CN116813574A - A kind of preparation method of 2,5-tetrahydrofurandimethanol - Google Patents

Abstract

The application discloses a preparation method of 2, 5-tetrahydrofuran dimethanol, belonging to the technical field of compound preparation. The application firstly prepares 2, 5-furan dimethanol under the hydrogen pressure of 0.5-3MPa, the reaction temperature of 60-160 ℃ and the action of a supported metal catalyst, and then prepares 2, 5-tetrahydrofuran dimethanol under the hydrogen pressure of 1-5MPa, the reaction temperature of 100-220 ℃ and the action of a supported metal nanoparticle catalyst. The preparation method of the application has the following advantages: 1) Easy to implement on a large scale; 2) The catalyst and the reaction conditions required by the two stages are different, so that the generation of byproducts can be effectively avoided, and the selectivity of the product is improved; 3) The generation of humines is effectively avoided, and the activity and stability of the catalyst are improved; 4) The product is easy to separate, environment-friendly and clean.

Description

A kind of preparation method of 2,5-tetrahydrofurandimethanol

Technical field

The invention belongs to the technical field of compound preparation, and specifically relates to a two-step hydrogenation method for preparing 2,5-tetrahydrofurandimethanol.

Background technique

2,5-Tetrahydrofurandimethanol, as a bio-based furan monomer containing a furan ring, is easier to hydrogenolyze than a benzene ring and causes less environmental pollution. The furan ring has strong rigidity, and a variety of new furan ring polymer materials can be prepared from 2,5-tetrahydrofurandimethanol; it also has great potential in the synthesis of degradable plastics.

The main traditional method for preparing 2,5-tetrahydrofurandimethanol is microbial fermentation. This method has a complex reaction process, is difficult to control, has relatively low yield and production efficiency, produces a large amount of waste liquid and waste materials, and is difficult to regenerate. Large-scale industrial application has not been achieved.

The synthesis of 2,5-tetrahydrofurandimethanol from biomass resources is a clean and renewable route. 5-hydroxymethylfurfural (HMF), as a biomass platform compound, can be converted into 2,5-tetrahydrofuran through catalytic hydrogenation. Dimethanol, but HMF is unstable and easily reacts by itself to form humins (ACS Sustain. Chem. Eng. 2021, 9, 2212–2223), resulting in catalyst deactivation and product separation difficulties. Therefore, there is an urgent need to research and develop a preparation method of 2,5-tetrahydrofurandimethanol suitable for industrial production.

Contents of the invention

In view of the problems existing in the background technology, the purpose of the present invention is to provide a preparation method of 2,5-tetrahydrofurandimethanol suitable for industrial production. The method uses 2,5-furandimethanol as raw material and adopts two-step hydrogenation. Preparing 2,5-tetrahydrofurandimethanol not only ensures the stability and activity of the catalyst, but also improves selectivity, making it more suitable for industrial production, while significantly reducing production costs.

In order to achieve the above objects, the present invention provides the following technical solutions:

The invention provides a preparation method of 2,5-tetrahydrofurandimethanol. The preparation method mainly includes the following steps:

(1) 2,5-furandimethanol is prepared from 2,5-furandimethanol under the action of a hydrogen pressure of 0.5-3MPa, a reaction temperature of 60-160°C, and a supported metal catalyst;

(2) 2,5-tetrahydrofuran is prepared from 2,5-furandimethanol prepared in step (1) under the action of a hydrogen pressure of 1-5MPa, a reaction temperature of 100-220°C, and a supported metal nanoparticle catalyst. dimethyl alcohol.

Based on the above technical solution, further, in step (1), the reaction temperature is 100-140°C, the hydrogen pressure is 1-2MPa, and the reaction time is 1-5h.

Based on the above technical solution, further, in step (2), the reaction temperature is 140-180°C, the hydrogen pressure is 2-4MPa, and the reaction time is 2-10h.

Based on the above technical solution, further, the preparation method is carried out in a pressurized fixed bed or batch reactor.

Based on the above technical solution, further, the solvent used in the preparation method is one or a mixed solution of two or more of methanol, ethanol, isopropyl alcohol, n-hexane, 1,4-dioxane, and water.

Based on the above technical solution, further, the concentration of 2,5-furandicarboxaldehyde is 1-200 mg/mL.

