CN111672482A - Preparation method of carboxymethyl hemicellulose/chitosan cross-linked spherical hydrogel - Google Patents
Preparation method of carboxymethyl hemicellulose/chitosan cross-linked spherical hydrogel Download PDFInfo
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Abstract
The invention discloses a preparation method of carboxymethyl hemicellulose/chitosan cross-linked spherical hydrogel. Dissolving perilla stem in NaOH solution, putting the mixed solution in ethanol for precipitation, extracting hemicellulose, and completely drying the hemicellulose; putting hemicellulose into an ethanol solvent, and adding a NaOH solution to react with the hemicellulose; and adding chloroacetic acid under a heating condition for etherification, and washing and drying a product to obtain the carboxymethyl hemicellulose. And then, respectively placing the carboxymethyl hemicellulose and the chitosan into deionized water, quickly stirring until the carboxymethyl hemicellulose and the chitosan are respectively and completely dispersed uniformly, mixing the carboxymethyl hemicellulose and the chitosan, slowly dropwise adding a glacial acetic acid solution under quick stirring, standing and defoaming the mixed solution, and then dropwise adding the mixed solution into a NaOH solution to obtain the carboxymethyl hemicellulose/chitosan crosslinking spherical hydrogel. The preparation method has the advantages of simple preparation process, easy control and less side reaction, and the obtained hydrogel has better adsorption treatment effect on heavy metal ions in water, has low cost and has good economic benefit in practical application.
Description
Technical Field
The invention belongs to the technical field of hydrogel, and particularly relates to a preparation method of carboxymethyl hemicellulose/chitosan cross-linked spherical hydrogel.
Background
With the rapid development of urbanization and industrialization, part of soil and water is polluted, and the social attention is attracted. Heavy metal ions are one of the major contaminants. Heavy metals have the characteristics of strong toxicity, difficult degradation and the like, and once being ingested by organisms, the heavy metals are enriched at the upper end of a biological chain, so that proteins, enzymes and the like are inactivated, and cumulative poisoning is caused. The biomass-based hydrogel has the advantages of good adsorption effect on heavy metal ions, low cost, wide application range and the like, and is increasingly emphasized in the research of heavy metal pollution treatment.
Chinese patent application No. CN201310405055.6 discloses a method for preparing a high-strength chitosan/cellulose composite hydrogel membrane, comprising the steps of weighing chitosan, cellulose, lithium hydroxide, sodium hydroxide, urea and water according to the weight percentage, mixing the components, and obtaining a transparent chitosan/cellulose alkaline system solution through swelling, freezing, unfreezing, filtering, centrifuging and defoaming; and (3) injecting the chitosan/cellulose alkaline system solution into a film forming die, and dipping in a coagulating bath to form the chitosan/cellulose hydrogel film. However, if the raw material lithium hydroxide used in the preparation process is not properly used, secondary pollution to the environment can be caused, and the preparation process is complex and the cost is high.
The invention discloses a hemicellulose-based hydrogel and a preparation method and application thereof, and belongs to Chinese patent application No. CN 201910331217.3. Carrying out graft modification on the viscose waste liquid by using allyl glycidyl ether, glycidyl acrylate or glycidyl methacrylate; then generating free radicals under the action of ammonium persulfate and N, N, N ', N' -tetramethyl ethylene diamine, and carrying out graft copolymerization with acrylic acid; adding a cross-linking agent N, N-methylene bisacrylamide, stirring for reaction to obtain a primary hydrogel product, and performing alkali treatment and drying to obtain the hemicellulose-based hydrogel. The method has good economic benefit, but the preparation process is more complex, the process comprises graft modification and graft copolymerization, and the cross-linking agent and the initiator have great influence on the adsorption performance of the method.
Therefore, the development of the carboxymethyl hemicellulose/chitosan crosslinking spherical hydrogel which has small influence on the environment, simple preparation process and good adsorption and energy absorption is necessary.
