TWI521056B - Methane recovery method and methane recovery unit - Google Patents
Methane recovery method and methane recovery unit Download PDFInfo
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- TWI521056B TWI521056B TW100149838A TW100149838A TWI521056B TW I521056 B TWI521056 B TW I521056B TW 100149838 A TW100149838 A TW 100149838A TW 100149838 A TW100149838 A TW 100149838A TW I521056 B TWI521056 B TW I521056B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C9/02—Aliphatic saturated hydrocarbons with one to four carbon atoms
- C07C9/04—Methane
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
- C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
- C01B3/26—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
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- 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
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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
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- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/20—Sludge processing
Description
本發明係關於一種回收生物氣體中所含有之甲烷的甲烷回收方法，尤其是關於一種自生物氣體除去雜質並以較高之回收率回收甲烷的甲烷回收方法及甲烷回收裝置。The present invention relates to a method for recovering methane from methane contained in a biogas, and more particularly to a methane recovery method and a methane recovery device for removing impurities from a biogas and recovering methane at a higher recovery rate.
生物氣體係藉由有機性資源之厭氧性醱酵等而生成，其組成一般以甲烷為主要成分，並含有二氧化碳及其他微量之氧、氮、硫化氫、矽氧烷等，且除去硫化氫、矽氧烷等有害雜質而用作鍋爐之熱源或發電機之燃料等。Biogas system is produced by anaerobic fermentation of organic resources, and its composition is generally composed of methane as a main component, and contains carbon dioxide and other traces of oxygen, nitrogen, hydrogen sulfide, helium oxide, etc., and removes hydrogen sulfide. It is used as a heat source for boilers or a fuel for generators, such as helium oxides.
先前，生物氣體中所含有之雜質係藉由以下除去方法而除去：藉由高壓水吸收法使CO2、硫系雜質溶解於水中(例如參照日本專利特開2006-95512號公報)，或使其吸附於吸附劑(例如參照日本專利特開2002-60767號公報)，或使其作為反應生成物而除去(例如參照日本專利特開2003-277779號公報)，或藉由多級分離膜而使其分離(例如參照日本專利特開2009-242773號公報)等。Previously, the impurities contained in the biogas were removed by the following removal method: CO 2 and sulfur-based impurities were dissolved in water by a high-pressure water absorption method (for example, refer to Japanese Laid-Open Patent Publication No. 2006-95512), or It is adsorbed to the adsorbent (for example, refer to JP-A-2002-60767), or is removed as a reaction product (for example, refer to Japanese Patent Laid-Open Publication No. 2003-277779), or by a multi-stage separation membrane. This is separated (for example, refer to Japanese Laid-Open Patent Publication No. 2009-242773).
又，如日本專利特開2006-16439號公報中所記載般，將以Li及Ca等作為交換陽離子之X型沸石作為二氧化碳吸附劑而填充至吸附塔，藉由變壓式吸附法除去二氧化碳及水而濃縮甲烷。Further, as described in Japanese Laid-Open Patent Publication No. 2006-16439, X-type zeolite containing Li and Ca as exchange cations is filled as a carbon dioxide adsorbent in an adsorption column, and carbon dioxide is removed by a pressure swing adsorption method. Methane is concentrated by water.
由於甲烷等以可燃性氣體為主要成分之氣體係用於燃燒用途，故於自生物氣體獲得之氣體中，可不含硫化氫等有害物質，而即便含有氧亦無任何問題。因此，先前，以甲烷為主要成分之生物氣體中所含之氧並非除去之對象。Since a gas system containing a combustible gas as a main component such as methane is used for combustion, the gas obtained from the biogas can contain no harmful substances such as hydrogen sulfide, and there is no problem even if it contains oxygen. Therefore, previously, the oxygen contained in the biogas containing methane as a main component is not the object of removal.
假設因某些原因而嘗試降低生物氣體中之氧含量時，使用觸媒使氧與甲烷反應，但是，若溫度未達約380℃以上，則使用了觸媒之甲烷與氧之反應無法充分產生，故為了加熱氣體而必需極大能量。If it is attempted to reduce the oxygen content in the biogas for some reason, the catalyst is used to react oxygen with methane. However, if the temperature is less than about 380 ° C, the reaction between methane and oxygen using the catalyst cannot be sufficiently produced. Therefore, in order to heat the gas, great energy is required.
又，提出有藉由精製生物氣體以除去二氧化碳等而製成以甲烷為主要成分之氣體，作為汽車及家庭用發電機等之燃料電池用燃料氣體而加以利用。就生物氣體之有效利用之觀點而言，較佳為使精製之生物氣體與主要包含天然氣之都市氣體混合。Further, it has been proposed to produce a gas containing methane as a main component by purifying a biogas to remove carbon dioxide or the like, and to use it as a fuel gas for a fuel cell such as an automobile or a household generator. From the viewpoint of efficient use of biogas, it is preferred to mix the purified biogas with an urban gas mainly containing natural gas.
然而，於作為燃料電池用燃料氣體而利用之情形時，由於氧會促進對天然氣進行水蒸氣改質之觸媒的劣化，故必須限制作為家庭用發電機之燃料而利用的都市氣體之氧含量。因此，於將精製之生物氣體與都市氣體混合之情形時，為了確保燃料氣體之品質，必須將生物氣體之氧含有率降低至未達10莫耳ppm。However, when it is used as a fuel gas for a fuel cell, since oxygen promotes deterioration of a catalyst for reforming natural gas by steam, it is necessary to limit the oxygen content of the city gas used as a fuel for a household generator. . Therefore, in the case where the purified biogas is mixed with the city gas, in order to secure the quality of the fuel gas, it is necessary to reduce the oxygen content of the biogas to less than 10 mol ppm.
此處，由於即便於高壓下氧溶於水之溶解度亦較小，故於如日本專利特開2006-95512號公報之高壓水吸收法中，氧與甲烷之分離在原理上便較為困難。又，於藉由如日本專利特開2002-60767號公報、日本專利特開2003-277779號公報、日本專利特開2009-242773號公報及日本專利特開2006-16439號公報之分離技術而分離氧之情形時，甲烷之回收率較低。Here, since the solubility of oxygen in water is small even under high pressure, the separation of oxygen and methane is difficult in principle in the high-pressure water absorption method of JP-A-2006-95512. Further, it is separated by a separation technique such as Japanese Patent Laid-Open Publication No. 2002-60767, Japanese Patent Laid-Open No. 2003-277779, Japanese Patent Laid-Open Publication No. 2009-242773, and Japanese Patent Laid-Open Publication No. Hei No. 2006-16439. In the case of oxygen, the recovery of methane is low.
本發明之目的在於提供一種可將氧抑制至特定含量以下、並且以較高之回收率自生物氣體回收甲烷的甲烷回收方法及甲烷回收裝置。It is an object of the present invention to provide a methane recovery method and a methane recovery apparatus which can suppress oxygen to a specific content or less and recover methane from a biogas at a high recovery rate.
本發明係一種甲烷回收方法，其特徵在於：其係自以甲烷為主要成分、並含有至少氧為雜質之生物氣體回收甲烷者，其包括：吸附除去步驟，其使生物氣體中之矽氧烷吸附於吸附劑而除去；反應除去步驟，其使生物氣體中之硫化氫與金屬氧化物反應，並作為金屬硫化物而除去；捕捉步驟，其使生物氣體中之氧與銅-氧化鋅反應，並作為氧化銅而捕捉；及濃縮步驟，其藉由變壓式吸附法使生物氣體中之二氧化碳分離而濃縮甲烷；藉由進行吸附除去步驟、反應除去步驟、捕捉步驟及濃縮步驟而自生物氣體回收甲烷。The present invention relates to a method for recovering methane, which is characterized in that it recovers methane from a biogas containing methane as a main component and containing at least oxygen as an impurity, and includes: an adsorption removal step for causing a helium alkane in the biogas The reaction is removed by adsorption to an adsorbent; the hydrogen sulfide in the biogas is reacted with the metal oxide and removed as a metal sulfide; and the capturing step is performed to react oxygen in the biogas with copper-zinc oxide. And capturing as copper oxide; and a concentration step of separating carbon dioxide in the biogas by a pressure swing adsorption method to concentrate methane; and performing the adsorption removal step, the reaction removal step, the capture step, and the concentration step from the biogas Recover methane.
根據本發明，藉由吸附除去步驟使生物氣體中之矽氧烷吸附於吸附劑而除去，並藉由反應除去步驟使生物氣體中之硫化氫與金屬氧化物反應並作為金屬硫化物而除去。於捕捉步驟中，使生物氣體中之氧與銅-氧化鋅反應並作為氧化銅而捕捉。於濃縮步驟中，藉由變壓式吸附法將生物氣體中之二氧化碳分離而濃縮甲烷。According to the present invention, the helium alkane in the biogas is removed by adsorption to the adsorbent by the adsorption removal step, and the hydrogen sulfide in the biogas is reacted with the metal oxide by the reaction removal step and removed as a metal sulfide. In the capturing step, oxygen in the biogas is reacted with copper-zinc oxide and captured as copper oxide. In the concentration step, methane is removed by separating the carbon dioxide in the biogas by a pressure swing adsorption method.
藉由進行該等各步驟，可將氧抑制至特定含量以下、例如10 ppm以下，並且以較高之回收率自生物氣體回收甲烷。By performing these steps, oxygen can be suppressed to a specific content or less, for example, 10 ppm or less, and methane can be recovered from the biogas at a higher recovery rate.
又，於本發明中，較佳為，於上述捕捉步驟中，於200℃～300℃之溫度條件下使被處理氣體與銅-氧化鋅接觸。Further, in the invention, it is preferable that the gas to be treated is brought into contact with copper-zinc oxide at a temperature of from 200 ° C to 300 ° C in the above-described capturing step.
根據本發明，於上述捕捉步驟中，於200℃～300℃之溫度條件下使被處理氣體與銅-氧化鋅接觸。According to the invention, in the above-described capturing step, the gas to be treated is brought into contact with copper-zinc oxide at a temperature of from 200 ° C to 300 ° C.
藉此，相較於使氧與甲烷反應之方法，可以較低之溫度自生物氣體除去氧。Thereby, oxygen can be removed from the biogas at a lower temperature than the method of reacting oxygen with methane.
又，於本發明中，較佳為，於上述濃縮步驟中，利用加壓使生物氣體中之二氧化碳吸附於吸附劑，並藉由設為大氣壓而使二氧化碳自吸附劑脫離。Further, in the present invention, it is preferable that in the concentration step, carbon dioxide in the biogas is adsorbed to the adsorbent by pressurization, and carbon dioxide is released from the adsorbent by being atmospheric pressure.
根據本發明，於上述濃縮步驟中，由於利用加壓使生物氣體中之二氧化碳吸附於吸附劑，並藉由設為大氣壓而使二氧化碳自吸附劑脫離，故可高效地分離二氧化碳。According to the present invention, in the concentration step, since carbon dioxide in the biogas is adsorbed to the adsorbent by pressurization, and carbon dioxide is released from the adsorbent by being at atmospheric pressure, carbon dioxide can be efficiently separated.
又，於本發明中，較佳為，上述捕捉步驟於上述反應除去步驟之後進行。Further, in the invention, it is preferred that the capturing step is performed after the reaction removing step.
根據本發明，於上述捕捉步驟中，由於導入除去了硫化氫之生物氣體，故不存在硫化氫與銅-氧化鋅反應，從而不會阻礙氧與銅-氧化鋅之反應。According to the present invention, in the above-described capturing step, since the biogas from which hydrogen sulfide is removed is introduced, there is no reaction between hydrogen sulfide and copper-zinc oxide, so that the reaction between oxygen and copper-zinc oxide is not inhibited.
又，本發明係一種甲烷回收裝置，其特徵在於：其係自以甲烷為主要成分、並含有至少氧為雜質之生物氣體回收甲烷者，其包括：吸附塔，其使生物氣體中之矽氧烷吸附於吸附劑而除去；硫化氫反應塔，其使生物氣體中之硫化氫與金屬氧化物反應，並作為金屬硫化物而除去；脫氧反應塔，其使生物氣體中之氧與銅-氧化鋅反應，並作為氧化銅而捕捉；及變壓式吸附裝置，其藉由變壓式吸附法使生物氣體中之二氧化碳分離而濃縮甲烷；藉由使吸附塔、硫化氫反應塔、脫氧反應塔及變壓式吸附裝置運作而自生物氣體回收甲烷。Further, the present invention is a methane recovery apparatus characterized in that it recovers methane from a biogas containing methane as a main component and containing at least oxygen as an impurity, and includes: an adsorption tower which causes helium in a biogas The alkane is adsorbed to the adsorbent to remove; the hydrogen sulfide reaction tower, which causes the hydrogen sulfide in the biogas to react with the metal oxide and is removed as a metal sulfide; the deoxygenation reaction tower, which oxidizes oxygen and copper in the biogas Zinc reaction, and captured as copper oxide; and a pressure swing adsorption device that separates methane in a biogas by a pressure swing adsorption method to concentrate methane; by using an adsorption tower, a hydrogen sulfide reaction tower, and a deoxygenation reaction tower And the pressure swing adsorption device operates to recover methane from the biogas.
根據本發明，利用吸附塔使生物氣體中之矽氧烷吸附於吸附劑而除去，並利用硫化氫反應塔使生物氣體中之硫化氫與金屬氧化物反應並作為金屬硫化物而除去。利用脫氧反應塔，使生物氣體中之氧與銅-氧化鋅反應並作為氧化銅而捕捉。利用變壓式吸附裝置，藉由變壓式吸附法分離生物氣體中之二氧化碳而濃縮甲烷。According to the present invention, the helium alkane in the biogas is adsorbed to the adsorbent by the adsorption tower, and the hydrogen sulfide in the biogas is reacted with the metal oxide by the hydrogen sulfide reaction column to be removed as a metal sulfide. The oxygen in the biogas is reacted with copper-zinc oxide by a deoxidation reaction tower and captured as copper oxide. Methane is concentrated by separating the carbon dioxide in the biogas by a pressure swing adsorption method using a pressure swing adsorption device.
藉由使該等各塔及裝置運作，可將氧抑制至特定含量以下、例如10 ppm以下，並且以較高之回收率自生物氣體回收甲烷。By operating the columns and apparatus, oxygen can be suppressed to below a specified level, such as below 10 ppm, and methane is recovered from the biogas at a higher recovery.
又，於本發明中，較佳為，進而包括如下氫導入裝置：將氫導入至脫氧反應塔內，使藉由反應而生成之氧化銅還原。Moreover, in the present invention, it is preferable to further include a hydrogen introduction device that introduces hydrogen into the deoxidation reaction column to reduce copper oxide formed by the reaction.
根據本發明，由於氫導入裝置將氫導入至脫氧反應塔內，使藉由反應而生成之氧化銅還原，故可使氧化銅-氧化鋅再生為銅-氧化鋅。According to the present invention, since the hydrogen introduction device introduces hydrogen into the deoxidation reaction column and reduces the copper oxide formed by the reaction, the copper oxide-zinc oxide can be regenerated into copper-zinc oxide.
又，於本發明中，較佳為，將預先利用上述硫化氫反應塔除去了硫化氫之生物氣體導入至上述脫氧反應塔。Further, in the invention, it is preferable that the biogas from which hydrogen sulfide has been removed by the hydrogen sulfide reaction column in advance is introduced into the deoxygenation reaction column.
根據本發明，由於將預先利用上述硫化氫反應塔除去了硫化氫之生物氣體導入至上述脫氧反應塔，故硫化氫不與上述脫氧反應塔內之銅-氧化鋅反應，從而不會阻礙氧與銅-氧化鋅之反應。According to the present invention, since the biogas from which the hydrogen sulfide has been removed in advance using the hydrogen sulfide reaction column is introduced into the deoxidation reaction column, the hydrogen sulfide does not react with the copper-zinc oxide in the deoxidation reaction column, thereby preventing oxygen and Copper-zinc oxide reaction.
本發明之目的、特點及優點可藉由下述之詳細說明與圖式而明確。The objects, features, and advantages of the invention will be apparent from the description and drawings.
以下，以圖式為參考，對本發明之較佳實施形態進行詳細說明。Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings.
本發明係自生物氣體回收甲烷之回收方法。生物氣體係自例如污水處理場之污泥等中產生之氣體，其主要成分包含約60莫耳%之甲烷及約40莫耳%之二氧化碳，除此以外含有微量之氧、氮、硫化氫及矽氧烷等。The present invention is a method for recovering methane from biogas. The biogas system is produced from a sludge such as a sewage treatment plant, and the main component thereof contains about 60 mol% of methane and about 40 mol% of carbon dioxide, and contains a trace amount of oxygen, nitrogen, hydrogen sulfide, and the like. Oxane and the like.
於使用生物氣體作為汽車用或都市氣體用氣體之情形時，甲烷濃度較佳為95莫耳%以上。於作為汽車用氣體而利用之情形時，由於係壓縮而使用，故必須避免作為生物氣體之主要雜質之二氧化碳壓縮而液化，因此需要甲烷濃度為95莫耳%以上。又，於作為都市氣體用氣體而利用之情形時，若濃度較低則熱量較低，故與汽車用一樣，需要甲烷濃度為95莫耳%以上。When biogas is used as a gas for automobile or city gas, the methane concentration is preferably 95 mol% or more. When it is used as a gas for automobiles, since it is used for compression, it is necessary to prevent carbon dioxide which is a main impurity of biogas from being compressed and liquefied. Therefore, the methane concentration is required to be 95 mol% or more. Further, when it is used as a gas for a city gas, if the concentration is low, the amount of heat is low. Therefore, like the automobile, the methane concentration is required to be 95 mol% or more.
以往，雖然生物氣體係作為用以燃燒之燃料氣體而利用，故不存在將氧作為雜質而除去之情形，但於面向燃料電池之利用中，由於生物氣體中所含之氧會使水蒸氣改質用之觸媒劣化，故必須除去氧。根據本發明，可將氧抑制至特定含量以下、例如10 ppm以下，並且以較高之回收率、例如80%以上之回收率回收甲烷。Conventionally, although the biogas system is used as a fuel gas for combustion, there is no case where oxygen is removed as an impurity. However, in the use of a fuel cell, the oxygen contained in the biogas changes the water vapor. The catalyst used for the deterioration is degraded, so oxygen must be removed. According to the present invention, oxygen can be suppressed to a specific content or less, for example, 10 ppm or less, and methane can be recovered at a higher recovery rate, for example, a recovery rate of 80% or more.
圖1係表示作為本發明之實施之一形態之甲烷回收方法的步驟圖。本發明之甲烷回收方法包括：吸附除去步驟，其為了自生物氣體除去雜質、並以較高之回收率回收甲烷而(步驟S1)除去矽氧烷；反應除去步驟，其(步驟S2)除去硫化氫；捕捉步驟，其(步驟S3)捕捉氧；及濃縮步驟，其(步驟S4)濃縮甲烷。Fig. 1 is a view showing a step of a method for recovering methane as one embodiment of the present invention. The methane recovery method of the present invention comprises: an adsorption removal step for removing impurities from the biogas and recovering methane at a higher recovery rate (step S1) to remove the oxime; a reaction removal step, which (step S2) removes the vulcanization Hydrogen; a capture step of (step S3) capturing oxygen; and a concentration step (step S4) of concentrating methane.
(步驟S1)吸附除去步驟(Step S1) adsorption removal step
於吸附除去步驟中，藉由將吸附劑填充至吸附塔並將生物氣體導入至吸附塔內，而使作為生物氣體中所含之雜質之矽氧烷吸附於吸附劑，從而自生物氣體中除去矽氧烷。作為吸附劑，係易於吸附矽氧烷者，亦可係不易吸附甲烷者，例如使用活性炭。活性炭雖然可使用椰殼及木炭等天然活性炭、瀝青及石油焦等礦物活性炭等，但由於活性炭無法再生而須更換新劑，故較佳為儘量採用廉價之椰殼活性炭。In the adsorption removal step, the adsorbent is filled into the adsorption tower and the biogas is introduced into the adsorption tower, so that the helium which is an impurity contained in the biogas is adsorbed to the adsorbent, thereby being removed from the biogas. Oxane. As the adsorbent, those which are easy to adsorb oxime or those which do not easily adsorb methane, for example, use activated carbon. Although activated carbon, such as natural activated carbon such as coconut shell and charcoal, mineral activated carbon such as pitch and petroleum coke, can be used, since the activated carbon cannot be regenerated and a new agent has to be replaced, it is preferable to use cheap coconut shell activated carbon as much as possible.
較佳為，藉由吸附除去步驟將生物氣體中之矽氧烷之含量設為2 mg/Nm3以下，更佳為1 mg/Nm3以下。Preferably, the content of the oxoxane in the biogas is 2 mg/Nm 3 or less, more preferably 1 mg/Nm 3 or less by the adsorption removal step.
(步驟S2)反應除去步驟(Step S2) Reaction removal step
於反應除去步驟中，藉由將金屬氧化物填充至反應塔並將生物氣體導入至吸附塔內，而將生物氣體中所含之雜質即硫化氫、硫醇等硫系化合物作為金屬硫化物而固定於反應塔內。作為金屬氧化物，可使用氧化鐵、氧化銅、氧化鋅等。例如，若該等金屬氧化物與硫化氫進行化學反應，則分別變為硫化鐵、硫化銅、硫化鋅等金屬硫化物。In the reaction removal step, a metal oxide is filled into the reaction column and the biogas is introduced into the adsorption tower, and a sulfur compound such as hydrogen sulfide or mercaptan contained in the biogas is used as the metal sulfide. It is fixed in the reaction tower. As the metal oxide, iron oxide, copper oxide, zinc oxide or the like can be used. For example, when the metal oxides are chemically reacted with hydrogen sulfide, they become metal sulfides such as iron sulfide, copper sulfide, and zinc sulfide.
較佳為藉由反應除去步驟將生物氣體中之硫化氫之含量設為3莫耳ppm以下，更佳為1莫耳ppm以下。The content of hydrogen sulfide in the biogas is preferably set to 3 mol ppm or less, more preferably 1 mol ppm or less by the reaction removal step.
藉由如上述般進行吸附除去步驟及反應除去步驟，可除去生物氣體中之矽氧烷及硫化氫。By carrying out the adsorption removal step and the reaction removal step as described above, the oxoxane and hydrogen sulfide in the biogas can be removed.
再者，吸附除去步驟與反應除去步驟中，可先進行任一步驟，並未特別限定步驟順序。Further, in the adsorption removal step and the reaction removal step, any step may be performed first, and the order of the steps is not particularly limited.
又，亦可於吸附除去步驟及反應除去步驟之前，進行壓縮生物氣體之壓縮步驟及除去生物氣體中之水分之除濕步驟。於除濕步驟中，例如，將生物氣體於0℃左右冷卻而脫水。又，亦可利用氧化鋁球、沸石(MS-3A)等吸附水分而脫水，亦可將氧化鋁球、沸石等水分吸附劑填充至吸附塔並導入生物氣體。進而，亦可將氧化鋁球、沸石等水分吸附劑填充至用以吸附除去矽氧烷之吸附塔，於進行吸附除去步驟之同時除濕。Further, before the adsorption removal step and the reaction removal step, a compression step of compressing the biogas and a dehumidification step of removing moisture in the biogas may be performed. In the dehumidifying step, for example, the biogas is cooled at about 0 ° C to be dehydrated. Further, it may be dehydrated by adsorbing moisture such as alumina balls or zeolite (MS-3A), or a moisture adsorbent such as alumina balls or zeolite may be filled in the adsorption tower to introduce biogas. Further, a moisture adsorbent such as alumina balls or zeolite may be filled in an adsorption tower for adsorbing and removing the decane, and dehumidification may be performed while performing the adsorption removal step.
(步驟S3)捕捉步驟(Step S3) Capture step
於捕捉步驟中，藉由將銅-氧化鋅之混合物作為氧捕獲劑填充至反應塔，並將除去了矽氧烷及硫化氫之生物氣體導入至吸附塔內，而將生物氣體中所含雜質之氧作為氧化銅加以捕捉。In the capturing step, the copper-zinc oxide mixture is filled into the reaction column as an oxygen scavenger, and the biogas from which the helium oxide and the hydrogen sulfide are removed is introduced into the adsorption tower to contain impurities contained in the biogas. The oxygen is captured as copper oxide.
銅-氧化鋅混合物與生物氣體接觸後，生物氣體中之氧與銅反應而成為氧化銅，並作為氧化銅-氧化鋅混合物而於反應塔內被捕捉。After the copper-zinc oxide mixture is brought into contact with the biogas, the oxygen in the biogas reacts with copper to form copper oxide, and is captured as a copper oxide-zinc oxide mixture in the reaction column.
於捕捉步驟中，使除去了矽氧烷及硫化氫之被處理氣體於200℃～300℃之溫度條件下與銅-氧化鋅接觸。於此情形時，即便二氧化碳以30～40%之比率共存於被處理氣體中，亦有可能產生氧化銅生成反應，故相較於使氧與甲烷反應而使氧含量降低之情形，可減少用以加熱被處理氣體之能量。In the capturing step, the gas to be treated from which helium oxide and hydrogen sulfide are removed is brought into contact with copper-zinc oxide at a temperature of from 200 ° C to 300 ° C. In this case, even if carbon dioxide coexists in the gas to be treated in a ratio of 30 to 40%, a copper oxide formation reaction may occur, so that the oxygen content may be lowered as compared with the reaction between oxygen and methane. To heat the energy of the gas being treated.
雖然銅-氧化鋅混合物可粒子化而直接填充至反應塔，但為了使其與導入至塔內之生物氣體之接觸效率提昇，較佳為使微粒子狀之銅-氧化鋅混合物擔載於氧化鋁、矽藻土等擔載體上而填充至反應塔。Although the copper-zinc oxide mixture can be directly filled into the reaction tower by particle formation, in order to improve the contact efficiency with the biogas introduced into the column, it is preferred to carry the particulate copper-zinc oxide mixture on the alumina. And a carrier such as diatomaceous earth is filled in the reaction tower.
於本發明之捕捉步驟中所使用之銅-氧化鋅混合物，係藉由利用惰性氣體稀釋後之氫氣將作為甲醇蒸汽重組觸媒而使用者還原而獲得之氧捕獲劑。例如，由於甲醇蒸汽重組觸媒有市售之氧化銅-氧化鋅擔載於氧化鋁上者，故使該甲醇蒸汽重組觸媒與利用氬、氮等惰性氣體稀釋至1～5%之氫氣於230～260℃之溫度條件下接觸，藉此氧化銅得以還原成為銅，並作為擔載於氧化鋁上之銅-氧化鋅混合物而獲得。The copper-zinc oxide mixture used in the capturing step of the present invention is an oxygen scavenger obtained by reduction of a hydrogen as a methanol vapor recombination catalyst by a hydrogen gas diluted with an inert gas. For example, since the methanol vapor recombination catalyst has a commercially available copper oxide-zinc oxide supported on alumina, the methanol vapor recombination catalyst is diluted with hydrogen gas of 1 to 5% by using an inert gas such as argon or nitrogen. The contact is carried out at a temperature of 230 to 260 ° C, whereby copper oxide is reduced to copper and obtained as a copper-zinc oxide mixture supported on alumina.
較佳為，藉由捕捉步驟將生物氣體中之氧含量設為10 ppm以下，更佳為1 ppm以下。Preferably, the oxygen content in the biogas is set to 10 ppm or less, more preferably 1 ppm or less by the capturing step.
此處，對用以除去硫化氫之反應除去步驟之實施效果、及其與捕捉氧之捕捉步驟之關聯性進行說明。Here, the effect of the reaction removal step for removing hydrogen sulfide and the correlation with the capture step of trapping oxygen will be described.
由於硫化氫等硫系化合物吸附於活性炭，故於用以除去矽氧烷之吸附除去步驟中，於使用活性炭作為吸附劑之情形時，雖然亦可除去些許硫化氫，但並不充分。於省略利用硫化氫與金屬氧化物之反應的反應除去步驟之情形時，捕捉步驟中之被處理氣體中會含有硫化氫。若銅-氧化鋅與硫化氫接觸，則硫化氫還原而產生硫，進而與氧反應而產生二氧化硫。又，氧化鋅與硫化氫反應而生成硫化鋅。如此，若捕捉步驟中之被處理氣體中含有硫化氫，則硫化氫會與銅-氧化鋅反應，故而阻礙氧與銅-氧化鋅之反應，從而無法充分捕捉氧。Since the sulfur-based compound such as hydrogen sulfide is adsorbed to the activated carbon, in the case of using the activated carbon as the adsorbent in the adsorption removal step for removing the deuterated alkane, a small amount of hydrogen sulfide may be removed, but it is not sufficient. In the case where the reaction removal step using the reaction of hydrogen sulfide with the metal oxide is omitted, the gas to be treated in the capturing step contains hydrogen sulfide. When copper-zinc oxide is brought into contact with hydrogen sulfide, hydrogen sulfide is reduced to generate sulfur, which in turn reacts with oxygen to generate sulfur dioxide. Further, zinc oxide reacts with hydrogen sulfide to form zinc sulfide. As described above, when hydrogen sulfide is contained in the gas to be treated in the capturing step, hydrogen sulfide reacts with copper-zinc oxide, thereby hindering the reaction between oxygen and copper-zinc oxide, and the oxygen cannot be sufficiently trapped.
為了使捕捉步驟中之氧與銅-氧化鋅充分反應而使氧含量為10 ppm以下，僅利用吸附除去步驟而吸附除去硫化氫並不充分，而利用硫化氫與金屬氧化物之反應的反應除去步驟則很有必要。In order to sufficiently react the oxygen in the capturing step with the copper-zinc oxide to have an oxygen content of 10 ppm or less, it is not sufficient to adsorb and remove hydrogen sulfide by only the adsorption removal step, and the reaction by the reaction of hydrogen sulfide with the metal oxide is removed. Steps are necessary.
(步驟S4)濃縮步驟(Step S4) Concentration step
藉由吸附除去步驟、反應除去步驟及捕捉步驟，充分地除去生物氣體中之雜質即矽氧烷、硫化氫及氧，而藉由濃縮步驟處理之被處理氣體僅包含甲烷與二氧化碳。於濃縮步驟中，藉由變壓式吸附法使二氧化碳吸附於吸附劑，從而獲得濃縮後之高純度甲烷。The impurities in the biogas, that is, helium oxide, hydrogen sulfide, and oxygen are sufficiently removed by the adsorption removal step, the reaction removal step, and the capture step, and the gas to be treated treated by the concentration step contains only methane and carbon dioxide. In the concentration step, carbon dioxide is adsorbed to the adsorbent by a pressure swing adsorption method to obtain concentrated high purity methane.
於變壓式吸附法中，例如為了自2種物質之混合氣體中濃縮而獲得1種氣體，使用吸附能力相對於一種物質較高而相對於另一種物質較低之吸附劑，於高壓下使一種物質吸附於吸附劑。其後，於低壓下使經吸附一種物質自吸附劑脫離，從而再生吸附劑。In the pressure swing adsorption method, for example, one gas is obtained by concentration in a mixed gas of two substances, and an adsorbent having a higher adsorption capacity relative to one substance and lower than the other substance is used, and the pressure is high under high pressure. A substance is adsorbed to the adsorbent. Thereafter, the adsorbed substance is detached from the adsorbent at a low pressure to regenerate the adsorbent.
於濃縮步驟中，將吸附二氧化碳之吸附能力相對較高、且吸附甲烷之吸附能力相對較低之吸附劑填充至複數個吸附塔，使塔內之壓力變化並且適時切換所使用之吸附塔，從而分離二氧化碳與甲烷，並回收高純度之甲烷。In the concentration step, the adsorbent having a relatively high adsorption capacity for adsorbing carbon dioxide and having a relatively low adsorption capacity for adsorbing methane is filled into a plurality of adsorption towers, so that the pressure in the column is changed and the adsorption tower used is switched at an appropriate timing, thereby Separate carbon dioxide from methane and recover high purity methane.
濃縮步驟係基於變壓式吸附法，反覆進行吸附操作與脫離操作。吸附操作係使填充有吸附劑之吸附塔內之壓力相對高於脫離操作時之壓力，於高壓條件下導入除去了矽氧烷、硫化氫及氧氣之生物氣體。於高壓條件下，雖然二氧化碳吸附於吸附劑，但甲烷幾乎不吸附於吸附劑，故於吸附塔內，二氧化碳與甲烷分離，獲得濃縮後之甲烷。若連續導入生物氣體至1個吸附塔內，則吸附劑中所吸附之二氧化碳増加，吸附能力下降，故藉由脫離操作再生吸附劑。The concentration step is based on a pressure swing adsorption method, and the adsorption operation and the detachment operation are repeated. The adsorption operation is such that the pressure in the adsorption column packed with the adsorbent is relatively higher than the pressure at the time of the desorption operation, and the biogas from which helium, hydrogen sulfide and oxygen are removed is introduced under high pressure. Under high pressure conditions, although carbon dioxide is adsorbed to the adsorbent, methane is hardly adsorbed to the adsorbent, so in the adsorption tower, carbon dioxide is separated from methane to obtain concentrated methane. When the biogas is continuously introduced into one adsorption tower, the carbon dioxide adsorbed in the adsorbent is increased, and the adsorption capacity is lowered, so that the adsorbent is regenerated by the detachment operation.
脫離操作係停止生物氣體之導入，並使吸附塔內之壓力相對低於吸附操作時之壓力，而使吸附劑中所吸附之二氧化碳自吸附劑脫離。脫離後之二氧化碳向吸附塔外排出。The detachment operation stops the introduction of the biogas and causes the pressure in the adsorption tower to be relatively lower than the pressure at the adsorption operation, so that the carbon dioxide adsorbed in the adsorbent is detached from the adsorbent. The carbon dioxide after the detachment is discharged to the outside of the adsorption tower.
於使用2個吸附塔之情形時，利用1個吸附塔進行脫離操作時，另一個吸附塔進行吸附操作，利用各個塔同時進行吸附操作與脫離操作。而且，於處理特定量之後，切換吸附操作與脫離操作。藉此，由於任一塔中必然進行著吸附操作，故可一面再生吸附劑，一面連續進行甲烷之分離濃縮。In the case where two adsorption towers are used, when one adsorption tower is used for the separation operation, the other adsorption tower performs the adsorption operation, and the adsorption operation and the separation operation are simultaneously performed by the respective columns. Moreover, after processing a certain amount, the adsorption operation and the detachment operation are switched. Thereby, since the adsorption operation is inevitably carried out in any of the columns, the separation and concentration of methane can be continuously performed while regenerating the adsorbent.
作為二氧化碳之吸附能力較高、甲烷之吸附能力較低之吸附劑，可使用碳系吸附劑，較佳為碳分子篩。進而，於根據目標產品氣體組成，例如欲降低產品氣體之所含氮濃度之情形時，於原料氣體之所含氮濃度較高時等必須除去氮之情形時，除碳分子篩以外亦可積層沸石。As the adsorbent having a high adsorption capacity of carbon dioxide and a low adsorption capacity of methane, a carbon-based adsorbent, preferably a carbon molecular sieve, can be used. Further, when the nitrogen content of the product gas is to be lowered according to the gas composition of the target product, for example, when nitrogen is necessary to be removed when the nitrogen concentration of the material gas is high, the zeolite may be laminated in addition to the carbon molecular sieve. .
作為吸附操作中之塔內之壓力P1，例如為大氣壓(0.101 MPa)～4.0 MPa。作為脫離操作中之塔內之壓力P2，例如為0.001～0.3 MPa(其中，P1＞P2)。The pressure P1 in the column in the adsorption operation is, for example, atmospheric pressure (0.101 MPa) to 4.0 MPa. The pressure P2 in the column in the detachment operation is, for example, 0.001 to 0.3 MPa (where P1 > P2).
如上述般經各步驟而獲得之氣體中，氧含量為10 ppm以下，從而獲得甲烷純度例如為98莫耳%以上之富甲烷氣體。The gas obtained by each step as described above has an oxygen content of 10 ppm or less, thereby obtaining a methane-rich gas having a methane purity of, for example, 98 mol% or more.
繼而，對本發明之自生物氣體回收甲烷之回收裝置進行說明。本發明之回收裝置，只要係能實施上述回收方法之裝置，則可為任意構成。Next, the apparatus for recovering methane recovered from biogas according to the present invention will be described. The recovery apparatus of the present invention may be of any configuration as long as it is a device capable of carrying out the above-described recovery method.
圖2係表示作為本發明之實施之一形態的回收裝置100之構成的概略圖。回收裝置100包括壓縮機1、除濕裝置2、矽氧烷吸附塔3、硫化氫反應塔4、脫氧反應塔5及變壓式吸附裝置6，並處理自氣體供給源7供給之生物氣體。氣體供給源7係例如污水處理場等產生生物氣體之產生源。Fig. 2 is a schematic view showing the configuration of a recovery apparatus 100 which is one embodiment of the present invention. The recovery device 100 includes a compressor 1, a dehumidification device 2, a helium-oxygen adsorption column 3, a hydrogen sulfide reaction column 4, a deoxidation reaction column 5, and a pressure swing adsorption device 6, and processes the biogas supplied from the gas supply source 7. The gas supply source 7 is a source for generating a biogas such as a sewage treatment plant.
自氣體供給源7供給之包含雜質之生物氣體係藉由壓縮機1壓縮，並送往用以除去水分之除濕裝置2。作為除濕裝置，例如可使用冷卻式脫水機、加壓吸附式脫水機、加熱再生式脫水機等，但較佳為將生物氣體於0℃左右冷卻而脫水之冷卻式脫水機。又，亦可使用填充有氧化鋁球或沸石(MS-3A)等水分吸附劑之吸附塔作為用以吸附脫水之、非使用脫水機之除濕裝置2。又，根據水分量，亦可於用以吸附矽氧烷之矽氧烷吸附塔3之後的各塔內，積層填充氧化鋁球、沸石等水分吸附劑。The biogas system containing impurities supplied from the gas supply source 7 is compressed by the compressor 1 and sent to the dehumidifying device 2 for removing moisture. As the dehumidifying apparatus, for example, a cooling type dehydrator, a pressure adsorption type dehydrator, a heating regenerative dehydrator or the like can be used, but a cooling type dehydrator in which biogas is cooled and dehydrated at about 0 ° C is preferable. Further, an adsorption tower filled with a water adsorbent such as alumina balls or zeolite (MS-3A) may be used as the dehumidifying apparatus 2 for adsorbing dehydration and not using a dehydrator. Further, depending on the amount of water, a moisture adsorbent such as alumina balls or zeolite may be laminated in each of the columns after the helium oxide adsorption column 3 for adsorbing helium oxide.
吸附除去矽氧烷之矽氧烷吸附塔3，係如吸附除去步驟中所說明般，將例如活性炭填充至吸附塔內作為用以吸附矽氧烷之吸附劑。反應除去硫化氫之硫化氫反應塔4，係如反應除去步驟中所說明般，將與硫化氫反應生成金屬硫化物之金屬氧化物填充至反應塔內。The azide adsorption column 3 for adsorbing and removing the azide is filled with, for example, activated carbon into the adsorption column as an adsorbent for adsorbing the siloxane, as described in the adsorption removal step. The hydrogen sulfide reaction column 4 for removing hydrogen sulfide is charged into a reaction column by reacting a metal oxide which reacts with hydrogen sulfide to form a metal sulfide as described in the reaction removal step.
將除去了矽氧烷與硫化氫之生物氣體導入至脫氧反應塔5。如捕捉步驟中所說明般，將銅-氧化鋅混合物以擔載於例如氧化鋁等擔載體上之形態而填充至脫氧反應塔5。導入後之生物氣體中所含之氧與銅-氧化鋅混合物之銅反應，並作為氧化銅而被捕捉。此時，脫氧反應塔5內係藉由未圖示之加熱器加熱至200～300℃。The biogas from which helium oxide and hydrogen sulfide have been removed is introduced into the deoxygenation reaction column 5. As described in the capturing step, the copper-zinc oxide mixture is charged to the deoxygenation reaction column 5 in a form supported on a support such as alumina. The oxygen contained in the introduced biogas reacts with the copper of the copper-zinc oxide mixture and is captured as copper oxide. At this time, the inside of the deoxidation reaction tower 5 is heated to 200 to 300 ° C by a heater (not shown).
較佳為進而包括如下氫導入裝置5a：將氫導入至脫氧反應塔5之塔內而還原氧化銅-氧化鋅，從而再生銅-氧化鋅。例如，設置利用自脫氧反應塔5之出口返回至入口之循環路徑的氮氣之旋轉鼓風機，可藉由氫導入裝置5a將氫添加至氮氣中，從而向脫氧反應塔5內提供再生用氫氣。It is preferable to further include a hydrogen introduction device 5a that introduces hydrogen into a column of the deoxygenation reaction column 5 to reduce copper oxide-zinc oxide, thereby regenerating copper-zinc oxide. For example, a rotary blower for nitrogen gas which is returned to the circulation path of the inlet from the outlet of the deoxidation reaction column 5 is provided, and hydrogen can be supplied to the deoxygenation reaction column 5 by supplying hydrogen to the nitrogen gas by the hydrogen introduction device 5a.
變壓式吸附裝置6可使用公知之PSA(Pressure Swing Absorption，變壓吸附)裝置，例如使用2塔式PSA裝置。The pressure swing type adsorption device 6 can use a well-known PSA (Pressure Swing Absorption) device, for example, a 2-tower PSA device.
圖3係表示變壓式吸附裝置6之一例的概略圖。變壓式吸附裝置6具有第1吸附塔12及第2吸附塔13，並將作為碳系吸附劑之碳分子篩填充至各吸附塔12、13。Fig. 3 is a schematic view showing an example of a pressure swing type adsorption device 6. The pressure swing adsorption device 6 includes a first adsorption tower 12 and a second adsorption tower 13, and a carbon molecular sieve as a carbon-based adsorbent is filled in each of the adsorption towers 12 and 13.
原料配管13f經由切換閥12b、13b與各吸附塔12、13之入口12a、13a連接。吸附塔12、13之入口12a、13a各自與切換閥12c、13c及消音器13e連接，以可向大氣中開放之方式而構成。又，吸附塔下部均壓配管13g經由切換閥13d而分別連接於吸附塔13之入口12a、13a。The raw material piping 13f is connected to the inlets 12a and 13a of the adsorption towers 12 and 13 via the switching valves 12b and 13b. The inlets 12a and 13a of the adsorption towers 12 and 13 are connected to the switching valves 12c and 13c and the muffler 13e, respectively, so as to be openable to the atmosphere. Further, the adsorption tower lower pressure equalizing pipe 13g is connected to the inlets 12a and 13a of the adsorption tower 13 via the switching valve 13d.
吸附塔12、13之出口12k、13k係各自經由切換閥121、131與流出配管13o連接，並經由切換閥12m、13m與洗淨配管13p連接，並經由切換閥13n與吸附塔上部均壓配管13q連接。The outlets 12k and 13k of the adsorption towers 12 and 13 are connected to the outflow pipe 13o via the switching valves 121 and 131, and are connected to the cleaning pipe 13p via the switching valves 12m and 13m, and are equally pressurized with the upper portion of the adsorption tower via the switching valve 13n. 13q connection.
流出配管13o經由止回閥13r及手動閥13s而與均壓槽14連接。均壓槽14經由壓力調節閥14a而與產品槽15連接。產品槽15係與變壓式吸附裝置6之出口配管15a連接。變壓式吸附裝置6之吸附壓力係藉由壓力調節閥14a控制。The outflow pipe 13o is connected to the pressure equalization tank 14 via the check valve 13r and the manual valve 13s. The pressure equalization tank 14 is connected to the product tank 15 via a pressure regulating valve 14a. The product tank 15 is connected to the outlet pipe 15a of the pressure swing adsorption device 6. The adsorption pressure of the pressure swing adsorption device 6 is controlled by a pressure regulating valve 14a.
洗淨配管13t經由流量控制閥13u、流量指示調節計13v而與洗淨配管13p連接，並調節洗淨配管13p之氣體流量至固定值，藉此，吸附塔12、13之填充劑得以洗淨至固定程度。The cleaning pipe 13t is connected to the cleaning pipe 13p via the flow rate control valve 13u and the flow rate indicating regulator 13v, and adjusts the gas flow rate of the cleaning pipe 13p to a fixed value, whereby the fillers of the adsorption columns 12 and 13 are washed. To a fixed degree.
於變壓式吸附裝置6之第1吸附塔12及第2吸附塔13之各自之內部，依次進行吸附操作、均壓操作、脫離操作、洗淨操作及均壓操作。The adsorption operation, the pressure equalization operation, the detachment operation, the cleaning operation, and the pressure equalization operation are sequentially performed in each of the first adsorption tower 12 and the second adsorption tower 13 of the pressure swing adsorption device 6.
打開切換閥12b，將所供給之生物氣體導入至第1吸附塔12，又，於第1吸附塔12中，與切換閥12b同時打開的僅有切換閥12l。藉此，藉由第1吸附塔12中所導入之生物氣體中之至少二氧化碳吸附於吸附劑而進行吸附操作，而未吸附於吸附劑之甲烷與二氧化碳分離並經由流出配管13o自第1吸附塔12導出。此時，送入至流出配管13o中之甲烷之一部分經由洗淨配管13p、13t、流量控制閥13u而送入至第2吸附塔13，於第2吸附塔13中進行洗淨操作。The switching valve 12b is opened, the supplied biogas is introduced into the first adsorption tower 12, and in the first adsorption tower 12, only the switching valve 121 is opened simultaneously with the switching valve 12b. Thereby, at least the carbon dioxide in the biogas introduced in the first adsorption tower 12 is adsorbed to the adsorbent, and the adsorption operation is performed, and the methane which is not adsorbed to the adsorbent is separated from the carbon dioxide and flows from the first adsorption tower via the outflow pipe 13o. 12 export. At this time, a part of the methane fed into the outflow pipe 13o is sent to the second adsorption tower 13 via the cleaning pipes 13p and 13t and the flow rate control valve 13u, and the second adsorption tower 13 performs a washing operation.
繼而，關閉切換閥12b、12l，打開切換閥13n、13d，進行使第1吸附塔12與第2吸附塔13之塔內壓力均勻的均壓操作。Then, the switching valves 12b and 12l are closed, the switching valves 13n and 13d are opened, and a pressure equalizing operation is performed in which the pressure in the column of the first adsorption tower 12 and the second adsorption tower 13 is uniform.
繼而，藉由關閉切換閥13n、13d，打開切換閥12c，而進行使包含二氧化碳之雜質自第1吸附塔12之吸附劑脫離的脫離操作，而包含二氧化碳之雜質與氣體一起經由消音器13e排放至大氣中。Then, by closing the switching valves 13n and 13d, the switching valve 12c is opened, and the detachment operation of removing the carbon dioxide-containing impurities from the adsorbent of the first adsorption tower 12 is performed, and the carbon dioxide-containing impurities are discharged together with the gas via the muffler 13e. To the atmosphere.
此時，於打開切換閥13b之同時，打開手動閥13s，自均壓槽14將降低了二氧化碳含量之甲烷氣體通過流出配管13o導入至第2吸附塔13，進行升壓操作及吸附操作。其後之各操作係以與對第1吸附塔12之操作相同之方式進行。At this time, the manual valve 13s is opened while the switching valve 13b is opened, and the methane gas having the reduced carbon dioxide content is introduced into the second adsorption tower 13 from the pressure equalizing tank 14 through the outflow pipe 13o, and the pressure increasing operation and the adsorption operation are performed. Each subsequent operation is performed in the same manner as the operation of the first adsorption tower 12.
藉由於第1吸附塔12、第2吸附塔13之各自之內部依次反覆進行該等各操作，而獲得包含二氧化碳之雜質之含量降低後之甲烷氣體。By performing the above operations in the respective steps of the first adsorption tower 12 and the second adsorption tower 13 in order, the methane gas having a reduced content of impurities including carbon dioxide is obtained.
再者，變壓式吸附裝置6並不限定於圖3所示之構成，塔數除可為2以外，例如亦可為3塔或4塔，通常為9塔以下。Further, the pressure swing type adsorption device 6 is not limited to the configuration shown in Fig. 3, and the number of the towers may be, for example, two or four columns, and usually nine or less, in addition to two.
根據此種回收裝置100，可自所供給之生物氣體除去水、矽氧烷及硫化氫之後，藉由使生物氣體中之氧與銅-氧化鋅反應而作為氧化銅加以捕捉，最後藉由變壓式吸附法分離二氧化碳而獲得經濃縮之高純度甲烷。According to the recovery apparatus 100, water, helium oxide, and hydrogen sulfide can be removed from the supplied biogas, and the oxygen in the biogas can be captured as copper oxide by reacting with copper-zinc oxide, and finally The carbon dioxide is separated by pressure adsorption to obtain concentrated high purity methane.
本發明並不限定於上述之構成，例如，可於壓縮機1之後設置硫化氫反應塔4，亦可調轉矽氧烷吸附塔3與硫化氫反應塔4之配置順序而設置，亦可調轉脫氧反應塔5與變壓式吸附裝置6之配置順序而設置。The present invention is not limited to the above configuration. For example, the hydrogen sulfide reaction column 4 may be disposed after the compressor 1, and the arrangement order of the xanoxane adsorption column 3 and the hydrogen sulfide reaction column 4 may be adjusted, and the deoxidation may be reversed. The reaction tower 5 and the pressure swing adsorption device 6 are arranged in the order of arrangement.
[實施例1][Example 1]
假定自污水處理場之污泥產生之生物氣體，並以甲烷60.0莫耳%、二氧化碳38.7莫耳%、氮0.5莫耳%、水0.3莫耳%、氧0.3莫耳%、硫化氫0.2莫耳%及矽氧烷50 mg/Nm3之混合氣體為處理對象氣體，以流量450 NL/hr進行供給。Assume that the biogas produced from the sludge of the sewage treatment plant is 60.0 mol% of methane, 38.7 mol% of carbon dioxide, 0.5 mol% of nitrogen, 0.3 mol% of water, 0.3 mol% of oxygen, 0.2 mol of hydrogen sulfide. The mixed gas of % and oxime 50 mg/Nm 3 was a treatment target gas, and was supplied at a flow rate of 450 NL/hr.
將處理對象氣體於25℃下導入至如下矽氧烷吸附塔3：於直徑為37 mm之圓筒狀吸附塔內部，積層有0.2 kg作為脫水劑之氧化鋁球(住友化學股份有限公司製造，KHD-24)、及0.5 kg作為矽氧烷之吸附劑之椰殼活性炭(Kuraray Chemical股份有限公司製造，GG)。繼而，將自矽氧烷吸附塔3導出之生物氣體於25℃下導入至如下硫化氫反應塔4：於與矽氧烷吸附塔3相同尺寸之反應器之內部，填充有2.0 kg氧化鋅(Hakusui Tech公司製造之1種JIS規格造粒品)。The treatment target gas was introduced at 25 ° C to the following oxane adsorption tower 3: inside a cylindrical adsorption tower having a diameter of 37 mm, and 0.2 kg of alumina balls as a dehydrating agent was laminated (manufactured by Sumitomo Chemical Co., Ltd., KHD-24), and 0.5 kg of coconut shell activated carbon (manufactured by Kuraray Chemical Co., Ltd., GG) as an adsorbent for decane. Then, the biogas derived from the decane adsorption column 3 is introduced at 25 ° C to the following hydrogen sulfide reaction column 4: inside the reactor of the same size as the siloxane adsorption column 3, filled with 2.0 kg of zinc oxide ( One JIS size granulated product manufactured by Hakusui Tech Co., Ltd.).
繼而，將1.2 kg氧化銅-氧化鋅觸媒(Sd-Chemie觸媒股份有限公司製造，MDC-3)導入至與矽氧烷吸附塔3相同尺寸之脫氧反應塔5，並藉由氫導入裝置5a將氫導入至脫氧反應塔5使氧化銅-氧化鋅觸媒還原而成為銅-氧化鋅混合物。將脫氧反應塔5之塔內溫度升溫至260℃為止並保持，導入自硫化氫反應塔4導出之生物氣體。Then, 1.2 kg of copper oxide-zinc oxide catalyst (S D-Chemie Catalyst Co., Ltd., MDC-3) is introduced into the deoxygenation reaction column 5 of the same size as the siloxane adsorption column 3, and hydrogen is introduced into the deoxygenation reaction column 5 by the hydrogen introduction device 5a to make copper oxide- The zinc oxide catalyst is reduced to form a copper-zinc oxide mixture. The temperature in the column of the deoxidation reaction column 5 is raised to 260 ° C and maintained, and the biogas derived from the hydrogen sulfide reaction column 4 is introduced.
繼而，將自脫氧反應塔5導出之生物氣體導入至如下變壓式吸附裝置6：於與矽氧烷吸附塔3尺寸相同之吸附塔內部，填充有0.6 kg微孔孔徑為3之碳分子篩(Kuraray Chemical製造，GN-UC-H)。變壓式吸附裝置6之操作與上述操作相同，將吸附操作中之最高壓力設為0.8 MPa，將脫離操作中之最低壓力設為大氣壓，從而將甲烷與二氧化碳分離而濃縮。Then, the biogas derived from the deoxygenation reaction column 5 is introduced into the following pressure swing adsorption device 6: inside the adsorption column having the same size as the xanoxane adsorption column 3, filled with 0.6 kg of microporous pore size of 3 Carbon molecular sieve (manufactured by Kuraray Chemical, GN-UC-H). The operation of the pressure swing type adsorption device 6 is the same as the above operation, and the highest pressure in the adsorption operation is set to 0.8 MPa, and the lowest pressure in the detachment operation is set to atmospheric pressure, thereby separating methane from carbon dioxide and concentrating it.
生物氣體中之二氧化碳及氮之濃度係使用股份有限公司島津製作所製造的GC-TCD(附有熱傳導性檢測器之氣相層析儀)進行測定，水分係藉由露點計進行測定，氧濃度係藉由DELTA F公司製造的微量氧氣濃度計(型號DF-150E)進行測定，矽氧烷濃度係使用島津製作所製造的GC/MS(氣相層析質量分析計)進行測定，硫化氫濃度係使用島津製作所製造的GC-FPD(附有火焰光度檢測器之氣相層析儀)進行測定。The concentration of carbon dioxide and nitrogen in the biogas was measured using a GC-TCD (gas chromatograph with a thermal conductivity detector) manufactured by Shimadzu Corporation, and the moisture was measured by a dew point meter. The measurement was carried out by a trace oxygen concentration meter (model DF-150E) manufactured by DELTA F. The concentration of the decane was measured using a GC/MS (gas chromatography mass spectrometer) manufactured by Shimadzu Corporation, and the concentration of hydrogen sulfide was used. The GC-FPD (gas chromatograph with flame photometric detector) manufactured by Shimadzu Corporation was used for measurement.
測定自脫氧反應塔5導出之氣體之組成，結果為：甲烷62.5莫耳%、二氧化碳37莫耳%、氮0.5莫耳%及水與氧與硫化氫與矽氧烷未達1莫耳ppm。The composition of the gas derived from the deoxygenation reaction column 5 was measured, and as a result, methane was 62.5 mol%, carbon dioxide was 37 mol%, nitrogen was 0.5 mol%, and water and oxygen and hydrogen sulfide and helium oxide were less than 1 mol ppm.
又，自變壓式吸附裝置6導出之產品氣體之甲烷濃度為98莫耳%之時，甲烷回收率為85.1%，且產品氣體中之氧濃度未達1莫耳ppm。Further, when the methane concentration of the product gas derived from the pressure swing adsorption device 6 was 98 mol%, the methane recovery rate was 85.1%, and the oxygen concentration in the product gas was less than 1 mol ppm.
[實施例2][Embodiment 2]
交換矽氧烷吸附塔3與硫化氫反應塔4，即調轉矽氧烷吸附步驟與脫硫化氫步驟之順序，除此以外，以與實施例1相同之方式自處理對象氣體濃縮甲烷。The methane was adsorbed from the treatment target gas in the same manner as in Example 1 except that the azide adsorption column 3 and the hydrogen sulfide reaction column 4 were exchanged, that is, the steps of the hafnium oxide adsorption step and the dehydrogenation step.
自變壓式吸附裝置6導出之產品氣體之甲烷濃度為98莫耳%之時，甲烷氣體回收率為84.9%，且產品氣體中之氧氣濃度未達1莫耳ppm。When the methane concentration of the product gas derived from the pressure swing adsorption device 6 is 98 mol%, the methane gas recovery rate is 84.9%, and the oxygen concentration in the product gas is less than 1 mol ppm.
[比較例1][Comparative Example 1]
不經由脫氧反應塔，即不進行氧之捕捉步驟，除此以外，以與實施例1相同之方式自處理對象氣體濃縮甲烷。Methane was concentrated from the treatment target gas in the same manner as in Example 1 except that the oxygen removal reaction column was not carried out, that is, the oxygen capture step was not performed.
自變壓式吸附裝置6導出之產品氣體之甲烷濃度為98莫耳%之時，甲烷氣體回收率為84.0%，且產品氣體中之氧濃度為90莫耳ppm。When the methane concentration of the product gas derived from the pressure swing adsorption device 6 was 98 mol%, the methane gas recovery rate was 84.0%, and the oxygen concentration in the product gas was 90 mol ppm.
[比較例2][Comparative Example 2]
不經由脫氧反應塔，即不進行氧之捕捉步驟，並藉由降低原料流量至370 NL/hr為止，使產品氣體中之氧濃度為1莫耳ppm，除此以外，以與實施例1相同之方式自處理對象氣體濃縮甲烷。The same as in Example 1, except that the oxygen removal reaction column was not carried out, that is, the oxygen capture step was not performed, and the oxygen concentration in the product gas was 1 mol ppm by reducing the flow rate of the raw material to 370 NL/hr. The method of concentrating methane from the treatment target gas.
使自變壓式吸附裝置6導出之產品氣體中之氧濃度為1莫耳ppm之時，產品氣體之甲烷濃度為99莫耳%以上，甲烷氣體之回收率為72.4%。When the oxygen concentration in the product gas derived from the pressure swing adsorption device 6 was 1 mol ppm, the methane concentration of the product gas was 99 mol% or more, and the recovery rate of methane gas was 72.4%.
如比較例1般，若欲獲得較高之回收率，則無法降低產品氣體中之氧濃度，如比較例2般，若欲降低產品氣體中之氧濃度，則甲烷氣體之回收率降低。相對於此，於實施例1、2中，可將產品氣體中之氧濃度設為未達1莫耳ppm，並以較高之回收率自生物氣體回收甲烷。As in Comparative Example 1, if a higher recovery rate is to be obtained, the oxygen concentration in the product gas cannot be lowered. As in Comparative Example 2, if the oxygen concentration in the product gas is to be lowered, the recovery rate of the methane gas is lowered. On the other hand, in Examples 1 and 2, the oxygen concentration in the product gas can be set to less than 1 mol ppm, and methane can be recovered from the biogas at a high recovery rate.
本發明可不脫離其精神或主要特徵，以其他各種形態進行實施。因此，上述實施形態於所有方面均僅為例示，本發明之範圍係為申請專利範圍中所示者，而絲毫不限定於說明書正文。進而，屬於申請專利範圍內的變形或變更，其所有內容均為本發明之範圍內之內容。The present invention may be embodied in other various forms without departing from the spirit or essential characteristics thereof. Therefore, the above-described embodiments are merely illustrative in all respects, and the scope of the present invention is as shown in the scope of the claims, and is not limited to the text of the specification. Further, all the changes or modifications within the scope of the claims are all within the scope of the invention.
1．．．壓縮機1. . . compressor
2．．．除濕裝置2. . . Dehumidifier
3．．．矽氧烷吸附塔3. . . Hexane adsorption tower
4．．．硫化氫反應塔4. . . Hydrogen sulfide reaction tower
5．．．脫氧反應塔5. . . Deoxygenation tower
5a．．．氫導入裝置5a. . . Hydrogen introduction device
6．．．變壓式吸附裝置6. . . Pressure swing adsorption device
7．．．氣體供給源7. . . Gas supply
12．．．第1吸附塔12. . . First adsorption tower
12a、13a．．．吸附塔入口12a, 13a. . . Adsorption tower inlet
12b、12c、12m、13b、13c、13d、13m、13n、12l、13l．．．切換閥12b, 12c, 12m, 13b, 13c, 13d, 13m, 13n, 12l, 13l. . . Switching valve
12k、13k．．．吸附塔出口12k, 13k. . . Adsorption tower outlet
13．．．第2吸附塔13. . . Second adsorption tower
13e．．．消音器13e. . . silencer
13f．．．原料配管13f. . . Raw material piping
13g．．．吸附塔下部均壓配管13g. . . Lower pressure equalizing pipe at the adsorption tower
13o．．．流出配管13o. . . Outflow piping
13p、13t．．．洗淨配管13p, 13t. . . Washing piping
13q．．．吸附塔上部均壓配管13q. . . Upper pressure equalizing pipe of adsorption tower
13r．．．止回閥13r. . . Check valve
13s．．．手動閥13s. . . Manual valve
13t．．．洗淨配管13t. . . Washing piping
13u．．．流量控制閥13u. . . Flow control valve
13v．．．流量指示調節計13v. . . Flow indicator regulator
14．．．均壓槽14. . . Pressure equalization groove
14a．．．壓力調節閥14a. . . A pressure regulating valve
15．．．產品槽15. . . Product slot
15a．．．出口配管15a. . . Export piping
100．．．回收裝置100. . . Recovery unit
S1．．．除去矽氧烷之吸附除去步驟S1. . . Removal step of removing oxane
S2．．．除去硫化氫之反應除去步驟S2. . . Reaction removal step for removing hydrogen sulfide
S3．．．捕捉氧氣之捕捉步驟S3. . . Capturing step to capture oxygen
S4．．．濃縮甲烷之濃縮步驟S4. . . Step of concentration of concentrated methane
圖1係表示作為本發明之實施之一形態之甲烷回收方法的步驟圖。Fig. 1 is a view showing a step of a method for recovering methane as one embodiment of the present invention.
圖2係表示作為本發明之實施之一形態的回收裝置之構成的概略圖。Fig. 2 is a schematic view showing the configuration of a recovery device which is one embodiment of the present invention.
圖3係表示變壓式吸附裝置之一例的概略圖。Fig. 3 is a schematic view showing an example of a pressure swing type adsorption device.
S1．．．除去矽氧烷之吸附除去步驟S1. . . Removal step of removing oxane
S2．．．除去硫化氫之反應除去步驟S2. . . Reaction removal step for removing hydrogen sulfide
S3．．．捕捉氧氣之捕捉步驟S3. . . Capturing step to capture oxygen
S4．．．濃縮甲烷之濃縮步驟S4. . . Step of concentration of concentrated methane
Claims (7)
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| JP2011007388A JP5713694B2 (en) | 2011-01-17 | 2011-01-17 | Methane recovery method and methane recovery device |
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| JP2014091766A (en) * | 2012-11-01 | 2014-05-19 | Ube Ind Ltd | System for utilizing biogas, and method for dehumidifying biogas |
| WO2014204131A1 (en) * | 2013-06-21 | 2014-12-24 | 현대건설 주식회사 | Device for refining biogas and method for controlling same |
| KR101444186B1 (en) * | 2013-06-21 | 2014-09-26 | 현대건설주식회사 | Purification device of biogas and purification method thereof |
| US10047310B2 (en) | 2014-09-18 | 2018-08-14 | Korea Research Institute Of Chemical Technology | Multistage membrane separation and purification process and apparatus for separating high purity methane gas |
| WO2016094830A1 (en) | 2014-12-12 | 2016-06-16 | Exxonmobil Research And Engineering Company | Methods of separating aromatic compounds from lube base stockes |
| CN107001859B (en) | 2014-12-12 | 2019-04-05 | 埃克森美孚研究工程公司 | Use the coating method and application thereof of organic silica (organosilica) material |
| US10022700B2 (en) | 2014-12-12 | 2018-07-17 | Exxonmobil Research And Engineering Company | Organosilica materials and uses thereof |
| EP3230409A1 (en) | 2014-12-12 | 2017-10-18 | ExxonMobil Research and Engineering Company | Organosilica materials and uses thereof |
| WO2016094803A1 (en) | 2014-12-12 | 2016-06-16 | Exxonmobil Research And Engineering Company | Membrane fabrication methods using organosilica materials and uses thereof |
| WO2016094861A1 (en) | 2014-12-12 | 2016-06-16 | Exxonmobil Chemical Patents Inc. | Olefin polymerization catalyst system comprising mesoporous organosilica support |
| WO2016094820A1 (en) | 2014-12-12 | 2016-06-16 | Exxonmobil Research And Engineering Company | Adsorbent for heteroatom species removal and uses thereof |
| US10351639B2 (en) | 2014-12-12 | 2019-07-16 | Exxonmobil Research And Engineering Company | Organosilica materials for use as adsorbents for oxygenate removal |
| WO2016094843A2 (en) | 2014-12-12 | 2016-06-16 | Exxonmobil Chemical Patents Inc. | Olefin polymerization catalyst system comprising mesoporous organosilica support |
| US10207249B2 (en) | 2014-12-12 | 2019-02-19 | Exxonmobil Research And Engineering Company | Organosilica materials and uses thereof |
| US10047304B2 (en) | 2014-12-12 | 2018-08-14 | Exxonmobil Research And Engineering Company | Aromatic hydrogenation catalysts and uses thereof |
| CA2998332A1 (en) * | 2015-09-17 | 2017-03-23 | Sekisui Chemical Co., Ltd. | Gas treatment method |
| CN108025254A (en) * | 2015-09-17 | 2018-05-11 | 积水化学工业株式会社 | Gas processing method and device |
| KR101869461B1 (en) * | 2015-12-10 | 2018-06-20 | 동국대학교 산학협력단 | Method for removing oxygen in methane mixture gas by using oxygen catalyst, perovskite type oxygen removing catalyst used in the same, and land fill gas refine device applying land fill gas mathane direct converting technology using the same |
| JP2019523746A (en) | 2016-06-10 | 2019-08-29 | エクソンモービル リサーチ アンド エンジニアリング カンパニーＥｘｘｏｎ Ｒｅｓｅａｒｃｈ Ａｎｄ Ｅｎｇｉｎｅｅｒｉｎｇ Ｃｏｍｐａｎｙ | Organosilica material, process for its production and use thereof |
| EP3468712A1 (en) | 2016-06-10 | 2019-04-17 | Exxonmobil Research And Engineering Company | Organosilica polymer catalysts and methods of making the same |
| US10179839B2 (en) | 2016-11-18 | 2019-01-15 | Exxonmobil Research And Engineering Company | Sulfur terminated organosilica materials and uses thereof |
| KR102081812B1 (en) * | 2016-12-27 | 2020-02-27 | 한국화학연구원 | High purity methane gas purification system from bio gas and method of bio gas purification using the same |
| CN111511465B (en) | 2017-12-21 | 2023-06-06 | 埃克森美孚科技工程公司 | Method for producing organic silicon dioxide material and use thereof |
| KR102199410B1 (en) * | 2018-12-31 | 2021-01-06 | 주식회사 태성공영 | Adsorbent for simultaneous removal of hydrogen sulfide ammonia siloxane using alum-sludge |
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| CN115532034A (en) * | 2022-10-22 | 2022-12-30 | 潍坊金信达生物化工有限公司 | Method and device for treating biodiesel mixed tail gas |
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| JP2006083311A (en) * | 2004-09-17 | 2006-03-30 | Ebara Corp | Apparatus for refining sewage gas and method for refining the same gas |
| JP2009249571A (en) * | 2008-04-09 | 2009-10-29 | Taiyo Nippon Sanso Corp | Method for eliminating hydrogen sulfide contained in biogas |
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