CN112778124A - Application of ionic liquid based on biimidazole in aspect of catalyzing biomass to prepare levulinic acid - Google Patents
Application of ionic liquid based on biimidazole in aspect of catalyzing biomass to prepare levulinic acid Download PDFInfo
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Abstract
The invention discloses an application of an ionic liquid based on biimidazole in preparation of levulinic acid by catalyzing biomass. When the ionic liquid based on the biimidazole is used for catalyzing biomass to prepare levulinic acid, on one hand, the catalyst can be recycled, on the other hand, the reaction rate can be effectively improved, the reaction time is shortened, the product yield is improved, and can reach about 76.5% at most, and the problems of equipment corrosion, waste acid pollution and the like caused by the fact that inorganic acid is used as the catalyst are effectively solved.
Description
Technical Field
The invention relates to application of an ionic liquid based on biimidazole in preparation of levulinic acid by catalyzing biomass.
Background
The levulinic acid contains a carboxyl group and a ketone group in a molecular structure, so the levulinic acid has good reactivity, can synthesize various chemical products through esterification, polymerization, hydrogenation and other reactions, and has wide application prospects in the fields of medicines, gasoline additives, daily chemicals, lubricants, surfactants, electronic materials, plastics, batteries and the like.
The existing method for preparing acetic acid propionic acid by using biomass mainly comprises two methods, namely a furfuryl alcohol hydrolysis method and a biomass direct hydrolysis method. Since furfuryl alcohol can also be prepared by hydrolysis of biomass, both processes are prepared from biomass as a raw material. The furfuryl alcohol hydrolysis method needs four steps of hydrolysis, dehydration, hydrogenation and hydrolysis, and has the disadvantages of long process flow, low yield and poor economical efficiency. The direct biomass hydrolysis method generally obtains the levulinic acid through continuous hydrolysis, and the process is simple. However, the catalysts used in the hydrolysis process are mainly inorganic acids including sulfuric acid, hydrochloric acid, hydrofluoric acid, etc., and these catalysts are highly corrosive to equipment and cannot be recycled, so that a large amount of waste liquid and waste residues are generated.
Disclosure of Invention
The purpose of the invention is as follows: the invention provides an application of an ionic liquid based on biimidazole as a catalyst in catalyzing biomass to prepare levulinic acid, aiming at solving the problems of high equipment corrosivity, incapability of recycling the catalyst and high waste liquid and waste residue amount existing in the process of preparing the levulinic acid by using an inorganic acid as the catalyst by a biomass direct hydrolysis method in the prior art.
The technical scheme is as follows: the application of the ionic liquid based on the biimidazole in the aspect of catalyzing biomass to prepare levulinic acid is disclosed.
Wherein the specific reaction process is as follows: mixing the biomass, the ionic liquid and a solvent, reacting at high temperature, and extracting the reaction solution after reaction by using an organic solvent to obtain the levulinic acid.
Wherein the mass ratio of the ionic liquid to the biomass is 0.1-20: 1, and the mass ratio of the solvent to the biomass is 0.3-2: 1.
Wherein the reaction temperature is not more than 200 ℃, and the reaction time is 0.1-10 h.
Wherein the structural general formula of the ionic liquid based on the biimidazole is as follows:
or
In the formula (I) and the formula (II), n is any value of 1-10; r1And R2Exists in ion form and can be F-、Cl-、Br-、I-、HSO4 -、H2PO4 -、CF3SO3 -、CH3SO3 -、FeCl4 -、AlCl4 -、HSiO3 -、H2PW12O40 -、
One kind of (1).
The preparation method of the ionic liquid based on the biimidazole comprises the following steps: mixing a sulfonic acid group compound containing biimidazole, a Bronsted acid compound and water, and refluxing for 4-8 hours at the temperature of 80-100 ℃ to obtain the biimidazole-based ionic liquid.
Wherein, the structural general formula of the sulfonic acid group compound containing the biimidazole is as follows:
wherein n is any number from 1 to 10.
Wherein the Bronsted acid compound is HF, HCl, HBr, HI, H2SO4、H3PO4、CF3SO3H、CH3SO3H、FeCl3、AlCl3、H2SiO3、H3PW12O40、
One kind of (1).
