Catalyst for producing linear end-terminated c5 and c3 diols and use thereof
By using a supported, inexpensive metal catalyst to catalyze the hydrogenation of tetrahydropyran hydroxypropionate, the problems of glutaric acid shortage and harsh production conditions of 1,3-propanediol were solved, enabling the efficient production of bio-based 1,5-pentanediol and 1,3-propanediol.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- DALIAN INSTITUTE OF CHEMICAL PHYSICS CHINESE ACADEMY OF SCIENCES
- Filing Date
- 2022-11-14
- Publication Date
- 2026-06-12
Smart Images
Figure CN118022751B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to a catalyst for producing linear C5 and C3 diols and its applications. Background Technology
[0002] 1,5-Pentanediol is an important odd-numbered carbon diol, primarily used in the production of polymeric materials such as polyesters and polyurethanes. It can also be used in the production of UV-curable coatings, plasticizers, fragrances, and inks. 1,3-Propanediol is also an important odd-numbered carbon diol, mainly used in the production of polyesters and polyurethanes.
[0003] Industrially, 1,5-pentanediol is produced from glutaric acid via direct hydrogenation or esterification with methanol followed by hydrogenation. The main companies possessing these technologies are BASF in Germany and UBE in Japan. Glutaric acid is a byproduct of the oxidation of cyclohexane to adipic acid; its limited availability and low yield restrict the production scale of 1,5-pentanediol.
[0004] The main methods for industrial production of 1,3-propanediol include DuPont's glycerol fermentation method, Evonik's acrolein hydration method, and Shell's ethylene oxide method. Currently, the fermentation method suffers from low efficiency, the acrolein method uses toxic raw materials, and the ethylene oxide method requires stringent high-temperature and high-pressure conditions.
[0005] Lignocellulosic biomass is the only abundant and CO2-neutral carbon-containing renewable resource, and its conversion and utilization align with the concept of sustainable green development. Furfural, currently the most widely used chemical in biomass industrial applications, is driving the development and progress of the biomass industry. The technologies for hydrogenating furfural to tetrahydrofurfuryl alcohol and dehydrating tetrahydrofurfuryl alcohol to dihydropyran are relatively mature and have been successfully applied industrially. Furthermore, the technology for producing 3-hydroxypropionic acid through biomass fermentation is developing rapidly, with extensive research propelling this technology towards industrial application. Dihydropyran and 3-hydroxypropionic acid can react via a C=C double bond addition reaction to produce tetrahydropyran hydroxypropionate, an important bio-based platform material.
[0006] Therefore, using tetrahydropyran hydroxypropionate as a raw material, 1,5-pentanediol and 1,3-propanediol can be co-produced through a hydrogenation process, simultaneously achieving the production of two key bio-based polyester odd-carbon diol monomers from bio-based platform compounds. This method uses inexpensive metal catalysts, the catalyst preparation method is simple, highly controllable, and exhibits high reaction activity and product selectivity. The process is green and simple. Summary of the Invention
[0007] The purpose of this invention is to provide a catalyst for the production of linear C5 and C3 diols and its application. By using the supported, inexpensive metal catalyst of this invention, the bio-based platform compound tetrahydropyran hydroxypropionate can be hydrogenated simultaneously to produce 1,5-pentanediol and 1,3-propanediol. The catalyst and its application overcome the problem of glutaric acid shortage in the existing 1,5-pentanediol production process, and also overcome the problems of harsh conditions, high feedstock toxicity, and low efficiency of fermentation methods in the 1,3-propanediol production process.
[0008] The technical solution adopted in this invention is as follows:
[0009] This invention discloses a catalyst for producing linear C5 and C3 diols and its application. The catalyst consists of two active metal components, M1 and M2, an auxiliary metal M3, and a support. M1 is copper, M2 is one or more of Co, Ni, and Fe, and M3 is one or more of Li, Na, K, Mg, Ca, Sr, Ba, La, Sm, and Ce. The support is coconut shell carbon.
[0010] In a preferred embodiment, the content of M1 is 5-40%, preferably 10-35%, more preferably 15-30%, and most preferably 18-25%; the content of M2 is 2-10%, preferably 3-8%, more preferably 3-6%, and most preferably 3-5%; and the content of M3 is 0.1-5%, preferably 0.2-4%, more preferably 0.5-3%, and most preferably 0.5-2%.
