煤加压转化过程中煤焦结构及煤灰矿物相演变规律

雷鸣; 孙岑; 王春波

煤加压转化过程中煤焦结构及煤灰矿物相演变规律

华北电力大学能源动力与机械工程学院, 河北保定 071003

基金项目:

河北省自然科学基金 E2016502094

中央高校基本科研业务费专项资金 2017MS120

详细信息

中图分类号: TK16
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- 被引次数: 0
出版历程
- 收稿日期: 2018-02-09
- 修回日期: 2018-05-02
- 网络出版日期: 2021-01-23
- 刊出日期: 2018-08-10

The crystal structure of coal char and the mineral transformation of coal ash during coal conversion under pressurized conditions

School of Energy Power and Mechanical Engineering, North China Electric Power University, Baoding 071003, China

Funds:

Hebei Province Natural Science Foundation E2016502094

Fundamental Research Funds for the Central Universities 2017MS120

More Information

Corresponding author: LEI Ming, Tel：0312-7522236, E-mail: ncepu_lm@126.com

摘要

摘要: 利用高温高压管式炉结合X射线衍射仪（XRD）和傅里叶红外光谱分析（FT-IR）研究了不同压力下（0.1-6 MPa）热解煤焦矿物相和碳微晶结构以及燃尽煤灰矿物相的演变规律。结果表明，在矿物相转化上，压力的升高对煤焦矿物相种类影响较小；在微晶结构上，温度和压力的升高使得焦炭的芳香层片堆叠高度变大，石墨化程度加深；在官能团特征上，压力对于煤焦中有机官能团结构的影响有限。压力变化对煤灰中主要矿物相种类的影响较小，但对其相对含量有一定影响，主要原因是不同压力下煤粉着火机理的转变造成燃烧温度有所不同；温度对煤灰物相转化的影响相较于压力更显著。
- 煤焦 /
- 煤灰 /
- 矿物相 /
- 碳微晶结构 /
- 有机官能团 /
- 高温高压
Abstract: The influence of pressure (0.1-6 MPa) on the mineral phase of coal char and the carbon crystal structure and the mineral conversion of coal ash were investigated by using the tube furnace at higher temperature and pressure combined with the analysis of X-ray diffractometer (XRD) and Fourier transform infrared (FT-IR) spectroscopy. The results indicate that the mineral phase of coal char is not significantly affected by the pyrolysis pressure; while, the average stacking height or the graphitization degree of coal char increases with increasing the temperature and pressure. With respect to functional groups, the pressure has little effect on the structure of organic functional group. Also, it is found that the pressure has little effect on the main mineral phases of coal ash, but it can affect the relative contents of mineral phases, which is mainly due to the varying of combustion temperatures caused by the transition of the ignition mechanism at different pressures. The effect of temperature on the mineral transformation is more significant than that of pressure.
- char /
- ash /
- mineral phase /
- crystal structure /
- organic functional group /
- high temperature and high pressure

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图 1 实验系统示意图

Figure 1 Schematic diagram of the experimental system

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图 2 原煤的XRD谱图

Figure 2 XRD patterns of coal samples

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图 3 1000 ℃时不同压力下煤焦矿物质XRD谱图

Figure 3 XRD spectra of coal chars at different pressures at 1000 ℃

F: ferrous sulfide; Q: quartz; P: periclase; G: graphite; O: oldhamite; K: K-feldspar

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图 4 4 MPa时不同温度煤焦矿物质的XRD谱图

Figure 4 XRD patterns of coal chars under 4 MPa at different temperatures

F: ferrous sulfide; M: muscovite; Q: quartz; P: periclase; G: graphite; Ge: gehlerite; O: oldhamite; K: K-feldspar

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图 5 1000 ℃下不同压力热解煤焦矿物质FT-IR谱图

Figure 5 FT-IR spectra of coal chars under different pressures at 1000 ℃

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图 6 1000 ℃下不同压力燃烧后煤灰矿物质XRD谱图

Figure 6 XRD patterns of coal ashes under different pressures at 1000 ℃

A: anhydrite; An: anorthite; C: calcite; F: forsterite; Ⅰ: illite; M: muscovite; Mu: mullite; H: hematite; O: orthoclasse; P: periclase; Q: quartz; S: sanidine; Ge: gehlenite

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图 7 0.1 MPa下不同温度煤灰矿物质XRD谱图

Figure 7 XRD spectra of coal ashes under different temperatures at 0.1 MPa

A: anhydrite; An: anorthite; C: calcite; D: diopside; H: hematite; M: muscovite; Mu: mullite; O: orthoclasse; P: periclase; Q: quartz; S: sanidine

