CN107915788B - Cyclodextrin-based micromolecular pollutant adsorption material and preparation method thereof - Google Patents
Cyclodextrin-based micromolecular pollutant adsorption material and preparation method thereof Download PDFInfo
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Abstract
Cyclodextrin high molecular polymer, which is obtained by reacting cyclodextrin with organic acid and contains chemical groups such as C-O, C-C and C-O-C. The preparation method of the cyclodextrin high-molecular polymer comprises the following steps: (1) adding cyclodextrin into a water-organic acid mixed system, wherein the water content in the water-organic acid mixed system is 0-50% by volume, and obtaining a ternary mixture system with the concentration of cyclodextrin being 0.05-1.0 g/ml; (2) heating to the reaction temperature of 50-180 ℃ and the reaction time of not less than 24 hours; (3) cooling, filtering, washing filter cakes with water, and drying to obtain the cyclodextrin high-molecular polymer with the yield of 50-70%. The cyclodextrin high molecular polymer has extremely high adsorption speed and extremely high selectivity on micromolecular pollutants. The adopted raw materials are simple, and the cost is lower; the preparation process has low toxicity to the environment, and the cyclodextrin is easy to biodegrade, environment-friendly and economical.
Description
Technical Field
The invention belongs to the field of water treatment, relates to a treatment material and a preparation method thereof, and particularly relates to a cyclodextrin-based micromolecular pollutant adsorption material and a preparation method thereof.
Background
The production wastewater and the domestic wastewater contain various toxic and harmful substances, and the pollution to water bodies is becoming serious day by day, so that the effective treatment of the wastewater is a social problem which is greatly concerned. In particular, in some waste water from pesticide and medicine industries, the waste water often contains a plurality of small molecule pollutants with high concentration, and the harm to the ecological environment and the human health is particularly serious. The common treatment method nowadays is to use porous material to adsorb these small molecules, so as to achieve the purpose of removal. The activated carbon has a high specific surface area and relatively low cost, so that the activated carbon becomes one of the most widely used small-molecule pollutant adsorbing materials. However, the disadvantages of activated carbon as a water treatment material are also quite obvious, mainly including the following points: (1) the material has strong hydrophobicity, which is not beneficial to the dispersion of the material in water; (2) the adsorption speed is relatively slow; (3) the material regeneration treatment needs to consume a large amount of energy, and the treatment efficiency is obviously reduced after regeneration.
In order to overcome the above-mentioned drawbacks of activated carbon, a large number of porous materials have been synthesized and applied to research in the field of wastewater treatment. One class of materials is inclusions (Inclusion complex) formed based on Host-guest chemistry (Host-guest chemistry) systems, which can form porous structures that effectively adsorb small molecule contaminants. Traditional host-guest chemical materials, such as calixarene and cyclodextrin, are representative systems that are widely used in wastewater treatment. Among them, the research on the water treatment porous material system using cyclodextrin as a raw material is more intensive.
Cyclodextrins are oligomeric polysaccharide structures formed by enzymatic conversion of starch, and are one of the most common materials in the field of water treatment. The method has the advantages that the method is used for treating the wastewater polluted by small molecules: (1) the numerous hydroxyl groups distributed around the molecules endow the hydrophilic polymer with good hydrophilicity, and meanwhile, the hydrophobic polymer has certain hydrophobicity in the cavity; therefore, the cyclodextrin molecule provides a cavity with a specific size, can contain organic small molecule pollutants and is a good carrier for removing the organic small molecule pollutants in the water body. (2) The chemical action of the host and the guest between the cyclodextrin and the micromolecular pollutants has stronger reversibility, so that the low-cost regeneration and use of the material become possible. (3) The cyclodextrin has low cost, can be completely biodegraded due to the rich polysaccharide structure, and is environment-friendly.
