CN111434657B - Preparation method of gamma-valerolactone and levulinate ester compound - Google Patents
Preparation method of gamma-valerolactone and levulinate ester compound Download PDFInfo
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- CN111434657B CN111434657B CN201910036909.5A CN201910036909A CN111434657B CN 111434657 B CN111434657 B CN 111434657B CN 201910036909 A CN201910036909 A CN 201910036909A CN 111434657 B CN111434657 B CN 111434657B
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Abstract
The invention discloses a preparation method of gamma-valerolactone and levulinate ester compounds. The preparation method of the gamma-valerolactone comprises the following steps of reacting furfural with secondary alcohol under the action of a catalyst to obtain the gamma-valerolactone, wherein the catalyst is M (R) n, M is selected from Ce, sc, Y, yb or Lu, and R is selected from trifluoromethane sulfonic acid group, perfluorobutane sulfonic acid group, heptadecafluoro octane sulfonic acid group, di (trifluoromethane sulfonyl) amino group or di (perfluorobutane sulfonyl) amino group. The method utilizes the commercialized single Lewis acid as the catalyst, avoids the step-by-step and complex product separation process in the traditional gamma-valerolactone preparation process, is simple and efficient, realizes the low-cost production of gamma-valerolactone, and particularly can realize the one-step conversion of biomass (such as xylose, xylan, corncob and the like) into gamma-valerolactone by utilizing the commercialized single catalyst.
Description
Technical Field
The invention relates to a preparation method of gamma-valerolactone and levulinate ester compounds.
Background
The non-renewable nature of fossil energy and the environmental degradation effects that result from use have forced people to review and adjust fossil energy development strategies over the long term. Future energy development will go to diversification, and common development of solar energy, wind energy, water energy, tidal energy, biomass energy, nuclear energy and the like will not take place in the past, and specific energy obtaining modes will be selected according to regional differences, for example: the solar energy in the Tibetan area is mainly developed, and the biomass energy in the northeast area is mainly biomass energy. Among all clean energy sources, biomass energy is the only carbon-containing energy source, has an irreplaceable position in the aspects of preparing fuel and chemicals, and long-term development planning in China has focused on development and utilization of biomass resources as a strategy for sustainable development. Lignocellulose is transformed from green plants through photosynthesis, and has wide sources, low price and non-food renewable biomass resources. The worldwide generation of lignocellulose by photosynthesis is about 170 hundred million tons each year, which has great development potential.
Currently, research on biomass in the world has made great progress, hundreds of small molecule platform products are available through "biomass refining", and in 2004 the U.S. department of energy has published a report of high value-added chemicals (chemicals from biomass), of which twelve important platform products are proposed: succinic acid, 2, 5-furandicarboxylic acid, aspartic acid, glutamic acid, itaconic acid, 3-hydroxypropionic acid, glucaric acid, levulinic acid, glycerol, xylitol and sorbitol (Green Chemistry,2015,17 (2): 959-972). However, considering the problems of raw material cost, production cost, environmental cost, market scale and price, technical feasibility and the like, at present, biomass refining products truly entering the market are graded and concentrated into refining products of grain crops. Most typically bioethanol, the third largest bioethanol producer after brazil has been statistically made us-next to the middle of 2007 (Renewable and Sustainable Energy Reviews,2009,13 (9): 2571-2579). At present, most bioethanol takes edible biomass such as corn, starch, syrup and the like as raw materials. This approach solves the energy problem to some extent in a short period of time, but solving the energy problem at the cost of grain necessarily causes a new problem. Therefore, the problem of energy is solved by using non-edible lignocellulose such as crop straws and the like to replace grains, and the trend of biomass energy development in the future is realized. The data shows that there are 4 million tons of crop waste (straw, rice husk, etc.) per year in China (Green Chemistry,2013,15 (3): 584) as an agricultural large country. While the annual crop waste in the united states can reach 13 billion tons (G.W.Huber, NSF, DOE, and American Chemical Society Workshop, washington, DC, 2007).
The lignocellulose contains abundant hemicellulose resources, and the hemicellulose has the characteristics of low polymerization degree, high branching degree and the like, is relatively easy to degrade, and xylose units in the hemicellulose are extremely easy to dehydrate and convert into furfural under the catalysis of protonic acid. As early as the 30 s of the last century, the preparation of furfural from hemicellulose in corncob has reached an industrial scale (Nature, 2016,531 (7593):215-219). According to the data, at present, china has rich furfural resources, is the largest furfural producing country in the world, and occupies 70 percent of annual furfural yield (Energy Environ Sci,2016,9 (4): 1144-1189) in the world. As the only fine chemical product which takes non-edible biomass resources as raw materials and realizes industrial mass production, the furfural provides an example for sustainable and renewable chemical development in the new era. However, due to the limitation of key problems such as high production cost and low profit, a large-scale renewable chemical product industry chain with furfural as a core is not formed in the last hundred years of industrial production of furfural.
Among the downstream products of furfural, gamma-valerolactone is a fine chemical product with high added value and high economic value, and the market price of gamma-valerolactone is 35484 dollars per ton, which is 30 times of the price of furfural (Journal of Industrial and Engineering Chemistry,2017,48,173-179). In 2010 James a.dumesic used gamma valerolactone as a starting material to prepare transportation fuels directly (Science, 2010,322,417-421). Subsequently, in 2014, james a.dumesic team found that gamma valerolactone is a good green biomass solvent with a high boiling point (207-208 ℃) which is miscible with water at any ratio and has low toxicity (half-lethal amount less than ethanol), and they degraded natural biomass such as rice hulls, cork, etc. using gamma valerolactone mixed with water as a solvent, achieving a monosaccharide yield of 90% (Science, 2014,343,277-280). The method for preparing the fine chemical product gamma-valerolactone by using the furfural as the raw material can inevitably make up for the economic disadvantages in the production process of the furfural, and provides a opportunity for the industrial chain development of the large-scale renewable chemical products by taking the furfural as the core.
At present, the production of gamma-valerolactone by using furfural as a starting material still has a great bottleneck in the technology and production route. The preparation of gamma valerolactone from furfural generally requires at least a three-step process, the synthetic route of which is shown below:
firstly, furfural is reduced into furfuryl alcohol, then the furfuryl alcohol is subjected to alcoholysis under the catalysis of acid to generate levulinic acid or levulinate, and finally, the obtained levulinic acid compound is subjected to reduction and cyclization to generate the final gamma-valerolactone.
In 1937, duPont (Du Pont de Nemours) improved the vapor phase production of furfuryl alcohol, and subsequently the quince chemical company (Quaker Oats) utilized Na 2 O·xSiO 2 The supported copper catalyst catalyzes the reduction of furfural at the temperature of 405-450K, and the yield of 99% is achieved. Conversion of furfural to furfuryl alcohol has now reached commercial scale, with 65% of the world's furfural being used annually to produce furfuryl alcohol (Furfural and Derivatives, wileyVCH Verlag GmbH)&KGaA, weinheim, 2012.). At present, the conversion of levulinic acid/levulinate to gamma valerolactone has also achieved high yields. In 2009, fu Yao research team produced 95% yield by in situ cleavage of formic acid to hydrogenate levulinic acid under ruthenium trichloride catalysis to produce gamma valerolactone (angelw.chem.int.ed.2009, 48, 6529-6532); the 2015 group Han Buxing study reduced levulinic acid in sec-butanol using a zirconium phytate catalyst to obtain 97% gamma valerolactone yield (angelw.chem.int.ed.2015, 54, 9399-9403.). The method avoids the safety problem caused by the use of hydrogen in the traditional reduction process, solves the most important problem in the reduction reaction of the organic matters at present, and replaces the traditional hydrogen by utilizing a safe and efficient hydrogen carrier and a release delivery system.
