臺灣博碩士論文加值系統

本研究是以共沉澱法來製備CeO2/ZrO2觸媒，並探討Ce/Zr比例以及製備時的煅燒溫度對觸媒反應活性的效應。
所合成出來的觸媒以X-光繞射光譜(XRD)、氣體吸附儀(BET)、傅立葉轉換紅外線光譜(FTIR)、熱重分析儀(TGA)、熱差分析儀(DTA) 、氨氣程式升溫脫附(NH3-TPD)及X光光電子能譜儀(ESCA)來鑑定其特性。
觸媒的活性是在常壓下以一個流動式的微反應器量測，反應時觸媒使用量為0.2 g，進料為二異丙醚，並通以氬氣為平衡氣來維持總壓為1atm，氬氣與進料的莫耳比以1:1.2為主。反應後的產物以氣相層析儀分析，再由所得的數據計算二異丙醚的轉化率及異丙醇選擇率。
由實驗結果可知，在Ce/Zr莫耳比例為1:9、3:7及5:5的觸媒中，以1:9的活性最佳，在煅燒溫度為500℃及800℃的觸媒中，以 500℃者得到的轉化率較佳，但選擇率則較差。
以改變溫度、帶入水蒸氣及改變進料比來探討不同反應條件的效應，結果顯示反應溫度介於140℃至190℃時，較低溫的反應得到的轉化率較低，但選擇率則較高;反應中有帶入水蒸氣所得到的轉化率較未帶入者高，但選擇率卻較低;在總壓力不變的情形下將進料分壓降低，轉化率會下降，但選擇率會提高。
反應時觸媒皆有嚴重的失活現象，積碳是觸媒失活的重要原因之ㄧ，比較二種不同的煅燒溫度下製備的觸媒，煅燒800℃的觸媒較500℃者穩定。

In this study CeO2/ZrO2 catalysts were prepared by coprecipitation. The effects of Ce/Zr ratio and calcination temperature on catalyst activity were examined.
The prepared catalysts were characterized by the use of XRD, N2-adsorption (BET), FTIR, TGA/DTA, NH3-TPD and ESCA.
The activities of the catalysts were tested in a continuous flow micro reactor. The reaction was carried out at atmospheric pressure. The mass of the catalysts used in each reaction is fixed at 0.2 g. Diisopropyl ether (DIPE) is fed to the reactor accompanied by Ar as the balance gas. The Ar:DIPE mole ratio was fixed at 1:1.2 for each reaction. The product from the reactor were analyzed by a gas chromatograph and then using the data to calculated the conversion of DIPE and selectivity of isopropyl alcohol.
The results showed that among the catalysts with Ce/Zr mole ratio of 1:9, 3:7 and 5:5 the 1:9 catalyst exhibited the highest activity. Between the catalysts calcined at 500℃ and 800℃. The 500℃ one displayed a higher DIPE conversion but lower IPA selectivity.
The effects of reaction condition were investigated through the changes of reaction temperature, the introduction of water in the feed and the partial pressure of DIPE. For reaction between 140℃ and 190℃, low temperature resulted in low conversion and high selectivity.
Incorporating water steam in the feed could yield a higher DIPE conversion but a lower product selectivity. Under a constant total pressure, decreasing the partial pressure of the reactant would decrease the DIPE conversion but increase the product selectivity.
Severe deactivation of the catalysts was observed during the reaction. Carbon deposit was believed to be one of the causes for the deactivation. Comparing the catalyst calcined at 800 ℃ with that at 500 ℃, the former was more stable.

誌謝.....................................................Ⅰ
中文摘要.................................................Ⅱ
英文摘要.................................................IV
第一章 緒論.............................................1
第二章 文獻回顧.........................................2
2.1 異丙醇..............................................2
2.1.1 異丙醇的基本介紹及應用..........................2
2.1.2 異丙醇的合成方法................................3
2.2 二異丙醚............................................6
2.2.1 二異丙醚的基本介紹及應用........................6
2.2.2 二異丙醚製異丙醇................................6
2.3 觸媒介紹...........................................9
2.3.1 CeO2的介紹......................................9
2.3.2 ZrO2的介紹.....................................11
2.3.3 CeO2/ZrO2觸媒的介紹............................13
第三章 實驗方法與製備....................................14
3.1 實驗藥品與製備.....................................14
3.1.1 實驗藥品.......................................14

3.1.2 實驗氣體.......................................15
3.1.3 實驗器材.......................................16
3.2 觸媒製備...........................................17
3.2.1共沉澱法製備CeO2/ZrO2觸媒.......................17
3.3 二異丙醚分解製異丙醇反應...........................18
3.3.1 實驗裝置.......................................18
3.3.2 分析方法及儀器.................................20
3.4 觸媒鑑定...........................................22
3.4.1 X光繞射光譜(XRD)...............................22
3.4.2 表面積測定(BET)與氣體吸附測定..................24
3.4.3氨氣程式升溫脫附(NH3-TPD) ..................... 26
3.4.4熱重/熱示差分析儀(TGA/DTA) .....................29
3.4.5傅立葉轉換紅外線光譜（FTIR）分析................30
3.4.6 化學分析電子光譜（ESCA）......................32 第四章 結果與討論........................................35
4.1觸媒鑑定............................................36
4.1.1 X光繞射光譜(XRD)...............................36
4.1.2熱重/熱示差分析儀(TGA/DTA)......................38
4.1.3表面積、孔徑分佈及化學吸附測定儀(BET)...........40

