CN117024784A - Method for preparing size-controllable energy-storage lignin micro/nanospheres - Google Patents
Method for preparing size-controllable energy-storage lignin micro/nanospheres Download PDFInfo
- Publication number
- CN117024784A CN117024784A CN202310940604.3A CN202310940604A CN117024784A CN 117024784 A CN117024784 A CN 117024784A CN 202310940604 A CN202310940604 A CN 202310940604A CN 117024784 A CN117024784 A CN 117024784A
- Authority
- CN
- China
- Prior art keywords
- lignin
- acid
- solid
- reaction
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920005610 lignin Polymers 0.000 title claims abstract description 121
- 239000004005 microsphere Substances 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000002077 nanosphere Substances 0.000 title claims abstract description 28
- 238000004146 energy storage Methods 0.000 title claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 239000011973 solid acid Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 229920002522 Wood fibre Polymers 0.000 claims abstract description 8
- 239000002025 wood fiber Substances 0.000 claims abstract description 8
- 230000035484 reaction time Effects 0.000 claims abstract description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 29
- 239000002904 solvent Substances 0.000 claims description 27
- 239000002253 acid Substances 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 16
- 239000002131 composite material Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 8
- 229960004889 salicylic acid Drugs 0.000 claims description 8
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 8
- 239000012498 ultrapure water Substances 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 7
- 238000007865 diluting Methods 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 8
- 238000007385 chemical modification Methods 0.000 abstract 1
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- 238000007796 conventional method Methods 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 231100000171 higher toxicity Toxicity 0.000 abstract 1
- 238000011084 recovery Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 229920000742 Cotton Polymers 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 5
- 230000005496 eutectics Effects 0.000 description 4
- 230000008014 freezing Effects 0.000 description 4
- 238000007710 freezing Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- 238000000502 dialysis Methods 0.000 description 3
- 229920000767 polyaniline Polymers 0.000 description 3
- 150000008378 aryl ethers Chemical class 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013043 chemical agent Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000019743 Choline chloride Nutrition 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 101100323029 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) alc-1 gene Proteins 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 description 1
- 229960003178 choline chloride Drugs 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 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
- 125000000524 functional group Chemical group 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011846 petroleum-based material Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 102220280436 rs1555280114 Human genes 0.000 description 1
- 102220011602 rs386833396 Human genes 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2397/00—Characterised by the use of lignin-containing materials
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Compounds Of Unknown Constitution (AREA)
Abstract
The application discloses a method for preparing an energy-storage lignin micro/nanosphere with controllable morphology, which mainly relates to the preparation of lignin spherical micro/nanospheres in a solid acid solvent-water system, and can achieve the purpose of controllable morphology and size by controlling reaction conditions such as solid acid concentration, reaction temperature and reaction time, and the prepared lignin micro/nanospheres have excellent electrochemical performance and better energy storage performance. The method realizes the high-efficiency separation of lignin from the wood fiber raw material under the conditions of low temperature and normal pressure, and simultaneously prepares the lignin into microspheres directly in the lignin recovery process; compared with the conventional method, the preparation method is simple, has high yield, can realize the large-scale preparation of lignin microspheres with controllable size, avoids the chemical modification of lignin and the use of chemical reagents with higher toxicity, saves the cost, reduces the environmental pollution, and has good practicability.
Description
Technical Field
The application belongs to the fields of efficient separation of wood fiber raw materials and high-value utilization of lignin, and particularly relates to a simple, convenient and green preparation method of lignin micro/nanospheres with controllable morphology and particle size.
Background
At present, along with the national and international economic development, people have increased or not dependence on fossil energy, but along with the increasing reduction of fossil energy and environmental problems caused by poor degradability of petroleum-based materials, people are forced to seek clean and degradable novel energy sources. Biomass energy is one of the most abundant renewable resources on earth, wherein lignocellulose is composed of cellulose, lignin and hemicellulose, and providing materials, fuels and chemicals through the three by using biorefinery technology is an important option for petroleum substitution strategy. Lignin is one of the main components of lignocellulose biomass, is a second abundant natural organic polymer aromatic compound in the world, has excellent biocompatibility and excellent antibacterial effect, and the unique chemical structure and higher reactivity of the lignin enable the lignin to be widely applied to the production and living fields. Over 7000 ten thousand tons of industrial lignin waste are produced annually worldwide, most of the lignin is burned, and only about 5% of the lignin is effectively utilized, so that an application way for efficiently separating and utilizing lignin is sought, and the high-value utilization of lignocellulose biomass is facilitated to be improved.
