Mg修饰Fe/Al载氧体煤化学链制氢

doi:10.16085/j.issn.1000-6613.2021-0561

摘要/Abstract

摘要：

目前化学链过程常用的Fe₂O₃/Al₂O₃载氧体会形成FeAl₂O₄，因热力学限制很难与水反应制氢。为了抑制FeAl₂O₄的形成，本文向Fe/Al载氧体中添加Mg，在固定床上进行煤化学链制氢（CLHG），深入分析Mg的作用机理并探究其对实验结果的影响。XRD结果表明，Mg质量分数从1%增加到26.5%时，MgAl₂O₄特征峰增强，FeAl₂O₄特征峰逐渐消失，说明Mg减弱了Fe和Al之间的相互作用。SEM显示Mg添加后载氧体颗粒减小，耐烧结性能优异。对比不同煤/载氧体质量比的实验，质量比为0.5/15时碳转化率和产氢量最高。在不同Mg含量的载氧体中，Fe40Mg20Al40具备最好的反应性能，碳转化率和产氢量为81.75%和1.7182L/g，比Fe40Al60分别增加10.2%和58.5%。Fe40Mg20Al40经10次循环，表面仅有轻微烧结，碳转化率和产氢量均在78%和1.52L/g以上，循环性能良好。添加Mg可以有效抑制FeAl₂O₄的生成，显著增强蒸汽氧化过程的反应活性，大幅提高氢气产量，十分适用于煤化学链制氢。

关键词: Fe基载氧体, FeAl₂O₄, MgAl₂O₄, 化学链制氢, 煤

Abstract:

Fe₂O₃/Al₂O₃ oxygen carrier used in chemical looping process will form FeAl₂O₄, which is difficult to react with water to produce hydrogen due to thermodynamic limitations. In order to solve this problem, Mg was added to Fe/Al oxygen carrier for coal chemical looping hydrogen generation, and the action mechanism of Mg was deeply analyzed and its influence on the experimental results was explored. The XRD results show that when the Mg content increases from 1% to 26.5%, the characteristic peak of MgAl₂O₄ increases, and the characteristic peak of FeAl₂O₄ gradually disappears, indicating that Mg weakens the interaction between Fe and Al. SEM shows that the size of oxygen carrier particles decrease after adding Mg, and the sintering resistance is excellent. Based on the experiments of different coal/oxygen-carrier mass ratio, the carbon conversion and hydrogen production were the highest when the mass ratio was 0.5/15. Among the oxygen carriers with different Mg contents, Fe40Mg20Al40 has the best reaction performance, and the carbon conversion and hydrogen production are 81.75% and 1.7182L/g, which increase by 10.2% and 58.5% compared with Fe40Al60, respectively. After 10 cycles, the surface of Fe40Mg20Al40 is only slightly sintered, and the carbon conversion and hydrogen production are above 78% and 1.52L/g, respectively, showing good cycling performance. The addition of Mg can effectively inhibit the formation of FeAl₂O₄, significantly enhance the reactivity of steam oxidation process, and greatly increase the yield of hydrogen, which is very suitable for coal chemical looping hydrogen generation.

Key words: Fe-based oxygen carrier, FeAl₂O₄, MgAl₂O₄, chemical looping hydrogen generation, coal

中图分类号:

TQ116.2

安阳, 袁思杰, 高振东, 吴曼, 王凌云, 郭庆杰. Mg修饰Fe/Al载氧体煤化学链制氢[J]. 化工进展, 2022, 41(2): 648-654.

AN Yang, YUAN Sijie, GAO Zhendong, WU Man, WANG Lingyun, GUO Qingjie. Chemical looping hydrogen generation of coal with oxygen carrier of Mg-modified Fe/Al[J]. Chemical Industry and Engineering Progress, 2022, 41(2): 648-654.

图/表 12

表1 煤的工业分析和元素分析

工业分析/%					元素分析/%
M_ad	A_ad	V_ad	FC_ad		C_ad	H_ad	N_ad	S_ad	O_ad
11.18	4.56	31.95	63.50		77.60	5.16	1.46	0.46	10.77

