KR20170123726A - Method for purification of biogas using adsorption-membrane combined process - Google Patents

Method for purification of biogas using adsorption-membrane combined process Download PDF

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KR20170123726A
KR20170123726A KR1020160042577A KR20160042577A KR20170123726A KR 20170123726 A KR20170123726 A KR 20170123726A KR 1020160042577 A KR1020160042577 A KR 1020160042577A KR 20160042577 A KR20160042577 A KR 20160042577A KR 20170123726 A KR20170123726 A KR 20170123726A
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biogas
separation membrane
adsorption
poly
carbon dioxide
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하성용
고형철
이충섭
임진혁
공동욱
김학은
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주식회사 한국가스기술공사
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Abstract

The present invention relates to a method for purifying biogas using an adsorption-membrane combined process, comprising the following steps: supplying biogas to a gas compressor; adsorbing carbon dioxide from the compressed biogas through an adsorption device; and separating and purifying desorption gas in the adsorption step through a separation membrane module, recycling purified methane with the biogas and separating and discharging carbon dioxide. The method contributes to upgrading biogas by improving the recovery rate of methane to over 95%.

Description

흡착-분리막 복합공정을 이용한 바이오가스 정제방법{Method for purification of biogas using adsorption-membrane combined process}BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method for purifying biogas using an adsorption-

본 발명은 흡착-분리막 복합공정을 이용한 바이오가스 정제방법에 관한 것으로, 보다 상세하게는 흡착공정에 의한 탈착가스를 분리막으로 정제하여 메탄은 재순환시키고 이산화탄소는 분리 배출하여 메탄의 회수율을 크게 향상시킬 수 있는 흡착-분리막 복합공정을 이용한 바이오가스 정제방법에 관한 것이다.
The present invention relates to a biogas purification method using an adsorption-separation membrane composite process, more specifically, purification of a desorption gas by an adsorption process by separating membrane, recycling methane, and separating and discharging carbon dioxide, The present invention relates to a biogas purification method using an adsorption-separation membrane composite process.

바이오가스는 슬러지류 및 음식물쓰레기, 가축분뇨 등의 유기성 폐기물이 혐기소화에 의해 분해하면서 생성되는 메탄과 이산화탄소 등을 포함하는 기체 상태의 연료를 일컫고, 이러한 바이오가스 중에서 이산화탄소 및 일부 다른 가스가 제거된 메탄가스를 바이오메탄이라고 하는데, 최근에는 천연가스와 같이 청정연료로 사용될 수 있어 에너지원으로 각광받고 있다.
Biogas refers to gaseous fuels including methane and carbon dioxide produced by decomposition of organic wastes such as sludge, food waste and livestock manure by anaerobic digestion. Among these biogas, carbon dioxide and some other gases are removed Methane gas is called biomethane, and recently it can be used as a clean fuel like natural gas, and is attracting attention as an energy source.

그런데 유기성 폐기물의 혐기소화를 통해 생산된 바이오가스는 계절과 유기성 폐기물의 투입량에 따라 그 조성 및 가스발생량이 변화된다. 또한, 바이오가스에 함유된 메탄 조성은 약 50~70% 수준으로 열량(5,000kcal/m3 이하)이 작아 운송용 연료나 도시가스로는 사용이 어려우며 천연가스와 비슷한 열량을 맞추기 위해서는 바이오가스 중의 메탄 함량을 95%이상으로 향상시켜야 하는 과제를 안고 있다. 따라서 바이오가스 중의 대부분을 차지하고 있는 이산화탄소/메탄 혼합기체를 분리하는 공정이 적용되어 고질화를 통해 원거리 공급이 가능해야 비로소 발전, 보일러, 공장 및 자동차 연료 또는 도시가스 등으로 사용이 가능하게 되는 것이다.
However, biogas produced through anaerobic digestion of organic wastes changes its composition and gas generation amount depending on the amount of seasonal and organic waste input. In addition, the methane composition contained in the biogas is heat to about 50 to 70% (5,000kcal / m 3 or less) methane content of the small transportation fuel or town gas is difficult and the use of biogas To meet the same amount of heat and gas To 95% or more. Therefore, the process of separating carbon dioxide / methane mixed gas, which accounts for most of the biogas, is applied and it can be used for power generation, boiler, factory, automobile fuel, city gas or the like.

