CN110804111A - Defluorination high polymer material, synthesis method thereof and application thereof in municipal water treatment - Google Patents

Defluorination high polymer material, synthesis method thereof and application thereof in municipal water treatment Download PDF

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CN110804111A
CN110804111A CN201911072296.7A CN201911072296A CN110804111A CN 110804111 A CN110804111 A CN 110804111A CN 201911072296 A CN201911072296 A CN 201911072296A CN 110804111 A CN110804111 A CN 110804111A
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resin
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sodium
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刘红院
张运
梅昂
冯志军
孙冰杰
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SHAANXI LANSHEN SPECIAL RESIN Co Ltd
Xi'an Lanshen Environmental Protection Technology Co Ltd
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SHAANXI LANSHEN SPECIAL RESIN Co Ltd
Xi'an Lanshen Environmental Protection Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
    • 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
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    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract

The invention discloses a defluorination polymer material, a synthesis method and an application thereof in municipal water treatment, amino carboxylic acid resin is filled into an ion exchange chromatographic column, hydrochloric acid solution is added, then pure water is used for washing to be neutral, sodium hydroxide solution is added, pure water is used for washing to be neutral in pH value, and a sodium type polymer material matrix is obtained; ALCL (alcohol-based Link)3And (3) washing the sodium-type high polymer material matrix obtained by passing the solution through a column with pure water until the pH value is 6-7 to obtain the aluminum-type modified defluorination high polymer material. The modified defluorination polymer material prepared by the invention can deeply remove low content in municipal waterThe fluorinion is controlled within 0.5ppm, no other pollution is generated, and the method is simple and easy to operate and can be recycled.

Description

Defluorination high polymer material, synthesis method thereof and application thereof in municipal water treatment
Technical Field
The invention belongs to the technical field of polymer separation materials, and particularly relates to a defluorination polymer material, a synthesis method thereof and application thereof in municipal water treatment.
Background
Fluorine is widely present in natural water bodies, and human tissues contain fluorine, but mainly accumulate in teeth and bone tendons. Proper fluorine is necessary for human bodies, excessive fluorine is harmful to the human bodies, the lethal dose of sodium fluoride to the human bodies is 6-12 g, and the fluorosis can occur when drinking water contains 2.4-5 mg/L. The fluorine content of underground water or surface water in a plurality of regions in the world is higher and can generally reach 2-6 mg/L. Hebei, Henan, Shaanxi, Gansu, Qinghai, Xinjiang and other places in China belong to high fluorine areas. The long-term drinking of the high fluorine water by human and livestock can cause chronic poisoning. In mild cases, osteoporosis, convulsion and spasm, and even death due to respiratory paralysis. In addition, various skin diseases can be caused. Therefore, the treatment of the high fluorine-containing water to reach the standard of drinking water and ensure the health of people becomes an urgent need for residents in the areas. The maximum allowable concentration of the fluorine ions in the domestic drinking water is 1mg/L, and the appropriate concentration is 0.5-1.0 mg/L.
At present, a plurality of fluorine removal methods are available, but a chemical precipitation method and an ion adsorption method are mainly available, the chemical precipitation method is to add cations and fluoride ions into a water body to form a precipitable compound so as to achieve the purpose of removing the fluoride ions, but the method is suitable for application of high-fluorine-containing wastewater, because the solubility of calcium fluoride and water at 18 ℃ is 16.3mg/L and 7.9mg/L calculated by the fluoride ions, the calcium fluoride with the solubility can form precipitates, and the speed of forming the precipitates is slowed down when the residual quantity of fluorine is 10-20 mg/L, so that the method is not suitable for treatment of low-concentration fluorine-containing wastewater.
The ion adsorption method is to remove F by ion exchange between ion exchange resin and fluorine ions in water-However, the premise is that there is no other anion in the water body to interfere with, because of the relative toOther anions, fluorine with small atomic radius, F-After the selectivity of (2), the competitive adsorption results in the pair F-The removal effect of (2) becomes poor.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a defluorination polymer material, its synthesis method and its application in municipal water treatment, aiming at the defects of the prior art, the polymer material is F-Has high selectivity and is not influenced by SO4 2-、Cl-Interference of plasma anions.
