CN115350681A - Carboxylated attapulgite composite material and preparation method and application thereof - Google Patents
Carboxylated attapulgite composite material and preparation method and application thereof Download PDFInfo
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- CN115350681A CN115350681A CN202210980632.3A CN202210980632A CN115350681A CN 115350681 A CN115350681 A CN 115350681A CN 202210980632 A CN202210980632 A CN 202210980632A CN 115350681 A CN115350681 A CN 115350681A
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/28—Treatment of water, waste water, or sewage by sorption
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a carboxylated attapulgite composite material and a preparation method and application thereof. The attapulgite/acidified attapulgite and the silane coupling agent with active NH are firstly modified by silanization, so that a large amount of active NH can be given to the surface of the attapulgite, and active hydrogen can react with sodium chloroacetate, thereby giving a large amount of functional carboxyl to the surface of the material. The prepared carboxylated attapulgite composite material is used for adsorbing heavy metal ions, has unique selectivity on ferric ions, and the adsorption capacity can reach more than 400 mg/g.
Description
Technical Field
The invention relates to the technical field of composite adsorbing materials, in particular to a carboxylated attapulgite composite material and a preparation method and application thereof.
Background
Environmental problems have been global problems facing the whole biosphere including animals and plants on the earth, and with the development of human society, the discharge of industrial wastewater has become more serious to damage human health and cause problems in water ecosystem, wherein heavy metal pollution of water is one of the most challenging problems. Heavy metal ions in the water body mainly come from the industries of electroplating, metallurgy, battery manufacturing, mining and the like, and the heavy metal ions have the characteristics of high migration, high toxicity, non-biodegradability and the like, so that the heavy metal ions cause great harm to the environment. Heavy metal ions can also be concentrated by the biological food chain, which can pose a serious threat to the ecosystem even at low concentrations. At present, in methods for treating heavy metal ion wastewater, an ion exchange method, an electrochemical method, a precipitation method, a membrane separation method, an adsorption method and the like are applied. The adsorption method has the unique advantages of low cost, simple operation, high removal rate and the like, and is considered to be one of the most economical and effective methods.
The adsorption material is one of the most important influencing factors for removing heavy metal ions in water, the traditional adsorbents comprise activated carbon, zeolite molecular sieves, clay, metal oxides and the like, and the novel adsorbents comprise nano materials, ion imprinting materials, metal organic framework polymers, porous organic polymers and the like and various composite materials. Since different adsorbents have different physicochemical properties, their adsorption properties and behavior also differ from one another. The particle size, specific surface area, pore diameter, pore structure and the like of the adsorbent are important physical properties of the adsorbent, and influence the adsorption equilibrium time, adsorption capacity, separation of the adsorbent and the like. The chemical properties of the adsorbent are represented by the type and number of functional groups contained on the surface of the adsorbent, and the oxidation and reduction performance of the adsorbent, and determine the chemical action between the adsorbent and the adsorbate.
In the prior art, a method for removing Fe (III) from a model water solution by using carboxylation modified siloxane gel (high-efficiency removal of Fe (III) through carboxylation modification of a siloxane gel adsorbent, von morning, laser fusion research center of China institute of engineering and physics) is disclosed, but the theoretical maximum adsorption capacity is only about 94 mg/g.
Attapulgite is a magnalium silicate clay mineral with a layer chain structure, which has a great specific surface area and excellent adsorption performance due to unique fibrous or rod-shaped crystal morphology and a layer chain crystal structure. The attapulgite has certain adsorption performance on pollutants such as heavy metals, fuels, organic matters and the like, but has low selectivity on heavy metal ions, and 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 heavy metals can be greatly improved due to the strong coordination and chelation performance of carboxylate radicals and the heavy metal ions, so that the attapulgite has a huge application prospect.
Disclosure of Invention
In view of the above, the invention provides a carboxylated 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 active NH are firstly subjected to silanization modification, so that a large amount of active NH can be given to the surface of the attapulgite, and active hydrogen can react with sodium chloroacetate, thereby giving a large amount of functional carboxyl to the surface of the material.
