CN115536618B - Preparation of MSH-GVL solvent system and method for efficiently preparing furan compound by dissolving and catalyzing agricultural biomass in one pot - Google Patents

Preparation of MSH-GVL solvent system and method for efficiently preparing furan compound by dissolving and catalyzing agricultural biomass in one pot Download PDF

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CN115536618B
CN115536618B CN202211203053.4A CN202211203053A CN115536618B CN 115536618 B CN115536618 B CN 115536618B CN 202211203053 A CN202211203053 A CN 202211203053A CN 115536618 B CN115536618 B CN 115536618B
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furfural
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CN115536618A (en
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任俊莉
刘慧莹
林琦璇
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South China University of Technology SCUT
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    • C07—ORGANIC CHEMISTRY
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    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
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Abstract

The invention discloses a method for preparing a furan compound by using an MSH-GVL solvent system and a method for efficiently preparing a furan compound by using agricultural biomass through dissolution catalysis in one pot. Comprising the following steps: liBr.3H in different volume ratios 2 Mixing O and GVL as a solvent, and adopting hydrates of different metal chloride salts as a catalyst to prepare the MSH-GVL solvent system. Carrying out microwave hydrothermal catalytic reaction on the solvent system and agricultural biomass under mild conditions to obtain hydrolysate rich in furfural, 5-hydroxymethylfurfural and lignin; ethanol-water two-step precipitation is carried out on the filtrate to obtain precipitated lignin, ethanol and water can be recovered by rotary evaporation, and furfural and 5-hydroxymethylfurfural are separated by distillation in the residual GVL. The MSH-GVL solvent system is environment-friendly, high in catalytic efficiency and simple to prepare, can dissolve all components of agricultural biomass under mild conditions, catalyzes carbohydrates to prepare furan compounds, and can reprecipitate dissolved lignin and recover the solvent.

Description

Preparation of MSH-GVL solvent system and method for efficiently preparing furan compound by dissolving and catalyzing agricultural biomass in one pot
Technical Field
The invention belongs to the technical field of biomass resource utilization, and particularly relates to a preparation method of a fused salt hydrate/gamma-valerolactone (MSH-GVL) solvent system and a method for efficiently preparing a furan compound by dissolving and catalyzing agricultural biomass in one pot.
Background
Furfural (FF), also called furaldehyde, is the most important derivative of furan ring system, has active chemical properties, can produce 1600 kinds of derivatives through reactions such as hydrogenation, oxidation, chlorination, nitration, condensation and the like, is an important organic chemical raw material and chemical solvent, and is regarded as one of 12 large value-added products by the United states department of energy. The 5-hydroxymethylfurfural (5-HMF or HMF) is a novel biomass-based chemical raw material with great potential, can be used as an intermediate for a plurality of reactions, a monomer synthesized by a high polymer material, a raw material synthesized by a macrocyclic compound and the like, and becomes one of renewable platform compounds important in modern chemical industry. Different furans can be obtained by respectively catalytic conversion of hemicellulose (polysaccharides) and cellulose in agricultural biomass, and furfural and 5-HMF are key platform chemicals produced by lignocellulose biorefinery, can be further converted into biofuel and useful chemicals, are widely applied to industries such as petroleum, plastics, medicines, agriculture and the like, and have wide development prospects. The raw materials for producing furan compound furfural and the like are various, and agricultural biomass which is loose in structure, rich in pentosan and low in lignification degree, such as corncob, wood dust, bagasse, wheat straw and the like, is preferred according to experience.
Molten Salt Hydrate (MSH) is a green, efficient, low boiling point cellulose raw material solvent, and has been used in a large number of fields such as dissolution, catalysis, saccharification, conversion, etc. of cellulose and hemicellulose. Wherein, lithium bromide trihydrate LiBr 3H 2 O was previously proven by a great deal of research to be an excellent solvent for biomass carbohydrates, which often requires relatively high temperatures ± the dissolution of carbohydrates>100 ℃ and the temperature and acidity required by the catalytic hydrolysis are higher, which increases the cost of raw materials and the problem of acid recovery, and byproducts such as coke, humus and the like are generated in the reaction process, thereby increasing the complexity of the process. If the catalyst can dissolve and catalyze the carbohydrate in the biomass under milder conditions, the catalyst is more beneficial to solid-liquid separation and recycling of the solvent. However, liBr.3H alone 2 The O system dissolves a large amount of cellulose and hemicellulose under mild conditions, and catalytically prepares high value-added products, which has not been reported in the prior publications.
