CN117659436A - Green high-efficiency pretreated biomass and application thereof in selective preparation of 2, 3-dihydrobenzofuran - Google Patents
Green high-efficiency pretreated biomass and application thereof in selective preparation of 2, 3-dihydrobenzofuran Download PDFInfo
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- 239000002028 Biomass Substances 0.000 title claims abstract description 51
- HBEDSQVIWPRPAY-UHFFFAOYSA-N 2,3-dihydrobenzofuran Chemical compound C1=CC=C2OCCC2=C1 HBEDSQVIWPRPAY-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 37
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 230000005496 eutectics Effects 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000000197 pyrolysis Methods 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 15
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 15
- 239000011592 zinc chloride Substances 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000002203 pretreatment Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 241000609240 Ambelania acida Species 0.000 claims description 63
- 239000010905 bagasse Substances 0.000 claims description 63
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- 235000019270 ammonium chloride Nutrition 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 239000008247 solid mixture Substances 0.000 claims description 12
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- 239000007791 liquid phase Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000012456 homogeneous solution Substances 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 230000005855 radiation Effects 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 238000010926 purge Methods 0.000 claims description 4
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 3
- 235000019743 Choline chloride Nutrition 0.000 claims description 3
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 3
- 229960003178 choline chloride Drugs 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 claims description 2
- 235000011613 Pinus brutia Nutrition 0.000 claims description 2
- 241000018646 Pinus brutia Species 0.000 claims description 2
- 229960003237 betaine Drugs 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000010902 straw Substances 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- 229960001939 zinc chloride Drugs 0.000 claims description 2
- 239000000370 acceptor Substances 0.000 claims 4
- 229920005610 lignin Polymers 0.000 abstract description 18
- 239000007787 solid Substances 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 7
- 238000001914 filtration Methods 0.000 abstract description 5
- 239000011259 mixed solution Substances 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 3
- 229910052725 zinc Inorganic materials 0.000 abstract description 3
- 239000011701 zinc Substances 0.000 abstract description 3
- 239000003446 ligand Substances 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 14
- 238000012216 screening Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000001913 cellulose Substances 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- -1 glycerol formal Substances 0.000 description 4
- 239000012263 liquid product Substances 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000004523 catalytic cracking Methods 0.000 description 3
- 238000004880 explosion Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002240 furans Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 208000001738 Nervous System Trauma Diseases 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012075 bio-oil Substances 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 229940074076 glycerol formal Drugs 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000000302 ischemic effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 208000028412 nervous system injury Diseases 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003248 quinolines Chemical group 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000008736 traumatic injury Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a green high-efficiency pretreated biomass and application thereof in selective preparation of 2, 3-dihydrobenzofuran, wherein the pretreatment comprises the following steps: and uniformly mixing the biomass raw material with the ternary eutectic solvent, reacting in a microwave synthesizer, washing, filtering, drying and collecting solid residues after the reaction to obtain the pretreated biomass. The ternary eutectic solvent is a mixed solution of zinc chloride, ethylene glycol and water, is simple to prepare, has easily obtained and harmless raw materials, and can be recycled. The zinc has the double effects of a solvent and a catalyst, can increase the number of total hydrogen bonds, promote the breaking of beta-O-4 bond energy, can also improve the acid site of the solvent, forms a metal ion complex with a water ligand, and promotes biomass pyrolysis; the pretreatment method can reach the lignin removal rate of more than 80% at low temperature, the required reaction time is short, the solvent is easy to obtain and harmless, the selectivity of the 2, 3-dihydrobenzofuran after the pyrolysis reaction is higher than 40%, and the technical support is provided for promoting the industrialized process.
Description
Technical Field
The invention belongs to the technical field of biomass energy utilization, and particularly relates to green high-efficiency pretreated biomass and application thereof in selective preparation of 2, 3-dihydrobenzofuran.
Background
Pyrolysis is one of the main methods for biomass energy conversion and utilization, pyrolysis reaction is a clean, environment-friendly and convenient-to-operate conversion method, and the obtained bio-oil contains various chemicals with high added value, wherein 2, 3-dihydrobenzofuran has high medicinal value, and can be used for traumatic injury, ischemic central nervous system injury and the like. Since 2, 3-dihydrobenzofuran is mainly obtained by reaction of cellulose and hemicellulose in lignocellulose biomass, separation of lignin from biomass is a major challenge for high-value utilization of biomass. The lignin can be selectively removed by proper pretreatment, so that the subsequent pyrolysis reaction has higher selectivity.
