an application in the preparation of 1,4-butanediol by hydrogenation of dimethyl succinate. BACKGROUND

[0002] 1,4-butanediol is an important organic and fine chemical raw material, which is widely used in pharmaceutical, textile, papermaking, automobile and daily chemical industry. The downstream products of 1,4-butanediol mainly include tetrahydrofuran, gamma-butyrolactone, polybutylene terephthalate, polyurethane resin, coating and plasticizer, etc. In recent years, the demand for thermoplastic elastic fiber and elastomer has grown rapidly, and the demand for its monomer polytetramethylene ether glycol and polytetrahydrofuran has also been increasing, which has led to a rapid increase in the demand for upstream 1,4-butanediol. At the same time, with the high-end of fine chemical products, 1,4-butanediol as an important organic chemical intermediate of fine chemicals has also been paid more and more attention by people. Therefore, the development of 1,4-butanediol production technology has very important significance.

[0003] Chinese patent with publication number CN103566945B discloses a copper-manganese-aluminum catalyst for preparing 1,4-butanediol by hydrogenation of dimethyl maleate. The activity evaluation test of the copper-manganese-aluminum catalyst is carried out in a granular form instead of the tablet form commonly used in industrial production, which weakens the reference significance of the activity of the copper-manganese-aluminum catalyst to actual production, and the stability of the copper-manganese-aluminum catalyst is unknown. Chinese patent with publication number CN105820038A discloses a method for preparing 1,4-butanediol by hydrogenation of dimethyl succinate, which adopts a method combining pre-hydrogenation and supplementary refining. The production process is relatively complicated, which leads to an increase in production cost. Chinese patent with publication number CN102784651B discloses a high-selectivity catalyst for preparing 1,4-butanediol by hydrogenation of dimethyl succinate and a preparation method thereof. The CuO / ZnO / CeO2 / support (the support is selected from Al2O3, SiO2, MgO, TiO2, activated carbon and mixtures thereof) catalyst exhibits very high activity and selectivity of 1,4-butanediol, but the reaction is carried out in a micro-reactor. Compared with the reactor used by industrial catalysts, the micro-reactor has great advantages in mass transfer, heat transfer and constant temperature. The micro-reactor is not suitable for large-scale process production of conventional chemicals, so the reaction process in the micro-reactor is not comparable to the reaction process of industrial grade, and the reaction process in the micro-reactor has the disadvantages of high cost and low yield. SUMMARY

[0004] The ester hydrogenation catalyst has high catalytic activity and excellent stability, and can maintain good catalytic performance in the reaction of preparing 1,4-butanediol by hydrogenation of dimethyl succinate for more than 1000 hours.

[0005] To achieve the above object, the ester hydrogenation catalyst is applied to the reaction of preparing 1,4-butanediol by hydrogenation of dimethyl succinate, and the ester hydrogenation catalyst comprises a main catalyst and a carrier.

[0006] The main catalyst comprises copper oxide, manganese oxide and aluminum oxide.

[0007] The carrier comprises silicon oxide and zirconium oxide.

[0008] The content of the copper oxide is 20-50%, the content of the manganese oxide is 5-15%, the content of the aluminum oxide is 10-25%, and the content of the carrier is 30-45%, based on the weight percentage of the ester hydrogenation catalyst.

[0009] The ester hydrogenation catalyst has the beneficial effects that: by comprising the main catalyst and the carrier, the main catalyst comprising copper oxide, manganese oxide and aluminum oxide, and the carrier comprising silicon oxide and zirconium oxide, the content of the copper oxide being 20-50%, the content of the manganese oxide being 5-15%, the content of the aluminum oxide being 10-25%, and the content of the carrier being 30-45%, based on the weight percentage of the ester hydrogenation catalyst, the carrier composed of the silicon oxide and the zirconium oxide has a large specific surface area, which is beneficial to the dispersion of the active centers of the ester hydrogenation catalyst on the surface of the carrier, thereby greatly improving the catalytic activity of the ester hydrogenation catalyst. There is a certain interaction between the zirconium species and the active centers of the ester hydrogenation catalyst, which limits the migration and aggregation of the active centers of the ester hydrogenation catalyst, so that the ester hydrogenation catalyst has excellent stability. At the same time, the ester hydrogenation catalyst can maintain good catalytic performance in the reaction of preparing 1,4-butanediol by hydrogenation of dimethyl succinate for more than 1000 hours.

[0010] Optionally, the molar ratio of the silicon oxide and the zirconium oxide is (2.0-6.0):1. Its beneficial effect lies in that when the content of the zirconium oxide is higher, it will be deposited in the pores of the ester hydrogenation catalyst, reducing the specific surface area of the ester hydrogenation catalyst, and being not conducive to the dispersion of the active centers of the ester hydrogenation catalyst; when the content of the zirconium oxide is lower, the number of Zr-O-Si bonds formed in the carrier is reduced, and the unbalanced charge sites formed on the surface of the carrier are also reduced, thereby reducing the sites for interaction between the carrier and the active centers of the ester hydrogenation catalyst, and ultimately affecting the catalytic performance of the ester hydrogenation catalyst.

