CN113788912A - Preparation method and application of imprinting material for removing nitrate in drinking underground water - Google Patents
Preparation method and application of imprinting material for removing nitrate in drinking underground water Download PDFInfo
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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
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
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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
- B01J20/22—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
- B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
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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
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
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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
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/163—Nitrates
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/044—Elimination of an inorganic solid phase
- C08J2201/0444—Salts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/24—Homopolymers or copolymers of amides or imides
- C08J2333/26—Homopolymers or copolymers of acrylamide or methacrylamide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2339/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
Abstract
The invention relates to a preparation method and application of a blotting material for removing nitrate in drinking groundwater. The invention respectively explores the influence of the preassembly time of the template and the functional molecule and the proportion of each component in the material on the saturated adsorption capacity of the material. The finally developed nitrate ion imprinted material has the saturated adsorption capacity of 14.876mg/L for nitrate nitrogen, has better adsorbability, and is relative to SO4 2‑Material to NO3 ‑The selectivity coefficient of (A) is 1.833, and good selectivity is achieved.
Description
Technical Field
The invention belongs to the technical field of new materials for removing nitrate in underground water, and particularly relates to a preparation method of a imprinted material for selectively adsorbing nitrate ions and application of the imprinted material in nitrate targeted adsorption of nitrate in distributed rural drinking underground water.
Background
Underground water is the most main source of drinking water in rural areas in northern areas of China, nitrate in the underground water can directly harm the body health of residents in the rural areas, the residents can cause human diseases if drinking water with excessive nitrate content is taken for a long time, and cancers are seriously caused. Compared with the characteristics that residents in rural areas in northern China are small in inhabitation and wide in area, the residents are relatively dispersed in urban population, the daily water consumption is small, the fluctuation is large along with seasonal variation, most of groundwater drinking water in the rural areas is taken by distributed self-exploiting wells, and the system has the typical characteristics of distributed groundwater water sources such as large quantity, wide distribution, small scale and the like. Because the centralized treatment amount per day is small, the centralized urban drinking water solution cannot be applied to removing nitrate from drinking underground water in vast rural areas, and the characteristic of distributed water collection in the rural areas brings great difficulty to the removal of nitrate. Therefore, a scheme for properly and efficiently removing nitrate is required to be provided aiming at the characteristics of distributed rural drinking water.
For counties with relatively concentrated resident population, the physical method of utilizing a semi-permeable membrane and ion exchange resin to adsorb nitrate in drinking water is common, and the main mechanism is to enrich and concentrate nitrate nitrogen and transfer the enriched concentrated solution to other places for secondary treatment. The ion enrichment process is non-selective, and the semi-permeable membrane and the ion exchange resin can adsorb non-target ions while adsorbing nitrate nitrogen in the polluted water body, so that the material utilization rate is reduced. In the chemical method for removing nitrate nitrogen, the reducing agent not only reduces the nitrate nitrogen into ammonia nitrogen or nitrogen, but also reduces other oxidizing substances in the polluted water body, so that the reducing agent is consumed purposelessly, nitrate is preferentially adsorbed on an anode due to negative electricity of the nitrate in electrochemical catalysis, nitrate reduction occurs on a cathode, and the electrochemical catalysis efficiency is reduced. In summary, the non-selectivity of nitrate removal methods reduces the efficiency of drinking water purification and increases the cost of decentralized drinking groundwater removal, which increases the cost of water usage in relatively laggard rural areas, and it is therefore desirable to find a method to reduce the unintended consumption of materials in the nitrate conversion removal process.
The imprinting material is an adsorbent with selective adsorption function, imprinting cavities formed in the preparation process are highly matched with the template in the aspects of size, space structure, binding sites and the like, so that the imprinting material has specific selectivity and excellent binding affinity to the template, and can selectively adsorb specific pollutants from drinking water. The imprinting material comprises molecular imprinting and ion imprinting, wherein the ion imprinting is divided into cationic imprinting material and anionic imprinting material. Nitrate radical is a common anionic pollutant of drinking water, the ionic radius of the nitrate radical is small, the ionic functionalization is weak, the complex effect with functional monomers is not easy to generate, effective template recognition sites are difficult to establish, the electrostatic adsorption capacity of the nitrate radical is poorer than that of cation in the adsorption process, but anions such as nitrate radical are also common pollutants in drinking underground water. Therefore, the development of the material with the nitrate radical targeted adsorption function has important significance for the high-efficiency treatment of nitrate in rural drinking underground water.
