KR100851493B1 - Carbon dioxide absorption method from mixed gas by ammonia liquor - Google Patents

Carbon dioxide absorption method from mixed gas by ammonia liquor Download PDF

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KR100851493B1
KR100851493B1 KR1020070054533A KR20070054533A KR100851493B1 KR 100851493 B1 KR100851493 B1 KR 100851493B1 KR 1020070054533 A KR1020070054533 A KR 1020070054533A KR 20070054533 A KR20070054533 A KR 20070054533A KR 100851493 B1 KR100851493 B1 KR 100851493B1
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South Korea
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ammonia water
absorption tower
carbon dioxide
absorption
cooled
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KR1020070054533A
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Korean (ko)
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김제영
이영봉
강기준
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주식회사 포스코
재단법인 포항산업과학연구원
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Priority to KR1020070054533A priority Critical patent/KR100851493B1/en
Priority to US12/131,452 priority patent/US7981196B2/en
Priority to CN2008101099019A priority patent/CN101318651B/en
Priority to JP2008147193A priority patent/JP2008296216A/en
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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
    • B01D53/14—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
    • 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
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Abstract

A method for absorbing carbon dioxide by using ammonia water is provided to increase carbon dioxide absorption efficiency of the absorption liquid by extracting a portion of an absorption liquid with a high temperature from an inner part of an absorption tower to an outer part of the absorption tower, cooling the absorption liquid, and supplying the cooled absorption liquid into the absorption tower, thereby lowering temperature of the absorption liquid. As a method for contacting carbon dioxide contained in flue gas with ammonia water in an absorption tower(10) to absorb and remove carbon dioxide, a method for absorbing carbon dioxide by using ammonia water comprises the steps of: recovering ammonia water with a high temperature at a preset position of the absorption tower; cooling the recovered ammonia water with a high temperature to a preset temperature; and supplying the cooled ammonia water into the absorption tower again. The ammonia water has a concentration of 1 to 4 wt.%. The ammonia water with a high temperature is recovered in the amount corresponding to 1/6 to 1/3 of an amount of the ammonia water supplied into the absorption tower. The recovered ammonia water with a high temperature is cooled to a temperature of 20 to 30 deg.C before the cooled ammonia water is supplied into the absorption tower again. The cooled ammonia water is supplied again into a position of the absorption tower that is the same as or higher than that of the absorption tower from which the ammonia water with a high temperature is recovered.

Description

암모니아수를 이용한 이산화탄소 흡수 방법{Carbon dioxide absorption method from mixed gas by ammonia liquor}Carbon dioxide absorption method from mixed gas by ammonia liquor}

도 1은 종래의 방법으로 암모니아수를 이용하여 이산화탄소를 흡수하는 공정을 설명하기 위한 종래 흡수탑의 구성을 나타낸 개략 구성도;1 is a schematic block diagram showing the configuration of a conventional absorption tower for explaining a process of absorbing carbon dioxide using ammonia water in a conventional method;

도 2는 종래의 방법으로 암모니아수를 이용하여 이산화탄소를 흡수하는 공정의 문제점을 설명하기 위한 도면으로서 도 1의 흡수탑 내부 온도의 분포를 나타낸 그래프도;2 is a graph illustrating a distribution of internal temperature of the absorption tower of FIG. 1 as a view for explaining a problem of a process of absorbing carbon dioxide using ammonia water in a conventional method;

도 3은 본 발명의 방법으로 암모니아수를 이용하여 이산화탄소를 흡수하는 공정을 설명하기 위한 새로운 흡수탑의 구성을 나타낸 개략 구성도;Figure 3 is a schematic block diagram showing the configuration of a new absorption tower for explaining the process of absorbing carbon dioxide using ammonia water in the method of the present invention;

도 4 내지 도 6은 본 발명의 방법으로 암모니아수를 이용하여 이산화탄소를 흡수할 때 흡수탑 내부 온도를 측정하여 나타낸 그래프도이다.4 to 6 is a graph showing the measurement of the temperature inside the absorption tower when absorbing carbon dioxide by using ammonia water in the method of the present invention.

