Ni-In based composite catalyst, preparation method thereof and application of the catalyst in preparation of 1,3-propanediol by hydrogenation of 3-hydroxypropanal
By preparing Ni-In based composite catalysts and utilizing the synergistic effect of indium and other additives, the problems of high cost and poor stability of existing catalysts are solved, achieving high conversion rate and selectivity, making them suitable for industrial applications.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- SHANGHAI PUJING CHEM NEW MATERIALS
- Filing Date
- 2024-11-19
- Publication Date
- 2026-05-29
AI Technical Summary
Existing catalysts for the hydrogenation of 3-hydroxypropanal to 1,3-propanediol suffer from high costs and cumbersome preparation methods due to the introduction of noble metal elements, and make it difficult to achieve high selectivity and yield of the target product and high catalyst stability.
The Ni-In based composite catalyst is used. By introducing the first promoter indium and the second promoter such as iron and cobalt, a synergistic effect is formed. Combined with a hydrophobic support, the active sites and reaction stability are improved. The preparation method is simple and easy to industrialize.
It achieves a 3-hydroxypropanal conversion rate of over 99.5%, a 1,3-propanediol selectivity of over 99%, a catalyst life of up to 2000 hours, high equipment utilization, low energy consumption, and excellent stability.
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of organic synthesis technology, and relates to a Ni-In-based composite catalyst, its preparation method, and its application in the hydrogenation of 3-hydroxypropanal to prepare 1,3-propanediol. Background Technology
[0002] Polypropylene terephthalate (PTT) is widely used in clothing, industrial, decorative, and engineering plastics due to its excellent properties such as high resilience, high bulkiness, and good softness, and has broad market prospects. 1,3-Propanediol and terephthalic acid are important raw materials for the synthesis of PTT. While the synthesis process of terephthalic acid is relatively mature, the synthesis process of 1,3-propanediol is limited, resulting in insufficient production capacity and an inability to meet market demand, leading to high prices and restricting the application of PTT. Therefore, the development of high-performance 1,3-propanediol is urgently needed.
[0003] Currently, the main methods for producing 1,3-propanediol include ethylene oxide carbonylation, biological methods, and acrolein hydration hydrogenation. Ethylene oxide carbonylation has low production costs and good product quality, but the process conditions are harsh, the reaction pressure is too high, and the catalytic system is complex. Biological methods have mild reaction conditions, but low production efficiency and difficulty in product purification. Acrolein hydration hydrogenation uses readily available raw materials, has lower technical difficulty, and is suitable for large-scale industrial production. The specific steps of acrolein hydration hydrogenation are as follows: first, acrolein is hydrated to produce 3-hydroxypropanal, and then 3-hydroxypropanal is hydrogenated to produce 1,3-propanediol. For the hydrogenation reaction, research focuses on catalyst development. Existing studies have shown that the composition and structure of the catalyst affect its activity and stability.
[0004] According to research reports, hydrogenation catalysts are mainly divided into Raney nickel catalysts and supported catalysts.
[0005] Chinese patent CN 1122568 C discloses a Raney nickel catalyst with an Al-Ni-A composition. This catalyst exhibits good activity and selectivity in the hydrogenation reaction of 3-hydroxypropanal, achieving 100% activity and selectivity under conditions of reaction temperature 50-130℃, pressure 6MPa, and 3-hydroxypropanal concentration of 12wt%. However, the reaction is carried out in a high-pressure reactor, making catalyst-product liquid separation difficult and hindering large-scale industrial application.
[0006] Chinese patent CN 114011432 A describes the synthesis of a catalyst using nickel oxide, ruthenium oxide, cerium oxide, and a support for the hydrogenation of 3-hydroxypropanal to 1,3-propanediol. The conversion rate of 3-hydroxypropanal in this reaction is higher than 99.9%, but the overall yield from acrolein to 1,3-propanediol is low, with a minimum of only 78%.
[0007] Chinese Patent CN 116262683 A describes the hydrogenation of 1,3-propanediol using a supported bimetallic catalyst, wherein the second metal is selected from one or two of Co, Cu, Zn, and Fe, and the reaction conditions are relatively mild: temperature 60-150℃, pressure 0.5-3 MPa, and space velocity 0.2-1.5 h⁻¹. -1 The yield of 1,3-propanediol after the reaction was low, ranging from 60% to 90%, and the stability of the catalyst was not investigated.
