CN110639513A - Preparation method and application of catalyst for preparing 1, 6-hexanediol by directly hydrogenating adipic acid - Google Patents
Preparation method and application of catalyst for preparing 1, 6-hexanediol by directly hydrogenating adipic acid Download PDFInfo
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- CN110639513A CN110639513A CN201910998872.4A CN201910998872A CN110639513A CN 110639513 A CN110639513 A CN 110639513A CN 201910998872 A CN201910998872 A CN 201910998872A CN 110639513 A CN110639513 A CN 110639513A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/468—Iridium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6567—Rhenium
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
Abstract
The invention belongs to the technical field of heterogeneous catalysis, and provides a preparation method and application of a catalyst for preparing 1, 6-hexanediol by directly hydrogenating adipic acid. Specifically, one or two of iridium, palladium, platinum and rhenium are used as active components, and are loaded on one or more carriers of carbon nanotubes, activated carbon, graphite and the like, and HCl, HF and Na are not used or added2CO3、NaHCO3Or one or more mixed auxiliary dispersing agents in NaOH, and the total metal content is 0.3-5.0wt percent. Catalytic hydrogenation is carried out in a continuous stirred tank reactor under the pressure of 2-10MPa and at the temperature of 80-220 DEG CAdipic acid for 2-10 h. Aiming at the problems of harsh preparation process, low productivity, complex process conditions and the like of the 1, 6-hexanediol, the invention develops a novel high-efficiency supported noble metal catalyst and has high practicability.
Description
Technical Field
The invention belongs to the technical field of heterogeneous catalysis, and particularly relates to a preparation method and application of a catalyst for preparing 1, 6-hexanediol by directly hydrogenating adipic acid. The high-efficiency supported noble metal catalyst is designed, and has high practicability aiming at solving the problems of harsh preparation process, low productivity, complex process conditions and the like of the 1, 6-hexanediol.
Background
1, 6-hexanediol is an important fine chemical raw material and is mainly used for producing high-quality chemical products such as polyurethane elastomer resin, polyester plasticizers, food additives and the like. In the production process of the dye and the polyester, the hexanediol can effectively improve the buffer performance, the color and the adsorption capacity of the product and has excellent light stability. In the production of polyurethane, the hexanediol can effectively improve the hydrolysis resistance and mechanical strength of products, and the performance of the polyurethane produced by using the hexanediol as a raw material is far higher than that of other types of polyurethane. Therefore, hexanediol is known as a new base stone for organic synthesis, and the development and optimization of the production process of hexanediol have important industrial application prospects.
At present, adipic acid is generally adopted as a raw material at home and abroad to produce 1, 6-hexanediol, and dimethyl adipate is firstly generated through an esterification reaction with methanol under the action of a catalyst, or the dimethyl adipate is directly adopted as the raw material to produce the 1, 6-hexanediol through catalytic hydrogenation. The intermittent esterification hydrogenation alcohol preparation process is generally carried out in a high-pressure reaction kettle, and the reaction pressure is too high and even exceeds 30 MPa. The harsh production conditions cause the danger coefficient of the production process to be extremely high, the stability to be poor and the industrialization process to be not facilitated; the continuous hydrogenation alcohol preparation process is adopted, although the esterification hydrogenation process can be carried out under the condition that the pressure is lower than 10MPa, the liquid space velocity is low, the hydrogen-ester molar ratio is as high as 300, and the energy utilization rate is extremely low.
Patent CN103124713 describes a process for preparing 1, 6-hexanediol by hydrogenation of caprolactone and/or its oligomer or polymer, the catalyst uses copper as main active center, Mn, Ba and other elements as auxiliary agent, and Cr2O3As a carrier, the conversion rate of raw materials reaches 99.7 percent, 1The selectivity of 6-hexanediol can reach 96.7%. However, the pressure required by the hydrogenation reaction is as high as 10-35 MPa, and great potential safety hazards exist.