Wherein the sulfonic acid group compound containing the biimidazole is prepared by adopting the following method: dissolving imidazole in dimethyl sulfoxide, and reacting under the conditions of sodium hydroxide and dichloroalkane or dibromoalkane to obtain a biimidazole compound B; mixing the biimidazole compound B and 1, 4-butanesultone, and stirring at normal temperature for not less than 72 hours to obtain a sulfonic compound C containing biimidazole; or mixing the biimidazole compound B and 1, 3-propane sultone, adding a solvent toluene, reacting at 90 ℃, washing the obtained solid compound with toluene and diethyl ether respectively, removing unreacted raw materials of 1, 3-propane sultone or 1, 4-butane sultone, and drying to obtain a sulfonic acid group compound C containing biimidazole;
wherein imidazole is
When imidazole is
When 1, 4-dichlorobutane or 1, 4-dibromobutane is used for reacting with the imidazole compound B, the bisimidazole compound B is obtained1The structural formula is as follows:
biimidazole compound B1Reacting 1, 3-propane sultone with the compound C to prepare the compound C1The structural formula is as follows:
biimidazole compound B1Reacting 1, 4-butanesultone with the compound C to obtain the compound C2The structural formula is as follows:
the ionic liquid has a reaction formula:
the ionic liquid synthesized by the invention takes units containing the biimidazole and the sulfonic group as cations and takes halogen ions (such as fluorine, chlorine, bromine and iodine), hydrogen sulfate, phosphate radical or triflate radical as anions to form the ionic liquid containing the cations and the anions.
Has the advantages that: when the ionic liquid based on the biimidazole is used for catalyzing biomass to prepare levulinic acid, on one hand, the catalyst can be recycled, on the other hand, the reaction rate can be effectively improved, the reaction time is shortened, the product yield is improved, and can reach about 76.5% at most, and the problems of equipment corrosion, waste acid pollution and the like caused by the fact that inorganic acid is used as the catalyst are effectively solved.
Drawings
FIG. 1 is a diagram of ultraviolet absorption spectra of different ionic liquids;
FIG. 2 is a thermogravimetric analysis of different ionic liquids.
FIG. 3 is a graph showing the yield of levulinic acid prepared by converting cellulose catalyzed by ionic liquid BSIM-Br after multiple recoveries;
FIG. 4 shows ionic liquid BSIM-HSO4The yield chart of the levulinic acid prepared by catalyzing the conversion of the cellulose after being recovered for a plurality of times.
Detailed Description
The technical solution of the present invention is further described with reference to the following specific embodiments.
Example 1
Synthesis of Biimidazole Compound B1：
Will imidazole
(27.48g, 403.6mmol, 2.0eq) and sodium hydroxide (16g, 400mmol) were added to 160mL of dimethyl sulfoxide, heated and stirred to 60 ℃ and reacted for 1 hour, then 1, 4-dichlorobutane was slowly added, followed by reaction at 60 ℃ for 2 hours and then cooled to room temperature; pouring the reaction solution into 600mL of ice sodium chloride aqueous solution, stirring for 20min, filtering, washing a filter cake twice with 400mL of deionized water, collecting solids, and drying in an oven at 80 ℃ for 12 hours to obtain a white solid product B1(22.4g, 117.7mmol, 58.3% yield). Biimidazole compound B1The structural formula of (A) is:
1H NMR(600MHz，DMSO-d6)δ7.59(s，1H)，7.12(t，J＝1.1Hz，1H)，6.86(s，1H)，3.94(s，2H)，1.60(s，2H).
synthesis of Compound C1：
A bisimidazole compound B1(5.76g, 30.3mmol, 1.0eq) was dissolved in 20mL acetonitrile, added to a flask, heated to 60 ℃ to dissolve, then cooled to 0 ℃; 1, 3-propanesultone (7.40g, 60.6mmol, 2.0eq) was dissolved in 6mL of toluene, after which the biimidazole compound B was slowly added dropwise1Heating and stirring the mixture and acetonitrile in a reaction solution to about 50 ℃, reacting for 2 hours, and cooling to room temperature; filtering to obtain white solid, washing the white solid with diethyl ether and toluene twice, and oven drying to obtain white solid C1(10.74g, 81.6%). Compound C1The structural formula of (A) is:
1H NMR(600MHz，D2O)δ8.87(s，2H)，7.56(d，J＝29.8Hz，4H)，4.39(t，J＝7.0Hz，4H)，4.31-4.25(m，4H)，2.93(t，J＝7.3Hz，4H)，1.87-1.97(m，4H)，1.93(s，4H).
