以無電鍍製備鈀膜及其純化氫氣之應用｜國立清華大學博碩士論文庫

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研究生：	張繼遠 Chi-yuan Chang
論文名稱：	以無電鍍製備鈀膜及其純化氫氣之應用 Preparation of Highly Selective Palladium Membranes for Hydrogen Purification by Electroless Plating
指導教授：	趙桂蓉 Kuei-jung Chao
口試委員:
學位類別：	碩士 Master
系所名稱：	理學院 - 化學系 Department of Chemistry
論文出版年：	2004
畢業學年度：	92
語文別：	英文
論文頁數：	91
中文關鍵詞：	鈀膜、氫氣純化、不□鋼管、選擇率
外文關鍵詞：	Palladium membrane, hydrogen purification, stainless steel tube, selectivity
相關次數：	點閱：3 下載：0
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摘要
本研究探討多孔性不□鋼(PSS)膜管為基材之金屬鈀複合膜管的製備以及特性鑑定。製備方法大致上可分為二個階段：不□鋼管的修飾和金屬鈀膜的沈積。製備的樣品則以氬氣通透性及氫氮選擇率來鑑定其特性。
修飾的主要目的即為平整化膜管的表面。PSS膜管經表面磨平、清洗，再以氧化鋁粉填充其表面上的孔洞並被覆Ludox二氧化矽後，可由光學顯微鏡觀察得知修飾後的表面已漸漸平整。並由氬氣通透性的實驗發現修飾後的PSS膜管仍具有很高的通透性，有利於氣體在修飾後的PSS膜管中擴散。
金屬鈀膜是以無電鍍的方式沈積在修飾過的PSS膜管上。首先，膜管以具有高度地催化活性的鈀奈米膠體溶液活化。此膠體能使後續鍍上的鈀膜產生向下紮根的結構，故附著力可大為提升。結合滲透作用的無電鍍使金屬鈀膜更趨緻密，其緻密程度可由鈀膜呈氣通透性得知。再者，緻密化之鈀膜選擇率在350 °C 及20 PSI的壓差下，H2對N2的通透選擇率可達到2070，同時氫氣的流量到達195 ml/min (約14 m3/m2.min.atm0.5)

Abstract
The preparation and characterization of dense Pd composite membrane on porous stainless steel (PSS) tube are reported. The preparation comprises two stages: modification of PSS tubular support and deposition of Pd membrane. The characterization includes argon permeability and selectivity of hydrogen to nitrogen.
The purpose of modification was to smooth the surface of PSS tube. The polished and cleaned PSS tubular membrane was modified by filling surface pores with alumina powders and coating with colloidal silica. After the modification, the surface was smooth observed by optical microscopy.
The Pd membrane was deposited on modified PSS tube by electroless plating. Before plating, the tube was activated by Pd nano-particles which has highly catalytic activity and has been found to inhance the adhesion of Pd membrane on modified PSS support. Electroless plating combined with osmosis was adopted to prepare the Pd membrane. The resulting Pd/PSS composite filters possess vert low argon permeability and the H2/N2 selectivity up to 2070 at 350 °C at the pressure difference of 20 PSI with the hydrogen flux of 195 ml/min (ca 14 m3/m2.min.atm0.5).

Contents
博碩士論文授權書    I
指導教授推薦書    II
考試委員審定書    III
Abstract    IV
摘要    V
謝誌    VI
Chapter 1. Introduction    1
1.1 Hydrogen Demand    1
1.2 Hydrogen Separation through Palladium Membrane    5
1.3 Preparation of Palladium Membrane    12
1.4 Permeability of a Porous Media    27
1.5 Purpose of This Research    32
Chapter 2. Experimental    33
2.1 Chemicals    33
2.2 Overview of experimental section    35
2.3 Surface Cleaning of PSS Tube    36
2.4 Surface Planarization of PSS Tubes    37
2.5 Colloid Coating    43
2.6 Deposition of Palladium Membranes    45
2.7 Characterization    50
Chapter 3. Results and Discussion    54
3.1 Surface Modification of PSS Tubes    54
3.2 Peeling of Pd membrane    66
3.3 Permeability through Pd membranes    71
3.4 Performance of Pd membranes    79
3.5 Characteristic of Pd Nano-colloids    85
Chapter 4. Conclusion    91


Figure Contents
Figure 1.1 Hydrogen diffusion through palladium film.    6
Figure 1.2 H/Pd phase diagram    10
Figure 1.3 The scheme for the electroless plating combined with osmosis.    20
Figure 1.4 MOCVD    22
Figure 1.5 Magnetron sputtering    23
Figure 1.6 Electroplating    25
Figure 1.7 Composite membrane    30
Figure 2.1 The scheme of preparation of Pd composite membranes    35
Figure 2.2 The schematic diagram of planarization    38
Figure 2.3 The set-up of the dip-coating    42
Figure 2.4 The set-up for Pd colloidal coating.    47
Figure 2.5 The set-up of electroless plating    49
Figure 2.6 The set-up for the measurement of permeability.    51
Figure 2.7 The set-up for the measurement of selectivity.    52
Figure 3.1 The Surface of original PSS tube    55
Figure 3.2 The Surface of polished PSS tube    55
Figure 3.3 The difference between polished surface and original surface    55
Figure 3.4 The Cleaned surface    56
Figure 3.5 The OM picture of PSS surface after the growth of MFI membrane    58
Figure 3.6 The OM picture of PSS surface after coating of colloidal MFI membrane    58
Figure 3.7 The OM picture of PSS surface after coating with colloidal MFI membrane and polish posttreatment    59
Figure 3.8 The OM picture of colloidal silica membrane after calcination    60
Figure 3.9 The argon permeability of Tube A    61
Figure 3.10 The argon permeability of Tube B    61
Figure 3.11 The PSS tube filled with alumina powders    62
Figure 3.12 The argon permeability of modified PSS tubes (the values of estimated pore sizes are listed in the parentheses)    63
Figure 3.13 The PSS surface after calcination    64
Figure 3.14 The argon permeability of modified PSS tubes    65
Figure 3.15 Time period of preparation    65
Figure 3.16 The peeling of Pd membrane    66
Figure 3.17 The peeling area    67
Figure 3.18 The anchoring effect    68
Figure 3.19 The line scan of EPMA    69
Figure 3.20 The argon permeability of modified PSS tubes    73
Figure 3.21 The relation between the permeability of Pd membrane and pore size of substrate    78
Figure 3.22 The selectivity and hydrogen flux of each tube    79
Figure 3.23 Hydrogen flux through Pd composite membrane    82
Figure 3.24 The result of the regression analysis    84
Figure 3.25 The path of x-ray    86
Figure 3.26 The original PXRD spectrum of Pd nanocolloids    86
Figure 3.27 The corrected PXRD spectrum    87
Figure 3.28 The differences of the peak positions at different angle    88
Figure 3.29 The lattice constant    89


Table Captions

Table 1.1 Comparison of different fuel cells    2
Table 1.2 Use of fuel cells1    2
Table 1.3 The thickness of Pd membrane and n value in literature    9
Table 1.4 The composition of the activation bath reported by Li et al    14
Table 1.5 The composition of the activation bath reported by Ma et al    15
Table 1.6 The composition of the activation bath reported by Varma et al    15
Table 1.7 The compositions of the plating bath    17
Table 1.8 The compositions of the plating bath reported by Hughes et al    18
Table 1.9 The compositions of the plating bath reported by Ma et al    18
Table 1.10 The calculation of the effective concentration in the plating bath    20
Table 2.1 The composition of the plating bath.    48
Table 3.1 Procedures of each tube    70
Table 3.2 The Ar permeability of Pd/Modified PSS    71
Table 3.3 The Ar permeability of Pd membranes    75
Table 3.4 Rise in permeability after heat treatment at 350 °C    77
Table 3.5 The selectivity and hydrogen flux at different pressure    80
Table 3.6 The result of calculation    83
Table 3.7 The calculation of PXRD    90

                                

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