Disclosure of Invention
According to the defects in the prior art, the invention provides the preparation method of the carboxymethyl hemicellulose/chitosan cross-linked spherical hydrogel, which has the advantages of small influence of the used raw materials on the environment, simple preparation process and good adsorption performance.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
dissolving perilla stem in NaOH solution, putting the mixed solution in ethanol for precipitation, extracting hemicellulose, and completely drying the hemicellulose; putting hemicellulose into an ethanol solvent, and adding a NaOH solution to react with the hemicellulose; and adding chloroacetic acid under a heating condition for etherification, and washing and drying a product to obtain the carboxymethyl hemicellulose. And then, respectively placing the carboxymethyl hemicellulose and the chitosan into deionized water, quickly stirring until the carboxymethyl hemicellulose and the chitosan are respectively and completely dispersed uniformly, mixing the carboxymethyl hemicellulose and the chitosan, slowly dropwise adding a glacial acetic acid solution under quick stirring, standing and defoaming the mixed solution, and then dropwise adding the mixed solution into a NaOH solution to obtain the carboxymethyl hemicellulose/chitosan crosslinking spherical hydrogel.
The method specifically comprises the following steps:
1) dissolving crushed perilla stems in 5-10% NaOH solution, placing the solution in a water bath kettle, extracting the solution for 2-3 hours at 70-80 ℃, and collecting a mixed solution. When the concentration of the NaOH solution is lower than 5%, the perilla stems are slowly dissolved and are not completely dissolved; and when the concentration of the NaOH solution is higher than 10%, the NaOH is greatly excessive, and waste is generated. When the extraction temperature is lower than 70 ℃, the extraction efficiency of the perilla stems is too low; when the temperature is higher than 80 ℃, the extraction efficiency of the perilla stems is not greatly improved, and the energy consumption is large. When the extraction time is less than 2h, the perilla stems are not completely extracted; when the extraction time is 3 hours, the perilla stems are basically completely extracted, and the extraction is not economical after more than 3 hours.
2) And (3) placing the mixed solution into an ethanol solvent with the volume being 7-8 times that of the mixed solution, precipitating and extracting hemicellulose, and completely freeze-drying the extracted hemicellulose to obtain powdery hemicellulose. When the volume ratio of the ethanol solvent to the mixed solution is less than 7, the hemicellulose is not completely extracted; when the volume ratio is more than 8, the ethanol solvent is wasted more and uneconomically.
3) Putting hemicellulose into an ethanol solvent, adding 15-20% NaOH solution, reacting for 1-1.5 h, then adding an etherifying agent chloroacetic acid, etherifying for 2-3 h at 70-90 ℃, washing and drying a product to obtain the carboxymethyl hemicellulose. When the concentration of the NaOH solution is lower than 15%, the alkalization speed of hemicellulose is slow, and the subsequent carboxymethylation efficiency is low; when the concentration of the NaOH solution is higher than 10%, the NaOH is greatly excessive, the pH value is too high, and waste is caused. When the reaction time is less than 1h, the hemicellulose is not completely alkalized; when the reaction time is 1.5 hours, the hemicellulose is basically completely alkalized, and is uneconomical when the reaction time exceeds 1.5 hours. When the etherification temperature is lower than 70 ℃, the etherification reaction is not completely carried out or longer reaction time is needed; when the etherification temperature is higher than 90 ℃, the etherification efficiency is not greatly improved, and the energy consumption is large and uneconomical.
4) Respectively placing carboxymethyl hemicellulose and chitosan into deionized water, quickly stirring until the carboxymethyl hemicellulose and the chitosan are completely and uniformly dispersed, mixing the carboxymethyl hemicellulose and the chitosan, slowly dropwise adding a glacial acetic acid solution under quick stirring, standing and defoaming for 20-30 min, and then dropwise adding the obtained mixed solution into a 10-15% NaOH solution to obtain the carboxymethyl hemicellulose/chitosan crosslinked spherical hydrogel. When the defoaming time is less than 20min, the defoaming of the mixed solution is incomplete; when the defoaming time is 30min, the mixed solution is almost completely defoamed. When the concentration of the NaOH solution is lower than 10%, the balling speed of the hydrogel is slow; and when the concentration of the NaOH solution is higher than 15%, the balling speed of the hydrogel is not obviously accelerated.
