FLASHCHAIN模型应用于汪清油页岩热解研究

王擎; 杨乾坤; 许祥成; 崔达; 张宏喜; 王一帆

FLASHCHAIN模型应用于汪清油页岩热解研究

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 51276034

详细信息

中图分类号: TK16
计量
- 文章访问数: 91
- HTML全文浏览量: 29
- PDF下载量: 6
- 被引次数: 0
出版历程
- 收稿日期: 2015-09-02
- 修回日期: 2015-10-19
- 网络出版日期: 2022-03-23
- 刊出日期: 2016-02-01

Application of FLASHCHAIN model in pyrolysis of Wangqing oil shale

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

More Information

Corresponding author: Tel：0432-64807366，E-mail：rlx888@126.com

摘要

摘要: 采用¹³C-NMR技术表征出汪清三个矿区油页岩的碳原子化学结构, 并获得碳骨架结构的12个重要参数。利用热重和傅里叶红外联用技术 (TG-FTIR) 得出了在50℃/min升温速率和热解终温600℃下油页岩热解时轻质气体的生成规律。采用基于燃料化学结构的FLASHCHAIN模型对热解产物的析出进行了模拟, 并与实验结果相比较。结果表明, FLASHCHAIN模型用来模拟汪清油页岩热解时, 在520℃之前有较好的效果, 当温度高于520℃时, 由于二次热解反应及页岩中矿物质分解对热解过程的影响, 导致模型的预测值与实验值存在一定的误差, 且随着温度的升高两者之间的误差也随之加大。
- 油页岩 /
- ¹³C-NMR /
- 热重红外 /
- FLASHCHAIN
Abstract: The carbon atom chemical structure of three Wangqing oil shales was characterized by ¹³C-NMR techniques, and twelve important parameters of the carbon skeleton structure were obtained.Thermogravimetric-Fourier transform infrared spectroscopy (TG-FTIR) tests were used to obtain the formation of light gases during pyrolysis at 50℃/min and the final temperature of 600℃.The FLASHCHAIN model, which was established based on the structure of fuel, was employed to simulate the evolution of pyrolysis products and compared with the experimental tests.The results show that the model has a good simulation below 520℃, some errors occur above 520℃ due to the influence of secondary pyrolysis reactions and decomposition of minerals in the shale.The errors increase gradually with the increasing pyrolysis temperature.
- oil shale /
- ¹³C-NMR /
- TG-FTIR /
- FLASHCHAIN

HTML全文

图 1 汪清油页岩的¹³C-NMR谱图

Figure 1 ¹³C-NMR spectrum of Wangqing oil shale

下载: 全尺寸图片幻灯片

图 2 FLASHCHAIN模型机理示意图

Figure 2 Schematic illustration of the machanisms in Flashchain

①: bridge scission; ②: gas from spontaneous condensation of bridges into char links; ③: phase equilibrium

下载: 全尺寸图片幻灯片

图 3 50℃/min升温速率下热解产物产量的预测曲线与实验曲线

Figure 3 Prediction curve and the experimental curves of the yield of the product at 50℃/min heating rate

下载: 全尺寸图片幻灯片

图 4 50℃/min升温速率下热解产物产量的预测曲线与实验曲线

Figure 4 Prediction and experimental curves of the product yield at 50℃/min

下载: 全尺寸图片幻灯片

表 1 油页岩样品的工业分析、元素分析和原子比

Table 1 Proximate analysis, ultimate analysis and atomic ratio of oil shale samples

Sample	Proximate analysis w_ad/%				Ultimate analysis w_ad/%					Atomic ratio
Sample	M	V	A	FC	C	H	O	N	S	H/C	O/C
WQ1	2.22	17.60	78.18	2.00	14.30	1.07	5.76	0.69	0.26	0.90	0.30
WQ3	1.78	15.02	81.17	2.03	11.23	1.41	5.44	0.55	0.20	1.51	0.36
WQ5	1.86	16.11	80.28	1.75	12.03	1.50	5.56	0.63	0.21	1.50	0.35

下载: 导出CSV

表 2 碳化学位移归属

Table 2 Assignments for peaks in ¹³C-NMR spectra

Chemical shift δ	Carbon functionality	WQ1	WQ3	WQ5
14-16	aliphatic methyl	2.48	2.22	3.02
16-22	aromatic methyl	7.75	6.06	9.94
22-36	methylene and aliphatic C (2) carbon	47.43	34.05	58.36
36-50	methine and quaternary carbon	18.91	12.97	21.49
50-55	oxy-methylene	2.79	2.32	1.57
55-75	oxy-methine	3.10	0.72	0.69
75-90	oxy-quaternary	0.31	0.75	0.00
100-129	ortho-oxyaromatic protonated	20.46	11.89	21.70
129-137	bridgehead aromatic carbon	8.06	6.84	10.59
137-148	aromatic branched	6.20	4.56	6.38
148-164	oxy-aromatic carbon	2.79	2.69	2.09
164-188	carboxyl	0.31	0.31	0.00
188-220	carbonyl	0.62	0.00	0.00

