CN117101186A - Method for regulating and controlling wettability of oil-water separation material - Google Patents
Method for regulating and controlling wettability of oil-water separation material Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 238000000034 method Methods 0.000 title claims abstract description 42
- 238000000926 separation method Methods 0.000 title claims abstract description 40
- 239000000463 material Substances 0.000 title claims abstract description 20
- 230000001276 controlling effect Effects 0.000 title claims abstract description 8
- 230000001105 regulatory effect Effects 0.000 title claims abstract description 8
- 239000010949 copper Substances 0.000 claims abstract description 195
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 189
- 229910052802 copper Inorganic materials 0.000 claims abstract description 188
- 230000003075 superhydrophobic effect Effects 0.000 claims abstract description 71
- 239000011259 mixed solution Substances 0.000 claims abstract description 47
- 238000002791 soaking Methods 0.000 claims abstract description 21
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 8
- 238000007789 sealing Methods 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 75
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 65
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 54
- 239000008367 deionised water Substances 0.000 claims description 36
- 229910021641 deionized water Inorganic materials 0.000 claims description 36
- 239000003921 oil Substances 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 21
- QJAOYSPHSNGHNC-UHFFFAOYSA-N octadecane-1-thiol Chemical group CCCCCCCCCCCCCCCCCCS QJAOYSPHSNGHNC-UHFFFAOYSA-N 0.000 claims description 10
- 239000000295 fuel oil Substances 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 230000009467 reduction Effects 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 239000004480 active ingredient Substances 0.000 claims description 4
- 239000003344 environmental pollutant Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 231100000719 pollutant Toxicity 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims 2
- 230000008569 process Effects 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- 235000019198 oils Nutrition 0.000 description 15
- 238000012360 testing method Methods 0.000 description 13
- 239000003513 alkali Substances 0.000 description 10
- 230000008859 change Effects 0.000 description 7
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 235000019476 oil-water mixture Nutrition 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 230000001066 destructive effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000013532 laser treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003361 porogen Substances 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001612 separation test Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- 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
- B01D17/12—Auxiliary equipment particularly adapted for use with liquid-separating apparatus, e.g. control circuits
-
- 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
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
Abstract
The invention belongs to the technical field of chemical engineering, and particularly discloses a method for regulating and controlling wettability of an oil-water separation material. The super-hydrophobic copper mesh is obtained by sealing and ultrasonic treatment in NaOH-absolute ethyl alcohol mixed solution for 10min, standing and soaking at normal temperature after ultrasonic treatment is finished, and the super-hydrophilic copper mesh is obtained by repeating the operation to realize the circulation of super-hydrophilic and super-hydrophobic. The super-hydrophobic copper net is converted into a super-hydrophilic copper net, the super-hydrophilic state lasts for 1-2 days, and then the super-hydrophilic copper net is spontaneously converted into the super-hydrophobic copper net; standing and soaking in the NaOH-absolute ethyl alcohol mixed solution again, and converting the super-hydrophobic copper net into a super-hydrophilic copper net; the process of converting the super-hydrophobic into super-hydrophilic and then spontaneously converting the super-hydrophilic into super-hydrophobic of the same copper net can be cycled for 8 times. The invention solves the technical problems of time consumption, complex operation and even destructiveness of the regulation and control method in the prior art. The wettability copper net obtained by the invention has stable mechanical structure, and the regulation and control method is simple and feasible and meets the requirement of mass production.
Description
Technical Field
The invention belongs to the technical field of chemical engineering, and particularly relates to a method for regulating and controlling wettability of an oil-water separation material.
Background
The wettability of a solid surface is one of the basic properties that can be tuned by changing the surface morphology and chemical composition. Superhydrophobicity with Water Contact Angles (WCA) greater than 150 ° and superhydrophilicity less than 10 ° are attracting attention because of their great potential in self-cleaning, protective coatings, microfluidics, oil-water separation, and the like. In recent years, intelligent super-wettability materials capable of reversibly switching between super-hydrophilicity and super-hydrophobicity are of great interest because of the characteristics of super-hydrophilicity and super-hydrophobicity. The wettability of the surface of a material is primarily dependent on the surface energy and roughness, so that the surface super-wettability can be reversibly switched by changing the surface composition and/or morphology by external stimuli, such as temperature, gravity loading, light, magnetic field, pH, etc.
