本論文使用計算流體力學(Computational Fluid Dynamics，CFD) 軟體FLUENT配合一系列之使用者自定函數(User Defined Function, UDF)完成了自二氧化碳合成甲醇之填充床式觸媒反應器(Packed Bed Catalytic Reactor，PBR)與觸媒薄膜反應器(Catalytic Membrane Reactor，CMR)之三維模式模擬，模式納入了填充床球型觸媒顆粒反應器中(1)巨相之流力、熱傳與質傳；(2)觸媒顆粒內之流力、熱傳、質傳與化學反應；(3)巨相與觸媒顆粒間之流力、熱傳與質傳；及(4)薄膜兩側巨相間之流力、熱傳與質傳。流體速度限制於層流範圍。
透過模擬探討了反應器內部之特性分佈，包括壓力、速度、溫度與組成，並探討了參數之影響，包括觸媒顆粒孔徑、粒徑、操作壓力、進料流量、是否具薄膜與膜厚等。針對填充床之摩擦因子以及觸媒顆粒與巨氣相間之熱傳係數與質傳係數，本研究並比較模擬結果與文獻關聯式，結果顯示摩擦因子較吻合，熱傳係數與質傳係數則有極大差異。

This thesis uses Computational Fluid Dynamics, combining with a set of User Defined Functions (UDF) to accomplish the simulation studies for the Packed Bed Catalytic Reactor (PBR) and the Catalytic Membrane Reactor (CMR) for methanol synthesis from carbon dioxide and hydrogen.

The model encompasses all important mechanisms for PBR and CMR, including (1) the hydraulic, heat and mass transfers of bulk gas; (2) the hydraulic, heat and mass transfers and chemical reaction of catalyst; (3) the hydraulic, heat and mass transfers between bulk gas and catalyst; (4) the hydraulic, heat and mass transfers between bulk gases and membrane. The fluid is in the laminar flow region.

The simulation facilitates the discussions on the profiles inside the reactor, including pressure, velocity, temperature and composition. The effects of catalyst particle pore size, diameter, operation pressure, feed flowrate, with or without membrane and membrane thickness are studied. The friction factor of the bed and the heat and mass transfer coefficients between catalyst particle and bulk gas are compared with the correlations reported in the literature. The friction factors are close to the correlations predictions, however, the heat and mass transfer coefficients are not and the data are very scattering.

致謝	………………………………………………………………i
中文摘要	…………………………………………………………….. .iii
英文摘要	...…………………………………………………………….iv
目錄	………………………………………………………………v
圖目錄	……………………………………..………………………viii
表目錄	.………………………………………………………...….xvii
第一章    前言 …………………………………………………….….1
第二章    文獻回顧 ……………………………………………….….4
2.1觸媒反應器 ……………………………………...………………..4
2.2薄膜反應器 ……………………………………………………….4
2.3甲醇合成 ………………………………………….………………5
第三章    甲醇合成系統 ……………………………………………..7
3.1化學反應和反應動力 …………………………………………….7
3.2薄膜特性 …………………………………………………….…...9
3.3設備配置 ………………………………………………………...10
第四章    一維數學模式 ……………………………………………12
4.1數學模式建立 …………………………………………………...12
4.2一維模式之數值方法及程式架構 ……………………………...15
第五章    計算流體力學模式 ……………........................................17
5.1統制方程式 ……………………………………………………...17
5.2系統配置與網格建立 …………………………………………..20
5.3FLUENT附加程式與設定 ……………………………………...29
5.3.1FLUENT附加程式 …………………………………………29
5.3.2FLUENT設定 ………………………………………………32
5.3.2.1觸媒反應器之FLUENT設定 …………………………33
5.3.2.2薄膜觸媒反應器之FLUENT設定 ……………………34
第六章    基本個案模擬結果 ……………………………..………..36
6.1基本個案/改變觸媒孔徑個案 …………………………………..40
6.1.1基本個案之設定條件 ………………………………………40
6.1.2質傳通量 ………………...………………………………….41
6.1.3有效因子 ……………………………………………………48
6.1.4反應程度 ……………………...…………………………….50
6.1.5壓力分佈 …………………………...……………………….51
6.1.6速度分佈比較 ……………………...……………………….57
6.1.7溫度分佈比較 ………………………………………………63
6.1.8組成分佈 ……………………………………………………69
6.2改變觸媒顆粒粒徑之影響 ………………………..…………….72
6.3改變進料流量之影響 ………………………….………………..79
6.4改變操作壓力之影響 …………………….…………………….82
6.5改變薄膜反應器薄膜厚度之影響 ………….………………….92
第七章    輸送參數分析 ……………………………………………96
7.1輸送係數之計算 ..………………………………………………97
7.1.1流力輸送係數 ………………………………………………97
7.1.2熱傳輸送係數 ………………………………………………98
7.1.3質傳輸送係數 ………………………………………………99
7.2 輸送係數與文獻關聯式之比較 ...……………………………101
7.2.1流力  ………………………………………………………101
7.2.2熱傳  ………………………………………………………108
7.2.3質傳  ………………………………………………………115
7.2.3.1擴散  …………………………………………………116
7.2.3.2對流與擴散……………………………………………147
第八章    結論 …..………………………………………………....178
符號說明	………………………………………………………….…182
參考文獻 ……………………………………………………………..188
附錄  …………………………...…………………………………….194
 

圖目錄
圖3-1	甲醇薄膜反應器之配置………………………………...11
圖4-1	觸媒薄膜反應器一維模式之程式架構………………...16
圖5-1	觸媒顆粒規則排列之配置……………………………...20
圖5-2	觸媒顆粒不規則排列之配置…………………………...21
圖5-3	進口端完整截面N=5示意圖………………...................22
圖5-4	管壁 管壁邊界層之網格示意圖-觸媒反應器….……….……23
圖5-5	管壁邊界層之網格示意圖-薄膜觸媒反應器…………..24
圖5-6	球型觸媒表面內外邊界層之示意圖.……….…………..25
圖5-7	進口端1/4截面，N=5示意圖………………………….25
圖5-8	觸媒反應器之系統尺寸配置示意圖…………………….26
圖5-9	薄膜觸媒反應器之系統尺寸配置示意圖……………….26
圖5-10	觸媒反應器之GAMBIT繪製圖(3D)…………………....27
圖5-11	薄膜觸媒反應器之GAMBIT繪製圖(3D)……………...28
圖6-1	觸媒反應器所討論之截面………………………..……...39
圖6-2	觸媒薄膜反應器所討論之截面……………….….……...39
圖6-3	S-A截面-改變觸媒孔徑對系統錶壓之影響……….…...52
圖6-4	S-B截面-改變觸媒孔徑對系統錶壓之影響……………53
圖6-5	S-C截面-改變觸媒孔徑對系統錶壓之影響………....…54
圖6-6	S-D截面-改變觸媒孔徑對系統錶壓之影響……………55
圖6-7	S-E截面-改變觸媒孔徑對系統錶壓之影響………..…..56
圖6-8	S-A截面-改變觸媒孔徑對系統流體速度之影響….…..58
圖6-9	S-B截面-改變觸媒孔徑對系統流體速度之影響…..…..59
