CN102869642A - Adipic acid composition - Google Patents

Adipic acid composition Download PDF

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Publication number
CN102869642A
CN102869642A CN2010800651905A CN201080065190A CN102869642A CN 102869642 A CN102869642 A CN 102869642A CN 2010800651905 A CN2010800651905 A CN 2010800651905A CN 201080065190 A CN201080065190 A CN 201080065190A CN 102869642 A CN102869642 A CN 102869642A
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Prior art keywords
composition
formula
weight
acid
hexanodioic acid
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CN2010800651905A
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Chinese (zh)
Inventor
T·R·布西尔
E·L·迪亚斯
Z·M·费雷斯科
V·J·墨菲
J·休梅克
R·阿切尔
H·蒋
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Archer Daniels Midland Co
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Rennovia Inc
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Priority claimed from US12/814,188 external-priority patent/US8669397B2/en
Application filed by Rennovia Inc filed Critical Rennovia Inc
Priority to CN201910397901.1A priority Critical patent/CN110078614A/en
Publication of CN102869642A publication Critical patent/CN102869642A/en
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    • 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

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

The hexanodioic acid composition
Invention field
The present invention relates to a kind of composition that comprises following material: the hexanodioic acid product of formula (1)
Wherein R is into the alkyl of salt ion, hydrogen, alkyl or replacement independently; With
Be selected from least a composition by the following group that forms: formula (2)
Figure BDA00002100219900012
Wherein R as hereinbefore defined, R 1Be the acyloxy of H, OH, acyloxy or replacement, yet condition is R 1In at least one be OH; And formula (3)
Figure BDA00002100219900013
Wherein R as hereinbefore defined, and R 1It is the acyloxy of H, OH, acyloxy or replacement.
The invention still further relates to the hexanodioic acid product that comprises formula (1) and be selected from the composition of top formula (2) with the material of at least two kinds of different compositions of the group of formula (3).
The present invention includes and comprise at least about the hexanodioic acid of 99 % by weight or its salt and the composition of the material of at least a composition of the formula of about 1 % by weight (2) at the most.
The present invention also comprises and comprising at least about the hexanodioic acid of 99 % by weight and the composition of the material of at least a composition that selects the group that free style (2) and formula (3) form of about 1 % by weight at the most.
The present invention also comprises and comprising at least about the hexanodioic acid of 99 % by weight and the composition of the material of at least two kinds of compositions that select the group that free style (2) and formula (3) form of about 1 % by weight at the most.
The invention still further relates to the industrial chemical by the composition production of this class material, for example adiponitrile, hexanediamine, hexanolactam, caprolactone, 1,6-hexylene glycol, adipic acid ester, polymeric amide (for example, nylon) and polyester.
Background of invention
Crude oil is the source of most of commodity and special-purpose organic chemicals at present.Manyly in these chemical be used to make polymkeric substance and other materials.Example comprises ethene, propylene, vinylbenzene, dihydroxyphenyl propane, terephthalic acid, hexanodioic acid, hexanolactam, hexanediamine, adiponitrile, caprolactone, vinylformic acid, vinyl cyanide, 1,6-hexylene glycol, 1,3-PD and other.Crude oil at first is refined into the hydrocarbon intermediate, for example ethene, propylene, benzene and hexanaphthene.Then usually use various techniques with these hydrocarbon intermediate selective oxidations to produce required chemical.For example, crude oil is refined into hexanaphthene, and then hexanaphthene optionally is oxidized to " KA oil ", and " KA oil " then is further oxided to produce hexanodioic acid, and hexanodioic acid is a kind of important industrial monomers for the production of nylon 6,6.The precursor of finding in the many known technique cause crude oil of industrial employing is produced these petroleum chemicals.For example, referring to Ullmann ' s Encyclopedia of Industrial Chemistry, Wiley 2009 (the 7th edition), it incorporates this paper by reference into.Chemical and its derived product of being produced by thick oil do not contain the C-14 composition.
For many years, interesting with replacement or additional crude oil as raw material to using biological recyclable materials.Referring to, for example, Klass, Biomass for Renewable Energy, Fuels, and Chemicals, the academic press, 1998, it incorporates this paper by reference into.In addition, made great efforts to use the technique cause renewable resources of the combination that comprises biocatalysis technique and chemical catalysis technique to produce hexanodioic acid.Referring to, for example, " Benzene-Free Synthesis of AdipicAcid ", the people Biotechnol.Prog.2002 such as Frost, the 18th volume, 201-211 page or leaf, and United States Patent (USP) the 4th, 400, No. 468 and the 5th, 487, No. 987.From different by the product of crude production, by biological recyclable materials, the visibly different feature of product introduction of more particularly being produced by the carbohydrate that is derived from it, one of them is to have the C-14 composition.
At the U. S. application series No.12/814 common in a review that finds to be submitted on June 11st, 2010 by people such as Boussie, in 188 before the disclosed technique, be used for biological renewable resources for example one of carbohydrate (glucose of for example, being derived by starch, Mierocrystalline cellulose or sucrose) main challenge of being converted into current commodity and specialty chemicals be optionally to remove Sauerstoffatom from carbohydrate.
