CN114082407A - Synthetic method of high-salinity medium-fluorine-removal adsorbent - Google Patents
Synthetic method of high-salinity medium-fluorine-removal adsorbent Download PDFInfo
- Publication number
- CN114082407A CN114082407A CN202111204940.9A CN202111204940A CN114082407A CN 114082407 A CN114082407 A CN 114082407A CN 202111204940 A CN202111204940 A CN 202111204940A CN 114082407 A CN114082407 A CN 114082407A
- Authority
- CN
- China
- Prior art keywords
- fluorine
- resin
- modified
- reaction
- synthesizing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000003463 adsorbent Substances 0.000 title claims abstract description 32
- 238000010189 synthetic method Methods 0.000 title abstract description 4
- 239000011347 resin Substances 0.000 claims abstract description 39
- 229920005989 resin Polymers 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000460 chlorine Substances 0.000 claims abstract description 20
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 238000006115 defluorination reaction Methods 0.000 claims abstract description 18
- SMWDFEZZVXVKRB-UHFFFAOYSA-N anhydrous quinoline Natural products N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 16
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- -1 quinoline amide Chemical class 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 150000001804 chlorine Chemical group 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 230000008961 swelling Effects 0.000 claims abstract description 7
- 150000003248 quinolines Chemical class 0.000 claims abstract description 6
- 238000010992 reflux Methods 0.000 claims abstract description 6
- 239000007790 solid phase Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 3
- 238000001308 synthesis method Methods 0.000 claims description 3
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 2
- 229940027991 antiseptic and disinfectant quinoline derivative Drugs 0.000 claims description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium nitrate Inorganic materials [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Inorganic materials [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 2
- 239000011324 bead Substances 0.000 claims 1
- 239000011737 fluorine Substances 0.000 abstract description 35
- 229910052731 fluorine Inorganic materials 0.000 abstract description 35
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 34
- 239000002351 wastewater Substances 0.000 abstract description 28
- 239000000463 material Substances 0.000 abstract description 11
- 238000011084 recovery Methods 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 238000001179 sorption measurement Methods 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000000967 suction filtration Methods 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 8
- 229910001385 heavy metal Inorganic materials 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- PUBYDOJONNWFJJ-UHFFFAOYSA-N 2-aminoquinoline-3-carboxylic acid Chemical group C1=CC=C2C=C(C(O)=O)C(N)=NC2=C1 PUBYDOJONNWFJJ-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 239000012266 salt solution Substances 0.000 description 5
- HFNTWGBMPAYPQY-UHFFFAOYSA-N 2-aminoquinoline-6-carboxamide Chemical group N1=C(N)C=CC2=CC(C(=O)N)=CC=C21 HFNTWGBMPAYPQY-UHFFFAOYSA-N 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- NMRWCMUREKFWON-UHFFFAOYSA-N 2-aminoquinoline-4-carboxamide Chemical compound C1=CC=C2C(C(=O)N)=CC(N)=NC2=C1 NMRWCMUREKFWON-UHFFFAOYSA-N 0.000 description 2
- UEFKMJWKPVAVND-UHFFFAOYSA-N 4-aminoquinoline-3-carboxylic acid Chemical compound C1=CC=C2C(N)=C(C(O)=O)C=NC2=C1 UEFKMJWKPVAVND-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- VQTOKXHLOLTVRS-UHFFFAOYSA-N benzamide quinolin-8-amine Chemical compound NC(=O)C1=CC=CC=C1.C1=CN=C2C(N)=CC=CC2=C1 VQTOKXHLOLTVRS-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000002289 effect on microbe Effects 0.000 description 1
- 238000009297 electrocoagulation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000015784 hyperosmotic salinity response Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
Images
Classifications
-
- 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
- B01J20/265—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
- 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
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
-
- 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
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Analytical Chemistry (AREA)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a method for synthesizing a high-salinity defluorination adsorbent, belonging to the technical field of separation of fluorine-containing wastewater. The synthetic method of the adsorbent comprises the following steps: (1) swelling chlorine ball resin in an organic solvent, respectively adding alkali and quinoline amide derivatives, stirring for reaction to obtain a mixture containing the resin, and performing solid-liquid separation to obtain a solid phase, wherein the solid phase is modified chlorine ball resin 1; (2) adding a quinoline derivative and an organic solvent into the modified chlorine ball resin 1 obtained in the step (1), stirring and mixing, and heating and refluxing for reaction to obtain a chlorine ball modified resin 2; (3) and (3) adding a nitrate solution into the chlorine ball modified resin 2 obtained in the step (2) for reaction, and obtaining the defluorination adsorbent after the reaction is finished. The modified defluorination material prepared by the invention has the advantages of simple preparation process, low cost, easy recovery and recycling and high defluorination efficiency in wastewater.
