CN109289251B - Oil-water separation composite filter material and preparation method thereof - Google Patents
Oil-water separation composite filter material and preparation method thereof Download PDFInfo
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- CN109289251B CN109289251B CN201811417203.5A CN201811417203A CN109289251B CN 109289251 B CN109289251 B CN 109289251B CN 201811417203 A CN201811417203 A CN 201811417203A CN 109289251 B CN109289251 B CN 109289251B
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Classifications
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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
-
- 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
- B01D17/047—Breaking emulsions with separation aids
-
- 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 relates to an oil-water separation composite filter material and a preparation method thereof. The substrate filtering material is a metal filter screen, filter cloth or filter paper, and the pore diameter range of the micropores is 5-300 mu m. The supporting material is a stainless steel supporting structure, and the aperture range is 0.5-10mm. The diameter of the nanometer microparticles is 200nm-2 μm. The nano microparticles are adhered to the surface of the substrate filter material in a dispersing and natural sedimentation mode, so that the change of the surface microstructure of the low-surface-energy coating and the surface modification treatment are realized, and the liquid-liquid two-phase separation material obtained by the method has the advantages of high strength, controllable surface wettability, long service life and the like.
Description
Technical Field
The invention relates to a composite filter material for realizing liquid-liquid two-phase separation by utilizing surface wettability, in particular to a composite filter material for oil-water separation, which can realize high-speed, economical and reliable oil-water separation by optimizing the configuration of a base material and the surface wettability modification treatment scheme. Can be used for treating the oil-water separation problem in the industries of petrochemical industry, machining, kitchen waste treatment and the like, and belongs to the technical fields of mechanical engineering, surface engineering, material science and environmental engineering.
Background
The waste water containing the grease and the oil is called oily waste water, and leakage occurring in the oil extraction, oil refining waste water and oil product transportation and storage processes in the petroleum and petrochemical industry is a main way for generating oily waste water. The discharge of oily wastewater which is not treated effectively in time can cause water quality deterioration, influence crop production, harm aquatic resources and even atmospheric pollution, and finally influence human health. The components with low boiling points in the oily wastewater are easy to volatilize into the atmosphere, so as to pollute the air. The ingestion of high concentrations of petroleum distillates by humans directly through respiration can cause acute poisoning, while accumulation of long-term low concentrations of harmful substances at lower concentrations can also produce toxic effects, ultimately potentially causing injury to the human lungs, central nerves and other organs. The oily wastewater invades into water areas such as lakes, rivers, underground and the like to pollute and destroy drinking water resources. In addition, the floating oil can isolate the contact between the water body and the air, so that the dissolved oxygen of the water body is reduced, and the ecological damage is caused by the influence of the deteriorated water quality on the living environment of aquatic organisms. The oil substances entering the water body or the soil can adhere to the rhizome parts of plants, so that the absorption of the plants to the nutrients in the soil is affected, and the plants can die seriously. If the oil-containing sewage is used for irrigating crops, the yield can be reduced, and the enrichment of harmful substances in the crops can finally influence human health.