[0011] Optionally, the ester hydrogenation catalyst further comprises a molding aid, and the content of the molding aid is not more than 2% by mass percentage of the ester hydrogenation catalyst.

[0012] Optionally, the particle strength of the ester hydrogenation catalyst is not less than 100 Newton. Its beneficial effect lies in that the ester hydrogenation catalyst is not easy to break during use, avoiding the formation of fine particles due to the breaking of the ester hydrogenation catalyst, which causes high bed pressure drop or flow deviation phenomenon, thereby shortening the service life of the ester hydrogenation catalyst.

[0013] Optionally, the specific surface area of the ester hydrogenation catalyst is 130-210 m 2 / g, the pore volume is 0.16-0.55 cm 3 / g, and the average pore size is 3.4-7.5 nm. Its beneficial effect lies in that suitable surface properties are provided, which is conducive to the good dispersion of the active centers of the ester hydrogenation catalyst.

[0014] Another object of the present application is to provide a preparation method of the ester hydrogenation catalyst, comprising the following steps:

[0015] S1: fully impregnating a zirconium precursor solution and a silicon precursor to obtain a wet carrier precursor, and sequentially performing drying treatment and calcination treatment on the wet carrier precursor to obtain a carrier;

[0016] S2: providing a precursor solution containing copper, manganese and aluminum and a suspension of the carrier, and using an aqueous precipitant solution and the precursor solution to perform co-precipitation treatment on the suspension at 50-80 degrees Celsius to obtain a co-precipitate slurry with a pH value of 6.5-8.0;

[0017] S3: performing aging treatment on the co-precipitate slurry at 30-60 degrees Celsius for 1-3 hours, and then performing filtration treatment and washing treatment on the co-precipitate slurry obtained after the aging treatment to obtain a catalyst precursor precipitate;

[0018] S4: sequentially performing drying treatment and calcination treatment on the catalyst precursor precipitate to obtain catalyst particle powder;

[0019] S5: performing molding treatment on the catalyst particle powder using a molding aid to obtain the ester hydrogenation catalyst.

[0020] The method for preparing the ester hydrogenation catalyst has the advantages that a precursor solution containing copper, manganese and aluminum and a suspension of the carrier are provided, a precipitant aqueous solution and the precursor solution are used to perform coprecipitation treatment on the suspension at 50-80 degrees Celsius to obtain a coprecipitate slurry with a pH value of 6.5-8.0, the coprecipitate slurry is subjected to aging treatment at 30-60 degrees Celsius for 1-3 hours, and then the coprecipitate slurry obtained after the aging treatment is subjected to filtration treatment and washing treatment to obtain a catalyst precursor precipitate; the catalyst precursor precipitate is sequentially subjected to drying treatment and calcination treatment to obtain catalyst particle powder; and the catalyst particle powder is subjected to molding treatment using a molding aid to obtain the ester hydrogenation catalyst. The carrier composed of the silicon oxide and the zirconium oxide has a large specific surface area, which is beneficial to the dispersion of active centers of the ester hydrogenation catalyst on the surface of the carrier, thereby greatly improving the catalytic activity of the ester hydrogenation catalyst. There is a certain interaction between the zirconium species and the active centers of the ester hydrogenation catalyst, which limits the migration and aggregation of the active centers of the ester hydrogenation catalyst, thereby making the ester hydrogenation catalyst have excellent stability. Meanwhile, the ester hydrogenation catalyst prepared by the method can still maintain good catalytic performance after running for more than 1000 hours in the reaction of preparing 1,4-butanediol by hydrogenating dimethyl succinate. Meanwhile, the method provided by the present application has the advantages of simple process, easy operation, easy availability of raw materials, economy, environmental protection and easy industrialization.

[0021] Optionally, the silicon precursor is fumed silica.

[0022] Optionally, the precursor in the precursor solution is any one of a nitrate, an acetate and an oxalate.

[0023] Optionally, the precipitant of the precipitant aqueous solution is one or more of sodium carbonate, sodium hydroxide, potassium carbonate and potassium hydroxide.

[0024] Optionally, in the step S1, the drying temperature of the drying treatment is 120-150 degrees Celsius, the drying time of the drying treatment is 10-14 hours, the calcination temperature of the calcination treatment is 600-800 degrees Celsius, and the calcination time of the calcination treatment is 4-8 hours.

[0025] Optionally, in the step S4, the drying temperature of the drying treatment is 100-120 degrees Celsius, the drying time of the drying treatment is 12-20 hours, the calcination temperature of the calcination treatment is 400-600 degrees Celsius, and the calcination time of the calcination treatment is 4-8 hours.

[0026] Optionally, the step of the forming treatment comprises: after mixing the forming aid with the catalyst particle powder, performing a tabletting treatment to obtain the ester hydrogenation catalyst, the mass percentage of the forming aid in the ester hydrogenation catalyst is not more than 2%, and the forming aid is graphite powder.

[0027] Another object of the present application is to provide an application of the ester hydrogenation catalyst in the preparation of 1,4-butanediol by hydrogenation of dimethyl succinate, the ester hydrogenation catalyst is loaded in a fixed bed reactor, the ester hydrogenation catalyst is reduced by a reducing gas to form a pretreated ester hydrogenation catalyst, liquid dimethyl succinate and hydrogen gas flow through the pretreated ester hydrogenation catalyst to perform a hydrogenation reaction to prepare 1,4-butanediol, and the temperature of the hydrogenation reaction is controlled to be 150-230 degrees Celsius, and the pressure of the hydrogenation reaction is 5-8 MPa.