While a number of wettability switchable surfaces have been developed, their switching ability is largely dependent on the stimulus response chemistry of the intrinsic substrate or additional coating. That is, switchable wettability can only be achieved on some specific stimulus-responsive substrates. For a normal surface without stimulus-responsive chemistry, it cannot change the surface wettability by responding to external stimuli (e.g., temperature, light, pH, potential, and magnetic field). The drawbacks of substrate dependence and slow response greatly limit the practical application of wettability switchable surfaces based on stimulus response chemistry. At the same time, the method for adjusting the surface wettability and realizing the surface super wettability transition is time-consuming, complex to operate and even destructive. Developing a fast, simple and non-destructive method to accurately and repeatedly adjust the surface wettability and to produce a reversible super-wetted surface remains a great challenge.
Jiang et al (adv. Funct. Mater.,27 (2017), pp. 1605446) modified by a low surface energy material to change the wettability of the coated magnesium alloy surface to achieve superhydrophobicity and further high temperature (350 ℃) treatment to convert to superhydrophilicity. However, this method is time-consuming and energy-consuming, and is not suitable for mass production.
Qu et al (ACS appl. Mater. Interfaces,11 (2019), pp. 24668-24682) developed a pH responsive super-wetted surface, but the use of a porogen negatively affected the surface structure and mechanical properties during the preparation process.
Jiao et al (ACS Applied Materials)&Interface (2018), 10 (19), 16867-16873) prepared multi-scale TiO on titanium surface by femtosecond (fs) laser treatment 2 Square microcolumns. The original sample shows super-oxygen-repellency in water, becomes underwater super-oxygen-hydrophilicity after being heated for 0.5h in a dark environment, and can recover the underwater super-oxygen-repellency after being irradiated by ultraviolet rays for 1 h. The instrumentation required for the implementation of the method creates a certain impediment to the implementation of the method.
Cheng et al (ACS Applied Materials)&Interfaces (2014), 6 (1), 636-641) produce layered microstructures on copper sheets by chemical etching. Roughened surface is-CH 3 and-COOH group modification. The carboxyl groups are responsive to the pH of the aqueous solution, so that the underwater wettability of the sample surface can be altered by changing the pH of the water. The sample surface shows superoleophobic property in alkaline water and superoleophilic property in acidic water. The disadvantage of this method is that the wettability changes depending on the drastic changes in pH, and the preparation process is complex.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for regulating and controlling the wettability of an oil-water separation material, which ensures that the wettability of the oil-water separation material can be changed through simple standing and soaking at normal temperature, and the wettability can circulate between super-hydrophobic and super-hydrophilic, so that the method has the advantages of simple process, simple and easily obtained material, no need of large-scale instruments and equipment, and capability of meeting the requirement of large-scale preparation, and the separation efficiency of the obtained oil-water separation material can reach more than 99 percent.
The invention provides a method for regulating and controlling the wettability of an oil-water separation material, which comprises the following steps,
step (1), preparation of super-hydrophilic oil-water separation material:
firstly, sequentially cleaning copper meshes (100 meshes, 200 meshes, 300 meshes, 400 meshes and 500 meshes respectively) with deionized water and acetone (or deionized water and ethanol) to remove pollutants on the surface;
secondly, the above-mentioned Jingqing is processedImmersing the washed copper net into NaOH and (NH) 4 ) 2 S 2 O 8 For 30 minutes, to obtain Cu (OH) formed on the surface 2 Is a super hydrophilic copper net; the chemical reaction involved in this process can be explained by the following chemical reaction equation:
Cu+4NaOH+(NH 4 ) 2 S 2 O 8 ＝Cu(OH) 2 +2Na 2 SO 4 +2NH 3 +2H 2 O
a step (2),The method for converting the super-hydrophilic copper net into the super-hydrophobic copper net comprises the following steps:
firstly, fixing the prepared super-hydrophilic copper net between two clamps of an oil-water separator (a schematic diagram of the oil-water separator is shown as figure 1 in the attached drawing of the specification); then pouring deionized water into the upper pipe; subsequently, n-hexane was added and deionized water was found to flow through the copper mesh while n-hexane remained over the copper mesh; then, a mixed solution of n-Octadecanethiol (ODT) -absolute ethanol was poured, and after a certain time, n-hexane, which was initially left above the prepared super-hydrophilic copper mesh, was flowed through the copper mesh. And taking out the copper net, and cleaning the copper net with enough ethanol and deionized water in sequence to obtain the super-hydrophobic copper net.
