KR102022864B1 - System for treating volatile organic compounds, comprising an absorption tower, a stripping tower, and a regenerative combustion device - Google Patents

System for treating volatile organic compounds, comprising an absorption tower, a stripping tower, and a regenerative combustion device Download PDF

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KR102022864B1
KR102022864B1 KR1020180041924A KR20180041924A KR102022864B1 KR 102022864 B1 KR102022864 B1 KR 102022864B1 KR 1020180041924 A KR1020180041924 A KR 1020180041924A KR 20180041924 A KR20180041924 A KR 20180041924A KR 102022864 B1 KR102022864 B1 KR 102022864B1
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volatile organic
tower
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organic compound
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백일현
박성열
남성찬
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한국에너지기술연구원
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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
    • B01D53/75—Multi-step processes
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    • 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
    • B01D53/005—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 heat treatment
    • 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
    • B01D53/02—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
    • B01D53/0462—Temperature swing adsorption
    • 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
    • B01D53/02—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
    • B01D53/047—Pressure swing adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B01D53/14—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 absorption
    • B01D53/1425—Regeneration of liquid absorbents
    • 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
    • B01D53/14—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 absorption
    • B01D53/1493—Selection of liquid materials for use as absorbents
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23C—METHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN  A CARRIER GAS OR AIR 
    • F23C13/00—Apparatus in which combustion takes place in the presence of catalytic material
    • F23C13/08—Apparatus in which combustion takes place in the presence of catalytic material characterised by the catalytic material
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

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Abstract

The present invention relates to treatment of volatile organic compounds. More specifically, the present invention relates to a regenerative thermal oxidation system including an absorption method for concentrating volatile organic compounds. The system of the present invention can concentrate volatile organic compounds even at low concentrations of polluted gas, the concentrate is combusted and the process heat can be recycled, and thus energy required for treating volatile organic compounds can be reduced.

Description

흡수탑과 탈거탑 및 축열식연소장치를 포함하는 휘발성유기화합물 처리 시스템{System for treating volatile organic compounds, comprising an absorption tower, a stripping tower, and a regenerative combustion device}System for treating volatile organic compounds, comprising an absorption tower, a stripping tower, and a regenerative combustion device

본 발명은 휘발성유기화합물을 포집하고 처리하는 시스템에 관한 것으로, 보다 구체적으로 흡수탑을 통과하는 배출가스의 휘발성유기화합물을 온도 또는 압력에 따른 용해도 차이를 나타내는 휘발성유기화합물 포집액으로 포집한 뒤 탈거탑에서 포집액으로부터 휘발성유기화합물을 분리하여 농축하는 흡수탑-탈거탑 공정으로 휘발성유기화합물을 농축하여 연소처리하는, 흡수탑과 탈거탑 및 축열식연소장치를 포함하는 휘발성유기화합물 처리 시스템에 관한 것이다.The present invention relates to a system for capturing and treating volatile organic compounds. More specifically, the present invention relates to a system for capturing and treating volatile organic compounds. The present invention relates to a volatile organic compound processing system including an absorption tower, a stripping column, and a regenerative combustion device, which concentrate and burn a volatile organic compound in an absorption tower-elimination tower process for separating and concentrating a volatile organic compound from a collection liquid in a tower. .

휘발성유기화합물(Volatile Organic Compounds; VOCs)은 중금속과 함께 특정 대기유해물질에 속하는 물질이다. 대형 및 중소 공단 기업체의 인쇄 및 도장, 화학제품 생산 과정이나 바이오매스 반탄화 공정 등에서 배출되며 대기 중에서 미세먼지 또는 질소산화물 등과 결합하여 오존을 생성하여 스모그의 원인이 되는 대표적 대기오염물질이다. 상온, 상압 에서 액체상이나 고체상으로 존재할 수 있지만 쉽게 증발되어 대기 중에서는 가스상으로 존재하기도 한다.Volatile Organic Compounds (VOCs), together with heavy metals, are substances belonging to certain airborne substances. It is emitted from printing and painting of large and small industrial enterprises, chemical production process and biomass semi-carbonization process, and is the representative air pollutant that causes ozone by combining ozone with fine dust or nitrogen oxide in the air. It can exist in liquid or solid phase at room temperature and atmospheric pressure, but can easily evaporate and exist in the gaseous state in the atmosphere.

휘발성유기화합물을 이루는 대부분의 물질들은 낮은 농도에서도 자극적이고 불쾌한 냄새를 발생시키며, 인체와의 피부 접촉이나 호흡기로 유입될 경우 신경계 등의 장애를 일으키는 발암물질로 분류되어 있기도 하다. 이러한 측면을 강조하여 HAPs(Hazardous Air Pollutants)라고도 하며 미국에서는 189개의 물질을, 국내에서는 가장 많이 사용되는 톨루엔을 포함하여 48개 물질을 휘발성유기화합물로 정하여 규제하고 있다. Most of the substances that make up volatile organic compounds generate irritating and unpleasant odors even at low concentrations, and are classified as carcinogens that cause disorders such as the nervous system when they come into contact with the skin or enter the respiratory tract. Emphasis on this aspect is also called Hazards Air Pollutants (HAPs), which regulates 189 substances in the US and 48 substances, including toluene, the most commonly used in Korea, as volatile organic compounds.

