跳到主要內容

臺灣博碩士論文加值系統

(216.73.216.17) 您好!臺灣時間:2025/09/03 05:04
字體大小: 字級放大   字級縮小   預設字形  
回查詢結果 :::

詳目顯示

: 
twitterline
研究生:王致凱
研究生(外文):Wang,Chih-Kai
論文名稱:乳酸酯化觸媒之研究
論文名稱(外文):Catalyst studies for lactic acid esterification
指導教授:李國禎李國禎引用關係
指導教授(外文):Li Kuo-Tseng
口試委員:王奕凱吳榮宗
口試日期:2010-07-22
學位類別:碩士
校院名稱:東海大學
系所名稱:化學工程與材料工程學系
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2011
畢業學年度:99
語文別:中文
論文頁數:118
中文關鍵詞:乳酸乳酸酯觸媒
相關次數:
  • 被引用被引用:6
  • 點閱點閱:309
  • 評分評分:
  • 下載下載:6
  • 收藏至我的研究室書目清單書目收藏:0
乳酸酯具有無毒、溶解性好、不易揮發、有果香味等特點,同時可生物降解,因此極具開發與應用前景,其消费的增長很快,是理想的”綠色溶劑 ”,主要用於微電子工廠作為電路板和電子原料的清洗劑。此外,乳酸丁酯以及乳酸和其他醇類所形成的酯類,是油漆、塗料、塑料等工廠中的溶劑。乳酸酯還可用於天然樹脂、油漆、印刷油墨、乾洗液、黏著劑等。

本論文探討使用酸性陽離子交換樹脂和各無機固體酸觸媒用來於催化乳酸和醇類間的酯化反應以製造乳酸酯。在酸性陽離子交換樹脂中,以Dowex 50wx8-100觸媒催化乳酸酯化反應性能最好(乳酸丁酯產率可達89%),而在無機固體酸觸媒中,TiO2-Al2O3觸媒有最好之催化乳酸酯化的能力(乳酸丁酯產率為95.7%)。

本研究使用共沉澱法製備不同莫耳比的TiO2-ZrO2觸媒及TiO2-Al2O3觸媒,利用X射線繞射儀(XRD)、熱場發射掃描式電子顯微鏡(TFSEM)、熱重分析儀(TGA)、表面積與孔洞分析儀(BET)、能量散射光譜儀(EDS) 來對混合雙金屬氧化觸媒作特性分析,並探討酯化反應之活性和觸媒酸性之關聯性。

Esters of lactic acid are non-toxic、soluble、non-volatile and have fruit flavor. It is also biodegradable and have wide applications, particularly as regulations and consumer preferences increase the demand for “green” chemicals. They are ideal green solvents which are used as the cleaning agents for the circuit board and electronic raw material. In addition, butyl lactate and esterification of lactic acid with other alcohol are solvents for paint and plastics. Esters of lactic acid also can be used to produce natural resins、 paints、printing inks, dry lotion, adhesive and so on.

The thesis uses acidic cation exchange resins and inorganic solid-acid catalysts to catalyze the esterification of lactic acid with alcohol. Among acidic cation exchange resins, Dowex 50wx8-100 had the best ester yield(butyl lactate yield was 89%).Among inorganic solid-acid catalysts, TiO2-Al2O3 had the best ester yield (butyl lactate yield was 95.7%).

We used XRD、TFSEM、TGA、BET and EDS to analyze TiO2-ZrO2 and TiO2-Al2O3 catalysts prepared by co- precipitation. The correlation between esterification activity and catalyst acidic properties were investigated

目錄
第一章. 緒論 1
1.1背景 1
1.2. 研究動機 2
第二章.文獻回顧 4
2.1 乳酸介紹 4
2.1.1 乳酸生產方法 5
2.2乳酸酯化介紹 7
2.2.1 乳酸甲酯 8
2.2.2乳酸乙酯 9
2.2.3 乳酸丙酯 9
2.2.4乳酸丁酯 10
2.3觸媒原理 11
2.3.1 觸媒擔體種類 12
2.3.2觸媒之合成方法 12
2.4 固體酸觸媒介紹 14
2.5混合金屬氧化物觸媒 15
2.5.1 各金屬氧化物觸媒介紹 17
第三章 觸媒製備與實驗設備 21
3.1 實驗材料 21
3.1.1實驗藥品 21
3.1.2實驗氣體 22
3.1.3實驗設備 23
3.2 觸媒製備 24
3.2.1 TiO2-ZrO2的製備 24
3.2.2 TiO2-Al2O3的製備 25
3.3 酯化反應實驗步驟 26
3.4 儀器設定與反應物產物定性、定量分析 29
3.4.1 氣相層析分析法 29
3.4.2 定性分析 31
3.4.3 定量分析(內部標準品法) 35
3.5熱場發射掃描式電子顯微鏡(TFSEM) 39
3.6 X射線繞射實驗(XRD) 40
3.7表面積與孔洞分析實驗(BET) 41
3.7.1 BET表面積之測定原理 41
3.7.2 BET表面積及孔徑大小之測定實驗 46
3.8熱重分析儀原理 48
3.9 傅立葉紅外線光譜儀 (FT-IR) 49
第四章.實驗結果與討論 50
4.1 乳酸酯化反應 51
4.1.1 乳酸濃度對乳酸酯化反應之影響 52
4.1.2時間對乳酸酯化反應之影響 53
4.1.3溫度對乳酸酯化反應之影響 54
4.2各陽離子交換樹脂催化性能之比較 55
4.3各無機觸媒催化性能之比較 56
4.4 金屬氧化物觸媒跟陽離子樹脂之優劣 57
4.5 TiO2-ZrO2催化乳酸酯化反應 58
4.5.1 TiO2-ZrO2催化乳酸丁酯生成 58
4.5.2 TiO2-ZrO2觸媒催化乳酸和其他醇類間之酯化反應 63
4.6 TiO2-ZrO2 觸媒特性分析 72
4.7. TiO2-Al2O3 催化乳酸丁酯 89
4.8. TiO2-Al2O3 觸媒分析 93
4.9. TOF、酸性點密度 107
第五章 結 論 110
第六章 參考文獻 113


