Cu-橄榄石载氧体煤焦化学链气化实验研究

宋洋博; 徐绍平; 李伶俐; 肖亚辉

Cu-橄榄石载氧体煤焦化学链气化实验研究

大连理工大学化工学院精细化工国家重点实验室, 辽宁大连 116024

详细信息

通讯作者:
徐绍平, E-mail: spxu@dlut.edu.cn

中图分类号: TQ546
计量
- 文章访问数: 92
- HTML全文浏览量: 36
- PDF下载量: 11
- 被引次数: 0
出版历程
- 收稿日期: 2017-03-29
- 修回日期: 2017-05-26
- 网络出版日期: 2021-01-23
- 刊出日期: 2017-08-10

Chemical looping gasification of coal char with Cu-olivine oxygen carriers

State Key Laboratory of Fine Chemicals, Chemical Engineering Institute, Dalian University of Technology, Dalian 116024, China

摘要

摘要: 用浸渍法以橄榄石为载体负载CuO制备了Cu-橄榄石载氧体，并在固定床上开展了载氧体存在下煤焦的水蒸气气化实验。结果表明，提高气化温度和水碳物质的量比可以提高煤焦气化的碳转化率和合成气产率；增加载氧体CuO负载量和载氧体/煤焦质量比能提高碳转化率和水转化率，但会消耗产气中的合成气，导致合成气产率降低。高温再生后载氧体依然能保持活性，表明橄榄石载体抑制了Cu/CuO的烧结。载氧体经950 ℃再生八次后用于煤焦气化，实现碳转化率42.3%，水转化率57.3%，合成气产率2.12 L/（g·h）。
- 化学链气化 /
- 煤焦 /
- Cu-橄榄石载氧体 /
- 固定床反应器
Abstract: A Cu-olivine oxygen carrier was prepared using impregnation method and used for steam gasification of coal char in a fixed bed reactor. It is shown that higher gasification temperature and steam/C molar ratio conduce to an increase in carbon conversion and syngas yield. The increase of CuO loading on the oxygen carrier and the oxygen carrier/char weight ratio leads to a higher carbon conversion but a lower syngas yield. The reaction activity of oxygen carrier has not been reduced after multiple regenerations at 950 ℃, which indicates that the olivine could inhibit the sintering of the supported Cu/CuO. The gasification at 800 ℃ in the presence of the oxygen carrier after 8th regeneration has a carbon conversion of 42.3%, a water conversion of 57.3% and a syngas yield of 2.12 L/(g·h).
- chemical looping gasification /
- coal char /
- Cu-olivine oxygen carrier /
- fixed bed reactor

HTML全文

图 1 固定床实验装置示意图

Figure 1 Schematic diagram of the fixed bed reactor

下载: 全尺寸图片幻灯片

图 2 不通水时碳转化率及产气组成

Figure 2 Carbon conversion and dry gas composition for the reaction without steam

下载: 全尺寸图片幻灯片

图 3 通入水蒸气时的碳转化率、水转化率及产气组成

Figure 3 Carbon conversion, water conversion and dry gas composition for the reaction with steam

下载: 全尺寸图片幻灯片

图 4 反应前、反应后和十次循环反应后载氧体CuO/olivine的XRD谱图

a: before reaction; b: after reaction; c: after ten regeneration cycles reaction

Figure 4 X-ray diffraction of CuO/olivine

下载: 全尺寸图片幻灯片

图 5 CuO负载量对煤焦化学链气化的影响

Figure 5 Influence of CuO loading on char chemical looping gasification

下载: 全尺寸图片幻灯片

图 6 温度对煤焦化学链气化的影响

Figure 6 Influence of temperature on char chemical looping gasification

下载: 全尺寸图片幻灯片

图 7 水碳物质的量比对煤焦化学链气化的影响

Figure 7 Influence of S/C molar ratio on char chemical looping gasification

下载: 全尺寸图片幻灯片

图 8 载氧体/煤焦质量比对煤焦化学链气化的影响

Figure 8 Influence of oxygen carrier/char weight ratio on char chemical looping gasification

下载: 全尺寸图片幻灯片

图 9 载氧体再生温度对煤焦化学链气化的影响

Figure 9 Influence of oxygen carrier regeneration temperature on char chemical looping gasification