Description
Technical Field
The invention belongs to the technical field of separation of fluorine-containing wastewater, and particularly relates to a synthetic method of a high-salt medium-fluorine-removing adsorbent.
Background
In recent years, the improvement of environmental protection processing capability of fluorine chemical enterprises is a necessary way to improve market competitiveness. The market demand of fluorine-containing chemicals in the world is rapidly increased, the number of enterprises such as chemical and pharmaceutical industries is increased sharply, and a large amount of fluorine-containing products such as fluorine-containing electronic chemicals, fluorine-containing fine chemicals, fluorine-containing polymers, fluorine-containing coatings and the like are produced, so that a large amount of fluorine-containing wastewater is generated, and the problem of treating fluorine-containing high-salt wastewater in the fluorine chemical industry is still a difficult point in the industry. The industrial high-salt fluorine-containing wastewater has great harm to the environment and human health, and the produced high-salt fluorine-containing wastewater can easily block pipelines in production. Usually, some water treatment agents such as acid and alkali are added in water treatment for neutralization and the like, so that water quality is mineralized, the concentration of soluble salts in wastewater is increased, and when the concentration of inorganic salts in wastewater is more than 10%, the inorganic salts have strong inhibition effect on microorganisms, so that high-salinity wastewater difficult to biochemically treat is formed. And therefore, some enterprises are faced with enormous discharge pressures. The selective separation and fluorine removal of inorganic salt is always an urgent problem to be solved in the treatment of waste water containing miscellaneous salts, and the currently common fluorine removal method mainly comprises the following steps: membrane separation, precipitation, electrocoagulation, reverse osmosis, and the like. However, most of the above methods require high operation and maintenance costs, and generate secondary pollution, and the removal efficiency of fluorine is not high in a high-salt environment.
Adsorption is one of the most effective methods for removing many contaminants from aqueous solutions. The most common of these adsorption processes is ion exchange, which has the major advantages of simplicity, relatively low cost and efficiency in water treatment compared to other processes.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for synthesizing a high-salinity fluorine-removing adsorbent.
A novel method for synthesizing a high-salt medium-fluorine-removal adsorbent comprises the following steps:
(1) swelling chlorine ball resin in an organic solvent, respectively adding alkali and quinoline amide derivatives, stirring for reaction to obtain a mixture containing the resin, and performing solid-liquid separation to obtain a solid phase, wherein the solid phase is modified chlorine ball resin 1;
(2) adding a quinoline derivative and an organic solvent into the modified chlorine ball resin 1 obtained in the step (1), stirring and mixing, and heating and refluxing for reaction to obtain a chlorine ball modified resin 2;
in one embodiment of the present invention, in step (1), the quinoline amide derivative is selected from 2-aminoquinoline-6-carboxamide, 2-aminoquinoline-4-carboxamide or 8-aminoquinoline benzamide.
In one embodiment of the present invention, in step (2), the quinoline derivative is selected from 2-aminoquinoline-3-carboxylic acid, 3-aminoquinoline-3-carboxylic acid or 4-aminoquinoline-3-carboxylic acid.