下载: 导出CSV

表 3 油页岩样品碳骨架结构参数

Table 3 Carbon structural parameters of oil shale sample

Sample	f_a	f′_a	f_a^c	f_a^H	f_a^N	f_a^P	f_a^S	f_a^B	f_al	f_al^H	f_al^*	f_al^O
WQ1	35.18	35.18	0	15.90	19.28	2.17	4.82	6.27	64.82	56.14	8.68	4.82
WQ3	36.07	36.07	0	13.39	22.68	3.03	5.13	7.70	63.93	56.36	7.57	4.27
WQ5	35.64	35.64	0	15.25	20.39	1.47	4.48	7.44	64.36	57.72	6.64	1.59
note：f_a: total aromatic carbon；f′_a: aromatic carbons；f_a^c: carbonyl carbon；f_a^H: protonated aromatic carbon；f_a^N: non-protonated aromatic carbon；f_a^P: phenolic hydroxyl carbon；f_a^S: alkyl substituted aromatic carbon；f_a^B: bridgehead aromatic carbon；f_al: totalaliphatic carbon；f_al^H: methylene or methane carbon；f_al^* : methyl and quaternary carbon；f_al^O: oxygen-kinked aliphatic carbon

下载: 导出CSV

表 4 结构参数的命名及计算公式

Table 4 Nomenclature and equations of structural parameters

No.	Symbol	Structural parameter	Equation
1	x_b	ratio of aromatic bridging carbons and aromatic ring carbons	${x_{\rm{b}}}=\frac{{f_{\rm{a}}^{\rm{B}}}}{{{{f'}_{\rm{a}}}}}$
2	C_a	carbons of aromatic cluster	${x_{\rm{b}}}=\frac{{1 -tan{\rm{h}}\frac{{\left ({{C_{\rm{a}}} -{C_0}} \right)}}{m}}}{2}{{x'}_{\rm{b}}} + \frac{{1 + tan{\rm{h}}\left ({\frac{{{C_{\rm{a}}} -{C_0}}}{m}} \right)}}{2}{{x''}_{\rm{b}}}$
3	C_cl	cluster carbons	${C_{{\rm{cl}}}}={C_{\rm{a}}} + {C_{{\rm{al}}}}$
4	C_al	aliphatic carbons	${C_{{\rm{al}}}}={C_{\rm{a}}}\frac{{{f_{{\rm{al}}}}}}{{{f_{\rm{a}}}}}$
5	C_p	circumferential carbons	${C_{\rm{p}}}={C_{{\rm{cl}}}}\left ({f_{\rm{a}}^{\rm{H}} + f_{\rm{a}}^{\rm{S}} + f_{\rm{a}}^{\rm{B}}} \right)$
6	R_a	aromatic rings	${R_{\rm{a}}}=\frac{1}{2}\left ({{C_{\rm{a}}} -{C_{\rm{p}}}} \right) + 1$

下载: 导出CSV

表 5 油页岩样品的团簇结构参数

Table 5 Structural parameters of oil shale aromatic cluster

Sample	x_b	C_a	C_cl	C_al	C_p	R_a
WQ1	0.1714	8.53	24.37	15.84	6.15	2.19
WQ3	0.2134	10.64	29.50	18.86	7.73	2.46
WQ5	0.2087	10.40	29.18	18.78	7.93	2.24

下载: 导出CSV

参考文献(22)

