Study of Catalytic Properties of the HoxMg1-xAl2O4 Modified HZSM-5 Zeolite in Conversion of Methanol to C2-C4 Alkenes and p-Xylene

N. I. Makhmudova, E. S. Mammadov, F. S. Kerimli, T. M. Ilyasli, N. Akhmedova, S. E. Mammadov
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Abstract

Selective conversion of methanol to C2-C4 alkenes and p-xylene is one of the appealing chemical routes. Currently, there are no effective catalysts for the co-production of C2-C4 alkenes and p-xylene from methanol. To date, modified medium-pore ZSM-5 zeolites are considered one of the excellent candidates for the development of selective catalysts for the conversion of methanol to lower alkenes and aromatic hydrocarbons. In this paper, nanosized (30-33nm) powders of HoхMg1-хAl2O4 spinel structure were obtained by the method of combustion of nitrate solutions of aluminium, magnesium, holmium, diethylmalonate and hydrazine monohydrate with the further calcination of nanopowders at 1000 °C. Obtained nanopowders used in the preparation of a solid-phase catalytic composition of HoхMg1-хAl2O4-HZSM-5. Various physico-chemical properties of the catalytic composition were investigated using X-ray diffraction (XRD), pyridine adsorption (BİO-RAD FTS 3000 MX) and low-temperature nitrogen adsorption (BET) techniques. The textural properties and acidity of the catalysts were altered by adjusting the nanopowder concentration (1.0-5.0 wt.%) in the catalytic composition. The conversion of methanol in the presence of the catalytic compositions was carried out in flow-type fixed-bed catalytic reactor at 400 °C, in the presence of nitrogen carrier gas with 1.0 h-1 flow rate. A correlation between the selectivity to C2-C4 alkenes and p-xylene with a ratio of Lewis (L) and Brønsted (B) acid sites and the volume of the catalyst pore, the amount of the modifier in the catalytic system has been established. As the amount of HoхMg1-хAl2O4 nanopowder increases, the ratio of B/L acid sites and the volume of the catalyst pore decrease, which play a significant role in the increase of the selectivity to C2-C4 alkenes and p-xylene. Maximum yield of C2-C4 alkenes (31.6%) and selectivity to p-xylene (80.5%) is achieved on a catalytic composition containing 5.0 wt.% HoxMg1-xAl2O4. Copyright © 2022 by Authors, Published by BCREC Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0). 
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HoxMg1-xAl2O4改性HZSM-5沸石催化甲醇转化为C2-C4烯烃和对二甲苯的性能研究
甲醇选择性转化为C2-C4烯烃和对二甲苯是很有吸引力的化学途径之一。目前还没有有效的催化剂用于甲醇联产C2-C4烯烃和对二甲苯。迄今为止,改性的中孔ZSM-5沸石被认为是开发甲醇转化为低烯烃和芳烃的选择性催化剂的优秀候选者之一。本文采用铝、镁、钬、丙二酸二乙酯和一水合肼的硝酸溶液,在1000℃下进一步煅烧的方法,得到了HoхMg1-хAl2O4尖晶石结构的纳米级(30-33nm)粉体。所得纳米粉末用于制备固体相催化组合物HoхMg1-хAl2O4-HZSM-5。采用x射线衍射(XRD)、吡啶吸附(BİO-RAD FTS 3000 MX)和低温氮吸附(BET)技术研究了催化组份的各种物理化学性质。通过调整催化剂组成中纳米粉的浓度(1.0 ~ 5.0 wt.%),可以改变催化剂的结构性质和酸度。在流量为1.0 h-1的氮气载气存在下,在400℃的流动式固定床催化反应器中对甲醇进行了催化组合物存在下的转化。建立了催化剂对C2-C4烯烃和对二甲苯的选择性与Lewis (L)和Brønsted (B)酸位比、催化剂孔体积、改性剂用量之间的关系。随着HoхMg1-хAl2O4纳米粉体用量的增加,B/L酸位比和催化剂孔体积的减小,对C2-C4烯烃和对二甲苯选择性的提高起着重要作用。在含有5.0 wt.% HoxMg1-xAl2O4的催化组合物上,C2-C4烯烃的最大收率为31.6%,对二甲苯的选择性为80.5%。版权所有©2022作者所有,BCREC集团出版。这是一篇基于CC BY-SA许可(https://creativecommons.org/licenses/by-sa/4.0)的开放获取文章。
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