Currently, the hydrolysis/alcoholysis process of furfuryl alcohol to levulinic acid/levulinate is a key step affecting the yield of the overall process. Furfuryl alcohol is typically subjected to hydrolysis/alcoholysis reactions under acidic conditions with side reactions such as: oxidation, polymerization, etc., to form the poorly soluble brown oligomer Humit (Journal of Industrial and Engineering Chemistry,2014,20,650-655). In 2009, the Lange group of subjects produced levulinate by the alcoholysis of furfuryl alcohol using H-ZSM-5, amberlyst and Dowex series of resins, respectively, achieved a high yield of 90% (ChemSusChem, 2009,2,437-441). In 2015, fu Yao, a task group of the university of science and technology, found that 80.6% yield of methyl levulinate (Green chem.,2016,18,1516-1523) was obtained by reacting aluminum sulfate as a catalyst under microwave conditions.
Although the three single-step reactions all achieve higher yields, the final yield of the whole production route is still not ideal (74%), and meanwhile, complicated production steps and complex catalytic systems bring difficult separation processes, and the energy and economic consumption in the production process are increased. And brings great obstruction to the industrialized popularization of the process. In 2013, the Yuriy Rom n-Leshkov research group at Cambridge university utilized Al-MFI-n @ 
acid) and Zr-Beta (Lewis acid) are combined with sec-butyl alcohol as a hydrogen source to realize one-pot conversion of furfural to gamma-GVL, so that the gamma-valerolactone yield (Angew.chem.int.ed.2013, 52, 8022-8025) of 78% is obtained, the complicated separation and purification process caused by three-step reaction is avoided, and the problems of complex catalytic system and severe catalyst preparation conditions still exist.
Disclosure of Invention
The invention aims to overcome the defects of complex production process, low efficiency and complicated separation process of gamma-valerolactone and levulinate compounds in the prior art, and provides a preparation method of gamma-valerolactone and levulinate compounds. The preparation method is simple, efficient and free of complicated separation processes, and particularly, the method can realize one-step conversion of biomass (such as xylose, xylan, corncob and the like) into gamma-valerolactone by utilizing a commercial single catalyst.
In order to achieve the above purpose, the present invention adopts the following technical scheme.
The invention provides a preparation method of gamma-valerolactone, which comprises the following steps of reacting furfural with secondary alcohol under the action of a catalyst to prepare gamma-valerolactone;
the catalyst is M (R) n, wherein M is selected from Ce, sc, Y, yb or Lu, and R is selected from trifluoro Methanesulfonyl (OTf), perfluorobutanesulfonyl (ONf), heptadecafluorooctanesulfonyl (OPf), bis (trifluoromethanesulfonyl) amino (NTf) 2 ) Or di (perfluorobutanesulfonyl) amino (NNf) 2 )；
In the present invention, M is preferably Sc.
In the present invention, the R is preferably a trifluoromethanesulfonic acid group (OTf) or a perfluorobutanesulfonic acid group (ONf).
In the present invention, n in M (R) n may be a positive integer according to the number of ligands R to which M can bind.
In the present invention, the catalyst is preferably Ce (OTf) 3 、Sc(ONf) 3 、Sc(OTf) 3 、Y(OTf) 3 、Yb(OTf) 3 、Lu(OTf) 3 、Sc(OPf) 3 、Sc(NTf 2 ) 3 And Sc (NNf) 2 ) 3 Such as Ce (OTf) 3 、Sc(ONf) 3 、Sc(OTf) 3 、Y(OTf) 3 、Yb(OTf) 3 、Lu(OTf) 3 、Sc(OPf) 3 、Sc(NTf 2 ) 3 Or Sc (NNf) 2 ) 3 。
Wherein the Sc (OTf) 3 The structural formula of (2) is as follows:
wherein the Sc (ONf) 3 The structural formula of (2) is as follows:
wherein the Sc (OPf) 3 The structural formula of (2) is as follows:
wherein the Sc (NTf) 2 ) 3 The structural formula of (2) is as follows:
wherein the Sc (NNf) 2 ) 3 The structural formula of (2) is as follows:
in the present invention, the molar ratio of the catalyst to the furfural is preferably (0.1 to 100): 100, more preferably (1-10): 100, e.g. 5:100.
In the present invention, the secondary alcohol refers to an alcohol in which two carbons (or substituents) are bonded to the carbon of the hydroxyl group (-OH) (i.e., the hydroxyl carbon), and the structural formula is R' -CH (R ") -OH. The secondary alcohol may be selected from C 3 ～C 10 Secondary alcohols of (C) are preferred 3 ～C 6 For example isopropanol.
In the present invention, preferably, the secondary alcohol may participate in the reaction as a solvent and a reactant.
In the present invention, the reaction may also be carried out in an inert solvent.
Wherein the inert solvent may be an inert solvent conventional in the art, generally refers to a solvent that does not react with the catalyst and reactants (e.g., furfural and secondary alcohols), such as one or more of hexane, benzene, carbon tetrachloride, and dichloroethane.
When the reaction is carried out in an inert solvent, the secondary alcohol may participate in the reaction as a solvent and as a reactant, or may only participate in the reaction as a reactant.
In the present invention, the molar (mmol) ratio of the volume (mL) of the secondary alcohol to the furfural is preferably 3 (0.01-1), more preferably 3 (0.05-0.5), for example 3:0.05, 3:0.1, 3:0.125, 3:0.25 or 3:0.5.
In the present invention, the temperature of the reaction may be a reaction temperature conventional in the art, preferably 100 to 200 ℃, for example 140 to 170 ℃, further for example 140 ℃, 150 ℃ or 170 ℃.
In the present invention, the reaction time may be a reaction time conventional in the art, preferably 6 to 48 hours, for example 24 to 48 hours, further for example 24 hours, 36 hours or 48 hours.
When the catalyst is Sc (ONf) 3 When the molar ratio of the catalyst to the furfural is preferably (1-10): 100 (e.g., 5:100), the ratio of the volume (mL) of the secondary alcohol to the molar (mmol) of the furfural is preferably 3 (0.05-0.5) (e.g., 3:0.05), the temperature of the reaction is preferably 140-170 ℃ (e.g., 150 ℃), and the time of the reaction is preferably 24-36 hours (e.g., 36 hours).
When the catalyst is Sc (OTf) 3 When the molar ratio of the catalyst to the furfural is preferably (1-10): 100 (e.g., 5:100), the molar (mmol) ratio of the volume of the secondary alcohol (mL) to the furfural is preferably 3 (0.05-0.5) (e.g., 3:0.05, 3:0.1, 3:0.125, 3:0.25 or 3:0.5), the temperature of the reaction is preferably 140-170 ℃ (e.g., 140 ℃, 150 ℃, or 170 ℃), and the time of the reaction is preferably 24-36 hours (e.g., 24 hours or 36 hours).
