CN113070046B - Preparation method of defluorination adsorbent modified by biopolymer composite material - Google Patents
Preparation method of defluorination adsorbent modified by biopolymer composite material Download PDFInfo
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- 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/28002—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 physical properties
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- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
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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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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- C02F1/00—Treatment of water, waste water, or sewage
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- C02F2101/00—Nature of the contaminant
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- C02F2101/14—Fluorine or fluorine-containing compounds
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Abstract
The preparation method of the defluorination adsorbent modified by the biopolymer composite material comprises the following steps: respectively dissolving chitosan and pectin in deionized water or acid, mixing the two solutions, and heating to perform biopolymer crosslinking reaction; adding a molecular sieve soaked by deionized water into the mixed solution, distilling under reduced pressure, adding chloroacetic acid and sodium hydroxide aqueous solution, and grafting chloroacetic acid to modify the chitosan-pectin biopolymer composite material; adding metal nitrate dissolved in a mixed solution of ethanol and water into the modified molecular sieve, distilling under reduced pressure, adding a sodium hydroxide solution, stirring at room temperature, and doping metal ions into crystal lattices of the modified polymer; and filtering the redundant mixed solution, removing the seed water, washing to be neutral, and drying in an oven to obtain the modified defluorination adsorbent. The method has the advantages of simple preparation process, low cost, easy recovery and recycling, and high fluorine removal efficiency in the wastewater.
Description
Technical Field
The invention relates to the technical field of preparation of a defluorination adsorbent, in particular to a defluorination adsorbent modified by a biopolymer composite material.
Background
In the fields of phosphate fertilizer production, aluminum smelting and electroplating, fluorine-containing waste gas, waste water and waste residues are generated in actual production operation and are discharged into the natural environment, and the fluorine-containing waste water and the waste gas and the waste residues dissolved in natural precipitation or surface runoff reach underground water in a permeation mode and the like. Fluorine is the most electronegative element and therefore has a negative charge in aqueous media and forms F - Ions. While trace fluorine is essential to human body, high concentration can cause serious problems such as Alzheimer's disease, infertility, osteoporosis, thyroid disease, brain damage, cancerSymptoms, brittle bones, etc. In view of the severity of the harm caused by excessive fluorine and the condition that most of the fluorine content in underground water exceeds the standard, the research on fluorosis and the research on fluorine removal technology and process of high-fluorine water arouse the wide attention of people. The commonly used defluorination methods at present mainly comprise: membrane separation, precipitation, adsorption, electrocoagulation, reverse osmosis, and the like. However, most of the above methods require high operation and maintenance costs and generate secondary pollution. The adsorption method is a method of reducing the fluorine ion content in a solution by adsorbing the surface of a fluorine ion-adsorbing material in water by using the adsorption property of a porous material or a substance having a large specific surface area, but the recovery and utilization thereof are low. Currently, a simple and cost-effective processing technique: ion exchange technology, the mechanism behind the adsorption of fluorine on these adsorbents, generally relies on the well-structured interactions that occur between the adsorbent and the fluoride, as well as hydrogen bonding and other types of interactions involving fluorine ions, and currently, leakage of metal ions for adsorbent loading, as well as high operating costs, poor cycle stability are common drawbacks of the adsorbents on the market. Also, the selective uptake of fluoride ions in the presence of competing anions (some common ones such as sulfate, bicarbonate and chloride) is becoming more and more necessary to better address the actual contamination problem.
Disclosure of Invention
The invention aims to provide a defluorination adsorbent modified by a biopolymer composite material, which has the advantages of simple preparation process, low cost, easy recovery and recycling and high defluorination efficiency in wastewater.
