A bio-based furfuryl alcohol hydrogenation catalyst, its preparation method, and a process for the hydrogenation of bio-based furfuryl alcohol to 1,2-pentanediol.

Abstract

This invention belongs to the field of biomass conversion into fine chemicals, and provides a bio-based furfuryl alcohol hydrogenation catalyst, its preparation method, and a process for preparing 1,2-pentanediol from bio-based furfuryl alcohol hydrogenation. The catalyst consists of a support, an active component supported on the support, and auxiliary agents; the support is Al2O3, the active component is Pt three-dimensional clusters, and the auxiliary agents are MgO and ZnO. x and WO y Wherein 0x1 and 0y3. The process includes: bio-based furfuryl alcohol hydrogenation: Under the action of the above-mentioned bio-based furfuryl alcohol hydrogenation catalyst, a reaction promoter is added to the furfuryl alcohol / ethanol solution to carry out a hydrogenation reaction. The reaction promoter is an aqueous nitric acid solution with a concentration of 1-3 mol / L; the reaction product is then subjected to rotary evaporation and distillation to obtain 1,2-pentanediol. The catalyst of this invention has a high conversion rate and 1,2-pentanediol selectivity, and this process can improve the conversion rate of furfuryl alcohol and the selectivity of 1,2-pentanediol.

Description

Technical Field

[0001] This invention belongs to the field of biomass conversion into fine chemicals technology. Specifically, it relates to a bio-based furfuryl alcohol hydrogenation catalyst and its preparation method, as well as a process for preparing 1,2-pentanediol by bio-based furfuryl alcohol hydrogenation. Background Technology

[0002] 1,2-Pentanediol is a water-soluble polyol with antibacterial activity, used as a preservative in cosmetics and disinfectants. It can also be used as a polyester monomer containing ester functional groups in its main chain. This polyester has wide applications, such as in textiles, packaging materials, and engineering plastics. Currently, the main production process for 1,2-pentanediol is the pentene process, which involves epoxidation, esterification, and hydrolysis of pentene with peroxides. This process suffers from drawbacks such as limited pentene raw material availability, complex processes, involvement of peroxides, high process safety risks, and the generation of corrosive wastewater, severely restricting the development of 1,2-pentanediol. Therefore, developing new technological routes that utilize widely available and inexpensive raw materials, achieving high production efficiency and minimizing environmental pollution, is of great significance and holds promising potential.

[0003] Furfuryl alcohol is a product obtained by hydrogenating furfural, a biomass. Furfural is readily available, produced by the hydrolysis of common agricultural byproducts such as corn cobs, and has a significant price advantage compared to other raw materials for producing 1,2-pentanediol. The preparation of 1,2-pentanediol via the hydrogenation of furfuryl alcohol is a simple method with relatively low equipment requirements. However, current methods mostly employ batch hydrogenation, which involves long reaction times and harsh reaction conditions. Low selectivity for 1,2-pentanediol is a major problem currently faced.

[0004] Patent document CN110845301A discloses a method for producing 1,2-pentanediol. This method involves selectively hydrogenating furfuryl alcohol to 1,2-pentanediol under the catalysis of a noble metal catalyst supported on a composite support. The yield of 1,2-pentanediol in the product obtained by this method is only about 40%, while the yield of the low-value byproduct tetrahydrofurfuryl alcohol reaches more than 50%.

[0005] Patent document CN104370702A discloses a method for the liquid-phase selective hydrogenolysis of furfuryl alcohol to prepare 1,2-pentanediol. In this method, furfuryl alcohol is selectively hydrogenated to 1,2-pentanediol under the catalysis of a supported copper catalyst. The operating pressure of this process is 4-10 MPa, the temperature is 130-180℃, and the reaction time is 1-18 h. The conversion rate of furfuryl alcohol is 87.8%, and the selectivity of 1,2-pentanediol is 41.4%. This method has a long reaction time, low catalyst activity and selectivity, and a low yield of the target product pentanediol. Summary of the Invention

[0006] In view of the above, the purpose of this invention is to provide a bio-based furfuryl alcohol hydrogenation catalyst and its preparation method, as well as a process for preparing 1,2-pentanediol from bio-based furfuryl alcohol hydrogenation. The bio-based furfuryl alcohol hydrogenation catalyst of this invention has a high conversion rate and 1,2-pentanediol selectivity. Using the process for preparing 1,2-pentanediol from bio-based furfuryl alcohol hydrogenation of this invention, the conversion rate of bio-based furfuryl alcohol can reach 98%, and 1,2-pentanediol with a purity of 99.8% can be obtained.

[0007] A first aspect of the present invention provides a bio-based furfuryl alcohol hydrogenation catalyst, the catalyst comprising a support, an active component supported on the support, and an auxiliary agent; wherein the support is Al2O3, the active component is a Pt three-dimensional cluster, and the auxiliary agent is MgO or ZnO. x and WO y , of which 0 x 1, 0 y 3.

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

[0009] 1) A composite hydroxide containing magnesium, zinc, aluminum, and tungsten was prepared using a rotating liquid film reactor, and calcined to obtain an Al2O3 support containing additives;

[0010] 2) The Pt precursor solution was impregnated onto an Al2O3 support containing an auxiliary agent to prepare a catalyst precursor;

[0011] 3) The catalyst precursor is calcined and reduced to obtain the catalyst.

[0012] A third aspect of the present invention provides a process for the hydrogenation of bio-based furfuryl alcohol to prepare 1,2-pentanediol, the process comprising:

[0013] (1) Bio-based furfuryl alcohol hydrogenation: Under the action of the above-mentioned bio-based furfuryl alcohol hydrogenation catalyst, a reaction aid is added to the furfuryl alcohol / ethanol solution to carry out the hydrogenation reaction. The reaction aid is an aqueous nitric acid solution with a concentration of 1-3 mol / L.

[0014] (2) The reaction product obtained in step (1) is subjected to rotary evaporation and distillation to obtain 1,2-pentanediol.

[0015] Compared with the prior art, the present invention has the following beneficial effects:

[0016] The catalyst of this invention exhibits significant performance advantages in both furfuryl alcohol conversion and 1,2-pentanediol selectivity. The performance improvement is primarily attributed to the synergistic effect of its components: MgO and ZnO. x and WOy As an additive, Pt nanoparticles can regulate the acid-base balance of the Al2O3 support, optimize the physicochemical properties of the catalyst, and enhance its activity and stability. Pt nanoparticles themselves possess excellent C=C double bond hydrogenation and CO activation capabilities, enabling efficient catalysis of furfuryl alcohol hydrogenation. By controlling the structure of Pt, the hydrogenation performance and selectivity of the catalyst are further enhanced. The preparation process of this invention ensures the directional hydrogenation of the C=C double bond and CO activation of furfuryl alcohol, suppresses side reactions, and improves furfuryl alcohol conversion.

[0017] Other features and advantages of the present invention will be described in detail in the following detailed description section. Detailed Implementation

[0018] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0019] According to a first aspect of the present invention, a bio-based furfuryl alcohol hydrogenation catalyst is provided, the catalyst comprising a support, an active component supported on the support, and an auxiliary agent; wherein the support is Al2O3, the active component is a Pt three-dimensional cluster, and the auxiliary agent is MgO or ZnO. x and WO y , of which 0 x 1, 0 y 3.

[0020] In this invention, based on the total weight of the catalyst, the content of Al2O3 is 45-78 wt%, the content of Pt is 3-5 wt%, the content of MgO is 6-15 wt%, and the content of ZnO is... x The content is 2-6 wt%, WO y The content is 10-30wt%.

[0021] According to the present invention, the particle size of Pt can be 1.5-5 nm. Specifically, it can be determined using a high-resolution scanning transmission electron microscope with spherical aberration correction.

[0022] According to a second aspect of the present invention, the present invention provides a method for preparing the above-mentioned bio-based furfuryl alcohol hydrogenation catalyst, the method comprising the following steps:

[0023] 1) A composite hydroxide containing magnesium, zinc, aluminum, and tungsten was prepared using a rotating liquid film reactor, and calcined to obtain an Al2O3 support containing additives;

[0024] 2) The Pt precursor solution was impregnated onto an Al2O3 support containing an auxiliary agent to prepare a catalyst precursor;

[0025] 3) The catalyst precursor is calcined and reduced to obtain the catalyst.

[0026] In this invention, in step 1), magnesium salt, zinc salt, tungsten salt and aluminum salt are dissolved in water to obtain mixed solution A, and sodium hydroxide and sodium carbonate are dissolved in water to obtain mixed solution B; mixed solution A and mixed solution B are simultaneously added to a rotating liquid film reactor, mixed and crystallized, filtered, washed and dried to obtain a composite hydroxide containing magnesium, zinc, aluminum and tungsten.

[0027] According to the present invention, the amount of each substance is expressed in molar amounts of metals, and the molar ratio of magnesium salt, zinc salt, tungsten salt, and aluminum salt is 10-20. 30-50 1-5 4-10, The molar concentration of mixed solution A is 0.1-1.0 mol / L; the molar ratio of sodium hydroxide to sodium carbonate is 5-8. 1. The molar concentration of mixed solution B is 0.2-2.0 mol / L.

