WO2011109051A1 - Composition d'acide adipique - Google Patents

Composition d'acide adipique Download PDF

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Publication number
WO2011109051A1
WO2011109051A1 PCT/US2010/060147 US2010060147W WO2011109051A1 WO 2011109051 A1 WO2011109051 A1 WO 2011109051A1 US 2010060147 W US2010060147 W US 2010060147W WO 2011109051 A1 WO2011109051 A1 WO 2011109051A1
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WO
WIPO (PCT)
Prior art keywords
formula
adipic acid
matter
compositions
catalyst
Prior art date
Application number
PCT/US2010/060147
Other languages
English (en)
Inventor
Thomas R. Boussie
Eric L. Dias
Zachary M. Fresco
Vincent J. Murphy
James Shoemaker
Raymond Archer
Hong Jiang
Original Assignee
Rennovia, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US12/814,188 external-priority patent/US8669397B2/en
Application filed by Rennovia, Inc. filed Critical Rennovia, Inc.
Priority to CA2791500A priority Critical patent/CA2791500C/fr
Priority to NZ601945A priority patent/NZ601945A/en
Priority to BR112012022136A priority patent/BR112012022136B1/pt
Priority to CN2010800651905A priority patent/CN102869642A/zh
Priority to AU2010347225A priority patent/AU2010347225B2/en
Priority to EP10812827A priority patent/EP2542519A1/fr
Publication of WO2011109051A1 publication Critical patent/WO2011109051A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
    • C07C55/02—Dicarboxylic acids
    • C07C55/14—Adipic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/377—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/16—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D309/28—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D309/30—Oxygen atoms, e.g. delta-lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids

Definitions

  • compositions of matter comprising an adipic acid product of formula (1)
  • R is independently a salt-forming ion, hydrogen, hydrocarbyl, or substituted hydrocarbyl
  • R 1 is H, OH, acyloxy or substituted acyloxy provided, however, at least one of R 1 is OH, and formula (3)
  • R is as above defined and R 1 is H, OH, acyloxy or substituted acyloxy.
  • the present invention is also directed to compositions of matter comprising an adipic acid product of formula (1) and at least two different constituents selected from the group of formula (2) and formula (3), above.
  • the present invention includes compositions of matter comprising at least about 99 wt% adipic acid or a salt thereof and up to about 1 wt% of at least one constituent of formula (2).
  • the present invention further includes compositions of matter comprising at least about 99 wt% adipic acid and up to about 1 wt% of at least one constituent selected from the group consisting of formula (2) and formula (3).
  • the present invention further includes compositions of matter comprising at least about 99 wt% adipic acid and up to about 1 wt% of at least two constituents selected from the group consisting of formula (2) and formula (3).
  • the present invention also relates to industrial chemicals such as adiponitrile, hexamethylene diamine, caprolactam, caprolactone, 1,6-hexanediol, adipate esters, polyamides (e.g., nylons) and polyesters produced from such compositions of matter.
  • industrial chemicals such as adiponitrile, hexamethylene diamine, caprolactam, caprolactone, 1,6-hexanediol, adipate esters, polyamides (e.g., nylons) and polyesters produced from such compositions of matter.
  • Crude oil is currently the source of most commodity and specialty organic chemicals. Many of these chemicals are employed in the manufacture of polymers and other materials. Examples include ethylene, propylene, styrene, bisphenol A, terephthalic acid, adipic acid, caprolactam, hexamethylene diamine, adiponitrile, caprolactone, acrylic acid, acrylonitrile, 1,6-hexanediol, 1,3-propanediol, and others. Crude oil is first refined into hydrocarbon intermediates such as ethylene, propylene, benzene, and cyclohexane. These hydrocarbon intermediates are then typically selectively oxidized using various processes to produce the desired chemical.
  • hydrocarbon intermediates such as ethylene, propylene, benzene, and cyclohexane.
  • crude oil is refined into cyclohexane which is then selectively oxidized to "KA oil” which is then further oxidized for the production of adipic acid, an important industrial monomer used for the production of nylon 6,6.
  • KA oil an important industrial monomer used for the production of nylon 6,6.
  • Many known processes are employed industrially to produce these petrochemicals from precursors found in crude oil. For example, see Ullmann 's Encyclopedia of Industrial Chemistry, Wiley 2009 (7th edition), which is incorporated herein by reference. Chemicals produced from crude oil, and the downstream products thereof, exhibit no C-14 constituents.
  • compositions of matter comprising an adipic acid product of formula (1)
  • R is independently a salt-forming ion, hydrogen, hydrocarbyl, or substituted hydrocarbyl
  • R is as defined above and each of R is H, OH, acyloxy or substituted acyloxy provided, however, that at least one of R 1 is OH, and formula (3)
  • R is as defined above and R 1 is H, OH, acyloxy or substituted acyloxy.
  • the present invention is also directed to compositions of matter comprising an adipic acid product of formula (1) and at least two different constituents selected from the group of formula (2) and formula (3), above.
  • the present invention includes compositions of matter comprising at least about 99 wt% adipic acid or a salt thereof and up to about 1 wt% of at least one constituent of formula (2).
  • the present invention further includes compositions of matter comprising at least about 99 wt% adipic acid and up to about 1 wt% of at least one constituent selected from the group consisting of formula (2) and formula (3).
  • the present invention further includes compositions of matter comprising at least about 99 wt% adipic acid and up to about 1 wt% of at least two constituents selected from the group consisting of formula (2) and formula (3).
  • the present invention also relates to industrial chemicals such as adiponitrile, hexamethylene diamine, caprolactam, caprolactone, 1,6-hexanediol, adipate esters, polyamides (e.g., nylons) and polyesters produced from such compositions of matter.
  • industrial chemicals such as adiponitrile, hexamethylene diamine, caprolactam, caprolactone, 1,6-hexanediol, adipate esters, polyamides (e.g., nylons) and polyesters produced from such compositions of matter.
  • compositions of matter heretofore not produced such compositions comprising an adipic acid product of formula (1), above, and at least one constituent selected from the group consisting of formulae (2) and (3), above, and methods of producing the same.
  • the compositions of matter of the present invention may be converted, according to processes known in the art, to various other industrially significant chemicals including, for example, adiponitrile, caprolactam, caprolactone, hexamethylene diamine, 1,6-hexanediol, adipate esters, polyamides (e.g., nylon) or polyesters.
  • Glucose a preferred feedstock for producing the products of the present invention, can be obtained from various carbohydrate-containing sources including conventional biorenewable sources such as corn grain (maize), wheat, potato, cassava and rice as well as alternative sources such as energy crops, plant biomass, agricultural wastes, forestry residues, sugar processing residues and plant-derived household wastes.