Based on the above technical solution, further, the supported metal catalyst includes an active component and a carrier, and the active component is one or two of gold, platinum, palladium, iridium, rhodium, ruthenium, nickel, cobalt, and copper. For the above combination, the carrier is one or a combination of two or more of metal oxides, carbon materials, diatomite, apatite, and molecular sieves.

Based on the above technical solution, further, the mass percentage of the metal element in the supported metal catalyst is 0.2%-20%.

Based on the above technical solution, further, the mass ratio of the supported metal catalyst and 2,5-furandicarbaldehyde is 1:100-1:0.1.

Based on the above technical solution, further, the supported metal nanoparticle catalyst includes an active component and a carrier, the active component is metal nanoparticles, the size of the nanoparticles is 1-50nm, preferably 2-10nm, and the metal is gold, One or a combination of two or more of platinum, palladium, iridium, rhodium, ruthenium, nickel, cobalt, and copper, and the carrier is one or two of metal oxides, carbon materials, diatomaceous earth, apatite, and molecular sieves. combinations of more than one species.

Based on the above technical solution, further, the mass percentage of the metal element in the supported metal catalyst is 1%-50%.

Based on the above technical solution, further, the term "nanoparticle size" used in this application is the average size determined by scanning electron microscope (SEM) or transmission electron microscope (TEM).

Based on the above technical solution, further, the mass ratio of the supported metal nanoparticle catalyst to 2,5-furandimethanol is 1:100-1:0.1.

Compared with the existing technology, the present invention has the following beneficial effects:

1) The two-step hydrogenation method of the present invention for preparing 2,5-tetrahydrofurandimethanol uses simple equipment and is easy to implement on a large scale. The raw material 2,5-furandimethanol used can be obtained from sufficient renewable sources (such as fructose, sucrose) preparation.

2) The method for preparing 2,5-tetrahydrofurandimethanol of the present invention consists of a first-stage reaction and a second-stage reaction. Since the first stage and the second stage require different catalysts and reaction conditions, adopting two stages can effectively Avoid the generation of by-products and improve product selectivity.

3) The method for preparing 2,5-tetrahydrofurandimethanol of the present invention effectively avoids the generation of humins and improves the activity and stability of the catalyst.

4) Due to the higher conversion rate of the method for preparing 2,5-tetrahydrofurandimethanol of the present invention, the product is easy to separate.

5) The method of preparing 2,5-tetrahydrofurandimethanol of the present invention uses bio-based raw materials, which is environmentally friendly and clean.

Description of the drawings

In order to explain the embodiments of the present invention more clearly, the drawings involved in the embodiments will be briefly introduced below.

Figure 1 is a GC analysis spectrum of 2,5-tetrahydrofurandimethanol prepared in Example 18.

Detailed ways

The present invention will be described in detail below with reference to the examples, but the implementation of the present invention is not limited thereto. Obviously, the embodiments described below are only some of the embodiments of the present invention. For those skilled in the art, without paying any attention to Under the premise of creative labor, other similar embodiments can be obtained and all fall within the protection scope of the present invention.

In the examples, Agilent 7890B high-performance gas chromatograph was used to analyze 2,5-furandicarboxaldehyde (DFF), 5-hydroxymethylfurfural (HMF), 2,5-furandimethanol (FDM) and 2,5-tetrahydrofurandiol. Methanol (THFDM) was analyzed and the external standard method was used for quantification. Test conditions in the example: chromatographic column is FFAP, hydrogen flame detector (FID), hydrogen is used as carrier gas, constant mode, split ratio 100:1, column oven temperature 75°C (2min), rising to 240°C at 30°C/min ℃ (maintain for 2 minutes).

The conversion rate of 2,5-furandimethanol (DFF) in the first stage, the selectivity of 2,5-furandimethanol (FDM) in the first stage, the conversion rate of 2,5-furandimethanol (FDM) in the second stage, the conversion rate of 2,5-furandimethanol (FDM) in the second stage, The calculation formula for the selectivity of stage 2,5-tetrahydrofurandimethanol (THFDM) is as follows:

Formula 1: Conversion rate of 2,5-furandicarbaldehyde (DFF) in the first stage = (mass of DFF actually participating in the reaction in the first stage/mass of raw material DFF) × 100%;

Formula 2: First-stage 2,5-furandimethanol (FDM) selectivity = (mass of FDM in the first-stage reaction product/theoretical mass of FDM produced in the first-stage reaction) × 100%;