[0028] In this invention, the crystallization temperature can be 60-150℃ and the time can be 12-48h.

[0029] According to the present invention, in step 1), the calcination temperature is 500-700℃ and the time is 1-6h;

[0030] Step 2 of this invention includes: impregnating the Pt precursor solution with an Al2O3 support containing an auxiliary agent in the same volume, shaking for 0.5-2 hours, and then drying at 90-130°C for 1-3 hours;

[0031] In this invention, the conditions for calcination reduction treatment may include: calcination at 200-800°C for 1-4 hours in an air atmosphere with a heating rate of 1-20°C / min, followed by calcination at 200-800°C for 1-4 hours in a hydrogen atmosphere.

[0032] According to a third aspect of the present invention, the present invention provides a process for preparing 1,2-pentanediol by hydrogenation of bio-based furfuryl alcohol, the process comprising:

[0033] (1) Bio-based furfuryl alcohol hydrogenation: Under the action of the above-mentioned bio-based furfuryl alcohol hydrogenation catalyst, a reaction aid is added to the furfuryl alcohol / ethanol solution to carry out the hydrogenation reaction. The reaction aid is an aqueous nitric acid solution with a concentration of 1-3 mol / L.

[0034] (2) The reaction product obtained in step (1) is subjected to rotary evaporation and distillation to obtain 1,2-pentanediol.

[0035] According to the present invention, in step (1), the hydrogenation reaction is carried out in a reactor, the amount of catalyst is 2-8% of the mass of furfuryl alcohol, and the reaction conditions include: reaction temperature of 100-300℃, reaction pressure of 3-12MPa, and reaction time of 2-10h.

[0036] In this invention, the mass fraction of furfuryl alcohol in the furfuryl alcohol / ethanol solution can be 5%-50%.

[0037] Preferably, the amount of the reaction aid is 1-5 wt% of the furfuryl alcohol / ethanol solution.

[0038] In step (2) of this invention, the temperature of rotary evaporation is 30-50℃.

[0039] According to the present invention, the distillation conditions may include: a vacuum degree of 15-25 mbar, a reflux ratio of 1-10:1, a reboiler temperature of 55-155°C, and a distillation column temperature of 50-150°C.

[0040] The substances and parameters not limited in this invention can be selected according to existing technology, which is a conventional technical means in this field.

[0041] The present invention will be further described below with reference to embodiments. However, the invention is not limited to these embodiments.

[0042] Example 1

[0043] The preparation of a bio-based furfuryl alcohol hydrogenation catalyst includes the following steps:

[0044] Step A: Dissolve Mg(NO3)2·6H2O (18 mmol), Al(NO3)3·6H2O (36 mmol), Zn(NO3)2·6H2O (2 mmol), and Na2WO4·2H2O (4 mmol) in 300 mL of deionized water to prepare mixed solution A. Dissolve NaOH (0.156 mol) and Na2CO3 (0.024 mol) in 300 mL of deionized water to prepare mixed solution B. Add solutions A and B simultaneously to a rotating liquid film reactor at 3000 rpm and mix for 5 min. After crystallization at 65 ℃ for 12 h, filter the solid, wash repeatedly with deionized water until the filtrate is neutral, and dry at 65 ℃ overnight to obtain a composite hydroxide containing magnesium, zinc, aluminum, and tungsten. Calcine the obtained composite hydroxide containing magnesium, zinc, aluminum, and tungsten in a muffle furnace at 600 ℃ for 2 h to obtain an Al2O3-1 support containing additives.

[0045] Step B: Impregnate an equal volume of H2PtCl6 solution (concentration 0.2 mol / L) into a round-bottom flask containing the Al2O3-1 support with additives prepared in step (A), shake until homogeneous, shake for 1 h, and dry at 120 ℃ for 2 h to obtain the catalyst precursor Pt. 2+ / Al2O3-1.

[0046] Step C: The Pt prepared in step (B) 2+ The / Al2O3-1 sample was placed in a tube furnace and calcined at 300 °C for 2 h in air at a heating rate of 2 °C / min. Subsequently, the sample was purged with N2 for 0.5 h and then reduced at 300 °C for 2 h in H2 atmosphere at a flow rate of 40 mL / min to obtain 4Pt / Al2O3-1. The actual Pt loading was 4.0 wt%, and the Pt structure was a three-dimensional cluster.

[0047] A process for preparing 1,2-pentanediol by hydrogenation of bio-based furfuryl alcohol includes the following steps:

[0048] Bio-based furfuryl alcohol hydrogenation process: 60 mL of a 20% furfuryl alcohol / ethanol solution was added to a 100 mL high-pressure reactor as the reaction solution. A 2 mol / L nitric acid aqueous solution was added as a reaction aid, with the amount of reaction aid being 2 wt% of the reaction solution. 0.6 g of the above-mentioned bio-based furfuryl alcohol hydrogenation catalyst was added. The catalytic hydrogenation reaction was carried out at a stirring speed of 700 rpm, a temperature of 220 ℃, and a reaction pressure of 8 MPa. The reaction was stopped after 5 h. The filtered reaction solution was analyzed by gas chromatography. The furfuryl alcohol conversion rate and 1,2-pentanediol selectivity are shown in Table 2.

[0049] Distillation Process: The liquid after hydrogenation was added to a rotary evaporator, and the heating temperature was set to 30℃. Ethanol and other low-boiling-point impurities were removed under vacuum. The remaining liquid was added to the reboiler of a distillation column packed with high-efficiency structured packing. A vacuum of 20 mbar was established, with the reboiler temperature at 95℃ and the distillation column temperature at 90℃. The reflux ratio was 3:1. The top liquid was sampled and analyzed every 2 hours. When there was no reflux at the top, the reboiler temperature and the distillation column temperature were increased by 10℃. When the reboiler temperature reached 125℃, no substances with boiling points lower than 1,2-pentanediol remained in the reboiler, and the top liquid was mostly 1,2-pentanediol. At this point, distillation was stopped, and the distillation column was thoroughly cleaned with ethanol, saving significant time and energy while increasing the distillate content. After cleaning, the reboiler temperature was raised to 125℃, and distillation continued. The purity of the 1,2-pentanediol obtained from the top liquid is shown in Table 2.

[0050] Example 2

[0051] The preparation of a bio-based furfuryl alcohol hydrogenation catalyst includes the following steps:

[0052] Step A: Dissolve Mg(NO3)2·6H2O (16 mmol), Al(NO3)3·6H2O (36 mmol), Zn(NO3)2·6H2O (4 mmol), and Na2WO4·2H2O (4 mmol) in 300 mL of deionized water to prepare mixed solution A. Dissolve NaOH (0.156 mol) and Na2CO3 (0.024 mol) in 300 mL of deionized water to prepare mixed solution B. Add solutions A and B simultaneously to a rotating liquid film reactor at 3000 rpm and mix for 5 min. After crystallization at 65 ℃ for 12 h, filter the solid, wash repeatedly with deionized water until the filtrate is neutral, and dry at 65 ℃ overnight to obtain a composite hydroxide containing magnesium, zinc, aluminum, and tungsten. Calcine the obtained composite hydroxide containing magnesium, zinc, aluminum, and tungsten in a muffle furnace at 600 ℃ for 2 h to obtain an Al2O3-2 support containing additives.

[0053] Step B: Impregnate an equal volume of H2PtCl6 solution (concentration 0.2 mol / L) into a round-bottom flask containing the Al2O3-2 support with additives prepared in step (A), shake thoroughly for 1 h, and dry at 120 ℃ for 2 h to obtain the catalyst precursor Pt. 2+ / Al2O3-2.

[0054] Step C: The Pt prepared in step (B) 2+ The / Al2O3-2 sample was placed in a tube furnace and calcined at 300 °C for 2 h in air at a heating rate of 2 °C / min. Subsequently, the sample was purged with N2 for 0.5 h and then reduced at 300 °C for 2 h in H2 atmosphere at a flow rate of 40 mL / min to obtain 4Pt / Al2O3-2. The actual Pt loading was 4.0 wt%, and the Pt structure was a three-dimensional cluster.

[0055] A process for preparing 1,2-pentanediol by hydrogenation of bio-based furfuryl alcohol includes the following steps:

[0056] Bio-based furfuryl alcohol hydrogenation process: 60 mL of a 20% furfuryl alcohol / ethanol solution was added to a 100 mL high-pressure reactor as the reaction solution. A 2 mol / L nitric acid aqueous solution was added as a reaction aid, with the amount of reaction aid being 2 wt% of the reaction solution. 0.6 g of the above-mentioned bio-based furfuryl alcohol hydrogenation catalyst was added. The catalytic hydrogenation reaction was carried out at a stirring speed of 700 rpm, a temperature of 220 ℃, and a reaction pressure of 8 MPa. The reaction was stopped after 5 h. The filtered reaction solution was analyzed by gas chromatography. The furfuryl alcohol conversion rate and 1,2-pentanediol selectivity are shown in Table 2.

