[BMIm]Br离子液体辅助HZSM-5催化乙酸环己酯高选择性水解反应

doi:10.11949/0438-1157.20191177

摘要/Abstract

摘要：

为提高HZSM-5催化乙酸环己酯水解反应生成环己醇的选择性，筛选得到了离子液体[BMIm]Br助剂。发现[BMIm]Br可抑制乙酸环己酯热分解副反应的发生，大幅度提高环己醇选择性。并且，[BMIm]Br可与HZSM-5发生离子交换反应，释放出的H⁺可促进乙酸环己酯水解反应的发生。在优化的条件下，[BMIm]Br辅助HZSM-5催化乙酸环己酯水解反应转化率为87.5%，环己醇选择性为97.3%。考察了[BMIm]Br和HZSM-5的重复使用性。前者具有较好的稳定性，而HZSM-5活性随循环使用的次数增加而下降。这是由于HZSM-5的骨架铝含量在反应中逐渐降低，导致Br?nsted酸中心数量减少，因此其催化活性逐渐降低。

关键词: 环己醇, 乙酸环己酯, 水解, HZSM-5, 离子液体

Abstract:

To improve the selectivity of HZSM-5 to catalyze the hydrolysis reaction of cyclohexyl acetate to cyclohexanol, an ionic liquid [BMIm]Br auxiliary was screened. It was found that [BMIm]Br could inhibit the side-reaction, thermal decomposition of cyclohexyl acetate, and increase the selectivity to cyclohexanol greatly. Moreover, the ion exchange between [BMIm]Br and HZSM-5 could promote the generation of H⁺, which could accelerate the hydrolyzation of cyclohexyl acetate. Under the optimized reaction conditions, cyclohexyl acetate conversion was 87.5% with 97.3% cyclohexanol selectivity over HZSM-5 assisted by [BMIm]Br. The reusability of [BMIm]Br and HZSM-5 was investigated respectively, and the former exhibited good stability. However, the catalytic activity of HZSM-5 decreased gradually with the recycling times. It was due to the decreasing of framework Al content of HZSM-5 during the reaction, which led to the reduction of Br?nsted acid sites and therefore resulted in the decreased activity.

Key words: cyclohexanol, cyclohexyl acetate, hydrolyzation, HZSM-5, ionic liquid

中图分类号:

O 643.3

朱林, 韩威, 李文松, 邬长城, 李芳, 薛伟, 王延吉. [BMIm]Br离子液体辅助HZSM-5催化乙酸环己酯高选择性水解反应[J]. 化工学报, 2020, 71(4): 1609-1617.

Lin ZHU, Wei HAN, Wensong LI, Changcheng WU, Fang LI, Wei XUE, Yanji WANG. Highly selective hydrolyzation of cyclohexyl acetate over HZSM-5 assisted by [BMIm]Br ionic liquid[J]. CIESC Journal, 2020, 71(4): 1609-1617.

图/表 13

图1 环己烯间接水合反应方程式

Fig.1 Reaction equations of indirect hydration of cyclohexene

表1 不同助剂对HZSM-5催化乙酸环己酯水解反应的影响

Table 1 Effect of different co-catalyts on hydrolyzation of cyclohexyl acetate over HZSM-5 catalyst

No.	Catalyst	Co-catalyst^①	Cyclohexyl acetate conversion /%	Cyclohexanol selectivity/%
1	—	—	1.0	32.0
2	HZSM-5	—	56.9	27.9
3	HZSM-5	[BMIm]BF₄	35.4	99.7
4	HZSM-5	[BMIm]Br	74.8	98.4
5	—	[BMIm]BF₄	2.6	100
6	—	[BMIm]Br	1.3	100
7	HZSM-5	[HSO₃BMIm]HSO₄^[20]	81.6	79.7
8	HZSM-5	NaBr ^[24]	56.1	48.0
9	HZSM-5	ZnSO₄^[24]	4.1	75.3
10	HZSM-5	NaHSO₄^[24]	67.7	42.8

图2 反应温度对HZSM-5/[BMIm]Br催化乙酸环己酯水解反应的影响

Fig.2 Effect of reaction temperature on hydrolyzation of cyclohexyl acetate over HZSM-5/[BMIm]Br(m(HZSM-5)=1.2 g,V(cyclohexyl acetate)=8 ml (55 mmol), V(H2O)=24 ml (1333 mmol), m([BMIm]Br)=2 g,t= 5 h)

图3 反应时间对HZSM-5/[BMIm]Br催化乙酸环己酯水解反应的影响

Fig.3 Effect of reaction time on hydrolyzation of cyclohexyl acetate over HZSM-5/[BMIm]Br (m(HZSM-5)=1.2 g, V(cyclohexyl acetate)=8 ml (55 mmol),V(H2O)=24 ml (1333 mmol),m([BMIm]Br)=2 g,T= 140℃)

图4 [BMIm]Br用量对HZSM-5催化乙酸环己酯水解反应的影响

Fig.4 Effect of [BMIm]Br dosage on hydrolyzation of cyclohexyl acetate over HZSM-5 catalyst(m(HZSM-5)=1.2 g, V(cyclohexyl acetate)=8 ml (55 mmol),V(H2O)=24 ml (1333 mmol), T= 140℃,t=5 h)

图5 [BMIm]Br辅助HZSM-5催化乙酸环己酯水解反应机理

Fig.5 Proposed mechanism of hydrolyzation of cyclohexyl acetate over HZSM-5 assisted by [BMIm]Br

图6 HZSM-5催化乙酸环己酯水解反应中[BMIm]Br的重复使用性能

Fig.6 Reusability of [BMIm]Br for hydrolyzation of cyclohexyl acetate catalyzed by HZSM-5 (m([BMIm]Br)=3 g, m(HZSM-5)=1.2 g,V(cyclohexyl acetate) = 8 ml, V(H2O)=24 ml,T=140℃, t=5 h)

图7 乙酸环己酯水解反应中HZSM-5重复使用性能

Fig.7 Reusability of HZSM-5 for hydrolyzation of cyclohexyl acetate(m([BMIm]Br)=3 g,m(HZSM-5)=1.2 g, V(cyclohexyl acetate) = 8 ml,V(H2O)=24 ml, T=140℃, t=5 h)

图8 HZSM-5的XRD谱图

Fig.8 XRD patterns of HZSM-5a—fresh HZSM-5; b—once used HZSM-5; c—HZSM-5 used for 4 times

图9 HZSM-5的NH3-TPD曲线

Fig.9 NH3-TPD profiles of HZSM-5a—fresh HZSM-5; b—once used HZSM-5; c—HZSM-5 used for 4 times

图10 使用前后HZSM-5分子筛的XRD谱图

Fig.10 XRD patterns of HZSM-5 before and after reactiona—fresh HZSM-5; b—recovered HZSM-5, washed with ethanol and dried at 120℃ for 12 h; c—recovered HZSM-5, sample b calcined at 550℃ for 5 h

图11 HZSM-5的红外光谱图

Fig.11 FT-IR spectra of HZSM-5

图12 乙酸环己酯水解反应转化率与HZSM-5骨架铝含量关联图

Fig.12 Correlation of cyclohexyl acetate conversion in hydrolyzation with framework Al content of HZSM-5

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