CN113893877B - Preparation method of hydrophobic composite material for efficiently adsorbing, catalyzing and degrading chloroform in water, obtained composite material and application of composite material - Google Patents

Preparation method of hydrophobic composite material for efficiently adsorbing, catalyzing and degrading chloroform in water, obtained composite material and application of composite material Download PDF

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CN113893877B
CN113893877B CN202111155900.XA CN202111155900A CN113893877B CN 113893877 B CN113893877 B CN 113893877B CN 202111155900 A CN202111155900 A CN 202111155900A CN 113893877 B CN113893877 B CN 113893877B
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composite material
carbon fiber
water
chloroform
graphene oxide
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CN113893877A (en
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陈亦力
莫恒亮
李锁定
丑树人
彭文娟
侯琴
许鑫
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Beijing Originwater Membrane Technology Co Ltd
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Abstract

The invention provides a preparation method of a hydrophobic composite material for efficiently adsorbing, catalyzing and degrading chloroform in water. The material can realize the reduction of the chloroform, degrade the chloroform into the methane which is indissolvable in water, and a small amount of dissolved metal ions are harmless to human bodies and can supplement mineral substances, so that the safety of drinking water can be ensured while the catalytic degradation of the chloroform in water is realized.

Description

Preparation method of hydrophobic composite material for efficiently adsorbing, catalyzing and degrading chloroform in water, obtained composite material and application of composite material
[ field of technology ]
The invention relates to a modified hydrophobic composite material, in particular to a composite material capable of efficiently adsorbing, catalyzing and degrading triple-filtered methane in water, and a preparation method and application thereof.
[ background Art ]
At present, 99.5% of drinking water treatment plants in China use chlorine disinfection mode to realize drinking water disinfection. Due to the residual organic matters in the water, disinfection byproducts are generated in the chlorination disinfection process, and the generation amount and the generation variety are relatively large. Among them, chloroform is a typical disinfection by-product that can enter the body through drinking water, respiration, or skin. Long-term drinking or exposure to drinking water containing halogenated disinfection byproducts is a health hazard to humans. Therefore, in order to ensure the safety of drinking water, developing a material capable of effectively removing chloroform for purifying water is an important and urgent problem to be solved.
In order to obtain safer drinking water, it is necessary to remove disinfection byproducts such as chloroform and the like from the water. The current control method for the disinfection byproducts comprises the following steps: 1. controlling from a source of production, reducing the amount and type of precursors capable of producing disinfection byproducts; 2. the use of chlorine disinfection is reduced, and a safe and reliable alternative disinfectant is selected; 3. a specific method is used to remove disinfection by-products that have been produced in water. In recent years, researchers in the relevant fields have conducted a series of studies on effective treatment methods for the toxic by-products. The removal of the disinfection byproducts in the practical application process is mainly divided into two major directions: removal of the disinfection by-product precursor or removal of the disinfection by-product itself:
reinforced coagulation method: for removal of disinfection by-product precursors. Humic acid and fulvic acid in water are removed through coagulation treatment. When natural organic matters are removed, obvious differences exist in the effects of different coagulants, concrete coagulation needs to be selected by combining the requirements of different water qualities, and the coagulation technology is often used in combination with other technologies.
Activated carbon adsorption method: the activated carbon has the characteristics of large adsorption capacity, high adsorption rate, good adsorption performance on various substances, wide application range, strong adaptability, high treatment capacity and the like because of a developed void structure and a large specific surface area of the activated carbon and various functional groups on the surface of the activated carbon. The water treatment agent is a good water treatment agent, can effectively remove organic matters in water, and is an effective method for controlling chloroform. Although the activated carbon can effectively adsorb part of the chloroform in water, the activated carbon has the conditions of adsorption saturation and desorption, and the chloroform is only enriched on the activated carbon and is not completely degraded, and the risk of secondary pollution exists.
