Synthesis method of 1, 6-hexanediol

Abstract

The invention relates to the technical field of organic synthesis, in particular to a synthesis method of 1, 6-hexanediol. The synthesis method of 1, 6-hexanediol provided by the invention comprises the following steps: mixing 5-hydroxymethylfurfural, a catalyst and a solvent, and introducing hydrogen into the mixed solution; and stirring the mixed solution at a first temperature for a first time to prepare the 1, 6-hexanediol, wherein the first temperature ranges from 80 DEG C to 200 DEG C, and the first time ranges from 1 h to 24 h. According to the synthesis method, renewable raw materials with rich sources are adopted, the preparation process is simple, the selectivity is high, the product purity is high, and compared with an existing synthesis method, the synthesis method has the advantages of being more efficient, more environmentally friendly and lower in cost.

Description

Technical Field

[0001] This application relates to the field of organic chemistry, and in particular to a method for synthesizing 1,6-hexanediol. Background Technology

[0002] 1,6-Hexanediol has the molecular formula C6H2O. 14 O2 is a six-carbon linear aliphatic diol containing two terminal primary hydroxyl groups. It appears as a white crystalline solid or a colorless, transparent liquid, is hygroscopic, and is soluble in polar solvents such as water, ethanol, and acetone. 1,6-Hexanediol is an important chemical intermediate and monomer, widely used in polyurethanes (e.g., as a raw material for synthesizing polyester polyols), polyester resins, coatings, adhesives, plasticizers, pharmaceuticals, and fragrances [Topics in Catalysis, 2012, Volume 55, Pages 612-619, Applied Catalysis A:General, 2008, Volume 351, Pages 259-266]. Its excellent weather resistance, chemical resistance, flexibility, and good compatibility with various resins make it an important material in high-performance materials. Polyester polyols and polycarbonate diols derived from it can be further designed as biodegradable materials, thereby indirectly promoting green applications. With the continuous expansion of downstream application markets, especially the increasing demand for environmentally friendly coatings and high-performance engineering plastics, the demand for 1,6-hexanediol continues to rise. Therefore, researching the preparation method of 1,6-hexanediol has great potential economic value.

[0003] Currently, there are two main methods for preparing 1,6-hexanediol: the first is the traditional petrochemical method, which uses petroleum-based raw materials (such as dimethyl adipate) to convert into 1,6-hexanediol; the second is the selective hydrogenolysis of lignocellulose and its derivatives (such as cellulose and sorbitol) to 1,6-hexanediol. The traditional petrochemical method generally suffers from problems such as non-renewable raw materials, high energy consumption, and unsatisfactory selectivity. The selective hydrogenolysis of lignocellulose and its derivatives faces challenges such as low yield, cumbersome steps, and low product purity.

[0004] Therefore, it is necessary to develop a more efficient green synthesis method for 1,6-hexanediol. Summary of the Invention

[0005] Based on this, the present invention develops a one-step synthesis method for 1,6-hexanediol using renewable biomass 5-hydroxymethylfurfural (5-HMF) as a raw material. This synthesis method utilizes abundant renewable raw materials, has a simple preparation process, high selectivity, and high product purity. Compared with existing synthesis methods, it has the advantages of being more efficient, more environmentally friendly, and lower in cost.

[0006] The method for synthesizing 1,6-hexanediol provided by this invention includes the following steps:

[0007] 5-hydroxymethylfurfural, catalyst and solvent are mixed, and hydrogen gas is introduced into the mixture;

[0008] The mixture is stirred at a first temperature for a first time to obtain the 1,6-hexanediol.

[0009] The first temperature is 80℃-200℃, and the first time is 1h-24h.

[0010] In some embodiments, the catalyst includes a support and a metal supported on the support;

[0011] The carrier includes at least one of molecular sieves and oxides.

[0012] Furthermore, in the catalyst, the metal includes at least one selected from Ni, Cu, Co, Mo, Zn, Ce, La, Fe, Pd, Pt, Ru, Re, and Ir;

[0013] The molecular sieve includes at least one of HZSM-5, SAPO-11, HY, La-Y, Hβ, Si-MCM-41, Al-MCM-41, Ti-MCM-41, SAPO-34, USY, MCM-22, MCM-48, ReY, KIT-6, MCM-48, Al-SBA-15, and Al-SBA-16;

[0014] The oxide includes TiO. x -ZrO y ZrO x -SiO2, SiO2-Al2O3, TiO x -SiO2, MoO x -SiO2, CoO x -SiO2, SiO2, Al2O3, CeMnO x and CeO x At least one of -SiO2,

[0015] The metal loading is 1wt%-20wt% of the carrier.

[0016] Further, the catalyst comprises 7wt% Pd / Al-MCM-41, 3wt% Co / TiO2-ZrO2, 5wt% Ni / SAPO-11, 7wt% Ni / HZSM-5, 3wt% Pt / ZrO2-SiO2, 7wt% Pd / HZSM-5, 5wt% Ru / Al2O3-SiO2, 9wt% Mo / HZSM-5, 7wt% Pd / HY, 7wt% Pd / La-Y, 7wt% Pd / Hβ, 7wt% Pd / Si-MCM-41, 7wt% Pt / Al-MCM-41, 3wt% Ni, and 5wt% Mo / TiO2. x -SiO2, 7wt%Pt3wt%Zn / SiO2-Al2O3, 3wt%Rh5wt%Ni / Ti-MCM-41, 9wt%Re3wt%Cu / Al-MCM-41, 7wt%Cu3wt%Co / SAPO-11, 1wt%Pd5wt%Cu / SiO 2、 7wt%Pd3wt%Co / CeMnO x , 1wt%Pt3wt%Co / Al-SBA-15, 7wt%Fe1wt%Ir / Al-SBA-16, 7wt%Pd7wt%Mo / HZSM-5, 5wt%Pd7wt%Ni / SAPO-34, 3wt%Ir3wt%Re / USY、5wt%Ni5wt%Cu / MCM-22、3wt%Ru1wt%Fe / ReY、7wt%Pd5wt%Co / Na-ZSM-5、5wt%Ce3wt%La / MCM-48、7wt%Ni3wt%La / CeO x -SiO2, 7wt%Pd7wt%Mo / KIT-6, 5wt%Pd7wt%Mo / Al2O3, 3wt%Rh5wt%Ni / MoO x -SiO2 and 7wt%Pt / CoO x At least one of -SiO2.

