CN115975216A - Low-temperature hydrophilic modification method for lignin - Google Patents
Low-temperature hydrophilic modification method for lignin Download PDFInfo
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- CN115975216A CN115975216A CN202111196579.XA CN202111196579A CN115975216A CN 115975216 A CN115975216 A CN 115975216A CN 202111196579 A CN202111196579 A CN 202111196579A CN 115975216 A CN115975216 A CN 115975216A
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention belongs to the technical field of biomass high-value utilization, and particularly relates to a low-temperature hydrophilic modification method for industrial lignin. The method comprises the following steps: adding industrial lignin into concentrated sulfuric acid (50-98 wt%) according to a certain proportion, uniformly stirring, then adding an electrophilic reaction reagent capable of grafting hydrophilic groups on the lignin, maintaining the reaction temperature at-20-60 ℃, reacting for 0.1-24 h, then filtering or centrifugally separating out reaction liquid, and washing with a small amount of clear water to obtain a hydrophilic modified product of the lignin; the invention uses concentrated sulfuric acid low-temperature system to carry out hydrophilic modification on lignin, and the concentrated sulfuric acid is used as a catalyst for grafting a hydrophilic group on the lignin. The invention provides a new way for the hydrophilic modification of lignin, can conveniently introduce different hydrophilic groups into the lignin, and broadens the application of the lignin in different fields.
Description
Technical Field
The invention belongs to high-value utilization of biomass resources. More particularly, the invention relates to a method for low-temperature hydrophilic modification of industrial lignin.
Background
The lignin is the third largest biomass resource with the content of the cellulose and the chitin in the nature, which accounts for about 15 to 30 percent of the weight of the plant body, and can generate more than 1000 hundred million tons of lignin every year all over the world. By proper technology and method, lignin can be depolymerized into a single benzene ring compound serving as a chemical raw material, can be used as a material through modification or carbonization, and can also be used as an additive and a dispersing agent through hydrophilic modification. With the increasing attention of people to the environment and sustainable development, the renewable biomass raw material lignin is bound to receive more important attention.
Because of containing more aromatic groups and strong intermolecular force, industrial lignin is generally insoluble in water, which affects the industrial application. Therefore, it is necessary to introduce hydrophilic groups into the lignin structure to increase its water solubility. At present, lignin hydrophilic modification mainly comprises sulfonation modification and amination modification.
The sulfonation reaction mainly comprises the introduction of sulfate groups, -SO in lignin molecules 3 - Or methylene sulfate, -CH 2 SO 3 - And the water solubility of the lignin is improved. The industrial lignin sulfonation method mainly comprises high temperature sulfonation and sulfomethylation, wherein the high temperature sulfonation generally uses inorganic sulfonate such as sodium bisulfite and the like as a sulfonating agent under the high temperature (150-200 ℃) and high pressure condition, and sulfonic acid groups are introduced into alpha carbon of lignin side chains (Chemosphere, 2005.60 (8): 1054-1061.). The method has high energy consumption and high requirement on equipment. The sulfomethylation reaction is generally carried out at about 90 ℃, lignin is firstly reacted with formaldehyde under the normal pressure alkaline condition, and then the hydroxymethylation is carried out, and sulfomethylation reaction is carried out with sodium sulfite and the like, and sulfonic groups are introduced into the ortho positions of phenolic hydroxyl groups on the guaiacyl and p-hydroxyphenyl structures; or firstly, formaldehyde and sulfite are reacted to generate a sodium hydroxymethyl sulfonate intermediate, and then the reaction intermediate is reacted with the ortho position of the phenolic hydroxyl group in the lignin to introduce a sulfonic group.
Free hydrogen in aldehyde group, ketone group and sulfonic group in lignin molecule is relatively active, and can be used for Mannich reaction with organic amine to introduce active primary amine, secondary amine or tertiary amine group into lignin structure (U.S. Pat. No. 2,27096A, 1955-05-31). Amination modification can improve the activity of lignin, so that the lignin becomes an industrial surfactant with multiple purposes. During Mannich reaction of lignin, hydrogen atoms on ortho positions of phenolic hydroxyl groups on benzene rings and alpha positions of carbonyl groups on side chains are relatively active and are easy to react with aldehyde and amine to generate lignin amine, and the reaction temperature is generally from room temperature to 100 ℃. Zeng Xiangqin et al (fine chemical, 2001.18 (4): 196-199.) prepared lignin amine by Mannich reaction, and the lignin modification rate was determined by acetate thin film electrophoresis. The result shows that the nitrogen content of lignin amine has a linear relation with the modification rate. Wang Xiaogong et al (journal of Guizhou university of Industrial science, 2000.29 (3): 65-69; shanghai environmental science, 2002,21 (4): 224-228.) A Mannich reaction was used to prepare the lignin amine cationic surfactant and to measure the nitrogen content of the modified sample, and the results showed that the temperature in the reaction conditions had the greatest effect on the modification rate, followed by formaldehyde.
In order to expand the application of lignin, a new lignin modification method needs to be developed, and particularly a modification method introducing different hydrophilic functional groups needs to be developed. For example, the introduction of N and P elements can enable lignin to be used as a soil conditioner and a desert sand fixing agent and provide necessary elements for plant growth, and meanwhile, the introduction of different hydrophilic functional groups has important significance on the aspects of heavy metal adsorption, dye and pesticide dispersion, high-performance carbonized material preparation and novel surfactant preparation of lignin.
Disclosure of Invention
Aiming at the problems that the existing lignin hydrophilic modification method is relatively fixed and the variety of introduced hydrophilic functional groups is not many, the invention aims to provide a novel lignin hydrophilic modification method, wherein different hydrophilic groups are introduced into lignin to obtain lignin products with different properties.
The invention also aims to improve the grafting rate of different hydrophilic groups on lignin by the catalytic action of concentrated sulfuric acid, and simultaneously inhibit the carbonization of the concentrated sulfuric acid on the lignin at lower reaction temperature.
The purpose of the invention is realized by the following scheme:
a method for low-temperature hydrophilic modification of lignin comprises the following steps:
adding industrial lignin into concentrated sulfuric acid (50-98 wt%) according to a certain proportion, uniformly stirring, then adding an electrophilic reaction reagent capable of grafting hydrophilic groups on the lignin, maintaining the reaction temperature at-20-60 ℃, reacting for 0.1-24 h, then filtering or centrifugally separating reaction liquid, washing with a small amount of water, and drying to obtain a hydrophilic modified product of the lignin;
the industrial lignin can be one or a combination of more of alkali lignin, enzymatic hydrolysis lignin, organic solvent lignin, high-boiling alcohol lignin, klason lignin and ground wood lignin which are obtained from different plant raw materials, and lignin extracted from different plant raw materials such as ionic liquid, deep eutectic solvent, hydrated molten salt system, solid acid solution and the like;
the plant raw material can be one or a combination of more of pine, eucalyptus, poplar, ash, sea buckthorn, cedar, fir, birch, corncob, corn stalk, wheat straw, bagasse, straw, rice hull, edible fungus matrix and peanut shell;
the solid-liquid ratio of the industrial lignin to the concentrated sulfuric acid solution is 1-20, and preferably 2-10;
the mass concentration of the concentrated sulfuric acid is 50-98%, preferably 70-98%;
the electrophilic reaction reagent capable of grafting the hydrophilic group on the lignin can be one or a combination of more of sulfur trioxide, phosphorus pentoxide, concentrated phosphoric acid or concentrated nitric acid;
the mass concentration of the used concentrated phosphoric acid and concentrated nitric acid is more than 50 percent; preferably the mass concentration is greater than 60%;
the mass ratio of the addition amount of the sulfur trioxide, the phosphorus pentoxide, the concentrated phosphoric acid and the concentrated nitric acid to the lignin is 0.1-2; the preferable mass ratio range is 0.2-1;
the reagents such as sulfur trioxide, phosphorus pentoxide, concentrated phosphoric acid, concentrated nitric acid and the like can be added into one or more of the reagents in the reaction process;
the sulfur trioxide, the phosphorus pentoxide, the concentrated phosphoric acid or the concentrated nitric acid are added into the concentrated sulfuric acid to cause heat release, so that the sulfur trioxide, the phosphorus pentoxide, the concentrated phosphoric acid or the concentrated nitric acid are slowly added during the addition, and a certain cooling system is ensured to maintain the temperature of the system not to be sharply increased in the process;
the reaction temperature is-20-60 ℃, and preferably 0-40 ℃;
the reaction time is 0.1-24 h, preferably 1-4 h;
the lignin product is cleaned by a small amount of water, the mass ratio of the water to the lignin is 1-10, and the preferred mass ratio is 2-8; a small amount of water can wash most of the residual acid in the lignin product, and the loss of a large amount of dissolved product is avoided.
The mechanism of the invention is as follows:
because lignin contains a large number of phenolic hydroxyl groups and methoxyl structures, the adjacent para positions of the lignin are good electrophilic reagent attack points, and under the action of concentrated sulfuric acid, sulfur trioxide, phosphorus pentoxide, concentrated phosphoric acid, concentrated nitric acid and the like can become good electrophilic reagents to attack the adjacent para positions of the phenolic hydroxyl groups or the methoxyl groups in the lignin, so that hydrophilic groups are introduced into the lignin. The reaction catalyzed by concentrated sulfuric acid can be carried out at low temperature, and the carbonization of lignin can be caused at an excessively high temperature, so that the hydrophilicity of the product is reduced.
Compared with the prior art, the invention has the following innovations and beneficial effects:
(1) The invention firstly proposes that lignin is subjected to hydrophilic modification by the catalysis of concentrated sulfuric acid at low temperature, and the method is original;
(2) The invention can simultaneously introduce a plurality of hydrophilic functional groups into the lignin, and can greatly expand the application of the lignin in different fields.
(3) In the invention, the lignin is not required to be dissolved in water or an organic solvent, and can be conveniently separated by centrifugation or filtration, thereby saving the separation cost.
Drawings
FIG. 1 is a graph showing the solubility in water before (left) and after (right) phosphorylation of lignin by wheat straw enzymatic hydrolysis at 1g/L, corresponding to example 5. From the figure, it can be seen that the enzymatic lignin of wheat straw after phosphorylation has a significant increase in water solubility, from water insoluble to completely water soluble.
Detailed Description
In order to further explain the present invention in detail, several specific embodiments are given below, but the present invention is not limited to these embodiments. Wherein example 1 is a comparative example to example 2.
Example 1:
pulping 10g birch wood by alkaline method (soaking 100g birch wood chips with particle size less than 0.5cm in 400g NaOH and Na 2 S solution, in which NaOH and Na 2 S is respectively 15 percent and 10 percent of the mass of wood, the treatment temperature is 170 ℃, the heat preservation time is 3 hours), the obtained alkali lignin is put into a 250mL three-mouth flask after acid precipitation of black liquor (the pH is adjusted to 2.0 by sulfuric acid with the mass fraction of 5 percent), 50g of concentrated sulfuric acid with the mass fraction of 98 percent is added, uniform stirring is carried out by using magnetons, the temperature of the system is controlled to be 10 ℃ by using a flowing cold water bath, the stirring speed of the magnetons in the flask is controlled to be 200rpm, the opening of the flask is sealed, after 10 hours of reaction, the reaction slurry is filtered by using a hydrophilic polytetrafluoroethylene membrane (the aperture is 0.8 mu m), the obtained filter cake is washed by 20mL pure water, the filter cake is dialyzed for one week in the pure water by using a dialysis bag with the molecular weight cutoff of 1000Da, then the liquid in the dialysis bag is dried, and the sulfonated lignin powder is obtained.
Example 2:
pulping 10g birch wood by alkaline method (soaking 100g birch wood chips with particle size less than 0.5cm in 400g NaOH and Na 2 S solution, in which NaOH and Na 2 S is respectively 15 percent and 10 percent of the mass of wood, the treatment temperature is 170 ℃, the heat preservation time is 3 hours), the obtained alkali lignin is put into a 250mL three-mouth flask after acid precipitation of black liquor (the pH is adjusted to 2.0 by sulfuric acid with the mass fraction of 5 percent), 50g of concentrated sulfuric acid with the mass fraction of 98 percent is added, after uniform stirring is carried out by a magneton, 2g of sulfur trioxide powder is slowly added, the temperature of the system is controlled to be 10 ℃ by a flowing cold water bath, the stirring speed of the magneton in the flask is controlled to be 200rpm, the opening of the flask is sealed, after 10 hours of reaction, the reaction slurry is filtered by a hydrophilic polytetrafluoroethylene membrane (the aperture is 0.8 mu m), the obtained filter cake is washed by 20mL of pure water, the filter cake is dialyzed for one week in the pure water by a dialysis bag with the molecular weight cutoff of 1000Da, and then the liquid in the dialysis bag is dried, and the sulfonated lignin powder is obtained.
Example 3:
pulping 5g of masson pine by alkaline method (soaking 100g of masson pine wood chips with particle size less than 0.5cm in 400g of NaOH and Na 2 In S solution, naOH and Na 2 The S mass is 15 percent and 10 percent of the wood mass respectively, the treatment temperature is 170 ℃, and the heat preservation time is 3 hours) to obtain black liquor acidPutting alkali lignin obtained after separation (regulating the pH to 2.0 by using sulfuric acid with the mass fraction of 5%) into a 100mL three-neck flask, adding 60g of concentrated sulfuric acid with the mass fraction of 72%, uniformly stirring by using magnetons, slowly adding 2g of phosphorus pentoxide powder, controlling the system temperature to be 0 ℃ by using an ice-water bath, controlling the stirring speed of the magnetons in the flask to be 150rpm, sealing the flask opening, filtering the reaction slurry after 5h reaction by using a hydrophilic polytetrafluoroethylene membrane (the pore diameter is 0.8 mu m), washing the obtained filter cake by using 10mL of pure water, performing ultrafiltration on the filter cake by using an ultrafiltration membrane with the molecular weight cutoff of 500Da, and drying the liquid after ultrafiltration to obtain the phosphorylated lignin powder.
Example 4:
1g of steam explosion treatment (100 g of wet eucalyptus pieces passing through a 20-mesh sieve are placed in an explosion box, the mass ratio of eucalyptus to water is 3:2, the explosion pressure is 3Mpa, and the time is 90 s), eucalyptus enzymatic hydrolysis lignin (obtained by hydrolyzing cellulase for 72 h) is placed in a 50mL three-neck flask, 20g of concentrated sulfuric acid with the mass fraction of 84% is added, after uniform stirring is carried out by using magnetons, 2g of concentrated phosphoric acid with the mass fraction of 60% is slowly added, the temperature of a system is controlled to be 0 ℃ by using an ice water bath, the stirring speed of the magnetons in the flask is controlled to be 250rpm, the flask opening is sealed, after 0.2h of reaction, reaction slurry is filtered by using a hydrophilic polytetrafluoroethylene membrane (with the pore diameter of 0.8 mu m), the obtained filter cake is washed by using 2mL, a dialysis bag with the molecular weight of 100Da is used for one week in pure water, and then the liquid in the dialysis filter cake is dried, and the phosphorylated lignin powder is obtained.
Example 5:
5g of alkaline treatment (100 g of wheat straw with a length of less than 2cm are soaked in 400g of NaOH and Na 2 S solution, in which NaOH and Na 2 S is 10 percent and 8 percent of the wood mass, the processing temperature is 150 ℃, the processing time is 3 hours), wheat straw enzymolysis lignin (obtained by hydrolyzing cellulase for 72 hours) is put into a 100mL three-mouth flask, 10g of concentrated sulfuric acid with the mass fraction of 60 percent is added, after uniform stirring is carried out by magnetons, 5g of concentrated phosphoric acid with the mass fraction of 80 percent is slowly added, the temperature of the system is controlled to be-10 ℃ by a circulating cooling system, the stirring speed of the magnetons in the flask is controlled to be 200rpm, the flask opening is sealed, after 24 hours of reaction, the reaction slurry is polymerized by hydrophilicFiltering with a tetrafluoroethylene membrane (pore diameter of 0.8 μm), washing the obtained filter cake with 10mL of pure water, ultrafiltering the filter cake with an ultrafiltration membrane with the molecular weight cutoff of 1000Da, and drying the ultrafiltered liquid to obtain phosphorylated lignin powder.
Example 6:
pulping 5g of masson pine by alkaline process (placing 100g of masson pine chips with particle size less than 0.5cm in 400g of NaOH and Na 2 S solution, in which NaOH and Na 2 S is respectively 15 percent and 10 percent of the mass of wood, the treatment temperature is 170 ℃, the treatment time is 3 hours), the obtained alkali lignin is put into a 100mL three-mouth flask after acid precipitation of black liquor (the pH is adjusted to 2.0 by sulfuric acid with the mass fraction of 5 percent), 20g of concentrated sulfuric acid with the mass fraction of 50 percent is added, after uniform stirring is carried out by a magneton, 0.5g of phosphorus dioxide with the mass fraction of 60 percent is slowly added, the system temperature is controlled to be-20 ℃ by a circulating cooling system, the stirring speed of the magneton in the flask is controlled to be 100rpm, the flask opening is sealed, after 5 hours of reaction, the reaction slurry is filtered by a hydrophilic polytetrafluoroethylene membrane (the pore diameter is 0.8 mu m), the obtained filter cake is washed by 20mL of pure water, the filter cake is dialyzed for one week in a dialysis bag with the molecular weight cutoff of 100Da, then the liquid in the dialysis bag is dried, and the phosphorylated powdered lignin is obtained.
Example 7:
1g of milled wood lignin of switchgrass (which is obtained by ball milling 40-mesh switchgrass for 24 hours by using a planetary ball mill and then repeatedly extracting the milled wood lignin by using dioxane/water solution with the volume ratio of 4:1) into a 50mL three-neck flask, adding 10g of concentrated sulfuric acid with the mass fraction of 90%, uniformly stirring by using magnetons, slowly adding 2g of concentrated nitric acid with the mass fraction of 60%, controlling the system temperature to be 0 ℃ by using an ice-water bath, controlling the stirring speed of the magnetons in the flask to be 250rpm, sealing the opening of the flask, reacting for 0.5 hour, filtering the reaction slurry by using a hydrophilic polytetrafluoroethylene membrane (with the pore diameter of 0.8 mu m), washing the obtained filter cake by using 4mL of pure water, dialyzing the filter cake for one week by using a dialysis bag with the molecular weight cutoff of 500Da, and drying the liquid in the dialysis bag to obtain the nitrated powdery lignin.
Example 8:
putting 1g of lignin dissolved out of ionic liquid 1-ethyl-3-methylimidazole acetate from bagasse (the bagasse passes through a 40-mesh sieve, the processing temperature is 80 ℃, the heat preservation time is 1h, and the liquid-solid mass ratio is 10.
Example 9:
1g of p-toluenesulfonic acid solution is extracted from peanut shells (10 g of peanut shells with 40 meshes are placed in 100g of p-toluenesulfonic acid aqueous solution, the treatment temperature is 80 ℃, the heat preservation time is 0.5h, and the concentration of p-toluenesulfonic acid is 60 wt%) and placed in a 100mL three-neck flask, 5g of concentrated sulfuric acid with the mass fraction of 90% is added, after uniform stirring is carried out by using magnetons, 2g of phosphorus pentoxide is slowly added, the system temperature is controlled to be 30 ℃ by using a water bath, the stirring speed of the magnetons in the flask is controlled to be 150rpm, the flask opening is sealed, after 2h of reaction, reaction slurry is filtered by using a hydrophilic polytetrafluoroethylene membrane (the pore diameter is 0.8 mu m), the obtained filter cake is washed by using 2mL of pure water, the filter cake is dialyzed in a dialysis bag with the molecular weight cutoff of 500Da for one week, and then the liquid in the dialysis bag is dried, so that phosphorylated powdery lignin is obtained.
Example 10:
1g of gamma-valerolactone aqueous solution is extracted from corncobs (50 g of corncobs which are processed by 40 meshes are placed in 400g of gamma-valerolactone aqueous solution, the processing temperature is 140 ℃, the heat preservation time is 0.5h, the volume ratio of the gamma-valerolactone to water is 8:1), the lignin is put into a 50mL three-neck flask, 3g of concentrated sulfuric acid with the mass fraction of 65% is added, after uniform stirring is carried out by using magnetons, 2g of concentrated phosphoric acid with the mass fraction of 60% is slowly added, the system temperature is controlled by using an ice water bath to be 60 ℃, the stirring speed of the magnetons in the flask is controlled to be 250rpm, the flask opening is sealed, after 0.5h of reaction, the reaction slurry is filtered by using a hydrophilic polytetrafluoroethylene membrane (the pore diameter is 0.8 mu m), the obtained filter cake is washed by using 2mL, the dialysis bag with the molecular weight of 500Da is used for one week, and then the liquid in the dialysis bag is dried, and the phosphorylated lignin powder after pure water is obtained.
Example 11:
putting 1g of lignin extracted from rice straws by 1,4-butanediol (40 g of rice straws with the length of less than 2cm are placed in 400g of 1, 4-butanediol, the treatment temperature is 160 ℃, the heat preservation time is 1 h) into a 50mL three-neck flask, adding 1g of concentrated sulfuric acid with the mass fraction of 85%, uniformly stirring by using magnetons, slowly adding 0.1g of concentrated nitric acid with the mass fraction of 80%, controlling the system temperature to be 50 ℃ by using a water bath, controlling the stirring speed of the magnetons in the flask to be 200rpm, sealing the flask opening, filtering reaction slurry by using a hydrophilic polytetrafluoroethylene membrane (with the pore diameter of 0.8 mu m) after reacting for 10h, washing the obtained filter cake by using 2mL of pure water, dialyzing the filter cake for one week by using a dialysis bag with the molecular weight cutoff of 500Da in the pure water, and drying the liquid in the dialysis bag to obtain the nitrated lignin powder.
Example 12:
putting 1g of lignin extracted from birch by 1,3-propylene glycol (100 g of birch passing through 40 meshes is placed in 400g of 1, 3-propylene glycol, the treatment temperature is 160 ℃, and the heat preservation time is 1 h) into a 50mL three-neck flask, adding 1g of concentrated sulfuric acid with the mass fraction of 85%, uniformly stirring by using a magneton, then slowly adding 0.1g of concentrated nitric acid with the mass fraction of 80% and 0.3g of concentrated phosphoric acid with the mass fraction of 80%, controlling the system temperature by using a water bath at 30 ℃, controlling the stirring speed of the magneton in the flask at 100rpm, sealing the flask opening, filtering the reaction slurry by using a hydrophilic polytetrafluoroethylene membrane (the pore diameter is 0.8 mu m) after 10h of reaction, washing the obtained filter cake by using 2mL of pure water, dialyzing the filter cake in pure water by using a dialysis bag with the molecular weight cut-off of 500Da for one week, and then drying the liquid in the dialyzing bag to obtain the modified lignin powder.
Example 13:
putting 1g of lignin extracted from rice straws by an ethanol water system (40 g of rice straws with the length less than 2cm are placed in 240g of ethanol water system, the volume ratio of ethanol to water is 3:2, the treatment temperature is 160 ℃, and the heat preservation time is 0.5 h) into a 50mL three-neck flask, adding 1g of concentrated sulfuric acid with the mass fraction of 85%, uniformly stirring by using magnetons, slowly adding 0.2g of phosphorus pentoxide and 0.2g of concentrated nitric acid with the mass fraction of 80%, controlling the system temperature to be 20 ℃ by using a water bath, controlling the stirring speed of the magnetons in the flask to be 200rpm, sealing the flask opening, filtering the reaction slurry by using a hydrophilic polytetrafluoroethylene membrane (the pore diameter is 0.8 mu m) after 10h of reaction, washing the obtained filter cake by using 2mL of pure water, dialyzing the filter cake in pure water by using a dialysis bag with the molecular weight cutoff of 500Da for one week, and drying the liquid in the dialysis bag to obtain the modified powdery lignin.
Example 14:
1g of lignin extracted from sorghum stalks by a formic acid water system (40 g of sorghum stalks passing through 40 meshes are placed in a 400g of formic acid water system, the treatment temperature is 120 ℃, the heat preservation time is 1h, the volume ratio of formic acid to water is 8:2), the lignin is placed in a 50mL three-neck flask, 1g of concentrated sulfuric acid with the mass fraction of 85% is added, the mixture is uniformly stirred by magnetons, then 0.2g of sulfur trioxide and 0.2g of phosphorus pentoxide are slowly added, the system temperature is controlled by a water bath to be 30 ℃, the stirring speed of the magnetons in the flask is controlled to be 200rpm, the flask opening is sealed and burnt, after reacting for 10h, the reaction slurry is filtered by a hydrophilic polytetrafluoroethylene membrane (the pore diameter is 0.8 mu m), the obtained filter cake is washed by 2mL of pure water, the filter cake is dialyzed in the pure water for one week by a dialysis bag with the molecular weight cutoff of 500Da, and then the liquid in the dialysis bag is dried, and modified lignin powder is obtained.
The contents of sulfonic acid group, phosphoric acid group and nitric acid group in the lignin products obtained in the examples are calculated from corresponding S, P and N element. Wherein the S and N elements are measured by an element analyzer, the brief flow is as follows: after drying the dialyzed sample, about 5mg of the sample was weighed and examined with an elemental analyzer (VARIO EL III, elementar, germany). The P element is measured by a molybdenum blue colorimetric method, and the brief flow is as follows: nitrifying a sample by using mixed acid of nitric acid and perchloric acid, converting organic phosphorus into inorganic phosphate radical, adding ammonium molybdate to generate ammonium phosphomolybdate, reducing the ammonium phosphomolybdate into a blue compound (molybdenum blue) by using hydroquinone and sodium sulfite, and measuring the light absorption value of the molybdenum blue at the position of 660nm of wavelength by using a spectrophotometer to measure the content of phosphorus.
TABLE 1 content of hydrophilic groups in the product after hydrophilic modification of lignin in a low temperature concentrated sulfuric acid system
The sulfonation degrees of the lignin raw materials in the embodiments 1-14 are all less than 0.1mmol/g measured by an element analyzer. Example 1 is a comparative example to example 2, the same lignin starting material was used, and it can be seen from the above table that example 1 can also sulfonate lignin to some extent with only concentrated sulfuric acid, but the degree of sulfonation is low, only 0.22mmol/g. In the corresponding example 2, the degree of lignosulphonation increased to 0.54mmol/g after addition of the reagent sulfur trioxide. From examples 2 to 14, it can be seen that, in the concentrated sulfuric acid system, after different hydrophilic reaction reagents are added, the hydrophilic groups of lignin are all obviously improved, and the content of the hydrophilic groups is 0.5 to 2.3mmol/g. From examples 12 to 14 it can be seen that in concentrated sulfuric acid systems, several hydrophilic reactive groups can be added at a time to simultaneously graft different hydrophilic groups.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A method for low-temperature hydrophilic modification of lignin is characterized by comprising the following steps: adding industrial lignin into concentrated sulfuric acid (50-98 wt%, preferably 70-98 wt%), stirring, adding electrophilic reacting reagent capable of grafting hydrophilic group onto lignin, maintaining the reaction temperature at-20-60 deg.c (preferably 0-40 deg.c), reacting for 0.1-24 hr (preferably 1-4 hr), filtering or centrifuging to eliminate reaction liquid, washing with water and drying to obtain the hydrophilic modified lignin product.
2. The method of claim 1, wherein: the industrial lignin is one or the combination of more than two of alkali lignin, enzymolysis lignin, organic solvent lignin, klason lignin, ground wood lignin and lignin extracted from different plant raw materials by ionic liquid, deep eutectic solvent or hydrated molten salt system and the like.
3. The method of claim 2, wherein: the plant raw material is one or a combination of more than two of pine, eucalyptus, poplar, ash, sea buckthorn, cedar, fir, birch, corncob, corn stalk, wheat straw, bagasse, straw, rice hull and peanut shell.
4. The method of claim 1, wherein: the solid-liquid mass ratio of the industrial lignin to the concentrated sulfuric acid solution is 1-20, preferably 2-10.
5. The method of claim 1, wherein: the electrophilic reaction reagent capable of grafting the hydrophilic group on the lignin is one or the combination of more than two of sulfur trioxide, phosphorus pentoxide, concentrated phosphoric acid or concentrated nitric acid.
6. The method as set forth in claim 5, wherein: the mass concentration of the concentrated phosphoric acid or concentrated nitric acid used is greater than 50%, preferably greater than 60%.
7. A method as claimed in claim 1 or 5, characterized in that: the mass ratio of the added amount of the electrophilic reagent capable of grafting the hydrophilic group on the lignin to the industrial lignin is 0.1-2, preferably 0.2-1.
8. A method as claimed in claim 1, characterized by: the lignin product is washed by water, and the mass ratio of the water to the lignin is 1-10, preferably 2-8.
9. The method of claim 1, wherein: the obtained lignin hydrophilic modified product can be purified in water by a dialysis bag or ultrafiltration equipment with the molecular weight cutoff of 100-2000 Da.
10. An industrial lignin hydrophilically modified by the method of any one of claims 1 to 9, wherein: the content of hydrophilic groups of lignin, such as one or more of sulfonic group, phosphoric group or nitric group, is increased to 0.3-2.5 mmol/g, and the hydrophilicity is obviously improved.
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