Step (3)、The method for converting the super-hydrophobic copper mesh obtained in the step (2) into the super-hydrophilic copper mesh comprises the following steps:
mixing the prepared NaOH solution (NaOH solution is referred to as "NaOH aqueous solution", hereinafter, not described in detail) with a proper amount of absolute ethyl alcohol to obtain a NaOH-absolute ethyl alcohol mixed solution, soaking the super-hydrophobic copper mesh prepared in the step (2), and carrying out ultrasonic treatment for 10min under a sealing condition together with the NaOH-absolute ethyl alcohol mixed solution to enable the super-hydrophobic copper mesh and the mixed solution to fully mutually react; after the ultrasonic treatment is finished, standing and soaking are carried out at normal temperature under a sealing condition until the wettability of the copper mesh is changed from super-hydrophobic to super-hydrophilic (the step is simply called "alkali soaking", and the details are not repeated later);
after the super-hydrophilic copper net obtained in the step (4) and the step (3) is kept in a super-hydrophilic state for 1-2 days, spontaneously converting the super-hydrophilic copper net into a super-hydrophobic copper net, and repeating the step (3) on the super-hydrophobic copper net to convert the super-hydrophobic copper net into the super-hydrophilic copper net again; thus, the circulation of the wettability of the copper mesh between superhydrophilic and superhydrophobic is realized in a reciprocating manner.
Further, in the step (1), the mesh number of the copper mesh is one or more of 100 mesh, 200 mesh, 300 mesh, 400 mesh and 500 mesh; said NaOH and (NH 4 ) 2 S 2 O 8 Is composed of NaOH solution and (NH) 4 ) 2 S 2 O 8 Solution ("(NH) 4 ) 2 S 2 O 8 Solution "refers" (NH) 4 ) 2 S 2 O 8 Aqueous solution ", the same shall apply hereinafter, not described in detail), the concentration of NaOH in the mixed solution is below 4M (M means mol/L, the same shall apply hereinafter, not described in detail), preferably below 1M, the concentration of (NH) in the mixed solution 4 ) 2 S 2 O 8 The concentration of the solution is below 2M, preferably 0.05M; the immersion in NaOH and (NH) 4 ) 2 S 2 O 8 The time in the mixed solution of (2) is 10 minutes to 1 hour, preferably 30 minutes; the active ingredient of the super-hydrophilic copper net is Cu (OH) 2 。
The length, width and thickness of the copper mesh adopted in the experimental process are 2.5cm, 2.5cm and 0.09mm in sequence;
further, in the step (2), the active ingredient of the super-hydrophobic copper mesh is n-octadecanethiol; the volume of the deionized water is 10-200 mL, preferably 10-100 mL; the volume of the n-hexane is 5-50 mL, preferably 5-25 mL; the concentration of the mixed solution of the n-octadecanethiol and the absolute ethyl alcohol is 0.01-1M (the concentration of the n-octadecanethiol in the mixed solution is the same and is not repeated), preferably 0.03-0.07M, and the volume is 5-100 mL, preferably 5-50 mL; for copper meshes with other sizes, the volumes of the deionized water, n-hexane, n-octadecanethiol and absolute ethyl alcohol mixed solutions are expanded or reduced in equal proportion along with the expansion or reduction of the area of the copper mesh surface.
Further, the super-hydrophobic copper mesh obtained in the step (2) or the super-hydrophilic copper mesh obtained in the steps (1) and (3) is adopted for oil-water separation, and when the super-hydrophobic copper mesh is used for heavy oil-water separation or the super-hydrophilic copper mesh is used for light oil-water separation, the oil/water volume ratio is 1:1.
Further, in the step (3), the concentration of the prepared NaOH solution is 2-6M, preferably 4M, and the volume is 10-40 mL, preferably 20mL; the volume of the absolute ethyl alcohol is 5-20 mL, preferably 10mL; the volume ratio of the prepared sodium hydroxide solution to the absolute ethyl alcohol is 2:1; the ultrasonic time of the ultrasonic wave is less than 1 hour, preferably 10 minutes; the standing and soaking time at the normal temperature is less than 90 hours, preferably 50 hours; for copper nets with other sizes, the volumes of the NaOH solution and the absolute ethyl alcohol are expanded or reduced in equal proportion along with the expansion or reduction of the area of the copper net list.
