JP2008045060A - Method for recovering and purifying methane from biofermented gas by using adsorbent - Google Patents

Method for recovering and purifying methane from biofermented gas by using adsorbent Download PDF

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JP2008045060A
JP2008045060A JP2006223211A JP2006223211A JP2008045060A JP 2008045060 A JP2008045060 A JP 2008045060A JP 2006223211 A JP2006223211 A JP 2006223211A JP 2006223211 A JP2006223211 A JP 2006223211A JP 2008045060 A JP2008045060 A JP 2008045060A
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methane
adsorbent
tower
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siloxane
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JP4956089B2 (en
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Jun Izumi
順 泉
Koko O
鴻香 王
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Adsorption Technology Industries Co Ltd
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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
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/20—Capture or disposal of greenhouse gases of methane
    • 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
    • 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
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/20—Sludge processing

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Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for recovering and purifying methane from a biofermented gas by using an adsorbent. <P>SOLUTION: Provided are (1) a pressure swing adsorption methane/coexisting gas separation method wherein one tower packed with an adsorbent staying at relatively high pressure after an adsorption step and another tower packed with an adsorbent staying at relatively low pressure after a desorption step are connected to each other through their downstream parts, whereupon the residual methane is transferred from the one tower after the adsorption step to the another tower after the desorption step to attain an improved methane recovery rate and (2) a pressure swing adsorption methane/coexisting gas separation method wherein gases mainly consisting of desorbed CO<SB>2</SB>is fed into the adsorbent-packed tower after an adsorption step through its upstream part, whereupon the methane remaining in the tower is purged from its downstream part and is recirculated into a raw material line to attain an improved methane recovery rate. The adsorbent used is acid-treated silica gel, silicalite or acid-treated silicalite, or silica-coated Ca-A or Na-A zeolite. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は、吸着剤を利用したバイオ発酵ガスからのメタンの回収、精製方法に関する。   The present invention relates to a method for recovering and purifying methane from biofermentation gas using an adsorbent.

資源の有効利用や環境の保全のため、生物由来の有機資源であるバイオマスを単に焼却するのでなく、有効利用するための検討が種々なされている。これらのバイオマスには、生ゴミなどの食品廃棄物、家畜糞尿、有機性廃水、下水処理場で発生する下水汚泥などの有機性廃棄物、資源作物あるいはその廃棄物が含まれる。これらのバイオマスを嫌気性発酵させることでバイオガスを発生させて、このバイオガスをエネルギーとして利用する技術の開発が進められている。下水処理場において沈殿池で発生する下水汚泥を嫌気性発酵させて生成させるバイオガス（消化ガス）は、メタン及びＣＯ２を主成分と、微量の不純物として硫化水素、メチルメルカプタンのような硫黄などを含むガスである。なお、都市部の消化ガスには、シャンプー由来のシロキサン化合物が含まれていることが知られている。 In order to effectively use resources and preserve the environment, various studies have been made to effectively use biomass, which is an organic resource derived from living organisms, instead of simply incineration. These biomass include food waste such as raw garbage, livestock manure, organic waste water, organic waste such as sewage sludge generated in a sewage treatment plant, resource crops or waste thereof. Development of technologies for generating biogas by anaerobic fermentation of these biomass and using this biogas as energy is being promoted. Biogas (digestion gas) produced by anaerobic fermentation of sewage sludge generated in a sedimentation basin at a sewage treatment plant is mainly composed of methane and CO 2 , and sulfur such as hydrogen sulfide and methyl mercaptan as trace impurities. It is a gas containing. It is known that shampoo-derived siloxane compounds are contained in urban digestion gas.

水分、ＣＯ２、シロキサン、硫化水素及びメチルメルカプタンの中の少なくとも１種以上を含有するメタンガスを主成分とするバイオ発酵ガスから、水分、ＣＯ２及びシロキサン、硫化水素、メチルメルカプタンを除去してメタンを回収、精製する方法として最も頻繁に採用されている方法は、次のようにして行なわれている。化学吸収法で硫化水素、メチルメルカプタンを吸収して除去し、シロキサンを活性炭吸着剤に吸着させて除去し、他の化学吸収法でＣＯ２を吸収して除去する方法である。 Water, CO 2, siloxane, methane from bio-fermentation gas mainly composed of methane containing at least one more of the hydrogen sulfide and methyl mercaptan, water, CO 2 and siloxane, hydrogen sulfide, to remove the methyl mercaptan The most frequently used method for recovering and purifying lysine is performed as follows. In this method, hydrogen sulfide and methyl mercaptan are absorbed and removed by a chemical absorption method, siloxane is adsorbed and removed by an activated carbon adsorbent, and CO 2 is absorbed and removed by another chemical absorption method.

この方法は、化学吸収法が大きなスケールアップ因子を有することから大容量処理には適しているものの、最大で２，０００ｍ３Ｎ／ｈ程度の中小容量のバイオ発酵ガスの精製には適さない。また、共存不純物による吸収剤の劣化は避けられず、吸収剤の継続的な補充、吸収剤処理に伴う２次汚染の問題等が生じる。同じく、活性炭吸着法についても、吸着されたシロキサンを除去した後に、活性炭を廃棄する必要があり、経年的な消費量は大きく活性炭の廃棄処理も負担となる。 Although this method is suitable for large-capacity treatment because the chemical absorption method has a large scale-up factor, it is not suitable for the purification of small and medium-sized biofermentation gas of about 2,000 m 3 N / h at the maximum. Further, the deterioration of the absorbent due to the coexisting impurities is unavoidable, and problems such as continuous replenishment of the absorbent and secondary contamination associated with the absorbent treatment occur. Similarly, in the activated carbon adsorption method, it is necessary to discard the activated carbon after removing the adsorbed siloxane, and the amount of consumption over time is large, and the disposal of activated carbon becomes a burden.

これらの課題を克服するものとして、吸着剤を使用して相対的に高い圧力で水分、シロキサン、硫化水素、メチルメルカプタンを吸着し、次いでＣＯ２を吸着してメタンを回収、精製し、吸着した終了後、シロキサン、硫化水素、メチルメルカプタン、ＣＯ２を相対的に低い圧力で除去する圧力スイング法（ＰＳＡ）が提案されている。 In order to overcome these problems, an adsorbent is used to adsorb moisture, siloxane, hydrogen sulfide, and methyl mercaptan at a relatively high pressure, and then adsorb CO 2 to recover, purify, and adsorb methane. After completion, a pressure swing method (PSA) in which siloxane, hydrogen sulfide, methyl mercaptan, and CO 2 are removed at a relatively low pressure has been proposed.

しかし、現在提案されているＰＳＡでは、ＣＯ２吸着剤として活性炭、Ｘ型ゼオライトが採用されているが、ＣＯ２吸着に伴うメタンの共吸着が無視できず、前処理に使用するシロキサン、硫化水素、メチルメルカプタンを吸着の為の高シリカゼオライトは、長期的な使用により徐々に硫化水素、メチルメルカプタンに起因する固体硫黄の析出、シロキサンに起因するシリカの析出で吸着性能が低下する。 However, in the currently proposed PSA, activated carbon and X-type zeolite are used as the CO 2 adsorbent. However, co-adsorption of methane accompanying CO 2 adsorption cannot be ignored, and siloxane and hydrogen sulfide used for pretreatment The adsorption performance of high-silica zeolite for adsorbing methyl mercaptan gradually deteriorates due to the precipitation of solid sulfur caused by hydrogen sulfide and methyl mercaptan and the precipitation of silica caused by siloxane with long-term use.

