CN112844332A - Preparation method and application of cyclodextrin-citric acid graft loaded ceramic ball - Google Patents
Preparation method and application of cyclodextrin-citric acid graft loaded ceramic ball Download PDFInfo
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- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/00—Nature of the contaminant
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Abstract
The invention discloses a preparation method and application of a cyclodextrin-citric acid graft loaded ceramic ball, which are prepared by taking cyclodextrin, citric acid and a porous ceramic ball as reactants and adding a catalyst into deionized water for reaction, wherein the cyclodextrin is any one of alpha-cyclodextrin, beta-cyclodextrin and gamma-cyclodextrin, and the catalyst is any one of sodium hypophosphite, sodium dihydrogen phosphate and disodium hydrogen phosphate; the cyclodextrin-citric acid graft loaded ceramic ball can be used as an adsorbent to adsorb triazole pesticides in water, has good adsorption stability and good stability at different pH values and different temperatures, and has a higher adsorption effect on the triazole pesticides; and the cyclodextrin-citric acid graft loaded ceramic ball has good cyclic utilization rate on triazole pesticides as an adsorbent, and even when the ceramic ball is recycled for the 10 th time, the initial capacity of the ceramic ball still reaches 80.1%, so that the ceramic ball is beneficial to repeated use and has high economic value.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method and application of a cyclodextrin-citric acid graft loaded ceramic ball.
Background
Triazole pesticides (flutrialcohol, diniconazole, butoconazole, hexazole, tebuconazole, difenoconazole) are widely used as bactericides for controlling diseases of turfgrass, vegetables, citrus, field crops, ornamental plants and the like worldwide, and although these triazole pesticides play an important role in agricultural production, unreasonable use thereof, potential threats to human health and pollution to the environment are receiving increasing attention (c.l. sanchez, c.l. souders II, c.j.pen-Delgado, k.t.nguyen, n.kroyter, n.e.ahmadie, j.j.arizional-Henao, j.a.bowden, c.j.j.tyniuk.neuro. toxicology.80 (76-86; c.y.ezierie, p.c.c.czezey, yang. m, c.20155. k, yang.2017. wak, pol. wak.7.g. wak.r.185. biochem, p.c.c.c.c.wo, c.20155, c.201j.20155. wak, c.7. waz. wo, r.7. waz. wo, r.169). Therefore, in many countries, the residue of triazole pesticides in vegetables and fruits is severely limited, with a maximum residue limit of 0.010 mg/kg; therefore, attention is paid to how to remove triazole pesticides in water, but no adsorbent has been found to have a good adsorption effect on triazole pesticides in water.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method and application of a cyclodextrin-citric acid graft loaded ceramic ball.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of a cyclodextrin-citric acid graft loaded ceramic ball comprises the following steps:
the method comprises the following steps: adding citric acid and a catalyst into a reaction container filled with deionized water, stirring and mixing, adding cyclodextrin, further stirring and mixing, uniformly mixing, and heating for reaction to obtain a first mixture;
step two: adding the ceramic balls into the first mixture, stirring and mixing, and uniformly mixing; reacting at the temperature of 100-180 ℃ for 1-6h to obtain a second mixture;
step three: and then, continuously reacting the second mixture for 20-40min at the temperature of 40-80 ℃, filtering to remove impurities, and finally drying to obtain the cyclodextrin-citric acid graft loaded ceramic ball.
As a further improvement of the invention, the cyclodextrin is any one of alpha-cyclodextrin, beta-cyclodextrin and gamma-cyclodextrin.
As a further improvement of the invention, the catalyst is any one of sodium hypophosphite, sodium dihydrogen phosphate and disodium hydrogen phosphate.
As a further improvement of the invention, the mass ratio of the cyclodextrin, the citric acid and the catalyst added in the step one is 8-12: 3-12: 3-12.
As a further improvement of the invention, the addition amount of the ceramic balls in the second step is 20-40 g.
As a further improvement of the invention, the step I of uniformly mixing and then heating for reaction specifically means that the reaction is carried out at the temperature of 40-70 ℃ for 0.5-3.0 h.
As a further improvement of the invention, the drying temperature of the cyclodextrin-citric acid graft loaded ceramic ball prepared by the third drying step is 50-90 ℃, and the drying time is 20-40 min.
