CN102666482B - Oxidation of hydrocarbons - Google Patents
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- CN102666482B CN102666482B CN201080053105.3A CN201080053105A CN102666482B CN 102666482 B CN102666482 B CN 102666482B CN 201080053105 A CN201080053105 A CN 201080053105A CN 102666482 B CN102666482 B CN 102666482B
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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
This application claims the U.S. Provisional Application right of priority that the sequence number submitted on November 25th, 2009 is 61/264399, the disclosure of this application is included in by reference of text at this.
Technical field
The present invention relates to for oxygenated hydrocarbon, specifically alkylaromatic hydrocarbon to produce the method for such as phenol and substituted phenol.
Background technology
The oxidation of hydrocarbon is important reaction in industrial organic chemistry.Therefore, such as commercial oxidation production hexalin and the pimelinketone utilizing hexanaphthene, hexalin and pimelinketone are the important as precursors of producing nylon, and utilize the oxidation of alkylaromatic hydrocarbon to produce phenol, phenol is the precursor producing polycarbonate and epoxy resin.
Known oxygenant such as KMnO can be used
4, CrO
3and HNO
3carry out the oxidation of hydrocarbon.But the shortcoming of these oxygenants is relatively costly, and their use is along with the undesired coupling product of generation, and this can bring handling problems.
Therefore, preferably use based on superoxide or N
2the oxygenant of O.But the most cheap oxygenant is the molecular oxygen of pure form or atmosphericoxygen form.But oxygen itself is not suitable for oxygenated hydrocarbon usually, because the O existed with the triplet state form that energy is favourable
2the reactivity of molecule is not enough.
By using redox metal catalyzer, molecular oxygen can be utilized to carry out oxidation of organic compounds, and therefore a large amount of commercial runs is based on the autoxidation of the hydrocarbon of metal catalytic.Therefore, such as, use cobalt salt, carry out hexanaphthene O
2be oxidized to hexalin and/or pimelinketone.These commercial runs based on free radical chain mechanism, wherein diradical oxygen and hydrocarbon free radical reaction, and form peroxy radical, subsequently by capturing H atom and chainpropagation from another hydrocarbon.But except metal-salt, organic molecule also can serve as radical initiator.
But the shortcoming of these methods is, along with transformation efficiency increases, selectivity greatly declines, and therefore the method must be implemented under very low-level transformation efficiency.Therefore, such as, hexanaphthene carries out under the transformation efficiency of 10-12% to the oxidation of cyclohexanol/cyclohexanone, selectivity is made to be 80-85% (" Industrielle Organische Chemie [industrial organic chemistry] 1994; 261; VCH-Verlag, D-69451 Weinheim ").
It is use organic mediation agent (mediator), such as HP (NHPI) that the one of metal salt catalyst substitutes.Therefore, United States Patent (USP) 6852893 and 6720462 discloses and (typically is N-hydroxyl carbon imide catalyzer at radical initiator and catalyzer, such as HP (NHPI)) exist under, by the method making hydrocarbon substrate and oxygen-containing gas contact oxygenated hydrocarbon substrate, wherein oxygen content is 5-100% volume.The method the temperature of 0 DEG C-500 DEG C, and is carried out at the pressure that normal atmosphere-100 clings to (100-10,000kPa).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, such as 1: 1-0.5: 1.The suitable substrate be oxidized by this quadrat method comprises cumene, phenylcyclohexane, cyclo-dodecyl benzene and sec-butylbenzene.
United States Patent (USP) 7038089 discloses the method being prepared hydroperoxide by the hydrocarbon being selected from uncle's hydrocarbon, secondary hydrocarbon and composition thereof, described method is included in the temperature range of 130-160 DEG C, containing described hydrocarbon and containing in the reaction mixture of catalyzer of cyclic imide compound and alkali metal compound, be oxidized described hydrocarbon with oxygen-containing gas.Suitable hydrocarbon it is said and comprises C
4-C
20tertiary alkane (such as, Trimethylmethane, iso-pentane, isohexane etc.), there is the C of 1-6 aromatic ring
7-C
20(alkyl) aromatic hydrocarbons, or there is the C of 1-6 aromatic ring
9-C
20(cycloalkyl) aromatic hydrocarbons (such as dimethylbenzene, cumene, isopropyltoluene, ethylbenzene, diisopropyl benzene, phenylcyclohexane, naphthane (tetralin), indane etc.) etc.The consumption of the cyclic imide compound used is based on reaction mixture weight, can be 0.0001-1%, the adducts of preferred 0.0005-0.5% or salt, and the consumption of alkali metal compound is based on the weight of reaction mixture, can be 0.000005-0.01%, preferred 0.00001-0.005%.
But, although current work continues the effectiveness of display cyclic imide as hydrocarbon oxidation catalyst, also show that their application needs in business method are further developed.Especially, cyclic imide, such as HP is expensive and is easily hydrolyzed under oxidation reaction condition.And unreacted imide catalyst and their degradation production (acid and ether) can bring significant problem to the division of downstream reaction such as hydroperoxide.Therefore, the oxidation that cyclic imide is successfully applied to hydrocarbon processing oxidation effluent by requiring, to remove unreacted imide and their degradation production, with if possible, collecting valuable unreacted imide.