현재까지 알려진 바이오가스의 고질화를 위한 이산화탄소/메탄 정제방법으로서는 흡착공정(adsorption process), 흡수공정(scrubbing process) 및 막분리공정(membrane separation process) 등이 있으며, 메탄회수율이 공정을 적용하는데 중요한 판단요소가 된다. 이 중에서 흡착공정만으로는 일정하게 설계된 바이오가스의 유량과 농도에서는 메탄회수율이 90% 이상일 수 있으나, 바이오가스의 유량과 농도가 변화되면 메탄회수율이 현저하게 감소하는 문제점이 있다(특허문헌 1).
The carbon dioxide / methane purification method for the solidification of the biogas known so far includes the adsorption process, the scrubbing process and the membrane separation process, and the methane recovery rate is important for the application of the process It becomes a judgment factor. Among them, the recovery rate of methane may be more than 90% at the flow rate and concentration of the biogas designed by the adsorption process alone. However, when the flow rate and concentration of the biogas change, the recovery rate of methane decreases remarkably (Patent Document 1).

한편, 막분리공정은 분리막을 사용하여 특정 성분을 선택적으로 투과하여 기체를 분리하는 방법으로서, 에너지 소모가 적고 설치면적이 작아 유지 보수가 용이하다는 장점이 있어 근래에 기체분리 및 정제기술로 주목받고 있다. 이러한 막분리공정을 이용한 바이오가스 중의 이산화탄소 제거에는 주로 중공사 복합막이 사용되고 있으나, 통상의 중공사 복합막은 이산화탄소의 투과도가 대개 100 GPU 미만으로 낮고, 단순한 분리공정을 적용함으로써 바이오가스 정제과정에서 메탄의 회수 손실이 발생하는 단점이 있다(특허문헌 2, 3).
On the other hand, the membrane separation process is a method of selectively separating gases by selectively permeating a specific component using a separation membrane, and is advantageous in that it is easy to maintain due to its low energy consumption and small installation area. have. Although the hollow fiber composite membrane is mainly used for the removal of carbon dioxide in biogas using such a membrane separation process, the hollow fiber composite membrane has a low permeability of carbon dioxide of usually less than 100 GPU and a simple separation process, There is a disadvantage in that recovery loss is generated (Patent Documents 2 and 3).

따라서 본 발명에서는 바이오가스의 고질화를 위하여 흡착공정에 의한 탈착가스를 분리막으로 정제하여 메탄은 재순환시키고, 이산화탄소는 분리 배출하는 흡착-분리막 복합공정을 이용하면, 메탄의 회수율을 95% 이상으로 크게 향상시킬 수 있음에 착안하여 본 발명을 완성하였다.
Therefore, in the present invention, when a desorption gas by adsorption process is purified by a separation membrane to recycle methane, and carbon dioxide is separated and discharged, a methane recovery rate of 95% or more And thus the present invention has been completed.

특허문헌 1. 한국등록특허 제10-1444186호Patent Document 1. Korean Patent No. 10-1444186 특허문헌 2. 미국등록특허 제4,230,463호Patent Document 2. United States Patent No. 4,230,463 특허문헌 3. 한국등록특허 제0644366호Patent Document 3. Korean Patent No. 0644366

본 발명은 상기와 같은 문제점을 감안하여 안출된 것으로, 본 발명의 목적은 바이오가스의 고질화를 위하여 흡착공정에 의한 탈착가스를 분리막으로 정제하여 메탄은 재순환시키고, 이산화탄소는 분리 배출함으로써 메탄의 회수율을 95% 이상으로 크게 향상시킬 수 있는 흡착-분리막 복합공정을 이용한 바이오가스 정제방법을 제공하고자 하는 것이다.
SUMMARY OF THE INVENTION The present invention has been accomplished in view of the above problems, and it is an object of the present invention to provide a method and apparatus for recovering methane by recovering methane by separating desorbed gas by adsorption process to solidify biogas, recycling methane, To 95% or more by using the adsorption-separation membrane composite process.

상기한 바와 같은 목적을 달성하기 위한 본 발명은, I) 바이오가스를 가스 압축기로 공급하는 단계; II) 상기 압축된 바이오가스로부터 흡착장치를 통하여 이산화탄소를 흡착하는 단계; 및 III) 상기 흡착단계에서의 탈착가스를 분리막 모듈을 통하여 분리 정제함으로써, 정제된 메탄은 바이오가스와 함께 재순환시키고 이산화탄소는 분리 및 배출하는 단계;를 포함하는 흡착-분리막 복합공정을 이용한 바이오가스 정제방법을 제공한다.According to an aspect of the present invention, there is provided a method for producing a biogas comprising: i) supplying a biogas to a gas compressor; II) adsorbing carbon dioxide from the compressed biogas through an adsorption device; And III) separating and purifying the desorbed gas in the adsorption step through a separation membrane module, recycling the purified methane together with the biogas, and separating and discharging the carbon dioxide. ≪ / RTI >

상기 분리막 모듈은 그 배출부에 감압장치가 구비된 것을 특징으로 한다.The separation membrane module is characterized in that the discharge unit is provided with a decompression device.

