CN112354524A - Molecularly imprinted chitosan/titanium dioxide composite hydrogel and application thereof in treating high-concentration phenolic wastewater - Google Patents
Molecularly imprinted chitosan/titanium dioxide composite hydrogel and application thereof in treating high-concentration phenolic wastewater Download PDFInfo
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 239000000017 hydrogel Substances 0.000 title claims abstract description 78
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000002131 composite material Substances 0.000 title claims abstract description 59
- 229920001661 Chitosan Polymers 0.000 title claims abstract description 37
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 36
- 239000002351 wastewater Substances 0.000 title claims abstract description 25
- 239000000126 substance Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 12
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 10
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 229960005070 ascorbic acid Drugs 0.000 claims description 5
- 235000010323 ascorbic acid Nutrition 0.000 claims description 5
- 239000011668 ascorbic acid Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 28
- 238000003795 desorption Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 239000004005 microsphere Substances 0.000 abstract description 3
- 239000002105 nanoparticle Substances 0.000 abstract description 3
- 125000003277 amino group Chemical group 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- 239000002077 nanosphere Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 8
- 239000012086 standard solution Substances 0.000 description 5
- 239000012528 membrane Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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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
- B01J20/24—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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- 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
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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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
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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Abstract
本发明公开了一种分子印迹的壳聚糖/二氧化钛复合水凝胶及处理高浓度含酚废水的应用，选用壳聚糖和二氧化钛复合成水凝胶，加入苯酚，使苯酚的羟基和壳聚糖的氨基通过氢键作用形成组装体，随后附着在二氧化钛纳米粒子表面形成分子印迹纳米微球，然后通过溶剂洗脱分子印迹微球中的模板分子苯酚，留下的空穴形状、大小与目标分子苯酚相吻合，从而实现吸附废水中的酚类物质。本发明复合水凝胶重复7次吸附、解吸试验，其对酚类物质的吸附能力仍然具有90％，可以有效保证水凝胶的反复使用性能，吸附性和可再生性能够满足工业去除废水中酚类物质的环保要求与经济要求。
The invention discloses a molecularly imprinted chitosan/titanium dioxide composite hydrogel and its application for treating high-concentration phenol-containing wastewater. Chitosan and titanium dioxide are selected to form a composite hydrogel, and phenol is added to make the hydroxyl groups of phenol and chitosan The amino group of sugar forms an assembly through hydrogen bonding, and then attaches to the surface of titanium dioxide nanoparticles to form molecularly imprinted nanospheres, and then the template molecule phenol in the molecularly imprinted microspheres is eluted by solvent, leaving the shape, size and target of the hole. Molecular phenol is consistent, so as to realize the adsorption of phenolic substances in wastewater. The composite hydrogel of the present invention repeats 7 times of adsorption and desorption tests, and its adsorption capacity to phenolic substances still has 90%, which can effectively ensure the repeated use performance of the hydrogel, and the adsorption and regenerability can meet the requirements of industrial removal of wastewater. Environmental requirements and economic requirements of phenolic substances.
Description
Technical Field
The invention belongs to the technical field of phenol removal of high-concentration phenol-containing wastewater, and particularly relates to molecularly imprinted composite hydrogel and application of the composite hydrogel in removing phenolic substances from the high-concentration phenol-containing wastewater.
Background
The phenol organic matters are main components of organic pollutants difficult to degrade in the semi-coke wastewater, have toxicity, bioaccumulation and semi-volatility, are harmful to the environment and human health, and inhibit biological activity, and are a difficulty in water pollution control. The principle of the adsorption method is that the adsorption of the adsorbent is utilized to adsorb organic pollutants in the wastewater on the surfaces of the pore channels of the adsorbent, and the adsorption method has the advantages of stable effect, simple process and no secondary pollution, but has the defects of small pore diameter of the adsorbent, easy occurrence of blockage phenomenon, high regeneration cost and the like; the membrane separation method mainly comprises a liquid membrane separation technology and a nanofiltration technology, has the advantages of no chemical reaction, no phase change, high separation efficiency, small volume, convenient operation, low energy consumption and the like, but also has the defects of difficult liquid membrane forming, complex process flow and difficult liquid membrane maintenance for a long time; the extraction method has the advantages that two phases are mutually soluble to a certain degree in the extraction process, so that the loss of an extractant and secondary pollution are easily caused; the biochemical treatment method is only suitable for low-concentration phenol-containing wastewater, but not for high-concentration phenol-containing wastewater, and valuable phenolic substances cannot be recovered. Therefore, the search for an adsorption material with the advantages of high treatment efficiency, low cost, low energy consumption and the like is the key of the efficiency and the environmental protection property for removing the phenolic substances in the high-concentration phenol-containing wastewater by an adsorption method.
