Effect of Mg modification on the catalytic performance of Co/γ-Al2O3-TiO2 in the combustion of propane
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摘要: 采用分步浸渍法制备了系列Mg改性的Co/γ-Al2O3-TiO2催化剂，通过X射线衍射（XRD）、紫外可见漫反射光谱（DR-UV-vis）、N2吸附-脱附（BET）、X射线光电子能谱（XPS）和H2程序升温还原（H2-TPR）等技术对催化剂进行表征，并考察了其对丙烷燃烧的催化性能。结果表明，Co在原始γ-Al2O3-TiO2载体和Mg改性MgO/γ-Al2O3-TiO2载体上均以Co3O4的形式存在；Mg掺入后与Al2O3作用形成MgAl2O4尖晶石，改善了载体的织构性质，提升了Co3O4在催化剂载体表面的暴露数量和分散程度。此外，MgAl2O4与Co3O4相互作用提升了Co3O4颗粒表面Co3+/Co2+和Oads/Olatt的比例，并削弱了Co-O键键能，从而提升了其对丙烷的催化燃烧活性。当Mg负载量为15%（质量分数）时，在Co/MgO（15%）/γ-Al2O3-TiO2催化剂上进行丙烷燃烧，丙烷90%转化率的温度比无Mg掺杂的Co/γ-Al2O3-TiO2催化剂的降低了45℃，并且连续反应40 h其活性保持稳定。
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关键词:
- Co3O4 /
- MgAl2O4尖晶石 /
- 催化燃烧 /
- 丙烷 /
- 相互作用
Abstract: A series of Mg-modified Co/MgO/γ-Al2O3-TiO2 catalysts were prepared by multi-step impregnation method and characterized by X-ray diffraction (XRD), diffuse reflectance visible ultra violet spectroscopy (DR-UV-vis), N2 adsorption-desorption, X-ray photoelectron spectroscopy (XPS) and H2 temperature-programmed reduction (H2-TPR); the effect of Mg modification on the catalytic performance of Co/MgO/γ-Al2O3-TiO2 in the combustion of propane was investigated. The results indicate that Co exists in the form of Co3O4 on both the pristine γ-Al2O3-TiO2 and Mg-modified MgO/γ-Al2O3-TiO2 supports; Mg added in the MgO/γ-Al2O3-TiO2 support interacts with Al2O3, forming MgAl2O4 spinel, which can improve the textural properties and promote the dispersion of Co3O4. Moreover, the interaction between MgAl2O4 and Co3O4 can increase the proportions of Co3+/Co2+ and Oads/Olatt on the catalyst surface, weaken the Co-O bond, and thereby enhance the activity of Co-based catalyst in propane combustion. For the propane combustion over the Co/MgO(15%)/γ-Al2O3-TiO2 catalyst with an Mg loading of 15%, the temperature to achieve a propane conversion of 90% is decreased by 45℃ in comparison with that over the Mg-free Co/γ-Al2O3-TiO2 catalyst; moreover, the Co/MgO(15%)/γ-Al2O3-TiO2 catalyst exhibits excellent stability and no decrease in the activity is observed in a 40 h continuous reaction test for propane combustion.-
Key words:
- Co3O4 /
- MgAl2O4 spinel /
- catalytic combustion /
- propane /
- interaction
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图 1 不同催化剂催化燃烧丙烷活性; (b)lnr与1/RT关系图; (c) Co/Mg(15%)/AlTi在不同GHSV下催化燃烧丙烷活性; (d)Co/Mg(15%)/AlTi的稳定性评价
Figure 1 (a) Activity of various catalysts in propane combustion; (b) Arrhenius plots of lnr and 1/RT for the Co/AlTi and Co/Mg(15)/AlTi catalysts; (c) catalytic activity of Co/Mg(15%)/AlTi in propane combustion under different GHSVs; (d) long-term stability test of Co/Mg(15%)/AlTi. The feed consisted of 0.3% (volume ratio) propane and balanced air, with a gas hourly space velocity (GHSV) of 15000mL/(h·g) in the graphs of (a), (b) and (d)
图 2 催化剂的XRD谱图
Figure 2 XRD patterns (a) and magnification at 55°-75° (b) of various catalysts
a: Co/AlTi; b: Mg(15%)/AlTi; c: Co/Mg(15%)/AlTi
图 3 催化剂的紫外可见漫反射光谱(DR-UV-vis)谱图
Figure 3 DR-UV-vis spectra of Co/Mg(15%)/AlTi (a), Co/AlTi (b), and Mg(15%)/AlTi (c)
图 4 催化剂的N2吸附-脱附等温线(a)和孔径分布(b)
Figure 4 N2 adsorption-desorption isotherms (a) and pore size distribution (b) of various catalysts
a: Co/AlTi; b: Mg(15%)/AlTi; c: Co/Mg(15%)/AlTi
图 5 催化剂的XPS谱图
Figure 5 Co 2p (a) and O 1s XPS spectra (b) of various catalysts
a: Co/Mg(15%)/AlTi; b: Co/AlTi; c: Mg(15%)/AlTi
图 6 催化剂的H2-TPR谱图
Figure 6 H2-TPR profiles of Co/Mg(15%)/AlTi (a), Co/AlTi (b) and Mg(15%)/AlTi (c)
表 1 催化剂与载体的织构性质
Table 1 Texture properties of catalysts and support
Sample Surface area A/(m2·g-1) Pore volume v/(cm3·g-1) Pore size d/nm AlTi 68.6 0.239 13.1 Mg(15%)/AlTi 73.3 0.225 8.4 Co/AlTi 61.6 0.216 13.1 Co/Mg(15%)/AlTi 69.3 0.229 8.3 
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表 2 催化剂的XPS参数
Table 2 XPS results of various catalysts
Catalyst Element contents wmol/% Binding energy E/eV Co2+ Co3+ Al Mg Co O Co3+/Co2+ Oads/Olatt Mg(15%)/AlTi 20.42 2.81 0.00 76.77 - - - 1.59 Co/AlTi 22.61 0.00 1.88 75.51 782.4 780.2 0.71 1.46 Co/Mg(15%)/AlTi 18.94 2.71 2.43 75.92 781.9 779.9 0.77 1.65
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