(19)
(11)EP 2 534 119 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
05.04.2017 Bulletin 2017/14

(21)Application number: 10784929.1

(22)Date of filing:  23.11.2010
(51)International Patent Classification (IPC): 
C07C 5/02(2006.01)
C07C 29/20(2006.01)
C07C 45/00(2006.01)
C07C 39/04(2006.01)
C07C 13/19(2006.01)
C07C 7/163(2006.01)
C07C 5/03(2006.01)
C07C 37/08(2006.01)
C07C 45/53(2006.01)
C07C 49/403(2006.01)
C07C 7/148(2006.01)
(86)International application number:
PCT/US2010/057753
(87)International publication number:
WO 2011/100013 (18.08.2011 Gazette  2011/33)

(54)

HYDROGENATION PROCESS

HYDRIERVERFAHREN

PROCÉDÉ D'HYDROGÉNATION


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 12.02.2010 US 304040 P

(43)Date of publication of application:
19.12.2012 Bulletin 2012/51

(73)Proprietor: ExxonMobil Chemical Patents Inc.
Baytown TX 77520-2101 (US)

(72)Inventors:
  • DAKKA, Jihad, M.
    Whitehouse Station NJ 08889 (US)
  • KUECHLER, Keith, H.
    Friendswood TX 77546 (US)
  • LATTNER, James, R.
    Laporte TX 77571 (US)
  • MOZELESKI, Edmund, J.
    Califon NJ 07830 (US)

(74)Representative: ExxonMobil Chemical Europe Inc. 
IP Law Europe Hermeslaan 2
1831 Machelen
1831 Machelen (BE)


(56)References cited: : 
WO-A1-2008/101616
US-A- 4 169 857
WO-A1-2009/038900
  
      
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description

    FIELD



    [0001] The present invention relates to a hydrogenation process. More particularly, the invention relates to a hydrogenation process that may be used in the production of phenol.

    BACKGROUND



    [0002] Various processes can be used to make phenol. For example, phenol can be made by the Hock process, which involves alkylation of benzene with propylene to produce cumene, oxidation of the cumene to the corresponding hydroperoxide, and cleavage of the hydroperoxide to produce phenol and acetone.

    [0003] Phenol can also be made by alkylation of benzene and a C4 alkylating agent to produce sec-butylbenzene, oxidation of the sec-butylbenzene to sec-butylbenzene hydroperoxide, and cleavage of the sec-butylbenzene hydroperoxide to produce phenol and methyl ethyl ketone.

    [0004] Another process for making phenol involves hydroalkylation of benzene to produce cyclohexylbenzene, oxidation of the cyclohexylbenzene to cyclohexylbenzene hydroperoxide, and cleavage of the cyclohexylbenzene hydroperoxide to produce phenol and cyclohexanone.

    [0005] However, one or more steps of the processes described above can produce substances that are detrimental to process efficiency. For example, and as illustrated in Figure 1A (with reference to Example 1), the inventors have discovered that the presence of olefins, such as those produced in the hydroalkylation/alkylation and cleavage steps described above, can interfere with oxidation and result in slower conversion and reduced selectivity to the corresponding hydroperoxide.

    [0006] Additionally, and as illustrated in Figure 1B (with reference to Example 2), the inventors have discovered that phenol and phenolics, which may be present in one or more recycle streams of a process for making phenol, can also interfere with oxidation.

    [0007] That said, many of these substances have boiling points very close to those of cumene, sec-butylbenzene and cyclohexylbenzene, making them difficult to separate by conventional techniques, such as distillation.

    [0008] As such, what is needed is a process for treating such substances to make them substantially inert relative to, more easily separable from, and/or directly remove them from, phenol production processes.

    SUMMARY



    [0009] The invention relates to a hydrogenation process in which a composition comprising: (i) greater than 50 wt% of cyclohexylbenzene, the wt% based upon total weight of the composition; and (ii) a hydrogenable component selected from cyclohexenylbenzene is contacted with hydrogen in the presence of a hydrogenation catalyst under hydrogenation conditions.

    [0010] In the present invention the conversion of the hydrogenable component is preferably at least 50% more selective to form cyclohexylbenzene than bicyclohexane.

    [0011] The invention also relates to a hydrogenation and oxidation process in which a feed comprising cyclohexenylbenzene is contacted with hydrogen in the presence of a hydrogenation catalyst under hydrogenation conditions to form cyclohexylbenzene. The cyclohexylbenzene is then reacted with oxygen (e.g., air) in the presence of an oxidation catalyst under oxidation conditions to form cyclohexylbenzene hydroperoxide.

    [0012] The invention also relates to a process for producing phenol comprising: (i) hydroalkylating benzene to form a composition having: (1) cyclohexylbenzene; and (2) a first hydrogenable component selected from cyclohexenylbenzene; (ii) hydrogenating at least a portion of the first hydrogenable component selected from cyclohexenylbenzene; (iii) oxidizing the cyclohexylbenzene to form an oxidized composition comprising a hydroperoxide; and (iv) cleaving the hydroperoxide to form phenol and/or cyclohexanone.

    BRIEF DESCRIPTION OF THE FIGURES



    [0013] 

    Figure 1A shows Time On Stream (T.O.S.) vs. CHB conversion of a composition having varying amounts of olefins during oxidation.

    Figure 1B shows T.O.S. vs. CHB conversion of a composition having varying amounts of phenol during oxidation.

    Figure 2 shows CHB conversion vs. cyclohexylbenzene hydroperoxide (CHBHP) selectivity of a composition having varying amounts of cyclohexanone during oxidation.