本発明者等は、気相でのバイオガスからシロキサン、硫化水素、メチルメルカプタンを吸着し、次いでＣＯ２を吸着除去してメタンの回収、精製試験を行う中で、Ｎａ−Ａ型ゼオライト又はＣａ−Ａ型ゼオライトおよびそれらの有機ケイ素化合物の加水分解生成物を気相又は液相でシリカコートしたゼオライトを水分選択型吸着剤として使用してメタン、ＣＯ２２成分ガスからのＣＯ２除去を行うと、メタン、ＣＯ２２成分ガス中のＣＯ２を選択的に吸着し、メタンを高い濃度、高い回収率で回収、生成し得ることを見出した。これは、上記吸着剤がメタン−ＣＯ２２成分系において高いＣＯ２／メタン分離係数でＣＯ２を選択的に吸着するためと判断される。 The present inventors adsorbed siloxane, hydrogen sulfide, and methyl mercaptan from biogas in the gas phase, and then absorbed and removed CO 2 to perform methane recovery and purification tests. performing CO 2 removal from methane, CO 2 2-component gas using -A-type zeolite and zeolite hydrolysis product was silica coated with a vapor phase or liquid phase of those organosilicon compound as a water-selective adsorbent If, methane, CO 2 2 CO 2 contained component in the gas is selectively adsorbed, it found that high methane concentration, recovered at a high recovery rate can be generated. This is because the adsorbent selectively adsorbs CO 2 with a high CO 2 / methane separation factor in the methane-CO 2 two-component system.

更にシロキサンについては酸処理したシリカゲルがシリカを殆ど析出することなく、安定して吸−脱着しうること、硫化水素、メチルメルカプタンについてはシリカライト又は酸処理をしたシリカライトが固体硫黄を殆ど析出することなく吸−脱着しうること、水分についてはシリカゲルが安定して吸−脱着しうることを見いだした。又前処理用の酸処理したシリカライト、シリカゲルは吸着負荷が大きいためハニカム型の吸着剤を使用することが最も適している事が確認された。   Furthermore, for siloxane, acid-treated silica gel can be stably adsorbed and desorbed without precipitating silica, and for hydrogen sulfide and methyl mercaptan, silicalite or acid-treated silicalite precipitates almost solid sulfur. It has been found that the silica gel can be stably adsorbed and desorbed with respect to moisture. Further, it was confirmed that the use of a honeycomb-type adsorbent was most suitable for pretreated acid-treated silicalite and silica gel because of their large adsorption load.

発明者等はシロキサン、硫化水素、メチルメルカプタン、水分を吸着し、次いでＣＯ２を吸着した上記吸着剤を減圧条件下、脱着して再生する連続的なメタン回収、精製の可能なことを見出した。 The inventors have found that methane, hydrogen sulfide, methyl mercaptan, moisture is adsorbed, and then the adsorbent adsorbed with CO 2 is desorbed and regenerated under reduced pressure conditions for continuous methane recovery and purification. .

また、メタンの回収率の向上法として、
（１）吸着工程終了後の相対的高圧の当該吸着剤で充填された１塔と脱着工程終了後の相対的低圧の当該吸着剤で充填された他塔を塔後方で結んで、吸着工程終了後の１塔から残留するメタンを脱着工程終了後の他塔に移行してメタン回収率を向上する共存ガスとの圧力スイング法による分離方法。
（２）脱着したＣＯ２を主成分とするガスを吸着工程終了後の当該吸着剤吸着塔に塔前方から供給して塔内に残留するメタンを塔後方からパージしてパージガスを原料ラインに還流してメタン回収率を向上する共存ガスとの圧力スイング法による分離方法。
の有効なことも見いだした。 In addition, as a method of improving the recovery rate of methane,
(1) The adsorption step is completed by connecting one column packed with the adsorbent at a relatively high pressure after the adsorption step and another column filled with the adsorbent at a relatively low pressure after the desorption step at the rear of the column. A separation method using a pressure swing method with a coexisting gas that improves the methane recovery rate by transferring methane remaining from one subsequent tower to the other tower after completion of the desorption process.
(2) A gas mainly composed of desorbed CO 2 is supplied to the adsorbent adsorption tower after completion of the adsorption process from the front of the tower, and the methane remaining in the tower is purged from the rear of the tower to return the purge gas to the raw material line. Separation method by pressure swing method with coexisting gas to improve methane recovery rate.
I also found that it was effective.

バイオ発酵ガスを含む排気ガスより、廃棄物を除去し、環境を汚すことが無い。また、メタンを有効に回収し、燃料その他に利用することができ、資源を有効に回収することができる。   Waste is removed from the exhaust gas containing biofermentation gas and the environment is not polluted. In addition, methane can be effectively recovered and used for fuel and the like, and resources can be recovered effectively.

本発明を以下に説明する。
本発明において水分、シロキサンを吸着させるのに用いる酸処理したシリカゲル吸着剤は、市販されているシリカゲルを酸水溶液で処理して得られる。シリカゲルは、水酸基とシロキサンとが反応し、シロキサンが加水分解して吸着活性点にケイ酸が析出して吸着性能の低下につながっている。ここで、シリカゲルの酸処理を行うと、水酸基はプロトン化されてシロキサンの加水分解が著しく抑制される。この為シロキサンの吸着は可逆的となり、円滑な吸−脱着が進行する。シリカゲルを処理するのに用いる酸は、特に限定されず、任意の酸を使用してよいが、入手の容易な硫酸、硝酸等を用いるのが一般的である。また、酸水溶液の酸濃度も特に限定されず、任意の濃度でよい。シリカゲルを酸水溶液で処理する際の温度や時間も特に限定されず、任意の温度を用いてよいが、温度が高い方が、処理時間も短くてすむ。 The present invention will be described below.
The acid-treated silica gel adsorbent used for adsorbing moisture and siloxane in the present invention is obtained by treating commercially available silica gel with an acid aqueous solution. Silica gel reacts with hydroxyl groups and siloxanes, hydrolyzing siloxanes and precipitating silicic acid at the adsorption active sites, leading to a decrease in adsorption performance. Here, when the silica gel is subjected to an acid treatment, the hydroxyl group is protonated and the hydrolysis of the siloxane is remarkably suppressed. For this reason, the adsorption of siloxane is reversible, and smooth adsorption / desorption proceeds. The acid used to treat the silica gel is not particularly limited, and any acid may be used, but it is common to use sulfuric acid, nitric acid, etc., which are easily available. Further, the acid concentration of the acid aqueous solution is not particularly limited, and may be any concentration. The temperature and time for treating the silica gel with the aqueous acid solution are not particularly limited, and any temperature may be used, but the higher the temperature, the shorter the treatment time.

本発明において硫化水素、メチルメルカプタンを吸着させるのに用いる吸着剤は、シリカライト又は酸処理を施したシリカライト吸着剤である。シリカライトは、市販されているものを用いてよい。酸処理を施したシリカライトは、酸として塩酸、リン酸、ホウ酸等を用い、酸を純粋又は脱イオン水に加えて、ｐＨ０．５〜６程度の水溶液を調製し、塩酸を用いる場合には水溶液にシリカライトを懸濁させて約１０分〜３時間攪拌して、シリカライトに酸を担持させる。   In the present invention, the adsorbent used for adsorbing hydrogen sulfide and methyl mercaptan is silicalite or an adsorbed silicalite adsorbent. A commercially available silicalite may be used. Silicalite that has been subjected to acid treatment uses hydrochloric acid, phosphoric acid, boric acid, or the like as the acid, and the acid is added to pure or deionized water to prepare an aqueous solution with a pH of about 0.5-6. Suspends silicalite in an aqueous solution and stirs it for about 10 minutes to 3 hours to allow the silicalite to carry an acid.

水酸基とＨ２Ｓ、メチルメルカプタンが反応して加水分解が進行して吸着活性点に元素硫黄が析出して吸着性能の低下につながっている。ここでシリカライトを用いると、吸着剤表面の水酸基濃度が低いため、元素硫黄の析出が抑制される。更に、シリカライトの酸処理を行うと、更に残留する水酸基はプロトン化されて元素硫黄の析出が著しく抑制される。このため、Ｈ２Ｓ、メチルメルカプタンの吸着は可逆的となり、円滑な吸−脱着が進行する。シリカライト及び酸処理を施したシリカライトは、混合して用いてもよい。 Hydrolysis proceeds by the reaction of the hydroxyl group with H 2 S and methyl mercaptan, and elemental sulfur is deposited at the adsorption active site, leading to a decrease in adsorption performance. When silicalite is used here, precipitation of elemental sulfur is suppressed because the hydroxyl group concentration on the adsorbent surface is low. Further, when the silicalite is subjected to an acid treatment, the remaining hydroxyl group is protonated and the precipitation of elemental sulfur is remarkably suppressed. For this reason, adsorption of H 2 S and methyl mercaptan is reversible, and smooth adsorption / desorption proceeds. You may mix and use the silicalite which performed the silicalite and the acid treatment.