The furfural is formed by hydrolyzing pentose into pentose under an acidic condition and then dehydrating and cyclizing the pentose; similar to furan-based HMF, cellulose is hydrolyzed to glucose and then dehydrated and cyclized, but the conditions required for HMF production are more complex than those for furfural. The method for preparing furan can be divided into dilute acid method and inorganic method according to different catalystsSalt catalysis, solid acid catalysis, and the like. In recent years, the technology of preparing energy and high-added-value chemicals by catalytically converting agricultural biomass by using inorganic metal salts is receiving more and more attention from scientists. The metal chloride has high catalytic efficiency, less corrosion to equipment than inorganic acid, better dissolubility than heterogeneous catalyst, low price and technical and economic feasibility. Wang et al used a number of different metal chlorides (CrCl) 3 、CrCl 2 、AlCl 3 、FeCl 3 、SnCl 4 、SnCl 2 、GeCl 4 And InCl 3 ) Catalytic production of furfural from commercial xylan in pure water systems, indicating SnCl 4 The catalytic effect of (2) is best, the highest yield of furfural is 48.8% after the reaction is carried out for 120min at 150 ℃, and the 2-MTHF/H is exchanged under the same condition 2 The furfural yield in the O two-phase system can reach 78.1 percent (Direct transformation of xylan-type hemicelluloses to furfural via SnCl, 4, catalysts in aqueous and biphasic systems, bioresource.technology, 183 (2015), 188);and Mazza evaluated 14 different metal halide salts (FeCl) 3 、LaCl 3 、CrCl 3 、AlCl 3 、NiCl 2 、MnCl 2 、MgCl 2 、CaCl 2 LiCl, naCl, KCl, liBr, liI and NaBr) can catalyze xylose to produce furfural under microwave hydrothermal conditions, wherein FeCl 3 Shows the best catalytic activity (Acid-catalyzed conversion of xylose, xylan and straw into furfural by microwave-assisted reaction. Bioresource. Technology, 102 (2011), 7371); organic solvents such as GVL, THF, 2-MTHF and inorganic chloride FeCl with Lewis acid are adopted 3 ·6H 2 O、SnCl 4 、AlCl 3 ·6H 2 Homogeneous catalysts such as O are widely used in the reaction of preparing furfuraldehyde by xylan catalysis. The catalytic preparation of furfural generally results in a weakening of the cellulose network in the biomass due to hemicellulose hydrolysis, with HMF being accompanied by furfural formation under suitable conditions. Yang et al AlCl 3 To prepare the furfuraldehyde by catalyzing the corncob by the catalyst in a water-NaCl/THF biphasic system (160 ℃),yields of 55% were obtained with concomitant HMF production (Synthesis of Furfural from Xylose, xylan, and Biomass Using AlCl center dot 6H (2) O in Biphasic Media via Xylose Isomerization to xylulose. Chemsuschem,5 (2012), 405.). Zhao et al compared to different metal chlorides (CrCl) 2 、CrCl 3 、FeCl 2 、FeCl 3 、CuCl 2 、VCl 3 、MoCl 3 、PdCl 2 、PtCl 2 、RuCl 3 RhCl in ionic liquid [ EMIM ]]The effect of catalyzing glucose in Cl, the metal chloride salt was found to be an excellent catalyst for the formation of HMF (Metal chlorides in ionic liquid solvents convert sugars to 5-hydroxymethylfurfural [ J)]Science,2007,316 (5831):1597.). Hu et al in SnCl 4 For the catalyst in [ EMim ]]In BF4, glucose was catalyzed to produce HMF in 67% (Efficient conversion of glucose into 5-hydroxymethylfurfural catalyzed by a common Lewis acid SnCl) 4 in an ionic liquid green chem 2009; 11:1746.). Sudipta et al with AlCl 3 The catalyst is heated in water phase by microwave to catalyze fructose and glucose to prepare HMF, the yield is 50% and 35% (Microwave assisted conversion of carbohydrates and biopolymers to-hydroxymethylfurfural with aluminium chloride catalyst in water. Green Chemistry 2011;13 (10): 2859.).