The university of northwest Dichtel group of the united states developed a very economical and efficient process for the preparation of beta cyclodextrin porous materials (alaeddin Alsbaiee, Brian j.smith, leileileilei Xiao, et al nature 2016,529, 190-. The method uses tetrafluoroterephthalonitrile as a monomer (shown in figure 1), tetrahydrofuran is used for forming a solvent, and the beta-cyclodextrin porous material P-CDP is obtained by copolymerization reaction for two days at the temperature of 80 ℃ and with the yield of-20%. Compared with activated carbon, the material can adsorb and remove various small molecular pollutants at a higher speed, and can be regenerated simply after being cleaned by methanol, and the small molecular adsorption performance of the regenerated material is not reduced basically.
However, this method still has certain disadvantages: (1) the tetrafluoroterephthalonitrile used in the method has large irritation and toxicity to human bodies; in addition, the material contains more fluorine elements, is not easy to biodegrade and is not environment-friendly; (2) the preparation steps are complex, alkali is required to be added into an organic solvent as a catalyst, and the preparation of the material can be completed only after 48 hours at 80 ℃, in addition, the whole process needs inert gas for protection, and the steps of drying and dewatering under the condition of vacuum liquid nitrogen are required after the preparation is completed, so that the preparation cost is greatly increased; (3) because the solubility of beta cyclodextrin in organic solvent is limited, and the efficiency of fluoro nucleophilic substitution reaction in the preparation process is relatively low, the yield is not high, and the method is not favorable for further industrial scale-up process.
Jaouadi et al prepared four types of activated carbon materials, including β cyclodextrin prepared porous material CCD (mount Jaouadi, Souhaira Hbaieb, Hanen Guedidi, et al, Journal of Saudi chemical Society2017,21, 822-829). The method was performed by dehydrating 3.26 g β cyclodextrin in a mixed solvent of toluene and sulfuric acid (30: 1 by volume) at a high temperature of 110 ℃ for 24 hours, then removing the solvent by vacuum rotary evaporation, thoroughly washing with water, performing Soxhlet extraction at a high temperature of 48 hours, and drying at a high temperature to obtain the target materialBET) Is one of the important indexes for representing the porosity of the porous material; the higher the specific surface area, the better the adsorption properties of the material tend to be. The specific surface area of the material is 90m2About/g, which is only one tenth of that of activated carbon (FIG. 2). However, the adsorption curve of the boron-containing wastewater demonstrates (fig. 3) that the adsorption efficiency of the material is significantly higher than that of activated carbon; this is because the surface of the material is rich in phenolic hydroxyl groups which interact with boron.
However, the drawbacks of this method are also quite evident: (1) a large amount of toluene is used as a main solvent, and the cyclodextrin is dehydrated under the condition of high-temperature reflux; after the material preparation is completed, the post-treatment of the waste liquid is very troublesome; (2) the purification after the material preparation is more complicated, the final product can be obtained only by vacuum rotary evaporation and long-time Soxhlet extraction, and the energy consumption is quite large; (3) toluene as a solvent and cyclodextrin as a raw material both have a possibility of undergoing a dehydration reaction with sulfuric acid, so that toluene and cyclodextrin have a competitive effect; and cyclodextrin has poor solubility in toluene, and thus, the yield is low.
Compared with other host-guest chemical systems, the technology in the above example treats small molecular pollutants in wastewater, the cyclodextrin raw material is cheaper, and the removal efficiency and the regeneration capacity are greatly improved compared with those of the traditional activated carbon material. However, the preparation steps of the method are complicated, and the preparation cost is greatly increased. Furthermore, neither is the selectivity of contaminant adsorption concerned.
Disclosure of Invention
Aiming at the problems existing in the treatment of small molecular pollutants in wastewater in the prior art, the invention provides the adsorbing material based on cyclodextrin, which has low toxicity, easy degradation and high selectivity, and has the advantages of simple preparation, high yield and greatly reduced production cost; in addition, the material also has the advantages of high hydrophilicity, fast adsorption and easy regeneration, and has wide market application prospect.
