Furfuryl alcohol hydrogenation catalyst as well as preparation method and application thereof

Abstract

The invention relates to the field of catalysts, in particular to a furfuryl alcohol hydrogenation catalyst and a preparation method and application thereof. The furfuryl alcohol hydrogenation catalyst provided by the invention comprises a carrier, MgO embedded in the carrier and Cu-Me alloy particles loaded on the carrier, the molar ratio of Cu element to Me element in the Cu-Me alloy particles is (1-20): 1, and based on the total mass of the furfuryl alcohol hydrogenation catalyst, the loading capacity of the Cu-Me alloy particles is 5wt%-20wt%; the carrier is Al2O3, and the Me element comprises at least one of precious metal elements. When the furfuryl alcohol hydrogenation catalyst provided by the invention is used for catalyzing furfuryl alcohol to prepare 1, 2-pentanediol, the technological process is simple, the reaction process is controllable, continuous preparation of a 1, 2-pentanediol product can be realized, the product quality is excellent and stable, the furfuryl alcohol hydrogenation conversion rate reaches 99.9%, and the selectivity of the product 1, 2-pentanediol reaches 88%.

Description

Technical Field

[0001] The present invention relates to the field of catalysts, and in particular to a furfuryl alcohol hydrogenation catalyst for preparing 1,2-pentanediol, and a preparation method and application thereof. Background Art

[0002] 1,2-Pentanediol is an important component of diol compounds, a key intermediate of the fungicide propiconazole, and an important raw material for the production of chemical products such as polyesters and surfactants. It can improve the water resistance of sunscreen products, is an excellent moisturizer, and has an antiseptic effect. In addition, 1,2-pentanediol can dissolve insoluble active ingredients and is often used in various skin care products such as skin creams, eye creams, skin lotions, baby care, and sunscreen. However, due to technical limitations, the synthesis of 1,2-pentanediol is difficult, the yield is low, and the cost is high, which seriously restricts the development and application of some chemical products such as propiconazole in the industry.

[0003] CN110845301A discloses a method for preparing 1,2-pentanediol by liquid phase selective hydrogenolysis of furfuryl alcohol, wherein a composite catalyst is obtained by loading precious metals on a composite carrier, wherein the composite carrier is an oxide mixture formed by blending any one or more of silicon dioxide, zirconium dioxide, titanium dioxide, aluminum oxide, and molecular sieves with manganese oxide, and the precious metal active component is any one or more of platinum, ruthenium, palladium, rhodium, and iridium, and the content thereof is 1% to 6%. Under the conditions of temperature 100 to 200°C, pressure 1 to 5MPa, air velocity 0.1 to 0.5, and hydrogen-alcohol ratio 4 to 10:1, the furfuryl alcohol conversion rate can reach more than 99.%, and the selectivity of 1,2-pentanediol can reach up to 45%. The method has mild reaction conditions, but the catalyst has a high precious metal content and high cost, and the catalytic activity needs to be further improved, and the selectivity for the target product 1,2-pentanediol is low.

[0004] CN116459831A discloses an amorphous alloy RuLa / MgO catalyst for selective hydrogenation of furfuryl alcohol to prepare 1,2-pentanediol. Under the conditions of reaction temperature of 200°C, reaction pressure of 1 MPa and reaction time of 2 h, the conversion rate of furfuryl alcohol is 100% and the selectivity of 1,2-pentanediol is 55%. The preparation method of the catalyst is simple, but the price is high and the selectivity of the target product 1,2-pentanediol still needs to be improved. Summary of the invention

[0005] The purpose of the invention is to overcome the technical problems of low conversion rate and low selectivity of the furfuryl alcohol hydrogenation catalyst in the reaction of preparing 1,2-pentanediol by hydrogenation of furfuryl alcohol in the prior art.

