CN115350682A - Attapulgite composite material rich in carboxyl and preparation method and application thereof - Google Patents
Attapulgite composite material rich in carboxyl and preparation method and application thereof Download PDFInfo
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- CN115350682A CN115350682A CN202210980634.2A CN202210980634A CN115350682A CN 115350682 A CN115350682 A CN 115350682A CN 202210980634 A CN202210980634 A CN 202210980634A CN 115350682 A CN115350682 A CN 115350682A
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Abstract
The invention discloses an attapulgite composite material rich in carboxyl and a preparation method and application thereof, the composite material is prepared by firstly carrying out silanization modification on attapulgite/acidified attapulgite and a silane coupling agent with epoxy groups, which can endow a large amount of epoxy groups on the surface of the attapulgite, and the epoxy groups can carry out ring opening reaction with active hydrogen of a compound rich in amino groups, so that the compound rich in amino groups is grafted on the surface of the attapulgite to obtain aminated attapulgite, then the aminated attapulgite reacts with glycidol to carry out hydroxylation modification, so that the attapulgite composite material rich in ortho-position hydroxyl is obtained, and a large amount of amino active hydrogen on the surface of the attapulgite can react with sodium chloroacetate, thereby endowing a large amount of functional carboxyl on the surface of the material. The obtained composite material can be used for adsorbing heavy metal ions, and the adsorption capacity of the composite material to ferric ions can reach more than 450mg/g.
Description
Technical Field
The invention relates to the technical field of composite adsorbing materials, in particular to an attapulgite composite material rich in carboxyl and a preparation method and application thereof.
Background
As one of the most important substances of all living things on earth including plants and animals, water covers almost 75% of the earth's surface, but less than 1% of water is available for human use. However, due to industrial activities such as mining, electroplating and metal processing, large amounts of wastewater contaminated with heavy metals are discharged every year. How to effectively treat heavy metal ions in wastewater has become one of the main problems of global attention. Common treatment methods for heavy metal ions in wastewater include a chemical precipitation method, a reverse osmosis method, an ion exchange method, a membrane separation method, an adsorption method and the like, but the adsorption method is the most common important method for removing the heavy metal ions in water at present due to the advantages of simple operation, low cost, good treatment effect and the like.
The attapulgite clay is a clay mineral which mainly contains water-containing magnesium-rich silicate, has the advantages of no toxicity, good mechanical property, strong thermal stability, abundant reserves, low cost and wide application range, and has great potential as an adsorbent. The attapulgite is a layered silicate material formed by staggered arrangement of silicon-oxygen tetrahedron and magnesium-aluminum octahedron structures, and an effective pore structure is formed by the attapulgite due to a special arrangement mode, so that the attapulgite is favorable for application in the field of adsorption.
The attapulgite has certain research as an adsorbent of heavy metal ions, xu Hui and the like prepare polyaniline/attapulgite nano composite material doped with hydrochloric acid by utilizing an in-situ polymerization method, and the adsorption capacity of the polyaniline/attapulgite nano composite material to Cr and Cu can reach 40mg/g and 30mg/g (Xu Hui, xu Kui, guo Donggong. Competitive adsorption of copper ions and hexavalent chromium ions on polyaniline/attapulgite nano composite material manufacturers [ J]Silicate science, 2011,39 (10): 1559-1563). 5363 adsorption of granulated, modified and acid-modified attapulgite to Cu (II), ni (II) and Cd (II) was studied by Zhao Chaofan, etc., and the adsorption amounts can reach 68mg/g, 73mg/g and 55mg/g (Zhao Chaofan, huang Xiaolan, zhang Yan, etc. modified granular attapulgite to Cu, ni, CStudy of adsorption Properties of d ions [ J]Environmental engineering. 2014,32 (7): 67-72). Li Bo, etc. through alkali modification, acid modification and silanization modification, the adsorption of modified attapulgite on copper ions is studied, and the maximum adsorption capacity is 9.77mg/g (Li Bo, wang Zhiru, li Gongji, etc.. Modified ATP has high adsorption capacity on heavy metal ions Cu 2+ Study of adsorption kinetics [ J]South river science, 2022, (8): 82-86).