[0008] In summary, most of the publicly disclosed supported hydrogenation catalysts introduce precious metal elements, resulting in high catalyst production costs and cumbersome preparation methods. They cannot simultaneously achieve high selectivity and yield of target products with high catalyst stability and activity. Summary of the Invention
[0009] The purpose of this invention is to provide a Ni-In based composite catalyst, its preparation method, and its application in the hydrogenation of 3-hydroxypropanal to 1,3-propanediol. By introducing dual promoter components to modify the catalyst, a catalyst with strong water resistance, high activity, and good stability is developed for hydrogenation reactions, showing good application prospects in the industrial production of 1,3-propanediol from the hydrogenation of 3-hydroxypropanal.
[0010] The objective of this invention can be achieved through the following technical solutions:
[0011] A first aspect of the present invention provides a Ni-In based composite catalyst, comprising a support and an active component, a first auxiliary component, and a second auxiliary component supported on the support;
[0012] The active component is nickel, with a mass fraction of 5-40%.
[0013] The first auxiliary agent component is indium, with a mass fraction of 0.1-10%;
[0014] The second auxiliary component is selected from at least one of iron, cobalt, manganese, silver, platinum, zinc, palladium, rhodium, ruthenium, tungsten, iridium, molybdenum, yttrium, and niobium, and has a mass fraction of 0.1% to 15%.
[0015] This invention introduces In as a first promoter, providing abundant active sites for the hydrogenation reaction. Hydrogen molecules adsorb and dissociate at these active sites, reducing the In₂O₃ surface to form oxygen vacancies. These oxygen vacancies enhance the adsorption and activation capacity of the reactants. Furthermore, the activated hydrogen molecules accelerate the reaction rate. Based on the synergistic effect between the active metal, the first promoter In, and the second promoter, the catalyst exhibits high activity and high selectivity.
[0016] As a preferred technical solution, the mass fraction of the first auxiliary agent component is 0.5-8%.
[0017] Furthermore, the carrier is selected from one or more combinations of alumina, silica, MCM-22, zirconium dioxide, diatomaceous earth, mordenite (HM), MCM-41, SBA-15, titanium dioxide, ZSM-5, and SAPO-34.
[0018] Furthermore, the carrier is a carrier grafted with hydrophobic groups. The hydrophobic properties of the carrier are improved by grafting the carrier with a hydrophobic modifier to silanize the hydroxyl groups on the carrier surface.
[0019] The hydrophobic catalyst surface is coated with a hydrophobic substance, which gives the catalyst surface a certain degree of hydrophobicity, reduces the diffusion resistance of hydrogen, promotes the reaction, and helps to improve the conversion rate of 3-hydroxypropionaldehyde per unit time. In addition, the reaction solution has a high water content. By applying the hydrophobic catalyst to the hydrogenation reaction, water molecules are prevented from covering the pores of the catalyst, and the probability of water molecules inducing the migration of active metals in the catalyst is reduced, thereby reducing the possibility of active metal agglomeration and giving the catalyst excellent stability.
[0020] A second aspect of the present invention provides a method for preparing a Ni-In-based composite catalyst, comprising: immersing a support in a solution containing an active component precursor, a first auxiliary component precursor, and a second auxiliary component precursor, drying, and calcining to obtain a Ni-In-based composite catalyst.
[0021] Furthermore, the active component precursor is a water-soluble salt containing the active component, the first auxiliary component precursor is a water-soluble salt containing the first auxiliary component, and the second auxiliary component precursor is a water-soluble salt containing the second auxiliary component.
[0022] As a preferred technical solution, the water-soluble salt is selected from at least one of nitrates, carbonates, acetates, oxalates, ammonium salts, and halides.
[0023] As a preferred technical solution, the drying temperature is 100-150℃ and the drying time is 2-8h.
[0024] Furthermore, in the roasting process, the roasting temperature is 300–700℃, and the roasting time is 2–6 hours.
[0025] Furthermore, the carrier is grafted with silane groups, and the grafting method includes: pre-calcining the carrier and then heating it in a hydrophobic modifier solution to obtain a carrier grafted with hydrophobic groups.
[0026] In the pre-firing process, the pre-firing temperature is 500-700℃, the pre-firing time is 3-6 hours, and the pre-firing atmosphere is air.
