CH4+C2H5OH+Ar体系热解的气相动力学研究

doi:10.15541/jim20240158

无机材料学报 ›› 2024, Vol. 39 ›› Issue (11): 1235-1244.DOI: 10.15541/jim20240158 CSTR: 32189.14.10.15541/jim20240158

CH₄+C₂H₅OH+Ar体系热解的气相动力学研究

马永杰¹(), 刘永胜¹, 关康²(), 曾庆丰³()

1.西北工业大学超高温结构复合材料重点实验室, 西安 710072
2.华南理工大学材料科学与工程学院, 广州 510640
3.天目山实验室高性能航空材料与先进制造中心, 杭州 311115

收稿日期:2024-04-01 修回日期:2024-06-21 出版日期:2024-11-20 网络出版日期:2024-06-24
通讯作者: 关康, 副教授. E-mail: mskguan@scut.edu.cn;
曾庆丰, 研究员. E-mail: bht0045@tmslab.cn
作者简介:马永杰(1999-), 男, 硕士研究生. E-mail: mayongjie@mail.nwpu.edu.cn
基金资助:
浙江省重点研发计划(2024SSYS0085);国家自然科学基金(51702100);国家自然科学基金(51972268);广东省基础与应用基础研究基金(2023A1515012156);广东省基础与应用基础研究基金(2024A1515011656);中央高校基本科研业务费专项资金(2022ZYGXZR026)

Gas-phase Kinetic Study of Pyrolysis in the System of CH₄+C₂H₅OH+Ar

MA Yongjie¹(), LIU Yongsheng¹, GUAN Kang²(), ZENG Qingfeng³()

1. Science and Technology on Thermostructural Composite Materials Laboratory, Northwestern Polytechnical University, Xi'an 710072, China
2. School of Materials Science and Engineering, South China University of Technology, Guangzhou 510640, China
3. High Performance Aviation Materials and Advanced Manufacturing Center, Tianmushan Laboratory, Hangzhou 311115, China

Received:2024-04-01 Revised:2024-06-21 Published:2024-11-20 Online:2024-06-24
Contact: GUAN Kang, associate professor. E-mail: mskguan@scut.edu.cn;
ZENG Qingfeng, professor. E-mail: bht0045@tmslab.cn
About author:MA Yongjie (1999-), male, Master candidate. E-mail: mayongjie@mail.nwpu.edu.cn
Supported by:
Key R&D Program of Zhejiang(2024SSYS0085);National Natural Science Foundation of China(51702100);National Natural Science Foundation of China(51972268);Guangdong Basic and Applied Basic Research Foundation(2023A1515012156);Guangdong Basic and Applied Basic Research Foundation(2024A1515011656);Fundamental Research Funds for the Central Universities(2022ZYGXZR026)

摘要/Abstract

摘要：

通过化学气相渗透工艺, 利用以CH₄和C₂H₅OH为前驱体制备碳/碳复合材料, 可以提高沉积速率且易得到高织构的热解炭。探究其反应机制可以更好地用于计算流体力学(CFD)研究。化学反应机制往往包含大量自由基和反应, 而以实验为主手动构建反应机制很容易遗漏重要物质和反应。本研究利用反应机制生成器(RMG)构建了CH₄+C₂H₅OH+Ar体系详细的气相热解动力学机制, 其涵盖31种核心物质和214个核心反应, 预测了主要物质形成和消耗的趋势, 模拟结果与实验结果趋势相吻合。通过详细的动力学机制研究和反应物以及部分重要产物灵敏度分析, 识别了影响关键物质生成和消耗的反应。反应路径分析揭示了详细机制中不同物质之间的关系, 并确定了机制中的核心物质。在温度1373 K、压力10 kPa条件下, 依据灵敏度分析和路径分析的结果对详细机制进行了简化, 得到包含18种物质和44个反应的气相简化动力学机制。该简化机制在保留关键物质的同时显著提高了计算效率, 为进一步CFD研究和应用提供了更为便利的基础。

关键词: 碳/碳复合材料, 气相动力学, 机制分析, 机制简化

Abstract:

Preparation of carbon-carbon composites through the chemical vapor infiltration (CVI) process, utilizing CH₄ and C₂H₅OH as precursors, can effectively improve the deposition rate and produce highly structured pyrolytic carbon. Understanding the reaction mechanism is essential for computational fluid dynamics (CFD) studies. Chemical reaction mechanisms typically involve numerous free radicals and reactions, and manually constructing such mechanisms based on experimental data alone risks omitting critical species and reactions. Hence, in this research, a thorough gas-phase pyrolysis kinetic mechanism for the CH₄+C₂H₅OH+Ar system was developed using the reaction mechanism generator (RMG). This mechanism included 31 core species and 214 core reactions, accurately predicting the evolution of major species' formation and consumption. The simulation results were consistent with experimental observations. Through a detailed analysis of the kinetics and sensitivity of reactants and critical products, reactions influencing the formation and consumption of crucial species were identified. Reaction pathway analysis further clarified relationships among different species, identifying core species within the mechanism. By simplifying the detailed mechanism based on sensitivity and rection pathway analysis at 1373 K and 10 kPa, a gas-phase kinetic mechanism was derived, composed of 18 species and 44 reactions. This streamlined model substantially boosts computational efficiency while retaining key species, providing a more convenient foundation for further CFD studies and applications.

Key words: carbon/carbon composite, gas-phase dynamic, mechanism analysis, mechanism simplification

中图分类号:

TB332

马永杰, 刘永胜, 关康, 曾庆丰. CH₄+C₂H₅OH+Ar体系热解的气相动力学研究[J]. 无机材料学报, 2024, 39(11): 1235-1244.

MA Yongjie, LIU Yongsheng, GUAN Kang, ZENG Qingfeng. Gas-phase Kinetic Study of Pyrolysis in the System of CH₄+C₂H₅OH+Ar[J]. Journal of Inorganic Materials, 2024, 39(11): 1235-1244.