In order to realize the purpose, the invention adopts the following technical scheme:
a method for preparing a defluorination adsorbent modified by a biopolymer composite material comprises the following steps:
step 1: dissolving 1-10g chitosan in 100-200ml deionized water or 2% -10% acid, and stirring for 1-6 hours under magnetic stirring;
and 2, step: dissolving 1-10g pectin in 100-200ml deionized water or 2% -10% acid, and stirring for 2-6 hours under magnetic stirring;
and step 3: mixing the two solutions obtained in the step 1 and the step 2, and stirring for 1-3 hours at 40-80 ℃;
and 4, step 4: soaking 2-10g of molecular sieve in deionized water for 1-3 hours, adding the molecular sieve into the mixed solution obtained in the step (3), and distilling the molecular sieve at 60-100 ℃ under reduced pressure to obtain 3-8h;
and 5: filtering the redundant mixed solution, and washing for 3 times by using deionized water; adding 1-5g chloroacetic acid and 20-200ml of 2% -10% sodium hydroxide aqueous solution, and stirring at room temperature for 2-3h;
step 6: dissolving 1-5mol of metal nitrate in a mixed solution of ethanol and water with the volume ratio of 1:1, and stirring for 10min at room temperature;
and 7: adding the solution filtered by the molecular sieve in the step 5 into the nitrate solution in the step 6, distilling the solution at 60-100 ℃ under reduced pressure for 3-8h, filtering the redundant solution, adding 20-50ml of 5% -50% sodium hydroxide, and stirring the solution at room temperature for 2-3 hours;
and 8: and filtering the redundant mixed solution, removing the seed water, washing to be neutral, and drying in an oven at 60-100 ℃ to obtain the defluorination adsorbent.
Preferably, the acid in step 1 and step 2 of the present invention is at least one of hydrochloric acid, acetic acid, sulfuric acid, and oxalic acid.
Preferably, the molecular sieve in step 4 of the present invention is 35 to 200 mesh.
Preferably, the metal nitrate in step 6 of the present invention is Fe (NO) 3 ) 3 、Mg(NO 3 ) 2 、Al(NO 3 ) 3 At least one of (a).
The invention takes chitosan and pectin as modified molecular sieve materials, the effective biological adsorbent has low cost, no toxicity and high content, and amino and hydroxyl functional groups have strong adsorption potential and can effectively remove fluorinion in water. In addition, a large amount of carboxyl groups are utilized to chelate metal ions, cheap metal ions are introduced in a bonding mode, the operation is simple, the metal ions can be repeatedly used, and the method is environment-friendly and economical. The biocompatibility and biodegradability of these natural materials make them effective chelating matrices for the incorporation of polyvalent metal ions, as compared to synthetic polymers. The general use of nano-adsorbents to remove F has limitations such as instability, non-recoverability and non-separability. Therefore, particulate molecular sieve adsorbents are more suitable for removing F than nano-adsorbents. The adsorbing material utilizes the dual functions of electrostatic adsorption, ion exchange and the like, thereby achieving efficient defluorination.
By adopting the technical scheme, compared with the prior art, the invention has the following advantages:
1. the invention discloses a method for removing fluorine by using a modified molecular sieve ion exchange adsorbent, which takes a mesoporous molecular sieve nano material as a carrier and has the advantages of large surface area, low relative density, light weight, good permeability and high chemical stability.
2. The invention adopts chitosan and pectin, has no toxicity, biocompatibility and hydrophilic property, has high chemical stability, and the reaction is green and environment-friendly.
3. The invention adopts a modified polymeric material synthesized by chloroacetic acid grafted chitosan, wherein the main chain of the modified polymeric material is provided with-COOH groups and cheap metal cations (Fe) 3+ 、Al 3+ 、Mg 2+ Etc.) exhibit higher defluorination capacity and affinity.
4. The invention uses chitosan and pectin to amidate, crosslink and modify molecular sieve materials, which are all natural polymers, and the molecular sieve materials have low cost, no toxicity and high content of effective biological adsorbents, and amino and hydroxyl functional groups have strong adsorption potential, and can effectively remove fluorine ions in water.
5. The incorporation of the metal ions of the present invention into the crystal lattice of the modified polymer results in a structural change. This rearrangement increases porosity and surface area, promoting dynamic adsorption of fluoride ions.
6. The adsorbing material utilizes the dual functions of electrostatic adsorption, ion exchange and the like, thereby achieving high-efficiency removal. The modified material can remove more than about 97% of fluoride at pH = 5-8.
7. The modified defluorinating material prepared by the invention contains different metal cations and anions (SO) 4 2- 、Cl - 、NO 3 - 、Na + 、K + 、Mg 2+ ) The fluorine-containing wastewater has good selectivity for fluorine ions.
