CN102083777A - Process for producing phenol - Google Patents
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- CN102083777A CN102083777A CN2009801249907A CN200980124990A CN102083777A CN 102083777 A CN102083777 A CN 102083777A CN 2009801249907 A CN2009801249907 A CN 2009801249907A CN 200980124990 A CN200980124990 A CN 200980124990A CN 102083777 A CN102083777 A CN 102083777A
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Abstract
In a process for producing phenol, cyclohexylbenzene is oxidized to produce cyclohexylbenzene hydroperoxide and then the resultant cyclohexylbenzene hydroperoxide is cleaved to produce an effluent stream comprising phenol and cyclohexanone. At least a portion of the effluent stream is then fed to at least one dehydrogenation reaction zone, where the effluent stream portion is contacted with a dehydrogenation catalyst under conditions effective to convert at least part of the cyclohexanone in the effluent portion into phenol and hydrogen.
Description
The cross reference of related application
The application requires the rights and interests of the U.S. Provisional Application sequence number of submitting on August 29th, 2,008 61/093,042 formerly and the European application of submitting on November 18th, 2008 number 08169307.9, and the full content of these two pieces of applications is combined in herein by reference.
The field
The present invention relates to produce the method for phenol.
Background
Phenol is product important in the chemical industry, and can be used for for example production of resol, dihydroxyphenyl propane, ε-Ji Neixianan, hexanodioic acid and softening agent.
At present, the most frequently used route that is used for phenol production is the Hock method.This is a kind of three one step process, and wherein first step relates to benzene with the propylene alkylation to produce isopropyl benzene, and isopropyl benzene is oxidized to corresponding hydroperoxide subsequently, and described then hydroperoxide are cleaved to produce the phenol and the acetone of equimolar amount.Yet the demand growth of world Pyrogentisinic Acid's demand comparison acetone is rapider.In addition, because the exploitation shortage of propylene, the cost of propylene increases probably.Therefore, use higher alkene more replace propylene as charging and coproduction more the method for higher ketone rather than acetone may be to produce the attractive alternative route of phenol.
For example, the oxidation of phenylcyclohexane (similar with cumene oxidation) can be provided for the alternative route of phenol production, and does not have the problem of cogeneration of propanone.This alternative route is undertaken by the phenylcyclohexane hydroperoxide, and described phenylcyclohexane hydroperoxide are cleaved to produce the phenol and the pimelinketone of equimolar amount basically.
Yet, be that pimelinketone and phenol produce the azeotropic mixture of being made up of 28wt% pimelinketone and 72wt% phenol in a problem of producing in the phenol by the cracking of phenylcyclohexane hydroperoxide.Therefore, any trial by simple distillation separating and cracking effluent all causes this azeotropic mixture.And, although pimelinketone is the valuable product with growing market, at present pimelinketone there is not big world commerce market; Most of pimelinketone are produced and are consumed at the scene as intermediate.Therefore, in some cases, may wish to increase the amount of phenol in the product mixtures that derives from the phenylcyclohexane oxidation, perhaps even produce all phenol and do not have pimelinketone.According to the present invention, a kind of integrated approach that is used for being produced by phenylcyclohexane phenol is provided, this method helps to control the amount of pimelinketone in the final product.
Especially, the invention provides and a kind ofly be oxidized to the method that phenol is produced in phenylcyclohexane hydroperoxide and phenylcyclohexane hydroperoxide cracking subsequently, wherein make at least a portion derive from the effluent experience dehydrogenation step of cleavage step by phenylcyclohexane.Described dehydrogenation not only makes at least a portion pimelinketone in the described effluent part change into other phenol, and generating hydrogen as by product, described hydrogen for example can be recycled to the initial benzene hydrogenation alkylation step that is used to produce the phenylcyclohexane charging.In addition, although the cracking effluent part of experience dehydrogenation step can be the pure basically pimelinketone cut of being produced from the phenol of original effluent and lightweight and heavy tailing by separating, but consider this isolating cost, described method also can be applied to contain the effluent part of some or all phenol that produce in cleavage step.In this mode, if the total cost of the final pimelinketone logistics of final phenol stream of purifying and existence can be minimized.
