201141598 l \\ \j\jyjyrr\. 六、發明說明： 【發明所屬之技術領域】 本發明是有關於一種二氧化碳捕獲系統，且特別是 關於一種可節省能源、降低成本且具極高效率的二氧化 碳捕獲系統。 【先前技術】 聯合國「跨政府氣候變遷小組」（Intergovernmental Panel • 〇n Climate Change ’簡稱IPCC)在二零零二年二月二日發表 了一份報告’該報告由全世界一百三十個國家，二千五百名201141598 l \\ \j\jyjyrr\. VI. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a carbon dioxide capture system, and more particularly to an energy-saving, cost-reducing and highly efficient carbon dioxide Capture system. [Prior Art] The United Nations "Intergovernmental Panel • 〇n Climate Change" (IPCC) published a report on February 2, 2002. The report is made up of 130 worldwide. Country, 2,500
科學家共同簽署，指出全球暖化的結果與碳排放量的相關性 是確切無疑的。為減緩氣候暖化速度，聯合國於一九九二年 制定〈氣候變化綱要公約〉，一九九七年通過〈京都議定書〉， 二零零七年訂定〈岑里行動計畫〉，對攸關氣候暖化的溫室氣 體排放提出一系列政策目標方向，希望世界各國共同努力， 維護人類生存環境。哥本哈根會議是為制定二零一零年後全 球減排二氧化碳目標而舉行的新一輪會議。 世、'己全球平均接近地面的大氣層溫度上升了攝氏 度在2〇世紀，全球平均接近地面的大氣層溫度上升了 改普遍來說’科學界發現過去5G年可觀察的氣候 化，幾乎年的雙倍。而目前全球平均溫度的變 開始，二氧變化是同步上升的，從工業革命 了#夫的31急劇增加，_植物的光合作用吸收 成碳萨鈣：化碳，海洋也溶解一部分二氧化碳並固定 义’ S空乳中二氧化碳的含量還是逐步增加。二氧化 201141598Scientists signed the agreement to point out that the correlation between global warming results and carbon emissions is unquestionable. In order to slow down the rate of climate warming, the United Nations enacted the "Climate Change Framework Convention" in 1992, the "Kyoto Protocol" in 1997, and the "Murray Action Plan" in 2007. The greenhouse gas emissions of climate warming propose a series of policy objectives, and we hope that all countries in the world will work together to safeguard the living environment of mankind. The Copenhagen conference is a new round of meetings to set the goal of global carbon dioxide emissions reductions after 2010. The world's average near-surface atmospheric temperature has risen by one degree Celsius in the second half of the century, and the global average near-surface atmospheric temperature has risen. Generally speaking, the scientific community has discovered observable climaticization in the past 5 years, almost double the year. . At present, the change of global average temperature begins, and the change of dioxins is synchronously rising. From the industrial revolution, the 31 of the company has increased sharply. The photosynthesis of plants has been absorbed into the carbon-salt: carbon, and the ocean also dissolves a part of carbon dioxide and fixes it. 'The amount of carbon dioxide in the S-empty milk is gradually increasing. Dioxide 201141598
Λ t r J K I二;=7"至氣體的含量不斷增加，正是全球暖化的人為因 素中主要。jl刀。另外人類活動中的燃燒化石燃料、清理林木 和耕：等等也都増強了溫室效應。 、、王球姓的溫度增量可能反過來導致其它方面的變動，包 括海平面上升和降雨量及降雪量在數額上和樣式上的變化。 ，些變動也許促使極端天氣事件更強更頻繁，譬如洪水、旱 、颶風和龍捲風。除此之外，還有其它後果，包括 種及產篁、冰河撤退、夏天時河流流量減少、物 :根據1PCC 2001年報告預估，全球暖化 因ΠΓ，將造成每年將超過三千億美元的損失， 因此減/大軋中的二氧化碳勢必為 解決的重要問題。 H R面對和 我國在西元2006年時如果 ^ Ah ^ ^ ^ ^ I 4門不分攤用電所排放 164,086千㈣，氧化破排放為 夂古M 放的61.86%。但如果就 各主要4門之二氧化碳排放分析， nr ^ y- ^ ^ ^在为擁用電排放之情 $下我國在西几2_年能源卫業（能源轉換）的二氧化 碳排放為18,509千公噸，占燃料概 a把沾 Ύ聲堤總排放的6.98%，由 别面的數據可以知道能源I業發電給各和使用所產生 的二氧化碳占燃料燃燒總排放的54觀。 氧化碳總排放量的〆半以上，冰田 t 因此電廠的二氧化碳排 ❹的被能大㈣少我國二氧化碳的排 放。 目前我國對於⑽減量Μ騎略，以能源效率 提升與再生能源和擴大天然氣使用為主，但由於再生能 201141598 源受本身自然環境所限制，無法大量取代化石能源使 用’而屬低碳之天然氣幾乎完全仰賴進口，價格受國際 市場波動大且售價昂貴，若大量使用將對國内電價與能 源價格造成影響。因此適當的結合co2捕獲以減少火力電 廠之C〇2的排放量，是考慮的方法之一，而能有效大量去 除C〇2排放的關鍵技術則以捕獲技術為先。 就現有方法採用吸收液如乙醇胺(Monoethanolamine， MEA)吸收二氧化碳為例，每公斤 的MEA可吸收60 g C〇2 (MEA吸收劑的容量（Capacity))，若以90%的捕獲率來說， 捕獲每噸C〇2需要1.0368 kWh的熱量，會耗用許多能 源’再者操作溫度需低於60°C ’因此進入吸收槽之煙氣需 先降’皿。此外，使用氣水（amm〇nia)或胺類（amine)有泡漏 疑慮，濃度高的吸收劑例如濃度超過3〇%的MEA對設備 具腐银性。 和高效率的C02捕獲系統， 減少能源浪費， 以lMWe燃煤電廠為例，排氣中c〇2濃度約為1〇% 〜_16%，氣體質量估算每小時約12噸，氣體質量如此大而 二氧化碳的濃度又低的情况下，若能研發出具有高性能 ’並且可有效整合與利用能源’Λ t r J K I II; =7" To the increasing gas content, it is the main factor in the global warming of human factors. Jl knife. In addition, burning fossil fuels, cleaning trees and ploughing in human activities have also strengthened the greenhouse effect. The temperature increase of Wang Qiu may in turn lead to other changes, including sea level rise and changes in the amount and pattern of rainfall and snowfall. These changes may make extreme weather events stronger and more frequent, such as floods, droughts, hurricanes and tornadoes. In addition, there are other consequences, including planting and calving, glacial retreat, and reduced river flow in summer. According to the 1PCC 2001 report, global warming will result in more than $300 billion per year. The loss, therefore, the carbon dioxide in the reduction/large rolling is bound to be an important issue to be solved. H R face and China in 2006, if ^ Ah ^ ^ ^ ^ I 4 non-allocated electricity emissions 164,086 thousand (four), oxidative emission is 61.86% of the ancient M. However, if we analyze the carbon dioxide emissions of the main four gates, nr ^ y- ^ ^ ^ in the case of electricity emissions, China's energy in the West 2 