A synthetic method of a fluorine-removing macromolecule comprises the following steps:
s1, filling amino carboxylic acid resin into an ion exchange chromatography column, adding a hydrochloric acid solution, washing with pure water to be nearly neutral, adding a sodium hydroxide solution, and washing with pure water to be neutral in pH to obtain a sodium type high polymer material matrix;
s2 ALCL3And (4) allowing the solution to pass through the sodium type high polymer material matrix obtained in the step S1, and washing the sodium type high polymer material matrix with pure water until the pH value is 6-7 to obtain the aluminum type modified defluorination high polymer material.
Specifically, in step S1, the aminocarboxylic acid resin has an exchange capacity of 6mmol/g or more and a particle diameter of 0.315 to 1.25 mm.
Specifically, in the step S1, the concentration of hydrochloric acid is 3-5%, and the volume ratio of the aminocarboxylic acid resin to the hydrochloric acid is 1 (1.5-2.5); the concentration of the sodium hydroxide is 3% -5%, the volume ratio of the aminocarboxylic acid resin to the sodium hydroxide is 1 (1.5-2.5), and the flow rate is 1-2 BV/h.
Specifically, in step S2, ALCL3The concentration of the solution is 5-20%, the flow rate of the column passing is 1-2 BV/h, and the flow rate of the water washing is 1-2 BV/h.
Specifically, in step S2, the volume ratio of the sodium matrix to aluminum trichloride is 1: (3-5).
The invention also provides a technical scheme that the defluorination polymer material is prepared according to a synthesis method, and has the structure that:
Figure BDA0002261334350000021
wherein P is a resin white ball.
The invention also provides a method for deeply removing fluorine from the fluorine-removing high polymer material in municipal water treatment, which comprises the following steps:
s1, filtering the fluorine-containing water with the pH value of 6-8 to be treated to remove impurity particles, wherein the turbidity of the water sample is less than 5 NTU;
s2, passing the water sample treated in the step S1 through an ion exchange chromatography column, wherein the ion exchange chromatography column is filled with the defluorinated macromolecular material prepared by the synthesis method of claim 1;
s3, stopping column passing adsorption when the content of the fluoride ions in the effluent liquid outlet of the step S2 is more than 0.5ppm, and desorbing the high polymer material by using 3-5 BV hydrochloric acid solution with the concentration of 3-5% to obtain high-concentration fluoride ion content solution;
s4, washing the resin in the step S3 by deionized water, adding a sodium hydroxide solution for transformation to obtain sodium amino-condensed acid resin;
s5, using ALCL for resin in the step S43And (4) allowing the solution to pass through a column to complete regeneration, thus obtaining the aluminum type modified high molecular organic material, and performing defluorination recycling.
Specifically, in the step S2, the content of fluorine ions in the water sample is 1-10 ppm, and the flow rate of column passing is 5-15 BV/h.
Specifically, in step S4, the resin is cleaned by 1-3 BV of deionized water, the concentration of the sodium hydroxide solution is 3% -5%, and the amount of the sodium hydroxide solution is 1-2 BV.
Specifically, in step S5, ALCL3The concentration of the solution is 5-20%, the using amount is 3-5 BV, and the flow rate is 0.5-1 BV/h.
Compared with the prior art, the invention has at least the following beneficial effects:
the invention relates to a synthetic method of a defluorination polymer material, step S1 obtains a sodium type polymer material matrix which is used as a reaction matrix of metallic aluminum, the polymer material matrix is amino carboxylic acid resin with higher exchange capacity, the mechanical strength is high, the physical and chemical properties are excellent, the service life is longHas strong service life and can be used for a long time, the resin is fully transformed by hydrochloric acid solution and sodium hydroxide solution, and 5 to 20 percent of ALCL (alcohol-based liquid) with the volume of 3 to 5 times of that of the resin is used3And (3) passing the solution through a column, and washing with pure water until the pH value is 6-7 to obtain the aluminum-type modified defluorination high polymer material with high loading capacity.
Furthermore, the exchange capacity of the amino carboxylic acid resin is more than 6mmol/g, the loading capacity can be improved, the particle size is 0.315-1.25 mm, and the yield of the resin can be improved to the maximum extent.
