淖毛湖次烟煤的热溶及热溶物的催化加氢转化

吴法鹏; 赵云鹏; 宋庆露; 司兴刚; 康国俊; 曹景沛; 魏贤勇

doi:10.19906/j.cnki.JFCT.2021040

淖毛湖次烟煤的热溶及热溶物的催化加氢转化

doi: 10.19906/j.cnki.JFCT.2021040

吴法鹏^1,,
赵云鹏^{1, 2, ,},
宋庆露¹,
司兴刚¹,
康国俊³,
曹景沛^1, ,,
魏贤勇¹

1.
中国矿业大学，江苏省碳资源精细化利用工程研究中心，江苏徐州 221116
2.
新疆大学化工学院，新疆维吾尔自治区煤炭清洁转化与化工过程重点实验室，新疆乌鲁木齐 830046
3.
中国矿业大学，低碳能源研究院，江苏徐州 221008

基金项目: 国家自然科学基金(21878325)，国家重点研发计划资助项目课题（2016YFB0600303）和江苏省高校优势学科项目资助

详细信息

作者简介:
吴法鹏：wufapeng1115@qq.com

通讯作者:
Email：zhaoyp@cumt.edu.cn

caojingpei@cumt.edu.cn

中图分类号: TQ530
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出版历程
- 收稿日期: 2020-11-23
- 修回日期: 2021-01-03
- 网络出版日期: 2021-03-08
- 刊出日期: 2021-04-10

Thermal dissolution of Naomaohu sub-bituminous coal and catalytic hydroconversion of its soluble portions

1.
Jiangsu Province Engineering Research Center of Fine Utilization of Carbon Resources, China University of Mining & Technology, Xuzhou 221116, China
2.
Key Laboratory of Coal Clean Conversion & Chemical Engineering Process of Xinjiang Uygur Autonomous Region, College of Chemical Engineering, Xinjiang University, Urumqi 830046, China
3.
Low Carbon Energy Institute, China University of Mining & Technology, Xuzhou 221008, China

Funds: The project was supported by the National Natural Science Foundation of China (21878325), National Key Research and Development Program of China (2016YFB0600303) and the Priority Academic Program Development of Jiangsu Higher Education Institutions

摘要

摘要: 采用等体积甲醇/甲苯混合溶剂对淖毛湖次烟煤（NMH）进行热溶得到热溶物和热溶残渣（R_TD），利用Co/C@N-700催化剂催化320 ℃热溶物（SP₃₂₀）加氢转化得到CSP₃₂₀。利用气相色谱质谱联用仪（GC/MS）分析了SP₃₂₀催化加氢前后的组成和结构特征，利用傅里叶变换红外光谱（FT-IR）、热重以及固体 ¹³C核磁共振（¹³C NMR）分析了NMH和R_TD的热解反应性和结构特征。热溶物收率随温度升高而增加，320 ℃达到最大值（36.46%）。GC/MS分析表明，烷烃、芳烃和酚类是SP₃₂₀中的主要族组分，相对含量分别为45.45%、18.03%和24.75%；经催化加氢后芳烃和酚类相对含量分别降低至3.86%和13.6%，烷烃和醇类含量分别提高至66.99%和9.36%，其中，环烷烃由8种增加至24种，这说明Co/C@N-700对SP₃₂₀中芳烃和酚类加氢转化具有较高活性。与NMH相比，R_TD具有较高的热稳定性，骨架结构中芳香碳含量较高，而羰基碳含量较低；R_TD的FT-IR谱图中O−H、−CH₂−、C=O以及C−O−C对应的吸收峰强度显著减弱，芳香C=C的吸收峰强度明显增强。
- 次烟煤 /
- 热溶 /
- 催化加氢转化 /
- 固体 ¹³C核磁共振
Abstract: Naomaohu sub-bituminous coal (NMH) was thermally dissolved in isometric methanol/toluene mixed solvent affording soluble portions (SPs) and thermal dissolution residues (R_TD), then hydroconversion of SP₃₂₀ was catalyzed over Co/C@N-700 catalyst affording CSP₃₂₀. The composition and structural characteristics of SP₃₂₀ before and after catalytic hydroconversion were analyzed with a gas chromatograph/mass spectrometer (GC/MS), and pyrolysis reactivity and structural characteristics of NMH and R_TD were characterized with Fourier transform-infrared spectroscopy (FT-IR), thermogravimetry, as well as solid state ¹³C nuclear magnetic resonance (¹³C NMR). The SPs yields increase with increasing temperature, and reach a maximum (36.46%) at 320 ^oC. GC/MS analysis shows that SP₃₂₀ are mainly composed of alkanes, phenols and arenes, and their relative contents are 45.45%, 18.03% and 24.75%, respectively. After catalytic hydroconversion, relative contents of arenes and phenols in CSP₃₂₀ decrease to 3.86% and 13.6%, respectively, while those of alkanes and alcohols increase to 66.99% and 9.36%, respectively, and kinds of cycloalkanes increase from 8 to 24. These results indicate that arenes and phenols in SP₃₂₀ could be hydrogenated into alkanes and alcohols catalyzed by Co/C@N-700. Compared to NMH, R_TDpossesses higher thermal stability, more aromatic carbons, and less carbonyl carbons in its skeleton structure. In addition, intensity of adsorption peaks attributed to O−H, −CH₂−, C=O and C−O−C in the FT-IR spectrum of R_TD are weaker, while adsorption peaks assigned to aromatic C=C are stronger than those of NMH.
- sub-bituminous coal /
- thermal dissolution /
- catalytic hydroconversion /
- solid state ¹³C NMR