At present, the common pretreatment method mainly comprises physical pretreatment, chemical pretreatment, physicochemical pretreatment, biological pretreatment and the like; the physical pretreatment is simple to operate, but the treatment effect is more biased to the crystallinity and the size of the substance, and the active bonds in the substance are difficult to break; the chemical pretreatment is mature at present, but the treatment cost of acid-base waste liquid is high, and the damage to the environment caused by improper treatment is larger; the physical and chemical pretreatment steam explosion or ammonia fiber explosion equipment has complex operation and higher cost; biological methods have harsh conditions and longer periods, and the enzyme activity is also lower.
Patent CN115772273a provides pretreatment of an organic solvent including glycerol formal, acid, alkali, etc., the reaction process is low in pressure, the solvent can be recycled, but the preparation process is complex, and the waste liquid generated by acid, alkali, etc. is expensive to treat, and is harmful to the environment. Patent CN115976116a provides a pretreatment method, and uses steam explosion and eutectic solvent to treat biomass, so that a higher lignin removal rate is obtained, but the structure of cellulose is affected, and the treatment effect is unstable. Patent CN115873136a provides a method for pretreating a eutectic solvent, the solvent is choline chloride-ethylene glycol-p-toluenesulfonic acid, the pretreatment time is short, but the p-toluenesulfonic acid has toxicity, strong corrosiveness, environmental hazard and easy corrosion to equipment and pipelines. Therefore, in the aspects of biomass pretreatment and application, the development of the eutectic solvent with environmental protection, high efficiency, low cost and high lignin removal rate is important.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention aims to provide green and efficient pretreated biomass and application thereof in selective preparation of 2, 3-dihydrobenzofuran. The invention provides a green and efficient biomass pretreatment method, which can realize the delignification efficiency of more than 80% at low temperature, and the selectivity of 2, 3-dihydrobenzofuran can be higher than 40%.
The technical scheme adopted by the invention is as follows:
a green, highly effective pretreatment biomass, the pretreatment method of biomass comprising the steps of:
1) Crushing biomass raw materials, and drying to obtain biomass powder;
2) Preparation of ternary eutectic solvent: uniformly mixing a hydrogen bond acceptor and water, adding hydrogen bond donor glycol into a beaker, heating and stirring to obtain a transparent homogeneous solution, and obtaining a ternary eutectic solvent;
3) Microwave reaction: uniformly mixing the ternary eutectic solvent in the step 2) and the biomass powder in the step 1), adding the mixture into a microwave synthesis tube, and placing the microwave synthesis tube under microwave radiation of a microwave synthesizer for microwave pretreatment; and centrifuging the mixture, collecting the lower-layer solid mixture after centrifuging, adding the lower-layer solid mixture into an ammonium chloride aqueous solution for washing, centrifuging the mixture after washing, washing the mixture with deionized water to be neutral, and drying to obtain pretreated biomass.
Further, the particle size of the biomass powder in step 1) is 20 to 200 mesh, preferably 40 to 60 mesh.
Further, the biomass is bagasse, wood chips, straw or pine leaves, preferably bagasse.
Further, the hydrogen bond acceptor comprises zinc chloride, choline chloride or betaine, preferably the hydrogen bond acceptor is zinc chloride.
Further, the mass ratio of the hydrogen bond acceptor to the ethylene glycol is 1:2-15, preferably 1:8-10; the mass ratio of water to glycol is 1:0.2-1.0, preferably 1:0.25-0.5.
Further, in the step 2), the temperature of heating and stirring is 70-90 ℃, the stirring time is 10-80min, and the stirring speed is 200-600r/min.
Further, in step 3), the mass ratio of biomass to ternary eutectic solvent is 1:5-30, preferably 1:10-20.
Further, the reaction conditions for performing microwave pretreatment in step 3) are as follows: the microwave power is 100-400W, the treatment temperature is 50-70 ℃, the treatment time is 10-60 min, the microwave power is preferably 250-300W, the treatment temperature is preferably 60-65 ℃, and the treatment time is preferably 25-30 min.