Furthermore, the leaving-factory type of the amino carboxylic acid resin is a sodium type, the resin needs to be thoroughly regenerated by using hydrochloric acid and a sodium hydroxide solution in the using process, the dosage standard is the maximum exchange capacity of hydrogen ions and sodium ions, and experiments prove that 3% -5% hydrochloric acid and 3% -5% sodium hydroxide solution which are 1.5-2.5 times of the volume of the resin can be thoroughly transformed.
Further, the cation in the water body is Ca2+、Mg2+、Na+、K+Mainly, and Al3+Has higher exchange capacity relative to low-valence cations, and needs to be adjusted in AlCl in order to ensure that the cations are sufficiently exchanged in the process of exchanging with the sodium-type aminocarboxylic acid resin3Concentration and exchange Rate of the solution, ALCL3The concentration of the solution is 5-20%, and the flow rate of the column passing is 1-2 BV/h.
Further, in order to sufficiently exchange Na on the phosphoramidate resin+，ALCL3The amount of the solution needs to be excessive, and the volume ratio of the sodium matrix to the aluminum trichloride is 1: (3-5) is most preferable.
The invention relates to a defluorination polymer material, which is an aluminum-loaded aminocarboxylic acid modified polymer material, the surface of which is loaded with aluminum ions, can selectively adsorb the fluorine ions in water and is not influenced by SO4 2-、Cl-And low-concentration fluorine ions in the municipal sewage can be deeply removed due to the interference of anions, the concentration of the treated fluorine ions can be reduced to be below 0.5ppm, and the high polymer material is regenerated by using a hydrochloric acid solution after reaching adsorption saturation and can be recycled.
The invention relates to defluorinationMethod for deeply removing fluorine from high-molecular material in municipal water treatment, and low-concentration F contained in water can be selectively and deeply removed-And is free from SO4 2-、Cl-、NO3 -The interference of anions is avoided, the concentration of the fluorine ions after treatment can be reduced to be below 0.5ppm, the method can be completely applied to removal of low-concentration fluorine ions in municipal water treatment, the fluorine removal material prepared by the method can exchange more fluorine ions in water, the treatment capacity is enhanced, the treatment effect is more remarkable, and the content of the fluorine ions can be reduced to be below 0.5 ppm.
Furthermore, in order to reduce the concentration of the fluorine ions to be below 0.5ppm, the content of the fluorine ions in the water sample is controlled to be 1-10 ppm before entering the resin treatment system, the flow rate of the column passing is 5-15 BV/h, and the fluorine ions can be deeply removed.
Further, when the content of the fluorine ions is more than 0.5ppm after treatment, stopping column passing adsorption, fully desorbing the high polymer material by using 3-5 BV hydrochloric acid solution with the concentration of 3% -5%, completely replacing the fluorine ions on the resin, and transforming the resin by using 1-2 BV sodium hydroxide solution to obtain the sodium amino phosphate resin.
Further, 3-5 BV 5% -15% AlCl is used3The solution thoroughly modifies the sodium type phosphoramidate resin to obtain the aluminum type defluorination adsorbing material.
In conclusion, the modified defluorination polymer material prepared by the invention can deeply remove low-content fluorine ions in municipal water, so that the fluorine ions are controlled within 0.5ppm, other pollution is avoided, and the method is simple and easy to operate and can be recycled.
The technical solution of the present invention is further described in detail by the accompanying drawings and embodiments.
Drawings
FIG. 1 is a schematic view of example 1 of the present invention;
FIG. 2 is a schematic view of example 2 of the present invention;
FIG. 3 is a schematic view of example 3 of the present invention;
FIG. 4 is a schematic view of example 4 of the present invention;
fig. 5 is a schematic view of embodiment 5 of the present invention.
Detailed Description
The invention relates to a defluorination polymer material, which is a metal aluminum type aminocarboxylic acid modified polymer material, metal aluminum ions and sodium aminocarboxylate resin are subjected to ion exchange reaction to obtain an aluminum-containing polymer organic material, the aluminum-containing polymer organic material can be selectively adsorbed with fluorine ions in water and is not subjected to SO4 2-、Cl-、NO3 -The interference of anions is equal, low-concentration fluorine ions in municipal sewage can be deeply removed, the concentration of the treated fluorine ions can be reduced to be below 0.5ppm, the adsorption capacity of a high-molecular organic material is 5850-9865 mg/L, the high-molecular material is regenerated by using a hydrochloric acid solution after reaching adsorption saturation, and the high-molecular material can be recycled after regeneration, and the characteristic structure is as follows:
Figure BDA0002261334350000061
wherein P is a resin white ball.
