CN105503566B - Glutaric acid and derivative are produced by the material of carbohydrate containing - Google Patents
Glutaric acid and derivative are produced by the material of carbohydrate containing Download PDFInfo
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- CN105503566B CN105503566B CN201510887722.8A CN201510887722A CN105503566B CN 105503566 B CN105503566 B CN 105503566B CN 201510887722 A CN201510887722 A CN 201510887722A CN 105503566 B CN105503566 B CN 105503566B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
- C07C51/313—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting with molecular oxygen
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- 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
Abstract
The present invention relates generally to the technique for pentose source chemical catalysis to be converted into glutaric acid product.The present invention includes being used for the technique that pentose is converted into glutaric acid product via valeric acid or derivatives thereof.Present invention additionally comprises comprising being valeric acid and by technique that valeric acid or derivatives thereof catalytic hydrodeoxygenation is glutaric acid product by pentose catalysis oxidation.
Description
The application is the divisional application of the application for a patent for invention of Application No. 201080026095.4, the applying date of original application
It is entitled on June 11st, 2010：Glutaric acid and derivative are produced by the material of carbohydrate containing.
Invention field
The present invention relates generally to the technique for pentose source chemical catalysis to be converted into glutaric acid product.The present invention includes using
In the technique that pentose is converted into glutaric acid product via valeric acid and/or its derivative.Present invention additionally comprises comprising pentose is urged
Change and be oxidized to valeric acid and by technique that valeric acid and/or its derivatives catalysis hydrogenation deoxidation are glutaric acid product.The invention further relates to
For preparing industrial chemical such as glycol (for example, 1,5-PD), diamines (for example, 1,5- diaminourea by glutaric acid product
Pentane), the technique of polyamide and polyester, the glutaric acid product by including catalytic hydrodeoxygenation valeric acid (for example, xylose diacid
And/or arabic acid) and/or its derivative be used for chemical catalysis conversion pentose source technique obtain.
Background of invention
Hemicellulose represents the second most abundant carbohydrate in nature, forms being up to about for wood fiber biomass
20-35%.Hemicellulose is the heteropolymer of pentose (for example, xylose and arabinose), hexose and saccharic acid.Known half is fine
Dimension element can be acid hydrolysis as xylose and then be cyclized dehydration to produce furfural.Per year over 350,000 tons of furfurals by wood
Sugar produces, for the application in plastics, medicine and agricultural chemicals.See, for example, Furfural：Hemicelluloses/
Xylose-derived biochemical (furfurals：Biochemicals derived from hemicellulose/xylose), Mamman et al.
Volume 2, the 438-454 pages of Biofuels, Bioprod.Bioref..
For by bio-renewable carbohydrate-derived pentose (for example, as derived from hemicellulose xylose and Ah
Draw uncle sugar) be converted into one of broader group of current commodity and the significant challenge of specialty chemicals be from carbohydrate selectivity
Ground removes oxygen atom.Method for carbon-oxygen singly-bound to be converted into carbon-hydrogen link is known.See, e.g.：U.S. Patent No.
No. 5,516,960；U.S. Patent Application Publication 2007/0215484 and Japanese Patent No. 78,144,506.These known methods
In each by various limitations, and it is believed that at present, in these methods no one industrially be used for manufacture work
Industry chemicals.
In view of the abundance of hemicellulose, to for by carbon-oxygen singly-bound optionally with it is commercial be meaningfully converted into carbon-
Hydrogen bond, especially as with as valeric acid (and/or its derivative) such as such as xylose diacid production of chemicals it is relevant apply, and
In particular for pentose (for example, xylose and arabinose) is converted into the new of valuable chemical intermediate such as glutaric acid
, industrial scalable method still suffer from demand, glutaric acid can be used for manufacturing glycol (for example, 1,5-PD), diamines
(for example, 1,5- 1,5-DAP), polyamide, polyester, polyester polyol, spices and medicine and others.Referring to
Ullmann ' s Encyclopedia of Industrial Chemistry (Liv Ullmann industrial chemistry encyclopaedia), Wiley-
VCH 2009 and referring further to United States Patent (USP) 5,290,852,5,281,647,4,439,551, WO 2008/144514 and 2008/
070762nd, Japan Patent 2005060447 and 2001316311 and U.S. Patent Application Publication 2008/0103232.
Summary of the invention
Therefore, briefly, the present invention relates to the technique for preparing glutaric acid product.According to an embodiment, there is provided
A kind of technique for being used to produce glutaric acid product by pentose source.The technique include by chemical catalysis mode by pentose source extremely
A few part is converted into glutaric acid product.
According to another embodiment, the technique for preparing glutaric acid product includes, in hydrogenation deoxidation catalyst and halogen
In the presence of plain source, C5- main chains matrix and hydrogen is set to react so that at least a portion of C5- main chain matrix is converted into glutaric acid production
Thing, wherein C5- main chains matrix include the compound of Formulas I
Wherein X is independently hydroxyl, oxo, halo, acyloxy or hydrogen, and condition is that at least one X is not hydrogen and R1It is independent
Ground is into salt ion, hydrogen, alkyl or substituted alkyl；Or its lactone.
According to another embodiment, the technique for preparing glutaric acid product includes turning at least a portion of pentose source
The C5- main chain matrix including valeric acid or derivatives thereof is turned to, and at least a portion of valeric acid or derivative is converted into glutaric acid
Product.
The invention further relates to the technique for preparing valeric acid.In one embodiment, the technique is included in oxidation catalysis
In the presence of agent and in the case where there is no the alkali of addition, make be selected from by xylose, arabinose, ribose, lyxose and
The pentose and oxygen reaction of the group of its mixture composition.
The invention further relates to for preparing valeric acid by making pentose in the presence of an oxidation catalyst with oxygen reaction
At least a portion weak carboxylic acids of technique, wherein pentose, preferably acetic acid dissolve.
The invention further relates to for by glutaric acid product prepare industrial chemical such as glycol (for example, 1,5-PD),
Diamines (for example, 1,5- 1,5-DAP), polyamide and polyester and other techniques, glutaric acid product is by including by pentose source
Chemical catalysis be converted into C5- main chains matrix and by C5- main chains matrix (for example, xylose diacid and/or arabic acid and/or its spread out
Biology) catalytic hydrodeoxygenation for glutaric acid product technique obtain.
The invention further relates at least in part by including hydrogenation deoxidation C5- main chains matrix and more specifically xylose diacid and/
Or derivatives thereof technique caused by glutaric acid product, glycol, diamines, polyamide and polyester.
Other objects and features will be apparent and/or will be noted below.