[0017] In some embodiments, the solvent includes at least one selected from water, methanol, ethanol, ethyl acetate, and dichloromethane.

[0018] In some embodiments, the weight ratio of 5-hydroxymethylfurfural to the catalyst is 1:(0.2-2).

[0019] In some embodiments, the ratio of the total weight of the 5-hydroxymethylfurfural and the catalyst to the amount of the solvent is 0.38-0.40 g: 9 mL.

[0020] Furthermore, the catalyst is 7wt% Pd / Al-MCM-41.

[0021] Furthermore, the first temperature is 80℃-200℃, and the first time is 1h-24h.

[0022] Furthermore, the first temperature is 160°C, and the first time is 4 hours.

[0023] This invention utilizes 5-HMF as a starting material and, in the presence of a catalyst at a suitable temperature, achieves the efficient and selective synthesis of 1,6-hexanediol through a one-step catalytic hydrogenation. The synthesis method of this invention combines the advantages of simple operation, mild conditions, and economical cost, while also significantly improving the conversion rate of the starting material and the yield of 1,6-hexanediol. Attached Figure Description

[0024] To more clearly illustrate the technical solutions in the specific embodiments of this application or the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of this application. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0025] Figure 1 The chemical structure of 1,6-hexanediol is given.

[0026] Figure 2 This is the reaction mechanism for the catalytic hydrogenation of 5-HMF to prepare 1,6-hexanediol in one embodiment of the present invention.

[0027] Figure 3 This is the gas phase detection result of Example 1 of the present invention. Detailed Implementation

[0028] The present application is further described below with reference to embodiments and examples. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the application. Furthermore, it should be understood that after reading the teachings of this application, those skilled in the art can make various alterations or modifications to this application, and these equivalent forms also fall within the protection scope of the appended claims.

[0029] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.

[0030] In this paper, the catalyst is expressed as A / B, where A is a metal, including at least one of Ni, Cu, Co, Mo, Zn, Ce, La, Fe, Pd, Pt, Ru, Re, and Ir; B is a support (i.e., molecular sieve), including at least one of HZSM-5, SAPO-11, HY, La-Y, Hβ, Si-MCM-41, Al-MCM-41, Ti-MCM-41, SAPO-34, USY, MCM-22, MCM-48, ReY, KIT-6, MCM-48, Al-SBA-15, and Al-SBA-16; or an oxide including TiO2. x -ZrO y ZrO x -SiO2, SiO2-Al2O3, TiO x -SiO2, MoO x -SiO2, CoO x -SiO2, SiO2, Al2O3, CeMnO x and CeO x At least one of -SiO2; the metal loading is 1wt%-20wt% of the metal in the carrier.

[0031] The catalyst used in this application was prepared in-house using an equal-volume impregnation method. Before preparation, the support needed to be activated in a muffle furnace at a specific temperature. Taking 7wt% Pd / Al-MCM-41 as an example, the specific preparation process is as follows: 0.08g of potassium chloride palladiumate (K2PdCl4) was added to 0.70 mL of deionized water, and after complete dissolution of the metal by sonication, it was added dropwise to 0.35g of Al-MCM-41 molecular sieve support. After stirring at room temperature for 10 min, the sample was allowed to stand at room temperature overnight for sufficient impregnation. The resulting sample was dried at 110℃ for 12 h, then calcined in a muffle furnace at 550℃ for 3 h, and reduced in a tube furnace at 350℃ for 2 h. After completing the above preparation steps, the resulting sample was stored in an inert gas atmosphere. The preparation methods for other catalysts are similar, with strict calculation and control of the required metal loading while ensuring a constant support weight.

[0032] One or more embodiments of this application provide a method for synthesizing 1,6-hexanediol, comprising the following steps:

[0033] 5-hydroxymethylfurfural, catalyst and solvent are mixed, and hydrogen gas is introduced into the mixture;

[0034] The mixture is stirred at a first temperature for a first time to obtain the 1,6-hexanediol.

[0035] The first temperature is 80℃-200℃, and the first time is 1h-24h.

[0036] In some embodiments, the catalyst includes a support and a metal supported on the support;

[0037] The carrier includes at least one of molecular sieves and oxides.

[0038] Furthermore, in the catalyst, the metal includes at least one selected from Ni, Cu, Co, Mo, Zn, Ce, La, Fe, Pd, Pt, Ru, Re, and Ir;

[0039] The molecular sieve includes at least one of HZSM-5, SAPO-11, HY, La-Y, Hβ, Si-MCM-41, Al-MCM-41, Ti-MCM-41, SAPO-34, USY, MCM-22, MCM-48, ReY, KIT-6, MCM-48, Al-SBA-15, and Al-SBA-16;

[0040] The oxide includes TiO. x -ZrO y ZrO x -SiO2, SiO2-Al2O3, TiO x -SiO2, MoO x -SiO2, CoO x -SiO2, SiO2, Al2O3, CeMnO x and CeO x At least one of -SiO2;

[0041] The metal loading is 1wt%-20wt% of the carrier.

