JP5314236B2 - Apparatus and method for removing siloxanes in digestion gas - Google Patents
Apparatus and method for removing siloxanes in digestion gas Download PDFInfo
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- -1 siloxanes Chemical class 0.000 title claims description 39
- 230000029087 digestion Effects 0.000 title claims description 26
- 238000000034 method Methods 0.000 title claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 94
- 239000011148 porous material Substances 0.000 claims description 28
- 239000003463 adsorbent Substances 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 4
- 239000002594 sorbent Substances 0.000 claims description 4
- 230000001079 digestive effect Effects 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 description 31
- 239000007789 gas Substances 0.000 description 26
- 239000000126 substance Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 239000002156 adsorbate Substances 0.000 description 5
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 5
- 238000000855 fermentation Methods 0.000 description 4
- 239000010801 sewage sludge Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000010800 human waste Substances 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 2
- 150000001923 cyclic compounds Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000010813 municipal solid waste Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- XMSXQFUHVRWGNA-UHFFFAOYSA-N Decamethylcyclopentasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 XMSXQFUHVRWGNA-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- YFCGDEUVHLPRCZ-UHFFFAOYSA-N [dimethyl(trimethylsilyloxy)silyl]oxy-dimethyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C YFCGDEUVHLPRCZ-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- FBZANXDWQAVSTQ-UHFFFAOYSA-N dodecamethylpentasiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C FBZANXDWQAVSTQ-UHFFFAOYSA-N 0.000 description 1
- 229940087203 dodecamethylpentasiloxane Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000010794 food waste Substances 0.000 description 1
- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
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- Separation Of Gases By Adsorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Description
本発明は下水汚泥、都市ごみ、またはし尿汚泥、生ごみ等を嫌気性醗酵させて発生したバイオガスなどからなる消化ガスをガスエンジンやボイラなどに有効利用する場合において、バイオガスを精製し、燃料として利用することができる消化ガス中のシロキサン類の除去装置及び方法に関し、詳しくは、例えばメタン醗酵バイオガスなどの消化ガス中のシロキサン類（有機シリカ化合物）の成分が多く含まれても、ほぼ１００％を除去することができ、長期にわたって高い効率を保つことができる消化ガス中のシロキサン類の除去装置及び方法に関する。 The present invention purifies biogas in the case of effectively using digestion gas consisting of biogas generated by anaerobic fermentation of sewage sludge, municipal waste, or human waste sludge, garbage, etc., for gas engines, boilers, etc. Regarding the apparatus and method for removing siloxanes in digestion gas that can be used as fuel, for example, even if many components of siloxanes (organosilica compounds) in digestion gas such as methane fermentation biogas are contained, The present invention relates to an apparatus and a method for removing siloxanes in digestion gas, which can remove almost 100% and can maintain high efficiency over a long period of time.
近年、エネルギー資源の有効利用を図る観点から、下水汚泥、都市ごみ、またはし尿汚泥、生ごみ等を嫌気性醗酵させて発生したバイオガスの積極的な利用が進められており、バイオガスをボイラ燃料に利用したり、エンジンに使用して発電したりする技術の開発が進められている。 In recent years, biogas generated from anaerobic fermentation of sewage sludge, municipal waste, human waste sludge, food waste, etc. has been promoted from the viewpoint of effective use of energy resources. Development of technology for use in fuel or power generation in engines is underway.
しかしながら、バイオガス中、特に下水汚泥消化工程から発生するバイオガス中には、シリコーンの構成物質であるシロキサン類がガス状で存在し、バイオガスに同伴することから、ガスの燃焼により固体の酸化ケイ素となり、エンジン室の弁などにシリカ結晶物として付着し、弁の開閉を妨げ異常燃焼を起こしたり、あるいは潤滑油中に混入して、シリンダーの磨耗を早めるなどエンジンの耐久性に支障をきたし、メンテナンスに必要な期間が短くなったり、補修費用の増加を招いたりする問題があった。 However, in biogas, especially biogas generated from the sewage sludge digestion process, siloxanes, which are silicone constituents, exist in gaseous form and are accompanied by biogas. It becomes silicon and adheres to the engine room valve as a silica crystal, causing the valve to open and close, causing abnormal combustion, or mixing into the lubricating oil, causing cylinder wear to be accelerated and hindering engine durability. There is a problem that the period required for maintenance is shortened and repair costs are increased.
