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Title: Renewable Acrylonitrile Production

Abstract

Acrylonitrile (ACN) is a petroleum-derived compound used in resins, polymers, acrylics, and carbon fiber. We present a process for renewable ACN production using 3-hydroxypropionic acid (3-HP), which can be produced microbially from sugars. The process achieves ACN molar yields exceeding 90% from ethyl 3-hydroxypropanoate (ethyl 3-HP) via dehydration and nitrilation with ammonia over an inexpensive titanium dioxide solid acid catalyst. We further describe an integrated process modeled at scale that is based on this chemistry and achieves near-quantitative ACN yields (98 +/- 2%) from ethyl acrylate. This endothermic approach eliminates runaway reaction hazards and achieves higher yields than the standard propylene ammoxidation process. Avoidance of hydrogen cyanide as a by-product also improves process safety and mitigates product handling requirements.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [1];  [1];  [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [1];  [1];  [1];  [2];  [2];  [3];  [3];  [3];  [4];  [5]
  1. National Renewable Energy Laboratory (NREL), Golden, CO (United States)
  2. University of Colorado
  3. Johnson Matthey Technology Centre
  4. MATRIC
  5. Formerly NREL
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Bioenergy Technologies Office (EE-3B)
OSTI Identifier:
1417799
Report Number(s):
NREL/JA-5100-69050
Journal ID: ISSN 0036-8075
DOE Contract Number:
AC36-08GO28308
Resource Type:
Journal Article
Resource Relation:
Journal Name: Science; Journal Volume: 358; Journal Issue: 6368
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; acrylonitrile; ACN; renewable; 3-hydroxypropionic acid; 3-HP; lignocellulose; sugars

Citation Formats

Beckham, Gregg T, Karp, Eric M, Eaton, Todd R, Sanchez i Nogue, Violeta, Vorotnikov, Vassili, Biddy, Mary J, Tan, Eric C, Brandner, David, Manker, Lorenz, Michener, William E, Vardon, Derek R, Bratis, Adam D, Liu, Rongming, Gill, Ryan T., Gilhespy, Michelle, Skoufa, Zinovia, Watson, Michael J., Fruchey, O. Stanley, and Cywar, Robin M. Renewable Acrylonitrile Production. United States: N. p., 2017. Web. doi:10.1126/science.aan1059.
Beckham, Gregg T, Karp, Eric M, Eaton, Todd R, Sanchez i Nogue, Violeta, Vorotnikov, Vassili, Biddy, Mary J, Tan, Eric C, Brandner, David, Manker, Lorenz, Michener, William E, Vardon, Derek R, Bratis, Adam D, Liu, Rongming, Gill, Ryan T., Gilhespy, Michelle, Skoufa, Zinovia, Watson, Michael J., Fruchey, O. Stanley, & Cywar, Robin M. Renewable Acrylonitrile Production. United States. doi:10.1126/science.aan1059.
Beckham, Gregg T, Karp, Eric M, Eaton, Todd R, Sanchez i Nogue, Violeta, Vorotnikov, Vassili, Biddy, Mary J, Tan, Eric C, Brandner, David, Manker, Lorenz, Michener, William E, Vardon, Derek R, Bratis, Adam D, Liu, Rongming, Gill, Ryan T., Gilhespy, Michelle, Skoufa, Zinovia, Watson, Michael J., Fruchey, O. Stanley, and Cywar, Robin M. Fri . "Renewable Acrylonitrile Production". United States. doi:10.1126/science.aan1059.
@article{osti_1417799,
title = {Renewable Acrylonitrile Production},
author = {Beckham, Gregg T and Karp, Eric M and Eaton, Todd R and Sanchez i Nogue, Violeta and Vorotnikov, Vassili and Biddy, Mary J and Tan, Eric C and Brandner, David and Manker, Lorenz and Michener, William E and Vardon, Derek R and Bratis, Adam D and Liu, Rongming and Gill, Ryan T. and Gilhespy, Michelle and Skoufa, Zinovia and Watson, Michael J. and Fruchey, O. Stanley and Cywar, Robin M.},
abstractNote = {Acrylonitrile (ACN) is a petroleum-derived compound used in resins, polymers, acrylics, and carbon fiber. We present a process for renewable ACN production using 3-hydroxypropionic acid (3-HP), which can be produced microbially from sugars. The process achieves ACN molar yields exceeding 90% from ethyl 3-hydroxypropanoate (ethyl 3-HP) via dehydration and nitrilation with ammonia over an inexpensive titanium dioxide solid acid catalyst. We further describe an integrated process modeled at scale that is based on this chemistry and achieves near-quantitative ACN yields (98 +/- 2%) from ethyl acrylate. This endothermic approach eliminates runaway reaction hazards and achieves higher yields than the standard propylene ammoxidation process. Avoidance of hydrogen cyanide as a by-product also improves process safety and mitigates product handling requirements.},
doi = {10.1126/science.aan1059},
journal = {Science},
number = 6368,
volume = 358,
place = {United States},
year = {Fri Dec 08 00:00:00 EST 2017},
month = {Fri Dec 08 00:00:00 EST 2017}
}
  • We report an approach for programming electrical conductivity of a bio-based leathery skin devised with a layer of 60 nm metallic nanoparticles. Lignin-based renewable shape-memory materials were made, for the first time, to program and restore the materials’ electrical conductivity after repeated deformation up to 100% strain amplitude, at a temperature 60–115 °C above the glass transition temperature (T g) of the rubbery matrix. We cross-linked lignin macromolecules with an acrylonitrile–butadiene rubbery melt in high quantities ranging from 40 to 60 wt % and processed the resulting thermoplastics into thin films. Chemical and physical networks within the polymeric materials significantlymore » enhanced key characteristics such as mechanical stiffness, strain fixity, and temperature-stimulated recovery of shape. The branched structures of the guaiacylpropane-dominant softwood lignin significantly improve the rubber’s T g and produced a film with stored and recoverable elastic work density that was an order of magnitude greater than those of the neat rubber and of samples made with syringylpropane-rich hardwood lignin. The devices could exhibit switching of conductivity before and after shape recovery.« less
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