CN110127781B - Modified graphene oxide composite material, preparation method and application - Google Patents
Modified graphene oxide composite material, preparation method and application Download PDFInfo
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- CN110127781B CN110127781B CN201910352237.9A CN201910352237A CN110127781B CN 110127781 B CN110127781 B CN 110127781B CN 201910352237 A CN201910352237 A CN 201910352237A CN 110127781 B CN110127781 B CN 110127781B
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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
- C02F1/00—Treatment of water, waste water, or sewage
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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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
- 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
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
Abstract
The invention discloses a modified graphene oxide composite material, a preparation method and application. According to the method, chitosan is adopted to modify graphene oxide to prepare modified graphene oxide; and then adding the modified graphene oxide into the nano calcium peroxide preparation solution to prepare a modified graphene oxide-nano calcium peroxide compound, and finally loading the modified graphene oxide-nano calcium peroxide compound on diatomite to prepare the modified graphene oxide composite material. The modified graphene oxide composite material has the advantages of large specific surface area, large quantity and rich varieties of active adsorption sites, and has high-efficiency adsorption capacity on organic pollutants, metal ions and dyes which are difficult to biochemically degrade in sewage. Meanwhile, the active ingredient nano calcium peroxide in the modified graphene oxide composite material can continuously release hydrogen peroxide to carry out oxidative degradation on organic matters which are difficult to be biochemically degraded in sewage, so as to generate biochemically degradable organic pollutants and inorganic matters.
Description
Technical Field
The invention relates to a sewage treatment material, a preparation method and application, in particular to a modified graphene oxide composite material, a preparation method and application.
Background
Adsorption is an effective strategy for removing pollutants in sewage and is widely applied in the field of sewage treatment. The graphene oxide is a novel adsorption material, the layered structure of the graphene is maintained, a large number of oxygen-based functional groups are introduced into each layer of graphene single sheet, and the problems of poor solubility and weak complexing capability of the graphene are solved. Due to low production cost, large specific surface area and strong interaction with various anions, cations and neutral substances in an aqueous medium, the method becomes a research hotspot in the field of water treatment materials. The target pollutant is used as a guide, the graphene oxide is directionally modified, new physical and chemical properties can be given to the graphene oxide, and the adsorption capacity of the target pollutant is enhanced.
Calcium peroxide is a classical high-efficiency oxidant, is slightly soluble in water, can be slowly decomposed in water to generate hydrogen peroxide, oxygen and calcium hydroxide, and is widely applied to the fields of agriculture, industry, aquaculture, medicine, environmental protection and the like. Compared with common calcium peroxide, the nano calcium peroxide has good dispersibility, large specific surface area and higher pollutant oxidative degradation efficiency. Therefore, the dosage of calcium peroxide can be reduced, and the use cost of the medicament can be reduced.
Disclosure of Invention
The purpose of the invention is as follows: the invention provides a modified graphene oxide composite material, a preparation method and application. The composite material is used as a sewage treatment agent, has dual performances of adsorption and oxidative degradation, forms an adsorption-oxidative degradation composite system, has high-efficiency adsorption and oxidative degradation capabilities on organic matters, metal ions and dyes which are difficult to be biochemically degraded in sewage, can play a role for a long time, is low in consumption rate and low in adding frequency, and solves the problems of low treatment efficiency, single pollutant treatment type and frequent adding of the traditional sewage treatment agent.
The technical scheme is as follows: according to the modified graphene oxide composite material, the skeleton structure of the composite material at least comprises one component of diatomite, and the skeleton structure is formed by bonding with a bonding agent; the framework structure is loaded with an active material, and the active material comprises modified graphene oxide and nano calcium peroxide attached to the surface of the modified graphene oxide; the modified graphene oxide is chitosan-modified graphene oxide.
The composite material can be cylindrical, spherical or irregular granular in shape.