Further, in the step (4), the number of cycles of the cycle is 8.
The invention also provides the super-hydrophobic copper mesh obtained in the step (2) or the super-hydrophilic copper mesh obtained in the step (3) in the regulation and control method.
The invention also provides application of the super-hydrophobic copper mesh obtained in the step (2) in oil-water separation, wherein the oil is heavy oil, and the volume ratio of the heavy oil to the water is 1:1; the super-hydrophilic copper net obtained in the step (1) or (3) is applied to oil-water separation, wherein the oil is light oil, and the volume ratio of the light oil to the water is 1:1.
Further, the super-hydrophilic copper mesh obtained in the step (3) has the following oil-water separation operation modes in oil-water separation: the deionized water and the light oil are measured according to the volume ratio of 1:1 and mixed together, the light oil is one or more of n-hexane, cyclohexane and benzene, and the mixed liquid of the light oil and the deionized water is poured into an oil-water separator which is clamped with a super-hydrophilic copper mesh, so that the separation efficiency is more than 99%.
Further, the super-hydrophobic copper mesh obtained in the step (2) has the following oil-water separation operation modes in oil-water separation: the deionized water and heavy oil (the heavy oil is preferably methylene dichloride) are measured according to the volume ratio of 1:1 and mixed together, and the mixed solution of the deionized water and the heavy oil is poured into an oil-water separator which is clamped with a super-hydrophobic copper mesh, so that the separation efficiency is more than 99%.
Compared with the prior art, the invention has the beneficial effects and advantages that:
1. the method adopts simple process to preparePreparing super-hydrophobic copper net, taking copper net as substrate, using NaOH and (NH) 4 ) 2 S 2 O 8 And (3) serving as a chemical etchant, and modifying by using the ODT to obtain the super-hydrophobic copper mesh. The super-hydrophobic structure is stable, the cost is low, the preparation method is simple and convenient, and the requirement of mass production is met.
2. In the prior art, the wettability of a material surface can be changed by external stimuli (e.g. temperature, light, pH, potential and magnetic field) only when the material surface is responsive to a chemical surface. In this regard, the present invention achieves a breakthrough. The regulating and controlling method of the invention ensures that the material surface wettability has the characteristics of simplicity, convenience, aging, no damage and the like in the cycle between superhydrophobicity and superhydrophilicity, and can provide a feasible way for large-scale manufacturing of intelligent surfaces with reversible superhydrophilicity.
Drawings
FIG. 1 is a schematic view of an oil-water separator used in an embodiment of the present invention; two identical sand core measuring cylinders (the diameter of the pipe orifice is 1.6 cm) are used as an upper pipe and a lower pipe, the pipe orifices are tightly connected, a copper net is clamped and placed at the joint of the pipe orifices of the two measuring cylinders by a clamp, the two measuring cylinders are fixed, and then the copper net is modified or oil-water separation is carried out; the whole copper mesh modification and oil-water separation process is shown in the figure, wherein deionized water is dyed with methyl orange for observation.
Fig. 2 is a graph of contact angle for various amounts of deionized water for various mesh copper grids.
FIG. 3 is a graph of contact angle for different concentrations of ODT-absolute ethanol mixed solution.
FIG. 4 is a graph of contact angle for different volumes of ODT-absolute ethanol mixed solution.
Fig. 5 is a graph of contact angles under different volumes of n-hexane.
Fig. 6 is a graph of contact angles under different types of light oils (n-hexane, cyclohexane, benzene).
FIG. 7 shows the comparison of the flow rates (a) and separation efficiency (b) of water and light oil (n-hexane) on the surface of the super-hydrophilic copper mesh obtained in the step (b) of example 1.
Fig. 8 is a graph of oil-water separation efficiency of the super-hydrophobic copper mesh for separating heavy oil.
Fig. 9 is a diagram showing the oil-water separation efficiency of light oil from a superhydrophobic copper mesh to a superhydrophilic copper mesh after alkali soaking.
Fig. 10 is an SEM image of the original copper mesh, super-hydrophilic copper mesh, super-hydrophobic copper mesh, and alkali blister copper mesh.
