MnFeO3和MnFe2O4氧载体在稻草化学链气化中的应用

陈智豪; 廖艳芬; 莫菲; 刘桂才; 余昭胜; 马晓茜

doi:10.11949/0438-1157.20190798

您当前的位置：

首页 >

文章列表页 >

MnFeO₃和MnFe₂O₄氧载体在稻草化学链气化中的应用

能源和环境工程 | 更新时间：2026-07-24

- MnFeO₃和MnFe₂O₄氧载体在稻草化学链气化中的应用
- Application of MnFeO₃ and MnFe₂O₄ as oxygen carriers for straw chemical looping gasification
- 化工学报 2019年70卷第12期页码：4835-4846
- 作者机构：
  
  华南理工大学电力学院，广东广州 510640
- 作者简介：
  
  陈智豪（1994—），男，硕士研究生，124164138@qq.com
  廖艳芬（1976—），女，博士，教授，yfliao@scut.edu.cn
- 基金信息：
  
  国家自然科学基金项目(51676074);广东省能源高效清洁利用重点实验室项目(2013A061401005)
- DOI：10.11949/0438-1157.20190798
  中图分类号： TK 6
- 收稿：2019-07-11，
  
  修回：2019-08-15，
  
  网络首发：2020-06-09，
  
  纸质出版：2019-12-05
- 稿件说明：
移动端阅览
陈智豪, 廖艳芬, 莫菲, 刘桂才, 余昭胜, 马晓茜. MnFeO₃和MnFe₂O₄氧载体在稻草化学链气化中的应用[J]. 化工学报, 2019, 70(12): 4835-4846 DOI: 10.11949/0438-1157.20190798.

CHEN Zhihao, LIAO Yanfen, MO Fei, LIU Guicai, YU Zhaosheng, MA Xiaoqian. Application of MnFeO₃ and MnFe₂O₄ as oxygen carriers for straw chemical looping gasification[J]. CIESC Journal, 2019, 70(12): 4835-4846 DOI: 10.11949/0438-1157.20190798.
陈智豪, 廖艳芬, 莫菲, 刘桂才, 余昭胜, 马晓茜. MnFeO₃和MnFe₂O₄氧载体在稻草化学链气化中的应用[J]. 化工学报, 2019, 70(12): 4835-4846 DOI: 10.11949/0438-1157.20190798. DOI：

CHEN Zhihao, LIAO Yanfen, MO Fei, LIU Guicai, YU Zhaosheng, MA Xiaoqian. Application of MnFeO₃ and MnFe₂O₄ as oxygen carriers for straw chemical looping gasification[J]. CIESC Journal, 2019, 70(12): 4835-4846 DOI: 10.11949/0438-1157.20190798. DOI：

摘要

通过溶胶凝胶燃烧法合成了MnFeO

和MnFe

两种锰铁复合氧载体。通过原位红外实验探究其与稻草的化学链气化过程，发现其加速了稻草热解产物的析出，并通过气化反应促进CO和CO

的产生，提高了碳转化率。固定床实验结果表明MnFeO

和MnFe

在与水蒸气耦合气化的条件下大幅提高了合成气中H

和CO的产率，气化效率分别达到94.49%和92.76%。并通过XRD分析，发现MnFeO

和MnFe

在气化过程主要还原为(Fe

Mn)O，且在氧化反应后能回到初始晶相。在固定床的10次循环实验以及SEM的结果表明，MnFeO

在循环反应中逐渐形成的颗粒状多孔结构有利于维持稳定的气化效率，而MnFe

由于团聚和烧结作用形成了块状结构，气化效率呈缓慢下降趋势。因此，认为MnFeO

在生物质化学链气化中具有更好的适用性。

Abstract

The reactivity of oxygen carriers is curial for biomass chemical looping gasification (CLG) process. Two kinds of manganese-iron composite oxygen carriers of MnFeO

and MnFe

were synthesized by sol-gel combustion method. Though the

in situ

infrared

CLG experiments with straw were carried out. It indicated that the ferromanganese composite oxides accelerated the release rate of pyrolysis products and enhanced the yield of CO and CO