With the increasing energy demand and the high-speed development of the energy industry, petroleum leakage accidents frequently occur worldwide, and in addition, a large amount of oil-water mixed liquid is generated in the industrial production activities of crude oil exploitation, mechanical processing, textile dyeing, bio-pharmaceuticals and the like, so that pollution is serious. With the development of national economy and the increasing importance of people on living environment requirements. Various oil-water two-phase separation technologies are proposed according to the difference between the physical and chemical properties of oil substances and water to be treated in the petrochemical industry, machining and other industries. The gravity method is based on the difference of oil substances and water in density to realize oil-water separation, and due to the different relative densities of oil, gas and water, an oil-water mixture with a certain composition forms oil, gas and water phases with a certain proportion under a certain pressure and temperature when the system is in balance. The heavier component droplets will settle under the force of gravity. Gravity settling separation devices are designed according to this basic principle. The air floatation method is mainly based on the density difference or chemical property difference of water and oil, forms tiny bubbles in water on the basis of utilizing the gravity sedimentation principle, and carries flocculation particles to float up to the liquid level to purify the water, thus being an oil-water separation method which is being studied in depth and popularized continuously at home and abroad. The conditions of the air-float process application are such that air bubbles attached to the oil droplets can form oil and gas particles. The rising speed can be obviously improved by replacing the oil density with the particle density because the density difference between water and particles is increased due to the occurrence of bubbles and the particle diameter is larger than that of crude oil drops. The method has the main advantages of simple operation, large investment, large occupied area, small operation elasticity, difficult recovery of oil resources, low separation efficiency and easy secondary pollution. The rotational flow method uses the difference of oil-water density to make the oil-water mixture rotating at high speed generate different centrifugal forces, so as to separate oil from water. Since the centrifugal device can reach very high rotational speed and generate centrifugal force which is up to hundreds of times of gravity acceleration, the centrifugal device can separate oil from water more thoroughly, and only needs short residence time and smaller device volume. Since the centrifugal apparatus has moving parts, it is difficult to maintain daily, and therefore, the centrifugal apparatus is applied only to laboratory analysis apparatuses and places where a reduction in floor space is required. One of the main devices operating using the principle of centrifugal separation is a cyclone, which is a device for physically separating a liquid as a continuous phase from solid particles, droplets or bubbles as a dispersed phase. The greater the density difference between oil and water, the easier the two phases will separate. The larger the particle diameter of the dispersed phase, the larger the difference in velocity of the reverse run between the two phases when equilibrium is reached in the gravity field, and thus the easier the separation, similarly to the case in the gravity field. Chemical methods such as adsorption require a large amount of agents; the cost of the biological filter is too high, and the biological filter is only suitable for treating a small amount of oily water. For oil-containing water in industries such as oil refining, coking, steel and the like, oil-water separation methods such as gravity separation, floatation and the like are generally adopted due to large treatment capacity, high oil-containing concentration and the like. The advantages are familiarity for the same technician and operator, the disadvantages are large investment, large occupied area, small operation elasticity, difficult recovery of oil resource and easy secondary pollution. The membrane filtration operation is simple, and the method is a physical separation method, does not cause secondary pollution and has good use prospect.
Aiming at the defects of the existing oil-water separation method and considering the advantages and defects of membrane filtration in the use process, the special wettability oil-water separation material based on a composite structure is provided, wherein the method comprises the steps of obtaining a novel oil-water separation filter material with high strength, good surface wettability and filtering performance through optimal design of a support material, a substrate filter material, a point surface energy modified adhesion material and nano microparticles.
Disclosure of Invention
The invention aims at overcoming the defects and limitations of materials used in the existing membrane method oil-water separation method, and provides an oil-water separation composite filter material with special wettability and a preparation method thereof based on the surface modification of composite structural materials and nano-microparticles to optimize the surface wettability of the filter material. The oil-water separation composite filter material is based on physical separation realized by the special wettability modified by the low surface energy adhesive material and the nano microparticles, has the characteristics of remarkable separation effect, convenient operation, low cost, easy engineering, no secondary pollution and the like, and is expected to be used for leakage in petroleum exploitation and transportation processes and treatment of oily sewage produced by various industries.
The technical scheme of the invention is as follows:
the invention provides an oil-water separation composite filter material, which comprises a substrate filter material and a support material, wherein the substrate filter material is arranged above the support material, a low-surface-energy adhesion material is arranged above the substrate filter material, and a nano-micro particle film is adhered to the surface of the low-surface-energy adhesion material.
Preferably, the substrate filtering material is a metal filter screen, filter cloth or filter paper, and the micropore size range is 5-300 mu m.
Preferably, the supporting material is a stainless steel supporting structure, and the pore diameter range is 0.5-10mm.
Preferably, the thickness of the nanoparticle film is 1-5 micro-nanoparticles, and the diameter of the nano-microparticles is 200nm-2 μm.
Preferably, the low surface energy adhesive material has a thickness of 10-150 μm.
