臺灣博碩士論文加值系統

本論文針對玉米澱粉與羥丙基甲基纖維素水溶液於1公升造粒機中，以三葉刀片進行濕式造粒形成二次顆粒以改善其流動性之研究；探討造粒時間(T)、液固比(L/S)與三葉片主刀轉速(S)、角度(θ)，對於所造粒生成二次粒徑分佈、顆粒流動性以及壓錠性質的影響。
結果顯示，隨著L/S上升，顆粒成長速率上升。L/S=0.4-0.5介於臨界飽和點和孔隙過飽和點間，可觀察到明顯顆粒增長。T=1 min, 3 min，隨著主刀轉速增加，顆粒間碰撞力增加，顆粒粒徑下降且粒徑分佈較窄。當100 rpm及300 rpm，過低的顆粒變形量無法使顆粒增長，在S=500 rpm，才可觀察到顆粒增長。在某些操作條件下(S=500 rpm, L/S=0.4, 0.5)可完整觀察到顆粒增長為成核→壓實→增長→破裂→增長的完整機制。以上階段發生速率，受到液固比的影響甚劇。使用ANOVA分析，液固比和轉速對於二次顆粒粒徑重量平均徑有顯著影響，且隨液固比、主刀轉速增加，二次顆粒球形度上升(不包含過飽和階段)以及流動性上升。在本系統中，改變主刀角度不改變顆粒與機械力碰撞的型態，故ANOVA分析顯示主刀角度對二次顆粒累積重量粒徑沒有顯著性。
使用0.5 mm-0.71 mm, 0.71 mm-1.00 mm二次顆粒壓錠，藥錠破裂力隨造粒階段的液固比變化無明顯差異。以S=500 rpm造粒之二次顆粒，壓錠所需力較S=100 rpm, S=300 rpm造粒之二次顆粒壓錠所需力低，但形成藥錠之破裂力卻較高，應與二次顆粒外型有關。雖然顆粒尺寸為0.71 mm-1.00 mm之二次顆粒所壓之藥錠藥錠硬度良好，但表面形態斑駁。當L/S=0.4-0.5, S=500 rpm造粒，使用介於0.5 mm-0.71 mm二次顆粒壓錠，此條件下形成的藥錠外表光滑，藥錠硬度佳，為本實驗中最適合壓錠顆粒操作條件。

Corn starch powders are granulated in a lab-scale high shear granulator using aqueous hydroxypropyl methylcellulose solution as the binder solution. The effects of the liquid-to-solid mass ratio (L/S), impeller speed (S), granulation time (T) and impeller inclined angle (θ) on the granule flowability, size and size distribution are investigated.
While L/S ratio increases, the granulation rate increases. The granule sphericity and flowability increases with the increasing of L/S and S. When L/S value is 0.3, granulation progress slowly and the granules are with wide distribution. When L/S is greater than 0.4, the granules show good flowability. When L/S is 0.4 and 0.5, the liquid binder is around the critical pore saturation and granule growth can be observed. When L/S is 0.6, some extra large granules (say > 4 mm) are found. When T = 1 min or 3 min, the collisional force between granules increases with the increasing of the impeller rotational speed. High collisional force at 500 rpm causes a smaller granule size and a narrower granule size distribution. A low impeller rotational speed of 100 rpm or 300 rpm causes little deformation during collision and thus granulation progresses slowly. When S = 500 rpm, L/S = 0.4 or 0.5, the three steps in granulation: wetting-nucleation, consolidation-coalescence, and attrition-breakage can be observed. By ANOVA analysis, L/S and S show significance on the granule mass mean diameter.
The as-prepared granules are then tabletted. The tablet breakage loading is independent of the L/S value during granulation process. Using granules with the size range between 0.71 mm and 1.00 mm for tabletting, the corresponding tablets are relative strong but the surface is bumpy. breakout force is well, but mottled surface morphology. Using granules (L/S=0.4-0.5, S=500 rpm) with the size range between 0.5 mm and 0.71 mm for tabletting, the corresponding tablets show smooth surface and high breakage loading.