[0006] In order to achieve the above object, the present invention provides a furfuryl alcohol hydrogenation catalyst, comprising a carrier, MgO embedded in the carrier and Cu-Me alloy particles loaded on the carrier, wherein the molar ratio of Cu element to Me element in the Cu-Me alloy particles is 1-20:1, and the loading amount of the Cu-Me alloy particles is 5wt%-20wt% based on the total mass of the furfuryl alcohol hydrogenation catalyst;

[0007] The carrier is Al2O3, and the Me element includes at least one of the noble metal elements.

[0008] A second aspect of the present invention provides a method for preparing a furfuryl alcohol hydrogenation catalyst, comprising the following steps:

[0009] S1: mixing the carrier with a Mg salt solution and crystallizing to obtain an intermediate;

[0010] S2: mixing the intermediate with a Cu-Me solution to obtain a precursor;

[0011] S3: Under a hydrogen atmosphere I, reducing the precursor to obtain the furfuryl alcohol hydrogenation catalyst;

[0012] Wherein, in step S1, the carrier is Al2O3;

[0013] In step S2, the solid-liquid ratio of the intermediate to the Cu-Me solution is 0.6 g / mL-0.7 g / mL, the molar ratio of the Cu element to the Me element in the Cu-Me solution is 1-20:1, and the Me element is at least one of the noble metal elements.

[0014] The third aspect of the present invention provides a furfuryl alcohol hydrogenation catalyst prepared by the preparation method provided by the second aspect of the present invention.

[0015] The fourth aspect of the present invention provides use of the furfuryl alcohol hydrogenation catalyst provided by the first aspect or the third aspect of the present invention in the catalytic preparation of 1,2-pentanediol.

[0016] The fifth aspect of the present invention provides a method for preparing 1,2-pentanediol, comprising the following steps: introducing a furfuryl alcohol solution into a reactor filled with a furfuryl alcohol hydrogenation catalyst under a hydrogen atmosphere II for hydrogenation reaction treatment to obtain 1,2-pentanediol;

[0017] Wherein, the furfuryl alcohol hydrogenation catalyst is the furfuryl alcohol hydrogenation catalyst described in the first aspect or the third aspect of the present invention.

[0018] The technical solution provided by the present invention has at least the following technical effects:

[0019] (1) The furfuryl alcohol hydrogenation catalyst provided by the present invention has good catalytic effect, mild reaction conditions, and the furfuryl alcohol hydrogenation conversion rate reaches 99.9%, and the selectivity of the product 1,2-pentanediol can reach 88%;

[0020] (2) The inventors of the present invention have discovered through creative work that active metals Cu and Me can form a special atomic cluster structure on the surface of the Al2O3 carrier embedded with MgO, thereby forming Cu-Me alloy particles, thereby strengthening the synergistic catalytic effect between the two, achieving high activity and high selectivity, and greatly reducing the manufacturing cost of the catalyst; and that the doping of active metals Cu and Me can effectively extend the stability and service life of the furfuryl alcohol hydrogenation catalyst;

[0021] (3) The method for preparing the furfuryl alcohol hydrogenation catalyst provided by the present invention can prepare the furfuryl alcohol hydrogenation catalyst provided by the first aspect of the present invention, and the preparation process is simple, the cost is low, and it is suitable for industrial scale-up production and application, and has high economic efficiency;

[0022] (4) The method for preparing 1,2-pentanediol provided by the present invention has a simple process flow and a controllable reaction process, and can realize continuous preparation of 1,2-pentanediol products. The product quality is excellent and stable, the furfuryl alcohol hydrogenation conversion rate reaches 99.9%, and the selectivity of the product 1,2-pentanediol reaches 88%. DETAILED DESCRIPTION

[0023] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0024] As mentioned above, the first aspect of the present invention provides a furfuryl alcohol hydrogenation catalyst, comprising a carrier, MgO embedded in the carrier, and Cu-Me alloy particles loaded on the carrier, wherein the molar ratio of Cu element to Me element in the Cu-Me alloy particles is 1-20:1, and the loading amount of the Cu-Me alloy particles is 5wt%-20wt% based on the total mass of the furfuryl alcohol hydrogenation catalyst;

[0025] The carrier is Al2O3, and the Me element includes at least one of the noble metal elements.