Formula 3: Conversion rate of 2,5-furandimethanol (FDM) in the second stage = (mass of FDM actually participating in the reaction in the second stage reaction/mass of FDM in the first stage reaction product) × 100%;

Formula 4: Second-stage 2,5-tetrahydrofurandimethanol (THFDM) selectivity = (mass of THFDM in the second-stage reaction product/theoretical mass of THFDM produced in the second-stage reaction) × 100%;

Unless otherwise specified, the test methods used in the following examples and test examples are conventional methods. The materials, reagents, and equipment used can be purchased through commercial channels unless otherwise specified. Among them, the first stage uses a Pt/Al ₂ O ₃ catalyst, which can be prepared by the impregnation method, and the second stage uses a palladium carbon catalyst, which can be prepared by the impregnation method; the loadings of platinum and palladium are 5% and 5% respectively; The above catalysts can also be purchased through commercial channels.

Example 1

Add 0.5g of 2,5-furandicardehyde raw material and 10mL of isopropanol into the polytetrafluoroethylene lining, then add 0.1g of Pt/Al ₂ O ₃ catalyst, and transfer the polytetrafluoroethylene lining to the high-pressure reactor. After three times of air replacement with inert gas, hydrogen gas was introduced until the reaction pressure was 3MPa, the reaction temperature was set to 120°C, the rotation speed was adjusted to 600rpm, the holding time was set to 4h, and the reactor was started to run. After the reaction is completed, the temperature of the reaction kettle is cooled to room temperature, the gas in the reaction kettle is released, and then the first reaction catalyst is filtered out to obtain a reaction liquid containing 2,5-furandimethanol. GC was used for analysis, and the analysis results are shown in Table 1.

Example 2

Add 0.5g of 2,5-furandicardehyde raw material and 10mL of isopropanol into the polytetrafluoroethylene lining, then add 0.1g of Pt/Al ₂ O ₃ catalyst, and transfer the polytetrafluoroethylene lining to the high-pressure reactor. After three times of air replacement with inert gas, hydrogen gas was introduced until the reaction pressure was 2MPa, the reaction temperature was set to 120°C, the rotation speed was adjusted to 600rpm, the holding time was set to 4h, and the reactor was started to run. After the reaction is completed, the temperature of the reaction kettle is cooled to room temperature, the gas in the reaction kettle is released, and then the first reaction catalyst is filtered out to obtain a reaction liquid containing 2,5-furandimethanol. GC was used for analysis, and the analysis results are shown in Table 1.

Example 3

Add 0.5g of 2,5-furandicardehyde raw material and 10mL of isopropanol into the polytetrafluoroethylene lining, then add 0.1g of Pt/Al ₂ O ₃ catalyst, and transfer the polytetrafluoroethylene lining to the high-pressure reactor. After three times of air replacement with inert gas, hydrogen gas was introduced until the reaction pressure was 1MPa, the reaction temperature was set to 120°C, the rotation speed was adjusted to 600rpm, the holding time was set to 6h, and the reactor was started to run. After the reaction is completed, the temperature of the reaction kettle is cooled to room temperature, the gas in the reaction kettle is released, and then the first reaction catalyst is filtered out to obtain a reaction liquid containing 2,5-furandimethanol. GC was used for analysis, and the analysis results are shown in Table 1.

Example 4

Add 0.5g of 2,5-furandicardehyde raw material and 10mL of isopropanol into the polytetrafluoroethylene lining, then add 0.1g of Pt/Al ₂ O ₃ catalyst, and transfer the polytetrafluoroethylene lining to the high-pressure reactor. After three times of air replacement with inert gas, hydrogen gas was introduced until the reaction pressure was 0.5MPa, the reaction temperature was set to 120°C, the rotation speed was adjusted to 600rpm, the holding time was set to 10h, and the reactor was started to run. After the reaction is completed, the temperature of the reaction kettle is cooled to room temperature, the gas in the reaction kettle is released, and then the first reaction catalyst is filtered out to obtain a reaction liquid containing 2,5-furandimethanol. GC was used for analysis, and the analysis results are shown in Table 1.

Comparing the analysis results of Examples 1, 2, 3 and 4, it can be seen that when the reaction pressure is 2MPa, the conversion rate and selectivity are both higher. From the perspective of economy and safety, it is more appropriate to use 2MPa as the reaction pressure.

