臺灣博碩士論文加值系統

摘要
具有高活性及高熱穩定性之非晶相Ni-Co-W-B/g-Al2O3觸媒以化學還原-含浸法製得，其中鈷和鎢為添加劑。觸媒的製備是以醋酸鎳及硝酸鈷水溶液含浸在g-Al2O3 擔體上，再逐滴加入不同莫耳比例的鎢酸鈉混合硼氫化鉀水溶液還原而得。觸媒的物性及化性是以ICP-AES、DSC、BET、TPR、SEM、TEM、EDS及XRD等儀器分析。觸媒活性分別以常壓下苯及正己烯的氣相氫化反應來測定，產物的定量定性分析是以氣相層析儀來測定。
由XRD、DSC及BET結果，可以發現Ni-Co-W-B觸媒確實以非晶相存在，且鎢促進劑提高了Ni-Co-B的結晶溫度及觸媒的BET表面積。從SEM及TEM圖中可以發現Ni-Co-W-B觸媒均勻分佈於g-Al2O3擔體上，Ni-Co-W-B粉末相當細微且有部分聚集的現象。在觸媒活性配合H2-TPR及BET表面積，添加鎢促進劑的Ni-Co-B觸媒其氫化活性大小排序，與其BET表面積大小排序相符，並與其H2-TPR還原波峰面積大小排序相反，也就是說，觸媒表面積愈大觸媒活性愈高，而H2-TPR還原波峰面積愈小，觸媒活性愈高，其可能原因是表面積大促進觸媒氫化活性，而H2-TPR還原面積小也就是觸媒被氧化量小，即觸媒本身屬於還原態較多，還原態使得觸媒中Ni原子周圍電子密度高，致使氫化活性較高。

ABSTRACT
The high performance amorphous Ni-Co-W-B/g-Al2O3 catalysts in which cobalt and tungsten were introduced as additives with high activity and thermal stability were synthesized by a chemical reduction-impregnation method. The samples were prepared by g-Al2O3 supported in various molar ratios of sodium tungsten to potassium borohydride solution which were added dropwise into an aqueous mixed solution of nickel acetate and cobalt nitrate with gentle stirring in an ice-water bath. The physical and chemical properties of catalysts were analyzed by using ICP-AES, AAS, DSC, BET, TPR SEM, TEM, EDS, and XRD. The catalytic activities of the prepared catalysts were measured through the hydrogenation of benzene under atmospheric pressure in vapor phase. Quantitative and qualitative analyses of the composites were monitored by gas chromatography.
XRD analyses proved the existence of amorphous Ni-Co-W-B catalysts. BET results showed that both tungsten promoter and γ-Al2O3 support increased the surface area of catalysts. SEM pictures showed the Ni-Co-W-B catalysts of homogeneous distribution on γ-Al2O3 carriers. In addition, TEM analyses explored that Ni-Co-W-B catalysts were fine powders. Ni-Co-W-B catalysts had higher catalytic activity for the hydrogenation of benzene than Ni-Co-B catalysts. The activities of catalysts were proportional to the surface area of catalysts, and disproportional to the H2-TPR reductive area. It is that the reactive state make high density of electron surround with nickel atoms. The state let catalysts have high hydrogenation activities.

