重质油高温快速热解自动反应网络的动力学建模

doi:10.11949/0438-1157.20240026

化工学报 ›› 2024, Vol. 75 ›› Issue (7): 2644-2655.DOI: 10.11949/0438-1157.20240026

重质油高温快速热解自动反应网络的动力学建模

姚宏哲¹(), 黄飞宇¹, 杨松¹, 钟梅¹, 代正华¹^,²()

^1.新疆大学化工学院，省部共建碳基能源资源化学与利用国家重点实验室，新疆煤炭清洁转化与化工过程重点实验室，新疆乌鲁木齐 830017
^2.华东理工大学资源与环境工程学院，上海市煤气化工程技术研究中心，上海 200237

收稿日期:2024-01-05 修回日期:2024-03-05 出版日期:2024-07-25 发布日期:2024-08-09
通讯作者: 代正华
作者简介:姚宏哲（1998—），男，硕士研究生，1693982164@qq.com
基金资助:
新疆自治区自然科学基金重点项目(2023D01D02);上海市科技创新行动计划课题(21DZ1209003)

Kinetic modeling of the high-temperature rapid pyrolysis auto-reaction network of heavy oil

Hongzhe YAO¹(), Feiyu HUANG¹, Song YANG¹, Mei ZHONG¹, Zhenghua DAI¹^,²()

^1.State Key Laboratory of Chemistry and Utilization of Carbon-based Energy Resources, Xinjiang Key Laboratory of Coal Clean Conversion & Chemical Engineering, School of Chemical Engineering, Xinjiang University, Urumqi 830017, Xinjiang, China
^2.School of Resources and Environmental Engineering, East China University of Science and Technology, Shanghai Coal Gasification Engineering Technology Research Center, Shanghai 200237, China

Received:2024-01-05 Revised:2024-03-05 Online:2024-07-25 Published:2024-08-09
Contact: Zhenghua DAI

摘要/Abstract

摘要：

重质油高温快速热解过程模型对提高产品收率、附加值及降低能耗具有重要意义。利用自动反应网络生成器RMG（reaction mechanism generator）构建重质油高温快速热解的机理模型。选择了分步构建方法，最终合并的模型包含230种物质和1468个反应。采用高频炉对二十烷、十氢萘、乙苯和不同质量比例混合物（二十烷、乙苯和十氢萘）进行快速热解实验验证，结果表明：机理模型可准确模拟出重质油高温快速热解主要气体产物生成结果，当重质油中链烷烃含量较多时和芳烃含量较多时，分别控制温度在1300℃左右和800℃左右有利于乙烯的生产。

关键词: 重质油, 高温快速热解, 自动反应网络生成器, 高频炉

Abstract:

The modeling of the high-temperature rapid pyrolysis process for heavy oil holds significant implications for enhancing product yields, adding value, and reducing energy consumption. In this paper, we employed the automatic reaction network generator, reaction mechanism generator (RMG), to construct a mechanistic model for the high-temperature rapid pyrolysis of heavy oil. A stepwise construction approach was selected, culminating in a model that encompasses 230 substances and 1468 reactions. Rapid pyrolysis experiments were conducted in a high-frequency furnace by using eicosane, decahydronaphthalene, ethylbenzene, and their mixtures at different ratios to validate the model. The mechanism model can accurately simulate the main gas product generation results of high-temperature rapid pyrolysis of heavy oil. Specifically, when heavy oil contains a higher amount of alkanes or aromatics, maintaining the temperature around 1300℃ and 800℃, respectively, is conducive to ethylene production.

Key words: heavy oil, high-temperature and rapid pyrolysis, automatic response network generator, high-frequency furnace

中图分类号:

TQ 519

姚宏哲, 黄飞宇, 杨松, 钟梅, 代正华. 重质油高温快速热解自动反应网络的动力学建模[J]. 化工学报, 2024, 75(7): 2644-2655.

Hongzhe YAO, Feiyu HUANG, Song YANG, Mei ZHONG, Zhenghua DAI. Kinetic modeling of the high-temperature rapid pyrolysis auto-reaction network of heavy oil[J]. CIESC Journal, 2024, 75(7): 2644-2655.

