CN112851623A - Method for preparing epsilon-caprolactone, 6-hydroxycaproic acid and ester thereof by using tetrahydrofurfuryl acetic acid and ester thereof - Google Patents

Method for preparing epsilon-caprolactone, 6-hydroxycaproic acid and ester thereof by using tetrahydrofurfuryl acetic acid and ester thereof Download PDF

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CN112851623A
CN112851623A CN202110254093.0A CN202110254093A CN112851623A CN 112851623 A CN112851623 A CN 112851623A CN 202110254093 A CN202110254093 A CN 202110254093A CN 112851623 A CN112851623 A CN 112851623A
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esters
tetrahydrofuran
caprolactone
acetic acid
epsilon
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CN112851623B (en
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李福伟
赵泽伦
高广
孙鹏
刘琪
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Lanzhou Institute of Chemical Physics LICP of CAS
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Abstract

The invention provides a method for preparing epsilon-caprolactone, 6-hydroxycaproic acid and esters thereof by utilizing tetrahydrofurfuryl acetic acid and esters thereof, which comprises the steps of carrying out reduction reaction on tetrahydrofurfuryl acetic acid and esters thereof for 0.5-48 hours under the conditions of 0.1-10MPa of pressure and 20-200 ℃ of temperature in a solvent under the action of a catalyst in a reducing atmosphere, separating the catalyst, and distilling the solvent to obtain target products of epsilon-caprolactone, 6-hydroxycaproic acid and esters thereof. The invention realizes the high-efficiency conversion of the bio-based tetrahydrofuran acetic acid and esters thereof under the relatively mild condition, and the produced epsilon-caprolactone, 6-hydroxycaproic acid and esters thereof are polymer monomers, have wide application and expand the application range of biomass; simultaneously solves the dilemma that the preparation of epsilon-caprolactone, 6-hydroxycaproic acid and ester thereof must depend on fossil resources.

Description

Method for preparing epsilon-caprolactone, 6-hydroxycaproic acid and ester thereof by using tetrahydrofurfuryl acetic acid and ester thereof
Technical Field
The invention relates to a preparation method of epsilon-caprolactone, 6-hydroxycaproic acid and ester thereof, in particular to a method for preparing epsilon-caprolactone, 6-hydroxycaproic acid and ester thereof by using tetrahydrofurfuryl acetic acid and ester thereof.
Background
Poly epsilon-caprolactone (PCL) is a high molecular organic polymer synthesized artificially. The appearance of the product is white solid powder, which is non-toxic, insoluble in water and easily soluble in various polar solvents. Has good biocompatibility, good organic polymer compatibility and good biodegradability, can be used as a cell growth support material, can be compatible with various conventional plastics, and can be completely degraded in natural environment within 6-12 months. In addition, PCL also has good shape memory temperature control property, and is widely applied to the production and processing fields of drug carriers, plasticizers, degradable plastics, nanofiber spinning and molding materials. The synthetic monomers of poly-epsilon-caprolactone, namely epsilon-caprolactone, 6-hydroxycaproic acid and esters thereof are synthesized by depending on the conversion of fossil resources at present.
With the development of the world economy, the exhaustion of fossil resources such as coal and petroleum and the increasing severity of environmental pollution problems, the development of biomass energy and biomass-based chemicals to (partially) replace fossil raw materials, and the realization of sustainable development of energy resources is highly regarded by countries in the world. The biomass-based furfural can be prepared by hydrolyzing cellulose, glucose, xylose, fructose and the like, has wide sources and is not limited by food, and becomes an important platform molecule for synthesizing renewable fuels and chemicals at present. Therefore, research on efficient conversion of furfural is attracting more and more attention, deriving a series of biologically-based commercially valuable end products and intermediates. The invention relates to a method for preparing epsilon-caprolactone, 6-hydroxycaproic acid and esters thereof by taking tetrahydrofurfuryl acetic acid and esters thereof as raw materials through long-term trial and exploration.
Disclosure of Invention
The invention mainly aims to provide a method for preparing epsilon-caprolactone, 6-hydroxycaproic acid and esters thereof by utilizing tetrahydrofurfuryl acetic acid and esters thereof, so as to overcome the defects in the prior art and expand the application of biomass platform compounds.
