Catalyst for preparing beta-angelica lactone from furfuryl alcohol and preparation method of catalyst

Abstract

The invention provides a catalyst for preparing beta-angelica lactone from furfuryl alcohol and a preparation method of the catalyst. Sodium metaaluminate, SiO2, a Beta molecular sieve seed crystal and a TEAOH solution are used as raw materials, a gelatinous precursor is prepared through mechanical grinding by adopting a mechanochemical method under the conditions of no additional solvent, less fluorine or no fluorine and no alkali, then a Na-Beta molecular sieve is obtained through reaction kettle heat treatment and roasting, and then the H-Beta molecular sieve is obtained through ion exchange. The H-Beta molecular sieve disclosed by the invention is simple and efficient to prepare, the hydrothermal reaction only needs 1-4 days, the Si / Al ratio can be regulated and controlled within 6-infinity, and the yield is close to 100%. Under the nitrogen atmosphere, the H-Beta molecular sieve catalyst provided by the invention realizes efficient preparation of beta-angelica lactone from furfuryl alcohol, overcomes the problems of great pollution, long period and low yield in preparation of a Beta molecular sieve catalyst, low selectivity in preparation of angelica lactone from furfuryl alcohol and the like, and has a wide application prospect.

Description

Technical Field

[0001] This invention belongs to the field of biomass high-value technology, specifically relating to a catalyst for the preparation of β-angelicol from furfuryl alcohol and its preparation method. Background Technology

[0002] With the continuous depletion of global energy resources, biomass, as the only renewable carbon resource on Earth, has attracted widespread attention from the scientific community due to its abundant reserves, zero emissions, and green, pollution-free characteristics. Angelica lactone, as a widely used biomass derivative, has immense potential for development. It can be used as a variety of food additives and flavorings, and is also an important intermediate in the production of antibiotics, γ-valerate, and other fine chemical products. In recent years, studies have found that angelica lactone can be polymerized to form angelica lactone dimers and angelica lactone trimers. These polymers undergo hydrogenation and deoxygenation under the action of noble metal catalysts, further reacting to produce C6-C6 carbon-containing compounds. 15 Biomass fuel has good application prospects.

[0003] Currently, angelica lactone is mainly prepared from levulinic acid using molecular sieve solid acid catalysts, which suffers from high cost and low yield. By tracing upstream raw materials and analyzing mature preparation methods, and linking the upstream raw materials of the existing reactant levulinic acid with the target product angelica lactone, a new reaction system for preparing angelica lactone can be established, omitting or shortening intermediate steps in the reaction process. This reduces reaction costs and increases the yield of angelica lactone, which is a crucial step in realizing the "biomass-biofuel" technology pathway.

[0004] Beta molecular sieve catalysts, as catalysts with significant acidity and bronsted acidic sites, still suffer from low yield and high pollution during their preparation. The Beta molecular sieve catalyst described in this invention offers high yield and is environmentally friendly and pollution-free. It also enables a one-step process for producing angelica lactone from furfuryl alcohol, an upstream feedstock of levulinic acid, solving the problems inherent in traditional angelica lactone preparation processes and providing a technological foundation for realizing a renewable green energy route based on biomass and fuel oil. Summary of the Invention

[0005] The purpose of this invention is to provide a method for preparing a catalyst for the production of β-angelicol from furfuryl alcohol, thereby addressing the problems mentioned in the background section. The catalyst of this invention can perform the directed conversion of furfuryl alcohol to β-angelicol under relatively mild conditions, achieving a raw material conversion rate of up to 100%. It also exhibits high selectivity for β-angelicol, exceeding 80%, thus solving the problems of high cost, poor selectivity, and low yield and high pollution associated with traditional angelicol production processes, as well as the issues of high pollution associated with the preparation of Beta molecular sieve catalysts.

[0006] To achieve the above objectives, the present invention adopts the following technical solution: A method for preparing a catalyst for the preparation of β-angelicin from furfuryl alcohol, comprising at least the following raw materials: sodium aluminate, SiO2, Beta molecular sieve seed crystals and tetraethylammonium hydroxide (TEAOH) solution.

