CN111153875A - Gamma valerolactone and method for preparing gamma valerolactone by utilizing levulinate - Google Patents
Gamma valerolactone and method for preparing gamma valerolactone by utilizing levulinate Download PDFInfo
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- CN111153875A CN111153875A CN202010010195.3A CN202010010195A CN111153875A CN 111153875 A CN111153875 A CN 111153875A CN 202010010195 A CN202010010195 A CN 202010010195A CN 111153875 A CN111153875 A CN 111153875A
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- gamma valerolactone
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
Abstract
The invention provides gamma valerolactone and a method for preparing gamma valerolactone by utilizing levulinate, which comprises the following steps: reacting levulinic acid ester, a framework type copper-based metal alloy catalyst and deionized water under the condition of hydrogen at the temperature of 140-180 ℃ for 1-3 h; carrying out solid-liquid separation after the reaction, collecting a liquid-phase product, and purifying to obtain gamma valerolactone; the framework type copper-based metal alloy catalyst is prepared by soaking copper-aluminum alloy in an aqueous solution of alkali, wherein the aqueous solution of the alkali is a sodium hydroxide aqueous solution with the weight percent of 20 +/-1 percent; the method uses the cheap framework type copper-based metal alloy catalyst, uses the green solvent deionized water, has mild reaction conditions, and adopts renewable biomass derivatives as reaction raw materials, so that the obtained gamma valerolactone has high yield, can be widely used as a green solvent, a biofuel and the like, and further provides a new way for the utilization of renewable biomass energy.
Description
Technical Field
The invention belongs to the technical field of energy chemical industry, and particularly relates to gamma valerolactone and a method for preparing gamma valerolactone by utilizing levulinate.
Background
The excessive dependence and consumption of fossil energy sources such as coal, oil and natural gas has caused human beings to face serious energy and environmental crisis. There is much interest in developing and utilizing renewable clean energy sources such as solar energy, wind energy, tidal energy, and biomass energy. The biomass energy has the advantages of low pollution, wide distribution, rich sources, large reserves and the like. The effective utilization of biomass resources can alleviate the human need for fossil energy to some extent. Gamma valerolactone is an important biofuel, can be used as an environment-friendly solvent with various functions, and has huge demand. Gamma valerolactone is generally prepared by catalytic hydrogenation of biomass derivative levulinate, and conventionally, precious metal catalysts (such as ruthenium, platinum, palladium, iridium and the like) and organic solvents are often required to be used, so that the operation cost is increased, and therefore, the development and the use of cheap and commercialized metal catalysts and cheap green solvents are of great significance for the production of the gamma valerolactone.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for preparing gamma valerolactone by utilizing levulinate.
It is a second object of the present invention to provide gamma valerolactone as described above.
In order to achieve the above purpose, the solution of the invention is as follows:
a method for preparing gamma valerolactone from levulinate ester, comprising the steps of:
reacting levulinic acid ester, a framework type copper-based metal alloy catalyst and deionized water under the condition of hydrogen at the temperature of 140-180 ℃ for 1-3 h; and carrying out solid-liquid separation after the reaction, collecting a liquid-phase product, and purifying to obtain gamma valerolactone.
The framework type copper-based metal alloy catalyst is prepared by soaking copper-aluminum alloy (active component) in an aqueous alkali solution, wherein the aqueous alkali solution is a 20 +/-1 wt% aqueous sodium hydroxide solution.
As a further improvement of the invention, the temperature of the aqueous alkali solution is 0-10 ℃.
As a further improvement of the invention, the soaking time is 1.5-4.5 h.
As a further improvement of the invention, the pressure of the hydrogen is 1-5 MPa.
In a further improvement of the present invention, the levulinic acid ester is selected from one or more of methyl levulinate, ethyl levulinate, propyl levulinate and butyl levulinate.
Gamma valerolactone, which is prepared by the method.
Due to the adoption of the scheme, the invention has the beneficial effects that:
firstly, the gamma valerolactone is synthesized by using a biomass derivative levulinate raw material, the levulinate can be prepared from biomass resource lignocellulose (from plants widely existing in the nature), fossil energy is not consumed, the global energy problem can be partially relieved, deionized water is used as a solvent, the reaction condition is mild, the highest yield of the gamma valerolactone can reach 98%, and thus the prepared gamma valerolactone can be widely used as a green solvent, a biofuel and the like, and a new way is further provided for the utilization of renewable biomass energy.
