CN102666482A - Oxidation of hydrocarbons - Google Patents
Oxidation of hydrocarbons Download PDFInfo
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- CN102666482A CN102666482A CN2010800531053A CN201080053105A CN102666482A CN 102666482 A CN102666482 A CN 102666482A CN 2010800531053 A CN2010800531053 A CN 2010800531053A CN 201080053105 A CN201080053105 A CN 201080053105A CN 102666482 A CN102666482 A CN 102666482A
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Abstract
In a process for oxidizing a hydrocarbon, the hydrocarbon is contacted with oxygen in the presence of an N-substituted cyclic imide and under conditions to oxidize the hydrocarbon to produce an oxidized hydrocarbon product and at least one decomposition product of the N-substituted cyclic imide. At least a portion of the at least one decomposition product is contacted with hydroxylamine or a salt thereof under conditions to convert the at least one decomposition product back to said imide.
Description
The cross reference of related application
The sequence number that the application requires on November 25th, 2009 to submit to is 61/264399 U.S. Provisional Application right of priority, and the disclosure of this application is included at this by reference in full.
Technical field
The present invention relates to be used for oxygenated hydrocarbon, alkylaromatic hydrocarbon to be to produce the for example method of phenol and substituted phenol specifically.
Background technology
The oxidation of hydrocarbon is important reaction in industrial organic chemistry.Therefore, for example commercial oxidation production hexalin and the pimelinketone that utilizes hexanaphthene, hexalin and pimelinketone are the important as precursors of producing nylon, utilize the oxidation of alkylaromatic hydrocarbon to produce phenol, phenol is the precursor of producing polycarbonate and epoxy resin.
Can use for example KMnO of known oxygenant
4, CrO
3And HNO
3Carry out the oxidation of hydrocarbon.Yet the shortcoming of these oxygenants is relatively costly, and their use is accompanied by and produces undesired coupling product, and this can bring handling problems.
Therefore, preferably use based on superoxide or N
2The oxygenant of O.Yet the most cheap oxygenant is the molecular oxygen of pure oxygen form or atmosphericoxygen form.But oxygen itself is not suitable for oxygenated hydrocarbon usually, because the O that exists with the favourable triplet state form of energy
2The reactive deficiency of molecule.
Through using the redox metal catalyst, molecular oxygen capable of using comes oxidation of organic compounds, and therefore a large amount of commercial runs is based on the autoxidation of the hydrocarbon of metal catalytic.Therefore, for example, use cobalt salt, carry out hexanaphthene is used O
2Be oxidized to hexalin and/or pimelinketone.These commercial runs are based on free radical chain mechanism, wherein diradical oxygen and hydrocarbon free radical reaction, and form peroxy radical, chainpropagation subsequently through from another hydrocarbon, capturing the H atom.But except metal-salt, organic molecule also can serve as radical initiator.
Yet the shortcoming of these methods is that along with transformation efficiency increases, selectivity greatly descends, so this method must be implemented under very low-level transformation efficiency.Therefore, for example, hexanaphthene carries out under the transformation efficiency of 10-12% to the oxidation of hexalin/pimelinketone; Make that selectivity is 80-85% (" Industrielle Organische Chemie [industrial organic chemistry] 1994; 261, VCH-Verlag, D-69451 Weinheim ").
A kind of the substituting of metal salt catalyst is to use organic mediation agent (mediator), for example N-hydroxyphthalimide (NHPI).Therefore; USP 6852893 and 6720462 discloses at radical initiator and catalyzer and (typically has been N-hydroxyl carbon imide catalyzer; N-hydroxyphthalimide (NHPI) for example) exists down; Through making hydrocarbon substrate and oxygen-containing gas contact the method for oxygenated hydrocarbon substrate, wherein oxygen content is the 5-100% volume.(100-10, pressure 000kPa) carries out this method 0 ℃-500 ℃ temperature with at normal atmosphere-100 crust.The mol ratio of catalyzer and hydrocarbon substrate can be 10
-6Mol%-1mol%, and the mol ratio of radical initiator and catalyzer can be 4: 1 or lower, for example 1: 1-0.5: 1.Can comprise cumene, phenylcyclohexane, cyclo-dodecyl benzene and sec.-butylbenzene through the suitable substrate of this quadrat method oxidation.
USP 7038089 discloses the method that is prepared hydroperoxide by the hydrocarbon that is selected from uncle's hydrocarbon, secondary hydrocarbon and composition thereof; Said method is included in 130-160 ℃ the TR; In the reaction mixture that contains said hydrocarbon and the catalyzer that contains cyclic imide compound and alkali metal cpd, with the said hydrocarbon of oxygen-containing gas oxidation.Suitable hydrocarbon it is said and comprises C
4-C
20Uncle's alkane (for example, Trimethylmethane, iso-pentane, isohexane etc.), has the C of 1-6 aromatic ring
7-C
20(alkyl) aromatic hydrocarbons, or have the C of 1-6 aromatic ring
9-C
20(naphthenic base) aromatic hydrocarbons (for example YLENE, cumene, isopropyltoluene, ethylbenzene, diisopropyl benzene, phenylcyclohexane, naphthane (tetralin), indane etc.) etc.The consumption of employed cyclic imide compound is based on reaction mixture weight; Can be 0.0001-1%, adducts or the salt of preferred 0.0005-0.5%, and the consumption of alkali metal cpd is based on the weight of reaction mixture; Can be 0.000005-0.01%, preferred 0.00001-0.005%.
Yet, further develop although present work continuation demonstration cyclic imide, also shows their application needs in business method as the effectiveness of hydrocarbon oxidation catalyst.Especially, cyclic imide, for example the N-hydroxyphthalimide is expensive and easy hydrolysis under oxidation reaction condition.And, unreacted imide catalyzer and their degradation production (acid and ether) can to downstream reaction for example the division of hydroperoxide bring significant problem.Therefore, cyclic imide successfully is applied in the oxidation of hydrocarbon will require to handle oxidation effluent, to remove unreacted imide and their degradation production and if possible, collect valuable unreacted imide.