[0007] Furthermore, the silicon-to-aluminum ratio of the Beta molecular sieve seed crystals should be close to or consistent with that of SiO2 / sodium aluminate, and the molar ratio of SiO2 / sodium aluminate should be 6~∞.

[0008] Furthermore, the concentration of the TEAOH solution is 20-40 wt%, and the molar ratio of SiO2 to TEAOH is 1.5-7.5.

[0009] Furthermore, the preparation process of the catalyst includes the following steps: 1) Sodium aluminate, TEAOH solution, SiO2, and Beta molecular sieve seed crystals were ground into a gel by mechanochemical method, and the gel was transferred into a hydrothermal reactor and kept at 130-190 °C for 24-96 h. 2) The product obtained in step 1) is washed with water, filtered, and the resulting solid is dried in an oven overnight; 3) The dried product obtained in step 2) is calcined in a muffle furnace at 450~650 ℃ for 3~6 h; 4) The calcined product obtained in 3) is subjected to ion exchange, that is, the calcined product is mixed with 2 M NH4Cl aqueous solution at a solid-liquid ratio of 1g:60mL, stirred at 40~80 ℃ for 4~10 h, then washed with water, filtered, and dried in an oven overnight; 5) The dried product obtained in step 4) is calcined in a muffle furnace at 450~650 ℃ for 3~6 h to obtain an H-Beta molecular sieve catalyst for the preparation of β-angelicolol from furfuryl alcohol.

[0010] Further, in step 4), three ion exchange operations are performed.

[0011] Furthermore, the pore volume of the H-Beta molecular sieve catalyst is 0.10~0.80 cm³. 3 / g, specific surface area of ​​200~800m² 2 / g.

[0012] Furthermore, an H-Beta molecular sieve catalyst prepared by the above method is applied in the conversion of furfuryl alcohol to β-angelicol. The specific steps involve reacting furfuryl alcohol, a reaction solvent, and a catalyst under the following conditions: an inert gas atmosphere, a C2-C5 low-carbon alcohol as the reaction solvent, a reaction temperature of 333-433 K, a reaction time of 0.2-5 h, a furfuryl alcohol to solvent mass percentage of 5-40 wt%, a catalyst to furfuryl alcohol mass ratio of 0.01-0.1 g / 1 ml, and the final target product being β-angelicol.

[0013] The advantages of the catalyst for the preparation of β-angelicol from furfuryl alcohol described in this invention are as follows: (1) The catalyst described in this invention catalyzes the preparation of β-angelica lactone from furfuryl alcohol. Compared with the traditional method of generating angelica lactone from levulinic acid, by tracing upstream, furfuryl alcohol is used as the reaction substrate to directly prepare angelica lactone in one step. By simplifying the reaction steps, shortening the synthesis cycle, and reducing the generation of intermediate levulinic acid and by-products, the production efficiency is significantly improved and the cost of preparing angelica lactone is reduced.

[0014] (2) The H-Beta molecular sieve catalyst of the present invention is prepared by mechanochemical method under conditions of no additional solvent, low or no fluorine, and no alkali. The preparation is simple and efficient, and the hydrothermal method only takes 1-4 days. The Si / Al ratio can be controlled from 6 to ∞, and the yield is close to 100%. It overcomes the problems of large pollution, long cycle and low yield in the preparation of Beta molecular sieve catalysts. It is more environmentally friendly and safe, and has a higher degree of industrialization and broad application prospects.

[0015] (3) The catalyst described in this invention benefits from abundant Bronsonted acidic sites, and prepares β-angelicin under normal pressure nitrogen and low reaction temperature. The reaction conditions are mild, the raw material conversion rate is high, and the target product selectivity is large, exhibiting high activity. It solves the problem of low selectivity in the preparation of angelicin from furfuryl alcohol, realizes the efficient preparation of β-angelicin from furfuryl alcohol, has excellent catalytic performance, realizes the conversion of low-value chemicals into high-value chemicals, and provides a technical route for the conversion of biomass derivatives. Attached Figure Description

[0016] Figure 1 The XRD patterns of H-Beta catalysts 1-5 for the preparation of β-angelicin from furfuryl alcohol according to the present invention are shown below. Figure 2 The H-Beta catalyst 2 for the production of β-angelicin from furfuryl alcohol described in this invention was tested at 120 °C. Detailed Implementation

[0017] To enable those skilled in the art to better understand the technical solution of the present invention, the present invention will be further described in detail below with reference to the accompanying drawings and preferred embodiments.

