CN112778124B - Application of ionic liquid based on biimidazole in preparation of levulinic acid by catalyzing biomass - Google Patents
Application of ionic liquid based on biimidazole in preparation of levulinic acid by catalyzing biomass Download PDFInfo
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Abstract
The invention discloses an application of ionic liquid based on biimidazole in preparing levulinic acid by catalyzing biomass. When the ionic liquid based on the biimidazole is used for preparing the levulinic acid by catalyzing biomass, the catalyst can be recycled, the reaction rate can be effectively improved, the reaction time can be shortened, the product yield can be improved to about 76.5%, and the problems of equipment corrosion, waste acid pollution and the like caused by using inorganic acid as the catalyst can be effectively solved.
Description
Technical Field
The invention relates to application of ionic liquid based on biimidazole in preparation of levulinic acid by catalyzing biomass.
Background
The levulinic acid has good reactivity because of containing a carboxyl group and a ketone group in the molecular structure, can synthesize various chemical products through reactions such as esterification, polymerization, hydrogenation and the like, and has wide application prospects in the fields of medicines, gasoline additives, daily chemicals, lubricants, surfactants, electronic materials, plastics, batteries and the like.
There are two main methods for preparing acetic acid propionic acid from biomass, one is furfuryl alcohol hydrolysis method, and the other is biomass direct hydrolysis method. Since furfuryl alcohol can also be produced by hydrolysis of biomass, both processes are produced from biomass as a feedstock. The furfuryl alcohol hydrolysis method needs four steps of hydrolysis, dehydration, hydrogenation and hydrolysis reaction, and has longer process, lower yield and poor economy. The direct hydrolysis method of biomass generally obtains levulinic acid through continuous hydrolysis, and the process is simpler. However, the catalysts used in the hydrolysis process are mainly inorganic acids including sulfuric acid, hydrochloric acid, hydrofluoric acid and the like, and 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 invention aims to: aiming at the problems of high equipment corrosion, incapability of recycling the catalyst and high waste liquid and slag amount existing in the process of preparing levulinic acid by adopting an inorganic acid as a catalyst in the direct hydrolysis method of biomass in the prior art, the invention provides the application of the ionic liquid based on biimidazole as the catalyst in the aspect of preparing levulinic acid by catalyzing biomass.
The technical scheme is as follows: the ionic liquid based on biimidazole is applied to the preparation of levulinic acid by catalyzing biomass.
The specific reaction process is as follows: mixing biomass, ionic liquid and solvent, reacting at high temperature, and extracting the reacted reaction liquid by an organic solvent to obtain 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.
The structural general formula of the ionic liquid based on biimidazole is as follows:
or (b)
Wherein in the formula (I) and the formula (II), the value of n is any value from 1 to 10; r is R 1 And R is 2 In the form of ions, the structure of which can be F - 、Cl - 、Br - 、I - 、HSO 4 - 、H 2 PO 4 - 、CF 3 SO 3 - 、CH 3 SO 3 - 、FeCl 4 - 、AlCl 4 - 、HSiO 3 - 、H 2 PW 12 O 40 - 、
One of them.
The preparation method of the ionic liquid based on biimidazole comprises the following steps: mixing the sulfonic compound containing biimidazole, the Bronsted acid compound and water, and refluxing for 4-8 hours at 80-100 ℃ to obtain the ionic liquid based on biimidazole.
Wherein, the structural general formula of the sulfonic acid group compound containing biimidazole is:
wherein n=any number from 1 to 10.
Wherein the Bronsted acid compound is HF, HCl, HBr, HI, H 2 SO 4 、H 3 PO 4 、CF 3 SO 3 H、CH 3 SO 3 H、FeCl 3 、AlCl 3 、H 2 SiO 3 、H 3 PW 12 O 40 、
One of them.