The adhesive (binding agent) used for the framework material can be natural adhesive or synthetic adhesive, the natural adhesive can be macromolecular polysaccharide such as starch, carboxymethyl cellulose, protein, dextrin, animal glue, shellac, hide glue or rosin, and can also be mineral adhesive such as asphalt and the like; synthetic adhesives include, for example, polyurethanes, polystyrenes, polyacrylates, polyvinyl alcohols, ethylene-vinyl acetate copolymers, and the like.
Water-soluble binders are preferred in the present invention, most preferably polyvinyl alcohol.
Preferably, the mass ratio of the skeleton structure and the active material forming the composite material is 8-15: 1; the mass ratio of the modified graphene oxide to the nano calcium peroxide in the active material is 1: 0.4 to 0.7; the mass of the graphene oxide and the chitosan in the modified graphene oxide is 1: 0.2 to 0.5.
The composite material is prepared by the following method: firstly, modifying graphene oxide by using chitosan to obtain modified graphene oxide, then placing the modified graphene oxide in a nano calcium peroxide preparation solution to obtain a modified graphene oxide-nano calcium peroxide compound, and finally loading the modified graphene oxide-nano calcium peroxide compound on diatomite to obtain the modified graphene oxide composite material.
The modified graphene oxide is chitosan-modified graphene oxide, and the modified graphene oxide is obtained by the following method:
firstly, dispersing graphene oxide in an aqueous solution to obtain a graphene oxide suspension, mixing the graphene oxide suspension with a chitosan aqueous solution, placing the mixed solution in a high-pressure reaction kettle, stirring for reaction at 160-190 ℃, reacting chitosan with carboxyl on the graphene oxide to obtain preliminarily modified graphene oxide, and then standing, precipitating, washing and precipitating the suspension of the reaction system;
and then adding the obtained solid precipitate into an aqueous solution containing a cross-linking agent, carrying out cross-linking fixation, fully stirring a reaction system, standing after the reaction is finished, and washing and drying the obtained precipitate to obtain the modified graphene oxide.
The crosslinking agents used may be: aldehyde crosslinking agents, such as glutaraldehyde, formaldehyde, glyoxal; carbodiimide crosslinking agents such as polycarbodiimide; epoxide crosslinking agents such as epichlorohydrin and the like.
Preferably, the cross-linking agent is an aldehyde cross-linking agent, most preferably glutaraldehyde, and the mass concentration of the adopted glutaraldehyde aqueous solution is 0.5-1.5%.
According to the invention, the chitosan and the graphene oxide are chemically combined through a covalent bond in a form of high-temperature high-pressure reaction and crosslinking of the crosslinking agent, so that the modified graphene oxide is formed.
The active material comprises modified graphene oxide and nano calcium peroxide attached to the surface of the modified graphene oxide, wherein the particle size D10-D90 of the nano calcium peroxide is preferably in the range of 24-174 nm.
The nano calcium peroxide used in the invention has better effect and higher oxidative degradation efficiency, and compared with common calcium peroxide, the nano calcium peroxide overcomes the defects of smaller specific surface area and low oxidative degradation efficiency on pollutants of common calcium peroxide; the nano calcium peroxide is attached to the surface of the modified graphene oxide, so that the defect that the nano calcium peroxide directly used in the prior art is easily washed away and lost along with water flow due to small particle size is overcome.
The invention attaches calcium peroxide to the surface of modified graphene oxide by the following method:
firstly, dissolving calcium chloride in an aqueous solution containing a cationic surfactant, and then adding modified graphene oxide, wherein the mass ratio of the modified graphene oxide to the calcium chloride is 1: 2.0 to 3.5;
then, after ultrasonic dispersion is carried out for 20-60 min, slowly stirring is carried out for 5-20 min to obtain a mixed solution, and then concentrated ammonia (NH) accounting for 2-6% of the volume of the mixed solution is added3The mass percentage of the modified graphene oxide-nano calcium peroxide composite is 25-28%), adjusting the pH value of the solution, uniformly mixing, adding hydrogen peroxide (the mass percentage of hydrogen peroxide is 30%) which is 4-8 times of the mass of calcium chloride while rapidly stirring, continuously and rapidly stirring for 40-120 min after adding, standing, removing a supernatant, washing and drying the obtained precipitate, and obtaining the active material consisting of the modified graphene oxide-nano calcium peroxide composite.
