CN113070045B - Preparation method of adsorbent for removing nitrate in industrial wastewater - Google Patents

Preparation method of adsorbent for removing nitrate in industrial wastewater Download PDF

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CN113070045B
CN113070045B CN202110471802.0A CN202110471802A CN113070045B CN 113070045 B CN113070045 B CN 113070045B CN 202110471802 A CN202110471802 A CN 202110471802A CN 113070045 B CN113070045 B CN 113070045B
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adsorbent
nitrate
stirring
chitosan
sio
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CN113070045A (en
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蔡建国
石洪雁
刘锐
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Anhui Bopu Nano New Materials Co.,Ltd.
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Linyi Haipu New Material Technology Co ltd
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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
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • 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
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—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
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • 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
    • 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
    • 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
    • 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
    • C02F2001/422—Treatment of water, waste water, or sewage by ion-exchange using anionic exchangers
    • 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

Abstract

A preparation method of an adsorbent for removing nitrate in industrial wastewater comprises the following steps: mixing SiO2Soaking the mesoporous nano material in acid to prepare SiO2Acidifying and hydrolyzing the mesoporous nano material; dissolving chitosan in deionized water or acid, and magnetically stirring; the acidified SiO2Adding into chitosan solution, stirring at room temperature, and vacuum filtering the excessive chitosan solution; adding epoxy chloropropane into the chitosan functionalized mesoporous silica nanoparticles, and adding KOH for refluxing; dropwise adding a solution consisting of N, N, N ', N' -tetraethyl-1, 3-propane diamine and ethanol, and stirring; and after filtering, alternately washing the obtained adsorbent by HCI, then washing the adsorbent by deionized water to neutral pH, and drying to obtain the nitrate-removed adsorbent. The method has the advantages of simple preparation process, low cost, easy recovery and recycling, and high nitrate radical removing efficiency.

Description

Preparation method of adsorbent for removing nitrate in industrial wastewater
Technical Field
The invention relates to the technical field of preparation methods of adsorbents, in particular to the technical field of preparation of adsorbents for removing nitrates from industrial wastewater.
Background
Nitrate pollution in surface water and ground water is an increasingly serious problem around the world, and as industry and agriculture rapidly develop, more three wastes are generated, and the concentration of nitrate in ground water is remarkably increased after the nitrate permeates underground. Moreover, nitrate is very soluble in water and can easily pass through the soil to the drinking water supply. High intake can result in abdominal pain, diarrhea, vomiting, hypertension, increased infant mortality, birth defects in the central nervous system, diabetes, spontaneous abortion, respiratory infections and alterations in the immune system. In recent years, several methods have been used for the removal of nitrate from wastewater. The nitrate can be removed by biological denitrification, catalytic reduction, reverse osmosis and electrodialysis, and ion exchange. Among these, biological denitrification offers the possibility of reducing nitrate to nitrogen by means of microbial degradation, but water is contaminated with bacteria and their metabolites. The catalytic reduction process has the advantage of being able to rapidly remove nitrates from water, but the disadvantage of this process is its high capital. Reverse osmosis and electrodialysis are because they are relatively expensive and only concentrate the nitrates into spent brine. Ion exchange technology, in turn, is generally more suitable for water decontamination and removal of inorganic ions due to its simplicity, effectiveness, selectivity, recovery, and relatively low cost.
Therefore, research on novel adsorbents based on ion exchange technology has received global attention in practical applications, and various adsorbents, including carbon-based adsorbents, layered double hydroxides, zeolites, clays, industrial wastes, and agricultural wastes, are used to remove nitrates from water. However, some of the common competing anions in industrial wastewater, such as sulfate, bicarbonate, and chloride, are widely present in wastewater. Although the concentration of non-toxic ions is low, their presence can significantly affect the completion of nitrate adsorption on the exchange sites. Therefore, the search for selective uptake of nitrate in the presence of competing anions is becoming increasingly necessary to better address the actual contamination problem.
Disclosure of Invention
The invention aims to provide a preparation method of an adsorbent for removing nitrate in industrial wastewater, which has the advantages of simple preparation process, low cost, easy recovery and recycling and high nitrate removal efficiency.