International application WO 2009/025939 discloses method hydrocarbon being oxidized to corresponding hydroperoxide, alcohol, ketone, carboxylic acid or dicarboxylic acid, wherein makes hydrocarbon and oxygen-containing gas under the catalyzer comprising cyclic imide exists, contact to produce the effluent of hydrocarbon product and the unreacted imide catalyst comprising oxidation.Use this effluent of aqueous solution process of alkali, particularly alkaline carbonate and/supercarbonate subsequently, to produce the organic phase of the aqueous phase comprising unreacted imido salt and the hydrocarbon product comprising oxidation.Subsequently by aqueous phase as acidified to precipitate unreacted imide catalyst, then will collect unreacted imide catalyst and be recycled to oxidation step.
According to the present invention, have now been found as catch unreacted imide with alkali and this imide is recycled to hydrocarbon oxidation step alternative or except catching unreacted imide with alkali and this imide being recycled to except hydrocarbon oxidation step, caught imide can be fed to imide manufacturing process and improve the imide productive rate of this technique thus.
Summary of the invention
On the one hand, the invention reside in the method for oxygenated hydrocarbon, the method comprises:
Under the existence of a cyclic imide that () makes hydrocarbon replace at N-with described hydrocarbon is being oxidized and is contacting under the condition of at least one degradation production of cyclic imide that replaces with this N-of the hydrocarbon product producing oxidation; With
B () makes contacting under described imido condition is returned in the conversion at least partially of this at least one degradation production with the first reactant being selected from oxyamine or its salt at least partially of this at least one degradation production.
In various embodiments, this degradation production is contacted with the second reactant being 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, the method comprised (a) further before contact (b), the at least one degradation production of the cyclic imide that the cyclic imide replaced with the hydrocarbon product of this oxidation of alkaline purification, unreacted N-and this N-replace, to be converted into adducts or salt by described unreacted imide at least partially and described degradation production; (b) removing from the hydrocarbon product of oxidation at least partially by this adducts or salt.
In one embodiment, this hydrocarbon comprises the Alkylaromatics of general formula (I):
Wherein R
1and R
2represent hydrogen independently of one another or have the alkyl of 1-4 carbon atom, prerequisite is R
1and R
2the cyclic group with 4-10 carbon atom can be connected to form, and R
3represent hydrogen, one or more alkyl or cyclohexyl with 1-4 carbon atom.
Advantageously, the Alkylaromatics of described general formula (I) be selected from ethylbenzene, cumene, sec-butylbenzene, sec.-amyl sec-pentyl secondary amyl benzene, to methyl-sec-butylbenzene, Isosorbide-5-Nitrae-diphenylcyclohexane, Sec-Hexyl benzene and phenylcyclohexane.
In another embodiment, hydrocarbon comprises alkane as Trimethylmethane, or naphthenic hydrocarbon is as hexanaphthene.
Advantageously, the cyclic imide that described N-replaces meets general formula (II):
Wherein R
4, R
5, R
6and R
7be selected from the alkyl and substituted hydrocarbon radical with 1-20 carbon atom independently of one another, or be selected from group SO
3h, NH
2, OH and NO
2, or be selected from atom H, F, Cl, Br and I; X and Z is selected from C, S, CH independently of one another
2, the element of the 4th race in N, P and periodictable; Y is O or OH; K is 0,1 or 2; 0,1 or 2 with l.
In one embodiment, the cyclic imide that described N-replaces comprises HP.
In one embodiment, described alkali comprises ammonia, and described amide salt precipitates from described effluent.
In another embodiment, described alkali comprises ammonium hydroxide aqueous solution or aqueous hydroxylamine, and described adducts or salt are dissolved in the described aqueous solution.
In further embodiment, described alkali comprises the aqueous solution of metal carbonate and/or supercarbonate, and described adducts or salt are dissolved in the described aqueous solution.
In further embodiment, described alkali comprises pyridine, and described adducts or salt precipitate from described effluent.
Accompanying drawing explanation
Fig. 1 is the schema of the hydrocarbon oxidation method according to one embodiment of this invention.
Describe in detail
There is described herein the method be oxidized to by hydrocarbon in corresponding hydroperoxide, alcohol, ketone, carboxylic acid or dicarboxylic acid one of at least.The method comprises the reaction medium making to comprise hydrocarbon and contacts with under the condition being oxidized described hydrocarbon under the existence of catalyzer comprising cyclic imide with oxygen-containing gas.This oxidizing reaction produces the effluent of the degradation production of the cyclic imide of hydrocarbon product and this N-replacement comprising oxidation.
In various embodiments, degradation production is made to contact under described imido condition is returned in the conversion at least partially of this at least one degradation production with the first reactant being selected from oxyamine or its salt subsequently.
In various embodiments, before contacting with the first reactant, one or more of the cyclic imide degradation production that the cyclic imide using alkaline purification oxygenated hydrocarbon product, unreacted N-to replace and N-replace, are converted into adducts or salt to make this unreacted imide at least partially and this degradation production.This adducts or salt can be separated subsequently, and optionally, be fed in the technique for the synthesis of cyclic imide, improve synthesis yield thus.
