论文总字数：32764字

摘 要

ε-己内酯是一种用途广泛的有机化工中间体，用于生产ε-己内酰胺、聚己内酯、聚己内酯多元醇等。环己酮在分子氧条件下B-V氧化制备ε-己内酯越来越受到人们的重视。氧气是一种安全、廉价的氧化剂，常温常压即可完成反应，反应条件温和，环己酮的转化率高，ε-己内酯的选择性好。由于分子氧氧化能力比较弱，因此在反应中需要添加苯甲醛为共氧剂，其用量往往是环己酮摩尔比的3倍，消耗量过大，如果以较低的苯甲醛消耗得到较高的环己酮的转化率和ε-己内酯的收率，便可以提高反应的经济性。
本文采用挥发诱导自组装法制备了介孔Sn-Al₂O₃，在分子氧存在条件下，考察了在环己酮B-V氧化反应中的催化性能。通过XRD、N₂吸附脱附、ICP、NH₃-TPD、TEM和UV-vis DRS表征结果表明，Sn分别以四配位和六配位进入介孔Al₂O₃中，当Sn的掺杂量为7%时即Sn-Al₂O₃-7，此时的比表面积、孔容、孔径和酸量最大。环己酮B-V氧化制备ε-己内酯的结果表明，以Sn-Al₂O₃-7为催化剂，催化剂与环己酮的质量比为0.28，苯甲醛与环己酮的质量比为2.8，溶剂乙腈与环己酮的质量比为30，70℃的条件下反应5h，环己酮的转化率为89.1%，ε-己内酯的选择性达到90.7%。

关键词：环己酮 EISA Baeyer-Villiger氧化 分子氧

Preparation of ε-caprolactone by Cyclohexanone Oxidation Using Molecular Oxygen

Abstract

ε-caprolactone is a kind of important organic chemical intermediate, which is mainly used for producing ε-caprolactam, polycaprolactone, polycaprolactone polyol, etc. The B-V oxidation of cyclohexanone to obtain ε-caprolactone by molecular oxygen is gradually attention. Oxygen is a safe and cheap oxidant.The synthesis method with mild reaction conditions can be completed under normal temperature and pressure, providing high conversion of cyclohexanone and good selectivity of ε-caprolactone.Due to the weak oxidize ability of molecular oxygen，the reaction need add benzaldehyde as pro-oxygenic agent .The similar point of benzoic acid and epsilon caprolactone increases the cost of production. In addition, it bring some trouble to product separation and purification.

In this paper, mesoporous Sn-Al₂O₃ were successfully prepared via a facile one-pot evaporation induced self-assembly (EISA) method. We have investigated the catalytic performance in the B-V oxidation of cyclohexanone by molecular oxygen.Different characterization techniques, such as XRD, N₂ adsorption desorption, ICP, NH₃-TPD, TEM and UV-vis spectra were employed to investigate their physical chemical properties, The characteristic results by UV-vis spectra showed that Sn species can be tetrahedrally or hexahedral incorporated into the framework of Al₂O₃. The Sn-Al₂O₃ catalyst when adding 7% the weight percent of Sn in the catalyst shows the highest BET surface area, pore volume and acid amount.The results show that Sn-Al₂O₃-7 as the catalyst,the quality of catalyst and cyclohexanone ratio is 0.28.The quality of benzaldehyde and cyclohexanone ratio is 2.8. The quality of the solvent acetonitrile and cyclohexanone ratio is 30.It reacted 5 hours at the temperature of 70.The conversion of cyclohexanone is 89.1%, The selectivity of ε- caprolactone reach 90.7%.

KEYWORDS: Cyclohexanone；EISA；Baeyer-Villiger oxidation；Molecular oxygen

目 录

摘 要 I

Abstract II

第一章 文献综述 1

1.1 概述 1

1.2 ε-己内酯的产业现状与前景 1

1.3 环己酮B-V氧化法 2

1.3.1 过氧酸氧化法 2

1.3.2 过氧化氢氧化法 3

1.3.3 分子氧氧化法 5

1.4 介孔金属氧化物 6

1.4.1 介孔金属氧化物的制备 6

1.4.2 介孔金属氧化物的应用 8

1.5 本课题研究意义及内容 9

第二章 实验方法 10

2.1 实验原料和设备 10

2.1.1 实验原料 10

2.1.2 实验装置和设备 11

2.2 催化剂的制备 11

2.3 催化剂的表征 12

2.3.1 X射线衍射 12

2.3.2 液氮吸附测试 12

2.3.3 NH₃-TPD 12

2.3.4 Py-IR 12

2.3.5 UV-vis DRS 12

2.3.6 SEM-EDX 13

2.3.7 ICP 13

2.3.8 TEM 13

2.4 B-V氧化制备ε-己内酯反应 13

2.5 实验结果分析 13

第三章 介孔Sn-TiO₂催化环己酮B-V氧化反应 15

3.1 催化剂表征 15

3.1.1 XRD表征 15

3.1.2 液N₂吸附-脱附表征 16

3.1.3 UV-vis DRS表征 17

3.1.4 Py-IR表征 18

3.1.5 TEM表征 19

3.1.6 SEM-EDX表征 19

3.2 不同催化剂的催化性能 20

3.2.1 Sn掺杂量的影响 20

3.2.2 反应温度的影响 21

3.2.3 催化剂用量的影响 21

3.2.4 溶剂用量的影响 22

3.2.5 助氧剂用量的影响 23

3.2.6 反应时间的影响 23

3.3 结论 24

第四章 结论 25

参考文献 26

致 谢 32

第一章 文献综述

1.1 概述

ε-己内酯，又称为6-己内酯，其化学结构式如图1-1所示：

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