WO2007143239A2 - Procédé de fabrication du sec-butylbenzène - Google Patents

Procédé de fabrication du sec-butylbenzène Download PDF

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Publication number
WO2007143239A2
WO2007143239A2 PCT/US2007/062043 US2007062043W WO2007143239A2 WO 2007143239 A2 WO2007143239 A2 WO 2007143239A2 US 2007062043 W US2007062043 W US 2007062043W WO 2007143239 A2 WO2007143239 A2 WO 2007143239A2
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catalyst
mcm
butylbenzene
alkylation
butene
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WO2007143239A3 (fr
Inventor
Jane C. Cheng
Christine N. Elia
Mohan Kalyanaraman
Terry E. Helton
Michael J. Brennan
John S. Buchanan
Jeffrey T. Elks
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ExxonMobil Chemical Patents Inc
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ExxonMobil Chemical Patents Inc
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Priority to PCT/EP2008/000664 priority Critical patent/WO2008098676A1/fr
Priority to TW097103312A priority patent/TW200904778A/zh
Publication of WO2007143239A3 publication Critical patent/WO2007143239A3/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
    • C07C2/66—Catalytic processes
    • 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
    • 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

Definitions

  • the present invention relates to a process for producing sec- butylbenzene and for converting the sec-butylbenzene to phenol and methyl ethyl ketone.
  • Phenol and methyl ethyl ketone are important products in the chemical industry.
  • phenol is useful in the production of phenolic resins, bisphenol A, ⁇ -caprolactam, adipic acid, alkyl phenols, and plasticizers
  • methyl ethyl ketone can be used as a lacquer, a solvent and for dewaxing of lubricating oils.
  • Sec-butylbenzene can be produced by alkylating benzene with n- butenes over an acid catalyst.
  • a feed comprising benzene and a C 4 alkylating agent is contacted under liquid phase alkylation conditions with a catalyst comprising zeolite beta or an MCM-22 family molecular sieve to produce an alkylation effluent comprising sec-butylbenzene.
  • the sec-butylbenzene is then oxidized to produce a hydroperoxide and the hydroperoxide is cleaved to produce the desired phenol and methyl ethyl ketone.
  • zeolite catalysts employed in hydrocarbon conversion processes are in the form of cylindrical extrudates.
  • the zeolite beta and MCM-22 catalysts used in the Examples of WO 06/15826 are in the form of cylindrical extrudates.
  • shaped catalyst particles having a high surface to volume ratio such as those having a polylobal cross-section, can produce improved results in processes which are diffusion limited, such as the hydrogenation of resid.
  • Example 8 of the '990 patent discloses that hollow trilobal and quadrulobal ZSM-5 catalysts are more active and selective for the ethylation of benzene at 770 0 F and 300 psig pressure than solid cylindrical catalysts of the same length. Under these conditions, the reagents are necessarily in the vapor phase.
  • US Patent No. 6,888,037 discloses a process for producing cumene by contacting benzene and propylene under at least partial liquid phase alkylating conditions with a particulate molecular sieve alkylation catalyst, wherein the particles of said alkylation catalyst have a surface to volume ratio of about 80 to less than 200 inch "1 .
  • the present invention resides in a process for producing sec-butylbenzene, the process comprising reacting benzene with at least one C 4 alkylating agent under alkylation conditions and in the presence of a particulate alkylation catalyst comprising zeolite beta and/or at least one molecular sieve of the MCM-22 family to produce an alkylation product comprising sec- butylbenzene, wherein the alkylation conditions are such that the benzene is at least partially in the liquid phase and wherein the particles of said alkylation catalyst have a surface to volume ratio of at least 80 inch "1 and conveniently less than 200 inch "1 .
  • the particles of said alkylation catalyst have a surface to volume ratio about 100 inch "1 to about 150 inch "1 .
  • said catalyst includes at least one molecular sieve of the MCM-22 family.
  • said at least one molecular sieve of the MCM- 22 family has 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 molecular sieve is selected from MCM-22, PSH-3, SSZ-25, ERB-I, ITQ-I, ITQ-2, MCM-36, MCM-49, MCM-56, UZM-8, and mixtures thereof.
  • the process further comprises, prior to said reacting, contacting said catalyst with water under conditions to improve the sec- butylbenzene selectivity of the catalyst.
