JP2003230810A - Method and apparatus for removing carbon dioxide in digestion gas - Google Patents
Method and apparatus for removing carbon dioxide in digestion gasInfo
- Publication number
- JP2003230810A JP2003230810A JP2002030911A JP2002030911A JP2003230810A JP 2003230810 A JP2003230810 A JP 2003230810A JP 2002030911 A JP2002030911 A JP 2002030911A JP 2002030911 A JP2002030911 A JP 2002030911A JP 2003230810 A JP2003230810 A JP 2003230810A
- Authority
- JP
- Japan
- Prior art keywords
- carbon dioxide
- solvent
- gas
- absorption
- removing carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- 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
Landscapes
- Degasification And Air Bubble Elimination (AREA)
- Gas Separation By Absorption (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、消化ガス中の二酸
化炭素の除去に係り、特に、消化ガスからメタンを回収
するプロセスにおいて、脱硫した消化ガス中にメタンと
共存する高濃度の二酸化炭素を溶媒によって除去する方
法と装置に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the removal of carbon dioxide in digestive gas, and more particularly, in the process of recovering methane from digestive gas, the high concentration of carbon dioxide coexisting with methane is contained in desulfurized digestive gas. A method and an apparatus for removing by a solvent.
【0002】[0002]
【従来の技術】有機性汚泥処理設備において、汚泥を消
化することで得られる消化ガスは有用なメタンの他に、
二酸化炭素や硫化水素等を含有している。高純度のメタ
ンを得るために、その他のガス成分を除去する必要があ
る。その手順としては、まず消化ガスを脱硫することで
硫化水素を除去すると、その処理したガス中には高濃度
のメタンと二酸化炭素が含有される。この二酸化炭素の
除去法としては、溶媒による吸収処理が一般的である。
ガス吸収方法には、二酸化炭素の形態を変えずに吸収さ
せる物理吸収と、化学反応を起こすことで吸収させる反
応吸収がある。二酸化炭素を吸収した吸収液は、物理吸
収の場合、減圧下でのブラッシング、反応吸収の場合、
加熱又はスチームストリッピングを行うことで、二酸化
炭素を放散させ再生することが可能である。2. Description of the Related Art In organic sludge treatment equipment, digestive gas obtained by digesting sludge is useful methane in addition to useful methane.
It contains carbon dioxide and hydrogen sulfide. In order to obtain high-purity methane, it is necessary to remove other gas components. The procedure is as follows: First, the digested gas is desulfurized to remove hydrogen sulfide, and the treated gas contains high concentrations of methane and carbon dioxide. Absorption treatment with a solvent is generally used as a method for removing carbon dioxide.
Gas absorption methods include physical absorption in which carbon dioxide is absorbed without changing the form and reactive absorption in which carbon dioxide is absorbed by causing a chemical reaction. Absorption liquid that has absorbed carbon dioxide, in the case of physical absorption, brushing under reduced pressure, in the case of reaction absorption,
Carbon dioxide can be released and regenerated by heating or steam stripping.
【0003】この吸収液の再生操作は、二酸化炭素の回
収を要する分野において、吸収液として高価な非水溶液
を用いてクローズド化したシステムで行われている。従
来、下水処理における汚泥消化設備で、消化ガスからの
メタンの精製を行う場合、溶媒として、消化ガス量と等
量にあたる大量の二次処理水をシャワーリングし、消化
ガスを洗浄することで、二酸化炭素を除去している例が
ある。この方法は、下水処理場の様に大量の用水が存在
するケースにおいては適用可能であるが、し尿処理場や
食品工場など下水処理場以外の多くの施設では、用水が
不足するため適用不可能である。This regeneration operation of the absorbing solution is carried out in a closed system using an expensive non-aqueous solution as the absorbing solution in the field where the recovery of carbon dioxide is required. Conventionally, when purifying methane from digested gas in a sludge digestion facility for sewage treatment, as a solvent, by showering a large amount of secondary treated water equivalent to the amount of digested gas and washing the digested gas, There is an example of removing carbon dioxide. This method is applicable in the case where a large amount of water is present such as in a sewage treatment plant, but it is not applicable in many facilities other than sewage treatment plants such as human waste treatment plants and food factories due to lack of water. Is.