TABLE OF CONTENTS
ACKNOWLEDGEMENTSⅢ
ABSTRACT (English)Ⅳ
ABSTRACT (Chinese)Ⅵ
TABLE OF CONTENTSⅦ
LIST OF TABLESⅩ
LIST OF FIGURESXI
CHAPTER 1. INTRDUCTION…………………………………… 1
CHAPTER 2. LITERATURE………………………………………6
2.1 Ultra fine metal boride catalyst…………………..6
2.1.1 Physical properties of metal boride catalyst6
2.1.2 Chemical adsorption properties…………………...7
2.1.3 Catalytic properties………………………………….8
2.1.4 Mechanism of alkene hydrogenation………………..8
2.2 Amorphous Ni-Co-B catalyst………………………….13
2.3 The composition of catalyst…………………………13
2.4 X-ray Diffraction Crystallospectray………………13
2.5 Differential Scanning Calorimetry (DSC)…………..14
2.6 Brunauer-Emmett-Teller (BET) Surface Measurement… 14
2.7 Temperature-programmed System………………………….16
2.8 Electronic Microscopy……………………………………17
CHAPTER 3. EXPERIMENTAL………………………………….18
3.1 Materials and gas………………………………………18
3.1.1 Materials………………………………………………..18
3.1.2 Gas………………………………………………………...18
3.2 Catalysts preparation…………………………………..18
3.2.1 Ni-Co-W-B catalysts preparation…………………18
3.2.2 Ni-Co-W-B/γ-Al2O3 catalyst preparation………..19
3.3 Catalysts properties characterized……………………21
3.3.1 Inductively Coupled Plasma (ICP-AES)…………….21
3.3.2 X-ray Diffraction (XRD) Analysis……………………21
3.3.3 Differential Scanning Calorimeter (DSC)………..21
3.3.4 Surface Area Measurement (BET)……………………..21
3.3.5 Temperature-Programmed Reduction (TPR)………..21
3.3.6 Scanning Electron Microscopy (SEM)…………………22
3.3.7 Transmission Electron Microscopy (TEM) Analysis22
3.4 Apparatus and procedure…………………………………22
3.4.1 Hydrogenation of n-hexene…………………………….22
3.4.2 Hydrogenation of benzene……………………………..23
CHAPTER 4. RESULT AND DISCUSSION…………………..25
4.1 Inductively Coupled Plasma-Atomic Emission Spectrometer(ICP-AES)……………………………………… ……...25
4.2 X-ray Diffraction (XRD) Analysis………………….28
4.3 Differential Scanning Calorimetry (DSC)…………..35
4.4 The BET Surface Area…………………………………...37
4.5 Temperature-Programed Reduction (TPR)…………….42
4.6 Scanning Electron Microscopy (SEM)……………..48
4.7 Transmission Electron Microscopy (TEM)………………56
4.8 EDS photoscopy……………………………………….…61
4.9 The hydrogenation of benzene…………………………..64
4.10 The hydrogenation of n-hexene………………………73
CHAPTER 5. CONCLUSIONS…………………………………..75
REFERENCE……………………………………………………...77
LIST OF TABLE
Table 2.1The composition and surface area of metal borides………...9
Table 4.1The composition of Ni-Co-W-B/γ-Al2O3 catalysts by use of ICP-AES………………………………………………….27
Table 4.2The composition of Ni-Co-W-B catalysts by use of ICP-AES………………………………………………………….27
Table 4.3The surface area of Ni-Co-W-B catalysts…………………..39
Table 4.4The surface area ofγ-Al2O3 and Ni-Co-W-B/γ-Al2O3 catalysts……………………………………………………..40
Table 4.5The surface area ofγ-Al2O3 and Ni-Co-W-B/γ-Al2O3 catalysts calcined at 573K for 3 hours………………………41
Table 4.6H2-TPR reductive area of Ni-Co-W-B catalyst……………..47
LIST OF FIGURE
Fig. 2.1A mechanism of heterogeneous catalysts in the hydrogenation of alkenes………………………………………………………11
Fig. 2.2A mechanism of heterogeneous catalysts in the hydrogenation of 1-hexene…………………………………………………….12