International Application No. WO 2009/025939 discloses the method that hydrocarbon is oxidized to corresponding hydroperoxide, alcohol, ketone, carboxylic acid or dicarboxylicacid, wherein makes hydrocarbon and oxygen-containing gas comprise the hydrocarbon product of oxidation and the elute of unreacted imide catalyzer comprising to contact in the presence of the catalyzer of cyclic imide with generation.Subsequently with alkali, particularly alkaline carbonate and/aqueous solution of supercarbonate handles this elute, comprises the water and the organic phase that comprises the hydrocarbon product of oxidation of unreacted imido salt with generation.Subsequently with aqueous phase as acidified to precipitate unreacted imide catalyzer, will collect unreacted imide catalyzer then and it will be recycled to oxidation step.
According to the present invention; Had now found that as catching unreacted imide with alkali and this imide being recycled to the alternative of hydrocarbon oxidation step or except that catching unreacted imide with alkali and this imide being recycled to the hydrocarbon oxidation step, can the imide of being caught being fed to the imide productive rate that the imide ME is also improved this technology thus.
Summary of the invention
On the one hand, the invention reside in the method that is used for oxygenated hydrocarbon, this method comprises:
(a) make hydrocarbon in the presence of the substituted cyclic imide of N-with said hydrocarbon oxidation and produce under the condition of hydrocarbon product and at least a degradation production of the substituted cyclic imide of this N-of oxidation and contact; With
(b) at least a portion that makes this at least a degradation production and first reactant that is selected from oxyamine or its salt transform back under the said imido condition at least a portion that will this at least a degradation production and contact.
In various embodiments, this degradation production is contacted with second reactant that is selected from acid or its acid anhydrides.In one embodiment, this acid or its acid anhydrides are poly carboxylic acid or acid anhydrides.
In one embodiment; This method comprises that further (a) in contact (b) before; With at least a degradation production of the hydrocarbon product of this oxidation of alkaline purification, the substituted cyclic imide of unreacted N-and the substituted cyclic imide of this N-, be converted into adducts or salt with said unreacted imide and said degradation production with at least a portion; (b) at least a portion of this adducts or salt is removed from the hydrocarbon product of oxidation.
In one embodiment, this hydrocarbon comprises the Alkylaromatics of general formula (I):
R wherein
1And R
2Represent hydrogen independently of one another or have the alkyl of 1-4 carbon atom, prerequisite is R
1And R
2Can be connected to form cyclic group with 4-10 carbon atom, and R
3Expression hydrogen, one or more alkyl or cyclohexyl with 1-4 carbon atom.
Advantageously, the Alkylaromatics of said general formula (I) is selected from ethylbenzene, cumene, sec.-butylbenzene, sec.-amyl sec-pentyl secondary amyl benzene, to methyl sec.-butylbenzene, 1,4-phenylbenzene hexanaphthene, Sec-Hexyl benzene and phenylcyclohexane.
In another kind of embodiment, hydrocarbon comprises alkane such as Trimethylmethane, or naphthenic hydrocarbon such as hexanaphthene.
Advantageously, the substituted cyclic imide general molecular formula of said N-(II):
R wherein
4, R
5, R
6And R
7Be selected from alkyl and substituted hydrocarbon radical independently of one another, perhaps be selected from group SO with 1-20 carbon atom
3H, NH
2, OH and NO
2, perhaps be selected from atom H, F, Cl, Br and I; X and Z are selected from C, S, CH independently of one another
2, the element of the 4th family in N, P and the periodictable; Y is O or OH; K is 0,1 or 2; With l be 0,1 or 2.
In one embodiment, the substituted cyclic imide of said N-comprises the N-hydroxyphthalimide.
In one embodiment, said alkali comprises ammonia, and said amide salt precipitates from said elute.
In another kind of embodiment, said alkali comprises the ammonium hydroxide aqueous solution or the oxyamine aqueous solution, and said adducts or salt are dissolved in the said aqueous solution.
In further embodiment, said alkali comprises the aqueous solution of metal carbonate and/or supercarbonate, and said adducts or salt are dissolved in the said aqueous solution.
more further in the embodiment, said alkali comprises pyridine, and said adducts or salt precipitate from said elute.
Description of drawings
Fig. 1 is the schema according to the hydrocarbon oxidation method of one embodiment of this invention.
Specify
The method that hydrocarbon one of is oxidized in corresponding hydroperoxide, alcohol, ketone, carboxylic acid or the dicarboxylicacid has at least been described among this paper.This method comprise make the reaction medium that comprises hydrocarbon and oxygen-containing gas in the presence of the catalyzer that comprises cyclic imide with under the condition of the said hydrocarbon of oxidation, contact.This oxidizing reaction produces the elute of the degradation production of the hydrocarbon product that comprises oxidation and the substituted cyclic imide of this N-.
In various embodiments, degradation production and first reactant that is selected from oxyamine or its salt are transformed back under the said imido condition at least a portion that will this at least a degradation production contact.
In various embodiments; With before first reactant contacts; One or more of use alkaline purification oxygenated hydrocarbon product, the substituted cyclic imide of unreacted N-and the substituted cyclic imide degradation production of N-are so that the unreacted imide of this of at least a portion is converted into adducts or salt with this degradation production.Can this adducts or salt be separated subsequently, and randomly, be fed into and be used for the imido technology of synthesis of cyclic, improve synthesis yield thus.
The hydrocarbon charging
Use method of the present invention, can the multiple replacement of selective oxidation or unsubstituted saturated or undersaturated hydrocarbon, for example alkane, naphthenic hydrocarbon, alkene, cycloolefin and aromatic hydrocarbons.Yet; Especially; This method can be used for the Trimethylmethane selective oxidation is become the tert-butyl hydroperoxide and the trimethyl carbinol, and the hexanaphthene selective oxidation is become cyclohexyl hydroperoxide, hexalin and pimelinketone, becomes corresponding hydroperoxide with Alkylaromatics selective oxidation with general formula (I):
R wherein
1And R
2Represent hydrogen independently of one another or have the alkyl of 1-4 carbon atom, prerequisite is R
1And R
2Can be connected to form cyclic group with 4-10 carbon atom, and R
3Expression hydrogen, one or more alkyl or cyclohexyl with 1-4 carbon atom.The instance of suitable Alkylaromatics is ethylbenzene, cumene, sec.-butylbenzene, sec.-amyl sec-pentyl secondary amyl benzene, to methyl sec.-butylbenzene, 1,4-phenylbenzene hexanaphthene, Sec-Hexyl benzene and phenylcyclohexane, wherein preferred sec.-butylbenzene and phenylcyclohexane.It is also understood that, therein R
1And R
2Be connected to form under the situation of cyclic group, the carbon number that forms cyclic rings is 4-10.Yet itself can be with one or more substituting group this ring, and for example one or more alkyl with 1-4 carbon atom, or one or more phenyl are as 1, in the situation of 4-phenylbenzene hexanaphthene.