The chloride salt of metal ions such as Al, fe, sn and the like contains Lewis acid sites and is considered as a catalyst for effectively catalyzing xylose, glucose and biomass raw materials to prepare furfural and HMF, but the method has the defects of higher required temperature, long time, poor yield and the like, needs to be improved, and rarely produces two furan products FF and HMF from the biomass raw materials directly. Therefore, the development of a green and efficient dissolution and catalysis solvent system breaks the natural anti-degradation barrier of biomass, efficiently prepares energy and high-added-value chemicals, is very important for the recycling utilization of three main elements, has important significance for biomass refining and biomass hydrocarbon fuel, and can assist the realization of a 'double carbon' target.
Disclosure of Invention
In order to solve the above disadvantages and shortcomings of the prior art, a primary object of the present invention is to provide a green and efficient method for preparing a solvent system, which shows good dissolution catalysis effect on agricultural biomass such as wheat straw, corn straw, corncob, etc.
The invention further aims to provide a method for preparing furan compounds furfural and HMF by efficiently dissolving and catalyzing carbohydrates in agricultural biomass in one pot by utilizing the solvent system.
The aim of the invention is achieved by the following technical scheme.
A method for preparing an MSH-GVL solvent system, comprising the following steps:
LiBr with H 2 O is as follows: 3, heating and stirring until a uniform solution is formed (stirring for 30min at 80 ℃ to enable the solution to be completely and rapidly dissolved uniformly) to obtain a LiBr-MSH solvent; then adding hydrated metal chloride into LiBr-MSH solvent; an organic reagent gamma-valerolactone (GVL) is introduced into the LiBr-MSH system to form a single-phase catalytic dissolution system, so as to obtain an MSH-GVL solvent system.
Preferably, the LiBr-MSH solvent is LiBr.3H 2 And the mass percentage of O is 61.7%.
Preferably, the metal chloride salt is SnCl 4 、FeCl 3 、AlCl 3 Is added in the form of a hydrate. Preferably, the addition amount of the hydrated metal chloride salt is 0 to 0.5mmol.
Preferably, the volume ratio of LiBr-MSH solvent to GVL is LiBr.3H 2 O: GVL is 1: (0.5-3).
An environmentally friendly MSH-GVL solvent system prepared by the above method.
A method for efficiently preparing furan compounds furfural and HMF by using the solvent system to dissolve and catalyze carbohydrates in agricultural biomass in one pot comprises the following steps:
crushing, sieving, extracting, cleaning and drying an agricultural biomass raw material, ultrasonically mixing the absolute dry agricultural biomass raw material with an MSH-GVL solvent system, and transferring the mixture into a microwave hydrothermal reaction kettle for microwave treatment; after the reaction is finished, cooling by tap water, centrifuging the reaction mixture, and separating out solid residues; filtering to obtain hydrolysate rich in furfural, HMF and lignin, filtering and diluting the liquid product with a 0.22 μm filter head, and detecting with high performance liquid chromatography; precipitating the filtrate with ethanol and water, standing to precipitate lignin, and centrifuging to collect the lignin; recovering ethanol and water by rotary evaporation, and distilling and separating furfural and HMF from the residual GVL.
Preferably, the mesh number of the absolute dry agricultural biomass raw material is 40-60 mesh.
Preferably, the solid to liquid ratio of the agricultural biomass feedstock to the MSH-GVL solvent system is 1: (30-120) g/ml.
Preferably, the conditions of the microwave treatment are as follows: the temperature is 80-130 ℃, the reaction time is 10-50 min, and the power is 400-600W.
The preparation method of the invention and the obtained product have the following advantages and beneficial effects:
(1) The MSH-GVL solvent system prepared by the invention is used as a catalyst and a reaction solvent, and has the advantages of strong dissolving power for agricultural biomass, high catalytic efficiency, environmental friendliness, simple preparation method and the like.
(2) In the process of catalyzing the carbohydrate of the agricultural biomass to generate the furan compounds furfural and HMF, the MSH-GVL solvent system prepared by the invention has mild reaction conditions, easy control of one-pot operation, no addition of mineral acid in the reaction process, equipment corrosion prevention, environmental friendliness and capability of achieving the purposes of energy conservation and emission reduction and reducing the production cost of the furan products furfural and HMF.
(3) The agricultural biomass in the MSH-GVL solvent system prepared by the invention presents a three-main-element utilization mode of 'full-component dissolution-lignin reprecipitation', the carbohydrate is converted into high-added-value products such as furfural, HMF and the like in situ, the furfural yield is as high as 78%, the HMF yield is close to 33%, the lignin can be precipitated and reused, and the solvent can be recovered. The invention provides a reference thinking for three-component resource utilization and biomass hydrocarbon fuel development.