8. The modified defluorination material of the invention adopts 0.5M NaOH to carry out the cycle of the adsorption and desorption processes, and the recovery rate reaches more than 98 percent.
9. The modified defluorinating material prepared by the invention has the advantages of simple preparation process, low cost, easy recovery and recycling and high defluorinating efficiency in wastewater.
Drawings
FIG. 1 is a graph comparing the effects of interfering cations contained in wastewater in example 1 of the present invention.
FIG. 2 is a graph comparing the fluorine concentration of the regenerated adsorbed water in example 5 of the present invention.
Detailed Description
A method for preparing a defluorination adsorbent modified by a biopolymer composite material comprises the following steps:
step 1: dissolving 1-10g chitosan in 100-200ml deionized water or 2% -10% acid, and stirring for 1-6 hours under magnetic stirring;
step 2: dissolving 1-10g pectin in 100-200ml deionized water or 2% -10% acid, and stirring for 2-6 hours under magnetic stirring;
and step 3: mixing the two solutions obtained in the step 1 and the step 2, and stirring for 1-3 hours at 40-80 ℃;
and 4, step 4: soaking 2-10g of molecular sieve in deionized water for 1-3 hours, adding the molecular sieve into the mixed solution obtained in the step (3), and distilling the molecular sieve at 60-100 ℃ under reduced pressure to obtain 3-8h;
and 5: filtering the redundant mixed solution, and washing for 3 times by using deionized water; adding 1-5g of chloroacetic acid and 20-200ml of 2% -10% sodium hydroxide aqueous solution, and stirring at room temperature for 2-3h;
and 6: dissolving 1-5mol of metal nitrate in a mixed solution of ethanol and water with the volume ratio of 1:1, and stirring for 10min at room temperature;
and 7: adding the solution filtered by the molecular sieve in the step 5 into the nitrate solution in the step 6, distilling the solution at 60-100 ℃ under reduced pressure for 3-8h, filtering the redundant solution, adding 20-50ml of 5% -50% sodium hydroxide, and stirring the solution at room temperature for 2-3 hours;
and 8: and filtering the redundant mixed solution, removing the seed water, washing to be neutral, and drying in an oven at 60-100 ℃ to obtain the defluorination adsorbent.
The acid in step 1 and step 2 of the invention is at least one of hydrochloric acid, acetic acid, sulfuric acid and oxalic acid.
The molecular sieve in step 4 of the invention is 35-200 meshes.
The metal nitrate in step 6 of the present invention is Fe (NO) 3 ) 3 、Mg(NO 3 ) 2 、Al(NO 3 ) 3 At least one of (1).
Example 1
Step 1: dissolving 1g chitosan in 100ml deionized water, stirring for 2 hours under magnetic stirring;
step 2: dissolving 1g pectin in 100ml2% acetic acid, stirring for 2 hours under magnetic stirring;
and step 3: mixing the two solutions obtained in the step 1 and the step 2, and stirring for 3 hours at 80 ℃;
and 4, step 4: 2g of molecular sieve (100 meshes) is soaked in deionized water for 1 hour, then added into the mixed solution in the step 3, and decompressed and distilled for 3 hours at 60 ℃;
and 5: filtering the redundant mixed solution, and washing for 3 times by using deionized water; adding 1g of chloroacetic acid and 50ml of 2% sodium hydroxide aqueous solution, and stirring at room temperature for 3 hours;
step 6: 1mol of metal nitrate: fe (NO) 3 ) 3 Dissolving in a mixed solution of ethanol and water with a volume ratio of 1:1, and stirring at room temperature for 10min;
and 7: adding the solution filtered by the molecular sieve in the step 5 into the nitrate solution in the step 6, carrying out reduced pressure distillation at 60 ℃ for 3h, carrying out suction filtration on the redundant solution, adding 50ml of 15% sodium hydroxide, and stirring at room temperature for 2h;
and 8: and filtering the redundant mixed solution, removing the seed water, washing to be neutral, and drying in an oven at 60 ℃ to obtain the defluorination adsorbent.