3. The method for preparing carboxymethyl hemicellulose/chitosan cross-linked spherical hydrogel according to claim 2, wherein the mass ratio of the crushed perilla stems in the step 1) to the NaOH solution is 1: 7-8. When the mass ratio of the crushed perilla stems to the NaOH solution is more than 1:7, the hemicellulose can not be completely dissolved out; if the mass ratio is less than 1:8, the dissolving speed of the hemicellulose in the alkali liquor is not obviously increased.
4. The preparation method of the carboxymethyl hemicellulose/chitosan cross-linked spherical hydrogel according to claim 2, wherein in the step 3), the concentration of the hemicellulose in the absolute ethyl alcohol is 30% -35%, the mass ratio of the NaOH solution to the hemicellulose is 1: 1-2, and the mass ratio of the hemicellulose to the chloroacetic acid is 1: 1-1.5. When the concentration of the hemicellulose in the absolute ethyl alcohol is 30% -35%, the hemicellulose is uniformly dispersed in the absolute ethyl alcohol and is not excessive. When the mass ratio of NaOH to hemicellulose is less than 1:2, a certain amount of alkali is consumed by side reaction to generate sodium chlorate which cannot be neutralized by alkali liquor, and the carboxymethylation efficiency is reduced; if the mass ratio is more than 1:1, the side reaction consumes excessive alkali liquor to generate chloroacetic acid, and the carboxymethylation efficiency is also reduced. When the mass ratio of the hemicellulose to the chloroacetic acid is less than 1:1.5, the chloroacetic acid is excessive and the etherification rate is not greatly improved; when the mass ratio is more than 1:1, the hemicellulose is not completely etherified, resulting in low yield.
5. The preparation method of the carboxymethyl hemicellulose/chitosan cross-linked spherical hydrogel according to claim 2, wherein in the step 4), the concentration of the carboxymethyl hemicellulose in deionized water is 5% -10%, the concentration of chitosan in deionized water is 5% -10%, the mass ratio of the carboxymethyl hemicellulose to the chitosan in a mixed solution of the carboxymethyl hemicellulose and the chitosan is 1: 1-2, and the volume ratio of the mixed solution to a NaOH solution is 1: 20-40. The optimal mass ratio of the carboxymethyl hemicellulose to the chitosan in the mixed solution is 1: 1-2, because the crosslinking effect of the chitosan and the carboxymethyl hemicellulose is poor due to excessive amount of the chitosan and the carboxymethyl hemicellulose. The mass ratio of the glacial acetic acid to the carboxymethyl hemicellulose to the chitosan is 1: 4-4.5, and the gel performance is poor due to the excessively high and excessively low mass ratios. When the volume ratio of the mixed solution to the NaOH solution is more than 1:20, negative influence is generated on the hydrogel balling; and when the volume ratio is less than 1:40, the NaOH solution is excessive and the hydrogel balling speed is not obviously accelerated.
Compared with the prior art, the invention has the following beneficial effects:
1. the preparation method provided by the invention has the advantages that no chemical cross-linking agent is used in the preparation process, the used raw materials have small influence on the environment, the preparation method is simple, the production efficiency is high, and the production cost is low.
2. The preparation method has few side reactions and easy control, and the obtained carboxymethyl hemicellulose/chitosan cross-linked spherical hydrogel has good stability and good adsorption effect on heavy metals.
3. The carboxymethyl hemicellulose/chitosan crosslinking spherical hydrogel prepared by the invention takes natural macromolecular hemicellulose and chitosan as raw materials, has rich raw material sources and low cost, and is easy to degrade. Therefore, the carboxymethyl hemicellulose/chitosan crosslinking spherical hydrogel has good social benefit and economic benefit in practical application.
Detailed Description
The present invention is further described in detail with reference to the following specific examples, which are not specifically described, and the raw materials used are common commercial products.
Example 1:
the carboxymethyl hemicellulose/chitosan cross-linked spherical hydrogel is prepared by the following method:
1) weighing a certain mass of crushed perilla stems, dissolving the crushed perilla stems in a 5% NaOH solution, placing the crushed perilla stems and the NaOH solution in a mass ratio of 1:7 in a water bath kettle, extracting for 3 hours at 80 ℃, and collecting a mixed solution.
2) And (3) putting the mixed solution into an ethanol solvent with the volume 8 times that of the mixed solution, precipitating and extracting hemicellulose, and completely freeze-drying the extracted hemicellulose to obtain powdery hemicellulose.
3) Putting hemicellulose into an ethanol solvent, wherein the mass concentration of the hemicellulose in absolute ethanol is 35%, adding a 20% NaOH solution, and reacting for 2 hours, wherein the mass ratio of NaOH to the hemicellulose is 1: 2. Adding etherifying agent chloroacetic acid with the mass ratio of 1:1 to hemicellulose into the solution, etherifying for 3 hours at 90 ℃, washing and drying the product to obtain the carboxymethyl hemicellulose.
5) Respectively placing carboxymethyl hemicellulose and chitosan into deionized water, and quickly stirring until the carboxymethyl hemicellulose and the chitosan are completely and uniformly dispersed, wherein the concentration of the carboxymethyl hemicellulose in the deionized water is 10%, and the concentration of the chitosan in the deionized water is 10%. And mixing the two components, wherein the mass ratio of the carboxymethyl hemicellulose to the chitosan is 1:1. Slowly dripping a glacial acetic acid solution under rapid stirring, wherein the mass ratio of the glacial acetic acid to the carboxymethyl hemicellulose to the chitosan is 1: 4; standing and defoaming for 20min, and dropwise adding the obtained mixed solution into a 10% NaOH solution, wherein the volume ratio of the mixed solution to the NaOH solution is 1:40, so as to obtain the carboxymethyl hemicellulose/chitosan crosslinked spherical hydrogel.
Example 2:
the carboxymethyl hemicellulose/chitosan cross-linked spherical hydrogel is prepared by the following method:
1) weighing a certain mass of crushed perilla stems, dissolving the crushed perilla stems in a 10% NaOH solution, placing the crushed perilla stems and the NaOH solution in a water bath kettle in a mass ratio of 1:8, extracting for 2 hours at 70 ℃, and collecting a mixed solution.
2) And (3) putting the mixed solution into an ethanol solvent with the volume 7 times that of the mixed solution, precipitating and extracting hemicellulose, and completely freeze-drying the extracted hemicellulose to obtain powdery hemicellulose.
3) Putting hemicellulose into an ethanol solvent, wherein the mass concentration of the hemicellulose in absolute ethanol is 30%, adding a 15% NaOH solution, and reacting for 1h, wherein the mass ratio of NaOH to the hemicellulose is 1:1. Adding etherifying agent chloroacetic acid with the mass ratio of 1:1.25 to the hemicellulose into the solution, etherifying for 2 hours at 70 ℃, and washing and drying the product to obtain the carboxymethyl hemicellulose.
5) Respectively placing carboxymethyl hemicellulose and chitosan into deionized water, and rapidly stirring until the carboxymethyl hemicellulose and the chitosan are completely and uniformly dispersed, wherein the concentration of the carboxymethyl hemicellulose in the deionized water is 5%, and the concentration of the chitosan in the deionized water is 5%. And mixing the two components, wherein the mass ratio of the carboxymethyl hemicellulose to the chitosan is 1:1. Slowly dripping a glacial acetic acid solution under rapid stirring, wherein the mass ratio of the glacial acetic acid to the carboxymethyl hemicellulose to the chitosan is 1: 4.5; standing and defoaming for 30min, and dropwise adding the obtained mixed solution into a 15% NaOH solution, wherein the volume ratio of the mixed solution to the NaOH solution is 1:20, so as to obtain the carboxymethyl hemicellulose/chitosan crosslinked spherical hydrogel.
Example 3:
the carboxymethyl hemicellulose/chitosan cross-linked spherical hydrogel is prepared by the following method:
1) weighing a certain mass of crushed perilla stems, dissolving the crushed perilla stems in a 5% NaOH solution, placing the crushed perilla stems and the NaOH solution in a water bath kettle with the mass ratio of 1:7.5, extracting for 2.5 hours at 75 ℃, and collecting a mixed solution.
2) And (3) placing the mixed solution into an ethanol solvent with the volume 7.5 times of that of the mixed solution, precipitating and extracting hemicellulose, and completely freeze-drying the extracted hemicellulose to obtain powdery hemicellulose.
3) Putting the hemicellulose into an ethanol solvent, wherein the mass concentration of the hemicellulose in absolute ethanol is 32.5%, adding a 17.5% NaOH solution, and reacting for 1.25h, wherein the mass ratio of NaOH to the hemicellulose is 1: 1.5. Adding etherifying agent chloroacetic acid with the mass ratio of 1:1.5 to the hemicellulose into the solution, etherifying for 2.5 hours at 80 ℃, and washing and drying the product to obtain the carboxymethyl hemicellulose.
5) And respectively placing the carboxymethyl hemicellulose and the chitosan into deionized water, and quickly stirring until the carboxymethyl hemicellulose and the chitosan are completely and uniformly dispersed, wherein the concentration of the carboxymethyl hemicellulose in the deionized water is 7.5 percent, and the concentration of the chitosan in the deionized water is 7.5 percent. And mixing the two components, wherein the mass ratio of the carboxymethyl hemicellulose to the chitosan is 1: 1.5. Slowly dripping a glacial acetic acid solution under rapid stirring, wherein the mass ratio of the glacial acetic acid to the carboxymethyl hemicellulose to the chitosan is 1: 4.25; standing and defoaming for 25min, and dropwise adding the obtained mixed solution into a 12.5% NaOH solution, wherein the volume ratio of the mixed solution to the NaOH solution is 1:30, so as to obtain the carboxymethyl hemicellulose/chitosan crosslinking spherical hydrogel.
Example 4:
the carboxymethyl hemicellulose/chitosan cross-linked spherical hydrogel is prepared by the following method:
1) weighing a certain mass of crushed perilla stems, dissolving the crushed perilla stems in a 5% NaOH solution, placing the crushed perilla stems and the NaOH solution in a mass ratio of 1:7 in a water bath kettle, extracting for 2 hours at 70 ℃, and collecting a mixed solution.
2) And (3) putting the mixed solution into an ethanol solvent with the volume 8 times that of the mixed solution, precipitating and extracting hemicellulose, and completely freeze-drying the extracted hemicellulose to obtain powdery hemicellulose.
3) Putting the hemicellulose into an ethanol solvent, wherein the mass concentration of the hemicellulose in absolute ethanol is 30%, adding a 15% NaOH solution, and reacting for 1.5h, wherein the mass ratio of NaOH to the hemicellulose is 1: 2. Adding etherifying agent chloroacetic acid with the mass ratio of 1:1 to hemicellulose into the solution, etherifying for 3 hours at 80 ℃, washing and drying the product to obtain the carboxymethyl hemicellulose.
5) Respectively placing carboxymethyl hemicellulose and chitosan into deionized water, and rapidly stirring until the carboxymethyl hemicellulose and the chitosan are completely and uniformly dispersed, wherein the concentration of the carboxymethyl hemicellulose in the deionized water is 5% and the concentration of the chitosan in the deionized water is 10%. And mixing the two components, wherein the mass ratio of the carboxymethyl hemicellulose to the chitosan is 1: 2. Slowly dripping a glacial acetic acid solution under rapid stirring, wherein the mass ratio of the glacial acetic acid to the carboxymethyl hemicellulose to the chitosan is 1: 4.5; standing and defoaming for 20min, and dropwise adding the obtained mixed solution into a 10% NaOH solution, wherein the volume ratio of the mixed solution to the NaOH solution is 1:40, so as to obtain the carboxymethyl hemicellulose/chitosan crosslinked spherical hydrogel.
Example 5:
the carboxymethyl hemicellulose/chitosan cross-linked spherical hydrogel is prepared by the following method:
1) weighing a certain mass of crushed perilla stems, dissolving the crushed perilla stems in a 10% NaOH solution, placing the crushed perilla stems and the NaOH solution in a water bath kettle in a mass ratio of 1:8, extracting for 3 hours at 80 ℃, and collecting a mixed solution.
2) And (3) putting the mixed solution into an ethanol solvent with the volume 7 times that of the mixed solution, precipitating and extracting hemicellulose, and completely freeze-drying the extracted hemicellulose to obtain powdery hemicellulose.
3) Putting hemicellulose into an ethanol solvent, wherein the mass concentration of the hemicellulose in absolute ethanol is 30%, adding a 15% NaOH solution, and reacting for 1h, wherein the mass ratio of NaOH to the hemicellulose is 1: 2. Adding etherifying agent chloroacetic acid with the mass ratio of 1:1.25 to the hemicellulose into the solution, etherifying for 2 hours at 80 ℃, and washing and drying the product to obtain the carboxymethyl hemicellulose.
5) Respectively placing carboxymethyl hemicellulose and chitosan into deionized water, and rapidly stirring until the carboxymethyl hemicellulose and the chitosan are completely and uniformly dispersed, wherein the concentration of the carboxymethyl hemicellulose in the deionized water is 10% and the concentration of the chitosan in the deionized water is 5%. And mixing the two components, wherein the mass ratio of the carboxymethyl hemicellulose to the chitosan is 1:1. Slowly dripping a glacial acetic acid solution under rapid stirring, wherein the mass ratio of the glacial acetic acid to the carboxymethyl hemicellulose to the chitosan is 1: 4; standing and defoaming for 30min, and dropwise adding the obtained mixed solution into a 10% NaOH solution, wherein the volume ratio of the mixed solution to the NaOH solution is 1:40, so as to obtain the carboxymethyl hemicellulose/chitosan crosslinked spherical hydrogel.
Example 6:
the carboxymethyl hemicellulose/chitosan cross-linked spherical hydrogel is prepared by the following method:
1) weighing a certain mass of crushed perilla stems, dissolving the crushed perilla stems in a 5% NaOH solution, placing the crushed perilla stems and the NaOH solution in a water bath kettle in a mass ratio of 1:8, extracting for 3 hours at 75 ℃, and collecting a mixed solution.
2) And (3) putting the mixed solution into an ethanol solvent with the volume 8 times that of the mixed solution, precipitating and extracting hemicellulose, and completely freeze-drying the extracted hemicellulose to obtain powdery hemicellulose.
3) Putting the hemicellulose into an ethanol solvent, wherein the mass concentration of the hemicellulose in absolute ethanol is 35%, adding a 20% NaOH solution, and reacting for 1.5h, wherein the mass ratio of NaOH to the hemicellulose is 1:1. Adding etherifying agent chloroacetic acid with the mass ratio of 1:1.5 to the hemicellulose into the solution, etherifying for 2 hours at 70 ℃, and washing and drying the product to obtain the carboxymethyl hemicellulose.
5) Respectively placing carboxymethyl hemicellulose and chitosan into deionized water, and quickly stirring until the carboxymethyl hemicellulose and the chitosan are completely and uniformly dispersed, wherein the concentration of the carboxymethyl hemicellulose in the deionized water is 10%, and the concentration of the chitosan in the deionized water is 10%. And mixing the two components, wherein the mass ratio of the carboxymethyl hemicellulose to the chitosan is 1:1. Slowly dripping a glacial acetic acid solution under rapid stirring, wherein the mass ratio of the glacial acetic acid to the carboxymethyl hemicellulose to the chitosan is 1: 4; standing and defoaming for 25min, and dropwise adding the obtained mixed solution into a 10% NaOH solution, wherein the volume ratio of the mixed solution to the NaOH solution is 1:20, so as to obtain the carboxymethyl hemicellulose/chitosan crosslinked spherical hydrogel.
The carboxymethyl hemicellulose/chitosan cross-linked spherical hydrogel prepared in examples 1 to 6 was measured for Cu in heavy metal-containing wastewater2+The adsorption rate of (D) is shown in Table 1.
TABLE 1 carboxymethyl hemicellulose/chitosan crosslinked spherical hydrogel vs Cu2+Adsorption rate of (2)
| Product(s) | Cu2+Adsorption Rate (%) |
| Example 1 | 91.2% |
| Example 2 | 90.8% |
| Example 3 | 91.0% |
| Example 4 | 90.2% |
| Example 5 | 90.4% |
| Example 6 | 89.8% |
As can be seen from Table 1 above, the present inventionThe carboxymethyl hemicellulose/chitosan crosslinking spherical hydrogel prepared by the invention can treat Cu in heavy metal-containing sewage2+The treatment effect is better, so that the carboxymethyl hemicellulose/chitosan crosslinking spherical hydrogel is proved to have good performance.