[1] Ghofa,A., Ogawa,S.,Kokugan,T., Production of L –lactic acid from fresh cassava roots slurried with tofu liquid waste by Streptococcus bovis,Journal of bioscience and bioengineering,6,606-612(2005).

[2] Reddy,G., Altaf,Md., Naveena,B.J.,Venkateshwar M., Vijay Kumar, E., Amololytic bacterial lactic acid fermentation-A review, Biotechnology Advances,26,22-34(2008).

[3] Narayanan ,K., Roychoudhury, P.K., Privastava ,A., L(+) lactic acid fementation and its product polymerization. Electronic Journal of Biotechnology, 7,1(2004).

[4]Datta,R.,Tsai,S.,Bonsignore,P.,Moon,S.,Rank,J.R.,Technological and economic potential of poly(lactic acid) and lactic acid derivatives. FEMS Microbiology Reviews,16,221-231 (2006).

[5]Schopmeyer, H.H., Arnold,C.R., Lactic Acid Purification .U.S.Patent 2,350,37 (1946).

[6]Kumar, R., Mahajani,S.M., Nanavati, H., Noronha , S.B., Recovery of Lactic Acid by Batch Reactive Distillation. J. Chem. Technol Biotechnol,80,1141(2006).

[7] Kumar, R., Mahajani,S.M., Nanavati, H., Noronha , S.B., A Continuous Process for the Recovery of Lactic Acid by Batch Reactive Distillation. J. Chem. Technol Biotechnol,81,1767 (2006).

[8] Cao,X.,Yun, H. S.,Koo,Y.M., Recovery of L(+) Lactic Acid by Anion Exchange Resin Amberlite IRA-400. Biochem. Eng.J.,11,189(2002).

[9]Cockrem,M .C.M., Johnson ,P.D., Recovery of lactate esters and lactic acid from fermentation broth. U.S. Patent 5,210,296 (1993).

[10]Liu,W.T. and C.S. Tan., Liquid-Phase Esterification of Propionic Acid with n-Butanol. Ind.Eng. Chem.Res.,40,3281-3286(2001).

[11]Yadav, G.D. and M.B. Thathagar, Esterification of Maleic Acid with Ethanol over Cation-Exchange Resin Catalyat, Reactive & Functional Polymers, 52,99-100(2002).

[12]Tanabe,K.,Hattori,H.,Sumiyoshi,T.,Tamaru,K.,and Kondo ,T.,Surface property and catalytic activity of MgO---TiO2 ,J Catal.53,1(1978).

[13] Arata ,K.,Akutagawa,S.,and Tanabe K. ,Epoxide Rearrangement III. Isomerization of 1-Methylcyclohexene Oxide over TiO 2–ZrO 2, NiSO 4 and FeSO 4, Bull Chem .Soc. Jan .49 , 390 (1976).


[14]Seiyama ,T., In Metal Oxide and their Catalytic Actions. Kodansha,Tokyo,1978.

[15]Tanabe,K., Hattor,H., Sumiyoshi,T., Tamaru,K., and Kondo,T. Isomerization and disproportionation of olefins over tungsten oxides supported on various oxides , J .Catal.53,1(1978).

[16] Itoh M., Hattroi H., and Tanabe, K, The nature of active sites on TiO2 and TiO2---SiO2 for the isomerization of butenes,J Catal.35,225(1974)

[17]Shibata,K., Kiyoura,T., Kitagawa,J., Sumiyoshi ,T.,and Tanabe,K., Acidic properties of binary metal oxides. Bull.Chem.Soc,Jpn. 46,2985(1973).

