油页岩干酪根化学键浓度与能量密度研究

王擎; 程枫; 潘朔

油页岩干酪根化学键浓度与能量密度研究

东北电力大学油页岩综合利用教育部工程研究中心, 吉林吉林 132012

基金项目:

国家自然科学基金 51676032

详细信息

通讯作者:
王擎, Tel:0432-64807366, Fax:0432-64806281, E-mail:rlx888@126.com

中图分类号: TK16
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- 被引次数: 0
出版历程
- 收稿日期: 2017-03-28
- 修回日期: 2017-06-28
- 网络出版日期: 2021-01-23
- 刊出日期: 2017-10-10

Chemical bond concentration and energy density of oil shale kerogen

Engineering Research Center of Ministry of Education for Comprehensive Utilization of Oil Shale, Northeast Dianli University, Jilin 132012, China

Funds:

the National Natural Science Foundation of China 51676032

摘要

摘要: 以抚顺、茂名油页岩干酪根¹³C NMR、XPS与元素分析数据为基础，构建了油页岩干酪根分子结构模型，同时以化学键为标准对抚顺、茂名干酪根结构模型进行了修改，构建的干酪根结构模型与实验化学键浓度匹配良好，从化学键角度验证了模型的准确性与合理性。以自建及文献中九个不同变质程度的油页岩干酪根结构模型为基础，研究了油页岩干酪根变质程度与各类化学键浓度及能量密度关系。结果表明，随油页岩干酪根变质程度的提高，芳香碳分别与芳香碳、脂肪碳、氢原子等原子形成的化学键浓度升高，脂肪碳与脂肪碳、氢原子等原子形成的化学键浓度下降，其中，芳香碳之间、脂肪碳与氢原子之间的化学键浓度变化最明显。组成油页岩干酪根势能的价电子能密度及非键能密度随干酪根变质程度的提高总体上呈现上升趋势，成为组成油页岩干酪根稳定的化学能。
- 油页岩 /
- 分子模拟 /
- 化学键 /
- 动力学 /
- 核磁共振
Abstract: The molecular structures of Fushun and Maoming kerogen were constructed based on the characterization techniques such as solid-state¹³C nuclear magnetic resonance (NMR), X-ray photoelectron spectroscopy (XPS) and ultimate analysis. Self-build kerogen models were modified on the basis of chemical bond concentration, chemical bonds concentration of experiment data and molecular structure match well, therefore constructed models have been proved to be accurate and reasonable from the perspective of chemical bonds. From the data of self-build and selected kerogen models, the relationship between metamorphic degree of oil shale kerogen with concentration of chemical bonds and energy density were studied. With the increase maturity of oil shale kerogen, the chemical bonds concentration between aromatic carbon and aromatic carbon, aliphatic carbon, hydrogen atom increase, the chemical bonds concentration between aliphatic carbon and aliphatic carbon, hydrogen atom decrease. Among them the chemical bonds concentration between the aromatic carbons, and that between aliphatic carbon and hydrogen atom change obviously. Valence electron energy and non-bond energy are two parts that make up total energy, being the steady chemical energy of oil shale kerogen and increase with increase of its metamorphic degree.
- oil shale /
- molecular simulation /
- chemical bonds /
- kinetics /
- ¹³C NMR

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图 1 11个油页岩干酪根结构模型示意图

Figure 1 Structure models of oil shale kerogens

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图 2 模型密度变化曲线

Figure 2 Model density variation curves

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图 3 不同类型碳碳化学键曲线

Figure 3 C-C chemical bonds curves

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图 4 碳氢化学键曲线

Figure 4 C-H bonds curves

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图 5 碳氧化学键曲线

Figure 5 C-O bonds curves

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图 6 总化学键曲线

Figure 6 Total chemical bonds curves

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图 7 总能量密度曲线

Figure 7 Total energy density curves

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图 8 价电子能密度曲线

Figure 8 Valence electron energy density curves

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图 9 非键能密度曲线

Figure 9 Non-bond energy density curves

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表 1 抚顺、茂名干酪根的元素分析

Table 1 Ultimate analysis of Fushun and Maoming kerogen

Sample	Ultimate analysis w_daf/%
Sample	C	H	O^a	N	S
FS	72.27	8.65	7.64	2.78	2.75
FS correction	76.81	9.19	8.12	2.95	2.92
MM	70.64	8.35	8.93	2.15	4.81
MM correction	74.45	8.80	9.41	2.27	5.07
daf: dry and ash-free base; a: by difference