Because attapulgite has certain adsorption performance to pollutants such as heavy metal, fuel, organic matters and the like, but the selectivity to heavy metal ions is not strong, the attapulgite is limited in the practical application process. The heavy metal ions can be selectively chelated with the ions with negative charges due to the positive charges, so that the selective adsorption of the heavy metal ions can be realized after the surface of the attapulgite is subjected to carboxylation modification, and the adsorption capacity of the heavy metal can be greatly improved due to the strong coordination and chelation performance of carboxylate radicals and the heavy metal ions, so that the attapulgite modified attapulgite has a huge application prospect.
Disclosure of Invention
In view of the above, the invention provides a carboxyl-rich attapulgite composite material and a preparation method and application thereof, and the principle is as follows: the attapulgite/acidified attapulgite and a silane coupling agent with epoxy groups are firstly subjected to silanization modification, so that a large number of epoxy groups can be endowed on the surface of the attapulgite, the epoxy groups can perform a ring opening reaction with active hydrogen of a compound rich in amino groups, so that the compound rich in amino groups is grafted on the surface of the attapulgite to obtain the aminated attapulgite, then the aminated attapulgite reacts with glycidol to perform hydroxylation modification, so that the attapulgite composite material rich in ortho-position hydroxyl groups is obtained, and a large number of active hydrogen of amino groups on the surface of the attapulgite can react with sodium chloroacetate, so that a large number of functional carboxyl groups are endowed on the surface of the material.
In order to achieve the purpose, the invention adopts the following technical scheme:
the attapulgite composite material rich in carboxyl comprises the following components in parts by weight:
10 parts of attapulgite/acidified attapulgite, 6-15 parts of epoxy silane, 1.05-4.65 parts of sodium chloroacetate, 0.36-1.60 parts of sodium hydroxide and 0.2-1.2 parts of amino-rich compound.
Preferably, the epoxy silane comprises one of 3-glycidoxypropyltrimethoxysilane, triethoxy (3-glycidoxypropyl) silane, 3- [ (2,3) -glycidoxy ] propylmethyldimethoxysilane, diethoxy (3-glycidoxypropyl) methylsilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
The beneficial effects brought by the optimization are as follows: the micromolecular organosilane coupling agent with 1 epoxy functional group can be modified by amino compounds with active hydrogen after the surface of the attapulgite is modified, thereby endowing the material with special functionality.
Preferably, the amino-rich compound includes one of ethylenediamine, melamine, diethylenetriamine, triethylenetetramine, phenylenediamine, and polyethyleneimine.
Preferably, the phenylenediamine comprises p-phenylenediamine or m-phenylenediamine;
the polyethyleneimine comprises one of PEI300, PEI600, PEI1200, PEI1800, PEI10000, and PEI 70000.
The above-mentioned preferable compounds have a high content of active hydrogen NH, and can be modified with a large amount of sodium chloroacetate to provide a material with a rich carboxyl functional group.
The invention also aims to provide a preparation method of the attapulgite composite material rich in carboxyl, which comprises the following steps:
(1) Weighing machine
Weighing the composite material raw materials for later use;
(2) Preparation of epoxy silanized attapulgite
The attapulgite or the acidified attapulgite is placed in a first solvent for dispersion, then epoxy silane is added, reflux reaction is carried out for 6-12h at the temperature of 70-90 ℃, the mixture is cooled and centrifuged, then the mixture is placed in a second solvent for dispersion, and then the mixture is centrifuged again, and is dried after repeated for 2-5 times, so as to obtain the epoxy silanized attapulgite;
(3) Preparation of aminated attapulgite
Weighing 10 parts of epoxy silanized attapulgite, dispersing in 200-400mL of water, introducing nitrogen for 20-40min, adding a compound rich in amino, reacting at 30-50 ℃ for 6-10h, heating to 60-70 ℃ for reaction for 4-8h, dispersing in water after the reaction is finished, centrifuging, repeating for 2-5 times, and drying to obtain the aminated attapulgite;
(4) Preparation of carboxyl-rich attapulgite composite material
Weighing 10 parts of aminated attapulgite, dispersing in 200-400mL of water, then adding sodium chloroacetate and sodium hydroxide, stirring and reacting for 5-10h at 70-100 ℃, centrifuging after the reaction is finished, then dispersing in water, repeating for 2-5 times, and drying to obtain the carboxyl-rich attapulgite composite material.
Wherein, the repetition of 2 to 5 times in the invention is the repetition of 2 to 5 times of centrifugation after dispersion or the repetition of 2 to 5 times of dispersion after centrifugation.
