Method for preparing 1, 3-propylene glycol through glycerol hydrogenolysis

Abstract

The invention relates to a method for preparing 1, 3-propylene glycol through glycerol hydrogenolysis. According to the present invention, the multi-active component catalyst is prepared by using the cylindrical Al2O3 carrier, the glycerol aqueous solution can be subjected to high conversion rate and high selectivity hydrogenolysis under a certain hydrogen pressure and temperature to generate the target product 1, 3-propylene glycol, and the catalyst has good structure stability and can be repeatedly used;

Description

Technical Field

[0001] This invention relates to a multi-active component catalyst supported on cylindrical alumina for the hydrogenolysis of glycerol to prepare 1,3-propanediol. Technical Background

[0002] The booming biodiesel production has benefited the world, ensuring a greener fuel supply and reducing dependence on non-renewable fossil fuels. However, it also has its downsides. The rapid development of biodiesel has generated a large amount of glycerol as a byproduct. The low cost and surplus supply of glycerol necessitate that the biodiesel industry seek value-added conversion pathways. To this end, various methods have been proposed to convert glycerol into valuable products, such as the hydrogenolysis of glycerol to produce 1,3-propanediol (1,3-PDO).

[0003] 1,3-Propanediol has broad industrial application prospects, including applications in various fields such as cosmetics, clinical and pharmaceutical industries. The synthesis of 1,3-PDO by hydrogenolysis of glycerol has good environmental and economic benefits. However, how to activate the secondary hydroxyl group in glycerol to inhibit the formation of 1,2-propanediol (1,2-PDO) remains a challenge. In addition to the selective competition between 1,3-PDO and 1,2-PDO, both can be deeply hydrogenated to generate n-propanol and isopropanol. In order to selectively catalyze the formation of 1,3-PDO and suppress side reactions, the precise construction of catalyst structure and the control of reaction conditions are extremely important. Summary of the Invention

[0004] This invention provides a multi-active component catalyst supported on cylindrical alumina for the hydrogenolysis of glycerol to 1,3-propanediol. Compared with existing technologies, this invention effectively improves the conversion rate of glycerol and the selectivity of 1,3-propanediol. The multi-active component catalyst supported on cylindrical alumina exhibits good structural stability and can be reused.

[0005] This invention provides a method for preparing 1,3-propanediol by hydrogenolysis of glycerol. A multi-active component catalyst is prepared using a cylindrical Al₂O₃ support, which is obtained based on a micelle template-guided precipitation method. The specific preparation process is as follows: 1) A 0.5-3.0 mol / L aluminate solution is mixed uniformly with sodium alkyl carboxylate as a template agent. The mass of the aluminate is 5-50 g based on Al₂O₃. The reaction temperature is 25-85℃, and the template agent is fully dissolved and a micelle solution is formed under stirring. 2) A 0.5-2.5 mol / L carbonate solution with a volume of 35-500 mL is added to the micelle solution at a slow rate of 1-5 mL / min. Through the guiding effect of the micelle template, an aluminum hydroxide precursor precipitate is generated. The aluminum hydroxide precursor precipitate is aged at 25-85℃ for 2-12 hours. The aged aluminum hydroxide is then subjected to ion exchange with a 0.1-2.0 mol / L solution in a volume of 4-30 L. The aluminum hydroxide filter cake is obtained by washing with an ammonium salt solution until the conductivity of the wash solution stabilizes at 35-45 μS / cm within 5-20 minutes. Guaranteed sesame powder is added to the aluminum hydroxide filter cake as an extrusion aid, with a mass of 1-3% based on the mass of the aluminum hydroxide filter cake. Deionized water is added to adjust the humidity, making the total moisture content of the mixture 30-50 wt%. After thorough mixing in a kneader, the mixture is aged for 0.5-5 hours and then extruded through a screw extruder with a die orifice diameter of 1-5 mm and a cutting length of 4-8 mm to obtain cylindrical wet aluminum hydroxide strips. The cylindrical wet aluminum hydroxide strips are then air-dried at room temperature for 8-36 hours, dried at 80-120℃ for 2-8 hours, and then transferred to a muffle furnace and calcined at 400-800℃ for 2-5 hours to obtain a cylindrical Al2O3 support with a pore size distribution of 1-12 nm, an average pore size of 2-4 nm, and a specific surface area of ​​150-400 m². 2 / g. The cylindrical Al2O3 support is used to prepare a multi-active component catalyst, wherein the platinum loading is 0.1%-10% based on the mass of Al2O3; the promoter is denoted as A, and promoter A is one or more of W, Mo, Fe, Al, La, Ce, Sn, Zr, Zn, Mn, Nd, and Ta, and the promoter metal loading is 0.01%-15% based on the mass of Al2O3, and the resulting catalyst is labeled as Pt / AOx / Al2O3 (AOx is the metal oxide corresponding to promoter A, and x ranges from 1 to 6).

[0006] In the cylindrical Al2O3 support, the selected sodium alkyl carboxylate salt has a carbon chain length of 10-18, including one or more combinations of sodium decanoate, sodium undecanoate, sodium laurate, sodium tridecanoate, sodium myristate, sodium stearate, sodium pentadecanoate, sodium palmitate, sodium isotriadecanoate, sodium 2-hexyldecanoate, and sodium isostearate, more preferably one or more combinations of sodium undecanoate, sodium laurate, sodium tridecanoate, sodium myristate, sodium stearate, and sodium pentadecanoate, with the aluminate being aluminate (AlO2). - The molar ratio of sodium alkylcarboxylate salt to aluminate used as a template agent (template agent / AlO2) is calculated. - The preferred value is 0.01-0.50, and more preferably 0.1-0.4.

[0007] In the cylindrical Al2O3 support, the selected aluminate solution includes one or a combination of two or more of sodium aluminate solution, potassium aluminate solution, and ammonium aluminate solution, with the aluminate being aluminate ions (AlO2). - The aluminate solution concentration is preferably 0.5-3.0 mol / L, more preferably 1.0-2.5 mol / L, and the aluminate mass, converted to Al2O3, is 5-50 g.

[0008] In the cylindrical Al2O3 support, the selected carbonate solution includes one or more of sodium bicarbonate solution, ammonium carbonate solution, and ammonium bicarbonate solution, and the aluminate is represented by aluminate (AlO2). - ) calculated, the molar ratio of added carbonate to aluminate (CO3) 2- / AlO2 - The concentration of carbonate solution is preferably 1.0-2.5 mol / L, more preferably 1.0-2.0 mol / L, and the volume is 35-500 mL.

[0009] In the cylindrical Al2O3 support, the ammonium salt solution used for washing after aging includes one or a combination of two or more of ammonium methylformate, ammonium carbonate, ammonium bicarbonate, and ammonium acetate. The concentration of the ammonium salt solution is preferably 0.1-2.0 mol / L, more preferably 0.5-1.5 mol / L, and the volume is 4-30 L.

[0010] The preparation method of the cylindrical Al2O3 support for the multi-active component catalyst is as follows: A platinum precursor and an auxiliary precursor are simultaneously or sequentially loaded onto the cylindrical Al2O3 support using a wet impregnation method. The platinum precursor is one or more of chloroplatinic acid, platinum nitrate, platinum acetate, and platinum acetylacetonate. The auxiliary precursor A is one or more of chlorides, nitrates, phosphates, acetylacetonates, and acetates of W, Mo, Fe, Al, La, Ce, Sn, Zr, Zn, Mn, Nd, and Ta. The platinum loading is based on the proportion of Al... The mass of Al2O3 is preferably 0.1%-10%, more preferably 1-8%; the additive is designated A, which is one or more of W, Mo, Fe, Al, La, Ce, Sn, Zr, Zn, Mn, Nd, and Ta. The metal loading of the additive, based on the mass of Al2O3, is preferably 0.01%-15%, more preferably 2-10%. The mixture is impregnated for 20-50 hours, then air-dried at room temperature for 20-50 hours, and calcined in a muffle furnace at a high temperature of 200-400°C for 1-3 hours to obtain the catalyst Pt / AOx / Al2O3.

[0011] A multi-active component catalyst supported on cylindrical alumina is used for the hydrogenolysis of glycerol to prepare 1,3-propanediol. The reaction is carried out in a fixed-bed reactor, and the reactant is an aqueous solution of glycerol with a mass concentration of 10-90%. The preferred glycerol liquid hourly space velocity is 0.06-1.5 h⁻¹. -1 More preferably 0.5-1.2h -1 The hydrogen reaction pressure is preferably 0.1-12 MPa, more preferably 5-9 MPa, and the hydrogen gas space velocity is preferably 50-200 h⁻¹. -1 More preferably 120-200h -1 The reaction temperature is preferably 100-250℃, more preferably 150-190℃.

