EP2542519A1 - Adipic acid composition - Google Patents

Adipic acid composition

Info

Publication number
EP2542519A1
EP2542519A1 EP10812827A EP10812827A EP2542519A1 EP 2542519 A1 EP2542519 A1 EP 2542519A1 EP 10812827 A EP10812827 A EP 10812827A EP 10812827 A EP10812827 A EP 10812827A EP 2542519 A1 EP2542519 A1 EP 2542519A1
Authority
EP
European Patent Office
Prior art keywords
formula
adipic acid
matter
compositions
catalyst
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP10812827A
Other languages
German (de)
French (fr)
Inventor
Thomas R. Boussie
Eric L. Dias
Zachary M. Fresco
Vincent J. Murphy
James Shoemaker
Raymond Archer
Hong Jiang
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Archer Daniels Midland Co
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
Publication of EP2542519A1 publication Critical patent/EP2542519A1/en
Withdrawn legal-status Critical Current

Links

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.

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  • Polyamides (AREA)

Abstract

Disclosed are compositions of matter comprising an adipic acid product of formula (1) wherein R is independently a salt-forming ion, hydrogen, hydrocarbyl, or substituted hydrocarbyl, and at least one constituent selected from the group consisting of formula (2) wherein R is as defined above and each of R1 is, independently, H, OH, acyloxy or substituted acyloxy provided, however, that at least one of R1 is OH, and formula (3) wherein R is as above defined and R1 is OH, acyloxy or substituted acyloxy. Also disclosed are compositions of matter comprising at least about 99 wt% adipic acid and least two constituents selected from the group consisting of formula (2) and formula (3), above.