Disclosure of Invention
The invention aims to provide a preparation method of a blotting material capable of selectively adsorbing nitrate ions and also provides application of the blotting material capable of selectively adsorbing nitrate ions in nitrate-targeted adsorption in dispersed rural drinking groundwater so as to solve the problems of low removal efficiency and difficult removal of nitrate in dispersed rural drinking water caused by non-targeted reaction in the existing method for removing nitrate in drinking groundwater through conversion.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a blotting material for removing nitrate in drinking underground water is characterized in that nitrate is used as template ions, dimethyl diallyl ammonium chloride and acrylamide are used as functional monomers, ethylene glycol dimethacrylate is used as a cross-linking agent, and azobisisobutyronitrile is used as an initiator, and the blotting material is prepared by a bulk polymerization method and is a porous solid.
The preparation method of the imprinting material for removing the nitrate in the drinking groundwater specifically comprises the following steps:
A. pre-assembling imprinting materials: respectively adding a proper amount of template molecule sodium nitrate, functional monomers dimethyl diallyl ammonium chloride and acrylamide into a mixed solution of N, N dimethyl formamide and methanol, and stirring and pre-assembling at normal temperature for 6-24 h;
B. polymerization of the material: heating the prepared liquid after pre-assembly in a 65 ℃ water bath, sequentially adding a proper amount of cross-linking agent ethylene glycol dimethacrylate and initiator azobisisobutyronitrile into a reaction vessel, and synthesizing a porous solid polymer by using a bulk polymerization method in a closed environment;
C. cleaning and drying materials: cooling the synthesized material to room temperature, and then washing the material with absolute ethyl alcohol, NaCl solution and deionized water until no nitrate is detected in the eluent; and (3) drying the cleaned imprinting material in a vacuum drying oven at 45 ℃ for 12h, and then transferring the imprinting material to a freeze drying oven for drying for 12 h.
Further, step a, the preassembly time is 12 h.
Further, the molar ratio of the template molecule, the functional monomer and the cross-linking agent is as follows: 1: 1-10: 1 to 7.
Further, the mole ratio of the template molecule, the functional monomer and the cross-linking agent is 1: 10: 5.
further, the molar ratio of the template molecule to the initiator is: 1: 5.
furthermore, the mole ratio of the functional monomers dimethyl diallyl ammonium chloride and acrylamide is as follows: 1: 1.
furthermore, the template molecule sodium nitrate is 0-1.7g, the functional monomer dimethyl diallyl ammonium chloride is 5.38g, the acrylamide is 1.421g, and the ethylene glycol dimethacrylate is 1.982-13.875 g.
The ionic imprinting material of the nitrate is applied to the nitrate nitrogen pollution treatment of drinking underground water, in particular to the application of nitrate target adsorption in the drinking underground water of distributed rural areas.
Compared with the prior art, the invention has the beneficial effects that:
the invention utilizes the ion exchange principle, uses dimethyl diallyl ammonium chloride and acrylamide containing C ═ C and amino as functional monomers, uses ethylene glycol dimethacrylate as a cross-linking agent, uses azobisisobutyronitrile as an initiator, prepares a nitrate ion imprinting material by a bulk polymerization method, and is applied to the treatment of nitrate nitrogen pollution of drinking groundwater, the saturated adsorption capacity of the ion imprinting material to the nitrate nitrogen is 14.876mg/L, the ion imprinting material has better adsorbability, and compared with SO, the ion imprinting material has the advantages that the saturated adsorption capacity is 14.876mg/L, the adsorption capacity is higher, and the adsorption capacity is higher4 2-Material to NO3 -The selectivity coefficient of (A) is 1.833, and good selectivity is achieved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a synthesized nitrate-targeted adsorption material;
2 a-2 d are SEM images of the surface of the nitrate-targeted adsorbent material particles;
FIG. 3 is a graph of the effect of different pre-assembly times on the adsorption performance of an ion imprinting material;
FIG. 4 shows the influence of the ratio of functional monomers to cross-linking agents on the adsorption performance of the ion imprinting material;
FIG. 5 shows the influence of the ratio of template molecules to functional monomers on the adsorption performance of the ion imprinted material;
FIG. 6 is a flow chart of a method of making a blotting material for removing nitrate from drinking groundwater.
