WO2011145801A2 - Matériau poreux à base de carbone sphérique actif en lumière visible, et son procédé de préparation - Google Patents

Matériau poreux à base de carbone sphérique actif en lumière visible, et son procédé de préparation Download PDF

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WO2011145801A2
WO2011145801A2 PCT/KR2011/001950 KR2011001950W WO2011145801A2 WO 2011145801 A2 WO2011145801 A2 WO 2011145801A2 KR 2011001950 W KR2011001950 W KR 2011001950W WO 2011145801 A2 WO2011145801 A2 WO 2011145801A2
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spherical carbon
visible light
titanium
exchange resin
transition metal
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PCT/KR2011/001950
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Korean (ko)
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WO2011145801A3 (fr
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서정권
정원채
홍지숙
정윤호
김범식
박유인
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한국화학연구원
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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
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/084—Decomposition of carbon-containing compounds into carbon
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/50—Silver
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
    • C02F1/325—Irradiation devices or lamp constructions
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/08—Ion-exchange resins
    • B01J31/10—Ion-exchange resins sulfonated
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/22—O2
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/10—Photocatalysts

Definitions

  • the present invention relates to a method for preparing visible light-activated spherical carbon-based pore material, and more specifically, titanium ion, which is a photoactive catalyst, is bound to an exchanger of a strongly acidic cation exchange resin by an ion exchange method, and then the same method. After the transition metal is supported on the ion exchange resin by using a heat treatment, the ion exchange resin loaded with the transition metal and titanium ions is heat treated to have a visible light active spherical carbon-based pore material which is active in the visible region and can be applied to the actual commercialization process. It relates to a manufacturing method.
  • Photocatalyst is a material having strong redox ability by light energy, and by such photocatalytic action, it can sterilize, antibacterial, decompose, antifouling, deodorize, and capture adhesion substances on the surface of material, air and contaminants in solution. Therefore, photocatalysts are used in a wide range of applications such as glass, tiles, exterior walls, food, factory walls, metal products, water tanks, marine pollution purification, building materials, mold prevention, UV protection, water purification, atmospheric purification, and hospital infection prevention. Among many photocatalysts used for such applications, titanium dioxide (TiO 2 ) having various advantages such as excellent photoactivity, chemical or biological stability, and durability is mainly used.
  • titanium dioxide shows a very good photocatalytic activity in the ultraviolet region, it is well known that it does not have a photocatalytic activity in the visible region, which occupies most of the sunlight.
  • various studies have been attempted to develop photocatalysts that are active under visible light.
  • a photoactive spherical carbon-based porous material having a favorable shape for application to a commercialization system Domestic Patent No. 672,906
  • the size is about 250 to 450 ⁇ m and the outer density is 1 to 2 g /
  • a spherical carbon-based pore material of ml allows the operation of a photo reactor in a fluidized bed type.
  • the well-developed spherical carbon-based pore material acts as a photocatalyst carrier, which has the advantage of increasing the mass transfer rate.It also shows high efficiency in the ultraviolet region due to the supported titanium dioxide. However, it has a disadvantage in that it does not exhibit photolysis efficiency in the visible light range outside the ultraviolet region.
  • the present inventors have studied to overcome the problems of the prior art as described above, by producing a visible light active spherical carbon-based pore material in which titanium and transition metals are mixed in a strong acid cation exchange resin, the prior art mentioned above Solving the disadvantages of these as well as maintaining a form that is advantageous to apply to the commercialization system has been found to have a high photolysis efficiency in the visible light region as well as ultraviolet light, and completed the present invention.
  • an object of the present invention is to provide a method for producing a visible light active spherical carbon-based pore material having high photolysis efficiency not only in the ultraviolet region but also in the visible region.
  • It relates to a method for producing a visible light active spherical carbon-based pore material comprising a.
  • Visible light-activated spherical carbon-based porous material prepared according to the present invention has the advantage of excellent organic matter removal efficiency in the wavelength range of the visible light region of 365 nm as well as the wavelength range of the strong ultraviolet energy of 254 nm, which has been widely used in general. There is this.