Description

RNVA 6358.1
1
ADIPIC ACID COMPOSITION
FIELD OF THE INVENTION
[0001 ] The present invention is directed to compositions of matter comprising an adipic acid product of formula (1)
1
wherein R is independently a salt-forming ion, hydrogen, hydrocarbyl, or substituted hydrocarbyl, and
at least one constituent selected from the group consisting of formula (2)
wherein R is as defined above, R1 is H, OH, acyloxy or substituted acyloxy provided, however, at least one of R1 is OH, and formula (3)
3
wherein R is as above defined and R1 is H, OH, acyloxy or substituted acyloxy.
[0002 ] 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.
[0003 ] 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). RNVA 6358.1
2
[0004] 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).
[0005] 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).
[0006] 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.
BACKGROUND OF THE INVENTION
[0007] 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. For example, 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. 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.
[0008] For many years there has been an interest in using biorenewable materials as a feedstock to replace or supplement crude oil. See, for example, Klass, Biomass for Renewable Energy, Fuels, and Chemicals, Academic Press, 1998, which is incorporated herein by reference. Moreover, there have been efforts to produce adipic acid from renewable resources using processes involving a combination of biocatalytic and chemocatalytic processes. See, for example, "Benzene-Free Synthesis of Adipic Acid", Frost et al. Biotechnol. Prog. 2002, Vol. 18, pp. 201-211, and U.S. Patent Nos. 4,400,468, and 5,487,987. Unlike products produced from crude oil, products produced from biorenewable materials, more particularly from carbohydrates RNVA 6358.1
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derived therefrom, exhibit distinctly different characteristics, among which is the presence of C- 14 constituents.
[0009 ] Until the discovery of the processes disclosed in co-pending U.S. Application Serial No. 12/814, 188, filed June 1 1, 2010, by Boussie et al, one of the major challenges for converting biorenewable resources such as carbohydrates (e.g. glucose derived from starch, cellulose or sucrose) to current commodity and specialty chemicals was the selective removal of oxygen atoms from the carbohydrate.
SUMMARY OF THE INVENTION
[0010 ] Briefly, the present invention is directed to compositions of matter comprising an adipic acid product of formula (1)
wherein R is independently a salt-forming ion, hydrogen, hydrocarbyl, or substituted hydrocarbyl, and
at least one constituent selected from the group consisting of formula (2)
2
wherein R is as defined above and each of R is H, OH, acyloxy or substituted acyloxy provided, however, that at least one of R1 is OH, and formula (3)
RNVA 6358.1
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wherein R is as defined above and R1 is H, OH, acyloxy or substituted acyloxy.
[0011 ] 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.
[0012 ] 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).
[0013 ] 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).
[0014 ] 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).
[0015 ] 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.
[0016] Other objects and features will become apparent and/or will be pointed out hereinafter.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0017 ] In accordance with the present invention, applicants disclose 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.
[0018 ] 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. Glucose may be isolated from biorenewable sources using methods that are known in the art. See, for example, Centi and van RNVA 6358.1
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Santen, Catalysis for Renewables , Wiley-VCH, Weinheim 2007; Kamm, Gruber and Kamm, Biorefineries-Industrial Processes and Products, Wiley-VCH, Weinheim 2006; Shang-Tian Yang, Bioprocessing for Value-Added Products from Renewable Resources New Technologies and Applications, Elsevier B.V. 2007; Furia, Starch in the Food Industry, Chapter 8, CRC Handbook of Food Additives 2nd Edition CRC Press, 1973. See also chapters devoted to Starch, Sugar and Syrups within Kirk-Othmer Encyclopedia of Chemical Technology 5th Edition, John Wiley and Sons 2001. Also, processes to convert starch to glucose are known in the art; see, for example, Schenck, "Glucose and Glucose containing Syrups" in Ullmann 's Encyclopedia of Industrial Chemistry, Wiley-VCH 2009. Furthermore, methods to convert cellulose to glucose are known in the art, see, for example, Centi and van Santen, Catalysis for Renewables, Wiley-VCH, Weinheim 2007; Kamm, Gruber and Kamm, Biorefineries-Industrial Processes and Products, Wiley-VCH, Weinheim 2006; Shang-Tian Yang, Bioprocessing for Value-Added Products from Renewable Resources New Technologies and Applications, Elsevier B.V. 2007.
[ 0019 ] In accordance with the present invention, the 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.
[ 0020 ] The hydrodeoxygenation substrate comprises a compound of the following formula (A):
A RNVA 6358.1
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wherein 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.
[0021] As used herein, the term "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,
cycloalkylalkyl, heterocyclyl, N-heterocyclyl, heterocyclylalkyl, aryl, aralkyl heteroaryl, N- heteroaryl, heteroarylalkyl, and the like. A hydrocarbyl may be optionally substituted hydrocarbyl. Hence, various hydrocarbyls can be further selected from substituted alkyl, substituted cycloalkyl and the like.
[0022] Salt forming ions include, without limitation, for example ammonium ions and metal ions (e.g., alkali and alkaline earth metals). When R is a salt forming ion (i.e., a cation), the carboxyl group may be considered to be anion (i.e., carboxylate anion).
[0023] In various embodiments, 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.
[0024] As shown in formula (A), the hydrodeoxygenation substrate contains a six carbon chain comprising four chiral centers. As a result several stereoisomers are possible. However, the preferred hydrodeoxygenation substrate comprises glucaric acid.
[0025] The hydrodeoxygenation substrate may also contain various ketones. For example, not wishing to be bound by theory, when glucaric acid is further oxidized, 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.
