CN111203187A - Repair material for removing pollutants in underground water, preparation method and application thereof - Google Patents
Repair material for removing pollutants in underground water, preparation method and application thereof Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000000463 material Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000003344 environmental pollutant Substances 0.000 title claims abstract description 8
- 231100000719 pollutant Toxicity 0.000 title claims abstract description 8
- 230000008439 repair process Effects 0.000 title claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 88
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 74
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000006004 Quartz sand Substances 0.000 claims abstract description 42
- 239000002131 composite material Substances 0.000 claims abstract description 26
- -1 graphene oxide/aminated quartz sand Chemical class 0.000 claims abstract description 26
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 21
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 18
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 17
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 14
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 41
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 28
- 238000005406 washing Methods 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000010907 mechanical stirring Methods 0.000 claims description 9
- 239000004576 sand Substances 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000005067 remediation Methods 0.000 claims description 2
- 239000003673 groundwater Substances 0.000 claims 5
- 239000000356 contaminant Substances 0.000 claims 3
- 230000035484 reaction time Effects 0.000 claims 2
- 238000000643 oven drying Methods 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 12
- 230000009471 action Effects 0.000 abstract description 4
- 239000011247 coating layer Substances 0.000 abstract description 4
- 125000000524 functional group Chemical group 0.000 abstract description 4
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- 238000002156 mixing Methods 0.000 abstract description 3
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- 238000012986 modification Methods 0.000 abstract description 3
- 238000007112 amidation reaction Methods 0.000 abstract description 2
- 238000005576 amination reaction Methods 0.000 abstract description 2
- 125000003277 amino group Chemical group 0.000 abstract description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 description 8
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 7
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000003895 groundwater pollution Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
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- 239000000376 reactant Substances 0.000 description 1
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- 238000000967 suction filtration Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- 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
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- 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
- 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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
- C02F2101/20—Heavy metals or heavy metal compounds
-
- 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
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
Abstract
The invention provides a repairing material for removing pollutants in underground water, and a preparation method and application thereof. The repair material is a graphene oxide/aminated quartz sand composite material formed by mixing and drying graphene oxide and aminated quartz sand according to the mass ratio of 1: 25-250. According to the method, tetraethoxysilane is hydrolyzed and polycondensed on the surface of quartz sand under the action of hexadecyl trimethyl ammonium bromide to form a silicon dioxide coating layer, 3-aminopropyl triethoxysilane is used for carrying out amination modification on the silicon dioxide coating layer on the surface of the quartz sand, and finally, carboxyl functional groups carried by graphene oxide and amino groups on the surface of the quartz sand are subjected to amidation reaction, so that the graphene oxide is coated on the surface of the quartz sand. The method has the advantages of simple reaction conditions, no generation of toxic and harmful substances, stable combination of the graphene oxide and the quartz sand, easy collection and treatment, capability of adsorbing and removing various heavy metal ions and organic pollutants, and no secondary pollution in the treatment process.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a repair material capable of removing heavy metals and organic pollutants in underground water simultaneously, and a preparation method and application thereof.
Background
Because of extensive environmental safety management mode, disordered industrial wastewater discharge or leakage and metal slag stacking for a long time, regional water body heavy metal and organic matter pollution is formed, heavy metal ions are easy to enrich in animals, plants and human bodies due to the durability and difficult removal of the heavy metal ions in water bodies, and people pay more and more attention to organic pollutants due to carcinogenicity of the organic pollutants. The increasingly serious water pollution poses serious threats and challenges to food safety, drinking water safety, regional ecological environment, sustainable development of economy and society and even social stability in China. Therefore, the treatment and purification technology of water pollution has become the hot direction of current research. Through many years of research, various methods such as chemical precipitation, electrochemistry, membrane filtration, ion exchange, adsorption and the like can effectively remove pollutants in water. Among these methods, adsorption methods are favored by researchers because of their advantages of low cost, ease of handling, recyclability, etc., and the key to adsorption methods is the search for suitable adsorbent materials. In addition to traditional adsorbents such as activated carbon and zeolite, researchers have adopted novel adsorbents such as chitosan, lignin and zero-valent nano-iron in succession in recent years, and a series of research progresses are made in the field of adsorption. Compared with other adsorption materials, the graphene oxide has good hydrophilicity as a novel carbon nano material, has an ultra-large specific surface area and carries a large amount of oxygen-containing functional groups, so that the graphene oxide has ultra-strong adsorption potential on heavy metals and organic pollutants in water and is far beyond the existing various repair materials including other carbon nano materials.
