KR101708389B1 - Photocatalyst complex composition for treating heavy metal in water and manufacturing method of the same - Google Patents
Photocatalyst complex composition for treating heavy metal in water and manufacturing method of the same Download PDFInfo
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- KR101708389B1 KR101708389B1 KR1020150061830A KR20150061830A KR101708389B1 KR 101708389 B1 KR101708389 B1 KR 101708389B1 KR 1020150061830 A KR1020150061830 A KR 1020150061830A KR 20150061830 A KR20150061830 A KR 20150061830A KR 101708389 B1 KR101708389 B1 KR 101708389B1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0209—Impregnation involving a reaction between the support and a fluid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/002—Catalysts characterised by their physical properties
- B01J35/004—Photocatalysts
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Abstract
The present invention relates to a photocatalytic composite for immobilizing a photocatalyst, laponite, zeolite, and red mud on an organic support such as butadiene rubber to treat a broadly contaminated target water and removing heavy metals, and a method for producing the same, Zeolite, and red mud to prepare a photocatalyst mixture, swelling / modifying the organic support, mixing the photocatalyst mixture with the photocatalyst mixture, heating the photocatalyst in an electric furnace, fixing the photocatalyst, and drying the photocatalyst at a predetermined temperature. According to the photocatalytic composite composition for removing heavy metals in the water and the method for producing the same, contaminants are decomposed by the photocatalyst material in the vicinity of the organic support when swelling the laponite, thereby efficiently removing not only heavy metals but also organic contaminants There is an advantage to be able to do.
Description
The present invention relates to a photocatalytic composite composition for removing heavy metals in water, a method for producing a photocatalytic composite composition, and a device for supporting a photocatalytic composite composition. More particularly, the present invention relates to a photocatalyst composition for removing heavy metals in water by mixing laconite The present invention provides a photocatalytic composite composition capable of removing heavy metals by swelling / modifying and drying the same, a method for producing a photocatalytic composite composition, and a device for supporting a photocatalytic composite composition.
Contaminants that are naturally present in water or generated by humans are composed mostly of complex substances rather than single substances, and they often exist in the form of organic complex substances or heavy metal complex substances.
Generally, in order to remove heavy metals present in the water, organic pollutants are treated first with microorganisms, activated carbon, AOP, etc., and then processed using a separate membrane, chemical precipitation, etc. to remove heavy metals. to be.
However, these existing methods must secure a lot of land for installing the facility, and raise the hard problems considering the power consumption for the employment of the driver and the operation of the facility.
Therefore, recently, the technology that is attracting attention for removing organic pollutants more effectively is the photocatalyst technology which is one of the advanced processing technologies (AOP), the laponite which has heavy metal adsorption ability, the zeolite and the red mud, It is a manufacturing technology of a photocatalytic composite capable of removing heavy metals.
In general, titanium dioxide (TiO 2 ) or zinc oxide (ZnO), which is most widely used as a metal oxide using a photocatalytic reaction, has a strong oxidation and reduction reaction by ultraviolet light, thereby exhibiting excellent optical activity, optical, chemical and biological stability, Durability and economical properties of the photocatalyst.
However, such a photocatalyst material is excellent in efficiency as a photocatalyst, but the necessity of immobilization due to the problem of recovery after water treatment and the decrease in efficiency due to the reduction of dispersion in aqueous solution is raised, and thus a process for immobilization on activated carbon, clay, have.
In addition, attempts have been made to immobilize the photocatalyst material using various binders when fixing the photocatalyst to various supports. However, when the immobilization is performed using a binder, the characteristics of the inorganic support can not be utilized.
A method of coating various photocatalysts on the surface of a conventional inorganic support has been developed, but there is a problem in that the water treatment efficiency is reduced sharply due to the poor water resistance of some combined bodies, resulting in the photocatalyst being eliminated.
Therefore, there is no attempt to bond the photocatalyst to the surfaces of various organic supports having a relatively high water resistance, and it is necessary to study the above.
SUMMARY OF THE INVENTION Accordingly, the present invention has been made to solve the above-mentioned problems occurring in the prior art, and it is an object of the present invention to provide a photocatalytic composite composition capable of removing organic contaminants by a photocatalyst material through a mechanism of laponite and water molecules.
The present invention can continuously maintain an excellent water resistance and high organic contaminant adsorption efficiency of an organic support, photodissociate organic contaminants through a photocatalyst bonded to the surface, and simultaneously perform adsorption and photolysis, Another object of the present invention is to provide a photocatalyst-organic composite composition for treating a refractory organic compound capable of significantly increasing treatment efficiency and a method for producing the same.
