第二章 文獻探討
3.1 實驗材料與 設備
4.3.5 比表面積的測定
表 4.19 水泥的比表面積
BET(m2/g)比表面積 Pore volume(cm3/g)平均孔容
Pore size(Å )平均孔徑。
Sample Hegiht BET(m2/g) Pore size(Å ) Pore volume(cm3/g) 水泥 0.2044 3.7010 0.001045 11.2985
4.3.6 熱重分析與熱差微熱分析(TGA&DTA)的測定 1.9 % weight loss
圖 4.66 水泥 TGA&DTA 圖
顯示熱重和差熱分析（DTA）的水泥催化劑的熱譜。從這個數字可以看出，三個階段的分 解在不同的溫度區的區別。熱對溫度的影響粘貼水泥評估已有報導【86,87】。人們普遍 認為在 120°C 水會完全蒸發消除，110°C-170°C 石膏和鈣礬石開始分解和碳水合物水部分 發生分解。180-300° C 分解水合物的矽酸鈣水合物(csh)和含碳的鋁酸鹽
(carboaluminate)中。結合水的損失和 portlandite 脫羥基反應之間發生脫水反應氫氧 化鈣的脫羥基（氫氧化鈣），大約需要 450-550° C。然後 700° C。以上碳酸鈣開始分解 去碳酸根。
實驗操作變數...
4.3.7 油與甲醇莫耳數比之影響
80 90 100
1/6 1/9 1/15 1/21 1/24
油醇比 轉
酯 率 (
) %
圖 4.67 油與甲醇莫耳數比之影響
反應條件:觸媒鍛燒溫度: 650 °C, 觸媒含量 4 %, 反應時間: 3 h, 反應溫度: 65 °C.
反應油醇比由 1:6~1:24，發現隨油醇比的增加轉酯率也上升。以 1:24 效果最好並以此設 定為最佳參數。
4.3.8 觸媒鍛燒溫度的影響
反應條件:油醇莫耳比:1/24， 觸媒含量 4 %, 反應時間: 3 h, 反應溫度: 65 °C.
觸媒鍛燒溫度條件為 85℃~950℃，發現在 350℃以下時，隨溫度上升轉酯率逐漸提高，
450℃以後反應趨於穩定轉酯率變化不大。不再提高。故以 450℃為最佳反應條件。
0
4.3.10 催化劑回收再利用對轉酯率影響
0 20 40 60 80 100
1 2 3 4 5 6 7
回收次數 轉
酯 率(
)%
圖 4.70 催化劑回收再利用對轉酯率影響
反應條件: 觸媒鍛燒溫度: 650 °C, 油醇莫耳比:1/24，反應時間: 3 h, 反應溫度: 65 °C. 觸 媒含量 4 %。由數據顯示水泥回收次數可重複 4 次，第 5 次開始觸媒逐漸毒化產生失效。
4.3.11 水泥氣相層析圖
圖 4.71 以水泥為催化劑轉酯大豆油氣相層析圖
表 4.20 水泥為催化劑轉酯大豆油氣相層析數據
A：C14 至 C24.1 脂肪酸甲酯成分峰之間的所有成分波峰之積分總面積=651642566 AEI：內標物十七烷酸甲酯之波峰面積=119548873
CEI：所用十七烷酸甲酯之濃度(mg/ml)=配標準品的濃度=10.192mg/ml VEI:所用十七烷酸甲酯之體積（ml）=2ml
m:樣品製備中精秤之樣品量(mg) =111.8mg
帶入以上公式求出 c=81.15%
Apex RT Area %Area
C16:0 4.21 57376689.4 4.53
C17:0 4.61 119,548,873 9.44
C18:0 5.39 281,217,659 22.21
C18:1 5.69 34,666,162 2.74
C18:2 5.76 2,986,253 0.24
C18:3 7.34 1,516,151 0.12
A 651642566
A EI 119548873
CEI 10.192
VEI 2
m 111.8
c 81.15%
4.3.12 以微波合成加熱方式轉酯大豆油為生質柴油之轉酯率
200 400 600 800
微波功率(w)
表 4.22 以微波合成加熱方式-改變不同時間
4.3.13 以水泥為催化劑轉酯大豆油反應機構圖【63-64】
Calcinated waste concrete has high activity for transesterification reaction from soybean oil.