General introduction
In one aspect, the invention reside in a kind of method of producing phenol, this method comprises:
(a) with the phenylcyclohexane oxidation, to produce the phenylcyclohexane hydroperoxide;
(b) the phenylcyclohexane hydroperoxide that will derive from (a) transform, and comprise the effluent logistics of phenol and pimelinketone with generation;
(c) the described effluent logistics of at least a portion is fed at least one dehydrogenation reaction zone; With
(d) make the logistics of described at least a portion effluent and dehydrogenation catalyst in described dehydrogenation reaction zone, contact under the dehydrogenation condition that will change into phenol and hydrogen effectively at least a portion pimelinketone in the logistics of described at least a portion effluent, described dehydrogenation condition comprises about 250 ℃-Yue 500 ℃ temperature.
In one embodiment, the described at least a portion effluent logistics that the is fed to described dehydrogenation reaction zone identical composition of effluent logistics that has and produce by described conversion (b).
In another embodiment, described method further comprises makes the effluent logistics that produces by described conversion (b) experience at least one separating step, makes the described at least a portion effluent logistics that is fed to described dehydrogenation reaction zone comprise the phenol that lacks than the effluent logistics that produces by described conversion (b).Expediently, make the effluent logistics that produces by described conversion (b) experience at least one separating step, make the described at least a portion effluent logistics that is fed to described dehydrogenation reaction zone comprise and be less than 50wt%, for example be less than 30wt%, for example be less than the phenol of 1wt%.In addition, before the logistics of described at least a portion effluent is fed to described dehydrogenation reaction zone, can makes the effluent logistics that produces by described conversion (b) experience at least one separating step and be lower than the component of 155 ℃ (measuring) and/or the component that boiling point is higher than 182 ℃ (measuring at 101kPa) at 101kPa to remove boiling point.
Expediently, the described dehydrogenation condition in (d) comprises about 300 ℃-Yue 450 ℃ temperature.
Expediently, (d) the described condition in comprises the about 20atm of about 0.01atm-(1kPa-2000kPa), the pressure of the about 3atm of for example about 1atm-(100kPa-300kPa).
Expediently, hydrogen is fed to described dehydrogenation reaction zone with the logistics of described at least a portion effluent, makes that usually the mol ratio of hydrogen and pimelinketone is about 0 in the charging of dehydrogenation reaction zone: about 4: 1 of 1-.Expediently, at least a portion hydrogen that is fed to described dehydrogenation reaction zone is the hydrogen that produces in described contact (d).
In yet another aspect, the invention reside in a kind of method of producing phenol by benzene, this method comprises:
(a1) benzene is contacted under the hydroalkylation condition with catalyzer with hydrogen, to produce phenylcyclohexane;
(a) will derive from the phenylcyclohexane oxidation of (a1), to produce the phenylcyclohexane hydroperoxide;
(b) the phenylcyclohexane hydroperoxide that will derive from (a) transform, and comprise the effluent logistics of phenol and pimelinketone with generation;
(c) the described effluent logistics of at least a portion is fed at least one dehydrogenation reaction zone; With
(d) make the logistics of described at least a portion effluent and dehydrogenation catalyst in described dehydrogenation reaction zone, under the dehydrogenation condition that will change into phenol and hydrogen effectively, contact at least a portion pimelinketone in the logistics of described at least a portion effluent; With
(e) at least a portion hydrogen gas recycle that will produce in described contact (d) is to described contact (a1).
Brief Description Of Drawings
Fig. 1 is based on the figure of transformation efficiency calculation of thermodynamics, pimelinketone dehydrogenation under normal pressure (101kPa) under the condition that adds and do not add nitrogen dilution agent and hydrogen to temperature.
The detailed description of embodiment
This paper has described a kind of method of producing phenol, and this method allows the pimelinketone of coproduction partly or entirely to be changed into other phenol.In the method, the phenylcyclohexane oxidation of the preparation of the shortening alkylation by benzene usually producing the phenylcyclohexane hydroperoxide, and is comprised the phenol of equimolar amount and the effluent logistics of pimelinketone basically with the cracking of described phenylcyclohexane hydroperoxide with generation then.Then, the described effluent of at least a portion is fed to dehydrogenation reaction zone, described there a part of effluent logistics contacts under the dehydrogenation condition that will change into other phenol and hydrogen effectively at the pimelinketone in described a part of effluent with dehydrogenation catalyst, and described hydrogen can be recycled to described benzene hydrogenation alkylation step (when existing).The production of phenylcyclohexane
The phenylcyclohexane that is used for present method can pass through any routine techniques, is included in acid catalyst such as zeolite beta or MCM-22 family molecular sieve and exists down with tetrahydrobenzene benzene alkylation, perhaps becomes biphenyl subsequently biphenyl hydrogenation to be produced by the benzene oxidative coupling.Yet in practice, by benzene and hydrogen are produced contacting under the hydroalkylation condition, in the presence of the hydroalkylation catalyzer, wherein the benzene following reaction of experience (1) is to produce phenylcyclohexane (CHB) usually for phenylcyclohexane:
The benzene charging of any commercially available acquisition can be used in the described hydroalkylation step, but preferably, described benzene has the purity level of 99wt% at least.Similarly, although the hydrogen source is not crucial, wish that usually described hydrogen is for 99wt% is pure at least.