Summary of the invention
Tout court, the present invention relates to a kind of composition that comprises following material: the hexanodioic acid product of formula (1)
Figure BDA00002100219900031
Wherein R is into the alkyl of salt ion, hydrogen, alkyl or replacement independently; With
Be selected from least a composition by the following group that forms: formula (2)
Figure BDA00002100219900041
Wherein R as hereinbefore defined, and R 1In each be the acyloxy of H, OH, acyloxy or replacement, yet condition is R 1In at least one be OH; And formula (3)
Figure BDA00002100219900042
Wherein R as hereinbefore defined, and R 1It is the acyloxy of H, OH, acyloxy or replacement.
The invention still further relates to the hexanodioic acid product that comprises formula (1) and be selected from the composition of top formula (2) with the material of at least two kinds of different compositions of the group of formula (3).
The present invention includes and comprise at least about the hexanodioic acid of 99 % by weight or its salt and the composition of the material of at least a composition of the formula of about 1 % by weight (2) at the most.
The present invention also comprises and comprising at least about the hexanodioic acid of 99 % by weight and the composition of the material of at least a composition that selects the group that free style (2) and formula (3) form of about 1 % by weight at the most.
The present invention also comprises and comprising at least about the hexanodioic acid of 99 % by weight and the composition of the material of at least two kinds of compositions that select the group that free style (2) and formula (3) form of about 1 % by weight at the most.
The invention still further relates to the industrial chemical by the composition production of this class material, for example adiponitrile, hexanediamine, hexanolactam, caprolactone, 1,6-hexylene glycol, adipic acid ester, polymeric amide (for example, nylon) and polyester.
Other purposes and feature will become obviously and/or will point out hereinafter.
The description of preferred embodiment
According to the present invention, the applicant discloses the composition of the material of not produced before this and the method for producing the composition of described material, and such composition comprises the hexanodioic acid product of top formula (1) and is selected from least a composition of the group that is comprised of top formula (2) and (3).The composition of material of the present invention can be converted into various other industrial important chemical according to process quilt known in the art, comprise, for example, adiponitrile, hexanolactam, caprolactone, hexanediamine, 1,6-hexylene glycol, adipic acid ester, polymeric amide (for example, nylon) or polyester.
Glucose, it is the preferred raw material for the production of product of the present invention, can be obtained by various carbohydrate containing source, the carbohydrate containing source comprises that for example for example energy crops, plant biomass, agricultural waste, forest residue, sugar are processed the domesti refuse of residue and plant derivation to conventional biological renewable origin corn particle (corn), wheat, potato, cassava and paddy rice and selectable source.Can use methods known in the art from the reproducible source of biology separating glucose.Referring to, for example, Centi and van Santen, Catalysis for Renewables, Wiley-VCH, Weinheim 2007; Kamm, Gruber and Kamm, Biorefineries-Industrial Processes and Products, Wiley-VCH, Weinheim2006; Shang-Tian Yang, Bioprocessing for Value-Added Products from Renewable Resources New Technologies and Applications, ElsevierB.V.2007; Furia, Starchinthe Food Industry, the 8th chapter, CRC Handbook of Food Additives, the 2nd edition, CRC Press, 1973.Also referring to Kirk-Othmer Encyclopedia of Chemical Technology, the 5th edition, the chapter of special discussion starch, sugar and syrup in the John Wiley and Sons2001.In addition, the technique that starch is converted into glucose is known in the art; Referring to, for example, Schenck, " Glucose and Glucose containing Syrups " is in Ullmann ' s Encyclopedia of Industrial Chemistry, among the Wiley-VCH 2009.In addition, be that the method for glucose is known in the art with cellulose conversion, referring to, for example, Centi and van Santen, Catalysis for Renewables, Wiley-VCH, Weinheim 2007; Kamm, Gruber and Kamm, Biorefineries-Industrial Processes and Products, Wiley-VCH, Weinheim2006; Shang-Tian Yang, Bioprocessing for Value-Added Products from Renewable Resources New Technologies and Applications, ElsevierB.V.2007.
According to the present invention, the composition of material of the present invention is by with the preparation of getting off: the source of glucose chemical catalysis is converted into the hydrogenation deoxidation substrate that comprises saccharic acid at least and/or its derivative, subsequently this substrate is transformed in the presence of the bromine source and in the presence of acetic acid solvent by the chemical catalysis method that employing comprises the heterogeneous catalyst of platinum or platinum and rhodium, the reaction product experience that wherein makes the hydrogenation deoxidation step by the technology that usually adopts in the purifying of the hexanodioic acid of common process production to produce the composition of material of the present invention, this type of technology comprises, for example washing, crystallization and recrystallization.
The hydrogenation deoxidation substrate comprises the compound of following formula (A):
Figure BDA00002100219900061
Wherein X is hydroxyl, oxo, halo, acyloxy or hydrogen independently, and condition is that at least one X is not hydrogen; R is into the alkyl of salt ion, hydrogen, alkyl or replacement independently; Or its single lactone or dilactone.
