本论文以生物质衍生化合物羟基丙酮的选择性氧化酯化制备高附加值丙酮酸甲酯为目标，围绕醇氧化酯化制备酯类化合物的过程展开讨论，针对选择性氧化酯化反应中催化剂酸碱性的影响进行研究，寻求能有效催化羟基丙酮转化制备丙酮酸甲酯的多功能催化剂。 本文比较了具有不同载体的负载型金催化剂催化反应性能，并用Hammett指示剂法对各个载体酸碱度进行测定，结果表明，酸碱两性催化剂催化性能优于单一酸碱性催化剂，以具有适宜酸碱两性的HAP载体上负载Au得到的Au/HAP催化剂表现出相对最佳催化活性。 为了进一步明确催化剂酸碱度的作用并由此研制丙酮酸甲酯合成的高效催化剂，本文制备了不同Ca/P比即具有一定酸碱度差异的...To develop an efficient process for the synthesis of methyl pyruvate from biomass-derived acetol, this dissertation has focused on the study of the effect of acid-base nature on the catalytic performances of supported Au catalyst and the reaction mechanisms involved. Au-based catalysts using different supports were investigated for the oxidative esterification of acetol to methyl pyruvate. The re...学位：理学硕士院系专业：化学化工学院_物理化学学号：2052014115162

庄梦琦

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Xiamen University Institutional Repository

  学校编码：10384                                分类号      密级         学号：20520141151627                                        UDC                硕  士  学  位  论  文     羟基丙酮一步氧化酯化制备丙酮酸甲酯的研究 Oxidation Esterification of Acetol with Methanol to Methyl Pyruvate over Supported Au Catalysts  庄梦琦  指导教师姓名：王 勇 教 授 万 绍 隆 副 教 授 专  业 名 称：物 理 化 学 论文提交日期：2017 年  月 论文答辩时间：2017 年  月 学位授予日期：2017 年  月    答辩委员会主席：          评    阅    人：           2017 年  月 厦门大学博硕士论文摘要库  A Thesis Submitted to the Graduate School for M. S. Degree  Oxidation Esterification of Acetol with Methanol to Methyl Pyruvate over Supported Au Catalysts By Mengqi Zhuang  Supervisor: Professor Yong Wang  Associate Professor Shaolong Wan  State Key Laboratory of Physical Chemistry of Solid Surfaces College of Chemistry and Chemical Engineering Xiamen University  May, 2017     厦门大学博硕士论文摘要库  厦门大学学位论文原创性声明  本人呈交的学位论文是本人在导师指导下,独立完成的研究成果。本人在论文写作中参考其他个人或集体已经发表的研究成果，均在文中以适当方式明确标明，并符合法律规范和《厦门大学研究生学术活动规范（试行）》。 另外，该学位论文为（                            ）课题（组）的研究成果，获得（               ）课题（组）经费或实验室的资助，在（               ）实验室完成。（请在以上括号内填写课题或课题组负责人或实验室名称，未有此项声明内容的，可以不作特别声明。）  声明人（签名）：                           年     月     日       厦门大学博硕士论文摘要库  厦门大学学位论文著作权使用声明 本人同意厦门大学根据《中华人民共和国学位条例暂行实施办法》等规定保留和使用此学位论文，并向主管部门或其指定机构送交学位论文（包括纸质版和电子版），允许学位论文进入厦门大学图书馆及其数据库被查阅、借阅。本人同意厦门大学将学位论文加入全国博士、硕士学位论文共建单位数据库进行检索，将学位论文的标题和摘要汇编出版，采用影印、缩印或者其它方式合理复制学位论文。 本学位论文属于： （     ）1.经厦门大学保密委员会审查核定的保密学位论文，于   年  月  日解密，解密后适用上述授权。 （     ）2.不保密，适用上述授权。 （请在以上相应括号内打“√”或填上相应内容。保密学位论文应是已经厦门大学保密委员会审定过的学位论文，未经厦门大学保密委员会审定的学位论文均为公开学位论文。此声明栏不填写的，默认为公开学位论文，均适用上述授权。）                                声明人（签名）： 年   月   厦门大学博硕士论文摘要库目录  i  目录  摘要 ........................................................................................................... Ⅰ Abstract  .................................................................................................. Ⅱ  第一章 绪论 .............................................................................................. 1 1.1 引言 ................................................................................................................. 1 1.2 生物质及其衍生平台化合物转化 ................................................................. 1 1.2.1 生物质.................................................................................................... 1 1.2.2 羟基丙酮................................................................................................ 3 1.2.3 丙酮酸甲酯简介及合成背景................................................................ 4 1.2.3.1 丙酮酸与甲醇缩合法.................................................................. 6 1.2.3.2 乳酸甲酯氧化法.......................................................................... 6 1.2.3.3 其他合成途径.............................................................................. 7 1.2.4 羟基丙酮氧化酯化制备丙酮酸甲酯.................................................... 7 1.3 醇氧化酯化制备酯类化合物 ......................................................................... 8 1.3.1 醇氧化酯化制备酯类化合物路径探讨................................................ 8 1.3.2 负载型金催化剂.................................................................................. 10 1.3.3 负载型金催化剂与碱性位点.............................................................. 10 1.3.4 催化剂酸性位点在醇氧化酯化体系中的作用.................................. 