[0026] According to some preferred embodiments of the present invention, the molar ratio of Cu element to Me element in the Cu-Me alloy particles is 5-10: 1. Under the preferred conditions, the conversion rate and selectivity of furfuryl alcohol hydrogenation catalyst to prepare 1,2-pentanediol are higher.

[0027] According to some preferred embodiments of the present invention, based on the total mass of the furfuryl alcohol hydrogenation catalyst, the content of MgO is 4wt%-7wt%.

[0028] According to some preferred embodiments of the present invention, based on the total mass of the furfuryl alcohol hydrogenation catalyst, the content of the carrier is 70 wt%-90 wt%.

[0029] According to some preferred embodiments of the present invention, the Me element is at least one of Pd element, Pt element, Ru element, Rh element and Ir element.

[0030] According to some preferred embodiments of the present invention, the average specific surface area of ​​the furfuryl alcohol hydrogenation catalyst is 200m 2 / g-250m 2 / g, average pore volume 0.6g / cm 3 -0.8g / cm 3 Under the preferred conditions, the conversion rate and selectivity of the furfuryl alcohol hydrogenation catalyst for preparing 1,2-pentanediol are higher.

[0031] A second aspect of the present invention provides a method for preparing a furfuryl alcohol hydrogenation catalyst, comprising the following steps:

[0032] S1: mixing the carrier with a Mg salt solution and crystallizing to obtain an intermediate;

[0033] S2: mixing the intermediate with a Cu-Me solution to obtain a precursor;

[0034] S3: Under a hydrogen atmosphere I, reducing the precursor to obtain the furfuryl alcohol hydrogenation catalyst;

[0035] Wherein, in step S1, the carrier is Al2O3;

[0036] In step S2, the solid-liquid ratio of the intermediate to the Cu-Me solution is 0.6 g / mL-0.7 g / mL, the molar ratio of the Cu element to the Me element in the Cu-Me solution is 1-20:1, and the Me element is at least one of the noble metal elements.

[0037] According to some preferred embodiments of the present invention, in step S1, the carrier is mixed with the Mg salt solution, the pH is adjusted to 10-11, and then crystallized to obtain the intermediate.

[0038] It should be noted that, in the present invention, a pH regulator is used to adjust the pH of the mixture formed by the carrier and the Mg salt solution to 10-11. The present invention does not make special requirements on the type of pH regulator, and the pH regulator conventionally used in the art can be used, for example, sodium bicarbonate solution.

[0039] According to some preferred embodiments of the present invention, in step S1, the mixing temperature of the carrier and the Mg salt solution is 30°C-60°C.

[0040] According to a particularly preferred embodiment of the present invention, step S1 is performed as follows:

[0041] Under heating conditions at 30°C-60°C in a water bath, the carrier is mixed with the Mg salt solution to obtain a mixture. After 1h-3h, 0.05mol / L-0.2mol / L sodium bicarbonate solution is added dropwise to adjust the pH of the mixture to 10-11. Stirring is continued for 1h-3h to crystallize the mixture, and then filtered to obtain an intermediate.

[0042] According to some preferred embodiments of the present invention, in step S1, the content of Mg element in the Mg salt solution is 0.9 mol / L-1.1 mol / L, and the solid-liquid ratio of the carrier to the Mg salt solution is 0.5 g / mL-0.7 g / mL.

[0043] It should be noted that the Mg salt solution is obtained by dissolving a soluble Mg salt in water. The present invention has no special requirements for the soluble Mg salt. Exemplarily, the soluble Mg salt is Mg(NO3)2.

[0044] According to some preferred embodiments of the present invention, in step S1, the average specific surface area of ​​the carrier is 200 m 2 / g-250m 2 / g, average pore volume 0.5g / cm 3 -0.8g / cm 3 Under the preferred conditions, the conversion rate and selectivity of the furfuryl alcohol hydrogenation catalyst to prepare 1,2-pentanediol are higher.