  • the visible light-activated spherical carbon-based porous material prepared according to the present invention exhibits an even surface spherical shape, the diameter is about 300 ⁇ 400 ⁇ m, has a strength of 8 ⁇ 9 kg / a unit to prevent collision between particles in the fluidized bed It can be prevented by the loss, and has the advantage that it has an advantageous form to be applied to the commercialization system.
  • Visible light-activated spherical carbon-based porous material of the present invention is expected to be applicable to the water treatment and air purification industry because it has a high photochemical activity in the visible light range, it is expected to have a tremendous impact when applied to various commercial processes using a photocatalyst do.
  • 1 is a flowchart illustrating a method of manufacturing Ti-M-SCM.
  • FIG. 2 is an SEM image of a visible light active spherical carbon-based pore material prepared from a strongly acidic cation exchange resin.
  • FIG. 3 is an EPMA image of a visible light activated spherical carbon-based pore material prepared from a strongly acidic cation exchange resin.
  • Figure 4 (a) is a graph showing the optical activity at 254nm UV wavelength of the titanium photoactive spherical carbon-based porous material prepared from a strongly acidic cation exchange resin and the visible light activated spherical carbon-based porous material of Examples 1 to 5 (initial humus (HA) ) Concentration 10 ppm).
  • Figure 4 (b) is a graph showing the light activity at 365nm UV wavelength of titanium photoactive spherical carbon-based pore material prepared from a strongly acidic cation exchange resin and the visible light active spherical carbon-based pore material of Examples 1 to 5 (initial humus ( HA) concentration 10 ppm).
  • FIG. 5 is a graph showing optical activity at 254 nm UV wavelength of a visible light active spherical carbon based porous material prepared from a strongly acidic cation exchange resin and a spherical carbon based porous material loaded with a transition metal alone (initial humic (HA) concentration of 10 ppm). ).
  • FIG. 6 is a graph showing optical activity at 365 nm UV wavelength of a visible light active spherical carbon based porous material prepared from a strongly acidic cation exchange resin and a spherical carbon based porous material carrying a transition metal alone (initial humic concentration (HA) concentration of 10 ppm). ).
  • the present invention relates to a visible light active spherical carbon-based pore material and a method of manufacturing the same. More specifically, the present invention ion-exchanged titanium as a photocatalyst ion to a solution phase in an ion exchanger of a strongly acidic cation exchange resin in order to express photoactivity even in the visible light region, and then additionally transition metals to ion-exchanged ions.
  • the present invention provides a visible light activated spherical carbon-based pore material that can be applied to various harmful substances and water treatment materials in the air in various light wavelength ranges as well as maintaining shape and strength by supporting the heat exchanger and heat-treating them.
  • the strong acid cation exchange resin is generally used as a carrier for immobilizing the photoreactive metal ions and then immobilizing it, and can be easily purchased and used.
  • the type of the strongly acidic cation exchange resin is not limited, but may be one including a combination of polystyrene and divinylbenzene (DVB) as a mother.
  • a functional group -SO 3 - can be used with the (sulfonate), it may be selected from the total ion exchange capacity of 2.0 ⁇ 2.3 meq / ml.
  • titanium is used as a basic photocatalyst component for imparting photoactivity
  • the transition metals supported together are preferably used in the form of a precursor such as a water-soluble compound that can be easily dissolved in water, more preferably chloride or It is good to support in the form of nitrate.
  • the titanium is supported by 2 to 9% by weight with respect to the strong acid cation exchange resin in the dry state, there is a problem that the light activity is weak when the supported amount is less than 2% by weight, the decomposition efficiency is more effective when the supported amount exceeds 9% by weight There is a problem that it does not rise.
  • due to the essential use of titanium and transition metal it plays a role of reducing the size of light energy required for photoactivity, and thus exhibits a different feature from that required for high photoactive energy in the existing Korean Patent No. 672,906.
  • the transition metal is used as a means for acting together with titanium to have photoreactive activity in a wider wavelength range, it is preferable to use a transition metal selected from Fe, Ag, Cu, Ni and Co, Most preferably, Fe is used.