[0012] This patent uses a cylindrical Al2O3 support to prepare a multi-active component catalyst, which can hydrogenolyze an aqueous solution of glycerol with high conversion rate and high selectivity to generate the target product 1,3-propanediol under certain hydrogen pressure and temperature. It also has good structural stability and can be reused. Detailed Implementation

[0013] Example 1

[0014] A 2.5 mol / L sodium aluminate aqueous solution was mixed thoroughly with sodium undecanoate as a template agent. Template agent / AlO2 - The molar ratio was 0.30. The aluminate mass, converted to Al₂O₃, was 20 g. The reaction temperature was 50℃, and the mixture was stirred to form a micelle solution. A 2.0 mol / L sodium bicarbonate solution was added dropwise to the above micelle solution at a rate of 5 mL / min. CO₃²⁻2- / AlO2 - With a molar ratio of 1.2 and a sodium bicarbonate volume of 235 mL, an aluminum hydroxide precursor precipitate was generated. The aluminum hydroxide precursor precipitate was aged at 50 °C for 4 hours. The aged aluminum hydroxide was washed with 2.0 mol / L ammonium carbonate by ion exchange, with a total ammonium carbonate volume of 15 L, until the conductivity of the washing liquid stabilized at 40 μS / cm within 20 minutes, resulting in an aluminum hydroxide filter cake. Guaranteed sesame powder was added to the aluminum hydroxide filter cake as an extrusion aid, with the guaranteed sesame powder mass being 2% based on the mass of the aluminum hydroxide filter cake. Deionized water was added to adjust the humidity, making the total water content of the mixture 45% by mass. After being thoroughly kneaded in a kneader, the mixture was aged for 2.5 hours and then extruded through a screw extruder at a pressure of 5 MPa, a die orifice diameter of 3.0 mm, and a cutting length of 4 mm to obtain cylindrical wet aluminum hydroxide strips. The strips were air-dried at room temperature for 24 hours, dried at 110 °C for 2 hours, and then transferred to a muffle furnace and calcined at 500 °C for 2 hours to obtain a cylindrical Al2O3 support. The carrier has a pore size distribution of 2.8-3.1 nm, an average pore size of 3.05 nm, and a specific surface area of ​​305 m². 2 / g. The cylindrical Al2O3 support is used to prepare a multi-active component catalyst. 20g of cylindrical Al2O3 support is used. The platinum precursor is chloroplatinic acid, with a platinum loading of 2% on the Al2O3 support. The auxiliary precursor is tungsten pentachloride, with a W loading of 7.5% on the Al2O3 support. The W precursor is dissolved in deionized water, with the water mass being 40% based on the cylindrical Al2O3 support. The cylindrical Al2O3 support is then added to the precursor. The Pt precursor was soaked in an aqueous solution for 24 hours, air-dried for 24 hours, and calcined in a muffle furnace at 500°C for 5 hours to obtain WO3 / Al2O3. The Pt precursor was dissolved in deionized water, with the water mass being 40% based on the cylindrical Al2O3 support. The WO3 / Al2O3 was added to the Pt precursor solution, soaked for 24 hours, air-dried for 24 hours, and calcined in a muffle furnace at 300°C for 1 hour to obtain the catalyst, denoted as 2Pt / 7.5WO3 / Al2O3.

[0015] The reaction was carried out in a fixed-bed reactor. The reactant was an aqueous glycerol solution with a mass concentration of 50% and a glycerol liquid hourly space velocity of 1.0 h⁻¹. -1 The hydrogen reaction pressure is 9 MPa, and the hydrogen gas space velocity is 200 h⁻¹. -1 The reaction temperature was 180℃. The results are shown in Table 1.

[0016] Example 2

[0017] A 2.5 mol / L sodium aluminate aqueous solution was mixed thoroughly with sodium stearate as a template agent. Template agent / AlO2 -The molar ratio was 0.25. The aluminate mass, converted to Al₂O₃, was 10 g. The reaction temperature was 50℃, and the mixture was stirred to form a micelle solution. A 2.0 mol / L sodium bicarbonate solution was added dropwise to the above micelle solution at a rate of 4 mL / min. CO₃²⁻ 2- / AlO2 - With a molar ratio of 1.2 and a sodium bicarbonate volume of 60 mL, an aluminum hydroxide precursor precipitate was generated. The aluminum hydroxide precursor precipitate was aged at 50 °C for 4 hours. The aged aluminum hydroxide was washed with 1.0 mol / L ammonium carbonate by ion exchange, with a total ammonium carbonate volume of 6 L, until the conductivity of the washing liquid stabilized at 40 μS / cm within 20 minutes, resulting in an aluminum hydroxide filter cake. Guaranteed sesame powder was added to the aluminum hydroxide filter cake as an extrusion aid, with the guaranteed sesame powder mass being 2% based on the mass of the aluminum hydroxide filter cake. Deionized water was added to adjust the humidity, making the total water content of the mixture 45% by mass. After being thoroughly kneaded in a kneader, the mixture was aged for 2.5 hours and then extruded through a screw extruder at a pressure of 5 MPa, a die orifice diameter of 3.0 mm, and a cutting length of 4 mm to obtain cylindrical wet aluminum hydroxide strips. The strips were air-dried at room temperature for 24 hours, dried at 110 °C for 2 hours, and then transferred to a muffle furnace and calcined at 500 °C for 2 hours to obtain a cylindrical Al2O3 support. The carrier has a pore size distribution of 3.5-4.0 nm, an average pore size of 3.75 nm, and a specific surface area of ​​280 m². 2 / g. The cylindrical Al2O3 support is used to prepare a multi-active component catalyst. 10g of cylindrical Al2O3 support is used. The platinum precursor is chloroplatinic acid, with a platinum loading of 2% on the Al2O3 support. The auxiliary precursor is tungsten pentachloride, with a W loading of 7.5% on the Al2O3 support. The W precursor is dissolved in deionized water, with the water mass being 40% based on the cylindrical Al2O3 support. The cylindrical Al2O3 support is then added to the precursor. The Pt precursor was soaked in an aqueous solution for 24 hours, air-dried for 24 hours, and calcined in a muffle furnace at 500°C for 5 hours to obtain WO3 / Al2O3. The Pt precursor was dissolved in deionized water, with the water mass being 40% based on the cylindrical Al2O3 support. The WO3 / Al2O3 was added to the Pt precursor solution, soaked for 24 hours, air-dried for 24 hours, and calcined in a muffle furnace at 300°C for 1 hour to obtain the catalyst, denoted as 2Pt / 7.5WO3 / Al2O3.

[0018] The reaction was carried out in a fixed-bed reactor. The reactant was an aqueous glycerol solution with a mass concentration of 50% and a glycerol liquid hourly space velocity of 1.0 h⁻¹. -1 The hydrogen reaction pressure is 9 MPa, and the hydrogen gas space velocity is 200 h⁻¹. -1 The reaction temperature was 180℃. The results are shown in Table 1.

[0019] Example 3

[0020] A 2.0 mol / L sodium aluminate aqueous solution was mixed thoroughly with sodium laurate as a template agent. Template agent / AlO2 - The molar ratio was 0.4. The aluminate mass, converted to Al₂O₃, was 20 g. The reaction temperature was 50℃, and the mixture was stirred to form a micelle solution. A 1.5 mol / L sodium bicarbonate solution was added dropwise to the above micelle solution at a rate of 3 mL / min. CO₃²⁻ 2- / AlO2 - With a molar ratio of 1.5 and a sodium bicarbonate volume of 390 mL, an aluminum hydroxide precursor precipitate was generated. The aluminum hydroxide precursor precipitate was aged at 50 °C for 4 hours. The aged aluminum hydroxide was washed with 1.0 mol / L ammonium carbonate by ion exchange, with a total ammonium carbonate volume of 6 L, until the conductivity of the washing liquid stabilized at 40 μS / cm within 20 minutes, resulting in an aluminum hydroxide filter cake. Guaranteed guar gum powder was added to the aluminum hydroxide filter cake as an extrusion aid, with the guar gum powder mass being 2% based on the mass of the aluminum hydroxide filter cake. Deionized water was added to adjust the humidity, making the total water content of the mixture 45% by mass. After being thoroughly kneaded in a kneader, the mixture was aged for 2.5 hours and then extruded through a screw extruder at a pressure of 5 MPa, a die orifice diameter of 3.0 mm, and a cutting length of 4 mm to obtain cylindrical wet aluminum hydroxide strips. The strips were air-dried at room temperature for 24 hours, dried at 110 °C for 2 hours, and then transferred to a muffle furnace and calcined at 500 °C for 2 hours to obtain a cylindrical Al2O3 support. The carrier has a pore size distribution of 2.5-3.2 nm, an average pore size of 2.90 nm, and a specific surface area of ​​320 m². 2 / g. The cylindrical Al2O3 support is used to prepare a multi-active component catalyst. 20g of cylindrical Al2O3 support is used. The platinum precursor is chloroplatinic acid, with a platinum content of 2% by mass on the Al2O3 support. The auxiliary precursor is tungsten pentachloride, with a W content of 7.5% by mass on the Al2O3 support. The W precursor is dissolved in deionized water, with the water mass being 40% based on the cylindrical Al2O3 support. The cylindrical Al2O3 support is then added to the precursor. The Pt precursor was soaked in an aqueous solution for 24 hours, air-dried for 24 hours, and calcined in a muffle furnace at 500°C for 5 hours to obtain WO3 / Al2O3. The Pt precursor was dissolved in deionized water, with the water mass being 40% based on the cylindrical Al2O3 support. The WO3 / Al2O3 was added to the Pt precursor solution, soaked for 24 hours, air-dried for 24 hours, and calcined in a muffle furnace at 300°C for 1 hour to obtain the catalyst, denoted as 2Pt / 7.5WO3 / Al2O3.

[0021] The reaction was carried out in a fixed-bed reactor. The reactant was an aqueous glycerol solution with a mass concentration of 50% and a glycerol liquid hourly space velocity of 1.0 h⁻¹. -1 The hydrogen reaction pressure is 9 MPa, and the hydrogen gas space velocity is 200 h⁻¹. -1 The reaction temperature was 180℃. The results are shown in Table 1.

