CN101115555B - Catalyst and process for preparing aromatic carboxylic acids - Google Patents
Catalyst and process for preparing aromatic carboxylic acids Download PDFInfo
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- CN101115555B CN101115555B CN2005800467554A CN200580046755A CN101115555B CN 101115555 B CN101115555 B CN 101115555B CN 2005800467554 A CN2005800467554 A CN 2005800467554A CN 200580046755 A CN200580046755 A CN 200580046755A CN 101115555 B CN101115555 B CN 101115555B
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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
- C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
- C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/163—X-type faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
- C07C63/14—Monocyclic dicarboxylic acids
- C07C63/15—Monocyclic dicarboxylic acids all carboxyl groups bound to carbon atoms of the six-membered aromatic ring
- C07C63/26—1,4 - Benzenedicarboxylic acid
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Abstract
The invention is directed to a catalytic principle based on zeolite crystallites attached to support or incorporated in a matrix and a catalytically active principle incorporated in the zeolite, the said crystallites having a diameter of between 20 and 300 nm and said catalytically active principle having a formula corresponding to: CoMn2(O)(R-COO)6 L<1>k1L<2>k2 wherein: R is an optionally substituted C1-C4 alkyl; L<1> is an optionally substituted nitrogen containing carboxylic acid or salts thereof; L<2> is selected from the group consisting of H2O, an optionally substituted C1-C4 alkyl containing carboxylic acid, an optionally substituted C5-C6 cycloalkyl or heterocycle, an optionally substituted C5-C6 heteroaryl or aryl; and k1 + k2 = 3; wherein the zeolite has an Si/Al atomic ratio of at least 8, as well as to a method for the oxidation of alkyl aromatics compounds employing the catalytic principle.
Description
Technical field
The present invention relates in general to the process chemistry field.More specifically, the present invention relates to be used to prepare the raw catelyst and the method that is used to prepare aromatic carboxylic acid of aromatic carboxylic acid.
Background technology
Aromatic carboxylic acid, for example, benzoic acid, phthalic acid, terephthalic acid (TPA), trimethylbenzoic acid, naphthalenedicarboxylic acid etc. are widely used in chemical industry as intermediate product.The preparation of aromatic carboxylic acid is (to see Suresh through their corresponding alkyl aromatic compounds of oxidation; A.; " Engineering Aspects of Industrial Liquid-Phase Air Oxidation ofHydrocarbons; ") Ind.Eng.Chem., Vol.39:p.3958-3997, (2000)).For example, the preparation of terephthalic acid (TPA) is through oxidation of p-xylene, as represented in the diagrammatic sketch below:
Terephthalic acid (TPA), i.e. TPA (1, the 4-benzene dicarboxylic acid), because it is making for example PETG (PET), 1, the purposes in the saturated polyesters such as 2-ethylene glycol and copolymer thereof is so have commercial interest for polymer industry.Press tonnage meter, the worldwide production of TPA and corresponding dimethyl ester thereof, dimethyl terephthalate (DMT) accounts for the 25th in all chemical products of producing in 1992, and accounts for the 10th in all organic chemistry products.
Be shown in the following figure, the oxidation of paraxylene be one by free radical cause, progressively (or substep) (step-wise) reaction of carrying out, it produces two kinds of main intermediate products, i.e. p-methylbenzoic acid and 4-formoxyl-benzoic acid.
The incomplete oxidation of 4-formoxyl-benzoic acid (4-CBA) has caused the pollution of TPA purity.4-CBA is owing to make the removal of 4-CBA become complicated with the TPA structural similarity with the fact of TPA cocrystallization.The pollution that 4-CBA produces possibly be sizable; For example; The production process of producing the TPA raw material can produce the 4-CBA of about 5000ppm (people such as Perniconea " An investigation of Pd/C industrial catalysts forthe purification of terephthalic acid; " Catalysis Today, Vol.44:p.129-135 (1998)).Like this; In order to obtain the TPA raw material of the synthetic required enough purity of high-grade polyester; The step that usually need after TPA produces, then carry out purifying (is seen Matsuzawa; K. wait " Technological Development of PurifiedTerephthalic Acid, " Chemical Economy & Engineering Review of people, Vol.8 (9): p.25-30 (1976)).
There is numerous processing methods to be applicable to and produces TPA; Each method wherein can be produced the TPA of different output and purity; And wherein most of processing methods all comprise: contain at least bore and/or the liquid phase of the metal of manganese, condition that homogeneous catalyst exists under, with oxygen source air or oxygen oxidation of p-xylene for example.In addition; Wherein most processing method all is under the condition that acid flux material exists, to carry out; Acetic acid for example, and use corrosive bromine to help the source of (catalysis) agent (promoters) usually, for example HBr, NaBr or other metal bromide (metal bromines) as group.Like this, these processing methods are normally carried out in the titanium lining reactor of the costliness that can allow this harsh reaction condition.Typical method patent and the publication below that is used for preparing TPA described, and its full content is incorporated into this, as a reference.
United States Patent (USP) has been reported for No. 2833816 and No. 3089906 in the acetate solvate of the catalyst that uses metal bromide and has been used O
2The method of the fragrant hydrocarbon compound of oxidation polyoxyethylene alkyl aryl.
United States Patent (USP) has been reported the method for using bromine source cacodyl oxide benzene and trimethylbenzene under the condition that the aliphatic acid in being present in nickel, zirconium and Mn catalyst system exists for No. 4786753.
United States Patent (USP) has been reported under the condition that heavy metal catalyst and bromine exist the method for carrying out two-stage oxidizing with molecular oxygen (molecular oxygen) for paraxylene for No. 4877900.Wherein, second stage comprises with molecular oxygen carries out rear oxidation, and second stage is carried out under the temperature higher than the phase I.
United States Patent (USP) has been reported the method for the two-stage oxidizing alkylbenzene under the condition of the metallic catalyst of cobalt, nickel or zirconium and bromine existence for No. 4892970, and wherein, extra bromine is added in the second stage of this method.
United States Patent (USP) has proposed at the C that contains cobalt, manganese and cerium catalyst and bromine source for No. 5453538
1-C
6In the aliphatic carboxylic acid solvent with the method for molecular oxygen oxidation xylenes.
United States Patent (USP) has been reported through almost pure O is provided in reactor for No. 5596129 and No. 5696285
2Gas source is come the method for oxidation of alkyl benzene.These methods are carried out in acetic acid/aqueous medium, and have used cobalt, manganese and bromine catalyst.
Cincotti; A. wait the people " Kinetics and related engineering aspects ofcatalytic liquid-phase oxidation of p-xylene to terephthalic acid; " Catalysis Today; Vol.52:p.331-347, the kinetic model that is used to produce TPA has been reported in (1999).This research evaluation paraxylene using cobalt naphthenate as the oxidation in the methyl benzoate solvent of catalyst.Use p-tolyl aldehyde as helping (catalysis) agent source, use pure oxygen or air as oxidation source.
Dunn; J. wait people's (Terephtahlic Acid Synthesis in High-TemperatureLiquid Water; Ind.Eng.Chem.Res., Vol.41:p.4460-4465, (2002)) reported and under 250 ℃ to 300 ℃ temperature, in aqueous water, carried out the synthetic method of TPA.The oxidant that this method is used is a hydrogen peroxide, rather than air or O
2Estimated following catalyst in this research: manganous bromide, cobaltous bromide, manganese acetate, nickelous bromide, bromination hafnium and zirconium bromide.
Partenheimer; W. wait the people " The effect of zirconium inmetal/bromide catalysts during the autoxidation of p-xylene; " Journalof Molecular Catalysis A:Chemical; Vol.206:p.105-119, (2003) have been reported and in acetic aid medium, have been used Zr catalyst, and the effect of cobalt or manganese/bromine or nickel/manganese/bromine or cobalt/manganese/bromine catalyst oxidation of p-xylene.
