Construction and Comparison of Macromolecular Models of Different Coal Rank Coals

doi:10.19657/j.geoscience.1000-8527.2024.013

Abstract

Abstract:

The construction of coal macromolecular model is of fundamental significance for studying the physical and chemical properties and efficient utilization of coal. However, there is still a lack of construction and comparison of macromolecular models reflecting the properties of different rank coals. Therefore, this study used industrial analysis and elemental analysis, as well as nuclear magnetic resonance carbon spectroscopy, infrared spectroscopy, X-ray photoelectron spectroscopy and other test methods, combined with previous data, constructed and collected Hequ coal, Xiaoyi coal, Dianping coal, Gaoyang coal, Yangquan coal, Zhaozhuang coal and other 13 different coal rank coal macromolecular model sequences across lignite to anthracite (R_o=0.46%-3.21%). The macromolecular structure parameters of coal show that the aromatic carbon rate in aromatic structure increases in three stages with the increase of coal rank. The bridged aromatic carbon and bridged aromatic carbon increase linearly, and the side-branched aromatic carbon and oxygenated aromatic carbon decrease rapidly before the first jump point of coal metamorphism. The lipid carbon ratio in the fat structure is opposite to the aromatic carbon ratio, showing a three-stage decreasing trend. The methyl carbon increases before the first jump point and finally decreases; The fluctuation of methylene carbon corresponds to the three coalification jumps; the change rule of oxygenated fat carbon is not obvious. The content of oxygen-containing functional groups decreases with the increase of coal rank. The decrease of van der Waals energy and bond stretching energy plays a leading role in molecular stability, and hydrogen bond energy only plays a role in low rank(lignite) and medium coal(long flame coal, gas coal) and between molecules. The total energy of multi-molecules in low and medium rank coal(lignite to lean coal) is lower than that of equivalent single molecules, while the energy of multi-molecules in high-rank coal(lean coal and anthracite) is higher than that of equivalent single molecules due to π-π interaction. In general, the macromolecular model sequence established in this paper reflects the law of coal metamorphism and reveals the energy composition of coal molecules. The research results are expected to provide basic coal molecular configuration for further coal macromolecular simulation work.

Key words: coal, molecular model, functional group, energy configuration, coal rank

CLC Number:

P591
P618.1

ZHANG Chen, ZHANG Songhang, TANG Shuheng, ZHANG Shouren, LI Zhe, FAN Zhihui. Construction and Comparison of Macromolecular Models of Different Coal Rank Coals[J]. Geoscience, 2025, 39(03): 839-855.

Figures/Tables 26

Fig.1 Coal sample collection point diagram

Table 1 Information of coal samples

序号	样品名	采样点	地层	沉积环境
1	五牧场煤^[18]	五牧场煤矿	白垩系大磨拐组	辫状河三角洲平原沉积
2	神东煤^[19]	神东煤矿	侏罗系延安组	三角洲前缘沉积
3	兖州煤^[21]	北宿煤矿	石炭-二叠系太原组	潮坪沉积
4	河曲煤	河曲煤矿	二叠系太原组	河流三角洲平原沉积
5	马脊梁煤^[22]	马脊梁煤矿	石炭系太原组	湖泊三角洲平原沉积
6	孝义煤	孝义煤矿	二叠系山西组	三角洲平原沉积
7	柳林煤^[24]	柳林沙曲煤矿	二叠系山西组	潮坪沉积
8	店坪煤	店坪煤矿	二叠系下石盒子组	曲流河三角洲平原沉积
9	杜儿坪煤^[17]	西山煤田	二叠系山西组	三角洲平原沉积
10	高阳煤	高阳煤矿	石炭-二叠系太原组	障壁-泻湖沉积
11	阳泉煤	阳泉煤矿	石炭-二叠系太原组	三角洲平原沉积
12	赵庄煤	赵庄煤矿	石炭-二叠系太原组	泻湖沉积
13	成庄煤^[20]	成庄煤矿	二叠系山西组	河控三角洲平原沉积

Table 2 Industrial analysis and elemental analysis results of different coal ranks