The invention relates to a method for preparing epsilon-caprolactone, 6-hydroxycaproic acid and esters thereof, which comprises the steps of carrying out reduction reaction on tetrahydrofuran acetic acid and esters thereof for 0.5-48 hours under the conditions of pressure of 0.1-10MPa and temperature of 20-200 ℃ in a solvent under the action of a catalyst in a reducing atmosphere, separating the catalyst, and distilling the solvent to obtain target products of epsilon-caprolactone, 6-hydroxycaproic acid and esters thereof. The synthetic formula is as follows:
Figure RE-DEST_PATH_IMAGE002
the solvent is at least one of methanol, benzene, pentanol, isopropanol, methyl tetrahydrofuran, cyclohexane, neobutanol, toluene, xylene, hexane, 1, 4-dioxane, heptane, ethanol, propanol, tetrahydrofuran, butanol, isobutanol, hexanol and ethyl acetate.
The reducing gas is hydrogen or a mixed gas containing hydrogen. Pure hydrogen is preferred.
The tetrahydrofuran acetic acid and the ester thereof are as follows: tetrahydrofurfuryl acetic acid and its esters include: at least one of tetrahydrofuran acetic acid, tetrahydrofuran methyl acetate, tetrahydrofuran ethyl acetate, tetrahydrofuran n-propyl acetate, tetrahydrofuran isopropyl acetate, tetrahydrofuran n-butyl acetate, tetrahydrofuran isobutyl acetate, tetrahydrofuran n-pentyl acetate, tetrahydrofuran isoamyl acetate, tetrahydrofuran neopentyl acetate, and tetrahydrofuran hexyl acetate.
The catalyst is a composite catalyst obtained by loading a catalytic active component on a carrier, wherein the carrier is at least one of active carbon, graphene, silicon dioxide, various molecular sieves, yttrium oxide, lanthanum oxide, zirconium dioxide, samarium oxide, titanium dioxide, hydroxyapatite, niobium pentoxide, scandium oxide, aluminum oxide, attapulgite, magnesium oxide, cerium oxide and montmorillonite. The catalytic active component comprises a synergistic catalytic element, a hydrogenation metal element and a precipitator. The synergistic catalytic element is at least one of molybdenum, rhenium, lanthanum, cerium, yttrium, tin, scandium, tungsten, vanadium, indium and praseodymium, and the content of the synergistic catalytic element in the catalyst is 0.01wt% -50 wt%. The hydrogenation metal element is at least one of rhodium, palladium, gold, cobalt, iridium, copper, silver, ruthenium, nickel, platinum and iron, and the content of the hydrogenation metal element in the catalyst is 0.01wt% -50 wt%. The precipitator is at least one of potassium hydroxide, sodium hydroxide, oxalic acid, ammonium oxalate, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, ammonia water, urea, ammonium bicarbonate and ammonium carbonate, the hydrogenation metal element is at least one of rhodium, palladium, gold, cobalt, iridium, copper, silver, ruthenium, nickel, platinum and iron, and the precipitator is 0.1-20 times of the hydrogenation metal. The dosage of the composite catalyst is 0.001-50% of the mass of the tetrahydrofuran acetic acid and the ester compound thereof.
The reduction reaction may be carried out in a tubular reactor or a batch tank reactor.
The composite catalyst has the characteristics of multiple functions and integration of directional adsorption, selective ring opening and selective hydrogenation, the directional adsorption and the selective ring opening are mainly completed by auxiliary elements in the catalyst, the selective hydrogenation is completed by hydrogenation metal, and the composite catalyst is directionally created according to the characteristics and the reaction of tetrahydrofuran acetic acid and ester compounds thereof.
FIG. 1 is a graph showing the results of the lifetime of 5% Pd/cerium oxide composite catalyst prepared according to the present invention. As can be seen from figure 1, the catalyst and the catalytic system have better conversion rate (more than 95%) of ethyl furanoate and high stability, and can continuously run for more than 200 h.
The principle of the invention for preparing epsilon-caprolactone, 6-hydroxycaproic acid and ester thereof is as follows: 1. the method comprises the following steps of realizing the directional adsorption of tetrahydrofuran acetic acid and esters thereof (realizing the simultaneous adsorption of oxygen and carbonyl of a tetrahydrofuran ring), 2, selectively opening a ring (directionally cutting off a carbon-oxygen bond of the tetrahydrofuran ring under the catalysis of an auxiliary element on the basis of realizing the directional adsorption), and 3, selectively hydrogenating (after opening the ring, the adjacent hydrogenation metal realizes hydrogenation through hydrogen overflow).