[0026] The hydrodeoxygenation substrate may comprise various lactones derived from glucaric acid. For example, not wishing to be bound by theory, it is believed that 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. Moreover, 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. For example see "Convenient Large-Scale Synthesis of D-Glucaro-l,4:6,3-dilactone" Gehret et al, J. Org. Chem., 74 (21), pp. 8373-8376 (2009). Also, lactones such as L-t/zreo-4-deoxy-hex- RNVA 6358.1
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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.
[ 0027 ] Therefore, in various embodiments, the hydrodeoxygenation substrate comprises D-glucaro- 1 ,4-lactone. In these and other embodiments, the hydrodeoxygenation substrate comprises D-glucaro-6,3-lactone. Still further, in these and other embodiments, the hydrodeoxygenation substrate comprises D-glucaro-l,4:6,3-dilactone. In these and other embodiments, the hydrodeoxygenation substrate comprises L-?/zreo4-deoxy-hex-4-enaro-6,3- lactone. Still even further, in these and other embodiments, the hydrodeoxygenation substrate comprises L-ery?/zro-4-deoxy-hex-4-enaro-6,3-lactone.
[ 0028 ] In accordance with the present invention, the 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:
wherein X and R are defined as described above, and at least one constituent selected from the group consisting of formula (2)
wherein R is as defined above and each of R1 is, independently, H, OH, acyloxy or substituted acyloxy provided, however, that at least one of R1 is OH, and formula (3) RNVA 6358.1
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3
wherein R is as defined above and Rl is H, OH, acyloxy or substituted acyloxy.
[0029] In preferred embodiments, the compositions of matter comprise adipic acid and/or salt thereof and at least two other constituents selected from formulae (2) and (3), above.
[0030] In certain preferred embodiments, the 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.
[0031] In certain preferred embodiments, the 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.
[0032] In certain preferred embodiments, the 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.
[0033] It should be recognized that 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. In various embodiments, the hydrodeoxygenation substrate is halogenated with hydrobromic acid to form a brominated intermediate (e.g., an alkyl bromide). In other embodiments, the hydrodeoxygenation substrate is halogenated with a molecular bromine to form the brominated intermediate (e.g., an alkyl bromide).
[0034 ] 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.
[0035] 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
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[0036] Generally, the reaction allows for recovery of the bromine, and catalytic quantities of bromine can be used, recovered and recycled for continued use.
[0037] The temperature of the hydrodeoxygenation reaction mixture is preferably between about 100°C and 180°C.
[0038] Typically, the partial pressure of hydrogen is in the range of about 800 psia (5516kPa) to about 1300 psia (8964kPa).
[0039] The hydrodeoxygenation reaction is conducted in the presence of solvents. Mixtures of water and weak carboxylic acid, or weak carboxylic acid are suitable solvents.
Preferably, the weak carboxylic acid is acetic acid.
[0040] In general, 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.
Examples of 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.
[0041] 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). Typically, the metals constitute not more than about 8%, preferably less than or equal to about 4%.
[0042 ] 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.
[0043] 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. In various preferred embodiments, 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.
[0044] 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. In various embodiments, following metal deposition, the catalyst is dried at a temperature of at least about RNVA 6358.1
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50°C, more typically at least about 120°C or more for a period of time of at least about 1 hour, more typically at least about 3 hours or more. In these and other embodiments, the catalyst is dried under sub-atmospheric conditions. In various embodiments, the catalyst is reduced after drying (e.g., by flowing 5% H2 in 2 at 350 °C for 3 hours). Still further, in these and other embodiments, 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).
[0045 ] The 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.
Downstream Chemical Products
[0046] Various methods are known in the art for conversion of 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. For conversions from adipic acid, see for example, without limitation, U.S. Patent Nos. 3,671,566, 3,917,707, 4,767,856, 5,900,511, 5,986, 127, 6,008,418, 6,087,296, 6,147,208, 6,462,220, 6,521,779, 6,569,802, and Musser, "Adipic Acid" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2005.
[0047 ] In various embodiments, the 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,
"Hexamethylenediamine" in Ullmann 's Encyclopedia of Industrial Chemistry, Wiley-VCH 2009. RNVA 6358.1
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Therefore, the compositions of matter of the present invention can be converted to
hexamethylene diamine.
[0048] 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
Ullmann's Encyclopedia of Industrial Chemistry, Wiley -VCH, Weinheim, 2005. 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,
Pagilagan, Redmond, "Polyamides" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley - VCH, Weinheim, 2005.
[0049] Accordingly, the 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, as used herein, refers to a monomer which can be converted to a polymer (or copolymer) under appropriate polymerization conditions. In various embodiments, the polyamide comprises nylon 6,6. In these embodiments, the polymer precursor comprises hexamethylene diamine which may be derived from the compositions of the present invention.
[0050] In other embodiments, 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.
[0051 ] In other embodiments, 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.
