COSMO-RS prediction, liquid-liquid equilibrium experiment and quantum chemistry calculation for the separation of methanol and dimethyl carbonate system using dihydrogen phosphate ionic liquids

IF 5.5 3区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of the Taiwan Institute of Chemical Engineers Pub Date : 2025-03-23 DOI:10.1016/j.jtice.2025.106102

Jiaxin Liu, Qinqin Zhang, Chao Wang, Yu Sheng, Jiahui Liu, Yulin Li, Hua Xin, Zhigang Zhang

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Abstract

Background

Dimethyl carbonate (DMC) is a high value-added chemical, and is also an important chemical raw material and solvent in industry, with a wide range of applications. During the synthesis of dimethyl carbonate, the azeotropic mixtures of DMC and methanol (MeOH), which cannot be separated through conventional distillation, will form inevitably.

Methods

In this paper, the feasibility of liquid-liquid extraction separation of DMC and MeOH using ionic liquids (ILs) was explored. 1-ethyl-3-methylimidazolium dihydrogen phosphate ([C₂MIM][H₂PO₄]), 1‑butyl‑3-methylimidazolium dihydrogen phosphate (C₄MIM] [H₂PO₄]), and 1-pentyl-3-methylimidazolium dihydrogen phosphate ( [C₅MIM] [H₂PO₄]) were selected as extractants based on the selectivity calculated by COSMO-RS model as well as the physio-chemical properties of ILs. Liquid-liquid equilibrium (LLE) data for the DMC (1)- MeOH (2)- IL (3) ternary systems were measured at 303.15 K and atmospheric pressure. Selectivity and partition coefficients were calculated based on the experimental LLE results to assess the separation performance of ILs. Othmer-Tobias, Bachman and Hand equations were used to check the quality of the experimental data. NRTL was utilized to correlate the experimental data to obtain the binary interaction parameters. The separation mechanism of the three ILs was explored by interaction energy, IGMH analysis, AIM topological analysis, and FT-IR. Finally, the feasibility of the proposed method in industrial scale was explored using Aspen plus software.

Significant findings

The experimental results demonstrated that all the three ILs could be used as potential extractants for liquid-liquid extraction separation of DMC and MeOH. Quantum chemistry calculation and FT-IR results showed it was hydrogen bond that played a key role in the separation of DMC and MeOH mixture using ionic liquids with [H₂PO₄] anions. Liquid-liquid extraction separation of DMC and MeOH in industrial scale is feasible.

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磷酸二氢离子液体分离甲醇和碳酸二甲酯体系的cosmos - rs预测、液-液平衡实验和量子化学计算

碳酸二甲酯（DMC）是一种高附加值化学品，也是工业上重要的化工原料和溶剂，具有广泛的应用前景。在碳酸二甲酯的合成过程中，不可避免地会形成DMC与甲醇（MeOH）的共沸混合物，这是常规蒸馏无法分离的。方法探讨了离子液体液液萃取分离DMC和MeOH的可行性。根据cosmos - rs模型计算的选择性和il的理化性质，选择1-乙基-3-甲基咪唑磷酸二氢（[C2MIM][H2PO4]）、1-丁基-3-甲基咪唑磷酸二氢（C4MIM] [H2PO4]）和1-戊基-3-甲基咪唑磷酸二氢（[C5MIM] [H2PO4]）作为萃取剂。在303.15 K和常压下测量了DMC (1)- MeOH (2)- IL(3)三元体系的液液平衡（LLE）数据。根据LLE实验结果计算了选择性系数和分配系数，评价了LLE的分离性能。采用other - tobias， Bachman和Hand方程来检验实验数据的质量。利用NRTL对实验数据进行关联，得到二元相互作用参数。通过相互作用能、IGMH分析、AIM拓扑分析和FT-IR分析，探讨了三种il的分离机理。最后，利用Aspen plus软件对该方法在工业规模下的可行性进行了探讨。实验结果表明，这3种il均可作为萃取剂用于DMC和MeOH的液液萃取分离。量子化学计算和FT-IR结果表明，在[H2PO4]阴离子液体中，氢键对DMC和MeOH混合物的分离起了关键作用。液液萃取分离DMC和MeOH在工业规模上是可行的。

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来源期刊

Journal of the Taiwan Institute of Chemical Engineers 工程技术-工程：化工

CiteScore

9.10

自引率

14.00%

发文量

362

审稿时长

35 days

期刊介绍： Journal of the Taiwan Institute of Chemical Engineers (formerly known as Journal of the Chinese Institute of Chemical Engineers) publishes original works, from fundamental principles to practical applications, in the broad field of chemical engineering with special focus on three aspects: Chemical and Biomolecular Science and Technology, Energy and Environmental Science and Technology, and Materials Science and Technology. Authors should choose for their manuscript an appropriate aspect section and a few related classifications when submitting to the journal online.