Patent CN101679157A reports a process for the preparation of 1, 5-pentanediol and/or 1, 6-hexanediol by esterification of monocarboxylic and dicarboxylic acids and hydrogenation in the presence of a copper-containing catalyst. However, the operating pressure of the method is up to 25MPa, the reaction temperature reaches 275 ℃, and the copper-based catalyst is easy to sinter and deactivate.
Patent CN104549254A reports a metal-supported catalyst for preparing 1, 6-hexanediol by directly reducing adipic acid, and Ru-based trimetal and/or tetrametallic catalysts are supported by taking activated carbon as a carrier, so that higher yield of hexanediol is obtained under the conditions of 5MPa and 180 ℃. However, the catalyst adopts 3-4 noble metal components, and the components and the preparation process are complicated and the cost is high.
In conclusion, the catalyst for preparing the 1, 6-hexanediol by directly hydrogenating the adipic acid, which is simple and efficient in preparation process, is developed, the preparation of the 1, 6-hexanediol with high yield is realized at lower reaction temperature and reaction pressure, the production process is simplified, the production cost is saved, the energy utilization rate is improved, and the catalyst has great strategic significance on the structure adjustment and transformation upgrading of petrochemical products.
Disclosure of Invention
The invention provides a catalyst for preparing 1, 6-hexanediol by directly hydrogenating adipic acid. Aiming at improving the energy utilization rate and solving the problems of harsh preparation process, low productivity, complex process conditions and the like of the 1, 6-hexanediol, a novel high-efficiency supported noble metal catalyst is developed, and the 1, 6-hexanediol is generated by directly hydrogenating adipic acid by adopting a continuous stirred tank reactor. The production process has low energy consumption and high energy utilization rate, and can effectively catalyze and convert the 1, 6-hexanediol as the target product.
The technical scheme of the invention is as follows:
a preparation method of a catalyst for preparing 1, 6-hexanediol by directly hydrogenating adipic acid comprises the following steps:
taking a carbon material as a carrier, taking a metal salt precursor solution of one or two of iridium, palladium, platinum and rhenium metal salts, and controlling the total metal loading amount to be 0.3-5 wt%; aging at room temperature for 12H without adding or adding auxiliary dispersion solution to adjust pH value of the solution, vacuum filtering, washing, transferring to a forced air drying oven, and drying overnight to obtain sample powder, and calcining at 200-600 deg.C for 2-8H in a tubular furnace mixed atmosphere of hydrogen and argon, wherein H2The volume fraction is not less than 10 percent, and the obtained adipic acid is directly hydrogenated to prepare the 1, 6-hexanediol catalyst.
The carbon material comprises one or more of carbon nano tube, activated carbon and graphite.
The auxiliary dispersion solution comprises HCl, HF and Na2CO3、NaHCO3And one or a mixture of two or more of NaOH.
The metal salt precursor comprises one or a mixture of more than two of acetylacetone salt, chloride, nitrate and ammonium salt.
The application of a catalyst for preparing 1, 6-hexanediol by directly hydrogenating adipic acid comprises the following steps:
adding adipic acid, a solvent and a reduced catalyst into a high-pressure reaction kettle, sealing the reaction kettle, filling hydrogen, replacing air in the kettle for 3 times, filling 2-10MPa pressure, and reacting at 80-220 ℃ for 2-10 h; and after the reaction is finished, cooling to room temperature, discharging gas to normal pressure, detecting reaction products by gas chromatography and liquid chromatography respectively after centrifugal separation, and separating to obtain the 1, 6-hexanediol product.
The mass concentration of the adipic acid in the solvent is 1-5%, the mass ratio of the catalyst to the adipic acid is 10-40%, and the solvent is one or a mixture of more than two of ethanol, water and ether.
