CN107684743B - Liquid-liquid separation method constructed by fiber bundle solid surface force field difference - Google Patents
Liquid-liquid separation method constructed by fiber bundle solid surface force field difference Download PDFInfo
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- CN107684743B CN107684743B CN201710764542.XA CN201710764542A CN107684743B CN 107684743 B CN107684743 B CN 107684743B CN 201710764542 A CN201710764542 A CN 201710764542A CN 107684743 B CN107684743 B CN 107684743B
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Abstract
The invention discloses a liquid-liquid separation method constructed by the difference of force fields on the solid surface of a fiber bundle. The method comprises the following steps: the oil-water mixed liquid to be separated flows through the gap between the fiber bundle A and the fiber bundle B, and the surfaces of the fiber bundle A and the fiber bundle B respectively have oleophylic hydrophobicity and hydrophilic oleophylic lipophobicity; different adhesion forces are generated by virtue of the surface force field difference of the surfaces of the fiber bundle A and the fiber bundle B to the oil-water mixed liquid, and the passing liquid is collected and is static to realize oil-water separation. The separation method provided by the invention not only comprises the coalescence and separation processes of the dispersed phase, but also comprises the coalescence and separation processes of the continuous phase, so that the separation time is shortened, the separation effect is improved, and the separation method has good effects in an oil-water separation process, a demulsification process and an extraction process.
Description
Technical Field
The invention particularly relates to a liquid-liquid separation method constructed by the difference of force fields on the solid surface of a fiber bundle.
Background
The physical and chemical changes generated in the preparation and use processes of the material are gradually performed from the surface of the material to the interior of the material, and the processes are performed depending on the surface structure and properties of the material. The materials that one normally encounters and uses are limited in their bulk size, i.e., the material always has a surface exposed to the medium with which it comes into contact. A series of physicochemical reactions occur at the interface where they are in contact with each other, either rapidly or slowly. The root cause of the surface phenomenon is that the particle arrangement on the surface of the material is different from that in the interior of the material, and the surface of the material is in a high-energy state.
The interface of a solid can be generally divided into a surface, an interface and a phase interface, wherein the surface refers to the interface between the solid and a vacuum (without considering adsorption), the interface refers to the interface between two adjacent crystallization spaces, also called a 'grain boundary', the phase interface refers to the interface between adjacent phases, and the phase interface has three types, such as the phase interface (s/s) between a solid phase and a solid phase, the phase interface (s/g) between a solid phase and a gas phase, and the phase interface (s/L) between a solid phase and a liquid phase.
Inhomogeneities in the solid surface are caused by production, processing conditions, lattice defects, vacancies or dislocations. Compared with liquid, the surface free energy and surface tension of solid have the following differences: 1) the surface free energy of a solid contains elastic energy. 2) The surface tension of the solid is anisotropic. 3) The surface of an actual solid is mostly in a non-equilibrium state, and the conditions under which the solid surface is formed and the history it experiences are the main factors that determine the morphology of the solid surface.
The attraction on the surface of a solid is generated by the interaction of the surface force field of the solid and the force field of the particle to be attracted, and the interaction is called solid surface force. Depending on the nature, the surface forces can be divided into: chemical forces and molecular attraction.
The presence of surface forces places the solid surface in a higher energy state. The system always reduces this excess energy through various means, which causes polarization, distortion, rearrangement of surface particles and distortion of the original lattice. The liquid reduces the surface energy of the system by forming a spherical surface, while crystals can only be achieved by means of ion polarization or displacement because the particles cannot flow freely, resulting in structural differences between the surface and the interior.
Aiming at the pretreatment of crude oil desalting and dewatering, the American MERICHEM company develops a static contact device by using a hydrophilic fiber membrane, a bundle of continuous small-diameter fibers with long beam lengths are arranged in a reactor, when an oil phase and a water phase flow downwards along the fibers respectively, the water phase is pulled into an extremely thin membrane by the fibers due to different surface tension and fiber affinity, so that the small-volume water phase is expanded into a large-area liquid membrane, at the moment, the oil phase flows down from the fibers soaked by the water phase, the liquid membrane is thinner due to the friction force between the oil phase and the liquid membrane, the two phases are in contact on the planar membrane, and mass transfer is performed in the contact process. The process is successfully applied to the alkali washing process of straight-run diesel oil and catalytic cracking diesel oil, so that the diesel oil and alkali flow through the metal fiber bundle in the fiber membrane contactor from top to bottom to reach the bottom of the alkali washing tank, the desulfurization reaction and the mass transfer process are completed in the process, and oil and alkali are separated when the diesel oil and the alkali reach the bottom. The process only utilizes the hydrophilic surface of the fiber to carry out water phase coalescence, and the device is easy to block in the practical application process, particularly the crude oil dehydration and desalination process.
