酸性可控的蒙脱土制备及其催化香兰醇合成香兰基丁醚

doi:10.16085/j.issn.1000-6613.2023-2108

摘要/Abstract

摘要：

使用不同浓度的盐酸溶液对钠基蒙脱土进行处理，考察不同酸浓度处理对蒙脱土结构及对香兰醇反应合成香兰基丁醚的影响。表征结果显示：对比钠基蒙脱土，蒙脱土经酸化处理后结构及酸性的变化较为明显，酸处理浓度较低时，蒙脱土层状骨架结构未受明显影响，酸处理浓度较高时，蒙脱土层状骨架结构遭到破坏；随着酸处理浓度的增加，催化剂比表面积逐渐增加，酸性先升高后降低，在酸处理浓度为0.11mol/L时，催化剂酸性最高，催化性能最好，所获得的香兰醇转化率和香兰基丁醚收率分别为99.9%和93.6%；对催化剂构效关系研究证实催化性能与催化剂酸性呈现线性正相关性，说明催化性能受蒙脱土结构和酸性所主导，在维持蒙脱土结构基础上提高酸性有助于提高催化活性。

关键词: 香兰醇, 蒙脱土, 酸处理, 香兰基丁醚

Abstract:

A series of montmorillonites were treated by using hydrochloric acid solutions with different concentrations, and the effect of treating montmorillonite with different acid concentrations on the conversion of vanillyl alcohol to vanillyl butyl ether was investigated. Characterization results showed that compared to sodium-based montmorillonite, it was found that the structure and acidity of acid-activated montmorillonite changed significantly, and the lamellar skeleton structure of montmorillonite was not significantly affected at a lower concentration of acid treatment, while the lamellar skeleton structure of montmorillonite was destroyed at a higher concentration of acid treatment. With the increase of acid treatment concentration, the specific surface area of the catalyst increased gradually, and the acidity was increased firstly and then decreased. The highest acidity and the best catalytic performance were obtained at the acid treatment concentration of 0.11mol/L, and the obtained vanillin alcohol conversion and vanillyl butyl ether yields were 99.9% and 93.6%, respectively. The study on the structure-performance relationship of the catalyst confirmed that the catalytic performance showed a linear positive correlation with the acidity of the catalyst, indicating that the catalytic performance was dominated by the structure of the montmorillonite and acidity. On the basis of maintaining the montmorillonite structure, the increase of the acidity could increase the catalytic activity.

Key words: vanillyl alcohol, montmorillonite, acid treatment, vanillyl butyl ether

中图分类号:

TQ658

赵曼玉, 张鹏, 张朋泽, 朱明远. 酸性可控的蒙脱土制备及其催化香兰醇合成香兰基丁醚[J]. 化工进展, 2024, 43(12): 6925-6932.

ZHAO Manyu, ZHANG Peng, ZHANG Pengze, ZHU Mingyuan. Preparation of acid-controlled montmorillonite and its catalytic synthesis of vanillin butyl ether from vanillyl alcohol[J]. Chemical Industry and Engineering Progress, 2024, 43(12): 6925-6932.

图/表 12

图1 不同催化剂对香兰醇醚化反应的影响[m(香兰醇)∶m(正丁醇)∶m(Acid-MMT-c)=1.5∶24∶1，T=80℃，t=3h]

图2 不同反应条件对香兰醇醚化反应的影响

图3 XRD表征a—Na-MMT；b—Acid-MMT-0.0011；c—Acid-MMT-0.011；d—Acid-MMT-0.11；e—Acid-MMT-1.1；f—Acid-MMT-1.8；g—Acid-MMT-2.2

图4 FT-IR图a—Na-MMT；b—Acid-MMT-0.0011；c—Acid-MMT-0.011；d—Acid-MMT-0.11；e—Acid-MMT-1.1；f—Acid-MMT-1.8；g—Acid-MMT-2.2

表1 各样品的XRF分析

样品	w(SiO₂)/%	w(Al₂O₃)/%	w(SiO₂)/w(Al₂O₃)
Na-MMT	73.14	16.02	4.56
Acid-MMT-0.011	75.12	16.28	4.61
Acid-MMT-0.11	77.25	16.56	4.66
Acid-MMT-2.2	95.85	2.91	32.94

图5 不同酸浓度处理蒙脱土的SEM和EDS图像

图6 不同酸处理浓度蒙脱土的N2吸附-脱附曲线

表2 不同浓度盐酸酸化蒙脱土的孔结构性质

催化剂	S_BET/m²·g^-1	V_pore/cm³·g^-1	D_pore/nm
Na-MMT	39.47	0.12	15.13
Acid-MMT-0.0011	53.36	0.12	12.99
Acid-MMT-0.011	62.22	0.14	13.41
Acid-MMT-0.11	80.21	0.15	12.69
Acid-MMT-1.1	261.67	0.44	7.68
Acid-MMT-1.8	226.47	0.45	9.43
Acid-MMT-2.2	219.40	0.59	12.50

图7 蒙脱土酸处理浓度、比表面积与活性构效关系

图8 Na-MMT、Acid-MMT-0.11、Acid-MMT-2.2的热重图

图9 NH3-TPD图

图10 蒙脱土酸处理浓度、酸性与活性构效关系

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