[0027] The hydrophobic modifier used is selected from one or more of trimethylchlorosilane, dimethyldiethoxysilane, n-octyltriethoxysilane, and dodecyltriethoxysilane; the mass ratio of the hydrophobic modifier to the carrier is 1:(1-4); the solvent used in the hydrophobic modifier solution is an organic solvent, preferably toluene or acetone. The volume ratio of the organic solvent to the hydrophobic modifier is (1-10):1.
[0028] In the heating reaction, the reaction temperature is 70–130°C and the reaction time is 2–30 h.
[0029] As a preferred technical solution, the carrier is pre-calcined, then placed in a desiccator for drying and cooling, and then refluxed in a hydrophobic modifier solution.
[0030] As a preferred technical solution, the product mixture obtained from the heating reaction is filtered, washed, and then dried.
[0031] As a preferred technical solution, the detergent used in the washing process is ethanol, and more preferably anhydrous ethanol.
[0032] As a preferred technical solution, the drying is carried out using vacuum drying at a temperature of 80–120°C.
[0033] As a preferred technical solution, the method for preparing the carrier grafted with hydrophobic groups includes the following steps:
[0034] 1) Pre-fire the carrier at a certain temperature;
[0035] 2) The pre-calcined carrier is placed in an organic solvent for ultrasonic dispersion, a hydrophobic modifier is added, and the mixture is refluxed at a certain temperature for a certain time.
[0036] 3) After the reaction is complete, the product is cooled and filtered, and washed with anhydrous ethanol 3-5 times. The product is then dried in a vacuum drying oven to obtain a hydrophobic support.
[0037] Furthermore, the hydrophobic catalyst is prepared by an impregnation method, wherein the impregnation method is selected from one of the following: equal volume impregnation, excess impregnation, and multiple impregnation. Preferably, it is the equal volume impregnation method or the multiple impregnation method.
[0038] This invention loads the active component, the first auxiliary component, and the second auxiliary component onto a carrier using an impregnation method, which has the advantages of being simple to operate and easy to industrialize.
[0039] A third aspect of the present invention provides an application of a Ni-In-based composite catalyst, comprising using the Ni-In-based composite catalyst in the hydrogenation reaction of 3-hydroxypropanal to prepare 1,3-propanediol, i.e., using an aqueous solution of 3-hydroxypropanal and hydrogen as raw materials, and under the catalysis of the Ni-In-based composite catalyst, the hydrogenation reaction is carried out to synthesize 1,3-propanediol.
[0040] Furthermore, before the hydrogenation of 3-hydroxypropanal to prepare 1,3-propanediol, a reduction treatment is performed; in the reduction treatment, the reducing gas is hydrogen, the reduction temperature is 200-400℃, the reducing gas pressure is 0.5-2MPa, and the reducing gas space velocity is 200-5000h. -1 The restoration time is 10–35 hours.
[0041] Furthermore, the hydrogenation reaction of 3-hydroxypropanal to prepare 1,3-propanediol is a one-step hydrogenation reaction.
[0042] Furthermore, the reaction temperature is 35–135°C, the reaction pressure is 2–12 MPa, the molar ratio of hydrogen to 3-hydroxypropanal is 5–40:1, and the liquid hourly space velocity of the 3-hydroxypropanal aqueous solution, calculated as 1–20 wt%, is 0.1–3 h⁻¹. -1 .
[0043] Compared with the prior art, the present invention has the following characteristics:
[0044] 1) This invention introduces In as a first promoter, providing abundant active sites for the hydrogenation reaction. Hydrogen molecules adsorb and dissociate at these active sites, reducing the In₂O₃ surface to form oxygen vacancies. These oxygen vacancies enhance the adsorption and activation capacity of the reactants. Furthermore, the activated hydrogen molecules accelerate the reaction rate. Based on the synergistic effect between the active metal, the first promoter In, and the second promoter, the catalyst exhibits high activity and high stability. Experiments show that the catalyst prepared in this invention can achieve a 3-hydroxypropanal conversion rate of over 99.5% and a lifetime of over 2000 hours.
[0045] 2) 3-Hydroxypropanal is thermosensitive and readily undergoes polymerization at high temperatures. Under this catalytic system, the reaction temperature is lower, which inhibits the side reactions of 3-hydroxypropanal and improves the selectivity of the catalyst. Experiments show that the catalyst prepared in this invention can achieve a selectivity of over 99% for 1,3-propanediol.
