CN116535370A - Method for co-producing furfural and lignin microspheres by one-pot method - Google Patents
Method for co-producing furfural and lignin microspheres by one-pot method Download PDFInfo
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- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 229920005610 lignin Polymers 0.000 title claims abstract description 104
- 238000000034 method Methods 0.000 title claims abstract description 55
- 239000004005 microsphere Substances 0.000 title claims abstract description 44
- 238000005580 one pot reaction Methods 0.000 title claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 41
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 230000002051 biphasic effect Effects 0.000 claims abstract description 13
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 229920002522 Wood fibre Polymers 0.000 claims abstract description 10
- 239000002025 wood fiber Substances 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- 239000002841 Lewis acid Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 239000012296 anti-solvent Substances 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 238000004108 freeze drying Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000004064 recycling Methods 0.000 claims abstract description 3
- 239000013557 residual solvent Substances 0.000 claims abstract description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- 230000005496 eutectics Effects 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 12
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 12
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 6
- 235000019743 Choline chloride Nutrition 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical group [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 6
- 229960003178 choline chloride Drugs 0.000 claims description 6
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 5
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 5
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 5
- 239000011425 bamboo Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 229940083957 1,2-butanediol Drugs 0.000 claims description 2
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 2
- 244000166124 Eucalyptus globulus Species 0.000 claims description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 2
- 241000219000 Populus Species 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 239000000370 acceptor Substances 0.000 claims 3
- 244000082204 Phyllostachys viridis Species 0.000 claims 1
- 229920002488 Hemicellulose Polymers 0.000 abstract description 23
- 238000000926 separation method Methods 0.000 abstract description 11
- 238000002360 preparation method Methods 0.000 description 10
- 238000011084 recovery Methods 0.000 description 5
- 241001330002 Bambuseae Species 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 238000000502 dialysis Methods 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- -1 and then dialysis Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 239000002029 lignocellulosic biomass Substances 0.000 description 1
- 239000012978 lignocellulosic material Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
- C07D307/48—Furfural
- C07D307/50—Preparation from natural products
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compounds Of Unknown Constitution (AREA)
Abstract
The invention discloses a method for co-producing furfural and lignin microspheres by a one-pot method, belonging to the technical field of clean separation and efficient utilization of wood fiber raw materials. The method comprises the steps of mixing a hydrogen bond acceptor, a hydrogen bond donor, lewis acid, inorganic strong acid and gamma-valerolactone to form a biphasic system; adding an antisolvent after the reaction of the wood fiber raw material and the solvent is finished, and stirring to fully separate lignin from the material; filtering to obtain lignin-rich pretreatment liquid; removing the organic solvent by rotary evaporation of the pretreatment liquid, adding deionized water, centrifuging, washing, and freeze-drying to obtain lignin microspheres; removing lignin pretreatment liquid, removing water by rotary evaporation, separating furfural, and recycling the residual solvent. The method utilizes a biphasic system to pretreat the lignocellulose raw material, removes a large amount of hemicellulose and lignin at a lower temperature, the removed hemicellulose is mostly converted into furfural, and the separated lignin exists in the form of lignin microspheres, so that the furfural and lignin microspheres are prepared by a one-pot method.
Description
Technical Field
The invention belongs to the technical field of clean separation and efficient utilization of wood fiber raw materials, and particularly relates to a method for co-producing furfural and lignin microspheres by a one-pot method.
Background
Fossil resources are increasingly reduced, but the demands of human beings on energy and chemical raw materials are gradually increased, so that the problems of environmental pollution, energy crisis and the like are caused, and the human beings are forced to seek a clean and renewable novel energy source. Lignocellulosic biomass is the most abundant renewable resource on earth with high calorific value, low cost and wide source, and is considered as the most potential fossil fuel substitute. Furfural is widely applied to the preparation of gasoline, diesel oil or aviation fuel oil as an important chemical raw material intermediate, and is an important platform compound. Lignin is the most widely available aromatic compound in nature, and is widely used in the fields of material preparation, fuel production and the like. The world pulp and paper making and biomass refining fields generate approximately 5000 ten thousand tons of lignin industrial waste each year, of which only less than 2% is effectively utilized and most is burned. In view of the two factors of high demand of furfural and low lignin utilization rate, an efficient furfural conversion way is sought, and meanwhile, high-valued utilization of lignin is realized, so that the problems caused by excessive consumption of fossil energy are solved, and the utilization rate of lignocellulose biomass is improved.