The above examples of the present invention are only illustrative of the present invention and are not intended to limit the embodiments of the present invention. Many modifications in different forms will be apparent to those skilled in the art in light of the above teachings. Not all embodiments are exhaustive. All obvious changes and modifications of the present invention are within the scope of the present invention.
Claims (5)
1. A preparation method of carboxymethyl hemicellulose/chitosan cross-linked spherical hydrogel is characterized in that perilla stems are dissolved in NaOH solution, then mixed solution is placed in ethanol for precipitation and hemicellulose extraction, and the hemicellulose is completely dried; putting hemicellulose into an ethanol solvent, and adding a NaOH solution to react with the hemicellulose; and adding chloroacetic acid under a heating condition for etherification, and washing and drying a product to obtain the carboxymethyl hemicellulose. And then, respectively placing the carboxymethyl hemicellulose and the chitosan into deionized water, quickly stirring until the carboxymethyl hemicellulose and the chitosan are respectively and completely dispersed uniformly, mixing the carboxymethyl hemicellulose and the chitosan, slowly dropwise adding a glacial acetic acid solution under quick stirring, standing and defoaming the mixed solution, and then dropwise adding the mixed solution into a NaOH solution to obtain the carboxymethyl hemicellulose/chitosan crosslinking spherical hydrogel.
2. The method for preparing carboxymethyl hemicellulose/chitosan cross-linked spherical hydrogel according to claim 1, comprising the steps of:
1) dissolving crushed perilla stems in 5-10% NaOH solution, placing the solution in a water bath kettle, extracting the solution for 2-3 hours at 70-80 ℃, and collecting a mixed solution;
2) placing the mixed solution in an ethanol solvent with the volume of 7-8 times that of the mixed solution, precipitating and extracting hemicellulose, and completely freeze-drying the extracted hemicellulose to obtain powdery hemicellulose;
3) putting hemicellulose into an ethanol solvent, adding 15-20% NaOH solution, reacting for 1-1.5 h, then adding an etherifying agent chloroacetic acid, etherifying for 2-3 h at 70-90 ℃, washing and drying a product to obtain carboxymethyl hemicellulose;
4) respectively placing carboxymethyl hemicellulose and chitosan into deionized water, quickly stirring until the carboxymethyl hemicellulose and the chitosan are completely and uniformly dispersed, mixing the carboxymethyl hemicellulose and the chitosan, slowly dropwise adding a glacial acetic acid solution under quick stirring, standing and defoaming for 20-30 min, and then dropwise adding the obtained mixed solution into a 10-15% NaOH solution to obtain the carboxymethyl hemicellulose/chitosan crosslinked spherical hydrogel.
3. The method for preparing carboxymethyl hemicellulose/chitosan cross-linked spherical hydrogel according to claim 2, wherein the mass ratio of the crushed perilla stems in the step 1) to the NaOH solution is 1: 7-8.
4. The preparation method of the carboxymethyl hemicellulose/chitosan cross-linked spherical hydrogel according to claim 2, wherein in the step 3), the concentration of the hemicellulose in the absolute ethyl alcohol is 30% -35%, the mass ratio of NaOH to the hemicellulose is 1: 1-2, and the mass ratio of the hemicellulose to the chloroacetic acid is 1: 1-1.5.
5. The preparation method of the carboxymethyl hemicellulose/chitosan cross-linked spherical hydrogel according to claim 2, wherein in the step 4), the concentration of the carboxymethyl hemicellulose in deionized water is 5% -10%, the concentration of chitosan in deionized water is 5% -10%, the mass ratio of the carboxymethyl hemicellulose to the chitosan in a mixed solution of the carboxymethyl hemicellulose and the chitosan is 1: 1-2, the mass ratio of glacial acetic acid to the sum of the carboxymethyl hemicellulose and the chitosan is 1: 4-4.5, and the volume ratio of the mixed solution to a NaOH solution is 1: 20-40.
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