【0004】[0004]
【発明が解決しようとする課題】本発明は、前記従来技
術の問題点を解決し、溶媒を減圧脱気することで二酸化
炭素を系外に排出し、この溶媒を循環再利用すること
で、溶媒使用量を大幅に軽減し、効率よく二酸化炭素の
除去を行うことが可能な消化ガス中の二酸化炭素除去方
法と装置を提供することを課題とする。DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, degasses the solvent under reduced pressure to discharge carbon dioxide to the outside of the system, and recycle and reuse this solvent. An object of the present invention is to provide a method and an apparatus for removing carbon dioxide from digestive gas, which can significantly reduce the amount of solvent used and efficiently remove carbon dioxide.
【0005】[0005]
【課題を解決するための手段】上記課題を解決するた
め、本発明では、消化ガス中に高濃度で含有する二酸化
炭素の除去方法において、前記消化ガス中の二酸化炭素
を溶媒に溶解吸収せしめ、二酸化炭素を吸収した溶媒を
減圧脱気処理することで二酸化炭素を溶媒から除去した
後、該溶媒を二酸化炭素の吸収に循環再利用することと
したものである。また、本発明では、消化ガス中に高濃
度で含有する二酸化炭素の除去装置において、前記消化
ガス中の二酸化炭素を溶媒に溶解吸収させる吸収装置
と、二酸化炭素を吸収した溶媒から二酸化炭素を除去す
る減圧脱気装置と、二酸化炭素が除去された溶媒を、前
記二酸化炭素を溶解吸収する吸収装置に循環する循環経
路とを有することとしたものである。前記除去装置にお
いて、減圧脱気装置は、真空容器と、該容器内に、前記
溶媒を連続的に受入れて、該容器の内壁を流下する溶媒
を薄膜状にする回転体を有する装置とするのがよい。In order to solve the above problems, in the present invention, in a method for removing carbon dioxide contained in a high concentration in a digestive gas, the carbon dioxide in the digestive gas is dissolved and absorbed in a solvent, The solvent absorbing carbon dioxide is degassed under reduced pressure to remove carbon dioxide from the solvent, and then the solvent is circulated and reused for absorbing carbon dioxide. Further, in the present invention, in a device for removing carbon dioxide contained in the digestive gas at a high concentration, an absorber for dissolving and absorbing carbon dioxide in the digestive gas in a solvent, and removing carbon dioxide from the solvent absorbing carbon dioxide. And a circulation path that circulates the solvent from which carbon dioxide has been removed into an absorption device that dissolves and absorbs the carbon dioxide. In the removing apparatus, the vacuum degassing apparatus is an apparatus having a vacuum container and a rotor for continuously receiving the solvent and for making the solvent flowing down the inner wall of the container into a thin film in the container. Is good.