The technical scheme of the invention is as follows:
a cyclodextrin high molecular polymer has a structural general formula:
wherein n is 5,6 or 7. The high-molecular polymer is a cyclodextrin high-molecular polymer which is obtained by reacting cyclodextrin with organic acid and contains chemical groups such as C-O, C-C and C-O-C.
The preparation method of the cyclodextrin high-molecular polymer comprises the following steps:
(1) adding cyclodextrin into a water-organic acid mixed system, wherein the water content in the water-organic acid mixed system is 0-50% by volume, and obtaining a ternary mixture system with the concentration of cyclodextrin being 0.05-1.0 g/ml; the organic acid is p-toluenesulfonic acid, trifluoromethanesulfonic acid, methanesulfonic acid, trifluoroacetic acid or acetic acid; the cyclodextrin is alpha cyclodextrin, beta cyclodextrin, gamma cyclodextrin or any combination of the three.
(2) Heating to the reaction temperature of 50-180 ℃ and the reaction time of not less than 24 hours;
(3) cooling, filtering, washing filter cake with water, and drying to obtain the cyclodextrin high molecular polymer, wherein the appearance of the cyclodextrin high molecular polymer is black or brown powder, and the yield is 50-70%.
Preferably, the water content in the water-organic acid mixed system in the step (1) is 0-40% by volume; the concentration of cyclodextrin in the ternary mixture system obtained in the step (1) is 0.05-0.50 g/ml.
More preferably, the water content of the water-organic acid mixed system in the step (1) is 0-30% by volume; the concentration of cyclodextrin in the ternary mixture system obtained in the step (1) is 0.05-0.20 g/ml.
Preferably, the reaction temperature in the step (2) is 50 to 150 ℃ and the reaction time is 24 to 72 hours.
More preferably, the reaction temperature in the step (2) is 50 to 120 ℃ and the reaction time is 24 to 48 hours.
The application of cyclodextrin high molecular polymer in wastewater treatment, wherein the wastewater contains micromolecular pollutants.
The application of the cyclodextrin high molecular polymer is applied to the preparation of a wastewater treatment device, wherein the wastewater treatment device is a filter element or a chromatographic column.
The invention has the beneficial effects that: compared with the prior art, the invention has the following advantages:
(1) the cyclodextrin high molecular polymer provided by the invention has extremely high adsorption speed and extremely high selectivity on small molecular pollutants.
(2) The preparation method of the cyclodextrin high molecular polymer can generate the adsorbing material based on cyclodextrin only by one-step reaction, and has simple steps and no need of complex synthesis; the post-treatment only needs to be cleaned by water, and the post-treatment is easy, simple and quick; and the synthesis yield (50% -70%) is obviously improved compared with the existing method (20%).
(3) The preparation method adopts cyclodextrin and solvent as raw materials, and has simple raw materials and lower cost; the preparation process has low toxicity to the environment, and the cyclodextrin is easy to biodegrade, environment-friendly and economical.
Drawings
FIG. 1 is a reaction scheme of beta cyclodextrin with tetrafluoroterephthalonitrile to form copolymer P-CDP;
FIG. 2 shows the specific surface area of a quasi-activated carbon material (CCD) prepared from beta-cyclodextrin and Activated Carbon (AC);
FIG. 3 is an adsorption curve of four materials for boron-containing wastewater (activated carbon: ●, CCD:tangle-solidup);
FIG. 4 is an infrared spectrum of a material of the present invention;
FIG. 5 shows the adsorption effect of cyclodextrin adsorption material prepared by the present invention on dye molecules of different sizes.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1:
a cyclodextrin high molecular polymer has a structural general formula:
wherein n is 6. The high-molecular polymer is a cyclodextrin high-molecular polymer which is obtained by reacting cyclodextrin with organic acid and contains chemical groups such as C-O, C-C and C-O-C.