The invention has the beneficial effects that: 1, 6-hexanediol is prepared by directly hydrogenating adipic acid at relatively low temperature and pressure by adopting a low-content supported noble metal-based catalyst. According to the method of the present invention, in some examples, the conversion of adipic acid was 87.98% and the selectivity of 1, 6-hexanediol was 40.88%, depending on the set reaction parameters.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of a 3 wt% Ir/C catalyst.
FIG. 2 is 3 wt% Ir1Re1X-ray diffraction (XRD) pattern of the/C catalyst.
FIG. 3 is 3 wt% Ir1Re1Transmission electron microscopy images of/C catalysts.
FIG. 4 is 3 wt% Ir1Re2Catalyst in H2And (5) characterization results of temperature programmed desorption under the atmosphere.
Detailed Description
The present invention is further illustrated by the following examples, which are intended to be purely exemplary of the invention and are not to be construed as limiting the scope of the invention.
Example 10.3 wt% Ir/C catalyst preparation
0.012g of iridium acetylacetonate was dissolved in 2.5mL of acetone, added to 1.5g of activated carbon, stirred and mixed uniformly at room temperature without adding an auxiliary dispersant, aged for 16 hours, filtered, washed and dried overnight, and the obtained powder was reduced at 400 ℃ for 4 hours in a tube furnace under a hydrogen-argon mixed atmosphere (volume ratio of hydrogen to argon: 1:2) to obtain 0.3% Ir/C catalyst powder.
Example 23 wt% Ir2Re1Preparation of the catalyst
Respectively weighing 0.077g of iridium acetylacetonate and 0.021g of ammonium perrhenate, respectively dissolving in acetone and deionized water, adding 1.5g of activated carbon, stirring and mixing uniformly at room temperature, aging for 16h, filtering, washing, drying overnight, and reducing the obtained powder at 400 ℃ for 4h in a tubular furnace under a hydrogen-argon mixed atmosphere (volume ratio is hydrogen: argon is 1:2) to obtain 3 wt% Ir2Re1a/C catalyst.
Example 33 wt% Pd1Re2Preparation of the catalyst
0.025g of palladium chloride and 0.043g of ammonium perrhenate were separately weighed, dissolved in deionized water, added to 1.5g of activated carbon, and 2mL of concentrated hydrochloric acid (37.5 wt%) was added as an auxiliary dispersant. Stirring and mixing uniformly at room temperature, aging for 16h, filtering, washing, drying overnight, and reducing the obtained powder at 400 ℃ for 4h in a tubular furnace under a hydrogen-argon mixed atmosphere (volume ratio of hydrogen to argon is 1:2) to obtain 3 wt% Pd1Re2a/C catalyst.
Example 4A reaction kettle was charged with 0.5g adipic acid, 20g deionized water, 0.2g 3 wt% Ir/C catalyst, and the X-ray diffraction (XRD) results for the catalyst are shown in FIG. 1. And (3) filling hydrogen after the reaction kettle is sealed, replacing the air in the kettle for 3 times, filling 8MPa pressure, heating to 180 ℃, and reacting for 10 hours. After the reaction is finished, cooling the reaction kettle to room temperature, discharging hydrogen in the kettle to normal pressure, after the reaction product is centrifugally separated, carrying out gas chromatography and liquid chromatography detection on the product, and separating to obtain the 1, 6-hexanediol product. The adipic acid conversion was 35.0% and the 1, 6-hexanediol selectivity was 18.0%.
Example 5 a reaction kettle was charged with 0.5g adipic acid, 20g deionized water, 0.2g of a 3 wt% Pd/C catalyst. And (3) sealing the reaction kettle, filling hydrogen, replacing the air in the kettle for 3 times, filling 8MPa pressure, heating to 180 ℃, and reacting for 8 hours. After the reaction is finished, discharging hydrogen in the kettle to normal pressure, after the reaction product is centrifugally separated, carrying out gas chromatography and liquid chromatography detection on the product, and separating to obtain the 1, 6-hexanediol product. The conversion of adipic acid was 18.5% and the selectivity to 1, 6-hexanediol was 15.7%.