In order to achieve the purpose, the invention adopts the following technical scheme:
the carboxylated attapulgite composite material comprises the following components in parts by weight:
10 parts of attapulgite/acidified attapulgite, 5-15 parts of amino silane, 0.70-3.71 parts of sodium chloroacetate and 0.24-1.28 parts of sodium hydroxide.
Preferably, the aminosilane is one of N- [3- (trimethoxysilyl) propyl ] ethylenediamine, N- (beta-aminoethyl-gamma-aminopropyl) methyldimethoxysilane, 3- (2-aminoethylamino) propyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, gamma-aminopropylmethyldiethoxysilane and 3- [2- (2-aminoethylamino) ethylamino ] propyl-trimethoxysilane.
The beneficial effects brought by the optimization are as follows: the micromolecular organosilane coupling agent with active hydrogen NH functional groups can modify the surface of the attapulgite, and the active hydrogen can react with sodium chloroacetate, thereby endowing a large amount of functional carboxyl on the surface of the material.
The invention also aims to provide a preparation method of the carboxylated attapulgite composite material, which is characterized by comprising the following steps:
(1) Weighing machine
Weighing the raw materials of the carboxylated attapulgite composite material for later use;
(2) Preparation of amino silanized attapulgite
Placing the attapulgite or the acidified attapulgite in a first solvent for dispersion, then adding aminosilane, carrying out reflux reaction for 6-12h at 70-90 ℃, cooling and centrifuging, then placing in a second solvent for dispersion and centrifugation, repeating for 2-5 times and drying to obtain the amino silanized attapulgite;
(3) Preparation of carboxylated attapulgite composite material
Weighing 10 parts of aminated attapulgite, dispersing in 200-400mL of deionized water, then adding sodium chloroacetate and sodium hydroxide, stirring at 70-100 ℃ for 5-10h, stopping reaction, centrifuging and dispersing after the reaction is finished, repeating for 2-5 times, and drying to obtain the carboxylated 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 at 70-90 deg.C for 1-3h, centrifuging, washing with deionized water, repeating for 2-5 times, and drying to obtain 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 (3) are 1000-10000r/min, and the centrifugation time is 3-20min;
drying in the steps (2) to (3) at 100-200 ℃ for 1-6h;
in the step (3), the stirring speed is 200-1000r/min.
The invention also aims to provide the application of the carboxylated attapulgite composite material in heavy metal ion adsorption.
According to the technical scheme, compared with the prior art, the invention discloses and provides a carboxylated attapulgite composite material and a preparation method and application thereof, the prepared carboxylated attapulgite composite material is used for adsorbing heavy metal ions, the adsorption capacity of the prepared carboxylated attapulgite composite material to ferric ions can reach more than 400mg/g, and the prepared carboxylated attapulgite composite material has unique selective adsorption to Fe (III) in a solution with Cr (III), cr (IV), pb (II), zn (II) and Cu (II) ions.
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 of the 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 amino silanized attapulgite
Dispersing 10 parts of attapulgite with a certain amount of ethanol, adding 9 parts of N- [3- (trimethoxysilyl) propyl ] ethylenediamine, and carrying out reflux reaction at 80 ℃ for 10 hours. Cooling, centrifuging, dispersing with a certain amount of ethanol, centrifuging, repeating for 2 times, and drying to obtain amino silanized attapulgite.
(2) Preparation of carboxylated attapulgite composite material
Dispersing 10 parts of amino silanized attapulgite in 300mL of deionized water, introducing nitrogen for 30min, then adding 1.88 parts of sodium chloroacetate, adding 0.65 part of sodium hydroxide, stirring for 5h at 95 ℃, stopping the reaction, centrifuging after the reaction is finished, dispersing by using the deionized water, repeating for 3 times, and drying to obtain the carboxylated attapulgite composite material.
The prepared carboxylated attapulgite composite material is used as a boron adsorbent for adsorbing heavy metal ions, and the adsorption capacity of the boron adsorbent to ferric ions can reach 420mg/g.
Example two
(1) Preparation of amino silanized attapulgite
Dispersing 10 parts of attapulgite with a certain amount of acetonitrile, adding 10 parts of N- (beta-aminoethyl-gamma-aminopropyl) methyldimethoxysilane, and carrying out reflux reaction at 85 ℃ for 8 hours. Cooling, centrifuging, dispersing with a certain amount of acetonitrile, centrifuging, repeating for 4 times, and drying to obtain amino silanized attapulgite.
