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通过调控锡改性 ZSM-5 催化剂的结构来调控生物质在位催化裂解制备低碳烯烃或芳烃。

Regulating light olefins or aromatics production in ex-situ catalytic pyrolysis of biomass by engineering the structure of tin modified ZSM-5 catalyst.

机构信息

State Key Lab of Heavy Oil Processing, China University of Petroleum, Qingdao 266580, China.

SINOPEC Qingdao Refining and Chemical Co., Ltd., Qingdao 266500, China.

出版信息

Bioresour Technol. 2021 Jun;330:124975. doi: 10.1016/j.biortech.2021.124975. Epub 2021 Mar 13.

Abstract

Valorization of biomass to olefin or aromatics harbours tremendous practical value due to growing concerns about sustainable production of chemicals. Herein, the olefin or aromatics yields of ex-situ catalytic pyrolysis of pine can be regulated by impregnating Sn on hollow-structured ZSM-5 (M-ZSM-5) and microporous ZSM-5 catalysts in fixed-bed reactor, respectively. Results showed that Sn/ZSM-5 catalyst simultaneously increased medium acidic sites and maintained strong acidic sites, which obtained the maximum carbon yield of aromatics (33.77%) due to enhanced cracking and deoxygenation reactions. In addition, Sn boosted alkylation between olefin and aromatics, generating more alkylbenzene. In contrast, Sn/M-ZSM-5 catalyst produced the highest olefins carbon yield (12.39%) because the reduction of strong acidic sites and microporous volume inhibited the olefin aromatization. Moreover, olefins were easier to desorb from Sn/M-ZSM-5 due to the enhanced mass transfer ability, which weakened the alkylation reactions. The synergistic effect harbours great significance to manipulate the distribution of products.

摘要

由于人们越来越关注化学品的可持续生产,因此将生物质转化为烯烃或芳烃具有巨大的实际价值。在此,通过在固定床反应器中分别浸渍 Sn 于中空结构 ZSM-5(M-ZSM-5)和微孔 ZSM-5 催化剂,可调节原位催化热解松针的烯烃或芳烃产率。结果表明,Sn/ZSM-5 催化剂同时增加了中强酸位并保持了强酸位,由于增强了裂解和脱氧反应,从而获得了芳烃(33.77%)的最大碳收率。此外,Sn 促进了烯烃和芳烃之间的烷基化反应,生成了更多的烷基苯。相比之下,Sn/M-ZSM-5 催化剂产生了最高的烯烃碳收率(12.39%),因为强酸位和微孔体积的减少抑制了烯烃芳构化。此外,由于增强了传质能力,烯烃更容易从 Sn/M-ZSM-5 中解吸,从而减弱了烷基化反应。协同效应对于控制产物分布具有重要意义。

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