焙烧温度对CO2-CH4重整制合成气NiO/γ-Al2O3催化剂性能的影响

doi:10.15541/jim20150382

无机材料学报 ›› 2016, Vol. 31 ›› Issue (3): 234-240.DOI: 10.15541/jim20150382 CSTR: 32189.14.10.15541/jim20150382

焙烧温度对CO₂-CH₄重整制合成气NiO/γ-Al₂O₃催化剂性能的影响

莫文龙, 马凤云(), 刘月娥, 刘景梅, 钟梅, 艾沙·努拉洪

新疆大学化学化工学院, 煤炭清洁转化与化工过程新疆维吾尔自治区重点实验室, 乌鲁木齐 830046

收稿日期:2015-08-13 修回日期:2015-10-07 出版日期:2016-03-20 网络出版日期:2016-02-24
作者简介:
莫文龙(1987-), 男, 博士研究生.
基金资助:
国家高技术研究发展计划(863计划)(2015AA050502);新疆大学博士研究生创新项目( XJUBSCX-2013008)

Influence of Calcination Temperature on Performance of NiO/γ-Al₂O₃ Catalyst for CO₂-CH₄ Reforming to Produce Syngas

MO Wen-Long, MA Feng-Yun(), LIU Yue-E, LIU Jing-Mei, ZHONG Mei, Aisha· Nulahong

Key Laboratory of Coal Clean Conversion & Chemical Engineering Process (Xinjiang Uyghur Autonomous Region), College of Chemistry and Chemical Engineering, Xinjiang University, Urumqi 830046, China

Received:2015-08-13 Revised:2015-10-07 Published:2016-03-20 Online:2016-02-24
Supported by:
National “863” Project of China(2015AA050502);Xinjiang University Science and Technology Innovation Project for Doctoral Student (XJUBSCX-2013008)

摘要/Abstract

摘要：

采用水解-沉积法, 在不同焙烧温度下制备了cat-500、cat-600、cat-700和cat-800系列NiO/γ-Al₂O₃催化剂。XRD和H₂-TPR分析表明, 焙烧温度高于700 ℃, 活性组分与载体具有强烈的金属-载体相互作用(SMSI), 具体表现为活性组分前驱体以尖晶石NiAl₂O₄的形式存在。反应后催化剂的XRD、TG-DTG、TPH等表征结果表明, cat-700和cat-800试样的Ni晶粒尺寸分别为9.8和8.7 nm, 小于cat-500和cat-600试样(分别为15.7和13.6 nm), 分散性更好; 且催化剂表面积炭为丝状碳, 其不会导致催化剂失活, 但大量积累会引起床层压降升高, 影响催化剂的反应性能。cat-800试样110 h寿命试验表明, 高温焙烧制备的Ni基催化剂活性和稳定性均较高, CO₂转化率达95%左右, 失活速率仅为0.0536%/h。

关键词: CH₄/CO₂重整, NiO/γ-Al₂O₃催化剂, 焙烧温度, NiAl₂O₄

Abstract:

A series of NiO/γ-Al₂O₃ catalysts for CH₄/CO₂ reforming were prepared by altering calcination temperature using hydrolysis-deposition method, and recorded as cat-500, cat-600, cat-700, and cat-800 according to the calcination temperature. XRD and H₂-TPR results showed that there was a strong metal-support interaction (SMSI) in the form of NiAl₂O₄ spinel in the prepared catalyst when the calcination temperature was as high as 700 ℃. Results of XRD, TG-DTG and TPH for the spent catalysts showed that the Ni grain size of cat-700 and cat-800 catalysts was 9.8 nm and 8.7 nm, respectively, lower than that of cat-500 and cat-600 catalysts (15.7 nm and 13.6 nm, respectively), indicating well dispersion of Ni grain. The deposited carbon during reaction was assigned to filamentous one, massive accumulation of which would increase bed pressure drop and decrease catalyst performance. Long term stability test demonstrated that the conversion of CO₂ over cat-800 catalyst was up to 95% and kept stable in 110 h.

Key words: CH₄/CO₂ reforming, NiO/γ-Al₂O₃ catalyst, calcination temperature, NiAl₂O₄ spinel

中图分类号:

O643

莫文龙, 马凤云, 刘月娥, 刘景梅, 钟梅, 艾沙·努拉洪. 焙烧温度对CO₂-CH₄重整制合成气NiO/γ-Al₂O₃催化剂性能的影响[J]. 无机材料学报, 2016, 31(3): 234-240.

MO Wen-Long, MA Feng-Yun, LIU Yue-E, LIU Jing-Mei, ZHONG Mei, Aisha· Nulahong. Influence of Calcination Temperature on Performance of NiO/γ-Al₂O₃ Catalyst for CO₂-CH₄ Reforming to Produce Syngas[J]. Journal of Inorganic Materials, 2016, 31(3): 234-240.

图/表 10

表1 催化剂的孔结构参数测试结果

Table 1 Textural properties of the catalysts

Catalysts	A/(m²·g^-1)	V/(m³·g^-1)	d/nm
γ-Al₂O₃	197	0.42	3.24
cat-500	154	0.22	3.90
cat-600	150	0.21	3.91
cat-700	133	0.20	4.05
cat-800	107	0.17	4.08

图1 催化剂的XRD图谱

Fig. 1 XRD patterns of the catalysts

图2 催化剂的H2-TPR结果

Fig. 2 H2-TPR spectra of the catalysts

图3 催化剂的(a)CO2-TPD和(b)CH4-TPD表征

Fig. 3 (a) CO2-TPD and (b) CH4-TPD profiles of the catalysts

图4 催化剂的活性和选择性评价结果

Fig. 4 Conversion and selectivity of the catalysts

图5 cat-800催化剂上CH4转化率随反应温度的变化

Fig. 5 Conversion of CH4 over cat-800 catalyst

图6 反应后催化剂的XRD图谱

Fig. 6 XRD patterns of spent catalysts

图7 反应后催化剂的TG-DTG曲线

Fig. 7 TG-DTG curves of spent catalysts

图8 反应后试样的TPH表征结果

Fig. 8 TPH results of spent catalysts

图9 cat-500和cat-800试样的寿命试验结果

Fig. 9 Stability test over cat-500 and cat-800 catalysts

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焙烧温度对CO₂-CH₄重整制合成气NiO/γ-Al₂O₃催化剂性能的影响

Influence of Calcination Temperature on Performance of NiO/γ-Al₂O₃ Catalyst for CO₂-CH₄ Reforming to Produce Syngas

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