Disclosure of Invention
The invention aims to provide a molecularly imprinted chitosan/titanium dioxide composite hydrogel for adsorbing and treating phenolic substances in high-concentration phenolic wastewater.
Aiming at the purposes, the molecularly imprinted chitosan/titanium dioxide composite hydrogel is prepared by the following method: adding chitosan and phenol into isopropanol, and uniformly mixing and stirring to obtain a chitosan-phenol solution; adding titanium dioxide, hydrochloric acid and ferric trichloride into deionized water, and stirring and mixing uniformly to obtain a nano titanium dioxide dispersion liquid; uniformly mixing and stirring the chitosan-phenol solution and the nano titanium dioxide dispersion liquid, adding ascorbic acid, stirring and reacting for 3-12 hours at 40-80 ℃, washing and soaking a product obtained by the reaction with distilled water to obtain hydrogel, then placing the hydrogel in a disodium hydrogen phosphate aqueous solution, eluting template molecular phenol in a molecular imprinting layer by using a potentiostatic method, adding distilled water again for washing, and finally obtaining the molecularly imprinted chitosan/titanium dioxide composite hydrogel.
In the preparation method, the molar ratio of the chitosan to the phenol is preferably 1: 0.2-0.4, the mass ratio of the phenol to the ferric trichloride and the HCl is preferably 1: 3-5: 40-45, and the mass ratio of the chitosan to the titanium dioxide and the ascorbic acid is preferably 1: 0.4-0.5: 0.07-0.1.
In the above preparation method, it is further preferable that the reaction is carried out at 50 to 70 ℃ for 5 to 6 hours with stirring.
In the preparation method, the soaking time with the deionized water is 2-3 days.
In the preparation method, the mass concentration of the disodium hydrogen phosphate in the disodium hydrogen phosphate aqueous solution is 2-5%.
The invention discloses an application of molecularly imprinted chitosan/titanium dioxide composite hydrogel in removing phenolic substances in high-concentration phenolic wastewater, which comprises the following steps: adding the composite hydrogel into high-concentration phenol-containing wastewater, controlling the mass ratio of the phenol substances to the composite hydrogel to be 1: 35-55 g, and adsorbing at the constant temperature of 30-40 ℃ for 2-3 hours.
In the application of the molecularly imprinted chitosan/titanium dioxide composite hydrogel in removing phenolic substances in high-concentration phenol-containing wastewater, the composite hydrogel after adsorbing the phenolic substances is preferably placed in a disodium hydrogen phosphate aqueous solution with the mass concentration of 2% -5%, the phenolic substances in the molecularly imprinted layer are eluted by a constant potential method, and then distilled water is added for washing and reusing.
The invention has the following beneficial effects:
according to the invention, the molecularly imprinted chitosan/titanium dioxide composite hydrogel is prepared by a hydrothermal method, an assembly can be formed by the action of an amino group in chitosan and-OH on phenol in wastewater through a hydrogen bond, phenol is embedded into chitosan through the interaction of the hydrogen bond in the polymerization process and is attached to the surface of titanium dioxide nanoparticles to form molecularly imprinted nano microspheres, then template molecular phenol in the molecularly imprinted microspheres is eluted by a solvent, and the shape and size of a remained cavity are matched with that of a target molecular phenol, so that phenol substances are selectively removed in a targeted manner in the subsequent wastewater treatment, other impurities are rejected from entering the hydrogel, and the pore channel blockage of the hydrogel can be avoided. The adsorption and desorption tests are repeated for 7 times by using the adsorbing material, and the adsorption capacity of the adsorbing material on the phenolic substances is still 90 percent. The composite hydrogel has abundant chemical functional groups and hole structures, so that the adsorption performance, the mechanical property and the utilization rate of the traditional gel can be obviously improved, and the repeated use performance of the hydrogel can be effectively ensured. Therefore, the adsorbability and the regenerability of the molecularly imprinted chitosan/titanium dioxide composite hydrogel can meet the environmental protection requirement and the economic requirement of industrially removing phenolic substances in wastewater.
Drawings
FIG. 1 is SEM images of the composite hydrogel before and after adsorption of high-concentration phenol-containing wastewater.
FIG. 2 is a graph showing the effect of temperature on phenol removal.
FIG. 3 is a graph showing the effect of adsorption time on phenol removal.
FIG. 4 shows the influence of the amount of the composite hydrogel charged on the phenol removal rate.
FIG. 5 is a graph showing the effect of the number of cycles of the composite hydrogel on the amount of phenol adsorbed.