휘발성유기화합물의 처리 방법으로는 연소법(열산화법), 생물학적 처리법, 흡착법, 촉매산화, 농축산화법 등이 적용되고 있다. 미국 Climate technologies Corp.은 흡착장치 및 탈착장치를 구비하고 송풍으로 흡착제를 각 장치로 주입하고 동시에 구동하여 포집된 휘발성유기화합물을 축열연소 및 산화처리장치 뿐만 아니라 엔진, 제너레이터 및 연료전지에 연료로 사용 가능한 휘발성유기화합물의 처리시스템을 구축하였다(A technical paper: Using Volatile Organic Compound Emissions from Industrial Painting P rocesseass a Source of Fuel Cell Energy, Mark R. Wherrett et al.). 하지만 이는 활성탄을 사용하는 시스템으로 마모방지를 위해 휘발성유기화합물의 흡착제를 제조과정이 복잡하며 고비용인 구형 활성탄을 사용한다.As a method for treating volatile organic compounds, a combustion method (thermal oxidation method), a biological treatment method, an adsorption method, a catalytic oxidation method, a concentrated oxidation method, and the like are applied. US Climate technologies Corp. is equipped with adsorption device and desorption device and injects adsorbents into each device by blowing and drives them simultaneously to use the collected volatile organic compounds as fuel in engines, generators and fuel cells as well as in regenerative combustion and oxidation treatment devices. A technical paper: Using Volatile Organic Compound Emissions from Industrial Painting P rocesseass a Source of Fuel Cell Energy, Mark R. Wherrett et al. However, this is a system that uses activated carbon to make the adsorbent of volatile organic compounds to prevent abrasion and to use spherical activated carbon which is complicated and expensive.

일반적으로 활성탄을 이용한 휘발성유기화합물 처리방법은 활성탄을 충진한 복수의 흡착탑을 설치하고 흡착과 탈착을 교대로 반복하는 고정상식 용제 회수장치 등이 알려져 있다. 활성탄에 의해 농축된 휘발성유기화합물은 연소, 응축에 의한 회수, 발전, 리포밍의 후처리를 통해 처리되고 활성탄은 재생된다. 그러나 휘발성유기화합물 오염가스의 농도가 매우 낮을 경우 10배 농축으로는 상기 후처리 방법들의 적용이 어렵고 탈착하는데 많은 에너지가 소비된다.In general, a method of treating volatile organic compounds using activated carbon is known, such as a fixed bed solvent recovery apparatus in which a plurality of adsorption towers filled with activated carbon are installed and the adsorption and desorption are alternately repeated. Volatile organic compounds concentrated by activated carbon are processed through post-treatment of recovery, power generation and reforming by combustion, condensation, and activated carbon is regenerated. However, when the concentration of volatile organic pollutant gases is very low, the application of the post-treatment methods is difficult with 10-fold concentration, and a lot of energy is consumed for desorption.

한편 농축된 휘발성유기화합물을 처리하기 위한 방법 중 축열연소법(RTO:Regenerative/Recuperative Thermal Oxidizer)은 산화온도를 800℃ 이상으로 유지하여 휘발성유기화합물을 고온으로 산화시키는 산화법으로 일반적으로 폐가스중의 휘발성유기화합물의 산화발열량에 의한 승온온도가 가스단위 입방미터당 40∼80℃인 경우에는 추가적인 연료의 공급없이 운전이 가능하다. 축열연소법은 휘발성 유기화합물의 소각처리에 따른 연료비용을 절감하고, 휘발성 유기화합물의 산화시 발생되는 폐열을 재활용할 수 있다는 장점으로 인하여, 국내 뿐만 아니라 해외에서도 많은 연구개발이 이루어지고 있다.On the other hand, regenerative / recuperative thermal oxidizer (RTO) is an oxidation method that oxidizes volatile organic compounds at high temperature by maintaining the oxidation temperature above 800 ℃ among the methods for treating concentrated volatile organic compounds. When the temperature rise temperature by the amount of oxidation calorific value of the compound is 40 ~ 80 ℃ per cubic meter of gas unit can be operated without supply of additional fuel. The regenerative combustion method reduces the fuel cost according to incineration of volatile organic compounds and recycles waste heat generated during oxidation of volatile organic compounds.

대한민국 등록특허 제1250940호는 악취 및 휘발성유기화합물을 처리하는 시스템으로, VOC를 고체 흡착제를 이용하여 농축하고, 이를 산화시키는 처리 시스템을 개시한다. 하지만 이는 고체 흡착제를 사용함에 따라 흡착과 탈착의 효율적인 연속적 공정이 어렵고 낮은 농도의 VOC 흡착에 어려움이 따른다. Korean Patent No. 1250940 discloses a treatment system for treating malodors and volatile organic compounds, concentrating VOCs using a solid adsorbent, and oxidizing them. However, this results in difficulty in efficient continuous process of adsorption and desorption due to the use of solid adsorbents and difficulties in adsorption of low concentrations of VOC.

따라서 효율적인 휘발성유기화합물 처리를 위해 저농도의 오염가스에서도 고농도로 흡탈착할 수 있고 에너지 소모가 적은 휘발성유기화합물 처리의 기술 개발이 요구된다.Therefore, in order to efficiently process volatile organic compounds, it is required to develop a technology for treating volatile organic compounds that can be adsorbed and desorbed at a high concentration even at low concentrations of polluted gases and has low energy consumption.