    Figure 3 shows T.O.S. vs. CHB conversion of a hydrogenated composition and pure CHB.

    Figure 4 illustrates an embodiment of a hydrogenation process.

    Figure 5 illustrates an embodiment of a process for producing a hydroperoxide.

    Figure 6 illustrates an embodiment of a process for producing phenol.

    Figure 7 illustrates an embodiment of a process for producing phenol comprising a recycle to the hydrogenation process.

    Figure 8 illustrates SBB conversion of samples having varying amounts of olefins.


    DETAILED DESCRIPTION OF THE EMBODIMENTS



    [0014] Various specific embodiments, versions and examples of the invention will now be described, including preferred embodiments and definitions that are adopted herein for purposes of understanding the claimed invention.

    [0015] That said, described herein is a hydrogenation process. This process may be conducted alone, or in conjunction with one or more steps of a process to produce phenol, such as: (i) alkylation and/or hydroalkylation; (ii) oxidation; (iii) cleavage; and/or (iv) dehydro genation.

    Hydrogenation Process



    [0016] In accordance with various embodiments, the hydrogenation process comprises contacting a composition having: (i) a first component; and (ii) a second component with hydrogen in the presence of a hydrogenation catalyst under hydrogenation conditions.

    [0017] The first component can be any substance that is present in a process for making phenol. In the present invention, the first component is cyclohexylbenzene (CHB) and the composition comprises greater than 50 wt% of the first component, or greater than 60 wt% of the first component, based upon total weight of the composition. The first component may be supplied from any source. For example, it may be supplied from a fresh source, produced during alkylation or hydroalkylation, and/or recycled from a step in the phenol production process.

    [0018] The second component (also referred to as a "hydrogenable component") can be any substance that can react with hydrogen. In the present invention, the second component is selected from cyclohexenylbenzene.

    [0019] In various embodiments, the composition comprises greater than 0.01 wt% of a hydrogenable component, or greater than 0.1 wt% of a hydrogenable component, or greater than 1 wt% of a hydrogenable component, based upon total weight of the composition. In various embodiments, the hydrogenable component is made during one or more of alkylation/hydroalkylation, oxidation, cleavage and dehydrogenation steps.

    [0020] By way of illustration, Figure 4 shows an embodiment of a hydrogenation process 400. Composition 410 comprises a first component and a hydrogenable component and is supplied to reactor 420 where it is contacted with hydrogen and a hydrogenation catalyst under hydrogenation conditions to form composition 430, which has less of the hydrogenable component.

    [0021] In various embodiments, the hydrogenation process described herein produces a composition comprising less than 1 wt%, or less than 0.1 wt%, or less than 0.01 wt% of the hydrogenable component, based upon total weight of the composition.

    [0022] It will be understood that the hydrogenation process may be carried out as a batch process, semi-batch process or continuous process.

    [0023] The hydrogen may be introduced to the hydrogenation process from any source. For example, fresh hydrogen may be used, or hydrogen may be obtained from one or more recycle streams of a phenol production process.

    [0024] The hydrogenation catalyst may be any catalyst that can facilitate hydrogenation. In an embodiment, the catalyst comprises: (i) a hydrogenation component; and (ii) a support.

    [0025] The hydrogenation component may comprise at least one metal component selected from Groups 6 to 10 of the Periodic Table of Elements, such as platinum, palladium and compounds and mixtures thereof. The hydrogenation component may be present in an amount between 0.1 and 10 wt%, or 0.2 to 0.5 wt%, or 0.3 wt%, wherein the wt% is based upon total weight of the hydrogenation catalyst.

    [0026] The term "metal component" is used herein to include a metal compound that may not be purely the elemental metal, but could, for example, be at least partly in another form, such as an oxide, hydride or sulfide form. The weight % (wt%) of the metal component is herein defined as being measured as the metal present based on the total weight of the catalyst composition irrespective of the form in which the metal component is present.

    [0027] The support may comprise one or more of aluminum oxide, silica, silicate, aluminosilicates including but not limited to zeolytes and MCM-41, carbon, and a carbon nanotube. Impurities may also be present in the support. For example, sodium salts such as sodium silicate can be present from anywhere from 0.01 to 2 wt% based upon total weight of the hydrogenation catalyst.

    [0028] The hydrogenation conditions may be any conditions suitable to cause the hydrogenable component to react with hydrogen. In various embodiments, the hydrogenation conditions comprise a pressure of 1 kPa (0 kPa,g) (kPa, gauge) to 3551 kPa (3450 kPa,g), or 601 kPa (500 kPa,g) to 2101 kPa (2000 kPa,g), or 851 kPa (750 kPa,g) to 1601 kPa (1500 kPa,g), or 1101 kPa (1000 kPa,g) and a temperature of 10°C to 100°C, or 40°C to 80°C, or 65°C.

    [0029] In the present invention, it has been advantageously discovered that the use of the hydrogenation conditions and hydrogenation catalyst disclosed herein results in selective hydrogenation of olefins and ketones without substantially affecting aromatic groups. In particular, cyclohexenylbenzene is selectively converted to CHB rather than bicyclohexane:

    [0030] In various embodiments, the conversion of the hydrogenable component is at least 50%, or 60%, or 70% more selective to CHB than to bicyclohexane. In various embodiments, the hydrogenation process produces less than 1 wt%, or less than 0.5 wt%, or less than 0.05 wt% bicyclohexane the wt%s based upon total weight of the composition.