※도면의 주요부분에 대한 부호의 설명※※ Explanation of symbols about main part of drawing ※

10 : 흡수탑10: absorption tower

11 : 트레이11: tray

12 : 흡수액 공급라인12: absorbent liquid supply line

14 : 흡수액 배출라인14: absorbent liquid discharge line

16 : 배가스 공급라인16: exhaust gas supply line

18 : 배가스 배출라인18: exhaust gas discharge line

20 : 고온흡수액 배출라인20: high temperature absorption liquid discharge line

22 : 저온흡수액 공급라인22: low temperature absorption liquid supply line

30 : 냉각기30: cooler

본 발명은 암모니아수를 이용한 이산화탄소 흡수 방법에 관한 것으로서, 보다 상세하게는 흡수탑의 내부에서 고온의 흡수액 일부를 외부로 빼내어 냉각시킨 후 다시 흡수탑의 내부로 공급함으로써 흡수액의 온도를 낮춤에 의해 흡수액의 이산화탄소 흡수효율을 높일 수 있는, 암모니아수를 이용한 이산화탄소 흡수 방법에 관한 것이다.The present invention relates to a method for absorbing carbon dioxide using ammonia water, and more particularly, by removing a portion of the hot absorbent liquid from the inside of the absorption tower to the outside, cooling it, and then supplying it to the inside of the absorption tower to lower the temperature of the absorbent liquid. It relates to a carbon dioxide absorption method using ammonia water, which can increase the carbon dioxide absorption efficiency.

배가스에 포함된 이산화탄소를 분리 제거하기 위해 사용하는 방법으로 흡착법, 흡수법, 막분리법 등이 알려져 있다.As a method for separating and removing carbon dioxide contained in exhaust gas, adsorption, absorption, and membrane separation are known.

본 발명에 관련된 흡수법에서는 이산화탄소 흡수액을 사용하며, 대표적으로 아민계 화합물로 이루어진 흡수액이 널리 이용되고 있다. 그러나 아민계 화합물은 가격이 비싸고 또한 기계 장치를 부식시킨다는 단점이 있다.In the absorption method which concerns on this invention, a carbon dioxide absorption liquid is used and the absorption liquid which consists of an amine compound typically is widely used. However, amine compounds have the disadvantage of being expensive and corrosive to machinery.

이러한 아민계 화합물과 함께 암모니아수도 이산화탄소 흡수액으로 오래전부터 사용되고 있다.Ammonia water, along with such amine compounds, has been used for a long time as a carbon dioxide absorption liquid.

최근, 암모니아수가 이산화탄소 흡수액으로 주목을 받고 있는데, 암모니아수 는 가격이 싸고 아민계 화합물에 비하여 기계 장치의 부식 문제를 덜 일으키기 때문이다.Recently, ammonia water has attracted attention as a carbon dioxide absorbent, because ammonia water is cheaper and causes less corrosion problems of mechanical devices than amine compounds.

Bai와 Yeh는 암모니아수를 이용하여 이산화탄소를 흡수 제거하는 것에 대한 연구논문을 발표하였으며(Ind.Eng.Chem. Res. 1997, 36권 2490쪽), 또한 Resnik 등도 Aqua ammonia process라는 암모니아의 이산화탄소흡수공정을 발표하였다(Int. J. of Env.Technology & Management, 4권,1호).Bai and Yeh published a research paper on the absorption and removal of carbon dioxide using ammonia water (Ind. Eng. Chem. Res. 1997, vol. 36, pp. 2490), and Resnik et al. (Int. J. of Env. Technology & Management, Vol. 4, No. 1).

또한 한국특허 10-0703999에서도 5-15wt%의 암모니아수를 이용하여 이산화탄소를 흡수하는 공정을 제시하고 있으며 이 공정은 기존에 발표된 논문(Int. J.of Thermodynamics, vol.7, pp.173-181)에서 제시한 공정과 유사하다.In addition, Korean Patent No. 10-0703999 also proposes a process for absorbing carbon dioxide using 5-15 wt% ammonia water, which was previously published in the paper (Int. J. of Thermodynamics, vol.7, pp.173-181). Similar to the process presented in

이들 공정들은 암모니아가 이산화탄소를 흡수한다는 사실을 이용하여 암모니아의 이산화탄소 흡수량 및 반응속도에 관한 기초연구 등을 주로 제시한 것으로 실험실적으로 실행 가능한 것이며 암모니아 농도가 5%~21%까지 매우 높은 암모니아수를 사용하고 있다는 공통점을 갖는다.These processes are mainly based on the fact that ammonia absorbs carbon dioxide, and mainly provide basic research on ammonia absorption and reaction rate of ammonia, and are feasible experimentally and use ammonia water with very high ammonia concentration of 5% ~ 21%. They have something in common.

