基于层状氢氧化物衍生复合氧载体的生物质化学链气化实验研究

魏国强; 何方; 赵增立; 赵伟娜; 黄振; 郑安庆; 赵坤; 冯宜鹏; 李海滨

基于层状氢氧化物衍生复合氧载体的生物质化学链气化实验研究

1.
中国科学院广州能源研究所, 中国科学院可再生能源重点实验室, 广东广州 510640
2.
广东机电职业技术学院, 广东广州 510515

基金项目:

国家自然科学基金 51406214

广东省科技计划项目 2015A020215023

详细信息

通讯作者:
何方, E-mail: hefang@ms.giec.ac.cn

中图分类号: TK16
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- 文章访问数: 95
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- PDF下载量: 10
- 被引次数: 0
出版历程
- 收稿日期: 2015-08-23
- 修回日期: 2015-11-30
- 网络出版日期: 2021-01-23
- 刊出日期: 2016-03-30

Chemical looping gasification of biomass based on the oxygen carrier derived from the layered double hydroxide (LDH) precursor

1.
CAS Key Laboratory of Renewable Energy, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences (CAS), Guangzhou 510640, China
2.
Guangdong Mechanical & Electrical College, Guangzhou 510515, China

Funds:

National Natural Science Foundation of China 51406214

and the Science and Technology Planning Project of Guangdong Province 2015A020215023

摘要

摘要: 通过低饱和共沉淀法合成了类水滑石结构的层状氢氧化物(Layered Double Hydroxide, LDH) 前驱体, 经煅烧获得衍生Cu/Al/Zn、Cu/Al/Ni、Cu/Al/Ni/Zn高分散复合氧载体.采用XRD、XRF、H₂-TPR、SEM及BET等分析手段对氧载体的结构及反应性能进行了表征, 并通过固定床反应器开展了氧载体与生物质化学链气化实验.结果表明, 合成的三种前驱体都具有典型的水滑石特征衍射峰, 且层板稳定.Cu/Al/Zn前驱体层间厚度为0.2642nm, Ni²⁺引入后, 层间距减小.前驱体煅烧后形成的复合氧载体中元素含量与制备试剂基本一致.氧载体中Zn、Ni元素的引入可提升CuO的反应活性, 降低H₂还原的反应温度, Zn元素与Cu具有更好的协同作用.Cu/Al/Ni/Zn氧载体在固定床化学链气化中具有较好的碳转化率和气体产率, 其碳转化率为82.03%.反应后氧载体比表面积为5.995m²/g, 具有较好的可再生性与抗烧结性, 是生物质化学链气化反应较为理想的氧载体.
- 层状氢氧化物 /
- 水滑石 /
- 化学链气化 /
- 氧载体 /
- 生物质
Abstract: Layered double hydroxide (LDH) precursors with different metal elements were prepared by co-precipitation method at constant pH value; highly dispersed Cu/Al/Zn, Cu/Al/Ni and Cu/Al/Ni/Zn mixed metal oxygen carriers were obtained by calculation of the corresponding precursors. These oxygen carriers were characterized by XRD, XRF, H₂-TPR, SEM and nitrogen adsorption and their activity in the chemical looping gasification (CLG) of biomass was investigated in a fixed bed reactor. The results indicated that typical hydrotalcite structure appears in the three precursors with stable layer board. The interlayer spacing of Cu/Al/Zn precursor is 0.2642nm, larger than that of the Cu/Al/Ni precursor. The oxygen carriers derived from the corresponding precursors display similar elements contents as the preparation reagents. Due to the synergy among various metals, the Cu/Al/Ni/Zn oxygen carrier shows the highest reaction activity and anti-sintering ability. The addition of Ni and Zn has a positive effect on the activity of CuO and reduce its reduction temperature; Zn shows a better synergistic effect than Ni with Cu. The carbon conversion reaches 82.03% for the CLG of biomass with Cu/Al/Ni/Zn as oxygen carrier; the surface area of Cu/Al/Ni/Zn remanis 5.995m²/g after the CLG reaction, suggesting that it could be an ideal candidate for the CLG of biomass.
- layered double hydroxide /
- hydrotalcite /
- chemical looping gasification /
- oxygen carrier /
- biomass

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图 1 镁铝水滑石结构示意图

Figure 1 Structure of hydrotalcite

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图 2 前驱体及煅烧后产物氧载体的XRD谱图

Figure 2 XRD patterns of the LDH precursor and oxygen carriers

a: Cu/Al/Zn LDH; b: Cu/Al/Ni LDH; c: Cu/Al/Ni/Zn LDH; d: Cu/Al/Zn oxygen carrier; e: Cu/Al/Ni oxygen carrier; f: Cu/Al/Ni/Zn oxygen carrier ◆: Cu/Al/Zn LDH; ▲: Cu/Al/Ni LDH; ●: Cu/Al/Ni/Zn LDH; ○: CuO; ■: Al₂O₃; △: NiO; ◇: ZnO