[0057] Distillation Process: The liquid after hydrogenation was added to a rotary evaporator, and the heating temperature was set to 30℃. Ethanol and other low-boiling-point impurities were removed under vacuum. The remaining liquid was added to the reboiler of a distillation column packed with high-efficiency structured packing. A vacuum of 20 mbar was established, with the reboiler temperature at 95℃ and the distillation column temperature at 90℃. The reflux ratio was 3:1. The top liquid was sampled and analyzed every 2 hours. When there was no reflux at the top, the reboiler temperature and the distillation column temperature were increased by 10℃. When the reboiler temperature reached 125℃, no substances with boiling points lower than 1,2-pentanediol remained in the reboiler, and the top liquid was mostly 1,2-pentanediol. At this point, distillation was stopped, and the distillation column was thoroughly cleaned with ethanol, saving significant time and energy while increasing the distillate content. After cleaning, the reboiler temperature was raised to 125℃, and distillation continued. The purity of the 1,2-pentanediol obtained from the top liquid is shown in Table 2.

[0058] Example 3

[0059] The preparation of a bio-based furfuryl alcohol hydrogenation catalyst includes the following steps:

[0060] Step A: Dissolve Mg(NO3)2·6H2O (18 mmol), Al(NO3)3·6H2O (32 mmol), Zn(NO3)2·6H2O (2 mmol), and Na2WO4·2H2O (8 mmol) in 300 mL of deionized water to prepare mixed solution A. Dissolve NaOH (0.156 mol) and Na2CO3 (0.024 mol) in 300 mL of deionized water to prepare mixed solution B. Add solutions A and B simultaneously to a rotating liquid film reactor at 3000 rpm and mix for 5 min. After crystallization at 65 ℃ for 12 h, filter the solid, wash repeatedly with deionized water until the filtrate is neutral, and dry at 65 ℃ overnight to obtain a composite hydroxide containing magnesium, zinc, aluminum, and tungsten. Calcine the obtained composite hydroxide containing magnesium, zinc, aluminum, and tungsten in a muffle furnace at 600 ℃ for 2 h to obtain an Al2O3-3 support containing additives.

[0061] Step B: Impregnate an equal volume of H2PtCl6 solution (concentration 0.2 mol / L) into a round-bottom flask containing the Al2O3-3 support with additives prepared in step (A), shake until homogeneous, shake for 1 h, and dry at 120 ℃ for 2 h to obtain the catalyst precursor Pt. 2+ / Al2O3-3.

[0062] Step C: The Pt prepared in step (B) 2+The / Al2O3-3 was placed in a tube furnace and calcined at 300 °C for 2 h in air at a heating rate of 2 °C / min. Subsequently, the sample was purged with N2 for 0.5 h and then reduced at 300 °C for 2 h in H2 atmosphere at a flow rate of 40 mL / min to obtain 4Pt / Al2O3-3. The actual Pt loading was 4.0 wt%, and the Pt structure was a three-dimensional cluster.

[0063] A process for preparing 1,2-pentanediol by hydrogenation of bio-based furfuryl alcohol includes the following steps:

[0064] Bio-based furfuryl alcohol hydrogenation process: 60 mL of a 20% furfuryl alcohol / ethanol solution was added to a 100 mL high-pressure reactor as the reaction solution. A 2 mol / L nitric acid aqueous solution was added as a reaction aid, with the amount of reaction aid being 2 wt% of the reaction solution. 0.6 g of the above-mentioned bio-based furfuryl alcohol hydrogenation catalyst was added. The catalytic hydrogenation reaction was carried out at a stirring speed of 700 rpm, a temperature of 220 ℃, and a reaction pressure of 8 MPa. The reaction was stopped after 5 h. The filtered reaction solution was analyzed by gas chromatography. The furfuryl alcohol conversion rate and 1,2-pentanediol selectivity are shown in Table 2.

[0065] Distillation Process: The liquid after hydrogenation was added to a rotary evaporator, and the heating temperature was set to 30℃. Ethanol and other low-boiling-point impurities were removed under vacuum. The remaining liquid was added to the reboiler of a distillation column packed with high-efficiency structured packing. A vacuum of 20 mbar was established, with the reboiler temperature at 95℃ and the distillation column temperature at 90℃. The reflux ratio was 3:1. The top liquid was sampled and analyzed every 2 hours. When there was no reflux at the top, the reboiler temperature and the distillation column temperature were increased by 10℃. When the reboiler temperature reached 125℃, no substances with boiling points lower than 1,2-pentanediol remained in the reboiler, and the top liquid was mostly 1,2-pentanediol. At this point, distillation was stopped, and the distillation column was thoroughly cleaned with ethanol, saving significant time and energy while increasing the distillate content. After cleaning, the reboiler temperature was raised to 125℃, and distillation continued. The purity of the 1,2-pentanediol obtained from the top liquid is shown in Table 2.

[0066] Example 4

[0067] The preparation of a bio-based furfuryl alcohol hydrogenation catalyst includes the following steps:

[0068] Step A: Dissolve Mg(NO3)2·6H2O (13 mmol), Al(NO3)3·6H2O (41 mmol), Zn(NO3)2·6H2O (2 mmol), and Na2WO4·2H2O (4 mmol) in 300 mL of deionized water to prepare mixed solution A. Dissolve NaOH (0.156 mol) and Na2CO3 (0.024 mol) in 300 mL of deionized water to prepare mixed solution B. Add solutions A and B simultaneously to a rotating liquid film reactor at 3000 rpm and mix for 5 min. After crystallization at 65 ℃ for 12 h, filter the solid, wash repeatedly with deionized water until the filtrate is neutral, and dry at 65 ℃ overnight to obtain a composite hydroxide containing magnesium, zinc, aluminum, and tungsten. Calcine the obtained composite hydroxide containing magnesium, zinc, aluminum, and tungsten in a muffle furnace at 600 ℃ for 2 h to obtain an Al2O3-4 support containing additives.

[0069] Step B: Impregnate an equal volume of H2PtCl6 solution (concentration 0.2 mol / L) into a round-bottom flask containing the Al2O3-4 support with additives prepared in step (A), shake until homogeneous, shake for 1 h, and dry at 120 ℃ for 2 h to obtain the catalyst precursor Pt. 2+ / Al2O3-4.

[0070] Step C: The Pt prepared in step (B) 2+ The / Al2O3-4 sample was placed in a tube furnace and calcined at 300 °C for 2 h in air at a heating rate of 2 °C / min. Subsequently, the sample was purged with N2 for 0.5 h and then reduced at 300 °C for 2 h in H2 atmosphere at a flow rate of 40 mL / min to obtain 4Pt / Al2O3-4. The actual Pt loading was 4.0 wt%, and the Pt structure was a three-dimensional cluster.

[0071] A process for preparing 1,2-pentanediol by hydrogenation of bio-based furfuryl alcohol includes the following steps:

[0072] Bio-based furfuryl alcohol hydrogenation process: 60 mL of a 20% furfuryl alcohol / ethanol solution was added to a 100 mL high-pressure reactor as the reaction solution. A 2 mol / L nitric acid aqueous solution was added as a reaction aid, with the amount of reaction aid being 2 wt% of the reaction solution. 0.6 g of the above-mentioned bio-based furfuryl alcohol hydrogenation catalyst was added. The catalytic hydrogenation reaction was carried out at a stirring speed of 700 rpm, a temperature of 220 ℃, and a reaction pressure of 8 MPa. The reaction was stopped after 5 h. The filtered reaction solution was analyzed by gas chromatography. The furfuryl alcohol conversion rate and 1,2-pentanediol selectivity are shown in Table 2.

[0073] Distillation Process: The liquid after hydrogenation was added to a rotary evaporator, and the heating temperature was set to 30℃. Ethanol and other low-boiling-point impurities were removed under vacuum. The remaining liquid was added to the reboiler of a distillation column packed with high-efficiency structured packing. A vacuum of 20 mbar was established, with the reboiler temperature at 95℃ and the distillation column temperature at 90℃. The reflux ratio was 3:1. The top liquid was sampled and analyzed every 2 hours. When there was no reflux at the top, the reboiler temperature and the distillation column temperature were increased by 10℃. When the reboiler temperature reached 125℃, no substances with boiling points lower than 1,2-pentanediol remained in the reboiler, and the top liquid was mostly 1,2-pentanediol. At this point, distillation was stopped, and the distillation column was thoroughly cleaned with ethanol, saving significant time and energy while increasing the distillate content. After cleaning, the reboiler temperature was raised to 125℃, and distillation continued. The purity of the 1,2-pentanediol obtained from the top liquid is shown in Table 2.

[0074] Example 5

[0075] The preparation of a bio-based furfuryl alcohol hydrogenation catalyst includes the following steps:

[0076] Step A: Dissolve Mg(NO3)2·6H2O (18 mmol), Al(NO3)3·6H2O (36 mmol), Zn(NO3)2·6H2O (2 mmol), and Na2WO4·2H2O (4 mmol) in 300 mL of deionized water to prepare mixed solution A. Dissolve NaOH (0.156 mol) and Na2CO3 (0.024 mol) in 300 mL of deionized water to prepare mixed solution B. Add solutions A and B simultaneously to a rotating liquid film reactor at 3000 rpm and mix for 5 min. After crystallization at 65 ℃ for 12 h, filter the solid, wash repeatedly with deionized water until the filtrate is neutral, and dry at 65 ℃ overnight to obtain a composite hydroxide containing magnesium, zinc, aluminum, and tungsten. Calcine the obtained composite hydroxide containing magnesium, zinc, aluminum, and tungsten in a muffle furnace at 600 ℃ for 2 h to obtain an Al2O3-1 support containing additives.