As a further improvement of the invention, the cyclodextrin-citric acid graft loaded ceramic ball can be used as an adsorbent for adsorbing triazole pesticides in water, and the triazole pesticides are at least one of flutrialcohol, diniconazole, fluconazole, hexaconazole, tebuconazole and difenoconazole.
The invention has the beneficial effects that: the cyclodextrin-citric acid graft loaded ceramic ball is prepared by taking cyclodextrin, citric acid and a porous ceramic ball as reactants to react, and is a novel solid phase adsorbent material, and the solid phase adsorbent has good stability at different pH values and different temperatures and has higher adsorption effect on triazole pesticides. The solid-phase adsorbent is applied to the solid-phase adsorption of triazole pesticides, the adsorption capacity of the cyclodextrin-citric acid graft loaded ceramic ball to the fluortriol within 3.5 hours is 15.98mg/g, the balance data accords with the Freundlich equation, and the adsorption of the fluortriol and the diniconazole accords with the quasi-second order kinetics. The cyclodextrin-citric acid graft loaded ceramic ball has good cyclic utilization rate on triazole pesticides, and even when the ceramic ball is recycled for the 10 th time, the initial capacity of the ceramic ball still reaches 80.1 percent; and the solid phase adsorbent is not limited to be applied to the adsorption of triazole pesticides.
Drawings
FIG. 1 is a schematic diagram of a solid phase adsorbent prepared by loading cyclodextrin-citric acid graft with ceramic balls;
FIG. 2 is an infrared spectrum of the cyclodextrin-citric acid graft-supported ceramic ball obtained in example 1; wherein a is a cyclodextrin-citric acid conjugate, b is a natural micro-ceramic ball, and c is a cyclodextrin-citric acid graft loaded ceramic ball;
fig. 3 is a schematic diagram of the degradation capability of the cyclodextrin-citric acid graft-loaded ceramic ball prepared in example 1 to recycle triazole pesticide (fluortriol).
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Example 1
A preparation method of a cyclodextrin-citric acid graft loaded ceramic ball comprises the following steps:
the method comprises the following steps: adding 10g of citric acid and 3.39g of sodium dihydrogen phosphate into a 100mL three-necked flask filled with 20mL of deionized water, magnetically stirring at normal temperature to dissolve, adding 10g of beta-cyclodextrin, further stirring and mixing, uniformly mixing, and reacting at 60 ℃ for 1h to obtain a first mixture;
step two: adding 40g of porous ceramic balls into the first mixture, stirring and mixing, uniformly mixing, and reacting at the temperature of 170 ℃ for 3 hours to obtain a second mixture, wherein the second mixture is light yellow;
step three: continuing to react the second mixture at 75 ℃ for 35min, dissolving the second mixture in deionized water to obtain yellow insoluble substance; centrifuging, washing with deionized water for 5 times until pH is 5, and separating; and finally, drying at the temperature of 80 ℃ for 30min to obtain the cyclodextrin-citric acid graft loaded ceramic ball.
Example 2
A preparation method of a cyclodextrin-citric acid graft loaded ceramic ball comprises the following steps:
the method comprises the following steps: adding 10g of citric acid and 4.44g of sodium dihydrogen phosphate into a 100mL three-necked flask filled with 30mL of deionized water, magnetically stirring at normal temperature to dissolve, adding 10g of gamma-cyclodextrin, further stirring and mixing, uniformly mixing, and reacting at 40 ℃ for 3h to obtain a first mixture;
step two: adding 35g of porous ceramic balls into the first mixture, stirring and mixing, uniformly mixing, and reacting at 105 ℃ for 6 hours to obtain a second mixture, wherein the second mixture is light yellow;
step three: continuing to react the second mixture for 20min at the temperature of 80 ℃, dissolving the second mixture into deionized water to obtain yellow insoluble substances; centrifuging, washing with deionized water for 5 times until pH is 5, and separating; and finally, drying at the temperature of 90 ℃ for 20min to obtain the cyclodextrin-citric acid graft loaded ceramic ball.