[0028] The application of the ester hydrogenation catalyst in the preparation of 1,4-butanediol by hydrogenation of dimethyl succinate has the beneficial effects that: the ester hydrogenation catalyst is loaded in a fixed bed reactor, the ester hydrogenation catalyst is reduced by a reducing gas to form a pretreated ester hydrogenation catalyst, liquid dimethyl succinate and hydrogen gas flow through the pretreated ester hydrogenation catalyst to perform a hydrogenation reaction to prepare 1,4-butanediol, and the temperature of the hydrogenation reaction is controlled to be 150-230 degrees Celsius, and the pressure of the hydrogenation reaction is 5-8 MPa. In the application of the ester hydrogenation catalyst in the preparation of 1,4-butanediol by hydrogenation of dimethyl succinate, dimethyl succinate is directly hydrogenated on the ester hydrogenation catalyst to prepare 1,4-butanediol product, the process is continuous, and the production efficiency is high. Moreover, under the condition of a relatively low reaction temperature, the raw material can be almost completely converted, and the selectivity of the 1,4-butanediol product is as high as 97% or more.

[0029] Optionally, the molar ratio of the hydrogen gas to the liquid dimethyl succinate is (100-500):1, the volume space velocity of the liquid dimethyl succinate is 0.1-2.0 hours -1 .

[0030] Optionally, the reducing gas comprises hydrogen and inert gas, the hydrogen in the reducing gas accounts for not less than 1% of the volume percentage of the reducing gas, the temperature for reducing the ester hydrogenation catalyst is 150-200 DEG C, and the time for reducing the ester hydrogenation catalyst is 2-20 hours. The beneficial effect lies in that the ester hydrogenation catalyst is reduced at a lower temperature, which is beneficial to energy saving and emission reduction, reduces energy consumption, and promotes the realization of the double carbon goal. DETAILED DESCRIPTION

[0031] To make the objectives, technical solutions, and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be described below in a clear and complete manner. Obviously, the described embodiments are only some, but not all of the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative work fall within the protection scope of the present application. Unless otherwise defined, the technical terms or scientific terms used herein should be understood as the general meanings understood by those of ordinary skill in the art to which the present application belongs. The terms such as “comprise” and the like used herein mean that the elements or objects before the terms encompass the elements or objects listed after the terms and their equivalents, without excluding other elements or objects.

[0032] To solve the problems in the prior art, the embodiments of the present application provide an ester hydrogenation catalyst applied to the reaction of preparing 1,4-butanediol by hydrogenating dimethyl succinate, wherein the ester hydrogenation catalyst comprises a main catalyst and a carrier.

[0033] The main catalyst comprises copper oxide, manganese oxide, and aluminum oxide.

[0034] The carrier comprises silicon oxide and zirconium oxide.

[0035] The content of the copper oxide is 20-50% by weight percentage of the ester hydrogenation catalyst, the content of the manganese oxide is 5-15% by weight percentage of the ester hydrogenation catalyst, the content of the aluminum oxide is 10-25% by weight percentage of the ester hydrogenation catalyst, and the content of the carrier is 30-45% by weight percentage of the ester hydrogenation catalyst. The carrier composed of the silicon oxide and the zirconium oxide has a large specific surface area, which is beneficial to the dispersion of the active centers of the ester hydrogenation catalyst on the surface of the carrier, thereby greatly improving the catalytic activity of the ester hydrogenation catalyst. There is a certain interaction between the zirconium species and the active centers of the ester hydrogenation catalyst, which limits the migration and aggregation of the active centers of the ester hydrogenation catalyst, thereby making the ester hydrogenation catalyst have excellent stability. Meanwhile, the ester hydrogenation catalyst can still maintain good catalytic performance after running for more than 1000 hours in the reaction of preparing 1,4-butanediol by hydrogenating dimethyl succinate.

[0036] In some embodiments of the present application, the molar ratio of the silicon oxide and the zirconium oxide is (2.0-6.0):1. When the content of the zirconium oxide is high, it will be deposited in the pores of the ester hydrogenation catalyst, reducing the specific surface area of the ester hydrogenation catalyst, and being not conducive to the dispersion of the active centers of the ester hydrogenation catalyst; when the content of the zirconium oxide is low, the number of Zr-O-Si bonds formed in the carrier is reduced, and the unbalanced charge sites formed on the surface of the carrier are also reduced, thereby reducing the interaction sites between the carrier and the active centers of the ester hydrogenation catalyst, and ultimately affecting the catalytic performance of the ester hydrogenation catalyst.

[0037] In some embodiments of the present application, the ester hydrogenation catalyst further comprises a molding aid, and the content of the molding aid is not more than 2% based on the mass percentage of the ester hydrogenation catalyst.

[0038] In some embodiments of the present application, the shape of the ester hydrogenation catalyst is cylindrical, and the diameter of the cylindrical shape is 4 mm and the height is 3 mm.

