CN113952927A - Double-channel 3D graphene ball prepared by CVD method and application thereof in emulsion separation - Google Patents
Double-channel 3D graphene ball prepared by CVD method and application thereof in emulsion separation Download PDFInfo
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- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 36
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 17
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- 238000005530 etching Methods 0.000 claims description 13
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- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 8
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
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- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 7
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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
- B01J20/02—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/0202—Separation of non-miscible liquids by ab- or adsorption
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/04—Breaking emulsions
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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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
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- B01J20/28019—Spherical, ellipsoidal or cylindrical
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Abstract
The invention provides a double-channel 3D graphene ball prepared by a CVD method and application thereof in emulsion separation, and belongs to the technical field of oil-water filter materials. The technical scheme is as follows: mesoporous MgO particles are prepared firstly, then 3D graphene spheres are prepared by a CVD method, and the separation of the emulsion is realized by utilizing the efficient separation capability of the graphene spheres. The invention has the beneficial effects that: the graphene ball prepared by the method has good reusability, is circulated for 10 times, has the emulsion separation efficiency of the graphene material still kept above 95%, has high-efficiency emulsion separation capability on different oil agents and organic solvents, and can be used for recovering the oil agents and the organic solvents with toxicity and volatility, so that the environmental pollution caused by experiments is effectively solved.
Description
Technical Field
The invention relates to the technical field of oil-water filter materials, in particular to a CVD method for preparing a double-channel 3D graphene ball and application of the double-channel 3D graphene ball in emulsion separation.
Background
With the increasing concern and protection of the environment, there is an increasing demand for materials that address organic pollutants and oil leaks. The existing adsorption materials include membrane materials (fabrics, fibrous membranes, nets, etc.), porous materials (sponges, aerogels, etc.), and some powder materials, etc., although they have been widely used in research and practical applications, there are still limitations. The membrane material and the porous material are not suitable for cleaning large-area oil leakage or organic pollutants, and the reported powder materials comprising carbon nano-particles, calcium carbonate particles, silica particles and the like have poor dispersion in a system and cannot be used for emulsion separation. However, many of the current wastewater pollutants are not only simple oil-water mixtures but also exist in emulsion systems, which greatly improves the separation difficulty.
In recent years, carbon materials, especially graphene materials, have been considered as suitable candidates for superhydrophobic surfaces due to their low surface energy and tunable topological nanostructures. In particular, porous graphene is also widely used as an electrode material for batteries and supercapacitors, as an adsorbent for separation processes and gas storage, and as a support for many important catalytic processes due to its high surface area and large pore volume. The combination of superhydrophobicity and porosity can broaden the potential application range of graphene materials, particularly in water filtration or water/oil separation. Currently, researchers have developed many techniques for synthesizing graphene materials, including chemical or physical activation, wet chemical routes, template replication processes, and Chemical Vapor Deposition (CVD). Among these methods, CVD is one of the most commonly used methods for the preparation of graphene materials.
Graphene materials usually have a channel, a hydrophobic channel or an oleophobic channel, and at present, organic synthesis is generally performed in organic solvents, and the organic solvents are often highly volatile and toxic, which causes great pollution to the environment, and in addition, some conventional 2D graphene sheets are easily aggregated in the solvents and cannot be well dispersed. Therefore, we propose a method for preparing a 3D mesoporous graphene material with dual channels by using spray drying and CVD techniques.
Disclosure of Invention
The invention aims to provide a CVD method for preparing a dual-channel 3D graphene ball and application of the dual-channel 3D graphene ball in emulsion separation.