Example 5

Add 0.5g of 2,5-furandicardehyde raw material, 10mL of isopropanol into the polytetrafluoroethylene lining, and then add 0.1g of Pt/Al ₂ O ₃ catalyst. Transfer the polytetrafluoroethylene lining to the high-pressure reactor. After replacing the air with inert gas three times, introduce hydrogen until the reaction pressure is 2MPa. Set the reaction temperature to 180°C, adjust the rotation speed to 600rpm, set the holding time to 4h, and start The reactor starts running. After the reaction is completed, the temperature of the reaction kettle is cooled to room temperature, the gas in the reaction kettle is released, and then the first reaction catalyst is filtered out to obtain a reaction liquid containing 2,5-furandimethanol. GC was used for analysis, and the analysis results are shown in Table 1.

Example 6

Add 0.5g of 2,5-furandicardehyde raw material, 10mL of isopropanol into the polytetrafluoroethylene lining, and then add 0.1g of Pt/Al ₂ O ₃ catalyst. Transfer the polytetrafluoroethylene lining to the high-pressure reactor. After replacing the air with inert gas three times, introduce hydrogen until the reaction pressure is 2MPa. Set the reaction temperature to 160°C, adjust the rotation speed to 600rpm, set the holding time to 4h, and start The reactor starts running. After the reaction is completed, the temperature of the reaction kettle is cooled to room temperature, the gas in the reaction kettle is released, and then the first reaction catalyst is filtered out to obtain a reaction liquid containing 2,5-furandimethanol. GC was used for analysis, and the analysis results are shown in Table 1.

Example 7

Add 0.5g of 2,5-furandicardehyde raw material, 10mL of isopropanol into the polytetrafluoroethylene lining, and then add 0.1g of Pt/Al ₂ O ₃ catalyst. Transfer the polytetrafluoroethylene lining to the high-pressure reactor. After replacing the air with inert gas three times, introduce hydrogen until the reaction pressure is 2MPa. Set the reaction temperature to 100°C, adjust the rotation speed to 600rpm, set the holding time to 4h, and start The reactor starts running. After the reaction is completed, the temperature of the reaction kettle is cooled to room temperature, the gas in the reaction kettle is released, and then the first reaction catalyst is filtered out to obtain a reaction liquid containing 2,5-furandimethanol. GC was used for analysis, and the analysis results are shown in Table 1.

Example 8

Add 0.5g of 2,5-furandicardehyde raw material, 10mL of isopropanol into the polytetrafluoroethylene lining, and then add 0.1g of Pt/Al ₂ O ₃ catalyst. Transfer the polytetrafluoroethylene lining to the high-pressure reactor. After replacing the air with inert gas three times, introduce hydrogen gas until the reaction pressure is 2MPa. Set the reaction temperature to 60°C, adjust the rotation speed to 600rpm, set the holding time to 10h, and start The reactor starts running. After the reaction is completed, the temperature of the reaction kettle is cooled to room temperature, the gas in the reaction kettle is released, and then the first reaction catalyst is filtered out to obtain a reaction liquid containing 2,5-furandimethanol. GC was used for analysis, and the analysis results are shown in Table 1.

Table 1 Experimental conditions and results of Examples 1-8

Example Temperature(℃) Pressure(MPa) Time(h) Conversion rate(%) Selectivity (%) 1 120 3 4 100 92 2 120 2 4 100 99 3 120 1 6 77 99 4 120 0.5 10 12 99 5 180 2 4 100 12 6 160 2 4 100 46 7 100 2 4 42 97 8 60 2 10 8 82

Comparing the analysis results of Examples 2, 5, 6, 7 and 8, it can be seen that the change of reaction temperature has a decisive effect on the selectivity. The optimal reaction temperature is 120°C.

Example 9

According to the optimal reaction conditions for preparing the intermediate product FDM from DFF in Example 2, the reaction was scaled up to a 200 mL reactor for the first stage reaction. The analysis results obtained were almost indistinguishable from those of the 25 mL reactor. Based on this, scale-up production can be carried out.

