TW201229017A - Processes for producing phenol - Google Patents

Abstract

In a process for producing phenol and cyclohexanone, a feed comprising cyclohexylbenzene is oxidized to produce an oxidation reaction product comprising cyclohexyl-1-phenyl-1-hydroperoxide. At least a portion of the oxidation reaction product is then cleaved to produce a cleavage reaction product comprising phenol, cyclohexanone, and at least one contaminant. At least a portion of the cleavage reaction product is contacted with an acidic material to convert at least a portion of the at least one contaminant to a converted contaminant and thereby produce a modified reaction product.

Description

201229017 VI. OBJECTS OF PRIORITY: PRIORITY CLAIM This application claims priority to and benefit from U.S. Provisional Application Serial No. 6 1/3,82,776, filed on Sep. 14, 2010. This article. TECHNICAL FIELD OF THE INVENTION The present invention relates to a process for producing phenol. [Prior Art] Phenol is most often produced by the Hock process. The Hock process involves the alkylation of benzene with propylene to produce cumene, the oxidation of cumene to the corresponding hydroperoxide and the cleavage of the hydroperoxide to produce a molar amount of phenol and acetone. The various steps involved in the manufacture of phenol and acetone from cumene produce a variety of contaminants that are difficult to separate from the desired phenol and acetone. If left in the phenol product, such contaminants can cause difficulty in downstream processing or render the phenol unusable for downstream processing, such as subsequent manufacture of bisphenol or polycarbonate. Therefore, techniques have been proposed to remove those contaminants: • Contain specific treatments. For example, U.S. Patent No. 5,064,507 discloses the production of high purity phenol by cleavage from cumene hydroperoxide via one or more amine treatment steps. The phenol mixture includes at least 0.5% by weight to not more than 10% by weight of α-methylstyrene, and further includes acetol, 2-phenylpropanal (2: fluorene), methyl benzofuran (MBF), and different Propylene ketone (oxime) and carbonyl impurities. Further, U.S. Patent No. 3,3,22,6,5,1, discloses a method of producing phenol by decomposing cumene hydroperoxide to -5 - 201229017. The phenol is purified by contacting the carbonyl compound with a nitrogen compound. Cyclohexanone is usually produced by oxidizing cyclohexane or hydrogenating a phenol. These methods can also produce various contaminants that are difficult to separate from the desired product and can render the cyclohexanone product less than standard or can not be used in downstream processes, such as the manufacture of caprolactam or adipic acid, or further use. These derivatives produce nylon of one or another substance type. Therefore, specific treatments for removing those contaminants from cyclohexanone have been described. For example, U.S. Patent No. 7,99,27,1 discloses a method of reducing the concentration of cyclohexenone in an organic mixture containing cyclohexanone. The method comprises contacting an organic mixture comprising cyclohexenone with at least one of an effective amount of sulfurous acid, a sulfite, an alkali metal hydroxide, or a mixture of two or more of the compounds. The manufacture of phenol from cyclohexylbenzene is an emerging technology with an interest in the simultaneous manufacture of cyclohexanone rather than acetone. Cyclohexylbenzene can be produced, for example, by direct alkylation of benzene with cyclohexene, or by the presence of a catalyst in the presence of a catalyst, as disclosed in U.S. Patent No. 6,037,513. Made by contact. The cyclohexylbenzene can then be oxidized to the corresponding hydroperoxide and the peroxide can be cleaved to phenol and cyclohexanone using an acidic cleavage catalyst. The manufacture of phenol and cyclohexanone from cyclohexylbenzene also produces a variety of contaminants that are difficult to separate from the desired product. However, those contaminants and isolates contained therein are substantially different from those conventionally used in the Hock process for phenol and acetone or the conventional process for producing cyclohexanone from cyclohexane or phenol. For example, the hydroalkylation of benzene produces particularly large amounts of cyclohexane and minor amounts of methylcyclopentane, cyclohexene, phenylcyclohexene and phenylcyclohexadiene. Similarly

S -6- 201229017, the oxidation reaction of cyclohexylbenzene usually produces a peroxide substance different from the Hock method, such as the desired cyclohexyl-1-phenyl-1-hydroperoxide (CHBHP) and undesired Hydroperoxide by-products such as cyclohexyl-1-phenyl-2-hydroperoxide, cyclohexyl-1-phenyl-3.hydroperoxide and cyclohexyl-1-phenyl-4-hydrogen .peroxide. Finally, the cleavage of the various hydroperoxide products produces both the desired product of the hydroperoxide and the desired by-product of the desired CHBHP, either Hock or cyclohexane or phenol hydrogenation. The chemical and technology of the law does not produce a wide range of contaminant substances. There is a need to manipulate a contaminant produced by the production of phenol and cyclohexyl copper from cyclohexylbenzene, and this method is capable of producing a high quality phenol or cyclohexanone product. [Invention] In various embodiments, the invention relates to a manufacturing A method of phenol and cyclohexanone, comprising: (a) oxidizing at least a portion of a feed comprising cyclohexylbenzene to produce an oxidized composition comprising cyclohexyl-1-phenyl-1-hydroperoxide; Catalyzing at least a portion of the oxidizing composition to produce a cleavage reaction mixture comprising phenol, cyclohexanone, and at least one contaminant; and (c) contacting at least a portion of the cleavage reaction mixture with the acidic material to render at least a portion of The contaminants are converted to converted contaminants, thereby producing a modified reaction mixture. [Embodiment] -7-201229017 Various specific embodiments of the present invention will be described in terms of variations and examples, including the preferred embodiments and definitions used herein for the purpose of understanding the claimed invention. While the following detailed description has set forth the preferred embodiments of the invention, The scope of the present invention is intended to mean any one or more of the scope of the appended claims, including equivalents, and equivalents. Any reference to "this invention" may mean one or more of the inventions defined by the scope of the patent application, but not necessarily all. The present invention relates to a process for producing phenol and cyclohexanone from cyclohexylbenzene, and more particularly to an integrated process for producing phenol and cyclohexanone from benzene via cyclohexylbenzene as an intermediate. In this method, cyclohexylbenzene is first oxidized to produce an oxidation reaction product comprising cyclohexyl-1-phenyl-1-hydroperoxide, and at least a portion of the oxidation reaction product is cleaved to produce a phenol-containing ring. A cleavage reaction product of ketone and one or more contaminants. Some or all of the contaminants in the cleavage reaction product are often difficult to separate from phenol and/or cyclohexanone by simple methods such as distillation. Thus, in the process of the present invention, at least a portion of the cleavage reaction product is contacted with an acidic material under conditions such that at least one of the contaminants is converted to a converted contaminant, the converted contaminant can be easily Separation of phenol and/or cyclohexanone. Manufacture of cyclohexylbenzene In an integrated process for the production of phenol and cyclohexanone from benzene, benzene is first converted to cyclohexylbenzene by any conventional technique, including benzene and cyclohexene in an acid catalyst.

S-8-201229017 An alkylation reaction underneath (such as zeolite/3 or MCM-22 family molecular sieves), or oxidative coupling of benzene to produce biphenyl, followed by hydrogenation of biphenyl. However, in practice cyclohexylbenzene is usually produced by contacting benzene with hydrogen under hydroalkylation conditions in the presence of a hydroalkylation catalyst, thus allowing benzene to undergo the following reaction (1) to produce cyclohexylbenzene. (CHB):

For an example of the hydro-alkylation reaction of benzene in the presence of hydrogen to produce cyclohexylbenzene, reference is made to U.S. Patent No. 6,730,625, the disclosure of which is incorporated herein by reference. Reference is also made to the international application WO 20 09 1 3 1 769 or W02009 1 28 9 84 for the catalytic hydroalkylation reaction of benzene in the presence of hydrogen to produce cyclohexylbenzene. Any commercially available benzene feed can be used in the hydroalkylation reaction, but benzene preferably has a purity of at least 99 wt. Likewise, although the hydrogen source is not critical, it is generally desirable that the hydrogen have a purity of at least 99% by weight. The hydroalkylation reaction can be carried out in a wide variety of reactor configurations including fixed bed, slurry reactors and/or catalysts. Distillation column. Alternatively, the hydroalkylation reaction can be carried out in a single reaction zone or in a plurality of reaction zones, wherein at least the hydrogen is introduced into the reaction in stages. A suitable reaction temperature is between about 100 ° C and about 4,000 ° C, such as between about 1 25 ° C and about 250 ° C, and the reaction pressure of 201229017 is between Between about 100 and about 7,000 kPa, such as between about 500 and about 5,000 kPa. Suitable hydrogen to benzene molar ratios are between about 0.15:1 and about 15:1, such as between about 0.4:1 and about 4:1, such as between about 0.4:1 and about 0.9. : 1 between. The catalyst used in the hydroalkylation reaction is a bifunctional catalyst comprising a molecular sieve of the MCM-22 family and a hydrogenation metal. The term AMCM-22 family material 〃 (or "MCM-22 family material 〃 or " MCM-22 family molecular sieve 〃) as used herein includes molecular sieves having a MWW architecture topology. (The crystal structures are discussed in the fifth edition of the Atlas of Zeolite Framework Types, 2001, which is incorporated herein by reference). Molecular sieves of the MCM-22 family typically have an X-ray diffraction pattern comprising a maximum d-spacing of 12.4 ± 0.25, 6.9 ± 0.15, 3.57 ± 0.0 7 and 3.42 ± 0.07 angstroms. The X-ray diffraction data used to describe the characteristics of the material (b) is a standard technique using a Κ-α doublet line of copper as the incident radiation line and a diffractometer equipped with a scintillation counter and combined with a computer as a collection system. And get. Molecular sieves of the MCM-22 family include MCM-22 (described in U.S. Patent No. 4,954,325), PSH-3 (described in U.S. Patent No. 4,439,409), SSZ-25 (described in U.S. Patent No. 4,826,667), ERB. -1 (described in European Patent No. 0293032), ITQ-1 (described in U.S. Patent No. 6,077,498), ITQ-2 (described in International Patent Publication No. WO97/1 7290), MCM-36 ( It is described in U.S. Patent No. 5,250,277, the disclosure of U.S. Patent No. 5,236,575, issued to U.S. Patent No. 5,236,575, issued to U.S. Patent No. 5,362,.