The sulfonic acid group compound containing biimidazole is prepared by the following method: dissolving imidazole in dimethyl sulfoxide, and reacting under the condition of sodium hydroxide and dichloroalkane or dibromoalkane to obtain a biimidazole compound B; mixing the biimidazole compound B with 1, 4-butyl sultone, and stirring at normal temperature for at least 72 hours to obtain a sulfonic compound C containing biimidazole; or mixing the biimidazole compound B and 1, 3-propane sultone, then adding solvent toluene, reacting at 90 ℃, washing the obtained solid compound with toluene and diethyl ether respectively, removing unreacted raw material 1, 3-propane sultone or 1, 4-butane sultone, and drying to obtain a sulfonic compound C containing biimidazole;
wherein the imidazole is
When imidazole is
When 1, 4-dichlorobutane or 1, 4-dibromobutane is used for reaction with the catalyst, the bisimidazole compound B is obtained 1 The structural formula is as follows:
biimidazole compound B 1 The 1, 3-propane sultone is used for reacting with the compound to prepare the compound C 1 The structural formula is as follows:
biimidazole compound B 1 The 1, 4-butanesulfonic acid lactone is reacted with the mixture to prepare the compound C 2 The structural formula is as follows:
the ionic liquid of the invention has the reaction formula:
the ionic liquid synthesized by the invention takes the unit containing biimidazole and sulfonic group as cations, and takes halogen ions (such as fluorine, chlorine, bromine and iodine), hydrogen sulfate, phosphate or trifluoro sulfonate as anions, so that the ionic liquid containing cations and anions is formed.
The beneficial effects are that: when the ionic liquid based on the biimidazole is used for preparing the levulinic acid by catalyzing biomass, the catalyst can be recycled, the reaction rate can be effectively improved, the reaction time can be shortened, the product yield can be improved to about 76.5%, and the problems of equipment corrosion, waste acid pollution and the like caused by using inorganic acid as the catalyst can be effectively solved.
Drawings
FIG. 1 is a graph of ultraviolet absorption spectra of different ionic liquids;
figure 2 is a thermogravimetric analysis of different ionic liquids.
FIG. 3 is a graph showing the yields of levulinic acid prepared by converting ionic liquid BSIM-Br catalyzed cellulose after multiple recoveries;
FIG. 4 shows an ionic liquid BSIM-HSO 4 Yield graphs of levulinic acid prepared by catalytic conversion of cellulose after multiple recovery.
Detailed Description
The technical scheme of the invention is further described below with reference to specific embodiments.
Example 1
Synthesis of Biimidazole Compound B 1 ：
Imidazole is used as the main component
(27.48 g,403.6mmol,2.0 eq) and sodium hydroxide (16 g,400 mmol) were added to 160mL of dimethyl sulfoxide, heated and stirred to 60℃and after 1 hour of reaction, 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 the filter cake with 400mL of deionized water twice, collecting solid, and drying in an oven at 80 ℃ for 12 hours to obtain a white solid product B 1 (22.4 g,117.7mmol, 58.3% yield). Biimidazole compound B 1 The structural formula is as follows:
1 H NMR(600MHz，DMSO-d 6 )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 C 1 ：
To the bisimidazole compound B 1 (5.76 g,30.3mmol,1.0 eq) in 20mL acetonitrile, added to the flask, heated to 60℃for dissolution, and then cooled to 0 ℃; 1, 3-propane sultone (7.40 g,60.6mmol,2.0 eq) was dissolved in 6mL of toluene, followed by slow dropwise addition of the bisimidazole compound B 1 Heating and stirring the mixture with acetonitrile 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 respectively, and oven drying to obtain white solid C 1 (10.74 g, 81.6%). Compound C 1 The structural formula is as follows:
1 H NMR(600MHz，D 2 O)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 an ionic liquid BSIM-C3Cl:
compound C 1 (3.43 g,7.89mmol,1.0 eq) was added to the flask together with 37% hydrochloric acid (0.58 g,15.8mmol,2.0 eq) by mass, heated to 80 ℃ for 2 hours, and then cooled to room temperature; the product was washed 2 times with toluene and diethyl ether, respectively, and dried to give BSIM-Cl (3.82 g, 95.5%) as an oily liquid. The structural formula of the ionic liquid BSIM-C3Cl is as follows:
1 H NMR(600MHz，D 2 O)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). 13 C NMR(150MHz，D 2 O)δ135.59，122.60，122.51，48.86，47.88，47.24，26.15，25.01.