Hydrocarbon charging
Use method of the present invention, can the multiple substituted or unsubstituted saturated or undersaturated hydrocarbon of selective oxidation, such as alkane, naphthenic hydrocarbon, alkene, cycloolefin and aromatic hydrocarbons.But, especially, the method can be used for Trimethylmethane selective oxidation to become tert-butyl hydroperoxide and the trimethyl carbinol, hexanaphthene selective oxidation is become cyclohexyl hydroperoxide, hexalin and pimelinketone, becomes corresponding hydroperoxide with by the Alkylaromatics selective oxidation of general formula (I):
Wherein R
1and R
2represent hydrogen independently of one another or have the alkyl of 1-4 carbon atom, prerequisite is R
1and R
2the cyclic group with 4-10 carbon atom can be connected to form, and R
3represent hydrogen, one or more alkyl or cyclohexyl with 1-4 carbon atom.The example of suitable Alkylaromatics be ethylbenzene, cumene, sec-butylbenzene, sec.-amyl sec-pentyl secondary amyl benzene, to methyl-sec-butylbenzene, Isosorbide-5-Nitrae-diphenylcyclohexane, Sec-Hexyl benzene and phenylcyclohexane, wherein preferably sec-butylbenzene and phenylcyclohexane.It is also understood that, wherein R
1and R
2when being connected to form cyclic group, the carbon number forming cyclic rings is 4-10.But this ring itself can be with one or more substituting group, such as one or more alkyl with 1-4 carbon atom, or one or more phenyl, in the situation as Isosorbide-5-Nitrae-diphenylcyclohexane.
In an actual embodiment, the Alkylaromatics of general formula (I) is sec-butylbenzene, and by under alkylating conditions and heterogeneous catalyst such as zeolite beta or more preferably MCM-22 race at least one molecular sieve (as giving a definition) exist under, use at least one C
4alkylating agent makes benzene alkylation and produces.Alkylation conditions comprises about 60 DEG C of-Yue 260 DEG C easily, such as the temperature of about 100 DEG C of-Yue 200 DEG C.Alkylation pressures is below 7000kPa easily, and such as about 1000-is about 3500kPa.Alkylation is easily based on C
4the about 0.1-of alkylating agent is about 50h
-1, such as about 1-is about 10h
-1weight hourly space velocity degree (WHSV) under carry out.
C
4alkylating agent comprises at least one linear butenes easily, that is butene-1, butene-2 or their mixture.Alkylating agent also can be the olefinic C containing linear butenes class
4hydrocarbon mixture, such as, by steam cracking ethane, propane, butane, LPG and light naphtha, cat cracked naphtha is with other refinery feedstock and pass through oxygenate, and such as methanol conversion becomes light alkene to obtain.Such as, following C
4hydrocarbon mixture all can obtain usually in adopting steam cracking with any refining producing alkene, and is suitable for as C
4alkylating agent: the thick butene stream of steam cracking, raffinate-1 (in solvent extraction or hydrogenation with product residual after remove divinyl from the thick butene stream of steam cracking) and raffinate-2 (product remained after remove divinyl and iso-butylene from the thick butene stream of steam cracking).
In further actual embodiment, the Alkylaromatics of general formula (I) is phenylcyclohexane, and occurs react with obtained phenylcyclohexane (CHB) and obtain as follows by making benzene and hydrogen carry out contacting benzene thus under hydroalkylation condition under the existence of hydroalkylation catalyzer:
The catalyzer used in this hydroalkylation is dual functional catalyst, and it comprises the molecular sieve and 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).Metal hydride known arbitrarily may be used for this hydroalkylation catalyzer, but suitable metal comprises palladium, ruthenium, nickel, zinc, tin and cobalt, particularly advantageously palladium.Usually, the amount of the metal hydride existed in this catalyzer is that the about 0.05-of this catalyzer is about 10wt%, and 0.1-is about 5wt% according to appointment.In one embodiment, when molecular sieve is aluminosilicate, the amount of the metal hydride of existence makes the mol ratio of the aluminium in molecular sieve and metal hydride be about 1.5-about 1500, such as about 75-about 750, according to appointment 100-about 300.
This metal hydride can such as by dipping or the direct load of ion-exchange over a molecular sieve.But, in a more preferred embodiment, by least 50wt%, such as at least 75wt% and usually substantially all metal hydride load to separate with molecular sieve but with on the inorganic oxide of its compound.Especially, find by by metal hydride load on inorganic oxide, compared with metal hydride load catalyzer of equal value over a molecular sieve, improve the activity of catalyzer and the selectivity to phenylcyclohexane and dicyclohexyl benzene thereof.
The inorganic oxide used in the hydroalkylation catalyzer of this compound there is no narrow restriction, as long as it is stable with inertia under hydroalkylation condition.Suitable inorganic oxide comprises the oxide compound of the periodic table of elements the 2nd, 4,13 and 14 race, as aluminum oxide, titanium dioxide and/or zirconium white.The numbering of periodictable race used herein is disclosed in Chemical and Engineering News, 63 (5), 27 (1985).
Advantageously by metallic inorganic oxide and described molecular sieve compound with obtained catalyst composite before, by metal hydride by immersion deposition on inorganic oxide.Typically, catalyst composite is obtained by altogether granulation, is wherein pellet by the mixture forming of molecular sieve and metallic inorganic oxide under high pressure (usually about 350-about 350,000kPa); Or obtained by coextrusion, wherein molecular sieve is optionally extruded by die head with the slurry of metallic inorganic oxide together with independent tackiness agent.If necessary, extra metal hydride can be deposited in the catalyst composite of gained subsequently.