As used herein, term " alkyl " refers to preferably comprise 1 to about 50 carbon atoms, preferably 1 to about 30 carbon atoms and even the 1 hydrocarbon part to about 18 carbon atoms more preferably, comprise side chain or unbranched and saturated or unsaturated kind.Preferred alkyl can be selected from the group that is comprised of following: alkyl, alkylidene group, alkoxyl group, alkylamino, alkylthio, haloalkyl, cycloalkyl, cycloalkylalkyl, heterocyclic radical, N-heterocyclic radical, Heterocyclylalkyl, aryl, aralkyl heteroaryl, N-heteroaryl, heteroarylalkyl and analogue.Alkyl can be the alkyl that randomly replaces.Therefore, various alkyl can also be selected from the alkyl of replacement, cycloalkyl and the analogue of replacement.
The salify ion includes but not limited to, for example ammonium ion and metal ion (for example, alkali and alkaline earth metal ions).When R was into salt ion (that is, positively charged ion), carboxyl can be considered to negatively charged ion (that is, carboxylate anion).
In various embodiments, the hydrogenation deoxidation substrate comprises the compound of formula (A), and wherein X is the alkyl that hydroxyl and R are into salt ion, hydrogen, alkyl or replacement independently.
Suc as formula shown in (A), the hydrogenation deoxidation substrate comprises six carbochains, and six carbochains comprise four chiral centres.Therefore, some steric isomers are possible.Yet preferred hydrogenation deoxidation substrate comprises saccharic acid.
The hydrogenation deoxidation substrate can also comprise various ketone.For example, be not wishing to be bound by theory, when saccharic acid is further oxided, can form ketone for example 2-ketone group-saccharic acid (2,3,4-trihydroxy--5-oxo hexanodioic acid) and 3-ketone group-saccharic acid (2,3,5-trihydroxy--4-oxo hexanodioic acid).
The hydrogenation deoxidation substrate can comprise the various lactones derived from saccharic acid.For example, be not wishing to be bound by theory, think, the saccharic acid balance in various single lactones and dilactone and the aqueous solution exists, saccharic acid for example comprises, D-saccharic acid-Isosorbide-5-Nitrae-lactone, D-saccharic acid-6,3-lactone and D-saccharic acid-Isosorbide-5-Nitrae: 6,3-dilactone.In addition, technique has been developed to the saccharic acid in the solution or its salt is converted into quantitatively one or more lactones and reclaims basically pure lactone stream.For example referring to people such as " Convenient Large-Scale Synthesis ofD-Glucaro-1; 4:6; 3-dilactone (D-saccharic acid-1; 4:6; easy to be extensive the synthesizing of 3-dilactone) " Gehret, J.Org.Chem., the 74 (21), the 8373rd 8376 pages of – (2009).In addition, for example L-Su Shi-4-deoxidation of lactone-oneself-obtusilic acid-6,3-lactone (L-threo-4-deoxy-hex-4-enaro-6,3-lactone) with L-erythro form-4-deoxidation-own-obtusilic acid-6, the 3-lactone can be by D-saccharic acid-Isosorbide-5-Nitrae: the thermolysis of 6,3-dilactone forms.
Therefore, in various embodiments, the hydrogenation deoxidation substrate comprises D-saccharic acid-Isosorbide-5-Nitrae-lactone.In these and other embodiments, the hydrogenation deoxidation substrate comprises D-saccharic acid-6, the 3-lactone.Also further, in these and other embodiments, the hydrogenation deoxidation substrate comprises D-saccharic acid-Isosorbide-5-Nitrae: 6,3-dilactone.In these and other embodiments, the hydrogenation deoxidation substrate comprises L-Su Shi-4-deoxidation-own-obtusilic acid-6,3-lactone.Also even in addition, in these and other embodiments, the hydrogenation deoxidation substrate comprise L-erythro form-4-deoxidation-oneself-obtusilic acid-6, the 3-lactone.
According to the present invention, the composition of material comprises: hexanodioic acid product (formula 1), hexanodioic acid product (formula 1) according to following reaction by in the presence of bromine source (preferably HBr), the hydrogenation deoxidation catalyst that comprises platinum or platinum and rhodium and solvent (preferably acetic acid), hydrogenation deoxidation substrate (formula A) and hydrogen reaction being prepared:
Figure BDA00002100219900081
Wherein X and R are defined as described above; With at least a composition that is selected from by the following group that forms: formula (2)
Figure BDA00002100219900082
Wherein R as hereinbefore defined, and R 1In each be the acyloxy of H, OH, acyloxy or replacement independently, yet condition is R 1In at least one be OH; And formula (3)
Figure BDA00002100219900083
Wherein R as hereinbefore defined, and R 1It is the acyloxy of H, OH, acyloxy or replacement.
In preferred embodiments, the composition of material comprises hexanodioic acid and/or its salt and at least two kinds of other compositions that are selected from top formula (2) and (3).