preparation of levulinic acid from cellulose catalyzed by ionic liquid BSIM-C3Cl:
cellulose (60 mg), ionic liquid BSIM-Cl (0.605 g) and 0.36mL deionized water were taken and mixed and reacted for 1 hour under stirring at 180 ℃, then cooled to room temperature, the reaction solution was extracted with methyl isobutyl ketone, and the organic phase was concentrated in vacuo to give levulinic acid (23.86 mg, 55.5%). Because the reaction mixture only contains the ionic liquid BSIM-C3Cl, solid residues, water, levulinic acid and formic acid, and because the levulinic acid is easy to dissolve in the methyl isobutyl ketone solvent, the ionic liquid is easy to dissolve in the water. The levulinic acid can be separated by first extracting with methyl isobutyl ketone, after which the reaction mixture is centrifuged to remove the solid residue, and then the aqueous phase is concentrated in vacuo to remove water and formic acid, the remaining solid being the ionic liquid BSIM-C3Cl.
Example 2
Synthesizing an ionic liquid BSIM-C3Br:
compound C 1 (3.10 g,7.13mmol,1.0 eq) was added to the flask together with 40% hydrobromic acid (2.88 g,14.25mmol,2.0 eq), heated to 80 ℃ and reacted for 6 hours, after which it was cooled to room temperature; the product was washed 2 times with toluene and diethyl ether, respectively, and dried to give BSIM-Br (4.12 g, 99.0%) as a brown solid.
The structural formula of the ionic liquid BSIM-C3Br is as follows:
1 H NMR(600MHz，D 2 O)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). 13 C NMR(150MHz，D 2 O)δ135.59，122.59，122.51，48.86，47.88，47.24，26.16，25.00.
preparation of levulinic acid from cellulose catalyzed by ionic liquid BSIM-C3Br:
cellulose (68 mg), ionic liquid BSIM-Br (0.683 g) and 0.41mL deionized water are taken and mixed, stirred at 180 ℃ for reaction for 40min, then cooled to room temperature, the reaction liquid is extracted by methyl isobutyl ketone, and the organic phase is concentrated in vacuum to obtain levulinic acid (26.73 mg, 54.9%), wherein the ionic liquid BSIM-Br can be recycled.
Example 3
Synthesis of Compound C 2 ：
To the bisimidazole compound B 1 (11.4 g,60mmol,1.0 eq) and 1, 4-butanesultone (32.64 g,240mmol,4.0 eq) were added to a 100mL flask, and after mechanical stirring at room temperature for 72 hours, washed three times with diethyl ether, dried to give a colorless viscous liquid C 2 (26.4g，95.2％)。
Compound C 2 The structural formula is as follows:
1 H NMR(600MHz，D 2 O)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 an ionic liquid BSIM-F:
compound C 2 (1.88 g,4.06mmol,1.0 eq) and 40% hydrofluoric acid (0.407 g,8.13mmol,2.0 eq) were added to a polytetrafluoroethylene bottle, heated to 100 ℃ C., reacted for 3 hours, then cooled to room temperature, and the product was washed 2 times with toluene and diethyl ether, respectively, and dried to give BSIM-F (2.01 g, 98.4%) as an oily liquid.
The structural formula of the ionic liquid BSIM-F is as follows:
1 H NMR(600MHz，D 2 O)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). 13 C NMR(150MHz，D 2 O)δ135.42，122.61，122.45，50.04，49.06，48.83，27.98，26.19，20.93.
preparation of levulinic acid by catalyzing cellulose by using ionic liquid BSIM-F:
cellulose (73 mg), ionic liquid BSIM-F (0.724 g) and 0.44mL of deionized water are taken and mixed, stirred at 180 ℃ for reaction for 5 hours, then cooled to room temperature, the reaction liquid is extracted by methyl isobutyl ketone, the organic phase is concentrated in vacuum to obtain levulinic acid (23.92 mg, 45.7%), and the ionic liquid BSIM-F can be recycled.