指導教授推薦書 i
口試委員會審定書 ii
國家圖書館博碩士論文電子檔案上網授權書 iii
長庚大學博碩士論文著作授權書 iv
致謝 v
摘要 vi
目錄 x
圖目錄 xii
表目錄 xx
第一章 緒論 1
第二章 文獻回顧 2
2.1高剪切濕式造粒機造粒程序 2
2.1.1顆粒成長機制 2
2.1.2操作參數 10
2.2固液分佈與相互作用力 17
2.3粉體流動性評估 20
第三章 實驗方法與分析 25
3.1材料與設備 25
3.2實驗步驟 33
第四章 結果與討論 37
4.1造粒時間對二次顆粒形成的影響 39
4.2液固比對二次顆粒形成的影響 53
4.3主刀轉速與主刀角度對二次顆粒形成的影響 63
4.4 統計分析 81
4.5 二次顆粒壓錠性質分析性 84
第五章 結論 92
第六章 參考文獻 94
附錄A “The effect of fill level on the granule size distribution a high shear granlator” (5th Asian Particle Technology Symposium, Singapore, July 2012)…………………….………….....……98
附錄B “ The Effect of Liquid-to-Solid Ratio on the Flowability and Size Distribution of the Granules Prepared from a High Shear Granulator” (Proceedings of the 3rd Asian Conference on Innovative Energy and Environmental Chemical Engineering, Hualien, November 2012)……………………….…….……..100
附錄C “The Effect of Liquid-to-Solid Ratio in the Granulation Process on the Characteristics of the Corresponding Tablets” (台灣化學工程學會59週年年會暨國科會化學工程學門成果發表會，台中，November 2012)…………………………………………106
附錄D “造粒時間及主刀轉速對玉米澱粉二次顆粒尺寸分佈和流動性的影響” (台塑關係企業應用技術研討會，桃園，June 2012)………………………………………………………….110
 
圖目錄
圖2. 1造粒過程示意圖(a) Sastry觀點(1977)；(b) Iveson觀點(2001) 2
圖2. 2成核五階段(Hapgood et al., 2003) 3
圖2. 3成核機制(a) Distribution mechanism; (b) Immersion mechanism (Mort, 2005) 5
圖2. 4壓縮、合併階段，顆粒間的碰撞情形(Mort , 2005) 7
圖2. 5 (a)碰撞應力；(b)剪切應力作用造成顆粒破裂和表面磨耗 7
圖2. 6顆粒成長階段圖(Iveson et al.,1998; Lister et al., 2001) 9
圖2. 7濕式造粒顆粒成長過程示意圖(Dries, 2004) 11
圖2. 8 MCC粉末和3wt％HPMC水溶液於不同液固比條件下造粒之最終顆粒 (Chitu et al., 2011) 12
圖2. 9平均顆粒尺寸隨液固比、造粒時間的變化圖(Hoornaert et al., 1998) 12
圖2. 10絹雲母二次顆粒粒徑分佈受液固比影響的說明圖(Oulahna et al.,2003) 13
圖2. 11 絹雲母顆粒造粒過程中，主刀轉動力矩隨液固比的變化圖(Oulahna et al.,2003) 14
圖2. 12不同主刀轉速下，二次顆粒平均尺寸之比較(Kristensen et al., 1985) 15
圖2. 13 不同主刀轉速對二次顆粒粒徑分佈影響(Oulahna et al., 2003) 16
圖2. 14一次顆粒間鐘擺狀之靜態液橋力作用(Iveson et al., 2001) 19
圖2. 15細川粉末測試儀(powder test)測量(a)蓬鬆密度；(b)壓實密度(Abdullah et al., 1999) 24
圖2. 16安息角測試方法(三輪茂雄/日高重助, 1984) 24
圖3. 1 玉米澱粉體積粒徑分佈 25
圖3. 2 Hydroxypropyl methylcellulose 結構 26
圖3. 3濕式混合造粒機外觀 26
圖3. 4 混合槽規格與槽體內部主刀與切刀配置圖 27
圖3. 5 三葉主刀片規格圖(a)20°主刀，(b)45°主刀，(c)60°主刀 28
圖3. 6 切刀示意圖 29
圖3. 7 Powder tester (粉體特性總合測定裝置) 30
圖3. 8 (a)壓錠機外觀；(b)壓錠模具結構圖 31
圖3. 9 多功能萬能材料試驗機 32
圖3. 10 實驗流程圖 34
圖3. 11打錠槽示意圖(Kendal et al., 2007) 35
圖3. 12 (a)顆粒特性負載本曲線和(b)顆粒破碎SEM圖 (Chitu et al., 2011 ) 36
圖4. 1玉米澱粉顆粒(a)未造粒, (b)造粒3 min, (c)8 min的外觀 (θ=45°, L/S=0.5) 41
圖4. 2 不同造粒時間下的二次顆粒粒徑分佈圖(L/S=0.3, θ=45°, S=500 rpm) 42
圖4. 3不同造粒時間下的二次顆粒粒徑分佈圖(L/S=0.4, θ=45°, S=500 rpm) 43
圖4. 4不同造粒時間下的二次顆粒粒徑分佈圖(L/S=0.5, θ=45°, S=500 rpm) 44
圖4. 5不同造粒時間下的二次顆粒粒徑分佈圖(L/S=0.6, θ=45°, S=500 rpm) 45
圖4. 6不同液固比下，二次顆粒重量平均粒徑隨造粒時間的變化圖(θ=45°, S=500 rpm) 46
圖4.7玉米澱粉附著於造粒槽內的情況 (L/S=0.5, S=500 rpm, T=13 min) 46
圖4. 8不同液固比下，二次顆粒Hausner ratio隨造粒時間的變化圖(θ=45°, S=500 rpm) 47
圖4. 9不同造粒時間的二次顆粒粒徑分佈圖(L/S=0.5, θ=45°, S=100 rpm) 49
圖4. 10不同造粒時間的二次顆粒粒徑分佈圖(L/S=0.5, θ=45°, S=300 rpm) 50
圖4. 11不同造粒時間的二次顆粒粒徑分佈圖(L/S=0.5, θ=45°, S=500 rpm) 51
圖4. 12 不同主刀轉速下，二次顆粒重量平均粒徑隨造粒時間的變化圖(L/S=0.5, θ=45°) 52
圖4. 13不同主刀轉速下，二次顆粒流動性隨造粒時間的變化圖(θ=45°, L/S=0.5) 52
圖4. 14不同液固比的二次顆粒累積重量粒徑分佈圖(θ=45°, S=100 rpm, T=1 min) 54
圖4. 15不同液固比的二次顆粒累積重量粒徑分佈圖(θ=45°, S=100 rpm, T=3 min) 54
圖4. 16不同液固比的二次顆粒累積重量粒徑分佈圖(θ=45°, S=300 rpm, T=1 min) 55
圖4. 17不同液固比的二次顆粒累積重量粒徑分佈圖(θ=45°, S=300 rpm, T=3 min) 55
圖4. 18不同液固比的二次顆粒累積重量粒徑分佈圖(θ=45°, S=500 rpm, T=1 min) 56
圖4. 19不同液固比的二次顆粒累積重量粒徑分佈圖(θ=45°, S=500 rpm, T=3 min) 56
圖4. 20玉米澱粉二次顆粒隨液固比增加的外觀變化(a) L/S=0.3, (b) L/S=0.4, (c)L/S=0.5, (d)L/S=0.6 (θ=45°, S=100 rpm, T=3 min) 58
