KR101318974B1 - Environmental cartridge unit to treat fluid containing VOC and malodor - Google Patents
Environmental cartridge unit to treat fluid containing VOC and malodor Download PDFInfo
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- KR101318974B1 KR101318974B1 KR1020110045453A KR20110045453A KR101318974B1 KR 101318974 B1 KR101318974 B1 KR 101318974B1 KR 1020110045453 A KR1020110045453 A KR 1020110045453A KR 20110045453 A KR20110045453 A KR 20110045453A KR 101318974 B1 KR101318974 B1 KR 101318974B1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L9/00—Disinfection, sterilisation or deodorisation of air
- A61L9/16—Disinfection, sterilisation or deodorisation of air using physical phenomena
- A61L9/18—Radiation
- A61L9/20—Ultraviolet radiation
- A61L9/205—Ultraviolet radiation using a photocatalyst or photosensitiser
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- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/0407—Constructional details of adsorbing systems
- B01D53/0415—Beds in cartridges
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2259/00—Type of treatment
- B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
- B01D2259/804—UV light
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
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Abstract
본 발명은 비교적 긴 체류시간을 필요로 하는 광촉매를 이용한 촉매산화 공정에 있어서 광촉매산화공정 내부에서의 체류시간을 연장하기 위하여 흡착과 광촉매산화공정으로 이루어진 크로마토그라프적 흡탈착을 활용한 휘발성유기화합물 또는 악취를 함유한 유체처리를 위한 환경 카트리지 유닛과 휘발성유기화합물 또는 악취를 함유한 유체처리 방법에 관한 것이다.
광촉매 층, 흡착 층과 광촉매 층의 순서로 구성된 환경 카트리지 유닛은, 앞과 뒤의 광촉매 층에서의 유체에 함유된 휘발성유기화합물 또는 악취의 광촉매반응을 위한 체류시간을 연장시켜서 유체에 함유된 휘발성유기화합물 또는 악취의 처리효율을 지속적으로 제고시킨다. 본 발명의 환경카트리지 유닛을 복수로 유체처리 방향에 직렬(in series)로 배치하였을 때에, 본 발명의 시스템 전 영역에 직렬로 배치된 복수의 흡착층에서의 크로마토그래프적 흡탈착에 의한 휘발성유기화합물 또는 악취의 광촉매반응에서의 체류시간 연장이 복수의 상기 유닛을 배치한 전 영역에서 이루어지는 것을 특징으로 하며, 유체에 포함된 휘발성유기화합물 또는 악취를 효과적으로 저감 또는 제거 처리할 수 있다. 광촉매반응에 의한 유체에 포함된 휘발성유기화합물 또는 악취의 저감 또는 제거처리 방법에 있어서, 휘발성유기화합물 또는 악취의 저감 또는 제거효율 제고를 목적으로 광원에 의하여 활성화된 광촉매에 의한 반응에서의 휘발성유기화합물 또는 악취의 체류시간을 증대시키기 위하여, 유체 진행방향으로 광촉매필터와 광촉매필터 사이에 흡착필터를 삽입하여, 광촉매필터-흡착필터-광촉매필터로 이루어진 유체에 포함된 휘발성유기화합물 또는 악취의 저감 또는 제거처리 유닛 또는 상기 환경 카트리지 유닛을 구성한다. 상기 유닛의 유체진행방향 전후에 광원을 조사하여 상기 유닛의 광촉매필터를 활성화시키며, 복수의 상기유닛을 배치하여 복수의 흡착필터에 의한 휘발성유기화합물 또는 악취의 광촉매반응에서의 체류시간 연장이 복수의 상기 유닛을 배치한 전 영역에서 이루어지는 것을 특징으로 하며, 유체에 포함된 휘발성유기화합물 또는 악취를 효과적으로 저감 또는 제거 처리할 수 있다.The present invention provides a volatile organic compound utilizing chromatographic adsorption and desorption consisting of adsorption and photocatalytic oxidation in order to prolong the residence time in the photocatalytic oxidation process in a catalytic oxidation process using a photocatalyst requiring a relatively long residence time. The present invention relates to an environmental cartridge unit for treating a malodorous fluid and a method for treating a fluid containing volatile organic compounds or malodors.