The synthesis and application principle is as follows:
Figure BDA0002261334350000062
a synthetic method of defluorination macromolecule material, firstly preparing amino carboxylic acid sodium resin; then preparing the aluminum type modified high polymer material, which comprises the following specific steps:
s1, preparing a sodium aminocarboxylate resin;
selecting amino carboxylic acid resin with the exchange capacity of more than 6mmol/g and the particle size of 0.315-1.25 mm, loading the amino carboxylic acid resin into an ion exchange chromatographic column, adding 2 times of hydrochloric acid solution with the volume concentration of 4% of the resin, adjusting the flow rate to be 1BV/h, washing the amino carboxylic acid resin with the particle size of 0.315-1.25 mm by using pure water to be nearly neutral, adding 2 times of sodium hydroxide solution with the volume of 4% of the resin, adjusting the flow rate to be 1BV/h, and finally washing the amino carboxylic acid resin with the pure water to be nearly neutral in.
S2, preparing an aluminum type modified high polymer material.
Preparing ALCL with concentration of 5-20%3And (4) passing the solution through the high polymer material matrix in the column passing step S1, adjusting the flow rate of passing the column to be 1-2 BV/h, and then washing with pure water until the pH value is 6-7 and the flow rate of washing is 1-2 BV/h to obtain the aluminum-type modified high polymer material.
AL3+With Na+Carrying out ion exchange reaction, wherein the volume ratio of the sodium matrix to the aluminum trichloride is 1: (3-5).
The application of the defluorination polymer material in municipal water treatment comprises the following steps:
s1, filtering the fluorine-containing water with nearly neutral pH value to be treated, and removing impurity particles, wherein the turbidity of the water sample is less than 5 NTU;
s2, enabling the water sample with the fluorine ion content of 1-10 ppm processed in the step S1 to pass through an ion exchange chromatographic column at the flow rate of 5-15 BV/h, wherein a certain amount of aluminum type modified high polymer organic material is filled in the ion exchange chromatographic column, and when a water body flows through the chromatographic column, fluorine ions in the water are exchanged to the high polymer material so as to achieve the purpose of removing the fluorine ions;
s3, when the effluent liquid outlet of the step S2 has the fluorine ion content>When the concentration is 0.5ppm, stopping column passing adsorption, and desorbing the high polymer material by using 4BV hydrochloric acid solution with the concentration of 4 percent to obtain high-concentration fluorine ion content solution; the analytic solution contains HF and AlCl3Chemical defluorination can be carried out by adding proper amount of precipitator Ca (OH)2Generation of CaF2The fluorine can be effectively removed by precipitation and the like;
s4, washing the resin in the step S3 by 2BV of deionized water, and adding 1.5BV of 4% sodium hydroxide solution for transformation to obtain sodium amino acid condensation resin;
s5, using ALCL with concentration of 4BV and 10% for the resin in the step S43The solution is passed through the column at a flow rate of 1BV/h, and the effluent liquid contains Al3+And the partial water sample enters a high-concentration chemical defluorination system, and the regeneration is completed to obtain the aluminum type modified high molecular organic material which can be subjected to defluorination recycling.
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 drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. The components of the embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. 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.
Example 1
Synthesis of LSF-02 aluminum type modified high molecular organic material and effect of deep defluorination in municipal water treatment
1) Preparation of sodium aminocarboxylate type resin
Selecting a certain amount of amino carboxylic acid resin with the exchange capacity of more than 6mmol/g and the particle size of 0.315-1.25 mm, loading the amino carboxylic acid resin into an ion exchange chromatographic column, adding 2 times of hydrochloric acid solution with the volume concentration of 3%, adjusting the flow rate to be 1BV/h, washing the amino carboxylic acid resin with pure water to be nearly neutral, adding 2 times of sodium hydroxide solution with the volume of 3% of the resin, adjusting the flow rate to be 1BV/h, and finally washing the amino carboxylic acid resin with pure water to be nearly neutral in pH value to obtain the sodium type high polymer material matrix.
2) Preparation of aluminum type modified high polymer material
5% of ALCL is prepared3And (3) enabling the solution to pass through a sodium type high polymer material matrix in the column 1), adjusting the flow rate of column passing to be 1BV/h and the using amount to be 4BV, washing with pure water until the pH value is 6-7 and the flow rate of water washing is 2BV/h, and obtaining the aluminum type modified high polymer material.
