霍州和兴和褐煤的热溶解聚及其有机氧的赋存形态

鲁浩; 杜姣姣; 肖剑; 魏豪; 赵云鹏; 魏贤勇

霍州和兴和褐煤的热溶解聚及其有机氧的赋存形态

鲁浩¹,
杜姣姣¹,
肖剑¹,
魏豪¹,
赵云鹏^{1, 2, ,},
魏贤勇¹

1.
中国矿业大学煤炭加工与高效利用教育部重点实验室, 江苏徐州 221116
2.
太原理工大学煤科学与技术省部共建国家重点实验室培育基地, 山西太原 030024

基金项目:

国家自然科学基金青年科学基金 21206188

煤科学与技术省部共建国家重点实验室培育基地开放基金 MKX201502

中国矿业大学国家大学生创新训练计划 201610290036

详细信息

中图分类号: TQ530
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出版历程
- 收稿日期: 2018-01-25
- 修回日期: 2018-06-07
- 网络出版日期: 2021-01-23
- 刊出日期: 2018-08-10

Thermal dissolution of Huozhou and Xinghe lignites and the occurrence forms of organic oxygen in them

1.
Key Laboratory of Coal Processing and Efficient Utilization, Ministry of Education, China University of Mining & Technology, Xuzhou 221116, China
2.
State Key Laboratory Breeding Base of Coal Science and Technology Co-founded by Shanxi Province and Ministry Education, Taiyuan University of Technology, Taiyuan 030024, China

Funds:

the National Natural Science Foundation of China 21206188

Open Foundation from State Key Laboratory Breeding Base of Coal Science and Technology Co-founded by Shanxi Province and Ministry Education MKX201502

National Undergraduate Training Programs for Innovation of China University of Mining and Technology 201610290036

More Information

Corresponding author: ZHAO Yun-peng, E-mail: yunpengzhao2009@163.com

摘要

摘要: 依次采用石油醚、二硫化碳、甲醇、丙酮和等体积的丙酮/二硫化碳混合溶剂对霍州（HZ）和兴和（XH）褐煤进行分级萃取得到萃取物（E₁-E₅）和萃取残渣（ER₁-ER₅），利用甲醇、甲苯、等体积甲醇/甲苯混合溶剂和丙酮等溶剂分别对ER₅在320℃进行热溶得到热溶物（SPs）。HZ和XH的累积萃取物产率分别为7.03%和7.86%，其中，E₃的产率最高；萃取残渣在甲醇/甲苯混合溶剂中的热溶物产率最高，ER_5，HZ和ER_5，XH的热溶物产率分别为45.76%和40.14%。E₁-E₅的傅里叶变换红外光谱（FT-IR）谱图中均有较强的脂肪C-H的伸缩振动峰，而SPs的FT-IR谱图中具有较强的C=C、C=O和缔合羟基的吸收峰。气相色谱质谱联用（GC/MS）分析表明，E₁-E₅中含氧化合物（OCOCs）以醇、醚和酮类化合物为主，而SPs中OCOCs以醇、酚和酮类化合物为主，且极性较强的溶剂有利于褐煤中OCOCs的溶出。与原煤FT-IR谱图相比，萃取残渣和热溶残渣的FT-IR谱图中缔合羟基、C=O和C-O-C的伸缩振动峰强度明显减弱。X射线光电子能谱（XPS）分析表明，两种褐煤中不同形态氧的相对含量为C-O > C=O > COO-，并且HZ具有更高的C-O和COO-含量。
- 褐煤 /
- 热溶 /
- 有机氧 /
- 气相色谱/质谱联用
Abstract: Huozhou (HZ)and Xinghe (XH) lignites were extracted in turn with petroleum ether, carbon disulfide, methanol, acetone and isometric acetone/carbon disulfide mixed solvent to obtain the extracts (E₁-E₅) and the extraction residues (ER₁-ER₅), then ER₅ was thermally dissolved at 320℃ using methanol, toluene, isometric methanol/toluene mixed solvent and acetone to gain the soluble portions (SPs). The total yields of extraction for HZ and XH are 7.03% and 7.86%, respectively, in which the yield of E₃ is the highest. The SPs yield of extraction residue with isometric methanol/toluene mixed solvent is the highest, and the SPs of ER_{5, HZ} and ER_{5, XH} with isometric methanol/toluene mixed solvent reaches 45.76% and 40.14%, respectively. There exist strong adsorption peaks ascribed to aliphatic C-H in the Fourier transform infrared (FT-IR) spectra of E₁-E₅, while the intensity of adsorption peaks ascribed to C=C, C=O and O-H in the FT-IR spectra of SPs is obviously higher than that of extracts. The gas chromatography/mass spectrometer (GC/MS) analyses show that the oxygen containing organic compounds (OCOCs) in E₁-E₅ are dominated with alcohols, ethers and ketones, while it is mainly composed of alcohols, phenols and ketones in the SPs, and the strong polar solvents contribute to dissolving the OCOCs in lignites. The adsorption peaks ascribed to associated O-H, C=O and C-O-C in the FT-IR spectra of extraction residues and thermal dissolution residues are weaker than those of raw coals. The X-ray photoelectron spectroscopy (XPS) analyses indicate that the relative content of oxygen forms in XH and HZ is C-O > C=O > COO-, and the relative content of C-O and COO-in HZ is higher than that in XH.
- lignite /
- thermal dissolution /
- organic oxygen /
- GC/MS