상기 감압장치는 -0.95 bar 내지 -0.5 bar에서 운전하는 것을 특징으로 한다.The decompression apparatus is characterized in that it operates at -0.95 bar to -0.5 bar.

상기 분리막 모듈은 이산화탄소의 투과도가 200 GPU 이상인 것을 특징으로 한다.The separation membrane module is characterized in that the permeability of carbon dioxide is 200 GPU or more.

상기 분리막 모듈은 이산화탄소/메탄의 선택도가 25 이상인 것을 특징으로 한다. The separation membrane module is characterized in that the selectivity of carbon dioxide / methane is 25 or more.

상기 분리막 모듈의 분리막 소재는 폴리술폰, 폴리에테르술폰, 폴리이미드, 폴리에테르이미드, 폴리아미드, 폴리카보네이트, 폴리아크릴로니트릴 및 셀룰로오즈아세테이트로 이루어진 군으로부터 선택된 어느 하나의 것을 특징으로 한다.The separation membrane material of the separation membrane module may be any one selected from the group consisting of polysulfone, polyethersulfone, polyimide, polyetherimide, polyamide, polycarbonate, polyacrylonitrile, and cellulose acetate.

상기 분리막은 중공사 복합막인 것을 특징으로 한다. And the separation membrane is a hollow fiber composite membrane.

상기 중공사 복합막은 중공사막의 표면에 폴리에틸렌 글리콜 또는 폴리에틸렌/프로필렌 글리콜을 포함하는 반복단위가 그라프트된 유기폴리실록산 공중합체로 코팅된 것을 특징으로 한다.The hollow composite membrane is characterized in that the surface of the hollow fiber membrane is coated with an organopolysiloxane copolymer having a repeating unit grafted with polyethylene glycol or polyethylene / propylene glycol.

상기 폴리에틸렌 글리콜 또는 폴리에틸렌/프로필렌 글리콜을 포함하는 반복단위가 그라프트된 유기폴리실록산 공중합체는 폴리[디메틸실록산-co-메틸(3-히드록시프로필)실록산]-그라프트-폴리(에틸렌 글리콜) 메틸 에테르, 폴리[디메틸실록산-co-메틸(3-히드록시프로필)실록산]-그라프트-폴리(에틸렌/프로필렌 글리콜) 메틸 에테르, 폴리[디메틸실록산-co-메틸(3-히드록시프로필)실록산]-그라프트-폴리(에틸렌 글리콜), 폴리[디메틸실록산-co-메틸(3-히드록시프로필)실록산]-그라프트-폴리(에틸렌/프로필렌 글리콜), 폴리[디메틸실록산-co-메틸(3-히드록시프로필)실록산]-그라프트-폴리(에틸렌 글리콜) 3-아미노프로필 에테르 또는 폴리[디메틸실록산-co-메틸(3-히드록시프로필)실록산]-그라프트-폴리(에틸렌 글리콜) [3-(트리메틸암모니오)프로필 클로라이드로 이루어진 군으로부터 선택된 어느 하나 또는 이들의 혼합물인 것을 특징으로 한다.
The organopolysiloxane copolymer in which the repeating unit grafted with polyethylene glycol or polyethylene / propylene glycol is grafted is poly [dimethylsiloxane-co-methyl (3-hydroxypropyl) siloxane] -graft-poly (ethylene glycol) , Poly [dimethylsiloxane-co-methyl (3-hydroxypropyl) siloxane] -graft-poly (ethylene / propylene glycol) methyl ether, poly [dimethylsiloxane- (Ethylene / propylene glycol), poly [dimethylsiloxane-co-methyl (3-hydroxy-3-hydroxypropyl) siloxane] graft-poly (ethylene glycol) (Ethyleneglycol) 3-aminopropyl ether or poly [dimethylsiloxane-co-methyl (3-hydroxypropyl) siloxane] - graft- Trimethylammonio) propyl chloride. Lauryl group, or a mixture thereof.

본 발명에 따르면, 바이오가스의 흡착공정에 의한 탈착가스를 분리막으로 정제하여 메탄은 재순환시키고, 이산화탄소는 분리 배출함으로써 메탄의 회수율을 95% 이상으로 크게 향상시킬 수 있는 흡착-분리막 복합공정을 이용하여 바이오가스의 고질화에 기여할 수 있다.According to the present invention, an adsorption-separation membrane composite process capable of greatly improving the recovery rate of methane to 95% or more by purifying desorbed gas by a biogas adsorption process using a separation membrane, recycling methane, and separating and discharging carbon dioxide It can contribute to the solidification of the biogas.

도 1은 본 발명의 실시예에 따른 흡착-분리막 복합공정을 이용한 바이오가스의 정제 공정도.BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a process diagram of a biogas purification process using an adsorption-separation membrane composite process according to an embodiment of the present invention. FIG.