which promoted the carbon conversion efficiency. Further tests in fix-bed were to prove the feasibility of MnFeO

and MnFe

and the influence by coupling with steam. It showed that components of H

and CO in syngas could be improved significantly by introducing steam and the gasification efficiency for MnFeO

and MnFe

was 94.49% and 92.76% individually. The XRD analysis demonstrated that MnFeO

and MnFe

transformed to a combination of (Fe

Mn)O during the reduction process and both of them exhibit recyclable crystalline phase variation. Moreover

multiple redox tests showed MnFe

exhibited a decreasing tendency of gasification efficiency because of agglomeration

its typical surface morphology changed from scattered particles to blocky structure. However

MnFeO

formed a granular porous structure which helped to maintain a stable reactivity. Thus

MnFeO

was considered to have better applicability in CLG process.

关键词

Keywords

references

Woolcock P J , Brown R C . A review of cleaning technologies for biomass-derived syngas [J ] . Biomass and Bioenergy , 2013 , 52 ( 3 ): 54 - 84 .

Caputo A C , Palumbo M , Pelagagge P M , et al . Economics of biomass energy utilization in combustion and gasification plants: effects of logistic variables [J ] . Biomass & Bioenergy , 2005 , 28 ( 1 ): 35 - 51 .

Huang Z , Zhang Y , Fu J J , et al . Chemical looping gasification of biomass char using iron ore as an oxygen carrier [J ] . International Journal of Hydrogen Energy , 2016 , 41 ( 40 ): 17871 - 17883 .

Diego L F D , Ortiz M , García-Labiano F , et al . Hydrogen production by chemical-looping reforming in a circulating fluidized bed reactor using Ni-based oxygen carriers [J ] . Journal of Power Sources , 2009 , 192 ( 1 ): 27 - 34 .

Adanez J , Abad A , Garcia-Labiano F , et al . Progress in chemical-looping combustion and reforming technologies [J ] . Progress in Energy & Combustion Science , 2012 , 38 ( 2 ): 215 - 282 .

Liu G C , Liao Y F , Wu Y T , et al . Synthesis gas production from microalgae gasification in the presence of Fe 2 O 3 oxygen carrier and CaO additive [J ] . Applied Energy , 2018 , 212 : 955 - 965 .

Guo L , Zhao H B , Zheng C G . Synthesis gas generation by chemical-looping reforming of biomass with natural copper ore as oxygen carrier [J ] . Waste & Biomass Valorization , 2015 , 6 ( 1 ): 81 - 89 .

Hu Z F , Jiang E C , Ma X Q . The effect of oxygen carrier content and temperature on chemical looping gasification of microalgae for syngas production [J ] . Journal of the Energy Institute , 2019 , 92 ( 3 ): 474 - 487 .

王保文 . 化学链燃烧技术中铁基氧载体的制备及其性能研究 [D ] . 武汉 : 华中科技大学 , 2008 .

Wang B W . Research on combustion synthesis of Fe 2 O 3 -based oxygen carrier and its performance used in chemical looping combustion [D ] . Wuhan : Huazhong University of Science and Technology , 2008 .

Zeng J M , Xiao R , Zhang H Y , et al . Chemical looping pyrolysis-gasification of biomass for high H 2 /CO syngas production [J ] . Fuel Processing Technology , 2017 , 168 : 116 - 122 .

Wu Y T , Liao Y F , Liu G C , et al . Reactivity investigation on biomass chemical looping conversion for syngas production [J ] . Journal of the Energy Institute , 2019 , 92 ( 4 ): 1137 - 1148 .

黄振 , 何方 , 李海滨 , 等 . 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 .

Huang Z , He F , Li H B , et al . synthesis gas generation by chemical-looping gasification of biomass using natural hematite as oxygen carrier [J ] . Journal of Fuel Chemistry and Technology , 2012 , 40 ( 3 ): 300 - 308 .

Bazhenova E , Honkala K . Screening the bulk properties and reducibility of Fe-doped Mn 2 O 3 from first principles calculations [J ] . Catalysis Today , 2017 , 285 : 104 - 113 .

Wang K , Yu Q B , Qin Q , et al . Thermodynamic analysis of syngas generation from biomass using chemical looping gasification method [J ] . International Journal of Hydrogen Energy , 2016 , 41 ( 24 ): 10346 - 10353 .

Rustamov V R , Abdullayev K M , Samedov E A . Biomass conversion to liquid fuel by two-stage thermochemical cycle [J ] . Energy Conversion and Management , 1998 , 39 ( 9 ): 869 - 875 .

Adánez-Rubio I , Pérez-Astray A , Mendiara T , et al . Chemical looping combustion of biomass: CLOU experiments with a Cu-Mn mixed oxide [J ] . Fuel Processing Technology , 2018 , 172 : 179 - 186 .

Schmitz M , Linderholm C . Chemical looping combustion of biomass in 10- and 100-kW pilots — analysis of conversion and lifetime using a sintered manganese ore [J ] . Fuel , 2018 , 231 : 73 - 84 .

梅道锋 . 煤化学链燃烧的铁/铜/锰基氧载体的实验及反应动力学研究 [D ] . 武汉 : 华中科技大学 , 2016 .

Mei D F . Experimental and kinetics investigation of iron/copper/manganese based oxygen carriers for chemical looping combustion of coal [D ] . Wuhan : Huazhong University of Science and Technology , 2016 .

牛鹏杰 . 基于钙铁复合氧载体的化学链气化研究 [D ] . 武汉 : 华中科技大学 , 2018 .

Niu P J . Investigation on chemical-looping gasification using calcium-ferrum mixed oxide as oxygen carriers [D ] . Wuhan : Huazhong University of Science and Technology , 2018 .

王旭锋 , 刘晶 , 刘丰 , 等 . 基于CoFe 2 O 4 载氧体的生物质化学链气化反应特性 [J ] . 化工学报 , 2019 , 70 ( 4 ): 1583 - 1590 .

Wang X F , Liu J , Liu F , et al . Characteristics of biomass chemical looping gasification with CoFe 2 O 4 as oxygen carrier [J ] . CIESC Journal , 2019 , 70 ( 4 ): 1583 - 1590 .

Larring Y , Braley C , Pishahang M , et al . Evaluation of a mixed Fe-Mn oxide system for chemical looping combustion [J ] . Energy & Fuels , 2015 , 29 ( 5 ): 3438 - 3445 .

Lambert A , Delquié C , Clémeneçon I , et al . Synthesis and characterization of bimetallic Fe/Mn oxides for chemical looping combustion [J ] . Energy Procedia , 2009 , 1 ( 1 ): 375 - 381 .

Rydén M , Lyngfelt A , Mattisson T . Combined manganese/iron oxides as oxygen carrier for chemical looping combustion with oxygen uncoupling (CLOU) in a circulating fluidized bed reactor system [J ] . Energy Procedia , 2011 , 4 : 341 - 348 .

Ghosh D , Dutta U , Haque A , et al . Evidence of low temperature spin glass transition in bixbyite type FeMnO 3 [J ] . Materials Science and Engineering: B, 2 017 , 226 : 206 - 210 .

Zhang C T , Zhang L J , Li Q Y , et al . Catalytic pyrolysis of poplar wood over transition metal oxides: correlation of catalytic behaviors with physiochemical properties of the oxides [J ] . Biomass and Bioenergy , 2019 , 124 : 125 - 141 .

Doroftei C , Popa P D , Rezlescu E , et al . Structural and catalytic characterization of nanostructured iron manganite [J ] . Composites Part B: Engineering , 2014 , 67 : 179 - 182 .

Wang B W , Gao C C , Wang W S , et al . Sulfur evolution in chemical looping combustion of coal with MnFe 2 O 4 oxygen carrier [J ] . J. Environ. Sci . , 2014 , 26 ( 5 ): 1062 - 1070 .