[0011] In a preferred embodiment, the activated carbon from fruit shells is one or more of the following: apricot shell carbon, coconut shell carbon, peach kernel shell carbon, pistachio shell carbon, ginkgo shell carbon, and plum shell carbon.
[0012] In a preferred embodiment, the catalyst is prepared by impregnation, specifically including first impregnating M1 and M2, then impregnating M3 after drying and calcination, and then drying and calcining again to obtain the catalyst; or first impregnating M3 on the support, then impregnating M1 and M2 after drying and calcination, and then drying and calcining again to obtain the catalyst; or simultaneously impregnating M1, M2 and M3 onto the support, and then drying and calcining to obtain the catalyst.
[0013] In a preferred embodiment, the drying temperature is 60–100°C, preferably 60–90°C, more preferably 60–80°C, and most preferably 60–70°C.
[0014] In a preferred embodiment, the calcination temperature is 250–600°C, preferably 280–550°C, more preferably 300–500°C, and most preferably 350–450°C. The calcination is carried out in one or more atmospheres of N2, Ar, and He, and the calcination time is 1–48 hours.
[0015] The present invention also discloses the application of the above-mentioned catalyst in the hydrogenation reaction of tetrahydropyran hydroxypropionate, which can catalyze the hydrogenation of tetrahydropyran hydroxypropionate in a hydrogen atmosphere to co-produce 1,5-pentanediol and 1,3-propanediol (linear terminal C5 and C3 diols).
[0016] In a preferred embodiment, the reaction temperature is 150–300°C, preferably 160–270°C, more preferably 170–250°C, and most preferably 180–230°C; the hydrogen pressure is 1–80 atm, preferably 5–60 atm, more preferably 10–50 atm, and most preferably 20–40 atm. The reactor used for the hydrogenation reaction is selected from a fixed-bed, slurry-bed, fluidized-bed, or reaction vessel.
[0017] In a preferred embodiment, tetrahydropyran hydroxypropionate is fed in solution form, and the solvent used is one or more of dioxane, tetrahydropyran, propanol, ethanol, and methanol. The concentration of tetrahydropyran hydroxypropionate is 5-100%, preferably 5-60%, more preferably 5-40%, and most preferably 5-30%.
[0018] Compared with existing technologies, the advantages of this invention are as follows: This invention can use the bio-based derivative tetrahydropyran hydroxypropionate as a raw material, and through a low-cost metal-catalyzed hydrogenation process, co-produce bio-based 1,5-pentanediol and 1,3-propanediol, achieving high reactivity and product selectivity. Furthermore, the catalyst preparation method is simple, highly controllable, and the catalyst preparation and application process is green and simple. Detailed Implementation
[0019] The present invention will be further illustrated below with specific embodiments. The contents and percentages in this application are all based on mass, and the product selectivity is calculated based on the theoretical selectivity.
[0020] Example 1
[0021] 1000g of coconut shell activated carbon carrier was washed three times by boiling in deionized water and dried at 393K for 12 hours to obtain the carrier material AC1 for preparing the catalyst.
[0022] Catalyst A has the composition 18Cu3Fe0.5K / AC1 (the numbers before the metals represent the mass percentage of the metal in the catalyst; the meaning is the same in the examples below). 40-60 mesh treated coconut shell activated carbon was used as the support. The catalyst preparation method was carried out according to the following steps: A certain amount of copper nitrate, ferric nitrate, and potassium nitrate were dissolved in deionized water to prepare a mixed solution with a metal salt concentration of 0.25M. The prepared solution was loaded onto the activated carbon support using an impregnation method. It was air-dried at room temperature for the time required for the catalyst to reach a dry state, then dried in air at 60°C for 12 hours, followed by calcination at 350°C in an argon atmosphere for 3 hours to obtain the catalyst A oxide precursor. 1g of catalyst A was loaded into a fixed-bed reactor and first underwent in-situ hydrogen activation under the conditions of a pressure of 0.1MPa and a space velocity of 1000h⁻¹. -1 The temperature was 350℃ for reduction for 10 hours. After activation, the temperature was lowered to 200℃, the hydrogen pressure was increased to 4 MPa, and a dioxane solution of tetrahydropyran hydroxypropionate (10% by mass) was used as the raw material, with a liquid hourly space velocity of 1 h⁻¹. -1 The molar ratio of hydrogen to ester was 20. After the reaction stabilized for 24 hours, the product was collected for analysis and calculation. The conversion rate of hydroxytetrahydropyran was 85%, the selectivity of 1,5-pentanediol was 88%, and the selectivity of 1,3-propanediol was 90%.