At present, the main preparation method of the furfural is to catalyze hemicellulose in a lignocellulose raw material by inorganic acid, and the method uses a large amount of inorganic strong acid, has certain corrosiveness to equipment and causes serious pollution to the environment; in addition, the yield of furfural in an aqueous phase system is low (< 60%), mainly because under the conditions of high temperature and strong acid, the furfural can be further degraded into other products in the aqueous phase system, so that the yield of the furfural is reduced. The bi-directional solvent system can effectively extract the furfural produced in the reaction process, reduce the subsequent side reaction of the furfural and improve the yield of the furfural. In current reports on biphasic systems, hemicellulose conversion is focused, whereas lignin is reported less in biphasic systems. Lignin microspheres (including nano-scale and micro-scale) are lignin macromolecular polymers which can be dispersed in aqueous solution to form stable jelly, so that the lignin microsphere has good application prospects in the fields of biological base materials, dispersing agents, adsorbents, drug carriers and the like. At present, the research of lignin microspheres is still in the starting stage, mainly because of the complicated preparation process. Conventional lignin microsphere preparation processes include dialysis (solvent exchange), mechanical, injection, drip, etc. However, whatever the preparation method, it has inherent disadvantages. For example, in the dialysis method, the injection method and the drip method, lignin is first separated to obtain, then the lignin is dissolved in an organic solvent, and then dialysis, injection or drip is performed. In these methods, the residual organic solvent limits the application, and in addition, the lignin microsphere yield of the method is low, and the method can only be carried out in a laboratory and is difficult to be applied in a large scale. Therefore, the search for a simpler and more efficient lignin microsphere preparation method is the key of industrialization.
The preparation of furfural is carried out by degrading and converting hemicellulose, and the preparation of lignin microspheres requires lignin separation. The solvents commonly used for dissociating hemicellulose and lignin in lignocellulosic materials mainly comprise alkaline solutions, organic solvents, ionic liquids and the like. In recent years, eutectic solvents have been widely used for component separation of lignocellulosic feedstocks, and in particular acidic eutectic solvents exhibit exceptionally excellent properties in terms of hemicellulose degradation and lignin removal. The eutectic solvent is composed of a hydrogen bond acceptor and a hydrogen bond donor. Hemicellulose is easily converted into furfural in an acidic eutectic solvent, but a series of side reactions are easily generated in the system by the furfural, so that the generated furfural is difficult to stably exist, and the existence of the furfural is not detected in the traditional acidic eutectic pretreatment. The production of furfural by gamma valerolactone in acidic aqueous systems has been widely reported, wherein gamma valerolactone can reduce the occurrence of side reactions to effectively protect the produced furfural.
Disclosure of Invention
Aiming at the problems of low yield, serious pollution and complex preparation method and low yield of the existing furfural production method, the invention provides a method for realizing the dissociation of a lignocellulose raw material by a one-pot method and simultaneously converting hemicellulose into furfural, and the lignin is directly self-assembled into microspheres and a used solvent. Through the pretreatment of the solvent, a large amount of hemicellulose can be converted into furfural and self-assembled into microspheres in the lignin precipitation recovery process, so that the one-pot method for co-production of furfural and lignin microspheres is realized.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a method for co-producing furfural and lignin microspheres by a one-pot method comprises the following steps:
1) The hydrogen bond acceptor, the hydrogen bond donor, the Lewis acid and the inorganic strong acid are mixed and then are continuously stirred until a uniform and clear solvent is formed, and then are mixed with gamma-valerolactone to form a biphasic solvent system;
2) Mixing wood fiber raw materials with a biphasic solvent system for reaction, adding an antisolvent after the reaction is finished, and stirring to fully separate lignin from materials;
3) Filtering after stirring to obtain lignin-rich pretreatment liquid; removing the organic solvent by rotary evaporation of the pretreatment liquid, adding deionized water to precipitate lignin, centrifuging, washing, and freeze-drying to obtain lignin microspheres;
4) Removing lignin pretreatment liquid, removing water by rotary evaporation, separating furfural, and recycling residual solvent.