[0022] Example 4

[0023] A 1.5 mol / L sodium aluminate solution was mixed thoroughly with sodium tridecanoate as a template agent. Template agent / AlO2 - The molar ratio was 0.2. The aluminate mass, converted to Al₂O₃, was 20 g. The reaction temperature was 50℃, and the mixture was stirred to form a micelle solution. A 1.5 mol / L sodium bicarbonate solution was added dropwise to the above micelle solution at a rate of 2 mL / min. CO₃²⁻ 2- / AlO2 - With a molar ratio of 1.3 and a sodium bicarbonate volume of 340 mL, an aluminum hydroxide precursor precipitate was generated. The aluminum hydroxide precursor precipitate was aged at 50 °C for 4 hours. The aged aluminum hydroxide was washed with 0.5 mol / L ammonium carbonate by ion exchange, with a total ammonium carbonate volume of 12 L, until the conductivity of the washing liquid stabilized at 40 μS / cm within 20 minutes, resulting in an aluminum hydroxide filter cake. Guaranteed guar gum powder was added to the aluminum hydroxide filter cake as an extrusion aid, with the guar gum powder mass being 2% based on the mass of the aluminum hydroxide filter cake. Deionized water was added to adjust the humidity, making the total water content of the mixture 45% by mass. After being thoroughly kneaded in a kneader, the mixture was aged for 2.5 hours and then extruded through a screw extruder at a pressure of 5 MPa, a die orifice diameter of 3.0 mm, and a cutting length of 4 mm to obtain cylindrical wet aluminum hydroxide strips. The strips were air-dried at room temperature for 24 hours, dried at 110 °C for 2 hours, and then transferred to a muffle furnace and calcined at 500 °C for 2 hours to obtain a cylindrical Al2O3 support. The carrier has a pore size distribution of 2.8-3.4 nm, an average pore size of 3.1 nm, and a specific surface area of ​​300 m². 2 / g. The cylindrical Al2O3 support is used to prepare a multi-active component catalyst. 20g of cylindrical Al2O3 support is used. The platinum precursor is chloroplatinic acid, with a platinum loading of 2% on the Al2O3 support. The auxiliary precursor is tungsten pentachloride, with a W loading of 7.5% on the Al2O3 support. The W precursor is dissolved in deionized water, with the water mass being 40% based on the cylindrical Al2O3 support. The cylindrical Al2O3 support is then added to the precursor. The Pt precursor was soaked in an aqueous solution for 24 hours, air-dried for 24 hours, and calcined in a muffle furnace at 500°C for 5 hours to obtain WO3 / Al2O3. The Pt precursor was dissolved in deionized water, with the water mass being 40% based on the cylindrical Al2O3 support. The WO3 / Al2O3 was added to the Pt precursor solution, soaked for 24 hours, air-dried for 24 hours, and calcined in a muffle furnace at 300°C for 1 hour to obtain the catalyst, denoted as 2Pt / 7.5WO3 / Al2O3.

[0024] The reaction was carried out in a fixed-bed reactor. The reactant was an aqueous glycerol solution with a mass concentration of 50% and a glycerol liquid hourly space velocity of 1.0 h⁻¹. -1 The hydrogen reaction pressure is 9 MPa, and the hydrogen gas space velocity is 200 h⁻¹. -1The reaction temperature was 180℃. The results are shown in Table 1.

[0025] Example 5

[0026] A 1.0 mol / L sodium aluminate solution was mixed thoroughly with sodium tridecanoate as a template agent. Template agent / AlO2 - The molar ratio was 0.1. The aluminate mass, converted to Al₂O₃, was 10 g. The reaction temperature was 50℃, and the mixture was stirred to form a micelle solution. A 1.0 mol / L sodium bicarbonate solution was added dropwise to the above micelle solution at a rate of 1 mL / min. CO₃²⁻ 2- / AlO2 - With a molar ratio of 1.0 and a sodium bicarbonate volume of 100 mL, an aluminum hydroxide precursor precipitate was generated. The aluminum hydroxide precursor precipitate was aged at 50 °C for 4 hours. The aged aluminum hydroxide was washed with 0.5 mol / L ammonium carbonate by ion exchange, with a total ammonium carbonate volume of 6 L, until the conductivity of the washing liquid stabilized at 40 μS / cm within 20 minutes, resulting in an aluminum hydroxide filter cake. Guaranteed sesame powder was added to the aluminum hydroxide filter cake as an extrusion aid, with the guaranteed sesame powder weight being 2% based on the weight of the aluminum hydroxide filter cake. Deionized water was added to adjust the humidity so that the total water content of the mixture was 45% by mass. After being thoroughly kneaded in a kneader, the mixture was aged for 2.5 hours and then extruded through a screw extruder at a pressure of 5 MPa, a die orifice diameter of 3.0 mm, and a cutting length of 4 mm to obtain cylindrical wet aluminum hydroxide strips. The strips were air-dried at room temperature for 24 hours, dried at 110 °C for 2 hours, and then transferred to a muffle furnace and calcined at 500 °C for 2 hours to obtain a cylindrical Al2O3 support. The carrier has a pore size distribution of 3.8-4.5 nm, an average pore size of 3.99 nm, and a specific surface area of ​​260 m². 2 / g. The cylindrical Al2O3 support is used to prepare a multi-active component catalyst. 10g of cylindrical Al2O3 support is used. The platinum precursor is chloroplatinic acid, with a platinum loading of 2% on the Al2O3 support. The auxiliary precursor is tungsten pentachloride, with a W loading of 7.5% on the Al2O3 support. The W precursor is dissolved in deionized water, with the water mass being 40% based on the cylindrical Al2O3 support. The cylindrical Al2O3 support is then added to the precursor. The Pt precursor was soaked in an aqueous solution for 24 hours, air-dried for 24 hours, and calcined in a muffle furnace at 500°C for 5 hours to obtain WO3 / Al2O3. The Pt precursor was dissolved in deionized water, with the water mass being 40% based on the cylindrical Al2O3 support. The WO3 / Al2O3 was added to the Pt precursor solution, soaked for 24 hours, air-dried for 24 hours, and calcined in a muffle furnace at 300°C for 1 hour to obtain the catalyst, denoted as 2Pt / 7.5WO3 / Al2O3.

[0027] The reaction was carried out in a fixed-bed reactor. The reactant was an aqueous glycerol solution with a mass concentration of 50% and a glycerol liquid hourly space velocity of 1.0 h⁻¹. -1The hydrogen reaction pressure is 9 MPa, and the hydrogen gas space velocity is 180 h⁻¹. -1 The reaction temperature was 180℃. The results are shown in Table 1.

[0028] Example 6

[0029] Sodium undecanoate was replaced with an equimolar amount of sodium pentadecanoate, and all other conditions were the same as in Example 1. The carrier pore size distribution was 3.2-3.8 nm, with an average pore size of 3.5 nm and a specific surface area of ​​290 m². 2 / g. The results are shown in Table 1.

[0030] Example 7

[0031] Sodium stearate was replaced with an equimolar amount of sodium myristate, and other conditions were the same as in Example 2. The carrier pore size distribution was 3.2-3.7 nm, with an average pore size of 3.45 nm and a specific surface area of ​​295 m². 2 / g. The results are shown in Table 1.

[0032] Example 8

[0033] Sodium lauryl was replaced with an equimolar amount of sodium palmitate, and other conditions were the same as in Example 3. The carrier pore size distribution was 3.6-4.2 nm, with an average pore size of 3.9 nm and a specific surface area of ​​270 m². 2 / g. The results are shown in Table 1.

[0034] Example 9

[0035] Replace sodium undecanoate with an equimolar amount of sodium decanoate, template agent / AlO2 - The molar ratio was 0.05, and other conditions were the same as in Example 1. The carrier pore size distribution was 3.5-4.5 nm, with an average pore size of 4.0 nm and a specific surface area of ​​240 m². 2 / g. The results are shown in Table 1.

[0036] Example 10

[0037] Replace sodium undecanoate with an equimolar amount of sodium isotriadecanoate, template agent / AlO2 - The molar ratio was 0.01, and other conditions were the same as in Example 1. The carrier pore size distribution was 7.0-9.0 nm, with an average pore size of 8.0 nm and a specific surface area of ​​201 m². 2 / g. The results are shown in Table 1.

[0038] Example 11

[0039] Sodium undecanoate was replaced with an equimolar amount of sodium 2-hexyldecanoate, and other conditions were the same as in Example 1. The carrier pore size distribution was 6.5-8.5 nm, with an average pore size of 7.5 nm and a specific surface area of ​​195 m². 2 / g. The results are shown in Table 1.

[0040] Example 12

[0041] A 2.5 mol / L sodium aluminate aqueous solution was mixed thoroughly with sodium undecanoate as a template agent. Template agent / AlO2 - The molar ratio was 0.30, the aluminate mass (calculated as Al2O3) was 20 g, the reaction temperature was 60 °C, and stirring was used to form a micelle solution. Other conditions were the same as in Example 1. The carrier pore size distribution was 3.5-4.5 nm, the average pore size was 4.0 nm, and the specific surface area was 285 m². 2 / g. The results are shown in Table 1.

[0042] Example 13

[0043] A 2.5 mol / L sodium aluminate aqueous solution was mixed thoroughly with sodium undecanoate as a template agent. Template agent / AlO2 - The molar ratio was 0.30, the aluminate mass (calculated as Al2O3) was 20 g, the reaction temperature was 70 °C, and stirring was used to form a micelle solution. Other conditions were the same as in Example 1. The carrier pore size distribution was 3.5-4.5 nm, the average pore size was 3.9 nm, and the specific surface area was 335 m². 2 / g. The results are shown in Table 1.

[0044] Example 14

[0045] A 2.5 mol / L sodium aluminate aqueous solution was mixed thoroughly with sodium undecanoate as a template agent. Template agent / AlO2 - The molar ratio was 0.30, the aluminate mass (calculated as Al2O3) was 20 g, the reaction temperature was 40 °C, and stirring was used to form a micelle solution. Other conditions were the same as in Example 1. The carrier pore size distribution was 2.2-2.7 nm, the average pore size was 2.45 nm, and the specific surface area was 345 m². 2 / g. The results are shown in Table 1.

[0046] Example 15

[0047] A 2.5 mol / L sodium aluminate aqueous solution was mixed thoroughly with sodium undecanoate as a template agent. Template agent / AlO2 - The molar ratio was 0.30, the aluminate mass (calculated as Al2O3) was 20 g, the reaction temperature was 30 °C, and stirring was used to form a micelle solution. Other conditions were the same as in Example 1. The carrier pore size distribution was 1.8-2.3 nm, the average pore size was 2.05 nm, and the specific surface area was 380 m². 2 / g. The results are shown in Table 1.

