碳酸二甲酯-甲醇共沸体系的节能分离技术研究进展

doi:10.11949/0438-1157.20251332

化工学报

• •

碳酸二甲酯-甲醇共沸体系的节能分离技术研究进展

张阳光¹(), 王顺¹, 刘杨¹, 储金科¹, 石慧², 汤吉海¹^,³, 崔咪芬¹, 乔旭¹^,³, 夏铭¹()

^1.南京工业大学化工学院材料化学工程全国重点实验室，江苏南京 211816
^2.南京工业大学化学与分子工程学院，江苏南京 211816
^3.国家“江苏先进生物与化学制造协同创新中心”，江苏南京 211816

收稿日期:2025-11-27 修回日期:2026-01-12 出版日期:2026-01-21
通讯作者: 夏铭
作者简介:张阳光（2001—），男，硕士研究生，18317637815@163.com
基金资助:
江苏省碳达峰碳中和科技创新专项资金项目(BT2025004);国家自然科学基金项目(22202225);国家自然科学基金项目(22208361);国家自然科学基金项目(22208154);南京工业大学新进人才启动项目(39801177);南京工业大学2025年校级教改课题(20250132);南京工业大学本科课程思政示范课程建设项目(20240030);南京工业大学化学与分子工程学院教育教学改革拔尖创新人才项目(2024YB02)

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

Yangguang ZHANG¹(), Shun WANG¹, Yang LIU¹, Jinke CHU¹, Hui SHI², Jihai TANG¹^,³, Mifen CUI¹, Xu QIAO¹^,³, Ming XIA¹()

^1.College of Chemical Engineering, Nanjing Tech University, Nanjing 211816, Jiangsu, China
^2.School of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing 211816, Jiangsu, China
^3.Jiangsu National Synergetic Innovation Center for Advanced Materials, Nanjing 211816, Jiangsu, China

Received:2025-11-27 Revised:2026-01-12 Online:2026-01-21
Contact: Ming XIA

摘要/Abstract

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

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

中图分类号:

TQ 028

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.

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.

图/表 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]

碳酸二甲酯-甲醇共沸体系的节能分离技术研究进展

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

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进料组成（wt%）		夹带剂	DMC纯度	净蒸汽单耗（吨/吨DMC）	类型	文献
DMC	MeOH	夹带剂	DMC纯度	净蒸汽单耗（吨/吨DMC）	类型	文献
42.8	51.9	1-丁基-3-甲基咪唑氯盐	99.9 wt%	3.92	DMC/MeOH/水体系	[73]
33	67	苯胺	99.5 wt%	3.11	萃取精馏	[66]
30	70	邻二甲苯	99.9 wt%	6.64	两塔萃取精馏	[60]
32.6	67.3	二甲基亚砜	99.8 wt%	1.94	热集成萃取精馏（萃取MeOH）	[69]
32.6	67.3	水杨酸甲酯	99.8 mol%	3.36	两塔萃取精馏	[68]
32.6	67.3	水杨酸甲酯	99.8 mol%	2.24	热集成萃取精馏	[68]
32.6	67.3	苯甲酸乙酯	99..8 mol%	5.70	两塔萃取精馏	[68]
32.6	67.3	苯甲酸乙酯	99.8 mol%	4.34	热集成萃取精馏	[68]
32.6	67.3	苯酚	99.8 mol%	4.70	萃取精馏工艺	[6]
32.6	67.3	苯酚	99.8 mol%	3.84	热耦合萃取精馏工艺	[6]

进料组成（wt%）		夹带剂	DMC纯度(wt%)	能耗	类型	文献
DMC	MeOH	夹带剂	DMC纯度(wt%)	蒸汽（吨/吨DMC）	类型	文献
		三氯乙烯	99.99		实验分析、工艺优化	[88]
30	70	正庚烷	99.5		模型分析、共沸精馏模拟	[90]
30	70	正庚烷	98.3		共沸精馏实验、优化	[91]
30	70	正己烷	98.7		共沸精馏实验、优化	[91]
30	70	环己烷	99.5		共沸精馏实验、优化	[91]
30	70	1,2-二氯乙烷	99.9		共沸精馏实验、优化	[91]
30	70	四氯化碳	98.8		共沸精馏实验、优化	[91]
30	70	苯	99.6		共沸精馏实验、优化	[91]
32.6	67.3	水	99.95	2.42	热集成双效共沸精馏工艺	[92]
32.6	67.3	环己烷	99.9	0.82吨低压蒸汽+约73.5吨热水（42~55℃）	热泵热集成非均相共沸精馏工艺	[77]

膜材料	进料DMC含量/wt%	膜通量/（g·m^-2·h^-1）	优先渗透	分离因子	选择性	文献
[C8MIM][NTf2] SILM	91.83	739.8	DMC	21.2	67	[94]
[C8C1Pyrr][NTf2] SILM	74	241	DMC	21	48.41	[94]
PDMS	30	7600	DMC	3.2		[96]
MTES-MFI/PDMS	30	11500	DMC	3.6		[96]
MOF-801-15%AA	90	3736	MeOH	629	157	[97]
GO-Zn2+	90	707	MeOH	61.9		[98]
PERVAP™1255	27.5	705	MeOH	14.41		[100]
SAPO-34 分子筛	10	14000-17000	MeOH	600-2000		[101]
PEEK-WC	3.8-96.2	78-227	MeOH	0.25-13.4	0.2-3.5	[102]

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