    [0031] The hydrogenation process may be performed as a stand-alone process or as part of a process to produce phenol. For example, the hydrogenation process may be performed in any sequence with one or more of the steps of: (a) alkylation or hydroalkylation; (b) oxidation; (c) cleavage; and (d) dehydrogenation. These steps are described in more detail below.

    Alkylation/Hydroalkylation



    [0032] As discussed above, the hydrogenation process may be part of a process to produce phenol that includes alkylation or hydroalkylation of benzene.

    [0033] In one embodiment, benzene is alkylated with cyclohexene in the presence of an acid catalyst, such as zeolite beta or an MCM-22 family molecular sieve, or by oxidative coupling of benzene to biphenyl followed by hydrogenation of the biphenyl. In another embodiment, alkylation involves hydroalkylating benzene with hydrogen under hydroalkylation conditions in the presence of a hydroalkylation catalyst whereby the benzene undergoes the following reaction to produce CHB:



    [0034] Any commercially available benzene feed can be used in the alkylation or hydroalkylation step, but preferably the benzene has a purity level of at least 99 wt%. Similarly, although the source of hydrogen is not critical, it is generally desirable that the hydrogen is at least 99 wt% pure.

    [0035] Conveniently, the total feed to the alkylation or hydroalkylation step contains less than 500 ppm, or less than 100 ppm, or 12-20 ppm, water. In addition, 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.

    [0036] The alkylation or hydroalkylation reaction can be conducted in a wide range of reactor configurations including fixed bed, slurry reactors, and/or catalytic distillation towers. In addition, the reaction can be conducted in a single reaction zone or in a plurality of reaction zones, in which at least the hydrogen is introduced to the reaction in stages. In one embodiment, hydrogen addition or benzene addition can be staged with internal recycle for cooling. Suitable reaction temperatures are between 100°C and 400°C, such as between 125°C and 250°C, while suitable reaction pressures are between 100 and 7,000 kPa, such as between 500 and 5,000 kPa. Suitable values for the molar ratio of hydrogen to benzene are between 0.15:1 and 15:1, such as between 0.4:1 and 4:1 for example between 0.4 and 0.9:1.

    [0037] The catalyst used in the alkylation or hydroalkylation reaction may be a bifunctional catalyst comprising a MCM-22 family molecular sieve and a hydrogenation metal. The MCM-22 family molecular sieve includes:
    • molecular sieves made from a common first degree crystalline 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. Such crystal structures are discussed in the "Atlas of Zeolite Framework Types", Fifth Edition, 2001, the entire content of which is incorporated as reference);
    • molecular sieves made from a common second degree building block, being a 2-dimensional tiling of such MWW framework topology unit cells, forming a monolayer of one unit cell thickness, preferably one c-unit cell thickness;
    • molecular sieves made from common second degree building blocks, being layers of one or more than one unit cell thickness, wherein the layer of more than one unit cell thickness is made from stacking, packing, or binding at least two monolayers of one unit cell thickness. The stacking of such second degree building blocks can be in a regular fashion, an irregular fashion, a random fashion, or any combination thereof; and
    • molecular sieves made by any regular or random 2-dimensional or 3-dimensional combination of unit cells having the MWW framework topology.


    [0038] Molecular sieves of MCM-22 family generally have an X-ray diffraction pattern including d-spacing maxima at 10.25, 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. 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. WO97/17290), MCM-36 (described in U.S. Patent No. 5,250,277), MCM-49 (described in U.S. Patent No. 5,236,575), MCM-56 (described in U.S. Patent No. 5,362,697), UZM-8 (described in U.S. Patent No. 6,756,030), and mixtures thereof. Preferably, the molecular sieve is selected from (a) EMM-10, (b) EMM-11, (c) EMM-12, (d) EMM-13, (e) MCM-49, (f) MCM-56 and (g) isotypes of MCM-49 and MCM-56, such as ITQ-2.

    [0039] 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. Generally, the amount of hydrogenation metal present in the catalyst is between 0.05 and 10 wt%, such as between 0.1 and 5 wt%, of the catalyst. In one embodiment, where the MCM-22 family molecular sieve is an aluminosilicate, 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 1.5 to 1500, for example from 75 to 750, such as from 100 to 300.

    [0040] The hydrogenation metal may be directly supported on the MCM-22 family molecular sieve by, for example, impregnation or ion exchange. However, in a more preferred embodiment, at least 50 wt%, for example at least 75wt%, and generally substantially all of the hydrogenation metal is supported on an inorganic oxide separate from but composited with the molecular sieve. In one embodiment, the hydrogenation metal is supported on an inorganic oxide.

    [0041] 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), p. 27 (1985).

    [0042] The hydrogenation metal is deposited on the inorganic oxide, conveniently by impregnation, before the metal-containing inorganic oxide is composited with said molecular sieve. Typically, the catalyst composite is produced by co-pelletization, in which a mixture of the molecular sieve and the metal-containing inorganic oxide are formed into pellets at high pressure (generally 350 to 350,000 kPa), or by co-extrusion, in which a slurry of the molecular sieve and the metal-containing inorganic oxide, optionally together with a separate binder, are forced through a die. If necessary, additional hydrogenation metal can subsequently be deposited on the resultant catalyst composite.

    [0043] 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.

    [0044] Transalkylation with additional benzene is typically effected in a transalkylation reactor, separate from the hydroalkylation reactor, over a suitable transalkylation catalyst, such as a molecular sieve of the MCM-22 family, zeolite beta, MCM-68 (see U.S. Patent No. 6,014,018), zeolite Y and mordenite. The transalkylation reaction is typically conducted under at least partial liquid phase conditions, which suitably include a temperature of 100 to 300°C, a pressure of 800 to 3500 kPa, a weight hourly space velocity of 1 to 10 hr-1 on total feed.