圖 4.74 以水泥為催化劑轉酯大豆油反應機構圖 precursory solid base
+H2O
Soybean oil FAME>96.5%
+ glycerine
calcium silicate hydrate fine aggregate
crush
∆ Ca(OH)2(s)
CaO (s) waste concrete block
∆>900°C cement, fine aggregate
and coarse aggregate coarse aggregate separateness
第五章 結論與建議
5.1 結論:以圖 4.75 表示
本研究先以正交法比較：Ca(NO3)2 、Ca(OH)2、CaO 三種催化劑轉酯反應條件發現以 CaO 效果最佳，進一步由天然物廢棄的蛋殼中經由鍛燒程序產生 CaO 用於生質柴油的轉 酯化反應催化劑提高轉酯反應效率。不但可減少廢棄物又兼具環保功效，所產生的生質 柴油可提供能量用於解決能源問題。在適當的條件下，甲醇/油莫耳比 12:1，催化劑用量 質量比為 2％，反應時間為 2h，蛋殼鍛燒溫度 900°C、鍛燒時間 2h。形成甲基酯轉酯率 可達 95％以上，可重複使用 10 次。水泥磨粉在煅燒後可得到高活性催化劑。煅燒水泥具 有很高的活性對大豆油酯交換生產生質柴油。甲醇/油摩爾比 24:1，水泥 4％的催化劑，
反應溫度 65℃得到了最好的結果，以及生質柴油轉酯超過 98％在 3 小時的反應下。該方 法的水泥塊，是利用廢棄物製備的催化劑，可以做廢物的回收，減少污染，降低催化劑 的成本，對環境友好的催化劑。
圖 4.75 以不同催化劑轉酯大豆油反應機構圖
5.2 未來方向與建議:
目前因為生質柴油的原料油價格關係，使生質柴油的產品製造成本仍然居高不下，價格 上無法與普遍使用的石化柴油競爭，因此要尋找便宜的原料和發展適合它的製程。以蛋 殼與水泥為觸媒轉酯生質柴油是可行的方法。
建議1.可建立廢棄蛋殼回收管道。一方面可達到廢棄物減量與降低生質柴油生產成本。
建議2.可從廢棄建築物混擬土中。將水泥成分分離出用於生產生質柴油。一方面可達到
參考資料
【1】 陳育智,生質柴油非均相催化轉酯製程之探討，未發表的碩士論文,2008, 台北: 國立 臺灣大學生農學院生物產業機電工程學系研究所.
【2】 李宗育, 利用廢棄沙拉油製造生質柴油之研究大豆,碩士論文,2006, 私立高苑科技 大學高分子環保材料研究所.
【3】 Y.H.Junog,H.Wu, Analysis of biodiesel promotion in Taiwan,Renewable and Sustainable Energy Reviews ,2008,12,1176-1186.
【4】 經濟部, 能源產業技術白皮書, 2010, p.281.
Faungnawakij ,Waste shells of mollusk and egg as biodiesel production catalysts.
Bioresource Technology , 2010, 101, 3765-3767.
【9】 Y.C.Sharma, B.Singh, J.Korstad, Application of an Efficient Nonconventional Heterogeneous Catalyst for Biodiesel Synthesis from Pongamia pinnata Oil, Energy Fuels , 2010, 24, 3223–3231.
【10】K.Noiroj, P.Intarapong, A.Luengnaruemitchai, S.Jai-In, A comparative study of KOH/Al2O3 and KOH/NaY catalysts for biodiesel production via transesterification from palm oil. Renew Energy , 2009, 34, 1145–1150.