The method for co-producing furfural and lignin microspheres by the one-pot method comprises the steps that a hydrogen bond donor is any one of ethylene glycol, 1, 2-butanediol, 1, 4-butanediol, 1, 2-pentanediol or 1, 5-pentanediol, a hydrogen bond acceptor is choline chloride, a Lewis acid is any one of aluminum sulfate, aluminum chloride, zinc chloride or tin chloride, and an inorganic strong acid is sulfuric acid or hydrochloric acid; mixing the above materials at 50-100 ℃; preferably, the hydrogen bond donor is 1, 4-butanediol; the above materials were mixed at 100deg.C.
In the method for co-producing furfural and lignin microspheres by the one-pot method, the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is 1:1-1:5, and preferably, the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is 1:2; the mass ratio of the eutectic solvent to the gamma-valerolactone is 1:0.5-1:5, and preferably, the mass ratio of the eutectic solvent to the gamma-valerolactone is 1:1; the addition amount of the Lewis acid and the inorganic strong acid is 0.01-1M, and the concentration of aluminum chloride and sulfuric acid is 0.075M and 0.15M respectively.
The method for co-producing furfural and lignin microspheres by the one-pot method has the mass ratio of the wood fiber raw material to the biphasic solvent system of 1:1-1:50; mixing wood fiber raw materials with a biphasic solvent system, and reacting for 10-120 min at 100-150 ℃; preferably, the mass ratio of the lignocellulosic feedstock to the solvent is 1:10; the wood fiber raw material is mixed with the solvent and then reacts for 60 minutes at the temperature of 120-140 ℃.
The method for co-producing furfural and lignin microspheres by the one-pot method comprises the steps that an antisolvent is an aqueous solution of acetone or ethanol, the volume fraction is 20% -100%, and the addition amount is 1-10 times of the volume of the solvent; preferably, the antisolvent is an aqueous acetone solution having a volume fraction of 50%.
The method for co-producing furfural and lignin microspheres by the one-pot method is characterized in that wood fiber raw materials are any one of poplar, eucalyptus or bamboo.
Compared with the prior art, the invention has the beneficial effects that:
the method has the advantages that trace Lewis acid and inorganic strong acid are added into the eutectic solvent formed by the polyalcohol and the choline chloride, and an appropriate amount of organic solvent (gamma-valerolactone) is matched, so that hemicellulose degradation and lignin efficient separation in the lignocellulose raw material can be realized, the complicated processes of lignin dissolution and microsphere regeneration in the conventional method and the problem of invalid degradation of furfural are avoided, and the method is a novel and efficient one-pot method for co-producing furfural and lignin microspheres.
The invention pretreats the lignocellulose raw material by using a biphasic solvent system consisting of a polyalcohol-based eutectic solvent and an organic solvent, a large amount of hemicellulose and lignin can be removed at a lower temperature, the removed hemicellulose is mostly converted into furfural, and the separated lignin exists in the form of lignin microspheres with the diameter of 1-3 mu m.
Drawings
FIG. 1 shows hemicellulose removal rate (1 a) and furfural yield (1 b) at different pretreatment temperatures;
FIG. 2 shows lignin removal rate (2 a) and lignin recovery rate (2 b) during pretreatment;
FIG. 3 is an electron microscope image of the recovered lignin after pretreatment at different pretreatment temperatures;
FIG. 4 is a graph showing the size distribution of lignin microspheres at various pretreatment temperatures.
Detailed Description
The invention is further described below in connection with specific embodiments.
Hemicellulose removal rate = hemicellulose in pretreatment material (g)/hemicellulose in feedstock (g);
example 1
A method for co-producing furfural and lignin microspheres by a one-pot method comprises the following steps:
1) Mixing choline chloride and 1, 4-butanediol according to a molar ratio of 1:2, adding aluminum chloride and sulfuric acid respectively at concentrations of 0.075M and 0.15M, and continuously stirring at 100deg.C until a uniform and clear solvent is formed; mixing gamma-valerolactone and the eutectic solvent according to the mass ratio of 1:1 for pretreatment;
2) Mixing 10g of bamboo wood with 100g of the solvent according to the mass ratio of 1:10, reacting for 60min at 120 ℃, adding 10 times of acetone aqueous solution (the volume fraction of the acetone is 50 percent) after pretreatment, and stirring for 2h;
3) Solid-liquid separation is carried out to obtain pretreatment liquid rich in lignin and pretreatment materials rich in cellulose; after the pretreated material is washed to be neutral by distilled water, the main component content of the pretreated material is analyzed, and the lignin removal rate is calculated;
4) Removing acetone in the pretreatment liquid by rotary evaporation at 50 ℃, adding 500mL of deionized water to precipitate lignin, centrifugally separating, washing for several times, freeze-drying to obtain lignin microspheres, weighing and calculating the yield;
5) And after removing water in the pretreatment solution after lignin separation by rotary evaporation, diluting the residual furfural-rich part, analyzing the furfural content in the residual furfural-rich part by high performance liquid chromatography, and calculating the furfural yield.