[0046] 3) The catalyst prepared by this invention can realize one-step hydrogenation of 3-hydroxypropanal, with high equipment utilization and low energy consumption;
[0047] 4) Since the hydrogenation reaction is a gas-liquid-solid three-phase reaction and the reaction liquid has a high water content, this invention applies a hydrophobic catalyst to the hydrogenation reaction to avoid water molecules covering the pores of the catalyst and to reduce the probability of water molecules inducing the migration of active metals in the catalyst, thereby reducing the possibility of active metal agglomeration and giving the catalyst excellent stability. Detailed Implementation
[0048] The present invention will now be described in detail with reference to specific embodiments. These embodiments are based on the technical solution of the present invention and provide detailed implementation methods and specific operating procedures. However, the scope of protection of the present invention is not limited to the following embodiments.
[0049] In the following embodiments, unless otherwise specified, the raw materials, reagents or processing techniques are all conventional commercial products or conventional processing techniques in the art.
[0050] In the following embodiments, the additives iron, cobalt, manganese, silver, platinum, zinc, palladium, rhodium, ruthenium, tungsten, iridium, molybdenum, yttrium, and niobium are added in the form of corresponding soluble salts, such as nitrates, carbonates, acetates, oxalates, ammonium salts, halides, etc.; more specifically, they include ferric nitrate, cobalt nitrate, manganese nitrate, silver nitrate, platinum nitrate, zinc nitrate, palladium nitrate, rhodium nitrate, ruthenium nitrate, ammonium tungstate, iridium chloride, ammonium molybdate, yttrium nitrate, and ammonium niobium oxalate used in the following embodiments.
[0051] Examples 1-16:
[0052] A Ni-In-B / A type catalyst was synthesized using an equal-volume impregnation method. Taking Example 1 as an example, the specific steps are as follows:
[0053] 5.71g of nickel nitrate hexahydrate, 0.49g of indium nitrate tetrahydrate, and 2.28g of cobalt nitrate hexahydrate were weighed and dissolved in 20g of water. 20g of alumina support (100% water absorption rate) was immersed in the above solution for 12 hours. After immersion, the solution was dried at 110℃ for 4 hours and then calcined at 600℃ for 5 hours in a muffle furnace under air atmosphere to obtain catalyst 5wt%Ni-1wt%In-4wt%Co / Al2O3.
[0054] Atomic emission spectroscopic elemental analysis was performed on each catalyst sample using inductively coupled plasma optical emission spectrometry (ICP-OES), and the results are shown in Table 1.
[0055] Comparative Example 1:
[0056] A Ni-Co / alumina catalyst was synthesized using an equal-volume impregnation method. The specific steps are as follows:
[0057] 5.63g of nickel nitrate hexahydrate and 2.24g of cobalt nitrate hexahydrate were weighed and dissolved in 20g of water. 20g of Al2O3 support was impregnated in the above solution for 12h. After impregnation, it was dried at 110℃ for 4h and then calcined in a muffle furnace at 600℃ for 5h in air atmosphere to obtain catalyst 5wt%Ni-4wt%Co / Al2O3.
[0058] Comparative Example 2:
[0059] A Ni / Al2O3 catalyst was synthesized using an equal-volume impregnation method. The specific steps are as follows:
[0060] 5.29 g of nickel nitrate hexahydrate was dissolved in 20 g of water. 20 g of Al2O3 support was immersed in the above solution for 12 h. After immersion, the solution was dried at 110 °C for 4 h and then calcined in a muffle furnace at 600 °C for 5 h in air atmosphere to obtain a catalyst of 5 wt% Ni / Al2O3.
[0061] Example 17:
[0062] Preparation of a hydrophobic catalyst:
[0063] I. Preparation of hydrophobic carriers
[0064] The Al2O3 support was pre-calcined in air at 600°C for 4 hours and then cooled in a desiccator. 20g of the dried support was ultrasonically dispersed in 40g of acetone. Then, 20g of trimethylchlorosilane was added to the solution, and the mixture was refluxed at 80°C for 24 hours. After the reaction was completed, the product was cooled and filtered. It was washed 3-5 times with anhydrous ethanol and then vacuum dried at 80°C to obtain the hydrophobic support Al2O3.