图1 管式炉反应器实验装置示意图

表2 实验条件

还原时间

蒸汽氧化阶段

空气氧化阶段

Ar流量

/mL·min^-1

煤/载氧体质量比

/g·g^-1

温度

/℃

反应时间

/min

Ar流量

/mL·min^-1

H₂O流量

/mL·min^-1

温度

/℃

反应时间

/min

空气流量

/mL·min^-1

温度

/℃

反应时间

/min

200

0.5/5，0.5/10，0.5/15，0.5/20

图2 不同镁含量的Fe-Mg-Al载氧体的XRD图谱

图3 Mg改性Fe2O3/Al2O3载氧体的SEM图像

图4 Mg对Fe2O3/Al2O3载氧体还原性质的影响

图5 不同Mg含量对碳转化率、氢气产量和氢气浓度的影响载氧体：1—Fe40Al60；2—Fe40MglAl59；3—Fe40Mg5Al55；

4—Fe40Mg10Al50；5—Fe40Mg15Al45；6—Fe40Mg17Al43；7—Fe40Mg20Al40；8—Fe40Mg25Al35；9—Fe40Mg26.5Al33.5

图6 还原阶段后载氧体的XRD图谱

图7 煤/载氧体质量比对碳转化率、氢气产量和氢气浓度的影响

图8 多循环中Fe40Mg20Al40和Fe40Al60载氧体的氢气产量和碳转化率

图9 多循环过程中Fe-Mg-Al载氧体的SEM图像

表3 循环过程中Fe40Mg20Al40载氧体的ICP分析

循环次数	Mg质量分数/%
新鲜载氧体	12.02
5次循环	11.97
10次循环	11.89

参考文献 24

1	DOU B L, ZHANG H, CUI G M, et al. Hydrogen production by sorption-enhanced chemical looping steam reforming of ethanol in an alternating fixed-bed reactor: sorbent to catalyst ratio dependencies[J]. Energy Conversion and Management, 2018, 155: 243-252.
2	韩丹华, 郭雪岩, 王志远. 化学链重整制氢NiO-CeO₂/γ-Al₂O₃复合载氧体的性能[J]. 化工进展, 2022, 41(1): 192-200.
	HAN Danhua, GUO Xueyan, WANG Zhiyuan. Performance of NiO-CeO₂/γ-Al₂O₃ composite oxygen carriers for hydrogen generation with chemical looping reforming[J]. Chemical Industry and Engineering Progress, 2022, 41(1): 192-200.
3	KRUGER P. Appropriate technologies for large-scale production of electricity and hydrogen fuel[J]. International Journal of Hydrogen Energy, 2008, 33(21): 5881-5886.
4	罗明, 王树众, 王龙飞, 等. 基于化学链技术制氢的研究进展[J]. 化工进展, 2014, 33(5): 1123-1133.
	LUO Ming, WANG Shuzhong, WANG Longfei, et al. Advances in hydrogen production using chemical-looping technology[J]. Chemical Industry and Engineering Progress, 2014, 33(5): 1123-1133.
5	梁皓, 宋喜军, 尹泽群, 等. 化学链制氢中Fe₂O₃/LaFeO₃载氧体的性能研究[J]. 燃料化学学报, 2013, 41(12): 1512-1519.
	LIANG Hao, SONG Xijun, YIN Zequn, et al. Performance of Fe₂O₃/LaFeO₃ as oxygen carrier in chemical-looping hydrogen generation[J]. Journal of Fuel Chemistry and Technology, 2013, 41(12): 1512-1519.
6	LIU W, ISMAIL M, DUNSTAN M T, et al. Inhibiting the interaction between FeO and Al₂O₃ during chemical looping production of hydrogen[J]. RSC Advances, 2015, 5(3): 1759-1771.
7	LIU T, YU Z L, LI G, et al. Performance of potassium-modified Fe₂O₃/Al₂O₃ oxygen carrier in coal-direct chemical looping hydrogen generation[J]. International Journal of Hydrogen Energy, 2018, 43(42): 19384-19395.
8	MA S W, LI M, WANG G B, et al. Effects of Zr doping on Fe₂O₃/CeO₂ oxygen carrier in chemical looping hydrogen generation[J]. Chemical Engineering Journal, 2018, 346: 712-725.
9	SOLUNKE R D, VESER G. Hydrogen production via chemical looping steam reforming in a periodically operated fixed-bed reactor[J]. Industrial & Engineering Chemistry Research, 2010, 49(21): 11037-11044.
10	LI F X, KIM H R, SRIDHAR D, et al. Syngas chemical looping gasification process: oxygen carrier particle selection and performance[J]. Energy & Fuels, 2009, 23(8): 4182-4189.
11	李金帅. 复合载氧体的西部煤化学链制氢反应特性[D]. 青岛: 青岛科技大学, 2020.
	LI Jinshuai. Study of western coal chemical looping hydrogen generation with iron-based oxygen carrier[D]. Qingdao: Qingdao University of Science & Technology, 2020.