[0039] In some embodiments of the present application, the particle strength of the ester hydrogenation catalyst is not less than 100 N. This makes the ester hydrogenation catalyst not easy to break during use, avoids the formation of fine particles due to the breaking of the ester hydrogenation catalyst, which causes high bed pressure drop or flow deviation phenomenon, thereby shortening the service life of the ester hydrogenation catalyst.

[0040] In some embodiments of the present application, the specific surface area of the ester hydrogenation catalyst is 130-210 m 2 / g, the pore volume is 0.16-0.55 cm 3 / g, and the average pore size is 3.4-7.5 nm. This provides suitable surface properties, which is conducive to the good dispersion of the active centers of the ester hydrogenation catalyst.

[0041] Embodiments of the present application provide a preparation method of the ester hydrogenation catalyst, comprising the following steps:

[0042] S1: fully impregnating a zirconium precursor solution and a silicon precursor to obtain a wet carrier precursor, and sequentially performing drying treatment and calcination treatment on the wet carrier precursor to obtain a carrier;

[0043] S2: providing a suspension of a carrier and a precursor solution containing copper, manganese and aluminum, and using an aqueous precipitant solution and the precursor solution to perform co-precipitation treatment on the suspension at 50-80°C to obtain a co-precipitate slurry with a pH value of 6.5-8.0;

[0044] S3: aging the coprecipitate slurry at 30-60 degrees Celsius for 1-3 hours, and then filtering and washing the coprecipitate slurry after the aging to obtain a catalyst precursor precipitate;

[0045] S4: sequentially drying and calcining the catalyst precursor precipitate to obtain a catalyst particle powder;

[0046] S5: using a forming aid to form the catalyst particle powder to obtain the ester hydrogenation catalyst. The carrier composed of the silicon oxide and the zirconium oxide has a large specific surface area, which is beneficial to the dispersion of active centers of the ester hydrogenation catalyst on the surface of the carrier, thereby greatly improving the catalytic activity of the ester hydrogenation catalyst. There is a certain interaction between the zirconium species and the active centers of the ester hydrogenation catalyst, which limits the migration and aggregation of the active centers of the ester hydrogenation catalyst, so that the ester hydrogenation catalyst has excellent stability. Meanwhile, the ester hydrogenation catalyst prepared by the preparation method can maintain good catalytic performance for more than 1000 hours in the reaction of preparing 1,4-butanediol by hydrogenating dimethyl succinate. Meanwhile, the preparation method provided by the present application has the advantages of simple process, easy operation, easy-to-obtain raw materials, economy, environmental protection, and easy industrialization.

[0047] In some embodiments of the present application, the silicon precursor is fumed silica.

[0048] In some embodiments of the present application, the precursor in the precursor solution is any one of a nitrate, an acetate and an oxalate.

[0049] In some embodiments of the present application, the precipitant of the precipitant aqueous solution is one or more of sodium carbonate, sodium hydroxide, potassium carbonate and potassium hydroxide.

[0050] In some embodiments of the present application, in the step S1, the drying temperature of the drying treatment is 120-150 degrees Celsius, the drying time of the drying treatment is 10-14 hours, the calcination temperature of the calcination treatment is 600-800 degrees Celsius, and the calcination time of the calcination treatment is 4-8 hours.

[0051] In some embodiments of the present application, in the step S2, the drying temperature of the drying treatment is 100-120 degrees Celsius, the drying time of the drying treatment is 12-20 hours, the calcination temperature of the calcination treatment is 400-600 degrees Celsius, and the calcination time of the calcination treatment is 4-8 hours.

[0052] In some embodiments of the present application, the step of the shaping treatment comprises tabletting the mixture of the shaping aid and the catalyst particle powder to obtain the ester hydrogenation catalyst, the mass percentage of the shaping aid in the ester hydrogenation catalyst is not more than 2%, and the shaping aid is graphite powder.

[0053] In some embodiments of the present application, the ester hydrogenation catalyst is used in the preparation of 1,4-butanediol by hydrogenation of dimethyl succinate. The ester hydrogenation catalyst is loaded in a fixed bed reactor, and the ester hydrogenation catalyst is reduced by a reducing gas to form a pretreated ester hydrogenation catalyst. Liquid dimethyl succinate and hydrogen gas flow through the pretreated ester hydrogenation catalyst to carry out a hydrogenation reaction to obtain 1,4-butanediol. The temperature of the hydrogenation reaction is controlled at 150-230℃, and the pressure of the hydrogenation reaction is controlled at 5-8 MPa. In the application of preparing 1,4-butanediol by hydrogenation of dimethyl succinate, dimethyl succinate is directly hydrogenated on the ester hydrogenation catalyst to prepare 1,4-butanediol product. The process is continuous, and the production efficiency is high. In addition, under the condition of lower reaction temperature, the raw material can be almost completely converted, and the selectivity of 1,4-butanediol product is as high as 97% or more.

[0054] In some embodiments of the present application, the molar ratio of hydrogen gas to liquid dimethyl succinate is (100-500):1, and the volume space velocity of the liquid dimethyl succinate is 0.1-2.0 h-1. -1 .