Example 2
Step 1: dissolving 1g chitosan in 100ml2% acetic acid, stirring for 1 hour under magnetic stirring;
step 2: dissolving 2g pectin in 150ml 3% acetic acid, stirring for 2 hours under magnetic stirring;
and step 3: mixing the two solutions obtained in the step 1 and the step 2, and stirring for 3 hours at 50 ℃;
and 4, step 4: soaking a 6 g molecular sieve (200 meshes) in deionized water for 1 hour, adding the obtained solution into the mixed solution obtained in the step (3), and distilling the obtained product at 60 ℃ under reduced pressure to obtain 2h;
and 5: filtering the redundant mixed solution, and washing for 3 times by using deionized water; adding 2g of chloroacetic acid and 100ml of 2% sodium hydroxide aqueous solution, and stirring at room temperature for 2 hours;
step 6: 2mol of metal nitrate: fe (NO) 3 ) 3 Dissolving in a mixed solution of ethanol and water with a volume ratio of 1:1, and stirring at room temperature for 10min;
and 7: adding the solution filtered by the molecular sieve in the step 5 into the nitrate solution in the step 6, distilling the 3h at 100 ℃ under reduced pressure, filtering the redundant solution in a suction manner, adding 20ml of 5% sodium hydroxide, and stirring at room temperature for 2 hours;
and 8: and filtering redundant mixed solution, washing the filtered mixed solution to be neutral, and drying the washed mixed solution in an oven at 80 ℃ to obtain the defluorination adsorbent.
Example 3
Step 1: dissolving 2g of chitosan in 200ml of 3% oxalic acid, and stirring for 1 hour under magnetic stirring;
step 2: dissolving 6 g pectin in 200ml 3% oxalic acid, stirring for 2 hours under magnetic stirring;
and step 3: mixing the two solutions obtained in the step 1 and the step 2, and stirring for 1 hour at 60 ℃;
and 4, step 4: 5g of molecular sieve (200 meshes) is soaked in deionized water for 1 hour, then is added into the mixed solution in the step 3, and 3h is distilled under reduced pressure at 80 ℃;
and 5: filtering the redundant mixed solution, and washing for 3 times by using deionized water; adding 5g of chloroacetic acid and 200ml of 5% sodium hydroxide aqueous solution, and stirring at room temperature for 2h;
step 6: 3mol of metal nitrate: mg (NO) 3 ) 2 Dissolving in a mixed solution of ethanol and water with a volume ratio of 1:1, and stirring at room temperature for 10min;
and 7: adding the solution filtered by the molecular sieve in the step 5 into the nitrate solution in the step 6, distilling the solution at 90 ℃ under reduced pressure for 3-8h, filtering the redundant solution in a suction manner, adding 30ml of 20% sodium hydroxide, and stirring the solution at room temperature for 3 hours;
and 8: and filtering the redundant mixed solution, removing the seed water, washing to be neutral, and drying in an oven at 100 ℃ to obtain the defluorination adsorbent.
Example 4
Step 1: dissolving 1g chitosan in 100ml2% sulfuric acid, stirring for 1 hour under magnetic stirring;
step 2: dissolving 4 g pectin in 200ml deionized water, and stirring for 2 hours under magnetic stirring;
and step 3: mixing the two solutions in the step 1 and the step 2, and stirring for 2 hours at 80 ℃;
and 4, step 4: 3g of molecular sieve (100 meshes) is soaked in deionized water for 1 hour, then is added into the mixed solution obtained in the step 3, and 3-8h is distilled under reduced pressure at 60 ℃;
and 5: filtering the redundant mixed solution, and washing for 3 times by using deionized water; adding 3g of chloroacetic acid and 100ml of 1% sodium hydroxide aqueous solution, and stirring at room temperature for 2h;
step 6: 2mol of metal nitrate: al (NO) 3 ) 3 Dissolving in a mixed solution of ethanol and water with a volume ratio of 1:1, and stirring at room temperature for 10min;
and 7: adding the solution filtered by the molecular sieve in the step 5 into the nitrate solution in the step 6, carrying out reduced pressure distillation on the 3h at the temperature of 80 ℃, carrying out suction filtration on the redundant solution, adding 50ml of 10% sodium hydroxide, and stirring for 2 hours at room temperature;
and 8: and filtering redundant mixed solution, washing the filtered mixed solution to be neutral, and drying the washed mixed solution in an oven at 60 ℃ to obtain the defluorination adsorbent.