12 1.4 羟基磷酸钙简介及其在催化中的应用 ....................................................... 15 1.5 论文的构思与目的 ....................................................................................... 17 1.6 论文的组成和概要 ....................................................................................... 18  第二章 实验部分 .................................................................................... 31 2.1 原料与试剂 ................................................................................................... 31 2.2 催化剂的制备 ............................................................................................... 33 厦门大学博硕士论文摘要库目录  ii  2.2.1 载体的制备.......................................................................................... 33 2.2.2 负载型金催化剂的制备...................................................................... 33 2.3 催化剂的性能测试与结果分析 ................................................................... 34 2.3.1 催化剂的性能测试.............................................................................. 34 2.3.2 催化反应结果分析.............................................................................. 34 2.4 催化剂的表征 ............................................................................................... 34 2.4.1 透射电子显微镜（TEM） ................................................................. 34 2.4.2 X 射线粉末衍射（XRD） .................................................................. 34 2.4.3 电感耦合等离子发射光谱（ICP-OES） .......................................... 35 2.4.4 傅立叶变换红外光谱（FT-IR） ........................................................ 35 2.4.5 N2 物理吸脱附（BET） ...................................................................... 35 2.4.6 NH3/CO2 程序升温脱附（NH3/CO2-TPD） ....................................... 35 2.4.7 哈米特指示剂法（Hammett titration） ............................................. 35  第三章 负载型金催化剂催化羟基丙酮一步氧化酯化反应的研究 .... 37 3.1 引言 ............................................................................................................... 37 3.2 结果与讨论 ................................................................................................... 38 3.2.1 不同载体及负载型金催化剂的表征.................................................. 38 3.2.2 不同载体的负载型金催化剂催化性能测试...................................... 41 3.2.3 HAP 和 Au/HAP 系列催化剂的表征.................................................. 43 3.2.3.1 FT-IR 表征 .................................................................................. 43 3.2.3.2 XRD 表征 ................................................................................... 44 3.2.3.3 ICP-OES 表征 ............................................................................ 45 3.2.3.4 BET 表征 .................................................................................... 46 3.2.3.5 TEM 表征 ................................................................................... 46 3.2.3.6 TPD 表征 .................................................................................... 49 3.2.3.7 吡啶吸附红外表征.................................................................... 51 3.2.4 载体酸碱度对 Au/HAP 系列催化剂的催化性能的影响.................. 51 3.2.5 Au 负载量对 Au/HAP 催化性能的影响 ............................................. 53 厦门大学博硕士论文摘要库目录  iii  3.2.6 羟基丙酮氧化酯化反应动力学的研究.............................................. 54 3.2.6.1 反应温度的影响........................................................................ 54 3.2.6.2 反应时间的影响........................................................................ 55 3.2.7 Au/HAP 催化剂稳定性考察 ................................................................ 56 3.2.7.1 焙烧气氛对 Au/HAP 催化剂稳定性的影响............................ 56 3.2.7.2 Au/HAP1.62 催化剂稳定性测试 ................................................. 57 3.3 本章小结 ....................................................................................................... 58  第四章 Au/HAP 催化剂催化羟基丙酮转化路径的研究 .................... 63 4.1 引言 ............................................................................................................... 63 4.2 Au/HAP 催化剂催化羟基丙酮转化路径的探讨 ......................................... 63 4.3 本章小结 ....................................................................................................... 