[0018] Example 1 The H-Beta catalyst for the production of β-angelicin from furfuryl alcohol described in this embodiment was prepared from the following raw materials: Sodium aluminate, 0.087 g; SiO2, 1.6 g; Beta molecular sieve seed crystals with a silicon-to-aluminum ratio of 25, 0.1 g; 35 wt% TEAOH solution, 1.46 ml, wherein the molar ratio of SiO2 to TEAOH is 7.5.

[0019] The preparation method of the H-Beta catalyst for the production of β-angelicol from furfuryl alcohol in this embodiment is as follows: 1) The above amounts of sodium aluminate, TEAOH solution, SiO2, and Beta molecular sieve seed crystals were ground into a gel by mechanochemical method, and the gel was transferred into a hydrothermal reactor and kept at 170 °C for 96 h. 2) The product obtained in step 1) is washed with water, filtered, and the resulting solid is dried in an oven overnight; 3) The dried product obtained in step 2) was calcined in a muffle furnace at 550 °C for 6 h. The calcined product was then subjected to ion exchange, that is, the calcined product was mixed with 2 M NH4Cl aqueous solution at a solid-liquid ratio of 1 g: 60 mL, stirred at 60 °C for 8 h, then washed with water, filtered, and dried at 80 °C. The ion exchange operation was repeated three times. 4) The dried product obtained in step 3) is calcined in a muffle furnace at 550 °C for 6 h to obtain the H-Beta catalyst for the preparation of β-angelicin from furfuryl alcohol, denoted as Cat.-1.

[0020] Example 2 The H-Beta catalyst for the production of β-angelicin from furfuryl alcohol described in this embodiment was prepared from the following raw materials: Sodium aluminate, 0.087 g; SiO2, 1.6 g; Beta molecular sieve seed crystals with a silicon-to-aluminum ratio of 25, 0.1 g; 35 wt% TEAOH solution, 1.83 ml, wherein the molar ratio of SiO2 to TEAOH is 6.

[0021] The preparation method of the H-Beta catalyst for the production of β-angelicol from furfuryl alcohol in this embodiment is as follows: 1) The above amounts of sodium aluminate, TEAOH solution, SiO2, and Beta molecular sieve seed crystals were ground into a gel by mechanochemical method, and the gel was transferred into a hydrothermal reactor and kept at 170 °C for 96 h. 2) The product obtained in step 1) is washed with water, filtered, and the resulting solid is dried in an oven overnight; 3) The dried product obtained in step 2) was calcined in a muffle furnace at 550 °C for 6 h. The calcined product was then subjected to ion exchange, that is, the calcined product was mixed with 2 M NH4Cl aqueous solution at a solid-liquid ratio of 1 g: 60 mL, stirred at 60 °C for 8 h, then washed with water, filtered, and dried at 80 °C. The ion exchange operation was repeated three times. 4) The dried product obtained in step 3) was calcined in a muffle furnace at 550 °C for 6 h to obtain the H-Beta catalyst for the preparation of β-angelicol from furfuryl alcohol, denoted as Cat.-2.

[0022] Example 3 The H-Beta catalyst for the production of β-angelicin from furfuryl alcohol described in this embodiment was prepared from the following raw materials: Sodium aluminate, 0.087 g; SiO2, 1.6 g; Beta molecular sieve seed crystals with a silicon-to-aluminum ratio of 25, 0.1 g; 35 wt% TEAOH solution, 2.45 ml, wherein the molar ratio of SiO2 to TEAOH is 4.5.

