CN109967008B - Hemicellulose-based hydrogel and preparation method and application thereof - Google Patents
Hemicellulose-based hydrogel and preparation method and application thereof Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0052—Preparation of gels
- B01J13/0065—Preparation of gels containing an organic phase
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- 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
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
- B01J20/267—Cross-linked polymers
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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
- B01J20/28014—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 form
- B01J20/28047—Gels
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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
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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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
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Abstract
The invention discloses a hemicellulose-based hydrogel and a preparation method and application thereof, belonging to the technical field of organic chemical industry. 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 invention directly uses the viscose waste liquid as the raw material to prepare the hemicellulose-based hydrogel, thereby not only effectively solving the treatment problem of the alkaline waste water generated in the viscose production process and improving the economic benefit of enterprise production, but also effectively solving the pollution problem of heavy metal ions in water because the hydrogel can be used for adsorbing the heavy metal ions.
Description
Technical Field
The invention belongs to the technical field of organic chemical industry, and particularly relates to a hemicellulose-based hydrogel as well as a preparation method and application thereof.
Background
The gel is also called as jelly glue, and is a network structure formed by connecting colloid particles or macromolecules in a solution under a certain condition, liquid (gas can be contained in the xerogel, so the gel is also called as aerogel) serving as a dispersion medium is filled in gaps of the gel, the hydrogel is a new material consisting of macromolecules containing hydrophilic groups and a crosslinking structure, and the macromolecule network can absorb a large amount of water and maintain a certain shape. Generally, the water absorption capacity of the high-molecular hydrogel can be dozens of times to thousands of times of the self-mass, and is different from the water absorption principle (capillary adsorption) of materials such as cotton sponge and the like, water molecules of the hydrogel are combined with hydrophilic groups in a network structure through chemical bonds, so that the hydrogel is not easy to lose water even under pressure and has strong water retention capacity. The hydrogel is widely applied to the medical field, environment, agriculture and the like, such as soft contact lenses, tissue engineering, drug delivery, wound dressings, biosensors, biomimetic mineralization and cancer treatment, heavy metal ion adsorbents, water-retaining agents and the like.
In recent years, the ecological environment damage and pollution are increasingly severe, which has serious influence on the health and survival of human beings, wherein the heavy metal elements have serious pollution and damage to the environment. Heavy metals are inorganic pollutants, which are highly toxic and potentially hazardous, can be enriched in water and organisms, can contaminate water and organisms, can be absorbed by crops and enriched into the food chain, and are potentially hazardous to human and animal health. It is statistically average that 340 tens of thousands of copper are discharged worldwide each year. Most of the heavy metal pollutants enter the water body through different ways, so that the water resource is polluted.
With the decreasing total amount of non-renewable resources such as petroleum and coal, the conversion of renewable resources to obtain new materials, high-valued energy, chemical raw materials and drugs is becoming a new trend of development, and hemicellulose becomes an important branch in the research of the utilization of renewable resources. The content of hemicellulose in plant resources is second to cellulose, and the plant resources are inexhaustible regenerative plant resources. The content of hemicellulose in plant resources is 1/4-1/3, and the content of hemicellulose in different plant species is different, for example, the content of hemicellulose in corn stalks is 28.0%, the content of hemicellulose in barley grass is 34.9%, the content of hemicellulose in wheat straw is 38.8%, the content of straw is 35.8%, and the content of hemicellulose in ryegrass is 36.9%. This relatively high hemicellulose content makes them useful as novel raw materials for industrial polymers to replace petrochemical products that are harmful to the environment.
The viscose fiber is cellulose fiber obtained by extracting and remolding fiber molecules from natural wood cellulose by taking wood pulp as a raw material, and is an important basic raw material of the textile industry of China as the natural renewable cellulose fiber. According to 2016 years of statistics, the annual output of the Chinese viscose fibers reaches 380 ten thousand t; however, viscose fiber produces a large amount of waste press liquor in the production process, wherein the content of hemicellulose is about 48g/L, and the total amount of hemicellulose is about 54.7 ten thousand t all the year round. At present, the membrane separation process is mainly adopted in China to effectively separate hemicellulose from alkali liquor in high-concentration waste alkali liquor, so that the alkali liquor is efficiently and economically recovered and treated, and the membrane separation process is quickly popularized and applied in industrial production; however, only lye is recovered by membrane separation, and the remaining high-concentration hemicellulose wastewater is discharged or concentrated and collected and then burned, which not only causes resource waste and increases product cost, but also causes serious environmental pollution.