years, energy and energy (energy conversion) carbon dioxide emissions of 18,509 thousand metric tons It accounts for 6.98% of the total emissions of the Diansheng Dyke. From other data, it can be seen that the energy generated by the energy I industry produces and accounts for 54% of the total emissions of fuel combustion. More than half of the total emissions of carbon oxides, ice field t, therefore, the carbon dioxide emissions of power plants are large (four) less emissions of carbon dioxide in China. At present, China is mainly responsible for (10) reducing the amount of energy, improving energy efficiency and renewable energy, and expanding natural gas use. However, because the renewable energy 201141598 source is limited by its natural environment, it cannot replace fossil energy use in large quantities. Fully relying on imports, the price is subject to fluctuations in the international market and the price is expensive. If used in large quantities, it will affect domestic electricity prices and energy prices. Therefore, proper combination of co2 capture to reduce the C〇2 emissions of thermal power plants is one of the methods considered, and the key technology that can effectively remove C〇2 emissions in large quantities is based on capture technology. For the current method, an absorption liquid such as Monoethanolamine (MEA) is used for absorbing carbon dioxide. For every kilogram of MEA, 60 g of C〇2 (the capacity of the MEA absorbent) can be absorbed. If the capture rate is 90%, Capturing 1.0368 kWh of heat per ton of C〇2 will consume a lot of energy. 'The operating temperature should be lower than 60 °C'. Therefore, the flue gas entering the absorption tank needs to be lowered first. In addition, the use of gas water (amm〇nia) or amines has a problem of bubble leakage, and a high concentration of an absorbent such as MEA having a concentration of more than 3% by weight is sulphur-staining to the device. And high-efficiency CO2 capture system to reduce energy waste. Take lMWe coal-fired power plant as an example. The concentration of c〇2 in the exhaust gas is about 1〇%~_16%, and the gas quality is estimated to be about 12 tons per hour. The gas quality is so large. If the concentration of carbon dioxide is low, if it can develop high performance 'and can effectively integrate and utilize energy'
【發明内容】 氧化碳捕獲系統，其特殊的 二氧化碳捕獲效率，更可節 本發明係有關於一種二_ 設計使得系統不但具極高的二 省能源、降低成本。 根據本發明，係提出〜 種一氧化碳捕獲系統，包括 201141598 進料排料部、一第一反應器、一第二反應器、一連通管 與-吸附劑儲料槽。第-反應器係具有—煙氣入口可導入 一含二氧化碳成份的煙氣，進料排料部係經過再生處理之 -吸附劑（可利用金屬氧化物作為吸附劑，如氧化妈）送至 第一反應器，係與二氧化碳進行—碳酸化反應形成一碳 酸化飽合吸附劑（如碳酸鈣），其中該再生處理例如煅燒。 第二反應器係位於第一反應器下側處並與第一反應器連 通：可煅燒來自第一反應器之碳酸化飽合吸附劑，以脫附 一氧化碳，產生再生處理（如煅燒）的吸附劑。連通管係連 接第-反絲之底部與第二反應器，第—反應諸形成之 碳酸化飽合吸附劑係因重力落下後經由連通管進入第二 反應器。吸附劑儲料槽係位於第二反應器之一出口端以承 載煅燒後的咬附劑。 在一實施例中，第一反應器例如是氣泡式流體化床 之碳酸化爐，第二反應器例如是煅燒爐，分別進行吸附反 應和脫附反應。碳酸化飽合吸附劑經過高溫锻燒會將吸附 的c〇2釋放出來再度形成吸附劑如氧化鈣（Ca〇)，再次循 環進入碳酸化爐進行捕獲c〇2。若煅燒氣體為蒸汽，第二 反應器排氣之高濃度C〇2與蒸汽可經由一冷凝器分離，所 捕獲的高濃度C〇2可以進行封存及再利用。 在一實施例中，第二反應器進行煅燒所需要的高溫可 藉由一富氧燃燒器供應，第二反應器產生的高溫氣體再以 迴流方式作為富氧燃燒器的輔助高溫氣體，以降低燃料使 用量，使整個C〇2捕獲系統更加節省燃料與降低成本。 為讓本發明之上述内容能更明顯易懂，下文特舉實 201141598 I vvuuv/7rw 施例，並配合所附圖式，作詳細說明如下： 【實施方式】 本發明係提出一種二氧化碳捕獲系統，利用吸附劑 在適當的溫度下吸附二氧化碳，繼而在適當的溫度下再 脫附二氧化碳，藉由吸附劑在兩反應器内分別進行碳酸 化程序及煅燒程序，達到吸附及脫附的循環來進行二氧化 碳的捕獲與分離。透過特殊的設計使得本發明之二氧化 • 碳捕獲系統不但具極高的二氧化碳捕獲效率，更可節省 能源、降低成本。 以下係根據本發明提出一實施例以詳細說明本發 明。然而，本領域相關技術者當知實施例所提出之二氧 化碳捕獲系統和捕獲流程等内容僅為舉例說明之用，並 非作為限縮本發明保護範圍。實際應用時，熟習相關技 術者除了根據實施例和實驗之揭露内容，仍應針對應用 時實際條件之需求在不悻離本發明之精神下對二氧化碳 • 捕獲系統做適當調整和修改。再者，實施例之圖示僅繪 示本發明技術之相關元件，省略不必要之元件，以清楚 顯示本發明之技術特點。 另外’可應用金屬氧化物做為吸附劑，例如是氧化約 (CaO)、氧化鋅(ZnO)、氧化鎮（MgO)、氧化猛(Μη02)、氧 化鎳(NiO)、氧化銅（Cu〇)、氧化鉛（PbO)或其他氧化物，而 實施例中則以氧化約（CaO)為吸附劑，以進行氧化弼之碳 酸化程序和碳酸鈣（即碳酸化飽合吸附劑）之煅燒程序的相 關說明’當然本發明並不以此種吸附劑為限。 201141598 ------ F 1» 請參照第1圖，其繪示依照本發明一實施例之二氧 化碳捕獲系統的示意圖。實施例之二氧化碳捕獲系統至 少包括一進料排料部、一第一反應器20、一第二反應器 30、一連通管200和一氧化鈣（CaO)儲料槽40。第一反應 器20係具有至少一煙氣入口可導入一含二氧化碳成份的 煙氣’進料排料部係將經過再生處理之一氧化鈣（CaO)(吸 附劑）送至第一反應器20，以與二氧化碳進行一碳酸化反 應形成碳酸鈣（CaC03)(碳酸化飽合吸附劑），其中該再生處 理例如煅燒。第二反應器30係位於第一反應器2〇下側處 並與第一反應器20連通，可煅燒來自第一反應器20之碳 酸鈣，以脫附二氧化碳，產生烺燒後的氧化鈣。連通管 200係連接第一反應器2〇之一底部與第二反應器3〇，而 第一反應器20所形成之碳酸弼，可因重力自然落下後經 由連通管200進入第二反應器30。氧化鈣(Ca〇)儲料槽4〇 係位於第二反應器30之一出口端以承載缎燒後的氧化 !弓。 於實施例中，進料排料部係可為一氣送系統U，包 括一送風機12(/風車）、一貯料槽13、一進料槽14、和一 輸送帶15。其中，送風機12(/風車）可提供進料排料部内 之一氣送方式；貯料槽13係鄰近第一反應器2〇，用以暫 貯進料排料部内之氧化鈣。輸送帶15則以氣送方式將貯 料槽13内之氧化妈（吸附劑）輸送至進料槽14。進料槽14 係位於第一反應器20之上方，視第一反應器20之需求適 時地進料。而進料槽14係以一旋轉閥（Rotary Valve)16及 一法藍(Flang)與第一反應器20相接，以控制進料槽14内 201141598 * * wv/ * i » 之吸附劑至第一反應器20的吸附劑量。 在一實施例中，第一反應器20係為一氣泡式流體化 床之碳酸化爐，並具有一佈風板21(或氣體分佈盤）可以將 煙氣均勻分佈地導入床體内，使氧化鈣產生流體化現 象。流體化的氧化鈣可與煙氣中所含有的C〇2進行碳酸化 反應’使氧化鈣形成碳酸鈣。而碳酸鈣（CaC03)(及小部份 未反應氧化鈣）會因分子重量增加而自然向下掉落，經由連 通管200設計而落入第二反應器3〇内。其中，碳酸化爐 • 係可在一操作溫度範圍約650°C〜750。(：下進行C02的吸附 反應。一應用例中’氣泡式流體化床之碳酸化爐高度例如 疋1〜2m(卽省空間），流化區域風速例如是0.5 m/s ~3m/s。 在一實施例中’第二反應器30係可在一高溫範圍約 800°C〜950°C下操作，使碳酸鈣(caC03)脫附C02再形成氧 化鈣（CaO)，回到該第一反應器2〇循環再利用。