本発明においてＣＯ２を吸着させるのに用いる結晶表面にシリカコートを施したＣａ−Ａ又はＮａ−Ａ型ゼオライトは、溶剤、例えばメチルアルコールにスラリー状にゼオライトパウダーを懸濁させ、これにテンプレート、例えばテトラエトキシオルソシリケート（ＴＥＯＳ）を結晶表面に必要厚さに相当する量加え、これにＨ２Ｏ／ＴＥＯＳ比５〜２０程度で水分を加えると、シリカが析出する。 In the present invention, a Ca-A or Na-A type zeolite having a silica coating on the crystal surface used for adsorbing CO 2 is obtained by suspending zeolite powder in a slurry form in a solvent, for example, methyl alcohol, to which a template, For example, when tetraethoxyorthosilicate (TEOS) is added to the crystal surface in an amount corresponding to the required thickness, and water is added thereto at a H 2 O / TEOS ratio of about 5 to 20, silica is precipitated.

コーティング終了後、シリカゾルを加えてゼオライト：シリカゾル：脱イオン水＝５〜３０：１〜１０：１００程度でスラリーを調製し、これをハニカム基材に浸積して担持させ、温度約９０〜１５０℃で約０．５〜３時間表面水分を除去し、約３０〜８０℃／ｈで昇温して約２５０〜４５０℃、約０．５〜３時間保持してケイ酸の脱水を完了してゼオライト結晶表面のＳｉ−Ｏ−Ｓｉのネットワークを完成し且つ、脱水による活性化が終了する。このコーテイング条件で結晶表面に０．０５〜０．１μｍのシリカ薄膜が精製する。   After coating is completed, silica sol is added to prepare a slurry of zeolite: silica sol: deionized water = 5 to 30: 1 to 10: 100, and the slurry is immersed and supported on the honeycomb substrate, and the temperature is about 90 to 150. The surface water was removed at about 0.5 to 3 hours at a temperature of about 30 to 80 ° C./h and the temperature was maintained at about 250 to 450 ° C. for about 0.5 to 3 hours to complete the dehydration of silicic acid. Thus, the Si—O—Si network on the zeolite crystal surface is completed and the activation by dehydration is completed. Under this coating condition, a silica thin film of 0.05 to 0.1 μm is purified on the crystal surface.

ＣＯ２吸着量はＣａ−Ａが大きく、ＣＯ２／ＣＨ４分離係数ではＮａ−Ａの方が大きい。このコーテイング条件で結晶表面に０．０５〜０．１μｍのシリカ薄膜が精製する。
Ｎａ−Ａの窓径が４Å、Ｃａ−Ａの窓径が５Å、ＣＯ２分子径が３．２Å、ＣＨ４分子径が４．２ÅのためＮａ−Ａ、Ｃａ−ＡともＣＯ２吸着速度はＣＨ４吸着速度よりも大きい。シリカコートを施したＣａ−Ａ及びＮａ−Ａ型ゼオライトは、混合して用いてもよい。 The amount of CO 2 adsorption is larger for Ca-A, and Na-A is larger for the CO 2 / CH 4 separation factor. Under this coating condition, a silica thin film of 0.05 to 0.1 μm is purified on the crystal surface.
Since Na-A has a window diameter of 4 mm, Ca-A has a window diameter of 5 mm, CO 2 molecular diameter is 3.2 mm, and CH 4 molecular diameter is 4.2 mm, both Na-A and Ca-A have CO 2 adsorption rates of CH 4 greater than the adsorption rate. The silica-coated Ca-A and Na-A zeolites may be mixed and used.

以下に、本発明の１実施態様のシーケンスを第１表に示し、第１図を用いて説明する。   In the following, the sequence of one embodiment of the present invention is shown in Table 1 and described with reference to FIG.

Figure 2008045060
Figure 2008045060

第１ステップ（Ａ塔、Ｂ塔−塔間均圧工程）
第１図に於いて、吸着工程の終了したＡ塔と再生工程の終了したＢ塔を塔後方のバルブ８ａ，８ｂを開くとＡ塔後方に残留するメタンがＢ塔に移行して高効率に回収され、又Ａ塔、Ｂ塔とも塔内圧力は均圧化されるため、吸着工程にとっては円滑な昇圧、減圧工程にとっては円滑な減圧が進行する。 1st step (A tower, B tower-tower uniform pressure process)
In FIG. 1, when the tower A after the adsorption process and the tower B after the regeneration process are opened, the valves 8a and 8b behind the tower are opened, and the methane remaining behind the tower A is transferred to the tower B for high efficiency. Since the pressure is recovered and the pressure in the towers A and B is equalized, smooth pressure increase for the adsorption process and smooth pressure decrease for the pressure reduction process proceed.

第２ステップ（Ａ塔−昇圧工程、Ｂ塔−減圧工程）
均圧に昇圧したＡ塔と製品タンク１２の間をバルブ８ｂで結ぶと、Ａ塔の後方から製品メタンが供給され、吸着圧力８０〜１５０ｋＰＡに近いところまで昇圧する。均圧に減圧したＢ塔をバルブ９ｂを通じて真空ポンプと結ぶと塔内圧力は減圧して吸着したシロキサン、硫化水素、メチルメルカプタン、水分、ＣＯ２が脱着する。ここで最下流のＣＯ２吸着剤から脱着するＣＯ２は、上流の強吸着成分であるシロキサン、硫化水素、メチルメルカプタン、水分脱着時のパージガスとして作用し、塔内のこれらガスの分圧を著しく引き下げるため高効率に脱着が進行する。 Second step (A tower-pressurization process, B tower-depressurization process)
When the tower A and the product tank 12 that have been pressurized to equal pressure are connected by a valve 8b, product methane is supplied from the rear of the tower A, and the pressure is increased to a position close to an adsorption pressure of 80 to 150 kPA. When the B tower decompressed to equal pressure is connected to a vacuum pump through the valve 9b, the pressure inside the tower is reduced and adsorbed siloxane, hydrogen sulfide, methyl mercaptan, moisture, and CO 2 are desorbed. Here CO 2 to desorb from the most downstream CO 2 adsorbent, siloxane is upstream of strongly adsorbed component, hydrogen sulfide, methyl mercaptan, to act as a purge gas at the time of moisture desorption significantly the partial pressure of these gases in the tower Desorption progresses with high efficiency because of lowering.

第３ステップ（Ａ塔−吸着工程、Ｂ塔−再生工程）
メタン、ＣＯ２、水分、硫化水素、メチルメルカプタン、シロキサンを含有するバイオ発酵ガスを流路１からブロワー２、バルブ３ａを通じて硫化水素、メチルメルカプタン吸着剤としてシリカライト又は酸処理を施したシリカライト、水分吸着剤、シロキサン吸着剤として酸処理したシリカゲルのハニカム、ＣＯ２吸着剤として結晶表面にシリカコートを施したＣａ−Ａ又はＮａ−Ａ型ゼオライトの粒状品又はハニカムの充填塔４ａに供給する。充填塔４ａには、シリカライト系硫化水素、メチルメルカプタン吸着剤、シリカゲル系シロキサン、水分選択型吸着剤、Ａ型ゼオライトシリカコート品のＣＯ２吸着剤がこの順番で上流から充填されたハニカム吸着剤５が充填されている。（充填塔４ａ後方からＣＯ２が流過する直前にバイオ発酵ガスの供給を停止する。充填塔４ｂは塔後方までＣＯ２吸着帯が減圧によりある程度移動した状態であり、流路７から供給される製品メタンを減圧弁１８、バルブ８ｂを通じて供給し、吸着剤ハニカム５と向流接触させることでシロキサン、硫化水素、メチルメルカプタン、水分、ＣＯ２が脱着する。 Third step (A tower-adsorption process, B tower-regeneration process)
Biolite gas containing methane, CO 2 , moisture, hydrogen sulfide, methyl mercaptan, siloxane is treated with silicalite or acidite treated with hydrogen sulfide, methyl mercaptan as an adsorbent through flow blower 2 and valve 3a, The catalyst is supplied to a water-soluble adsorbent, an acid-treated silica gel honeycomb as a siloxane adsorbent, and a Ca-A or Na-A type zeolite granular product having a silica coating on the crystal surface as a CO 2 adsorbent or a packed tower 4a of the honeycomb. In the packed tower 4a, a honeycomb adsorbent filled with silicalite-based hydrogen sulfide, methyl mercaptan adsorbent, silica gel-based siloxane, moisture selective adsorbent, and CO 2 adsorbent of A-type zeolite silica coated product in this order from the upstream. 5 is filled. (The biofermentation gas supply is stopped immediately before CO 2 flows from the back of the packed tower 4a. The packed tower 4b is in a state in which the CO 2 adsorption zone has moved to some extent by decompression to the rear of the tower, and is supplied from the flow path 7. The product methane is supplied through the pressure reducing valve 18 and the valve 8b and brought into countercurrent contact with the adsorbent honeycomb 5, whereby siloxane, hydrogen sulfide, methyl mercaptan, moisture, and CO 2 are desorbed.