Preferably, the cationic surfactant is cetyl trimethyl ammonium bromide, and the mass fraction is 0.02-0.06%.
The cationic surfactant is used for generating nano-scale calcium peroxide, so that the nano-scale calcium peroxide can be successfully attached to the surface of the modified graphene oxide.
In order to solve the problem that the water treatment agent is added once every batch of wastewater is treated in the application process of the water treatment agent, the invention further loads the obtained active material.
Firstly, preparing a framework structure for loading an active material: the skeleton structure is composed of diatomite, the diatomite is added into an aqueous solution containing a viscosity agent, an active material is added, stirring is continued, standing is carried out after stirring is finished, the obtained precipitate is dried until the water content is 15-40%, and the precipitate is crushed into particles;
and then, placing the obtained particles in a muffle furnace, and calcining for 1-2 hours at 190-220 ℃ to obtain the composite material.
Through the treatment, the strength of the modified graphene oxide composite material is ensured, the modified graphene oxide composite material can be slowly dispersed in water, the treatment effect on wastewater is achieved, and the waste of products caused by the fact that the modified graphene oxide composite material is consumed at one time is avoided.
The preparation method of the modified graphene oxide composite material comprises the following steps:
(1) mixing the graphene oxide aqueous suspension and the chitosan aqueous solution, placing the mixture in a high-pressure reaction kettle, and reacting at 160-190 ℃ to obtain solid precipitate;
(2) adding the solid precipitate obtained in the step (1) into an aqueous solution containing a cross-linking agent for cross-linking, and separating the solid precipitate after cross-linking to obtain modified graphene oxide;
(3) dissolving calcium chloride in an aqueous solution containing a cationic surfactant, adding the modified graphene oxide obtained in the step (2), adding concentrated ammonia water accounting for 2-6% of the volume of the mixed solution, then adding hydrogen peroxide while stirring, and after the reaction is finished, filtering and precipitating to obtain an active material consisting of the modified graphene oxide and nano calcium peroxide;
(4) adding diatomite into an aqueous solution containing a viscosity agent, adding the active material obtained in the step (3), continuously stirring, standing after stirring is finished, drying the obtained precipitate until the water content is 15-40%, and crushing into particles;
(5) and (4) calcining the crushed particles obtained in the step (4) for 1-2 hours at the temperature of 190-220 ℃ to obtain the modified graphene oxide composite material.
In the step (1), the mass ratio of the graphene oxide to the chitosan is 1: 0.2 to 0.5.
The preferable preparation method of the graphene oxide suspension liquid comprises the following steps: carrying out ultrasonic dispersion on graphene oxide in water for 20-60 min, and then stirring at a low speed for 1-3 h to obtain a graphene oxide suspension.
The preferable preparation method of the chitosan aqueous solution comprises the following steps: adding chitosan into an acetic acid solution with the mass fraction of 1-5%, and quickly stirring for 20-60 min to obtain a chitosan aqueous solution.
After mixing the graphene oxide suspension and the chitosan aqueous solution, firstly performing ultrasonic dispersion for 20-60 min, then stirring at a low speed for 1-3 h to obtain a suspension, pouring the suspension into a high-pressure reaction kettle, sealing, placing in a muffle furnace, reacting for 1-2 h at 160-190 ℃, cooling to room temperature after the reaction is finished, and obtaining a precipitate which is a reaction product;
in the step (2), the preferable mass concentration of the cross-linking agent in the aqueous solution is 0.5-1.5%.
Preferably the cross-linking agent is one or more of an aldehyde cross-linking agent, a carbodiimide cross-linking agent or an epoxide, and most preferably the cross-linking agent is glutaraldehyde.
In the step (2), fully stirring a reaction system during a crosslinking reaction, wherein the preferred fully stirring mode is slow stirring for 6-12 hours, and crosslinking of chitosan and graphene oxide is performed.
