Kinetics of Direct Olefin Synthesis from Syngas over Mixed Beds of Zn–Zr Oxides and SAPO-34

DeWilde, Joseph F.; Ho, Christopher R.; Conner, James; Smith, Austin; Kirilin, Alexey V.; Malek, Andrzej; Witt, Paul M.

doi:10.1021/acs.iecr.1c03246

Kinetics of Direct Olefin Synthesis from Syngas over Mixed Beds of Zn–Zr Oxides and SAPO-34

Journal Article · Fri Sep 24 00:00:00 EDT 2021 · Industrial and Engineering Chemistry Research

DOI:https://doi.org/10.1021/acs.iecr.1c03246· OSTI ID:2007396

^[1]; ^[2]; Conner, James ^[2]; Smith, Austin ^[2]; ^[3]; Malek, Andrzej ^[2]; Witt, Paul M. ^[2]

The Dow Chemical Company, Midland, MI (United States); Dow Chemical Company
The Dow Chemical Company, Midland, MI (United States)
Dow Benelux B.V., Hoek (Netherlands)

A packed bed containing a physical mixture of both Zn–Zr mixed oxide catalyst and SAPO-34 converts syngas directly into a mixture of C₂–C₅ olefins and paraffins. Specifically, the mixed oxide catalyst is responsible for intermediate oxygenate synthesis from syngas while the molecular sieve catalyzes olefin synthesis from the oxygenate intermediates. Kinetic measurements with cofed propylene over each catalyst independently confirm olefin hydrogenation activity over both components of the composite bed. The addition of either water or CO to the feed drops the activity of propylene hydrogenation over the Zn–Zr oxide. In sum, under reaction conditions of syngas feed and produced water, olefin hydrogenation predominantly occurs over the SAPO-34 catalyst, rather than over the catalyst responsible for hydrogenating CO into oxygenate intermediates. Here, a developed kinetic model consistent with this conclusion describes measurements at differing feed compositions, temperatures, space velocities, and bed catalyst mixing ratios. Technoeconomic analysis of the process indicates that the olefin-to-paraffin ratio is a key performance metric for commercial scale syngas conversion and highlights the importance of considering olefin hydrogenation rates over the molecular sieve component.

View Accepted Manuscript (DOE)

Research Organization:: RAPID Manufacturing Institute, New York, NY (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: EE0007888

OSTI ID:: 2007396

Journal Information:: Industrial and Engineering Chemistry Research, Journal Name: Industrial and Engineering Chemistry Research Journal Issue: 39 Vol. 60; ISSN 0888-5885

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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