201124195 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種二氧化碳吸附裝置，特別是關於一 種可以有效去除電廒或工薇排放廢氣中二氧化碳之裝置。 【先前技術】 隨著溫室效應日漸顯著，京都議定書也正式生效，同 日卞一氧化故捕獲及封存技術（Carbon dioxide Capture and Storage，簡稱CCS)也於2〇〇5年被聯合國之Ιρ(χ組織評估 為可行方式之一，相關文獻與專利不勝枚舉。其中包括最 普遍被探討的濕式吸收MEA法、乾式吸附法、薄膜法等。 經搜哥二氧化碳吸附相關專利，於中華民國專利有「由 一含二氧化碳之氣流中吸附二氧化碳的方法、二氧化碳吸 附劑及其製造方法（證書號：176857)」、「二氧化礙自氣流 中之移除（公告號：592788)」及「從空氣進料流中除去水、 氧化炭和—氮的方法及設備、空氣分離方法及設 備（Α σ號.4555Q5)」”等’然於此三個專利中的應用範 圍或其所使用之材料均與本專利不相同。 此外’於中國專利中，則有「利用氧化转和稻殼灰製 備二氧化碳吸附劑的方法(2〇〇81〇156154 4)」、「含硅鈉米氧 化詞高溫二氧化碳吸附劑和該吸附劑的製備方法以及在製 氫工藝中的應用（申請號：20〇51006091M)」及「固觫二 氧化礙吸附劑及其製傷方*(.申請.號：仙9387.2)」，^ 個專利中所使用之材料與本專利亦並不相同。而「二氧化 201124195 碳回收裝置（申請號：200720034221.6)」之裝置則屬於工 業應用如啤酒工業裝置設備，其並非應用於電廠或工業廢 氣中。 美國專利中之相關專利有Gray et al.(2003)” AMINE ENRICHED SOLID SORBENTS FOR CARBON DIOXIDE CAPTURE(Pat. #: US 6,547,854 Bl)"，其内容係為將吸附 基材經酸鹼液處理後，再經金屬氧化物、胺鹽等處理以達 到官能化之目的，其基材雖然包括奈米碳管及分子篩等， 但於此方法中所得之二氧化碳吸附量較低，最高僅 0.17mmole/g (7.48mg/g)，且該專利僅揭示吸附劑本身，並 未與裝置進一步結合。 而 Pennline and Haffman (2002)之，’ Carbon dioxide capture process with regenerable sobents (Pat. #: US 6,387,337 Bl) ’則是使用驗金屬（aikali metals)或驗土金 屬（alkali earth metals)做為吸附劑，於一個雙床式反應器中 與二氧化碳溫室氣體反應，其所使用之吸附劑及裝置亦與 本案所揭示之内容並不相同。 另於 Gray et al. (2007)之專利” HIGH CAPACITY IMMOBILIZED AMINE SORBENTS (Pat.#: US 7,288,136 Bl)” ，則是使用二級胺做為改質劑，其所使用之吸附基材 可以為奈米碳管或分子篩，而其專利揭露範圍僅涵蓋吸附 劑本身，且該吸附劑之最佳吸附量亦低於本專利所揭示裝 置之結果，故亦與本發明所揭示之内容不同。 其他相關文獻包括Lu et al,(2〇〇8)之“Comparative 201124195 study of C02 capture by carbon nanotubes, activated carbon and zeolites (Energy & Fuels, 22, 3050-3056)”，CNTs、活性 碳、沸石經APTS處理後，顯示CNT(APTS)具有最佳二氧 化碳吸附能力。Su et al.(2009)之 “C02 Capture from flue gas via multiwalled carbon nanotubes (Science of the Total Environment，407, 3017-3023)”。以 CNTs 利用 APTS、EDA 及PEI改質後，以APTS改質的C02吸附量為最佳，其吸 附量於低溫(20-60°C)下有較佳之吸附效果，唯其未針對含 水率之影響加以探討，且未與吸附裝置進行結合。 因此，於習知文獻或專利中尚未見有效結合吸附劑與 吸附實驗裝置之相關研究成果，可於低溫吸附(<8〇。〇下將 二氧化碳進行連續性快速吸附，且該吸附材具不易劣化之 功效。故本發明提供一種二氧化碳吸附系統，其係藉由一 調濕器與一吸附裝置（内含吸附材）之結合，以提升二氧 化碳之吸附能力並降低能資源消耗，同時遠成降低成本效 益以有效吸附廢氣中二氧化碳之目的。 【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 在提供一種二氧化碳之吸附系統，其係包含： 凋濕器，其係用於調整一待處理廢氣之濕度；以及 ^ 吸附裝置，其係用於提供二氣化碳吸附材以吸附該 待處理廢氣中之二氧化碳。 如上所述之吸附系統，其中該吸附材係玎為經201124195 VI. Description of the Invention: [Technical Field] The present invention relates to a carbon dioxide adsorption apparatus, and more particularly to an apparatus capable of effectively removing carbon dioxide in an exhaust gas of an electric raft or a weiwei. [Prior Art] With the increasing greenhouse effect, the Kyoto Protocol has also come into effect. On the same day, the Carbon dioxide Capture and Storage (CCS) technology was also adopted by the United Nations in 2005. Evaluation is one of the feasible methods, and the related literatures and patents are numerous, including the most commonly discussed wet absorption MEA method, dry adsorption method, thin film method, etc. According to the search for carbon dioxide adsorption related patents, the Republic of China patent has " Method for adsorbing carbon dioxide from a carbon dioxide-containing gas stream, carbon dioxide adsorbent and its method of manufacture (Certificate No.: 176857), "Removal of dioxin from airflow (Announcement No.: 592788)" and "feeding from air" Method and equipment for removing water, carbon oxide and nitrogen in the stream, air separation method and equipment (Ασ.4555Q5)", etc., but the application scope of the three patents or the materials used therein are The patents are different. In addition, in the Chinese patent, there is a method for preparing carbon dioxide adsorbents by using oxidative conversion and rice husk ash (2〇〇81〇156154 4). "Sodium-containing sodium sulphur word high-temperature carbon dioxide adsorbent and preparation method of the adsorbent and application in hydrogen production process (application number: 20〇51006091M)" and "solid bismuth dioxide oxidizing agent and its injured party" *(.Application No.: 9387.2)", the materials used in the ^ patents are not the same as this patent. The device of "Second Energy 201124195 Carbon Recovery Unit (Application No.: 200720034221.6)" is an industrial application. Beer industry equipment, which is not used in power plants or industrial waste gas. The related patents in the US patent are Gray et al. (2003) "AMINE ENRICHED SOLID SORBENTS FOR CARBON DIOXIDE CAPTURE (Pat. #: US 6,547,854 Bl)", The content thereof is that the adsorbed substrate is treated with an acid-base solution, and then treated with a metal oxide, an amine salt or the like to achieve functionalization. The substrate includes a carbon nanotube and a molecular sieve, etc., but in this method, The resulting carbon dioxide adsorption is low, up to only 0.17 mmole/g (7.48 mg/g), and the patent only reveals the adsorbent itself and does not further bind to the device. Pennline and Haffman (2002) 'Carbon dioxide capture process with regenerable sobents (Pat. #: US 6,387,337 Bl)' is the use of aikali metals or alkaline earth metals as adsorbents in a two-bed reactor The carbon dioxide greenhouse gas reaction, the adsorbents and devices used therein are also different from the contents disclosed in the present case. In addition, the patent "High CAPACITY IMMOBILIZED AMINE SORBENTS (Pat. #: US 7,288,136 Bl)" by Gray et al. (2007) uses a secondary amine as a modifier, and the adsorption substrate used can be Nai. The carbon nanotube or molecular sieve, and the scope of its patent disclosure only covers the adsorbent itself, and the optimum adsorption amount of the adsorbent is also lower than that of the device disclosed in the patent, and thus is different from the disclosure of the present invention. Other relevant literature includes Lu et al, (2〇〇8) "Comparative 201124195 study of C02 capture by carbon nanotubes, activated carbon and zeolites (Energy & Fuels, 22, 3050-3056)", CNTs, activated carbon, zeolite After treatment with APTS, it was shown that CNT (APTS) has the best carbon dioxide adsorption capacity. Su et al. (2009) "C02 Capture from flue gas via multiwalled carbon nanotubes (Science of the Total Environment, 407, 3017-3023)". After the CNTs were modified by APTS, EDA and PEI, the adsorption amount of C02 modified by APTS was the best, and the adsorption amount was better at low temperature (20-60 °C), but it was not for moisture content. The effects were explored and not combined with the adsorption unit. Therefore, in the conventional literature or patent, the relevant research results of the effective combination of the adsorbent and the adsorption experimental device have not been found, and the adsorption can be carried out at low temperature (<8〇. The carbon dioxide is continuously and rapidly adsorbed under the armpit, and the adsorbing material is not easy to be used. The invention provides a carbon dioxide adsorption system, which combines a humidity regulator and an adsorption device (containing an adsorption material) to enhance the adsorption capacity of carbon dioxide and reduce the energy consumption, and at the same time reduce the distance. It is cost-effective to effectively adsorb carbon dioxide in the exhaust gas. SUMMARY OF THE INVENTION In order to improve the problems faced by the above-mentioned prior art, the object of the present invention is to provide a carbon dioxide adsorption system comprising: a humidifier, which is used for Adjusting the humidity of the waste gas to be treated; and the adsorption device for supplying the carbon dioxide adsorbing material to adsorb the carbon dioxide in the waste gas to be treated. The adsorption system as described above, wherein the adsorbent material is a