It is another object of the present invention to provide a supporting device capable of effectively supporting a photocatalytic-organic composite composition in water.
The present invention has been made in view of the above problems, and it is an object of the present invention to provide an apparatus and method for controlling the same.
According to one aspect of the present invention, there is provided a method for preparing a photocatalytic composite composition for removing heavy metals in water, the method comprising: A photocatalyst mixture preparation step of mixing a photocatalyst, laponite, zeolite, and red mud to prepare a photocatalyst mixture; A photocatalyst adhering step of attaching the photocatalyst mixture to an organic support containing a butadiene rubber by using a swelling-reforming solvent; A photocatalyst complete fixing step of post-treating the photocatalyst mixture attached to the organic support to fix the photocatalyst mixture; And a step of finishing the photocatalytic composite to complete the photocatalytic composite through a post-treatment including the step of completely fixing the photocatalyst and drying.
In the photocatalyst mixture preparation step of the present invention, the photocatalyst mixture is preferably prepared by adjusting the viscosity.
In the photocatalytic mixture preparation step of the present invention, the photocatalyst mixture may be prepared by mixing the photocatalyst and the laponite at a predetermined ratio, swelling the mixture, and adding the zeolite and the red mud at a predetermined ratio.
In the photocatalyst mixture preparation step of the present invention, the photocatalyst, the laponite, the water, the zeolite and the red mud are preferably mixed in a ratio of 3: 3: 100: 0.1: 0.1 to 3: 3: 100: 1: 1 Do.
In the photocatalyst mixture preparation step of the present invention, the photocatalyst mixture is preferably prepared by adjusting the concentration.
The photocatalyst mixture of the present invention may be prepared by mixing the photocatalyst and the laponite at a predetermined ratio, mixing the zeolite and the red mud at a predetermined ratio, and adjusting the concentration according to the degree of contamination of the target water body, .
In the photocatalyst mixture preparation step of the present invention, the photocatalyst, the laponite, the zeolite, and the red mud are mixed in a ratio of 1: 1: 0.1: 0.1 to 1:10: 1: 1, respectively.
The step of adhering the photocatalyst according to the present invention is carried out by swelling and modifying the swollen and modified support by being supported on the swelling-reforming solvent so as to form pores and channels of various sizes on the surface of the organic support, and the swollen and modified organic support is dropped on the photocatalyst mixture, To the substrate.
The organic-based support of the present invention is preferably supported on the swelling-reforming solvent for 60 minutes or more and stirred.
In the step of adhering the photocatalyst of the present invention, it is preferable that the swelling-reforming solvent and the photocatalyst mixture are supported on the photocatalyst-tetrahydrofuran slurry and the organic-based support is stirred to adhere the photocatalyst mixture to the organic-based support.
The step of completely fixing the photocatalyst of the present invention preferably includes thermoforming the organic support having the photocatalyst.
The step of completely fixing the photocatalyst of the present invention preferably includes drying the organic support having the photocatalyst mixture at 130 to 180 ° C for 5 minutes.
In the step of preparing the photocatalyst-organic composite according to the present invention, it is preferable that the photocatalyst-organic composite is dried at 100 ° C for 1 hour and cooled at room temperature.
It is preferable to further include an incomplete attached photocatalytic desorption step of desorbing the photocatalyst imperfectly attached to the organic support after the step of completely fixing the photocatalyst and the step of completing the photocatalytic composite of the present invention.
The photocatalytic composite composition of the present invention is preferably prepared by a method for producing a photocatalytic composite composition for removing heavy metals in water.
The photocatalytic composite composition supporting apparatus of the present invention comprises a head part; A body portion extending downward from the head portion and having a plurality of mesh-type supporting pipes connected to each other to receive the photocatalytic composite composition in the supporting tube; And a light source unit provided inside the body.
The body portion of the present invention preferably includes an opening / closing lid provided at the lower end of the supporting tube.
The effects of the photocatalytic composite composition for removing water heavy metals according to the present invention, the method for producing the photocatalytic composite composition, and the apparatus for supporting the photocatalytic composite composition are as follows.
The present invention is characterized in that contaminants moving together with water molecules during swelling of laponite become close to the butadiene rubber and thus a rapid sorption occurs and an environment in which sorbed contaminants are reacted with the photocatalyst located on the butadiene rubber surface is created , An increase in the decomposition efficiency of contaminants, and the removal of not only heavy metals but also organic pollutants.
