油页岩半焦燃烧动力学研究

doi:10.11949/j.issn.0438-1157.20190099

摘要/Abstract

摘要：

燃烧动力学是研究油页岩半焦颗粒燃烧特性的基础。利用热重分析仪对油页岩半焦进行了恒温燃烧实验研究，在排除外扩散影响的基础上，分析了燃烧温度、氧气浓度对油页岩半焦燃烧过程的影响。在实验范围内，氧气浓度和燃烧温度均能对油页岩半焦燃烧速率产生重要影响，更高的氧气浓度和燃烧温度可以加快油页岩半焦燃烧速率。结合实验结果，建立了考虑氧气浓度影响的油页岩半焦燃烧动力学模型，发现油页岩半焦燃烧速率与氧气浓度的0.97次方呈线性关系。模型计算结果与实验结果符合较好，为进一步研究油页岩半焦大颗粒燃烧特性提供了燃烧动力学基础。

关键词: 油页岩半焦, 燃料, 燃烧, 动力学, 模型

Abstract:

Combustion kinetics is the basis for studying the combustion characteristics of oil shale semi-coke particles. Thermal gravimetric analyzer (TGA) was used to conduct isothermal combustion experiments of oil shale semi-coke. Effects of combustion temperature and oxygen concentration on kinetics of oil shale semi-coke combustion were analyzed. Higher combustion temperature and oxygen concentration would lead to faster combustion rate. A kinetic model considering oxygen concentration effects was developed. It was found that the combustion rate of oil shale semi-coke is proportional to oxygen concentration to the 0.97 power. The kinetic model yielded good agreements with the experiments results, and could provide a base for further investigation on the combustion of large oil shale semi-coke particles.

Key words: oil shale semi-coke, fuel, combustion, kinetics, model

中图分类号:

TQ 028.8

黄逸群, 张缦, 苗苗, 邓博宇, 蔡晋, 吴玉新, 吕俊复, 金燕, 杨海瑞. 油页岩半焦燃烧动力学研究[J]. 化工学报, 2019, 70(8): 3033-3039.

Yiqun HUANG, Man ZHANG, Miao MIAO, Boyu DENG, Jin CAI, Yuxin WU, Junfu LYU, Yan JIN, Hairui YANG. Combustion kinetics study of oil shale semi-coke[J]. CIESC Journal, 2019, 70(8): 3033-3039.

图/表 11

表1 实验所用油页岩样品工业分析及发热量

Table 1 Proximate analysis and heat value of Huadian oil shale semicoke used in experiments

样品	工业分析/%				Q_ar,net/(kJ/kg)
样品	M_ar	A_ar	V_ar	FC_ar	Q_ar,net/(kJ/kg)
桦甸油页岩	7.06	62.08	26.60	4.26	9517.9
桦甸油页岩半焦	0.64	83.14	5.74	10.48	3767.2

图1 实验过程中典型的升温、失重曲线（YO2=18.9%, T=700℃, 流量100 ml/min）

Fig.1 Typical heating and mass loss curves in experiments（YO2=18.9%, T=700℃, flow rate=100 ml/min）

图2 气体流量对油页岩半焦燃烧的影响（YO2=18.9%，T=800℃）

Fig.2 Effects of gas flow rate on oil shale semicoke combustion（YO2=18.9%，T=800℃）

图3 燃烧温度对油页岩半焦燃烧的影响 (YO2=12.6%)

Fig.3 Effects of combustion temperature on oil shale semicoke combustion (YO2=12.6%)

图4 氧气浓度对油页岩半焦燃烧的影响 (T =800℃)

Fig.4 Effects of oxygen concentration on oil shale semicoke combustion (T =800℃)

表2 动力学模型参数结果

Table 2 Kinetic model parameters

燃烧温度/℃	氧气浓度/(mol/m³)	n	m	k
800	2.178	0.995	1.115	0.112
	1.936	0.926	1.115	0.112
	1.694	0.774	1.115	0.112
	1.452	0.703	1.115	0.112
750	2.277	0.790	0.850	0.093
	2.024	0.655	0.850	0.093
	1.771	0.473	0.850	0.093
	1.518	0.398	0.850	0.093
700	2.394	0.686	0.815	0.084
	2.128	0.609	0.815	0.084
	1.862	0.496	0.815	0.084
	1.596	0.557	0.815	0.084
650	2.529	1.019	1.149	0.060
	2.248	0.782	1.149	0.060
	1.967	0.805	1.149	0.060
	1.686	0.579	1.149	0.060
600	2.673	1.055	0.897	0.055
	2.376	0.688	0.897	0.055
	2.079	0.743	0.897	0.055
	1.782	0.503	0.897	0.055

图5 反应常数回归结果

Fig.5 Regression results of reaction rate constant

图8 模型计算结果与实验对比 (T=800℃，YO2=18.9%)

Fig.8 Comparison between model prediction and experiment results (T=800℃，YO2=18.9%)