Expediently, the combined feed total feed of described hydroalkylation step comprises and is less than 1000ppm, for example is less than 500ppm, for example is less than the water of 100ppm.Expediently, described combined feed total feed comprises usually and is less than 100ppm, for example is less than 30ppm, for example is less than the sulphur of 3ppm.Expediently, described combined feed total feed comprises usually and is less than 10ppm, for example is less than 1ppm, for example is less than the nitrogen of 0.1ppm.
Described hydroalkylation reaction can comprise in fixed bed, slurry-phase reactor and/or the catalytic distillation tower and carrying out at the structure of reactor of wide region.In addition, the reaction of described hydroalkylation can be carried out in single reaction zone or in a plurality of reaction zones, introduces reaction to the classification of major general's hydrogen in described a plurality of reaction zones.Suitable reaction temperature is about 100 ℃-Yue 400 ℃, for example about 125 ℃-Yue 250 ℃.Suitable reaction pressure is about 7 for about 100-, 000kPa, and for example about 500-is about 5,000kPa.The desired value of the mol ratio of hydrogen and benzene is about 0.15: about 15: 1 of 1-, for example about 0.4: about 4: 1 of 1-, about 0.9: 1 of for example about 0.4-.
Be used for described hydroalkylation catalyst for reaction and preferably comprise the molecular sieve of MCM-22 family and the dual-function catalyst of hydrogenation metal.Term used herein " MCM-22 family material " (perhaps " material of MCM-22 family " or " molecular sieve of MCM-22 family ") comprises one or more in the following material:
● make up the molecular sieve that piece (buildingblock) structure cell constitutes by first common degree (first degree) crystallinity, this structure cell has MWW framework form.(structure cell is that atoms in space is arranged, and has described crystalline structure if it spreads in the three-dimensional space.At " Atlasof Zeolite Framework Types ", the 5th edition, such crystalline structure has been discussed in 2001, the whole contents of the document is incorporated herein by reference);
● make up the molecular sieve that piece constitutes by common second degree (second degree), described structure piece is the 2-dimension tiling of such MWW framework form structure cell, has formed the individual layer of a structure cell thickness, a preferred c-structure cell thickness;
● make up the molecular sieve that piece constitutes by the second common degree, described structure piece is one or more than the layer of a structure cell thickness, is wherein made by the piling up, tamp of the individual layer of at least two structure cell thickness (packing) or bonding (binding) more than the layer of a structure cell thickness.Second degree like this makes up piling up of piece can be the mode of rule, irregular mode, random mode or their arbitrary combination; With
● the molecular sieve that any rule of the structure cell by having MWW framework form or random 2-dimension or 3-dimension constitute.
The molecular sieve of MCM-22 family has the peaked x-ray diffraction pattern of d-spacing that is included in 12.4 ± 0.25,6.9 ± 0.15,3.57 ± 0.07 and 3.42 ± 0.07 dusts usually.The X-ray diffraction data that are used to characterize described material are used copper by standard technique K α two-wire is as incident radiation and scintillometer is housed and the diffractometer of correlation computer obtains as gathering system.The molecular sieve of MCM-22 family comprises that MCM-22 (is described in U.S. Patent number 4,954,325), PSH-3 (is described in U.S. Patent number 4,439,409), SSZ-25 (is described in U.S. Patent number 4,826,667), ERB-1 (being described in european patent number 0293032), ITQ-1 (is described in U.S. Patent number 6,077,498), ITQ-2 (being described in International Patent Publication No. WO 97/17290), MCM-36 (is described in U.S. Patent number 5,250,277), MCM-49 (is described in U.S. Patent number 5,236,575), MCM-56 (is described in U.S. Patent number 5,362,697), UZM-8 (is described in U.S. Patent number 6,756,030) and their mixture.Preferably, described molecular screening is from (a) MCM-49, (b) MCM-56 and (c) isotype (isotype) of MCM-49 and MCM-56, for example ITQ-2.