  • the transition metal elements are preferably used in the form of precursors such as chloride or nitrate, which are water-soluble compounds that can be easily dissolved in water, and more preferably FeCl 3 , AgNO 3 , CuCl 2 ⁇ 2H 2 O, Ni (NO 3 ) It is preferable to use at least one selected from 2 ⁇ 6H 2 O and Co (NO 3 ) 2 ⁇ 6H 2 O.
  • the transition metal is preferably supported to be 0.2 ⁇ 1.0% by weight with respect to the dry acid strong cation exchange resin, if the supported amount is less than 0.2% by weight there is a problem that does not sufficiently express the photoactivity, the supported amount exceeds 1.0% by weight In this case, there is a problem that the change in efficiency according to the increase of the loading amount does not change much and is almost constant.
  • the titanium and the transition metal are complexly supported, and in particular, titanium is essentially supported.
  • the transition metal contained in the lattice of titanium traps electrons in electrons (e ⁇ ) and holes (h + ) generated by receiving energy above the band gap present in the photocatalyst. Therefore, it is possible to increase the light activity by preventing the recombination of electrons and holes, and there is an important technical significance to increase the wavelength range to the visible light region. Therefore, it selects and supports one type of photocatalyst element, and its technical characteristics are completely different from the existing technology that showed photoactivity only in the ultraviolet region. In addition, existing technologies showing photoactivity in visible light show photoactivity in the visible light region, but there are big problems that they have nano-sizes that are difficult to commercialize.
  • the present invention unlike the present invention, by ion-exchanging titanium and transition metals in the form of an aqueous solution of a precursor sequentially in an ion exchange resin carrier, it is possible to solve the environmental problem by eliminating the use of an organic solvent, as well as to easily support titanium and It has the advantage of freely controlling the amount of transition metal supported. That is, by using an ion exchange resin which is converted to a carbon-based pore material as a carrier starting material, the present invention is to provide a spherical carbon-based pore material and a process for manufacturing the titanium and transition metals having optical activity in the visible light region I am doing it.
  • an ion exchange reaction of titanium in the form of a precursor to the strongly acidic cation exchange resin is used, and titanium in the form of the precursor is used in the form of a water-soluble compound, such as TiCl 3 or TiCl 4 and dissolved in an aqueous solution at 1 to 3% by weight.
  • a strong acid cation exchange resin is reacted for 0.5 to 5 hours, and Ti 3+ or Ti 4+ ions are ion-exchanged on the exchanger of the ion exchange resin.
  • the amount of titanium supported on the carrier can be adjusted by adjusting the concentration of the water-soluble compound.
  • the transition metal in the form of a precursor is supported on the ion exchange resin in which the titanium ion exchange takes place.
  • the transition metal in the form of the precursor is dissolved in an aqueous solution at 0.1 to 0.5% by weight, followed by a strong acid cation exchange resin and 0.5 to 5 The reaction is carried out for a period of time and supported on an ion exchange resin.
  • the ion exchange resin subjected to the ion exchange treatment as described above is then subjected to a drying process, and the drying process is not limited. For example, it may be dried for 5 to 24 hours at 100 ⁇ 150 °C.
  • an incompatibility process is performed.
  • the incompatibility is performed in an air atmosphere for 2 to 8 hours at a temperature of 200 to 400 ° C.
  • the temperature increase rate is preferably 1 to 5 °C / min to reduce the deformation of the sample.
  • a carbonization process is performed to convert the photoactive activated carbon, and the carbonization is performed for 0.1 to 2 hours at a temperature of 400 to 1000 ° C. under an inert gas atmosphere selected from nitrogen, helium, and argon.
  • the temperature increase rate is preferably 1 to 5 °C / min to reduce the deformation of the sample.
  • the temperature increase rate is preferably 1 to 5 °C / min to reduce the deformation of the sample.
  • the form of the visible light-activated spherical carbon-based pore material thus obtained has an even surface spherical shape like that of the initial ion exchange resin, and the diameter is about 300 to 400 ⁇ m.
  • Intensity is a unit of weight that the particles of visible light activated spherical carbon-based porous material prepared can withstand, the visible light active spherical carbon-based porous material of the present invention shows an intensity of 8 ⁇ 9 kg / a unit.