Drawings
FIG. 1 is a process flow diagram of a method for preparing furan compounds furfural and 5-hydroxymethylfurfural by one-pot efficient preparation of MSH-GVL solvent system and dissolution catalysis of agricultural biomass.
FIG. 2 is a high performance liquid chromatogram of the filtrate after the reaction of example 1.
FIG. 3 is a high performance liquid chromatogram of the filtrate after the reaction of example 2.
FIG. 4 is a high performance liquid chromatogram of the filtrate after the reaction of example 3.
FIG. 5 is a high performance liquid chromatogram of the filtrate after the reaction of example 4.
FIG. 6 is a high performance liquid chromatogram of the filtrate after the reaction of example 5.
FIG. 7 is a high performance liquid chromatogram of the filtrate after the reaction of example 6.
FIG. 8 is a high performance liquid chromatogram of the filtrate after the reaction of example 7.
FIG. 9 is a high performance liquid chromatogram of the filtrate after the reaction of example 7 after secondary hydrolysis.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but embodiments of the present invention are not limited thereto.
Example 1
A method for preparing MSH-GVL solvent system and dissolving catalytic wheat straw to prepare furan compound efficiently in one pot is shown in figure 1. The preparation method comprises the following specific steps:
(1) Preparation of MSH-GVL solvent System LiBr.3H 2 O-GVL+AlCl 3 ·6H 2 O: into a pressure-resistant bottle were charged 43.5g of LiBr and 27g H 2 O is mixed, and is placed in an oil bath in a sealing way, heated and stirred for 30min at 80 ℃, and is evenly mixed and cooled to obtain LiBr.3H 2 O; 15ml LiBr.3H was taken 2 O is added with 0.0723g AlCl 3 ·6H 2 O; 15ml GVL was added to this MSH system.
(2) Microwave hydrothermal reaction to prepare furan products: uniformly mixing 0.5g of wheat straw and 30ml of the MSH-GVL solvent system prepared in the step (1), placing the mixture in a microwave (600W) hydrothermal reaction kettle, reacting for 50min at 90 ℃, and stirring; after the reaction is finished, cooling by tap water, centrifuging the reaction mixture, and separating out solid residues; the liquid product was filtered with a 0.22 μm filter head, and was subjected to detection of FF, HMF, monosaccharides, etc. by high performance liquid chromatography, and the different peak-off times of the filtrate product after the reaction were marked in fig. 2, and qualitative and quantitative detection of FF, HMF, monosaccharides, etc. was possible depending on the time and peak area. Adding ethanol-water into the filtrate, standing for precipitation, centrifuging, and collecting; excess ethanol and water were recovered by rotary evaporation, and FF, HMF were separated by distillation from the remaining GVL.
The content of monosaccharides and furfural and HMF in the filtrate were all determined by High Performance Liquid Chromatography (HPLC).
Xylose yield= (moles of xylose measured by HPLC)/moles of xylose in wheat straw x 100%;
furfural yield= (moles of furfural measured by HPLC)/moles of xylose in wheat straw x 100%;
xylose conversion= (mass of xylose in wheat straw-mass of xylose in residue)/mass of xylose in wheat straw x 100%;
glucose yield= (moles of glucose measured by HPLC)/moles of glucose in wheat straw x 100%;
HMF yield= (HMF moles measured by HPLC)/glucose moles in wheat straw x 100%;
glucose conversion= (mass of glucose in wheat straw-mass of glucose in residue)/mass of glucose in wheat straw x 100%;
through calculation, the furfural yield of the embodiment is 64.25%, the HMF yield is 10.74%, the xylose yield is 32.61%, the xylose conversion rate is 98%, the glucose yield is 66.28%, and the glucose conversion rate is 91%.
Example 2
A method for preparing MSH-GVL solvent system and dissolving catalytic wheat straw to prepare furan compound efficiently in one pot is shown in figure 1. The preparation method comprises the following specific steps:
(1) Preparation of MSH-GVL solvent System LiBr.3H 2 O-GVL+SnCl 4 ·5H 2 O: into a pressure-resistant bottle were charged 43.5g of LiBr and 27g H 2 O is mixed, and is placed in an oil bath in a sealing way, heated and stirred for 30min at 80 ℃, and is evenly mixed and cooled to obtain LiBr.3H 2 O; 15ml LiBr was taken·3H 2 O is added with 0.1052g of SnCl 4 ·5H 2 O; 15ml GVL was added to this MSH system.
