成功大學博碩士論文系統

簡易檢索 / 詳目顯示

回結果列表

研究生：	羅文詩 Potestades, Maria Lourdes
論文名稱：	鹼土金屬氧化物固溶體作為生質柴油轉酯化反應之非均質催化劑 Alkali Earth Metal Oxide Solid Solution as Heterogeneous Catalyst for Tranesterification in Biodiesel Production
指導教授：	林士剛 Lin, Shih-Kang
學位類別：	碩士 Master
系所名稱：	工學院 - 尖端材料國際碩士學位學程 International Curriculum for Advanced Materials Program
論文出版年：	2017
畢業學年度：	105
語文別：	英文
論文頁數：	82
中文關鍵詞：	生質柴油、鹼性催化劑、轉酯化反應
外文關鍵詞：	biodiesel, basic catalyst, transesterification
相關次數：	點閱：85 下載：4
分享至:	分享至facebook 分享至twitter

查詢本校圖書館目錄查詢臺灣博碩士論文知識加值系統勘誤回報

近幾年，隨著全球暖化、土地汙染、安全議題等永續議題的持續延燒，再生能源的需求日益提升，其中以生質柴油作為替代石油的再生能源，係從動物油脂或是植油脂中轉化而成。生質柴油無毒、永續且是生物可分解。

本篇研究係著重於製造生質柴油中所使用的異質鹼性催化劑的開發。製造生質柴油的方式稱為轉酯化，係將動物或植物油脂混合乙醇及催化劑的輔助，產物即為生質柴油與副產物甘油。使用鹼性催化劑的缺點其一在於生成生質柴油的過程中會伴隨淋溶作用的發生，生成皂類，使催化劑無法重複使用。因此本篇研究的目標為開發一可防止轉酯化過程中伴隨的淋溶作用及皂類生成的異質鹼性催化劑，並希望能理解異質鹼性催化劑CaxSr1-xO系統中單相及兩相對於轉酯化過程的效果。

在本篇研究中，我們使用了三種不同的方法來合成催化劑，分別為共析出法、固相燒結法、以及聚合物錯合溶液法。實驗結果發現，相較於固相燒結法及共析出法，聚合物錯合溶液法能使原子混合的程度整體達最均質，且能藉由螯合機制來捕捉陽離子，此法為合成出高均勻性、高純度催化劑的最佳合成方法。

其中，以單相Ca0.2Sr0.8O系統表現出最好的生質柴油產率，而兩相的CaxSr1-xO系統則表現出一固定區間的產率。淋溶作用的發生以及催化劑粒子大小也隨著兩相的出現而下降。實驗結果也顯示，副產物Sr(OH)2 亦會對生質柴油的產率有顯著的影響。

Through the years, the demand for renewable sources of energy increases significantly as we are facing serious problems with safety hazards, air and land pollution, global warming and many other ecological complications. Biodiesel is an alternative diesel fuel derived from animal fats or vegetable oils. It is purely biodegradable, non-toxic and sustainable.

Biodiesel is made from the process called transesterification wherein animal fats or vegetable oils (triglyceride) are mixed with alcohol, and with an aid of a catalyst, will produce biodiesel and glycerol. For this study, we focused our research on the catalyst, a heterogeneous basic catalyst to be specific. One of the drawbacks of using basic catalyst is the low biodiesel yield due to soap formation and lack of reusability due to serious problems of leaching. The goal was to develop a catalyst that will hinder soap formation and leaching during transesterification. We also wanted to determine the effects of single-phase versus two-phase oxides using CaxSr1-xO system.

In this study, we performed three various methods for catalyst synthesis – Co-Precipitation (CP), Solid State Sintering (SSS) and Polymer Complex Method (PCM). It was found out that PCM is the best method for synthesizing a high purity and homogeneous sample due to atoms mixed atomistically rather than just surface reactions for solid state sintering. PCM offers more purity than co-precipitation since the chelating agent catches the cations, which ensures random mixing and homogeneity.

Single phase Ca0.2Sr0.8O, exhibited the highest yield amongst all the catalysts. However, the two-phase system has stabilized the yield within its range. Leaching was also decreased within the two-phase region, as well as the particle size of the catalysts. It was also found out that Sr(OH)2 contributes significantly to the biodiesel conversion.