  • biorenewable sources such as corn grain (maize), wheat, potato, cassava and rice as well as alternative sources such as energy crops, plant biomass, agricultural wastes, forestry residues, sugar processing residues and plant-derived household wastes.
  • Glucose may be isolated from biorenewable sources using methods that are known in the art. See, for example, Centi and van RNVA 6358.1
  • compositions of matter of the present invention are prepared by chemocatalytic conversion of a glucose source to a hydrodeoxygenation substrate comprising at least glucaric acid and/or derivatives thereof, which substrate is subsequently converted by chemocatalytic means employing a heterogeneous catalyst comprising platinum or platinum and rhodium, in the presence of a source of bromine and in the presence of an acetic acid solvent, wherein the reaction product of the
  • hydrodeoxygenation step is subjected to techniques commonly employed in the purification of adipic acid produced by conventional processes, such techniques including, for example, washing, crystallization and recrystallization to produce the compositions of matter of the present invention.
  • the hydrodeoxygenation substrate comprises a compound of the following formula (A):
  • X is independently hydroxyl, oxo, halo, acyloxy or hydrogen provided that at least one X is not hydrogen;
  • R is independently a salt- forming ion, hydrogen, hydrocarbyl, or substituted hydrocarbyl; or a mono- or di-lactone thereof.
  • hydrocarbyl refers to hydrocarbyl moieties, preferably containing 1 to about 50 carbon atoms, preferably 1 to about 30 carbon atoms, and even more preferably 1 to about 18 carbon atoms, including branched or unbranched, and saturated or unsaturated species.
  • Preferred hydrocarbyl can be selected from the group consisting of alkyl, alkylene, alkoxy, alkylamino, thioalkyl, haloalkyl, cycloalkyl,
  • hydrocarbyl may be optionally substituted hydrocarbyl.
  • various hydrocarbyls can be further selected from substituted alkyl, substituted cycloalkyl and the like.
  • Salt forming ions include, without limitation, for example ammonium ions and metal ions (e.g., alkali and alkaline earth metals).
  • R is a salt forming ion (i.e., a cation)
  • the carboxyl group may be considered to be anion (i.e., carboxylate anion).
  • the hydrodeoxygenation substrate comprises a compound of formula (A), wherein X is hydroxyl and R is independently a salt- forming ion, hydrogen, hydrocarbyl, or substituted hydrocarbyl.
  • the hydrodeoxygenation substrate contains a six carbon chain comprising four chiral centers. As a result several stereoisomers are possible.
  • the preferred hydrodeoxygenation substrate comprises glucaric acid.
  • the hydrodeoxygenation substrate may also contain various ketones.
  • ketones such as 2-keto-glucaric acid (2,3,4-trihydroxy-5-oxohexanedioic acid) and 3-keto-glucaric acid (2,3,5- trihydroxy-4-oxohexanedioic acid) may be formed.
  • the hydrodeoxygenation substrate may comprise various lactones derived from glucaric acid.
  • various mono- and di-lactones are present in equilibrium with glucaric acid in aqueous solution, including for example, D-glucaro-l,4-lactone, D-glucaro-6,3 -lactone, and D-glucaro-l,4:6,3- dilactone.
  • processes have been developed to quantitatively convert glucaric acid or a salt thereof in solution to one or more lactones and recover a substantially pure lactone stream.
  • 4-enaro-6,3-lactone and L-er ⁇ /zro-4-deoxy-hex-4-enaro-6,3-lactone may form from the thermal decomposition of D-Glucaro-l,4:6,3-dilactone.
  • the hydrodeoxygenation substrate comprises D-glucaro- 1 ,4-lactone.
  • the hydrodeoxygenation substrate comprises D-glucaro-6,3-lactone.
  • the hydrodeoxygenation substrate comprises D-glucaro-l,4:6,3-dilactone.
  • the hydrodeoxygenation substrate comprises L-?/zreo4-deoxy-hex-4-enaro-6,3- lactone.
  • the hydrodeoxygenation substrate comprises L-ery?/zro-4-deoxy-hex-4-enaro-6,3-lactone.
  • compositions of matter comprise an adipic acid product (formula 1) prepared by reacting, in the presence of a source of bromine, preferably HBr, a hydrodeoxygenation catalyst comprising platinum or platinum and rhodium and a solvent, preferably acetic acid , a hydrodeoxygenation substrate (formula A) and hydrogen, according to the following reaction:
  • R is as defined above and each of R 1 is, independently, H, OH, acyloxy or substituted acyloxy provided, however, that at least one of R 1 is OH, and formula (3) RNVA 6358.1
  • R is as defined above and Rl is H, OH, acyloxy or substituted acyloxy.
  • compositions of matter comprise adipic acid and/or salt thereof and at least two other constituents selected from formulae (2) and (3), above.
  • compositions of matter comprises at least about 99% adipic acid or salt thereof and up to 1% of at least one constituent selected from formula (2) and formula (3), above.
  • compositions of matter comprises at least about 99% adipic acid or salt thereof and up to 1% of at least one constituent of formula (2), above.
  • compositions of matter comprises at least about 99% adipic acid or salt thereof and up to 1% of at least two constituents selected from formula (2) and formula (3), above.
  • the hydrodeoxygenation reaction can be conducted by first forming and optionally purifying or isolating various intermediates formed by combining a hydrodeoxygenation substrate and the source of bromine and subsequently reacting the intermediate with hydrogen in the presence of the hydrodeoxygenation catalyst and, optionally, in the absence of any additional halogen source.
  • the hydrodeoxygenation substrate is halogenated with hydrobromic acid to form a brominated intermediate (e.g., an alkyl bromide).
  • the hydrodeoxygenation substrate is halogenated with a molecular bromine to form the brominated intermediate (e.g., an alkyl bromide).
