CN111203192B - Preparation method and application of modified chitosan microsphere adsorbent for adsorbing perchlorate - Google Patents
Preparation method and application of modified chitosan microsphere adsorbent for adsorbing perchlorate Download PDFInfo
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Abstract
The invention belongs to the technical field of environmental management, and particularly relates to a preparation method and application of a modified chitosan microsphere adsorbent for adsorbing perchlorate, which comprises the following steps: weighing chitosan, dissolving the chitosan in an acetic acid solution, stirring for a certain time, refrigerating and standing to remove bubbles; dripping the chitosan solution into NaOH solution to perform gel reaction to obtain chitosan gel microspheres; after being cleaned to be neutral, carrying out crosslinking reaction according to a certain proportion of the molar mass of the chitosan monomer in the microsphere and the molar mass of the crosslinking agent ECH; adding the chitosan microspheres after the crosslinking reaction into ZrOCl2·8H2And reacting in an O aqueous solution for a certain time, and drying the obtained zirconium-containing microspheres to obtain the chitosan microsphere adsorbent. By improving the preparation process of the chitosan microsphere adsorbent, the perchlorate adsorption capacity of the chitosan microsphere adsorbent is greatly improved, and the method has the advantages of strong practicability, good treatment effect and good commercial application prospect.
Description
Technical Field
The invention belongs to the technical field of environmental management, and particularly relates to a preparation method and application of a modified chitosan microsphere adsorbent for adsorbing perchlorate.
Background
Perchlorate (ClO)4 -) Is a novel pollutant which is difficult to degrade, and the perchlorate in the environment is from natural synthesis and artificial synthesis. The naturally synthesized perchloric acid ions can be prepared from Cl in the atmosphere-And O3The perchlorate generated by oxidation reaction and synthesized by manpower is widely applied to a plurality of fields such as fertilizer, rocket propellant, detergent, military fire industry, highway safety flashing board and the like as chemical products. At present, China has a large number of chemical plants taking perchlorate as a direct product, and as a traditional big country for manufacturing and consuming fireworks, a large number of perchlorate pollutants are released in the manufacturing and setting-off processes of the fireworks. Research shows that perchlorate is detected in surface water, underground water, drinking water, sludge, air, dust, food and other environment medium in different degree. Toxicological studies show that perchlorate competes with iodine absorption after entering human body, so that normal synthesis of thyroid hormone in human body is interfered, and skeleton system is affectedAnd development of the central nervous system. Based on the physiological toxicity of perchloric acid, the U.S. environmental protection agency has placed perchlorate on a candidate list of environmental pollutants and has proposed an officially recommended safe concentration limit of 0.7 μ g/kg/day. Compared with the United states, no relevant law and regulation is provided at present in China to regulate the discharge standard of the perchlorate-containing sewage and the safe concentration of the perchlorate-containing sewage in drinking water. Since perchlorate is highly soluble, highly diffusive and stable, it will diffuse and sustain the pollution once it is discharged into the environment. Therefore, there is a need for an effective treatment method for treating perchlorate-containing wastewater, which is controlled from the source to reduce the pollution of the wastewater environment and reduce the exposure risk of human beings to perchlorate.
Because the adsorption separation method has the advantages of wide application, simple and convenient operation, controllable cost and the like, the method for removing the pollutants difficult to degrade by utilizing the adsorption separation method is considered to be a method with high feasibility. The perchlorate is difficult to be adsorbed by solid due to extremely high water solubility, and the special physicochemical property of the perchlorate puts higher requirements on developing an adsorbing material with high-efficiency adsorption capacity. Chitosan is a natural polymer material with the content second to that of cellulose in nature, and gel microsphere adsorbents prepared by taking chitosan as a carrier have been researched more. The chitosan adsorbent has the advantages of simple preparation process, good adsorption effect and the like, and the actual cost is equivalent to the cost of the activated carbon, so the chitosan adsorbent has extremely wide commercial application prospect. In recent years, domestic scholars have begun to study the adsorption treatment of perchlorate by using chitosan adsorbent, and some studies have been made on the preparation of chitosan adsorbent by using pentanediol (GA) as a cross-linking agent, but GA and amino group (-NH) in chitosan monomer2) The groups are subjected to a crosslinking reaction, and the amino groups are often active groups participating in an adsorption reaction, so that the perchlorate adsorption capacity of the chitosan adsorbent obtained by GA crosslinking is generally low, which limits the application of preparing a perchlorate adsorbent with more practical performance by using a chitosan material. Therefore, further optimization and innovation are needed, and a new preparation process of the chitosan adsorbent is adopted, so that the treatment capacity of the chitosan adsorbent on perchlorate is enhanced.