U.S. Pat. No. 6,2012,290, the entire disclosure of U.S. Patent No. 6, 756, 030, and U.S. Patent No. 6,756,030. The molecular sieve is preferably selected from the group consisting of (a) MCM-49, (b) MCM-56 and (c) isoforms of MCM-49 and MCM-56, such as iTQ-2. Any known hydrogenation metal can be used in the hydroalkylation catalyst, although suitable metals include palladium, rhodium, nickel, zinc, tin and cobalt, with palladium being particularly advantageous. The amount of hydrogenation metal typically present in the catalyst is between about 〇5〇 and about 10% by weight, such as between about 0.1 and about 5% by weight, based on the catalyst. Suitable binder materials include synthetic or naturally occurring materials as well as inorganic materials such as clay, vermiculite and/or metal oxides. The latter may be naturally occurring or in the form of a gelatinous precipitate or gel comprising a mixture of vermiculite and metal oxide. Naturally occurring clays that can be used as binders include those of the microcrystalline kaolinite and kaolin families, including subbentonite and kaolin, commonly known as Dixie, McNamee, Georgia, and Florida clays, or the main mineral component thereof. Others of the Syrian Stone, Kaolinite, Dick Stone, Pearl Stone or Fuyu Kaolinite. These clays may be used in their original state or may be initially calcined, acid treated or chemically modified. Suitable metal oxide binders include vermiculite, alumina, zirconia, titania, vermiculite-alumina, vermiculite-magnesia, vermiculite-chromia, vermiculite-yttria, vermiculite-alumina Vermiculite-titanium oxide, and ternary compositions such as vermiculite-alumina-yttria, vermiculite-alumina-chromia, vermiculite-alumina-magnesia, and vermiculite-magnesia-chromium oxide. While the hydroalkylation reaction has a high selectivity towards cyclohexylbenzene, the effluent from the hydroalkylation reaction typically contains some dialkylated product as well as unreacted benzene and the desired monoalkylated material. Unreacted benzene is normally recovered by -11 - 201229017 and recycled to the alkylation reactor by distillation. The bottoms fraction from the benzene distillation can be further distilled to separate the monocyclohexylbenzene product from any dicyclohexylbenzene and other heavy ends. Depending on the amount of dicyclohexylbenzene present in the reaction effluent, it may be desirable to (a) transalkylate the dicyclohexylbenzene with additional benzene, or (b) dealkylate the dicyclohexylbenzene to the desired The manufacture of monoalkylated materials is maximized. The additional benzene transalkylation reaction is usually carried out on a suitable transalkylation catalyst in a transalkylation reactor separate from the hydroalkylation reactor, such as molecular sieves of the MCM-2 2 family, zeolite/3, MCM. -68 (see U.S. Patent No. 6,014,018), zeolite Y, zeolite USY and mordenite. The transalkylation reaction is generally carried out under at least a portion of the liquid phase conditions, suitably comprising a temperature of from about 100 to about 300 ° C, a pressure of from about 800 to about 3 500 kPa, from about 1 to about 10 hours on a total feed. -1 weight hourly space velocity and a weight ratio of benzene to dicyclohexylbenzene of from about 1:1 to about 5:1. After removing unreacted benzene and polyalkylated benzene and other heavy fraction materials, cyclohexylbenzene is fed to the oxidation reaction. However, this cyclohexylbenzene feed typically contains the following contaminants produced as a by-product of its synthesis: . between 1 wp pm and 1 wt% of bicyclohexane' or between 10 wppm and 8000 wppm. Bicyclohexyl; • Biphenyl between 1 wppm and 1 wt% or biphenyl between 10 wppm and 8000 wppm; methylcyclopentyl group between 1 wppm and 2 wt% Benzene' or a methylcyclopenta group between 10 wppm and 1 wt% wppm can be any of the following isomers: 丨_phenyl-1-methylcyclopentane, 1-phenyl- 2-

-12- S 201229017 methylcyclopentane and 1-phenyl-3-methylcyclopentane; and • less than about 1 000 wppm, such as less than 100 wppm of phenol, olefin or alkylbenzene, such as Cyclohexenylbenzene. Oxidation reaction As discussed above, the process comprises oxidizing at least a portion of the feed comprising cyclohexylbenzene to produce an oxidized composition comprising cyclohexyl-1-phenyl-1-hydroperoxide. As used herein, yttria means that an oxidative reaction occurs. The feed comprising cyclohexylbenzene can be made by any method known in the prior art 'although it is desirable to be a pure feed, but it may contain a small amount of a specific by-product component that is difficult to remove from cyclohexylbenzene, as later. Discussed. The hydroalkylation process can produce the by-product dicyclohexylbenzene, and thus is accompanied by and integrated with the transalkylation reaction of the by-product dicyclohexylbenzene with benzene to produce additional cyclohexylbenzene' and can further include various The unreacted benzene is recovered and recycled and the separation of the heavy alkylate and other unselected by-products is removed. Another known method of making a feed comprising cyclohexylbenzene comprises a catalyst alkylation reaction of benzene with cyclohexene. Further, in a specific example, a portion of the feed comprising cyclohexylbenzene may be a recycle stream comprising cyclohexylbenzene produced by processing the treated cracking reaction mixture' as discussed later. In this manner, all or a portion of the cyclohexylbenzene that is not reacted in the oxidation reaction can be recovered and reused to produce additional phenol. Regardless of one or more sources, in various embodiments, the feed comprising cyclohexyl-13-201229017 benzene contains at least about 10% by weight, or at least about 25% by weight, or at least about 50% by weight, or at least about 65 wt%, or at least about 75 wt%, or at least about 95 wt%, or at least about 99 wt% cyclohexylbenzene. In various embodiments, it may contain another component. For example, the feed comprising cyclohexylbenzene may contain at least 1 wppm and no more than 1 wt% bicyclohexane, or at least 10 wPpm and no more than 8000 wppm bicyclohexane. The feed may contain at least 1 wppm and no more than 1% by weight of biphenyl, or at least 10 wppm and no more than 8000 wppm of biphenyl. The feed may contain at least 1 wppm and no more than 2 wt% methylcyclopentylbenzene, or at least 10 wppm and no more than 1 wt% methylcyclopentylbenzene, which may be one of the following isomers : 1-phenyl-1-methylcyclopentane, 1-phenyl-2-methylcyclopentane and 1-phenyl-3-methylcyclopentane. There may be other components which are present alone or in any combination, although it is desirable to have a low concentration, such as no more than 1 000 wppm, or no more than 100 wppm of phenol, olefin or alkylene benzene, such as cyclohexenylbenzene. . The cyclohexylbenzene-containing feed which introduces oxygen to cause an oxidation reaction may contain cyclohexylbenzene and any combination of any of the above-mentioned other components or other components as described above, and the amount may be the ratio of each of the other components described above. Or any combination thereof. In various exemplary embodiments, the oxidation reaction can be achieved by contacting oxygen (e.g., oxygen-containing gases such as various derivatives of air and air) with a feed comprising cyclohexylbenzene. For example, air that is compressed and filtered to remove particulates, condensed by compression and cooling, and air removed, or cooled by air, concentrated at low temperature, or within the knowledge of those skilled in the art In other ways, it is about 21 moles more oxygen than normal air.

