CN112844067A - Oil-water separation ceramic membrane, preparation method and oil-water separation method - Google Patents
Oil-water separation ceramic membrane, preparation method and oil-water separation method Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
- B01D71/025—Aluminium oxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
- B01D71/027—Silicium oxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to an oil-water separation ceramic membrane, a preparation method and an oil-water separation method, wherein the method comprises the steps of carrying out hydrophobic modification on a common hydrophilic porous ceramic membrane by using a modification liquid, and carrying out plasma etching on the modified hydrophobic ceramic membrane to obtain a novel ceramic membrane with one hydrophobic property and the other hydrophilic property; the special structure of the emulsion breaking device is utilized to realize the emulsion breaking function, and simultaneously, the water phase is obtained when an oil-in-water system is separated, and the oil phase is obtained in a water-in-oil system; the ceramic membrane has better pollution resistance in both high-concentration and low-concentration oil-water emulsion. And has faster separation speed and higher retention rate. The invention has simple preparation process, easily obtained raw materials and lower environmental requirement, and can be used in an actual oil-water separation system.
Description
Technical Field
The invention belongs to the field of oil-water separation, and particularly relates to an oil-water separation ceramic membrane, a preparation method and an oil-water separation method.
Background
Water is an indispensable resource for maintaining human survival, and the safety of water is closely related to our lives. With the rapid development of society and industry, a large amount of oily wastewater is often generated in the industrial production and transportation processes of oil exploitation, oil refining, pharmacy, food, leather textile and the like, which becomes one of global important pollution sources and seriously threatens the stability of an ecosystem. The oily wastewater has wide sources and very complex components, such as insoluble oil compounds of gasoline, diesel oil, kerosene, animal oil, vegetable oil and the like. Oily wastewater has great harm to the living environment and ecological balance of human beings, such as water resource pollution, serious pollution and damage to the ecological environment, water quality pollution, harm to the health of human beings, potential safety hazard caused by combustion of coalesced oil products and the like.
The oily wastewater contains four forms, which can be generally divided into oil slick, dispersed oil, emulsified oil and dissolved oil according to the difference of oil drop particle sizes, and the oil slick and the dispersed oil with larger particle sizes are generally easier to treat, while the emulsified oil and the dissolved oil with smaller particle sizes are more difficult to treat. The traditional methods for separating oil and water include a gravity method, a flotation method, an adsorption method, a biological oxidation method and the like. A gravity method: oil-water separation is carried out by strong centrifugal force by utilizing different oil-water densities. The method has high requirement on equipment, high energy consumption and single function, and can not treat organic pollutants in water. The gravity method is a physical method for separating impurities such as oil drops, suspended matters and the like from water in an oil-water separation device in a flowing state or a static state by utilizing the principle that oil and water have different densities and cannot be dissolved mutually. For example, chinese patents CN205258165U, CN209797646 and CN110384954A disclose devices and processes for oil-water separation by gravity method. However, this method still has disadvantages that practical application is limited, for example, only oily wastewater with large particle size such as dispersed oil and oil slick can be treated, and in the case of emulsified oil, dissolved oil is difficult to remove. The separation under the condition of gravity only by means of the density difference of two phases takes long time, the separation efficiency is low, and the occupied area of equipment is large. The air floatation separation method is characterized in that air is introduced into water to generate micro bubbles, and the micro bubbles are caused to adhere to removed oil stains and solid particles under the combined action of various forces such as interfacial tension, bubble rising buoyancy, purified water pressure difference and the like after entering the water and float to the water surface due to the fact that the adhesive density is smaller than that of the water surface, so that the oil stains and the fixed particles in the water are separated and removed by the oil scraping device. For example, Chinese patents CN109574116A, CN210163271U and CN210121354U disclose an air-flotation oil-water separation technology, which has the advantages of good separation effect, simple operation and mature process. However, although the above patent can remove the dissolved oil and emulsified oil, there are cases where the waste water having an excessively high oil concentration cannot be treated in time and the recovered waste oil has too many impurities to be recycled. An adsorption method: the adsorption method generally utilizes a porous structure rich in porous materials to physically adsorb oil drops, and has the advantages of simple process, high recovery efficiency, greenness, high efficiency and the like, but most of adsorbents have relatively small adsorption capacity, high use and recovery cost and complicated subsequent reprocessing. Biological oxidation method: the biological oxidation method decomposes organic matters into pollution-free small molecular organic matters by utilizing the metabolism of microorganisms, but has low treatment efficiency and long time consumption, and is difficult to be suitable for large-scale oily sewage treatment. These conventional methods for treating wastewater have various problems such as low efficiency, possibility of causing secondary pollution, high energy consumption, residue, and inability to effectively separate emulsified oil-water mixture.
The membrane separation technology has the advantages of simple separation device, easy operation, high efficiency, energy conservation, wide application range and the like, and is widely applied to treating various oil-water mixtures.
Chinese patent publication No. CN103521095A discloses a method for preparing a tubular ceramic membrane for oil-water separation, which comprises coating a membrane-making solution containing polytetrafluoroethylene or polyvinylidene fluoride on a ceramic membrane by using an alumina ceramic membrane tube as a substrate; then preparing a hydrophobic and oleophylic tubular ceramic membrane by a sintering and drying method; chinese patent publication No. CN110354701A discloses a preparation method of a high pollution-resistant oil-water separation ultrafiltration membrane, which adopts perfluorocarbon surfactant Zonyl FSO to modify to prepare a macroinitiator, utilizes an atom transfer radical polymerization method to synthesize a compound containing a perfluoro group, and adopts a non-solvent induced phase inversion method to prepare the oil-water separation ultrafiltration membrane after a membrane preparation liquid is mature, thereby improving the recovery rate of the relative flux of the membrane and being beneficial to reducing the operation cost of the membrane separation process. The modifier reduces the surface energy of the material through fluorine-containing compounds, and has the problems of environmental pollution, high price, limited source and the like.
Chinese patent No. CN109173346A discloses a preparation method of an oil-water separation membrane with a smooth surface and a method thereof, wherein a polymer membrane composed of a fiber membrane and a porous membrane is subjected to roughening and fluorination treatment to obtain a polymer membrane substrate with a silicon dioxide rough structure, then excessive lubricating oil is poured into the rough structure on the surface of the polymer, and then the excessive lubricating oil is removed to obtain the oil-water separation membrane with the smooth surface. The separation membrane has high separation efficiency and separation rate; chinese patent No. CN110526337A discloses a preparation method of an oil-water separation membrane, which is used for constructing SiO on cotton fabric by a sol-gel method2And (3) coating polythiophene on the surface by using a solid-phase coupling method, and washing and drying to obtain the oil-water separation membrane. The preparation method is simple and easy to operate, and the cotton fabric has oleophobic property and good separation effect. The oil-water separation membrane prepared above is suitable for treating water-in-oil emulsion, and is not suitable for separating oil-in-water emulsion
Chinese patent publication No. CN110585930A discloses a preparation method for an oil-water separation ceramic membrane, which comprises the steps of taking a silicon nitride ceramic membrane as a substrate, immersing the silicon nitride ceramic membrane into a mixed solution prepared by adding epoxy acrylate, alkannin, 3-allyloxy-1, 2-propylene glycol and the like into an ethyl acetate solvent and uniformly stirring the mixture for modification, taking the modified ceramic membrane to cure and crosslink under a UV lamp, and washing and drying the ceramic membrane to obtain the oil-water separation ceramic membrane; chinese patent publication No. CN106861435A discloses a preparation method of a polyacrylonitrile bionic film for oil-water emulsion separation, which takes an alumina ceramic membrane with the thickness of 1mm as a support body, scrapes a polymer solution prepared from polyacrylonitrile powder onto the support body, and then puts the polymer solution into a non-solvent for coagulation bath to obtain the super-hydrophilic/underwater super-oleophobic bionic polyacrylonitrile film. The oil-water separation membrane prepared by the method is complicated in modification process, a water phase is obtained when an oil-in-water system is treated, the efficiency is low, and the pollution is serious.