In conclusion, the invention realizes the high-efficiency conversion of the bio-based tetrahydrofuran acetic acid and esters thereof under the relatively mild condition, and the produced epsilon-caprolactone, 6-hydroxycaproic acid and esters thereof are polymer monomers, so that the application range of the biomass is expanded; simultaneously solves the dilemma that the preparation of epsilon-caprolactone, 6-hydroxycaproic acid and ester thereof must depend on fossil resources.
Drawings
FIG. 1 is a graph showing the results of the service life of the catalyst in example 12 of the present invention.
Detailed Description
The preparation of epsilon-caprolactone and 6-hydroxycaproic acid and esters thereof according to the present invention is further illustrated by the following specific examples.
Example 1
Preparation of 5% Pd/ceria catalyst: adding 2g of cerium oxide powder into 0.05mol/L palladium nitrate mixed solution, fully stirring for 1h, slowly adding 0.5mol/L sodium carbonate solution to PH =11, heating to 60 ℃, fully stirring for 12h, filtering, washing with water, vacuum drying for 12h at 50 ℃, calcining for 3h at 500 ℃ in air, and reducing for 3h at 300 ℃ in 10% hydrogen and 90% nitrogen mixed gas to obtain a composite catalyst;
placing 0.5g of composite catalyst and 30ml of methanol in a high-pressure reaction kettle, adding 2.0g of tetrahydrofuran methyl acetate, replacing with hydrogen for three times, finally, heating to 160 ℃ under the pressure of 5MPa, reacting for 20 hours under full stirring, cooling the reaction kettle to room temperature with water, slowly discharging gas, unloading the high-pressure reaction kettle, filtering, and carrying out chromatographic analysis on the filtrate, wherein the filtrate adopts agilent6890 gas chromatography to prepare an SE-54 capillary column, the conversion rate of the tetrahydrofuran methyl acetate is 98%, the selectivity of the 6-hydroxycaproic acid methyl ester is 83%, and the selectivity of epsilon-caprolactone is 15%.
Example 2
Preparation of 5% Ag3% Ir/activated carbon composite catalyst: adding 2g of activated carbon powder into a mixed solution containing 0.05mol/L silver nitrate and 0.03mol/L iridium chloride, fully stirring for 24h, drying, calcining at 500 ℃ in nitrogen for 3h, and then reducing in a mixed gas of 10% hydrogen and 90% nitrogen at 300 ℃ for 3h to obtain a composite catalyst;
placing 0.5g of composite catalyst and 30ml of ethanol in a high-pressure reaction kettle, adding 2.0g of tetrahydrofuran ethyl acetate, replacing with hydrogen for three times, finally, heating to 200 ℃ under the pressure of 0.1MPa, reacting for 0.5 hour under full stirring, cooling the reaction kettle to room temperature with water, slowly discharging gas, unloading the high-pressure reaction kettle, filtering, performing chromatographic analysis on the filtrate, and preparing an SE-54 capillary column for the filtrate by adopting an agilent6890 gas chromatography, wherein the conversion rate of the tetrahydrofuran ethyl acetate is 91%, the selectivity of the 6-ethyl hydroxycaproate is 70%, and the selectivity of the epsilon-caprolactone is 21%.
Example 3
Preparation of 8Ni%2% Ru/10% Re/alumina composite catalyst: adding 2g of aluminium oxide powder into a mixed solution containing 0.08 mol/nickel nitrate, 0.02mol/L ruthenium chloride and 0.1mol/L ammonium nitrate, fully stirring for 12h, carrying out vacuum drying at 40 ℃ for 12h, calcining at 550 ℃ in air for 3h, and then reducing at 350 ℃ in a mixed gas of 10% hydrogen and 90% nitrogen for 3h to obtain a composite catalyst;
placing 0.5g of composite catalyst and 30ml of isopropanol into a high-pressure reaction kettle, adding 2.0g of tetrahydrofuran isopropyl acetate, replacing with hydrogen for three times, finally, heating to 20 ℃ under the pressure of 10MPa, reacting for 48 hours under full stirring, cooling the reaction kettle to room temperature with water, slowly discharging gas, unloading the high-pressure reaction kettle, filtering, and carrying out chromatographic analysis on the filtrate, wherein the filtrate adopts agilent6890 gas chromatography and is provided with an SE-54 capillary column, the conversion rate of the tetrahydrofuran isopropyl acetate is 98%, the selectivity of 6-hydroxy isopropyl hexanoate is 76%, and the selectivity of epsilon-caprolactone is 22%.