图/表 11

图 1 自动反应网络生成过程示意图

Fig.1 Schematic diagram of automatic reaction network generation process

图 2 RMG与Chemkin结合原理示意图

Fig.2 Schematic diagram of the combination principle of RMG and Chemkin

表 1 模型化合物数据库的选择

Table 1 Selection of model compound database

数据库	二十烷	十氢萘	乙苯
热力学库	‘primaryThermoLibrary’	‘DFT_QCI_thermo’	‘primaryThermoLibrary’
反应库	—	—	‘AromaticsPyrolysis’
动力学库	‘H_Abstraction’、‘R_Addition_MultipleBond’、‘R_Recombination’、‘Disproportionation’、‘Intra_R_Add_Exocyclic’、‘Intra_R_Add_Endocyclic’

图 3 高频炉快速升温热解装置

Fig.3 High frequency furnace rapid heating pyrolysis device

表 2 模型化合物高温快速热解的工况条件

Table 2 Operating conditions for rapid high-temperature pyrolysis of model compounds

进料	进料速度/（ml/min）	载气流量/（ml/min）	温度/℃	进料时间/s
二十烷	2	400	600~1000	600
十氢萘	2	400	600~1000	600
乙苯	2	400	600~1000	600
二十烷∶十氢萘∶乙苯（1∶1∶1）	2	400	600~1000	600
二十烷∶十氢萘∶乙苯（1∶3∶6）	2	400	600~1000	600

表 3 反应机理生成器模拟结果

Table 3 Simulation results of the mechanism of the reaction

项目	二十烷	十氢萘		乙苯
机制合并	物质	230	反应		1468
用户指定容差	0.05	0.1		0.1
（DD∶HH∶MM∶SS）执行时间	00∶00∶07∶31	00∶21∶51∶12		05∶05∶20∶56
核心物质	64	83		122
核心反应	477	545		477
边缘物质	839	7980		5900
边缘反应	5449	19063		9014

图 4 不同原料的热解转化率及主要气体摩尔分数

Fig.4 Pyrolysis conversion rate of different raw materials and molar fraction of main gases

图 5 二十烷-十氢萘-乙苯不同质量比混合热解转化率及主要气体摩尔分数

Fig.5 Mixed pyrolysis conversion ratio and molar fraction of main gas of eicosane, decahydronaphthalene and ethylbenzene with different mass ratios

图 6 二十烷、十氢萘、乙苯以1∶3∶6比例混合热解生成主要气体的反应路径分析

Fig.6 Reaction pathway analysis of the main gas generated by the pyrolysis of a mixture of eicosane, decahydronaphthalene, and ethylbenzene in a ratio of 1∶3∶6