[0042] Further, the catalyst comprises 7wt% Pd / Al-MCM-41, 3wt% Co / TiO2-ZrO2, 5wt% Ni / SAPO-11, 7wt% Ni / HZSM-5, 3wt% Pt / ZrO2-SiO2, 7wt% Pd / HZSM-5, 5wt% Ru / Al2O3-SiO2, 9wt% Mo / HZSM-5, 7wt% Pd / HY, 7wt% Pd / La-Y, 7wt% Pd / Hβ, 7wt% Pd / Si-MCM-41, 7wt% Pt / Al-MCM-41, 3wt% Ni, and 5wt% Mo / TiO2. x -SiO2, 7wt%Pt3wt%Zn / SiO2-Al2O3, 3wt%Rh5wt%Ni / Ti-MCM-41, 9wt%Re3wt%Cu / Al-MCM-41, 7wt%Cu3wt%Co / SAPO-11, 1wt%Pd5wt%Cu / SiO 2、7wt%Pd3wt%Co / CeMnO x , 1wt%Pt3wt%Co / Al-SBA-15, 7wt%Fe1wt%Ir / Al-SBA-16, 7wt%Pd7wt%Mo / HZSM-5, 5wt%Pd7wt%Ni / SAPO-34, 3wt%Ir3wt%Re / USY、5wt%Ni5wt%Cu / MCM-22、3wt%Ru1wt%Fe / ReY、7wt%Pd5wt%Co / Na-ZSM-5、5wt%Ce3wt%La / MCM-48、7wt%Ni3wt%La / CeO x -SiO2, 7wt%Pd7wt%Mo / KIT-6, 5wt%Pd7wt%Mo / Al2O3, 3wt%Rh5wt%Ni / MoO x -SiO2 and 7wt%Pt / CoO x At least one of -SiO2.

[0043] In some embodiments, the solvent includes at least one selected from water, methanol, ethanol, ethyl acetate, and dichloromethane.

[0044] In some embodiments, the weight ratio of 5-hydroxymethylfurfural to the catalyst is 1:(0.2-2). Examples include 1:0.2, 1:0.5, 1:0.8, 1:1, 1:1.2, 1:1.5, 1:1.8, 1:2, etc.

[0045] In some embodiments, the ratio of the total weight of the 5-hydroxymethylfurfural and the catalyst to the amount of the solvent is 0.38-0.4 g:9 mL. Examples include 0.38 g:9 mL, 0.39 g:9 mL, and 0.4 g:9 mL.

[0046] Furthermore, the catalyst is 7wt% Pd / Al-MCM-41.

[0047] Furthermore, the first temperature is 80℃-200℃, for example 80℃, 100℃, 120℃, 150℃, 180℃, 200℃, etc., and the first time is 1h-24h, for example 1h, 2h, 5h, 8h, 12h, 18h, 20h, 24h, etc.

[0048] Furthermore, the first temperature is 160°C, and the first time is 4 hours.

[0049] The following are some specific embodiments. The raw materials and reagents involved in the following specific embodiments can be obtained commercially, or can be prepared by those skilled in the art using known methods.

[0050] Example 1

[0051] This embodiment is a synthesis embodiment of the present invention, providing a specific method for preparing 1,6-hexanediol, including the following steps: 0.19 g of 5-HMF, 9 mL of solvent water, and 0.19 g of catalyst 7% Pd / Al-MCM-41 are placed in a reaction vessel. N2 is repeatedly introduced to replace the air in the vessel, followed by the introduction of 3 MPa of H2. Stirring is then started to homogenize the reactants. The temperature of the reaction solution is controlled at 160°C, and the reaction is kept at this temperature for 4 hours. After the reaction is complete, the reaction vessel is cooled to room temperature to obtain a reaction solution containing 1,6-hexanediol.

[0052] Example 2

[0053] This embodiment is a synthesis embodiment of the present invention, providing a specific method for preparing 1,6-hexanediol, including the following steps: 0.19 g of 5-HMF, 9 mL of methanol solvent, and 0.19 g of 3% Co / TiO2-ZrO2 catalyst are placed in a reaction vessel. N2 is repeatedly introduced to replace the air in the vessel, followed by the introduction of 3 MPa of H2. Stirring is then started to homogenize the reactants. The temperature of the reaction solution is controlled at 130°C, and the reaction is kept at this temperature for 15 hours. After the reaction is complete, the reaction vessel is cooled to room temperature to obtain a reaction solution containing 1,6-hexanediol.

[0054] Example 3

[0055] This embodiment is a synthesis embodiment of the present invention, providing a specific method for preparing 1,6-hexanediol, including the following steps: 0.19 g of 5-HMF, 9 mL of solvent water, and 0.19 g of catalyst 5% Ni / HZSM-5 are placed in a reaction vessel. N2 is repeatedly introduced to replace the air in the vessel, followed by the introduction of 6 MPa of H2. Stirring is started to make the reactants homogeneous. The temperature of the reaction solution is controlled at 120°C, and the reaction is kept at this temperature for 12 hours. After the reaction is completed, the reaction vessel is cooled to room temperature to obtain a reaction solution containing 1,6-hexanediol.