In order to achieve the purpose, the invention adopts the following technical scheme: a CVD method for preparing a double-channel 3D graphene ball and application of the double-channel 3D graphene ball in emulsion separation comprises the following steps:
step 1, adding Na2CO3Particles and MgCl2Adding the particles into deionized water respectively, stirring, and adding Na2CO3The solution was slowly added dropwise to MgCl while stirring2In solution, the resulting milky Mg2CO3Carrying out suction filtration and deionized water washing on the solution, repeating the steps for three times, and finally carrying out spray drying on the obtained solution to obtain powder particles;
3, etching the sample catalyzed in the step 2 by using hydrochloric acid, removing impurities in the step 1, repeatedly etching and washing for 3 times, and finally performing suction filtration and drying to obtain 3D graphene powder;
step 4, mixing oil and water according to a volume ratio of 1:9, and stirring for 2 hours at 25-30 ℃ to obtain oil-water emulsion without surfactant; dissolving Sodium Dodecyl Sulfate (SDS) in water as an emulsifier, then adding related oil into the water, fixing the volume ratio of the oil to the water at 1:99, and stirring at 25-30 ℃ for 1h to obtain an oil-water emulsion with stable surfactant;
and 5, respectively adding the two emulsions obtained in the step 4 into the 3D graphene powder obtained in the step 3, stirring for 10min, filtering, and observing the emulsion separation effect.
As a scheme for preparing double-channel 3D graphene spheres by a CVD method and further optimizing the application of the double-channel 3D graphene spheres in emulsion separation, in the step 1, Na is added2CO3The particles are7-10g，MgCl2The granules are 7-10g, and are respectively added into 50-80ml and 80-160ml of deionized water.
As a scheme for further optimizing the preparation of the double-channel 3D graphene ball by the CVD method and the application of the double-channel 3D graphene ball in emulsion separation, in the step 2, the temperature of the muffle furnace is increased to 600 ℃ at the temperature increase rate of 5 ℃/min, and the temperature is kept for two hours; introducing Ar2The flow rate is 500sccm, and the temperature is increased to 900 ℃ at the temperature rising rate of 10 ℃/min; introducing acetonitrile for 10min at 65 ℃ at the flow rate of 150 sccm; the methane was passed for 20min at a flow rate of 400 sccm.
As a further optimization scheme for preparing the double-channel 3D graphene ball by the CVD method and applying the double-channel 3D graphene ball to emulsion separation, in the step 3, the hydrochloric acid concentration is 1mol/L, and etching is performed at the temperature of 60-70 ℃.
As a scheme for preparing a double-channel 3D graphene ball by a CVD method and further optimizing the application of the double-channel 3D graphene ball in emulsion separation, in the step 4, the surfactant-free water-oil emulsion is stable for 4 hours; the surfactant stabilized oil-in-water emulsion is stable for at least 24 hours.
Compared with the prior art, the invention has the beneficial effects that: the graphene ball prepared by the method has good reusability, is circulated for 10 times, and the emulsion separation efficiency of the graphene material is still kept above 95%. The graphene spheres have high-efficiency emulsion separation capacity for different oil agents and organic solvents. The toxic and volatile oil and organic solvent are recovered, so that the pollution of the experiment to the environment is effectively solved.
Drawings
Fig. 1 is a schematic view of a preparation process of a 3D graphene ball according to the present invention.
In FIG. 2, (a) is an MgO pellet of the present invention; (b) is a graphene/MgO sphere; (c) is an SEM photograph of the 3D graphene spheres; (D-f) is a TEM photograph of the 3D graphene spheres; (g-i) elemental scan of 3D graphene spheres.
In FIG. 3, (a) is MgCO of the present invention3XRD spectra of spheres, MgO/graphene spheres, and 3D graphene spheres; (b) raman light as 3D graphene spheresA spectrogram; XPS spectra of (C) C1s and (D) N1s in 3D graphene spheres; (e, f) nitrogen adsorption-desorption analysis graphs of MgO spheres and 3D graphene spheres.
In FIG. 4, (a) is a diagram of the oil-water emulsion separation process of the present invention; (b) is a contact angle picture of a pure graphene material.
FIG. 5 is a light microscopy analysis of emulsifier free (SFE) and emulsifier with (SSE) systems of the invention before and after isolation.
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications or substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit and scope of the invention. The experimental methods and reagents of the formulations not specified in the examples are in accordance with the conventional conditions in the art.
Example 1
Step 1, 8.836g of Na2CO3Particles and 8g of MgCl2The granules were added to 80ml and 160ml of deionized water respectively and stirred well, then Na was added2CO3The solution was slowly added dropwise to MgCl while stirring2In solution, the resulting milky Mg2CO3And carrying out suction filtration and deionized water washing on the solution, repeating the steps for three times, and finally carrying out spray drying on the obtained solution to obtain powder.