[0052] In other embodiments, the 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. Accordingly, in various embodiments, 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
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[0053 ] In various embodiments 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.
[0054 ] When introducing elements of the present invention or the preferred embodiments(s) thereof, the articles "a", "an", "the" and "said" are intended to mean that there are one or more of the elements. The terms "comprising", "including" and "having" are intended to be inclusive and mean that there may be additional elements other than the listed elements.
[0055 ] In view of the above, it will be seen that the several objects of the invention are achieved and other advantageous results attained.
[0056] As various changes could be made in the above compositions and processes without departing from the scope of the invention, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense.
[0057 ] Having described the invention in detail, it will be apparent that modifications and variations are possible without departing from the scope of the invention defined in the appended claims.
EXAMPLES
[0058 ] The following non-limiting examples are provided to further illustrate the present invention.
[0059 ] Reactions were conducted in 1 mL glass vials housed in a pressurized vessel in accordance with the procedures described in the examples below. Product yields were determined using a Dionex ICS-3000 Chromatography system. For Example 1, the products were first separated on an Ionpac® AS1 1-HC column and then quantified by conductivity detection through comparison with calibration standards. For Example 2, the products were first separated on an Acclaim® Organic Acid column and then quantified by a UV detector through comparison with calibration standards.
EXAMPLE 1: GLUCOSE TO GLUCARIC ACID
[0060 ] Several catalysts were obtained from commercial vendors: Johnson Matthey 5% Pt/C (three examples; JM-23 [B103032-5, Lot #C-9090]; JM-25 [B 103014-5, Lot #C9230]; and JM-27 [B-501032-5, Lot #C-9188]), Johnson Matthey 5% Pt/Al203 (two examples; JM-32 [B301013-5, Lot #C8959] and JM-33 [B301099-5, Lot #C9218]), and BASF Escat 2351 5% RNVA 6358.1
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Pt/Si02 [Lot #A4048107]; and 1.5% Au/Ti02 [Sud Chemie 02-10]. Other catalysts were prepared in accordance with the procedure described herein.
Preparation of Supported Platinum Catalysts
[0061 ] Multiple portions of suitably concentrated aqueous Pt( 03)2 solutions (Heraeus) were added to the appropriate support (wherein the total combined volume of the Pt( 03)2 solutions was matched to equal to the pore volume of the chosen support) with agitation between additions. Post impregnation, the product was dried in a furnace at 120 °C for 12 hours, Material for catalyst testing was prepared by reduction under flowing 5 vol.% H2 in N2 for 3 hours at either 200 °C or 350 °C. Note that this procedure was used for all supports except carbon. See the later description for the preparation of a Pt/Carbon catalyst.
Preparation of Pt/M2/Support Catalysts (M2 = Mn, Co, Fe, Re, Cu)
[ 0062 ] Approximately 7 - 8 mg of dried supported platinum catalyst (taken post drying but prior to reduction) was dispensed into an 8 x 12 array containing 1 mL glass vials. To select vials within the array, 6 - 7 μΐ (where the total addition volume was matched to equal to the pore volume of the support weighed into the vial) of suitably concentrated M2 stock solutions were added (M2 = Mn, Fe, Co, Re, Cu obtained from Strem or Sigma-Aldrich, see Table 1). Post M2 addition, the mixtures were agitated via a multi-tube vortexer to impregnate the supports. Post impregnation, 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. % H2 in N2 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. In this case Ρί(Ν(¾)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. % H2 in N2 at 350 °C for 3 hours.
Preparation of 4 wt.% Pt/Carbon Catalyst
[0063 ] Multiple portions of suitably concentrated aqueous Pt(N03)2 solution (Heraeus) were added to 2 g of dried Degussa HP-160 furnace black carbon (3.94 mL total addition volume) with agitation between additions. Post impregnation, the 4 wt.% Pt/Carbon RNVA 6358.1
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was dried under vacuum for one hour at 50°C, followed by reduction under flowing 5 vol.% H2 in 2 for three hours at 350°C.
Glucose to Glucaric Acid Reactions
[0064 ] 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 μΐ., 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. After the reaction time had elapsed shaking was stopped and the reactor cooled to room temperature whereupon the reactors were vented. Samples for ion- chromatography (IC) analysis were prepared by adding to each reaction vial 750 μϊ^ of a 1.067 wt.% citric acid solution (as internal standard) then the plate was covered and mixed followed by centrifugation to separate catalyst particles. Each reaction sample was further diluted by performing two 20-fold dilutions then analyzed by Ion Chromatography. In some instances, HCl was used as alternative internal standard through the addition of 100 μϊ^ of 50 ppm solution during the second 20-fold dilution. The results are presented in Table 1.
Table 1
Catalyst Glucaric
Ml Temp. Time Amount Acid Yield
Catalyst (wt.% M2 wt.% Pt/Support) Precursor M2 Precursor (°C) (Hours) (mg) (%)
1 0.06% Mn 4% Pt / Silica Davisil 635 Pt(N03)2 Mn(N03)2 80 5 7 38
2 0.06% Fe 4% Pt / Silica Davisil 635 Pt(N03)2 Fe(N03)3 80 5 8 28
3 0.06% Co 4% Pt / Silica Davisil 635 Pt(N03)2 Co(N03)2 80 5 8 34
4 4% Pt / Silica Davisil 635 Pt(N03)2 None 80 5 8 34
5 4% Pt / Silica 5 μτη Cariact Pt(N03)2 None 90 5 8 50
6 4% Pt / Silica 5 μτη Cariact Pt(N03)2 None 90 8 8 66
7 4% Pt / Silica Merck 10180 Pt(N03)2 None 90 5 8 40
8 1.91% Re 4% Pt / Silica Merck 10180 Pt(N03)2 HRe04 90 5 8 39
9 0.65% Cu 4% Pt / Silica Merck 10180 Pt(N03)2 Cu(N03)2 90 5 8 39
10 0.10% Mo 4% Pt / Silica Merck 10180 Pt(N03)2 (NH4)6Mo7024 90 5 8 38
11 4% Pt / Carbon Degussa HP-160 Pt(N03)2 None 80 5 8 53
12 4% Pt / Carbon Degussa HP-160 Pt(N03)2 None 90 8 8 60
13 5% Pt / C [JM-23] None 80 5 10 52
14 5% Pt / C [JM-25] None 80 5 10 57
15 5% Pt / C [JM-27] None 80 5 10 57
16 5% Pt / Al203 [JM-32] None 80 5 10 23
17 5% Pt / Al203 [JM-33] None 80 5 10 31
18 5% Pt / Si02 [BASF Escat 2351] Pt(N03)2 None 80 5 10 15
19 8% Pt / Zirconia Daiichi Kigenso Z-1044 Pt(NQ3)2 None 90 5 8 52 RNVA 6358.1