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图 8 4 MPa下不同温度燃烧后煤灰矿物质XRD谱图

Figure 8 XRD patterns of coal ashes under different temperatures at 4 MPa

A: anhydrite; An: anorthite; C: calcite; Cl: clinoenstatit; F: forsterite; M: muscovite; Mu: mullite; H: hematite; O: orthoclasse; P: periclase; Q: quartz; S: sanidine

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表 1 实验所用煤样的煤质分析

Table 1 Properties of pulverized coal sample

Proximate analysis w_ad/%					Ultimate analysis w_ad/%
M	A	V	FC		C	H	N	S	O
2.3	35.4	21.7	40.6		50.04	3.18	0.57	0.30	8.22
Ash composition w/%
Al₂O₃	SiO₂	CaO	Fe₂O₃	MgO	TiO₂	SO₃	K₂O	Na₂O	P₂O₅
25.1	58.6	4.47	5.03	1.42	1.17	0.461	2.29	0.678	0.324

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表 2 1000 ℃不同压力下煤焦微晶结构参数

Table 2 Crystallite structure parameters of coal char under different pressures at 1000 ℃

Pressure	Diffraction angle /(°)		Microcrystalline structure parameters /10^-1 nm
Pressure	002 peak	100 peak	d	L_c	L_a
0.1 MPa	26.59	44.67	3.353	9.43	9.10
2 MPa	26.61	44.64	3.350	9.80	10.54
4 MPa	26.63	44.68	3.347	12.73	12.78

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表 3 4 MPa不同温度下热解煤焦微晶结构参数

Table 3 Crystallite structure parameters of coal char under different temperatures at 4 MPa

Temperature	Diffraction angle /(°)		Microcrystalline structure parameters /10^-1 nm
Temperature	002 peak	100 peak	d	L_c	L_a
800 ℃	26.57	44.58	3.355	9.93	11.19
900 ℃	26.63	44.67	3.348	10.7	10.72
1000 ℃	26.63	44.68	3.347	12.78	12.78
1100 ℃	26.65	44.67	3.345	12.73	9.79

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参考文献(19)

[1]	李帆, 邱建荣, 郑瑛, 郑楚光.煤燃烧过程矿物质行为研究[J].工程热物理学报, 1999, 20(2):258-260. http://cdmd.cnki.com.cn/Article/CDMD-10112-2003094017.htm LI Fan, QIU Jan-rong, ZHANG Ying, ZHENG Chu-guang. Study on behavior of mineral matters in coal burring burning process[J]. J Eng Therm, 1999, 20(2):258-260. http://cdmd.cnki.com.cn/Article/CDMD-10112-2003094017.htm
[2]	YANG H P, CHEN H P, JU F D, YAN R, ZHANG S H. Influence of pressure on coal pyrolysis and char gasification[J]. Energy Fuels, 2007, 21(6):3165-3170. doi: 10.1021/ef700254b
[3]	王贤华, 徐健, 杨海平, 陈汉平.加压热解对煤焦理化结构特性的影响[J].华中科技大学学报(自然科学版), 2011, 39(7):123-127. http://www.cnki.com.cn/Article/CJFDTOTAL-DDPL201204000.htm WANG Xian-hua, XU Jian, YANG Hai-ping, CHEN Han-ping. Influence of pyrolysis pressure on coal char physic-chemical property[J]. J Huazhong Univ Sci Technol (Nat Sci Ed), 2011, 39(7):123-127. http://www.cnki.com.cn/Article/CJFDTOTAL-DDPL201204000.htm
[4]	JING N J, WANG Q H, CHENG L M, LUO Z Y, CEN K F. The sintering behavior of coal ash under pressurized conditions[J]. Fuel, 2013, 103:87-93. doi: 10.1016/j.fuel.2011.09.025
[5]	JING N J, WANG Q H, CHENG L M, LUO Z Y, CEN K F. Effect of temperature and pressure on the mineralogical and fusion characteristics of Jincheng coal ash in simulated combustion and gasification environments[J]. Fuel, 2013, 104:647-655. doi: 10.1016/j.fuel.2012.05.040
[6]	WANG C B, LEI M, YAN W P, WANG S L, JIA L F. Combustion characteristics and ash formation of pulverized coal under pressurized oxy-fuel conditions[J]. Energy Fuels, 2011, 25(10):4333-4344. doi: 10.1021/ef200956q
[7]	MAYORAL M C, IZQUIERDO M T, ANDRÉS J M, RUBIO B. Aluminosilicates transformations in combustion followed by DSC[J]. Thermochim Acta, 2001.373(2):173-180. doi: 10.1016/S0040-6031(01)00459-2
[8]	赵松海, 魏丽颖, 刘松辉, 汪澜, 管学茂.高温液相对熟料方镁石形成的影响[J].硅酸盐通报, 2014, 33(7):1599-1603. http://www.cqvip.com/QK/95401A/201310/47789215.html ZHAO Song-hai, WEI Li-ying, LIU Song-hui, WANG Lan, GUAN Xue-mao. Effect of high temperature liquid phase on the formed of periclase in clinker[J]. Bull Chin Ceram Soc, 2014, 33(7):1599-1603. http://www.cqvip.com/QK/95401A/201310/47789215.html
[9]	GADIOU R, BOUZIDI Y, PRADO G. The devolatilisation of millimetre sized coal particles at high heating rate:the influence of pressure on the structure and reactivity of the char[J]. Fuel, 2002, 81(16):2121-2130. doi: 10.1016/S0016-2361(02)00144-8
[10]	韩克鑫. 煤中矿物质赋存及高温演变规律对灰熔融特性的影响研究[D]. 杭州: 浙江大学, 2016. HAN Ke-xin. Mode of occurrence and high-temperature behaviors of mineral matter in coals and their effects on ash fusibility[D]. Hangzhou: ZheJiang University, 2016.
[11]	LI W, ZHU Y M. Structural characteristics of coal vitrinite during pyrolysis[J]. Energy Fuels, 2014, 28(6):3645-3654. doi: 10.1021/ef500300r
[12]	YEN T F, ERDMAN J G, POLLACK S S. Investigation of the structure of petroleum asphaltenes by X-Ray diffraction[J]. Anal Chem, 1961, 33(11):1587-1594. doi: 10.1021/ac60179a039
[13]	许凯, 胡松, 苏胜, 帅超.孙路石.徐超芬.向军.不同热解压力对煤焦结构的影响[J].工程热物理学报, 2013, 34(2):372-375. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=rlhxxb200702005 XU-Kai, HU-Song, SU-Sheng, SHUAI Chao, SUN Lu-shi, XU Chao-fen, XIANG Jun.The effect of pyrolysis pressure on char physicochemical structure[J]. J Eng Therm, 2013, 34(2):372-375. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=rlhxxb200702005
[14]	刘冬冬, 高继慧, 吴少华, 秦裕琨.热解过程煤焦微观结构变化的XRD和Raman表征[J].哈尔滨工业大学学报, 2016, 48(07):39-45. http://www.oalib.com/paper/4968450 LIU Dong-dong, GAO Ji-hui, WU Shao-hua, QIN Yu-kun. XRD and Raman characterization of microstructure changes of char during pyrolysis[J]. J Harbin Inst Technol, 2016, 48(07):39-45. http://www.oalib.com/paper/4968450
[15]	SHEN C D, LI Y. Experimental study of ash formation during pulverized coal combustion in O₂/CO₂ mixtures[J]. Fuel, 2008, 87(7):1297-1305. doi: 10.1016/j.fuel.2007.07.023
[16]	雷鸣, 王春波, 阎维平, 王松岭.大同烟煤增压富氧燃烧的热重实验研究[J].中国电机工程学报, 2012, 32(5):21-26. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=zgdjgcxb201205005 LEI Ming, WANG Chun-bo, YAN Wei-ping, WANG Song-ling. Thermogravimetric research on pressurized oxy-fuel combustion of datong bituminous coal[J]. Proc CSEE, 2012, 32(5):21-26. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=zgdjgcxb201205005
[17]	王春波, 雷鸣, 阎维平, 王松岭.煤粉的增压富氧燃烧特性及煤灰矿物演变[J].燃料化学学报, 2012, 40(7):790-794. http://manu60.magtech.com.cn/rlhxxb/CN/abstract/abstract17980.shtml WANG Chun-bo, LEI Ming, YAN Wei-ping, WANG Song-ling. Combustion characteristics of pulverized coal and mineral conversion under pressurized oxy-fuel condition[J]. J Fuel Chem Technol, 2012, 40(7):790-794. http://manu60.magtech.com.cn/rlhxxb/CN/abstract/abstract17980.shtml
[18]	谷成儒. 钾长石磷矿综合利用技术研究[D]. 合肥: 合肥工业大学, 2014. GU Cheng-ru. Research on Potash Feldspar Phosphate Rock Comprehensive Utilization Technology[D]. Hefei: Hefei University of Technology, 2014.
[19]	任雪娇. 石膏、钾长石热反应基础研究[D]. 昆明: 昆明理工大学, 2013. REN Xue-jiao. Basic study on thermal reaction of gypsum and potash feldspar[D]. Kunming: Kunming University of Science and Technology, 2013.