    Oxidation



    [0045] The hydrogenation process may be conducted as part of a process that includes oxidation (e.g., CHB oxidation).

    [0046] Oxidation may be accomplished by introducing an oxygen-containing gas, such as air or enriched air into a liquid phase. The oxidation may be conducted in the presence or absence of a catalyst.

    [0047] Suitable catalysts for the oxidation step are the N-hydroxy substituted cyclic imides described in U.S. Patent No. 6,720,462, such as N-hydroxyphthalimide, 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(pyromellitic diimide), 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-norbornene-2,3-dicarboximide, exo-N-hydroxy-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-hydroxy-cis-cyclohexane-1,2-dicarboximide, N-hydroxy-cis-4-cyclohexene-1,2 dicarboximide, N-hydroxynaphthalimide sodium salt or N-hydroxy-o-benzenedisulphonimide.

    [0048] These materials can be used either alone or in the presence of a free radical initiator and can be used as liquid-phase, homogeneous catalysts or can be supported on a solid carrier to provide a heterogeneous catalyst. Typically, the N-hydroxy substituted cyclic imide or the N,N',N"-trihydroxyisocyanuric acid is employed in an amount between 0.0001 mol% to 15 wt%, such as between 0.001 to 5 wt%, of the cumene, SBB or CHB.

    [0049] Suitable oxidation conditions include a temperature between 70°C and 200°C, such as 90°C to 130°C, and a pressure of 50 to 10,000 kPa. Any oxygen-containing gas, preferably air, can be used as the oxidizing medium. The reaction can take place in batch reactors or continuous flow reactors. In one embodiment, the acids generated during oxidation are in the off gas streams and are neutralized with caustic (e.g., sodium carbonate) and separated or eliminated with the use of equipment such as chillers, decanter drums and adsorbers. The aqueous effluent from the oxidizers may then be neutralized and sent to waste water.

    Cleavage



    [0050] The hydrogenation process may be conducted as part of a process that includes peroxide cleavage (e.g., CHB peroxide cleavage).

    [0051] Cleavage of the peroxide can be effected by contacting the hydroperoxide with a catalyst in the liquid phase at a temperature of 20°C to 150°C, such as 40°C to 120°C, a pressure of 50 to 2,500 kPa, such as 100 to 1000 kPa. The hydroperoxide is preferably diluted in an organic solvent inert to the cleavage reaction, such as methyl ethyl ketone (MEK), cyclohexanone, phenol or CHB, to assist in heat removal. The cleavage reaction is conveniently conducted in a series of heat exchangers, one or more well mixed reaction vessels, or a catalytic distillation unit.

    [0052] The catalyst employed in the cleavage step can be a homogeneous catalyst or a heterogeneous catalyst. Suitable homogeneous cleavage catalysts include sulfuric acid, perchloric acid, phosphoric acid, hydrochloric acid and p-toluenesulfonic acid. Ferric chloride, boron trifluoride, sulfur dioxide and sulfur trioxide are also effective homogeneous cleavage catalysts. The preferred homogeneous cleavage catalyst is sulfuric acid, with preferred concentrations in the range of 0.05 to 0.5 wt%. For a homogeneous acid catalyst, a neutralization step preferably follows the cleavage step. Such a neutralization step typically involves contact with a basic component, with subsequent decanting of a salt-enriched aqueous phase.

    [0053] Any suitable heterogeneous catalyst may be used, such as those described in U.S. Patent No. 4,870,217.

    Dehydrogenation



    [0054] The hydrogenation process may be conducted as part of a process that includes dehydrogenation of a ketone that is made during the production of phenol (e.g., acetone, MEK or cyclohexanone). Dehydrogenation generally involves contacting the ketone with a dehydrogenation catalyst.

    [0055] The catalyst may comprise: (i) a support; (ii) a first component; and (iii) a hydrogenable component produced such that the catalyst exhibits an oxygen chemisorption of greater than 0.5, preferably greater than 0.6 and more preferably greater than 0.7.

    [0056] Conveniently, the support employed in the dehydrogenation catalyst is selected from the group consisting of silica, a silicate, an aluminosilicate such as including zeolytes and MCM-41, zirconia, carbon and carbon nanotubes, and preferably comprises silica. Impurities which can be present in the catalyst support (e.g., silica) are, for example, sodium salts such as sodium silicate which can be present from anywhere from 0.01 to 2 wt%.

    [0057] Generally, the first component employed in the present catalyst comprises at least one metal selected from Groups 6 to 10 of the Periodic Table of Elements and compounds and mixtures thereof, such as platinum, palladium and compounds and mixtures thereof. In another embodiment, the first component comprises at least one metal selected from Group 10 of the Periodic Table of Elements and compounds and mixtures thereof. Typically, the first component is present in an amount between 0.1 and 10 wt% of the catalyst.

    [0058] In addition, the catalyst comprises a second component comprising at least one metal or compound thereof selected from Group 1 and Group 2 of the Periodic Table of Elements wherein, said at least one metal or compound thereof selected from Group 1 and Group 2 of the Periodic Table of Elements is present in an amount of at least 0.1 wt%, at least 0.2 wt%, at least 0.3 wt%, at least 0.4 wt% and at least 0.5 wt%. In one embodiment, the second component comprises at least one metal or compound thereof selected from Group 1 of the Periodic Table of Elements, such as potassium, cesium and rubidium and compounds and mixtures thereof; preferably potassium and potassium compounds. In another embodiment, the second component comprises at least one metal or compound thereof selected from Group 1 or 2 of the Periodic Table of Elements. Typically, the second component is present in an amount between 0.1 and 5 wt% of the catalyst.