[0055] In some embodiments of the present application, the reducing gas comprises hydrogen gas and inert gas, the volume percentage of hydrogen gas in the reducing gas is not less than 1%, the temperature for reducing the ester hydrogenation catalyst is 150-200℃, and the time for reducing the ester hydrogenation catalyst is 2-20 hours. The ester hydrogenation catalyst is reduced at a lower temperature, which is beneficial to energy saving and emission reduction, reduces energy consumption, and promotes the realization of the double carbon goal.

[0056] In some embodiments of the present application, the zirconium precursor solution is a zirconium nitrate pentahydrate solution.

[0057] In some embodiments of the present application, the step S1 in embodiments 1-6 is: weighing a zirconium precursor, dissolving it in deionized water to prepare a zirconium precursor solution, and then dripping and impregnating the zirconium precursor solution into fumed silica, mixing uniformly, and then standing and aging at room temperature for 4-6 hours to obtain a wet carrier precursor. Then, the wet carrier precursor is sequentially subjected to drying treatment and calcination treatment to obtain the carrier.

[0058] The step S2 in the embodiments 1-6 of the present application is: weighing copper precursor, manganese precursor and aluminum precursor, and dissolving them in deionized water to obtain a precursor solution containing copper, manganese and aluminum, i.e. a metal ion salt solution; weighing sodium carbonate and sodium hydroxide, and dissolving them in deionized water to obtain the precipitant aqueous solution; weighing the carrier and adding it to deionized water to prepare a suspension of the carrier. Under the condition of water bath stirring at 50-80 degrees Celsius, the metal ion salt solution and the precipitant aqueous solution are added to the suspension in parallel flow, and the pH value of the solution is controlled at 6.5-8.0 during the adding process. After the adding process is completed, a coprecipitate slurry is obtained.

[0059] The step S3 in the embodiments 1-6 of the present application is: aging the coprecipitate slurry, and then filtering and washing the coprecipitate slurry obtained after the aging to obtain a catalyst precursor precipitate.

[0060] The step S4 in the embodiments 1-6 of the present application is: washing the catalyst precursor precipitate with deionized water, and then sequentially drying and calcining the catalyst precursor precipitate after the washing to obtain a catalyst particle powder.

[0061] The step S5 in the embodiments 1-6 of the present application is: tabletting the catalyst particle powder using graphite powder to obtain the ester hydrogenation catalyst.

[0062] In the embodiments 1-6 of the present application, the zirconium precursor is zirconium nitrate pentahydrate, and the aluminum precursor is aluminum nitrate nonahydrate.

[0063] In the embodiment 1 of the present application, the copper precursor is copper acetate monohydrate, the manganese precursor is manganese nitrate tetrahydrate, the drying in the step S1 is performed at a drying temperature of 130 degrees Celsius for 13 hours, the calcination in the step S1 is performed at a calcination temperature of 700 degrees Celsius for 6 hours, the aging in the step S3 is performed at an aging temperature of 40 degrees Celsius for 2 hours, the drying in the step S4 is performed at a drying temperature of 110 degrees Celsius for 16 hours, and the calcination in the step S4 is performed at a calcination temperature of 450 degrees Celsius for 4 hours.

[0064] In the embodiment 2 of the present application, the copper precursor is copper sulfate pentahydrate, the manganese precursor is manganese acetate tetrahydrate, the drying in the step S1 is performed at a drying temperature of 140 degrees Celsius for 10 hours, the calcination in the step S1 is performed at a calcination temperature of 600 degrees Celsius for 4 hours, the aging in the step S3 is performed at an aging temperature of 50 degrees Celsius for 2 hours, the drying in the step S4 is performed at a drying temperature of 100 degrees Celsius for 18 hours, and the calcination in the step S4 is performed at a calcination temperature of 500 degrees Celsius for 4 hours.

[0065] In the embodiment 3 of the present application, the copper precursor is copper sulfate pentahydrate, the manganese precursor is manganese sulfate tetrahydrate, the drying treatment in the step S1 is drying for 11 hours at a drying temperature of 120 degrees Celsius, the calcination treatment in the step S1 is calcination for 5 hours at a calcination temperature of 750 degrees Celsius, the aging treatment in the step S3 is aging for 3 hours at an aging temperature of 40 degrees Celsius, the drying treatment in the step S4 is drying for 12 hours at a drying temperature of 120 degrees Celsius, and the calcination treatment in the step S4 is calcination for 6 hours at a calcination temperature of 500 degrees Celsius.

[0066] In the embodiment 4 of the present application, the copper precursor is copper nitrate trihydrate, the manganese precursor is manganese nitrate tetrahydrate, the drying treatment in the step S1 is drying for 12 hours at a drying temperature of 120 degrees Celsius, the calcination treatment in the step S1 is calcination for 4 hours at a calcination temperature of 650 degrees Celsius, the aging treatment in the step S3 is aging for 2 hours at an aging temperature of 45 degrees Celsius, the drying treatment in the step S4 is drying for 14 hours at a drying temperature of 120 degrees Celsius, and the calcination treatment in the step S4 is calcination for 6 hours at a calcination temperature of 450 degrees Celsius.