The description of preferred embodiment
According to the present invention, applicant discloses the technique for pentose source chemical catalysis to be converted into glutaric acid product.
In addition, according to the present invention, applicant discloses for being glutaric acid product by C5- main chain matrix catalytic hydrodeoxygenation
Technique.Catalytic hydrodeoxygenation is included in hydrogenation deoxidation catalyst (that is, the catalyst for being suitable for hydrogenation deoxidation reaction) and halogen
In the presence of source, C5- main chains matrix and hydrogen is set to react so that at least a portion of C5- main chain matrix is converted into glutaric acid production
Thing.The hydrogenation deoxidation catalyst of the present invention includes d- areas metal (that is, transition metal；The 3-12 races of periodic table), its be hydroxyl,
Halo, oxo or acyl-oxygen based selective, more generally hydroxyl selectivity, increases yield and modified technique economics.
The invention further relates to for by selected from the group being made up of xylose, arabinose, ribose, lyxose and its mixture
The technique of pentose catalytic production valeric acid and/or its derivative.The technique is included in the presence of an oxidation catalyst and substantially
Making pentose and oxygen in the case of the alkali not added, (wherein oxygen as air, oxygen-enriched air, single oxygen or has pair
The oxygen of the substantially inert one or more other compositions of reaction is provided to reaction) reaction.It there is no addition
Oxidation reaction is carried out in the case of alkali and is beneficial to product recovery and modified technique economics.In addition, the reaction can be in dissolving pentose
At least one of weak carboxylic acids such as acetic acid in the presence of carry out.
, can be according to this area according to glutaric acid product prepared by disclosed technique in another aspect of the present invention
The technique known is converted into various other industrial important chemicals, and the chemicals includes, for example, glycol is (for example, 1,5-
Pentanediol), diamines (for example, 1,5- 1,5-DAP), polyamide and polyester and others.Therefore, glycol is (for example, 1,5-
Pentanediol), diamines (for example, 1,5- 1,5-DAP) polyamide and polyester and others, can be by fine derived from including half
It is prepared by the pentose for tieing up the biorenewable source of element.
I. raw material
Pentose is the sugar comprising five carbon and generally includes xylose, arabinose, ribose and lyxose.Pentose can be by each
Source (source that particularly comprises hemicellulose) of the kind comprising carbohydrate obtains, and the source comprising carbohydrate can including biology
Renewable source, such as energy crops, plant biomass, agricultural wastes, forest residues, sugar handle the family of residue and plant derivation
Front yard waste.More generally, any reproducible organic substance can be included with biorenewable source used according to the invention, it includes
Hemicellulose source, for example, such as switchgrass, straw (for example, rice straw, barley culm, wheat straw, straw from rye, oat straw), oat shell,
Awns genus, cassava, tree (hardwood and cork), vegetation and crops residue (for example, bagasse and corn stalk).Other sources can wrap
Include, for example, waste materials (for example, waste paper, green waste, municipal waste etc.).Methods known in the art can be used from bag
Biorenewable source isolation pentose containing hemicellulose.In addition, the method that pentose is converted into the chemicals of limitation group is also this
Known to field.For illustrating for these methods, see, e.g., Saha, J.Ind.Microbiol.Biotechnol. the 30th
Volume, the 279-291 pages (2003), and Kamm, Gruber and Kamm, Biorefineries-Industrial Processes
And Products (biological refiner-industrial technology and product), Wiley-VCH, Weinheim 2006.
II. the preparation of valeric acid
According to the present invention, the pentose quilt selected from the group being made up of xylose, arabinose, ribose, lyxose and its mixture
It is converted into valeric acid and/or its derivative.The system of various valeric acids (valeric acid includes xylose diacid, arabic acid, nucleic acid and lysol acid)
It is standby to be completed using method for oxidation commonly known in the art by pentose.See, e.g., Journal of Molecular
Catalysis, volume 77, the 75-85 pages (1992), it is illustrated for using platinum catalyst in the presence of oxygen and alkali by penta
The method that aldose prepares valeric acid.Other method for oxidation can also be used, see, for example, U.S. Patent No. 6,049,004, the 5th,
599, No. 977 and the 6th, 498, No. 269, and U.S. Patent Application Publication the 2008/033205th.Similarly, U.S. Patent No.
No. 5,731,467 disclose by producing xylose two using oxygen come oxidative degradation 5- ketogluconates or its salt in alkaline medium
The method of acid.However, these techniques by by process recovery ratio limit and the needs and others of other reacted constituent are drawn
The economical disadvantages risen.
It has been discovered by the applicants that penta selected from the group being made up of xylose, arabinose, ribose, lyxose and its mixture
Sugared (that is, oxidation matrix) can pass through in the presence of an oxidation catalyst and without making oxidation under the alkali of addition according to following reaction
Matrix and oxygen (wherein oxygen as air, oxygen-enriched air, single oxygen or with to react substantially inert one kind or
The oxygen of various other compositions is provided to reaction) react and valeric acid is converted into high yield：
Surprisingly, the alkali that does not add and carrying out oxidation reaction according to reaction condition set forth herein, will not cause
Significant catalyst poisoning effect and catalyst oxidation activity is maintained.The alkali not added advantageously facilitate valeric acid separation and
Isolation, thus provides the technique more stood commercial Application and total process economics are improved by elimination reaction composition.Such as
" alkali not added " used herein means (for example, composition as raw material) if present, with to reaction the effect of
It there is no alkali existing for the concentration of influence；That is, oxidation reaction is carried out under the alkali that there is no addition.Also send out
It is existing, when being reacted under substantially without the alkali added, mixed in increased oxygen partial pressure and/or higher oxidation reaction
The yield that oxidation reaction tends to increase valeric acid is carried out at a temperature of thing.It has also been found that the oxidation reaction can be in pentose at it
In carry out in the presence of solvable weak carboxylic acids such as acetic acid.Term " weak carboxylic acids " as used herein means there is at least about 3.5,
More preferably at least about 4.5 pKa any unsubstituted or substitution carboxylic acid, and more specifically unsubstituted acid,
Such as acetic acid, propionic acid or butyric acid or its mixture.
In these and various other embodiments, when using weak carboxylic acids to dissolve at least a portion of pentose, reaction
The initial pH of mixture is not greater than about 7, and typically smaller than 7, such as 6 or smaller.According to the present invention, the initial pH of reactant mixture
It is the pH before reactant mixture contacts with oxygen in the presence of an oxidation catalyst.Expected response mixture contacts it in oxygen
PH afterwards will be carried out and changed with reaction.Think, when the concentration increase of valeric acid (when reacting progress), pH will be under initial pH
Drop.