[0065] II. Catalyst Synthesis
[0066] 5.71g of nickel nitrate hexahydrate, 0.49g of indium nitrate tetrahydrate, and 2.28g of cobalt nitrate hexahydrate were weighed and dissolved in 20g of water. 20g of hydrophobic support Al2O3 (100% water absorption rate) was impregnated in the above solution for 12h. After impregnation, it was dried at 110℃ for 4h and then calcined at 600℃ for 5h in a muffle furnace under air atmosphere to obtain catalyst Y-5wt%Ni-1wt%In-4wt%Co / Al2O3.
[0067] Table 1 Catalyst composition of Examples 1-17 and Comparative Examples 1-2
[0068]
[0069]
[0070] Application Example 1:
[0071] This embodiment is used to evaluate the activity of the catalysts prepared in Examples 1-17 and Comparative Examples 1-2, specifically including:
[0072] 5g of catalyst was loaded into a fixed-bed reactor and subjected to an incubation period of 350℃, 0.5MPa, and 200h⁻¹. -1 Hydrogen was reduced for 20 hours under the specified conditions, and then the temperature was lowered to the reaction temperature after the reduction was completed.
[0073] A 10 wt% aqueous solution of 3-hydroxypropanal was mixed with hydrogen gas, preheated at 50°C, and then fed into a fixed-bed reactor for reaction. The resulting product solution was cooled and analyzed by gas chromatography to determine its composition. The reactant conversion rate and product selectivity were calculated using the following formulas:
[0074] 3-Hydroxypropanal conversion rate = (Amount of 3-hydroxypropanal converted in the reaction / Amount of 3-hydroxypropanal entering the reactor) * 100%
[0075] 1,3-Propanediol selectivity = Amount of 1,3-propanediol produced / Amount of 3-hydroxypropanal converted in the reaction * 100%.
[0076] The reaction conditions and results are shown in Table 2, where the hydrogen-aldehyde ratio is the molar ratio of hydrogen to 3-hydroxypropanal, and the liquid hourly space velocity is the liquid hourly space velocity of 3-hydroxypropanal relative to the catalyst bed.
[0077] Table 2 Reaction conditions and results for each embodiment
[0078]
[0079] As shown in Table 2, the catalysts in Comparative Example 1 without indium and Comparative Example 2 without indium and cobalt exhibited poor conversion and selectivity in the hydrogenation of 3-hydroxypropanal to 1,3-propanediol. After 50 hours of reaction, the conversion rates were only 89.9% and 88.8%, respectively, and the selectivities were only 98.5% and 97.6%. However, for the catalysts with indium, namely the Ni-In-B / A catalysts prepared in Examples 1-17, the conversion and selectivity were significantly improved, reaching 99.6-100% and 99.1-99.9% after 50 hours of reaction.
[0080] Application Example 2:
[0081] This embodiment is used to evaluate the stability of the catalysts prepared in Example 1 and Comparative Examples 1-2. The specific process differs from that in Application Example 1 only in that:
[0082] For the catalyst prepared in Example 1, the reaction times were 50 h, 100 h, 500 h, 1000 h, 1500 h, and 2100 h, respectively.
[0083] For the catalysts prepared in Comparative Example 1 and Comparative Example 2, the reaction times were 50 h, 100 h, 500 h, and 1000 h, respectively.
[0084] The rest is the same as in Application Example 1.
[0085] Table 3 Stability test of Example 1
[0086] Reaction run time / h Conversion rate / % Selectivity / % 50 99.6 99.2 100 99.6 99.1 500 99.6 99.2 1000 99.6 99.0 1500 99.6 99.1 2100 99.6 99.2
[0087] Table 4 shows the stability test results of the catalysts prepared in Comparative Example 1.
[0088]
[0089]
[0090] Table 5 shows the stability test results of the catalysts prepared in Comparative Example 2.
[0091] Reaction run time / h Conversion rate / % Selectivity / % 50 88.8 97.6 100 87.6 96.1 500 85.9 95.2 1000 79.9 90.1
[0092] Comparing Tables 3 to 5, it can be seen that for the catalyst without the first auxiliary agent indium and the second auxiliary agent cobalt (Comparative Example 2), the conversion rate of 3-hydroxypropanal decreased by 8.9% and the selectivity of 1,3-propanediol decreased by 7.5% after 1000 h of reaction compared to 50 h. Based on this, the catalyst with only the second auxiliary agent cobalt introduced (Comparative Example 1) showed a 7.5% decrease in conversion rate and a 5.3% decrease in selectivity after 1000 h of reaction compared to 50 h, indicating that the introduction of the second auxiliary agent cobalt can improve the stability of conversion rate and selectivity to a certain extent. When both the first auxiliary agent indium and the second auxiliary agent cobalt were introduced, the resulting catalyst (Example 1) did not show significant changes in conversion rate and selectivity during a reaction time of up to 2100 h, with the maximum fluctuation in selectivity being only 0.2%.