And (3) drying the precipitate obtained after the reaction is finished at 103-105 ℃ for 3-5 h.
In the step (3), the mass ratio of the modified graphene oxide to the calcium chloride is 1: 2.0 to 3.5; the mass ratio of the calcium chloride to the hydrogen peroxide is 1: 4 to 8.
In the step (3), the surfactant is a cationic surfactant. Hexaalkyltrimethylammonium bromide is preferred.
In step (3), it is preferableThe reaction conditions are as follows: preparing a surfactant aqueous solution with the mass fraction of 0.02-0.06%, adding calcium chloride with the weight 2.0-3.5 times that of the modified graphene oxide for dissolving, then adding the modified graphene oxide, performing ultrasonic dispersion for 20-60 min, then slowly stirring for 5-20 min to obtain a mixed solution, and then adding concentrated ammonia water (NH) accounting for 2-6% of the volume of the mixed solution3The content of the modified graphene oxide/nano calcium peroxide composite is 25-28%), uniformly mixing, quickly stirring while adding hydrogen peroxide (the content of hydrogen peroxide is 30%) 4-8 times the weight of calcium chloride, continuously and quickly stirring for 40-120 min after adding, standing, removing supernatant, washing and drying the obtained precipitate, and obtaining the active material consisting of the modified graphene oxide/nano calcium peroxide composite.
In the step (4), the mass ratio of the diatomite to the active material is 8-15: 1.
In the step (4), the preferable preparation method is as follows: drying and grinding diatomite, adding the diatomite into a polyvinyl alcohol solution with the mass fraction of 1% -2%, quickly stirring for 30-60 min, then adding an active material, continuously and quickly stirring for 30-60 min, standing, drying the obtained precipitate at 50-80 ℃ to enable the water content of the precipitate to reach 15-40% to obtain a modified graphene oxide composite material raw material, and crushing the obtained modified graphene oxide composite material raw material by using a crusher to obtain composite material particles.
And (5) calcining the obtained particles based on the modified graphene oxide composite material in a muffle furnace.
Through the treatment in the steps (4) and (5), the strength of the modified graphene oxide composite material is ensured, the modified graphene oxide composite material can be slowly dispersed in water to achieve the effect of treating wastewater, and the modified graphene oxide composite material is not consumed at one time and causes product waste.
Preferably, the method comprises the following steps:
the slow stirring speed is 150-300 rpm, and the fast stirring speed is 301-500 rpm.
The ultrasonic intensity of ultrasonic dispersion in the invention is 4-10 kw/m2。
Preferably, the particle size of the crushed modified graphene oxide raw material is 5-25 mm.
When the diatomite is used as a framework material, the diatomite is not bonded by polyvinyl alcohol serving as a bonding agent, and the composite material cannot be shaped.
In addition, in the preparation process, the temperature for calcining the modified graphene oxide composite particles is found to be too high, such as 250 ℃, the strength of the composite material is too high, the active material contained in the composite material cannot effectively play a role in the sewage treatment process, but the calcining temperature is too low, such as 160 ℃, so that the prepared modified graphene oxide composite material is disintegrated into powder and cannot be granular in the sewage treatment process. In the invention, the modified graphene oxide composite material or the composite material prepared by the preparation method is applied to sewage treatment.
According to the application method of the composite material in sewage treatment, the modified graphene oxide composite material is laid on a bearing material layer at the bottom of a water treatment reactor, and the filling volume of the composite material is 20-80% of the effective volume of the water treatment reactor.
The composite material in the technical scheme is a sustained-release medicament with sustainable action, and by selecting the diatomite as the matrix of the composite material and selecting proper calcination temperature, the problems that the material is easy to disperse when meeting water, is easy to wash away along with water flow and has low utilization rate are solved. The technical scheme has the advantages of long-term use, simple operation and high utilization rate by one-time adding.