Suitable adhesive material comprises synthesis or naturally occurring material, and inorganic materials is as clay, silica and/or metal oxide.The latter can be naturally occurring, or comprises gelatinous precipitate or the gel form of silica and metal oxide.The naturally occurring clay that can be used as tackiness agent comprises those of polynite and kaolin series, described series comprises sub-bentonite (subbentonite) and kaolin, usually be known as Dixie, McNamee, Georgia and Florida clay, or wherein main mineral constituent is other series of halloysite, kaolinite, dickite, nakrite or anauxite.These clays can carry out calcining, acid treatment or chemical modification to use with the virgin state of original exploitation or at first.Suitable metal oxide binder comprises silica, aluminum oxide, zirconium white, titanium dioxide, silica-alumina, silica-magnesia, silica-zirconia, silica-Thorotrast, silica-beryllia, silica-titania, and ternary composition is as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia.
Hydroalkylation can carry out in the reactor configurations of wide region, comprises fixed bed, slurry-phase reactor and/or catalytic distillation tower.In addition, this hydroalkylation can carry out in single reaction zone or in multiple reaction zone, wherein introduces reaction by stages to major general's hydrogen.Suitable temperature of reaction be about 50 DEG C of-Yue 400 DEG C, according to appointment 100 DEG C of-Yue 250 DEG C, and the reaction pressure be suitable for is about 7000kPa for about 100-, and 500-is about 5000kPa according to appointment.The Appropriate of the mol ratio of hydrogen and benzene is about 0.01-about 100, and be more particularly about 15:1 for about 0.15:1-, 0.4:1-is about 4:1 according to appointment, and such as about 0.4-is about 0.9:1.The weight hourly space velocity of benzene is generally about 0.01-and is about 100hr
-1.This hydroalkylation is heat release, and this reaction system must consider that heat controls thus.Preferred method is by a part for the effluent from hydroalkylation device via cooling heat exchanger recirculation, and is mixed with charging by the recycle stream of cooling.Advantageously can also adopt more than one hydroalkylation bed or reactor, and add hydrogen by stages.
Term as used herein " MCM-22 race material " (or " material of MCM-22 race " or " MCM-22 family molecular sieves " or " MCM-22 race zeolite ") comprise following in one or more:
The molecular sieve be made up of common first degree crystalline tectonic element structure cell, described structure cell has MWW framework morphology.(structure cell is the spatial disposition of atom, and it describes the structure of crystal in three-dimensional space during laying.At " Atlas of Zeolite Framework Types ", the 5th edition, discuss this crystalline structure in 2001, its full content is included in as a reference at this);
The molecular sieve be made up of common secondary crystallization tectonic element, it is the two-dimentional laying of the structure cell of this MWW framework morphology, forms a unit cell thickness, the preferably individual layer of a c-unit cell thickness;
The molecular sieve be made up of common secondary crystallization tectonic element, it is one or is greater than the layer of a unit cell thickness, and the layer being wherein greater than a unit cell thickness is made up of stacking (stacking), the individual layer of filling (packing) or bonding at least two unit cell thickness.The stacking of this secondary building unit can be regular fashion, irregular mode, random placement, or their any combination; With
By having the molecular sieve that any rule of the structure cell of MWW framework morphology or random two dimension or three-dimensional array are made.
MCM-22 family molecular sieves comprises those molecular sieves with X-ray diffraction pattern, and described 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 X-ray diffraction data that exosyndrome material uses such as use the K-α doublet of copper as the radiation of incidence by standard technique and are furnished with scintillometer and associated computer and obtain as the diffractometer of gathering system.
MCM-22 race material comprises MCM-22 (described in United States Patent (USP) 4954325), PSH-3 (described in United States Patent (USP) 4439409), SSZ-25 (described in United States Patent (USP) 4826667), ERB-1 (described in European patent 0293032), ITQ-1 (described in United States Patent (USP) 6077498), ITQ-2 (described in international patent publications WO97/17290), MCM-36 (described in United States Patent (USP) 5250277), MCM-49 (described in United States Patent (USP) 5236575), MCM-56 (described in United States Patent (USP) 5362697), UZM-8 (described in United States Patent (USP) 6756030) and their mixture.MCM-22 family molecular sieves is preferably as alkylation catalyst, because find compared with other butylbenzene isomers, they have high selectivity to production sec-butylbenzene.Preferably, the phenogen (isotype) of molecular screening oneself (a) MCM-49, (b) MCM-56 and (c) MCM-49 and MCM-56, such as ITQ-2.
Hydrocarbon is oxidized
Under existing at the catalyzer of the cyclic imide comprising general formula (II), hydrocarbon substrate is contacted with oxygen-containing gas, realizes the oxidation step in the inventive method:
Wherein R
4, R
5, R
6and R
7be selected from the alkyl and substituted hydrocarbon radical with 1-20 carbon atom independently of one another, or be selected from group SO
3h, NH
2, OH and NO
2, or be selected from atom H, F, Cl, Br and I; X and Z is selected from C, S, CH independently of one another
2, the element of the 4th race in N, P and periodictable; Y is O or OH; K is 0,1 or 2; 0,1 or 2 with l.
In an actual embodiment, cyclic imide catalyzer comprises HP.