그러나 암모니아의 농도가 높은 암모니아수를 실 공정에 적용하는 경우 휘발성이 큰 암모니아의 특성 등으로 인한 문제점이 발생할 염려가 있다. 즉, 암모니아는 휘발성이 강하여 단지 대기중에 방치만 하는 경우에도 쉽게 휘발해 버리기 때문에, 농도가 높은 암모니아수를 이용하는 경우, 상당량의 암모니아가 흡수탑 내부에서 흡수제로서의 역할을 하기 전에 흡수탑 상부에서 기체와 접촉하여 휘발해 버리는 문제점이 있다. 또한 암모니아수와 배가스의 이산화탄소가 접촉하여 이산화탄소의 흡수가 이루어질 때 반응열에 의한 온도 상승이 예상되며, 이러한 온도 상승시 휘발 현상이 더욱 뚜렷이 나타나게 되어 높은 농도의 암모니아수를 이용하여 얻고자 하는 효과는 상실된다.However, when ammonia water having a high concentration of ammonia is applied to a real process, there is a concern that a problem occurs due to the characteristics of ammonia, which is highly volatile. In other words, ammonia is highly volatile and easily volatilizes even when it is left in the air. Therefore, when ammonia water with high concentration is used, a considerable amount of ammonia is contacted with gas at the top of the absorption tower before acting as an absorbent in the absorption tower. There is a problem that will volatilize. In addition, when ammonia water and carbon dioxide in the exhaust gas is in contact with the absorption of carbon dioxide is expected to increase the temperature by the reaction heat, the volatilization phenomenon is more pronounced when the temperature rises, the effect of using a high concentration of ammonia water is lost.

암모니아수를 이용한 이산화탄소 흡수 공정을 도 1을 참조하여 구체적으로 살펴본다. 도 1은 종래의 방법으로 암모니아수를 이용하여 이산화탄소를 흡수하는 공정을 설명하기 위한 종래 흡수탑의 구성을 나타낸 개략 구성도이다.The carbon dioxide absorption process using ammonia water will be described in detail with reference to FIG. 1. Figure 1 is a schematic block diagram showing the configuration of a conventional absorption tower for explaining a process for absorbing carbon dioxide using ammonia water in a conventional method.

이산화탄소를 흡수하기 위한 흡수액(암모니아수)은 흡수탑(1)의 상부로 공급되어 흡수탑(1)의 하부 쪽으로 이동하며 이산화탄소가 포함된 배가스는 흡수탑(1)의 하부로 공급되어 흡수탑(1)의 상부 쪽으로 이동한다.Absorption liquid (ammonia water) for absorbing carbon dioxide is supplied to the upper portion of the absorption tower (1) to move toward the lower portion of the absorption tower (1) and exhaust gas containing carbon dioxide is supplied to the lower portion of the absorption tower (1) To the top of the

따라서 흡수탑(1)의 내부에서 흡수액과 배가스가 접촉하고 화학반응에 의해 배가스의 이산화탄소가 흡수액에 용해됨으로써 이산화탄소가 제거된 배가스는 흡수탑(1)의 상부로 배출되고 이산화탄소를 흡수한 흡수액은 흡수탑(1)의 하부로 배출된다. 물론 흡수탑(1)의 하부로 배출되는 흡수액에는 이산화탄소를 흡수한 암모니아수 및 암모니아와 결합한 염의 형태가 일부 포함될 것이다.Therefore, the absorbent liquid and the exhaust gas contact inside the absorption tower 1 and the carbon dioxide of the exhaust gas is dissolved in the absorption liquid by a chemical reaction, so that the exhaust gas from which carbon dioxide is removed is discharged to the upper portion of the absorption tower 1, and the absorption liquid absorbing carbon dioxide is absorbed. It is discharged to the bottom of the tower (1). Of course, the absorbent liquid discharged to the lower portion of the absorption tower 1 will include some form of ammonia water and ammonia combined with the absorption of carbon dioxide.

