WO2012067711A1 - Procédé de production de phénol - Google Patents

Procédé de production de phénol Download PDF

Info

Publication number
WO2012067711A1
WO2012067711A1 PCT/US2011/052474 US2011052474W WO2012067711A1 WO 2012067711 A1 WO2012067711 A1 WO 2012067711A1 US 2011052474 W US2011052474 W US 2011052474W WO 2012067711 A1 WO2012067711 A1 WO 2012067711A1
Authority
WO
WIPO (PCT)
Prior art keywords
cyclohexylbenzene
catalyst
polar solvent
cleavage
oxidation
Prior art date
Application number
PCT/US2011/052474
Other languages
English (en)
Inventor
Kun Wang
Roberto Garcia
Original Assignee
Exxonmobil Chemical Patents Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Exxonmobil Chemical Patents Inc. filed Critical Exxonmobil Chemical Patents Inc.
Publication of WO2012067711A1 publication Critical patent/WO2012067711A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/53—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of hydroperoxides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/08—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by decomposition of hydroperoxides, e.g. cumene hydroperoxide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C407/00—Preparation of peroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • the present invention relates to a process for producing phenol.
  • Phenol is an important product in the chemical industry and is useful in, for example, the production of phenolic resins, bisphenol A, ⁇ -caprolactam, adipic acid, and plasticizers.
  • cyclohexylbenzene can be produced by contacting benzene with hydrogen in the presence of a bifunctional catalyst comprising a molecular sieve of the MCM-22 family and at least one hydrogenation metal selected from palladium, ruthenium, nickel, cobalt and mixtures thereof.
  • a bifunctional catalyst comprising a molecular sieve of the MCM-22 family and at least one hydrogenation metal selected from palladium, ruthenium, nickel, cobalt and mixtures thereof.
  • the '513 patent also discloses that the resultant cyclohexylbenzene can be oxidized to the corresponding hydroperoxide which is then decomposed to the desired phenol and cyclohexanone co-product.
  • 5,254,751 discloses a method of producing phenol and acetone by decomposing cumene hydroperoxide in a non-isothermal manner in the presence of excess acetone whereby the molar ratio of acetone to phenol in a decomposition reactor is from about 1.1 : 1 to 1.5: 1.
  • the feed contains about 80% hydrocarbon and has very different solubility for the cleavage catalyst, typically sulfuric acid. Consequently, the cleavage products for cyclohexylbenzene hydroperoxide generally contain about 20% polar components which significantly affects the cleavage rate.
  • cyclohexylbenzene hydroperoxide is much more complicated than that for cumene hydroperoxide, particularly since more routes for by-product formation exist with cyclohexylbenzene hydroperoxide cleavage.
  • cyclohexanone is much more prone to acid-catalyzed aldol condensation reactions than acetone so that significant yield loss is possible unless the cyclohexylbenzene hydroperoxide cleavage is closely controlled.
  • cyclohexylbenzene can be converted into phenol and cyclohexanone in high yield by oxidizing the cyclohexylbenzene in the presence of a catalyst, such as N-hydroxyphthalimide (NHPI), and then, optionally without concentrating the oxidation product or removing the NHPI catalyst, cleaving the resultant hydroperoxide in the presence of a polar solvent, such as acetone, at a temperature in excess of 50°C.
  • a catalyst such as N-hydroxyphthalimide (NHPI)
  • a polar solvent such as acetone
  • U.S. Patent No. 3,959,381 discloses a method of producing phenol and cyclohexanone by contacting cyclohexylbenzene, preferably in the presence of a member selected from the group consisting of cumene and cumene hydroperoxide, with an oxygen containing gas to form 1 -phenylcyclohexyl hydroperoxide containing intermediate product, optionally purifying said intermediate, contacting the 1 -phenylcyclohexyl hydroperoxide intermediate product with an acid cleavage catalyst in the presence of an alkanone of from 3 to 6 carbons at a temperature of 20°C to 50°C, and recovering the formed phenol and cyclohexanone.
  • the oxidation is conducted in the absence of a catalyst.
  • U.S. Patent No. 4,480, 141 discloses a process in which secondary alkyl-substituted hydroperoxides, such as cyclohexylbenzene hydroperoxide, are cleaved to phenols and ketones by contacting the secondary alkyl-substituted benzene hydroperoxide with boron phosphate, at a temperature of about 20°C to 200°C.
  • the cleavage reaction can be carried out in the presence of a solvent, such as acetone and methylethyl ketone.
  • U.S. Patent No. 4,487,970 discloses a process in which secondary-alkyl substituted benzene hydroperoxides, such as cyclohexylbenzene hydroperoxide, are cleaved to form phenols and ketones by contacting the secondary-alkyl substituted benzene hydroperoxide with a catalyst consisting essentially of about 3 : 1 to 1 : 10 by weight of SbFs and graphite in the presence of an aromatic or ketone solvent at a temperature of from about 0°C to 100°C.
  • the solvent can be acetone.
  • the invention resides in one aspect in a process for producing phenol, the process comprising:
  • said first catalyst comprises a cyclic imide, such as N- hydroxyphthalimide.
  • the weight ratio of the polar solvent to the cyclohexylbenzene hydroperoxide supplied to said cleavage reaction zone is in the range of about 1 : 100 to about 100: 1, such as about 1 :20 to about 10: 1.
  • the polar solvent comprises acetone.
  • the second catalyst is an acid catalyst, such as sulfuric acid.
  • the sulfuric acid is present in an amount between about 0.005 wt% and 0.5 wt% of the total weight of polar solvent and cyclohexylbenzene hydroperoxide supplied to said cleavage reaction zone.
  • the oxidation product supplied to said cleavage reaction zone comprises about 10 wt% to about 40 wt% of said cyclohexylbenzene hydroperoxide.