Still other methods are available for the removal of chloroform, such as membrane processes, which are primarily used in potable water treatment to remove chloroform and other disinfection byproducts from water by using reverse osmosis and nanofiltration membranes. Although the membrane treatment method can efficiently remove most of organic matters, the defects of short service life, high cost, difficult cleaning and the like limit the wide application of the membrane treatment method. In addition, the reduction method provides electrons for reduction reaction through active metal to perform reduction effect, and the electrons react with chloroform, so that the purpose of degradation is achieved. At present, many researches are carried out on reducing the chloroform by utilizing nano zero-valent iron, and the nano zero-valent iron has high reactivity and strong reducing capability and can efficiently react with the chloroform. However, the nano zero-valent iron is easy to oxidize when being contacted with air, and a layer of ferric oxide is generated on the surface, so that the reactivity of the nano zero-valent iron is lost, the service life of the nano zero-valent iron is shortened, and the nano zero-valent iron is difficult to be widely applied to practical water treatment application.
[ invention ]
The invention aims to provide a preparation method of a hydrophobic composite material for efficiently adsorbing and catalyzing and degrading chloroform in water, which ensures that the obtained composite material has hydrophobicity and can efficiently remove the chloroform in water.
The invention adopts reduced graphene oxide modified carbon fiber (RGO-ACF), PVDF polymer skeleton and Mg-Fe-Zn-Si alloy as main preparation raw materials. Wherein, the reduced graphene oxide modified carbon fiber (RGO-ACF) has larger specific surface area and porous structure, and is expected to be capable of rapidly adsorbing chloroform; after absorbing chloroform in enriched water by RGO-ACF, the Mg-Fe-Zn-Si alloy reduces the chloroform enriched around, and the Mg-Fe-Zn-Si alloy is used as an electron donor to directly reduce the chloroform. At electron and H + Under the combined action, dechlorination reaction is carried out, and after dechlorination reaction is carried out for a plurality of times, the reduced chloroform is finally converted into methane which is difficult to dissolve in water. During the reaction, magnesium, iron and zinc ions in the Mg-Fe-Zn-Si alloy are partially dissolved out, but due to Mg 2+ ，Zn 2+ ，Fe 2+ Harmless to human body and in safe concentration range, thereby ensuring the safety of drinking water.
Based on the thought, the invention provides a preparation method of a hydrophobic composite material for efficiently adsorbing, catalyzing and degrading chloroform in water, which comprises the following steps:
(1) Preparation of reduced graphene oxide modified carbon fiber
Taking carbon fiber with high iodine value, cleaning and drying for later use;
weighing carbon fiber and graphene oxide dispersion liquid according to a mass ratio of 10:1, mixing, performing ultrasonic treatment for 30min, adding concentrated ammonia water which is 10-20 times of the total mass of the carbon fiber and the graphene oxide dispersion liquid, stirring for 2-4h at 80-100 ℃, and drying to obtain reduced graphene oxide modified carbon fiber;
(2) Preparation of Mg-Fe-Zn metal mixture
Weighing FeSi45 type iron-silicon alloy powder, alSi10Mg type magnesium-aluminum-silicon alloy powder and CuZn5050 type zinc-copper alloy powder according to the mass ratio of 3:4:3, and uniformly mixing to obtain a Mg-Fe-Zn metal mixture;
(3) Preparation of composite materials
Crushing the reduced graphene oxide modified carbon fiber obtained in the step (1), and sieving the crushed reduced graphene oxide modified carbon fiber with a 100-mesh sieve to obtain reduced graphene oxide modified carbon fiber powder;
weighing reduced graphene oxide modified carbon fiber powder and Mg-Fe-Zn metal mixture according to a mass ratio of 1:1, and mixing to obtain a solid phase mixture; weighing the solid phase mixture and polyvinylidene fluoride according to the mass ratio of 6:4-8.5:1.5, mixing, adding a dimethylacetamide solution until the polyvinylidene fluoride is completely dissolved, and uniformly stirring to obtain a phase change mixture;
and (3) the phase-change mixture is dropped into water through a thin pipe or a thin opening to perform phase change, so that the composite material is obtained.