Disclosure of Invention
The invention aims to provide a liquid-liquid separation method constructed by the force field difference of the solid surface of a fiber bundle, so that the liquid-liquid separation method has good application effects in an oil-water separation process, a demulsification process and an extraction process.
In order to achieve the purpose, the technical effects are as follows:
a liquid-liquid separation method constructed by the difference of the force field of the solid surface of a fiber bundle comprises the following steps:
the oil-water mixed liquid to be separated flows through the gap between the fiber bundle A and the fiber bundle B, and the surfaces of the fiber bundle A and the fiber bundle B respectively have oleophylic hydrophobicity and hydrophilic oleophylic lipophobicity; by means of the difference of the surface force fields of the fiber bundle A and the fiber bundle B, different adhesion forces are generated on an oil phase and a water phase in the oil-water mixed liquid, and the passing liquid is collected and stands still to realize oil-water separation.
According to the scheme, the fiber bundle A and the fiber bundle B are cylindrical fiber bundles, and the ring layers of the fiber bundle A and the ring layers of the fiber bundle B are closely and alternately arranged.
According to the scheme, the fiber bundle A is copper fiber bundle which is treated with NaOH and K2S2O8After the solution is soaked, a layer of uniform needle-shaped copper hydroxide film is generated on the surface, and then the needle-shaped copper hydroxide film is soaked by an ethanol solution of n-dodecyl mercaptan, so that a super-hydrophobic and super-oleophylic surface is obtained.
According to the scheme, the fiber bundle B is a stainless steel fiber bundle, the surface of the fiber bundle B is coated with thermosetting resin solution, after the coating is cured, silicon carbide powder is sprayed on the surface of the fiber bundle B, and the silicon carbide powder is heated and cured to form the silicon carbide hydrophilic oleophobic surface.
According to the scheme, the fiber bundle A is a copper fiber bundle, which is etched in a nitric acid solution and then soaked in hexadecyl mercaptan to form the super-hydrophobic and super-oleophilic surface.
According to the scheme, the fiber bundle B is an ABS resin fiber bundle, and the surface of the fiber bundle B is sprayed with a polyvinylpyrrolidone solution to form a hydrophilic oleophobic surface.
According to the scheme, the fiber bundle A is a polyester resin fiber bundle, and a layer of organic silicon nanowires is deposited on the surface of polyester at room temperature and in air atmosphere by a one-step method through a chemical vapor deposition method, so that the organic silicon nanowires have super-hydrophobicity and super-lipophilicity.
According to the scheme, the fiber bundle B is a stainless steel fiber bundle, the surface of the fiber bundle B is coated with a thermosetting resin solution, after the coating is cured, nano titanium dioxide powder is sprayed on the surface of the fiber bundle B, and the nano titanium dioxide powder is heated and cured to form the hydrophilic and oleophobic surface of the titanium dioxide.
According to the scheme, the fiber bundle A is a stainless steel fiber bundle, the surface of the stainless steel fiber bundle is coated with a thermosetting resin solution, graphite powder is sprayed on the surface of the stainless steel fiber bundle after the coating is cured, and the graphite powder is heated and cured to form a hydrophobic oleophilic surface of the graphite powder.
According to the scheme, the fiber bundle B is a stainless steel fiber bundle, polyethylene glycol diacrylate and ethoxylated trimethylolpropane triacrylate are used as film forming substances, and hydrophilic nano SiO is doped2The sol structure rough structure and the end alkenyl long-chain methoxy polyethylene glycol acrylate structure molecular brush structure are coated on the surface of stainless steel, and the ultra-hydrophilic and ultra-oleophobic surface is prepared by adopting a UV curing method.
