CN112023888B - Preparation method of tannin-cyclodextrin gel type adsorption material, prepared adsorption material and application - Google Patents
Preparation method of tannin-cyclodextrin gel type adsorption material, prepared adsorption material and application Download PDFInfo
- Publication number
- CN112023888B CN112023888B CN202010850947.7A CN202010850947A CN112023888B CN 112023888 B CN112023888 B CN 112023888B CN 202010850947 A CN202010850947 A CN 202010850947A CN 112023888 B CN112023888 B CN 112023888B
- Authority
- CN
- China
- Prior art keywords
- cyclodextrin
- tannin
- tannic acid
- adsorption
- gel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The invention discloses a preparation method of a tannin-cyclodextrin gel type adsorbing material, which relates to the technical field of adsorbing materials and comprises the following steps: (1) dissolving tannic acid and cyclodextrin in an organic solvent 1 to prepare a mixed solution of tannic acid and cyclodextrin; (2) dissolving terephthaloyl chloride in an organic solvent 2 to prepare a terephthaloyl chloride mixed solution; (3) dropwise adding the terephthaloyl chloride mixed solution prepared in the step (2) into the tannic acid and cyclodextrin mixed solution, sealing after dropwise adding, preserving heat, taking out and cooling, filtering the solution, purifying the obtained solid, and drying to obtain the tannic acid-cyclodextrin gel type adsorbing material. The invention has the beneficial effects that: the preparation method is simple, convenient to operate, green and environment-friendly, and can be used for selectively recovering lead ions in the wastewater.
Description
Technical Field
The invention relates to the technical field of adsorption materials, and particularly relates to a preparation method of a tannin-cyclodextrin gel type adsorption material, a prepared adsorption material and application.
Background
With the rapid development of industrialization, a large amount of pollutants are released into aquatic environments, which poses serious environmental challenges on a global scale. On the other hand, heavy metal resources are increasingly exhausted, and selective recovery of heavy metal resources is a major challenge in realizing sustainable development. The environment of the heavy metal polluted wastewater is generally complex, and a plurality of symbiotic ions exist, so that the selective recovery of the heavy metal ions is difficult. The traditional method for repairing the heavy metal polluted water body comprises chemical precipitation, electrocoagulation, membrane filtration, ion exchange and the like. However, these methods have some disadvantages, such as high cost of chemical sludge process, difficulty in regeneration and fouling. Adsorption is considered one of the most effective, the simplest, and the most economical techniques.
In general, conventional adsorbents (including activated carbon, clays, activated alumina, and zeolites) have poor selectivity, which results in difficult and less pure targeted recovery of heavy metals from complex aqueous environments. Therefore, it is necessary to develop a new method for enhancing the selectivity of the adsorbent to heavy metal ions.
Vegetable tannins of natural polyphenols are very common in various higher plants, and Tannic Acid (TA) molecules are excellent in adsorption of metal ions, especially in selective adsorption of lead ions, due to abundant functional groups. However, the individual tannic acid molecules tend to aggregate together so that the adsorption sites are masked and do not sufficiently contact the lead ions.
The patent application with publication number CN107970897A discloses a preparation method of a tannin-based adsorbent for removing heavy metal ions in water, and the prepared tannin-based adsorbent has good performance of adsorbing heavy metal ions and can be applied to various wastewater treatments, but the adsorbent in the prior art has crossed selectivity, so that the heavy metal is difficult to be recovered in a targeted manner.
Disclosure of Invention
The invention aims to solve the technical problem that an adsorbent in the prior art has poor selectivity, so that heavy metals are difficult to be recovered in a targeted manner, and provides a preparation method of a tannin-cyclodextrin gel type adsorption material.
The invention solves the technical problems through the following technical means:
a preparation method of a tannin-cyclodextrin gel type adsorption material comprises the following steps:
(1) dissolving tannic acid and cyclodextrin in an organic solvent 1 to prepare a mixed solution of tannic acid and cyclodextrin;
(2) dissolving terephthaloyl chloride in an organic solvent 2 to prepare a terephthaloyl chloride mixed solution;
(3) and (3) dripping the terephthaloyl chloride mixed solution prepared in the step (2) into the tannic acid and cyclodextrin mixed solution, sealing after dripping, preserving heat, taking out and cooling, filtering the solution, purifying the obtained solid, and drying to obtain the tannic acid-cyclodextrin gel-type adsorbing material.
