KR102140116B1 - Fluidized membrane reactor for water purification possessing ability of decomposing organics - Google Patents

Abstract

The present invention is formed by a non-solvent-induced phase separation method from a polymer solution containing ZIF-8 or TiO ₂ @ZIF-8 as a photocatalyst on a ceramic support having pores having an average diameter of 0.1 to 5 μm in size and one surface of the support. , A polyvinylidene fluoride (PVDF) composite separation membrane comprising a nanofiltration membrane, and a UV lamp positioned at a distance from the side of the nanofiltration membrane parallel to the length of the composite separation membrane and having a UV resolution A fluidized bed separation membrane reactor for water treatment, and a method for treating water using the same.

Description

Fluidized membrane reactor for water purification possessing ability of decomposing organics

The present invention is formed by a non-solvent-induced phase separation method from a polymer solution containing ZIF-8 or TiO ₂ @ZIF-8 as a photocatalyst on a ceramic support having pores having an average diameter of 0.1 to 5 μm in size and one surface of the support. , A polyvinylidene fluoride (PVDF) composite separation membrane comprising a nanofiltration membrane, and a UV lamp positioned at a distance from the side of the nanofiltration membrane parallel to the length of the composite separation membrane and having a UV resolution A fluidized bed separation membrane reactor for water treatment, and a method for treating water using the same.

Due to the diversification of the industrial field, micro-organic pollutants that are difficult to decompose in water, such as natural organic matters, endocrine disruptors, pharmacologically active substances, and carbon nano-organic substances, are increasing and diversifying.

Generally, wastewater treatment methods are classified into biological treatment and physicochemical treatment methods. Biological treatment is used for oxidation of biodegradable organic substances, and physicochemical treatment is used for removal and oxidation of suspended solids and organic substances. Substances having a predetermined size can be removed relatively easily by a method such as filtration, but it is difficult to remove small molecule compounds such as lower carbon compounds of C6 or less. These small molecule organic compounds can be removed by oxidation or reduction to decomposition. To this end, enzymes such as biological decomposition methods can be used, but this requires a high cost, has a large restriction by the reaction environment, and is difficult to use repeatedly over a long period of time.

Advanced oxidation technology (AOT/AOP: Advanced Oxidation Technology/Process) refers to a water treatment technology that increases oxidative efficiency and oxidation rate of organic materials by generating OH radicals with much stronger oxidizing power than chemical oxidizing agents. OH radical, which exerts strong oxidizing power, has been spotlighted as a water treatment technology in that it is a process capable of completely oxidizing not only biodegradable substances present in water, but also toxic and hardly decomposable organic substances with CO ₂ and H ₂ O.

This advanced oxidation technology can be divided into various types depending on the method of generating OH groups. The advanced oxidation technology consists of a photocatalyst, ultraviolet light, ozone, H ₂ O _2, etc., and possible combinations thereof, and the existing chemical, biological, Since various problems have been pointed out, such as the physical adsorption and catalyst use method, etc., due to the burden of a large amount of oxidizing agent, the availability of microorganisms, and the need for secondary treatment, and the economical reasons for using expensive precious metal catalysts, it is economical. In the meantime, it is developing in the direction of seeking environmentally friendly methods and technologies are being developed.

In general, photocatalyst (Photocatalyst) is a compound of light (Photo) and catalyst (catalyst), which means a catalyst that accelerates a photoreaction or a catalyst using light, and refers to a substance that proceeds a catalytic reaction using light as an energy source. It not only consumes directly by participating in it, but also provides a mechanism different from the existing photoreaction, which satisfies the basic conditions as a general catalyst that can accelerate the reaction rate, and absorbs ultraviolet light when irradiated with light to the material to be expressed. Therefore, semiconducting metal oxides or sulfur compounds that can have strong reducing power and oxidizing power are mainly used. However, when fine photocatalytic particles are used as such, there is a need for a subsequent process using a membrane reactor to remove them. On the other hand, in this process, it is difficult to recover the total amount of photocatalyst due to the contamination of the film, and there is a problem that the treatment cost increases due to the loss of the photocatalyst flowing out of the processing apparatus. In addition, it is difficult to smoothly contact the organic material to be decomposed with the photocatalyst, so the decomposition efficiency of the organic material using the photocatalyst is not very high.

