乙醇两步法制备 1,3- 丁二烯的催化剂研究

1. 乙醇两步法制备1,3-丁二烯的催化剂研究 指导老师：刘宗章 教授 报 告 人：李翔 报告时间：2013年9月13日

2. 主要内容

3. 一、拟选课题国内外的研究动态及背景 1,3-丁二烯的基本性质

4. 一、拟选课题国内外的研究动态及背景 1,3-丁二烯的应用 合成橡胶工业是丁二烯最重要的应用领域，其消费量占全球丁二烯消费总量的80%以上。随着汽车行业、国防军事等行业的大量需求，丁二烯的生产与消费引起了广泛的关注。

5. 一、拟选课题国内外的研究动态及背景 优势：可再生资源为原料 不足：丁二烯收率低 王德义 燕丰 丁二烯的生产技术及国内市场分析[J], 石化技术，2003,10（4）：60 童刘 刘宗章 张敏华 乙醇法制备1，3-丁二烯的研究进展[J], 化学工业与工程，2012,29（4）：38

6. 一、拟选课题国内外的研究动态及背景 文献中的反应机理 E.V. Makshina,W. Janssens, B.F. Sels, P.A. Jacobs，Catalytic study of the conversion of ethanol into 1,3-butadiene[J]， Catalysis Today, 2012,198:338~344

7. 一、拟选课题国内外的研究动态及背景

8. 一、拟选课题国内外的研究动态及背景 搜索关键词为：乙醇，乙醛，丁二烯

9. 一、拟选课题国内外的研究动态及背景 • Jones H E, Stahly E E, Corson B B, Butadiene from Ethanol. Reaction Mechanism, Journal of the American Chemical Society, 1949, 71: 1822~1828 • Toussaint W J, Dunn. J T, Production of Butadiene from alcohol, Industrial and engieering chemistry, 1947, 39: 120~125 • P.M.Kampmeyer, E.E.Stahly, Butadiene from Ethyl Alcohol[J],Industrial and Engineering Chemistry,1947,41(3):550~555 • Corson B B, Jones H E, Butadiene from ethyl alcohol, Industrial and engineering chemistry, 1950, 42: 359~373 • Bhattacharyya S K, Avasithi B N, Catalytic conversion of ethanol to butadiene by two-step process in fluidized bed, Journal of Applied Chemistry, 1966, 16: 239~244

10. 一、拟选课题国内外的研究动态及背景 • Niiyama H, Saburo M, Butadiene Formation from Ethanol over Silica-Magnesia Catalysts, Bulletin of the chemical society of Japan, 1972, 45: 655~659 • Ohnishi R, Takao A, Kozo T, Pronounced Catalytic Activity and selectivity of MgO-SiO2-Na2O for Synthesis of Buta-1, 3-diene from ethanol, Journal of the chemical society, Chemical communications, 1985, 22: 1613~1614 • Gruver V, Sun A, Fripiat J J, Catalytic properties of aluminatedsepiolite in ethanol conversion, Catalysis letters, 1995, 34: 359~364 • Marta León, Eva Díaz∗, Salvador Ordó˜nez,Ethanol catalytic condensation over Mg–Al mixed oxides derived from hydrotalcites,Catalysis Today,2011(164):436~442 • E.V. Makshina,W. Janssens, B.F. Sels, P.A. Jacobs，Catalytic study of the conversion of ethanol into 1,3-butadiene[J]， Catalysis Today, 2012,198:338~344

11. 小结

12. 二、课题拟解决的主要问题 基于文献和近期高美香实验，选取活性氧化铝为活性组分

13. 三、拟选课题在理论和应用方面的意义 理论方面 一、进一步研究催化剂结构和酸碱性对反应活性的影响 二、为新催化体系的选取提供一定的理论依据和技术支持 应用方面 一、能在一定程度上提高丁二烯的收率，为以后乙醇法的工业化提供了一定的理论基础 二、采用生物质乙醇为原料，缓解能源危机