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图 1 分级萃取实验流程示意图

Figure 1 Fractional extraction procedure

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图 2 ER₅热溶实验流程示意图

Figure 2 Thermal dissolution procedure of ER₅

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图 3 分级萃取萃取物产率

Figure 3 Yields of extracts from fractional extraction

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图 4 不同溶剂热溶物产率

Figure 4 Yields of SPs with different solvents

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图 5 E₁-E₅的FT-IR谱图

Figure 5 FT-IR spectra of E₁-E₅

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图 6 SP_S的FT-IR谱图

Figure 6 FT-IR spectra of SP_S

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图 7 E₁-E₅中OCOCs的分布

: furans; : carboxylic acids; : esters; : aldehydes; : ketones; : ethers; : phenols; : alcohols

Figure 7 Distribution of OCOCs in E₁-E₅

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图 8 SPs中OCOCs的相对含量

: furans; : carboxylic acids; : esters; : aldehydes; : ketones; : ethers; : phenols; : alcohols

Figure 8 Relative contents of OCOCs in SPs

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图 9 HZ、XH及其ER和TDR的FT-IR谱图

Figure 9 FT-IR spectra of HZ, XH, ER and TDR

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图 10 HZ、XH及其ER₅和TDRs的O 1s XPS谱图

: C= O; : C-O; : COO-

Figure 10 O 1s XPS spectra of HZ, XH, ER₅ and TDRs

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表 1 褐煤的工业分析和元素分析

Table 1 Proximate and ultimate analyses of coal samples

Sample	Proximate analysis w/%			Ultimate analysis w_daf/%
Sample	M_ad	A_d	V_daf	C	H	N	S	O^a
HZ	18.49	30.01	53.36	55.03	4.05	1.41	0.62	38.44
XH	13.26	13.74	48.14	60.22	6.23	0.81	2.67	30.07
^a: by difference

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表 2 E₁-E₅的GC/MS可检测化合物分布

Table 2 Distribution of group components in E₁-E₅ identified by GC/MS

Component	Relative content w/%
	HZ					XH
	E₁	E₂	E₃	E₄	E₅	E₁	E₂	E₃	E₄	E₅
AHs	59.15	51.72	8.91	46.12	2.95	49.21	48.71	0.80	43.41	2.44
ARs	9.87	29.50	21.15	6.93	40.45	34.42	33.27	13.14	10.06	40.92
OCOCs	24.50	13.31	43.34	38.97	41.24	14.48	13.36	56.74	42.54	47.43
NCOCs	4.98	2.89	17.56	6.69	13.80	1.39	1.87	20.40	3.99	8.16
OCs	1.50	2.58	9.04	1.29	1.56	0.50	2.79	8.92	0.00	1.05

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表 3 SPs的GC/MS可检测化合物分布

Table 3 Distribution of group components in SPs identified by GC/MS

Component	Relative content w/%
	HZ				XH
	SP_TOL	SP_MET	SP_TOL/MET	SP_AC	SP_TOL	SP_MET	SP_TOL/MET	SP_AC
AHs	40.76	2.79	8.43	1.68	5.81	4.44	8.01	1.86
ARs	49.04	17.97	25.51	15.82	45.52	12.17	29.94	22.65
OCOCs	7.53	66.34	52.36	80.03	46.95	76.00	53.69	71.11
NCOCs	2.44	10.83	12.83	1.91	1.17	5.75	6.72	3.63
OCs	0.23	2.07	0.87	0.56	0.55	1.64	1.64	0.75

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表 4 HZ、XH、ERs和TDRs有机氧形态(O 1s)及其相对含量

Table 4 Relative content of organic oxygen forms (O 1s) in HZ, XH, ERs and TDRs

Sample	Relative content w/%
Sample	C=O	C-O	COO-
HZ	9.60	79.04	11.36
ER_{5, HZ}	30.94	52.50	16.56
TDR_{MET/TOL, HZ}	21.28	56.15	22.57
TDR_{AC, HZ}	22.38	46.56	31.06
XH	25.99	63.26	10.78
ER_{5, XH}	33.98	47.99	18.03
TDR_{MET/TOL, XH}	16.11	52.96	30.93
TDR_{AC, XH}	16.69	34.58	48.73

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