[0048] Example 16

[0049] Sodium aluminate was replaced with an equimolar amount of potassium aluminate, and other conditions were the same as in Example 1. The carrier pore size distribution was 2.9-3.2 nm, with an average pore size of 3.08 nm and a specific surface area of ​​302 m². 2 / g. The results are shown in Table 1.

[0050] Example 17

[0051] Sodium aluminate was replaced with an equimolar amount of potassium aluminate, and other conditions were the same as in Example 2. The carrier pore size distribution was 3.4-4.0 nm, with an average pore size of 3.70 nm and a specific surface area of ​​282 m². 2 / g. The results are shown in Table 1.

[0052] Example 18

[0053] The sodium bicarbonate was replaced with ammonium carbonate in a different molar amount, while other conditions remained the same as in Example 1. The carrier had a pore size distribution of 2.9-3.2 nm, an average pore size of 3.06 nm, and a specific surface area of ​​308 m². 2 / g. The results are shown in Table 1.

[0054] Example 19

[0055] The aged aluminum hydroxide was washed with 1.0 mol / L ammonium methylformate via ion exchange, with a total ammonium methylformate volume of 6 L. Other conditions were the same as in Example 1. The support had a pore size distribution of 2.9-3.2 nm, an average pore size of 3.07 nm, and a specific surface area of ​​303 m². 2 / g. The results are shown in Table 1.

[0056] Example 20

[0057] The aged aluminum hydroxide was washed with 1.5 mol / L ammonium acetate via ion exchange, with a total ammonium acetate volume of 6 L. Other conditions were the same as in Example 1. The support had a pore size distribution of 2.9-3.2 nm, an average pore size of 3.06 nm, and a specific surface area of ​​307 m². 2 / g. The results are shown in Table 1.

[0058] Example 21

[0059] Tungsten pentachloride was replaced with ferric nitrate nonahydrate, and the Fe loading was 2.5%, with other conditions remaining the same as in Example 1. The pore size distribution of the support was 2.8-3.1 nm, with an average pore size of 3.05 nm and a specific surface area of ​​305 m². 2 / g. The results are shown in Table 1.

[0060] Example 22

[0061] Tungsten pentachloride was replaced with ferric nitrate nonahydrate, and the Fe loading was 7.5%, with other conditions remaining the same as in Example 2. The pore size distribution of the support was 3.5-4.0 nm, with an average pore size of 3.75 nm and a specific surface area of ​​280 m². 2 / g. The results are shown in Table 1.

[0062] Example 23

[0063] Tungsten pentachloride was replaced with tungsten tetrachloride, and the W loading was 4%, with other conditions remaining the same as in Example 1. The pore size distribution of the support was 2.8-3.1 nm, with an average pore size of 3.05 nm and a specific surface area of ​​305 m². 2 / g. The results are shown in Table 1.

[0064] Example 24

[0065] Tungsten pentachloride was replaced with tantalum pentachloride, and the Ta loading was 4%, while other conditions remained the same as in Example 16. The pore size distribution of the support was 2.9-3.2 nm, with an average pore size of 3.08 nm and a specific surface area of ​​302 m². 2 / g. The results are shown in Table 1.

[0066] Example 25

[0067] Tungsten pentachloride was replaced with lanthanum nitrate hexahydrate, and the La loading was 6%, with other conditions remaining the same as in Example 1. The pore size distribution of the support was 2.8-3.1 nm, with an average pore size of 3.05 nm and a specific surface area of ​​305 m². 2 / g. The results are shown in Table 1.

[0068] Example 26

[0069] Tungsten pentachloride was replaced with cerium chloride heptahydrate, and the Ce loading was 6%, with other conditions remaining the same as in Example 1. The pore size distribution of the support was 2.8-3.1 nm, with an average pore size of 3.1 nm and a specific surface area of ​​300 m². 2 / g. The results are shown in Table 1.

[0070] Example 27

[0071] Tungsten pentachloride was replaced with zirconium tetrachloride, and the Zr loading was 4%, with other conditions remaining the same as in Example 1. The pore size distribution of the support was 2.8-3.1 nm, with an average pore size of 3.05 nm and a specific surface area of ​​305 m². 2 / g. The results are shown in Table 1.

[0072] Example 28

[0073] Tungsten pentachloride was replaced with zinc nitrate hexahydrate, and the Zn loading was 3%, with other conditions remaining the same as in Example 1. The pore size distribution of the support was 2.8-3.1 nm, with an average pore size of 3.05 nm and a specific surface area of ​​303 m². 2 / g. The results are shown in Table 1.

[0074] Example 29

[0075] Tungsten pentachloride was replaced with manganese acetate, and the Mn loading was 2.5%, with other conditions remaining the same as in Example 1. The pore size distribution of the support was 2.8-3.1 nm, with an average pore size of 3.02 nm and a specific surface area of ​​301 m². 2 / g. The results are shown in Table 1.

[0076] Example 30

[0077] Tungsten pentachloride was replaced with tantalum pentachloride, and the Ta loading was 7.5%, with other conditions remaining the same as in Example 2. The pore size distribution of the support was 3.5-4.0 nm, with an average pore size of 3.75 nm and a specific surface area of ​​280 m². 2 / g. The results are shown in Table 1.

[0078] Example 31

[0079] Tungsten pentachloride was replaced with molybdenum pentachloride and tantalum pentachloride. The Mo loading was 2.8%, the Ta loading was 2.8%, and the Mo+Ta loading was 5.6%. Other conditions were the same as in Example 1. The pore size distribution of the support was 2.8-3.1 nm, the average pore size was 3.05 nm, and the specific surface area was 307 m². 2 / g. The results are shown in Table 1.

[0080] Example 32

[0081] Tungsten pentachloride was replaced with molybdenum pentachloride and tungsten oxyacetylacetone. The Mo loading was 2.8%, the W loading was 2.9%, and the Mo+W loading was 5.7%, with other conditions remaining the same as in Example 1. The pore size distribution of the support was 2.8-3.1 nm, with an average pore size of 3.03 nm and a specific surface area of ​​302 m². 2 / g. The results are shown in Table 1.

[0082] Example 33

[0083] Cylindrical aluminum hydroxide wet strips were air-dried at room temperature for 12 hours, then dried at 110°C for 3 hours, with other conditions the same as in Example 1. The carrier had a pore size distribution of 3.0-3.6 nm, an average pore size of 3.30 nm, and a specific surface area of ​​295 m². 2 / g. The results are shown in Table 1.

[0084] Example 34

[0085] Cylindrical aluminum hydroxide wet strips were air-dried at room temperature for 8 hours, then dried at 110°C for 8 hours, with other conditions the same as in Example 1. The carrier had a pore size distribution of 3.8-5.0 nm, an average pore size of 4.40 nm, and a specific surface area of ​​265 m². 2 / g. The results are shown in Table 1.

[0086] Example 35

[0087] Cylindrical aluminum hydroxide wet strips were air-dried at room temperature for 36 hours, then dried at 110°C for 5 hours, with other conditions the same as in Example 1. The carrier had a pore size distribution of 2.5-2.9 nm, an average pore size of 2.70 nm, and a specific surface area of ​​335 m². 2 / g. The results are shown in Table 1.

[0088] Example 36

[0089] Cylindrical aluminum hydroxide wet strips were air-dried and then calcined in a muffle furnace at 450°C for 3 hours, under the same conditions as in Example 1. The carrier had a pore size distribution of 2.5-2.9 nm, an average pore size of 2.72 nm, and a specific surface area of ​​340 m². 2 / g. The results are shown in Table 1.

[0090] Example 37

[0091] Cylindrical aluminum hydroxide strips were air-dried and then calcined in a muffle furnace at 550°C for 2.5 hours, under the same conditions as in Example 1. The carrier had a pore size distribution of 2.8-3.8 nm, an average pore size of 3.30 nm, and a specific surface area of ​​368 m². 2 / g. The results are shown in Table 1.

[0092] Example 38

[0093] Cylindrical aluminum hydroxide wet strips were air-dried and then calcined in a muffle furnace at 400°C for 5 hours, under the same conditions as in Example 1. The carrier had a pore size distribution of 2.2-2.7 nm, an average pore size of 2.45 nm, and a specific surface area of ​​365 m². 2 / g. The results are shown in Table 1.

[0094] Example 39

[0095] The chloroplatinic acid was replaced with platinum nitrate, the platinum loading was 1%, the W loading was 6%, and other conditions were the same as in Example 1. The pore size distribution of the support was 2.8-3.2 nm, the average pore size was 3.05 nm, and the specific surface area was 301 m². 2 / g. The results are shown in Table 1.

[0096] Example 40

[0097] The platinum loading was 1.5%, the W loading was 7%, and other conditions were the same as in Example 1. The pore size distribution of the support was 2.8-3.1 nm, the average pore size was 3.01 nm, and the specific surface area was 302 m². 2 / g. The results are shown in Table 1.

[0098] Example 41

[0099] The platinum loading was 3%, the W loading was 8%, and other conditions were the same as in Example 39. The pore size distribution of the support was 2.8-3.1 nm, the average pore size was 3.06 nm, and the specific surface area was 303 m². 2 / g. The results are shown in Table 1.

[0100] Example 42

[0101] The platinum loading was 4%, the W loading was 9%, and other conditions were the same as in Example 1. The pore size distribution of the support was 2.8-3.1 nm, the average pore size was 3.05 nm, and the specific surface area was 305 m². 2 / g. The results are shown in Table 1.

[0102] Example 43

[0103] The platinum loading was 5%, the W loading was 10%, and other conditions were the same as in Example 39. The pore size distribution of the support was 2.8-3.1 nm, the average pore size was 3.07 nm, and the specific surface area was 309 m². 2 / g. The results are shown in Table 1.