下载: 全尺寸图片幻灯片

图 10 载氧体再生次数对煤焦化学链气化的影响

Figure 10 Influence of cycle number on char chemical looping gasification

下载: 全尺寸图片幻灯片

表 1 橄榄石的XRF组成

Table 1 Composition of olivine by XRF analysis

表 2 褐煤及煤焦的工业分析和元素分析

Table 2 Proximate and ultimate analyses of lignite and coal char

参考文献(23)

[1]	FAN L S. Chemical Looping Systems for Fossil Energy Conversions[M]. John Wiley & Sons, 2011.
[2]	LYNGFELT A, LECKNER B, MATTISSON T. A fluidized-bed combustion process with inherent CO₂ separation; Application of chemical-looping combustion[J]. Chem Eng Sci, 2001, 56(10): 3101-3113. doi: 10.1016/S0009-2509(01)00007-0
[3]	MATTISSON T, LYNGFELT A, LEION H. Chemical-looping with oxygen uncoupling for combustion of solid fuels[J]. Int J Green Gas Con, 2009, 3(1): 11-19. doi: 10.1016/j.ijggc.2008.06.002
[4]	ADANEZ J, ABAD A, GARCIA-LABIANO F, GAYAN P, LUIS F. Progress in chemical-looping combustion and reforming technologies[J]. Prog Energy Combust Sci, 2012, 38(2): 215-282. doi: 10.1016/j.pecs.2011.09.001
[5]	SIRIWARDANE R, RILEY J, TIAN H, RICHARDS G. Chemical looping coal gasification with calcium ferrite and barium ferrite via solid-solid reactions[J]. Appl Energ, 2016, 165: 952-966. doi: 10.1016/j.apenergy.2015.12.085
[6]	YONGZHUO L I U, QINGJIE G U O. Investigation into syngas generation from solid fuel using CaSO₄-based chemical looping gasification process[J]. Chin J Chem Eng, 2013, 21(2): 127-134. doi: 10.1016/S1004-9541(13)60450-4
[7]	黄摇振, 何摇方, 李海滨, 赵增立.天然铁矿石为氧载体的生物质化学链气化制合成气实验研究[J].燃料化学学报, 2012, 40(3), 300-308. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract17900.shtml HUANG Zhen-yao, HE Yao-fang, LI Hai-bin, ZHAO Zeng-li. Synthesis gas generation by chemical-looping gasification of biomass using natural hematite as oxygen carrier[J]. J Fuel Chem Technol, 2012, 40(3), 300-308. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract17900.shtml
[8]	冉景煜, 张松, 秦昌雷, 禹建功, 付范萱, 杨琳.生物质半焦/铜基载氧体气化反应特性研究[J].燃料化学学报, 2014, 42(11), 1316-1323. doi: 10.3969/j.issn.0253-2409.2014.11.007 RAN Jing-yu, ZHANG Song, QIN Chang-lei, YU Jian-gong, FU Fan-xuan, YANG Lin. Gasification reactivity of biomass char with oxygen carrier CuO[J]. J Fuel Chem Technol, 2014, 42(11), 1316-1323. doi: 10.3969/j.issn.0253-2409.2014.11.007
[9]	CORBELLA B, PALACIOS J M. Titania-supported iron oxide as oxygen carrier for chemical-looping combustion of methane[J]. Fuel, 2007, 86(2): 113-122. http://www.sciencedirect.com/science/article/pii/S0016236101000515
[10]	GAYÁN P, FORERO C R, ABAD A, DIEGO L F, GARCIA-LABIANO F, ADANEZ J. Effect of support on the behavior of Cu-based oxygen carriers during long-term CLC operation at temperatures above 1073 K[J]. Energy Fuels, 2011, 25(3): 1316-1326. doi: 10.1021/ef101583w
[11]	ISHIDA M, JIN H. A novel combustor based on chemical-looping reactions and its reaction kinetics[J], J Chem Eng Jpn, 1994, 27(3): 296-301. doi: 10.1252/jcej.27.296
[12]	ADDNEZ J, DE DIEGO L F, GARCIA-LABIANO F, GAYAN P, ABAD A. Selection of oxygen carriers for chemical-looping combustion[J]. Energy Fuels, 2004, 18(2): 371-377. doi: 10.1021/ef0301452