Fig. 11 is an XPS diagram of a superhydrophobic copper mesh (left) and a superhydrophilic copper mesh (right) after alkali soaking.
Fig. 12 is a graph of the time relationship between the transition of wettability of a copper mesh from superhydrophobic to superhydrophilic at the time of alkali soaking: the contact angle measurements in the left plot were spaced 1 hour apart; the right plot is the reduction of the contact angle measurement interval to 20 minutes for the 49 th to 50 th hour period in the left plot.
Detailed Description
The technical solution of the present invention is further described below with reference to the drawings and specific examples in the specification, and is only for illustrating the present invention, and should not be construed as limiting the present invention.
Copper mesh of each mesh used in the following examples was a red copper mesh (purity: 99%) having a length, width and thickness of 2.5cm, 2.5cm and 0.09mm in this order.
Example 1
This example is used to illustrate the method of making a super-wettable copper net.
The preparation method of the super-hydrophobic copper mesh comprises the following steps in sequence:
(a) Sequentially cleaning copper nets with deionized water and ethanol, wherein the copper nets are respectively 100 meshes, 200 meshes, 300 meshes and 500 meshes so as to remove pollutants on the surfaces of the copper nets;
(b) Immersing the copper mesh cleaned in the step (a) into NaOH and (NH) 4 ) 2 S 2 O 8 For 30 minutes, the concentration of NaOH in the mixed solution is 1M, (NH) 4 ) 2 S 2 O 8 Is 0.05M to obtain Cu (OH) formed on the surface 2 Is a super hydrophilic copper net.
(c) Fixing the super-hydrophilic copper mesh in step (b) at a proper position between two clamps of the oil-water separator; then pouring deionized water into the upper pipe; subsequently, n-hexane is added, the deionized water poured in before flows through the copper mesh, and the n-hexane is remained above the copper mesh; then, a mixed solution of n-Octadecanethiol (ODT) and absolute ethyl alcohol is poured in, and after a certain time, n-hexane initially remained above the super-hydrophilic copper mesh flows through the copper mesh. And taking out the copper mesh, and then sequentially cleaning the copper mesh with enough ethanol and deionized water to obtain the super-hydrophobic copper mesh.
Example 2
The present example is to illustrate the effect of deionized water amount on copper mesh superhydrophobicity.
In the process of modifying the super-hydrophilic copper mesh into super-hydrophobic, the ODT concentration of the mixed solution of the ODT and the absolute ethyl alcohol is respectively 0.03M, 0.04M, 0.05M, 0.06M and 0.07M, the volume of the mixed solution is 20mL, the volume of the n-hexane is 15mL, and the amount of the poured deionized water is respectively 10, 20, 40, 60, 80 and 100mL. Then measuring contact angles of 100 meshes, 200 meshes, 300 meshes and 500 meshes (the contact angle measuring instrument JC2000D1 is the same and is not repeated, and the test result is shown in the specification of figure 2 (1)
(5) The change in contact angle was observed for different amounts of deionized water (contact angle was relatively large when the copper mesh was modified with ODT/ethanol at a concentration of 0.05M).
Example 3
The embodiment is used for explaining the influence of the mixed solution of ODT (on-the-fly) and absolute ethyl alcohol with different concentrations on the superhydrophobicity of the copper mesh.
In the process of modifying the super-hydrophilic copper mesh into super-hydrophobic copper mesh, the deionized water amount is 10mL, the volume of n-hexane is 15mL, the volume of ODT-ethanol solution is 20mL, and the ODT concentration of the ODT and absolute ethanol mixed solution is 0.03M, 0.04M, 0.05M, 0.06M and 0.07M respectively. The contact angle was then measured and the test results are shown in fig. 3, and the change in contact angle was observed for different concentrations of ODT and absolute ethanol mixed solutions.
Example 4
This example is used to illustrate the effect of different volumes of ODT and absolute ethyl alcohol mixed solutions on copper mesh superhydrophobicity.