Table of Contents
Acknowledgements.......................i  
摘要 ...................ii
Abstract ....................................... iv
Table of Contents ...................................... v 
Table of Figures ................................. vii
Table of Tables................................... ix
Chapter 1 Introduction ........................... 1
1.1. Preface ..................................... 1
1.2. Bioenergy ................................. 2
1.3. Pros and Cons .................................. 2
1.4. Energy Issues ................................ 2
1.5. Motivations, Objectives, and Limitations of the Study ...................... 3
Chapter 2 Review of Related Literature ................... 5
2.1 Biodiesel ....................................... 5
2.2 Different Feed stocks for Biodiesel............... 6
2.3 Transesterification Reaction ......................... 6
2.4 Acid and Basic Catalysts ............................ 8
2.5 Byproducts Formation ................................. 9
2.6 Current Advancements on Alkali Earth Metal Oxide Catalysts ....... 10
2.7 Low-order Phase Diagrams...................... 11
2.8 Alloying Effects in Catalysts .................. 15
2.9 Polymer Complex Method (PCM)........................ 16
2.10 CaSrO system for biodiesel production .............. 16
Chapter 3 Methodology .............................. 22
3.1. Catalyst Preparation .............................. 22
3.1.1 Co- Precipitation Method .....................22
3.1.2 Solid State Sintering......................... 22
3.1.3 Polymer Complex Method ........................... 23
3.2. Transesterification Process .................. 24
Table 3-2 Different Transesterification Parameters...... 24
3.3. Characterization Techniques................. 25
3.3.1 X-ray Diffraction (XRD) ............. 25
3.3.2 Nuclear Magnetic Resonance (NMR)................. 26
3.3.3 Inductively Coupled Plasma – Mass Spectroscopy (ICP-MS) .................... 26
3.3.4 Differential Scanning Calorimetry (DSC) / Thermogravimetric Analysis (TGA) .............. 26
3.3.5 Scanning Electon Microscopy (SEM) ............... 26
Chapter 4 Results and Discussion....................... 28
4.1. Effect of Different Synthesis Routes in Catalyst Preparation............... 28
4.1.1. Co-precipitation Method....................... 28
4.1.2. Solid State Sintering .................... 36
4.1.3. Polymer Complex Method................... 39
4.1.3.1. Effects of Heating/Cooling rates and Calcination Temperature ............. 41
4.1.3.2 Effect of pH .............................. 42
4.1.3.3 Effect of Different Precursors.................. 43
4.2 Morphology and Particle Size................. 46
4.3 Ternary Oxide (Ba doped CaSrO) ........... 47
4.4 Transesterification Reaction ....................... 49
4.4.1 Effect of Different Reaction Times................ 49
4.4.2 Effect of Single-Phase and Two-Phase system (ICP-MS RESULTS) ........... 50
4.4.3. Effect of Impurity Sr(OH)2 .................. 51
4.4.4. Leaching Tests ........................... 52
Chapter 5 Conclusion ............................ 55
Chapter 6 Recommendation ............................... 56
BIBLIOGRAPHY ...................... 57
A. NMR Results of SrO, CaO and Various CaxSr1-xO compounds ........... 62
B. NMR Results of Impurities Sr(OH)2 and Ca(OH)2 ........ 73
C. NMR Results of Reused Catalysts ................. 76
                                    