Has the advantages that: according to the invention, tannic acid and cyclodextrin are crosslinked to prepare the aerogel material, functional groups of tannic acid are reserved, and with the help of a macromolecular framework of cyclodextrin, tannic acid can enable adsorption sites to be exposed in a water environment to a large extent under effective support, and under the crosslinking action of cyclodextrin, the adsorption selectivity and adsorption capacity of the material on lead ions are enhanced, so that the material is separated from other heavy metal ions in a water body, and the selective recovery of the lead ions is realized.
The preparation method is simple, convenient to operate, green and environment-friendly, can selectively recover lead ions in the wastewater, reduces the pollution of water, and simultaneously realizes the selective recovery of metal resources.
Preferably, the organic solvent 1 in the step (1) is pyridine or triethylamine, the mass ratio of the tannic acid to the cyclodextrin is 1:1, and the volume ratio of the tannic acid to the organic solvent 1 is 37.5g: 1L.
Has the advantages that: the organic solvent 1 is used to dissolve tannic acid and cyclodextrin on the one hand and to absorb the acid in the reaction with alkali on the other hand.
Preferably, the cyclodextrin is β -cyclodextrin.
Preferably, the organic solvent 2 in the step (2) is tetrahydrofuran, dimethylformamide or dimethyl sulfoxide, and the ratio of the mass of the terephthaloyl chloride to the volume of the organic solvent 2 is 100g: 1L.
Has the advantages that: the organic solvent 2 dissolves terephthaloyl chloride, and DMF and DMSO also dissolve terephthaloyl chloride, but these two solvents are not easily removed.
Preferably, in the step (3), the terephthaloyl chloride mixed solution is dropwise added into the tannin and cyclodextrin mixed solution under stirring at-5 to 5 ℃.
Preferably, the dropping time in the step (3) is within 30 min.
Preferably, the temperature in the step (3) is kept at 75-85 ℃ for 20-24 h.
Has the advantages that: the reaction time has an influence on the preparation of the adsorbent material, and too short a time may result in low yield.
Preferably, the purification step in step (3) comprises: the obtained solid is washed by ethanol and then by deionized water.
Has the advantages that: excess tannic acid is washed away with ethanol, and then residual ethanol is washed away with deionized water.
Preferably, the solid purified in step (3) is dried in a vacuum oven at 50 ℃ for 48 h.
The invention aims to solve the technical problem that an adsorbent in the prior art has poor selectivity, so that heavy metals are difficult to be recovered in a targeted manner from a complex water environment, and provides a tannin-cyclodextrin gel type adsorption material.
The invention solves the technical problems through the following technical means:
a tannin-cyclodextrin gel type adsorption material prepared by the above preparation method is provided.
Has the advantages that: the tannin-cyclodextrin gel type adsorption material has good adsorption selectivity and adsorption capacity for lead ions.
Preferably, the pore diameter of the mesoporous structure of the tannin-cyclodextrin gel type adsorbing material is less than 10nm, and the specific surface area of the tannin-cyclodextrin gel type adsorbing material is 2.31m2 g-1。
Has the advantages that: the adsorption of lead ions mainly occurs on the surface of the tannin-cyclodextrin gel type adsorption material, which is reflected in the rapid kinetics of the adsorption of lead ions by the adsorbent material, and shows that the adsorption of lead ions by the tannin-cyclodextrin gel type adsorption material can rapidly reach the balance in a short time, which is beneficial to efficiently treating a large amount of lead-containing practical wastewater in industrial application.
The invention aims to solve the technical problem that an adsorbent in the prior art has poor selectivity, so that heavy metals are difficult to be recovered in a targeted manner from a complex water environment, and provides an application of a tannic acid-cyclodextrin gel type adsorption material in lead ion adsorption.
The invention solves the technical problems through the following technical means:
an application of the tannin-cyclodextrin gel type adsorption material prepared by the preparation method in adsorption of lead ions.
Has the advantages that: the tannin-cyclodextrin gel type adsorption material is applied to adsorption of lead ions, has good selectivity and adsorption capacity, can be used for pertinently recovering the lead ions in a complex water environment, and is high in recovery rate.
Preferably, the tannic acid-cyclodextrin gel-type adsorbing material is placed in a solution containing lead ions for adsorption.
Preferably, the lead ion concentration of the lead ion-containing solution is 200mg/L, the solution volume is 400mL, the mass of the tannin-cyclodextrin gel-type adsorbing material is 400mg, and the adsorption time is 15 min.
Has the advantages that: lead ions are adsorbed under the conditions, so that adsorption balance can be achieved within 15min, and good adsorption performance is shown.