In the process of modifying the super-hydrophilic copper mesh into super-hydrophobic copper mesh, the deionized water amount is 10mL, the volume of n-hexane is 15mL, the ODT concentration of the mixed solution of ODT and absolute ethyl alcohol is 0.05M, and the volumes of the added ODT and absolute ethyl alcohol mixed solution are 5mL, 10mL, 15mL, 20mL, 25mL, 30 mL, 35 mL, 40mL, 45 mL and 50mL respectively. The contact angle was then measured and the test results are shown in fig. 4, and the change in contact angle for different volumes of ODT and absolute ethanol mixed solution was observed.
Example 5
This example illustrates the effect of different volumes of n-hexane on copper mesh superhydrophobicity.
In the process of modifying the super-hydrophilic copper net into super-hydrophobic copper net, the deionized water amount is 10mL, the ODT concentration of the mixed solution of the ODT and the absolute ethyl alcohol is 0.05M, the volume is 20mL, and the volumes of the added n-hexane are 5mL, 10mL, 15mL, 20mL and 25mL respectively. The contact angle was then measured and the test results are shown in fig. 5, observing the change in contact angle under different volumes of n-hexane.
Example 6
The embodiment is used for explaining the influence of three different types of light oil, namely n-hexane, cyclohexane and benzene, on the superhydrophobicity of the copper net.
In the process of modifying the super-hydrophilic copper net into super-hydrophobic copper net, deionized water is 10mL, ODT concentration of the ODT-ethanol solution is 0.05M, the volume is 20mL, and n-hexane, cyclohexane and benzene are respectively added into the solution in a parallel test mode, wherein 15mL of each of the n-hexane, cyclohexane and benzene is added into the solution. The contact angle was then measured and the test results are shown in fig. 6, and the change of the contact angle under different types of light oil such as n-hexane, cyclohexane and benzene was observed.
Example 7
This example is used to illustrate the oil-water separation of a super-wettable copper net.
The super hydrophilic copper net with different mesh numbers, which is obtained in the step (b) of the example 1, is adopted to measure the oil flux and the oil-water separation, and the subsequent copper net required by the subsequent test is selected from the super hydrophilic copper net. The test results are shown in fig. 7, wherein the 100-mesh super-hydrophilic copper mesh is too large to separate the oil-water mixture, and the subsequent experiments are no longer used. 200 mesh, 300 mesh and 500 mesh super hydrophilic copper mesh has oil-water mixture separation efficiency (eta= (m) 1 /m 0 ) 100%, η represents the separation efficiency of the immiscible oil-water mixture, m 0 And m 1 Respectively representing the weight of the water before and after separation, and not described in detail below) can be achieved99% or more.
Selecting proper super-hydrophobic copper net: selecting a proper super-hydrophobic copper net according to the contact angle shown in the graph of the test result, the deionized amount, the concentration and the volume of the mixed solution of ODT and absolute ethyl alcohol, the volume of n-hexane and the contact angle under different types of light oil conditions:
the 200-mesh super-hydrophilic copper mesh is treated by 10mL of deionized water, 10mL of normal hexane, 0.05M ODT and 20mL of absolute ethyl alcohol mixed solution to obtain the super-hydrophobic copper mesh;
the 300-mesh super-hydrophilic copper mesh is treated by 20mL of deionized water, 15mL of n-hexane, 0.05M ODT and 20mL of absolute ethyl alcohol mixed solution to obtain the super-hydrophobic copper mesh;
the 500-mesh super-hydrophilic copper mesh is treated by 20mL of deionized water, 15mL of n-hexane, 0.04M ODT and 20mL of absolute ethyl alcohol mixed solution to obtain the super-hydrophobic copper mesh.
And (3) carrying out heavy oil (the heavy oil is methylene dichloride) separation test on the selected super-hydrophobic copper net, wherein the test results are shown in figure 8, and the separation efficiency is over 99 percent.
Alkali soaking the selected super-hydrophobic copper net: preparing 20mL of 4M NaOH solution, adding 10mL of absolute ethyl alcohol, mixing to obtain a mixed solution, putting the selected super-hydrophobic copper mesh into the mixed solution, and carrying out ultrasonic treatment under a sealing condition for 10min to enable the super-hydrophobic copper mesh and the mixed solution to fully mutually dissolve and react; after the ultrasonic treatment is finished, standing and soaking are carried out at normal temperature under a sealing condition until the wettability of the copper mesh is changed from super-hydrophobic to super-hydrophilic.