However, at present, the independent application of graphene oxide to actual groundwater pollution remediation has certain difficulty, for example, strong pi-pi bond action exists between graphene oxides, which causes the graphene oxides to easily agglomerate, reduces the specific surface area, and affects the treatment effect; due to the excellent hydrophilicity of graphene oxide, graphene oxide is difficult to effectively separate from underground water, and is easy to cause secondary pollution. The quartz sand is widely applied to the field of water pollution treatment due to stable physicochemical properties, biocompatibility, surface modification and other properties, so that the quartz sand becomes an ideal graphene oxide carrier and a series of researches are carried out, however, the current preparation method of the graphene oxide/quartz sand composite material is still difficult to be practically applied to groundwater pollution treatment. For example, patent application document (application number: 201811108081.1) discloses a preparation method of graphene oxide-supported quartz sand, which is simple, and the graphene oxide/iron chloride modified quartz sand can be obtained by supporting iron chloride and graphene oxide on the quartz sand under the action of high temperature, and has a certain removal effect on pollutants in water. However, the graphene oxide is loaded on quartz sand mainly by physical loading, the stability between the graphene oxide and the quartz sand is insufficient, and the graphene oxide is easy to separate in the using process to cause secondary pollution; in addition, part of oxygen-containing functional groups of the graphene oxide are reduced due to high temperature during the synthesis process of the graphene oxide, so that the adsorption performance of the graphene oxide on heavy metals is reduced.
Disclosure of Invention
The invention aims to provide a repair material capable of removing heavy metals and organic pollutants in underground water simultaneously, a preparation method and application thereof, so as to overcome the defects and shortcomings of the existing graphene oxide and effectively solve the problems of instability, poor adsorption performance and the like of the existing graphene oxide and quartz sand after combination.
The purpose of the invention is realized as follows: a preparation method of a repairing material for removing pollutants in underground water comprises the following steps:
(1) adding hexadecyl trimethyl ammonium bromide into water containing quartz sand at 60 ℃, continuously stirring until the hexadecyl trimethyl ammonium bromide is completely dissolved, adding 0.3mol/L sodium hydroxide solution and tetraethoxysilane, continuously reacting for 3 hours, carrying out suction filtration on the reactant, washing by using pure water and absolute ethyl alcohol, and drying in an oven at 40 ℃ to obtain the silica-coated quartz sand. Wherein V (water): m (quartz sand): m (hexadecyltrimethylammonium bromide): v (sodium hydroxide solution): v (ethyl orthosilicate) ═ 1: 20-80: 6-10: 0.1-0.5: 0.03-0.1, V is the volume of the solution (mL), and m is the weight of the substance (mg).
(2) And (2) adding the product into an absolute ethyl alcohol solution at 70 ℃, dropwise adding 3-aminopropyltriethoxysilane while mechanically stirring, reacting for 6 hours to obtain amino-modified quartz sand, washing the product for a plurality of times by using pure water, and drying the product in an oven at 40 ℃. Wherein V (absolute ethanol): m (silica-coated quartz sand): v (3-aminopropyltriethoxysilane) ═ 1: 25-100: 0.005-0.05, V is the volume of the solution (mL), and m is the weight of the substance (mg).
(3) Dissolving graphene oxide in water, performing ultrasonic dispersion treatment for 2 hours, adding 0.4mL of newly-configured mixed solution of 10 mmol/L1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 5mmol/L N-hydroxysuccinimide into the graphene oxide solution, stirring for 0.5 hour, adding the product obtained in the step (2), continuously stirring for 12 hours to obtain graphene oxide coated quartz sand, washing for a plurality of times by using pure water, and drying in an oven at 40 ℃, wherein m (graphene oxide): m (amino-modified quartz sand) ═ 1:25 to 250.