Preferably, the acidified attapulgite is prepared by the following method:
dispersing 10 parts of attapulgite in 300-600 parts of hydrochloric acid solution with the concentration of 1.5-3mol/L, refluxing for 1-3h at 70-90 ℃, centrifuging, washing with deionized water, repeating for 2-5 times, and drying to obtain the acidified attapulgite.
The beneficial effects brought by the optimization are as follows: the acidified attapulgite has larger specific surface area, and can improve the modification degree of the attapulgite by the following operation, thereby endowing more functional groups on the surface of the attapulgite.
Preferably, the first solvent and the second solvent are respectively one of ethanol, acetonitrile, DMF and DMSO.
Preferably, the centrifugation speeds in the steps (2) to (4) are 1000-10000r/min, and the centrifugation time is 3-20min;
drying in the steps (2) to (4) for 1 to 6 hours at the temperature of between 100 and 200 ℃;
in the step (4), the stirring speed is 200-1000r/min.
The invention also aims to provide the application of the attapulgite composite material rich in carboxyl in heavy metal ion adsorption.
According to the technical scheme, compared with the prior art, the invention discloses and provides the attapulgite composite material rich in carboxyl, and the preparation method and the application thereof. The attapulgite composite material rich in carboxyl prepared by the invention can be used for adsorbing heavy metal ions, and the adsorption capacity of the attapulgite composite material to ferric ions can reach more than 450mg/g.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example one
(1) Preparation of epoxy silanized attapulgite
Dispersing 10 parts of attapulgite with a certain amount of acetonitrile, adding 12 parts of 3-glycidyloxypropyl trimethoxy silane, and carrying out reflux reaction for 10h at 75 ℃. Cooling, centrifuging, dispersing with a certain amount of acetonitrile, centrifuging, repeating for 3 times, and drying to obtain epoxy silanized attapulgite.
(2) Preparation of aminated attapulgite
Dispersing 10 parts of epoxy silanized attapulgite in 200mL of deionized water, introducing nitrogen for 20min, adding 0.6 part of melamine, reacting for 8h at 40 ℃, and heating to 60 ℃ for reacting for 8h. And dispersing with deionized water, centrifuging after the reaction is finished, repeating for 2 times, and drying to obtain the aminated attapulgite.
(3) Preparation of attapulgite composite material rich in carboxyl
Weighing 10 parts of aminated attapulgite, dispersing in 250mL of deionized water, adding 2.76 parts of sodium chloroacetate, adding 0.95 part of sodium hydroxide, stirring at 80 ℃ for 8h, stopping reaction, centrifuging after the reaction is finished, dispersing in deionized water, repeating for 4 times, and drying to obtain the attapulgite composite material rich in carboxyl.
The prepared attapulgite composite material rich in carboxyl is used as a boron adsorbent for adsorbing heavy metal ions, and the adsorption capacity of the attapulgite composite material to ferric ions can reach 480mg/g.
Example two
(1) Preparation of epoxy silanized attapulgite
Dispersing 10 parts of attapulgite with a certain amount of DMF, adding 8 parts of triethoxy (3-epoxypropyloxypropyl) silane, and carrying out reflux reaction at 80 ℃ for 8 hours. Cooling, centrifuging, dispersing with a certain amount of DMF, centrifuging, repeating for 4 times, and drying to obtain epoxy silanized attapulgite.
(2) Preparation of aminated attapulgite
Dispersing 10 parts of epoxy silanized attapulgite in 400mL of deionized water, introducing nitrogen for 35min, adding 0.2 part of ethylenediamine, reacting at 30 ℃ for 10h, and heating to 70 ℃ for 4h. And dispersing the attapulgite by using deionized water after the reaction is finished, centrifuging, repeating the steps and drying to obtain the aminated attapulgite.
(3) Preparation of carboxyl-rich attapulgite composite material
Weighing 10 parts of aminated attapulgite, dispersing in 300mL of deionized water, introducing nitrogen for 20min, then adding 1.05 parts of sodium chloroacetate, adding 0.36 parts of sodium hydroxide, stirring for 10h at 70 ℃, stopping the reaction, centrifuging after the reaction is finished, dispersing in deionized water, repeating for 5 times, and drying to obtain the attapulgite composite material rich in carboxyl.