Secondly, the invention uses cheap framework type copper-based metal alloy as the raw material of the catalyst, thereby avoiding the use of noble metal catalyst and saving the cost; in addition, the preparation process of the catalyst is simple.
Drawings
FIG. 1 is a GC-FID spectrum of gamma valerolactone according to example 1 of the invention.
Detailed Description
The invention provides gamma valerolactone and a method for preparing gamma valerolactone by utilizing levulinate.
The method for preparing gamma valerolactone by utilizing levulinate comprises the following steps:
reacting levulinic acid ester, a framework type copper-based metal alloy catalyst and deionized water under the condition of hydrogen at the temperature of 140-180 ℃ for 1-3 h; and carrying out solid-liquid separation after the reaction, collecting a liquid-phase product, and purifying to obtain gamma valerolactone.
The reaction route is as follows:
in particular, the amount of the solvent to be used,
firstly, both acetyl of ethyl levulinate and externally added H molecules are adsorbed on the surface of skeleton copper (Raney Cu), H attacks acetyl to form an extremely unstable gamma-hydroxyphenylanoic ester, and secondly, one molecule of ethanol is removed from the substance to obtain a target product gamma valerolactone.
When the pressure is less than 1MPa, the reaction is slower, and the yield of gamma valerolactone is too low; when the pressure is more than 5MPa, the yield of gamma valerolactone is not obviously improved. Therefore, the pressure of the hydrogen is 1-5 MPa.
When the temperature is lower than 140 ℃, the reaction is slower, and the yield of gamma valerolactone is too low; when the temperature is more than 180 ℃, the yield of gamma valerolactone is not obviously improved. Therefore, the reaction temperature is 140-180 ℃.
The framework type copper-based metal alloy catalyst is prepared by soaking copper-aluminum alloy in an aqueous solution of alkali. The temperature of the aqueous alkali solution may be 0-10 deg.C, and too high a temperature may result in a decrease in the specific surface area of the catalyst. The soaking time is 1.5-4.5 h.
The catalyst only contains copper element and aluminum element, and can selectively synthesize the gamma valerolactone.
The levulinic acid ester is selected from more than one of methyl levulinate, ethyl levulinate, propyl levulinate and butyl levulinate.
The gamma valerolactone is prepared by the method.
The present invention will be further described with reference to the following examples.
Example 1:
the method for preparing gamma valerolactone by using ethyl levulinate in the embodiment comprises the following steps:
sequentially putting 1mmol of ethyl levulinate, 50mg of framework type copper-based metal alloy catalyst and 10mL of deionized water into a 100mL closed reactor, filling 1MPa of hydrogen into the reactor, slowly discharging through a pressure reducing valve, repeatedly replacing air in the reactor for 3 times, filling 4MPa of hydrogen into the reactor, reacting for 3 hours at 160 ℃, taking out a solid-liquid mixture after reaction, separating and purifying to obtain a gamma valerolactone solution.
The product after the reaction was analyzed by GC-FID (see FIG. 1), which showed that the conversion of ethyl levulinate reached 93.6% while gamma valerolactone was the major product with a yield of 89.1%. The industrial application adopts a proper high-pressure reactor as required, the reaction temperature can be controlled to be 160 ℃, and the reaction lasts for 3 hours. By the reaction, the gamma valerolactone can be synthesized by taking ethyl levulinate as a raw material, the operation is simple and convenient, and the reaction selectivity is good.
Example 2:
the method for preparing gamma valerolactone by using ethyl levulinate in the embodiment comprises the following steps:
sequentially filling 1mmol of ethyl levulinate, 25mg of framework type copper-based metal alloy catalyst and 10mL of deionized water into a 100mL closed reactor, filling 1MPa of hydrogen into the reactor, slowly discharging through a pressure reducing valve, repeatedly replacing air in the reactor for 3 times, filling 4MPa of hydrogen into the reactor, reacting for 3 hours at 160 ℃, taking out a solid-liquid mixture after reaction, and separating to obtain a gamma valerolactone solution.