The invention also provides a preparation method of the oil-water separation composite filter material, which comprises the following steps:
step one: preparing a support material and a base filter material;
selecting a supporting material and a substrate filtering material, and arranging the substrate filtering material on the surface of the supporting material to form a composite structure;
step two: uniformly coating an adhesive material on the surface of a substrate filter material;
step three: and (3) adhering the surface of the adhesive material to the nanoparticle film, and curing the adhesive material to prepare the adhesive material.
Preferably, in the first step, the substrate filter material is disposed on the surface of the support material by sintering or mechanical fixing; the substrate filtering material is selected from a metal filter screen, a filter cloth or a filter paper, and the pore diameter range of the micropores is 5-300 mu m; the supporting material is a stainless steel supporting structure, and the aperture range is 0.5-10mm.
Preferably, in the second step, the adhesive material is uniformly coated on the surface of the substrate filter material by using a spraying or dipping mode; the adhesive material is paint.
Preferably, the thickness of the nanoparticle film in the third step is 1-5 micro-nanoparticles, and the diameter of the nano-nanoparticles is 200nm-2 μm.
Preferably, in the third step, the surface of the adhesive material is adhered with the nanoparticle film, the composite structure obtained in the first step is arranged in the closed space, the nanoparticles are dispersed and suspended in the closed space, and the surface of the substrate filter material forms the nanoparticle film through natural precipitation and adsorption.
The invention has the advantages that:
1. the oil-water separation composite filter material provided by the invention adopts various materials to organically combine: the composite filter material fully plays the functions of all components and has the advantages of high strength, high filtering performance and the like.
2. The invention uniformly coats the low surface energy adhesive material on the surface of the substrate filter material, has the double effects of surface modification and adhesive action, not only can protect the substrate filter material and improve the corrosion resistance and wetting, but also can control the coating thickness by optimizing the coating components and the proportion thereof, thereby realizing the adjustment of the pore size of the substrate filter material.
3. According to the invention, the nano microparticles are adhered to the surface of the substrate filter material in a dispersing and natural sedimentation mode, so that the surface modification of the surface microstructure of the low-surface-energy coating (adhesive material) is realized, the control of the wettability of the surface of the substrate filter material can be realized by using microparticles with different particle sizes, different structural shapes and different deposition densities, and the efficient and rapid selective oil-water separation of oil substances in an oil-water mixture can be realized.
4. The oil-water separation composite filter material with special wettability and the preparation method thereof provided by the invention have the remarkable characteristics of simplicity in operation, low cost, environmental friendliness and the like, and have good engineering application prospects.
Drawings
FIG. 1 is a schematic diagram of a composite screen composed of a support material and a base filter material;
FIG. 2 is a schematic illustration of the formation of a coating of an adhesive material on a surface;
fig. 3 is a schematic diagram of a nanoparticle deposition process.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides an oil-water separation composite filter material, as shown in figures 1-3, which comprises a substrate filter material 2 and a support material 1. The substrate filter material 2 is a porous filter material such as a metal filter screen, filter cloth or filter paper, the pore diameter range of the micropores is 5-300 mu m, and the thickness of the substrate filter material in the pore diameter range is about 0.1-0.5 mm. The supporting material 1 is a stainless steel supporting structure with the aperture range of 0.5-10mm or other supporting framework structures without limiting the aperture range, and the thickness is generally about 0.2-0.5 mm. The substrate filter material 2 is attached above the support material 1, the support material is used as a support framework, and the support material 1 has certain strength, so that the support material 1 can be enclosed to be cylindrical, and the substrate filter material 2 can be attached to the outer surface of the cylindrical support material 1 and fixed in the direction of the upper opening and the lower opening of the cylindrical support material; as shown in fig. 1, the high-strength support material 1 and the base filter material 2 may be sintered to form a composite filter material. The surface of the substrate filter material 2 is provided with a low surface energy adhesive material 3 which has double functions of adhesion and surface modification, the viscosity of the low surface energy adhesive material 3 and the component proportion of curing time are adjusted, parameters such as the film thickness of the adhesive material 3 on the surface of the substrate filter material 2 can be controlled, the viscosity of the low surface energy adhesive material 3 is controlled by adding a thinner, and the