Fig. 3.1The preparation of Ni-Co-W-B catalysts………………………20
Fig. 3.2Schematic diagram of experimental setup……………………...24
Fig. 4.1XRD profiles of γ-Al2O3、Ni-Co-W-B and Ni-Co-W-B/γ-Al2O3 catalysts…….………………………………………….30
Fig. 4.2XRD profiles of Ni-Co-W-B、Ni-Co-B and Ni-W-B catalysts..31
Fig. 4.3XRD profiles of Ni-Co-W-B/γ-Al2O3、Ni-Co-B/γ-Al2O3 and Ni-W-B/γ-Al2O3 catalysts…………………………………….32
Fig. 4.4XRD profiles of γ-Al2O3 and Ni-Co-W(wt%)-B/γ-Al2O3 catalysts…………………………………………………………33
Fig. 4.5XRD profiles of γ-Al2O3 and Ni-Co-W(wt%)-B/γ-Al2O3 catalysts…………………………………………………………34
Fig. 4.6DSC profiles of Ni-Co-B and Ni-Co-W(0.49wt%)-B catalysts...36
Fig. 4.7TPR profiles of Ni-Co-W-B、Ni-Co-B and Ni-W-B catalysts…44
Fig. 4.8TPR profiles of Ni-Co-W（wt%）-B catalysts ………………..45
Fig. 4.9TPR profiles of Ni-Co-W（wt%）-B catalysts ……………….46
Fig. 4.10SEM photograph of A12 : Ni-Co-W(0.77wt%)-B/γ-Al2O3 catalyst………………………………………………………….51
Fig. 4.11SEM photograph of A11 : Ni-Co-W-B/γ-Al2O3 catalyst……..51
Fig. 4.12SEM photograph of A12 : Ni-Co-W(0.77wt%)-B/γ-Al2O3 catalyst………………………………………………………….52
Fig. 4.13SEM photograph of A13 : Ni-Co-W(0.88wt%)-B/γ-Al2O3 catalyst………………………………………………………….52
Fig. 4.14SEM photograph of A14 : Ni-Co-W(0.94wt%)-B/γ-Al2O3 catalyst………………………………………………………….53
Fig. 4.15SEM photograph of A15 : Ni-Co-W(2.15wt%)-B/γ-Al2O3 catalyst………………………………………………………….53
Fig. 4.16SEM photograph of A16 : Ni-Co-W(4.34wt%)-B/γ-Al2O3 catalyst………………………………………………………….54
Fig. 4.17SEM photograph of A17 : Ni-Co-W(4.96wt%)-B/γ-Al2O3 catalyst………………………………………………………….54
Fig. 4.18SEM photograph of A18 : Ni-Co-B/γ-Al2O3 catalyst…………55
Fig. 4.19SEM photograph of A19 : Ni-W-B/γ-Al2O3 catalyst………….55
Fig. 4.20TEM photograph in 120K times of A2 : Ni-Co-W(0.49wt%)-B catalysts…………………………………………………………57
Fig. 4.21TEM photograph in 120K times of A12: Ni-Co-W(0.77wt%)-B/γ-Al2O3 catalysts……………….…..…58
Fig. 4.22TEM photograph in 100K times of A18 : Ni-Co-B/γ-Al2O3 catalysts…………………………………………………………59
Fig. 4.23TEM photograph in 100K times of A19 : Ni-W-B/γ-Al2O3 catalysts…………………………………………………………60
Fig. 4.24EDS profile of A2: Ni-Co-W(0.49wt%)-B catalyst…………….62
Fig. 4.25EDS profile of A12: Ni-Co-W(0.77wt%)-B/g-Al2O3 catalyst….63
Fig. 4.26The conversion of benzene vs. running time over A2: Ni-Co-W(0.49wt%)-B catalysts over different temperatures..……….…………………………………………. 68
Fig. 4.27The conversion of benzene vs. running time over Ni-Co-W(wt%)-B catalysts at 373K……………………………69
Fig. 4.28The conversion of benzene vs. running time of Ni-Co-W(wt%)-B catalysts at 423K…………………………...70
Fig. 4.29Hydrogen uptake rate of benzene hydrogenation vs. running time over A2: Ni-Co-W(0.49wt%)-B and A12: Ni-Co-W(0.77wt%)-B/γ-Al2O3 catalysts at 373K……………71
Fig. 4.30The conversion of Benzene vs. running time over A2: Ni-Co-W(0.49wt%)-B, A8: Ni-Co-B and A12:Ni-Co-W(0.77wt%)-B/γ-Al2O3 catalysts at 373K……….72
Fig. 4.31Hydrogen uptake rate of n-hexene hydrogenation vs. running time of Ni-Co-W(wt%)-B、Ni-Co-B and Ni-W-B catalysts at 373K…………………………………………………………….74

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