In certain preferred aspects, the composition of material comprises at least about 99% hexanodioic acid or its salt and 1% at least a composition that is selected from top formula (2) and (3) at the most.
In certain preferred aspects, the composition of material comprises at least about 99% hexanodioic acid or its salt and at least a composition of 1% top formula (2) at the most.
In certain preferred aspects, the composition of material comprises at least about 99% hexanodioic acid or its salt and two kinds of compositions that are selected from top formula (2) and (3) of 1% at the most at least.
Will be appreciated that, hydrogenation deoxidation reaction can be by carrying out to get off: at first form various intermediates with purifying randomly or separate various intermediates, described various intermediates are by combined hydrogenation deoxidation substrate and bromine source and under without any other halogen source intermediate and hydrogen reaction are formed in the presence of the hydrogenation deoxidation catalyst and randomly subsequently.In various embodiments, the hydrogenation deoxidation substrate uses the Hydrogen bromide halogenation to form brominated intermediates (for example, alkyl bromide).In other embodiments, the hydrogenation deoxidation substrate uses the molecular bromine halogenation to form brominated intermediates (for example, alkyl bromide).
The bromine source can be the form that is selected from by the following group that forms: atomic form, ionic species, molecular form and composition thereof.The bromine source is hydrogen bromide most preferably.
The mol ratio of bromine and hydrogenation deoxidation substrate is less than 1.In various embodiments, the mol ratio of halogen and hydrogenation deoxidation substrate is usually less than about 0.5.
Usually, reaction allows to reclaim bromine, and the bromine of catalytic amount can be used, reclaims and be cycled to used in continuous use.
The temperature of hydrogenation deoxidation reaction mixture is preferably between about 100 ℃ and 180 ℃.
Usually, hydrogen partial pressure at about 800psia (5516kPa) to the scope of about 1300psia (8964kPa).
The hydrogenation deoxidation reaction is carried out in the presence of solvent.The mixture of water and weak carboxylic acids, or weak carboxylic acids is suitable solvent.Preferably, weak carboxylic acids is acetic acid.
Generally speaking, reaction can be carried out in any other design of using the batch reactor design of fixed-bed reactor, trickle-bed reactor, slurry-phase reactor, moving-burden bed reactor, semi batch reactor design or flow reactor design or permission heterogeneous catalytic reaction.The example of reactor can see Chemical Process Equipment-Selection and Design, the people such as Couper, and Elsevier 1990, and it incorporates this paper by reference into.Should be understood that hydrogenation deoxidation substrate, halogen source, hydrogen, any solvent and hydrogenation deoxidation catalyst can be introduced in the suitable reactor individually or with various combinations.
Hydrogenation deoxidation catalyst is the solid-phase heterogenous catalysts that comprises platinum or platinum and rhodium that is present in (preferably, in one or more surfaces, outside or inner) on the carrier.Usually, metal is constituted to how about 8%, preferably is less than or equal to about 4%.
The Pt:Rh molar ratio can change, and for example, about 20:1 is to about 0.1:1, about 10:1 about 0.5:1 and more preferably extremely, and about 5:1 is about 1:1 extremely.
Preferred support of the catalyst comprises charcoal, silicon-dioxide, titanium dioxide, zirconium white, zeolite, clay, silicon carbide and version thereof, mixture or combination.Preferred carrier can come modification by methods known in the art, for example such as thermal treatment, acid treatment, introducing doping agent.In various preferred embodiments, the hydrogenation deoxidation catalyst carrier is selected from the group that is comprised of silicon-dioxide, zirconium white and titanium dioxide.Preferred catalyzer is included in platinum and the rhodium on the carrier that comprises silicon-dioxide.
Can deposit metal on the carrier with program known in the art, described program includes but not limited to just wet impregnation method, ion-exchange, deposition-precipitation and vacuum impregnation.Metal can be deposited according to priority or side by side.In various embodiments, after metal deposition, at least about 50 ℃, more generally at least about dry catalyst under 120 ℃ or the higher temperature at least about 1 hour, more generally at least 3 hours or longer time period.In these and other embodiments, dry catalyst under subatmospheric condition.In various embodiments, reducing catalyst is (for example, by flowing through N at 350 ℃ after drying 2In 5%H 2, continue 3 hours).Also further, in these and other embodiments, with catalyzer for example at least about temperature lower calcination for some time (for example, at least about 3 hours) of 500 ℃.
The composition of material of the present invention can reclaim from the hydrogenation deoxidation reaction mixture by one or more conventional methods known in the art, and described method comprises, for example solvent extraction, crystallization or evaporative process.The reaction product that reclaims from hydrogenation deoxidation reaction comprise the hexanodioic acid product and, usually several with the top formula (2) of liquid form and/or the other composition of (3).The reaction product that reclaims is dried.Dry can be in the atmosphere of any suitable inertia, in air or under vacuum, carry out.Carrying out dry temperature should be enough to so that the composition of material will be settled out solution.Usually, temperature will about 25 ℃ to about 120 ℃ scope.Then, throw out can experience for the conventional processing that reclaims the hexanodioic acid of producing by common process, and this type of processing comprises, for example, for example wash with water, subsequently for example again dissolving and recrystallization (once or how extra inferior), with rear decoloring process and, for example, final recrystallization and washing.