The invention has the advantages that: the tannin and the cyclodextrin are crosslinked to prepare the aerogel material, functional groups of the tannin are reserved, the tannin can be effectively supported by virtue of a macromolecular framework of the cyclodextrin to enable adsorption sites to be exposed in a water environment to a large extent, and the adsorption selectivity and the adsorption capacity of the material to lead ions are enhanced under the crosslinking action of the cyclodextrin, so that the tannin is separated from other heavy metal ions in a water body, and the selective recovery of the lead ions is realized.
The tannin-cyclodextrin gel type adsorption material has good adsorption selectivity and adsorption capacity for lead ions.
Drawings
FIG. 1 is a scanning electron microscope image of a tannin-cyclodextrin gel-type adsorbent material prepared in example 1 of the present invention;
FIG. 2 is a data chart of lead ion adsorption amounts of the tannin-cyclodextrin gel-type adsorbent material prepared in example 1 of the present invention in lead ion solutions with different concentrations;
FIG. 3 is a data graph showing the change of the lead ion adsorption amount of the tannin-cyclodextrin gel-type adsorbent material prepared in example 1 of the present invention in a lead ion solution with time;
FIG. 4 is a graph showing the adsorption amounts of tannin-cyclodextrin gel-type adsorbent materials prepared in example 1 of the present invention to different metal ions under the same conditions;
FIG. 5 is a data graph showing the adsorption amount of lead ions after the tannin-cyclodextrin gel-type adsorbent material prepared in example 1 of the present invention is recycled;
fig. 6 is a graph showing the measurement results of the specific surface area of the tannic acid-cyclodextrin gel-type adsorbent produced in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The specific techniques or conditions not specified in the examples can be performed according to the techniques or conditions described in the literature in the field or according to the product specification.
Example 1
The preparation method of the tannin-cyclodextrin gel type adsorption material comprises the following steps:
(1) dissolving tannic acid and beta-cyclodextrin in a pyridine-containing round-bottom flask to obtain a mixed solution of tannic acid and cyclodextrin, wherein the solvent is pyridine, the mass ratio of the tannic acid to the cyclodextrin is 1:1, and the volume ratio of the tannic acid to the pyridine is 37.5g: 1L;
(2) dissolving terephthaloyl chloride in Tetrahydrofuran (THF) to obtain a solution of terephthaloyl chloride with a solvent of THF; wherein the mass ratio of the terephthaloyl chloride to the volume of the THF is 100g: 1L;
(3) dropwise adding the terephthaloyl chloride solution prepared in the step (1) into a tannic acid cyclodextrin mixed solution at the temperature of-5 ℃, controlling the time dropwise adding within half an hour, immediately sealing after dropwise adding, putting into an oil bath pot, preserving heat at 80 ℃ for 24 hours, taking out from the oil bath pot, cooling, filtering the solution, filtering the obtained solid with 500mL of ethanol to remove tannic acid excessive in reaction, filtering with 500mL of deionized water to remove residual ethanol, and finally drying in a vacuum oven at 50 ℃ for 48 hours to obtain the tannic acid-cyclodextrin gel type adsorbing material.
Example 2
This embodiment is different from embodiment 1 in that: the organic solvent 1 is triethylamine.
Example 3
This embodiment is different from embodiment 1 in that: the organic solvent 2 is dimethylformamide.
Example 4
This embodiment is different from embodiment 1 in that: the organic solvent 2 is dimethyl sulfoxide.
Example 5
This embodiment is different from embodiment 1 in that: in the step (3): dropwise adding the terephthaloyl chloride solution prepared in the step (1) into the tannic acid cyclodextrin mixed solution at the temperature of 0 ℃, controlling the time dropwise adding within half an hour, immediately sealing after dropwise adding, putting into an oil bath pot, preserving heat at 85 ℃ for 20 hours, taking out from the oil bath pot, cooling, filtering the solution, filtering the obtained solid with 500mL of ethanol to remove tannic acid excessive in reaction, filtering with 500mL of deionized water to remove residual ethanol, and finally drying in a vacuum oven at 50 ℃ for 48 hours to obtain the tannic acid-cyclodextrin gel type adsorbing material.
Example 6
This embodiment is different from embodiment 1 in that: in the step (3): dropwise adding the terephthaloyl chloride solution prepared in the step (1) into the tannic acid cyclodextrin mixed solution at the temperature of 0 ℃, controlling the time dropwise adding within half an hour, immediately sealing after dropwise adding, putting into an oil bath pot, preserving heat for 22 hours at the temperature of 75 ℃, taking out from the oil bath pot, cooling, filtering the solution, filtering the obtained solid with 500mL of ethanol to remove tannic acid excessive in reaction, filtering with 500mL of deionized water to remove residual ethanol, and finally drying in a vacuum oven at the temperature of 50 ℃ for 48 hours to obtain the tannic acid-cyclodextrin gel type adsorbing material.
