Toluene-Templated Synthesis of ZIF-93 and Its Adsorptive Separation of 1，3-Propanediol and 2，3-Butanediol

doi:10.19894/j.issn.1000-0518.230087

Chinese Journal of Applied Chemistry ›› 2023, Vol. 40 ›› Issue (9): 1302-1311.DOI: 10.19894/j.issn.1000-0518.230087

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Toluene-Templated Synthesis of ZIF-93 and Its Adsorptive Separation of 1，3-Propanediol and 2，3-Butanediol

Meng-Yao WANG, Mei-Zhen GAO, Qi SHI(), Jin-Xiang DONG

College of Chemical Engineering and Technology，Taiyuan University of Technology，Taiyuan 030024，China

Received:2023-04-03 Accepted:2023-07-19 Published:2023-09-01 Online:2023-09-14
Contact: Qi SHI
About author:shiqi594@163.com
Supported by:
the National Natural Science Foundation of China(22278289)

Abstract

Abstract:

The bio-based 1，3-propanediol （1，3-PDO） stock solution after pretreatment is mainly composed of low concentration of 1，3-PDO and 2，3-butanediol （2，3-BDO）. 1，3-PDO and 2，3-BDO are diols and contain two hydroxyl groups that can form strong hydrogen bonds with the large amount of water present， increasing the difficulty of separation. However， conventional hydrophobic adsorbents with only van der Waals cannot achieve effective separation of diols by dynamic column adsorption. Therefore， ZIF-93 with van der Waals group —CH₃ and hydrogen bonding group —CHO is selected to investigate its batch and dynamic column adsorption capacity on low concentration of 2，3-BDO/1，3-PDO. Firstly， toluene is introduced as solvent and template agent in the synthesis of ZIF-93， and the structural unit lta cage of ZIF-93 is supported by π?-?π interaction between toluene and imidazole-based ligands as well as toluene molecules， which effectively increases the BET surface area and microporous pore volume of ZIF-93. The results show that the dynamic column adsorption capacity of ZIF-93 for 2，3-BDO/1，3-PDO （50/50 g/L） is 69.9 mg/g/17.3 mg/g， and the selectivity for 2，3-BDO/1，3-PDO is 4.0. Compared with the conventional hydrophobic adsorbent， ZIF-93 with hydrogen-bonding groups has an increased slope of the breakthrough curve， a shorter mass transfer interval， and an increased breakthrough time， thus improving the effective utilization of the adsorption bed and facilitating the continuous separation operation in industry. The simulation results show that the hydrogen bonding interaction formed between —CHO of ZIF-93 and —OH/—CH₃ of 2，3-BDO is higher than that with 1，3-PDO， thus achieving effective separation of low concentration of 2，?3-BDO/1，?3-PDO. After three adsorption-resolution cycle experiments， the adsorption capacity of ZIF-93 on 2，3-BDO does not change， and ZIF-93 still maintains good stability. Therefore， ZIF-93 is an efficient adsorbent for the separation of diols in aqueous solution.

Key words: Zeolitic imidazolate frameworks, ZIF-93, Template agent, Adsorptive separation, Bio-diols

CLC Number:

O647.3

Meng-Yao WANG, Mei-Zhen GAO, Qi SHI, Jin-Xiang DONG. Toluene-Templated Synthesis of ZIF-93 and Its Adsorptive Separation of 1，3-Propanediol and 2，3-Butanediol[J]. Chinese Journal of Applied Chemistry, 2023, 40(9): 1302-1311.

Figures/Tables 7

Fig.1 （A） PXRD patterns，（B） solid 13C NMR spectra，（C） N2 adsorption-desorption isotherm and （D） pore size analysis of ZIF-93

Fig.2 The arrangement of toluene in ZIF-93：（A） 8-Membered ring towards the front；（B） 4-Membered ring over the front

Fig.3 （A） ATR-FTIR characterization，（B） TG curves，（C） SEM analysis and （D） water vapor adsorption isotherm and contact angle of ZIF-93

Fig.4 （A） Single-component and （B） competitive binary-component adsorption isotherms for 2，3-BDO and 1，3-PDO of ZIF-93

Fig.5 Dynamic column breakthrough curves for binary-component 2，3-BDO （50 g/L）/1，3-PDO （50 g/L） of （A） ZIFf-71 and （B） ZIF-93

Fig.6 Adsorption sites on ZIF-93 for 2，3-BDO and 1，3-PDO

Fig.7 （A） Adsorption capacity of binary-components 2，3-BDO（50 g/L）/1，3-PDO（50 g/L） and （B） PXRD patterns of ZIF-93 during cyclic adsorption-desorption process

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[1]	Wang LI. Morphology Control and Catalytic Dehydrogenation Performance of Zeolitic Imidazolate Frameworks⁃8 [J]. Chinese Journal of Applied Chemistry, 2022, 39(7): 1065-1072.
[2]	Jian-Shuang ZHANG, Mei-Zhen GAO, Meng-Yao WANG, Qi SHI, Jin-Xiang DONG. Zeolitic Imidazolate Framework ZIF‑71 for Adsorption and Separation of 2，3‑Butanediol/1，3‑Propanediol From Dilute Aqueous Solutions [J]. Chinese Journal of Applied Chemistry, 2022, 39(11): 1735-1745.

Toluene-Templated Synthesis of ZIF-93 and Its Adsorptive Separation of 1，3-Propanediol and 2，3-Butanediol

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