球形氧化铝的制备及其在丙烷脱氢催化剂中的应用

doi:10.11962/1006-4990.2019-0412

摘要/Abstract

摘要：

以中和法、水热法、醇铝法和铝粉盐酸回流法合成的氧化铝前驱体为原料分别制备球形氧化铝载体（记为ZH、SR、ST和SOL）,通过强度仪、X射线荧光光谱仪（XRF）、低温氮气吸附-脱附、扫描电镜（SEM）、氨程序升温脱附（NH₃-TPD）等手段对氧化铝载体进行表征,以丙烷脱氢为探针反应研究了氧化铝的制备方法对催化剂（Pt-Sn-K/Al₂O₃）脱氢性能的影响。实验结果表明：不同方法合成的氧化铝前驱体均制备出高强度的球形氧化铝载体,其中水热法和醇铝法制备的载体还具有较大的孔容和适中的比表面积;前驱体的制备方法对催化剂的酸性影响较大,中和法制备的氧化铝载体制备的催化剂主要是弱-中强酸中心,其他方法制备的氧化铝载体制备的催化剂为弱酸中心,催化剂酸量由大到小的顺序为ZH-CAT、SOL-CAT、ST-CAT、SR-CAT;评价结果表明,醇铝法和水热法制备的载体应用于丙烷脱氢催化剂表现出良好的性能,相当于甚至优于工业剂水平。

关键词: 脱氢, 丙烷, 氧化铝, 催化剂

Abstract:

Alumina precursors synthesized by neutralization method,hydrothermal method,alcoholic aluminium method and aluminium powder-hydrochloric acid reflux method were used as raw materials to prepare spherical alumina carriers which are marked as ZH、SR、ST and SOL respectively.The samples were characterized by strength tester,XRF,BET,SEM and NH₃-TPD,etc.The effect of the alumina support on the performance of Pt-Sn-K/Al₂O₃ catalysts in the dehydrogenation of propane was investigated.The results showed that the alumina precursors synthesized by different methods have been used to prepared spherical alumina supports with high strength.Especially the alumina supports prepared by hydrothermal method and alcoholic aluminium method also had large pore volume and moderate specific surface area.The preparation methods of precursors had greater influence on the acidity of catalysts,while neutralization catalyst was mainly weak-medium-strong acid center and other catalysts were mainly weak acid center,and the order of acidity was ZH-CAT>SOL-CAT>ST-CAT>SR-CAT.The evaluation results showed that the supports prepared by alcoholic aluminium method and hydrothermal method had good performance for propane dehydrogenation catalyst,which was equivalent to or even superior to the industrial catalyst.

Key words: dehydrogenation, propane, alumina, catalyst

中图分类号:

TQ133.1

杨文建,孟广莹,李晓云,孙彦民,蔡奇,郭秋双. 球形氧化铝的制备及其在丙烷脱氢催化剂中的应用[J]. 无机盐工业, 2020, 52(6): 87-91.

Yang Wenjian,Meng Guangying,Li Xiaoyun,Sun Yanmin,Cai Qi,Guo Qiushuang. Preparation of spherical alumina and its application in PDH[J]. Inorganic Chemicals Industry, 2020, 52(6): 87-91.

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参考文献 11

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样品	w（Al₂O₃）	w（Na₂O）	w（SiO₂）	w（Fe₂O₃）	w（Cl）
ZH	99.6	0.050	0.062	0.010	—
ST	99.8	0.005	0.010	—	—
SR	99.6	0.041	0.061	0.009	—
SOL	98.5	0.008	0.007	0.013	0.9

样品	孔容/（mL·g^-1）	比表面积/（m²·g^-1）	平均孔径/nm
ZH	0.59	141	16.7
SOL	0.79	81	39.0
ST	0.68	106	25.7
SR	0.66	89	29.7

样品	平均强度/N	表观密度/（g·mL^-1）	强度离散系数
ZH	51.2	0.67	0.17
SOL	34.1	0.58	0.26
ST	42.0	0.64	0.19
SR	38.7	0.64	0.21

样品	酸量/（mmol·g^-1）	样品	酸量/（mmol·g^-1）
ZH-CAT	0.294	SR-CAT	0.187
ST-CAT	0.225	SOL-CAT	0.240

催化剂	平均转化率/%	平均选择性/%	平均收率/%
ZH-CAT	41.8	93.2	39.0
SOL-CAT	42.0	94.5	39.7
ST-CAT	41.9	95.1	39.8
SR-CAT	42.0	95.2	40.0
DH-CAT	41.9	95.2	39.8

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