Any known hydrogenation metal can be used in the described hydroalkylation catalyzer, although suitable metal comprises palladium, ruthenium, nickel, zinc, tin and cobalt, palladium is particularly advantageous.Usually, the amount of the hydrogenation metal that exists in the catalyzer is the about 10wt% of about 0.05-of catalyzer, the about 5wt% of for example about 0.1-.The MCM-22 family molecular sieve is in the embodiment of silico-aluminate therein, and the amount of the hydrogenation metal of existence makes that the mol ratio of aluminium in the molecular sieve and hydrogenation metal is about 1500 for about 1.5-, and for example about 75-is about 750, for example about 100-about 300.
Hydrogenation metal can directly be supported on the MCM-22 family molecular sieve by for example dipping or ion-exchange.Yet, in a preferred embodiment, 50wt% at least, 75wt% at least for example, and usually whole basically hydrogenation metal be supported on described molecular sieve independent but with its compound inorganic oxide on.Especially, find that by hydrogenation metal is supported on the inorganic oxide, compare with the catalyzer of equal value that hydrogenation metal wherein is supported on the molecular sieve, activity of such catalysts and its selectivity to phenylcyclohexane and dicyclohexyl benzene increase.
The inorganic oxide that is used for so compound hydroalkylation catalyzer needn't straitly limit, as long as it is stable under the condition of hydroalkylation reaction and is inert.Suitable inorganic oxide comprises the oxide compound of the periodic table of elements the 2nd, 4,13 and 14 families, for example aluminum oxide and/or titanium dioxide and/or zirconium dioxide.The numbering plan that is used for periodictable family used herein is disclosed in Chemical and Engineering News, 63 (5), 27 (1985).
Before metallic inorganic oxide and described molecular sieve is compound, described hydrogenation metal is deposited on the described inorganic oxide, expediently by dipping.Usually, described catalyst composite is produced by being total to granulation, the mixture quilt of wherein said molecular sieve and described metallic inorganic oxide is at high pressure (about usually 350-about 350,000kPa) compacted under is a pellet, perhaps described catalyst composite is produced by coextrusion, wherein said molecular sieve and described metallic inorganic oxide, randomly and independent tackiness agent, slurries are forced through die orifice.If necessary, can subsequently other hydrogenation metal be deposited on the catalyst composite of gained.
The suitable binder material comprises synthetic or naturally occurring material and inorganic materials such as clay and/or silicon-dioxide and/or metal oxide.The latter can be naturally occurring or be the form of gelatinous precipitate or gel, comprise the mixture of silicon-dioxide and metal oxide.The naturally occurring clay that can be used as tackiness agent comprises those of polynite and kaolin families, described family comprises change wilkinite and the kaolin that is commonly referred to Dixie, McNamee, Georgia and Florida clay, and perhaps wherein the essential mineral component is other material of halloysite, kaolinite, dickite, nakrite or anauxite.Such clay can use with the virgin state of initial exploitation, perhaps at first experiences calcining, acid treatment or chemical modification, is used then.Suitable metal oxide binder comprises silicon-dioxide, aluminum oxide, zirconium dioxide, titanium dioxide, silica-alumina, silica-magnesia, silicon-dioxide-zirconium dioxide, silica-thorium oxide, silica-beryllia, silica-titania and ternary composition such as silica-alumina-Thorotrast, silica-alumina-zirconium dioxide, silica-alumina-magnesium oxide and silica-magnesia-zirconium dioxide.
Although described hydroalkylation step is a high selectivity to phenylcyclohexane, the effluent that derives from described hydroalkylation reaction contains the product of some dialkyl groupization and unreacted aromatic feed and desirable monoalkylation species usually.Unreacted aromatic feed reclaims and is recycled to alkylation reactor by distillation usually.The bottom material that derives from benzene distillation is further distilled, so that monocycle hexyl benzene product is separated with other heavy constituent with any dicyclohexyl benzene.The amount that depends on the dicyclohexyl benzene that exists in the reaction effluent may wish to make described dicyclohexyl benzene and other benzene to carry out the alkyl exchange, so that the maximum production of desirable monoalkylation species.