Add 10 mL of the solution containing 2,5-furandimethanol from which the first reaction catalyst was filtered out after the first stage reaction to the polytetrafluoroethylene liner, and then add 0.1 g of palladium carbon catalyst. Transfer the polytetrafluoroethylene lining to the high-pressure reactor. After replacing the air with inert gas three times, introduce hydrogen gas until the reaction pressure is 1MPa. Set the reaction temperature to 160°C, adjust the rotation speed to 600rpm, set the holding time to 10h, and start The reactor starts running. After the reaction is completed, the temperature of the reaction kettle is cooled to room temperature, the gas in the reaction kettle is released, and then the second reaction catalyst is filtered out to obtain a reaction liquid containing 2,5-tetrahydrofurandimethanol. GC was used for analysis, and the analysis results are shown in Table 2.

Example 10

As in Example 9, 10 mL of the solution containing 2,5-furandimethanol obtained after the first stage reaction was filtered and the first reaction catalyst was filtered was added to the polytetrafluoroethylene liner, and then 0.1g of palladium carbon catalyst was added. . Transfer the polytetrafluoroethylene lining to the high-pressure reactor. After replacing the air with inert gas three times, introduce hydrogen until the reaction pressure is 2MPa. Set the reaction temperature to 160°C, adjust the rotation speed to 600rpm, set the holding time to 5h, and start The reactor starts running. After the reaction is completed, the temperature of the reaction kettle is cooled to room temperature, the gas in the reaction kettle is released, and then the second reaction catalyst is filtered out to obtain a reaction liquid containing 2,5-tetrahydrofurandimethanol. GC was used for analysis, and the analysis results are shown in Table 2.

Example 11

As in Example 9, 10 mL of the solution containing 2,5-furandimethanol obtained after the first stage reaction was filtered and the first reaction catalyst was filtered was added to the polytetrafluoroethylene liner, and then 0.1g of palladium carbon catalyst was added. . Transfer the polytetrafluoroethylene lining to the high-pressure reactor. After replacing the air with inert gas three times, introduce hydrogen until the reaction pressure is 3MPa. Set the reaction temperature to 160°C, adjust the rotation speed to 600rpm, set the holding time to 5h, and start The reactor starts running. After the reaction is completed, the temperature of the reaction kettle is cooled to room temperature, the gas in the reaction kettle is released, and then the second reaction catalyst is filtered out to obtain a reaction liquid containing 2,5-tetrahydrofurandimethanol. GC was used for analysis, and the analysis results are shown in Table 2.

Example 12

As in Example 9, 10 mL of the solution containing 2,5-furandimethanol obtained after the first stage reaction was filtered and the first reaction catalyst was filtered was added to the polytetrafluoroethylene liner, and then 0.1g of palladium carbon catalyst was added. . Transfer the polytetrafluoroethylene lining to the high-pressure reactor. After replacing the air with inert gas three times, introduce hydrogen gas until the reaction pressure is 5MPa. Set the reaction temperature to 160°C, adjust the rotation speed to 600rpm, set the holding time to 5h, and start The reactor starts running. After the reaction is completed, the temperature of the reaction kettle is cooled to room temperature, the gas in the reaction kettle is released, and then the second reaction catalyst is filtered out to obtain a reaction liquid containing 2,5-tetrahydrofurandimethanol. GC was used for analysis, and the analysis results are shown in Table 2.

Comparing the analysis results of Examples 9, 10, 11, and 12, it can be seen that increasing the reaction pressure is conducive to rapid reaction, and at the same time, high pressure is conducive to improving selectivity. From the perspective of economy and safety, it is more appropriate to use 3MPa as the reaction pressure.

Example 13

As in Example 9, 10 mL of the solution containing 2,5-furandimethanol obtained after the first stage reaction was filtered and the first reaction catalyst was filtered was added to the polytetrafluoroethylene liner, and then 0.1g of palladium carbon catalyst was added. . Transfer the polytetrafluoroethylene lining to the high-pressure reactor. After replacing the air with inert gas three times, introduce hydrogen until the reaction pressure is 3MPa. Set the reaction temperature to 170°C, adjust the rotation speed to 600rpm, set the holding time to 5h, and start The reactor starts running. After the reaction is completed, the temperature of the reaction kettle is cooled to room temperature, the gas in the reaction kettle is released, and then the second reaction catalyst is filtered out to obtain a reaction liquid containing 2,5-tetrahydrofurandimethanol. GC was used for analysis, and the analysis results are shown in Table 2.

