Battelle Memorial Institute

Michigan State University

Bioamber International S.a.r.l.

James F White

Alan H Zacher

Richard T Hallen

Michel J Gray

Johnathan E Holladay

Todd A Werpy

Michael A Lilga

Jianli Hu

John G Frye

Yong Wang

Karl O Albrecht

Heather M Brown

Danielle S Muzatko

Leo E Manzer

Thomas Peterson

James J Strohm

Vanessa Lebarbier

Dennis J Miller

Douglas Charles Elliott

Chunshe J Cao

Robert A Dagle

Robert L Augustine

Setrak K Tanielyan

Jamelyn D Holladay

Yasuo Yoshikuni

Lars Peereboom

Rick J Orth

Adam Joseph Wargacki

Lou Kapicak

Ramesh D Bhagat

Balaraju Miryala

Don J Stevens

Susan R Cooper

John G Frey, Jr

Provided are methods of producing 2,5-furandicarboxylic acid (FDCA) from renewable sources such as seaweed, alginate, oligoalginate, pectin, oligopectin, polygalacturonate, galacturonate, and/or oligogalacturonate. The sugars in the renewable sources can be converted into one or more intermediates such as 4-deoxy-L-erythro-5-hexoseulose uronate (DEHU), 4-deoxy-L-threo-5-hexosulose uronate (DTHU), 5-hydroxymethyl furfural (HMF), 2,5-dihydroxymethyl furan (DHMF), and 5-formyl-2-furancarboxylic acid (FFA), which can be converted into FDCA by dehydration and cyclization to produce 5-formyl-2-furancarboxylic acid (FFA), followed by oxidation to produce FDCA. DEHU or DTHU may also be converted into FDCA by oxidation to produce 2,3-dihydroxy-5-oxohexanedioic acid (DOHA), which then undergoes dehydration and cyclization to produce FDCA.

Methods for preparing 2,5-furandicarboxylic acid

A reduced metallic catalyst or pre-activated catalyst is formed by contacting a precursor catalyst or a reduced metallic catalyst with a modifier solution in the presence of a source of hydrogen and heat treating the precursor catalyst or the reduced metallic catalyst at super-atmospheric pressure to obtain the reduced metallic catalyst from the precursor catalyst or the pre-activated catalyst from the reduced metallic catalyst. A method of hydrogenating a hydrogenatable precursor includes providing a reduced metallic catalyst or the pre-activated catalyst prepared with modifier buffer and contacting the reduced metallic catalyst or pre-activated catalyst with the hydrogenatable precursor in the presence of hydrogen and, optionally, in the presence of a modifier solution.

Preparation of catalyst for selective hydrogenation of hydrogenatable precursors

Hydrogenolysis systems are provided that can include a reactor housing an Ru-comprising hydrogenolysis catalyst and wherein the contents of the reactor is maintained at a neutral or acidic pH. Reactant reservoirs within the system can include a polyhydric alcohol compound and a base, wherein a weight ratio of the base to the compound is less than 0.05. Systems also include the product reservoir comprising a hydrogenolyzed polyhydric alcohol compound and salts of organic acids, and wherein the moles of base are substantially equivalent to the moles of salts or organic acids. Processes are provided that can include an Ru-comprising catalyst within a mixture having a neutral or acidic pH. A weight ratio of the base to the compound can be between 0.01 and 0.05 during exposing.

Chemical production processes and systems

The present disclosure relates to facilities, systems, methods and/or catalysts for use in chemical production. In particular, the disclosure provides innovations relating to dehydration of multihydric compounds such as glycerol to form acrolein. Some of these innovations include continuous reaction systems as well as system parameters that allow for long term production.

Multihydric compound dehydration systems, catalyst compositions, and methods

Embodiments of methods for making renewable diesel by deoxygenating (decarboxylating/decarbonylating/dehydrating) fatty acids to produce hydrocarbons are disclosed. Fatty acids are exposed to a catalyst selected from a) Pt and MOon ZrO(M is W, Mo, or a combination thereof), or b) Pt/Ge or Pt/Sn on carbon, and the catalyst decarboxylates at least 10% of the fatty acids. In particular embodiments, the catalyst consists essentially of 0.7 wt % Pt and 12 wt % WO, relative to a mass of catalyst, or the catalyst consists essentially of a) 5 wt % Pt and b) 0.5 wt % Ge or 0.5 wt % Sn, relative to a mass of catalyst. Deoxygenation is performed without added hydrogen and at less than 100 psi. Disclosed embodiments of the catalysts deoxygenate at least 10% of fatty acids in a fatty acid feed, and remain capable of deoxygenating fatty acids for at least 200 minutes to more than 350 hours.

Deoxygenation of fatty acids for preparation of hydrocarbons

A method of reducing hydroxymethylfurfural (HMF) where a starting material containing HMF in a solvent comprising water is provided. His provided into the reactor and the starting material is contacted with a catalyst containing at least one metal selected from Ni, Co, Cu, Pd, Pt, Ru, Ir, Re and Rh, at a temperature of less than or equal to 250&#xb0; C. A method of hydrogenating HMF includes providing an aqueous solution containing HMF and fructose. Hand a hydrogenation catalyst are provided. The HMF is selectively hydrogenated relative to the fructose at a temperature at or above 30&#xb0; C. A method of producing tetrahydrofuran dimethanol (THFDM) includes providing a continuous flow reactor having first and second catalysts and providing a feed comprising HMF into the reactor. The feed is contacted with the first catalyst to produce furan dimethanol (FDM) which is contacted with the second catalyst to produce THFDM.

Hydroxymethylfurfural reduction methods and methods of producing furandimethanol

The invention includes methods of processing an initial di-carbonyl compound by conversion to a cyclic compound. The cyclic compound is reacted with an alkylating agent to form a derivative having an alkylated ring nitrogen. The invention encompasses a method of producing an N-alkyl product. Ammonia content of a solution is adjusted to produce a ratio of ammonia to di-carboxylate compound of from about 1:1 to about 1.5:1. An alkylating agent is added and the initial compound is alkylated and cyclized. The invention includes methods of making N-methyl pyrrolidinone (NMP). Aqueous ammonia and succinate is introduced into a vessel and ammonia is adjusted to provide a ratio of ammonia to succinate of less than 2:1. A methylating agent is reacted with succinate at a temperature of from greater than 100&#xb0; C. to about 400&#xb0; C. to produce N-methyl succinimide which is purified and hydrogenated to form NMP.

Process for producing cyclic compounds

A method of oxidizing hydroxymethylfurfural (HMF) includes providing a starting material which includes HMF in a solvent comprising water into a reactor. At least one of air and Ois provided into the reactor. The starting material is contacted with the catalyst comprising Pt on a support material where the contacting is conducted at a reactor temperature of from about 50&#xb0; C. to about 200&#xb0; C. A method of producing an oxidation catalyst where ZrOis provided and is calcined. The ZrOis mixed with platinum (II) acetylacetonate to form a mixture. The mixture is subjected to rotary evaporation to form a product. The product is calcined and reduced under hydrogen to form an activated product. The activated product is passivated under a flow of 2% O.

Hydroxymethyl furfural oxidation methods

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Richland, WA, United States of America

James F White