When a certain amount of liquid capable of wetting two solid surfaces exists between the two closely-spaced solid surfaces, a connected system called a liquid bridge can be formed between the two solid surfaces under the action of the adhesion force of the liquid and the two solid surfaces. The liquid bridge mainly has the functional characteristics of both transportation and connection. Transport characteristics are expressed as mass transfer and heat convection of the liquid. The coupling characteristic is expressed as a pulling force of the liquid on the two solid surfaces and a continuous liquid film is formed between the two solid surfaces. The root cause is the surface tension of the liquid, and the liquid bridge force is characterized by the surface tension effect of the curved surface of the liquid, and the substantial cause is the adhesion of the liquid and the solid and the cohesion between the liquid and the liquid. When the liquid contacts the wettable solid, the liquid and the solid surface are adhered, and at the same time, the liquid has cohesion, so that the liquid in the liquid bridge system has a pulling effect on the solid surface. Studies have shown that when solids are hydrophilic, their adhesive strength is greater than the cohesive strength. Therefore, the super-hydrophilic and super-oleophobic net film is considered to have the potential hydrophilicity of the film, so that water can generate an adhesion and pulling effect in capillary pores of the film to form a liquid bridge, and meanwhile, a water source is continuously transmitted based on the mass transfer effect of the liquid bridge. And because the liquid film formed by the water plays a role in isolating mass transfer on the oil, the oil cannot contact the surface of the film and cannot penetrate. Therefore, when the water-oil emulsion forms a liquid bridge on two different solid surfaces which are close to each other, one solid surface generates an adhesion effect on water, the other solid surface generates an adhesion effect on oil, and the oil and the water can be separated by the pulling effect in different directions.
The invention arranges two materials with different surface force fields oppositely, so that oil-water mixed liquid to be separated passes through the materials, and because the surface force fields of the materials are different and the affinity to oil phase and water phase is different, the liquid can automatically coalesce to the surface with the affinity to form large liquid drops, thereby achieving the effect of liquid-liquid separation.
The invention has the following beneficial effects:
the liquid-liquid separation method constructed by the force field difference of the solid surface is applied to the liquid-liquid separation process in the chemical field, such as an oil-water separation process, a demulsification process and an extraction process, and has good effect.
The separation of the two phases, liquid-liquid, is in fact a process in which the droplets of the dispersed phase coalesce and separate in the continuous phase, the coalescence process being carried out in three stages: droplet capture, droplet coalescence, and droplet settling. The separation method of the invention not only comprises the coalescence and separation processes of the dispersed phase, but also comprises the coalescence and separation processes of the continuous phase, thereby shortening the separation time and improving the separation effect.
In addition, because the separation device designed by the invention has close distance between different solid surfaces, the liquid-liquid mixture passes through the middle in a film mode, thereby greatly improving the separation area and further increasing the separation effect.
Drawings
FIG. 1: the invention discloses a schematic diagram of a construction method of fiber bundle solid surface force field difference.
Detailed Description
The following examples further illustrate the technical solutions of the present invention, but should not be construed as limiting the scope of the present invention.
Example 1
The fiber bundle A is copper fiber bundle, and is treated with NaOH and K2S2O8After the copper fiber bundle is soaked in the solution, a layer of uniform needle-shaped copper hydroxide film is generated on the surface of the Cu, and then the copper fiber bundle is soaked in an ethanol solution of n-dodecyl mercaptan, so that the copper fiber bundle with super-hydrophobicity and super-lipophilicity is obtained. The contact angle of the copper fiber bundle with water was 151 °.
And selecting a stainless steel fiber bundle as the fiber bundle B, coating the surface of the stainless steel fiber bundle with a thermosetting resin solution, spraying silicon carbide powder on the surface of the stainless steel fiber bundle after the solvent is volatilized, and heating and curing to form the silicon carbide hydrophilic oleophobic surface coating.
According to the technical principle and scheme of the patent, the fiber bundles A and B after surface modification are oppositely arranged according to the attached drawing 1, an oil-water mixture passes between the fiber bundles A and B, different adhesion forces are generated due to the difference of surface force fields of the surfaces of the fiber bundles A and B to oil water, and the passing liquid is collected and is static to realize oil-water separation.
Example 2
The fiber bundle A is copper fiber bundle, which is etched with 4 mol/L nitric acid solution for 4min, and then soaked in 1 mmol/L hexadecyl mercaptan for 1hr to produce super-hydrophobic super-oleophylic copper net with contact angle between copper fiber bundle and water maintained at 150 deg.