그러나, 전술한 것처럼, 상당량의 흡수액이 이산화탄소를 흡수하지 않고 흡수탑의 하부로 배출됨으로써 흡수액의 이산화탄소 흡수효율이 매우 낮은 문제점이 있으며, 이는 암모니아수의 암모니아 농도가 높고, 또한 도 2에 도시된 것처럼, 흡수탑 내부의 온도가 고온으로 형성되는 것에 기인한다. 도 2는 종래의 방법으로 암모니아수를 이용하여 이산화탄소를 흡수하는 공정의 문제점을 설명하기 위한 도면으로서 도 1의 흡수탑 내부 온도의 분포를 나타낸 그래프도이다.However, as described above, there is a problem that a significant amount of the absorption liquid is discharged to the lower portion of the absorption tower without absorbing carbon dioxide, so the carbon dioxide absorption efficiency of the absorption liquid is very low, which is high in the ammonia concentration of the ammonia water, as shown in FIG. The temperature inside the absorption tower is due to the high temperature formed. 2 is a graph illustrating a distribution of internal temperature of the absorption tower of FIG. 1 as a view for explaining a problem of a process of absorbing carbon dioxide using ammonia water in a conventional method.

한편, 상기한 문제점을 해결하기 위하여 낮은 농도의 암모니아수를 이용하는 것이 바람직하나 여전히 흡수탑 내부의 온도가 고온으로 형성되어 흡수액의 이산화탄소 흡수효율이 낮은 문제점이 있다.On the other hand, in order to solve the above problems, it is preferable to use a low concentration of ammonia water, but there is still a problem that the temperature inside the absorption tower is formed at a high temperature, the carbon dioxide absorption efficiency of the absorbent liquid is low.

본 발명자 등은 오랜 연구와 시험을 수행한 결과 흡수탑의 내부에서 고온의 흡수액 일부를 외부로 빼내어 냉각시킨 후 다시 흡수탑의 내부로 공급함으로써 흡수액의 온도를 낮춤에 의해 흡수액의 이산화탄소 흡수효율을 높일 수 있음을 알았다.The present inventors have conducted a long research and test to improve the carbon dioxide absorption efficiency of the absorbent liquid by lowering the temperature of the absorbent liquid by lowering the temperature of the absorbent liquid by removing a portion of the high temperature absorbent liquid from the inside of the absorption tower to the outside and cooling it. I knew I could.

따라서, 본 발명은 상기한 종래의 문제점을 해결하기 위한 것으로, 흡수탑으로 공급되어 흡수탑의 하부 쪽으로 이동하는 흡수액의 일부를 냉각시킴으로써 이산화탄소 흡수효율을 향상시킨, 암모니아수를 이용한 이산화탄소 흡수 방법을 제공하는 것을 그 목적으로 한다.Accordingly, the present invention is to solve the above-mentioned problems, to provide a carbon dioxide absorption method using ammonia water, which improves the carbon dioxide absorption efficiency by cooling a portion of the absorption liquid supplied to the absorption tower to move toward the bottom of the absorption tower. For that purpose.

상기한 목적을 달성하기 위한 기술적인 구성으로서, 본 발명은, 배가스중에 포함된 이산화탄소를 흡수탑의 내부에서 암모니아수와 접촉시킴에 의해 흡수 제거하는 방법으로서, 상기 흡수탑의 미리 설정된 위치에서 고온의 암모니아수를 회수하는 단계와, 상기 단계에서 회수된 고온의 암모니아수를 미리 설정된 온도로 냉각하는 단계와, 상기 단계에서 냉각된 암모니아수를 상기 흡수탑의 내부로 재공급하는 단계를 포함하여 구성된, 암모니아수를 이용한 이산화탄소 흡수 방법을 마련함에 의한다.As a technical configuration for achieving the above object, the present invention is a method for absorbing and removing carbon dioxide contained in the exhaust gas by contacting with ammonia water in the absorption tower, the hot ammonia water at a predetermined position of the absorption tower Recovering the carbon dioxide, cooling the hot ammonia water recovered in the step to a predetermined temperature, and supplying the ammonia water cooled in the step to the inside of the absorption tower. By providing an absorption method.

이하, 본 발명의 바람직한 실시예를 첨부된 도면을 참조하여 설명한다.Hereinafter, exemplary embodiments of the present invention will be described with reference to the accompanying drawings.

도 3은 본 발명의 방법으로 암모니아수를 이용하여 이산화탄소를 흡수하는 공정을 설명하기 위한 새로운 흡수탑의 구성을 나타낸 개략 구성도이다.Figure 3 is a schematic diagram showing the configuration of a new absorption tower for explaining the process of absorbing carbon dioxide by using ammonia water in the method of the present invention.