  • the invention resides in a process for producing phenol, the process comprising:
  • Figure 1 is a graph of cyclohexylbenzene hydroperoxide conversion against time on stream with and without the addition of 5 wt% acetone to the cleavage feed in the cleavage process of Example 3.
  • Figure 2 is a graph of phenol yield against time on stream with and without the addition of 5 wt% acetone to the cleavage feed in the cleavage process of Example 3.
  • Figure 3 is a graph of cyclohexanone yield against time on stream with and without the addition of 5 wt% acetone to the cleavage feed in the cleavage process of Example 3.
  • Described herein is a process for producing phenol from cyclohexylbenzene in which the cyclohexylbenzene is contacted with an oxygen-containing compound in the presence of a first catalyst under oxidation conditions effective to produce an oxidation product comprising cyclohexylbenzene hydroperoxide. Thereafter at least part of the oxidation product and a polar solvent are contacted with a second catalyst under cleavage conditions including a temperature in excess of 50°C effective to convert at least a portion of the cyclohexylbenzene hydroperoxide in the oxidation product into phenol and cyclohexanone.
  • cyclohexanone can either be recovered from cleavage reaction effluent or can be dehydrogenated to produce additional phenol.
  • any commercially available benzene feed can be used in the hydroalkylation step, but preferably the benzene has a purity level of at least 99 wt%.
  • the source of hydrogen is not critical, it is generally desirable that the hydrogen is at least 99 wt% pure.
  • the total feed to the hydroalkylation step contains less than 1000 ppm, such as less than 500 ppm, for example less than 100 ppm, water.
  • the total feed typically contains less than 100 ppm, such as less than 30 ppm, for example less than 3 ppm, sulfur and less than 10 ppm, such as less than 1 ppm, for example less than 0.1 ppm, nitrogen.
  • Hydrogen can be supplied to the hydroalkylation step over a wide range of values, but typically is arranged such that the molar ratio of hydrogen to benzene in the hydroalkylation feed is between about 0.15: 1 and about 15: 1, such as between about 0.4: 1 and about 4: 1 , for example between about 0.4 and about 0.9: 1.
  • the hydroalkylation reaction may be effected in the presence of a bifunctional catalyst comprising a molecular sieve and a hydrogenation metal.
  • the molecular sieve comprises an MCM-22 family material.
  • MCM-22 family material (or “material of the MCM-22 family” or “molecular sieve of the MCM-22 family”), as used herein, includes molecular sieves made from a building block unit cell, which unit cell has the MWW framework topology.
  • a unit cell is a spatial arrangement of atoms which if tiled in three-dimensional space describes the crystal structure.
  • MWW framework topology is disclosed and described in the "Atlas of Zeolite Framework Types", Fifth Edition, 2001, the entire content of which is incorporated as reference.
  • Molecular sieves of MCM-22 family generally have an X-ray diffraction pattern including d-spacing maxima at 12.4 ⁇ 0.25, 6.9 ⁇ 0.15, 3.57 ⁇ 0.07 and 3.42 ⁇ 0.07 Angstrom.
  • the X-ray diffraction data used to characterize the material (b) are obtained by standard techniques using the K-alpha doublet of copper as the incident radiation and a diffractometer equipped with a scintillation counter and associated computer as the collection system.
  • Molecular sieves of 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.
  • the molecular sieve is selected from (a) MCM- 49; (b) MCM-56; and (c) isotypes of MCM-49 and MCM-56, such as ITQ-2.
  • any known hydrogenation metal can be employed in the hydroalkylation catalyst, although suitable metals include palladium, ruthenium, nickel, zinc, tin, and cobalt, with palladium being particularly advantageous.
  • the amount of hydrogenation metal present in the catalyst is between about 0.05 wt% and about 10 wt%, such as between about 0.1 wt% and about 5 wt%, of the catalyst.
  • the amount of hydrogenation metal present is such that the molar ratio of the aluminum in the molecular sieve to the hydrogenation metal is from about 1.5 to about 1500, for example from about 75 to about 750, such as from about 100 to about 300.
  • the inorganic oxide employed in such a composite hydroalkylation catalyst is not narrowly defined provided it is stable and inert under the conditions of the hydroalkylation reaction.
  • Suitable inorganic oxides include oxides of Groups 2, 4, 13, and 14 of the Periodic Table of Elements, such as alumina, titania, and/or zirconia. As used herein, the numbering scheme for the Periodic Table Groups is as disclosed in Chemical and Engineering News, 63(5), 27 (1985).
  • Suitable binder materials include synthetic or naturally occurring substances as well as inorganic materials such as clay, silica and/or metal oxides. The latter may be either naturally occurring or in the form of gelatinous precipitates or gels including mixtures of silica and metal oxides.
  • Naturally occurring clays which can be used as a binder include those of the montmorillonite and kaolin families, which families include the subbentonites and the kaolins commonly known as Dixie, McNamee, Georgia and Florida clays or others in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite or anauxite. Such clays can be used in the raw state as originally mined or initially subjected to calcination, acid treatment or chemical modification.
  • Suitable metal oxide binders include silica, alumina, zirconia, titania, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia, silica- alumina-magnesia and silica-magnesia-zirconia.
  • the hydroalkylation reaction using an MCM-22 family zeolite catalyst described herein is highly selective towards cyclohexylbenzene
  • the effluent from the hydroalkylation reaction may contain some dicyclohexylbenzene by-product.