Compare with NaBr or HBr, the less bromine anthracene of corrosivity is used as the bromine source in the oxidation reaction of paraxylene.People such as Saha (" Bromoanthracenes andmetal co-catalysts for the autoxidation of para-xylene; " Journal ofMolecular Catalysis A:Chemical; Vol.207:p.121-127, (2004)) reported at Co (OAc)
2And Mn (OAc)
2Or Ce (OAc)
3Or ZrOCl
2The condition that exists of co-catalyst (co-catalyst) under, in acetic acid, use 9,10-dibromoanthracene or 9-bromine anthracene oxidation of p-xylene.
The method of using solid catalyst to prepare TPA comprises people's such as Chavan " Selective Oxidation of para-Xylene to Terephthalic Acid by μ
3-oxo-bridged Co/Mn Cluster Complexes Encapsulated in Zeolite-Y; " Journal of Catalysis; Vol.24:p.409-419, people's such as (2001) and Srinivas (No. the 6649791st, United States Patent (USP) and U.S. Patent application disclose No. 2003/0008770).In these methods, solid catalyst is the μ that is coated among zeolite-Y
3The Co/Mn basigamy compound [Co that oxo bridge connects
3(O) (CH
3COO)
6(pyridine)
3]
+, [Mn
3(O) (CH
3COO)
6(pyridine)
3]
+And CoMn
2(O) (CH
3COO)
6(pyridine)
3In, and these oxidation processes are using sodium bromide to carry out in as the acetic acid/aqueous solvent of radical initiator.
Also can not use bromide ion, and use solid catalyst to prepare TPA.People's such as Jacob (Journal Applied Catalysis A:General; Vol.182:p.91-96; (1999)) describe the use tert-butyl hydroperoxide as initator, on salen, saltin and the salcyhexen complex of cobalt that coats zeolite or manganese, carried out the air oxidation of paraxylene.This method can transform 50%～60% paraxylene, and still, TPA yields poorly, and the primary product that obtains is a p-methylbenzoic acid.
At present, for fear of additional purification step, need be able to synthesize the method for the suitable aromatic carboxylic acid of enough high yields and purity and high-grade preparation technology subsequently.It is environmentally harmful like corrosive charge raw material or other methods that processes raw material such as acetic acid, NaBr or HBr also to need those to avoid the use of.
Summary of the invention
The present invention relates to new solid catalyst and prepare the application in the process of aromatic carboxylic acid in oxidation through alkyl aromatic compound.The present invention also provides the one-step method with this catalyst, and it can avoid the needs of subsequent purification step, for example, is used to prepare the hydrogenization of high-grade alkyl aromatic compound.The specific embodiment of this method has been avoided the inorganic bromide reagent of use corrosivity through using (more environmentally sensible) the organic bromide reagent that on environment, more is prone to discover.This raw catelyst itself is made up of the little crystallite of this catalyst component; The narrow particle diameter that crystallite has appointment distributes; And be attached to or be coated on carrier, more specifically, be coated in the host material mesoporous property (meso-porous), that possibly on function, be able to strengthen.
The present invention aims to provide a kind of based on being attached on the carrier or being coated on catalytic component and a kind of catalytic active component that is combined in the zeolite of the zeolite crystallite in the matrix; To between the 300nm, said catalytic active component has corresponding following chemical formula to the diameter of said catalyst at 20nm:
CoMn
2(O) (R-COO)
6L
1 K1L
2 K2, wherein:
R is optional substituted C
1～C
4Alkyl;
L
1Be carboxylic acid or its salt that contains optional substituted nitrogen;
L
2Be selected from by H
2O, comprise optional substituted C
1～C
4The carboxylic acid of alkyl, optional substituted C
5～C
6Cycloalkyl or heterocycle, optional substituted C
5～C
6The group that heteroaryl or aryl constitute; And
k1+k2＝3；
Wherein, the Si/Al atomic ratio of zeolite is at least 8.
The specific embodiment comprises the catalyst of above-mentioned chemical formulation, and wherein, R is-CH
3Or-C
2H
5, L
1Be pyridine carboxylic acid, nicotinic acid or different-nicotinic acid, L
2Be acetic acid or H
2O.
The present invention also aims to provide the catalyst component with corresponding following chemical formula:
CoMn
2(O) (R-COO)
6-k3L
3 K4L
4 K4, wherein:
R is optional substituted C
1～C
4Alkyl;
L
3It is the carboxylate that contains optional substituted nitrogen;
L
4Be selected from by H
2O, contain optional substituted nitrogen carboxylic acid, contain optional substituted C
1～C
4The carboxylic acid of alkyl, optional substituted C
5～C
6Cycloalkyl or heterocycle and optional substituted C
5～C
6The group that heteroaryl or aryl constitute;
K3 is 1,2 or 3; And
k3+k4＝3。
The preferred specific embodiment comprises the catalyst component of above-mentioned chemical formula, and here, R is-CH
3Or-C
2H
5, L
3Be 1-pyridine-COO
-, 2-pyridine-COO
-, or 3-pyridine-COO
-, L
4Be pyridine carboxylic acid, nicotinic acid or isonicotinic acid, acetic acid or H
2O.
Wherein, the objective of the invention is to the catalytic active component that this is specific and be incorporated in the zeolite of special selection, this zeolite preferably has following characteristic: the Si/Al atomic ratio in this zeolite is at least 8.Preferred Si/Al atomic ratio is at most 12.Preferably, the size of this passage (channels) can make catalytic active component can not move through passage too greatly.But the infall of passage is enough big, can capture (trap) this catalytic active component.Therefore, although zeolite also can synthesize around said complete component, in the present invention, said component is synthetic in position, that is, at described infall, this method is a method for optimizing.
The channel diameter that is fit to be not more than 8
scope in.
Zeolite crystallite is quite little, promptly between 20nm to 300nm.Bigger crystallite may produce diffusion restriction (diffusion limitation), causes active and the selectivity reduction, thereby reaches one object of the present invention, and promptly can not need carry out subsequent purification and handle and produce aromatic carboxylic acid, for example, terephthalic acids.
Another aspect of the present invention is that matrix seals (matrix encapsulation).This matrix is supporting crystallite, and can have mesoporous property structure.Carrier or host material preferably in oxidation reaction not or have limited effect, thereby do not hinder reactive component to diffuse into crystallite or from crystallite, leave.The host material of fitting order comprises mesoporous silicon oxide, carbon, CNT etc.
The catalyst component that here proposes has the metal complex of formation (host) in the zeolite that possibly on function, be able to strengthen, this zeolite include, but not limited to MEI, β (
*BEA) (type), and also comprise unordered family (associateddisorder family) composition relevant like cellulosic etc., and based on the microporosity structure of the mixture of above-mentioned zeolite and complex thereof.List of references tabulation about the special construction information of the illustrated in detail of structural similarity in the zeolite and relevant zeolite; Can referring to; For example, United States Patent (USP) No. 4344851, No. 4503023, No. 4840779, and people such as Baerlocher " Atlas ofZeolite Framework Types; " ELSEVIER Fifth Revised Edition, (2001).The zeolite that preferably is used to hold (host) current metal complex comprises the β zeolite.
Term " alkyl " is meant the hydrocarbyl group that comprises one to 20 carbon atom.Term " alkyl " comprises the straight chained alkyl group, like methyl, ethyl, propyl group etc.This term also comprises the side chain isomer of straight chained alkyl group.In addition, alkyl can be substituted according to following definition is optional.Therefore, alkyl group comprises primary alkyl group, secondary alkyl group and tertiary alkyl groups.At present, preferred alkyl group comprises and contains a unsubstituted alkyl group to four carbon atom, and even this alkyl group that is more preferably contain one to three carbon atom.