[13]	RYU H J, SEO Y, JIN G T. Development of chemical-looping combustion technology: long-term operation of a 50 kW/h chemical-looping combustor with Ni-and CO-based oxygen carrier particles[C]. In: Proc of the Regional Symp on Chem Eng Hanoi, Vietnam, 2005.
[14]	SONG Q, XIAO R, DENG Z, SHEN L, XIAO J, ZHANG M. Effect of temperature on reduction of CaSO₄ oxygen carrier in chemical-looping combustion of simulated coal gas in a fluidized bed reactor[J]. Ind Eng Chem Res, 2008, 47(21): 8148-8159. doi: 10.1021/ie8007264
[15]	RYDÉN M, LYNGFELT A, MATTISSON T, CHEN D, HOLMEN A, BJØRGUM E. Novel oxygen-carrier materials for chemical-looping combustion and chemical-looping reforming; La_xSr_1xFeyCo_1-yO_3-δ perovskites and mixed-metal oxides of NiO, Fe₂O₃ and Mn₃O₄[J]. Int J Green Gas Con, 2008, 2(1): 21-36. doi: 10.1016/S1750-5836(07)00107-7
[16]	GUO Q, CHENG Y, LIU Y, JIA W, RYU H J. Coal chemical looping gasification for syngas generation using an iron-based oxygen carrier[J]. Ind Eng Chem Res, 2013, 53(1): 78-86. doi: 10.1021/ie401568x
[17]	葛晖骏, 郭万军, 沈来宏, 宋涛, 顾海明, 蒋守席.铁矿石载氧体生物质化学链气化实验研究[J].工程热物理学报, 2015, 36(6): 1371-1375. http://www.cnki.com.cn/Article/CJFDTOTAL-RKXS201701013.htm GE Hui-jun, GUO Wan-jun, SHEN Lai-hong, SONG Tao, Gu Hai-ming, JIANG Shou-xi. Experiments on chemical looping gasification of biomass with natural hematite as oxygen carrier[J]. J Eng Thermophys, 2015, 36(6): 1371-1375. http://www.cnki.com.cn/Article/CJFDTOTAL-RKXS201701013.htm
[18]	刘永强, 王志奇, 吴晋沪, 武景丽, 徐梅.铜基载氧体与可燃固体废弃物化学链燃烧特性研究[J].燃料化学学报, 2013, 41(9): 1056-1063. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18251.shtml LIU Yong-qiang, WANG Zhi-qi, WU Jin-hu, WU Jing-li, XU Mei. Investigation on Cu-based oxygen carrier for chemical looping combustion of combustible solid waste[J]. J Fuel Chem Technol, 2013, 41(9): 1056-1063. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18251.shtml
[19]	YANG W, ZHAO H, MA J, MEI D, ZHENG C. Copper-decorated hematite as an oxygen carrier for in situ gasification chemical looping combustion of coal[J]. Energy Fuels, 2014, 28(6): 3970-3981. doi: 10.1021/ef5001584
[20]	NIU X, SHEN L, JIANG S, GU H, XIAO J. Combustion performance of sewage sludge in chemical looping combustion with bimetallic Cu-Fe oxygen carrier[J]. Chem Eng J, 2016, 294: 185-192. doi: 10.1016/j.cej.2016.02.115
[21]	LI F, LUO S, SUN Z, BAO X, FAN L S. Role of metal oxide support in redox reactions of iron oxide for chemical looping applications: experiments and density functional theory calculations[J]. Energ Environ Sci, 2011, 4(9): 3661-3667. doi: 10.1039/c1ee01325d
[22]	魏立纲, 徐绍平, 刘长厚, 刘淑芹.预煅烧对橄榄石生物质气化催化性能的影响[J].燃料化学学报, 2008, 36(4): 426-430. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract17325.shtml WEI Li-gang, XU Shao-ping, LIU Chang-hou, LIU Shu-qin. Effects of pre-calcination on catalytic activity of olivine in biomass gasification[J]. J Fuel Chem Technol, 2008, 36(4): 426-430. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract17325.shtml
[23]	ŚWIERCZYŃSKI D, COURSON C, BEDEL L, KIENNEMANN A, VILMINOT S. Oxidation reduction behavior of iron-bearing olivines (Fe_xMg_1-x)₂SiO₄ used as catalysts for biomass gasification[J]. Chem Mater, 2006, 18(4): 897-905. doi: 10.1021/cm051433+