[0104] Example 44

[0105] The platinum loading was 6%, the W loading was 11%, and other conditions were the same as in Example 1. The pore size distribution of the support was 2.8-3.1 nm, with an average pore size of 3.06 nm and a specific surface area of ​​308 m². 2 / g. The results are shown in Table 1.

[0106] Example 45

[0107] The platinum loading was 8%, the W loading was 13.5%, and other conditions were the same as in Example 1. The pore size distribution of the carrier was 2.8-3.1 nm, the average pore size was 3.05 nm, and the specific surface area was 305 m². 2 / g. The results are shown in Table 1.

[0108] Example 46

[0109] The platinum loading was 0.5%, the W loading was 1.5%, and other conditions were the same as in Example 1. The pore size distribution of the support was 2.7-3.1 nm, the average pore size was 3.01 nm, and the specific surface area was 304 m². 2 / g. The results are shown in Table 1.

[0110] Example 47

[0111] Tungsten pentachloride was replaced with tungsten oxyacetylacetone, and other conditions were the same as in Example 1. The pore size distribution of the support was 2.8-3.1 nm, with an average pore size of 3.05 nm and a specific surface area of ​​305 m². 2 / g. The results are shown in Table 1.

[0112] Example 48

[0113] Tungsten pentachloride was replaced with tungsten oxyacetylacetone, impregnated for 36 hours, air-dried for 36 hours, and calcined in a muffle furnace at 200°C for 3 hours, with other conditions the same as in Example 1. The pore size distribution of the support was 2.8-3.1 nm, with an average pore size of 3.05 nm and a specific surface area of ​​305 m². 2 / g. The results are shown in Table 1.

[0114] Example 49

[0115] Tungsten pentachloride was replaced with tungsten oxyacetylacetone, impregnated for 48 hours, air-dried for 48 hours, and calcined in a muffle furnace at 250°C for 2.5 hours, with other conditions the same as in Example 1. The pore size distribution of the support was 2.8-3.1 nm, with an average pore size of 3.05 nm and a specific surface area of ​​305 m². 2 / g. The results are shown in Table 1.

[0116] Example 50

[0117] Tungsten pentachloride was replaced with tungsten oxyacetylacetone, impregnated for 20 hours, air-dried for 20 hours, and calcined in a muffle furnace at 400°C for 3 hours, with other conditions the same as in Example 1. The pore size distribution of the support was 2.8-3.1 nm, with an average pore size of 3.05 nm and a specific surface area of ​​305 m². 2 / g. The results are shown in Table 1.

[0118] Example 51

[0119] Ferric nitrate nonahydrate was replaced with ferric chloride hexahydrate, and all other conditions were the same as in Example 22. The carrier pore size distribution was 3.5-4.0 nm, with an average pore size of 3.75 nm and a specific surface area of ​​280 m². 2 / g. The results are shown in Table 1.

[0120] Example 52

[0121] The platinum loading was 0.1%, the Fe loading was 0.01%, and other conditions were the same as in Example 22. The carrier pore size distribution was 3.5-4.0 nm, the average pore size was 3.75 nm, and the specific surface area was 280 m². 2 / g. The results are shown in Table 1.

[0122] Example 53

[0123] The chloroplatinic acid was replaced with platinum acetate, the platinum loading was 6%, the Fe loading was 12.5%, and other conditions were the same as in Example 22. The carrier pore size distribution was 3.5-4.0 nm, the average pore size was 3.75 nm, and the specific surface area was 280 m². 2 / g. The results are shown in Table 1.

[0124] Example 54

[0125] The platinum loading was 10%, the Fe loading was 15%, and other conditions were the same as in Example 22. The carrier pore size distribution was 3.5-4.0 nm, the average pore size was 3.75 nm, and the specific surface area was 280 m². 2 / g. The results are shown in Table 1.

[0126] Example 55

[0127] Lanthanum nitrate hexahydrate was replaced with lanthanum chloride hexahydrate, and all other conditions were the same as in Example 25. The support had a pore size distribution of 2.8-3.1 nm, an average pore size of 3.05 nm, and a specific surface area of ​​305 m². 2 / g. The results are shown in Table 1.

[0128] Example 56

[0129] The chloroplatinic acid was replaced with platinum nitrate, the platinum loading was 1%, the La loading was 1.5%, and other conditions were the same as in Example 55. The carrier pore size distribution was 2.8-3.1 nm, the average pore size was 3.05 nm, and the specific surface area was 305 m². 2 / g. The results are shown in Table 1.

[0130] Example 57

[0131] The platinum loading was 8%, the la loading was 12%, and other conditions were the same as in Example 55. The carrier pore size distribution was 2.8-3.1 nm, the average pore size was 3.05 nm, and the specific surface area was 305 m². 2 / g. The results are shown in Table 1.

[0132] Example 58

[0133] The platinum loading was 3%, the Ce loading was 5%, and other conditions were the same as in Example 26. The pore size distribution of the support was 2.8-3.1 nm, with an average pore size of 3.1 nm and a specific surface area of ​​300 m². 2 / g. The results are shown in Table 1.

[0134] Example 59

[0135] The liquid hourly space velocity (LHSV) of glycerol is 1.2 h⁻¹. -1 Other conditions were the same as in Example 1. The results are shown in Table 1.

[0136] Example 60

[0137] The glycerol aqueous solution had a mass concentration of 10%, the reaction temperature was 190℃, and other conditions were the same as in Example 1. The results are shown in Table 1.

[0138] Example 61

[0139] The glycerol aqueous solution had a mass concentration of 20%, and other conditions were the same as in Example 60. The results are shown in Table 1.

[0140] Example 62

[0141] The glycerol aqueous solution had a mass concentration of 40%, the hydrogen reaction pressure was 8 MPa, and other conditions were the same as in Example 1. The results are shown in Table 1.

[0142] Example 63

[0143] The glycerol aqueous solution had a mass concentration of 30%, and other conditions were the same as in Example 62. The results are shown in Table 1.

[0144] Example 64

[0145] The hydrogen reaction pressure is 6 MPa, and the hydrogen gas space velocity is 150 h⁻¹. -1 The reaction temperature was 170℃, and other conditions were the same as in Example 1. The results are shown in Table 1.

[0146] Example 65

[0147] The glycerol aqueous solution had a mass concentration of 70%, the reaction temperature was 160℃, and other conditions were the same as in Example 1. The results are shown in Table 1.

[0148] Example 66

[0149] The glycerol aqueous solution has a mass concentration of 80%, the hydrogen reaction pressure is 10 MPa, and the hydrogen gas space velocity is 150 h⁻¹. -1 The reaction temperature was 220℃, and other conditions were the same as in Example 1. The results are shown in Table 1.

[0150] Example 67

[0151] The glycerol aqueous solution had a mass concentration of 90%, the hydrogen reaction pressure was 12 MPa, the reaction temperature was 240 °C, and other conditions were the same as in Example 1. The results are shown in Table 1.

[0152] Example 68

[0153] The glycerol aqueous solution had a mass concentration of 10%, the hydrogen reaction pressure was 0.1 MPa, and the hydrogen gas hourly space velocity was 100 h⁻¹. -1 Other conditions were the same as in Example 59. The results are shown in Table 1.

[0154] Example 69

[0155] The liquid hourly space velocity (LHSV) of glycerol is 0.8 h⁻¹. -1 Other conditions were the same as in Example 1. The results are shown in Table 1.

[0156] Example 70

[0157] The hydrogen reaction pressure was 5 MPa, the reaction temperature was 150 °C, and other conditions were the same as in Example 1. The results are shown in Table 1.

[0158] Example 71

[0159] The hydrogen reaction pressure was 4 MPa, the reaction temperature was 130 °C, and other conditions were the same as in Example 1. The results are shown in Table 1.

[0160] Comparative Example 1

[0161] To a 2.5 mol / L sodium aluminate aqueous solution (calculated as Al₂O₃, 20 g), a 2.0 mol / L sodium bicarbonate solution (CO₃) is added dropwise at a rate of 5 mL / min. 2- / AlO2 - With a molar ratio of 1.2 and a sodium bicarbonate volume of 235 mL, an aluminum hydroxide precursor precipitate was generated. The aluminum hydroxide precursor precipitate was aged at 50 °C for 4 hours. The aged aluminum hydroxide was washed with 2.0 mol / L ammonium carbonate by ion exchange, with a total ammonium carbonate volume of 15 L, until the conductivity of the washing liquid stabilized at 40 μS / cm within 20 minutes, resulting in an aluminum hydroxide filter cake. Guaranteed sesame powder was added to the aluminum hydroxide filter cake as an extrusion aid, with the guaranteed sesame powder mass being 2% based on the mass of the aluminum hydroxide filter cake. Deionized water was added to adjust the humidity, making the total water content of the mixture 45% by mass. After being thoroughly kneaded in a kneader, the mixture was aged for 2.5 hours and then extruded through a screw extruder at a pressure of 5 MPa, a die orifice diameter of 3.0 mm, and a cutting length of 4 mm to obtain cylindrical wet aluminum hydroxide strips. The strips were air-dried at room temperature for 24 hours, dried at 110 °C for 2 hours, and then transferred to a muffle furnace and calcined at 500 °C for 2 hours to obtain a cylindrical Al2O3 support. The carrier has a pore size distribution of 5.0-15.0 nm, an average pore size of 9.5 nm, and a specific surface area of ​​185 m². 2 / g. The cylindrical Al2O3 support is used to prepare a multi-active component catalyst. 20g of cylindrical Al2O3 support is used. The platinum precursor is chloroplatinic acid, with a platinum loading of 2% on the Al2O3 support. The auxiliary precursor is tungsten pentachloride, with a W loading of 7.5% on the Al2O3 support. The W precursor is dissolved in deionized water, with the water mass being 40% based on the cylindrical Al2O3 support. The cylindrical Al2O3 support is then added to the precursor. The Pt precursor was soaked in an aqueous solution for 24 hours, air-dried for 24 hours, and calcined in a muffle furnace at 500°C for 5 hours to obtain WO3 / Al2O3. The Pt precursor was dissolved in deionized water, with the water mass being 40% based on the cylindrical Al2O3 support. The WO3 / Al2O3 was added to the Pt precursor solution, soaked for 24 hours, air-dried for 24 hours, and calcined in a muffle furnace at 300°C for 1 hour to obtain the catalyst, denoted as 2Pt / 7.5WO3 / Al2O3.