Schuppen et al, in "preparation and functional research of hemicellulose hydrogel" disclose that hemicellulose is used as a raw material, and is graft-copolymerized with Acrylic Acid (AA) under the action of an initiator Ammonium Persulfate (APS), and hydrogel is prepared under the action of a crosslinking agent N, N-Methylene Bisacrylamide (MBA). The raw material hemicellulose is hemicellulose powder after extraction and purification, and the extraction process of the hemicellulose in viscose waste water comprises the steps of viscose waste water neutralization, solvent extraction, solvent removal and drying, so that the problems of long process flow, large equipment investment, high neutralization acid consumption, high salt concentration in the waste water, high solvent loss, energy consumption and the like exist. The invention discloses a hydrogel for soil improvement and application thereof, which is named as CN 201711401140X and takes hemicellulose waste liquid as a solvent to be directly mixed with a hydrogel monomer and a cross-linking agent to prepare the hydrogel, so that the problems of high reaction temperature and long reaction time exist in the reaction process.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a hemicellulose-based hydrogel. The invention also aims to provide a preparation method of the hemicellulose-based hydrogel, which takes viscose waste water as a raw material and modifies the viscose waste water by glycidyl methacrylate. The invention also aims to provide the application of the hemicellulose hydrogel in adsorbing heavy metal ions in water.
The technical scheme is as follows: in order to solve the problems, the technical scheme adopted by the invention is as follows:
a preparation method of hemicellulose-based hydrogel comprises the following steps of carrying out graft modification on viscose waste liquid by using allyl glycidyl ether (XY680), Glycidyl Acrylate (GA) or Glycidyl Methacrylate (GMA); then generating free radicals under the action of Ammonium Persulfate (APS) and N, N, N ', N' -Tetramethylethylenediamine (TEMDA), and carrying out graft copolymerization with Acrylic Acid (AA); adding a cross-linking agent N, N-Methylene Bisacrylamide (MBA), stirring and reacting to obtain a primary hydrogel product, and performing alkali treatment and drying to obtain the hemicellulose-based hydrogel. The method comprises the following specific steps:
step 1, adding viscose waste liquid into a reactor, stirring, and heating to 60-80 ℃ to obtain initial raw material liquid;
step 2, dripping XY680, GA or GMA into the liquid, stirring for 2-3 h, and cooling to room temperature;
step 3, introducing nitrogen to remove air in the reactor, adding APS and TEMDA to react for 1-5min, then dropwise adding AA, reacting for 1-2min after dropwise adding, adding MBA, and reacting for 20-60min with stirring;
step 4, standing in a nitrogen atmosphere to obtain a primary hydrogel product;
and 5, soaking the primary hydrogel product in a sodium hydroxide solution, washing with distilled water, and drying to obtain the hemicellulose-based hydrogel.
Preferably, the volume ratio of the XY680, GA or GMA to the viscose waste liquid is 0.35-0.7: 1.
Preferably, the dosage ratio of the APS to the viscose waste liquid is 5mg/mL, and the dosage ratio of the TEMDA to the viscose waste liquid is 7.5 mg/mL.
Preferably, the volume ratio of the AA to the viscose waste liquid is 0.2-0.4: 1.
Preferably, the ratio of the MBA dosage to the viscose waste liquid dosage is 2.5-7.5 mg/mL.
Preferably, the drying temperature is 60 ℃.
The hemicellulose-based hydrogel obtained by the preparation method of the hemicellulose-based hydrogel.
The hemicellulose-based hydrogel is applied to adsorption of heavy metal ions.
Has the advantages that: compared with the prior art, the invention has the advantages that:
(1) the viscose waste liquid is used as a raw material, and hemicellulose molecules in the viscose waste liquid contain a large amount of hydrophilic groups, so that the viscose waste liquid is an important raw material for synthesizing hydrogel.
(2) The method has the advantages of renewable raw materials, environmentally degradable products, wide application and the like, reasonably utilizes the viscose waste liquid, modifies the viscose waste liquid by using GMA, effectively converts the biomass hemicellulose into the hydrogel with high added value, and has great significance for realizing waste recycling and environmental protection.