The products after the reaction were analyzed by GC-FID, which showed that the conversion of ethyl levulinate was 89.8%, whereas gamma valerolactone was the main product, with a yield of 83.9%. The industrial application adopts a proper high-pressure reactor as required, the reaction temperature can be controlled to be 160 ℃, and the reaction lasts for 3 hours. By the reaction, the gamma valerolactone can be synthesized by taking ethyl levulinate as a raw material, the operation is simple and convenient, and the reaction selectivity is good.
Example 3:
the method for preparing gamma valerolactone by using ethyl levulinate in the embodiment comprises the following steps:
sequentially filling 1mmol of ethyl levulinate, 100mg of framework type copper-based metal alloy catalyst and 10mL of deionized water into a 100mL closed reactor, filling 1MPa of hydrogen into the reactor, slowly discharging through a pressure reducing valve, repeatedly replacing air in the reactor for 3 times, filling 4MPa of hydrogen into the reactor, reacting for 3 hours at 160 ℃, taking out a solid-liquid mixture after reaction, and separating to obtain a gamma valerolactone solution.
After the reaction, the product was analyzed by GC-FID, and the GC-FID analysis showed that the conversion rate of ethyl levulinate reached 99.6%, while gamma valerolactone was the main product, with a yield of 98.3%. The industrial application adopts a proper high-pressure reactor as required, the reaction temperature can be controlled to be 160 ℃, and the reaction lasts for 3 hours. By the reaction, the gamma valerolactone can be synthesized by taking ethyl levulinate as a raw material, the operation is simple and convenient, and the reaction selectivity is good.
Example 4:
the method for preparing gamma valerolactone by using ethyl levulinate in the embodiment comprises the following steps:
sequentially filling 1mmol of ethyl levulinate, 100mg of framework type copper-based metal alloy catalyst and 10mL of deionized water into a 100mL closed reactor, filling 1MPa of hydrogen into the reactor, slowly discharging through a pressure reducing valve, repeatedly replacing air in the reactor for 3 times, filling 1MPa of hydrogen into the reactor, reacting for 3 hours at 160 ℃, taking out a solid-liquid mixture after reaction, and separating to obtain a gamma valerolactone solution.
The products after the reaction were analyzed by GC-FID, and the GC-FID analysis showed that the conversion of ethyl levulinate was 95.3%, while gamma valerolactone was the main product, with a yield of 82.4%. The industrial application adopts a proper high-pressure reactor as required, the reaction temperature can be controlled to be 160 ℃, and the reaction lasts for 3 hours. By the reaction, the gamma valerolactone can be synthesized by taking ethyl levulinate as a raw material, the operation is simple and convenient, and the reaction selectivity is good.
Example 5:
the method for preparing gamma valerolactone by using ethyl levulinate in the embodiment comprises the following steps:
sequentially filling 1mmol of ethyl levulinate, 100mg of framework type copper-based metal alloy catalyst and 10mL of deionized water into a 100mL closed reactor, filling 1MPa of hydrogen into the reactor, slowly discharging through a pressure reducing valve, repeatedly replacing air in the reactor for 3 times, filling 5MPa of hydrogen into the reactor, reacting for 3 hours at 160 ℃, taking out a solid-liquid mixture after reaction, and separating to obtain a gamma valerolactone solution.
After the reaction, the product was analyzed by GC-FID, and the GC-FID analysis showed that the conversion rate of ethyl levulinate reached 99.9%, while gamma valerolactone was the main product, with a yield of 98.0%. The industrial application adopts a proper high-pressure reactor as required, the reaction temperature can be controlled to be 160 ℃, and the reaction lasts for 3 hours. By the reaction, the gamma valerolactone can be synthesized by taking ethyl levulinate as a raw material, the operation is simple and convenient, and the reaction selectivity is good.
Example 6:
the method for preparing gamma valerolactone by using ethyl levulinate in the embodiment comprises the following steps:
sequentially filling 1mmol of ethyl levulinate, 100mg of framework type copper-based metal alloy catalyst and 10mL of deionized water into a 100mL closed reactor, filling 1MPa of hydrogen into the reactor, slowly discharging through a pressure reducing valve, repeatedly replacing air in the reactor for 3 times, filling 4MPa of hydrogen into the reactor, reacting for 3 hours at 140 ℃, taking out a solid-liquid mixture after reaction, and separating to obtain a gamma valerolactone solution.