The lignin microsphere/nanosphere is a lignin polymer and has good application prospects in the fields of lignin-based materials, high-molecular assistants, catalysts, drug carriers and the like. At present, the research of lignin microspheres is still in a starting stage, mainly because the preparation method is complicated, and the preparation process needs a large amount of chemical agents and has low yield. At present, the preparation process of the main lignin microspheres mainly comprises the following steps: three general categories, physical, chemical and biological. The physical method mainly comprises the following steps: high shear homogenizing, ultrasonic and ultrasonic spray freezing methods, etc.; chemical method: acid precipitation, solvent exchange, dialysis, etc.; the biological method is mainly an enzymolysis method, and stable and dispersed lignin micro/nanospheres can be obtained by the method. However, the above-described method for preparing lignin nanomicrospheres still has inherent disadvantages. For example, in the ultrasonic method, the dialysis method and the enzymolysis method, lignin is firstly required to be separated to obtain lignin, then the lignin is dissolved in a corresponding organic solvent, and then the lignin microspheres are obtained through ultrasonic or dialysis separation. In addition, the lignin microsphere prepared by the method has low yield, can be only applied on a laboratory scale, and is difficult to apply on a large scale.
CN113426388A discloses a method for preparing lignin microsphere with controllable size, which comprises the steps of constructing eutectic solvent system, treating wood fiber raw material by adopting eutectic solvent system, separating reaction system to obtain lignin microsphere; wherein, the size-controllable preparation of lignin microspheres is realized by adjusting the water consumption in a eutectic solvent system, which mainly comprises the steps of adding trace AlC1 into the eutectic solvent formed by 1, 4-butanediol and choline chloride 3 Can realize the efficient separation of lignin in lignocellulose raw materials, and the separated lignin can be prepared into microsphere characteristics.
Therefore, the search for a simpler and more efficient lignin microsphere preparation method is the key of lignin microsphere industrialization.
Disclosure of Invention
The application aims to: aiming at the problems of complicated preparation method, large chemical use amount and low yield of the existing lignin microsphere, the application aims to provide a method for preparing lignin microsphere/nanosphere with controllable size and good electrochemical performance, which is used for preparing the microsphere in the lignin separation process and has controllable size.
In order to solve the technical problems, the application discloses a method for preparing morphology-controllable energy-storage lignin micro/nanospheres, which is characterized by firstly constructing a composite acid-water solvent system, adopting the composite acid-water solvent system to treat wood fiber raw materials, and then separating lignin in a reaction system to obtain microspheres, wherein the composite acid-water solvent system is obtained by mixing solid acid with strong acid, adding water, and heating and dissolving; the controllable preparation of lignin microsphere appearance and size is realized by controlling the reaction temperature, reaction time, acid concentration and solid-liquid ratio of the reaction system.
Wherein the solid acid is any one of salicylic acid, maleic acid and p-toluenesulfonic acid; the strong acid is sulfuric acid or hydrochloric acid.
The compound acid-water solvent reminder is prepared by the following method: mixing dilute sulfuric acid and salicylic acid according to the mass ratio of 1:0.1-1:1 to obtain a compound acid, wherein the acid concentration in a compound acid-water solvent system is 10-80wt.%, the dilute sulfuric acid concentration is 1-10wt.%, then adding water into the compound acid, heating and dissolving at 40-50 ℃, and continuously stirring until a clear and uniform solid acid-water solution system is formed.
The wood fiber raw material is mixed with a complex acid-water solvent system and then reacts for 10-60min at the temperature of 60-110 ℃.
The solid-liquid ratio of the wood fiber raw material to the composite acid-water solvent system is 1:5-1:15.