Detailed Description
The present invention will be further described with reference to specific embodiments, which are implemented on the premise of the technology of the present invention, and detailed embodiments are given, but the scope of the present invention is not limited to the following examples.
A preparation method of a blotting material for removing nitrate in drinking underground water is characterized in that nitrate is used as template ions, dimethyl diallyl ammonium chloride and acrylamide are used as functional monomers, ethylene glycol dimethacrylate is used as a cross-linking agent, and azobisisobutyronitrile is used as an initiator, and the blotting material is prepared by a bulk polymerization method and is a porous solid.
The preparation method of the imprinting material for removing the nitrate in the drinking groundwater specifically comprises the following steps:
A. pre-assembling imprinting materials: weighing 0-1.7g of template molecule sodium nitrate, 5.38g of functional monomer dimethyl diallyl ammonium chloride and 1.421g of acrylamide, adding into a mixed solution of N, N-dimethylformamide and methanol, stirring at normal temperature, and pre-assembling for 6-24 h;
B. polymerization of the material: heating the prepared liquid after pre-assembly in a water bath kettle at 65 ℃, sequentially adding 1.982-13.875g of cross-linking agent ethylene glycol dimethacrylate and 0.821g of initiator azobisisobutyronitrile into a reaction container, sealing the container after the material addition is finished, and synthesizing a porous solid polymer by a bulk polymerization method;
C. cleaning and drying materials: cooling the synthesized material to room temperature, then placing the cooled material in absolute ethyl alcohol for washing for 5 times to remove a mixed solvent and unreacted organic materials in a reaction system, then placing the material in 5g/L NaCl solution for washing for 5 times to elute template ion nitrate radicals in the material until no nitrate radical is detected in an eluent, and finally washing impurities remained on the surface of solid particles by deionized water; and (3) drying the cleaned imprinting material in a vacuum drying oven at 45 ℃ for 12h, and then transferring the imprinting material to a freeze drying oven for drying for 12 h.
The nitrate ion imprinting material can be applied to nitrate target adsorption in the drinking underground water in the decentralized rural areas.
Examples 1-4 mainly explore the effect of pre-assembly time on the adsorption capacity of the ion imprinted material.
Example 1
A preparation method of a blotting material for removing nitrate in drinking groundwater comprises the following steps:
A. weighing 0.85g of template molecule sodium nitrate, 5.38g of functional monomer dimethyl diallyl ammonium chloride and 1.421g of acrylamide in a 250mL silk-mouth reagent bottle, simultaneously weighing 40mL of N, N-dimethylformamide and 10mL of methanol, adding the mixture into the silk-mouth reagent bottle, placing the bottle in a water bath shaker at 25 ℃, and oscillating for 12 hours to obtain a polymerization reaction preparation solution.
B. Transferring the silk reagent bottle containing the preparation solution into a 65 ℃ water bath kettle, sequentially adding 9.911g of crosslinking agent ethylene glycol dimethacrylate and 0.821g of initiator azobisisobutyronitrile into the reaction container, and sealing the container after the materials are added. The polymerization was heated for 3 h.
C. And cooling the synthesized solid material to room temperature, then placing the cooled solid material in absolute ethyl alcohol for washing for 5 times to remove a mixed solvent and unreacted organic materials in a reaction system, then placing the imprinted material in a 5g/L NaCl solution for washing for 5 times, eluting template ion nitrate in the material until no nitrate is detected in the eluent, and finally washing impurities remained on the surfaces of solid particles by using deionized water. And (3) drying the cleaned imprinting material in a vacuum drying oven at 45 ℃ for 12h, and then transferring the imprinting material into a freeze drying oven for drying for 12 h.