APTS 201124195 改質奈米碳管、經ΤΕΡΑ改質奈米碳管或經ΤΕΡΑ改質之矽 在呂比60的Υ型沸石。 如上所述之吸附系統，其中該吸附單元係可為一固定 床式吸附器或旋轉轉環式吸附器或一轉輪式吸附器或流體 化浮動式吸附器。 如上所述之吸附系統，當該吸附單元為該旋轉轉環式 吸附器時，進一步包含複數個二氧化碳吸附箱塊，其係用 於填充二氧化碳吸附材。 如上所述之吸附系統，當該吸附材為經APTS改質奈 米碳管時，其濕度範圍較佳為〇〜17%，更佳為2〜5%。 如上所述之吸附系統，當該吸附材為經ΤΕΡΑ改質奈 米碳管時，其濕度範圍較佳為〇〜17%，更佳為2〜5%。. 如上所述冬吸附系統，當該吸.附材為經ΤΕΡΑ改質之 矽鋁比60的Υ型沸石時，其濕度範圍較佳為2〜17%，更 佳為7〜8%。 上述之二氧化碳吸附系統，其係藉由一調濕器與一吸 附裝置（内含吸附材）之結合，以提升二氧化碳之吸附能 力並降低能資源消耗，同時達成降低成本效益以有效吸附 廢氣中二氧化碳之目的。 下列實驗設計係為說明，不應限制本發明之範疇，合 理的變化，諸如對於熟習此項技藝者顯而易見為合理者， 可於不脫離本發明之範疇下進行。 【實施方式】 201124195 马使充分瞭解本發 述具體之實施例，並配合^的、特徵及功效，兹藉由下 說明，說明如後： 、之圖式，對本發明做—禅細APTS 201124195 Modified carbon nanotubes, modified ternary carbon nanotubes or modified ruthenium. The adsorption system as described above, wherein the adsorption unit is a fixed bed adsorber or a rotary toroidal adsorber or a rotary wheel adsorber or a fluidized floating adsorber. The adsorption system as described above further comprises a plurality of carbon dioxide adsorption block blocks for filling the carbon dioxide adsorbing material when the adsorption unit is the rotary rotary ring adsorber. In the adsorption system as described above, when the adsorbent material is an APTS modified carbon nanotube, the humidity is preferably in the range of 〇 17%, more preferably 2 5%. In the adsorption system as described above, when the adsorbent is a rhodium-modified carbon nanotube, the humidity is preferably in the range of 〇 17%, more preferably 2 5%. In the winter adsorption system as described above, when the absorbent material is a ruthenium-modified zeolite having a ruthenium-alumina ratio of 60, the humidity is preferably in the range of 2 to 17%, more preferably 7 to 8%. The carbon dioxide adsorption system described above is combined with a humidifier and an adsorption device (containing an adsorbent material) to enhance the adsorption capacity of carbon dioxide and reduce energy consumption, and at the same time achieve cost-effectiveness to effectively adsorb carbon dioxide in the exhaust gas. The purpose. The following experimental design is intended to be illustrative, and is not intended to limit the scope of the invention, and it is obvious that such modifications may be made without departing from the scope of the invention. [Embodiment] 201124195 The horse fully understands the specific embodiments of the present invention, and cooperates with the features, functions and effects of the present invention, and the following descriptions are given to illustrate the following:
請參見第1圖H 附系統之—示意圖，‘圖：為本發明-種二氧化碳吸 濕器2及一吸附襞置20:“氧化碳吸附系統係包含—調Please refer to Figure 1 for the system attached to the system. ‘Figure: The present invention is a carbon dioxide absorber 2 and an adsorption device 20: “The carbon oxide adsorption system contains
…自-廢氣一進，濕 濕氣後之待處理廢氣再;^之濕氣含量’接著經調節 理廢氣進人該吸附裝置，當該待處 附二氧化碳之吸附材，會二吸：裝置内含有可吸 ^^ 霄針對該待處理廢氣中之_ 之 氧化^1 吸附作用’最後經吸附淨化 σ 乳化兔之淨化純再流出該吸附裂置2G，流經該氣體出 B排出。 一...from the exhaust gas, the exhaust gas to be treated after the wet moisture; the moisture content of the ^ is then adjusted to the exhaust gas into the adsorption device, and when the adsorbent material to be attached with carbon dioxide is sucked: the device Containing absorbing ^ 霄 霄 霄 霄 霄 霄 霄 霄 ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' 氧化 ' ' ' ' 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化One
