Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/11214
標題: 鎂合金廢料再生為氫氣能源及其生命週期評估之研究
Production of Hydrogen Energy from Magnesium Scraps and its Life Cycle Assessment
作者: 卓錡淵
Cho, Chi-Yuan
關鍵字: Magnesium scraps
鎂合金廢料
Recycling
Hydrogen generation
Catalyst
life cycle assessment
回收
氫氣生產
觸媒
生命週期評估
出版社: 材料工程學系所
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摘要: 鎂合金材料在應用面上具多項優異特性例如抑振性能佳、比強度高及良好的電磁遮蔽效果等,因此,隨著輕量化的優勢,鎂合金所製成的零組件已逐漸運用於交通運輸工具。此外,目前個人行動電子產品的零組件亦已大量使用鎂合金製品。預料鎂合金廢棄物將會逐漸增多,因此廢棄物資源的處理方式將成為未來鎂合金發展的重要課題之一。基於此,本研究乃將鎂合金廢料轉換為一種無二次污染、可製備氫氣能源的方式。 本研究首先使用金屬觸媒(白金鈦網)是以正向固定荷重(6 ± 0.5 kg)和旋轉磨擦(6 ± 0.5 kg、8 ± 1 rpm)的方式與鎂廢料試片緊密接觸,形成伽凡尼耦合(galvanic couple)。將其置入於5 wt.%氯化鈉水溶液中,即可在無需耗費額外能量之下,進行電解水反應而迅速產出氫氣。實驗結果顯示,白金鈦網以固定荷重方式之平均氫氣產生速率約為302.3 ml min-1 (g of catalyst)-1;而以旋轉磨擦的方式其產氫速率約為432.4 ml min-1 (g of catalyst)-1。利用固定荷重的方式產出氫氣,當反應時間增長時,伴隨氫氣產出所生成的副產物-氫氧化鎂會逐漸阻隔於金屬觸媒(白金鈦網)與鎂廢料試片之間,造成氫氣產量不再繼續增加。而使用旋轉磨擦方式,則在長時間(8000 sec)的製氫反應,仍能維持穩定的產氫量。而白金鈦網表面所披覆的白金會有少許損耗(約為0.0278 g)。經由氣相層析儀鑑定實驗所產出的氣體成份乃為氫氣和水氣,而氫氣純度約為97.2 mol.%。此外,在反應時間50 min內,當氯化鈉水溶液濃度約為3.5 wt.%,其產出氫氣總累積量會達到最大值。 為了使金屬觸媒能與鎂合金廢料之接觸方式無須藉由任何外力輔助,將會使用金屬觸媒(白金鈦網和AISI 304不鏽鋼網)以沾黏半固態鎂合金廢料方式進行耦合。實驗結果顯示藉由較高溫度的半固態鎂廢料(580 ± 5 °C)在凝固過程中所形成的收縮,可將其兩者緊密接觸。若將其置於3.5 wt.%氯化鈉水溶液中,在50 min時間內,使用白金鈦網和AISI 304不鏽鋼網為觸媒,其平均產氫量分別約為28.2 ± 5.7 liter和16.1 ± 7.8 liter。而此兩種金屬觸媒皆能催化每1 g的鎂合金廢料產出約1 liter的氫氣量。此外,白金鈦網和AISI 304不鏽鋼網分別經過10次及5次以上重複使用,仍具有催化鎂合金廢料產出氫氣的效果。實驗過程中所產出的氫氣將導入質子交換型燃料電池,轉換為電能形式呈現。使用白金鈦網(重複使用第4次,共20片)為觸媒,在50 min內可產出11.3 liter的氫氣量,計算總發電功率約為498.1 Wh (1.79 MJ)。而使用AISI 304不鏽鋼網(第1次使用,共20片)約有10.4 liter氫氣產量,其總發電功率約為424.4 Wh (1.53 MJ)。 為了更進一步地瞭解本研究使用鎂合金廢料轉換為氫氣能源對於環境所造成之影響與衝擊,將藉由生命週期評估(Life cycle assessment)之系統化架構,從能源使用量、製氫過程中污染物排放量等方面進行綜合評析。而評估分析結果亦與目前鎂合金廢料處理方式(重新回收廢料製成符合ASTM B93規範標準之鎂錠)及其他製氫方式(利用金屬粉末以及電解水法)進行分析比較。評估結果顯示本研究中採用白金鈦網和AISI 304不鏽鋼網為觸媒,在製造1 kg氫氣之能源使用量,其分別約為35.1 MJ或34.9 MJ。而能源使用量主要集中於產氫試片的製作過程。此外,使用純鋁或純鎂金屬粉末為產氫來源,製造1 kg 氫氣之能源使用量約為11804 MJ或6240 MJ。主要由於製作金屬粉末需經長時間研磨,導致能源使用量陡增。另外,電解水製氫方式的能源使用量亦高於本研究。並於製氫過程中會有能量耗損(約15 %),而在製氫與電力供給等過程會釋放汙染物(例如CO2、SO2和NOx等)。相較於目前回收鎂廢料製程(重製為符合標準之鎂錠),若回收1 kg鎂廢料的能源用量僅約為151 MJ 或164 MJ。而本研究僅需2.8 MJ (kg of Mg scraps)-1。
Due to excellent properties such as high specific strength, excellent vibration damping property and good EMI (electromagnetic interference), Mg alloys has an increasingly number of uses in transportation vehicle (e.g., door frame, engineering covering, oil pan, wheel, etc.) and the outer shell of 3C electronic products (e.g., the upper cover and base seat of notebook computer, the outer covering of personal mobile communication tool, etc.). Recycling of Mg scraps (i.e., post-consumed or end-of-life Mg products) has become increasingly important. This study proposes a new method for generating H2 gas in aqueous NaCl by the hydrolysis of Mg scraps. The experimental findings of this study not only indicate a method for generating hydrogen but also promote the recycling of the Mg scraps. Pt-coated Ti net (i.e., ~ 2.5 μm of platinum film being electroplated on the surface of Ti net) was adopted as a catalyst to promote the hydrolytic reaction of an Mg sample in aqueous NaCl (5 wt.%) to generate H2 without extra supply of power. Two experiments were conducted and the volumes of H2 generated were compared. In one of the experiments, the Pt-coated Ti net was statically loaded on the top surface of the Mg sample, with a loading force of 6 ± 0.5 kg. In the other, the Pt-coated Ti net was ground against the surface of the Mg sample (6 ± 0.5 kg, 8 ± 1 rpm). When a Pt-coated Ti net was statically loaded (6 ± 0.5 kg) on the Mg sample, the average H2 generation rate of about 302.3 ml min-1(g of catalyst)-1 was measured. The curve of cumulative volume of generated H2 reached a plateau after the hydrolysis reaction proceeded a certain time. Mg(OH)2 passive layer which prevented contact between the catalyst (Pt/Ti net) and the Mg sample was the major reason leading to the plateau. When the Pt-coated Ti net was ground (6 ± 0.5 kg, 8 ± 1 rpm) onto the Mg sample surface, more H2 gas was produced than was generated by static loading. The cumulative volume of H2 gas generated was almost linearly proportional to the reaction time. The average H2 generation rate was calculated to be 432.4 ml min-1(g of catalyst)-1. No Mg(OH)2 passive layer formed on the Mg sample surface, because the Pt-coated Ti net ground against the sample, removing the Mg(OH)2 layer. A little of the Pt had been consumed (~ 0.0278 g). The generated gas was analyzed by GC (gas chromatography). Only hydrogen and water vapor were detected. The purity of the hydrogen was analyzed to be around ~ 97.2 % mole fraction. Additionally, the maximum volume of generated H2 was observed in 3.5 wt.% aqueous NaCl. In order to improve the H2 generation efficiency of the Mg scraps, platinum-coated Ti (Pt-Ti) net and AISI 304 stainless steel (S.S.) net were dipped in the semi-solid Mg scraps. The average cumulative volume of generated H2 in 3.5 wt.% NaCl solution at 25 ˚C using Mg scraps/Pt-Ti samples and Mg scraps/S.S. samples was about 28.2 ± 5.7 liter and 16.1 ± 7.8 liter. The generated H2 volume per one gram of Mg scraps consumption was 1.0 ± 0.1 liters from Mg scraps/Pt-Ti samples, which was similar to the result by using Mg scraps/S.S. samples (1.1 ± 0.1 liters). In addition, both of these two metallic net catalysts showed a good durability of more than 5 experimental cycles to be re-used for H2 generation. The generated H2 in this study was converted into the electrical energy by fuel cell. A set of used Pt-coated Ti nets (20 pieces, the 4th time of use) was applied to be the catalyst metal, the cumulative H2 volume was about 11.3 liters in 50 min. The power generated was about 1.79 MJ (498.1 Wh) during the H2 generation. New AISI 304 stainless steel nets (20 pieces) were used as the catalyst. The cumulative H2 volume within 50 min was about 10.4 liters. The generation of power was about 1.53 MJ (424.4 Wh). The systematic analytical method of life cycle assessment (LCA) was carried out to investigate the environmental impacts of proposed H2 production process. The H2 production processes from metallic materials (i.e., Al powders, Mg powders) and the recycling process of Mg scraps were considered for comparison with LCA method. The energy requirement using Mg scraps/Pt-Ti couples to generate 1 kg of H2 was about 35.1 MJ. Around 34.9 MJ was needed by applying Mg scraps/S.S. couples to produce 1 kg of H2. The main energy consumption resulted from the preparation of Mg scraps/Pt-Ti and Mg scraps/S.S. couples. Moreover, the energy requirement of 1 kg H2 production by Al and Mg powders was about 11804 MJ and 6240 MJ. The energy requirements for generating 1 kg of H2 are mainly because of the energy being consumed to prepare the metallic powders. In addition, the energy requirement for producing 1 kg H2 by electrolysis water method (235 MJ or 243 MJ) was much higher than that of present study. Also, the H2 production process by this method, the air pollutants such as CO2, SO2 and NOx was released. From the viewpoint of recycling process of Mg scraps, the energy requirement and pollutant released of present study and conventional process were compared. The proposed process in present study for the recycle of 1 kg Mg scraps was about 2.9 MJ. The energy requirement for recycling 1 kg Mg scraps is about 151 MJ or 164 MJ in conventional processes.
URI: http://hdl.handle.net/11455/11214
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