With the alkyl exchange of other benzene usually in the transalkylation reactor of separating with described hydroalkylation reactor, at the molecular sieve of suitable alkyl exchange catalysts such as MCM-22 family, zeolite beta, MCM-68 (referring to U.S. Patent number 6,014,018), carries out on zeolite Y or the mordenite.Transalkylation reaction is being carried out under the Partial Liquid Phase condition usually at least, and described condition comprises the pressure of temperature that about 100-is about 300 ℃ and/or the about 3500kPa of about 800-and/or aptly based on the weight hourly space velocity and/or about 1 of the about 10hr-1 of the about 1-of whole feed charging meter: the benzene that 1-is about 5: 1/dicyclohexyl benzene weight ratio.
The phenylcyclohexane oxidation
In order to make phenylcyclohexane change into phenol and pimelinketone, at first phenylcyclohexane is oxidized to corresponding hydroperoxide.This finishes by oxygen-containing gas such as air are introduced in the liquid phase that contains phenylcyclohexane.Different with isopropyl benzene, very slow at the atmospheric oxidn that does not have phenylcyclohexane in the presence of the catalyzer, and therefore oxidation is carried out in the presence of catalyzer usually.
The suitable catalyst that is used for the phenylcyclohexane oxidation step is to be described in U.S. Patent number 6,720, the cyclic imide that the N-hydroxyl of 462 (being combined in herein by reference) replaces, N-hydroxyphthalimide for example, 4-amino-N-hydroxyphthalimide, 3-amino-N-hydroxyphthalimide, tetrabromo-N-hydroxyphthalimide, tetrachloro-N-hydroxyphthalimide, N-hydroxyl hetimide, N-hydroxyl himimide, N-hydroxyl trimellitic acid imide, N-hydroxybenzene-1,2,4-tricarboxylic acid imide, N, N '-dihydroxyl (pyromellitic diimide), N, N '-dihydroxyl (benzophenone-3,3 ', 4,4 '-tetracarboxylic acid diimide), N-hydroxyl maleimide, pyridine-2, the 3-dicarboxylic acid imides, N-hydroxy-succinamide, N-hydroxyl (tartrate imide), N-hydroxyl-5-norbornylene-2, the 3-dicarboxylic acid imides, outward-N-hydroxyl-7-oxabicyclo [2.2.1] heptan-5-alkene-2, the 3-dicarboxylic acid imides, N-hydroxyl-cis-hexanaphthene-1, the 2-dicarboxylic acid imides, N-hydroxyl-cis-4-tetrahydrobenzene-1, the 2-dicarboxylic acid imides, N-hydroxyl naphthalimide sodium salt or N-hydroxyl-adjacent benzene disulfonyl imines.Preferably, described catalyzer is the N-hydroxyphthalimide.Another kind of appropriate catalyst is N, N ', N " trihydroxy-isocyanuric acid.
These materials can use separately or use in the presence of radical initiator, and can be used as the homogeneous catalyst use of liquid phase, perhaps can be supported on the solid carrier so that heterogeneous catalyst to be provided.Usually, " the trihydroxy-isocyanuric acid is with the 0.0001mol%-15wt% of phenylcyclohexane, and for example the amount of 0.001-5wt% is used for cyclic imide or N that described N-hydroxyl replaces, N ', N.
The conditions suitable that is used for described oxidation step comprises about 70 ℃-Yue 200 ℃, for example about 90 ℃-Yue 130 ℃ temperature and/or about 50-10, and the pressure of 000kPa.Any oxygen-containing gas, preferred air can be used as oxidizing medium.Reaction can be carried out in batch reactor or continuous flow reactor.Can add ealkaline buffer, with and the acidic by-products that between oxidation period, may form reaction.In addition, can introduce water, it can help dissolve basic compounds, for example yellow soda ash.
The cracking of hydroperoxide
Change into the cracking that final reaction step in phenol and the pimelinketone relates to the phenylcyclohexane hydroperoxide at phenylcyclohexane, its expediently by make described hydroperoxide and catalyzer in liquid phase at about 20 ℃-Yue 150 ℃, for example about 40 ℃-Yue 120 ℃ temperature and/or about 50-about 2,500kPa, the pressure of the about 1000kPa of for example about 100-contact down carry out.Described phenylcyclohexane hydroperoxide preferably are diluted in described scission reaction organic solvent inert such as methylethylketone, pimelinketone, phenol or the phenylcyclohexane, to help heat extraction.Described scission reaction is carried out in the catalytic distillation device expediently.