And selecting a stainless steel fiber bundle as the fiber bundle B, coating the surface of the stainless steel fiber bundle with a thermosetting resin solution, spraying silicon dioxide powder on the surface of the stainless steel fiber bundle after the solvent is volatilized, and heating and curing to form the silicon dioxide hydrophilic oleophobic surface coating.
According to the technical principle and scheme of the patent, the fiber bundles A and B after surface modification are oppositely arranged according to the attached drawing 1, an oil-water mixture passes between the fiber bundles A and B, different adhesion forces are generated due to the difference of surface force fields of the surfaces of the fiber bundles A and B to oil water, and the passing liquid is collected and is static to realize oil-water separation.
Example 3
The fiber bundle A is made of stainless steel fiber bundles, a layer of vertically arranged carbon nanotubes is deposited on the stainless steel by a thermal chemical vapor deposition method, and the carbon nanotubes are hydrophobic and have super-hydrophobicity.
And selecting an ABS resin fiber bundle as the fiber bundle B, and spraying a polyvinylpyrrolidone solution on the surface of the fiber bundle B to form a hydrophilic oleophobic surface coating.
According to the technical principle and scheme of the patent, the fiber bundles A and B after surface modification are oppositely arranged according to the attached drawing 1, an oil-water mixture passes between the fiber bundles A and B, different adhesion forces are generated due to the difference of surface force fields of the surfaces of the fiber bundles A and B to oil water, and the passing liquid is collected and is static to realize oil-water separation.
Example 4
The fiber bundle A is polyester resin fiber bundle, and a layer of organic silicon nanowires is deposited on the surface of polyester by one step at room temperature and in air atmosphere by using a chemical vapor deposition method, so that the organic silicon nanowires have super hydrophobicity and super lipophilicity.
And selecting a stainless steel fiber bundle as the fiber bundle B, coating the surface of the stainless steel fiber bundle with a thermosetting resin solution, spraying nano titanium dioxide powder on the surface of the stainless steel fiber bundle after the solvent is volatilized, and heating and curing to form the titanium dioxide hydrophilic and oleophobic surface coating.
According to the technical principle and scheme of the patent, the fiber bundles A and B after surface modification are oppositely arranged according to the attached drawing 1, an oil-water mixture passes between the fiber bundles A and B, different adhesion forces are generated due to the difference of surface force fields of the surfaces of the fiber bundles A and B to oil water, and the passing liquid is collected and is static to realize oil-water separation.
Example 5
The fiber bundle A is a stainless steel fiber bundle, the surface of the stainless steel fiber bundle is coated with a thermosetting resin solution, after a solvent is volatilized, graphite powder is sprayed on the surface of the stainless steel fiber bundle, and the graphite powder is heated and cured to form a graphite powder hydrophobic oleophylic surface coating.
The fiber bundle B is stainless steel fiber bundle, and is prepared by doping hydrophilic nanometer SiO with polyethylene glycol diacrylate and ethoxylated trimethylolpropane triacrylate as main film forming substances2Coating sol-structured coarse structure and alkenyl long-chain methoxy polyethylene glycol acrylate-structured molecular brush structure on the surface of fiber bundle by adopting UV (ultraviolet) methodThe curing method is used for preparing the super-hydrophilic and super-oleophobic surface, the contact angle of the surface to water and oil in the air is 0 degrees, but the contact angle to oil drops under water is more than 150 degrees, and the surface has the characteristic of low adhesion to the oil drops.
According to the technical principle and scheme of the patent, the fiber bundles A and B after surface modification are oppositely arranged according to the attached drawing, an oil-water mixture passes between the fiber bundles A and B, different adhesion forces are generated due to the difference of surface force fields of the surfaces of the fiber bundles A and B to oil water, and the passing liquid is collected and is static to realize oil-water separation.
The above description is only a preferred embodiment of the present invention, and not intended to limit the scope and the embodiments of the present invention, and it should be appreciated by those skilled in the art that obvious variations such as the use of ABAB multi-stage parallel, or multi-layer structures, etc. may be made by equivalent substitutions and repeated overlapping of the descriptions and illustrations of the present invention.