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aThese catalysts were calcined at 500 °C for 3 hours prior to reduction.
bThese reactions were run under 500 psig of air, all other reactions in Table 1 were run under 75 psig of 02.
Catalysts in examples 4-7, 11-12 were reduced at 200 °C under flowing 5 vol.% H2 in N2 for 3 hours.
Catalysts in examples 1-3, 8-10, 19-25 were reduced at 350 °C under flowing 5 vol.% H2 in N2 for 3 hours.
Commercial catalysts in examples 13-18 were screened directly.
EXAMPLE 2: GLUCARIC ACID TO ADIPIC ACID
Preparation of Pt/Rh Supported Catalyst by Co-impregnation
[0065 ] 8 mg of 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. Post impregnation, 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.
Glucaric Acid to Adipic Acid Reaction
[0066] 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). Upon solution addition, 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 μΐ 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
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the catalyst particles. The reaction sample was then diluted 2-fold with water to generate a sample for analysis by HPLC. The results are presented in Table 2.
Table 2.
Recovery of Composition of Matter of the Present Invention
[0067 ] Solution is collected from the outlet of a reactor. The solution is evaporated to dryness. Acetic acid is added in sufficient quantity to dissolve the material at 90 °C. The dissolved material is allowed to crystallize at room temperature. Crystals are recovered by filtration and further recrystallized an additional 3 times from water using a concentration of lg of crystals in 5 mL of water. During a second recrystallization, the hot solution is filtered through decolorizing carbon. Finally, the crystals a dried under vacuum at 60 °C. The composition is determined to be >99+ wt% purity adipic acid by ¾ NMR. Mass spectrometry reveals peaks consistent with the presence the molecules represented by formula (2) and formula (3), above, depicted below, in cumulative amount <1.0 wt%.
EXAMPLE 3: The Preparation of Adipic Acid from Glucose Using Continuous Fixed Bed Reactors
Preparation of 4 wt.% Pt-4 wt.% Au/Titania Catalyst
[0068 ] 625 μΐ of an aqueous solution of HAuCU (containing 22.54 wt.% Au) was added to a suspension of 5.0 g Titania ST 31 119 (Saint-Gobain Norpro) in deionized water (500 ml) while stirring. The suspension was stirred at room temperature for 30 minutes. 30 ml of an aqueous solution of urea (20 wt.%) was added to above suspension and the resulting suspension was heated at 80°C overnight with stirring. The suspension was then cooled to room temperature, centrifuged and supernatant was decanted. 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% H2 and 95% N2) atmosphere for 3 hours with 2°C/min temperature ramp rate to give 4.90 g purple solid.
[0069 ] 1.225 ml of an aqueous solution of Pt( 03)2 (containing 1 1.4 wt% Pt) was added to the purple solid in 4 portions. After each addition, the mixture was agitated to impregnate the Au-containing support. The sample was dried in a 60°C oven overnight under a RNVA 6358.1
17
dry air purge. The sample was then reduced at 350°C under a forming gas (5% H2 and 95% N2) 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.
Preparation of 2.3 wt.% Pt-0.8 wt.% Rh/Silica Catalyst
[0070 ] 2 g of dried Silica Davisil 635, pore size 60 A, 60-100 mesh (Aldrich) was weighed into a vial. A suitably concentrated Pt-Rh stock solution was prepared from
concentrated acidic stock solutions purchased from Heraeus. Multiple additions of the Pt-Rh stock solution were added to the silica (silica pore volume = 0.88 mL/g) until a total volume of 1.76 ml was reached. After each addition, the mixture was agitated to impregnate the silica. Post impregnation, the Pt-Rh/Silica mixtures were dried in a furnace at 120 °C for 12 hours, followed by calcination at 500 °C for 3 hours. Upon cooling the catalysts were stored in a dessicator until used.
Conversion of Glucose to Glucaric Acid
[0071 ] The reaction was performed in a ¼-inch OD by 401mm long 321 stainless steel tube with 2μιη 316 stainless steel frits at both ends of the catalyst bed. Catalyst beds were vibration packed with silicon carbide (180 - 300 μιη) at the bottom to approximately 40mm depth followed by catalyst (1.757g) then silicon carbide (180 - 300μιη) to the top. The packed reactor tube was clamped in an aluminum block heater equipped with PID controller. All reactions were performed with gas and liquid entering at the top of the reactor with the conditions described in Table 3. Gas and liquid flows were regulated by mass flow controller and HPLC pump, respectively. 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.
Table 3:
Glucose Reactor Liquid Gas flowrate / Glucose Glucaric
Reactor
Example concentration / pressure / flowrate / mL min"1 conversion / acid yield / temperature / °C
wt% psi min"1 (STP) % %
1 105 20 350 100 114 100.0 59.4 RNVA 6358.1
18
Conversion to Adipic Acid
[0072 ] Product from the oxidation fixed bed reactor was concentrated by evaporation and dried to produce a glucaric acid product containing 1.2% water (determined by Karl-Fischer titration). This material was redissolved in acetic acid and HBr to make 250mL of a solution which was 0.2 M in HBr and contained 9.6 g of the glucaric acid product. This solution was run through a fixed bed reactor containing 2.5 g of 2.3 wt.% Pt-0.8 wt.% Rh on Davisil 635 silica at a flow rate of 50 μΕ/ηήη with a concurrent hydrogen flow rate of 5 seem at lOOOpsi. The reactor has two heated zones. The first zone was a 6-inch zone heated at 1 10 °C and next zone was another 6 inch zone heated at 140 °C.
Recovery of composition of matter of the present invention
[0073 ] 200 mL of solution collected from the outlet of the fixed bed reactor was evaporated to dryness. Acetic acid was added (3mL AcOH per gram crude) and the material was dissolved at 90 °C and allowed to crystallize at room temperature. Crystals were recovered by filtration and further recrystallized an additional 3 times from water using a concentration of lg of crystals in 5 mL of water. During the second recrystallization, the hot solution was filtered through decolorizing carbon. Finally, the crystals were dried under vacuum at 60 °C. The adipic acid crystals were determined to be > 99.5 wt % pure by XH NMR. Mass spectrometry revealed peaks consistent with the presence the molecules depicted below, at levels <0.5 wt %.