Yet another advantage of the present invention is that it there is no the nitrogen as active reaction composition.Generally, nitrogen is in known work
It is used as oxidant in skill, such as in the form of nitrate, nitric acid is used as in many examples.Use using its as active reaction into
The nitrogen of the form such as nitrate or nitric acid that divide, causes to NOxThe needs of reduction technology and acid regeneration technology, two kinds of technologies are notable
Add by the cost of these known technique productions valeric acids, and the equipment that can deleteriously influence for carrying out technique is provided
Corrosive environment.On the contrary, for example, in the case where air or oxygen-enriched air are used for the oxidation reaction of the present invention as oxygen source, nitrogen
It is substantially inactive or inert composition.Thus, for example, according to the present invention, the oxidation using air or oxygen-enriched air is anti-
Should there is no the reaction that will be carried out by it under nitrogen in the form of being active reaction composition.
In each embodiment, pentose is selected from the group being made up of xylose, arabinose and its mixture.These and its
In his embodiment, pentose is converted into the valeric acid selected from the group being made up of xylose diacid, arabic acid and its mixture.
Generally, the temperature of oxidation mixtures is at least about 40 DEG C, more generally 60 DEG C or higher.In each embodiment
In, the temperature of oxidation mixtures is about 40 DEG C to about 150 DEG C, about 60 DEG C to about 150 DEG C, about 70 DEG C to about 150 DEG C or about
70 DEG C to about 140 DEG C or about 80 DEG C to about 120 DEG C.
Generally, the partial pressure of oxygen is at least about 15 pound per square inches (absolute value) (psia) (104kPa), at least about
25psia (172kPa), at least about 40psia (276kPa), at least about 60psia (414kPa).In each embodiment, oxygen
The partial pressure of gas is is up to about 1000psia (6895kPa) or, more generally, in about 15psia (104kPa) to about 500psia
In the range of (3447kPa).
Oxidation reaction is generally carried out in the presence of the solvent of pentose is suitable for.Being suitable for the solvent of oxidation reaction includes water
With weak carboxylic acids such as acetic acid.The cost of technique is added by the use of weak carboxylic acids as solvent, as it is actual the problem of, the cost is necessary
Balance is kept with any benefit by being obtained using weak carboxylic acids.Therefore, suitable solvent of the invention includes water, water and weak carboxylic acids
Mixture or weak carboxylic acids.
In general, oxidation reaction can use fixed bed reactors, trickle bed reactor, slurry-phase reactor, movement
Batch reactor design, semi batch reactor design or the flow reactor design of bed reactor allow heterogeneous catalysis anti-
Carried out in any other design answered.The example of reactor can see Chemical Process Equipment-
Selection and Design (chemical process equipment-selection and design), Couper et al., Elsevier 1990, it passes through
It is incorporated herein by reference.It should be understood that pentose, oxygen, any solvent and oxidation catalyst can be drawn individually or with various combinations
Enter in suitable reactor.
Being suitable for the catalyst (" oxidation catalyst ") of oxidation reaction includes heterogeneous catalysis, including comprising a kind of or more
The solid-phase catalyst of metal that is kind load or not being supported.In each embodiment, metal is present at the surface of carrier
(that is, at one or more surfaces, outside or internal).Generally, metal is selected from the group being made up of palladium, platinum and combinations thereof.
There may be other other metals, including combine individually or with one or more rare earth metals (such as lanthanide series),
Or one or more d- areas that are single or being combined with one or more main group metals (such as Al, Ga, Tl, In, Sn, Pb or Bi)
Metal.In general, metal can be in a variety of manners (for example, element, metal oxide, metal hydroxides, metal ion
Deng) exist.Generally, metal at the surface of carrier form about 0.25% to about 10% or about the 1% of total catalyst weight to
About 8% or about 2.5% to about 7.5% (for example, 5%).
In each embodiment, oxidation catalyst is included in the first metal (M1) and the second metal at the surface of carrier
(M2), wherein M1 metals are selected from the group being made up of palladium and platinum, and M2 metals are selected from by d- areas metal, rare earth metal and main group metal
The group of composition, wherein M1 metals are the metals different from M2 metals.In various preferred embodiments, M1 metals are platinum, and
M2 metals are selected from the group being made up of manganese, iron and cobalt.
M1：M2 mol ratios can change, for example, about 500：1 to about 1：1st, about 250：1 to about 1：1st, about 100：1 to about 1：
1st, about 50：1 to about 1：1st, about 20：1 to about 1：1 or about 10：1 to about 1：1.In various other embodiments, M1：M2 mol ratios
It can change, for example, about 1：100 to about 1：1st, about 1：50 to about 1：1st, about 1：10 to about 1：1st, about 1：5 to about 1：1 or about 1：2
To about 1：1.
In addition, M1 and M2 can change relative to the percentage by weight of catalyst weight.Generally, M1 percentage by weight
0.5% to about 10% is can range from about, more preferably about 1% to about 8%, and still more preferably about 2.5% to about 7.5%
(for example, about 5%).M2 percentage by weight can range from about 0.25% to about 10%, about 0.5% to about 8% or about
0.5% to about 5%.
In various other embodiments, the 3rd metal (M3) can be added to produce M1/M2/M3 catalyst, wherein M3
Metal is the metals different from M1 metals and M2 metals.In other embodiments, the 4th metal (M4) can be added to produce
M1/M2/M3/M4 catalyst, wherein M4 metals are the metals different from M1 metals, M2 metals or M3 metals.M3 metals and M4 gold
Category can each be selected from by d- areas metal, rare earth metal (such as lanthanide series) or main group metal (such as Al, Ga, Tl, In, Sn,
Pb or Bi) composition group.
Suitable catalyst carrier includes charcoal, aluminum oxide, silica, ceria, titanium dioxide, zirconium oxide, oxidation
Niobium, zeolite, magnesia, clay, iron oxide, carborundum, alumino-silicate and its version, mixture or combination.Carrier material
It can be modified using methods known in the art, such as heat treatment, acid treatment or by introducing dopant (for example, metal is mixed
Miscellaneous titanium dioxide, metal-doped zirconium oxide (for example, tungstated zirco), metal-doped ceria and metal-modified
Niobium oxide).Preferable carrier is charcoal (it can be activated carbon, carbon black, coke or charcoal), aluminum oxide and silica.
In each embodiment, the carrier of oxidation catalyst is selected from the group being made up of charcoal, aluminum oxide and silica.
