基于本质安全与经济性的环己烷氧化工艺参数多目标优化研究

doi:10.11949/0438-1157.20241457

摘要/Abstract

摘要：

由于氧化反应在化工行业存在的普遍性及其危险性，针对典型工艺环己烷氧化进行研究。首先利用Aspen Plus进行建模及动力学修正，修正前主产物中最大误差为28.56%，修正后主产物中最大误差为3.11%。使用遗传算法（GA），以Dow火灾爆炸指数（F&EI）、年总费用（TAC）和尾氧浓度为目标函数，对环己烷无催化氧化这一过程进行多目标优化，获得了Pareto前沿。优化结果表明，与原操作条件相比，新操作条件在维持尾氧浓度小于工业预警值3%的情况下，设备费用基本维持不变，操作费用减少了34.7%，F&EI指数从156降到76.66，危险程度从较危险降为较轻。

关键词: 环己烷无催化氧化, 优化设计, 本质安全, 遗传算法, 多目标优化, Pareto前沿

Abstract:

Due to the Due to the prevalence and danger of oxidation reactions in the chemical industry, a study was conducted on the typical process of cyclohexane oxidation. Aspen Plus was employed for process modeling and kinetic modifications. Before correction, the maximum error among the main products was 28.56%, which was reduced to 3.11% after correction. A multi-objective optimization of the non-catalytic oxidation of cyclohexane was conducted using the genetic algorithm (GA), with Dow's fire and explosion index (F&EI), total annual cost (TAC), and residual oxygen concentration as objective functions. The optimization generated a Pareto front. The results demonstrated that, compared to the original operating conditions, the optimized conditions achieved significant improvements. Under the constraint of maintaining the tail oxygen concentration below the industrial warning threshold of 3%, the equipment cost remained largely unchanged, while operating costs decreased by 34.7%. Additionally, the F&EI index was reduced from 156 to 76.66, lowering the risk level from “moderate risk” to “low risk”.

Key words: uncatalyzed oxidation of cyclohexane, optimal design, inherent safety, genetic algorithm, multi-objective optimization, Pareto front

中图分类号:

TQ 086

王一非, 任婧杰, 毕明树, 叶昊天. 基于本质安全与经济性的环己烷氧化工艺参数多目标优化研究[J]. 化工学报, 2025, 76(6): 2722-2732.

Yifei WANG, Jingjie REN, Mingshu BI, Haotian YE. Multi-objective optimization of cyclohexane oxidation process parameters based on inherent safety and economic performance[J]. CIESC Journal, 2025, 76(6): 2722-2732.