Disclosure of Invention
Aiming at the technical problem that the existing chitosan adsorbent is low in perchlorate adsorption capacity, the invention provides a preparation method and application of a modified chitosan microsphere adsorbent for adsorbing perchlorate, and the preparation method is characterized in that the preparation process of the chitosan microsphere adsorbent is improved, Epoxy Chloropropane (ECH) is used as a cross-linking agent, and active oxide, namely zirconium oxide, is added, so that the perchlorate adsorption capacity of the chitosan microsphere adsorbent on perchlorate can be greatly improved.
The technical scheme of the invention is as follows:
the preparation method of the modified chitosan microsphere adsorbent for adsorbing perchlorate comprises the following steps:
(1) weighing chitosan, dissolving the chitosan in an acetic acid solution, stirring for a certain time, refrigerating and standing to remove bubbles;
(2) dripping the chitosan solution obtained in the step (1) into a NaOH solution at a speed of 0.5-1.5 mL/min by using a peristaltic pump to perform a gel reaction to obtain chitosan gel microspheres;
(3) cleaning chitosan gel microspheres to be neutral, adding the microspheres and ECH into ultrapure water under the condition that the molar mass ratio of chitosan monomers in the microspheres to the molar mass of a crosslinking agent ECH is 0.5: 1-1.5: 1, adjusting the pH to 6-12, and then placing the microspheres on a shaking table for crosslinking reaction;
(4) adding the chitosan microspheres subjected to the crosslinking reaction into ZrOCl2·8H2And reacting in an O aqueous solution for 12-48 h, and drying the obtained zirconium-containing microspheres to obtain the modified chitosan microsphere adsorbent.
Further, ZrOCl in the step (4)2·8H2The adding mass volume ratio of the O is 0.01-5.0%.
Further, ZrOCl2·8H2The adding mass volume ratio of O is 0.05-1.0%.
Further, 5g of chitosan powder in the step (1) is weighed and dissolved in 200mL of 8% (V/V) acetic acid solution, stirred for 2h, and then placed in a refrigerator at 4 ℃ for standing overnight to remove bubbles.
Further, in the step (2), a peristaltic pump with a pinhole injector is adopted, and the chitosan solution is dropped into the NaOH solution with the concentration of 0.5-2.5 mol/L at the speed of 1mL/min for reaction.
Further, the parameters of the shaking table in the step (3) are set to be 40-80 ℃, 40-80 rpm, and the reaction lasts 12-24 hours.
Further, in the step (4), 5-15 g of chitosan microspheres cleaned after the crosslinking reaction is finished are added into 100-500 mLZrOCl2·8H2And (4) performing mixed reaction in the O aqueous solution.
Further, the drying operation in the step (4) is drying by using an oven, the temperature of the oven is set to be 40-80 ℃, and the drying is carried out for 12-48 hours.
The modified chitosan microsphere adsorbent prepared by the method is used for adsorbing and treating perchlorate-containing wastewater.
Further, the required pH range of the chitosan microsphere adsorbent is 3-10, and the temperature range is 25-50 ℃.
The invention has the beneficial effects that:
the invention firstly proposes that the chitosan microspheres prepared by using ECH as a cross-linking agent are used for adsorbing and treating perchlorate, and ECH only has a cross-linking reaction with hydroxyl (-OH) so as to reserve amino groups with adsorption activity, so that the ECH cross-linked chitosan adsorbent can obtain a better perchlorate adsorption effect. Meanwhile, in order to further improve the perchlorate adsorption capacity of the chitosan microspheres, the chitosan microspheres doped with zirconium oxide are prepared for the first time on the basis of the method, and remarkable effects are achieved, wherein the theoretical adsorption capacity of the chitosan adsorbent doped with 0.1% of zirconium oxide on perchlorate is 163.1 +/-8.5 mg/g.
Drawings
FIG. 1 shows ZrOCl2·8H2A relation graph between the addition proportion of O and the adsorption capacity of perchlorate;
FIG. 2 is a bar graph of the effect of pH on perchlorate adsorption capacity;
FIG. 3 is a bar graph of the effect of temperature on perchlorate adsorption capacity;
FIG. 4 is a bar graph of the effect of different coexisting ions on perchlorate adsorption.