[0023] Example 2
[0024] 1000g of coconut shell activated carbon carrier was washed three times by boiling in deionized water and dried at 393K for 12 hours to obtain the carrier material AC1 for preparing the catalyst.
[0025] Catalyst B has a composition of 20Cu5Ni1Ce / AC1 and uses 40-60 mesh treated coconut shell activated carbon as a support. The catalyst preparation method is as follows: A certain amount of copper nitrate, nickel nitrate, and cerium nitrate were dissolved in deionized water to prepare a mixed solution with a metal salt concentration of 0.25M. The prepared solution was loaded onto the activated carbon support by impregnation. It was air-dried at room temperature for the time required for the catalyst to reach a dry state, then dried in air at 60°C for 12 hours, followed by calcination at 450°C in an argon atmosphere for 2 hours to obtain the catalyst B oxide precursor. The reaction conditions of the catalyst were the same as in Example 1. After the reaction stabilized for 24 hours, the product was collected for analysis and calculation. The conversion rate of hydroxytetrahydropyran was 91%, the selectivity of 1,5-pentanediol was 90%, and the selectivity of 1,3-propanediol was 93%.
[0026] Example 3
[0027] 1000g of coconut shell activated carbon carrier was washed three times by boiling in deionized water and dried at 393K for 12 hours to obtain the carrier material AC1 for preparing the catalyst.
[0028] Catalyst C has the composition 25Cu4Co2Sr / AC1, using 40-60 mesh treated coconut shell activated carbon as a support. The catalyst preparation method is as follows: A certain amount of copper nitrate, cobalt nitrate, and strontium nitrate were dissolved in deionized water to prepare a mixed solution with a metal salt concentration of 0.25M. The prepared solution was loaded onto the activated carbon support by impregnation. It was air-dried at room temperature for the time required for the catalyst to reach a dry state, then dried in air at 60°C for 12 hours, followed by calcination at 400°C in an argon atmosphere for 2 hours to obtain the catalyst C oxide precursor. The reaction conditions for the catalyst were the same as in Example 1. After the reaction stabilized for 24 hours, the products were collected for analysis and calculation. The conversion rate of hydroxytetrahydropyran was 93%, the selectivity for 1,5-pentanediol was 92%, and the selectivity for 1,3-propanediol was 93%.
[0029] Example 4
[0030] 1000g of coconut shell activated carbon carrier was washed three times by boiling in deionized water and dried at 393K for 12 hours to obtain the carrier material AC1 for preparing the catalyst.
[0031] Catalyst D has a composition of 25Cu4Co1Mg / AC1, using 40-60 mesh treated coconut shell activated carbon as a support. The catalyst preparation method is as follows: A certain amount of copper nitrate, cobalt nitrate, and magnesium nitrate were dissolved in deionized water to prepare a mixed solution with a metal salt concentration of 0.25M. The prepared solution was loaded onto the activated carbon support by impregnation. It was air-dried at room temperature for the time required for the catalyst to reach a dry state, then dried in air at 60°C for 12 hours, followed by calcination at 400°C in an argon atmosphere for 2 hours to obtain the catalyst D oxide precursor. The reaction conditions for the catalyst were the same as in Example 1. After the reaction stabilized for 24 hours, the products were collected for analysis and calculation. The conversion rate of hydroxytetrahydropyran was 89%, the selectivity for 1,5-pentanediol was 90%, and the selectivity for 1,3-propanediol was 91%.
[0032] Example 5
[0033] 1000g of coconut shell activated carbon carrier was washed three times by boiling in deionized water and dried at 393K for 12 hours to obtain the carrier material AC1 for preparing the catalyst.