(3) And (3) adding a nitrate solution into the chlorine ball modified resin 2 obtained in the step (2) for reaction, and obtaining the defluorination adsorbent after the reaction is finished.
In one embodiment of the present invention, step (1), the reaction conditions are: reacting for 3-4h at 40-60 ℃.
In one embodiment of the present invention, in step (1), the organic solvent is one or more of ethanol, DMF, toluene, acetone and dichloroethane.
In one embodiment of the present invention, in step (2), the organic solvent is one or more of DMSO, DMF, toluene, and acetone.
In one embodiment of the present invention, in the step (1), the mass concentration of the alkali in the mixture is 20 to 60%. The alkali is selected from potassium hydroxide or sodium hydroxide.
In one embodiment of the invention, in the step (2), the molar ratio of the 2-aminoquinoline-3-carboxylic acid to the modified chlorine ball resin 1 is 1-5: 1-5.
In one embodiment of the present invention, in the step (3), the nitrate is selected from Cu (NO)3)2、Ce(NO3)3、Zr(NO3)4And Ni (NO)3)2One or more of (a).
In one embodiment of the present invention, in the step (3), the nitrate solution has a concentration of 1% to 90%.
In one embodiment of the invention, the solvent of the nitrate solution is an aqueous ethanol solution, wherein the volume ratio of ethanol to water is 1-4: 1-4.
In one embodiment of the present invention, in step (3), the reaction conditions are: vacuum distilling at 60-100 deg.C for 3-8 hr.
The invention also provides the defluorination adsorbent prepared by the synthesis method.
The chelating adsorbent is used for adsorbing the fluoride, and is beneficial to removing the fluoride in a high-salinity wastewater environment, the adsorbent belongs to a quinoline modified chelating adsorbent, the resin is modified in a bonding mode, the flow rate of the modifier is not easy, and the adsorption performance is relatively stable. Because quinoline is weak in alkalinity, the quinoline is difficult to form salt under acidic conditions by utilizing the special physical and chemical properties of quinoline, is difficult to protonate and is easy to chelate with metal ions (Cu)2+/Ni2+Etc.) has excellent salt tolerance and high selectivity in removing fluorine from fluorine-containing high-salt wastewater. The prepared adsorbent has good stability, high adsorption capacity to fluorine ions and good flexibility: chemically stable, such as durability and salt resistance.
Compared with the prior art, the technical scheme of the invention has the following advantages:
the invention takes the chlorine ball as a carrier, modifies the chlorine-containing group into the pyridine group through chemical reaction, has high chemical stability, modifies the original resin, and has low cost, less energy consumption and environmental protection.
The invention adopts quinoline amide derivatives and quinoline derivatives to modify the chlorine spheres, has high chemical stability, and the reaction is green and environment-friendly.
The invention adopts a one-pot two-step method, changes the reaction conditions, and the 2-aminoquinoline-6-formamide amino and the 2-aminoquinoline-3-carboxylic acid carboxyl are subjected to dehydration condensation to form peptide bonds, and has high chemical stability.
Two quinoline groups are introduced into the chlorine ball, and the quinoline is not easy to protonate under an acidic condition due to weak alkalinity, and has strong salt resistance.
According to the modified polymeric material synthesized by the quinoline grafted chlorine ball, N on a quinoline group contains a lone electron pair, so that a stable coordination structure is easily formed with heavy metal ions. When the high-salt fluorine-containing wastewater passes through the resin, fluorine forms a coordination structure with heavy metal ions so as to be adsorbed on the resin. Higher defluorination capacity and affinity are shown in high salt environment.
The adsorbing material of the invention utilizes the dual functions of electrostatic adsorption, ion exchange and the like, thereby achieving high-efficiency defluorination. The modified material has the fluorine removal rate of more than 98% in high-salt fluorine-containing wastewater with the pH value of 4-8, wherein the high-salt fluorine-containing wastewater refers to wastewater with the total salt mass fraction of more than 1%.