In order to achieve the technical effects, the invention adopts the following technical scheme:
a preparation method of an adsorbent for removing nitrate in industrial wastewater comprises the following steps:
step 1: 2-10g of SiO2Soaking the mesoporous nano material in 50-200ml of 2% -10% acid for 5-12 hours, and then soaking SiO2Acidifying and hydrolyzing the mesoporous nano material;
step 2: dissolving 2-10g of chitosan in 100-200ml of deionized water or 2-10% of acid, and stirring for 2-6 hours under magnetic stirring;
and step 3: will be provided withAcidified SiO2Adding into the chitosan solution, stirring at room temperature for 4-8 hr, and vacuum filtering to obtain excessive chitosan oligosaccharide solution;
and 4, step 4: adding 2-4g of epoxy chloropropane into the chitosan functionalized mesoporous silica nano particles, adding 20-100ml of 1-5% KOH, and refluxing for 2-8 hours at 60-100 ℃;
and 5: filtering the polymer particles obtained in the step 4 to obtain a suspension; dropwise adding a solution consisting of 2-10g N, N, N ', N' -tetraethyl-1, 3-propanediamine and 20-40g of ethanol, and stirring at 40-60 ℃ for 2-8 h;
step 6: after the reaction is finished, filtering, washing the obtained adsorbent by using 1.0-3.0M HCI alternately, washing the adsorbent by using deionized water until the pH value is neutral, and drying the adsorbent in an oven at 60-100 ℃ to obtain the nitrate-removed adsorbent.
Preferably, the SiO of the present invention2 The mesoporous nano material is 35-200 meshes.
Preferably, the acid of the present invention is at least one of hydrochloric acid, acetic acid, sulfuric acid, and oxalic acid.
Preferably, the chitosan of the present invention is CS.
The invention uses chitosan mesoporous SiO2 The modified nano material reacts with epichlorohydrin and N, N, N ', N' -tetraethyl-1, 3-propane diamine to introduce two functional groups NR3 +Meanwhile, the selectivity of the resin to nitrate can be improved by increasing the number of carbon atoms around the N atom. Successfully synthesizes a novel asymmetric amino strong-base anion adsorbent which has stronger adsorption capacity to nitrate no matter whether competitive anions exist in the solution or not. And under the condition that both nitrate and sulfate exist, the adsorbent is preferentially exchanged for nitrate and is not influenced by sulfate in water. The selective sequence of the nitrate removing adsorbent to nitrate is as follows in sequence: HCO3 -＜Cl-＜SO4 2-＜NO3 - 。
By adopting the technical scheme, compared with the prior art, the invention has the following advantages:
1. the invention discloses a preparation method for removing nitrate in wastewater by using an asymmetric amino strong-base anion exchange adsorbent, which has strong adsorption capacity on nitrate no matter whether competitive anions exist in a solution or not.
2. The invention uses SiO2The mesoporous nano material is a carrier, has large surface area, low relative density, light weight, good permeability and high chemical stability, has amino (-OH) on the surface, is convenient for introducing other chemical substances, and has relatively stable chemical bonds.
3. The invention adopts the following biological adsorbents: the chitosan, which is an effective biosorbent with low cost, no toxicity and high content, has strong adsorption potential of amino and hydroxyl functional groups, and the protonated cationic ammonium salt and the anionic nitrate radical are adsorbed by electrostatic attraction.
4. The invention adopts epichlorohydrin, which is an important organic synthetic raw material and an intermediate, and introduces chlorine-containing groups onto the chitosan-modified silica adsorbent through chemical reaction, so that the chemical stability is high, and the reaction is green and environment-friendly.
5. The invention adopts N, N, N ', N' -tetraethyl-1, 3-propane diamine, and introduces two functional groups NR by an ethanol hydrothermal method3 +Meanwhile, the number of carbon atoms around the N atom is also increased, so that the selectivity of the adsorbent to nitrate can be improved.
6. The modified silicon dioxide adsorbent is crosslinked with chitosan and N, N, N ', N' -tetraethyl-1, 3-propane diamine to generate quaternary ammonium salt double exchange sites to replace short-chain trimethylamine to be used as an amination reagent of a traditional adsorbent.
7. The selective sequence of the nitrate removing adsorbent to nitrate is as follows in sequence: HCO3 -＜Cl-＜SO4 2-＜NO3 - 
8. The present invention quantitatively extracts nitrate from the adsorbent using a 0.6m nacl solution. Sodium chloride was used as desorbent: the regeneration of the nitrate-removing material of the modified silicon dioxide is convenient, and other impurities are not introduced.
9. The nitrate in the wastewater is adsorbed by means of electrostatic adsorption, ion exchange and the like, and the nitrate can be removed by more than about 99% by the modified material when the pH = 7.
10. The modified nitrate radical removing adsorbent prepared by the invention has the advantages of simple preparation process, low cost, easy recovery and recycling and high nitrate radical removing efficiency.
Drawings
FIG. 1 is a graph comparing the adsorption capacities of example 1 of the present invention in wastewater of different pH.
FIG. 2 is a graph comparing the effect of coexisting ions on nitrate removal in example 1 of the present invention.
FIG. 3 is a graph comparing the retained adsorption efficiency of example 5 of the present invention for nitrates at different cycles.
Detailed Description
A preparation method of an adsorbent for removing nitrate in industrial wastewater comprises the following steps:
step 1: 2-10g of SiO2Soaking the mesoporous nano material in 50-200ml of 2% -10% acid for 5-12 hours, and then soaking SiO2Acidifying and hydrolyzing the mesoporous nano material;
step 2: dissolving 2-10g of chitosan in 100-200ml of deionized water or 2-10% of acid, and stirring for 2-6 hours under magnetic stirring;
and step 3: the acidified SiO2Adding into the chitosan solution, stirring at room temperature for 4-8 hr, and vacuum filtering to obtain excessive chitosan solution;
and 4, step 4: adding 2-4g of epoxy chloropropane into the chitosan functionalized mesoporous silica nano particles, adding 20-100ml of 1-5% KOH, and refluxing for 2-8 hours at 60-100 ℃;
and 5: filtering the polymer particles obtained in the step 4 to obtain a suspension; dropwise adding a solution consisting of 2-10g N, N, N ', N' -tetraethyl-1, 3-propanediamine and 20-40g of ethanol, and stirring at 40-60 ℃ for 2-8 h;
and 6: after the reaction is finished, filtering, washing the obtained adsorbent by using 1.0-3.0M HCI alternately, washing the adsorbent by using deionized water until the pH value is neutral, and drying the adsorbent in an oven at 60-100 ℃ to obtain the nitrate-removed adsorbent.
SiO of the invention2 The mesoporous nano material is 35-200 meshes.
The acid of the invention is at least one of hydrochloric acid, acetic acid, sulfuric acid and oxalic acid.
The chitosan of the invention is CS.
Example 1
Step 1: 2g of SiO2 Soaking (100 mesh) mesoporous nano material in 100ml of 2% acetic acid for 5 hours, and acidifying and hydrolyzing the mesoporous nano material;
and 2, step: 2g of Chitosan (CS) was dissolved in 100ml of 2% acetic acid and stirred for 2 hours under magnetic stirring;
and step 3: the acidified SiO2Adding into the chitosan solution, stirring at room temperature for 4 hours, and filtering the redundant chitosan solution;
and 4, step 4: adding 4g of epichlorohydrin into the chitosan functionalized mesoporous silica nanoparticles, adding 20ml of 1% KOH, and refluxing for 3 hours at 60 ℃;
and 5: the suspension is filtered off from the polymer particles. Dropwise adding a solution consisting of 4g N, N, N ', N' -tetraethyl-1, 3-propanediamine and 20g of ethanol, and stirring at 40 ℃ for 2 hours;
step 6: after the reaction is finished, filtering, washing the obtained adsorbent by using 1.0M HCI alternately, washing the adsorbent to neutral pH by using deionized water, and drying the adsorbent in an oven at 60 ℃ to obtain the nitrate-removed adsorbent.
Example 2
Step 1: 3g of SiO2 Soaking (50 mesh) mesoporous nano material in 100ml of 3% hydrochloric acid for 5 hours, and acidifying and hydrolyzing the mesoporous nano material;
step 2: dissolving 5g of Chitosan (CS) in 200ml of deionized water, and stirring for 2 hours under magnetic stirring;
and step 3: the acidified SiO2Adding into the chitosan solution, stirring at room temperature for 5 hours, and filtering the redundant chitosan solution;
and 4, step 4: adding 3g of epichlorohydrin into the chitosan functionalized mesoporous silica nanoparticles, adding 20ml of 1% KOH, and refluxing for 2 hours at 100 ℃;
and 5: the suspension is filtered off from the polymer particles. Dropwise adding a solution consisting of 5g N, N, N ', N' -tetraethyl-1, 3-propanediamine and 30g of ethanol, and stirring at 60 ℃ for 3 hours;
step 6: after the reaction is finished, filtering, washing the obtained adsorbent by using 1.5M HCI alternately, washing the adsorbent by using deionized water until the pH value is neutral, and drying the adsorbent in an oven at 80 ℃ to obtain the nitrate-removed adsorbent.
Example 3
Step 1: 5g of SiO2 Soaking (200 mesh) mesoporous nano material in 50ml of 3.2% acid sulfuric acid for 5 hours, and acidifying and hydrolyzing the mesoporous nano material;
step 2: 4g of Chitosan (CS) was dissolved in 150ml of 3% hydrochloric acid and stirred for 3 hours with magnetic stirring;
and step 3: the acidified SiO2Adding into the chitosan solution, stirring at room temperature for 4-8 hr, and vacuum filtering to obtain excessive chitosan solution;
and 4, step 4: adding 2-4g of epoxy chloropropane into the chitosan functionalized mesoporous silica nano particle, adding 40ml of 4% KOH, and refluxing for 2 hours at 80 ℃;
and 5: the suspension is filtered off from the polymer particles. Dropwise adding a solution consisting of 6g N, N, N ', N' -tetraethyl-1, 3-propanediamine and 40g of ethanol, and stirring at 50 ℃ for 2.5 hours;
step 6: after the reaction is finished, filtering, washing the obtained adsorbent by using 2.0M HCI alternately, washing the adsorbent by using deionized water until the pH value is neutral, and drying the adsorbent in an oven at 100 ℃ to obtain the nitrate-removed adsorbent.
Example 4
Step 1: 3g of SiO2 Soaking (35 mesh) mesoporous nano material in 50ml of 5% oxalic acid for 5 hours, and acidifying and hydrolyzing the mesoporous nano material;
step 2: dissolving 2g of Chitosan (CS) in 100ml of deionized water or 2.5% oxalic acid, and stirring for 2-6 hours under magnetic stirring;
and step 3: the acidified SiO2Adding into the chitosan solution, stirring at room temperature for 4 hours, and filtering the redundant chitosan solution;
and 4, step 4: adding 3g of epichlorohydrin into the chitosan functionalized mesoporous silica nanoparticles, adding 20ml of 1.25 percent KOH, and refluxing for 2-8 hours at 60 ℃;
and 5: the suspension is filtered off from the polymer particles. Dropwise adding a solution consisting of 3g N, N, N ', N' -tetraethyl-1, 3-propanediamine and 40g of ethanol, and stirring at 60 ℃ for 4 hours;
step 6: after the reaction is finished, filtering, washing the obtained adsorbent by using 1.6M HCI alternately, washing the adsorbent by using deionized water to neutral pH, and drying the adsorbent in an oven at 70 ℃ to obtain the nitrate-removed adsorbent.
Example 5
Step 1: 4g of SiO2 Soaking (100 mesh) mesoporous nano material in 100ml of 2% hydrochloric acid for 5 hours, and acidifying and hydrolyzing the mesoporous nano material;
step 2: dissolving 4g of Chitosan (CS) in 100-200ml of deionized water, and stirring for 4 hours under magnetic stirring;
and step 3: the acidified SiO2Adding into the chitosan solution, stirring at room temperature for 4 hours, and filtering the redundant chitosan solution;
and 4, step 4: adding 3g of epichlorohydrin into the chitosan functionalized mesoporous silica nanoparticles, adding 20ml of 1.6 percent KOH, and refluxing for 6 hours at 60 ℃;
and 5: the suspension is filtered off from the polymer particles. Dropwise adding a solution consisting of 5g N, N, N ', N' -tetraethyl-1, 3-propanediamine and 40g of ethanol, and stirring at 40 ℃ for 3 hours;
step 6: after the reaction is finished, filtering, washing the obtained adsorbent by using 1.2M HCI alternately, washing the adsorbent to neutral pH by using deionized water, and drying the adsorbent in an oven at 60 ℃ to obtain the nitrate-removed adsorbent.
1) 5mL of the modified nitrate-removing material (adsorbent) of each of the above experimental examples 1 to 5 were placed in 5 identical 100mL beakers.
2) Nitrate-containing wastewater (nitrate concentration C =1000ppm, pH = 7) was taken and 50mL each was added to the above five beakers.
3) Stirring was continued in a temperature-controlled constant-temperature shaker for 2 hours at a stirring speed of 500 rpm.
4) After adsorption was completed, the adsorbent was separated from the nitrate-containing wastewater using filter paper. Then, the change in the nitrate concentration in the solution was measured in batches using a multiparameter water quality meter (5B-6C (V8)).
The results of the experiments are shown in the following table:
Figure 661968DEST_PATH_IMAGE002
FIG. 1 is a graph comparing the adsorption capacities of example 1 of the present invention in wastewater of different pH. The specific test process is as follows:
1) 5g of the modified nitrate-removing material (adsorbent) of the above experimental example 1 was placed in 8 identical 100mL beakers, respectively.