In the embodiment of a reality; The Alkylaromatics of general formula (I) is a sec.-butylbenzene; And, use at least a C through under alkylation conditions and in heterogeneous catalyst zeolite beta or more preferably in the presence of at least a molecular sieve (as giving a definition) of MCM-22 family for example
4Alkylating agent makes benzene alkylation and produces.Alkylation conditions comprises about 60 ℃-Yue 260 ℃ easily, for example about 100 ℃-Yue 200 ℃ temperature.Alkylation pressures is below the 7000kPa easily, the about 3500kPa of for example about 1000-.Alkylation is easily based on C
4The about 50h of about 0.1-of alkylating agent
-1, the about 10h of for example about 1-
-1Weight hourly space velocity degree (WHSV) under carry out.
C
4Alkylating agent comprises at least a linear butenes easily, that is butene-1, butene-2 or their mixture.Alkylating agent also can be the olefinic C that contains the linear butenes class
4Hydrocarbon mixture for example can be through steam cracking ethane, propane, butane, LPG and light naphtha, catalytic cracking petroleum naphtha and other refinery feedstock and through with oxygenate, and for example methanol conversion becomes light alkene to obtain.For example, following C
4Hydrocarbon mixture all can obtain in any refining of adopting steam cracking with generation alkene usually, and is suitable for as C
4Alkylating agent: the cymogene alkene logistics of steam cracking, raffinate-1 (in solvent extraction or hydrogenation with residual product after from the cymogene alkene logistics of steam cracking, removing divinyl) and raffinate-2 (from the cymogene alkene logistics of steam cracking, removing divinyl and iso-butylene residual product afterwards).
In further actual embodiment; The Alkylaromatics of general formula (I) is a phenylcyclohexane, and through benzene takes place to react as follows to make to make phenylcyclohexane (CHB) in the presence of the hydroalkylation catalyzer, making benzene contact thus with hydrogen under the hydroalkylation condition:
The catalyzer that uses in this hydroalkylation reaction is a dual functional catalyst, and it comprises molecular sieve and the metal hydride with acid function.Suitable molecular sieve comprises zeolite beta, X zeolite, zeolite Y and MCM-22 family molecular sieves (as giving a definition).The metal hydride of any known can be used for this hydroalkylation catalyzer, but suitable metal comprises palladium, ruthenium, nickel, zinc, tin and cobalt, and particularly advantageous is palladium.Usually, the amount of the metal hydride that exists in this catalyzer is the about 10wt% of about 0.05-of this catalyzer, the about 5wt% of 0.1-according to appointment.In one embodiment, when molecular sieve was aluminosilicate, the amount of the metal hydride of existence made that the mol ratio of aluminium and metal hydride in the molecular sieve is about 1500 for about 1.5-, and for example about 75-is about 750, and 100-about 300 according to appointment.
This metal hydride can for example directly load on the molecular sieve through dipping or IX.But, in a more preferred embodiment, will be at least 50wt%, for example at least 75wt% and usually basically all metal hydride load on separate with molecular sieve but with its compound inorganic oxide on.Especially, find to compare with the catalyzer of equal value that metal hydride loads on the molecular sieve, improved activity of such catalysts and the selectivity of phenylcyclohexane and dicyclohexyl benzene through metal hydride is loaded on the inorganic oxide.
The inorganic oxide that in this compound hydroalkylation catalyzer, uses does not have narrow limits, as long as it is stable and inert under the hydroalkylation reaction conditions.Suitable inorganic oxide comprises the oxide compound of the periodic table of elements the 2nd, 4,13 and 14 families, like aluminum oxide, titanium oxide and/or zirconium white.The numbering of the periodictable family that uses among this paper is disclosed in Chemical and Engineering News, 63 (5), 27 (1985).
Advantageously, metal hydride is passed through immersion deposition on inorganic oxide in that metallic inorganic oxide and said molecular sieve is compound with before making catalyst composite.Typically, catalyst composite makes through granulation altogether, and wherein (about usually 350-is about 350, is pellet with the mixture forming of molecular sieve and metallic inorganic oxide under 000kPa) at high pressure; Perhaps make, wherein the slurry of molecular sieve and metallic inorganic oxide is randomly extruded through die head with independent tackiness agent through coextrusion.If necessary, can extra metal hydride be deposited on the catalyst composite of gained subsequently.
Suitable adhesive material comprises synthetic or naturally occurring material, and inorganic materials such as clay, silica and/or MOX.The latter can be naturally occurring, or comprises the gelatinous precipitate or the gel form of silica and MOX.Can comprise those that polynite and kaolin are serial as the naturally occurring clay of tackiness agent; Said series comprises sub-bentonite (subbentonite) and kaolin; Usually be known as Dixie, McNamee, Georgia and Florida clay, perhaps wherein the essential mineral composition is other series of halloysite, kaolinite, dickite, nakrite or anauxite.These clays can perhaps carry out calcining, s.t. or chemical modification at first with the virgin state of original exploitation to be used.Suitable metal oxide binder comprises silica, aluminum oxide, zirconium white, titanium oxide, silica-alumina, silica-Natural manganese dioxide, silica-zirconium white, silica-Thorotrast, silica-beryllium oxide, silica-titanium oxide, and ternary composition such as silica-alumina-Thorotrast, silica-alumina-zirconium white, silica-alumina-Natural manganese dioxide and silica-Natural manganese dioxide-zirconium white.