脱着されたシロキサン、ＣＯ２については無害なので系外に排出する。硫化水素、メチルメルカプタンについてはアルカリ溶液への吸収固定化が一般的である。このように、本発明に従えば、有害物質を環境に放出することが無い。 Since the desorbed siloxane and CO 2 are harmless, they are discharged out of the system. Hydrogen sulfide and methyl mercaptan are generally absorbed and fixed in an alkaline solution. Thus, according to the present invention, no harmful substances are released into the environment.

ここで第１〜３ステップと同じ操作をＡ塔とＢ塔を変更して、第４〜６ステップで実施する。
以下実施例により本発明をさらに具体的に説明する。 Here, the same operation as the first to third steps is performed in the fourth to sixth steps by changing the A tower and the B tower.
Hereinafter, the present invention will be described more specifically with reference to examples.

本発明の方法を、第１及び２図に示す装置を使用して、下記の条件で実施した。
第１ステップ（Ａ塔、Ｂ塔−塔間均圧工程）
第１図において、吸着工程の終了した吸着圧力１２０ｋＰＡのＡ塔と再生工程の終了した再生圧力５ｋＰａのＢ塔を塔後方のバルブ８ａ，８ｂを開くとＡ塔後方に残留するメタンがＢ塔に移行して高効率に回収され、又Ａ塔、Ｂ塔とも塔内圧力は６０ｋＰａ程度に均圧化されるため、吸着工程にとっては円滑な昇圧、減圧工程にとっては円滑な減圧が進行する。 The method of the present invention was carried out using the apparatus shown in FIGS. 1 and 2 under the following conditions.
1st step (A tower, B tower-tower uniform pressure process)
In FIG. 1, when the tower A having an adsorption pressure of 120 kPa after completion of the adsorption process and the tower B having a regeneration pressure of 5 kPa after completion of the regeneration process are opened, the valves 8a and 8b at the rear of the tower are opened. Since the pressure in the towers A and B is equalized to about 60 kPa, smooth pressure increase for the adsorption process and smooth pressure reduction for the pressure reduction process proceed.

第２ステップ（Ａ塔−昇圧工程、Ｂ塔−減圧工程）
６０ｋＰａ程度に昇圧したＡ塔と製品タンク１２の間をバルブ８ｂで結ぶと、Ａ塔の後方から製品メタンが供給され、吸着圧力１２０ｋＰＡに近いところまで昇圧する。６０ｋＰａ程度に減圧したＢ塔をバルブ９ｂを通じて真空ポンプと結ぶと塔内圧力は１０ｋＰＡ以下に減圧して吸着したシロキサン、硫化水素、メチルメルカプタン、水分、ＣＯ２が脱着する。ここで最下流のＣＯ２吸着剤から脱着するＣＯ２は、上流の強吸着成分であるシロキサン、硫化水素、メチルメルカプタン、水分脱着時のパージガスとして作用し、塔内これらガスの分圧を著しく引き下げるため高効率に脱着が進行する。 Second step (A tower-pressurization process, B tower-depressurization process)
When the A tower boosted to about 60 kPa and the product tank 12 are connected by the valve 8b, the product methane is supplied from the rear of the A tower and the pressure is increased to a position close to the adsorption pressure of 120 kPa. When the column B reduced in pressure to about 60 kPa is connected to a vacuum pump through the valve 9b, the adsorbed siloxane, hydrogen sulfide, methyl mercaptan, moisture, and CO 2 are desorbed by reducing the pressure in the column to 10 kPa or less. CO 2 to desorb from the most downstream CO 2 adsorbent Here, siloxane is upstream of strongly adsorbed component, hydrogen sulfide, methyl mercaptan, to act as a purge gas at the time of moisture desorption, lowering considerably the partial pressure of these gases in the column Therefore, desorption proceeds with high efficiency.

第３ステップ（Ａ塔−吸着工程、Ｂ塔−再生工程）
メタン６０ｖｏｌ％、ＣＯ２ ３５ｖｏｌ％、水分５ｖｏｌ％、硫化水素１００ｐｐｍ、メチルメルカプタン１０ｐｐｍ，シロキサン１００ｐｐｍ程度を含有するバイオ発酵ガス１００ｍ３Ｎ／ｈを流路１からブロワー２、バルブ３ａを通じて硫化水素、メチルメルカプタン吸着剤としてシリカライト又は酸処理を施したシリカライト、水分吸着剤、シロキサン吸着剤として酸処理したシリカゲルのハニカム、ＣＯ２吸着剤として結晶表面にシリカコートを施したＣａ−Ａ又はＮａ−Ａ型ゼオライトの粒状品又はハニカムの充填塔４ａに供給する。充填塔４ａは直径３０ｃｍ、高さ１２０ｃｍの大きさでありここに９０ｌのシリカライト系硫化水素、メチルメルカプタン吸着剤、シリカゲル系シロキサン、水分選択型吸着剤、Ａ型ゼオライトシリカコート品のＣＯ２吸着剤がこの順番で上流から充填されたハニカム５が充填されている。（空塔速度は０．５ｍ／ｓｅｃ、吸着負荷は６５０ｍ３Ｎ／ｈ／ｔｏｎで有る。）充填塔４ａ後方からＣＯ２が流過する直前にバイオ発酵ガスの供給を停止する。充填塔４ｂは塔後方までＣＯ２吸着帯が減圧によりある程度移動した状態であり、流路１７から供給される４ｍ３Ｎ／ｈの製品メタンを減圧弁１８、バルブ８ｂを通じて供給し、吸着剤ハニカム５と向流接触することでシロキサン、硫化水素、メチルメルカプタン、水分、ＣＯ２が脱着する。 Third step (A tower-adsorption process, B tower-regeneration process)
Methane 60vol%, CO 2 35vol%, water 5 vol%, hydrogen sulfide 100 ppm, methyl mercaptan 10 ppm, the blower 2 bio fermentation gas 100m3N / h from the channel 1 containing approximately siloxane 100 ppm, hydrogen sulfide through valve 3a, methyl mercaptan adsorption silicalite or acid-treated silicalite subjected as agents, water absorbent, honeycomb silica gel acid treated as siloxane adsorbent, Ca-a, or Na-a type zeolite was subjected to silica coated on the crystal surface as a CO 2 adsorbent To the packed column 4a. Packed column 4a diameter 30 cm, height 120cm of a size where the silicalite-based hydrogen sulfide 90l, methyl mercaptan adsorbents, silica gel-based siloxane, moisture-selective adsorbent, A-type zeolite silica-coated article of CO 2 adsorption The honeycomb 5 filled with the agent from the upstream in this order is filled. (The superficial velocity is 0.5 m / sec and the adsorption load is 650 m3 N / h / ton.) The supply of biofermentation gas is stopped immediately before CO 2 flows from the back of the packed tower 4a. The packed tower 4b is in a state in which the CO 2 adsorption zone has moved to some extent by decompression to the rear of the tower, and 4 m 3 N / h product methane supplied from the flow path 17 is supplied through the pressure reducing valve 18 and the valve 8b, Silica, hydrogen sulfide, methyl mercaptan, moisture, and CO 2 are desorbed by the countercurrent contact.

ここで第１〜３ステップと同じ操作をＡ塔とＢ塔を変更して、第４〜６ステップで実施する。   Here, the same operation as the first to third steps is performed in the fourth to sixth steps by changing the A tower and the B tower.

実施例１：ＣＯ２選択型吸着剤としてのシリカコートを施したＣａ−Ａ、Ｎａ−Ａ型ゼオライトの調製例及び性能評価
ＣＯ２選択型吸着剤ハニカム５として、Ｎａ−Ａ、Ｃａ−Ａ、Ｎａ−Ａ（１０ｎｍ）、Ｃａ−Ａ（１０ｎｍ）、Ｎａ−Ａ（５０ｎｍ）、Ｃａ−Ａ（５０ｎｍ）、Ｎａ−Ａ（１００ｎｍ）、Ｃａ−Ａ（１００ｎｍ）の比較評価を行った。 Example 1: Ca-A was subjected to silica-coated as CO 2 selective adsorbent, Preparation Examples and Evaluation CO 2 selective adsorbent honeycomb 5 of Na-A type zeolite, Na-A, Ca-A , Comparative evaluation of Na-A (10 nm), Ca-A (10 nm), Na-A (50 nm), Ca-A (50 nm), Na-A (100 nm), and Ca-A (100 nm) was performed.

ここでＮａ−Ａ、Ｃａ−Ａの（ ）内はシリカコートの薄膜厚さである。ここでＮａ−Ａ、Ｃａ−Ａのシリカコートによるゼオライト結晶上の薄膜成長には、メチルアルコールにスラリー状にゼオライトパウダーを懸濁させ、これにテトラエトキシオルソシリケート（ＴＥＯＳ）を結晶表面に必要厚さに相当する量加え、これにＨ２Ｏ／ＴＥＯＳ比１０程度で水分を加えると、シリカが析出する。（今回は１回のコーティングで１０〜２０ｎｍのシリカが析出するように調整し、今回は３回で５０ｎｍ、５回で１００ｎｍになるように調整した。） Here, the inside of () of Na-A and Ca-A is the thin film thickness of the silica coat. Here, for the thin film growth on the zeolite crystal by the silica coating of Na-A and Ca-A, the zeolite powder is suspended in a slurry form in methyl alcohol, and tetraethoxyorthosilicate (TEOS) is added to the crystal surface at the required thickness. When an amount corresponding to the above is added and moisture is added to this at an H 2 O / TEOS ratio of about 10, silica is precipitated. (This time, adjustment was made so that 10 to 20 nm of silica was deposited by one coating, and this time, adjustment was made to be 50 nm by 3 times and 100 nm by 5 times.)

コーティング終了後、シリカゾルを加えてゼオライト：シリカゾル：脱イオン水＝１５：３：１００でスラリーを調製し、これをハニカム基材に浸積して嵩比重０．４程度に担持し、１１０℃１時間で表面水分を除去し、５０℃／ｈで昇温して３５０℃、１時間保持してケイ酸の脱水を完了してゼオライト結晶表面のＳｉ−Ｏ−Ｓｉのネットワークを完成し且つ、脱水による活性化が終了する。
結果を第２表に示す。 After coating is completed, silica sol is added and a slurry is prepared with zeolite: silica sol: deionized water = 15: 3: 100, and this is immersed in a honeycomb base material to carry a bulk specific gravity of about 0.4. Remove surface moisture over time, heat up at 50 ° C / h and hold at 350 ° C for 1 hour to complete silicic acid dehydration to complete the Si-O-Si network on the zeolite crystal surface and dehydration The activation by ends.
The results are shown in Table 2.

Figure 2008045060
Figure 2008045060

いずれも原料ガス中メタン濃度６０ｖｏｌ％を越えており、又現在ＣＯ２吸着剤として使用されているＬｉ−Ｘ（ＳｉＯ２／Ａｌ２Ｏ３比２）のメタン回収率を越えており、本発明の有効性が示される。 In any case, the methane concentration in the raw material gas exceeds 60 vol%, and the methane recovery rate of Li—X (SiO 2 / Al 2 O 3 ratio 2) currently used as a CO 2 adsorbent is exceeded. The effectiveness of is shown.

特にＮａ−Ａ、Ｃａ−Ａ及びこれらのシリカコート品はメタンに対し分子篩効果を示す高いＣＯ２吸着性能を示した。最も高いＣＯ２除去性能を示したのはＣａ−Ａ（５０ｎｍ）であった。これは比較的大きなＣＯ２吸着速度とメタンに対する分子篩効果を有する程度の窓径（結晶のガスの通り道）で有るためと思われる。 In particular, Na-A, Ca-A, and these silica-coated products showed high CO 2 adsorption performance showing a molecular sieve effect on methane. Ca-A (50 nm) showed the highest CO 2 removal performance. This seems to be due to the relatively large CO 2 adsorption rate and the window diameter (crystal gas passage) that has a molecular sieving effect on methane.

実施例２：硫黄化合物選択型吸着剤としての酸処理をしたシリカライトの調製例及び性能評価
硫黄化合物選択型吸着剤ハニカム５として、酸処理をしたシリカライトＳｉｌｉｃａｌｉｔｅ（１），Ｓｉｌｉｃａｌｉｔｅ（４）、Ｓｉｌｉｃａｌｉｔｅ（ＰＯ４−０．５）、Ｓｉｌｉｃａｌｉｔｅ（ＰＯ４−０．５）、Ｓｉｌｉｃａｌｉｔｅ（ＰＯ４−１）、Ｓｉｌｉｃａｌｉｔｅ（ＰＯ４−２）、Ｓｉｌｉｃａｌｉｔｅ（ＰＯ４−４）、Ｓｉｌｉｃａｌｉｔｅ（ＢＯ３−０．５）、Ｓｉｌｉｃａｌｉｔｅ（ＢＯ３−０．５）、Ｓｉｌｉｃａｌｉｔｅ（ＢＯ３−１）、Ｓｉｌｉｃａｌｉｔｅ（ＢＯ３−２）、Ｓｉｌｉｃａｌｉｔｅ（ＢＯ３−４）と未処理のシリカライトの比較評価を行った。 Example 2: Preparation Example and Performance Evaluation of Silicalite Treated with Acid as Sulfur Compound-Selective Adsorbent Silicalite Silicalite (1), Silicalite (4), acid-treated as sulfur compound-selective adsorbent honeycomb 5 Siliconeite (PO4-0.5), Siliconeite (PO4-0.5), Siliconeite (PO4-1), Siliconelite (PO4-2), Siliconelite (PO4-4), Siliconelite (BO3-0.5), Siliconeite ( BO3-0.5), Silicalite (BO3-1), Silicalite (BO3-2), Silicalite (BO3-4) and untreated silicalite were comparatively evaluated.

ここでＳｉｌｉｃａｌｉｔｅの（ ）内はＨＣｌで酸処理をしたときの処理液のｐＨ又はリン酸処理をしたときの担持量（質量％）、ホウ酸を担持したときの担持量（質量％）である。先ずＨＣｌ溶液処理に溶液によるシリカライトの酸処理には、純水にＨＣｌを加えてｐＨ１及びｐＨ４のＨＣｌ溶液を調製し、これら水溶液にシリカライトを懸濁させて３０分間攪拌した。   Here, the values in () of Silicalite are the pH of the treatment liquid when it is acid-treated with HCl, the loading amount (mass%) when phosphoric acid treatment is carried, and the loading quantity (mass%) when boric acid is supported. . First, for the acid treatment of silicalite by solution in HCl solution treatment, HCl was added to pure water to prepare HCl solutions of pH 1 and pH 4, and silicalite was suspended in these aqueous solutions and stirred for 30 minutes.

攪拌終了後、ろ過してシリカゾルを加えてゼオライト：シリカゾル：脱イオン水＝１５：３：１００でスラリーを調製し、これをハニカム基材に浸積して嵩比重０．４程度に担持し、１１０℃１時間で表面水分を除去し、５０℃／ｈで昇温して３５０℃、１時間保持してシリカライトの酸処理が終了する。   After completion of stirring, filtration is performed, silica sol is added, and a slurry is prepared with zeolite: silica sol: deionized water = 15: 3: 100, and this is immersed in a honeycomb base material to carry a bulk specific gravity of about 0.4, The surface moisture is removed at 110 ° C. for 1 hour, the temperature is raised at 50 ° C./h, and the temperature is maintained at 350 ° C. for 1 hour to complete the acid treatment of silicalite.

次にリン酸及びホウ酸については脱イオン水１００ｇにシリカライト１５ｇ、リン酸又はホウ酸Ａグラム（ｇ）を加え、ここでＡグラム（ｇ）は目標担持率をＣｗ％とすると（１）式で計算する。
Ａ ＝ １５×Ｃ×１／１００ （１） Next, for phosphoric acid and boric acid, 15 g of silicalite and A gram (g) of phosphoric acid or boric acid are added to 100 g of deionized water, where A gram (g) is Cw% (1) Calculate with the formula.
A = 15 × C × 1/100 (1)

結果を第３表に示す。   The results are shown in Table 3.

Figure 2008045060

ＨＣｌ処理、リン酸ドープ、ホウ酸ドープのいずれも未処理のシリカライトに比べ長時間運転時の硫化水素、メチルメルカプタンとの除去に対する耐久性を示している。これは吸着剤への７２０時間運転後の硫黄析出量が未処理シリカライトに比べ抑制されていることからも確認される。ここでＨＣｌ処理についてはｐＨ１のものがもっと優れた耐久性を示し、リン酸ドープ、ホウ酸ドープについては２ｇ程度の添加が最適と評価された。
Figure 2008045060
HCl treatment, phosphoric acid dope, and boric acid dope all show durability against removal of hydrogen sulfide and methyl mercaptan during long-time operation compared to untreated silicalite. This is also confirmed from the fact that the amount of sulfur deposited on the adsorbent after operation for 720 hours is suppressed compared to untreated silicalite. Here, with regard to HCl treatment, those with pH 1 showed more excellent durability, and it was evaluated that the addition of about 2 g was optimal for phosphoric acid dope and boric acid dope.

これは吸着活性点近傍の酸点強度が上昇すると、硫化水素、メチルメルカプタンの化学吸着量が減少し、吸着活性点でのクラウス反応（（２．１〜２．３）式）が減少するためと思われる。
Ｈ２Ｓ ＋ １／２Ｏ２ → Ｓ ＋ Ｈ２Ｏ （２．１）
Ｈ２Ｓ ＋ ３／２Ｏ２ → ＳＯ２ ＋ Ｈ２Ｏ （２．２）
２Ｈ２Ｓ ＋ ＳＯ２ → ３Ｓ ＋ ２Ｈ２Ｏ （２．３） This is because when the acid point strength in the vicinity of the adsorption active point increases, the amount of chemical adsorption of hydrogen sulfide and methyl mercaptan decreases, and the Claus reaction (formula (2.1 to 2.3)) at the adsorption active point decreases. I think that the.
H2S + 1 / 2O 2 → S + H 2 O (2.1)
H2S + 3 / 2O 2 → SO 2 + H 2 O (2.2)
2H2S + SO 2 → 3S + 2H 2 O (2.3)

実施例３：シロキサン選択型吸着剤としたの酸処理をしたシリカゲルの調製例及び性能評価
シロキサン選択型吸着剤ハニカム５として、酸処理をしたシリカライトシリカゲル（１）、シリカゲル（４）、シリカゲル（ＰＯ４−０．５）、シリカゲル（ＰＯ４−０．５）、シリカゲル（ＰＯ４−１）、シリカゲル（ＰＯ４−２）、シリカゲル（ＰＯ４−４）、シリカゲル（ＢＯ３−０．５）、シリカゲル（ＢＯ３−０．５）、シリカゲル（ＢＯ３−１）、シリカゲル（ＢＯ３−２）、シリカゲル（ＢＯ３−４）と未処理のシリカゲルの比較評価を行った。 Example 3 Preparation Example and Performance Evaluation of Acid-treated Silica Gel as Siloxane-Selective Adsorbent As Siloxane-Selective Adsorbent Honeycomb 5, acid-treated silicalite silica gel (1), silica gel (4), silica gel ( PO4-0.5), silica gel (PO4-0.5), silica gel (PO4-1), silica gel (PO4-2), silica gel (PO4-4), silica gel (BO3-0.5), silica gel (BO3- 0.5), silica gel (BO3-1), silica gel (BO3-2), silica gel (BO3-4) and untreated silica gel were comparatively evaluated.

ここでシリカゲルの（ ）内はＨＣｌで酸処理をしたときの処理液のｐＨ又はリン酸処理をしたときの担持量（質量％）、ホウ酸を担持したときの担持量（質量％）である。先ずＨＣｌ溶液処理に溶液によるシリカゲルの酸処理には、純水にＨＣｌを加えてｐＨ１及びｐＨ４のＨＣｌ溶液を調製し、これら水溶液にシリカゲルを懸濁させて３０分間攪拌した。   Here, the values in () of the silica gel are the pH of the treatment solution when it is acid-treated with HCl or the loading amount (mass%) when phosphoric acid treatment is carried out, and the loading amount (mass%) when boric acid is carried. . First, for the acid treatment of silica gel with the solution in the HCl solution treatment, HCl was added to pure water to prepare HCl solutions of pH 1 and pH 4, and the silica gel was suspended in these aqueous solutions and stirred for 30 minutes.

攪拌終了後、ろ過してシリカゾルを加えてシリカゲル：シリカゾル：脱イオン水＝１５：３：１００でスラリーを調製し、これをハニカム基材に浸積して嵩比重０．４程度に担持し、１１０℃１時間で表面水分を除去し、５０℃／ｈで昇温して３５０℃、１時間保持してシリカゲルの酸処理が終了する。   After completion of stirring, filtration is performed, silica sol is added, and a slurry is prepared with silica gel: silica sol: deionized water = 15: 3: 100, and this is immersed in a honeycomb base material to carry a bulk specific gravity of about 0.4, The surface moisture is removed at 110 ° C. for 1 hour, the temperature is raised at 50 ° C./h, the temperature is maintained at 350 ° C. for 1 hour, and the acid treatment of the silica gel is completed.

次にリン酸及びホウ酸については脱イオン水１００ｇにシリカゲル１５ｇ、リン酸又はホウ酸Ａグラム（ｇ）を加え、ここでＡグラム（ｇ）は目標担持率をＣｗ％とすると（１）式で計算する。
Ａ ＝ １５×Ｃ×１／１００ （１） Next, for phosphoric acid and boric acid, 15 g of silica gel and phosphoric acid or boric acid A gram (g) are added to 100 g of deionized water, where A gram (g) is the formula (1) where the target loading is Cw%. Calculate with
A = 15 × C × 1/100 (1)

結果を第４表に示す。   The results are shown in Table 4.

Figure 2008045060
Figure 2008045060

ＨＣｌ処理シリカゲルは、未処理のシリカゲルに比べ長時間運転時のシロキサン除去に対する耐久性を示している。これは吸着剤への７２０時間運転後のシリカ析出量が未処理シリカゲルに比べ抑制されていることからも確認される。ここでＨＣｌ処理についてはｐＨ１のものがもっと優れた耐久性を示し、リン酸ドープ、ホウ酸ドープについては２ｇ程度の添加が最も最適と評価された。   HCl-treated silica gel shows durability against siloxane removal during long-time operation compared to untreated silica gel. This is also confirmed from the fact that the amount of silica deposited on the adsorbent after operation for 720 hours is suppressed compared to untreated silica gel. Here, with regard to the HCl treatment, those having a pH of 1 showed more excellent durability, and it was evaluated that the addition of about 2 g was the most optimal for the phosphoric acid dope and the boric acid dope.

これは吸着活性点近傍の酸点強度が上昇すると、シロキサンの化学吸着量が減少し、吸着活性点でのシロキサンの加水分解反応（（３）式）が減少するためと思われる。
Ｒｌ・Ｓｉｍ・Ｏｎ ＋ ｋＨ２Ｏ → ｍＳｉＯ２ ＋ ｌＲＯＨ （４） This seems to be because when the acid point strength near the adsorption active site increases, the amount of siloxane chemisorption decreases, and the hydrolysis reaction of siloxane at the adsorption active site (formula (3)) decreases.
Rl · Sim · On + kH 2 O → mSiO 2 + lROH (4)

次に吸着剤としてシロキサン吸着剤としてｐＨ１のＨＣｌ溶液で酸処理したシリカゲル、硫化水素、メチルメルカプタン吸着剤としてｐＨ１のＨＣｌ溶液で酸処理したシリカライト、水分吸着剤としてシリカゲルのハニカム、ＣＯ２吸着剤として結晶表面にＴＥＯＳを使用して３回シリカコート（コート厚さ５０ｎｍ）を施したＣａ−Ａ型ゼオライトの粒状成型品（直径１．６ｍｍペレット）を使用し、原料流量と製品メタン濃度、製品メタン回収率の関係を調べた。結果を第５表に示す。 Next, silica gel acid-treated with a pH 1 HCl solution as a siloxane adsorbent, hydrogen sulfide, silicalite acid-treated with a pH 1 HCl solution as a methyl mercaptan adsorbent, a silica gel honeycomb as a water adsorbent, a CO 2 adsorbent Using a granular molded product of Ca-A type zeolite (diameter 1.6mm pellets) with silica coating (coating thickness 50nm) three times using TEOS on the crystal surface, raw material flow rate, product methane concentration, product The relationship of methane recovery was investigated. The results are shown in Table 5.

Figure 2008045060
Figure 2008045060

原料流量の減少に伴い吸着塔出口のメタン濃度は増大するが、メタン回収率は減少する。この為流量を８０ｍ3Ｎ／ｈ程度に減少するとメタン濃度は９６ｖｏｌ％に上昇し、一方原料流量を１５０ｍ3Ｎ／ｈに上昇すると、メタン回収率は９５％に上昇する。 As the raw material flow rate decreases, the methane concentration at the outlet of the adsorption tower increases, but the methane recovery rate decreases. Therefore, when the flow rate is reduced to about 80 m 3 N / h, the methane concentration increases to 96 vol%, while when the raw material flow rate is increased to 150 m 3 N / h, the methane recovery rate increases to 95%.

次に、同一吸着剤充填条件での原料ガス流量１００ｍ3Ｎ／ｈにおけるサイクルタイムと製品メタン濃度、製品メタン回収率の関係を調べた。結果を第６表に示す。 Next, the relationship between the cycle time, the product methane concentration, and the product methane recovery rate at a raw material gas flow rate of 100 m 3 N / h under the same adsorbent filling conditions was examined. The results are shown in Table 6.

Figure 2008045060
Figure 2008045060

サイクルタイムの短縮に伴い製品濃度は増大し、製品メタン回収率も増大する。サイクルタイム１分で製品メタン濃度は９５ｖｏｌ％に達し、製品メタン回収率も９４％に達した。これはＣａ−Ａの分子篩効果で分子径の小さなＣＯ２は短サイクルタイムでも吸着されるが、大きな分子径のメタンは吸着されにくいためと思われる。従ってサイクルタイムの短縮で吸着剤の使用量を削減、製品メタン濃度の向上、製品メタン回収率の向上が同時に達成できることとなる。 As the cycle time decreases, the product concentration increases and the product methane recovery rate also increases. With a cycle time of 1 minute, the product methane concentration reached 95 vol% and the product methane recovery rate reached 94%. This is probably because CO 2 having a small molecular diameter is adsorbed even in a short cycle time due to the molecular sieve effect of Ca-A, but methane having a large molecular diameter is hardly adsorbed. Therefore, it is possible to simultaneously reduce the amount of adsorbent used by shortening the cycle time, improve the product methane concentration, and improve the product methane recovery rate.

次に製品メタンパージガス量と製品メタン濃度、製品メタン回収率の関係を調べた。結果を第７表に示す。   Next, the relationship between the amount of product methane purge gas, product methane concentration, and product methane recovery rate was investigated. The results are shown in Table 7.

Figure 2008045060
Figure 2008045060

製品メタンパージ量の増大に伴い製品メタン濃度は上昇し、８ｍ3Ｎ／ｈでは９８ｖｏｌ％に達する。しかし一度回収したメタンをパージガスに使用するためメタン回収率は８６％に低下する。一方製品メタンパージ量を２ｍ３Ｎ／ｈに削減すると、製品メタン濃度は８４％に低下する。回収率は９４％に上昇するので高いメタン濃度を要求しない場合はこの条件を採用することもあり得る。 As the product methane purge amount increases, the product methane concentration increases and reaches 98 vol% at 8 m 3 N / h. However, since the methane once recovered is used as the purge gas, the methane recovery rate is reduced to 86%. On the other hand, when the product methane purge amount is reduced to 2 m3 N / h, the product methane concentration decreases to 84%. Since the recovery rate increases to 94%, this condition may be adopted when a high methane concentration is not required.

ここまでの製品メタン回収は全て吸着工程終了後の吸着塔（吸着圧力１２０ｋＰＡ）と再生終了後の吸着塔（再生圧力５ｋＰａ）を後方で結んで、塔内圧力を６２．５ｋＰａ程度にする塔間均圧を採用した。ここで塔間均圧を採用せず、吸着工程終了後減圧工程に移行し、一方で再生工程終了後昇圧工程に移行した場合との、製品メタン濃度、製品メタン回収率の関係を調べた。結果を第８表に示す。   All of the product methane recovery so far is between the towers by connecting the adsorption tower (adsorption pressure 120 kPa) after completion of the adsorption process and the adsorption tower (regeneration pressure 5 kPa) after the regeneration to make the pressure in the tower about 62.5 kPa. A pressure equalization was adopted. Here, the relationship between the product methane concentration and the product methane recovery rate with the case of shifting to the depressurization step after the end of the adsorption step and shifting to the pressurization step after the end of the regeneration step was examined without adopting the uniform pressure between the columns. The results are shown in Table 8.

Figure 2008045060
Figure 2008045060

塔間均圧が無い場合は製品メタン濃度は９４ｖｏｌ％に上昇するが、製品メタン回収率は７２％に留まる。一方これまで紹介した塔間均圧を採用すると製品メタン濃度は９２ｖｏｌ％と若干低下するが、回収率は９２％と非常に高い。塔間均圧は吸着−脱着−吸着の圧力変化を容易に移行できるので、回収率の向上、円滑なＰＳＡ操作の観点から非常に有効であることが判る。   When there is no inter-column pressure, the product methane concentration increases to 94 vol%, but the product methane recovery rate remains at 72%. On the other hand, if the uniform pressure between the columns introduced so far is adopted, the product methane concentration is slightly reduced to 92 vol%, but the recovery rate is very high at 92%. It can be understood that the uniform pressure between the columns can be easily transferred from the pressure change of adsorption-desorption-adsorption, and is very effective from the viewpoint of improving the recovery rate and smooth PSA operation.

実施例４
第１実施例に於いては「吸着工程」では塔間均圧−昇圧−吸着、「再生工程」では塔間均圧−減圧−向流パージで製品メタンの回収を行ったが、この方法では向流パージにおけるパージガスとして製品メタンを使用するため、製品メタンの損失が無視できない。メタンの損失を避ける方法としては、「再生工程」において吸着工程終了後の吸着塔に塔前方からＣＯ２を主成分とする脱着ガスでパージすると吸着塔に残留するメタンがＣＯ２と置換して、塔後方からメタンが流過し、脱着工程に於けるメタンの損失が著しく低下する。 Example 4
In the first embodiment, the product adsorption of methane was performed in the "adsorption process" by means of pressure equalization-pressure increase-adsorption between the columns, and in the "regeneration process", the pressure in the column was reduced by pressure reduction-counterflow. Since product methane is used as the purge gas in the countercurrent purge, the loss of product methane cannot be ignored. As a method for avoiding the loss of methane, in the “regeneration process”, when the adsorption tower after the adsorption process is purged with a desorption gas mainly composed of CO 2 from the front of the tower, the methane remaining in the adsorption tower is replaced with CO 2. Methane flows from the back of the tower, and the loss of methane in the desorption process is significantly reduced.

この時の装置のフローシートを第２図に、装置フローシ−トを第９表に示す。   The flow sheet of the apparatus at this time is shown in FIG. 2, and the apparatus flow sheet is shown in Table 9.

Figure 2008045060
Figure 2008045060

図中第１図と同一の番号は同一の部品を示す。第２図において吸着工程終了後のＢ塔に脱着ガスタンク１４から真空ポンプ１１をブロワーとして使用し、バルブ１５，１６，１９、９ｂ、２０ｂを開くと塔に残留する製品メタンが流過して流路２１から流路１に還流して回収される。   In the figure, the same reference numerals as those in FIG. 1 denote the same parts. In FIG. 2, when the vacuum pump 11 is used as a blower from the desorption gas tank 14 and the valves 15, 16, 19, 9b, and 20b are opened, the product methane remaining in the tower flows through the tower B after completion of the adsorption process. It is refluxed from the channel 21 to the channel 1 and collected.

この操作を並流パージと呼ぶが脱着ガス量をＧ２（ｍ３Ｎ／ｈ），並流パージガス流量をＧ４（ｍ３Ｎ／ｈ）とすると並流パージ率Ｋを、
Ｋ ＝ Ｇ４／Ｇ２
で定義する。なお脱着ガス量Ｇ３はＧ３＝Ｇ２−Ｇ４である。 This operation is called a cocurrent purge. If the desorption gas amount is G2 (m3N / h) and the cocurrent purge gas flow rate is G4 (m3N / h), the cocurrent purge rate K is
K = G4 / G2
Define in. The desorption gas amount G3 is G3 = G2-G4.

ここで並流パージ率と製品メタン濃度、製品メタン回収率の関係を調べた。結果を第１０表に示す。   Here, the relationship between the cocurrent purge rate, product methane concentration, and product methane recovery rate was investigated. The results are shown in Table 10.

Figure 2008045060
Figure 2008045060

並流パージ率の増加に伴ない、製品メタン回収率は上昇し、並流パージ率７０％で回収率は９８％に達する。しかし並流パージ率の増大で製品メタン濃度も低下するので並流パージ率の最大値は７０％程度にとどめるべきである。   As the co-current purge rate increases, the product methane recovery rate increases, reaching a co-current purge rate of 70% and a recovery rate of 98%. However, since the product methane concentration decreases as the cocurrent purge rate increases, the maximum value of the cocurrent purge rate should be limited to about 70%.

バイオ発酵ガスを含む排気ガスより廃棄物を除去することができ、廃棄物を外部に排出しない。また、メタンを有効に回収し、燃料その他に資源として有効利用することができる。   Waste can be removed from exhaust gas containing biofermentation gas, and waste is not discharged outside. In addition, methane can be effectively recovered and used effectively as a resource for fuel and others.

本発明の第一の実施態様を示す。1 shows a first embodiment of the present invention. 本発明の第二の実施態様を示す。2 shows a second embodiment of the present invention.

符号の説明Explanation of symbols

４ａ、４ｂ 充填塔
５ 吸着剤ハニカム
１２ 製品タンク
１４ 脱着ガスタンク
１８ 減圧弁 4a, 4b packed tower 5 adsorbent honeycomb 12 product tank 14 desorption gas tank 18 pressure reducing valve

Claims (5)

有機廃棄物を嫌気性発酵させることによって発生されたバイオガスを圧力スイング法によってメタンガスを回収し、精製する方法であって、下記の工程：
（１）バイオガスを昇圧して吸着塔に供給し、
（２）水分、ＣＯ２及びシロキサン、硫化水素、メチルメルカプタンの中の少なくとも一種以上を含有するメタンガスを水分吸着剤、シロキサン吸着剤として酸処理したシリカゲル、硫化水素、メチルメルカプタン吸着剤としてシリカライト又は酸処理を施したシリカライト、ＣＯ２吸着剤として結晶表面にシリカコートを施したＣａ−Ａ又はＮａ−Ａ型ゼオライトを使用し、相対的高圧条件で水分、シロキサン、硫化水素、メチルメルカプタン、水分を先ず吸着させて、次いでＣＯ２を吸着させてメタンと分離した後、水分、シロキサン、硫化水素、メチルメルカプタン、ＣＯ２を吸着した当該吸着剤を相対的低圧条件に導いて離脱することによる、メタンと水分、シロキサン、硫化水素、メチルメルカプタンの少なくとも１種以上の共存ガスとの圧力スイング法によるメタンの回収、精製方法。 A method of recovering and purifying methane gas from a biogas generated by anaerobic fermentation of organic waste by a pressure swing method, the following steps:
(1) Pressurize the biogas and supply it to the adsorption tower.
(2) Silicalite or hydrogen sulfide, silica gel treated with acid as a moisture adsorbent, siloxane adsorbent, methane gas containing at least one of moisture, CO 2 and siloxane, hydrogen sulfide, methyl mercaptan or silicalite as a methyl mercaptan adsorbent Silicalite with acid treatment, Ca-A or Na-A type zeolite with silica coating on the crystal surface as CO 2 adsorbent, moisture, siloxane, hydrogen sulfide, methyl mercaptan, moisture under relative high pressure conditions By first adsorbing, then adsorbing CO 2 and separating it from methane, and then introducing the adsorbent adsorbing moisture, siloxane, hydrogen sulfide, methyl mercaptan, CO 2 to a relatively low pressure condition and releasing it. A combination of methane and moisture, at least one of siloxane, hydrogen sulfide, and methyl mercaptan. Recovery and purification method of methane by pressure swing method with existing gas. 請求項１工程で大気圧近傍で水分、シロキサン、硫化水素、メチルメルカプタン、ＣＯ２を吸着せしめ、真空減圧条件で脱着せしめるメタンと共存ガスとの圧力スイング法による分離方法。 A method for separating water by adsorbing moisture, siloxane, hydrogen sulfide, methyl mercaptan, and CO 2 in the vicinity of atmospheric pressure in the first step, and methane and coexisting gas that are desorbed under vacuum decompression conditions. 吸着工程終了後の相対的高圧の当該吸着剤で充填された１塔と脱着工程終了後の相対的低圧の当該吸着剤で充填された他塔を塔後方で結んで、吸着工程終了後の１塔から残留するメタンを脱着工程終了後の他塔に移行してメタン回収率を向上する共存ガスとの圧力スイング法による分離方法。   One column filled with the adsorbent at a relatively high pressure after completion of the adsorption step and another column filled with the adsorbent at a relatively low pressure after the completion of the desorption step are connected at the rear of the column. Separation method by pressure swing method with coexisting gas to improve methane recovery rate by transferring methane remaining from tower to other tower after completion of desorption process. 脱着したＣＯ２を主成分とするガスを吸着工程終了後の当該吸着剤吸着塔に塔前方から供給して塔内に残留するメタンを塔後方からパージしてパージガスを原料ラインに還流してメタン回収率を向上する共存ガスとの圧力スイング法による分離方法。 A gas mainly composed of desorbed CO 2 is supplied to the adsorbent adsorption tower after the adsorption step from the front of the tower, methane remaining in the tower is purged from the rear of the tower, and a purge gas is refluxed to the raw material line to methane. Separation method by pressure swing method with coexisting gas to improve recovery. バイオ発酵ガスが、水分、ＣＯ２、シロキサン、硫化水素、メチルメルカプタン及びメタンを含有する請求項１記載の精製方法。 Biofermentation gas, water, CO 2, siloxane, hydrogen sulfide, the purification method according to claim 1, further comprising the methyl mercaptan and methane.
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