[0067] In the embodiment 5 of the present application, the copper precursor is copper acetate monohydrate, the manganese precursor is manganese sulfate tetrahydrate, the drying treatment in the step S1 is drying for 10 hours at a drying temperature of 130 degrees Celsius, the calcination treatment in the step S1 is calcination for 6 hours at a calcination temperature of 700 degrees Celsius, the aging treatment in the step S3 is aging for 3 hours at an aging temperature of 50 degrees Celsius, the drying treatment in the step S4 is drying for 14 hours at a drying temperature of 110 degrees Celsius, and the calcination treatment in the step S4 is calcination for 8 hours at a calcination temperature of 550 degrees Celsius.

[0068] In the embodiment 6 of the present application, the copper precursor is copper nitrate trihydrate, the manganese precursor is manganese nitrate tetrahydrate, the drying treatment in the step S1 is drying for 12 hours at a drying temperature of 120 degrees Celsius, the calcination treatment in the step S1 is calcination for 5 hours at a calcination temperature of 650 degrees Celsius, the aging treatment in the step S3 is aging for 3 hours at an aging temperature of 45 degrees Celsius, the drying treatment in the step S4 is drying for 12 hours at a drying temperature of 120 degrees Celsius, and the calcination treatment in the step S4 is calcination for 6 hours at a calcination temperature of 450 degrees Celsius.

[0069] Table 1: Proportions of components and catalyst parameters in embodiments 1-6

[0070]

[0071] The present application also provides Comparative Examples 1-3 to prepare reference catalysts.

[0072] In some embodiments of the present application, the carrier of Comparative Example 1 and Comparative Example 2 does not contain zirconium nitrate pentahydrate, and the remaining components in Comparative Example 1 and the components in Examples 1-6 are the same; the metal ion salt solution in Comparative Example 2 is composed of copper nitrate trihydrate, zinc nitrate hexahydrate and aluminum nitrate nonahydrate, and the remaining components in Comparative Example 2 and the components in Examples 1-6 are the same; Comparative Example 3 does not contain a carrier, and the remaining components in Comparative Example 3 and the components in Examples 1-6 are the same.

[0073] In some embodiments of the present application, the preparation methods of Comparative Example 1, Comparative Example 2 and Comparative Example 3 are the same as the preparation methods of Examples 1-6, and finally reference catalyst 1, reference catalyst 2 and reference catalyst 3 are prepared.

[0074] Specifically, the content of each component in the reference catalyst 1 is as follows: the content of copper oxide is 41.0%, the content of manganese oxide is 9.0%, the content of aluminum oxide is 15.1%, and the content of silicon oxide is 34.0%; the specific surface area of the reference catalyst 1 is 189.2 m 2 / g, the pore volume is 0.45 cm 3 / g, and the average pore size is 5.6 nm.

[0075] Specifically, the content of each component in the reference catalyst 2 is as follows: the content of copper oxide is 53.5%, the content of zinc oxide is 35.7%, and the content of aluminum oxide is 10.8%; the specific surface area of the reference catalyst 2 is 35.0 m 2 / g, the pore volume is 0.09 cm 3 / g, and the average pore size is 7.3 nm; the shape of the reference catalyst 2 is cylindrical, the diameter of the reference catalyst 2 is 5 mm, and the height of the reference catalyst 2 is 5 mm.

[0076] Specifically, the content of each component in the reference catalyst 3 is as follows: the content of copper oxide is 55.8%, the content of manganese oxide is 7.3%, and the content of aluminum oxide is 36.9%; the specific surface area of the reference catalyst 3 is 34.1 m 2 / g, the pore volume is 0.11 cm 3 / g, and the average pore size is 8.5 nm; the shape of the reference catalyst 3 is cylindrical, the diameter of the reference catalyst 3 is 5 mm, and the height of the reference catalyst 3 is 3 mm.

[0077] The application provides an application of the ester hydrogenation catalyst in preparation of 1,4-butanediol by hydrogenation of dimethyl succinate, the ester hydrogenation catalyst is filled in a fixed bed reactor, the ester hydrogenation catalyst is reduced by a reducing gas to form a pretreated ester hydrogenation catalyst, liquid dimethyl succinate and hydrogen gas flow through the pretreated ester hydrogenation catalyst to perform a hydrogenation reaction to prepare 1,4-butanediol, and the temperature of the hydrogenation reaction is controlled to be 150-230 DEG C, the pressure of the hydrogenation reaction is 5-8 MPa, the molar ratio of the hydrogen gas to the liquid dimethyl succinate is (100-500):1, the volume space velocity of the liquid dimethyl succinate is 0.1-2.0 h-1, the reducing gas comprises hydrogen gas and inert gas, the hydrogen gas accounts for not less than 1% of the reducing gas in terms of volume percentage, the temperature of the reduction of the ester hydrogenation catalyst is 150-200 DEG C, and the reduction time of the ester hydrogenation catalyst is 2-20 hours. -1

[0078] Specifically, the ester hydrogenation catalysts in embodiments 1-6 and the reference catalysts in comparative examples 1-3 are respectively reduced to form pretreated ester hydrogenation catalysts and pretreated reference catalysts, a mixed gas of hydrogen gas and helium gas is used as the reducing gas, the volume percentage of the hydrogen gas in the reducing gas is 50%, the pretreated ester hydrogenation catalysts and the pretreated reference catalysts are first reduced and activated at a first reduction temperature of 150 DEG C for 8 hours, and then are reduced and activated at a second reduction temperature of 180 DEG C for 4 hours; after the reduction is completed, the reaction temperature is adjusted to 170 DEG C, the pressure is increased to 6 MPa, the liquid dimethyl succinate is mixed with the hydrogen gas by a laminar pump and then is introduced into the fixed bed reactor and passes through the bed to contact the pretreated ester hydrogenation catalysts and the pretreated reference catalysts to perform a catalytic hydrogenation reaction.