(0001) 대한민국 등록특허 1250940호(0001) Republic of Korea Patent 1250940

본 발명은, 전술한 종래기술의 제반 문제점을 해결하기 위해 안출된 것으로 흡수액으로 흡수탑 및 탈거탑에서 휘발성유기화합물을 농축하고 축열식 연소기에서 산화처리하는 농축-처리 일관공정의 휘발성유기화합물 농축 및 처리 시스템을 제공하고자 한다.The present invention has been made to solve the above-mentioned problems of the prior art, and concentrates and treats volatile organic compounds in a concentrated-treatment integrated process, which concentrates volatile organic compounds in absorption tower and stripping tower with absorption liquid and oxidizes them in a regenerative combustor. We want to provide a system.

상기 과제를 해결하기 위하여, 본 발명자들은 산업현장에서 배출되는 휘발성유기화합물의 처리를 위해 흡수탑과 탈거탑을 이용하여 휘발성유기화합물을 흡수-농축하고 축열식연소기로 산화처리하며 연소기에서 배출되는 배가스는 상기 탈거탑의 열원으로 사용하여 에너지 효율을 극대화할 수 있음을 발견하여 본 발명을 완성하였다. In order to solve the above problems, the present inventors absorb-concentrate volatile organic compounds using an absorption tower and stripping tower for the treatment of volatile organic compounds discharged from industrial sites, oxidize them with a regenerative combustion furnace, and exhaust gas discharged from the combustor. The present invention was completed by discovering that energy efficiency can be maximized using the stripping column as a heat source.

본 발명은 흡수탑과 탈거탑 및 축열식연소기를 포함하는 휘발성유기화합물 처리시스템으로, 상기 시스템은 흡수액을 이용하여 휘발성유기화합물을 흡수하는 흡수탑; 상기 흡수탑에서 휘발성유기화합물을 흡수한 흡수액을 공급받아 흡수액으로부터 휘발성유기화합물을 탈거하여 농축하는 탈거탑; 및 상기 탈거탑에서 농축된 휘발성유기화합물을 산화하는 축열식 연소기(RTO)를 포함하고, 상기 탈거탑에서 재생된 흡수액은 흡수탑으로 공급되어 재사용되고, 상기 축열식 연소기에서 배출되는 배가스는 상기 탈거탑의 열원으로 사용되는, 흡수탑과 탈거탑 및 축열식연소장치를 포함하는 휘발성유기화합물 처리 시스템을 제공한다.The present invention relates to a volatile organic compound processing system including an absorption tower, a stripping column, and a regenerative combustion apparatus, wherein the system includes: an absorption tower for absorbing a volatile organic compound using an absorption liquid; A stripping column receiving the absorbing liquid absorbing the volatile organic compound from the absorption tower and removing the concentrated volatile organic compound from the absorbing liquid and concentrating it; And a regenerative combustor (RTO) for oxidizing the volatile organic compound concentrated in the stripping column, and the absorbent liquid regenerated in the stripping column is supplied to the absorption tower for reuse, and the exhaust gas discharged from the regenerative combustor is Provided is a volatile organic compound treatment system including an absorption tower, stripping column, and a regenerative combustion device, which is used as a heat source.

본 발명은 또한, 상기 흡수액은 휘발성유기화합물의 종류에 따라 서로 쌍을 이루며, 상기 흡수액-휘발성유기화합물 쌍은 하기 표 1로 이루어진 군에서 선택되는 하나 이상의 휘발성유기화합물-흡수액 쌍인, 흡수탑과 탈거탑 및 축열식연소장치를 포함하는 휘발성유기화합물 처리 시스템을 제공한다.In the present invention, the absorbent liquid is paired with each other according to the type of volatile organic compound, the absorbent liquid-volatile organic compound pair is one or more volatile organic compound-absorbent liquid pair selected from the group consisting of Table 1, absorption tower and de Provided is a volatile organic compound processing system including a tower and a regenerative combustion device.

[표 1]TABLE 1

Figure 112018035842410-pat00001
Figure 112018035842410-pat00001

본 발명은 또한, 상기 축열식 연소기는 Co, Ni, Mo. V, W, Pt 및 Pd으로 이루어진 군에서 선택되는 하나 이상의 촉매를 담지한 촉매층을 포함하는, 흡수탑과 탈거탑 및 축열식연소장치를 포함하는 휘발성유기화합물 처리 시스템을 제공한다.The present invention, the regenerative combustor is Co, Ni, Mo. Provided is a volatile organic compound treatment system including an absorption tower, a stripping column, and a regenerative combustion device, including a catalyst layer carrying at least one catalyst selected from the group consisting of V, W, Pt, and Pd.

본 발명은 또한, 상기 흡수탑과 탈거탑의 흡수 및 탈거 온도 및 압력은, 상기 흡수액-휘발성유기화합물 쌍에 따라 조정 가능한, 흡수탑과 탈거탑 및 축열식연소장치를 포함하는 휘발성유기화합물 처리 시스템을 제공한다.The present invention also provides a volatile organic compound treatment system comprising an absorption tower, a stripping column, and a regenerative combustion device, wherein absorption and stripping temperatures and pressures of the absorption tower and the stripping column are adjustable according to the absorbing liquid-volatile organic compound pair. to provide.

본 발명은 또한, 상기 열원은 탈거탑의 리보일러에 공급되거나 또는 직접적으로 탈거탑을 가열하는, 흡수탑과 탈거탑 및 축열식연소장치를 포함하는 휘발성유기화합물 처리 시스템을 제공한다.The present invention also provides a volatile organic compound processing system comprising an absorption tower, a stripping column and a regenerative combustion device, wherein the heat source is supplied to the reboiler of the stripping column or directly heats the stripping column.