Claims

RNVA 6358.1 19 WHAT IS CLAIMED IS:
1. A composition of matter comprising an adipic acid product of formula (1)
1
wherein R is independently a salt-forming ion, hydrogen, hydrocarbyl, or substituted hydrocarbyl, and
at least one constituent selected from the group consisting of formula (2)
wherein R is as defined above, Rl is H, OH, acyloxy or substituted acyloxy provided, however, at least one of Rl is OH, and formula (3)
3
wherein R is as above defined and Rl is H, OH, acyloxy or substituted acyloxy.
2. The composition of matter of claim 1 comprising the adipic acid product of formula (1) and at least two different constituents selected from the group of formula (2) and formula (3).
3. The composition of matter of claim 1 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). RNVA 6358.1
20
4. The composition of matter of claim 1 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).
5. The composition 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).
6. Adiponitrile prepared at least in part from the composition of matter of any one of claims 1 to 5.
7. A polyamide produced at least in part from the composition of matter of any of claims 1 to 5.
8. Caprolactam produced at least in part from the composition of matter of any of claims 1 to 5.
9. A polyester produced in least in part from the composition of matter of any of claims 1 to
5.
EP10812827A 2010-03-05 2010-12-13 Adipic acid composition Withdrawn EP2542519A1 (en)

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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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