(2) Microwave hydrothermal reaction to prepare furan products: uniformly mixing 0.5g of wheat straw and 30ml of the MSH-GVL solvent system prepared in the step (1), placing the mixture into a microwave (400W) hydrothermal reaction kettle, and reacting for 30min at 120 ℃ without stirring; after the reaction is finished, cooling by tap water, centrifuging the reaction mixture, and separating out solid residues; the liquid product was filtered with a 0.22 μm filter head, and was subjected to detection of FF, HMF, monosaccharides, etc. by high performance liquid chromatography, and the different peak-off times of the filtrate product after the reaction were marked in fig. 3, and qualitative and quantitative detection of FF, HMF, monosaccharides, etc. was possible depending on the time and peak area. Adding ethanol-water into the filtrate, standing for precipitation, centrifuging, and collecting; excess ethanol and water were recovered by rotary evaporation, and FF, HMF were separated by distillation from the remaining GVL.
The contents of glucose, xylose, furfural and HMF in the filtrate were all determined by High Performance Liquid Chromatography (HPLC).
Xylose yield= (moles of xylose measured by HPLC)/moles of xylose in wheat straw x 100%;
furfural yield= (moles of furfural measured by HPLC)/moles of xylose in wheat straw x 100%;
xylose conversion= (mass of xylose in wheat straw-mass of xylose in residue)/mass of xylose in wheat straw x 100%;
glucose yield= (moles of glucose measured by HPLC)/moles of glucose in wheat straw x 100%;
HMF yield= (HMF moles measured by HPLC)/glucose moles in wheat straw x 100%;
glucose conversion= (mass of glucose in wheat straw-mass of glucose in residue)/mass of glucose in wheat straw x 100%;
calculated, the furfural yield of this example was 33.28%, the HMF yield was 3.29%, the xylose yield was 14.16%, the xylose conversion was 90%, the glucose yield was 3.28%, and the glucose conversion was 49%.
Example 3
A method for preparing MSH-GVL solvent system and dissolving and catalyzing corncob to prepare furan compound in one pot is shown in figure 1. The preparation method comprises the following specific steps:
(1) Preparation of MSH-GVL solvent System LiBr.3H 2 O-GVL+AlCl 3 ·6H 2 O: into a pressure-resistant bottle were charged 43.5g of LiBr and 27g H 2 O is mixed, and is placed in an oil bath in a sealing way, heated and stirred for 30min at 80 ℃, and is evenly mixed and cooled to obtain LiBr.3H 2 O; 15ml LiBr.3H was taken 2 O is added with 0.0723g AlCl 3 ·6H 2 O; 15ml GVL was added to this MSH system;
(2) Microwave hydrothermal reaction to prepare furan products: uniformly mixing 0.5g of corncob and 30ml of MSH-GVL solvent system prepared in the step (1), placing the mixture in a microwave (600W) hydrothermal reaction kettle, reacting for 20min at 100 ℃, and stirring; after the reaction is finished, cooling by tap water, centrifuging the reaction mixture, and separating out solid residues; the liquid product was filtered with a 0.22 μm filter head, and was subjected to detection of FF, HMF, monosaccharides, etc. by high performance liquid chromatography, and the different peak-off times of the filtrate product after the reaction were marked in fig. 4, and qualitative and quantitative detection of FF, HMF, monosaccharides, etc. was possible depending on the time and peak area. Adding ethanol-water into the filtrate, standing for precipitation, centrifuging, and collecting; excess ethanol and water were recovered by rotary evaporation, and FF, HMF were separated by distillation from the remaining GVL.
The contents of glucose, xylose, furfural, HMF and the like in the filtrate are all determined by a High Performance Liquid Chromatograph (HPLC).
Xylose yield= (moles of xylose measured by HPLC)/moles of xylose in corn cob x 100%;
furfural yield= (moles of furfural measured by HPLC)/moles of xylose in corn cob x 100%;
xylose conversion= (mass of xylose in corncob-mass of xylose in residue)/mass of xylose in corncob x 100%;
glucose yield = (moles of glucose measured by HPLC)/moles of glucose in corn cob x 100%;
HMF yield= (HMF moles HPLC)/glucose moles in corn cob x 100%;
glucose conversion= (mass of glucose in corn cob-mass of glucose in residue)/mass of glucose in corn cob x 100%;
calculated, the furfural yield of this example was 75.32%, the HMF yield was 32.09%, the xylose conversion was-99%, the xylose yield was 17.14%, the glucose yield was 60.51%, and the glucose conversion was-96%.
