反应精馏合成甲基丙烯酸甲酯工艺优化及节能

doi:10.16085/j.issn.1000-6613.2023-0389

摘要/Abstract

摘要：

以等摩尔下甲基丙烯酸和甲醇反应精馏合成甲基丙烯酸甲酯过程为研究对象，探究了塔内耦合反应精馏工艺（RD）和带侧反应器的反应精馏工艺（SRC）。在MAA处理量为10kmol/h、MAA的转化率为98.6%条件下，以最小年总费用（TAC）为目标函数，采用序贯优化迭代法，经Aspen Plus对RD工艺和SRC工艺进行模拟计算与优化研究，得到优化后的RD工艺和SRC工艺参数；以TAC和CO₂排放量为考察指标，对比了RD工艺和SRC工艺。研究结果表明：相比于RD工艺，SRC工艺具有显著优势，TAC降低8.5%，CO₂排放量降低16.3%，此时SRC工艺参数为：N_T=26，N_R=3，3台侧反应器（R1/R2/R3）的进料位置N_F分别为第6、第11和第14块塔板，SRC塔侧线采出进侧反应器（R2/R3）的进料位置为第23和第24块塔板，进3台侧反应器（R1/R2/R3）的MeOH的分配比为0.58∶0.22∶0.2，TAC为115.23×10⁴ CNY/a。

关键词: 反应精馏, 酯化, 甲基丙烯酸甲酯, 最小年度总费用, 二氧化碳排放量, 优化设计

Abstract:

Two processes, conventional reactive distillation (RD) processes combining reaction and separation unit, and the distillation column coupled with side reactors (SRC) processes, were explored for the reactive distillation process for the synthesis of methyl methacrylate, by the equal mole ratio of methacrylic acid and methanol, in this study. At the MAA mole flow of 10 kmol/h and the conversion efficiency of 98.6%, the optimal operating conditions for minimizing the total annual cost (TAC) were determined via the Aspen Plus sequential iterative optimization procedure. The above two techniques were simulated and optimized in terms of the minimization of the total annual cost and the CO₂ emission. The results showed that SRC process had significant advantages, and comparing with RD process, TAC can be reduced by 8.5%, CO₂ emission can be reduced by 16.3%. The minimum TAC was 115.23 million yuan per year under the optimal operating conditions, which included SRC column stages of 26, reactors of 3, side reactors (R1/R2/R3) feed location at the 6th, 11th, and 14th trays respectively, the SRC tower side line that entered the side reactors (R2/R3) feed locations at the 23rd and 24th trays, respectively, and the MeOH distribution ratio of the three side reactors (R1/R2/R3) was at 0.58︰0.22︰0.2.

Key words: reactive distillation, esterification, methyl methacrylate, minimum total annual cost(TAC), carbon dioxide emissions, optimal design

中图分类号:

TQ032

孙玉玉, 蔡鑫磊, 汤吉海, 黄晶晶, 黄益平, 刘杰. 反应精馏合成甲基丙烯酸甲酯工艺优化及节能[J]. 化工进展, 2023, 42(S1): 56-63.

SUN Yuyu, CAI Xinlei, TANG Jihai, HUANG Jingjing, HUANG Yiping, LIU Jie. Optimization and energy-saving of a reactive distillation process for the synthesis of methyl methacrylate[J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 56-63.