The hydroalkylation reaction can be carried out in the reactor configurations of wide region, comprises fixed bed, slurry-phase reactor and/or catalytic distillation tower.In addition, the reaction of this hydroalkylation can be carried out in single reaction zone or in a plurality of reaction zone, wherein introduces reaction by stages to major general's hydrogen.Suitable temperature of reaction is about 50 ℃-Yue 400 ℃, 100 ℃ according to appointment-Yue 250 ℃, and suitable reaction pressure is the about 7000kPa of about 100-, and the about 5000kPa of 500-according to appointment.The suitable value of the mol ratio of hydrogen and benzene is about 100 for about 0.01-, more particularly is the about 15:1 of about 0.15:1-, the about 4:1 of 0.4:1-according to appointment, the about 0.9:1 of for example about 0.4-.The weight hourly space velocity of benzene is generally the about 100hr of about 0.01-
-1This hydroalkylation reaction is heat release, and this reaction system must be considered heat control thus.Preferred method be with from the part of the elute of hydroalkylation reactor drum via cooling heat exchanger recycling, and the refrigerative recycle stream mixed with charging.Can also advantageously adopt more than one hydroalkylation bed or reactor drum, and add hydrogen by stages.
Term as used herein " MCM-22 family material " (or " material of MCM-22 family " or " MCM-22 family molecular sieves " or " MCM-22 family zeolite ") comprises one or more in following:
By the molecular sieve that common one-level crystal structure unit structure cell is processed, said structure cell has the MWW framework morphology.(structure cell is that atoms in space is arranged, and it has described the crystalline structure during laying in three-dimensional space.At " Atlas of Zeolite Framework Types ", the 5th edition, this crystalline structure has been discussed in 2001, its full content is included in as a reference at this);
By the molecular sieve that common secondary crystallization tectonic element is processed, it is the two-dimentional laying of the structure cell of this MWW framework morphology, forms a structure cell thickness, the individual layer of a preferred c-structure cell thickness;
The molecular sieve of processing by common secondary crystallization tectonic element; It is one or greater than the layer of a structure cell thickness, is wherein processed by the individual layer that piles up (stacking), fills (packing) or at least two structure cell thickness of bonding greater than the layer of a structure cell thickness.Piling up of this secondary building unit can be regular fashion, irregular mode, random placement, or their any combination; With
The molecular sieve that any rule of the structure cell through having the MWW framework morphology or random two dimension or three-dimensional array are processed.
The MCM-22 family molecular sieves comprises those molecular sieves with X-ray diffraction pattern, and said X-ray diffraction pattern is included in the maximum d-spacing at 12.4 ± 0.25,6.9 ± 0.15,3.57 ± 0.07 and 3.42 ± 0.07 dust places.The employed X-ray diffraction data of exosyndrome material are for example used copper through standard technique K-α doublet is as the incident radiation and be furnished with scintillometer and associated computer obtains as the diffractometer of gathering system.
MCM-22 family material comprises MCM-22 (described in the USP 4954325); PSH-3 (described in the USP 4439409); SSZ-25 (described in the USP 4826667); ERB-1 (described in the European patent 0293032); ITQ-1 (described in the USP 6077498); ITQ-2 (described in the international patent publications WO97/17290); MCM-36 (described in the USP 5250277); MCM-49 (described in the USP 5236575); MCM-56 (described in the USP 5362697); UZM-8 (described in the USP 6756030) and their mixture.The MCM-22 family molecular sieves is preferably as alkylation catalyst, because find to compare with other butylbenzene-isomer, they have high selectivity to producing sec.-butylbenzene.Preferably, molecular screening is from (a) MCM-49, (b) MCM-56 and (c) phenogen (isotype) of MCM-49 and MCM-56, for example ITQ-2.
The hydrocarbon oxidation
Through in the presence of the catalyzer of the cyclic imide that comprises general formula (II), the hydrocarbon substrate is contacted with oxygen-containing gas, realize the oxidation step in the inventive method:
R wherein
4, R
5, R
6And R
7Be selected from alkyl and substituted hydrocarbon radical independently of one another, perhaps be selected from group SO with 1-20 carbon atom
3H, NH
2, OH and NO
2, perhaps be selected from atom H, F, Cl, Br and I; X and Z are selected from C, S, CH independently of one another
2, the element of the 4th family in N, P and the periodictable; Y is O or OH; K is 0,1 or 2; With l be 0,1 or 2.
In the embodiment of a reality, the cyclic imide catalyzer comprises the N-hydroxyphthalimide.
Carrying out the employed condition of oxidation step changes with the type of the hydrocarbon substrate of wanting oxidation significantly; But normally suitable condition comprises about 20 ℃-Yue 150 ℃; For example about 70 ℃-Yue 130 ℃ temperature and the about 500kPa of about 15kPa-, for example pressure of the about 150kPa of 15kPa-.
The character that depends on the hydrocarbon substrate, the product of oxidation step can comprise one or more in hydroperoxide, alcohol, ketone, carboxylic acid or the dicarboxylicacid of corresponding hydrocarbon.Yet, except containing required hydrocarbon oxidation products, also contain the degradation production of unreacted cyclic imide catalyzer and cyclic imide from the elute of oxidation step.If catalyzer is the N-hydroxyphthalimide, these degradation productions comprise 2-(hydroxyl amino formyl radical) phenylformic acid, phthalic acid and the alkoxyl group-phthalic imidine that produces according to following reaction:
Unreacted imide catalyzer and degradation production thereof are not merely downstream reaction, particularly step toward division and bring significant problem, and they make and have lost valuable catalyzer.The inventive method catches and removes these materials from this oxidation effluent thus, and with this material feeding in the imide synthesis step, in synthesis step, produce improved imide yield thus.Can reuse subsequently and reclaim thus and regenerated imide catalyzer.
Catching unreacted imide catalyzer and degradation production thereof can comprise at first and be converted into adducts or salt with the alkaline purification elute with unreacted imide and degradation production thereof with at least a portion.This alkali can be the aqueous solution of metal carbonate and/or supercarbonate, and it will be caught as the unreacted imide and the degradation production thereof that dissolve in the salt of this alkali aqueous solution.But such alkali will not react with the ether degradation production.Preferred thus alkali is nitrogenous alkali, because it will not only produce adducts with unreacted imide and sour degradation production thereof, but also produces adducts with the ether degradation production.Suitable nitrogenous alkali comprises (i) ammonia, and this moment, adducts precipitated from oxidation effluent; The (ii) ammonium hydroxide aqueous solution or the oxyamine aqueous solution, this moment, adducts was dissolved in this aqueous solution; (iii) pyridine, this moment, adducts precipitated from oxidation effluent.