【11】F.R. Ma, M.A.Hanna, Biodiesel production: a review. Bioresource Technolog, , 1999, 70(1), 1-15.
【12】J.W.Mellor, A Comprehensive Treatise on Inorganic and Theoretical Chemistry, vol. III, Longmans, Green and Co., London, 1981.
【13】 M.L. Granados, M.D.Z. Poves, D.M. Alonso, R. Mariscal, F.C. Galisteo, R.
Moreno-Tost, J. Santamaria, J.L.G. Fierro, Biodiesel from sunflower oil by using activated calcium oxide, Appl. Catal. B: Environ. , 2007, 73, 317–326.
【14】M. Kouzu, S.Y. Yamanaka, J.S. Hidaka, M. Tsunomori, Heterogeneous catalysis of calcium oxide used for transesterification of soybean oil with refluxing methanol, Appl.
Catal. A: Gen , 2009, 355, 94–99.
【15】M. Kouzu, T. Kasuno, M. Tajika, Y. Sugimoto, S. Yamanaka, J. Hidaka, Calcium oxide as a solid base catalyst for transesterification of soybean oil and its application to
biodiesel production, Fuel , 2008, 7, 2798–2806.
【16】Z.Wei, C.Xu, B. Li,Application of waste eggshell as low-cost solid catalyst for biodiesel production . Bioresource Technology, 2009, 100, 2883-2885.
【17】N. Nakatani, H. Takamori, K. Takeda, H. Sakugawa, Transesterification of soybean oil using combusted oyster shell waste as a catalyst, Bioresour. Technol,2009,100, 1510–1513.
【18】P.L. Boey, G.P. Maniam, S.A. Hamid, Biodiesel production via transesterification of palm olein using waste mud crab (Scylla serrata) shell as a heterogeneous catalyst, Bioresour. Technol, 2009, 100, 6362–6368.
【19】P.L. Boey, G.P. Maniam, S.A. Hamid, Utilization of waste crab shell (Scylla serrata) as a catalyst in palm olein transesterification, J. Oleo Sci., 2009, 58, 499–502.
【20】P.L. Boey, G.P. Maniam, S.A. Hamid, D.M.H. Ali, Crab and cockle shells as catalysts for the preparation of methyl esters from low FFA chicken fat, J. Am. Oil Chem. Soc. ,2011, doi:10.1007/s11746-010-1660-4.
【21】R.Chakraborty, S. Bepari, A. Banerjee, Application of calcined waste fish (Labeo rohita) scale as low-cost heterogeneous catalyst for biodiesel synthesis ,Bioresource
【22】J.Boro, D. Deka, A. J. Thakur，A review on solid oxide derived from waste shells as catalyst for biodiesel production， Renewable and Sustainable Energy Reviews,2011, xxx ,xxx– xxx.
【23】W. Xie, H. Li, Alumina-supported potassium iodide as a heterogeneous catalyst for biodiesel production from soybean oil, J. Mol. Catal. A: Chem. ,2006, 255 , 1–9.
【24】X.Liu, H. He, Y.Wang, S.Zhu, X.Piao, Transesterification of soybean oil to biodiesel using CaO as a solid base catalyst. Fuel ,2008, 87, 216–221.
【25】P.L.Boey, G. P.Maniam,, S.A.Hamid, Performance of calcium oxide as a heterogeneous catalyst in biodiesel production: A review , Chemical Engineering Journal ,2011, 168 15–22.
【26】A. Kawashima, K. Matsubara, K. Honda, Acceleration of catalytic activity of calcium oxide for biodiesel production, Bioresour Technol , 2009, 100 696–700.
【27】X. Liu, X. Piao, Y. Wang, S. Zhu, H. He, Calcium methoxide as a solid base catalyst for the transesterification of soybean oil to biodiesel with methanol, Fuel , 2008,
87 ,1076–1082.