Carry out condition that oxidation step uses to change significantly with the type of the hydrocarbon substrate that will be oxidized, but normally suitable condition comprises about 20 DEG C of-Yue 150 DEG C, the such as temperature of about 70 DEG C of-Yue 130 DEG C, and about 15kPa-is about 500kPa, such as 15kPa-is about the pressure of 150kPa.
Depend on the character of hydrocarbon substrate, the product of oxidation step can comprise in the hydroperoxide of corresponding hydrocarbon, alcohol, ketone, carboxylic acid or dicarboxylic acid one or more.But, except containing except required hydrocarbon oxidation products, from the degradation production of effluent also containing unreacted cyclic imide catalyzer and cyclic imide of oxidation step.If catalyzer is HP, these degradation productions comprise 2-(Hydroxycarboamoyl) phenylformic acid, phthalic acid and the alkoxyl group-phthalic imidine that produce according to following reaction:
Unreacted imide catalyst and degradation production thereof are not only downstream reaction, particularly step toward division and bring significant problem, and they make to have lost valuable catalyzer.The inventive method is caught and is removed these materials from this oxidation effluent thus, and by this material feeding in imide synthesis step, produces the imide yield of improvement thus in synthesis step.Can reuse subsequently and reclaim thus and the imide catalyst regenerated.
Catch unreacted imide catalyst and degradation production thereof can comprise first with alkaline purification effluent so that unreacted imide at least partially and degradation production thereof are converted into adducts or salt.This alkali can be the aqueous solution of metal carbonate and/or supercarbonate, and it is using the unreacted imide of catching as the salt dissolving in this alkali aqueous solution and degradation production thereof.But such alkali will not react with ether degradation production.Preferred alkali is nitrogenous alkali thus, because it not only will produce adducts with unreacted imide and sour degradation production thereof, but also produces adducts with ether degradation production.Suitable nitrogenous alkali comprises (i) ammonia, and now adducts precipitates from oxidation effluent; (ii) ammonium hydroxide aqueous solution or aqueous hydroxylamine, now adducts is dissolved in this aqueous solution; (iii) pyridine, now adducts precipitates from oxidation effluent.
Using unreacted imide catalyst and degradation production thereof as after adducts and/or salt are caught, this adducts and/or salt are removed from oxidation effluent, typically via filtration or be separated, and are fed in imide building-up reactions.In imide building-up reactions, make this adducts and/or salt and be selected from oxyamine or its salt contacts with at least one reactant of acid or its acid anhydrides.Thus, when imide is HP, usually by adducts and/or salt be selected from oxyamine or its salt contacts with at least one reactant of phthalic acid or Tetra hydro Phthalic anhydride.Such as, when degradation production is phthalic acid, oxyamine can be added in degradation production so that phthalic acid is transformed back HP.In one embodiment, phthalic acid and oxyamine all being added, with except regenerating back except HP by degradation production, also producing extra HP.
Typically, imide building-up reactions be less than 7 pH, preferably carry out at the pH of about 2-about 6, with at least one degradation production is transformed back N-replace cyclic imide.In one embodiment, degradation production, adducts or salt are transformed back described imide under making described poly carboxylic acid or acid anhydrides and described oxyamine or its reactant salt with the condition of the cyclic imide producing extra N-and replace.It is about 0.5-about 10.0 that suitable condition comprises the mol ratio being added to poly carboxylic acid in building-up reactions or its acid anhydrides and oxyamine or its salt, such as about 0.8-about 2.0,1.0-about 1.8, and temperature is according to appointment about 0 DEG C of-Yue 100 DEG C, and the reaction times is about 0.5-about 24 hours.
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 dicarboxylic acid, particularly hydroperoxide.
Such as, when hydrocarbon substrate is Trimethylmethane, oxidation products comprises tert-butyl hydroperoxide (it can be used as oxidising agent and for the production of propylene oxide) and the trimethyl carbinol (it can be used as gasoline dope).
When hydrocarbon substrate is hexanaphthene, oxidation products comprises cyclohexyl hydroperoxide, hexalin and pimelinketone.The easy thermolysis of cyclohexyl hydroperoxide or resolve into extra hexalin and pimelinketone under catalyzer is assisted.Aqueous nitric acid can be adopted to be oxidized hexalin to produce hexanodioic acid, and hexanodioic acid is synthetic nylon 6, the precursor in 6, and pimelinketone can change into hexamethylene oxime, and pimelinketone carries out acid catalyzed rearrangement to produce hexanolactam, and it is the precursor in synthetic nylon 6.
When hydrocarbon substrate is the Alkylaromatics of general formula (I), the product of oxidizing reaction comprises the hydroperoxide of general formula (III):
Wherein R
1, R
2and R
3there is the implication identical with formula (I).Preferably, hydroperoxide are sec-butylbenzene hydroperoxide, cyclohexylbenzene hydroperoxide or cumene hydroperoxide.Then by acid division, such hydroperoxide are changed into phenol or substituted phenol and general formula R
1cOCH
2r
2(IV) aldehydes or ketones, wherein R
1and R
2there is the implication identical with formula (I).Phenol can react to produce dihydroxyphenyl propane with acetone certainly, and it is producing the precursor in polycarbonate and epoxy resin.