實施例1 : 本發明第〆具體實施例之一種二氧化碳吸附系統J係 如第2圖所示，其中該系統係包含：一調濕器1〇及一吸附 裴置20;其中該吸附裝置20之内包含複數個二氧化碳吸附 單元11，並該二氧化碳吸附單元11填充有二氧化碳吸附材 13。 當該二氧化碳吸附系統1進行二氧化碳吸附淨化時， 待處理廢氣自〆氣體入口 Α經由一風車5·吹入該二氧化碳 7 201124195 吸附系統1之中，首先流經該調濕器10之中，本實施例之 調濕器10係為一水喷霧加濕器具有加濕與兼具降溫之功 能，以調節該待處理廢氣之濕氣，接著經調濕之待處理廢 氣進入該吸附裝置20之内，而隨著第2圖中該吸附裝置10 内之箭頭進行氣體之流動，而該待處理廢氣中之二氧化碳 則被該二氧化碳吸附單元11中之二氧化碳吸附材13所吸 附，其中該二氧化碳吸附材13係為二氧化碳吸附基材，而 該二氧化碳吸附基材係可為奈米碳管、沸石分子篩或純矽 中孔洞吸附材等低溫吸附材，並可進一步經改質劑改質， 於本實施例中之改質劑係為含胺官能基之改質劑，而使用 之二氧化碳之吸附材係為經APTS改質之奈米碳管、經 ΤΕΡΑ改質之奈米碳管或經ΤΕΡΑ改質之矽鋁比60之Y型 沸石；而該待處理廢氣流經該等二氧化碳吸附單元11之 後，其内包含之二氧化碳即為該二氧化碳吸附材13所吸 附，完成二氧化碳之吸附作用，最後經吸附淨化二氧化碳 之淨化廢氣再流出該吸附裝置20,流經該氣體出口 Β排出。 實施例2 : 本發明第二具體實施例之一種二氧化碳吸附系統2係 如第3圖所示，其中該系統係包含：一調濕器10及一旋轉 轉環式吸附器30;其中旋轉轉環式吸附器30係由複數個二 氧化碳吸附箱塊22組合而成，並該等二氧化碳吸附箱塊22 .係填充有二氧化碳吸附材，該等二氧化碳吸附箱塊22便於 二氧化碳吸附材之更換。 201124195 當该有二Embodiment 1 : A carbon dioxide adsorption system J according to a third embodiment of the present invention is shown in FIG. 2, wherein the system comprises: a humidity regulator 1 and an adsorption device 20; wherein the adsorption device 20 A plurality of carbon dioxide adsorption units 11 are contained therein, and the carbon dioxide adsorption unit 11 is filled with a carbon dioxide adsorbing material 13. When the carbon dioxide adsorption system 1 performs carbon dioxide adsorption purification, the exhaust gas to be treated is blown into the carbon dioxide 7 201124195 adsorption system 1 through a wind turbine 5, and first flows through the humidity control device 10, and the present embodiment is implemented. The humidifier 10 is a water spray humidifier having a function of humidifying and cooling, so as to adjust the moisture of the exhaust gas to be treated, and then the waste gas to be treated that has been conditioned to enter the adsorption device 20 And the gas flows in the adsorption device 10 in FIG. 2, and the carbon dioxide in the exhaust gas to be treated is adsorbed by the carbon dioxide adsorbing material 13 in the carbon dioxide adsorption unit 11, wherein the carbon dioxide adsorbing material 13 The carbon dioxide adsorption substrate is a low temperature adsorption material such as a carbon nanotube, a zeolite molecular sieve or a pore-adsorbing material in a pure crucible, and can be further modified by a modifier, in this embodiment. The modifier is an amine functional group-containing modifier, and the carbon dioxide adsorbent used is an APTS modified carbon nanotube, a ruthenium modified carbon nanotube or The yttrium-modified yttrium aluminum has a ratio of 60 to the Y-type zeolite; and after the exhaust gas to be treated flows through the carbon dioxide adsorption unit 11, the carbon dioxide contained therein is adsorbed by the carbon dioxide adsorbing material 13 to complete the adsorption of carbon dioxide, and finally The purified exhaust gas which has been adsorbed and purified by carbon dioxide flows out of the adsorption device 20, and flows through the gas outlet port. Embodiment 2: A carbon dioxide adsorption system 2 according to a second embodiment of the present invention is shown in FIG. 3, wherein the system comprises: a humidity regulator 10 and a rotating rotary ring adsorber 30; wherein the rotating rotating ring The adsorber 30 is composed of a plurality of carbon dioxide adsorption tanks 22, and the carbon dioxide adsorption tanks 22 are filled with carbon dioxide adsorbing materials, and the carbon dioxide adsorbing tanks 22 facilitate the replacement of the carbon dioxide adsorbing materials. 201124195 When there are two
箭頭進行氣體之流動 鲁 一 S /卜Z由ηΏ l 二”附箱塊22中之二氧化碳吸附材所：附，：二 氧化反及附材係為二氧化碳吸附基材，而該二氧化碳吸 附土材係~7為奈米碳管、彿石分子篩或純石夕中孔洞吸附材 等低溫吸附材，並可進一步經改質劑改質，於本實施例中 之改質劑係為含胺官能基之改質劑，而使用之二氧化碳之 吸附材係為經APTS改質之奈米碳管、經ΤΕΡΑ改質之奈米 碳管或經ΤΕΡΑ改質之矽鋁比60之Υ型沸石；而該待處理 廢氣流經該等二氧化碳吸附箱塊22之後’其内包含之二氧 化石反即為一氧化碳吸附材所吸附，完成二氧化碳之吸附作 用’最後經吸附淨化二氧化碳之淨化廢氣再流出該旋轉轉 環式吸附器30，流經該氣體出口 Β排出。 實施例3 : 本發明第三具體實施例之一種二氧化碳吸附系統3係 如第4圖所示，其中該系統係包含：一調濕器1〇及一蜂巢 狀轉輪式吸附器40;其中蜂巢狀轉輪式吸附器40係由複數 201124195 個經氧::巢狀二氧化碳吸附基材組合而成。 時，待處犧自吸附淨化 化碳吸附系統3之中，首先流：^ 人入該二氧 例之調濕器1〇係為一 Λ，、° 之中，本實施 以調節該域轉㈣之功能， 二綠轉輪式_4。