Example 7
Scanning electron microscope observation is carried out on the tannin-cyclodextrin gel-type adsorbing material prepared in the example 1
FIG. 1 is an SEM image of a tannin-cyclodextrin gel-type adsorbing material, and it can be seen from the SEM image that tannin and cyclodextrin are crosslinked with each other to form a three-dimensional porous structure, so that a gel-like material is prepared, the surface of the gel-like material is rough, and the gel-like material has more adsorption sites, and the structure is favorable for the adsorption of heavy metal ions by the material.
The porous structure, the rough surface and more adsorption sites of the adsorption material are brought by the cross-linking of the tannic acid and the cyclodextrin. Tannic acid provides an adsorption site for heavy metal ions, and beta-cyclodextrin provides a material structure. Under the condition of cross-linking of the two raw materials, functional groups of the tannic acid are reserved to a certain extent, and meanwhile, with the help of a macromolecular skeleton of the cyclodextrin, the tannic acid can enable adsorption sites to be exposed in a water environment to a large extent under effective support, and the tannic acid and the cyclodextrin jointly influence the performance of the final material in a water body and the adsorption of heavy metal ions.
Example 8
The tannin-cyclodextrin gel type adsorbing materials prepared in example 1 are adopted to adsorb lead ion aqueous solutions with different concentrations
The determination method comprises the following steps:
(1) weighing 1.598g of lead nitrate and dissolving the lead nitrate in 1L of deionized water to obtain an initial solution with the lead element concentration of 1 g/L; taking 4mL, 6mL, 8mL, 10mL, 12mL, 15mL, 20mL and 25mL of initial solution to perform constant volume in a 100mL volumetric flask to obtain lead ion aqueous solutions with the concentrations of 40mg/L, 60mg/L, 80mg/L, 100mg/L, 120mg/L, 150mg/L, 200mg/L and 250mg/L respectively; each 20mL of these concentrations of solution was taken in eight 50mL standard erlenmeyer flasks;
(2) weighing 20mg and 8 parts in total of the tannin-cyclodextrin gel type adsorbing materials prepared in the example 1, respectively adding 20mg of the adsorbing materials into conical flasks containing lead ion aqueous solutions with different concentrations, putting the conical flasks into a shaking table for an adsorption experiment, and setting the parameters of the shaking table as follows: the temperature is 25 ℃, the rotating speed is 180 ℃, and the time is 12 hours;
(3) taking 0.5mL of each mixed ion solution before and after adsorption, respectively measuring the change of the lead ion concentration before and after adsorption of the lead ion solutions with different concentrations by using an atomic absorption spectrometer, and calculating the adsorption amount.
And (3) measuring results: the gel-type adsorption material can expose adsorption sites for lead ions after swelling in water, fig. 2 is a data diagram of lead ion adsorption capacity of tannin-cyclodextrin gel-type adsorption material in lead ion solutions with different concentrations, and C in the data diagrameThe lead ion concentration is shown, and it can be seen that the lead ion adsorption capacity of the tannin-cyclodextrin gel type adsorption material gradually increases with the increase of the lead ion concentration, and when the lead ion concentration is 120mg/L, the tannin-cyclodextrin gel type adsorption material achieves the saturated adsorption capacity of 93mg/g, and the material has good adsorption effect on the lead ions.
Example 9
The lead ion adsorption amount of the tannin-cyclodextrin gel-type adsorbent material prepared in example 1 was measured at different times
The determination method comprises the following steps:
(1) weighing 1.598g of lead nitrate and dissolving in 1L of deionized water to obtain a solution with the lead element concentration of 1g/L, weighing 100mL of the solution with the lead element concentration of 1g/L and fixing the volume in a 500mL volumetric flask to obtain a solution with the lead element concentration of 200mg/L, and taking lead ions (Pb ions)2+) 400mL of the aqueous solution in a 500mL beaker;
(2) taking 400mg of the tannin-cyclodextrin gel-type adsorbing material prepared in the example 1, placing the lead ion aqueous solution obtained in the step (1) on a stirrer, stirring at the rotating speed of 500r/min, then adding 400mg of the tannin-cyclodextrin gel-type adsorbing material into the lead ion aqueous solution, simultaneously taking 1mL of the solution, setting the solution as a time point of 0, then respectively taking 1mL of the solution when the time points are 0.5min, 1min, 3min, 10min, 15min, 20min, 50min and 180min, respectively measuring the change of the lead ion concentration in the lead ion solution at different time points in the adsorption process by using an atomic absorption spectrometer, and calculating the adsorption quantity.