(2) Preparation of carboxylated attapulgite composite material
Dispersing 10 parts of amino silanized attapulgite in 250mL of deionized water, introducing nitrogen for 20min, then adding 2.19 parts of sodium chloroacetate, adding 0.76 part of sodium hydroxide, stirring at 85 ℃ for 7h, stopping reaction, centrifuging after the reaction is finished, dispersing by using the deionized water, repeating for 4 times, and drying to obtain the carboxylated attapulgite composite material.
The prepared carboxylated attapulgite composite material is used as a boron adsorbent for adsorbing heavy metal ions, and the adsorption quantity of the boron adsorbent to ferric ions can reach 480mg/g.
EXAMPLE III
(1) Preparation of amino silanized attapulgite
Dispersing 10 parts of attapulgite with a certain amount of DMF, adding 12 parts of 3- (2-aminoethylamino) propyl triethoxysilane, and carrying out reflux reaction for 10h at 80 ℃. Cooling, centrifuging, dispersing with DMF, centrifuging, repeating for 5 times, and drying to obtain amino silanized attapulgite.
(2) Preparation of carboxylated attapulgite composite material
Dispersing 10 parts of amino silanized attapulgite in 350mL of deionized water, introducing nitrogen for 30min, then adding 1.38 parts of sodium chloroacetate, adding 0.48 part of sodium hydroxide, stirring at 90 ℃ 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 carboxylated attapulgite composite material.
The prepared carboxylated attapulgite composite material is used as a boron adsorbent for adsorbing heavy metal ions, and the adsorption quantity of the boron adsorbent to ferric ions can reach 456mg/g.
Example four
(1) Preparation of amino silanized attapulgite
Preparing acidified attapulgite: dispersing 10 parts of attapulgite in 600 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 by a certain amount of DMSO, adding 5 parts of 3-aminopropyl dimethoxy methylsilane, and carrying out reflux reaction at 70 ℃ for 12h. Cooling, centrifuging, dispersing with certain amount of DMSO, centrifuging, repeating for 3 times, and drying to obtain amino silanized attapulgite.
(2) Preparation of carboxylated attapulgite composite material
Dispersing 10 parts of amino silanized attapulgite in 200mL of deionized water, introducing nitrogen for 10min, then adding 0.70 part of sodium chloroacetate, adding 0.24 part of sodium hydroxide, stirring for 10h at 70 ℃, stopping the reaction, centrifuging after the reaction is finished, dispersing by using the deionized water, repeating for 2 times, and drying to obtain the carboxylated attapulgite composite material.
The prepared carboxylated attapulgite composite material is used as a boron adsorbent for adsorbing heavy metal ions, and the adsorption quantity of the boron adsorbent to ferric ions can reach 632mg/g.
EXAMPLE five
(1) Preparation of amino silanized attapulgite
Preparing acidified attapulgite: dispersing 10 parts of attapulgite in 300 parts of hydrochloric acid solution with the concentration of 3mol/L, refluxing for 2h 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 7 parts of gamma-aminopropyl methyl diethoxy silicon, and carrying out reflux reaction at 75 ℃ for 12 hours. Cooling, centrifuging, dispersing with a certain amount of ethanol, centrifuging, repeating for 2 times, and drying to obtain amino silanized attapulgite.
(2) Preparation of carboxylated attapulgite composite material
Dispersing 10 parts of amino silanized attapulgite in 300mL of deionized water, introducing nitrogen for 30min, then adding 0.94 part of sodium chloroacetate, adding 0.32 part of sodium hydroxide, stirring for 8h at 80 ℃, stopping the reaction, centrifuging after the reaction is finished, dispersing by using the deionized water, repeating for 2 times, and drying to obtain the carboxylated attapulgite composite material.
The prepared carboxylated attapulgite composite material is used as a boron adsorbent for adsorbing heavy metal ions, and the adsorption quantity of the boron adsorbent to ferric ions can reach 580mg/g.