當然，實 際應用時，锻燒爐的锻燒溫度係依選擇的吸附劑種類不同 (金屬氧化物吸附劑例如是氧化鈣（Ca〇)、氧化辞(Zn〇)、氧 •化鎂（MgO)、氧化錳(Mn〇2)、氧化鎳(Ni〇)、氧化銅（Cu〇)、 氧化鉛(PbO)或其他氧化物），煅燒時間例如是維持3〇分鐘 至180分鐘’使吸附劑能煅燒完全有利於捕獲c〇2。 另外’锻燒—新料時則將完全未反應的石灰石（CaC03) 輸送進煅燒爐煅燒成石灰(Ca〇)後，排入氧化鈣(Ca〇)儲料 槽40儲存。可應用之第二反應器30例如是一移（蠕）動床 型式之煅燒爐、或一旋轉窯型式之煅燒爐、一流體化床 型式之煅燒爐、或一固定床式之煅燒爐、或其他型式之煅 燒爐。在第1圖中，係以移（蹲)動床型式之缎燒爐為例做 201141598 如第1圖所式’移（蠕）動床型式之煅燒爐（即第二反 應器30)具有多支佈風管31。適合的煅燒氣體經由佈風管 31方式將氣體導入煅燒爐内並均勻分佈在煅燒爐内空 間，使氣體產生重疊擾動（蠕動）現象，煅燒爐内之碳酸鈣 因擾動或流化而緩慢由煅燒爐前端向尾端被推動，一路 被推動而通過煅燒爐，前進至煅燒爐之出口端後可排入氧 化鈣（CaO)儲料槽40，達到完全煅燒目的（即碳酸化飽合 吸附劑經過高溫煅燒後將吸附的C〇2釋放出來再度形成吸 附劑-氧化鈣）。在一實施例中，氧化鈣（Ca0)儲料槽40係 可以一高溫液位計監控排入氧化鈣吸附劑之一粉體高 度，當粉體高度達到某一定值時則停止進料，並啟動進 料排料部以輸送料或排料。 在實施例中’可應用之煅燒氣體如水蒸汽、氮氣 (N2)、二氧化碳、空氣(air)、氦氣、氖氣、或氬氣、或前 述任二或多種混合氣體。佈風管31氣量可進行調整，若 採用水蒸汽為煅燒氣體，則可藉由佈風管31控制水蒸汽 的喷注量及噴注氣體的區域與方式，在溫度約 300°C〜50(TC，產生中間產物氫氧化鈣(Ca(0H)2)以改質煅 燒後的氧化鈣。在一應用例中，例如在煅燒爐内創造不同 脈度區’再導入不同蒸汽量，使得煅燒後形成的氧化約 (CaO)具有改質效果。 在一應用例中’若使用蒸汽作為使移（蠕）動床型式煅 燒爐内部CaC〇3產生移動的氣體，除了降低煅燒爐内c〇2 的分壓’使吸附飽合之碳酸鈣内的C〇2易於脫附以外，也 201141598 1 ννυνν/7ΓΛ 容易將蒸汽與煅燒爐内產生的高純度C〇2彼此分離。擾動 的氣體少量即可達到使碳酸鈣（CaC〇3)向前移動，煅燒所 需的時間可由碳酸鈣經過爐長的時間來控制與設計。除 此之外，亦可藉由控制煅燒爐内溫度區域及蒸汽量的多 寡而製造出不同量的氫氧基(OH')，將CaC03煅燒成為 CaO之後再與(OH )反應形成Ca(OH)2。形成的Ca(OH)2在 高溫下（>500°C)將水分子趕出，使煅燒後之CaO增加吸附 劑内孔體積及比表面積，當CaO再循環進入碳酸化爐， • 其捕獲C02效率將會提升及衰減率會因此減少。相關反應 式如下述：SUMMARY OF THE INVENTION The carbon oxide capture system, which has a special carbon dioxide capture efficiency, can also be described in terms of a second design that allows the system to not only have a very high energy saving but also reduce costs. According to the present invention, there is proposed a carbon monoxide capture system comprising a 201141598 feed discharge section, a first reactor, a second reactor, a communication tube and a sorbent storage tank. The first reactor has a flue gas inlet for introducing a flue gas containing a carbon dioxide component, and the feed discharge portion is subjected to a regenerative treatment-adsorbent (a metal oxide can be used as an adsorbent, such as an oxidation mother). A reactor is carbonic acid-carbonated to form a carbonation-saturated adsorbent (such as calcium carbonate), wherein the regeneration treatment is, for example, calcination. The second reactor is located at the lower side of the first reactor and is in communication with the first reactor: the carbonated saturated adsorbent from the first reactor can be calcined to desorb carbon monoxide to produce adsorption for regeneration treatment (such as calcination) Agent. The communication pipe is connected to the bottom of the first-reverse wire and the second reactor, and the carbonation-saturated adsorbent formed by the first reaction is dropped into the second reactor via the communication pipe after being dropped by gravity. The sorbent sump is located at one of the outlet ends of the second reactor to carry the calcined occluding agent. In one embodiment, the first reactor is, for example, a carbonation furnace of a bubble fluidized bed, and the second reactor is, for example, a calciner, which performs an adsorption reaction and a desorption reaction, respectively. After the high-temperature calcination of the carbonation-saturated adsorbent, the adsorbed c〇2 is released to form an adsorbent such as calcium oxide (Ca〇), which is recycled to the carbonation furnace to capture c〇2. If the calcination gas is steam, the high concentration C〇2 of the second reactor exhaust gas and the steam can be separated by a condenser, and the captured high concentration C〇2 can be sequestered and reused. In one embodiment, the high temperature required for the second reactor to be calcined can be supplied by an oxy-combustion burner, and the high-temperature gas generated by the second reactor is used as an auxiliary high-temperature gas of the oxygen-enriched burner in a reflux manner to reduce The amount of fuel used makes the entire C〇2 capture system more fuel efficient and less costly. In order to make the above-mentioned contents of the present invention more comprehensible, the following is a detailed description of the 201141598 I vvuuv/7rw embodiment, and is described in detail with reference to the following drawings: [Embodiment] The present invention provides a carbon dioxide capture system. The carbon dioxide is adsorbed at an appropriate temperature by the adsorbent, and then the carbon dioxide is desorbed at an appropriate temperature, and the carbonation process and the calcination process are respectively carried out in the two reactors by the adsorbent to achieve a cycle of adsorption and desorption to carry out carbon dioxide. Capture and separation. Through special design, the carbon dioxide capture system of the present invention not only has high carbon dioxide capture efficiency, but also saves energy and reduces cost. The following is an embodiment in accordance with the present invention to explain the present invention in detail. However, it is to be understood by those skilled in the art that the carbon dioxide capture system and the capture process proposed in the embodiments are for illustrative purposes only and are not intended to limit the scope of the present invention. In practical applications, the skilled artisan should make appropriate adjustments and modifications to the carbon dioxide capture system without departing from the spirit of the present invention, in addition to the disclosure of the embodiments and experiments. Further, the illustrations of the embodiments only show the related elements of the technology of the present invention, and unnecessary elements are omitted to clearly show the technical features of the present invention. In addition, 'metal oxides can be used as adsorbents, such as oxidation (CaO), zinc oxide (ZnO), oxidized town (MgO), oxidized Μ (Μη02), nickel oxide (NiO), copper oxide (Cu 〇) Lead oxide (PbO) or other oxides, and in the examples, oxidizing about (CaO) as an adsorbent for the carbonation process of cerium oxide and the calcination procedure of calcium carbonate (ie, carbonated saturated adsorbent) Related Description 'Of course, the present invention is not limited to such an adsorbent. 201141598 ------ F 1» Please refer to FIG. 1 , which illustrates a schematic diagram of a carbon dioxide capture system in accordance with an embodiment of the present invention. The carbon dioxide capture system of the embodiment includes at least one feed discharge portion, a first reactor 20, a second reactor 30, a communication tube 200, and a calcium oxide (CaO) hopper 40. The first reactor 20 has at least one flue gas inlet for introducing a flue gas containing a carbon dioxide component. The feed discharge portion sends a calcium oxide (CaO) (adsorbent) to the first reactor 20 through regeneration treatment. The carbonation reaction with carbon dioxide forms calcium carbonate (CaC03) (carbonated saturated adsorbent), wherein the regeneration treatment is, for example, calcination. The second reactor 30 is located at the lower side of the first reactor 2 and is in communication with the first reactor 20, and calcium carbonate from the first reactor 20 can be calcined to desorb carbon dioxide to produce calcined calcium oxide. The communication tube 200 is connected to one of the bottoms of the first reactor 2 and the second reactor 3, and the cesium carbonate formed by the first reactor 20 can be naturally dropped by gravity and then enter the second reactor 30 via the communication tube 200. . A calcium oxide (Ca〇) hopper 4 is located at one of the outlet ends of the second reactor 30 to carry the satin-fired oxidized bow. In an embodiment, the feed discharge portion may be an air delivery system U, including a blower 12 (/windmill), a hopper 13 , a feed chute 14, and a conveyor belt 15. Wherein, the blower 12 (/windmill) can provide a gas delivery mode in the feed discharge portion; the storage tank 13 is adjacent to the first reactor 2〇 for temporarily storing the calcium oxide in the feed discharge portion. The conveyor belt 15 conveys the oxidizing mother (adsorbent) in the sump 13 to the feed tank 14 by air. The feed tank 14 is positioned above the first reactor 20 and is fed as appropriate to the needs of the first reactor 20. The feed tank 14 is connected to the first reactor 20 by a rotary valve 16 and a flange (Flang) to control the adsorbent of the 201141598 * * wv / * i » in the feed tank 14 to The adsorbed dose of the first reactor 20. In one embodiment, the first reactor 20 is a carbonation furnace of a bubble fluidized bed, and has a distribution plate 21 (or a gas distribution plate) for uniformly distributing the flue gas into the bed body. Calcium oxide produces fluidization. The fluidized calcium oxide can be carbonated with C〇2 contained in the flue gas to cause the calcium oxide to form calcium carbonate. Calcium carbonate (CaC03) (and a small portion of unreacted calcium oxide) will naturally fall downward due to an increase in molecular weight, and will fall into the second reactor 3 via the design of the communication tube 200. Among them, the carbonation furnace can be operated at an operating temperature range of about 650 ° C ~ 750. (: The adsorption reaction of C02 is carried out. In an application example, the height of the carbonation furnace of the bubble type fluidized bed is, for example, 疋1 to 2 m (the space is saved), and the wind speed in the fluidization region is, for example, 0.5 m/s to 3 m/s. In one embodiment, the second reactor 30 can be operated at a high temperature range of about 800 ° C to 950 ° C to desorb C02 from calcium carbonate (caC03) to form calcium oxide (CaO), returning to the first The reactor 2 is recycled and reused. Of course, in practical applications, the calcination temperature of the calciner is different depending on the type of adsorbent selected (the metal oxide adsorbent is, for example, calcium oxide (Ca〇), oxidized (Zn〇). , Magnesium Oxide (MgO), Manganese Oxide (Mn〇2), Nickel Oxide (Ni〇), Copper Oxide (Cu〇), Lead Oxide (PbO) or other oxides, the calcination time is, for example, maintained for 3 minutes. By 180 minutes, the calcination of the adsorbent is completely beneficial for capturing c〇2. In addition, when calcining the new material, the completely unreacted limestone (CaC03) is transferred into the calciner and calcined into lime (Ca〇), and then discharged. The calcium oxide (Ca〇) storage tank 40 is stored. The second reactor 30 that can be used is, for example, a shifting (creep) moving bed type calciner, A rotary kiln type calciner, a fluidized bed type calciner, or a fixed bed type calciner, or other type of calciner. In Fig. 1, a shifting (蹲) moving bed type satin is used. The furnace is taken as an example for 201141598. The calciner of the type of shifting (creep) moving bed (that is, the second reactor 30) has a plurality of cloth ducts 31. Suitable calcining gas will be passed through the air duct 31. The gas is introduced into the calciner and evenly distributed in the space inside the calciner, causing overlapping disturbance (creeping) of the gas. The calcium carbonate in the calciner is slowly pushed from the front end to the tail end of the calciner due to disturbance or fluidization, and is pushed all the way. And through the calcining furnace, after advancing to the outlet end of the calcining furnace, it can be discharged into the calcium oxide (CaO) storage tank 40 to achieve the purpose of complete calcination (that is, the carbonized saturated adsorbent is released after high temperature calcination to adsorb the adsorbed C〇2. The adsorbent-calcium oxide is formed again. In an embodiment, the calcium oxide (Ca0) storage tank 40 can monitor the powder height of one of the calcium oxide adsorbents by a high temperature level gauge, when the powder height reaches a certain height. Stop at a certain value And initiating the feed discharge to feed or discharge. In the examples, 'applicable calcination gas such as water vapor, nitrogen (N2), carbon dioxide, air, helium, neon, or argon, Or any one or more of the foregoing mixed gases. The air volume of the air duct 31 can be adjusted. If water vapor is used as the calcining gas, the amount of water vapor injected and the area and manner of the injected gas can be controlled by the air duct 31. Calcium oxide after calcination at a temperature of about 300 ° C to 50 (TC, producing intermediate calcium hydroxide (Ca (0H) 2 ). In an application, for example, creating different pulse zones in the calciner' Further introduction of different amounts of steam allows the oxidation (CaO) formed after calcination to have a modifying effect. In an application example, if steam is used as a gas to move the CaC〇3 inside the moving bed type calciner, in addition to lowering the partial pressure of c〇2 in the calciner, the adsorbed saturated calcium carbonate is C〇2 is easy to desorb, and also 201141598 1 ννυνν/7ΓΛ It is easy to separate the steam and the high-purity C〇2 produced in the calciner from each other. A small amount of disturbed gas can move calcium carbonate (CaC〇3) forward, and the time required for calcination can be controlled and designed by the time of calcium carbonate passing through the length of the furnace. In addition, different amounts of hydroxyl groups (OH') can be produced by controlling the temperature region and the amount of steam in the calciner, and CaC03 is calcined to CaO and then reacted with (OH) to form Ca(OH). )2. The formed Ca(OH)2 drives water molecules out at high temperature (>500 °C), so that CaO after calcination increases the pore volume and specific surface area of the adsorbent, when CaO is recycled into the carbonation furnace, • its capture C02 efficiency will increase and the attenuation rate will be reduced. The relevant reaction formula is as follows:
CaO + H20 Ca (〇H \CaO + H20 Ca (〇H \
Ca (OH \ ^ CaO + H 20 AH〇298k=353.5kcal/kg Ca(OH)2 (endothermic)Ca (OH \ ^ CaO + H 20 AH〇298k=353.5kcal/kg Ca(OH)2 (endothermic)