图/表 11

参考文献 28

[1]	CHEN S, QIU X, ZHANG B, et al. Advances in antioxidation coating materials for carbon/carbon composites. Journal of Alloys and Compounds, 2021, 886: 161143.
[2]	JIN X, FAN X, LU C, et al. Advances in oxidation and ablation resistance of high and ultra-high temperature ceramics modified or coated carbon/carbon composites. Journal of the European Ceramic Society, 2018, 38(1): 1.
[3]	FU Q, ZHANG P, ZHUANG L, et al. Micro/nano multiscale reinforcing strategies toward extreme high-temperature applications: take carbon/carbon composites and their coatings as the examples. Journal of Materials Science & Technology, 2022, 96: 31.
[4]	BHONG M, KHAN T K H, DEVADE K, et al. Review of composite materials and applications. Materials Today: Proceedings, 2023, DOI: 10.1016/j.matpr.2023.10.026.
[5]	MANAWI Y M, IHSANULLAH, SAMARA A, et al. A review of carbon nanomaterials’ synthesis via the chemical vapor deposition (CVD) method. Materials, 2018, 11(5): 822.
[6]	ZHENG L, WANG Y, QIN J, et al. Scalable manufacturing of carbon nanotubes on continuous carbon fibers surface from chemical vapor deposition. Vacuum, 2018, 152: 84.
[7]	SHAH K A, TALI B A. Synthesis of carbon nanotubes by catalytic chemical vapour deposition: a review on carbon sources, catalysts and substrates. Materials Science in Semiconductor Processing, 2016, 41: 67.
[8]	WEI X, CHENG L, ZHANG L, et al. Numerical simulation of effect of methyltrichlorosilane flux on isothermal chemical vapor infiltration process of C/SiC composites. Journal of the American Ceramic Society, 2006, 89(9): 2762.
[9]	LI H, LI A, BAI R, et al. Numerical simulation of chemical vapor infiltration of propylene into C/C composites with reduced multi-step kinetic models. Carbon, 2005, 43(14): 2937
[10]	KIM H G, JI W, KWON H J, et al. Full-scale multi-physics numerical analysis of an isothermal chemical vapor infiltration process for manufacturing C/C composites. Carbon, 2021, 172: 174.
[11]	REN B, ZHANG S, HE L, et al. Effect of oxygen and hydrogen on microstructure of pyrolytic carbon deposited from thermal decomposition of methane and ethanol. Journal of Solid State Chemistry, 2018, 261: 86.
[12]	REN J, LI K, ZHANG S, et al. Preparation of carbon/carbon composite by pyrolysis of ethanol and methane. Materials & Design, 2015, 65: 174.
[13]	LI A, ZHANG S, REZNIK B, et al. Chemistry and kinetics of chemical vapor deposition of pyrolytic carbon from ethanol. Proceedings of the Combustion Institute, 2011, 33(2): 1843.
[14]	LI A, ZHANG S, REZNIK B, et al. Synthesis of pyrolytic carbon composites using ethanol as precursor. Industrial & Engineering Chemistry Research, 2010, 49(21): 10421.
[15]	MARINOV N M. A detailed chemical kinetic model for high temperature ethanol oxidation. International Journal of Chemical Kinetics, 1999, 31(3): 183.
[16]	MINAKOV A V, SIMUNIN M M, RYZHKOV I I. Modelling of ethanol pyrolysis in a commercial CVD reactor for growing carbon layers on alumina substrates. International Journal of Heat and Mass Transfer, 2019, 145: 118764.
[17]	HU C, LI H, ZHANG S, et al. A molecular-level analysis of gas-phase reactions in chemical vapor deposition of carbon from methane using a detailed kinetic model. Journal of Materials Science, 2016, 51(8): 38976.
[18]	SHINDE V M, PRADEEP P. Detailed gas-phase kinetics and reduced reaction mechanism for methane pyrolysis involved in CVD/CVI processes. Journal of Analytical and Applied Pyrolysis, 2021, 154: 104998.
[19]	GAO C W, ALLEN J W, GREEN W H, et al. Reaction mechanism generator: automatic construction of chemical kinetic mechanisms. Computer Physics Communications, 2016, 203: 212.
[20]	CURTISS C F, HIRSCHFELDER J O. Integration of stiff equations. Proceedings of the National Academy of Sciences, 1952, 38(3): 235.
[21]	BENSON S W, BUSS J H. Additivity rules for the estimation of molecular properties. Thermodynamic properties. Journal of Chemical Physics, 1958, 29(3): 546.
[22]	BENSON S W. Thermochemical kinetics:methods for the estimation of thermochemical data and rate parameters. New York: John Wiley and Sons, 1976.
[23]	HASHEMI H, CHRISTENSEN J M, GLARBORG P. High- pressure pyrolysis and oxidation of ethanol. Fuel, 2018, 218: 247.
[24]	SUSNOW R G, DEAN A M, GREEN W H, et al. Rate-based construction of kinetic models for complex systems. Journal of Physical Chemistry A, 1997, 101(20): 3731.
[25]	LIU M, GRINBERG D A, JOHNSON M S, et al. Reaction mechanism generator v3.0: advances in automatic mechanism generation. Journal of Chemical Information and Modeling, 2021, 61(6): 2686.
[26]	HUANG Q, CHEN Y, BAO Z, et al. PFR model for high-pressure reaction flow of fuel. Combustion Science and Technology, 2022, 194(11): 2268.
[27]	GUPTA A, NIGAM S, SHINDE V M. Gas-phase kinetic of boron carbide chemical vapor deposition using BCl₃+ CH₄+ H₂ mixture. Journal of the American Ceramic Society, 2022, 105(6): 3885.
[28]	BRÜGGERT M, HU Z, HÜTTINGER K J. Chemistry and kinetics of chemical vapor deposition of pyrocarbon: VI. influence of temperature using methane as a carbon source. Carbon, 1999, 37(12): 2021.

No.	Reaction	*A	n	E/(kJ·mol^-1)
1	C₂H₄+M<=>H+C₂H₃+M	3.98×10¹⁷	0	411.144
2	H+C₂H₄<=>H₂+C₂H₃	1.32×10⁷	2.5	47.168
3	H+H+M<=>H₂+M	1.0	0	0
4	CH₄+M<=>H+CH₃+M	1.0×10¹⁷	0	359.232
5	CH₃+C₂H₄<=>CH₄+C₂H₃	5.0×10¹²	0	54.428
6	H₂+CH₃<=>H+CH₄	2.75×10⁴	2.5	39.435
7	2CH₃+M<=>C₂H₆+M	3.08×10⁴¹	-7.0	11.568
8	CH₃+CH₄<=>H+C₂H₆	8.0×10¹³	2.0	167.472
9	C₂H₅<=>H+C₂H₄	2.04×10¹⁵	0	144.713
10	C₂H₆<=>H+C₂H₅	2.08×10³⁸	-7.1	445.928
11	2CH₃<=>H+C₂H₅	3.01×10¹³	0	56.576
12	CH₃+CH₄<=>H₂+C₂H₅	1.0×10¹³	0	96.296
13	H+C₂H₅<=>H₂+C₂H₄	2.0×10¹²	0	0
14	2C₂H₄<=>C₂H₃+C₂H₅	1.82×10¹⁴	0	270.183
15	C₂H₃+C₂H₆<=>C₂H₄+C₂H₅	1.08×10^-3	4.5	14.653
16	H+C₂H₆<=>H₂+C₂H₅	5.4×10²	3.5	21.813
17	CH₃+C₂H₆<=>CH₄+C₂H₅	5.5×10^-1	4.0	37.757
18	H+C₃H₆<=>CH₃+C₂H₄	3.4×10¹³	0	14.650
19	C₃H₆<=>CH₃+C₂H₃	2.5×10¹⁴	0	417.378
20	C₂H₄+M<=>H₂+C₂H₂+M	8.0×10¹²	0.4	371.641
21	H+C₂H₃<=>H₂+C₂H₂	3.0×10¹³	0	0
22	C₃H₆<=>CH₄+C₂H₂	1.8×10¹²	0	293.076
23	C₂H₃+M<=>H+C₂H₂+M	7.94×10¹⁴	0	130.088
24	2H+H₂<=>2H₂	9.0×10¹⁶	-0.6	0
25	CH₃+C₂H₃<=>CH₄+C₂H₂	2.0×10¹³	0	0
26	2H+H₂O<=>H₂+H₂O	6.0×10¹⁹	-1.25	0
27	H₂O+C₂H₄(+M)<=>C₂H₅OH(+M)	1.0×100	0	0
28	2C₂H₅<=>C₂H₄+C₂H₆	6.9×10¹³	-0.35	0
29	2C₂H₃<=>C₂H₂+C₂H₄	2.9597×10¹³	-0.312	0
30	CH₃+C₂H₅<=>CH₄+C₂H₄	6.57×10¹⁴	-0.68	0
31	C₂H₃+C₂H₅<=>C₂H₂+C₂H₆	2.1064×10¹³	-0.251	0
32	CH₃+CH₂OH(+M)<=>C₂H₅OH(+M)	1.0	0	0
33	CH₃+CH₂OH(+M)<=>H₂O+C₂H₄(+M)	1.0	0	0
34	C₂H₅OH(+M)<=>H₂+CH₃CHO(+M)	7.24×10¹¹	0.095	381.028
35	HCO+CH₃(+M) <=>CH₃CHO(+M)	1.0	0	0
36	H+HCO<=>H₂+CO	7.34×10¹³	0	0
37	HCO+CH₃<=>CO+CH₄	2.648×10¹³	0	0
38	H₂O+HCO<=>H+H₂O+CO	1.5×10¹⁸	-1.0	71.176
39	H+CH₃CHO<=>H₂+CO+CH₃	2.05×10⁹	1.16	10.069
40	CH₃+CH₃CHO<=>CO+CH₃+CH₄	2.72×10⁶	1.77	24.786
41	HCO+M<=>CO+H+M	1.87×10¹⁷	-1.0	71.176
42	CH₃CHO(+M)<=>CO+CH₄(+M)	1.0	0	0
43	HCO+C₂H₃<=>CO+C₂H₄	9.033×10¹³	0	0
44	HCO+C₂H₅<=>CO+C₂H₆	4.3×10¹³	0	0