【28】C.R.V. Reddy, R. Oshel, J.G. Verkade, Room-temperature conversion of soybean oil and poultry fat to biodiesel catalyzed by nanocrystalline calcium oxides, Energy Fuels , 2006, 20, 1310–1314.
【29】X.Liu, H.He, Y.Wang, S.Zhu, Transesterification of soybean oil to biodiesel using SrO as a solid base catalyst. Catal. Commun., 2007, 8, 1107–1111.
【30】K. Noiroj,P. Intarapong , Apanee Luengnaruemitchai , Samai Jai-In , A comparative study of KOH/Al2O3 and KOH/NaY catalysts for biodiesel production via transesterification from palm oil, Renewable Energy , 2009, 34, 1145–1150.
【31】C.S. MacLeod, A.P. Harvey, A.F. Lee, K. Wilson, Evaluation of the activity and
stability of alkali-doped metal oxide catalysts for application to an intensified method of biodiesel production, Chem. Eng. J., 2008, 135, 63–70.
【32】E.S. Umdu, M. Tuncer, E. Seker, Transesterification of Nannochloropsis oculata
microalga’s lipid to biodiesel on Al2O3 supported CaO andMgOcatalysts, Bioresour.
Technol, 2009, 100, 2828–2831.
【33】G. Arzamendi, E. Argui narena, I. Campo, S. Zabala, L.M. Gandia, Alkaline and alkaline-earth metals compounds as catalysts for the methanolysis of sunflower oil, Catal. Today , 2008, 133–135, 305–313.
【34】J.Shen, M.Tu, C.Hu, Structural and Surface Acid/Base Properties of
Hydrotalcite-Derived MgAlO Oxides Calcined at Varying Temperatures. Journal of Solid State Chemistry , 1998, 137, 295-301.
【35】楊政翰,大豆油與甲醇製備生質柴油使用 MgO/CaO 異相觸媒製程探討, 2010, 中興 大學化學工程研究所
【36】M.C.G. Albuquerque, D.C.S. Azevedo, C.L. Cavalcante Jr., J. Santamaria-Gonzalez, J.M. Merida-Robles, R. Moreno-Tost, E. Rodriguez-Castellon, A. Jimenez-Lopez,P.
Maireles-Torres, Transesterification of ethyl butyrate with methanol using MgO/CaO catalysts, J. Mol. Catal. A: Chem, 2009, 300, 19–24.
【37】C. Ana, A.Rubio, J. Santamarı, A.Gonza´ lez, M.Josefa, M.Robles, M.T. Ramo,M.
David, M.Alonso, A.Jime, M.T. Pedro, Heterogeneous transesterification processes by using CaO supported on zinc oxide as basic catalysts, Catalysis Today , 2010, 149, 281–287.
【38】C. Ngamcharussrivichai, P. Totarat, K. Bunyakiat, Ca and Zn mixed oxide as a
heterogeneous base catalyst for transesterification of palm kernel oil, Appl.Catal. A: Gen.
2008, 341, 77–85.
【39】H.Sun, J.Duan,P.Chen, H.Lou, X.Zheng,,Room temperature transesterification of soybean oil to biodiesel catalyzed by rod-like CaxSiOx+2 solid base Catalysis Communications, 2011, 12, 1005–1008.
【40】R.S. Watkins, F.L. Adam, K.Wilson, Li-CaO catalysed tri-glyceride transesterification
using Li/CaO catalysts: activation process and homogeneous contribution, Catal. Today , 2009, 143, 167–171.
【42】M.C. Albuquerque, I. Urbistondo, J. Gonzalez, J.Robles, R..Tost, E. Castellon, A. Lopez, D. Azevedo, C.Cavalcante, P.Torres, CaO supported on mesoporous silicas as basic catalysts for transesterification reactions, Appl. Catal. A: Gen, 2008 , 334,35–43.
【43】G. Albuquerque, J. Gonzalez, J.Robles, R..Tost, E. Castellon, A. Jimenez-Lopez, D.C.S.
