乙烷裂解制乙烯过程反应动力学模型的研究进展

doi:10.12034/j.issn.1009-606X.220208

摘要/Abstract

摘要： 随着乙烯工业的不断发展及能源结构的不断调整，裂解乙烯原料呈现多样性。近年来，乙烷裂解制乙烯技术逐渐成为工业生产的热点。乙烷作为乙烯生产的优选原料，不仅具有收率高、纯度高、质量高的产品优势，同时具有投资低、成本低、能耗低的生产优势。作为裂解炉模拟的核心，研究乙烷裂解过程中的反应动力学模型可为工业生产提供精准预判。随工业应用范围的逐步扩大，该领域的理论研究也将迎来新的高潮。本工作对乙烷裂解的工艺优势、乙烷裂解反应动力学模型及结焦反应动力学模型的研究现状进行了总结。裂解反应动力学模型被分为经验模型、机理模型、分子反应动力学模型，结焦反应动力学模型被分为催化结焦、自由基结焦。针对未来的研究方向提出了新的展望，认为经验模型在裂解炉自动控制中的应用、自由基反应动力学模型的深入研究、乙烷与其他原料的共裂过程、裂解反应动力学与CFD技术的融合及基于多种生成机理建立结焦反应动力学模型五个方面将是今后需要关注的领域。

关键词: 乙烷, 乙烯, 裂解, 结焦, 动力学模型

Abstract: As the basic raw material for the production of various petrochemical products, ethylene plays an important role in the petrochemical field. With the global energy structure adjustment brought about by the shale gas revolution, ethane has gradually become the preferred raw material for ethylene production. Ethane pyrolysis technology has the advantages of high yield, low cost and low energy consumption. As the core content of cracking furnace mathematical model, the establishment of reaction kinetics model is the basis of simulation, control and optimization of cracking process. Therefore, under the current energy environment, it is of great significance for the development of domestic ethylene industry to study and summarize the kinetic model of ethane pyrolysis. In this work, the research status of ethane cracking process, pyrolysis reaction kinetic model and coking reaction kinetic model are summarized. The kinetic models of pyrolysis reaction are divided into empirical model, mechanism model and molecular reaction dynamics model. The kinetic models of coking reaction are divided into catalytic coking and free radical coking. This work not only introduces the basic models, but also compares and summarizes the process of gradual optimization of the models. In addition, this work puts forward new prospects for the future research direction. In the future, the combinations of the empirical model with the automatic control technology of cracking furnace and the reaction kinetics model with CFD technology are of great necessity. The co-cracking process of ethane and propane and optimization the product distribution needs to be further researched. The establishment of reaction kinetics model which can accurately predict the coking process need to be explored. In conclusion, ethane pyrolysis not only brings opportunities for industrial production, but also provides a new direction for researchers.

Key words: ethane, ethylene, thermal cracking, coking, kinetic model

中图分类号:

TQ221.211

王娟, 徐皓晗, 解凯, 余海艳. 乙烷裂解制乙烯过程反应动力学模型的研究进展[J]. 过程工程学报, 2021, 21(7): 752-761.

Juan WANG, Haohan XU, Kai XIE, Haiyan YU. Research progress on kinetic models of ethane pyrolysis[J]. The Chinese Journal of Process Engineering, 2021, 21(7): 752-761.

图/表 10

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Furnace type	Gas furnace	Liquid furnace
Cracking raw materials	Ethane propane	Naphtha ethane propane
Radiant section furnace tube form	Four tubes or six tubes	Two tubes
Dilution steam heating coil	No	Yes
Raw material preheating two-stage coil	No	Yes
Quench heat exchanger	Level 1, Level 2, Level 3	Level 1
Burner fuel	Hydrogen-rich fuel (hydrogen content greater than 60%)	Methane hydrogen (20% hydrogen) fuel

Furnace type	Gas furnace	Liquid furnace
Cracking raw materials	Ethane propane	Naphtha ethane propane
Radiant section furnace tube form	Four tubes or six tubes	Two tubes
Dilution steam heating coil	No	Yes
Raw material preheating two-stage coil	No	Yes
Quench heat exchanger	Level 1, Level 2, Level 3	Level 1
Burner fuel	Hydrogen-rich fuel (hydrogen content greater than 60%)	Methane hydrogen (20% hydrogen) fuel

Feedstocks	H₂	CH₄	C₂H₄	C₃H₈	1,3-butadiene	C₄H₁₀+C₄H₈	Benzene
Ethane	8.82	6.27	77.73	2.76	1.81	1.81	0.87
Propane	2.27	27.43	42.01	16.82	3.01	3.01	2.47
N-butane	1.57	22.12	40.00	17.27	3.50	3.50	3.02
Naphtha	1.56	17.20	33.62	15.53	4.56	4.56	6.74
Atmospheric diesel	0.94	11.19	25.92	16.15	4.56	4.56	6.03
Vacuum residue	0.78	8.75	20.49	14.07	5.38	5.38	3.73

Feedstocks	H₂	CH₄	C₂H₄	C₃H₈	1,3-butadiene	C₄H₁₀+C₄H₈	Benzene
Ethane	8.82	6.27	77.73	2.76	1.81	1.81	0.87
Propane	2.27	27.43	42.01	16.82	3.01	3.01	2.47
N-butane	1.57	22.12	40.00	17.27	3.50	3.50	3.02
Naphtha	1.56	17.20	33.62	15.53	4.56	4.56	6.74
Atmospheric diesel	0.94	11.19	25.92	16.15	4.56	4.56	6.03
Vacuum residue	0.78	8.75	20.49	14.07	5.38	5.38	3.73

Project	Ethane	Propane	Butane	Light naphtha	Light diesel oil	Vacuum gas oil
Investment/USD million	413.5	508.5	516.2	554.1	644.4	668.1
Relative investment	1.00	1.25	1.25	1.34	1.56	1.62
Cost/(USD/t)	241.9	201.5	201.8	355.3	397.3	363.5
Relative energy consumption	1.00	1.44	1.50	1.53	1.72	2.04