The present invention is advantageous in that it is possible to provide a customized photocatalytic composite composition optimized for a target water area by varying the blending ratio of laponite, photocatalyst, and other additives according to the situation of the area to be polluted.
The present invention has the effect of decomposing contaminants through photocatalyst-adsorption reaction for a long period of time without replacing the catalyst material by bonding the photocatalyst to the surface of various organic supports having relatively high water resistance according to the increase in water resistance of the photocatalyst bonded body.
Since the photocatalytic composite can be effectively carried in water by utilizing the photocatalytic composite support device, the photocatalytic complex can improve the photocatalytic decomposition efficiency.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flow chart showing a method for producing a photocatalytic composite composition for removing heavy metals in water according to the present invention. FIG.
2 is a front view showing a photocatalytic composite composition supporting apparatus for supporting a photocatalytic composite composition for removing water heavy metals according to the present invention in water.
Fig. 3 is an enlarged view of the lower end of Fig. 2; Fig.
The description of the present invention is merely an example for structural or functional explanation, and the scope of the present invention should not be construed as being limited by the embodiments described in the text. That is, the embodiments are to be construed as being variously embodied and having various forms, so that the scope of the present invention should be understood to include equivalents capable of realizing technical ideas. Also, the purpose or effect of the present invention should not be construed as limiting the scope of the present invention, since it does not mean that a specific embodiment should include all or only such effect.
Meanwhile, the meaning of the terms described in the present application should be understood as follows.
The terms "first "," second ", and the like are intended to distinguish one element from another, and the scope of the right should not be limited by these terms. For example, the first component may be referred to as a second component, and similarly, the second component may also be referred to as a first component.
It is to be understood that when an element is referred to as being "connected" to another element, it may be directly connected to the other element, but there may be other elements in between. On the other hand, when an element is referred to as being "directly connected" to another element, it should be understood that there are no other elements in between. On the other hand, other expressions that describe the relationship between components, such as "between" and "between" or "neighboring to" and "directly adjacent to" should be interpreted as well.
It is to be understood that the singular " include " or "have" are to be construed as including the stated feature, number, step, operation, It is to be understood that the combination is intended to specify that it does not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.
In each step, the identification code (e.g., a, b, c, etc.) is used for convenience of explanation, the identification code does not describe the order of each step, Unless otherwise stated, it may occur differently from the stated order. That is, each step may occur in the same order as described, may be performed substantially concurrently, or may be performed in reverse order.
All terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, unless otherwise defined. Commonly used predefined terms should be interpreted to be consistent with the meanings in the context of the related art and can not be interpreted as having ideal or overly formal meaning unless explicitly defined in the present application.
The present invention relates to a photocatalytic material and a method for producing a photocatalyst composition which comprises a photocatalyst material and a laponite which is an artificial clay having a property of swelling when water molecules are encountered and transmitting light therethrough and a laponite which is widely contaminated by using zeolite and red mud. The present invention relates to a photocatalytic composite capable of treating various groundwater and river water and removing various heavy metals in the water.
The present invention relates to a photocatalytic composite comprising a photocatalyst and laponite immobilized on an organic support such as butadiene rubber (BR), which is formed by adding zeolite and red mud which are specialized for removing heavy metals.
The laponite included in the present invention absorbs water molecules in the water and swells the water molecules so that contaminants present in the water as the water molecules are absorbed by the laponite are adsorbed by the excellent organic contaminant sorption efficiency of the butadiene rubber, Contaminants such as photocatalysts and heavy metals on the surface of the rubber are brought close to each other, and the pollutants can be removed through an excellent photocatalytic mechanism.
The present invention relates to a photocatalyst mixture preparation step (S100) for mixing photocatalyst, laponite, zeolite, and red mud; An organic support swelling-reforming step (S200) for swelling and modifying the organic support to form pores and channels on the surface of the organic support; (S300) of impregnating or adhering the photocatalyst mixture to the swollen-modified organic support; (S400) for post-treating the photocatalyst adhered to the organic support to completely fix the photocatalyst; An incomplete attached photocatalytic desorption step (S500) for desorbing a photocatalyst imperfectly attached to the organic support; And a photocatalytic composite preparation step (S600) through a post-treatment including the incomplete attached photocatalytic desorption step (S500) and drying.
Hereinafter, each step will be described in detail.