The environmental cartridge unit consisting of a photocatalyst layer, an adsorption layer and a photocatalyst layer in order, extends the residence time for the photocatalytic reaction of volatile organic compounds or odors contained in the fluid in the front and rear photocatalyst layers, thereby volatile organic matter contained in the fluid. Continuously improve the treatment efficiency of compounds or odors. Volatile organic compounds by chromatographic adsorption and desorption in a plurality of adsorption layers arranged in series in the whole area of the system when the plurality of environmental cartridge units of the present invention are arranged in series in the fluid treatment direction Or extending the residence time in the photocatalytic reaction of the odor is carried out in the whole region in which the plurality of units are arranged, and the volatile organic compound or odor contained in the fluid can be effectively reduced or removed. In the method for reducing or removing volatile organic compounds or odors contained in a fluid by a photocatalytic reaction, a volatile organic compound in a reaction by a photocatalytically activated light source for the purpose of reducing or removing volatile organic compounds or odors. Alternatively, in order to increase the residence time of the odor, an adsorption filter is inserted between the photocatalyst filter and the photocatalyst filter in the fluid advancing direction to reduce or eliminate volatile organic compounds or odors contained in the fluid consisting of the photocatalyst filter, the adsorption filter, and the photocatalyst filter. Configure the processing unit or the environmental cartridge unit. The photocatalyst filter of the unit is activated by irradiating a light source before and after the fluid running direction of the unit, and the plurality of units are arranged to extend the residence time in the photocatalytic reaction of volatile organic compounds or odors by the plurality of adsorption filters. It is made in the whole area | region which arrange | positioned the said unit, The volatile organic compound or odor contained in a fluid can be effectively reduced or removed.
Description
현재 악취 물질 및 휘발성유기화합물(VOCs) 배출 산업현장에서 활용하고 있는 유해가스 제거용 대기오염방지시설은 주로 흡수 및 흡착의 원리를 이용한 Wet Scrubber와 Activated Carbon Tower 그리고 소각의 원리를 이용한 RTO(regenerative thermal oxidation)와 RCO(regenerative catalytic oxidation) 등이 있다. 최근 친환경 개념의 Bio Filter가 적용되어오고 있으나 미생물의 활성유지를 위한 처리대상 유해 VOC의 농도 제한 및 이에 따른 제거 효율의 지속성, 용수 및 전력사용량, 연료사용량 그리고 폐기물 및 폐수처리 비용 등의 개선의 여지가 많은 실정으로 에너지 절약 및 향후 점차 강화되어질 환경법의 준수를 통한 경쟁력 확보를 위한 보다 경제적인 VOC 제어 설비의 필요성이 강조되고 있다. 대기로 방출되는 휘발성 유기화합물(VOC : Volatile Organic Compound)에 대한 환경 규제 강화에 대비하여 VOC 배출을 방지할 수 있는 기술의 중요성이 점차 강조되고 있다. 그래서 VOC 환경 규제 배출 농도가 급격하게 낮아짐에 따라 그 경제성을 고려하여 다양한 종류의 VOC에 대한 흡착을 이용한 최적의 운전이 가능한 기술개발이 활발히 진행되고 현장에 적용되고 있다. 광촉매 기술은 광을 받으면 촉매 반응을 일으키는 물질을 이용하는 기술로서, 인체에 무해하고, 여러 분야에서 응용가능하다. 이 기술의 특징은 특별한 에너지를 가하지 않고 광만을 이용하여 대기 및 수질의 유해한 유기 오염물 및 무기 오염물을 분해 제거 하여 인체에 무해한 물질로 전환 시키고, 또한 향균 및 살균작용으로 유해한 병원균도 제거가 가능하다. 광촉매 물질로는 주로 반도체물질로서 TiO2가 가장 많이 사용되고 있으며 n형 반도체로서 UV 영역에서 활성을 나타내는 광촉매 물질의 band-gab은 3.0 - 3.2 eV이고, 자외선(400nm)을 받으면 수분 존재시 전자(Electron), 전공대(Electron hole)가 형성되어 강한 산화력을 가진 하이드록시 라디칼(-OH)과 슈퍼 옥사이드(O2 -)를 생성한다. 흡착공정을 비교적 긴 체류시간을 필요로 하는 광촉매를 이용한 촉매산화 공정에 연계하여 복합시스템 내부에서의 체류시간을 연장하기 위하여 흡착 및 광촉매산화공정의 최적 배치 및 흡착 및 탈착을 활용한 최적 운전기법 등의 복합시스템의 최적설계가 절실히 필요하다.Air pollution prevention facilities for the removal of odorous substances and volatile organic compounds (VOCs) currently used in industrial sites are mainly used for wet scrubber and activated carbon towers using absorption and adsorption and regenerative thermal using incineration. oxidation) and regenerative catalytic oxidation (RCO). Recently, the eco-friendly concept of Bio Filter has been applied, but there is room for limiting the concentration of harmful VOC to be treated and maintaining the efficiency of removal, consequently, water and power consumption, fuel consumption and waste and waste water treatment costs. In many cases, the need for more economical VOC control equipment is being emphasized to secure competitiveness through energy saving and compliance with environmental laws that will be strengthened in the future. In preparation for tightening environmental regulations on volatile organic compounds (VOCs) released into the atmosphere, the importance of technologies to prevent VOC emissions is increasingly being emphasized. Therefore, as the concentration of VOC regulated emission is drastically lowered, considering the economical efficiency, technology