By the temperature about 20 DEG C of-Yue 150 DEG C, such as about 40 DEG C of-Yue 120 DEG C, and/or about 50-is about the pressure of 2500kPa, such as about 100-is about 1000kPa, and/or is about 100h based on the about 0.1-of hydroperoxide
-1, preferably about 1-is about 50h
-1liquid hourly (LHSV) under, make hydroperoxide and catalyst exposure in the liquid phase, carry out the dissociative reaction of hydroperoxide easily.Preferably hydroperoxide are diluted, with auxiliary removing heat in organic solvent such as methylethylketone, phenol or the sec-butylbenzene of dissociative reaction inertia.Dissociative reaction is carried out easily in catalytic distillation unit.
The catalyzer used in step toward division can be homogeneous catalyst or heterogeneous catalyst.In a kind of embodiment of reality, can by cyclic imide is fixed or load on solid material, homogeneous phase cyclic imide is converted into heterogeneous catalyst.Exemplarily, can by various functional group as imide-, amide group-or sulfoamido-, cyclic imide is fixed on fluoropolymer resin.As another example, by chemical bond via aminoalkyl group, cyclic imide can be fixed on solid carrier as on silica gel.The advantage of heterogeneous cyclic imide is, it can more easily be separated and recirculation compared with homogeneous phase cyclic imide.In addition, heterogeneous cyclic imide may reside in fixed bed, wherein need not be separated the cyclic imide Sum decomposition product that N-replaces.Oxidation reactor can run in parallel, and fixed bed catalyst can be regenerated when off-line.
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 are also effective homogeneous phase cleavage catalysts.Preferred homogeneous phase cleavage catalysts is sulfuric acid.
The suitable heterogeneous catalyst used in division sec-butylbenzene hydroperoxide comprises montmorillonitic clay, such as acid polynite silica-alumina clay, described in United States Patent (USP) 4870217 (Texaco), its whole disclosure is included in by reference at this.
With reference to accompanying drawing, Fig. 1 is the oxidation step of a kind of embodiment of the inventive method and the schema of oxidation effluent treatment step.In such an implementation, hydrocarbon stream 7, oxygenate stream 8 and optional supplementary imide logistics 9 are fed in oxidation reactor 10 to produce oxidation effluent.Oxidation effluent 11 and gas phase or liquid phase alkali logistics 12 are led to process and segregation section 13.In process and segregation section 13, alkali logistics 12 and oxidation effluent are merged to make with unreacted imide and degradation production thereof react to form adducts or salt at least partially.Subsequently this adducts or salt be separated from oxidation effluent and be fed to imide synthesis reactor 15 as logistics 14 to produce the imide of regeneration.Typically the imide of this regeneration is circulated back to oxidation reactor via recirculation stream 18.Remaining oxidation effluent is led to downstream reactor 17 as logistics 16, at this typically via being oxidized or dividing the product this effluent being converted into expectation.
By reference to following nonlimiting examples, more specifically the present invention is described.
Embodiment 1: use HP (NHPI) to carry out cyclohexylbenzene hydroperoxide (CHB) as catalyzer
The 150g that weighs is added to the Parr reactor being furnished with agitator, thermopair, gas inlet, sampling port and the condenser containing the Dean-Stark trap for dewatering from the NHPI of TCI from the phenylcyclohexane of TCI America and 0.16g.Under atmospheric pressure with 1000rpm reactor contents, and with the flow velocity of 250cc/min nitrogen purging 5 minutes.Under nitrogen purge reactor is heated to 110 DEG C in maintenance subsequently.When reaching temperature of reaction, gas is converted to air from nitrogen, and with 250cc/min air purge reactor 4 hours.Sampling per hour, and analyzed by gas-chromatography.After 4 hours, gas is converted back nitrogen and stops heating.At the end of HPLC analyzes display oxidizing reaction, NHPI concentration is 926ppm.
Embodiment 2: use solution of ammonium hydroxide removing NHPI
By 0.1069 gram of NH
4the OH aqueous solution (28-32wt%) is added in the oxidation effluent of 30 grams of embodiments 1.Stir the mixture 15 minutes and sample from organic phase subsequently and analyze for NHPI.HPLC analyzes and is presented at NH
4at the end of OH process, NHPI concentration is 38.5ppm, and except NHPI level reduces, this oxidation effluent composition keeps identical before and after the treatments.
Embodiment 3: use ammonia removing NHPI
By nitrogen gas stream via 30 grams of NH
4the OH aqueous solution (28-32wt%) passes through, and by gained gas sparging by the oxidation effluent of 30 grams of embodiments 1 30 minutes.From the organic phase of this effluent, sampling is used for analyzing.At the end of HPLC analyzes and is presented at ammonia treatment, NHPI concentration is 16.5ppm, and except NHPI level reduces, this oxidation effluent composition keeps identical before and after the treatments.
Above-mentioned data clearly illustrate, pass through NH
4oH and ammonia treatment reduce the NHPI level in oxidation effluent, and hydroperoxide product can not be made to decompose.
In various embodiments, the method relates to:
Contact under the existence of 1, (a) cyclic imide that hydrocarbon and oxygen are replaced at N-with under the condition described hydrocarbon being oxidized at least one degradation production to produce the cyclic imide that the hydrocarbon product that is oxidized replaces with N-; With
B () makes contacting under described imido condition is returned in the conversion at least partially of this at least one degradation production with the first reactant being selected from oxyamine or its salt at least partially of this at least one degradation production.