When the catalyst is Y (OTf) 3 When the molar ratio of the catalyst to the furfural is preferably (1 to 10): 100 (e.g., 5:100), the ratio of the volume (mL) of the secondary alcohol to the moles (mmol) of the furfural is preferably 3 (0.05 to 0.5) (e.g., 3:0.05), the temperature of the reaction is preferably 140 to 170 ℃ (e.g., 150 ℃), and the time of the reaction is preferably 24 to 36 hours (e.g., 36 hours).
When the catalyst is Yb (OTf) 3 When the molar ratio of the catalyst to the furfural is preferably (1 to 10): 100 (e.g., 5:100), the ratio of the volume (mL) of the secondary alcohol to the moles (mmol) of the furfural is preferably 3 (0.05 to 0.5) (e.g., 3:0.05), the temperature of the reaction is preferably 140 to 170 ℃ (e.g., 150 ℃), and the time of the reaction is preferably 24 to 36 hours (e.g., 36 hours).
When the catalyst is Lu (OTf) 3 When the molar ratio of the catalyst to the furfural is preferably (1 to 10): 100 (e.g., 5:100), the volume of the secondary alcohol (mL) and theThe molar (mmol) ratio of furfural is preferably 3 (0.05 to 0.5) (e.g., 3:0.05), the reaction temperature is preferably 140 to 170 ℃ (e.g., 150 ℃), and the reaction time is preferably 24 to 36 hours (e.g., 36 hours).
When the catalyst is Ce (OTf) 3 When the molar ratio of the catalyst to the furfural is preferably (1-10): 100 (e.g., 5:100), the ratio of the volume (mL) of the secondary alcohol to the molar (mmol) of the furfural is preferably 3 (0.05-0.5) (e.g., 3:0.05), the temperature of the reaction is preferably 140-170 ℃ (e.g., 150 ℃), and the time of the reaction is preferably 24-36 hours (e.g., 36 hours).
In the invention, after the gamma-valerolactone is prepared, the catalyst can be recycled after conventional regeneration treatment in the field, for example, after gamma-valerolactone, secondary alcohol and byproducts are separated by reduced pressure distillation, the catalyst is dried, and the catalyst can be recycled.
In the invention, in the process of preparing gamma-valerolactone by using furfural as a raw material, ketone substances are the only byproducts in the preparation process, and the separation is simple, thereby being beneficial to realizing the industrialized production of gamma-valerolactone. For example, when the secondary alcohol is isopropanol, the only byproduct is acetone.
In the process of generating gamma-valerolactone by taking furfural as a raw material, intermediate products generally comprise furfuryl alcohol and levulinate compounds.
The invention also provides a preparation method of gamma-valerolactone, which comprises the following steps of reacting furfuryl alcohol with secondary alcohol under the action of a catalyst to prepare gamma-valerolactone; the definition of the catalyst is as described above;
wherein the molar ratio of the catalyst to the furfuryl alcohol is preferably (0.1-100): 100, more preferably (1 to 10): 100, e.g., 5:100.
Wherein the secondary alcohol is as defined above.
Wherein preferably the secondary alcohol participates in the reaction as solvent and reactant.
Wherein the reaction may also be carried out in an inert solvent. The definition of the inert solvent is as described above.
When the reaction is carried out in an inert solvent, the secondary alcohol may participate in the reaction as a solvent and as a reactant, or may only participate in the reaction as a reactant.
Wherein the ratio of the volume (mL) of the secondary alcohol to the moles (mmol) of furfuryl alcohol is preferably 3: (0.01-1), more preferably 3 (0.05-0.5), for example 3:0.125.
The reaction temperature may be any reaction temperature conventional in the art, and is preferably 100 to 200 ℃, for example 140 to 170 ℃, and more for example 150 ℃.
Wherein the reaction time is as described above. The reaction time may be a reaction time conventional in the art, preferably 6 to 48 hours, for example 24 to 48 hours, further for example 36 hours.
When the catalyst is Sc (OTf) 3 When the molar ratio of the catalyst to the furfuryl alcohol is preferably (1 to 10): 100 (e.g., 5:100), the ratio of the volume (mL) of the secondary alcohol to the moles (mmol) of the furfuryl alcohol is preferably 3 (0.05 to 0.5) (e.g., 3:0.125), the temperature of the reaction is preferably 140 to 170 ℃ (e.g., 150 ℃), and the time of the reaction is preferably 24 to 36 hours (e.g., 36 hours).
The invention also provides a preparation method of gamma-valerolactone, which comprises the following steps of reacting levulinic acid ester compounds shown as a formula I with secondary alcohol under the action of a catalyst to prepare gamma-valerolactone;
the definition of the catalyst is as described above;
the R is 1 Is H or C 1 ～C 4 Alkyl of (a);
Wherein the secondary alcohol is as defined above.
Wherein preferably the secondary alcohol participates in the reaction as solvent and reactant.
Wherein the reaction may also be carried out in an inert solvent. The definition of the inert solvent is as described above.
When the reaction is carried out in an inert solvent, the secondary alcohol may participate in the reaction as a solvent and as a reactant, or may only participate in the reaction as a reactant.
Wherein the C 1 ～C 4 The alkyl group of (a) may be methyl, ethyl, isopropyl or tert-butyl.
Wherein the molar ratio of the catalyst to the levulinate compound shown in the formula I is preferably (0.1-100): 100, more preferably (1 to 10): 100, for example 5:100 or 10:100.
Wherein the ratio of the volume (mL) of the secondary alcohol to the molar (mmol) of the levulinate compound as shown in formula I is preferably 3: (0.01 to 1), more preferably 3: (0.05 to 0.5), for example 3:0.5.
The reaction temperature may be any reaction temperature conventional in the art, and is preferably 100 to 200 ℃, for example 140 to 170 ℃, and more for example 150 ℃.
The reaction time may be a reaction time which is conventional in the art, and is preferably 6 to 48 hours, for example, 24 to 48 hours, and further for example, 24 hours.
When the catalyst is Sc (OTf) 3 And said R 1 In the case of H, the molar ratio of catalyst to levulinic acid is preferably (1-10): 100 (e.g., 10:100), the ratio of the volume (mL) of the secondary alcohol to the molar (mmol) of levulinic acid is preferably 3 (0.05-0.5) (e.g., 3:0.5), the temperature of the reaction is preferably 140-170 ℃ (e.g., 150 ℃), and the time of the reaction is preferably 24-36 hours (e.g., 24 hours).
When the catalyst is Sc (OTf) 3 And said R 1 Is C 1 ～C 4 The molar ratio of the catalyst to the levulinate compound of formula I is preferably (1-10): 100 (e.g., 5:100), the volume (mL) of the secondary alcohol to the levulinate compound of formula I is preferably 3 (0.05-0.5) (e.g., 3:0.5), the reaction temperature is preferably 140-170 ℃ (e.g., 150 ℃), and the reaction time is preferably 24-36 hours (e.g., 24 hours).