序号	煤样	煤阶		R_O(%)	M_ad(%)	A_ad(%)	V_daf(%)	C_daf(%)	H_daf(%)	O_daf(%)	N_daf(%)	S_daf(%)	H/C	O/C
1	五牧场^[18]	褐煤	低阶煤	0.46	5.14	16.15	33.15	77.79	4.47	16.02	1.29	0.43	0.69	0.15
2	神东^[19]	长焰煤	中阶煤	0.51	9.77	1.77	41.17	77.93	4.71	16.18	4.71	0.18	0.73	0.16
3	兖州^[21]	长焰煤		0.62	1.92	14.32	46.23	80.17	5.61	8.12	1.43	4.68	0.84	0.08
4	河曲	长焰煤		0.67	2.96	36.66	28.47	75.69	5.35	16.55	1.68	0.73	0.85	0.16
5	马脊梁^[22]	气煤		0.74	1.70	20.30	38.18	81.69	5.09	11.14	1.35	0.73	0.75	0.10
6	孝义	肥煤		1.27	0.73	5.63	28.15	83.54	4.93	2.63	1.43	1.80	0.71	0.02
7	柳林^[24]	焦煤		1.38	4.68	3.39	28.94	79.30	5.73	8.92	1.36	0.69	0.87	0.08
8	店坪	焦煤		1.50	0.60	4.17	18.80	90.38	4.76	2.09	1.48	1.30	0.63	0.02
9	杜儿坪^[17]	瘦煤		1.74	0.62	8.61	17.04	90.13	4.56	3.32	1.44	0.55	0.61	0.03
10	高阳	瘦煤		1.96	0.56	6.89	17.22	84.18	4.30	1.40	1.26	1.93	0.61	0.01
11	阳泉	贫煤	高阶煤	2.04	1.50	3.18	8.28	89.25	3.44	1.49	1.48	1.11	0.46	0.01
12	赵庄	无烟煤		2.21	0.86	10.61	10.84	91.31	3.58	3.12	1.62	0.37	0.47	0.03
13	成庄^[20]	无烟煤		3.21	0.74	14.76	11.30	89.22	3.51	5.61	1.10	0.56	0.47	0.05

Fig.2 The C content of coal sample changes with RO(a), H/C and O/C changes with RO(b)

Table 3 Carbon chemical shift region attribution of coal samples

化学位移(10^-6)	6主要归属	化学位移(10^-6)	主要归属
16	脂甲基(R—CH₃)	75~95	环内氧接脂碳(R—O—R)
20	芳甲基(Ar—CH₃)	100~129	质子化芳碳(Ar—H)
23	和脂甲基相连的亚甲基(CH₃—CH₂)	129~137	桥接芳碳(Bridgehead)
33	亚甲基(CH₂)	137~148	侧支芳碳(Ar—C)
36~50	季碳、次甲基碳(C,CH)	148~165	氧取代芳碳(Ar—O)
50~60	甲氧基及氧接亚甲基碳(O—CH_3,O—CH₂)	165~190	羧基碳(COOH)
60~70	氧接次甲基碳(O—CH)	190~220	羰基碳(CO)

Table 4 Structural parameters of different rank coal samples

序号	煤样	煤阶	f_a(%)	$f a C$ (%)	$f a'$ (%)	$f a H$ (%)	$f a N$ (%)	$f a P$ (%)	$f a S$ (%)	$f a B$ (%)	f_al(%)	$f a l *$ (%)	$f a l H$ (%)	$f a l O$ (%)	X_BP(%)
1	五牧场^[18]	低阶煤	66.00	9.00	63.27	18.00	39.00	11.00	16.00	12.00	30.55	9.00	24.00	0	0.13
2	神东^[19]	中阶煤	71.00	6.00	65.00	42.00	23.00	3.00	11.00	9.00	29.00	5.00	22.00	3.00	0.16
3	兖州^[21]		74.00	1.00	64.00	45.00	19.00	8.00	5.00	6.00	26.00	11.00	12.00	3.00	0.10
4	河曲		72.78	1.40	71.37	45.63	25.75	5.09	10.63	10.02	27.22	19.92	5.83	1.47	0.16
5	马脊梁^[22]		74.24	5.10	69.14	45.68	23.46	6.08	4.06	13.32	25.76	10.05	12.64	3.07	0.24
6	孝义		60.13	0	60.13	42.00	18.12	0	7.88	10.25	39.87	20.15	10.36	9.36	0.21
7	柳林^[24]		71.99	1.55	70.44	46.88	23.56	2.78	5.42	15.36	28.01	17.41	10.60	0	0.28
8	店坪		81.77	0.86	80.92	59.98	20.94	2.82	2.02	16.10	18.23	10.26	7.16	0.81	0.25
9	杜儿坪^[17]		79.81	3.93	75.88	48.98	26.90	1.88	6.33	18.69	20.19	6.93	9.60	3.66	0.33
10	高阳		72.41	9.98	62.42	44.25	18.17	1.46	0	12.89	27.59	6.39	7.95	13.25	0.26
11	阳泉	高阶煤	82.08	13.36	68.82	38.65	30.17	0	0	16.31	17.92	3.33	1.58	13.01	0.30
12	赵庄		84.47	2.42	82.05	45.49	36.56	0	13.14	23.42	15.53	11.26	1.94	2.33	0.40
13	成庄^[20]		86.59	10.18	84.43	54.47	21.94	0.97	0.65	20.32	13.41	5.03	7.93	0.45	0.36