The prepared attapulgite composite material rich in carboxyl is used as a boron adsorbent for adsorbing heavy metal ions, and the adsorption capacity of the attapulgite composite material to ferric ions can reach 450mg/g.
EXAMPLE III
(1) Preparation of epoxy silanized attapulgite
Dispersing 10 parts of attapulgite with a certain amount of ethanol, adding 6 parts of 3- [ (2,3) -glycidoxy ] propyl methyl dimethoxy silane, and carrying out reflux reaction at 90 ℃ for 6h. Cooling, centrifuging, dispersing with a certain amount of ethanol, centrifuging, repeating for 2 times, and drying to obtain epoxy silanized attapulgite.
(2) Preparation of aminated attapulgite
Dispersing 10 parts of epoxy silanized attapulgite in 400mL of deionized water, introducing nitrogen for 40min, adding 0.54 part of phenylenediamine, reacting for 10h at 35 ℃, and heating to 65 ℃ for reacting for 6h. And dispersing with deionized water, centrifuging after the reaction is finished, repeating for 5 times, and drying to obtain the aminated attapulgite.
(3) Preparation of carboxyl-rich attapulgite composite material
Weighing 10 parts of aminated attapulgite, dispersing in 200mL of deionized water, introducing nitrogen for 10min, then adding 1.74 parts of sodium chloroacetate, adding 0.60 parts of sodium hydroxide, stirring for 7h at 85 ℃, stopping the reaction, centrifuging after the reaction is finished, dispersing by using the deionized water, repeating for 2 times, and drying to obtain the carboxyl-rich attapulgite composite material.
The prepared attapulgite composite material rich in carboxyl is used as a boron adsorbent for adsorbing heavy metal ions, and the adsorption quantity of the attapulgite composite material to ferric ions can reach 430mg/g.
Example four
(1) Preparation of epoxy silanized attapulgite
The preparation of the acidified attapulgite comprises the following steps: dispersing 10 parts of attapulgite in 400 parts of hydrochloric acid solution with the concentration of 2mol/L, refluxing for 2h at 80 ℃, centrifuging, washing with deionized water, repeating for 3 times, and drying to obtain the acidified attapulgite.
Dispersing 10 parts of acidified attapulgite by a certain amount of DMSO, adding 9 parts of diethoxy (3-glycidyloxypropyl) methylsilane, and carrying out reflux reaction at 85 ℃ for 8 hours. Cooling, centrifuging, dispersing with a certain amount of DMSO, centrifuging, repeating for 5 times, and drying to obtain epoxy silanized attapulgite.
(2) Preparation of aminated attapulgite
Dispersing 10 parts of epoxy silanized attapulgite in 300mL of deionized water, introducing nitrogen for 30min, adding 1.2 parts of triethylenetetramine, reacting for 7h at 50 ℃, and heating to 65 ℃ for reacting for 6h. And dispersing with deionized water, centrifuging, repeating for 3 times, and drying to obtain the aminated attapulgite.
(3) Preparation of carboxyl-rich attapulgite composite material
Weighing 10 parts of aminated attapulgite, dispersing in 400mL of deionized water, introducing nitrogen for 40min, then adding 4.65 parts of sodium chloroacetate, adding 1.60 parts of sodium hydroxide, stirring for 8h at 90 ℃, stopping the reaction, centrifuging after the reaction is finished, dispersing in deionized water, repeating for 4 times, and drying to obtain the attapulgite composite material rich in carboxyl.
The prepared attapulgite composite material rich in carboxyl is used as a boron adsorbent for adsorbing heavy metal ions, and the adsorption quantity of the attapulgite composite material to ferric ions can reach 560mg/g.
EXAMPLE five
(1) Preparation of epoxy silanized attapulgite
The preparation of the acidified attapulgite comprises the following steps: dispersing 10 parts of attapulgite in 350 parts of hydrochloric acid solution with the concentration of 1.5mol/L, refluxing for 1h at 90 ℃, centrifuging, washing with deionized water, repeating for 2 times, and drying to obtain the acidified attapulgite.
Dispersing 10 parts of acidified attapulgite with a certain amount of ethanol, adding 15 parts of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and carrying out reflux reaction at 70 ℃ for 12 hours. Cooling, centrifuging, dispersing with a certain amount of ethanol, centrifuging, repeating for 5 times, and drying to obtain epoxy silanized attapulgite.