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表 2 抚顺、茂名干酪根的XPS分析

Table 2 XPS analysis of Fushun and Maoming kerogen

Elemental peaks	Functionalities	Relative content w /%
Elemental peaks	Functionalities	FS	MM
C 1s	C-C/C-H	94.44	94.01
	C-O/C-OH	4.94	5.00
	C=O/O-C-O	0.00	0.10
	O-C=O	0.62	0.89
N 1s	pyridine	15.94	9.30
	amino	11.53	12.08
	pyrrolic	45.48	45.07
	quaternary	23.34	27.18
	nitrogen oxides	3.71	6.37
S 2p	pyrite	0.99	1.81
	aromatic sulfur	10.66	4.08
	C-S	38.58	34.80
	sulfoxide	14.16	18.55
	sulfone	35.61	40.76

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表 3 抚顺、茂名干酪根碳结构分布参数

Table 3 Structural carbon parameters of Fushun and Maoming kerogen

Parameters	Carbon structure	FS	MM
f_ar		0.2538	0.2298
f_ar^H		0.1062	0.1122
f_ar^C		0.0562	0.0479
f_ar^O		0.0309	0.0251
f_a^C	-COOH/R	0.0062	0.0089
f_a^O		0.0000	0.0010
f_al		0.7352	0.7479
f_al^O		0.0185	0.0249
S^R		0.3858	0.3480
S^O		0.1416	0.1855
S^T		0.3561	0.4076
N^R		0.8476	0.8155

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表 4 实验与模型化学键浓度

Table 4 Experiment and model chemical bond concentration

Parameter	FS experiment	FS model	MM experiment	MM model
f_ar	0.253 8	0.262 5	0.229 8	0.229 5
f_ar^H	0.106 2	0.108 3	0.112 2	0.118 9
f_ar^B	0.060 5	0.055 3	0.044 6	0.041 0
f_ar^C	0.056 2	0.062 5	0.047 9	0.045 1
f_ar^O	0.030 9	0.033 3	0.025 1	0.024 6
f_al	0.735 2	0.729 2	0.747 9	0.758 2
H/C	1.436 2	1.441 7	1.410 8	1.409 8
O/C	0.079 2	0.079 2	0.094 9	0.094 3
N/C	0.033 0	0.033 3	0.025 5	0.024 6
S/C	0.014 3	0.012 5	0.025 5	0.024 6
C_ar-C_ar	0.016 0	0.016 6	0.013 8	0.013 8
C_al-C_ar	0.003 6	0.004 0	0.003 0	0.002 8
C_al-C_al	0.051 7	0.050 6	0.052 5	0.053 4
C_ar-H	0.006 8	0.007 0	0.007 0	0.007 4
C_al-H	0.080 9	0.080 3	0.077 2	0.075 8
C_ar-O	0.002 0	0.002 1	0.001 6	0.001 5
C_al-O	0.001 6	0.001 6	0.002 1	0.002 6
C_al=O	0.000 4	0.000 5	0.000 6	0.000 8
O-H	0.004 3	0.003 7	0.003 7	0.003 6
Total	0.167 2	0.166 4	0.164 7	0.161 7

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表 5 11个油页岩干酪根结构模型化学键浓度及芳碳率参数

Table 5 Chemical bond concentration and aromatic carbon parameters of eleven kerogen structure models

