CN112275260A - Chitosan/fibroin-based dual-structure porous adsorption filter material with polyethylene glycol as pore-foaming agent and preparation method thereof - Google Patents
Chitosan/fibroin-based dual-structure porous adsorption filter material with polyethylene glycol as pore-foaming agent and preparation method thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The invention provides a chitosan/silk fibroin-based dual-structure porous adsorption filtering material taking polyethylene glycol as a pore-foaming agent, which consists of silk fibroin, chitosan and the pore-foaming agent, wherein the mass ratio of the silk fibroin to the chitosan is 1-9:9-1, the molecular weight of the chitosan is 50000-100000, the deacetylation degree of the chitosan is 80-95%, and the pore-foaming agent is polyethylene glycol. The chitosan/silk fibroin-based dual-structure porous adsorption filter material taking polyethylene glycol as a pore-forming agent has a good adsorption effect on metal ions, and can be used as an adsorption filter material to be applied to the fields of biomedical materials, heavy metal treatment, wastewater decomposition and filtration, precious metal recovery, hygienic products, liquid absorbing materials and the like.
Description
Technical Field
The invention relates to the field of adsorption materials, in particular to a chitosan/fibroin-based dual-structure porous adsorption filter material taking polyethylene glycol as a pore-foaming agent and a preparation method thereof.
Background
Common adsorbents are broadly divided into three types: natural organic adsorbents, inorganic adsorbents, and synthetic adsorbents. The different types of adsorbents are obviously different, wherein the inorganic adsorbent mainly comprises zeolite, bentonite, alumina and the like, and the material characteristics are as follows: the raw materials of the adsorbent are abundant and low in price, but the self adsorption capacity of the material is small, the adsorption effect is poor when the material is directly put into use, and further improvement is still needed; the natural organic adsorbent mainly comprises chitosan, cellulose-property waste materials (such as wood chips, rice husks, straws and the like), humic acid and the like, and is characterized by comprising the following materials: the raw materials of the adsorbent are mainly processing wastes in the production process of other industries, the cost is low, the source is wide, the resource utilization of waste materials is facilitated, meanwhile, the material is used as a natural organic matter, the characteristic of easy degradation is realized, the secondary pollution is avoided, but the material per se has weak adsorbability on heavy metals, and the adsorption capacity is further improved; the artificial synthetic adsorbent mainly comprises polyacrylamide, polystyrene and the like, and is characterized by comprising the following materials: the adsorbent has various types and large adsorption capacity, but the material preparation cost is high, and the adsorbent is difficult to be put into use on a large scale. The specific surface area and structure of the adsorbent material are major factors affecting the adsorption efficiency of the adsorbent material. The larger the specific surface area, the higher the efficiency of the adsorbent material.
The chitosan is light yellow powder in a general state, and can be prepared into a semitransparent semicrystalline solid material after being dissolved and dried in dilute acid. As a safe, nontoxic and biodegradable natural high polymer, the macromolecular structure of the chitosan contains a large amount of free amino and hydroxyl active groups, and the groups can be combined with heavy metal ions, so that the effect of adsorbing the heavy metal ions in the solution is achieved, the chitosan is an excellent heavy metal adsorption raw material, and meanwhile, the chitosan has the advantages of low preparation cost, wide source, good heavy metal adsorption effect, greenness, no pollution and the like, and has attracted extensive attention of researchers. However, the chitosan material has the problems of poor mechanical properties in a water absorption state, low material structure density porosity, unstable adsorption effect in a slightly acidic environment and the like in the process of treating heavy metal pollution in water, and needs to be further improved in the aspect of being used as an adsorbent.