본 발명은 또한, 상기 흡수탑 및 탈거탑에서 VOCs를 흡수 및 탈거하는 것은 온도조절법(temperature swing absorption, TSA) 또는 압력조절법(Pressure swing absorption, PSA)으로 수행되며, 상기 온도조절법은 상기 흡수탑을 10 내지 60℃로 유지하면서 VOCs를 흡수하고, 상기 탈거탑을 70 내지 150℃로 유지하면서 VOCs를 탈거하는 것이며, 상기 압력조절법은 상기 흡수탑을 2 내지 80bar로 유지하면서 VOCs를 흡수하고, 상기 탈거탑을 0.1 내지 2bar로 유지하면서 VOCs를 탈거하는 것인, 흡수탑과 탈거탑 및 축열식연소장치를 포함하는 휘발성유기화합물 처리 시스템을 제공한다.In the present invention, the absorption and removal of the VOCs in the absorption tower and stripping column is performed by temperature swing absorption (TSA) or pressure swing absorption (PSA), the temperature control method is the absorption tower Absorbing VOCs while maintaining at 10 to 60 ℃, while removing the VOCs while maintaining the stripping tower at 70 to 150 ℃, the pressure control method absorbs VOCs while maintaining the absorption tower at 2 to 80 bar, The present invention provides a volatile organic compound treatment system including an absorption tower, a stripping column, and a regenerative combustion device, wherein the VOCs are removed while maintaining the column at 0.1 to 2 bar.

본 발명의 흡수탑과 탈거탑 및 축열식연소장치를 포함하는 휘발성유기화합물 처리 시스템은 저농도의 휘발성유기화합물을 포함하는 오염가스 또는 배기가스에서도 연속공정으로 휘발성유기화합물을 농축하고 이를 축열식연소장치로 열처리하며 공정열을 재활용할 수 있어서, 연속공정을 통한 처리효율 향상과 에너지절감을 통한 경제성을 확보할 수 있다.The volatile organic compound treatment system including the absorption tower, the stripping column, and the regenerative combustion device of the present invention concentrates the volatile organic compound in a continuous process even in a pollutant gas or exhaust gas containing a low concentration of volatile organic compound and heat-treats it with a regenerative combustion device. In addition, the process heat can be recycled, thereby improving economic efficiency through energy efficiency and improving treatment efficiency through a continuous process.

도 1은 본 발명의 한 구현예에 따른 흡수탑과 탈거탑 및 축열식연소장치를 포함하는 휘발성유기화합물 처리시스템의 개략도이다.
도 2는 본 발명의 한 구현예에 따른 흡수탑과 탈거탑을 포함하는 휘발성유기화합물 농축부를 나타내는 개략도이다.1 is a schematic diagram of a volatile organic compound processing system including an absorption tower, a stripping column, and a regenerative combustion apparatus according to an embodiment of the present invention.
Figure 2 is a schematic diagram showing a volatile organic compound concentrate comprising an absorption tower and stripping column according to an embodiment of the present invention.

이하 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있을 정도로 바람직한 실시예를 도면을 참조하여 상세하게 설명하면 다음과 같다. 본 발명의 상세한 설명에 앞서, 이하에서 설명되는 본 명세서 및 청구범위에 사용된 용어나 단어는 통상적이거나 사전적인 의미로 한정해서 해석되어서는 아니 된다. 따라서, 본 명세서에 기재된 실시예와 도면에 도시된 구성은 본 발명의 가장 바람직한 일실시예에 불과할 뿐이고 본 발명의 기술적 사상을 모두 대변하는 것은 아니므로, 본 출원시점에 있어서 이들을 대체할 수 있는 다양한 균등물과 변형예들이 있을 수 있음을 이해하여야 한다. Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily perform the following. Prior to the description of the invention, the terms or words used in the specification and claims described below should not be construed as limiting in their usual or dictionary meanings. Therefore, the embodiments described in the specification and the drawings shown in the drawings are only one of the most preferred embodiments of the present invention and do not represent all of the technical idea of the present invention, various modifications that can be replaced at the time of the present application It should be understood that there may be equivalents and variations.