흡수탑(10)의 내부에는 여러 개의 트레이(11)가 일정 간격을 두고 다단으로 설치될 수 있으며, 이러한 트레이(11) 대신 충진물을 충진하는 구성을 채택하여도 좋다.Inside the absorption tower 10, a plurality of trays 11 may be installed in multiple stages at regular intervals, and instead of the trays 11, a configuration for filling the filling material may be adopted.

상기 트레이(11)는 체(Sieve) 혹은 스크린(Screen) 등 통상적으로 알려진 구조의 것으로 사용되면 충분하며, 또한 충진물의 경우도 통상적으로 알려진 것으로 사용하면 충분하다.The tray 11 is sufficient to be used in a commonly known structure such as a sieve or screen, and it is sufficient to use a commonly known one for the filling material.

상기 흡수탑(10)의 상부 일측에 흡수액인 암모니아수를 공급하기 위한 흡수액 공급라인(12)이 연결 설치되며 이 흡수액 공급라인(12)을 통해 흡수탑(10)의 내부로 공급된 흡수액, 즉 암모니아수는 상기 트레이(11)들을 통과하면서 흡수탑(10)의 하부 쪽으로 이동된다.An absorbent liquid supply line 12 for supplying ammonia water, which is an absorbent liquid, is connected to an upper one side of the absorber 10, and the absorbent liquid supplied to the inside of the absorber 10 through the absorbent liquid supply line 12, that is, ammonia water. Moves toward the bottom of the absorption tower 10 while passing through the trays 11.

이들 트레이(11)를 모두 통과한 암모니아수는 상기 흡수탑(10)의 하단에 설치된 흡수액 배출라인(14)을 통해 흡수탑(10)의 외부로 배출된다.The ammonia water passing through all of these trays 11 is discharged to the outside of the absorption tower 10 through the absorption liquid discharge line 14 installed at the lower end of the absorption tower 10.

그리고, 상기 흡수탑(10)의 하부 일측에 이산화탄소가 포함된 배가스를 공급하기 위한 배가스 공급라인(16)이 연결 설치되며 이 배가스 공급라인(16)을 통해 흡수탑(10)의 내부로 공급된 배가스는 상기 흡수액에 접촉하면서 그 흡수액과 반대 방향, 즉 흡수탑(10)의 상부로 쪽으로 이동된다.In addition, an exhaust gas supply line 16 for supplying exhaust gas containing carbon dioxide is connected to one lower side of the absorption tower 10 and is supplied into the absorption tower 10 through the exhaust gas supply line 16. The exhaust gas is moved in the direction opposite to the absorbent liquid, i.e., toward the top of the absorption tower 10 while contacting the absorbent liquid.

또한 상기 흡수탑(10)의 상단에는 이산화탄소가 제거된 배가스를 흡수탑(10)의 외부로 배출시키기 위한 배가스 배출라인(18)이 설치된다.In addition, an exhaust gas discharge line 18 for discharging the exhaust gas from which carbon dioxide is removed to the outside of the absorption tower 10 is installed at the upper end of the absorption tower 10.

상기 흡수탑(10)의 선택된 위치, 바람직하게는 흡수탑(10) 내에서 가장 온도가 높은 위치에서 고온의 흡수액을 외부로 빼낼 수 있도록 고온흡수액 배출라인(20)을 연결 설치하고 그 고온흡수액 배출라인(20)을 통해 외부로 빼내어진 흡수액은 냉각기(30)에서 냉각된다.The hot absorbent liquid discharge line 20 is connected and installed to discharge the hot absorbent liquid to the outside at a selected position of the absorption tower 10, preferably at the highest temperature in the absorber 10. The absorbent liquid drawn out through the line 20 is cooled in the cooler 30.

그리고, 상기 냉각기(30)에서 냉각된 흡수액은 상기 흡수탑(10)의 선택된 위치, 바람직하게는 상기 고온흡수액 배출라인(20)이 설치된 부위보다 더 높은 위치에 설치된 저온흡수액 공급라인(22)을 통해 상기 흡수탑(10)의 내부로 재공급된다.In addition, the absorbent liquid cooled by the cooler 30 is a cold absorbent liquid supply line 22 installed at a position higher than a selected position of the absorption tower 10, preferably, a portion where the hot absorbent liquid discharge line 20 is installed. Through the absorption tower 10 is supplied back.