  • Transalkylation with additional benzene is typically effected in a trans alky lation reactor, separate from the hydroalkylation reactor, over a suitable transalkylation catalyst, including large pore molecular sieves such as a molecular sieve of the MCM-22 family, zeolite beta, MCM-68 (see U.S. Patent No. 6,014,018), zeolite Y, zeolite USY, and mordenite.
  • a large pore molecular sieve has an average pore size in excess of 7 A in some embodiments or from 7 A to 12 A in other embodiments.
  • the transalkylation reaction is typically conducted under at least partial liquid phase conditions, which suitably include a temperature of about 100°C to about 300°C, a pressure of about 800 kPa to about 3500 kPa, a weight hourly space velocity of about 1 hr 1 to about 10 hr 1 on total feed, and a benzene/dicyclohexylbenzene weight ratio about of 1 : 1 to about 5: 1.
  • the transalkylation reaction effluent can then be returned to the second distillation tower to recover the additional monocyclohexylbenzene product produced in the transalkylation reaction.
  • Another significant by-product of the hydroalkylation reaction is cyclohexane.
  • a C6-rich stream comprising cyclohexane and unreacted benzene can be readily removed from the hydroalkylation reaction effluent by distillation, owing to the similarity in the boiling points of benzene and cyclohexane, the C6-rich stream is difficult to further separate by simple distillation.
  • some or all of the C6-rich stream can be recycled to the hydroalkylation reactor to provide not only part of the benzene feed but also part of the diluents mentioned above.
  • the C6-rich stream may be contacted with a dehydrogenation catalyst under dehydrogenation conditions sufficient to convert at least part of the cyclohexane in the C6-rich stream portion to benzene, which again can be recycled to the hydroalkylation reaction.
  • the dehydrogenation catalyst generally comprises (a) a support; (b) a hydrogenation- dehydrogenation component; and (c) an inorganic promoter.
  • the support (a) is selected from the group consisting of silica, a silicate, an aluminosilicate, zirconia, and carbon nanotubes, and preferably comprises silica.
  • Suitable hydrogenation-dehydrogenation components (b) comprise at least one metal selected from Groups 6 to 10 of the Periodic Table of Elements, such as platinum, palladium and compounds and mixtures thereof. Typically, the hydrogenation-dehydrogenation component is present in an amount between about 0.1 and about 10 wt% of the catalyst.
  • a suitable inorganic promoter (c) comprises at least one metal or compound thereof selected from Group 1 of the Periodic Table of Elements, such as a potassium compound.
  • the promoter is present in an amount between about 0.1 wt% and about 5 wt% of the catalyst.
  • Suitable dehydrogenation conditions include a temperature of about 250°C to about 500°C, a pressure of about atmospheric to about 500 psig (100 kPa to 3550 kPa), a weight hourly space velocity of about 0.2 hr 1 to 50 hr 1 , and a hydrogen to hydrocarbon feed molar ratio of about 0 to about 20.
  • BCH bicyclohexyl
  • MCPB methylcyclopentylbenzene
  • 1,2-methylcyclopentylbenzene (2-MCPB), and 1,3- methylcyclopentylbenzene (3 -MCPB) are readily converted in the subsequent oxidation/cleavage steps to the phenol and methylcyclopentanones, which are valuable products
  • 1, 1-methylcyclopentylbenzene (1-MCPB) is substantially inert to the oxidation step and so, if not removed, will build up in the C 12 stream.
  • bicyclohexyl (BCH) can lead to separation problems downstream.
  • at least part of the hydroalkylation reaction product may be treated with a catalyst under conditions to remove at least 1, 1- methylcyclopentylbenzene and/or bicyclohexyl from the product.
  • the catalyst is generally an acid catalyst, such as an aluminosilicate zeolite, and especially faujasite and the treatment may be conducted at a temperature of about 100°C to about 350°C, such as about 130°C to about 250°C, for a time of about 0.1 to about 3 hours, such as about 0.1 to about 1 hours.
  • the catalytic treatment is believed to isomerize the 1, 1-methylcyclopentylbenzene to the more readily oxidizable 1,2-methylcyclopentylbenzene (2-MCPB), and 1,3- methylcyclopentylbenzene (3-MCPB).
  • the bicyclohexyl is believed to react with benzene present in the hydroalkylation reaction product to produce cyclohexane and more of the desired cyclohexylbenzene according to the following reaction:
  • the catalytic treatment can be conducted on the direct product of the hydroalkylation reaction or after distillation of the hydroalkylation reaction product to separate the Ce and/or the heavies fraction.
  • the cyclohexylbenzene is initially oxidized to the corresponding hydroperoxide. This is accomplished by contacting the cyclohexylbenzene with an oxygen-containing compound, such as air and various derivatives of air. For example, it is possible to use air that has been compressed and filtered to removed particulates, air that has been compressed and cooled to condense and remove water, or air that has been enriched in oxygen above the natural approximately 21 mol% in air through membrane enrichment of air, cryogenic separation of air or other conventional means.
  • the oxidation is conducted in the presence of a catalyst.
  • Suitable oxidation catalysts include N-hydroxy substituted cyclic imides described in U.S. Patent No. 6,720,462, which is incorporated herein by reference for this purpose.
  • N- hydroxyphthalimide NHPI
  • 4-amino-N-hydroxyphthalimide 3-amino-N- hydroxyphthalimide
  • tetrabromo-N-hydroxyphthalimide tetrachloro-N-hydroxyphthalimide
  • N-hydroxyhetimide N-hydroxyhimimide
  • N-hydroxytrimellitimide N-hydroxybenzene- 1,2,4- tricarboximide
  • N,N'-dihydroxy(benzophenone- 3,3',4,4'-tetracarboxylic diimide N-hydroxymaleimide
  • pyridine-2,3-dicarboximide N- hydroxysuccinimide
  • N-hydroxy(tartaric imide) N-hydroxy-5-norborn