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FIG. 605. FIG. 605.

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图 1 NMH的热溶及热溶物的催化加氢转化

Figure 1 Procedure for thermal dissolution of NMH and catalytic hydroconversion of SP₃₂₀

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图 2 不同温度下可溶物的收率

Figure 2 Yield of the soluble portion under different temperatures

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图 3 (a) TG曲线和(b) DTG曲线

Figure 3 (a) TG curves and (b) DTG curves

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图 4 NMH和R_TD的 ¹³C NMR谱图和拟合曲线

Figure 4 ¹³C NMR spectra and their fitting curves of NMH and R_TD

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图 5 NMH和R_TD的FT-IR谱图

Figure 5 FT-IR spectra of NMH and R_TD

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图 6 SP₃₂₀和CSP₃₂₀的族组分分布

Figure 6 Distributions of group components of SP₃₂₀ and CSP₃₂₀

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表 1 NMH的工业分析和元素分析

Table 1 Proximate and ultimate analyses of NMH

Sample	Proxiamte analysis w/%			Ultimate analysis w_daf/%
Sample	M_ad	A_d	V_daf	C	H	N	S	O_diff
NMH	7.65	5.68	50.80	68.55	5.34	0.91	0.26	24.94
diff: by difference

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表 2 NMH和R_TD的TG/DTG曲线特征参数

Table 2 Characteristic parameters of NMH and R_TD from TG/DTG curves

Sample	W_110−900 /%	W_110−330 /%	W_330−600 /%	W_600−900 /%	t_p /℃
NMH	46.49	7.14	29.19	10.16	450
R_TD	34.29	4.44	19.72	10.13	463
W_110−900：total weight loss; W_110−330: weight loss assigned to release of bonded water and decarboxylation; W_330−600: weight loss ascribed to cleavage of covalent bonds; W_600−900: weight loss attributed to decomposition of carbonates and condensation of aromatic rings; t_p: peak temperature of maximum weight loss rate