The present inventors, in a water treatment process using a membrane reactor, using photocatalytic reactions, as a result of earnest research to devise an apparatus for efficiently removing small molecule organic compounds, as a photocatalyst on a ceramic support having micro-sized pores Nanofiltration membrane by constructing a fluidized bed reactor having a PVDF nanofiltration membrane formed by a non-solvent-induced phase separation method from a polymer solution containing ZIF-8 carrying or without TiO ₂ and inducing a fluid flow toward the pores of the nanofiltration membrane The present invention was completed by confirming that the decomposition rate by ultraviolet irradiation can be improved by increasing the contact with the photocatalyst by standing the organic substances to be decomposed.

As one aspect for achieving the above object, the present invention is a ceramic support having pores having an average diameter of 0.1 to 5 μm, and on one side of the support, ZIF-8 or TiO having an average diameter of 100 to 300 nm as a photocatalyst ₂ containing pores having an average diameter of 20 to 200 nm, formed by nonsolvent induced phase separation from a polymer solution containing @ZIF-8 at 0.01 to 5% by weight, 10 to 100 A composite separation membrane comprising a polyvinylidene fluoride (PVDF) nanofiltration membrane, and a UV lamp positioned at a distance from the side of the nanofiltration membrane parallel to the longitudinal direction of the composite separation membrane, and decomposing organic matter As a fluidized-bed separation membrane reactor for water treatment, the influent to be treated with water flows from the PVDF nanofiltration membrane containing a photocatalyst to the ceramic support, and the organic material to be decomposed is retained in the PVDF nanofiltration membrane and can be decomposed by photocatalyst. It provides a fluidized bed separator reactor.

The present invention is to maximize the efficiency of decomposition of organic matter using a photocatalyst by using a water separation reactor using a polymer membrane to remove small molecule organic pollutants and to provide an apparatus that can prevent contamination of the membrane by deposition of these organic matter. It is designed.

Accordingly, the present inventors utilize the pores of the nanofiltration membrane as a microreactor by using the property of adsorbing the organic matter due to the hydrophobicity of the PVDF nanofiltration membrane, thereby improving the contact with the photocatalyst contained in the PVDF thin film, and of the water permeability due to the hydrophobicity. The reduction is to be overcome by causing an artificial flow of fluid in the reactor.

The reactor of the present invention may be configured based on a composite separation membrane based on a nanofiltration membrane of PVDF material. At this time, the PVDF nanofiltration membrane can be formed by a non-solvent-induced phase separation method. On the other hand, as described above, in the reactor of the present invention, the PVDF nanofiltration membrane is to use its pores as a microreactor, organic matter to be decomposed into the microreactor can be introduced and the surface area is widened to limit the space It can provide an increased surface area to enable a more efficient reaction within and can be formed on a ceramic support having micro-level pores through which fluid can flow through the pores. In order to form such pores, after blocking the lower surface of the ceramic tube used as a support, dipping it in a dip-coater containing the PVDF solution and pulling it out of the vacuum from the top surface to make the thin film uniformly to the surface and inner depth of the ceramic tube To be coated. At this time, the pores of the PVDF to be formed can be determined by considering the size of the organic material to be decomposed so that the organic material to be decomposed stays but the water to move it is permeable.