Term " replacement " is meant that an atom or one group of atom can replace with another substituting group.Term " replacement " comprises any grade replacement, that is, a replacement, two replaces, three replacements, four replace and five replacements, and this here being substituted in chemically is admissible.Replacement can occur on any chemically accessible position and occur on any atom, as occurs in the replacement on the carbon.For example, substituted compound is such compound, and the key that the one or more key that wherein is connected in the hydrogen that contained or carbon atom is connected to non-hydrogen and/or non-carbon atom replaces.
Term " contains nitronic acid " and is meant and contains at least one carboxyl (COOH) with the compound of at least one optional substituted nitrogen-atoms.Nitrogenous carboxylic acid compound comprises no ring structure and circulus, and wherein nitrogen can be replaced by annular atoms (ring member) alternatively.For example, contain nitronic acid contain pyridine, picoline, pyrimidine, piperidines and similarly contain at least one-COOH (compound).Preferably contain nitronic acid and comprise pyridine carboxylic acid, nicotinic acid and isonicotinic acid (its structure is as follows):
Term " contains C
1～C
4The carboxylic acid of alkyl " be meant and contain at least one carboxylic moiety (COOH) with at least one optional substituted C
1～C
4The compound of alkyl group.This term contain comprise at least one-C of straight chain, side chain and the ring-type of COOH
1～C
4Alkyl group.And the C that contains any degree of saturation also contained in this term
1～C
4Alkyl group.For example, contain C
1～C
4The carboxylic acid compound of alkyl comprises the substituent of acetic acid, propionic acid, butyric acid and its halo, like CH
2FCOOH, CH
2ClCOOH, CH
2BrCOOH etc.Preferably contain C
1～C
4The carboxylic acid of alkyl comprises CH
3COOH.
Term " nitrogenous carboxylate " is meant and contains at least one carboxylic acid ion (COO
-) and the compound of at least one optional substituted nitrogen-atoms.Nitrogenous carboxylate compounds comprises no ring structure or circulus, and wherein nitrogen can be annular atoms (ring member) alternatively.For example, nitrogenous carboxylate contain pyridine, picoline, pyrimidine, piperidines, morpholine and similarly contain at least one-COO
-(compound).Preferred nitrogenous carboxylate comprises 1-pyridine-COO
-, 2-pyridine-COO
-With 3-pyridine-COO
-(its structure is as follows):
Term " cycloalkyl " is meant the saturated or unsaturated alicyclic moiety that contains one to 20 carbon atom.Group of naphthene base comprises cyclohexyl and suberyl.Term " substituted cycloalkyl " refers to according to the substituted group of naphthene base of above-mentioned definition.Substituted group of naphthene base can contain one or more can be by the substituted atom of straight or branched alkyl group, and may further include other cyclosubstituted group of naphthene base that can be comprised condensed ring.Representational substituted group of naphthene base can be mono-substituted, for example, but is not limited to, and 2-replacement, 3-replacement, 4-replacement, the substituted cyclohexyl groups of 5-or single substituted radical, for example, alkyl or halo group (halo groups).
Term " heterocycle " or " heterocycle " are meant aromatic rings and non-aromatic ring alkyl compound.Heterocyclic group comprises monocycle and the bicyclic compound that contains three or more annular atoms (ring member), and wherein one or more are hetero atom, for example, but are not limited to N and O.The example of heterocyclic group include, but not limited to contain one to three nitrogen-atoms unsaturated three to hexatomic ring, for example; But be not limited to pyrrole radicals, pyrrolinyl, imidazole radicals, pyrazolyl, pyridine radicals, dihydropyridine base, pyrimidine radicals, pyrazinyl, pyridazinyl, triazolyl (for example, 4H-1; 2,4-triazolyl, 1H-1,2; 3-triazolyl and 2H-1,2, the 3-triazolyl); Contain one to four nitrogen-atoms saturated three to octatomic ring, for example, but be not limited to pyrrolidinyl, imidazolidinyl, piperidyl, piperazinyl; What contain one to three nitrogen-atoms condenses the unsaturated heterocycle group, for example, but is not limited to indyl, isoindolyl, indyl, indolizine base, benzimidazolyl, quinolyl, isoquinolyl, indazolyl, BTA base; Contain one to two oxygen atom and one to three nitrogen-atoms undersaturated three to octatomic ring, for example, but be not limited to ， oxazolyl 、 isoxazolyl 、 oxadiazole base (for example, 1,2,4-oxadiazole base, 1,3,4-oxadiazole base, and 1,2,5-oxadiazole base); Contain one to two oxygen atom and one to three nitrogen-atoms saturated three to octatomic ring, for example, but be not limited to morpholinyl; The unsaturated annelated heterocycles group that contains one to two oxygen atom and one to three nitrogen-atoms, for example, benzoxazolyl, Ben Bing oxadiazole base and benzoxazinyl (for example, 2H-1,4-benzoxazinyl).Preferred heterocyclic group comprises five or six annular atomses.The heterocyclic group that is more preferably comprises morpholine, piperazine, piperidines, pyrrolidines, imidazoles, pyrazoles, 1; 2; 3-triazole, 1; 2,4-triazole, tetrazolium, thiomorpholine, wherein thiomorpholine, pyrroles, high piperazine (homopiperazine), oxazolidine-2-ketone, pyrrolidin-2-one, oxazole, quinuclidine, thiazole and the isoxazole of sulphur atom and one or more O atom bondings.Term " substituted heterocycle " or " substituted heterocycle " are meant according to the substituted heterocyclic group of above-mentioned definition.The example of substituted heterocyclic group includes, but not limited to 2-tolimidazole base, 5-tolimidazole base, 1-methyl piperazine base, 2-chloropyridine base and similar group.
Term " aryl " is meant by three to 20 aromatic groups that carbon atom is formed.Aromatic group includes, but not limited to phenyl, diphenyl, anthryl and naphthenyl.Term " substituted aromatic yl group " is meant the substituted aromatic yl group of definition that provides above the basis.For example, substituted aromatic yl group can be bonded to one or more carbon atoms, oxygen atom or nitrogen-atoms, also comprises such aromatic yl group, and promptly its one or more aromatic carbons are bonded to substituted and/or unsubstituted alkyl, alkenyl or alkynyl group.Thereby these two carbon atom bondings that comprise aromatic yl group are wherein arranged in the bonding that two atoms of alkyl, alkenyl or alkynyl group limit a condensed ring system (for example, dihydro naphthyl or tetralyl).Therefore, term " substituted aryl " includes, but not limited to tolyl, hydroxyphenyl etc.Preferably, aromatic group with alkyl, carboxylic acid (COOH) and/or carboxylate groups (COO
-) replace.
Term " heteroaryl " is meant the aromatic ring of (i) three to 20 annular atomses, and it is made up of carbon atom and for example hetero atom such as N and O; Or two rings of eight to ten annular atomses (ii) forming by carbon atom and hetero atom or the ring system of many rings, it is made up of hetero atoms such as carbon atom and N and O, and wherein: second cycle line has at least one to be aromatic ring in uniting.Hetero-aromatic ring can be connected in arbitrary hetero atom or carbon atom.Representational heteroaryl compound comprises, for example, and pyridine radicals, pyrazinyl, pyrimidine radicals, Bi Ding Bing oxazolyl, pyridazine Bing oxazolyl and Mi Ding Bing oxazolyl.Term " substituted heteroaryl " is meant according to the substituted heteroaryl groups of above-mentioned definition.