Example 4
Preparation of 3% Rh10% Y/silica composite catalyst: adding 2.0g of silicon dioxide into a mixed solution of 0.03mol/L rhodium chloride and 0.1mol/L iridium nitrate, fully stirring for 12h, carrying out vacuum drying at 50 ℃ for 12h, calcining at 500 ℃ in air for 6h, and then reducing in a mixed gas of 10% of hydrogen and 90% of nitrogen at 300 ℃ for 3h to obtain a composite catalyst;
placing 0.5g of composite catalyst and 30ml of water in a high-pressure reaction kettle, adding 2.0g of tetrahydrofuran acetic acid, replacing with hydrogen for three times, finally heating to 140 ℃ under the pressure of 5MPa, reacting for 24 hours under full stirring, cooling the reaction kettle to room temperature with water, slowly discharging gas, unloading the high-pressure reaction kettle, filtering, and carrying out chromatographic analysis on the filtrate, wherein the filtrate adopts agilent6890 gas chromatography to prepare an SE-54 capillary column, the conversion rate of the tetrahydrofuran methyl acetate is 95%, the selectivity of the 6-hydroxycaproic acid is 15%, and the selectivity of the epsilon-caprolactone is 77%.
Example 5
Preparation of 10% Cu/10% Sc/titanium dioxide complexing agent: adding 2g of titanium dioxide into a mixed solution containing 0.1mol/L of copper nitrate and 0.1mol/L of scandium nitrate, fully stirring for 1h, slowly dropwise adding 0.5mol/L of sodium hydroxide solution until the pH is =11, heating to 80 ℃, fully stirring for 12h, filtering, washing with water, carrying out vacuum drying at 50 ℃ for 12h, calcining at 500 ℃ in air for 3h, and then reducing at 300 ℃ in a mixed gas of 10% of hydrogen and 90% of nitrogen for 3h to obtain a composite catalyst;
placing 0.5g of composite catalyst and 30ml of methyl tetrahydrofuran into a high-pressure reaction kettle, adding 2.0g of tetrahydrofuran ethyl acetate, replacing with hydrogen for three times, finally, heating to 150 ℃ under the hydrogen pressure of 5MPa, reacting for 10 hours under full stirring, cooling the reaction kettle to room temperature with water, slowly discharging gas, unloading the high-pressure reaction kettle, filtering, and carrying out chromatographic analysis on the filtrate, wherein the filtrate adopts agilent6890 gas chromatography and is provided with an SE-54 capillary column, the conversion rate of the tetrahydrofuran isopropyl acetate is 96%, the selectivity of the 6-methyl hydroxycaproate is 10%, the selectivity of the 6-hydroxycaproic acid is 15%, and the selectivity of the epsilon-caprolactone is 71%.
Example 6
Preparation of cerium oxide catalyst: 2g of cerium oxide powder was added to 40ml of ammonia (NH)3·H2O content of 23-27%), slowly heating to 60 ℃, fully stirring for 12h, filtering, washing, vacuum drying at 50 ℃ for 12h, calcining at 600 ℃ in air for 5h, and reducing in a mixed gas of 10% hydrogen and 90% nitrogen at 350 ℃ for 3h to obtain a cerium oxide catalyst;
placing 0.5g of composite catalyst and 30ml of methanol in a high-pressure reaction kettle, adding 2.0g of tetrahydrofuran methyl acetate, replacing with hydrogen for three times, finally, heating to 150 ℃ under the pressure of 6MPa, reacting for 20 hours under full stirring, cooling the reaction kettle to room temperature with water, slowly discharging gas, unloading the high-pressure reaction kettle, filtering, and carrying out chromatographic analysis on the filtrate, wherein the filtrate adopts agilent6890 gas chromatography to prepare an SE-54 capillary column, the conversion rate of the tetrahydrofuran ethyl acetate is 91%, the selectivity of the 6-hydroxy methyl hexanoate is 76%, and the selectivity of epsilon-caprolactone is 21%.
