Three-dimensional ordered mesoporous nickel-based catalyst, preparation method and application thereof

Abstract

The application discloses a three-dimensional ordered mesoporous nickel-based catalyst, which has a three-dimensional ordered mesoporous structure, an active component of nickel, an alumina carrier and one or more of lanthanum, cerium, praseodymium, neodymium or yttrium as an additive, and the content of Ni and the additive in the catalyst is 15-40wt% and 1-5wt% respectively. The application also discloses a preparation method and application of the catalyst. The catalyst is prepared by mixing PMMA microspheres with a nickel salt solution, an additive precursor and an aluminum salt solution, adding lye to obtain a precipitate, filtering, drying, shaping and high-temperature calcination. The catalyst can be used for preparing 1,3-propanediol by hydrogenating 3-hydroxypropanal after reduction. The catalyst provided by the application has good stability and low cost, can be used for fixed-bed continuous hydrogenation reaction, has high catalytic activity and selectivity in the preparation of 1,3-propanediol by hydrogenating 3-hydroxypropanal, and is suitable for industrialized continuous production of 1,3-propanediol.

Description

Technical Field

[0001] The present invention belongs to the technical field of catalyst preparation and application, and specifically relates to a three-dimensional ordered mesoporous nickel-based catalyst and a preparation method and application thereof. Background Art

[0002] 1,3-Propanediol (1,3-PDO) is an important organic chemical raw material, widely used in the synthesis of plasticizers, detergents, preservatives, emulsifiers, polyesters, and polyurethanes. Its most important application is as the primary raw material for polytrimethylene terephthalate (PTT). PTT is a high-performance polyester fiber, but production capacity falls far short of market demand. Developing low-cost 1,3-PDO synthesis technology is key to its production.

[0003] The three main methods currently used industrially to produce 1,3-propylene glycol (1,3-PD) are ethylene oxide hydroformylation-hydrogenation (Shell), acrolein hydration-hydrogenation (Degussa), and biomass fermentation (DuPont). The acrolein method uses acrolein as a raw material and an ion exchange resin containing methyleneiminodiacetic acid chelating groups as a catalyst for hydration to produce 3-hydroxypropanal. 3-hydroxypropanal is then hydrogenated to produce 1,3-PDO. This process offers advantages such as mild reaction conditions, mature technology, and suitability for large-scale industrial production. The hydrogenation catalyst is a core technology in the acrolein hydration-hydrogenation method.

[0004] Among existing 3-hydroxypropanal hydrogenation technologies, the invention patent application with publication number CN 1122568 A discloses a catalyst for hydrogenating 3-hydroxypropanal to produce 1,3-propylene glycol. The catalyst is a granular Raney nickel-type metal alloy with a particle size of 0.01 to 0.1 mm. This catalyst has the advantages of high activity and good selectivity, and its large particles make it easy to separate from the reaction products and can be reused multiple times. However, this catalyst is suitable for batch-type hydrogenation reactions, not fixed-bed continuous hydrogenation reactions, making it difficult to apply to large-scale or ultra-large-scale industrial production of 1,3-propylene glycol.

[0005] Invention patent application CN 1428322 A discloses a Ni-A-type hydrogenation catalyst, where A is any one of Cr, Zn, Mo, or Fe. This catalyst was used to produce 1,3-propylene glycol from 3-hydroxypropanal via a two-stage hydrogenation reaction. The conversion of 3-hydroxypropanal was 100%, but the catalyst had poor stability.

[0006] Invention patent application CN 105709778 A discloses a catalyst for the catalytic hydrogenation of 3-hydroxypropanal to produce 1,3-propylene glycol, comprising a carrier A and active components Ni, Rh, and metal X. The catalyst incorporates the precious metal rhodium, which reduces reaction pressure and improves catalyst selectivity. However, rhodium is expensive, making it a cost-effective catalyst.

[0007] In view of the above-mentioned deficiencies of the hydrogenation catalysts in the prior art, it is particularly important to develop a catalyst with high activity, long service life, good stability, low cost, and suitable for fixed-bed continuous hydrogenation reactions, so as to achieve the hydrogenation reaction of 3-HPA and more economical production of 1,3-PDO. Summary of the Invention

[0008] In order to solve the problems in the prior art of poor stability of hydrogenation catalysts, unsuitability for fixed-bed continuous hydrogenation reactions, and excessively high catalyst costs, the present invention provides a three-dimensional ordered mesoporous nickel-based catalyst. The catalyst has a three-dimensional ordered mesoporous structure and has high catalytic activity and high selectivity in the catalytic hydrogenation of 3-hydroxypropionaldehyde to produce 1,3-propylene glycol. It can be used for fixed-bed continuous hydrogenation reactions and is suitable for the industrial continuous production of 1,3-propylene glycol.

[0009] A three-dimensional ordered mesoporous nickel-based catalyst, wherein the three-dimensional ordered mesoporous nickel-based catalyst is a Ni / Al2O3 catalyst having a three-dimensional ordered mesoporous structure and containing an additive.

[0010] The three-dimensional ordered mesoporous structure is an ordered hollow spherical cavity structure with a diameter of 150-200 nm;

[0011] The auxiliary agent is one or more of lanthanum, cerium, praseodymium, neodymium or yttrium.

[0012] Preferably, the content of Ni in the three-dimensional ordered mesoporous nickel-based catalyst is 15-40 wt%, and the content of the auxiliary agent is 1-5 wt%.

[0013] The present invention innovates in the structure of the catalyst. The structure of the catalyst of the present invention is a three-dimensional ordered mesoporous structure, which facilitates the adsorption and desorption of reactants and catalysts in the catalytic reaction. At the same time, the present invention selects nickel as the active component and alumina as the carrier, and on this basis introduces auxiliary agents such as lanthanum, cerium, praseodymium, neodymium or yttrium, thereby further optimizing the catalytic performance of the catalyst.

[0014] The present invention also provides a method for preparing the three-dimensional ordered mesoporous nickel-based catalyst. In this method, PMMA microspheres are mixed into the catalyst during the preparation process, and then removed during calcination after molding, thereby preparing a catalyst structure with three-dimensional ordered mesopores, which provides convenience for the adsorption and desorption of reactants and catalysts in the catalytic reaction. At the same time, the addition of auxiliary agents such as lanthanum, cerium, praseodymium, neodymium or yttrium improves the reaction activity and selectivity of the catalyst.

[0015] A method for preparing a three-dimensional ordered mesoporous nickel-based catalyst comprises the following steps:

[0016] (1) nickel nitrate, additive precursor, and aluminum nitrate were added to deionized water and mixed evenly, and PMMA microspheres were added to form an emulsion;

[0017] (2) Slowly adding alkali solution to the emulsion prepared in step (1) under stirring, filtering, drying, shaping, and calcining at high temperature to obtain a catalyst.

[0018] Preferably, in step (1), the concentration of nickel nitrate in the emulsion is 0.15-2 mol / L; the auxiliary agent precursor is one or more of lanthanum nitrate, cerium nitrate, praseodymium nitrate, neodymium nitrate or yttrium nitrate, and the concentration of the auxiliary agent precursor in the emulsion is 0.01-0.1 mol / L; the concentration of aluminum nitrate in the emulsion is 0.5-5 mol / L, the diameter of the PMMA microspheres is 150-200 nm, and the content of PMMA microspheres in the emulsion is 1-8 wt%.

[0019] Preferably, in step (1), the PMMA microspheres are prepared by the following method:

[0020] In a nitrogen atmosphere, deionized water is heated, a methyl methacrylate solution containing p-hydroxybenzoic acid is added, the mixture is stirred at a constant temperature, potassium persulfate is added for reaction, and the mixture is centrifuged and dried to obtain PMMA microspheres.

[0021] Preferably, in step (2), the alkaline solution includes but is not limited to alkaline solutions such as sodium hydroxide solution, sodium carbonate solution, sodium bicarbonate solution, and ammonia water.

[0022] Preferably, in step (2), the high-temperature calcination temperature is 600-700° C. and the time is 2-12 hours.

[0023] The present invention also provides the use of the three-dimensional ordered mesoporous nickel-based catalyst in the hydrogenation of 3-hydroxypropionaldehyde to produce 1,3-propylene glycol. The three-dimensional ordered mesoporous nickel-based catalyst has high catalytic activity and selectivity in the reaction of hydrogenating 3-hydroxypropionaldehyde to produce 1,3-propylene glycol, is suitable for fixed-bed continuous hydrogenation reactions, and can be used in the industrial production of 3-hydroxypropionaldehyde hydrogenation to produce 1,3-propylene glycol.

[0024] Preferably, before use, the three-dimensional ordered mesoporous nickel-based catalyst is pretreated by using H2 reduction at a H2 space velocity of 100h -1 The reduction temperature is 450-550°C and the reduction time is more than 3 hours.

[0025] The present invention also provides a method for preparing 1,3-propylene glycol by hydrogenating 3-hydroxypropanal, wherein the method uses the pre-treated three-dimensional ordered mesoporous nickel-based catalyst as a hydrogenation catalyst, and carries out a hydrogenation reaction in a two-stage fixed bed reactor, wherein the concentration of the aqueous solution of 3-hydroxypropanal is 5-20wt%, and the liquid hourly space velocity is 1-3h -1 , the airspeed of H2 is 200-1000h -1 The first-stage hydrogenation reaction temperature is 55-65°C, the second-stage hydrogenation reaction temperature is 110-120°C, the reaction pressure is 6-7MPa, and the mass ratio of the first-stage hydrogenation reaction catalyst to the second-stage hydrogenation reaction catalyst is 1-5:1.

[0026] Preferably, the content of Ni in the hydrogenation catalyst is 30-40 wt%, the auxiliary agent is cerium, and the content of cerium is 3.6-5 wt%.

[0027] Preferably, the content of Ni in the hydrogenation catalyst is 30-40 wt%, the auxiliary agent is praseodymium, and the content of praseodymium is 3.6-5 wt%.

[0028] In the method for preparing 1,3-propylene glycol by hydrogenating 3-hydroxypropionaldehyde provided by the present invention, the conversion rate of 3-hydroxypropionaldehyde can reach 100%, and the selectivity can reach more than 96%. The method has good application prospects in the industrial production of preparing 1,3-propylene glycol from 3-hydroxypropionaldehyde.

[0029] Compared with the prior art, the present invention has at least the following beneficial effects:

[0030] 1. The present invention solves the problems of poor stability of hydrogenation catalysts in the prior art, unsuitability for fixed-bed continuous hydrogenation reactions, and high catalyst costs. It provides a three-dimensional ordered mesoporous nickel-based catalyst with high catalytic activity and high selectivity, which can be used for fixed-bed continuous hydrogenation reactions and is suitable for the industrial continuous production of 1,3-propylene glycol.

[0031] 2. The present invention mixes PMMA microspheres into the catalyst during the preparation process, and removes them during the calcination process after forming, thereby forming a Ni / Al2O3 catalyst with a three-dimensional ordered mesoporous structure, which provides convenience for the adsorption and desorption of reactants and catalysts in the catalytic reaction. At the same time, the addition of auxiliary agents such as lanthanum, cerium, praseodymium, neodymium or yttrium improves the reaction activity and selectivity of the catalyst.

[0032] 3. The catalyst provided by the present invention has high catalytic activity and selectivity in the reaction of hydrogenating 3-hydroxypropionaldehyde to prepare 1,3-propylene glycol. The conversion rate of 3-hydroxypropionaldehyde can reach 100%, and the selectivity can reach more than 96%. It has good application prospects in the industrial production of 3-hydroxypropionaldehyde to prepare 1,3-propylene glycol. DETAILED DESCRIPTION

[0033] The technical solution of the present invention is described below through specific embodiments. It should be understood that one or more method steps mentioned in the present invention do not exclude the presence of other method steps before or after the combination steps to which they belong, or that other method steps may be inserted before these explicitly mentioned steps; it should also be understood that these examples are only used to illustrate the present invention and are not used to limit the scope of the present invention. Moreover, unless otherwise specified, the numbering of each method step is only a convenient tool for identifying each method step, and is not intended to limit the order of arrangement of each method step or to define the scope of the present invention. Changes or adjustments to their relative relationships, without substantially changing the technical content, should also be regarded as the scope of the present invention.

[0034] Example 1

[0035] The catalyst preparation process of this embodiment is as follows:

[0036] (1) In a nitrogen atmosphere, 1 L of deionized water was heated to 70°C and stirred continuously. A methyl methacrylate solution mixed with 0.1 g of p-hydroxybenzoic acid was added. After constant stirring for 30 min, potassium persulfate was added. Stirring was continued for 1 h, and the mixture was centrifuged and dried to obtain PMMA microspheres.

[0037] (2) adding 1 mol of nickel nitrate hexahydrate, 0.07 mol of lanthanum nitrate, and 2.5 mol of aluminum nitrate to 1 L of deionized water and mixing them uniformly to form a solution, and adding 50 g of the PMMA microspheres prepared in step (1) to form an emulsion;

[0038] (3) Slowly adding sodium bicarbonate solution to the emulsion obtained in step (2) under stirring, maintaining the pH at 9 during the addition process, filtering the obtained precipitate, drying, shaping, and calcining at 600° C. for 10 h to obtain catalyst 1.

[0039] Example 2

[0040] The catalyst preparation process of this embodiment is as follows:

[0041] (1) In a nitrogen atmosphere, 1 L of deionized water was heated to 70°C and stirred continuously. A methyl methacrylate solution mixed with 0.1 g of p-hydroxybenzoic acid was added. After constant stirring for 30 min, potassium persulfate was added. Stirring was continued for 1 h, and the mixture was centrifuged and dried to obtain PMMA microspheres.

[0042] (2) adding 0.8 mol of nickel nitrate hexahydrate, 0.02 mol of cerium nitrate, and 5 mol of aluminum nitrate to 1 L of deionized water and mixing them uniformly to form a solution, and adding 80 g of the PMMA microspheres prepared in step (1) to form an emulsion;

[0043] (3) Slowly adding sodium bicarbonate solution to the emulsion obtained in step (2) under stirring, maintaining the pH at 9 during the addition process, filtering the obtained precipitate, drying, shaping, and calcining at 700° C. for 12 h to obtain catalyst 2.

[0044] Example 3

[0045] The catalyst preparation process of this embodiment is as follows:

[0046] (1) In a nitrogen atmosphere, 1 L of deionized water was heated to 70°C and stirred continuously. A methyl methacrylate solution mixed with 0.1 g of p-hydroxybenzoic acid was added. After constant stirring for 30 min, potassium persulfate was added. Stirring was continued for 1 h, and the mixture was centrifuged and dried to obtain PMMA microspheres.

[0047] (2) adding 1.35 mol of nickel nitrate hexahydrate, 0.035 mol of yttrium nitrate, and 2.3 mol of aluminum nitrate to 1 L of deionized water and mixing them uniformly to form a solution, and adding 30 g of the PMMA microspheres prepared in step (1) to form an emulsion;

[0048] (3) Slowly adding sodium bicarbonate solution to the emulsion obtained in step (2) under stirring, maintaining the pH at 9 during the addition process, filtering the obtained precipitate, drying, shaping, and calcining at 700° C. for 2 h to obtain catalyst 3.

[0049] Example 4

[0050] The catalyst preparation process of this embodiment is as follows:

[0051] (1) In a nitrogen atmosphere, 1 L of deionized water was heated to 70°C and stirred continuously. A methyl methacrylate solution mixed with 0.1 g of p-hydroxybenzoic acid was added. After constant stirring for 30 min, potassium persulfate was added. Stirring was continued for 1 h, and the mixture was centrifuged and dried to obtain PMMA microspheres.

[0052] (2) adding 2 mol of nickel nitrate hexahydrate, 0.1 mol of praseodymium nitrate, and 5 mol of aluminum nitrate to 1 L of deionized water and mixing them uniformly to form a solution, and adding 100 g of the PMMA microspheres prepared in step (1) to form an emulsion;

[0053] (3) Slowly adding sodium bicarbonate solution to the emulsion obtained in step (2) under stirring, maintaining the pH at 9 during the addition process, filtering the obtained precipitate, drying, shaping, and calcining at 600° C. for 10 h to obtain catalyst 4.

[0054] Example 5

[0055] The catalyst preparation process of this embodiment is as follows:

[0056] (1) In a nitrogen atmosphere, 1 L of deionized water was heated to 70°C and stirred continuously. A methyl methacrylate solution mixed with 0.1 g of p-hydroxybenzoic acid was added. After constant stirring for 30 min, potassium persulfate was added. Stirring was continued for 1 h, and the mixture was centrifuged and dried to obtain PMMA microspheres.

[0057] (2) adding 0.15 mol of nickel nitrate hexahydrate, 0.01 mol of neodymium nitrate, and 0.5 mol of aluminum nitrate to 1 L of deionized water and mixing them uniformly to form a solution, and adding 11 g of the PMMA microspheres prepared in step (1) to form an emulsion;

[0058] (3) Slowly add sodium bicarbonate solution to the emulsion obtained in step (1) under stirring, maintaining the pH at 9 during the addition process. The obtained precipitate is filtered, dried, formed, and calcined at 700° C. for 10 h to obtain catalyst 5.

[0059] Example 6

[0060] The catalyst preparation process of this embodiment is as follows:

[0061] (1) In a nitrogen atmosphere, 1 L of deionized water was heated to 70°C and stirred continuously. A methyl methacrylate solution mixed with 0.1 g of p-hydroxybenzoic acid was added. After constant stirring for 30 min, potassium persulfate was added. Stirring was continued for 1 h, and the mixture was centrifuged and dried to obtain PMMA microspheres.

[0062] (2) adding 2 mol of nickel nitrate hexahydrate, 0.1 mol of cerium nitrate, and 5 mol of aluminum nitrate to 1 L of deionized water and mixing them uniformly to form a solution, and adding 50 g of the PMMA microspheres prepared in step (1) to form an emulsion;

[0063] (3) Slowly add sodium hydroxide solution to the emulsion obtained in step (2) under stirring, maintaining the pH at 9 during the addition process. The obtained precipitate is filtered, dried, formed, and calcined at 600°C for 10 hours to obtain catalyst 6.

[0064] Example 7

[0065] The catalyst preparation process of this embodiment is as follows:

[0066] (1) In a nitrogen atmosphere, 1 L of deionized water was heated to 70°C and stirred continuously. A methyl methacrylate solution mixed with 0.1 g of p-hydroxybenzoic acid was added. After constant stirring for 30 min, potassium persulfate was added. Stirring was continued for 1 h, and the mixture was centrifuged and dried to obtain PMMA microspheres.

[0067] (2) adding 2 mol of nickel nitrate hexahydrate, 0.05 mol of yttrium nitrate, and 5 mol of aluminum nitrate to 1 L of deionized water and mixing them uniformly to form a solution, and adding 50 g of the PMMA microspheres prepared in step (1) to form an emulsion;

[0068] (3) Slowly add aqueous ammonia to the emulsion obtained in step (2) under stirring, maintaining the pH at 9 during the addition process. The obtained precipitate is filtered, dried, formed, and calcined at 600°C for 10 hours to obtain catalyst 7.

[0069] Example 8

[0070] The catalyst preparation process of this embodiment is as follows:

[0071] (1) In a nitrogen atmosphere, 1 L of deionized water was heated to 70°C and stirred continuously. A methyl methacrylate solution mixed with 0.1 g of p-hydroxybenzoic acid was added. After constant stirring for 30 min, potassium persulfate was added. Stirring was continued for 1 h, and the mixture was centrifuged and dried to obtain PMMA microspheres.

[0072] (2) adding 0.8 mol nickel nitrate hexahydrate, 0.02 mol lanthanum nitrate, and 5 mol aluminum nitrate to 1 L of deionized water and mixing uniformly to form a solution, and adding 50 g of PMMA microspheres prepared in step (1) to form an emulsion;

[0073] (3) Slowly add sodium carbonate solution to the emulsion obtained in step (2) under stirring, maintaining the pH at 9 during the addition process. The obtained precipitate is filtered, dried, formed, and calcined at 600°C for 10 hours to obtain catalyst 8.

[0074] Comparative Example 1

[0075] The catalyst preparation process of this embodiment is as follows:

[0076] 0.76 mol of nickel nitrate hexahydrate and 5 mol of aluminum nitrate were added to 1 L of deionized water and mixed uniformly to form a solution. Sodium hydroxide solution was added to the solution. The resulting precipitate was filtered, dried, formed, and calcined at 600° C. for 10 h to obtain comparative catalyst 1.

[0077] Comparative Example 2

[0078] The catalyst preparation process of this embodiment is as follows:

[0079] 1.9 mol of nickel nitrate hexahydrate and 5 mol of aluminum nitrate were added to 1 L of deionized water and mixed evenly to form a solution. Sodium hydroxide solution was added to the solution. The resulting precipitate was filtered, dried, formed, and calcined at 600° C. for 10 h to obtain comparative catalyst 2.

[0080] Application Examples

[0081] The catalysts prepared in Examples 1-8 and Comparative Examples 1-2 were used in the hydrogenation of 3-hydroxypropanal to produce 1,3-propylene glycol. The catalytic performance of the prepared catalysts was evaluated based on the conversion of 3-hydroxypropanal and the selectivity of 1,3-propylene glycol.

[0082] First, the prepared catalyst was loaded into two fixed-bed reactors connected in series, with the loading amount of the two fixed-bed reactors being 200 g. Before the catalytic reaction, the prepared catalyst was reduced with H2 at a space velocity of 200 h -1 , the reduction temperature is 500℃, and the reduction time is 8h. In the catalytic reaction, the raw material is a 10wt% 3-hydroxypropionaldehyde aqueous solution, and the liquid hourly space velocity is 2h -1 , the airspeed of H2 is 500h -1 The first stage hydrogenation reaction temperature was controlled at 55-65°C, the second stage hydrogenation reaction temperature was controlled at 110-120°C, and the reaction pressure was controlled at 6-7 MPa. Gas chromatography and other means were used to detect and analyze the products and evaluate the catalytic performance of the catalyst.

[0083] Among them, the conversion rate calculation formula of 3-hydroxypropanal is:

[0084]

[0085] The selectivity calculation formula for 1,3-propylene glycol is:

[0086]

[0087] Table 1 shows the conversion of 3-hydroxypropanal and the selectivity for 1,3-propylene glycol in the catalytic hydrogenation of 3-hydroxypropanal to 1,3-propylene glycol using the catalysts in Examples 1-8 and Comparative Examples 1-2. As can be seen from Table 1, the catalysts in both the Examples and Comparative Examples of the present invention can achieve near or even complete conversion of 3-hydroxypropanal. However, when comparing the catalysts in the Examples and Comparative Examples with the same Ni content, the catalysts prepared in the Examples of the present invention significantly improve the selectivity for 1,3-propylene glycol.

[0088] The catalysts in Examples 1-8 all achieved selectivities for 1,3-propylene glycol exceeding 75%. When the Ni content in the catalysts prepared in these examples was between 30 and 40 wt%, adjusting the additive and its content allowed the selectivity for 1,3-propylene glycol to remain stable at above 96.5%. In particular, when the Ni content in the catalyst was 30 wt%, the catalyst additive was cerium, and the cerium content in the catalyst was 3.6 wt%, the selectivity for 1,3-propylene glycol reached as high as 98.5%. Furthermore, when the Ni content in the catalyst was 30 wt%, the catalyst additive was praseodymium, and the praseodymium content in the catalyst was 3.6 wt%, the selectivity for 1,3-propylene glycol was also high, reaching 97.7%.

[0089] It can be seen that the catalyst prepared by the present invention has very high catalytic activity and selectivity in the reaction of hydrogenating 3-hydroxypropionaldehyde to prepare 1,3-propylene glycol, and has good application prospects in the industrial production of catalytic hydrogenation of 3-hydroxypropionaldehyde to prepare 1,3-propylene glycol.