One aspect of the present invention is to provide, under the condition that the catalyst that provides herein exists, through prepare the method or the manufacturing process of aromatic carboxylic acid with oxygen source contact alkyl aromatic compound.Preferably, this method is under the condition that the solvent of the said aromatic carboxylic acid of solubilized exists, to carry out.
The present invention also is to be provided for preparing the one-step method (or one-step method) of aromatic carboxylic acid, under the condition comprising the catalyst existence that provides herein, through contacting alkyl aromatic compound with oxygen source.In the preparation process of high-grade alkyl aromatic compound, this one-step method efficient is high, thereby does not need the subsequent purification step of hydrogenization for example or crystallization.
More preferably, the purpose of this method is, oxidation of p-xylene prepares terephthalic acid (TPA) under the condition that exists through the catalyst that provides herein.Other aromatic carboxylic acid that can prepare comprises different-terephthalic acid (TPA) and naphthoic acid.
Term " aromatic carboxylic acid " is meant that any at least one carboxylic acid that contains (COOH) substituent can be by substituted aromatic series alternatively.Representational aromatic carboxylic acid includes, but not limited to benzoic acid, M-phthalic acid, phthalic acid, terephthalic acid (TPA), trimethylbenzoic acid, naphthalene dicarboxylic acids etc.Preferred aromatic carboxylic acid comprises terephthalic acid (TPA) (TPA).
Term " alkyl aromatic " is meant any optional substituted aromatic group, and like top definition, this aromatic group comprises that at least one is like top defined optional substituted alkyl group.Representational alkyl aromatic compound includes, but not limited to toluene, xylenes (paraxylene), trimethylbenzene, methyl naphthalene, dimethylnaphthalene and similar compound.Preferred alkyl aromatic compound comprises paraxylene.
Term " oxygen source " is meant any source that in current method required for protection, can directly or indirectly supply oxygen.Oxygen source can be supplied with by external source, but also original position generates.Preferably, with oxygen source be provided at identical with solvent mutually in.For example, can pass through to absorb from oxygen-saturated supercritical solvent, or under high pressure seeing through the gaseous oxygen of selective membrane, with O
2Supply with the liquid phase solvent of paraxylene.Perhaps, can be through for example under high pressure absorbing oxygen-containing gas such as air or molecular oxygen and with O
2Absorb in the solvent, and in the direct supply response device, and/or through supplying with recirculation flow via the selective membrane diffusion and from reactor.According to the characteristics of the solvent of oxygen, also can be through evaporation or the dissolving and the absorption in comprising the solvent of supercritical fluid of liquid oxygen, with O
2Provide and supply to the reaction medium from saturated solution directly or indirectly.Representational oxygen source includes, but not limited to air, gaseous state and liquid molecular oxygen, hydrogen peroxide etc.Preferably, the oxygen content of oxygen source used herein is at least 99%, is at least 90%, is at least 85% or be at least 80%.
The specific embodiment of the present invention relates to the method that under the condition that solvent exists, prepares aromatic carboxylic acid, the said aromatic carboxylic acid of solubilized in this solvent.Preferably, used solvent is identical with alkyl aromatic compound in this method.For example, in the specific embodiment of the method that is used for preparing TPA, preferred solvent and alkyl aromatic compound all are paraxylene.
The preferred specific embodiment is included in and implements this method when not having acid flux material.Because for example acid flux material such as acetic acid is a highly corrosive, therefore, generally adopt reactor in the steel lining to use the reaction of said solvent.The method that here proposes provides improvement to state of the art, and can partly avoid the use of reactor in the steel lining through in nonacid solvent, reacting.
Term " solvent " is meant a kind of material, is generally liquid, the another kind of material of its solubilized, for example, alkyl aromatic compound.The purity of solvent used herein is at least 99%, or is at least 97%, or is at least 95%.The solvent that preferably is used for this method comprises paraxylene.
Term " soluble " is meant the solubility of the given compound of aromatic carboxylic acid of producing in the solvent for example etc.Solubility can be that unit measures with g/L or mole/L, and wherein, the applicable elements of this measuring method is: temperature range is 150 ℃～250 ℃, and pressure limit is 20atm～50atm.In the preferred specific embodiment, the solubility of terephthalic acid (TPA) in paraxylene 25 ℃, be 0.0028g/L during latm.
The pH value that term " acid " is meant solvent or solution is less than 7, and for example 5 or lower, even be for example 3 or lower.
Use the reaction rate of the method for the Catalyst Production aromatic carboxylic acid among the present invention to increase through adding halogen reagent.Term " halogen reagent " is meant the organic or inorganic reagent that contains such as halogen ions such as F, Cl, Br and I.Preferred halogen reagent can be used as media and impels (mediate) group to generate and hydrogen abstraction reaction, and does not obviously introduce free halogen or halogen ion, for example, and F
, F
-, Cl
, Cl
-, Br
Or Br
-Typical halogen reagent comprises the alkyl bromating agent, for example, and bromobenzene, 9-bromine anthracene and 9,10-dibromoanthracene.
Term " alkyl " be meant any have can direct-connected carbon atom organic group.Hydrocarbyl group comprises saturated and unsaturated hydrocarbons, straight chain and chain aliphatic hydrocarbon, cyclic hydrocarbon and aromatic hydrocarbon.Representational hydrocarbyl group comprises alkyl, thiazolinyl, alkynyl, cycloalkyl, aryl (for example anthracene) and aralkyl.
Description of drawings
Fig. 1 and Fig. 2 are the sketch mapes that expression is used for the typical method of oxidation of alkyl arene compound.Provide in the following instance and the relevant more details of oxidation of p-xylene generation terephthalic acid (TPA).
Fig. 3 has specified the solubility range of terephthalic acid (TPA) and the operated concentration range of catalyst.
The specific embodiment
1. catalyst of the present invention
A. the preparation of catalyst component of the present invention
The present invention is through will be like foregoing and CoMn
2(O) (R-COO)
6L
1 K1L
2 K2And CoMn
2(O) (R-COO)
6-k3L
3 K3L
4 K4Corresponding catalyst component is stabilized in the micro porous zeolite, or as through in the zeolite composite construction, synthesizing and the aggregation (clustered aggregate) of the cluster that quilt is coated especially, the new compositions with unique catalysis is provided.This catalyst is made up of the suitable undersized zeolite crystallite that is embedded in the mesoporous matrix of inert material or be attached to suitable carrier.
The preferred embodiment of the metal complex of catalyst provided herein comprises CoMn
2(O) (CH
3-COO)
6(2-NC
6H
4COOH)
3And CoMn
2(O) (CH
3-COO)
5(1-NC
6H
4COO) (1-NC
6H
4COOH)
2/ in mesoporous property SiC matrix, have little crystallite (～100nm) a β zeolite.
As far as those of ordinary skills, the whole bag of tricks that is used to prepare the component of catalyst of the present invention is all known.For example; Synthetic Preparation of catalysts technology of the present invention is included in the preparation technology described in the following document: people's such as Kennet J. " Applicable Zeolite Encapsulation Methods Flexible Ligand Method "; J.Inclus; Phenom., Vol.21:159-184 (1995); Vandermade, people's such as A.W. J.Chem.Soc.Chem.Commun., Vol.1204 (1983); With people's such as Viswanathan J.Energy Heat and Mass Transfer, Vol.8:281 (1996).The production of mesoporous property zeolite is described, for example, and at " TailoredPorous Materials " Chem.Mater.1999 of people such as Walter G.Klemperer, 11,2633-2656.