(3) The method fully utilizes the viscose waste liquid to prepare the hemicellulose-based hydrogel, the hemicellulose in the viscose waste liquid does not need to be extracted, the hydrogel is prepared by directly grafting with GMA, a hemicellulose extraction process is not needed, the cost is low, the process is simple, and the method is easy to put into industrial production.
(4) The invention directly takes the viscose waste liquid as the raw material to prepare the hemicellulose-based hydrogel, the whole process has no discharge, not only effectively solves the treatment problem of alkaline waste water generated in the viscose production process and improves the economic benefit of enterprise production, but also the hydrogel can be used for heavy metal ion adsorption, can effectively solve the pollution problem of heavy metal ions in water and can treat Cu2+And Cd2+The adsorption amounts of (A) and (B) were 195mg/g and 344mg/g, respectively.
(5) The invention adopts the viscose waste liquid as the raw material, the alkali in the waste liquid is utilized, the addition of alkali and water is not needed when the hydrogel is prepared, and the hydrogel preparation cost is further reduced.
(6) According to the invention, GMA is used for directly modifying hemicellulose in the waste liquid, double bonds are introduced under the condition of not reducing the quantity of hydroxyl functions of the hemicellulose, so that the reaction temperature is lower, the reaction time is shorter, and the formed hydrogel also has a certain swelling property.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below.
The viscose waste liquid used in the invention is provided by Yibin Silya group Limited, and the waste alkali liquid is squeezed: the concentration is 18.5% (185g/L), and the hemicellulose is 40-45 g/L; XY680, GA, GMA are industrial grade, offered by New and remote technologies, Inc., Anhui.
The hemicellulose-based hydrogel contains a large amount of carboxyl and hydroxyl, has certain swelling performance, and has the following calculation formula of swelling ratio:
wherein SR refers to the swelling ratio of the hydrogel, g/g; ws refers to the weight of the hydrogel at swelling equilibrium, g; wd refers to the dry weight of the hydrogel, g.
The hydrogel is used for adsorbing heavy metal ions, and the calculation formula of the adsorption amount is as follows:
wherein Q is adsorption capacity, mg/g; v is the volume of the added metal solution, L; m is the mass of the added xerogel, g; c0、CeThe concentration of the metal ions in the solution before and after adsorption is mg/L.
Example 1
Step 1, taking 20mL of viscose waste liquid into a 100mL four-neck flask, and heating to 60 ℃ under the stirring condition to obtain initial raw material liquid;
step 2, dripping 10mL of GMA into the liquid, stirring for 2h, and cooling to room temperature;
step 3, introducing nitrogen to remove air in the reactor, adding 0.10g of APS and 0.15g of TEMDA, reacting for 2min, then dropwise adding 8mL of AA, reacting for 2min after dropwise adding, adding 0.15g of MBA, and stirring to react for 60 min;
step 4, pouring the liquid in the reactor into a beaker, and standing for 12 hours in a nitrogen atmosphere to obtain a primary hydrogel product;
step 5, soaking the obtained primary hydrogel product in a sodium hydroxide solution for 24 hours; then washed three times with 100mL of distilled water and dried at 60 c to obtain a hemicellulose-based hydrogel.
Swelling ratio test: a certain amount of xerogel is taken, the mass of the xerogel before and after the xerogel is balanced by swelling is weighed, and the swelling ratio of the xerogel is calculated to be 29 according to a formula.
Heavy metal ion adsorption experiment: 0.01g of the obtained hydrogel was added to 50mL of 100mg/L Cu2+And Cd2+In the solution, sampling is carried out after 24 hours of adsorption, the ion concentration after adsorption is detected by an atomic spectrophotometer, and Cu is obtained by calculation2+And Cd2+The adsorption amounts were 115mg/g and 230mg/g, respectively.
Example 2
Step 1, taking 20mL of viscose waste liquid into a 100mL four-neck flask, and heating to 80 ℃ under the stirring condition to obtain initial raw material liquid;
step 2, dripping 10mL of GMA into the liquid, stirring for 2h, and cooling to room temperature;
and 3, when the temperature is reduced to room temperature, introducing nitrogen to remove air in the reactor, adding 0.10g of APS and 0.15g of TEMDA, reacting for 2min, then dropwise adding 8mL of AA, completing the dropwise addition reaction for 2min, adding 0.15g of MBA, and stirring and reacting for 60 min.