12	魏国强, 何方, 黄振, 等. 化学链燃烧技术的研究进展[J]. 化工进展, 2012, 31(4): 713-725.
	WEI Guoqiang, HE Fang, HUANG Zhen, et al. Research development in chemical-looping combustion[J]. Chemical Industry and Engineering Progress, 2012, 31(4): 713-725.
13	程煜, 刘永卓, 田红景, 等. 铁基复合载氧体煤化学链气化反应特性及机理[J]. 化工学报, 2013, 64(7): 2587-2595.
	CHENG Yu, LIU Yongzhuo, TIAN Hongjing, et al. Chemical-looping gasification reaction characteristics and mechanism of coal and Fe-based composite oxygen carriers[J]. CIESC Journal, 2013, 64(7): 2587-2595.
14	燕希敏, 苗鹏, 常国璋, 等. Fe/赤泥催化水蒸气气化煤焦的反应性与微结构特性[J]. 化工进展, 2018, 37(5): 1753-1759.
	YAN Ximin, MIAO Peng, CHANG Guozhang, et al. Characteristics of microstructures and reactivities during steam gasification of coal char catalyzed by red mud[J]. Chemical Industry and Engineering Progress, 2018, 37(5): 1753-1759.
15	杨明明, 刘永卓, 贾伟华, 等. Fe₂O₃/ATP载氧体制备及煤化学链燃烧性能研究[J]. 燃料化学学报, 2015, 43(2): 167-176.
	YANG Mingming, LIU Yongzhuo, JIA Weihua, et al. Preparation and performance of the Fe₂O₃/ATP oxygen carriers in coal chemical looping combustion[J]. Journal of Fuel Chemistry and Technology, 2015, 43(2): 167-176.
16	BOHN C D, CLEETON J P, MÜLLER C R, et al. Stabilizing iron oxide used in cycles of reduction and oxidation for hydrogen production[J]. Energy & Fuels, 2010, 24(7): 4025-4033.
17	YU Z L, LIU T, LI C Y, et al. Coal direct chemical looping hydrogen production with K-Fe-Al composite oxygen carrier[J]. International Journal of Greenhouse Gas Control, 2018, 75: 24-31.
18	张思文, 沈来宏, 顾海明, 等. 钠修饰铁矿石载氧体的串行流化床煤化学链燃烧试验[J]. 化工学报, 2013, 64(11): 4187-4195.
	ZHANG Siwen, SHEN Laihong, GU Haiming, 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.
19	JOHANSSON M, MATTISSON T, LYNGFELT A. Investigation of Fe₂O₃ with MgAl₂O₄ for chemical-looping combustion[J]. Industrial & Engineering Chemistry Research, 2004, 43(22): 6978-6987.
20	GARCÍA-LABIANO F, DE DIEGO L F, ADÁNEZ J, et al. Temperature variations in the oxygen carrier particles during their reduction and oxidation in a chemical-looping combustion system[J]. Chemical Engineering Science, 2005, 60(3): 851-862.
21	JERNDAL E, LEION H, AXELSSON L, et al. Using low-cost iron-based materials as oxygen carriers for chemical looping combustion[J]. Oil & Gas Science and Technology, 2011, 66(2): 235-248.
22	FENG Y C, WANG N N, GUO X, et al. Dopant screening of modified Fe₂O₃ oxygen carriers in chemical looping hydrogen production[J]. Fuel, 2020, 262: 116489.
23	苑宏刚. MgO含量对Fe₂O₃/MgO/Al₂O₃载氧体性能影响[J]. 天津化工, 2016, 30(2): 19-22.
	YUAN Honggang. Effect of MgO loadings on the performance of Fe₂O₃/MgO/Al₂O₃ oxygen carrier[J]. Tianjin Chemical Industry, 2016, 30(2): 19-22.
24	梁皓, 尹泽群, 方向晨, 等. 助剂对Fe₂O₃/Al₂O₃载氧体在化学链制氢反应性能的影响[J]. 中国稀土学报, 2018, 36(3): 301-307.
	LIANG Hao, YIN Zequn, FANG Xiangchen, et al. Effect of additives on reaction performances of Fe₂O₃/Al₂O₃ as oxygen carriers applied in chemical-looping hydrogen generation[J]. Journal of the Chinese Society of Rare Earths, 2018, 36(3): 301-307.

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