In order to prepare the zeolite that uses with bigger ligand, can adopt alternative preparation method.When ligand molecule more greatly or too not flexible (inflexible) and can not penetrate zeolite the time, can pass through utilization structure guide molecule (structure directing molecules) at preformed μ
3-oxo bridge connects synthetic zeolite around the complex of metal-complexing.This kind technology is described in following document, for example, and Mitchell, people's such as M. Z.Phys.B, Vol.97:353 (1995); Lobo, people's such as R. J.Inclusion Phenom.Mol.Recognit.Chem., Vol.21:47 (1995); And Barton, people's such as T.J. " Tailored PorousMaterials ", Chem.Mater., Vol.11:2633-2656 (1999).Nearest description also can be found, for example, at " Microporous materials " ScienceProgress (2002) of Martin P.Attfield, 85 (4), among the 319-345.
In addition, component of the present invention further comprises zeolite.In the preferred specific embodiment, catalyst of the present invention is made up of the crystallite that coats the zeolite catalysis component.The catalyst component that some zeolite provides can more preferably be used in the method for application of the present invention.
The Si/Al atomic ratio that is suitable for zeolite of the present invention is at least 8.These zeolites are poromerics; Hole by size is not more than
constitutes, and does not preferably have zeolite cages (zeolite cages).
The β zeolite that preferred zeolite is mesoporous property (
*BEA), it is to have the little crystallite that size is about 20nm～200nm, but also comprises relevant unordered family, as cellulosic.The specific specific embodiment of bunch position catalyst provided herein (clustered sites catalysts) comprises being coated on imbeds (embeded) in mesoporous property SiO
2CoMn in the β zeolite in the matrix
2(O) (CH
3-COO)
6(2-NC
6H
4COOH)
3, hold the CoMn in (hosted) β zeolite on the carbon that is supported in mesoporous property
2(O) (CH
3-COO)
5(1-NC
6H
4COO) (1-NC
6H
4COOH)
2
The exemplary process that is used for coating catalyst component of the present invention comprises the catalytic structure of usefulness " method of flexible ligand " foundation " bottle ship " formula.This method of knowing comprises that ligand diffuses through the micropore of the zeolite that metal exchange takes place.Discussion more specifically about the preparation method of demonstration can be referring to for example, people's such as Raja J.catal.Vol.170, p.244 (1997); People's such as Subbarao Chem.Comm., Vol.355, (1997); With people's such as Balkus J.Inclus.Phenom., Vol.21:p.159 (1995).
B. the matrix of catalyst of the present invention coats
The situation that little zeolite crystallite original position in its building-up process is embedded in the mesoporous property inert base comes into question in below the document, for example, and people's such as J.C.Jansen Chem.commun., p.713 (2001); People's such as Z.shan chem.Eur.J., 7, p.1437 (2001), people's such as J.C.Jansen Micro.Meso.Mater.; 21, p.213 (1998), and S.Basso; J.P.Tessonnier, C.Pham-Huu, the french patent application 02-00541 (2002) of M.J.Ledoux number.
Coating provides mechanical strength for catalyst component, and catalyst of the present invention is prepared to be used for fixing several kinds of bed, slurry grain, film and other structure multi-form.
This preferable methods is with zeolite synthetic that depends on catalyst component simultaneously and coating host material.The preparation method can comprise the zeolite that scion grafting prepares in addition on inert host material, or alternatively, this synthetic can original position be synthetic through in specific zeolite synthesized gel rubber, adding the host material that is fit to.These methods, the hydrothermal synthesis method that for example is fit to is all known those of ordinary skills.The synthetic method of synthetic, for example hydro-thermal synthesis process comes into question; For example; At people such as Camblor M.A. " Characterization of nanocrystalline zeolite Beta ", Microporous andMesoporous Materials 25 is p.59-74 in (1998).The synthetic of zeolite Y that is coated on the SiC comes into question, for example, at G.Clet, the poster at 12 of J.C.Jansen and H.van Bekkum
ThIZC, Baltimore, in (1998), and scion grafting β zeolite has come into question on SiC, for example, the Nature of S.Feng and T.Bein, 368, p.834 (1994).M.V. deposition zeolite crystallite comes into question on silica, for example, at Landau, N.Zaharur, the Appl.Catal.115 of M.Herskowitz is among the L7-L14 (1994).The method that zeolite is deposited on the carbon comes into question, and for example, at C.Madsen, the Chem.Commun.8 of C.J.H.Jacobsen is p.673-674 in (1999).Use the method micella template, that synthesize the mesoporous property structure of high-sequential through the self assembly of preformed zeolite nuclear group bunch of surfactant to be described; As; Angew.Chem. at Z.T.Zhang, Y.Han, L.Zhu, R.W.Wang, Y.Yu, S.L.Qiu, D.Y.Zhao and F.S.Xiao; 113; The Microporous Mesoporous Mater. of 1298-1301 (2001) and W.PGuo, L.M.Huang, P.Deng, Z.Y.Xue and Q.Z.Li, 44,427-434 (2001).
Preferred coating host material comprises the silica and the carbon of mesoporous property, for example, and CNT, and SiC.
The original position of metal complex self is synthetic can carry out after zeolite being coated in the host material.The method of preferred preparation catalyst of the present invention is as second production stage after coating, in matrix, to generate catalyst component itself.
II. Application of Catalyst of the present invention
Catalyst provided herein can be used in multiple synthetic method.For example, catalyst of the present invention can be used for synthetic multiple organic compound, for example, but is not limited to, and contains the compound of alkyl, thiazolinyl, alkynyl, cycloalkyl, heterocyclic radical, aryl or heteroaryl.In addition, it is synthetic that catalyst of the present invention can be used for the stereoselectivity of organic compound.And catalyst of the present invention can be used for preparing macrocyclic compound, like bactericide, antibiotic, natural products analogies etc.
More preferably, catalyst of the present invention is used for the oxidation of alkyl arene compound, to generate aromatic carboxylic acid.As far as those of ordinary skills, the whole bag of tricks of oxidation of alkyl arene compound is all known under the condition that catalyst exists.Described in the example below is that general representational method is arranged, and the factor that this method can be in the scope of routine test method be known according to for example synthetic scale (scale) etc. changes.
The preparation of aromatic carboxylic acid can be carried out in a reactor, also can in the series reaction device, carry out.Term " reactor " is meant any container that oxidation reaction described herein provides the place that is well-suited for.For example, the oxidation of alkyl aromatic compound can be carried out in an independent big pot type stirred reactor.Perhaps, the oxidation of alkyl aromatic compound also can be carried out in a continuous tandem reactor.For example, can oxygen source be offered each reactor in this (tandem reactor) series, thereby promote the efficient oxidation of alkyl aromatic compound.In addition, this reactor series can use blocking device (lock) to regulate, thereby prevents feed back.
The reactor and the steel reactor that can comprise titanium lining according to the typical reactor that method provided herein is used.
This method that is used to prepare aromatic carboxylic acid can be carried out under following condition: temperature range is 200 ℃～250 ℃, and pressure limit is 280psig～750psig.
According to method provided herein, alkyl aromatic compound is offered at least one reactor.Alkyl aromatic compound comprises having at least one oxidable substituent aromatic hydrocarbon, and this substituting group can be oxidized to corresponding carboxylic acid or its derivative products.Preferred alkyl aromatic compound comprises the raw material of disubstituted benzenes, and this raw material has any substituting group in for example alkyl, hydroxyalkyl, acetaldehyde, carbon alkyl group and their the multiple substituting groups such as mixture.Preferred alkyl aromatic compound comprises having alkyl group as substituent contraposition-two base substituted (para-disubstituted) benzene derivative.Preferred especially alkyl aromatic compound is a paraxylene and/or to toluic acid.
Usually, alkyl aromatic compound is offered at least one reactor with about 310kg/s to the amount of about 1010kg/s scope.
In the preferred specific embodiment, under the condition that the solvent of the aromatic carboxylic acid that solubilized generated exists, implement this method.For example, this solvent comprises, but is not limited to paraxylene; Basic solvent, for example ester of chlorobenzene, morpholine, carboxylic acid etc.; Carboxylic acid anhydrides; And acid flux material, for example acetic acid.