Further, in the step 3), the concentration of the aqueous ammonium chloride solution is 0.5 to 3moL/L, preferably 1 to 2moL/L.
The invention also provides an application of the green high-efficiency pretreated biomass in selectively preparing 2, 3-dihydrobenzofuran, which comprises the following steps: carrying out pyrolysis reaction in a pyrolysis furnace, filling pretreated biomass in a constant temperature zone of the pyrolysis furnace, and introducing N 2 Purge the exhaust air, then at N 2 The reaction is carried out in the atmosphere, the temperature is raised to the reaction temperature of 500-550 ℃ from the room temperature at the speed of 30-60 ℃/min, the constant temperature is kept for 1-30min, preferably 5-10 min, the gas product generated by pyrolysis is discharged and condensed and collected, and the liquid phase product containing the pyrolysis target product 2, 3-dihydrobenzofuran is obtained.
Compared with the prior art, the invention has the following beneficial effects:
1) The green efficient pretreatment method adopts the zinc chloride-ethylene glycol-water ternary eutectic solvent for treatment, has simple preparation, can effectively reduce the viscosity of the eutectic solvent, is easy to obtain and harmless in raw materials, can be recycled, and reduces the production cost.
2) In the zinc chloride-ethylene glycol-water ternary eutectic solvent provided by the invention, zinc has the dual effects of a solvent and a catalyst, the total hydrogen bond quantity is increased, the breaking of beta-O-4 bond energy is promoted, the heating of zinc can improve the acid site of the solvent, and a metal ion complex is formed with a water ligand, so that the biomass pyrolysis is promoted.
3) According to the green efficient pretreatment method, the ternary eutectic solvent and microwaves are adopted to act cooperatively, and the reaction time of pretreatment can be remarkably reduced through dipole rotation and ion conduction, so that more uniform heat transfer can be realized with lower energy consumption, and the high lignin removal rate at low temperature can be realized; the eutectic solvent and the microwaves cooperate to improve the polarity of the solution and the stability of the active protons.
4) Compared with the method for directly cracking the biomass, the method has the advantages that the reaction activation energy is reduced, the product types are greatly reduced, and the difficulty of the subsequent purification step is reduced after the biomass is pretreated by the eutectic solvent and is applied to the aspect of biomass catalytic cracking; the total product species is reduced to within ten, and the selectivity of the 2, 3-dihydrobenzofuran can reach 42.718 percent.
Drawings
Fig. 1 is an SEM image of bagasse after pretreatment of example 1.
Fig. 2 is an infrared image of bagasse after various pretreatments.
Detailed Description
The invention will be further illustrated with reference to specific examples, but the scope of the invention is not limited thereto.
In the examples and comparative examples of the present invention, bagasse was dried in an oven at 110℃for 24 hours before use, and the particle size of the bagasse after screening and drying was 40 to 60 mesh.
Example 1
1g of zinc chloride is dissolved in 20ml of deionized water and uniformly mixed, 10g of ethylene glycol is added into the mixed solution of zinc chloride and deionized water, and the mixture is stirred for 1h at the temperature of 80 ℃ and the speed of 500r/min to obtain a transparent homogeneous solution, so as to obtain the ternary eutectic solvent. Uniformly mixing 1.5g of bagasse after screening and drying with the ternary eutectic solvent, loading the mixture into a microwave synthesis tube, and carrying out microwave pretreatment for 0.5h under the microwave radiation of a microwave synthesizer at the microwave power of 300W and the treatment temperature of 60 ℃; centrifuging the solid-liquid product in the microwave synthesis tube, collecting the lower layer solid mixture after centrifuging, adding the lower layer solid mixture into an ammonium chloride aqueous solution (2.1397 g of ammonium chloride is dissolved in 20ml of deionized water and uniformly mixed), washing, and stirring at 600r/min for 1.5h at 90 ℃; and (3) after stirring, filtering and washing the product to be neutral by deionized water, and drying the obtained pretreated bagasse at 110 ℃ for 24 hours to obtain the pretreated bagasse.
In the solid bagasse obtained after pretreatment, the bagasse mass is 1.35g, and the lignin removal rate is 83.04%.