S -14- 201229017 The oxidation reaction can be carried out in the presence or absence of a catalyst. Suitable oxidizing catalysts include the N-hydroxy substituted cyclic quinone imines described in U.S. Patent No. 6,720,462, the disclosure of which is incorporated herein by reference. For example, N-hydroxy quinone imine (NHPI), 4-amino-N-hydroxy quinone imine, 3-amino-N-hydroxy quinone imine, tetrabromo-N-hydroxy quinone can be used. Amine, tetrachloro-N-hydroxy quinone imine, N-hydroxyheimide, N-hydroxyhimimide 'N-pyridyltrimethyleneimine (N-hydroxytrimellitimide), N-p-phenylene-1,2,4-trimethylimine, N,N'-dihydroxy (benzimidommine), hydrazine, Ν'-dihydroxy (two Phenyl ketone-3,3',4,4'-tetracarboxylic acid diimenimine), hydrazine hydroxy cis-iminyl imine, pyridine-2,3-dimethylimine, hydrazine-hydroxy succinate醯 醯 imine, Ν-hydroxy (tartarium imine), Ν-hydroxy-5-nordecene-2,3-dimethylimine, exo-quinone-hydroxy-7-oxabicyclo[2.2. 1]hept-5-ene-2,3-dimethylimine, hydrazine-hydroxy-cis-cyclohexane-1,2-dimethylimine, hydrazine-hydroxy-cis-4-cyclohexene- 1,2-dimethylimine, quinone-hydroxynaphthylimine sodium salt or hydrazine-hydroxy-o-benzenedisulfonimide. The catalyst is preferably quinone-hydroxy quinone imine. Another suitable catalyst is Ν,Ν',Ν"-trihydroxyisocyanuric acid. The oxidizing catalysts may be used alone or in combination with a free radical initiator and may be further used in the form of a liquid phase homogeneous catalyst or may be supported on a solid support to provide a heterogeneous catalyst. The cyclic quinone imine or hydrazine, Ν', Ν"-trihydroxyisocyano cyanide substituted by hydrazine-hydroxyl is usually used in an amount of between 0.000 1 and 15% by weight, such as 0.001, based on cyclohexylbenzene. Between 5% by weight. In various embodiments, the 'oxidation reaction occurs under oxidizing conditions. Suitable oxidizing conditions include temperatures between about 70 ° C and about 200 ° C, such as from about 90 -15 to 201229017 ° C to A pressure of about 130 t, and a pressure of about 50 to 10,000 kPa. An alkaline buffer may be added to react with acidic by-products that may form during oxidation. Additionally, an aqueous phase may be introduced. The reaction may occur in a batch or continuous flow manner. The oxidation product of the feed of benzene (i.e., the oxidized composition) typically contains at least 5% by weight, such as at least 10% by weight, such as at least 15% by weight, or at least 20% by weight, based on the total weight of the oxidized composition, of cyclohexyl. · 1 · Phenyl-1 -hydroperoxide. In other forms, the oxidizing composition contains no more than 80% by weight, or no more than 60% by weight, or no more than 40% by weight based on the total weight of the oxidized composition. % by weight, or no more than 30 5% by weight or less than 25% by weight of cyclohexyl-1-phenyl-1 hydroperoxide. The oxidizing composition may further comprise a quinone imine catalyst and unreacted cyclohexyl benzene. The invention may include oxidation At least 50% by weight, or at least 60% by weight, or at least 65% by weight, or at least 70% by weight, or at least 80% by weight, or at least 90% by weight of the cyclohexylbenzene based on the total weight of the composition of the oxidized composition In addition, the oxidizing composition may contain one or more by-products derived from the oxidation reaction of cyclohexylbenzene other than cyclohexyl-1-phenyl-1-hydroperoxide or may be included in the ring undergoing the oxidation reaction. Hydroperoxides of oxidation products of some of the oxidizable components of hexylbenzene (other than cyclohexylbenzene). These oxidizable contaminants include methylcyclopentylbenzene having various isomers, and bicyclohexane. Other examples of hydroperoxide contaminants present in the oxidizing composition include at least 0.1% by weight to no more than 10% by weight, or at least 0.5% by weight to not more than 5, based on the total weight of the oxidizing composition. 0% by weight, At least 1 wt% and not more than 4 wt% of any one of the following contaminants

S-16-201229017 or any combination thereof: cyclohexyl-1-phenyl-2-hydroperoxide, cyclohexyl 1-phenyl-3-hydroperoxide, cyclohexyl.. 1-phenyl- 4-hydroperoxide, cyclopentyl-1-methyl-2-phenyl-2-hydroperoxide, cyclopentyl-1-methyl-3-phenyl-3-hydroperoxide, ring Amyl-1-methyl-1-phenyl-2-hydroperoxide, cyclopentyl-1-methyl-1-phenyl-3-hydroperoxide; and cyclohexyl-l-phenyl- 1.2-Dihydroperoxide, cyclohexyl-1-phenyl-1,3-dihydroperoxide, cyclohexyl-1-phenyl·1,4-dihydroperoxide, cyclopentyl-1- Methyl-2-phenyl-1.2-dihydroperoxide, cyclopentyl-1-methyl-2-phenyl-2,3-dihydroperoxide, cyclopentyl-1-methyl-2 -Phenyl-2,4-dihydroperoxide and cyclopentyl-1-methyl-2-phenyl-2,5-dihydroperoxide. A reactor for the oxidation reaction of cyclohexylbenzene (i.e., an oxidation reactor) may be any type of reactor that allows oxygen to be introduced into cyclohexylbenzene and which can further effectively provide oxygen in contact with cyclohexylbenzene for oxidation reaction. . For example, the oxidation reactor can comprise a simple, open-ended vessel having a dispenser inlet for the oxygen-containing stream in the pipeline. In various embodiments, the oxidation reactor can have a means of extracting and pumping a portion of the contents through a suitable cooling device and returning the cooled portion to the reactor, thereby manipulating the exotherm of the oxidation reaction. Alternatively, a cooling coil that provides indirect cooling (e.g., with cooling water) can be operated within the oxidation reactor to remove the heat generated. In other embodiments, the oxidation reactor may comprise a plurality of reactors in series, each performing a portion of the oxidation reaction, optionally operating under selected different conditions to increase the relationship between cyclohexylbenzene or oxygen or both. The oxidation reaction in each reactor under the conversion range. The oxidation reactor can be operated in batch, semi-batch or continuous flow processes well known to those skilled in the art. -17- 201229017 may cleave at least a portion of the oxidizing composition, which may include all or a portion of the oxidizing composition that is directly fabricated without any separation (eg, from transferring some directly produced oxidizing composition to another Configuration (such as temporary storage) of the resulting part). Therefore, at least a part of the oxidized composition may have the same composition as the oxidized composition. Furthermore, all or some of the oxidized compositions produced directly may be subjected to one or more separations, and at the present time, the separated (or multiple separated) suitable products (with compositional changes) may provide at least relative to the directly produced oxidized composition. A portion of the oxidizing composition is subjected to a cleavage reaction. For example, all or a portion of the directly produced oxidic composition may be subjected to high vacuum distillation to produce a product rich in unreacted cyclohexylbenzene relative to the oxidized composition and at least a portion of the oxidized composition as a residue (wherein The concentration of the desired cyclohexyl-1-phenyl-1-hydroperoxide is increased, and the cleavage reaction can be carried out. Cyclohexylbenzene is essentially a diluent in the cleavage reaction and neutralization reaction, and it is not a good solvent for most of the acid catalysts (especially for sulfuric acid). However, unlike the Hock method described earlier, the present invention is suitably such that the oxidized composition carrying out at least a part of the cleavage reaction has the same cyclohexylbenzene composition as the directly produced oxidized composition. In other words, it is suitable that at least a portion of the oxidizing composition is not subjected to concentration of the hydroperoxide prior to introduction of the acid catalyst because the starting alkylbenzene (cyclohexylbenzene) has a significantly lower starting alkyl group than found in the Hock process. The normal boiling point of benzene (cumene). However, within the scope of the present invention, any actual separation intended to concentrate cyclohexyl-1-phenyl-1-hydroperoxide from cyclohexylbenzene and other hydroperoxides is likely to be required prior to the cleavage reaction. -18- 201229017 Unsuitable distillation equipment for very low vacuum pressures, and even then very high temperatures are likely to be required, which can cause thermal decomposition of dangerous and uncontrolled hydroperoxides. Alternatively, all or a portion of the oxidizing composition, or all or a portion of the vacuum distillation residue, may be cooled to cause unreacted quinone imine oxidation catalyst crystals, which may then be filtered or scraped for use. The crystallization heat exchanger is surface separated and provides at least a portion of the oxidizing composition that is reduced or liberated from the ruthenium oxide catalyst, which can be subjected to a cleavage reaction. As another example, all or a portion of the oxidized composition produced can be water washed and then passed through an adsorbent (such as a 3A molecular sieve) to separate water and other adsorbable compounds, and provide at least a portion of reduced water or hydrazine. An oxidizing composition of an imine content which can be subjected to a cleavage reaction. Likewise, all or a portion of the oxidizing composition can be subjected to chemical or physical based adsorption, such as removal of a ruthenium oxide catalyst (eg, NHPI) or other adsorbable component by a sodium carbonate bed, and providing At least a portion of the oxidizing composition (wherein the oxidation catalyst or other adsorbable component is reduced in content) can be subjected to a cleavage reaction. Another possible separation method involves contacting all or a portion of the oxidized composition produced with a liquid containing a base such as an alkali metal carbonate or aqueous bicarbonate solution to form a water comprising a salt of a ruthenium oxide catalyst. The phase and the quinone imine oxidation catalyst reduced organic phase provide the organic phase as an oxidizing composition capable of undergoing at least a portion of the cleavage reaction. Cleavage reaction -19-201229017 As discussed above, 'the method comprises cleavage of at least a portion of the oxidized composition in the presence of an acid catalyst to produce a cleavage reaction mixture comprising an acid catalyst, phenol and cyclohexanone" as herein The use of cleavage 〃 means that the cleavage reaction occurs. In the cleavage reaction, at least a portion of the desired cyclohexyl-1-phenyl-1-hydroperoxide will be decomposed into cyclohexanone and phenol with high selectivity and any other hydroperoxide present will be further decomposed into Various products are discussed below. In various embodiments, the acid catalyst is at least partially soluble in the cleavage reaction mixture, is stable at a temperature of at least 185 ° C and has a lower volatility (higher normal boiling point) than cyclohexylbenzene. In various embodiments, the acid catalyst is also at least partially soluble in the treated cleavage reaction mixture. Acid catalysts include, but are not limited to, Bronsted acid, Lewis acid, sulfonic acid, perchloric acid, phosphoric acid, hydrochloric acid, p-toluenesulfonic acid, aluminum chloride, fuming sulfuric acid, trioxide Sulfur, ferric chloride, boron trifluoride, sulfur dioxide and sulfur trioxide. Sulfuric acid is a preferred acid catalyst. In various embodiments, the cleavage reaction mixture contains at least 50 parts by weight (wppm) and no more than 3000 wppm acid catalyst, or at least 150 wppm and no more than 2000 wppm, based on the total weight of the cleavage reaction mixture. Acid catalyst, or an acid catalyst of at least 300 wppm and no more than 1500 wppm. In various embodiments of the invention, the cleavage reaction mixture comprises at least 50% by weight, or at least 60% by weight, or at least 6% by weight, or at least 70% by weight, or at least 8 based on the total weight of the cleavage reaction mixture. 0% by weight, or at least 90% by weight of cyclohexylbenzene.