4.1.4傅立葉轉換紅外線光譜(FTIR)..........................42
4.1.5氨氣程式升溫脫附(NH3-TPD).......................44
4.1.6 X光光電子能譜儀(ESCA) .........................45
4.2二異丙醚裂解製異丙醇的氣相反應......................50
4.2.1煅燒條件及Ce/Zr比例效應.........................50
4.2.2觸媒的穩定性....................................53
4.2.3水蒸氣對轉化率及選擇率的影響....................54
4.2.4二異丙醚分壓對轉化率及選擇率的影響..............54
第五章 結論..............................................59第六章 參考文獻..........................................61










圖目錄
圖3.3-1 反應裝置圖.......................................19
圖3.3-2二異丙醚裂解製異丙醇反應出料之FID氣相層析圖......21
圖3.3-3二異丙醚裂解製異丙醇反應出料之TCD氣相層析圖......21
圖3.4-1晶體的X光繞射圖..................................23
圖3.4-2 表面積與孔徑測量(Autosorb-1) ....................25
圖3.4-3 程式升溫脫附裝置(TPD) ...........................27
圖3.4-4 TPD-NH3實驗程式升溫圖............................27
圖3.4-6. FTIR光譜儀......................................31
圖3.4-7 ESCA之光電子.....................................33
圖4.1-1 CeO2/ZrO2 XRD繞射圖...............................37
圖4.1-2未煅燒前觸媒TGA圖................................39
圖4.1-3未煅燒前觸媒DTA圖................................39
圖4.1-4 Pyridine吸附型態.................................42
圖4.1-5 CeO2/ZrO2吸附Pyridine後的FTIR吸收圖譜............43
圖4.1-6 CeO2/ZrO2之FTIR吸收圖譜..........................43
圖4.1-7 CeO2/ZrO2觸媒的TPD-NH3脫附圖.....................44
圖4.1-8 Ce/Zr-500-10 ESCA粗勘圖..........................46
圖4.1-9 Ce/Zr-800-10 ESCA粗勘圖..........................46

圖4.1-10 碳之ESCA細勘圖.................................47
圖4.1-11 Ce/Zr-500-10 ESCA細勘圖.........................47
圖4.1-12 Ce/Zr-800-10 ESCA細勘圖.........................48
圖4.1-13 Ce/Zr-500-10 ESCA細勘圖.........................48
圖4.1-14 Ce/Zr-800-10 ESCA細勘圖.........................49
圖4.2-1 反應溫度對二異丙醚轉化率的影響..................51
圖4.2-2 反應溫度對異丙醇選擇率的影響....................52
圖4.2-3 CeO2/ZrO2觸媒的穩定性...........................53
圖4.2-4 水蒸氣對二異丙醚轉化率的影響....................55
圖4.2-5 水蒸氣對異丙醇選擇率的影響......................56
圖4.2-6 二異丙醚進料分壓對其轉化率的影響................57
圖4.2-7 二異丙醚進料分壓對異丙醇選擇率的影響............58









表目錄
表2.1-1 直接水合法生產異丙醇工業比較......................5
表3.1-1 實驗藥品.........................................14
表3.1-2 實驗氣體.........................................15
表3.1-3 實驗器材.........................................16
表4.1-1 觸媒命名.........................................35
表4.1-2觸媒的物理性質....................................41
表4.1-3失活反應後觸媒物理性質............................41
表4.1-4表面分析元素比例..................................49

