Catalytic isomerization of α-terpineol to 1,8-cineole in supercritical carbon dioxide

doi:10.11949/0438-1157.20201838

Abstract

Abstract:

This work proposes a method for supercritical carbon dioxide to intervene α-terpineol to synthesize 1,8-cineole. In addition, the diode-array detector was employed to measure the maximum absorption wavelength of the α-terpineol/cyclohexane mixture in supercritical carbon dioxide for analysis of the relationship between the amount of carbon dioxide and the polarity of the system. The catalytic isomerization was studied by considering the effects of polarity, solvent amount, and carbon dioxide pressure. The plausible mechanism for isomerization of α-terpineol to 1,8-cineole by phosphotungstic acid/poly(ionic liquid) (PW/PIL) in supercritical carbon dioxide was proposed. This work offers a novel green and efficient supercritical technique for the synthesis of 1,8-cineole. In supercritical carbon dioxide, 89.3% conversion of α-terpineol and 54.6% selectivity to 1,8-cineole were obtained with the mass ratio of cyclohexane to α-terpineol 10∶1 and the molar ratio of PW/PIL catalyst to α-terpineol 0.0163∶1, at 19.0 MPa, 50℃ for 8 h. The results showed that supercritical carbon dioxide as co-solvent expanded the applied solvent as well as reducing the polarity of the system; therefore, the catalyst aggregation was alleviated obviously, and as a result the selectivity of 1,8-cineole was increased.

Key words: α-terpineol, 1,8-cineole, supercritical carbon dioxide, diode-array detector, polarity

摘要：

提出超临界二氧化碳介入α-松油醇异构合成1,8-桉叶素的方法，并采用二极管阵列检测器测量超临界二氧化碳下α-松油醇/环己烷体系的最大吸收波长研究二氧化碳加入量与极性的关系。考察了溶剂体系极性、溶剂量和二氧化碳压力对磷钨酸/聚离子液体（PW/PIL）催化剂催化α-松油醇异构合成1,8-桉叶素的影响，并探讨了超临界二氧化碳介质中，PW/PIL催化剂催化α-松油醇异构合成1,8-桉叶素可能的反应机理。开发了一种绿色高效的1,8-桉叶素合成工艺，当环己烷/α-松油醇的质量比10∶1，PW/PIL催化剂/α-松油醇的摩尔比0.0163∶1，CO₂压力19.0 MPa，50℃反应8 h时，α-松油醇的转化率为89.3%，1,8-桉叶素的选择性为54.6%。研究表明，超临界二氧化碳起到共溶剂、膨胀溶剂、降低溶剂体系极性的三重作用，从而改善了催化剂的团聚现象，提高了1,8-桉叶素的选择性。

关键词: α-松油醇, 1,8-桉叶素, 超临界二氧化碳, 二极管阵列检测器, 极性

CLC Number:

TQ 032.4

HONG Yanzhen, WANG Di, LI Zhuoyu, XU Yanan, WANG Hongtao, SU Yuzhong, PENG Li, LI Jun. Catalytic isomerization of α-terpineol to 1,8-cineole in supercritical carbon dioxide[J]. CIESC Journal, 2021, 72(7): 3680-3685.

洪燕珍, 王笛, 李卓昱, 徐亚南, 王宏涛, 苏玉忠, 彭丽, 李军. 超临界二氧化碳介入的α-松油醇催化合成1，8-桉叶素[J]. 化工学报, 2021, 72(7): 3680-3685.

Figures/Tables 7

Fig.1 The schematic diagram for reaction in supercritical CO21—back pressure regulator; 2—compressor; 3—high pressure reactor; 4—cylinder; 5—water bath; 6—magnetic stirrer; 7—buffer tank; V-1—V-3—valves; T—temperature controller; P—pressure gage

Fig.2 Effect of solvent usage on catalytic activity and polarity

Table 1 The maximum absorption wavelength of the α-terpineol/cyclohexane mixture

压力/MPa	$V C O 2$ ︰V_环己烷	最大吸收波长 /nm	仪器
9	9∶1	211	SFC Pre30
9	8∶2	215	SFC Pre30
9	7∶3	222	SFC Pre30
0.1	—	224	常压UV-780

Table 1 The maximum absorption wavelength of the α-terpineol/cyclohexane mixture

压力/MPa	$V C O 2$ ︰V_环己烷	最大吸收波长 /nm	仪器
9	9∶1	211	SFC Pre30
9	8∶2	215	SFC Pre30
9	7∶3	222	SFC Pre30
0.1	—	224	常压UV-780

Fig.3 The maximum absorption wavelength of the α-terpineol/cyclohexane mixture in supercritical carbon dioxide

Fig.4 Volume expansion of the supercritical carbon dioxide/α-terpineol/cyclohexane systems

Fig.5 Effect of solvent usage in supercritical carbon dioxide on catalytic activity

Fig.6 Effect of pressure in supercritical carbon dioxide on catalytic activity

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