14. 四、拟采取的技术措施和办法

15. 四、拟采取的技术措施和办法

16. 参考文献 • [1]Jones H E, Stahly E E, Corson B B, Butadiene from Ethanol. Reaction Mechanism, Journal • of the American Chemical Society, 1949, 71: 1822~1828 • [2]Toussaint W J, Dunn. J T, Production of Butadiene from alcohol, Industrial and engieering • chemistry, 1947, 39: 120~125 • [3]P.M.Kampmeyer, E.E.Stahly, Butadiene from Ethyl Alcohol[J],Industrial and Engineering • Chemistry,1947,41(3):550~555 • [4]M.H.Whitlock, G.J.Haddad, E.E.Stahly,System for Rapid Evaluation of Catalysts for • Production of Butadiene from Ethanol • [5]1944 US Patent: Method for Producing Butadiene • [6]Corson B B, Jones H E, Butadiene from ethyl alcohol, Industrial and engineering chemistry, • 1950, 42: 359~373 • [7]Bhattacharyya S K, Ganguly N D, One-step catalytic conversion of ethanol to butadiene in • the fixed bed .I. Single-oxide catalysts, Journal of Applied Chemistry, 1962, 12:97~104 • [8]Bhattacharyya S K, Ganguly N D, One-step catalytic conversion of ethanol to butadiene in • the fixed bed. I. Binary- and ternary-oxide catalysts, Journal of Applied Chemistry, 1962, 12(3): • 105~110 • [9]Bhattacharyya S K, Avasthi B N, One-step catalytic conversion of ethanol to butadiene in a • fluidized bed, Journal of Applied Chemistry, 1963, 2(1): 45~51 • [10]Bhattacharyya S K, Avasithi B N, Catalytic conversion of ethanol to butadiene by two-step • process in fluidized bed, Journal of Applied Chemistry, 1966, 16: 239~244 • [11]Bhattacharyya S K, Kinetic Study on the Mechanism of the Catalytic Conversion of Ethanol • to Butadiene , Journal of Catalysis,1967,7:152~158

17. [12]NiiyamaH, Saburo M, Butadiene Formation from Ethanol over Silica-Magnesia Catalysts, • Bulletin of the chemical society of Japan, 1972, 45: 655~659 • [13]KvisleS, Aguero A, Sneeden R P, Transformation of ethanol into 1, 3-butadiene over • magnesium oxide/silica catalysts, Applied Catalysis, 1988, 43: 117~131 • [14]Ohnishi R, Takao A, Kozo T, Pronounced Catalytic Activity and selectivity of • MgO-SiO2-Na2O for Synthesis of Buta-1, 3-diene from ethanol, Journal of the chemical society, • Chemical communications, 1985, 22: 1613~1614 • [15]Gruver V, Sun A, Fripiat J J, Catalytic properties of aluminatedsepiolite in ethanol conversion, • Catalysis letters, 1995, 34: 359~364 • [16]KitayamaY, Mitsuru S, Preparation of large surface area nickel magnesium silicate and its • catalytic activity for conversion of ethanol into buta-1,3-diene, Catalysis Letters, 1996, 36: 95~97 • [17]Marta León, Eva Díaz∗, Salvador Ordó˜nez,Ethanol catalytic condensation over Mg–Al mixed • oxides derived from hydrotalcites,Catalysis Today,2011(164):436~442 • [18]Ho-JeongChae, Tae-Wan Kim, Young-Kyun Moon, Kwang-EunJeong, Chul-UngKim • Butadiene Production from Bioethanol and Acetaldehyde over Tantalum Oxide-Supported Ordered • MesoporousSilica Catalysts,2013 • [19]US Patent: One-step Method for Butadiene Production • [20]Yang Wang, ShijieLiu,Butadiene Production from Ethanol,Journalof Bioprocess Engineering • and Biorefinery,2012(1):33~43 • [21]Carlo Angelici, Bert M. Weckhuysen, and Pieter C. A. Bruijnincx，Chemocatalytic Conversion • of Ethanol into Butadiene and Other Bulk Chemicals，ChemSusChem 2013, 6, 1–21 • [22]E.V. Makshina,W. Janssens, B.F. Sels, P.A. Jacobs，Catalytic study of the conversion of • ethanol into 1,3-butadiene，Catalysis Today, 2012,198:338~344

18. [23]FegwenChang , Hsienchang Yang, L. SelvaRoselin, WenyaoKuo Ethanol • dehydrogenation over copper catalysts on rice husk ash prepared by ion exchange, Applied Catalysis A: General, 2006,304:30~39 • [24]N. P. Bhat，H.U.Borgstedt, Corrosion behaviour of structural materials in sodium influenced by formation of ternary oxides, Werkstoffe und Korrosion, 1988,39:115~123 • [25]V. N. Iptieef, G. S. Monroe,L. E. Fisher, Decompostion of Alcohol over Niekel-Icieselguhrand other Catalysts , Industrial and engieering chemistry, 1949 • HirooNiiyama, EtsuroEchigoya，Hydrogen Transfer Reaction between Alcohols and • Acetone，Bulletin of the Chemical Society of Japan,1972,45:938~939 [26]周卉，董志仪，包珠娣等，氮气中乙烯、丙烯、乙炔、1，3一丁二烯、 一氯甲烷、氯乙烷、乙烯基乙炔混合气体标准样品的研制,低温与特气, 2010, 28(3):27~33 [27]周竞先，远拯月，谢筱帆 乙醇合成丁二烯反应中液相产物的气相色谱分析, 1966

19. 五、完成课题的条件 与老师和同学的交流学习（课题组报告，讲座，会议） 个人能力的培养（基础的催化相关的知识储备以及仪器的使用方法） 强壮的身体以及和睦的家庭

20. 六、课题进展计划

21. 敬请各位老师、同学批评指正！ 谢谢