Al2O3-SiO2-CaO-FeO四元体系煤灰结构及流动性关系的实验和理论研究

代鑫; 白进; 李东涛; 袁苹; 颜婷珪; 孔令学; 李文

Al₂O₃-SiO₂-CaO-FeO四元体系煤灰结构及流动性关系的实验和理论研究

代鑫^{1, 2},
白进^3, ,,
李东涛^{1, 2},
袁苹⁴,
颜婷珪⁵,
孔令学³,
李文³

1.
首钢技术研究院, 北京 100043
2.
绿色可循环钢铁流程北京市重点实验室, 北京 100043
3.
中国科学院山西煤炭化学研究所煤转化国家重点实验室, 山西太原 030001
4.
清华大学山西清洁能源研究院, 山西太原 030032
5.
贵州大学化学与化工学院, 贵州贵阳 550025

基金项目:

NSFC-新疆联合基金 U1703252

NSFC-山西省联合基金 U1510201

中德国际合作项目 21761132032

国家自然科学基金青年项目 21808045

国家重点研发计划专项 2017YFB0304300 & 2017YFB0304303

详细信息

中图分类号: TQ53
计量
- 文章访问数: 199
- HTML全文浏览量: 44
- PDF下载量: 21
- 被引次数: 0
出版历程
- 收稿日期: 2019-01-14
- 修回日期: 2019-03-25
- 网络出版日期: 2021-01-23
- 刊出日期: 2019-06-10

Experimental and theoretical investigation on relationship between structures of coal ash and its fusibility for Al₂O₃-SiO₂-CaO-FeO system

DAI Xin^{1, 2},
BAI Jin^{3
, ,},
LI Dong-tao^{1, 2},
YUAN Ping⁴,
YAN Ting-gui⁵,
KONG Ling-xue³,
LI Wen³

1.
Shougang Group Research Institute of Technology, Beijing 100043, China
2.
Beijing Key Laboratory of Green Recyclable Process for Iron & Steel Production Technology, Beijing 100043, China
3.
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
4.
Shanxi Research Institute for Clean Energy, Tsinghua University, Taiyuan 030032, China
5.
School of Chemistry and Chemical Engineering, Guizhou University, Guiyang 550025, China

Funds:

Joint Foundation of the Natural Science Foundation of China and Xinjiang Province U1703252

Joint Foundation of the Natural Science Foundation of China and Shanxi Province U1510201

NSFC-DFG 21761132032

National Natural Science Foundation of China 21808045

National Key R & D Program of China 2017YFB0304300 & 2017YFB0304303

More Information

Corresponding author: BAI Jin, Tel/Fax: 0351-4040289, E-mail: stone@sxicc.ac.cn

摘要

摘要: 将分子动力学、热力学计算与实验结合研究了Al₂O₃-SiO₂-CaO-FeO四元体系灰渣黏度变化机理。在Al₂O₃-SiO₂-CaO-FeO四元体系中，钙铁质量比（简称钙铁比，下同）增加，黏度下降，黏温曲线类型由结晶渣转变为玻璃渣，钙铁比为2时为黏温特性转变的拐点。钙铁比小于2时，体系中的矿物质主要是结晶矿物质，体系中降温过程中生成晶体矿物较多，当钙铁比大于2时，体系以无定形矿物质为主；从微观角度分析，钙铁比增加导致体系中Al由六配位（[AlO₆]^9-）转变为四配位（[AlO₄]^5-），钙铁两种原子对体系中六配位铝的影响存在竞争作用。体系中的桥氧含量降低，体系的聚合程度降低，稳定性降低。通过四元体系的氧键为桥梁，建立了碱性组分含量与黏度的函数关系。
- 分子动力学 /
- 热力学计算 /
- 煤灰结构 /
- 氧键类型 /
- 钙铁比
Abstract: The molecular dynamics simulation, thermal dynamic calculation and experimental investigation were combined to illustrate ash slag viscosity variation mechanism for Al₂O₃-SiO₂-CaO-FeO system. The viscosity declines and the viscosity curve is transformed from crystalline slag to glassy slag with increasing mass ratio (C/F) of calcium to ferrous oxide in Al₂O₃-SiO₂-CaO-FeO system. There is an inflexion point when the C/F is equal to 2. When the C/F is below 2, there are mainly crystalline minerals in the system. While the C/F is above 2, there are mainly amorphous minerals in the system. With the increase of C/F, six-coordinated Al ([AlO₆]^9-) is transformed to four coordinated Al([AlO₄]^5-) microscopically. Besides, the content of bridging oxygen decreases while that of non-bridging oxygen increases. Quantified function between base composition and viscosity are constructed based on the stability coefficients defined by oxygen bond species.
- molecular dynamics simulation /
- thermal dynamic calculation /
- coal ash structure /
- oxygen bond species /
- calcium and ferrous oxide ratio