And (3) measuring results: fig. 3 is a data diagram of the change of the lead ion adsorption capacity of the tannin-cyclodextrin gel-type adsorption material in the lead ion solution with time, and it can be seen from the data diagram that the tannin-cyclodextrin gel-type adsorption material has a high adsorption rate for the lead ions, and reaches adsorption equilibrium at 15min, which indicates that the material can rapidly remove the lead ions in water and exhibits good adsorption performance.
Example 10
Effect of the tannin-cyclodextrin gel-type adsorbent prepared in example 1 on the adsorption selectivity of lead ions was measured
The determination method comprises the following steps:
(1) weighing 33.12mg of lead nitrate, 24.16mg of copper nitrate trihydrate, 29.10mg of cobalt nitrate hexahydrate, 29.08mg of nickel nitrate hexahydrate, 29.75mg of zinc nitrate hexahydrate and 30.85mg of cadmium nitrate tetrahydrate in a 100mL volumetric flask for constant volume to obtain a solution with the concentration of mixed metal ions of 1mmol/L, and putting 20mL of the solution in a 50mL conical flask;
(2) weighing 20mg of the tannin-cyclodextrin gel-type adsorbent material prepared in example 1, adding the adsorbent material into a conical flask containing a mixed ion aqueous solution, placing the conical flask in a shaking table for adsorption experiments, and setting the parameters of the shaking table as follows: the temperature is 25 ℃, the rotating speed is 180r/min, the mixture is kept for 12h, 0.5mL of mixed ion solution before and after adsorption is taken, the change of the concentration of each metal ion in the electrolyte solution before and after adsorption is respectively measured by using an atomic absorption spectrometer, and the adsorption capacity is calculated.
And (3) measuring results: fig. 4 is a data graph of the adsorption amount of the tannin-cyclodextrin gel-type adsorption material to each metal ion in the mixed ion solution under the same adsorption condition, and it can be seen that, under the same adsorption condition, the adsorption amount of the adsorption material to lead ions is the highest among six metal ions and is much higher than that to other metal ions, indicating that the tannin-cyclodextrin gel-type adsorption material has high selectivity to lead ions.
Example 11
The adsorption selectivity of the tannin-cyclodextrin gel-type adsorbent material prepared in example 1 to lead ions after cyclic regeneration was measured.
The determination method comprises the following steps:
(1) weighing 1.598g of lead nitrate and dissolving in 1L of deionized water to obtain an initial solution with the lead element concentration of 1g/L, taking 10mL of the initial solution with the lead element concentration of 1g/L and fixing the volume in a 500mL volumetric flask to obtain a solution with the lead element concentration of 20mg/L, and taking lead ions (Pb ions)2+) 400mL of the aqueous solution in a 500mL beaker;
(2) weighing 400mg of the tannic acid-cyclodextrin gel-type adsorbing material prepared in the example 1, placing the lead ion aqueous solution obtained in the step (1) on a stirrer, stirring at the rotating speed of 500r/min, adding the 400mg of the tannic acid-cyclodextrin gel-type adsorbing material into the lead ion aqueous solution, stirring for 2 hours, taking 1mL of the solution, measuring the change of the concentration of lead ions in the solution by using an atomic absorption spectrometer, and calculating the adsorption amount;
(3) performing suction filtration on the remaining suspension liquid mixed with the tannin-cyclodextrin gel-type adsorbing material prepared in the example 1 and the lead ion aqueous solution obtained in the step (1) to obtain a wet state of powder of the adsorbed tannin-cyclodextrin gel-type adsorbing material, washing the powder in a beaker by 200mL of 0.1M/L HCl, placing the beaker on a stirrer, performing lead ion elution, stirring at the rotating speed of 500r/min, performing suction filtration after 1 hour to obtain 5mL of filtrate, determining the change of the lead ion concentration in the solution by using an atomic absorption spectrometer, repeating the operation for at least 5 times until the lead ion concentration in the solution approaches to 0, and drying the eluted and suction-filtered tannin-cyclodextrin gel-type adsorbing material in an oven at 60 ℃ for 6 hours to obtain a regenerated tannin-cyclodextrin gel-type adsorbing material;
(4) preparing a solution with the lead element concentration of 20mg/L according to the step (1), and taking lead ions (Pb)2+) 300mL of the aqueous solution in a 500mL beaker;
(5) weighing 300mg of the regenerated tannic acid-cyclodextrin gel-type adsorbing material obtained in the step (3), placing the lead ion aqueous solution obtained in the step (4) on a stirrer, and repeating the operation of the step (2);
(6) performing suction filtration on the residual regenerated tannin-cyclodextrin gel type adsorbing material obtained in the step (3) and the suspension liquid of the lead ion aqueous solution obtained in the step (4) to obtain the wet powder of the adsorbed tannin-cyclodextrin gel type adsorbing material, and repeating the operation of the step (3);
(7) preparing a solution with the lead element concentration of 20mg/L according to the step (1), and taking lead ions (Pb)2+) 200mL of the aqueous solution in a 500mL beaker;
(8) weighing 200mg of the regenerated tannic acid-cyclodextrin gel-type adsorbing material obtained in the step (6), placing the lead ion aqueous solution obtained in the step (7) on a stirrer, and repeating the operation of the step (2);
(9) performing suction filtration on the residual regenerated tannin-cyclodextrin gel type adsorbing material obtained in the step (6) and the suspension liquid of the lead ion aqueous solution obtained in the step (7) to obtain the wet powder of the adsorbed tannin-cyclodextrin gel type adsorbing material, and repeating the operation of the step (3);
(10) preparing a solution with the lead element concentration of 20mg/L according to the step (1), and taking lead ions (Pb)2+) 100mL of the aqueous solution in a 250mL beaker;
(11) weighing 300mg of the regenerated tannic acid-cyclodextrin gel-type adsorbing material obtained in the step (9), placing the lead ion aqueous solution obtained in the step (10) on a stirrer, and repeating the operation of the step (2);
(12) performing suction filtration on the residual regenerated tannin-cyclodextrin gel-type adsorbing material obtained in the step (9) and the suspension liquid of the lead ion aqueous solution obtained in the step (10) to obtain the wet powder of the adsorbed tannin-cyclodextrin gel-type adsorbing material, and repeating the operation of the step (3);
(13) preparing a solution with the lead element concentration of 20mg/L according to the step (1), and taking lead ions (Pb)2+) 100mL of the aqueous solution in a 250mL beaker;
(14) weighing 300mg of the regenerated tannic acid-cyclodextrin gel-type adsorbing material obtained in the step (12), placing the lead ion aqueous solution obtained in the step (13) on a stirrer, and repeating the operation of the step (2);
(15) and (3) carrying out suction filtration on the residual regenerated tannin-cyclodextrin gel-type adsorbing material obtained in the step (12) and the suspension liquid of the lead ion aqueous solution obtained in the step (13) to obtain the wet powder of the adsorbed tannin-cyclodextrin gel-type adsorbing material, and repeating the operation in the step (3).
And (3) measuring results: as can be seen from fig. 5, the lead ion adsorption capacity of the tannin-cyclodextrin gel-type adsorption material is substantially unchanged after 5 times of cyclic regeneration.
Example 12
The specific surface area of the tannin-cyclodextrin gel-type adsorbent material of example 1 was measured
As shown in FIG. 6, it can be seen from FIG. 6 that the tannin-cyclodextrin gel-type adsorbent exhibited a relatively low specific surface area (2.31 m)2 g-1) And the aperture of the mesoporous structure is mainly less than 10 nm. The adsorption of lead ions is mainly generated on the surface of the tannin-cyclodextrin gel type adsorption material, which is reflected in the rapid kinetics of the adsorption of lead ions by the adsorbent material, and the result shows that the adsorption of lead ions by the tannin-cyclodextrin gel type adsorption material can rapidly reach the equilibrium in a short time, which is beneficial to efficiently treating a large amount of lead-containing actual wastewater in industrial application.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (7)
1. A preparation method of a tannin-cyclodextrin gel type adsorption material is characterized by comprising the following steps: the method comprises the following steps:
(1) dissolving tannic acid and cyclodextrin in an organic solvent 1 to prepare a mixed solution of tannic acid and cyclodextrin; the organic solvent 1 is pyridine or triethylamine, the mass ratio of the tannic acid to the cyclodextrin is 1:1, and the volume ratio of the tannic acid to the organic solvent 1 is 37.5g: 1L;
(2) dissolving terephthaloyl chloride in an organic solvent 2 to prepare a terephthaloyl chloride solution; the organic solvent 2 is tetrahydrofuran, dimethylformamide or dimethyl sulfoxide, and the mass ratio of the terephthaloyl chloride to the volume of the organic solvent 2 is 100g: 1L;
(3) dropwise adding the terephthaloyl chloride solution prepared in the step (2) into the mixed solution of tannic acid and cyclodextrin, sealing after dropwise adding, keeping the temperature at 75-85 ℃ for 20-24h, taking out, cooling, filtering the solution, purifying the obtained solid, and drying to obtain the tannic acid-cyclodextrin gel-type adsorbing material.