한 양태에서 본 발명은 휘발성유기화합물을 농축하기 위한 흡수방법을 포함하는 축열식 연소(RTO) 시스템으로, 상기 시스템은 흡수액을 이용하여 휘발성유기화합물(Volatile Organic Compounds, VOCs)을 흡수하는 흡수탑; 상기 흡수탑에서 휘발성유기화합물을 흡수한 흡수액을 공급받아 흡수액으로부터 휘발성유기화합물을 탈거하고 농축하는 탈거탑; 및 상기 탈거탑에서 농축된 휘발성유기화합물을 산화하는 축열식 연소기를 포함한다. 본 발명의 휘발성유기화합물이란 증기압이 높아 대기 중으로 쉽게 증발되는 액체 또는 기체상 유기화합물의 총칭이며, VOCs(Volatile Organic Compounds)라고도 한다. 대기오염물질이며 발암성을 지닌 독성 화학물질이고, 대기 중에서 질소산화물과 공존하면 햇빛의 작용으로 광화학반응을 일으켜 오존 및 팬(PAN: eroxyacetyl nitrate) 등 광화학 산화성 물질을 생성시켜 광화학스모그를 유발하는 물질을 통틀어 일컫는 말이다. 또한 지구온난화의 원인물질이며 악취를 일으키기도 한다. 벤젠, 자일렌, 아세틸렌, 클로로포름, 휘발유 등을 비롯하여 산업체에서 사용되는 용매 등이 포함된다. 본 발명에서는 휘발성유기화합물을 농축하고 처리하기 위한 흡수방법 및 처리방법을 제공한다. In one aspect, the present invention provides a regenerative combustion (RTO) system including an absorption method for concentrating volatile organic compounds, the system comprising: an absorption tower for absorbing volatile organic compounds (VOCs) using an absorption liquid; A stripping column receiving the absorbing liquid absorbing the volatile organic compound from the absorption tower and removing and concentrating the volatile organic compound from the absorbing liquid; And a regenerative combustor for oxidizing the volatile organic compound concentrated in the stripping column. The volatile organic compounds of the present invention are generic terms of liquid or gaseous organic compounds that are easily vaporized into the atmosphere due to high vapor pressure, and are also referred to as VOCs (Volatile Organic Compounds). It is an air pollutant and a toxic chemical with carcinogenicity. When coexisted with nitrogen oxide in the air, it causes photochemical reaction by the action of sunlight to generate photochemical oxidizing substances such as ozone and pan (eroxyacetyl nitrate) to induce photochemical smog. The term is used throughout. It is also a source of global warming and can cause odors. Benzene, xylene, acetylene, chloroform, gasoline and the like, as well as solvents used in industry. The present invention provides an absorption method and a treatment method for concentrating and treating volatile organic compounds.

도 1은 한 구현예에 따른 흡수탑과 탈거탑 및 축열식연소장치를 포함하는 휘발성유기화합물 처리 시스템의 개략도이다. 상기 흡수탑(10)은 휘발성유기화합물(VOCs)을 흡수액을 이용하여 흡수하는 장치로, 예를 들면 액상의 흡수제를 흡수탑 상부에서 분사하고 하부로 공급되는 VOCs 함유 가스 중 VOCs를 흡수한다. 상기 VOCs를 흡수한 흡수액은 VOCs를 흡수한 흡수액 공급라인(11)을 통하여 흡수탑(10)으로부터 탈거탑(20)으로 공급된다. 상기 탈거탑(20)은 VOCs를 흡수한 흡수액에서 VOCs를 탈거하고 농축한다. 상기 흡수탑(10)과 탈거탑(20)에서의 VOCs의 흡수 및 탈거는 헨리의 법칙(Henry's law)에 기인하여 수행된다. 일정한 온도에서 일정 부피의 액체 용매에 녹는 기체의 질량, 즉 용해도는 용매와 평형을 이루고 있는 그 기체의 부분압력에 비례하는 법칙이다. 본 발명의 흡수 및 탈거는 흡수탑과 탈거탑의 온도조건 또는 압력조건을 일정한 차이를 이용하여 VOCs가 흡수액에 흡수되도록 한다. 흡수탑에서는 VOCs가 높은 용해도를 갖기 위해 비교적 낮은 온도 또는 높은압력을 유지하여 VOCs를 흡수하고, 탈거탑에서는 VOCs가 낮은 용해도 조건에서 흡수액으로부터 탈거되기 위해 비교적 높은 온도 또는 낮은 압력을 유지하여 VOCs를 흡수액으로 부터 탈거할 수 있다. 한 구현예에서 상기 흡수탑 및 탈거탑에서 VOCs를 흡수 및 탈거하는 방법은 온도조절법(Temperature swing absorption, TSA)으로 압력조건 1bar에서 낮은 온도인 10 내지 60℃ 온도 조건의 흡수탑에서 VOCs를 흡수하고 높은 온도인 70 내지 150℃ 온도 조건의 탈거탑에서 VOCs를 탈거한다. 또 다른 구현에에서 VOCs를 흡수 및 탈거하는 방법은 압력조절법(Pressure swing absorption, PSA)로 일정한 온도 예를 들면 상온에서 높은 압력인 2 내지 80bar 압력 조건의 흡수탑에서 VOCs를 흡수하고 낮은 압력인 0.1 내지 2bar 압력 조건의 탈거탑에서 VOCs를 탈거한다. 흡수탑으로 공급되는 가스 중 VOCs의 각 종류 포함량에 따라 흡수액을 조절하여 사용할 수 있으며, 이는 휘발성유기화합물 종의 헨리상수에 따라 흡수액을 조절하여 사용할 수 있다(Fluid Phase Equilibria 241 (2006) 96?102,Henry’s constants of gases and volatile organic compounds in aqueous solutions, James B. Falabella, Austin C. Kizzie, Amyn S. Teja *). 한 구현예에서 상기 흡수액은 하기 표 1의 흡수액-휘발성유기화합물 쌍에서 선택되는 하나 이상으로 사용하며, 상기 휘발성유기화합물은 하기 표 1의 동일 행에 속한 군에서 선택되는 하나 이상이고, 상기 흡수탑과 탈거탑의 흡수 및 탈거 온도는, 상기 휘발성유기화합물-흡수액쌍에 따라 조정 가능하다. 상기 흡수액-휘발성유기화합물 쌍의 선택은 예를 들면 벤젠을 처리하고 할 경우 1-methyl-3-octyl-imidazolium chlloride([moim]Cl)-벤젠 및 1,2-dimethyl-2-imidazolidinone(DMI)-벤젠 쌍을 선택하는 것으로, 1-methyl-3-octyl-imidazolium chlloride([moim]Cl) 및 2-dimethyl-2-imidazolidinone(DMI)를 흡수액으로 사용할 수 있다.1 is a schematic diagram of a volatile organic compound processing system including an absorption tower, a stripping column, and a regenerative combustion apparatus according to one embodiment. The absorption tower 10 is a device that absorbs volatile organic compounds (VOCs) using an absorption liquid. For example, a liquid absorbent is injected from an upper portion of the absorption tower and absorbs VOCs from a VOCs-containing gas supplied to the lower portion. The absorbent liquid absorbing the VOCs is supplied from the absorption tower 10 to the stripping column 20 through the absorbent liquid supply line 11 absorbing the VOCs. The stripping column 20 removes and concentrates the VOCs in the absorbent liquid that absorbs the VOCs. Absorption and stripping of VOCs in the absorption tower 10 and stripping column 20 is performed due to Henry's law. The mass of a gas, ie solubility, dissolved in a volume of liquid solvent at a constant temperature is a law proportional to the partial pressure of the gas in equilibrium with the solvent. Absorption and stripping of the present invention allows the VOCs to be absorbed into the absorbent liquid using a constant difference in temperature or pressure conditions between the absorption tower and the stripping column. The absorption tower absorbs VOCs at a relatively low temperature or high pressure to have high solubility, and the stripping tower absorbs VOCs at a relatively high temperature or low pressure to remove VOCs from the absorbent at low solubility. Can be removed from In one embodiment, the absorption and removal of the VOCs in the absorption tower and stripping column is a temperature control method (Temperature swing absorption, TSA) to absorb the VOCs in the absorption tower at a temperature of 10 to 60 ℃ low temperature at 1 bar pressure The VOCs are stripped off in a stripping column at a high temperature of 70 to 150 ° C. In another embodiment, the method of absorbing and removing VOCs is pressure swing absorption (PSA), which absorbs VOCs in an absorption tower at a constant temperature, e. The VOCs are removed in a stripping column at a pressure of 2 bar. The absorption liquid can be adjusted according to the amount of VOCs contained in the gas supplied to the absorption tower, and the absorption liquid can be adjusted according to the Henry's constant of the volatile organic compound species (Fluid Phase Equilibria 241 (2006) 96? 102, Henry's constants of gases and volatile organic compounds in aqueous solutions, James B. Falabella, Austin C. Kizzie, Amyn S. Teja *). In one embodiment, the absorbent liquid is used in at least one selected from the absorbent liquid-volatile organic compound pairs in Table 1, and the volatile organic compounds are at least one selected from the group belonging to the same row in Table 1, and the absorption tower The absorption and stripping temperatures of the stripping column can be adjusted according to the volatile organic compound-absorption liquid pair. The selection of the absorbent liquid-volatile organic compound pair is, for example, 1-methyl-3-octyl-imidazolium chlloride ([moim] Cl) -benzene and 1,2-dimethyl-2-imidazolidinone (DMI) when treated with benzene. By selecting a -benzene pair, 1-methyl-3-octyl-imidazolium chlloride ([moim] Cl) and 2-dimethyl-2-imidazolidinone (DMI) can be used as an absorbent liquid.