The invention also provides a preparation method of the levulinate compound shown in the formula II, which comprises the following steps of reacting furfuryl ether compound shown in the formula III, water and fatty alcohol of non-secondary alcohol under the action of a catalyst to prepare the levulinate compound shown in the formula II;
The equivalent ratio of the furfuryl ether compound to the water is 1: (1-5);
the catalyst is M 1 (R 1 )n 1 Wherein M is 1 Selected from Ce, sc, Y, yb or Lu, R 1 Selected from trifluoromethanesulfonic acid group, perfluorobutanesulfonic acid group, heptadecafluorooctanesulfonic acid group, bis (trifluoromethanesulfonyl) amino group or bis (perfluorobutanesulfonyl) amino group;
the R is 3 Is C 1 ～C 4 Alkyl of (a);
the R is 2 An aliphatic hydrocarbon moiety that is a fatty alcohol that is not a secondary alcohol.
Wherein the M 1 (R 1 )n 1 N in (2) 1 Can be according to M 1 Bindable ligand R 1 The number of (2) is generally a positive integer.
Wherein the M 1 Sc is preferred.
Wherein the R is 1 Preferably a trifluoromethanesulfonic acid group or a perfluorobutanesulfonic acid group.
Wherein the catalyst is preferably Ce (OTf) 3 、Sc(ONf) 3 、Sc(OTf) 3 、Y(OTf) 3 、Yb(OTf) 3 And Lu (OTf) 3 、Sc(OPf) 3 、Sc(NTf 2 ) 3 And Sc (NNf) 2 ) 3 Such as Ce (OTf) 3 、Sc(ONf) 3 、Sc(OTf) 3 、Y(OTf) 3 、Yb(OTf) 3 、Lu(OTf) 3 、Sc(OPf) 3 、Sc(NTf 2 ) 3 Or Sc (NNf) 2 ) 3 。
Wherein the R is 3 Can be C 1 、C 2 Or C 4 For example methyl, ethyl or tert-butyl.
Wherein the molar ratio of the furfuryl ether compound to the water is preferably 1:5 or 1:1, more preferably 1:1.
Wherein the molar ratio of the catalyst to the furfuryl ether compound represented by formula III is preferably (0.1 to 100): 100, more preferably (1 to 10): 100, for example, 5:100.
Wherein the fatty alcohol other than secondary alcohol is preferably methanol, ethanol and C 3 ～C 10 One or more of the non-secondary alcohols of the aliphatic alcohols, such as one or more of methanol, ethanol and t-butanol, and further such as methanol, ethanol or t-butanol.
When the fatty alcohol other than the secondary alcohol is methanol, the R 2 Is methyl.
When the fatty alcohol other than the secondary alcohol is ethanol, the R 2 Is ethyl.
When the fatty alcohol other than the secondary alcohol is t-butanol, the R 2 Is tert-butyl.
Wherein preferably the fatty alcohol other than secondary alcohol participates in the reaction as a solvent and reactant.
Wherein the reaction may also be carried out in an inert solvent. The definition of the inert solvent is as described above.
When the reaction is carried out in an inert solvent, the fatty alcohol other than the secondary alcohol may participate in the reaction as a solvent and a reactant, or may only participate in the reaction as a reactant.
Wherein the ratio of the volume (mL) of the fatty alcohol other than the secondary alcohol to the molar (mmol) of the furfuryl ether compound represented by formula III is preferably 3 (0.01-1), more preferably 3 (0.1-1), for example 3:0.5.
The temperature of the reaction may be a reaction temperature conventional in the art, and is preferably 100 to 200 ℃, for example 100 ℃.
The reaction time may be a reaction time conventional in the art, and is preferably 6 to 48 hours, for example 12 hours.
The preparation method of the levulinate compound shown in the formula II can further comprise the following steps: under the action of a catalyst, furfuryl alcohol and fatty alcohol of non-secondary alcohol react to prepare furfuryl ether compounds shown in a formula III;
the catalyst is M 1 (R 1 )n 1 The definition of which is as described above;
the R is 3 Is as defined above;
the molar ratio of the catalyst to the furfuryl alcohol is preferably (0.1 to 100): 100, more preferably (1 to 10): 100, for example 5:100.
The ratio of the volume (mL) of the fatty alcohol other than secondary alcohol to the molar (mmol) of furfuryl alcohol is preferably 3 (0.125 to 0.5), such as 3:0.125 or 3:0.5.
The invention also provides a preparation method of the levulinate compound shown in the formula II, which comprises the following steps of reacting furfuryl alcohol with fatty alcohol of non-secondary alcohol under the action of a catalyst to prepare the levulinate compound shown in the formula II;
the catalyst is M 1 (R 1 )n 1 The definition of which is as described above;
the R is 2 Is as defined above;
wherein the catalyst is preferably Ce (OTf) 3 、Sc(ONf) 3 、Sc(OTf) 3 、Y(OTf) 3 、Yb(OTf) 3 And Lu (OTf) 3 、Sc(OPf) 3 、Sc(NTf 2 ) 3 And Sc (NNf) 2 ) 3 Such as Ce (OTf) 3 、Sc(ONf) 3 、Sc(OTf) 3 、Y(OTf) 3 、Yb(OTf) 3 、Lu(OTf) 3 、Sc(OPf) 3 、Sc(NTf 2 ) 3 Or Sc (NNf) 2 ) 3 。
Wherein the molar ratio of the catalyst to the furfuryl alcohol is preferably (0.1 to 100): 100, more preferably (1 to 10): 100, for example 5:100.
Wherein the fatty alcohol other than secondary alcohol is preferably methanol, ethanol and C 3 ～C 10 One or more of the non-secondary alcohols of the aliphatic alcohols, such as one or more of methanol, ethanol and t-butanol, and further such as methanol, ethanol or t-butanol.
Wherein preferably the fatty alcohol other than secondary alcohol participates in the reaction as a solvent and reactant.
Wherein the reaction may also be carried out in an inert solvent. The definition of the inert solvent is as described above.
When the reaction is carried out in an inert solvent, the fatty alcohol other than the secondary alcohol may participate in the reaction as a solvent and a reactant, or may only participate in the reaction as a reactant.
Wherein the ratio of the volume (mL) of the fatty alcohol other than secondary alcohol to the molar (mmol) of the furfuryl alcohol compound is preferably 3 (0.01-1), more preferably 3 (0.05-0.5), for example 3:0.5.
The temperature of the reaction may be a reaction temperature conventional in the art, and is preferably 100 to 200 ℃, for example 100 ℃.
The reaction time may be a reaction time conventional in the art, and is preferably 6 to 48 hours, for example 12 hours.
When the catalyst is Sc (OTf) 3 And the molar ratio of the catalyst to the furfuryl alcohol is preferably (1 to 10): 100 (e.g., 5:100), the molar (mL) ratio of the fatty alcohol of the non-secondary alcohol to the furfuryl alcohol is preferably 3 (0.05 to 0.5) (e.g., 3:0.5), the temperature of the reaction is preferably 100 to 200 ℃ (e.g., 100 ℃), and the time of the reaction is preferably 6 to 48 hours (e.g., 12 hours).