[0056] Example 4

[0057] This embodiment is a synthesis embodiment of the present invention, providing a specific method for preparing 1,6-hexanediol, comprising the following steps: 0.19 g of 5-HMF, 9 mL of solvent water, and 0.19 g of catalyst 5%Pd2%Ni / SAPO-11 are placed in a reaction vessel. N2 is repeatedly introduced to replace the air inside the vessel, followed by the introduction of 5 MPa of H2. Stirring is then started to homogenize the reactants. The temperature of the reaction solution is controlled at 80°C, and the reaction is kept at this temperature for 15 hours. After the reaction is complete, the reaction vessel is cooled to room temperature to obtain a reaction solution containing 1,6-hexanediol.

[0058] Example 5

[0059] This embodiment is a synthesis embodiment of the present invention, providing a specific method for preparing 1,6-hexanediol, including the following steps: 0.19 g of 5-HMF, 9 mL of solvent ethanol, and 0.19 g of catalyst 3% Pt / ZrO2. X -SiO2 was placed in a reactor, and N2 was repeatedly introduced to replace the air in the reactor. Then, H2 at 4 MPa was introduced, and the reactants were stirred until homogeneous. The temperature of the reaction solution was controlled at 100℃, and the reaction was kept at this temperature for 8 hours. After the reaction was completed, the reactor was cooled to room temperature to obtain a reaction solution containing 1,6-hexanediol.

[0060] Example 6

[0061] This embodiment is a synthetic embodiment of the present invention, providing a specific method for preparing 1,6-hexanediol, comprising the following steps: 0.19 g of 5-HMF, 9 mL of ethyl acetate solvent, and 0.19 g of 7% Pd / HZSM-5 catalyst are placed in a reaction vessel. N2 is repeatedly introduced to replace the air in the vessel, followed by the introduction of 3 MPa of H2. Stirring is then started to homogenize the reactants. The temperature of the reaction solution is controlled at 160°C, and the reaction is kept at this temperature for 8 hours. After the reaction is complete, the reaction vessel is cooled to room temperature to obtain a reaction solution containing 1,6-hexanediol.

[0062] Example 7

[0063] This embodiment is a synthesis embodiment of the present invention, providing a specific method for preparing 1,6-hexanediol, comprising the following steps: 0.19 g of 5-HMF, 9 mL of solvent water, and 0.19 g of catalyst 5%Ru / Al2O3-SiO2 are placed in a reaction vessel. N2 is repeatedly introduced to replace the air inside the vessel, followed by the introduction of 3 MPa of H2. Stirring is then started to homogenize the reactants. The temperature of the reaction solution is controlled at 140°C, and the reaction is kept at this temperature for 10 hours. After the reaction is complete, the reaction vessel is cooled to room temperature to obtain a reaction solution containing 1,6-hexanediol.

[0064] Example 8

[0065] This embodiment is a synthesis embodiment of the present invention, providing a specific method for preparing 1,6-hexanediol, comprising the following steps: 0.19 g of 5-HMF, 9 mL of methanol solvent, and 0.19 g of 9%Mo / HZSM-5 catalyst are placed in a reaction vessel. N2 is repeatedly introduced to replace the air in the vessel, followed by the introduction of 5 MPa of H2. Stirring is started to bring the reactants to a uniform consistency. The temperature of the reaction solution is controlled at 160°C, and the reaction is kept at this temperature for 12 hours. After the reaction is complete, the reaction vessel is cooled to room temperature to obtain a reaction solution containing 1,6-hexanediol.

[0066] Example 9

[0067] This embodiment is a synthesis embodiment of the present invention, providing a specific method for preparing 1,6-hexanediol, comprising the following steps: 0.19 g of 5-HMF, 9 mL of solvent water, and 0.19 g of catalyst 7% Pd / HY are placed in a reaction vessel. N2 is repeatedly introduced to replace the air inside the vessel, followed by the introduction of 1 MPa of H2. Stirring is started to bring the reactants to a uniform consistency. The temperature of the reaction solution is controlled at 120°C, and the reaction is kept at this temperature for 4 hours. After the reaction is complete, the reaction vessel is cooled to room temperature to obtain a reaction solution containing 1,6-hexanediol.

[0068] Example 10

[0069] This embodiment is a synthesis embodiment of the present invention, providing a specific method for preparing 1,6-hexanediol, comprising the following steps: 0.19 g of 5-HMF, 9 mL of solvent water, and 0.19 g of catalyst 7% Pd / La-Y are placed in a reaction vessel. N2 is repeatedly introduced to replace the air in the vessel, followed by the introduction of 3 MPa of H2. Stirring is started to bring the reactants to a uniform consistency. The temperature of the reaction solution is controlled at 180°C, and the reaction is kept at this temperature for 4 hours. After the reaction is complete, the reaction vessel is cooled to room temperature to obtain a reaction solution containing 1,6-hexanediol.

[0070] Example 11

[0071] This embodiment is a synthesis embodiment of the present invention, providing a specific method for preparing 1,6-hexanediol, comprising the following steps: 0.19 g of 5-HMF, 9 mL of solvent water, and 0.19 g of catalyst 7% Pd / Hβ are placed in a reaction vessel. N2 is repeatedly introduced to replace the air in the vessel, followed by the introduction of 3 MPa of H2. Stirring is started to homogenize the reactants. The temperature of the reaction solution is controlled at 150°C, and the reaction is kept at this temperature for 6 hours. After the reaction is complete, the reaction vessel is cooled to room temperature to obtain a reaction solution containing 1,6-hexanediol.

[0072] Example 12

[0073] This embodiment is a synthesis embodiment of the present invention, providing a specific method for preparing 1,6-hexanediol, including the following steps: 0.19 g of 5-HMF, 9 mL of solvent water, and 0.19 g of catalyst 7% Pd / Si-MCM-41 are placed in a reaction vessel. N2 is repeatedly introduced to replace the air in the vessel, followed by the introduction of 5 MPa of H2. Stirring is then started to homogenize the reactants. The temperature of the reaction solution is controlled at 200°C, and the reaction is kept at this temperature for 8 hours. After the reaction is complete, the reaction vessel is cooled to room temperature to obtain a reaction solution containing 1,6-hexanediol.

[0074] Example 13

[0075] This embodiment is a synthesis embodiment of the present invention, providing a specific method for preparing 1,6-hexanediol, comprising the following steps: 0.19 g of 5-HMF, 9 mL of solvent water, and 0.19 g of catalyst 7% Pt / Al-MCM-41 are placed in a reaction vessel. N2 is repeatedly introduced to replace the air inside the vessel, followed by the introduction of 6 MPa of H2. Stirring is then started to homogenize the reactants. The temperature of the reaction solution is controlled at 180°C, and the reaction is kept at this temperature for 10 hours. After the reaction is complete, the reaction vessel is cooled to room temperature to obtain a reaction solution containing 1,6-hexanediol.

[0076] Example 14

[0077] This embodiment is a synthesis embodiment of the present invention, providing a specific method for preparing 1,6-hexanediol, including the following steps: 0.19 g of 5-HMF, 9 mL of methanol as solvent, and 0.19 g of 3%Ni5%Mo / TiO2 catalyst. X -SiO2 was placed in a reaction vessel, and N2 was repeatedly introduced to replace the air inside the vessel. Then, H2 at 6 MPa was introduced, and the reaction mixture was stirred until homogeneous. The temperature of the reaction solution was controlled at 160℃, and the reaction was kept at this temperature for 15 hours. After the reaction was completed, the reaction vessel was cooled to room temperature to obtain a reaction solution containing 1,6-hexanediol.

[0078] Example 15

[0079] This embodiment is a synthesis embodiment of the present invention, providing a specific method for preparing 1,6-hexanediol, including the following steps: 0.19 g of 5-HMF, 9 mL of methanol solvent, and 0.19 g of 7%Pt3%Zn / SiO2-Al2O3 catalyst are placed in a reaction vessel. N2 is repeatedly introduced to replace the air in the vessel, followed by the introduction of 3 MPa of H2. Stirring is then started to homogenize the reactants. The temperature of the reaction solution is controlled at 160°C, and the reaction is kept at this temperature for 12 hours. After the reaction is complete, the reaction vessel is cooled to room temperature to obtain a reaction solution containing 1,6-hexanediol.

[0080] Example 16

[0081] This embodiment is a synthesis embodiment of the present invention, providing a specific method for preparing 1,6-hexanediol, including the following steps: 0.19 g of 5-HMF, 9 mL of solvent ethanol, and 0.19 g of catalyst 3%Rh5%Ni / Ti-MCM-41 are placed in a reaction vessel. N2 is repeatedly introduced to replace the air in the vessel, followed by the introduction of 5 MPa of H2. Stirring is then started to homogenize the reactants. The temperature of the reaction solution is controlled at 120°C, and the reaction is kept at this temperature for 12 hours. After the reaction is complete, the reaction vessel is cooled to room temperature to obtain a reaction solution containing 1,6-hexanediol.

[0082] Example 17

[0083] This embodiment is a synthesis embodiment of the present invention, providing a specific method for preparing 1,6-hexanediol, comprising the following steps: 0.19 g of 5-HMF, 9 mL of ethyl acetate solvent, and 0.19 g of 9%Re3%Cu / Al-MCM-41 catalyst are placed in a reaction vessel. N2 is repeatedly introduced to replace the air in the vessel, followed by the introduction of 4 MPa of H2. Stirring is then started to homogenize the reactants. The temperature of the reaction solution is controlled at 100°C, and the reaction is kept at this temperature for 10 hours. After the reaction is complete, the reaction vessel is cooled to room temperature to obtain a reaction solution containing 1,6-hexanediol.

[0084] Example 18

[0085] This embodiment is a synthetic example of the present invention, providing a specific method for preparing 1,6-hexanediol, comprising the following steps: 0.19 g of 5-HMF, 9 mL of ethyl acetate solvent, and 0.19 g of 7%Cu3%Co / SAPO-11 catalyst are placed in a reaction vessel. N2 is repeatedly introduced to replace the air in the vessel, followed by the introduction of 6 MPa of H2. Stirring is then started to homogenize the reactants. The temperature of the reaction solution is controlled at 90°C, and the reaction is kept at this temperature for 20 hours. After the reaction is complete, the reaction vessel is cooled to room temperature to obtain a reaction solution containing 1,6-hexanediol.

[0086] Example 19

[0087] This embodiment is a synthesis embodiment of the present invention, providing a specific method for preparing 1,6-hexanediol, comprising the following steps: 0.19 g of 5-HMF, 9 mL of dichloromethane solvent, and 0.19 g of 1%Pd5%Cu / SiO2 catalyst are placed in a reaction vessel. N2 is repeatedly introduced to replace the air in the vessel, followed by the introduction of 4 MPa of H2. Stirring is then started to homogenize the reactants. The temperature of the reaction solution is controlled at 80°C, and the reaction is kept at this temperature for 15 hours. After the reaction is complete, the reaction vessel is cooled to room temperature to obtain a reaction solution containing 1,6-hexanediol.

[0088] Example 20

[0089] This embodiment is a synthetic embodiment of the present invention, providing a specific method for preparing 1,6-hexanediol, including the following steps: 0.19 g of 5-HMF, 9 mL of ethyl acetate solvent, and 0.19 g of 7%Pd3%Co / CeMnO catalyst. x The mixture was placed in a reaction vessel, and N2 was repeatedly introduced to replace the air inside the vessel. Then, H2 at 6 MPa was introduced, and the mixture was stirred until homogeneous. The temperature of the reaction solution was controlled at 200℃, and the reaction was kept at this temperature for 12 hours. After the reaction was completed, the reaction vessel was cooled to room temperature to obtain a reaction solution containing 1,6-hexanediol.

[0090] Example 21

[0091] This embodiment is a synthesis embodiment of the present invention, providing a specific method for preparing 1,6-hexanediol, comprising the following steps: 0.19 g of 5-HMF, 9 mL of solvent water, and 0.19 g of catalyst 1%Pt3%Co / Al-SBA-15 are placed in a reaction vessel. N2 is repeatedly introduced to replace the air in the vessel, followed by the introduction of 5 MPa of H2. Stirring is then started to homogenize the reactants. The temperature of the reaction solution is controlled at 150°C, and the reaction is kept at this temperature for 10 hours. After the reaction is complete, the reaction vessel is cooled to room temperature to obtain a reaction solution containing 1,6-hexanediol.

[0092] Example 22

[0093] This embodiment is a synthesis embodiment of the present invention, providing a specific method for preparing 1,6-hexanediol, comprising the following steps: 0.19 g of 5-HMF, 9 mL of solvent ethanol, and 0.19 g of catalyst 7%Fe1%Ir / Al-SBA-16 are placed in a reaction vessel. N2 is repeatedly introduced to replace the air in the vessel, followed by the introduction of 3 MPa of H2. Stirring is then started to homogenize the reactants. The temperature of the reaction solution is controlled at 160°C, and the reaction is kept at this temperature for 8 hours. After the reaction is complete, the reaction vessel is cooled to room temperature to obtain a reaction solution containing 1,6-hexanediol.

[0094] Example 23

[0095] This embodiment is a synthesis embodiment of the present invention, providing a specific method for preparing 1,6-hexanediol, comprising the following steps: 0.19 g of 5-HMF, 9 mL of solvent ethanol, and 0.19 g of catalyst 7%Pd7%Mo / HZSM-5 are placed in a reaction vessel. N2 is repeatedly introduced to replace the air in the vessel, followed by the introduction of 1 MPa of H2. Stirring is then started to homogenize the reactants. The temperature of the reaction solution is controlled at 120°C, and the reaction is kept at this temperature for 12 hours. After the reaction is complete, the reaction vessel is cooled to room temperature to obtain a reaction solution containing 1,6-hexanediol.

[0096] Example 24

[0097] This embodiment is a synthesis embodiment of the present invention, providing a specific method for preparing 1,6-hexanediol, comprising the following steps: 0.19 g of 5-HMF, 9 mL of ethyl acetate solvent, and 0.19 g of 5%Pd7%Ni / SAPO-34 catalyst are placed in a reaction vessel. N2 is repeatedly introduced to replace the air in the vessel, followed by the introduction of 3 MPa of H2. Stirring is then started to homogenize the reactants. The temperature of the reaction solution is controlled at 180°C, and the reaction is kept at this temperature for 4 hours. After the reaction is complete, the reaction vessel is cooled to room temperature to obtain a reaction solution containing 1,6-hexanediol.

[0098] Example 25

[0099] This embodiment is a synthesis embodiment of the present invention, providing a specific method for preparing 1,6-hexanediol, comprising the following steps: 0.19 g of 5-HMF, 9 mL of methanol solvent, and 0.19 g of catalyst 3%Ir3%Re / USY are placed in a reaction vessel. N2 is repeatedly introduced to replace the air in the vessel, followed by the introduction of 5 MPa of H2. Stirring is started to bring the reactants to a uniform consistency. The temperature of the reaction solution is controlled at 100°C, and the reaction is kept at this temperature for 2 hours. After the reaction is complete, the reaction vessel is cooled to room temperature to obtain a reaction solution containing 1,6-hexanediol.

[0100] Example 26

[0101] This embodiment is a synthesis embodiment of the present invention, providing a specific method for preparing 1,6-hexanediol, including the following steps: 0.19 g of 5-HMF, 9 mL of dichloromethane solvent, and 0.19 g of 5%Ni5%Cu / MCM-22 catalyst are placed in a reaction vessel. N2 is repeatedly introduced to replace the air in the vessel, followed by the introduction of 6 MPa of H2. Stirring is then started to bring the reactants to a uniform consistency. The temperature of the reaction solution is controlled at 140°C, and the reaction is kept at this temperature for 6 hours. After the reaction is complete, the reaction vessel is cooled to room temperature to obtain a reaction solution containing 1,6-hexanediol.

[0102] Example 27

[0103] This embodiment is a synthetic example of the present invention, providing a specific method for preparing 1,6-hexanediol, comprising the following steps: 0.19 g of 5-HMF, 9 mL of ethyl acetate solvent, and 0.19 g of 3%Ru1%Fe / ReY catalyst are placed in a reaction vessel. N2 is repeatedly introduced to replace the air in the vessel, followed by the introduction of 2 MPa of H2. Stirring is then started to homogenize the reactants. The temperature of the reaction solution is controlled at 150°C, and the reaction is kept at this temperature for 8 hours. After the reaction is complete, the reaction vessel is cooled to room temperature to obtain a reaction solution containing 1,6-hexanediol.

[0104] Example 28

[0105] This embodiment is a synthesis embodiment of the present invention, providing a specific method for preparing 1,6-hexanediol, comprising the following steps: 0.19 g of 5-HMF, 9 mL of methanol solvent, and 0.19 g of 7%Pd5%Co / Na-ZSM-5 catalyst are placed in a reaction vessel. N2 is repeatedly introduced to replace the air in the vessel, followed by the introduction of 5 MPa of H2. Stirring is then started to homogenize the reactants. The temperature of the reaction solution is controlled at 160°C, and the reaction is kept at this temperature for 10 hours. After the reaction is complete, the reaction vessel is cooled to room temperature to obtain a reaction solution containing 1,6-hexanediol.