Azevedo, C.L. Cavalcante Jr., P. Maireles-Torres, MgM (M=Al and Ca) oxides as basic catalysts in transesterification processes, Appl. Catal. A: Gen., 2008, 347, 162–168
【44】謝志誠,農業機械學刊,利用鎂鋁水滑石將黃豆油轉酯成生質柴油, 農業機械學刊 ,
【53】S. Gryglewicz, Rapeseed oil methyl esters preparation using heterogeneous catalysts,
Bioresour. Technol., 1999, 70, 249–253.
【54】C.Ngamcharussrivichai, P.Nunthasanti, S.Tanachai, K.Bunyakiat, Biodiesel production through transesterification over natural calciums,Fuel Processing Technology, 2010, 91, 1409–1415.
【55】W. Wiwatnimit, S. Wangnoi, Modified dolomites as catalysts for palm kernel oil transesterification, J. Mol. Catal. A: Chem., 2007, 27, 624–633.
【56】A.k.Sarma; Konmer D; Bordoloi P.K.,”Comprehensive.Analysis of Propeties of Biodiesel from Koroch Seed Oil, Enegy Fulels, 2005, 19, 656-657.
【57】M .Mittelbach, P. Tritthart, Dieselfuel Derived from Vegetable Oils, III.Emission Tests Using Methyl Esters of Used Frying Oil, Journal of the American Oil Chemists Society, 1988, 65, 1185-1187.
【58】P.Patil, V.G .Gude, S Deng, Biodiesel Production from, Jatropha Curcas, Waste Cooking, and Camelina Sativa Oils. Ind. Eng. Chem. Res, 2009, 48, 10850–10856.
【59】B.P. Lim, G.P. Maniam, S.A. Hamid, Biodiesel from adsorbed waste oil on spent bleaching clay using CaO as a heterogeneous catalyst, Eur. J. Sci. Res., 2009, 33 347–357.
【60】S. Kent,B. Amber,R. Curtis , C.Eric , N.Mani , Review of biodiesel composition, properties, and specifications, Renewable and Sustainable Energy Reviews, 2011, xxx,xxx– xxx
【61】熱分析儀專題,科儀新知, 2007,第 18 卷第四期
【62】T. Wao , P. Yu, S. Wang, Y. Luo,Application of Aluminate As a Heterogenous Base Catalyst for Biodiesel Production from Soybean Oil,Energy&Fuels, 2009, 23,1089-1092
【63】J.X.Wang,K-T.Chen,B.Z.Wen,Y.H.Liao,C.C.Chen,Transesterification of soybean oil to biodiesel using cement as a solid base catalyst,Journal of the Taiwan Institute of Chemical Engineers , 2011, xxx ,xxx–xxx
【64】王建勛，溫碧洲，陳吉南，許正興，陳錦章,以水泥等建築廢棄物為生質柴油轉酯觸媒，
【65】劉文豹,趙德智,韓雪梅,苗樹運,楊培志, 正交法探討製備生物柴油的優化條件,化工 時刊, 2006, 20,5.
【66】A.P.Chouhan, A.K. Sarma Modern heterogeneous catalysts for biodiesel production: A comprehensive review. Renew Sustain Energy Rev , 2011 , oi:10.1016/j.rser.2011.07.112
【67】S.K.Hoekman, et al. Review of biodiesel composition, properties, and specifications.
Renew Sustain Energy Rev ,2011, doi:10.1016/j.rser.2011.07.143
【68】E.Lotero, Y.Liu, E. Lopez, K.Suwannakarn, D.Bruce, A. Goodwin, Synthesis of
Biodiesel via Acid Catalysis. Industrial and Engineering, Chemistry Research, 2005, 44, 5353-5363.
【69】H .Fukuda; A .Kondo, H.Noda,”Biodiesel Fuel Production by Transeterification of Oils.”, J Bioscience Bioengineering, 2001, 92, 5, 405-416.
