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B助剂对Ni2P/MCM-41催化剂结构及其加氢性能的影响
宋华1,代雪亚1,朱天汉1,秦浩1,宋华林2,李锋1
(1.东北石油大学化学化工学院,黑龙江大庆 163318;2.牡丹江医学院,黑龙江牡丹江 157011)
摘要:
采用程序升温还原法制备B改性的Ni2P/MCM-41催化剂,结合X-射线衍射(XRD)、N2等温吸附、CO吸附、吡啶吸附红外光谱(Py-FTIR)、X-射线光电子能谱(XPS)、透射电镜(TEM)等手段对催化剂进行表征。考察不同B质量分数(1%~3%)对Ni2P/MCM-41催化剂的结构和加氢脱氧(HDO)、加氢脱硫(HDS)性能的影响。结果表明:B的引入能促进较小粒径、较高分散度的Ni2P相的生成,减少催化剂表面的磷富集,增加暴露的Ni活性位的数量,增大催化剂的比表面积;B的引入显著增加催化剂的L酸量,进而增加总酸量;B改性催化剂的HDO和HDS活性均高于不含B的催化剂,且当B的质量分数为2%时催化活性最佳,此时HDO反应转化率达到95%,无氧产率达82%,HDS反应转化率达到97%。
关键词:  磷化镍    加氢脱氧  加氢脱硫  改性
DOI:10.3969/j.issn.1673-5005.2019.05.019
分类号::O 643.361
文献标识码:A
基金项目:国家自然科学基金项目(21276048);黑龙江省自然科学基金项目(ZD201201);黑龙江省教育厅面上项目(12541060)
Effect of boron promoter on structure and hydrogenation activity of Ni2P/MCM-41 catalysts
SONG Hua1, DAI Xueya1, ZHU Tianhan1, QIN Hao1, SONG Hualin2, LI Feng1
(1.Chemical Engineering in Northeast Petroleum University, Daqing 163318, China;2.Mudanjiang Medical University, Mudanjiang 157011, China)
Abstract:
A series of boron modified Ni2P/MCM-41 catalysts were prepared by temperature programmed reduction, which were characterized by X-ray diffraction (XRD), N2-adsorption specific surface area measurements, CO uptake, Py-FT-IR, X-ray photoelectron spectroscopy (XPS), and TEM. The effect of boron content (from 1% to 3%) on the structure and catalytic activity of Ni2P/MCM-41 was investigated. The results indicate that the boron can promote the formation of smaller crystallite size and better dispersion of Ni2P active phase particles. The enrichment of phosphorus on the surface of catalyst is suppressed, through which the specific surface area is increased and more Ni active sites are exposed. It is also found that the L acidity of catalyst is enhanced significantly after the incorporation of boron, which results in the improvement of total acidity. The HDO and HDS activity of the boron modified catalyst is higher than those of the original catalyst. When the boron content is 2%, the catalytic acitivity is the best. The HDO conversion reaches 95% and the yield of O-free products reaches 82%. And the HDS conversion is 97%.
Key words:  nickel phosphide  boron  hydrodeoxygenation  hydrodesulfurization  modification
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