Table 4 Structural parameters of different rank coal samples

序号	煤样	煤阶	f_a(%)	$f a C$ (%)	$f a'$ (%)	$f a H$ (%)	$f a N$ (%)	$f a P$ (%)	$f a S$ (%)	$f a B$ (%)	f_al(%)	$f a l *$ (%)	$f a l H$ (%)	$f a l O$ (%)	X_BP(%)
1	五牧场^[18]	低阶煤	66.00	9.00	63.27	18.00	39.00	11.00	16.00	12.00	30.55	9.00	24.00	0	0.13
2	神东^[19]	中阶煤	71.00	6.00	65.00	42.00	23.00	3.00	11.00	9.00	29.00	5.00	22.00	3.00	0.16
3	兖州^[21]		74.00	1.00	64.00	45.00	19.00	8.00	5.00	6.00	26.00	11.00	12.00	3.00	0.10
4	河曲		72.78	1.40	71.37	45.63	25.75	5.09	10.63	10.02	27.22	19.92	5.83	1.47	0.16
5	马脊梁^[22]		74.24	5.10	69.14	45.68	23.46	6.08	4.06	13.32	25.76	10.05	12.64	3.07	0.24
6	孝义		60.13	0	60.13	42.00	18.12	0	7.88	10.25	39.87	20.15	10.36	9.36	0.21
7	柳林^[24]		71.99	1.55	70.44	46.88	23.56	2.78	5.42	15.36	28.01	17.41	10.60	0	0.28
8	店坪		81.77	0.86	80.92	59.98	20.94	2.82	2.02	16.10	18.23	10.26	7.16	0.81	0.25
9	杜儿坪^[17]		79.81	3.93	75.88	48.98	26.90	1.88	6.33	18.69	20.19	6.93	9.60	3.66	0.33
10	高阳		72.41	9.98	62.42	44.25	18.17	1.46	0	12.89	27.59	6.39	7.95	13.25	0.26
11	阳泉	高阶煤	82.08	13.36	68.82	38.65	30.17	0	0	16.31	17.92	3.33	1.58	13.01	0.30
12	赵庄		84.47	2.42	82.05	45.49	36.56	0	13.14	23.42	15.53	11.26	1.94	2.33	0.40
13	成庄^[20]		86.59	10.18	84.43	54.47	21.94	0.97	0.65	20.32	13.41	5.03	7.93	0.45	0.36

Fig.3 13C-NMR spectrum of different coal samples

Fig.4 Peak fitting and relative content of aliphatic hydrocarbons in different coal samples

Table 5 Different coal samples 2800-3000 cm-1 peak fitting absorption peak parameters

煤样	波值(cm^-1)	比例(%)	结构式
河曲长焰煤	2841.35	4.71	对称的CH₂
	2864.99	24.04	对称的CH₃
	2903.44	20.02	CH
	2927.20	24.18	不对称的CH₂
	2951.04	17.37	不对称的CH₃
	2968.72	9.67	不对称的CH₃
店坪焦煤	2840.40	6.70	对称的CH₂
	2864.90	24.14	对称的CH₃
	2894.50	11.78	CH
	2923.50	26.96	不对称的CH₂
	2953.60	24.26	不对称的CH₃
	2968.14	6.16	不对称的CH₃
赵庄贫煤	2835.18	5.67	对称的CH₂
	2861.23	19.87	对称的CH₃
	2889.55	18.69	CH
	2917.65	30.95	不对称的CH₂
	2941.62	15.97	不对称的CH₃
	2962.70	8.85	不对称的CH₃