The invention also provides a preparation method of gamma-valerolactone, which comprises the following steps of reacting xylose biomass with secondary alcohol under the action of a catalyst to prepare gamma-valerolactone;
the catalyst is M 1 (R 1 )n 1 The definition of which is as described above;
in the present invention, the xylose-type biomass is generally subjected to grinding and drying treatment before the reaction.
Wherein the catalyst is preferably Sc (OTf) 3 。
Wherein the xylose-type biomass refers to plant organisms containing xylose structural units formed through photosynthesis, such as corncobs and/or stalks, and further such as one or more of hemicellulose, xylan and xylose.
The hemicellulose generally refers to a polymer composed of one or several different types of monosaccharides, and is composed of xylose units as shown in formula 1:
the xylose is shown as a formula 2:
wherein the secondary alcohol is as defined above.
Wherein preferably the secondary alcohol participates in the reaction as solvent and reactant.
Wherein the reaction may also be carried out in an inert solvent. The definition of the inert solvent is as described above.
When the reaction is carried out in an inert solvent, the secondary alcohol may participate in the reaction as a solvent and as a reactant, or may only participate in the reaction as a reactant.
Wherein the molar ratio of the catalyst to the biomass is preferably (0.1 to 100): 100, more preferably (10 to 30): 100, e.g., 20:100.
Wherein the ratio of the volume (mL) of the secondary alcohol to the mole (mmol) of the biomass is preferably 3 (0.001 to 0.1), more preferably 3 (0.025 to 0.05), for example 3:0.025 or 3:0.05.
Wherein the ratio of the volume (mL) of the secondary alcohol to the mass (mg) of the biomass is preferably 3 (10-100), more preferably 3 (20-50), for example 3:25.
The reaction temperature may be any reaction temperature conventional in the art, and is preferably 150 to 250 ℃, for example 170 to 210 ℃, and still more for example 190 ℃.
The reaction time may be a reaction time which is conventional in the art, and is preferably 6 to 48 hours, for example 24 to 48 hours, and further for example 24 hours or 48 hours.
When the biomass is xylose, the catalyst is preferably Sc (OTf) 3 The molar ratio of the catalyst to the biomass is preferably 20:100, the volume of secondary alcohol (mL) to the molar (mmol) ratio of the biomass is preferably 3:0.05, the temperature of the reaction is preferably 190 ℃, and the time of the reaction is preferably 24 hours.
When the biomass is xylan, the catalyst is preferably Sc (OTf) 3 The molar ratio of the catalyst to the biomass is preferably 20:100, the volume of secondary alcohol (mL) to the molar (mmol) ratio of the biomass is preferably 3:0.05 or 3:0.025, the temperature of the reaction is preferably 190 ℃, and the time of the reaction is preferably 24 hours.
When the biomass is corncob, the catalyst is preferably Sc (OTf) 3 The molar ratio of the catalyst to the biomass is preferably 20:100, the ratio of the volume of the secondary alcohol (mL) to the mass of the biomass (mg) is preferably 3:25, the temperature of the reaction is preferably 190 ℃, and the time of the reaction is preferably 48h.
In the present invention, the catalyst may be immobilized by a resin, which may be Nafion resin (available from the southern da synthesis). For example, the catalyst is immobilized by Nafion resin to prepare the catalyst with the M-Nafion structure. In the invention, after the catalyst is immobilized by resin, the catalyst is regenerated, and the regeneration process is simple and convenient and is easy to operate.
On the basis of conforming to the common knowledge in the field, the above preferred conditions can be arbitrarily combined to obtain the preferred examples of the invention.
The reagents and materials used in the present invention are commercially available.
The invention has the positive progress effects that:
(1) The invention realizes the preparation of gamma-valerolactone directly from biomass and fine chemical products derived from biomass (such as hemicellulose, xylose, furfural, furfuryl alcohol and the like) as raw materials through a series of processes of dehydration, reduction, ring opening, isomerization, esterification, reduction and ring closure, wherein the yield of the gamma-valerolactone prepared from the furfural as the raw material can reach 95%, the yield of the gamma-valerolactone prepared from xylose as the raw material can reach 53%, and the yield of the gamma-valerolactone prepared from xylan as the raw material can reach 51%.
(2) The method utilizes the commercialized single Lewis acid as the catalyst, avoids the step-by-step and complex product separation process in the traditional gamma-valerolactone preparation process, is simple and efficient, and realizes the low-cost production of gamma-valerolactone; the secondary alcohol can be used as a solvent and a hydrogen source, so that the safety problem caused by the use of hydrogen in the traditional reduction process is avoided; the catalyst can be reused, the separation process is simple (distillation), and the problems of complex and complicated separation and purification process and severe catalyst preparation conditions and complex catalytic system in the conventional production route and technology are avoided.
(3) The method utilizes the commercialized single Lewis acid as a catalyst to prepare the levulinate compound by catalysis, wherein the yield of the levulinate compound prepared by using furfuryl alcohol as a raw material can reach 90 percent, and the yield of the levulinate compound prepared by using furfuryl ether compound, fatty alcohol of non-secondary alcohol and water as raw materials can reach 68 percent.
(4) In the preparation method, macromolecular biomass can be used as a raw material to directly prepare gamma-valerolactone, and a trigger is provided for the development of industrial chains of large-scale renewable chemical products with biomass such as corncobs as cores.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of furfural 1 H NMR(CDCl 3 ,500MHz)。
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of furfuryl alcohol 1 H NMR(CDCl 3 ,500MHz)。
FIG. 3 is a nuclear magnetic resonance spectrum of isopropyl levulinate 1 H NMR(CDCl 3 ,500MHz)。
FIG. 4 shows a nuclear magnetic resonance hydrogen spectrum of gamma valerolactone 1 H NMR(CDCl 3 ,500MHz)。
FIG. 5 is an in situ nuclear magnetic resonance hydrogen spectrum of example 24 1 H NMR(CDCl 3 ,500MHz)。
FIG. 6 is an in situ nuclear magnetic resonance hydrogen spectrum of example 25 1 H NMR(CDCl 3 ,500MHz)。
FIG. 7 is a nuclear magnetic resonance hydrogen spectrum of example 26 1 H NMR(CDCl 3 ,500MHz)。
FIG. 8 is an in situ nuclear magnetic resonance spectrum of example 27 13 C NMR(C 6 D 6 ,126MHz)。
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
In the following examples, the preparation process was carried out in a pressure-resistant Schlenk tube, and after the reaction was completed, the reaction was cooled to room temperature and then examined.
In the examples below, the detection of the product was carried out by 1 H NMR、 13 C NMR and GC-MS determine their composition and content tests were carried out by GC (Agilent 6890).
Test conditions: agilent US0769531J (DB-WAX 15 m.times.0.320 mm.times.0.25 μm) capillary column, flame ionization detector, N 2 Carrier gas (2 mL/min); temperature program: retained at 60 ℃ for 5 minutes); heating to 70deg.C (keeping for 10 min) at 5deg.C/min; heating to 80 ℃ at a rate of 2 ℃/min (4 minutes of retention); heating to 200deg.C (2 min for 2 min) at 5deg.C/min; sample inlet temperature: 250 ℃; detector temperature: 250 ℃; injection amount: 10 muL. Naphthalene is used as an internal standard, and the content of the product is measured by an internal standard method.