2. The method of preparing a tannic acid-cyclodextrin gel-type adsorbent material of claim 1, comprising: the cyclodextrin is beta-cyclodextrin.
3. The method of preparing a tannic acid-cyclodextrin gel-type adsorbent material of claim 1, comprising: and (3) dropwise adding the terephthaloyl chloride mixed solution into the tannin and cyclodextrin mixed solution at the temperature of-5-5 ℃ under stirring.
4. The method of preparing a tannic acid-cyclodextrin gel-type adsorbent material of claim 1, comprising: and (4) drying the solid purified in the step (3) in a vacuum oven at 50 ℃ for 48 hours.
5. A tannin-cyclodextrin gel-type adsorbent material produced by the production method according to any one of claims 1 to 4.
6. Use of the tannin-cyclodextrin gel-type adsorbent material prepared by the preparation method of any one of claims 1 to 4 for adsorbing lead ions.
7. The use of the tannin-cyclodextrin gel-type adsorbent material of claim 6, wherein: placing tannin-cyclodextrin gel type adsorbing material in lead ion-containing solution for adsorption.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010850947.7A CN112023888B (en) | 2020-08-21 | 2020-08-21 | Preparation method of tannin-cyclodextrin gel type adsorption material, prepared adsorption material and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010850947.7A CN112023888B (en) | 2020-08-21 | 2020-08-21 | Preparation method of tannin-cyclodextrin gel type adsorption material, prepared adsorption material and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112023888A CN112023888A (en) | 2020-12-04 |
| CN112023888B true CN112023888B (en) | 2021-09-21 |
Family
ID=73580473
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010850947.7A Active CN112023888B (en) | 2020-08-21 | 2020-08-21 | Preparation method of tannin-cyclodextrin gel type adsorption material, prepared adsorption material and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112023888B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112481833A (en) * | 2020-12-31 | 2021-03-12 | 华南农业大学 | Environment-friendly micro-nano fiber film material, preparation method thereof and application thereof in water lead pollution treatment |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05277467A (en) * | 1992-03-30 | 1993-10-26 | Nobuo Ogura | Adsorption removal of heavy metal salt by tannin-containing wood |
| CN101992064A (en) * | 2009-08-25 | 2011-03-30 | 付华峰 | Method for preparing novel tannic acid curing chitosan heavy metal ion adsorbent |
| WO2011116222A2 (en) * | 2010-03-17 | 2011-09-22 | Northwestern University | Nanoporous carbohydrate frameworks and the sequestration and detection of molecules using the same |
| CN102266754A (en) * | 2011-07-29 | 2011-12-07 | 湖北食为天药业科技有限公司 | Method for preparing activated carbon-persimmon tannin compound absorbent |
| CN103877946A (en) * | 2014-04-14 | 2014-06-25 | 福建农林大学 | Preparation method of tannin-loaded collagen/cellulose composite biological adsorption material |
| CN104497231A (en) * | 2015-01-08 | 2015-04-08 | 中山大学惠州研究院 | Method for preparing modified oil-absorptive resin immobilized with cyclodextrin molecules |
| BR102015025482A2 (en) * | 2015-09-25 | 2018-01-02 | Universidade Estatual De Santa Cruz | Adsorbent Preparation Process for PB (II) ION REMOVAL IN WATER FROM TANINE AND CARBON NANOTUBES |
-
2020
- 2020-08-21 CN CN202010850947.7A patent/CN112023888B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05277467A (en) * | 1992-03-30 | 1993-10-26 | Nobuo Ogura | Adsorption removal of heavy metal salt by tannin-containing wood |
| CN101992064A (en) * | 2009-08-25 | 2011-03-30 | 付华峰 | Method for preparing novel tannic acid curing chitosan heavy metal ion adsorbent |
| WO2011116222A2 (en) * | 2010-03-17 | 2011-09-22 | Northwestern University | Nanoporous carbohydrate frameworks and the sequestration and detection of molecules using the same |
| CN102266754A (en) * | 2011-07-29 | 2011-12-07 | 湖北食为天药业科技有限公司 | Method for preparing activated carbon-persimmon tannin compound absorbent |
| CN103877946A (en) * | 2014-04-14 | 2014-06-25 | 福建农林大学 | Preparation method of tannin-loaded collagen/cellulose composite biological adsorption material |
| CN104497231A (en) * | 2015-01-08 | 2015-04-08 | 中山大学惠州研究院 | Method for preparing modified oil-absorptive resin immobilized with cyclodextrin molecules |