synthesizing ionic liquid BSIM-C3 Cl:
compound C1(3.43g, 7.89mmol, 1.0eq) and 37% by mass of hydrochloric acid (0.58g, 15.8mmol, 2.0eq) were added together in a flask, heated to 80 ℃ for reaction for 2 hours, and then cooled to room temperature; the product was washed 2 times with toluene and ether, respectively, and dried to give BSIM-Cl (3.82g, 95.5%) as an oily liquid. The structural formula of the ionic liquid BSIM-C3Cl is as follows:
1H NMR(600MHz，D2O)δ8.84(s，2H)，7.53(d，J＝25.0Hz，4H)，4.36(t，J＝7.1Hz，4H)，4.29-4.22(m，4H)，2.92-2.86(m，4H)，2.35-2.27(m，4H)，1.94-1.85(m，4H).13C NMR(150MHz，D2O)δ135.59，122.60，122.51，48.86，47.88，47.24，26.15，25.01.
the ionic liquid BSIM-C3Cl catalyzes cellulose to prepare levulinic acid:
cellulose (60mg), ionic liquid BSIM-Cl (0.605g) and 0.36mL of deionized water were mixed, stirred at 180 ℃ for 1 hour, then cooled to room temperature, the reaction mixture was extracted with methyl isobutyl ketone, and the organic phase was concentrated in vacuo to give levulinic acid (23.86mg, 55.5%). Because the reaction mixed liquor only contains ionic liquid BSIM-C3Cl, solid residue, water, levulinic acid and formic acid, the levulinic acid is easily dissolved in the methyl isobutyl ketone solvent, and the ionic liquid is easily dissolved in the water. The levulinic acid was isolated by first extraction with methyl isobutyl ketone, after which the reaction mixture was centrifuged and the solid residue was removed, and the aqueous phase was concentrated in vacuo to remove water and formic acid, leaving a solid as ionic liquid BSIM-C3 Cl.
Example 2
Synthesizing ionic liquid BSIM-C3 Br:
compound C1(3.10g, 7.13mmol, 1.0eq) with 40% by weight hydrobromic acid (2.88g, 14.25mmol, 20eq) are added into a flask together, heated to 80 ℃, reacted for 6 hours, and then cooled to room temperature; the product was washed with toluene and ether 2 times each and dried to give BSIM-Br (4.12g, 99.0%) as a brown solid.
The structural formula of the ionic liquid BSIM-C3Br is as follows:
1H NMR(600MHz，D2O)δ8.86(s，2H)，7.55(d，J＝27.9Hz，4H)，4.38(t，J＝7.1Hz，4H)，4.33-4.23(m，4H)，2.92(t，J＝7.3Hz，4H)，2.37-2.29(m，4H)，1.98-1.85(d，J＝3.1Hz，4H).13C NMR(150MHz，D2O)δ135.59，122.59，122.51，48.86，47.88，47.24，26.16，25.00.
the ionic liquid BSIM-C3Br catalyzes cellulose to prepare levulinic acid:
cellulose (68mg), ionic liquid BSIM-Br (0.683g) and 0.41mL of deionized water are mixed, stirred and reacted for 40min at 180 ℃, then cooled to room temperature, the reaction solution is extracted by methyl isobutyl ketone, the organic phase is concentrated in vacuum to obtain levulinic acid (26.73mg, 54.9%), and the ionic liquid BSIM-Br can be recycled.