In the following examples and comparative examples: sc (Sc) 2 O 3 Purchased from Annaiji pharmaceutical Co, scCl 3 ·6H 2 O was purchased from Ann Ji drug Co., scCl 3 Purchased from Annaiji pharmaceutical Co., ltd., sc (OTf) 3 Purchased from Annaiji pharmaceutical Co, Y (OTf) 3 Yb (OTf) from Annaiji pharmaceutical Co 3 Purchased from Annaiji pharmaceutical Co., ltd., al (OTf) 3 Purchased from Annaiji pharmaceutical Co., ltd., al (iPrO) 3 Purchased from carbofuran pharmaceutical company, phy-Zr is self-prepared, and HOTf is purchased from carbofuran pharmaceutical company.
In the following examples, sc (ONf) 3 The preparation method of (2) comprises the following steps: scandium oxide Sc 2 O 3 Reflux-extracting with perfluorobutanesulfonic acid in water, filtering to collect solid, and oven drying to obtain Sc (ONf) 3 。
In example 10, the catalyst was immobilized on Nafion (perfluorosulfonic acid resin) resin by the following method: scCl is put into 3 ·6H 2 Dissolving O in ethanol, adding Nafion resin, dispersing thoroughly, adding ammonia water, refluxing, filtering, washing and drying. After the resin is solidified, the catalyst is Sc-Nafion (scandium perfluorosulfonate resin).
EXAMPLE 1 preparation of gamma valerolactone
Pressure-resistant Shi Laike pipe was taken and 0.05mmol of furfural and 5% mmol of Sc (ONf) were added 3 3mL of isopropanol was added, stirred, and reacted at 150℃for 36 hours to determine the conversion of the raw materials and the yield of the product, as shown in Table 1.
Furfural: 1 H NMR(CDCl 3 500 MHz) see fig. 1.
Furfuryl alcohol: 1 H NMR(CDCl 3 500 MHz) see fig. 2.
Isopropyl levulinate: 1 H NMR(CDCl 3 500 MHz) see fig. 3.
Gamma valerolactone: 1 H NMR(CDCl 3 500 MHz) see fig. 4.
The preparation methods of examples 2 to 22 were the same as in example 1. The raw materials, the types of the catalysts and the reaction conditions are shown in Table 1, and the yields of the products and the by-products are also shown in Table 1.
TABLE 1
Note that: "/" indicates that no detection was performed.
Example 23
Pressure-resistant Shi Laike tube was taken and 250mg of corncob, 20% mmol of Sc (OTf) was added 3 30mL of isopropanol was added thereto and stirred to react at 190℃for 48 hours, and the yield of the product was determined to be 18% of gamma valerolactone.
Examples 1 to 23 show that:
(1) Examples 1-6 illustrate that when furfural is used as a raw material, the triflate of cerium, scandium, yttrium, ytterbium and lutetium can directly prepare gamma-valerolactone, and that metal scandium and lanthanide metal salts are suitable for catalyzing furfural to generate gamma-valerolactone by a one-pot method; especially, the yield of gamma-valerolactone prepared by catalyzing the triflate of scandium, yttrium, ytterbium and lutetium can reach more than 90%, and the catalysis effect is good;
(2) Example 7 illustrates that the yield of gamma valerolactone can reach 92% when furfuryl alcohol is used as a raw material, and that scandium metal salt and lanthanide metal salt are also suitable for catalyzing furfuryl alcohol to produce gamma valerolactone;
(3) Examples 8 to 9 and 22 to 23 show that the yield of gamma valerolactone can reach 53% when biomass (xylose, xylan and corncob) is used as a raw material, and that metal scandium and lanthanide metal salts are also suitable for catalyzing biomass to generate gamma valerolactone;
(4) Example 10 illustrates that after the catalyst is immobilized by Nafion resin, the catalyst can still catalyze furfural to generate gamma-valerolactone, the yield is more than 60%, and the industrial application mode of the catalyst is enlarged;
(5) Examples 11 to 14 show that the yield of gamma-valerolactone can reach more than 90% when levulinate compounds are used as raw materials, and that scandium metal salt and lanthanide metal salt are also suitable for catalyzing levulinate compounds to generate gamma-valerolactone;
(6) Examples 15 to 18 demonstrate that, within a certain range, an extension of the reaction time and an increase in the reaction temperature are advantageous for increasing the yield of gamma-valerolactone; however, too high a reaction temperature and too long a reaction time may adversely result in a decrease in the yield of gamma valerolactone;
(7) Examples 17, 19 to 21 show that when the ratio of furfural (mmol) to secondary alcohol (mL) is in the range of (0.1-0.5): 3, the yield of gamma valerolactone increases with decreasing concentration of furfural. The inventor finds that in the preparation method, the side reaction is increased after the concentration of the furfural is increased, so that the yield of gamma-valerolactone is increased along with the decrease of the concentration of the furfural under the condition of unchanged total volume.
Example 2 separation of the product by distillation after completion of the reaction and recovery of Sc (OTf) 3 The catalyst can be repeatedly used after being washed by methylene dichloride and dried, and the yield of gamma-valerolactone after 4 times of circulation can still reach 95% under the condition of 150 ℃ and 36 hours for the catalytic concentration of 0.05mmol/3 mL. The reaction conditions and the amounts of the starting materials were the same as in example 2. Specific data can be seen in table 2 below.
TABLE 2
From the above, the catalyst in the application can be reused, the catalytic efficiency does not change obviously after multiple uses, the separation process of the product and the catalyst is simple, and the generation cost can be effectively reduced.
Example 24
Take pressure-resistant Shi Laike tube, add 1.95mmol furfural, 5% mmol Sc (OTf) 3 1.5mL of isopropanol is added, stirred, reacted for 2 hours at the temperature of 100 ℃, sampled and subjected to nuclear magnetic resonance detection, and an in-situ nuclear magnetic resonance chart can be seen in FIG. 5.
As can be seen from fig. 5, in the process of producing gamma valerolactone using furfural as a substrate under the above reaction conditions, an intermediate process of furfuryl alcohol was performed, in which-OH in furfuryl alcohol is an active hydrogen, which cannot be confirmed from fig. 5.
Example 25
Based on example 24, the reaction was continued for 3 hours after the temperature was raised to 150℃and a sample was taken for nuclear magnetic resonance detection, and the in-situ nuclear magnetic resonance chart was shown in FIG. 6.
As can be seen from fig. 6, in the process of producing gamma valerolactone using furfural as a substrate under the above reaction conditions, an intermediate process of isopropyl levulinate was undergone. In fig. 6, methyl groups 5 and 6 overlap with the solvent peaks, and cannot be confirmed.
Example 26
Pressure-resistant Shi Laike pipe was taken and 0.05mmol of furfural and 5% mmol of Sc (OTf) were added 3 3mL of isopropanol was added, stirred, reacted at 150℃for 36 hours, and after removal of isopropanol, a sample was taken for nuclear magnetic resonance examination, and the nuclear magnetic resonance chart was shown in FIG. 7.