When using catalyst carrier, deposited metal can be carried out using program known in the art, included but is not limited to just
Wet impregnated with method, ion exchange, deposition-precipitation and vacuum impregnation.When by two or more metal deposits on identical carrier
When, they can according to priority or simultaneously be deposited.In each embodiment, after metal deposition, at least about 50
DEG C, dry catalyst about 1 hour, the period of more generally 3 hours or longer at a temperature of more generally at least about 120 DEG C.At this
In a little and other embodiments, the dry catalyst under subatmospheric pressure condition.In each embodiment, in drying
Reducing catalyst at 350 DEG C (for example, by flowing through N afterwards2In 5%H2, continue 3 hours).Also further, these and
In other embodiments, catalyst is calcined into a period of time (for example, at least about 3 is small at a temperature of for example, at least about 500 DEG C
When).
Various other pentanoate derivants, such as salt, ester, ketone and lactone can will be converted into according to the valeric acid produced above.
It is known in the art by the method that carboxylic acid is converted into such derivative, see, e.g., Wade, Organic Chemistry
(organic chemistry) the 3rd edition, Prentice Hall 1995.
III. the preparation of glutaric acid product
According to the present invention, glutaric acid product can convert pentose source to prepare by chemical catalysis.In each embodiment
In, the preparation of glutaric acid product includes pentose source chemical catalysis being converted into valeric acid.In these and other embodiments, it will wrap
At least one of C5- main chains matrix for including valeric acid or derivatives thereof is converted into glutaric acid product.The derivative of valeric acid is included such as
Undefined compound.
C5- main chains matrix includes the compound of Formulas I：
Wherein X is independently hydroxyl, oxo, halo, acyloxy or hydrogen, and condition is that at least one X is not hydrogen and R1It is independent
Ground is into salt ion, hydrogen, alkyl or substituted alkyl；Or its lactone.
As used herein, term " alkyl " refers to preferably include 1 to about 50 carbon atom, preferably 1 to about 30
Carbon atom and even more preferably still the hydrocarbon part of 1 to about 18 carbon atom, including side chain or it is unbranched and saturation or not
The species of saturation.Preferable alkyl can be selected from the group consisted of：It is alkyl, alkylidene, alkoxy, alkyl amino, thio
Alkyl, haloalkyl, cycloalkyl, cycloalkyl-alkyl, heterocyclic radical, N- heterocyclic radicals, Heterocyclylalkyl, aryl, aralkyl heteroaryl, N-
Heteroaryl, heteroaryl alkyl and the like.Alkyl can optionally be the alkyl of substitution.Therefore, various alkyl are also selected from
Substituted alkyl, the cycloalkyl and the like of substitution.
Include but is not limited into salt ion, such as ammonium ion and metal ion (for example, alkali and alkaline earth metal ions).Work as R1
When being into salt ion (that is, cation), carboxyl is considered anion (that is, carboxylate anion).
In each embodiment, C5- main chains matrix includes the compound of Formulas I, and wherein X is independently hydroxyl, oxo, halogen
Generation, C1-C6Acyloxy or hydrogen, condition are that at least one X is not hydrogen.In other embodiments, C5- main chains matrix includes Formulas I
Compound, wherein X are hydroxyl and R1Independently it is into salt ion, hydrogen, alkyl or substituted alkyl.
As shown in Formulas I, C5- main chains matrix includes five carbochains, and five carbochains include three chiral centres.Cause
This, several stereoisomers are possible.In each embodiment, preferable C5- main chains matrix includes being selected from by xylose
The valeric acid of the group of diacid, arabic acid and its mixture composition.
C5- main chains matrix can also include various ketone.For example, it is not wishing to be bound by theory, when valeric acid is further oxided
When, ketone such as α -one base-xylose diacid (2,3- dihydroxy -4- ketoglutaric acids) and its various stereoisomer can be formed.
C5- main chains matrix can include the various lactones as derived from valeric acid.For example, it is not wishing to be bound by theory, it is believed that, respectively
Kind single lactone can balance with the various valeric acids in the aqueous solution to be present, including for example, xylose diacid -5,2- lactone, arabic acid -
5,2- lactones, ribonic acid -5,2- lactones and glutaric acid -5,2- lactones or its stereoisomer.In addition, technique has been developed to
Valeric acid in solution or its salt are quantitatively converted into one or more lactones and reclaim substantially pure lactone stream.Referring to example
Such as, U.S. Patent Application Publication No. 2006/0084817 and No. 2006/0084800.
According to the present invention, glutaric acid product (Formula II) can be according to following reaction by hydrogenation deoxidation catalyst and halogen
Make in the presence of source C5- main chains matrix (Formulas I) and hydrogen (it should be understood that hydrogen mean substantial hydrogen or with to reacting basic
The hydrogen of upper inert other compositions combination) react to prepare：
Wherein X and R1As defined above.
In preferred embodiments, glutaric acid product (Formula II) includes glutaric acid.
In above-mentioned reaction, C5- main chains matrix is converted into glutaric acid product by catalytic hydrodeoxygenation, wherein carbon-hydroxyl
Base group is converted into carbon-hydrogen group.In each embodiment, catalytic hydrodeoxygenation is hydroxyl selectivity, wherein in reality
Reaction is completed during other the one or more non-hydroxyl functional groups for not having to convert matrix in matter.
According to the present invention, C5- main chains matrix is in the presence of hydrogen, halogen source and hydrogenation deoxidation catalyst by catalytic hydrogenation
Deoxidation.It is without being bound by theory, it is believed that, during the reaction, C5- main chains matrix includes carbon-halogen by halogen source halogenation, to be formed
The halogenation intermediate (for example, the secondary alcohol groups on valeric acid are converted into halide to produce alkyl halide) of key.Think among halogenation
Carbon-halogen bond of body is converted into carbon-hydrogen link via one or more of following approach.In the first approach, make in halogenation
Mesosome reacts with hydrogen in the presence of hydrogenation deoxidation catalyst, results in carbon-hydrogen link, and generate halogen acids.Second
In approach, halogenation intermediate undergoes de-hydrogen halide to form alkene intermediates and halogen acids.Alkene is also urged in hydrogenation deoxidation
It is reduced in the presence of agent, resulting in carbon-hydrogen link, (or alkene can be the Enol forms of ketone, and the Enol forms of ketone can be with
Keto form with that can be reduced to alcohol radical exchanges, and alcohol radical can undergo further hydrogenation deoxidation).According to above-mentioned first approach and
Second approach realizes halogen acids of the reaction generation as accessory substance, and the halogen acids can be used for further reaction.In the 3rd approach,
Halogenation intermediate reacts with halogen acids, results in carbon-hydrogen link, and form molecular halogen (or inter-halogen compounds).According to
Three approach realize molecular halogen of the reaction generation as accessory substance, and molecular halogen can be used for further reaction.Above-mentioned various approach
In one or more can occur simultaneously.