The catalyzer that is used for described cleavage step can be homogeneous catalyst or heterogeneous catalyst.
Suitable homogeneous cleavage catalyst 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 cleavage catalyst.Preferred homogeneous cleavage catalyst is a sulfuric acid, and preferred concentration is 0.05-0.5wt%.For homogeneous acid catalyst, after cleavage step, be preferably neutralization procedure.Such neutralization procedure is usually directed to contact with basic component, subsequently with rich saliniferous water decantation.
The suitable heterogeneous catalyst of cracked that is used for the phenylcyclohexane hydroperoxide comprises smectic clays, for example be described in U.S. Patent number 4,870,217 acid polynite silica-alumina clay, whole disclosures of this patent are combined in herein by reference.
The aftertreatment of cracking effluent
The effluent that derives from scission reaction comprises the phenol and the pimelinketone of equimolar amount basically.Present method contacts with dehydrogenation catalyst so that some or all pimelinketone in the effluent are changed into other phenol according to reaction (2) by making at least a portion cracking effluent, and the favourable route of the amount that increases the phenol of being produced by original CHB or benzene charging is provided:
Any suitable dehydrogenation catalyst can be used to reaction (2), for example is described in U.S. Patent number 4,417, the promoted nickel catalyzator in 076.The conditions suitable that is used for described dehydrogenation step comprises about 250 ℃-Yue 500 ℃ temperature and/or the pressure of the about 20atm of about 0.01atm-(1kPa-2000kPa), for example about 300 ℃-Yue 450 ℃ temperature and the pressure of the about 3atm of about 1atm-(100kPa-300kPa).
In the said temperature scope, the dehydrogenation of pimelinketone is an equilibrium-limited.Fig. 1 is the maximum figure that is presented at dehydrogenation reaction under the specified requirements, described figure is based on using D.R.Stull, E.F.Westrum, and G.C.Sinke, The Chemical Thermodynamics ofOrganic Compounds, Robert E.Krieger Publishing Company publishes, Malabar, the calculation of thermodynamics that the free energy data among the Florida (1987) are carried out.Use standard thermodynamic to calculate (referring to for example Chemical Engineering Thermodynamics, R.E.Balzhiser, M.R.Samuels, and J.D.Eliassen; Prentice-Hall, Englewood Cliffs, NJ (1972) estimates the equilibrium conversion of pimelinketone to phenol.Fig. 1 indicates, and under 1 normal atmosphere (101kPa) stagnation pressure and adopt pure fed cyclohexanone,, must operate under the temperature more than 275 ℃ or 275 ℃ to phenol conversion in order to realize at least 90% pimelinketone.Under lower stagnation pressure, move or use gas such as nitrogen and/or methane dilution, increased equilibrium conversion, and co-fed hydrogen tends to reduce equilibrium conversion reactionlessness.Yet co-fed hydrogen helps to be extracted in the hydrogen that generates in the described dehydrogenation reaction, to be used for other processing step, especially for (choosing wantonly) benzene hydrogenation alkylation step, and also improves catalyst stability usually.Hydrogen by co-fed to the situation of described dehydrogenation reaction, the speed that hydrogen adds makes that usually the mol ratio of hydrogen and pimelinketone is about 0 in the charging of dehydrogenation reaction: about 4: 1 of 1-.
The reactor configuration that is used for described method of dehydrogenating generally includes one or more fixed-bed reactor that contain the solid catalyst with dehydrogenation functionality.The single of pimelinketone passes through transformation efficiency usually greater than 70%, and is preferably greater than 90%.Can be ready to the heat absorption of reaction, preferably by having a plurality of heat insulation bed of interstage heat exchanger.The temperature of reactant flow reduces by each catalyst bed the time, and raises by described heat exchanger then.Preferably, use 3-5 bed, wherein reduce to 30-100 ℃ by the temperature of each.Preferably, last in this series moved under the temperature out than first height of bed in this series.