之内；處==進 所：===:;，吸附材 ^ 化及附材係為二氧化碳吸附美讨， 而=-氧化碳吸附基材係可為奈米碳管^ Π::附材等低溫吸附材，並可進-二： 使用财之改質劑係為含胺官能基之改質劑，而 二一=1吸附議經apts改質之奈来碳管、 型、、弗石.J 未碳管或經T E P A改質之矽鋁比6 0之γ /弗，而該贿理廢氣流經該蜂巢狀轉輪式吸附器仙之 後—其内包含之二氧化碳即為二氧化碳吸附材所吸附，完 t氧化碳之吸附作用，最後經吸附淨化二氧化碳之淨化 廢亂再流出該蜂巢狀轉輪式吸附器4G，流經該氣體出口 B 排出。 實施例4 : 本發明第四具體實施例之一種二氧化碳吸附系統4係 如第5圖所示，其中該系統係包含：一調墀器1〇及一流體 化浮動床式吸附器（Fluidized Bed Adsorber)50 ;其中兮流體 201124195 化浮動床式吸附契 體化床或㈣床如包含複數個球狀吸附材55經過流 改質的球狀或而該等球狀吸附材55係為經 _ _體狀或®柱狀二氧化碳吸附基材。 化碳吸附系統4之中乱首由一風車5吹人該二氧 ，首先流經該調濕器1〇之中，太 例之調濕器10係為— T本貫施 以調節該待處理廢具^祕加濕與降溫之功能， 入該 ^之錢，接㈣賴之減理廢氣進 »瓜體子動床式吸附器％之内，而該待處理 ^氧化碳則被該流體化縣床式吸_5Q中之球狀== 所吸附，其中該球狀吸附材％係為二氧化碳吸附基材， 而，-氧化&吸附基材係可為活性碳、奈米碳管、沸石分 子筛或純⑪巾孔洞°及_等低溫吸Μ (但不設限於前述 吸附基材）’並可進—步經改質财質，於本實施例中之改 質劑係為含胺官能基之改質劑，而使狀二氧化碳之吸附 材係為經ΤΕΡΑ改質之雜比6〇之球狀γ型彿石或球狀活 性碳；而該待處理廢氣流經該流體化浮動床式吸附器5〇之 後’其内包含之二氧化碳即為球狀吸附材55所吸附，完成 二氧化碳之吸附作用，最後經吸附淨化二氧化碳之淨化廢 氣再流出該流體化浮動床式吸附器50，流經該氣體出口 β 排出。 吸附基材改質： 本發明實施例之吸附基材之改質方式為·將吸附基材如 201124195 奈米碳管、沸石分子篩、中孔洞純矽材料等低溫吸附材（但 不設限於前述吸附基材），且該基材之成形型式可為粉狀、 顆粒狀、片狀、球狀、圓柱狀、纖維狀、蜂巢狀或其任一 組合型式，將之與胺基類溶劑，如 3-aminopropyl-Triethoxysilane(APTS)、 Tetraethylenepentamine (ΤΕΡΑ)或其他胺基類化合物等經混 合攪拌(但不設限於前述改質劑），並可選擇適度加入結合劑 如環氧樹脂增進其吸脫附效能並加熱後，使基材表面具胺 類官能基，能夠吸附二氧化碳氣體，其改質步驟如下： (1) 將吸附基材與特定濃度之胺基溶劑（亦可適度再加 入環氧樹脂）混合攪拌； (2) 以密閉迴流加熱法將混合溶液加熱至沸騰維持數 小時；.· . (3) 待溶液冷卻後以過濾法將吸附材由溶液中分離出； (4) 將過濾出的吸附材烘乾，得到具胺類官能基的改質 吸附材。 實施例之結果： 以含C〇2廢氣進行該裝置效能之測試評估，其中該含 C〇2廢氣之成份範圍為：C〇2 10〜5〇%(v/v)、水氣:二 〇 1:·5%(ν/ν)、其餘為氮氣，且入流吸附溫度範圍為抑 〜;而於該等二氧化碳之吸附裝置中分別填充：純石夕中 7 =料如MCM_41等（蜂巢狀或顆粒狀或薄膜狀）、沸石 (蜂巢狀或顆粒狀或薄膜狀）、奈米碳管（蜂巢狀或顆粒狀 12 201124195 或薄膜狀），進行含co2廢氣之二氧化碳吸附淨化測試。 於不進行濕度調整缺乏水氣的環境下，以已知廢氣進 行胺基改質奈米碳管吸附二氧化碳之測試評估（co2 15%(v/v)，溫度50-60°C)，其吸附量結果，分別以APTS及 ΤΕΡΑ胺基改質之奈米碳管為例，其結果如表1 : 吸附材 二氧化碳吸附量（mg/g) APTS改質奈米碳管 70-90 ΤΕΡΑ改質奈米碳管 95-120 表1、二氧化碳吸附材之吸附量 由上表1之結果可知，於未調整待處理廢氣之濕度時， 經APTS改質奈米碳管之吸附量為70〜90mg/g，而經ΤΕΡΑ 改質奈米碳管之吸附量則為95〜120mg/g。 再以吸附溫度50〜60°C、脫附溫度120°C、15%C02、 無水氣之煙道氣環境下進行變溫吸附，持續20次吸附、脫 附後，來測試各吸附材之再生後吸附回覆率，其結果如下 表2 : 吸附材 再生20次後回覆率（％) APTS改質奈米碳管 90-95 ΤΕΡΑ改質奈米碳管 85-95 表2、二氧化碳吸附材之再生回覆率 由上表2中可知，該等改質奈米碳管的平均吸附回覆 率可高於90%以上，由此得知該等改質奈米碳管吸附C02 13 201124195 的持續能力高’其中又以經APTS改質奈求碳管的再生後 吸附回覆率較經ΤΕΡΑ改質奈米碳管為高。 再將經改質之奈米碳管於5〇〜6〇 t溫度條件、 15%C〇2、水氣含量〇〜17%之廢氣環境下進行％吸附測 试’其吸附效能如下表3所示The arrow carries out the flow of gas. Luyi S/Bu Z is composed of ηΏ l II" in the carbon dioxide adsorbing material in the box 22: attached: the dioxide is opposite to the carbon dioxide adsorption substrate, and the carbon dioxide adsorption soil system ~7 is a low temperature adsorption material such as a carbon nanotube, a smectite molecular sieve or a pure stone smatter adsorption material, and can be further modified by a modifier. The modifier in this embodiment is an amine-containing functional group. The modifier, and the carbon dioxide adsorbent used is an APTS modified nano carbon tube, a ruthenium modified carbon nanotube or a ruthenium modified ruthenium ratio of 60 ruthenium type zeolite; After the exhaust gas flows through the carbon dioxide adsorption block 22, the sulfur dioxide contained therein is adsorbed by the carbon monoxide adsorbing material, and the carbon dioxide is adsorbed. Finally, the purified carbon dioxide is adsorbed and purified, and then the gas is discharged. The adsorber 30 is discharged through the gas outlet port. Embodiment 3: A carbon dioxide adsorption system 3 according to a third embodiment of the present invention is shown in FIG. 4, wherein the system comprises: a humidity regulator 1 and One The nested rotor type adsorber 40; wherein the honeycomb-shaped wheel type adsorber 40 is composed of a plurality of 201124195 oxygen-containing: nested carbon dioxide adsorption substrate. When the self-adsorption purification carbon adsorption system is to be sacrificed 3 Among them, the first flow: ^ person into the two oxygen example of the humidity regulator 1 〇 system is a Λ, ° °, this implementation to adjust the function of the domain (4), two green runner type _4. ; ===入入:===:;, adsorption material ^ and attached materials for carbon dioxide adsorption, and =- oxidized carbon adsorption substrate can be carbon nanotubes Adsorbent material, and can enter - two: the use of the modifier is a modifier containing amine functional groups, while the two-one = 1 adsorption of the apts modified carbon nanotubes, type, and Fu Shi. J The carbon nanotubes or the TEPA-modified bismuth aluminum ratio is 60 γ / 弗, and the bribe exhaust gas flows through the honeycomb-shaped rotator-type adsorber, and the carbon dioxide contained therein is adsorbed by the carbon dioxide adsorbing material. After the adsorption of carbon monoxide, the purification of carbon dioxide by adsorption and purification, and then the flow of the honeycomb-shaped adsorber 4G, flowing through the gas outlet B Embodiment 4: A carbon dioxide adsorption system 4 according to a fourth embodiment of the present invention is shown in FIG. 5, wherein the system comprises: a regulator 1〇 and a fluidized floating bed adsorber (Fluidized Bed Adsorber) 50; wherein the turbulent fluid 201124195 is a floating bed type adsorption bed or (4) bed, if a plurality of spherical adsorption materials 55 are included in the flow-modified spherical shape or the spherical adsorption materials 55 are _ _ 体 体 or ® columnar carbon dioxide adsorption substrate. The carbon adsorption system 4 is smashed by a windmill 5 to blow the dioxin, first flowing through the humidity damper 1 ,, the humidity regulator 10 of the example The system is - T is applied to adjust the function of the waste to be treated, the secret humidification and cooling, into the money of the ^, and (4) to reduce the exhaust gas into the melon body moving bed type adsorber%, The carbon monoxide to be treated is adsorbed by the spherical shape of the fluidized county bed suction_5Q, wherein the spherical adsorbent% is a carbon dioxide adsorption substrate, and the -oxidation & adsorption substrate Can be activated carbon, carbon nanotubes, zeolite molecular sieves or pure 11-zone pores and _ low temperature suction (but not set It is limited to the aforementioned adsorption substrate)' and can be modified to be modified. In the present embodiment, the modifier is an amine-functional modifier, and the carbon dioxide adsorbent is tamper-modified. a spherical γ-type phoenix or spherical activated carbon having a mass ratio of 6 ;; and the carbon dioxide contained therein is a spherical adsorbent 55 after the waste gas to be treated flows through the fluidized floating bed adsorber 5 〇 After being adsorbed, the adsorption of carbon dioxide is completed, and finally, the purified exhaust gas which is adsorbed and purified by carbon dioxide flows out of the fluidized floating bed adsorber 50, and is discharged through the gas outlet β. Adsorption substrate modification: The modification method of the adsorption substrate in the embodiment of the invention is: adsorption of a substrate such as 201124195 carbon nanotube, zeolite molecular sieve, medium pore pure material such as low temperature adsorption material (but not limited to the aforementioned adsorption a substrate), and the formed form of the substrate may be in the form of powder, granules, flakes, spheres, cylinders, fibers, honeycombs or any combination thereof, and an amine-based solvent such as 3 -aminopropyl-Triethoxysilane (APTS), Tetraethylenepentamine (ΤΕΡΑ) or other amine-based compounds are mixed and stirred (but not limited to the above modifiers), and can be appropriately added with a binder such as epoxy resin to enhance its adsorption and desorption efficiency. After heating, the surface of the substrate is provided with an amine functional group, which can adsorb carbon dioxide gas. The modification procedure is as follows: (1) mixing the adsorbed substrate with a specific concentration of an amine-based solvent (may also be moderately added to the epoxy resin) (2) The mixed solution is heated to boiling for several hours by closed reflux heating; (3) After the solution is cooled, the adsorbent is separated from the solution by filtration; (4) filtered The adsorbent material is dried to obtain a modified adsorbent having an amine functional group. Results of the Example: The test of the performance of the device was carried out by using C〇2 exhaust gas, wherein the composition of the C〇2-containing exhaust gas was: C〇2 10~5〇% (v/v), water gas: two 1:·5% (ν/ν), the rest is nitrogen, and the in-flow adsorption temperature range is 〜~; and in the adsorption device of the carbon dioxide, respectively, it is filled: pure stone in the evening 7 = material such as MCM_41, etc. (honeycomb or In the form of granules or films, zeolite (honeycomb or granules or film), carbon nanotubes (honeycomb or granules 12 201124195 or film), carbon dioxide adsorption purification test with co2 exhaust gas. Tested for the adsorption of carbon dioxide by amine-modified carbon nanotubes with known exhaust gas (co2 15% (v/v), temperature 50-60 ° C), adsorption without known humidity adjustment in the absence of moisture As a result, APTS and amidoxime-modified carbon nanotubes were taken as examples. The results are shown in Table 1: Adsorption materials carbon dioxide adsorption capacity (mg/g) APTS modified carbon nanotubes 70-90 ΤΕΡΑ 质Meter carbon tube 95-120 Table 1, the adsorption amount of carbon dioxide adsorbent material As shown in the results of Table 1 above, when the humidity of the exhaust gas to be treated is not adjusted, the adsorption amount of the APTS modified carbon nanotube is 70~90mg/g. The adsorption amount of the modified carbon nanotubes is 95 to 120 mg/g. Then, the temperature is adsorbed at a temperature of 50 to 60 ° C, a desorption temperature of 120 ° C, a 15% CO 2 gas, and an anhydrous gas flue gas atmosphere, and after 20 adsorptions and desorptions, the regeneration of each adsorbent material is tested. The adsorption recovery rate, the results are shown in the following Table 2: Recycled rate after the adsorption of the adsorbent material 20 times (%) APTS modified carbon nanotubes 90-95 ΤΕΡΑ modified carbon nanotubes 85-95 Table 2, carbon dioxide adsorption material regeneration reply As can be seen from Table 2 above, the average adsorption recovery rate of the modified carbon nanotubes can be higher than 90%, and it is known that the enhanced capacity of the modified carbon nanotubes to adsorb CO 2 13 201124195 is high. Moreover, the adsorption recovery rate of the carbon nanotubes after the modification of the APTS is higher than that of the modified carbon nanotubes. The modified carbon nanotubes were subjected to a % adsorption test under the conditions of 5 〇 to 6 〇t temperature conditions, 15% C 〇 2, and water gas content 〇 17%. The adsorption performance is shown in Table 3 below. Show
表3、二氧化碳吸附材於不同水氣含量下之二氧化碳吸附量 — 〜〜〜 I、 吸附材 由表3可證明’經改質奈米碳管受廢氣濕度影響後， ^倾轉度之提高而增加，其中經APTS改質奈米碳 : = 85〜U〇，二氧化碳吸附量，而經艱 改質奈米碳管則能夠接斗不丨 Ί叔升到100〜150 mg/g二氧化碳吸附 量，即顯示調節待處理㈣”， ^ 廢氣之濕氣可有效提高二氧化碳之 吸附罝。 而Y60沸石塗藪 ΤΕΡΑ改質後，進行洚度影變 (C02=15%、溫度甘沾w 〜曰 測武’其結果如第6圖所示，由 第6圖可見當濕度範圍盔 Μ。諸¥ ®^ ’隨著濕度含量增加，二 二、里思之增加’當濕度含量為7〜8%時達到-氧 化碳最高吸附值19〇mg/g以上。 τq 一軋 由上述結果可知，本發明所提供之 系統，藉由-調濕ϋ及 吸附 ^ ^ ώ 附裝置’可有效提升待處理麻 氣中二氧化碳之吸附量。 了处.埋廢 201124195 當該吸附裝置之吸附材係為經APTS改質奈米碳管或 經ΤΕΡΑ改質奈米碳管時，較佳濕度範圍為0〜17%，更佳 濕度範圍為2〜5% ;當該吸附裝置之吸附材為經ΤΕΡΑ改質 之矽鋁比60的Υ型沸石時，較佳濕度範圍為2〜17%，最 佳之濕度範圍為7〜8%。 由上述之具體實施例可知，本發明所提供二氧化碳吸 附系統，其係利用一調濕器及具吸附材之一吸附裝置，可 有效吸附待處理廢氣中之二氧化碳，同時該吸附裝置中之 吸附材亦可重覆利用，即利用脫附作用而移除吸附材上之 二氧化碳，可有效降低二氧化碳淨化之成本，同時有效達 成資源重覆利用功效’並完成節能減礙之目的。 