The downstream chemical product
The whole bag of tricks that hexanodioic acid is converted into downstream chemical product or intermediate known in the art, downstream chemical product or intermediate comprise adipic acid ester, polyester, adiponitrile, hexanediamine (HMDA), hexanolactam, caprolactone, 1, and 6-hexylene glycol, hexosamine and polymeric amide be nylon for example.For being transformed by hexanodioic acid, referring to such as, but not limited to, United States Patent (USP) the 3rd, 671, No. 566, the 3rd, 917, No. 707, the 4th, 767, No. 856, the 5th, 900, No. 511, the 5th, 986, No. 127, the 6th, 008, No. 418, the 6th, 087, No. 296, the 6th, 147, No. 208, the 6th, 462, No. 220, the 6th, 521, No. 779, the 6th, 569,802 and Musser, " Adipic Acid " is in Ullmann ' s Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim is in 2005.
In various embodiments, the composition that comprises at least about the material of the present invention of the hexanodioic acid of 99 % by weight can be converted into adiponitrile.Adiponitrile can be industrial for the manufacture of hexanediamine, and referring to Smiley, " Hexamethylenediamine " is in Ullmann ' s Encyclopedia of Industrial Chemistry, among the Wiley-VCH 2009.Therefore, the composition of material of the present invention can be converted into hexanediamine.
Hexanodioic acid can be used for producing polymeric amide, for example nylon 6,6 and nylon 4,6.Referring to, for example, United States Patent (USP) the 4th, 722, No. 997, and Musser, " Adipic Acid ", and in Ullmann ' s Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim is in 2005.The hexanediamine that is formed by the composition that comprises at least about the material of the present invention of the hexanodioic acid of 99 % by weight similarly can be further used for preparing polymeric amide for example nylon 6,6 and nylon 6,12.Referring to, Kohan for example, Mestemacher, Pagilagan, Redmond, " Polyamides ", and in Ullmann ' s Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim is in 2005.
Therefore, comprise at least about the composition of the material of the present invention of 99 % by weight hexanodioic acids and the polymer precursor that is derived from such composition and can react to produce polymeric amide.Polymer precursor refers to can be converted into the monomer of polymkeric substance (or multipolymer) under suitable polymerizing condition as used herein.In various embodiments, polymeric amide comprises nylon 6,6.In these embodiments, polymer precursor comprises the hexanediamine that can be derived from composition of the present invention.
In other embodiments, the composition that comprises at least about the material of the present invention of 99 % by weight hexanodioic acids can be converted into hexanolactam.Formed hexanolactam can be further used for preparing polymeric amide by the common known method in this area.Especially, hexanolactam can be further used for preparing nylon 6.Referring to, Kohan for example, Mestemacher, Pagilagan, Redmond, " Polyamides ", and in Ullmann ' s Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim is in 2005.
In other embodiments, hexanodioic acid and polymer precursor can react to produce polyester, and wherein the hexanodioic acid product prepares according to the present invention.
In other embodiments, the composition that comprises at least about the material of the present invention of 99 % by weight hexanodioic acids can be converted into 1,6-hexylene glycol.1,6-hexylene glycol is the valuable chemical intermediate for the production of polyester and urethane.Therefore, in various embodiments, polyester can by make comprise at least about the composition of the material of the present invention of 99 % by weight hexanodioic acids be derived from 1 of such composition of the present invention, the 6-hexylene glycol reacts to prepare.
In various embodiments, can produce the salt of hexanodioic acid, wherein technique comprises and makes composition and the hexanediamine reaction that comprises at least about the material of the present invention of 99 % by weight hexanodioic acids, forms thus salt.
When introducing the key element of the present invention or its preferred embodiment, article " (a) ", " one (an) ", " should (the) " and " described (said) " be intended to refer to exist one or more in the key element.Term " comprises (comprising) ", " comprising (including) " and " having (having) " be intended that included and mean to exist the other key element that is different from the key element of listing.
In view of foregoing, will see that some purposes of the present invention are implemented and obtain other favourable results.
When above-mentioned composition and technique are carried out various variation, do not depart from scope of the present invention, all the elements that comprise in the expection foregoing description should be interpreted as illustrative and not be with restrictive meaning.
Described the present invention in detail, be apparent that, modifications and variations are possible, and do not depart from the scope of the invention that defines in the appended claim.
Embodiment
Provide following non-limiting example with further explaination the present invention.
According to the program of describing among the embodiment below, react in the 1mL vial in being accommodated in pressurizing vessel.Use Dionex ICS-3000 chromatography system to determine product yield.For embodiment 1, at first exist
Figure BDA00002100219900131
Separated product and then detecting by relatively quantizing product with the calibration criterion product by specific conductivity on the AS11-HC post.For embodiment 2, at first exist
Figure BDA00002100219900132
On the organic acid post separated product and then by the UV detector by relatively quantizing product with the calibration criterion product.