As previously mentioned, pimelinketone and phenol produce the azeotropic mixture of being made up of 28wt% pimelinketone and 72wt% phenol, therefore cause this azeotropic mixture by the simple distillation separation from any trial of the effluent of phenylcyclohexane hydroperoxide cleavage step.Yet, by in partial vacuum at least, distill being lower than under the pressure of 101kPa usually, can improve separation efficiency.In addition, known extractive distillation process can be used for separating ring hexanone and phenol, referring to for example U.S. Patent number 4,021,490,4,019,965,4,115,207,4,115,204,4,115,206,4,201,632,4,230,638,4,167,456,4,115,205 and 4,016,049.Yet phenol/pimelinketone separates the process that remains expensive, and therefore in one embodiment, the charging of dehydrogenation step has the composition identical with the cracking effluent, has avoided the needs to the separating step of initial costliness thus.The efficient that depends on the pimelinketone dehydrogenation, final product can contain whole basically phenol, has reduced the problem of separating phenol from the cracking effluent thus at least.
In another embodiment, before dehydrogenation, make the cracking effluent experience one or more sepn processes, with one or more components that reclaim or remove described effluent.Especially, make described cracking effluent experience at least the first separating step expediently,, make the effluent logistics of sending into described dehydrogenation reaction comprise usually and be less than 50wt% from described effluent, to reclaim some or all phenol, for example be less than 30wt%, for example be less than the phenol of 1wt%.The separation of phenol is undertaken by vacuum and/or extractive distillation expediently.Before dehydrogenation reaction is sent in described effluent logistics, can use other distilation steps, removing component such as benzene and the tetrahydrobenzene that boiling point is lower than 155 ℃ (measuring at 101kPa), and/or boiling point is higher than component such as the 2-phenylphenol and the phenyl ether of 185 ℃ (measuring at 101kPa).
By adopting method of dehydrogenating of the present invention, the whole basically pimelinketone in phenylcyclohexane hydroperoxide cracking effluent can be converted to phenol.Yet, in practice, depend on market situation, have remarkable demand to the pimelinketone product.This can adopt present method to depend on the reversible character of reaction (2), promptly by making at least some phenol hydrogenation winding hexanones come easily to satisfy.This can for example easily realize in the following manner: make phenol and hydrogen in the presence of hydrogenation catalyst such as platinum or palladium, comprising for example about 20 ℃-Yue 250 ℃ temperature and/or the pressure and/or about 1 of the about 10000kPa of about 101kPa-: contact under the condition of the hydrogen that 1-is about 100: 1/phenol mol ratio.
Although described and for example clear the present invention, it will be appreciated by the skilled addressee that the present invention is suitable for not necessarily illustrational in this article modification with reference to particular.Therefore, in order to determine true scope of the present invention, should be only with reference to the appended claims.
Claims (15)
1. method of producing phenol, this method comprises:
(a) oxidation phenylcyclohexane is to produce the phenylcyclohexane hydroperoxide;
(b) the phenylcyclohexane hydroperoxide that will derive from (a) transform, and comprise the effluent logistics of phenol and pimelinketone with generation;
(c) the described effluent logistics of at least a portion is fed at least one dehydrogenation reaction zone; With
(d) logistics of described at least a portion effluent is contacted in described dehydrogenation reaction zone under the dehydrogenation condition that will change into phenol and hydrogen effectively at least a portion pimelinketone in the logistics of described at least a portion effluent with dehydrogenation catalyst, described dehydrogenation condition comprises 250 ℃-500 ℃ temperature.
2. method of producing phenol by benzene, this method comprises:
(a1) benzene is contacted under the hydroalkylation condition with catalyzer with hydrogen, to produce phenylcyclohexane;
(a) will derive from the phenylcyclohexane oxidation of described contact (a1), to produce the phenylcyclohexane hydroperoxide;
(b) the phenylcyclohexane hydroperoxide that will derive from described oxidation (a) transform, and comprise the effluent logistics of phenol and pimelinketone with generation;
(c) the described effluent logistics of at least a portion is fed at least one dehydrogenation reaction zone;
(d) logistics of described at least a portion effluent is contacted in described dehydrogenation reaction zone under the dehydrogenation condition that will change into phenol and hydrogen effectively at least a portion pimelinketone in the described effluent of described at least a portion with dehydrogenation catalyst; With
(e) at least a portion hydrogen gas recycle that will produce in (d) is to described contact (a1).
3. the method for claim 2, wherein said dehydrogenation condition comprises 250 ℃-500 ℃ temperature.
4. the identical composition of effluent logistics that the method for arbitrary aforementioned claim, the described at least a portion effluent logistics that wherein is fed to described dehydrogenation reaction zone have and produce by described conversion (b).