Example six
(1) Preparation of amino 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 3 hours at 80 ℃, centrifuging, washing with deionized water, repeating for 3 times, and drying to obtain the acidified attapulgite.
Dispersing 10 parts of acidified attapulgite with a certain amount of acetonitrile, adding 15 parts of 3- [2- (2-aminoethylamino) ethylamino ] propyl-trimethoxy silane, and carrying out reflux reaction at 90 ℃ for 6h. Cooling, centrifuging, dispersing with a certain amount of acetonitrile, centrifuging, repeating for 5 times, and drying to obtain amino silanized attapulgite.
(2) Preparation of carboxylated attapulgite composite material
Dispersing 10 parts of amino silanized attapulgite in 400mL of deionized water, introducing nitrogen for 40min, then adding 3.71 parts of sodium chloroacetate, adding 1.28 parts of sodium hydroxide, stirring for 5h at 100 ℃, stopping the reaction, centrifuging after the reaction is finished, dispersing by using the deionized water, repeating for 5 times, and drying to obtain the carboxylated attapulgite composite material.
The prepared carboxylated attapulgite composite material is used as a boron adsorbent for adsorbing heavy metal ions, and the adsorption quantity of the boron adsorbent to ferric ions can reach 650mg/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 (6)
1. The carboxylated attapulgite composite material is characterized by comprising the following components in parts by weight:
10 parts of attapulgite/acidified attapulgite, 5-15 parts of amino silane, 0.70-3.71 parts of sodium chloroacetate and 0.24-1.28 parts of sodium hydroxide.
2. The carboxylated attapulgite composite material according to claim 1, wherein the aminosilane is one of N- [3- (trimethoxysilyl) propyl ] ethylenediamine, N- (beta-aminoethyl-gamma-aminopropyl) methyldimethoxysilane, 3- (2-aminoethylamino) propyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, gamma-aminopropylmethyldiethoxysilane, 3- [2- (2-aminoethylamino) ethylamino ] propyl-trimethoxysilane.
3. The preparation method of the carboxylated attapulgite composite material according to claim 1 or 2, characterized by comprising the following steps:
(1) Weighing machine
Weighing each raw material of the carboxylated attapulgite composite material according to claim 1 or 2 for later use;
(2) Preparation of amino silanized attapulgite
Placing the attapulgite or the acidified attapulgite in a first solvent for dispersion, then adding aminosilane, carrying out reflux reaction for 6-12h at 70-90 ℃, cooling and centrifuging, then placing in a second solvent for dispersion and centrifugation, repeating for 2-5 times and drying to obtain the amino silanized attapulgite;
(3) Preparation of carboxylated attapulgite composite material
Weighing 10 parts of aminated attapulgite, dispersing in 200-400mL of deionized water, then adding sodium chloroacetate and sodium hydroxide, stirring at 70-100 ℃ for 5-10h, stopping reaction, centrifuging and dispersing after the reaction is finished, repeating for 2-5 times, and drying to obtain the carboxylated attapulgite composite material.
4. The preparation method of the carboxylated attapulgite composite material according to claim 3, wherein 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 deg.C for 1-3h, centrifuging, washing with deionized water, repeating for 2-5 times, and drying to obtain acidified attapulgite.
5. The method for preparing the carboxylated attapulgite composite material according to claim 3, wherein the first solvent and the second solvent are respectively one of ethanol, acetonitrile, DMF and DMSO.
6. Use of a carboxylated attapulgite composite material according to claim 1 or 2 in the adsorption of heavy metal ions.
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| 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 |
| CN110575823A (en) * | 2018-06-08 | 2019-12-17 | 中国科学院大连化学物理研究所 | Carboxymethylated polyethyleneimine modified magnetic nano material and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104888709A (en) * | 2014-03-06 | 2015-09-09 | 范力仁 | Magnetic aminocarboxyl chelating adsorption granular material and preparation method thereof |
| CN104722265A (en) * | 2015-03-27 | 2015-06-24 | 陕西科技大学 | Preparation method and application of modified attapulgite adsorbent |
| CN110575823A (en) * | 2018-06-08 | 2019-12-17 | 中国科学院大连化学物理研究所 | Carboxymethylated polyethyleneimine modified magnetic nano material and application thereof |
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