Example 3
Synthesis of Compound C2：
A bisimidazole compound B1(11.4g, 60mmol, 1.0 eq.) and 1, 4-butanesultone (32.64g, 240mmol, 4.0 eq.) were added to a 100mL flask, mechanically stirred at room temperature for 72 hours, washed three times with diethyl ether, and dried to give colorless viscous liquid C2(26.4g，95.2％)。
Compound C2The structural formula of (A) is:
1H NMR(600MHz，D2O)δ8.77(s，2H)，7.45(d，J＝19.8Hz，4H)，4.28-4.12(m，8H)，2.86(t，J＝6.2Hz，4H)，2.07-1.92(m，4H)，1.85-1.76(d，J＝2.6Hz，4H)，1.71-1.55(m，4H).
synthesizing ionic liquid BSIM-F:
compound C2(1.88g, 4.06mmol, 1.0eq) and 40% hydrofluoric acid (0.407g, 8.13mmol, 2.0eq) were added to a teflon bottle, heated to 100 ℃ for reaction for 3 hours, then cooled to room temperature, the product was washed with toluene and ether for 2 times, and dried to obtain BSIM-F (2.01g, 98.4%) as an oily liquid.
The structural formula of the ionic liquid BSIM-F is as follows:
1H NMR(600MHz，D2O)δ8.86(s，2H)，7.57-7.51(m，4H)，4.27(t，J＝6.9Hz，8H)，2.94(t，4H)，2.14-2.00(m，4H)，1.91(dd，J＝6.2，3.1Hz，4H)，1.78-1.70(m，4H).13C NMR(150MHz，D2O)δ135.42，122.61，122.45，50.04，49.06，48.83，27.98，26.19，20.93.
the ionic liquid BSIM-F catalyzes cellulose to prepare levulinic acid:
cellulose (73mg), ionic liquid BSIM-F (0.724g) and 0.44mL of deionized water are mixed, stirred and reacted for 5 hours at 180 ℃, then the temperature is reduced to room temperature, the reaction solution is extracted by methyl isobutyl ketone, the organic phase is concentrated in vacuum to obtain levulinic acid (23.92mg, 45.7%), and the ionic liquid BSIM-F can be recycled.
Example 4
Synthesizing ionic liquid BSIM-Cl:
compound C2(3.70g, 8.00mmol, 1.0eq) and 37% by mass of hydrochloric acid (1.578g, 16.00mmol, 2.0eq) were added to a flask, 0.60mL of water was added thereto, the mixture was heated to 60 ℃ and reacted for 4.5 hours, and then the temperature was lowered to room temperature. Washed with toluene and ether 2 times, respectively, and dried to give BSIM-Cl (4.25g, 98%) as an oily liquid.
The structural formula of the ionic liquid BSIM-Cl is as follows:
1H NMR(600MHz，D2O)δ8.78(s，2H)，7.46(d，J＝13.4Hz，4H)，4.19(s，8H)，2.85(dd，J＝10.5，4.4Hz，4H)，2.04-1.93(m，4H)，1.88-1.77(m，4H)，1.75-1.62(m，4H).13C NMR(125MHz，D2O)δ135.30，122.48，122.34，49.98，48.94，48.73，27.93，26.10，20.85.
preparing levulinic acid by catalyzing cellulose with ionic liquid BSIM-Cl:
cellulose (95mg), ionic liquid BSIM-Cl (0.949g) and 0.37mL of deionized water are taken, stirred and reacted for 1 hour at 180 ℃, then the temperature is reduced to room temperature, the reaction solution is extracted by methyl isobutyl ketone, the organic phase is concentrated in vacuum to obtain levulinic acid (43.49mg, 63.9%), and the ionic liquid BSIM-Cl can be recycled.
Example 5
Synthesizing ionic liquid BSIM-Br:
compound C2(2.66g, 5.75mmol, 1.0eq) and 40% by mass hydrobromic acid (2.33g, 11.50mmol, 2.0eq) were added to the flask, 0.40mL of water was added, the mixture was heated to 80 ℃ and reacted for 4 hours, and then the temperature was lowered to room temperature. Washed with toluene and ether 2 times, respectively, and dried to obtain BSIM-Br (3.45g, 96.1%) as an oily liquid.