The photocatalyst mixture preparation step (S100) is a step for preparing a photocatalyst mixture by mixing photocatalyst material, laponite, zeolite and red mud. The photocatalyst material is at least one of a nano-sized titanium dioxide (TiO 2 ) powder and a zinc oxide (ZnO) powder.
The photocatalyst mixture preparation step (S100) may include a step (S100-1) of preparing a photocatalyst mixture by adjusting viscosity, or a step (S100-2) of preparing a photocatalyst mixture by adjusting the concentration.
In the step (S100-1) of preparing the photocatalyst mixture by controlling the viscosity, 3 g of photocatalyst, 3 g of laponite and 100 g of water are mixed and swelled to form a gel state. In this gel state mixture, zeolite 0.1 g to 1 g each of red mud powder is added to prepare a photocatalyst mixture. That is, the photocatalyst mixture is mixed at a ratio of 3: 3: 100: 0.1: 0.1 to 3: 3: 100: 1: 1 in the ratio of photocatalyst: laponite: water: zeolite: redmud.
The step (S100-1) of preparing the photocatalyst mixture by adjusting the viscosity is a method for adjusting the workability while adjusting the amount of the additive material to meet the condition when the viscosity of the mixture is low or the model is difficult to implement .
In the step (S100-2) of preparing the photocatalyst mixture by adjusting the concentration, the photocatalyst and the laponite powder are mixed at a ratio of 1: 1 to 1:10, respectively, and then the zeolite and the red mud powder are mixed at a ratio of 0.1 to 1 To prepare a photocatalyst mixture. That is, the photocatalyst mixture is mixed at a ratio of 1: 1: 0.1: 0.1 to 1: 10: 1: 1 of the photocatalyst: laponite: zeolite: redmud.
The step (S100-2) of preparing the photocatalyst mixture by adjusting the concentration is a method for preparing a customized photocatalytic composite by controlling the concentration of the complex according to the degree of heavy metal contamination on the site.
When the photocatalyst mixture is prepared as described above, an organic support swelling-reforming step (S200) is performed to swell and modify the organic support to form voids and channels on the surface of the organic support.
The organic support provided in the organic support swelling-reforming step S200 may be composed of butadiene rubber (BR), styrene-butadiene rubber (SBR), and nitrile rubber (NBR), each of which is made of polybutadiene And is preferably composed mainly of butadiene rubber (BR).
The swelling and modification of the organic support in the organic support swelling-reforming step (S200) allows the swelling-reforming solvent to form pores and channels of varying sizes on the surface of the organic support. The swelling-reforming solvent is preferably tetrahydrofuran (THF).
In the swelling-modifying step (S200) of the organic support, the organic support is held for at least 1 hour (60 minutes or more) in a pure THF solution which is a swelling-reforming solvent and stirred to uniformly dissolve the surface of the organic support, Forming a void and a channel of the photocatalyst, and dropping the photocatalyst powder to attach the photocatalyst.
Here, the concentration of tetrahydrofuran (THF) is preferably about 250 mg / L, and the capacity capable of flooding is suitable so that the organic support can be evenly dissolved. When the organic-based support is supported on tetrahydrofuran (THF), the organic-based support is denser than tetrahydrofuran, so that the organic-based support initially floats. However, after about 15 minutes, the organic-based support swells and sinks So that sufficient swelling and modification of the organic support may take place.
Subsequently, the photocatalyst completely fixing step (S400) of post-treating the photocatalyst adhering to the organic support is completed, comprising thermoforming the photocatalyst-coated (attached) organic support.
More specifically, the step of completely fixing the photocatalyst (S400) includes dropping the organic support onto the photocatalytic mixture prepared in the photocatalytic mixture preparation step (S100), and drying the photocatalyst mixture at a temperature of about 130 to 180 DEG C for 5 minutes in an electric furnace do. When the organic support is dried in this way, tetrahydrofuran (THF) volatilizes and the swollen organic support shrinks again to fix the photocatalyst on the surface. Tetrahydrofuran (V THF) is instantaneously volatilized, And a relatively large surface area can be ensured.
Next, an incomplete attached photocatalytic desorption step (S500) is performed in which the photocatalyst is incompletely adhered to the organic support after the step of completely fixing the photocatalyst (S400). The imperfect attached photocatalytic desorption step (S500) includes ultrasonic cleaning at 700 W for 30 minutes in order to desorb the photocatalyst which is incompletely adhered to the surface of the organic support having various sizes of pores and channels .