[0077] Step B: Impregnate an equal volume of H2PtCl6 solution (concentration 0.2 mol / L) into a round-bottom flask containing the Al2O3-1 support with additives prepared in step (A), shake until homogeneous, shake for 1 h, and dry at 120 ℃ for 2 h to obtain the catalyst precursor Pt. 2+ / Al2O3-1.

[0078] Step C: The Pt prepared in step (B) 2+The / Al2O3-1 sample was placed in a tube furnace and calcined at 300 °C for 2 h in air at a heating rate of 2 °C / min. Subsequently, the sample was purged with N2 for 0.5 h and then reduced at 300 °C for 2 h in H2 atmosphere at a flow rate of 40 mL / min to obtain 4Pt / Al2O3-1. The actual Pt loading was 4.0 wt%, and the Pt structure was a three-dimensional cluster.

[0079] A process for preparing 1,2-pentanediol by hydrogenation of bio-based furfuryl alcohol includes the following steps:

[0080] Bio-based furfuryl alcohol hydrogenation process: 60 mL of a 20% furfuryl alcohol / ethanol solution was added to a 100 mL high-pressure reactor as the reaction solution. A 2 mol / L nitric acid aqueous solution was added as a reaction aid, with the amount of reaction aid being 1 wt% of the reaction solution. 0.6 g of the above-mentioned bio-based furfuryl alcohol hydrogenation catalyst was added. The catalytic hydrogenation reaction was carried out at a stirring speed of 700 rpm, a temperature of 220 ℃, and a reaction pressure of 8 MPa. The reaction was stopped after 5 h. The filtered reaction solution was analyzed by gas chromatography. The furfuryl alcohol conversion rate and 1,2-pentanediol selectivity are shown in Table 2.

[0081] Distillation Process: The liquid after hydrogenation was added to a rotary evaporator, and the heating temperature was set to 30℃. Ethanol and other low-boiling-point impurities were removed under vacuum. The remaining liquid was added to the reboiler of a distillation column packed with high-efficiency structured packing. A vacuum of 20 mbar was established, with the reboiler temperature at 95℃ and the distillation column temperature at 90℃. The reflux ratio was 3:1. The top liquid was sampled and analyzed every 2 hours. When there was no reflux at the top, the reboiler temperature and the distillation column temperature were increased by 10℃. When the reboiler temperature reached 125℃, no substances with boiling points lower than 1,2-pentanediol remained in the reboiler, and the top liquid was mostly 1,2-pentanediol. At this point, distillation was stopped, and the distillation column was thoroughly cleaned with ethanol, saving significant time and energy while increasing the distillate content. After cleaning, the reboiler temperature was raised to 125℃, and distillation continued. The purity of the 1,2-pentanediol obtained from the top liquid is shown in Table 2.

[0082] Example 6

[0083] The preparation of a bio-based furfuryl alcohol hydrogenation catalyst includes the following steps:

[0084] Step A: Dissolve Mg(NO3)2·6H2O (18 mmol), Al(NO3)3·6H2O (36 mmol), Zn(NO3)2·6H2O (2 mmol), and Na2WO4·2H2O (4 mmol) in 300 mL of deionized water to prepare mixed solution A. Dissolve NaOH (0.156 mol) and Na2CO3 (0.024 mol) in 300 mL of deionized water to prepare mixed solution B. Add solutions A and B simultaneously to a rotating liquid film reactor at 3000 rpm and mix for 5 min. After crystallization at 65 ℃ for 12 h, filter the solid, wash repeatedly with deionized water until the filtrate is neutral, and dry at 65 ℃ overnight to obtain a composite hydroxide containing magnesium, zinc, aluminum, and tungsten. Calcine the obtained composite hydroxide containing magnesium, zinc, aluminum, and tungsten in a muffle furnace at 600 ℃ for 2 h to obtain an Al2O3-1 support containing additives.

[0085] Step B: Impregnate an equal volume of H2PtCl6 solution (concentration 0.2 mol / L) into a round-bottom flask containing the Al2O3-1 support with additives prepared in step (A), shake until homogeneous, shake for 1 h, and dry at 120 ℃ for 2 h to obtain the catalyst precursor Pt. 2+ / Al2O3-1.

[0086] Step C: The Pt prepared in step (B) 2+ The / Al2O3-1 sample was placed in a tube furnace and calcined at 300 °C for 2 h in air at a heating rate of 2 °C / min. Subsequently, the sample was purged with N2 for 0.5 h and then reduced at 300 °C for 2 h in H2 atmosphere at a flow rate of 40 mL / min to obtain 4Pt / Al2O3-1. The actual Pt loading was 4.0 wt%, and the Pt structure was a three-dimensional cluster.

[0087] A process for preparing 1,2-pentanediol by hydrogenation of bio-based furfuryl alcohol includes the following steps:

[0088] Bio-based furfuryl alcohol hydrogenation process: 60 mL of 20% furfuryl alcohol / ethanol solution was added to a 100 mL high-pressure reactor as the reaction solution. A 2 mol / L nitric acid aqueous solution was added as a reaction aid, with the amount of reaction aid being 5 wt% of the reaction solution. 0.6 g of the above-mentioned bio-based furfuryl alcohol hydrogenation catalyst was added. The catalytic hydrogenation reaction was carried out at a stirring speed of 700 rpm, a temperature of 220 ℃, and a reaction pressure of 8 MPa. The reaction was stopped after 5 h. The filtered reaction solution was analyzed by gas chromatography. The furfuryl alcohol conversion rate and 1,2-pentanediol selectivity are shown in Table 2.

[0089] Distillation Process: The liquid after hydrogenation was added to a rotary evaporator, and the heating temperature was set to 30℃. Ethanol and other low-boiling-point impurities were removed under vacuum. The remaining liquid was added to the reboiler of a distillation column packed with high-efficiency structured packing. A vacuum of 20 mbar was established, with the reboiler temperature at 95℃ and the distillation column temperature at 90℃. The reflux ratio was 3:1. The top liquid was sampled and analyzed every 2 hours. When there was no reflux at the top, the reboiler temperature and the distillation column temperature were increased by 10℃. When the reboiler temperature reached 125℃, no substances with boiling points lower than 1,2-pentanediol remained in the reboiler, and the top liquid was mostly 1,2-pentanediol. At this point, distillation was stopped, and the distillation column was thoroughly cleaned with ethanol, saving significant time and energy while increasing the distillate content. After cleaning, the reboiler temperature was raised to 125℃, and distillation continued. The purity of the 1,2-pentanediol obtained from the top liquid is shown in Table 2.

[0090] Example 7

[0091] The preparation of a bio-based furfuryl alcohol hydrogenation catalyst includes the following steps:

[0092] Step A: Dissolve Mg(NO3)2·6H2O (18 mmol), Al(NO3)3·6H2O (36 mmol), Zn(NO3)2·6H2O (2 mmol), and Na2WO4·2H2O (4 mmol) in 300 mL of deionized water to prepare mixed solution A. Dissolve NaOH (0.156 mol) and Na2CO3 (0.024 mol) in 300 mL of deionized water to prepare mixed solution B. Add solutions A and B simultaneously to a rotating liquid film reactor at 3000 rpm and mix for 5 min. After crystallization at 65 ℃ for 12 h, filter the solid, wash repeatedly with deionized water until the filtrate is neutral, and dry at 65 ℃ overnight to obtain a composite hydroxide containing magnesium, zinc, aluminum, and tungsten. Calcine the obtained composite hydroxide containing magnesium, zinc, aluminum, and tungsten in a muffle furnace at 600 ℃ for 2 h to obtain an Al2O3-1 support containing additives.

[0093] Step B: Impregnate an equal volume of H2PtCl6 solution (concentration 0.2 mol / L) into a round-bottom flask containing the Al2O3-1 support with additives prepared in step (A), shake until homogeneous, shake for 1 h, and dry at 120 ℃ for 2 h to obtain the catalyst precursor Pt. 2+ / Al2O3-1.

[0094] Step C: The Pt prepared in step (B) 2+The / Al2O3-1 sample was placed in a tube furnace and calcined at 300 °C for 2 h in air at a heating rate of 2 °C / min. Subsequently, the sample was purged with N2 for 0.5 h and then reduced at 300 °C for 2 h in H2 atmosphere at a flow rate of 40 mL / min to obtain 4Pt / Al2O3-1. The actual Pt loading was 4.0 wt%, and the Pt structure was a three-dimensional cluster.