  • the bromine source may be in a form selected from the group consisting of atomic, ionic, molecular, and mixtures thereof.
  • the bromine source is most preferably hydrogen bromide.
  • the molar ratio of bromine to the hydrodeoxygenation substrate is less than 1. In various embodiments, the mole ratio of halogen to the hydrodeoxygenation substrate is typically less than about 0.5. RNVA 6358.1
  • reaction allows for recovery of the bromine, and catalytic quantities of bromine can be used, recovered and recycled for continued use.
  • the temperature of the hydrodeoxygenation reaction mixture is preferably between about 100°C and 180°C.
  • the partial pressure of hydrogen is in the range of about 800 psia (5516kPa) to about 1300 psia (8964kPa).
  • the hydrodeoxygenation reaction is conducted in the presence of solvents.
  • Mixtures of water and weak carboxylic acid, or weak carboxylic acid are suitable solvents.
  • the weak carboxylic acid is acetic acid.
  • the reaction can be conducted in a batch, semi-batch, or continuous reactor design using fixed bed reactors, trickle bed reactors, slurry phase reactors, moving bed reactors, or any other design that allows for heterogeneous catalytic reactions.
  • reactors can be seen in Chemical Process Equipment - Selection and Design, Couper et al, Elsevier 1990, which is incorporated herein by reference. It should be understood that the hydrodeoxygenation substrate, halogen source, hydrogen, any solvent, and the hydrodeoxygenation catalyst may be introduced into a suitable reactor separately or in various combinations.
  • the hydrodeoxygenation catalyst is a solid-phase heterogeneous catalyst comprising platinum, or platinum and rhodium, present on a support (preferably, at one or more surfaces, external or internal).
  • the metals constitute not more than about 8%, preferably less than or equal to about 4%.
  • the Pt:Rh molar ratio may vary, for example, from about 20: 1 to about 0.1 : 1, from about 10: 1 to about 0.5: 1, and, more preferably, from about 5: 1 to about 1 : 1.
  • Preferred catalyst supports include carbon, silica, titania, zirconia, zeolite, clays, silicon carbide, and modifications, mixtures or combinations thereof.
  • the preferred supports may be modified through methods known in the art such as, for example, heat treatment, acid treatment or the introduction of a dopant.
  • the hydrodeoxygenation catalyst support is selected from the group consisting of silica, zirconia and titania. More preferred catalysts comprise platinum and rhodium on a support comprising silica.
  • the metals may be deposited on the support using procedures known in the art including, but not limited to incipient wetness, ion-exchange, deposition-precipitation and vacuum impregnation.
  • the metals may be deposited sequentially or simultaneously.
  • the catalyst is dried at a temperature of at least about RNVA 6358.1
  • the catalyst is dried under sub-atmospheric conditions.
  • the catalyst is reduced after drying (e.g., by flowing 5% H 2 in 2 at 350 °C for 3 hours).
  • the catalyst is calcined, for example, at a temperature of at least about 500°C for a period of time (e.g., at least about 3 hours).
  • compositions of matter of the present invention may be recovered from the hydrodeoxygenation reaction mixture by one or more conventional methods known in the art including, for example, solvent extraction, crystallization or evaporative processes.
  • the reaction product recovered from the hydrodeoxygenation reaction comprises adipic acid product and, typically, several of the additional constituents of formulae (2) and/or (3), above, in liquid form.
  • the recovered reaction product is dried. Drying can be conducted in any suitable inert atmosphere, in air or under a vacuum.
  • the temperature at which drying should be sufficient such that the compositions of matter will precipitate out of solution. Typically, the temperature will be in the range of about 25°C to about 120°C.
  • the precipitate may then be subjected to conventional treatments employed for the recovery of adipic acid produced by conventional processes, such treatments including, for example, washing, for example, with water followed by, for example, redissolution and recrystallization (one or more additional times), followed by a decolorization treatment and, for example, a final recrystallization and wash.
  • treatments including, for example, washing, for example, with water followed by, for example, redissolution and recrystallization (one or more additional times), followed by a decolorization treatment and, for example, a final recrystallization and wash.
  • adipic acid to downstream chemical products or intermediates including adipate esters, polyesters, adiponitrile, hexamethylene diamine (HMD A), caprolactam, caprolactone, 1,6-hexanediol, aminocaproic acid, and polyamide such as nylons.
  • HMD A hexamethylene diamine
  • caprolactam caprolactone
  • 1,6-hexanediol aminocaproic acid
  • polyamide such as nylons.
  • compositions of matter of the present invention comprising at least about 99 wt% adipic acid can be converted to adiponitrile.
  • Adiponitrile can be used industrially for the manufacture of hexamethylene diamine, see Smiley,
  • compositions of matter of the present invention can be converted to
  • Adipic acid is useful in the production of polyamides, such as nylon 6,6 and nylon 4,6. See, for example, U.S. Patent No. 4,722,997, and Musser, "Adipic Acid" in
  • the hexamethylene diamine formed from the compositions of matter of the present invention comprising at least about 99 wt% adipic acid can likewise be further used for the preparation of polyamides such as nylon 6,6 and nylon 6, 12. See, for example Kohan, Mestemacher,
  • compositions of matter of the present invention comprising at least about 99 wt% adipic acid and a polymer precursor derived from such compositions may be reacted to produce a polyamide.