[18]Tanabe,K.,Ishiya, I., Matsuzaki, I., Ichikawa, I., and Hattori,H., Acidic Property and Catalytic Activity of TiO 2• ZnO. Bull. Chem. Soc, Jpn. 45, 47(1972).

[19]Nishiwaki, K.,Kakuta,N.,Ueno,A.,and Nakabayashi,H.,Generation of acid sites on finely divided TiO2,J Catal. 118,498(1989).

[20]Yamaguchi, T., Recent progress in solid superacid, Appl. Catal. 61,1(1990).


[21]Phase Diagrams for Ceramists, The American Ceramic Society, inc., 76,4150-4999(1975).

[22] Yamaguchi, T., and Tanabe ,K., J.,Catalytic sites on SnO2 and TiO2&SnO2 for the isomerization of 1-butene, Phys.Chem. 79, 2409(1975).

[23] Yamaguchi, T., and Tanabe ,K., J. Preparation and characterization of ZrO2 and SO42−-promoted ZrO2 ,Phys.Chem, 80, 1723(1976).

[24]Tanaka,T. ,Kumagai,H. ,Hattori,H. ,Kudo,M. ,and Hasegawa,S.,Generation of basic sites on TiO2 by reduction with H2 , J. Catal. 127,221(1991).

[25]Anderson, J.B.F., Burch,R., and Cairns, J,A., The influence of metal-support interactions on the reaction of methylcyclopentane over supported Pt catalysts, J. Catal. 107,364(1987)

[26]Herrmann, J.M., Room temperature photocatalytic oxidation of liquid cyclohexane into cyclohexanone over neat and modified TiO2 , J. Catal. 118,43(1989).

[27]Clarke, J.K.A., Dempsey, R.J.,Baird, T., and Rooney ,J.J., Selectivities for hydrocarbon reactions on SMSI titania-supported platinum formed by high-temperature reduction, J. Catal. 126,370(1980).

[28] Nakano,Y., Yamaguchi ,T., and Tanabe,K., Hydrogenation of conjugated dienes over ZrO2 by H2 and cyclohexadiene,J. Catal. 80,307(1983).

[29] Nakano,Y.,Iizuka, T., Hattori , H., and Tanabe,K., Surface properties of zirconium oxide and its catalytic activity for isomerization of 1-butene, J. Catal. 57,1(1979).

[30]Maehashi, T., Maruya, K., Domen,k., Aiko, K., and Onishi,T. Surface and catalytic properties of TiO2---Al2O3, Chem. Lett., 747(1984).

[31]Shibata , K., Kivoura , T., Kitagawa, j., Sumiyoshi, T., and Tanabe,K. ,A new hypothesis regarding the surface acidity of binary metal oxides, Bull. Chem. Soc.Jan.46,2985(1973).

[32]汪建民,陶瓷技術手冊,中華民國粉末冶金協會出版,民國八十三年七月。

[33]Hattori, H.,et al., The nature of active site on TiO2 and TiO2-SiO2 for the isomerization of 1-butene , J Catal, 43,172,(1975).

[34] Wang,I., Chang,W.F., Shiau,R.J., Wu, J.C., and Chung C.C., Nonoxidative dehydrogenation of ethylbenzene over TiO2---ZrO2 catalysts : II. The effect of pretreatment on surface properties and catalytic activities, J. Catal. 83,428(1983).
[35]Kutty,T.R.N., Ahuja, S., Retarding effect of surface hydroxylation on preparation methods of TiO2 on the photocatalytic degradation of phenol in aqueous dispersion , J. Phys.Chem., 94,829-832,(1990).

[36]吳榮宗, “含氧化鈦混合型金屬氧化物觸媒之製備極其應用研究”,博士論文,國立清華大學化學工程研究所,(1985).

[37]房靜玲,”利用氧化鈦-氧化鋯酸-鹼雙功能之特性進行觸媒重組反應之探討”,博士論文,國立清華大學化學工程學系,(1990).

[38]王志銘,”以TiO2-ZrO2為主的觸媒進行正庚烷的轉化反應研究”,碩士論文,國立清華大學化學工程學系,(2005).

[39] 王堯展,東海大學化學工程研究所論文,“丙烯醇環氧化成環氧丙醇之觸媒研究”,(2000)。

[40] Stephane, D., Hughes, W., Fernad C,T., Kinetics of the Liquid Phase Synthesis and Hydrolysis of Butyl Lactate Catalysed by Cation Exchange Resin, J Chem Tech. Biotechnol.,59,149-156,( 1994)

連結至畢業學校之論文網頁點我開啟連結
註: 此連結為研究生畢業學校所提供,不一定有電子全文可供下載,若連結有誤,請點選上方之〝勘誤回報〞功能,我們會盡快修正,謝謝!
QRCODE
 
 
 
 
 
                                                                                                                                                                                                                                                                                                                                                                                                               
第一頁 上一頁 下一頁 最後一頁 top