Example 3
A preparation method of a cyclodextrin-citric acid graft loaded ceramic ball comprises the following steps:
the method comprises the following steps: adding 3.4g of citric acid and 6.25g of disodium hydrogen phosphate into a 100mL three-necked flask containing 20mL of deionized water, magnetically stirring at normal temperature to dissolve, adding 10g of beta-cyclodextrin, further stirring and mixing, uniformly mixing, and reacting at 45 ℃ for 2.5 hours to obtain a first mixture;
step two: adding 40g of porous ceramic balls into the first mixture, stirring and mixing, uniformly mixing, and reacting at the temperature of 150 ℃ for 2.5 hours to obtain a second mixture, wherein the second mixture is light yellow;
step three: continuously reacting the second mixture for 25min at the temperature of 75 ℃, dissolving the second mixture into deionized water to obtain yellow insoluble substances; centrifuging, washing with deionized water for 5 times until pH is 5, and separating; and finally, drying at the temperature of 80 ℃ for 25min to obtain the cyclodextrin-citric acid graft loaded ceramic ball.
Example 4
A preparation method of a cyclodextrin-citric acid graft loaded ceramic ball comprises the following steps:
the method comprises the following steps: adding 3.95g of citric acid and 4.44g of sodium phosphite into a 100mL three-necked flask filled with 25mL of deionized water, magnetically stirring at normal temperature for dissolving, adding 10g of alpha-cyclodextrin, further stirring and mixing, uniformly mixing, and reacting at 65 ℃ for 0.6h to obtain a first mixture;
step two: adding 20g of porous ceramic balls into the first mixture, stirring and mixing, uniformly mixing, and reacting at 140 ℃ for 2 hours to obtain a second mixture, wherein the second mixture is light yellow;
step three: continuing to react the second mixture at 45 ℃ for 32min, dissolving the second mixture in deionized water to obtain yellow insoluble substance; centrifuging, washing with deionized water for 5 times until pH is 5, and separating; and finally, drying at the temperature of 50 ℃ for 37min to obtain the cyclodextrin-citric acid graft loaded ceramic ball.
Example 5
A preparation method of a cyclodextrin-citric acid graft loaded ceramic ball comprises the following steps:
the method comprises the following steps: adding 6.77g of citric acid and 5.29g of sodium dihydrogen phosphate into a 100mL three-necked flask containing 35mL of deionized water, magnetically stirring at normal temperature to dissolve, adding 10g of beta-cyclodextrin, further stirring and mixing, uniformly mixing, and reacting at 58 ℃ for 2h to obtain a first mixture;
step two: adding 35g of porous ceramic balls into the first mixture, stirring and mixing, uniformly mixing, and reacting at 120 ℃ for 5 hours to obtain a second mixture, wherein the second mixture is light yellow;
step three: continuously reacting the second mixture at 60 ℃ for 30min, dissolving the second mixture in deionized water to obtain yellow insoluble substances; centrifuging, washing with deionized water for 5 times until pH is 5, and separating; and finally, drying at the temperature of 70 ℃ for 28min to obtain the cyclodextrin-citric acid graft loaded ceramic ball.
Example 6
A preparation method of a cyclodextrin-citric acid graft loaded ceramic ball comprises the following steps:
the method comprises the following steps: adding 8.46g of citric acid and 9.52g of sodium phosphite into a 100mL three-necked flask filled with 40mL of deionized water, magnetically stirring at normal temperature for dissolving, adding 11g of beta-cyclodextrin, further stirring and mixing, uniformly mixing, and reacting at 60 ℃ for 3h to obtain a first mixture;
step two: adding 40g of porous ceramic balls into the first mixture, stirring and mixing, uniformly mixing, and reacting at 160 ℃ for 3 hours to obtain a second mixture, wherein the second mixture is light yellow;
step three: continuously reacting the second mixture for 35min at the temperature of 60 ℃, dissolving the second mixture into deionized water to obtain yellow insoluble substances; centrifuging, washing with deionized water for 5 times until pH is 5, and separating; and finally, drying at the temperature of 60 ℃ for 37min to obtain the cyclodextrin-citric acid graft loaded ceramic ball.