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图 3 合成氧载体的H₂-TPR谱图

Figure 3 H₂-TPR profiles of various oxygen carriesr

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图 4 氧载体生物化学链气化实验反应前后的SEM照片

Figure 4 SEM images of the oxygen carriers before and after CLG reaction

(a): Cu/Al/Zn fresh; (b): Cu/Al/Zn used; (c): Cu/Al/Ni fresh; (d): Cu/Al/Ni used; (e): Cu/Al/Ni/Zn fresh; (f): Cu/Al/Ni/Zn used

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图 5 氧载体生物化学链气化实验反应前后XRD谱图

Figure 5 XRD patterns of the oxygen carrier before and after CLG reaction

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表 1 氧载体前驱体晶胞参数

Table 1 Cell parameters of the oxygen carrier precursors

Cell parameter	Cu/Al/Zn LDH	Cu/Al/Ni LDH	Cu/Al/Ni/Zn LDH
a	3.072 0	3.054 0	3.063
b	3.072 0	3.054 0	3.063
c	22.620	22.966 0	22.713
d₀₀₃ /nm	0.264 2	0.263 2	0.263 7
d₀₀₆ /nm	0.228 7	0.194 0	0.211 4
d₀₀₉ /nm	0.171 7	0.152 6	0.162 2
d₁₁₀ /nm	0.153 6	0.141 8	0.147 7
Cell volume (10⁶ /pm³)	183.56	185.50	184.53

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表 2 层状氢氧化物前驱体及相应氧载体的元素分析

Table 2 Elemental analysis of the LDH precursors and corresponding oxygen carrier

	Content w/%
	Cu/Al/Zn LDH	Cu/Al/Zn OC	Cu/Al/Ni LDH	Cu/Al/Ni OC	Cu/Al/ Ni/Zn LDH	Cu/Al/ Ni/Zn OC
O	43.1	27.91	48.72	23.59	59.74	26.22
Zn	18.15	22.56	0.026 5	0.028 4	8.865	18.29
Cu	17.75	21.52	15.7	30.27	8.133	17.06
Na	6.147	13.56	6.383	8.64	3.524	7.373
Al	7.831	13.4	5.362	11.66	1.947	9.973
Ni	0.715	0.937 4	16.91	33.72	9.81	20.71
C	6.216	-	6.834	-	7.925	-
Ca	0.021	0.028	0.017	0.084	0.012	0.033
Si	0.015	0.023	0.012	0.470	0.007	0.234
Fe	0.014	0.019	0.012	0.037	0.008	0.021
Mn	0.015	0.015	0.006	0.018	0.009	0.017
note: “-” means the element was undetected

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表 3 生物质的元素分析与工业分析

Table 3 Elemental analysis and proximate analysis of biomass

Proximate analysis w_db/%				Element analysis w_db/%					Q_LHV/ (MJ·kg^-1, db)
M	V	FC	A	C	H	O	N	S	Q_LHV/ (MJ·kg^-1, db)
8.39	84.31	6.88	0.42	46.44	6.21	47.29	0.05	0.01	18.707
note: M moisture, V volatile matter, FC fixed carbon, A ash, db dry basis, LHV lower heating value

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表 4 合成氧载体生物质化学链气化实验结果

Table 4 Experimental results of biomass CLG on the basis of various oxygen carriers

Item	Cu/Al/Zn	Cu/Al/Ni	Cu/Al/Ni/Zn	Fe/Al
CH₄/%	7.05	7.60	7.14	13.15
C₂H_m/%	2.39	1.71	2.34	-
CO₂/%	24.12	24.01	23.88	18.09
CO/%	32.32	45.43	32.37	47.94
H₂/%	34.12	21.25	34.26	20.32
Gas yield/(m³·kg^-1)	1.09	0.95	1.12	0.95
Q_LHV/(MJ·m^-3)	11.92	11.88	11.90	12.65
Carbon conversion x/%	80.23	82.16	82.03	78.47
Gasification efficiency η%	69.46	60.36	71.25	64.27

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表 5 氧载体生物质化学链气化反应后BET比表面积

Table 5 Surface area of the oxygen carriers after CLG reaction

	BET area A/(m²·g^-1)
	Cu/Al/Zn OC	Cu/Al/Ni OC	Cu/Al/Ni/Zn OC
Before	2.480	2.287	3.821
After	5.243	2.828	5.995

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