Example 4
Synthesizing an ionic liquid BSIM-Cl:
compound C 2 (3.70 g,8.00mmol,1.0 eq) and 37% hydrochloric acid (1.578 g,16.00mmol,2.0 eq) were added to the flask, 0.60mL of water was added, heated to 60℃for 4.5 hours, and then cooled to room temperature. Washing with toluene and diethyl ether for 2 times, respectively, and oven drying to give oily liquid BSIM-Cl (4.25 g, 98%).
The structural formula of the ionic liquid BSIM-Cl is as follows:
1 H NMR(600MHz，D 2 O)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). 13 C NMR(125MHz，D 2 O)δ135.30，122.48，122.34，49.98，48.94，48.73，27.93，26.10，20.85.
preparation of levulinic acid from cellulose catalyzed by ionic liquid BSIM-Cl:
cellulose (95 mg), ionic liquid BSIM-Cl (0.949 g) and 0.37mL deionized water are taken and stirred at 180 ℃ for reaction for 1 hour, then the temperature is reduced to room temperature, the reaction liquid is extracted by methyl isobutyl ketone, the organic phase is concentrated in vacuum to obtain levulinic acid (43.49 mg, 63.9%), and the ionic liquid BSIM-Cl can be recycled.
Example 5
Synthesizing an ionic liquid BSIM-Br:
compound C 2 (2.66 g,5.75mmol,1.0 eq) and 40% hydrobromic acid (2.33 g,11.50mmol,2.0 eq) were added to the flask, 0.40mL of water was added, heated to 80℃and reacted for 4 hours, after which the temperature was lowered to room temperature. Toluene and diethyl ether are used respectivelyWashing 2 times and drying gave BSIM-Br (3.45 g, 96.1%) as an oily liquid.
The structural formula of the ionic liquid BSIM-Br is as follows:
1 H NMR(600MHz，D 2 O)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). 13 C NMR(150MHz，D 2 O)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 C 18 H 30 N 4 NaO 6 S 2 ：485.15045；Found 485.15134.
preparation of levulinic acid by catalyzing cellulose by using ionic liquid BSIM-Br:
cellulose (48.3 mg), ionic liquid BSIM-Br (0.433 g) and 0.39mL deionized water are taken and mixed, stirred at 180 ℃ for reaction for 20 minutes, then cooled to room temperature, the reaction liquid is extracted by methyl isobutyl ketone, and the organic phase is concentrated in vacuum to obtain levulinic acid (26.45 mg, 76.5%), wherein the ionic liquid BSIM-Br can be recycled.
Example 6
Synthesizing an ionic liquid BSIM-I:
compound C 2 (3.19 g,6.89mmol,1.0 eq) and 55% hydrobromic acid (3.2 g,13.78mmol,2.0 eq) by mass were added to the flask, 0.60mL of water was added, heated to 80℃for 5 hours, and then cooled to room temperature. Washing with toluene and diethyl ether respectively for 2 times, and drying gave BSIM-I (4.72 g, 95.3%) as a brown oily liquid.
The structural formula of the ionic liquid BSIM-I is as follows:
1 H NMR(600MHz，D 2 O)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). 13 C NMR(150MHz，D 2 O)δ135.40，122.66，122.54，50.15，49.19，48.95，28.08，26.31，21.02.
preparation of levulinic acid by catalyzing cellulose by ionic liquid BSIM-I:
cellulose (48.3 mg), ionic liquid BSIM-I (0.829 g) and 0.50mL deionized water are taken and mixed, stirred at 180 ℃ for reaction for 2 hours, then cooled to room temperature, the reaction liquid is extracted by methyl isobutyl ketone, the organic phase is concentrated in vacuum to obtain levulinic acid (4.62 mg, 7.9%), and the ionic liquid BSIM-I can be recycled.