Example 7
A preparation method of a cyclodextrin-citric acid graft loaded ceramic ball comprises the following steps:
the method comprises the following steps: adding 3.95g of citric acid and 5.84g of disodium hydrogen phosphate into a 100mL three-necked flask containing 30mL of deionized water, magnetically stirring at normal temperature to dissolve, adding 9g of alpha-cyclodextrin, further stirring and mixing, uniformly mixing, and reacting at 62 ℃ for 1h to obtain a first mixture;
step two: adding 32g of porous ceramic balls into the first mixture, stirring and mixing, uniformly mixing, and reacting at the temperature of 170 ℃ for 1h to obtain a second mixture, wherein the second mixture is light yellow;
step three: continuing to react the second mixture at 50 deg.C for 27min, dissolving the second mixture with deionized water to obtain yellow insoluble substance; centrifuging, washing with deionized water for 5 times until pH is 5, and separating; and finally, drying at the temperature of 70 ℃ for 25min to obtain the cyclodextrin-citric acid graft loaded ceramic ball.
Example 8
A preparation method of a cyclodextrin-citric acid graft loaded ceramic ball comprises the following steps:
the method comprises the following steps: adding 3.7g of citric acid and 3.83g of disodium hydrogen phosphate into a 100mL three-necked flask containing 30mL of deionized water, magnetically stirring at normal temperature to dissolve, adding 9g of gamma-cyclodextrin, further stirring and mixing, uniformly mixing, and reacting at 55 ℃ for 1.5h to obtain a first mixture;
step two: adding 20g of porous ceramic balls into the first mixture, stirring and mixing, uniformly mixing, and reacting at 145 ℃ for 2 hours to obtain a second mixture, wherein the second mixture is light yellow;
step three: continuing to react the second mixture for 25min at the temperature of 72 ℃, dissolving the second mixture into deionized water to obtain yellow insoluble substances; centrifuging, washing with deionized water for 5 times until pH is 5, and separating; and finally, drying at 85 ℃ for 23min to obtain the cyclodextrin-citric acid graft loaded ceramic ball.
Example 9
A preparation method of a cyclodextrin-citric acid graft loaded ceramic ball comprises the following steps:
the method comprises the following steps: adding 6.67g of citric acid and 4.20g of sodium dihydrogen phosphate into a 100mL three-necked flask containing 20mL of deionized water, magnetically stirring at normal temperature to dissolve, adding 11g of gamma-cyclodextrin, further stirring and mixing, uniformly mixing, and reacting at 56 ℃ for 3h to obtain a first mixture;
step two: adding 30g of porous ceramic balls into the first mixture, stirring and mixing, uniformly mixing, and reacting at the temperature of 170 ℃ for 3 hours to obtain a second mixture, wherein the second mixture is light yellow;
step three: continuing to react the second mixture at 63 deg.C for 31min, dissolving the second mixture with deionized water to obtain yellow insoluble substance; centrifuging, washing with deionized water for 5 times until pH is 5, and separating; and finally, drying at the temperature of 80 ℃ for 28min to obtain the cyclodextrin-citric acid graft loaded ceramic ball.
Example 10
A preparation method of a cyclodextrin-citric acid graft loaded ceramic ball comprises the following steps:
the method comprises the following steps: adding 4.23g of citric acid and 5.29g of sodium dihydrogen phosphate into a 100mL three-necked flask containing 40mL of deionized water, magnetically stirring at normal temperature to dissolve, adding 9g of beta-cyclodextrin, further stirring and mixing, uniformly mixing, and reacting at 68 ℃ for 0.5h to obtain a first mixture;
step two: adding 35g of porous ceramic balls into the first mixture, stirring and mixing, uniformly mixing, and reacting at 105 ℃ for 2 hours to obtain a second mixture, wherein the second mixture is light yellow;
step three: continuing to react the second mixture at 70 ℃ for 40min, dissolving the second mixture in deionized water to obtain yellow insoluble substance; centrifuging, washing with deionized water for 5 times until pH is 5, and separating; and finally, drying at the temperature of 70 ℃ for 30min to obtain the cyclodextrin-citric acid graft loaded ceramic ball.