The non-solvent-induced phase separation method, which is a method used for manufacturing the PVDF nanofiltration membrane, is the most commonly used method for preparing a polymer-based porous membrane, and is a method using precipitation of a polymer solution by solvent-non-solvent exchange. Specifically, in the solvent-non-solvent exchange method, a polymer material is dissolved in an appropriate solvent at around room temperature to form a homogeneous solution, molded into a desired shape such as a film type, a tube type, or a hollow fiber type, and then immersed in a non-solvent solidification tank for the polymer. do. Subsequently, in the non-solvent, an exchange is made by diffusion of the solvent and the non-solvent, the composition of the polymer solution changes, and eventually the polymer is separated by liquid-liquid phase separation beyond the binodal or spinodal curve indicating the solubility limit. As precipitation occurs, the portion occupied by the solvent and non-solvent is formed into pores. At this time, the size of the pores formed according to the selection of the solvent and non-solvent, and the temperature and/or humidity during film formation can be controlled. This is related to the solvent-non-solvent exchange rate. When using a delayed phase separation in which solvent and non-solvent exchange is very slow, a symmetric membrane having uniform pores in the form of a sponge without macropores is formed, and when using fast phase separation, It is also possible to obtain an asymmetric membrane having a gradient in pore distribution of the cross-sectional structure of the skin layer and the membrane.

The PVDF nanofiltration membrane is a widely used separation membrane for water treatment, but the material itself, polyvinylidene fluoride, contains fluorine in the hydrocarbon main chain, and thus exhibits hydrophobicity. In order to improve the hydrophilicity, the surface may be modified. However, in the present invention, in addition to the function of the PVDF nanofiltration membrane as a water treatment membrane, each pore has the ability to permeate water for the purpose of being used as a microreactor for the reaction of organic substances using the photocatalyst contained therein, as well as to decompose. It is also necessary to maintain the adsorption power with organic matter. In this way, the unmodified PVDF thin film is used as it is to promote the adsorption of organic matter, but the reduced water permeability uses the porosity of the support and the filtration membrane and the fluid flow due to external stimuli.

Furthermore, the fluidized-bed separation membrane reactor for water treatment of the present invention discharges filtered water during the water treatment process and continuously operates in a manner of continuously reacting while adding influent water, so that a predetermined distance from the outer wall surface of the tubular ceramic support It is composed of a partition wall spaced apart and parallel to it, an upper plate connecting the upper portion of the partition wall and the upper portion of the ceramic support body, and a lower plate connecting the lower portion of the partition wall and the lower portion of the ceramic support body. By blocking the entry and exit of the influent, it is further provided with a space for storing the treated water transmitted through the PVDF nanofiltration membrane and an outlet formed at the bottom thereof to discharge the stored treated water to the outside. Can. An example of the structure of a specific reactor is schematically illustrated in FIG. 2.

TiO ₂ is the most representative material used as a catalyst in water treatment using a photolysis reaction. In particular, TiO ₂ has been attracting more attention because it has a stronger oxidizing power than ozone, which can decompose a wide variety of organic chemicals and ultimately decompose CO ₂ and H ₂ O. However, leaving the bench and applying it to a pilot-scale reactor reveals some limitations. First, due to the nature of using ultraviolet light, a photocatalytic reaction is possible only in a region that receives light from an ultraviolet lamp. For example, when a chemical treatment method such as ozone or a Fenton method is used, ozone or chemicals may spread evenly over the entire solution to be treated, while TiO ₂ is in the form of an opaque powder. In the case of scattering it, the reaction is possible only at a very shallow depth, which leads directly to low reaction efficiency. In addition, a process of separating the TiO ₂ powder used for water treatment again after the photocatalytic reaction is required. As a method for resolving these drawbacks, a thin film prepared by immobilizing TiO ₂ on a specific support can be used, but the efficiency is somewhat lower when manufacturing a thin film compared to the powder itself, and can be inserted into a certain volume of solution. The amount of the thin film and the content of TiO ₂ that can be contained in the individual thin film are still limited.

Thus, i) a catalyst with a higher photodecomposition efficiency than TiO ₂ was discovered, ii) immobilized to a high content, iii) increased contact of the organic material to be decomposed with the photocatalyst, and iv) of a reactor to achieve efficient light irradiation We want to improve the reaction by devising a form.