Specifically, the separation steps are: vacuum filtering the reaction mixture on filter paper, separating the reaction liquid from the solid, washing the solid by ultrapure water until the washing liquid is neutral (the washing water is combined with the reaction liquid and finally reaches more than 5-10 times of the original volume, the concentration of the diluted reaction liquid is reduced to below 10 wt%) until the total acid content in the reaction liquid is diluted to 5-10wt%, precipitating lignin, standing the reaction liquid for 6-8h, centrifugally separating the obtained reaction liquid, washing the obtained solid lignin with water, freeze-drying to obtain lignin microspheres, and rotationally evaporating the water in the liquid obtained after centrifugation to recover the solid acid for recycling.
The lignin micro/nanospheres prepared by the method are also within the protection scope of the application.
The beneficial effects are that: compared with the prior art, the application has the advantages that:
(1) The salicylic acid type solid acid which can be recovered by heating and evaporating is used, the recovered solid acid can be recycled, and the used water can be recovered by rotary evaporation for continuous use;
(2) The lignin micro/nanospheres with different shapes and sizes are directly separated from the wood fiber raw material in the process of dissolving out lignin by controlling the reaction intensity (reaction temperature, reaction time, acid concentration and solid-liquid ratio);
(3) The lignin micro/nanospheres have good electrochemical performance and better lignin energy storage performance than that of ground wood lignin, alkali lignin and the like;
(4) Compared with the traditional method, the preparation method is simple (lignin micro/nanospheres can be obtained by dissolution, dilution and precipitation), has high yield, no use of chemical agents, reduced toxic and harmful pollution, and good practicality and operability.
Drawings
FIG. 1 is a graph of lignin morphology pretreated with a complex acid-water solvent system under different reaction conditions;
FIG. 2 is a graph of lignin microsphere size distribution versus particle size under various reaction conditions, wherein a, MWL; b, lignin obtained under the condition of C40T70T 30; c, lignin obtained under the condition of C50T90T 30; lignin obtained under the condition of C60T110T 30;
FIG. 3 is the electrochemical performance of lignin under different reaction conditions, where a is the Cyclic Voltammetry (CV) curve of lignin composite electrode (measured at a scan rate of 100 mV/s); b is a constant current charge-discharge (GCD) curve (measured at 1A/g current density) of the lignin composite electrode; c is the specific capacitance of the lignin composite electrode; d is the cyclic stability of the lignin composite electrode at a current density of 1/g; PAn is polyaniline, PAn/MWL is lignin composite electrode prepared by compounding polyaniline with wood-milling lignin, and PAn/L-C60 is lignin composite electrode prepared by compounding polyaniline with lignin prepared under the condition of C60T110T 30.
Detailed Description
The foregoing and/or other advantages of the application will become more apparent from the following detailed description of the application when taken in conjunction with the accompanying drawings and detailed description.
Example 1
A method for preparing lignin microspheres with controllable size, comprising the following steps:
1) 0.1mol/L dilute sulfuric acid and salicylic acid according to a mass ratio of 1:0.5 (mixing, adding ultrapure water, adjusting the total acid concentration to 40wt.%, heating at 50 ℃ until a uniform and clear liquid is formed;
2) Mixing cotton stalk powder (cotton stalk powder is ground to 10 meshes by using a disc mill) with a compound acid-water solvent system according to a solid-liquid ratio of 1:5, reacting for 30min at 70 ℃, separating a reaction liquid from a solid substance by using a Buchner funnel after pretreatment is finished, adding 10-15 times volume of ultrapure water solution to wash the solid substance, diluting the reaction liquid at the same time, diluting the reaction liquid to a total acid concentration of below 10wt.%, and freezing and standing the reaction liquid for 6-8h.
3) And (3) centrifuging the reaction liquid after standing by using a centrifuge, separating lignin from the reaction liquid in a solid-liquid manner, recovering lignin micro/nanospheres, washing the lignin micro/nanospheres by using clear water until the washing liquid becomes neutral, freeze-drying to obtain purified lignin micro/nanospheres, analyzing the main structural composition and content of the purified lignin micro/nanospheres, and calculating the lignin removal rate.
4) And (3) rotationally evaporating the diluted reaction liquid at 60 ℃, recovering clean water, evaporating to dryness, and recovering solid acid for recycling.