And (3) performance testing:
preparing a solid phase adsorbent (column) by using the product prepared in each example, wherein FIG. 1 is a schematic diagram of preparing the solid phase adsorbent by loading cyclodextrin-citric acid graft on ceramic balls;
the solid phase adsorption process of the solid phase adsorbent to the pesticide (diniconazole) is as follows: 60g of each example product was packed in a 20mm diameter glass column as shown in FIG. 1; different concentrations of pesticide were then added to the column and held in the column for different times. At regular intervals, 0.1ml of the solution was filtered through a 0.45mm microporous glass fiber membrane. Measuring the pesticide content in the filtrate by high performance liquid chromatography; high performance liquid chromatography: the mobile phase is 60% methanol water solution, the flow rate is 1.0ml/min, the detection wavelength is 220 nm, the column temperature is 27 ℃, the mobile phase is 80% methanol, the flow rate is 1.0ml/min, the detection wavelength is 254nm, and the column temperature is 40 ℃.
Calculating the formula: w1, initial weight; w2, weight hold; DE%, adsorption (degradation) efficiency; DE% ((W1-W2)/W1 ×)
Example 1 degradation efficiency of cyclodextrin-citric acid graft loaded ceramic ball on pesticide at a certain temperature, a certain pH and within 10 days: unit%
| pH＝4.2 | pH＝7.0 | pH＝7.7 | pH＝8.5 | pH＝10.5 | |
| 25℃ | 3.42 | 0.31 | 0.78 | 3.11 | 3.26 |
| 35℃ | 7.87 | 1.80 | 4.09 | 6.47 | 7.43 |
Example 2 degradation efficiency of cyclodextrin-citric acid graft loaded ceramic ball on pesticide at a certain temperature, a certain pH and within 10 days: unit%
| pH＝4.2 | pH＝7.0 | pH＝7.7 | pH＝8.5 | pH＝10.5 | |
| 25℃ | 3.24 | 0.25 | 0.63 | 2.94 | 3.15 |
| 35℃ | 7.73 | 1.74 | 3.98 | 6.36 | 7.32 |
Example 4 degradation efficiency of cyclodextrin-citric acid graft loaded ceramic beads on pesticides at a certain temperature, a certain pH, within 10 days: unit%
| pH＝4.2 | pH＝7.0 | pH＝7.7 | pH＝8.5 | pH＝10.5 | |
| 25℃ | 3.15 | 0.12 | 0.44 | 2.81 | 3.13 |
| 35℃ | 7.57 | 1.63 | 3.76 | 6.03 | 7.09 |
Example 6 degradation efficiency of cyclodextrin-citric acid graft loaded ceramic beads on pesticide fluortriol at a certain temperature, a certain pH and within 10 days: unit%
| pH＝4.2 | pH＝7.0 | pH＝7.7 | pH＝8.5 | pH＝10.5 | |
| 25℃ | 3.36 | 0.28 | 0.69 | 3.01 | 3.25 |
| 35℃ | 7.81 | 1.76 | 4.10 | 6.37 | 7.36 |
Example 7 degradation efficiency of cyclodextrin-citric acid graft loaded ceramic beads on pesticides at a certain temperature, a certain pH, within 10 days: unit%
| pH＝4.2 | pH＝7.0 | pH＝7.7 | pH＝8.5 | pH＝10.5 | |
| 25℃ | 3.14 | 0.16 | 0.48 | 2.87 | 3.06 |
| 35℃ | 7.56 | 1.63 | 3.74 | 6.09 | 7.18 |
Example 9 degradation efficiency of cyclodextrin-citric acid graft loaded ceramic beads on pesticides at a certain temperature, a certain pH, within 10 days: unit%
| pH＝4.2 | pH＝7.0 | pH＝7.7 | pH＝8.5 | pH＝10.5 | |
| 25℃ | 3.27 | 0.21 | 0.57 | 2.95 | 3.15 |
| 35℃ | 7.53 | 1.75 | 3.98 | 6.19 | 7.25 |
Example 10 degradation efficiency of cyclodextrin-citric acid graft loaded ceramic beads on pesticides at a certain temperature, a certain pH, within 10 days: unit%
| pH＝4.2 | pH＝7.0 | pH＝7.7 | pH＝8.5 | pH＝10.5 | |
| 25℃ | 3.24 | 0.23 | 0.53 | 2.98 | 312 |
| 35℃ | 7.77 | 1.73 | 3.94 | 6.14 | 7.29 |
From the table, the cyclodextrin-citric acid graft loaded ceramic ball prepared by the invention can be used as an adsorbent to adsorb triazole pesticides in water, has good adsorption stability and good adsorption (degradation) capacity at different pH values and different temperatures, and ensures solid phase adsorption and cyclic utilization.