  • Polymer precursor refers to a monomer which can be converted to a polymer (or copolymer) under appropriate polymerization conditions.
  • the polyamide comprises nylon 6,6.
  • the polymer precursor comprises hexamethylene diamine which may be derived from the compositions of the present invention.
  • the compositions of matter of the present invention comprising at least about 99 wt%adipic acid may be converted to caprolactam.
  • the caprolactam formed can be further used for the preparation of polyamides by means generally known in the art. Specifically, caprolactam can be further used for the preparation of nylon 6. See, for example Kohan, Mestemacher, Pagilagan, Redmond, "Polyamides" in Ullmann 's Encyclopedia of Industrial Chemistry, Wiley -VCH, Weinheim, 2005.
  • adipic acid and a polymer precursor may be reacted to produce a polyester, wherein the adipic acid product is prepared in accordance with the present invention.
  • compositions of matter of the present invention comprising at least about 99 wt% adipic acid may be converted to 1,6-hexanediol.
  • 1,6- hexanediol is a valuable chemical intermediate used in the production of polyesters and polyurethanes.
  • polyester may be prepared by reacting the compositions of matter of the present invention comprising at least about 99 wt% adipic acid and 1,6-hexandiol derived from such compositions of the present invention. RNVA 6358.1
  • a salt of adipic acid may be produce wherein the process comprises reacting the compositions of matter of the present invention comprising at least about 99 wt% adipic acid with hexamethylene diamine, thereby forming the salt.
  • the glass vial arrays of Pt/M2/Support catalysts were dried in a furnace at 120 °C for 1 hour, followed by calcination at 500 °C for 3 hours followed by reduction under flowing 5 vol. % H 2 in N 2 at either 200 °C or 350 °C for 3 hours. Note that this procedure was used to prepare all Pt/M2/Support catalysts with the exception of the 1.5 % Pt/1.5% Au/Titania catalyst.
  • ⁇ ( ⁇ (3 ⁇ 4) 2 solution was added to a dried sample of the commercial 1.5% Au/Titania catalyst [Sud Chemie 02-10] (wherein the total volume of the Pt(NOs) 2 volume was matched to equal to the pore volume of the catalyst) with agitation, whereupon the material was dried in a furnace at 120 °C for 1 hour, followed by reduction under flowing 5 vol. % H 2 in N 2 at 350 °C for 3 hours.
  • Catalysts were dispensed into lmL vials within a 96-well reactor insert (Symyx Solutions).
  • the reaction substrate was D-glucose (Sigma-Aldrich, 0.552M in water).
  • To each vial was added 250 ⁇ ., of glucose solution.
  • the vials were each covered with a Teflon pinhole sheet, a silicone pin-hole mat and steel gas diffusion plate (Symyx Solutions).
  • the reactor insert was placed in a pressure vessel and charged three times with oxygen to 100 psig with venting after each pressurization step. The reactor was then charged to 75 psig with oxygen, or to 500 psig with air, closed and placed on a shaker, heated at the designated temperature for the specified reaction time.
  • Catalysts in examples 4-7, 11-12 were reduced at 200 °C under flowing 5 vol.% H 2 in N 2 for 3 hours.
  • Catalysts in examples 1-3, 8-10, 19-25 were reduced at 350 °C under flowing 5 vol.% H 2 in N 2 for 3 hours.
  • silica support (Davisil 635 W.R. Grace & Co.) was dispensed into a 1 mL glass vial.
  • the support was dried at 120 °C for 12 hours prior to use.
  • To the vial (where the total addition volume was matched to equal to the pore volume of the support weighed into the vial) suitably concentrated pre-mixed stock solutions were added (obtained from Heraeus).
  • Post metal addition the mixture was agitated via a multi-tube vortexer to impregnate the support.
  • the glass vial array of catalyst was dried in a furnace at 120 °C for 1 hour, followed by calcination at 500 °C for 3 hours. Upon cooling, the catalyst was stored in a dessicator until used.
  • the catalyst was transferred to a 1 mL glass vial within a 96- well reactor insert (Symyx Solutions).
  • the vial received a glass bead, 250 of 0.2 M Glucaric Acid (prepared from calcium glucarate) (Sigma-Aldrich), and 0.2 M HBr (Sigma-Aldrich) in Acetic Acid (Sigma-Aldrich).
  • the vial was covered with a Teflon pin-hole sheet, a silicone pin-hole mat and steel gas diffusion plate (Symyx Solutions).
  • the reactor insert was placed in a pressure vessel pressurized and vented 3 times with nitrogen and 3 times with hydrogen before being pressurized with hydrogen to 710 psig, heated to 160 °C and shaken for 3 hours. After 3 hours the reactor was cooled, vented and purged with nitrogen. 750 ⁇ of water was then added to the vial. Following the water addition, the vial was covered and shaken to ensure adequate mixing. Subsequently, the covered vial was placed in a centrifuge to separate RNVA 6358.1
  • the light yellow solid was washed with deionized water (3 x 400 ml) at 50°C before it was dried in a 60° C oven overnight under a dry air purge. The sample was then reduced at 200°C under a forming gas (5% H 2 and 95% N 2 ) atmosphere for 3 hours with 2°C/min temperature ramp rate to give 4.90 g purple solid.
  • the sample was then reduced at 350°C under a forming gas (5% H 2 and 95% N 2 ) atmosphere for 3 hours with 2°C/min temperature ramp rate.
  • the final catalyst was composed of ca. 4.0 wt% Au and 4.0 wt% Pt.
  • Glucose solutions were prepared by dissolving D-(+)-Glucose (Sigma-Aldrich, >99.5%) in water.
  • a back pressure regulator controlled reactor pressure as indicated in Table 3. All reactions were performed with zero grade air (Matheson Tri-Gas, Santa Clara, CA). Reactor product was collected over 122 hours and concentrated under reduced pressure without further purification.