It should be understood that hydrogenation deoxidation reaction can be by being initially formed these various intermediates and optionally purifying or isolate
These various intermediates are carried out, and these various intermediates are by combining C5- main chains matrix and halogen source and being then hydrogenated with
Intermediate in the presence of dehydrogenation catalyst and is optionally set to be reacted with hydrogen to be formed under no any other halogen source.
In each embodiment, C5- main chains matrix is by halogen acids halogenation to form halogenation intermediate (for example, halo
Alkane).In other embodiments, C5- main chains matrix by molecular halogen halogenation to form halogenation intermediate (for example, alkyl halide).
Halogen source can be in the form of selected from the group consisted of：Atomic form, ionic species, molecular forms and its
Mixture.Halogen source includes halogen acids (for example, HBr, HI, HCl and its mixture；Preferably HBr and/or HI)；Halide salts；
(substituted or unsubstituted) alkyl halide；Or elemental chlorine, bromine or iodine or its mixture (preferably bromine and/or iodine).Each
In embodiment, halogen source is with molecular forms and more preferably bromine or iodine.In a more preferred embodiment, halogen source is
Halogen acids, specifically hydrogen bromide or hydrogen iodide.
Generally, halogen and the mol ratio of C5- main chain matrix are equal to or less than about 1.In each embodiment, halogen with
The mol ratio typically about 0.1 of C5- main chain matrix：1 to about 1：1, more typically from about 0.3：1 to about 0.7：1 and even more typically about
0.5：1.
Generally, reaction allows to reclaim halogen source, and halogen (the wherein halogen and the mol ratio of C5- main chain matrix of catalytic amount
It is used to continuously be used as halogen source less than about 1) being used, reclaiming and being circulated.
Generally, the temperature of hydrogenation deoxidation reactant mixture is at least about 80 DEG C, at least about more generally 100 DEG C.In each reality
Apply in scheme, the temperature of hydrogenation deoxidation reactant mixture is about 80 DEG C to about 250 DEG C, more preferably about 100 DEG C to about 200 DEG C and
Still more preferably about 120 DEG C to about 180 DEG C.
Generally, the partial pressure of hydrogen is at least about 25psia (172kPa), more generally, at least about 200psia (1379kPa),
Or at least about 400psia (2758kPa).In each embodiment, the partial pressure of hydrogen is about 25psia (172kPa) to about
2500psia (17237kPa), about 200psia (1379kPa) to about 2000psia (13,790kPa) or about 400psia
(2758kPa) to about 1500psia (10,343kPa).
Hydrogenation deoxidation reaction is generally carried out in the presence of the solvent.Being suitable for the solvent of selective hydrogenation deoxygenation includes
Water and carboxylic acid, acid amides, ester, lactone, sulfoxide, sulfone and its mixture.Preferable solvent include water, water and weak carboxylic acids mixture,
And weak carboxylic acids.Preferable weak carboxylic acids are acetic acid.
In general, reaction can be anti-using fixed bed reactors, trickle bed reactor, slurry-phase reactor, moving bed
The batch reactor of device is answered to design, semi batch reactor design or flow reactor design or allow heterogeneous catalytic reaction
Carried out in any other design.The example of reactor can see Chemical Process Equipment-Selection
And Design (chemical process equipment-selection and design), Couper et al., Elsevier 1990, it is incorporated by reference into this
Text.It should be understood that C5- main chains matrix, halogen source, hydrogen, any solvent and hydrogenation deoxidation catalyst can be individually or with various
Combination is introduced into suitable reactor.
In each embodiment, hydrogenation deoxidation catalyst is heterogeneous, but can use suitable homogeneous catalyst.
In these and various other preferred embodiments, hydrogenation deoxidation catalyst includes solid-phase heterogenous catalysts, one of which
Or various metals are present at the surface of carrier (that is, at one or more surfaces, outside or internal).Preferable metal
Be can individually, be combined with each other, combine with one or more rare earth metals (such as lanthanide series) or with one or more main groups
The d- areas metal that metal (for example, Al, Ga, Tl, In, Sn, Pb or Bi) is applied in combination.Preferable d- areas metal be selected from by cobalt, nickel,
The group of ruthenium, rhodium, palladium, osmium, iridium, platinum and combinations thereof composition.Preferred d- areas metal is selected from by ruthenium, rhodium, palladium, platinum and combinations thereof group
Into group.In general, metal can be in a variety of manners (for example, element, metal oxide, metal hydroxides, metal ion
Deng) exist.Generally, the metal at the surface of carrier may be constructed about the 0.25% to about 10% or about 1% of catalyst weight
To about 8% or about 2.5% to about 7.5% (for example, 5%).
In each embodiment, catalyst includes two or more metals.For example, two kinds of (M1 in various metals
And M2) can be loaded on identical carrier or interior (for example, as the mixed metal catalyst on silica；M1/M2/
SiO 2 catalyst), or they can be loaded on different carrier materials.In each embodiment, hydrogenation deoxidation
Catalyst is included in the first metal (M1) and the second metal (M2) at the surface of carrier, and wherein M1 metals include d- areas metal,
And M2 metals are selected from the group being made up of d- areas metal, rare earth metal and main group metal, wherein M1 metals are different from M2 metals
Metal.In various preferred embodiments, M1 metals are selected from the group being made up of ruthenium, rhodium, palladium and platinum.In each embodiment
In, M2 metals are selected from the group consisted of：Titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, molybdenum, ruthenium, rhodium, palladium, silver, tungsten, iridium, platinum and
Gold.In a more preferred embodiment, M2 metals are selected from the group consisted of：Molybdenum, ruthenium, rhodium, palladium, iridium, platinum and gold.
In a more preferred embodiment, M1 metals are selected from the group of platinum, rhodium and palladium, and M2 metals are selected from what is consisted of
Group：Ruthenium, rhodium, palladium, iridium, platinum and gold.
In each embodiment, M1：M2 mol ratios can change, for example, about 500：1 to about 1：1st, about 250：1 to about
1：1st, about 100：1 to about 1：1st, about 50：1 to about 1：1st, about 20：1 to about 1：1 or about 10：1 to about 1：1.In various other implementations
In scheme, M1：M2 mol ratios can change, for example, about 1：100 to about 1：1st, about 1：50 to about 1：1st, about 1：10 to about 1：1st, about
1：5 to about 1：1 or about 1：2 to about 1：1.