Example 6A reaction kettle was charged with 0.5g of adipic acid, 20g of deionized water, 0.2g of 3 wt% Re/C catalyst. And (3) sealing the reaction kettle, filling hydrogen, replacing the air in the kettle for 3 times, filling 8MPa pressure, heating to 180 ℃, and reacting for 10 hours. After the reaction is finished, cooling the reaction kettle to room temperature, discharging hydrogen in the kettle to normal pressure, after the reaction product is centrifugally separated, carrying out gas chromatography and liquid chromatography detection on the product, and separating to obtain the 1, 6-hexanediol product. The conversion of adipic acid was 20.3% and the selectivity to 1, 6-hexanediol was 20.2%.
Example 7A reaction kettle was charged with 0.5g adipic acid, 20g deionized water, 0.2g 3 wt% Ir1Re1The catalyst/C, the X-ray diffraction (XRD) result and the micro-morphology of the catalyst are shown in figures 2-3. And (3) sealing the reaction kettle, filling hydrogen, replacing the air in the kettle for 3 times, filling 8MPa pressure, heating to 180 ℃, and reacting for 10 hours. After the reaction is finished, cooling the reaction kettle to room temperature, discharging hydrogen in the kettle to normal pressure, after the reaction product is centrifugally separated, detecting the product by gas chromatography and liquid chromatography, and separating to obtain the 1, 6-hexanediAn alcohol product. The adipic acid conversion was 88.0% and the 1, 6-hexanediol selectivity was 40.9%.
Example 8A reaction kettle was charged with 0.5g adipic acid, 20g deionized water, 0.2g 3 wt% Ir2Re1a/C catalyst. And (3) sealing the reaction kettle, filling hydrogen, replacing the air in the kettle for 3 times, filling 8MPa pressure, heating to 180 ℃, and reacting for 10 hours. After the reaction is finished, cooling the reaction kettle to room temperature, discharging hydrogen in the kettle to normal pressure, after the reaction product is centrifugally separated, carrying out gas chromatography and liquid chromatography detection on the product, and separating to obtain the 1, 6-hexanediol product. The adipic acid conversion was 66.3% and the 1, 6-hexanediol selectivity was 35.8%.
Example 9A reaction kettle was charged with 0.5g adipic acid, 20g deionized water, 0.2g 3 wt% Ir1Re2Catalyst in H2The temperature program curve under the atmosphere is shown in fig. 4. And (3) sealing the reaction kettle, filling hydrogen, replacing the air in the kettle for 3 times, filling 8MPa pressure, heating to 180 ℃, and reacting for 10 hours. After the reaction is finished, cooling the reaction kettle to room temperature, discharging hydrogen in the kettle to normal pressure, after the reaction product is centrifugally separated, carrying out gas chromatography and liquid chromatography detection on the product, and separating to obtain the 1, 6-hexanediol product. The adipic acid conversion was 47.5% and the 1, 6-hexanediol selectivity was 33.3%.
EXAMPLE 10A reaction kettle was charged with 0.5g adipic acid, 20g deionized water, 0.2g 3 wt% Pd1Re1a/C catalyst. And (3) sealing the reaction kettle, filling hydrogen, replacing the air in the kettle for 3 times, filling 8MPa pressure, heating to 180 ℃, and reacting for 8 hours. After the reaction is finished, discharging hydrogen in the kettle to normal pressure, after the reaction product is centrifugally separated, carrying out gas chromatography and liquid chromatography detection on the product, and separating to obtain the 1, 6-hexanediol product. The adipic acid conversion was 32.8% and the 1, 6-hexanediol selectivity was 25.6%.