Conventionally in place of the TiO ₂ used as the photolysis reaction catalyst, in a water treatment reactor according to the present invention uses a ZIF-8 or in which TiO ₂ carrying a @ ZIF-8 TiO ₂ on the ZIF-8 as a photocatalyst. It has been reported that ZIF-8, in particular TiO ₂ @ZIF-8, by itself exhibits a photodegradation rate of organics compared to TiO ₂ (ChemistrySelect, 2017, 2: 7711-7722). Furthermore, in a specific embodiment of the present invention, both ZIF-8 and TiO ₂ @ZIF-8 have better resolution in methanol and ethanol decomposition reactions using a composite separator made of PVDF membrane formed by including these photocatalysts on a ceramic support. It confirmed that it showed. Specifically, in a relatively short time, the decomposition rate of TiO ₂ @ZIF-8 was high, and the final decomposition rate after long-term decomposition was the highest in ZIF-8.

The zeolitic imidazolate framework (ZIF)-8 used in the present invention is a type of metal-organic framework (MOF) that is topologically isomorphic with zeolite, and imidazolate as a ligand ( imidazolate) is composed of transition metals such as Fe, Co, Cu, and Zn that are tetrahedrally coordinated, and the angle formed by the metal-imidazole-metal is 145° of Si-O-Si in zeolite Is similar to Accordingly, ZIF-8 has MOF-specific micropores, and catalyst particles, such as TiO ₂ particles in the present invention, may be supported therein.

In addition, the present invention uses the point of including the organic molecule imidazole as a ligand. Specifically, in the present invention, the photocatalyst is fixed by dispersing it in a polymer PVDF nanofiltration membrane as a means for providing a large surface area. At this time, inorganic materials such as TiO ₂ are poorly miscible with the organic polymer PVDF and are not evenly dispersed and aggregated with each other or phase-separated and attached only to the surface of the PVDF thin film, which can be easily desorbed by the flow of the fluid. The used ZIF-8 and TiO ₂ @ZIF-8 include an imidazole which is an organic ligand in the skeleton, and thus has an advantage of being evenly dispersed in the PVDF solution. In addition, it is possible to remain attached to the PVDF nanofiltration membrane without being detached from external stimuli such as fluid flow.

Next, in order to minimize the decrease in the amount of catalyst that can be ultimately used when implemented as a thin film, a solution containing photocatalytic particles and PVDF is applied to a ceramic support having micrometer-level pores as a support, and then a non-solvent-induced phase separation method is applied. By forming a PVDF nanofiltration membrane containing a photocatalyst by to prepare a composite separator. By using the ceramic support having micrometer-level pores as described above, it is possible to form a PVDF nanofiltration film with a significantly increased surface area, as compared to forming on a flat support along the inner surface of the pores. Furthermore, since the PVDF nanofiltration membrane also includes nanometer-level pores, the photocatalyst may be contained on the increased surface of the PVDF thin film and/or inside the pores.

Furthermore, the use of a PVDF nanofiltration membrane comprising a photocatalyst supported by a ceramic support with micrometer-level pores can increase the contact of the photocatalyst with organics in the treated water to be decomposed. The pores of the ceramic support enable the flow of fluid through it, which can have the effect of continuously adjacent the decomposition organic substance contained in the fluid to the photocatalyst. On the other hand, the hydrophobicity of PVDF can provide the effect of increasing the residence time adjacent to the photocatalyst by inducing adsorption and/or trapping within the pores.

On the other hand, in order to achieve efficient light irradiation in a limited space, the ceramic support may be used in the form of a tube. At this time, a PVDF nanofiltration membrane containing a photocatalyst can be formed on the inner surface of the tubular support (FIG. 1).

Furthermore, as described above, a UV lamp for inducing a photocatalytic reaction can be positioned at the center of the tubular composite separator manufactured such that the photocatalyst faces the inner surface. By configuring the reactor with the above structure, it is possible to induce the reaction by irradiating the entire surface of the composite membrane with one lamp. Preferably, the UV lamp can be formed long enough to cover all the lengths of the PVDF nanofiltration membrane including the photocatalyst inside the tubular support so that no place where UV does not reach occurs. This can be configured by using a lamp of sufficient length alone or by connecting several lamps of a predetermined length in series. However, it is possible to introduce a transparent tube capable of transmitting UV at a position where the lamp is positioned so that the power of the lamp can illuminate the front surface without contacting the fluid, but is not limited thereto.

