基于铁基载氧体的无烟煤化学链燃烧过程中硫分布特性

doi:10.11949/j.issn.0438-1157.20170838

摘要/Abstract

摘要：

在间歇式固定床反应器上，基于Fe₂O₃/Al₂O₃载氧体，研究了还原阶段反应温度和Fe₂O₃负载量对无烟煤化学链燃烧产物及S元素分布的影响。研究结果表明，含碳气体释放量随反应温度升高而增加，随Fe₂O₃负载量先增加后减少。产物中CO₂比例随反应温度升高先增加后减少，在850℃时达到最高（37.6%）。在实验条件下，未检测到SO₂生成。反应2 h时，载氧体中S元素的富集程度随温度和Fe₂O₃负载量升高而增加；5.5 h时，载氧体中S元素分布比例随温度升高而显著降低。利用SEM分析了载氧体表面微观形态结构。分析表明，Fe₂O₃负载量大于40%会导致载氧体轻微烧结。

关键词: 化学链燃烧, 无烟煤, 铁基载氧体, 硫

Abstract:

In a batch fixed bed reactor, distribution of sulfur was studied during chemical looping combustion of anthracite based Fe₂O₃/Al₂O₃ oxygen carrier(OC). Reduction temperature and content of Fe₂O₃ were tested as variables. The work showed that the carbonaceous gas quantity increased with increasing temperature, while it increased first and then decreased with content of Fe₂O₃ improved. The proportion of CO₂ reached the highest value 37.6% at 850℃ and there were no SO₂ detected at experiments. At 2 h, the occupation of sulfur in OC increased with improvement of both temperature and the content of Fe₂O₃. At 5.5 h, the occupation of sulfur in OC decreased obviously with improvement of temperature. Surface microstructure of reacted OC was also evaluated using a scanning electron microscope. The results showed that OC sintered gradually with increase of content of Fe₂O₃.

Key words: chemical looping combustion, anthracite, Fe-based oxygen carrier, sulfur

中图分类号:

TK16

张志丰, 王亦飞, 朱龙雏, 李季林, 王辅臣, 于广锁. 基于铁基载氧体的无烟煤化学链燃烧过程中硫分布特性[J]. 化工学报, 2018, 69(4): 1578-1585.

ZHANG Zhifeng, WANG Yifei, ZHU Longchu, LI Jilin, WANG Fuchen, YU Guangsuo. Distribution of sulfur in chemical looping combustion of anthracite based on Fe-based oxygen carrier[J]. CIESC Journal, 2018, 69(4): 1578-1585.