[0162] The reaction was carried out in a fixed-bed reactor. The reactant was an aqueous glycerol solution with a mass concentration of 50% and a glycerol liquid hourly space velocity of 1.0 h⁻¹. -1 The hydrogen reaction pressure is 9 MPa, and the hydrogen gas space velocity is 200 h⁻¹.-1 The reaction temperature was 180℃. The results are shown in Table 1.

[0163] Comparative Example 2

[0164] A 2.5 mol / L sodium aluminate aqueous solution was mixed thoroughly with sodium stearate as a template agent. Template agent / AlO2 - The molar ratio was 0.001. The aluminate mass, converted to Al₂O₃, was 10 g. The reaction temperature was 50℃, and the mixture was stirred to form a micelle solution. A 0.05 mol / L sodium bicarbonate solution was added dropwise to the above micelle solution at a rate of 4 mL / min. CO₃²⁻ 2- / AlO2 - With a molar ratio of 0.05 and a sodium bicarbonate volume of 20 mL, an aluminum hydroxide precursor precipitate was generated. The aluminum hydroxide precursor precipitate was aged at 50 °C for 4 hours. The aged aluminum hydroxide was washed with 1.0 mol / L ammonium carbonate by ion exchange, with a total ammonium carbonate volume of 6 L, until the conductivity of the washing liquid stabilized at 40 μS / cm within 20 minutes, resulting in an aluminum hydroxide filter cake. Guaranteed sesame powder was added to the aluminum hydroxide filter cake as an extrusion aid, with the guaranteed sesame powder mass being 2% based on the mass of the aluminum hydroxide filter cake. Deionized water was added to adjust the humidity, making the total water content of the mixture 45% by mass. After being thoroughly kneaded in a kneader, the mixture was aged for 2.5 hours and then extruded through a screw extruder at a pressure of 5 MPa, a die orifice diameter of 3.0 mm, and a cutting length of 4 mm to obtain cylindrical wet aluminum hydroxide strips. The strips were air-dried at room temperature for 24 hours, dried at 110 °C for 2 hours, and then transferred to a muffle furnace and calcined at 500 °C for 2 hours to obtain a cylindrical Al2O3 support. The carrier has a pore size distribution of 8.0-20.0 nm, an average pore size of 10.5 nm, and a specific surface area of ​​195 m². 2 / g. The cylindrical Al2O3 support is used to prepare a multi-active component catalyst. 10g of cylindrical Al2O3 support is used. The platinum precursor is chloroplatinic acid, with a platinum loading of 2% on the Al2O3 support. The auxiliary precursor is tungsten pentachloride, with a W loading of 7.5% on the Al2O3 support. The W precursor is dissolved in deionized water, with the water mass being 40% based on the cylindrical Al2O3 support. The cylindrical Al2O3 support is then added to the precursor. The Pt precursor was soaked in an aqueous solution for 24 hours, air-dried for 24 hours, and calcined in a muffle furnace at 500°C for 5 hours to obtain WO3 / Al2O3. The Pt precursor was dissolved in deionized water, with the water mass being 40% based on the cylindrical Al2O3 support. The WO3 / Al2O3 was added to the Pt precursor solution, soaked for 24 hours, air-dried for 24 hours, and calcined in a muffle furnace at 300°C for 1 hour to obtain the catalyst, denoted as 2Pt / 7.5WO3 / Al2O3.

[0165] The reaction was carried out in a fixed-bed reactor. The reactant was an aqueous glycerol solution with a mass concentration of 50% and a glycerol liquid hourly space velocity of 1.0 h⁻¹.-1 The hydrogen reaction pressure is 9 MPa, and the hydrogen gas space velocity is 30 h⁻¹. -1 The reaction temperature was 180℃. The results are shown in Table 1.

[0166] Comparative Example 3

[0167] A 0.2 mol / L sodium aluminate aqueous solution was mixed thoroughly with sodium laurate as a template agent. Template agent / AlO2 - The molar ratio was 0.005. The aluminate mass, converted to Al₂O₃, was 20 g. The reaction temperature was 50℃, and the mixture was stirred to form a micelle solution. A 1.5 mol / L sodium bicarbonate solution was added dropwise to the above micelle solution at a rate of 3 mL / min. CO₃²⁻ 2- / AlO2 - With a molar ratio of 1.5 and a sodium bicarbonate volume of 390 mL, an aluminum hydroxide precursor precipitate was generated. The aluminum hydroxide precursor precipitate was aged at 50 °C for 4 hours. The aged aluminum hydroxide was washed with 1.0 mol / L ammonium carbonate by ion exchange, with a total ammonium carbonate volume of 6 L, until the conductivity of the washing liquid stabilized at 40 μS / cm within 20 minutes, resulting in an aluminum hydroxide filter cake. Guaranteed guar gum powder was added to the aluminum hydroxide filter cake as an extrusion aid, with the guar gum powder mass being 2% based on the mass of the aluminum hydroxide filter cake. Deionized water was added to adjust the humidity, making the total water content of the mixture 45% by mass. After being thoroughly kneaded in a kneader, the mixture was aged for 2.5 hours and then extruded through a screw extruder at a pressure of 5 MPa, a die orifice diameter of 3.0 mm, and a cutting length of 4 mm to obtain cylindrical wet aluminum hydroxide strips. The strips were air-dried at room temperature for 24 hours, dried at 110 °C for 2 hours, and then transferred to a muffle furnace and calcined at 500 °C for 2 hours to obtain a cylindrical Al2O3 support. The carrier has a pore size distribution of 4.0-12.0 nm, an average pore size of 7.8 nm, and a specific surface area of ​​220 m². 2 / g. The cylindrical Al2O3 support is used to prepare a multi-active component catalyst. 20g of cylindrical Al2O3 support is used. The platinum precursor is chloroplatinic acid, with a platinum loading of 2% on the Al2O3 support. The auxiliary precursor is tungsten pentachloride, with a W loading of 7.5% on the Al2O3 support. The W precursor is dissolved in deionized water, with the water mass being 40% based on the cylindrical Al2O3 support. The cylindrical Al2O3 support is then added to the precursor. The Pt precursor was soaked in an aqueous solution for 24 hours, air-dried for 24 hours, and calcined in a muffle furnace at 500°C for 5 hours to obtain WO3 / Al2O3. The Pt precursor was dissolved in deionized water, with the water mass being 40% based on the cylindrical Al2O3 support. The WO3 / Al2O3 was added to the Pt precursor solution, soaked for 24 hours, air-dried for 24 hours, and calcined in a muffle furnace at 300°C for 1 hour to obtain the catalyst, denoted as 2Pt / 7.5WO3 / Al2O3.

[0168] The reaction was carried out in a fixed-bed reactor. The reactant was an aqueous glycerol solution with a mass concentration of 50% and a glycerol liquid hourly space velocity of 1.0 h⁻¹. -1 The hydrogen reaction pressure is 9 MPa, and the hydrogen gas space velocity is 200 h⁻¹. -1 The reaction temperature was 180℃. The results are shown in Table 1.

[0169] Comparative Example 4

[0170] A 6 mol / L sodium aluminate aqueous solution was mixed thoroughly with sodium tridecanoate as a template agent. (Template agent / AlO2) - The molar ratio is 4, the mass of aluminate is converted to Al2O3, 20 g, the reaction temperature is 50℃, and the mixture is stirred to form a micelle solution; a 1.5 mol / L sodium bicarbonate solution is added dropwise to the above micelle solution at a rate of 2 mL / min, and CO3 is added. 2- / AlO2 - With a molar ratio of 1.3 and a sodium bicarbonate volume of 340 mL, an aluminum hydroxide precursor precipitate was generated. The aluminum hydroxide precursor precipitate was aged at 50 °C for 4 hours. The aged aluminum hydroxide was washed with 0.5 mol / L ammonium carbonate by ion exchange, with a total ammonium carbonate volume of 12 L, until the conductivity of the washing liquid stabilized at 40 μS / cm within 20 minutes, resulting in an aluminum hydroxide filter cake. Guaranteed guar gum powder was added to the aluminum hydroxide filter cake as an extrusion aid, with the guar gum powder mass being 2% based on the mass of the aluminum hydroxide filter cake. Deionized water was added to adjust the humidity, making the total water content of the mixture 45% by mass. After being thoroughly kneaded in a kneader, the mixture was aged for 2.5 hours and then extruded through a screw extruder at a pressure of 5 MPa, a die orifice diameter of 3.0 mm, and a cutting length of 4 mm to obtain cylindrical wet aluminum hydroxide strips. The strips were air-dried at room temperature for 24 hours, dried at 110 °C for 2 hours, and then transferred to a muffle furnace and calcined at 500 °C for 2 hours to obtain a cylindrical Al2O3 support. The carrier has a pore size distribution of 5.0-25.0 nm, an average pore size of 14.5 nm, and a specific surface area of ​​165 m². 2 / g. The cylindrical Al2O3 support is used to prepare a multi-active component catalyst. 20g of cylindrical Al2O3 support is used. The platinum precursor is chloroplatinic acid, with a platinum loading of 2% on the Al2O3 support. The auxiliary precursor is tungsten pentachloride, with a W loading of 7.5% on the Al2O3 support. The W precursor is dissolved in deionized water, with the water mass being 40% based on the cylindrical Al2O3 support. The cylindrical Al2O3 support is then added to the precursor. The Pt precursor was soaked in an aqueous solution for 24 hours, air-dried for 24 hours, and calcined in a muffle furnace at 500°C for 5 hours to obtain WO3 / Al2O3. The Pt precursor was dissolved in deionized water, with the water mass being 40% based on the cylindrical Al2O3 support. The WO3 / Al2O3 was added to the Pt precursor solution, soaked for 24 hours, air-dried for 24 hours, and calcined in a muffle furnace at 300°C for 1 hour to obtain the catalyst, denoted as 2Pt / 7.5WO3 / Al2O3.

[0171] The reaction was carried out in a fixed-bed reactor. The reactant was an aqueous glycerol solution with a mass concentration of 50% and a glycerol liquid hourly space velocity of 1.0 h⁻¹. -1 The hydrogen reaction pressure is 9 MPa, and the hydrogen gas space velocity is 20 h⁻¹. -1 The reaction temperature was 180℃. The results are shown in Table 1.

[0172] Comparative Example 5

[0173] A 1.0 mol / L sodium aluminate aqueous solution was mixed thoroughly with sodium tridecanoate as a template agent. Template agent / AlO2 - The molar ratio was 0.1. The aluminate mass, converted to Al₂O₃, was 10 g. The reaction temperature was 50℃, and the mixture was stirred to form a micelle solution. A 2.5 mol / L sodium bicarbonate solution was added dropwise to the above micelle solution at a rate of 10 mL / min. CO₃²⁻ 2- / AlO2 - With a molar ratio of 5 and a sodium bicarbonate volume of 392 mL, an aluminum hydroxide precursor precipitate was formed and aged at 50 °C for 4 hours. The aged aluminum hydroxide was then washed with 0.5 mol / L ammonium carbonate via ion exchange (total ammonium carbonate volume: 6 L) until the conductivity of the washings stabilized at 40 μS / cm within 20 minutes, yielding an aluminum hydroxide filter cake. Guaranteed sesame powder was added to the aluminum hydroxide filter cake as an extrusion aid (2% by weight of the aluminum hydroxide filter cake). Deionized water was added to adjust the humidity, bringing the total moisture content of the mixture to 45%. After thorough mixing in a kneader, the mixture was aged for 2.5 hours and then extruded through a screw extruder at a pressure of 5 MPa with a die orifice diameter of 3.0 mm and a cutting length of 4 mm to obtain cylindrical wet aluminum hydroxide strips. These strips were then air-dried at room temperature for 24 hours, dried at 110 °C for 2 hours, and then transferred to a muffle furnace and calcined at 500 °C for 2 hours to obtain a cylindrical Al2O3 support. The carrier has a pore size of 1.5-4.0 nm, an average pore size of 1.9 nm, and a specific surface area of ​​195 m². 2 / g. The cylindrical Al2O3 support is used to prepare a multi-active component catalyst. 10g of cylindrical Al2O3 support is used. The platinum precursor is chloroplatinic acid, with a platinum loading of 2% on the Al2O3 support. The auxiliary precursor is tungsten pentachloride, with a W loading of 7.5% on the Al2O3 support. The W precursor is dissolved in deionized water, with the water mass being 40% based on the cylindrical Al2O3 support. The cylindrical Al2O3 support is then added to the precursor. The Pt precursor was soaked in an aqueous solution for 24 hours, air-dried for 24 hours, and calcined in a muffle furnace at 500°C for 5 hours to obtain WO3 / Al2O3. The Pt precursor was dissolved in deionized water, with the water mass being 40% based on the cylindrical Al2O3 support. The WO3 / Al2O3 was added to the Pt precursor solution, soaked for 24 hours, air-dried for 24 hours, and calcined in a muffle furnace at 300°C for 1 hour to obtain the catalyst, denoted as 2Pt / 7.5WO3 / Al2O3.

[0174] The reaction was carried out in a fixed-bed reactor. The reactant was an aqueous glycerol solution with a mass concentration of 50% and a glycerol liquid hourly space velocity of 1.0 h⁻¹. -1 The hydrogen reaction pressure is 9 MPa, and the hydrogen gas space velocity is 45 h⁻¹. -1 The reaction temperature was 180℃. The results are shown in Table 1.

[0175] Comparative Example 6

[0176] Sodium undecanoate was replaced with an equimolar amount of sodium valerate, and other conditions were the same as in Example 1. The carrier pore size was 1.5-20 nm, the average pore size was 9.0 nm, and the specific surface area was 195 m². 2 / g. The results are shown in Table 1.

[0177] Comparative Example 7

[0178] Sodium stearate was replaced with an equimolar amount of sodium formate, and other conditions were the same as in Example 2. The carrier pore size was 5-18 nm, the average pore size was 10.5 nm, and the specific surface area was 175 m². 2 / g. The results are shown in Table 1.

[0179] Comparative Example 8

[0180] Guisena powder was added to the aluminum hydroxide filter cake as an extrusion aid, with the guisena powder accounting for 10% of the weight of the aluminum hydroxide filter cake. Other conditions were the same as in Example 1. The results are shown in Table 1.

[0181] Comparative Example 9

[0182] The aluminum hydroxide precursor precipitate was aged at 120°C for 6 hours. Other conditions were the same as in Example 1. The results are shown in Table 1.

[0183] Comparative Example 10

[0184] A 2.5 mol / L sodium aluminate aqueous solution was mixed thoroughly with sodium acetate as a template agent. Template agent / AlO2 - The molar ratio was 0.30. The aluminate mass, converted to Al₂O₃, was 20 g. The reaction temperature was 50°C. 2.5 L of 0.1 mol / L hydrochloric acid solution was added dropwise until pH = 4, and the mixture was stirred to form a micelle solution. Other conditions were the same as in Example 1. The carrier pore size was 0.05-1 nm, with an average pore size of 0.6 nm and a specific surface area of ​​150 m². 2 / g. Other conditions were the same as in Example 1. The results are shown in Table 1.

[0185] Comparative Example 11

[0186] Cylindrical aluminum hydroxide wet strips were air-dried at room temperature for 24 hours, then dried at 150°C for 1 hour, and subsequently transferred to a muffle furnace for calcination at 200°C for 2 hours. Other conditions were the same as in Example 1. The results are shown in Table 1.

[0187] Comparative Example 12

[0188] The precursor tungsten pentachloride was replaced with magnesium nitrate, and the Mg loading was 18%. Other conditions were the same as in Example 1. The results are shown in Table 1.

[0189] Comparative Example 13

[0190] The Pt loading was 15%. Other conditions were the same as in Example 1. The results are shown in Table 1.

[0191] Comparative Example 14

[0192] The aluminum hydroxide precursor precipitate was aged at 20°C for 12 hours. Other conditions were the same as in Comparative Example 9. The results are shown in Table 1.

[0193] Comparative Example 15

[0194] Add 15% guar gum powder. Other conditions were the same as in Comparative Example 8. The results are shown in Table 1.

[0195] Comparative Example 16

[0196] Cylindrical aluminum hydroxide wet strips were air-dried at room temperature for 48 hours, then dried at 60°C for 1 hour, and subsequently transferred to a muffle furnace and calcined at 300°C for 1 hour. Other conditions were the same as in Comparative Example 11. The results are shown in Table 1.

[0197] Comparative Example 17

[0198] WO3 / Al2O3 was added to the Pt precursor solution, impregnated for 5 hours, air-dried for 5 hours, and calcined in a muffle furnace at 800℃ for 5 hours. Other conditions were the same as in Comparative Example 1. The results are shown in Table 1.

[0199] Comparative Example 18

[0200] The glycerol aqueous solution had a mass concentration of 5%, and the reaction temperature was 60℃. Other conditions were the same as in Comparative Example 1. The results are shown in Table 1.

[0201] Comparative Example 19

[0202] A 2.5 mol / L sodium aluminate aqueous solution was mixed thoroughly with sodium stearate as a template agent. Template agent / AlO2 - The molar ratio was 5, the mass of aluminate (converted to Al2O3) was 10 g, and the reaction temperature was 100℃. Other conditions were the same as in Comparative Example 2. The results are shown in Table 1.

[0203] Comparative Example 20

[0204] CO3 2- / AlO2 - The molar ratio was 0.05. Other conditions were the same as in Comparative Example 2. The results are shown in Table 1.

[0205] Comparative Example 21

[0206] The screw extruder was used to cut 1 mm. Other conditions were the same as in Comparative Example 1. The results are shown in Table 1.

[0207] Comparative Example 22

[0208] Tungsten pentachloride was replaced with nickel nitrate. Other conditions were the same as in Comparative Example 1. The results are shown in Table 1.

[0209] Comparative Example 23

[0210] Cylindrical wet aluminum hydroxide strips were directly calcined in a muffle furnace at 200°C for 1 hour. Other conditions were the same as in Comparative Example 2. The results are shown in Table 1.

[0211] Comparative Example 24

[0212] The platinum loading was 0.5%, and the Fe loading was 20%. Other conditions were the same as in Example 22. The results are shown in Table 1.

[0213] Comparative Example 25

[0214] Fe₂O₃ / Al₂O₃ was added to the Pt precursor solution, impregnated for 2 hours, air-dried for 4 hours, and calcined in a muffle furnace at 120°C for 5 hours. Other conditions were the same as in Comparative Example 24. The results are shown in Table 1.

[0215] Comparative Example 26

[0216] The platinum precursor chloroplatinic acid was replaced with copper nitrate, and the Cu loading was 0.05%. Other conditions were the same as in Example 1. The results are shown in Table 1.

[0217] Comparative Example 27

[0218] The Cu loading was 15%. Other conditions were the same as in Comparative Example 26. The results are shown in Table 1.

[0219] Comparative Example 28

[0220] The precursor lanthanum nitrate hexahydrate was replaced with copper nitrate. Other conditions were the same as in Example 25. The results are shown in Table 1.

