Ammonia-Assisted Light Alkane Anti-coke Reforming on Isolated ReOxSites in Zeolite

Siavash Fadaeerayeni; Xinbin Yu; Erik Sarnello; Zhenghong Bao; Xiao Jiang; Raymond R. Unocic; Lingzhe Fang; Zili Wu; Tao Li; Yizhi Xiang

doi:10.1021/acscatal.2c00230

Ammonia-Assisted Light Alkane Anti-coke Reforming on Isolated ReO_xSites in Zeolite

Siavash Fadaeerayeni, Xinbin Yu, Erik Sarnello, Zhenghong Bao, Xiao Jiang, Raymond R. Unocic, Lingzhe Fang, Zili Wu, Tao Li, Yizhi Xiang

Research output: Contribution to journal › Article › peer-review

8 Scopus citations

Abstract

The conventional reforming produces H₂with stoichiometric amounts of CO and CO₂from hydrocarbons. Here, we show that CO_x-free H₂can be produced from ammonia-assisted reforming (ammoreforming) of natural gas liquids (C_nH_2n+2+ nNH₃= nHCN + (2n + 1) H₂, n = 2 or 3) at the same conditions as the steam reforming. Such a process co-produces HCN, which can be easily separated from H₂and used as value-added chemicals or for NH₃recycling through hydrolysis. The ammoreforming of ethane and propane was realized over the Re-modified HZSM-5 zeolite rather than the traditional Pt-based catalyst for the BMA process (methane ammoreforming). The specific activity of the Re/HZSM-5 catalysts at 650 °C is up to 1 mol_H₂/g_Re/min (or 180 min^-1) during ethane ammoreforming. The catalyst is highly coke resistant and shows only slight deactivation with a time-on-stream up to 20 h. Characterization of the fresh and used catalysts by X-ray absorption and Raman spectroscopies suggested that the isolated ReO_xsite grafted by AlO₄^-tetrahedral in the zeolite framework is responsible for the outstanding catalytic activity and coke resistibility.

Original language	English
Pages (from-to)	3165-3172
Number of pages	8
Journal	ACS Catalysis
Volume	12
Issue number	5
DOIs	https://doi.org/10.1021/acscatal.2c00230
State	Published - Mar 4 2022

Funding

Y.X. is grateful for the startup support from Mississippi State University. This research used resources of the Advanced Photon Source (XAS) and the Center for Nanophase Materials Sciences (Raman and STEM), the U.S. Department of Energy (DOE) Office of Science User Facilities operated for the DOE Office of Science by Argonne National Laboratory and Oak Ridge National Laboratory (ORNL), respectively. Work at ORNL was partly supported by DOE, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, Catalysis Science program.

Keywords

CO-free H
ammonia reforming
anti-coke
isolated ReO
light alkanes

Access to Document

10.1021/acscatal.2c00230

Cite this

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title = "Ammonia-Assisted Light Alkane Anti-coke Reforming on Isolated ReOxSites in Zeolite",

abstract = "The conventional reforming produces H2with stoichiometric amounts of CO and CO2from hydrocarbons. Here, we show that COx-free H2can be produced from ammonia-assisted reforming (ammoreforming) of natural gas liquids (CnH2n+2+ nNH3= nHCN + (2n + 1) H2, n = 2 or 3) at the same conditions as the steam reforming. Such a process co-produces HCN, which can be easily separated from H2and used as value-added chemicals or for NH3recycling through hydrolysis. The ammoreforming of ethane and propane was realized over the Re-modified HZSM-5 zeolite rather than the traditional Pt-based catalyst for the BMA process (methane ammoreforming). The specific activity of the Re/HZSM-5 catalysts at 650 °C is up to 1 molH2/gRe/min (or 180 min-1) during ethane ammoreforming. The catalyst is highly coke resistant and shows only slight deactivation with a time-on-stream up to 20 h. Characterization of the fresh and used catalysts by X-ray absorption and Raman spectroscopies suggested that the isolated ReOxsite grafted by AlO4-tetrahedral in the zeolite framework is responsible for the outstanding catalytic activity and coke resistibility.",

keywords = "CO-free H, ammonia reforming, anti-coke, isolated ReO, light alkanes",

author = "Siavash Fadaeerayeni and Xinbin Yu and Erik Sarnello and Zhenghong Bao and Xiao Jiang and Unocic, {Raymond R.} and Lingzhe Fang and Zili Wu and Tao Li and Yizhi Xiang",

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AU - Fadaeerayeni, Siavash

AU - Yu, Xinbin

AU - Sarnello, Erik

AU - Bao, Zhenghong

AU - Jiang, Xiao

AU - Unocic, Raymond R.

AU - Fang, Lingzhe

AU - Wu, Zili

AU - Li, Tao

AU - Xiang, Yizhi

PY - 2022/3/4

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AB - The conventional reforming produces H2with stoichiometric amounts of CO and CO2from hydrocarbons. Here, we show that COx-free H2can be produced from ammonia-assisted reforming (ammoreforming) of natural gas liquids (CnH2n+2+ nNH3= nHCN + (2n + 1) H2, n = 2 or 3) at the same conditions as the steam reforming. Such a process co-produces HCN, which can be easily separated from H2and used as value-added chemicals or for NH3recycling through hydrolysis. The ammoreforming of ethane and propane was realized over the Re-modified HZSM-5 zeolite rather than the traditional Pt-based catalyst for the BMA process (methane ammoreforming). The specific activity of the Re/HZSM-5 catalysts at 650 °C is up to 1 molH2/gRe/min (or 180 min-1) during ethane ammoreforming. The catalyst is highly coke resistant and shows only slight deactivation with a time-on-stream up to 20 h. Characterization of the fresh and used catalysts by X-ray absorption and Raman spectroscopies suggested that the isolated ReOxsite grafted by AlO4-tetrahedral in the zeolite framework is responsible for the outstanding catalytic activity and coke resistibility.

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