Chinese patent CN209338347U discloses an oil-water separation device, which comprises a water inlet area, a mixing area, a biomembrane filtering area, an oil-water separation area I, an oil-water separation area II and a water outlet area. The device can well remove emulsified oil in sewage, separate liquid and coagulated animal fat and grease, need not to add flocculating agent. Chinese patent CN210151034U discloses an oil-water separation device based on graphene film, which comprises a cylinder, a rotary tray, a rotary power mechanism and a preheating device, wherein the device is heated uniformly, makes full use of waste heat, and can well separate water in crude oil. Although the above patent can solve the oil-water separation problem well, it cannot complete two separation tasks in one device.
With the development of chemical equipment towards the direction of energy conservation, high efficiency and multifunction integration, one machine has multiple functions, and a new multistage integrated equipment becomes the current development direction.
Chinese patent CN109652117A discloses an oil-water separation system and a separation method process. The process comprises a membrane filtration system, a pre-separation system, a light phase separation system and a heavy phase separation system. The light phase separation area and the heavy phase separation area can realize the separation of water-in-oil or oil-in-water type materials, and have the advantages of high efficiency, simple equipment and the like. Although the method can be used for treating both oil-in-water emulsions and water-in-oil emulsions, the hollow filter element needs to be replaced by an oleophilic hydrophobic material or a hydrophilic oleophobic material according to the change of a system, the steps are complicated, and the membrane pollution is also a serious problem in the long-time operation process.
Based on the above problems, it is urgently needed to develop a novel oil-water separation process and apparatus, which utilize the advantages of the membrane separation method and combine the centrifugal sedimentation operation, the flushing operation, and the heating operation to separate the oil-water emulsions with different concentrations.
Disclosure of Invention
The first invention point to be solved by the invention is: the existing membrane technology is used for oil-water separation operation, most of the operation periods are long, pollution is easy, and the modification process is complex. In order to overcome the drawbacks of the prior art, there is a need to prepare a novel ceramic membrane with asymmetric wetting properties. Therefore, the preparation method of the novel oil-water separation ceramic membrane, which can separate an oil-in-water system to obtain a water phase and a water-in-oil system to obtain an oil phase, is provided, the separation precision is ensured, the separation efficiency is improved, the anti-pollution capacity is enhanced, and the modification steps are greatly simplified.
The invention also aims to solve the problems that: the novel membrane method oil-water separation process and device are provided, wherein a heating device, a membrane switching type separation device, a buffer device, a flushing device and a centrifugal sedimentation device are respectively arranged, and the heating device realizes viscosity reduction treatment on water-in-oil emulsion; the buffer device and the centrifugal settling device realize the recycling of the residual liquid of the oil-water emulsion; the washing device realizes the cleaning of the separation membrane, thereby greatly reducing the pollution degree of the membrane; the membrane switching type separation device realizes the switching type separation of oil-in-water and water-in-oil emulsions to obtain pure water phase or oil phase. The device can efficiently realize the separation of oil-water emulsion and the removal of impurities, the process flow is reasonable and feasible, the device equipment is simple and easy to operate, the operation is stable, and the retention rate of oil or water in the oil-water emulsion reaches more than 99%.
In a first aspect of the present invention, there is provided:
a ceramic membrane for separating oil from water, the main body of which has a water drop contact angle of hydrophobicity, and the surface of one side of which has a water drop contact angle of hydrophilicity.
In one embodiment, the hydrophilic water drop contact angle is from 0 to 90 °, and the hydrophobic water drop contact angle is from 91 to 180 °.
In one embodiment, the ceramic membrane is of a sheet or tubular structure and has an average pore size of 0.5 to 5 μm.
In a second aspect of the present invention, there is provided:
the preparation method of the oil-water separation ceramic membrane comprises the following steps:
and 2, carrying out hydrophilic modification on one side of the porous ceramic membrane obtained in the step 1 to obtain the oil-water separation ceramic membrane.
In one embodiment, the ceramic material of the porous ceramic membrane is one or a mixture of several of zirconia, alumina, ceria, silica, titania, mullite and kaolin.
In one embodiment, the hydrophobic modifier in step 1 is an organic solvent containing a silane coupling agent.
In one embodiment, the silane coupling agent is one of octaalkyltrimethoxysilane, tridecyltrimethoxysilane, or hexadecyltrimethoxysilane solvents.
In one embodiment, the organic solvent is one of acetone, ethanol, or hexane.
In one embodiment, the silane coupling agent concentration is from 0.01mmol/L to 0.15 mol/L.
In one embodiment, the process for preparing the hydrophobic modifier is: dissolving silane coupling agent in organic solvent, heating to 30-60 deg.C in water bath, and stirring for 10-15 hr.
In one embodiment, the modification reaction parameters are: heating to 50-60 deg.C, and standing for more than 12 hr.
In one embodiment, the porous ceramic membrane is cleaned and dried after the modification reaction in the step 1, and the treatment temperature in the drying process is 80-180 ℃ and the treatment time is 16-30 h.
In one embodiment, before step 1, the porous ceramic membrane needs to be pretreated, wherein the pretreatment refers to that the porous ceramic membrane is immersed in absolute ethyl alcohol to be cleaned and remove impurities in pore channels and on the surface of the porous ceramic membrane, and then the porous ceramic membrane is dried.
In one embodiment, the hydrophilic modification in step 2 is treatment with a plasma generator.
In one embodiment, the ionized gas in the plasma generator treatment process is one or a mixture of air, argon, oxygen or nitrogen, the power is 30-150W, and the modification time is 20-300 s.
In a third aspect of the present invention, there is provided:
an oil-water separation method comprises the following steps:
and 5, carrying out centrifugal sedimentation treatment on the first trapped fluid and/or the second trapped fluid, feeding the water-in-oil raw material liquid obtained from the upper layer into the step 3 for continuous treatment, and feeding the oil-in-water raw material obtained from the lower layer into the step 1 for continuous treatment.
In one embodiment, the set ratio in step 2 and/or step 4 is 30 to 70wt.%, or 40 to 60wt.%, or 45 to 55 wt.%.
In one embodiment, the method further comprises a step of washing the oil-water separation ceramic membrane with a washing solution after the oil-water separation is stopped in the step 2 and/or the step 4.
In one embodiment, the time interval of the rinsing process is 60min, the rinsing time is 10min, the rinsing liquid is pure water or hypochlorous acid with the concentration of 1% -10%, and the rinsing pressure is 1-5 Mpa.
In one embodiment, in step 3, increasing the temperature means raising the temperature to 30-60 ℃ for 30-60 min.
In one embodiment, in step 1 and/or step 3, the operation pressure in the separation process of the oil-water separation process is 0.1-3Mpa, and the filtration mode is cross-flow filtration.
In one embodiment, in step 5, the centrifugation time is 10-50 min.
In a fourth aspect of the present invention, there is provided:
an oil-water separation device comprising:
the switching type membrane separation component is internally provided with the oil-water separation ceramic membrane;
the oil-in-water storage tank and the water-in-oil storage tank are respectively used for storing an oil-in-water raw material liquid and a water-in-oil raw material liquid;
the oil-in-water storage tank is connected to one side, with a hydrophilic water drop contact angle, of the oil-water separation ceramic membrane in the switching type membrane separation assembly;
the water-in-oil storage tank is connected to one side of the oil-water separation ceramic membrane in the switching type membrane separation assembly, wherein the side has a hydrophobic water drop contact angle.