이하에서는 본 발명에 따른 흡착-분리막 복합공정을 이용한 바이오가스 정제방법에 관하여 첨부된 도면과 함께 상세히 설명하기로 한다.Hereinafter, a biogas purification method using the adsorption-separation membrane composite process according to the present invention will be described in detail with reference to the accompanying drawings.

본 발명은 I) 바이오가스를 가스 압축기로 공급하는 단계; II) 상기 압축된 바이오가스로부터 흡착장치를 통하여 이산화탄소를 흡착하는 단계; 및 III) 상기 흡착단계에서의 탈착가스를 분리막 모듈을 통하여 분리 정제함으로써, 정제된 메탄은 바이오가스와 함께 재순환시키고 이산화탄소는 분리 및 배출하는 단계;를 포함하는 흡착-분리막 복합공정을 이용한 바이오가스 정제방법을 제공한다.
The present invention relates to a method for producing a biogas comprising the steps of: I) supplying a biogas to a gas compressor; II) adsorbing carbon dioxide from the compressed biogas through an adsorption device; And III) separating and purifying the desorbed gas in the adsorption step through a separation membrane module, recycling the purified methane together with the biogas, and separating and discharging the carbon dioxide. ≪ / RTI >

도 1에는 본 발명의 실시예에 따른 흡착-분리막 복합공정을 이용한 바이오가스의 정제 공정도를 나타내었다. 먼저, 상기 I) 및 II) 단계는 바이오가스의 통상적인 흡착공정에 관한 것으로, 도 1에서 보는 바와 같이, 일반적으로는 바이오가스(1000)가 가스 압축기(100)로 공급되어 압축되고, 흡착장치(200)에서 이산화탄소를 흡착하여 정제된 바이오메탄(2000)은 흡착장치의 정제부(202)를 통하여 이송된다. 이때, 흡착공정에서 흡착된 이산화탄소는 탈착되어 흡착장치의 배출부(201)를 통하여 대기로 방출되는데, 흡착공정에서 일정하게 설계된 바이오가스보다 많은 양의 바이오가스가 공급되면 흡착공정에서 탈착가스의 메탄 농도가 높아지게 되어 메탄의 회수율이 낮아지는 문제점이 발생한다.
FIG. 1 shows a process of purifying a biogas using an adsorption-separation membrane composite process according to an embodiment of the present invention. 1, the biogas 1000 is generally supplied to the gas compressor 100 and compressed, and the adsorbent is adsorbed to the adsorbing device 100. [ The purified biomethane 2000 adsorbed by the carbon dioxide adsorption unit 200 is transferred through the purification unit 202 of the adsorption apparatus. At this time, the carbon dioxide adsorbed in the adsorption process is desorbed and discharged to the atmosphere through the exhaust unit 201 of the adsorption apparatus. When a larger amount of biogas than the biogas designed in the adsorption process is supplied, The concentration is increased and the recovery rate of methane is lowered.

따라서 본 발명에서는, 상기 III) 단계에서처럼 흡착공정에 분리막공정을 조합함으로써 메탄의 회수율이 낮아지는 문제점을 극복할 수 있었다. 즉, 상기 흡착공정의 탈착가스를 흡착장치의 배출부(201)를 통하여 분리막 모듈(300)에 공급하여 분리 정제하되, 분리 정제된 메탄은 분리막 모듈(300)의 정제부(302)를 통하여 가스 압축기(100)의 전단으로 공급하여 바이오가스(1000)와 함께 가스 압축기(100)의 유입부(101)로 재순환시킨다.
Therefore, in the present invention, it is possible to overcome the problem that the recovery rate of methane is lowered by combining the separation membrane process in the adsorption process as in the step III). That is, the desorbed gas in the adsorption process is supplied to the separation membrane module 300 through the discharge unit 201 of the absorption apparatus to separate and purify the separated methane. The purified and separated methane is supplied to the separation membrane module 300 through the purification unit 302, Is supplied to the front end of the compressor (100) and recycled together with the biogas (1000) to the inlet (101) of the gas compressor (100).