And (3) carrying out light oil-water separation on the copper mesh after the alkali soaking. The test result is shown in fig. 9, the 200 mesh copper net has no separation effect due to large aperture, and the separation efficiency of 300 mesh and 500 mesh copper nets can basically reach more than 99%. The alkali soaking time of the 300-mesh and 500-mesh copper mesh is respectively 50h and 90h, and finally, the superhydrophobic copper mesh obtained by treating the 300-mesh superhydrophilic copper mesh with 20mL of deionized water, 15mL of n-hexane, 0.05M ODT and 20mL of absolute ethyl alcohol mixed solution is selected for subsequent experiments.
Example 8
This example is an SEM characterization of a super-wettable copper mesh.
SEM characterization of the copper mesh obtained in example 1, as shown in fig. 10 of the specification, revealed that the cleaned copper mesh had a smooth surface (fig. 10a 1 -a 4 ) The method comprises the steps of carrying out a first treatment on the surface of the After alkaline oxidation, the copper mesh surface forms Cu (OH) 2 Surface structure, cu (OH) 2 In the form of nanoneedle structure (FIG. 10b 1 -b 4 ) The method comprises the steps of carrying out a first treatment on the surface of the The superhydrophobic copper net of example 7 modified with the mixed solution of deionized water, n-hexane, ODT and absolute ethanol, on which nanowires were tightly adhered to each other on the surface (fig. 10c 1 -c 4 ) The method comprises the steps of carrying out a first treatment on the surface of the In example 7, the super-hydrophilic copper mesh obtained after soaking in a mixed solution of sodium hydroxide and absolute ethyl alcohol was subjected to SEM characterization, and a microchip structure was formed on the surface (FIG. 10d 1 -d 3 )。
Example 9
This example is an XPS characterization of a super-wettability copper mesh.
XPS characterization was performed on the super-hydrophobic copper mesh (300 mesh) obtained in example 7 and the super-hydrophilic copper mesh (300 mesh) after alkali soaking, and the results are shown in the left and right graphs of FIG. 11, respectively, wherein the peak value of two XPS spectra S2P appears at 163.3eV. Comparing the proportion of S element, the proportion of S element is high when hydrophobic, and the S element content of the hydrophilic copper net after alkali soaking is low.
Example 10
This example is a contact angle test of a 300 mesh superhydrophobic copper net obtained in example 7. The super-hydrophobic copper mesh is converted from super-hydrophobic to super-hydrophilic in the alkaline soaking stage, the test result is shown in fig. 12, and the super-hydrophobic copper mesh is converted into super-hydrophilic copper mesh from 50 h.
Example 11
The embodiment is a recycling process of converting the 300-mesh super-hydrophobic copper mesh into the super-hydrophilic copper mesh in the embodiment 7, and one copper mesh can be recycled for 8 times.
Claims (10)
1. The method for regulating and controlling the wettability of the oil-water separation material is characterized by comprising the following steps of:
step (1), preparing a super-hydrophilic oil-water separation material:
firstly, sequentially cleaning a copper mesh by deionized water and acetone or deionized water and ethanol to remove pollutants on the surface of the copper mesh;
next, the cleaned copper mesh was immersed in NaOH and (NH) 4 ) 2 S 2 O 8 To obtain Cu (OH) formed on the surface 2 Is a super hydrophilic copper net;
step (2), converting the super-hydrophilic copper mesh obtained in the step (1) into a super-hydrophobic copper mesh:
firstly, fixing the super-hydrophilic copper mesh prepared in the step (1) at a proper position between two clamps of an oil-water separator; then pouring deionized water into the upper pipe; subsequently, adding n-hexane into the upper pipe, and allowing deionized water to flow through the super-hydrophilic copper mesh, wherein the n-hexane is remained above the super-hydrophilic copper mesh; then pouring the mixed solution of n-octadecanol and absolute ethyl alcohol into the upper pipe, and after a certain time, enabling the n-hexane initially remained above the super-hydrophilic copper net to flow through the super-hydrophilic copper net; finally, taking out the super-hydrophilic copper net, and sequentially cleaning the super-hydrophilic copper net with ethanol and deionized water, wherein the super-hydrophilic copper net is converted into a super-hydrophobic copper net;
step (3), converting the super-hydrophobic copper mesh obtained in the step (2) into a super-hydrophilic copper mesh:
mixing the prepared NaOH solution and a proper amount of absolute ethyl alcohol to obtain a NaOH-absolute ethyl alcohol mixed solution, soaking the super-hydrophobic copper mesh prepared in the step (2), and carrying out ultrasonic treatment under a sealing condition together with the NaOH-absolute ethyl alcohol mixed solution to enable the super-hydrophobic copper mesh and the NaOH-absolute ethyl alcohol mixed solution to fully mutually dissolve and react; after the ultrasonic treatment is finished, standing and soaking for not more than 96 hours at normal temperature under a sealing condition, wherein the super-hydrophobic copper mesh is converted into a super-hydrophilic copper mesh;
after the super-hydrophilic copper net obtained in the step (4) and the step (3) is kept in a super-hydrophilic state for 1-2 days, spontaneously converting the super-hydrophilic copper net into a super-hydrophobic copper net, and repeating the step (3) on the super-hydrophobic copper net to convert the super-hydrophobic copper net into the super-hydrophilic copper net again; thus, the circulation of the wettability of the copper mesh between superhydrophilic and superhydrophobic is realized in a reciprocating manner.