The preparation method of the cyclodextrin high-molecular polymer comprises the following steps:
(1) weighing 5g of beta cyclodextrin, adding the beta cyclodextrin into a water-organic acid mixed system, wherein the volume part of water in the water-organic acid mixed system is 10%, and obtaining a ternary mixture system with the concentration of the cyclodextrin being 0.05 g/ml; the organic acid is p-toluenesulfonic acid.
(2) Heating to the reaction temperature of 90 ℃ and the reaction time of 72 hours;
(3) cooling, filtering, washing filter cake with water, and drying to obtain the cyclodextrin high molecular polymer, wherein the appearance of the cyclodextrin high molecular polymer is black powder, and the yield is 70%.
Example 2:
in contrast to the embodiment 1, the process of the invention,
the preparation method of the cyclodextrin high-molecular polymer comprises the following steps:
(1) weighing 5g of beta cyclodextrin, adding the beta cyclodextrin into a water-organic acid mixed system, wherein the volume part of water in the water-organic acid mixed system is 20%, and obtaining a ternary mixture system with the concentration of the cyclodextrin being 0.1 g/ml; the organic acid is trifluoromethanesulfonic acid.
(2) Heating to the reaction temperature of 120 ℃ and the reaction time of 24 hours;
(3) cooling, filtering, washing filter cake with water, and drying to obtain the cyclodextrin high molecular polymer, wherein the appearance of the cyclodextrin high molecular polymer is black powder, and the yield is 62%.
Example 3:
different from the embodiment 1, the cyclodextrin high molecular polymer has the structural general formula:
wherein n is 7.
The preparation method of the cyclodextrin high-molecular polymer comprises the following steps:
(1) weighing 1g of gamma cyclodextrin, and adding the gamma cyclodextrin into a water-organic acid mixed system, wherein the volume part of water in the water-organic acid mixed system is 30%, so as to obtain a ternary mixture system with the concentration of cyclodextrin being 0.2 g/ml; the organic acid is methanesulfonic acid.
(2) Heating to the reaction temperature of 150 ℃ and the reaction time of 36 hours;
(3) cooling, filtering, washing filter cake with water, and drying to obtain the cyclodextrin high molecular polymer, wherein the appearance of the cyclodextrin high molecular polymer is black powder, and the yield is 63%.
Example 4:
different from the embodiment 1, the cyclodextrin high molecular polymer has the structural general formula:
wherein n is 5 or 6.
The preparation method of the cyclodextrin high-molecular polymer comprises the following steps:
(1) weighing 1g of alpha cyclodextrin and 3g of beta cyclodextrin, adding the alpha cyclodextrin and the beta cyclodextrin into a water-organic acid mixed system, wherein the volume part of water in the water-organic acid mixed system is 40%, and obtaining a ternary mixture system with the concentration of the cyclodextrin being 0.5 g/ml; the organic acid is trifluoroacetic acid.
(2) Heating to the reaction temperature of 180 ℃ and the reaction time of 48 hours;
(3) cooling, filtering, washing the filter cake with water, and drying to obtain the cyclodextrin high molecular polymer, wherein the appearance of the cyclodextrin high molecular polymer is black powder, and the yield is 52%.
Example 5:
different from the embodiment 1, the cyclodextrin high molecular polymer has the structural general formula:
wherein n is 6 or 7.
The preparation method of the cyclodextrin high-molecular polymer comprises the following steps:
(1) weighing 3.5g of beta cyclodextrin and 0.5g of gamma cyclodextrin, adding the beta cyclodextrin and the gamma cyclodextrin into a water-organic acid mixed system, wherein the volume part of water in the water-organic acid mixed system is 50%, and obtaining a ternary mixture system with the concentration of the cyclodextrin being 1.0 g/ml; the organic acid is acetic acid.