한편, 흡착공정의 탈착가스로부터 이산화탄소를 분리 농축하여 배출하는데, 분리막 모듈(300)의 배출부(301)에 감압장치(400)를 구비함으로써, 분리막 모듈(300)에서 압력차를 발생하여 이산화탄소의 선택적 분리가 가능하고 감압장치(400)에 연결된 배출부(401)를 통하여 이산화탄소 농축가스(3000)를 대기로 배출한다.
The decompression device 400 is provided in the discharge part 301 of the separation membrane module 300 to separate and concentrate the carbon dioxide from the desorption gas in the adsorption process so that a pressure difference is generated in the separation membrane module 300, The carbon dioxide concentrated gas 3000 is discharged to the atmosphere through the discharge portion 401 which is selectively separable and connected to the decompressor 400. [

상기 감압장치(400)는 -0.95 bar 내지 -0.5 bar에서 운전하는 것이 바람직한데, -0.95 bar 미만으로 운전하면 장치 및 운전비용이 증가하고, -0.5 bar를 초과하여 운전하는 경우에는 분리막 모듈(300)에서 이산화탄소의 선택적 분리가 어려워질 수 있다.It is preferable that the decompression apparatus 400 operates at a range of -0.95 bar to -0.5 bar. If the operation is performed at less than -0.95 bar, the apparatus and operation cost increase. If the operation exceeds -0.5 bar, the separation membrane module 300 ), It may become difficult to selectively remove carbon dioxide.

또한, 상기 분리막 모듈(300)은 이산화탄소의 투과도가 200 GPU 이상인 것이 바람직한바, 이산화탄소의 투과도가 200 GPU 미만인 분리막 모듈을 사용하면, 상기 운전조건에서 이산화탄소 배출가스의 양이 적어 전체 공정에서 메탄의 회수율이 떨어질 수 있다.
The separator module 300 preferably has a permeability of not less than 200 GPU. When the separator module having a carbon dioxide permeability of less than 200 GPU is used, the amount of the carbon dioxide exhaust gas in the operation condition is small, Can fall.

아울러 상기 분리막 모듈(300)은 이산화탄소/메탄의 선택도가 25 이상인 것이 바람직한데, 이산화탄소/메탄의 선택도가 25 미만인 분리막 모듈을 사용하면, 이산화탄소의 선택적 분리가 어려워 역시 전체 공정에서 메탄의 회수율이 저하될 수 있다.
In addition, it is preferable that the separation membrane module 300 has a selectivity of carbon dioxide / methane of 25 or more. If the separation membrane module having a selectivity of carbon dioxide / methane of less than 25 is used, it is difficult to selectively remove carbon dioxide. Can be degraded.

한편, 본 발명에 따른 분리막 모듈(300)의 분리막 소재는 상대적으로 높은 선택도를 갖는 점에서 고분자 사슬간의 인력이 높은 유리상 고분자를 사용하는바, 폴리술폰, 폴리에테르술폰, 폴리이미드, 폴리에테르이미드, 폴리아미드, 폴리카보네이트, 폴리아크릴로니트릴 및 셀룰로오즈아세테이트로 이루어진 군으로부터 선택된 어느 하나의 것을 사용할 수 있다. 특히, 폴리술폰 또는 폴리에테르이미드가 더욱 바람직하며, 분리막의 형태로서는 중공사 복합막을 더욱 바람직하게 사용한다.
Meanwhile, since the separation membrane material of the separation membrane module 300 according to the present invention has a relatively high selectivity, it uses a glassy polymer having a high attraction force between chains of the polymer. As the glassy polymer, polysulfone, polyether sulfone, polyimide, polyetherimide , Polyamide, polycarbonate, polyacrylonitrile, and cellulose acetate can be used. Particularly, polysulfone or polyetherimide is more preferable, and a hollow composite membrane is more preferably used as a separation membrane.

이때, 상기 중공사 복합막은 중공사막의 표면에 폴리에틸렌 글리콜 또는 폴리에틸렌/프로필렌 글리콜을 포함하는 반복단위가 그라프트된 유기폴리실록산 공중합체로 코팅된 것이 바람직하다.At this time, it is preferable that the hollow composite membrane is coated with an organopolysiloxane copolymer having a repeating unit grafted with polyethylene glycol or polyethylene / propylene glycol on the surface of the hollow fiber membrane.

