Ce0.8Cu0.2O2氧载体耦合S-1分子筛对化学链反应性能的影响

侯凯源; 王禹皓; 蒋丽红; 范浩熙; 郑燕娥

doi:10.19906/j.cnki.JFCT.2022079

Ce_0.8Cu_0.2O₂氧载体耦合S-1分子筛对化学链反应性能的影响

doi: 10.19906/j.cnki.JFCT.2022079

侯凯源^1,,
王禹皓^{2, 3, ,},
蒋丽红¹,
范浩熙¹,
郑燕娥^{1, 2, ,}

1.
昆明理工大学化学工程学院, 云南昆明 650093
2.
昆明理工大学复杂有色金属资源清洁利用国家重点实验室, 云南昆明 650093
3.
昆明理工大学冶金与能源工程学院, 云南昆明 650093

基金项目: 国家自然科学基金（21706108）和云南省应用基础研究项目（2018FD032）资助

详细信息

作者简介:
侯凯源（1999—），男，硕士研究生，1136729494@qq.com

通讯作者:
E-mail: wangyuhao@xmu.edu.cn

zhengyane87@yeah.net

中图分类号: TQ519
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- 被引次数: 0
出版历程
- 收稿日期: 2022-09-05
- 修回日期: 2022-10-06
- 录用日期: 2022-10-12
- 网络出版日期: 2022-10-26
- 刊出日期: 2023-06-15

Effects of Ce_0.8Cu_0.2O₂ oxygen carrier-coupled S-1 molecular sieve on chemical-looping performance

HOU Kai-yuan^1
,,
WANG Yu-hao^{2, 3
, ,},
JIANG Li-hong¹,
FAN Hao-xi¹,
ZHENG Yan-e^{1, 2
, ,}

1.
Faculty of Chemical Engineering, Kunming University of Science and Technology, Kunming 650093, China
2.
State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization, Kunming University of Science and Technology, Kunming 650093, China
3.
Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming 650093, China

Funds: The project was supported by National Natural Science Foundation of China (21706108) and Applied Basic Research Plan in Yunnan Province of China Project(2018FD032)

摘要

摘要: 在Ce_0.8Cu_0.2O₂氧载体中添加不同质量S-1分子筛，并利用XRD、BET、XPS、SEM、TEM和CH₄-TPR ＆ CO₂-TPO等表征对氧载体的物化特性和反应性能进行了研究。考察了S-1分子筛添加量对Ce_0.8Cu_0.2O₂氧载体在化学链甲烷重整耦合CO₂还原反应中的性能的影响。与单纯的Ce_0.8Cu_0.2O₂氧载体相比，添加了0.3 g S-1分子筛后复合氧载体的比表面积明显增大，从15.44 m²/g提高至73.27 m²/g。同时热稳定性和结构稳定性也得到了很大的改善。添加了0.3 g S-1分子筛的复合氧载体CH₄转化率由38.93%提升至56.03%，CO₂还原过程中CO产率由1.18 mmol/g增加至2.16 mmol/g。
- 化学链 /
- S-1分子筛 /
- 甲烷重整 /
- CO₂还原 /
- 合成气
Abstract: Ce_0.8Cu_0.2O₂ oxygen carrier has excellent performance in chemical-looping reforming of methane coupled with CO₂ reduction technology. Different mass of S-1 molecular sieve was added to Ce_0.8Cu_0.2O₂ oxygen carrier. The physicochemical properties and reactivity of the carrier were characterized by XRD, BET, XPS, SEM, TEM and CH₄-TPR & CO₂-TPO. The effect of S-1 molecular sieve on the performance of Ce_0.8Cu_0.2O₂ oxygen carrier in chemical-looping reforming of methane coupled with CO₂ reduction was systematically investigated. Compared with Ce_0.8Cu_0.2O₂ oxygen carrier alone, the specific surface area of the composite oxygen carrier increased from 15.44 to 73.27 m²/g after adding 0.3 g S-1 molecular sieve. At the same time, its thermal stability and structural stability were greatly improved. The CH₄ conversion rate of composite oxygen carrier with 0.3 g S-1 molecular sieve increased from 38.93% to 56.03%, and the CO yield increased from 1.18 to 2.16 mmol/g during CO₂ reduction.
- chemical-looping /
- S-1 molecular sieves /
- reforming of methane /
- CO₂ reduction /
- syngas

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FIG. 2383. FIG. 2383.