Fig.5 Peak fitting diagram of O element in different coal samples

Table 6 The content and existence form of O element in different coal samples

煤样	结合能(eV)	比例(%)	存在形式
河曲长焰煤	531.43	19.29	C=O
	532.42	50.63	C—O—H,C—O—C
	533.51	30.08	C—O—C=O
店坪焦煤	531.39	20.73	C=O
	532.40	43.37	C—O—H,C—O—C
	533.62	35.90	C—O—C=O
赵庄贫煤	531.75	19.35	C=O
	532.45	53.80	C—O—H,C—O—C
	533.66	26.85	C—O—C=O

Table 7 The content and existence form of N element in different coal samples

煤样	结合能(eV)	比例(%)	存在形式
河曲长焰煤	398.97	31.83	吡啶型氮
	400.33	40.70	吡咯型氮
	401.81	16.57	季氮
	405.95	10.90	氮氧化物
店坪焦煤	398.29	60.57	吡啶型氮
	400.14	27.18	吡咯型氮
	401.96	12.25	季氮
赵庄贫煤	398.49	33.63	吡啶型氮
	400.38	48.55	吡咯型氮
	401.74	8.46	季氮
	402.99	9.36	氮氧化物

Fig.6 Peak fitting diagram of N element in different coal samples

Table 8 The content and existence form of S element in different coal samples

煤样	结合能(eV)	比例(%)	存在形式
河曲长焰煤	164.00	35.60	噻吩型硫
	165.14	24.22	亚砜型硫
	168.60	15.92	砜型硫
	171.86	24.26	无机硫
店坪焦煤	164.00	30.60	噻吩型硫
	165.14	29.22	亚砜型硫
	168.60	20.92	砜型硫
	169.86	19.26	无机硫
赵庄贫煤	164.27	55.80	噻吩型硫
	165.62	19.06	亚砜型硫
	169.34	25.14	砜型硫

Fig.7 Peak fitting diagram of S element in different coal samples

Table 9 Aromatic carbon structure parameters of different coal samples

芳香环结构	数量
芳香环结构	五牧场^[18]	神东^[19]	兖州^[21]	河曲	马脊梁^[22]	孝义	柳林^[24]	店坪	杜儿坪^[17]	高阳	阳泉	赵庄	成庄^[20]
1环	8	6	11	7	4	3	2	4	3	3	3	1	2
2环	7	9	2	7	5	6	3	7	2	5	3	2	5
3环	0	0	2	2	5	3	5	3	5	2	2	1	3
4环	0	0	0	0	0	0	0	1	2	2	1	4	2
5环	0	0	0	0	0	0	0	0	0	0	2	2	1

Table 10 Existence form of heteroatoms in different coalmolecules

元素	样品	数量		存在形式
O	河曲长焰煤	34		4个C=O(2个羧基,2个羰基) 30个C—O(28个羟基,2个醚氧基)
	店坪焦煤	3		1个C=O(醛基),2个C—O(2个羟基)
	赵庄贫煤	5		1个C=O(羰基),4个C—O(3个醚氧基,1个羟基)
N	河曲长焰煤	3	1个吡啶2个吡咯
	店坪焦煤	2	2个吡啶
	赵庄贫煤	3	1个吡啶2个吡咯
S	河曲长焰煤	1	噻吩型硫
	店坪焦煤	1	噻吩型硫
	赵庄贫煤	0	0

Fig.8 Comparison of experimental spectra and calculated spectra of different coal samples