图/表 19

参考文献 29

[1]	赵劲松, 粟镇宇, 贺丁, 等. 化工过程安全管理[M]. 北京: 化学工业出版社, 2021: 1-10.
	Zhao J S, Su Z Y, He D, et al. Safety Management of Chemical Process[M]. Beijing: Chemical Industry Press, 2021: 1-10.
[2]	王杭州, 陈丙珍, 赵劲松, 等. 面向本质安全化的化工过程设计多稳态及其稳定性分析[M]. 北京: 清华大学出版社, 2017: 166-167.
	Wang H Z, Chen B Z, Zhao J S, et al. Inherently Safer Design Oriented Analysis of Steady-state Multiplicity and Stability of Chemical Processes[M]. Beijing: Tsinghua University Press, 2017: 166-167.
[3]	Swuste P, Theunissen J, Schmitz P, et al. Process safety indicators, a review of literature[J]. Journal of Loss Prevention in the Process Industries, 2016, 40: 162-173.
[4]	赵劲松. 化工过程安全[M]. 北京: 化学工业出版社, 2015: 1-7.
	Zhao J S. Chemical Process Safety[M]. Beijing: Chemical Industry Press, 2015: 1-7.
[5]	Sanders R E. Chemical Process Safety[M]. 4th ed. Oxford·Waltham: Elsevier, 2015.
[6]	Kletz T. Inherently safer design: the growth of an idea[J]. Process Safety Progress, 1996: 15(1): 5-8.
[7]	Chen J R. An inherently safer process of cyclohexane oxidation using pure oxygen: an example of how better process safety leads to better productivity[J]. Process Safety Progress, 2004, 23(1): 72-81.
[8]	周权. 环己烷无催化氧化工艺优化研究[D]. 大连: 大连理工大学, 2006.
	Zhou Q. Study on optimization of cyclohexane non-catalytic oxidation process[D]. Dalian: Dalian University of Technology, 2006.
[9]	尹华清, 罗和安. 环己烷富氧氧化反应器内气相空间危险性研究[J]. 湖南大学学报(自然科学版), 2009, 36(5): 63-66.
	Yin H Q, Luo H A. Study of the risks of gas phases inside the reator of cyclohexane oxidation with oxygen-enriched air[J]. Journal of Hunan University (Natural Sciences), 2009, 36(5): 63-66.
[10]	郑婷, 李秀喜, 曹丽琦. 基于CFD的环己烷无催化氧化反应工况分析[C]//2019年中国过程系统工程年会论文集. 杭州, 2019: 150-158.
	Zheng T, Li X X, Cao L Q.Analysis of operating conditions of cyclohexane non-catalytic oxidation by CFD[C].Proceedings of the 2019 China Annual Conference on Process Systems Engineering.Hangzhou,China,2019:150-158.
[11]	李秀喜, 曹丽琦, 王兴. 环己烷氧化生产环己酮过程建模与参数分析[J]. 清华大学学报(自然科学版), 2018, 58(5): 523-528.
	Li X X, Cao L Q, Wang X. Process modeling and analysis of the parameters for oxidation of cyclohexane into cyclohexanone[J]. Journal of Tsinghua University (Science and Technology), 2018, 58(5): 523-528.
[12]	Huo H H, Guo B R, Ma G X, et al. Recent progress in strategies to enhance the photocatalytic oxidation performance of cyclohexane[J]. Journal of Environmental Chemical Engineering, 2024, 12(5): 113504.
[13]	Zhang X H, Chen Z, Chen J, et al. Liquid-phase oxidation of cyclohexane with air in a microreactor: kinetics and process intensification[J]. Chemical Engineering Science, 2024, 288: 119777.
[14]	陈纪忠, 费黎明, 范镇, 等. 环己烷液相无催化剂的氧化动力学研究[J]. 化学反应工程与工艺, 1992, 8(3): 237-245.
	Chen J Z, Fei L M, Fan Z, et al. A study on the kinetics of liquid phase oxidation of cyclohexane without catalyst[J]. Chemical Reaction Engineering and Technology, 1992, 8(3): 237-245.
[15]	Tarantola A. Inverse Problem Theory and Methods for Model Parameter Estimation[M]. Philadelphia, PA: Society for Industrial and Applied Mathematics, 2005.
[16]	Aspen Technology, Inc. Aspen Plus User Guide[EB/OL]. (2020-11-03).
[17]	孙兰义. 化工过程模拟实训: Aspen Plus教程[M]. 2版. 北京: 化学工业出版社, 2017.
	Sun L Y. Chemical Process Simulation Training: Aspen Plus Course[M]. 2nd ed. Beijing: Chemical Industry Press, 2017.
[18]	Pan D T, Li G X, Su Y H, et al. Kinetic study for the oxidation of cyclohexanol and cyclohexanone with nitric acid to adipic acid[J]. Chinese Journal of Chemical Engineering, 2021, 29: 183-189.
[19]	Li G X, Liu S E, Dou X Y, et al. Synthesis of adipic acid through oxidation of K/A oil and its kinetic study in a microreactor system[J]. AIChE Journal, 2020, 66(9): e16289.
[20]	Pohorecki R, Moniuk W, Wierzchowski P T. Kinetic model of uncatalyzed oxidation of cyclohexane[J]. Chemical Engineering Research and Design, 2009, 87(3): 349-356.
[21]	Silke E J, Pitz W J, Westbrook C K, et al. Detailed chemical kinetic modeling of cyclohexane oxidation[J]. The Journal of Physical Chemistry A, 2007, 111(19): 3761-3775.
[22]	Gao X M, Abdul Raman A A, Hizaddin H F, et al. Review on the inherently safer design for chemical processes: past, present and future[J]. Journal of Cleaner Production, 2021, 305: 127154.
[23]	AIChE. Dow's Fire & Explosion Index Hazard Classification Guide: AIChE/Dow's[M]. Hoboken, NJ, USA: John Wiley & Sons Inc, 1994
[24]	Willett M. Oxygen sensing for industrial safety - evolution and new approaches[J]. Sensors, 2014, 14(4): 6084-6103.
[25]	王兴. 环己烷无催化氧化反应过程模拟与关键参数分析[D]. 广州: 华南理工大学, 2013.
	Wang X. Simulation and key parameters analysis of cyclohexane non-catalytic oxidation reaction process[D]. Guangzhou: South China University of Technology, 2013.
[26]	Nelson D A, Kirkwood R L, Douglas J M. Conceptual design of chemical processes[J]. Advances in AI and Simulation, 1989,20:180-184.
[27]	Mei W G, Zhai R R, Zhao Y X, et al. Exergoeconomic analysis and multi-objective optimization using NSGA-Ⅱ in a novel dual-stage Selexol process of integrated gasification combined cycle[J]. Energy, 2024, 286: 129663.
[28]	Patro S G K, Sahu K K. Normalization: a preprocessing stage[J]. Iarjset, 2015: 20-22.
[29]	Abrahamsen E B, Milazzo M F, Selvik J T, et al. Prioritising investments in safety measures in the chemical industry by using the Analytic Hierarchy Process[J]. Reliability Engineering & System Safety, 2020, 198: 106811.

反应参数	数值
反应温度/K	438.00
压力/MPa	1.30
气相流率/(m³/h)	6530.00
进料氧气体积分数/%	21.00
有效体积/m³	82.24

反应参数	数值
反应温度/K	438.00
压力/MPa	1.30
气相流率/(m³/h)	6530.00
进料氧气体积分数/%	21.00
有效体积/m³	82.24

组分	实际值/ (kmol/m³)	计算值/ (kmol/m³)	相对误差/%
环己烷	7.0265	7.2113	2.63
环己基过氧化氢	0.1806	0.1290	-28.56
环己醇	0.0556	0.0477	-14.13
环己酮	0.0254	0.0202	-20.55
酸	0.0141	0.0069	-50.85
酯类	0.0060	0.0030	-49.48

组分	实际值/ (kmol/m³)	计算值/ (kmol/m³)	相对误差/%
环己烷	7.0265	7.2113	2.63
环己基过氧化氢	0.1806	0.1290	-28.56
环己醇	0.0556	0.0477	-14.13
环己酮	0.0254	0.0202	-20.55
酸	0.0141	0.0069	-50.85
酯类	0.0060	0.0030	-49.48

组分	实际值/ (kmol/m³)	计算值/ (kmol/m³)	相对误差/%
环己烷	7.0157	7.1157	1.43
环己基过氧化氢	0.1826	0.1626	-10.95
环己醇	0.0404	0.0394	-12.38
环己酮	0.0247	0.0226	-16.76
酸	0.0132	0.0101	-23.48
酯类	0.0060	0.0020	-66.67