Example 5
Step 1: dissolving 2g of chitosan in 100ml of 2% hydrochloric acid, and stirring for 1 hour under magnetic stirring;
and 2, step: dissolving 2g pectin in 100ml2% hydrochloric acid, and stirring for 1 hour under magnetic stirring;
and step 3: mixing the two solutions in the step 1 and the step 2, and stirring for 1 hour at 80 ℃;
and 4, step 4: 2g of molecular sieve (100 meshes) is soaked in deionized water for 1 hour, then is added into the mixed solution in the step 3, and 3h is distilled under reduced pressure at 60 ℃;
and 5: filtering the redundant mixed solution, and washing for 3 times by using deionized water; adding 2g of chloroacetic acid and 20ml of 2% sodium hydroxide aqueous solution, and stirring at room temperature for 2 hours;
step 6: 2mol of metal nitrate: al (NO) 3 ) 3 Dissolving in a mixed solution of ethanol and water with the volume ratio of 1:1, and stirring for 10min at room temperature;
and 7: adding the solution filtered by the molecular sieve in the step 5 into the nitrate solution in the step 6, distilling the solution at 70 ℃ under reduced pressure for 3h, filtering the redundant solution in a suction manner, adding 20ml of 10% sodium hydroxide, and stirring at room temperature for 2 hours;
and 8: and filtering the redundant mixed solution, removing the seed water, washing to be neutral, and drying in an oven at 60 ℃ to obtain the defluorination adsorbent.
1) 5mL of the modified fluorine-removing materials (adsorbents) of the above experimental cases 1 to 5 were respectively placed in 5 identical 100mL beakers.
2) Respectively taking fluorine-containing wastewater (containing fluorine C) F- =2000ppm, ph = 7), 50mL each was added to the above five beakers.
3) Stirring was continued in a temperature-controlled constant temperature shaker for 4 hours at a stirring speed of 600 rpm.
4) After adsorption was completed, the adsorbent was separated from the fluorine-containing wastewater using filter paper. The change in fluoride concentration in the batch solution was then measured using a fluoride ion selective electrode (model Lei Ci PHS-3C pH meter).
The results of the experiments are shown in the following table:
FIG. 1 is a graph comparing the effects of interfering cations contained in wastewater in example 1 of the present invention. The specific test process is as follows:
1) 5mL of the modified fluorine-removing material (adsorbent) of example 1 was placed in 7 identical 100mL beakers.
2) Respectively taking out the cation and anion (SO) containing different metals 4 2- 、Cl - 、NO 3 - 、Na + 、K + 、Mg 2+ ) The fluorine-containing wastewater (pH =7,C) F- =2000 ppm), 50mL each was added to the above 6 beakers.
3) Stirring was continued in a temperature-controlled constant temperature shaker for 4 hours at a stirring speed of 600 rpm.
4) After the adsorption was completed, the adsorbent was separated from the fluorine-containing wastewater using filter paper. The change in fluoride concentration in the batch solution was then measured using a fluoride ion selective electrode (model Lei Ci PHS-3C pH meter).
The following test procedure was used for example 3 of the present invention:
1) 5mL of the modified fluorine-removing material (adsorbent) obtained in example 3 was placed in a 100mL beaker.
2) Fluorine-containing wastewater of Anhui metal materials Co., ltd (pH =6,C) F- =1500 ppm) 500ml was added to the beaker.
3) Stirring was continued in a temperature-controlled constant temperature shaker for 4 hours at a stirring speed of 600 rpm.
4) After the adsorption was completed, the adsorbent was separated from the fluorine-containing wastewater using filter paper.
The change in fluoride concentration in the batch solution was then measured using a fluoride ion selective electrode (model Lei Ci PHS-3C pH meter).
The test results are shown in the following table:
FIG. 2 is a graph comparing the fluorine concentration in the regenerated and adsorbed water of example 5 of the present invention. The specific test process is as follows:
1) 5mL of the modified defluorinating material (adsorbent) obtained in example 5 was placed in a glass column at a height-diameter ratio of 4:1 and a flow rate of 1BV/H, and 50mL of fluoride wastewater (raw water C) was pumped into the column by a peristaltic pump F- =1000ppm，pH=8）。
2) After adsorption of 10BV of the fluorine-containing wastewater is completed, 0.5M NaOH 1BV is used for desorption (3 BV/H), and the adsorption process is repeated to test the relative stability.