[1] Veba-Chemie, “Catalytic hydration of ethylene and propylene”,
French, 2072568, Sept 24 (1971).
[2] Neier, W., “Use cation catalyst for IPA”, Hydrocarbon Process,
51(11) ,113-116 (1972).
[3] Izumi, Y., “Hydration of olefins”, Japanese KoKai, 47-30608 Nov
9 (1972).
[4] Burton, P. E., “Process for hydrolyzing diisopropyl ether to
isopropyl alcohol by catalytic distillation using a solid acid
catalyst”, U.S. Pat., No. 6906229 (to Exxonmobil ) (2005).
[5] Neier, W., W. Webbers and M. Dettmer, “Process for continuously
producing alcohols ”, U.S. Pat., No. 4, 581, 475 (to Deutsche
Texaco Aktiengesellschaft) (1986).
[6] Bezman, S. A., “Diisopropyl ether hydration in isopropanol
production ”, U.S. Pat., No. 4,405,882(to Chevron) (1983).
[7] Bezman, S. A., “Diisopropyl ether reversion and oligomerization in isoproanol production”, U.S. Pat., No., 4,357,147 (to Chevron) (1982a).
[8] Bezman, S. A., “Diisopropyl ether reversion and oligomerization in isoproanol production”, U.S. Pat., No. 4,352,945 (to Chevron) (1982b).
[9] Levin, D., S. Luo, J. C. Vartuli, C. M. Yarbrough and D. C. Grenoble, “Selective decomposition of ethers”, U.S. Pat.,
No. 7,102,037 B2 (to Exxonmobil) (2006).
[10] Yabrough, C. M., B. W. Roberts, D. J. Davoren, K. J. Bturla, C. S. Katzenstein, D. Levin, H. G. Korsten and V. Swarup, “Process for alcohol production by selective ether decomposition”, U.S. Pat.,
No. 7,399,891 B2 (to Exxonmobil) (2008).
[11] Song, X. L., G. Z. Qiu and P. Qu, “Advances in research on
applications and synthesis methods of CeO2 nanoparticles”,
Rare Metal mater. Eng., 33, 29-34 (2004).
[12] Trovarelli, A., “Catalyst properties of ceria and CeO2-containing
materials”, Catal. Rev., 38, 439-520 (1996).
[13] Martinez-Arias, A., M. Fernandez-Garcia, L. N. Salamanca, R. X. Valenzuela, J. C. Conesa and J. Soria, “Structural and redox properties of ceria in alumina-supported ceria catalyst supports”, Phys. Chem., B104, 4038 (2000).
[14] Logan, A.D. and M. Shelef, “Oxygen availability in mixed cerium/praseodymium oxides and the effect of noble metals”, J. Mater. Res., 9, 468 (1994).
[15] Shannon, R. D., and C. T. Prewitt, “Coordination and volume changes accompanying high-pressure phase transformations of oxides”, Mater. Res. Bull., 4 (1), 57-62 (1969).
[16] Yashima, M., H. Arashi, M. Kakihana and M. Yoshimura, “Raman scattering study of cubic-tetragonal phase transition in Zr1-xCexO2 solid solution” J. Am. Ceram. Soc., 77, 1067 (1994) .
[17] Zhang, Y., A. Anderson and M. Muhammed, “Nanophase catalytic oxides: I. Synthesis of doped cerium oxides as oxygen storage promoters” Appl. Catal. B Environ., 6, 325 (1995).
[18] Lammonier, C., A. Bennani, A. D. Huysser, A. Aboukais and G.
Wrobel, “Evidence for different copper species in precursors of
copper-cerium oxide catalysts for hydrogenation reactions: An
X-ray diffraction, EPR and X-ray photoelectron spectroscopy
study” J. Chem. Soc. Faraday Trans., 92, 131 (1996).
[19] Imamura, S., M. shono, N. okamoto, A. Haneda and S. Ishida,
“Effect of cerium on the mobility of oxygen on manganese
oxides”Appl. Catal. A, General, 142, 279 (1996) .
[20] Rossignol, S., Y. Madier and D. Duprez, “Preparation of zirconia-ceria materials by soft chemistry”, Catal. Today, 50, 261-270 (1990).
[21] Colon, G., F. Valdivieso, M. Pijolat, R. T. Baker, J. J. Calvino and S. Bernal, “Textural and phase stability of CexZr1-xO2 mixed oxides under high temperature oxidizing condition”, Catal. Today, 50, 271-284 (1999).
[22] Brezesinski, T., M. Antonietti, M. Groenewolt, N. Pinna and B. Smarsly, “The generation of mesostructured crystalline CeO2, ZrO2 and CeO2-ZrO2 films using evaporation-induced self-assembly”, New J. Chem., 29, 237-242 (2005).
[23] Tani, E., M. Yoshimura and S. Smiya, “Revised phase diagram of the system ZrO2-CeO2 below 1400℃”, J. Am. Ceram. Soc., 66 (7), 506-510 (1994).
[24] 劉繼進，何莉萍，陳宗章。 “氧化釔摻雜四方氧化鋯電性研究”
矽酸鹽學報，31 (3)，241-245，(2003).
[25] 王大寧，梁開明，萬菊林。“碳的氧化鋯陶瓷” 矽酸鹽學報， 26 (2)，230-236，(1998).
[26] Ozawa, M., M. Kimura, A. Isogai“The application of CeZr oxide
solid solution to oxygen storage promoters in automotive
catalysts”, J. Alloys, Comp., 193, 73 (1993).
[27] Ingo, G. M., R. Dal Maschio and L. Scoppio, “Thermal and
surface characterizations of 25.5(wt.%) CeO2-2.5Y2O3-72ZrO2
fine powder”, Surf. interface anal., vol. 18, 661-666
(1992).
[28] Roberta, D. M., and J. Kasper, “Nanostructure CeO2-ZrO2 mixed
oxides”, j. Mater chem., 15, 633-648 (2005).
[29] Terribile, D., A. Trovarelli, J. Lorca, C. de Leitenburg and
G. Dolcetti, ”The preparation of high surface area CeO2–ZrO2
mixed oxides by a surfactant-assisted approach” Catal. Today, 43,
79, (1998).
[30] Reddy, B. M., P. Saikia, P. Bharali, L. Katta and G. Thrimurthulu,
“Highly dispersed ceria and ceria-zirconia nano composites over
silica surface for catalytic applications”, Catal. Today, 141,
109-114 (2009).