5. each method among the claim 1-3, further comprise making the effluent logistics that produces by described conversion (b) experience at least one separating step, make the described at least a portion effluent logistics that is fed to described dehydrogenation reaction zone contain the phenol that lacks than the effluent logistics that produces by described conversion (b).
6. the method for claim 5, further comprise and make the effluent logistics that produces by described conversion (b) experience at least one separating step, make the described at least a portion effluent logistics that is fed to described dehydrogenation reaction zone contain and be less than 50wt%, preferably be less than the phenol of 1wt%.
7. each method among the claim 1-3,5 and 6, further be included in the logistics of described at least a portion effluent is fed to before the described dehydrogenation reaction zone, make the effluent logistics that produces by described conversion (b) experience at least one separating step, be lower than the component of 155 ℃ (measuring) at 101kPa to remove boiling point.
8. each method among claim 1-3 and the 5-7, further be included in the logistics of described at least a portion effluent is fed to before the described dehydrogenation reaction zone, make the effluent logistics that produces by described conversion (b) experience at least one separating step, be higher than the component of 182 ℃ (measuring) at 101kPa to remove boiling point.
9. the method for arbitrary aforementioned claim, wherein said dehydrogenation condition comprises 300 ℃-450 ℃ temperature.
10. the method for arbitrary aforementioned claim, wherein said dehydrogenation condition comprises the pressure of 1kPa-2000kPa (0.01atm-20atm).
11. the method for claim 10, wherein said pressure are 100kPa-300kPa (1atm-3atm).
12. the method for arbitrary aforementioned claim wherein in described charging (c), is fed to described dehydrogenation reaction zone with hydrogen with the logistics of described at least a portion effluent.
13. the method for claim 12, at least a portion hydrogen that wherein is fed to described dehydrogenation reaction zone in described charging (c) are the hydrogen that produces in described contact (d).
14. the method for claim 12 or 13, wherein the mol ratio of hydrogen and pimelinketone is 0 in the charging of dehydrogenation reaction zone: 1-4: 1.
15. the method for arbitrary aforementioned claim wherein is fed to a plurality of dehydrogenation reaction zones that are connected in series with the logistics of described at least a portion effluent.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US9304208P | 2008-08-29 | 2008-08-29 | |
| US61/093,042 | 2008-08-29 | ||
| PCT/US2009/050497 WO2010024975A1 (en) | 2008-08-29 | 2009-07-14 | Process for producing phenol |
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| CN102083777A true CN102083777A (en) | 2011-06-01 |
| CN102083777B CN102083777B (en) | 2014-11-12 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107008253A (en) * | 2017-05-02 | 2017-08-04 | 湖南大学 | A kind of method of high-selectivity oxidation benzene synthesizing phenol |
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|---|---|---|---|---|
| US2291585A (en) * | 1939-12-27 | 1942-07-28 | Du Pont | Process for producing phenol from cyclohexanol and cyclohexanone |
| US6037513A (en) * | 1998-07-09 | 2000-03-14 | Mobil Oil Corporation | Hydroalkylation of aromatic hydrocarbons |
| US20030083527A1 (en) * | 2000-03-30 | 2003-05-01 | Adolf Kuhnle | Method for producing aromatic alcohols, especially phenol |
| WO2008128638A1 (en) * | 2007-04-19 | 2008-10-30 | Exxonmobil Chemical Patents Inc. | Process for oxidizing alkylaromatic compounds |
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2009
- 2009-07-14 CN CN200980124990.7A patent/CN102083777B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2291585A (en) * | 1939-12-27 | 1942-07-28 | Du Pont | Process for producing phenol from cyclohexanol and cyclohexanone |
| US6037513A (en) * | 1998-07-09 | 2000-03-14 | Mobil Oil Corporation | Hydroalkylation of aromatic hydrocarbons |
| US20030083527A1 (en) * | 2000-03-30 | 2003-05-01 | Adolf Kuhnle | Method for producing aromatic alcohols, especially phenol |
| WO2008128638A1 (en) * | 2007-04-19 | 2008-10-30 | Exxonmobil Chemical Patents Inc. | Process for oxidizing alkylaromatic compounds |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107008253A (en) * | 2017-05-02 | 2017-08-04 | 湖南大学 | A kind of method of high-selectivity oxidation benzene synthesizing phenol |
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