The infrared spectrum test was performed on the product obtained in example 1, and the infrared spectrum test was performed on the cyclodextrin-citric acid conjugate and the natural micro-ceramic spheres, thereby obtaining fig. 2, and it can be seen from fig. 2 that the product obtained in example 1 is indeed the cyclodextrin-citric acid graft-loaded ceramic spheres required in the present invention.
In addition, when the cyclodextrin-citric acid graft-loaded ceramic ball prepared in example 1 is applied to solid phase adsorption of triazole pesticides (taking the example of the fluortriol), the adsorption amount of the cyclodextrin-citric acid graft-loaded ceramic ball to the fluortriol within 3.5 hours is 15.98 mg/g; the cyclodextrin-citric acid graft loaded ceramic ball has good cyclic utilization rate on triazole pesticides, and even when the ceramic ball is recycled for the 10 th time, the initial capacity of the ceramic ball still reaches 80.1% (as shown in figure 3), so that the ceramic ball can be recycled and reused, and the economic benefit is high.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.
Claims (8)
1. A preparation method of a cyclodextrin-citric acid graft loaded ceramic ball is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the following steps: adding citric acid and a catalyst into a reaction container filled with deionized water, stirring and mixing, adding cyclodextrin, further stirring and mixing, uniformly mixing, and heating for reaction to obtain a first mixture;
step two: adding the ceramic balls into the first mixture, stirring and mixing, and uniformly mixing; reacting at the temperature of 100-180 ℃ for 1-6h to obtain a second mixture;
step three: and then, continuously reacting the second mixture for 20-40min at the temperature of 40-80 ℃, filtering to remove impurities, and finally drying to obtain the cyclodextrin-citric acid graft loaded ceramic ball.
2. The preparation method of the cyclodextrin-citric acid graft-loaded ceramic ball according to claim 1, wherein the preparation method comprises the following steps: the cyclodextrin is any one of alpha-cyclodextrin, beta-cyclodextrin and gamma-cyclodextrin.
3. The preparation method of the cyclodextrin-citric acid graft-loaded ceramic ball according to claim 1, wherein the preparation method comprises the following steps: the catalyst is any one of sodium hypophosphite, sodium dihydrogen phosphate and disodium hydrogen phosphate.
4. The preparation method of the cyclodextrin-citric acid graft-loaded ceramic ball according to claim 1, wherein the preparation method comprises the following steps: the mass ratio of the cyclodextrin, the citric acid and the catalyst added in the first step is 8-12: 3-12: 3-12.
5. The preparation method of the cyclodextrin-citric acid graft-loaded ceramic ball according to claim 1, wherein the preparation method comprises the following steps: the addition amount of the ceramic balls in the second step is 20-40 g.
6. The preparation method of the cyclodextrin-citric acid graft-loaded ceramic ball according to claim 1, wherein the preparation method comprises the following steps: the step one, after being uniformly mixed, is heated to carry out reaction, in particular to carry out reaction at the temperature of 40-70 ℃ for 0.5-3.0 h.
7. The preparation method of the cyclodextrin-citric acid graft-loaded ceramic ball according to claim 1, wherein the preparation method comprises the following steps: and step three, drying the cyclodextrin-citric acid graft loaded ceramic ball at the drying temperature of 50-90 ℃ for 20-40 min.
8. The use of the cyclodextrin-citric acid graft-loaded ceramic beads according to any one of claims 1 to 7, wherein: the cyclodextrin-citric acid graft loaded ceramic ball can be used as an adsorbent for adsorbing triazole pesticides in water, and the triazole pesticides are at least one of flutrialcohol, diniconazole, butoconazole, hexazole, tebuconazole and difenoconazole.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113842897A (en) * | 2021-10-23 | 2021-12-28 | 河南农业大学 | Preparation method of cyclodextrin polymer for adsorbing organic dye |
| CN114177897A (en) * | 2021-07-30 | 2022-03-15 | 华东理工大学 | Preparation method and application of silane modified cyclodextrin-based adsorbent |
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| CN116199945A (en) * | 2022-09-19 | 2023-06-02 | 福建中烟工业有限责任公司 | Cyclodextrin complex and preparation method and application thereof |
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