Example 7
Synthesis of ionic liquid BSIM-HSO 4 ：
Compound C 2 (3.34 g,7.22mmol,1.0 eq) and sulfuric acid (1.416 g,14.44mmol,2.0 eq) were added to the flask, heated to 60℃and reacted for 8 hours, after which they were cooled to room temperature. Washing with toluene and diethyl ether respectively for 2 times, and oven drying to obtain oily liquid BSIM-HSO 4 (4.51g，95％)。
Ionic liquid BSIM-HSO 4 The structural formula is as follows:
1 H NMR(600MHz，D 2 O)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). 13 C NMR(100MHz，D 2 O)δ135.15，122.36，122.23，49.87，48.82，48.62，27.81，25.97，20.74.
preparation of levulinic acid from cellulose catalyzed by ionic liquid BSIM-HSO 4:
taking cellulose (54.2 mg) and ionic liquid BSIM-HSO 4 (0.552 g) and 0.435mL of deionized water were mixed, reacted at 180℃for 3 hours with stirring, 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 (25.39 mg, 65.4%) as an ionic liquid BSIM-HSO 4 Can be recycled.
Example 8
Synthesis of ionic liquid BSIM-H 2 PO 4 ：
Compound C 2 (2.64 g,5.72mmol,1.0 eq) and phosphoric acid (1.12 g,11.43mmol,2.0 eq) were added to the flask, heated to 80℃and reacted for 4 hours before cooling to room temperature. Washing with toluene and diethyl ether respectively for 2 times, and oven drying to obtain white solid BSIM-H 2 PO 4 (3.61g，96％)。
Ionic liquid BSIM-H 2 PO 4 The structural formula is as follows:
1 H NMR(600MHz，D 2 O)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). 13 C NMR(150MHz，D 2 O)δ135.38，122.59，122.42，49.99，49.04，48.81，27.94，26.17，20.89.
ionic liquid BSIM-H 2 PO4 catalyzed cellulose preparation of levulinic acid:
taking cellulose (86 mg) and ionic liquid BSIM-H 2 PO 4 (0.854 g) and 0.52mL of deionized water are mixed, stirred at 180 ℃ for reaction for 4 hours, cooled to room temperature, the reaction solution is extracted by methyl isobutyl ketone, and the organic phase is concentrated in vacuo to obtain levulinic acid (15.43 mg, 25.1%) which is an ionic liquid BSIM-H 2 PO 4 Can be recycled.
Example 9
Synthesis of ionic liquid BSIM-CF 3 SO 3 ：
Compound C 2 (2.63 g,5.68mmol,1.0 eq) and triflic acid (1.71 g,11.36mmol,2.0 eq) were added to the flask, heated to 60℃and reacted for 4.5 hours before cooling to room temperature. Washing with toluene and diethyl ether respectively for 2 times, and oven drying to obtain oily liquid BSIM-CF 3 SO 3 (4.25g，98％)。
Ionic liquid BSIM-CF 3 SO 3 The structural formula is as follows:
1 H NMR(600MHz，D 2 O)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). 13 C NMR(125MHz，D 2 O)δ135.15，122.41，122.25，120.76，118.23，49.90，48.87，48.66，27.86，27.80，26.01，20.79. 19 F NMR(375MHz，D 2 O)δ-78.90(s).
ionic liquid BSIM-CF 3 SO 3 Catalytic cellulose preparation of levulinic acid:
taking cellulose (51 mg) and ionic liquid BSIM-CF 3 SO 3 (0.516 g) and 0.305mL of deionized water are mixed, stirred at 180 ℃ for reaction for 40min, cooled to room temperature, the reaction solution is extracted by methyl isobutyl ketone, and the organic phase is concentrated in vacuo to obtain levulinic acid (19.43 mg, 53.2%) as an ionic liquid BSIM-CF 3 SO 3 Can be recycled.