Example 2
A method for preparing lignin microspheres with controllable size, comprising the following steps:
1) Mixing 0.1mol/L dilute sulfuric acid and salicylic acid according to a mass ratio of 1:1, adding ultrapure water, adjusting the total acid concentration to 50wt.%, and heating at 50 ℃ until a uniform and clear liquid is formed.
2) Mixing cotton stalk powder and a complex acid-water solvent system according to a solid-liquid ratio of 1:5, reacting for 30min at 90 ℃, separating the reaction liquid from solid matters by using a Buchner funnel after pretreatment, adding 10-15 times of ultrapure water solution to wash the solid matters and dilute the reaction liquid at the same time, diluting the reaction liquid until the total acid concentration is below 10wt.%, and freezing and standing the reaction liquid for 6-8h.
3) And (3) centrifuging and separating the reaction liquid after standing by using a centrifuge, carrying out solid-liquid separation on lignin and the reaction liquid, recovering lignin micro/nanospheres, washing the lignin micro/nanospheres by using clear water until the washing liquid becomes neutral, carrying out freeze drying to obtain purified lignin micro/nanospheres, analyzing the main component content of the purified lignin micro/nanospheres, and calculating the lignin removal rate.
4) The diluted reaction solution is rotationally evaporated at 60 ℃, clear water is recovered, and solid acid is recovered after evaporation to dryness for recycling.
Example 3
A method for preparing lignin microspheres with controllable size, comprising the following steps:
1) Mixing 0.1mol/L dilute sulfuric acid and salicylic acid according to a mass ratio of 1:1, adding ultrapure water, adjusting the total acid concentration to 60wt.%, and heating at 50 ℃ until a uniform and clear liquid is formed.
2) Mixing cotton stalk powder and a complex acid-water solvent system according to a solid-liquid ratio of 1:5, reacting for 30min at 110 ℃, separating the reaction liquid and solid matters by using a Buchner funnel after pretreatment, adding 10-15 times of ultrapure water solution to wash the solid matters and dilute the reaction liquid at the same time, diluting the reaction liquid until the total acid concentration is below 10wt.%, and freezing and standing the reaction liquid for 6-8h.
3) And (3) centrifuging and separating the reaction liquid after standing by using a centrifuge, carrying out solid-liquid separation on lignin and the reaction liquid, recovering lignin micro/nanospheres, washing the lignin micro/nanospheres by using clear water until the washing liquid becomes neutral, carrying out freeze drying to obtain purified lignin micro/nanospheres, analyzing the main component content of the purified lignin micro/nanospheres, and calculating the lignin removal rate.
4) The diluted reaction solution is rotationally evaporated at 60 ℃, clear water is recovered, and solid acid is recovered after evaporation to dryness for recycling.
Example 4
Characterization of lignin prepared in examples 1-3 was performed.
As shown in Table 1, the yield of lignin increased from 23% to 81% with the increase in reaction intensity (reaction temperature, reaction time and acid concentration) during pretreatment, indicating that the increase in reaction intensity favors lignin fragmentation (molecular weight decreased from 7544g/mol to 1822 g/mol) and the fragmented lignin is more soluble, and the yield of lignin microspheres increased with the increase in reaction intensity.
TABLE 1 pretreatment lignin removal rate, molecular weight, lignin microsphere aryl ether linkage content and microsphere size with complex acid-water solvent system
Wherein, cxxtytzz, C represents complex acid concentration (wt.%), mass fraction; t represents the reaction temperature (. Degree. C.); t represents
Reaction time (min);
MWL is a ground lignin, a lignin sample isolated by the traditional beckerman method, generally as the original structure of lignin in lignocellulosic feedstock, as a comparative sample, the MWL in this experiment was isolated from cotton stalks.
The recovered lignin was examined for aryl ether linkage content (beta-O-4' linkage, table 1) using nuclear magnetic resonance. After the beta-O-4 ' bond content in the wood grinding lignin (MWL) is 51 percent and is treated by a compound acid-water solvent system, the beta-O-4 ' bond content of the lignin is low in change under the condition of C40T50T30, the reaction intensity (C50T 90T 30) is continuously increased, the beta-O-4 ' bond content is gradually reduced to 42 percent, the beta-O-4 ' bond content is still 29 percent under the strongest reaction condition, the beta-O-4 ' bond content is higher, the phenolic hydroxyl content is higher, and the phenolic hydroxyl content is 1.54mmol/g, so that the lignin degraded in the pretreatment process still has a more complete structure, has more functional groups and is favorable for further high-value application. As can be seen from FIG. 3, the electrochemical performance of the lignin sample prepared by the complex acid-water solvent system is better, for example, L-C60 is prepared at C60T110T30, and the specific capacitance of the prepared lignin capacitor is far higher than that of the lignin capacitor prepared by MWL.