Embodiment 1: glucose is to saccharic acid
Some catalyzer obtain from commercial supplier: Johnson Matthey 5%Pt/C (three examples; JM-23[B103032-5, Lot#C-9090]; JM-25[B103014-5, Lot#C9230]; And JM-27[B-501032-5, Lot#C-9188]), Johnson Matthey 5%Pt/Al 2O 3(two examples; JM-32[B301013-5, Lot#C8959] and JM-33[B301099-5, Lot#C9218]), and BASF Escat 23515%Pt/SiO 2[Lot#A4048107]; And 1.5%Au/TiO 2[S ü d Chemie 02-10].Other catalyzer prepare according to program described herein.
The preparation of load platinum catalyst
With suitably concentrated Pt (NO 3) 2The a plurality of parts of the aqueous solution (Heraeus) add in the suitable carrier (Pt (NO wherein 3) 2Total combined volume coupling of solution equals the pore volume of selected carrier), and between adding, stir.Behind the dipping, with product in stove 120 ℃ of dryings 12 hours.By 200 ℃ or 350 ℃ current downflow at N 2In 5 volume %H 2The material that lower reduction came for the preparation of catalyst test in 3 hours.Notice that this program is used for all carriers except carbon.Referring to the description for the preparation of Pt/ Pd/carbon catalyst after a while.
The preparation of Pt/M2/ carried catalyst (M2=Mn, Co, Fe, Re, Cu)
The load platinum catalyst of the drying of about 7-8mg (after drying but gathered before reduction) is dispensed in the 8x12 array that comprises the 1mL vial.In order to select the bottle in the array, the M2 stock solution (M2=Mn, Fe, Co, Re, the Cu that suitably concentrate that add 6-7 μ l (wherein making total adding volume matched equal to be weighed the pore volume of the carrier in the bottle), obtain from Strem or Sigma-Aldrich, referring to table 1).After M2 added, mixture stirred with impregnated carrier via multitube vortex vibrator.After the dipping, with the vial array of Pt/M2/ carried catalyst in stove 120 ℃ lower dry 1 hour, subsequently 500 ℃ of lower calcinings 3 hours, subsequently 200 ℃ or 350 ℃ current downflow at N 2In 5 volume %H 2Lower reduction 3 hours.Notice that this program is for the preparation of all the Pt/M2/ carried catalysts except the 1.5%Pt/1.5%Au/ titanium deoxide catalyst.In this case, under agitation with Pt (NO 3) 2Solution adds dry commercial 1.5%Au/ titanium deoxide catalyst sample [S ü d Chemie 02-10] (wherein makes Pt (NO 3) 2The cumulative volume of volume coupling equals the pore volume of catalyzer), afterwards, with material in stove 120 ℃ lower dry 1 hour, subsequently 350 ℃ of current downflow at N 2In 5 volume %H 2Lower reduction 3 hours.
The preparation of 4 % by weight Pt/ Pd/carbon catalysts
With suitably concentrated Pt (NO 3) 2A plurality of parts of the aqueous solution (Heraeus) add the Degussa HP-160 black (3.94mL always adds volume) of 2g drying, and stir between adding.Behind the dipping, with 4 % by weight Pt/ charcoals under vacuum 50 ℃ lower dry one hour, subsequently 350 ℃ of current downflow at N 2In 5 volume %H 2Lower reduction 3 hours.
Glucose to saccharic acid reacts
Catalyzer is distributed in the interior 1mL bottle of 96 hole reactor insets (Symyx Solutions).Reaction substrate is D-Glucose (Sigma-Aldrich, 0.552M is in water).Add 250 μ L glucose solutions to each bottle.Each personal teflon pin-and-hole sheet of bottle, siloxanes pin-and-hole pad and steel gas diffusion plate (Symyx Solutions) are covered.The reactor inset is placed in the pressurized vessel and loads three times with oxygen, until 100psig, and exhaust after each pressurization steps.Then reactor is loaded into 75psig with oxygen or is loaded into 500psig, seals and is placed on the wobbler with air, the reaction times of heating appointment under the temperature of appointment.After passing by in the reaction times, stop to shake and with reactor cooling to room temperature, make afterwards the reactor exhaust.Be used for sample that ion-chromatography (IC) analyzes by with the preparation of getting off: add the 1.067 % by weight citric acid solutions (as interior mark) of 750L to each reaction bottle, then wrapper plate and mixing are centrifugal with separating catalyst particles afterwards.Each response sample further dilutes by carrying out twice 20 times of dilutions, then analyzes by ion chromatography.In some cases, by the 50ppm solution that during 20 times of dilutions second time, adds 100 μ L HCl is used as selectable interior mark.In table 1, present the result.
Table 1
Figure BDA00002100219900151
Figure BDA00002100219900161
aThese catalyzer were being calcined 3 hours under 500 ℃ before the reduction.
bThese reactions are carried out under the air of 500psig, and the every other reaction in the table 1 is at the O of 75psig 2Under carry out.