圖6-10	S-C截面-改變觸媒孔徑對系統流體速度之影響………60
圖6-11	S-D截面-改變觸媒孔徑對系統流體速度之影響…...….61
圖6-12	S-E截面-改變觸媒孔徑對系統流體速度之影響…..…..62
圖6-13	S-A截面-改變觸媒孔徑對系統溫度之影響……………64
圖6-14	S-B截面-改變觸媒孔徑對系統溫度之影響……...…….65
圖6-15	S-C截面-改變觸媒孔徑對系統溫度之影響………..…..66
圖6-16	S-D截面-改變觸媒孔徑對系統溫度之影響…...……….67
圖6-17	S-E截面-改變觸媒孔徑對系統溫度之影響……………68
圖6-18	S-A截面-改變觸媒孔徑對產物之影響
(ex. CH3OH)…………………………………...…………70
圖6-19	S-A截面-改變觸媒孔徑對反應物之影響 (ex. H2)….....71
圖6-20	S-A截面-改變觸媒粒徑對壓力分佈之影響………..…..73
圖6-21	S-B截面-相同觸媒孔徑下改變觸媒粒徑
對速度之影響…………………………………….………76
圖6-22	S-B截面-改變進料流量對觸媒顆粒尾流之影響.……...80
圖6-23	S-A截面-改變操作壓力對壓力分佈之影響……….…..84
圖6-24	S-A截面-改變操作壓力對速度分佈之影響……….…..86
圖6-25	S-A截面-改變操作壓力對生成物組成(CH3OH)
分佈之影響……………………………………..….…….88
圖6-26	S-A截面-改變操作壓力對反應物組成(H2)
分佈之影響……………………………………..….…….90
圖6-27	S-C截面-薄膜厚度對生成物組成(CH3OH)
分佈之影響……………………………………..………..94
圖6-28	S-C截面-薄膜厚度對反應物組成(H2)
分佈之影響………………………………………....……95
圖7-1	摩擦因子之比較-觸媒反應器, Ptube=40bar…………….102
圖7-2	摩擦因子之比較-觸媒反應器, Ptube=4.3bar……………103
圖7-3	摩擦因子之比較-薄膜觸媒反應器
(δ=50μm),Ptube =40bar…….……………………….…….104
圖7-4	摩擦因子之比較-薄膜觸媒反應器
(δ=315μm),Ptube =40bar…….…...………………….……105
圖7-5	摩擦因子之比較-薄膜觸媒反應器
(δ=50μm), Ptube =4.3bar……………………..…….…….106
圖7-6	摩擦因子之比較-薄膜觸媒反應器
(δ=315μm), Ptube =4.3bar………………………………..107
圖7-7	熱傳係數之比較-觸媒反應器, Ptube =40bar...…….……109
圖7-8	熱傳係數之比較-觸媒反應器, Ptube =4.3bar………...…110
圖7-9	熱傳係數之比較-薄膜觸媒反應器
(δ=50μm),Ptube=40bar………..…………….……...……111
圖7-10	熱傳係數之比較-薄膜觸媒反應器
(δ=315μm),Ptube=40bar……….…………….….…...……112
圖7-11	熱傳係數之比較-薄膜觸媒反應器
(δ=50μm),Ptube=4.3bar………………….................……113
圖7-12	熱傳係數之比較-薄膜觸媒反應器
(δ=315μm),Ptube=4.3bar……….….……….………....…114
圖7-13	質傳係數(Sh_D)之比較-觸媒反應器,
Ptube=40bar, CH3OH….............................................…….117
圖7-14	質傳係數(Sh_D)之比較-觸媒反應器,
Ptube=40bar,H2O…………………………..….………….118
圖7-15	質傳係數(Sh_D)之比較-觸媒反應器,
Ptube=40bar,CO……………………………….………….119
圖7-16	質傳係數(Sh_D)之比較-觸媒反應器,
Ptube=40bar,H2…………………………….……………..120
圖7-17	質傳係數(Sh_D)之比較-觸媒反應器,
Ptube=40bar,CO2……………………………….…………121
圖7-18	質傳係數(Sh_D)之比較-觸媒反應器,
Ptube=4.3bar,CH3OH…………………………….….……122
圖7-19	質傳係數(Sh_D)之比較-觸媒反應器,
Ptube=4.3bar,H2O…………………………………..……..123
圖7-20	質傳係數(Sh_D)之比較-觸媒反應器,
Ptube=4.3bar,CO………………….…………..…....……..124
圖7-21	質傳係數(Sh_D)之比較-觸媒反應器,
Ptube=4.3bar,H2………………………………….……….125
圖7-22	質傳係數(Sh_D)之比較-觸媒反應器,
Ptube=4.3bar,CO2……..……………………………..……126
圖7-23	質傳係數(Sh_D)之比較-薄膜觸媒反應器
(δ=50μm),Ptube=40bar,CH3OH…………………….….…127
圖7-24	質傳係數(Sh_D)之比較-薄膜觸媒反應器
 (δ=50μm),Ptube=40bar,H2O……………....................….128
圖7-25	質傳係數(Sh_D)之比較-薄膜觸媒反應器
 (δ=50μm),Ptube=40bar,CO…………………….………..129
圖7-26	質傳係數(Sh_D)之比較-薄膜觸媒反應器
 (δ=50μm),Ptube=40bar,H2……………………….….…..130
圖7-27	質傳係數(Sh_D)之比較-薄膜觸媒反應器
 (δ=50μm),Ptube=40bar,CO2………………...….……….131
圖7-28	質傳係數(Sh_D)之比較-薄膜觸媒反應器
 (δ=315μm),Ptube=40bar,CH3OH………………….……132
圖7-29	質傳係數(Sh_D)之比較-薄膜觸媒反應器
 (δ=315μm),Ptube=40bar,H2O……………………...……133
圖7-30	質傳係數(Sh_D)之比較-薄膜觸媒反應器
 (δ=315μm),Ptube=40bar,CO……………………..……..134
圖7-31	質傳係數(Sh_D)之比較-薄膜觸媒反應器
 (δ=315μm),Ptube=40bar,H2……………………….…….135
圖7-32	質傳係數(Sh_D)之比較-薄膜觸媒反應器
 (δ=315μm),Ptube=40bar,CO2………………………..….136
圖7-33	質傳係數(Sh_D)之比較-薄膜觸媒反應器
 (δ=50μm),Ptube=4.3bar,CH3OH……………….….……137
圖7-34.	質傳係數(Sh_D)之比較-薄膜觸媒反應器
 (δ=50μm),Ptube=4.3bar,H2O……….……….……….….138
圖7-35	質傳係數(Sh_D)之比較-薄膜觸媒反應器
 (δ=50μm),Ptube=4.3bar,CO………………….…...…….139
圖7-36	質傳係數(Sh_D)之比較-薄膜觸媒反應器
 (δ=50μm),Ptube=4.3bar,H2…………………….………..140
圖7-37	質傳係數(Sh_D)之比較-薄膜觸媒反應器
 (δ=50μm),Ptube=4.3bar,CO2…………………..….……..141
圖7-38	質傳係數(Sh_D)之比較-薄膜觸媒反應器
 (δ=315μm),Ptube=4.3bar,CH3OH……………….………142
圖7-39	質傳係數(Sh_D)之比較-薄膜觸媒反應器
(δ=315μm),Ptube=4.3bar,H2O…………………...……….143
圖7-40	質傳係數(Sh_D)之比較-薄膜觸媒反應器
(δ=315μm),Ptube=4.3bar,CO……………………………..144
圖7-41	質傳係數(Sh_D)之比較-薄膜觸媒反應器
(δ=315μm),Ptube=4.3bar,H2……………………...…..…..145
圖7-42	質傳係數(Sh_D)之比較-薄膜觸媒反應器
(δ=315μm),Ptube=4.3bar,CO2………………...…...……..146
圖7-43	質傳係數(Sh)之比較-觸媒反應器Ptube=40bar,CH3OH………………………………148
圖7-44	質傳係數(Sh)之比較-觸媒反應器Ptube=40bar,H2O…………………………………149
圖7-45	質傳係數(Sh)之比較-觸媒反應器 
Ptube=40bar,CO…………………….…………..150
圖7-46	質傳係數(Sh)之比較-觸媒反應器
Ptube=40bar,H2……………………………………151
圖7-47	質傳係數(Sh)之比較-觸媒反應器Ptube=40bar,CO2……….…………………………152
圖7-48	質傳係數(Sh)之比較-觸媒反應器Ptube=4.3bar,CH3OH………………………………153
圖7-49	質傳係數(Sh)之比較-觸媒反應器Ptube=4.3bar,H2O…………………………………154
圖7-50	質傳係數(Sh)之比較-觸媒反應器Ptube=4.3bar,CO……………………………………155
圖7-51	質傳係數(Sh)之比較-觸媒反應器Ptube=4.3bar,H2……………………………………156
圖7-52	質傳係數(Sh)之比較-觸媒反應器Ptube=4.3bar,CO2…………………………………157
圖7-53	質傳係數(Sh)之比較-薄膜觸媒反應器
(δ=50μm),Ptube=40bar,CH3OH………………………….158
圖7-54	質傳係數(Sh)之比較-薄膜觸媒反應器
(δ=50μm), Ptube=40bar,H2O……….……………...……..159
圖7-55	質傳係數(Sh)之比較-薄膜觸媒反應器
(δ=50μm),Ptube=40bar,CO……………………….………160
圖7-56	質傳係數(Sh)之比較-薄膜觸媒反應器
(δ=50μm),Ptube=40bar,H2……………………….………..161
圖7-57	質傳係數(Sh)之比較-薄膜觸媒反應器
(δ=50μm),Ptube=40bar,CO2……………………..………..162
圖7-58	質傳係數(Sh)之比較-薄膜觸媒反應器
(δ=315μm),Ptube=40bar,CH3OH…………………...…….163
圖7-59	質傳係數(Sh)之比較-薄膜觸媒反應器
(δ=315μm),Ptube=40bar,H2O……………….……….……164
圖7-60	質傳係數(Sh)之比較-薄膜觸媒反應器
(δ=315μm),Ptube=40bar,CO………...……………………165
圖7-61	質傳係數(Sh)之比較-薄膜觸媒反應器
(δ=315μm),Ptube=40bar,H2………………………..……..166
圖7-62	質傳係數(Sh)之比較-薄膜觸媒反應器
(δ=315μm),Ptube=40bar,CO2………………….….………167
圖7-63	質傳係數(Sh)之比較-薄膜觸媒反應器
(δ=50μm),Ptube=4.3bar,CH3OH………………….………168
圖7-64	質傳係數(Sh)之比較-薄膜觸媒反應器
(δ=50μm),Ptube=4.3bar,H2O…………….………………..169
圖7-65	質傳係數(Sh)之比較-薄膜觸媒反應器
(δ=50μm),Ptube=4.3bar,CO……….……...………………170
圖7-66	質傳係數(Sh)之比較-薄膜觸媒反應器
(δ=50μm),Ptube=4.3bar,H2…………….……...………….171
圖7-67	質傳係數(Sh)之比較-薄膜觸媒反應器
(δ=50μm),Ptube=4.3bar,CO2………….……...………..…172
圖7-68	質傳係數(Sh)之比較-薄膜觸媒反應器
(δ=315μm),Ptube=4.3bar,CH3OH……….……...…….….173
圖7-69	質傳係數(Sh)之比較-薄膜觸媒反應器
(δ=315μm),Ptube=4.3bar,H2O……….……...……...…….174
圖7-70	質傳係數(Sh)之比較-薄膜觸媒反應器
(δ=315μm),Ptube=4.3bar,CO……………….……...…….175
圖7-71	質傳係數(Sh)之比較-薄膜觸媒反應器
(δ=315μm),Ptube=4.3bar,H2………….……...……..……176
圖7-72	質傳係數(Sh)之比較-薄膜觸媒反應器
(δ=315μm),Ptube=4.3bar,CO2……….……...………..…..177


表目錄
表3-1	甲醇合成系統反應速率常數之參數……………..……...8
表3-2	甲醇合成系統吸附係數之參數值………………..……...	8
表3-3	     Nafion膜之滲透係數－CH3OH, H2O………………….	9
表3-4	     Nafion膜之滲透係數－H2, CO2…..................................10
表5-1	管壁之邊界層設定參數………………………………....23
表5-2	觸媒反應器之低鬆弛因子設定……………...…………34
表5-3      觸媒薄膜反應器之低鬆弛因子設定……………………35
表6-1      個案彙整表………………………………………………37
表6-2      基本個案於管側之初始條件(模擬位置Z=0.5m)……....40
表6-3      基本個案於殼側之初始條件(模擬位置Z=0.5m)……....40
表6-4      CH3OH質傳量 (kg/s) (自觸媒顆粒至管中流體為正值)……43
表6-5      H2O質傳量 (kg/s) (自觸媒顆粒至管中流體為正值)…..44
表6-6      CO質傳量 (kg/s) (自觸媒顆粒至管中流體為正值)…...45
表6-7      H2質傳量 (kg/s) (自觸媒顆粒至管中流體為正值)…….46
表6-8      CO2質傳量 (kg/s) (自觸媒顆粒至管中流體為正值)…..47
表6-9      有效因子(R-1)………………………………………...….49
表6-10     有效因子(R-2)……………………………………………49
表6-11     有效因子(R-3)………………………………………...…49
表6-12     反應程度－甲醇生成量(kmole/s kgcat)……….………...50
表6-13     改變顆粒粒徑對反應程度-甲醇生成量之影響………..72
表6-14     改變進料流量對反應程度－甲醇生成量之影響…..…..79
表6-15     改變系統操作壓力對薄膜通量之影響……………...….83
表6-16     改變操作壓力對反應程度－甲醇生成量之影響……....83
表6-17     改變薄膜厚度對薄膜通量之影響…………………....…93
表6-18     改變薄膜厚度對反應程度－甲醇生成量之影響……....93

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