Example 7
Preparation of 2% Pd/3% Rh/5% W/yttria composite catalyst: adding 2g of yttrium oxide powder into a mixed solution containing 0.03 mol/rhodium chloride, 0.02mol/L palladium nitrate and 0.05mol/L ammonium tungstate, fully stirring for 12 hours, filtering, washing with water, carrying out vacuum drying at 50 ℃ for 12 hours, calcining at 550 ℃ in air for 4 hours, and then reducing in a mixed gas of 10% hydrogen and 90% nitrogen at 350 ℃ for 3 hours to obtain a composite catalyst;
placing 0.5g of composite catalyst and 30ml of toluene in a high-pressure reaction kettle, adding 2.0g of tetrahydrofuran acetic acid, replacing with hydrogen for three times, finally heating to 140 ℃ under the pressure of 5MPa, reacting for 12 hours under full stirring, cooling the reaction kettle to room temperature with water, slowly discharging gas, unloading the high-pressure reaction kettle, filtering, and carrying out chromatographic analysis on the filtrate, wherein the filtrate adopts agilent6890 gas chromatography to prepare an SE-54 capillary column, the conversion rate of the tetrahydrofuran methyl acetate is 91%, the selectivity of the 6-ethyl hydroxycaproate is 6%, the selectivity of the 6-hydroxycaproic acid is 7% and the selectivity of the epsilon-caprolactone is 80%.
Example 8
Preparation of 5% Au50% Sn/hydroxyapatite composite catalyst: adding 2g of hydroxyapatite powder into a mixed solution of 0.05 mol/chloroauric acid and 0.5mol/L stannic chloride, fully stirring for 24 hours, carrying out vacuum drying at 40 ℃ for 12 hours, calcining at 550 ℃ in air for 3 hours, and then reducing in a mixed gas of 10% hydrogen and 90% nitrogen at 300 ℃ for 3 hours to obtain a composite catalyst;
placing 0.5g of composite catalyst and 30ml of methanol in a high-pressure reaction kettle, adding 2.0g of tetrahydrofuran methyl acetate, replacing with hydrogen for three times, finally, heating to 120 ℃ under the pressure of 6MPa, reacting for 20 hours under full stirring, cooling the reaction kettle to room temperature with water, slowly discharging gas, unloading the high-pressure reaction kettle, filtering, and carrying out chromatographic analysis on the filtrate, wherein the filtrate adopts agilent6890 gas chromatography to prepare an SE-54 capillary column, the conversion rate of the tetrahydrofuran methyl acetate is 96%, the selectivity of the 6-hydroxycaproic acid methyl ester is 78%, and the selectivity of epsilon-caprolactone is 16%.
Example 9
Preparation of 50% Co/10% Mo/zirconium dioxide composite catalyst: adding 2g of zirconium dioxide powder into a mixed solution of 0.5mol/L cobalt nitrate and 0.1mol/L ammonium molybdate, fully stirring for 20h, carrying out vacuum drying at 50 ℃ for 6h, calcining at 600 ℃ in air for 5h, and then reducing in a mixed gas of 10% hydrogen and 90% nitrogen at 350 ℃ for 3h to obtain a composite catalyst;
placing 0.5g of composite catalyst and 30ml of neopentyl alcohol in a high-pressure reaction kettle, adding 2.0g of tetrahydrofuran acetic acid neopentyl ester, performing hydrogen replacement for three times, finally performing reaction under the condition that the hydrogen pressure is 7MPa, heating to 180 ℃, fully stirring for 10 hours, cooling the reaction kettle to room temperature by using water, slowly discharging gas, unloading the high-pressure reaction kettle, filtering, performing chromatographic analysis on the filtrate, and preparing an SE-54 capillary column for the filtrate by adopting an agilent6890 gas chromatography, wherein the conversion rate of the tetrahydrofuran acetic acid n-amyl ester is 90%, the selectivity of the 6-hydroxyl caproic acid neopentyl ester is 71%, and the selectivity of epsilon-caprolactone is 22%.