[0023] The preparation method of the H-Beta catalyst for the production of β-angelicol from furfuryl alcohol in this embodiment is as follows: 1) The above amounts of sodium aluminate, TEAOH solution, SiO2, and Beta molecular sieve seed crystals were ground into a gel by mechanochemical method, and the gel was transferred into a hydrothermal reactor and kept at 170 °C for 96 h. 2) The product obtained in step 1) is washed with water, filtered, and the resulting solid is dried in an oven overnight; 3) The dried product obtained in step 2) was calcined in a muffle furnace at 550 °C for 6 h. The calcined product was then subjected to ion exchange, that is, the calcined product was mixed with 2 M NH4Cl aqueous solution at a solid-liquid ratio of 1 g: 60 mL, stirred at 60 °C for 8 h, then washed with water, filtered, and dried at 80 °C. The ion exchange operation was repeated three times. 4) The dried product obtained in step 3) is calcined in a muffle furnace at 550 °C for 6 h to obtain the H-Beta catalyst for the preparation of β-angelicol from furfuryl alcohol, denoted as Cat.-3.

[0024] Example 4 The H-Beta catalyst for the production of β-angelicin from furfuryl alcohol described in this embodiment was prepared from the following raw materials: Sodium aluminate, 0.087 g; SiO2, 1.6 g; Beta molecular sieve seed crystals with a silicon-to-aluminum ratio of 25, 0.1 g; 3.65 ml of 35 wt% TEAOH solution, wherein the molar ratio of SiO2 to TEAOH is 3.

[0025] The preparation method of the H-Beta catalyst for the production of β-angelicol from furfuryl alcohol in this embodiment is as follows: 1) The above amounts of sodium aluminate, TEAOH solution, SiO2, and Beta molecular sieve seed crystals were ground into a gel by mechanochemical method, and the gel was transferred into a hydrothermal reactor and kept at 170 °C for 96 h. 2) The product obtained in step 1) is washed with water, filtered, and the resulting solid is dried in an oven overnight; 3) The dried product obtained in step 2) was calcined in a muffle furnace at 550 °C for 6 h. The calcined product was then subjected to ion exchange, that is, the calcined product was mixed with 2 M NH4Cl aqueous solution at a solid-liquid ratio of 1 g: 60 mL, stirred at 60 °C for 8 h, then washed with water, filtered, and dried at 80 °C. The ion exchange operation was repeated three times. 4) The dried product obtained in step 3) is calcined in a muffle furnace at 550 °C for 6 h to obtain the H-Beta catalyst for the preparation of β-angelicin from furfuryl alcohol, denoted as Cat.-4.

[0026] Example 5 The H-Beta catalyst for the production of β-angelicin from furfuryl alcohol described in this embodiment was prepared from the following raw materials: Sodium aluminate, 0.087 g; SiO2, 1.6 g; Beta molecular sieve seed crystals with a silicon-to-aluminum ratio of 25, 0.1 g; 35 wt% TEAOH solution, 7.30 ml, wherein the molar ratio of SiO2 to TEAOH is 1.5.

[0027] The preparation method of the H-Beta catalyst for the production of β-angelicol from furfuryl alcohol in this embodiment is as follows: 1) The above amounts of sodium aluminate, TEAOH solution, SiO2, and Beta molecular sieve seed crystals were ground into a gel by mechanochemical method, and the gel was transferred into a hydrothermal reactor and kept at 170 °C for 96 h. 2) The product obtained in step 1) is washed with water, filtered, and the resulting solid is dried in an oven overnight; 3) The dried product obtained in step 2) was calcined in a muffle furnace at 550 °C for 6 h. The calcined product was then subjected to ion exchange, that is, the calcined product was mixed with 2 M NH4Cl aqueous solution at a solid-liquid ratio of 1 g: 60 mL, stirred at 60 °C for 8 h, then washed with water, filtered, and dried at 80 °C. The ion exchange operation was repeated three times. 4) The dried product obtained in step 3) is calcined in a muffle furnace at 550 °C for 6 h to obtain the H-Beta catalyst for the preparation of β-angelicin from furfuryl alcohol, denoted as Cat.-5.

[0028] Comparative Example 1 Commercial H-beta molecular sieves with a silicon-to-aluminum ratio of 12.5 were calcined in a muffle furnace at 550 °C for 6 h to obtain the furfuryl alcohol catalyst for the preparation of β-angelicin, denoted as Cat.-6.