[0034] Catalyst E has the composition 22Cu3Co2Ni0.5Li / AC1, using 40-60 mesh treated coconut shell activated carbon as a support. The catalyst preparation method is as follows: A certain amount of copper nitrate, cobalt nitrate, nickel nitrate, and lithium nitrate were dissolved in deionized water to prepare a mixed solution with a metal salt concentration of 0.25M. The prepared solution was loaded onto the activated carbon support by impregnation. It was air-dried at room temperature for the time required for the catalyst to reach a dry state, then dried in air at 60°C for 12 hours, followed by calcination at 350°C in an argon atmosphere for 2 hours to obtain the catalyst E oxide precursor. The reaction conditions for the catalyst were the same as in Example 1. After the reaction stabilized for 24 hours, the product was collected for analysis and calculation. The conversion rate of hydroxytetrahydropyran was 92%, the selectivity for 1,5-pentanediol was 88%, and the selectivity for 1,3-propanediol was 90%.
[0035] Example 6
[0036] 1000g of coconut shell activated carbon carrier was washed three times by boiling in deionized water and dried at 393K for 12 hours to obtain the carrier material AC1 for preparing the catalyst.
[0037] Catalyst F has the composition 25Cu1Fe2Ni0.8Na / AC1, and uses coconut shell activated carbon treated with 40-60 mesh as a support. The catalyst preparation method is as follows: A certain amount of copper nitrate, ferric nitrate, nickel nitrate, and sodium nitrate were dissolved in deionized water to prepare a mixed solution with a metal salt concentration of 0.25M. The prepared solution was loaded onto the activated carbon support by impregnation. It was air-dried at room temperature for the time required for the catalyst to reach a dry state, then dried in air at 60°C for 12 hours, followed by calcination at 350°C in an argon atmosphere for 2 hours to obtain the catalyst F oxide precursor. The reaction conditions of the catalyst were the same as in Example 1. After the reaction stabilized for 24 hours, the product was collected for analysis and calculation. The conversion rate of hydroxytetrahydropyran was 94%, the selectivity of 1,5-pentanediol was 90%, and the selectivity of 1,3-propanediol was 92%.
[0038] Example 7
[0039] 1000g of apricot shell activated carbon carrier was washed three times by boiling in deionized water and dried at 393K for 12 hours to obtain the carrier material AC2 for preparing the catalyst.
[0040] Catalyst G had a composition of 25Cu4Co2Sr / AC2, and its metal composition, preparation method, and parameters were consistent with those in Example 3, except that treated apricot shell activated carbon AC2 was used instead of coconut shell activated carbon AC1. The evaluation methods and conditions for the catalyst were consistent with those in Example 1. After the reaction stabilized for 24 hours, the products were collected for analysis and calculation. The conversion rate of hydroxytetrahydropyran was 95%, the selectivity for 1,5-pentanediol was 90%, and the selectivity for 1,3-propanediol was 92%.
[0041] Example 8
[0042] 1000g of apricot shell activated carbon carrier was washed three times by boiling in deionized water and dried at 393K for 12 hours to obtain the carrier material AC2 for preparing the catalyst.
[0043] Catalyst G had the composition 22Cu3Co2Ni0.5Li / AC2, and its metal composition, preparation method, and parameters were consistent with those of Example 5, except that treated apricot shell activated carbon AC2 was used instead of coconut shell activated carbon AC1. The evaluation methods and conditions for the catalyst were consistent with those of Example 1. After the reaction stabilized for 24 hours, the products were collected for analysis and calculation. The conversion rate of hydroxytetrahydropyran was 93%, the selectivity for 1,5-pentanediol was 91%, and the selectivity for 1,3-propanediol was 93%.
[0044] Comparative Example 1
[0045] 1000g of coconut shell activated carbon carrier was washed three times by boiling in deionized water and dried at 393K for 12 hours to obtain the carrier material AC1 for preparing the catalyst.
[0046] 1g of treated coconut shell activated carbon AC1 was loaded into a fixed-bed reactor, and in-situ hydrogen treatment was first performed under the conditions of 0.1MPa pressure and 1000h space velocity. -1 The temperature was maintained at 350℃ for 10 hours for reduction. Afterwards, the temperature was lowered to 200℃, the hydrogen pressure was increased to 4 MPa, and a self-made dioxane solution of tetrahydropyran hydroxypropionate (10% concentration) was used as the raw material, with a liquid hourly space velocity (LHSV) of 1 h⁻¹. -1 The molar ratio of hydrogen to ester was 20. After the reaction stabilized for 24 hours, the product was collected for analysis and calculation. The conversion rate of hydroxytetrahydropyran was 2%, and 1,5-pentanediol and 1,3-propanediol were not detected in the product.