2, the method for embodiment 1, it comprises further makes this at least one degradation production at least partially contact with the second reactant being selected from acid or its acid anhydrides.
3, the method for embodiment 1, comprises further:
A () is before contact (b), the at least one degradation production of the cyclic imide that the cyclic imide replaced with the hydrocarbon product of alkaline purification oxidation, unreacted N-and N-replace, to be converted into adducts or salt by described unreacted imide at least partially and described degradation production; With
(b) removing this adducts or salt from the hydrocarbon product of oxidation at least partially.
4, the method for embodiment 1, wherein this acid or its acid anhydrides are poly carboxylic acid or its acid anhydrides, and the wherein cyclic imide that replaces to produce extra N-with described oxyamine or its reactant salt of this poly carboxylic acid or its acid anhydrides.
5, the method for embodiment 1, wherein said hydrocarbon comprises the Alkylaromatics of general formula (I):
Wherein R
1and R
2represent hydrogen independently of one another or have the alkyl of 1-4 carbon atom, prerequisite is R
1and R
2the cyclic group with 4-10 carbon atom can be connected to form, and R
3represent hydrogen, one or more alkyl with 1-4 carbon atom or cyclohexyl.
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, Isosorbide-5-Nitrae-diphenylcyclohexane, 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):
Wherein R
1, R
2and R
3there is the implication identical with formula (I), and the method comprises the phenol and the general formula R that described hydroperoxide are transformed into phenol or replacement further
1cOCH
2r
2(IV) aldehydes or ketones, wherein R
1and R
2there is the implication identical with formula (I).
8, the method for embodiment 1, wherein said degradation production comprises phthalic acid.
9, the method for embodiment 1, wherein said degradation production comprises alkoxyl group phthalic imidine.
10, the method for embodiment 1, wherein said hydrocarbon comprises hexanaphthene, and the hydrocarbon product of described oxidation comprises hexalin, and the method comprises further hexalin is converted into hexanodioic acid.
11, the method for embodiment 1, wherein said hydrocarbon comprises hexanaphthene, and the hydrocarbon product of described oxidation comprises pimelinketone, and the method comprises further pimelinketone is converted into hexanolactam.
12, the method for embodiment 1, wherein said hydrocarbon comprises Trimethylmethane, and the hydrocarbon product of described oxidation comprises tert-butyl hydroperoxide, and the method comprises this tert-butyl hydroperoxide of use further as oxide catalyst.
13, the method for embodiment 1, the cyclic imide that wherein said N-replaces meets general formula (II):
Wherein R
4, R
5, R
6and R
7be selected from the alkyl and substituted hydrocarbon radical with 1-20 carbon atom independently of one another, or be selected from group SO
3h, NH
2, OH and NO
2, or be selected from atom H, F, Cl, Br and I; X and Z is selected from C, S, CH independently of one another
2, the element of the 4th race in N, P and periodictable; Y is O or OH; K is 0,1 or 2; 0,1 or 2 with l.
14, the method for embodiment 1, the cyclic imide that wherein said N-replaces comprises HP.
15, the method for embodiment 1, the pressure that wherein said contact (a) is about 500kPa in the temperature of about 20-about 150 DEG C and about 15kPa-carries out.
16, the method for embodiment 1, the pressure that wherein said contact (a) is about 150kPa in the temperature of about 70-about 130 DEG C and about 15kPa-carries out.
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 described adducts precipitates from described response composite.
19, the method for embodiment 1, wherein said alkali comprises ammonium hydroxide aqueous solution, and described adducts is dissolved in the described aqueous solution.
20, the method for embodiment 1, wherein said alkali comprises the aqueous solution of metal carbonate and/or supercarbonate, and described adducts or salt are dissolved in the described aqueous solution.
21, the method for embodiment 1, wherein said alkali comprises pyridine.
22, the method for embodiment 1, is wherein added to the mol ratio of described poly carboxylic acid in described contact procedure (d) or its acid anhydrides and described oxyamine or its salt for about 0.5-about 10.0.
23, the method for embodiment 1, is wherein added to the mol ratio of described poly carboxylic acid in described contact procedure (d) or its acid anhydrides and described oxyamine or its salt for about 1.0-about 1.8.
24, the method for embodiment 1, wherein said contact (b) is carried out in the temperature of about 0-about 100 DEG C.
In various embodiments, the method relates to:
Comprise sec-butylbenzene hydroperoxide with described hydrocarbon being oxidized and producing, contact under the condition of the effluent of the degradation production of cyclic imide that cyclic imide that unreacted N-replaces replaces with N-under the existence of a cyclic imide that () makes described sec-butylbenzene and oxygen-containing gas replace at N-; With
B this effluent alkali processes by (), so that described unreacted imide at least partially and described degradation production are converted into adducts or salt;
C () is separated at least partially by described adducts or salt from described effluent; With
(d) contacting the adducts of separation or salt with oxyamine or its salt with poly carboxylic acid or its acid anhydrides at least partially.
In various embodiments, described adducts or salt, at the pH being less than 7, are being transformed back described imide and are carrying out under making described poly carboxylic acid or its acid anhydrides and described oxyamine or its reactant salt with the condition of the cyclic imide producing extra N-and replace by contact (d).