In the invention, the carbon fiber with high iodine value is selected to be beneficial to improving the adsorption performance of the product. Preferably, an iodine value above 1200 gives better performance to the product, but an iodine value exceeding 1800 results in a significant increase in manufacturing costs. Accordingly, the present invention selects carbon fibers having an iodine value in the range of 1200-1800 as a raw material.
In the present invention, in order to ensure thorough denaturation of the carbon fibers, the carbon fibers in step (1) have a diameter of 3 to 5 μm and a length of 0.5 to 2mm.
In the present invention, the graphene oxide dispersion is a commercially available product such as SE3521 type product sold by the company of science and technology of sixth element materials, in everstate, and the mass concentration of graphene oxide is 3%.
According to a preferred embodiment, in the step (1), the cleaning place of the carbon fiber comprises immersing the carbon fiber with deionized water, and cleaning the carbon fiber with deionized water three times after ultrasonic treatment for 5 min.
Optionally, the alloy powder adopted by the invention has smaller particle size, the particle size of FeSi45 type ferrosilicon alloy powder is 200 meshes, the particle size of AlSi10Mg type magnesium aluminum silicon alloy powder is 1 mu m, and the particle size of CuZn5050 type zinc copper alloy powder is 200 meshes. These alloy powders are commercially available products, for example FeSi 45-type ferrosilicon alloy powder is purchased from Hebei's metal material sales company, alSi10 Mg-Al-Si alloy powder is purchased from Shanghai Landa nanomaterials company, and CuZn 5050-type zinc-copper alloy powder is purchased from Beijing Xingrong source technology Co.
In the present invention, the step (3) makes the phase-changed composite material into a particle shape or a wire shape by controlling the inner diameter of the tubule or the thin opening or controlling the flow rate of the phase-change mixture through the tubule or the thin opening, preferably, the particle shape or the wire shape composite material has a diameter of 0.5mm to 1.5mm.
The working principle of the composite material of the invention is as follows: the reduced graphene oxide modified carbon fiber (RGO-ACF) utilizes the larger specific surface area and the porous structure of the reduced graphene oxide modified carbon fiber to quickly adsorb the chloroform, and the chloroform is adsorbed on the surfaces and the pores of the reduced graphene oxide and the carbon fiber. The Mg-Fe-Zn metal material is contacted with chloroform adsorbed in the pores, and the magnesium in the Mg-Fe-Zn metal materialThe iron and zinc lose electrons and provide electrons for the reduction of chloroform. Firstly, mg, zn and Fe in Mg-Fe-Zn-Si alloy undergo oxidation reaction, lose electrons and take the form of Mg 2+ ，Zn 2+ ，Fe 2+ The ionic form exists, and simultaneously, the chloroform and the water molecules obtain electrons, and the generated hydrogen ions, electrons and the chloroform undergo a reduction reaction, so that the chloroform undergoes a dechlorination reaction. After three dechlorination reactions, the chloroform can be finally degraded into methane which is difficult to dissolve in water. During this reaction, mg in the Mg-Fe-Zn metal material 2+ ，Zn 2+ ，Fe 2+ Some of the ions are dissolved out, but the ions are harmless to human bodies, and can supplement minerals, so that the safety of drinking water can be ensured. The basic reaction of the whole process is as follows:
the reaction process of reducing chloroform by Mg-Fe-Zn metal material comprises the following steps:
Mg－2e - ＝＝Mg 2+
Fe－2e - ＝＝Fe 2+
Zn－2e - ＝＝Zn 2+
CHCl 3 +2e - +H + ＝＝＝CH 2 Cl 2 +Cl -
CH 2 Cl 2 +2e - +H + ＝＝＝CH 3 Cl+Cl -
CH 3 Cl+2e - +H + ＝＝＝CH 4 +Cl -
the trichloromethane is a hydrophobic molecule, and the hydrophobic material is more selective to the adsorption of the trichloromethane by utilizing the principle of similar compatibility, so that the hydrophobic polyvinylidene fluoride (PVDF) is adopted as a binder to bond and compound the RGO-ACF and Mg-Fe-Zn metal mixture of the modified carbon fiber, thereby being beneficial to improving the adsorption selectivity of the composite material to the trichloromethane.