이렇게 고온의 흡수액 일부를 흡수탑의 외부로 배출시켜 적정 온도로 냉각시킨 후 다시 흡수탑의 일정 위치에 공급하면 흡수탑 내의 온도가 낮추어지며, 이에 의하여 이산화탄소 흡수효율이 향상된다.When a part of the hot absorbent liquid is discharged to the outside of the absorption tower and cooled to an appropriate temperature and then supplied to a predetermined position of the absorption tower, the temperature in the absorption tower is lowered, thereby improving carbon dioxide absorption efficiency.

이하, 실시예를 통하여 본 발명을 설명한다.Hereinafter, the present invention will be described through examples.

먼저, 도 1에 도시된 흡수탑을 이용한 종래의 방법으로 이산화탄소 흡수시험을 행하여 이를 비교예로 하였다.First, a carbon dioxide absorption test was conducted by a conventional method using the absorption tower shown in FIG. 1, which was used as a comparative example.

[비교예][Comparative Example]

비교예를 수행하기 위한 흡수탑의 크기는 직경 50mm, 높이 1500mm로 하였고, 흡수탑의 내부 충진재는 6mm raschig ring을 이용하였다. 그리고 흡수탑은 150mm 를 한 개의 단으로 구분하여 총 10개 단으로 구성하였다.The size of the absorption tower for carrying out the comparative example was 50mm in diameter, 1500mm in height, and the internal filler of the absorption tower was used for 6mm raschig ring. The absorption tower was divided into one stage and 150 mm in total.

시험조건으로 이산화탄소 25 체적%, 질소 75 체적%의 모델가스를 이용하였고 흡수탑으로 공급되는 모델가스의 유량은 30000cc/min로 하였다.As the test conditions, model gas of 25 vol% carbon dioxide and 75 vol% nitrogen was used, and the flow rate of the model gas supplied to the absorption tower was 30000 cc / min.

또한 흡수액은 4 중량%의 농도를 가지는 암모니아수를 이용하였으며 흡수액 의 공급유량은 300cc/min로 하였다.As the absorbent liquid, ammonia water having a concentration of 4% by weight was used, and the supply flow rate of the absorbent liquid was 300 cc / min.

이와 같은 조건으로 시험을 하였을 때 이산화탄소 흡수제거효율은 70%였으며 흡수탑내의 온도분포는 도 2와 같았다.When tested under these conditions, carbon dioxide absorption removal efficiency was 70% and the temperature distribution in the absorption tower was as shown in FIG.

다음, 도 2에 도시된 흡수탑을 이용한 본 발명의 방법으로 이산화탄소 흡수시험을 행하여 이를 실시예 1 내지 실시예 3으로 하였다.Next, a carbon dioxide absorption test was performed by the method of the present invention using the absorption tower shown in FIG. 2 to be Examples 1 to 3.

[실시예 1]Example 1

비교예와 동일한 구조 및 크기를 갖는 흡수탑과 동일한 조성의 모델가스를 이용하였고, 흡수탑에서 가장 온도가 높은 부위인 상부에서 4번째 단에서 흡수액을 회수하여 30℃로 냉각한 후 다시 상부에서 4번째 단으로 재공급하였다. 이때 흡수액 회수량은 초기 흡수탑 상부 공급량의 1/6로 하였다.The model gas of the same composition as that of the absorption tower having the same structure and size as the comparative example was used. To the second stage. At this time, the absorption liquid recovery amount was set to 1/6 of the initial absorption tower upper supply amount.

실시예 1의 결과, 흡수탑 내부 온도 측정 결과는 도 4와 같았으며 이산화탄소 흡수제거효율은 88%였다.As a result of Example 1, the results of measuring the temperature inside the absorption tower were as shown in FIG. 4 and the carbon dioxide absorption removal efficiency was 88%.

[실시예 2]Example 2

비교예와 동일한 구조 및 크기를 갖는 흡수탑과 동일한 조성의 모델가스를 이용하였고, 흡수탑에서 가장 온도가 높은 부위인 상부에서 4번째 단에서 흡수액을 회수하여 20℃로 냉각한 후 다시 상부에서 4번째 단으로 재공급하였다. 이때 흡수액 회수량은 초기 흡수탑 상부 공급량의 1/3로 하였다.The model gas of the same composition as that of the absorption tower having the same structure and size as the comparative example was used, and the absorption liquid was recovered at the fourth stage from the upper portion of the upper portion of the absorption tower, cooled to 20 ° C., and then again restored to 4 To the second stage. At this time, the absorbed liquid recovery amount was 1/3 of the initial absorption tower upper supply amount.