Claims (7)
1. A liquid-liquid separation method constructed by the force field difference of the solid surface of a fiber bundle is characterized by comprising the following steps:
the oil-water mixed liquid to be separated flows through the gap between the fiber bundle A and the fiber bundle B, and the surfaces of the fiber bundle A and the fiber bundle B respectively have oleophylic hydrophobicity and hydrophilic oleophylic lipophobicity; by means of the difference of surface force fields of the fiber bundle A and the fiber bundle B, different adhesion forces are generated on an oil phase and a water phase in the oil-water mixed solution, and the passing liquid is collected and is static to realize oil-water separation;
the fiber bundle A and the fiber bundle B are cylindrical fiber bundles, and the ring layers of the fiber bundle A and the ring layers of the fiber bundle B are closely and alternately arranged;
the fiber bundle A is copper fiber bundle, and is treated with NaOH and K2S2O8After the solution is soaked, a layer of uniform needle-shaped copper hydroxide film is generated on the surface, then the needle-shaped copper hydroxide film is soaked by ethanol solution of n-dodecyl mercaptan to obtain a super-hydrophobic and super-oleophylic surface,
and the fiber bundle B is a stainless steel fiber bundle, the surface of the fiber bundle B is coated with a thermosetting resin solution, after the coating is cured, silicon carbide powder is sprayed on the surface of the fiber bundle B, and the surface is heated and cured to form the silicon carbide hydrophilic and oleophobic surface.
2. The method for liquid-liquid separation based on the force field difference between the solid surfaces of fiber bundles according to claim 1, wherein the fiber bundle A is made of copper fiber bundle, which is then etched in nitric acid solution and soaked in hexadecyl mercaptan to form a super-hydrophobic and super-oleophilic surface.
3. The method for liquid-liquid separation based on the difference in force field on the solid surface of a fiber bundle according to claim 1, wherein the fiber bundle B is an ABS resin fiber bundle, and a polyvinylpyrrolidone solution is sprayed on the surface of the fiber bundle B to form a hydrophilic oleophobic surface.
4. The method for liquid-liquid separation based on the difference of force field on solid surface of fiber bundle as claimed in claim 1, wherein the fiber bundle A is polyester resin fiber bundle, and a layer of organic silicon nanowires is deposited on the surface of the polyester by one step method at room temperature and in air atmosphere by chemical vapor deposition to make it super-hydrophobic and super-oleophilic.
5. The liquid-liquid separation method based on the differential construction of the force fields on the solid surfaces of the fiber bundles according to claim 1, wherein the fiber bundle B is a stainless steel fiber bundle, the surface of the stainless steel fiber bundle B is coated with a thermosetting resin solution, after the coating is cured, nano titanium dioxide powder is sprayed on the surface of the stainless steel fiber bundle B, and the nano titanium dioxide powder is heated and cured to form a hydrophilic and oleophobic surface of titanium dioxide.
6. The method of claim 1, wherein the fiber bundle A is a stainless steel fiber bundle, the surface of the fiber bundle A is coated with a thermosetting resin solution, and after the coating is cured, graphite powder is sprayed on the surface of the fiber bundle A, and the graphite powder is heated and cured to form a hydrophobic and oleophilic graphite powder surface.
7. Solid surface force field differentiation of fiber bundles according to claim 1The constructed liquid-liquid separation method is characterized in that the fiber bundle B is a stainless steel fiber bundle, polyethylene glycol diacrylate and ethoxylated trimethylolpropane triacrylate are used as film forming substances, and hydrophilic nano SiO is doped2The sol structure rough structure and the end alkenyl long-chain methoxy polyethylene glycol acrylate structure molecular brush structure are coated on the surface of stainless steel, and the ultra-hydrophilic and ultra-oleophobic surface is prepared by adopting a UV curing method.
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| SU1018680A1 (en) * | 1982-02-22 | 1983-05-23 | Томский Инженерно-Строительный Институт Мв И Ссо Рсфср | Apparatus for cleaning liquid oil products from water |
| CN85200013U (en) * | 1985-04-10 | 1985-09-10 | 清华大学 | A device with phase separating membrane for liquid-liquid extracting |
| CN1299693A (en) * | 1999-12-15 | 2001-06-20 | 中国科学院生态环境研究中心 | Oil-water separator with spiral flow channel film |
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| CN103055968A (en) * | 2012-12-31 | 2013-04-24 | 苏州汶颢芯片科技有限公司 | Oil-water-separation micro-fluidic chip and preparation method thereof |
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