HTML全文

下载: 全尺寸图片幻灯片

图 1 Al₂O₃-SiO₂-FeO-CaO四元体系中钙铁比对黏度的影响

Figure 1 Viscosity variation for Al₂O₃-SiO₂-FeO-CaO quaternary system as a function of calcium oxide and ferrous oxide ratio

下载: 全尺寸图片幻灯片

图 2 Al₂O₃-SiO₂-FeO-CaO四元体系不同钙铁比样品黏温曲线及不同温度下的固液相组成

Figure 2 Viscosity variation solid and liquid phase contents for various C/F Al₂O₃-SiO₂-FeO-CaO quaternary systems as a function of temperature

(a): C/F=0.66; (b): C/F=1.44; (c): C/F=2.00; (d): C/F=4.00; (e): C/F=14.00

下载: 全尺寸图片幻灯片

图 3 Al₂O₃-SiO₂-FeO-CaO四元体系中不同钙铁比样品黏度测试后灰渣的XRD谱图

Figure 3 XRD patterns for various C/F Al₂O₃-SiO₂-FeO-CaO quaternary systems after viscosity measurement

下载: 全尺寸图片幻灯片

图 4 Al₂O₃-SiO₂-FeO-CaO四元体系中不同钙铁比样品的XPS谱图

Figure 4 XPS analysis for various C/F Al₂O₃-SiO₂-FeO-CaO quaternary systems

: [AlO₄]^5-; : [AlO₆]^9-

下载: 全尺寸图片幻灯片

图 5 Al₂O₃-SiO₂-FeO-CaO四元体系中不同钙铁比样品的NMR谱图

Figure 5 NMR analysis for various C/F Al₂O₃-SiO₂-FeO-CaO quaternary systems

下载: 全尺寸图片幻灯片

图 6 Al₂O₃-SiO₂-FeO-CaO四元体系中不同钙铁比样品的氧键含量

Figure 6 Oxygen bond species for various C/F Al₂O₃-SiO₂-FeO-CaO quaternary systems

: bridging oxygen;
: nonbridging oxygen

下载: 全尺寸图片幻灯片

图 7 不同钙铁比的Al₂O₃-SiO₂-FeO-CaO四元体系桥氧和非桥氧组成

Figure 7 Composition of bridging and nonbridging oxygen for various C/F Al₂O₃-SiO₂-FeO-CaO quaternary systems

: Al-O-Si; : Al-O-Al; : Si-O-Si

下载: 全尺寸图片幻灯片

图 8 Al₂O₃-SiO₂-CaO-FeO四元体系的黏度与稳定性系数的关系

Figure 8 Relationship between viscosity and stability coefficient for Al₂O₃-SiO₂-CaO-FeO quaternary systems

下载: 全尺寸图片幻灯片

图 9 Al₂O₃-SiO₂-CaO-FeO四元体系的稳定性系数与钙铁比的关系

Figure 9 Relationship between stability coefficient and C/F for Al₂O₃-SiO₂-CaO-FeO quaternary systems

下载: 全尺寸图片幻灯片

表 1 煤灰样品的组成

Table 1 Composition of coal ash samples

C/F	Composition (percent in weight) w/%
C/F	SiO₂	Al₂O₃	CaO	Fe₂O₃
0.66(R4)	56.67	28.33	6.00	9.00
1.14(R5)	56.67	28.33	8.00	7.00
2.00(R6)	56.67	28.33	10.00	5.00
4.00(R7)	56.67	28.33	12.00	3.00
14.00(R8)	56.67	28.33	14.00	1.00

下载: 导出CSV

表 2 Bertrand等拟合的适合不同四元体系势函数参数^{[16, 17]}

Table 2 Potential function coefficients fitted by Bertrand et al for various quaternary systems^{[16, 17]}