[0045] According to some preferred embodiments of the present invention, in step S2, the molar ratio of Cu element to Me element in the Cu-Me solution is 5-10: 1. Under this preferred condition, the conversion rate and selectivity of the prepared furfuryl alcohol hydrogenation catalyst for preparing 1,2-pentanediol are higher.

[0046] According to some preferred embodiments of the present invention, in step S2, the Me element is at least one of the Pd element, the Pt element, the Ru element, the Rh element, and the Ir element.

[0047] It should be noted that the Cu element exists in the Cu-Me solution in the form of a soluble Cu salt, and the Me element exists in the Cu-Me solution in the form of a soluble Me salt. The present invention has no special requirements for the soluble Cu salt and the soluble Me salt. Exemplarily, the soluble Cu salt is Cu(NO3)2, and the soluble Me salt is Me chloride, Me nitrate, etc.

[0048] It should also be noted that the present invention has no special requirements for the solvent of the Cu-Me solution. Exemplarily, the solvent of the Cu-Me solution can be water.

[0049] According to some preferred embodiments of the present invention, in step S3, the content of hydrogen in the hydrogen atmosphere I is 10 vol%-30 vol%, and the remainder is nitrogen or inert gas such as helium and argon. In this preferred case, the conversion rate and selectivity of the prepared furfuryl alcohol hydrogenation catalyst for catalytic preparation of 1,2-pentanediol are higher.

[0050] According to some preferred embodiments of the present invention, in step S3, the temperature of the reduction treatment is 150°C-400°C, the pressure is 0.1MPa-5MPa in gauge pressure, and the time is 2h-10h.

[0051] The third aspect of the present invention provides a furfuryl alcohol hydrogenation catalyst prepared by the preparation method provided by the second aspect of the present invention.

[0052] The fourth aspect of the present invention provides use of the furfuryl alcohol hydrogenation catalyst provided by the first aspect or the third aspect of the present invention in catalyzing the hydrogenation of furfuryl alcohol to prepare 1,2-pentanediol.

[0053] The fifth aspect of the present invention provides a method for preparing 1,2-pentanediol, comprising the following steps: introducing a furfuryl alcohol solution into a reactor filled with a furfuryl alcohol hydrogenation catalyst under a hydrogen atmosphere II for hydrogenation reaction treatment to obtain 1,2-pentanediol;

[0054] Wherein, the furfuryl alcohol hydrogenation catalyst is the furfuryl alcohol hydrogenation catalyst described in the first aspect or the third aspect of the present invention.

[0055] According to some preferred embodiments of the present invention, the concentration of furfuryl alcohol in the furfuryl alcohol solution is 10wt%-50wt%. More preferably, the concentration of furfuryl alcohol in the furfuryl alcohol solution is 10wt%-30wt%.

[0056] According to some preferred embodiments of the present invention, the solvent of the furfuryl alcohol solution is selected from at least one of anhydrous ethanol, isopropanol, water and methanol.

[0057] It should be noted that the present invention has no special requirements for the solvent of the furfuryl alcohol solution. The solvent only needs to be able to form a uniform solution with furfuryl alcohol and not participate in the reaction during the hydrogenation reaction. Exemplarily, the solvent of the furfuryl alcohol solution is one of methanol, ethanol, propanol, butanol, pentanol or water.

[0058] According to some preferred embodiments of the present invention, the hydrogen atmosphere II is such that the molar ratio of hydrogen for the hydrogenation reaction to furfuryl alcohol in the furfuryl alcohol solution is 10-100: 1. Under this preferred condition, the conversion rate and selectivity in the reaction of hydrogenating furfuryl alcohol to prepare 1,2-pentanediol can be improved.

[0059] According to some preferred embodiments of the present invention, the hydrogen atmosphere II is such that the molar ratio of hydrogen for the hydrogenation reaction to furfuryl alcohol in the furfuryl alcohol solution is 15-30: 1. Under this preferred condition, the conversion rate and selectivity in the reaction of hydrogenating furfuryl alcohol to prepare 1,2-pentanediol are higher.