development capable of optimal operation using adsorption on various types of VOC is actively progressed and applied to the site. Photocatalyst technology is a technology that uses a substance that generates a catalytic reaction upon receiving light, which is harmless to the human body, and is applicable to various fields. This technology uses only light to decompose and remove harmful organic and inorganic pollutants in the air and water without using special energy, and converts them into harmless substances. Also, it is possible to remove harmful pathogens by antibacterial and bactericidal action. TiO 2 is mainly used as a photocatalyst, and as an n-type semiconductor, the band-gab of the photocatalytic material exhibiting activity in the UV region is 3.0-3.2 eV, and in the presence of moisture when exposed to ultraviolet (400 nm) electrons (Electron) ), is formed for the major (Electron hole), hydroxy radical (having a strong oxidizing power-generates) - OH) and superoxide (O 2. In order to extend the residence time in the complex system by linking the adsorption process with a catalytic oxidation process using a photocatalyst requiring a relatively long residence time, the optimum arrangement of the adsorption and photocatalytic oxidation processes and the optimum operation technique utilizing the adsorption and desorption Optimal design of complex system is urgently needed.
특허공개공보 10-2005-0047045(2005.05.19)는 1차적으로 흡착제에 의하여 오염된 공기의 악취나 VOC를 고농도로 흡착하여 제거하고, 2차적으로 광촉매/자외선의 광촉매 분해구간에서 오염된 공기의 잔류 악취나 VOC를 처리하는 하이브리드식 악취정화처리방법 및 그에 따른 시스템에 관하여 공개하였다. 그러나 특허공개공보 10-2005-0047045(2005.05.19)의 경우는 유동상 광촉매담체를 사용하기 때문에 제시한 오염된 공기의 악취정화처리방법 및 그에 따른 시스템이 전반부의 흡착탑과 후반부의 유동상의 광촉매담체가 오염된 공기와 접촉하는 광촉매반응기로 공간적으로 양분 될 수 밖 에 없다. 따라서 오염된 공기의 악취나 VOC를 고농도로 흡착하는 하이브리드 시스템 전반부에 위치하는 흡착제는, 하이브리드 시스템 후반부에 위치하는 광촉매반응구간 중에서 오로지 흡착제와 경계하는 광촉매반응구간에 의하여 광촉매반응구간과 경계하는 극히 일부분의 흡착제만이 재생된다. 따라서 전술한 바와 같이 특허공개공보 10-2005-0047045(2005.05.19)는 하이브리드시스템이 1차적인 흡착구간과 2차적인 광반응구간으로 공간적으로 분리되어서, 1차적으로 흡착제에 의하여 오염된 공기의 악취나 VOC를 고농도로 흡착하여 제거하고, 2차적으로 광촉매/자외선의 광촉매 분해구간에서 오염된 공기의 잔류 악취나 VOC를 처리하는 한 가지 단위공정에 다른 단위공정을 부가한 시스템으로서 본 발명의 구성에서 실현화되는 크로마토그래프적 흡탈착이 이루어지지 못하므로 하이브리드시스템으로서의 시너지효과는 거의 없거나 매우 적다. 또한 특허공개공보 10-2005-0047045(2005.05.19)는 고안의 구성 및 작용에서 제시하는 하이브리드시스템과 광촉매반응시스템과의 효과에 있어서의 비교를 실시하지 않았고, 실시예에서도 휘발성유기화합물과 악취성분이 혼합된 복합악취가 아닌 단일 악취성분을 함유한 공기를 대상으로 하였다. Patent Publication No. 10-2005-0047045 (2005.05.19) primarily removes odors or VOCs contaminated by adsorbents at a high concentration and removes air contaminated in the photocatalyst / ultraviolet photocatalytic decomposition section. A hybrid malodor treatment method and a system for treating residual malodor or VOC are disclosed. However, in the case of Patent Publication No. 10-2005-0047045 (2005.05.19), since the fluidized bed photocatalyst carrier is used, the proposed method for treating odor of polluted air and the resulting system are the adsorption tower of the first half and the fluidized bed photocatalyst of the second half. Can only be spatially bifurcated into the photocatalytic reactor in contact with contaminated air. Therefore, the adsorbent located in the first half of the hybrid system that adsorbs the odor of polluted air or VOC at a high concentration is a very small part of the photocatalyst reaction section located in the second half of the hybrid system, which borders the photocatalytic reaction section only by the photocatalytic reaction section that borders with the adsorbent. Only adsorbent of is regenerated. Therefore, as described above, Patent Publication No. 10-2005-0047045 (2005.05.19) discloses that a hybrid system is spatially separated into a primary adsorption section and a secondary photoreaction section, so that the air contaminated by the adsorbent is The structure of the present invention is a system in which another unit process is added to one unit process for removing odors or VOCs at a high concentration and secondarily treating residual odors or VOCs of contaminated air in a photocatalyst / ultraviolet photocatalytic decomposition section. Since the chromatographic adsorption and desorption cannot be realized in the system, the synergy effect of the hybrid system is little or very little. In addition, Patent Publication No. 10-2005-0047045 (2005.05.19) does not compare the effect of the hybrid system and the photocatalytic reaction system proposed in the design and operation of the invention, and the volatile organic compounds and odor components in the examples The air containing a single malodorous component was used instead of the mixed complex malodor.