[0029] Comparative Example 2 Commercial H-beta molecular sieves with a silicon-to-aluminum ratio of 25 were calcined in a muffle furnace at 550 °C for 6 h to obtain the furfuryl alcohol catalyst for the preparation of β-angelicin, denoted as Cat.-7.

[0030] Comparative Example 3 Commercial H-beta molecular sieves with a silicon-to-aluminum ratio of 50 were calcined in a muffle furnace at 550 °C for 6 h to obtain the furfuryl alcohol catalyst for the preparation of β-angelicin, denoted as Cat.-8.

[0031] Application Example 1 Accurately weigh 0.087 ml of furfuryl alcohol and 5 ml of 2-pentanol, add them to a 50 ml three-necked flask, adjust the stirring speed of the magnetic stirrer to 550 r / min, seal the flask, and purge with high-purity nitrogen for 5 min, maintaining a nitrogen atmosphere at 50 m... 3 The mixture was purged at a flow rate of [flow rate missing] / h, heated to 120 °C, and 0.1 g of Cat.-1 catalyst was added. The reaction was allowed to proceed for 5 h. After the reaction, the reaction solution was filtered to obtain the liquid product and the solid catalyst. The liquid product was analyzed by GC-MS, and the results were calculated using the area normalization method. The test results are shown in Table 1.

[0032] Application Example 2 Accurately weigh 0.087 ml of furfuryl alcohol and 5 ml of 2-pentanol, add them to a 50 ml three-necked flask, adjust the stirring speed of the magnetic stirrer to 550 r / min, seal the flask, and purge with high-purity nitrogen for 5 min, maintaining a nitrogen atmosphere at 50 m... 3 The mixture was purged at a flow rate of [flow rate missing] / h, heated to 120 °C, and 0.1 g of Cat.-2 catalyst was added. The reaction was allowed to proceed for 5 h. After the reaction, the reaction solution was filtered to obtain the liquid product and the solid catalyst. The liquid product was analyzed by GC-MS, and the results were calculated using the area normalization method. The test results are shown in Table 1.

[0033] Application Example 3 Accurately weigh 0.087 ml of furfuryl alcohol and 5 ml of 2-pentanol, add them to a 50 ml three-necked flask, adjust the stirring speed of the magnetic stirrer to 550 r / min, seal the flask, and purge with high-purity nitrogen for 5 min, maintaining a nitrogen atmosphere at 50 m... 3The mixture was purged at a flow rate of [flow rate missing] / h, heated to 120 °C, and 0.1 g of Cat.-3 catalyst was added. The reaction was allowed to proceed for 5 h. After the reaction, the reaction solution was filtered to obtain the liquid product and the solid catalyst. The liquid product was analyzed by GC-MS, and the results were calculated using the area normalization method. The test results are shown in Table 1.

[0034] Application Example 4 Accurately weigh 0.087 ml of furfuryl alcohol and 5 ml of 2-pentanol, add them to a 50 ml three-necked flask, adjust the stirring speed of the magnetic stirrer to 550 r / min, seal the flask, and purge with high-purity nitrogen for 5 min, maintaining a nitrogen atmosphere at 50 m... 3 The mixture was purged at a flow rate of [flow rate missing] / h, heated to 120 °C, and 0.1 g of Cat.-4 catalyst was added. The reaction was allowed to proceed for 5 h. After the reaction, the reaction solution was filtered to obtain the liquid product and the solid catalyst. The liquid product was analyzed by GC-MS, and the results were calculated using the area normalization method. The test results are shown in Table 1.

[0035] Application Example 5 Accurately weigh 0.087 ml of furfuryl alcohol and 5 ml of 2-pentanol, add them to a 50 ml three-necked flask, adjust the stirring speed of the magnetic stirrer to 550 r / min, seal the flask, and purge with high-purity nitrogen for 5 min, maintaining a nitrogen atmosphere at 50 m... 3 The mixture was purged at a flow rate of [flow rate missing] / h, heated to 120 °C, and 0.1 g of Cat.-5 catalyst was added. The reaction was allowed to proceed for 5 h. After the reaction, the reaction solution was filtered to obtain the liquid product and the solid catalyst. The liquid product was analyzed by GC-MS, and the results were calculated using the area normalization method. The test results are shown in Table 1.