【圖式簡單說明】 第1圖係為本發明一種二氧化碳吸附系統之一示意 圖。 第2圖係為本發明第一具體實施例一種二氧化碳吸 附系統之一示意圖。 第3圖係為本發明第二具體實施例一種二氧化碳吸 附系統之一示意圖。 第4圖係為本發明第三具體實施例一種二氧化碳吸 附系統之一示意圖。 第5圖係為本發明第四具體實施例一種二氧化碳吸 附系統之一示意圖。 第6圖為濕度對於Υ60(ΤΕΡΑ)之二氧化碳吸附率之 15 201124195 影響。 【主要元件符號說明】 1 二氧化碳吸附系統 2 二氧化碳吸附系統 3 二氧化碳吸附系統 5 風車 10 調濕器 11 二氧化碳吸附單元 13 二氧化碳吸附材 20 吸附裝置 22 二氧化礙吸附箱塊 30 旋轉轉環式吸附器 40 蜂巢狀轉輪式吸附器 50 流體化浮動床式吸附器 55 球狀吸附材 16Table 3, carbon dioxide adsorption capacity of carbon dioxide adsorbent at different water vapor content - ~ ~ ~ I, adsorbent material from Table 3 can prove that 'the modified nanocarbon tube is affected by the humidity of the exhaust gas, ^ the degree of tilt increase Increase, which is modified by APTS nanocarbon: = 85~U〇, the amount of carbon dioxide adsorption, and the difficult carbon nanotubes can be lifted to 100~150 mg/g carbon dioxide adsorption capacity. That is to say, the adjustment is to be treated (4)", ^ The moisture of the exhaust gas can effectively increase the adsorption of carbon dioxide. After the modification of the Y60 zeolite, the temperature is changed (C02 = 15%, the temperature is smeared w ~ 曰 武'The results are shown in Fig. 6. It can be seen from Fig. 6 that when the humidity range is helmeted, the numbers of the two parts are increased as the humidity content increases, and the increase in the second and second levels is reached when the humidity content is 7 to 8%. - The highest adsorption value of carbon oxide is 19 〇mg/g or more. τq One rolling According to the above results, the system provided by the present invention can effectively improve the gas to be treated by using the -humidifier and the adsorption device. The amount of carbon dioxide adsorbed. The place is buried. 201124195 when the adsorption device When the adsorbent material is an APTS modified carbon nanotube or a ruthenium modified carbon nanotube, the preferred humidity range is 0 to 17%, and the better humidity range is 2 to 5%; when the adsorption device is adsorbed The preferred humidity range is from 2 to 17%, and the optimum humidity range is from 7 to 8%, which is modified by the above specific examples. The carbon dioxide provided by the present invention is known from the above specific examples. The adsorption system utilizes a humidity regulator and an adsorption device with an adsorbent material to effectively adsorb carbon dioxide in the exhaust gas to be treated, and the adsorbent material in the adsorption device can also be reused, that is, moved by desorption In addition to the carbon dioxide on the adsorbent, it can effectively reduce the cost of carbon dioxide purification, and at the same time effectively achieve the resource reuse effect 'and complete the energy saving and reducing the effect. [Simplified schematic] Figure 1 is a carbon dioxide adsorption system of the present invention Figure 2 is a schematic view showing a carbon dioxide adsorption system according to a first embodiment of the present invention. Figure 3 is a second embodiment of the present invention. Fig. 4 is a schematic view showing a carbon dioxide adsorption system according to a third embodiment of the present invention. Fig. 5 is a schematic view showing a carbon dioxide adsorption system according to a fourth embodiment of the present invention. ΤΕΡΑ) Carbon dioxide adsorption rate 15 201124195 Effect. [Main component symbol description] 1 Carbon dioxide adsorption system 2 Carbon dioxide adsorption system 3 Carbon dioxide adsorption system 5 Windmill 10 Humidifier 11 Carbon dioxide adsorption unit 13 Carbon dioxide adsorption material 20 Adsorption device 22 Oxidation Adsorption box 30 Rotary toroidal adsorber 40 Honeycomb-shaped reel adsorber 50 Fluidized floating bed adsorber 55 Spherical adsorbent 16