흡착공정을 비교적 긴 체류시간을 필요로 하는 광촉매를 이용한 촉매산화 공정에 연계하여 복합시스템 내부에서의 체류시간을 연장하기 위하여 흡착 및 광촉매산화공정의 최적 배치 및 흡착 및 탈착을 활용한 최적 운전기법 등의 복합시스템의 최적설계가 절실히 필요하다.In order to extend the residence time in the complex system by linking the adsorption process with a catalytic oxidation process using a photocatalyst requiring a relatively long residence time, the optimum arrangement of the adsorption and photocatalytic oxidation processes and the optimum operation technique utilizing the adsorption and desorption Optimal design of complex system is urgently needed.
본 발명의 과제해결수단은 다음과 같다. 휘발성유기화합물 또는 악취의 저감 또는 제거효율 제고를 목적으로 광원에 의하여 활성화된 광촉매에 의한 반응에서의 휘발성유기화합물 또는 악취의 체류시간을 증대시키기 위하여, 유체 진행방향으로 광촉매필터와 광촉매필터 사이에 흡착필터를 삽입하여, 광촉매필터-흡착필터-광촉매필터로 이루어진 유체에 포함된 휘발성유기화합물 또는 악취의 저감 또는 제거처리 유닛을 구성한다. 상기 유닛은 고정상 및 유동상 유닛을 모두 포함한다. 고정상 유닛의 경우에 유체진행방향으로 상기 유닛의 전후에 광원을 조사하여 상기 유닛의 광촉매필터를 활성화시키며, 복수의 상기유닛을 배치하여 복수의 흡착필터에 의한 휘발성유기화합물 또는 악취의 광촉매반응에서의 체류시간 연장이 크로마토그래프적 흡탈착으로 인하여 복수의 상기 유닛을 배치한 전 영역에서 이루어지는 것을 특징으로 하며, 유체에 포함된 휘발성유기화합물 또는 악취를 효과적으로 저감 또는 제거 처리할 수 있다.The problem solving means of the present invention is as follows. Adsorption between the photocatalyst filter and the photocatalyst filter in the fluid direction to increase the residence time of the volatile organic compound or odor in the reaction by the photocatalyst activated by the light source for the purpose of reducing or eliminating volatile organic compounds or odors. The filter is inserted to form a processing unit for reducing or removing volatile organic compounds or odors contained in a fluid consisting of a photocatalyst filter, an adsorption filter, and a photocatalyst filter. The unit includes both stationary and fluidized bed units. In the case of the stationary phase unit, the photocatalyst filter of the unit is activated by irradiating a light source before and after the unit in the fluid advancing direction, and the plurality of units are arranged in the photocatalytic reaction of volatile organic compounds or odors by the plurality of adsorption filters. The residence time is extended in the entire region in which a plurality of the units are arranged due to chromatographic adsorption and desorption, and the volatile organic compound or odor contained in the fluid can be effectively reduced or removed.