S -20- 201229017 Due to the possible high amount of cyclohexylbenzene in the cleavage reaction mixture, which is considerably higher than the cumene in the Hock process material for the cleavage reaction, it can be suitably used in the present invention than in the Hock method. The acid catalyst, which is considered to be optimal in the amount of catalyst, is subjected to a cleavage reaction to at least partially overcome the insolubility of the acid in the cleavage reaction mixture. However, higher hydroxyl peroxide conversion can be achieved by applying a lower acid catalyst amount to the present invention, plus an appropriate additional cleavage reactor volume and residence time of the cleavage reaction mixture in the cleavage reactor. In various embodiments, the cleavage reaction occurs under cleavage conditions. Suitable cracking conditions include at least 20 ° C and no more than 200 ° C, or a temperature of at least 40 ° C and no more than 120 ° C, and at least 1 and no more than 3 70 psig (at least 7 and no more than 2,550 kPa gauge) Or a pressure of at least 14.5 and no more than 145 psig (at least 100 and no more than 1 〇〇〇 kPa gauge) such that the cleavage reaction mixture is completely or predominantly in the liquid phase during the cleavage reaction. Any hydroperoxide (such as cyclohexyl-1-phenyl-1-hydroperoxide, and suitably all cyclohexyl-1-phenyl-1-hydroperoxide and other hydroperoxides) There is typically a very high conversion in the cleavage reaction, for example at least 90.0% by weight, or at least 9.5 % by weight, or at least 9.8 % by weight, or at least 99.0% by weight, or at least 99.5% by weight, or at least 99.9% by weight, or even 100% by weight, based on the hydroperoxide or all of the cyclohexyl-1-phenyl-1- which is present in the oxidizing composition present in at least a portion of the cleavage reaction. The weight of the hydroperoxide and other hydroperoxide materials is based on the weight. This is satisfactory 'because any hydroperoxide (even cyclohexyl-1 -phenyl-1 -hydroperoxide) becomes a cleavage reaction mixture and a contaminant in the treated cleavage reaction mixture, as discussed below -21 - 201229017. When decomposed under uncontrolled conditions outside the range of the cracking reaction (e.g., thermal decomposition under conditions in a distillation column), the hydroperoxide causes undesirable chemistry. The main products of the cleavage reaction of cyclohexyl-1-phenyl-1-hydroperoxide are phenol and cyclohexanone, each typically from about 40 to about 60% by weight of the cleavage reaction mixture, or from about 4 to about 5 5% by weight, based on the weight of the cleavage reaction mixture other than unreacted cyclohexylbenzene and acid catalyst, the cleavage reaction mixture may comprise not more than 30% by weight based on the total weight of the cleavage reaction mixture, Or no more than about 25% by weight, or no more than about 15% by weight of phenol, or it may comprise at least 1% by weight, or at least 3% by weight, or at least 5% by weight, or at least 1% by weight of phenol. Further, the cleavage reaction mixture may comprise no more than 30% by weight, or no more than 25% by weight, or no more than about 15% by weight, based on the total weight of the cleavage reaction mixture, of cyclohexanone, or it may comprise at least 1% by weight , or at least 3% by weight, or at least 5% by weight, or at least 10% by weight of cyclohexanone. The cleavage reaction mixture may further comprise at least 0.1 and not more than 1% by weight, or at least 〇.5 and not more than 7% by weight, or at least 1 and not more than 5% by weight, or at least 1.5, based on the total weight of the cleavage reaction mixture. And no more than 3% by weight of any one or combination of pollutant by-products. *Contaminant " or contaminant by-product" as used herein may include any unwanted helium or oxygen in the cracking reaction mixture or the mixture of the neutralized cracking reaction mixture or any portion thereof. a hydrocarbon component; it is any substance other than phenol, cyclohexanone, and cyclohexylbenzene. Do not want

S -22- 201229017 These contaminants, because the presence of such contaminants show a decrease in the yield of the desired product phenol and cyclohexanone from cyclohexylbenzene, or the contaminants cause phenol, cyclohexanone or unconverted Difficulties in the separation and purification of cyclohexylbenzene or some combination thereof. The contaminants in the cleavage reaction mixture or the neutralized cleavage reaction mixture or any part thereof may be produced in any of the components of the present invention or may contain a cyclohexylbenzene-containing feed for the oxidation reaction. in. For example, contaminants may be present in the cleavage reaction mixture due to one or more of the following: (i) contaminants contained within cyclohexylbenzene (eg, by-products produced using hydroalkylation or alkylation reactions) (ii) a contaminant produced by an oxidation reaction of a feed comprising cyclohexylbenzene and possibly an oxidation reaction from an oxidizable component of (i); and/or (iii) from (ii) Contaminants produced by the cleavage reaction of at least a portion of the oxidizing composition. Examples of contaminants in the cleavage reaction mixture and their possible amounts include (parts per million by weight (wppm) and weight percent based on the total weight of the cleavage reaction mixture): • water, for example at least 1 〇〇wp Pm and not more than 3.0% by weight; • a bicyclic hydrocarbon having 12 carbon atoms other than cyclohexylbenzene, such as bicyclohexane, cyclohexenylcyclohexane, cyclohexanediylcyclohexane, cyclohexenylbenzene , cyclohexadienylbenzene and biphenyl, for example, each or a total of at least 1 〇 wppm and not more than 3.0% by weight; • saturated and unsaturated ketones such as pentanone, methylcyclopentanone, ketone, 1-phenyl Hexa-1-one and 1-cyclohexylhexan-1-one, phenylcyclohexanone and benzylcyclopentanone, for example, each or a total of at least 10 wppm and not more than 4. 〇 weight -23-201229017%; • Cyclohexanedione, for example a total of at least 10 wppm and not more than 1.0% by weight; • unsaturated hydrocarbons of less than 12 carbon atoms, cyclic and acyclic hydrocarbons, or combinations thereof, such as cyclohexene, For example, each or a total of at least 1 〇 wppm and not more than 1.0% by weight; • cyclohexanol, for example at least 10 wppm and Not more than 1.0% by weight; • Cyclohexenone, such as 2·cyclohexenone or 3-cyclohexenone, for example, each or a total of at least 10 wppm and not more than 2.0% by weight; • hydroxycyclohexanone, For example, a total of at least 10 wppm and not more than 2.0% by weight; • carboxylic acids, such as benzoic acid, for example each or a total of at least 10 wppm and not more than 1. 〇 by weight; • phenylcyclohexanol, such as 1-phenylcyclohexane 1-propanol, 2-phenylcyclohexan-1-ol, 3-phenylcyclohexan-1-ol, and 4-phenylcyclohexan-1-ol, for example, each or a total of at least about 10 wppm and no more than 5.0% by weight; • Cyclohexylcyclohexanol, such as 1-cyclohexylcyclohexan-1-ol, 2-cyclohexylcyclohexan-1-ol, 3-cyclohexylcyclohexan-1-ol, and 4-cyclohexyl ring Hex-1-ol, for example, each or a total of at least 1 〇W ppm and not more than 1.0% by weight; • an unsaturated alkyl oxocyclohexane such as cyclohexenylcyclohexanol and cyclohexenylcyclohexanone, and Methylcyclopentenylcyclohexanol and methylcyclopentenylcyclohexanone, for example, each or a total of at least 1 〇W ppm and not more than 1.00 wt%. > • Aldehydes, especially valeraldehyde, hexanal, cyclohexyl or methylcyclopentane

