Archer Daniels Midland Company

Washington State University

University of Kansas

Padmesh Venkitasubramanian

Kevin J Martin

Junming Sun

Changjun Liu

Yong Wang

Kenneth Stensrud

Mark D Welch

Sridhar Govindarajan

William Schroeder

Colin Smith

Bala Subramaniam

Daryle Hadley Busch

Mitchell J Schultz

Joshua Terrian

Xiaobin Zuo

Will Schroeder

This disclosure provides epimerase enzymes useful for commercial scale production of allulose from fructose. The disclosed enzymes ('epimerase variants') are variants ofCGD1 xylose isomerase engineered to have improved catalytic activity of about 1.5- to 2-fold compared with the parent enzyme.

Epimerase enzymes and their use

Wholly biobased MTBE and ETBE fuel additive materials are described, together with fuel compositions including such additives and processes for making the wholly biobased MTBE and ETBE using isobutene prepared from acetic acid in the presence of a ZnZrOmixed oxide catalyst.

Process for making biobased fuel additives

Disclosed herein are three geneses of proteins herein established to exhibit a fructose to allulose epimerase activity that are useful for production of allulose from fructose at high temperatures and at low pH in the range of 4.5 to 6.0. Two of the three geneses descend phylogenetically from a common ancestral protein defined herein, and these geneses are distinguished from each other by different parental descendant proteins also defined herein. The proteins with high levels of sequence identity to the parental nodes defining from these two geneses generally exhibit higher levels of specific fructose to glucose epimerase activity than prior known fructose to allulose epimerases and exhibit such activity at low pH. A third genus is not defined by phylogenetic origin except by not descending from the same ancestor as the first two geneses but generally exhibit similar levels of fructose to allulose epimerase activities as prior art epimerases described to be useful for fructose to allulose conversion.

Genus of epimerase enzymes for conversion of fructose to allulose at high temperature and low pH

A method of making a furan dicarboxylate by means of reacting 2,5-furan dicarboxylic acid (FDCA) with an alcohol or mixture of alcohols in a CO-predominant atmosphere without the presence of any other acid catalyst is described. The reaction is conducted under conditions that correspond to either supercritical, critical or near-critical temperatures and pressures for the alcohol species and/or COgas.

Esterification of 2,5-furan-dicarboxylic acid

A process for producing biofuels compounds directly from carboxylic acid esters recovered from a fermentation system is described. The process involves taking a fermentation broth that has been reduced to a dry powder containing free organic acids; reacting the carboxylic acid in the powder with an alcohol solvent under a CO-containing atmosphere in substantial absence of any other acid catalyst at a reaction temperature and pressure that corresponds to supercritical, critical or near critical conditions for at least one of the alcohol or COto synthesize an ester, then subjecting the ester to either hydrogenolysis or hydrogenation to form a biofuel.

Biofuels production from bio-derived carboxylic-acid esters

Processes are described for making biobased isoprene, wherein a biobased isobutene prepared from acetic acid in the presence of a catalyst is combined with a formaldehyde source to form a reaction mixture, and the reaction mixture is reacted to yield biobased isoprene. In certain embodiments, methyl-tert-butyl ether prepared by reacting the same biobased isobutene with methanol serves as a formaldehyde source, being oxidatively cracked to produce formaldehyde as well as isobutene for being converted to the biobased isoprene.

Process for making biobased isoprene

The production of organic acids in low-cost, high-efficiency fermentation system makes available a new route to chemical production from biomass. A process for producing a hydrogenation product involving carboxylic acid esters recovered directly from a fermentation process is described.

Hydrogenation products from biologically-derived carboxylic-acid esters

A method of preparing a glycol mono-ether or mono-acetate, or carbonate involving either one of two pathways from alkylene glycols, HMF or its reduction derivative products (i.e., FDM, bHMTHFs), is provided. In particular, according to one pathway, the alkylene glycol, HMF or FDM, bHMTHFs are reacted with a dialkyl carbonate in the presence of a deprotonating agent, in substantial absence of an extrinsic catalyst, to produce an ether, and subsequently reacting the ether with an acid base. According to the other pathway, alkylene glycols are reacted with an acetate donor in the presence of an acid, base, to generate an alkylene mono-acetate, and etherified with a carbonate in the presence of a deprotonating agent.

Direct synthesis of bio-based alkyl and furanic diol ethers, acetates, ether-acetates, and carbonates

A process for recovering and using an organic/carboxylic acid or furanic molecule by means of making an ester of a free carboxylic acid or furanic molecule with an alcohol in carbon dioxide (CO) without the presence of any other acid catalyst at a reaction temperature and pressure that corresponds to supercritical, critical or near critical conditions for the alcohol and/or COis described. The process can constitute part of a general process of refining carboxylic acids derived from a fermentation broth or use in the production of a variety of chemical compounds, such as Cplatform compounds or polymers.

Use of carboxylic acids and furanic molecules for esterification

Processes are described for making methacrylic acid via methacrolein from a biobased isobutene, wherein the biobased isobutene is prepared from ethanol or from acetic acid in the presence of a ZnZrOmixed oxide catalyst, the biobased isobutene is oxidized to methacrolein and the methacrolein is further oxidized to methacrylic acid.

Processes for making methacrylic acid

A process is disclosed for converting acetic acid to isobutene in the presence of a catalyst. In certain embodiments, a ZnZrOmixed oxide catalyst is used for carrying out a gas phase process for converting acetic acid to isobutene. In some embodiments, a ZnZrOmixed oxide catalyst made by an incipient wetness impregnation method is used and is indicated to be very stable for carrying out the conversion.

Process and catalyst for conversion of acetic acid to isobutene

A process is provided for carrying out an oxidation on a sprayable feed including a furanic substrate to be oxidized and a catalytically effective combination of cobalt, manganese, and bromide components for catalyzing the oxidation of the furanic substrate, which process comprises spraying the feed into a reactor vessel as a mist, supplying an oxidant, reacting the furanic substrate and the oxidant, and managing the exothermic temperature rise due to the reaction through a selection and control of the operating pressure within the reactor vessel. A crude dehydration product from the dehydration of fructose, glucose or both, including 5-hydroxymethylfurfural, can be directly oxidized by the process to produce 2,5-furandicarboxylic acid in surprisingly increased yields.

Spray oxidation process for producing 2,5-furandicarboxylic acid from hydroxymethylfurfural

A process is disclosed for converting acetic acid to propylene and isobutene as the principal hydrocarbon products made, in the presence of a catalyst and in the further presence of hydrogen. In certain embodiments, a ZnZrOmixed oxide catalyst is used for carrying out a gas phase process, and propylene is produced preferentially to isobutene by using at least a certain amount of hydrogen in the process. In some embodiments, a ZnZrOmixed oxide catalyst made by an incipient wetness impregnation method is used and is indicated to be very stable for carrying out the conversion.

Process and catalyst for conversion of acetic acid to isobutene and propylene

A process is described for making renewable para-xylene, comprising converting acetic acid to isobutene in the presence of a catalyst then converting the acetic acid-derived isobutene to a product composition including para-xylene. The catalyst can be a ZnZrOmixed oxide catalyst.

Growing community of inventors

Forsyth, IL, United States of America

Padmesh Venkitasubramanian