图/表 11

参考文献 26

1	LIANG Taotao, GUO Xiaogang, ABDULMOSEEN Segun Giwa, et al. Design and optimization of a process for the production of methyl methacrylate via direct methylation[J]. Process, 2019, 7(6): 377.
2	李斌, 解铭, 齐翔, 等. 乙烯路线制备甲基丙烯酸甲酯研究进展[J]. 化工进展, 2019, 38(4): 1739-1745.
	LI Bin, XIE Ming, QI Xiang, et al. Progress in preparation of methyl methacrylate by ethylene route[J]. Chemical Industry and Engineering Progress, 2019, 38(4): 1739-1745.
3	NAGAI Koichi. New developments in the production of methyl methacrylate[J]. Appl. Catal. A Gen., 2001, 221: 367-377.
4	LEI Liang, TAO Ran, SHI Jianming, et al. Rapid and continuous synthesis of methacrolein with high selectivity by condensation of propanal with formaldehyde in laboratory[J]. The Canadian Journal of Chemical Engineering, 2017, 95(10): 1985-1992.
5	YAN R, LI Z, DIAO Y, et al. Green process for methacrolein separation with ionic liquids in the production of methyl methacrylate[J]. AIChE Journal, 2011, 57(9): 2388-2396.
6	李华胤, 李洁, 谭媛, 等. 甲基丙烯酸甲酯生产工艺及所用贵金属催化剂研究进展[J]. 化工进展, 2021, 40(1): 183-194.
	LI Huayin, LI Jie, TAN Yuan, et al. Research progress on production technology and noble metal catalyst for synthesis of methyl methacrylate[J]. Chemical Industry and Engineering Progress, 2021, 40(1): 183-194.
7	舒月锋, 罗明陨, 马建学, 等. 甲基丙烯酸甲酯合成工艺条件的研究[J]. 上海化工, 2013, 38(6): 7-10.
	SHU Yuefeng, LUO Mingyun, MA Jianxue, et al. Study on synthetic conditions of methyl methacrylate [J]. Shanghai Chemical Industry, 2013, 38(6): 7-10.
8	JURGEN Gmehling, JOCHEN Menke, KRAFCZYK J, et al. Azeotropic Data[M]. Wiley-VCH: Weinheim, 2004.
9	YASUYUKIC S, PETROCHEMICAL C M. Process for producing acrylic or methacrylic esters: EP0618187A1[P]. 1994-10-05.
10	Kiss ANTON A, MEGAN Jobson, GAO Xin. Reactive distillation: Stepping up to the next level of process intensification[J]. Industrial & Engineering Chemistry Research, 2018, 58(15): 5909-5918.
11	高鑫, 赵悦, 李洪, 等. 反应精馏过程耦合强化技术基础与应用研究述评[J]. 化工学报, 2018, 69(1): 218-238.
	GAO Xin, ZHAO Yue, LI Hong, et al. Review of basic and application investigation of reactive distillation technology for process intensification[J]. CIESC Journal, 2018, 69(1): 218-238.
12	陆佳伟, 孔倩, 汤吉海, 等. “背包式”反应精馏集成过程研究进展[J]. 化工进展, 2020, 39(12): 4940-4953.
	LU Jiawei, KONG Qian, TANG Jihai, et al. Review on investigation of side-reactor column configuration technology[J]. Chemical Industry and Engineering Progress, 2020, 39(12): 4940-4953.
13	LI Xingang, WANG Rui, YAN Yutao, et al. Ethylene glycol recovery from 2 - e t h y l - 1,3 - d i o x o l a n e hydrolysis via reactive distillation: Pilotscale experiments and process analysis[J]. Industrial & Engineering Chemistry Research, 2019, 58(45): 20746-20757.
14	王振松, 许戈, 汤吉海, 等. 常压反应-减压精馏集成生产甲酸环己酯的过程模拟[J]. 高校化学工程学报, 2016, 30(5): 1021-1026.
	WANG Zhensong, XU Ge, TANG Jihai, et al. Process simulation of cyclohexyl formate production with an atmospheric reaction-vacuum distillation integrated system[J]. Journal of Chemical Engineering of Chinese Universities, 2016, 30(5): 1021-1026.
15	GAO Xin, WANG Fangzhou, LI Hong, et al. Heat-integrated reactive distillation process for TAME synthesis[J]. Separation and Purification Technology, 2014, 132: 468-478.
16	孙玉玉, 汤吉海, 陈献, 等. 带多台侧反应器的间歇反应精馏生产氯化苄非稳态模拟与过程设计[J]. 高校化学工程学报, 2015, 29(2): 388-394.
	SUN Yuyu, TANG Jihai, CHEN Xian, et al. Unsteady state simulation and process design of a batch reactive distillation column with multiple side reactors for benzyl chloride production[J]. Journal of Chemical Engineering of Chinese Universities, 2015, 29(2): 388-394.
17	WU Yichang, HSU C S, Huang HSIAO-PING. Design and control of a methyl methacrylate separation process with a middle decanter[J]. Industrial & Engineering Chemistry Research, 2011, 50: 4595-4607.
18	WANG Gang, CAI Guangming. Cooperative catalytic effects between Brønsted and Lewis acid sites and kinetics for production of methyl methacrylate on S O 4 2 - /TiO₂-SiO₂ [J]. Chemical Engineering Science, 2021, 229: 116165.
19	LUYBEN William L. Comparison of extractive distillation and pressure-swing distillation for acetone/chloroform separation[J]. Computers & Chemical Engineering, 2013, 50: 1-7.
20	DOUGLAS J M. Conceptual design of chemical processes[M]. New York: Mc Graw-Hill, 1988: 345-350.
21	WANG Yinglong, ZHANG Zhen, XU Dongfang, et al. Design and control of pressure-swing distillation for azeotropes with different types of boiling behavior at different pressures[J]. Journal of Process Control, 2016, 42: 59-76.
22	XIA Hui, YE Qing, FENG Shenyao, et al. A novel energy-saving pressure swing distillation process based on self-heat recuperation technology[J]. Energy, 2017, 141: 770-781.
23	CARLO James Cunanan, CARLO Andres Elorza Casas, MITCHELL Yorke, et al. Design and analysis of an offshore wind power to ammonia production system in Nova Scotia [J]. Energies 2022, 15, 9558.
24	LE Cao Nhien, NGUYEN Van Duc Lone, SANGYONG Kim, et al. Novel reaction-hybrid- extraction-distillation process for furfuryl alcohol production from raw bio-furfural[J]. Biochemical Engineering Journal, 2019, 148: 143-151.
25	李乔, 田思琪, 冯泽民, 等. 甲醇和三甲氧基硅烷共沸物分离过程模拟和优化[J]. 化工进展, 2021, 40(5): 2431-2439.
	LI Qiao, TIAN Siqi, FENG Zeming, et al. Simulation and optimization for separation processes of methanol and trimethoxysilane azeotrope[J]. Chemical Industry and Engineering Progress, 2021, 40(5): 2431-2439.
26	曹贵平, 朱中南, 乐慧慧, 等.“饥饿”反应器中自由基聚合动力学(Ⅱ)——甲基丙烯酸甲酯聚合动力学[J]. 化工学报, 1996, 47(1): 35-41.
	CAO Guiping, ZHU Zhongnan, LE Huihui, et al. “Hunger” Kinetics of free radical polymerization in reacto r ( Ⅱ ) ——A polymerization kinetics of methyl methacrylate[J]. CIESC Journal, 1996, 47(1): 35-41.