  • the above results can be predicted to prevent the loss caused by the collision between particles in the fluidized bed, which indirectly shows that a commercial process can be applied.
  • the use of the carrier to make it commercially available is designed to perform only the role of the carrier in the conventional case, in this study, not only the role of the carrier but also titanium and transition metals are sequentially ion-exchanged to have a uniform distribution.
  • a carrier in the form of an ion exchange resin is converted to a carbon-based pore material through heat treatment, in addition to the role of a carrier in evaluating the photodegradation efficiency of the organic material, the adsorption of the organic material can be induced to increase the photodegradation efficiency. It also has a function.
  • the obtained visible light activated spherical carbon-based porous material When the obtained visible light activated spherical carbon-based porous material is applied to the water treatment process, it exhibits an organic removal efficiency of about 15 to 50% at a wavelength of 254 nm and an organic removal efficiency of about 40 to 60% at a wavelength of 365 nm. It can be seen that it can be used as a photocatalyst having a photolysis efficiency.
  • a visible light active spherical carbon-based pore material was prepared using a strongly acidic cation exchange resin (SK1BH) as a matrix.
  • SK1BH strongly acidic cation exchange resin
  • titanium ions which are inexpensive, chemically and biologically stable and readily available in the metal, are used as photocatalysts.
  • Titanium was dissolved in water in the form of titanium chloride (TiCl 3 ) and stirred for 1 hour to carry out ion exchange of titanium ions.
  • the content of titanium was adjusted so that the content of titanium per unit weight of the dry ion exchange resin was in the range of 3% by weight.
  • ion exchange was performed at 75 g of TiCl 3 so that the weight ratio of TiCl 3 to ion exchange resin and distilled water was 1: 4: 30. 300 g of resin and 2250 g of distilled water were used.
  • Transition metals Fe 3+ , Ag 3+ , Cu 2+ , Ni 2+ and Co 2+ were supported on the ion exchange resin in which titanium was ion-exchanged in the same manner as the method of titanium ion exchange.
  • Precursor of each transition metal used the form of FeCl 3 , AgNO 3 , CuCl 2 ⁇ 2H 2 O, Ni (NO 3 ) 2 ⁇ 6H 2 O, Co (NO 3 ) 2 ⁇ 6H 2 O ,
  • the content of the transition metal to the content of the dry resin was adjusted to 0.3% by weight, 0.3% by weight, 0.5% by weight, 0.5% by weight, 0.5% by weight, respectively.
  • the ion exchange resin used as a carrier has a spherical carbon-based pore material, and the ion exchanged metal is converted into a photoactive component through a heat treatment process.
  • the total amount of the visible light-activated spherical carbon-based porous material thus obtained was 45.36 g, 46.24 g, 45.82 g, 50.48 g and 51.50 g in order of iron, silver, copper, nickel and cobalt, respectively. burn off) was 55.02%, 53.93%, 54.41%, 49.65%, 48.90%, respectively, and the amount of titanium supported on the visible light spherical carbon-based porous material was 6.14%, 5.71%, 5.60%, 5.97%, 5.13 wt%.
  • Visible light-activated spherical carbon-based porous material prepared using a strong acid cation exchange resin as a matrix was about 350 ⁇ m in size, and its shape had a spherical shape suitable for application to a fluidized bed process as shown in FIG. It was easy to adsorb organic matter.
  • EPMA electron probe micro analyzer
  • Example 1 only the transition metal supporting process was omitted, and all others were the same. That is, titanium was supported alone by an ion exchange method to prepare a photoactive spherical carbon-based pore material.
  • the ion exchange resin on which the transition metals were ion exchanged and supported was dried in an oven at 110 ° C. for 12 hours, and after being infusible at 300 ° C. for 5 hours, The temperature was raised to 1 ° C / min to 700 ° C under a nitrogen atmosphere to carry out a carbonization process.
  • Spherical carbon-based pore materials were prepared after a 0.5 hour activation process at 900 ° C. under nitrogen and water vapor.