[표 1]TABLE 1

Figure 112019067022517-pat00007
Figure 112019067022517-pat00007

상기 탈거탑에서 탈거된 휘발성유기화합물은 농축되어 산화처리되는데 본 발명의 한 구현예에서 상기 산화처리는 축열식 연소기(Regenerative/Recuperative Thermal Oxidizer, RTO)(30)로 공급하여 처리한다. 상기 탈거탑에서 탈거 및 농축된 휘발성유기화합물은 농축 VOCs 공급라인(21)을 통해 축열식 연소기(30)로 공급되어 산화처리 된다. 상기 농축 VOCs는 축열식 연소기로 공급되어 열교환기(301)에서 연소기에서 발생한 고온의 배가스와 열교환하여 예열된 후 연소될 수 있다. VOCs 연소시 산화연료 공급라인(31)을 통해 공기 또는 산소를 공급하여 효과적으로 휘발성유기화합물을 산화처리할 수 있으며, VOCs을 연소하기 위해 VOCs 연소 연료 공급라인(32)을 통해 연료를 공급하여 연소할 수 있다. 또한 상기 축열식 연소기는 연소실내의 온도가 750 내지 900℃를 유지하기 위해 필요한 연료량을 절감하기 위해 촉매에 의한 연소를 추가할 수 있다. 한 구현에에서 상기 촉매는 Co, Ni, Mo. V, W, Pt 및 Pd으로 이루어진 군에서 선택되는 하나 이상의 촉매를 담지한 촉매층(302)이다. The volatile organic compound removed from the stripping column is concentrated and oxidized. In one embodiment of the present invention, the oxidizing is supplied to a regenerative / recuperative thermal oxide (RTO) 30 to be treated. The volatile organic compounds removed and concentrated in the stripping column are supplied to the regenerative combustor 30 through the concentrated VOCs supply line 21 and are oxidized. The concentrated VOCs may be supplied to a regenerative combustor to be preheated by heat exchange with a high temperature exhaust gas generated in the combustor in the heat exchanger 301 and then combusted. When VOCs are burned, air or oxygen may be supplied through the oxidized fuel supply line 31 to effectively oxidize volatile organic compounds, and to burn VOCs, fuel may be supplied through the VOCs combustion fuel supply line 32 to combust VOCs. Can be. In addition, the regenerative combustor may add combustion by a catalyst to reduce the amount of fuel required to maintain the temperature in the combustion chamber 750 to 900 ℃. In one embodiment the catalyst is Co, Ni, Mo. A catalyst layer 302 carrying at least one catalyst selected from the group consisting of V, W, Pt and Pd.

