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在三重整甲烷工艺的进料流中比较二氧化碳与甲烷部分氧化的效果。

The effect of carbon dioxide in the feed stream of tri-reforming of methane process compared to the partial oxidation of methane.

机构信息

Department of Chemical Engineering, University of São Paulo, São Paulo, SP, Brazil.

Department of Chemical Engineering, São Paulo, Brazil.

出版信息

Environ Sci Pollut Res Int. 2023 Feb;30(7):19111-19119. doi: 10.1007/s11356-022-23474-y. Epub 2022 Oct 12.

Abstract

In this work, we studied the effect of CO in the feed stream of the TRM process performance of nickel supported on LaFeO perovskite for hydrogen production compared to the POM reaction. The perovskite and nickel supported on LaFeO were synthesized and characterized by thermogravimetric analysis (TGA/DTA), X-ray diffraction (XRD), transmission electron microscopy (TEM), and programmed reduction temperature (TPR). The catalytic tests were carried out in temperatures varying from 700 to 800 °C with feed flow of 350 cm/min and 200 cm/min for TRM and POM, respectively. The hydrogen selectivity for the tri-reforming was 78%, while for the partial oxidation reaction, only 55% H at 700 °C. Results showed that the hydrogen selectivity for the Ni/LaFeO catalyst is significantly higher for the tri-reforming process, suggesting that CO enhanced the hydrogen selectivity compared to the partial oxidation of methane. Analyses by Raman spectroscopy and thermogravimetric calculations showed structural modifications of the catalysts after the reaction. The Raman spectrum showed segregated NiO and FeO and low carbon formation at 700 °C. The proposed mechanism suggests methane and oxygen adsorption, lattice oxygen and CO on surface active sites, and vacancies for both reactions.

摘要

在这项工作中,我们研究了在 TRM 过程中,与 POM 反应相比,进料流中 CO 对负载于 LaFeO 钙钛矿上的镍的制氢性能的影响。通过热重分析(TGA/DTA)、X 射线衍射(XRD)、透射电子显微镜(TEM)和程序升温还原(TPR)对钙钛矿和负载于 LaFeO 上的镍进行了合成和表征。在 700 至 800°C 的温度范围内进行了催化测试,TRM 和 POM 的进料流量分别为 350 cm/min 和 200 cm/min。三重整的氢气选择性为 78%,而在 700°C 时,部分氧化反应的氢气选择性仅为 55%。结果表明,对于三重整过程,Ni/LaFeO 催化剂的氢气选择性显著提高,这表明与甲烷的部分氧化相比,CO 提高了氢气选择性。拉曼光谱和热重计算分析表明,反应后催化剂的结构发生了变化。拉曼光谱显示在 700°C 时 NiO 和 FeO 发生了分离,且形成了少量的碳。提出的反应机理表明,甲烷和氧气在活性位上吸附,晶格氧和 CO 在表面活性位上吸附,两种反应都形成了空位。

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