Alternatively, reactors having a composite separator prepared by forming PVDF nanofiltration membranes including photocatalysts on both surfaces of the tubular support, that is, inside and outside surfaces, are also included in the scope of the present invention. At this time, the reactor may further include one or more UV lamps on the outer wall surface of the reactor, or the reactor may be made of a transparent material capable of transmitting UV and may further include a UV lamp provided outside, but is not limited thereto. Does not.

In addition, in order to maximize the contact surface of the photocatalyst and the organic material to be decomposed, and to efficiently irradiate UV, the longitudinal direction of the composite separator and the UV lamp may be vertically arranged with the bottom surface of the reactor.

Furthermore, the fluidized-bed separation membrane reactor for water treatment of the present invention may further include an air blower located at the bottom of the lamp provided therein. By using the air injector, it is possible to increase the contact between the fluid containing the organic material and the photocatalyst by rising from the bottom of the reactor where the air injector is located, and forming a vortex that goes down the inner wall of the reactor. More specifically, as described above, the use of a porous ceramic support allows the composite separator of the present invention to provide a fluid flow therethrough and through the wall. However, the fluid rising by the air injected from the bottom of the reactor is intended to gradually descend under the influence of gravity, and the continuous flow from below collides with this to distribute the fluid flow to the outside of the reactor. That is, through this process, a flow in the direction of the PVDF nanofiltration membrane containing the photocatalyst occurs from the center of the reactor. The flow of the main fluid inside the reactor induced by the air injector has a pattern of rising from the center of the reactor and descending on the outer wall of the reactor, as indicated by arrows in FIG. 2. However, the flow to the side toward the composite membrane, which is derived from the flow from the rising reactor center, which is not shown in the figure, occurs, which is a factor that causes an increased contact between the photocatalyst and the organic material to be decomposed.

The fluidized-bed separation membrane reactor for water treatment of the present invention includes a composite membrane composed of a combination of materials and/or shapes capable of maximizing the resolution of organic substances in wastewater while stably fixing the MOF-based photocatalyst, and is provided on the inner surface of the tubular porous ceramic support. As a photocatalyst, a composite separation membrane having an increased photocatalyst content is formed by forming a PVDF nanofiltration membrane containing ZIF-8 or TiO ₂ @ZIF-8, a UV lamp at the center thereof, and an air injector at the bottom of the reactor to provide proper fluid flow. By forming, it is possible to increase the light irradiation efficiency and the contact with the organic material to be decomposed, thereby exhibiting an improved photodecomposition rate.

1 is a view showing the XRD results for the photocatalyst, TiO ₂ , ZIF-8 and TiO ₂ @ZIF-8 used in a specific embodiment of the present invention.
2 is a schematic view showing the configuration of a membrane reactor according to a specific embodiment of the present invention.
3 is a view showing an actual photograph of a membrane reactor according to a specific embodiment of the present invention.

Hereinafter, the present invention will be described in more detail through examples. These examples are intended to illustrate the present invention more specifically, but the scope of the present invention is not limited by these examples.

Manufacturing example One: TiO ₂ Produce

Titanium isopropoxide (TTIP) was added to acetic acid (AA) at room temperature, and the solution was vigorously mixed, and water was added at a molar ratio of TTIP:AA:water=1:10:350. It was added dropwise over 1 hour. The prepared solution was reacted by ultrasonic treatment for 30 minutes, and stirred for 5 hours until TiO ₂ nanocrystals formed and became transparent. The solution was aged in an oven at 70° C. for 24 hours, dried at 100° C., crushed into powder, and fired at 400° C. for 5 hours.