Fig.9 Macromolecularmodel of different rank coals

Fig. 10 Chart of aromatic structure parameters changing with RO

Fig.11 Chart of aromatic ring structure changing with RO

Fig.12 The variation of fat structure parameters with RO

Fig.13 Change of oxygen-containing functional groups with RO

Fig.14 Optimized single moleculemodel of different rank coals

Table 11 Energy minimum potential energy composition of different coal molecules

煤样	状态及分子数	总能量 (kcal/mol)		价电子能(kcal/mol)									非成键能(kcal/mol)
煤样	状态及分子数	总能量 (kcal/mol)		键伸缩能		键角能		扭转能		反转能			氢键能		范德华能		库仑能
五牧场煤^[18]	初始	5846.008		1868.095		56.127		118.401		3.559		-0.951			3739.855		60.920
	1	971.812		187.040		178.624		152.965		14.013		-0.429			348.740		90.858
	5	3027.266		353.368		385.551		838.160		26.609		-14.046			1232.564		238.143
神东煤^[19]	初始	8968.083		2994.571		117.362		230.430		10.106		-0.629			5621.903		-5.659
	1	1263.070		279.124		285.429		200.747		26.813		-4.556			489.894		-14.381
	5	3581.678		465.871		723.635		952.538		49.822		-57.037			1788.856		-289.382
兖州煤^[21]	初始	12234.661		3156.597		112.885		158.326		8.454		-0.120			8863.438		-64.919
	1	1574.102		328.196		331.488		349.085		37.477		-1.272			560.424		-31.296
	5	5633.303		623.121		1044.490		1850.008		86.334		-14.700			2285.219		-241.169
河曲煤	初始	6639.620		3302.872		106.379		225.003		4.349		-1.145			3093.571		-81.409
	1	1333.196		337.187		291.524		216.334		30.43		-5.271			569.64		-106.648
	5	4089.757		619.655		945.793		1336.767		8.255		-92.972			2259.568		-997.348
马脊梁煤^[22]	初始	9510.260	3217.678		125.725		263.856		8.008		-0.111			5925.887		-30.783
	1	1580.153	307.412		278.358		362.437		35.546		-1.510			604.621		-6.710
	5	5622.458	534.633		696.414		1890.059		109.116		-53.869			2758.167		-242.256
孝义煤	初始	10459.508	2157.635		209.393		279.505		27.183		0			7797.335		-11.542
	1	1796.588	346.846		428.809		341.316		36.474		0			623.652		19.490
	5	6997.366	646.953		1419.982		1796.970		137.872		0			2944.902		125.733
柳林煤^[24]	初始	8850.111	2438.258		67.046		92.720		3.972		0			6267.59		-19.475
	1	1162.936	226.496		230.302		233.552		27.969		0			442.439		2.177
	5	4161.200	453.144		633.397		1314.695		64.903		-4.099			1712.473		36.848
店坪煤	初始	10135.187	2980.915		24.986		72.081		5.424		0			7066.01		-14.227
	1	1196.052	275.209		196.991		188.589		25.482		0			516.431		-6.649
	5	5136.259	497.384		602.810		1395.260		120.404		-3.475			2632.154		-44.049
杜儿坪煤^[17]	初始	11060.348	3368.228		55.384		122.916		7.467		0			7525.731		-19.378
	1	1425.323	295.723		210.248		286.397		37.503		0			599.680		-4.229
	5	5118.068	474.562		584.682		1643.104		122.399		-3.037			2391.470		-24.949
高阳煤	初始	13977.685	2708.752		119.257		188.087		10.245		0			10950.638		0.706
	1	1610.075	302.724		301.396		391.288		37.136		0			569.426		8.106
	5	6373.633	559.727		997.870		2266.804		187.885		-1.896			2391.944		30.669
阳泉煤	初始	12076.706	2649.659		76.068		100.651		4.918		0			9249.571		-4.161
	1	1256.130	254.973		258.088		221.732		22.922		0			495.939		2.476
	5	4627.835	381.731		652.363		1386.379		100.809		-0.825			2146.007		21.142
赵庄煤	初始	10072.577	3045.705		44.616		92.246		5.425		0			6904.543		-19.958
	1	1364.943	266.017		208.645		308.096		30.438		0			561.795		-10.047
	5	7446.697	505.463		810.363		2630.553		224.734		-0.008			3364.964		-89.390
成庄煤^[20]	初始	9630.872	3198.255		42.296		86.200		5.789		-0.084			6242.854		55.561
	1	1182.040	236.028		176.868		209.128		33.166		0			454.062		72.789
	5	8224.441	449.844		807.630		2667.112		194.856		-2.751			4335.885		771.865