general weight percentage of the thinner is 20-30%; the curing time is the standing time (crosslinking curing) after adding the curing agent and stirring uniformly, the curing time is 5-15 minutes, and the general usage amount (mass percent) of the curing agent is 5-15%; the brush thickness of the low surface energy adhesive material 3 when formed into a film is generally 10 to 150 μm. Typically the low surface energy adhesive material 3 is a paint. The control of the thickness of the coating formed by the low surface energy adhesive material 3 as shown in fig. 2 can be optimized for the filter material structure; the material treated by the low surface energy adhesive has certain hydrophobic and oleophylic properties and has an adhesive function, the surface of the low surface energy adhesive material 3 is adhered with a nano-micro particle layer 4, the thickness of the nano-micro particle layer 4 is 1-5 times of the diameter of the nano-micro particle 5, and generally, the diameter of the nano-micro particle 5 is 200nm-2 mu m, and the nano-micro particle can be hydrophobic silicon dioxide or other nano-micro particles. When the nano-microparticles 5 are adhered, the nano-microparticles 5 with the particle size of 200nm-2 μm are dispersed in a closed space, and the nano-microparticles 5 are adsorbed on the surface of the substrate filter material coated with the adhesive material 3 in a natural sedimentation mode, as shown in fig. 3, and the nano-microparticles 5 are deposited to modify the surface microstructure of the substrate filter material 2, so that the surface wettability of the substrate filter material 2 is further optimized.
The preparation method of the oil-water separation composite filter material comprises the following steps:
step one: preparation of support and base Filter Material
A metal or other material filter screen with good rigidity strength and aperture of 0.5-10mm is selected as a supporting material, the thickness of the metal or other material filter screen with the aperture of 5-300 mu m is selected as a base filter material, the thickness of the base filter material is 0.1-0.5mm, and the base filter material is arranged on the surface of the supporting material in a mode of sintering, mechanical fixing, and the like to form a composite structure.
Step two: the surface of the substrate filter material is uniformly coated with the adhesive material by spraying or dipping, etc., the thickness is 10-150 μm, the dipping is preferably 10-50 μm, and the spraying is preferably 50-150 μm. When the curing agent is added into the adhesive material, the adhesive material is stirred uniformly, and then the adhesive material is kept still for a certain time to increase the viscosity of the adhesive material, and then the adhesive material is uniformly coated on the surface of the substrate filter material by adopting modes such as spraying or dipping.
Step three: and (3) adhering the surface of the adhesive material to the nanoparticle film, and curing the adhesive material to prepare the adhesive material.
The method comprises the steps of dispersing and suspending nanometer microparticles such as hydrophobic silica with the particle size of 200nm-2 mu m in a closed space by utilizing a blowing stirring mode (the compressed air pressure is 0.4-0.8MPa and the caliber of a nozzle is 2 mm), forming a nanometer particle film on the surface of a substrate filtering material through natural precipitation and adsorption, thus obtaining the oil-water separation composite filtering material with special wetting effect, and finishing the surface drying process of the adhesive material in the closed space, wherein the surface drying time is generally 10-60 min. And then taking out the adhered nanoparticle film from the closed space, thoroughly curing the adhesive material layer, and adopting different adhesive materials, wherein the curing time is different, and the complete curing is generally completed within 12-24 hours.
The composite oil-water separation filter material prepared by the method has good mechanical strength due to the high-strength support material, and the low-surface-energy adhesion material can form complete coverage on the surface of the substrate filter material, so that the substrate filter material is protected while the surface modification is realized, and the service life of the material is further prolonged. The filtration mode is not to realize physical interception by making the pore diameter of the substrate filtration material smaller than the diameter of emulsified liquid drops in the oil-water mixture, but to realize the removal of emulsified oil drops by selectively adsorbing oil substances through the surface modification of low surface energy materials and nano microparticles, so that the pore diameter of micropores of the substrate filtration material can be higher than that of other filtration materials, and the removal of trace impurities in the oil-water mixture can be realized under the condition of ensuring the filtration speed performance of the substrate filtration material. In addition, the surface modification of the hydrophobic nanometer microparticles can expose the nanometer microparticles outside, so that the physical and chemical properties of the surfaces of the nanometer microparticles are fully exerted, the special surface wettability of the nanometer microparticles is improved, and the nanometer microparticles are wrapped by materials such as resin in a method of dispersing the nanometer microparticles in the corresponding resin, so that an ideal surface modification effect cannot be achieved.