Example 14

As in Example 9, 10 mL of the solution containing 2,5-furandimethanol obtained after the first stage reaction was filtered and the first reaction catalyst was filtered was added to the polytetrafluoroethylene liner, and then 0.1g of palladium carbon catalyst was added. . Transfer the polytetrafluoroethylene lining to the high-pressure reactor. After replacing the air with inert gas three times, introduce hydrogen until the reaction pressure is 3MPa. Set the reaction temperature to 180°C, adjust the rotation speed to 600rpm, set the holding time to 5h, and start The reactor starts running. After the reaction is completed, the temperature of the reaction kettle is cooled to room temperature, the gas in the reaction kettle is released, and then the second reaction catalyst is filtered out to obtain a reaction liquid containing 2,5-tetrahydrofurandimethanol. GC was used for analysis, and the analysis results are shown in Table 2.

Example 15

As in Example 9, 10 mL of the solution containing 2,5-furandimethanol obtained after the first stage reaction was filtered and the first reaction catalyst was filtered was added to the polytetrafluoroethylene liner, and then 0.1g of palladium carbon catalyst was added. . Transfer the polytetrafluoroethylene lining to the high-pressure reactor. After replacing the air with inert gas three times, introduce hydrogen until the reaction pressure is 3MPa. Set the reaction temperature to 200°C, adjust the rotation speed to 600rpm, set the holding time to 5h, and start The reactor starts running. After the reaction is completed, the temperature of the reaction kettle is cooled to room temperature, the gas in the reaction kettle is released, and then the second reaction catalyst is filtered out to obtain a reaction liquid containing 2,5-tetrahydrofurandimethanol. GC was used for analysis, and the analysis results are shown in Table 2.

Example 16

As in Example 9, 10 mL of the solution containing 2,5-furandimethanol obtained after the first stage reaction was filtered and the first reaction catalyst was filtered was added to the polytetrafluoroethylene liner, and then 0.1g of palladium carbon catalyst was added. . Transfer the polytetrafluoroethylene lining to the high-pressure reactor. After replacing the air with inert gas three times, introduce hydrogen gas until the reaction pressure is 3MPa. Set the reaction temperature to 220°C, adjust the rotation speed to 600rpm, set the holding time to 5h, and start The reactor starts running. After the reaction is completed, the temperature of the reaction kettle is cooled to room temperature, the gas in the reaction kettle is released, and then the second reaction catalyst is filtered out to obtain a reaction liquid containing 2,5-tetrahydrofurandimethanol. GC was used for analysis, and the analysis results are shown in Table 2.

Example 17

As in Example 9, 10 mL of the solution containing 2,5-furandimethanol obtained after the first stage reaction was filtered and the first reaction catalyst was filtered was added to the polytetrafluoroethylene liner, and then 0.1g of palladium carbon catalyst was added. . Transfer the polytetrafluoroethylene lining to the high-pressure reactor. After replacing the air with inert gas three times, introduce hydrogen until the reaction pressure is 3MPa. Set the reaction temperature to 120°C, adjust the rotation speed to 600rpm, set the holding time to 15h, and start The reactor starts running. After the reaction is completed, the temperature of the reaction kettle is cooled to room temperature, the gas in the reaction kettle is released, and then the second reaction catalyst is filtered out to obtain a reaction liquid containing 2,5-tetrahydrofurandimethanol. GC was used for analysis, and the analysis results are shown in Table 2.

Table 2 Experimental conditions and results of Examples 9-17

Example Temperature(℃) Pressure(MPa) Time(h) Conversion rate(%) Selectivity (%) 9 160 1 10 6 92 10 160 2 5 34 98 11 160 3 5 87 99 12 160 5 5 100 99 13 170 3 5 100 99 14 180 3 5 100 77 15 200 3 5 100 46 16 220 3 5 100 twenty one 17 120 3 15 4 95

Comparing the analysis results of Examples 11 and 13-17, it can be seen that the reaction temperature affects the selectivity, and if the reaction temperature is too high, it is easy to cause side reactions. It is more appropriate to use 170°C as the reaction temperature.