Manufacturing example 2: ZIF -8 Manufacturing

1.1 g of zinc nitrate was dissolved in 20 mL water to prepare a first solution, and 10.54 g of 2-methylimiziazole was dissolved in 50 mL water to prepare a second solution. The two solutions were mixed to obtain a milky suspension. The solution was placed in an oven for 18 hours and centrifuged at 8000 rpm for 2 hours. The separated sample was washed 3 times with water and dried at 100° C. for 12 hours.

Manufacturing example 3: TiO ₂ @ZIF-8 manufacture

1.3595 g of zinc nitrate and 0.036 g of TiO ₂ were added to 70 mL methanol and mixed by ultrasonic treatment. A 70 mL methanol solution in which 3 g of 2-methylimidazole was dissolved was mixed with a solution containing zinc nitrate and TiO ₂ prepared in advance to obtain a milky suspension. After mixing for 6 hours, the product was recovered by centrifugation at 8000 rpm for 20 minutes, and the final sample was washed three times with methanol and then vacuum dried at 70°C for 6 hours.

remind Manufacturing example Catalyst particles prepared according to 1 to 3 are average diameter 50 to 200 nm The size is shown.

Manufacturing example 4: Photocatalyst Preparation of containing membrane

Porous separators were prepared using nonsolvent induced phase separation (NIPS). Specifically, 50 g of polyvinylidene fluoride (PVDF), the main material, is dissolved in 250 g of dimethylacetamide (DMAc), a solvent heated to 80° C., and polyvinylpyrrolidone, a pore-forming agent ( 0.5 g of polyvinylpyrrolidone (PVP) K15 was added. At this time, the temperature and relative humidity were maintained at 25°C and 60% or more, respectively. As the photocatalyst, P25 (Comparative Example 1), TiO ₂ (Comparative Example 2), ZIF-8 (Example 1), and TiO ₂ @ZIF-8 (Example 2) were respectively added to the solution by 1.0 wt% compared to PVDF. To prepare a separator by dip coating a polymer solution in which the photocatalyst is dispersed on a support made of ceramic, eg, alumina or silica. Water was used as a non-solvent, and coagulation with water was induced after coating.

In the thus prepared separator, photocatalyst particles are uniformly dispersed and mixed in PVDF by the NIPS, and the PVDF thin film is uniformly formed even inside the pores of the ceramic by using a vacuum pump.

Experimental Example One: Photocatalytic XRD analysis

XRD was measured to confirm the crystal structures of three types of photocatalysts synthesized according to Preparation Examples 1 to 3, TiO ₂ , ZIF-8 and TiO ₂ @ZIF-8, and the results are shown in FIG. 1. As shown in FIG. 1, TiO ₂ @ZIF-8 was found to include both characteristic peaks appearing in TiO ₂ and ZIF-8, which TiO ₂ @ZIF-8 retained the crystal structure of ZIF-8. while, it indicates that contain TiO ₂ in the pores.

Experimental Example 2: Photocatalyst Removal of organic matter in water by a membrane reactor equipped with a containing membrane

Methanol and ethanol as an organic material to be removed in 2.5 kg of water were mixed with 0.444 kg and 0.639 kg, respectively, to prepare wastewater having a molar ratio of 10:1:1. The thus prepared wastewater was continuously introduced into the reactors having separation membranes of Comparative Examples 1 and 2, and Examples 1 and 2 prepared according to Preparation Example 4 to recover the permeate and concentrate as a concentrate. Separated and circulated. The methanol and ethanol concentrations of the double permeate were measured to calculate respective removal yields. The specific structure of the used reactor is schematically illustrated in FIG. 2, and a real picture of the actual implemented reactor is illustrated in FIG. 3. As shown in FIG. 2, a double-walled tubular separator was vertically placed in the reactor, and a lamp capable of irradiating ultraviolet rays was provided at the center thereof. In addition, an air blower was placed at the bottom of the reactor so that the waste liquid could circulate in the vertical direction.