| BR102015025482A2 (en) * | 2015-09-25 | 2018-01-02 | Universidade Estatual De Santa Cruz | Adsorbent Preparation Process for PB (II) ION REMOVAL IN WATER FROM TANINE AND CARBON NANOTUBES |
Non-Patent Citations (3)
| Title |
|---|
| "Competitive biosorption of Pb2+, Cu2+ and Zn2+ ions from aqueous solutions onto valonia tannin resin";I.Ayhan Sengil et al.;《Journal of Hazardous Materials》;20081224;第166卷;第1488-1494页 * |
| "Pyromellitic Dianhydride-Modified β-Cyclodextrin Microspheres for Pb(II) and Cd(II) Adsorption";Fengyu Li et al.;《Journal of Applied Polymer Science》;20070530;第105卷;第3418-3425页 * |
| "环糊精基吸附剂的制备及对水中有机污染物去除的研究进展";于飞邓;《材料导报》;20181025;第32卷(第10期);第3645-3653页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112023888A (en) | 2020-12-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | Adsorption behavior of Au (III) and Pd (II) on persimmon tannin functionalized viscose fiber and the mechanism | |
| Ma et al. | Fast adsorption of heavy metal ions by waste cotton fabrics based double network hydrogel and influencing factors insight | |
| Yan et al. | Enhanced and selective adsorption of copper (II) ions on surface carboxymethylated chitosan hydrogel beads | |
| Lin et al. | Enhanced and selective adsorption of Hg2+ to a trace level using trithiocyanuric acid-functionalized corn bract | |
| Zhang et al. | Amino modification of rice straw-derived biochar for enhancing its cadmium (II) ions adsorption from water | |
| Sharma et al. | A perspective on diverse adsorbent materials to recover precious palladium and the way forward | |
| Li et al. | Preparation and characterization of multi-carboxyl-functionalized silica gel for removal of Cu (II), Cd (II), Ni (II) and Zn (II) from aqueous solution | |
| Wen et al. | Carbonaceous sulfur-containing chitosan–Fe (III): A novel adsorbent for efficient removal of copper (II) from water | |
| Liu et al. | Development and characterization of chitosan functionalized dialdehyde viscose fiber for adsorption of Au (III) and Pd (II) | |
| CN109608655B (en) | Difunctional group MOFs material and preparation method and application thereof | |
| CN102247799B (en) | Method for removing humic acid in water by utilizing surfactant modified attapulgite | |
| Xiao et al. | Fabrication of novel carboxyl and amidoxime groups modified luffa fiber for highly efficient removal of uranium (VI) from uranium mine water | |
| Park et al. | Fibrous polyethylenimine/polyvinyl chloride crosslinked adsorbent for the recovery of Pt (IV) from acidic solution: Adsorption, desorption and reuse performances | |
| Gan et al. | Synergistic action of multiple functional groups enhanced uranium extraction from seawater of porous phosphorylated chitosan/coal-based activated carbon composite sponge | |
| Li et al. | Highly selective adsorption of dyes and arsenate from their aqueous mixtures using a silica-sand/cationized-starch composite | |
| Song et al. | Synthesis of cross-linking chitosan-PVA composite hydrogel and adsorption of Cu (II) ions | |
| CN111589416A (en) | Lanthanum modified biochar and preparation method and application thereof | |
| Zhuqing et al. | Ion imprinted sol-gel nanotubes membrane for selective separation of copper ion from aqueous solution | |
| Yu et al. | Selective biosorption of U (VI) from aqueous solution by ion-imprinted honeycomb-like chitosan/kaolin clay composite foams | |
| Wang et al. | Highly effective and selective adsorption of Au (III) from aqueous solution by poly (ethylene sulfide) functionalized chitosan: Kinetics, isothermal adsorption and thermodynamics | |
| CN112844301B (en) | Dimer carboxyl adsorbent and preparation method and application thereof | |
| Xu et al. | Uptake of perchlorate from aqueous solutions by amine-crosslinked cotton stalk | |
| Ouyang et al. | Immobilization of carboxyl-modified multiwalled carbon nanotubes in chitosan-based composite membranes for U (VI) sorption | |
| Chen et al. | Recovery and investigation of Cu (II) ions by tannin immobilized porous membrane adsorbent from aqueous solution | |
| Feng et al. | Removal of copper (II) from an aqueous solution with copper (II)‐imprinted chitosan microspheres |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |