奈米化非晶態NiB觸媒之製備與氫化反應研究

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江淑媜(Shu-jen Chiang) 查詢紙本館藏

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化學工程與材料工程學系

論文名稱

奈米化非晶態NiB觸媒之製備與氫化反應研究
(Preparation and hydrogenation of nano-amorphous NiB catalysts)

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摘要(中)

本研究利用三種硼氫化鈉化學還原法製備奈米均一化NiB觸媒，在傳統化學還原法製備過程中導入水溶性高分子PVP穩定劑製得PVP-NiB觸媒；以H2O/CTAB/n-hexanol逆微胞技術配合化學還原法製得ME-NiB觸媒；另以含浸法配合中溫煅燒將先驅鹽固著，再以化學還原法將NiB觸媒負載於SiO2擔體上製得NiB/SiO2觸媒。藉由丁醛液相氫化為模式反應，尋找三種奈米化NiB觸媒製備之最適條件，探討糠醛、巴豆醛及檸檬醛的選擇性氫化反應性質。
非負載式觸媒以醋酸鎳鹽為佳，負載式觸媒由於需經中溫煅燒固著，則以不易分解的氯化鎳鹽為佳。在添加硼氫化鈉的還原過程中，NiB與PVP-NiB觸媒都有一最適添加速率，可是ME-NiB與NiB/SiO2觸媒是以一次瞬間加入為佳。
PVP-NiB、ME-NiB及NiB/SiO2觸媒為非晶態結構，粒徑分布2~5 nm明顯小於NiB觸媒的7.7~40 nm。經奈米化之PVP-NiB、ME-NiB及NiB/SiO2觸媒於丁醛、巴豆醛、糠醛及檸檬醛等反應都有優越的催化活性，約為NiB觸媒的3~10倍，因此，可於較低的溫度下進行反應，其活性不但媲美貴金屬觸媒，亦可以得到較多主產物之產率。
奈米化PVP-NiB、ME-NiB與NiB/SiO2觸媒可有效應用於檸檬醛選擇性氫化反應，檸檬醛(citral)為具有一共軛C=C/C=O鍵及孤立C=C鍵之多官能基不飽和醛，可經由選擇氫化成不同的產物，奈米化NiB觸媒於檸檬醛氫化反應中，主產物是先氫化共軛C=C鍵得到香茅醛，爾後繼續氫化C=O鍵得到香茅醇，香茅醛與香茅醇都是具經濟價值的香料產物。若以環己烷為反應溶劑、80°C下，PVP-NiB觸媒活性為NiB觸媒的4.9倍，ME-NiB觸媒為9.8倍，NiB/SiO2觸媒更高達10倍以上，遠優於商用Raney Ni 觸媒。
NiB與PVP-NiB觸媒中添加鉻、釷、鉬及鎢均能促進反應活性，其中又以鉻的促進效果最佳，這些促進劑反不利ME-NiB與NiB/SiO2觸媒。反應溶劑明顯影響觸媒活性，且因觸媒而不同，NiB與PVP-NiB觸媒以極性溶劑為佳，活性大小影響依序為甲醇>乙醇>環己烷>正己烷，ME-NiB與NiB/SiO2觸媒以非極性溶劑為佳，溶劑效應則相反。若香茅醛與香茅醇同為主產物，選擇高活性觸媒與溶劑，可得98%以上的高產率。若以香茅醛為單一主產物，以PVP-NiB為觸媒，50°C下可得最大產率為92%；以ME-NiB與NiB/SiO2為觸媒，30°C下可得最大產率分別為88%與90%。
動力學探討中發現，NiB系列觸媒於檸檬醛選擇氫化成香茅醛初活性隨H2壓力上升而上升，表觀反應級數分別為0.53 (NiB)、0.2 (PVP-NiB)、0.36 (ME-NiB) 與0.41 (NiB/SiO2)。初活性亦隨檸檬醛濃度上升而上升，表觀反應級數分別為0.45 (NiB)、0.2 (ME-NiB)與0.23 (NiB/SiO2)；PVP-NiB觸媒例外，初活性幾乎不受濃度影響。檸檬醛選擇氫化成香茅醛表觀活化能，NiB觸媒(70~100°C)為9.7 kJ/mol，PVP-NiB觸媒(50~100°C)為3.2 kJ/mol，ME-NiB觸媒(30~60°C)為3.1 kJ/mol，NiB/SiO2觸媒(30~50°C)為2.4 kJ/mol。

摘要(英)

The PVP-stabilized NiB catalysts were prepared using the chemical reduction method with NaBH4, dissolving the water-soluble polymer of polyvinylpyrrolidone (PVP) in the precursor salt solution as a protective reagent. The PVP-NiB catalysts were characterized and examined for their catalysis on the hydrogenation of furfural, crotonaldehyde and citral. PVP polymer could adsorb on the nano-particles of NiB via a weak coordination bonding and stabilize it; the molecular weight of PVP about 10,000 was suitable, and the optimal quantity of PVP (PVP/Ni) in the salt solution for preparing catalysts was around 20. The PVP-NiB samples were characterized by XRD as an amorphous structure and by TEM with a particle size distribution in the range of 2.5–7.7 nm. On catalysis, the PVP-NiB catalyst was significantly more active and slightly more selective than NiB for hydrogenating furfural to furfuryl alcohol and crotonaldehyde to butyraldehyde. A good yield of citronellal about 92% could be obtained by reducing citral in cyclohexane at a low reaction temperature of 50ºC over the PVP-NiB catalyst.
Surfactant-stabilized NiB catalysts (ME-NiB) were prepared using the chemical reduction method in the ternary microemulsion system of water/CTAB/n-hexanol. The surfactant molecules could adsorb on the surface of the formed particles; they act as a protective agent and restrict the growth of nano-particles. The size of nano-particles was not completely determined by the size of the microemulsion droplets, but also depended on the composition of the solution. Additionally, the concentration of nickel salt, the amount and speed of addition of NaBH4, and the temperature influenced the sizes of the particles and the reactivity of the ME-NiB nano-particles. The ME-NiB catalyst was characterized and examined for its catalysis on the hydrogenation of furfural, crotonaldehyde and citral. It was thus compared with the NiB and PVP polymer-stabilized NiB catalysts. The ME-NiB sample was characterized by XRD as an amorphous structure and by TEM with a particle size distribution in the range 1.2–5.0 nm. The ME-NiB catalyst was markedly more active and slightly more selective than NiB or PVP polymer-stabilized NiB in the hydrogenation of furfural to furfuryl alcohol and crotonaldehyde to butyraldehyde. A good yield of citronellal, around 88%, was obtained by reducing citral in cyclohexane at a room temperature of 30ºC over the ME-NiB catalyst.
A super-active supported nickel catalyst-NiB/SiO2 could be obtained with chemical reduction method for liquid-phase hydrogenation. The precursor salt of nickel was mounted on SiO2 by impregnating, drying and calcination at an appropriate temperature without being decomposed, and then reduced with aqueous NaBH4 solution. The influential factors for preparation NiB/SiO2 catalysts were examined by the hydrogenation of butyraldehyde. The NiB/SiO2 catalysts were characterized as an ultrafine and amorphous structure, which are much more active than NiB and Ni/SiO2 a conventional supported nickel catalyst reduced by H2. The optimal catalyst of 5%NiB/SiO2 was used for hydrogenating citral to citronellal and cironellol, which was about fourteen times as active as NiB, but less selective than it. Nevertheless, the reaction could be performed at room temperature to promote the selectivity. A good yield of citronellal/cironellol about 90% and a yield of citronellal about 81% over 5%NiB/SiO2 could be obtained at a low temperature of 30ºC.

關鍵字(中)

★ 氫化反應
★ 奈米顆粒
★ 非晶態
★ 鎳硼觸媒

關鍵字(英)

★ nanoparticle
★ hydrogenation
★ amorphous
★ NiB catalyst

論文目次

中文摘要 I
英文摘要 III
誌謝 V
目錄 VII
圖目錄 XII
表目錄 XVII
第一章緒論 1
第二章文獻回顧 3
2-1 奈米非晶態金屬-硼觸媒 3
2-1-1 非負載式NiB觸媒 3
2-1-1-A 物理性質 4
2-1-1-B 催化性質 11
2-1-2 負載式金屬-硼觸媒 14
2-1-2-A 物理性質 14
2-1-2-B 催化性質 16
2-2 金屬奈米微粒的製備技術 19
2-2-1 逆微胞技術製備金屬奈米微粒 19
Part A 19
A-1 微胞與微乳液的形成 19
A-1-1 界面活性劑的基本結構 20
A-1-2 微胞與逆微胞 22
A-1-3 微乳液 24
A-2 水/界面活性劑/油三成份系統之微胞形狀分子堆疊模型 27
A-3 油包水型微乳液(w/o)之動態行為 29
A-4 微乳液性質的主要影響因素 29
A-4-1 ωo值對微乳液性質之影響 29
A-4-2 溫度效應 31
A-4-3 水相鹽類效應 33
A-4-5 油相種類的影響 33
Part B 34
B-1 逆微胞系統於奈米粒子之製備 34
B-2 奈米粒子生成過程 35
B-3 製備粒徑之主要影響變因 38
B-3-1 ωo值(Nwater/Nsurfactant)對奈米粒子的影響 38
B-3-2 油相的影響 38
B-3-3 界面活性劑的影響 39
B-3-4 鹽類濃度的影響 40
B-3-5 還原劑濃度的影響 40
B-3-6 溫度的影響 40
2-2-2 PVP高分子穩定法製備金屬奈米微粒 42
Part A 製備奈米微粒粒徑之影響變因 42
A-1 還原劑種類 42
A-2 PVP/金屬之添加量 45
A-3 PVP分子量 46
Part B 金屬觸媒之催化應用 49
2-3 不飽和醛選擇性氫化反應 52
2-3-1 糠醛選擇性氫化反應 52
2-3-2 巴豆醛選擇性氫化反應 55
2-3-2-1 氫化C=O鍵主產物為巴豆醇 55
2-3-2-2 氫化C=C鍵主產物為丁醛 57
2-3-3 檸檬醛選擇性氫化反應 62
2-3-3-1 Ru金屬觸媒之先趨鹽類與反應溶劑的影響 63
2-3-3-2 Ru金屬顆粒大小的影響 64
2-3-3-3 Ru金屬觸媒之促進劑效應的影響 65
2-3-3-4 Ru金屬觸媒之擔體效應的影響 67
2-3-3-5 Ru以外其它金屬觸媒之檸檬醛氫化反應 68
2-3-3-6 檸檬醛氫化反應之動力研究 71
第三章實驗方法與設備 77
3-1 觸媒製備 77
3-1-1 非負載式NiB與PVP-NiB觸媒之製備 77
3-1-2 非負載式ME-NiB觸媒之製備 79
3-1-3 負載式NiB/SiO2觸媒之製備 79
3-1-4 負載式鎳觸媒(Ni/SiO2)之製備 81
3-1-5 倫尼鎳(Raney Ni)觸媒之製備 81
3-2 觸媒性質鑑定 81
3-2-1 鎳金屬表面積測量(H2 impulse adsorption) 81
3-2-2 元素組成分析(ICP) 84
3-2-3 X-射線繞射分析(XRD) 84
3-2-4 比表面積測定(BET) 85
3-2-5 示差掃瞄熱量測定(DSC) 86
3-2-6 熱重分析儀(TGA) 86
3-2-7 X-射線光電子光譜(XPS, ESCA) 86
3-2-8 電子顯微鏡(TEM, SEM) 87
3-2-9 反應活性測定 88
3-2-10 實驗藥品及氣體 91
第四章奈米化NiB系列觸媒之製備與鑑定 95
4-1 PVP-NiB觸媒製備與鑑定分析 95
4-1-1 PVP-NiB觸媒之製備 95
4-1-2 PVP-NiB觸媒之ICP整體組成分析 98
4-1-3 PVP-NiB觸媒之BET表面積分析 99
4-1-4 PVP-NiB觸媒之XRD粉末繞射分析 99
4-1-5 PVP-NiB觸媒之DSC熱穩定分析 102
4-1-6 PVP-NiB觸媒之TGA熱重分析 102
4-1-7 PVP-NiB觸媒之SEM掃描式電子顯微影像分析 105
4-1-8 PVP-NiB觸媒之TEM穿透式電子顯微影像分析 105
4-1-9 PVP-NiB觸媒之XPS表面組成分析 106
4-2 ME-NiB觸媒製備與鑑定分析 112
4-2-1 ME-NiB觸媒之製備 113
4-2-2 ME-NiB觸媒之ICP整體組成分析 116
4-2-3 ME-NiB觸媒之BET表面積分析 117
4-2-4 ME-NiB觸媒之XRD粉末繞射分析 117
4-2-5 ME-NiB觸媒之DSC熱穩定分析 120
4-2-6 ME-NiB觸媒之TGA熱重分析 121
4-2-7 ME-NiB觸媒之SEM掃描式電子顯微影像分析 121
4-2-8 ME-NiB觸媒之TEM穿透式電子顯微影像分析 121
4-2-9 ME-NiB觸媒之XPS表面組成分析 126
4-3 NiB/SiO2觸媒製備與鑑定分析 128
4-3-1 NiB/SiO2觸媒之製備 128
4-3-2 NiB/SiO2觸媒之ICP組成分析 130
4-3-3 NiB/SiO2觸媒之BET全表面積及孔徑量測 131
4-3-4 NiB/SiO2觸媒之鎳金屬表面積量測 132
4-3-5 NiB/SiO2觸媒之X-射線繞射分析 133
4-3-6 NiB/SiO2觸媒之DSC熱穩定性分析 133
4-3-7 NiB/SiO2觸媒之TGA熱重分析 136
4-3-8 NiB/SiO2觸媒之SEM掃描式電子顯微影像分析 136
4-3-9 NiB/SiO2觸媒之TEM顯微影像分析 136
4-3-10 NiB/SiO2觸媒之XPS表面組成分析 137
4-4 PVP-NiB、ME-NiB與NiB/SiO2觸媒之比較 142
第五章 NiB系列觸媒之催化性質的探討 150
5-1 丁醛氫化反應測試 150
5-2 糠醛氫化 151
5-3 巴豆醛氫化 157
5-4 檸檬醛氫化 161
第六章檸檬醛氫化反應之探討 169
6-1 溫度效應 169
6-2 溶劑的影響 176
6-3 添加促進劑的影響 188
6-4 NiB系列觸媒於檸檬醛氫化反應之動力探討 197
6-4-1 NiB觸媒添加inert SiO2探討 197
6-4-2 反應溫度影響 201
6-4-3 反應壓力影響 204
6-4-4 反應濃度影響 204
6-4-5 檸檬醛氫化成香茅醛的反應機制 209
第七章結論 210
第八章總結 213
參考文獻 214

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指導教授

陳吟足、廖炳傑
(Yin-zu Chen、Biing-jye Liaw)

審核日期

2008-7-16

推文