EXAMPLE 11A reaction kettle was charged with 0.5g adipic acid, 20g deionized water, 0.2g 3 wt% Pd1Re2a/C catalyst. And (3) sealing the reaction kettle, filling hydrogen, replacing the air in the kettle for 3 times, filling 8MPa pressure, heating to 180 ℃, and reacting for 10 hours. After the reaction is finished, cooling the reaction kettle to room temperature, and discharging hydrogen in the kettle to normal temperatureAnd (3) after centrifugal separation of reaction products, carrying out gas chromatography and liquid chromatography detection on the products, and separating to obtain the 1, 6-hexanediol product. The adipic acid conversion was 36.8% and the 1, 6-hexanediol selectivity was 27.9%.
EXAMPLE 12A reaction kettle was charged with 0.5g adipic acid, 20g deionized water, 0.2g 3 wt% Pd2Re1a/C catalyst. And (3) sealing the reaction kettle, filling hydrogen, replacing the air in the kettle for 3 times, filling 8MPa pressure, heating to 180 ℃, and reacting for 8 hours. After the reaction is finished, discharging hydrogen in the kettle to normal pressure, after the reaction product is centrifugally separated, carrying out gas chromatography and liquid chromatography detection on the product, and separating to obtain the 1, 6-hexanediol product. The adipic acid conversion was 26.1% and the 1, 6-hexanediol selectivity was 22.7%.
EXAMPLE 13A reaction kettle was charged with 0.5g adipic acid, 20g deionized water, 0.2g 3 wt% Ir1Re1a/C catalyst. And (3) sealing the reaction kettle, filling hydrogen, replacing the air in the kettle for 3 times, filling 8MPa pressure, heating to 140 ℃, and reacting for 10 hours. After the reaction is finished, cooling the reaction kettle to room temperature, discharging hydrogen in the kettle to normal pressure, after the reaction product is centrifugally separated, carrying out gas chromatography and liquid chromatography detection on the product, and separating to obtain the 1, 6-hexanediol product. The adipic acid conversion was 40.3% and the 1, 6-hexanediol selectivity was 16.7%.
Example 14A reaction kettle was charged with 0.5g adipic acid, 20g deionized water, 0.2g 3 wt% Ir1Re1a/C catalyst. And (3) sealing the reaction kettle, filling hydrogen, replacing the air in the kettle for 3 times, filling 8MPa pressure, heating to 160 ℃, and reacting for 10 hours. After the reaction is finished, cooling the reaction kettle to room temperature, discharging hydrogen in the kettle to normal pressure, after the reaction product is centrifugally separated, carrying out gas chromatography and liquid chromatography detection on the product, and separating to obtain the 1, 6-hexanediol product. The adipic acid conversion was 41.3% and the 1, 6-hexanediol selectivity was 25.8%.
Example 15A reaction kettle was charged with 0.5g adipic acid, 20g deionized water, 0.2g Ir1Re1a/C catalyst. And (3) sealing the reaction kettle, filling hydrogen, replacing the air in the kettle for 3 times, filling 8MPa pressure, heating to 200 ℃, and reacting for 10 hours. After the reaction is finished, the reaction kettle is loweredAnd (3) discharging hydrogen in the kettle to normal pressure after the temperature is reduced to room temperature, carrying out gas chromatography and liquid chromatography detection on the product after the reaction product is centrifugally separated, and separating to obtain the 1, 6-hexanediol product. The conversion of adipic acid was 99.0% and the selectivity to 1, 6-hexanediol was 26.4%.
EXAMPLE 16A reaction kettle was charged with 0.5g adipic acid, 20g deionized water, 0.2g 3 wt% Ir1Re1a/C catalyst. And (3) sealing the reaction kettle, filling hydrogen, replacing air in the kettle for 3 times, filling 7MPa pressure, heating to 180 ℃, and reacting for 10 hours. After the reaction is finished, cooling the reaction kettle to room temperature, discharging hydrogen in the kettle to normal pressure, after the reaction product is centrifugally separated, carrying out gas chromatography and liquid chromatography detection on the product, and separating to obtain the 1, 6-hexanediol product. The adipic acid conversion was 82.5% and the 1, 6-hexanediol selectivity was 42.9%.