Example 1 SEM images of bagasse after pretreatment are shown in figure 1.
Example 2
1g of zinc chloride is dissolved in 20ml of deionized water and uniformly mixed, 5g of ethylene glycol is added into the mixed solution of zinc chloride and deionized water, and the mixture is stirred for 1h at the temperature of 80 ℃ and at the speed of 500r/min to obtain a transparent homogeneous solution, so as to obtain the ternary eutectic solvent. Uniformly mixing 1.50g of bagasse after screening and drying with the ternary eutectic solvent, loading the mixture into a microwave synthesis tube, and carrying out microwave pretreatment for 0.5h at the treatment temperature of 60 ℃ under the microwave radiation of a microwave synthesizer at the microwave power of 300W; centrifuging the solid-liquid product in the microwave synthesis tube, collecting the lower layer solid mixture after centrifuging, adding the lower layer solid mixture into an ammonium chloride aqueous solution (2.1397 g of ammonium chloride is dissolved in 20ml of deionized water and uniformly mixed), washing, and stirring at 600r/min for 1.5h at 90 ℃; and (3) after stirring, filtering and washing the product to be neutral by deionized water, and drying the obtained pretreated bagasse at 110 ℃ for 24 hours to obtain the pretreated bagasse.
In the solid bagasse obtained after pretreatment, the bagasse mass was 1.36g, and the lignin removal rate was 75.43%.
Example 3
5g of zinc chloride is dissolved in 20ml of deionized water and uniformly mixed, 10g of ethylene glycol is added into the mixed solution of zinc chloride and deionized water, and the mixture is stirred for 1h at the temperature of 80 ℃ at the speed of 500r/min to obtain a transparent homogeneous solution, so as to obtain the ternary eutectic solvent. Uniformly mixing 1.50g of bagasse after screening and drying with the ternary eutectic solvent, putting the mixture into a microwave synthesis tube, and placing the microwave synthesis tube under the microwave radiation of a microwave synthesizer, and carrying out microwave treatment for 0.5h at the temperature of 300W and 60 ℃; centrifuging the solid-liquid product in the microwave synthesis tube, collecting the lower layer solid mixture after centrifuging, adding the lower layer solid mixture into an ammonium chloride aqueous solution (2.1397 g of ammonium chloride is dissolved in 20ml of deionized water and uniformly mixed), washing, and stirring at 600r/min for 1.5h at 90 ℃; and (3) after stirring, filtering and washing the product to be neutral by deionized water, and drying the obtained pretreated bagasse at 110 ℃ for 24 hours to obtain the pretreated bagasse.
In the solid bagasse obtained after pretreatment, the bagasse mass is 1.30g, and the lignin removal rate is 78.35%.
Comparative example 1
Uniformly mixing 1.50g of bagasse after screening and drying with 20mL of deionized water, filling the mixture into a beaker, and stirring the mixture at 90 ℃ for 6 hours; and (3) carrying out suction filtration on the product after stirring, and drying the obtained pretreated bagasse at 110 ℃ for 24 hours to obtain the pretreated bagasse.
In the solid bagasse obtained after pretreatment, the bagasse mass was 1.38g, and the lignin removal rate was 50.39%.
Comparative example 2
Comparative example 2 differs from example 1 only in that the "treatment temperature for microwave pretreatment was replaced with 40 ℃, and other conditions were unchanged, to finally obtain bagasse after pretreatment.
In the solid bagasse obtained after pretreatment, the bagasse mass was 1.34g, and the lignin removal rate was 78.36%.
Comparative example 3
Comparative example 3 differs from example 1 only in that the "treatment temperature for microwave pretreatment was replaced with 80 ℃, and other conditions were unchanged, to finally obtain bagasse after pretreatment.
In the solid bagasse obtained after pretreatment, the bagasse mass was 1.33g, and the lignin removal rate was 79.87%.
An infrared image of the original untreated bagasse, the bagasse after pretreatment of example 1, and the bagasse after pretreatment of comparative example 3 is shown in fig. 2.
Comparative example 4
Comparative example 4 differs from example 1 only in that in the "preparation of ternary eutectic solvent, 1g of zinc chloride was replaced with 1g of choline chloride", and other conditions were unchanged, to finally obtain bagasse after pretreatment.