Example 10
Synthesizing an ionic liquid BSIM-TsO:
compound C 2 (3.41 g,7.36mmol,1.0 eq) and p-toluene sulfonic acid (2.80 g, 14.73mmol,2.0 eq) were added to the flask, heated to 80℃and reacted for 5 hours, after which it was cooled to room temperature. Washing with toluene and diethyl ether respectively for 2 times, and oven drying to obtain oily liquid BSIM-TsO (6.10 g, 98.2%).
The structural formula of the ionic liquid BSIM-TsO is as follows:
1 H NMR(600MHz，D 2 O)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). 13 C NMR(150MHz，D 2 O)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.
preparation of levulinic acid by catalyzing cellulose by using ionic liquid BSIM-TsO:
cellulose (86 mg), ionic liquid BSIM-TsO (0.861 g) and 0.52mL of deionized water are taken and mixed, stirred at 180 ℃ for reaction for 40min, then cooled to room temperature, the reaction liquid is extracted by methyl isobutyl ketone, and the organic phase is concentrated in vacuum to obtain levulinic acid (34.57 mg, 56.1%), wherein the ionic liquid BSIM-TsO can be recycled.
The acidity of the ionic liquid is calculated by a Hammett acidity calculation method, and based on fig. 1, a formula H is applied 0 ＝pKa(I)+log([I]/[IH+]) The Hammett acidity was calculated and its acidity data are listed in Table 1.
Table 1 shows the Hammett acidity of various ionic liquids and the yield of levulinic acid from catalytic cellulose
For ionic liquids BSIM-F, BSIM-Cl and BSIM-Br containing different halogen anions, the Hammett acidity gradually increases with the increase of the radius of the anion atoms, and the Hammett acidity is increased to be beneficial to promoting the hydrolysis of cellulose. At the same time, the reaction rate and yield of the catalytic conversion of cellulose into levulinic acid are increased, and the reaction time is shortened. The ionic liquid BSIM-Br containing Br ions catalyzes cellulose with the yield of 76.5%, the reaction time is only 20 minutes, and the ionic liquid is used for catalyzing cellulose to prepare levulinic acid with high yield, because 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 cellulose to open the hydrogen bond structure in cellulose molecules, so that the cellulose is promoted to hydrolyze into glucose, and meanwhile, the ionic liquid containing halogen ions has good solubility for cellulose. For the ionic liquids BSIM-C3Cl and BSIM-C3Br containing short-chain sulfonic groups, as the two ionic liquids are solid at normal temperature, the ionic liquids without long chains are good for dissolution of cellulose, the yield of the levulinic acid prepared by catalyzing cellulose is reduced, and the reaction rate is also slowed. For ionic liquids BSIM-HSO containing different acidic anions 4 ，BSIM-TsO，BSIM-CF 3 SO 3 And BSIM-H 2 PO 4 In which BSIM-HSO 4 The most acidic, the best yields up to 65.4% are obtained for the preparation of levulinic acid from catalytic cellulose. This result demonstrates that the high Hammett acidity is advantageous for the reaction of cellulose to catalytically convert levulinic acid. Fig. 2 is a thermogravimetric analysis diagram of different ionic liquids, and as can be seen from fig. 2, the water in the ionic liquid gradually volatilizes between 50 and 200 ℃, and the ionic liquid gradually decomposes at a temperature between 300 and 400 ℃, and the decomposition temperature is greater than 200 ℃, which indicates that the ionic liquid has good thermal stability in an experimental temperature range.
Table 2 shows the yields of levulinic acid produced using 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), H 2 O (0.8 g) at 180 degrees; when using BSIM-HSO 4 As a catalyst, the reaction conditions: raw material (100 mg), catalyst BSIM-HSO 4 (1.0 g), H 2 O (0.8 g) was reacted at 180 degrees.
