Catalyst for preparing 1, 2-pentanediol from furfuryl alcohol as well as preparation method and application of catalyst

Abstract

The invention provides a catalyst for preparing 1, 2-pentanediol from furfuryl alcohol as well as a preparation method and application of the catalyst. The catalyst comprises a carrier and active components loaded on the carrier, the carrier comprises magnesium oxide and aluminum oxide, and the active components comprise a main active component and an auxiliary active component; the main active component comprises platinum, and the auxiliary active component comprises any one or a combination of at least two of yttrium, zirconium or manganese. The catalyst provided by the invention has the advantages of high stability, high activity, strong reusability and the like, the preparation method is simple, high-selectivity and high-yield 1, 2-pentanediol can be prepared from furfuryl alcohol as a raw material under mild conditions, the reaction time is short, the dosage of the catalyst is small, and the catalyst has extremely high application value.

Description

Technical Field

[0001] The present invention belongs to the field of preparing pentanediol by ring-opening hydrogenolysis of furfuryl alcohol, and relates to a catalyst for preparing 1,2-pentanediol from furfuryl alcohol, a preparation method thereof, and an application thereof. Background Art

[0002] As one of the most valuable hydrogenolysis products of furfuryl alcohol (FA) and furfural (FFA), 1,2-pentanediol (1,2PeD) is widely used in the cosmetic industry or as a key intermediate for low-toxic microbicides. At the same time, due to its excellent moisturizing and antibacterial properties, 1,2-pentanediol is widely used in baby products, bath products, cleaning products, skin care products, etc. Therefore, the direct production of 1,2-pentanediol from FA / FFA under mild conditions has attracted extensive attention from scientific researchers.

[0003] Currently, the main production process of 1,2-pentanediol is the pentene method, which mainly involves processes such as epoxidation, esterification, and hydrolysis of pentene with peroxides. However, this process has limitations in the source of pentene raw materials, and commonly used peracids (such as meta-chloroperoxybenzoic acid MCPBA) or transition metal catalytic systems are costly and pose an explosion risk during storage / use, restricting the development of 1,2-pentanediol. Therefore, developing a synthetic process route with mild reaction conditions, high continuous automation, low cost, high yield, long stability, and environmental friendliness using the widely available and inexpensive raw material furfuryl alcohol is the key to breaking through the current production bottleneck of 1,2-pentanediol.

[0004] CN201911107004.9 discloses a production method of 1,2-pentanediol, in which furfuryl alcohol is selectively hydrogenated to 1,2-pentanediol under the catalysis of a noble metal catalyst supported on a composite support. However, the highest yield of 1,2-pentanediol in the product of this process is only about 40%, and the yield of the low-value by-product tetrahydrofurfuryl alcohol reaches more than 50%.

[0005] CN108911949A discloses a method for preparing 1,2-pentanediol by liquid-phase catalytic selective hydrogenolysis of furfuryl alcohol under the action of a Cu-based catalyst. The reaction pressure of this method is 7 MPa, and the reaction temperature is 140 °C. The conversion rate of furfuryl alcohol and the selectivity of 1,2-pentanediol are 95% and 48% respectively. The limitation of this method is that when the concentration of furfuryl alcohol increases to more than 80%, the conversion rate of furfuryl alcohol drops to 23%, and the pressure required during the reaction reaches 7 MPa, and the reaction conditions are not mild enough.

[0006] Therefore, developing an efficient and stable heterogeneous catalyst to achieve high-efficiency preparation of 1,2-pentanediol under mild conditions is of great significance. Summary of the Invention

[0007] Aiming at the deficiencies of the existing technology, the purpose of the present invention is to provide a catalyst for preparing 1,2-pentanediol from furfuryl alcohol, its preparation method and application. The catalyst provided by the present invention has the advantages of high stability, high activity and strong reusability. The preparation method is simple, and 1,2-pentanediol with high selectivity and high yield can be prepared from furfuryl alcohol as a raw material under mild conditions. The reaction time is short and the catalyst dosage is small, which has extremely high application value.

[0008] To achieve this purpose, the present invention adopts the following technical solutions:

[0009] In the first aspect, the present invention provides a catalyst for preparing 1,2-pentanediol from furfuryl alcohol, the catalyst includes a carrier and an active component supported on the carrier, the carrier includes magnesium oxide and alumina, and the active component includes a main active component and a co-active component;

[0010] The main active component includes platinum, and the co-active component includes any one or a combination of at least two of yttrium, zirconium or manganese.