실시예 2의 결과, 흡수탑 내부 온도 측정 결과는 도 5와 같았으며 이산화탄소 흡수제거효율은 91%였다.As a result of Example 2, the results of measuring the temperature inside the absorption tower were as shown in FIG. 5 and the carbon dioxide absorption removal efficiency was 91%.

[실시예 3]Example 3

비교예와 동일한 구조 및 크기를 갖는 흡수탑과 동일한 조성의 모델가스를 이용하였고, 흡수탑에서 가장 온도가 높은 부위인 상부에서 4번째 단에서 흡수액을 회수하여 25℃로 냉각한 후 다시 상부에서 3번째 단으로 재공급하였다. 이때 흡수액 회수량은 초기 흡수탑 상부 공급량의 1/3로 하였다.The model gas of the same composition as the absorption tower having the same structure and size as that of the comparative example was used. To the second stage. At this time, the absorbed liquid recovery amount was 1/3 of the initial absorption tower upper supply amount.

실시예 3의 결과, 흡수탑 내부 온도 측정 결과는 도 6과 같았으며 이산화탄소 흡수제거효율은 91%였다.As a result of Example 3, the absorption tower internal temperature measurement results were the same as in FIG. 6, and the carbon dioxide absorption removal efficiency was 91%.

상기한 실시예 1 내지 3에서 알 수 있듯이 고온의 흡수액 일부를 회수하여 냉각시킨 후 다시 흡수탑의 내부로 공급함으로써 이산화탄소 흡수제거효율이 비교예에 비하여 현저하게 향상되었다.As can be seen in Examples 1 to 3 above, by recovering and cooling a part of the high temperature absorbent liquid and then supplying it to the inside of the absorption tower, the carbon dioxide absorption removal efficiency was remarkably improved as compared with the comparative example.

본 발명에서 냉각을 위해 회수하는 흡수액의 양은 초기 흡수탑 상부 공급량의 1/6 내지 1/3이 바람직하며, 1/6보다 적은 양을 회수하면 흡수탑 내부 온도를 적절한 정도로 낮추는 것이 곤란하여 바람직하지 않으며 1/3보다 많은 양을 회수하면 회수된 흡수액을 냉각하기 위한 냉각기의 크기가 과도하게 커지는 문제점이 있어 바람직하지 않다.In the present invention, the amount of the absorbent liquid to be recovered for cooling is preferably 1/6 to 1/3 of the initial supply of the absorption tower, and when recovering less than 1/6, it is difficult to lower the temperature inside the absorption tower to an appropriate level. In addition, if the recovery amount is larger than 1/3, the size of the cooler for cooling the recovered absorbing liquid is excessively large, which is not preferable.

또한, 흡수액은 4 중량% 이하의 농도를 갖는 암모니아수가 바람직하며, 더 바람직하게는 1 중량% 내지 4 중량%의 농도를 갖는 암모니아수가 좋다. 여기에서, 암모니아수의 농도가 1 중량% 미만인 경우 충분한 양의 이산화탄소를 흡수하지 못하여 바람직하지 않으며 4 중량% 이상인 경우 휘발해 버리는 암모니아의 양이 증가하여 바람직하지 않다.Further, the absorbent liquid is preferably ammonia water having a concentration of 4% by weight or less, more preferably ammonia water having a concentration of 1% by weight to 4% by weight. Here, when the concentration of ammonia water is less than 1% by weight, it is not preferable because it does not absorb a sufficient amount of carbon dioxide, and when it is 4% by weight or more, the amount of ammonia which volatilizes is not preferable.

또한, 흡수액은 흡수탑 내부에서 가장 온도가 높게 형성된 부위에서 회수하 는 것이 바람직하다.In addition, the absorbent liquid is preferably recovered at the site where the temperature is formed highest inside the absorption tower.