    [0059] Suitable conditions for the dehydrogenation step include a temperature of 250°C to 750°C, a pressure of atmospheric to 3548 kPa [500 psi-gauge (psig), 3447 kPa-gauge (kPa,g)], a weight hourly space velocity of 0.2 to 50 hr-1, and a hydrogen to cyclohexanone-containing feed molar ratio of 0 to 20.

    [0060] The temperature of the dehydrogenation process may be from 300°C to 750°C and from 400°C to 500°C.

    [0061] The pressure of the dehydrogenation process may be from 101 to 2169 kPa (0 to 300 psig, (0 to 2068 kPa,g) or from 790 to 2169 kPa (100 to 300 psig, 689 to 2068 kPa,g).

    [0062] The reactor configuration used for the dehydrogenation process generally comprises one or more fixed bed reactors containing a solid catalyst with a dehydrogenation function.

    [0063] In one embodiment, separation can be enhanced by conducting the distillation under at least partial vacuum, typically at below 101 kPa. Moreover, extractive distillation processes are known. See for example, U.S. Patent Nos. 4,021,490; 4,019,965; 4,115,207; 4,115,204; 4,115,206; 4,201,632; 4,230,638; 4,167,456; 4,115,205; and 4,016,049.

    [0064] In another embodiment, the cleavage effluent is subjected to one or more separation processes to recover or remove one or more components of the effluent prior to dehydrogenation. In particular, the cleavage effluent is conveniently subjected to at least a first separation step to recover some or all of the phenol from the effluent, typically so that the effluent stream fed to said dehydrogenation reaction contains less than 50 wt%, for example less than 30 wt%, such as less than 1 wt%, phenol. The first separation step is conveniently effected by vacuum distillation and the same, or additional vacuum distillation steps, can be used to remove components boiling below 155°C (as measured at 101 kPa), such as benzene and cyclohexene, and/or components boiling above 185°C (as measured at 101 kPa), such as 2-phenyl phenol and diphenyl ether, prior to feeding the effluent stream to the dehydrogenation reaction.

    [0065] By employing the present dehydrogenation process, substantially all the ketone can be converted to phenol. This can readily be achieved by, for example, contacting the phenol with hydrogen in the presence of a hydrogenation catalyst, such as platinum or palladium, under conditions including a temperature of 20°C to 250°C, a pressure of 101 kPa to 10000 kPa and a hydrogen to phenol molar ratio of 1:1 to 100:1.

    Exemplary Processes



    [0066] Figure 5 illustrates phenol process 500 comprising Step 510: hydrogenating composition 505 comprising a first component and a hydrogenable component in the presence of a hydrogenation catalyst under hydrogenation conditions to form composition 515; and Step 520: oxidizing the first component in composition 515 in the presence of an oxidation catalyst under oxidation conditions to form composition 525 comprising a peroxide or hydroperoxide.

    [0067] In the embodiment illustrated in Figure 6, phenol process 600 comprises Step 610: alkylating or hydroalkylating benzene feed 605 to form composition 615 comprising first component and a hydrogenable component; Step 620: hydrogenating at least a portion of the hydrogenable component to form composition 625; Step 630: oxidizing at least a portion of the first component in composition 625 to form composition 635 comprising a peroxide; and Step 640: cleaving the peroxide in the composition 635 to form composition 645 comprising phenol and a ketone (e.g., acetone, MEK or cyclohexanone). Optionally, system 600 may further comprise one or more additional steps, such as Step 650: hydrogenating at least a portion of any hydrogenable component that is present in composition 645; and/or Step 660: dehydrogenating the ketone.

    [0068] In various embodiments, hydrogenable components produced in different steps of a phenol process are hydrogenated in a single step. For example, as illustrated in Figure 7, phenol process 700 comprises Step 710: alkylating or hydroalkylating feed 705 comprising benzene to form composition 715 comprising a first component and a hydrogenable component; Step 720: hydrogenating at least a portion of the hydrogenable component in composition 715 to form composition 725; Step 730: oxidizing composition 725 to form composition 735 comprising a peroxide; and Step 740: cleaving the peroxide to form composition 745 comprising phenol, a ketone and hydrogenable component; and Step 750: recycling at least a portion of the hydrogenable component in composition 745 to hydrogenating step 720. Optionally, process 700 may further comprise Step 760: dehydrogenating the ketone present in composition 745.

    [0069] The invention will now be more particularly described with reference to the following non-limiting Examples and the accompanying figures.

    Example 1: Effect of Olefins on Oxidation



    [0070] One hundred and fifty (150) grams of CHB was oxidized in the presence of 5, 1, 0.1, 0.5 and 0 wt% of an olefin (namely, cyclohexenylbenzene) to determine the effect of olefins on CHB conversion. Oxidation was conducted using 0.1 wt% NHPI catalyst at 110°C and 1 atm. As shown in Figure 1A, reducing olefin content improves CHB conversion.

    Example 2: Effect of Phenol on Oxidation (not according to the invention)



    [0071] One hundred and fifty (150) grams of CHB was oxidized in the presence of: (i) 0.16 wt% phenol and 1 wt% hydroperoxide (HP); and (ii) 0 wt% phenol to determine the effect of phenol on CHB conversion. Oxidation was conducted using 0.1 wt% NHPI catalyst at 110°C and 1 atm (101kPa). As shown in Figure 1B, reducing phenol content improves CHB conversion.