Has the advantages that: (1) the modified graphene oxide and the diatomite both have adsorption performance, the active adsorption sites are rich in types and quantity, and the adsorption of organic matters, metal ions and dyes which are difficult to be biochemically degraded in sewage is efficient and broad-spectrum; (2) the water treatment agent prepared by the invention has the advantages of low consumption rate, low adding frequency, simple operation and low operation cost; (3) the water treatment agent prepared by the invention has stable chemical properties, has no safety risks such as explosion, corrosion, poisoning and the like, and is convenient to transport and store.
Drawings
Fig. 1 is a scanning electron microscope image of a modified graphene oxide composite material prepared in example 1 of the present invention;
FIG. 2 is a particle size distribution diagram of nano calcium peroxide separately prepared by step (4) of example 1 of the present invention;
fig. 3 is a graph illustrating the treatment effect of the modified graphene oxide composite material on the membrane filtrate of the landfill leachate in example 3 of the present invention;
fig. 4 is a graph showing the treatment effect of the modified graphene oxide composite material on printing and dyeing wastewater in embodiment 4 of the present invention.
Detailed Description
The technical scheme of the invention is further illustrated by the following examples.
Firstly, the source of raw materials
And (3) graphene oxide: the preparation method comprises the following steps of (1) preparing by a Hummers method;
molecular weight of chitosan: 60-120 kDa;
molecular weight of polyvinyl alcohol: 64-114 kDa;
diatomite: SiO 22The content is more than or equal to 85 percent.
Second, sample preparation
Example 1: preparing a modified graphene oxide composite material:
step (1): 5g of graphene oxide was added to 200g of distilled water, followed by 8kw/m2The ultrasonic intensity is dispersed for 30min, and then the mixture is stirred for 2h at the rotating speed of 200rpm, so that the graphene oxide suspension is obtained. Adding 1.5g of chitosan into 200g of acetic acid solution with the mass fraction of 2%, and stirring at 400rpm for 40min to obtain a chitosan aqueous solution.
Step (2): adding the chitosan aqueous solution obtained in the step (1) into the graphene oxide suspension obtained in the step (1) while stirring the graphene oxide suspension at the rotating speed of 400rpm, and using the chitosan aqueous solution at the rotating speed of 8kw/m2Ultrasonic dispersing for 30min, and stirring at 200rpm for 2h to obtain suspension. And pouring the suspension into a high-pressure reaction kettle, sealing, placing in a muffle furnace, reacting for 1h at 185 ℃, cooling to room temperature after the reaction is finished, and washing the precipitate for 3 times by using distilled water to obtain a reaction product.
And (3): and (3) adding the reaction product obtained in the step (2) into 200g of aqueous solution of glutaraldehyde with the mass fraction of 0.8%, stirring at 200rpm for 8h, and performing crosslinking of chitosan and graphene oxide. And standing after stirring, washing the precipitate for 3 times by using distilled water, and drying for 4 hours at the temperature of 103-105 ℃ to obtain the modified graphene oxide.
And (4): adding calcium chloride which is 2.5 times the weight of the modified graphene oxide in the step (3) into 500g of cationic surfactant cetyl trimethyl ammonium bromide aqueous solution with the mass fraction of 0.02%, stirring at 200rpm for 5min until the calcium chloride is dissolved, adding the modified graphene oxide obtained in the step (3), and stirring at 10kw/m2Ultrasonically dispersing for 30min by using the ultrasonic intensity, stirring for 10min at 200rpm, then adding 15mL of concentrated ammonia water, uniformly mixing, stirring at 400rpm while adding hydrogen peroxide with the weight 5 times that of calcium chloride, and continuously and rapidly stirring for 60min after the hydrogen peroxide is added. And (3) standing, removing supernatant, washing the precipitate with distilled water for 3 times, and drying at 103-105 ℃ for 3 hours to obtain the modified graphene oxide-nano calcium peroxide compound.