또한, 흡수탑에서 회수된 흡수액은 20~30℃로 냉각되는 것이 바람직하며, 너무 낮은 온도로 냉각하면 냉각기(30)의 용량을 크게 할 필요가 있어 바람직하지 않으며 너무 높은 온도로 냉각하면 냉각된 흡수액이 흡수탑 내부로 재공급되었을 때 흡수탑 내부 온도가 원하는 정도로 떨어지지 않기 때문에 이산화탄소 흡수제거효율을 향상시키는데 큰 도움이 되지 않는다.In addition, the absorbent liquid recovered from the absorption tower is preferably cooled to 20 ~ 30 ℃, if the cooling to a too low temperature it is necessary to increase the capacity of the cooler 30 is not preferable, if the cooling to a too high temperature cooled absorbent liquid When resupplied into the absorption tower, the temperature inside the absorption tower does not drop to the desired degree, which does not help to improve the carbon dioxide absorption removal efficiency.

상술한 바와 같이 본 발명에 따른 암모니아수를 이용한 이산화탄소 흡수 방법에 의하면, 흡수탑의 내부에서 고온의 흡수액 일부를 외부로 빼내어 냉각시킨 후 다시 흡수탑의 내부로 공급함으로써 흡수액의 온도를 낮춤에 의해 흡수액의 이산화탄소 흡수효율을 높일 수 있는 우수한 효과를 갖는다.As described above, according to the carbon dioxide absorption method using the ammonia water according to the present invention, by removing a portion of the high temperature absorbent liquid from the inside of the absorption tower to the outside, cooling it and supplying it to the inside of the absorption tower to lower the temperature of the absorbent liquid. It has an excellent effect to increase the carbon dioxide absorption efficiency.

Claims (5)

배가스중에 포함된 이산화탄소를 흡수탑의 내부에서 암모니아수와 접촉시킴에 의해 흡수 제거하는 방법으로서,As a method of absorbing and removing carbon dioxide contained in the exhaust gas by contacting ammonia water in the absorption tower, 상기 흡수탑의 미리 설정된 위치에서 고온의 암모니아수를 회수하는 단계와,Recovering hot ammonia water at a predetermined position of the absorption tower; 상기 단계에서 회수된 고온의 암모니아수를 미리 설정된 온도로 냉각하는 단계와,Cooling the hot ammonia water recovered in the step to a predetermined temperature; 상기 단계에서 냉각된 암모니아수를 상기 흡수탑의 내부로 재공급하는 단계를 포함하여 구성된, 암모니아수를 이용한 이산화탄소 흡수 방법.Recharging the ammonia water cooled in the step into the inside of the absorption tower, comprising a carbon dioxide absorption method using ammonia water. 청구항 1에 있어서,The method according to claim 1, 상기 암모니아수는 1 중량% 내지 4 중량%의 농도를 가짐을 특징으로 하는 암모니아수를 이용한 이산화탄소 흡수 방법.The ammonia water has a concentration of 1% by weight to 4% by weight of carbon dioxide absorption method using ammonia water. 청구항 1에 있어서,The method according to claim 1, 상기 고온의 암모니아수는 상기 흡수탑에 공급되는 양의 1/6 내지 1/3이 회수됨을 특징으로 하는 암모니아수를 이용한 이산화탄소 흡수 방법.The high temperature ammonia water is carbon dioxide absorption method using ammonia water, characterized in that 1/6 to 1/3 of the amount supplied to the absorption tower is recovered. 청구항 1에 있어서,The method according to claim 1, 상기 회수된 고온의 암모니아수는 20℃ 내지 30℃로 냉각되어 재공급됨을 특 징으로 하는 암모니아수를 이용한 이산화탄소 흡수 방법.The recovered high temperature ammonia water is cooled to 20 ℃ to 30 ℃ carbon dioxide absorption method using ammonia water, characterized in that the re-supplied. 청구항 1에 있어서,The method according to claim 1, 상기 냉각된 암모니아수는 고온의 암모니아수를 회수하는 위치와 동일하거나 더 높은 위치로 재공급됨을 특징으로 하는 암모니아수를 이용한 이산화탄소 흡수 방법.The cooled ammonia water is carbon dioxide absorption method using ammonia water, characterized in that the re-supply to the same or higher position to recover the hot ammonia water.
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US12/131,452 US7981196B2 (en) 2007-06-04 2008-06-02 Apparatus and method for recovering carbon dioxide from flue gas using ammonia water
CN2008101099019A CN101318651B (en) 2007-06-04 2008-06-04 Apparatus and method for recovering carbon dioxide from flue gas using ammonia water
JP2008147193A JP2008296216A (en) 2007-06-04 2008-06-04 Carbon dioxide-recovering device using aqueous ammonia, and method therefor

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