Preferred especially solvent is the solvent identical with alkyl aromatic compound.For example, in the specific embodiment of the method for preparing TPA, preferred solvent and alkyl aromatic compound all are moisture by weight 0～18% paraxylene.In other specific embodiment of the method for preparing TPA, preferably can dissolve the solvent of terephthalic acid (TPA) and intermediate product 4-CBA.Do not hope to receive the restriction of any particular theory, but can believe, 4-CBA is remained on the further oxidation that can promote 4-CBA in the solution.Consequently, more most 4-CBA is converted to terephthalic acid (TPA) in the reaction medium, has therefore reduced the formation of color precursor.In addition, this method need be from not removing 4-CBA in the precipitated solid product reaction medium, and can allow step preparation TPA.
Usually, solvent is offered at least one reactor with the speed of about 310kg/s～1010kg/s scope.
According to method provided herein, at least a catalyst of the present invention is offered at least one reactor.For example; Catalyst of the present invention can be used as slurry (entrained slurry), the fluid bed (fluidized bed) carried secretly and offers each reactor; Or in each reactor of tandem reactor, be installed in various forms of fixed beds, film, filling device (packing arrangement) etc.Catalyst component can be provided individually or provided as the zeolite crystallite that is embedded in the inert base.Usually, catalyst of the present invention is offered at least one reactor with the amount of 700 weight portions/100 weight portion paraxylene to 1400 weight portions/100 weight portion paraxylene scopes (form that coats with matrix).Under the condition that catalyst of the present invention exists, the oxidation reaction of alkyl aromatic compound can occur in the time of about 8min～20min scope.
The raising of the reaction rate of the oxidizing process that here proposes can be carried out through adding halogen reagent or halogen releasing agent.Preferred halogen reagent comprises bromination alkyl reagent, for example, and 9-bromine anthracene and 9,10-dibromoanthracene.Halogen reagent or halogen releasing agent can join at least one reactor, for example, and each reactor in the tandem reactor.In addition, identical or different halogen reagent or halogen releasing agent can join in each reactor of same tandem reactor.Usually, halogen reagent or halogen releasing agent are offered at least one reactor can make the amount of bromine content in the scope of about 2 weight portions～4.5 weight portion bromines/100 weight portion paraxylene.
According to the method for confession mentioned herein, oxygen source is offered at least one reactor.For example, can an oxygen source be offered each reactor in the tandem reactor.Preferred oxygen source comprises that purity is at least 95% gaseous state O
2Usually, oxygen source is offered at least one reactor with the amount of the scope of about 10～15kg oxygen/ton reactant mixture.
The specific embodiment of this method comprises at least one reactor and adds little a spot of catalyst component that contains zirconium and/or cerium and/or nickel and/or hafnium and/or molybdenum and/or copper and/or zinc.Come into question in the adding effect document below of this metal; For example; At Partenheimer " The effect of zirconium in metal/bromide catalysts during theautoxidation of p-xylene, Part I.Activation and changes inbenzaldehyde intermediate formation, " Journal of Molecular CatalysisA:Chemical; Vol.206:p.105-119, (2003); With Partenheimer " Theeffect of zirconium in metal/bromide catalysts during the autoxidationof p-xylene; Part II.Alternative metals to zirconium and the effect ofzirconium on manganese (IV) dioxide formation and precipitation withpyromellitic acid; " Journal of Molecular Catalysis A:Chemical; Vol.206:p.131-144; (2003), its full content all is incorporated into this, as a reference.Do not hope to receive the restriction of any particular theory, but believe, zirconium and/or cerium are included in the catalyst can be through for the deactivation (deactivation) of Co (III) excitation state provides parallel path, thereby improves reaction rate.
Embodiment
Embodiment is provided below, to further specify various aspects of the present invention.These embodiment are nonrestrictive, should not be understood that to limit any aspect of the present invention.
Embodiment 1
Synthesizing of representational catalyst of the present invention
The following illustrative method provides the exemplary process for preparing catalyst of the present invention.Except method described herein; Those of ordinary skills can use other numerous methods to prepare the intermediate product that is used to make up catalyst of the present invention; Be included in the intermediate product described in the following document, for example, people's such as Kennet J. " Applicable ZeoliteEncapsulation Methods Flexible Ligand Method "; J.Inclus.Phenom., Vol.21:159-184 (1995); Vandermade, people's such as A.W. (J.Chem.Soc.Chem.Commun., Vol.1204 (1983); With people's such as Viswanathan J.EnergyHeat and Mass Transfer, Vol.8:281 (1996).The synthetic of β zeolite can be used several different methods, for example, the xerogel transformation technology, it describes visible, for example the patent (WO2004/050555) of the aeroge method of people's such as P.R.Hari PrasadaRao Chem.Commun.1441 (1996) and modification.
Below the method for embodiment be according to No. the 3308069th, people's such as R.LWadlinger United States Patent (USP), 1967 revise, to be used for synthetic this catalyst.What the multistep preparation was used is through the synthetic β zeolite of hydrothermal synthesis method original position; Flexible ligand exchange method is used for little part is incorporated into zeolite.Step 1 comprises β zeolite synthetic of transformation and in order to remove the calcining of any organic structure directed agents, to make up the catalyst framework.In step 2, zeolite is coated on the (SiO among the embodiment in the host material
2).Step 3 comprises Co (II) and Mn (II) is absorbed on the zeolite of proper sourness.After subsequently and ion-exchange metal, the dry synthetic that supports metal that is obtained.Step 4 comprises the coordination of metal and nitrogen acid and strengthens the state of oxidation of (enhance) metal through adding oxygen, to prepare the metal complex of suitable catalyst component.After this, then carry out the drying of catalyst.
Step 1: β zeolite synthetic
Stir on one side, on one side with 39.3g (0.654mol) SiO
2Silica gel Cab-o-sil M-5 slowly joins in the aqueous solution of tetraethylammonium hydroxide (TEAOH) of 171.3g (0.407mol) 35wt%: obtain white gels.
Stir on one side and hand mix, on one side with 4.89g (5.97 * 10
-2Mol) NaAlO
2Be dissolved in 69.3ml deionization H
2The solution that the back forms among the O joins in the gel: obtain thicker gel.
Behind mix and aging (aging), this gel becomes and has more flowability.
This gel was stirred 2 hours, then it is transferred in the stainless steel autoclave of teflon lined.Autoclave is airtight, and in baking oven, be heated to 150 ℃ still.
After keeping 6 days under 150 ℃ the temperature, autoclave is shifted out from baking oven, and make its cool to room temperature.
The gelatinous precipitate and the supernatant (surnatant solution) of light yellow (white-yellow) are housed in the autoclave.Through centrifugal process sediment is separated with supernatant.Then, use H repeatedly
2O flushing and centrifugalize this sediment, up to the pH of cleaning fluid value less than 9.
The sample of white is following dry 12 hours at 110 ℃ in baking oven; Obtain the 29.150g white fine powder.
The XRD of powder shows that this white powder is the pure β zeolite of highly crystalline.
Carry out sample characterization through SEM, EDX and ICP-OES elementary analysis.
Si/Al＝8.3，Na/Al＝0.22(EDX)。
Si/Al＝8.8，Na/Al＝0.20(ICP-OES)。
The crystal diameter of primary particle is about 20nm～40nm (by drawing in XRD and the SEM data).The diameter of primary particle aggregation is about 200nm～300nm.
Step 2: the β zeolite particles is included in the TUD-1 matrix
This preparation method is people's such as P.Waller Chem.Eur.J., and steps outlined improves one's methods in 2004,10,4970.