[0060] According to some preferred embodiments of the present invention, the mass space velocity of the furfuryl alcohol solution is 0.1 kg / h-1.0 kg / h.

[0061] According to some preferred embodiments of the present invention, the mass space velocity of the furfuryl alcohol solution is 0.3 kg / h-0.5 kg / h. Under the preferred conditions, the conversion rate and selectivity in the reaction of hydrogenating furfuryl alcohol to prepare 1,2-pentanediol are higher.

[0062] According to some preferred embodiments of the present invention, the reactor is a fixed bed reactor, the ratio of the filling height of the furfuryl alcohol hydrogenation catalyst to the tube diameter of the fixed bed reactor is 4-10:1, and the ratio of the filling thickness of the furfuryl alcohol hydrogenation catalyst to the tube diameter of the fixed bed reactor is 0.5-0.8:1.

[0063] According to some preferred embodiments of the present invention, the temperature of the hydrogenation reaction treatment is 100° C.-200° C., and the pressure is 3 MPa-8 MPa in gauge pressure.

[0064] More preferably, the temperature of the hydrogenation reaction treatment is 120°C-160°C, and the pressure is 5MPa-7MPa in gauge pressure.

[0065] The present invention will be described in detail below through examples. In the following examples, the instruments, reagents, materials, etc. involved, unless otherwise specified, are all conventional instruments, reagents, materials, etc. already in the prior art and can be obtained through regular commercial channels. The experimental methods, detection methods, etc. involved in the following examples, unless otherwise specified, are all conventional experimental methods, detection methods, etc. already in the prior art.

[0066] In the following examples, the Cu-Me solution is prepared by dissolving nitrate of Cu(NO3)2 and Me in water.

[0067] Carrier I: Al2O3, average specific surface area 220m 2 / g, average pore volume 0.65g / cm 3 ;

[0068] Carrier II: Al2O3, average specific surface area of ​​170m 2 / g, average pore volume 0.5g / cm 3 .

[0069] Preparation Example 1

[0070] S1: mixing the carrier with a Mg salt solution and crystallizing to obtain an intermediate;

[0071] S2: mixing the intermediate with a Cu-Me solution to obtain a precursor;

[0072] S3: Under a hydrogen atmosphere I, reducing the precursor to obtain the furfuryl alcohol hydrogenation catalyst;

[0073] Other parameters are shown in Table 1 below.

[0074] Preparation Example 2-3

[0075] The preparation was carried out in the manner of Preparation Example 1, except that the concentration of the Mg salt solution, the type of Me element in the Cu-Me solution, and the solid-to-liquid ratio II of the intermediate and the Me element in the Cu-Me solution were adjusted, specifically, as shown in Table 1 below.

[0076] Preparation Example 4

[0077] The method of Preparation Example 1 is followed, except that the molar ratio of the Cu element to the Me element in the Cu-Me solution is adjusted, specifically, as shown in Table 1 below.

[0078] Preparation Example 5

[0079] The method of Preparation Example 1 was followed, except that the type of carrier was replaced.

[0080] Preparation Example 6

[0081] The method of Preparation Example 1 is followed, except that the temperature of the reduction treatment in step S3 is adjusted.

[0082] Comparative Preparation Example 1

[0083] The method of Preparation Example 1 is followed, except that step S1 is not performed, and the carrier is directly mixed with the Cu-Me solution to obtain a precursor, and then the precursor is reduced in a hydrogen atmosphere I to obtain the furfuryl alcohol hydrogenation catalyst.

[0084] Comparative Preparation Example 2

[0085] The preparation was carried out in the manner of Preparation Example 1, except that the Cu-Me solution in step S2 was replaced by a Cu-containing solution (without Me element).