The change in fluoride concentration in the batch solution was measured using a fluoride ion selective electrode (model Lei Ci PHS-3C pH meter).
It is to be emphasized that: the above embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and all simple modifications, equivalent changes and modifications made to the above embodiments according to the technical spirit of the present invention are within the scope of the technical solution of the present invention.
Claims (3)
1. A method for preparing a defluorination adsorbent modified by a biopolymer composite material is characterized by comprising the following steps:
step 1: dissolving 1-10g of chitosan in 100-200ml of deionized water or 2% -10% of acid, and stirring for 1-6 hours under magnetic stirring;
and 2, step: dissolving 1-10g pectin in 100-200ml deionized water or 2% -10% acid, stirring under magnetic stirring for 2-6 hr;
and step 3: mixing the two solutions obtained in the step 1 and the step 2, and stirring for 1-3 hours at 40-80 ℃;
and 4, step 4: soaking 2-10g of molecular sieve in deionized water for 1-3 hours, adding into the mixed solution in the step (3), and distilling at 60-100 ℃ under reduced pressure for 3-8 hours;
and 5: filtering the redundant mixed solution, and washing for 3 times by using deionized water; adding 1-5g of chloroacetic acid and 20-200ml of 2% -10% sodium hydroxide aqueous solution, and stirring at room temperature for 2-3h;
step 6: dissolving 1-5mol of metal nitrate in a mixed solution of ethanol and water with the volume ratio of 1:1, and stirring for 10min at room temperature; the metal nitrate is Fe (NO) 3 ) 3 、Mg(NO 3 ) 2 、Al(NO 3 ) 3 At least one of;
and 7: adding the solution filtered by the molecular sieve in the step 5 into the nitrate solution in the step 6, carrying out reduced pressure distillation at 60-100 ℃ for 3-8h, carrying out suction filtration on the redundant solution, adding 20-50ml of 5% -50% sodium hydroxide, and stirring at room temperature for 2-3h;
and 8: and filtering the redundant mixed solution, removing the seed water, washing to be neutral, and drying in an oven at 60-100 ℃ to obtain the defluorination adsorbent.
2. The method for preparing the defluorination adsorbent modified by biopolymer composite according to claim 1, wherein the acid in step 1 and step 2 is at least one of hydrochloric acid, acetic acid, sulfuric acid and oxalic acid.
3. The method for preparing the fluorine removal adsorbent modified by biopolymer composite according to claim 1, wherein the molecular sieve in step 4 is 35-200 mesh.
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| CN105126770A (en) * | 2015-07-10 | 2015-12-09 | 西南科技大学 | Preparation method of pectin core-shell-structured microsphere adsorption material |
| CN108017219A (en) * | 2017-12-12 | 2018-05-11 | 北京理工水环境科学研究院有限公司 | A kind of high-fluorine water processing equipment |
| WO2018122871A1 (en) * | 2016-12-30 | 2018-07-05 | INDIAN INSTITUTE OF TECHNOLOGY MADRAS (IIT Madras) | Chitosan reinforced mixed oxyhydroxide nanocomposite for fluoride and arsenic removal from water and a device thereof |
| CN111013549A (en) * | 2019-12-26 | 2020-04-17 | 西南石油大学 | Preparation method and application of modified chitosan fluoride ion adsorbent |
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| CN105126770A (en) * | 2015-07-10 | 2015-12-09 | 西南科技大学 | Preparation method of pectin core-shell-structured microsphere adsorption material |
| WO2018122871A1 (en) * | 2016-12-30 | 2018-07-05 | INDIAN INSTITUTE OF TECHNOLOGY MADRAS (IIT Madras) | Chitosan reinforced mixed oxyhydroxide nanocomposite for fluoride and arsenic removal from water and a device thereof |
| CN108017219A (en) * | 2017-12-12 | 2018-05-11 | 北京理工水环境科学研究院有限公司 | A kind of high-fluorine water processing equipment |
| CN111013549A (en) * | 2019-12-26 | 2020-04-17 | 西南石油大学 | Preparation method and application of modified chitosan fluoride ion adsorbent |
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