基于反应分子动力学的烟煤分子模型构建及热解机制

doi:10.16265/j.cnki.issn1003-3033.2026.07.1961

中国安全科学学报 ›› 2026, Vol. 36 ›› Issue (7): 153-163.doi: 10.16265/j.cnki.issn1003-3033.2026.07.1961

基于反应分子动力学的烟煤分子模型构建及热解机制

李静静¹^,²(), 江丙友¹^,²^,^**(), 许颇³, 苏明清⁴^,⁵, 鲁昆仑¹^,², 余昌飞¹^,²

¹ 安徽理工大学工业粉尘防控与职业安全健康教育部重点实验室, 安徽淮南 232001
² 安徽理工大学安全科学与工程学院, 安徽淮南 232001
³ 锦浪科技股份有限公司, 浙江宁波 315712
⁴ 中国安全生产科学研究院, 北京 100012
⁵ 重大危险源与化工园区系统安全应急管理部重点实验室, 北京 100012

收稿日期:2026-03-06 修回日期:2026-05-15 出版日期:2026-07-28
通信作者:
^**江丙友(1987—),男,安徽利辛人,博士,教授,主要从事工业粉尘防控与气体粉尘爆炸防治方面的研究。E-mail: cumtjiangby@163.com。
作者简介:
李静静 (1999—),女,山西长治人,博士研究生,主要研究方向为气体粉尘爆炸防治技术。E-mail:lijing_eudemonia@163.com。
苏明清, 工程师;
鲁昆仑, 副教授
基金资助:
安徽省自然科学基金杰出青年资助(2308085J19); 安徽省教育厅高校杰出青年资助项目(2022AH020057); 国家自然科学基金资助(52504198); 工业粉尘防控与职业健康教育部重点实验室开放基金资助(EK20241001)

Construction of a bituminous coal molecular model and its pyrolysis mechanism based on reactive molecular dynamics

Li Jingjing¹^,²(), Jiang Bingyou¹^,²^,^**(), Xu Po³, Su Mingqing⁴^,⁵, Lu Kunlun¹^,², Yu Changfei¹^,²

¹ Key Laboratory of Industrial Dust Control and Occupational Health and Safety, Ministry of Education, Anhui University of Science and Technology, Huainan Anhui 232001, China
² School of Safety Science and Engineering, Anhui University of Science and Technology, Huainan Anhui 232001, China
³ Ginlong Technologies Co., Ltd., Ningbo Zhejiang 315712, China
⁴ China Academy of Safety Science and Technology, Beijing 100012, China
⁵ Key Laboratory of Major Hazard and Chemical Industry Park System Safety, Beijing 100012, China

Received:2026-03-06 Revised:2026-05-15 Published:2026-07-28

摘要/Abstract

摘要：

为揭示烟煤热解过程中分子结构演化及产物生成特性,以平顶山烟煤为研究对象,采用试验表征与反应力场分子动力学(ReaxFF-MD)模拟相结合的方法,通过X射线光电子能谱(XPS)、红外光谱(FTIR)、固态核磁共振波谱(¹³C NMR)等表征技术获取煤样结构参数,结合密度泛函理论(DFT)构建并验证煤分子模型;基于ReaxFF-MD模拟研究烟煤热解产物分布特性与结构演化机制,并与宏观热解特征相互印证。结果表明:烟煤碳骨架由71.23%芳香碳和28.77%脂肪碳构成,芳香结构以苯环和萘环为主;构建的煤分子式为C₁₃₀H₈₂O₁₈N₆S,其DFT计算分子振动频率与试验红外光谱在1 500~1 000 cm^-1和3 700~2 800 cm^-1范围内宽峰特征一致;煤分子热解过程中,含氧官能团脱除,芳香结构逐步缩聚,并伴随CH₄、CO、CO₂、H₂和H₂O等气相产物生成,其总产量随升温速率增大而降低,低升温速率更有利于二次重组反应;烟煤热解的质量残余率、特征峰温度迁移趋势和气相产物种类与模拟结果一致,其中质量残余率对应偏差均小于5%;烟煤分子模型能够较好反映烟煤热解过程中的结构演化与产物生成特征。

关键词: 反应力场分子动力学(ReaxFF-MD), 烟煤, 分子模型, 热解, 含氧官能团

Abstract:

To reveal the molecular structure evolution and product generation characteristics during bituminous coal pyrolysis, Pingdingshan bituminous coal was selected as the research object. A method combining experimental characterization and ReaxFF-MD simulations was adopted. Structural parameters of the coal sample were obtained using X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), and solid-state nuclear magnetic resonance spectroscopy (¹³C NMR). A coal molecular model was constructed and validated based on density functional theory (DFT). Subsequently, the product distribution and structural evolution during bituminous coal pyrolysis were investigated using ReaxFF-MD simulation. The simulation results were further compared with macroscopic pyrolysis characteristics. The results show that the carbon skeleton of bituminous coal is consisted of 71.23% aromatic carbon and 28.77% aliphatic carbon. The aromatic structures are mainly composed of benzene and naphthalene rings. The constructed coal molecular formula is C₁₃₀H₈₂O₁₈N₆S. The molecular vibrational frequencies calculated by DFT are consistent with the broad peaks in the experimental FTIR spectra within the ranges of 1 500~1 000 cm^-1 and 3 700~2 800 cm^-1. During coal molecular pyrolysis, oxygen-containing functional groups are removed. Aromatic structures are gradually condensed. Gaseous products including CH₄, CO, CO₂, H₂, and H₂O, are generated simultaneously. Their total yield decreases with increasing heating rate. A lower heating rates is more favorable for secondary recombination reactions. The mass residual ratio, characteristic peak temperature shift trend, and gaseous product types of bituminous coal pyrolysis are consistent with the simulation results. The corresponding deviations in mass residual ratio are all less than 5%. The bituminous coal molecular model can well reflect the structural evolution and product generation behaviors during bituminous coal pyrolysis.