[0221] Comparative Example 29

[0222] Sodium aluminate was replaced with an equimolar amount of strontium aluminate. Other conditions were the same as in Example 1. The results are shown in Table 1.

[0223] Comparative Example 30

[0224] Sodium aluminate was replaced with an equimolar amount of cobalt aluminate. Other conditions were the same as in Example 1. The results are shown in Table 1.

[0225] Comparative Example 31

[0226] Sodium tridecanoate was replaced with an equimolar amount of sodium hexanoate. Other conditions were the same as in Example 4. The results are shown in Table 1.

[0227] Comparative Example 32

[0228] Sodium tridecanoate was replaced with an equimolar amount of sodium heptate. Other conditions were the same as in Example 5. The results are shown in Table 1.

[0229] Comparative Example 33

[0230] The hydrogen gas was replaced with nitrogen gas, and the reaction pressure was 5 MPa. Other conditions were the same as in Example 1. The results are shown in Table 1.

[0231] Comparative Example 34

[0232] The reaction pressure was 9 MPa. Other conditions were the same as in Comparative Example 33. The results are shown in Table 1.

[0233] Comparative Example 35

[0234] The hydrogen gas was replaced with air, and the reaction pressure was 1 MPa. Other conditions were the same as in Example 1. The results are shown in Table 1.

[0235] Comparative Example 36

[0236] The reaction pressure was 7 MPa. Other conditions were the same as those in Comparative Example 35. The results are shown in Table 1.

[0237] Comparative Example 37

[0238] The glycerol aqueous solution had a mass concentration of 95%, and the reaction temperature was 80°C. Other conditions were the same as in Example 1. The results are shown in Table 1.

[0239] Comparative Example 38

[0240] The reaction temperature was 30℃. Other conditions were the same as in Comparative Example 37. The results are shown in Table 1.

[0241] Comparative Example 39

[0242] The glycerol aqueous solution had a mass concentration of 3%, and the reaction temperature was 60°C. Other conditions were the same as in Example 57. The results are shown in Table 1.

[0243] Comparative Example 40

[0244] The reaction temperature was 30℃. Other conditions were the same as those for Comparative Example 58. The results are shown in Table 1.

[0245] Comparative Example 41

[0246] The cylindrical alumina support was replaced with an equal mass of rutile titanium dioxide. The support had a pore size distribution of 0.8-1.2 nm, an average pore size of 1.02 nm, and a specific surface area of ​​25 m². 2 / g.

[0247] Other conditions were the same as in Example 1. The results are shown in Table 1.

[0248] Comparative Example 42

[0249] The cylindrical alumina support was replaced with an equal mass of SBA-15. The support had a pore size distribution of 5.5-6.5 nm, an average pore size of 6.32 nm, and a specific surface area of ​​915 m². 2 / g. Other conditions were the same as in Example 1. The results are shown in Table 1.

[0250] Comparative Example 43

[0251] The cylindrical alumina support was replaced with an equal mass of MCM-41. The support had a pore size distribution of 7.0-8.2 nm, an average pore size of 7.65 nm, and a specific surface area of ​​915 m². 2 / g. Other conditions were the same as in Example 1. The results are shown in Table 1.

[0252] Table 1. A multi-active component catalyst supported on cylindrical alumina for the preparation of 1,3-propanediol via glycerolysis.

[0253]

[0254]

[0255]

[0256]

[0257]

[0258]

[0259]

[0260] The products include small amounts of propane, methanol, ethanol, ethylene glycol, etc., and the total mass is conserved.

[0261] Summarize

[0262] This invention uses sodium alkyl carboxylate with a carbon chain length within a specific range as a micelle template agent to regulate the template agent / AlO2 ratio. - molar ratio, CO3 2- / AlO2 - Molar ratio, using micellar template-guided precipitation, successfully prepared pores with a pore size distribution of 1-12 nm, an average pore size of 2-4 nm, and a specific surface area of ​​150-400 m². 2 / g cylindrical alumina support. This support is further loaded with metal Pt and specific auxiliary metals, exhibiting high glycerol conversion and 1,3-propanediol yield in the hydrogenolysis of glycerol to 1,3-propanediol.

[0263] The above descriptions are all preferred embodiments of the present invention and are not intended to limit the present invention in any form or substance. It should be noted that those skilled in the art can make some modifications, alterations, and variations to the disclosed technical content without departing from the spirit and scope of the present invention; these are all equivalent embodiments of the present invention. Furthermore, any equivalent modifications, alterations, and variations made to the above embodiments based on the essential technology of the present invention still fall within the scope of the present invention's technical solution.

Claims

1. A method for preparing 1,3-propanediol by hydrogenolysis of glycerol, characterized in that: The catalyst used is a supported catalyst, with shaped cylindrical alumina (Al2O3) as the support. The active component is platinum metal (Pt) and its auxiliary agent. The auxiliary agent is designated as A and contains one or more of W, Mo, Fe, Al, La, Ce, Sn, Zr, Zn, Mn, Nd, and Ta. The platinum metal loading is 0.1%-10% based on the mass of Al2O3, and the metal loading of auxiliary agent A is 0.01%-15% based on the mass of Al2O3. The resulting catalyst is labeled Pt / AOx / Al2O3. The cylindrical Al2O3 support was prepared by a micelle template-guided precipitation method. Specific preparation process: 1) Mix a 0.5-3.0 mol / L aluminate solution with sodium alkylcarboxylate as a template agent until homogeneous, and stir at 25-85℃ to fully dissolve the template agent and form a micelle solution. The aluminate content, calculated as Al2O3, is 5-50g. 2) Add a carbonate solution with a concentration of 0.5-2.5 mol / L and a volume of 35-500 mL to the above micelle solution at a rate of 1-5 mL / min. Under the guidance of the micelle template, an aluminum hydroxide precursor precipitate is generated. The aluminum hydroxide precursor precipitate is aged at 25-85℃ for 2-12 hours. The aged aluminum hydroxide is washed with an ammonium salt solution of 0.1-2.0 mol / L and 4-30 L in volume by ion exchange until the conductivity of the washing solution stabilizes at 35-45 μS / cm within 5-20 minutes, resulting in an aluminum hydroxide filter cake. Guaranteed sesame powder is added to the aluminum hydroxide filter cake as an extrusion aid, with the mass of sesame powder being 1-3% of the mass of the aluminum hydroxide filter cake. Deionized water is added to adjust the humidity so that the total moisture content of the mixture is 30-50 wt%. After being thoroughly kneaded in a kneader, the mixture is aged for 0.5-5 hours and then extruded through a screw extruder with a die orifice diameter of 1-5 mm and a cutting length of 4-8 mm to obtain cylindrical wet aluminum hydroxide strips. 3) Dry the cylindrical aluminum hydroxide wet strips in the shade at room temperature for 8-36 hours, dry them at 80-120℃ for 2-8 hours, and then transfer them to a muffle furnace and calcine them at 400-800℃ for 2-5 hours to obtain a cylindrical Al2O3 support.

2. The method according to claim 1, characterized in that: Cylindrical Al₂O₃ supports were obtained, with pore sizes ranging from 1 to 12 nm, an average pore size of 2 to 4 nm, and a specific surface area of ​​150 to 400 m². 2 / g; AOx represents the metal oxide corresponding to additive A, and x ranges from 1 to 6.

3. The method according to claim 1, characterized in that: The selected sodium alkyl carboxylate salts have a carbon chain length of 10-18, including sodium decanoate, sodium undecanoate, sodium laurate, sodium tridecanoate, sodium myristate, sodium stearate, sodium pentadecanoate, sodium palmitate, sodium isotriadecanoate, sodium 2-hexyldecanoate, and sodium isostearate, or a combination of two or more of these. The aluminate is represented by the aluminate ion (AlO2). - The molar ratio of sodium alkylcarboxylate salt to aluminate used as a template agent (template agent / AlO2) is calculated. - ): 0.01-0.

50.

4. The carrier according to claim 1, characterized in that: The selected aluminate solution includes one or a combination of two or more of sodium aluminate solution, potassium aluminate solution, and ammonium aluminate solution, wherein the aluminate is represented by aluminate ions (AlO2). - )count.

5. The method according to claim 1, characterized in that: The selected carbonate solution includes one or more of sodium bicarbonate solution, ammonium carbonate solution, and ammonium bicarbonate solution, with aluminate (AlO2) as the ion. - ) calculated, the molar ratio of added carbonate to aluminate (CO3) 2- / AlO2 - ): 1.0-1.

5.

6. The method according to claim 1, characterized in that: The ammonium salt solution used for washing after aging includes one or more of the following: ammonium methylformate, ammonium carbonate, ammonium bicarbonate, and ammonium acetate. The concentration of the ammonium salt solution is 0.1-2.0 mol / L.

7. The method according to claim 1, characterized in that: A wet impregnation method is used to simultaneously or sequentially load platinum precursors and auxiliary precursors onto a cylindrical Al2O3 support. The platinum precursor is one or more of chloroplatinic acid, platinum nitrate, platinum acetate, and platinum acetylacetonate. The auxiliary precursor A is one or more of chlorides, nitrates, phosphates, acetylacetonates, and acetates of W, Mo, Fe, Al, La, Ce, Sn, Zr, Zn, Mn, Nd, and Ta. The impregnation is carried out for 20-50 hours, followed by air drying at room temperature for 20-50 hours. The catalyst is then calcined in a muffle furnace at a high temperature of 200-400℃ for 1-3 hours to obtain the Pt / AOx / Al2O3 catalyst.

8. The method according to claim 1, characterized in that: A fixed-bed reactor was used, with the reactant being an aqueous glycerol solution at a mass concentration of 10-90% and a glycerol liquid hourly space velocity of 0.06-1.5 h⁻¹. -1 The hydrogen reaction pressure is 0.1-12 MPa, and the hydrogen gas space velocity is 50-200 h⁻¹. -1 The reaction temperature is between 100-250℃.

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