[0095] A process for preparing 1,2-pentanediol by hydrogenation of bio-based furfuryl alcohol includes the following steps:

[0096] Bio-based furfuryl alcohol hydrogenation process: 60 mL of a 20% furfuryl alcohol / ethanol solution was added to a 100 mL high-pressure reactor as the reaction solution. A 2 mol / L nitric acid aqueous solution was added as a reaction aid, with the amount of reaction aid being 2 wt% of the reaction solution. 0.6 g of the above-mentioned bio-based furfuryl alcohol hydrogenation catalyst was added. The catalytic hydrogenation reaction was carried out at a stirring speed of 700 rpm, a temperature of 180 ℃, and a reaction pressure of 8 MPa. The reaction was stopped after 5 h. The filtered reaction solution was analyzed by gas chromatography. The furfuryl alcohol conversion rate and 1,2-pentanediol selectivity are shown in Table 2.

[0097] Distillation Process: The liquid after hydrogenation was added to a rotary evaporator, and the heating temperature was set to 30℃. Ethanol and other low-boiling-point impurities were removed under vacuum. The remaining liquid was added to the reboiler of a distillation column packed with high-efficiency structured packing. A vacuum of 20 mbar was established, with the reboiler temperature at 95℃ and the distillation column temperature at 90℃. The reflux ratio was 3:1. The top liquid was sampled and analyzed every 2 hours. When there was no reflux at the top, the reboiler temperature and the distillation column temperature were increased by 10℃. When the reboiler temperature reached 125℃, no substances with boiling points lower than 1,2-pentanediol remained in the reboiler, and the top liquid was mostly 1,2-pentanediol. At this point, distillation was stopped, and the distillation column was thoroughly cleaned with ethanol, saving significant time and energy while increasing the distillate content. After cleaning, the reboiler temperature was raised to 125℃, and distillation continued. The purity of the 1,2-pentanediol obtained from the top liquid is shown in Table 2.

[0098] Example 8

[0099] The preparation of a bio-based furfuryl alcohol hydrogenation catalyst includes the following steps:

[0100] Step A: Dissolve Mg(NO3)2·6H2O (18 mmol), Al(NO3)3·6H2O (36 mmol), Zn(NO3)2·6H2O (2 mmol), and Na2WO4·2H2O (4 mmol) in 300 mL of deionized water to prepare mixed solution A. Dissolve NaOH (0.156 mol) and Na2CO3 (0.024 mol) in 300 mL of deionized water to prepare mixed solution B. Add solutions A and B simultaneously to a rotating liquid film reactor at 3000 rpm and mix for 5 min. After crystallization at 65 ℃ for 12 h, filter the solid, wash repeatedly with deionized water until the filtrate is neutral, and dry at 65 ℃ overnight to obtain a composite hydroxide containing magnesium, zinc, aluminum, and tungsten. Calcine the obtained composite hydroxide containing magnesium, zinc, aluminum, and tungsten in a muffle furnace at 600 ℃ for 2 h to obtain an Al2O3-1 support containing additives.

[0101] Step B: Impregnate an equal volume of H2PtCl6 solution (concentration 0.2 mol / L) into a round-bottom flask containing the Al2O3-1 support with additives prepared in step (A), shake until homogeneous, shake for 1 h, and dry at 120 ℃ for 2 h to obtain the catalyst precursor Pt. 2+ / Al2O3-1.

[0102] Step C: The Pt prepared in step (B) 2+ The / Al2O3-1 sample was placed in a tube furnace and calcined at 300 °C for 2 h in air at a heating rate of 2 °C / min. Subsequently, the sample was purged with N2 for 0.5 h and then reduced at 300 °C for 2 h in H2 atmosphere at a flow rate of 40 mL / min to obtain 4Pt / Al2O3-1. The actual Pt loading was 4.0 wt%, and the Pt structure was a three-dimensional cluster.

[0103] A process for preparing 1,2-pentanediol by hydrogenation of bio-based furfuryl alcohol includes the following steps:

[0104] Bio-based furfuryl alcohol hydrogenation process: 60 mL of a 20% furfuryl alcohol / ethanol solution was added to a 100 mL high-pressure reactor as the reaction solution. A 2 mol / L nitric acid aqueous solution was added as a reaction aid, with the amount of reaction aid being 2 wt% of the reaction solution. 0.6 g of the above-mentioned bio-based furfuryl alcohol hydrogenation catalyst was added. The catalytic hydrogenation reaction was carried out at a stirring speed of 700 rpm, a temperature of 220 ℃, and a reaction pressure of 4 MPa. The reaction was stopped after 5 h. The filtered reaction solution was analyzed by gas chromatography. The furfuryl alcohol conversion rate and 1,2-pentanediol selectivity are shown in Table 2.

[0105] Distillation Process: The liquid after hydrogenation was added to a rotary evaporator, and the heating temperature was set to 30℃. Ethanol and other low-boiling-point impurities were removed under vacuum. The remaining liquid was added to the reboiler of a distillation column packed with high-efficiency structured packing. A vacuum of 20 mbar was established, with the reboiler temperature at 95℃ and the distillation column temperature at 90℃. The reflux ratio was 3:1. The top liquid was sampled and analyzed every 2 hours. When there was no reflux at the top, the reboiler temperature and the distillation column temperature were increased by 10℃. When the reboiler temperature reached 125℃, no substances with boiling points lower than 1,2-pentanediol remained in the reboiler, and the top liquid was mostly 1,2-pentanediol. At this point, distillation was stopped, and the distillation column was thoroughly cleaned with ethanol, saving significant time and energy while increasing the distillate content. After cleaning, the reboiler temperature was raised to 125℃, and distillation continued. The purity of the 1,2-pentanediol obtained from the top liquid is shown in Table 2.

[0106] Comparative Example 1

[0107] The preparation of a bio-based furfuryl alcohol hydrogenation catalyst includes the following steps:

[0108] Step A: Dissolve Mg(NO3)2·6H2O (18 mmol), Al(NO3)3·6H2O (36 mmol), Zn(NO3)2·6H2O (2 mmol), and Na2WO4·2H2O (4 mmol) in 300 mL of deionized water to prepare mixed solution A. Dissolve NaOH (0.156 mol) and Na2CO3 (0.024 mol) in 300 mL of deionized water to prepare mixed solution B. Add solutions A and B simultaneously to a rotating liquid film reactor at 3000 rpm and mix for 5 min. After crystallization at 65 ℃ for 12 h, filter the solid, wash repeatedly with deionized water until the filtrate is neutral, and dry at 65 ℃ overnight to obtain a composite hydroxide containing magnesium, zinc, aluminum, and tungsten. Calcine the obtained composite hydroxide containing magnesium, zinc, aluminum, and tungsten in a muffle furnace at 600 ℃ for 2 h to obtain an Al2O3-1 support containing additives.

[0109] Step B: Impregnate an equal volume of H2PtCl6 solution (concentration 0.1 mol / L) into a round-bottom flask containing the Al2O3-1 support with additives prepared in step (A), shake thoroughly for 1 h, and dry at 120 ℃ for 2 h to obtain the catalyst precursor Pt. 2+ / Al2O3-1.

[0110] Step C: The Pt prepared in step (B) 2+The / Al2O3-1 sample was placed in a tube furnace and calcined at 600 °C for 2 h in air at a heating rate of 2 °C / min. Subsequently, the sample was purged with N2 for 0.5 h and then reduced at 300 °C for 2 h in H2 atmosphere at a flow rate of 40 mL / min to obtain 2Pt / Al2O3-1. The actual Pt loading was 2.0 wt%, and the Pt structure was a two-dimensional cluster.

[0111] A process for preparing 1,2-pentanediol by hydrogenation of bio-based furfuryl alcohol includes the following steps:

[0112] Bio-based furfuryl alcohol hydrogenation process: 60 mL of a 20% furfuryl alcohol / ethanol solution was added to a 100 mL high-pressure reactor as the reaction solution. A 2 mol / L nitric acid aqueous solution was added as a reaction aid, with the amount of reaction aid being 2 wt% of the reaction solution. 0.6 g of the above-mentioned bio-based furfuryl alcohol hydrogenation catalyst was added. The catalytic hydrogenation reaction was carried out at a stirring speed of 700 rpm, a temperature of 220 ℃, and a reaction pressure of 8 MPa. The reaction was stopped after 5 h. The filtered reaction solution was analyzed by gas chromatography. The furfuryl alcohol conversion rate and 1,2-pentanediol selectivity are shown in Table 2.

[0113] Distillation Process: The liquid after hydrogenation was added to a rotary evaporator, and the heating temperature was set to 30℃. Ethanol and other low-boiling-point impurities were removed under vacuum. The remaining liquid was added to the reboiler of a distillation column packed with high-efficiency structured packing. A vacuum of 20 mbar was established, with the reboiler temperature at 95℃ and the distillation column temperature at 90℃. The reflux ratio was 3:1. The top liquid was sampled and analyzed every 2 hours. When there was no reflux at the top, the reboiler temperature and the distillation column temperature were increased by 10℃. When the reboiler temperature reached 125℃, no substances with boiling points lower than 1,2-pentanediol remained in the reboiler, and the top liquid was mostly 1,2-pentanediol. At this point, distillation was stopped, and the distillation column was thoroughly cleaned with ethanol, saving significant time and energy while increasing the distillate content. After cleaning, the reboiler temperature was raised to 125℃, and distillation continued. The purity of the 1,2-pentanediol obtained from the top liquid is shown in Table 2.