상기 폴리에틸렌 글리콜 또는 폴리에틸렌/프로필렌 글리콜을 포함하는 반복단위가 그라프트된 유기폴리실록산 공중합체는 폴리[디메틸실록산-co-메틸(3-히드록시프로필)실록산]-그라프트-폴리(에틸렌 글리콜) 메틸 에테르, 폴리[디메틸실록산-co-메틸(3-히드록시프로필)실록산]-그라프트-폴리(에틸렌/프로필렌 글리콜) 메틸 에테르, 폴리[디메틸실록산-co-메틸(3-히드록시프로필)실록산]-그라프트-폴리(에틸렌 글리콜), 폴리[디메틸실록산-co-메틸(3-히드록시프로필)실록산]-그라프트-폴리(에틸렌/프로필렌 글리콜), 폴리[디메틸실록산-co-메틸(3-히드록시프로필)실록산]-그라프트-폴리(에틸렌 글리콜) 3-아미노프로필 에테르 또는 폴리[디메틸실록산-co-메틸(3-히드록시프로필)실록산]-그라프트-폴리(에틸렌 글리콜) [3-(트리메틸암모니오)프로필 클로라이드로 이루어진 군으로부터 선택된 어느 하나 또는 이들의 혼합물을 사용한다. 종래 대부분의 중공사 복합막이 중공사막 표면에 단지 폴리디메틸실록산만을 코팅한 것과는 달리 본 발명에 따라 중공사막의 표면에 다양한 코팅제로서 폴리에틸렌 글리콜 또는 폴리에틸렌/프로필렌 글리콜을 포함하는 반복단위가 그라프트된 유기폴리실록산 공중합체를 코팅함으로써 이산화탄소의 용해도가 크게 증가하여 이산화탄소/메탄의 혼합기체로부터 이산화탄소의 투과도가 현저하게 향상되는 것이다.
The organopolysiloxane copolymer in which the repeating unit grafted with polyethylene glycol or polyethylene / propylene glycol is grafted is poly [dimethylsiloxane-co-methyl (3-hydroxypropyl) siloxane] -graft-poly (ethylene glycol) , Poly [dimethylsiloxane-co-methyl (3-hydroxypropyl) siloxane] -graft-poly (ethylene / propylene glycol) methyl ether, poly [dimethylsiloxane- (Ethylene / propylene glycol), poly [dimethylsiloxane-co-methyl (3-hydroxy-3-hydroxypropyl) siloxane] graft-poly (ethylene glycol) (Ethyleneglycol) 3-aminopropyl ether or poly [dimethylsiloxane-co-methyl (3-hydroxypropyl) siloxane] - graft- Trimethylammonio) propyl chloride. Lauryl group, or a mixture thereof. Unlike conventional hollow fiber composite membranes coated with only polydimethylsiloxane on the surface of the hollow fiber membrane according to the present invention, various kinds of coating agents, such as polyethylene glycol or polyethylene / propylene glycol-grafted repeating units, By coating the copolymer, the solubility of carbon dioxide is greatly increased and the permeability of carbon dioxide from the mixed gas of carbon dioxide / methane is remarkably improved.

또한, 본 발명의 분리막 모듈(300)은 막 모듈의 하우징 내에 1,000~150,000 가닥의 중공사 다발이 삽입되고, 막 모듈의 양 말단은 포팅제에 의해 차단된다. 상기 막 모듈의 하우징은 알루미늄, 탄소강 또는 스테인레스 소재로 제작한다.In addition, the separator module 300 of the present invention has 1,000 to 150,000 hollow fiber bundles inserted into the housing of the membrane module, and both ends of the membrane module are blocked by the potting agent. The housing of the membrane module is made of aluminum, carbon steel or stainless steel.

(실시예)(Example)

먼저, 중공사 복합막 및 막 모듈은 본 발명자 등의 선등록특허인 특허 제10-1461199호에 개시된 방법에 따라 제작하였다(이산화탄소의 투과도는 200 GPU, 선택도는 25).First, a composite hollow fiber membrane and a membrane module were produced according to the method disclosed in Japanese Patent No. 10-1461199, which is a registered trademark of the present inventors (the permeability of carbon dioxide is 200 GPU, the selectivity is 25).

도 1에 나타낸 바와 같이 장치를 구성하여 흡착-분리막 복합공정으로 바이오가스 정제공정을 수행하였으며, 각 단계별 공정에 따른 바이오가스(1000), 가스 압축기(100)의 유입부(101) 및 압축부(102), 흡착장치(200)의 배출부(201), 정제부(202) 및 바이오메탄(2000), 분리막 모듈(300)의 배출부(301) 및 정제부(302), 감압장치에 연결된 배출부(401) 및 이산화탄소 농축가스(3000) 각각의 유량 및 메탄(CH4), 이산화탄소(CO2) 농도는 아래 표 1과 같았다.
As shown in FIG. 1, the apparatus is constituted to perform a biogas purification process by an adsorption-separation membrane composite process. The biogas 1000, the inlet portion 101 of the gas compressor 100, and the compression portion The discharge unit 201 of the adsorption apparatus 200, the purification unit 202 and the biomethane 2000, the discharge unit 301 and the purification unit 302 of the separation membrane module 300, The flow rates and methane (CH 4 ) and carbon dioxide (CO 2 ) concentrations of the unit 401 and the carbon dioxide-enriched gas 3000 were as shown in Table 1 below.