[1]	刘招君, 柳蓉.中国油页岩特征及开发利用前景分析[J].地学前缘, 2005, 12(3):315-322. http://www.cnki.com.cn/Article/CJFDTOTAL-DXQY200503044.htm LIU Zhao-jun, LIU Rong.Oil shale resource state and evaluating system[J].Earth Science Frontiers, 2005, 12(3):315-323. http://www.cnki.com.cn/Article/CJFDTOTAL-DXQY200503044.htm
[2]	HOU X L.Prospect of oil shale and shale oil industry.Proceedings international conference on oil shale oil[M].Beijing:Chemical Industry Press, 1988:7-15.
[3]	QIAN J L, YIN L.Oil shale-petroleum alternative[M].Beijing:China Petrochemical Press, 2008:30-34.
[4]	NIKSA S.FLASHCHAIN theory for rapid coal devolatilization.1.Formulation[J].Energy Fuels, 1991, 5(5):647-665. doi: 10.1021/ef00029a006
[5]	NIKSA S.FLASHCHAIN theory for rapid coal devolatilization.2.Impact of operating conditions[J].Energy Fuels, 1991, 5(5):665-673. doi: 10.1021/ef00029a007
[6]	NIKSA S.FLASHCHAIN theory for rapid coal devolatilization.3.Modeling the Behavior of Various Coals[J].Energy Fuels, 1991, 5(5):673-683. doi: 10.1021/ef00029a008
[7]	NIKSA S.FLASHCHAIN theory for rapid coal devolatilization.4.Predicting ultimate yields from ultimate analyses alone[J].Energy Fuels, 1994, 8(3):659-670. doi: 10.1021/ef00045a022
[8]	NIKSA S.FLASHCHAIN Theory for rapid coal devolatilization.5.Interpredicting rates of devolatilization for various coal types and operating conditions[J].Energy Fuels, 1994, 8(3):671-679. doi: 10.1021/ef00045a023
[9]	NIKSA S.FLASHCHAIN theory for rapid coal devolatilization.6.Predicting the evolution of fuel nitrogen from various coals[J].Energy Fuels, 1995, 9(3):467-478. doi: 10.1021/ef00051a011
[10]	NIKSA S.FLASHCHAIN theory for rapid coal devolatilization.7.Predicting the release of oxygen species from various coals[J].Energy Fuels, 1996, 10(1):173-187. doi: 10.1021/ef950067l
[11]	SOLOMON P R, HAMBIEN D G, CARANGRLO R M.General model of coal devolatilization[J].Energy Fuels, 1988, 2(4):405-422. doi: 10.1021/ef00010a006
[12]	GRANT D M, PUGMIRE R J, FLETCHER T H.Chemical model of coal devolatilization using percolation lattice statistics[J].Energy Fuels, 1989, 3(2):175-186. doi: 10.1021/ef00014a011
[13]	FLETCHER T H, KERSTEIN A R, PUGMIRE R J.Chemical percolation model for devolatilization.2.Temperature and heating rate effects on product yields[J].Energy Fuels, 1990, 4(1):54-60. doi: 10.1021/ef00019a010
[14]	THOMAS FLETCHER.Chemical percolation model for devolatilization[J].Energy Fuels, 1992, 6(1):414-431.
[15]	JUPUDI R S, ZAMANSKY V, FLETCHER T H.Prediction of light gas composition in coal devolatilization[J].Energy Fuels, 2009, 23(6):3063-3067. doi: 10.1021/ef9001346
[16]	NIKSA S.Predicting the rapid devolatilization of diverse forms of biomass with bio-FLASHCHAIN[J].Proc Combust Inst, 2000, 28(2):2727-2733. doi: 10.1016/S0082-0784(00)80693-1
[17]	CHEN Y, CHARPENAY S, JENSEN A.Modeling of biomass pyrolysis kinetics[J].Symp (Int) Combust, 1998, 27(1):1327-1334. doi: 10.1016/S0082-0784(98)80537-7
[18]	FLETCHER T H, HARLAND R, WEBSTER J.Prediction of tar and light gas during pyrolysis of black liquor and biomass[J].Energy Fuels, 2012, 26(6):3381-3387. doi: 10.1021/ef300574n
[19]	DOMINIC B.An advanced model of coal devolatilization based on chemical structure[D].Provo:Brigham Young University, 1999:39-40.
[20]	秦匡宗, 劳永新.茂名和抚顺油页岩组成结构的研究I.有机质的芳碳结构[J].燃料化学学报, 1985, 13(2):133-140. QIN Kuang-zong, LAO Yong-xin.Investigation on the constitution and structure of Maoming and Fushun oil shale I.The structural components of the organic matter[J].J Fuel Chem Technol, 1985, 13(2):133-140.
[21]	TONG J, HAN X, WANG S.Evaluation of structural characteristics of huadian oil shale kerogen using direct techniques (Solid-State ¹³C-NMR, XPS, FT-IR and XRD)[J].Energy Fuels, 2011, 25(9):4006-4013. doi: 10.1021/ef200738p
[22]	SOLUM M S, PUGMIRE R J, GRANT D M.¹³C solid-state NMR argonne premium coals[J].Energy Fuels, 1989, 3(2):187-193. doi: 10.1021/ef00014a012