3) Water sample pretreatment and column adsorption
Laboratory simulation water sample index: f-Content 9.3ppm, SO4 2-Content 150ppm, NO3 -Content 20ppm, CL-The content was 50 ppm. Filtering a water sample with nearly neutral pH value to remove impurity particles, passing the treated water sample through an ion exchange chromatography column at a flow rate of 3BV/h, and when the content of fluorine ions at an effluent outlet is low>At 0.5ppm, the column chromatography is stoppedThe physical multiple is 650 BV.
4) Desorption regeneration of modified high molecular organic material
Desorbing the high polymer material by using 2BV hydrochloric acid solution with the concentration of 4 percent, cleaning by using 2BV deionized water, adding 1.5BV sodium hydroxide solution with the concentration of 4 percent for transformation to obtain sodium amino condensed acid resin, wherein the volume ratio of a sodium matrix to aluminum trichloride is 1: 5. finally, 4BV ALCL with the concentration of 5 percent is used3And (4) passing the solution through a column at the flow rate of 1BV/h, washing with pure water until the solution is nearly neutral, then completing regeneration, and continuing to perform periodic test verification. In the second period, when the content of the fluorine ions at the outlet is more than or equal to 0.5ppm, the treatment multiple is 485BV, and the high polymer material desorption is carried out by adopting 3BV hydrochloric acid solution with the concentration of 4 percent, and the rest are the same as above. The third cycle treatment multiple is 550BV, the fourth cycle uses hydrochloric acid solution with the concentration of 4BV and the concentration of 4% to desorb the high polymer material, the fourth cycle treatment multiple is 645BV, and the fifth cycle repeats the fourth cycle desorption scheme, and the treatment multiple is 655 BV. The processing ability of the high molecular organic material did not decay after going through 5 cycles, as shown in fig. 1.
Therefore, the desorption of the high molecular organic material is preferably performed by using 4BV of a 4% hydrochloric acid solution.
Example 2
Synthesis of LSF-02 aluminum type modified high molecular organic material and effect of deep defluorination in municipal water treatment
1) Preparation of sodium aminocarboxylate type resin
Selecting a certain amount of amino carboxylic acid resin with the exchange capacity of more than 6mmol/g and the particle size of 0.315-1.25 mm, loading the amino carboxylic acid resin into an ion exchange chromatographic column, adding 1.5 times of hydrochloric acid solution with the volume concentration of 4% of the resin, adjusting the flow rate to be 2BV/h, washing the amino carboxylic acid resin with pure water to be nearly neutral, adding 1.5 times of sodium hydroxide solution with the volume of 4% of the resin, adjusting the flow rate to be 2BV/h, and finally washing the amino carboxylic acid resin with pure water to be nearly neutral in pH value to obtain the sodium type high polymer material matrix.
2) Preparation of aluminum type modified high polymer material
10% of ALCL is prepared3The solution passes through a sodium type polymer material matrix in the column 1), the flow rate of the column is adjusted to be 2BV/h, the using amount is 4BV, the solution is washed by pure water until the pH value is 6 to 7,the water washing flow rate is 1BV/h, and the aluminum type modified high polymer material is obtained.
3) Water sample pretreatment and column adsorption
Laboratory simulation water sample index: f-Content 9.3ppm, SO4 2-Content 150ppm, NO3 -Content 20ppm, CL-The content was 50 ppm. Filtering a water sample with nearly neutral pH value to remove impurity particles, passing the treated water sample through an ion exchange chromatography column at a flow rate of 3BV/h, and when the content of fluorine ions at an effluent outlet is low>When the concentration is 0.5ppm, the column chromatography is stopped, and the treatment multiple is 650 BV.
4) Desorption regeneration of modified high molecular organic material
Desorbing the high polymer material by using 4BV hydrochloric acid solution with the concentration of 4 percent, cleaning by using 2BV deionized water, adding 1.5BV sodium hydroxide solution with the concentration of 4 percent for transformation to obtain sodium amino condensed acid resin, wherein the volume ratio of a sodium matrix to aluminum trichloride is 1: 4. finally, 4BV ALCL with the concentration of 10 percent is used3And (4) passing the solution through a column at the flow rate of 1BV/h, washing with pure water until the solution is nearly neutral, then completing regeneration, and continuing to perform periodic test verification. In the second period, when the content of the fluorine ions at the outlet is more than or equal to 0.5ppm, the treatment multiple is 980 BV; the third cycle processing multiple was 972BV, the fourth cycle processing multiple was 975BV, and the processing capacity did not decay after 3 cycles, as shown in FIG. 2.