(2) Heating to the reaction temperature of 50 ℃ and the reaction time of 60 hours;
(3) cooling, filtering, washing filter cake with water, and drying to obtain the cyclodextrin high molecular polymer, wherein the appearance of the cyclodextrin high molecular polymer is black powder, and the yield is 50%.
Example 6:
different from the embodiment 1, the cyclodextrin high molecular polymer has the structural general formula:
wherein n is 5,6 or 7.
The preparation method of the cyclodextrin high-molecular polymer comprises the following steps:
(1) weighing 1g of alpha cyclodextrin, 2.5g of beta cyclodextrin and 0.5g of gamma cyclodextrin, adding the alpha cyclodextrin, the 2.5g of beta cyclodextrin and the 0.5g of gamma cyclodextrin into a water-organic acid mixed system, wherein the volume fraction of water in the water-organic acid mixed system is 30%, and obtaining a ternary mixture system with the concentration of the cyclodextrin being 0.5 g/ml; the organic acid is p-toluenesulfonic acid.
(2) Heating to the reaction temperature of 70 ℃ and the reaction time of 24 hours;
(3) cooling, filtering, washing filter cake with water, and drying to obtain the cyclodextrin high molecular polymer, wherein the appearance of the cyclodextrin high molecular polymer is black powder, and the yield is 65%.
Example 7: confirmation of structural aspects of materials
The cyclodextrin high molecular polymers prepared in examples 1-6 were insoluble in water and various organic solvents.
As can be seen from the IR spectrum of FIG. 5, several new peaks with higher intensity appeared in the cyclodextrin polymers prepared in examples 1-6, compared to the cyclodextrin used as the starting material. Wherein, the thickness is 3000cm-1The new peak is the stretching vibration of C-H in olefin; at 1714cm-1And 1650cm-1The new peak appeared at (A) can be attributed to the stretching vibration peak of the C ═ O bond and the C ═ C bond; furthermore, it is located at 1153cm-1The stretching vibration peak intensity of the ether bond is obviously increased, which indicates that a large amount of ether bonds are generated in the preparation process of the material.
According to the results of element analysis, no other new elements appear before and after the reaction, the content of the carbon element after the reaction is obviously increased, and the content of the hydrogen element and the oxygen element are obviously reduced.
TABLE 1 elemental analysis results of the materials obtained in examples 1 to 6
| Examples | Cyclodextrin | Cyclodextrin adsorption material |
| 1 | C:H:O＝44.45:6.22:49.33 | C:H:O＝65.52:4.71:28.77 |
| 2 | Same as above | C:H:O＝67.02:4.74:28.24 |
| 3 | Same as above | C:H:O＝68.14:4.52:27.34 |
| 4 | Same as above | C:H:O＝68.07:4.49:27.44 |
| 5 | Same as above | C:H:O＝63.22:4.90:31.88 |
| 6 | Same as above | C:H:O＝65.72:4.63:29.65 |
By combining the properties of the material and the characterization results, the material is a high molecular polymer obtained by losing part of water molecules from cyclodextrin, and the material contains more C ═ O bonds and C ═ C bonds. At the same time, the cyclic structure of the cyclodextrin is still maintained.
Example 8: treatment of wastewater containing small molecular pollutants
Dye molecules are commonly used to study and simulate small molecule contaminants in wastewater. The materials prepared in the embodiments 1 to 6 are added into a plurality of aqueous solutions containing dyes with higher concentration, and the absorption intensity of the residual dyes is tested by an ultraviolet-visible spectrometer at intervals, so that the adsorption balance removal efficiency of the cyclodextrin on the dye molecules can be calculated. The time at which the absorption intensity of the residual dye no longer changed was marked as the adsorption equilibrium time, and the specific results are detailed in tables 2 to 7.
Results similar to those in tables 2 to 7 can also be obtained if a mixed solution of two or more dyes is passed through a column or cartridge packed with the materials prepared in examples 1 to 6.