【0006】[0006]
【発明の実施の形態】本発明者らは、鋭意検討を重ねた
結果、消化ガスを脱硫して硫化水素を除去した処理ガス
に、水もしくは非水溶媒をシャワーリングして二酸化炭
素を吸収した処理液に対して、減圧脱気処理を施すこと
によって、吸収した二酸化炭素を系外に分離排出させる
ことで、この溶媒を循環再利用できることを見出し、こ
れらの知見に基づき本発明を完成するに至った。以下
に、本発明を図面に基づいて詳細に説明する。図1は、
本発明の二酸化炭素除去装置の一例を示すフロー構成図
である。図1のように、本発明は基本的には、処理対象
排ガス11を吸収塔1を通過させて、吸収液をシャワー
2することで、ガス中の二酸化炭素を吸収させ、その処
理液を処理液槽9に貯めて、減圧脱気装置5に導入し、
処理液を脱気することで二酸化炭素13を系外に排出
し、液排出ポンプによって吸収液として吸収液貯留槽3
に戻すことで循環利用する。脱気装置5において、処理
液に減圧脱気処理を施すが、減圧脱気処理としては、薄
膜を形成させて容器壁面に衝突させような脱気装置を使
用することが望ましい。BEST MODE FOR CARRYING OUT THE INVENTION As a result of intensive studies, the present inventors absorbed carbon dioxide by showering water or a non-aqueous solvent on a treatment gas obtained by desulfurizing a digestion gas to remove hydrogen sulfide. By subjecting the treatment liquid to degassing under reduced pressure, the absorbed carbon dioxide is separated and discharged out of the system, and it is found that this solvent can be circulated and reused, and the present invention is completed based on these findings. I arrived. Hereinafter, the present invention will be described in detail with reference to the drawings. Figure 1
It is a flow lineblock diagram showing an example of the carbon dioxide removal device of the present invention. As shown in FIG. 1, according to the present invention, basically, the target exhaust gas 11 is passed through the absorption tower 1 and the absorption liquid is showered 2 to absorb carbon dioxide in the gas and process the treatment liquid. It is stored in the liquid tank 9 and introduced into the vacuum degassing device 5,
Carbon dioxide 13 is discharged to the outside of the system by degassing the treatment liquid, and the absorption liquid storage tank 3 is used as an absorption liquid by the liquid discharge pump.
It is recycled by returning to. In the degassing apparatus 5, the treatment liquid is subjected to depressurizing degassing processing. As the depressurizing degassing processing, it is desirable to use a degassing apparatus that forms a thin film and collides it against the wall surface of the container.
【0007】以下において、該脱気装置を使用した液体
の脱気処理方法に関して、詳細に説明する。二酸化炭素
を吸収した処理液は、送液ポンプ10により連続的に脱
気装置5に供給される。該脱気装置内は、装置上部から
配管接続された真空ポンプ6により、常時真空の状態を
保っている。該装置に供給された処理液は、該装置内で
高速回転する円盤表面で遠心力を受けて加速され、該円
盤上で薄膜状にされる。薄膜状の処理液は、真空下にお
いて効率よく脱気され、さらに該遠心力により該真空容
器内の壁面に衝突することで、脱気効果が促進される。
これらの物理的処理により、処理液中の二酸化炭素が除
去され、ガスの溶解平衡反応式から、溶解成分までもが
平衡移動し、ガス化されて除去される。脱気された処理
液は、再び吸収液として該脱気装置の下部から系外に連
続的に引抜かれる。一方、上部から引き抜かれた二酸化
炭素13は系外に排出する。The liquid degassing method using the degasser will be described in detail below. The treatment liquid that has absorbed carbon dioxide is continuously supplied to the deaerator 5 by the liquid feed pump 10. The inside of the deaerator is always kept in a vacuum state by a vacuum pump 6 connected by piping from the upper part of the apparatus. The treatment liquid supplied to the apparatus is subjected to a centrifugal force on the surface of the disk rotating at high speed in the apparatus to be accelerated and is made into a thin film on the disk. The thin-film processing liquid is efficiently degassed under vacuum, and further, the centrifugal force collides with the wall surface in the vacuum container to accelerate the degassing effect.
By these physical treatments, carbon dioxide in the treatment liquid is removed, and from the gas dissolution equilibrium reaction equation, even dissolved components are equilibrium-transferred, gasified and removed. The degassed processing liquid is continuously withdrawn from the lower part of the degassing device to the outside of the system as an absorption liquid again. On the other hand, the carbon dioxide 13 extracted from the upper part is discharged out of the system.