(4) And (3) removing residual template agent cetyl trimethyl ammonium bromide in the product obtained in the step (3) by adopting an ethanol solution containing 0.1mol/L hydrochloric acid at 70 ℃, and finally obtaining the graphene oxide/aminated quartz sand composite material.
The particle size of the quartz sand used in the step (1) is 60-100 meshes.
The repairing material capable of removing heavy metals and organic pollutants in underground water simultaneously is a graphene oxide/aminated quartz sand composite material formed by mixing and drying graphene oxide and aminated quartz sand according to the mass ratio of 1: 25-250. According to the method, tetraethoxysilane is hydrolyzed and polycondensed on the surface of quartz sand under the action of hexadecyl trimethyl ammonium bromide to form a silicon dioxide coating layer, 3-aminopropyl triethoxysilane is used for carrying out amination modification on the silicon dioxide coating layer on the surface of the quartz sand, and finally, carboxyl functional groups carried by graphene oxide and amino groups on the surface of the quartz sand are subjected to amidation reaction, so that the graphene oxide is coated on the surface of the quartz sand. The method has the advantages of simple reaction conditions, no generation of toxic and harmful substances, stable combination of the graphene oxide and the quartz sand, easy collection and treatment, capability of adsorbing and removing various heavy metal ions (such as lead, cadmium, copper and the like) and organic pollutants (such as rhodamine B and the like), and no generation of secondary pollution in the treatment process.
When the graphene oxide/aminated quartz sand composite material prepared by the method disclosed by the invention is specifically applied: according to the mass ratio of heavy metal ions or organic pollutants to the graphene oxide/aminated quartz sand composite material of 1: and (3) putting the composite material into water containing heavy metal ions or organic pollutants in a ratio of 40-300, fully stirring and mixing for 3-48 h, standing after treatment until solid-liquid separation is completed, and obtaining the clean water after the heavy metal ions or the organic pollutants are removed.
The invention has the beneficial effects that: the graphene oxide/aminated quartz sand composite material prepared by the method is safe, environment-friendly and stable in structure, can effectively remove heavy metal ions and organic pollutants in water, and does not generate secondary pollution when existing in a natural water body environment for a long time.
Drawings
Fig. 1 is a schematic representation of a 60 mesh grade graphene oxide/aminated quartz sand composite AA5 prepared in example 5 of the present invention.
Detailed Description
Example 1
1) Weighing 3g of quartz sand (60 meshes) and adding the quartz sand into a conical flask in which 50mL of pure water is placed, then adding 0.54g of hexadecyl trimethyl ammonium bromide, quickly stirring at 60 ℃ (the mechanical stirring speed is 400rpm) until the hexadecyl trimethyl ammonium bromide is completely dissolved, then adding 15mL of 0.3mol/L NaOH solution to keep the solution alkaline, then adding 2.7mL of ethyl orthosilicate, quickly stirring for 3h, washing for a plurality of times by using pure water and absolute ethyl alcohol in sequence, and then drying in an oven at 40 ℃ to obtain the product A1.
2) Adding the product obtained in the step 1) into a conical flask filled with 60mL of absolute ethyl alcohol, adding 1.2mL of 3-aminopropyltriethoxysilane, quickly stirring for 6h at 70 ℃, washing with pure water for several times, and drying in an oven.
3) Weighing 20mg of graphene oxide, dissolving the graphene oxide in 20mL of water, placing the solution under a cell disruptor for ultrasonic dispersion for 2h, adding 0.4mL of newly-configured mixed solution of 10 mmol/L1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 5mmol/L N-hydroxysuccinimide, quickly stirring and activating the graphene oxide for 30min to obtain a graphene oxide solution, adding 1g of the product obtained in the step 2) into the graphene oxide solution, controlling the temperature to be 60 ℃, quickly stirring for 12h until the graphene oxide is completely attached to quartz sand, finally washing the solution for a plurality of times by pure water, and placing the solution in an oven for drying.