In addition, in each embodiment, M1 and M2 can change relative to the percentage by weight of total catalyst weight.It is logical
Often, M1 percentage by weight can range from about 0.5% to about 10%, and more preferably about 1% to about 8% and still more preferably
About 2.5% to about 7.5% (for example, about 5%).M2 percentage by weight can range from about 0.25% to about 10%, about
0.5% to about 8% or about 0.5% to about 5%.
In various other embodiments, the 3rd metal (M3) can be added to produce M1/M2/M3 catalyst, wherein M3
Metal is the metals different from M1 metals and M2 metals.In other embodiments, the 4th metal (M4) can be added to produce
M1/M2/M3/M4 catalyst, wherein M4 metals are the metals different from M1 metals, M2 metals or M3 metals.M3 metals and M4 gold
Category can each be selected from by d- areas metal, rare earth metal (such as lanthanide series) or main group metal (such as Al, Ga, Tl, In, Sn,
Pb or Bi) composition group.
Preferable catalyst carrier includes charcoal, aluminum oxide, silica, ceria, titanium dioxide, zirconium oxide, oxidation
Niobium, zeolite, magnesia, clay, iron oxide, carborundum, alumino-silicate and its version, mixture or combination.Carrier can be with
It is modified using methods known in the art, such as heat treatment, acid treatment, introducing dopant are (for example, metal-doped titanium dioxide
Titanium, metal-doped zirconium oxide (such as tungstated zirco), metal-doped ceria and metal-modified niobium oxide).
In various preferred embodiments, hydrogenation deoxidation catalyst carrier is selected from the group being made up of silica or titanium dioxide.
When using catalyst carrier, deposited metal can be carried out using program known in the art, included but is not limited to just
Wet impregnated with method, ion exchange, deposition-precipitation and vacuum impregnation.When by two or more metal deposits on identical carrier
When, they can according to priority or simultaneously be deposited.In each embodiment, after metal deposition, at least about 50
DEG C, dry catalyst at least about 1 hour, the time of more generally at least 3 hours or longer at a temperature of more preferably at least about 120 DEG C
Section.In these and other embodiments, the dry catalyst under subatmospheric pressure condition.In each embodiment
In, reducing catalyst at 350 DEG C (for example, by flowing through N after drying2In 5%H2, continue 3 hours).Also further,
In these and other embodiments, catalyst is calcined into a period of time (for example, extremely at a temperature of for example, at least about 500 DEG C
It is few about 3 hours).
Do not fettered by the theory not fairly set out in the claims, include the catalyst mixture of more than one metal
(co-catalyst or mixed metal catalyst) can realize the independent step of automatic reaction approach.
By one or more conventional methods known in the art penta 2 can be reclaimed from hydrogenation deoxidation reactant mixture
Acid product, methods described include, such as solvent extraction, crystallization or evaporation process.
IV. downstream chemical product
The various methods known in the art for being used to for glutaric acid to be converted into downstream chemical product or intermediate, downstream chemical production
Product or intermediate include glycol (for example, 1,5-PD), diamines (for example, 1,5- 1,5-DAP), polyamide and polyester with
It is and other.See, e.g. Ullmann ' s Encyclopedia of Industrial Chemistry, (Liv Ullmann industrializes
Learn encyclopedia), Wiley-VCH 2009, and referring further to United States Patent (USP) 5,290,852,5,281,647,4,439,551, WO
2008/144514 and 2008/070762, JP 2005060447, JP 2001316311, U.S. Patent application 20080103232.
In each embodiment, glutaric acid product is converted into 1,5-PD, and wherein glutaric acid product is according to this hair
It is bright to prepare.1,5- pentanediols are the speciality chemical intermediates for producing various polymer and plasticizer.See, e.g., JP
2001316311。
In other embodiments, glutaric acid product is converted into 1,5- 1,5-DAPs, wherein glutaric acid product according to
It is prepared by the present invention.1,5- 1,5-DAPs can be used for producing polyamide.See, e.g., JP 2005060447.
In other embodiments, glutaric acid product is converted into polyester, and wherein glutaric acid product is made according to the present invention
It is standby.
In addition, known in the art be used to xylose diacid being converted into downstream chemical product such as polyhydroxy polycarboxylic amide polymer
Various methods.See, e.g., U.S. Patent No. 4,833,230.Therefore, in each embodiment, xylose diacid is with gathering
To form polyhydroxy polycarboxylic amide polymer, wherein xylose diacid is prepared compound forerunner precursor reactant according to the present invention.
When introducing the key element of the present invention or its preferred embodiment, article " one (a) ", " one (an) ", " being somebody's turn to do (the) "
" (said) " is intended to refer to one or more of key element be present.Term " including (comprising) ", " including
(including) ", " contain (containing) " and " having (having) " is intended that being included and means there may be
Different from the other key element for the key element listed.
In view of the above, it will be seen that, several objects of the invention is implemented and obtains other favourable results.
When carrying out various change to above-mentioned composition and technique, without departing from the scope of the present invention, it is contemplated that in foregoing description
Comprising all the elements should be interpreted illustrative and not be with restricted meaning.
The present invention is described in detail, it will therefore be apparent that modifications and variations form is possible, without departing from appended power
The scope of the invention defined in profit requirement.
Embodiment
Following non-limiting example is provided further to explain the present invention.
According to the program described in embodiment below, carried out in the 1mL vials being accommodated in pressurizing vessel
Reaction.Product yield is determined using Dionex ICS-3000 chromatography systems.For embodiment 1, exist first
Separation product and then detected by electrical conductivity by relatively quantifying product with calibration standard items on ASII-HC posts.For reality
Example 2 is applied, is existed firstOn organic acid post separation product and then by ICS- Series P DA-1UV detectors by with
Calibration standard items relatively quantify product.
Embodiment 1：The oxidation of xylose, ribose and arabinose
The preparation of 4wt.%Pt/ SiO 2 catalysts
Pt (the NO that will suitably concentrate3)2The some of the aqueous solution (Heraeus) adds (wherein Pt in appropriate carrier
(NO3)2Pore volume of the total combined volume matching of solution equal to silica supports), and be stirred between addition.Dipping
Afterwards, product is dried 12 hours in stove at 120 DEG C.By being flowed at 200 DEG C in N2In 5vol.%H2Lower reduction 3 is small
When prepare the material for catalyst test.