[0011] In the present invention, on the one hand, by using magnesium oxide and alumina as the carrier, compared with using a single oxide, it is more conducive to adjusting the basic sites of the catalyst to achieve a basic environment suitable for the reaction of preparing 1,2-pentanediol from furfuryl alcohol; and, magnesium oxide and alumina have different crystal structures and surface properties. When the two are used in combination, they can influence each other to form a surface structure and pore distribution more conducive to the reaction. On the other hand, adding any one or at least two of yttrium, zirconium or manganese as the co-active component can change the electron cloud distribution of platinum, which is beneficial to the activation of the C-O bond in the furfuryl alcohol molecule, reduce the activation energy of the reaction, and thus improve the catalytic activity; secondly, the co-active component has an adsorption configuration different from that of platinum, and will preferentially adsorb specific reactants or intermediate products, guiding the reaction to proceed in the direction of generating 1,2-pentanediol and improving the selectivity of 1,2-pentanediol; in addition, yttrium, zirconium or manganese can form a more stable alloy structure or complex with platinum, reduce the agglomeration phenomenon of platinum, and improve the stability of the catalyst. The above characteristics interact with each other, not only regulating the basic sites of the catalyst, but also improving the selectivity and stability of the catalyst for preparing 1,2-pentanediol from furfuryl alcohol.

[0012] The following are the preferred technical solutions of the present invention, but do not limit the technical solutions provided by the present invention. Through the following preferred technical solutions, the technical objectives and beneficial effects of the present invention can be better achieved and realized.

[0013] Preferably, the co-active component at least includes yttrium.

[0014] In the present invention, yttrium has a unique adsorption selectivity for specific functional groups in furfuryl alcohol molecules. For example, it can selectively adsorb the hydroxyl groups of furfuryl alcohol, enabling furfuryl alcohol to react on the platinum surface in a specific orientation. Therefore, by using a co-active component containing yttrium, it is more conducive to improving the selectivity of 1,2-pentanediol.

[0015] Preferably, based on the mass of the carrier being 100 wt%, the loading amount of the main active component on the carrier is 0.15 wt% to 1.00 wt%, such as 0.15 wt%, 0.18 wt%, 0.36 wt%, 0.40 wt%, 0.50 wt%, 0.60 wt%, 0.70 wt%, 0.80 wt%, 0.90 wt% or 1.00 wt%, etc., and the loading amount of the co-active component on the carrier is 0.5 wt% to 1.5 wt%, such as 0.50 wt%, 0.65 wt%, 0.80 wt%, 1.00 wt%, 1.20 wt%, 1.33 wt%, 1.40 wt% or 1.50 wt%, etc. However, it is not limited to the listed values, and other unlisted values within this numerical range are equally applicable.

[0016] Preferably, the molar ratio of magnesium oxide to alumina is (2 to 4):1, such as 2.0:1.0, 2.3:1.0, 2.5:1.0, 3.0:1.0, 3.3:1.0, 3.5:1.0, 3.8:1.0 or 4.0:1.0, etc. However, it is not limited to the listed values, and other unlisted values within this numerical range are equally applicable.

[0017] In the present invention, the molar ratio of magnesium oxide to alumina affects the performance of the catalyst. By controlling it within the range of (2 to 4):1, the catalyst can have an appropriate number of basic sites, making the reaction system in an alkaline environment suitable for the reaction of furfuryl alcohol to prepare 1,2-pentanediol, which is conducive to improving the selectivity of the catalyst for the reaction of 1,2-pentanediol.

[0018] Preferably, the mass ratio of the main active component to the co-active component is 1.0:(1.5 to 4.0), such as 1.0:1.5, 1.0:1.8, 1.0:3.3, 1.0:3.7 or 1.0:4.0, etc. However, it is not limited to the listed values, and other unlisted values within this numerical range are equally applicable.

[0019] In the present invention, the loading amounts of the main active component and the co-active component on the carrier and the mass ratio between the two affect the performance of the catalyst. By controlling them within the above preferred ranges, the main active component platinum can provide sufficient active centers for the hydrogenation reaction, while the co-active component can effectively regulate the reaction path and inhibit the occurrence of side reactions. Within this range, the two interact with each other, enabling the activity and selectivity of the catalyst to reach a better balance.

[0020] In a second aspect, the present invention provides a method for preparing a catalyst for preparing 1,2-pentanediol from furfuryl alcohol as described in the first aspect, the preparation method comprising:

[0021] (1) Mix magnesium oxide and alumina to obtain a mixed powder, and then perform a first calcination treatment on the mixed powder to obtain a first calcined product;

[0022] (2) Mix the first calcined product obtained in step (1), the main active component source, the co-active component source and the solvent, perform an impregnation treatment, and obtain a precursor after drying;

[0023] (3) Perform a second calcination treatment on the precursor obtained in step (2) to obtain the catalyst for preparing 1,2-pentanediol from furfuryl alcohol;

[0024] The main active component source includes a platinum source, and the co-active component source includes any one or a combination of at least two of a yttrium source, a zirconium source or a manganese source.

[0025] In the present invention, only simple mixing, impregnation and calcination of raw materials are required to prepare a catalyst with excellent performance. Compared with the co-precipitation method, the method provided by the present invention not only has a simpler preparation process, but also is easier to control the loading amount of the active component on the carrier. And, it is worth mentioning that the carrier is calcined before impregnation in the present invention. This process will change the microstructure of the carrier, make the pore structure of the carrier more developed, increase its specific surface area, and is more conducive to the uniform dispersion of the active component on the surface of the carrier; moreover, during the calcination process, the chemical properties of the carrier surface will also change, making the active component more firmly attached to the carrier, avoiding agglomeration or loss of the active component during the reaction process; in addition, the calcination treatment can also make the crystal structure of the carrier more stable and enhance the mechanical strength of the carrier.