(2) Preparation of aminated attapulgite
Dispersing 10 parts of epoxy silanized attapulgite in 250mL of deionized water, introducing nitrogen for 25min, adding 0.48 part of diethylenetriamine, reacting for 8h at 40 ℃, and heating to 60 ℃ for reacting for 8h. And dispersing with deionized water, centrifuging, repeating for 3 times, and drying to obtain the aminated attapulgite.
(3) Preparation of carboxyl-rich attapulgite composite material
Weighing 10 parts of aminated attapulgite, dispersing in 350mL of deionized water, introducing nitrogen for 30min, then adding 2.16 parts of sodium chloroacetate, adding 0.75 part of sodium hydroxide, stirring for 10h at 75 ℃, stopping the reaction, centrifuging after the reaction is finished, dispersing by using the deionized water, repeating for 5 times, and drying to obtain the attapulgite composite material rich in carboxyl.
The prepared attapulgite composite material rich in carboxyl is used as a boron adsorbent for adsorbing heavy metal ions, and the adsorption quantity of the attapulgite composite material to ferric ions can reach 530mg/g.
EXAMPLE six
(1) Preparation of epoxy silanized attapulgite
Preparing acidified attapulgite: dispersing 10 parts of attapulgite in 600 parts of hydrochloric acid solution with the concentration of 3mol/L, refluxing for 3 hours at 70 ℃, centrifuging, washing with deionized water, repeating for 5 times, and drying to obtain the acidified attapulgite.
Dispersing 10 parts of acidified attapulgite with a certain amount of ethanol, adding 10 parts of triethoxy (3-epoxypropyloxypropyl) silane, and carrying out reflux reaction at 80 ℃ for 10 hours. Cooling, centrifuging, dispersing with a certain amount of ethanol, centrifuging, repeating for 3 times, and drying to obtain epoxy silanized attapulgite.
(2) Preparation of aminated attapulgite
Dispersing 10 parts of epoxy silanized attapulgite in 350mL of deionized water, introducing nitrogen for 35min, adding 0.88 part of polyethyleneimine (Mn = 1200), reacting at 60 ℃ for 6h, and heating to 65 ℃ for 6h. And dispersing with deionized water, centrifuging after the reaction is finished, repeating for 2 times, and drying to obtain the aminated attapulgite.
(3) Preparation of carboxyl-rich attapulgite composite material
Weighing 10 parts of aminated attapulgite, dispersing in 300mL of deionized water, introducing nitrogen for 30min, then adding 2.30 parts of sodium chloroacetate, adding 0.80 part of sodium hydroxide, stirring at 95 ℃ for 6h, stopping reaction, centrifuging after the reaction is finished, dispersing by using the deionized water, repeating for 3 times, and drying to obtain the attapulgite composite material rich in carboxyl.
The prepared attapulgite composite material rich in carboxyl is used as a boron adsorbent for adsorbing heavy metal ions, and the adsorption quantity of the attapulgite composite material to ferric ions can reach 630mg/g.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. The attapulgite composite material rich in carboxyl is characterized by comprising the following components in parts by weight:
10 parts of attapulgite/acidified attapulgite, 6-15 parts of epoxy silane, 1.05-4.65 parts of sodium chloroacetate, 0.36-1.60 parts of sodium hydroxide and 0.2-1.2 parts of amino-rich compound.
2. The attapulgite composite material rich in carboxyl groups according to claim 1,
the epoxy silane comprises one of 3-glycidyloxypropyltrimethoxysilane, triethoxy (3-glycidyloxypropyl) silane, 3- [ (2,3) -glycidoxy ] propylmethyldimethoxysilane, diethoxy (3-glycidyloxypropyl) methylsilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
3. The attapulgite composite material rich in carboxyl groups according to claim 1,
the amino-rich compound comprises one of ethylenediamine, melamine, diethylenetriamine, triethylenetetramine, phenylenediamine and polyethyleneimine.
4. The attapulgite composite material rich in carboxyl groups according to claim 1,
the phenylenediamine comprises p-phenylenediamine or m-phenylenediamine;
the polyethyleneimine comprises one of PEI300, PEI600, PEI1200, PEI1800, PEI10000 and PEI 70000.