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图 1 实验系统示意图

Figure 1 Schematic diagram of the experimental system

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图 2 氧载体的XRD谱图（a）和新鲜氧载体的氮气吸附-脱附等温曲线（b）

Figure 2 XRD patterns (a) of oxygen carriers and nitrogen adsorption-desorption (b) isotherms of oxygen carriers

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图 3 Ce_0.8Cu_0.2O₂(a)、Ce_0.8Cu_0.2O₂/0.2 g S-1(b)、Ce_0.8Cu_0.2O₂/0.3 g S-1(c)新鲜氧载体和S-1的XPS谱图

Figure 3 XPS spectra of Ce_0.8Cu_0.2O₂ (a), Ce_0.8Cu_0.2O₂/0.2 g S-1 (b), Ce_0.8Cu_0.2O₂/0.3g S-1 (c) fresh oxygen carriers and S-1

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图 4 S-1分子筛（(a1)，(a2)）以及Ce_0.8Cu_0.2O₂/0.3 g S-1氧载体（(b1)，(b2)）的SEM照片

Figure 4 SEM images of S-1 ((a1), (a2)) and Ce_0.8Cu_0.2O₂/0.3 g S-1 ((b1), (b2)) oxygen carrier

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图 5 Ce_0.8Cu_0.2O₂/0.3 g S-1氧载体的TEM照片

Figure 5 TEM images of Ce_0.8Cu_0.2O₂/0.3 g S-1 oxygen carrier

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图 6 Ce_0.8Cu_0.2O₂ (a)、Ce_0.8Cu_0.2O₂/0.1 g S-1 (b)、Ce_0.8Cu_0.2O₂/0.2 g S-1 (c)、Ce_0.8Cu_0.2O₂/0.3 g S-1 (d)和Ce_0.8Cu_0.2O₂/0.4 g S-1 (e)氧载体和S-1(f)的CH₄-TPR谱图

Figure 6 CH₄-TPR profiles of Ce_0.8Cu_0.2O₂ (a), Ce_0.8Cu_0.2O₂/0.1 g S-1 (b), Ce_0.8Cu_0.2O₂/0.2 g S-1 (c), Ce_0.8Cu_0.2O₂/0.3 g S-1 (d) and Ce_0.8Cu_0.2O₂/0.4 g S-1 (e) oxygen carriers and S-1(f)

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图 7 Ce_0.8Cu_0.2O₂ (a)、Ce_0.8Cu_0.2O₂/0.1 g S-1 (b)、Ce_0.8Cu_0.2O₂/0.2 g S-1 (c)、Ce_0.8Cu_0.2O₂/0.3 g S-1 (d)和Ce_0.8Cu_0.2O₂/0.4 g S-1 (e)氧载体的CO₂-TPO谱图

Figure 7 CO₂-TPO curves of Ce_0.8Cu_0.2O₂ (a), Ce_0.8Cu_0.2O₂/0.1 g S-1 (b), Ce_0.8Cu_0.2O₂/0.2 g S-1 (c), Ce_0.8Cu_0.2O₂/0.3 g S-1 (d) and Ce_0.8Cu_0.2O₂/0.4 g S-1 (e) oxygen carriers

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图 8 Ce_0.8Cu_0.2O₂ (a)、Ce_0.8Cu_0.2O₂/0.1 g S-1 (b)、Ce_0.8Cu_0.2O₂/0.2 g S-1 (c)、Ce_0.8Cu_0.2O₂/0.3 g S-1 (d)和Ce_0.8Cu_0.2O₂/0.4 g S-1(e)氧载体和S-1(f)在850 ℃下甲烷部分氧化反应中气体含量的变化