The structural formula of the ionic liquid BSIM-Br is as follows:
1H NMR(600MHz，D2O)δ8.80(s，2H)，7.48(dt，J＝13.3，1.8Hz，4H)，4.21(t，J＝6.9Hz，8H)，2.88(t，J＝7.67Hz，4H)，2.03-1.94(m，4H)，1.91-1.82(m，4H)，1.75-1.61(m，4H).13C NMR(150MHz，D2O)δ135.34，122.55，122.42，50.05，49.04，48.82，27.99，26.18，20.92.HMMS(ESI)m/z：calcd for[M-2HBr]+Na C18H30N4NaO6S2：485.15045；Found 485.15134.
preparing levulinic acid by catalyzing cellulose with ionic liquid BSIM-Br:
cellulose (48.3mg), ionic liquid BSIM-Br (0.433g) and 0.39mL of deionized water are mixed, stirred and reacted for 20 minutes at 180 ℃, then cooled to room temperature, the reaction solution is extracted by methyl isobutyl ketone, the organic phase is concentrated in vacuum to obtain levulinic acid (26.45mg, 76.5%), and the ionic liquid BSIM-Br can be recycled.
Example 6
Synthesizing ionic liquid BSIM-I:
compound C2(3.19g, 6.89mmol, 1.0eq) and 55% by mass hydrobromic acid (3.2g, 13.78mmol, 2.0eq) were added to the flask, 0.60mL of water was added, the mixture was heated to 80 ℃ and reacted for 5 hours, and then the temperature was lowered to room temperature. Washed with toluene and ether 2 times, respectively, and dried to obtain BSIM-I (4.72g, 95.3%) as brown oily liquid.
The structural formula of the ionic liquid BSIM-I is as follows:
1H NMR(600MHz，D2O)δ8.85(s，2H)，7.52(d，J＝14.0Hz，4H)，4.26(t，J＝6.8Hz，8H)，2.93(t，J＝7.5Hz，4H)，2.06-1.99(m，4H)，1.96-1.87(m，4H)，1.76-1.66(m，4H).13C NMR(150MHz，D2O)δ135.40，122.66，122.54，50.15，49.19，48.95，28.08，26.31，21.02.
the ionic liquid BSIM-I catalyzes cellulose to prepare levulinic acid:
cellulose (48.3mg), ionic liquid BSIM-I (0.829g) and 0.50mL of deionized water are mixed, stirred and reacted for 2 hours at 180 ℃, then cooled to room temperature, the reaction solution is extracted by methyl isobutyl ketone, the organic phase is concentrated in vacuum to obtain levulinic acid (4.62mg, 7.9%), and the ionic liquid BSIM-I can be recycled.
Example 7
Synthesis of ionic liquid BSIM-HSO4：
Compound C2(3.34g, 7.22mmol, 1.0eq) and sulfuric acid (1.416g, 14.44mmol, 2.0eq) were added to the flask, heated to 60 ℃ and reacted for 8 hours, after which it was cooled to room temperature. Washing with toluene and diethyl ether for 2 times, and oven drying to obtain oily liquid BSIM-HSO4(4.51g，95％)。
Ionic liquid BSIM-HSO4The structural formula of (A) is:
1H NMR(600MHz，D2O)δ8.77(s，2H)，7.46(d，J＝17.1Hz，4H)，4.19(t，J＝6.9Hz，8H)，2.92-2.83(m，4H)，2.03-1.91(m，4H)，1.87-1.79(m，4H)，1.70-1.59(m，4H).13C NMR(100MHz，D2O)δ135.15，122.36，122.23，49.87，48.82，48.62，27.81，25.97，20.74.
the ionic liquid BSIM-HSO4 is used for catalyzing cellulose to prepare levulinic acid:
taking cellulose (54.2mg) and ionic liquid BSIM-HSO4(0.552g) was mixed with 0.435mL of deionized water, the mixture was stirred at 180 ℃ for 3 hours, then cooled to room temperature, the reaction mixture was extracted with methyl isobutyl ketone, and the organic phase was concentrated in vacuo to give levulinic acid (25.39mg, 65.4%) as an ionic liquid BSIM-HSO4Can be recycled.