The fibroin is a natural protein material, and polar and nonpolar amino acid residue sequences in the molecule of the fibroin are alternately arranged to easily form a beta-sheet (twist II) structure with stable physicochemical properties under the condition of external environment change (such as temperature, pH, cross-linking agent and the like), namely the self-assembly behavior of the fibroin. Analysis shows that the silk fibroin material does not have the function of a heavy metal adsorbent because the structure and property of the material are changed to cause the material to have poor adsorbability on heavy metal ions. However, when the silk fibroin is used as a safe, nontoxic, degradable and biocompatible macromolecular substance and is compounded with a macromolecular degradable polymer (such as cellulose, chitosan and the like) with certain adsorption capacity, certain specific properties of the prepared material (such as improvement of mechanical properties, reduction of leaching rate and the like) can be obviously improved, and the silk fibroin serving as a modifier of the macromolecular material has certain research value.
Disclosure of Invention
The technical problem to be solved is as follows: the invention aims to provide a chitosan/fibroin-based dual-structure porous adsorption filtering material taking polyethylene glycol as a pore-forming agent, which has a good adsorption effect on metal ions and can be used as an adsorption filtering material to be applied to the fields of biomedical materials, heavy metal treatment, wastewater decomposition and filtration, precious metal recovery, hygienic products, liquid absorbing materials and the like.
The technical scheme is as follows: a porous adsorption filter material with a chitosan/silk fibroin-based dual structure comprises silk fibroin, chitosan and a pore-forming agent, wherein the mass ratio of the silk fibroin to the chitosan is 1-9:9-1, the molecular weight of the chitosan is 50000-100000, the deacetylation degree of the chitosan is 80-95%, and the pore-forming agent is polyethylene glycol.
A preparation method of a chitosan/fibroin-based dual-structure porous adsorption filter material taking polyethylene glycol as a pore-foaming agent comprises the following steps:
s1, preparing a chitosan solution;
s2, preparing a fibroin solution;
s3, mixing and stirring the chitosan solution, the pore-forming agent and the fibroin solution to obtain a mixed solution;
s4, preparing the composite material with a specified shape and structure from the mixed solution;
s5, carrying out pore-foaming agent dissolution treatment on the composite material prepared in the step S4 to obtain the porous material with the chitosan/silk fibroin-based dual structure.
Preferably, the preparation method of the chitosan/fibroin-based dual-structure porous adsorption filter material with polyethylene glycol as a pore-foaming agent comprises the following steps:
s1, dissolving chitosan in a low-concentration formic acid solution, adding high-concentration formic acid after the chitosan is completely dissolved, and adjusting the chitosan to a proper concentration to obtain a chitosan solution;
s2, dissolving the regenerated silk fibroin into a formic acid solution to obtain a silk fibroin solution;
s3, adding a pore-foaming agent into the chitosan solution prepared in the step S1, mixing and stirring uniformly, adding the fibroin solution prepared in the step S2, mixing and stirring uniformly, standing and defoaming to obtain a mixed solution;
s4, preparing a specified shape structure from the mixed solution after standing, and treating the completely dried composite material with alkali liquor to dissolve out acid to obtain a chitosan/silk fibroin-based composite material;
s5, dissolving the composite material prepared in the step S4 in water at a certain temperature to obtain the porous material with the chitosan/silk fibroin-based dual structure.
Preferably, the concentration of the low-concentration formic acid solution in the step S1 is 1-10wt%, and the concentration of the high-concentration formic acid solution is 30-100%.
Preferably, the concentration of the formic acid solution in the step S2 is 88-98 wt%.
Preferably, in the step S3, the mass ratio of the silk fibroin and the chitosan in the mixed solution is 1-9:9-1, and the content of the pore-forming agent is 0.5-5 wt%.
Preferably, the shape of the composite material in step S4 is any one of a film, a porous sponge, a tube, a granule, a powder and a regenerated fiber.
Preferably, the sodium hydroxide solution is used in the dissolution treatment in step S4, and the concentration of the sodium hydroxide solution is 0.5-5 wt%.
Preferably, the temperature in the step S5 is 0-90 ℃, and the dissolution treatment time is 0.5-7 h.
A porous adsorption filtering material with chitosan/silk fibroin-based dual structure is applied to biomedical materials, heavy metal treatment, wastewater decomposition and filtration, precious metal recovery, hygienic products and liquid absorption materials.