Detailed Description
The technical solutions of the present invention will be described in detail and fully with reference to the following specific embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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.
For a further understanding of the present invention, reference will now be made in detail to the following examples.
Example 1
Weighing 5g of low-viscosity chitosan powder, dissolving in 200mL of 8% (V/V) acetic acid solution, stirring for 2h, placing in a refrigerator at 4 ℃ and standing for one night to remove bubbles; dripping the chitosan solution into NaOH solution with the concentration of 2mol/L at the speed of 1mL/min by using a peristaltic pump with a pinhole injector to carry out gel reaction to obtain milky chitosan gel microspheres; cleaning milky chitosan gel microspheres to neutral pH, adding the microspheres and a crosslinking agent into ultrapure water under the condition that the molar mass ratio of chitosan monomers to the crosslinking agent ECH in the microspheres is 1:1, adjusting the pH to 10, placing the microspheres on a shaking table for oscillation reaction, setting the parameters of the shaking table at 50 ℃, 60rpm, and carrying out the crosslinking reaction for 16 hours; adding 10g of chitosan microspheres which are cleaned after the crosslinking reaction is finished into 200mLZrOCl2·8H2And (3) carrying out mixing reaction in an aqueous solution with the mass-volume ratio (M/V) of 0.5% of O, reacting for 24 hours, and drying the zirconium-containing microspheres in an oven at 60 ℃ for 24 hours to obtain the chitosan microsphere adsorbent.
Example 2
Weighing 5g of low-viscosity chitosan powder, dissolving in 200mL of 8% (V/V) acetic acid solution, stirring for 2h, placing in a refrigerator at 4 ℃ and standing for one night to remove bubbles; dripping the chitosan solution into 0.5mol/L NaOH solution at a speed of 0.5mL/min by using a peristaltic pump with a pinhole syringe to generate gel reactionObtaining milky chitosan gel microspheres; cleaning milky chitosan gel microspheres to neutral pH, adding the microspheres and a crosslinking agent into ultrapure water under the condition that the molar mass ratio of chitosan monomers to the crosslinking agent ECH in the microspheres is 0.5:1, adjusting the pH to 8, placing the microspheres and the crosslinking agent ECH on a shaking table for oscillation reaction, setting the parameters of the shaking table at 40 ℃ and 80rpm, and carrying out the crosslinking reaction for 16 hours; adding 6g of chitosan microspheres which are cleaned after the crosslinking reaction is finished into 100mLZrOCl2·8H2And (3) carrying out mixing reaction in an aqueous solution with the mass-volume ratio (M/V) of 0.1%, after reacting for 36h, drying the zirconium-containing microspheres in an oven at 40 ℃ for 48h to obtain the chitosan microsphere adsorbent.
Example 3
Weighing 5g of low-viscosity chitosan powder, dissolving the chitosan powder in 200mL of 8% (V/V) acetic acid solution, stirring for 2h, and placing the mixture into a refrigerator at 4 ℃ for standing for one night to remove bubbles; dripping the chitosan solution into NaOH solution with the concentration of 2.5mol/L at the speed of 1.5mL/min by using a peristaltic pump with a pinhole injector to carry out gel reaction to obtain milky chitosan gel microspheres; cleaning milky chitosan gel microspheres to neutral pH, adding the microspheres and a crosslinking agent into ultrapure water under the condition that the molar mass ratio of chitosan monomers to the crosslinking agent ECH in the microspheres is 1.5:1, adjusting the pH to 12, placing the microspheres on a shaking table for oscillation reaction, setting the parameters of the shaking table at 60 ℃, and setting the speed of 40rpm to carry out the crosslinking reaction for 12 hours; 15g of chitosan microspheres which are washed clean after the crosslinking reaction is finished are added into 500mLZrOCl2·8H2And (3) carrying out mixing reaction in an aqueous solution with the mass volume ratio (M/V) of 1.0%, after 12h of reaction, drying the zirconium-containing microspheres in an oven at 80 ℃ for 12h to obtain the chitosan microsphere adsorbent.
