反应时间对淖毛湖煤加氢液化中间产物自由基浓度影响研究

宁奕飞; 张媛媛; 周扬; 陈丽诗; 潘铁英; 张德祥

反应时间对淖毛湖煤加氢液化中间产物自由基浓度影响研究

1.
华东理工大学能源化工系煤气化及能源化工教育部重点实验室, 上海 200237
2.
华东理工大学分析测试中心, 上海 200237

基金项目:

国家重点研发计划项目 2016YFB0600303

详细信息

中图分类号: TQ529.1;TQ530
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- 被引次数: 0
出版历程
- 收稿日期: 2018-06-04
- 修回日期: 2018-09-03
- 网络出版日期: 2021-01-23
- 刊出日期: 2018-11-10

Effect of reaction time on free radical concentration in hydrogenation liquefaction of Naomaohu coal

1.
Department of Chemical Engineering for Energy Resources, East China University of Science and Technology, Key Laboratory of Coal Gasification and Energy Chemical Engineering of Ministry of Education, Shanghai 200237, China
2.
Analysis and Research Center, East China University of Science and Technology, Shanghai 200237, China

Funds:

the National Key Research and Development Program of China 2016YFB0600303

More Information

Corresponding author: ZHANG De-xiang, Tel:021-64252367, E-mail:zdx@ecust.edu.cn

摘要

摘要: 以新疆淖毛湖煤（NMH）为原料，在间歇高压反应釜中进行加氢液化实验，通过电子顺磁共振波谱仪（EPR）分析了加氢液化过程中间产物-沥青质（PAA）自由基浓度随停留时间的变化。结果表明，在实验温度下NMH煤加氢液化总转化率先升高后降低，在60 min达到峰值96.87%，油产率为53.01%；淖毛湖原煤自由基浓度为2.6654×10¹⁸/g，PAA自由基浓度在1.2519×10¹⁸/g-1.9121×10¹⁸/g，随着反应停留时间的延长先上升后下降，中间产物PAA自由基浓度数值可以反映液化反应进行的程度，与油产率变化趋势一致；反应中间产物PAA的g值小于原煤g值（2.00434），在2.00301-2.00403，在液化加氢过程中其g值呈先上升后下降的趋势，与PAA中N、S、O等杂原子成分的变化一致，与元素分析结果相吻合。
- 淖毛湖煤 /
- 顺磁共振 /
- 自由基浓度 /
- 沥青质 /
- 加氢液化机理
Abstract: Coal from Naomaohu (NMH) in Xinjiang as raw material, hydroliquefaction experiments were performed in a batch high-pressure liquefaction reactor. Variations of free radical concentration of PAA and the intermediate products of hydroliquefaction with reaction residence time were examined with an EPR spectrometer. The results show that conversion rate of NMH coal hydroliquefaction first rises and then decreases. The maximum conversion rate and oil yield is 96.87% and 53.01% in 60 min. The free radical concentration of NMH is 2.6654×10¹⁸/g. PAA's free radical concentration ranges between 1.2519×10¹⁸/g and 1.9121×10¹⁸/g, which first increases and then decreases with increasing reaction time. As for the intermediate products, PAA, its free radical concentration could reflect extent of hydroliquefaction reaction, which has the same variation tendency with the oil yield. PAA's g value is between 2.00301 and 2.00403, which is lower than that of NMH (2.00434). In the process of hydroliquefaction, its g value first rises and then decreases, which is closely related with the heteroatom content of N, S, O in PAA and is consistent with the element analysis result.
- Naomaohu coal /
- EPR /
- free radical concentration /
- asphaltene /
- hydrogenation liquefaction

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图 1 不同反应时间油和沥青质产率的变化

Figure 1 Oil and PAA conversion at different times

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图 2 不同反应时间气产率和总转化率的变化

Figure 2 Gas and total conversion at different reaction times

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图 3 煤直接加氢液化反应机理示意图

Figure 3 Reaction mechanism for direct liquefaction of coal

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图 4 不同反应时间自由基浓度与油产率的变化

Figure 4 Free radical concentration and conversion rate at different reaction times

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图 5 不同反应时间g因子与杂原子浓度的变化

Figure 5 g-factor and hetero atom concentration at different reaction times

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表 1 煤样的工业分析和元素分析

Table 1 Proximate and ultimate analyses of sample

Sample	Proximate analysis w/%				Ultimate analysis w_daf/%					H/C (atomic ratio)
Sample	M_ad	A_d	V_daf	FC_daf	C	H	N	S_t	O^*	H/C (atomic ratio)
NMH coal	15.59	4.98	51.82	48.18	73.52	5.68	0.96	0.24	19.60	0.93
^*：by difference

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表 2 NMH煤的液化气体产物分析

Table 2 Liquefaction gas products analysis of NMH sample

NMH coal	φ/%
NMH coal	H₂	CO	CO₂	CH₄	C_2-4
5 min	90.68	1.19	5.07	2.19	0.87
15 min	90.61	1.30	5.34	1.79	0.96
30 min	89.53	1.46	5.42	2.31	1.28
45 min	88.96	1.54	5.51	2.59	1.40
60 min	88.43	1.52	5.59	3.10	1.36
90 min	86.60	1.68	6.48	3.53	1.71

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表 3 原煤和液化中间产物自由基浓度

Table 3 Free-radicals concentrations analysis of raw coal and PAAs

t/min	Raw coal	5	15	30	45	60	90
Ng/(×10¹⁶·g^-1)	266.54	125.19	138.22	177.80	191.21	183.24	164.78

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表 4 原煤和液化中间产物的g因子值

Table 4 g-factors analysis of raw coal and PAAs

t/min	Raw coal	5	15	30	45	60	90
g	2.00434	2.00347	2.00301	2.00403	2.00384	2.00313	2.00305
Heteroatom	20.80%	10.51%	11.44%	13.22%	11.88%	11.39%	11.58%

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表 5 PAA元素分析

Table 5 Ultimate analysis of PAAs

Ultimate analysis w_daf/%	Time t/min
Ultimate analysis w_daf/%	0	5	15	30	45	60	90
O	19.60	9.17	10.11	11.74	9.58	9.96	10.28
N	0.96	1.17	1.16	1.25	1.34	1.22	1.14
S_t	0.24	0.17	0.17	0.23	0.26	0.21	0.16

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