Models	H/C	f_ar%	C_ar-C_ar	C_ar-C_al	C_al-C_al	C-C	C_ar-H
(1)	1.674 9	0.115 2	0.007 3	0.003 4	0.051 2	0.063 2	0.001 6
(2)	1.553 2	0.174 5	0.011 3	0.003 8	0.046 7	0.064 2	0.003 2
(3)	0.582 9	0.794 3	0.067 3	0.008 9	0.010 9	0.087 2	0.017 8
(4)	0.875 5	0.566 5	0.043 9	0.007 5	0.027 8	0.079 4	0.011 5
(5)	1.034 0	0.417 0	0.029 5	0.010 6	0.022 1	0.073 8	0.014 8
(6)	1.327 7	0.280 9	0.016 5	0.007 2	0.029 1	0.060 0	0.007 5
(7)	1.515 4	0.228 0	0.014 3	0.004 7	0.048 2	0.067 6	0.006 2
(8)	0.905 0	0.586 8	0.048 5	0.011 3	0.022 8	0.082 5	0.010 1
(9)	1.579 2	0.251 6	0.016 8	0.007 9	0.045 7	0.071 4	0.007 2
(10)	1.441 7	0.262 5	0.016 6	0.004 0	0.040 4	0.066 1	0.007 0
(11)	1.409 8	0.229 5	0.013 8	0.002 8	0.039 6	0.063 1	0.007 4
Models	C_al-H	C-H	C_ar-O	C_al-O	C_al=O	C-O	O-H
(1)	0.102 1	0.103 7	0.001 3	0.006 0	0.002 4	0.009 7	0.001 0
(2)	0.091 6	0.094 8	0.001 9	0.006 7	0.001 1	0.009 7	0.002 1
(3)	0.022 7	0.040 6	0.002 8	0.004 1	0.000 0	0.006 9	0.000 4
(4)	0.043 6	0.055 0	0.004 6	0.005 2	0.001 4	0.011 2	0.002 9
(5)	0.054 0	0.068 8	0.000 6	0.003 2	0.000 6	0.004 4	0.001 5
(6)	0.065 4	0.072 9	0.001 3	0.010 6	0.000 8	0.012 6	0.004 6
(7)	0.087 7	0.093 9	0.003 7	0.004 4	0.001 2	0.009 3	0.002 9
(8)	0.051 9	0.062 0	0.001 2	0.004 3	0.000 9	0.006 3	0.000 3
(9)	0.097 7	0.104 9	0.000 3	0.001 1	0.000 7	0.002 1	0.000 3
(10)	0.080 3	0.087 2	0.002 1	0.001 6	0.000 5	0.004 3	0.003 7
(11)	0.075 8	0.083 2	0.001 5	0.002 6	0.000 8	0.004 9	0.003 6

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表 6 干酪根结构模型能量密度组成

Table 6 Energy density composition of kerogen structure models

Models	Total energy	Valence electron energy	Bond energy	Angle energy	Torsion energy
(1)	0.156 4	0.075 9	0.019 8	0.038 5	0.017 5
(2)	0.152 4	0.092 6	0.022 2	0.047 9	0.022 2
(3)	0.421 7	0.235 3	0.056 0	0.128 3	0.048 2
(4)	0.252 1	0.131 3	0.033 6	0.063 7	0.033 3
(5)	0.174 5	0.088 7	0.020 6	0.034 0	0.033 5
(6)	0.149 5	0.084 8	0.019 8	0.041 5	0.023 2
(7)	0.162 3	0.079 8	0.023 7	0.039 7	0.016 2
(8)	0.270 4	0.120 2	0.036 8	0.052 6	0.030 4
(9)	0.179 1	0.089 3	0.026 7	0.045 1	0.017 1
(10)	0.174 5	0.096 6	0.023 9	0.058 7	0.013 8
(11)	0.178 6	0.102 1	0.023 3	0.061 5	0.017 1
Models	Inversion energy	Non-bond energy	Hydrogen bond energy	Van der waals energy	Electrostatic energy
(1)	0.000 14	0.080 5	-0.000 26	0.094 9	-0.014 2
(2)	0.000 27	0.059 8	-0.000 01	0.100 7	-0.040 9
(3)	0.002 79	0.186 4	0.000 00	0.188 3	-0.001 9
(4)	0.000 57	0.120 9	-0.001 14	0.143 4	-0.021 4
(5)	0.000 62	0.085 8	-0.001 48	0.097 3	-0.010 1
(6)	0.000 27	0.064 7	-0.002 42	0.095 0	-0.028 0
(7)	0.000 15	0.082 5	-0.000 57	0.100 6	-0.017 5
(8)	0.000 37	0.150 2	0.000 00	0.161 8	-0.011 6
(9)	0.000 23	0.089 8	-0.000 56	0.099 4	-0.009 0
(10)	0.000 22	0.077 9	-0.001 40	0.094 4	-0.015 1
(11)	0.000 23	0.076 4	-0.000 02	0.096 2	-0.019 7

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