Has the advantages that: the blending adsorption material of the invention has the following advantages:
1. excessive polyethylene glycol and surface part of fibroin in the polyethylene glycol-fibroin/chitosan-based blended membrane are dissolved out by pure water, a dual-structure blended membrane with micron-sized holes and gully-shaped coarse macroporous surfaces can be prepared, the specific surface area of the blended material is greatly increased, the material has higher adsorption rate, and the blended membrane is an adsorption material with excellent performance;
2. the chitosan/silk fibroin based dual-structure porous adsorption filter material can be applied to the fields of heavy metal treatment, wastewater decomposition and filtration, precious metal recovery, hygienic products, liquid absorption materials and the like, and chitosan and silk fibroin which are used as main raw materials are widely applied to the field of biomedical materials due to good biocompatibility and no immune rejection, so that the chitosan/silk fibroin based blend material is applied to the fields for exploration.
Description of the drawings:
FIG. 1 is a stress-strain curve of a membrane prepared by dissolving chitosan with formic acid or acetic acid at different concentrations;
FIG. 2 SEM of a formic acid-solubilized chitosan membrane;
FIG. 3 the effect of formic acid concentration on the mechanical properties of the blended film when blended;
FIG. 4 is the effect of silk fibroin and chitosan ratio on the mechanical performance of a blended membrane during blending;
FIG. 5 the effect of polyethylene glycol addition on the mechanical properties of blend membranes;
FIG. 6 is the effect of temperature on the mechanical properties of the blend membrane during the polyethylene glycol leaching treatment;
FIG. 7 the effect of polyethylene glycol dissolution treatment time on the mechanical properties of porous membranes;
FIG. 8 is SEM pictures of polyethylene glycol-fibroin and chitosan blend membrane (PEG-SF/CS) under different magnification, wherein a is the surface of the PEG-SF/CS membrane; b is the cross section of the PEG-SF/CS membrane.
Detailed Description
Example 1
Preparation of Chitosan Membrane
The first step is as follows: 20mL of prepared formic acid and acetic acid solutions with the concentration of 1% -5% are respectively placed in a beaker, 0.6g of chitosan is respectively weighed and poured into the beaker, the temperature of a heat collection type constant temperature magnetic stirrer is set to be 30 ℃, stirring is carried out at a constant speed of 200r/min, and the chitosan is completely dissolved.
The second step is that: standing and defoaming the dissolved chitosan solution for 30min, pouring the solution into a plastic dish by adopting a tape casting method, naturally volatilizing and drying for 24h at room temperature, and forming a film.
The third step: the dried chitosan membrane was soaked in 0.5% sodium hydroxide solution for 2h to neutralize the residual acid in the membrane. And then repeatedly washing the membrane with deionized water, soaking the membrane in 1000mL of deionized water for 24h to remove redundant sodium hydroxide residues, and finally drying the membrane at room temperature for later use.
As can be seen from fig. 1, formic acid-dissolved chitosan films are harder and more brittle, while acetic acid-dissolved chitosan films are more ductile, especially as the acid concentration increases, the difference is more pronounced. Analysis shows that the formic acid dissolved chitosan film forms a new structure or improves the crystallinity in the forming process; as can be seen from the combination of FIG. 2, the chitosan mold dissolved with acetic acid has a lamellar-like structure, while the chitosan mold dissolved with formic acid has an obvious fibrillating structure, and the chitosan is analyzed to be capable of self-assembling into a fibrillar structure in the formic acid.
Therefore, the difference of the contrast formic acid and acetic acid as chitosan solvents is comprehensively carried out, and formic acid is selected as a proper solvent of the chitosan in consideration of the application aspect of the solvent and the reduction of the introduction of organic matters in the subsequent blending test of the chitosan and the fibroin, and the concentration of the formic acid for dissolving the chitosan is preferably 3%.