And 4, pouring the liquid in the reactor into a beaker, and standing for 12 hours under the nitrogen atmosphere to obtain a primary hydrogel product.
Step 5, soaking the obtained primary hydrogel product in a sodium hydroxide solution for 24 hours; then washed three times with 100mL of distilled water and dried at 60 c to obtain a hemicellulose-based hydrogel.
Swelling ratio test: a certain amount of xerogel is taken, the mass of the xerogel before and after the xerogel is balanced by swelling is weighed, and the swelling ratio is calculated to be 35 according to a formula.
Heavy metal ion adsorption experiment: 0.01g of the obtained hydrogel was added to 50mL of 100mg/L Cu2+And Cd2+In the solution, sampling is carried out after 24 hours of adsorption, the ion concentration after adsorption is detected by an atomic spectrophotometer, and Cu is obtained by calculation2+And Cd2+The adsorption amounts were 159mg/g and 294mg/g, respectively.
Example 3
Step 1, taking 20mL of viscose waste liquid into a 100mL four-neck flask, and heating to 60 ℃ under the stirring condition to obtain initial raw material liquid;
step 2, dropwise adding 14mL of GMA into the liquid, stirring for 2h, and cooling to room temperature;
and 3, when the temperature is reduced to room temperature, introducing nitrogen to remove air in the reactor, adding 0.10g of APS and 0.15g of TEMDA, reacting for 2min, then dropwise adding 8mL of AA, completing the dropwise addition reaction for 2min, adding 0.15g of MBA, and stirring and reacting for 60 min.
And 4, pouring the liquid in the reactor into a beaker, and standing for 12 hours under the nitrogen atmosphere to obtain a primary hydrogel product.
Step 5, soaking the obtained primary hydrogel product in a sodium hydroxide solution for 24 hours; then washed three times with 100mL of distilled water and dried at 60 c to obtain a hemicellulose-based hydrogel.
Swelling ratio test: a certain amount of xerogel is taken, the mass of the xerogel before and after the xerogel is balanced by swelling is weighed, and the swelling ratio of the xerogel is calculated to be 16 according to a formula.
Heavy metal ion adsorption experiment: 0.01g of the obtained hydrogel was added to 50mL of 100mg/L Cu2+And Cd2+In the solution, sampling is carried out after 24 hours of adsorption, the ion concentration after adsorption is detected by an atomic spectrophotometer, and Cu is obtained by calculation2+And Cd2+The adsorption amounts were 181mg/g and 337mg/g, respectively.
Example 4
Step 1, taking 20mL of viscose waste liquid into a 100mL four-neck flask, and heating to 60 ℃ under the stirring condition to obtain initial raw material liquid;
step 2, dripping 10mL of GMA into the liquid, stirring for 2h, and cooling to room temperature;
step 3, when the temperature is reduced to room temperature, introducing nitrogen to remove air in the reactor, adding 0.10g of APS and 0.15g of TEMDA, reacting for 2min, then dropwise adding 4mL of AA, completing the dropwise addition reaction for 2min, adding 0.15g of MBA, and stirring and reacting for 60 min;
step 4, pouring the liquid in the reactor into a beaker, and standing for 12 hours in a nitrogen atmosphere to obtain a primary hydrogel product;
step 5, soaking the obtained primary hydrogel product in a sodium hydroxide solution for 24 hours; then washed three times with 100mL of distilled water and dried at 60 c to obtain a hemicellulose-based hydrogel.
Swelling ratio test: a certain amount of xerogel is taken, the mass of the xerogel before and after the xerogel is balanced by swelling is weighed, and the swelling ratio is calculated to be 31 according to a formula.
Heavy metal ion adsorption experiment: 0.01g of the obtained hydrogel was added to 50mL of 100mg/L Cu2+And Cd2+In the solution, sampling is carried out after 24 hours of adsorption, the ion concentration after adsorption is detected by an atomic spectrophotometer, and Cu is obtained by calculation2+And Cd2+The adsorption amounts were 134mg/g and 209mg/g, respectively.