Example 2
The present embodiment is different from embodiment 1 in that:
in the step one, the oscillation time of the template molecule and the functional monomer during preassembling is 6 h.
Example 3
The present embodiment is different from embodiment 1 in that:
in the step one, the oscillation time of the template molecule homofunctional monomer during preassembling is 18 h.
Example 4
The present embodiment is different from embodiment 1 in that:
in the step one, the oscillation time of the template molecule and the functional monomer during preassembling is 24 h.
Examples 1 and 5 to 7 mainly investigate the influence of the ratio of the functional monomer to the cross-linking agent on the adsorption capacity of the ion imprinting material.
Example 5
The present embodiment is different from embodiment 1 in that:
and the amount of the crosslinking agent ethylene glycol dimethacrylate added in the second step is 1.982 g.
Example 6
The present embodiment is different from embodiment 1 in that:
the amount of the crosslinking agent ethylene glycol dimethacrylate added in the second step was 3.964 g.
Example 7
The present embodiment is different from embodiment 1 in that:
the amount of the crosslinking agent ethylene glycol dimethacrylate added in the second step was 13.867 g.
Examples 1 and 8 to 11 mainly investigate the influence of the matching ratio of the template molecule and the functional monomer on the adsorption capacity of the ion imprinted material.
Example 8
The present embodiment is different from embodiment 1 in that:
the amount of template molecules added in step one was 0.17 g.
And the amount of the crosslinking agent ethylene glycol dimethacrylate added in the second step is 1.982 g.
Example 9
The present embodiment is different from embodiment 1 in that:
the amount of template molecules added in step one was 0.243 g.
And the amount of the crosslinking agent ethylene glycol dimethacrylate added in the second step is 1.982 g.
Example 10
The present embodiment is different from embodiment 1 in that:
the amount of template molecules added in step one was 0.425 g.
And the amount of the crosslinking agent ethylene glycol dimethacrylate added in the second step is 1.982 g.
Example 11
The present embodiment is different from embodiment 1 in that:
the amount of template molecules added in step one was 1.7 g.
And the amount of the crosslinking agent ethylene glycol dimethacrylate added in the second step is 1.982 g.
Comparative example 1
The comparative example is a preparation process of a non-imprinted material, and is mainly used for comparing with an imprinted material and exploring the specific adsorption performance of the imprinted material.
A. In the comparative example, template molecules are not added, 5.38g of functional monomers dimethyl diallyl ammonium chloride and 1.421g of acrylamide are added into a 250mL silk-mouth reagent bottle, 40mL of N, N-dimethylformamide and 10mL of methanol are simultaneously measured and added into the silk-mouth reagent bottle, the silk-mouth reagent bottle is placed into a water bath shaking table at 25 ℃, and the shaking table is shaken for 12 hours to obtain a polymerization reaction preparation solution.
B. Transferring the silk reagent bottle containing the preparation solution into a 65 ℃ water bath kettle, sequentially adding 1.982g of crosslinking agent ethylene glycol dimethacrylate and 0.821g of initiator azobisisobutyronitrile into the reaction vessel, and sealing the vessel after the materials are added. The polymerization was heated for 3 h.
C. And cooling the synthesized solid material to room temperature, then placing the cooled solid material in absolute ethyl alcohol for washing for 5 times to remove a mixed solvent and unreacted organic materials in a reaction system, then placing the imprinted material in a 5g/L NaCl solution for washing for 5 times, eluting template ion nitrate in the material until no nitrate is detected in the eluent, and finally washing impurities remained on the surfaces of solid particles by using deionized water. And (3) drying the cleaned imprinting material in a vacuum drying oven at 45 ℃ for 12h, and then transferring the imprinting material into a freeze drying oven for drying for 12 h.
Adsorption experiment:
0.5g of nitrate ion imprinted material and non-imprinted material are weighed and respectively added into 100mL of nitrate solution with the concentration of 300mg/L, the mixture is adsorbed for 30min under the normal temperature condition, then a 0.22 mu m filter membrane is used for filtration, and the concentration of nitrate ions in the filtrate is measured by an ultraviolet spectrophotometer. According to the change of ion concentration before and after adsorption, the saturated adsorption capacity of the ion imprinting material and the non-ion imprinting material is calculated according to the following formula:
comparative example 2
The comparative example is a sulfate ion competitive adsorption process of the nitrate ion imprinted material, and is mainly used for exploring the selective adsorption performance of the imprinted material by comparing the process of adsorbing nitrate ions by the imprinted material.