The β zeolite (seeing first section) of 16g is suspended in the NH of 6.8g (0.116mol)
4The OH aqueous solution (NH
3ACS reagent, 28wt%～30wt%NH
3The aqueous solution) and 40.65g deionization H
2Among the O, while vigorous stirring: obtain white suspension.
With 30.45g (0.2mol) triethanolamine (98%) and 25.00g deionization H
2O mixes, and then it is joined in the white suspension, simultaneously vigorous stirring.
84.92g (0.4mol) tetraethyl orthosilicate (TEOS, 98%) is dropwise added (10g/min), simultaneously vigorous stirring.Behind the stir about 1 hour, form gel.
The 35wt% aqueous solution of 16.83g (0.04mol) TEAOH is dropwise added, simultaneously vigorous stirring.The gel multiviscosisty can not be rotated (becomeineffective) up to magnetic agitation.
Make the white gels age overnight of thickness.Then, under 99 ℃ temperature in baking oven dry 10 hours.At last, it is transferred in the stainless steel autoclave of teflon lined, autoclave is heated to 170 ℃ still, continue 4 hours.Obtain oldlace (lightbeige) solid.This solid is ground in porcelain mortar, and in stove, calcine:, rise to 600 ℃ from 30 ℃ with 1 ℃/min;
600 ℃, 10 hours;
With 20 ℃/min, reduce to 30 ℃ from 600 ℃;
Obtain the 7.448g white fine powder.
Powder X-ray RD illustrates the existence of the mesoporous property structure of TUD-1, and the main peak of the β zeolite that is included in the TUD-1 matrix is shown simultaneously.
Use N
2The physical absorption mensuration has been confirmed the mesoporous property of sample.Other data (the mesoporous size: about 10nm, S that from these are measured, obtains
BETSurface area: 663 ± 14m
2/ g; External area: 336m
2/ g, total pore size volume: 0.78cm
3/ g, micro pore volume: 0.14m
3/ g) all have good uniformity with data in literature.
Transmission electron microscope (TEM) photo shows that diameter is that the zeolite particles of about 26nm is evenly dispersed in the TUD-l matrix.
Step 3: Co (II) and Mn (II) are absorbed on the acid zeolite
35g β zeolite in the TUD-1 matrix (seeing second section) contains 1.69 * 10
-2The Al of mol.Through stirring, this solid is suspended in 3L deionization H
2Among the O.
With 0.252g Co (CH
3CO
2)
24H
2O (1.01 * 10
-3Mol Co/Al=0.06) is dissolved in 50ml deionization H
2Among the O: stir on one side, should pink solution join in suspension on one side.
Suspension after stirring is heated to 60 ℃ continues 12 hours (in water-bath), at room temperature placed then 4 hours.Pink solid is separated with vacuum filtration process and spent IONS OF H
2O cleans repeatedly.
This pink solid is through the CH of stirring suspension at 325ml
3CO
2Among the H (glacial acetic acid).
Through stirring Mn (CH with 0.414g
3CO
2)
24H
2O (1.69 * 10
-3Mol Mn/Al=0.10) is dissolved in the CH of 325ml
3CO
2Among the H (glacial acetic acid): stir on one side, on one side this solution is joined in the suspension.
Suspension after stirring is heated to 60 ℃, continues 12 hours (in water-bath), at room temperature placed then 4 hours.Separate this solid with vacuum filtration process, and with acetic acid and the deionization H of 700ml
2O is that 1: 1 solution cleans repeatedly.
With the wet powder of this milky (off white) in baking oven, under 120 ℃, dry 2 days: obtain the 34.59g sample.
ICP-OES analyzes:
Co/Al=0.045 (cobalt exchange rate: 74%);
Co weight %:0.111%;
Mn/Al=0.079 (manganese exchange rate: 79%);
Mn weight %:0.184%;
Mn/Co=1.778 (desired value is Mn/Co=2);
Any variation has taken place after analyzing and not being illustrated in Co and Mn exchange in IR.
Step 4: the coordination of the zeolite of metal exchange and nitrogen acid (nitrogen acids)
Contain the β zeolite 0.5g (seeing for the 3rd step) of Co and Mn exchange in the sample that uses, it contains Co+Mn is 2.04 * 10
-4Mol.
With 6.0 * 10
-3The NaOH of mol (0.24g) is dissolved in 4g deionization H
2Among the O.With 5.0 * 10
-3Mol nicotinic acid (0.62g) joins this aqueous solution, and dissolves through stirring.Then, stir on one side, add 4.08 * 10 on one side
-3Mol acetic acid (0.025g) (that is, and as in complex, 2 molar acetates/1 mole metal).Obtain the pH value and approximate 11 colourless transparent solution.
Stir on one side, on one side this aqueous solution is joined in the zeolite sample of 0.5g: light brown suspension obtained.
Add 2.0 * 10
-3The H of mol
2O
2, through with 0.150gH
2O
2The 35wt% aqueous solution and 0.314g deionization H
2O mixes, and obtain 0.060g solution: emit bubble, the brown of suspension becomes darker.
Stir after 1 hour, with 2.5 * 10
-4The NaBr of mol (0.026g) is dissolved in the deionization H of 0.5g in advance
2Among the O, and then stir on one side, on one side it is joined in the suspension.
Stir after 30 minutes, with Buchner funnel suspension is carried out vacuum filtration, using the ethanol of 100ml and acetic acid again is the solution washing of 1: 1 (volume ratio).
With solid residue in baking oven 110 ℃ of following dried overnight: the light grey powder that obtains 0.44g.
Embodiment 2
The illustrative methods of preparation aromatic carboxylic acid
Illustrated in fig. 1 is a preferred embodiment producing terephthalic acid (TPA).
Method of the present invention provides following convenient feature, and to a certain extent, this is to be produced by the low-conversion of paraxylene in the oxidation reactor.
The temperature of reactant mixture raises is enough to dissipation reaction heat, thereby need not cool off oxidation reactor.
The oxygen that is applied to oxidation reactor is dissolved, can not form the vapour phase of segregation.
The water that chemical reaction produces can not form the liquid phase of segregation.
The terephthalic acid (TPA) that chemical reaction produces can not form the solid phase of segregation.
Reactor
The oxidation reaction of paraxylene is carried out in the continuous oxidation reaction device, this reaction is designed to this mode can avoids back-mixing, and wherein, each reactor has all been supplied with an oxygen source.Contain the fluidized-bed reactor of circulation in the catalyst or contain the fixed bed reactors of catalyst stationary arrangement or contain the reactor and the barrier film reactor of cross-current movable bed, can use.Like Fig. 1 illustrated, oxidation reactor can be made up of one or several reaction vessel.
Oxidation reaction
As shown in Figure 1, oxygen source and paraxylene are supplied with oxidation reactor.The terephthalic acid (TPA) that generates in the oxidation reaction (TPA) in whole oxidation reaction process, remains dissolved in the paraxylene.Therefore, oxidation mixtures is the single-phase liquid mixture basically.Operating condition in the oxidation reactor makes can not form second phase, that is, can not be steam, liquid or solid.
Catalyst of the present invention keeps being suspended in the paraxylene with solid form, can add oxidation reactor with the form of slurry, and reactant mixture is stayed in the reactor.Perhaps can arrange, for example fixed bed, radial bed (radial bed), barrier film etc. with various forms.
Reactant mixture is leaving oxidation reactor after reduced pressure by choke valve.
The separation of catalyst of the present invention
When the solid-state catalyst of the present invention that uses in the oxidation reaction was used to slurry or fluidized-bed structure, this catalyst separated emanate before (for example, through hydrocyclone) in product from reactant mixture.After separation, catalyst of the present invention with the anhydrous paraxylene of new (fresh) paraxylene, recovery or in countercurrent washing the combination of above-mentioned two kinds of flows wash.Then, can reclaim as slurry, turn back in the oxidation reactor of continuous oxidation reaction with catalyst of the present invention with paraxylene and a large amount of remaining set compounds that reclaim solvent.