4) And 3g of the product obtained in the step 3) is placed in 50mL of ethanol solution containing 0.1mol/L hydrochloric acid, and the mixture is rapidly stirred for 10min at 70 ℃, so that the graphene oxide/aminated quartz sand composite material AA1 is finally obtained.
Example 2
In contrast to example 1, in this example, after the product a1 was obtained in step 1), step 1) in example 1 was repeated using the product a1 instead of silica sand, namely: adding the product A1 and hexadecyl trimethyl ammonium bromide into water, dissolving the hexadecyl trimethyl ammonium bromide under mechanical stirring, adding NaOH solution to make the solution alkaline, adding tetraethoxysilane, stirring, washing with pure water and absolute ethyl alcohol, and drying by using an oven to obtain the product A2. The product A2 was actually obtained by repeating step 1) twice as compared with the product A1, thereby increasing the number of hydroxyl groups on the surface of the silica sand.
The other steps in this example are the same as those in example 1, and finally, the graphene oxide/aminated quartz sand composite material AA2 is obtained.
Example 3
In contrast to example 2, in this example, after the product a2 was obtained in step 1), step 1) in example 1 was repeated again, replacing the silica sand with the product a2, namely: adding the product A2 and hexadecyl trimethyl ammonium bromide into water, dissolving the hexadecyl trimethyl ammonium bromide under mechanical stirring, adding NaOH solution to make the solution alkaline, adding tetraethoxysilane, stirring, washing with pure water and absolute ethyl alcohol, and drying by using an oven to obtain the product A3. Product A3 was compared with product a1 from example 1, in fact in three replicates of step 1) from example 1.
The other steps in this example are the same as those in example 2, and finally, the graphene oxide/aminated quartz sand composite material AA3 is obtained.
Example 4
In contrast to example 3, in this example, after the product A3 was obtained in step 1), step 1) in example 1 was repeated again, replacing the silica sand with the product A3, namely: adding the product A3 and hexadecyl trimethyl ammonium bromide into water, dissolving the hexadecyl trimethyl ammonium bromide under mechanical stirring, adding NaOH solution to make the solution alkaline, adding tetraethoxysilane, stirring, washing with pure water and absolute ethyl alcohol, and drying by using an oven to obtain the product A4. Product a4 was compared with product a1 from example 1, and step 1) from example 1 was repeated four times.
The other steps in this example are the same as those in example 3, and finally, the graphene oxide/aminated quartz sand composite material AA4 is obtained.
Example 5
In contrast to example 4, in this example, after the product a4 was obtained in step 1), step 1) in example 1 was repeated again, replacing the quartz sand with the product a4, namely: adding the product A4 and hexadecyl trimethyl ammonium bromide into water, dissolving the hexadecyl trimethyl ammonium bromide under mechanical stirring, adding NaOH solution to make the solution alkaline, adding tetraethoxysilane, stirring, washing with pure water and absolute ethyl alcohol, and drying by using an oven to obtain the product A5. Product a5 was compared with product a1 in example 1, and step 1) in example 1 was repeated five times.
The other steps in this example are the same as those in example 4, and finally, the graphene oxide/aminated quartz sand composite material AA5 is obtained. The photo of the graphene oxide/aminated quartz sand composite material prepared in this example is shown in fig. 1.
Example 6
1) 3g of quartz sand was weighed and put into a conical flask in which 50mL of pure water had been placed, 0.54g of cetyltrimethylammonium bromide was added, and the mixture was rapidly stirred (mechanical stirring speed 400rpm) at 60 ℃ until the cetyltrimethylammonium bromide was completely dissolved, followed by addition of 15mL of a 0.3mol/L NaOH solution to keep the solution alkaline, addition of 1.35mL of ethyl orthosilicate, after rapid stirring for 3 hours, washing with pure water and absolute ethanol in this order several times, drying in an oven at 40 ℃ and repeating this step five times (similar to step 1 in example 5).
2) Adding the product obtained in the step 1) into a conical flask filled with 60mL of absolute ethyl alcohol, adding 0.1mL of 3-aminopropyltriethoxysilane, quickly stirring for 6h at 70 ℃, washing with pure water for several times, and drying in an oven.