【70】D. Leung , X. Wu, M.K.H. Leung, A review on biodiesel production using catalyzed transesterification, Applied Energy , 2010, 87, 1083–1095
【71】M.C.G.Albuquerque,I.Jimenez-Urbistondo,J. Santamaria-Gonzalez, J.M. Merida-Robles, R. Moreno-Tost, E. Rodriguez-Castellon, A. Jimenez-Lopez, D.C.S. Azevedo, C.L.
Cavalcante Jr., P. Maireles-Torres, CaO supported on mesoporous silicas as basic catalysts for transesterification reactions, Appl. Catal. A:Gen ,2008, 334, 35–43.
【72】A.Demirbas, Biodiesel_A realistic fuel alternative for diesel engines. Springer, 2008, 208
【73】G.R. Peterson, W.P. Scarrah, Rapeseed oil transesterification by heterogeneous catalysis, J. Am. Oil Chem. Soc. , 1984, 61, 1593–1597.
【74】B. Yoosuk, P. Udomsap, B. Puttasawat, P. Krasae, Modification of calcite by hydration–dehydration method for heterogeneous biodiesel production process: the effects of water on properties and activity, Chem. Eng. J., 2010, 162, 135–141.
【75】A.M. Ruppert, J.D. Meeldijk, B.M.W. Kuipers, B.H. Erne, B.M. Weckhuysen, Glycerol etherification over highly active CaO-based materials: new mechanistic aspects and related colloidal particle formation, Chem. Eur. J. 2008, 14, 2016–2024.
【76】M. Kouzu, T. Kasuno, M. Tajika, S. Yamanaka, J. Hidaka, Active phase of calcium oxide used as solid base catalyst for transesterification of soybean oil with refluxing methanol, Appl. Catal. A: Gen., 2008, 334 , 357–365.
【77】A.P.Singh Chouhan,A.K.Sarma,Modern heterogeneous catalysts for biodiesel
production:A comprehensive review,Renewable and Sustainable Energy Reviews, 2011, xxx , xxx-xxx
【78】L.S. Hsieh, U. Kumar, J.C.S. Wu, Continuous production of biodiesel in a packedbed reactor using shell–core structural Ca(C3H7O3)2/CaCO3 catalyst, Chem. Eng.J., 2010 , 158 ,250–256.
【79】W.J .Stadelman, Egg and egg products.In:Francis,F.J.(ED.),Encyclopedia of Food Science and Technology,second ed.John Wiley and Sons,New York, 2000, p539-599
【80】F. Chen, S.M .Lu *, E. Wang, K.T. Tseng, Renewable and Sustainable Energy Reviews, Renewable and Sustainable, Energy Reviews , 2010, 14, 2029–2038.
【81】B.Freedman, E. H. Pryde, T. L.Mounts,Variables affecting the yields of fatty esters from transesterified vegetable oils. JAOCS, 2010, 61, 1638-1642.
【82】Y.C.Chien, M.Lu, M. Chai, F.J.Boreo, Characterization of Biodiesel and Biodiesel Particulate Matter by TG, TG-MS, and FTIR, Energy & Fuels ,2009, 23, 202–206.
【83】C. Ngamcharussrivichai, P. Totarat, K. Bunyakiat, Appl. Catal. A Gen, 2008, 341.
【84】H. Wang, M.H. Wang, S.G. Liu, N. Zhao, W. Wei, Y.H. Sun, J. Mol. Catal. A Chem. , 2006, 258,308–312.77–85.
【85】Infrared Spectroscopy:Fundamentals and Applications p 96-115
【86】W .Sha, O.Neill EA, Z Guo. Differential scanning calorimetry study of ordinary portland cement. Cem Concr Res, 1999, 29, 1487-1489.
【87】L .A.Ruiz, G. Platret, E .Massieu, A.Ehrlacher The use of thermal analysis in assessing the effect of temperature on a cement paste. Cem Concr Res , 2005, 35,609-613.