The technology of the proposed composite oil-water separation filter film is further described in detail below with reference to examples.
Example 1
A high-strength refined steel mesh with the thickness of 1mm and the aperture of 2mm is selected as a supporting material, a metal felt with the aperture of 10 mu m and the thickness of 100 mu m is selected as a substrate filtering material, and hydrophobic silica microspheres with the particle size of 500nm are selected as surface morphology modifying particles (nanometer microparticles). The two support materials and the base filter material are formed into a composite filter screen by sintering. And (3) immersing the composite filter screen in fluorocarbon resin for 20min, taking out, immediately (within 1 min) suspending the composite filter screen in a silica microsphere suspension space, taking out after the fluorocarbon resin is dried and solidified, blowing off superfluous particles on the surface, taking out the closed space, and thoroughly solidifying to form the oil-water separation composite filter material with special wettability. The prepared oil-water separation composite filter material is used for separating an oil-water mixture (the oil-water mixture is formed by mixing and stirring diesel oil and water according to the proportion of 1:10), and can realize the separation effect of more than 99 percent.
Example 2
Selecting a metal filter screen with the thickness of 0.5mm and the aperture of 1mm as a supporting material; the metal microporous filter material with the aperture of 10 mu m and the thickness of 100 mu m is selected as a base filter material, and the composite structure net is formed by pressing and sintering. And immersing the composite filter screen in organic silicon resin for 20min, taking out, suspending in a suspension space of silicon dioxide microspheres with the particle size of 500nm, taking out after 10min, and solidifying at room temperature to form the oil-water separation composite filter material with special wettability. The prepared oil-water separation composite filter material is used for separating an oil-water mixture (oil-water mixture is formed by mixing and stirring diesel oil and water according to the proportion of 1:10), and can realize the separation effect of more than 99 percent.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. The oil-water separation composite filter material is characterized by comprising a substrate filter material and a support material, wherein the substrate filter material is arranged above the support material, a low surface energy adhesion material is arranged above the substrate filter material, and a nano-micro particle film is adhered to the surface of the low surface energy adhesion material; the substrate filtering material is a metal filter screen, filter cloth or filter paper, and the pore diameter range of the micropores is 5-300 mu m; the supporting material is a stainless steel supporting structure, the aperture range is 0.5-10mm, the supporting material is enclosed to be cylindrical, and the substrate filtering material is attached to the outer surface of the cylindrical supporting material and fixed in the direction of the upper opening and the lower opening of the cylindrical material;
the preparation method of the oil-water separation composite filter material comprises the following steps:
step one: preparing the support material and the base filter material; selecting the supporting material and the substrate filtering material, and arranging the substrate filtering material on the surface of the supporting material to form a composite structure;
step two: uniformly coating the adhesive material on the surface of the substrate filter material;
step three: adhering the surface of the adhesion material to the nano-microparticle film, and curing the adhesion material to prepare the nano-microparticle film;
and in the third step, the nano-micro particle film is adhered to the surface of the adhesive material, namely, the composite structure obtained in the first step is arranged in a closed space, the nano-micro particles are dispersed and suspended in the closed space, and the nano-micro particle film is formed on the surface of the substrate filter material through natural precipitation and adsorption.
2. The oil-water separation composite filter material according to claim 1, wherein the thickness of the nano-micro particle film is 1-5 nano-micro particles, and the diameter of the nano-micro particles is 200nm-2 μm.
3. The oil-water separation composite filter according to claim 1, wherein the low surface energy adhesion material has a thickness of 10 to 150 μm.
4. The oil-water separation composite filter according to claim 1, wherein in the first step, the base filter is disposed on the surface of the support material by sintering or mechanical fixing.
5. The oil-water separation composite filter material according to claim 4, wherein in the second step, the adhesive material is uniformly coated on the surface of the base filter material by spraying or dipping; the adhesive material is paint.
Priority Applications (1)
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