[0079] The product obtained through the catalytic hydrogenation reaction is subjected to gas-liquid separation after condensation, and then composition analysis is performed on the liquid-phase product obtained by using a gas chromatograph, and specific results can be seen from Table 2. Table 2 also provides the reaction temperature T, the reaction pressure P, the dimethyl succinate volume space velocity V and the hydrogen-ester ratio of different embodiments and comparative examples.

[0080] Table 2 Activity evaluation results of ester hydrogenation catalysts

[0081]

[0082] Note: In Table 2, C DMS represents the conversion rate of dimethyl succinate, S BDO represents the selectivity of 1,4-butanediol, S GBL represents the selectivity of gamma-butyrolactone, S THF represents the selectivity of tetrahydrofuran.​

[0083] From the evaluation data in Table 2, it can be found that the introduction of the zirconium oxide has a beneficial effect on the improvement of the catalytic activity and selectivity of the ester hydrogenation catalyst compared with Comparative Example 1; the ester hydrogenation catalyst provided by the present application exhibits more excellent catalytic performance compared with Comparative Examples 2 and 3, which shows that the active center of the ester hydrogenation catalyst and the carrier achieve good synergy.

[0084] Further, in order to verify the catalytic activity of the ester hydrogenation catalyst in Example 4 at different temperatures, the present application maintains other process conditions unchanged, and respectively carries out activity evaluation of the ester hydrogenation catalyst in Example 4 at 150 degrees Celsius, 170 degrees Celsius, 190 degrees Celsius, 210 degrees Celsius and 230 degrees Celsius. The specific evaluation data is shown in Table 3.

[0085] Table 3 Activity evaluation results of the ester hydrogenation catalyst in Example 4

[0086]

[0087] Note: In Table 3, C DMS represents the conversion rate of dimethyl succinate, S BDO represents the selectivity of 1,4-butanediol, S GBL represents the selectivity of γ-butyrolactone, S THF represents the selectivity of tetrahydrofuran.

[0088] From the evaluation data in Table 3, it can be found that with the increase of the reaction temperature, the liquid dimethyl succinate can be completely converted, and the by-product tetrahydrofuran gradually increases, which is because high temperature is beneficial to the occurrence of dehydration reaction, and therefore in order to realize the high selectivity of the raw material to generate 1,4-butanediol product, it is not suitable to carry out at too high reaction temperature.

[0089] Further, in order to investigate the chemical stability of the ester hydrogenation catalyst in the present application, the ester hydrogenation catalyst in Example 4, Comparative Example 1, Comparative Example 2 and Comparative Example 3 are selected to carry out long-period life test experiment for more than 1000 hours. The specific evaluation data is shown in Table 4.

[0090] Table 4 Activity evaluation results of the ester hydrogenation catalyst

[0091]

[0092] Note: In Table 4, C DMS represents the conversion rate of dimethyl succinate, S BDO represents the selectivity of 1,4-butanediol, S GBL represents the selectivity of γ-butyrolactone, S THFselectivity of tetrahydrofuran.

[0093] As can be seen from Table 4, the performance of the ester hydrogenation catalyst in Example 4 of the present application does not show obvious decline after long period operation for more than 1000 hours, which indicates that the ester hydrogenation catalyst provided by the present application has excellent catalytic activity, stability and service life.

[0094] Furthermore, the present application also provides comparative data of the particle strength of the catalyst in Example 4 and Comparative Examples 1-3 before and after long period operation, and the specific data can be seen from Table 5.

[0095] Table 5 Physical property data of the catalyst in Example 4 and Comparative Examples 1-3

[0096]

[0097] As can be seen from Table 4 and Table 5, the particle strength of the ester hydrogenation catalyst in Example 4 of the present application is obviously higher than that of the reference catalyst in Comparative Examples 1-3, which indicates that the particle strength of the catalyst also plays a very important role in the performance, stability and service life of the catalyst.

[0098] Although the embodiments of the present application have been described in detail above, it is obvious for those skilled in the art that various modifications and changes can be made to the embodiments. However, it should be understood that such modifications and changes all belong to the scope and spirit of the present application described in the claims. Moreover, the present application described herein can have other embodiments and can be implemented or realized in various ways.