Example 2
Preparing a chitosan/silk fibroin blend membrane:
the first step is as follows: preparing 3% formic acid dissolved chitosan, setting the temperature of a heat collection type constant temperature magnetic stirrer to be 30 ℃, stirring at a constant speed of 200r/min, adding 98% formic acid into the chitosan solution after the chitosan powder is completely dissolved, and uniformly stirring for later use after the formic acid content in the solution reaches a preset concentration (30%, 40%, 50%, 60%, 70% and 98%).
The second step is that: dissolving regenerated silk fibroin directly with 98% formic acid, stirring at 30 deg.C at 20 r/min, pouring appropriate amount of silk fibroin solution into high-speed stirred chitosan solution to make silk fibroin and chitosan reach appropriate ratio (0: 10, 2:8, 4:6, 5:5, 6:4, 7:3, 8:2, 9:1, 10: 0), stirring at rotating speed for 5min, and standing for one day to remove foam.
The third step: pouring the blend solution after standing and defoaming into a plastic dish by adopting a tape casting method, and drying at a proper temperature (20 ℃, 30 ℃, 50 ℃, 70 ℃ and natural drying) to form a film.
The fourth step: and soaking the dried blend membrane part in absolute ethyl alcohol, and then airing for later use.
The fifth step: the entire treated blended membrane was soaked in 0.5% sodium hydroxide solution for 30min to neutralize the residual acid in the membrane. And then repeatedly washing the membrane by using deionized water, soaking the membrane in 1000mL of deionized water for 24h to remove redundant sodium hydroxide residues, and finally drying the membrane at room temperature for later use.
According to the concentration of the chitosan solution set in the above embodiment, the mechanical property of the blended membrane material is tested, and as can be seen from fig. 3, when the formic acid concentration in the blended solution is higher (50-70%), the mechanical property difference of the prepared blended membrane is smaller, and under the conditions of maintaining higher mechanical property, uniformly blending silk fibroin and chitosan and saving the sample preparation cost, the formic acid concentration is most suitable for being selected to be 50% when blending silk fibroin and chitosan.
After the concentration of formic acid in the chitosan solution is determined, the blending ratio of chitosan and fibroin is determined through the mechanical property test of the blending film, as can be seen from fig. 4, the higher the content of chitosan is, the better the mechanical property of the blending film is, and considering the research direction of the blending material and the important role of the chitosan content in the material in the subsequent heavy metal adsorption research, the ratio of fibroin to chitosan is preferably selected to be 4: 6.
It can be seen from table 1 that the higher the drying temperature, the poorer the mechanical properties, and when the drying temperature is lowered, the film structure of the blend film is tighter, the mechanical properties are improved, and the swelling degree is lowered. Meanwhile, considering the corrosion and damage of formic acid volatilization to drying instruments such as an oven and the like in the drying process of the blending material, the drying at room temperature is selected to be proper.
TABLE 1 statistics of mechanical properties data of blend membranes made at different drying temperatures
Therefore, the differences of the mechanical properties of the blending film dried at different temperatures are obvious, wherein the mechanical properties of the blending film are different, and the mass ratio of the fibroin to the chitosan is different. The fibroin/chitosan blended membrane is prepared by blending the fibroin/chitosan blended membrane under the conditions that the concentration of 50% formic acid and the ratio of chitosan to fibroin are 6:4, drying the mixture at room temperature to form a membrane, and soaking the membrane in ethanol for 30min and then neutralizing the membrane.
Example 3
Preparation of chitosan/fibroin porous membrane by using polyethylene glycol as pore-foaming agent
The first step is as follows: preparing 3% formic acid dissolved chitosan, stirring at a constant speed of 200r/min at a temperature of 30 ℃, adding 98% formic acid into the chitosan solution after the chitosan powder is completely dissolved, enabling the formic acid content in the solution to reach a preset concentration, and uniformly stirring for later use;
the second step is that: directly dissolving regenerated fibroin by 98% formic acid, and stirring at a constant speed of 20 r/min at 30 ℃ until the regenerated fibroin is completely dissolved;
the third step: adding polyethylene glycol (0.2 g, 0.4g, 0.6g, 0.8g, 1 g) into chitosan solution, mixing with chitosan solution, quickly pouring appropriate amount of fibroin solution, stirring at high speed for 5min, standing, and removing foam for one day;
the fourth step: pouring the blend solution after standing and defoaming into a plastic dish by adopting a tape casting method, and drying at proper temperature (room temperature, 30, 50 and 70 ℃) to form a film.