After unreacted imide catalyzer and degradation production thereof are caught as adducts and/or salt, this adducts and/or salt are removed from oxidation effluent, typically through filtering or be separated, and be fed in the imide building-up reactions.In the imide building-up reactions, make this adducts and/or salt and be selected from oxyamine or its salt and contact with the acid or at least a reactant of its acid anhydrides.Thus, when imide is the N-hydroxyphthalimide, usually adducts and/or salt are contacted with at least a reactant that is selected from oxyamine or its salt and phthalic acid or Tetra hydro Phthalic anhydride.For example, when degradation production is phthalic acid, can oxyamine be added in the degradation production phthalic acid is transformed back the N-hydroxyphthalimide.In one embodiment, phthalic acid and oxyamine are all added,, also produce extra N-hydroxyphthalimide with except N-hydroxyphthalimide that degradation production is regenerated back.
Typically, the imide building-up reactions less than 7 pH, preferably the pH at about 2-about 6 carries out, at least a degradation production is transformed back the substituted cyclic imide of N-.In one embodiment, make said poly carboxylic acid or acid anhydrides and said oxyamine or its reactant salt transform back said imide under with the condition that produces the extra substituted cyclic imide of N-degradation production, adducts or salt.Suitable condition comprises that the poly carboxylic acid that is added in the building-up reactions or the mol ratio of its acid anhydrides and oxyamine or its salt are about 0.5-about 10.0; For example about 0.8-about 2.0; According to appointment 1.0-about 1.8 and temperature be about 0 ℃-Yue 100 ℃ and reaction times is about 24 hours of about 0.5-.
Oxidation products
The product of method for oxidation of the present invention depends on the character of oxidized hydrocarbon substrate, but is typically hydroperoxide, alcohol, ketone, carboxylic acid or dicarboxylicacid, particularly hydroperoxide.
For example, when the hydrocarbon substrate was Trimethylmethane, oxidation products comprised the tert-butyl hydroperoxide (it can be used as oxidising agent and is used to produce propylene oxide) and the trimethyl carbinol (it can be used as gasoline dope).
When the hydrocarbon substrate was hexanaphthene, oxidation products comprised cyclohexyl hydroperoxide, hexalin and pimelinketone.The easy thermolysis of cyclohexyl hydroperoxide or at auxiliary extra hexalin and the pimelinketone of resolving into down of catalyzer.Can adopt aqueous nitric acid oxidation hexalin to produce hexanodioic acid, hexanodioic acid is the precursor in the synthetic nylon 6,6, and pimelinketone can change into the hexamethylene oxime, and pimelinketone carries out acid catalyzed rearrangement to produce hexanolactam, and it is the precursor in the synthetic nylon 6.
Be that the product of oxidizing reaction comprises the hydroperoxide of general formula (III) under the situation of Alkylaromatics of general formula (I) at the hydrocarbon substrate:
R wherein
1, R
2And R
3Have with formula (I) in identical implication.Preferably, hydroperoxide are sec-butylbenzene hydroperoxide, phenylcyclohexane hydroperoxide or cumene hydroperoxide.Can such hydroperoxide be changed into phenol or substituted phenol and general formula R through the acid division then
1COCH
2R
2(IV) aldehydes or ketones, wherein R
1And R
2Have with formula (I) in identical implication.Phenol certainly reacts to produce dihydroxyphenyl propane with acetone, and it is the precursor in producing polycarbonate and epoxy resin.
Through about 20 ℃-Yue 150 ℃ temperature, for example about 40 ℃-Yue 120 ℃, and/or the pressure of the about 2500kPa of about 50-, the about 1000kPa of for example about 100-, and/or based on the about 100h of about 0.1-of hydroperoxide
-1, the about 50h of preferably about 1-
-1Liquid hourly space velocity degree (LHSV) under, hydroperoxide are contacted with catalyzer, carry out the dissociative reaction of hydroperoxide easily.Preferably hydroperoxide are for example being diluted in methylethylketone, phenol or the sec.-butylbenzene the dissociative reaction organic solvent inert, with the auxiliary heat of removing.In the catalytic distillation unit, carry out dissociative reaction easily.
Employed catalyzer can be homogeneous catalyst or heterogeneous catalyst in step toward division.In a kind of embodiment of reality, can the homogeneous phase cyclic imide be converted into heterogeneous catalyst through cyclic imide being fixed or loaded on the solid material.As an example, can through various functional groups such as imide-, carboxamido-group-or sulfoamido-, cyclic imide is fixed on the fluoropolymer resin.As another example, can cyclic imide be fixed on solid carrier such as the silica gel through chemical bond via aminoalkyl group.The advantage of heterogeneous cyclic imide is that it is compared with the homogeneous phase cyclic imide and can more easily separate and recycling.In addition, heterogeneous cyclic imide may reside in the fixed bed, wherein needn't separate substituted cyclic imide of N-and degradation production.Oxidation reactor can move parallelly connectedly, makes fixed bed catalyst when off-line, to regenerate.
Suitable homogeneous phase cleavage catalysts comprises sulfuric acid, perchloric acid, phosphoric acid, hydrochloric acid and tosic acid.Iron(ic)chloride, boron trifluoride, sulfurous gas and sulphur trioxide also are effective homogeneous phase cleavage catalysts.Preferred homogeneous phase cleavage catalysts is a sulfuric acid.
The suitable heterogeneous catalyst that in the division sec-butylbenzene hydroperoxide, uses comprises montmorillonitic clay; For example acid polynite silica-alumina clay; Described in USP 4870217 (Texaco), its whole disclosures are included at this by reference.