Example 3
Synthesis of LSF-02 aluminum type modified high molecular organic material and effect of deep defluorination in municipal water treatment
1) Preparation of sodium aminocarboxylate type resin
Selecting a certain amount of amino carboxylic acid resin with the exchange capacity of more than 6mmol/g and the particle size of 0.315-1.25 mm, loading the amino carboxylic acid resin into an ion exchange chromatographic column, adding 2.5 times of hydrochloric acid solution with the volume concentration of 5%, adjusting the flow rate to be 1BV/h, washing the amino carboxylic acid resin with pure water to be nearly neutral, adding 2.5 times of sodium hydroxide solution with the volume of 5% of the resin, adjusting the flow rate to be 1BV/h, and finally washing the amino carboxylic acid resin with pure water to be nearly neutral in pH to obtain the sodium type high polymer material matrix.
2) Preparation of aluminum type modified high polymer material
Preparation of15% of ALCL3And (3) enabling the solution to pass through a sodium type high polymer material matrix in the column 1), adjusting the flow rate of column passing to be 1BV/h and the using amount to be 4BV, washing with pure water until the pH value is 6-7 and the flow rate of water washing is 2BV/h, and obtaining the aluminum type modified high polymer material.
3) Water sample pretreatment and column adsorption
Laboratory simulation water sample index: f-Content 9.3ppm, SO4 2-Content 150ppm, NO3 -Content 20ppm, CL-The content was 50 ppm. Filtering a water sample with nearly neutral pH value to remove impurity particles, passing the treated water sample through an ion exchange chromatography column at a flow rate of 5BV/h, and when the content of fluorine ions at an effluent outlet is low>When the concentration is 0.5ppm, the column chromatography is stopped, and the treatment multiple is 974 BV.
4) Desorption regeneration of modified high molecular organic material
Desorbing the high polymer material by using 4BV hydrochloric acid solution with the concentration of 4 percent, cleaning by using 2BV deionized water, adding 1.5BV sodium hydroxide solution with the concentration of 4 percent for transformation to obtain sodium amino condensed acid resin, wherein the volume ratio of a sodium matrix to aluminum trichloride is 1: 3. finally, 4BV ALCL with the concentration of 10 percent is used3And (4) passing the solution through a column at the flow rate of 1BV/h, washing with pure water until the solution is nearly neutral, then completing regeneration, and continuing to perform periodic test verification. In the second period, when the content of the outlet fluorine ions is more than or equal to 0.5ppm, the treatment multiple is 975 BV; the third cycle processing multiple was 982BV, the fourth cycle processing multiple was 976BV, and the processing capacity did not decay after going through 4 cycles, as shown in fig. 3.
In example 3, the process flow rate was adjusted to 5BV/h compared to example 2, and no significant decrease in adsorption capacity occurred compared to 3 BV/h.
Example 4
Synthesis of LSF-02 aluminum type modified high molecular organic material and effect of deep defluorination in municipal water treatment
1) Preparation of sodium aminocarboxylate type resin
Selecting a certain amount of amino carboxylic acid resin with the exchange capacity of more than 6mmol/g and the particle size of 0.315-1.25 mm, loading the amino carboxylic acid resin into an ion exchange chromatographic column, adding 2 times of hydrochloric acid solution with the volume concentration of 4 percent of the resin, adjusting the flow rate to be 2BV/h, washing the amino carboxylic acid resin with pure water to be nearly neutral, adding 2 times of sodium hydroxide solution with the volume of 4 percent of the resin, adjusting the flow rate to be 2BV/h, and finally washing the amino carboxylic acid resin with pure water to be nearly neutral in pH value to obtain the sodium type high polymer material matrix.
2) Preparation of aluminum type modified high polymer material
Preparing 18% ALCL3And (3) enabling the solution to pass through a sodium type high polymer material matrix in the column 1), adjusting the flow rate of column passing to be 2BV/h and the using amount to be 4BV, washing with pure water until the pH value is 6-7 and the flow rate of water washing is 1BV/h, and obtaining the aluminum type modified high polymer material.
