IP Library › Granted Patent US 12,286,390
Granted Patent B2
US 12,286,390 · App. 17/244,172 · Granted Apr 29, 2025

Systems and methods for producing nitriles

Inventors: Eric M. Karp (Denver, CO); Gregg Tyler Beckham (Golden, CO); Derek Richard Vardon (Lakewood, CO); Todd R. Eaton (Denver, CO)
Assignee: Alliance for Sustainable Energy, LLC
C07C253/22B01D3/009B01D15/08B01J21/04B01J21/063B01J21/08B01J23/20B01J27/16
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Quick Facts
Patent No.
US 12,286,390
App. No.
17/244,172
Granted
Apr 29, 2025
Kind
B2
Abstract

An aspect of the present disclosure is a method that includes a first reacting a molecule from at least one of a carboxylic acid, an ester of a carboxylic acid, and/or an anhydride with ammonia to form a nitrile, where the first reacting is catalyzed using an acid catalyst. In some embodiments of the present disclosure, the molecule may include at least one of acetic acid, lactic acid, and/or 3-hydroxyproprionic acid (3-HPA). In some embodiments of the present disclosure, the molecule may include at least one of methyl acetate, ethyl lactate, and/or ethyl 3-hydroxypropanoate (ethyl 3-HP). In some embodiments of the present disclosure, the anhydride may be acetic anhydride.

Claims (17)

1. A method comprising:

reacting a molecule comprising at least one of a carboxylic acid, an ester of a carboxylic acid, or an anhydride with ammonia to form acrylonitrile, wherein:

the reacting is catalyzed using a metal oxide catalyst excluding TiO 2 .

2. The method of claim 1 , wherein the molecule comprises at least one of lactic acid or 3-hydroxypropionic acid.

3. The method of claim 1 , wherein the molecule comprises at least one of ethyl lactate or ethyl 3-hydroxypropanoate.

4. The method of claim 1 , wherein the metal oxide catalyst comprises at least one of AlPO 4 , SiO 2 , Al 2 O 3 , NbO 2 , or Nb 2 O 5 .

5. A method comprising:

esterifying a carboxylic acid with an alcohol to produce an ester and water; and

nitrilating the ester to produce acrylonitrile, the alcohol, and water, wherein:

the nitrilating is performed by reacting the ester with ammonia over a metal oxide catalyst excluding TiO 2 .

6. The method of claim 5 , wherein the nitrilating is performed with both the ester and the ammonia in a gas phase.

7. The method of claim 5 , wherein the esterifying is performed by contacting the carboxylic acid and the alcohol with a mineral acid.

8. The method of claim 5 , wherein the nitrilating is performed at a molar ratio of the ester to the ammonia between 1:1 and 10:1.

9. The method of claim 5 , further comprising,

after the esterifying, dehydrating the ester to produce an unsaturated ester.

10. The method of claim 9 , wherein the dehydrating and the nitrilating are performed at substantially the same time.

11. The method of claim 5 , wherein the metal oxide catalyst comprises at least one of AlPO 4 , SiO 2 , Al 2 O 3 , NbO 2 , or Nb 2 O 5 .