The products after the reaction were analyzed by GC-FID, and the GC-FID analysis showed that the conversion of ethyl levulinate was 92.6%, while gamma valerolactone was the main product, with a yield of 72.3%. The industrial application adopts a proper high-pressure reactor as required, the reaction temperature can be controlled at 140 ℃, and the reaction lasts for 3 hours. By the reaction, the gamma valerolactone can be synthesized by taking ethyl levulinate as a raw material, the operation is simple and convenient, and the reaction selectivity is good.
Example 7:
the method for preparing gamma valerolactone by using ethyl levulinate in the embodiment comprises the following steps:
sequentially filling 1mmol of ethyl levulinate, 100mg of framework type copper-based metal alloy catalyst and 10mL of deionized water into a 100mL closed reactor, filling 1MPa of hydrogen into the reactor, slowly discharging through a pressure reducing valve, repeatedly replacing air in the reactor for 3 times, filling 4MPa of hydrogen into the reactor, reacting for 3 hours at 180 ℃, taking out a solid-liquid mixture after reaction, and separating to obtain a gamma valerolactone solution.
After the reaction, the product was analyzed by GC-FID, and the GC-FID analysis showed that the conversion rate of ethyl levulinate reached 99.3%, while gamma valerolactone was the main product, with a yield of 96.0%. In industrial application, a proper high-pressure reactor is adopted according to requirements, the reaction temperature can be controlled to be 180 ℃, and the reaction lasts for 3 hours. By the reaction, the gamma valerolactone can be synthesized by taking ethyl levulinate as a raw material, the operation is simple and convenient, and the reaction selectivity is good.
Example 8:
the method for preparing gamma valerolactone by using ethyl levulinate in the embodiment comprises the following steps:
sequentially filling 1mmol of ethyl levulinate, 100mg of framework type copper-based metal alloy catalyst and 10mL of deionized water into a 100mL closed reactor, filling 1MPa of hydrogen into the reactor, slowly discharging through a pressure reducing valve, repeatedly replacing air in the reactor for 3 times, filling 4MPa of hydrogen into the reactor, reacting for 1h at 160 ℃, taking out a solid-liquid mixture after reaction, and separating to obtain a gamma valerolactone solution.
The products after the reaction were analyzed by GC-FID, which showed that the conversion of ethyl levulinate was 83.0%, while gamma valerolactone was the main product, with a yield of 78.0%. The industrial application adopts a proper high-pressure reactor as required, the reaction temperature can be controlled to be 160 ℃, and the reaction lasts for 1 hour. By the reaction, the gamma valerolactone can be synthesized by taking ethyl levulinate as a raw material, the operation is simple and convenient, and the reaction selectivity is good.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments and the generic principles defined herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments. Those skilled in the art should appreciate that many modifications and variations are possible in light of the above teaching without departing from the scope of the invention.
Claims (8)
1. A method for preparing gamma valerolactone by utilizing levulinate ester is characterized in that: which comprises the following steps:
reacting levulinic acid ester, a framework type copper-based metal alloy catalyst and deionized water under the condition of hydrogen, carrying out solid-liquid separation after the reaction, collecting a liquid-phase product, and purifying to obtain gamma valerolactone;
the active components of the framework type copper-based metal alloy catalyst are copper and aluminum.
2. The method of claim 1, wherein: the framework type copper-based metal alloy catalyst is prepared by soaking copper-aluminum alloy in an aqueous solution of alkali;
the aqueous alkali solution is a 20 + -1 wt% aqueous sodium hydroxide solution.
3. The method of claim 2, wherein: the temperature of the aqueous alkali solution is 0-10 ℃.
4. The method of claim 2, wherein: the soaking time is 1.5-4.5 h.
5. The method of claim 1, wherein: the pressure of the hydrogen is 1-5 MPa.
6. The method of claim 1, wherein: the reaction temperature is 140-180 ℃, and the reaction time is 1-3 h.
7. The method of claim 1, wherein: the levulinic acid ester is selected from more than one of methyl levulinate, ethyl levulinate, propyl levulinate and butyl levulinate.
8. Gamma valerolactone, characterized by: prepared by the process of any one of claims 1 to 7.
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