Examples of the experiments
The chitosan microsphere adsorbent provided by the embodiment of the invention is used for carrying out an adsorption capacity test experiment, and the experimental process is as follows: a plurality of 20mg of the adsorbent was weighed and placed in 10mL of sodium perchlorate solutions (calculated as the perchlorate ion concentration) with concentrations ranging from 50, 100, 150, 200, 300, 500, 700, 1000, 1500 and 2000mg/L, respectively, and adsorption tests were carried out under reaction conditions of no initial pH adjustment, 30 ℃ and contact at a shaker speed of 150rpm for 8 hours. After the reaction is finished, the concentration of the residual perchloric acid ions is analyzed, and the obtained experimental data is substituted into a Langmuir adsorption isotherm equation to obtain that the adsorption capacity of the adsorbent in the embodiment of the invention reaches 163.1 mg/g.
Test example 1
ZrOCl2·8H2Relationship between O addition ratio and adsorption capacity
Using at different ZrOCl2·8H2The chitosan microsphere adsorbent obtained under the condition of the addition proportion of O is tested, and the test process is as follows: a plurality of 20mg chitosan microsphere adsorbents are weighed and respectively added into 10mL of 200mg/L sodium perchlorate solution (calculated by the concentration of perchloric acid ions), and adsorption experiments are carried out under the reaction conditions that the initial pH is not adjusted, the contact is carried out for 24 hours at 30 ℃ and the shaking table speed of 150 rpm. After the reaction is finished, the residual perchloric acid ion concentration is analyzed, and the adsorption capacity (mg/g) corresponding to different adsorbents can be obtained through calculation.
As can be seen from FIG. 1, ZrOCl is increased within a certain range2·8H2O addition amount and perchlorate adsorption capacity are increased, and excessive ZrOCl is generated after the peak value is reached2·8H2ZrOCl will inhibit the adsorption effect due to the addition of O2·8H2The mass volume ratio (M/V) range of the added O is 0.05-1.0%; this is a key point in distinction to other adsorbents, namely control of the amount of addition, a phenomenon related to the properties of perchlorate ions. Perchloric acid ions have strong hydrophobicity, excessive zirconium oxide is added to increase the hydrophilicity of the surface of the adsorbent, a water film is formed on the surface of the hydrophilic adsorbent, and the hydrophobic perchloric acid ions cannot break through the water film and cannot be combined with adsorption sites to be adsorbed.
Test example 2
Experiment on influence of pH of water body on adsorption effect
The chitosan microsphere adsorbent provided by the embodiment of the invention is used for carrying out adsorption capacity test tests under different pH conditions, and the test process is as follows: weighing 20mg of adsorbent in multiple portions, respectively placing the adsorbent in 10mL of 100mg/L sodium perchlorate solution (calculated by the concentration of perchloric acid ions), adjusting different initial pH values by using 1mol/L hydrochloric acid solution or sodium hydroxide solution, and carrying out adsorption experiments under the reaction conditions of 30 ℃ and 150rpm shaking table speed contact for 8 hours. After the reaction is completed, the residual perchloric acid ion concentration is analyzed, and the adsorption capacity (mg/g) of the adsorbent under different pH conditions can be calculated.
As shown in FIG. 2, a stable perchlorate adsorption amount can be maintained in a relatively common pH range of a natural water body, namely, the pH value is 3-10, and the influence of the pH on the adsorption effect is small.
Test example 3
Test for Effect of temperature on adsorption
The chitosan microsphere adsorbent provided by the embodiment of the invention is used for carrying out adsorption capacity test tests under different temperature conditions, and the experimental process is as follows: a plurality of 20mg of adsorbent is weighed and placed into 10mL of 200mg/L sodium perchlorate solution (calculated by the concentration of perchloric acid ions), and adsorption experiments are carried out under the reaction conditions that the temperature is 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃ and 50 ℃ are contacted for 8 hours at the shaking table speed of 150 rpm. After the reaction is finished, the concentration of the residual perchloric acid ions is analyzed, and the adsorption capacity (mg/g) of the adsorbent under different temperature conditions can be calculated.
As shown in FIG. 3, in a common temperature range, i.e., a temperature range of 25 to 50 ℃, the effect of temperature on perchlorate adsorption is limited, which indicates that the adsorbent can maintain good adsorption capacity under different temperature conditions.