3) Water sample pretreatment and column adsorption
Laboratory simulation water sample index: f-Content 9.3ppm, SO4 2-Content 150ppm, NO3 -Content 20ppm, CL-The content was 50 ppm. Filtering a water sample with nearly neutral pH value to remove impurity particles, passing the treated water sample through an ion exchange chromatography column at a flow rate of 10BV/h, and when the content of fluorine ions at an effluent outlet is low>When the concentration is 0.5ppm, the column chromatography is stopped, and the treatment multiple is 965 BV.
4) Desorption regeneration of modified high molecular organic material
Desorbing the high polymer material by using 4BV hydrochloric acid solution with the concentration of 4 percent, cleaning by using 2BV deionized water, adding 1.5BV sodium hydroxide solution with the concentration of 4 percent for transformation to obtain sodium amino condensed acid resin, wherein the volume ratio of a sodium matrix to aluminum trichloride is 1: 4. finally, 4BV ALCL with the concentration of 10 percent is used3And (4) passing the solution through a column at the flow rate of 1BV/h, washing with pure water until the solution is nearly neutral, then completing regeneration, and continuing to perform periodic test verification. In the second period, when the content of the outlet fluorine ions is more than or equal to 0.5ppm, the treatment multiple 962 BV; the third cycle processing multiple is 955BV, the fourth cycle processing multiple is 960BV, and the processing capacity does not fade after 4 cycles. When the adsorption flow rate was adjusted to 15BV/h, the 5 th cycle treatment multiple was 910BV, as shown in FIG. 4.
Compared with example 2, example 3 adjusts the treatment flow rate to 10BV/h, the adsorption capacity is reduced by about 2% compared with the flow rate of 5BV/h, and no obvious attenuation occurs. When the treatment flow rate is adjusted to 15BV/h, the treatment times are 890BV and are reduced by 9 percent, and the flow rate is preferably 10BV/h in consideration of the water quantity, the economic investment and the effect analysis.
Example 5
Synthesis of LSF-02 aluminum type modified high molecular organic material and effect of deep defluorination in municipal water treatment
1) Preparation of sodium aminocarboxylate type resin
Selecting a certain amount of amino carboxylic acid resin with the exchange capacity of more than 6.5mmol/g and the particle size range of 0.315-1.25 mm, loading the amino carboxylic acid resin into an ion exchange chromatographic column, adding 2 times of hydrochloric acid solution with the volume concentration of 3%, adjusting the flow rate to be 1BV/h, washing the amino carboxylic acid resin with pure water to be nearly neutral, adding 2 times of sodium hydroxide solution with the volume of 3% of the resin, adjusting the flow rate to be 1BV/h, and finally washing the amino carboxylic acid resin with pure water to be nearly neutral in pH to obtain the sodium type high polymer material matrix.
2) Preparation of aluminum type modified high polymer material
Preparing 20% ALCL3And (3) enabling the solution to pass through a sodium type high polymer material matrix in the column 1), adjusting the flow rate of column passing to be 1BV/h and the using amount to be 4BV, washing with pure water until the pH value is 6-7 and the flow rate of water washing is 2BV/h, and obtaining the aluminum type modified high polymer material.
3) Water sample pretreatment and column adsorption
Laboratory simulation water sample index: f-Content 9.3ppm, SO4 2-Content 150ppm, NO3 -Content 20ppm, CL-The content was 50 ppm. Filtering a water sample with nearly neutral pH value to remove impurity particles, passing the treated water sample through an ion exchange chromatography column at a flow rate of 10BV/h, and when the content of fluorine ions at an effluent outlet is low>At 0.5ppm, the column adsorption was stopped, and the treatment magnification was 1060 BV.
4) Desorption regeneration of modified high molecular organic material
Desorbing the high polymer material by using 4BV hydrochloric acid solution with the concentration of 4 percent, cleaning by using 2BV deionized water, adding 1.5BV sodium hydroxide solution with the concentration of 4 percent for transformation to obtain sodium amino condensed acid resin, wherein the volume ratio of a sodium matrix to aluminum trichloride is 1: 5, finally using 4BV ALCL with the concentration of 10 percent3The solution is passed through a column with the flow rate of 1BV/h, and the regeneration is completed after the solution is washed to be nearly neutral by pure waterAnd continuing to periodically test and verify. In the second period, when the content of the outlet fluorine ions is more than or equal to 0.5ppm, the treatment multiple is 1045 BV; the third cycle processing multiple is 1058BV, and the processing capacity of the high molecular organic material does not decay after 3 cycles, as shown in FIG. 5.