Example 4
A method for preparing MSH-GVL solvent system and dissolving catalytic wheat straw to prepare furan compound efficiently in one pot is shown in figure 1. The preparation method comprises the following specific steps:
(1) Preparation of MSH-GVL solvent System LiBr.3H 2 O-GVL+FeCl 3 ·6H 2 O: into a pressure-resistant bottle were charged 43.5g of LiBr and 27g H 2 O is mixed, and is placed in an oil bath in a sealing way, heated and stirred for 30min at 80 ℃, and is evenly mixed and cooled to obtain LiBr.3H 2 O; 20ml LiBr.3H was taken 2 O adding 0.054g FeCl 3 ·6H 2 O; to this MSH system 10ml GVL was added.
(2) Microwave hydrothermal reaction to prepare furan products: uniformly mixing 0.5g of wheat straw and 30ml of the MSH-GVL solvent system prepared in the step (1), placing the mixture into a microwave (400W) hydrothermal reaction kettle, and reacting for 30min at 120 ℃ without stirring; after the reaction is finished, cooling by tap water, centrifuging the reaction mixture, and separating out solid residues; the liquid product was filtered with a 0.22 μm filter head, and was subjected to detection of FF, HMF, monosaccharides, etc. by high performance liquid chromatography, and the different peak-off times of the filtrate product after the reaction were marked in fig. 5, and qualitative and quantitative detection of FF, HMF, monosaccharides, etc. was possible depending on the time and peak area. Adding ethanol-water into the filtrate, standing for precipitation, centrifuging, and collecting; excess ethanol and water were recovered by rotary evaporation, and FF, HMF were separated by distillation from the remaining GVL.
The content of monosaccharides and furfural and HMF in the filtrate were all determined by High Performance Liquid Chromatography (HPLC).
Xylose yield= (moles of xylose measured by HPLC)/moles of xylose in wheat straw x 100%;
furfural yield= (moles of furfural measured by HPLC)/moles of xylose in wheat straw x 100%;
xylose conversion= (mass of xylose in wheat straw-mass of xylose in residue)/mass of xylose in wheat straw x 100%;
glucose yield= (moles of glucose measured by HPLC)/moles of glucose in wheat straw x 100%;
HMF yield= (HMF moles measured by HPLC)/glucose moles in wheat straw x 100%;
cellulose retention = mass of glucose in residue/mass of glucose in wheat straw x 100%;
through calculation, the furfural yield of the embodiment is 31.24%, the xylose yield is 22.25%, the xylose conversion rate is 88%, no obvious glucose and HMF are generated, and the cellulose retention rate is 90%.
Example 5
A method for preparing MSH-GVL solvent system and dissolving catalytic wheat straw to prepare furan compound efficiently in one pot is shown in figure 1. The preparation method comprises the following specific steps:
(1) Preparation of MSH-GVL solvent System LiBr.3H 2 O-GVL+AlCl 3 ·6H 2 O: into a pressure-resistant bottle were charged 43.5g of LiBr and 27g H 2 O is mixed, and is placed in an oil bath in a sealing way, heated and stirred for 30min at 80 ℃, and is evenly mixed and cooled to obtain LiBr.3H 2 O; 20ml LiBr.3H was taken 2 O is added with 0.1205g of AlCl 3 ·6H 2 O; to this MSH system 10ml GVL was added.
(2) Microwave hydrothermal reaction to prepare furan products: uniformly mixing 1.0g of wheat straw and 30ml of the MSH-GVL solvent system prepared in the step (1), placing the mixture in a microwave (600W) hydrothermal reaction kettle, reacting for 10min at 110 ℃, and stirring; after the reaction is finished, cooling by tap water, centrifuging the reaction mixture, and separating out solid residues; the liquid product was filtered with a 0.22 μm filter head, and was subjected to detection of FF, HMF, monosaccharides, etc. by high performance liquid chromatography, and the different peak-off times of the filtrate product after the reaction were marked in fig. 6, and qualitative and quantitative detection of FF, HMF, monosaccharides, etc. was possible depending on the time and peak area. Adding ethanol-water into the filtrate, standing for precipitation, centrifuging, and collecting; excess ethanol and water were recovered by rotary evaporation, and FF, HMF were separated by distillation from the remaining GVL.
The content of monosaccharides and furfural and HMF in the filtrate were all determined by High Performance Liquid Chromatography (HPLC).
Xylose yield= (moles of xylose measured by HPLC)/moles of xylose in wheat straw x 100%;
furfural yield= (moles of furfural measured by HPLC)/moles of xylose in wheat straw x 100%;
xylose conversion= (mass of xylose in wheat straw-mass of xylose in residue)/mass of xylose in wheat straw x 100%;
glucose yield= (moles of glucose measured by HPLC)/moles of glucose in wheat straw x 100%;
HMF yield= (HMF moles measured by HPLC)/glucose moles in wheat straw x 100%;
glucose conversion= (mass of glucose in wheat straw-mass of glucose in residue)/mass of glucose in wheat straw x 100%;
calculated, the furfural yield of this example was 77.22%, the HMF yield was 32.57%, the xylose yield was 4.45%, the xylose conversion was 97%, the glucose yield was 28.33%, and the glucose conversion was 89%.
Example 6
A method for preparing MSH-GVL solvent system and dissolving and catalyzing corncob to prepare furan compound in one pot is shown in figure 1. The preparation method comprises the following specific steps:
(1) Preparation of MSH-GVL solvent System LiBr.3H 2 O-GVL+AlCl 3 ·6H 2 O: into a pressure-resistant bottle were charged 43.5g of LiBr and 27g H 2 O is mixed, and is placed in an oil bath in a sealing way, heated and stirred for 30min at 80 ℃, and is evenly mixed and cooled to obtain LiBr.3H 2 O; 20ml LiBr.3H was taken 2 O is added with 0.0482g of AlCl 3 ·6H 2 O; 15ml GVL was added to this MSH system.
(2) Microwave hydrothermal reaction to prepare furan products: uniformly mixing 0.5g of corncob and 30ml of MSH-GVL solvent system prepared in the step (1), placing the mixture in a microwave (600W) hydrothermal reaction kettle, reacting for 40min at 80 ℃, and stirring; after the reaction is finished, cooling by tap water, centrifuging the reaction mixture, and separating out solid residues; the liquid product was filtered with a 0.22 μm filter head, and was subjected to detection of FF, HMF, monosaccharides, etc. by high performance liquid chromatography, and the different peak-off times of the filtrate product after the reaction were marked in fig. 7, and qualitative and quantitative detection of FF, HMF, monosaccharides, etc. was possible depending on the time and peak area. Adding ethanol-water into the filtrate, standing for precipitation, centrifuging, and collecting; excess ethanol and water were recovered by rotary evaporation, and FF, HMF were separated by distillation from the remaining GVL.
The content of monosaccharides and furfural and HMF in the filtrate were all determined by High Performance Liquid Chromatography (HPLC).
Xylose yield= (moles of xylose measured by HPLC)/moles of xylose in corn cob x 100%;
furfural yield= (moles of furfural measured by HPLC)/moles of xylose in corn cob x 100%;
xylose conversion= (mass of xylose in corncob-mass of xylose in residue)/mass of xylose in corncob x 100%;
glucose yield = (moles of glucose measured by HPLC)/moles of glucose in corn cob x 100%;
HMF yield= (HMF moles HPLC)/glucose moles in corn cob x 100%;
glucose conversion= (mass of glucose in corn cob-mass of glucose in residue)/mass of glucose in corn cob x 100%;
through calculation, the furfural yield of the embodiment is 38.20%, the HMF yield is 1.78%, the xylose yield is 54.53%, the xylose conversion rate is 93%, the glucose yield is 17.13%, and the glucose conversion rate is 49%.
Example 7
A method for preparing MSH-GVL solvent system and dissolving catalytic wheat straw to prepare furan compound efficiently in one pot is shown in figure 1. The preparation method comprises the following specific steps:
(1) Preparation of MSH-GVL solvent System LiBr.3H 2 O-GVL+ no catalyst: adding into pressure-resistant bottle43.5g LiBr and 27g H 2 O is mixed, and is placed in an oil bath in a sealing way, heated and stirred for 30min at 80 ℃, and is evenly mixed and cooled to obtain LiBr.3H 2 O; 10ml LiBr.3H was taken 2 O, 20ml GVL was added and mixed.
