化學迴路燃燒程序為一種同時兼具有低成本、高能源效率及二氧化碳捕獲的新穎燃燒程序，其技術原理為使用金屬氧化物擔任載氧體於兩個反應器之間進行交互還原/氧化反應，傳遞熱能與氧氣，以防止燃料與空氣直接接觸產生二氧化碳、二氧化硫及氮氧化物之混合性氣體，進而達到二氧化碳捕獲的效果。一般而言，載氧體於化學迴路燃燒程序中之效益將受到各載氧體性能、反應器設計及燃料選擇影響，其中又以載氧體之性能最為重要，扮演著熱與氧的傳遞樞紐，為影響整體反應是否連續操作之關鍵。常見的載氧體中，鐵系載氧體具有高機械強度、低成本及對環境無衝擊性等優點，為運用於化學迴路燃燒程序中最廣泛且具高商業化價值之金屬氧化物系統；但是，鐵系載氧體之多氧化相態，於燃料/空氣反應器中進行還原/氧化反應時，多重結構成分之變化將導致還原速率複雜及燃料轉換效果略低等問題，成為使用該系統載氧體於化學迴路燃燒程序中之主要障礙。因此，本研究將藉由海水中之鹼金屬、鹼土金屬元素摻雜改質鐵系載氧體，試圖提升其於化學迴路燃燒程序中之還原動力。
首先，針對氧化鐵活性載氧體分別於不同氣體燃料中進行還原性能之探討，隨後並添加不同比例之氧化鋁惰性擔體於氧化鐵載氧體系統中，嚴選一種適合比例之氧化鐵/氧化鋁載氧體。可以發現，氧化鐵於各氣體料氣氛下之初始還原溫度將隨有所不同，且依序所表現之初始還原溫度由高至低依序為一氧化碳、合成氣與氫氣，顯示於一氧化碳氣氛下，較低之能量即可以使氧化鐵進行還原。而當氧化鐵與氧化鋁比例為60：40時，該系統載氧體則具有較佳之抗磨耗能力、反應活性以及反應穩定性，故本實驗將使用該比例氧化鐵/氧化鋁載氧體進行後續之摻雜改質程序之評估，並且透過常壓電漿噴束製備含鈉水溶液，以1-10 wt. %的濃度摻雜改質氧化鐵/氧化鋁載氧體，以探討鈉摻雜改質濃度對於氧化鐵/氧化鋁載氧體之影響。結果顯示，不同鈉摻雜改質濃度將造成氧化鐵氧化鋁載氧體之結晶結構、表面形貌及比表面積發生變化，進而影響其於實際操作條件下之燃料轉化能力及高溫循環穩定性。其中，當鈉摻雜改質濃度為1 wt. %時，微量之鈉將促使該載氧體系統於還原/氧化反應下進行離子擴散，使載氧體內部形成孔洞，提升載氧體之反應比表面積，進而促進該載氧體系統於反應氣氛下之氣-固反應，維持鈉摻雜改質氧化鐵/氧化鋁載氧體於高溫多圈反應下之循環穩定性，以利該系統載氧體運用於化學迴路燃燒程序。
另一方面，海水以常壓電金噴束製備無氯之鹼金屬、鹼土金屬水溶液摻雜改質失活氧化鐵/氧化鋁載氧體將依據上述之製備參數加以研究，以評估海水摻雜改質失活氧化鐵/氧化鋁載氧體之可行性。結果顯示，常壓電漿噴束將依照前驅物霧化、電漿氧化及氧化物顆粒溶解之程序，製備獲得無氯之鹼金屬、鹼土金屬水溶液。若加以摻雜改質於失活氧化鐵/氧化鋁載氧體中，將可使該系統載氧體於實驗級半套式流體化床反應器中進行五十圈之燃料轉化率高達0.93值，表現明顯優於原始之氧化鐵/氧化鋁載氧體及失活氧化鐵/氧化鋁載氧體佳，故以常壓電漿噴束製備海水摻雜改質失活氧化鐵/氧化鋁載氧體運用於化學迴路燃燒程序中將極具優越之前瞻性。

Chemical looping combustion (CLC) is classified as an emerging clean combustion process, where metal oxide (MexOy) as oxygen carrier is used to provide the oxygen sources for the combustion reaction, thereby achieving the inherent CO2 capture for the indirect contact between fuel and air. It is widely discussed that the development of the oxygen carriers, reactor design and fuel selection are the critical issues for the CLC process. Especially the development of oxygen carriers, the transfer ability of the heat and oxygen within the fuel/air reactor, avoiding the air direct connecting to the fuel are concerned. Of the feasible candidates, iron-based oxygen carrier (hematite, Fe2O3) is the most promising oxygen carrier for the commercial CLC application, because of its relative thermal stability, mechanical strength and low price. Unfortunately, the poor reduction kinetics of Fe2O3 is the major drawback during the high temperature operation, attributing to the three intermediate states in the reduction period. Therefore, the feasibility of using alkali- and alkaline earth-metals contained in the seawater can be utilized as the catalytic agents for Fe2O3 oxygen carrier in chemical looping combustion process was investigated to improve the reduction kinetics in this study.
The reduction kinetics of Fe2O3 oxygen carrier in fuel gases and different ratios of Fe2O3/Al2O3 as oxygen carriers are primarily discussed. The initial reduction temperature is found to be strongly depended on the fuels with the order of carbon monoxide > syngas > hydrogen. The Fe2O3/Al2O3 oxygen carrier with 60wt% Fe2O3 (FA32) shows successful attrition behavior, reaction activity and thermal stability in the CLC process. Furthermore, the formation mechanism for sodium-contained solution preparation via air atmospheric pressure plasma jet (Air-APPJ) method is also investigated, as well as assessing the sodium-modified FA32 oxygen carrier. With the Sodium dopant loading in the FA32 oxygen carrier increasing from 1 wt. % to 10 wt. %, Nax_FA32 samples with different crystalline structure and surface morphology caused the fuel conversion ability and the stability performance in the practical operation process. The enhanced properties such as the reduction behavior, thermal stability and attrition resistance of Na1_FA32 without degradation were feasibly achieved in the lab-scaled semi-fluidized bed reactor (semi-FzBR). Optimistic results were attributed to the promotion of the pore structure and the improvement on the selectivity of the fuel conversion from the sodium promoter.
Moreover, the use of seawater as a precursor to prepare the alkali- and alkaline earth- dopants using an Air-APPJ method. A three-step of the preparation route is proposed as ultrasonic atomization, plasma oxidation and dissolution. Based on the formation mechanism, dopants without any chlorine-containing residues modifying inreactive FA32 oxygen carrier (Na1_inFA32_seawater) has been established, which led to an improved reduction performance as compared to the raw FA32 and inreactive FA32 oxygen carriers. The high gas yield for syngas as fuel (Ysyngas) around 0.93 after fifty redox cycles for the Na1_inFA32_seawater oxygen carrier is achieved. It can be anticipated that the alkali- and alkaline earth metals-modified Fe2O3/Al2O3 samples from seawater by an Air-APPJ system as an oxygen carrier candidate in a reversible CLC process would be notably attractive.

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