Figure 8 Gas content change curve of Ce_0.8Cu_0.2O₂ (a), Ce_0.8Cu_0.2O₂/0.1 g S-1 (b), Ce_0.8Cu_0.2O₂/0.2 g S-1 (c), Ce_0.8Cu_0.2O₂/0.3 g S-1 (d), Ce_0.8Cu_0.2O₂/0.4 g S-1 (e) oxygen carriers and S-1 (f) in the CH₄ partial oxidation reactions at 850 ℃

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图 9 氧载体在850 ℃下CO₂还原反应中的CO和CO₂含量的变化

Figure 9 Variation curve of CO and CO₂ contents in CO₂ reduction reactions of oxygen carriers at 850 ℃ over Ce_0.8Cu_0.2O₂ (a), Ce_0.8Cu_0.2O₂/0.1 g S-1 (b), Ce_0.8Cu_0.2O₂/0.2 g S-1 (c), Ce_0.8Cu_0.2O₂/0.3 g S-1 (d), Ce_0.8Cu_0.2O₂/0.4 g S-1 (e)

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图 10 Ce_0.8Cu_0.2O₂((a)/(d))、 Ce_0.8Cu_0.2O₂/0.2 g S-1 ((b)/(e))和Ce_0.8Cu_0.2O₂/0.3 g S-1 ((c)/(f))氧载体在850 ℃时20次redox循环的CH₄部分氧化反应和CO₂还原反应的气体含量变化

Figure 10 Gas content of Ce_0.8Cu_0.2O₂ ((a)/(d)), Ce_0.8Cu_0.2O₂/0.2 g S-1 ((b)/(e)) and Ce_0.8Cu_0.2O₂/0.3 g S-1 ((c)/(f)) oxygen carriers in CH₄ partial oxidation reactions and CO₂ reduction reactions during 20 redox cycles at 850 ℃

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图 11 经历20次redox循环后的Ce_0.8Cu_0.2O₂、Ce_0.8Cu_0.2O₂/0.2 g S-1 和Ce_0.8Cu_0.2O₂/0.3 g S-1 氧载体的XRD谱图和氮气吸附-脱附等温曲线

Figure 11 XRD patterns and nitrogen adsorption-desorption isotherms of Ce_0.8Cu_0.2O₂、Ce_0.8Cu_0.2O₂/0.2 g S-1 and Ce_0.8Cu_0.2O₂/0.3 g S-1 oxygen carriers after 20 redox cycles

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表 1 Ce_0.8Cu_0.2O₂ 样品和耦合不同比例S-1分子筛的Ce_0.8Cu_0.2O₂ 样品的平均孔径、比表面积和孔容

Table 1 Average pore diameter, BET surface area and total pore volume of Ce_0.8Cu_0.2O₂ samples and Ce_0.8Cu_0.2O₂ samples coupled with different proportions of S-1 zeolites

Sample	Average pore diameter/nm	Surface area/(m²·g⁻¹)	Total pore volume/(cm³·g⁻¹)
S-1	2.61	382.07	0.25
Ce_0.8Cu_0.2O₂	28.38	15.44	0.11
Ce_0.8Cu_0.2O₂/0.1 g S-1	13.79	33.21	0.11
Ce_0.8Cu_0.2O₂/0.2 g S-1	8.15	69.40	0.14
Ce_0.8Cu_0.2O₂/0.3 g S-1	5.11	73.27	0.09
Ce_0.8Cu_0.2O₂/0.4 g S-1	6.62	79.00	0.13