Example 18

This embodiment provides a two-step hydrogenation method for preparing 2,5-tetrahydrofurandimethanol. The chemical reaction route is as follows:

Specifically, it includes the following steps:

(1) First stage reaction

Add 0.5g of 2,5-furandicardehyde raw material and 10mL of isopropanol into the polytetrafluoroethylene lining, then add 0.1g of Pt/Al ₂ O ₃ catalyst, and transfer the polytetrafluoroethylene lining to the high-pressure reactor. After three times of air replacement with inert gas, hydrogen gas was introduced until the reaction pressure was 2MPa, the reaction temperature was set to 120°C, the rotation speed was adjusted to 600rpm, the holding time was set to 4h, and the reactor was started to run. After the reaction is completed, the temperature of the reaction kettle is cooled to room temperature, the gas in the reaction kettle is released, and then the catalyst is filtered out to obtain a reaction liquid containing 2,5-furandimethanol. It was analyzed by GC, and the analysis results were basically the same as those in Example 2.

(2) Second stage reaction

Add the 2,5-furandimethanol reaction solution obtained in the first stage and 0.1g of palladium carbon catalyst to the polytetrafluoroethylene lining, transfer the polytetrafluoroethylene lining to the high-pressure reactor, and undergo three inert gas replacements After air is added, hydrogen gas is introduced until the reaction pressure is 3MPa, the reaction temperature is set to 170°C, the rotation speed is adjusted to 600rpm, the holding time is set to 5h, and the reaction kettle is started to run. After the reaction is completed, the temperature of the reaction kettle is cooled to room temperature, the gas in the reaction kettle is released, and then the catalyst is filtered out to obtain a reaction liquid containing 2,5-tetrahydrofurandimethanol. The reaction solution was distilled under reduced pressure to remove isopropyl alcohol at 60°C, and then other impurities were removed under reduced pressure at 150°C. Finally, the final product was analyzed by GC. The analytical spectrum is shown in Figure 1. The purity of 2,5-tetrahydrofurandimethanol is higher than 99%.

Claims (10)

1. The preparation method of the 2, 5-tetrahydrofuran dimethanol is characterized by mainly comprising the following steps of:

(1) 2, 5-furan dicarboxaldehyde is prepared under the action of a supported metal catalyst at the hydrogen pressure of 0.5-3MPa and the reaction temperature of 60-160 ℃ to obtain 2, 5-furan dicarboxaldehyde;

(2) The 2, 5-furandimethanol prepared in the step (1) is prepared under the action of a supported metal nanoparticle catalyst under the hydrogen pressure of 1-5MPa and the reaction temperature of 100-220 ℃ to obtain the 2, 5-tetrahydrofurandimethanol.

2. The preparation method according to claim 1, wherein the reaction temperature in the step (1) is 100-140 ℃, the hydrogen pressure is 1-2MPa, and the reaction time is 1-5h.

3. The preparation method according to claim 1, wherein the reaction temperature in the step (2) is 140-180 ℃, the hydrogen pressure is 2-4MPa, and the reaction time is 2-10h.

4. The process according to claim 1, wherein the process is carried out in a pressurized fixed bed or batch reactor.

5. The preparation method according to claim 1, wherein the solvent used in the preparation method is one or more of methanol, ethanol, isopropanol, n-hexane, 1, 4-dioxane, and water.

6. The process according to claim 5, wherein the concentration of 2, 5-furandicarboxaldehyde is 1-200mg/mL.

7. The preparation method of claim 1, wherein the supported metal catalyst comprises an active component and a carrier, the active component is one or more of gold, platinum, palladium, iridium, rhodium, ruthenium, nickel, cobalt and copper, and the carrier is one or more of metal oxide, carbon material, diatomite, apatite and molecular sieve.

8. The preparation method according to claim 7, wherein the mass percentage of the metal element in the supported metal catalyst is 0.2% -20%; the mass ratio of the supported metal catalyst to the 2, 5-furan dicarboxaldehyde is 1:100-1:0.1.

9. The preparation method of the supported metal nanoparticle catalyst according to claim 1, wherein the supported metal nanoparticle catalyst comprises an active component and a carrier, the active component is metal nanoparticles, the size of the nanoparticles is 1-50nm, the metal is one or a combination of more than two of gold, platinum, palladium, iridium, rhodium, ruthenium, nickel, cobalt and copper, and the carrier is one or a combination of more than two of metal oxide, carbon material, diatomite, apatite and molecular sieve.

10. The preparation method according to claim 9, wherein the mass percentage of the metal element in the supported metal catalyst is 1% -50%; the mass ratio of the supported metal nanoparticle catalyst to the 2, 5-furandimethanol is 1:100-1:0.1.