臺灣博碩士論文加值系統

鈀複合膜廣泛的應用於氫氣分離與純化，一般的製備方法為利用無電鍍法在一多孔基材上析鍍緻密的鈀膜。多孔不鏽鋼因為容易和反應器組裝、具有好的機械強度與熱穩定性且其熱膨脹係數和鈀金屬相近，因此適合作為鈀複合膜的基材。然而，多孔不鏽鋼基材的表面孔洞大且分布廣、粗糙度高，造成製備一薄且緻密鈀膜的困難。多孔不鏽鋼基材表面存在的最大孔洞與粗糙度為影響緻密鈀膜厚度的主要因素，本研究利用氧化鋁粒子來修飾多孔不鏽鋼基材的孔洞大小與粗糙度來降低緻密鈀膜所需的厚度與提高氫氣通量。
　　第一階段分別利用規格大小<10 μm與1 μm的氧化鋁粒子來修飾基材孔洞大小，其中 < 10 μm的氧化鋁粒子在修飾時不會阻塞氣體的有效通道，由SEM觀察到基材表面孔洞大小在修飾後有明顯的下降。以<10 μm與1 μm的氧化鋁粒子修飾的基材所製備的緻密鈀膜厚度分別為22.9 μm、18.9 μm，而氫氣通量在壓差8 bar、溫度為773 K環境下為70.2及51.6 m3/m2-h，和未修飾的多孔不鏽鋼基材相較之下，其緻密鈀膜厚度為31.5 μm，而氫氣通量為44.8 m3/m2-h，在此階段的修飾能有效的降低鈀膜厚度並且提升氫氣通量。
第二階段修飾著重於降低多孔不鏽鋼基材的粗糙度，先以<10 μm的氧化鋁粒子修飾基材表面孔洞，再利用規格大小1 μm的氧化鋁粒子來修飾基材的粗糙度，藉由改變不同的抽氣壓力差來比較修飾基材粗糙度的效果。多孔不鏽鋼基材在經過第二階段，抽氣壓力差分別為100和200 mmHg的操作條件下修飾後，緻密的鈀膜厚度分別可降低至10.5和4.4 μm，而氫氣通量可提升至85.4和155.5 m3/m2-h，和第一階段修飾相較之下，經過兩階段修飾的基材對於降低緻密鈀膜厚度與提升氫氣通量有更顯著的幫助。

Palladium-based composite membranes have been used in hydrogen separation. In general, a dense Pd membrane is prepared on the porous substrate by an electroless plating process. Porous stainless steel (PSS) is suitable for the formation of composite membrane due to its thermal expansion coefficient close to the Pd-based films, ease to assemble with reactors, high mechanical strength and thermal stability. However, it is difficult to prepare thin and defect-free membranes on PSS because of the surface roughness, largest pore size and wide pore-size distribution on its surface. As a consequence, the thickness of the Pd membrane is largely dependent on the surface roughness and largest pores existed in PSS. In this work, the Al2O3 particles were employed to modify the pore size and the surface roughness of PSS to reduce the thickness of Pd membranes and improve hydrogen permeability.
　In the first part of the research, aluminum oxide particles with two different size distributions were used to modify the pore size of PSS. The effective number of passage through the porous substrates was kept and the maximum pore size has decreased based on SEM observations after modification with Al2O3 particles. The thicknesses of the Pd membrane supported on 10 μm and 1 μm Al2O3-modified PSS are 22.9 and 18.9 μm, and the hydrogen fluxes at 773K and ΔP=8 bar are 70.2 and 51.6 m3/m2-h, respectively. For comparison, the thickness and hydrogen flux of the membrane without modification is 31.5 μm and 44.8 m3/m2-h. It is evident that suitable substrate pretreatment will reduce the thickness of Pd membranes and improve hydrogen permeability.
　In order to decrease the surface pore size distribution as well as the surface roughness, two-step modification strategy was utilized. In the second part of the research, aluminum oxide particles with particle size ~1 micron were employed to modify the surface roughness of 10 μm Al2O3-modified PSS. The pressure difference across the PSS during suction procedure was changed in the second modification. The thicknesses of the Pd membrane supported on ΔP=100 and 200 mmHg Al2O3-modified PSS are 10.5

中文摘要
英文摘要
總目錄
圖目錄
表目錄

第一章　緒論

第二章　文獻回顧
2.1　鈀膜之簡介
2.2　鈀複合膜之製備方法
2.3　多孔基材
2.4　氣體穿透鈀複合膜之行為
2.4.1　氫氣滲透鈀膜之傳送機制
2.4.2　氣體於多孔基材的穿透行為
2.5　無電鍍法製備鈀複合膜
2.5.1　活化
2.5.2　無電鍍法製備鈀複合膜

第三章　實驗
3.1　實驗藥品
3.2　實驗儀器與器材
3.3　實驗步驟
3.3.1　基材清潔
3.3.2　基材孔洞修飾
3.3.2.1　一階段修飾孔洞
3.3.2.2　二階段修飾孔洞
3.3.3　氧化層製備
3.3.4　活化
3.3.5　無電鍍
3.3.6　氣體量測
3.3.7　鈀膜厚度量測

第四章　結果與討論
4.1　多孔不鏽鋼基材一階段修飾
4.1.1　第ㄧ階段修飾
4.1.2　鍍膜表現
4.1.3　氫氣通量
4.1.4　討論
4.2　多孔不鏽鋼基材二階段修飾
4.2.1　第二階段修飾
4.2.2　鍍膜表現
4.2.3　氫氣通量
4.2.4　討論
4.2.5　長期測試

第五章　結論

參考文獻

[1] A. Kleinert, G. Grubert, X. Pan, C. Hamel, A.S. Morgenstern, J. Caro, Compatibility of hydrogen transfer via Pd-membranes with the rates of heterogeneously catalysed steam reforming, Catal. Today 104 (2005) 267.
[2] J. Tong, Y. Matsumura, Pure hydrogen production by methane steam reforming with hydrogen-permeable membrane reactor, Catal. Today 111 (2006) 147.
[3] J. Tong, Y. Matsumura, H. Suda, K. Haraya, Experimental study of steam reforming of methane in a thin (6