TABLE 2
Table 2 lists the ionic liquid catalysts BSIM-Br and BSIM-HSO 4 Catalytic effect on different biomass. For the BSIM-Br catalyst, the catalyst disaccharide feed sucrose, cellobiose and starch all have high levulinic acid yield, and the levulinic acid yield is more than 63 percent. For the amidated saccharides chitin and chitosan, the catalyst BSIM-Br catalyzes its conversion to levulinic acid in yields of 58.3% and 48.6%, respectively. Catalyst BSIM-HSO 4 Also has better catalytic effect on different saccharides, and the yield of the catalytic saccharides is between 45 and 65 percent. These results indicate that the catalysts BSIM-Br and BSIM-HSO 4 Can be used for preparing levulinic acid by catalyzing different saccharides, and has higher yield.
FIGS. 3 and 4 are FIGS. 3 and 4 show the respective BSIM-Br and BSIM-HSO 4 Preparation of ethyl by catalyzing cellulose hydrolysis as catalystAs can be seen from the experimental diagram of recovering the acyl propionic acid, in FIG. 3, the ionic liquid BSIM-Br is subjected to 5 recovery experiments, the yield of the levulinic acid prepared by catalyzing the cellulose hydrolysis is about 41.5%, which indicates 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 4 5 recovery experiments were performed which catalyzed the hydrolysis of cellulose to levulinic acid with a yield of 37.8%, which is indicative of the catalyst BSIM-HSO 4 In the recycling process, the catalyst also has higher activity, and the purity of the recovered ionic liquid is higher and the structure is not changed through nuclear magnetic hydrogen spectrum detection. These results demonstrate that the ionic liquid BSIM-HSO 4 The stability is good, the recovery is easy, and the recovery rate is more than 90%.
Claims (2)
1. The application of the ionic liquid based on biimidazole in preparing levulinic acid by catalyzing biomass is characterized in that the specific reaction process is as follows: mixing 48.3mg of cellulose, 0.433g of ionic liquid BSIM-Br and 0.39mL of deionized water, stirring at 180 ℃ for reaction for 20 minutes, cooling to room temperature, extracting the reaction liquid with methyl isobutyl ketone, and concentrating an organic phase in vacuum to obtain levulinic acid with the yield of 76.5%;
wherein, the structural formula of the ionic liquid BSIM-Br is as follows:
the preparation method of the ionic liquid BSIM-Br comprises the following steps: 2.66g of a sulfonic acid group compound containing bisimidazole and 2.33g of hydrobromic acid with the mass fraction of 40% are added into a flask, 0.40mL of water is added, the mixture is heated to 80 ℃ for 4 hours of reaction, and then the mixture is cooled to room temperature; washing with toluene and diethyl ether for 2 times respectively, and oven drying to obtain oily liquid BSIM-Br.
2. Use of a biimidazole-based ionic liquid according to claim 1 for catalyzing biomass to prepare levulinic acid, characterized in that:the sulfonic acid group compound containing biimidazole is prepared by the following method: 27.48g of imidazole and 16g of sodium hydroxide are added into 160mL of dimethyl sulfoxide, heated and stirred to 60 ℃,1, 4-dichlorobutane is slowly added after the reaction for 1 hour, and then the reaction is carried out for 2 hours at 60 ℃, and then the reaction is cooled to room temperature; pouring the reaction solution into 600mL of ice sodium chloride aqueous solution, stirring for 20min, filtering, washing the filter cake with 400mL of deionized water twice, collecting the solid, and drying in an oven at 80 ℃ for 12 hours to obtain a white solid product B 1 The method comprises the steps of carrying out a first treatment on the surface of the Biimidazole compound B 1 The structural formula is as follows:
11.4g of bisimidazole compound B 1 And 32.64g of 1, 4-butanesulfonic acid lactone are added into a 100mL flask, and after being mechanically stirred for 72 hours at room temperature, the mixture is washed three times by diethyl ether and dried to obtain colorless viscous liquid C 2 ；
Sulfonic acid group compound C containing bisimidazole 2 The structural formula is as follows:
wherein the imidazole compound is
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