The Chinese Journal of Process Engineering ›› 2021, Vol. 21 ›› Issue (7): 752-761.DOI: 10.12034/j.issn.1009-606X.220208
• Review • Previous Articles Next Articles
Juan WANG1,2(
), Haohan XU1,2, Kai XIE1,2, Haiyan YU1,2
Received:2020-07-01
Revised:2020-08-26
Online:2021-07-28
Published:2021-07-27
王娟1,2(
), 徐皓晗1,2, 解凯1,2, 余海艳1,2
作者简介:王娟(1977-),女,辽宁省丹东市人,博士,副教授,化工过程机械,E-mail: wangjuan@cup.edu.cn.
CLC Number:
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.
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.
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URL: https://jproeng.ipe.ac.cn/EN/10.12034/j.issn.1009-606X.220208
| 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 |
Table 1 Comparison of cracking furnace configuration[16]
| 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 |
Table 2 Product distribution of different cracking raw materials (wt%)[17]
| 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 |
Table 3 Comparison of ethylene plant investment, cost and relative energy consumption with different cracking raw materials[18]
| 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 |
| Reaction stage | Primitive reaction | A/ [m3/(mol∙s)] | E/(kcal/mol) |
|---|---|---|---|
| Chain initiation | C2H6→2CH3* | 6.3×1016 | 86.0 |
| Chain growth | CH3*+C2H6→CH4+C2H5* | 2.5×1011 | 10.8 |
| C2H5*→C2H4+H* | 5.3×1014 | 40.8 | |
| H*+C2H6→C2H5*+H2 | 3.8×1012 | 7.0 | |
| Chain termination | H*+C2H5*→C2H6 | 7.0×1013 | 0.0 |
Table 4 Radical mechanics of ethane cracking[29]
| Reaction stage | Primitive reaction | A/ [m3/(mol∙s)] | E/(kcal/mol) |
|---|---|---|---|
| Chain initiation | C2H6→2CH3* | 6.3×1016 | 86.0 |
| Chain growth | CH3*+C2H6→CH4+C2H5* | 2.5×1011 | 10.8 |
| C2H5*→C2H4+H* | 5.3×1014 | 40.8 | |
| H*+C2H6→C2H5*+H2 | 3.8×1012 | 7.0 | |
| Chain termination | H*+C2H5*→C2H6 | 7.0×1013 | 0.0 |
| Froment | Zou | ||||
|---|---|---|---|---|---|
| Cracking reaction system | Ethane | Propane | Ethane-propane | Ethane-propane | |
| Number of reactions | 49 | 80 | 17 | 18 | |
| Number of species | Molecule | 11 9 | 11 11 | 6 6 | 6 5 |
| Free radicals | |||||
| Number of parameters | 81 | 134 | 32 | 34 | |
| Pseudo-steady state hypothesis | No | No | No | No | |
| Valuation method | Try method | Try method | Taken from the separate pyrolysis system | Improved simplex algorithm | |
Table 5 Comparison of various free radical mechanism models[33]
| Froment | Zou | ||||
|---|---|---|---|---|---|
| Cracking reaction system | Ethane | Propane | Ethane-propane | Ethane-propane | |
| Number of reactions | 49 | 80 | 17 | 18 | |
| Number of species | Molecule | 11 9 | 11 11 | 6 6 | 6 5 |
| Free radicals | |||||
| Number of parameters | 81 | 134 | 32 | 34 | |
| Pseudo-steady state hypothesis | No | No | No | No | |
| Valuation method | Try method | Try method | Taken from the separate pyrolysis system | Improved simplex algorithm | |
| No. | Reaction | ΔH/(kcal/mol) |
|---|---|---|
| 1 | C2H6↔C2H4+H2 | 3.257×107 |
| 2 | 2C2H6→C3H8+CH4 | -2.761×106 |
| 3 | C3H6↔C2H2+CH4 | 3.188×107 |
| 4 | C2H2+C2H4 →C4H6 | -4.173×106 |
| 5 | C2H6+C2H4→C3H6+CH4 | -5.489×106 |
Table 6 Reaction scheme for ethane cracking[46]
| No. | Reaction | ΔH/(kcal/mol) |
|---|---|---|
| 1 | C2H6↔C2H4+H2 | 3.257×107 |
| 2 | 2C2H6→C3H8+CH4 | -2.761×106 |
| 3 | C3H6↔C2H2+CH4 | 3.188×107 |
| 4 | C2H2+C2H4 →C4H6 | -4.173×106 |
| 5 | C2H6+C2H4→C3H6+CH4 | -5.489×106 |
| No. | Reaction | ΔH/(kcal/mol) |
|---|---|---|
| 1 | C2H6↔C2H4+H2 | 3.257×107 |
| 2 | 2C2H6→C3H8+CH4 | -2.761×106 |
| 3 | C3H8→C3H6+H2 | 2.984×107 |
| 4 | C3H8→C2H4+CH4 | 1.974×107 |
| 5 | C3H6↔C2H2+CH4 | 3.188×107 |
| 6 | C2H2+C2H4→C4H6 | -4.173×106 |
| 7 | 2C2H6→C2H4+2CH4 | 1.698×106 |
| 8 | C2H6+C2H4→C3H6+CH4 | -5.489×106 |
Table 7 Reaction scheme for ethane propane cracking[46]
| No. | Reaction | ΔH/(kcal/mol) |
|---|---|---|
| 1 | C2H6↔C2H4+H2 | 3.257×107 |
| 2 | 2C2H6→C3H8+CH4 | -2.761×106 |
| 3 | C3H8→C3H6+H2 | 2.984×107 |
| 4 | C3H8→C2H4+CH4 | 1.974×107 |
| 5 | C3H6↔C2H2+CH4 | 3.188×107 |
| 6 | C2H2+C2H4→C4H6 | -4.173×106 |
| 7 | 2C2H6→C2H4+2CH4 | 1.698×106 |
| 8 | C2H6+C2H4→C3H6+CH4 | -5.489×106 |
| No. | 1 | 2 | 3 | 4 |
|---|---|---|---|---|
| Kinetic model | X+S→XS XS→C+S+nH2 | X+S↔XS XS→C+S+nH2 | X+S→XS XS→C+S+nH2 CS→eS+fC+gCS | X+S↔XS XS→C+S+nH2 CS→eS+fC+gCS |
| Model accuracy | Poor | Poor | More accurate | Accurate |
Table 8 Kinetic model of catalytic mechanism[66]
| No. | 1 | 2 | 3 | 4 |
|---|---|---|---|---|
| Kinetic model | X+S→XS XS→C+S+nH2 | X+S↔XS XS→C+S+nH2 | X+S→XS XS→C+S+nH2 CS→eS+fC+gCS | X+S↔XS XS→C+S+nH2 CS→eS+fC+gCS |
| Model accuracy | Poor | Poor | More accurate | Accurate |
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