Atom type	Q/e	A/(kJ·mol^-1)	ρ/nm	C/(10^-6·nm⁶·kJ·mol^-1)
Al	1.4175	2753544	0.0172	3336.26
Ca	0.945	15019679	0.0178	4077.45
O	-0.945	870570	0.0265	8210.17
Si	1.890	4853816	0.0161	4467.07
Fe²⁺	0.945	1257488	0.0190	0

下载: 导出CSV

参考文献(21)

[1]	BP Statistical Review of World Energy 2017[R]. BP Public limited company, London, 2017.
[2]	王辅臣.大规模高效气流床煤气化技术基础研究进展[J].中国基础科学, 2008, 10(3):4-13. doi: 10.3969/j.issn.1009-2412.2008.03.002 WANG Fu-chen. Progress on the large-scale and high-efficiency energy entrained flow coal gasification technology[J]. China Basic Sci, 2008, 10(3):4-13. doi: 10.3969/j.issn.1009-2412.2008.03.002
[3]	王辅臣, 于广锁, 龚欣, 刘海峰, 王亦飞, 梁钦峰, 大型煤气化技术的研究与发展[J].化工进展, 2009, 28(2):173-180. doi: 10.3321/j.issn:1000-6613.2009.02.001 WANG Fu-chen, YU Guang-suo, GONG Xin, LIU Hai-feng, WANG Yi-fei, LIANG Qin-feng. Research and development of large-scale coal gasification technology[J]. Chem Ind Eng Prog, 2009, 28(2):173-180. doi: 10.3321/j.issn:1000-6613.2009.02.001
[4]	宫经德, 壳牌煤气化技术及其工程应用[J].化肥设计, 2007, 6:8-12+18. http://d.old.wanfangdata.com.cn/Periodical/hfsj200706002 GONG Jing-de. Shell coal gasification technology and its engineering application[J]. Chem Fert Des, 2007, 6:8-12+18. http://d.old.wanfangdata.com.cn/Periodical/hfsj200706002
[5]	白进, 李文, 李保庆, 高温弱还原气氛下煤中矿物质变化的研究[J].燃料化学学报, 2006, 34(3):292-297. doi: 10.3969/j.issn.0253-2409.2006.03.007 BAI Jin, LI Wen, LI Bao-qing. Mineral behavior in coal under reducing atmosphere at high temperature[J]. J Fuel Chem Technol, 2006, 34(3):292-297. doi: 10.3969/j.issn.0253-2409.2006.03.007
[6]	廖敏, 郭庆华, 梁钦锋, 袁海平, 倪建军, 于广锁, 气化条件下煤灰高温物相变化及其对黏度的影响[J].中国电机工程学报, 2010, 30(17):45-50. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=zgdjgcxb201017009 LIAO Min, GUO Qing-hua, LIANG QIN-feng, YUAN Hai-ping, NI Jian-jun, YU Guang-suo. Phase transformation of coal ash at high temperature under gasification conditions and its influence on viscosity[J]. Proc CSEE, 2010, 30(17):45-50. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=zgdjgcxb201017009
[7]	陈晓东, 孔令学, 白进, 白宗庆, 李文.高温气化条件下Na₂O对煤灰中矿物质演化行为的影响[J].燃料化学学报, 2016, 44(3):263-272. http://manu60.magtech.com.cn/rlhxxb/CN/abstract/abstract18789.shtml CHEN Xiao-dong, KONG Ling-xue, BAI Jin, BAI Zong-qing, LI Wen. Effect of Na₂O on mineral transformation of coal ash under high temperature gasificaiton condition[J]. J Fuel Chem Technol, 2006, 44(3):263-272. http://manu60.magtech.com.cn/rlhxxb/CN/abstract/abstract18789.shtml
[8]	KONG L X, BAI J, LI W, WEN X D, LI X, BAI Z Q, GUO Z X, LI H Z. The internal and external factor on coal ash slag viscosity at high temperatures, Part 3:Effect of CaO on the pattern of viscosity-temperature curves of slag[J]. Fuel, 2016, 179:10-16. doi: 10.1016/j.fuel.2016.03.063
[9]	KONG L X, BAI J, LI W, WEN X D, LI X, BAI Z Q, GUO Z X, LI H Z. The internal and external factor on coal ash slag viscosity at high temperatures, Part 1:Effect of cooling rate on slag viscosity, measured continuously[J]. Fuel, 2015, 158:968-975. doi: 10.1016/j.fuel.2015.02.055