The electrochemical performance test method comprises the following steps: and placing the prepared electrode material sample into a dilute sulfuric acid solution with the concentration of 0.1mol/L, and testing the electrochemical performance of the electrode material by adopting a three-electrode system by using an electrochemical workstation, wherein the lignin composite electrode material is used as a working electrode, a carbon rod is used as a counter electrode and mercury oxide is used as a reference electrode. Cyclic Voltammetry (CV): the test was performed at a scan rate of 100mV/s over a voltage range of 0.2-0.8V. Constant current charge-discharge test (GCD): the test was carried out at a current density of 1A/g in the voltage range of 0.2-0.8V. From the GCD curve, the specific capacitance of the electrode material was calculated according to the following formula.
Wherein C is the specific capacitance (F/g), I is the discharge current (A), Δt is the total discharge time(s), m is the mass (g) of the active material in the working electrode, and DeltaV is the potential window (V). The cycling stability of the electrode material was evaluated by performing 200 cycles of charge and discharge at 1A/g by GCD.
The morphology and size of the lignin microspheres were observed by a scanning electron microscope, and the results are shown in fig. 1. MWL is rod-shaped. After the treatment with the composite solid acid-water solvent system of the present application, the recovered lignin becomes spherical and becomes smaller in size (decreasing from micron scale to nanometer scale), as can be seen from fig. 2 and 3. The prepared lignin microsphere gradually changes from a rod shape to a uniform spherical shape along with the change of the reaction intensity. The method is characterized in that at the time of C40T90T30, the size of lignin microspheres is reduced, the shape is transited from a rod shape to a sphere shape, and when the strongest condition is reached (C60T 110T 30), the size of the microspheres is the lowest and the morphology becomes the sphere shape.
The application provides a thought and a method for preparing lignin microspheres with controllable size, and the method and the way for realizing the technical scheme are numerous, the above is only a preferred embodiment of the application, and it should be noted that, for those skilled in the art, several improvements and modifications can be made without departing from the principle of the application, and the improvements and modifications should be regarded as the protection scope of the application. The components not explicitly described in this embodiment can be implemented by using the prior art.
Claims (7)
1. The method for preparing the morphology-controllable energy-storage lignin micro/nanospheres is characterized by comprising the steps of firstly constructing a composite acid-water solvent system, adopting the composite acid-water solvent system to treat wood fiber raw materials, and then separating lignin in a reaction system to obtain microspheres, wherein the composite acid-water solvent system is obtained by mixing solid acid with strong acid, adding water, and heating and dissolving; the controllable preparation of lignin microsphere appearance and size is realized by controlling the reaction temperature, reaction time, acid concentration and solid-liquid ratio of the reaction system.
2. The method according to claim 1, wherein the solid acid is any one of salicylic acid, maleic acid, and p-toluenesulfonic acid; the strong acid is sulfuric acid or hydrochloric acid.
3. The method according to claim 1 or 2, wherein the complex acid-water solvent reminder is prepared by: mixing dilute sulfuric acid and salicylic acid according to the mass ratio of 1:0.1-1:1 to obtain a compound acid, wherein the acid concentration in a compound acid-water solvent system is 10-80wt percent, the dilute sulfuric acid concentration is 1-10wt percent, adding water into the compound acid, heating and dissolving at 40-50 ℃, and continuously stirring until a clear and uniform solid acid-water solution system is formed.
4. The method of claim 1, wherein the lignocellulosic feedstock is reacted at 60-110 ℃ for 10-60 minutes after being mixed with the complex acid-water solvent system.
5. The method of claim 1, wherein the lignocellulosic feedstock is present in a solids to liquids ratio of from 1:5 to 1:15 in the complex acid-water solvent system.