Detailed Description
The invention will be further described in detail with reference to the following figures and examples, but the scope of the invention is not limited to these examples.
Example 1
Adding 0.48g (3mmol) of chitosan and 0.066g (0.7mmol) of phenol into 12mL of isopropanol, and uniformly mixing and stirring to obtain a chitosan-phenol solution; adding 0.2g of titanium dioxide, 0.2g of ferric trichloride and 28.32g of hydrochloric acid with the mass concentration of 10% into 30g of deionized water, and uniformly mixing and stirring to obtain a titanium dioxide dispersion liquid; then the obtained chitosan-phenol solution and the titanium dioxide dispersion liquid are stirred and mixed evenly, 10mL of deionized water solution containing 0.035g of ascorbic acid is added, and the mixture is stirred and reacted for 6 hours in a constant temperature water bath at 60 ℃. Washing the product obtained by the reaction with distilled water, soaking the product in deionized water for 3 days, changing water every day to remove the unreacted gel part, then placing the hydrogel in a disodium hydrogen phosphate aqueous solution with the mass concentration of 2.7%, eluting the template molecule phenol in the molecular imprinting layer by using a potentiostatic method (working voltage of 1.5V), adding distilled water again for washing, and finally obtaining the molecularly imprinted chitosan/titanium dioxide composite hydrogel.
As can be seen from FIG. 1, the prepared composite hydrogel has uneven surface and numerous protrusions and ravines, and cylindrical protrusions with the diameter ranging from 30 nm to 50nm are distributed on the surface of the hydrogel, so that the specific surface area of the hydrogel is increased, and the hydrogel can adsorb phenol. The free nanoparticles present alone are not seen in the figure, indicating that the synthesized hydrogel has good stability. The hydrogel after adsorbing phenol has a more obvious difference from the hydrogel before adsorbing. The surface of the hydrogel after adsorbing the phenol becomes relatively smooth and has no obvious unevenness any more, because the hydrogel has better phenol adsorption capacity, so that the surface of the hydrogel becomes smooth.
Example 2
Application of molecularly imprinted chitosan/titanium dioxide composite hydrogel prepared in example 1 in treatment of high-concentration phenol-containing wastewater
1. Effect of temperature on phenol removal
6 parts of 100mL phenol standard solution (the content of phenol is 0.4g/L) is taken, 1.6g of composite hydrogel is added, the concentration of phenol is tested after adsorption for 2h at constant temperature of 15, 20, 25, 30, 35 and 40 ℃, the removal rate of phenol is calculated, and the result is shown in figure 2. As can be seen from fig. 2: the suitable temperature for adsorbing phenol by the composite hydrogel is 30-35 ℃, and the removal rate of resorcinol at 35 ℃ is 95%. When the temperature is lower than 30 ℃, the removal rate of phenol is obviously reduced, and when the temperature is higher than 35 ℃, the removal rate is basically unchanged. This is because the number of active groups on the surface of the composite hydrogel is temperature dependent, and increasing the temperature increases the number of active groups on the surface, thereby increasing the adsorption effect. But when reaching a certain temperature, the surface active groups are saturated, and the adsorption reaches dynamic balance.
2. Effect of adsorption time on phenol removal
6 parts of 100mL phenol standard solution (the content of phenol is 0.4g/L) is taken, 1.6g of composite hydrogel is added, the phenol concentration is tested after 1.2, 1.7, 2.2, 2.7, 3.2 and 3.7h of constant temperature adsorption at 30 ℃, the phenol removal rate is calculated, and the result is shown in figure 3. As can be seen from fig. 3: the ideal adsorption time of the composite hydrogel for adsorbing phenol is 2.2-2.7 h, and the removal rate of resorcinol after 2.2h adsorption reaches 92%. After the adsorption time is longer than 2.7h, phenol is resolved, and the removal rate is reduced.
3. Influence of input amount of composite hydrogel on phenol removal rate
6 parts of 100mL phenol standard solution (the content of phenol is 0.4g/L) are respectively added with 0.3, 0.7, 1.1, 1.5, 1.8 and 2.1g of composite hydrogel, the mixture is adsorbed at the constant temperature of 30 ℃ for 2.7h, then the phenol concentration is tested by adopting a spectrophotometry method, and the phenol removal rate is calculated, and the result is shown in figure 4. As can be seen from fig. 4: when the amount of the composite hydrogel charged was 1.5, 1.8 and 2.1g, the removal rates of phenol were 93.3%, 93.4% and 93.5%, respectively. The input amount of the composite hydrogel is too low, the phenol removal effect is poor, and the phenol removal rate is improved along with the increase of the input amount of the composite hydrogel; however, when the amount of the phenol is increased to a certain amount, the adsorption tends to be balanced, and the phenol removal rate is not changed much by increasing the input amount. The test result shows that: the best molecular engrafted chitosan/titanium dioxide composite hydrogel input amount is 1.5g for 100mL of phenol standard solution.