    Example 3: Effect of Cyclohexanone on Oxidation (not according to the invention)



    [0072] One hundred and fifty (150) grams of CHB was oxidized in the presence of: (i) 0.15 wt% cyclohexanone (CHO); and (ii) 0 wt% CHO to determine the detrimental effect of cyclohexanone on cyclohexylbenzene hydroperoxide (CHBHP) selectivity. Oxidation was conducted using 0.1 wt% NHPI catalyst at 110°C and 101kPa (14.7 psi). As shown in Figure 2, the presence of cyclohexanone does not significantly affect selectivity to CHBHP.

    Example 4: Oxidation



    [0073] One hundred and fifty (150) grams of a composition comprising CHB and olefins was hydrogenated at 65°C and 1,000 psi,g to form a hydrogenated composition. The hydrogenated composition was then oxidized for comparison with pure CHB. Oxidation was conducted using 0.1 wt% NHPI catalyst at 110°C and 101kPa (14.7psi). As shown in Figure 3, both compositions have similar activity indicating that the hydrogenation removes the olefins to a level where they have substantially no impact on the oxidation.

    Example 5: SBB Production (not according to the invention)



    [0074] One (1) gram of MCM-22 catalyst (65% MCM-22/35% alumina binder) was used for the alkylation of benzene with 2-butene. The catalyst was in the form of a 1.6 mm (1/16") diameter cylindrical extrudate, chopped to 1/16" length, and diluted with sand to 3 cm3 and loaded into an isothermal, down-flow, fixed-bed, tubular reactor having an outside diameter of 4.76mm (3/16"). The catalyst was dried at 150°C and 1 atm with 100 cm3/min flowing nitroten for two hours. The nitrogen was turned off and benzene was fed to the reactor at 60 cm3/hr until the reactor pressure reached 300 psig. Benzene flow was then reduced to 7.63 cm3/hr (6.67 Weight Hourly Space Velocity (WHSV)). Butene feed (57.1% cis-butene, 37.8% trans-butene, 2.5% n-butane, 0.8% isobutene and 1-butene, and 1.8% other) was introduced from a syringe pump at 2.57 cc/hr (1.6 WHSV). Benzene/butene feed molar ratio was maintained at 3:1. The reactor temperature was adjusted to 160°C. 2-butene conversion was determined by measuring unreacted 2-butene (does butene need to be capitalized) relative to feed 2-butene. The catalyst was on stream for 4 days at 1.6 WHSV of butene with 97% 2-butene conversion, 2 days at 4.8 WHSV with 95% conversion, then 1 day at 7.2 WHSV with 86% conversion, and followed by 4 days at 1.6 WHSV with 97% conversion.

    Example 6: Hydrotreatment of SBB (not according to the invention)



    [0075] SBB (518 grams, 0.3864 mole), rhodium trichloride hydrate from Engelhard (0.52g, 0.0025 mole) and trioctyl methyl ammonium chloride (Aliquat™ 336) from Aldrich Chemical Co. (0.52 grams, 0.001286 mole) were combined in a 100 cm3 Parr autoclave. The autoclave was pressurized to 345 kPa (50 psig) with hydrogen and the contents were stirred at room temperature for 19 hours. Hydrogen pressure was maintained at 345 kPa (50 psig). SBB was collected at a boiling point of 108°C/105 mm vacuum.

    Example 7: Hydrotreatment of SBB (not according to the invention)



    [0076] Same procedure as Example 6, except with the SBB from Example 5 (43.2 grams, 0.322 mole).

    Example 8: Hydrotreatment of SBB (not according to the invention)



    [0077] Same procedure as Example 6, except with the SBB from Example 5 (43.2 grams, 0.322 mole) and 1% palladium on alumina powder from Aldrich Chemical Co. (1.6 grams).

    Example 9: Oxidation of SBB (not according to the invention)



    [0078] Pure SBB (518 grams, 0.3864 mole) and n-hydroxyphthalimide (NHPI) (0.185 grams, 0.001134 mole) from Aldrich Chemical Co were added into a 100 cm3 Parr autoclave. The contents were pressurized with nitrogen, followed by oxygen, to obtain 80:20 mixture at 1,480 kPa (215 psig) at room temperature. The contents of the autoclave were elevated to 115°C and 1,720 kPa (250 psig). The oxygen concentration was maintained at approx. 20% throughout the six hour heating period by refilling with pure oxygen. At the completion of the run, the contents were cooled to room temperature and the product was removed from the autoclave and sampled using gas chromatography. See Figure 8.

    Example 10: Oxidation of SBB (not according to the invention)



    [0079] The hydrogenation product of Example 6 was oxidized following the procedure of Example 9, except the following quantities were used: SBB (36.25 grams, 0.2705 mole) and NHPI (0.155 grams, 0.00095 mole). See Figure 8.

    Example 11: Oxidation of SBB (not according to the invention)



    [0080] The hydrogenation product of Example 5 was oxidized following the procedure of Example 9, except the following quantities were used: SBB (36.25 grams, 0.2705 mole) and NHPI (0.155 grams, 0.00095 mole). See Figure 8.

    Example 12: Oxidation of SBB (not according to the invention)



    [0081] The hydrogenation product of Example 7 was oxidized following the procedure of Example 9, except the following quantities were used: SBB (41 grams, 0.306 mole) and NHPI (0.176 grams, 0.00011 mole). See Figure 8.