Claims

1. An ester hydrogenation catalyst characterized by, The ester hydrogenation catalyst is applied to the reaction of preparing 1,4-butanediol by hydrogenating dimethyl succinate, and comprises a main catalyst and a carrier; The main catalyst comprises copper oxide, manganese oxide and aluminum oxide; The carrier comprises silicon oxide and zirconium oxide, and the molar ratio of the silicon oxide to the zirconium oxide is (2.0-6.0):1; The content of the copper oxide is 20-50% by weight percentage of the ester hydrogenation catalyst, the content of the manganese oxide is 5-15% by weight percentage of the ester hydrogenation catalyst, the content of the aluminum oxide is 10-25% by weight percentage of the ester hydrogenation catalyst, and the content of the carrier is 30-45% by weight percentage of the ester hydrogenation catalyst, The particle strength of the ester hydrogenation catalyst is not less than 100 Newton.

2. The ester hydrogenation catalyst of claim 1, wherein, A molding aid is further included, and the content of the molding aid is not more than 2% by mass percentage of the ester hydrogenation catalyst.

3. The ester hydrogenation catalyst of claim 1, wherein The specific surface area of the ester hydrogenation catalyst is 130-210 m 2 / g, the pore volume is 0.16-0.55 cm 3 / g, and the average pore diameter is 3.4-7.5 nm.

4. A process for preparing an ester hydrogenation catalyst as claimed in any one of claims 1 to 3, characterized in that The method comprises the following steps: S1: a zirconium precursor solution and a silicon precursor are fully impregnated and mixed to obtain a wet carrier precursor, and the wet carrier precursor is sequentially subjected to a drying treatment and a calcination treatment to obtain a carrier; S2: a suspension of a carrier and a precursor solution containing copper, manganese and aluminum are provided, and a co-precipitation treatment is performed on the suspension at 50-80 degrees Celsius by using an aqueous precipitant solution and the precursor solution to obtain a co-precipitate slurry with a pH value of 6.5-8.0; S3: an aging treatment is performed on the co-precipitate slurry at 30-60 degrees Celsius for 1-3 hours, and then a filtration treatment and a washing treatment are performed on the co-precipitate slurry obtained after the aging treatment to obtain a catalyst precursor precipitate; S4: a drying treatment and a calcination treatment are sequentially performed on the catalyst precursor precipitate to obtain a catalyst particle powder; S5: a molding treatment is performed on the catalyst particle powder by using a molding aid to obtain the ester hydrogenation catalyst.

5. The method of preparing an ester hydrogenation catalyst according to claim 4, characterized in that, The silicon precursor is fumed silica.

6. The method of making an ester hydrogenation catalyst of claim 4, wherein, The precursors in the precursor solution are any one of nitrate, acetate and oxalate.

7. The method of making an ester hydrogenation catalyst of claim 4, wherein, The precipitant in the aqueous precipitant solution is one or more of sodium carbonate, sodium hydroxide, potassium carbonate and potassium hydroxide.

8. The method of making an ester hydrogenation catalyst of claim 4, wherein, In the step S1, the drying temperature of the drying treatment is 120-150 degrees Celsius, the drying time of the drying treatment is 10-14 hours, the calcination temperature of the calcination treatment is 600-800 degrees Celsius, and the calcination time of the calcination treatment is 4-8 hours.

9. The method of making an ester hydrogenation catalyst of claim 4, wherein, In the step S4, the drying temperature of the drying treatment is 100-120 degrees Celsius, the drying time of the drying treatment is 12-20 hours, the calcination temperature of the calcination treatment is 400-600 degrees Celsius, and the calcination time of the calcination treatment is 4-8 hours.

10. The method of making an ester hydrogenation catalyst of claim 4, wherein, The step of the molding treatment comprises that the molding aid is mixed with the catalyst particle powder and then tabletting treatment is performed to obtain the ester hydrogenation catalyst, the content of the molding aid is not more than 2% by mass percentage of the ester hydrogenation catalyst, and the molding aid is graphite powder.

11. Use of an ester hydrogenation catalyst as claimed in any one of claims 1 to 3 for the production of 1,4-butanediol by hydrogenation of dimethyl succinate, characterized in that, The ester hydrogenation catalyst is loaded into a fixed bed reactor, the ester hydrogenation catalyst is reduced by a reducing gas to form a pretreated ester hydrogenation catalyst, liquid dimethyl succinate and hydrogen gas flow through the pretreated ester hydrogenation catalyst to carry out a hydrogenation reaction to prepare 1,4-butanediol, and the temperature of the hydrogenation reaction is controlled to be 150-230 degrees Celsius, and the pressure of the hydrogenation reaction is 5-8 MPa.

12. Use of the ester hydrogenation catalyst according to claim 11 for the production of 1,4-butanediol by hydrogenation of dimethyl succinate, characterized in that, The molar ratio of the hydrogen gas to the liquid dimethyl succinate is (100-500): 1, and the liquid dimethyl succinate has a volume space velocity of 0.1-2.0 hours -1 .

13. Use of the ester hydrogenation catalyst according to claim 11 for the production of 1,4-butanediol by hydrogenation of dimethyl succinate, characterized in that, The reducing gas comprises hydrogen and inert gas, the hydrogen in the reducing gas accounts for not less than 1% of the volume percentage of the reducing gas, the temperature of the reduction of the ester hydrogenation catalyst is 150-200 degrees Celsius, and the time of the reduction of the ester hydrogenation catalyst is 2-20 hours.

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