항목Item 10001000 101101 102102 201201 201, 2000201, 2000 301301 302302 401, 3000401, 3000 유량(LPM)Flow rate (LPM) 110.0110.0 132.0132.0 132.0132.0 66.066.0 66.066.0 44.044.0 22.022.0 44.044.0 CH4(mol.%)CH 4 (mol.%) 60.060.0 60.060.0 60.060.0 23.323.3 96.796.7 5.05.0 60.060.0 5.05.0 CO2(mol.%)CO 2 (mol.%) 40.040.0 40.040.0 40.040.0 76.776.7 3.33.3 95.095.0 40.040.0 95.095.0

상기 실시예에 따른 표 1의 결과로부터 메탄의 회수율을 계산해 보면, 바이오가스의 흡착공정만을 수행하였을 경우 메탄의 회수율은 80.6%인 반면[80.6%=흡착공정 배출메탄 총량(202 메탄 농도 x 유량)/흡착공정 공급메탄 총량(102 메탄농도 x 유량) x 100%], 바이오가스의 흡착-분리막 복합공정을 수행하였을 경우 메탄의 회수율은 96.7%로[96.7%=흡착-분리막 복합공정 배출메탄 총량(202 메탄 농도 x 유량)/흡착-분리막 복합공정 공급메탄 총량(1000 메탄 농도 x 유량) x 100%], 본 발명에 따른 흡착-분리막 복합공정을 이용한 바이오가스 정제방법에 의하면, 종래 흡착공정만을 이용하여 바이오가스를 정제하는 방법에 비하여 메탄의 회수율이 양적으로 현저하게 증가하는 것을 확인할 수 있었다.
The recovery rate of methane from the results of Table 1 according to the above example is 80.6% when the adsorption process of biogas is performed only [80.6% = total amount of methane discharged from adsorption process (202 methane concentration x flow rate) / Methane recovery rate of 96.7% [96.7% = total amount of methane discharged from adsorption-separation membrane complex process (total methane concentration) x 100% 202 methane concentration x flow rate) / adsorption-separation membrane composite process total amount of methane supplied (1000 methane concentration x flow rate) x 100%]. According to the biogas purification method using the adsorption-separation membrane composite process according to the present invention, It was confirmed that the recovery rate of methane was significantly increased in comparison with the method of purifying the biogas.

그러므로 본 발명에 따르면, 바이오가스의 흡착공정에 의한 탈착가스를 분리막으로 정제하여 메탄은 재순환시키고, 이산화탄소는 분리 배출함으로써 메탄의 회수율을 95% 이상으로 크게 향상시킬 수 있는 흡착-분리막 복합공정을 이용하여 바이오가스의 고질화에 기여할 수 있다.
Therefore, according to the present invention, the desorption gas by the adsorption process of the biogas is purified by the separation membrane to recycle the methane, and by separating and discharging the carbon dioxide, the adsorption-separation membrane composite process capable of greatly improving the recovery rate of methane to 95% Thereby contributing to the stabilization of the biogas.

1000 : 바이오가스 2000 : 바이오메탄 3000 : 이산화탄소 농축 가스
100 : 가스 압축기 101 : 유입부 102 : 압축부
200 : 흡착장치 201 : 배출부 202 : 정제부
300 : 분리막 모듈 301 : 배출부 302 : 정제부
400 : 감압장치 401 : 배출부1000: Biogas 2000: Biomethane 3000: Carbon dioxide Concentrated gas
100: gas compressor 101: inflow section 102: compression section
200: adsorption device 201: discharging part 202: refining part
300: separation membrane module 301: discharging part 302: refining part
400: Pressure reducing device 401:

Claims (9)