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表 3 NMH和R_TD中不同类型碳的相对含量

Table 3 Relative contents of different carbon types in NMH and R_TD

Carbon type	Symbol	Chemical shift	Molar content/%
Carbon type	Symbol	Chemical shift	NMH	R_TD
RCH₃	${f}_{{\rm{al}}}^{1}$	16.1/15.3	0.66	5.06
ArCH₃	${f}_{ {\rm{al}} }^{a}$	19.8/19.9	2.78	5.33
RCH₂CH₃	${f}_{ {\rm{al}} }^{2}$	25.8/25.1	5.88	4.25
RCH₂R	${f}_{ {\rm{al}} }^{3}$	32.6/31.6	10.53	6.10
R₃CH	${f}_{{\rm{al}}}^{4}$	37.1/37.1	3.63	1.39
CR₄	${f}_{{\rm{al}}}^{5}$	42.7/42.8	10.45	6.85
RCH₂OR	${f}_{{\rm{al}}}^{{\rm{O}}1}$	55.7/52.8−61.2	8.32	4.49
R₂CHOR	${f}_{{\rm{al}}}^{{\rm{O}}2}$	72.1−82.5/84.1	1.10	2.42
R₃COR	${f}_{{\rm{al}}}^{{\rm{O}}3}$	72.1−82.5/84.1	0.95	8.02
	${f}_{{\rm{a}}}^{{\rm{O}}1}$	105.7/105.2	0.62	4.35
	${f}_{{\rm{a}}}^{{\rm{O}}2}$	115.9/115.8	4.51	7.35
	${f}_{{\rm{a}}}^{{\rm{H}}}$	125.7/125.5	3.99	15.95
	${f}_{{\rm{a}}}^{{\rm{b}}}$	132.7/132.1	10.17	12.23
	${f}_{{\rm{a}}}^{{\rm{s}}}$	143.0/140.0	8.19	4.13
	${f}_{{\rm{a}}}^{{\rm{O}}3}$	158.9/152.4	16.10	9.66
RCOOH/R	${f}_{{\rm{a}}}^{{\rm{c}}1}$	185.2/176.9−185.0	10.12	2.12
RCOH/R/Ar	${f}_{{\rm{a}}}^{{\rm{c}}2}$	215.8/215.5	2.00	0.30

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表 4 SP₃₂₀和CSP₃₂₀中GC/MS可检测芳烃

Table 4 Arenes identified by GC/MS in SP₃₂₀ and CSP₃₂₀

Compound	RC/%		Compound	RC/%
Compound	SP₃₂₀	CSP₃₂₀	Compound	SP₃₂₀	CSP₃₂₀
Ethylbenzene	6.73		2-ethyl-1,3-dimethylbenzene	0.28	0.14
p-xylene	4.77		1,2,3,4-tetramethylbenzene	0.21	0.17
m-xylene	1.54	0.38	naphthalene		0.11
o-xylene		0.33	(1-methyl-but-1-enyl)benzene	0.05
1-ethyl-2-methylbenzene	0.18		1,2,3,4,5-pentamethylbenzene		0.18
Propylbenzene	0.62		1,1,3-trimethyl-1H-indene	0.16
1-ethyl-3-methylbenzene		0.10	1-methylnaphthalene		0.13
Mesitylene	0.12		(1,4-dimethyl-pent-2-enyl)benzene		0.20
1,2,4-trimethylbenzene	0.55	0.32	2,3-dimethylnaphthalene		·0.24
1-ethyl-2-methylbenzene		0.27	1,4-dimethylnaphthalene	0.06
1-ethyl-4-methylbenzene	0.47	0.32	1,2,4-triethylbenzene
Isobutylbenzene	0.07		1,4,6-trimethylnaphthalene	0.43	0.38
Allylbenzene	0.14		1,4-diisopropyl-2,5-dimethylbenzene		0.20
1-ethyl-3,5-dimethylbenzene	0.12		3,4-dimethylbiphenyl	1.23	0.17
1,2,3,5-tetramethylbenzene		0.20	1-ethyl-3,5-diisopropylbenzene	0.30

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表 5 SP₃₂₀和CSP₃₂₀中GC/MS可检测酚类

Table 5 Phenols identified by GC/MS in SP₃₂₀ and CSP₃₂₀

Compound	RC/%		Compound	RC/%
Compound	SP₃₂₀	CSP₃₂₀	Compound	SP₃₂₀	CSP₃₂₀
Phenol		0.02	2,5-diethylphenol	0.30
o-cresol		0.38	2-isopropyl-5-methylphenol	1.13	0.67
p-cresol		0.05	5-isopropyl-2-methylphenol	0.94
2,6-dimethylphenol	1.53	1.2	2,3,4,6-tetramethylphenol	5.86	2.13
2,4-dimethylphenol		0.62	2,3,5,6-tetramethylphenol	3.89	1.76
2,5-dimethylphenol		0.37	2-(tert-butyl)-5-methylphenol	0.2
2-isopropyl-5-methylphenol		0.26	2,3,5-trimethylbenzene-1, 4-diol		1.05
2,4,6-trimethylphenol	2.89	2.7	2,5-di-tert-butylphenol	0.71
2,4,5-trimethylphenol	6.23		2,6-di-tert-butyl-4-methylphenol	1.07
2,3,6-trimethylphenol		1.17	2,3,5,6-teramethyl-benzene-1, 4-diol		0.11
3,4,5-trimethylphenol		0.49	5,7-dimethyl-naphthalen-1-ol		0.04
2-ethyl-4,5-dimethylphenol		0.42	2,5,8-trimethyl-naphthalen-1-ol		0.16

