CN111203192A - 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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- 229920001661 Chitosan Polymers 0.000 title claims abstract description 85
- 239000004005 microsphere Substances 0.000 title claims abstract description 69
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000003463 adsorbent Substances 0.000 title claims abstract description 52
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 239000000243 solution Substances 0.000 claims abstract description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 27
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000004132 cross linking Methods 0.000 claims abstract description 17
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 12
- 229910006213 ZrOCl2 Inorganic materials 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000007935 neutral effect Effects 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000005303 weighing Methods 0.000 claims abstract description 6
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 6
- 230000002572 peristaltic effect Effects 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 5
- 239000012498 ultrapure water Substances 0.000 claims description 5
- 239000002351 wastewater Substances 0.000 claims description 4
- 238000010981 drying operation Methods 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 45
- 230000000694 effects Effects 0.000 abstract description 15
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 15
- -1 perchloric acid ions Chemical class 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 10
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 7
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 4
- 241000282414 Homo sapiens Species 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- AUYYCJSJGJYCDS-LBPRGKRZSA-N Thyrolar Chemical class IC1=CC(C[C@H](N)C(O)=O)=CC(I)=C1OC1=CC=C(O)C(I)=C1 AUYYCJSJGJYCDS-LBPRGKRZSA-N 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 238000005457 optimization Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 229940036555 thyroid hormone Drugs 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000041 toxicology testing Toxicity 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
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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; the chitosan after the crosslinking reaction is finishedMicrospheres were added to 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. Toxicology studies show that perchlorate competes with iodine absorption after entering the human body, so that the normal synthesis of thyroid hormone in the human body is interfered, and the perchlorate also influences the development of a skeletal system and a 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 safety 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 physical and chemical properties of the perchlorate are absorption for developing high-efficiency adsorption capacityThe additional materials put higher demands. 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.
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; the chitosan solution was injected at a rate of 1mL/min using a peristaltic pump with a syringe having a needle holeDripping the mixture into NaOH solution with the concentration of 2mol/L to perform 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 NaOH solution with the concentration of 0.5mol/L at the speed of 0.5mL/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 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 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 chitosan solution into NaOH solution with concentration of 2.5mol/L at a speed of 1.5mL/min by using peristaltic pump with pinhole injector to perform gel reaction to obtain milk whiteChitosan 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, in a certain range, ZrO increases with increasing amountCl2·8H2O 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: a plurality of 20mg of adsorbent is weighed and placed into 10mL of 100mg/L sodium perchlorate solution (calculated by the concentration of perchloric acid ions), the initial pH is adjusted by 1mol/L hydrochloric acid solution or sodium hydroxide solution, and the adsorption experiment is carried out under the reaction conditions of 30 ℃ and 150rpm shaking table speed contact for 8 h. 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 completed, the residual perchloric acid ion concentration 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). In the experiment of single coexisting ion influence, the four ions exist independently in a 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 for the preferred embodiment of the present invention and should not be taken as limiting the invention, and any modifications, equivalents, improvements and the like made within the scope of the present invention should be included in the patent protection scope of the present invention.
Claims (10)
1. The preparation method of the modified chitosan microsphere adsorbent for adsorbing perchlorate is characterized by comprising 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.
2. The method of claim 1, wherein ZrOCl in step (4)2·8H2The adding mass volume ratio of the O is 0.01-5.0%.
3. The method of claim 2, wherein the ZrOCl2·8H2The adding mass volume ratio of O is 0.05-1.0%.
4. The method 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 bubbles.
5. The method of claim 1, wherein in the step (2), a peristaltic pump with a pinhole syringe 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.
6. The method 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 hours.
7. The method according to claim 1, wherein in the step (4), 5-15 g of chitosan microspheres cleaned after the crosslinking reaction is completed are added into 100-500 mL of ZrOCl2·8H2And (4) performing mixed reaction in the O aqueous solution.
8. The method as claimed in claim 1, wherein the drying operation in the step (4) is oven drying, the oven temperature is set to be 40-80 ℃, and the drying is carried out for 12-48 hours.
9. The modified chitosan microsphere adsorbent prepared by the method according to the claims 1-8 is applied to adsorbing and treating perchlorate-containing wastewater.
10. The use of claim 9, wherein the modified chitosan microsphere adsorbent requires a pH in the range of 3 to 10 and a temperature in the range of 25 to 50 ℃.
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| CN114100587A (en) * | 2021-12-08 | 2022-03-01 | 国网湖北省电力有限公司孝感供电公司 | Large-scale production method of chitosan adsorbent for regeneration of deteriorated insulating oil |
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| CN114100587A (en) * | 2021-12-08 | 2022-03-01 | 国网湖北省电力有限公司孝感供电公司 | Large-scale production method of chitosan adsorbent for regeneration of deteriorated insulating oil |
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