  • the catalyst is N-hydroxyphthalimide.
  • Another suitable catalyst is ⁇ , ⁇ ', ⁇ "- thihydroxyisocyanuric acid.
  • oxidation catalysts can be used either alone or in conjunction with a free radical initiator, and further can be used as liquid-phase, homogeneous catalysts or can be supported on a solid carrier to provide a heterogeneous catalyst.
  • the N-hydroxy substituted cyclic imide or the ⁇ , ⁇ ', ⁇ ''-trihydroxyisocyanuric acid is employed in an amount between 0.0001 wt% to 15 wt%, such as between 0.001 wt% to 5 wt%, of the cyclohexylbenzene.
  • Suitable conditions for the oxidation step include a temperature between about 70°C and about 200°C, such as about 90°C to about 130°C, and a pressure of about 50 kPa to 10,000 kPa.
  • a basic buffering agent may be added to react with acidic by-products that may form during the oxidation.
  • an aqueous phase may be introduced. The reaction can take place in a batch or continuous flow fashion.
  • the reactor used for the oxidation reaction may be any type of reactor that allows for introduction of oxygen to cyclohexylbenzene, and may further felicitously provide contacting of oxygen and cyclohexylbenzene to effect the oxidation reaction.
  • the oxidation reactor may comprise a simple, largely open vessel with a distributor inlet for the oxygen-containing stream.
  • the oxidation reactor may have means to withdraw and pump a portion of its contents through a suitable cooling device and return the cooled portion to the reactor, thereby managing the exothermicity of the oxidation reaction.
  • cooling coils providing indirect cooling, say by cooling water, may be operated within the oxidation reactor to remove the generated heat.
  • the oxidation reactor may comprise a plurality of reactors in series, each conducting a portion of the oxidation reaction, optionally operating at different conditions selected to enhance the oxidation reaction at the pertinent conversion range of cyclohexylbenzene or oxygen, or both, in each.
  • the oxidation reactor may be operated in a batch, semi-batch, or continuous flow manner.
  • the product of the cyclohexylbenzene oxidation reaction contains at least 5 wt%, such as at least 10 wt%, for example at least 15 wt%, or at least 20 wt% cyclohexyl-1 - phenyl-1 -hydroperoxide based upon the total weight of the oxidation reaction effluent.
  • the oxidation reaction effluent contains no greater than 80 wt%, or no greater than 60 wt%, or no greater than 40 wt%, or no greater than 30 wt%, or no greater than 25 wt% of cyclohexyl-1 -phenyl- 1 -hydroperoxide based upon the total weight of the oxidation reaction effluent.
  • the oxidation reaction effluent may further comprise imide catalyst and unreacted cyclohexylbenzene.
  • the oxidation reaction effluent may include unreacted cyclohexylbenzene in an amount of at least 50 wt%, or at least 60 wt%, or at least 65 wt%, or at least 70 wt%, or at least 80 wt%, or at least 90 wt%, based upon total weight of the oxidation reaction effluent.
  • At least a portion of the oxidation reaction effluent may be subjected to a cleavage reaction, with or without undergoing any prior separation or treatment.
  • all or a fraction of the oxidation reaction effluent may be subjected to high vacuum distillation to generate a product enriched in unreacted cyclohexylbenzene and leave a residue which is concentrated in the desired cyclohexyl-1 -phenyl- 1 -hydroperoxide and which is subjected to the cleavage reaction.
  • concentration of the cyclohexyl-1 -phenyl- 1- hydroperoxide is neither necessary nor preferred.
  • all or a fraction of the oxidation effluent, or all or a fraction of the vacuum distillation residue may be cooled to cause crystallization of the unreacted imide oxidation catalyst, which can then be separated either by filtration or by scraping from a heat exchanger surface used to effect the crystallization. At least a portion of the resultant oxidation composition reduced or free from imide oxidation catalyst may be subjected to the cleavage reaction.
  • all or a fraction of the oxidation effluent may be subjected to water washing and then passage through an adsorbent, such as a 3A molecular sieve, to separate water and other adsorbable compounds, and provide an oxidation composition with reduced water or imide content that may be subjected to the cleavage reaction.
  • an adsorbent such as a 3A molecular sieve
  • all or a fraction of the oxidation effluent may undergo a chemically or physically based adsorption, such as passage over a bed of sodium carbonate to remove the imide oxidation catalyst (e.g., NHPI) or other adsorbable components, and provide an oxidation composition reduced in oxidation catalyst or other adsorbable component content that may be subjected to the cleavage reaction.
  • a chemically or physically based adsorption such as passage over a bed of sodium carbonate to remove the imide oxidation catalyst (e.g., NHPI) or other adsorbable components, and provide an oxidation composition reduced in oxidation catalyst or other adsorbable component content that may be subjected to the cleavage reaction.
  • Another possible separation involves contacting all or a fraction of the oxidation effluent with a liquid containing a base, such as an aqueous solution of an alkali metal carbonate or hydrogen carbonate, to form an aqueous phase comprising a salt of the imide oxidation catalyst, and an organic phase reduced in imide oxidation catalyst.
  • a base such as an aqueous solution of an alkali metal carbonate or hydrogen carbonate
  • the final reactive step in the conversion of the cyclohexylbenzene into phenol and cyclohexanone involves the catalyzed cleavage of the cyclohexyl-1 -phenyl- 1 -hydroperoxide produced in the oxidation step.
  • the catalyst used in the cleavage reaction is an acid catalyst that is at least partially soluble in the cleavage reaction mixture being supplied to the cleavage reaction zone, is stable at a temperature of at least 185°C and has a lower volatility (higher normal boiling point) than cyclohexylbenzene.
  • the acid catalyst is also at least partially soluble in the cleavage reaction product that is being produced in the cleavage reaction zone.
  • Suitable acid catalysts include, but are not limited to, Bronsted acids, Lewis acids, sulfonic acids, perchloric acid, phosphoric acid, hydrochloric acid, p-toluene sulfonic acid, aluminum chloride, oleum, sulfur trioxide, ferric chloride, boron trifluoride, sulfur dioxide and sulfur trioxide. Sulfuric acid is a preferred acid catalyst.
  • the cleavage reaction mixture contains at least 50 weight- parts-per-million (wppm) and no greater than 5000 wppm of the acid catalyst, or at least 100 wppm and no greater than 3000 wppm, or at least 150 wppm and no greater than 2000 wppm of the acid catalyst, or at least 300 wppm and no greater than 1500 wppm of the acid catalyst, based upon total weight of the cleavage reaction mixture.
  • wppm weight- parts-per-million
  • the cleavage reaction zone is supplied with a polar solvent, such as an alcohol containing less than 6 carbons, such as methanol, ethanol, iso-propanol, and/or ethylene glycol; a nitrile, such as acetonitrile and/or propionitrile; nitromethane; and a ketone containing 6 carbons or less such as acetone, methylethyl ketone, 2- or 3-pentanone, cyclohexanone, and methylcyclopentanone.
  • a polar solvent such as an alcohol containing less than 6 carbons, such as methanol, ethanol, iso-propanol, and/or ethylene glycol
  • a nitrile such as acetonitrile and/or propionitrile
  • nitromethane and a ketone containing 6 carbons or less
  • the preferred polar solvent that is added to the cleavage reaction zone is acetone.
  • the polar solvent is added to the cleavage reaction zone such that the weight ratio of the polar solvent to the cyclohexylbenzene hydroperoxide supplied to the cleavage reaction zone is in the range of about 1 : 100 to about 100: 1, such as about 1 :20 to about 10: 1, and the cleavage reaction mixture being supplied to the cleavage reaction zone comprises about 10 wt% to about 40 wt% of the cyclohexylbenzene hydroperoxide.
  • the addition of the polar solvent is found not only to increase the degree of conversion of the cyclohexylbenzene hydroperoxide in the cleavage reaction but also to increase the selectivity of the conversion to phenol and cyclohexanone.
  • the polar solvent reduces the free radical induced conversion of the cyclohexylbenzene hydroperoxide to undesired products such as hexanophenone and phenylcyclohexanol.
  • the cleavage reaction mixture includes cyclohexylbenzene in an amount of at least 50 wt%, or at least 55 wt%, or at least 60 wt%, or at least 65 wt%, or at least 70 wt%, or at least 80 wt%, or at least 90 wt%, based upon total weight of the cleavage reaction mixture.
  • Suitable cleavage conditions include a temperature of greater than 50°C and no greater than 200°C, or at least 55°C and no greater than 200°C, or at least 60°C and no greater than 200°C, or at least 70°C and no greater than 200°C, or at least 80°C and no greater than 200°C, or at least 90°C and no greater than 200°C, or at least 100°C and no greater than 200°C, and a pressure of at least 1 and no greater than 370 psig (at least 7 and no greater than 2,550 kPa, gauge), or at least 14.5 and no greater than 145 psig (at least 100 and no greater than 1 ,000 kPa, gauge) such that the cleavage reaction mixture is completely or predominantly in the liquid phase during the cleavage reaction.
  • the reactor used to effect the cleavage reaction may be any type of reactor known to those skilled in the art.
  • the cleavage reactor may be a simple, largely open vessel operating in a near-continuous stirred tank reactor mode, or a simple, open length of pipe operating in a near-plug flow reactor mode.
  • the cleavage reactor comprises a plurality of reactors in series, each performing a portion of the conversion reaction, optionally operating in different modes and at different conditions selected to enhance the cleavage reaction at the pertinent conversion range.
  • the cleavage reactor is a catalytic distillation unit.
  • the cleavage reactor is operable to transport a portion of the contents through a cooling device and return the cooled portion to the cleavage reactor, thereby managing the exothermicity of the cleavage reaction.
  • the reactor may be operated adiabatically.
  • cooling coils operating within the cleavage reactor(s) remove any heat generated.
  • the major products of the cleavage reaction of cyclohexyl- 1 -phenyl- 1 - hydroperoxide are phenol and cyclohexanone, each of which generally comprise about 40 wt% to about 60 wt%, or about 45 wt% to about 55 wt% of the cleavage reaction product, such wt% based on the weight of the cleavage reaction product exclusive of unreacted cyclohexylbenzene and acid catalyst.
  • the cleavage reaction product also typically contains unreacted acid catalyst and hence at least a portion of the cleavage reaction product is normally neutralized with a basic material to remove or reduce the level of acid in the product.
  • Suitable basic materials include alkali metal hydroxides and oxides, alkali earth metal hydroxides and oxides, such as sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, calcium oxide, and barium hydroxide.
  • Sodium and potassium carbonates may also be used, optionally at elevated temperatures.
  • the basic material comprises one or more of: a caustic exchange resin; ammonia or ammonium hydroxide; a basic clay such as limestone, dolomite, magnesite, sepiolite and olivine; an activated carbon and/or impregnated activated carbon; an anionic exchange resin, such as a weakly basic ion exchange resin having a styrene-divinyl benzene polymer backbone and an amine functional structure selected from -N(CH 3 ) 2 , -NRH or -NR 2 , where R is a hydrogen or an alkyl group containing 1 to 20 carbon atoms; an amine polysiloxane functionalized with ethylenediamine; an organic basic material grafted on microporous or mesoporous metal oxides; other organo-inorganic solids, such as zeolites exchanged with a metal selected from the group of lithium, sodium potassium, rubidium, cesium, calcium, bar