In one embodiment, the oil-water separation ceramic membrane in the switching membrane separation module is further provided with an oil-in-water circulation liquid outlet on the side with the hydrophilic water drop contact angle, and the oil-in-water circulation liquid outlet is connected with the oil-in-water storage tank.
In one embodiment, the water phase outlet is further provided on the side of the oil-water separation ceramic membrane in the switching membrane separation module having the hydrophobic water drop contact angle.
In one embodiment, a water-in-oil circulation liquid outlet is further arranged on one side of the oil-water separation ceramic membrane in the switching type membrane separation module, which has a hydrophobic water drop contact angle, and the water-in-oil circulation liquid outlet is connected with the water-in-oil storage tank.
In one embodiment, the oil-water separation ceramic membrane in the switching membrane separation module is further provided with an oil phase outlet on the side having the hydrophilic water drop contact angle.
In one embodiment, further comprising: the buffer tank is respectively connected with the oil-in-water storage tank and the water-in-oil storage tank;
the centrifugal settling machine and the buffer tank are used for carrying out centrifugal separation treatment on the feed liquid in the buffer tank; an upper layer liquid outlet of the centrifugal settling machine is connected with the water-in-oil storage tank, and a lower layer liquid outlet of the centrifugal settling machine is connected with the oil-in-water storage tank.
In one embodiment, the exterior of the water-in-oil storage tank is provided with a heating jacket.
In one embodiment, the switching membrane separation module is further provided with a washing liquid inlet and a washing liquid outlet for washing two sides of the oil-water separation ceramic membrane.
In a fifth aspect of the present invention, there is provided:
the novel ceramic oil-water separation membrane is applied to oil-water separation of oil-in-water emulsion and/or water-in-oil emulsion.
In a sixth aspect of the present invention, there is provided:
the oil-water separation device is applied to oil-water separation of oil-in-water emulsion and/or water-in-oil emulsion.
Advantageous effects
1. The prepared novel oil-water separation ceramic membrane has the functions of pollution resistance and easy cleaning while ensuring the separation precision.
2. When the oil-in-water emulsion is separated, the emulsion breaking function is realized by utilizing the affinity effect of the hydrophilic side to water, and the separation efficiency is improved.
3. The surface of the novel oil-water separation ceramic membrane has asymmetric wettability, one surface has hydrophilic property, and the other surface has hydrophobic property. The membrane surface can be flexibly switched according to the system.
4. The preparation process of the oil-water separation membrane is simple and convenient, the complex modification process is avoided, and the prepared oil-water separation ceramic membrane has good chemical stability.
5. The oil-water separation process does not need to add chemical substances such as flocculating agents and the like, has no secondary pollution, is environment-friendly, realizes the separation of oil-water emulsion by utilizing a screening mechanism, and has lower energy consumption. The high-pressure washing process can effectively reduce pollution of the ceramic membrane in the operation process, ensure the separation efficiency and prolong the service life of the ceramic membrane. The heating process can effectively reduce the viscosity of the water-in-oil emulsion, improve the temperature of materials and increase the flux. The oil-water separation device has high flux, large interception rate, low working pressure, small occupied area and continuous operation. The switching type membrane separation process can be flexibly switched according to a system, realizes the high-efficiency separation of oil-water emulsion, realizes one machine with multiple functions and multi-stage integration, accords with the current development direction, and is suitable for large-scale industrial application.
Drawings
FIG. 1 is a schematic diagram of the preparation process of a novel oil-water separation ceramic membrane
FIG. 2 is a raw material side microscope and digital photograph of a novel oil-water separation ceramic membrane on a soybean oil-in-water emulsion: (a) after filtration (b) before filtration at 200ppm and (c) before filtration at 5000ppm
FIG. 3 is a raw material side microscope and digital photograph of a novel oil-water separation ceramic membrane on a hexane-in-water emulsion: (d) after filtration (e) before filtration at 200ppm and (f) before filtration at 5000ppm
FIG. 4 is a schematic structural diagram of the novel membrane method oil-water separation device;
wherein T-1 is a centrifugal settler, T-2 is an oil-in-water storage tank, T-3 is a water-in-oil storage tank, T-4 is a flushing liquid storage tank, T-5 is a buffer storage tank, T-6 is a product storage tank, T-7 is a heating control device, T-8 is a jacket, T-9 is an insulating layer, and T-10 is a switching type membrane separation component; p-1 is an oil-water emulsion delivery pump, P-2 is an oil-in-water circulating pump, P-3 is a flushing pump, and P-4 is a water-in-oil circulating pump; v-1, V-2, V-3, V-4, V-5, V-6, V-7 and V-8 are valves; y-1, Y-2, Y-3, Y-4, Y-5 and Y-6 are pressure gauges; t-11 is a temperature sensor, J-1 is a high-pressure flushing valve, F-1 and F-2 are flow meters, and 1,2 and 3 are respectively an oil-water emulsion outlet, an oil-in-water surplus liquid inlet and a water-in-oil surplus liquid inlet on a buffer storage tank; 4.5, 6 are respectively an oil-in-water residual liquid outlet, an oil-in-water raw material liquid outlet and an oil-in-water circulating liquid inlet on the oil-in-water storage tank; 7. 8, 9, 10, 11, 12, 13 and 14 are respectively an oil-in-water circulation liquid outlet, a flushing liquid inlet, a flushing liquid outlet, an oil-in-water raw material liquid inlet, a water phase outlet, an oil phase outlet, a water-in-oil circulation liquid outlet and a water-in-oil raw material liquid inlet on the switching type membrane separation assembly; 17. 19 are respectively a heating medium inlet and a heating medium outlet on the jacket; 15. 16 and 18 are respectively a water-in-oil residual liquid outlet, a water-in-oil raw material liquid outlet and a water-in-oil circulating liquid inlet on the water-in-oil storage tank;
FIG. 5 is a schematic view of the internal structure of a switching membrane separation module;
FIG. 6 is a graph of the flux of a hexane-in-water emulsion film treated with the hydrophilic side of an alumina ceramic membrane as a function of time in example 7;
FIG. 7 is a graph of the viscosity of a water-in-oil emulsion of soy beans treated with the hydrophobic side of an alumina ceramic membrane as a function of time in example 9;
FIG. 8 is a graph showing the time-dependent change in the flux of a soybean water-in-oil emulsion film treated with the hydrophobic side of an alumina ceramic membrane in example 9;
Detailed Description
One aspect of the invention relates to a preparation method of a novel ceramic membrane for separating an oil-in-water system, which comprises the steps of carrying out hydrophobic modification on a common hydrophilic porous ceramic membrane by using a modification liquid, enabling the whole obtained ceramic membrane to present hydrophobicity (including the surface of the membrane and internal pore channels), and carrying out plasma etching on the modified hydrophobic ceramic membrane to obtain the novel ceramic membrane which has hydrophobicity on the main body and hydrophilic property on the surface of one single side; the special structure of the water-in-oil emulsion breaking device is utilized to realize the demulsification function, and simultaneously realize that a water phase is obtained at a permeation side when an oil-in-water system is separated, and an oil phase is obtained at a permeation side in the separation of the water-in-oil system; the ceramic membrane has better pollution resistance in both high-concentration and low-concentration oil-water emulsion. And has improved separation speed, filtration flux and higher rejection rate. The invention has simple preparation process, easily obtained raw materials and lower environmental requirement, and can be used in an actual oil-water separation system.
In an exemplary embodiment, the above steps may be:
1) immersing the porous ceramic membrane into absolute ethyl alcohol, cleaning to remove impurities in a pore channel and on the surface of the porous ceramic membrane, and drying for later use;
2) preparing a modifier: dissolving silane solvent in organic solvent, heating to 30-60 deg.C in water bath, stirring for 10-15 hr, and standing.