Example 17A reaction kettle was charged with 0.5g adipic acid, 20g deionized water, 0.2g 3 wt% Ir1Re1a/C catalyst. And (3) sealing the reaction kettle, filling hydrogen, replacing air in the kettle for 3 times, filling 6MPa pressure, heating to 180 ℃, and reacting for 10 hours. After the reaction is finished, cooling the reaction kettle to room temperature, discharging hydrogen in the kettle to normal pressure, after the reaction product is centrifugally separated, carrying out gas chromatography and liquid chromatography detection on the product, and separating to obtain the 1, 6-hexanediol product. The adipic acid conversion was 76.1% and the 1, 6-hexanediol selectivity was 25.8%.
EXAMPLE 18A reaction kettle was charged with 0.5g adipic acid, 20g deionized water, 0.2g 3 wt% Ir1Re1a/C catalyst. And (3) sealing the reaction kettle, filling hydrogen, replacing the air in the kettle for 3 times, filling 5MPa pressure, heating to 180 ℃, and reacting for 10 hours. After the reaction is finished, discharging hydrogen in the kettle to normal pressure, after the reaction product is centrifugally separated, carrying out gas chromatography and liquid chromatography detection on the product, and separating to obtain the 1, 6-hexanediol product. The adipic acid conversion was 67.8% and the 1, 6-hexanediol selectivity was 31.1%.
Claims (7)
1. A preparation method of a catalyst for preparing 1, 6-hexanediol by directly hydrogenating adipic acid is characterized by comprising the following steps:
using carbon material as carrierTaking a metal salt precursor solution of one or two of iridium, palladium, platinum and rhenium metal salts, and controlling the total metal loading amount to be 0.3-5 wt%; aging at room temperature for 12H without adding or adding auxiliary dispersion solution to adjust pH value of the solution, vacuum filtering, washing, transferring to a forced air drying oven, and drying overnight to obtain sample powder, and calcining at 200-600 deg.C for 2-8H in a tubular furnace mixed atmosphere of hydrogen and argon, wherein H2The volume fraction is not less than 10 percent, and the obtained adipic acid is directly hydrogenated to prepare the 1, 6-hexanediol catalyst.
2. The method of claim 1, wherein the auxiliary dispersing solution comprises HCl, HF, Na2CO3、NaHCO3And one or a mixture of two or more of NaOH.
3. The method according to claim 1 or 2, wherein the carbon material comprises one or a mixture of two or more of carbon nanotubes, activated carbon, and graphite.
4. The method according to claim 1 or 2, wherein the metal salt precursor comprises one or a mixture of two or more of acetylacetone salt, chloride, nitrate, and ammonium salt.
5. The method according to claim 3, wherein the metal salt precursor comprises one or more of acetylacetone salt, chloride, nitrate, and ammonium salt.
6. The application of the catalyst for preparing 1, 6-hexanediol by directly hydrogenating adipic acid is characterized by comprising the following steps of:
adding adipic acid, a solvent and a reduced catalyst into a high-pressure reaction kettle, sealing the reaction kettle, filling hydrogen, replacing air in the kettle for 3 times, filling 2-10MPa pressure, and reacting at 80-220 ℃ for 2-10 h; and after the reaction is finished, cooling to room temperature, discharging gas to normal pressure, detecting reaction products by gas chromatography and liquid chromatography respectively after centrifugal separation, and separating to obtain the 1, 6-hexanediol product.
7. The use of claim 6, wherein the mass concentration of the adipic acid in the solvent is 1-5%, the mass ratio of the catalyst to the adipic acid is 10-40%, and the solvent is one or a mixture of more than two of ethanol, water and diethyl ether.
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2019
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