상기 유닛을 모듈화한 것은 도 1과 같은 광촉매 층(layer)과 흡착 층(layer)의 조합으로 구성된 다층(multi-layer)인 것을 특징으로 하는 유체에 포함된 휘발성 유기화합물 또는 악취의 저감 또는 제거처리를 위한 환경 카트리지 유닛이다. 환경카트리지 유닛의 다층(multi-layer)은 광촉매 층, 흡착 층과 광촉매 층의 순서로 구성된다. 여기서 광촉매 층(layer)은 모듈화된 환경카트리지 유닛을 구성하는 광촉매 필터로서 유체가 통과할 수 있도록 기공(pore)이 설비된 광촉매가 코팅된 단수 또는 복수의 막필터, 광촉매가 코팅된 입자상 담체로 충전된 광촉매 필터 또는 광촉매가 코팅된 허니컴 필터 중의 하나이고, 흡착 층(layer)은 모듈화된 환경카트리지 유닛을 구성하는 흡착필터로서 유체가 통과할 수 있도록 기공(pore)을 포함하는 흡착제로 표면 처리된 단수 또는 복수의 막필터, 흡착제 입자로 충전된 흡착제필터 또는 흡착제가 코팅되거나 흡착제로 성형된 허니컴 필터 중의 하나인 것을 특징으로 한다.The modularized unit is a multi-layer composed of a combination of a photocatalytic layer and an adsorption layer as shown in FIG. 1 to reduce or remove volatile organic compounds or odors contained in a fluid. Environmental cartridge unit. The multi-layer of the environmental cartridge unit consists of a photocatalytic layer, an adsorption layer and a photocatalytic layer. The photocatalyst layer is a photocatalyst filter constituting a modular environmental cartridge unit, and is filled with a single or a plurality of membrane filters coated with a photocatalyst equipped with pores so that fluid can pass therethrough, and a particulate carrier coated with a photocatalyst. Is either a photocatalyst filter or a honeycomb filter coated with a photocatalyst, and the adsorption layer is an adsorption filter constituting a modular environmental cartridge unit, the surface treated with an adsorbent comprising pores to allow fluid to pass therethrough. Or a honeycomb filter which is coated with a plurality of membrane filters, an adsorbent filter filled with adsorbent particles, or an adsorbent or molded into an adsorbent.
환경카트리지 유닛의 광촉매층 중에서 유체진행방향으로 첫 번째 상기 광촉매 층과 마지막 상기 광촉매 층의 흡착 층과 접하지 않고 유체와 접촉하는 양면들인 상기 환경 카트리지 유닛의 바깥 양면들이 각각 광원들과 마주하게 배치하고, 환경 카트리지 유닛은 하나 또는 복수로 도 2에서와 같이 유체처리 방향에 직렬(in series)로 배치할 수 있다. 또한 본 발명에서 실리카와 같이 반투명하여, UV광이 도달할 수 있는 광촉매를 함침한 흡착능이 있는 담체를 사용하여 흡착공정과 광촉매공정을 일체화하여 흡착 및 광촉매산화를 환경카트리지 유닛 내의 같은 광촉매필터에서 발생시킬 수도 있다.Among the photocatalyst layers of the environmental cartridge unit, the outer both sides of the environmental cartridge unit, which are both surfaces in contact with the fluid without contacting the adsorption layer of the first photocatalyst layer and the last photocatalyst layer in the fluid direction, are disposed to face the light sources, respectively. In one or more environmental cartridge units, the environmental cartridge units may be arranged in series in the fluid treatment direction as shown in FIG. 2. In addition, in the present invention, adsorption and photocatalytic oxidation are generated in the same photocatalyst filter in an environmental cartridge unit by integrating the adsorption process and the photocatalytic process using a carrier having a adsorption capacity that is translucent like silica and impregnated a photocatalyst capable of reaching UV light. You can also
본 발명의 효과는 다음과 같다. 광촉매 층, 흡착 층과 광촉매 층의 순서로 구성된 환경 카트리지 유닛은, 앞과 뒤의 광촉매 층에서의 유체에 함유된 휘발성유기화합물 또는 악취의 광촉매반응을 위한 체류시간을 연장시켜서 유체에 함유된 휘발성유기화합물 또는 악취의 처리효율을 지속적으로 제고시킨다. 본 발명의 효과는 이와 같은 환경카트리지 유닛을 복수로 유체처리 방향에 직렬(in series)로 배치하였을 때에, 본 발명의 시스템 전 영역에 직렬로 배치된 복수의 흡착층에서의 크로마토그래프적 흡탈착에 의한 휘발성유기화합물 또는 악취의 광촉매반응에서의 체류시간 연장이 복수의 상기 유닛을 배치한 전 영역에서 이루어지는 것을 특징으로 하며, 유체에 포함된 휘발성유기화합물 또는 악취를 기존의 기술보다 효과적으로 저감 또는 제거 처리할 수 있다. The effects of the present invention are as follows. The environmental cartridge unit consisting of a photocatalyst layer, an adsorption layer and a photocatalyst layer in order, extends the residence time for the photocatalytic reaction of volatile organic compounds or odors contained in the fluid in the front and rear photocatalyst layers, thereby volatile organic matter contained in the fluid. Continuously improve the treatment efficiency of compounds or odors. The effect of the present invention is that when the plurality of such environmental cartridge units are arranged in series in the fluid treatment direction, the chromatographic adsorption and desorption on a plurality of adsorption layers arranged in series in the entire region of the system of the present invention is applied. Extending the residence time in the photocatalytic reaction of volatile organic compounds or odors by means of the entire area in which a plurality of the units are arranged, and reduces or removes volatile organic compounds or odors contained in the fluid more effectively than conventional techniques. can do.