图6 模型计算结果与实验对比 (T=700℃,YO2=12.6%)

Fig.6 Comparison between model prediction and experiment results (T=700℃, YO2=12.6%)

图7 模型计算结果与实验对比 (T=750℃，YO2=16.8%)

Fig.7 Comparison between model prediction and experiment results (T=750℃，YO2=16.8%)

图9 式(9)与式(10)计算对比

Fig.9 Comparison between Eq.(9) and Eq.(10)

参考文献 30

1	胡文瑞, 翟光明, 李景明. 中国非常规油气的潜力和发展[J]. 中国工程科学, 2010,12(5): 25-29.
	HuW R, ZhaiG M, LiJ M. Potential and development of unconventional hydrocarbon resources in China[J]. Engineering Sciences, 2010,12(5):25-29.
2	贾承造, 郑民, 张永峰. 中国非常规油气资源与勘探开发前景[J]. 石油勘探与开发, 2012, 39(2):129-136.
	JiaC Z, ZhengM, ZhangY F. Unconventional hydrocarbon resources in China and the prospect of exploration and development[J]. Petroleum Exploration and Development, 2012, 39(2): 129-136.
3	王擎, 黄宗越, 迟铭书, 等. 油页岩干酪根化学结构特性分析[J]. 化工学报, 2015, 66(5): 1861-1866.
	WangQ, HuangZ Y, ChiM S, et al. Chemical structure analysis of oil shale kerogen[J]. CIESC Journal, 2015, 66(5):1861-1866.
4	刘德勋, 赵群, 王红岩, 等. 国内外小颗粒油页岩干馏工艺现状与展望[J]. 广州化工, 2010, 38(12): 7-11.
	LiuD X, ZhaoQ, WangH Y, et al. Current status and prospect of small-size oil shale retort process[J]. Guangzhou Chemical Industry, 2010, 38(12): 7-11.
5	熊耀, 马名杰, 黄山秀, 等. 国内油页岩干馏炼油技术发展现状[J]. 现代化工, 2013,33(8):40-44.
	XiongY, MaM J, HuangS X, et al. Current status of carbonization process of oil shale in China[J]. Modern Chemical Industry, 2013, 33(8):40-44.
6	杨庆春, 周怀荣, 杨思宇, 等. 油页岩开发利用技术及系统集成的研究进展[J]. 化工学报, 2016, 67(1): 109-118.
	YangQ C, ZhouH R, YangS Y, et al. Research progress on utilization and systemic integration technologies of oil shale[J]. CIESC Journal, 2016, 67(1): 109-118.
7	韩向新. 油页岩半焦燃烧机理与循环流化床燃烧利用[D]. 上海: 上海交通大学, 2007.
	HanX X. Combustion mechanism of oil shale semicoke and combustion utilization in CFB boilers[D]. Shanghai: Shanghai Jiao Tong University, 2007.
8	柏静儒, 王擎, 孙佰仲, 等. 桦甸油页岩半焦基础理化特性[J]. 吉林大学学报(地球科学版), 2010, 40(4): 905-911.
	BaiJ R, WangQ, SunB Z, et al. Basic physicochemical characteristics of the Huadian oil shale semi-cokes[J]. Journal of Jilin University(Earth Science Edition) , 2010, 40(4): 905-911.
9	王擎, 徐峰, 柏静儒, 等. 桦甸油页岩基础物化特性研究[J]. 吉林大学学报(地球科学版), 2006, 36(6): 1006-1011.
	WangQ, XuF, BaiJ R, et al. Study on the basic physicochemical characteristics of the Huadian oil shales[J]. Journal of Jilin University(Earth Science Edition) , 2006, 36(6): 1006-1011.
10	王剑秋, 王贤清. 颗粒页岩半焦燃烧反应模型的研究[J]. 石油学报(石油加工), 1987, 3(3): 4-12.
	WangJ Q, WangX Q. A study of the combustion reaction model of oil shale particles[J]. Acta Pettrolei Sinica(Petroleum Processing Section), 1987, 3(3): 4-12.
11	严君伟, 姜秀民, 韩向新, 等. 油页岩半焦循环流化床燃烧的工业实验研究[J]. 动力工程学报, 2014, 34(7): 518-523.
	YanJ W, JiangX M, HanX X, et al. Industrial experimental study on combustion of oil shale semicoke in a CFB boiler[J]. Journal of Chinese Society of Power Engineering, 2014, 34(7): 518-523.
12	崔志刚, 吴晓燕, 马素霞. 油页岩半焦流化床混烧特性实验研究[J]. 电站系统工程, 2015, (4): 1-5.
	CuiZ G, WuX Y, MaS X. Experimental study on co-combustion of oil shale and its semicoke in fluidized bed[J]. Power System Engineering, 2015, (4): 1-5.
13	李晓栋, 樊保国, 金燕, 等. 油页岩半焦燃烧特性试验研究[J]. 煤炭学报, 2016, 41(10): 2473-2478.
	LiX X, FanB G, JinY, et al. Experimental study on combustion characteristics of oil shale semi-coke[J]. Journal of China Coal Society, 2016, 41(10): 2473-2478.
14	韩向新, 姜秀民, 崔志刚, 等. 油页岩半焦燃烧特性的研究[J]. 中国电机工程学报, 2005, 25(15): 106-110.