With the catalyzer among embodiment 4-7, the 11-12 under 200 ℃ flow at N 2In 5 volume %H 2Lower reduction 3 hours.
With the catalyzer among embodiment 1-3,8-10, the 19-25 under 350 ℃ flow at N 2In 5 volume %H 2Lower reduction 3 hours.
Directly screen the commercial catalysts among the embodiment 13-18.
Embodiment 2: saccharic acid is to hexanodioic acid
Catalyzer by total immersion stain preparation Pt/Rh load
Silica supports (Davisil 635W.R.Grace﹠amp with 8mg; Co.) be assigned in the 1mL vial.Carrier is lower dry 12 hours at 120 ℃ before use.Add the premixed stock solution (obtaining from Heraeus) that (wherein making total adding volume matched equal to be weighed the pore volume of the carrier in the bottle) suitably concentrates to bottle.After metal added, mixture stirred with impregnated carrier via multitube vortex vibrator.After the dipping, with the vial array of catalyzer in stove 120 ℃ lower dry 1 hour, subsequently 500 ℃ of lower calcinings 3 hours.After cooling, catalyzer was stored in the moisture eliminator before being used.
Saccharic acid to hexanodioic acid reacts
Catalyzer is transferred in the interior 1mL vial of 96 hole reactor insets (Symyx Solutions).The 0.2M saccharic acid in acetic acid (Sigma-Aldrich) (by the calglucon preparation) that bottle receives granulated glass sphere, 250 μ L (Sigma-Adrich) and 0.2M HBr (Sigma-Aldrich).After solution adds, bottle is covered with teflon pin-and-hole sheet, siloxanes pin-and-hole pad and steel gas diffusion plate (Symyx Solutions).The reactor inset is placed in the pressurized vessel, and pressurized vessel is with nitrogen pressurization and exhaust 3 times and usefulness pressurized with hydrogen and exhaust 3 times, then with pressurized with hydrogen to 710psig, be heated to 160 ℃ and shook 3 hours.After 3 hours, with reactor cooling, exhaust and use nitrogen purging.Then the water that adds 750 μ L to bottle.After water adds, bottle is covered and shakes to guarantee sufficient mixing.Subsequently, capped bottle is placed in the whizzer with separating catalyst particles.Then 2 times of response sample dilute with waters are used for the sample analyzed by HPLC to produce.In table 2, present the result.
Table 2.
Figure BDA00002100219900181
The recovery of the composition of material of the present invention
Collect solution from the outlet of reactor.Solution evaporation is extremely done.The acetic acid that adds q.s is with at 90 ℃ of lower dissolved materials.Make the at room temperature crystallization of material of dissolving.Crystal is by filtering to reclaim and using the concentration of 1g crystal in 5mL water from the further recrystallization of water other for 3 times.During the second recrystallization, the solution of heat is filtered by decolorizing charcoal.At last, crystal is lower dry at 60 ℃ under vacuum.According to 1H NMR, composition is confirmed as〉hexanodioic acid of 99+ % by weight purity.Mass spectroscopy shows that the existence of the molecule that peak and the following top formula (2) of being described and formula (3) with cumulative amount＜1.0 % by weight represent is consistent.
Embodiment 3: use continuous fixed-bed reactor to prepare hexanodioic acid by glucose
The preparation of 4 % by weight Pt-4 % by weight Au/ titanium deoxide catalysts
HAuCl with 625 μ l 4The aqueous solution joins (comprising 22.54 % by weight Au) deionized water (500ml) suspension of 5.0g titanium dioxide ST 31119 (Saint-Gobain Norpro), stirs simultaneously.Suspension was at room temperature stirred 30 minutes.The urea aqueous solution (20 % by weight) of 30ml is joined top suspension, and with resulting suspension heated overnight under agitation under 80 ℃.Then suspension is cooled to room temperature, centrifugal and supernatant decanted liquid.With the washing of the deionized water (3x400ml) of 50 ℃ of pale yellow colored solid body and functions, afterwards, with its under dry air purges in 60 ℃ of baking ovens dried overnight.Then with sample under 200 ℃ at synthesis gas (5%H 2And 95%N 2) under the atmosphere with 2 ℃/min temperature rise rate reduction 3 hours, to produce 4.90g purple solid.
Pt (NO with 1.225ml 3) 2The aqueous solution (comprising 11.4 % by weight Pt) joins in the purple solid with 4 parts.After adding each time, stir the mixture to flood the carrier that comprises Au.With sample under dry air purges in 60 ℃ of baking ovens dried overnight.Then with sample under 350 ℃ at synthesis gas (5%H 2And 95%N 2) under the atmosphere with 2 ℃/min temperature rise rate reduction 3 hours.Final catalyzer mainly is comprised of about 4.0 % by weight Au and 4.0 % by weight Pt.