도 1은 광촉매 층(layer)과 흡착 층(layer)의 조합으로 구성된 다층(multi-layer)인 것을 특징으로 하는 유체에 포함된 휘발성유기화합물 또는 악취의 저감 또는 제거처리를 위한 환경 카트리지 유닛을 도시한 도면
도 2는 광원에 의하여 활성화된 광촉매에 의한 반응에서의 휘발성유기화합물 또는 악취의 체류시간을 증대시키기 위하여,
유체 진행방향으로 광촉매필터와 광촉매필터 사이에 흡착필터를 삽입하여, 광촉매필터-흡착필터-광촉매필터로 이루어진 유체에 포함된 휘발성유기화합물 또는 악취의 저감 또는 제거처리 유닛 또는 환경 카트리지 유닛을 구성하고, 유체진행방향으로 상기 유닛의 전후에 광원을 조사하여 상기 유닛의 광촉매필터를 활성화시키며, 복수의 상기 유닛을 유체진행 방향으로 배치하여 복수의 흡착필터에 의한 휘발성유기화합물 또는 악취의 광촉매반응에서의 체류시간 연장이 복수의 상기 유닛을 배치한 전 영역에서 이루어지는 것을 특징으로 하는, 유체에 포함된 휘발성유기화합물 또는 악취의 저감 또는 제거처리 시스템을 도시한 도면
도 3은 본 발명의 구성인, 유체에 포함된 휘발성유기화합물 또는 악취의 저감 또는 제거처리 시스템을 사용하여 톨루엔 50 ppm (300시간에서 230 ppm으로 농도 높임), 에탄올 50 ppm, 황화수소 10 ppm을 함유한 공기를 580 시간 처리하였을 때에 톨루엔, 에탄올 및 황화수소의 처리농도를 도시한 도면
도 4는 본 발명의 구성에서 흡착필터만을 제외한 휘발성유기화합물 또는 악취의 저감 또는 제거처리 시스템을 사용하여 톨루엔 50 ppm (300시간에서 230 ppm으로 농도 높임), 에탄올 50 ppm, 황화수소 10 ppm을 함유한 공기를 580 시간 처리하였을 때에 톨루엔, 에탄올 및 황화수소의 처리농도를 도시한 도면1 shows an environmental cartridge unit for reducing or removing volatile organic compounds or odors contained in a fluid, which is a multi-layer composed of a combination of a photocatalytic layer and an adsorption layer. One drawing
Figure 2 is to increase the residence time of volatile organic compounds or odor in the reaction by the photocatalyst activated by the light source,
An adsorption filter is inserted between the photocatalyst filter and the photocatalyst filter in the fluid advancing direction to form a volatile organic compound or an odor reduction or removal processing unit or an environmental cartridge unit included in the fluid consisting of the photocatalyst filter, the adsorption filter, and the photocatalyst filter. The photocatalyst filter of the unit is activated by irradiating a light source before and after the unit in the fluid advancing direction, and the plurality of units are arranged in the fluid advancing direction to retain the volatile organic compounds or odors in the photocatalytic reaction by the plurality of adsorptive filters. A diagram showing a system for reducing or removing volatile organic compounds or odors contained in a fluid, wherein the time extension is performed in the entire region in which the plurality of units are arranged.
FIG. 3 contains 50 ppm of toluene (increase in concentration from 230 hours to 230 ppm), 50 ppm of ethanol, and 10 ppm of hydrogen sulfide using a volatile organic compound or odor reduction or removal treatment system included in the fluid of the present invention. Figure showing the treatment concentration of toluene, ethanol and hydrogen sulfide when 580 hours of air treatment
FIG. 4 shows 50 ppm of toluene (increase in concentration from 230 hours to 230 ppm), 50 ppm of ethanol, and 10 ppm of hydrogen sulfide using a volatile organic compound or odor reduction or removal treatment system except the adsorption filter in the configuration of the present invention. Figure showing the treatment concentration of toluene, ethanol and hydrogen sulfide when air was treated for 580 hours
본 발명은 비교적 긴 체류시간을 필요로 하는 광촉매를 이용한 촉매산화 공정에 있어서 광촉매산화공정 내부에서의 체류시간을 연장하기 위하여 흡착과 광촉매산화공정으로 이루어진 크로마토그라프적 흡탈착을 활용한 휘발성유기화합물 또는 악취를 함유한 유체처리를 위한 환경 카트리지 유닛과 휘발성유기화합물 또는 악취를 함유한 유체처리 방법에 관한 것이다.The present invention provides a volatile organic compound utilizing chromatographic adsorption and desorption consisting of adsorption and photocatalytic oxidation in order to prolong the residence time in the photocatalytic oxidation process in a catalytic oxidation process using a photocatalyst requiring a relatively long residence time. The present invention relates to an environmental cartridge unit for treating a malodorous fluid and a method for treating a fluid containing volatile organic compounds or malodors.