Example 5
Step 1, taking 20mL of viscose waste liquid into a 100mL four-neck flask, and heating to 60 ℃ under the stirring condition to obtain initial raw material liquid;
step 2, dropwise adding 7mL of GMA into the liquid, stirring for 2h, and cooling to room temperature;
step 3, when the temperature is reduced to room temperature, introducing nitrogen to remove air in the reactor, adding 0.10g of APS and 0.15g of TEMDA, reacting for 2min, then dropwise adding 8mL of AA, completing the dropwise addition reaction for 2min, adding 0.05g of MBA, and stirring and reacting for 60 min;
and 4, pouring the liquid in the reactor into a beaker, and standing for 12 hours under the nitrogen atmosphere to obtain a primary hydrogel product.
Step 5, soaking the obtained primary hydrogel product in a sodium hydroxide solution for 24 hours; then washed three times with 100mL of distilled water and dried at 60 c to obtain a hemicellulose-based hydrogel.
Swelling ratio test: a certain amount of xerogel is taken, the mass of the xerogel before and after the xerogel is balanced by swelling is weighed, and the swelling ratio of the xerogel is 111 according to a formula.
Heavy metal ion adsorption experiment: 0.01g of the obtained hydrogel was added to 50mL of 100mg/L Cu2+And Cd2+In the solution, sampling is carried out after 24 hours of adsorption, the ion concentration after adsorption is detected by an atomic spectrophotometer, and Cu is obtained by calculation2+And Cd2+The adsorption amounts were 148mg/g and 263mg/g, respectively.
Example 6
Step 1, taking 20mL of viscose waste liquid into a 100mL four-neck flask, and heating to 80 ℃ under the stirring condition to obtain initial raw material liquid;
step 2, dripping 10mL of XY680 into the liquid, stirring for 2h, and cooling to room temperature;
and 3, when the temperature is reduced to room temperature, introducing nitrogen to remove air in the reactor, adding 0.10g of APS and 0.15g of TEMDA, reacting for 2min, then dropwise adding 8mL of AA, completing the dropwise addition reaction for 2min, adding 0.15g of MBA, and stirring and reacting for 60 min.
And 4, pouring the liquid in the reactor into a beaker, and standing for 12 hours under the nitrogen atmosphere to obtain a primary hydrogel product.
Step 5, soaking the obtained primary hydrogel product in a sodium hydroxide solution for 24 hours; then washed three times with 100mL of distilled water and dried at 60 c to obtain a hemicellulose-based hydrogel.
Swelling ratio test: a certain amount of xerogel is taken, the mass of the xerogel before and after the xerogel is balanced by swelling is weighed, and the swelling ratio of the xerogel is calculated to be 28 according to a formula.
Heavy metal ion adsorption experiment: 0.01g of the obtained hydrogel was added to 50mL of 100mg/L Cu2+And Cd2+In the solution, sampling is carried out after 24 hours of adsorption, the ion concentration after adsorption is detected by an atomic spectrophotometer, and Cu is obtained by calculation2+And Cd2+The adsorption amounts were 155mg/g and 206mg/g, respectively.
Example 7
Step 1, taking 20mL of viscose waste liquid into a 100mL four-neck flask, and heating to 80 ℃ under the stirring condition to obtain initial raw material liquid;
step 2, dripping 10mL of GA into the liquid, stirring for 2h, and cooling to room temperature;
and 3, when the temperature is reduced to room temperature, introducing nitrogen to remove air in the reactor, adding 0.10g of APS and 0.15g of TEMDA, reacting for 2min, then dropwise adding 8mL of AA, completing the dropwise addition reaction for 2min, adding 0.15g of MBA, and stirring and reacting for 60 min.
And 4, pouring the liquid in the reactor into a beaker, and standing for 12 hours under the nitrogen atmosphere to obtain a primary hydrogel product.
Step 5, soaking the obtained primary hydrogel product in a sodium hydroxide solution for 24 hours; then washed three times with 100mL of distilled water and dried at 60 c to obtain a hemicellulose-based hydrogel.
Swelling ratio test: a certain amount of xerogel is taken, the mass of the xerogel before and after the xerogel is balanced by swelling is weighed, and the swelling ratio is calculated to be 41 according to a formula.