In various embodiments, the method relates to:
Comprise cyclohexylbenzene hydroperoxide with being oxidized described hydrocarbon and producing, contact under the condition of the effluent of the degradation production of cyclic imide that cyclic imide that unreacted N-replaces replaces with N-under the existence of a cyclic imide that () makes described phenylcyclohexane and oxygen-containing gas replace at N-;
B this effluent alkali processes by (), so that described unreacted imide at least partially and described degradation production are converted into adducts or salt;
C () is separated at least partially by described adducts or salt from described effluent; With
(d) contacting the adducts of separation or salt with oxyamine or its salt with poly carboxylic acid or its acid anhydrides at least partially.
In various embodiments, described adducts or salt, at the pH being less than 7, are being transformed back described imide and are carrying out under making described poly carboxylic acid or its acid anhydrides and described oxyamine or its reactant salt with the condition of the cyclic imide producing extra N-and replace by contact (d).
In various embodiments, the method relates to:
Under the existence of a cyclic imide that () makes described hydrocarbon charging and oxygen replace at N-, be enough to be oxidized described hydrocarbon charging at least partially with the condition of the effluent of at least one degradation production of the cyclic imide producing the charging that at least comprises oxidation and replace with N-under contact;
B () removes the degradation production of the cyclic imide that N-replaces at least partially from this effluent;
The remove portion of the degradation production of c cyclic imide that () makes N-replace be selected from acid or its acid anhydrides contacts with at least one reactant of oxyamine or its salt, so that described imide is returned in the conversion at least partially of degradation production; With
D imide that step (c) obtains by () is recycled to step (a).
Although describe with reference to particular and explain the present invention, those skilled in the art will appreciate that the present invention is embodied in the modification that may not illustrate in this article.Thus, for this reason, only true scope of the present invention should be determined with reference to the appended claims.
Claims (13)
1., for phenylcyclohexane being oxidized to a method for cyclohexylbenzene hydroperoxide, the method comprises:
Produce and comprise cyclohexylbenzene hydroperoxide with being oxidized described cyclohexyl benzo, contact under the condition of the effluent of the degradation production of cyclic imide that cyclic imide that unreacted N-replaces replaces with this N-under the existence of a cyclic imide that () makes described phenylcyclohexane and oxygen-containing gas replace at N-;
(b) with this effluent of alkaline purification being selected from (i) ammonia, (ii) ammonium hydroxide aqueous solution, (iii) aqueous hydroxylamine and (iv) pyridine, so that described unreacted imide at least partially and described degradation production are converted into adducts or salt;
C () is separated at least partially by described adducts or salt from described effluent; With
D () is fed to imide building-up reactions at least partially by the adducts of separation or salt, wherein with oxyamine or its salt, this part of the adducts of separation or salt is carried out contacting that the adducts be separated or salt regenerated back the cyclic imide that N-replaces at least partially with poly carboxylic acid or its acid anhydrides, and the cyclic imide that further wherein said poly carboxylic acid or its acid anhydrides replace to produce extra N-with described oxyamine or its reactant salt.
2. the process of claim 1 wherein that contact (d) is carried out under the pH being less than 7.
3. the process of claim 1 wherein that the cyclic imide that described N-replaces meets general formula (II):
Wherein R
4, R
5, R
6and R
7be selected from the alkyl and substituted hydrocarbon radical with 1-20 carbon atom independently of one another, or be selected from group SO
3h, NH
2, OH and NO
2, or be selected from atom H, F, Cl, Br and I; X and Z is selected from C, S, CH independently of one another
2, the element of the 4th race in N, P and periodictable; Y is O or OH; K is 0,1 or 2; 0,1 or 2 with l.
4. the process of claim 1 wherein that the cyclic imide that described N-replaces comprises HP.
5. the process of claim 1 wherein that described contact (a) is carried out in the temperature of 20-150 DEG C and the pressure of 15kPa-500kPa.
6. the method for claim 5, the described temperature wherein for described contact (a) is 70-130 DEG C.
7. the method for claim 5, the described pressure wherein for described contact (a) is 15kPa-150kPa.
8. the process of claim 1 wherein that described alkali comprises ammonia, and described adducts precipitates from described response composite.
9. the process of claim 1 wherein that described alkali comprises ammonium hydroxide aqueous solution, and described adducts is dissolved in the described aqueous solution.
10. the process of claim 1 wherein that the mol ratio being added to described poly carboxylic acid in described contact procedure (d) or its acid anhydrides and described oxyamine or its salt is 0.5-10.0.
11. the process of claim 1 wherein that the mol ratio being added to described poly carboxylic acid in described contact procedure (d) or its acid anhydrides and described oxyamine or its salt is 0.8-2.0.
12. the process of claim 1 wherein that the mol ratio being added to described poly carboxylic acid in described contact procedure (d) or its acid anhydrides and described oxyamine or its salt is 1.0-1.8.
13. the process of claim 1 wherein that described contact (b) is carried out the temperature of 0-100 DEG C.
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| PCT/US2010/050970 WO2011066037A1 (en) | 2009-11-25 | 2010-09-30 | Oxidation of hydrocarbons |
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| EP1862442A1 (en) * | 2005-03-07 | 2007-12-05 | Daicel Chemical Industries, Ltd. | Process for oxidation of organic compounds |
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