S-24-201229017 aldehydes such as 5-cyclohexylhexanal and 6-hydroxy-5-cyclohexylhexanal are, for example, each or a total of at least 1 〇wppm and not more than 1. 〇% by weight; • 1-phenyl- 6-hydroxyhexan-1-one (also known as 6-hydroxyphenylhexanone), for example at least 10 wppm and not more than 4-0 wt%; • 1-cyclohexyl-6-hydroxyhexan-1-one 'for example at least 1 〇 wppm And not more than 1.0% by weight; • benzoic acid esters, for example, each or a total of at least 10 wppm and not more than 1.0% by weight; and • hydroperoxides (for example, unreacted hydroperoxides). Non-limiting examples include: the desired cyclohexyl-1 -phenyl-1 -hydroperoxide, and other hydroperoxides such as cyclohexyl-1-phenyl-2-hydroperoxide, cyclohexyl 1-phenyl-3-hydroperoxide, cyclohexyl-1-phenyl-4-hydroperoxide; cyclopentyl-1-methyl-2-phenyl-2-hydroperoxide, ring Amyl-1-methyl-3-phenyl-3-hydroperoxide, cyclopentyl-1-methyl-1-phenyl-2-hydroperoxide, cyclopentyl-1-methyl- 1-phenyl-3-hydroperoxide; cyclohexyl-1-phenyl-1,2-dihydroperoxide, cyclohexyl-1-phenyl-1,3-dihydroperoxide, cyclohexyl -1-phenyl-1,4-dihydroperoxide; cyclopentyl-1-methyl-2-phenyl-1,2-dihydroperoxide, cyclopentyl-1-methyl-2 -phenyl-2,3-dihydroperoxide, cyclopentyl-1-methyl-2-phenyl-2,4-dihydroperoxide, cyclopentyl-1 -methyl-2-benzene Base-2,5-dihydroperoxides, for example, each or a total of at least 1 wppm and not more than 1. 〇% by weight = a reactor for carrying out the cleavage reaction (ie cleavage reactor) can be used by those skilled in the art Any type of reactor known. For example, the cleavage reactor can be a simple open vessel operated in a tank reactor mode with nearly continuous agitation, or a simple open tubular tube operated in a nearly piston fluid reactor mode. In other embodiments, the cleavage reactor comprises a plurality of reactors in series, each undergoing a portion of the conversion reaction, optionally operating in a selected different mode and under different conditions to increase the cleavage reaction under the relevant conversion range. . In one embodiment, the cleavage reactor is a catalytic distillation unit. In various embodiments, the cleavage reactor can operate by transporting a portion of the contents through the cooling unit and the cooled portion back to the cleavage reactor, thereby manipulating the exotherm of the cleavage reaction. Alternatively, the reactor can be operated adiabatically. In one embodiment, the cooling coil operating within the cleavage reactor removes any heat generated. Neutralizing the at least a portion of the cleavage reaction mixture, which may include all or a portion of the cleavage reaction mixture that is directly produced without any separation (eg, from transferring some directly produced cleavage reaction mixture to another configuration) Ji temporarily stores) some of the parts obtained). Thus, at least a portion of the cleavage reaction mixture can have the same composition as the cleavage reaction mixture. Furthermore, all or some of the directly produced cleavage reaction mixtures may be subjected to one or more separations, and at this point the composition of the separation (or multiple separations) of the composition is modified relative to the directly produced cleavage reaction mixture (wherein The compositional change) can provide at least a portion of the cleavage reaction mixture for the neutralization reaction. Contaminant treatment As discussed in _h, the cleavage reaction mixture can contain one or more contaminations.

S -26- 201229017. In various embodiments disclosed herein, the methods disclosed herein further comprise contacting at least a portion of the contaminant with an acidic material to convert at least a portion of the contaminant to the converted contaminant, thereby producing a modified Reaction mixture. Acidic materials suitable for use in the treatment of cracking reaction products include microporous acidic materials such as zeolites, aluminas and aluminosilicates, especially zeolites having a pore diameter in excess of 4 angstroms; cation exchange resins, especially sulfonic resins, such as Rohm & Haas Amberlyst 16; Brinellic acid such as formic acid, acetic acid, hydrochloric acid and sulfuric acid; sulfurous acid or a salt thereof such as sodium sulfite, sodium hydrogen sulfite and sodium metabisulfite; and an aqueous acid solution. In one embodiment, the acidic material used to treat the cleavage reaction product comprises at least a portion of an acid catalyst used to promote the cleavage reaction. The acidic material suitably has a relatively low volatility and has a higher boiling point than phenol and/or cyclohexylbenzene, allowing distillation of the bottoms product for subsequent fractionation operations that can be carried out. Contaminant treatment can be carried out directly with the cleavage reaction mixture or after one or more separations of the cleavage reaction mixture. For example, the cleavage reaction mixture can be separated (e. g., by distillation) into a phenol-rich and cyclohexanone-rich fraction before or after the contaminant treatment of the contaminant. Suitable pollution treatment conditions vary with the acidic materials used. Processing conditions include at least about 30 ° C, or at least about 35 ° C, or at least about 40 ° C, or at least about 50 ° C, or at least about 60 ° C, or at least about 70 ° C, or at least about 80 ° C, or at least about 90 ° C, or at least about 100 ° C temperature. In various embodiments, the temperature is below 250 ° C, or below about 225 ° C, or below about -27-201229017 190 ° C, or below about 180 ° C, or below about 170 t, or below About 160 ° C, or less than about 150 ° C, or less than about 140 ° C. The temperature can be in any range of the aforementioned temperatures. The pressure can range from about 0.75 psig to about 500 psig (5 kPa to 3450 kPa), or from about 10 psig to 200 psig (70 kPa to 1380 kPa), such that the cracking reaction mixture is completely or predominantly in the liquid phase during processing. In various embodiments, the pressure can be from about 10 to 200 psig (170 kP a to 1 3 80 kPa) and the temperature can be from about 60 ° C to about 160 ° C such that most of the cleavage reaction mixture is in the liquid phase. In a specific example in which the acidic material is a solid microporous material (for example, zeolite, alumina, etc.), the pressure may be about 10 to 200 psig (70 to 1 3 80 kPa) and the temperature may be about 10 ° C to At about 25 ° C, most of the cleavage reaction mixture is in the liquid phase. In various embodiments in which the acidic material is a cation exchange resin, the pressure may be from about 10 to 200 psig (70 to 1380 kPa) and the temperature may be from about 30 ° C to 100 ° C, such that most of the cleavage reaction mixture It is a liquid phase. It will be appreciated that all or a portion of the effluent reaction mixture can be contacted with an acidic material as disclosed herein. For example, contaminants in the distillate fraction containing the entire cleavage reaction mixture enriched or depleted of phenol and/or cyclohexanone relative to the cleavage reaction mixture can be contacted with an acidic material as described herein. When the logistics is described as "enriched""specific substances, it means that the weight percent of the particular material in the stream is elevated relative to the feed stream prior to separation. When a logistics is described as a "depletion" of a specific substance, it means the weight % of the specific substance in the stream.

S -28- 201229017 is reduced for the feed stream prior to separation. Alternatively, the filtered fraction of the entire cracking reaction mixture (which may be reduced in amount of the furnace component) may be contacted with an acidic material as described herein. Alternatively, a portion of the cleavage reaction mixture is subjected to an absorption operation, such as water washing, prior to contact with the acidic material to reduce the concentration of the absorbable component. Additionally or alternatively, a portion of the cleavage reaction mixture is subjected to an absorption operation prior to contact with the acidic material, such as by molecular sieves to remove water (e.g., 3A molecular sieves) such that the concentration of one or more adsorbable components is reduced. The contaminant reactor can be any vessel that allows the contaminant to contact the alkaline material for a suitable residence time. For example, the contaminant reactor can be an open or substantially open vessel reactor or reaction tube. In various embodiments, the process for making phenol and cyclohexanone comprises: (i) cleavage of a stream comprising cyclohexyl-1-phenyl-1-hydroperoxide in the presence of an acidic cleavage catalyst, Making a cleavage reaction mixture comprising phenol, cyclohexanone, an acidic cleavage catalyst, and one or more contaminants; and (ii) reacting at least a portion of the acidic cleavage catalyst with a basic material to form a neutralized stream; Iii) separating the neutralized stream into one or more streams which are enriched in cyclohexanone, phenol and/or cyclohexylbenzene relative to the neutralized stream; and (iv) a portion enriched in cyclohexanone, One or more of the phenol-rich portion and the cyclohexylbenzene-rich portion are contacted with an acidic material to remove - or multiple contaminants. In various embodiments, the cleavage reaction mixture is separated into: (1) an overhead product comprising greater than about 98% by weight or greater than -29 to 201229017 of about 99% by weight of cyclohexanone based on the total weight of the overhead product. And (2) a bottom product comprising an azeotropic ratio of phenol and cyclohexanone. The impurities contained in the overhead product may include methylcyclopentanone. As used herein, "azeotropic ratio" means about 65 to 75% by weight of phenol and about 23 to 35% by weight of cyclohexanone, or about 72% by weight of phenol and about 28, based on the total weight of the stream. % by weight of cyclohexanone. In various embodiments, a portion or the entire cleavage reaction mixture can be combined with another stream from the overall phenol production process. For example, the cleavage reaction mixture can be combined with a stream containing cyclohexanone produced by a hydrogenation process using phenol. Alternatively, the cleavage reaction mixture can be combined with a stream comprising phenol produced by a dehydrogenation process of cyclohexanone. Alternatively, the cleavage reaction mixture can be combined with one or more additives, such as an antifoaming agent or a surfactant. In various embodiments, more than one portion of the cleavage reaction mixture can be contacted with the acidic material. For example, the cleavage reaction mixture can be separated into one or more streams that are enriched in cyclohexanone, phenol, and/or cyclohexylbenzene relative to the cleavage reaction mixture, and each stream can be contacted with an acidic material. The acidic materials used for the respective fractions may be the same or different. In various embodiments, the fraction of the cleavage reaction mixture supplied can be contacted with the acidic material more than once. For example, the cyclohexanone-rich fraction obtained from the entire cracking reaction mixture may be first contacted with a first acidic material (e.g., sulfuric acid) and then separately exposed to a second acidic material (e.g., a cation exchange resin). Non-limiting examples of reactions that can occur when contaminants in the cracking reaction product are converted to converted contaminants include: • Aldol condensation reactions, especially condensation reactions of ketones and aldehydes;

S -30- 201229017 • Dehydration reaction, especially for the dehydration of alcohols; • Alkylation, especially for the alkylation of olefins and alcohols with phenol or alkylating aromatics; • Oligomerization of olefins; • Alkylation a combination of alkylation and cyclization of the product; • esterification, especially esterification of carboxylic acids and alcohols; • cracking, especially cracking of alkyl and aryl groups; • contaminant by-products Phenol molecular reaction; • where the by-product of the pollutant reacts with the cyclohexanone molecule; • where the by-product of the pollutant reacts with another pollutant by-product of the same or different species; and • any combination of the above. In various embodiments, the converted contaminants include: • characteristics that distinguish them from phenol and/or cyclohexanone more than the starting contaminants. "Separable 〃 can mean distillation, for example, the converted contaminant does not form an azeotrope with phenol and / or cyclohexanone, but will form an azeotrope with the starting pollutant by-product, or can be filtered, or Absorbable (for example, in water or aqueous acidic materials), or adsorbable; • Higher molecular weight than the starting contaminant; • Lower molecular weight than the starting contaminant; • Lower volatility than the starting contaminant. And suitably less volatile than cyclohexanone and/or phenol; • higher volatility than the starting contaminant, suitably higher than the volatility of cyclohexanone and/or phenol; -31 - 201229017 • Aldol condensation The product, usually an aldehyde and a ketone; • water that is usually neutralized from the base; • an alcohol from the saponification of the ester; and • an acid salt from a neutralization or saponification reaction. In various embodiments, it will be at least about 20.0% by weight, or at least about 5% by weight, or at least about 80.0% by weight. , or at least about 90% by weight, or at least about 99.9% by weight, or essentially all of the contaminants are converted to converted contaminants. In various embodiments, at least about 20.0% by weight, or at least about 5% by weight, or at least about 8% by weight, or at least about 0.001% by weight, or at least about 99.9% by weight of any olefinic contaminant (including The furan and alcohol) are converted to converted contaminants based on the total weight of the stream. In various embodiments, it will be at least about 20.0% by weight, or at least about 5% by weight, or at least about 8.0% by weight, or at least about 9.0% by weight, or at least about 99.9% by weight, Or substantially all of the contaminants present in the stream are converted to converted contaminants, based on the total weight of the stream. Processing of the treated cleavage reaction mixture In various embodiments, after contacting one or more of the cleavage reaction mixture, the contaminant is contacted with the acidic material, the stream can be separated into one or more scorpions, and the feed stream is rich. Containing phenol, cyclohexanone and/or cyclohexylbenzene & These streams may be substantially or completely free of contaminants.

S-32-201229017 In various exemplary embodiments, the method further comprises separating the treated stream of the contaminated material into a first stream enriched in cyclohexanone or phenol or both with respect to the treated stream of the contaminant And a second stream enriched with converted contaminants. Heat Treatment In various embodiments, some or all of the contaminants (e.g., in the cracking reaction mixture or a portion of the cracking reaction mixture) are subjected to heat treatment conditions upstream or downstream of the contaminant treatment. For example, the temperature of all or a portion of the cleavage reaction mixture can be raised by at least about 100 ° C, or from about 150 ° C to about 185 ° C, or at least about 200 ° C to produce a heat treated cracking reaction mixture. In various embodiments, the temperature can be less than about 250 ° C, or less than about 225 ° C. The temperature can be in any range of the aforementioned temperatures. In various embodiments, the heat treatment conditions include a residence time of at least 1 minute, 2 minutes, 3 minutes, 5 minutes, 10 minutes, or 15 minutes. The residence time can be less than about 120 minutes, 60 minutes, or 30 minutes. The residence time can be within any reasonable range of the foregoing time. In one embodiment, it will be at least about 1% by weight, or 1% by weight, or 20.0% by weight, or 50.0% by weight, or 80.0% by weight, or 90.0% by weight, or 99.0% by weight, Or 99.9% by weight, or all of any contaminant (eg, hydroxycyclohexanone, or other oxyketones such as benzophenone, 6-hydroxyphenylhexanone, 6-hydroperoxybenzophenone benzoic acid) , valeraldehyde, pentanone, 2-hydroxycyclohexanone, phenylcyclohexanone, or unreacted peroxide) are converted to converted contaminants during heat treatment. -33- 201229017 In various embodiments, it will not exceed about 80.0% by weight, or 50% by weight, or 30% to 0% by weight, or 20.0% by weight, or 10.0% by weight of pollution. Hydroxycyclohexanone or other oxyketone (such as 6-hydroxyphenylhexanone) or both are converted to converted contaminants, including furans having both olefin and oxygen moieties, such as 1,2,4a,9b _Tetrahydrodibenzo[b,d]furan, which can be formed from the dehydration, alkylation and cyclization of phenylhydrazine and hydroxycyclohexanone. In various embodiments, the heat treated stream can be separated into one or more streams that are one or more rich in cyclohexanone, phenol, and/or cyclohexylbenzene relative to the heat treated stream. These fractions may contain little or no unconverted contaminants. The heat treatment can be carried out in a simple vessel or tube, which can be open or have a mixing device such as a baffle or a static mixer for spoiler. Further, heat treatment can occur in the fractionation column wherein the fractionation operating conditions are selected such that the distilled component is exposed to any temperature or residence time marked at any point or points in the column. The heat treated component can be withdrawn from any point in the fractionation column as a product of the top, bottom or side column. The heat treatment typically converts at least some of the contaminants or converted contaminants into other compounds that are more easily removed from the phenol and/or cyclohexanone. After contaminant treatment and/or heat treatment, or combined contaminants and heat treatment, the converted contaminants typically have such characteristics that they are more separable from the phenol and/or cyclohexanone or both than the starting contaminants. The detachable may be distillable, e.g., the converted contaminant does not form an azeotrope with phenol or cyclohexanone. Instead, the starting contaminant forms an azeotrope, and/or may be filtered, and/or sorbable. As a result, after the pollutant treatment and / or heat treatment, the logistics can be

S-34-201229017 One or more separations result in a stream containing mainly cyclohexanone, phenol and converted contaminants. Uses of Cyclohexanone and Phenol The cyclohexanone produced by the method disclosed herein can be used, for example, as an industrial solvent, as an activator in an oxidation reaction, and for producing adipic acid, cyclohexanone resin, cyclohexene. Ketone oxime, caprolactam and nylon (such as nylon 6 and resistant wheels 6,6). The phenol produced by the method disclosed herein can be used, for example, to produce a phenol resin, bisphenol A, ε-caprolactam, adipic acid, and/or a plasticizer. DESCRIPTION OF THE INVENTION The present invention will now be described more particularly with reference to the accompanying drawings. Referring to Figure 1, there is shown a process 100 for producing phenol and cyclohexanone from cyclohexylbenzene according to a first example of the present invention, wherein a feed comprising cyclohexylbenzene is supplied to the oxidation reactor as a line 1 〇2. . A stream comprising oxygen, suitably air, is also supplied to oxidation reactor 106 as line 104. The stream in line i 〇4 can also be derived from air: for example, air that removes particulates by compression and filtration, condenses and removes water by compression and cooling, or undergoes membrane enrichment, cryogenic separation or other The way is to increase the logistics of about 21 moles of oxygen than normal air. Oxidation reactor 106 can be any type of reactor and, for example, comprises a simple, open-ended vessel having a distributor inlet for the oxygen-containing stream in line 104, or otherwise ensuring the effectiveness of oxygen and cyclohexylbenzene. contact. The -35-201229017 oxidation reactor 106 can have a means for withdrawing and pumping a portion of its contents through a suitable cooling device and a cooled portion back to the reactor 106, thereby manipulating the exotherm of the oxidation reaction. Alternatively, a cooling coil that provides indirect cooling (e.g., with cooling water) can be operated in the oxidation reactor 106 to remove the heat generated. In other embodiments, the oxidation reactor 106 can comprise a plurality of reactors in series, each performing a portion of the conversion reaction, optionally operating under selected different conditions to increase the respective conversion ranges in the respective reactors. The oxidation reaction in the middle. The conditions within the oxidation reactor 106 are such that an oxidation reaction occurs, converting the cyclohexylbenzene to the associated hydroperoxide. The suitably selected conditions facilitate the formation of cyclohexyl-1-phenyl-1-hydroperoxides which are superior to the other hydroperoxides and dihydroperoxides discussed herein. In a particular embodiment, N-hydroxy quinone imine (NHPI) can also be introduced into oxidation reactor 106 in a device not shown in Figure 1 to enhance cyclohexyl-1-phenyl-1- Hydroperoxide selectivity. As the oxidation reaction continues, oxygen is depleted and the oxygen depleted stream is removed from oxidation reactor 106 via line 108. When the stream comprising oxygen in line 104 is air, then the oxygen depleted stream in line 1 通常 8 is typically enriched in nitrogen. When the oxidation reaction is carried out at or near atmospheric pressure, the oxygen depletion stream in line 1 0 8 may also contain lower volatility oxidation by-products (such as water) and a small amount of cyclohexylbenzene and in the oxidation reaction. The other components of the vapor can be used under the condition of 16. In the operation not shown in Fig. 1, the oxygen depletion stream in the line 108 can be further processed to recover cyclohexylbenzene, remove water' and otherwise make cyclohexylbenzene suitable for recycling as an oxidation counter.

S -36- 201229017 The feed of the reactor 106 and other streams are suitable for other uses or disposal. The oxidation reaction product comprising cyclohexylbenzene hydroperoxide is withdrawn from oxidation reactor 106 via line 110, which is suitably enriched in cyclohexyl-1-phenyl-1-hydroperoxide, but may also include other hydrogen radicals. Oxides and dihydroperoxides. When NHPI is introduced into the oxidation reactor 106, the oxidation reaction product removed by line 1 10 may also contain NHPI. The oxidation product comprising cyclohexylbenzene hydroperoxide in line 110 is supplied to a cracking reactor 114 which also receives a catalyst for promoting the cracking reaction, such as sulfuric acid, in the manner of line 112. The conditions in the cleavage reactor 1 are such that the cleavage reaction occurs, causing cyclohexyl-1-phenyl-1-hydroperoxide and any other hydroperoxide and dihydroperoxide present to decompose into phenol, ring Hexone and pollutant by-products. The cracking reaction product is withdrawn from the cracking reactor 1 14 via line 1 16 and includes phenol, cyclohexanone, contaminant by-products, and possibly unreacted cracking catalyst. The cleavage reactor 114 can be any type of reactor known to those skilled in the art, such as a simple open-type vessel containing a tank reactor mode operating in almost continuous agitation, or operating in a nearly piston fluid reactor mode. Simple open type long tube. The cleavage reactor 114 can have a means for withdrawing and withdrawing a portion of the contents through a suitable cooling device and a cooled portion back to the cleavage reactor Π4, thereby manipulating the exotherm of the cleavage reaction, or it can be operated adiabatically. In one embodiment, the catalyst that promotes the cracking reaction can be introduced into the contents of the cooled or uncooled recycled portion of the cracking reactor 114. Alternatively, a cooling coil that provides indirect cooling (e.g., with cooling water) can be operated in the cracking reactor 1 14 to remove the resulting -37-201229017 heat. In other embodiments, the cleavage reactor 114 can comprise a plurality of reactors in series, each performing a portion of the conversion reaction, optionally operating in a selected different mode and under different conditions to enhance the relevant conversion range. The cleavage reaction in each reactor. The cleavage reaction product in line 116 is directed to an acidic material contacting apparatus 1 18 containing an acidic material. The conditions within the contacting apparatus 118 are such that a purification reaction occurs and at least some of the pollutant by-products in the cleavage reaction product are converted to a purified reaction product. The acid treated stream is removed from contacting apparatus 1 1 8 via line 1 2 0, which contains reduced contaminant by-product content relative to the cracking reaction product, and may be further processed by the apparatus not shown in FIG. 1, eg Further purification of phenol and cyclohexanone, separation of cyclohexanone and phenol, and similar processing. The acidic material contacting device 118 can be any device suitable for interlinking with the acid materials utilized herein. In the specific example depicted in Figure 1, no acidic material is supplied to the contacting device 1 18 in a separate line. Such a specific example is represented by, for example, a solid acidic material such as an ion exchange resin or a zeolite. In a variation of this specific example, the acidic material is the same as the acid used as the catalyst for promoting the cracking reaction, and the acidic material contacting device 118 may be a simple large open type container reactor or a large open type long tube. It allows the acid and the cleavage reaction product to be continuously exposed to the desired residence time. In another embodiment, the acidic material can be a liquid aqueous acid, and the acidic material contacting device Π8 can be a countercurrent scrubber, or a liquid-liquid extraction column or a countercurrent series of liquid-liquid contacting drums. In this embodiment, a line not shown in Figure 1 may be present to carry fresh liquid acidic material to acidity.

The S-38-201229017 material "Μ contact device 118 and the used liquid acidic material are removed from the apparatus. In the specific example, the cracked product additionally contains an unreacted cracking catalyst' and the material is not a favorable purification reaction. Acidic material. One option in this state provides for the removal of unreacted catalyst from the cracked product from line 1丨6, or neutralizing the material and making it substantially inert, and providing the resulting cracked product A device to the acidic material contacting device 118 (not shown in Figure 1). In this manner, the desired acidic material and acidic material contacting device 118 can independently and optimally aid in the purification reaction of the cleavage product. Referring to Figure 2, there is shown the production of phenol from cyclohexylbenzene according to a second example of the present invention. A process 200 of cyclohexanone wherein a feed comprising cyclohexylbenzene is fed to oxidation reactor 206 in line 202. A stream comprising oxygen (which may have the same composition as in line i 〇 4 of Figure 1) is also supplied via line 204 to oxidation reactor 206. The oxidation reactor 206 is constructed and operated in the same manner as the oxidation reactor 106 of FIG. 1, including withdrawing the oxygen depleted stream from the reactor in line 208 and withdrawing the oxidation reaction product including cyclohexylbenzene hydroperoxide from line 210. . The oxidation reaction product is supplied to the cracking reactor 2 1 4 in line 2 10 , which also receives sulfuric acid which promotes the cracking reaction in the manner of line 2 1 2 . The configuration and operation of the cracking reactor 214 is the same as that of the cracking reactor 114 of FIG. 1, including the extraction of a cracking reaction product comprising phenol, 'cyclohexanone, contaminant by-products, and unreacted sulfuric acid from the cracking reactor 214 in line 216. . The cleavage reaction product in line 216 is combined with the amine compound in line 218 (-39-201229017 is suitably a relatively high molecular weight amine such as 2-methylpentane-1,5-diamine) for complexation and neutralization. The sulfuric acid in the reaction is cracked and the neutralized cracked product in line 220 is produced. The neutralized cracking product in line 220 thus contains phenol, cyclohexanone, contaminant by-products and amine-sulfate. The amine-sulfate is completely soluble in the remainder of the neutralized cleavage product and additionally has a relatively low volatility compared to cyclohexylbenzene. In one embodiment, the amount of amine compound supplied in line 218 exceeds the stoichiometry of the sulfuric acid neutralization in cracked product line 216, so the neutralized cracked product in line 220 has a relatively alkaline or less The acid traits feed the neutralized cracked product in line 220 to a first fractionator 2 22 which is operated to provide a first overhead product in line 224 which is rich in volatility The material having a high cyclohexanone, for example, methylcyclopentanone in the neutralized cleavage product which may be present in the line 22, and the overhead product are suitably additionally having a very low content of cyclohexanone, phenol, cyclohexyl Benzene and lower volatile components. The first fractionation column 222 is operated to provide the opposite bottoms product in line 226, which is rich in cyclohexanone and lower volatility components, and additionally includes contamination that is difficult to fractionate from cyclohexanone and phenol. The by-product of the product, and the bottom product, are suitably of a material having a very low content of volatility higher than cyclohexanone. Further, the first bottoms product in line 226 is enriched with amine-sulfate (suitably containing all of the salt) introduced into the neutralized cracked product of first fractionation column 22 by line 220. The first bottoms product in line 226 is fed to a second distillation column 228 which is operated to provide a second overhead product in line 232, the column

S -40- 201229017 Top product is rich in Benzo and cyclohexanone' and includes by-products of pollutants, and the top product is deficient in cyclohexylbenzene and lower volatile components, and the recycled reaction product is depleted. . Operating the second distillation column 2 2 8 to provide the second bottom product of the opposite of the line 2 3 0 'the bottom of the column, which is rich in cyclohexylbenzene and lower volatile components' and rich in recycling The reaction product is purified, and the overhead product is suitably depleted of phenol and cyclohexanone. Further, the second bottoms product in line 230 is enriched with amine-sulfate (suitably containing all of the salt) introduced into the first bottoms product of second fractionation column 228 via line 226. The second overhead product in line 232 is directed to acidic material contacting device 234. The acidic material contacting device 234 contains an acidic material which contacts the conditions within the apparatus 234 such that a purification reaction occurs and some contaminant by-products are converted to a purified reaction product. From the acid material contacting apparatus 234, the acid treated stream is removed via line 23, which contains a reduced amount of contaminant by-product relative to the amount supplied by the second overhead product in line 23 2 . The configuration and operation of the acid material contacting device 234 is the same as the device 1 18 of Figure 1, including withdrawing the acid treated stream from the device via line 23 6 . The acid-treated stream containing reduced contaminant by-product content and a purified reaction product rich in volatility lower than phenol and cyclohexanone is directed to a third fractionation column 238 via line 23 6 to operate the fractionation column to provide The third overhead product in line 242 is rich in phenol and cyclohexanone, and depleted by-products of the contaminants and purified reaction products. The third fractionation column 238 is operated to provide an opposite third bottoms product in line 240 which is enriched in the purified reaction product and suitably depleted in phenol and cyclohexanone. In a specific example -41 - 201229017, the third bottoms product in line 240 contains sufficient phenol, or phenol and cyclohexanone, to carry some of the impurities that may not be purified in the acidic material contacting apparatus 234. Contaminant by-product. The third bottoms product in line 240 containing the purified reaction product and random phenol and cyclohexanone is recycled to second fractionation column 228. In this manner, any phenol and cyclohexanone present in the third bottoms product in line 240 are recovered in the second overhead product in line 23 2 and the purified reaction product is removed from line 230. In the bottom product of the second column. In one embodiment, the operation of the first fractionation column 222 or the second fractionation column 22 8 or both is performed in such a manner that the contaminant by-products in the column are exposed to the heat treatment conditions at the residence time, causing at least a portion The pollutant by-product undergoes a second purification reaction and converts the pollutant by-product into a second purified reaction product having a lower volatility than cyclohexanone, phenol or both. This second purification reaction, which is heat treated, can optionally be enhanced by additives such as superstoichiometric addition of an amine having a lower volatility than cyclohexylbenzene to the cracking product, as discussed above, which is then introduced into a fractionation column. The second purified reaction product can then be passed to the fractionation column either from the first bottoms product in line 226 or from the second bottoms product in line 230 or both. Although the present invention has been described and illustrated by reference to the specific embodiments thereof, those skilled in the art will understand that the invention may be modified by the invention. For this reason, the scope of the appended claims should be individually referenced for the purpose of determining the true scope of the invention. [Simple description of the map]

S-42 - 201229017 Figure 1 is a simplified flow diagram of a process according to a specific example of the invention for the production of phenol and cyclohexanone from cyclohexylbenzene. Figure 2 is a simplified flow diagram of a process for making phenol and cyclohexanone from cyclohexylbenzene in accordance with another embodiment of the present invention. [Explanation of main component symbols] 100: Method for producing phenol and cyclohexanone from cyclohexylbenzene 102, 104, 108, 110, 112, 116, 120, 202, 204, 208, 210, 212, 216, 218, 220, 224, 226 > 230, 232, 236, 240, 242: line 106: oxidation reactor 1 1 4: cleavage reactor 1 18: acid material contacting apparatus 200: method of producing phenol and cyclohexanone from cyclohexylbenzene 206 : Oxidation Reactor 214: Cracking Reactor 222: First Separator 22 8 : Second Distillation Column 234: Acid Material Contact Equipment 23 8 : Third Fractionation Column - 43 -

Claims (1)

201229017 VII. Patent Application Range: 1. A method for producing phenol, the method comprising: (a) oxidizing at least a portion of a feed comprising cyclohexylbenzene to produce a cyclohexyl-1-phenyl-1.hydroperoxide comprising An oxidizing composition of the substance; (b) cleavage of at least a portion of the oxidizing composition to produce a cleavage reaction mixture comprising phenol, cyclohexanone, and at least one contaminant: and (c) at least a portion of the cleavage reaction The mixture is contacted with an acidic material to convert at least a portion of the contaminant to converted contaminants, thereby producing a modified reaction mixture. 2. According to the method of claim 1, wherein the pollutant is acyclic aliphatic hexanal, acyclic aliphatic ketone, cyclohexenone, cyclohexanedione, hydroxycyclohexanone, benzoic acid, benzene Formate, cyclohexenylcyclohexanone, methylcyclopentenylcyclohexanone, 1-phenyl-6-hydroxyhexan-1-one, 1-cyclohexyl-6-hydroxyhex-1-one and One or more of bicyclododecan hydroperoxides. The method of claim 1, wherein the acidic material comprises at least one of a microporous acidic material, a cation exchange resin, a solid acid catalyst, a Bronsted acid, and a sulfurous acid or an acid salt. 4. The method of claim 1, wherein the contacting (c) is carried out at a temperature of from about 30 ° C to about 25 ° C and a pressure of from about 5 to about 345 0 kPa. 5. The method of claim 1, further comprising: heating the at least one contaminant at least a portion of the upstream of the contacting (c) to a temperature of at least 100 ° C to manufacture the at least one contaminant Heat treated cracking reaction mixture. S-44 - 201229017 6. The method of claim 1, further comprising: separating at least a portion of the modified reaction mixture into cyclohexanone-rich and phenol-rich relative to the modified reaction product A first stream of at least one of the first stream, and a reaction product relative to the reformed product is a second stream enriched in converted contaminants. 7. A phenol oxime produced by the method of claim 1 of the patent scope 8. A cyclohexanone produced by the method of claim 1 of the patent application. A phenol resin, at least one of bisphenol a, ε-caprolactam, adipic acid or a plasticizer, which is obtained from phenol according to item 7 of the patent application. 10. At least one of adipic acid, cyclohexanone resin, cyclohexanone oxime, caprolactam or nylon, which is obtained from cyclohexanone as in claim 8 of the patent application. 11. A method of making phenol, the method comprising: (a) introducing oxygen into a feed comprising cyclohexylbenzene to cause an oxidation reaction to occur and producing a cyclohexyl..b phenyl-i-hydroperoxide comprising An oxidizing composition; (b) introducing an acid catalyst into at least a portion of the oxidizing composition to cause a cracking reaction to occur and to produce a cleavage reaction mixture comprising phenol, cyclohexanone, and at least one contaminant, & (c) Introducing an acidic material into at least a portion of the cleavage reaction mixture to convert at least a portion of the contaminant to a converted contaminant, -45-201229017 thereby producing a modified reaction mixture. 12. A method of producing phenol, the method comprising: (a) oxidizing cyclohexylbenzene to produce an oxidized composition comprising a cyclohexylphenyl-hydroperoxide; (b) at least a portion of the cyclohexyl group a -1-phenyl-1. hydroperoxide cleavage to produce a cleavage reaction mixture comprising phenol, cyclohexanone, and at least one contaminant; and (c) contacting at least a portion of the contaminant with an acidic material, At least a portion of the contaminant is converted to the converted contaminant, thereby producing a modified reaction mixture. S -46-