4. Influence of composite hydrogel recycling times on phenol adsorption capacity
Taking 100mL of phenol standard solution (the content of phenol is 0.4g/L), adding 1.5g of composite hydrogel, adsorbing at 30 ℃ for 2.7h at constant temperature, airing the hydrogel adsorbing high-concentration phenol-containing wastewater at room temperature, placing the composite hydrogel in a disodium hydrogen phosphate aqueous solution with the mass concentration of 2.7%, and eluting phenol in a molecular imprinting layer by a potentiostatic method. The adsorption and desorption tests were repeated 7 times on the obtained composite hydrogel, and the adsorption amount of the composite hydrogel to phenol was measured, and the results are shown in fig. 5. As can be seen from fig. 5, the composite hydrogel had a small decrease in the amount of phenol adsorbed after being reused 7 times, and thus was recyclable. This is because the large amount of charged charges on the polymer chains can generate repulsive forces to the adsorbed species, thereby desorbing the phenol. Therefore, the composite hydrogel has good adsorption and desorption functions and can be repeatedly used.
Claims (10)
1. A molecularly imprinted chitosan/titanium dioxide composite hydrogel is characterized in that the composite hydrogel is prepared by the following method: adding chitosan and phenol into isopropanol, and uniformly mixing and stirring to obtain a chitosan-phenol solution; adding titanium dioxide, hydrochloric acid and ferric trichloride into deionized water, and stirring and mixing uniformly to obtain a nano titanium dioxide dispersion liquid; uniformly mixing and stirring the chitosan-phenol solution and the nano titanium dioxide dispersion liquid, adding ascorbic acid, stirring and reacting for 3-12 hours at 40-80 ℃, washing and soaking a product obtained by the reaction with distilled water to obtain hydrogel, then placing the hydrogel in a disodium hydrogen phosphate aqueous solution, eluting template molecular phenol in a molecular imprinting layer by using a potentiostatic method, adding distilled water again for washing, and finally obtaining the molecularly imprinted chitosan/titanium dioxide composite hydrogel.
2. The molecularly imprinted chitosan/titanium dioxide composite hydrogel according to claim 1, characterized in that: the molar ratio of the chitosan to the phenol is 1: 0.2-0.4.
3. The molecularly imprinted chitosan/titanium dioxide composite hydrogel according to claim 1, characterized in that: the mass ratio of the phenol to the ferric trichloride to the HCl is 1: 3-5: 40-45.
4. The molecularly imprinted chitosan/titanium dioxide composite hydrogel according to claim 1, characterized in that: the mass ratio of the chitosan to the titanium dioxide to the ascorbic acid is 1: 0.4-0.5: 0.07-0.1.
5. The molecularly imprinted chitosan/titanium dioxide composite hydrogel according to claim 1, characterized in that: stirring and reacting for 5-6 hours at 50-70 ℃.
6. The molecularly imprinted chitosan/titanium dioxide composite hydrogel according to claim 1, characterized in that: soaking in deionized water for 2-3 days.
7. The molecularly imprinted chitosan/titanium dioxide composite hydrogel according to claim 1, characterized in that: the mass concentration of the disodium hydrogen phosphate in the disodium hydrogen phosphate aqueous solution is 2-5%.
8. The use of the molecularly imprinted chitosan/titanium dioxide composite hydrogel of claim 1 for removing phenolic substances from high-concentration phenol-containing wastewater.
9. The use of the molecularly imprinted chitosan/titanium dioxide composite hydrogel according to claim 8 for removing phenolic substances in high-concentration phenol-containing wastewater, wherein the molecularly imprinted chitosan/titanium dioxide composite hydrogel comprises the following components: adding the composite hydrogel into high-concentration phenol-containing wastewater, controlling the mass ratio of the phenol substances to the composite hydrogel to be 1: 35-55 g, and adsorbing at the constant temperature of 30-40 ℃ for 2-3 hours.
10. The use of the molecularly imprinted chitosan/titanium dioxide composite hydrogel according to claim 9 for removing phenolic substances in high-concentration phenol-containing wastewater, wherein the molecularly imprinted chitosan/titanium dioxide composite hydrogel comprises the following components: and (3) placing the composite hydrogel after adsorbing the phenolic substances into a disodium hydrogen phosphate aqueous solution with the mass concentration of 2-5%, eluting the phenolic substances in the molecularly imprinted layer by using a potentiostatic method, and adding distilled water for washing and then repeatedly using.
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