And (5): drying diatomite at 103-105 ℃ for 4h, grinding, weighing diatomite 9 times the mass of the modified graphene oxide-nano calcium peroxide compound obtained in the step (4), adding the diatomite into 500g of a polyvinyl alcohol solution with the mass fraction of 1%, stirring at 400rpm for 40min, adding the modified graphene oxide-nano calcium peroxide compound obtained in the step (4), and continuing to stir at 400rpm for 60 min. And standing, and drying the obtained precipitate at 80 ℃ to enable the water content of the precipitate to reach 25-35% to obtain the modified graphene oxide composite material raw material.
And (6): and (4) crushing the modified graphene oxide composite material raw material obtained in the step (5) by using a crusher, and controlling the particle size after crushing to be 5-15 mm to obtain modified graphene oxide composite material particles.
And (7): and (4) placing the modified graphene oxide composite material particles obtained in the step (6) in a muffle furnace, and calcining for 1h at 210 ℃ to obtain the modified graphene oxide composite material.
Example 2: preparation of modified graphene oxide composite material
Step (1): 5g of graphene oxide was added to 200g of distillationIn water, then using 10kw/m2The ultrasonic intensity is dispersed for 30min, and then the mixture is stirred for 1h at the rotating speed of 200rpm, so that the graphene oxide suspension is obtained. 2.5g of chitosan is added into 200g of acetic acid solution with the mass fraction of 5 percent, and the mixture is stirred for 60min at the rotating speed of 400rpm, so as to obtain the chitosan aqueous solution.
Step (2): adding the chitosan aqueous solution obtained in the step (1) into the graphene oxide suspension obtained in the step (1) while stirring the graphene oxide suspension at the rotating speed of 400rpm, and using 10kw/m2Ultrasonically dispersing for 60min at the ultrasonic intensity, and stirring for 3h at the rotating speed of 200rpm to obtain a suspension; pouring the suspension into a high-pressure reaction kettle, sealing, placing in a muffle furnace, reacting at 190 ℃ for 1.5h, cooling to room temperature after the reaction is finished, and washing the precipitate for 3 times by using distilled water to obtain a reaction product.
And (3): and (3) adding the reaction product obtained in the step (2) into 200g of aqueous solution of glutaraldehyde with the mass fraction of 1.5%, stirring at the rotating speed of 200rpm for 12h, and performing crosslinking of chitosan and graphene oxide. And standing after stirring, washing the precipitate for 3 times by using distilled water, and drying for 4 hours at the temperature of 103-105 ℃ to obtain the modified graphene oxide.
And (4): adding calcium chloride which is 3.5 times the weight of the modified graphene oxide in the step (3) into 500g of cationic surfactant cetyl trimethyl ammonium bromide aqueous solution with the mass fraction of 0.06%, stirring at the rotating speed of 200rpm for 20min until the calcium chloride is dissolved, then adding the modified graphene oxide obtained in the step (3), and stirring at the rotating speed of 10kw/m2Ultrasonically dispersing for 60min by using the ultrasonic intensity, stirring for 20min at 200rpm, then adding 30mL of concentrated ammonia water, uniformly mixing, stirring at 400rpm while adding hydrogen peroxide 8 times the weight of calcium chloride, and continuously and rapidly stirring for 120min after the hydrogen peroxide is added. And (3) standing, removing supernatant, washing the precipitate with distilled water for 3 times, and drying at 103-105 ℃ for 3 hours to obtain the modified graphene oxide-nano calcium peroxide compound.
And (5): drying diatomite at 103-105 ℃ for 4h, grinding, weighing diatomite 15 times the mass of the modified graphene oxide-nano calcium peroxide compound obtained in the step (4), adding the diatomite into 500g of polyvinyl alcohol solution with the mass fraction of 2%, stirring at 400rpm for 60min, adding the modified graphene oxide-nano calcium peroxide compound obtained in the step (4), and continuing to stir at 400rpm for 60 min. And standing, and drying the obtained precipitate at 80 ℃ to enable the water content of the precipitate to reach 25-35% to obtain the modified graphene oxide composite material raw material.
And (6): and (6) crushing the modified graphene oxide composite material raw material obtained in the step (5) by using a crusher, and controlling the particle size after crushing to be 5-15 mm to obtain modified graphene oxide composite material particles.