With reference to accompanying drawing, Fig. 1 is oxidation step and the schema of oxidation effluent treatment step of a kind of embodiment of the inventive method.In this embodiment, hydrocarbon stream 7, oxygen logistics 8 and optional additional imide logistics 9 are fed in the oxidation reactor 10 to produce oxidation effluent.Oxidation effluent 11 and gas phase or liquid phase alkali logistics 12 are led to processing and segregation section 13.In processing and segregation section 13, alkali logistics 12 and oxidation effluent are merged so that react to form adducts or salt with unreacted imide of at least a portion and degradation production thereof.Subsequently with this adducts or salt separates from oxidation effluent and be fed to imide synthesis reactor 15 to produce the regenerated imide as logistics 14.Typically this regenerated imide is circulated back to oxidation reactor via recirculation stream 18.Remaining oxidation effluent is led to downstream reactor 17 as logistics 16, typically this elute is converted into the product of expectation through oxidation or division at this.
Through with reference to following indefiniteness embodiment, the present invention is described more specifically.
Embodiment 1: use N-hydroxyphthalimide (NHPI) to come oxidation phenylcyclohexane (CHB) as catalyzer
Weigh 150g from the phenylcyclohexane of TCI America and 0.16g from the NHPI of TCI be added to be furnished with whisking appliance, thermopair, gas inlet, sampling port and contain the Parr reactor drum of the condensing surface of the Dean Rodney Stark water trap that is used to dewater.Under atmospheric pressure with the 1000rpm reactor contents, and with the flow velocity of 250cc/min with nitrogen purging 5 minutes.Reactor drum is heated to 110 ℃ remaining under the nitrogen purging subsequently.When reaching temperature of reaction, convert gas into air from nitrogen, and with 250cc/min with air purge reactor drum 4 hours.Per hour take a sample, and analyze through gc.After 4 hours, gas is changed back nitrogen and stopped heating.HPLC analyzes and shows that NHPI concentration was 926ppm when oxidizing reaction finished.
Embodiment 2: use solution of ammonium hydroxide to remove NHPI
With 0.1069 gram NH
4The OH aqueous solution (28-32wt%) is added in the oxidation effluent of 30 gram embodiment 1.Stirred the mixture 15 minutes and from organic phase, took a sample subsequently and be used for the NHPI analysis.HPLC analyzes and is presented at NH
4NHPI concentration was 38.5ppm when the OH processing finished, and except the NHPI level reduces, and this oxidation effluent was formed before handling and kept identical afterwards.
Embodiment 3: use ammonia to remove NHPI
Nitrogen gas stream is restrained NH via 30
4The OH aqueous solution (28-32wt%) passes through, and with the oxidation effluent 30 minute of gained gas bubbling through 30 gram embodiment 1.Sampling is used for analyzing from the organic phase of this elute.NHPI concentration was 16.5ppm when HPLC analyzed and to be presented at ammonia treatment and to finish, and except the NHPI level reduces, and this oxidation effluent was formed before handling and kept identical afterwards.
Above-mentioned data clearly illustrate, through NH
4OH and ammonia treatment have reduced the NHPI level in the oxidation effluent, and hydroperoxide product is decomposed.
In various embodiments, this method relates to:
1, (a) contacting hydrocarbon and oxygen in the presence of the substituted cyclic imide of N-with under with the condition of said hydrocarbon oxidation with the hydrocarbon product that produces oxidation and at least a degradation production of the substituted cyclic imide of N-; With
(b) at least a portion that makes this at least a degradation production and first reactant that is selected from oxyamine or its salt transform back under the said imido condition at least a portion that will this at least a degradation production and contact.
2, the method for embodiment 1, it further comprises makes this at least a degradation production of at least a portion contact with second reactant that is selected from acid or its acid anhydrides.
3, the method for embodiment 1 further comprises:
(a) before in contact (b); With at least a degradation production of the hydrocarbon product of alkaline purification oxidation, the substituted cyclic imide of unreacted N-and the substituted cyclic imide of N-, be converted into adducts or salt with said unreacted imide and said degradation production with at least a portion; With
(b) at least a portion of this adducts or salt is removed from the hydrocarbon product of oxidation.
4, the method for embodiment 1, wherein should acid or its acid anhydrides be poly carboxylic acid or its acid anhydrides, and wherein this poly carboxylic acid or its acid anhydrides and said oxyamine or its reactant salt to produce the substituted cyclic imide of extra N-.
5, the method for embodiment 1, wherein said hydrocarbon comprises the Alkylaromatics of general formula (I):
R wherein
1And R
2Represent hydrogen independently of one another or have the alkyl of 1-4 carbon atom, prerequisite is R
1And R
2Can be connected to form cyclic group with 4-10 carbon atom, and R
3Expression hydrogen, have one or more alkyl or the cyclohexyl of 1-4 carbon atom.
6, the method for embodiment 1, the Alkylaromatics of wherein said general formula (I) be selected from ethylbenzene, cumene, sec.-butylbenzene, sec.-amyl sec-pentyl secondary amyl benzene, to methyl sec.-butylbenzene, 1,4-phenylbenzene hexanaphthene, Sec-Hexyl benzene and phenylcyclohexane.
7, the method for embodiment 1, the hydrocarbon product of wherein said oxidation comprises the hydroperoxide of general formula (III):
R wherein
1, R
2And R
3Have with formula (I) in identical implication, and this method further comprises said hydroperoxide is transformed into phenol or substituted phenol and general formula R
1COCH
2R
2(IV) aldehydes or ketones, wherein R
1And R
2Have with formula (I) in identical implication.
8, the method for embodiment 1, wherein said degradation production comprises phthalic acid.
9, the method for embodiment 1, wherein said degradation production comprises the alkoxyl group phthalic imidine.
10, the method for embodiment 1, wherein said hydrocarbon comprises hexanaphthene, the hydrocarbon product of said oxidation comprises hexalin, and this method further comprises hexalin is converted into hexanodioic acid.
11, the method for embodiment 1, wherein said hydrocarbon comprises hexanaphthene, the hydrocarbon product of said oxidation comprises pimelinketone, and this method further comprises pimelinketone is converted into hexanolactam.
12, the method for embodiment 1, wherein said hydrocarbon comprises Trimethylmethane, the hydrocarbon product of said oxidation comprises tert-butyl hydroperoxide, and this method comprises that further this tert-butyl hydroperoxide of use is as oxide catalyst.