圖4. 21不同液固比、主刀轉速下造粒形成的二次顆粒表面形狀，顆粒顯微鏡圖(θ=45°, T=3 min) 59
圖4. 22 不同液固比造粒下的二次顆粒Hausner ratio 與安息角的比較圖(θ=45°, S=100 rpm, T=1 min) 60
圖4. 23不同液固比造粒下的二次顆粒Hausner ratio 與安息角的比較圖(θ=45°, S=100 rpm, T=3 min) 60
圖4. 24不同液固比造粒下的二次顆粒Hausner ratio 與安息角的比較圖(θ=45°, S=300 rpm, T=1 min) 61
圖4. 25不同液固比造粒下的二次顆粒Hausner ratio 與安息角的比較圖(θ=45°, S=300 rpm, T=3 min) 61
圖4. 26不同液固比造粒下的二次顆粒Hausner ratio 與安息角的比較圖(θ=45°, S=500 rpm, T=1 min) 62
圖4. 27不同液固比造粒下的二次顆粒Hausner ratio 與安息角的比較圖(θ=45°, S=500 rpm, T=3 min) 62
圖4. 28不同品種玉米澱粉糊化分析(A) African Tall, (B) Ageti, (C) Early Composite, (D) Girja, (E) Navjot, (F) Parbhat, (G) Partap, (H) Pb Sathi, (I) Vijay. (kawaljit et al., 2007) 63
圖4. 29 不同主刀轉速的二次顆粒累積粒徑分佈圖(L/S=0.3，θ=45°，T=1 min) 66
圖4. 30不同主刀轉速的二次顆粒累積粒徑分佈圖(L/S=0.3，θ=45°，T=3 min) 66
圖4. 31不同主刀轉速的二次顆粒累積粒徑分佈圖(L/S=0.4，θ=45°，T=1 min) 67
圖4. 32不同主刀轉速的二次顆粒累積粒徑分佈圖(L/S=0.4，θ=45°，T=3 min) 67
圖4. 33不同主刀轉速的二次顆粒累積粒徑分佈圖(L/S=0.5，θ=45°，T=1 min) 68
圖4. 34不同主刀轉速的二次顆粒累積粒徑分佈圖(L/S=0.5，θ=45°，T=3 min) 68
圖4. 35不同主刀轉速的二次顆粒累積粒徑分佈圖(L/S=0.6，θ=45°，T=1 min) 69
圖4. 36不同主刀轉速的二次顆粒累積粒徑分佈圖(L/S=0.6，θ=45°，T=3 min) 69
圖4. 37玉米澱粉二次顆粒隨主刀轉速增加的外觀變化(a)S=100 rpm, (b)S=300 rpm, (c)S=500 rpm (L/S=0.5, θ=45°, T=3 min) 71
圖4. 38不同主刀轉速下，二次顆粒重量平均粒徑隨液固比的變化圖(θ=45°, T=1 min) 72
圖4. 39不同主刀轉速下，二次顆粒重量平均粒徑隨液固比的變化圖(θ=45°, T=3 min) 72
圖4. 40 過大二次顆粒的外觀 (a)S=100 rpm, (b)S=300 rpm, (c)S=500 rpm (L/S=0.6, θ=45°, T=3 min) 74
圖4. 41 不同主刀轉速造粒下的二次顆粒Hausner ratio與安息角的比較圖(L/S=0.3, θ=45°, T=1 min) 75
圖4. 42不同主刀轉速造粒下的二次顆粒Hausner ratio與安息角的比較圖 (L/S=0.3, θ=45°, T=3 min) 75
圖4. 43不同主刀轉速造粒下的二次顆粒Hausner ratio與安息角的比較圖 (L/S=0.4, θ=45°, T=1 min) 76
圖4. 44不同主刀轉速造粒下的二次顆粒Hausner ratio與安息角的比較圖(L/S=0.4, θ=45°, T=3 min) 76
圖4. 45不同主刀轉速造粒下的二次顆粒Hausner ratio與安息角的比較圖 (L/S=0.5, θ=45°, T=1 min) 77
圖4. 46不同主刀轉速造粒下的二次顆粒Hausner ratio與安息角的比較圖 (L/S=0.5, θ=45°, T=3 min) 77
圖4. 47不同主刀轉速造粒下的二次顆粒Hausner ratio與安息角的比較圖(L/S=0.6, θ=45°, T=1 min) 78
圖4. 48不同主刀轉速造粒下的二次顆粒Hausner ratio與安息角的比較圖(L/S=0.6, θ=45°, T=3min) 78
圖4. 49 不同主刀角度的二次顆粒累積重量粒徑分佈圖(L/S=0.5, S=100 rpm, T=3 min) 79
圖4. 50不同主刀角度的二次顆粒累積重量粒徑分佈圖(L/S=0.5, S=300 rpm, T=3 min) 80
圖4. 51不同主刀角度的二次顆粒累積重量粒徑分佈圖(L/S=0.5, S=500 rpm, T=3 min) 80
圖4. 52 細小粉末於壓錠機中壓錠時的粉末飛散狀態(granule size < 0.25 mm) 85
圖4. 53 藥錠外觀 (Granule size < 0.25mm, θ=45°, S=500 rpm, L/S=0.3, T=3 min) 86
圖4. 54 藥錠外觀 (Granule size = 0.25-0.5 mm, θ=45°, S=500 rpm, L/S=0.5, T=3 min) 86
圖4. 55 藥錠外觀 (Granule size = 0.5-0.71 mm, θ=45°, S=500 rpm, L/S=0.5, T=3 min) 87
圖4. 56 藥錠外觀 (Granule size = 0.71-1.00mm, θ=45°, S=500 rpm, L/S=0.5, T=3 min) 87
圖4. 57藥錠外觀 (Granule size < 1.68mm, θ=45°, S=500 rpm, L/S=0.5, T=3 min) 88
圖4. 58不同造粒條件之二次顆粒壓錠所需最大力(左側長條)；藥錠破裂力(右側長條)比較圖(granule size=0.25 mm-0.5 mm, θ=45°, T=1 min) 89
圖4. 59不同造粒條件之二次顆粒壓錠所需最大力(左側長條)；藥錠破裂力(右側長條)比較圖(granule size=0.25 mm-0.5 mm, θ=45°, T=3 min) 89
圖4. 60不同造粒條件之二次顆粒壓錠所需最大力(左側長條)；藥錠破裂力(右側長條)比較圖(granule size=0.5 mm-0.71 mm, θ=45°, T=1 min) 90
圖4. 61不同造粒條件之二次顆粒壓錠所需最大力(左側長條)；藥錠破裂力(右側長條)比較圖(granule size=0.5 mm-0.71 mm, θ=45°, T=3 min) 90
圖4. 62不同造粒條件之二次顆粒壓錠所需最大力(左側長條)；藥錠破裂力(右側長條)比較圖(granule size=0.71 mm-1.00 mm, θ=45°, T=1 min) 91
圖4. 63不同造粒條件之二次顆粒壓錠所需最大力(左側長條)；藥錠破裂力(右側長條)比較圖(granule size=0.71 mm-1.00 mm, θ=45°, T=3 min) 91
 
表目錄
表2-1粉末間隙液體飽和度及相應液橋形態 (孫其誠/王光謙, 2009) 18
表2-2流動性指數評分表 (Carr, 1965) 21
表2-3以Hausner Ratio評估粉體的流體化特性 23
表4-1二次顆粒形成影響的實驗參數 38
表4-2液固比和主刀轉速條件下造粒時間對顆粒重量平均粒徑的顯著性質分析(θ=45°、T=1-15 min) 82
表4-3液固比、主刀轉速和角度對顆粒重量平均粒徑影響ANOVA統計分析 83

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