  • the photoreactor manufactured 2.4 L cylindrical batch reactors with stainless steel (Stainless) to prevent the transmission of other light from the outside during the reaction.
  • the inner diameter of the reactor was fixed at 10 cm in consideration of UV transmittance and the height was 45 cm.
  • dissolved oxygen (DO) measurement was possible, and in the lower part, a sampling port for collecting analytical samples and an aeration device were installed to facilitate the activity and photocatalytic flow of the photocatalyst.
  • Visible light-activated spherical carbon-based pores were dosed at 20 g / L.
  • the pollutant is the source of DBPs (disinfection by-products) in the existing water treatment disinfection process and selected a HA (humic acid) that plays a decisive role in drinking water quality and affects the bioavailability of compounds such as pesticides in the soil.
  • Standard solution preparation of HA was used after dissolving ALDRICH's first-class reagent in distilled water for 24 hours, filtering with 0.45 ⁇ m membrane filter paper to remove ash components remaining insoluble.
  • the HA concentration in the reactor was fixed at 10 ppm, taking into account the BOD 5 and COD of domestic constant raw water and 4.4 ppm, the average TOC concentration of US surface water.
  • the HA removal efficiency of the visible light activated spherical carbon-based porous material at the wavelength of 254 nm was about 15 to 42% after 6 hours, and the visible light activated spherical carbon at the wavelength of 365 nm.
  • the HA removal efficiency of the pore material showed about 40 ⁇ 53% HA removal efficiency after 6 hours.
  • the treatment efficiency was about 5 to 10% higher than that of other transition metals. The results are shown in Tables 1 and 4 (a) and 4 (b) below.
  • the removal efficiency is high even in the visible region, which indicates that the transition metal contained in the lattice of titanium of the visible light active spherical carbon-based porous material produced by the present invention absorbs energy above the band gap in the photocatalyst. This is the result of enhancing the photoactivity by trapping electrons in the generated electrons and holes to prevent recombination of electrons and holes.
  • Comparative Examples 2 to 6 which are spherical carbon-based pore materials supporting only transition metals, as shown in Table 1 and FIGS. 5-6, changes in initial concentration and concentration after reaction in both wavelength ranges of 254 nm and 365 nm It did not happen that it was found that HA was not removed at all.
  • the visible light-activated spherical carbon-based porous material of the present invention supports titanium and a transition metal element together, and has a catalytic activity of 40% or more in the visible region as well as in the ultraviolet region. Compared to the photoactive spherical carbon-based porous material loaded with transition metal alone, it can be used as a material for removing harmful substances in the air and water treatment materials in a wider light range. Visible light-activated spherical carbon-based pore material according to the present invention is useful compared to the existing catalyst in terms of economics because it exhibits activity in the visible light range, it is expected to bring a large ripple effect when applied to commercial processes.

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Abstract

La présente invention concerne un procédé de préparation d'un matériau poreux à base de carbone sphérique actif en lumière visible, et plus particulièrement, un procédé de préparation d'un matériau poreux à base de carbone sphérique actif en lumière visible (Ti-M-SCM) en introduisant un ion titane, qui est un catalyseur photoactif, dans un groupe échangeur d'ions appartenant à une résine échangeuse de cations fortement acide par le biais d'un procédé d'échange d'ions, en introduisant également des métaux de transition dans la résine échangeuse d'ions, et en traitant thermiquement celle-ci. Le matériau poreux à base de carbone sphérique actif en lumière visible selon la présente invention est photoactif dans la plage de longueurs d'onde s'étendant à la plage de lumière visible et a une forme, une taille et une résistance appropriées pour une application à un système commercial, et peut ainsi être utilisé de manière efficace comme photocatalyseur, adsorbant et équivalents pour éliminer un polluant organique dans la large gamme des longueurs d'onde lumineuses.
PCT/KR2011/001950 2010-05-17 2011-03-22 Matériau poreux à base de carbone sphérique actif en lumière visible, et son procédé de préparation WO2011145801A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR20100045899A KR101183518B1 (ko) 2010-05-17 2010-05-17 가시광 활성 구형 탄소계 기공소재 및 그의 제조방법
KR10-2010-0045899 2010-05-17

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