[10]	KONG L X, BAI J, LI W, WEN X D, LI X, BAI Z Q, GUO Z X, LI H Z. The internal and external factor on coal ash slag viscosity at high temperatures, Part 2:Effect of residual carbon on slag viscosity[J]. Fuel, 2015, 158:976-982. doi: 10.1016/j.fuel.2015.06.055
[11]	XUAN W W, WHITTY K J, GUAN Q L, BI D P, ZHAN Z, ZHANG J S. Influence of CaO on crystallization characteristics of synthetic coal slags[J]. Energy Fuels, 2014, 28(10):6627-6634. doi: 10.1021/ef501215u
[12]	DAI X, BAI J, HUANG Q, LIU Z, BAI X J, CAO R G, WEN X D, LI W, DU S Y. Viscosity temperature properties from molecular dynamics simulation:The role of calcium oxide, sodium oxide and ferrous oxide[J]. Fuel, 2019, 237:163-169. doi: 10.1016/j.fuel.2018.09.127
[13]	WU T, WANG Q, YU C F, HE S P. Structural and viscosity properties of CaO-SiO₂-Al₂O₃-FeO slags based on molecular dynamic simulation[J]. J Non-Cryst Solids, 2016, 450:23-31. doi: 10.1016/j.jnoncrysol.2016.07.024
[14]	李洁, 杜梅芳, 闫博, 张忠孝.添加硼砂助熔剂煤灰熔融性的量子化学与实验研究[J].燃料化学学报, 2008, 36(5):519-523. doi: 10.3969/j.issn.0253-2409.2008.05.002 LI Jie, DU Mei-fang, YAN Bo, ZHANG Zhong-xiao. Quantum and experimental study on coal ash fusion with borax fluxing agent[J]. J Fuel Chem Technol, 2008, 36(5):519-523. doi: 10.3969/j.issn.0253-2409.2008.05.002
[15]	陈玉爽, 张忠孝, 乌晓江, 李洁, 管嵘清, 闫博.配煤对煤灰熔融特性影响的实验与量化研究[J].燃料化学学报, 2009, 37(5):521-526. doi: 10.3969/j.issn.0253-2409.2009.05.002 CHEN Yu-shuang, ZHANG Zhong-xiao, WU Xiao-jiang, LI Jie, GUAN Rong-qing, YAN Bo. Quantum chemistry calculation and experimental study on coal ash fusion characeristics of blend coal[J]. J Fuel Chem Technol, 2009, 37(5):521-526. doi: 10.3969/j.issn.0253-2409.2009.05.002
[16]	GUILLOT B, SATOR N. A computer simulation study of natural silicate melts. Part Ⅱ:High pressure properties[J]. Geochim Cosmochim Acta, 2007, 71(5):4538-4556. http://www.sciencedirect.com/science/article/pii/S0016703707003936
[17]	GUILLOT B, SATOR N. A computer simulation study of natural silicate melts. Part Ⅰ:Low pressure properties[J]. Geochim Cosmochim Acta, 2007, 71(5):1249-1265. doi: 10.1016/j.gca.2006.11.015
[18]	BALE C W, BELISLE E, CHARTRAND P, DE CTEROV S A, ERIKSSON G, GHERIBI A E, HACK K, JUNG I H, KANG Y B, MELANCON J, PELTON A D, PETERSEN S, ROBELIN C, SANGSTER J, SPENCER P, VAN ENDE M A. FactSage thermochemical software and databases, 2010-2016, CALPHAD[J]. 2016, 54: 35-53.
[19]	BALE C W, BELISLE E, CHARTRAND P, DECTEROV S A, ERIKSSON G, HACK K, JUNG I H, KANG Y B, MELANCON J, PELTON A D, ROBELIN C, PETERSEN S. FactSage thermochemical software and databases-recent developments[J]. Calphad, 2009, 33:295-311. doi: 10.1016/j.calphad.2008.09.009
[20]	BALE C W, CHARTRAND P, BELISLE E, DECTEROV S A, ERIKSSON G, HACK K, MAHFOUD R J, PELTON A D, PETERSEN S. Factsage thermochemical software and databases[J]. Calphad, 2002, 26:189-228. doi: 10.1016/S0364-5916(02)00035-4
[21]	SONG W J, TANG L H, ZHU X D, WU Y Q, ZHU Z B, KOYAMA S. Effect of coal ash composition on ash fusion temperatures[J]. Energy Fuels, 2010, 24(1):182-189. doi: 10.1021/ef900537m