  • amines in the form of their salts with weak organic acids may be used.
  • the basic material is a diamine, such as 2-methylpentamethyenediamine or hexamethylenediamine, which are commercially available from Invista S.a r.l. Corporation under the trade designations DYTEKTM A and DYTEKTM HMD.
  • Suitable solid basic materials include: basic metal oxide families; alkali on metal oxides; alkaline-earth on metal oxides; alkali and alkaline-earth zeolites; transition metals, rare earth and high valence oxides; hydrotalcites, calcined hydrotalcites and spinels, specifically hydrotalcites treated with an alkali metal selected from lithium, potassium, sodium, rubidium, cesium, and combinations thereof; perovskites; and beta-aluminas.
  • the basic material is one or more of the hindered amines described in U.S. Patent No. 6,201,157. It will be understood that the basic material may be added in the anhydrous state or may be an aqueous solution of any of the foregoing basic materials, particularly the metal hydroxides and salts with basic hydrolysis.
  • a liquid basic material employed in a neutralization reaction in the present invention such as an amine or diamine as has been discussed, has a relatively low volatility, with a normal boiling point temperature above that of cyclohexylbenzene, such that it will tend to remain in the bottoms product in subsequent fractionation operations that may be conducted on the least a portion of the treated cleavage reaction product that may contain such liquid basic material.
  • the conditions at which the neutralization reaction is effected vary with the acid catalyst and basic material employed. Suitable neutralization conditions include a temperature of at least 30°C, or at least 40°C, or at least 50°C, or at least 60°C, or at least 70°C, or at least 80°C, or at least 90°C. Other suitable neutralization conditions include a temperature of no greater than 200°C, or no greater than 190°C, or no greater than 180°C, or no greater than 170°C, or no greater than 160°C, or no greater than 150°C, or no greater than 140°C, or no greater than 130°C, or no greater than 120°C, or no greater than 110°C, or no greater than 100°C.
  • the neutralization conditions include a temperature that is reduced from cleavage reaction conditions, for example, the temperature may be 1°C, or 5°C, or 10°C, or 15°C, or 20°C, or 30°C, or 40°C lower than the temperature of the cleavage reaction.
  • Suitable neutralization conditions may include a pressure of about 1 psig to about 500 psig (5 kPa, gauge to 3450 kPa, gauge), or about 10 psig to 200 psig (70 kPa, gauge to 1380 kPa, gauge) such that the treated cleavage reaction mixture is completely or predominantly in the liquid phase during the neutralization reaction.
  • the neutralized acid product can be removed from the cleavage product leaving a crude mixture of phenol and cyclohexanone which can be purified and separated by methods well known in the art.
  • the cyclohexanone produced through the processes disclosed herein may be used, for example, as an industrial solvent, as an activator in oxidation reactions and in the production of adipic acid, cyclohexanone resins, cyclohexanone oxime, caprolactam and nylons, such as nylon 6 and nylon 6,6.
  • the phenol produced through the processes disclosed herein may be used, for example, to produce phenolic resins, bisphenol A, ⁇ -caprolactam, adipic acid and/or plasticizers.
  • Example 2 To help determine conversion and selectivity, the product from Example 2 was mixed with anhydrous dodecane ( ⁇ 8 wt%, Aldrich) as an internal standard for mass balance. Typically 30 grams of the feed generated in this fashion was placed in a 50-cc jacketed glass reactor with a circulating temperature bath. The bath was set to the desired temperature (55°C) and the reactor content was allowed to equilibrate. Once the temperature stabilized, a GC sample was taken for the hot feed. The desired amount of concentrated sulfuric acid (96%, triple-distilled, Aldrich) was then added via a micro-syringe.
  • anhydrous dodecane ⁇ 8 wt%, Aldrich
  • Table 1 and Figures 1 to 3 compare the CHBHP conversion and the yield of phenol and cyclohexanone with and without the use of acetone. Clearly presence of acetone in the cleavage feed improves both conversion and selectivity to desired products.
  • CHBHP conversion means the amount of cyclohexylbenzene hydroperoxide converted to any product.
  • Phenol selectivity is relative to the theoretical phenol yield based upon the amount of cyclohexylbenzene hydroperoxide converted.
  • Cyclohexanone selectivity is relative to the theoretical cyclohexanone yield based upon the amount of cyclohexylbenzene hydroperoxide converted.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé de production de phénol dans le cadre duquel du cyclohexylbenzène est mis en contact avec un composé contenant de l'oxygène en présence d'un premier catalyseur dans des conditions d'oxydation permettant la production d'un produit d'oxydation comprenant de l'hydroperoxyde de cyclohexylbenzène. Au moins une partie du produit d'oxydation et un solvant polaire sont ensuite amenés jusqu'à une zone où va se produire une réaction de clivage, zone dans laquelle ledit produit d'oxydation et le solvant polaire sont mis en contact en présence d'un second catalyseur dans des conditions de clivage, impliquant notamment une température supérieure à 50 °C, pour convertir au moins une partie de l'hydroperoxyde de cyclohexylbenzène en phénol et en cyclohexanone.
PCT/US2011/052474 2010-11-16 2011-09-21 Procédé de production de phénol WO2012067711A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US41404210P 2010-11-16 2010-11-16
US61/414,042 2010-11-16

Publications (1)

Publication Number Publication Date
WO2012067711A1 true WO2012067711A1 (fr) 2012-05-24

Family

ID=44720183

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2011/052474 WO2012067711A1 (fr) 2010-11-16 2011-09-21 Procédé de production de phénol

Country Status (1)

Country Link
WO (1) WO2012067711A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014189623A1 (fr) * 2013-05-22 2014-11-27 Exxonmobil Chemical Patents Inc. Procédé de production de phénol
US9334218B2 (en) 2012-12-20 2016-05-10 Exxonmobil Chemical Patents Inc. Process for making phenol and/or cyclohexanone
DE102015000810A1 (de) * 2015-01-23 2016-07-28 Oxea Gmbh Verfahren zur Herstellung von 3-Hydroxyalkanalen
US9475745B2 (en) 2012-11-21 2016-10-25 Exxonmobil Chemical Patents Inc. Process for producing phenol
US9656934B2 (en) 2013-06-28 2017-05-23 Exxonmobil Chemical Patents Inc. Process for producing phenol and/or cyclohexanone

Citations (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3959381A (en) 1970-10-22 1976-05-25 Texaco Inc. Phenol and cyclohexanone manufacture
US4439409A (en) 1981-04-30 1984-03-27 Bayer Aktiengesellschaft Crystalline aluminosilicate PSH-3 and its process of preparation
US4480141A (en) 1983-06-24 1984-10-30 Phillips Petroleum Company Cleavage of hydroperoxides
US4487970A (en) 1983-06-03 1984-12-11 Phillips Petroleum Company Cleavage of hydroperoxides
EP0293032A2 (fr) 1987-05-26 1988-11-30 ENIRICERCHE S.p.A. Matériau synthétique cristallin et poreux contenant des oxydes de silicium et de bore
US4826667A (en) 1986-01-29 1989-05-02 Chevron Research Company Zeolite SSZ-25
US4954325A (en) 1986-07-29 1990-09-04 Mobil Oil Corp. Composition of synthetic porous crystalline material, its synthesis and use
US5236575A (en) 1991-06-19 1993-08-17 Mobil Oil Corp. Synthetic porous crystalline mcm-49, its synthesis and use
US5250277A (en) 1991-01-11 1993-10-05 Mobil Oil Corp. Crystalline oxide material
US5254751A (en) 1992-09-14 1993-10-19 General Electric Company Method for the decomposition of cumene hydroperoxide by acidic catalyst to phenol and acetone
US5362697A (en) 1993-04-26 1994-11-08 Mobil Oil Corp. Synthetic layered MCM-56, its synthesis and use
WO1997017290A1 (fr) 1995-11-08 1997-05-15 Shell Internationale Research Maatschappij B.V. Materiaux a base d'oxyde et compositions de catalyseur les contenant
US6014018A (en) 1998-06-19 2000-01-11 United Microelectronics Corp. Voltage-reducing device with low power dissipation
US6037513A (en) 1998-07-09 2000-03-14 Mobil Oil Corporation Hydroalkylation of aromatic hydrocarbons
US6077498A (en) 1995-11-23 2000-06-20 Consejo Superior Investigaciones Cientificas Zeolite ITQ-1
US6201157B1 (en) 2000-01-10 2001-03-13 Sunoco, Inc. (R&M) Method for production of phenol and acetone by decomposition of cumene hydroperoxide
US6720462B2 (en) 2000-03-30 2004-04-13 Degussa Ag Method for producing aromatic alcohols, especially phenol
US6756030B1 (en) 2003-03-21 2004-06-29 Uop Llc Crystalline aluminosilicate zeolitic composition: UZM-8
WO2009025939A2 (fr) 2007-08-22 2009-02-26 Exxonmobil Chemical Patents Inc. Oxydation d'hydrocarbures
WO2010042261A1 (fr) * 2008-10-10 2010-04-15 Exxonmobil Chemical Company Procédé de production de phénol
WO2010098916A2 (fr) * 2009-02-26 2010-09-02 Exxonmobil Chemical Patents Inc. Procédé de production de phénol
WO2011001244A1 (fr) * 2009-06-29 2011-01-06 Polimeri Europa S.P.A. Procédé pour la préparation de phénol et de cyclohexanone