[0047] Comparative Example 2
[0048] 1000g of coconut shell activated carbon carrier was washed three times by boiling in deionized water and dried at 393K for 12 hours to obtain the carrier material AC1 for preparing the catalyst.
[0049] Catalyst H has a composition of 18Cu / AC1 and uses 40-60 mesh treated coconut shell activated carbon as a support. The catalyst preparation method is as follows: A certain amount of copper nitrate was dissolved in deionized water to prepare a mixed solution with a metal salt concentration of 0.25M. The prepared solution was loaded onto the activated carbon support by impregnation. It was air-dried at room temperature for the time required for the catalyst to reach a dry state, then dried in air at 60°C for 12 hours, followed by calcination at 350°C in an argon atmosphere for 3 hours to obtain the catalyst H oxide precursor. The catalyst evaluation methods and conditions were the same as in Example 1. After the reaction stabilized for 24 hours, the product was collected for analysis and calculation. The conversion rate of hydroxytetrahydropyran was 65%, the selectivity for 1,5-pentanediol was 71%, and the selectivity for 1,3-propanediol was 78%.
[0050] Comparative Example 3
[0051] 1000g of coconut shell activated carbon carrier was washed three times by boiling in deionized water and dried at 393K for 12 hours to obtain the carrier material AC1 for preparing the catalyst.
[0052] Catalyst I has a composition of 3Fe / AC1 and uses coconut shell activated carbon treated with 40-60 mesh as a support. The catalyst preparation method is as follows: A certain amount of ferric nitrate was dissolved in deionized water to prepare a mixed solution with a metal salt concentration of 0.25M. The prepared solution was loaded onto the activated carbon support by impregnation. It was air-dried at room temperature for the time required for the catalyst to reach a dry state, and then dried in air at 60°C for 12 hours, followed by calcination at 350°C in an argon atmosphere for 3 hours to obtain the catalyst I oxide precursor. The catalyst evaluation method and conditions were the same as in Example 1. After the reaction stabilized for 24 hours, the product was collected for analysis and calculation. The conversion rate of hydroxytetrahydropyran was 5%, the selectivity of 1,5-pentanediol was 50%, and the selectivity of 1,3-propanediol was 56%.
[0053] Comparative Example 4
[0054] 1000g of coconut shell activated carbon carrier was washed three times by boiling in deionized water and dried at 393K for 12 hours to obtain the carrier material AC1 for preparing the catalyst.
[0055] Catalyst J has the composition 18Cu0.5K / AC1, using 40-60 mesh treated coconut shell activated carbon as a support. The catalyst preparation method is as follows: A certain amount of copper nitrate and potassium nitrate were dissolved in deionized water to prepare a mixed solution with a metal salt concentration of 0.25M. The prepared solution was loaded onto the activated carbon support by impregnation. It was air-dried at room temperature for the time required for the catalyst to reach a dry state, then dried in air at 60°C for 12 hours, followed by calcination at 350°C in an argon atmosphere for 3 hours to obtain the catalyst J oxide precursor. The catalyst evaluation methods and conditions were the same as in Example 1. After the reaction stabilized for 24 hours, the products were collected for analysis and calculation. The conversion rate of hydroxytetrahydropyran was 67%, the selectivity of 1,5-pentanediol was 74%, and the selectivity of 1,3-propanediol was 81%.
[0056] Comparative Example 5
[0057] 1000g of coconut shell activated carbon carrier was washed three times by boiling in deionized water and dried at 393K for 12 hours to obtain the carrier material AC1 for preparing the catalyst.
[0058] The catalyst K had a composition of 3Fe0.5K / AC1, using 40-60 mesh treated coconut shell activated carbon as a support. The catalyst preparation method was carried out according to the following steps: A certain amount of ferric nitrate and potassium nitrate were dissolved in deionized water to prepare a mixed solution with a metal salt concentration of 0.25M. The prepared solution was loaded onto the activated carbon support by impregnation. It was air-dried at room temperature for the time required for the catalyst to reach a dry state, then dried in air at 60°C for 12 hours, followed by calcination at 350°C in an argon atmosphere for 3 hours to obtain the catalyst K oxide precursor. The catalyst evaluation methods and conditions were the same as in Example 1. After the reaction stabilized for 24 hours, the product was collected for analysis and calculation. The conversion rate of hydroxytetrahydropyran was 6%, the selectivity for 1,5-pentanediol was 52%, and the selectivity for 1,3-propanediol was 59%.