In the specific embodiment of catalyst with the form haptoreaction mixture of fixed bed or fluid bed, catalyst can not leave oxidation reactor.Therefore, there is no need catalyst is separated from reactant mixture.
Reduce pressurization
In the process that reduces pressurization, reactant mixture can come to life, and the result is that the temperature of liquid and vapor capacity all begins to reduce.The boiling the result be, can evaporate from the water in the oxidation reactor, gaseous component and paraxylene, terephthalic acid (TPA) is stayed with solid form.
The removal of reaction impurities
As shown in Figure 1, through distillation or successive flash vaporization, the water that oxidation reaction generates is removed from remaining solvent streams (containing paraxylene, water and residual impurity).In this process, volatile accessory substance also is removed.Nonvolatile product can be used as the washing tributary and removes from the bottom of segregation section (separation stage), so that can individual processing and remove heavy component and prevent it and in reactor, build up.
The crystallization of terephthalic acid (TPA)
After the catalyst separation, cooling does not contain the main flow of catalyst, causes the crystallization of terephthalic acid (TPA).From solvent, reclaim crystal (for example), and handle through countercurrent washing, to be used for follow-up use with new paraxylene through hydrocyclone or filtration.
Be recovered in the oxidation reactor continuously
With " anhydrous " paraxylene, reclaim liquid (for example, from flash distillation or distillation top layer cut decant (or being separated), catalyst detergent etc.) back into the recovery solvent flow of expecting oxidation reactor with several kinds of other paraxylene.Circulating solvent can divide and (for example flows in several flow of liquor; For the terephthalic acid crystals of washing and recycling, the catalyst of recovery etc.), but the most at last these xylenes flows are all collected and are directly supplied with the slurry of the catalyst that oxidation reactor or preparation be used to reclaim.To forming of constituting also join in the regenerant after the merging by catalyst and brominated component.
Claims (18)
1. catalyst component; Said catalyst component based on attached on the carrier or be combined in the zeolite crystallite in the matrix and be combined in the catalytic active component in the said zeolite; The diameter of said crystallite is between 20nm to 300nm, and said catalytic active component has corresponding following chemical formula:
CoMn
2(O) (R-COO)
6L
1 K1L
2 K2, wherein:
R is optional substituted C
1～C
4Alkyl;
L
1Be carboxylic acid or the carboxylate that contains optional substituted nitrogen;
L
2Be selected from by H
2O, comprise optional substituted C
1～C
4The carboxylic acid of alkyl, optional substituted C
5～C
6Cycloalkyl or heterocycle, optional substituted C
5～C
6The group that heteroaryl or aryl constitute; And
k1+k2＝3；
Wherein, the Si/Al atomic ratio of said zeolite is at least 8.
2. catalyst component according to claim 1, wherein, the R of said catalytic active component is-CH
3Or-C
2H
5
3. catalyst component according to claim 1, wherein, the L of said catalytic active component
1Be selected from the group that constitutes by pyridine carboxylic acid, nicotinic acid and isonicotinic acid or their salt, and and L
1Selection independent mutually, L
2Be CH
3COOH or H
2O.
4. catalyst component according to claim 2, wherein, the L of said catalytic active component
1Be selected from the group that constitutes by pyridine carboxylic acid, nicotinic acid and isonicotinic acid or their salt, and and L
1Selection independent mutually, L
2Be CH
3COOH or H
2O.
5. catalyst component; Said catalyst component based on attached on the carrier or be combined in the zeolite crystallite in the matrix and be combined in the catalytic active component in the said zeolite; The diameter of said crystallite is between 20nm to 300nm, and said catalytic active component has corresponding following chemical formula:
CoMn
2(O) (R-COO)
6-k3L
3 K3L
4 K4, wherein:
R is optional substituted C
1～C
4Alkyl;
L
3It is the carboxylate that contains optional substituted nitrogen;
L
4Be selected from by H
2O, contain optional substituted nitrogen carboxylic acid, contain optional substituted C
1～C
4The carboxylic acid of alkyl, optional substituted C
5～C
6Cycloalkyl or heterocycle and optional substituted C
5～C
6The group that heteroaryl or aryl constitute;
K3 is 1,2 or 3;
k3+k4＝3。
6. according to each described catalyst component in the claim 1～5, wherein, said zeolite belongs to MEI or β type, but also contains relevant unordered family composition and based on the microcellular structure of above-mentioned zeolite and its mixture.
7. based on the catalyst of each described catalyst component in the claim 1～5, wherein, zeolite crystallite is embedded in, quilt is implanted or be covered by and contain SiO
2And/or in the mesoporous matrix of carbon.
8. based on the catalyst of the described catalyst component of claim 6, wherein, zeolite crystallite is embedded in, quilt is implanted or be covered by and contain SiO
2And/or in the mesoporous matrix of carbon.
9. a method that is used to prepare aromatic carboxylic acid comprises: in claim 1～6, contact with alkyl aromatic compound with oxygen source in the presence of each described catalyst component or claim 7 or the 8 described catalyst.
10. method according to claim 9, wherein, said method is under the condition that does not have acid flux material, to carry out.
11. method according to claim 9, wherein, said solvent is identical with described alkyl aromatic compound.
12. method according to claim 11, wherein, said solvent is a paraxylene, and said alkyl aromatic compound is a paraxylene.
13. method according to claim 12, wherein, said aromatic carboxylic acid is a terephthalic acid (TPA).
14., further comprise the adding halogen reagent according to each described method in the claim 9～13.
15. method according to claim 14, wherein, said halogen reagent is the agent of alkyl bromo.
16. method according to claim 15, wherein, the agent of said alkyl bromo is 9-bromine anthracene or 9, the 10-dibromoanthracene.
17. one-step method that is used to prepare aromatic carboxylic acid; Comprise: in the presence of according to each described catalyst component or claim 7 in the claim 1～6 or 8 described catalyst, contact with alkyl aromatic compound with oxygen source, said catalyst is embedded in the mesoporous matrix.
18. method for preparing according to each described catalyst component in the claim 1～6; Wherein, Through continuous production catalysis active principle in the passage infall in zeolite; The said catalytic active component of definition in the claim 1～6 is supplied with said zeolite crystallite, and the crystallite size of said zeolite is between 20nm～300nm, and the Si/Al atomic ratio of said zeolite is at least 8.
Applications Claiming Priority (5)
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| US63802104P | 2004-12-20 | 2004-12-20 | |
| US60/638,021 | 2004-12-20 | ||
| US65498605P | 2005-02-22 | 2005-02-22 | |
| US60/654,986 | 2005-02-22 | ||
| PCT/NL2005/000876 WO2006068471A1 (en) | 2004-12-20 | 2005-12-20 | Catalyst and method for preparing aromatic carboxylic acids |
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| CN101115555B true CN101115555B (en) | 2012-01-04 |
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| CN2005800467554A Expired - Fee Related CN101115555B (en) | 2004-12-20 | 2005-12-20 | Catalyst and process for preparing aromatic carboxylic acids |
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| CN101531588B (en) * | 2008-03-13 | 2016-02-24 | 周向进 | The manufacture method of a kind of new pure terephthalic acid |
| CN101575284B (en) * | 2008-05-05 | 2014-11-26 | 周向进 | Novel method for manufacturing PIA |
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| CN1062852C (en) * | 1998-02-16 | 2001-03-07 | 中国石化辽阳石油化纤公司 | Process for recovering cobalt and manganese catalysts from production of terephthalic acid |
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