Heavy metal ion adsorption experiment: 0.01g of the obtained hydrogel was added to 50mL of 100mg/L Cu2+And Cd2+In the solution, sampling is carried out after 24 hours of adsorption, the ion concentration after adsorption is detected by an atomic spectrophotometer, and Cu is obtained by calculation2+And Cd2+The adsorption amounts were 162mg/g and 286mg/g, respectively.
Example 8
Step 1, taking 20mL of viscose waste liquid into a 100mL four-neck flask, and heating to 80 ℃ under the stirring condition to obtain initial raw material liquid;
step 2, dripping 10mL of GMA into the liquid, stirring for 2h, and cooling to room temperature;
and 3, when the temperature is reduced to room temperature, introducing nitrogen to remove air in the reactor, adding 0.10g of APS and 0.15g of TEMDA, reacting for 2min, then dropwise adding 12mL of AA, completing the dropwise addition reaction for 2min, adding 0.15g of MBA, and stirring and reacting for 60 min.
And 4, pouring the liquid in the reactor into a beaker, and standing for 12 hours under the nitrogen atmosphere to obtain a primary hydrogel product.
Step 5, soaking the obtained primary hydrogel product in a sodium hydroxide solution for 24 hours; then washed three times with 100mL of distilled water and dried at 60 c to obtain a hemicellulose-based hydrogel.
Regeneration adsorption test experiment: 50mg of hydrogel was weighed, placed in a 250mL Erlenmeyer flask, and added200mL of 100mg/L Cu2+And Cd2+A heavy metal ion solution. Shaking for 24h at room temperature, sampling in a 10mL centrifuge tube, adding HCl solution into the rest solution, adjusting pH to 1, shaking for 24h, filtering, drying, recycling for four times, measuring the concentration of heavy metal ions in the solution before and after each recycling by using an atomic spectrophotometer, and calculating the corresponding adsorption capacity.
The results are given in the following table:
| number of cycles | Cu2+Adsorption Capacity (mg/g) | Cd2+Adsorption Capacity (mg/g) |
| 0 | 179 | 261 |
| 1 | 103 | 212 |
| 2 | 50 | 167 |
| 3 | 23 | 78 |
| 4 | 17 | 72 |
Claims (4)
1. The preparation method of the hemicellulose-based hydrogel is characterized in that allyl glycidyl ether, glycidyl acrylate or glycidyl methacrylate is used for carrying out graft modification on hemicellulose in viscose waste liquid; 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 a hemicellulose-based hydrogel; the volume ratio of the allyl glycidyl ether, the glycidyl acrylate or the glycidyl methacrylate to the viscose waste liquid is 0.35-0.7: 1; the mass dosage of the ammonium persulfate and the volume dosage of the viscose waste liquid are 5mg/mL, and the mass dosage of the N, N, N ', N' -tetramethyl ethylenediamine and the volume dosage of the viscose waste liquid are 7.5 mg/mL; the volume ratio of the acrylic acid to the viscose waste liquid is 0.2-0.4: 1; the mass dosage of the N, N-methylene bisacrylamide and the volume dosage of the viscose waste liquid are in a ratio of 2.5-7.5 mg/mL; the method comprises the following specific steps:
step 1, adding viscose waste liquid into a reactor, stirring, and heating to 60-80 ℃ to obtain initial raw material liquid;
step 2, dripping allyl glycidyl ether, glycidyl acrylate or glycidyl methacrylate into the raw material liquid, stirring for reacting for 2-3 hours, and then cooling to room temperature;
step 3, introducing nitrogen to remove air in the reactor, adding ammonium persulfate and N, N, N ', N' -tetramethylethylenediamine to react for 1-5min, then dropwise adding acrylic acid, reacting for 1-2min after dropwise adding, adding N, N-methylene bisacrylamide, and stirring to react for 20-60 min;
step 4, standing in a nitrogen atmosphere to obtain a primary hydrogel product;
and 5, soaking the primary hydrogel product in a sodium hydroxide solution, washing with distilled water, and drying to obtain the hemicellulose-based hydrogel.
2. The method for preparing a hemicellulose-based hydrogel according to claim 1, wherein the drying temperature is 60 ℃.
3. The hemicellulose-based hydrogel obtained by the method of preparing the hemicellulose-based hydrogel of claim 1 or 2.
4. Use of the hemicellulose-based hydrogel of claim 3 for adsorbing heavy metal ions.
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