68  第五章 结论............................................................................................. 70 致谢 ........................................................................................................... 71              厦门大学博硕士论文摘要库厦门大学博硕士论文摘要库CONTENTS  i  CONTENTS  Abstract in Chinese ....................................... Ⅰ Abstract in English  ...................................... Ⅱ  Chapter 1. General Introduction ............................................................. 1 1.1 Introduction .................................................. 1 1.2 Introduction of Biomass ........................................ 1 1.2.1 Biomass ................................................. 1 1.2.2 Acetol ................................................... 3 1.2.3 Methyl pyruvate and its preparation ........................... 4 1.2.2.1 Condensation Method ................................. 6 1.2.2.2 Methyl Lactate Oxidation Method ........................ 6 1.2.2.2 The other synthsis methods ............................. 7 1.2.4 Oxidative Esterification of Acetol into Methyl Pyruvate ........... 7 1.3 Studies on the Oxidative Esterification of Alcohols .................. 8 1.3.1 Reaction mechanism for the Oxidative Esterification of Alcohols .... 8 1.3.2 Supported Au Catalysts .................................... 10 1.3.3 Cooperative Effect between Au and Base Sites .................. 10 1.3.3 Effect of Acid Sites on the Oxidative Esterification of Alcohols .... 12 1.4 Introduction of Hydroxyapatite ................................. 15 1.5 Objectives of this Thesis ....................................... 17 1.6 Outline of this Thesis ......................................... 18  Chapter 2. Experimental ................................... 31 2.1 Marterials and Reagents ...................................... 31 2.2 Preparation of Catalysts ....................................... 33 2.2.1 Preparation of Supports .................................... 33 厦门大学博硕士论文摘要库CONTENTS  ii  2.2.2 Preparation of Catalysts .................................... 33 2.3 Catalytic Reaction ............................................ 34 2.3.1 Catalysts Performance Evaluation ............................ 34 2.3.2 Analysis ................................................ 34 2.4 Characterizations of Catalysts .................................. 34 2.4.1 TEM Characterizations .................................... 34 2.4.2 XRD Characterizations .................................... 34 2.4.3 ICP-OES Analysis ........................................ 35 2.4.4 FT-IR Characterizations .................................... 35 2.4.5 N2 Physisorption Characterizations ........................... 35 2.4.6 NH3/CO2 Adsortion Measurements ........................... 35 2.4.7 Hammett titration Analysis ................................. 35  Chapter 3. Oxidation Esterification of Acetol to Methyl Pyruvate . 37 3.1 Introduction ................................................ 37 3.2 Results and Discussions ....................................... 38 3.2.1 Characterizations of Various Supports and Catalysts ............. 38 3.2.2 Catalytic Behaviors of Au Catalysts Loaded on Different Supports .. 41 3.2.3 Characterizations of HAPs and Au/HAPs ...................... 43 3.2.3.1 FT-IR Characterizations ............................... 43 3.2.3.2 XRD Characterizations ............................... 44 3.2.3.3 ICP-OES Analysis ................................... 45 3.2.3.4 N2 Physisorption Characterizations ...................... 46 3.2.3.5 TEM Characterizations ............................... 46 3.2.3.6 NH3/CO2 Adsortion Measurements ...................... 49 3.2.3.7 FT-IR Spectra of Pyridine Adsorption .................... 51 3.2.4 Effect of Acid-Base Properties on Catalytic Behaviour of Au/HAP Catalysts .................................................... 51 3.2.5 Effect of Au Loading on the Catalytic Performances ............. 53 厦门大学博硕士论文摘要库CONTENTS  iii  3.2.6 Kinetic Studies of the Oxidative Esterification of Acetol .......... 