[0036] Application Comparative Example 1 Accurately weigh 0.087 ml of furfuryl alcohol and 5 ml of 2-pentanol, add them to a 50 ml three-necked flask, adjust the stirring speed of the magnetic stirrer to 550 r / min, seal the flask, and purge with high-purity nitrogen for 5 min, maintaining a nitrogen atmosphere at 50 m... 3 The mixture was purged at a flow rate of [flow rate missing] / h, heated to 120 °C, and 0.1 g of Cat.-6 catalyst was added. The reaction was allowed to proceed for 5 h. After the reaction, the reaction solution was filtered to obtain the liquid product and the solid catalyst. The liquid product was analyzed by GC-MS, and the results were calculated using the area normalization method. The test results are shown in Table 1.

[0037] Application Comparative Example 2 Accurately weigh 0.087 ml of furfuryl alcohol and 5 ml of 2-pentanol, add them to a 50 ml three-necked flask, adjust the stirring speed of the magnetic stirrer to 550 r / min, seal the flask, and purge with high-purity nitrogen for 5 min, maintaining a nitrogen atmosphere at 50 m... 3The mixture was purged at a flow rate of [flow rate missing] / h, heated to 120 °C, and 0.1 g of Cat.-7 catalyst was added. The reaction was allowed to proceed for 5 h. After the reaction, the reaction solution was filtered to obtain the liquid product and the solid catalyst. The liquid product was analyzed by GC-MS, and the results were calculated using the area normalization method. The test results are shown in Table 1.

[0038] Application Comparative Example 3 Accurately weigh 0.087 ml of furfuryl alcohol and 5 ml of 2-pentanol, add them to a 50 ml three-necked flask, adjust the stirring speed of the magnetic stirrer to 550 r / min, seal the flask, and purge with high-purity nitrogen for 5 min, maintaining a nitrogen atmosphere at 50 m... 3 The mixture was purged at a flow rate of [flow rate missing] / h, heated to 120 °C, and 0.1 g of Cat.-8 catalyst was added. The reaction was allowed to proceed for 5 h. After the reaction, the reaction solution was filtered to obtain the liquid product and the solid catalyst. The liquid product was analyzed by GC-MS, and the results were calculated using the area normalization method. The test results are shown in Table 1.

[0039] Table 1. Texture parameters and activity test results at 120 °C for the catalysts of the examples and comparative examples. The results show that the H-Beta molecular sieve catalyst prepared in Example 2 of this invention, with a SiO2 to TEAOH molar ratio of 6, catalyzes the preparation of β-angelicol from furfuryl alcohol at a reaction temperature of 120 °C under normal pressure and nitrogen conditions. The conversion rate of furfuryl alcohol and the selectivity for β-angelicol are significantly higher than those of catalysts with other TEAOH addition ratios (Examples 1, 3, 4, and 5), and also higher than those of commercial Beta molecular sieve catalysts with different Si / Al ratios (Comparative Examples 1, 2, and 3). This can be attributed to the large specific surface area and abundant Bronsted acidic sites of the synthesized H-Beta molecular sieve. Therefore, the catalyst described in this invention for the preparation of β-angelicol from furfuryl alcohol exhibits superior catalytic activity compared to other catalysts, realizing the conversion of the low-value chemical furfuryl alcohol into the high-value chemical angelicol, and demonstrating promising industrial application prospects.

[0040] The activity of the prepared Cat.-2 catalyst was tested at different time points. The specific procedure was as follows: 0.087 ml of furfuryl alcohol and 5 ml of 2-pentanol were accurately weighed and added to a 50 ml three-necked flask. The magnetic stirrer was adjusted to a stirring speed of 550 r / min, the flask was sealed, and the mixture was purged with high-purity nitrogen for 5 min, maintaining a nitrogen atmosphere of 50 m. 3 The mixture was purged at a flow rate of [flow rate missing] / h, heated to 120 °C, and 0.1 g of Cat.-2 catalyst was added. Reaction times were 5, 30, 60, 180, and 300 min, respectively. The reaction solution was filtered to obtain the liquid product and solid catalyst. The liquid product was analyzed by GC-MS, and the results were calculated using the area normalization method. The determination results are shown in the attached figure. Figure 2 As shown.