A. In the comparative example, 0.17g of template molecule, 5.38g of functional monomer dimethyldiallylammonium chloride and 1.421g of acrylamide are added into a 250mL silk reagent bottle, 40mL of N, N-dimethylformamide and 10mL of methanol are simultaneously measured and added into the silk reagent bottle, and the silk reagent bottle is placed into a water bath shaking table at 25 ℃ and is shaken for 12 hours to obtain a polymerization reaction preparation solution.
B. Transferring the silk reagent bottle containing the preparation solution into a 65 ℃ water bath kettle, sequentially adding 1.982g of crosslinking agent ethylene glycol dimethacrylate and 0.821g of initiator azobisisobutyronitrile into the reaction vessel, and sealing the vessel after the materials are added. The polymerization was heated for 3 h.
C. And cooling the synthesized solid material to room temperature, then placing the cooled solid material in absolute ethyl alcohol for washing for 5 times to remove a mixed solvent and unreacted organic materials in a reaction system, then placing the imprinted material in a 5g/L NaCl solution for washing for 5 times, eluting template ion nitrate in the material until no nitrate is detected in the eluent, and finally washing impurities remained on the surfaces of solid particles by using deionized water. And (3) drying the cleaned imprinting material in a vacuum drying oven at 45 ℃ for 12h, and then transferring the imprinting material into a freeze drying oven for drying for 12 h.
Adsorption experiment:
1g of nitrate ion imprinted material and non-imprinted material are weighed, respectively added into 100mL of nitrate and sulfate solution with the concentration of 80mg/L, adsorbed for 30min at normal temperature, filtered by a 0.22 mu m filter membrane, and the concentrations of nitrate and sulfate ions in the filtrate are respectively measured by an ultraviolet spectrophotometer and an ion chromatography. The adsorption partition coefficients of the ion imprinted material for two ions and the selectivity coefficient for nitrate are shown in table 1.
Table 1 partition coefficient and selection coefficient of nitrate ion imprinted material under two ion mixed solution
Summarizing the experimental data in fig. 1-3, it can be found that when the pre-assembly time of the template molecule and the functional monomer is 12h, the material ratio of the template molecule, the functional monomer and the cross-linking agent is 1: 10: and 5 is the optimal preparation condition of the ion imprinting material, and the maximum saturated adsorption amount of the ion imprinting material to nitrate is 14.876 mg/g and is obviously higher than that of the non-ion imprinting material (3.450 mg/g). In summary of table 1, the adsorption capacity of the imprinted material for sulfate ions is low compared with that of nitrate ions, and the selectivity coefficient for nitrate ions is 1.833 > 1, which shows that the imprinted material has certain selectivity for nitrate ions. Therefore, the material can be used for the specific and selective recognition of nitrate ions.
The invention utilizes the selective adsorption principle of the imprinted material, takes the cationic monomer as the core of the target adsorption material, solves the difficulties existing in the preparation process of the anionic imprinted material, and simultaneously solves the problem of low removal efficiency caused by non-target reaction in the existing method for removing nitrate from drinking groundwater, thereby solving the problem of difficult removal of nitrate from distributed drinking water in rural areas.
It is to be noted that the foregoing is only illustrative of the preferred embodiments of the present invention and the technical principles employed. It will be understood by those skilled in the art that the present invention is not limited to the particular embodiments described herein, but is capable of various obvious changes, rearrangements and substitutions as will now become apparent to those skilled in the art without departing from the scope of the invention. Therefore, although the present invention has been described in greater detail by the above embodiments, the present invention is not limited to the above embodiments, and may include other equivalent embodiments without departing from the spirit of the present invention, and the scope of the present invention is determined by the scope of the appended claims.