Assignments (3)
CHANGE OF NAME Recorded Dec 16, 2025
From: ALLIANCE FOR SUSTAINABLE ENERGY, LLC
To: ALLIANCE FOR ENERGY INNOVATION, LLC
Reel/Frame 073993/0276 →
CONFIRMATORY LICENSE Recorded May 7, 2021
From: ALLIANCE FOR SUSTAINABLE ENERGY
To: UNITED STATES DEPARTMENT OF ENERGY
Reel/Frame 056168/0450 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded May 3, 2021
From: BECKHAM, GREGG TYLER; EATON, TODD R.; KARP, ERIC M.; VARDON, DEREK RICHARD
To: ALLIANCE FOR SUSTAINABLE ENERGY, LLC
Reel/Frame 056115/0372 →
Continuity (4)
Continuation In Part 15775632
Provisional Application 62437303 · Dec 21, 2016
Provisional Application 62297187 · Feb 19, 2016
Related Publication 20210253516A1 · Aug 19, 2021
References Cited (52)
US 2668175A · Reppe et al. · 1954 [cited by applicant]
US 3337610A · Bellringer et al. · 1967 [cited by applicant]
US 4008179A · Gasson et al. · 1977 [cited by applicant]
US 4179462A · Olivéet al. · 1979 [cited by applicant]
US 5138086A · Honda et al. · 1992 [cited by applicant]
US 5210296A · Cockrem et al. · 1993 [cited by applicant]
US 6005134A · Terasaka et al. · 1999 [cited by applicant]
US 6475759B1 · Carlson et al. · 2002 [cited by applicant]
US 20100048850A1 · Dubois et al. · 2010 [cited by applicant]
US 20110105791A1 · Kuppinger et al. · 2011 [cited by applicant]
US 20130313192A1 · Wang et al. · 2013 [cited by applicant]
US 20140045231A1 · Lynch et al. · 2014 [cited by applicant]
US 20140309451A1 · Tengler et al. · 2014 [cited by applicant]
US 20140330032A1 · Lynch et al. · 2014 [cited by applicant]
US 20140357880A1 · Brandhorst et al. · 2014 [cited by applicant]
US 20160264509A1 · Kaller et al. · 2016 [cited by applicant]
US 20180346411A1 · Karp et al. · 2018 [cited by applicant]
CN 10308032B · 2014 [cited by applicant]
EP 1520851A1 · 2005 [cited by applicant]
JP 2893216B2 · 1999 [cited by applicant]
JP 2002284753A · 2002 [cited by applicant]
RU 2440331C1 · 2012 [cited by applicant]
WO 2012033845A2 · 2012 [cited by applicant]
WO 2013192451A1 · 2013 [cited by applicant]
WO 2016068068A1 · 2016 [cited by applicant]
WO 2020185420A1 · 2020 [cited by applicant]
Vafaeezadeh et al., DFT investigation for “Fischer” esterification mechanism over silica-propyl-SO3H catalyst: Is the reaction reversible. Computational and Theoretical Chemistry, 2015, 1071, 27-32. [cited by examiner]
International Search Report and Written Opinion for International (PCT) Application PCT/US22/18345, mailing date Jul. 7, 2022, pp. 1-13. [cited by applicant]
Bedia et al., “A Kinetic Study of 2-propanol Dehydration on Carbon Acid Catalysts”, Journal of Catalysis, 2010, vol. 271, pp. 33-42. [cited by applicant]
Gao et al., “Structure—activity Relationships in NH3-SCR Over Cu-SSZ-13 as Probed by Reaction Kinetics and EPR Studies”, Journal of Catalysis, Apr. 2013, vol. 300, pp. 20-29. [cited by applicant]
Ghaffar et al., “Recent Trends in Lactic Acid Biotechnology: A Brief Review on Production to Purification”, Journal of Radiation Research and Applied Sciences, Apr. 2014, vol. 7, No. 2, pp. 222-229. [cited by applicant]
Guerrero-Perez et al., “New Reaction: Conversion of Glycerol into Acrylonitrile”, Chemistry & Sustainability Energy & Materials (ChemSusChem), 2008, vol. 1, pp. 511-513. [cited by applicant]
Hiofvendahl et al., “Factors Affecting the Fermentative Lactic Acid Production from Renewable Resources”, Enzyme and Microbial Technology, Feb. 2000, vol. 26, No. 2-4, pp. 87-107. [cited by applicant]
Tagaki et al., “A Monovacant Lacunary Silicotungstate as an Efficient Heterogeneous Catalyst for Dehydration of Primary Amides to Nitriles”, ChemCatChem, Jul. 2013, vol. 5, No. 7, pp. 1725-1728. [cited by applicant]
Kostestkyy et al., “Structure-activity Relationships on Metal-oxides: Alcohol Dehydration”, Catalysis Science & Technology, Nov. 2014, vol. 4, No. 11, pp. 3735-4102. [cited by applicant]
Kumar et al., “A Continuous Process for the Recovery of Lactic Acid by Reactive Distillation”, Journal of Chemical Technology & Biotechnology, 2006, vol. 81, pp. 1767-1777. [cited by applicant]
Le Notre et al., “Biobased Synthesis of Acrylonitrile from Glutamic Acid”, Green Chemistry, 2011, vol. 13, pp. 807-809. [cited by applicant]
Lim et al. “Processing Technologies for Poly(lactic Acid)”, Progress in Polymer Science, Aug. 2008, vol. 33, No. 8, pp. 820-852. [cited by applicant]
Liebig et al., “Glycerol Conversion to Acrylonitrile by Consecutive Dehydration over WO3/TiO2 and Ammoxidation Over Sb-(Fe,V)-O”, Applied Catalysis B: Environmental, Mar. 2013, vol. 132-133, pp. 170-182. [cited by applicant]
Mekki-Berrada et al., “Fatty Acid Methyl Esters into Nitriles: Acid-base Properties for Enhanced Catalysts”, Journal of Catalysis, 2013, vol. 306, pp. 30-37. [cited by applicant]
Mitchell et al., “Silica Gel as a Catalyst in the Preparation of Nitriles”, Journal of the American Chemical Society, Jan. 1931 vol. 53, pp. 321-330. [cited by applicant]
Orjuela, “A Novel Process for Recovery of Fermentation-derived Succinic Acid”, Separation and Purification Technology, 2011, vol. 83, pp. 31-37. [cited by applicant]
Pasternak et al., “Products of Ammonolysis of Dimethyl Esters of Aliphatic Dicarboxylic Acids”, Journal of Applied Chemistry USSR, 1973, vol. 47, No. 11, pp. 2590-2592. [cited by applicant]
Stevenson, “Ammonolysis”, Industrial & Engineering Chemistry, Sep. 1951, vol. 43, No. 9, pp. 1920-1924. [cited by applicant]
Suvorov et al., “Ammonolysis of Esters of Hydroxybenzoic Acids on a Boron Phosphate Catalyst”, Journal of Applied Chemistry USSR, Sep. 10, 1987, vol. 60, No. 3, pp. 677-679. [cited by applicant]
Vassena, “Nitration of Toluene and Nitrotoluene with Solid Acids”, A Dissertation Submitted to the Swiss Federal Institute of Technology Zurich, 2000, Diss. ETH No. 13600, pp. 1-151. [cited by applicant]
Extended European Search Report for European Application No. 17753876.6, dated Sep. 18, 2019, pp. 1-7. [cited by applicant]
International Search Report and Written Opinion for International (PCT) Application PCT/US17/18272, mailing date Apr. 25, 2017, pp. 1-9. [cited by applicant]
Fetzer et al., “Transition-Metal Catalysts for Controlled Radical Polymerization: A First Update”, Israel Journal of Chemistry, 2012, vol. 52, Nos. 3-4, pp. 221-229. [cited by applicant]
Tollefson et al., “Development of a process for production of acetonitrile from acetic acid and ammonia”, The Canadian Journal of Chemical Engineering, 1970, vol. 48, No. 2, pp. 219-223. [cited by applicant]
Galanov et al., “Catalytic synthesis of acetonitrile by ammonolysis of acetic acid over γ Al2O3 catalyst catalyst”, Science and Technology, 2001, vol. 2, pp. 175-177. [cited by applicant]
Karp et al., “Renewable acrylonitrile production”, Science, 2017, vol. 358, No. 6368, pp. 1307-1310. [cited by applicant]