3) Immersing the ceramic membrane obtained after drying in the step 1) into a modifier, heating the ceramic membrane to 50-60 ℃ in a water bath, standing the ceramic membrane for 12 hours, cleaning the ceramic membrane for a plurality of times by using an organic solvent, and drying the ceramic membrane for later use
4) Placing the hydrophobic ceramic membrane obtained in the step 3) in a plasma generator for single-side hydrophilic modification to obtain the hydrophobic ceramic membrane.
Preferably, the ceramic material in the step 1) is one or a mixture of more of zirconia, alumina, ceria, silica, titania, mullite and kaolin
Preferably, the porous ceramic membrane in step 1) has a sheet-like or tubular structure, and the average pore diameter is 0.5-5 μm. The drying temperature is 60-150 deg.C, and the treatment time is 6-15 h.
Preferably, the silane solvent in step 2) is one of octaalkyltrimethoxysilane, tridecyltrimethoxysilane and hexadecyltrimethoxysilane.
Preferably, the organic solvent in step 2) is one of acetone, ethanol and hexane.
Preferably, the concentration of the modifier in the step 2) is 0.01mmol/L-0.15 mol/L.
Preferably, the organic solvent in step 3) is one of acetone, ethanol and hexane. The drying temperature is 80-180 deg.C, and the treatment time is 16-30 h.
Preferably, the gas ionized by the plasma generator in the step 4) is one or a mixture of air, argon, oxygen and nitrogen. The power is 30-150W, and the modification time is 20-300 s.
In another aspect of the invention, a novel membrane method oil-water separation process and a novel membrane method oil-water separation device are provided, and the process comprises the following steps: heating process, switching type membrane separation process, buffering process, centrifugal settling process and high-pressure washing process. The heating process realizes the viscosity reduction treatment of the emulsion, and the centrifugal sedimentation process realizes the full utilization of the residual liquid of the oil-water emulsion. The switching type membrane separation process adopts a ceramic porous membrane, and the ceramic porous membrane has high mechanical strength, corrosion resistance and good chemical stability; the membrane of the invention has the characteristic of asymmetric wetting property, and different membrane surfaces are selected to complete separation operation according to different systems. The process and the device have the advantages of simple and convenient operation, high flexibility, environmental friendliness, low energy consumption, good application prospect and great economic value, and provide a new idea for the oil-water separation process and equipment.
The device shown in fig. 4, in which the above-mentioned ceramic membrane containing both hydrophilic and hydrophobic properties is used, has a structure including: a novel membrane method oil-water separation device is shown in figure 4 and comprises a heating device, a membrane switching type separation device, a buffering device, a flushing device, a centrifugal sedimentation device and a product storage tank; the heating device consists of a jacket T-8, a heat preservation layer T-9, a heating control device T-7 and a temperature sensor T-11; the membrane switching type separation device consists of an oil-in-water storage tank T-2, a water-in-oil storage tank T-3, an oil-in-water circulating pump P-2, a water-in-oil circulating pump P-4, a flow meter F-1, a flow meter F-2, a pressure gauge Y-3, a pressure gauge Y-5, a pressure gauge Y-6 and a switching type membrane separation component T-10; the buffer device consists of an oil-water emulsion delivery pump P-1, a pressure gauge Y-1 and a buffer storage tank T-5; the flushing device consists of a flushing fluid storage tank T-4, a pipeline, a flushing pump P-3, a flushing valve J-1 and a pressure gauge Y-4, wherein the centrifugal settling device consists of a centrifugal settling machine T-1, a valve V-2 and a valve V-5; wherein, the left and right side walls of the centrifugal settling machine T-1 are provided with a raw material liquid outlet which is respectively connected to the upper parts of an oil-in-water storage tank T-2 and a water-in-oil storage tank T-3 through a pipeline, a valve V-2 and a valve V-5; the lower end of the oil-in-water storage tank is provided with an oil-in-water residual liquid outlet 4 which is connected to a centrifugal settling machine T-1 through a pipeline, a valve V-3, an oil-in-water residual liquid inlet 2, a buffer storage tank T-5, an oil-water emulsion outlet 1, a pressure gauge Y-1 and an oil-water emulsion delivery pump P-1; the switching type membrane separation component T-10 is provided with a flushing liquid outlet 9, an oil-in-water raw material liquid inlet 10, an oil-in-water circulating liquid outlet 7, a flushing liquid inlet 8, a water-in-oil raw material liquid inlet 14, a water phase outlet 11, an oil phase outlet 12 and a water-in-oil circulating liquid outlet 13; the switching type membrane separation component T-10 is internally provided with an oil-water separation ceramic membrane; the oil-in-water storage tank T-2 and the water-in-oil storage tank T-3 are respectively used for storing oil-in-water raw material liquid and water-in-oil raw material liquid; the oil-in-water storage tank T-2 is connected to one side, with a hydrophilic water drop contact angle, of the oil-water separation ceramic membrane in the switching type membrane separation component T-10; the water-in-oil storage tank T-3 is connected to one side of the oil-water separation ceramic membrane in the switching type membrane separation component T-10, wherein the side has a hydrophobic water drop contact angle; an oil-in-water circulation liquid outlet 7 is further formed in one side, having a hydrophilic water drop contact angle, of the oil-water separation ceramic membrane in the switching type membrane separation assembly T-10, and the oil-in-water circulation liquid outlet 7 is connected with the oil-in-water storage tank T-2; a water phase outlet 11 is also arranged on one side of the oil-water separation ceramic membrane in the switching type membrane separation component T-10, which has a hydrophobic water drop contact angle; a water-in-oil circulating liquid outlet 13 is also formed in one side, with a hydrophobic water drop contact angle, of the oil-water separation ceramic membrane in the switching type membrane separation assembly T-10, and the water-in-oil circulating liquid outlet 13 is connected with a water-in-oil storage tank T-3; an oil phase outlet 12 is also arranged on one side of the oil-water separation ceramic membrane in the switching type membrane separation component T-10, which has a hydrophilic water drop contact angle; an oil-in-water raw material liquid outlet 5 is also formed in the lower portion of the oil-in-water storage tank T-2 and is connected to an oil-in-water circulating liquid inlet 6 formed in the right side of the oil-in-water storage tank T-2 through a pipeline, a valve V-4 and a pressure gauge Y-2, an oil-in-water circulating pump P-2, an oil-in-water raw material liquid inlet 10, a switching type membrane separation component T-10, an oil-in-water circulating liquid outlet 7, a flow meter F-1 and a pressure gauge Y-3 in; the upper flushing liquid inlet 8 of the switching type membrane separation assembly T-10 is connected to a flushing liquid outlet 9 on the switching type membrane separation assembly T-10 through a valve V-8, a flushing valve J-1, a pipeline, a pressure gauge Y-4, a flushing pump P-3 and a flushing tank T-4; the right side wall of the water-in-oil storage tank T-3 is provided with a water-in-oil circulating liquid inlet 18, the lower part is provided with a water-in-oil residual liquid outlet 15 and a water-in-oil raw material liquid outlet 16; a water-in-oil residual liquid outlet 15 is connected with a water-in-oil residual liquid inlet 3 at the lower part of the right side wall of the buffer tank T-5 through a valve V-6 and a pipeline, and a water-in-oil raw material liquid outlet 16 at the lower part of the water-in-oil storage tank T-3 is connected to a water-in-oil circulating liquid inlet 18 through a pipeline, a pressure gauge Y-5, a valve V-7, a water-in-oil circulating pump P-4, a water-in-oil raw material liquid inlet 14, a switching type membrane separation assembly T-10, a water-in-oil circulating; a heating jacket T-8 is arranged on the outer side of the water-in-oil storage tank T-3, and a heat insulation layer T-9 is arranged outside the heating jacket T-8; the right side wall of the heating jacket T-8 is provided with a heating medium inlet 17 and a heating medium outlet 19, and the heating medium returns to the inlet of the heating controller T-7 through the outlet of the heating controller T-7, the pipeline, the heating medium inlet 17 and the heating jacket T-8 in sequence. More specifically, the interfacing relationship in the membrane-switched separation device is shown in fig. 5.