Example 8
Synthesis of ionic liquid BSIM-H2PO4：
Compound C2(2.64g, 5.72mmol, 1.0 eq.) and phosphoric acid (1.12g, 11.43mmol, 2.0 eq.) were added to the flask, heated to 80 ℃ and reacted for 4 hours, after which it was cooled to room temperature. Washing with toluene and diethyl ether for 2 times, and oven drying to obtain white solid BSIM-H2PO4(3.61g，96％)。
Ionic liquid BSIM-H2PO4The structural formula of (A) is:
1H NMR(600MHz，D2O)δ8.85(s，2H)，7.53(d，J＝20.0Hz，4H)，4.26(t，J＝6.9Hz，8H)，2.93(t，J＝7.4Hz，4H)，2.09-1.98(m，4H)，1.96-1.87(m，4H)，1.77-1.68(m，4H).13C NMR(150MHz，D2O)δ135.38，122.59，122.42，49.99，49.04，48.81，27.94，26.17，20.89.
ionic liquid BSIM-H2PO4 catalysisCellulose preparation of levulinic acid:
taking cellulose (86mg) and ionic liquid BSIM-H2PO4(0.854g) was mixed with 0.52mL of deionized water, the mixture was stirred at 180 ℃ for 4 hours, then cooled to room temperature, the reaction mixture was extracted with methyl isobutyl ketone, and the organic phase was concentrated in vacuo to give levulinic acid (15.43mg, 25.1%) as an ionic liquid BSIM-H2PO4Can be recycled.
Example 9
Synthesis of ionic liquid BSIM-CF3SO3：
Compound C2(2.63g, 5.68mmol, 1.0 eq.) and trifluorosulfonic acid (1.71g, 11.36mmol, 2.0 eq.) were added to the flask, heated to 60 ℃ and reacted for 4.5 hours, after which it was allowed to cool to room temperature. Washing with toluene and diethyl ether for 2 times, and oven drying to obtain oily liquid BSIM-CF3SO3(4.25g，98％)。
Ionic liquid BSIM-CF3SO3The structural formula of (A) is:
1H NMR(600MHz，D2O)δ8.82(s，2H)，7.51(dt，J＝19.4，1.8Hz，4H)，4.24(t，J＝6.9Hz，8H)，2.95-2.85(m，4H)，2.09-1.97(m，4H)，1.93-1.85(m，4H)，1.74-1.67(m，4H).13C NMR(125MHz，D2O)δ135.15，122.41，122.25，120.76，118.23，49.90，48.87，48.66，27.86，27.80，26.01，20.79.19F NMR(375MHz，D2O)δ-78.90(s).
ionic liquid BSIM-CF3SO3Catalysis of cellulose to levulinic acid:
taking cellulose (51mg) and ionic liquid BSIM-CF3SO3(0.516g) was mixed with 0.305mL of deionized water, and the mixture was stirred at 180 ℃ for 40min, then cooled to room temperature, the reaction mixture was extracted with methyl isobutyl ketone, and the organic phase was concentrated in vacuo to give levulinic acid (19.43mg, 53.2%) as an ionic liquid BSIM-CF3SO3Can be recycled.
Example 10
Synthesizing ionic liquid BSIM-TsO:
compound C2(3.41g, 7.36mmol, 1.0eq) and p-toluenesulfonic acid (2.80g, 14.73mmol, 2.0eq) were added to the flask, heated to 80 ℃ for 5 hours, and then cooled to room temperature. Washed with toluene and ether 2 times respectively, and dried to obtain BSIM-TsO (6.10g, 98.2%) as oily liquid.
The structural formula of the ionic liquid BSIM-TsO is as follows:
1H NMR(600MHz，D2O)δ8.78(s，2H)，7.65(d，J＝8.3Hz，4H)，7.46(dt，J＝18.2，1.8Hz，4H)，7.32(d，J＝8.0Hz，4H)，4.23-4.17(m，8H)，2.95-2.85(m，4H)，2.35(s，6H)，2.04-1.90(m，4H)，1.86-1.81(m，4H)，1.72-1.63(m，4H).13C NMR(150MHz，D2O)δ142.30，139.64，135.20，129.39，125.31，122.50，122.36，50.02，48.98，48.74，27.96，26.11，20.92，20.45.
the ionic liquid BSIM-TsO catalyzes cellulose to prepare levulinic acid:
cellulose (86mg), ionic liquid BSIM-TsO (0.861g) and 0.52mL of deionized water are mixed, stirred and reacted for 40min at 180 ℃, then cooled to room temperature, the reaction solution is extracted by methyl isobutyl ketone, the organic phase is concentrated in vacuum to obtain levulinic acid (34.57mg, 56.1%), and the ionic liquid BSIM-TsO can be recycled.