Example 10
Preparation of 5% Pt/10% La/niobium pentoxide composite catalyst: adding 2g of niobium pentoxide powder into a mixed solution containing 0.05mol/L chloroplatinic acid and 0.05mol/L lanthanum nitrate, fully stirring for 24h, carrying out vacuum drying at 40 ℃ for 12h, calcining at 500 ℃ in air for 3h, and then reducing in a mixed gas of 10% hydrogen and 90% nitrogen at 300 ℃ for 3h to obtain a composite catalyst;
placing 0.5g of composite catalyst and 30ml of ethanol in a high-pressure reaction kettle, adding 2.0g of tetrahydrofuran ethyl acetate, replacing with hydrogen for three times, finally, heating to 160 ℃ under the pressure of 5MPa, reacting for 12 hours under full stirring, cooling the reaction kettle to room temperature with water, slowly discharging gas, unloading the high-pressure reaction kettle, filtering, and carrying out chromatographic analysis on the filtrate, wherein the filtrate adopts agilent6890 gas chromatography to prepare an SE-54 capillary column, the conversion rate of the tetrahydrofuran n-butyl acetate is 91%, the selectivity of the 6-hydroxyl ethyl caproate is 72%, and the selectivity of the epsilon-caprolactone is 18%.
Example 11
Preparation of 2% Pd/3% Rh/5% W/yttria composite catalyst: adding 2g of yttrium oxide powder into a mixed solution containing 0.03 mol/rhodium chloride, 0.02mol/L palladium nitrate and 0.05mol/L ammonium tungstate, fully stirring for 12 hours, filtering, washing with water, carrying out vacuum drying at 50 ℃ for 12 hours, calcining at 550 ℃ in air for 4 hours, and then reducing in a mixed gas of 10% hydrogen and 90% nitrogen at 350 ℃ for 3 hours to obtain a composite catalyst;
2.0g of the composite catalyst is loaded into a continuous tubular reaction, 5.0MPa hydrogen is filled, the temperature is raised to 150 ℃, 200g of tetrahydrofuran methyl acetate is dissolved in 1000ml of methanol, a high-pressure injection pump is used for continuously injecting the tetrahydrofuran methyl acetate into a reactor, the space velocity is 45g/g.h, reaction liquid is collected in a liquid storage tank of the device, the chromatographic analysis is carried out on the reaction liquid, and the reaction liquid adopts agilent6980 gas chromatography and is equipped with an SE-54 capillary column. The conversion rate of tetrahydrofuran methyl acetate is 98%, the selectivity of 6-hydroxy methyl caproate is 73%, and the selectivity of epsilon caprolactone is 25%.
Example 12
Preparation of 5% Pd/ceria composite catalyst: adding 2g of cerium oxide powder into 0.05mol/L palladium nitrate mixed solution, fully stirring for 1h, slowly adding 0.5mol/L sodium carbonate solution to PH =11, heating to 60 ℃, fully stirring for 12h, filtering, washing with water, vacuum drying for 12h at 50 ℃, calcining for 3h at 500 ℃ in air, and reducing for 3h at 300 ℃ in 10% hydrogen and 90% nitrogen mixed gas to obtain a composite catalyst;
2.0g of the composite catalyst is loaded into a continuous tubular reaction, 4.0MPa hydrogen is filled, the temperature is raised to 130 ℃, 200g of tetrahydrofuran methyl acetate is dissolved in 1000ml of methanol, a high-pressure injection pump is used for continuously injecting the tetrahydrofuran methyl acetate into a reactor, the space velocity is 40g/g.h, reaction liquid is collected in a liquid storage tank of the device, samples are taken every 5h, the reaction liquid is subjected to chromatographic analysis, the reaction liquid adopts an agilent6980 gas chromatography and is provided with an SE-54 capillary column, and the result is shown in figure 1, so that the catalyst and the catalytic system have better conversion rate (more than 95 percent) of tetrahydrofuran ethyl acetate and high stability (more than 200h of continuous operation).

Claims (10)

1. A process for preparing epsilon-caprolactone, 6-hydroxycaproic acid and their esters from tetrahydrofuran acetic acid and their esters includes such steps as reducing reaction of tetrahydrofuran acetic acid and its esters at 20-200 deg.C under 0.1-10MPa for 0.5-48 hr in solvent and under the action of catalyst, separating catalyst, and distilling to obtain the target products epsilon-caprolactone, 6-hydroxycaproic acid and their esters.