Abstract

Les compositions de matière ci-décrites comprennent un produit d'acide adipique de formule (1), R dans la formule (1) étant indépendamment un ion formant sel, un atome d'hydrogène, un hydrocarbyle ou hydrocarbyle substitué, et au moins un constituant choisi dans le groupe constitué par la formule (2), R dans la formule (2) étant tel que défini ci-dessus et chaque R1 étant, indépendamment, H, OH, un acyloxy or acyloxy substitué à condition, toutefois, qu'au moins un des R1 soit OH, et la formule (3), R dans la formule (3) étant tel que défini ci-dessus et R1 étant OH, un acyloxy ou acyloxy substitué. Des compositions de matière comprenant au moins environ 99 % en poids d'acide adipique et au moins deux constituants choisis dans le groupe constitué par la formule (2) et la formule (3), ci-dessus, sont également décrites.
PCT/US2010/060147 2010-03-05 2010-12-13 Composition d'acide adipique WO2011109051A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
CA2791500A CA2791500C (fr) 2010-03-05 2010-12-13 Procede de preparation d'une composition d'acide adipique
NZ601945A NZ601945A (en) 2010-03-05 2010-12-13 Adipic acid composition
BR112012022136A BR112012022136B1 (pt) 2010-03-05 2010-12-13 composição de ácido adípico
CN2010800651905A CN102869642A (zh) 2010-03-05 2010-12-13 己二酸组合物
AU2010347225A AU2010347225B2 (en) 2010-03-05 2010-12-13 Adipic acid composition
EP10812827A EP2542519A1 (fr) 2010-03-05 2010-12-13 Composition d'acide adipique

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US31119010P 2010-03-05 2010-03-05
US61/311,190 2010-03-05
US12/814,188 2010-06-11
US12/814,188 US8669397B2 (en) 2009-06-13 2010-06-11 Production of adipic acid and derivatives from carbohydrate-containing materials

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WO2011109051A1 true WO2011109051A1 (fr) 2011-09-09

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PCT/US2010/060147 WO2011109051A1 (fr) 2010-03-05 2010-12-13 Composition d'acide adipique

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EP (1) EP2542519A1 (fr)
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JP2015517977A (ja) * 2012-02-23 2015-06-25 レノビア・インコーポレイテッドＲｅｎｎｏｖｉａ，Ｉｎｃ． アジピン酸からのカプロラクタムの生成

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JP2015517977A (ja) * 2012-02-23 2015-06-25 レノビア・インコーポレイテッドＲｅｎｎｏｖｉａ，Ｉｎｃ． アジピン酸からのカプロラクタムの生成
DE102012006946A1 (de) 2012-04-10 2013-10-10 Stratley Ag Verfahren zur Herstellung von Caprolactam
WO2013152999A1 (fr) 2012-04-10 2013-10-17 Stratley Ag Procédé de production de caprolactame
WO2013173372A1 (fr) * 2012-05-15 2013-11-21 Rennovia, Inc. Catalyseurs de réduction
CN104582847A (zh) * 2012-05-15 2015-04-29 莱诺维亚公司 还原催化剂
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