The acidity of the ionic liquid is calculated by a Hammett acidity calculation method, based on figure 1, by using a formula H0＝pKa(I)+log([I]/[IH+]) The Hammett acidity was calculated and the acidity data are shown in Table 1.
TABLE 1 Hammett acidity and yield of catalytic cellulose to levulinic acid for different ionic liquids
For ionic liquids BSIM-F, BSIM-Cl and BS containing different halogen anionsIn the case of IM-Br, the Hammett acidity gradually increases with the increase of the anion atomic radius, and the increase of the Hammett acidity is beneficial to promoting the hydrolysis of cellulose. Meanwhile, the reaction rate and the yield of catalyzing the conversion of the cellulose into the levulinic acid are increased, and the reaction time is shortened. The ionic liquid BSIM-Br containing Br ions catalyzes the yield of the cellulose to reach 76.5 percent, the reaction time is only 20 minutes, the reason that the ionic liquid catalyzes the cellulose to prepare the levulinic acid has high yield is that BSIM-Br has the strongest acidity in the ionic liquid containing halogen anions, and meanwhile, bromine ions can act on a hydrogen bond network structure of the cellulose to open the hydrogen bond structure in cellulose molecules to promote the hydrolysis of the cellulose into glucose, and meanwhile, the ionic liquid containing the halogen ions has good solubility for the cellulose. For ionic liquids BSIM-C3Cl and BSIM-C3Br containing short chain sulfonic acid groups, as the ionic liquids are solid at normal temperature, the ionic liquids without long chains are good for dissolving cellulose, the yield of the catalytic cellulose for preparing levulinic acid is reduced, and the reaction rate is slowed. For ionic liquid BSIM-HSO containing different acidic anions4，BSIM-TsO，BSIM-CF3SO3And BSIM-H2PO4In particular, wherein BSIM-HSO4The acidity is the strongest, and the yield of the levulinic acid prepared by catalyzing cellulose is the best, and the yield is as high as 65.4%. This result indicates that Hammett's acidity is highly favorable for the reaction of cellulose to catalyze the conversion of levulinic acid. FIG. 2 is a thermogravimetric analysis diagram of different ionic liquids, and it can be seen from FIG. 2 that, between 50 and 200 ℃, the moisture in the ionic liquid is gradually volatilized, and when the temperature is between 300 and 400 ℃, the ionic liquid is gradually decomposed, and the decomposition temperature is greater than 200 ℃, which indicates that the ionic liquid has good thermal stability in the experimental temperature range.
Table 2 shows the yields of levulinic acid prepared with different biomass feedstocks based on different catalysts, when BSIM-Br is used as catalyst, the reaction conditions: raw material (100 mg), catalyst BSIM-Br (0.9 g), H2O (0.8 g), reacted at 180 ℃; when BSIM-HSO is used4As catalyst, reaction conditions: raw material (100 mg), catalyst BSIM-HSO4(1.0 g), H2O (0.8 g) at 180 ℃ CShould be used.
TABLE 2
Table 2 lists ionic liquid catalysts BSIM-Br and BSIM-HSO4Catalytic effect for different biomasses. For BSIM-Br catalyst, the catalytic disaccharide raw materials of sucrose, cellobiose and starch have high levulinic acid yield which is more than 63 percent. For the amidated saccharides chitin and chitosan, the yield of the catalyst BSIM-Br catalyzing the conversion of the amidated saccharides into levulinic acid reaches 58.3 percent and 48.6 percent respectively. Catalyst BSIM-HSO4The catalyst also has a good catalytic effect on different saccharides, and the yield of the catalytic saccharides is 45-65%. These results indicate that the catalysts BSIM-Br and BSIM-HSO4Can be used for preparing levulinic acid by catalyzing different saccharides, and has higher yield.