도 1에서와 같이 광촉매 층, 흡착 층과 광촉매 층의 순서로 구성된 환경 카트리지 유닛은, 앞과 뒤의 광촉매 층에서의 유체에 함유된 휘발성유기화합물 또는 악취의 광촉매반응을 위한 체류시간을 연장시켜서 유체에 함유된 휘발성유기화합물 또는 악취의 처리효율을 지속적으로 제고시킨다. 본 발명의 환경카트리지 유닛을 복수로 유체처리 방향에 직렬(in series)로 배치하였을 때에, 본 발명의 시스템 전 영역에 직렬로 배치된 복수의 흡착층에서의 크로마토그래프적 흡탈착에 의한 휘발성유기화합물 또는 악취의 광촉매반응에서의 체류시간 연장이 복수의 상기 유닛을 배치한 전 영역에서 이루어지는 것을 특징으로 하며, 유체에 포함된 휘발성유기화합물 또는 악취를 효과적으로 저감 또는 제거 처리할 수 있다. 광촉매반응에 의한 유체에 포함된 휘발성유기화합물 또는 악취의 저감 또는 제거처리 방법에 있어서, 휘발성유기화합물 또는 악취의 저감 또는 제거효율 제고를 목적으로 광원에 의하여 활성화된 광촉매에 의한 반응에서의 휘발성유기화합물 또는 악취의 체류시간을 증대시키기 위하여, 유체 진행방향으로 광촉매필터와 광촉매필터 사이에 흡착필터를 삽입하여, 광촉매필터-흡착필터-광촉매필터로 이루어진 유체에 포함된 휘발성유기화합물 또는 악취의 저감 또는 제거처리 유닛 또는 상기 환경 카트리지 유닛을 도 2와 같이 구성한다. 상기 유닛의 유체진행방향 전후에 광원을 조사하여 상기 유닛의 광촉매필터를 활성화시키며, 복수의 상기유닛을 배치하여 복수의 흡착필터에 의한 휘발성유기화합물 또는 악취의 광촉매반응에서의 체류시간 연장이 복수의 상기 유닛을 배치한 전 영역에서 이루어지는 것을 특징으로 하며, 유체에 포함된 휘발성유기화합물 또는 악취를 효과적으로 저감 또는 제거 처리할 수 있다. 본 발명의 실시 예로서, 본 발명의 구성과 본 발명의 구성에서 흡착필터만을 제외한 각각의 휘발성유기화합물 또는 악취의 저감 또는 제거처리 시스템들에서의 톨루엔, 에탄올 및 황화수소로 이루어진 복합악취의 처리농도 비교를 각각 도 3과 도 4와 같이 나타내었다.As shown in FIG. 1, the environmental cartridge unit configured in the order of the photocatalyst layer, the adsorption layer, and the photocatalyst layer extends the residence time for the photocatalytic reaction of volatile organic compounds or odors contained in the fluid in the front and rear photocatalyst layers. It continuously improves the treatment efficiency of volatile organic compounds or odors contained in. Volatile organic compounds by chromatographic adsorption and desorption in a plurality of adsorption layers arranged in series in the whole area of the system when the plurality of environmental cartridge units of the present invention are arranged in series in the fluid treatment direction Or extending the residence time in the photocatalytic reaction of the odor is carried out in the whole region in which the plurality of units are arranged, and the volatile organic compound or odor contained in the fluid can be effectively reduced or removed. In the method for reducing or removing volatile organic compounds or odors contained in a fluid by a photocatalytic reaction, a volatile organic compound in a reaction by a photocatalytically activated light source for the purpose of reducing or removing volatile organic compounds or odors. Alternatively, in order to increase the residence time of the odor, an adsorption filter is inserted between the photocatalyst filter and the photocatalyst filter in the fluid advancing direction to reduce or eliminate volatile organic compounds or odors contained in the fluid consisting of the photocatalyst filter, the adsorption filter, and the photocatalyst filter. The processing unit or the environmental cartridge unit is configured as shown in FIG. The photocatalyst filter of the unit is activated by irradiating a light source before and after the fluid running direction of the unit, and the plurality of units are arranged to extend the residence time in the photocatalytic reaction of volatile organic compounds or odors by the plurality of adsorption filters. It is made in the whole area | region which arrange | positioned the said unit, The volatile organic compound or odor contained in a fluid can be effectively reduced or removed. As an embodiment of the present invention, the treatment concentration of the complex odor consisting of toluene, ethanol and hydrogen sulfide in each of the volatile organic compounds or odor reduction or removal systems except the adsorption filter in the configuration of the present invention and the configuration of the present invention is compared. It is shown as shown in Figure 3 and 4, respectively.