Based on the above, the invention also provides application of the composite material prepared by the preparation method in water purification.
In particular, the composite material of the invention is used for removing chloroform from water.
According to the invention, the carbon fiber is modified to realize rapid adsorption of the chloroform, and the appropriate alloy material is selected to enable the Mg-Fe-Zn metal material to be in contact with the chloroform adsorbed in the pores, so that reduction of the chloroform is realized, thereby dechlorination reaction is carried out on the chloroform, and finally the chloroform is degraded into methane which is insoluble in water. By specific alloy selection, mg in the Mg-Fe-Zn metal material during the reaction process 2+ ，Zn 2+ ，Fe 2+ Some of the ions are dissolved out, but the ions are harmless to human bodies, and can supplement minerals, so that the safety of drinking water can be ensured while the catalytic degradation of chloroform in the water is realized.
[ description of the drawings ]
FIG. 1 is a schematic diagram of the operation of the composite material of the present invention;
FIG. 2 is the concentration of chloroform in water after treatment of the composite material and pure carbon fiber of example 2;
FIG. 3 is the concentration of chloroform in water after treatment of the hydrophilic and hydrophobic composite of comparative example 1;
FIG. 4 is the concentration of chloroform in water after treatment of the hydrophilic and hydrophobic composite of comparative example 2.
[ detailed description ] of the invention
The following examples serve to illustrate the technical solution of the invention without limiting it.
Example 1 preparation of composite materials
Carbon fiber with the iodine value of 1800, the diameter range of 3-5 mu m and the length range of 0.5-2mm is taken, soaked in ionized water and treated by ultrasonic for 5min, and then washed by deionized water for 3 times. Drying in an oven at 105 ℃ for 5 hours for standby.
And weighing the carbon fiber and the graphene oxide dispersion liquid according to a mass ratio of 10:1, mixing, performing ultrasonic treatment for 30min, and then adding concentrated ammonia water with a mass which is 10 times of the total mass of the carbon fiber and the graphene oxide dispersion liquid to reduce the graphene oxide. And then stirring for 3 hours at 90 ℃, and drying at 90 ℃ to obtain the reduced graphene oxide modified carbon fiber (RGO-ACF).
Mixing 200-mesh FeSi 45-type ferrosilicon alloy powder (purchased from Hebei's metal material sales Co., ltd.), alSi10 Mg-Al-Si alloy powder with a particle size of 1 μm (purchased from Shanghai Landa nanometer materials Co., ltd.) and 200-mesh CuZn 5050-type zinc-copper alloy powder (purchased from Beijing Xingrong source technology Co., ltd.) according to a mass ratio of 3:4:3 to obtain a Mg-Fe-Zn metal mixture containing active metals such as magnesium, iron, zinc and the like.
Crushing the reduced graphene oxide modified carbon fiber, and sieving the crushed reduced graphene oxide modified carbon fiber with a 100-mesh sieve to obtain reduced graphene oxide modified carbon fiber powder.
Weighing reduced graphene oxide modified carbon fiber powder and Mg-Fe-Zn metal mixture according to a mass ratio of 1:1, and mixing to obtain a solid phase mixture; mixing the solid phase mixture and polyvinylidene fluoride according to the mass ratio of 8.5:1.5, then adding a dimethylacetamide solution until the polyvinylidene fluoride is completely dissolved, and stirring for 3 hours until a uniform phase change mixture is obtained. And (3) dripping the phase-change mixture into water by using a needle tube, and carrying out phase change on the mixture in water to obtain the composite material.
EXAMPLE 2 removal Rate of chloroform from the composite Material of the present invention
The removal performance of the composite material of example 1 on chloroform was verified by an overcurrent experiment.
5g of the composite material was packed into a plexiglas column having a height of 10cm, an outer diameter of 3.5cm and an inner diameter of 2.5cm, and cotton was plugged at both ends to prevent loss of material. Wrapping tinfoil around the column to perform light-shielding treatment.