[0114] Comparative Example 2

[0115] The preparation of a bio-based furfuryl alcohol hydrogenation catalyst includes the following steps:

[0116] Step A: Dissolve Mg(NO3)2·6H2O (18 mmol), Al(NO3)3·6H2O (36 mmol), Zn(NO3)2·6H2O (2 mmol), and Na2WO4·2H2O (4 mmol) in 300 mL of deionized water to prepare mixed solution A. Dissolve NaOH (0.156 mol) and Na2CO3 (0.024 mol) in 300 mL of deionized water to prepare mixed solution B. Add solutions A and B simultaneously to a rotating liquid film reactor at 3000 rpm and mix for 5 min. After crystallization at 65 ℃ for 12 h, filter the solid, wash repeatedly with deionized water until the filtrate is neutral, and dry at 65 ℃ overnight to obtain a composite hydroxide containing magnesium, zinc, aluminum, and tungsten. Calcine the obtained composite hydroxide containing magnesium, zinc, aluminum, and tungsten in a muffle furnace at 600 ℃ for 2 h to obtain an Al2O3-1 support containing additives.

[0117] Step B: Impregnate an equal volume of H2PtCl6 solution (concentration 0.05 mol / L) in a round-bottom flask containing the Al2O3-1 support with additives prepared in step (A), shake thoroughly for 1 h, and dry at 120 ℃ for 2 h to obtain the catalyst precursor Pt. 2+ / Al2O3-1.

[0118] Step C: The Pt prepared in step (B) 2+ Al₂O₃⁻ was placed in a tubular furnace and reduced at 600 °C for 2 h in an H₂ atmosphere with a flow rate of 40 mL / min to obtain 1Pt / Al₂O₃⁻. The actual Pt loading was 1.0 wt%, and the Pt structure was a single atom.

[0119] A process for preparing 1,2-pentanediol by hydrogenation of bio-based furfuryl alcohol includes the following steps:

[0120] Bio-based furfuryl alcohol hydrogenation process: 60 mL of a 20% (w / w) furfuryl alcohol / ethanol solution was added to a 100 mL high-pressure reactor as the reaction solution. A 2 mol / L nitric acid aqueous solution was added as a reaction aid (2 wt% of the reaction solution). 0.6 g of the aforementioned bio-based furfuryl alcohol hydrogenation catalyst was added. The catalytic hydrogenation reaction was carried out at a stirring speed of 700 rpm, a temperature of 220 ℃, and a reaction pressure of 8 MPa. The reaction was stopped after 5 h. The filtered reaction solution was analyzed by gas chromatography. The furfuryl alcohol conversion rate and 1,2-pentanediol selectivity are shown in Table 2. Due to the low selectivity of 1,2-pentanediol, further distillation was not performed.

[0121] Comparative Example 3

[0122] The preparation of a bio-based furfuryl alcohol hydrogenation catalyst includes the following steps:

[0123] Step A: Dissolve Al(NO3)3·6H2O (36 mmol) in 300 mL of deionized water to prepare mixed solution A. Dissolve NaOH (0.156 mol) and Na2CO3 (0.024 mol) in 300 mL of deionized water to prepare mixed solution B. Add solutions A and B simultaneously to a rotating liquid film reactor at 3000 rpm and mix for 5 min. After crystallization at 65 ℃ for 12 h, filter the solid, wash repeatedly with deionized water until the filtrate is neutral, and dry at 65 ℃ overnight to obtain aluminum hydroxide. Calcine the obtained aluminum hydroxide in a muffle furnace at 600 ℃ for 2 h to obtain Al2O3-D1 support.

[0124] Step B: Impregnate an equal volume of H2PtCl6 solution (concentration 0.2 mol / L) in a round-bottom flask containing the Al2O3-D1 support prepared in step (A), shake until homogeneous, shake for 1 h, and dry at 120 ℃ for 2 h to obtain the catalyst precursor Pt. 2+ / Al2O3-D1.

[0125] Step C: The Pt prepared in step (B) 2+ The / Al2O3-D1 sample was placed in a tube furnace and calcined at 300 °C for 2 h in air at a heating rate of 2 °C / min. Subsequently, the sample was purged with N2 for 0.5 h and then reduced at 300 °C for 2 h in H2 atmosphere at a flow rate of 40 mL / min to obtain 4Pt / Al2O3-D1. The actual Pt loading was 4.0 wt%, and the Pt structure was a three-dimensional cluster.

[0126] A process for preparing 1,2-pentanediol by hydrogenation of bio-based furfuryl alcohol includes the following steps:

[0127] Bio-based furfuryl alcohol hydrogenation process: 60 mL of a 20% furfuryl alcohol / ethanol solution was added to a 100 mL high-pressure reactor as the reaction solution. A 2 mol / L nitric acid aqueous solution was added as a reaction aid, with the amount of reaction aid being 2 wt% of the reaction solution. 0.6 g of the above-mentioned bio-based furfuryl alcohol hydrogenation catalyst was added. The catalytic hydrogenation reaction was carried out at a stirring speed of 700 rpm, a temperature of 220 ℃, and a reaction pressure of 8 MPa. The reaction was stopped after 5 h. The filtered reaction solution was analyzed by gas chromatography. The furfuryl alcohol conversion rate and 1,2-pentanediol selectivity are shown in Table 2.

[0128] Distillation Process: The liquid after hydrogenation was added to a rotary evaporator, and the heating temperature was set to 30℃. Ethanol and other low-boiling-point impurities were removed under vacuum. The remaining liquid was added to the reboiler of a distillation column packed with high-efficiency structured packing. A vacuum of 20 mbar was established, with the reboiler temperature at 95℃ and the distillation column temperature at 90℃. The reflux ratio was 3:1. The top liquid was sampled and analyzed every 2 hours. When there was no reflux at the top, the reboiler temperature and the distillation column temperature were increased by 10℃. When the reboiler temperature reached 125℃, no substances with boiling points lower than 1,2-pentanediol remained in the reboiler, and the top liquid was mostly 1,2-pentanediol. At this point, distillation was stopped, and the distillation column was thoroughly cleaned with ethanol, saving significant time and energy while increasing the distillate content. After cleaning, the reboiler temperature was raised to 125℃, and distillation continued. The purity of the 1,2-pentanediol obtained from the top liquid is shown in Table 2.

[0129] Comparative Example 4

[0130] The preparation of a bio-based furfuryl alcohol hydrogenation catalyst includes the following steps:

[0131] Step A: Dissolve Mg(NO3)2·6H2O (18 mmol) and Al(NO3)3·6H2O (36 mmol) in 300 mL of deionized water to prepare mixed solution A. Dissolve NaOH (0.156 mol) and Na2CO3 (0.024 mol) in 300 mL of deionized water to prepare mixed solution B. Add solutions A and B simultaneously to a rotating liquid film reactor at 3000 rpm and mix for 5 min. After crystallization at 65 ℃ for 12 h, filter the solid, wash repeatedly with deionized water until the filtrate is neutral, and dry at 65 ℃ overnight to obtain a magnesium-aluminum composite hydroxide. Calcine the obtained magnesium-aluminum composite hydroxide in a muffle furnace at 600 ℃ for 2 h to obtain an Al2O3-D2 support containing additives.

[0132] Step B: Impregnate an equal volume of H2PtCl6 solution (concentration 0.2 mol / L) into a round-bottom flask containing the Al2O3-D2 support with additives prepared in step (A), shake until homogeneous, shake for 1 h, and dry at 120 ℃ for 2 h to obtain the catalyst precursor Pt. 2+ / Al2O3-D2.

[0133] Step C: The Pt prepared in step (B) 2+The / Al2O3-D2 sample was placed in a tube furnace and calcined at 300 °C for 2 h in air at a heating rate of 2 °C / min. Subsequently, the sample was purged with N2 for 0.5 h and then reduced at 300 °C for 2 h in H2 atmosphere at a flow rate of 40 mL / min to obtain 4Pt / Al2O3-D2. The actual Pt loading was 4.0 wt%, and the Pt structure was a three-dimensional cluster.

[0134] A process for preparing 1,2-pentanediol by hydrogenation of bio-based furfuryl alcohol includes the following steps:

[0135] Bio-based furfuryl alcohol hydrogenation process: 60 mL of a 20% furfuryl alcohol / ethanol solution was added to a 100 mL high-pressure reactor as the reaction solution. A 2 mol / L nitric acid aqueous solution was added as a reaction aid, with the amount of reaction aid being 2 wt% of the reaction solution. 0.6 g of the above-mentioned bio-based furfuryl alcohol hydrogenation catalyst was added. The catalytic hydrogenation reaction was carried out at a stirring speed of 700 rpm, a temperature of 220 ℃, and a reaction pressure of 8 MPa. The reaction was stopped after 5 h. The filtered reaction solution was analyzed by gas chromatography. The furfuryl alcohol conversion rate and 1,2-pentanediol selectivity are shown in Table 2.