Oxidation reaction
By in 1mL bottles of the catalyst distribution in 96 hole reactor inserts (Symyx Solutions).Response matrix
It is the aqueous solution of D- (+)-xylose, D- (-)-ribose and D- (-)-arabinose (all being from Acros Organics).To every
One bottle adds 250 μ L matrix solutions.By bottle each personal teflon pin-and-hole piece, siloxanes pin-and-hole pad and steel gas diffusion plate
(Symyx Solutions) is covered.Reactor insert is placed in pressure vessel and loaded three times with oxygen, until
100psig, and in the final vacuum of each pressurization steps.Then reactor is loaded to 75psig, closing and placed with oxygen
Heated 8 hours on shaking machine and at 90 DEG C.After the reaction time passes by, stop shaking and reactor is cooled to room
Temperature, then it is vented reactor.Sample for ion-chromatography (IC) analysis is prepared by following：Reacted to each
Bottle adds 750 μ L water, then cover plate and mixes, centrifuges afterwards with separating catalyst particles.Each response sample passes through
The 100 μ L 50ppm HCl solutions that internal standard addition is used as during the second serial dilution step carry out 16 times of dilutions twice to enter
One step dilutes.Result is shown in table 1.
The oxidation reaction of the 4wt.%Pt catalyst of table 1.
Embodiment 2：Xylose diacid is to glutaric acid
The preparation of M1/ SiO 2 catalysts (M1=Rh, Pd, Pt).
The dried 5 μm of silica Cariact (Fuji Silysia) of 2g are weighed in bottle.The M1 suitably concentrated
Stock solution (M1=Rh, Pd, Pt) is prepared (referring to table 1) by the acid stock solution for the concentration bought from Heraeus.For every
A kind of M1, multiple addition parts of the M1 stock solutions of dilution are added into carrier (silica pore volume=0.7mL/g), until
Reach 1.4ml cumulative volume.After adding each time, stirring mixture is with impregnated carrier.After dipping, 5wt.%M1/ is carried
Body mixture is dried 12 hours in stove at 120 DEG C, is calcined 3 hours at 500 DEG C afterwards.After cooling, catalyst is stored up
Exist in drier, until using.
Xylose diacid to glutaric acid reacts.
Catalyst array is transferred in the 1mL vials in 96 hole reactor inserts (Symyx Solutions).
Each bottle in each array receives the 0.2M xyloses diacid of bead and 250 μ L, 0.1 to 0.3M HBr (in second
In acid, Sigma-Aldrich) or HI (Sigma-Aldrich).After solution addition, bottle array teflon pin-and-hole piece,
Siloxanes pin-and-hole pad and steel gas diffusion plate (Symyx Solutions) covering.Reactor insert is placed on pressure vessel
In, pressurization and be vented 3 times with nitrogen and with hydrogen exhaust 3 times, then with pressurized with hydrogen to 710psig, be heated to 140 DEG C and shake
It is dynamic 3 hours.After 3 hours, reactor is cooled down, be vented and purged with nitrogen.Then it is small 750 μ L water to be added each
Bottle.After water addition, array is covered and shaken to ensure to be sufficiently mixed.Then, capped array is placed on centrifugation
With separating catalyst particles in machine.Then, each response sample is diluted with water 2 times to produce the sample for being used for analyzing by HPLC
Product.Result is shown in table 2.
Table 2.
Claims (65)
1. a kind of technique for being used to prepare C5- main chain matrix, the technique include：
Make pentose in the presence of heterogeneous oxidation catalyst with oxygen reaction so that at least a portion pentose is converted into C5- main chains
Matrix, wherein heterogeneous oxidation catalyst include being selected from the metal by Pd, Pt and combinations thereof group formed, wherein reactant mixture
PH be not more than 7, the C5- main chains matrix be Formulas I compound or its lactone
Wherein X is independently hydroxyl, oxo, halo, acyloxy or hydrogen, and condition is that at least one X is not hydrogen and R1Independently it is into
Salt ion, hydrogen, alkyl or substituted alkyl.
2. technique as claimed in claim 1, wherein X are hydroxyl and R1Independently it is into salt ion, hydrogen, alkyl or substituted hydrocarbon
Base.
3. technique as claimed in claim 1, wherein C5- main chains matrix include valeric acid.
4. technique as claimed in claim 3, wherein valeric acid include being selected from by xylose diacid, arabic acid, nucleic acid and combinations thereof
The acid of the group of composition.
5. technique as claimed in claim 3, wherein C5- main chains matrix include xylose diacid.
6. technique as claimed in claim 1, wherein Pd and/or Pt metals form the 0.25-10% of total catalyst weight.
7. technique as claimed in claim 1, wherein Pd and/or Pt metals form the 1-8% of total catalyst weight.
8. technique as claimed in claim 1, wherein heterogeneous oxidation catalyst include be selected from by charcoal, aluminum oxide, silica,
The catalyst carrier of the group of titanium dioxide, zirconium oxide and zeolite composition.
9. the pH of technique as claimed in claim 1, wherein reactant mixture is less than 7.
10. the pH of technique as claimed in claim 9, wherein reactant mixture is less than 6.
11. technique as claimed in claim 1, carried out wherein reacting in the case where there is no nitrogen as active reaction composition.
12. technique as claimed in claim 1, wherein reactant mixture are free of nitrate and nitric acid.
13. technique as claimed in claim 1, wherein at least a part of pentose is dissolved with weak carboxylic acids.
14. technique as claimed in claim 1, wherein reactant mixture maintain at least 60 DEG C of temperature.
15. technique as claimed in claim 1, wherein reactant mixture maintain at least 90 DEG C of temperature.
16. technique as claimed in claim 1, wherein reactant mixture maintain 60-150 DEG C of temperature.
17. technique as claimed in claim 1, wherein reactant mixture maintain 80-120 DEG C of temperature.
18. technique as claimed in claim 1, carried out wherein reacting under at least 60psia oxygen partial pressure.
19. technique as claimed in claim 1, enter wherein reacting under the oxygen partial pressure in the range of 15psia to 2000psia
OK.
20. technique as claimed in claim 1, wherein at least a part of pentose obtains from carbohydrate source.
21. technique as claimed in claim 1, wherein pentose are selected from what is be made up of xylose, arabinose, ribose and combinations thereof
Group.
22. technique as claimed in claim 1, wherein oxygen are as air, oxygen-enriched air, single oxygen or have one kind
Or a variety of oxygen supplies to reacting substantially inert other compositions extremely react.
23. the pH of technique as claimed in claim 3, wherein reactant mixture is less than 6.
24. technique as claimed in claim 3, wherein reactant mixture maintain 80-120 DEG C of temperature.
25. technique as claimed in claim 3, wherein reactant mixture maintain at least 90 DEG C of temperature.
26. technique as claimed in claim 3, carried out wherein reacting under at least 60psia oxygen partial pressure.
27. technique as claimed in claim 24, carried out wherein reacting under at least 60psia oxygen partial pressure.