In the solid bagasse obtained after pretreatment, the bagasse mass was 1.34g, and the lignin removal rate was 74.39%.
Comparative example 5
Comparative example 5 differs from example 1 only in that in the "formulation of ternary eutectic solvent, 10g of ethylene glycol was replaced by 10g of propylene glycol", the other conditions being unchanged, and finally a bagasse after pretreatment was obtained.
In the solid bagasse obtained after pretreatment, the bagasse mass was 1.33g, and the lignin removal rate was 75.69%.
Comparative example 6
1g of zinc chloride is dissolved in 20ml of deionized water and uniformly mixed, 10g of ethylene glycol is added into the mixed solution of zinc chloride and deionized water, and the mixture is stirred for 1h at the temperature of 80 ℃ and the speed of 500r/min to obtain a transparent homogeneous solution, so as to obtain the ternary eutectic solvent. Uniformly mixing 1.50g of bagasse after screening and drying with the ternary eutectic solvent, filling the mixture into a beaker, stirring the mixture for 6 hours at the temperature of 90 ℃ in an oil bath pot, centrifuging a solid-liquid product, collecting a lower layer solid mixture after centrifuging, adding the lower layer solid mixture into an ammonium chloride aqueous solution (2.1397 g of ammonium chloride is dissolved in 20ml of deionized water and uniformly mixed), washing the mixture, and stirring the mixture for 1.5 hours at the temperature of 90 ℃ at 600 r/min; and (3) after stirring, filtering and washing the product to be neutral by deionized water, and drying the obtained pretreated bagasse at 110 ℃ for 24 hours to obtain the pretreated bagasse. In the solid bagasse obtained after pretreatment, the bagasse mass is 1.35g, and the lignin removal rate is 69.87%.
The reaction performance evaluation of the catalyst is carried out in a vertical cracking furnace, and the cracking process comprises the following steps: weighing 0.4g of pretreated bagasse, placing the bagasse into a quartz crucible, and loading the bagasse into a constant temperature area of a pyrolysis furnace; introducing nitrogen to purge for 30min, removing oxygen in the reactor, heating to 500 ℃ at a speed of 50 ℃/min after purging, then keeping the temperature for 5min, discharging gas products generated by pyrolysis, condensing and collecting, collecting liquid phase products, analyzing organic matter distribution in the liquid phase products by GC-MS, and the results are shown in table 1.
TABLE 1 pretreatment of bagasse pyrolysis liquid phase product mass distribution
In addition, the gas products produced by the catalytic cracking of the bagasse after pretreatment of examples 1 to 3 and comparative examples 1 to 6 were discharged and condensed to collect the liquid phase product, and the water content of the liquid phase product was relatively small and negligible, probably because the bagasse was dried in an oven at 110℃for 24 hours before use, the water content of the bagasse itself was low, and the water content produced in the catalytic cracking was also small.
As seen in Table 1, the yields of furans in the examples and comparative examples were improved compared to the results for the liquid phase product of the untreated bagasse, and were both the target 2, 3-dihydrobenzofuran (i.e., about 100% of the furans in the liquid phase product were present as 2, 3-dihydrobenzofuran), with 2, 3-dihydrobenzofuran in example 1 accounting for 42.72% of the liquid phase product.
As can be seen from table 1, in the example 1 of the present invention, the ratio of the ternary eutectic solvent is m (zinc chloride): m (ethylene glycol): m (water) =1:10:20, the microwave power is 300W, and the selectivity of the target product 2, 3-dihydrobenzofuran can reach 42.72% when the reaction is performed for 0.5h at the treatment temperature of 60 ℃.
As can be seen from fig. 1, the surface of the treated sample has a porous or network structure, which indicates that the pretreatment can damage the cell wall structure of bagasse to a certain extent, and the flat structure of the bagasse after the pretreatment is obviously damaged to form granular and fibrous entities, which indicates that the bagasse after the pretreatment has larger specific surface area and pores, can increase the adsorption of metal active sites, and promotes the rupture of intermolecular bonds. As can be seen from fig. 2, compared with untreated bagasse, the peaks representing cellulose hydroxyl groups and β -1,4 glycosidic bonds were increased in intensity after pretreatment, indicating that more cellulose was exposed after bagasse pretreatment, representing the c=c aromatic skeleton in the lignin aromatic ring, and the peaks of the bagasse after DES pretreatment were more gentle here, because DES was able to form hydrogen bonds with lignin and other phenolic compounds, removing lignin, more favorable for the formation of the target product.
Those skilled in the art will appreciate that suitable modifications to the invention, such as changing the mesh size, changing the temperature, biomass usage, cracking mode selection, etc., are within the scope of the invention. What has been described in this specification is merely an enumeration of possible forms of implementation for the inventive concept and may not be considered limiting of the scope of the present invention to the specific forms set forth in the examples.
What has been described in this specification is merely an enumeration of possible forms of implementation for the inventive concept and may not be considered limiting of the scope of the present invention to the specific forms set forth in the examples.
Claims (10)
1. The green and efficient pretreated biomass is characterized in that the pretreatment method of the biomass comprises the following steps:
1) Crushing biomass raw materials, and drying to obtain biomass powder;
2) Preparation of ternary eutectic solvent: uniformly mixing a hydrogen bond acceptor and water, adding hydrogen bond donor glycol into a beaker, heating and stirring to obtain a transparent homogeneous solution, and obtaining a ternary eutectic solvent;
3) Microwave reaction: uniformly mixing the ternary eutectic solvent in the step 2) and the biomass powder in the step 1), adding the mixture into a microwave synthesis tube, and placing the microwave synthesis tube under microwave radiation of a microwave synthesizer for microwave pretreatment; and centrifuging the mixture, collecting the lower-layer solid mixture after centrifuging, adding the lower-layer solid mixture into an ammonium chloride aqueous solution for washing, centrifuging the mixture after washing, washing the mixture with deionized water to be neutral, and drying to obtain pretreated biomass.
2. The green and efficient pretreated biomass of claim 1, wherein the biomass powder in step 1) has a particle size of 20-200 mesh, preferably 40-60 mesh.
3. A green and highly efficient pretreated biomass according to claim 1, characterized in that the biomass is bagasse, wood chips, straw or pine leaves, preferably bagasse.
4. A green highly pretreated biomass according to claim 1, characterised in that said hydrogen bond acceptors comprise zinc chloride, choline chloride or betaine, preferably the hydrogen bond acceptors are zinc chloride.
5. The green and efficient pretreated biomass according to claim 1, wherein the mass ratio of hydrogen bond acceptors to ethylene glycol is 1:2-15, preferably 1:8-10; the mass ratio of water to glycol is 1.2-1.0, preferably 1.25-0.5.
6. The green and efficient pretreated biomass of claim 1, wherein the temperature of heating and stirring in step 2) is 70-90 ℃, the stirring time is 10-80min, and the stirring speed is 200-600r/min.
7. A green highly pretreated biomass according to claim 1, characterized in that in step 3) the mass ratio of biomass to ternary eutectic solvent is 1:5-30, preferably 1:10-20.
8. A green highly effective pretreated biomass according to claim 1 characterized in that the reaction conditions for microwave pretreatment in step 3) are: the microwave power is 100-400W, the treatment temperature is 50-70 ℃, the treatment time is 10-60 min, the microwave power is preferably 250-300W, the treatment temperature is preferably 60-65 ℃, and the treatment time is preferably 25-30 min.
9. The green and efficient pretreated biomass of claim 1, wherein in step 3) the concentration of the aqueous ammonium chloride solution is 0.5-3moL/L, preferably 1-2 moL/L.
10.The use of a green, highly effective pretreated biomass for the selective production of 2, 3-dihydrobenzofuran as claimed in claim 1, characterized in that the pyrolysis reaction is carried out in a pyrolysis furnace, the pretreated biomass is packed in the constant temperature zone of a vertical pyrolysis furnace, and N is introduced 2 Purge the exhaust air, then at N 2 And (3) carrying out reaction under the atmosphere, heating to a reaction temperature of 500-550 ℃ from room temperature at a speed of 30-60 ℃/min, keeping the reaction temperature at the constant temperature of 500-550 ℃ for 1-30min, preferably 5-10 min, discharging a gas product generated by pyrolysis, condensing and collecting the gas product, and obtaining a liquid-phase product containing the pyrolysis target product 2, 3-dihydrobenzofuran.
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