Table 11 Energy minimum potential energy composition of different coal molecules

煤样	状态及分子数	总能量 (kcal/mol)		价电子能(kcal/mol)									非成键能(kcal/mol)
煤样	状态及分子数	总能量 (kcal/mol)		键伸缩能		键角能		扭转能		反转能			氢键能		范德华能		库仑能
五牧场煤^[18]	初始	5846.008		1868.095		56.127		118.401		3.559		-0.951			3739.855		60.920
	1	971.812		187.040		178.624		152.965		14.013		-0.429			348.740		90.858
	5	3027.266		353.368		385.551		838.160		26.609		-14.046			1232.564		238.143
神东煤^[19]	初始	8968.083		2994.571		117.362		230.430		10.106		-0.629			5621.903		-5.659
	1	1263.070		279.124		285.429		200.747		26.813		-4.556			489.894		-14.381
	5	3581.678		465.871		723.635		952.538		49.822		-57.037			1788.856		-289.382
兖州煤^[21]	初始	12234.661		3156.597		112.885		158.326		8.454		-0.120			8863.438		-64.919
	1	1574.102		328.196		331.488		349.085		37.477		-1.272			560.424		-31.296
	5	5633.303		623.121		1044.490		1850.008		86.334		-14.700			2285.219		-241.169
河曲煤	初始	6639.620		3302.872		106.379		225.003		4.349		-1.145			3093.571		-81.409
	1	1333.196		337.187		291.524		216.334		30.43		-5.271			569.64		-106.648
	5	4089.757		619.655		945.793		1336.767		8.255		-92.972			2259.568		-997.348
马脊梁煤^[22]	初始	9510.260	3217.678		125.725		263.856		8.008		-0.111			5925.887		-30.783
	1	1580.153	307.412		278.358		362.437		35.546		-1.510			604.621		-6.710
	5	5622.458	534.633		696.414		1890.059		109.116		-53.869			2758.167		-242.256
孝义煤	初始	10459.508	2157.635		209.393		279.505		27.183		0			7797.335		-11.542
	1	1796.588	346.846		428.809		341.316		36.474		0			623.652		19.490
	5	6997.366	646.953		1419.982		1796.970		137.872		0			2944.902		125.733
柳林煤^[24]	初始	8850.111	2438.258		67.046		92.720		3.972		0			6267.59		-19.475
	1	1162.936	226.496		230.302		233.552		27.969		0			442.439		2.177
	5	4161.200	453.144		633.397		1314.695		64.903		-4.099			1712.473		36.848
店坪煤	初始	10135.187	2980.915		24.986		72.081		5.424		0			7066.01		-14.227
	1	1196.052	275.209		196.991		188.589		25.482		0			516.431		-6.649
	5	5136.259	497.384		602.810		1395.260		120.404		-3.475			2632.154		-44.049
杜儿坪煤^[17]	初始	11060.348	3368.228		55.384		122.916		7.467		0			7525.731		-19.378
	1	1425.323	295.723		210.248		286.397		37.503		0			599.680		-4.229
	5	5118.068	474.562		584.682		1643.104		122.399		-3.037			2391.470		-24.949
高阳煤	初始	13977.685	2708.752		119.257		188.087		10.245		0			10950.638		0.706
	1	1610.075	302.724		301.396		391.288		37.136		0			569.426		8.106
	5	6373.633	559.727		997.870		2266.804		187.885		-1.896			2391.944		30.669
阳泉煤	初始	12076.706	2649.659		76.068		100.651		4.918		0			9249.571		-4.161
	1	1256.130	254.973		258.088		221.732		22.922		0			495.939		2.476
	5	4627.835	381.731		652.363		1386.379		100.809		-0.825			2146.007		21.142
赵庄煤	初始	10072.577	3045.705		44.616		92.246		5.425		0			6904.543		-19.958
	1	1364.943	266.017		208.645		308.096		30.438		0			561.795		-10.047
	5	7446.697	505.463		810.363		2630.553		224.734		-0.008			3364.964		-89.390
成庄煤^[20]	初始	9630.872	3198.255		42.296		86.200		5.789		-0.084			6242.854		55.561
	1	1182.040	236.028		176.868		209.128		33.166		0			454.062		72.789
	5	8224.441	449.844		807.630		2667.112		194.856		-2.751			4335.885		771.865

Fig.15 The ratio of total energy of multimolecule to total energy of single molecule

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