[0086] Table 1

[0087]

[0088] Note: Solid-liquid ratio I represents the solid-liquid ratio of the carrier and the Mg salt solution used for mixing in step S1;

[0089] Solid-liquid ratio II represents the solid-liquid ratio of the intermediate used for mixing to the Cu-Me solution in step S2; Special note: In comparative preparation example 1, solid-liquid ratio II represents the solid-liquid ratio of the carrier used for mixing to the Cu-Me solution;

[0090] The hydrogen atmosphere I consisted of hydrogen and nitrogen; the room temperature was 23°C (±2°C).

[0091] The composition of the furfuryl alcohol hydrogenation catalysts prepared in the preparation examples of the present invention and the comparative preparation examples was detected by an ICP (inductively coupled plasma) instrument. The specific results are shown in Table 2 below.

[0092] The average specific surface area and average pore volume of the furfuryl alcohol hydrogenation catalysts prepared in the preparation examples of the present invention and the comparative preparation examples were detected by nitrogen adsorption and desorption method. The specific results are shown in Table 2 below.

[0093] Table 2

[0094] Furfuryl alcohol hydrogenation catalyst number C1 C2 C3 C4 C5 C6 DC1 DC2 Cu-Me alloy particle content / wt% 10 10 10 10 10 10 10 / Cu:Me / mol 10:1 10:1 10:1 20:1 10:1 10:1 10:1 Cu content / wt% / / / / / / / 10 MgO content / wt% 7 7 7 7 7 7 / 7 <![CDATA[Al2O3 content / wt%]]> 83 83 83 83 83 83 83 83 <![CDATA[Average specific surface area / m 2 / g]]> 215 215 214 217 170 216 214 213 <![CDATA[Average pore volume / g / cm 3 > 0.63 0.63 0.63 0.62 0.45 0.62 0.65 0.61

[0095] Example 1

[0096] Under hydrogen atmosphere II, the furfuryl alcohol solution is introduced into a fixed bed reactor filled with a furfuryl alcohol hydrogenation catalyst for hydrogenation reaction treatment to obtain 1,2-pentanediol, wherein the furfuryl alcohol hydrogenation catalyst is C1.

[0097] Wherein, the solvent of the furfuryl alcohol solution is water. Specifically, other parameters are shown in Table 3 below.

[0098] Embodiment 2-6

[0099] The process was carried out in the same manner as in Example 1, except that the type of furfuryl alcohol hydrogenation catalyst was changed.

[0100] Specifically, the parameters are shown in Table 3 below.

[0101] Example 7

[0102] The method of Example 1 is followed, except that the molar ratio of the hydrogen gas treated by the hydrogenation reaction to the furfuryl alcohol in the furfuryl alcohol solution is adjusted.

[0103] Comparative Example 1-2

[0104] The process was carried out in the same manner as in Example 1, except that the type of furfuryl alcohol hydrogenation catalyst was changed.

[0105] Specifically, the parameters are shown in Table 3 below.

[0106] Table 3

[0107]

[0108] Note: hydrogen-to-alcohol ratio refers to the molar ratio of hydrogen gas used in the hydrogenation reaction to furfuryl alcohol in the furfuryl alcohol solution;

[0109] The conversion rate refers to the weight ratio of furfuryl alcohol consumption to the total furfuryl alcohol raw materials;

[0110] Selectivity refers to the weight ratio of the target product (1,2-pentanediol) to the total products (including 1,2-pentanediol and other impurity products);

[0111] The conversion rate and selectivity in Table 3 are the data corresponding to the time point of the maximum selectivity measured during the operation of the furfuryl alcohol hydrogenation catalyst from 0 to 200 hours.

[0112] Stability test of furfuryl alcohol hydrogenation catalyst: The furfuryl alcohol hydrogenation catalyst prepared in this example was continuously operated for 1000 h under the preparation conditions of Example 1. The conversion rate and selectivity of the furfuryl alcohol hydrogenation catalyst were measured at different time points and are shown in Table 4 below.

[0113] Table 4

[0114]

[0115]

[0116] Note: The data corresponding to 200h represent the average conversion rate and average selectivity of the furfuryl alcohol hydrogenation catalyst during operation from 0 to 200h;

[0117] The data corresponding to 400 h represent the average conversion and average selectivity of the furfuryl alcohol hydrogenation catalyst during operation from 0 to 400 h;

[0118] The data corresponding to 600 h represent the average conversion rate and average selectivity of the furfuryl alcohol hydrogenation catalyst during operation from 0 to 600 h;

[0119] The data corresponding to 800 h represent the average conversion rate and average selectivity of the furfuryl alcohol hydrogenation catalyst during operation from 0 to 800 h;

[0120] The data corresponding to 1000 h represent the average conversion rate and average selectivity of the furfuryl alcohol hydrogenation catalyst during operation from 0 to 1000 h.

[0121] It can be seen from Tables 1 to 4 that the furfuryl alcohol hydrogenation catalyst provided by the present invention has good catalytic effect and strong stability. After continuous operation for 1000 hours, the furfuryl alcohol hydrogenation conversion rate can be maintained at more than 99.5%, and the selectivity can be maintained at more than 64%.

[0122] In particular, when the average specific surface area of ​​the furfuryl alcohol hydrogenation catalyst is 200m 2 / g-250m 2 / g, average pore volume 0.6g / cm 3 -0.8g / cm 3 When the furfuryl alcohol hydrogenation catalyst was continuously operated for 1000 hours, the furfuryl alcohol hydrogenation conversion rate could be maintained above 99.6%, and the selectivity could be maintained above 77.85%.

[0123] Furthermore, when the temperature of the reduction treatment in step S3 is 150° C.-400° C. and the pressure is 0.1 MPa-5 MPa in terms of gauge pressure during the preparation of the furfuryl alcohol hydrogenation catalyst, the furfuryl alcohol hydrogenation conversion rate can be maintained at above 99.7% and the selectivity can be maintained at above 79.12% after the obtained furfuryl alcohol hydrogenation catalyst is continuously operated for 1000 hours;

[0124] Furthermore, when the molar ratio of Cu element to Me element in the Cu-Me alloy particles in the furfuryl alcohol hydrogenation catalyst is 5-10:1, the furfuryl alcohol hydrogenation conversion rate can be maintained above 99.7% and the selectivity can be maintained above 86.33% after the prepared furfuryl alcohol hydrogenation catalyst is continuously operated for 1000 hours.

[0125] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A furfuryl alcohol hydrogenation catalyst, characterized in that The catalyst comprises a carrier, MgO embedded in the carrier, and Cu-Me alloy particles loaded on the carrier, wherein the molar ratio of Cu element to Me element in the Cu-Me alloy particles is 1-20:1, and the loading amount of the Cu-Me alloy particles is 5wt%-20wt% based on the total mass of the furfuryl alcohol hydrogenation catalyst; The carrier is Al2O3, and the Me element includes at least one of the noble metal elements.

2. The furfuryl alcohol hydrogenation catalyst according to claim 1, characterized in that The molar ratio of the Cu element to the Me element in the Cu-Me alloy particles is 5-10:

1.

3. The furfuryl alcohol hydrogenation catalyst according to claim 1 or 2, characterized in that Based on the total mass of the furfuryl alcohol hydrogenation catalyst, the content of MgO is 4wt%-7wt%; And / or, based on the total mass of the furfuryl alcohol hydrogenation catalyst, the content of the carrier is 70wt%-90wt%.

4. The furfuryl alcohol hydrogenation catalyst according to claim 1 or 2, characterized in that The Me element is at least one of the Pd element, the Pt element, the Ru element, the Rh element, and the Ir element.

5. The furfuryl alcohol hydrogenation catalyst according to claim 1 or 2, characterized in that The average specific surface area of ​​the furfuryl alcohol hydrogenation catalyst is 200 m 2 / g-250m 2 / g, average pore volume 0.6g / cm 3 -0.8g / cm 3 .