    Example 13: Oxidation of SBB (not according to the invention)



    [0082] The hydrogenation product of Example 8 was oxidized following the procedure of Example 9, except the following quantities were used: SBB (41 grams, 0.306 mole) and NHPI (0.176 grams, 0.00011 mole). See Figure 8.

    [0083] In various embodiments, this invention relates to:
    1. 1. A hydrogenation process comprising:

      contacting a composition having:

      1. (i) greater than 50 wt% of sec-butylbenzene, the wt% based upon total weight of the composition; and
      2. (ii) a hydrogenable component selected from cyclohexenylbenzene.
      with hydrogen in the presence of a hydrogenation catalyst under hydrogenation conditions.

    2. 2. The process according to embodiment 1, wherein the contacting converts at least a portion of the cyclohexenylbenzene to cyclohexylbenzene.
    3. 3. The process of any of embodiments 12, wherein the composition has greater than 1 wt% of the hydrogenable component, the wt% based upon total weight of the composition.
    4. 4. The process according to embodiment 1, wherein the contacting produces a second composition comprising less than 1 wt% of the hydrogenable component, based upon the total weight of the second composition.
    5. 5. The process of any of embodiments 14, wherein the hydrogenation conditions comprise a temperature of 10°C to 200°C.
    6. 6. The process of any of embodiments 15, wherein the hydrogenation conditions comprise a temperature of 40°C to 80°C.
    7. 7. The process of any of embodiments 16, wherein the hydrogenation conditions comprise a temperature of 65°C.
    8. 8. The process of any of embodiments 17, wherein the hydrogenation conditions comprise a pressure of 101 kPa to 3551 kPa (0 kPa,g to 3450 kPa,g).
    9. 9. The process of any of embodiments 1-8, wherein the hydrogenation conditions comprise a pressure of 851 kPa to 1601 kPa (750 kPa,g to 1500 kPa,g).
    10. 10. The process of any of embodiments 19, wherein the hydrogenation catalyst comprises a hydrogenation component and a support.
    11. 11. The process of embodiment 10, wherein the hydrogenation component comprises at least one metal component selected from Groups 6 to 10 of the Periodic Table of Elements.
    12. 12. The process of embodiment 11. wherein the hydrogenation component comprises palladium.
    13. 13. The process of embodiment 12, wherein the hydrogenation catalyst comprises 0.1 to 10 wt% of the hydrogenation component, the wt% based upon total weight of the hydrogenation catalyst.
    14. 14. The process of embodiment 13, wherein the hydrogenation catalyst comprises 0.3 wt% of the hydrogenation component, the wt% based upon total weight of the hydrogenation catalyst.
    15. 15. The process of embodiment 10, wherein the support comprises at least one of aluminum oxide, silica, silicate, aluminosilicate, carbon and a carbon nanotube.
    16. 16. The process of any of embodiments 1-15, wherein the process is continuous.
    17. 17. A process for producing phenol comprising:
      1. (a) alkylating benzene to form a composition having: (i) cyclohexylbenzene; and (ii) a first hydrogenable component selected from cyclohexenylbenzene;
      2. (b) hydrogenating at least a portion of the first hydrogenable component selected from cyclohexenylbenzene;
      3. (c) oxidizing the cyclohexylbenzene to form a oxidized composition comprising a hydroperoxide; and
      4. (d) cleaving the hydroperoxide to form at least some phenol and cyclohexanone.
    18. 18. The process of embodiments 17, wherein the oxidizing (c) is conducted in the presence of less than 0.1 wt% phenol, the wt% based upon total weight of the oxidized composition.
    19. 19. The process of any of embodiments 17-18, wherein the hydrogenating (b) is conducted in the presence of a hydrogenation catalyst comprising a hydrogenation component and a support, wherein the hydrogenation component comprises at least one metal component selected from Groups 6 to 10 of the Periodic Table of and the support comprises at least one of aluminum oxide, silica, silicate, aluminosilicate and a carbon nanotube.
    20. 20. The process of embodiment 19, wherein the hydrogenation component comprises palladium.
    21. 21. The process of any of embodiments 17-20, wherein the hydrogenating (b) occurs at a temperature of 10°C to 200°C and a pressure of 101 to 3551 kPa (0 to 3450 kPa,g).



    Claims

    1. A hydrogenation process comprising:

    contacting a composition having:

    (i) greater than 50 wt% of cyclohexylbenzene, the wt% based upon total weight of the composition; and

    (ii) a hydrogenable component selected from cyclohexenylbenzene;

    with hydrogen in the presence of a hydrogenation catalyst under hydrogenation conditions.


     
    2. The process of claim 1, wherein the contacting converts at least a portion of the cyclohexenylbenzene to cyclohexylbenzene.
     
    3. The process of any of the preceeding claims, wherein the composition has greater than 1 wt% of the hydrogenable component, the wt% based upon total weight of the composition.
     
    4. The process of any preceding claim, wherein the contacting produces a second composition comprising less than 1 wt% of the hydrogenable component, the wt% based upon the total weight of the second composition.
     
    5. The process of any of the preceding claims, wherein the conversion of the hydrogenable component is at least 50% more selective to cyclohexylbenzene than to bicyclohexane.
     
    6. The process of any preceding claim, wherein the contacting produces a second composition comprising less than 0.5 wt% of bicyclohexane, the wt % based upon total weight of the second composition.
     