FIGS. 3 and 4 are BSIM-Br and BSIM-HSO, respectively4As a recovery experimental diagram for preparing levulinic acid by catalyzing hydrolysis of cellulose by using the catalyst, as can be seen from FIG. 3, the ionic liquid BSIM-Br is subjected to 5 recovery experiments, the yield of the levulinic acid prepared by catalyzing hydrolysis of the cellulose is about 41.5%, which shows that the catalytic activity of the ionic liquid BSIM-Br is slowly reduced in the repeated use process, and the catalyst is easy to recycle and has good stability. As can be seen from FIG. 4, the ionic liquid BSIM-HSO 45 recovery experiments were carried out which also gave a yield of 37.8% for the catalytic hydrolysis of cellulose to levulinic acid, indicating that the catalyst BSIM-HSO4In the recycling process, the catalyst also has higher activity, and the nuclear magnetic hydrogen spectrum detection finds that the recycled ionic liquid has higher purity and the structure is not changed. These results demonstrate that the ionic liquid BSIM-HSO4Good stability and easy recovery, and the recovery rate is more than 90%.
Claims (9)
1. Application of ionic liquid based on biimidazole in catalyzing biomass to prepare levulinic acid.
2. The application of the biimidazole-based ionic liquid in catalyzing biomass to prepare levulinic acid according to claim 1, wherein the specific reaction process is as follows: mixing the biomass, the ionic liquid and a solvent, reacting at high temperature, and extracting the reaction solution after reaction by using an organic solvent to obtain the levulinic acid.
3. The use of a biimidazole-based ionic liquid as claimed in claim 2 for catalyzing the production of levulinic acid from biomass, characterized in that: the mass ratio of the ionic liquid to the biomass is 0.1-20: 1, and the mass ratio of the solvent to the biomass is 0.3-2: 1.
4. The use of a biimidazole-based ionic liquid as claimed in claim 2 for catalyzing the production of levulinic acid from biomass, characterized in that: the reaction temperature is not more than 200 ℃, and the reaction time is 0.1-10 h.
5. The use of a biimidazole-based ionic liquid as claimed in claim 1 for catalyzing the production of levulinic acid from biomass, characterized in that: the structural general formula of the ionic liquid based on the biimidazole is as follows:
in the formula (I) and the formula (II), n is any value of 1-10; r1 and R2 are F-、Cl-、Br-、I-、HSO4 -、H2PO4 -、CF3SO3 -、CH3SO3 -、FeCl4 -、AlCl4 -、HSiO3 -、H2PW12O40 -、
One kind of (1).
6. The use of a biimidazole-based ionic liquid as claimed in claim 1 for catalyzing the production of levulinic acid from biomass, characterized in that: the preparation method of the ionic liquid based on the biimidazole comprises the following steps: mixing a sulfonic acid group compound containing biimidazole, a Bronsted acid compound and water, and refluxing for 4-8 hours at the temperature of 80-100 ℃ to obtain the biimidazole-based ionic liquid.
7. The application of the biimidazole-based ionic liquid as claimed in claim 6 in catalyzing biomass to prepare levulinic acid, wherein: the sulfonic acid group compound containing the biimidazole has the structural general formula:
wherein n is any number from 1 to 10.
8. The application of the biimidazole-based ionic liquid as claimed in claim 6 in catalyzing biomass to prepare levulinic acid, wherein: the Bronsted acid compound is HF, HCl, HBr, HI, H2SO4、H3PO4、CF3SO3H、CH3SO3H、FeCl3、AlCl3、H2SiO3、H3PW12O40、
One kind of (1).
9. The application of the biimidazole-based ionic liquid as claimed in claim 6 in catalyzing biomass to prepare levulinic acid, wherein: the sulfonic acid group compound containing the biimidazole is prepared by adopting the following method: dissolving imidazole in dimethyl sulfoxide, and reacting under the conditions of sodium hydroxide and dichloroalkane or dibromoalkane to obtain a biimidazole compound B; mixing the biimidazole compound B and cyclic sultone, and stirring at normal temperature for not less than 72 hours to obtain a sulfonic compound C containing biimidazole; or mixing the biimidazole compound B and 1, 3-propane sultone, adding a solvent toluene, reacting at 90 ℃, washing the obtained solid compound with toluene and diethyl ether respectively, and drying to obtain a sulfonic acid group compound C containing biimidazole;
wherein the imidazole compound is
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