[0136] Distillation Process: The liquid after hydrogenation was added to a rotary evaporator, and the heating temperature was set to 30℃. Ethanol and other low-boiling-point impurities were removed under vacuum. The remaining liquid was added to the reboiler of a distillation column packed with high-efficiency structured packing. A vacuum of 20 mbar was established, with the reboiler temperature at 95℃ and the distillation column temperature at 90℃. The reflux ratio was 3:1. The top liquid was sampled and analyzed every 2 hours. When there was no reflux at the top, the reboiler temperature and the distillation column temperature were increased by 10℃. When the reboiler temperature reached 125℃, no substances with boiling points lower than 1,2-pentanediol remained in the reboiler, and the top liquid was mostly 1,2-pentanediol. At this point, distillation was stopped, and the distillation column was thoroughly cleaned with ethanol, saving significant time and energy while increasing the distillate content. After cleaning, the reboiler temperature was raised to 125℃, and distillation continued. The purity of the 1,2-pentanediol obtained from the top liquid is shown in Table 2.

[0137] Comparative Example 5

[0138] The preparation of a bio-based furfuryl alcohol hydrogenation catalyst includes the following steps:

[0139] Step A: Dissolve Mg(NO3)2·6H2O (18 mmol), Al(NO3)3·6H2O (36 mmol), and Zn(NO3)2·6H2O (2 mmol) in 300 mL of deionized water to prepare mixed solution A. Dissolve NaOH (0.156 mol) and Na2CO3 (0.024 mol) in 300 mL of deionized water to prepare mixed solution B. Add solutions A and B simultaneously to a rotating liquid film reactor at 3000 rpm and mix for 5 min. After crystallization at 65 ℃ for 12 h, filter the solid, wash repeatedly with deionized water until the filtrate is neutral, and dry at 65 ℃ overnight to obtain a magnesium-zinc-aluminum composite hydroxide. Calcine the obtained magnesium-zinc-aluminum composite hydroxide in a muffle furnace at 600 ℃ for 2 h to obtain an Al2O3-D3 support containing additives.

[0140] Step B: Impregnate an equal volume of H2PtCl6 solution (concentration 0.2 mol / L) into a round-bottom flask containing the Al2O3-D3 support with additives prepared in step (A), shake until homogeneous, shake for 1 h, and dry at 120 ℃ for 2 h to obtain the catalyst precursor Pt. 2+ / Al2O3-D3.

[0141] Step C: The Pt prepared in step (B) 2+ The / Al2O3-D3 sample was placed in a tube furnace and calcined at 300 °C for 2 h in air at a heating rate of 2 °C / min. Subsequently, the sample was purged with N2 for 0.5 h and then reduced at 300 °C for 2 h in H2 atmosphere at a flow rate of 40 mL / min to obtain 4Pt / Al2O3-D3. The actual Pt loading was 4.0 wt%, and the Pt structure was a three-dimensional cluster.

[0142] A process for preparing 1,2-pentanediol by hydrogenation of bio-based furfuryl alcohol includes the following steps:

[0143] Bio-based furfuryl alcohol hydrogenation process: 60 mL of a 20% furfuryl alcohol / ethanol solution was added to a 100 mL high-pressure reactor as the reaction solution. A 2 mol / L nitric acid aqueous solution was added as a reaction aid, with the amount of reaction aid being 2 wt% of the reaction solution. 0.6 g of the above-mentioned bio-based furfuryl alcohol hydrogenation catalyst was added. The catalytic hydrogenation reaction was carried out at a stirring speed of 700 rpm, a temperature of 220 ℃, and a reaction pressure of 8 MPa. The reaction was stopped after 5 h. The filtered reaction solution was analyzed by gas chromatography. The furfuryl alcohol conversion rate and 1,2-pentanediol selectivity are shown in Table 2.

[0144] Distillation Process: The liquid after hydrogenation was added to a rotary evaporator, and the heating temperature was set to 30℃. Ethanol and other low-boiling-point impurities were removed under vacuum. The remaining liquid was added to the reboiler of a distillation column packed with high-efficiency structured packing. A vacuum of 20 mbar was established, with the reboiler temperature at 95℃ and the distillation column temperature at 90℃. The reflux ratio was 3:1. The top liquid was sampled and analyzed every 2 hours. When there was no reflux at the top, the reboiler temperature and the distillation column temperature were increased by 10℃. When the reboiler temperature reached 125℃, no substances with boiling points lower than 1,2-pentanediol remained in the reboiler, and the top liquid was mostly 1,2-pentanediol. At this point, distillation was stopped, and the distillation column was thoroughly cleaned with ethanol, saving significant time and energy while increasing the distillate content. After cleaning, the reboiler temperature was raised to 125℃, and distillation continued. The purity of the 1,2-pentanediol obtained from the top liquid is shown in Table 2.

[0145] Comparative Example 6

[0146] The preparation of a bio-based furfuryl alcohol hydrogenation catalyst includes the following steps:

[0147] Step A: Dissolve Mg(NO3)2·6H2O (18 mmol), Al(NO3)3·6H2O (36 mmol), and Na2WO4·2H2O (4 mmol) in 300 mL of deionized water to prepare mixed solution A. Dissolve NaOH (0.156 mol) and Na2CO3 (0.024 mol) in 300 mL of deionized water to prepare mixed solution B. Add solutions A and B simultaneously to a rotating liquid film reactor at 3000 rpm and mix for 5 min. After crystallization at 65 ℃ for 12 h, filter the solid, wash repeatedly with deionized water until the filtrate is neutral, and dry at 65 ℃ overnight to obtain a composite hydroxide containing magnesium, aluminum, and tungsten. Calcine the obtained composite hydroxide containing magnesium, aluminum, and tungsten in a muffle furnace at 600 ℃ for 2 h to obtain an Al2O3-D4 support containing additives.

[0148] Step B: Impregnate an equal volume of H2PtCl6 solution (concentration 0.2 mol / L) into a round-bottom flask containing the Al2O3-D4 support with additives prepared in step (A), shake until homogeneous, shake for 1 h, and dry at 120 ℃ for 2 h to obtain the catalyst precursor Pt. 2+ / Al2O3-D4.

[0149] Step C: The Pt prepared in step (B) 2+The / Al2O3-D4 sample was placed in a tube furnace and calcined at 300 °C for 2 h in air at a heating rate of 2 °C / min. Subsequently, the sample was purged with N2 for 0.5 h and then reduced at 300 °C for 2 h in H2 atmosphere at a flow rate of 40 mL / min to obtain 4Pt / Al2O3-D4. The actual Pt loading was 4.0 wt%, and the Pt structure was a three-dimensional cluster.

[0150] A process for preparing 1,2-pentanediol by hydrogenation of bio-based furfuryl alcohol includes the following steps:

[0151] Bio-based furfuryl alcohol hydrogenation process: 60 mL of a 20% furfuryl alcohol / ethanol solution was added to a 100 mL high-pressure reactor as the reaction solution. A 2 mol / L nitric acid aqueous solution was added as a reaction aid, with the amount of reaction aid being 2 wt% of the reaction solution. 0.6 g of the above-mentioned bio-based furfuryl alcohol hydrogenation catalyst was added. The catalytic hydrogenation reaction was carried out at a stirring speed of 700 rpm, a temperature of 220 ℃, and a reaction pressure of 8 MPa. The reaction was stopped after 5 h. The filtered reaction solution was analyzed by gas chromatography. The furfuryl alcohol conversion rate and 1,2-pentanediol selectivity are shown in Table 2.

[0152] Distillation Process: The liquid after hydrogenation was added to a rotary evaporator, and the heating temperature was set to 30℃. Ethanol and other low-boiling-point impurities were removed under vacuum. The remaining liquid was added to the reboiler of a distillation column packed with high-efficiency structured packing. A vacuum of 20 mbar was established, with the reboiler temperature at 95℃ and the distillation column temperature at 90℃. The reflux ratio was 3:1. The top liquid was sampled and analyzed every 2 hours. When there was no reflux at the top, the reboiler temperature and the distillation column temperature were increased by 10℃. When the reboiler temperature reached 125℃, no substances with boiling points lower than 1,2-pentanediol remained in the reboiler, and the top liquid was mostly 1,2-pentanediol. At this point, distillation was stopped, and the distillation column was thoroughly cleaned with ethanol, saving significant time and energy while increasing the distillate content. After cleaning, the reboiler temperature was raised to 125℃, and distillation continued. The purity of the 1,2-pentanediol obtained from the top liquid is shown in Table 2.

[0153] Comparative Example 7

[0154] The preparation of a bio-based furfuryl alcohol hydrogenation catalyst includes the following steps:

[0155] Step A: Dissolve Mg(NO3)2·6H2O (18 mmol), Al(NO3)3·6H2O (36 mmol), Zn(NO3)2·6H2O (2 mmol), and Na2WO4·2H2O (4 mmol) in 300 mL of deionized water to prepare mixed solution A. Dissolve NaOH (0.156 mol) and Na2CO3 (0.024 mol) in 300 mL of deionized water to prepare mixed solution B. Add solutions A and B simultaneously to a rotating liquid film reactor at 3000 rpm and mix for 5 min. After crystallization at 65 ℃ for 12 h, filter the solid, wash repeatedly with deionized water until the filtrate is neutral, and dry at 65 ℃ overnight to obtain a composite hydroxide containing magnesium, zinc, aluminum, and tungsten. Calcine the obtained composite hydroxide containing magnesium, zinc, aluminum, and tungsten in a muffle furnace at 600 ℃ for 2 h to obtain an Al2O3-1 support containing additives.