The modified defluorination material of the invention adopts 1MNaOH to carry out the circulation of the adsorption and desorption processes, and the recovery rate reaches more than 97 percent.
The modified defluorination material prepared by the invention has the advantages of simple preparation process, low cost, easy recovery and recycling and high defluorination efficiency in wastewater.
Drawings
In order that the present disclosure may be more readily and clearly understood, reference is now made to the following detailed description of the embodiments of the present disclosure taken in conjunction with the accompanying drawings, in which
FIG. 1 is a graph showing the fluorine concentration in the regenerated adsorbed effluent in test example 3 of the present invention.
Detailed Description
The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.
Example 1
1. 2g of chlorine ball resin (made by Jiangsu Heipu functional materials Co., Ltd.) was added into a three-necked flask, 50mL of absolute ethanol was added thereto for swelling, and the mixture was stirred at room temperature for 8 hours.
2. 10mL of 20% NaOH aqueous solution and 2g of 2-aminoquinoline-6-carboxamide were added thereto, and the mixture was stirred at 40 ℃ for 3 hours, followed by suction filtration of the excess reaction solution.
3. 2g of 2-aminoquinoline-3-formic acid and 50ml of DMSO are added into the resin, and reflux reaction is carried out for 4h at 80 ℃. And (5) carrying out suction filtration, and washing with ethanol and deionized water for 3 times.
4. 1g of heavy metal salt solution: cu (NO)3)2Dissolved in 50mL of a 1:1 volume ratio mixture of ethanol and water.
5. And adding the resin into the nitrate solution, distilling at 80 ℃ under reduced pressure for 4h, filtering the redundant solution, washing with deionized water to be neutral, and drying in an oven at 60 ℃.
Example 2
1. 3g of chlorine ball resin (made by Jiangsu Heipu functional materials Co., Ltd.) was added into a three-neck flask, 60ml of DMF was added for swelling, and the mixture was stirred at room temperature for 8 hours.
2. 10mL of a 30% NaOH aqueous solution and 2g of 2-aminoquinoline-4-carboxamide were added, and the mixture was stirred at 50 ℃ for 3 hours, followed by suction filtration of the excess reaction solution.
3. 2g of 2-aminoquinoline-3-carboxylic acid and 60ml of DMF are added into the resin, and reflux reaction is carried out for 4h at the temperature of 80 ℃. And (5) carrying out suction filtration, and washing with ethanol and deionized water for 3 times.
4. 2g of heavy metal salt solution: ce (NO)3)3Dissolved in 50mL of a 1:2 volume ratio mixture of ethanol and water.
5. And adding the resin into the nitrate solution, distilling at 70 ℃ under reduced pressure for 4h, filtering the redundant solution, washing with deionized water to be neutral, and drying in an oven at 70 ℃.
Example 3
1. 8g of chlorine ball resin (made by Jiangsu Heipu functional materials Co., Ltd.) was added to a three-necked flask, 100mL of toluene was added thereto for swelling, and the mixture was stirred at room temperature for 10 hours.
2. 10mL of 50% NaOH aqueous solution and 4g of 2-aminoquinoline-6-carboxamide were added, and the mixture was stirred at 60 ℃ for 6 hours, followed by suction filtration of the excess reaction solution.
3. 5g of 4-aminoquinoline-3-carboxylic acid and 100mL of acetone were added to the resin, and the mixture was refluxed at 100 ℃ for 7 hours. And (5) carrying out suction filtration, and washing with ethanol and deionized water for 3 times.
4. And (3) mixing 7g of heavy metal salt solution: zr (NO)3)4Dissolved in 100mL of a mixed solution of ethanol and water at a volume ratio of 1: 4.
5. And adding the resin into the nitrate solution, distilling at 100 ℃ under reduced pressure for 6 hours, filtering the redundant solution, washing with deionized water to be neutral, and drying in an oven at 60 ℃.
Example 4
1. 6g of chlorine ball resin (made by Jiangsu Heipu functional materials Co., Ltd.) was added into a three-necked flask, and 70mL of acetone was added thereto to swell the mixture, followed by stirring at room temperature for 8 hours.
2. 10mL of 40% NaOH aqueous solution and 4g of 8-aminoquinoline benzamide were added thereto, and the mixture was stirred at 50 ℃ for 6 hours, followed by suction filtration of the excess reaction solution.
3. 3g of 2-aminoquinoline-3-carboxylic acid and 50mL of toluene were added to the resin, and the mixture was refluxed at 90 ℃ for 4 hours. And (5) carrying out suction filtration, and washing with ethanol and deionized water for 3 times.
4. Adding heavy metal salt solution 2gNi (NO)3)2Dissolved in 60mL of a mixed solution of ethanol and water at a volume ratio of 3:1, respectively.
5. And adding the resin into the nitrate solution, distilling at 60 ℃ under reduced pressure for 3h, filtering the redundant solution, washing with deionized water to be neutral, and drying in an oven at 80 ℃.
Example 5
1. 6g of chlorine ball resin is added into a three-neck flask, 50mL of dichloroethane is added for swelling, and the mixture is stirred for 8 hours at room temperature.
2. 10mL of 20% NaOH aqueous solution and 2g of 2-aminoquinoline-6-carboxamide were added, and the mixture was stirred at 50 ℃ for 4 hours, followed by suction filtration of the excess reaction solution.
3. 5g of 3-aminoquinoline-3-carboxylic acid and 90ml of DMF are added into the resin, and the reflux reaction is carried out for 7h at the temperature of 90 ℃. And (5) carrying out suction filtration, and washing with ethanol and deionized water for 3 times.
4. And (3) mixing 5g of heavy metal salt solution: cu (NO)3)2Dissolved in 100mL of a mixed solution of ethanol and water at a volume ratio of 1:1, respectively.
5. And adding the resin into the nitrate solution, distilling at 60 ℃ under reduced pressure for 5h, filtering the redundant solution, washing with deionized water to be neutral, and drying in an oven at 90 ℃.
Test example 1
1. 10mL of each of the modified fluorine-removing materials (adsorbents) and chlorine spheres obtained in the above-mentioned experimental examples 1 to 5 was put into 6 identical 250mL Erlenmeyer flasks.
2. Respectively taking high-salt fluorine-containing wastewater (containing fluorine C)F -2000ppm, pH 7, TDS 100000mg/L, and different metal cations and anions (SO) contained in the waste water4 2-、Cl-、NO3 -、Na+、K+、Mg2+) 100mL of each was added to the six beakers described above.
3. Stirring was continued in a temperature-controlled constant temperature shaker for 5 hours at a stirring speed of 700 rpm.
4. After adsorption, the adsorbent is separated from the high-salt fluorine-containing wastewater by using filter paper. Then, the change in fluoride concentration in the batch solution was measured with a fluoride ion selective electrode (Reye PHS-3C type pH meter). The results are shown in Table 1.
TABLE 1
From the above experimental results, it can be seen that: in the presence of different metal cations, anions (SO)4 2-、Cl-、NO3 -、Na+、K+、Mg2+) The self-made modified defluorination adsorbent has good selectivity in the high-salt fluorine-containing wastewater.
Test example 2
1. 5mL of the modified fluorine-removing material (adsorbent) of the above experimental example 1 was placed in a 100mL beaker.
2. High-salt fluorine-containing wastewater (pH 6, C) of some metal materials Co., Ltd in JiangsuF -2500ppm TDS 200000mg/L) 500mL was added to the beaker.
3. Stirring was continued in a temperature-controlled constant temperature shaker for 8 hours at a stirring speed of 500 rpm.
4. After the adsorption was completed, the adsorbent was separated from the fluorine-containing wastewater using filter paper. Then, the change in fluoride concentration in the batch solution was measured with a fluoride ion selective electrode (Reye PHS-3C type pH meter). The results are shown in Table 2.
TABLE 2
| Material | Throughput of treatment | Water outlet CF-(ppm) | Raw water |
| Example 3 | 100BV | 24 | 2500ppm |
And (4) conclusion: the self-made modified defluorination adsorbent has large adsorption capacity when used for treating high-salt fluorine-containing wastewater.
Test example 3
1. 5mL of the modified fluorine-removing material (adsorbent) of the above test example 3 was put in a 100mL Erlenmeyer flask, and 50mL of high-salt fluorine-containing wastewater (raw water CF)-2000ppm, pH 8, TDS 100000mg/L) was stirred continuously in a temperature-controlled thermostated oscillator for 8 hours at a stirring speed of 500 rpm.
2. After adsorption of every 10BV of the fluorine-containing wastewater was completed, the wastewater was filtered, and then desorbed by 0.2M NaOH1BV (600rpm), and the above adsorption and desorption process was repeated to test the relative stability.
3. The change in fluoride concentration in the batch solution was measured using a fluoride ion selective electrode (Retzen PHS-3C type pH meter).
The results are shown in FIG. 1: the abscissa in fig. 1 is the number of times of adsorption-desorption regeneration; the ordinate represents the concentration (ppm) of fluorine in the effluent.
And (4) conclusion: after the modified material is subjected to adsorption, desorption and regeneration for 30 times, the adsorbed water is stable below 3ppm, and the stability is good.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (10)
1. A method for synthesizing a high-salt medium-fluorine-removal adsorbent is characterized by comprising the following steps:
(1) swelling chlorine ball resin in an organic solvent, respectively adding alkali and quinoline amide derivatives, stirring for reaction to obtain a mixture containing the resin, and performing solid-liquid separation to obtain a solid phase, wherein the solid phase is modified chlorine ball resin 1;
(2) adding a quinoline derivative and an organic solvent into the modified chlorine ball resin 1 obtained in the step (1), stirring and mixing, and heating and refluxing for reaction to obtain a chlorine ball modified resin 2;
(3) and (3) adding a nitrate solution into the chlorine ball modified resin 2 obtained in the step (2) for reaction, and obtaining the defluorination adsorbent after the reaction is finished.
2. The new synthesis method of the high-salt defluorination adsorbent in accordance with claim 1, wherein in step (1), the organic solvent is one or more of ethanol, DMF, toluene, acetone and dichloroethane.
3. The method for synthesizing the high-salt defluorination adsorbent according to claim 1, wherein in the step (2), the organic solvent is one or more of DMSO, DMF, toluene and acetone.
4. The method for synthesizing the high-salt defluorination adsorbent according to the claim 1, wherein in the step (1), the mass fraction of the alkali in the mixture is 20-60%.
5. The method for synthesizing the high-salinity fluorine-removing adsorbent according to claim 1, wherein in the step (2), the molar ratio of the quinoline derivatives to the modified chloromethylated bead resin 1 is 1-5: 1-5.
6. The method for synthesizing the high-salinity fluorine-removing adsorbent according to claim 1, wherein in the step (3), the nitrate is selected from Cu (NO)3)2、Ce(NO3)3、Zr(NO3)4And Ni (NO)3)2One or more of (a).
7. The method for synthesizing the high-salinity medium-fluorine-removing adsorbent according to claim 1, wherein in the step (3), the mass fraction of the nitrate solution is 1-90%.
8. The method for synthesizing the high-salinity fluorine-removing adsorbent according to claim 7, wherein the solvent of the nitrate solution is an ethanol aqueous solution, and the volume ratio of ethanol to water in the ethanol aqueous solution is 1-4: 1-4.
9. The method for synthesizing the high-salinity fluorine-removing adsorbent according to claim 1, wherein in the step (3), the reaction conditions are as follows: vacuum distilling at 60-100 deg.C for 3-8 hr.
10. A defluorination adsorbent prepared by the synthesis method of any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111204940.9A CN114082407A (en) | 2021-10-15 | 2021-10-15 | Synthetic method of high-salinity medium-fluorine-removal adsorbent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111204940.9A CN114082407A (en) | 2021-10-15 | 2021-10-15 | Synthetic method of high-salinity medium-fluorine-removal adsorbent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114082407A true CN114082407A (en) | 2022-02-25 |
Family
ID=80296989
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111204940.9A Withdrawn CN114082407A (en) | 2021-10-15 | 2021-10-15 | Synthetic method of high-salinity medium-fluorine-removal adsorbent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114082407A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115228437A (en) * | 2022-08-18 | 2022-10-25 | 四川轻化工大学 | Surface modification method for making surface of activated carbon positive |
-
2021
- 2021-10-15 CN CN202111204940.9A patent/CN114082407A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115228437A (en) * | 2022-08-18 | 2022-10-25 | 四川轻化工大学 | Surface modification method for making surface of activated carbon positive |
| CN115228437B (en) * | 2022-08-18 | 2023-10-31 | 四川轻化工大学 | Surface modification method for making active carbon surface positive |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20190023585A1 (en) | Method and apparatus for the recovery and deep treatment of polluted acid | |
| CN102198407B (en) | Positive ion exchanger and method for removing heavy metal ion in waste water | |
| CN101973618B (en) | Method for removing and recycling hexavalent chromium ions by using chitosan-iron complex | |
| CN104024168A (en) | Coking wastewater treatment | |
| CN104129831A (en) | Method for simultaneous removal and recovery of heavy metal ions and organic acid by using chelating resin | |
| CN105854811A (en) | Preparation of sodium alginate intercalated hydrotalcite adsorbent and application thereof | |
| CN114082407A (en) | Synthetic method of high-salinity medium-fluorine-removal adsorbent | |
| CN112755972A (en) | Preparation of silicon-based resin and application of silicon-based resin as defluorination adsorbent | |
| CN113877550B (en) | Preparation method of polymeric adsorbent for boron element in water phase | |
| He et al. | Research progress on removal methods of Cl-from industrial wastewater | |
| CN112452308B (en) | Synthetic method and application of pyridine amide-containing adsorption polymer | |
| CN109382004B (en) | Method for separating and recovering mixed heavy metal by using calcium alginate membrane | |
| CN117282412A (en) | Interpenetrating network adsorbent for adsorbing noble metal and preparation method and application thereof | |
| CN111790359A (en) | Adsorbent for treating hexavalent chromium in wastewater | |
| CN112777672B (en) | Functionalized silica modified defluorination material and preparation and application thereof | |
| CN113070046B (en) | Preparation method of defluorination adsorbent modified by biopolymer composite material | |
| CN102942274B (en) | Treatment method of saline and alkaline wastewater in copper oxide production process | |
| CN113070045B (en) | Preparation method of adsorbent for removing nitrate in industrial wastewater | |
| CN116251563A (en) | Preparation method of coal coking industrial wastewater purifying agent based on modified zeolite | |
| CN114804456A (en) | Recovery system and method for alkaline washing wastewater generated in chloroethylene production by oxychlorination method | |
| CN114082408B (en) | Chelating ion exchange adsorbent and preparation and application thereof | |
| CN110201638B (en) | Preparation and application of MOF material | |
| CN211367244U (en) | Pretreatment system for C9 resin production and anthraquinone process hydrogen peroxide production wastewater | |
| Arabi | Adsorption of Orange 3R by chitosan modified montmorillonite nanocomposite | |
| CN112174248A (en) | Method for adsorbing electroplating wastewater containing heavy metal nickel by using fly ash-based zeolite |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20220225 |
|
| WW01 | Invention patent application withdrawn after publication |