参考文献 30

[1]	张帅, 肖睿, 李延兵, 等. 燃煤化学链燃烧技术的研究进展[J]. 热能动力工程, 2017, 32(4):1-12. ZHANG S, XIAO R, LI Y B, et al. Research development on coal-based chemical looping combustion[J]. Journal of Engineering for Thermal Energy and Power, 2017, 32(4):1-12.
[2]	何映龙, 于敦喜, 雷体蔓, 等. 铁基氧载体化学链CO2重整CH4方法制备合成气[J]. 化工学报, 2016, 67(12):5222-5228. HE Y L,YU D X,LEI T M, et al. Chemical looping CO2/CH4 reforming using Fe-based oxygen carrier for syngas production[J]. CIESC Journal, 2016, 67(12):5222-5228.
[3]	OLAJIRE A A. CO2 capture and separation technologies for end-of-pipe applications-a review[J]. Energy, 2010, 35(6):2610-2628.
[4]	DAVID J, HERZOG H. The cost of carbon capture[EB/OL]. http://sequestration.mit.edu/pdf/David_and_Herzog.pdf.
[5]	DAVISON J. Performance and costs of power plants with capture and storage of CO2[J]. Energy, 2007, 32(7):1163-1176.
[6]	许迪恺, TONG Andrew, 曾亮, 等. 铁基移动床化学链技术进展[J]. 化工学报, 2014, 65(7):2410-2416. XU D K, TONG A, ZENG L, et al. Development on iron-based moving bed chemical looping process[J]. CIESC Journal, 2014, 65(7):2410-2416.
[7]	NOORMAN S, ANNALAND M V, KUIPERS H. Packed bed reactor technology for chemical-looping combustion[J]. Industrial & Engineering Chemistry Research, 2007, 46(12):4212-4220.
[8]	NANDY A, LOHA C, GU S, et al. Present status and overview of chemical looping combustion technology[J]. Renewable and Sustainable Energy Reviews, 2016, 59:597-619.
[9]	ADANEZ J, ABAD A, GARCIA-LABIANO F. Progress in chemical-looping combustion and reforming technologies[J]. Progress in Energy and Combustion Science, 2012, 38(2):215-268.
[10]	BRYANT S, LAKE L W. Effect of impurities on subsurface CO2 storage processes[M]//THOMAS D C, BENSON S M. Carbon Dioxide Capture for Storage in Deep Geologic Formations:Results from the CO2 Capture Project:vol. 2. Oxford, UK:Elsevier, 2005.
[11]	TIAN X, WANG K, ZHAO H B, et al. Chemical looping with oxygen uncoupling of high-sulfur coal using copper ore as oxygen carrier[J]. Proceedings of the Combustion Institute, 2017, 36:3381-3388.
[12]	GARCÍA-LABIANO F, DE DIEGO L F, GAYÁN P, et al. Effect of fuel gas composition in chemical-looping combustion with Ni-based oxygen carriers(Ⅰ):Fate of sulphur[J]. Industrial & Engineering Chemistry Research, 2009, 48(5):2499-2508.
[13]	JERNDAL E, MATTISSON T, LYNGFELT A. Thermal analysis of chemical-looping combustion[J]. Chemical Engineering Research and Design, 2006, 84(9):795-806.
[14]	李乾军, 章名耀, 施爱阳, 等. 钙基脱硫剂增压喷动流化床煤气化炉的炉内脱硫[J]. 化工学报, 2008, 59(1):189-194. LI Q J, ZHANG M Y, SHI A Y, et al. Removal of hydrogen sulfide in pressurized spout-fluid bed coal gasifier with calcium-based sorbents[J]. Journal of Chemical Industry and Engineering(China), 2008, 59(1):189-194.
[15]	MATTISSON T, JÄRDNÄS A, LYNGFELT A. Reactivity of some metal oxides supported on alumina with alternating methane and oxygen-application for chemical-looping combustion[J]. Energy & Fuels, 2003, 17(3):643-651.
[16]	MATTISSON T, JOHANSSON M, LYNGFELT A. Multicycle reduction and oxidation of different types of iron oxide particles-application to chemical-looping combustion[J]. Energy & Fuels, 2004, 18(3):628-637.
[17]	VITTORIN T, JULES H. Quantitative thin-layer chromatography of triazophos[J]. Steel Research International, 1989, 60(6):241-245.
[18]	胡净宇, 邵光玓, 胡晓燕, 等. 氧化铝柱与分离-离子色谱法测定钢铁中痕量硫[J]. 分析化学, 1997, 27(11):1313-1316. HU J Y, SHAO G D, HU X Y, et al. Method for determination of trace sulfur in iron and steel by ion chromatography with alumina column preseparation[J]. Chinese Journal of Analytical Chemistry, 1997, 27(11):1313-1316.
[19]	兰宇卫, 陆建平, 章张法, 等. 微波消解-吸附柱分离-离子色谱法测定钢样中微量硫[J]. 冶金分析, 2008, 28(1):24-26. LAN Y W, LU J P, ZHANG Z F, et al. Ion chromatographic determination of trace sulfur in steel with microwave digestion and adsorption column separation[J]. Metallurgical Analysis, 2008, 28(1):24-26.
[20]	郝建刚, 吴家桦, 王雷, 等. 基于Fe基载氧体的生物质化学链燃烧试验研究[J]. 锅炉技术, 2010, 41(2):65-70. HAO J G, WU J H, WANG L, et al. Experiments on chemical looping combust ion of biomass with a Fe2O3 based oxygen carrier[J]. Boiler Technology, 2010, 41(2):65-70.
[21]	高正平, 沈来宏, 肖军, 等. 煤化学链燃烧Fe2O3载氧体的反应性研究[J]. 燃料化学学报, 2009, 37(5):513-520. GAO Z P, SHEN L H, XIAO J, et al. Analysis of reactivity of Fe-based oxygen carrier with coal during chemical-looping combustion[J]. Journal of Fuel Chemistry and Technology, 2009, 37(5):513-520.
[22]	张思文, 沈来宏, 顾海明, 等. 钠修饰铁矿石的串行流化床煤化学链燃烧实验[J]. 化工学报, 2013, 64(11):4187-4195. ZHANG S W, SHEN L H, GU H M, et al. Chemical-looping combustion of coal in interconnected fluidized bed using Na-loaded iron ore as oxygen carrier[J]. CIESC Journal, 2013, 64(11):4187-4195.
[23]	BOLT P H, HABRAKEN F H P M, GEUS J W. Formation of nickel, cobalt, copper, and iron aluminates form α-and γ-alumina-supported oxides:a comparative study[J]. Journal of Solid State Chemistry, 1998, 135(135):59-69.
[24]	ABAD A, MATTISSON T, LYNGFELT A. The use of iron oxide as oxygen carrier in a chemical-looping reactor[J]. Fuel, 2007, 86(7/8):1021-1035.
[25]	BAO J, LIU W, CLEETON J P E. Interaction between Fe-based oxygen carriers and n-heptane during chemical looping combustion[J]. Proceedings of the Combustion Institute, 2013, 34(2):2839-2846.
[26]	樊惠玲. 氧化铁高温煤气脱硫行为及助剂影响规律的研究[D]. 太原:太原理工大学, 2004. FAN H L. Hot gas desulfurization by iron oxide sorbent and effects of additives on the performances of desulfurizer[D]. Taiyuan:Taiyuan University of Technology, 2004.
[27]	关怀. 氧化铁高温煤气脱硫剂再生动力学研究[D]. 太原:太原理工大学, 2015. GUAN H. Regeneration kinetics of iron oxide high temperature coal gas desulfurization sorbent[D]. Taiyuan:Taiyuan University of Technology, 2015.
[28]	肖申, 沈来宏, 肖军, 等. 基于赤铁矿的生物质化学链燃烧过程中氮氧化物的释放特性[J]. 燃料化学学报, 2015, 43(4):490-498. XIAO S, SHEN L H, XIAO J, et al. NOx release in chemical looping combustion of biomass based on hematite[J]. Journal of Fuel Chemistry and Technology, 2015, 43(4):490-498.
[29]	WHITE J D, GROVES E R, HARRISON D. Element sulfur production during the regeneration of iron oxide high-temperature desulfurization sorbent[J]. Catalysis Today, 1998, 40(1):47-57.
[30]	吴宗泽, 米杰, 武蒙蒙, 等. H2O/O2气氛下半焦负载氧化铁高温煤气脱硫剂再生行为研究[J]. 太原理工大学学报, 2015, 46(1):22-28. WU Z Z, MI J, WU M M, et al. Regeneration characteristics of modified semi-coke supported (Fe2O3) desulfurization sorbents in H2O/O2[J]. Journal of Taiyuan University of Technology, 2015, 46(1):22-28.