【0008】図3に本発明で使用できる減圧脱気装置の
一例を示す。図3において、真空容器20には蓋21が
付いており、真空ポンプにより常時一定の真空度に維持
することができる。供給管23を介して容器内に流入す
る汚泥は、一定速度で回転する回転円盤26に衝突し、
遠心力で真空容器20の内壁に叩き付けられる。汚泥に
対してこの衝撃による破泡効果がある。さらに、汚泥
は、薄膜状となって、壁面を重力によって落ちる過程
で、真空下において効率よく脱気される。FIG. 3 shows an example of a vacuum degassing apparatus that can be used in the present invention. In FIG. 3, the vacuum container 20 is provided with a lid 21 and can always maintain a constant degree of vacuum by a vacuum pump. The sludge flowing into the container via the supply pipe 23 collides with the rotating disk 26 rotating at a constant speed,
The inner wall of the vacuum container 20 is struck by the centrifugal force. This impact has a bubble breaking effect on sludge. Further, the sludge becomes a thin film and is efficiently degassed under vacuum in the process of falling on the wall surface by gravity.
【0009】[0009]
【実施例】以下、本発明を実施例により具体的に説明す
る。
実施例1
この実施例は、本発明を実際に組込んだ消化ガスからメ
タンを精製する処理を目的とした二酸化炭素除去法につ
いて、詳細に説明する。図2に、下水処理場における汚
泥を消化処理する、従来法を行う処理のフロー(b)
と、本発明のフロー(a)を併せて示す。従来法及び本
発明方法の処理フローは、共に汚泥の消化槽14から消
化ガスを補集し、凝結水やミストを除去するための水抜
き15、消化ガス内に含まれるH 2Sを除去する脱硫塔
16、更にCO2を吸収除去する吸収塔17もしくは1
9を介して、CH4をガスホルダ18に補集する。従来
方法及び本方法の違いは、本方法では、CO2吸収液循
環吸収塔17に減圧脱気装置を用いて、図1に示すよう
に吸収液の循環を行う点である。EXAMPLES Hereinafter, the present invention will be specifically described with reference to Examples.
It
Example 1
This example illustrates a digestion gas that actually incorporates the present invention.
A carbon dioxide removal method for the purpose of purifying tan
Will be described in detail. Fig. 2 shows the pollution at the sewage treatment plant.
Flow of conventional method for digesting mud (b)
And the flow (a) of the present invention are also shown. Conventional method and book
The processing flow of the method of the invention is the same as that of the sludge digestion tank 14.
Drainage for collecting condensed gas and removing condensed water and mist
15 、 H contained in digestion gas 2Desulfurization tower for removing S
16, more CO2Absorption tower 17 or 1 that absorbs and removes
CH through 9FourAre collected in the gas holder 18. Conventional
The difference between the method and this method is that2Absorption liquid circulation
Using a vacuum degasser for the ring absorption tower 17, as shown in FIG.
This is the point where the absorption liquid is circulated.
【0010】本発明による方法では、CO2吸収液循環
吸収塔17において、吸収液の循環使用を可能としたこ
とで、使用水量の大幅な軽減と水処理設備への負荷の軽
減を図ることが可能である。表1に、下水処理場の消化
ガス処理設備において、本発明方法を採用した場合の処
理成績と、従来方法による処理成績を示す。In the method according to the present invention, since the absorption liquid can be circulated and used in the CO 2 absorption liquid circulation absorption tower 17, it is possible to greatly reduce the amount of water used and the load on the water treatment facility. It is possible. Table 1 shows the treatment results when the method of the present invention is adopted in the digestion gas treatment equipment of the sewage treatment plant and the treatment results by the conventional method.
【0011】[0011]
【表1】
従来方法による処理では、CO2吸収塔19において吸
収水を循環せずに使ったため、水使用量は400〜54
0m3/日になった。本発明方法では、吸収水を循環利
用したが、不純物による水質の悪化を防ぐため、0.5
m3/時の速度でドレンを行ったため、水使用量は15
〜18m3/日になった。それでも、水使用量は大幅に
軽減された。その後のガスホルダ内のガス組成は、CO
2も0.4〜0.5%となり、従来方法と全く遜色無い
除去成果を示した。[Table 1] In the treatment by the conventional method, since the absorbed water was used without being circulated in the CO 2 absorption tower 19, the amount of water used was 400 to 54.
It became 0 m 3 / day. In the method of the present invention, the absorbed water was circulated and used, but in order to prevent deterioration of water quality due to impurities, 0.5
Since the drainage was performed at a speed of m 3 / hour, the water consumption was 15
It became ~18m 3 / day. Nevertheless, water usage has been significantly reduced. The gas composition in the gas holder after that is CO
2 also became 0.4 to 0.5%, showing a result of removal which is quite comparable to the conventional method.
【0012】[0012]
【発明の効果】以上に詳細に説明したように、本発明に
よれば、消化ガス中の二酸化炭素を吸収液にて吸収除去
し、その処理液を減圧脱気処理することで、二酸化炭素
を再び気相に排出させ、吸収液として再生循環利用する
ことで、従来大量に必要であった水を削減でき、下水処
理場のみならず、多くの施設においてメタンガスの精製
が可能となる。As described in detail above, according to the present invention, carbon dioxide in digestive gas is absorbed and removed by an absorption liquid, and the treatment liquid is degassed under reduced pressure to remove carbon dioxide. By discharging it to the gas phase again and recycling it as an absorbent, a large amount of water, which was required in the past, can be reduced, and methane gas can be purified not only at sewage treatment plants but also at many facilities.
【図1】本発明の除去装置の一例を示すフロー構成図。FIG. 1 is a flow configuration diagram showing an example of a removing device of the present invention.
【図2】(a)本発明を用いる消化処理の処理フロー
図、(b)従来法の消化処理の処理フロー図。FIG. 2A is a process flow chart of a digestion process using the present invention, and FIG. 2B is a process flow diagram of a digestion process of a conventional method.
【図3】本発明に使用する減圧脱気装置の一例を示す断
面構成図。FIG. 3 is a cross-sectional configuration diagram showing an example of a vacuum degassing apparatus used in the present invention.
1:吸収塔、2:シャワー、3:吸収液貯留槽、4:液
供給ポンプ、5:減圧脱気装置、6:真空ポンプ、7:
分配機モータ、8:液排出ポンプ、9:処理液槽、1
0:送液ポンプ、11:処理対象ガス、12:排ガス、
13:二酸化炭素、14:消化槽、15:水抜き、1
6:脱硫塔、17:CO2吸収液循環吸収塔、18:ガ
スホルダ、19:CO2吸収塔、20:真空容器、2
1:蓋、22:仕切体、23:供給管、24:軸受、2
5:主軸、26:回転円盤、M:モータ1: Absorption tower, 2: Shower, 3: Absorption liquid storage tank, 4: Liquid supply pump, 5: Reduced pressure degassing device, 6: Vacuum pump, 7:
Distributor motor, 8: Liquid discharge pump, 9: Treatment liquid tank, 1
0: liquid feed pump, 11: target gas, 12: exhaust gas,
13: carbon dioxide, 14: digestion tank, 15: drainage, 1
6: Desulfurization tower, 17: CO 2 absorption liquid circulation absorption tower, 18: Gas holder, 19: CO 2 absorption tower, 20: Vacuum container, 2
1: lid, 22: partition body, 23: supply pipe, 24: bearing, 2
5: Spindle, 26: Rotating disk, M: Motor
───────────────────────────────────────────────────── フロントページの続き (72)発明者 西本 将明 東京都大田区羽田旭町11番1号 株式会社 荏原製作所内 (72)発明者 入内嶋 義治 東京都大田区羽田旭町11番1号 株式会社 荏原製作所内 Fターム(参考) 4D011 AA16 AB02 AC01 AC03 AC04 4D020 AA03 BA15 BB04 BC02 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Masaaki Nishimoto 11-1 Haneda Asahi-cho, Ota-ku, Tokyo Co., Ltd. Inside the EBARA CORPORATION (72) Inventor Yoshiharu Iriuchi 11-1 Haneda Asahi-cho, Ota-ku, Tokyo Co., Ltd. Inside the EBARA CORPORATION F-term (reference) 4D011 AA16 AB02 AC01 AC03 AC04 4D020 AA03 BA15 BB04 BC02
Claims (3)
素の除去方法において、前記消化ガス中の二酸化炭素を
溶媒に溶解吸収せしめ、二酸化炭素を吸収した溶媒を減
圧脱気処理することで二酸化炭素を溶媒から除去した
後、該溶媒を二酸化炭素の吸収に循環再利用することを
特徴とする消化ガス中の二酸化炭素除去方法。1. A method for removing carbon dioxide contained in a high concentration in a digestive gas, wherein the carbon dioxide in the digestive gas is dissolved and absorbed in a solvent, and the solvent absorbing the carbon dioxide is deaerated under reduced pressure. A method for removing carbon dioxide from a digestive gas, comprising removing carbon from a solvent and then recycling the solvent for absorption of carbon dioxide.
素の除去装置において、前記消化ガス中の二酸化炭素を
溶媒に溶解吸収させる吸収装置と、二酸化炭素を吸収し
た溶媒から二酸化炭素を除去する減圧脱気装置と、二酸
化炭素が除去された溶媒を、前記二酸化炭素を溶解吸収
する吸収装置に循環する循環経路とを有することを特徴
とする消化ガス中の二酸化炭素除去装置。2. A device for removing carbon dioxide contained in digestive gas at a high concentration, wherein the carbon dioxide in the digestive gas is dissolved and absorbed in a solvent, and carbon dioxide is removed from the solvent absorbing carbon dioxide. An apparatus for removing carbon dioxide from digestive gas, comprising: a vacuum degassing apparatus and a circulation path for circulating a solvent from which carbon dioxide has been removed to an absorption apparatus for dissolving and absorbing the carbon dioxide.
器内に、前記溶媒を連続的に受入れて、該容器の内壁を
流下する溶媒を薄膜状にする回転体を有する装置である
ことを特徴とする請求項2記載の消化ガス中の二酸化炭
素除去装置。3. The vacuum degassing apparatus is an apparatus having a vacuum container and a rotating body for continuously receiving the solvent and for making the solvent flowing down the inner wall of the container into a thin film in the container. The device for removing carbon dioxide from digestive gas according to claim 2, wherein.
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JP2002030911A JP2003230810A (en) | 2002-02-07 | 2002-02-07 | Method and apparatus for removing carbon dioxide in digestion gas |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005255700A (en) * | 2004-03-09 | 2005-09-22 | Mitsui Eng & Shipbuild Co Ltd | Biogas purification method and biogas purification system |
JP2008013649A (en) * | 2006-07-05 | 2008-01-24 | Mitsui Eng & Shipbuild Co Ltd | Biogas-producing system and method |
EP2161068A2 (en) | 2008-09-08 | 2010-03-10 | Politechnika Lubelska | Method and device for methane enrichment of biogas using purified municipal waste |
-
2002
- 2002-02-07 JP JP2002030911A patent/JP2003230810A/en active Pending
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005255700A (en) * | 2004-03-09 | 2005-09-22 | Mitsui Eng & Shipbuild Co Ltd | Biogas purification method and biogas purification system |
JP2008013649A (en) * | 2006-07-05 | 2008-01-24 | Mitsui Eng & Shipbuild Co Ltd | Biogas-producing system and method |
EP2161068A2 (en) | 2008-09-08 | 2010-03-10 | Politechnika Lubelska | Method and device for methane enrichment of biogas using purified municipal waste |
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