And (7): and (4) placing the modified graphene oxide composite material particles obtained in the step (6) in a muffle furnace, and calcining for 1h at 210 ℃ to obtain the modified graphene oxide composite material.
Example 3: the method in the step (4) in the embodiment 1 is used for preparing the nano calcium peroxide, the modified graphene oxide is not added during preparation, the obtained nano calcium peroxide is measured by a Winner802 photon-related nano laser particle size analyzer, the measurement result is shown in fig. 2, as can be seen from fig. 2, the particle size range of the nano calcium peroxide is 24-174 nm from D10-D90, and 77nm from D50, and the nano calcium peroxide has higher oxidative degradation efficiency by attaching the nano calcium peroxide to the surface of the modified graphene oxide.
Third, the invention modified graphene oxide composite material is applied in sewage treatment
Application example 1:
the modified graphene oxide composite material prepared in example 1 is applied as a sewage treatment agent, and is implemented by taking a landfill leachate membrane concentrated solution of a certain landfill as a treatment object through the following steps:
the method comprises the following steps: the water treatment reactor who uses is the retort, and the material is organic glass, and high 620mm, diameter 232mm, and effective volume is 23.4L, and the lateral wall and the reactor bottom of retort apart from 20mm department in top respectively have a diameter to be 12 mm's trompil.
Step two: pebbles with the particle size of 15-25 mm are placed at the bottom of the reactor, the filling height is 80mm, and then 5.8kg of the modified graphene oxide composite material prepared by the method in the embodiment 1 is added.
Step three: the landfill leachate membrane concentrated solution flows in from the opening at the bottom of the reactor and is discharged from the opening at the side wall of the upper part of the reaction tank, the inflow speed is 0.7L/min, the Hydraulic Retention Time (HRT) is 24min, and the whole operation period is 12 d.
As can be seen from fig. 3, the modified graphene oxide composite material always maintains an efficient and stable treatment effect on the landfill leachate membrane concentrated solution in the operating period of 12 d. COD and Ca2+、Mg2+The average removal rates of (a) were 67.9%, 82.8% and 75.6%, respectively.
Example 4:
the modified graphene oxide composite material prepared in example 1 is applied as a sewage treatment agent, and printing and dyeing wastewater of a certain printing and dyeing mill is taken as a treatment object, and the application is implemented through the following steps:
the method comprises the following steps: the same procedure as in application example 1.
Step two: the same applies to example 1, step two.
Step three: printing and dyeing wastewater flows in from an opening at the bottom of the reactor and is discharged from an opening at the side wall of the upper part of the reaction tank, the inflow speed is 0.93L/min, the HRT is 18min, and the whole operation period is 12 d.
As can be seen from FIG. 4, the modified graphene oxide composite material has a good treatment effect on printing and dyeing wastewater, and the removal rates of COD and chromaticity respectively reach 75.0% and 79.8%.
Claims (6)
1. The modified graphene oxide composite material is characterized in that a skeleton structure of the composite material at least comprises one component of diatomite, the skeleton structure is formed by bonding with a bonding agent, and the bonding agent is polyvinyl alcohol; the framework structure is loaded with an active material, and the active material comprises modified graphene oxide and nano calcium peroxide attached to the surface of the modified graphene oxide; the modified graphene oxide is chitosan-modified graphene oxide; the mass ratio of the skeleton structure to the active material is 8-15: 1; the mass ratio of the modified graphene oxide to the nano calcium peroxide in the active material is 1: 0.4 to 0.7; the mass of the graphene oxide and the chitosan in the modified graphene oxide is 1: 0.2 to 0.5; the graphene oxide and the chitosan are crosslinked through glutaraldehyde;
the composite material is prepared by the following steps: preparing a framework structure loaded with an active material, wherein the framework structure is composed of diatomite, adding the diatomite into an aqueous solution containing a viscosity agent, adding the active material, continuously stirring, standing after stirring is finished, drying the obtained precipitate until the water content is 15-40%, and crushing into particles; placing the obtained particles in a muffle furnace, and calcining for 1-2 h at 190-220 ℃ to obtain a composite material;
the active material is prepared by the following method: dissolving calcium chloride in an aqueous solution containing a cationic surfactant, adding modified graphene oxide, adding concentrated ammonia water accounting for 2-6% of the volume of the mixed solution, then adding hydrogen peroxide while stirring, and after the reaction is finished, filtering and precipitating to obtain an active material consisting of the modified graphene oxide and nano calcium peroxide; the cationic surfactant is cetyl trimethyl ammonium bromide.