    7. The process of any of the preceding claims, wherein the hydrogenation conditions comprise a temperature of 40°C to 80°C
     
    8. A process for producing phenol comprising:

    (a) hydroalkylating benzene to form a composition having: (i) cyclohexylbenzene; and (ii) a first hydrogenable component selected from cyclohexenylbenzene;

    (b) hydrogenating at least a portion of the first hydrogenable component selected from cyclohexenylbenzene;

    (c) oxidizing the cyclohexylbenzene to form an oxidized composition comprising a hydroperoxide; and

    (d) cleaving the hydroperoxide to form at least some phenol and cyclohexanone.


     


    Ansprüche

    1. Hydrierverfahren, bei dem:

    eine Zusammensetzung, die aufweist:

    i) mehr als 50 Gew.% Cyclohexylbenzol, wobei sich die Gew.%-Angabe auf das Gesamtgewicht der Zusammensetzung bezieht, und

    ii) eine hydrierbare Komponente ausgewählt aus Cyclohexenylbenzol,

    in Gegenwart eines Hydrierkatalysators unter Hydrierbedingungen mit Wasserstoff in Kontakt gebracht wird.


     
    2. Verfahren nach Anspruch 1, bei dem das Inkontaktbringen mindestens einen Teil des Cyclohexenylbenzols in Cyclohexylbenzol umwandelt.
     
    3. Verfahren nach einem der vorhergehenden Ansprüche, bei dem die Zusammensetzung mehr als 1 Gew.% von der hydrierbaren Komponente aufweist, wobei sich die Gew.%-Angabe auf das Gesamtgewicht der Zusammensetzung bezieht.
     
    4. Verfahren nach einem der vorhergehenden Ansprüche, bei dem das Inkontaktbringen eine zweite Zusammensetzung produziert, die weniger als 1 Gew.% der hydrierbaren Komponente aufweist, wobei sich die Gew.%-Angabe auf das Gesamtgewicht der zweiten Zusammensetzung bezieht.
     
    5. Verfahren nach einem der vorhergehenden Ansprüche, bei dem die Umwandlung der hydrierbaren Komponente um mindestens 50% selektiver zu Cyclohexylbenzol als zu Bicyclohexan ist.
     
    6. Verfahren nach einem der vorhergehenden Ansprüche, bei dem das Inkontaktbringen eine zweite Zusammensetzung produziert, die weniger als 0,5 Gew.% Bicyclohexan umfasst, wobei sich die Gew.%-Angaben auf das Gesamtgewicht der zweiten Zusammensetzung beziehen.
     
    7. Verfahren nach einem der vorhergehenden Ansprüche, bei dem die Hydrierbedingungen eine Temperatur von 40°C bis 80°C umfassen.
     
    8. Verfahren zur Herstellung von Phenol, bei dem:

    (a) Benzol hydroalkyliert wird, um eine Zusammensetzung zu bilden, die (i) Cyclohexylbenzol und (ii) eine erste hydrierbare Komponente ausgewählt aus Cyclohexenylbenzol aufweist,

    (b) mindestens ein Teil der ersten hydrierbaren Komponente ausgewählt aus Cyclohexenylbenzol hydriert wird,

    (c) das Cyclohexylbenzol oxidiert wird, um eine oxidierte Zusammensetzung zu bilden, die ein Hydroperoxid umfasst, und

    (d) das Hydroperoxid gespalten wird, um mindestens etwas Phenol und Cyclohexanon zu bilden.


     


    Revendications

    1. Procédé d'hydrogénation comprenant : la mise en contact d'une composition comportant :

    (i) plus de 50 % en poids de cyclohexylbenzène, le % en poids étant basé sur le poids total de la composition ; et

    (ii) un composant hydrogénable choisi parmi le cyclohexénylbenzène ;

    avec de l'hydrogène en présence d'un catalyseur d'hydrogénation dans des conditions d'hydrogénation.
     
    2. Procédé de la revendication 1, dans lequel la mise en contact convertit au moins une partie du cyclohexénylbenzène en cyclohexylbenzène.
     
    3. Procédé de l'une quelconque des revendications précédentes, dans lequel la composition comporte plus de 1 % en poids du composant hydrogénable, le % en poids étant basé sur le poids total de la composition.
     
    4. Procédé de l'une quelconque des revendications précédentes, dans lequel la mise en contact produit une deuxième composition comprenant moins de 1 % en poids du composant hydrogénable, le % en poids étant basé sur le poids total de la deuxième composition.
     
    5. Procédé de l'une quelconque des revendications précédentes, dans lequel la conversion du composant hydrogénable est au moins 50 % plus sélectif pour le cyclohexylbenzène que pour le bicyclohexane.
     
    6. Procédé de l'une quelconque des revendications précédentes, dans lequel la mise en contact produit une deuxième composition comprenant moins de 0,5 % en poids de bicyclohexane, le % en poids étant basé sur le poids total de la deuxième composition.
     
    7. Procédé de l'une quelconque des revendications précédentes, dans lequel les conditions d'hydrogénation comprennent une température de 40 °C à 80 °C.
     
    8. Procédé de production de phénol comprenant :

    (a) l'hydroalkylation de benzène pour former une composition comportant : (i) du cyclohexylbenzène ; et (ii) un premier composant hydrogénable choisi parmi le cyclohexénylbenzène ;

    (b) l'hydrogénation d'au moins une partie du premier composant hydrogénable choisi parmi le cyclohexénylbenzène ;

    (c) l'oxydation du cyclohexylbenzène pour former une composition oxydée comprenant un hydroperoxyde ; et

    (d) le clivage de l'hydroperoxyde pour former au moins du phénol et de la cyclohexanone.


     




    Drawing




















    Cited references

    REFERENCES CITED IN THE DESCRIPTION



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    Patent documents cited in the description




    Non-patent literature cited in the description