축열식 연소기에서 배출되는 청정가스인 배가스(41)는 고온의 가스인데, 기존 축열식 연소기에서는 이를 이용하여 축열재를 가열하는 방식이다. 그러나 본 발명의 한 구현예에서는 상기 탈거탑(20)의 리보일러(200)에 공급하여 탈거탑으로 공급되는 VOCs를 흡수한 흡수액으로부터 휘발성유기화합물을 탈거하고 예열하는 열원으로 사용된다. 상기 탈거탑(20)은 휘발성유기화합물이 탈거된 재생된 흡수액을 재생된 흡수액 공급라인(22)를 통해 흡수탑으로 재공급하고, 흡수탑에서 재사용한다. 도 2는 본 발명의 탈거탑을 예열하는 방식에 관한 개략도로, 도 2(a)와 같이 연소기에서 배출되는 배가스를 탈거탑 외부 둘레를 따라 가열하는 방식과 도2(b)와 같이 탈거탑 내부를 직접 가열하는 방식을 사용할 수 있다. 도 2(a)의 외부 가열 방식은 탑 외부에 열교환 라인을 설치하고 탑내 열을 공급하는 것으로 열교환기 설치가 용이하고 흡수용액에 의한 장치의 부식을 감소시킬 수 있다. 도 2(b)의 내부 가열 방식은 탑 내부에 열교환 라인을 유체가 지나가는 방향으로 설치하고 탑내 열을 공급하는 것으로 높은 열 전달 효율을 나타낼 수 있으나 흡액과 직접적으로 접촉하기 때문에 흡수 용액에 의한 부식이 발생할 수 있어 흡수용액에 부식 방지제 등을 첨가하여 사용할 수 있다. 본 발명의 흡수탑과 탈거탑 및 축열식연소장치를 포함하는 휘발성유기화합물 처리 시스템은 흡수탑 및 탈거탑을 사용하여 낮은 농도의 VOCs를 흡수-농축할 수 있으며, 축열식 연소기에서 발생하는 배가스를 농축 VOCs의 예열 및 탈거탑의 흡수액 재생에 사용함에 따라 저에너지 소비형 VOCs 처리를 가능하게 한다.The exhaust gas 41, which is a clean gas discharged from the regenerative combustor, is a high temperature gas, and in the existing regenerative combustor, the regenerative material is heated using the same. However, in one embodiment of the present invention is supplied to the reboiler 200 of the stripping column 20 is used as a heat source for removing and preheating the volatile organic compounds from the absorption liquid absorbed VOCs supplied to the stripping tower. The stripping column 20 supplies the regenerated absorbent liquid from which the volatile organic compound has been removed to the absorption tower through the regenerated absorbent liquid supply line 22 and reused in the absorption tower. Figure 2 is a schematic diagram of a method of preheating the stripping column of the present invention, a method of heating the exhaust gas discharged from the combustor as shown in Figure 2 (a) along the outer circumference of the stripping tower and inside the stripping tower as shown in Figure 2 (b) Direct heating can be used. In the external heating method of FIG. 2 (a), a heat exchange line is installed outside the tower and heat is supplied to the tower, so that the heat exchanger can be easily installed and the corrosion of the device due to the absorption solution can be reduced. In the internal heating method of FIG. 2 (b), the heat exchange line is installed inside the tower in the direction in which the fluid passes and the heat is supplied in the tower, thereby exhibiting high heat transfer efficiency. It may be generated, it may be used by adding a corrosion inhibitor to the absorption solution. The volatile organic compound treatment system including the absorption tower, stripping column, and regenerative combustion device of the present invention can absorb and concentrate low concentrations of VOCs using the absorption tower and stripping column, and concentrate the exhaust gas generated from the regenerative combustor. It can be used for preheating and regeneration of absorbent liquid in stripping towers, thus enabling the treatment of low energy consumption VOCs.

이상에서 본원의 예시적인 실시예에 대하여 상세하게 설명하였지만 본원의 권리범위는 이에 한정되는 것은 아니고 다음의 청구범위에서 정의하고 있는 본원의 기본 개념을 이용한 당업자의 여러 변형 및 개량 형태 또한 본원의 권리범위에 속하는 것이다.Although the exemplary embodiments of the present application have been described in detail above, the scope of the present application is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concepts of the present invention defined in the following claims are also provided. It belongs to.

본 발명에서 사용되는 모든 기술용어는, 달리 정의되지 않는 이상, 본 발명의 관련 분야에서 통상의 당업자가 일반적으로 이해하는 바와 같은 의미로 사용된다. 본 명세서에 참고문헌으로 기재되는 모든 간행물의 내용은 본 발명에 도입된다. All technical terms used in the present invention, unless defined otherwise, are used in the meaning as commonly understood by those skilled in the art in the related field of the present invention. The contents of all publications described herein by reference are incorporated into the present invention.