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表 2 样品的XPS特性参数

Table 2 XPS characteristic parameters of sample

Sample	Surface element composition
Sample	O_ads / O_latt	Cu⁺ / Cu^{2 +}	Ce^{3 +} / Ce^{4 +}
Ce_0.8Cu_0.2O₂	1.01	0.47	0.11
Ce_0.8Cu_0.2O₂/0.2 g S-1	2.58	0.44	0.13
Ce_0.8Cu_0.2O₂/0.3 g S-1	2.45	0.34	0.15

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表 3 样品在850 ℃下甲烷部分氧化反应中的气体含量

Table 3 Gas content of sample in the CH₄ partial oxidation reactions at 850 ℃

Sample	Percent conversion of CH₄/%	Yield of CO / (mmol·g⁻¹)	Yield of CO₂ / (mmol·g⁻¹)	Yield of carbon deposition / (mmol·g⁻¹)
Ce_0.8Cu_0.2O₂	38.93	1.25	0.19	0.014
Ce_0.8Cu_0.2O₂/0.1 g S-1	44.87	1.68	0.20	0.015
Ce_0.8Cu_0.2O₂/0.2 g S-1	51.07	1.83	0.21	0.033
Ce_0.8Cu_0.2O₂/0.3 g S-1	56.03	2.24	0.19	0.031
Ce_0.8Cu_0.2O₂/0.4 g S-1	57.30	2.20	0.18	0.034

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表 4 样品在850 ℃下CO₂还原反应中的气体含量

Table 4 Gas content of samples in CO₂ reduction reaction at 850 ℃

Sample	Yield of CO / (mmol·g⁻¹)
Ce_0.8Cu_0.2O₂	1.18
Ce_0.8Cu_0.2O₂/0.1 g S-1	1.53
Ce_0.8Cu_0.2O₂/0.2 g S-1	1.91
Ce_0.8Cu_0.2O₂/0.3 g S-1	2.16
Ce_0.8Cu_0.2O₂/0.4 g S-1	2.03

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表 5 样品在850 ℃时20次循环过程得失氧量与积炭量变化

Table 5 Amount of oxygen gained and lost during the 20 cycles at 850 ℃ and the amount of carbon deposition variated

Sample	Ce_0.8Cu_0.2O₂/（mmol·g⁻¹）			Ce_0.8Cu_0.2O₂/0.2 g S-1/（mmol·g⁻¹）			Ce_0.8Cu_0.2O₂/0.3 g S-1/（mmol·g⁻¹）
Sample	oxygen loss	oxygen gain	carbon deposition	oxygen loss	oxygen gain	carbon deposition	oxygen loss	oxygen gain	carbon deposition
2	2.07	1.20	0.020	2.42	2.20	0.041	2.30	2.08	0.042
4	1.23	0.71	0.051	1.33	1.27	0.049	1.56	1.57	0.043
6	0.93	0.74	0.048	1.15	1.20	0.048	1.00	1.14	0.046
8	0.90	0.81	0.052	1.00	0.97	0.054	1.17	1.18	0.044
10	0.97	0.66	0.049	0.91	0.89	0.051	1.09	1.12	0.044
12	1.93	1.52	0.016	1.26	0.82	0.028	1.75	1.36	0.017
14	0.87	1.08	0.050	0.65	0.62	0.043	1.10	1.04	0.035
16	1.02	0.95	0.048	0.57	0.54	0.043	0.98	1.04	0.035
18	0.99	0.95	0.049	0.59	0.48	0.044	0.93	0.95	0.038
20	0.87	0.88	0.049	0.48	0.39	0.044	0.88	0.86	0.037

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表 6 20次redox循环后样品的平均孔径、比表面积和孔容

Table 6 Average pore diameter, BET surface area and total pore volume of samples after 20 redox cycles

Sample	Average pore diameter / nm	Surface area / (m²·g⁻¹)	Total pore volume / (cm³·g⁻¹)
Ce_0.8Cu_0.2O₂	10.48	3.01	0.008
Ce_0.8Cu_0.2O₂/0.2 g S-1	4.02	33.94	0.03
Ce_0.8Cu_0.2O₂/0.3 g S-1	3.52	51.50	0.04

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