[1] IEA, World Energy Outlook 2016 (2016).
[2] International Energy Agency, "Renewables energy outlook," World Energy Outlook 2012 210 (2012).
[3] H. Long, X. Li, H. Wang, and J. Jia, "Biomass resources and their bioenergy potential estimation: A review," Renew. Sustain. Energy Rev. 26, 344 (2013).
[4] S. Shafiee, and E. Topal, "When will fossil fuel reserves be diminished?," Energy Policy 37, 181 (2009).
[5] A.C. Pinto, L.L.N. Guarieiro, M.J.C. Rezende, N.M. Ribeiro, E.A. Torres, W.A. Lopes, P.A.P. De Pereira, and J.B. De Andrade, "Biodiesel: An overview," J. Braz. Chem. Soc. 16, 1313 (2005).
[6] M. Fangrui, and M. Hanna, "Biodiesel production : A review " Bioresour. Technol. 70, 1 (1999).
[7] M. Lapuerta, O. Armas, and J. Rodriguez Fernandez, "Effect of biodiesel fuels on diesel engine emissions," Prog. Energy Combust. Sci. 34, 198 (2008).
[8] I. Barabás, and I.-A. Todorut, in Biodiesel Qual. Emiss. by-Products (2011), pp. 3–28.
[9] G. Knothe, "Dependence of biodiesel fuel properties on the structure of fatty acid alkyl esters," Fuel Process. Technol. 86, 1059 (2005).
[10] M.S.E. Technology, and T. Akhtar, "Synthesis of Biodiesel from Triglyceride oil," Mycotoxin Res. 6, 100 (1990).
[11] U. Schuchardt, R. Sercheli, and R.M. Vargas, "Transesterification of vegetable oils: A review," J. Braz. Chem. Soc. 9, 199 (1998).
[12] L.A. Anderson, and A.K. Franz, "Real-time monitoring of transesterification by 1H NMR spectroscopy: Catalyst comparison and improved calculation for biodiesel conversion," Energy and Fuels 26, 6404 (2012).
[13] B.R. Moser, "Biodiesel production, properties, and feedstocks," Vitr. Cell. Dev. Biol. - Plant 45, 229 (2009).
[14] B. Freedman, E.H. Pryde, and T.L. Mounts, "Variables affecting the yields of fatty esters from transesterified vegetable oils," J. Am. Oil Chem. Soc. 61, 1638 (1984).
[15] I.M. Atadashi, M.K. Aroua, A.R. Abdul Aziz, and N.M.N. Sulaiman, "The effects of catalysts in biodiesel production: A review," J. Ind. Eng. Chem. 19, 14 (2013).
[16] M.K. Lam, K.T. Lee, and A.R. Mohamed, "Homogeneous, heterogeneous and enzymatic catalysis for transesterification of high free fatty acid oil (waste cooking oil) to biodiesel: A review," Biotechnol. Adv. 28, 500 (2010).
[17] Z. Helwani, M.R. Othman, N. Aziz, J. Kim, and W.J.N. Fernando, "Solid heterogeneous catalysts for transesterification of triglycerides with methanol: A review," Appl. Catal. A Gen. 363, 1 (2009).
[18] L.T. Thanh, K. Okitsu, L. van Boi, and Y. Maeda, "Catalytic Technologies for Biodiesel Fuel Production and Utilization of Glycerol: A Review," Catalysts 2, 191 (2012).
[19] Z. Yang, and W. Xie, "Soybean oil transesterification over zinc oxide modified with alkali earth metals," Fuel Process. Technol. 88, 631 (2007).
[20] W. Xie, and Z. Yang, "Ba-ZnO catalysts for soybean oil transesterification," Catal. Letters 117, 159 (2007).
[21] S. Furuta, H. Matsuhashi, and K. Arata, "Biodiesel fuel production with solid amorphous-zirconia catalysis in fixed bed reactor," Biomass and Bioenergy 30, 870 (2006).
[22] M. Kouzu, and J.S. Hidaka, "Transesterification of vegetable oil into biodiesel catalyzed by CaO: A review," Fuel 93, 1 (2012).
[23] T.-L. Kwong, and K.-F. Yung, "Heterogeneous alkaline earth metal–transition metal bimetallic catalysts for synthesis of biodiesel from low grade unrefined feedstock," RSC Adv. 5, 83748 (2015).
[24] Z. Kesic, I. Lukic, M. Zdujic, H. Liu, and D. Skala, in Procedia Eng. (2012), pp. 1169–1178.
[25] Y. Syamsuddin, and B.H. Hameed, "Synthesis of glycerol free-fatty acid methyl esters from Jatropha oil over Ca-La mixed-oxide catalyst," J. Taiwan Inst. Chem. Eng. 58, 181 (2016).
[26] A. Molaei Dehkordi, and M. Ghasemi, "Transesterification of waste cooking oil to biodiesel using Ca and Zr mixed oxides as heterogeneous base catalysts," Fuel Process. Technol. 97, 45 (2012).
[27] Y.H. Taufiq-Yap, H. V. Lee, R. Yunus, and J.C. Juan, "Transesterification of non-edible jatropha curcas oil to biodiesel using binary Ca-Mg mixed oxide catalyst: Effect of stoichiometric composition," Chem. Eng. J. 178, 342 (2011).
[28] A. Tangy, I.N. Pulidindi, and A. Gedanken, "SiO2 Beads Decorated with SrO Nanoparticles for Biodiesel Production from Waste Cooking Oil Using Microwave Irradiation," Energy & Fuels 30, 3151 (2016).