No.	Reaction	*A	n	E/(kJ·mol^-1)
1	C₂H₄+M<=>H+C₂H₃+M	3.98×10¹⁷	0	411.144
2	H+C₂H₄<=>H₂+C₂H₃	1.32×10⁷	2.5	47.168
3	H+H+M<=>H₂+M	1.0	0	0
4	CH₄+M<=>H+CH₃+M	1.0×10¹⁷	0	359.232
5	CH₃+C₂H₄<=>CH₄+C₂H₃	5.0×10¹²	0	54.428
6	H₂+CH₃<=>H+CH₄	2.75×10⁴	2.5	39.435
7	2CH₃+M<=>C₂H₆+M	3.08×10⁴¹	-7.0	11.568
8	CH₃+CH₄<=>H+C₂H₆	8.0×10¹³	2.0	167.472
9	C₂H₅<=>H+C₂H₄	2.04×10¹⁵	0	144.713
10	C₂H₆<=>H+C₂H₅	2.08×10³⁸	-7.1	445.928
11	2CH₃<=>H+C₂H₅	3.01×10¹³	0	56.576
12	CH₃+CH₄<=>H₂+C₂H₅	1.0×10¹³	0	96.296
13	H+C₂H₅<=>H₂+C₂H₄	2.0×10¹²	0	0
14	2C₂H₄<=>C₂H₃+C₂H₅	1.82×10¹⁴	0	270.183
15	C₂H₃+C₂H₆<=>C₂H₄+C₂H₅	1.08×10^-3	4.5	14.653
16	H+C₂H₆<=>H₂+C₂H₅	5.4×10²	3.5	21.813
17	CH₃+C₂H₆<=>CH₄+C₂H₅	5.5×10^-1	4.0	37.757
18	H+C₃H₆<=>CH₃+C₂H₄	3.4×10¹³	0	14.650
19	C₃H₆<=>CH₃+C₂H₃	2.5×10¹⁴	0	417.378
20	C₂H₄+M<=>H₂+C₂H₂+M	8.0×10¹²	0.4	371.641
21	H+C₂H₃<=>H₂+C₂H₂	3.0×10¹³	0	0
22	C₃H₆<=>CH₄+C₂H₂	1.8×10¹²	0	293.076
23	C₂H₃+M<=>H+C₂H₂+M	7.94×10¹⁴	0	130.088
24	2H+H₂<=>2H₂	9.0×10¹⁶	-0.6	0
25	CH₃+C₂H₃<=>CH₄+C₂H₂	2.0×10¹³	0	0
26	2H+H₂O<=>H₂+H₂O	6.0×10¹⁹	-1.25	0
27	H₂O+C₂H₄(+M)<=>C₂H₅OH(+M)	1.0×100	0	0
28	2C₂H₅<=>C₂H₄+C₂H₆	6.9×10¹³	-0.35	0
29	2C₂H₃<=>C₂H₂+C₂H₄	2.9597×10¹³	-0.312	0
30	CH₃+C₂H₅<=>CH₄+C₂H₄	6.57×10¹⁴	-0.68	0
31	C₂H₃+C₂H₅<=>C₂H₂+C₂H₆	2.1064×10¹³	-0.251	0
32	CH₃+CH₂OH(+M)<=>C₂H₅OH(+M)	1.0	0	0
33	CH₃+CH₂OH(+M)<=>H₂O+C₂H₄(+M)	1.0	0	0
34	C₂H₅OH(+M)<=>H₂+CH₃CHO(+M)	7.24×10¹¹	0.095	381.028
35	HCO+CH₃(+M) <=>CH₃CHO(+M)	1.0	0	0
36	H+HCO<=>H₂+CO	7.34×10¹³	0	0
37	HCO+CH₃<=>CO+CH₄	2.648×10¹³	0	0
38	H₂O+HCO<=>H+H₂O+CO	1.5×10¹⁸	-1.0	71.176
39	H+CH₃CHO<=>H₂+CO+CH₃	2.05×10⁹	1.16	10.069
40	CH₃+CH₃CHO<=>CO+CH₃+CH₄	2.72×10⁶	1.77	24.786
41	HCO+M<=>CO+H+M	1.87×10¹⁷	-1.0	71.176
42	CH₃CHO(+M)<=>CO+CH₄(+M)	1.0	0	0
43	HCO+C₂H₃<=>CO+C₂H₄	9.033×10¹³	0	0
44	HCO+C₂H₅<=>CO+C₂H₆	4.3×10¹³	0	0