[0106] Example 29

[0107] This embodiment is a synthesis embodiment of the present invention, providing a specific method for preparing 1,6-hexanediol, including the following steps: 0.19 g of 5-HMF, 9 mL of solvent water, and 0.19 g of catalyst 5%Ce3%La / MCM-48 are placed in a reaction vessel. N2 is repeatedly introduced to replace the air in the vessel, followed by the introduction of 6 MPa of H2. Stirring is then started to homogenize the reactants. The temperature of the reaction solution is controlled at 150°C, and the reaction is kept at this temperature for 15 hours. After the reaction is complete, the reaction vessel is cooled to room temperature to obtain a reaction solution containing 1,6-hexanediol.

[0108] Example 30

[0109] This embodiment is a synthesis embodiment of the present invention, providing a specific method for preparing 1,6-hexanediol, including the following steps: 0.19 g of 5-HMF, 9 mL of solvent water, and 0.19 g of catalyst 7%Ni3%La / CeO x -SiO2 was placed in a reactor, and N2 was repeatedly introduced to replace the air in the reactor. Then, H2 at 6 MPa was introduced, and the reactants were stirred until homogeneous. The temperature of the reaction solution was controlled at 180℃, and the reaction was kept at this temperature for 20 hours. After the reaction was completed, the reactor was cooled to room temperature to obtain a reaction solution containing 1,6-hexanediol.

[0110] Example 31

[0111] This embodiment is a synthesis embodiment of the present invention, providing a specific method for preparing 1,6-hexanediol, comprising the following steps: 0.19 g of 5-HMF, 9 mL of solvent water, and 0.19 g of catalyst 7%Pd7%Mo / KIT-6 are placed in a reaction vessel. N2 is repeatedly introduced to replace the air inside the vessel, followed by the introduction of 6 MPa of H2. Stirring is then started to homogenize the reactants. The temperature of the reaction solution is controlled at 180°C, and the reaction is kept at this temperature for 20 h. After the reaction is complete, the reaction vessel is cooled to room temperature to obtain a reaction solution containing 1,6-hexanediol.

[0112] Example 32

[0113] This embodiment is a synthesis embodiment of the present invention, providing a specific method for preparing 1,6-hexanediol, including the following steps: 0.19 g of 5-HMF, 9 mL of methanol, and 0.19 g of catalyst (5%Pd7%Mo / Al2O3) are placed in a reaction vessel. N2 is repeatedly introduced to replace the air in the vessel, followed by the introduction of 6 MPa of H2. Stirring is then started to homogenize the reactants. The temperature of the reaction solution is controlled at 180°C, and the reaction is kept at this temperature for 20 hours. After the reaction is complete, the reaction vessel is cooled to room temperature to obtain a reaction solution containing 1,6-hexanediol.

[0114] Example 33

[0115] This embodiment is a synthesis embodiment of the present invention, providing a specific method for preparing 1,6-hexanediol, including the following steps: 0.19 g of 5-HMF, 9 mL of ethanol, and 0.19 g of catalyst (3% Rh, 5% Ni / MoO) are added. x -SiO2 was placed in a reactor, and N2 was repeatedly introduced to replace the air in the reactor. Then, H2 at 6 MPa was introduced, and the reactants were stirred until homogeneous. The temperature of the reaction solution was controlled at 180℃, and the reaction was kept at this temperature for 20 hours. After the reaction was completed, the reactor was cooled to room temperature to obtain a reaction solution containing 1,6-hexanediol.

[0116] Example 34

[0117] This embodiment is a synthetic embodiment of the present invention, providing a specific method for preparing 1,6-hexanediol, including the following steps: 0.19 g of 5-HMF, 9 mL of ethyl acetate, and 0.19 g of 7% Pt / CoO2 catalyst are added. x -SiO2 was placed in a reactor, and N2 was repeatedly introduced to replace the air in the reactor. Then, H2 at 6 MPa was introduced, and the reactants were stirred until homogeneous. The temperature of the reaction solution was controlled at 180℃, and the reaction was kept at this temperature for 20 hours. After the reaction was completed, the reactor was cooled to room temperature to obtain a reaction solution containing 1,6-hexanediol.

[0118] Example 35

[0119] This embodiment is a test embodiment of the present invention, providing the detection method and results of 5-HMF conversion rate and selectivity in Examples 1-30.

[0120] The detection methods are as follows: Quantitative analysis was performed using a gas chromatograph (GC-2010 Pro) and an HP-5 capillary column (30 m × 0.32 mm × 0.25 μm). The area normalization method in quantitative analysis was used to analyze the composition of the products after the catalytic reaction. Qualitative analysis was performed using an Agilent 7890B / 5975C gas chromatograph-mass spectrometer (GC-MS) equipped with an HP-5 capillary column (30 m × 0.32 mm × 0.25 μm). The temperature was maintained at 50 °C for 1 min, then increased to 170 °C at a rate of 6 °C / min and held at 170 °C for 1 min. The GC detection results of Example 1 are shown below. Figure 3 .

[0121] The statistical results of 5-HMF conversion and 1,6-hexanediol yield for each embodiment are shown in Table 1.

[0122] Table 1. 5-HMF conversion and 1,6-hexanediol yield of the synthesis methods in Examples 1-34.