10. 흡수탑
11. VOCs를 흡수한 흡수액 공급라인
20. 탈거탑
21. 농축 VOCs 공급라인
22. 재생된 흡수액 공급라인
30. 축열식 연소기
31. 산화연료 주입라인
32. 연소연료 주입라인
41. 배가스 공급라인
200. 리보일러
302. 촉매층10. Absorption Tower
11. Absorption liquid supply line absorbing VOCs
20. Extraction Tower
21. Concentrated VOCs Supply Line
22. Recycled Absorbent Supply Line
30. Regenerative Combustor
31. Oxide fuel injection line
32. Combustion fuel injection line
41. Flue Gas Supply Line
200. Reboiler
302. Catalyst bed

Claims (6)

흡수탑과 탈거탑 및 축열식연소기를 포함하는 휘발성유기화합물 처리시스템으로,
상기 시스템은 흡수액을 이용하여 휘발성유기화합물을 흡수하는 흡수탑;
상기 흡수탑에서 휘발성유기화합물을 흡수한 흡수액을 공급받아 흡수액으로부터 휘발성유기화합물을 탈거하고 농축하는 탈거탑; 및
상기 탈거탑에서 농축된 휘발성유기화합물을 산화하는 축열식 연소기(RTO)를 포함하고,
상기 탈거탑에서 재생된 흡수액은 흡수탑으로 공급되어 재사용되고,
상기 축열식 연소기에서 배출되는 배가스는 상기 탈거탑의 열원으로 사용되고,
상기 축열식 연소기는 Co, Ni, Mo. V, W, Pt 및 Pd으로 이루어진 군에서 선택되는 하나 이상의 촉매를 담지한 촉매층을 포함하며,
상기 흡수액은 휘발성유기화합물의 종류에 따라 서로 쌍을 이루며,
상기 흡수액-휘발성유기화합물 쌍은 하기 표 1로 이루어진 군에서 선택되는 하나 이상의 휘발성유기화합물-흡수액 쌍이고,
상기 휘발성유기화합물은 하기 표 1의 동일 행에 속한 군에서 선택되는 하나 이상인,
[표 1]
Figure 112019067022517-pat00009

상기 흡수탑 및 탈거탑에서 VOCs를 흡수 및 탈거하는 것은 온도조절법(temperature swing absorption, TSA) 또는 압력조절법(Pressure swing absorption, PSA)으로 수행되며,
상기 온도조절법은 상기 흡수탑을 10 내지 60℃로 유지하면서 VOCs를 흡수하고, 상기 탈거탑을 70 내지 150℃로 유지하면서 VOCs를 탈거하는 것이며,
상기 압력조절법은 상기 흡수탑을 2 내지 80bar로 유지하면서 VOCs를 흡수하고, 상기 탈거탑을 0.1 내지 2bar로 유지하면서 VOCs를 탈거하는 것인,
흡수탑과 탈거탑 및 축열식연소장치를 포함하는 휘발성유기화합물 처리 시스템.
A volatile organic compound treatment system including absorption tower, stripping tower and regenerative combustion machine,
The system includes an absorption tower for absorbing volatile organic compounds using the absorption liquid;
A stripping column receiving the absorbing liquid absorbing the volatile organic compound from the absorption tower and removing and concentrating the volatile organic compound from the absorbing liquid; And
It includes a regenerative combustion (RTO) for oxidizing the volatile organic compounds concentrated in the stripping column,
The absorbent liquid regenerated in the stripping column is supplied to the absorption tower and reused.
The exhaust gas discharged from the regenerative combustor is used as a heat source of the stripping tower,
The regenerative combustor is Co, Ni, Mo. A catalyst layer carrying at least one catalyst selected from the group consisting of V, W, Pt and Pd,
The absorption liquid is paired with each other according to the type of volatile organic compounds,
The absorbent liquid-volatile organic compound pair is at least one volatile organic compound-absorbent liquid pair selected from the group consisting of Table 1 below,
The volatile organic compound is at least one selected from the group belonging to the same row of Table 1 below,
TABLE 1
Figure 112019067022517-pat00009

Absorption and removal of VOCs in the absorption tower and stripping column is carried out by temperature swing absorption (TSA) or pressure swing absorption (PSA),
The temperature control method is to absorb the VOCs while maintaining the absorption tower at 10 to 60 ℃, remove the VOCs while maintaining the stripping tower at 70 to 150 ℃,
The pressure control method is to absorb the VOCs while maintaining the absorption tower at 2 to 80 bar, and to remove the VOCs while maintaining the stripping tower at 0.1 to 2 bar,
Volatile organic compound treatment system including absorption tower, stripping tower and regenerative combustion device.
삭제delete 삭제delete 제 1 항에 있어서,
상기 흡수탑과 탈거탑의 흡수 및 탈거 온도 및 압력은, 상기 흡수액-휘발성유기화합물 쌍에 따라 조정 가능한,
흡수탑과 탈거탑 및 축열식연소장치를 포함하는 휘발성유기화합물 처리 시스템.
The method of claim 1,
Absorption and stripping temperature and pressure of the absorption tower and stripping column can be adjusted according to the absorbing liquid-volatile organic compound pair,
Volatile organic compound treatment system including absorption tower, stripping tower and regenerative combustion device.
◈청구항 5은(는) 설정등록료 납부시 포기되었습니다.◈Claim 5 was abandoned upon payment of a set-up fee. 제 1 항에 있어서,
상기 열원은 탈거탑의 리보일러에 공급되거나 또는 직접적으로 탈거탑을 가열하는,
흡수탑과 탈거탑 및 축열식연소장치를 포함하는 휘발성유기화합물 처리 시스템.
The method of claim 1,
The heat source is supplied to the reboiler of the stripping column or directly heating the stripping column,
Volatile organic compound treatment system including absorption tower, stripping tower and regenerative combustion device.
삭제delete
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