The fifth step: the whole treated blended film was soaked in a 0.5% sodium hydroxide solution for 30min to neutralize the residual acid in the film, after which the film was dried at room temperature for use.
And a sixth step: and soaking the neutralized and dried blend membrane in 500mL of deionized water, dissolving out polyethylene glycol (at room temperature, 30 ℃, 50 ℃, 70 ℃ and 90 ℃), controlling the dissolving-out time (0.5 h, 1h, 3h, 5h and 7 h), and finishing the polyethylene glycol leaching operation. And drying the dissolved blend membrane at room temperature for later use.
According to the content of the polyethylene glycol in the blending solution set in the above examples, the mechanical properties of the blending film material were tested, and as can be seen from fig. 5, the mechanical properties of the blending film generally showed a decreasing trend, reaching the maximum value when the amount of the polyethylene glycol added was 0.2 g.
As can be seen from Table 2, the higher the drying temperature, the better the adsorption effect of the blend membrane after drying, and the membrane material can be dried by properly selecting 50-70 ℃ under the allowable conditions.
TABLE 2 statistics of Cu2+ adsorption performance data for blend membranes made at different drying temperatures
| Drying temperature/. degree.C | Concentration before adsorption/mg.L-1 | Concentration after adsorption/mg.L-1 | Adsorption rate/%) |
| Room temperature (20) | 300 | 211.94 | 29.35 |
| 30 | 300 | 217.19 | 27.60 |
| 50 | 300 | 208.03 | 30.65 |
| 70 | 300 | 195.07 | 34.98 |
In addition to considering the content of the polyethylene glycol and the drying temperature of the blend film, the influence of the temperature of deionized water when the water-soluble polyethylene glycol is in the blend film and the leaching time on the blend film needs to be considered, as can be seen from fig. 6 and 7, the temperature and the time have certain influence on the mechanical properties of the blend film, but the leaching treatment at higher temperature can effectively accelerate the soaking time of the material in water and reduce the dissolution loss of the material, and the temperature is selected to be 90 ℃ and the time is 0.5 h.
FIG. 8 is an SEM image showing polyethylene glycol-fibroin and chitosan blend membrane (PEG-SF/CS) under different magnification. As can be seen from the figure, the addition amount of the polyethylene glycol is 0.2g, after drying at 50 ℃, the PEG-SF/CS membrane obtained by leaching with deionized water at 90 ℃ for 0.5h is distributed with uniform and dense small pit-shaped structures, and the pit diameter distribution is 0.5-1.2 μm.
The blended membrane, pure silk fibroin and pure chitosan are prepared into membranes for comparison of adsorption effects, and as can be seen from table 3, the blended membrane added with polyethylene glycol is greatly improved compared with the pure silk fibroin and pure chitosan membranes.
TABLE 3 showsStatistics of adsorption performance data of co-adsorption material on Cu2+
| Material | Concentration before adsorption/mg.L-1 | Concentration after adsorption/mg.L-1 | Adsorption rate/%) |
| Mean value of SF | 300 | 294.27 | 1.91 |
| CS mean value | 300 | 217.96 | 27.35 |
| PEG-SF/CS mean | 300 | 121.38 | 59.54 |
Claims (10)
1. A chitosan/fibroin-based dual-structure porous adsorption filter material taking polyethylene glycol as a pore-foaming agent is characterized in that: the porous adsorption filter material consists of fibroin, chitosan and a pore-forming agent, the mass ratio of the fibroin to the chitosan is 1-9:9-1, the molecular weight of the chitosan is 50000-100000, the deacetylation degree of the chitosan is 80-95%, and the pore-forming agent is polyethylene glycol.