And 3, etching the sample catalyzed in the step 2 at 60 ℃ by using 1mol/L hydrochloric acid, removing impurities in the step 1, repeatedly etching and washing for 3 times, and finally performing suction filtration and drying to obtain the double-channel 3D graphene powder.
Step 4, surfactant-free oil-water emulsion: mixing oil and water at a volume ratio of 1:9, and stirring at 25-30 deg.C for 2 hr to obtain emulsion. Surfactant-stabilized oil-water emulsions: SDS was first dissolved in water as an emulsifier and the relevant oil was then added to the water, with the volume ratio of oil to water being fixed at 1: 99. Then, the mixture was stirred at 25 to 30 ℃ for 1 hour to obtain an emulsion.
And 5, adding the 3D graphene powder obtained in the step 3 into the emulsion obtained in the step 4, stirring for 10min, and observing the system separation condition.
As shown in fig. 1(a), a schematic flow chart of the preparation of the 3D graphene ball of the present embodiment is shown. First of all from Na2CO3And MgCl2Reacting to obtain MgCO3The preparation method comprises the following steps of (1) carrying out particle preparation, then carrying out spray drying to obtain mesoporous MgO spheres, carrying out CVD catalysis on the obtained MgO spheres, wherein the MgO spheres can be used as a template and a catalyst for graphene in-situ growth, and can effectively promote the formation of a regular graphene shell in the CVD process, and in order to obtain double channels, two carbon sources are used: acetonitrile and methane, forming a super-hydrophilic N-doped graphene layer by using the acetonitrile, forming a super-hydrophobic graphene layer by using the methane, and finally etching the MgO template by using a hydrochloric acid solution to obtain the double-channel 3D graphene ball.
The 3D graphene ball prepared in the embodiment separates the emulsion, the separation process and the dispersion condition are shown in fig. 3, the separation of the water phase and the graphene adsorbing the oil phase is observed, the clear and transparent water phase is obtained by filtering, and the separation efficiency is high. Example 2
Step 1, 8.836g of Na2CO3Particles and 8g of MgCl2The granules were added to 50ml and 80ml of deionized water respectively and stirred well, then Na was added2CO3The solution was slowly added dropwise to MgCl while stirring2In solution, the resulting milky Mg2CO3And carrying out suction filtration and deionized water washing on the solution, repeating the steps for three times, and finally carrying out spray drying on the obtained solution to obtain powder.
And 3, etching the sample catalyzed in the step 2 at 65 ℃ by using 1mol/L hydrochloric acid, removing impurities in the step 1, repeatedly etching and washing for 3 times, and finally performing suction filtration and drying to obtain the N-doped 3D graphene powder.
Step 4, surfactant-free oil-water emulsion: mixing oil and water at a volume ratio of 1:9, and stirring at 25-30 deg.C for 2 hr to obtain emulsion. Surfactant-stabilized oil-water emulsions: SDS was first dissolved in water as an emulsifier and the relevant oil was then added to the water, with the volume ratio of oil to water being fixed at 1: 99. Then, the mixture was stirred at 25 to 30 ℃ for 1 hour to obtain an emulsion.
And 5, adding the 3D graphene powder obtained in the step 3 into the emulsion obtained in the step 4, stirring for 10min, and observing the system separation condition. .
The N-doped 3D graphene ball prepared in the embodiment only has a hydrophilic group, and cannot separate an emulsion, and the obtained product after filtration is an oil-water mixture.
Example 3
Step 1, 9g of Na2CO3Particles and 7g of MgCl2The granules were added to 80ml and 160ml of deionized water respectively and stirred well, then Na was added2CO3The solution was slowly added dropwise to MgCl while stirring2In solution, the resulting milky Mg2CO3And carrying out suction filtration and deionized water washing on the solution, repeating the steps for three times, and finally carrying out spray drying on the obtained solution to obtain powder.
And 3, etching the sample catalyzed in the step 2 by using 1mol/L hydrochloric acid at 70 ℃, removing impurities in the step 1, repeatedly etching and washing for 3 times, and finally performing suction filtration and drying to obtain 3D graphene powder.