图 7 不同气体产物的产率及敏感性

Fig.7 Yield of different gas products and sensitivity

表 4 主要基元反应动力学参数

Table 4 Translation of the main elementary reaction kinetic parameters

序号	主要基元反应	动力学参数
序号	主要基元反应	指前因子	温度指数	活化能/(kJ/mol)
1	H(2)+CH₄(5) $⇌$ H₂(3)+CH₃(4)	4.10×10³	3.16	8.76
2	H(2)+C₃H₆(213) $⇌$ npropyl(172)	1.36×10⁸	1.64	1.86
3	H(2)+C₂H₄(7) $⇌$ H₂(3)+C₂H₃(8)	2.40×10²	3.62	11.27
4	H(2)+C₁₀H₁₈(120) $⇌$ H₂(3)+C₁₀H₁₇(121)	9.52×10^-1	4.34	2.00
5	H(2)+C₁₀H₁₈(120) $⇌$ H₂(3)+C₁₀H₁₇(122)	2.55×10²	3.68	4.70
6	H(2)+C₁₀H₁₈(120) $⇌$ H₂(3)+C₁₀H₁₇(123)	2.55×10²	3.68	4.70
7	H(2)+C₈H₁₀(1) $⇌$ H₂(3)+C₈H₉(12)	1.60×10¹³	0	8.17
8	H(2)+C₆H₆(29) $⇌$ H₂(3)+C₆H₅(10)	4.57×10⁸	1.88	14.84
9	H(2)+C₁₀H₁₆(124) $⇌$ H₂(3)+C₁₀H₁₅(127)	2.55×10²	3.68	4.70
10	H(2)+C₇H₈(23) $⇌$ H₂(3)+C₇H₇(9)	7.54×10⁴	2.57	3.15
11	H(2)+C₇H₈(22) $⇌$ H₂(3)+C₇H₇(9)	8.94×10^-1	4.34	-0.40
12	H(2)+C₈H₈(27) $⇌$ H₂(3)+C₈H₇(33)	2.81×10⁵	2.41	8.84
13	H(2)+C₁₀H₁₆(126) $⇌$ C₁₀H₁₇(123)	1.46×10⁸	1.64	1.37
14	CH₃(4)+C₇H₇(9) $⇌$ C₈H₁₀(1)	6.75×10¹⁶	-1.29	0
15	H(2)+C₁₀H₁₆(126) $⇌$ C₁₀H₁₇(122)	1.46×10⁸	1.64	1.37
16	C₂H₄(7)+C₂H₅(6) $⇌$ C₄H₉(175)	4.24×10³	2.41	5.06
17	H(2)+C₂H₃(8)(M) $⇌$ C₂H₄(7)(M)	3.90×10¹³	0.20	0
18	H(2)+C₄H₈(222) $⇌$ C₄H₉(175)	3.01×10⁸	1.60	2.40
19	H(2)+C₂H₄(7)(M) $⇌$ C₂H₅(6)(M)	1.40×10⁹	1.46	1.36
20	C₅H₁₀(195) $⇌$ C₂H₄(7)+C₃H₆(213)	8.70×10¹¹	0	55.69
21	CH₃(4)+C₃H₆(213) $⇌$ CH₄(5)+allyl(224)	7.20×10^-2	4.25	7.53
22	CH₃(4)+C₈H₈(27) $⇌$ CH₄(5)+C₈H₇(33)	3.21×10⁷	1.82	14.16
23	CH₃(4)+C₂H₄(7) $⇌$ CH₄(5)+C₂H₃(8)	6.00×10⁷	1.56	16.63
24	CH₃(4)+C₈H₁₀(1) $⇌$ CH₄(5)+C₈H₉(12)	6.00×10¹²	0	12.62
25	CH₃(4)+C₈H₈(27) $⇌$ CH₄(5)+C₈H₇(31)	3.21×10⁷	1.82	14.16
26	CH₃(4)+C₇H₈(23) $⇌$ CH₄(5)+C₇H₇(9)	1.07×10⁶	2.27	4.39
27	CH₃(4)+C₁₀H₁₈(120) $⇌$ CH₄(5)+C₁₀H₁₇(123)	6.42×10^-2	4.34	6.61
28	CH₃(4)+C₁₀H₁₈(120) $⇌$ CH₄(5)+C₁₀H₁₇(122)	6.42×10^-2	4.34	6.61
29	CH₃(4)+C₆H₆(29) $⇌$ CH₄(5)+C₆H₅(10)	5.15×10³	2.90	15.31
30	CH₃(4)+C₈H₇(32) $⇌$ CH₄(5)+C₈H₆(90)	8.20×10⁶	1.88	-1.12
31	CH₃(4)+C₈H₈(27) $⇌$ CH₄(5)+C₈H₇(32)	9.80×10^-2	4.01	12.90
32	CH₃(4)+C₁₀H₁₆(124) $⇌$ CH₄(5)+C₁₀H₁₅(127)	6.42×10^-2	4.34	6.61
33	CH₃(4)+C₁₀H₁₈(120) $⇌$ CH₄(5)+C₁₀H₁₇(121)	2.26×10^-2	4.34	7.69
34	C₇H₇(9) $⇌$ C₇H₇(21)	9.78×10⁹	0.58	28.56
35	C₄H₆(133)+C₆H₁₀(132) $⇌$ C₁₀H₁₆(129)	1.71×10⁴	1.53	23.41
36	H(2)+C₁₀H₁₆(125) $⇌$ C₁₀H₁₇(122)	7.72×10⁷	1.64	2.17
37	H(2)+C₈H₈(27) $⇌$ C₈H₉(11)	6.00×10⁷	1.64	1.55
38	H(2)+allyl(224) $⇌$ C₃H₆(213)	5.84×10¹³	0.18	0.12
39	H(2)+C₃H₆(213) $⇌$ H₂(3)+allyl(224)	3.36×10³	3.14	4.29
40	CH₃(4)+C₃H₆(213) $⇌$ C₄H₉(223)	2.10×10⁴	2.41	5.32
41	C₂H₅(6)+allyl(224) $⇌$ C₂H₄(7)+C₃H₆(213)	1.37×10¹⁴	-0.35	-0.13
42	H(2)+C₃H₆(213) $⇌$ C₃H₇(214)	1.84×10⁹	1.55	1.57
43	C₃H₆(213)+npropyl(172) $⇌$ C₆H₁₃(199)	2.13×10³	2.41	4.75
44	C₇H₈(22)+C₈H₇(31) $⇌$ C₇H₇(9)+C₈H₈(27)	2.90×10^-2	4.34	-5.60
45	C₂H₄(7)+C₈H₁₂(130) $⇌$ C₁₀H₁₆(125)	2.64×10¹¹	0	29.61
46	C₂H₄(7)+C₄H₆(133) $⇌$ C₆H₁₀(132)	1.00×10¹⁰	0	20.00
47	C₂H₃(8)+C₈H₈(27) $⇌$ C₂H₄(7)+C₈H₇(32)	3.91×10^-3	4.50	3.67
48	C₂H₃(8)+C₈H₁₀(1) $⇌$ C₂H₄(7)+C₈H₉(11)	5.56×10^-3	4.34	0.20
49	C₂H₄(7)+npropyl(172) $⇌$ C₅H₁₁(178)	4.24×10³	2.41	5.06
50	C₂H₄(7)+C₈H₇(31) $⇌$ C₂H₃(8)+C₈H₈(27)	2.20×10^-2	4.40	4.75
51	C₂H₄(7)+C₈H₇(33) $⇌$ C₂H₃(8)+C₈H₈(27)	2.20×10^-2	4.40	4.75
52	H(2)+CH₃(4)(M) $⇌$ CH₄(5)(M)	2.10×10¹⁴	0	0
53	H(2)+C₈H₉(12) $⇌$ C₈H₁₀(1)	9.17×10¹³	0.12	0
54	C₈H₉(12)+C₈H₁₁(16) $⇌$ 2C₈H₁₀(1)	8.43×10¹¹	0	0
55	CH₃(4)+C₈H₁₁(16) $⇌$ CH₄(5)+C₈H₁₀(1)	3.38×10¹¹	-0.18	-0.01
56	H(2)+C₈H₁₀(1) $⇌$ C₈H₁₁(16)	8.76×10⁷	1.71	6.09
57	2CH₃(4) $⇌$ H(2)+C₂H₅(6)	5.40×10¹³	0	16.06
58	CH₃(4)+C₂H₅(6) $⇌$ CH₄(5)+C₂H₄(7)	9.00×10¹¹	0	0
59	C₂H₅(6)+C₈H₉(12) $⇌$ C₂H₄(7)+C₈H₁₀(1)	6.90×10¹³	-0.35	0
60	2H(2)+H₂(3) $⇌$ 2H₂(3)	1.00×10¹⁷	-0.60	0
61	2H(2)(M) $⇌$ H₂(3)(M)	7.00×10¹⁷	-1.00	0
62	H(2)+C₈H₁₁(16) $⇌$ H₂(3)+C₈H₁₀(1)	1.00×10¹⁰	0	0
63	H(2)+C2H5(6) $⇌$ H₂(3)+C₂H₄(7)	1.08×10¹³	0	0
64	C₂H₃(8)+C₈H₁₁(16) $⇌$ C₂H₄(7)+C₈H₁₀(1)	8.43×10¹¹	0	0
65	C₂H₃(8)+C₈H₁₀(1) $⇌$ C₂H₄(7)+C₈H₉(12)	5.40×10^-4	4.55	3.50
66	C₂H₃(8)+C₂H₅(6) $⇌$ 2C₂H₄(7)	4.56×10¹⁴	-0.70	0
67	H(2)+C₁₀H₁₇(122) $⇌$ C₁₀H₁₈(120)	1.95×10¹²	0.35	0
68	H(2)+C₁₀H₁₇(123) $⇌$ C₁₀H₁₈(120)	1.58×10¹³	-0.22	0
69	C₁₀H₁₇(122) $⇌$ C₁₀H₁₇(123)	6.76×10⁹	0.88	38.00
70	C₁₀H₁₇(122) $⇌$ C₁₀H₁₇(123)	2.84×10⁷	1.625	35.45
71	C₁₀H₁₇(122) $⇌$ C₁₀H₁₇(123)	2.28×10^-3	3.95	11.17
72	C₁₀H₁₇(122) $⇌$ C₁₀H₁₇(123)	5.64×10^-2	3.28	5.91
73	C₁₀H₁₇(122) $⇌$ C₁₀H₁₇(123)	6.76×10⁹	0.88	38.00
74	C₁₀H₁₇(122)+C₁₀H₁₈(120) $⇌$ C₁₀H₁₇(123)+C₁₀H₁₈(120)	1.03×10^-2	4.29	7.71
75	C₂H₅(6)+C₁₀H₁₇(123) $⇌$ C₂H₄(7)+C₁₀H₁₈(120)	6.33×10¹⁴	-0.70	0
76	npropyl(172)+C₁₇H₃₅(171) $⇌$ C₂₀H₄₂(170)	3.19×10¹⁶	-1.18	0
77	CH₃(4)+C₂H₄(7) $⇌$ npropyl(172)	4.18×10⁴	2.41	5.63
78	CH₃(4)+npropyl(172) $⇌$ CH₄(5)+C₃H₆(213)	2.30×10¹³	-0.32	0
79	H(2)+npropyl(172) $⇌$ H₂(3)+C₃H₆(213)	3.62×10¹²	0	0
80	allyl(224)+npropyl(172) $⇌$ 2C₃H₆(213)	5.80×10¹²	0	-0.13

表 4 主要基元反应动力学参数

Table 4 Translation of the main elementary reaction kinetic parameters

序号	主要基元反应	动力学参数
序号	主要基元反应	指前因子	温度指数	活化能/(kJ/mol)
1	H(2)+CH₄(5) $⇌$ H₂(3)+CH₃(4)	4.10×10³	3.16	8.76
2	H(2)+C₃H₆(213) $⇌$ npropyl(172)	1.36×10⁸	1.64	1.86
3	H(2)+C₂H₄(7) $⇌$ H₂(3)+C₂H₃(8)	2.40×10²	3.62	11.27
4	H(2)+C₁₀H₁₈(120) $⇌$ H₂(3)+C₁₀H₁₇(121)	9.52×10^-1	4.34	2.00
5	H(2)+C₁₀H₁₈(120) $⇌$ H₂(3)+C₁₀H₁₇(122)	2.55×10²	3.68	4.70
6	H(2)+C₁₀H₁₈(120) $⇌$ H₂(3)+C₁₀H₁₇(123)	2.55×10²	3.68	4.70
7	H(2)+C₈H₁₀(1) $⇌$ H₂(3)+C₈H₉(12)	1.60×10¹³	0	8.17
8	H(2)+C₆H₆(29) $⇌$ H₂(3)+C₆H₅(10)	4.57×10⁸	1.88	14.84
9	H(2)+C₁₀H₁₆(124) $⇌$ H₂(3)+C₁₀H₁₅(127)	2.55×10²	3.68	4.70
10	H(2)+C₇H₈(23) $⇌$ H₂(3)+C₇H₇(9)	7.54×10⁴	2.57	3.15
11	H(2)+C₇H₈(22) $⇌$ H₂(3)+C₇H₇(9)	8.94×10^-1	4.34	-0.40
12	H(2)+C₈H₈(27) $⇌$ H₂(3)+C₈H₇(33)	2.81×10⁵	2.41	8.84
13	H(2)+C₁₀H₁₆(126) $⇌$ C₁₀H₁₇(123)	1.46×10⁸	1.64	1.37
14	CH₃(4)+C₇H₇(9) $⇌$ C₈H₁₀(1)	6.75×10¹⁶	-1.29	0
15	H(2)+C₁₀H₁₆(126) $⇌$ C₁₀H₁₇(122)	1.46×10⁸	1.64	1.37
16	C₂H₄(7)+C₂H₅(6) $⇌$ C₄H₉(175)	4.24×10³	2.41	5.06
17	H(2)+C₂H₃(8)(M) $⇌$ C₂H₄(7)(M)	3.90×10¹³	0.20	0
18	H(2)+C₄H₈(222) $⇌$ C₄H₉(175)	3.01×10⁸	1.60	2.40
19	H(2)+C₂H₄(7)(M) $⇌$ C₂H₅(6)(M)	1.40×10⁹	1.46	1.36
20	C₅H₁₀(195) $⇌$ C₂H₄(7)+C₃H₆(213)	8.70×10¹¹	0	55.69
21	CH₃(4)+C₃H₆(213) $⇌$ CH₄(5)+allyl(224)	7.20×10^-2	4.25	7.53
22	CH₃(4)+C₈H₈(27) $⇌$ CH₄(5)+C₈H₇(33)	3.21×10⁷	1.82	14.16
23	CH₃(4)+C₂H₄(7) $⇌$ CH₄(5)+C₂H₃(8)	6.00×10⁷	1.56	16.63
24	CH₃(4)+C₈H₁₀(1) $⇌$ CH₄(5)+C₈H₉(12)	6.00×10¹²	0	12.62
25	CH₃(4)+C₈H₈(27) $⇌$ CH₄(5)+C₈H₇(31)	3.21×10⁷	1.82	14.16
26	CH₃(4)+C₇H₈(23) $⇌$ CH₄(5)+C₇H₇(9)	1.07×10⁶	2.27	4.39
27	CH₃(4)+C₁₀H₁₈(120) $⇌$ CH₄(5)+C₁₀H₁₇(123)	6.42×10^-2	4.34	6.61
28	CH₃(4)+C₁₀H₁₈(120) $⇌$ CH₄(5)+C₁₀H₁₇(122)	6.42×10^-2	4.34	6.61
29	CH₃(4)+C₆H₆(29) $⇌$ CH₄(5)+C₆H₅(10)	5.15×10³	2.90	15.31
30	CH₃(4)+C₈H₇(32) $⇌$ CH₄(5)+C₈H₆(90)	8.20×10⁶	1.88	-1.12
31	CH₃(4)+C₈H₈(27) $⇌$ CH₄(5)+C₈H₇(32)	9.80×10^-2	4.01	12.90
32	CH₃(4)+C₁₀H₁₆(124) $⇌$ CH₄(5)+C₁₀H₁₅(127)	6.42×10^-2	4.34	6.61
33	CH₃(4)+C₁₀H₁₈(120) $⇌$ CH₄(5)+C₁₀H₁₇(121)	2.26×10^-2	4.34	7.69
34	C₇H₇(9) $⇌$ C₇H₇(21)	9.78×10⁹	0.58	28.56
35	C₄H₆(133)+C₆H₁₀(132) $⇌$ C₁₀H₁₆(129)	1.71×10⁴	1.53	23.41
36	H(2)+C₁₀H₁₆(125) $⇌$ C₁₀H₁₇(122)	7.72×10⁷	1.64	2.17
37	H(2)+C₈H₈(27) $⇌$ C₈H₉(11)	6.00×10⁷	1.64	1.55
38	H(2)+allyl(224) $⇌$ C₃H₆(213)	5.84×10¹³	0.18	0.12
39	H(2)+C₃H₆(213) $⇌$ H₂(3)+allyl(224)	3.36×10³	3.14	4.29
40	CH₃(4)+C₃H₆(213) $⇌$ C₄H₉(223)	2.10×10⁴	2.41	5.32
41	C₂H₅(6)+allyl(224) $⇌$ C₂H₄(7)+C₃H₆(213)	1.37×10¹⁴	-0.35	-0.13
42	H(2)+C₃H₆(213) $⇌$ C₃H₇(214)	1.84×10⁹	1.55	1.57
43	C₃H₆(213)+npropyl(172) $⇌$ C₆H₁₃(199)	2.13×10³	2.41	4.75
44	C₇H₈(22)+C₈H₇(31) $⇌$ C₇H₇(9)+C₈H₈(27)	2.90×10^-2	4.34	-5.60
45	C₂H₄(7)+C₈H₁₂(130) $⇌$ C₁₀H₁₆(125)	2.64×10¹¹	0	29.61
46	C₂H₄(7)+C₄H₆(133) $⇌$ C₆H₁₀(132)	1.00×10¹⁰	0	20.00
47	C₂H₃(8)+C₈H₈(27) $⇌$ C₂H₄(7)+C₈H₇(32)	3.91×10^-3	4.50	3.67
48	C₂H₃(8)+C₈H₁₀(1) $⇌$ C₂H₄(7)+C₈H₉(11)	5.56×10^-3	4.34	0.20
49	C₂H₄(7)+npropyl(172) $⇌$ C₅H₁₁(178)	4.24×10³	2.41	5.06
50	C₂H₄(7)+C₈H₇(31) $⇌$ C₂H₃(8)+C₈H₈(27)	2.20×10^-2	4.40	4.75
51	C₂H₄(7)+C₈H₇(33) $⇌$ C₂H₃(8)+C₈H₈(27)	2.20×10^-2	4.40	4.75
52	H(2)+CH₃(4)(M) $⇌$ CH₄(5)(M)	2.10×10¹⁴	0	0
53	H(2)+C₈H₉(12) $⇌$ C₈H₁₀(1)	9.17×10¹³	0.12	0
54	C₈H₉(12)+C₈H₁₁(16) $⇌$ 2C₈H₁₀(1)	8.43×10¹¹	0	0
55	CH₃(4)+C₈H₁₁(16) $⇌$ CH₄(5)+C₈H₁₀(1)	3.38×10¹¹	-0.18	-0.01
56	H(2)+C₈H₁₀(1) $⇌$ C₈H₁₁(16)	8.76×10⁷	1.71	6.09
57	2CH₃(4) $⇌$ H(2)+C₂H₅(6)	5.40×10¹³	0	16.06
58	CH₃(4)+C₂H₅(6) $⇌$ CH₄(5)+C₂H₄(7)	9.00×10¹¹	0	0
59	C₂H₅(6)+C₈H₉(12) $⇌$ C₂H₄(7)+C₈H₁₀(1)	6.90×10¹³	-0.35	0
60	2H(2)+H₂(3) $⇌$ 2H₂(3)	1.00×10¹⁷	-0.60	0
61	2H(2)(M) $⇌$ H₂(3)(M)	7.00×10¹⁷	-1.00	0
62	H(2)+C₈H₁₁(16) $⇌$ H₂(3)+C₈H₁₀(1)	1.00×10¹⁰	0	0
63	H(2)+C2H5(6) $⇌$ H₂(3)+C₂H₄(7)	1.08×10¹³	0	0
64	C₂H₃(8)+C₈H₁₁(16) $⇌$ C₂H₄(7)+C₈H₁₀(1)	8.43×10¹¹	0	0
65	C₂H₃(8)+C₈H₁₀(1) $⇌$ C₂H₄(7)+C₈H₉(12)	5.40×10^-4	4.55	3.50
66	C₂H₃(8)+C₂H₅(6) $⇌$ 2C₂H₄(7)	4.56×10¹⁴	-0.70	0
67	H(2)+C₁₀H₁₇(122) $⇌$ C₁₀H₁₈(120)	1.95×10¹²	0.35	0
68	H(2)+C₁₀H₁₇(123) $⇌$ C₁₀H₁₈(120)	1.58×10¹³	-0.22	0
69	C₁₀H₁₇(122) $⇌$ C₁₀H₁₇(123)	6.76×10⁹	0.88	38.00
70	C₁₀H₁₇(122) $⇌$ C₁₀H₁₇(123)	2.84×10⁷	1.625	35.45
71	C₁₀H₁₇(122) $⇌$ C₁₀H₁₇(123)	2.28×10^-3	3.95	11.17
72	C₁₀H₁₇(122) $⇌$ C₁₀H₁₇(123)	5.64×10^-2	3.28	5.91
73	C₁₀H₁₇(122) $⇌$ C₁₀H₁₇(123)	6.76×10⁹	0.88	38.00
74	C₁₀H₁₇(122)+C₁₀H₁₈(120) $⇌$ C₁₀H₁₇(123)+C₁₀H₁₈(120)	1.03×10^-2	4.29	7.71
75	C₂H₅(6)+C₁₀H₁₇(123) $⇌$ C₂H₄(7)+C₁₀H₁₈(120)	6.33×10¹⁴	-0.70	0
76	npropyl(172)+C₁₇H₃₅(171) $⇌$ C₂₀H₄₂(170)	3.19×10¹⁶	-1.18	0
77	CH₃(4)+C₂H₄(7) $⇌$ npropyl(172)	4.18×10⁴	2.41	5.63
78	CH₃(4)+npropyl(172) $⇌$ CH₄(5)+C₃H₆(213)	2.30×10¹³	-0.32	0
79	H(2)+npropyl(172) $⇌$ H₂(3)+C₃H₆(213)	3.62×10¹²	0	0
80	allyl(224)+npropyl(172) $⇌$ 2C₃H₆(213)	5.80×10¹²	0	-0.13

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重质油高温快速热解自动反应网络的动力学建模

Kinetic modeling of the high-temperature rapid pyrolysis auto-reaction network of heavy oil

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