54 3.2.6.1 Effect of Reaction Temperature ......................... 54 3.2.6.2 Effect of Reaction Time ............................... 55 3.2.7 Stability of Au/HAP catalysts ............................... 56 3.2.7.1 Effect of Calcination Atmosphere on the Stability of Au/HAP . 56 3.2.7.2 Stability of Au/HAP1.62 ............................... 57 3.3 Conclusions ................................................. 58  Chapter 4. Reaction Pathways for the Conversion of Acetol over Au/HAP Catalysts ........................................ 63 4.1 Introduction ................................................ 63 4.2 Discussion on the Reaction Pathways for the Conversion of Acetol over Au/HAP catalysts ............................................... 63 4.3 Conclusions ................................................. 68  Chapter 5. Conclusions .................................... 70  Acknowledgements ....................................... 71   厦门大学博硕士论文摘要库厦门大学博硕士论文摘要库摘要  I  摘 要  本论文以生物质衍生化合物羟基丙酮的选择性氧化酯化制备高附加值丙酮酸甲酯为目标，围绕醇氧化酯化制备酯类化合物的过程展开讨论，针对选择性氧化酯化反应中催化剂酸碱性的影响进行研究，寻求能有效催化羟基丙酮转化制备丙酮酸甲酯的多功能催化剂。 本文比较了具有不同载体的负载型金催化剂催化反应性能，并用 Hammett指示剂法对各个载体酸碱度进行测定，结果表明，酸碱两性催化剂催化性能优于单一酸碱性催化剂，以具有适宜酸碱两性的 HAP 载体上负载 Au 得到的 Au/HAP催化剂表现出相对最佳催化活性。 为了进一步明确催化剂酸碱度的作用并由此研制丙酮酸甲酯合成的高效催化剂，本文制备了不同 Ca/P 比即具有一定酸碱度差异的 Au/HAP 系列催化剂。结合催化剂的 TEM、ICP-OES、NH3/CO2-TPD 等表征结果与反应性能测试结果发现，不同 Ca/P 比的 Au/HAP 系列催化剂上 Au 含量和 Au 粒径基本一致，而催化剂的酸碱度是影响该系列催化剂催化性能的重要因素。具有适宜酸碱度的Au/HAP1.62 催化剂表现出最佳性能，催化反应可得羟基丙酮转化率为 62%，丙酮酸甲酯选择性为 87%。该催化剂稳定性良好，经 5 次循环使用，催化性能仍与初次反应性能维持一致。 通过对反应中间体和产物的研究发现，由羟基丙酮制备丙酮酸甲酯的反应经历半缩醛中间体而非丙酮酸中间体，具体过程为：羟基丙酮先脱氢氧化生成丙酮醛，丙酮醛与甲醇缩合形成半缩醛，半缩醛进一步氧化生成丙酮酸甲酯。在反应过程中，缩酮产物 2，2-二甲氧基丙酸甲酯由半缩酮与溶剂甲醇缩合生成，该缩酮产物可作为中间产物进一步氧化生成丙酮酸甲酯。  关键词：羟基丙酮；丙酮酸甲酯；酸碱性；羟基磷酸钙；金 厦门大学博硕士论文摘要库  厦门大学博硕士论文摘要库厦门大学博硕士论文摘要库Abstract  II  Abstract  To develop an efficient process for the synthesis of methyl pyruvate from biomass-derived acetol, this dissertation has focused on the study of the effect of acid-base nature on the catalytic performances of supported Au catalyst and the reaction mechanisms involved. Au-based catalysts using different supports were investigated for the oxidative esterification of acetol to methyl pyruvate. The results showed that the amphoteric catalysts are superior compared to other catalysts, especially HAP with appropriate acid-base nature exhibiting the best performances.  The acid/base properties of HAP-based catalysts can be regulated by adjusting the Ca/P molar ratio. Au/HAP1.62, possessing optimum acid and base sites, was identified as an optimum catalyst exhibiting 62% conversion of acetol and 87% selectivity to methyl pyruvate. The results reconfirmed the key role of acid-base sites in the oxidative esterification of acetol to methyl pyruvate.  In order to understand the reaction network involved in acetol oxidative esterification to methyl pyruvate, we have carried out time course studies using acetol as well as the possible intermediates as the substrate. The oxidative esterification of acetol to methyl pyruvate was found to proceed via a hemiacetal intermediate arising from the condensation of pyruvic aldehyde and methanol, which is subsequently oxidized to the methyl pyruvate. The ketal is formed via the condensation of hemiketal and methanol, and is converted into desired methyl pyruvate.  Key words: Acetol; Methyl pyruvate; Acid-base properties; Hydroxyapatites; Gold.  厦门大学博硕士论文摘要库Degree papers are in the “Xiamen University Electronic Theses and Dissertations Database”. Fulltexts are available in the following ways: 1. If your library is a CALIS member libraries, please log on http://etd.calis.edu.cn/ and submitrequests online, or consult the interlibrary loan department in your library. 2. For users of non-CALIS member libraries, please mail to etd@xmu.edu.cn for delivery details.厦门大学博硕士论文摘要库

Oxidation Esterification of Acetol with Methanol to Methyl Pyruvate over Supported Au Catalysts

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Oxidation Esterification of Acetol with Methanol to Methyl Pyruvate over Supported Au Catalysts

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