H2O2/乙腈体系下MgO催化环己酮Baeyer-Villiger绿色氧化合成ε-己内酯的研究

doi:10.11949/0438-1157.20201245

摘要/Abstract

摘要：

在H₂O₂/乙腈体系下以沉淀法制备的MgO为催化剂催化Baeyer-Villiger（B-V）氧化环己酮合成ε-己内酯，考察了制备条件和反应条件对环己酮转化率和己内酯收率的影响。根据实验结果，Mg(NO₃)₂·6H₂O为前体，在煅烧温度为600℃、煅烧时间为2 h时制备MgO氧化性能最佳，由X射线衍射（XRD）、扫描电镜（SEM）进行了分析，可知随温度升高MgO粒径逐渐增大，500~800℃范围内，MgO晶粒尺寸由9.53 nm增大到29.49 nm。在n（催化剂）∶n（环己酮）=0.45∶1、n（乙腈）∶n（环己酮）=12∶1、n（双氧水）∶n（环己酮）=10∶1、70℃、6 h时获得环己酮转化率95.2%及ε-己内酯收率83.1%。对双氧水B-V氧化环己酮机理进行了深入的研究，采用在线原位红外光谱对反应进行实时监测与分析，验证了其过氧缩酰胺反应路径。

关键词: 环己酮, ε-己内酯, 有机化合物, 氧化, 反应机理

Abstract:

In the H₂O₂/acetonitrile system, MgO prepared by precipitation method was used as a catalyst to catalyze the Baeyer-Villiger (B-V) oxidation of cyclohexanone to synthesize ε-caprolactone. The effect of the preparation conditions and reaction conditions on the conversion to cyclohexanone and the yield to ε-caprolactone were discussed. According to the experimental results, Mg(NO₃)₂·6H₂O was used as the precursor, and the best oxidation performance was obtained when the calcination temperature was 600℃ and the calcination time was 2 h. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used. The analysis results show that the MgO particle increases from 9.53 nm to 29.49 nm when the temperature is in the range of 500℃ to 800℃. In n(catalyst)∶n(cyclohexanone) = 0.45∶1, n(acetonitrile)∶n(cyclohexanone) = 12∶1, n(hydrogen peroxide)∶ n(cyclohexanone) = 10∶1, 70℃, 6 h, the conversion rate of cyclohexanone was 95.2% and the yield of ε-caprolactone was 83.1%. The mechanism of hydrogen peroxide B-V oxidation of cyclohexanone was studied in-depth, and the reaction was analyzed in real time by online in-situ infrared spectroscopy. The peroxyacetal reaction path was verified.

Key words: cyclohexanone, ε-caprolactone, organic compound, oxidation, reaction mechanism

中图分类号:

TQ 255

朱倩倩, 靳海波, 郭晓燕, 何广湘, 马磊, 张荣月, 谷庆阳, 杨索和. H₂O₂/乙腈体系下MgO催化环己酮Baeyer-Villiger绿色氧化合成ε-己内酯的研究[J]. 化工学报, 2021, 72(5): 2638-2646.

ZHU Qianqian, JIN Haibo, GUO Xiaoyan, HE Guangxiang, MA Lei, ZHANG Rongyue, GU Qingyang, YANG Suohe. Study on synthesis of ε-caprolactone with MgO catalysis by Baeyer-Villiger green oxidation of cyclohexanone in H₂O₂/acetonitrile system[J]. CIESC Journal, 2021, 72(5): 2638-2646.

图/表 13

图1 不同制备条件对催化剂性能的影响

Fig.1 Effect of different preparation conditions on catalyst performance

图2 不同煅烧温度下MgO的XRD谱图

Fig.2 XRD patterns of MgO at different calcination temperatures

图3 不同煅烧温度下MgO的SEM图（a）~（d）放大倍数为5千倍，（e）~（h）放大倍数为10万倍；（a）~（d）和（e）~（h）的煅烧温度都依次为500、600、700、800℃

Fig.3 SEM images of MgO at different calcination temperatures

图4 催化剂用量对反应的影响（反应条件：环己酮30 mmol；30%（质量分数）双氧水35 ml；乙腈20 ml；60℃；5 h）

Fig.4 The influence of the amount of catalyst on the reaction

图5 溶剂用量对反应的影响（反应条件：环己酮30 mmol；30%（质量分数）双氧水35 ml；催化剂0.54 g；60℃；5 h）

Fig.5 The effect of the amount of solvent on the reaction

图6 双氧水用量对反应的影响（反应条件：环己酮30 mmol；乙腈15 ml；催化剂0.54 g；60℃；5 h）

Fig.6 The effect of hydrogen peroxide on the reaction

图7 反应温度对反应的影响（反应条件：环己酮30 mmol；30%（质量分数）双氧水30.7 ml；催化剂0.54 g；5 h）

Fig.7 The effect of temperature on the reaction

图8 反应时间对反应的影响（反应条件：环己酮30 mmol；30%（质量分数）双氧水30.7 ml；催化剂0.54 g； 70℃）

Fig.8 The effect of time on the reaction

图9 环己酮B-V氧化副反应路线

Fig.9 Cyclohexanone B-V oxidation side reaction route

图10 路线Ⅰ：H2O2/乙腈体系下MgO催化环己酮B-V氧化反应机理（仅酮基碳被活化）

Fig.10 Route Ⅰ: MgO-catalyzed oxidation mechanism of cyclohexanone B-V in H2O2/acetonitrile system

图11 路线Ⅱ：H2O2/乙腈体系下MgO催化环己酮B-V氧化反应机理（酮羰基与H2O2分子均被活化）

Fig.11 Route Ⅱ: MgO-catalyzed oxidation mechanism of cyclohexanone B-V in H2O2/acetonitrile system

图12 MgO催化环己酮B-V氧化合成ε-己内酯原位红外光谱图

Fig.12 In-situ infrared spectroscopy of MgO catalytic cyclohexanone B-V oxidation to ε-caprolactone

图13 MgO催化B-V氧化合成ε-己内酯中乙酰胺与过氧缩酰胺原位红外光谱峰强变化

Fig.13 MgO catalyzed oxidation of B-V to synthesize ε-caprolactone acetamide and peroxyacetal in-situ infrared spectrum peak intensity changes

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H₂O₂/乙腈体系下MgO催化环己酮Baeyer-Villiger绿色氧化合成ε-己内酯的研究

Study on synthesis of ε-caprolactone with MgO catalysis by Baeyer-Villiger green oxidation of cyclohexanone in H₂O₂/acetonitrile system

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