[0041] Depend on Figure 2 According to relevant theories, during the catalytic preparation of β-angelicin (β-AL) by furfuryl alcohol (FA), the intermediate product furfuryl ether (FE) is rapidly generated, gradually decreasing over time and transforming into α-angelicin (α-AL), β-angelicin (β-AL), and levulinate (LE). At 5 h, the selectivity of β-angelicin is the highest, reaching 82.63%. Due to the limited number of Bronsted acidic sites on the catalyst, not all furfuryl ether can be converted into angelicin, and a small amount of the byproduct levulinate is present in the product.

[0042] The above description is only a preferred embodiment of the present invention. All equivalent changes and modifications made within the scope of the claims of the present invention should be included in the scope of the present invention.

Claims

1. A catalyst for the preparation of β-angelicol from furfuryl alcohol, characterized in that, It is prepared from at least the following raw materials: sodium aluminate, SiO2, Beta molecular sieve seed crystals and TEAOH solution.

2. The catalyst for the preparation of β-angelicol from furfuryl alcohol according to claim 1, characterized in that, The molar ratio of SiO2 to sodium aluminate is 6~∞.

3. The catalyst for the preparation of β-angelicol from furfuryl alcohol according to claim 1, characterized in that, The silicon-to-aluminum ratio of Beta molecular sieve seed crystals should be close to or consistent with the silicon-to-aluminum ratio of SiO2 / sodium aluminate.

4. The catalyst for the preparation of β-angelicol from furfuryl alcohol according to claim 1, characterized in that, The concentration of the TEAOH solution is 20-40 wt%, and the molar ratio of SiO2 to TEAOH is 1.5-7.

5.

5. The catalyst for the preparation of β-angelicol from furfuryl alcohol according to any one of claims 1-4, characterized in that, The preparation process of the catalyst includes the following steps: 1) Sodium aluminate, TEAOH solution, SiO2, and Beta molecular sieve seed crystals were ground into a gel by mechanochemical method and transferred into a hydrothermal reactor and kept at 130-190 °C for 24-96 h. 2) The product obtained in step 1) is washed with water, filtered, and then dried overnight in an oven; 3) The dried product obtained in step 2) is calcined in a muffle furnace at 450~650 ℃ for 3~6 h; 4) The calcined product obtained in step 3) is subjected to ion exchange, that is, the calcined product is mixed with 2 M NH4Cl aqueous solution at a solid-liquid ratio of 1g:60mL, stirred at 40~80 ℃ for 4~10 h, then washed with water, filtered, and dried in an oven overnight. 5) The product obtained in step 4) is calcined in a muffle furnace at 450~650 °C for 3~6 h to obtain an H-Beta molecular sieve catalyst for the preparation of β-angelicin from furfuryl alcohol.

6. The catalyst for the preparation of β-angelicol from furfuryl alcohol according to claim 5, characterized in that, Step 4) involves three ion exchange operations.

7. The catalyst for the preparation of β-angelicol from furfuryl alcohol according to claim 5, characterized in that, The pore volume of the H-Beta molecular sieve catalyst is 0.10~0.80 cm³. 3 / g, specific surface area of ​​200~800 m² 2 / g.

8. The application of the H-Beta molecular sieve catalyst according to claim 6 or 7 in the conversion of furfuryl alcohol to β-angelicol.

9. The application according to claim 8, characterized in that, The reaction conditions for the preparation of β-angelic lactone from furfuryl alcohol catalyzed by H-Beta molecular sieve are as follows: the reaction atmosphere is an inert gas, the reaction solvent is a low carbon alcohol of C2-C5, the reaction temperature is 333~433 K, and the reaction time is 0.2~5 h.

10. The application according to claim 9, characterized in that, The mass percentage of furfuryl alcohol raw material to solvent is 5~40wt%, and the ratio of catalyst to furfuryl alcohol raw material is 0.01~0.1 g / 1 ml.

Images