① 흡착 층 또는 흡착필터
② 광촉매 층 또는 광촉매필터
③ 광원
④ 환경 카트리지 유닛① Adsorption layer or adsorption filter
② photocatalyst layer or photocatalyst filter
③ light source
④ environmental cartridge unit
Claims (7)
상기 광촉매 층(layer)은 유체가 통과할 수 있도록 기공(pore)이 설비된 광촉매가 코팅된 단수 또는 복수의 막필터, 광촉매가 코팅된 입자상 담체로 충전된 광촉매 필터 또는 광촉매가 코팅된 허니컴 필터 중의 하나이고;
상기 흡착 층(layer)은 유체가 통과할 수 있도록 기공(pore)을 포함하는 흡착제로 표면 처리된 단수 또는 복수의 막필터, 흡착제 입자로 충전된 흡착제 필터 또는 흡착제가 코팅되거나 흡착제로 성형된 허니컴 필터 중의 하나인 것을 특징으로 하는 유체에 포함된 휘발성유기화합물 또는 악취의 저감 또는 제거처리를 위한 환경 카트리지 유닛.A multi-layer composed of a combination of a photocatalyst layer and an adsorption layer, the photocatalyst layer being configured in the order of the adsorption layer and the photocatalyst layer;
The photocatalyst layer may include a single or a plurality of membrane filters coated with a photocatalyst equipped with pores to allow fluid to pass therethrough, a photocatalyst filter filled with a photocatalyst coated particulate carrier, or a photocatalyst coated honeycomb filter. One;
The adsorption layer is a single or plural membrane filters surface-treated with an adsorbent including pores to allow fluid to pass therethrough, an adsorbent filter filled with adsorbent particles, or a honeycomb filter coated with an adsorbent or molded into an adsorbent. An environmental cartridge unit for reducing or eliminating volatile organic compounds or odor contained in a fluid, characterized in that one of the.
유체에 포함된 휘발성유기화합물 또는 악취의 저감 또는 제거처리를 위한 환경 카트리지 유닛.2. The outer side surfaces of the environmental cartridge unit according to claim 1, wherein each of the outer side surfaces of the environmental cartridge unit which are both sides in contact with the fluid without contacting the adsorption layer of the first photocatalyst layer and the last photocatalyst layer in the direction of fluid flow in the photocatalyst layer of the environmental cartridge unit, respectively Characterized in that it is disposed facing the light sources;
An environmental cartridge unit for reducing or eliminating volatile organic compounds or odors contained in a fluid.
유체에 포함된 휘발성유기화합물 또는 악취의 저감 또는 제거처리를 위한 환경 카트리지 유닛.5. The method of claim 1 or 4, wherein the environmental cartridge unit is arranged in series in one or more fluid treatment directions;
An environmental cartridge unit for reducing or eliminating volatile organic compounds or odors contained in a fluid.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030033545A (en) * | 2001-10-23 | 2003-05-01 | 양오봉 | Photocatalytic system and method for the removal of volatile organic compounds |
| KR20030050386A (en) * | 2001-12-18 | 2003-06-25 | 주식회사 한국클리너지 | Preparation of catalyst for removal of volatile organic compounds |
| KR100436109B1 (en) | 2001-06-25 | 2004-06-23 | 세신전자(주) | Coupling system of low-temperature catalyst and photocatalyst for indoor air quality control |
| JP2006280428A (en) * | 2005-03-31 | 2006-10-19 | Koha Co Ltd | Disinfection deodorization filter and disinfection deodorization apparatus |
-
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100436109B1 (en) | 2001-06-25 | 2004-06-23 | 세신전자(주) | Coupling system of low-temperature catalyst and photocatalyst for indoor air quality control |
| KR20030033545A (en) * | 2001-10-23 | 2003-05-01 | 양오봉 | Photocatalytic system and method for the removal of volatile organic compounds |
| KR20030050386A (en) * | 2001-12-18 | 2003-06-25 | 주식회사 한국클리너지 | Preparation of catalyst for removal of volatile organic compounds |
| JP2006280428A (en) * | 2005-03-31 | 2006-10-19 | Koha Co Ltd | Disinfection deodorization filter and disinfection deodorization apparatus |
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