i	j	b_ij	b_ji
MEOH	H₂O	165.2623	-254.7308
MEOH	MAA	-388.6473	206.1569
MEOH	MMA	44.6284	-411.6194
MAA	H₂O	-308.6900	-52.3360
MAA	MMA	162.7822	-238.5464
MMA	H₂O	-474.3300	-194.0000

i	j	b_ij	b_ji
MEOH	H₂O	165.2623	-254.7308
MEOH	MAA	-388.6473	206.1569
MEOH	MMA	44.6284	-411.6194
MAA	H₂O	-308.6900	-52.3360
MAA	MMA	162.7822	-238.5464
MMA	H₂O	-474.3300	-194.0000

组成	100kPa		8kPa
组成	沸点/℃	共沸点/℃	沸点/℃	共沸点/℃
MAA	161.23	—	93.04	—
MeOH	64.53	—	11.55	—
MMA	100.05	—	34.34	—
H₂O	100.02	—	41.51	—
MAA-H₂O	—	99.56	—	41.23
MeOH-MMA	—	64.41	—	11.34
MMA-H₂O	—	76.41	—	21.11

组成	100kPa		8kPa
组成	沸点/℃	共沸点/℃	沸点/℃	共沸点/℃
MAA	161.23	—	93.04	—
MeOH	64.53	—	11.55	—
MMA	100.05	—	34.34	—
H₂O	100.02	—	41.51	—
MAA-H₂O	—	99.56	—	41.23
MeOH-MMA	—	64.41	—	11.34
MMA-H₂O	—	76.41	—	21.11

工艺流程	T_C	T_E	T_R	TOC_冷却水	TOC_加热蒸汽	TEC	TOC	TAC
RD	15.19	8.73	0	7.23	94.83	23.92	102.06	125.98
SRC	22.13	7.08	1.48	5.10	79.44	30.69	84.54	115.23