5. The preparation method of the attapulgite composite material rich in carboxyl according to any one of claims 1 to 4, characterized by comprising the following steps:
(1) Weighing machine
Weighing the composite material raw material as defined in any one of claims 1 to 4 for later use;
(2) Preparation of epoxy silanized attapulgite
The attapulgite or the acidified attapulgite is placed in a first solvent for dispersion, then epoxy silane is added, reflux reaction is carried out for 6-12h at the temperature of 70-90 ℃, the mixture is cooled and centrifuged, then the mixture is placed in a second solvent for dispersion, and then the mixture is centrifuged again, and is dried after repeated for 2-5 times, so as to obtain the epoxy silanized attapulgite;
(3) Preparation of aminated attapulgite
Weighing 10 parts of epoxy silanized attapulgite, dispersing in 200-400mL of water, introducing nitrogen for 20-40min, adding a compound rich in amino, reacting at 30-50 ℃ for 6-10h, heating to 60-70 ℃ for reaction for 4-8h, dispersing in water after the reaction is finished, centrifuging, repeating for 2-5 times, and drying to obtain the aminated attapulgite;
(4) Preparation of carboxyl-rich attapulgite composite material
Weighing 10 parts of aminated attapulgite, dispersing in 200-400mL of water, then adding sodium chloroacetate and sodium hydroxide, stirring and reacting at 70-100 ℃ for 5-10h, centrifuging after the reaction is finished, then placing in water for dispersing, repeating for 2-5 times, and drying to obtain the attapulgite composite material rich in carboxyl.
6. The preparation method of the attapulgite composite material rich in carboxyl according to claim 5, characterized in that the acidified attapulgite is prepared by the following method:
dispersing 10 parts of attapulgite in 300-600 parts of hydrochloric acid solution with the concentration of 1.5-3mol/L, refluxing at 70-90 ℃ for 1-3h, centrifuging, washing with deionized water, repeating for 2-5 times, and drying to obtain the acidified attapulgite.
7. The method for preparing the attapulgite composite material rich in carboxyl according to claim 5, characterized in that the first solvent and the second solvent are respectively one of ethanol, acetonitrile, DMF and DMSO.
8. The method for preparing the attapulgite composite material rich in carboxyl according to claim 5, characterized in that the centrifugation speeds in the steps (2) to (4) are both 1000 to 10000r/min, and the centrifugation time is both 3 to 20min;
drying in the steps (2) to (4) for 1 to 6 hours at the temperature of between 100 and 200 ℃;
in the step (4), the stirring speed is 200-1000r/min.
9. Use of the attapulgite composite material rich in carboxyl in heavy metal ion adsorption according to any one of claims 1 to 4.
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| CN104226263A (en) * | 2014-09-29 | 2014-12-24 | 陕西科技大学 | Method I for preparing amino-modified attapulgite adsorbent and method II for removing hexavalent chromium from water |
| CN104722265A (en) * | 2015-03-27 | 2015-06-24 | 陕西科技大学 | Preparation method and application of modified attapulgite adsorbent |
| CN104888709A (en) * | 2014-03-06 | 2015-09-09 | 范力仁 | Magnetic aminocarboxyl chelating adsorption granular material and preparation method thereof |
| CN110523371A (en) * | 2019-09-10 | 2019-12-03 | 河海大学 | It is a kind of attapulgite modified and its preparation method and application |
| US20220023851A1 (en) * | 2018-11-28 | 2022-01-27 | Cube Biotech Gmbh | Solid-phase chelator material, method for producing thereof and use thereof for the purification of proteins |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104888709A (en) * | 2014-03-06 | 2015-09-09 | 范力仁 | Magnetic aminocarboxyl chelating adsorption granular material and preparation method thereof |
| CN104226263A (en) * | 2014-09-29 | 2014-12-24 | 陕西科技大学 | Method I for preparing amino-modified attapulgite adsorbent and method II for removing hexavalent chromium from water |
| CN104722265A (en) * | 2015-03-27 | 2015-06-24 | 陕西科技大学 | Preparation method and application of modified attapulgite adsorbent |
| US20220023851A1 (en) * | 2018-11-28 | 2022-01-27 | Cube Biotech Gmbh | Solid-phase chelator material, method for producing thereof and use thereof for the purification of proteins |
| CN110523371A (en) * | 2019-09-10 | 2019-12-03 | 河海大学 | It is a kind of attapulgite modified and its preparation method and application |
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