またガスエンジンには、一般にＮＯx対策として三元触媒、卑金属系触媒などによる脱硝設備が設けられている。シロキサン類、または燃焼によって生成した、ヒューム状の酸化ケイ素は、この触媒に作用し、触媒細孔内や表面で酸化し、SiO2が触媒細孔内部や触媒表面を覆うことから、急速な触媒の劣化を招く問題があった。 Gas engines are generally provided with a denitration facility using a three-way catalyst, a base metal catalyst, or the like as a measure against NOx. Silica or fumed silicon oxide produced by combustion acts on this catalyst and oxidizes in the catalyst pores and on the surface, and SiO 2 covers the catalyst pores and on the catalyst surface, so rapid catalyst There was a problem that caused deterioration.
したがって、消化ガスの有効利用においては、これらの問題を解決する必要があり、そのためには、バイオガス中のシロキサン類の確実な除去が求められる。 Therefore, in the effective utilization of digestion gas, it is necessary to solve these problems, and for that purpose, reliable removal of siloxanes in biogas is required.
バイオガス中のシロキサン類の除去技術としては、活性炭による吸着技術が知られている（特許文献１−７）。
特許文献１−７は、シロキサンの吸着容量が大きなものを選択使用する観点で、活性炭の細孔径と細孔容積を評価要素として規定している。 Patent documents 1-7 prescribe | regulate the pore diameter and pore volume of activated carbon as an evaluation element from a viewpoint of selecting and using what has a large adsorption capacity of siloxane.
しかし、本発明者は、活性炭の従来の評価要素に加え、吸着容量の高い吸着剤の選定の要素として、吸着剤のｐＨの影響について研究を継続したところ、特定ｐＨ範囲を有する活性炭を使用することにより、消化ガス中の有機シリカ化合物の成分をほぼ１００％除去することができることを見出し、本発明に至ったものである。 However, the present inventor has continued research on the influence of the pH of the adsorbent as an element for selecting an adsorbent having a high adsorption capacity in addition to the conventional evaluation element for activated carbon, and uses activated carbon having a specific pH range. Thus, it has been found that almost 100% of the components of the organic silica compound in the digestion gas can be removed, and the present invention has been achieved.
そこで、本発明の課題は、消化ガス中の有機シリカ化合物の成分が多く含まれても、ほぼ１００％除去することができる消化ガス中のシロキサン類の除去装置及び方法を提供することにある。 Accordingly, an object of the present invention is to provide an apparatus and a method for removing siloxanes in digestion gas, which can be removed almost 100% even when a large amount of the organic silica compound component in digestion gas is contained.
また本発明の他の課題は、以下の記載によって明らかとなる。 Other problems of the present invention will become apparent from the following description.
上記課題は、以下の各発明によって解決される。 The above problems are solved by the following inventions.
（請求項１）
シロキサン類以外の不純物を実質的に含まないバイオガスからなる消化ガスを、吸着剤を充填した充填塔を通過させて前記シロキサン類を前記吸着剤により吸着除去処理するシロキサン類の除去装置において、
前記吸着剤が、比表面積５００ｍ2／ｇ以上であり、細孔分布ピークが１０〜３０Åの範囲にあり、かつｐＨが９．０以上のアルカリ処理を施すことによりシロキサン吸着能が高められた活性炭であることを特徴とする消化ガス中のシロキサン類の除去装置。
(Claim 1)
In an apparatus for removing siloxanes, a digestion gas consisting of a biogas substantially free of impurities other than siloxanes is passed through a packed tower filled with an adsorbent and the siloxanes are adsorbed and removed by the adsorbent.
Activated carbon whose sorbent is enhanced by applying an alkali treatment having a specific surface area of 500 m 2 / g or more, a pore distribution peak in the range of 10 to 30 mm, and a pH of 9.0 or more. An apparatus for removing siloxanes from digestive gas, characterized in that:
（請求項２）
シロキサン類以外の不純物を実質的に含まないバイオガスからなる消化ガスを、吸着剤と接触させて前記シロキサン類を前記吸着剤により吸着除去処理するシロキサン類の除去方法において、
前記吸着剤が、比表面積５００ｍ2／ｇ以上であり、細孔分布ピークが１０〜３０Åの範囲にあり、かつｐＨが９．０以上のアルカリ処理を施すことによりシロキサン吸着能が高められた活性炭であることを特徴とする消化ガス中のシロキサン類の除去方法。
(Claim 2)
In the method for removing siloxanes, the digestion gas comprising a biogas substantially free of impurities other than siloxanes is brought into contact with an adsorbent and the siloxanes are adsorbed and removed by the adsorbent.
Activated carbon whose sorbent is enhanced by applying an alkali treatment having a specific surface area of 500 m 2 / g or more, a pore distribution peak in the range of 10 to 30 mm, and a pH of 9.0 or more. A method for removing siloxanes in digestion gas, characterized in that
本発明によると、アルカリ処理された活性炭を使用したことにより、物理吸着作用に加えて化学吸着作用を相乗的に利用して、消化ガス中の有機シリカ化合物の成分が多く含まれても、ほぼ１００％除去することができる消化ガス中のシロキサン類の除去装置及び方法を提供することができる。 According to the present invention, by using activated carbon that has been treated with alkali, synergistically utilizing the chemical adsorption action in addition to the physical adsorption action, even if a large amount of the organic silica compound component in the digestion gas is contained, An apparatus and method for removing siloxanes in digestion gas that can be removed by 100% can be provided.
本発明によると、ｐＨ８．０以上１２．０以下の活性炭を使用したことにより、物理吸着作用に加えて化学吸着作用を相乗的に利用して、消化ガス中の有機シリカ化合物の成分が多く含まれても、ほぼ１００％除去することができる消化ガス中のシロキサン類の除去装置及び方法を提供することができる。 According to the present invention, the use of activated carbon having a pH of 8.0 or more and 12.0 or less synergistically uses the chemical adsorption action in addition to the physical adsorption action, and contains many components of the organic silica compound in the digestion gas. Even so, it is possible to provide an apparatus and a method for removing siloxanes in digestion gas which can be removed almost 100%.
以下、本発明の実施の形態について説明する。 Embodiments of the present invention will be described below.
本発明において、消化ガスは、下水汚泥、都市ごみ、またはし尿汚泥、生ごみ等を嫌気性醗酵させて発生したバイオガスなどからなり、これらの消化ガス中に含まれるにはシロキサン類（有機シリカ化合物）としては、シロキサン結合（Ｓｉ−Ｏ−Ｓｉ）を有する鎖状または環状の化合物があり、鎖状化合物としては、例えば、メトキシトリメチルシラン、ジメトキシジメチルシラン、ヘキサメチルジシロキサン、オクタメチルトリシロキサン、デカメチルテトラシロキサン、およびドデカメチルペンタシロキサンなどが挙げられ、環状化合物としては、例えばヘキサメチルシクロトリシロキサン（Ｄ３体）、オクタメチルシクロテトラシロキサン（Ｄ４体）、デカメチルシクロペンタシロキサン（Ｄ５体）、およびドデカメチルシクロヘキサシロキサン（Ｄ６体）などが挙げられる。 In the present invention, digestion gas comprises biogas generated by anaerobic fermentation of sewage sludge, municipal waste, human waste sludge, garbage, etc., and siloxanes (organosilica) are included in these digestion gases. Compound) includes a chain or cyclic compound having a siloxane bond (Si-O-Si). Examples of the chain compound include methoxytrimethylsilane, dimethoxydimethylsilane, hexamethyldisiloxane, and octamethyltrisiloxane. , Decamethyltetrasiloxane, dodecamethylpentasiloxane, and the like. Examples of the cyclic compound include hexamethylcyclotrisiloxane (D3 form), octamethylcyclotetrasiloxane (D4 form), decamethylcyclopentasiloxane (D5 form). ), And dodecamethylcyclohex Siloxane (D6 body), and the like.
バイオガス中に含まれるシロキサン類は、主に環状シロキサンであり、鎖状のシロキサン類は少ないことが分かっており、この中でもオクタメチルシクロシロキサン（Ｄ４体）、デカメチルシクロシロキサン（Ｄ５体）の含有量が多い。 The siloxanes contained in the biogas are mainly cyclic siloxanes, and it is known that there are few chain siloxanes. Among them, octamethylcyclosiloxane (D4 form) and decamethylcyclosiloxane (D5 form) High content.
活性炭の吸着能力の因子としては、従来から比表面積、細孔分布、細孔容積などがあげられているが、これらは吸着作用において吸着される物質（吸着質）が吸着質の構造をほぼ保ったまま吸着する、いわゆる物理吸着を想定したものである。 As factors of the adsorption capacity of activated carbon, the specific surface area, pore distribution, pore volume, etc. have been conventionally mentioned, but these substances that are adsorbed in the adsorption action (adsorbate) almost maintain the structure of the adsorbate. It assumes what is called physical adsorption that adsorbs as it is.
本発明において、活性炭の比表面積は５００ｍ2／ｇ以上おいて、好ましくは８００ｍ2／ｇ以上である。比表面積はＢＥＴ法による測定値である。比表面積が５００ｍ2／ｇ以上と大きいために、バイオガス中に含まれるガス状のシロキサン類の活性炭による吸着量は大きい。 In the present invention, the specific surface area of the activated carbon is 500 m 2 / g or more, preferably 800 m 2 / g or more. The specific surface area is a value measured by the BET method. Since the specific surface area is as large as 500 m 2 / g or more, the adsorption amount of gaseous siloxanes contained in biogas by activated carbon is large.
また本発明では、細孔分布は対象とする吸着質の分子径の２〜３倍が好ましい点に着目して、シロキサン類の径が１０Å弱であることから、シロキサン類の吸着には、細孔分布ピークが１０〜３０Åの範囲にある活性炭を使用している。本発明において、細孔分布の測定はＢＪＨ法による。本発明において好ましいのは、細孔分布ピークが１５〜３０Åの範囲にある活性炭を用いることである。 In the present invention, focusing on the fact that the pore distribution is preferably 2 to 3 times the molecular diameter of the target adsorbate, the diameter of the siloxanes is less than 10 mm. Activated carbon having a pore distribution peak in the range of 10 to 30 mm is used. In the present invention, the pore distribution is measured by the BJH method. In the present invention, it is preferable to use activated carbon having a pore distribution peak in the range of 15 to 30%.
本発明において使用している活性炭は、上記の物理的な特性に加えて、ｐHによる吸着容量の変化に着目し、調査した結果、アルカリ処理された活性炭、あるいはｐＨが高い活性炭がその吸着容量が大きいことがわかった。 In the activated carbon used in the present invention, in addition to the above physical characteristics, attention is paid to the change in adsorption capacity due to pH. As a result of investigation, activated carbon treated with alkali or activated carbon having a high pH has an adsorption capacity of I found it big.
本発明において、アルカリ処理とは、活性炭にアルカリ物質を添着したり、あるいはアルカリ物質を含浸させたりすることである。アルカリには水酸化ナトリウムや水酸化カリウムなどのアルカリ金属の水酸化物や塩やマグネシウムやカルシウムなどのアルカリ土類金属の水酸化物や塩、アンモニウム塩などを用いることができる。 In the present invention, the alkali treatment is to impregnate activated carbon with an alkaline substance or impregnate an alkaline substance. Alkali metal hydroxides and salts such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides and salts such as magnesium and calcium, ammonium salts and the like can be used as the alkali.
本発明においては、上記アルカリ物質から吸着質（目的）に適合する物質を選択する。 In the present invention, a substance that matches the adsorbate (purpose) is selected from the alkaline substances.
本発明において、活性炭のｐＨは８．０以上１２．０以下であり、好ましくは８．５以上１２．０以下であり、さらに好ましくは９．０以上１２．０以下である。ｐＨの測定方法は、ＪＩＳＫ１４７４による。 In the present invention, the activated carbon has a pH of 8.0 or more and 12.0 or less, preferably 8.5 or more and 12.0 or less, and more preferably 9.0 or more and 12.0 or less. The measuring method of pH is based on JISK1474.
活性炭のｐＨは８．０以上１２．０以下にするには、活性炭にアルカリ物質を添着したり、あるいはアルカリ物質を含浸させたりすることにより実現できる。 The pH of the activated carbon can be adjusted to 8.0 or more and 12.0 or less by adding an alkaline substance to the activated carbon or impregnating the activated substance with an alkaline substance.
かかるアルカリ物質の存在により、吸着質と何らかの化学反応を伴いながら、吸着を起こしていることから、吸着量が高いものと考えられる。すなわち、物理吸着作用に加えて化学吸着作用を相乗的に利用して吸着能力を更に向上させたものと考えられる。 The presence of such an alkaline substance causes adsorption while causing some chemical reaction with the adsorbate. Therefore, it is considered that the amount of adsorption is high. That is, it is considered that the adsorption capacity is further improved by synergistically using the chemical adsorption action in addition to the physical adsorption action.
活性炭による吸着容量が向上すれば、装置のコンパクト化、ランニングコストの低下を可能にする。 If the adsorption capacity by activated carbon is improved, the apparatus can be made compact and the running cost can be reduced.
本発明の消化ガス中のシロキサン類の除去方法は、活性炭とシロキサン類が接触できれば格別限定されず、活性炭吸着塔による接触でもよいし、バグフィルターなどを用いた接触でもよい。活性炭吸着塔を用いる場合、固定床式でも流動床式でもよい。接触の仕方は向流方式でも並流方式でもよい。 The method for removing siloxanes in the digestion gas of the present invention is not particularly limited as long as activated carbon and siloxanes can contact each other, and contact using an activated carbon adsorption tower or contact using a bag filter or the like may be used. When an activated carbon adsorption tower is used, a fixed bed type or a fluidized bed type may be used. The contact method may be a countercurrent method or a parallel flow method.
以下、実施例によって本発明の効果を例証する。 The effects of the present invention are illustrated below by examples.
実施例１
＜活性炭試料の作製＞
同種の活性炭（原料、比表面積、細孔分布ピーク）を用い、苛性ソーダによるアルカリ処理をすることによって、ｐＨの異なる活性炭を複数作製した。
Example 1
<Preparation of activated carbon sample>
A plurality of activated carbons having different pH values were prepared by performing alkali treatment with caustic soda using the same kind of activated carbon (raw material, specific surface area, pore distribution peak).
＜消化ガスサンプル＞
Ｎ2ガスにＤ４、Ｄ５を含むシロキサン類を消化ガスサンプルとした。
<Digestion gas sample>
Siloxanes containing D4 and D5 in N 2 gas were used as digestion gas samples.
＜試験方法＞
消化ガスサンプルを活性炭吸着塔に通過させ、通過前後のサンプルを、有機溶剤に流通し、ＦＩＤガスクロマトグラフで有機溶媒中のＤ４、Ｄ５を測定し、供給量と通過量から、吸着量を算出した。
<Test method>
The digestion gas sample was passed through the activated carbon adsorption tower, the sample before and after passing was passed through the organic solvent, D4 and D5 in the organic solvent were measured with an FID gas chromatograph, and the adsorption amount was calculated from the supply amount and the passage amount. .
吸着率＝吸着量÷活性炭量×100 Adsorption rate = adsorption amount ÷ activated carbon amount × 100
（１）活性炭物性
活性炭物性を表１に示す。
(1) Activated carbon properties Table 1 shows the activated carbon properties.
（２）テスト条件
テスト条件を表２に示す。
(2) Test conditions Table 2 shows the test conditions.
（３）テスト結果
活性炭ＡのｐＨと吸着量の関係を図１に示す。また活性炭ＢのｐＨと吸着量の関係を図２に示す。
(3) Test results The relationship between the pH of activated carbon A and the amount of adsorption is shown in FIG. The relationship between the pH of activated carbon B and the amount of adsorption is shown in FIG.
（４）考察
図１からわかるように、活性炭Ａでは活性炭のｐＨが８以上でシロキサンの吸着量が高くなり、ｐＨが９以上では急激に上昇している。また図２からわかるように、活性炭Ｂでも同様に活性炭のｐＨが８以上でシロキサンの吸着量が高くなり、ｐＨが９以上では急激に上昇している。またこの結果はアルカリ処理された活性炭Ａ、Ｂが急激にシロキサンの吸着量を高くしていることを表わしている。
(4) Consideration As can be seen from FIG. 1, in activated carbon A, the activated carbon has a pH of 8 or higher, and the amount of siloxane adsorbed is high. In addition, as can be seen from FIG. 2, the activated carbon B similarly has a high siloxane adsorption amount when the pH of the activated carbon is 8 or higher, and rapidly increases when the pH is 9 or higher. This result also shows that the activated carbons A and B treated with alkali rapidly increase the adsorption amount of siloxane.
Claims (2)
前記吸着剤が、比表面積５００ｍ2／ｇ以上であり、細孔分布ピークが１０〜３０Åの範囲にあり、かつｐＨが９．０以上のアルカリ処理を施すことによりシロキサン吸着能が高められた活性炭であることを特徴とする消化ガス中のシロキサン類の除去装置。 In an apparatus for removing siloxanes, a digestion gas consisting of a biogas substantially free of impurities other than siloxanes is passed through a packed tower filled with an adsorbent and the siloxanes are adsorbed and removed by the adsorbent.
Activated carbon whose sorbent is enhanced by applying an alkali treatment having a specific surface area of 500 m 2 / g or more, a pore distribution peak in the range of 10 to 30 mm, and a pH of 9.0 or more. An apparatus for removing siloxanes from digestive gas, characterized in that:
前記吸着剤が、比表面積５００ｍ2／ｇ以上であり、細孔分布ピークが１０〜３０Åの範囲にあり、かつｐＨが９．０以上のアルカリ処理を施すことによりシロキサン吸着能が高められた活性炭であることを特徴とする消化ガス中のシロキサン類の除去方法。 In the method for removing siloxanes, the digestion gas comprising a biogas substantially free of impurities other than siloxanes is brought into contact with an adsorbent and the siloxanes are adsorbed and removed by the adsorbent.
Activated carbon whose sorbent is enhanced by applying an alkali treatment having a specific surface area of 500 m 2 / g or more, a pore distribution peak in the range of 10 to 30 mm, and a pH of 9.0 or more. A method for removing siloxanes in digestion gas, characterized in that
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