Untreated carbon fiber particles (ACF) were used as a control.
A chloroform solution was prepared in tap water as simulated water inlet, and the concentration of chloroform in tap water was 0.2mg/L. The prepared chloroform aqueous solution is fed from the lower end of the column by a pump, slowly rises and flows out from the upper end of the column after contact reaction with the composite material, the flow speed is about 2L/min, and the concentration of the chloroform in the fed water and produced water is monitored in the running process. The overcurrent experiment was continuously performed in the daytime and not operated at night, and the result is shown in fig. 2.
Experimental results show that under the requirement of water quality that the concentration of the chloroform in the water is lower than 5ppb, 5g of the composite material can continuously and stably treat 5.8t of water, and the treatment capacity of the chloroform is about 2 times of that of pure ACF. In the treatment capacity range, the removal rate of the composite material disclosed by the invention to the chloroform is up to 99%, and the composite material accords with the effluent concentration of the chloroform in the national drinking water.
Comparative example 1
Another composite was prepared in the same manner as in example 1, except that Polyacrylonitrile (PAN) was used instead of the hydrophobic PVDF to prepare a hydrophilic RGO-ACF/Mg-Fe-Zn-Si/PAN composite.
The composite material of this example and the material of example 1 were tested for chloroform removal by the same method as in example 2, and the results are shown in FIG. 3.
Experimental results show that under the requirement that the concentration of the chloroform in the effluent is lower than 5ppb, the hydrophilic composite material can continuously and stably treat 3.8t of water, and the treatment capacity of the chloroform is lower than that of the hydrophobic composite material, so that the removal effect of the hydrophobic composite material is better than that of the hydrophilic composite material in the chloroform removal experiment.
Comparative example 2
Another composite material was prepared in the same manner as in example 1, except that the alloy material was prepared by the following steps: mixing HZ-FeCu30 type iron-copper alloy powder with the particle size of 200 meshes (purchased from Hebei Hua Ding alloy welding materials Co., ltd.), ALMg50 type magnesium-aluminum alloy powder with the particle size of 200 meshes (purchased from Beijing Xingrong source technology Co., ltd.) and CuZn70-30 type zinc-copper alloy powder with the particle size of 200 meshes (purchased from Hebei Yibai Bai Ding alloy welding materials Co., ltd.) according to the mass ratio of 3:4:3 to obtain another Mg-Fe-Zn-II metal mixture containing active metals such as magnesium, iron, zinc and the like, so as to compare the degradation capability of the composite material of the embodiment 1 on chloroform in water.
The composite material of this example and the material of example 1 were tested for chloroform removal by the same method as in example 2, and the results are shown in fig. 4.
The experimental result shows that under the requirement that the concentration of the effluent chloroform is lower than 5ppb, the composite material-II which takes the Mg-Fe-Zn-II metal mixture as a metal component can continuously and stably treat 4.2t of water, and the treatment capacity of the chloroform is lower than the treatment capacity (5.8 t) of the filter element which takes the Mg-Fe-Zn metal mixture obtained by compounding the FeSi45 type ferrosilicon alloy powder, the AlSi10Mg type magnesium-aluminum-silicon alloy powder and the CuZn5050 type zinc-copper alloy powder which are prepared by the mass ratio of 3:4:3. The selection of the metal materials has outstanding influence on the removal of the chloroform in water, and the filter element prepared by taking metal powder materials consisting of different alloy materials as raw materials has different performances although the magnesium, the iron and the zinc are all active metals, while the composite material taking the Mg-Fe-Zn metal mixture as the metal component has better removal effect, and proves that the selection of the alloy components in the technology is particularly effective.
In summary, the invention realizes the rapid adsorption of the chloroform by modifying the carbon fiber, realizes the reduction of the chloroform by selecting proper alloy materials, improves the treatment capacity of the filter element, and finally degrades the chloroform into the methane which is indissolvable in water, thereby realizing the catalytic degradation of the chloroform in water and ensuring the safety of drinking water.