3) Weighing 4mg of graphene oxide, dissolving in 20mL of water, placing under a cell disruptor for ultrasonic dispersion for 2h, adding 0.4mL of newly-configured mixed solution of 10 mmol/L1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 5mmol/L N-hydroxysuccinimide, quickly stirring and activating the graphene oxide for 30min to obtain a graphene oxide solution, adding 1g of the product obtained in the step 2) into the graphene oxide solution, controlling the temperature to be 60 ℃, quickly stirring for 12h until the graphene oxide is completely attached to quartz sand, finally washing with pure water for a plurality of times, and placing in an oven for drying.
4) And 3g of the product obtained in the step 3) is placed in 50mL of ethanol solution containing 0.1mol/L hydrochloric acid, and the mixture is rapidly stirred for 10min at 70 ℃, so that the graphene oxide/aminated quartz sand composite material B is finally obtained.
Example 7
1) 3g of quartz sand was weighed and put into a conical flask in which 50mL of pure water had been placed, 0.54g of cetyltrimethylammonium bromide was added, and the mixture was rapidly stirred (mechanical stirring speed 400rpm) at 60 ℃ until the cetyltrimethylammonium bromide was completely dissolved, followed by addition of 15mL of a 0.3mol/L NaOH solution to keep the solution alkaline, addition of 2.7mL of ethyl orthosilicate, after rapid stirring for 3 hours, washing with pure water and absolute ethanol in this order several times, drying in an oven at 40 ℃ and repeating this step five times (similar to step 1 in example 5).
2) Adding the product obtained in the step 1) into a conical flask filled with 60mL of absolute ethyl alcohol, adding 1.2mL of 3-aminopropyltriethoxysilane, quickly stirring for 6h at 70 ℃, washing with pure water for several times, and drying in an oven.
3) Weighing 40mg of graphene oxide, dissolving the graphene oxide in 20mL of water, placing the solution under a cell disruptor for ultrasonic dispersion for 2h, adding 0.4mL of newly-configured mixed solution of 10 mmol/L1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 5mmol/L N-hydroxysuccinimide, quickly stirring and activating the graphene oxide for 30min to obtain a graphene oxide solution, adding 1g of the product obtained in the step 2) into the graphene oxide solution, controlling the temperature to be 60 ℃, quickly stirring for 12h until the graphene oxide is completely attached to quartz sand, finally washing the solution for a plurality of times by pure water, and placing the solution in an oven for drying.
4) And 3g of the product obtained in the step 3) is placed in 50mL of ethanol solution containing 0.1mol/L hydrochloric acid, and the mixture is rapidly stirred for 10min at 70 ℃, so that the graphene oxide/aminated quartz sand composite material C is finally obtained.
Example 8
The application of the graphene oxide/aminated quartz sand composite material in water containing heavy metal lead ions comprises the following steps:
1) preparing 7 water samples containing heavy metal lead ions, wherein the lead concentration in each water sample is 100mg/L, and each water sample is 20mL and is respectively placed in a 50mL conical flask; 0.1g each of the composite materials AA1, AA2, AA3, AA4, AA5 and B, C prepared in the above examples 1 to 7 parts of a water sample containing heavy metal lead ions was added, and the mixture was placed in a constant temperature oscillator and sufficiently oscillated for 24 hours.
2) The water sample after shaking was filtered through a 0.22 μm filter membrane, and the concentration of the remaining lead ions in the water was measured by ICP, the results of which are shown in table 1. Table 1 shows the lead removal effect of the graphene oxide/aminated quartz sand composite materials prepared in examples 1 to 7.
Table 1:
example 9
The application of the graphene oxide/aminated quartz sand composite material in water containing an organic pollutant rhodamine B is as follows:
1) preparing 7 water samples containing rhodamine B, wherein the concentration of rhodamine B in each water sample is 100mg/L, and each water sample is 20mL and is respectively placed in a 50mL conical flask; 0.1g of each of the composite materials AA1, AA2, AA3, AA4, AA5 and B, C prepared in the above examples 1 to 7 parts of water sample containing rhodamine B is added, placed in a constant temperature oscillator and fully oscillated for 24 hours.