By utilizing the novel membrane method oil-water separation process of the device, pure water phase or oil phase can be obtained by sequentially carrying out a heating process, a switching type membrane separation process, a buffering process and a centrifugal sedimentation process on oil-water emulsion, and a high-pressure washing process is periodically carried out while separation is carried out; the method comprises the following specific steps: the oil-water emulsion is poured into an oil-in-water reservoir or a water-in-oil reservoir depending on the composition of its main phase, when the liquid to be treated is an oil-in-water emulsion: pouring the oil-in-water emulsion into an oil-in-water storage tank, conveying the oil-in-water emulsion to a switching type membrane separation component, carrying out membrane separation on the oil-in-water emulsion to obtain a pure water phase, collecting the pure water phase into a product storage tank, gradually reducing the water phase in the oil-in-water emulsion along with the separation, and conveying the rest liquid of the oil-in-water emulsion to a buffer tank when the ratio of the water phase to the oil phase reaches a set value, and when the liquid to be treated is a: pouring the water-in-oil emulsion into a water-in-oil storage tank, and then performing viscosity reduction treatment on the oil-water emulsion by the aid of a heating system consisting of a jacket, a heat insulation layer, a heating control device and a temperature sensor; and then the oil-water emulsion is separated in a switching type membrane separation device to obtain a pure oil phase, the pure oil phase is collected in a product storage tank, the oil phase in the water-in-oil phase is gradually reduced along with the separation, when the ratio of the oil phase to the water phase reaches a set value, the residual liquid of the water-in-oil emulsion enters a buffer tank and is conveyed to a centrifugal sedimentation machine together with the residual liquid of the oil-in-water emulsion, the oil-water emulsion is separated into layers after centrifugation, the water-in-oil emulsion with light density is conveyed to the water-in-oil storage tank at the upper layer, and the oil-in. The membrane is subjected to a high-pressure washing process while being separated.
Preferably, the membrane is a ceramic membrane made of one or a mixture of more of zirconia, titania, mullite and kaolin.
Preferably the above membrane is one with asymmetric wetting properties, wherein the hydrophilic side is used for handling oil-in-water emulsions and the hydrophobic side is used for handling water-in-oil emulsions; the pore size of the membrane is 2-10000 nm; the operation pressure is 0.1-3Mpa in the separation process, and the filtration mode is cross-flow filtration.
The viscosity reducing treatment is preferably carried out at a heating temperature of 30-60 deg.C for 30-60 min.
The centrifugal sedimentation operation is preferably carried out for 10-50 min.
Preferably, the time interval of the washing process is 60min, the washing time is 10min, the washing liquid is pure water or hypochlorous acid with the concentration of 1-10%, and the washing pressure is 1-5 Mpa.
The centrifugal settling machine is preferably higher than the oil-in-water storage tank and the water-in-oil storage tank; the product storage tank is lower than the switching type membrane separation device, and the oil-water emulsion, the water phase and the oil phase are conveyed by means of gravity.
The switching type membrane separation process is an innovative design process, the switching type membrane separation process is used for treating oil-water emulsions with different properties by utilizing the asymmetric property of the wettability of two sides of a ceramic membrane, different oil-water emulsions are conveyed to different inlets of a switching type membrane separation device, the hydrophilic side of the membrane faces the inlet of the oil-in-water type emulsion, and the hydrophobic side of the membrane faces the inlet of the water-in-oil type emulsion, so that the separation of two systems in one device is completed. The membrane material is divided into an organic membrane material and an inorganic membrane material, the organic membrane has higher requirements on an operation system, is not corrosion-resistant and high temperature resistant, and is easy to swell, and the ceramic membrane has the advantages of high temperature resistance, stable operation, high mechanical strength and the like. The process can well realize the separation of oil-water emulsion, and has simple and convenient operation and reasonable process.
Example 1
An aluminum oxide membrane with the average pore diameter of 0.5 micron is taken as a substrate, the diameter of the membrane is 30mm, and the thickness of the membrane is 2 mm. Hexadecyl trimethoxy silane is added into the ethanol solution, the mixture is heated to 40 ℃ in a water bath and stirred for 12 hours to prepare the modified solution with the concentration of 0.01 mmol/L. And (3) immersing the membrane into the modification solution, heating the membrane to 55 ℃ in a water bath, and reacting for 12 hours to obtain the hydrophobic ceramic membrane. And repeatedly cleaning the hydrophobic ceramic membrane for 3 times by using ethanol, putting the hydrophobic ceramic membrane into an oven, and drying the hydrophobic ceramic membrane for 16 hours at the temperature of 110 ℃. The water contact angle of the modified ceramic film is 128.6 degrees. Placing the obtained hydrophobic ceramic membrane on a cavity platform of a plasma generator, carrying out plasma etching on one side of the membrane, wherein ionized gas is oxygen/nitrogen mixed gas, the etching power is 50W, the frequency is 450kHz, and the etching time is 20s, so that the novel oil-water separation ceramic membrane is obtained, the water contact angle of the hydrophilic side of the novel oil-water separation ceramic membrane is 0 degrees, and the preparation diagram is shown in figure 1; in the obtained sheet-type ceramic membrane, hydrophobic groups are modified in one surface and pore channels in the membrane, and the other surface is subjected to plasma etching to show hydrophilicity. The oil-water separation ceramic membrane is subjected to filtration experiments in 200ppm and 5000ppm soybean oil-in-water emulsions (raw material liquid is in contact with a hydrophilic side), and a pure water phase can be obtained on a permeation side, so that high separation efficiency is realized. The 5000ppm soybean oil-in-water oil phase retention was 95%, and the presence of oil droplets was hardly observed in the water phase, and the microscopic and digital photographs are shown in fig. 2. The prepared novel oil-water separation ceramic membrane has unchanged retention rate and good chemical stability after being subjected to heat treatment at the high temperature of 200 ℃ for 10 hours.
Example 2
Taking a zirconia membrane with the average pore diameter of 0.5 micron as a substrate, wherein the diameter of the membrane is 30mm, and the thickness of the membrane is 2 mm. Hexadecyl trimethoxy silane is added into the ethanol solution, the mixture is heated to 40 ℃ in a water bath and stirred for 12 hours to prepare the modified solution with the concentration of 0.05 mmol/L. And (3) immersing the membrane into the modification solution, heating the membrane to 55 ℃ in a water bath, and reacting for 12 hours to obtain the hydrophobic ceramic membrane. And (3) repeatedly cleaning the hydrophobic ceramic membrane by using ethanol for 3 times, putting the hydrophobic ceramic membrane into an oven, and drying the hydrophobic ceramic membrane for 12 hours at the temperature of 110 ℃. The water contact angle of the modified ceramic film is 128.5 degrees. Placing the obtained hydrophobic ceramic membrane on a cavity platform of a plasma generator, and carrying out plasma etching on one side of the membrane, wherein ionized gas is oxygen/nitrogen mixed gas, the etching power is 60W, the frequency is 450kHz, and the etching time is 30s, so that the novel oil-water separation ceramic membrane is obtained, and the water contact angle of the hydrophilic side of the novel oil-water separation ceramic membrane is 0 degree; in the obtained sheet-type ceramic membrane, hydrophobic groups are modified in the pore channels on one surface and in the membrane, and the other surface is subjected to plasma etching to show hydrophilicity. The oil-water separation ceramic membrane is subjected to filtration experiments in 200ppm and 5000ppm soybean oil-in-water emulsions (raw material liquid is in contact with a hydrophilic side), and a pure water phase can be obtained on a permeation side, so that high separation efficiency is realized. The 5000ppm soybean oil-in-water phase retention was 96%, and the presence of oil droplets was hardly observed in the water phase. The prepared novel oil-water separation ceramic membrane has unchanged retention rate and good chemical stability after being subjected to heat treatment at the high temperature of 200 ℃ for 10 hours.
Example 3
A zirconia membrane with the average pore diameter of 1 micron is taken as a substrate, the diameter of the membrane is 30mm, and the thickness of the membrane is 2 mm. Adding hexadecyl trimethoxy silane into the ethanol solution, heating to 40 ℃ in water bath, and stirring for 12 hours to prepare the modified solution with the concentration of 0.02 mmol/L. And (3) immersing the membrane into the modification solution, heating the membrane to 60 ℃ in a water bath, and reacting for 12 hours to obtain the hydrophobic ceramic membrane. And (3) repeatedly cleaning the hydrophobic ceramic membrane by using ethanol for 3 times, putting the hydrophobic ceramic membrane into an oven, and drying the hydrophobic ceramic membrane for 12 hours at the temperature of 110 ℃. The water contact angle of the modified ceramic film is 128 degrees. Placing the obtained hydrophobic ceramic membrane on a cavity platform of a plasma generator, and carrying out plasma etching on one side of the membrane, wherein ionized gas is oxygen/nitrogen mixed gas, the etching power is 45W, the frequency is 450kHz, and the etching time is 30s, so that the novel oil-water separation ceramic membrane is obtained, and the water contact angle of the hydrophilic side of the novel oil-water separation ceramic membrane is 0 degree; in the obtained sheet-type ceramic membrane, hydrophobic groups are modified in the pore channels on one surface and in the membrane, and the other surface is subjected to plasma etching to show hydrophilicity. The oil-water separation ceramic membrane is subjected to filtration experiments in 200ppm and 5000ppm soybean oil-in-water emulsions (raw material liquid is in contact with a hydrophilic side), and a pure water phase can be obtained on a permeation side, so that high separation efficiency is realized. The oil phase retention rate of 5000ppm soybean oil in water is 99%, and oil drops are hardly observed in the water phase; for 200ppm of soybean oil-in-water emulsionThe water flux tends to be stabilized to 600L/m after 30min of filtration2·h-1(ii) a The water flux after filtering the 5000ppm soybean oil-in-water emulsion for 30min tended to stabilize to 80L/m2·h-1. The prepared novel oil-water separation ceramic membrane has unchanged retention rate and good chemical stability after being subjected to heat treatment at the high temperature of 200 ℃ for 10 hours.
Example 4
Taking a zirconia membrane with the average pore diameter of 0.5 micron as a substrate, wherein the diameter of the membrane is 30mm, and the thickness of the membrane is 2 mm. Adding octaalkyltrimethoxysilane into the ethanol solution, heating to 40 ℃ in a water bath, and stirring for 12 hours to prepare a modified solution with the concentration of 0.1 mmol/L. And (3) immersing the membrane into the modification solution, heating the membrane to 55 ℃ in a water bath, and reacting for 12 hours to obtain the hydrophobic ceramic membrane. And (3) repeatedly cleaning the hydrophobic ceramic membrane by using ethanol for 3 times, putting the hydrophobic ceramic membrane into an oven, and drying the hydrophobic ceramic membrane for 12 hours at the temperature of 110 ℃. The water contact angle of the modified ceramic film is 133.4 degrees. Placing the obtained hydrophobic ceramic membrane on a cavity platform of a plasma generator, and carrying out plasma etching on one side of the membrane, wherein ionized gas is oxygen/nitrogen mixed gas, the etching power is 150W, the frequency is 450kHz, and the etching time is 150s, so that the novel oil-water separation ceramic membrane is obtained, and the water contact angle of the hydrophilic side of the novel oil-water separation ceramic membrane is 0 degree; in the obtained sheet-type ceramic membrane, hydrophobic groups are modified in the pore channels on one surface and in the membrane, and the other surface is subjected to plasma etching to show hydrophilicity. The oil-water separation ceramic membrane is subjected to a filtration experiment (raw material liquid is contacted with a hydrophobic side) in 1000ppm and 5000ppm hexane-in-water emulsions, and a pure oil phase can be obtained at a permeation side, so that high separation efficiency is embodied. The water-in-hexane phase retention of 5000ppm was 96%, and the presence of water droplets in the oil phase was hardly observed, as shown in FIG. 3. The prepared novel oil-water separation ceramic membrane has unchanged retention rate and good chemical stability after being subjected to heat treatment at the high temperature of 200 ℃ for 10 hours.
Example 5
A zirconia membrane with the average pore diameter of 1 micron is taken as a substrate, the diameter of the membrane is 30mm, and the thickness of the membrane is 2 mm. Tridecyl trimethoxy silane is added into ethanol solution, heated to 40 ℃ in water bath, stirred for 12 hours to prepare modified solution with the concentration of 0.15 mmol/L. Immersing the membrane into the modified liquid, heating in water bath untilReacting for 12 hours at 55 ℃ to obtain the hydrophobic ceramic membrane. And (3) repeatedly cleaning the hydrophobic ceramic membrane by using ethanol for 3 times, putting the hydrophobic ceramic membrane into an oven, and drying the hydrophobic ceramic membrane for 12 hours at the temperature of 110 ℃. The water contact angle of the modified ceramic film is 137.2 degrees. Placing the obtained hydrophobic ceramic membrane on a cavity platform of a plasma generator, and carrying out plasma etching on one side of the membrane, wherein ionized gas is oxygen/argon mixed gas, the etching power is 150W, the frequency is 450kHz, and the etching time is 150s, so that the novel oil-water separation ceramic membrane is obtained, and the water contact angle of the hydrophilic side of the novel oil-water separation ceramic membrane is 0 degree; in the obtained sheet-type ceramic membrane, hydrophobic groups are modified in the pore channels on one surface and in the membrane, and the other surface is subjected to plasma etching to show hydrophilicity. The oil-water separation ceramic membrane is subjected to a filtration experiment (raw material liquid is contacted with a hydrophobic side) in 1000ppm and 5000ppm hexane-in-water emulsions, and a pure oil phase can be obtained at a permeation side, so that high separation efficiency is embodied. The retention rate of 5000ppm water-in-hexane aqueous phase is 99%, the existence of water drops in the oil phase is hardly observed, and for filtering in 1000ppm water-in-hexane emulsion, the oil flux tends to be stable to 450L/m after 30min2·h-1(ii) a For filtration in 5000ppm water-in-hexane emulsion, the oil flux tended to stabilize at 100L/m after 30min2·h-1(ii) a . The prepared novel oil-water separation ceramic membrane has unchanged retention rate and good chemical stability after being subjected to heat treatment at the high temperature of 200 ℃ for 10 hours.