[0093] Therefore, it can be seen that by using indium as the first additive and supplementing it with silver, rhodium, ruthenium, tungsten, yttrium, molybdenum and other modified nickel-based catalysts, this invention not only effectively improves the activity and selectivity of the catalyst, but also significantly improves its stability, which is conducive to its industrial application.
[0094] The above description of the embodiments is provided to enable those skilled in the art to understand and use the invention. It will be apparent to those skilled in the art that various modifications can be made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the invention should be within the protection scope of the present invention.
Claims
1. A Ni-In based composite catalyst, characterized in that, It includes a carrier and an active component, a first auxiliary component, and a second auxiliary component loaded on the carrier; The active component is nickel, with a mass fraction of 5-40%. The first auxiliary agent component is indium, with a mass fraction of 0.1-10%; The second auxiliary component is selected from at least one of iron, cobalt, manganese, silver, platinum, zinc, palladium, rhodium, ruthenium, tungsten, iridium, molybdenum, yttrium, and niobium, and has a mass fraction of 0.1% to 15%.
2. The Ni-In based composite catalyst according to claim 1, characterized in that, The carrier is selected from one or more combinations of alumina, silica, MCM-22, zirconium dioxide, diatomaceous earth, mordenite, MCM-41, SBA-15, titanium dioxide, ZSM-5, and SAPO-34.
3. The Ni-In based composite catalyst according to claim 1 or 2, characterized in that, The carrier is a carrier grafted with hydrophobic groups.
4. A method for preparing a Ni-In based composite catalyst as described in any one of claims 1 to 3, characterized in that, The method includes: immersing a support in a solution containing an active component precursor, a first auxiliary component precursor, and a second auxiliary component precursor, drying, and calcining to obtain a Ni-In based composite catalyst.
5. The method for preparing the Ni-In based composite catalyst according to claim 4, characterized in that, The active component precursor is a water-soluble salt containing the active component, the first auxiliary component precursor is a water-soluble salt containing the first auxiliary component, and the second auxiliary component precursor is a water-soluble salt containing the second auxiliary component.
6. The method for preparing the Ni-In based composite catalyst according to claim 4, characterized in that, During the roasting process, the roasting temperature is 300–700℃ and the roasting time is 2–6 hours.
7. The method for preparing the Ni-In based composite catalyst according to claim 4, characterized in that, The carrier is grafted with hydrophobic groups. The grafting method includes: pre-burning the carrier and then heating it in a hydrophobic modifier solution to obtain a carrier grafted with hydrophobic groups. Preferably, the hydrophobic modifier used is selected from one or more of trimethylchlorosilane, dimethyldiethoxysilane, n-octyltriethoxysilane, and dodecyltriethoxysilane; the mass ratio of the hydrophobic modifier to the carrier is 1:(1-4).
8. The application of a Ni-In based composite catalyst as described in any one of claims 1 to 3, characterized in that, The Ni-In based composite catalyst is used for the hydrogenation of 3-hydroxypropionaldehyde to prepare 1,3-propanediol.
9. The application of the Ni-In based composite catalyst according to claim 8, characterized in that, Before the hydrogenation of 3-hydroxypropanal to prepare 1,3-propanediol, a reduction treatment is performed. In the reduction process, the reducing gas is hydrogen, the reduction temperature is 200–400°C, the reducing gas pressure is 0.5–2 MPa, and the reducing gas space velocity is 200–5000 h⁻¹. -1 The restoration time is 10–35 hours.
10. The application of the Ni-In based composite catalyst according to claim 8, characterized in that, The hydrogenation reaction of 3-hydroxypropanal to prepare 1,3-propanediol is a one-step hydrogenation reaction; Preferably, the reaction temperature is 35–135°C, the reaction pressure is 2–12 MPa, the molar ratio of hydrogen to 3-hydroxypropanal is 5–40:1, and the liquid hourly space velocity of 3-hydroxypropanal is 0.1–3 h⁻¹, based on a 1–20 wt% aqueous solution of 3-hydroxypropanal. -1 .