Test example 4
Test for influence of coexisting ions on perchlorate adsorption
The modified chitosan microsphere adsorbent provided by the embodiment of the invention is used for carrying out an adsorption capacity test experiment under the condition that different ions (chloride ions, nitrate ions, sulfate ions and phosphate ions) coexist, and the experimental process is as follows: a plurality of 20mg portions of the adsorbent was weighed and placed in 10mL of 10mg/L sodium perchlorate solution (calculated as the perchlorate ion concentration). When the experiment of the influence of single coexisting ion is carried out, the four ions exist independently in 10mg/L sodium perchlorate solution, and three concentration gradients of 10, 50 and 100mg/L are respectively considered for each ion;in the experiment of the effect of a plurality of coexisting ions, the four ions were present together in a 10mg/L sodium perchlorate solution and the concentration gradient was 10, 50 and 100mg/L, respectively. The adsorption experiments were carried out at 30 ℃ under reaction conditions of contact for 8h at a shaker speed of 150 rpm. After the reaction is finished, the concentration of the residual perchloric acid ions is analyzed, and the adsorption capacity C of the adsorbent under different coexisting ion conditions can be calculated1(mg/g). C is to be1Adsorption capacity C of the adsorbent without any addition of coexisting ions2(mg/g) were compared by using the formula [ (C)2-C1)/C2]The percentage perchlorate absorption inhibition was calculated at 100%.
The experimental results are as follows: as can be seen from fig. 4, when the concentration of the coexisting ions is the same as that of the perchlorate ions, the effect of the adsorption of the perchlorate ions is negligible, and even if the concentration of the other ions is ten times that of the perchlorate, more than 50% of the perchlorate can be adsorbed, indicating that the adsorbent provided by the present invention has selectivity for the perchlorate.
The above description is only a preferred embodiment of the present invention and should not be taken as limiting the invention, and any modifications, equivalents, changes, etc. made within the scope of the present invention should be included in the claims of the present invention.
Claims (6)
1. The application of the modified chitosan microsphere adsorbent in adsorption treatment of perchlorate-containing wastewater is characterized in that the preparation method of the modified chitosan microsphere adsorbent comprises the following steps:
(1) weighing chitosan, dissolving the chitosan in an acetic acid solution, stirring for a certain time, refrigerating and standing to remove bubbles;
(2) dripping the chitosan solution obtained in the step (1) into a NaOH solution at a speed of 0.5-1.5 mL/min by using a peristaltic pump to perform a gel reaction to obtain chitosan gel microspheres;
(3) cleaning chitosan gel microspheres to be neutral, adding the microspheres and epoxy chloropropane into ultrapure water under the condition that the molar ratio of chitosan monomers to a cross-linking agent epoxy chloropropane in the microspheres is 0.5: 1-1.5: 1, adjusting the pH to 6-12, and then placing the microspheres on a shaking table for a cross-linking reaction;
(4) adding the chitosan microspheres subjected to the crosslinking reaction into ZrOCl2·8H2In an aqueous O solution, said ZrOCl2·8H2The adding mass volume ratio of O is 0.05-1.0%, and after the reaction is carried out for 12-48 h, the obtained zirconium-containing microspheres are dried to obtain the modified chitosan microsphere adsorbent;
the prepared modified chitosan microsphere adsorbent is applied to adsorption treatment of perchlorate-containing wastewater; in application, the pH range of the modified chitosan microsphere adsorbent is 3-10, and the temperature range is 25-50 ℃.
2. The use according to claim 1, wherein 5g of chitosan powder is weighed in step (1), dissolved in 200mL of 8% (V/V) acetic acid solution, stirred for 2h, and placed in a refrigerator at 4 ℃ for standing overnight to remove air bubbles.
3. The use of claim 1, wherein the step (2) comprises dropping the chitosan solution into NaOH solution with concentration of 0.5-2.5 mol/L at a speed of 1mL/min by using a peristaltic pump with a pinhole syringe.
4. The use of claim 1, wherein the shaking table in step (3) is set to have a temperature of 40-80 ℃ and a rpm of 40-80 for 12-24 h.
5. The use of claim 1, wherein in the step (4), 5-15 g of chitosan microspheres cleaned after the crosslinking reaction is completed are added to 100-500 mL of ZrOCl2·8H2And (4) performing mixed reaction in the O aqueous solution.
6. The application of claim 1, wherein the drying operation in the step (4) is drying in an oven, the temperature of the oven is set to be 40-80 ℃, and the drying is carried out for 12-48 h.
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