[0026] Preferably, the alumina in step (1) includes neutral alumina or basic alumina.

[0027] In the present invention, by using neutral alumina or basic alumina, the number of basic sites in the catalyst can be increased; in addition, the types of magnesium oxide, platinum source, yttrium source, zirconium source or manganese source are not limited in the present invention. Exemplarily, the magnesium oxide includes light magnesium oxide, the platinum source includes chloroplatinic acid hexahydrate, and the yttrium source, zirconium source or manganese source each independently includes a nitrate.

[0028] Preferably, the mixing in step (1) includes ball milling or stirring.

[0029] Preferably, the mixing time in step (1) is 0.5 h to 12.0 h, such as 0.5 h, 1.0 h, 2.0 h, 4.0 h, 6.0 h, 8.0 h, 10.0 h or 12.0 h, etc., but not limited to the listed values, and other unlisted values within this value range are equally applicable.

[0030] Preferably, the temperature of the first calcination treatment in step (1) is 400 °C to 700 °C, such as 400 °C, 450 °C, 500 °C, 550 °C, 600 °C, 650 °C or 700 °C, etc., but not limited to the listed values, and other unlisted values within this value range are equally applicable.

[0031] Preferably, the time of the first calcination treatment in step (1) is 2 h to 5 h, such as 2.0 h, 2.5 h, 3.0 h, 3.2 h, 3.4 h, 3.6 h, 3.8 h or 4.0 h, etc., but not limited to the listed values, and other unlisted values within this value range are equally applicable.

[0032] Preferably, the temperature of the impregnation treatment in step (2) is 20 °C to 30 °C, such as 20 °C, 22 °C, 24 °C, 25 °C, 26 °C, 28 °C or 30 °C, etc., but not limited to the listed values, and other unlisted values within this value range are equally applicable.

[0033] Preferably, the time of the impregnation treatment in step (2) is 8 h to 15 h, such as 8 h, 9 h, 10 h, 11 h, 12 h, 13 h, 14 h or 15 h, etc., but not limited to the listed values, and other unlisted values within this value range are equally applicable.

[0034] Preferably, the temperature of the drying in step (2) is 60 °C to 120 °C, such as 60 °C, 70 °C, 80 °C, 90 °C, 100 °C, 110 °C or 120 °C, etc., but not limited to the listed values, and other unlisted values within this value range are equally applicable.

[0035] Preferably, the time of the drying in step (2) is 8 h to 16 h, such as 8 h, 9 h, 10 h, 11 h, 12 h, 13 h, 14 h, 15 h or 16 h, etc., but not limited to the listed values, and other unlisted values within this value range are equally applicable.

[0036] Preferably, the temperature of the second calcination treatment in step (3) is 250 °C to 500 °C, such as 250 °C, 300 °C, 330 °C, 350 °C, 370 °C, 400 °C, 420 °C, 450 °C, 480 °C or 500 °C, etc., but not limited to the listed values, and other unlisted values within this value range are equally applicable.

[0037] Preferably, the time of the second calcination treatment in step (3) is 0.5 h to 3.0 h, such as 0.5 h, 0.8 h, 1.0 h, 1.2 h, 1.5 h, 2.0 h, 2.5 h or 3.0 h, etc., but not limited to the listed values, and other unlisted values within this numerical range are equally applicable.

[0038] In the present invention, the temperature and time of the second calcination treatment will affect the structure and performance of the catalyst. By controlling them within the above-preferred range, it is more conducive to obtaining a catalyst with an appropriate number and depth of oxygen vacancies. At the same time, it is also conducive to the full migration and redistribution of oxygen atoms in the lattice, making the distribution of oxygen vacancies more uniform, and more conducive to improving the activity and stability of the catalyst.

[0039] Preferably, the atmosphere of the second calcination in step (3) includes N2 and H2.

[0040] As a preferred technical solution of the present invention, the preparation method includes the following steps:

[0041] (1) Mix magnesium oxide and aluminum oxide under stirring for 0.5 h to 12 h to obtain a mixed powder, and then perform a first calcination treatment on the mixed powder at 400 °C to 700 °C for 2 h to 5 h to obtain a first calcination product;

[0042] (2) Mix the first calcination product obtained in step (1), the main active component source, the co-active component source and the solvent, impregnate at 20 °C to 30 °C for 8 h to 15 h, and then dry at 60 °C to 120 °C for 8 h to 16 h to obtain a precursor;

[0043] (3) Under the atmosphere of N2 and H2, perform a second calcination treatment on the precursor obtained in step (2) at 250 °C to 500 °C for 0.5 h to 3.0 h to obtain the catalyst for preparing 1,2-pentanediol from furfuryl alcohol;

[0044] The main active component source includes a platinum source, and the co-active component source includes any one or a combination of at least two of a yttrium source, a zirconium source or a manganese source.