Example 2
A method for co-producing furfural and lignin microspheres by a one-pot method comprises the following steps:
1) Mixing choline chloride and 1, 4-butanediol according to a molar ratio of 1:2, adding aluminum chloride and sulfuric acid respectively at concentrations of 0.075M and 0.15M, and continuously stirring at 100deg.C until a uniform and clear solvent is formed; mixing gamma-valerolactone and the eutectic solvent according to the mass ratio of 1:1 for pretreatment;
2) Mixing 10g of bamboo wood with 100g of the solvent according to the mass ratio of 1:10, reacting for 60min at 130 ℃, adding 10 times of acetone aqueous solution (the volume fraction of the acetone is 50 percent) after pretreatment, and stirring for 2h;
3) Solid-liquid separation is carried out to obtain pretreatment liquid rich in lignin and pretreatment materials rich in cellulose; after the pretreated material is washed to be neutral by distilled water, the main component content of the pretreated material is analyzed, and the lignin removal rate is calculated;
4) Removing acetone in the pretreatment liquid by rotary evaporation at 50 ℃, adding 500mL of deionized water to precipitate lignin, centrifugally separating, washing for several times, freeze-drying to obtain lignin microspheres, weighing and calculating the yield;
5) And after removing water in the pretreatment solution after lignin separation by rotary evaporation, diluting the residual furfural-rich part, analyzing the furfural content in the residual furfural-rich part by high performance liquid chromatography, and calculating the furfural yield.
Example 3
A method for co-producing furfural and lignin microspheres by a one-pot method comprises the following steps:
1) Mixing choline chloride and 1, 4-butanediol according to a molar ratio of 1:2, adding aluminum chloride and sulfuric acid respectively at concentrations of 0.075M and 0.15M, and continuously stirring at 100deg.C until a uniform and clear solvent is formed; mixing gamma-valerolactone and the eutectic solvent according to the mass ratio of 1:1 for pretreatment;
2) Mixing 10g of bamboo wood with 100g of the solvent according to the mass ratio of 1:10, reacting for 60min at 140 ℃, adding 10 times of acetone aqueous solution (the volume fraction of the acetone is 50 percent) after pretreatment, and stirring for 2h;
3) Solid-liquid separation is carried out to obtain pretreatment liquid rich in lignin and pretreatment materials rich in cellulose; after the pretreated material is washed to be neutral by distilled water, the main component content of the pretreated material is analyzed, and the lignin removal rate is calculated;
4) Removing acetone in the pretreatment liquid by rotary evaporation at 50 ℃, adding 500mL of deionized water to precipitate lignin, centrifugally separating, washing for several times, freeze-drying to obtain lignin microspheres, weighing and calculating the yield;
5) And after removing water in the pretreatment solution after lignin separation by rotary evaporation, diluting the residual furfural-rich part, analyzing the furfural content in the residual furfural-rich part by high performance liquid chromatography, and calculating the furfural yield.
Examples 1-3 were run with different pretreatment temperatures and the results of hemicellulose removal (1 a) and furfural yield (1 b) are shown in figure 1. As can be seen from FIG. 1, the hemicellulose removal rate after pretreatment can reach 90.39% (120 ℃), which shows that the solvent can efficiently remove hemicellulose. With the increase of the temperature, the hemicellulose removal rate is slightly increased from 90.39% (120 ℃) to 92.67% (130 ℃); the furfural yield increased from 38.29% (120 ℃) to 50.9% (130 ℃), indicating that the hemicellulose removal rate increased and the furfural yield increased with increasing temperature. When the temperature continues to rise to 140 ℃, hemicellulose is completely removed, and the furfural yield is significantly reduced, because the rise in temperature leads to an increase in the subsequent side reactions of furfural, thus reducing the furfural yield.