Example 6
A zirconia membrane with the average pore diameter of 1 micron is taken as a substrate, the diameter of the membrane is 30mm, and the thickness of the membrane is 2 mm. Hexadecyl trimethoxy silane is added into the ethanol solution, the mixture is heated to 40 ℃ in a water bath and stirred for 12 hours to prepare the modified solution with the concentration of 0.15 mmol/L. And (3) immersing the membrane into the modification solution, heating the membrane to 55 ℃ in a water bath, and reacting for 12 hours to obtain the hydrophobic ceramic membrane. And (3) repeatedly cleaning the hydrophobic ceramic membrane by using ethanol for 3 times, putting the hydrophobic ceramic membrane into an oven, and drying the hydrophobic ceramic membrane for 12 hours at the temperature of 110 ℃. The water contact angle of the modified ceramic film is 137.2 degrees. Placing the obtained hydrophobic ceramic membrane on a cavity platform of a plasma generator, and carrying out plasma etching on one side of the membrane, wherein ionized gas is oxygen/argon mixed gas, the etching power is 150W, the frequency is 450kHz, and the etching time is 150s, so that the novel oil-water separation ceramic membrane is obtained, and the water contact angle of the hydrophilic side of the novel oil-water separation ceramic membrane is 0 degree; in the obtained sheet-type ceramic membrane, hydrophobic groups are modified in the pore channels on one surface and in the membrane, and the other surface is subjected to plasma etching to show hydrophilicity. The oil-water separation ceramic membrane is subjected to a filtration experiment (raw material liquid is contacted with a hydrophobic side) in 1000ppm and 5000ppm hexane-in-water emulsions, and a pure oil phase can be obtained at a permeation side, so that high separation efficiency is embodied. The water-in-hexane phase retention of 5000ppm was 99%, and the presence of water droplets in the oil phase was hardly observed. The prepared novel oil-water separation ceramic membrane has unchanged retention rate and good chemical stability after being subjected to heat treatment at the high temperature of 200 ℃ for 10 hours.
Comparative example 1
The difference from example 3 is that: the hydrophilic ceramic membrane is directly adopted to carry out the oil-in-water filtration experiment.
Taking an aluminum oxide membrane with the average pore diameter of 1 micron, wherein the diameter of the membrane is 30mm, and the thickness of the membrane is 2 mm. When the hydrophilic ceramic membrane is applied to a filtration experiment of 200ppm soybean oil-in-water emulsion, the water flux tends to be stable to 200L/m after 30min2·h-1Lower than 600L/m of the novel oil-water separation ceramic membrane2·h-1(ii) a When the hydrophilic ceramic membrane is applied to a 5000ppm soybean oil-in-water emulsion filtration experiment, the water flux tends to be stable to 40L/m after 30min2·h-1Is lower than 80L/m of the novel oil-water separation ceramic membrane2·h-1
(ii) a The 5000ppm soybean oil-in-water phase retention rate is 94% lower than 99% of that of the novel ceramic separation membrane.
Comparative example 2
The difference from example 5 is that: the other side of the hydrophobic ceramic membrane is not subjected to plasma etching treatment.
A zirconia membrane with the average pore diameter of 1 micron is taken as a substrate, the diameter of the membrane is 30mm, and the thickness of the membrane is 2 mm. Tridecyl trimethoxy silane is added into ethanol solution, heated to 40 ℃ in water bath, stirred for 12 hours to prepare modified solution with the concentration of 0.15 mmol/L. And (3) immersing the membrane into the modification solution, heating the membrane to 55 ℃ in a water bath, and reacting for 12 hours to obtain the hydrophobic ceramic membrane. Repeatedly cleaning hydrophobic ceramic membrane with ethanol for 3 times, placing in oven, and heating at 110 deg.CDrying for 12 hours under the condition. When the hydrophobic ceramic membrane is applied to a filtration experiment of 1000ppm water-in-hexane emulsion, the oil flux tends to be stable to 400L/m after 30min2·h-1Lower than 450L/m of the novel oil-water separation membrane2·h-1(ii) a When the hydrophobic ceramic membrane is applied to a 5000ppm hexane-in-water emulsion filtration experiment, the oil flux tends to be stable to 80L/m after 30min2·h-1Is lower than 100L/m of the novel oil-water separation ceramic membrane2·h-1(ii) a The 5000ppm water-in-hexane water phase rejection was 95% lower than 99% for the novel separation ceramic membrane.
Example 7
By using the novel membrane method oil-water separation process, a hexane-in-water emulsion prepared in a laboratory is separated, and the hydrophilic-hydrophobic ceramic membrane prepared in example 3 is adopted, so that the concentration of the emulsion is 200 mg/L. Pouring the emulsion into an oil-in-water storage tank, inputting the emulsion into a switching type membrane separation assembly through an oil-in-water circulating pump for separation, and contacting with a hydrophilic side for filtration to obtain a pure water phase, wherein the retention rate of hexane is 99.1%; the aperture of the ceramic membrane in the membrane module is 1 μm, and the transmembrane pressure difference in the operation process is 0.2 MPa. The running time of the device is 3 hours, and the water flux is stably maintained at 500L/m after 0.5 hour2·h-1As shown in fig. 6. And flushing the separation membrane at high pressure every 1 hour, wherein the flushing liquid is hypochlorous acid solution with the concentration of 5%, the flushing time is 10min, and the flushing pressure is 4.5 MPa. When the ratio of the water phase to the oil phase in the oil-in-water storage tank reaches a set value, the remaining liquid of the hexane-in-water emulsion is conveyed to a buffer tank. The residual liquid in the buffer tank is then conveyed to a centrifugal settling machine by an oil-water emulsion conveying pump, and the centrifugal time is 15 min. After centrifugation, the upper layer water-in-oil emulsion is conveyed to an oil-in-water storage tank for re-separation, and the water flux is stably maintained at 480L/m2·h-1In the vicinity, the retention was 99.2%, and the lower oil-in-water emulsion was transferred to a water-in-oil reservoir for separation.
Example 8
The novel membrane method oil-water separation process is used for separating the water-in-soybean oil emulsion prepared by a laboratory, and the hydrophilic-hydrophobic oil prepared in the example 3 is adoptedCeramic membrane, emulsion concentration is 5000 mg/L. Pouring the emulsion into an oil-in-water storage tank, inputting the emulsion into a switching type membrane separation assembly through an oil-in-water circulating pump for separation to obtain a pure water phase, wherein the rejection rate of hexane is 99.5%; the aperture of the ceramic membrane in the membrane module is 1 μm, and the transmembrane pressure difference in the operation process is 0.3 MPa. The running time of the device is 3 hours, and the water flux is stably maintained at 120L/L/m after 0.5 hour2·h-1. And flushing the separation membrane at high pressure every 1 hour, wherein the flushing liquid is 6% hypochlorous acid solution, the flushing time is 10min, and the flushing pressure is 5 MPa. When the water phase and oil phase occupancy in the oil-in-water reservoir reached the set point, the residue of the soy oil-in-water emulsion was transferred to a buffer tank. The residual liquid in the buffer tank is then conveyed to a centrifugal settling machine by an oil-water emulsion conveying pump, and the centrifugal time is 15 min. After centrifugation, the upper layer water-in-oil emulsion is conveyed to an oil-in-water storage tank for re-separation, and the water flux is stably maintained at 115L/m2·h-1In the vicinity, the retention was 99.2%, and the lower oil-in-water emulsion was transferred to a water-in-oil reservoir for separation.