As can be seen from fig. 7, under the above reaction conditions, furfural was used as a substrate, and gamma valerolactone was used as an end product.
Example 27
A pressure-resistant Shi Laike tube was taken and charged with 0.24mmol furfuryl alcohol, 5% mmol Sc (OTf) 3 0.3mL of absolute ethanol and 0.2mL of C were added 6 D 6 Stirring, reacting at 100deg.C for 30min, sampling, and performing nuclear magnetic detection, wherein the nuclear magnetic pattern is shown in FIG. 8.
As can be seen from FIG. 8, in the above reaction conditions, furfuryl ethyl ether and 4, 5-triethoxy-2-pentanone were subjected to an intermediate process in the production of ethyl levulinate from furfuryl alcohol as a substrate.
EXAMPLE 28 preparation of levulinate Compounds
Taking a pressure-resistant Shi Laike pipe, adding furfuryl ethyl ether and water (molar ratio 1:1), and adding Sc (OTf) 3 3mL of ethanol was added thereto, stirred, and reacted at 100℃for 12 hours to determine the conversion of the raw materials and the yield of the product, as shown in Table 3.
The preparation methods of examples 29 to 31 were the same as in example 28. The starting materials, the catalyst types and the reaction conditions are shown in Table 3, and the levulinate yields are also shown in Table 3.
TABLE 3 Table 3
From the above table, it can be seen that:
(1) Example 28 and comparative example 7 are described as Sc (OTf) 3 In the reaction of catalyzing furfuryl ethyl ether to generate ethyl levulinate, when the raw material does not contain water, the yield of the ethyl levulinate is obviously reduced (from 68% to 22%);
(2) Examples 29 to 31 illustrate Sc (OTf) 3 In the reaction of catalyzing furfuryl ethyl ether to generate levulinate compounds, the influence of an alcohol source on the yield of the levulinate compounds is remarkable, and under the same reaction conditions, when the alcohol source is tertiary butanol, the yield of the levulinate compounds is highest and can reach 90%.
Comparative example 1
Taking a pressure-resistant Shi Laike pipe, adding 0.5mmol of furfural and 5% mmol of Sc 2 O 3 3mL of isopropanol was added and stirred to react at 150℃for 36 hours, and the furfuryl alcohol yield, isopropyl levulinate yield and gamma-valerolactone yield were all 0%.
Comparative example 2
Pressure-resistant Shi Laike pipe was taken and 0.5mmol of furfural and 5% mmol of Al (iPrO) were added 3 3mL of isopropyl alcohol was added, and the mixture was stirred and reacted at 150℃for 36 hours, with a furfuryl alcohol yield of 93%, an isopropyl levulinate yield of 0% and a gamma valerolactone yield of 0%.
Comparative example 3
Taking a pressure-resistant Shi Laike pipe, adding 0.5mmol of furfural and 5% mmol of Phy-Zr, adding 3mL of isopropanol, stirring, and reacting for 36h at 150 ℃, wherein the furfuryl alcohol yield is 99%, the isopropyl levulinate yield is 0%, and the gamma-valerolactone yield is 0%.
Comparative example 4
Taking a pressure-resistant Shi Laike pipe, adding 0.5mmol of furfural and 5% mmol of ScCl 3 ·6H 2 O, 3mL of isopropanol was added, and the mixture was stirred and reacted at 150℃for 36 hours, with an isopropyl levulinate yield of 35% and a gamma valerolactone yield of 0%.
Comparative example 5
Taking a pressure-resistant Shi Laike pipe, adding 0.5mmol of furfural and 5% mmol of ScCl 3 3mL of isopropanol was added, and the mixture was stirred and reacted at 150℃for 36 hours, with an isopropyl levulinate yield of 33% and a gamma valerolactone yield of 0%.
Comparative example 6
Pressure-resistant Shi Laike pipe was taken and 0.5mmol of furfural and 5% mmol of Al (OTf) were added 3 3mL of isopropyl alcohol was added and stirred to react at 150℃for 36 hours, with a furfuryl alcohol yield of 35%, an isopropyl levulinate yield of 32% and a gamma valerolactone yield of 0%.
Comparative example 7
A pressure-resistant Shi Laike tube was taken and charged with 0.5mmol furfuryl ethyl ether, 5% mmol Sc (OTf) 3 3mL of ethanol was added thereto, and the mixture was stirred and reacted at 100℃for 12 hours, whereby the yield of ethyl levulinate was 22%.
Claims (20)
1. The preparation method of gamma-valerolactone is characterized by comprising the following steps of reacting furfural with secondary alcohol under the action of a catalyst to prepare gamma-valerolactone;
the catalyst is M (R) n, wherein M is selected from Ce, sc, Y, yb or Lu; r is selected from trifluoromethanesulfonic acid group or perfluorobutanesulfonic acid group; n is 3;
the secondary alcohol is selected from C 3 ～C 6 Secondary alcohols of (a);
2. the process for preparing gamma valerolactone as claimed in claim 1, wherein M is Sc.
3. The method for preparing gamma valerolactone as claimed in claim 1, wherein the catalyst is Ce (OTf) 3 、Sc(ONf) 3 、Sc(OTf) 3 、Y(OTf) 3 、Yb(OTf) 3 And Lu (OTf) 3 One or more of the following;
and/or the molar ratio of the catalyst to the furfural is (0.1-100): 100;
And/or, the secondary alcohol is isopropanol;
and/or, the reaction is carried out in an inert solvent;
and/or the molar mmol ratio of the volume mL of the secondary alcohol to the furfural is 3 (0.01-1);
and/or, the temperature of the reaction is 100-200 ℃;
and/or the reaction time is 6-48 h.
4. A process for the preparation of gamma valerolactone as claimed in claim 3, wherein the catalyst is Ce (OTf) 3 、Sc(ONf) 3 、Sc(OTf) 3 、Y(OTf) 3 、Yb(OTf) 3 Or Lu (OTf) 3 ；
And/or the molar ratio of the catalyst to the furfural is (1-10): 100;
and/or the inert solvent is one or more of hexane, benzene, carbon tetrachloride and dichloroethane;
and/or the molar mmol ratio of the volume mL of the secondary alcohol to the furfural is 3 (0.05-0.5);
and/or, the temperature of the reaction is 140-170 ℃;
and/or the reaction time is 24-48 h.
5. The method for preparing gamma valerolactone as claimed in claim 4, wherein the molar ratio of catalyst to furfural is 5:100;
and/or the molar mmol ratio of the volume mL of secondary alcohol to the furfural is 3:0.05, 3:0.1, 3:0.125, 3:0.25 or 3:0.5;
and/or the temperature of the reaction is 140 ℃, 150 ℃ or 170 ℃;
And/or the reaction time is 24 hours, 36 hours or 48 hours.
6. The preparation method of gamma-valerolactone is characterized by comprising the following steps of reacting furfuryl alcohol with secondary alcohol under the action of a catalyst to prepare gamma-valerolactone;
the catalyst is M (R) n, wherein M is selected from Ce, sc, Y, yb or Lu; r is selected from trifluoromethanesulfonic acid group or perfluorobutanesulfonic acid group; n is 3;
the secondary alcohol is selected from C 3 ～C 6 Secondary alcohols of (a);
7. the method of claim 6, wherein M is Sc.