[0045] In the third aspect, the present invention also provides an application of a catalyst, and the application includes using the catalyst as described in the first aspect or the catalyst prepared by the preparation method described in the second aspect for the selective hydrogenation of furfuryl alcohol to prepare 1,2-pentanediol.

[0046] Preferably, the method of the application includes: mixing furfuryl alcohol, water and the catalyst for preparing 1,2-pentanediol from furfuryl alcohol, and then performing a heating hydrogenation treatment to obtain 1,2-pentanediol.

[0047] During the synthesis process of the present invention, there is no need for harsh conditions such as organic solvents, high temperature and high pressure. The synthesis conditions are mild and the catalyst dosage is small, which is suitable for industrial applications.

[0048] Preferably, the mass ratio of the furfuryl alcohol to water is 1:(30 - 50), such as 1:30, 1:35, 1:40, 1:45 or 1:50, etc., but not limited to the listed values. Other unlisted values within this numerical range are equally applicable.

[0049] Preferably, the mass ratio of the furfuryl alcohol to the catalyst is 1.0:(0.2 - 0.5), such as 1.0:0.2, 1.0:0.3, 1.0:0.4 or 1.0:0.5, etc., but not limited to the listed values. Other unlisted values within this numerical range are equally applicable.

[0050] Preferably, the temperature of the heating and hydrogenation treatment is 140°C - 160°C, such as 140°C, 145°C, 150°C, 155°C or 160°C, etc., but not limited to the listed values. Other unlisted values within this numerical range are equally applicable.

[0051] Preferably, the heat preservation time of the heating and hydrogenation treatment is 240 min - 360 min, such as 240 min, 250 min, 260 min, 280 min, 300 min, 320 min, 340 min, 350 min or 360 min, etc., but not limited to the listed values. Other unlisted values within this numerical range are equally applicable.

[0052] In the present invention, the temperature and heat preservation time of the heating and hydrogenation treatment will affect the reaction rate and selectivity. By controlling them within the above - mentioned preferred ranges, not only can the reaction have a relatively fast reaction rate, but also the yield and selectivity of the product 1,2 - pentanediol can be at a relatively high level.

[0053] Preferably, during the heating and hydrogenation treatment, the pressure of hydrogen is 1 MPa - 2 MPa, such as 1.0 MPa, 1.1 MPa, 1.2 MPa, 1.3 MPa, 1.4 MPa, 1.5 MPa, 1.6 MPa, 1.7 MPa, 1.8 MPa, 1.9 MPa or 2.0 MPa, etc., but not limited to the listed values. Other unlisted values within this numerical range are equally applicable.

[0054] In the present invention, the hydrogen pressure also affects the reaction rate and selectivity. An appropriate hydrogen pressure can not only enable the reactant furfuryl alcohol to exhibit a relatively high conversion rate, but also help improve the selectivity of 1,2-pentanediol. At an appropriate pressure, the adsorption and reaction processes of hydrogen and furfuryl alcohol on the catalyst surface can be better controlled, which is conducive to the reaction proceeding along the path of generating the target product 1,2-pentanediol and inhibiting the occurrence of side reactions. If the hydrogen pressure is too low, it may lead to incomplete hydrogenation of furfuryl alcohol, while if the hydrogen pressure is too high, some side reactions of over-hydrogenation may be triggered.

[0055] Compared with the prior art, the present invention has the following beneficial effects:

[0056] (1) The present invention provides a heterogeneous catalyst for synthesizing 1,2-pentanediol. The catalyst has low production cost, high stability, and high activity, and has the advantages of easy separation of the catalyst from the product and high product selectivity compared with homogeneous catalysts.

[0057] (2) When the catalyst prepared by the present invention is applied to the synthesis of 1,2-pentanediol, the process is simple and the experimental conditions are mild. Compared with other synthesis routes, it does not require harsh conditions such as solvents, high temperature and high pressure, has a shorter reaction time, less catalyst dosage, and the selectivity for 1,2-pentanediol can be as high as 81.3%. Specific Embodiments

[0058] The technical solutions of the present invention will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations on the present invention.

[0059] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the technical field to which this application belongs; the terms used herein are only for the purpose of describing specific embodiments and are not intended to limit this application; the terms "including" and "having" and any variations thereof in the specification and claims of this application and the above drawings are intended to cover non-exclusive inclusion.

[0060] Example 1

[0061] This example provides a catalyst for preparing 1,2-pentanediol from furfuryl alcohol, which includes the carriers magnesium oxide and alumina, and the main active component platinum and the co-active component yttrium loaded on the carriers; wherein, the molar ratio of magnesium oxide to alumina is 3:1, and the loading amounts of platinum and yttrium are 0.36 wt% and 1.33 wt% respectively. The preparation method is as follows:

[0062] (1) Put 2.2660 g of light magnesium oxide and 1.9121 g of basic aluminum oxide into a ball milling jar, ball mill for 8 h to obtain a mixed powder, and then place the obtained mixed powder in a muffle furnace and calcine at 500 °C for 3 h to obtain the MgO and Al2O3 catalyst supports.

[0063] (2) Weigh 0.0401 g of chloroplatinic acid hexahydrate and 0.2400 g of yttrium nitrate hexahydrate and add them to the support, then add deionized water to cover the surface of the solid. After stirring until the chloroplatinic acid hexahydrate and yttrium nitrate hexahydrate are dissolved, let it stand and impregnate at 25 °C for 12 h, and then put it into an oven and dry at 80 °C for 12 h to obtain the precursor.

[0064] (3) Place the obtained precursor in a tubular furnace, introduce a mixed gas of N2 and H2, and reduce it at 300 °C for 1 h to obtain the catalyst for preparing 1,2-pentanediol from furfuryl alcohol.

[0065] Example 2

[0066] This example provides a catalyst for preparing 1,2-pentanediol from furfuryl alcohol, including the supports magnesium oxide and aluminum oxide, and the main active component platinum and the co-active component yttrium supported on the supports; wherein, the molar ratio of magnesium oxide to aluminum oxide is 2:1, and the loading amounts of platinum and yttrium are 0.15 wt% and 0.5 wt% respectively. The preparation method is as follows:

[0067] (1) Put 1.8450 g of light magnesium oxide and 2.3361 g of basic aluminum oxide into a ball milling jar, ball mill for 0.5 h to obtain a mixed powder, and then place the obtained mixed powder in a muffle furnace and calcine at 400 °C for 5 h to obtain the MgO and Al2O3 catalyst supports.

[0068] (2) Weigh 0.0166 g of chloroplatinic acid hexahydrate and 0.0900 g of yttrium nitrate hexahydrate and add them to the support, then add deionized water to cover the surface of the solid. After stirring until the chloroplatinic acid hexahydrate and yttrium nitrate hexahydrate are dissolved, let it stand and impregnate at 20 °C for 15 h, and then put it into an oven and dry at 60 °C for 16 h to obtain the precursor.

[0069] (3) Place the obtained precursor in a tubular furnace, introduce a mixed gas of N2 and H2, and reduce it at 250 °C for 3 h to obtain the catalyst for preparing 1,2-pentanediol from furfuryl alcohol.

[0070] Example 3

[0071] This example provides a catalyst for preparing 1,2-pentanediol from furfuryl alcohol, including the supports magnesium oxide and aluminum oxide, and the main active component platinum and the co-active component yttrium supported on the supports; wherein, the molar ratio of magnesium oxide to aluminum oxide is 4:1, and the loading amounts of platinum and yttrium are 1 wt% and 1.5 wt% respectively. The preparation method is as follows:

[0072] (1) Put 2.5600 g of light magnesium oxide and 1.6211 g of basic aluminum oxide into a ball milling jar, ball mill for 12 h to obtain a mixed powder, and then place the obtained mixed powder in a muffle furnace and calcine at 700 °C for 2 h to obtain the MgO, Al2O3 catalyst support.

[0073] (2) Weigh 0.1110 g of chloroplatinic acid hexahydrate and 0.2701 g of yttrium nitrate hexahydrate and add them to the support, then add deionized water to submerge the solid surface, stir until the chloroplatinic acid hexahydrate and yttrium nitrate hexahydrate are dissolved, stand and soak at 30 °C for 8 h, and then put it into an oven and dry at 120 °C for 8 h to obtain the precursor.

[0074] (3) Place the obtained precursor in a tubular furnace, introduce a mixed gas of N2 and H2, and reduce it at 500 °C for 0.5 h to obtain the catalyst for preparing 1,2 - pentanediol from furfuryl alcohol.

[0075] Example 4

[0076] The difference between this example and Example 1 is that in this example, the co - active component in the catalyst is manganese, and yttrium nitrate hexahydrate is replaced by manganese nitrate in the preparation method;

[0077] The remaining preparation methods and parameters are the same as those in Example 1.

[0078] Example 5

[0079] The difference between this example and Example 1 is that in this example, the co - active component in the catalyst is zirconium, and yttrium nitrate hexahydrate is replaced by zirconium nitrate in the preparation method;

[0080] The remaining preparation methods and parameters are the same as those in Example 1.

[0081] Example 6

[0082] The difference between this example and Example 1 is that in this example, the co - active component in the catalyst is tin, and yttrium nitrate hexahydrate is replaced by tin nitrate in the preparation method;

[0083] The remaining preparation methods and parameters are the same as those in Example 1.

[0084] Example 7

[0085] The difference between this example and Example 1 is that in this example, the molar ratio of magnesium oxide to aluminum oxide in the catalyst is 1:1, and 1.1842 g of magnesium oxide and 2.9940 g of aluminum oxide are weighed in the preparation method;

[0086] The remaining preparation methods and parameters are the same as those in Example 1.

[0087] Example 8

[0088] The difference between this example and Example 1 is that in this example, the loadings of platinum and yttrium in the catalyst are 0.18 wt% and 0.65 wt% respectively, and 0.0201 g of chloroplatinic acid hexahydrate and 0.1200 g of yttrium nitrate hexahydrate are added in step (1) of the preparation method;

[0089] The remaining preparation methods and parameters are the same as those in Example 1.

[0090] Example 9

[0091] The difference between this example and Example 1 is that in this example, the loading of platinum in the catalyst is 0.13 wt%, and 0.0145 g of chloroplatinic acid hexahydrate is added in step (1) of the preparation method;

[0092] The remaining preparation methods and parameters are the same as those in Example 1.

[0093] Example 10

[0094] The difference between this example and Example 1 is that in this example, the loading of yttrium in the catalyst is 0.36 wt%, and 0.0648 g of yttrium nitrate hexahydrate is added in step (1) of the preparation method;

[0095] The remaining preparation methods and parameters are the same as those in Example 1.

[0096] Example 11

[0097] The difference between this example and Example 1 is that in this example, reduction is carried out at 300 °C for 2 h in step (3) of the preparation method;

[0098] The remaining preparation methods and parameters are the same as those in Example 1.

[0099] Example 12

[0100] The difference between this example and Example 11 is that in this example, the loading of yttrium in the catalyst is 0.65 wt%, and 0.1175 g of yttrium nitrate hexahydrate is added in step (1) of the preparation method;

[0101] The remaining preparation methods and parameters are the same as those in Example 11.

[0102] Example 13

[0103] The difference between this example and Example 1 is that in this example, reduction is carried out at 300 °C for 25 min in step (3) of the preparation method;

[0104] The remaining preparation methods and parameters are the same as those in Example 1.

[0105] Example 14

[0106] The difference between this example and Example 1 is that in this example, in step (3) of the preparation method, the reduction is carried out at 300 °C for 4 h;

[0107] The remaining preparation methods and parameters are the same as those in Example 1.

[0108] Comparative Example 1

[0109] The difference between this comparative example and Example 1 is that in this comparative example, the catalyst does not contain the main active component platinum, and chloroplatinic acid hexahydrate is not added in the preparation method;

[0110] The remaining preparation methods and parameters are the same as those in Example 1.

[0111] Comparative Example 2

[0112] The difference between this comparative example and Example 1 is that in this comparative example, the catalyst does not contain the co-active component yttrium, and yttrium nitrate hexahydrate is not added in the preparation method;

[0113] The remaining preparation methods and parameters are the same as those in Example 1.

[0114] Comparative Example 3

[0115] The difference between this comparative example and Example 1 is that in this comparative example, the catalyst does not contain the carrier alumina and the co-active component yttrium, and alumina and yttrium nitrate hexahydrate are not added in the preparation method;

[0116] The remaining preparation methods and parameters are the same as those in Example 1.

[0117] Comparative Example 4

[0118] The difference between this comparative example and Example 1 is that in this comparative example, the catalyst does not contain the carrier magnesium oxide and the co-active component yttrium, and magnesium oxide and yttrium nitrate hexahydrate are not added in the preparation method;

[0119] The remaining preparation methods and parameters are the same as those in Example 1.

[0120] Comparative Example 5

[0121] The difference between this comparative example and Example 1 is that in this comparative example, the catalyst does not contain the carrier alumina and the main active component platinum, and alumina and chloroplatinic acid hexahydrate are not added in the preparation method;

[0122] The remaining preparation methods and parameters are the same as those in Example 1.

[0123] Comparative Example 6

[0124] The difference between this comparative example and Example 1 is that in this comparative example, the catalyst does not contain the carrier magnesium oxide and the main active component platinum. In the preparation method, magnesium oxide and chloroplatinic acid hexahydrate are not added.

[0125] The remaining preparation methods and parameters are the same as those in Example 1.

[0126] Comparative Example 7

[0127] The difference between this comparative example and Example 1 is that in this comparative example, the catalyst does not contain the main active component platinum and the co-active component yttrium. In the preparation method, chloroplatinic acid hexahydrate and yttrium nitrate hexahydrate are not added.

[0128] The remaining preparation methods and parameters are the same as those in Example 1.

[0129] Comparative Example 8

[0130] The difference between this comparative example and Example 4 is that in this comparative example, the catalyst does not contain the main active component platinum. In the preparation method, chloroplatinic acid hexahydrate is not added.

[0131] The remaining preparation methods and parameters are the same as those in Example 4.

[0132] Comparative Example 9

[0133] The difference between this comparative example and Example 5 is that in this comparative example, the catalyst does not contain the main active component platinum. In the preparation method, chloroplatinic acid hexahydrate is not added.

[0134] The remaining preparation methods and parameters are the same as those in Example 5.

[0135] Comparative Example 10

[0136] The difference between this example and Example 1 is that in this example, step (1) is not carried out. In step (2), 2.2660 g of light magnesium oxide and 1.9121 g of basic alumina without calcination treatment are directly used as the carrier.

[0137] The remaining preparation methods and parameters are the same as those in Example 1.

[0138] Application Example 1.1

[0139] Take 0.1 g of the catalyst provided in Example 1, 0.2 g of furfuryl alcohol and 8 g of water and put them into a 50 mL autoclave. Charge 1 MPa of hydrogen and react at 140 °C for 360 min to obtain 1,2-pentanediol.

[0140] Application Example 1.2

[0141] Take 0.04 g of the catalyst provided in Example 1, 0.2 g of furfuryl alcohol and 6 g of water and put them into a 50 mL autoclave. Charge 1 MPa of hydrogen and react at 150 °C for 300 min to obtain 1,2-pentanediol.

[0142] Application Example 1.3

[0143] Take 0.07 g of the catalyst provided in Example 1, 0.2 g of furfuryl alcohol and 10 g of water and put them into a 50 mL autoclave. Charge 1 MPa of hydrogen and react at 160 °C for 240 min to obtain 1,2-pentanediol.

[0144] Application Example 1.4

[0145] The difference between this application example and Application Example 1.1 is that in this application example, 1.5 MPa of hydrogen is charged;

[0146] The remaining preparation methods and parameters are all the same as those in Application Example 1.1.

[0147] Application Example 1.5

[0148] The difference between this application example and Application Example 1.1 is that in this application example, 2 MPa of hydrogen is charged;

[0149] The remaining preparation methods and parameters are all the same as those in Application Example 1.1.

[0150] Application Example 1.6

[0151] The difference between this application example and Application Example 1.1 is that in this application example, 0.8 MPa of hydrogen is charged;

[0152] The remaining preparation methods and parameters are all the same as those in Application Example 1.1.

[0153] Application Example 1.7

[0154] The difference between this application example and Application Example 1.1 is that in this application example, the reaction is carried out at 130 °C for 360 min;

[0155] The remaining preparation methods and parameters are all the same as those in Application Example 1.1

[0156] Application Example 1.8

[0157] The difference between this application example and Application Example 1.1 is that in this application example, the reaction is carried out at 200 °C for 360 min;

[0158] The remaining preparation methods and parameters are all the same as those in Application Example 1.1.

[0159] Application Example 2 - 14

[0160] The difference between Application Example 2-14 and Application Example 1.1 is that Application Example 2-14 respectively uses the catalysts prepared in Examples 2-14;

[0161] The remaining preparation methods and parameters are the same as those in Application Example 1.1.

[0162] Comparative Application Example 1-10

[0163] The difference between Comparative Application Example 1-10 and Application Example 1.1 is that Comparative Application Example 1-10 respectively uses the catalysts prepared in Comparative Examples 1-10;

[0164] The remaining preparation methods and parameters are the same as those in Application Example 1.1.

[0165] Performance test

[0166] After centrifuging the reaction solutions obtained from Application Examples 1-14 and Comparative Application Examples 1-10, an appropriate amount of the supernatant was taken and biphenyl as the internal standard was added, and quantitative analysis was carried out by gas chromatography internal standard method. The test results are shown in Table 1:

[0167] Table 1

[0168]

[0169] From Application Example 1.1, Application Example 2, and Application Example 3 in Table 1, it can be seen that the catalyst provided by the present invention shows high catalytic activity through the synergistic cooperation among the carrier, the main active component, and the promoter; from the data comparison between Application Example 1.1 and Comparative Application Examples 1-9 in Table 1, it can be seen that in the present invention, the carrier, the main active component, and the promoter interact with each other, and the absence of any one of them will significantly reduce the performance of the catalyst; from the data comparison between Application Example 1.1 and Comparative Application Example 10 in Table 1, it can be seen that in the present invention, the pre-calcination treatment of the carrier plays an important role in improving the catalyst performance.

[0170] From the data comparison between Application Example 1.1, Application Examples 4-6 in Table 1, it can be seen that in the present invention, different promoters have different degrees of improvement in the selectivity of 1,2-pentanediol, and the effect is the best when yttrium is selected as the promoter; from the data comparison between Application Example 1.1 and Application Examples 8-14 in Table 1, it can be seen that the loading amount of the main active component and the promoter on the carrier, the ratio between the two, and the time of the second calcination treatment during the preparation process will all affect the performance of the catalyst. By controlling them within the preferred range of the present invention, the catalytic effect can be made more excellent.

[0171] As can be seen from the data of Application Examples 1.1 - 1.3 in Table 1, in the application process of the present invention, only mild synthesis conditions and less catalyst are required to achieve high conversion rate and selectivity, which is suitable for industrial application. From the comparison of the data of Application Example 1.1 and Application Examples 1.4 - 1.8 in Table 1, it can be seen that in the application process of the present invention, both hydrogen pressure and hydrogenation temperature will affect the performance of the catalyst. By controlling them within the preferred range of the present invention, the conversion rate of furfuryl alcohol and the selectivity of the catalyst to 1,2 - pentanediol can be further improved.

[0172] The applicant declares that the above - mentioned is only the specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by any person skilled in the art within the technical scope disclosed by the present invention fall within the protection scope and the disclosure scope of the present invention.

Claims

1. A catalyst for preparing 1,2-pentanediol from furfuryl alcohol, characterized in that, The catalyst includes a support and an active component supported on the support. The support includes magnesium oxide and aluminum oxide, and the active component includes a main active component and a promoter active component; The main active component includes platinum, and the promoter active component includes any one or a combination of at least two of yttrium, zirconium, or manganese.

2. The catalyst for preparing 1,2-pentanediol from furfuryl alcohol according to claim 1, wherein, The promoter active component includes at least yttrium; Preferably, based on the mass of the support being 100 wt%, the loading amount of the main active component on the support is 0.15 wt% to 1.00 wt%, and the loading amount of the promoter active component on the support is 0.5 wt% to 1.5 wt%; Preferably, the molar ratio of magnesium oxide to aluminum oxide is (2 - 4):1; Preferably, the mass ratio of the main active component to the promoter active component is 1.0:(1.5 - 4.0).

3. A method for preparing a catalyst for the preparation of 1,2-pentanediol from furfuryl alcohol as described in claim 1 or 2, characterized in that, The preparation method includes: (1) Mix magnesium oxide and aluminum oxide to obtain a mixed powder, and then perform a first calcination treatment on the mixed powder to obtain a first calcined product; (2) Mix the first calcined product obtained in step (1), a main active component source, a promoter active component source, and a solvent, perform an impregnation treatment, and obtain a precursor after drying; (3) Perform a second calcination treatment on the precursor obtained in step (2) to obtain the catalyst for preparing 1,2 - pentanediol from furfuryl alcohol; The main active component source includes a platinum source, and the promoter active component source includes any one or a combination of at least two of a yttrium source, a zirconium source, or a manganese source.

4. The preparation method of the catalyst for preparing 1,2-pentanediol from furfuryl alcohol according to claim 3, characterized in that, The aluminum oxide in step (1) includes neutral aluminum oxide or basic aluminum oxide; Preferably, the mixing in step (1) includes ball milling or stirring; Preferably, the mixing time in step (1) is 0.5 h to 12.0 h; Preferably, the temperature of the first calcination treatment in step (1) is 400°C to 700°C; Preferably, the time of the first calcination treatment in step (1) is 2 h to 5 h.

5. The preparation method of the catalyst for preparing 1,2-pentanediol from furfuryl alcohol according to claim 3 or 4, characterized in that, The temperature of the impregnation treatment in step (2) is 20°C to 30°C; Preferably, the impregnation treatment time in step (2) is 8 h to 15 h; Preferably, the drying temperature in step (2) is 60°C to 120°C; Preferably, the drying time in step (2) is 8 h to 16 h.

6. The preparation method of the catalyst for preparing 1,2-pentanediol from furfuryl alcohol according to any one of claims 3-5, characterized in that, The temperature of the second calcination treatment in step (3) is 250°C to 500°C; Preferably, the time of the second calcination treatment in step (3) is 0.5 h to 3.0 h; Preferably, the atmosphere of the second calcination treatment in step (3) includes N2 and H2.

7. The preparation method of the catalyst for preparing 1,2-pentanediol from furfuryl alcohol according to claim 3, characterized in that, The preparation method includes the following steps: (1) Mix magnesium oxide and aluminum oxide under stirring for 0.5 h to 12.0 h to obtain a mixed powder, and then perform a first calcination treatment on the mixed powder at 400°C to 700°C for 2 h to 5 h to obtain a first calcined product; (2) Mix the first calcined product obtained in step (1), a main active component source, a promoter active component source, and a solvent, impregnate at 20°C to 30°C for 8 h to 15 h, and then dry at 60°C to 120°C for 8 h to 16 h to obtain a precursor; (3) Under the atmosphere of N2 and H2, the precursor described in step (2) is subjected to a second calcination treatment at 250 °C to 500 °C for 0.5 h to 3.0 h to obtain the catalyst for the preparation of 1,2-pentanediol from furfuryl alcohol; The main active component source includes a platinum source, and the co-active component source includes any one or a combination of at least two of a yttrium source, a zirconium source, or a manganese source.

8. Application of a catalyst, characterized in that, The application includes using the catalyst as claimed in claim 1 or 2 or the catalyst prepared by the preparation method as claimed in any one of claims 3-7 for the selective hydrogenation of furfuryl alcohol to prepare 1,2-pentanediol.

9. Use of the catalyst according to claim 8, characterized in that, The method of the application includes: mixing furfuryl alcohol, water and the catalyst for the preparation of 1,2-pentanediol from furfuryl alcohol, and then performing a heating hydrogenation treatment to obtain 1,2-pentanediol.

10. The use of the catalyst according to claim 9, wherein, The mass ratio of the furfuryl alcohol to water is 1:(30-50); Preferably, the mass ratio of the furfuryl alcohol to the catalyst is 1.0:(0.2-0.5); Preferably, the temperature of the heating hydrogenation treatment is 140 °C to 160 °C; Preferably, the heat preservation time of the heating hydrogenation treatment is 240 min to 360 min; Preferably, during the heating hydrogenation treatment, the pressure of hydrogen is 1 MPa to 2 MPa.

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