Research progress on energy-saving separation of dimethyl carbonate/methanol azeotropic mixture

doi:10.11949/0438-1157.20251332

Abstract

Abstract:

Dimethyl carbonate (DMC), as a crucial green chemical intermediate and solvent for lithium battery electrolytes, In production, DMC and methanol (MeOH) often form an azeotrope with pinch regions, making separation difficult and energy-intensive. The DMC/MeOH composition varies with synthesis routes, including transesterification, oxidation carbonylation, urea alcoholysis, and direct CO₂ synthesis. which directly influences separation complexity, energy demand, and technology applicability, necessitating investigation and research on efficient, low-carbon separation technologies tailored to diverse feed characteristics. To address this, this systematic review examines the mechanisms, key parameters, and application characteristics of four mainstream separation technologies for DMC/MeOH azeotropic systems: pressure swing distillation, azeotropic distillation, extraction distillation, and membrane separation. It focuses on analyzing the adaptability patterns of these technologies based on different feed compositions: For a low concentration of DMC feeding, extractive distillation demonstrates operational flexibility and economic advantages. For the high-concentration DMC feedstocks (near the azeotropic composition), heterogeneous azeotropic distillation and pressure swing distillation become more competitive. Membrane coupling technology provides crucial support for energy-saving separation. It also prospects that the research and development focus will be on the integrated process of coupling distillation with low-cost green membrane materials and other separation media to promote the production of energy-saving and low-carbon DMC.

Key words: dimethyl carbonate, azeotrope, separation, distillation, membrane

摘要：

碳酸二甲酯（DMC）是重要的绿色化工中间体和锂电池电解液溶剂，然而，在DMC生产过程中，DMC与甲醇（MeOH）往往形成共沸体系且存在夹点区域，导致分离难度大，能耗占比高，是制约DMC节能高效生产的关键瓶颈。不同合成工艺如酯交换法、氧化羰基化法、尿素醇解法和二氧化碳直接合成法等所产生的DMC/MeOH混合物组成存在差异，直接影响分离难度、能耗、节能策略及技术适配性，因此亟需开展针对不同进料特性的节能高效分离技术的调研与研究。为此，针对DMC/MeOH共沸体系的节能分离，系统综述了变压精馏、萃取精馏、非均相共沸精馏及膜分离四种技术的基本原理、工艺流程、关键参数、节能方向和应用特性，重点分析了基于不同进料组成的技术适配规律：较低浓度的DMC进料时，萃取精馏展现操作弹性与经济性优势；较高浓度（近共沸组成）的DMC进料时，热集成非均相共沸精馏与变压精馏更具竞争力，精馏-膜耦合技术为节能分离提供重要支撑。展望未来，开发传统精馏耦合低成本绿色材料（膜、离子液体等）的集成工艺，将成为推动DMC节能、低碳和高值化发展的重点研发方向。

关键词: 碳酸二甲酯, 共沸物, 分离, 精馏, 膜

CLC Number:

TQ 028

Yangguang ZHANG, Shun WANG, Yang LIU, Jinke CHU, Hui SHI, Jihai TANG, Mifen CUI, Xu QIAO, Ming XIA. Research progress on energy-saving separation of dimethyl carbonate/methanol azeotropic mixture[J]. CIESC Journal, DOI: 10.11949/0438-1157.20251332.

张阳光, 王顺, 刘杨, 储金科, 石慧, 汤吉海, 崔咪芬, 乔旭, 夏铭. 碳酸二甲酯-甲醇共沸体系的节能分离技术研究进展[J]. 化工学报, DOI: 10.11949/0438-1157.20251332.

Figures/Tables 10

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项目		指标
项目		电子级	优级	一级
碳酸二甲酯，（wt%）	≥	99.99	99.9	99.5
甲醇，（wt%）	≤	0.002	0.020	0.050
水，（wt%）	≤	0.003	0.020	0.10
密度，(ρ)/(g/cm³)		1.071±0.005
钠，/(μg/mL)	≤	1.0
钾，/(μg/mL)	≤	1.0
铜，/(μg/mL)	≤	1.0
铁，/(μg/mL)	≤	1.0
铅，/(μg/mL)	≤	1.0
锌，/(μg/mL)	≤	1.0
铬，/(μg/mL)	≤	1.0
镍，/(μg/mL)	≤	1.0

项目		指标
项目		电子级	优级	一级
碳酸二甲酯，（wt%）	≥	99.99	99.9	99.5
甲醇，（wt%）	≤	0.002	0.020	0.050
水，（wt%）	≤	0.003	0.020	0.10
密度，(ρ)/(g/cm³)		1.071±0.005
钠，/(μg/mL)	≤	1.0
钾，/(μg/mL)	≤	1.0
铜，/(μg/mL)	≤	1.0
铁，/(μg/mL)	≤	1.0
铅，/(μg/mL)	≤	1.0
锌，/(μg/mL)	≤	1.0
铬，/(μg/mL)	≤	1.0
镍，/(μg/mL)	≤	1.0

企业名称	工艺路线	产能（万吨/年）	合计
浙江石化	EC酯交换法	20	酯交换法产能64.1万吨/年
石大胜华	PC酯交换法	12.5
铜陵金泰	PC酯交换法	9
万华化学	PC酯交换法	8
东营海科	PC酯交换法	6
维尔斯化工	PC酯交换法	6
江苏奥克	EC酯交换法	2.6
重庆东能	液相羰基化	7	氧化羰基化法产能18万吨/年
重庆万盛	液相羰基化	6
安徽红四方	气相羰基化	5
中科惠安	尿素醇解	5	尿素醇解法产能5万吨/年

企业名称	工艺路线	产能（万吨/年）	合计
浙江石化	EC酯交换法	20	酯交换法产能64.1万吨/年
石大胜华	PC酯交换法	12.5
铜陵金泰	PC酯交换法	9
万华化学	PC酯交换法	8
东营海科	PC酯交换法	6
维尔斯化工	PC酯交换法	6
江苏奥克	EC酯交换法	2.6
重庆东能	液相羰基化	7	氧化羰基化法产能18万吨/年
重庆万盛	液相羰基化	6
安徽红四方	气相羰基化	5
中科惠安	尿素醇解	5	尿素醇解法产能5万吨/年

进料组成（wt%）		DMC纯度（wt%）	能耗		类型	高压塔压力（MPa）	文献
DMC	MeOH	DMC纯度（wt%）	净蒸汽单耗（吨/吨DMC）	电力（MW/吨）	类型	高压塔压力（MPa）	文献
30	70	99.5	16.79	0	高压-低压两塔变压精馏	1.32	[50]
5	95	99.99	25.80	0	常压-加压-常压三塔精馏（含加压-常压塔热集成）	1.3	[53]
10.9	89.1	99.5	32.73	0	完全热集成变压精馏（低压-高压流程）	1.2	[54]
33.8	66.2	99.99	5.41	0	热耦合变压精馏（高压-低压流程）	1.5	[55]
30	70	99.9	3.33	0.15	中间再沸器的热泵辅助（高压-低压流程）	0.7	[56]
30	70	99.9	0.54	0.84	塔底产品闪蒸式热泵精馏（高压-低压流程）	0.7	[56]
30	70	99.9	0	0.85	蒸汽再压缩热泵精馏（高压-低压流程）	0.7	[56]
30	70	99.9	0	0.84	串级换热蒸汽压缩式精馏（高压-低压流程）	0.7	[56]
30	70	99.9	2.85	0	反应变压精馏	0.76	[57]
10.89	89.91	99.5	16.95	0	变压精馏（高压-低压流程）	1.2	[59]