2. A preparation method of a chitosan/silk fibroin-based dual-structure porous adsorption filter material is characterized by comprising the following steps:
s1, preparing a chitosan solution;
s2, preparing a fibroin solution;
s3, mixing and stirring the chitosan solution, the pore-forming agent and the fibroin solution to obtain a mixed solution;
s4, preparing the composite material with a specified shape and structure from the mixed solution;
s5, carrying out dissolution treatment on the composite material prepared in the step S4 to obtain the porous material with the chitosan/silk fibroin-based dual structure.
3. The preparation method of the chitosan/silk fibroin-based dual-structure porous adsorption filter material as claimed in claim 2, which is characterized by comprising the following steps:
s1, dissolving chitosan in a low-concentration formic acid solution, adding high-concentration formic acid after the chitosan is completely dissolved, and adjusting the chitosan to a proper concentration to obtain a chitosan solution;
s2, dissolving the regenerated silk fibroin into a formic acid solution to obtain a silk fibroin solution;
s3, adding a pore-foaming agent into the chitosan solution prepared in the step S1, mixing and stirring uniformly, adding the fibroin solution prepared in the step S2, mixing and stirring uniformly, standing and defoaming to obtain a mixed solution;
s4, preparing a specified shape structure from the mixed solution after standing, and treating the completely dried composite material with alkali liquor to dissolve out acid to obtain a chitosan/silk fibroin-based composite material;
s5, dissolving the composite material prepared in the step S4 in water at a certain temperature to obtain the porous material with the chitosan/silk fibroin-based dual structure.
4. The method for preparing the porous adsorption filter material with the chitosan/fibroin-based dual structure by using polyethylene glycol as the pore-foaming agent according to claim 3, is characterized in that: the concentration of the low-concentration formic acid solution is 1-10wt% and the concentration of the high-concentration formic acid solution is 30-100% in the step S1.
5. The method for preparing the porous adsorption filter material with the chitosan/fibroin-based dual structure by using polyethylene glycol as the pore-foaming agent according to claim 3, is characterized in that: the concentration of the formic acid solution in the step S2 is 88-98 wt%.
6. The method for preparing the porous adsorption filter material with the chitosan/fibroin-based dual structure by using polyethylene glycol as the pore-foaming agent according to claim 3, is characterized in that: in the step S3, the mass ratio of the silk fibroin to the chitosan in the mixed solution is 1-9:9-1, and the content of the pore-forming agent is 0.5-5%.
7. The method for preparing the porous adsorption filter material with the chitosan/fibroin-based dual structure by using polyethylene glycol as the pore-foaming agent according to claim 3, is characterized in that: the shape of the composite material in the step S4 is any one of a film shape, a porous sponge shape, a tubular shape, a granular shape, a powder shape or a regenerated fiber shape.
8. The method for preparing the porous adsorption filter material with the chitosan/fibroin-based dual structure by using polyethylene glycol as the pore-foaming agent according to claim 3, is characterized in that: in the step S4, sodium hydroxide solution is selected for dissolution treatment, and the concentration of the sodium hydroxide solution is 0.5-5 wt%.
9. The method for preparing the porous adsorption filter material with the chitosan/fibroin-based dual structure by using polyethylene glycol as the pore-foaming agent according to claim 3, is characterized in that: in the step S5, the temperature is 0-90 ℃, and the dissolution treatment time is 0.5-7 h.
10. A porous adsorption filter material with dual structure of chitosan/silk fibroin by using polyethylene glycol as pore-forming agent is applied to biomedical materials, heavy metal treatment, wastewater decomposition and filtration, precious metal recovery, hygienic products and liquid absorption materials.
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| CN114249924A (en) * | 2021-12-27 | 2022-03-29 | 江苏恒富新材料科技有限公司 | Acid and alkali resistant KHA modified wood pulp cotton material and preparation method and application thereof |
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