TABLE 2 comparison of the selective adsorption properties of the dyes prepared in example 1
TABLE 3 comparison of the selective adsorption properties of the dyes prepared in example 2
TABLE 4 comparison of the selective adsorption properties of the dyes prepared in example 3
TABLE 5 comparison of the selective adsorption properties of the dyes prepared in example 4
Table 6 comparison of selective adsorption properties of dyes prepared in example 5
TABLE 7 comparison of the selective adsorption properties of the dyes prepared in example 6
As shown in tables 2-7, firstly, the cyclodextrin adsorbing material prepared by the invention has extremely high adsorption speed on small molecule pollutants with specific sizes, and can completely adsorb high-content (0.1mM,32ppm) methylene blue dye in only 10 seconds under the condition of concentration of 1 mg/mL. Bisphenol a, a common industrial wastewater contaminant, can be completely adsorbed within 10 minutes.
Second, the material has very high selectivity for adsorption of small molecule contaminants. The cyclodextrin forms an inclusion compound with the small molecules with a certain volume, such as bisphenol A and methylene blue, because the cyclodextrin and the cyclodextrin can form an inclusion compound with stability. In contrast, dye molecules with larger sizes cannot enter the intramolecular cavity of the cyclodextrin, and the adsorption speed and efficiency of the dye molecules are greatly reduced.
In conclusion, according to the preparation method disclosed by the invention, the adsorbing material based on the cyclodextrin can be obtained by only one-step reaction, the steps are simple, and complex synthesis is not needed; the post-treatment only needs to be cleaned by water, and the post-treatment is easy, simple and quick; and the synthesis yield (50% -70%) is obviously improved compared with the existing method (20%). In addition, the method has the advantages of simple raw materials and low cost; the preparation process has low toxicity to the environment, and the cyclodextrin is easy to biodegrade, environment-friendly and economical. Therefore, the method has wide application prospect in the field of wastewater treatment and generates great economic benefit.
Claims (7)
1. The preparation method of the cyclodextrin high-molecular polymer is characterized by comprising the following steps: the method comprises the following steps: (1) adding cyclodextrin into a water-organic acid mixed system to obtain a ternary mixture system with a certain concentration; the organic acid is p-toluenesulfonic acid, trifluoromethanesulfonic acid, methanesulfonic acid, trifluoroacetic acid or acetic acid, the water content in the water-organic acid mixed system is 10-50% by volume, and the concentration of cyclodextrin in the ternary mixed system is 0.05-1.0 g/ml; (2) heating to the reaction temperature of 50-180 ℃ and the reaction time of not less than 24 hours; (3) cooling, filtering, washing a filter cake with water, and drying to obtain the cyclodextrin high molecular polymer.
2. The method for producing a cyclodextrin high-molecular polymer according to claim 1, wherein: the cyclodextrin in the step (1) is alpha cyclodextrin, beta cyclodextrin, gamma cyclodextrin or any combination of the three.
3. The method for producing a cyclodextrin high-molecular polymer according to claim 2, wherein: the water content of the water-organic acid mixed system in the step (1) is 10-30% by volume ratio; the concentration of cyclodextrin in the ternary mixture system obtained in the step (1) is 0.05-0.20 g/ml.
4. The method for producing a cyclodextrin high-molecular polymer according to any one of claims 1 to 3, wherein: in the step (2), the reaction temperature is 50-150 ℃, and the reaction time is 24-72 hours.
5. The method for producing a cyclodextrin high-molecular polymer according to any one of claims 1 to 3, wherein: in the step (2), the reaction temperature is 50-120 ℃, and the reaction time is 24-48 hours.
6. The use of a cyclodextrin polymer obtained by the process according to claim 1, wherein: the method is applied to wastewater treatment, and the wastewater contains small molecular pollutants.
7. The use of a cyclodextrin polymer obtained by the process according to claim 1, wherein: the method is applied to the preparation of a wastewater treatment device which is a filter element or a chromatographic column.
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