2) And filtering the water sample after the oscillation is finished by adopting a 0.22-micron filter membrane, and measuring the concentration of the residual rhodamine B in the water by adopting an ultraviolet-visible spectrophotometer to obtain a result shown in a table 2. Table 2 shows the effect of the graphene oxide/aminated quartz sand composite material prepared in examples 1 to 7 on the removal of rhodamine B.
TABLE 2
Claims (10)
1. A preparation method of a repairing material for removing pollutants in underground water is characterized by comprising the following steps:
(1) adding quartz sand and hexadecyl trimethyl ammonium bromide into water, mechanically stirring until the hexadecyl trimethyl ammonium bromide is completely dissolved, then adding a sodium hydroxide solution to make the solution alkaline, then adding tetraethoxysilane to make the tetraethoxysilane hydrolyzed on the surface of the quartz sand to obtain silica-coated quartz sand, washing the silica-coated quartz sand by using pure water and absolute ethyl alcohol, and then placing the quartz sand in an oven for drying;
(2) adding the product obtained in the step (1) into an absolute ethyl alcohol solution, dropwise adding 3-aminopropyltriethoxysilane under mechanical stirring, obtaining amino modified quartz sand after reaction is completed, washing the obtained amino modified quartz sand by pure water, and then placing the quartz sand in an oven for drying;
(3) dissolving graphene oxide in water, firstly performing ultrasonic dispersion treatment, then adding a mixed solution of 10 mmol/L1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 5mmol/L N-hydroxysuccinimide, stirring, adding the product obtained in the step (2), continuously stirring to obtain graphene oxide coated quartz sand, washing with pure water, and then placing in an oven for drying;
(4) and (4) placing the product obtained in the step (3) in a mixed solution of absolute ethyl alcohol and concentrated hydrochloric acid, and stirring to remove hexadecyl trimethyl ammonium bromide in the product obtained in the step (3) so as to obtain the graphene oxide/aminated quartz sand composite material.
2. The method of claim 1, wherein the step (1) is repeated several times to increase the number of hydroxyl groups on the surface of the silica sand before the step (2).
3. The method of claim 1, wherein in the step (1), the silica sand has a particle size of 60 to 100 mesh.
4. The method for preparing a repairing material for removing pollutants from groundwater according to claim 1, wherein in the step (1), the proportion of water, quartz sand, cetyl trimethyl ammonium bromide, sodium hydroxide solution and ethyl orthosilicate is 1: 20-80: 6-10: 0.1-0.5: 0.03 to 0.1; wherein, the unit of the water, the sodium hydroxide solution and the ethyl orthosilicate is mL according to the volume content, and the unit of the quartz sand and the hexadecyl trimethyl ammonium bromide is mg according to the weight content.
5. The method according to claim 1, wherein in the step (2), the ratio of the absolute ethyl alcohol to the silica-coated silica sand to the 3-aminopropyltriethoxysilane is 1: 25-100: 0.005 to 0.05; wherein, the unit of the absolute ethyl alcohol and the 3-aminopropyl triethoxysilane is mL according to the volume content, and the unit of the silica-coated quartz sand is mg according to the weight content.
6. The method according to claim 1, wherein in the step (3), the weight ratio of the graphene oxide to the amino-modified quartz sand is 1:25 to 250.
7. The method for preparing a repair material for removing contaminants from groundwater according to claim 1, wherein the experimental reaction temperature is 60 to 80 ℃, the oven drying temperature is 30 to 60 ℃, and the mechanical stirring speed is 300 to 1000 rpm.
8. The method for preparing a remediation material for the removal of contaminants from groundwater as claimed in claim 1, wherein the stirring reaction time in steps (1) and (4) is 0.1 to 6 hours, and the stirring reaction time in steps (2) and (3) is 6 to 24 hours.
9. A graphene oxide-aminated quartz sand composite material for removing contaminants from groundwater prepared by the method of any one of claims 1-8.
10. Use of the graphene oxide-aminated quartz sand composite material of claim 9 for removing heavy metals and/or organic pollutants from groundwater.
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