2.3 the preparation of % by weight Pt-0.8 % by weight Rh/ SiO 2 catalyst
With the silicon-dioxide Davisil 635 of 2g drying, pore size 60-100 order (Aldrich) weighing enters in the bottle.Suitably dense Pt-Rh stock solution is by the dense acid stock solution preparation of buying from Heraeus.The a plurality of interpolations part of Pt-Rh stock solution is joined silicon-dioxide, and (silicon-dioxide volume of voids=0.88mL/g) is until reach the cumulative volume of 1.76ml.After adding each time, stir the mixture with impregnation of silica.Behind the dipping, with the Pt-Rh/ silica mixture in stove 120 ℃ lower dry 12 hours, subsequently 500 ℃ of lower calcinings 3 hours.After cooling, catalyzer was stored in the moisture eliminator before being used.
With conversion of glucose to saccharic acid
Reaction has 2 μ m, 316 stainless steel glass material at the place, two ends of catalyst bed 1/ 4Inch OD multiply by in the 321 long stainless steel tubes of 401mm and carries out.With catalyst bed silicon carbide (180-300 μ m) on vibrating bottom is filled, until about 40mm degree of depth is filled upper catalyzer (1.757g) subsequently, then fill upper silicon carbide (180-300 μ m), until the top.The reactor tube of filling is clipped in the aluminium block well heater that is provided with the PID controller.All reactions are used in gas and the liquid that the top of reactor enters and carry out with the condition of describing in the table 3.Gas and liquid flow rate are regulated by mass flow controller and HPLC pump respectively.Glucose solution prepares by D-(+)-glucose (Sigma-Aldrich, 〉=99.5%) is dissolved in the water.Back pressure regulator control reactor pressure is as pointing out in the table 3.All reactions are carried out with zero level air (MathesonTri-Gas, Santa Clara, CA).Reactor product was collected in 122 hours and under reduced pressure concentrated, do not carry out further purifying.
Table 3:
Figure BDA00002100219900201
Be converted into hexanodioic acid
The product of autoxidation fixed-bed reactor is by evaporation concentration and the dry saccharic acid product (determining by Ka Er-Karl Fischer titration) that comprises 1.2% water with generation in the future.With this material be dissolved in again among acetic acid and the HBr take preparation in HBr as 0.2M and comprise the 250mL solution of 9.6g saccharic acid product.Make this solution with the flow rate of 50 μ L/min, use the parallel 5sccm hydrogen gas rate under 1000psi, move the fixed-bed reactor by the 2.3 % by weight Pt-0.8 % by weight Rh on Davisil 635 silicon-dioxide that hold 2.5g.Reactor has two heating zone.The first district is in 6 inches districts of 110 ℃ of lower heating, and another district is another the 6 inches districts 140 ℃ of lower heating.
The recovery of the composition of material of the present invention
To extremely do from the 200mL solution evaporation that the outlet of fixed-bed reactor is collected.Add acetic acid (the every gram raw product of 3mL AcOH), and material dissolved under 90 ℃ and allow at room temperature crystallization.Crystal is by filtering to reclaim and using the concentration of 1g crystal in 5mL water from the further recrystallization of water other for 3 times.During the second recrystallization, the solution of heat is filtered by decolorizing charcoal.At last, crystal is lower dry at 60 ℃ under vacuum.According to 1H NMR, adipic acid crystals is confirmed as〉99.5 % by weight are pure.Mass spectroscopy shows that the peak is consistent with the existence with the following molecule of being described of level＜0.5 % by weight:
Figure BDA00002100219900202

Claims (9)

1. composition that comprises following material: the hexanodioic acid product of formula (1)
Figure FDA00002100219800011
Wherein R is into the alkyl of salt ion, hydrogen, alkyl or replacement independently; With
Be selected from least a composition by the following group that forms: formula (2)
Figure FDA00002100219800012
Wherein R as hereinbefore defined, R1 is the acyloxy of H, OH, acyloxy or replacement, however condition is that among the R1 at least one is OH; And formula (3)
Figure FDA00002100219800013
Wherein R as hereinbefore defined, and R1 is the acyloxy of H, OH, acyloxy or replacement.
2. the composition of material according to claim 1 comprises the hexanodioic acid product of described formula (1) and at least two kinds of different compositions of the group that is selected from formula (2) and formula (3).
3. the composition of material according to claim 1 comprises at least about the hexanodioic acid of 99 % by weight or its salt and at least a composition of the formula of about 1 % by weight (2) at the most.
4. the composition of material according to claim 1 comprises at least about the hexanodioic acid of 99 % by weight and at least a composition that selects the group that free style (2) and formula (3) form of about 1 % by weight at the most.
5. the composition of a material comprises at least about the hexanodioic acid of 99 % by weight and two kinds of compositions that select the group that free style (2) and formula (3) form of about 1 % by weight at the most at least.
6. at least in part by the adiponitrile of the composition of each described material in the claim 1 to 5 preparation.
7. at least in part by the polymeric amide of the composition production of each described material in the claim 1 to 5.
8. at least in part by the hexanolactam of the composition production of each described material in the claim 1 to 5.
9. at least in part by the polyester of the composition production of each described material in the claim 1 to 5.
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