[29] K. Faungnawakij, B. Yoosuk, S. Namuangruk, N. Viriya-Empikul, P. Krasae, and W. Nualpaeng, in Proc. IEEE Conf. Nanotechnol. (2013), pp. 929–932.
[30] Q. Liu, S. Wang, H. Tan, Z. Yang, and J. Zeng, "Preparation and doping mode of doped LiMn2O4 for Li-ion batteries," Energies 6, 1718 (2013).
[31] K.W. Kim, S.-W. Lee, K.-S. Han, H.J. Chung, and S.I. Woo, "Characterization of Al-doped spinel LiMn2O4 thin film cathode electrodes prepared by Liquid Source Misted Chemical Deposition (LSMCD) technique," Electrochim. Acta 48, 4223 (2003).
[32] N. Metals, "Preparation and property of spinel," Trans. Nonferrous Met. Soc. China (2006).
[33] M.-R. Yang, and W.-H. Ke, "The Doping Effect on the Electrochemical Properties of LiFe0.95M0.05PO4 (M=Mg2+, Ni2+, Al3+, or V3+) as Cathode Materials for Lithium-Ion Cells," J. Electrochem. Soc. 155, A729 (2008).
[34] Z. Liu, X. Zhang, and L. Hong, "Preparation and electrochemical properties of spherical LiFePO4 and LiFe0.9Mg0.1PO4 cathode materials for lithium rechargeable batteries," J. Appl. Electrochem. 39, 2433 (2009).
[35] Z. Yang, W. Yang, and Z. Tang, "Pillared layered Li1-2xCaxCoO2 cathode materials obtained by cationic exchange under hydrothermal conditions," J. Power Sources 184, 557 (2008).
[36] I.B. Bankovi-Ili, M.R. Miladinovi, O.S. Stamenkovi, and V.B. Veljkovi, "Application of nano CaO-based catalysts in biodiesel synthesis," Renew. Sustain. Energy Rev. 72, 746 (2017).
[37] M. Kouzu, T. Kasuno, M. Tajika, S. Yamanaka, and J. Hidaka, "Active phase of calcium oxide used as solid base catalyst for transesterification of soybean oil with refluxing methanol," Appl. Catal. A Gen. 334, 357 (2008).
[38] S. Yan, M. Kim, S. Mohan, S.O. Salley, and K.Y.S. Ng, "Effects of preparative parameters on the structure and performance of Ca-La metal oxide catalysts for oil transesterification," Appl. Catal. A Gen. 373, 104 (2010).
[39] Y.C. Wong, Y.P. Tan, Y.H. Taufiq-Yap, I. Ramli, and H.S. Tee, "Biodiesel production via transesterification of palm oil by using CaO–CeO2 mixed oxide catalysts," Fuel 162, 288 (2015).
[40] W. Xie, and L. Zhao, "Heterogeneous CaO-MoO3-SBA-15 catalysts for biodiesel production from soybean oil," Energy Convers. Manag. 79, 34 (2014).
[41] L. Yang, P. Lv, Z. Wang, Z. Yuan, W. Luo, H. Li, L. Yu, and H. Sun, "Promotional effect of transition metal doping on the properties of KF/CaO catalyst for biodiesel synthesis," Int. J. Green Energy 0, 1 (2017).
[42] B. Tabah, A.P. Nagvenkar, N. Perkas, and A. Gedanken, "Solar-Heated Sustainable Biodiesel Production from Waste Cooking Oil Using a Sonochemically Deposited SrO Catalyst on Microporous Activated Carbon," Energy & Fuels 31, 6228 (2017).
[43] M. Kakihana, "Invited review  sol-gel preparation of high temperature superconducting oxides," J. Sol-Gel Sci. Technol. 6, 7 (1996).
[44] H. Li, S. Niu, C. Lu, and J. Li, "Calcium oxide functionalized with strontium as heterogeneous transesterification catalyst for biodiesel production," Fuel 176, 63 (2016).
[45] S. Weinbruch, H. Büttner, and M. Rosenhauer, "The orthorhombic-hexagonal phase transformation in the system BaCO3-SrCO3 to pressures of 7000 bar," Phys. Chem. Miner. 19, 289 (1992).
[46] L.C. De Jonghe, and M.N. Rahaman, in Handb. Adv. Ceram. Mater. Appl. Process. Prop. (2003), pp. 187–264.
[47] D. Levy, and M. Zayat, The Sol-Gel Handbook (2015).
[48] L. Zhao, "Novel Solid Base Catalysts for the Production of Biodiesel from Lipids By Novel Solid Base Catalysts for the Production of Biodiesel from Lipids," (2010).
[49] S.L. Suib, New and Future Developments in Catalysis: Catalytic Biomass Conversion (2013).
[50] M. Behrens, and M. Armbruster, in Catal. Altern. Energy Gener. (2012), p. 538.
[51] X. Liu, H. He, Y. Wang, S. Zhu, and X. Piao, "Transesterification of soybean oil to biodiesel using CaO as a solid base catalyst," Fuel 87, 216 (2008).
[52] M. Ončák, R. Włodarczyk, and J. Sauer, "Hydration Structures of MgO, CaO, and SrO (001) Surfaces," J. Phys. Chem. C 120, 24762 (2016).
[53] H.S. Huang, and Z.H. Liu, "Transesterification of glyceryl tributyrate with methanol using strontium borate as the solid base catalyst," Sci. China Chem. 56, 1727 (2013).
[54] factsage.cn/fact/documentation

校內：2022-06-01公開
校外：2022-06-01公開

簡易檢索 / 詳目顯示

相關論文