Claims (9)

1. A preparation method of a hydrophobic composite material for efficiently adsorbing, catalyzing and degrading chloroform in water comprises the following steps:
(1) Preparation of reduced graphene oxide modified carbon fiber
Taking carbon fiber with high iodine value, cleaning and drying for later use;
weighing carbon fiber and graphene oxide dispersion liquid according to a mass ratio of 10:1, mixing, performing ultrasonic treatment for 30min, adding concentrated ammonia water which is 10-20 times of the total mass of the carbon fiber and the graphene oxide dispersion liquid, stirring for 2-4h at 80-100 ℃, and drying to obtain reduced graphene oxide modified carbon fiber;
(2) Preparation of Mg-Fe-Zn metal mixture
Weighing FeSi45 type iron-silicon alloy powder, alSi10Mg type magnesium-aluminum-silicon alloy powder and CuZn5050 type zinc-copper alloy powder according to the mass ratio of 3:4:3, and uniformly mixing to obtain a Mg-Fe-Zn metal mixture;
(3) Preparation of composite materials
Crushing the reduced graphene oxide modified carbon fiber obtained in the step (1), and sieving the crushed reduced graphene oxide modified carbon fiber with a 100-mesh sieve to obtain reduced graphene oxide modified carbon fiber powder;
weighing reduced graphene oxide modified carbon fiber powder and Mg-Fe-Zn metal mixture according to a mass ratio of 1:1, and mixing to obtain a solid phase mixture; weighing the solid phase mixture and polyvinylidene fluoride according to the mass ratio of 6:4-8.5:1.5, mixing, adding a dimethylacetamide solution until the polyvinylidene fluoride is completely dissolved, and uniformly stirring to obtain a phase change mixture;
and (3) the phase-change mixture is dropped into water through a thin pipe or a thin opening to perform phase change, so that the composite material is obtained.
2. The method according to claim 1, wherein the carbon fiber in the step (1) has a diameter of 3 to 5 μm and a length of 0.5 to 2mm.
3. The production method according to claim 1, characterized in that the mass concentration of graphene oxide in the graphene oxide dispersion in step (1) is 3%.
4. The method according to claim 1, wherein in the step (1), the cleaning of the carbon fiber comprises immersing the carbon fiber in deionized water, ultrasonic treating for 5min, and cleaning with deionized water three times.
5. The preparation method according to claim 1, wherein in the step (2), the particle size of the FeSi45 type ferrosilicon alloy powder is 200 meshes, the particle size of the AlSi10Mg type magnesium aluminum silicon alloy powder is 1 μm, and the particle size of the CuZn5050 type zinc copper alloy powder is 200 meshes.
6. The method according to claim 1, wherein in the step (3), the phase-changed composite material is formed into a pellet or a wire by controlling the inner diameter of the tubule or the orifice or controlling the flow rate of the phase-change mixture through the tubule or the orifice.
7. The method of producing a composite material according to claim 6, wherein the diameter of the granular or wire-like composite material is 0.5mm to 1.5mm.
8. The method of claim 1, wherein the composite material is used in water purification.
9. Use according to claim 8, characterized in that the composite material is used for removing chloroform from water.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109772454A (en) * 2019-02-28 2019-05-21 清华大学深圳研究生院 Photocatalysis membrana and preparation method thereof and degradation application to disinfection by-products formation potential
CN113304726A (en) * 2021-05-28 2021-08-27 北京碧水源净水科技有限公司 Preparation method of disinfection by-product adsorption type carbon membrane filter element, product obtained by preparation method and application of product

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109772454A (en) * 2019-02-28 2019-05-21 清华大学深圳研究生院 Photocatalysis membrana and preparation method thereof and degradation application to disinfection by-products formation potential
CN113304726A (en) * 2021-05-28 2021-08-27 北京碧水源净水科技有限公司 Preparation method of disinfection by-product adsorption type carbon membrane filter element, product obtained by preparation method and application of product

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