Key words: reactive force field molecular dynamics (ReaxFF-MD), bituminous coal, molecular model, pyrolysis, oxygen-containing functional groups

中图分类号:

X936

李静静, 江丙友, 许颇, 苏明清, 鲁昆仑, 余昌飞. 基于反应分子动力学的烟煤分子模型构建及热解机制[J]. 中国安全科学学报, 2026, 36(7): 153-163.

Li Jingjing, Jiang Bingyou, Xu Po, Su Mingqing, Lu Kunlun, Yu Changfei. Construction of a bituminous coal molecular model and its pyrolysis mechanism based on reactive molecular dynamics[J]. China Safety Science Journal, 2026, 36(7): 153-163.

图/表 19

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工业分析				元素分析
M_ad	A_ad	V_ad	FC_ad	C	H	O	S	N
0.7	7.9	27.5	63.9	77.7	4.1	13.9	0.3	4.0

元素峰	官能团	结合能/eV	相对含量/%
C 1s	COOH	290.28	5. 169 63
	C-O-C	285.72	32. 977 81
	C-C/C=C	284.80	61. 852 57
O 1s	C=O	533.59	51. 620 22
O 1s	C-O	532.62	48. 379 78
N 1s	N-X	401.23	18. 247 73
	N-Q	400.64	16. 611 68
	N-5	399.91	42. 775 53
	N-6	398.53	22. 365 06
S 2p	砜	170.45	13. 897 43
	亚砜	166.60	16. 257 78
	噻吩	165.24	19. 142 05
	噻吩	164.02	50. 702 74

波数范围/ cm^-1	波数/ cm^-1	峰面积	官能团	相对含量/%	波数范围/ cm^-1	波数/ cm^-1	峰面积	官能团	相对含量/%
900~700	872.2	0. 850 10	五取代苯	22.57		1 097.8	2. 152 65	C-OH拉伸振动	3.12
	853.1	0. 201 05	五取代苯	22.57		1 029.4	6. 991 23	C-O-C拉伸振动	10.15
	814.3	0. 885 18	四取代苯	19.01	3 000~2 800	2 953.7	3. 052 24	CH₃不对称拉伸振动	18.64
	793.4	0. 776 29	三取代苯	58.42		2 925.1	4. 415 97	CH₂不对称拉伸振动	26.97
	751.8	1. 944 53	三取代苯	58.42		2 905.4	2. 849 96	CH拉伸振动	17.40
1 800~ 1 000	1 719	1. 113 30	C=O拉伸振动	9.31		2 882.7	2. 078 29	CH₃对称拉伸振动	12.69
	1 653.4	5. 302 16	C=O拉伸振动	9.31		2 856.7	2. 871 38	CH₂对称拉伸振动	24.30
	1 615.7	10. 642 89	C=C拉伸振动	28.73		2 834.2	1. 107 36	CH₂对称拉伸振动	24.30
	1 585.5	7. 433 99			3 600~3 000	3 545.5	2. 792 15	OH…π	37.14
	1 550.8	1. 716 26				3 503.7	4. 363 83
	1 492.2	2. 769 61	CH₃变形振动	29.39		3 459.1	6. 190 90
	1 449.5	8. 566 95				3 417.2	6. 630 59	OH…OH	44.61
	1 415.5	4. 423 83				3 374.8	5. 747 91
	1 375.3	4. 488 36				3 329	3. 651 45
	1 333.6	3. 330 70	Ar-O-C拉伸振动	13.63		3 279.3	2. 455 88	OH…OR	11.63
	1 297.7	2. 735 69				3 230.8	1. 723 99	OH…OR	11.63
	1 260.1	3. 320 63				3 182	0. 993 59	环形OH	2.77
	1 221.6	2. 317 16	C-O拉伸振动	5.67		3 036	1. 382 72	C-H拉伸振动	3.85
	1 181.5	1. 586 09	C-O拉伸振动	5.67		3 036	1. 382 72	C-H拉伸振动	3.85

化学位移/10^-6	相对含量/%	归属
174.73	0.71	C=O
161.82	1.19	Ar-O
152.44	4.77	Ar-O
143.13	6.30	Ar-C
136.79	12.56	C-C
127.39	27.00	Ar-H
120.33	13.74	Ar-H
111.86	4.27	Ar-H
102.14	1.08	Ar-H
62.34	1.36	O-CH₃
50.39	3.11	O-CH₃
40.38	6.23	C, CH
31.97	8.73	CH₂
20.71	7.32	Ar-CH₃
15.13	1.64	R-CH₃

类型	芳香单元结构	数量
苯		1
萘		4
吡咯		4
吡啶		2
噻吩		1

基于反应分子动力学的烟煤分子模型构建及热解机制

Construction of a bituminous coal molecular model and its pyrolysis mechanism based on reactive molecular dynamics

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模型	E_a/(kJ/mol)					平均E_a/ (kJ/mol)
模型	0.3	0.4	0.5	0.6	0.7	平均E_a/ (kJ/mol)
FWO	237.59	263.00	287.29	366.49	688.01	368.48
KAS	238.11	264.48	289.74	372.72	710.39	375.09

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