[0156] Step B: Impregnate an equal volume of H2PtCl6 solution (concentration 0.2 mol / L) into a round-bottom flask containing the Al2O3-1 support with additives prepared in step (A), shake until homogeneous, shake for 1 h, and dry at 120 ℃ for 2 h to obtain the catalyst precursor Pt. 2+ / Al2O3-1.

[0157] Step C: The Pt prepared in step (B) 2+ The / Al2O3-1 sample was placed in a tube furnace and calcined at 300 °C for 2 h in air at a heating rate of 2 °C / min. Subsequently, the sample was purged with N2 for 0.5 h and then reduced at 300 °C for 2 h in H2 atmosphere at a flow rate of 40 mL / min to obtain 4Pt / Al2O3-1. The actual Pt loading was 4.0 wt%, and the Pt structure was a three-dimensional cluster.

[0158] A process for preparing 1,2-pentanediol by hydrogenation of bio-based furfuryl alcohol includes the following steps:

[0159] Bio-based furfuryl alcohol hydrogenation process: 60 mL of 20% furfuryl alcohol / ethanol solution was added to a 100 mL high-pressure reactor as the reaction solution, along with 0.6 g of the above-mentioned bio-based furfuryl alcohol hydrogenation catalyst. The catalytic hydrogenation reaction was carried out at a stirring speed of 700 rpm, a temperature of 220 ℃, and a reaction pressure of 8 MPa. The reaction was stopped after 5 h. The filtered reaction solution was analyzed by gas chromatography. The furfuryl alcohol conversion rate and 1,2-pentanediol selectivity are shown in Table 2.

[0160] Distillation Process: The liquid after hydrogenation was added to a rotary evaporator, and the heating temperature was set to 30℃. Ethanol and other low-boiling-point impurities were removed under vacuum. The remaining liquid was added to the reboiler of a distillation column packed with high-efficiency structured packing. A vacuum of 20 mbar was established, with the reboiler temperature at 95℃ and the distillation column temperature at 90℃. The reflux ratio was 3:1. The top liquid was sampled and analyzed every 2 hours. When there was no reflux at the top, the reboiler temperature and the distillation column temperature were increased by 10℃. When the reboiler temperature reached 125℃, no substances with boiling points lower than 1,2-pentanediol remained in the reboiler, and the top liquid was mostly 1,2-pentanediol. At this point, distillation was stopped, and the distillation column was thoroughly cleaned with ethanol, saving significant time and energy while increasing the distillate content. After cleaning, the reboiler temperature was raised to 125℃, and distillation continued. The purity of the 1,2-pentanediol obtained from the top liquid is shown in Table 2.

[0161] The catalyst compositions of each embodiment and comparative example are shown in Table 1.

[0162] Table 1

[0163]

[0164] The conversion rates, selectivity, and purity of 1,2-pentanediol for each example and comparative example are shown in Table 2.

[0165] Table 2

[0166]

[0167] As shown in Tables 1-2, compared with the comparative example, the catalyst of the present invention exhibits significant performance advantages in both furfuryl alcohol conversion and 1,2-pentanediol selectivity. The performance improvement is mainly attributed to the synergistic effect of the components: MgO and ZnO. x and WO y As an additive, Pt nanoparticles can regulate the acid-base balance of the Al2O3 support, optimize the physicochemical properties of the catalyst, and enhance its activity and stability. Pt nanoparticles themselves possess excellent C=C double bond hydrogenation and CO activation capabilities, enabling efficient catalysis of furfuryl alcohol hydrogenation. By controlling the structure of Pt, the hydrogenation performance and selectivity of the catalyst are further enhanced. The preparation process of this invention ensures the directional hydrogenation of the C=C double bond and CO activation of furfuryl alcohol, suppresses side reactions, and improves furfuryl alcohol conversion.

[0168] The various embodiments of the present invention have been described above. These descriptions are exemplary and not exhaustive, nor are they limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments.

Claims

1. A bio-based furfuryl alcohol hydrogenation catalyst, characterized in that, The catalyst consists of a support, an active component and a promoter supported on the support; the support is Al2O3, the active component is a Pt three-dimensional cluster, and the promoter is MgO and ZnO x and WO y , where 0 < x < 1 and 0 < y < 3; the particle size of Pt is 1.9 - 5 nm; The catalyst preparation method includes the following steps: 1) A composite hydroxide containing magnesium, zinc, aluminum, and tungsten was prepared using a rotating liquid film reactor, and calcined to obtain an Al2O3 support containing additives; 2) The Pt precursor solution was impregnated onto an Al2O3 support containing an auxiliary agent to prepare a catalyst precursor; 3) The catalyst precursor is calcined and reduced to obtain the catalyst; In step 1), magnesium salt, zinc salt, tungsten salt and aluminum salt are dissolved in water to obtain mixed solution A, and sodium hydroxide and sodium carbonate are dissolved in water to obtain mixed solution B. Mixed solution A and mixed solution B are added to a rotating liquid film reactor at the same time, mixed and crystallized, filtered, washed and dried to obtain a composite hydroxide containing magnesium, zinc, aluminum and tungsten.

2. The bio-based furfuryl alcohol hydrogenation catalyst according to claim 1, wherein, Based on the total weight of the catalyst, the content of Al2O3 is 45-78 wt%, the content of Pt is 3-5 wt%, the content of MgO is 6-15 wt%, and the content of ZnO is... x The content is 2-6 wt%, WO y The content is 10-30wt%.

3. The method for preparing the bio-based furfuryl alcohol hydrogenation catalyst according to claim 1 or 2, characterized in that, The preparation method includes the following steps: 1) A composite hydroxide containing magnesium, zinc, aluminum, and tungsten was prepared using a rotating liquid film reactor, and calcined to obtain an Al2O3 support containing additives; 2) The Pt precursor solution was impregnated onto an Al2O3 support containing an auxiliary agent to prepare a catalyst precursor; 3) The catalyst precursor is calcined and reduced to obtain the catalyst.

4. The method for preparing the bio-based furfuryl alcohol hydrogenation catalyst according to claim 3, wherein, In step 1), magnesium salt, zinc salt, tungsten salt and aluminum salt are dissolved in water to obtain mixed solution A, and sodium hydroxide and sodium carbonate are dissolved in water to obtain mixed solution B. Mixed solution A and mixed solution B are added to a rotating liquid film reactor at the same time, mixed and crystallized, filtered, washed and dried to obtain a composite hydroxide containing magnesium, zinc, aluminum and tungsten.

5. The method for preparing the bio-based furfuryl alcohol hydrogenation catalyst according to claim 4, wherein, The molar concentration of mixed solution A is 0.1-1.0 mol / L; the molar ratio of sodium hydroxide to sodium carbonate is 5-8:1; the molar concentration of mixed solution B is 0.2-2.0 mol / L; the crystallization temperature is 60-150℃ and the time is 12-48h.

6. The method for preparing the bio-based furfuryl alcohol hydrogenation catalyst according to claim 3, wherein, In step 1), the calcination temperature is 500-700℃ and the time is 1-6 hours; Step 2) includes: impregnating the Pt precursor solution with an Al2O3 support containing additives in the same volume, shaking for 0.5-2 hours, and then drying at 90-130℃ for 1-3 hours; The conditions for calcination reduction treatment include: calcination at 200-800℃ for 1-4 hours in an air atmosphere with a heating rate of 1-20℃ / min, followed by calcination at 200-800℃ for 1-4 hours in a hydrogen atmosphere.

7. A process for preparing 1,2-pentanediol by hydrogenation of bio-based furfuryl alcohol, characterized in that, The process includes: (1) Bio-based furfuryl alcohol hydrogenation: Under the action of the bio-based furfuryl alcohol hydrogenation catalyst according to claim 1 or 2, a reaction aid is added to the furfuryl alcohol / ethanol solution to carry out the hydrogenation reaction, wherein the reaction aid is an aqueous nitric acid solution with a concentration of 1-3 mol / L; (2) The reaction product obtained in step (1) is subjected to rotary evaporation and distillation to obtain 1,2-pentanediol.

8. The process for preparing 1,2-pentanediol by hydrogenation of bio-based furfuryl alcohol according to claim 7, wherein, In step (1), the hydrogenation reaction is carried out in a reactor, the amount of catalyst is 2-8% of the mass of furfuryl alcohol, and the reaction conditions include: reaction temperature of 100-300℃, reaction pressure of 3-12MPa, and reaction time of 2-10h. The furfuryl alcohol / ethanol solution contains 5%-50% furfuryl alcohol by mass, and the amount of the reaction aid is 1-5 wt% of the furfuryl alcohol / ethanol solution.

9. The process for preparing 1,2-pentanediol by hydrogenation of bio-based furfuryl alcohol according to claim 7, wherein, In step (2), the temperature of rotary evaporation is 30-50℃; the distillation conditions include: vacuum degree of 15-25mbar, reflux ratio of 1-10:1, bottom temperature of 55-155℃, and distillation column temperature of 50-150℃.

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