论文总字数：27090字

摘 要

环氧苯乙烯又称氧化苯乙烯，在化工生产中时一种关键的有机化学合成体，在有机合成、医疗产业、香料制备等领域都有着重要的作用和宽泛的运用。苯甲醛作为最简单的芳香醛，在实际工业生产中扮演着重要的角色，其在香料产业、染制工业、医疗产业和农药化学等领域都有所涉及。环氧苯乙烯和苯甲醛主要由氧化苯乙烯来制备。而对于氧化反应，氧化剂的选择是其中最重要的环节。与无机氧化剂、有机氧化剂相比，分子氧价格低廉,在工业成本上有相对优势,其绿色环保且不引入杂质,在环境保护上符合社会大力倡导的绿色化学方向,是一种非常合适的绿色氧源。在使用分子氧为氧化剂的基础上，采用合适的催化剂能有效地提高苯乙烯的转化率和选择性，为工业生产提供了更优的方案。本论文的主要内容如下：

对于分子氧氧化苯乙烯，我们配置了α-ZrP和γ-ZrP载体，并取其与相对应的金属盐前体（Co，Ti，Fe，Mn）制备成M-α/γ-ZrP催化剂。经过对空白组和10种催化剂的活性测试，得到Co-γ-ZrP催化剂催化活性较好的结论，所以继续选择Co-γ-ZrP催化剂作为研究对象，DMF作为反应溶剂，探究了温度、钴含量、催化剂质量以及氧气添加方式四个参数对苯乙烯氧化反应的影响。经过探究，我们得到了最佳的反应条件，即反应温度和反应时间分别设置在100℃和10小时，苯乙烯称取0.5 ml，（5%）Co-γ-ZrP 催化剂称取0.05g，溶剂DMF称取10 ml，氧气添加方式为鼓泡O₂，速率为V（O2） = 6-8 ml min⁻¹。在此条件下，我们成功转化了84.7%的苯乙烯，制得产物所得率达到57.1%，环氧苯乙烯和苯甲醛在反应中的选择性能分别达到67.4%和26.2%。

关键词：环氧苯乙烯；苯乙烯；分子氧；氧化；催化剂

Study on oxidation of styrene by molecular oxygen

Abtract

Epoxy styrene, also known as styrene oxide, is a key organic chemical synthesis in chemical production. It plays an important role and is widely used in organic synthesis, medical industry, perfume preparation and other fields. Benzaldehyde, as the simplest aromatic aldehyde, plays an important role in the actual industrial production. It is involved in the perfume industry, dyeing industry, medical industry, pesticide chemistry and other fields. Epoxy styrene and benzaldehyde are mainly prepared from styrene oxide. For oxidation reaction, the selection of oxidant is the most important link. Compared with inorganic oxidant and organic oxidant, molecular oxygen has low price and comparative advantage in industrial cost. It is green and does not introduce impurities. It is a very suitable green oxygen source, which conforms to the direction of green chemistry advocated by the society in environmental protection. On the basis of using molecular oxygen as oxidant, the conversion and selectivity of styrene can be effectively improved by using appropriate catalyst, which provides a better scheme for industrial production. The main contents of this paper are as follows:

For the oxidation of styrene by molecular oxygen, α - ZrP and γ - ZrP supports were prepared, and the corresponding metal salt precursors (CO, Ti, Fe, Mn) were taken to prepare M - α / γ - ZrP catalysts. Through the activity test of blank group and 10 kinds of catalysts, we get the conclusion that the catalytic activity of Co - γ - ZrP catalyst is better. So we continue to choose Co - γ - ZrP catalyst as the research object, DMF as the reaction solvent, and explore the influence of temperature, cobalt content, catalyst quality and oxygen addition formula on styrene oxidation. After investigation, we got the best reaction conditions, that is, the reaction temperature and time were set at 100 ℃ and 10 hours respectively, styrene weighed 0.5 ml, (5%) Co - γ - ZrP catalyst weighed 0.05g, solvent DMF weighed 10 ml, oxygen added in the way of bubbling O2, the rate was V (O2) = 6-8 mL min − 1. Under these conditions, 84.7% of styrene was successfully converted and the yield of the product was 57.1%. The selectivity of styrene epoxide and benzaldehyde in the reaction was 67.4% and 26.2%, respectively.

Keywords: Epoxy styrene; Styrene; Molecular oxygen,;Oxidation;Catalyst

目 录

摘要.......................................................................................................................Ⅰ

Abtract..................................................................................................................Ⅱ

第一章 绪论.........................................................................................................1

1.1 引言............................................................................................................2

1.2 苯乙烯的分子氧氧化过程简述................................................................2

1.2.1 苯乙烯............................................................................................2

1.2.2 苯乙烯的分子氧氧化....................................................................2

1.2.3 苯甲醛、环氧苯乙烯.....................................................................3

1.3 氧化剂——分子氧...................................................................................4

1.3.1 氧化苯乙烯的氧化剂研究进展.....................................................4

1.3.2 分子氧作为氧化剂的优势............................................................5

1.4 苯乙烯分子氧氧化的催化剂研究进展....................................................6

1.4.1金属-有机配体化合物催化剂........................................................6

1.4.2 金属氧化物催化剂.........................................................................6

1.4.3 无机分子筛催化剂........................................................................7

1.4.4 多氧金属盐类催化剂.....................................................................7

1.4.5 负载型催化剂.................................................................................7

1.5 苯乙烯分子氧氧化的应用........................................................................8

1.5.1 苯乙烯氧化产物的应用.................................................................8

1.5.2 研究技术的应用.............................................................................8

1.6 磷酸锆概述................................................................................................8

1.6.1 磷酸锆.............................................................................................8

1.6.2 磷酸锆的制备.................................................................................9

第二章 实验部分...............................................................................................10

2.1 实验试剂与仪器......................................................................................10

2.1.1 实验试剂.......................................................................................10

2.1.2 实验仪器.......................................................................................10

2.2 催化剂的制备..........................................................................................11

2.2.1 α-ZrP和γ-ZrP制备过程.........................................................11

2.2.2 M-α/γ-ZrP制备过程................................................................11

2.3 催化剂表征..............................................................................................11

2.4 催化剂反应测试......................................................................................12

第三章 结果与讨论..........................................................................................13

3.1 催化剂活性测试......................................................................................13

3.2 反应工艺参数优化..................................................................................14

3.3 催化剂的表征..........................................................................................17

3.3.1 催化剂的XRD图谱.......................................................................17

3.3.2 催化剂的SEM和TEM图谱...........................................................18

请支付后下载全文，论文总字数：27090字