(2) Microwave hydrothermal reaction: uniformly mixing 0.5g of wheat straw and 30ml of the MSH-GVL solvent system prepared in the step (1), placing the mixture in a microwave (600W) hydrothermal reaction kettle, reacting for 30min at 100 ℃, and stirring; after the reaction is finished, cooling by tap water, centrifuging the reaction mixture, separating out solid residues, and carrying out component analysis; filtering the liquid product with a 0.22 μm filter head, detecting by high performance liquid chromatography, marking different peak time of the filtrate product after reaction in FIG. 8, and qualitatively and quantitatively detecting xylose, glucose and the like according to the time and the peak area; the filtrate was subjected to secondary hydrolysis and then again to high performance liquid chromatography, as shown in FIG. 9, and the difference between the two xylose fractions was the amount of xylooligosaccharide. Adding ethanol-water into the filtrate, standing for precipitation, centrifuging, and collecting; excess ethanol and water were recovered by rotary evaporation, and the remaining GVL was recovered by distillation.
The content of monosaccharide and xylooligosaccharide in the filtrate was determined by High Performance Liquid Chromatography (HPLC).
Xylose yield= (moles of xylose measured by HPLC)/moles of xylose in wheat straw x 100%;
xylooligosaccharide yield= (difference of xylose mole number measured by two HPLC)/xylose mole number in wheat straw is multiplied by 100%;
xylose conversion= (mass of xylose in wheat straw-mass of xylose in residue)/mass of xylose in wheat straw x 100%;
glucose yield= (moles of glucose measured by HPLC)/moles of glucose in wheat straw x 100%;
cellulose retention = mass of glucose in residue/mass of glucose in wheat straw x 100%;
according to calculation, no catalyst is added in the embodiment, no furfural or HMF is generated, the xylose yield is 3.25%, the xylooligosaccharide yield is 54.09%, the xylose conversion rate is 67%, the glucose yield is less than 1%, and the cellulose retention rate is 98%.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.

Claims (6)

1. A method for preparing an MSH-GVL solvent system, comprising the steps of:
LiBr with H 2 O is as follows: 3, mixing the components in a molar ratio, heating and stirring the components until a uniform solution is formed, and obtaining a LiBr-MSH solvent; then adding hydrated metal chloride into LiBr-MSH solvent; introducing an organic reagent GVL into the LiBr-MSH system to form a single-phase catalytic dissolution system, so as to obtain an MSH-GVL solvent system;
the LiBr-MSH solvent is LiBr.3H 2 O, the mass percentage is 61.7%;
the metal chloride salt is SnCl 4 、FeCl 3 、AlCl 3 Is added in the form of a hydrate;
the addition amount of the hydrated metal chloride salt is 0-0.5 mmol;
the volume ratio of the LiBr-MSH solvent to the GVL is 1: (0.5-3).
2. A MSH-GVL solvent system prepared by the method of claim 1.
3. A method for preparing furan compounds furfural and HMF by using the MSH-GVL solvent system to dissolve and catalyze carbohydrates in agricultural biomass in one pot, which is characterized by comprising the following steps:
crushing, sieving, extracting, cleaning and drying an agricultural biomass raw material, ultrasonically mixing the absolute dry agricultural biomass raw material with an MSH-GVL solvent system, and transferring the mixture into a microwave hydrothermal reaction kettle for microwave treatment; after the reaction is finished, cooling by tap water, centrifuging the reaction mixture, and separating out solid residues; filtering to obtain hydrolysate rich in furfural, HMF and lignin, filtering and diluting the liquid product, and detecting by high performance liquid chromatography; precipitating the filtrate with ethanol and water, standing to precipitate lignin, and centrifuging to collect the lignin; recovering ethanol and water by rotary evaporation, and distilling and separating furfural and HMF from the residual GVL; the microwave treatment conditions are as follows: the temperature is 90-110 ℃ and the reaction time is 10-50 min.
4. A method for preparing furan compounds furfural and HMF by dissolving and catalyzing carbohydrates in agricultural biomass in a one-pot manner by using an MSH-GVL solvent system according to claim 3, wherein the mesh number of the absolute dry agricultural biomass raw material is 40-60 mesh.
5. A method for preparing furan compounds furfural and HMF by dissolving and catalyzing carbohydrates in agricultural biomass in an MSH-GVL solvent system according to claim 3, wherein the solid-to-liquid ratio of the agricultural biomass raw material to the MSH-GVL solvent system is 1: (30-120) g/ml.
6. A method for preparing furan compounds furfural and HMF by dissolving and catalyzing carbohydrates in agricultural biomass in a one-pot manner by using an MSH-GVL solvent system according to claim 3, wherein the power of the microwave treatment is 400-600W.
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