2. The process for producing epsilon-caprolactone and 6-hydroxycaproic acid and esters thereof using tetrahydrofurfuryl acetic acid and esters thereof as claimed in claim 1, wherein: the tetrahydrofuran acetic acid and the ester thereof are as follows: at least one of tetrahydrofuran acetic acid, tetrahydrofuran methyl acetate, tetrahydrofuran ethyl acetate, tetrahydrofuran n-propyl acetate, tetrahydrofuran isopropyl acetate, tetrahydrofuran n-butyl acetate, tetrahydrofuran isobutyl acetate, tetrahydrofuran n-pentyl acetate, tetrahydrofuran isoamyl acetate, tetrahydrofuran neopentyl acetate, and tetrahydrofuran hexyl acetate.
3. The process for producing epsilon-caprolactone and 6-hydroxycaproic acid and esters thereof using tetrahydrofurfuryl acetic acid and esters thereof as claimed in claim 1, wherein: the solvent is as follows: methanol, benzene, pentanol, isopropanol, methyltetrahydrofuran, cyclohexane, neobutanol, toluene, xylene, hexane, 1, 4-dioxane, heptane, ethanol, propanol, tetrahydrofuran, butanol, isobutanol, hexanol, ethyl acetate.
4. The process for producing epsilon-caprolactone and 6-hydroxycaproic acid and esters thereof using tetrahydrofurfuryl acetic acid and esters thereof as claimed in claim 1, wherein: the reducing gas is hydrogen or a mixed gas containing hydrogen.
5. The process for producing epsilon-caprolactone and 6-hydroxycaproic acid and esters thereof using tetrahydrofurfuryl acetic acid and esters thereof as claimed in claim 1, wherein: the catalyst is a composite catalyst obtained by loading a catalytic active component on a carrier, wherein the catalytic active component comprises a synergistic catalytic element, a hydrogenation metal element and a precipitator.
6. The process for producing epsilon-caprolactone and 6-hydroxycaproic acid and esters thereof using tetrahydrofurfuryl acetic acid and esters thereof as claimed in claim 5, wherein: the carrier is at least one of activated carbon, graphene, silicon dioxide, various molecular sieves, yttrium oxide, lanthanum oxide, zirconium dioxide, samarium oxide, titanium dioxide, hydroxyapatite, niobium pentoxide, scandium oxide, aluminum oxide, attapulgite, magnesium oxide, cerium oxide and montmorillonite.
7. The process for producing epsilon-caprolactone and 6-hydroxycaproic acid and esters thereof using tetrahydrofurfuryl acetic acid and esters thereof as claimed in claim 5, wherein: the synergistic catalytic element is at least one of molybdenum, rhenium, lanthanum, cerium, yttrium, tin, scandium, tungsten, vanadium, indium and praseodymium, and the content of the synergistic catalytic element in the catalyst is 0.01wt% -50 wt%.
8. The process for producing epsilon-caprolactone and 6-hydroxycaproic acid and esters thereof using tetrahydrofurfuryl acetic acid and esters thereof as claimed in claim 5, wherein: the hydrogenation metal element is at least one of rhodium, palladium, gold, cobalt, iridium, copper, silver, ruthenium, nickel, platinum and iron, and the content of the hydrogenation metal element in the catalyst is 0.01wt% -50 wt%.
9. The process for producing epsilon-caprolactone and 6-hydroxycaproic acid and esters thereof using tetrahydrofurfuryl acetic acid and esters thereof as claimed in claim 5, wherein: the precipitator is at least one of potassium hydroxide, sodium hydroxide, oxalic acid, ammonium oxalate, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, ammonia water, urea, ammonium bicarbonate and ammonium carbonate, the hydrogenation metal element is at least one of rhodium, palladium, gold, cobalt, iridium, copper, silver, ruthenium, nickel, platinum and iron, and the amount of the precipitator is 0.1-20 times of the mass of the hydrogenation metal.
10. The process for producing epsilon-caprolactone and 6-hydroxycaproic acid and esters thereof using tetrahydrofurfuryl acetic acid and esters thereof as claimed in claim 1, wherein: the dosage of the composite catalyst is 0.001-50% of the mass of the tetrahydrofuran acetic acid and the ester compound thereof.
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