Example 9
By using the novel membrane method oil-water separation process, the water-in-soybean oil emulsion prepared by a laboratory is separated, and the hydrophilic-hydrophobic ceramic membrane prepared in the example 3 is adopted, so that the concentration of the emulsion is 1000 mg/L. Pouring the emulsion into a water-in-oil storage tank, heating at 60 deg.C with silicone oil as heating medium, and reducing the viscosity of the emulsion from 15 mPas to 1.3 mPas after heating for 50min, as shown in FIG. 7. Then conveying the emulsion to a switching type membrane separation component through a water-in-oil circulating pump for separation to obtain a pure oil phase, wherein the retention rate of water is 99.5%; the aperture of the ceramic membrane in the membrane module is 1 μm, and the transmembrane pressure difference in the operation process is 0.5 MPa. The running time of the device is 3 hours, and the oil flux is stably maintained at 1100/L/m after 0.6 hour2·h-1As shown in fig. 8. And flushing the separation membrane at high pressure every 1 hour, wherein the flushing liquid is hypochlorous acid solution with the concentration of 10%, the flushing time is 10min, and the flushing pressure is 5 MPa. And when the ratio of the oil phase to the water phase in the water-in-oil storage tank reaches a set value, conveying the residual solution of the water-in-isooctane emulsion to a buffer tank. Buffer tankThe residual liquid in the process is then conveyed to a centrifugal settling machine by an oil-water emulsion conveying pump, and the centrifugal time is 15 min. After centrifugation, the upper layer water-in-oil emulsion is conveyed to an oil-in-water storage tank for separation, the lower layer oil-in-water emulsion is conveyed to a water-in-oil storage tank for re-separation, and the oil flux is stably maintained at 960L/m2·h-1The rejection was about 99.5%.
Example 10
By using the novel membrane method oil-water separation process, the water-in-hexane emulsion prepared in a laboratory is separated, and the hydrophilic-hydrophobic ceramic membrane prepared in the example 3 is adopted, so that the concentration of the emulsion is 1000 mg/L. Pouring the emulsion into a water-in-oil storage tank for heating treatment at 50 ℃, wherein the heating medium is silicone oil, and the heating time is 20 min. Then conveying the emulsion to a switching type membrane separation component through a water-in-oil circulating pump for separation to obtain a pure oil phase, wherein the retention rate of water is 99.8%; the aperture of the ceramic membrane in the membrane module is 1 μm, and the transmembrane pressure difference in the operation process is 0.4 MPa. The running time of the device is 3 hours, and the oil flux is stably maintained at 1700L/L/m after 0.6 hour2·h-1. And flushing the separation membrane at high pressure every 1 hour, wherein the flushing liquid is hypochlorous acid solution with the concentration of 10%, the flushing time is 10min, and the flushing pressure is 5 MPa. When the ratio of the oil phase to the water phase in the water-in-oil storage tank reaches a set value, the remaining liquid of the water-in-hexane emulsion is conveyed to a buffer tank. The residual liquid in the buffer tank is then conveyed to a centrifugal settling machine by an oil-water emulsion conveying pump, and the centrifugal time is 15 min. After centrifugation, the upper layer water-in-oil emulsion is conveyed to a water-in-oil storage tank for separation, the lower layer oil-in-water emulsion is conveyed to an oil-in-water storage tank for separation again, and the oil flux is stably maintained at 1650L/m2·h-1The rejection was about 99.5%.
Claims (10)
1. A ceramic membrane for oil-water separation, characterized in that the main body of the ceramic membrane has a water droplet contact angle that is hydrophobic, and the surface on one side of the ceramic membrane has a water droplet contact angle that is hydrophilic.
2. The ceramic membrane for water-oil separation according to claim 1, wherein in one embodiment, the contact angle of the hydrophilic water drop is 0 to 90 ° and the contact angle of the hydrophobic water drop is 91 to 180 °;
in one embodiment, the ceramic membrane is of a sheet or tubular structure and has an average pore size of 0.5 to 5 μm.
3. A method for producing a ceramic membrane for oil-water separation according to claim 1, comprising the steps of:
step 1, immersing a porous ceramic membrane into a hydrophobization modifier for modification reaction;
and 2, carrying out hydrophilic modification on one side of the porous ceramic membrane obtained in the step 1 to obtain the oil-water separation ceramic membrane.
4. The method for preparing a ceramic membrane for oil-water separation according to claim 3, wherein in one embodiment, the ceramic material of the porous ceramic membrane is one or a mixture of zirconia, alumina, ceria, silica, titania, mullite and kaolin;
in one embodiment, the hydrophobic modifier in step 1 refers to an organic solvent containing a silane coupling agent;
in one embodiment, the silane coupling agent is one of octaalkyltrimethoxysilane, tridecyltrimethoxysilane or hexadecyltrimethoxysilane solvent;
in one embodiment, the organic solvent is one of acetone, ethanol, or hexane;
in one embodiment, the silane coupling agent concentration is from 0.01mmol/L to 0.15 mol/L;
in one embodiment, the process for preparing the hydrophobic modifier is: dissolving a silane coupling agent in an organic solvent, heating to 30-60 ℃ in a water bath, and stirring for 10-15 hours;
in one embodiment, the modification reaction parameters are: heating to 50-60 deg.C, and standing for more than 12 hr.
5. The method for preparing a ceramic membrane for oil-water separation according to claim 3, wherein in step 1, the porous ceramic membrane is cleaned and dried after the modification reaction, and the drying process is carried out at a temperature of 80-180 ℃ for 16-30 h;
in one embodiment, before step 1, the porous ceramic membrane needs to be pretreated, wherein the pretreatment refers to that the porous ceramic membrane is immersed into absolute ethyl alcohol to be cleaned and the impurities in the pore channels and on the surface of the porous ceramic membrane are removed, and then the porous ceramic membrane is dried;
in one embodiment, the hydrophilic modification in step 2 is treatment with a plasma generator;
in one embodiment, the ionized gas in the plasma generator treatment process is one or a mixture of air, argon, oxygen or nitrogen, the power is 30-150W, and the modification time is 20-300 s.
6. An oil-water separation method is characterized by comprising the following steps:
step 1, sending an oil-in-water raw material liquid into the oil-water separation ceramic membrane of claim 1 for oil-water separation, wherein the oil-in-water raw material liquid is contacted with one side with a hydrophilic water drop contact angle, the separated water enters a permeation side, and the separated trapped fluid is continuously subjected to circulating separation;
step 2, stopping oil-water separation when the oil-water ratio in the trapped liquid is increased to a set ratio to obtain a first trapped liquid;
step 3, after the temperature of the water-in-oil raw material liquid is increased, the water-in-oil raw material liquid is sent into the oil-water separation ceramic membrane for oil-water separation, the water-in-oil raw material liquid is contacted with one side of a water drop contact angle with hydrophobicity, the separated oil enters a permeation side, and the separated trapped fluid is continuously subjected to circulating separation;
step 4, stopping oil-water separation when the proportion of water and oil in the trapped liquid is increased to a set proportion, and obtaining second trapped liquid;
and 5, carrying out centrifugal sedimentation treatment on the first trapped fluid and/or the second trapped fluid, feeding the water-in-oil raw material liquid obtained from the upper layer into the step 3 for continuous treatment, and feeding the oil-in-water raw material obtained from the lower layer into the step 1 for continuous treatment.
7. The oil-water separation method according to claim 6, wherein the set ratio in the 2 nd step and/or the 4 th step is 30 to 70wt.%, or 40 to 60wt.%, or 45 to 55wt.% in one embodiment;
in one embodiment, in the step 2 and/or the step 4, after the oil-water separation is stopped, a step of washing the oil-water separation ceramic membrane with a cleaning solution is further included;
in one embodiment, the time interval of the rinsing process is 60min, the rinsing time is 10min, the rinsing liquid is pure water or hypochlorous acid with the concentration of 1% -10%, and the rinsing pressure is 1-5 Mpa.
8. The oil-water separation method according to claim 6, wherein in step 3, the temperature is raised to 30 to 60 ℃ for 30 to 60 min.
9. The method according to claim 6, wherein in step 1 and/or step 3, the operating pressure during oil-water separation is 0.1-3Mpa, and the filtration is cross-flow filtration;
in one embodiment, in step 5, the centrifugation time is 10-50 min.
10. Use of the novel ceramic membrane for oil-water separation according to claim 1 for oil-water separation of oil-in-water and/or water-in-oil emulsions.
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Application publication date: 20210528 |