CH₄+C₂H₅OH+Ar体系热解的气相动力学研究

Gas-phase Kinetic Study of Pyrolysis in the System of CH₄+C₂H₅OH+Ar

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 11

参考文献 28

相关文章 14

编辑推荐

Metrics

本文评价

[1]	刘宇峰, 俸翔, 王金明, 许正辉, 李同起, 焦星剑, 王雅雷, 熊翔. 高性能针刺碳/碳复合材料的制备与性能[J]. 无机材料学报, 2020, 35(10): 1105-1111.
[2]	闫明洋, 杨敏, 李红, 任慕苏, 俞鸣明, 孙晋良. 原位生长的气相生长碳纤维增强C/C复合材料的制备及其弯曲性能[J]. 无机材料学报, 2018, 33(11): 1161-1166.
[3]	郑金煌, 李贺军, 崔红, 王毅, 邓海亮, 殷忠义, 姚冬梅, 苏红. C/C复合材料拉伸强度与针刺成型参数相关性研究[J]. 无机材料学报, 2017, 32(11): 1147-1153.
[4]	张雨雷,李贺军,姚西媛,付前刚,李克智. C/SiC/Si-Mo-Cr复合涂层碳/碳复合材料力学性能研究[J]. 无机材料学报, 2008, 23(4): 725-728.
[5]	张磊磊,李贺军,李克智,李新涛,翟言强,张雨雷. 碳/碳复合材料表面粗糙度对成骨细胞生长行为的影响[J]. 无机材料学报, 2008, 23(2): 341-345.
[6]	孙万昌,李贺军,卢锦花,白瑞成,黄勇. 不同层次界面对C/C复合材料断裂行为的影响[J]. 无机材料学报, 2005, 20(6): 1457-1462.
[7]	李劲,陈振华. 催化型化学液相气化渗透沉积制备碳/碳复合材料工艺研究[J]. 无机材料学报, 2005, 20(6): 1450-1456.
[8]	孙万昌,李贺军,卢锦花,白瑞成,黄勇. 不同层次界面对C/C复合材料断裂行为的影响[J]. 无机材料学报, 2005, 20(6): 1257-1462.
[9]	孙万昌,李贺军,白瑞成,黄勇. 微观组织结构对C/C复合材料力学行为的影响[J]. 无机材料学报, 2005, 20(3): 671-676.
[10]	孙万昌,李贺军,陈三平,张守阳,李克智. CLVI制备C/C复合材料的微观结构及力学性能研究[J]. 无机材料学报, 2003, 18(1): 121-128.
[11]	付涛,憨勇,宋忠孝,李金勇,徐可为. 碳/碳复合材料表面诱导沉积生理磷灰石层[J]. 无机材料学报, 2002, 17(1): 189-192.
[12]	张守阳1,李贺军,李克智,孙军. C/C复合材料层间裂纹扩展研究[J]. 无机材料学报, 2002, 17(1): 91-95.
[13]	孙乐民,李贺军,张守阳. 沥青基碳/碳复合材料的组织特性[J]. 无机材料学报, 2000, 15(6): 1111-1116.
[14]	罗瑞盈,金志浩. 添加剂对快速LARGE CVD抗氧化LARGE C/C复合材料力学性能影响[J]. 无机材料学报, 1997, 12(4): 627-631.