2. The method according to claim 1, wherein in the step (1), the mesh number of the copper mesh is one or more of 100 mesh, 200 mesh, 300 mesh, 400 mesh, and 500 mesh; said NaOH and (NH 4 ) 2 S 2 O 8 Is composed of NaOH solution and (NH) 4 ) 2 S 2 O 8 The solution is mixed to obtain a mixed solution, the concentration of NaOH in the mixed solution is below 4M, preferably 1M, and the concentration of (NH in the mixed solution 4 ) 2 S 2 O 8 The concentration of (2) is 2M or less, preferably 0.05M; the immersion in NaOH and (NH) 4 ) 2 S 2 O 8 The time in the mixed solution of (2) is 10 minutes to 1 hour, preferably 30 minutes; the active ingredient of the super-hydrophilic copper net is Cu (OH) 2 。
3. The method according to claim 1, wherein in the step (2), the active ingredient of the superhydrophobic copper net is n-octadecanethiol; for copper nets with the length, the width and the thickness of 2.5cm, 2.5cm and 0.09mm in sequence, the volume of deionized water is 10-200 mL, preferably 10-100 mL; the volume of the n-hexane is 5-50 mL, preferably 5-25 mL; the concentration of the n-octadecanethiol in the mixed solution of the n-octadecanethiol and the absolute ethyl alcohol is 0.01-1M, preferably 0.03-0.07M, and the volume is 5-100 mL, preferably 5-50 mL; for copper meshes with other sizes, the volumes of the deionized water, n-hexane, n-octadecanethiol and absolute ethyl alcohol mixed solutions are expanded or reduced in equal proportion along with the expansion or reduction of the area of the copper mesh surface.
4. The method according to claim 1, wherein in the step (3), for copper mesh with length, width and thickness of 2.5cm, 2.5cm and 0.09mm in order, the concentration of the prepared NaOH solution is 2-6M, preferably 4M, and the volume is 10-40 mL, preferably 20mL; the volume of the absolute ethyl alcohol is 5-20 mL, preferably 10mL; the volume ratio of the prepared sodium hydroxide solution to the absolute ethyl alcohol is 2:1; the ultrasonic time of the ultrasonic wave is less than 1 hour, preferably 10 minutes; the standing and soaking time at the normal temperature is less than 90 hours, preferably 50 hours; for copper nets with other sizes, the volumes of the NaOH solution and the absolute ethyl alcohol are expanded or reduced in equal proportion along with the expansion or reduction of the area of the copper net list.
5. The method according to claim 1, wherein in the step (4), the number of cycles is 8.
6. The use of the super-hydrophobic copper mesh obtained in step (2) in the regulation method of any one of claims 1 to 4 in oil-water separation, wherein the oil is heavy oil or light oil.
7. The use according to claim 6, characterized in that: the volume ratio of the oil to the water is 1:1.
8. The use of the super-hydrophilic copper mesh obtained in step (3) in the regulation method of any one of claims 1 to 4 for oil-water separation, wherein the oil is light oil.
9. The use according to claim 8, characterized in that: the volume ratio of the oil to the water is 1:1.
10. A superhydrophobic copper net obtained in step (2) or a superhydrophilic copper net obtained in step (3) in the regulation method of any one of claims 1-4.
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