6. A method for preparing a furfuryl alcohol hydrogenation catalyst, characterized in that: The following steps are involved: S1: mixing the carrier with a Mg salt solution and crystallizing to obtain an intermediate; S2: mixing the intermediate with a Cu-Me solution to obtain a precursor; S3: Under a hydrogen atmosphere I, reducing the precursor to obtain the furfuryl alcohol hydrogenation catalyst; Wherein, in step S1, the carrier is Al2O3; In step S2, the solid-liquid ratio of the intermediate to the Cu-Me solution is 0.6 g / mL-0.7 g / mL, the molar ratio of the Cu element to the Me element in the Cu-Me solution is 1-20:1, and the Me element is at least one of the noble metal elements.

7. The preparation method according to claim 6, characterized in that: In step S1, the carrier is mixed with the Mg salt solution, the pH is adjusted to 10-11, and then crystallized to obtain the intermediate; And / or, in step S1, the content of Mg element in the Mg salt solution is 0.9 mol / L-1.1 mol / L, and the solid-liquid ratio of the carrier to the Mg salt solution is 0.5 g / mL-0.7 g / mL; And / or, in step S1, the average specific surface area of ​​the carrier is 200m 2 / g-250m 2 / g, average pore volume 0.5g / cm 3 -0.8g / cm 3 .

8. The preparation method according to claim 6, characterized in that: In step S2, the Me element is at least one of Pd element, Pt element, Ru element, Rh element and Ir element.

9. The preparation method according to any one of claims 6 to 8, characterized in that: In step S3, the content of hydrogen in the hydrogen atmosphere I is 10 vol%-30 vol%; And / or, in step S3, the temperature of the reduction treatment is 150°C-400°C, and the pressure is 0.1MPa-5MPa in gauge pressure.

10. The furfuryl alcohol hydrogenation catalyst obtained by the preparation method according to any one of claims 6 to 9.

11. Use of the furfuryl alcohol hydrogenation catalyst according to any one of claims 1 to 5 and 10 in the catalytic preparation of 1,2-pentanediol.

12. A method for preparing 1,2-pentanediol, characterized in that: The following steps are involved: Under hydrogen atmosphere II, the furfuryl alcohol solution is introduced into a reactor filled with a furfuryl alcohol hydrogenation catalyst for hydrogenation reaction treatment to obtain 1,2-pentanediol; Wherein, the furfuryl alcohol hydrogenation catalyst is the furfuryl alcohol hydrogenation catalyst according to any one of claims 1-5 and 10.

13. The preparation method according to claim 12, characterized in that: The concentration of furfuryl alcohol in the furfuryl alcohol solution is 10wt%-50wt%; And / or, the solvent of the furfuryl alcohol solution is selected from at least one of anhydrous ethanol, isopropanol, water and methanol.

14. The preparation method according to claim 12 or 13, characterized in that: The hydrogen atmosphere II is such that the molar ratio of hydrogen in the hydrogenation reaction to furfuryl alcohol in the furfuryl alcohol solution is 10-100:1; Preferably, the hydrogen atmosphere II is such that the molar ratio of hydrogen used for the hydrogenation reaction to furfuryl alcohol in the furfuryl alcohol solution is 15-30:

1.

15. The preparation method according to claim 12 or 13, characterized in that: The mass space velocity of the furfuryl alcohol solution is 0.1kg / h-1.0kg / h; Preferably, the mass space velocity of the furfuryl alcohol solution is 0.3kg / h-0.5kg / h.

16. The preparation method according to claim 12 or 13, characterized in that: The reactor is a fixed bed reactor, the ratio of the filling height of the furfuryl alcohol hydrogenation catalyst to the tube diameter of the fixed bed reactor is 4-10:1, and the ratio of the filling thickness of the furfuryl alcohol hydrogenation catalyst to the tube diameter of the fixed bed reactor is 0.5-0.8:1; And / or, the temperature of the hydrogenation reaction treatment is 100° C.-200° C., and the pressure is 3 MPa-8 MPa in gauge pressure.

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