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表 6 SP₃₂₀和CSP₃₂₀中GC/MS可检测醇类

Table 6 Alcohols identified by GC/MS in SP₃₂₀ and CSP₃₂₀

Compound	RC/%		Compound	RC/%
Compound	SP₃₂₀	CSP₃₂₀	Compound	SP₃₂₀	CSP₃₂₀
4-isopropenyl-1-methylcyclohexanol	0.32		2-isopropyl-5-methylcyclohexanol		2.59
(4-tert-butyl-phenyl)methanol	1.21	1.36	2,4,5-trimethylcyclohexanol		1.41
1,2-dimethylcyclohexanol		1.64	4-methyl-heptan-4-ol		1.73
Cyclohexanol		0.28	3-phenyl-propan-1-ol		0.35

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表 7 SP₃₂₀和CSP₃₂₀中GC/MS可检测烷烃

Table 7 Alkanes identified by GC/MS in SP₃₂₀ and CSP₃₂₀

Compound	RC/%		Compound	RC/%
Compound	SP₃₂₀	CSP₃₂₀	Compound	SP₃₂₀	CSP₃₂₀
Octane	1.08	1.03	8-methylheptadecane	0.30
1,2,3-trimethylcyclohexane	0.48	2.15	1,1,3-trimethylindan		0.49
1,2-dimethylcyclohexane	0.44	4.64	tridecane		1.86
isopropylcyclopentane		0.31	1,4,7-trimethylindan		0.08
1,4-dimethylcyclohexane	0.55	4.17	2,3,6-trimethyldecane	0.35
2,4-dimethylheptane	0.38	0.32	tetradecane	0.71	0.98
1-ethyl-2-methylcyclopentane		2.14	4,5,7-trimethylindan		0.13
2-methyl-bicycloheptane		0.51	pentadecane	1.68	1.08
2,5-dimethylheptane	0.17		hexadecane	2.73	2.46
ethylcyclohexane		0.12	3-methyltridecane	0.60
propylcyclopentane		0.04	2,6,10-trimethylpentadecane	0.14	0.04
nonane	0.22	0.42	heptadecane	3.89	4.01
1-ethyl-4-methylcyclohexane		1.01	2-methylnonadecane	0.10
1,1-dimethylcyclopentane		0.58	3,6-dimethyldecane	0.31
methylcycloheptane	0.36	0.48	2,6,10-trimethyltetradecane	0.17
cycloheptane		0.06	octadecane	7.25	5.96
decane	0.17		9-methylnonadecane	0.46
2,2,3-trimethylbicycloheptane		0.08	3-methylheptadecane	2.23
4-methyldecane	0.08		nonadecane	0.60	3.84
cyclooctane		0.08	2-methylheptadecane	0.48
indan		0.10	icosane	9.36	12.85
4-ethyldecane	0.81		henicosane	2.18	1.94
1-methylindan	0.30	0.32	2-methylhexadecane	1.62
undecane	0.24	0.57	3-methylhexadecane	0.15	0.12
1,2-dimethylindan	0.15		docosane	0.41
1,3-dimethylindan		0.55	3-methylhenicosane	0.46
1,6-dimethylindan	0.35	0.43	tetracosane	0.84	5.85
5-methylindan		0.25	2-methyloctadecane	0.22
4-methylindan	0.48	0.64	pentacosane	0.30
dodecane	0.56	0.78	heptacosane	0.55	2.53
4,7-dimethylindan		0.19	2,6,11-trimethyldodecane	0.24
2,4-dimethylundecane	0.30		octacosane		0.80

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