[0123] Example 5-HMF conversion rate (%) 1,6-Hexanediol yield (%) 1 100 93.6 2 50.8 32.9 3 60.9 22.9 4 100 97.4 5 80.9 66.0 6 100 87.9 7 99.7 85.8 8 70.9 58.9 9 100 89.7 10 100 90.0 11 100 89.4 12 100 88.6 13 98.4 79.9 14 80.7 70.0 15 95.8 87.7 16 100 87.9 17 100 92.0 18 85.8 73.9 19 100 91.3 20 100 90.2 21 99.3 89.1 22 100 88.5 23 100 90.8 24 100 94.9 25 100 86.4 26 87.5 90.5 27 100 90.7 28 100 93.5 29 78.6 76.4 30 79.9 82.5 31 95.1 93.3 32 93.7 91.6 33 100 89.3 34 100 87.5

[0124] The technical features of the above-described embodiments and examples can be combined in any suitable manner. For the sake of brevity, not all possible combinations of the technical features in the above-described embodiments and examples are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0125] The embodiments described above merely illustrate several implementation methods of this application and should not be construed as limiting the scope of the patent application. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the protection scope of this application. Furthermore, it should be understood that after reading the above teachings, those skilled in the art can make various alterations or modifications to this application, and the equivalent forms obtained also fall within the protection scope of this application. It should also be understood that technical solutions obtained by those skilled in the art based on the technical solutions provided in this application through logical analysis, reasoning, or limited experimentation are all within the protection scope of the appended claims. Therefore, the protection scope of this patent application should be determined by the appended claims, and the specification can be used to interpret the content of the claims.

Claims

1. 1,6-Hexanediol synthesis method, characterized in that, Includes the following steps: 5-hydroxymethylfurfural, catalyst and solvent are mixed, and hydrogen gas is introduced into the mixture; The mixture is stirred at a first temperature for a first time to obtain the 1,6-hexanediol. The first temperature is 80℃-200℃, and the first time is 1h-24h.

2. The synthesis method according to claim 1, characterized in that, The catalyst includes a support and a metal supported on the support; The carrier includes at least one of molecular sieves and oxides.

3. The synthesis method according to claim 2, characterized in that, In the catalyst, the metal includes at least one selected from Ni, Cu, Co, Mo, Zn, Ce, La, Fe, Pd, Pt, Ru, Re, and Ir; The molecular sieve includes at least one of HZSM-5, SAPO-11, HY, La-Y, Hβ, Si-MCM-41, Al-MCM-41, Ti-MCM-41, SAPO-34, USY, MCM-22, MCM-48, ReY, KIT-6, MCM-48, Al-SBA-15, and Al-SBA-16; The oxide includes TiO. x -ZrO y ZrO x -SiO2, SiO2-Al2O3, TiO x -SiO2, MoO x -SiO2, CoO x -SiO2, SiO2, Al2O3, CeMnO x and CeO x At least one of -SiO2; The metal loading is 1wt%-20wt% of the carrier.

4. The synthesis method according to claim 3, characterized in that, The catalyst comprises 7wt% Pd / Al-MCM-41, 3wt% Co / TiO2-ZrO2, 5wt% Ni / SAPO-11, 7wt% Ni / HZSM-5, and 3wt% Pt / ZrO2. x -SiO2, 7wt%Pd / HZSM-5, 5wt%Ru / Al2O3-SiO2, 9wt%Mo / HZSM-5, 7wt%Pd / HY, 7wt%P d / La-Y, 7wt%Pd / Hβ, 7wt%Pd / Si-MCM-41, 7wt%Pt / Al-MCM-41, 3wt%Ni5wt%Mo / TiO x -SiO2, 7wt%Pt3wt%Zn / SiO2-Al2O3, 3wt%Rh5wt%Ni / Ti-MCM-41, 9wt%Re3wt%Cu / Al-MCM-41, 7wt%Cu3wt%Co / SAPO-11, 1wt%Pd5wt%Cu / SiO2, 7wt%Pd3wt%Co / CeMnO x , 1wt%Pt3wt%Co / Al-SBA-15, 7wt%Fe1wt%Ir / Al-SBA-16, 7wt%Pd7wt%Mo / HZSM-5, 5wt%Pd7wt%Ni / SAPO-34, 3wt%Ir3wt%Re / USY、5wt%Ni5wt%Cu / MCM-22、3wt%Ru1wt%Fe / ReY、7wt%Pd5wt%Co / Na-ZSM-5、5wt%Ce3wt%La / MCM-48、7wt%Ni3wt%La / CeO x -SiO2, 7wt%Pd7wt%Mo / KIT-6, 5wt%Pd7wt%Mo / Al2O3, 3wt%Rh5wt%Ni / MoO x -SiO2 and 7wt%Pt / CoO x At least one of -SiO2.

5. The synthesis method according to any one of claims 1-4, characterized in that, The solvent includes at least one of water, methanol, ethanol, ethyl acetate, and dichloromethane.

6. The synthesis method according to any one of claims 1-4, characterized in that, The weight ratio of 5-hydroxymethylfurfural to the catalyst is 1:(0.2-2).

7. The synthesis method according to any one of claims 1-4, characterized in that, The ratio of the total weight of the 5-hydroxymethylfurfural and the catalyst to the amount of the solvent is 0.38-0.40 g: 9 mL.

8. The synthesis method according to any one of claims 1-4, characterized in that, The catalyst is 7%wtPd / Al-MCM-41.

9. The synthesis method according to any one of claims 1-4, characterized in that, The first temperature is 80℃-200℃, and the first time is 1h-24h.

10. The synthesis method according to any one of claims 1-4, characterized in that, The first temperature is 160℃, and the first time is 4 h.

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