Abstract

The direct hydrogenation of CO2 to dimethyl ether (DME) is a promising technology for CO2 valorisation. In this work, a 1D phenomenological reactor model is developed to evaluate and optimize the performance of a membrane reactor for this conversion, otherwise limited by thermodynamic equilibrium and temperature gradients. The co-current circulation of a sweep gas stream through the permeation zone promotes both water and heat removal from the reaction zone, thus increasing overall DME yield (from 44% to 64%). The membrane properties in terms of water permeability (i.e., 4·10−7 mol·Pa−1m−2s−1) and selectivity (i.e., 50 towards H2, 30 towards CO2 and CO, 10 towards methanol), for optimal reactor performance have been determined considering, for the first time, non-ideal separation and non-isothermal operation. Thus, this work sheds light into suitable membrane materials for this applications. Then, the non-isothermal performance of the membrane reactor was analysed as a function of the process parameters (i.e., the sweep gas to feed flow ratio, the gradient of total pressure across the membrane, the inlet temperature to the reaction and permeation zone and the feed composition). Owing to its ability to remove 96% of the water produced in this reaction, the proposed membrane reactor outperforms a conventional packed bed for the same application (i.e., with 36% and 46% improvement in CO2 conversion and DME yield, respectively). The results of this work demonstrate the potential of the membrane reactor to make the CO2 conversion to DME a feasible process.

Highlights

  • The growing concerns about CO2 emissions [1,2], and its impact on climate change are driving the research agenda towards more sustain­ able processes

  • Owing to its ability to remove 96% of the water produced in this reaction, the proposed membrane reactor outperforms a conventional packed bed for the same application

  • While the existing technologies for both methanol and dimethyl ether (DME) rely on fossil-based syngas [19,20], leading again to environmental problems [21,22], recent research assesses the prospects of replacing the syngas by CO2/H2 feed [7,23], according to the following scheme: CO2 hydrogenation: CO2 + 3H2 CH3OH + H2O ΔH0=− 49.5 kJ/mol (1)

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Summary

Introduction

The growing concerns about CO2 emissions [1,2], and its impact on climate change are driving the research agenda towards more sustain­ able processes. DME is a clean burning fuel that can replace LPG or diesel without any (or limited) changes in the existing engines [15,16]. The indirect route is based on the initial conversion of syngas to methanol as intermediate product, and its subsequent dehydration to DME. The second route is the direct synthesis of DME from syngas in a single reactor. While the existing technologies for both methanol and DME rely on fossil-based syngas [19,20], leading again to environmental problems [21,22], recent research assesses the prospects of replacing the syngas by CO2/H2 feed [7,23], according to the following scheme: CO2 hydrogenation: CO2 + 3H2 CH3OH + H2O ΔH0=− 49.5 kJ/mol (1)

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