[0090] Table 1 Catalytic reaction performance of the catalysts prepared in the examples of the present invention and the comparative examples

[0091]

Claims

1. Application of a three-dimensional ordered mesoporous nickel-based catalyst in the hydrogenation of 3-hydroxypropanal to produce 1,3-propylene glycol, characterized in that: The three-dimensional ordered mesoporous nickel-based catalyst is a Ni / Al2O3 catalyst having a three-dimensional ordered mesoporous structure and containing an additive, wherein the three-dimensional ordered mesoporous structure is an ordered hollow spherical cavity structure with a diameter of 150-200 nm; The auxiliary agent is one or more of lanthanum, cerium, praseodymium, neodymium or yttrium; The method for preparing the three-dimensional ordered mesoporous nickel-based catalyst is characterized by comprising the following steps: (1) adding nickel nitrate, an additive precursor, and aluminum nitrate to deionized water and mixing them uniformly, and adding PMMA microspheres to form an emulsion; (2) slowly adding alkali solution to the emulsion prepared in step (1) under stirring, filtering, drying, shaping, and calcining at high temperature to obtain a catalyst; The three-dimensional ordered mesoporous nickel-based catalyst was pretreated before use, and the pretreatment was carried out by H2 reduction with a H2 space velocity of 100 h -1 Above, the reduction temperature is 450-550 ℃, and the reduction time is more than 3 h; The three-dimensional ordered mesoporous nickel-based catalyst after pretreatment is used as a hydrogenation catalyst to carry out a hydrogenation reaction in a two-stage fixed bed reactor. The concentration of the aqueous solution of 3-hydroxypropanal is 5-20 wt%, and the liquid hourly space velocity is 1-3 h -1 , the space velocity of H2 is 200-1000 h -1 The first-stage hydrogenation reaction temperature is 55-65°C, the second-stage hydrogenation reaction temperature is 110-120°C, the reaction pressure is 6-7 MPa, and the mass ratio of the first-stage hydrogenation reaction catalyst to the second-stage hydrogenation reaction catalyst is 1-5:

1.

2. The use of the three-dimensional ordered mesoporous nickel-based catalyst according to claim 1 in the hydrogenation of 3-hydroxypropionaldehyde to produce 1,3-propylene glycol, characterized in that: The content of Ni in the three-dimensional ordered mesoporous nickel-based catalyst is 15-40 wt%, and the content of the auxiliary agent is 1-5 wt%.

3. Use of the three-dimensional ordered mesoporous nickel-based catalyst according to claim 1 in the hydrogenation of 3-hydroxypropionaldehyde to produce 1,3-propylene glycol, characterized in that: In step (1), the concentration of nickel nitrate in the emulsion is 0.15-2 mol / L; the auxiliary agent precursor is one or more of lanthanum nitrate, cerium nitrate, praseodymium nitrate, neodymium nitrate or yttrium nitrate, and the concentration of the auxiliary agent precursor in the emulsion is 0.01-0.1 mol / L; the concentration of aluminum nitrate in the emulsion is 0.5-5 mol / L, the diameter of the PMMA microspheres is 150-200 nm, and the content of PMMA microspheres in the emulsion is 1-8 wt%.

4. Use of the three-dimensional ordered mesoporous nickel-based catalyst according to claim 1 in the preparation of 1,3-propylene glycol by hydrogenation of 3-hydroxypropionaldehyde, characterized in that: In step (2), the alkali solution is sodium hydroxide solution, sodium carbonate solution, sodium bicarbonate solution or ammonia water; the temperature of the high-temperature calcination is 600-700 ° C, and the time is 2-12 h.

5. Use of the three-dimensional ordered mesoporous nickel-based catalyst according to claim 1 in the hydrogenation of 3-hydroxypropionaldehyde to produce 1,3-propylene glycol, characterized in that: The Ni content in the hydrogenation catalyst is 30-40 wt%, the auxiliary agent is cerium, and the cerium content is 3.6-5 wt%.

6. Use of the three-dimensional ordered mesoporous nickel-based catalyst according to claim 1 in the hydrogenation of 3-hydroxypropionaldehyde to produce 1,3-propylene glycol, characterized in that: The Ni content in the hydrogenation catalyst is 30-40 wt%, the auxiliary agent is praseodymium, and the praseodymium content is 3.6-5 wt%.

Images