2) Nitrate-containing waste water (nitrate concentration C =500 ppm) having different pH (2-9) was taken and 5g each was added to the above 8 beakers.
3) Stirring was continued in a temperature-controlled constant temperature shaker for 5 hours at a stirring speed of 600 rpm.
4) After adsorption was completed, the adsorbent was separated from the nitrate-containing wastewater using filter paper.
Then, the change in the nitrate concentration in the solution was measured in batches using a multiparameter water quality meter (5B-6C (V8)).
FIG. 2 is a graph comparing the effect of coexisting ions on nitrate removal in example 1 of the present invention. The specific test process is as follows:
1) 5g of the nitrate-removing material (adsorbent) of the above experimental example 1 was placed in 4 identical 100mL beakers, respectively.
2) Respectively taking out the solution containing different anions (SO)4 2-、Cl-、NO3 -、HCO3 -) 50mL of each nitrate-containing wastewater (pH =7, nitrate concentration C =500 ppm) was added to the above 4 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 nitrate-containing wastewater using filter paper.
Then, the change in the nitrate concentration in the solution was measured in batches using a multiparameter water quality meter (5B-6C (V8)).
FIG. 3 is a graph comparing the retained adsorption efficiency of example 5 of the present invention for nitrates at different cycles. The specific test process is as follows:
1) 5mL of the nitrate-removing material (adsorbent) of the above experimental example 5 was loaded into a glass column at a height-diameter ratio of 4:1 and a flow rate of 1BV/H, and 50mL of nitrate-containing wastewater was introduced by a peristaltic pump (raw water nitrate concentration C =1000ppm, pH = 7).
2) After every 10BV of nitrate-containing wastewater was adsorbed, 0.6M NaCl 1BV was used for desorption (1 BV/H), and the above adsorption process was repeated to test the relative stability.
The change in nitrate concentration in the solution was measured in batches using a multiparameter water quality tester (5B-6C (V8)).
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 preparation method of an adsorbent for removing nitrate in industrial wastewater is characterized by comprising the following steps:
step 1: 2-10g of SiO2Soaking the mesoporous nano material in 50-200mL of 2% -10% acid for 5-12 hours, and soaking SiO2Acidifying and hydrolyzing the mesoporous nano material;
step 2: dissolving 2-10g of chitosan in 100-200mL of deionized water or 2-10% acid, and stirring for 2-6 hours under magnetic stirring;
and step 3: the acidified SiO2Adding into the chitosan solution, stirring at room temperature for 4-8 hr, and vacuum filtering to obtain excessive chitosan solution;
and 4, step 4: adding 2-4g of epichlorohydrin into the chitosan functionalized mesoporous silica nanoparticles, adding 20-100mL of 1-5% KOH, and refluxing for 2-8 hours at 60-100 ℃;
and 5: filtering the polymer particles obtained in the step 4 to obtain a suspension; dropwise adding a solution consisting of 2-10g of N, N, N ', N' -tetraethyl-1, 3-propanediamine and 20-40g of ethanol, and stirring at 40-60 ℃ for 2-8 h;
step 6: and after the reaction is finished, filtering, washing the obtained adsorbent by using 1.0-3.0M HCl, washing the adsorbent to neutral pH by using deionized water, and drying the adsorbent in an oven at 60-100 ℃ to obtain the nitrate-removed adsorbent.
2. The method for preparing an adsorbent for removing nitrates from industrial wastewater according to claim 1, wherein the SiO in step 1 is2The mesoporous nano material is 35-200 meshes.
3. The method for preparing an adsorbent for removing nitrates from industrial wastewater according to claim 1, wherein the acid in the steps 1 and 2 is at least one of hydrochloric acid, acetic acid, sulfuric acid, and oxalic acid.
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CN109967044A (en) * 2019-04-08 2019-07-05 青岛农业大学 The chitosan multi-porous gel rubber material and preparation method thereof that in Pickering- high prepared by phase solution template

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CN102580687A (en) * 2012-01-19 2012-07-18 沈阳化工大学 Polyamine-modified chitosan base expanded bed adsorbing medium and preparation method thereof
CN105126790A (en) * 2015-09-06 2015-12-09 河南师范大学 Synthesis and application method of composite function resin for selectively removing nitrate and phosphate at same time
CN109133252A (en) * 2018-10-12 2019-01-04 北京师范大学 A kind of nitrate in groundwater selective removal technique and equipment
CN109967044A (en) * 2019-04-08 2019-07-05 青岛农业大学 The chitosan multi-porous gel rubber material and preparation method thereof that in Pickering- high prepared by phase solution template

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