I) 바이오가스를 가스 압축기로 공급하는 단계;
II) 상기 압축된 바이오가스로부터 흡착장치를 통하여 이산화탄소를 흡착하는 단계; 및
III) 상기 흡착단계에서의 탈착가스를 분리막 모듈을 통하여 분리 정제함으로써, 정제된 메탄은 바이오가스와 함께 재순환시키고 이산화탄소는 분리 및 배출하는 단계;를 포함하는 흡착-분리막 복합공정을 이용한 바이오가스 정제방법.I) supplying biogas to a gas compressor;
II) adsorbing carbon dioxide from the compressed biogas through an adsorption device; And
III) separating and purifying the desorbed gas in the adsorption step through a separation membrane module, recycling the purified methane together with the biogas, and separating and discharging the carbon dioxide, and a biogas purification method using the adsorption- . 제1항에 있어서, 상기 분리막 모듈은 그 배출부에 감압장치가 구비된 것을 특징으로 하는 흡착-분리막 복합공정을 이용한 바이오가스 정제방법.The biogas purification method according to claim 1, wherein the separation membrane module is provided with a decompression device at its discharge part. 제2항에 있어서, 상기 감압장치는 -0.95 bar 내지 -0.5 bar에서 운전하는 것을 특징으로 하는 흡착-분리막 복합공정을 이용한 바이오가스 정제방법.The biogas purification method according to claim 2, wherein the decompression apparatus operates at a flow rate of from -0.95 bar to -0.5 bar. 제1항에 있어서, 상기 분리막 모듈은 이산화탄소의 투과도가 200 GPU 이상인 것을 특징으로 하는 흡착-분리막 복합공정을 이용한 바이오가스 정제방법.The method for purifying biogas using the adsorption-separation membrane composite process according to claim 1, wherein the separation membrane module has a permeability of carbon dioxide of 200 GPU or more. 제1항에 있어서, 상기 분리막 모듈은 이산화탄소/메탄의 선택도가 25 이상인 것을 특징으로 하는 흡착-분리막 복합공정을 이용한 바이오가스 정제방법.The biogas purification method according to claim 1, wherein the separation membrane module has a selectivity of carbon dioxide / methane of 25 or more. 제1항에 있어서, 상기 분리막 모듈의 분리막 소재는 폴리술폰, 폴리에테르술폰, 폴리이미드, 폴리에테르이미드, 폴리아미드, 폴리카보네이트, 폴리아크릴로니트릴 및 셀룰로오즈아세테이트로 이루어진 군으로부터 선택된 어느 하나의 것을 특징으로 하는 흡착-분리막 복합공정을 이용한 바이오가스 정제방법.The separator according to claim 1, wherein the separation membrane material of the separation membrane module is any one selected from the group consisting of polysulfone, polyethersulfone, polyimide, polyetherimide, polyamide, polycarbonate, polyacrylonitrile and cellulose acetate Wherein the adsorbent is adsorbed on the adsorbent. 제6항에 있어서, 상기 분리막은 중공사 복합막인 것을 특징으로 하는 흡착-분리막 복합공정을 이용한 바이오가스 정제방법.[7] The method of claim 6, wherein the separation membrane is a hollow fiber composite membrane. 제7항에 있어서, 상기 중공사 복합막은 중공사막의 표면에 폴리에틸렌 글리콜 또는 폴리에틸렌/프로필렌 글리콜을 포함하는 반복단위가 그라프트된 유기폴리실록산 공중합체로 코팅된 것을 특징으로 하는 흡착-분리막 복합공정을 이용한 바이오가스 정제방법. The method of claim 7, wherein the hollow composite membrane is coated with an organopolysiloxane copolymer having a repeating unit grafted with polyethylene glycol or polyethylene / propylene glycol on the surface of the hollow fiber membrane. Biogas purification method. 제8항에 있어서, 상기 폴리에틸렌 글리콜 또는 폴리에틸렌/프로필렌 글리콜을 포함하는 반복단위가 그라프트된 유기폴리실록산 공중합체는 폴리[디메틸실록산-co-메틸(3-히드록시프로필)실록산]-그라프트-폴리(에틸렌 글리콜) 메틸 에테르, 폴리[디메틸실록산-co-메틸(3-히드록시프로필)실록산]-그라프트-폴리(에틸렌/프로필렌 글리콜) 메틸 에테르, 폴리[디메틸실록산-co-메틸(3-히드록시프로필)실록산]-그라프트-폴리(에틸렌 글리콜), 폴리[디메틸실록산-co-메틸(3-히드록시프로필)실록산]-그라프트-폴리(에틸렌/프로필렌 글리콜), 폴리[디메틸실록산-co-메틸(3-히드록시프로필)실록산]-그라프트-폴리(에틸렌 글리콜) 3-아미노프로필 에테르 또는 폴리[디메틸실록산-co-메틸(3-히드록시프로필)실록산]-그라프트-폴리(에틸렌 글리콜) [3-(트리메틸암모니오)프로필 클로라이드로 이루어진 군으로부터 선택된 어느 하나 또는 이들의 혼합물인 것을 특징으로 하는 흡착-분리막 복합공정을 이용한 바이오가스 정제방법.The process of claim 8, wherein the organopolysiloxane copolymer in which the repeating unit grafted with polyethylene glycol or polyethylene / propylene glycol is grafted is poly [dimethylsiloxane-co-methyl (3-hydroxypropyl) siloxane] -graft- Methyl (3-hydroxypropyl) siloxane] -graft-poly (ethylene / propylene glycol) methyl ether, poly [dimethylsiloxane-co- Poly [dimethylsiloxane-co-methyl (3-hydroxypropyl) siloxane] -graft-poly (ethylene / propylene glycol) Methyl (3-hydroxypropyl) siloxane] -graft-poly (ethylene glycol) 3-aminopropyl ether or poly [dimethylsiloxane- Glycol) [3- (trimethylammonio) propyl Chloride, and a mixture thereof. The method for purifying biogas using the adsorption-separation membrane composite process according to claim 1,
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