5 hours 20 hours Comparative Example 1 (P25) 4.7% 16.7% Comparative Example 2 (TiO ₂ ) 4.5% 14.1% Example 1 (ZIF-8) 10.1% 50.5% Example 2 (TiO ₂ @ZIF-8) 15.3% 39.1%

5 hours 20 hours Comparative Example 1 (P25) 8.1% 17.9% Comparative Example 2 (TiO ₂ ) 9.2% 18.6% Example 1 (ZIF-8) 8.6% 47.9% Example 2 (TiO ₂ @ZIF-8) 14.3% 37.2%

Claims (9)

A non-solvent-derived phase from a ceramic support having pores having an average diameter of 0.1 to 5 μm in size, and a polymer solution containing ZIF-8 having an average diameter of 100 to 300 nm as a photocatalyst in an amount of 0.01 to 5% by weight on one side of the support. Composite membrane comprising a polyvinylidene fluoride (PVDF) nanofiltration membrane having pores having an average diameter of 20 to 200 nm and formed by nonsolvent induced phase separation. And
A fluidized-bed separation membrane reactor for water treatment with organic matter resolution, having a UV lamp positioned at a distance from it on the wall surface of the nanofiltration membrane parallel to the longitudinal direction of the composite membrane,
The influent to be treated with water flows from the PVDF nanofiltration membrane containing a photocatalyst to the ceramic support, and the organic material to be decomposed is retained in the PVDF nanofiltration membrane and can be decomposed by a photocatalyst, a fluidized bed separation membrane reactor for water treatment.
According to claim 1,
The ceramic support is a fluidized-bed separation membrane reactor for water treatment.
According to claim 2,
The UV lamp is a fluidized bed membrane reactor for water treatment, which is located inside the tubular composite membrane.
According to claim 2,
The PVDF nanofiltration membrane is formed by blocking the lower surface of a tubular ceramic support, dipping it in a coating container containing a PVDF solution, and extracting it by vacuum from the upper surface to form a uniform coating on the surface and pores of the ceramic support.
According to claim 4,
Consists of a partition wall spaced apart from the outer wall surface of the tubular ceramic support and spaced at a predetermined distance, the upper plate connecting the upper portion of the partition wall and the upper portion of the ceramic support body, and a lower plate connecting the lower portion of the partition wall to the lower portion of the ceramic support body. The partition wall, the upper plate and the lower plate block the flow of liquid to block the inflow and out of the inflow water, and are formed at the bottom of the space to store the treated water transmitted through the PVDF nanofiltration membrane and at the bottom thereof to discharge the stored treated water to the outside. A fluidized-bed separation membrane reactor for water treatment, which is further provided with an outlet capable of being continuously driven.
According to claim 1,
Longitudinal direction of the composite membrane and the UV lamp is a fluidized bed membrane reactor for water treatment that is arranged perpendicular to the bottom surface of the reactor.
According to claim 1,
A fluidized bed separation membrane reactor for water treatment, further comprising an air blower located at the bottom of the lamp.
A method for water treatment using the reactor according to any one of claims 1 to 7.
A ceramic support having pores having an average diameter of 0.1 to 5 μm, and one surface of the support, cost from a polymer solution containing 0.01 to 5% by weight of TiO ₂ @ZIF-8 having an average diameter of 100 to 300 nm as a photocatalyst Contains pores having an average diameter of 20 to 200 nm, formed by nonsolvent induced phase separation, and includes 10 to 100 μm thick polyvinylidene fluoride (PVDF) nanofiltration membrane A composite separator; And
A fluidized-bed separation membrane reactor for water treatment with organic matter resolution, having a UV lamp positioned at a distance from it on the wall surface of the nanofiltration membrane parallel to the longitudinal direction of the composite membrane,
The influent that is the water treatment object flows from the PVDF nanofiltration membrane containing the photocatalyst to the ceramic support, and the organic material to be decomposed is retained in the PVDF nanofiltration membrane and can be decomposed by a photocatalyst,
The PVDF nanofiltration membrane is formed by blocking the lower surface of the tubular ceramic support, dipping it in a coating container containing the PVDF solution, and extracting it by vacuum from the upper surface to form a uniform coating on the surface of the ceramic support and inside the pores.

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