After the incompletely adhered photocatalyst is desorbed as described above, a photocatalytic composite body completion step (S600) for completing the photocatalytic-organic complex is performed. The step of completing the photocatalytic composite (S600) includes a step of recovering the organic support on which the photocatalyst is fixed and drying it at about 100 DEG C for one hour so as to evaporate moisture, and then leaving it at room temperature.
Since the photocatalytic composite having the above-described structure has floating characteristics in water, it is preferable that the photocatalytic composite body is installed in the photocatalytic composite
The photocatalytic composite
The
As shown in FIG. 3, the opening /
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit and scope of the present invention as defined by the following claims It can be understood that
S100: Photocatalytic mixture preparation step
S200: Organic support swelling-reforming step
S300: Step of attaching photocatalyst
S400: Step of completely fixing the photocatalyst
S500: incomplete attached photocatalytic desorption step
S600: Photocatalytic complex completion stage
Claims (15)
A photocatalyst mixture preparation step of mixing a photocatalyst, laponite, zeolite, and red mud to prepare a photocatalyst mixture;
A photocatalyst adhering step of attaching the photocatalyst mixture to an organic support containing a butadiene rubber by using a swelling-reforming solvent;
A photocatalyst complete fixing step of post-treating the photocatalyst mixture attached to the organic support to fix the photocatalyst mixture; And
The photocatalytic complex is completed by a post-treatment including drying after the photocatalytic complete fixing step,
The photocatalyst mixture is prepared by a method of preparing a viscous mixture. The photocatalyst is mixed with the laponite at a predetermined ratio and swelled. The photocatalyst mixture is prepared by adding the zeolite and the red mud at a predetermined ratio,
The photocatalyst, the laponite, the water, the zeolite, and the red mud are mixed in a ratio of 3: 3: 100: 0.1: 0.1 to 3: 3: 100: 1: 1,
A method for preparing a photocatalytic composite composition for removing heavy metals in water.
A photocatalyst mixture preparation step of mixing a photocatalyst, laponite, zeolite, and red mud to prepare a photocatalyst mixture;
A photocatalyst adhering step of attaching the photocatalyst mixture to an organic support containing a butadiene rubber by using a swelling-reforming solvent;
A photocatalyst complete fixing step of post-treating the photocatalyst mixture attached to the organic support to fix the photocatalyst mixture; And
The photocatalytic complex is completed by a post-treatment including drying after the photocatalytic complete fixing step,
The step of preparing the photocatalyst mixture is a concentration-controlled manufacturing type. The photocatalyst and the laponite are mixed at a predetermined ratio, and the zeolite and the red mud are mixed at a predetermined ratio to adjust the concentration according to the degree of contamination Thereby preparing the photocatalyst mixture,
The photocatalyst, the laponite, the zeolite, and the red mud are mixed at a ratio of 1: 1: 0.1: 0.1 to 1:10: 1: 1, respectively
A method for preparing a photocatalytic composite composition for removing heavy metals in water.
The step of attaching the photocatalyst
Reforming solvent so as to form pores and channels of various sizes on the surface of the organic-based support, and swelling and modifying the swelling-
Subjecting the swollen and modified organic support to the photocatalytic mixture to attach the photocatalyst
A method for preparing a photocatalytic composite composition for removing heavy metals in water.
The step of completely fixing the photocatalyst
And thermoforming the organic support having the photocatalyst thereon
A method for preparing a photocatalytic composite composition for removing heavy metals in water.
The step of completely fixing the photocatalyst
And drying the organic-based support having the photocatalyst mixture at 130 to 180 ° C for 5 minutes
A method for preparing a photocatalytic composite composition for removing heavy metals in water.
Further comprising an imperfect attached photocatalytic desorption step for desorbing the photocatalyst imperfectly adhered to the organic support after the step of completely fixing the photocatalyst and before the step of completing the photocatalytic complex
A method for preparing a photocatalytic composite composition for removing heavy metals in water.
Head portion;
A body portion extending downward from the head portion and having a plurality of mesh-type supporting pipes connected to each other to receive the photocatalytic composite composition in the supporting tube;
And a light source unit provided in the body portion
Wherein the photocatalytic composite composition supporting apparatus comprises:
The body
And an opening / closing lid provided at the lower end of the supporting pipe
Wherein the photocatalytic composite composition supporting apparatus comprises:
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| J. C. Joo et al., Journal of Hazardous Materials 2013, 263, 596-574.* |
| 장대규 외 6인, J. Kor. Soc. Environ. Eng., 2014, 36, 771-780.* |
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