Step 4, surfactant-free oil-water emulsion: mixing oil and water at a volume ratio of 1:9, and stirring at 25-30 deg.C for 2 hr to obtain emulsion. Surfactant-stabilized oil-water emulsions: SDS was first dissolved in water as an emulsifier and the relevant oil was then added to the water, with the volume ratio of oil to water being fixed at 1: 99. Then, the mixture was stirred at 25 to 30 ℃ for 1 hour to obtain an emulsion.
And 5, adding the 3D graphene powder obtained in the step 3 into the emulsion obtained in the step 4, stirring for 10min, and observing the system separation condition.
The 3D graphene ball prepared by the embodiment has super-hydrophobicity, no hydrophilic group, easy agglomeration in a system and low separation efficiency.
The two-channel 3D graphene ball prepared in the example was used for testing as shown in fig. 1.
The above description is only a preferred embodiment of the present invention, and should not be taken as limiting the invention, and any local variations in the formulation and process thereof should be considered within the scope of the present invention.
Claims (5)
1. A CVD method for preparing a double-channel 3D graphene ball and application of the double-channel 3D graphene ball in emulsion separation are characterized by comprising the following steps:
step 1, adding Na2CO3Particles and MgCl2Adding the particles into deionized water respectively, stirring, and adding Na2CO3The solution was slowly added dropwise to MgCl while stirring2In solution, the resulting milky Mg2CO3Carrying out suction filtration and deionized water washing on the solution, repeating the steps for three times, and finally carrying out spray drying on the obtained solution to obtain powder particles;
step 2, placing the powder particles obtained in the step 1 into a muffle furnace for pretreatment; then carrying out CVD catalysis, and introducing Ar in the whole process2Then is introduced intoReplacing a carbon source, closing acetonitrile, introducing methane, and naturally cooling to room temperature after the acetonitrile is ended;
3, etching the sample catalyzed in the step 2 by using hydrochloric acid, removing impurities in the step 1, repeatedly etching and washing for 3 times, and finally performing suction filtration and drying to obtain 3D graphene powder;
step 4, mixing oil and water according to a volume ratio of 1:9, and stirring for 2 hours at 25-30 ℃ to obtain oil-water emulsion without surfactant; dissolving Sodium Dodecyl Sulfate (SDS) in water as an emulsifier, then adding related oil into the water, fixing the volume ratio of the oil to the water at 1:99, and stirring at 25-30 ℃ for 1h to obtain an oil-water emulsion with stable surfactant;
and 5, respectively adding the two emulsions obtained in the step 4 into the 3D graphene powder obtained in the step 3, stirring for 10min, filtering, and observing the emulsion separation effect.
2. The CVD method for preparing two-channel 3D graphene balls according to claim 1, and the application of the graphene balls in emulsion separation, wherein in the step 1, Na is added2CO3The particles are 7-10g of MgCl2The granules are 7-10g, and are respectively added into 50-80ml and 80-160ml of deionized water.
3. The CVD method for preparing the dual-channel 3D graphene ball and the application thereof in emulsion separation according to claim 1 or 2, wherein in the step 2, the temperature of the muffle furnace is raised to 600 ℃ at a temperature raising rate of 5 ℃/min, and the temperature is kept for two hours; introducing Ar2The flow rate is 500sccm, and the temperature is increased to 900 ℃ at the temperature rising rate of 10 ℃/min; introducing acetonitrile for 10min at 65 ℃ at the flow rate of 150 sccm; the methane was passed for 20min at a flow rate of 400 sccm.
4. The CVD method for preparing the two-channel 3D graphene ball and the application thereof in emulsion separation according to claim 1, wherein in the step 3, the hydrochloric acid concentration is 1mol/L, and etching is performed at 60-70 ℃.
5. The CVD method for preparing two-channel 3D graphene balls and the application thereof in emulsion separation according to claim 1, wherein in the step 4, the surfactant-free water-oil emulsion is stable for 4 h; the surfactant stabilized oil-in-water emulsion is stable for at least 24 hours.
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