Patent Citations (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3959381A (en) 1970-10-22 1976-05-25 Texaco Inc. Phenol and cyclohexanone manufacture
US4439409A (en) 1981-04-30 1984-03-27 Bayer Aktiengesellschaft Crystalline aluminosilicate PSH-3 and its process of preparation
US4487970A (en) 1983-06-03 1984-12-11 Phillips Petroleum Company Cleavage of hydroperoxides
US4480141A (en) 1983-06-24 1984-10-30 Phillips Petroleum Company Cleavage of hydroperoxides
US4826667A (en) 1986-01-29 1989-05-02 Chevron Research Company Zeolite SSZ-25
US4954325A (en) 1986-07-29 1990-09-04 Mobil Oil Corp. Composition of synthetic porous crystalline material, its synthesis and use
EP0293032A2 (fr) 1987-05-26 1988-11-30 ENIRICERCHE S.p.A. Matériau synthétique cristallin et poreux contenant des oxydes de silicium et de bore
US5250277A (en) 1991-01-11 1993-10-05 Mobil Oil Corp. Crystalline oxide material
US5236575A (en) 1991-06-19 1993-08-17 Mobil Oil Corp. Synthetic porous crystalline mcm-49, its synthesis and use
US5254751A (en) 1992-09-14 1993-10-19 General Electric Company Method for the decomposition of cumene hydroperoxide by acidic catalyst to phenol and acetone
US5362697A (en) 1993-04-26 1994-11-08 Mobil Oil Corp. Synthetic layered MCM-56, its synthesis and use
WO1997017290A1 (fr) 1995-11-08 1997-05-15 Shell Internationale Research Maatschappij B.V. Materiaux a base d'oxyde et compositions de catalyseur les contenant
US6077498A (en) 1995-11-23 2000-06-20 Consejo Superior Investigaciones Cientificas Zeolite ITQ-1
US6014018A (en) 1998-06-19 2000-01-11 United Microelectronics Corp. Voltage-reducing device with low power dissipation
US6037513A (en) 1998-07-09 2000-03-14 Mobil Oil Corporation Hydroalkylation of aromatic hydrocarbons
US6201157B1 (en) 2000-01-10 2001-03-13 Sunoco, Inc. (R&M) Method for production of phenol and acetone by decomposition of cumene hydroperoxide
US6720462B2 (en) 2000-03-30 2004-04-13 Degussa Ag Method for producing aromatic alcohols, especially phenol
US6756030B1 (en) 2003-03-21 2004-06-29 Uop Llc Crystalline aluminosilicate zeolitic composition: UZM-8
WO2009025939A2 (fr) 2007-08-22 2009-02-26 Exxonmobil Chemical Patents Inc. Oxydation d'hydrocarbures
WO2010042261A1 (fr) * 2008-10-10 2010-04-15 Exxonmobil Chemical Company Procédé de production de phénol
WO2010098916A2 (fr) * 2009-02-26 2010-09-02 Exxonmobil Chemical Patents Inc. Procédé de production de phénol
WO2011001244A1 (fr) * 2009-06-29 2011-01-06 Polimeri Europa S.P.A. Procédé pour la préparation de phénol et de cyclohexanone

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL AND ENGINEERING NEWS, vol. 63, no. 5, 1985, pages 27

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9475745B2 (en) 2012-11-21 2016-10-25 Exxonmobil Chemical Patents Inc. Process for producing phenol
US9334218B2 (en) 2012-12-20 2016-05-10 Exxonmobil Chemical Patents Inc. Process for making phenol and/or cyclohexanone
WO2014189623A1 (fr) * 2013-05-22 2014-11-27 Exxonmobil Chemical Patents Inc. Procédé de production de phénol
US9382178B2 (en) 2013-05-22 2016-07-05 Exxonmobil Chemical Patents Inc. Process for producing phenol
US9656934B2 (en) 2013-06-28 2017-05-23 Exxonmobil Chemical Patents Inc. Process for producing phenol and/or cyclohexanone
DE102015000810A1 (de) * 2015-01-23 2016-07-28 Oxea Gmbh Verfahren zur Herstellung von 3-Hydroxyalkanalen
DE102015000810B4 (de) * 2015-01-23 2021-05-27 Oq Chemicals Gmbh Verfahren zur Herstellung von 3-Hydroxyalkanalen

Similar Documents

Publication Publication Date Title
US9815759B2 (en) Processes for producing phenol
US8884067B2 (en) Phenol and cyclohexanone mixtures
US9169175B2 (en) Cyclohexylbenzene compositions
US9321709B2 (en) Processes for producing phenol
US9115060B2 (en) Process for producing phenol
US8946484B2 (en) Method for producing phenol and/or cyclohexanone
US9365474B2 (en) Processes for producing phenol
WO2012036820A1 (fr) Compositions d'hydroperoxyde de cyclohexylbenzène
WO2012067711A1 (fr) Procédé de production de phénol
EP2928854B1 (fr) Procédé de production de phénol
US8921604B2 (en) Process for producing cyclohexylbenzene
US20130277605A1 (en) Cyclohexylbenzene Compositions
WO2013043272A1 (fr) Procédé de production de phénol

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11761798

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11761798

Country of ref document: EP

Kind code of ref document: A1