Claims (9)
1. A preparation method of a blotting material for removing nitrate in drinking underground water is characterized in that nitrate is used as template ions, dimethyl diallyl ammonium chloride and acrylamide are used as functional monomers, ethylene glycol dimethacrylate is used as a cross-linking agent, and azobisisobutyronitrile is used as an initiator, and the blotting material is prepared by a bulk polymerization method and is a porous solid.
2. The method for preparing the blotting material for removing nitrate from drinking groundwater according to claim 1, comprising the steps of:
A. pre-assembling imprinting materials: respectively adding a proper amount of template molecule sodium nitrate, functional monomers dimethyl diallyl ammonium chloride and acrylamide into a mixed solution of N, N dimethyl formamide and methanol, and stirring and pre-assembling at normal temperature for 6-24 h;
B. polymerization of the material: heating the prepared liquid after pre-assembly in a 65 ℃ water bath, sequentially adding a proper amount of cross-linking agent ethylene glycol dimethacrylate and initiator azobisisobutyronitrile into a reaction vessel, and synthesizing a porous solid polymer by using a bulk polymerization method in a closed environment;
C. cleaning and drying materials: cooling the synthesized material to room temperature, and then washing the material with absolute ethyl alcohol, NaCl solution and deionized water until no nitrate is detected in the eluent; and (3) drying the cleaned imprinting material in a vacuum drying oven at 45 ℃ for 12h, and then transferring the imprinting material to a freeze drying oven for drying for 12 h.
3. The method for preparing the blotting material for removing nitrate from drinking groundwater as claimed in claim 2, wherein: step A, the preassembly time is 12 h.
4. The method for preparing the blotting material for removing nitrate from drinking groundwater according to claim 3, wherein: the molar ratio of the template molecules to the functional monomers to the cross-linking agent is as follows: 1: 1-10: 1 to 7.
5. The method for preparing the blotting material for removing nitrate from drinking groundwater according to claim 4, wherein: the molar ratio of the template molecules to the functional monomers to the cross-linking agent is 1: 10: 5.
6. the method for preparing the blotting material for removing nitrate from drinking groundwater according to claim 4, wherein: the molar ratio of the template molecules to the initiator is as follows: 1: 5.
7. the method for preparing the blotting material for removing nitrate from drinking groundwater according to claim 4, wherein: the molar ratio of the functional monomers dimethyl diallyl ammonium chloride to acrylamide is as follows: 1: 1.
8. the method for preparing the blotting material for removing nitrate from drinking groundwater as claimed in claim 2, wherein: the template molecule sodium nitrate is 0-1.7g, the functional monomer dimethyl diallyl ammonium chloride is 5.38g, the acrylamide is 1.421g, and the ethylene glycol dimethacrylate is 1.982-13.875 g.
9. The method for preparing the blotting material for removing nitrate from drinking groundwater as claimed in claim 1, wherein: the prepared nitrate imprinting material can be applied to nitrate target adsorption treatment in underground water for drinking in distributed rural areas.
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| CN115501865A (en) * | 2022-09-30 | 2022-12-23 | 上海昱茗科技有限公司 | Nitrate nitrogen magnetic molecularly imprinted composite material using polyurethane hydrogel as carrier, and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030113234A1 (en) * | 2001-10-16 | 2003-06-19 | Murray George M. | Polymer based permeable membrane for removal of ions |
| CN102068968A (en) * | 2010-11-29 | 2011-05-25 | 大连海洋大学 | Lead ion imprinting integral column and preparation method thereof |
-
2021
- 2021-07-28 CN CN202110854997.7A patent/CN113788912A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030113234A1 (en) * | 2001-10-16 | 2003-06-19 | Murray George M. | Polymer based permeable membrane for removal of ions |
| CN102068968A (en) * | 2010-11-29 | 2011-05-25 | 大连海洋大学 | Lead ion imprinting integral column and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| ISHAK, NOORHIDAYAH ET.AL: "Theoretical and Experimental Studies of Ion Imprinted Polymer for Nitrate Detection", 《POLYMER SCIENCE, SERIES A. PHYSICS》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115501865A (en) * | 2022-09-30 | 2022-12-23 | 上海昱茗科技有限公司 | Nitrate nitrogen magnetic molecularly imprinted composite material using polyurethane hydrogel as carrier, and preparation method and application thereof |
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