6. The method of claim 1, wherein the separating step is: vacuum filtering the reaction mixture on filter paper, separating the reaction liquid from the solid, washing the solid by ultrapure water until the washing liquid is neutral, diluting the total acid content in the reaction liquid to 5-10wt%, precipitating lignin, standing the reaction liquid for 6-8h, centrifugally separating the obtained reaction liquid, washing the obtained solid lignin with water, freeze-drying to obtain lignin microspheres, rotationally evaporating the centrifuged liquid to remove water, and recovering the solid acid for recycling.
7. The lignin micro/nanospheres produced by the method of any one of claims 1-6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310940604.3A CN117024784A (en) | 2023-07-28 | 2023-07-28 | Method for preparing size-controllable energy-storage lignin micro/nanospheres |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310940604.3A CN117024784A (en) | 2023-07-28 | 2023-07-28 | Method for preparing size-controllable energy-storage lignin micro/nanospheres |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117024784A true CN117024784A (en) | 2023-11-10 |
Family
ID=88638261
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310940604.3A Pending CN117024784A (en) | 2023-07-28 | 2023-07-28 | Method for preparing size-controllable energy-storage lignin micro/nanospheres |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117024784A (en) |
-
2023
- 2023-07-28 CN CN202310940604.3A patent/CN117024784A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2021036156A1 (en) | Eutectic solvent and application thereof in extracting lignin | |
| Ci et al. | New ternary deep eutectic solvents for effective wheat straw deconstruction into its high-value utilization under near-neutral conditions | |
| CN110485188B (en) | Method for synchronously preparing high-purity cellulose and lignin nanoparticles from wood fibers and application of method | |
| Xu et al. | Production of hierarchical porous bio‑carbon based on deep eutectic solvent fractionated lignin nanoparticles for high-performance supercapacitor | |
| AU2020102758A4 (en) | Method for preparing lignin with high yield and high aryl ether bond structure from lignocellulosic biomass | |
| Liu et al. | Dissolution of cellulose from AFEX-pretreated Zoysia japonica in AMIMCl with ultrasonic vibration | |
| CN111440248B (en) | Preparation method of xylose residue cellulose nanocrystal and composite hydrogel thereof | |
| CN110551295A (en) | Method for separating chemical components of gramineous plants and purifying lignin | |
| Hasan et al. | A brief review on applications of lignin | |
| Xu et al. | Experimental study on the separation of bagasse lignin and cellulose by using deep eutectic solvent based on alkaline pretreatment | |
| Zhang et al. | Valorization of heavy metal enriched phytoremediation biomass using a deep eutectic solvent (DES) | |
| Gu et al. | Study on preparation of lignin-containing nanocellulose from bamboo parenchyma | |
| He et al. | Lewis acid/base mediated deep eutectic solvents intensify lignocellulose fractionation to facilitate enzymatic hydrolysis and lignin nanosphere preparation | |
| CN108997596B (en) | Method for recycling ionic liquid from waste liquid for preparing cellulose nano-fibers | |
| CN117024784A (en) | Method for preparing size-controllable energy-storage lignin micro/nanospheres | |
| CN113426388B (en) | Method for preparing size-controllable lignin microspheres | |
| CN112029115A (en) | Method for separating and extracting lignin by in-situ synthesis of deep eutectic solvent | |
| Liu et al. | Synergistic effects of heteropoly acids and sulfolane on fractionation and utilization of willow | |
| CN114874343B (en) | Spherical nanocrystalline cellulose based on furfural residues and preparation method thereof | |
| CN113292747B (en) | Preparation method and application of biomass lignin nanoshell | |
| CN114108350A (en) | Method for quickly separating main components of wood biomass by using eutectic solvent | |
| Wang et al. | Recycled Biorefinery System Integrating Phosphoric Acid/Acetone Pretreatment of Sugarcane Bagasse with Subsequent Platform Chemicals Generation | |
| CN109024037B (en) | Method for preparing strip-shaped nanocellulose by compound enzyme enzymolysis and method thereof | |
| CN116988331A (en) | Method for efficiently separating and utilizing all components of wood fiber raw material | |
| Nie et al. | Efficient fractionation of kenaf chemical components by using recyclable acidic DES |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |