201039910 、發明說明： 【發明所屬之技術領域】 本發明係關於一種含硫廢氣淨化及沼氣曱烷回收之 裝置及方法，特別是關於一種可以有效去除含硫廢氣中含 硫化合物之裝置，並該含硫廢氣淨化裝置再結合一甲烷回 收裝置，可同時有效去除沼氣中之含硫化合物並回收該沼 氣中之甲烧。 【先前技術】 沼氣是有機物質於厭氧環境中，於一定的溫度、濕度 及酸鹼度的條件下，經過微生物醱酵作用，產生的一種可 燃氣體，並由於此種氣體最初是在沼澤、湖泊或池塘中發 現的，所以被人們稱之為沼氣。而沼氣中含有多種氣體成 分，其中最主要的可燃成分是曱烷(ch4)。 此外，沼氣細菌分解有機物質，進而產生沼氣的過 程，則稱之為沼氣醱酵。依據沼氣醱酵過程中各類細菌的 作用，其中沼氣細菌可以分為兩大類：第一類細菌稱之 為：分解菌，該等分解菌之作用是將複雜的有機物質分解 成簡單的有機物質及二氧化碳(co2)等。於該等分解菌當 中有專門分解纖維素者，稱之為纖維分解菌；亦有專門分 解蛋白質者，則稱之為蛋白分解菌；另有專門分解脂肪 者，另稱之為脂肪分解菌；而第二類細菌稱之為：含曱烷 細菌，一般亦有稱之為曱烧菌，該等曱烧細菌之作用則是 將簡單的有機物質及二氧化碳氧化還原成曱烷。因此，有 機物質醱酵轉變為沼氣之過程，就如同工廠生產一種產品 3 201039910 的兩道程序：首先是經由分解細菌將糞便、秸稈、雜草等 複雜的有機物質加工成半成品—結構簡早的化合物，其次 則是利用曱烷細菌的醱酵作用，將簡單的化合物加工成產 品一即生成曱烷。 沼氣為一種混合氣體，其主要成分為曱烷，其次則含 有二氧化碳、硫化氬(h2s)、氮及其他一些成分。沼氣的組 成中，可燃成分包括曱烧、硫化氫、曱硫醇、一氧化石炭和 重烴等氣體；不可燃成分包括二氧化碳、氮和氨等氣體。 於沼氣成分中曱烷含量為55%〜70%、二氧化碳含量為 28%〜44%、硫化氩平均含量為0.034%、微量之甲硫醇（其 中硫化氫及曱硫醇同屬惡臭氣與其氧化後具腐蝕性）。 再者，沼氣是一種無色、有味、有毒、有臭的氣體， 其主要成分甲烷在常溫下是一種無色、無味、無臭、無毒 的氣體。曱烷分子式是CH4，是由一個碳原子與四個氫原 子所結合的簡單碳氫化合物。甲烷相對於空氣之重量比為 0.54，相較於空氣的重量而言，其重量約為空氣的一半。 曱烷溶解度很低，於20°C、0.1 KPa時，100單位體積的 水，只能溶解3個單位體積的甲烷。 曱烷係為一簡單的有機化合物，亦為一優質的氣體燃 料，甲烷燃燒時呈藍色火焰，最高溫度可達1400 °C左右， 同時，純曱烷每立方米發熱量為36.8千焦。沼氣每立方米 的發熱量約23.4千焦，相當於0.55千克柴油或0.8千克煤 炭充分燃燒後放出的熱量。從熱效率分析，每立方米沼氣 所能利用的熱量，相當於燃燒3.03千克煤所能利用的熱 201039910 量0 而沼氣可被視為一種生 化’其特㈣與以氣無異體只要經過淨 中的水份、硫化氣及微粒等雜質，=:需去除生化氣體 更能完全雜，_供應商會得淨化後之氣體201039910, invention description: [Technical field of invention] The present invention relates to a device and method for purifying sulfur-containing exhaust gas and recovering biogas decane, and more particularly to a device capable of effectively removing sulfur compounds in sulfur-containing exhaust gas, and The sulfur-containing exhaust gas purifying device is combined with a methane recovery device, which can simultaneously effectively remove sulfur compounds in the biogas and recover the methane in the biogas. [Prior Art] Biogas is a kind of combustible gas produced by microorganisms in an anaerobic environment under conditions of temperature, humidity and pH, and because the gas is originally in swamps, lakes or Found in the pond, so it is called biogas. The biogas contains a variety of gas components, the most important of which is decane (ch4). In addition, biogas bacteria decompose organic matter, which in turn produces biogas, which is called biogas fermentation. According to the role of various bacteria in the biogas fermentation process, biogas bacteria can be divided into two categories: the first type of bacteria is called decomposition bacteria, and the decomposition bacteria are used to decompose complex organic substances into simple organic substances. And carbon dioxide (co2) and the like. Among these decomposing bacteria, there are those who decompose cellulose specifically, which are called fibrinolytic bacteria; those who specialize in decomposing proteins are called proteolytic bacteria; others who specialize in decomposing fat are also called lipolytic bacteria; The second type of bacteria is called: tropane-containing bacteria, which are also commonly known as smoldering bacteria. The function of these smoldering bacteria is to oxidize and reduce simple organic substances and carbon dioxide into decane. Therefore, the process of converting organic matter into biogas is like two processes in which the factory produces a product 3 201039910: firstly, through the decomposition of bacteria, the complex organic matter such as feces, straw, weeds, etc. is processed into semi-finished products - the structure is simple. Compounds, followed by the fermentation of decane bacteria, process simple compounds into products, ie, decane. Biogas is a mixed gas whose main component is decane, and secondly contains carbon dioxide, argon sulfide (h2s), nitrogen and other components. In the composition of biogas, combustible components include gas, hydrogen sulfide, barium mercaptan, carbon monoxide and heavy hydrocarbons; non-combustible components include carbon dioxide, nitrogen and ammonia. In the biogas component, the decane content is 55%~70%, the carbon dioxide content is 28%~44%, the average content of argon sulfide is 0.034%, and the trace amount of methyl mercaptan (in which hydrogen sulfide and sulfonium thiol are both malodorous gases and oxidized) After corrosive). In addition, biogas is a colorless, odorous, toxic, and odorous gas. Its main component, methane, is a colorless, odorless, odorless, non-toxic gas at room temperature. The decane formula is CH4, a simple hydrocarbon combined with one hydrogen atom and four hydrogen atoms. The weight ratio of methane to air is 0.54, which is about half the weight of air compared to the weight of air. The solubility of decane is very low. At 20 ° C and 0.1 KPa, 100 units of water can only dissolve 3 unit volumes of methane. The decane system is a simple organic compound and is also a good gas fuel. When methane is burned, it has a blue flame with a maximum temperature of about 1400 °C. At the same time, the pure decane has a calorific value of 36.8 kJ per cubic meter. The calorific value per cubic meter of biogas is about 23.4 kJ, which is equivalent to the heat released by 0.55 kg of diesel or 0.8 kg of coal after full combustion. From the thermal efficiency analysis, the amount of heat that can be utilized per cubic meter of biogas is equivalent to the amount of heat that can be utilized by burning 3.03 kilograms of coal. The amount of heat can be regarded as a kind of biochemicals, and the gas can be regarded as a kind of biochemical. Impurities such as moisture, sulfurized gas and particulates, =: It is more complete to remove biochemical gases, _ suppliers will get purified gas
量。倘若未經上•化程序處理的m?1"*氧化石炭含 合燃燒，但當生化氣體之淨化達/有日诗與天然氣混 等氣體即可被稱之為「可再生天^運輪的品質後，此 此等經申化之氣體於應 發電及爐具等，而_縮的_二，無異，可運麟 替品，可用在汽車的内燃機或燃^池=縮天然氣的代 而台灣地區沼氣來源相當豐富，以往大都未被充份利 用而任其排放，減能狀㈣且有空氣污染之虞，原因 是於沼氣中含有大量的二氧化碳及少量的硫化氫，不但敎 值較天然氣為低且具有臭味及腐趣，使制用上頗受限 制。 本發明之目的即在於提供-種有效淨化含硫廢氣之 裝置及方法，以有效淨化含硫廢氣中所含之硫化合物，其 係亦可運用於淨化沼氣中之含硫化合物，並進一步結合— 曱烷回收之裝置，以獲得純度較高之可再生天然氣。 【發明内容】 為了改善上述習知技術所面臨的問題，本發明之目的 在提供一種含硫廢氣淨化裝置，其係包含：一鼓風機、一 真空幫浦、一閥件組合及至少一個以上之硫化物淨化塔， 201039910 其特徵在於該硫化物淨化塔用以脫附含硫化合物，並該硫 化物淨化塔填充一高矽鋁比沸石吸附材，且該高矽鋁比沸 石吸附材之石夕結比為1 〇以上。（上述裝置中，若有加壓源 則可省略鼓風機；若無須進行吸附材之再生，該真空幫浦 亦可省略） 本發明之含硫廢氣淨化裝置中，當該硫化物淨化塔係 為兩個以上時，該等硫化物淨化塔係可為同時淨化操作或 批次式淨化操作。 姐上述之含硫廢氣淨化裝置中，該硫化物淨化塔所脫 附之含硫化合物係為硫化氫(¾s)或/及甲醇硫(CH3sH);再 者，其中該高矽鋁比沸石吸附材係為MCM-41沸石、γ型 沸石或南矽彿石（Silicaiite) 叫取>1主你两咼哥彿石。 石 此外，於上述之含硫廢氣淨化裝置中，該高矽鋁比 吸附材之成形形狀為顆粒狀或蜂巢狀。 本發明另-目的係提供-_氣甲如收 盆 包含：-鼓風機、一真空幫浦、—閥件組合及一個： 浴氣甲=，其特徵在於㈣氣甲㈣收塔二t 1化物赌劑，其係用以脫时硫化 化物吸附劑係為一高矽鋁比沸且该 吸附材之抑比為1G以上；f材該㈣銘比彿 甲如㈣，該沼氣甲細收劑係用以八離 氣中：二化碳及甲燒’且沼氣甲燒回收劑係由活“ 彿石=成。（上述裝置中，若有加壓源則可省 ς 若無須進行吸附材之再生，該真空幫浦亦£ 6 201039910 本發明之沼氣甲烷 係為兩個以上時，諸A 虽該沼氣曱烷回收塔 作或批次切化_ f邱f咖㈣係可制時淨化操 並上述之沼氣甲 附之含硫化合物心、㈣絲置巾，該魏物㈣劑所脫 者，其中高賴比、、i _2_/及甲醇硫仰3呵；再 石或高石夕彿石；㈣石吸附材係為MCM-41沸石、¥型彿 Ο 〇 之活性浐.日兮Μ活性碳係為缝Ca2+、Mg2+或Cu2+改質 反，且5玄X型池=& & τ 或Na_X型滞石。彿石係為WX、Ca-X、Sr-X、Mg-X 而上述沼氣甲烷 最佳為高石夕沸石.今 置中，該高石夕1呂比沸石吸附材 碳；且該讀碳係最佳為經以+改質之活性 W型冻石最佳為Li-X型沸石。 此外’於上述之、”产 石 石 吸附从+ > k軋甲烷回收裝置中，該高矽鋁比沸 之成形形狀蜂巢狀；而該活性碳及彿 時易產生爆聲） 果狀（右為顇粒狀，於進行吸附作用 本發明又一目的抱 置，1 .幻係楗供—種兩階段沼氣曱烷回收裝 少—:糸匕含：二鼓風機、二真空幫浦、二閥件組合、至 Μ上之硫化物淨化塔及上之甲化 其特徵在於： 化拔^爪化物/爭化塔用以脫附含硬化合物，並該硫化物淨 比i !〇t"上高石夕銘比沸石吸附持，且該沸石吸附材之石夕銘 該甲烧淨化塔用以分離沼氣中之二氧化破及曱燒’且 201039910 該沼氣曱烷淨化塔係由活性碳及沸石 中，若有加壓源則可省略鼓風機；若無、’。（上逑裝置 生，該真浦亦可省略) …、仃吸附材之再 於本發明之兩階段沿氣尹燒回收裝 淨化塔及甲燒淨化塔係為兩個以上時 ：：硫化物 及甲==塔係可為同時淨化操作或塔 塔所脫附之含 =:'Γ二其一淨化 (C糊；再者，其中高仙 =7(蝴⑽甲醇硫 7鋁比沸石吸附材係為MCM-41 i =沸石或高紙而該活性碳係為經。2+、 g或广改質之活性碳;且該χ型彿石係為Μ、 Ca-X、Sr_X、Mg-x 或知X 型彿石。 2述兩階段〉召氣甲燒回收裝置中，該高石夕銘比沸石 取佳為高石夕沸石;該活性碳最佳為經Μ改質之活 反，且該X型沸石係為U_x型沸石。 卜於上述之/召氣曱規回收裝置，其中該高石夕銘比 吸附材之成形形狀為顆粒狀或蜂巢狀；而該活性破及 沸:之成形形狀為蜂巢狀(若為顆粒狀，於進行吸附作用 時易產生爆裂）。 —田X上述t兩階段沼氣甲燒时裝置，其躺—步包含 儲存單7L，用以儲存經淨化之沼氣甲烧。 ^發明之另-目的係提供—種含硫廢氣淨化之方 法，其係包含下列步驟： 供:It上所述之含硫廢氣淨化裝置，用以脫附含硫 201039910 化合物； (2) 經由鼓風機將所欲處理之含硫廢氣導入該裝置，開 啟或/及關閉相關閥組，以進行含硫化合物之脫附，並同時 排放經吸附含硫化合物後淨化氣體； (3) 開啟或/及關閉相關閥組，利用真空幫浦抽吸該裝 置内之含硫化合物，以進行吸附材之再生。 本發明之再一目的係提供一種沼氣曱烷回收之方 法，其係包含下列步驟： ❹ （1)提供如上所述之沼氣曱烷回收裝置，用以回收沼氣 甲烷； (2) 經由鼓風機將所欲處理之沼氣導入該裝置，開啟或 /及關閉相關閥組，以進行含硫化合物之脫附及二氧化碳與 曱烷之分離，並同時回收經淨化處理之甲烷； (3) 開啟或/及關閉相關閥組，利用真空幫浦抽吸該裝 置内之含硫化合物及二氧化碳，以進行吸附材之再生。 Q 藉此，本發明之含硫廢氣淨化及沼氣曱烷回收之方法 及裝置，係可有效的淨化含硫廢氣，並同時回收沼氣曱 烷，可充分有效利用沼氣資源，達成自然資源之有效利用。 【實施方式】 為使充分瞭解本發明之目的、特徵及功效，茲藉由下 述具體之實施例，並配合所附之圖式，對本發明做一詳細 說明，說明如後： 實施例1 本發明第一具體實施例之一種含硫廢氣淨化裝置1係 9 201039910 如第一圖所示，其中該裝置係包含：一鼓風機10、一真空 幫浦20、一閥件組合(21〜30)及二硫化物淨化塔11、12。 並以下各閥組除另有說明外，皆為關閉狀態。 含硫廢氣之淨化 首先，開啟鼓風機10，並進入： 第一步驟： 開啟閥21、24、25及29，經由該鼓風機10可將氣體 入口 A將所欲處理之含硫廢氣導入該等硫化物淨化塔11 進行吸附淨化程序，於該硫化物淨化塔11中填充有高矽 鋁比沸石吸附材，用於將所欲淨化之含硫廢氣中之含硫化 合物吸附，進而將淨化後之氣體經由25及29至氣體出口 C排放；此時硫化物淨化塔12進行減壓脫附程序，則藉 由真空幫浦20之開啟於用減壓真空方式，使原本吸附於 該等硫化物淨化塔12内之硫化物及曱硫醇被脫附，而經 廢氣出口 B所排放或回收；其間硫化物淨化塔12進行減 壓脫附程序完成時，可進一步將閥28及30開啟並引入氣 流自氣體入口 D進行硫化物淨化塔12沖洗程序(purge)。 第二步驟： 開啟閥22、23、26及29，經由該鼓風機10可將氣體 入口 A將所欲處理之含硫廢氣導入該等硫化物淨化塔12 進行吸附淨化程序，於該硫化物淨化塔12中填充有高矽 鋁比沸石吸附材，用於將所欲淨化之含硫廢氣中之含硫化 合物吸附，進而將淨化後之氣體經由26及29至氣體出口 C排放；此時硫化物淨化塔11進行減壓脫附程序，則藉由 10 201039910 真空幫浦20之開啟於用減壓真空方式，使原本吸附於該 等硫化物淨化塔11内之硫化物及曱硫醇被脫附，而經廢 氣出口 B所排放或回收；其間硫化物淨化塔11進行減壓 脫附程序完成時，可進一步將閥27及30開啟並引入氣流 D進行硫化物淨化塔11沖洗程序(purge)。 而上述之氣體淨化過程中，亦可使用單一硫化物淨化 塔11進行淨化處理，唯使用單一硫化物淨化塔11進行含 硫廢氣淨化時，僅開啟閥21、25及29 ;並於上述兩硫化 〇 物淨化塔係同時淨化操作使用，唯亦可利用該等閥組之開 關，而達成批次淨化操作。 於上述之硫化物淨化塔中所填充之高矽鋁比沸石吸 附材，其中該高矽鋁比沸石吸附材之矽鋁比為10以上， 且所脫附之含硫化合物係為硫化氫或/及甲醇硫；並該等高 矽鋁比吸附材係為MCM-41沸石、Y型沸石或高矽沸石， 並該等高矽鋁比沸石吸附材之成形形狀為顆粒狀或蜂巢 〇 狀。 以含硫化物廢氣進行該裝置效能之測試評估，其中該 含硫化物廢氣之成份為：硫化氫600ppm、甲硫醇150ppm、 水氣25000ppm、曱烧65%及二氧化石炭32.5%，且入流溫度 為25°C ;而於該等硫化物淨化塔中分別填充：MCM-41沸 石（蜂巢狀）、Y型沸石（蜂巢狀）、高矽沸石（蜂巢狀與顆粒 狀)及活性碳(蜂巢狀），進行含硫化物廢氣淨化測試，其結 果如下表一： 11 201039910 化氫及甲醇y之淨化效能評估 吸附齊J 材質/型I MCM-411JJ-(蜂巢^ Y型沸石 (蜂巢狀 1 高矽沸^ (蜂巢狀） 南石夕滞石 (顆粒@ 活性碳 (蜂巢狀 去除效率 CH3SH 去除效率 效能評估 > 99 % > 95 % > 99 % > 85 % 50% • 50 % > 70 % > 99 % > 80 % < 10 % H2s效率較佳 -¾尹淨化h2s) h2s效率較佳 於淨化h2s) 效率佳 效率適中 —〜· . _____ 效率受水氣 jjg〇之影響 由 μ 主^---~~~~~~~ijg〇 之影響 及古2 果可知，當使用MCM-41滞石、γ型沸石 二C石：，皆可有效去除硫化氣’同時亦可去除甲硫 石於甲硫醇之去除效率僅達50%以上； 仁方乂活性碳為硫化物之吸附材，其效果不彰，僅可 硫化虱5〇%’甲硫醇更低於1〇 ” 於作為硫化物吸附材使用。下故杨W並不適 且該等吸附材MCM-41彿石、γ _石 =比皆大於Η)以上，其中該丫型沸石 弗二 石夕沸石之石夕銘比係為350，且_#物 =3 高矽沸石為最佳。 又从5亥 硫化物淨化塔之再生 當該含硫廢氣淨化完成之後，關閉原淨化操 啟之間門，娜咖23或/及24及真空幫浦2G，、= 減壓真空方式，使原本吸附於該等硫化物淨値u或^ 12内之硫化物及甲硫醇被脫附，而經廢氣出σ°Β所排放 或回收。 12 201039910 並上述脫附反應中，亦可同步開啟閥門27或/及28 及30，利用一氣體入口 D，同時提供臭氧、水氣或蒸氣， 以加速硫化氫及曱硫醇之脫附作用。 實施例2 本發明第二具體實施例之一種沼氣曱烷回收裝置2係 如第二圖所示，其中該裝置係包含：一鼓風機10、一真空 幫浦20、一閥件組合(41〜57)及二沼氣甲烷回收塔31、32。 〇 並以下各閥組除另有說明外，皆為關閉狀態。 沼氣曱烧之回收 首先，關啟鼓風機10，並根據表二操作步驟程序及閥 件開啟說明之順序進行開啟與關閉狀態，在吸附程序時經 由該鼓風機10可將氣體入口 A將所欲處理之沼氣導入該 等沼氣曱烷回收塔31或/及32,於該沼氣曱烷回收塔31、 3 2中填充一硫化物吸附劑及一沼氣甲烷回收劑，用於淨化 Q 於沼氣中之含硫化合物及二氧化碳，進而將淨化後曱烷經 由44、54及57至氣體出口 C1排放。 而上述之沼氣甲烷回收過程中，亦可使用單一沼氣甲 烷回收塔31進行淨化處理，唯使用單一沼氣曱烷回收塔 31進行含硫廢氣淨化時，僅開啟閥41、44及57 ;並於上 述二沼氣甲烷回收塔係同時淨化操作使用，唯亦可利用該 等閥組之開關控制，而達成批次淨化操作。 表二：操作步驟程序及閥件開啟說明 操作步驟 開啟的閥件 回收塔31 回收塔32 13 201039910 a.進料加壓吸附程序 d逆向減壓脫附程序 41,48,52 b.持續進料吸附程序 e.持續減壓脫附程序 41,44,48,52,57 C.同向減壓脫附程序 £產物回壓程序 44,56,57 d.逆向減壓脫附程序 a.進料加壓吸附程序 42,48,51 e.持續減壓脫附程序 b.持續進料吸附程序 42,48,51,54,57 f.產物回壓程序 C.同向減壓脫附程序 46,54,57 其中，回收塔31進行a+b + c今d+e + f循環程序時， 同時回收塔32則進行d+e+f+a+b + c之對應循環程序； 其中，d步驟逆向減壓脫附程序之後可進一步增加dl 低壓沖洗程序，此時回收塔31、32進行閥件43、45、51、 54及57開啟，或者回收塔31、32進行閥件41、44、53、 55及57開啟； 或者，d步驟逆向減壓脫附程序之後可進一步增加d2 高壓產物沖洗程序，此時回收塔31、32進行閥件42、46、 51、 54及57開啟，或者回收塔31、32進行閥件41、44、 52、 56及57開啟； 於上述之沼氣曱烷回收塔中所填充之硫化物吸附劑 係為一高矽鋁比沸石吸附材，其中該高矽鋁比沸石吸附材 之矽鋁比為10以上，且所脫附之含硫化合物係為硫化氫 或/及曱醇硫；並該等高矽鋁比吸附材係為MCM-41沸石、 Y型沸石或高矽沸石，並該等高矽鋁比沸石吸附材之成形 形狀為顆粒狀或蜂巢狀；並其中之沼氣曱烷回收劑係用以 分離沼氣中之二氧化碳及曱烷，且沼氣甲烷回收劑係由活 性碳及沸石所組成，而該活性碳係為經Ca2+、Mg2+或Cu2+ 改質之活性碳；且該X型沸石係為Li-X、Ca-X、Sr-X、 Mg-X或Na-X型沸石。 14 201039910 以沼氣進行該裝置致能之測試 份為：硫化氳⑽鹏、甲㈣2nW估’其中該沼氣之成 分比/ PPm、水氣3.5%體積百 刀比甲& 68/〇及一钱碳28 5〇/〇,且入产 填充之硫化物吸附材高矽沸石（矽銪n”，、，而 jk山乂么π 2+n併 匕為45〇)、而該活性 厌係為及C u改質之活性石炭；且該彿石係為⑽， 進行沼氣甲烷回收測試。the amount. If m?1"* oxidized carbon charcoal is not burned without the processing procedure, when the biochemical gas is purified/gas mixed with natural gas and natural gas, it can be called "renewable day" After the quality, this kind of gas that has been applied to the power generation and the stove, etc., and the _ contraction _ two, no different, can be used for the internal combustion engine or combustion pool = gas The source of biogas in Taiwan is quite rich. In the past, most of them were not fully utilized and were discharged. The energy-reducing (4) and air pollution were caused by the large amount of carbon dioxide and a small amount of hydrogen sulfide in the biogas, which was not only devalued compared with natural gas. The invention is low in content and has an odor and is rot, which is limited in its manufacture. The object of the present invention is to provide an apparatus and method for effectively purifying a sulfur-containing waste gas, thereby effectively purifying a sulfur compound contained in a sulfur-containing exhaust gas. The system can also be used to purify sulfur-containing compounds in biogas, and further combined with a decane recovery device to obtain a higher purity renewable natural gas. SUMMARY OF THE INVENTION In order to improve the problems faced by the above-mentioned prior art, The object of the invention is to provide a sulfur-containing exhaust gas purifying device, comprising: a blower, a vacuum pump, a valve member combination and at least one sulfide purification tower, 201039910, characterized in that the sulfide purification tower is used for taking off A sulfur-containing compound is added, and the sulfide purification tower is filled with a sorghum-aluminum ratio zeolite adsorbing material, and the ratio of the high-alumina aluminum to the zeolite adsorbing material is more than 1 。. (In the above device, if there is a pressurized source The blower can be omitted; if the regeneration of the adsorbent material is not required, the vacuum pump can be omitted.) In the sulfur-containing exhaust gas purification device of the present invention, when the sulfide purification tower is two or more, the sulfide purification tower The system may be a simultaneous purification operation or a batch purification operation. In the sulfur-containing exhaust gas purification device described above, the sulfur-containing compound desorbed by the sulfide purification tower is hydrogen sulfide (3⁄4s) or/and methanol sulfur (CH3sH). Further, wherein the sorghum aluminum specific zeolite adsorbent is MCM-41 zeolite, γ-type zeolite or Silicaiite, and is called the two masters of the buddha stone. Stone, in addition to the above Sulfur-containing exhaust gas purification In the middle, the shape of the sorghum aluminum specific adsorbing material is granular or honeycomb. The other object of the present invention is to provide a gas basin such as a blower, a vacuum pump, a valve assembly and a : Bathing air A =, which is characterized by (4) gas armor (4) collecting tower two t1 compound gambling agent, which is used for desulfurization when the sulfide adsorbent is a high bismuth aluminum specific boiling ratio and the adsorption material is more than 1G. (f) The (four) Ming than the Buddha A (4), the biogas fine collection agent is used in eight gas: carbon dioxide and a burning 'and the biogas a burning recovery agent is from the living "fo stone = Cheng. (In the above device, if there is a pressurized source, the vacuum pump can be saved. If the regeneration of the adsorbent material is not required, the vacuum pump is also 6 6 201039910. When the biogas methane system of the present invention is two or more, the A is recovered by the biogas decane. Tower or batch cutting _ f Qiu f coffee (four) can be used to purify the operation and the above-mentioned biogas attached to the sulfur-containing compound heart, (four) silk towel, the Wei (4) agent is removed, of which high ratio, , i _2_ / and methanol sulfur up to 3 ah; re-stone or high stone buddha stone; (four) stone adsorption material is MCM-41 zeolite, ¥ type Ο Ο 〇 activity 浐. Japanese 兮Μ active carbon is the seam Ca2+, Mg2+ Or Cu2+ is reversed, and 5 Xuan X-type pool = && τ or Na_X type stagnant stone. Foshan system is WX, Ca-X, Sr-X, Mg-X and the above biogas methane is best for Gao Shixi Zeolite. In this case, the high-stone Xilu-Lime zeolite adsorbs carbon; and the read carbon system is preferably the active-type W-type frozen stone which is preferably modified to be Li-X-type zeolite. "The stone is adsorbed from the + > k rolling methane recovery device, the high bismuth aluminum is formed in a honeycomb shape than the boiling shape; and the activated carbon and the Buddha is easy to produce a popping sound) (right顇 granules, for adsorption, another object of the present invention, 1. Phantom 楗 supply - two-stage biogas decane recovery less -: 糸匕: two blower, two vacuum pump, two valve combination The sulphide purification tower and the above-mentioned sulphide are characterized in that: the claw-paste/distribution tower is used to desorb the hard compound, and the sulphide net ratio is i !〇t" It is held by zeolite adsorption, and the zeolite adsorption material of Shi Ximing is used to separate the dioxane and the smoldering gas in the biogas and 201039910. The biogas decane purification tower is made of activated carbon and zeolite. The pressure source can omit the blower; if not, '. (The upper device can be omitted, the Zhenpu can be omitted) ..., the 仃 adsorbent material is further purified in the two stages of the invention along the gas-burning recovery purification tower and the A-burn purification When the tower system is more than two:: Sulfide and A == tower system can be the simultaneous purification operation or the desorption of the tower. =: 'Γ二一一一净化 (C paste; in addition, among them, Gaoxian = 7 (Butterfly (10) methanol sulfur 7 aluminum specific zeolite adsorption material is MCM-41 i = zeolite or high paper and the activated carbon system is 2+ , g or a modified activated carbon; and the 佛-type buddha is Μ, Ca-X, Sr_X, Mg-x or X-type fossil. 2 In the two-stage 〉 召 甲 甲 回收 recovery device, Gao Shi Xi Ming is better than zeolite as high-stone zeolite; the activated carbon is preferably the reverse of hydrazine modification, and the X-type zeolite is U_x-type zeolite. The shape of the high-stone Ximing than the adsorbent material is granular or honeycomb; and the activity is broken and boiling: the formed shape is honeycomb-shaped (if it is granular, it is prone to burst when adsorbed). t Two-stage biogas ablation device, the lying-step includes a storage unit 7L for storing the purified biogas. The invention further provides a method for purifying a sulfur-containing exhaust gas comprising the steps of: supplying: a sulfur-containing exhaust gas purifying device as described in It for desorbing a sulfur-containing 201039910 compound; (2) passing a blower Introducing the sulfur-containing waste gas to be treated into the device, opening or/and closing the relevant valve group for desorption of the sulfur-containing compound, and simultaneously discharging the adsorbed sulfur-containing compound to purify the gas; (3) opening or/and closing The related valve group uses a vacuum pump to pump the sulfur-containing compound in the device to perform regeneration of the adsorbent material. A further object of the present invention is to provide a method for recovering biogas decane comprising the steps of: (1) providing a biogas decane recovery unit as described above for recovering biogas methane; (2) passing the blower The biogas to be treated is introduced into the device to open or/and close the relevant valve group for the desorption of sulfur compounds and the separation of carbon dioxide and decane, and at the same time recover the purified methane; (3) open or / and close The relevant valve group uses a vacuum pump to pump sulfur compounds and carbon dioxide in the device to regenerate the adsorbent material. Q, the method and device for purifying sulfur-containing exhaust gas and recovering biogas decane according to the present invention can effectively purify sulfur-containing waste gas and simultaneously recover biogas decane, and can fully utilize biogas resources to achieve effective utilization of natural resources. . DETAILED DESCRIPTION OF THE INVENTION In order to fully understand the objects, features and effects of the present invention, the present invention will be described in detail by the following specific embodiments and the accompanying drawings. A sulfur-containing exhaust gas purifying device 1 of the first embodiment of the present invention is a first embodiment, wherein the device comprises: a blower 10, a vacuum pump 20, a valve member combination (21 to 30), and Disulfide purification towers 11, 12. The following valve groups are all closed unless otherwise stated. Purification of sulfur-containing waste gas First, the blower 10 is turned on and enters: First step: The valves 21, 24, 25 and 29 are opened, through which the gas inlet A can introduce the sulfur-containing waste gas to be treated into the sulfides. The purification tower 11 performs an adsorption purification process, and the sulfide purification tower 11 is filled with a strontium-aluminum-specific zeolite adsorbing material for adsorbing the sulfur-containing compound in the sulfur-containing exhaust gas to be purified, and further, the purified gas is passed through 25 and 29 to the gas outlet C discharge; at this time, the sulfide purification tower 12 performs the decompression desorption procedure, and the vacuum pump 20 is opened to the desulfurization vacuum to be originally adsorbed to the sulfide purification tower 12 The sulfides and bismuth thiols are desorbed and discharged or recovered through the exhaust gas outlet B. During the completion of the decompression desorption process of the sulfide purification tower 12, the valves 28 and 30 can be further opened and introduced into the gas stream from the gas. The inlet D is subjected to a sulphide purification tower 12 purge. The second step: opening the valves 22, 23, 26 and 29, through which the gas inlet A can introduce the sulfur-containing waste gas to be treated into the sulfide purification tower 12 for adsorption purification process, in the sulfide purification tower 12 is filled with a sorghum-aluminum ratio zeolite adsorbing material for adsorbing the sulfur-containing compound in the sulfur-containing exhaust gas to be purified, and then discharging the purified gas through the 26 and 29 to the gas outlet C; The column 11 is subjected to a vacuum desorption process, and the sulfide and the thiol which are originally adsorbed in the sulfide purification tower 11 are desorbed by the vacuuming of the vacuum pump 20 by 10 201039910. The exhaust gas outlet B is discharged or recovered; during the completion of the decompression desorption process by the sulfide purification tower 11, the valves 27 and 30 can be further opened and introduced into the gas stream D for the purge of the sulfide purification tower 11. In the above gas purification process, a single sulfide purification tower 11 can also be used for purification treatment, and only the single sulfur sulfide purification tower 11 is used for purifying the sulfur-containing exhaust gas, only the valves 21, 25 and 29 are opened; The waste purification tower is simultaneously used for purification operation, and only the switches of the valve groups can be used to achieve the batch purification operation. The high bismuth aluminum ratio zeolite adsorbing material filled in the above-mentioned sulfide purification tower, wherein the samarium aluminum ratio of the high bismuth aluminum to the zeolite adsorbing material is 10 or more, and the desorbed sulfur-containing compound is hydrogen sulfide or And methanol sulphur; and the sorghum aluminum specific adsorbing material is MCM-41 zeolite, Y-type zeolite or sorghum zeolite, and the sorghum aluminum specific zeolite adsorbing material has a formed shape of granular or honeycomb. The test of the performance of the device is carried out by using a sulfide-containing exhaust gas, wherein the composition of the sulfide-containing exhaust gas is: hydrogen sulfide 600 ppm, methyl mercaptan 150 ppm, water gas 25000 ppm, barium burned 65%, and carbon dioxide carbon 32.5%, and the inflow temperature. 25 ° C; and filled in these sulfide purification towers: MCM-41 zeolite (honeycomb), Y-type zeolite (honeycomb), sorghum zeolite (honeycomb and granular) and activated carbon (honeycomb) The test results of sulfide-containing exhaust gas purification are as follows: 11 201039910 Purification efficiency evaluation of hydrogen and methanol y adsorption J material / type I MCM-411JJ- (honeycomb type Y zeolite (honeycomb 1 sorghum) Boiling ^ (Hive) Nanshi Xishi Stone (Particle @ Activated Carbon (Honeycomb Removal Efficiency CH3SH Removal Efficiency Effectiveness Evaluation > 99 % > 95 % > 99 % > 85 % 50% • 50 % > 70 % > 99 % > 80 % < 10 % H2s efficiency is better -3⁄4 Yin purification h2s) h2s efficiency is better in purifying h2s) Efficiency is good efficiency -~· . _____ Efficiency is affected by water and gas jjg〇 by μ The influence of the main ^---~~~~~~~ijg〇 and the ancient 2 results, when using MCM-41 stagnation, Type zeolite II C stone: can effectively remove the vulcanized gas' and also remove the removal efficiency of methyl mercaptan to methyl mercaptan by only 50% or more; Renfang antimony activated carbon is the adsorbent of sulfide, its effect is not good Only sulphuric acid 虱5〇% 'methyl mercaptan is less than 1 〇" is used as a sulfide adsorbing material. The lower Yang W is not suitable and the adsorbing materials MCM-41 Fossil, γ _ stone = ratio are greater than Η) Above, wherein the 丫-type zeolite 二二石 沸石 之 石 铭 比 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 。 。 。 。 。 。 。 。 。 。 After the exhaust gas purification is completed, close the door between the original purification operation, the Naca 23 or / and 24 and the vacuum pump 2G, = vacuum decompression mode, so that it is originally adsorbed in the sulfides or the ^ 12 Sulfide and methyl mercaptan are desorbed and discharged or recovered by NOx. 12 201039910 In the above desorption reaction, valves 27 or/and 28 and 30 may be simultaneously opened, using a gas inlet D, At the same time, ozone, moisture or steam is provided to accelerate the desorption of hydrogen sulfide and hydrazine thiol. A biogas decane recovery device 2 of the embodiment is as shown in the second figure, wherein the device comprises: a blower 10, a vacuum pump 20, a valve member combination (41 to 57) and a second biogas methane recovery tower. 31, 32. The following valve groups are all closed unless otherwise stated. Recovery of biogas smoldering First, the blower 10 is turned off, and the opening and closing states are performed according to the sequence of the operation procedure of Table 2 and the opening instruction of the valve member, and the gas inlet A can be processed by the blower 10 during the adsorption process. The biogas is introduced into the biogas decane recovery towers 31 or/and 32, and the biogas decane recovery towers 31, 32 are filled with a sulfide adsorbent and a biogas methane recovery agent for purifying the sulfur contained in the biogas. The compound and carbon dioxide, and then the purified decane is discharged via 44, 54 and 57 to the gas outlet C1. In the above-mentioned biogas methane recovery process, a single biogas methane recovery tower 31 may be used for purification treatment, and only a single biogas decane recovery tower 31 is used to purify the sulfur-containing exhaust gas, and only the valves 41, 44 and 57 are opened; The second biogas methane recovery tower is used for simultaneous purification operations, and the batch cleaning operation can be achieved only by using the switch control of the valve groups. Table 2: Operation procedure and valve opening explanation Operation steps Open valve recovery tower 31 Recovery tower 32 13 201039910 a. Feed pressure adsorption program d Reverse decompression desorption procedure 41, 48, 52 b. Continuous feeding Adsorption procedure e. Continuous decompression desorption procedure 41, 44, 48, 52, 57 C. Co-decompression desorption procedure £ product back pressure procedure 44, 56, 57 d. Reverse decompression desorption procedure a. Feeding Pressurization adsorption procedure 42, 48, 51 e. continuous decompression desorption procedure b. continuous feed adsorption procedure 42, 48, 51, 54, 57 f. product back pressure procedure C. co-directional decompression desorption procedure 46, 5457, wherein the recovery tower 31 performs the a+b + c present d+e + f cycle program, and at the same time, the recovery tower 32 performs a corresponding cycle program of d+e+f+a+b + c; wherein, the d step The DL low pressure flushing procedure can be further increased after the reverse pressure desorption detachment procedure, at which time the recovery towers 31, 32 are opened for the valve members 43, 45, 51, 54 and 57, or the recovery towers 31, 32 are operated for the valve members 41, 44, 53 55, 57 and 57; or, d step reverse decompression detachment procedure can further increase the d2 high pressure product rinsing procedure, at this time the recovery towers 31, 32 for valve members 42, 46, 51, 54 and 57 Opening, or the recovery towers 31, 32 are opened for the valve members 41, 44, 52, 56 and 57; the sulfide adsorbent filled in the biogas decane recovery tower is a sorghum aluminum ratio zeolite adsorbent, wherein The strontium aluminum has a ratio of bismuth to aluminum of 10 or more, and the desorbed sulfur-containing compound is hydrogen sulfide or/and sterol sulphur; and the sorghum-aluminum specific adsorbent is MCM-41 zeolite. , Y-type zeolite or sorghum zeolite, and the sorghum-aluminum ratio zeolite shaped material is formed into a granular or honeycomb shape; and the biogas decane recovery agent is used for separating carbon dioxide and decane in the biogas, and The biogas methane recovery agent is composed of activated carbon and zeolite, and the activated carbon is activated carbon modified by Ca2+, Mg2+ or Cu2+; and the X-type zeolite is Li-X, Ca-X, Sr-X, Mg-X or Na-X type zeolite. 14 201039910 The test for enabling the device with biogas is: bismuth sulfide (10) Peng, A (four) 2nW estimate 'the composition ratio of the biogas / PPm, water vapor 3.5% volume 100% A & 68 / 〇 and a carbon 28 5〇 / 〇, and into the filled sulfide adsorbent sorghum zeolite (矽铕n", and jk 乂 π π 2+n and 匕 匕 45 〇), and the active anaesthesia and C u modified activated charcoal; and the Buddha stone is (10), biogas methane recovery test.
於上述測試後之結果，該沼氣 ^ 烷回收之效率為：該 |化風之去除㈣99%m醇叙去除率為98%以 上、二氧化狀去除率為98%以上，並該^之回收率係 為90%以上，可有效去除沼氣中之硫化氯、甲醇硫及二氧 化碳，而淨化回收90%以上之甲燒。 沼氣曱烷回收塔之再生 富該沼氣甲烧回收完成之後’關閉原甲燒回收操作時 所開啟之閥門，再開啟閥門42、52、48及真空幫浦20， 於用減壓真空方式，使原本吸附於該等沼氣曱燒回收塔 31、32内之硫化物、甲硫醇及二氧化碳被脫附，而經廢氣 出口 B1所排放或回收。 實施例3 本發明第三具體實施例之一種兩階段沼氣曱燒回收 楚置3係如第三圖所示，其中該裝置係包含：二鼓風機 1〇、10-1、二真空幫浦20、20-1、二閥件組合(21〜30)、 (41〜57)、二硫化物淨化塔11、12及二曱烷淨化塔61、62。 教以下各閥組除另有說明外，皆為關閉狀態。 15 201039910 沼氣曱烧之回收 首先’關啟鼓風機10、〗〇」、閥2丨、22、25、26、 29、41、51、44、d - 汉57，經由該鼓風機10可將氣體入 口 A將所欲處理之沼氣導入該硫化物淨化塔11及12，於 該等硫化物淨化塔η、12中係填充硫化物吸附劑，用於 淨化於沼氣中之含硫化合物，而經吸附硫化物之沼氣再流 紅闕25、26及29 ’並經氣體出口 c再流經鼓風機1〇] 及閥41、51導人遠等甲燒回收塔61、62之中，進而分離 氣體中所含之二氧化碳及甲烧，再將淨化後甲炫經由44、 54及57至氣體出口 C2排放。 而上述之❺氣曱烧回收過程中，亦可使用單一 疏化物淨化塔11及單—甲垸回收塔61進行淨化處理，唯 使用單-沼氣伐回收塔31進行含㈣氣淨化時，僅開 啟相關需求之㈤組即可；並於上料階段减代回收操 作k H硫化物淨化塔及二沼氣伐回收塔係同時淨 化操作使用，唯亦可利用該等閥組之開關控制，而達成批 次淨化操作。 於上述之硫化物淨化塔中所填充之硫化物吸附劑係 為一咼矽鋁比沸石吸附材，其中該高矽鋁比沸石吸附材之 矽鋁比為10以上，且所脫附之含硫化合物係為硫化氫或/ 及曱醇硫；並該等高矽鋁比吸附材係為MCM-41沸石、Y 型沸石或高石夕沸石，並該等高矽鋁比沸石吸附材之成形形 狀為顆粒狀或蜂巢狀；並其中之沼氣甲烷回收塔係用以分 離沼氣中之二氧化碳及甲烷，且内之沼氣甲烷回收劑係由 16 201039910 %2+或 、Sr-X、 活性碳及沸石所組成，而該活性碳係為經Ca2+、 Cu2+改質之活性碳；且該χ型沸石係為Li_x、ca_x Mg-X或]sia-X型沸石。 以沼氣進行該裝置效能之測試評估，其中該绍氣 、 份為：硫化氫120ppm、曱硫醇20pPm、水氣3.5%體浐〇 分比、曱烧68〇/。及二氧化礙28.5〇/〇，且入流溫為29t：二= 填充之硫化物吸附材高石夕彿石（石夕铭比為450)、而該活性As a result of the above test, the efficiency of the biogas recovery is: the removal of the chemical wind (four) 99% m alcohol removal rate of 98% or more, the dioxide removal rate of 98% or more, and the recovery rate of the ^ It is more than 90%, which can effectively remove sulphurized chlorine, methanol sulphur and carbon dioxide in biogas, and purify and recover more than 90% of smoldering. The regeneration of the biogas decane recovery tower is completed. After the recovery of the biogas recovery, the valve opened when the original A-burn recovery operation is closed, and then the valves 42, 52, 48 and the vacuum pump 20 are opened, and the vacuum vacuum method is used. The sulfide, methyl mercaptan and carbon dioxide originally adsorbed in the biogas scrub recovery towers 31, 32 are desorbed and discharged or recovered through the exhaust gas outlet B1. Embodiment 3 A two-stage biogas smoldering recovery of the third embodiment of the present invention is as shown in the third figure, wherein the apparatus comprises: two blowers 1〇, 10-1, and two vacuum pumps 20, 20-1, two valve member combinations (21 to 30), (41 to 57), disulfide purification columns 11, 12 and dioxane purification columns 61, 62. The following valve groups are taught to be closed unless otherwise stated. 15 201039910 Recycling of biogas smoldering first, 'closed blower 10, 〗 〇 』, valves 2 丨, 22, 25, 26, 29, 41, 51, 44, d - han 57, gas inlet A can be passed through the blower 10 Introducing the biogas to be treated into the sulfide purification towers 11 and 12, and filling the sulfide purification towers η and 12 with a sulfide adsorbent for purifying the sulfur-containing compound in the biogas, and adsorbing the sulfide The biogas recirculates the red enthalpy 25, 26 and 29 ' and flows through the blower 1 through the gas outlet c] and the valves 41, 51 lead into the recovery tower 61, 62, which is contained in the separation gas. Carbon dioxide and smoldering will be released after the purification of A, Hyun, through 44, 54 and 57 to the gas outlet C2. In the above-mentioned helium gas calcination recovery process, a single sparging purification tower 11 and a mono-methane recovery tower 61 may be used for purification treatment, and only the single-biogas recovery tower 31 is used for purifying (4) gas, only the gas is turned on. The relevant requirements (5) group can be used; and in the loading stage, the recovery operation k H sulfide purification tower and the second biogas recovery tower are simultaneously cleaned and used, but only the switch control of the valve groups can be used to achieve the batch Secondary purification operation. The sulfide adsorbent filled in the above-mentioned sulfide purification tower is a mono-alumina-specific zeolite adsorbing material, wherein the high-alumina aluminum has a ratio of germanium to aluminum of 10 or more, and the desorbed sulfur-containing material The compound is hydrogen sulfide or/and sterol sulfur; and the sorghum aluminum specific adsorbing material is MCM-41 zeolite, Y-type zeolite or high-stone zeolite, and the shape of the sorghum-aluminum specific zeolite adsorbing material is Granular or honeycomb; and the biogas methane recovery tower is used to separate carbon dioxide and methane from the biogas, and the biogas methane recovery agent is composed of 16 201039910 % 2+ or Sr-X, activated carbon and zeolite. The activated carbon is activated carbon modified by Ca2+ or Cu2+; and the zeolite of the cerium type is Li_x, ca_x Mg-X or sia-X type zeolite. The biogas was used to evaluate the performance of the device. The gas content was 120 ppm hydrogen sulfide, 20 pPm bismuth thiol, 3.5% body water content, and 68 〇. And the oxidation of 28.5 〇 / 〇, and the inlet temperature is 29t: two = filled sulfide adsorbent material Shishi Xifo stone (Shi Ximing ratio is 450), and the activity
碳係為經Cu2+改質之活性碳；且該沸石係為Li_Xs沸石， 進行沼氣曱烷回收測試。 於上述測試後之結果，該沼氣甲烷回收之效率為：該 硫化氫之去除率為95%以上、曱醇硫之去除率為 70〇/〇 以 上一氧化奴之去除率為98%以上，並該甲炫之回收率係 為85/〇以上，可有效去除沼氣中之硫化氫、甲醇硫及二氧 化碳，而淨化回收85%以上之甲烷。 此外，本發明之兩階段沼氣甲燒回收裝置可進一步包 含一曱烷儲存單元63，其係用於貯存經淨化回收之甲烷， 其操作係利用相關閥門57、58及59之操作，即可達到貯 存淨化曱烷之功效，並該曱烷儲存單元63係可由經磷酸 活化製備之活性礙所構成。 硫化物淨化塔及沼氣甲烷回收塔之再生 當該沼氣曱烷回收完成之後，關閉原沼氣曱烷回收操 作時所開啟之閥門’再麟適當閥Η及真空幫浦，利用減 壓真空方式，使原本吸附於該等硫化物淨化塔及沼氣曱烷 回收塔之硫化物、甲硫醇及二氡化碳被麟，而分別經由 17 201039910 廢氣出口 B及B2所排放或回收。 藉由上述裝置本發明亦提供一種含硫廢氣淨化之方 法，其係包含下列步驟： (1) 提供如上所述之含硫廢氣淨化裝置，用以脫附含硫 化合物； (2) 經由鼓風機將所欲處理之含硫廢氣導入該裝置，開 啟或/及關閉相關閥組，以進行含硫化合物之脫附，並同時 排放經吸附含硫化合物後淨化氣體； (3) 開啟或/及關閉相關閥組，利用真空幫浦抽吸該裝 置内之含硫化合物，以進行吸附材之再生。 同時，本發明亦提供一種沼氣甲烷回收之方法，其係 包含下列步驟： (1) 提供如上所述之沼氣曱烷回收裝置，用以回收沼氣 曱烷； (2) 經由鼓風機將所欲處理之沼氣導入該裝置，開啟或 /及關閉相關閥組，以進行含硫化合物之脫附及二氧化碳與 曱烷之分離，並同時回收經淨化處理之曱烷； (3) 開啟或/及關閉相關閥組，利用真空幫浦抽吸該裝 置内之含硫化合物及二氧化碳，以進行吸附材之再生。 藉此，本發明之含硫廢氣淨化及沼氣曱烷回收之方法 及裝置，係可有效的淨化含硫廢氣，並同時回收沼氣曱 烷，可充分有效利用沼氣資源，達成自然資源之有效利用。 18 201039910 【圖式簡單說明】 第一圖係為本發明第一具體實施例之含硫廢氣淨化裝置 之示意圖。 第二圖係為本發明第二具體實施例之沼氣甲烷回收裝置 之示意圖。 第三圖係為本發明第三具體實施例之兩階段沼氣甲烷回 收裝置之示意圖。 【主要元件符號說明】 1 含硫廢氣淨化裝置 2 沼氣曱烷回收裝置‘ 3 兩階段沼氣曱烷回收裝置 10 鼓風機 10-1 鼓風機 20 真空幫浦 20-1 真空幫浦 11、12 硫化物淨化塔 21 〜30 閥門 3卜32 沼氣曱烧回收塔 41〜59 閥門 61 > 62 甲烷淨化塔 63 甲烷儲存裝置 A 氣體入口 B、B卜 B2 廢氣出口 19 201039910 c 氣體出口 D 氣體入口The carbon system is a Cu2+-modified activated carbon; and the zeolite is a Li_Xs zeolite, and a biogas decane recovery test is performed. As a result of the above test, the methane recovery efficiency of the biogas is: the removal rate of the hydrogen sulfide is more than 95%, the removal rate of the mercaptan sulfur is 70〇/〇, and the removal rate of the niobium is 98% or more. The recovery rate of the product is 85/〇 or more, which can effectively remove hydrogen sulfide, methanol sulfur and carbon dioxide in the biogas, and purify and recover more than 85% of methane. In addition, the two-stage biogas calcination recovery unit of the present invention may further comprise a decane storage unit 63 for storing the purified and recovered methane, the operation of which is achieved by the operation of the associated valves 57, 58 and 59. The effect of purifying decane is stored, and the decane storage unit 63 is composed of an active substance prepared by activation of phosphoric acid. Regeneration of the sulphide purification tower and the biogas methane recovery tower After the recovery of the biogas decane is completed, the valve opened by the original biogas decane recovery operation is closed, and the vacuum valve is used to reduce the pressure and vacuum. Sulfide, methyl mercaptan and dibasic carbon which are originally adsorbed in the sulfide purification tower and the biogas decane recovery tower are discharged or recovered through the exhaust gas outlets B and B2 of 17 201039910, respectively. The present invention also provides a method for purifying sulfur-containing exhaust gas, which comprises the steps of: (1) providing a sulfur-containing exhaust gas purifying device as described above for desorbing a sulfur-containing compound; (2) passing a blower The sulfur-containing waste gas to be treated is introduced into the device, and the relevant valve group is opened or/closed to perform desorption of the sulfur-containing compound, and at the same time, the sulfur-containing compound is discharged to purify the gas; (3) opening or/and closing The valve block uses a vacuum pump to pump the sulfur-containing compound in the device to perform regeneration of the adsorbent material. At the same time, the present invention also provides a method for recovering methane from biogas, which comprises the following steps: (1) providing a biogas decane recovery device as described above for recovering biogas decane; (2) treating the desired gas via a blower Biogas is introduced into the device to open or/and close the relevant valve block for the desorption of sulfur compounds and the separation of carbon dioxide from decane, and at the same time to recover the purified decane; (3) opening or / closing the relevant valve In the group, a vacuum pump is used to pump the sulfur-containing compound and carbon dioxide in the device to regenerate the adsorbent. Accordingly, the method and apparatus for purifying sulfur-containing exhaust gas and recovering biogas decane of the present invention can effectively purify sulfur-containing waste gas and simultaneously recover biogas decane, thereby fully utilizing biogas resources and achieving effective utilization of natural resources. 18 201039910 BRIEF DESCRIPTION OF THE DRAWINGS The first drawing is a schematic view of a sulfur-containing exhaust gas purifying apparatus according to a first embodiment of the present invention. The second drawing is a schematic view of a biogas methane recovery unit according to a second embodiment of the present invention. The third figure is a schematic diagram of a two-stage biogas methane recovery unit according to a third embodiment of the present invention. [Explanation of main components] 1 Sulfur-containing exhaust gas purification device 2 Biogas decane recovery unit 3 Two-stage biogas decane recovery unit 10 Blower 10-1 Blower 20 Vacuum pump 20-1 Vacuum pump 11, 12 Sulfide purification tower 21 ～30 Valve 3 卜 32 Biogas smoldering recovery tower 41~59 Valve 61 > 62 Methane purification tower 63 Methane storage unit A Gas inlet B, B Bu B2 Exhaust gas outlet 19 201039910 c Gas outlet D Gas inlet
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