8. The method for producing gamma valerolactone as claimed in claim 6, wherein the molar ratio of said catalyst to said furfuryl alcohol is (0.1 to 100): 100;
and/or the catalyst is Ce (OTf) 3 、Sc(ONf) 3 、Sc(OTf) 3 、Y(OTf) 3 、Yb(OTf) 3 And Lu (OTf) 3 One or more of the following;
and/or, the secondary alcohol is isopropanol;
and/or, the reaction is carried out in an inert solvent;
and/or the molar ratio of the volume mL of the secondary alcohol to the furfuryl alcohol is 3: (0.01-1);
and/or, the temperature of the reaction is 100-200 ℃;
and/or the reaction time is 6-48 h.
9. The method for producing gamma valerolactone as claimed in claim 8, wherein the molar ratio of said catalyst to said furfuryl alcohol is (1 to 10): 100;
And/or the catalyst is Ce (OTf) 3 、Sc(ONf) 3 、Sc(OTf) 3 、Y(OTf) 3 、Yb(OTf) 3 Or Lu (OTf) 3 ；
And/or the inert solvent is one or more of hexane, benzene, carbon tetrachloride and dichloroethane;
and/or the molar mmol ratio of the volume mL of the secondary alcohol to the furfuryl alcohol is 3 (0.05-0.5);
and/or, the temperature of the reaction is 140-170 ℃;
and/or the reaction time is 24-48 h.
10. The method for producing gamma valerolactone as claimed in claim 8, wherein the molar ratio of said catalyst and said furfuryl alcohol is 5:100;
and/or the molar mmol ratio of the volume mL of secondary alcohol to the furfuryl alcohol is 3:0.125;
and/or, the temperature of the reaction is 150 ℃;
and/or the reaction time is 36h.
11. The preparation method of gamma-valerolactone is characterized by comprising the following steps of reacting levulinic acid ester compounds shown as a formula I with secondary alcohol under the action of a catalyst to prepare gamma-valerolactone; r is R 1 Is H or C 1 ～C 4 Alkyl of (a);
the catalyst is M (R) n, wherein M is selected from Ce, sc, Y, yb or Lu; r is selected from trifluoromethanesulfonic acid group or perfluorobutanesulfonic acid group; n is 3;
the secondary alcohol is selected from C 3 ～C 6 Secondary alcohols of (a);
12. the process for preparing gamma valerolactone as claimed in claim 11, wherein M is Sc.
13. The method for preparing gamma valerolactone as claimed in claim 11, wherein the molar ratio of the catalyst to levulinate compound as shown in formula I is (0.1-100): 100;
and/or the catalyst is Ce (OTf) 3 、Sc(ONf) 3 、Sc(OTf) 3 、Y(OTf) 3 、Yb(OTf) 3 And Lu (OTf) 3 One or more of the following;
and/or, the secondary alcohol is isopropanol;
and/or, the reaction is carried out in an inert solvent;
and/or, the C 1 ～C 4 Is selected from methyl, ethyl, isopropyl or tert-butyl;
and/or the molar ratio of the volume mL of the secondary alcohol to the levulinate compound shown as the formula I is 3: (0.01-1);
and/or, the temperature of the reaction is 100-200 ℃;
and/or the reaction time is 6-48 h.
14. The method for producing gamma valerolactone as claimed in claim 13, wherein the molar ratio of the catalyst to levulinate compound represented by formula I is (1 to 10): 100;
and/or the catalyst is Ce (OTf) 3 、Sc(ONf) 3 、Sc(OTf) 3 、Y(OTf) 3 、Yb(OTf) 3 Or Lu (OTf) 3 ；
And/or the inert solvent is one or more of hexane, benzene, carbon tetrachloride and dichloroethane;
and/or the molar ratio of the volume mL of the secondary alcohol to the levulinate compound shown as the formula I is 3: (0.05 to 0.5);
And/or, the temperature of the reaction is 140-170 ℃;
and/or the reaction time is 24-48 h.
15. The method for preparing gamma valerolactone as claimed in claim 14, wherein the molar ratio of catalyst to levulinate compound of formula I is 5:100 or 10:100;
and/or the molar ratio of the volume mL of the secondary alcohol to the levulinate compound shown as the formula I is 3:0.5;
and/or, the temperature of the reaction is 150 ℃;
and/or the reaction time is 24h.
16. The preparation method of gamma-valerolactone is characterized by comprising the following steps of reacting xylose biomass with secondary alcohol under the action of a catalyst to prepare gamma-valerolactone;
the catalyst is M 1 (R 1 )n 1 Wherein M is 1 Selected from Ce, sc, Y, yb or Lu; r is R 1 Selected from trifluoromethanesulfonic acid groups or perfluorobutanesulfonic acid groups; n is n 1 3;
the xylose type biomass is one or more of corncob, xylan and xylose;
the secondary alcohol is selected from C 3 ～C 6 Secondary alcohols of (a);
17. the method for producing gamma valerolactone as claimed in claim 16, wherein M is selected from the group consisting of 1 Sc.
18. The method for producing gamma valerolactone as claimed in claim 16, wherein the xylose-type biomass is subjected to grinding and drying treatment before the reaction;
And/or the catalyst is Ce (OTf) 3 、Sc(ONf) 3 、Sc(OTf) 3 、Y(OTf) 3 、Yb(OTf) 3 And Lu (OTf) 3 One or more of the following;
and/or, the secondary alcohol is isopropanol;
and/or, the reaction is carried out in an inert solvent;
and/or the molar ratio of the catalyst to the biomass is (0.1-100): 100;
and/or the molar mmol ratio of the volume mL of the secondary alcohol to the biomass is 3 (0.001-0.1); alternatively, the ratio of the volume mL of the secondary alcohol to the mass mg of the biomass is 3 (10-100);
and/or, the temperature of the reaction is 150-250 ℃;
and/or the reaction time is 6-48 h.
19. The method for preparing gamma valerolactone as claimed in claim 18, wherein the catalyst is Ce (OTf) 3 、Sc(ONf) 3 、Sc(OTf) 3 、Y(OTf) 3 、Yb(OTf) 3 Or Lu (OTf) 3 ；
And/or the inert solvent is one or more of hexane, benzene, carbon tetrachloride and dichloroethane;
and/or the molar ratio of the catalyst to the biomass is (10-30): 100;
and/or the molar mmol ratio of the volume mL of the secondary alcohol to the biomass is 3 (0.025-0.05); alternatively, the ratio of the volume mL of the secondary alcohol to the mass mg of the biomass is 3 (20-50);
and/or, the temperature of the reaction is 170-210 ℃;
and/or the reaction time is 24-48 h.
20. The method of producing gamma valerolactone of claim 19, wherein the molar ratio of said catalyst to said biomass is 20:100;
and/or the molar mmol ratio of the volume mL of secondary alcohol to the biomass is 3:0.025 or 3:0.05; alternatively, the ratio of the volume mL of the secondary alcohol to the mass mg of biomass is 3:25;
and/or, the temperature of the reaction is 190 ℃;
and/or the reaction time is 24 or 48 hours.
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