28. technique as claimed in claim 27, wherein pentose are selected from what is be made up of xylose, arabinose, ribose and combinations thereof
Group.
29. such as the technique any one of claim 1-28, carried out wherein reacting under the alkali that there is no addition.
30. such as the technique any one of claim 1-28, wherein heterogeneous oxidation catalyst includes Pt.
31. technique as claimed in claim 30, carried out wherein reacting under the alkali that there is no addition.
32. such as the technique any one of claim 1-28, wherein heterogeneous oxidation catalyst includes Pd.
33. technique as claimed in claim 32, carried out wherein reacting under the alkali that there is no addition.
34. a kind of technique for being used to prepare glutaric acid product, the technique include：
A) pentose is made in the presence of solvent and heterogeneous oxidation catalyst with oxygen reaction so that at least a portion pentose to be converted
For at least one valeric acid and/or its lactone, wherein heterogeneous oxidation catalyst is included selected from the group being made up of Pd, Pt and combinations thereof
Metal, the wherein pH of oxidation mixtures be not more than 7, and
B) presence of the hydrogenation deoxidation catalyst selected from the Zu d- areas metal being made up of ruthenium, rhodium, palladium, platinum and combinations thereof is being included
Under at least a portion of halogen source and hydrogen, at least one valeric acid and/or its lactone is reacted with by least one
At least a portion of valeric acid and/or its lactone is converted into glutaric acid product, and wherein glutaric acid product is Formula II compound
Wherein R1Independently be into salt ion, hydrogen, alkyl or substituted alkyl, wherein halogen source be selected from by HCl, HBr, HI, chlorine,
The group of bromine, iodine and its mixture composition.
35. technique as claimed in claim 34, wherein valeric acid are selected from by xylose diacid, arabic acid, nucleic acid and combinations thereof group
Into group.
36. technique as claimed in claim 34, wherein valeric acid include xylose diacid.
37. technique as claimed in claim 34, wherein glutaric acid product include glutaric acid.
38. technique as claimed in claim 35, wherein glutaric acid product include glutaric acid.
39. technique as claimed in claim 34, wherein Pd and/or Pt metals form heterogeneous oxidation catalyst gross weight
0.25-10%.
40. technique as claimed in claim 34, wherein Pd and/or Pt metals form the 1- of heterogeneous oxidation catalyst gross weight
8%.
41. technique as claimed in claim 34, wherein heterogeneous oxidation catalyst include being selected from by charcoal, aluminum oxide, titanium dioxide
The catalyst carrier for the group that silicon, titanium dioxide, zirconium oxide and zeolite form.
42. the pH of technique as claimed in claim 34, wherein oxidation mixtures is less than 7.
43. technique as claimed in claim 34, wherein oxidation reaction are entered in the case where there is no nitrogen as active reaction composition
OK.
44. technique as claimed in claim 34, wherein oxidation mixtures are free of nitrate and nitric acid.
45. technique as claimed in claim 34, wherein at least a part of pentose is dissolved with weak carboxylic acids.
46. technique as claimed in claim 34, wherein oxidation mixtures maintain at least 60 DEG C of temperature.
47. technique as claimed in claim 34, wherein oxidation mixtures maintain at least 90 DEG C of temperature.
48. technique as claimed in claim 34, wherein oxidation mixtures maintain 60-150 DEG C of temperature.
49. technique as claimed in claim 34, wherein oxidation mixtures maintain 80-120 DEG C of temperature.
50. technique as claimed in claim 34, wherein oxidation reaction are carried out under at least 60psia oxygen partial pressure.
51. the oxygen partial pressure of technique as claimed in claim 34, wherein oxidation reaction in the range of 15psia to 2000psia
Lower progress.
52. technique as claimed in claim 34, wherein at least a part of pentose obtains from carbohydrate source.
53. technique as claimed in claim 34, wherein pentose are selected from what is be made up of xylose, arabinose, ribose and combinations thereof
Group.
54. technique as claimed in claim 34, wherein oxygen are as air, oxygen-enriched air, single oxygen or with one
Kind or it is a variety of to reacting the oxygen supplies of substantially inert other compositions to oxidation reaction.
55. the pH of technique as claimed in claim 38, wherein oxidation mixtures is less than 6.
56. technique as claimed in claim 38, wherein oxidation mixtures maintain 80-120 DEG C of temperature.
57. technique as claimed in claim 38, wherein oxidation mixtures maintain at least 90 DEG C of temperature.
58. technique as claimed in claim 38, wherein oxidation reaction are carried out under at least 60psia oxygen partial pressure.
59. technique as claimed in claim 56, wherein oxidation reaction are carried out under at least 60psia oxygen partial pressure.
60. technique as claimed in claim 59, wherein pentose are selected from what is be made up of xylose, arabinose, ribose and combinations thereof
Group.
61. such as the technique any one of claim 34-60, wherein oxidation reaction is entered under the alkali that there is no addition
OK.
62. such as the technique any one of claim 34-60, wherein heterogeneous oxidation catalyst includes Pt.
63. technique as claimed in claim 62, wherein oxidation reaction are carried out under the alkali that there is no addition.
64. such as the technique any one of claim 34-60, wherein heterogeneous oxidation catalyst includes Pd.
65. the technique as described in claim 64, wherein oxidation reaction are carried out under the alkali that there is no addition.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US26841409P | 2009-06-13 | 2009-06-13 | |
| US61/268,414 | 2009-06-13 | ||
| CN201080026095.4A CN102803194B (en) | 2009-06-13 | 2010-06-11 | By material production pentanedioic acid and the derivative of carbohydrate containing |
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| CN201080026095.4A Division CN102803194B (en) | 2009-06-13 | 2010-06-11 | By material production pentanedioic acid and the derivative of carbohydrate containing |
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Non-Patent Citations (2)
| Title |
|---|
| Platinum-catalyzed oxidation of aldopentoses to aldaric acids;Fokko R. Venema等;《Joumal of Molecular Catalysis》;19921231;第77卷;75-85 * |
| Ueber eine neue pentosaure und die zweite inactive trioxyglutarsaure;FISCHER,E et al.;《BERICHTE DER DEUTSCHEN CHEMISCHEN GESELLSCHAFT》;18911231;第24卷(第2期);4214-4225 * |
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| PE20120661A1 (en) | 2012-05-31 |
| PE20120662A1 (en) | 2012-05-31 |
| CO6470815A2 (en) | 2012-06-29 |
| ECSP11011519A (en) | 2012-06-29 |
| CA2972533A1 (en) | 2010-12-16 |
| NZ622579A (en) | 2015-10-30 |
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