	HanX X, JiangX M, CuiZ G, et al. Study of combustion performance of oil shale semi-coke[J]. Proceedings of the CSEE, 2005, 25(15): 106-110.
15	HanX X, JiangX M, CuiZ G. Study of the combustion mechanism of oil shale semicoke in a thermogravimetric analyzer[J]. Journal of Thermal Analysis & Calorimetric, 2008, 92(2): 595-600.
16	王擎, 吴吓华, 孙佰仲, 等. 桦甸油页岩半焦燃烧反应动力学研究[J]. 中国电机工程学报, 2006, 26(7): 29-34.
	WangQ, WuX H, SunB Z, et al. Combustion reaction kinetics study of Huadian oil shale semi-coke[J]. Proceeding of the CSEE, 2006, 26(7):29-34.
17	GoldfarbJ L, Amico AD, CulinC, et al. Oxidation kinetics of oil shale semicokes: reactivity as a function of pyrolysis temperature and shale origin[J]. Energy & Fuels, 2013, 27(2): 666-672.
18	BaiF, SunY, LiuY, et al. Kinetic investigation on partially oxidized Huadian oil shale by thermogravimetric analysis[J]. Oil Shale, 2014, 4(31): 377-393.
19	张少冲. 油页岩半焦燃烧过程中含氧官能团和孔隙结构的演变研究[D]. 吉林: 东北电力大学, 2017.
	ZhangS C. Study on the changes of oxygen containing functional group and pore structure during oil shale semi-coke combustion[D]. Jilin: Northeast Electric Power University, 2017.
20	LooL, MaatenB, NeshumayevD, et al. Oxygen influence on Estonian Kukersite oil shale devolatilization and char combustion[J]. Oil Shale, 2017, 3(34): 219-231.
21	FujimotoF D, BraunR L, TaylorR W, et al. Intrinsic kinetics of oxidation of residual organic carbon in rapidly pyrolyzed oil shale[J]. Energy & Fuels, 1987, 1(4): 320-323.
22	HongY S, SunK K. Intrinsic kinetics of the reaction between oxygen and carbonaceous residue in retorted oil shale[J]. Industrial & Engineering Chemistry Process Design & Development, 1980, 19(4): 550-555.
23	王贤清, 王剑秋, 钱家麟, 等. 油页岩半焦燃烧中灰分层的扩散动力学研究[J]. 石油学报(石油加工), 1987, 3(4): 4-11.
	WangX Q, WangJ Q, QianJ L, et al. Diffusion effects in the ash layer of the oil shale char combustion[J]. Acta Petrolei Sinica(Petroleum Processing Section) , 1987, 3(4): 4-11.
24	梅琳. 高灰分低热值工业固体废弃物流化床燃烧特性的实验研究[D]. 重庆:重庆大学, 2015.
	MeiL. Experimental study on combustion characteristics of high ash content and low calorific value industrial solid waste in a CFB combustor[D]. Chongqing: Chongqing University, 2015.
25	张守玉, 吕俊复, 王文选, 等. 热处理对煤焦反应性及微观结构的影响[J]. 燃料化学学报, 2004, 32(6): 673-678.
	ZhangS Y, LyuJ F, WangW X, et al. Effect of heat treatment on the reactivity and microstructure of coal-char[J]. Journal of Fuel Chemistry and Technology, 2004, 32(6): 673-678.
26	YoshizawaN, MaruyamaK, YamashitaT, et al. Dependence of microscopic structure and swelling property of DTF chars upon heat-treatment temperature[J]. Fuel, 2006, 85(14): 2064-2070.
27	SalatinoP, SennecaO, MasiS. Assessment of thermodeactivation during gasification of a bituminous coal char[J]. Energy & Fuels, 1999, 13(6): 1154-1159.
28	SennecaO, SalatinoP. Loss of gasification reactivity toward O₂ and CO₂ upon heat treatment of carbons[J]. Proceedings of the Combustion Institute, 2002, 29(1): 485-493.
29	DongS, AlvarezP, PatersonN, et al. Study on the effect of heat treatment and gasification on the carbon structure of coal chars and metallurgical cokes using Fourier transform Raman spectroscopy[J]. Energy & Fuels, 2013, 23(3): 1651-1661.
30	张志, 李振山, 蔡宁生. 焦炭燃烧模型的改进及其Fluent实现与实验验证[J]. 中国电机工程学报, 2015, 35(7): 1681-1688.
	ZhangZ, LiZ S, CaiN S. An improved char combustion model and its implement in Fluent and experimental validation[J]. Proceedings of the CSEE, 2015, 35(7): 1681-1688.

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