Yang Y J , Liu J , Zhang B K , et al . Mechanistic studies of mercury adsorption and oxidation by oxygen over spinel-type MnFe 2 O 4 [J ] . Journal of Hazardous Materials , 2017 , 321 : 154 - 161 .

Abián M , Abad A , Izquierdo M T , et al . Titanium substituted manganese-ferrite as an oxygen carrier with permanent magnetic properties for chemical looping combustion of solid fuels [J ] . Fuel , 2017 , 195 : 38 - 48 .

Chen J , Zhao K , Zhao Z L , et al . Identifying the roles of MFe 2 O 4 (M=Cu, Ba, Ni, and Co) in the chemical looping reforming of char, pyrolysis gas and tar resulting from biomass pyrolysis [J ] . International Journal of Hydrogen Energy , 2019 , 44 ( 10 ): 4674 - 4687 .

付鹏 . 生物质热解气化气相产物释放特性和焦结构演化行为研究 [D ] . 武汉 : 华中科技大学 , 2010 .

Fu P . Study on gas release characteristics and char structural evolution during pyrolysis and gasification of biomass [D ] . Wuhan : Huazhong University of Science and Technology , 2010 .

郭振戈 . 基于PY-GC/MS及原位红外纤维素热解机理研究 [D ] . 广州 : 华南理工大学 , 2016 .

Guo Z G . cellulose pyrolysis mechanism research based on the in situ infrared and PY-GC/MS [D ] . Guangzhou : South China University of Technology , 2016 .

Dong Q , Zhang S P , Ding K , et al . Pyrolysis behavior of raw/torrefied rice straw after different demineralization processes [J ] . Biomass and Bioenergy , 2018 , 119 : 229 - 236 .

Li J J , Mei X L , Zhang L J , et al . A comparative study of catalytic behaviors of Mn , Fe , Co , Ni , Cu and Zn-based catalysts in steam reforming of methanol , acetic acid and acetone [J/OL ] . International Journal of Hydrogen Energy , 2019 , https : // doi . org/ 10 . 1016/j. ijhydene. 2019 . 03 . 269.

Andrew R , Gokak D T , Sharma P , et al . Practical achievements on biomass steam gasification in a rotary tubular coiled-downdraft reactor [J ] . Waste Manag . Res . , 2016 , 35 ( 12 ): 818 - 825 .

Franco C , Pinto F , Gulyurtlu I , et al . The study of reactions influencing the biomass steam gasification process [J ] . Fuel , 2003 , 82 ( 7 ): 835 - 842 .

Huang Z , He F , Zheng A Q , et al . Synthesis gas production from biomass gasification using steam coupling with natural hematite as oxygen carrier [J ] . Energy , 2013 , 53 : 244 - 251 .

Liu G C , Liao Y F , Wu Y T , et al . Characteristics of microalgae gasification through chemical looping in the presence of steam [J ] . International Journal of Hydrogen Energy , 2017 , 36 ( 42 ): 22730 - 22742 .

安梅 , 马晶晶 , 吴唯 , 等 . 基于CuFe 2 O 4 载氧体的羊肠煤化学链气化特性 [J ] . 石油学报(石油加工) , 2019 , 35 ( 3 ): 561 - 568 .

An M , Ma J J , Wu W , et al . Chemical looping gasification of Yangchang coal with CuFe 2 O 4 as oxygen carrier [J ] . Acta Petrolei Sinica (Petroaleum Processing Section) , 2019 , 35 ( 3 ): 561 - 568 .

浏览量

下载量

CSCD

文章被引用时，请邮件提醒。

提交

工具集

关联资源

基于CoFe2O4载氧体的生物质化学链气化反应特性

熔融盐辅助生物质热化学高值化转化研究进展

改性BaFe2O4载氧体生物质化学链气化特性

生物质化学链气化原位补氢制H2/CO可控合成气

高速高温箔片端面密封热气弹耦合性能分析