[0059] As shown in Comparative Example 1, tetrahydropyran hydroxypropionate does not undergo hydrogenation to produce 1,5-pentanediol and 1,3-propanediol in the absence of a metal component. Examples 1 and Comparative Examples 2-5 demonstrate that activated carbon-supported copper-based catalysts, activated carbon-supported iron catalysts, activated carbon-supported copper-potassium catalysts, and activated carbon-supported iron-potassium catalysts can all catalyze the hydrogenation of tetrahydropyran hydroxypropionate, but their activity and selectivity are relatively low. Using the three-component catalyst of this invention can significantly improve the catalyst activity and product selectivity. Furthermore, Examples 1-8 show that the multi-component catalysts of this invention all exhibit excellent performance in the hydrogenation of tetrahydropyran hydroxypropionate to terminal linear diols. Therefore, the method of this invention can achieve highly active and selective co-production of bio-based 1,5-pentanediol and 1,3-propanediol from the bio-based platform compound tetrahydropyran hydroxypropionate via a low-cost metal catalyst.
Claims
1. The application of a catalyst in the production of linear terminal C5 and C3 diols in the hydrogenation reaction of tetrahydropyran hydroxypropionate, characterized in that: The catalyst consists of two metallic active components, M1 and M2, an auxiliary agent, M3, and a support. M1 is metallic copper, M2 is one or more of Co, Ni, and Fe, and M3 is one or more of Li, Na, K, Mg, Ca, Sr, Ba, La, Sm, and Ce. The support is coconut shell activated carbon. The catalyst oxide precursor is prepared by an impregnation method, specifically including first impregnating M1 and M2, drying and calcining, then impregnating M3, and drying and calcining to obtain the catalyst oxide precursor; or, first impregnating the support with M3, drying and calcining... The catalyst is prepared by dry calcination, impregnation with M1 and M2, and drying and calcination to obtain a catalyst oxide precursor; or, M1, M2 and M3 are simultaneously impregnated onto a support, dried and calcined to obtain a catalyst oxide precursor, and the catalyst oxide precursor is activated in a hydrogen atmosphere to obtain the catalyst, which is then used to catalyze the hydrogenation of tetrahydropyran hydroxypropionate to co-produce 1,5-pentanediol and 1,3-propanediol in a hydrogen atmosphere. The mass content of M1 in the catalyst is 5-40%, the mass content of M2 is 2-10%, and the mass content of M3 is 0.1-5%.
2. The application according to claim 1, characterized in that, The catalyst contains 10-35% M1 by mass, 3-8% M2 by mass, and 0.2-4% M3 by mass.
3. The application according to claim 1, characterized in that, Fruit shell activated carbon is one or more of the following: apricot shell carbon, coconut shell carbon, peach kernel shell carbon, pistachio shell carbon, ginkgo shell carbon, and plum shell carbon.
4. The application according to claim 1, characterized in that, When M1, M2 and M3 are simultaneously impregnated onto the carrier, the drying temperature is 60~100℃.
5. The application according to claim 1, characterized in that, When M1, M2 and M3 are simultaneously impregnated onto the carrier, the calcination temperature is 250~600℃, and the calcination is carried out in one or more atmospheres of N2, Ar and He, for 1-48 hours.
6. The application according to claim 1, characterized in that, The reaction temperature is 150~300℃; the hydrogen pressure is 1~80 atm; and the reactor used for the hydrogenation reaction is selected from one of the following: fixed bed, slurry bed, fluidized bed, or reaction vessel.
7. The application according to claim 6, characterized in that, The reaction temperature is 160~270℃; the hydrogen pressure is 5~60 atm.
8. The application according to claim 1, characterized in that, Tetrahydropyran hydroxypropionate is fed in solution form, and the solvent used is one or more of dioxane, tetrahydropyran, propanol, ethanol, and methanol. The mass concentration of tetrahydropyran hydroxypropionate in the solution is 5-100%.
9. The application according to claim 1, characterized in that, The activation is carried out in a hydrogen-containing atmosphere, with a hydrogen content of 0.05% to 100%, and the remaining gases being nitrogen and / or argon. The activation conditions are: temperature 100 to 800°C, time 0.5 to 72 h, and space velocity 10 to 10000 h⁻¹. -1 .