Therefore, the specific exchange capacity of the aminocarboxylic acid resin with the selective exchange capacity of the aluminum-type modified macromolecular organic material of more than 6.5mmol/g is more than 6.0mmol/g, and the defluorination effect can be improved by about 8 percent.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.

Claims (10)

1. A synthetic method of a fluorine-removing polymer is characterized by comprising the following steps:
s1, filling amino carboxylic acid resin into an ion exchange chromatography column, adding a hydrochloric acid solution, washing with pure water to be nearly neutral, adding a sodium hydroxide solution, and washing with pure water to be neutral in pH to obtain a sodium type high polymer material matrix;
s2 ALCL3And (4) allowing the solution to pass through the sodium type high polymer material matrix obtained in the step S1, and washing the sodium type high polymer material matrix with pure water until the pH value is 6-7 to obtain the aluminum type modified defluorination high polymer material.
2. The synthesis method according to claim 1, wherein in step S1, the aminocarboxylic acid resin has an exchange capacity of 6mmol/g or more and a particle diameter of 0.315 to 1.25 mm.
3. The synthesis method according to claim 1, wherein in step S1, the concentration of hydrochloric acid is 3-5%, and the volume ratio of the aminocarboxylic acid resin to the hydrochloric acid is 1 (1.5-2.5); the concentration of the sodium hydroxide is 3% -5%, the volume ratio of the aminocarboxylic acid resin to the sodium hydroxide is 1 (1.5-2.5), and the flow rate is 1-2 BV/h.
4. According to the claimsThe synthesis method according to claim 1, wherein in step S2, ALCL3The concentration of the solution is 5-20%, the flow rate of the column passing is 1-2 BV/h, and the flow rate of the water washing is 1-2 BV/h.
5. The synthesis method according to claim 1, wherein in step S2, the volume ratio of the sodium matrix to the aluminum trichloride is 1: (3-5).
6. The defluorination polymer material is characterized by being prepared by the synthesis method of claim 1 and having the structure as follows:
wherein P is a resin white ball.
7. A method for deeply removing fluorine from a fluorine-removing high polymer material in municipal water treatment is characterized by comprising the following steps:
s1, filtering the fluorine-containing water with the pH value of 6-8 to be treated to remove impurity particles, wherein the turbidity of the water sample is less than 5 NTU;
s2, passing the water sample treated in the step S1 through an ion exchange chromatography column, wherein the ion exchange chromatography column is filled with the defluorinated macromolecular material prepared by the synthesis method of claim 1;
s3, stopping column passing adsorption when the content of the fluoride ions in the effluent liquid outlet of the step S2 is more than 0.5ppm, and desorbing the high polymer material by using 3-5 BV hydrochloric acid solution with the concentration of 3-5% to obtain high-concentration fluoride ion content solution;
s4, washing the resin in the step S3 by deionized water, adding a sodium hydroxide solution for transformation to obtain sodium amino-condensed acid resin;
s5, using ALCL for resin in the step S43And (4) allowing the solution to pass through a column to complete regeneration, thus obtaining the aluminum type modified high molecular organic material, and performing defluorination recycling.
8. The method according to claim 7, wherein in step S2, the content of fluorine ions in the water sample is 1-10 ppm, and the flow rate through the column is 5-15 BV/h.
9. The method according to claim 7, wherein in step S4, the resin is washed with 1-3 BV deionized water, and the concentration of the sodium hydroxide solution is 3% -5% by weight and the amount is 1-2 BV.
10. The method of claim 7, wherein in step S5, ALCL3The concentration of the solution is 5-20%, the using amount is 3-5 BV resin volume, and the flow rate is 0.5-1 BV/h.
CN201911072296.7A 2019-11-05 2019-11-05 Defluorination high polymer material, synthesis method thereof and application thereof in municipal water treatment Pending CN110804111A (en)

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Application publication date: 20200218