磷酸处理提高Hβ催化剂低温醚化活性的研究

石油炼制与化工 ›› 2016, Vol. 47 ›› Issue (3): 48-53.

磷酸处理提高Hβ催化剂低温醚化活性的研究

颜曦明,柯明,蒋庆哲,宋昭峥

中国石油大学（北京）重质油国家重点实验室

收稿日期:2015-08-04 修回日期:2015-09-06 出版日期:2016-03-12 发布日期:2016-02-26
通讯作者: 柯明 E-mail:keming@cup.edu.cn

IMPROVING LOW TEMPERATURE ACTIVITY OF Hβ ETHERIFICATION CATALYST BY PHOSPHORIC ACID TREATMENT

Received:2015-08-04 Revised:2015-09-06 Online:2016-03-12 Published:2016-02-26

摘要/Abstract

摘要：

针对分子筛低温醚化活性较差的缺点，采用磷酸溶液对Hβ基底催化剂进行处理，用XRD，BET，NH3-TPD，Py-IR等手段对酸处理前后的样品进行表征，并对其低温醚化性能进行考察。结果表明：磷酸处理对催化剂晶体结构无破坏作用，可提高硅铝比，使孔分布范围变宽，扩孔效果明显，催化剂的酸量和酸强度得到适度降低，而中强酸和B酸位数量明显增加；磷酸处理可以显著提高催化剂的低温醚化活性，酸处理形成的大孔有利于反应物和产物在孔道内的扩散，提高催化效率，而中强酸比例和B酸位的增加是提高低温醚化活性的关键，其中经0.5 mol/L磷酸处理的催化剂样品醚化效果最佳，异戊烯转化率可达65.04%，甲基叔戊基醚选择性为97.55%。

关键词: 醚化, 低温活性, Hβ, 甲基叔戊基醚, 磷酸

Abstract:

The low temperature etherification activity of molecular sieve is poor. Aimed at this shortcoming, using phosphoric acid solution acid treatment catalyst, the samples of before and after processing were characterized by XRD, XRF, BET, NH3-TPD and Py-IR. Results show that phosphoric acid treatment can maintaining catalyst crystal structure, increase the silica alumina mole ratio, wider pore size distribution, reaming effect obviously, acid amount and acid strength reduce moderately, but the number of strong acid site and the Br?nsted acid site increase significantly. The low temperature etherification activity of above catalysts was investigated in a micro fixed bed reactor. Results indicate that phosphoric acid treatment can significantly improve the low temperature etherification activity. The large pore size generated by acid treatment was beneficial to the diffusion of reactants and products and improved the catalytic efficiency. The increase of strong acid ratio and Br?nsted acid sites is the key to improve the low temperature etherification activity, while too high or too low of acid strength unfavorable to the etherification. The sample of 0.5PA has the best etherification activity, the conversion rate of isoamylene was 65.04%, and the selectivity of TAME was 97.55%.

Key words: etherification, low-temperature activity, Hβ, tertamyl methyl ether, phosphoric acid

颜曦明柯明蒋庆哲宋昭峥. 磷酸处理提高Hβ催化剂低温醚化活性的研究[J]. 石油炼制与化工, 2016, 47(3): 48-53.

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