The results of lignin removal rate (2 a) and lignin recovery rate (2 b) during pretreatment of examples 1-3 are shown in FIG. 2. In the pretreatment process, the temperature is increased from 120 ℃ to 130 ℃, and the lignin removal rate is increased from 78.20% (120 ℃) to 88.61% (130 ℃), which shows that the temperature increase is favorable for degradation and removal of lignin; and the temperature is continuously increased to 140 ℃, the lignin removal rate is reduced to 79.72%, and the lignin degraded at high temperature is subjected to polycondensation reaction, so that the lignin is deposited on the surface of the fiber, and the lignin removal rate of the pretreated material is reduced. In addition, lignin in the pretreatment liquid is recovered, and the calculated yield is as shown in fig. 2b, and more than 95% of lignin can be recovered. As the pretreatment temperature increases, lignin recovery decreases slightly because the degree of lignin fragmentation increases at high temperatures, resulting in increased loss of fragmented lignin during recovery.
FIG. 3 is an electron microscope image of the recovered lignin after pretreatment at different temperatures, and FIG. 4 is a graph showing the size distribution of lignin microspheres at different temperatures. As can be seen from fig. 3 and fig. 4, the enzymatic lignin separated from the raw material is in an irregular block shape, and the lignin has obvious agglomeration phenomenon. The lignin recovered after being treated by the solvent is in a regular spherical shape, and the agglomeration phenomenon is less. And the lignin microspheres obtained at different temperatures have different particle sizes, and are characterized in that the particle sizes slightly increase with the increase of the pretreatment temperature (fig. 4). The average particle diameters of the lignin microspheres are 1.29 mu m, 1.64 mu m and 2.1 mu m at 120, 130 and 140 ℃ respectively, and the uniformity of the lignin particle diameter increases with the increase of the temperature.
Claims (6)
1. The method for co-producing the furfural and lignin microspheres by the one-pot method is characterized by comprising the following steps of:
1) The hydrogen bond acceptor, the hydrogen bond donor, the Lewis acid and the inorganic strong acid are mixed and then are continuously stirred until a uniform and clear solvent is formed, and then are mixed with gamma-valerolactone to form a biphasic solvent system;
2) Mixing wood fiber raw materials with a biphasic solvent system for reaction, adding an antisolvent after the reaction is finished, and stirring to fully separate lignin from materials;
3) Filtering after stirring to obtain lignin-rich pretreatment liquid; removing the organic solvent by rotary evaporation of the pretreatment liquid, adding deionized water to precipitate lignin, centrifuging, washing, and freeze-drying to obtain lignin microspheres;
4) Removing lignin pretreatment liquid, removing water by rotary evaporation, separating furfural, and recycling residual solvent.
2. The method for co-producing furfural and lignin microspheres by a one-pot method according to claim 1, wherein the hydrogen bond donor is any one of ethylene glycol, 1, 2-butanediol, 1, 4-butanediol, 1, 2-pentanediol or 1, 5-pentanediol, the hydrogen bond acceptor is choline chloride, the lewis acid is any one of aluminum sulfate, aluminum chloride, zinc chloride or tin chloride, and the strong inorganic acid is sulfuric acid or hydrochloric acid; the above materials are mixed at 50-100 ℃.
3. The method for co-producing furfural and lignin microspheres by the one-pot method according to claim 1, wherein the molar ratio of the hydrogen bond acceptors to the hydrogen bond donors is 1:1-1:5, the mass ratio of the eutectic solvent to the gamma valerolactone is 1:0.5-1:5, and the addition amounts of Lewis acid and inorganic strong acid are 0.01-1M.
4. The method for co-producing furfural and lignin microspheres by the one-pot method according to claim 1 wherein the mass ratio of lignocellulosic feedstock to biphasic solvent system is 1:1 to 1:50; the wood fiber raw material is mixed with the biphasic solvent system and then reacts for 10 to 120 minutes at the temperature of 100 to 150 ℃.
5. The method for co-producing furfural and lignin microspheres by the one-pot method according to claim 1, wherein the antisolvent is an aqueous solution of acetone or ethanol, the volume fraction is 20% -100%, and the addition amount is 1-10 times the volume of the solvent.
6. The method for co-producing furfural and lignin microspheres according to claim 1 wherein the lignocellulosic feedstock is any one of poplar, eucalyptus or bamboo.
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