CaCO 3 -> CaO + CO 2 AH〇298k=427.5kcal/kg CaC03 (endothermic) 再者，實施例之二氧化碳捕獲系統更包括一分離C02 冷凝槽50、一粉塵捕集設備60和一控制程序。其中分離 C〇2冷凝槽50係銜接於第二反應器30的一排氣口端，將 所排出之一煅燒氣體冷凝並分離所含之c〇2 ;例如若煅燒 氣體為蒸汽’分離C02冷凝槽50可將第二反應器30排氣 之高濃度C〇2與蒸汽分離，而所捕獲的高濃度c〇2可以進 行封存及再利用。粉塵捕集設備60係銜接於第一反應器 20的一端’將第一反應器20的一排放氣體過濾後排放。 201141598 a ** ν» 14» 控制程序則可自動化控制捕獲系統之操作。在一應用例， 中，粉塵捕集設備60可為一高溫粉塵捕集設備6〇,可耐 溫度例如是高達約600。〇〜90(TC，以捕集第一反應器2〇或 第二反應器30隨煙氣所排出之粉塵，可應用之設備例如 是陶磁袋濾器、或一高溫旋風分離器。 如則述之二氧化碳捕獲系統，在碳酸化爐設備中利 用金屬氧化物作為吸附劑，若應用在高溫下捕獲電廠排 氣中之C〇2，對降低電廠排氣排放量將有極大的助益。再 者系統的咼溫緞燒爐中對已經吸附C〇2的吸附劑進行脫附鲁 (再生）反應，可使吸附劑不斷再利用。但高溫操作涉及到 熱量的供應及再利用，如果完全依賴燃料的提供則將是 非常耗能。因此’在此實施例中，亦將高溫氣體的迴流至 煅燒爐再利用’不但節省燃料，亦可以產生蒸汽使用， 使整個C〇2捕獲系統更加節能與降低成本。 在一實施例中’煅燒爐可採用直接加熱方法或一間接 加熱方法’將高溫氣體的迴流至般燒爐再利用。第2圖和 第3圖係分別繪示本發明實施例之煅燒爐直接熱交換和間 φ 接熱交換之示意圖。 如第2圖所示，係以富氧燃燒器301對煅燒爐302直 接加熱，而煅燒爐302所產生之高溫煙氣則經過除塵（例如 旋風集塵器303)和透過引風機304再迴流至富氧燃燒器 301助燃，以提升般燒爐302溫度，如此可大幅降低燃料 使用量。經數次迴流之後煙氣所產生的蒸汽可以作為烺燒 用氣體。 如第3圖所示’亦可間接加熱煅燒爐302，例如對煅 12 201141598 1 wouuyr/\ 燒爐302外管加熱，藉由熱傳導方式將熱均勻分佈在烺燒 爐302各區域’煅燒爐302產生之高溫煙氣經引風機304 以迴流方式再進入富氧燃燒器301，以大幅降低燃料使用 量。再者’亦可經適當設計，使煅燒爐302適當攪拌或翻 滾使煅燒完全，煅燒爐302内部可更具有至少一沉降板， 將攪拌時產生碰撞的粉塵先攔截。 根據上述，一實施例中，二氧化碳捕獲系統係由進料 • 及排料系統、氣泡式流體化床型式碳酸化爐（第一反應器 2〇)、移（蠕）動床型式煅燒爐（第二反應器30)、氧化鈣（Ca〇) 儲料槽40、分離C02冷凝槽50、粉塵捕集設備6〇及控制 程序組成。主要是以2組反應器：第一反應器20-碳酸化 爐和第二反應器30-煅燒爐來分別進行吸附反應和脫附反 應。系統運作時，係將含C〇2成份之煙氣引進碳酸化爐， 内载有氧化鈣（CaO)溫度控制介於650°C〜750°C。在碳酸化 爐内C〇2與CaO反應後形成碳酸鈣(CaC03)，因分子重量 春增加會自然經由連通管200而從第一反應器20碳酸化爐 内進入第二反應器30煅燒爐内，煅燒爐内溫度則控制在 850°C〜950°C。緞燒爐以蒸氣（或氮氣或空氣或氬氣或其他 惰性氣體)作為煅燒氣體。烺燒氣體以佈風管31方式將氣 體均勻分佈在煅燒爐内空間製造不同氣體分佈量，使锻燒 爐内部產生氣體重疊擾動現象，進而推動吸附劑往出口端 移動通過煅燒爐以達到完全煅燒的目的。經過高溫烺燒的 CaC〇3會將吸附的C〇2釋放出來再度形成CaO，循環進入 碳酸化爐進行捕獲C02。而烺燒爐排氣之高濃度c〇2與蒸 13 201141598 二广由冷凝③(即分離C。2冷凝槽5°)分離，捕獲的高濃 二2可以進仃封存及再利用n施例中，锻燒爐般 A古X:所需要的高溫藉由富氧燃燒器供應，煅燒爐產生 ^冋孤乳體再以迴流方式作為富氧燃燒器的輔助高溫氣 以降低燃料使用量，達到節能及熱再利用的目的。而 貫施例中’整㈣統為自動化操作，包括：吸附脫附 補充新鮮吸附劑⑽、輸送吸附劑C及排出已經失 活=的吸附劑(廢料排丨）皆是制連續式循環操作模式， 而監控各儲槽料位控制的操作則可採用高溫液位計、、 取時=控制方式(timer)進行監控。例如吸附劑儲料槽可利 用同/m液位计監控排入該吸附劑之一粉體高度，當粉 體南度達到某-定值時則停止進料，並啟動進 輸送料或排料。 目前C〇2捕獲系統實際測試，連續循環操作，當入 口 C〇2濃度為12%〜14%之間，在排放口量測c〇2排放 濃度，連續操作6小時，捕獲c〇2效率可高達99%〜1〇〇 %以上。 請參照第4A、4B圖，其分別為本發明—實驗例之碳 酸化爐捕獲C〇2之曲線圖，和C〇2去除效率之曲線圖。實 驗例中’吸附劑CaO進料16.5公斤，碳酸化爐壓力 160-165cmH2O,碳酸化爐溫度650°C，C〇2氣體流量〇 147 立方公尺/分鐘(CMM/min)。如第4A圖所示，c〇2在碳酸 化爐之入口濃度13%-16% ’出口濃度近乎於。因此， C〇2去除效率高達99%〜100%，如第4B圖所示。CaCO 3 -> CaO + CO 2 AH 〇 298k = 427.5 kcal / kg CaC03 (endothermic) Further, the carbon dioxide capture system of the embodiment further includes a separation CO 2 condensation tank 50, a dust collection device 60 and a control program. Wherein the separation C〇2 condensation tank 50 is connected to a discharge port end of the second reactor 30, and condenses one of the discharged calcination gases and separates the contained c〇2; for example, if the calcination gas is steam 'separation CO 2 condensation The tank 50 separates the high concentration C〇2 of the second reactor 30 from the vapor, and the captured high concentration c〇2 can be sequestered and reused. The dust trapping device 60 is coupled to one end of the first reactor 20 to filter an exhaust gas of the first reactor 20 and discharge it. 201141598 a ** ν» 14» Control program automatically controls the operation of the capture system. In one application, the dust capture device 60 can be a high temperature dust capture device 6 可 having a temperature resistance of, for example, up to about 600. 〇~90 (TC, to capture the dust discharged from the first reactor 2〇 or the second reactor 30 with the flue gas, the applicable equipment is, for example, a ceramic bag filter, or a high-temperature cyclone separator. Carbon dioxide capture system, which uses metal oxide as adsorbent in carbonator equipment, if it is used to capture C〇2 in power plant exhaust at high temperature, it will be of great help to reduce power plant emissions. The desorption (regeneration) reaction of the adsorbent that has adsorbed C〇2 in the swarovski furnace can continuously reuse the adsorbent. However, the high temperature operation involves the supply and reuse of heat, if it is completely dependent on fuel. Providing will be very energy intensive. Therefore, 'in this embodiment, the return of high temperature gas to the calciner is reused' not only saves fuel, but also generates steam, which makes the entire C〇2 capture system more energy efficient and lowers cost. In one embodiment, the "calcining furnace may adopt a direct heating method or an indirect heating method" to reflow the high temperature gas to the general furnace for reuse. Fig. 2 and Fig. 3 respectively illustrate the implementation of the present invention. A schematic diagram of direct heat exchange and inter-φ heat exchange of a calciner. As shown in Fig. 2, the calciner 302 is directly heated by the oxygen-enriched burner 301, and the high-temperature flue gas generated by the calciner 302 is subjected to dust removal. (for example, the cyclone 303) and the backflow through the induced draft fan 304 to the oxygen-enriched burner 301 to promote combustion to increase the temperature of the furnace 302, which can greatly reduce the amount of fuel used. The steam generated by the flue gas after several reflows It can be used as a gas for simmering. As shown in Fig. 3, the calciner 302 can also be heated indirectly, for example, by heating the outer tube of the calcined 12 201141598 1 wouuyr/\ furnace 302, and distributing the heat uniformly in the crucible furnace by heat conduction. The high-temperature flue gas generated by the calcining furnace 302 in each region of 302 is re-introduced into the oxygen-enriched burner 301 by the induced draft fan 304 to greatly reduce the amount of fuel used. Further, the calcining furnace 302 can be appropriately stirred or appropriately designed or The tumbling completes the calcination, and the interior of the calciner 302 may further have at least one settling plate to intercept the dust which is generated during the agitation. According to the above, in one embodiment, the carbon dioxide capture system is fed. And discharge system, bubble fluidized bed type carbonation furnace (first reactor 2〇), moving (creep) moving bed type calciner (second reactor 30), calcium oxide (Ca〇) storage tank 40 Separating the CO 2 condensing tank 50, the dust collecting device 6〇 and the control program composition, mainly by two sets of reactors: a first reactor 20-carbonation furnace and a second reactor 30-calcining furnace, respectively, to carry out adsorption reaction and Desorption reaction. When the system is operating, the flue gas containing C〇2 component is introduced into the carbonation furnace, and the temperature of the calcium oxide (CaO) is controlled to be between 650 ° C and 750 ° C. In the carbonation furnace C〇 2 reacts with CaO to form calcium carbonate (CaC03), which will naturally enter the second reactor 30 calciner from the first reactor 20 carbonation furnace due to the increase in molecular weight spring, and the temperature in the calciner is controlled. At 850 ° C ~ 950 ° C. The satin burner uses steam (or nitrogen or air or argon or other inert gas) as the calcining gas. The smoldering gas is uniformly distributed in the space of the calciner by means of the air duct 31 to produce different gas distribution amounts, so that the gas overlap interference phenomenon is generated inside the dig furnace, and then the adsorbent is moved to the outlet end to pass through the calciner to achieve complete calcination. the goal of. After high temperature calcination, CaC〇3 releases the adsorbed C〇2 to form CaO, which is recycled to the carbonation furnace for CO2 capture. The high concentration of chopping furnace exhaust gas c〇2 and steaming 13 201141598 is widely separated by condensation 3 (ie, separation C. 2 condensation tank 5 °), and the captured high concentration 2 can be sealed and reused. In the case of a calciner, the ancient X: the required high temperature is supplied by an oxygen-rich burner, and the calciner generates a soaked milk body and then uses the reflux method as an auxiliary high-temperature gas of the oxygen-enriched burner to reduce the amount of fuel used. The purpose of energy saving and heat recycling. In the example, the whole process is automated, including: adsorption and desorption of fresh adsorbent (10), transport of adsorbent C, and discharge of deactivated = adsorbent (waste drain) are continuous cycle operation modes. The operation of monitoring the control of the material level of each storage tank can be monitored by using a high temperature level gauge, and taking time = control mode (timer). For example, the adsorbent storage tank can use the same /m level gauge to monitor the powder height of one of the adsorbents, and when the powder reaches a certain value, the feed is stopped, and the feed or discharge is started. . At present, the C〇2 capture system is actually tested, continuous cycle operation, when the inlet C〇2 concentration is between 12% and 14%, the c〇2 emission concentration is measured at the discharge port, and the operation is continuously operated for 6 hours, and the c〇2 efficiency can be captured. Up to 99%~1〇〇% or more. Please refer to Figs. 4A and 4B, which are respectively a graph of C〇2 captured by the carbonation furnace of the present invention, and a graph of C〇2 removal efficiency. In the experimental example, the adsorbent CaO feed was 16.5 kg, the carbonator pressure was 160-165 cm H2O, the carbonator temperature was 650 ° C, and the C〇2 gas flow rate was 147 m ^ 3 /min (CMM/min). As shown in Fig. 4A, the concentration of c〇2 at the inlet of the carbonator is 13%-16%'. Therefore, the C〇2 removal efficiency is as high as 99% to 100%, as shown in Fig. 4B.
201141598 I VVUW7I /-V 綜合來說’實施例所提出之二氧化碳捕獲系統具有許 多項優點，例如： (1) 碳酸化爐為氣泡式流體化床，與循環流化床比 較所需空間少。且有連通管設計不需動力以重量自然落 下’將吸附劑推入煅燒爐内。 (2) 锻燒爐為移動床除可充份烺燒並可設計成不同 溫度區域控制溫度及蒸汽曝氣量進行吸附劑改質。 (3) 锻燒爐升溫燃燒器採用富氧燃燒方式，將煅燒 爐排出的高溫煙氣予以迴流，充份節省燃料消耗。 (4) 若使用蒸汽作為煅燒氣體，煅燒所需要的蒸汽 則可經由迴流煙氣獲得，不需引用另外蒸汽源。 (5) 經過實驗連續操作6小時，可證實c〇2捕獲效率 達 99-100%。 實施例所提出之二氧化碳捕獲系統，亦可應用在許多 不同的技術領域’例如電力業、鋼鐵業（2〇〇5年c〇2排放 2,900萬嘲）、石化業（2〇〇7年c〇2排放2,4〇〇萬噸）、水泥 業（2006年C〇2排放764萬噸）等等，都可用來捕獲所排放 的二氧化碳，故極富應用價值。另外，所捕獲的二氧化碳 可進行再利用’例如甲醇原料（目前曱醇需求超過3,4〇〇萬 噸’每噸550美元計，年產值高達6,〇〇〇億台幣），碳酸二 甲月曰（DMC，全球需求2〇萬噸，每噸ι，2〇〇美元計，年產 值向達80億台幣）’二曱基醚(DME，全球需求375萬噸， 每噸510美元計，年產值高達630億台幣）等等，故極具技 術衍生價值。 15 201141598 綜上所述，雖然本發明已以實施例揭露如上，然其 並非用以限定本發明。本發明所屬技術領域中具有通常 知識者，在不脫離本發明之精神和範圍内，當可作各種 之更動與潤飾。因此，本發明之保護範圍當視後附之申 請專利範圍所界定者為準。 【圖式簡單說明】 第1圖，其繪示依照本發明一實施例之二氧化碳捕 獲糸統的不意圖。 第2圖係繪示本發明實施例之煅燒爐直接熱交換之 示意圖。 第3圖係繪示本發明實施例之煅燒爐間接熱交換之 示意圖。 第4A圖為本發明一實驗例之碳酸化爐捕獲C02之曲 線圖。 第4B圖為本發明一實驗例之碳酸化爐之C02去除效 率之曲線圖。 【主要元件符號說明】 11 :氣送系統 12 :送風機(/風車） 13 :貯料槽 14 :進料槽 15 :輸送帶 16 :旋轉閥 201141598 1 VV 星·τν 20 :第一反應器 21 :佈風板（或氣體分佈盤） 200 :連通管 30 :第二反應器 31 :佈風管 301 :富氧燃燒器 302 :煅燒爐 303 :旋風集塵器 φ 304 :引風機 40 :氧化鈣（CaO)儲料槽 50 :分離C02冷凝槽 60 :粉塵捕集設備201141598 I VVUW7I /-V In general, the carbon dioxide capture system proposed in the embodiment has many advantages, such as: (1) The carbonation furnace is a bubble fluidized bed, which requires less space than a circulating fluidized bed. And there is a connecting tube design that does not require power to naturally drop in weight to push the adsorbent into the calciner. (2) The calciner is a moving bed except that it can be fully calcined and can be designed to control the temperature and steam aeration in different temperature zones for the modification of the adsorbent. (3) The calciner heating furnace adopts an oxy-combustion mode to reflow the high-temperature flue gas discharged from the calciner to fully save fuel consumption. (4) If steam is used as the calcining gas, the steam required for calcination can be obtained by refluxing flue gas without reference to another steam source. (5) After continuous operation for 6 hours, the c〇2 capture efficiency was confirmed to be 99-100%. The carbon dioxide capture system proposed in the examples can also be applied in many different technical fields, such as the power industry, the steel industry (2〇〇5 years, c〇2 emissions, 29 million taunts), and the petrochemical industry (2〇〇7 years) 2 emissions of 240,000 tons), cement industry (2006 C〇2 emissions 7.64 million tons), etc., can be used to capture the carbon dioxide emissions, so it is of great value. In addition, the captured carbon dioxide can be reused 'for example, methanol raw materials (currently sterol demand exceeds 30,000 tons, 550 US dollars per ton, annual output value is up to 6, 100 million Taiwan dollars), carbonic acid DM (DMC, global demand 2 million tons, per ton of ι, 2 〇〇, annual output value of 8 billion Taiwan dollars) 'D-decyl ether (DME, global demand 3.75 million tons, 510 US dollars per ton, year The output value is as high as 63 billion Taiwan dollars, etc., so it has great technological value. In the above, the present invention has been disclosed in the above embodiments, but it is not intended to limit the present invention. A person skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, the scope of protection of the present invention is defined by the scope of the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing a carbon dioxide capture system according to an embodiment of the present invention. Fig. 2 is a schematic view showing direct heat exchange of a calciner according to an embodiment of the present invention. Figure 3 is a schematic view showing the indirect heat exchange of the calciner of the embodiment of the present invention. Fig. 4A is a graph showing the capture of CO 2 in a carbonation furnace according to an experimental example of the present invention. Fig. 4B is a graph showing the removal efficiency of CO 2 of the carbonation furnace of an experimental example of the present invention. [Description of main component symbols] 11: Air delivery system 12: blower (/windmill) 13: Storage tank 14: Feeding tank 15: Conveyor belt 16: Rotary valve 201141598 1 VV Star·τν 20 : First reactor 21 : Air distribution plate (or gas distribution plate) 200: communication pipe 30: second reactor 31: air distribution pipe 301: oxygen-enriched burner 302: calciner 303: cyclone dust collector φ 304: induced draft fan 40: calcium oxide ( CaO) hopper 50: separation CO 2 condensing tank 60: dust trapping equipment
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