13, the method for embodiment 1, the substituted cyclic imide general molecular formula of wherein said N-(II):
R wherein
4, R
5, R
6And R
7Be selected from alkyl and substituted hydrocarbon radical independently of one another, perhaps be selected from group SO with 1-20 carbon atom
3H, NH
2, OH and NO
2, perhaps be selected from atom H, F, Cl, Br and I; X and Z are selected from C, S, CH independently of one another
2, the element of the 4th family in N, P and the periodictable; Y is O or OH; K is 0,1 or 2; With l be 0,1 or 2.
14, the method for embodiment 1, the substituted cyclic imide of wherein said N-comprises the N-hydroxyphthalimide.
15, the method for embodiment 1, wherein said contact (a) is carried out at the pressure of about 150 ℃ temperature of about 20-and the about 500kPa of about 15kPa-.
16, the method for embodiment 1, wherein said contact (a) is carried out at the pressure of about 130 ℃ temperature of about 70-and the about 150kPa of about 15kPa-.
17, the method for embodiment 1, wherein said alkali comprises inorganic nitrogen compound.
18, the method for embodiment 1, wherein said alkali comprises ammonia, and said adducts precipitates from said response composite.
19, the method for embodiment 1, wherein said alkali comprises ammonium hydroxide aqueous solution, and said adducts is dissolved in the said aqueous solution.
20, the method for embodiment 1, wherein said alkali comprises the aqueous solution of metal carbonate and/or supercarbonate, and said adducts or salt are dissolved in the said aqueous solution.
21, the method for embodiment 1, wherein said alkali comprises pyridine.
22, the method for embodiment 1, the mol ratio that wherein is added to said poly carboxylic acid or its acid anhydrides and said oxyamine or its salt in the said contacting step (d) is about 0.5-about 10.0.
23, the method for embodiment 1, the mol ratio that wherein is added to said poly carboxylic acid or its acid anhydrides and said oxyamine or its salt in the said contacting step (d) is about 1.0-about 1.8.
24, the method for embodiment 1, wherein said contact (b) is carried out in the about 100 ℃ temperature of about 0-.
In various embodiments, this method relates to:
(a) make said sec.-butylbenzene and oxygen-containing gas in the presence of the substituted cyclic imide of N-with said hydrocarbon oxidation and produce under the condition that comprises sec-butylbenzene hydroperoxide, the substituted cyclic imide of unreacted N-and the elute of the degradation production of the substituted cyclic imide of N-and contact; With
(b) this elute is handled with alkali, be converted into adducts or salt with said unreacted imide and said degradation production with at least a portion;
(c) at least a portion of said adducts or salt is separated from said elute; With
(d) contact with at least a portion of isolating adducts or salt and poly carboxylic acid or its acid anhydrides and with oxyamine or its salt.
In various embodiments, contact (d) is less than 7 pH, said adducts or salt transformed back said imide and making said poly carboxylic acid or its acid anhydrides and said oxyamine or its reactant salt carry out under with the condition that produces the extra substituted cyclic imide of N-.
In various embodiments, this method relates to:
(a) said phenylcyclohexane is being contacted in the presence of the substituted cyclic imide of N-with also producing under the condition that comprises phenylcyclohexane hydroperoxide, the substituted cyclic imide of unreacted N-and the elute of the degradation production of the substituted cyclic imide of N-at the said hydrocarbon of oxidation with oxygen-containing gas;
(b) this elute is handled with alkali, be converted into adducts or salt with said unreacted imide and said degradation production with at least a portion;
(c) at least a portion of said adducts or salt is separated from said elute; With
(d) contact with at least a portion of isolating adducts or salt and poly carboxylic acid or its acid anhydrides and with oxyamine or its salt.
In various embodiments, contact (d) is less than 7 pH, said adducts or salt transformed back said imide and making said poly carboxylic acid or its acid anhydrides and said oxyamine or its reactant salt carry out under with the condition that produces the extra substituted cyclic imide of N-.
In various embodiments, this method relates to:
(a) make said hydrocarbon charging and oxygen in the presence of the substituted cyclic imide of N-, contact under with the condition that produces the charging comprise oxidation at least and the elute of at least a degradation production of the substituted cyclic imide of N-being enough to the said hydrocarbon charging of oxidation at least a portion;
(b) from this elute, remove at least a portion of the degradation production of the substituted cyclic imide of N-;
(c) part of removing of the degradation production of the substituted cyclic imide of N-is contacted with at least a reactant that is selected from acid or its acid anhydrides and oxyamine or its salt, transform back said imide with at least a portion with degradation production; With
(d) imide that step (c) is obtained is recycled to step (a).
Although describe and explained the present invention, those skilled in the art will appreciate that the present invention is embodied in the modification that may not explain in this article with reference to particular.Thereby, for this reason, only should confirm true scope of the present invention with reference to the appended claims book.
Claims (25)
1. the method for an oxygenated hydrocarbon, this method comprises:
(a) hydrocarbon and oxygen are being contacted in the presence of the substituted cyclic imide of N-with under with the condition of said hydrocarbon oxidation with the hydrocarbon product that produces oxidation and at least a degradation production of the substituted cyclic imide of this N-; With
(b) at least a portion that makes this at least a degradation production and first reactant that is selected from oxyamine or its salt transform back under the said imido condition at least a portion that will this at least a degradation production and contact.
2. the method for claim 1 comprises that further at least a portion that makes this at least a degradation production contacts with second reactant that is selected from acid or its acid anhydrides.
3. the process of claim 1 wherein that contact (a) further forms the substituted cyclic imide of unreacted N-, and this method comprises further:
(i) before in contact (b); With at least a degradation production of the hydrocarbon product of this oxidation of alkaline purification, the substituted cyclic imide of unreacted N-and the substituted cyclic imide of this N-, be converted into adducts or salt with said unreacted imide and said degradation production with at least a portion; With
(ii) at least a portion of this adducts or salt is removed from the hydrocarbon product of this oxidation.
4. the method for claim 2, wherein should acid or its acid anhydrides be poly carboxylic acid or its acid anhydrides, and wherein this poly carboxylic acid or its acid anhydrides and said oxyamine or its reactant salt to produce the substituted cyclic imide of extra N-.