2. The modified graphene oxide composite material according to claim 1, wherein the cationic surfactant cetyl trimethylammonium bromide is present in an amount of 0.02 to 0.06% by mass; and/or the polyvinyl alcohol is 1-2% of polyvinyl alcohol solution.
3. The preparation method of the modified graphene oxide composite material is characterized by comprising the following steps:
(1) mixing the graphene oxide aqueous suspension and the chitosan aqueous solution, placing the mixture in a high-pressure reaction kettle, and reacting at 160-190 ℃ to obtain solid precipitate; the mass ratio of the graphene oxide to the chitosan is 1: 0.2 to 0.5;
(2) adding the solid precipitate obtained in the step (1) into an aqueous solution containing a cross-linking agent for cross-linking, and separating the solid precipitate after cross-linking to obtain modified graphene oxide; the cross-linking agent is glutaraldehyde;
(3) dissolving calcium chloride in an aqueous solution containing a cationic surfactant, adding the modified graphene oxide obtained in the step (2), adding concentrated ammonia water accounting for 2-6% of the volume of the mixed solution, then adding hydrogen peroxide while stirring, and after the reaction is finished, filtering and precipitating to obtain an active material consisting of the modified graphene oxide and nano calcium peroxide; the mass ratio of the modified graphene oxide to the calcium chloride is 1: 2.0 to 3.5; the mass ratio of the calcium chloride to the hydrogen peroxide is 1: 4-8;
(4) adding diatomite into an aqueous solution containing a viscosity agent, adding the active material obtained in the step (3), continuously stirring, standing after stirring is finished, drying the obtained precipitate until the water content is 15-40%, and crushing into particles; the mass ratio of the diatomite to the active material is 8-15: 1;
(5) and (4) calcining the crushed particles obtained in the step (4) for 1-2 hours at the temperature of 190-220 ℃ to obtain the modified graphene oxide composite material.
4. The method for preparing the modified graphene oxide composite material according to claim 3, wherein in the step (2), the cross-linking agent is glutaraldehyde with a mass concentration of 0.5-1.5%.
5. The method for preparing the modified graphene oxide composite material according to claim 3, wherein in the step (3), the cationic surfactant is cetyl trimethyl ammonium bromide, and the mass fraction of the cationic surfactant is 0.02-0.06%.
6. The preparation method of the modified graphene oxide composite material according to claim 3, wherein in the step (4), diatomite is dried and ground, then the diatomite is added into a polyvinyl alcohol solution with the mass fraction of 1% -2%, the mixture is rapidly stirred for 30-60 min, then an active material is added, the mixture is continuously and rapidly stirred for 30-60 min, the obtained precipitate is dried at 50-80 ℃ after standing, the water content of the precipitate reaches 15-40%, a modified graphene oxide composite material raw material is obtained, and the obtained modified graphene oxide composite material raw material is crushed by a crusher, so that composite material particles are obtained.
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| US10759681B2 (en) * | 2018-06-28 | 2020-09-01 | Board Of Trustees Of The University Of Arkansas | Water purification compositions and the method of producing the same |
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| US10759681B2 (en) * | 2018-06-28 | 2020-09-01 | Board Of Trustees Of The University Of Arkansas | Water purification compositions and the method of producing the same |
| CN109019825A (en) * | 2018-10-09 | 2018-12-18 | 宁波沸柴机器人科技有限公司 | A kind of efficient treating agent for papermaking wastewater and its preparation method and application |
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