5. each method in the aforementioned claim, wherein said hydrocarbon comprises the Alkylaromatics of general formula (I):
R wherein
1And R
2Represent hydrogen independently of one another or have the alkyl of 1-4 carbon atom, prerequisite is R
1And R
2Can be connected to form cyclic group with 4-10 carbon atom, and R
3Expression hydrogen, one or more alkyl or cyclohexyl with 1-4 carbon atom.
6. each method in the aforementioned claim, the Alkylaromatics of wherein said general formula (I) be selected from ethylbenzene, cumene, sec.-butylbenzene, sec.-amyl sec-pentyl secondary amyl benzene, to methyl sec.-butylbenzene, 1,4-phenylbenzene hexanaphthene, Sec-Hexyl benzene and phenylcyclohexane.
7. each method in the aforementioned claim, the hydrocarbon product of wherein said oxidation comprises the hydroperoxide of general formula (III):
R wherein
1, R
2And R
3Have with formula (I) in identical implication, and this method further comprises said hydroperoxide is split into phenol or substituted phenol and general formula R
1COCH
2R
2(IV) aldehydes or ketones, wherein R
1And R
2Have with formula (I) in identical implication.
8. the process of claim 1 wherein that said degradation production comprises phthalic acid.
9. the process of claim 1 wherein that said degradation production comprises the alkoxyl group phthalic imidine.
10. the process of claim 1 wherein that said hydrocarbon comprises alkane such as Trimethylmethane, perhaps naphthenic hydrocarbon such as hexanaphthene.
11. each method in the aforementioned claim, the substituted cyclic imide general molecular formula of wherein said N-(II):
R wherein
4, R
5, R
6And R
7Be selected from alkyl and substituted hydrocarbon radical independently of one another, perhaps be selected from group SO with 1-20 carbon atom
3H, NH
2, OH and NO
2, perhaps be selected from atom H, F, Cl, Br and I; X and Z are selected from C, S, CH independently of one another
2, the element of the 4th family in N, P and the periodictable; Y is O or OH; K is 0,1 or 2; With l be 0,1 or 2.
12. each method in the aforementioned claim, the substituted cyclic imide of wherein said N-comprises the N-hydroxyphthalimide.
13. each method in the aforementioned claim, wherein said contact (a) is carried out at the pressure of 20-150 ℃, preferred 70-130 ℃ temperature and 15kPa-500kPa, preferred 15kPa-150kPa.
14. each method among the claim 3-13, wherein said alkali comprises inorganic nitrogen compound.
15. each method among the claim 3-13, wherein said alkali comprises ammonia, and said adducts precipitates from said response composite.
16. each method among the claim 3-13, wherein said alkali comprises ammonium hydroxide aqueous solution, and said adducts is dissolved in the said aqueous solution.
17. each method among the claim 3-13, wherein said alkali comprises the aqueous solution of metal carbonate and/or supercarbonate, and said adducts or salt are dissolved in the said aqueous solution.
18. each method among the claim 3-13, wherein said alkali comprises pyridine.
19. each method among the claim 4-18, the said poly carboxylic acid or the mol ratio of its acid anhydrides and said oxyamine or its salt that wherein are added in the said contacting step (d) are 0.5-10.0, are preferably 0.8-2.0, more preferably 1.0-1.8.
20. each method in the aforementioned claim, wherein said contact (b) is carried out 0-100 ℃ temperature.
21. one kind is used for sec-butylbenzene oxidation is the method for sec-butylbenzene hydroperoxide, this method comprises:
(a) make said sec.-butylbenzene and oxygen-containing gas in the presence of the substituted cyclic imide of N-with said hydrocarbon oxidation and produce under the condition that comprises sec-butylbenzene hydroperoxide, the substituted cyclic imide of unreacted N-and the elute of the degradation production of the substituted cyclic imide of this N-and contact; With
(b), be converted into adducts or salt with said unreacted imide and said degradation production with at least a portion with this elute of alkaline purification;
(c) at least a portion of said adducts or salt is separated from said elute; With
(d) contact with at least a portion of isolating adducts or salt and poly carboxylic acid or its acid anhydrides and with oxyamine or its salt.
22. the method for claim 21, wherein contact (d) less than 7 pH, said adducts or salt are being transformed back said imide and are making said poly carboxylic acid or its acid anhydrides and said oxyamine or its reactant salt carry out under with the condition that produces the extra substituted cyclic imide of N-.
23. a method that is used for phenylcyclohexane is oxidized to the phenylcyclohexane hydroperoxide, this method comprises:
(a) said phenylcyclohexane is being contacted in the presence of the substituted cyclic imide of N-with also producing under the condition that comprises phenylcyclohexane hydroperoxide, the substituted cyclic imide of unreacted N-and the elute of the degradation production of the substituted cyclic imide of this N-at the said hydrocarbon of oxidation with oxygen-containing gas;
(b), be converted into adducts or salt with said unreacted imide and said degradation production with at least a portion with this elute of alkaline purification;
(c) at least a portion of said adducts or salt is separated from said elute; With
(d) contact with at least a portion of isolating adducts or salt and poly carboxylic acid or its acid anhydrides and with oxyamine or its salt.
24. the method for claim 23, wherein contact (d) less than 7 pH, said adducts or salt are being transformed back said imide and are making said poly carboxylic acid or its acid anhydrides and said oxyamine or its reactant salt carry out under with the condition that produces the extra substituted cyclic imide of N-.
25. a method that is used for the oxygenated hydrocarbon charging, this method may further comprise the steps:
(a) said hydrocarbon charging and oxygen are contacted under with the condition that produces the charging that comprises oxidation at least and the elute of at least a degradation production of the substituted cyclic imide of this N-at least a portion that is being enough to the said hydrocarbon charging of oxidation in the presence of the substituted cyclic imide of N-;
(b) from this elute, remove at least a portion of the degradation production of the substituted cyclic imide of this N-;
(c) part of removing of the degradation production of the substituted cyclic imide of this N-is contacted with at least a reactant that is selected from acid or its acid anhydrides and oxyamine or its salt, transform back said imide with at least a portion with this degradation production; With
(d) will be recycled to step (a) from the imide that step (c) obtains.
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