  • said contacting with water is conducted under conditions including a temperature of at least 0 0 C for a time of at least 0.5 hour, for example a temperature of about 10 0 C to about 50 0 C for a time of about 2 hours to about 24 hours.
  • said catalyst comprises about 50 to about 90 wt%, such as about 60 to about 80 wt%, of zeolite beta or said at least one molecular sieve of the MCM-22 family.
  • said catalyst has a cumulative pore volume in the 2 to 8 nanometer range, as measured by nitrogen porosimetry, of greater than 0.04 cc/gm, such as greater than 0.07 cc/gm, for example greater than 0.10 cc/gm.
  • said C 4 alkylating agent comprises a linear butene, such as butene- 1, butene-2 or a mixture thereof.
  • said linear butene is added to the process in stages such that said alkylation conditions include an overall molar ratio of benzene to butene from about 1 to about 20, preferably about 2 to aboutlO, more preferably about 3 to about 6.
  • said alkylation conditions also include a temperature of from about 60 0 C to about 260 0 C, a pressure of 7000 kPa or less, and a feed weight hourly space velocity (WHSV) based on C 4 alkylating agent of from about 0.1 to
  • the present invention resides in a process for producing phenol and methyl ethyl ketone, the process comprising:
  • the oxidizing (b) is conducted in the presence of a catalyst, such as a catalyst selected from (i) an oxo (hydroxo) bridged tetranuclear metal complex comprising manganese, (ii) an oxo (hydroxo) bridged tetranuclear metal complex having a mixed metal core, one metal of the core being a divalent metal selected from Zn, Cu, Fe, Co, Ni, Mn and mixtures thereof and another metal being a trivalent metal selected from In, Fe, Mn, Ga, Al and mixtures thereof, (iii) an N-hydroxy substituted cyclic imide either alone or in the presence of a free radical initiator, and (iv) N,N',N"-trihydroxyisocyanuric acid either alone or in the presence of a free radical initiator.
  • a catalyst such as a catalyst selected from (i) an oxo (hydroxo) bridged tetranuclear metal complex comprising manganese, (i
  • the oxidizing (b) is conducted at a temperature of about 70 0 C to about 200 0 C and a pressure of about 0.5 to about 20 atmospheres (50 to 2000 kPa).
  • the cleaving (c) is conducted in the presence of a catalyst.
  • the catalyst can be a homogeneous or heterogeneous catalyst.
  • the catalyst is a homogeneous catalyst, such as sulfuric acid.
  • the cleaving (c) is conducted at a temperature of about 40 0 C to about 120 0 C, a pressure of about 100 to about 2500 kPa, and a liquid hourly space velocity (LHSV) based on the hydroperoxide of about 0.1 to about 100 hf l .
  • LHSV liquid hourly space velocity
  • Figure 1 is a graph plotting sec-butylbenzene selectivity against cumulative pore volume in the 2-8 nm range for the MCM-49 catalysts of Examples 1 to 5.
  • Figure 2 is a graph plotting by-product selectivity against cumulative pore volume in the 2-8 nm range for the MCM-49 catalysts of Examples 1 to 5.
  • Figure 3 is a graph comparing the sec-butylbenzene selectivity and the dibutylbenzene selectivity of the MCM-49 catalysts of Examples 11 to 14. DETAILED DESCRIPTION OF THE EMBODIMENTS
  • the present invention is directed to a process for producing sec- butylbenzene by alkylating benzene with a C 4 alkylating agent in the presence of a particulate catalyst comprising zeolite beta or a zeolite of the MCM-22 family, wherein the catalyst particle is shaped, for example by having a quadrulobe cross- section, such that the catalyst particles have a surface to volume ratio of at least 80 inch "1 and conveniently less than 200 inch "1 .
  • the selectivity of the catalyst to the desired monoalkylated species, sec-butylbenzene is increased relative to a catalyst with a surface to volume ratio of less than 80 inch "1
  • the alkylation activity of the catalyst is increased even more markedly, for example by more than 60% relative to a catalyst with a surface to volume ratio of less than 80 inch "1 .
  • the amount and type of binder in the catalyst is important in determining the activity and monoalkylation selectivity of the catalyst.
  • the catalyst should contain about 50 to about 90 wt%, such as about 60 to about 80 wt%, of zeolite beta or said at least one molecular sieve of the MCM-22 family, with the remainder being a binder, particularly an alumina binder. It is also found that improved sec- butylbenzene selectivity is obtained if the amount and type of binder employed in the alkylation catalyst is such that the catalyst has a cumulative pore volume in the 2 to 8 nanometer range, as measured by nitrogen porosimetry, of greater than 0.04 cc/gm, such as greater than 0.07 cc/gm, for example greater than 0.10 cc/gm.
  • the benzene employed in the alkylation step to produce sec- butylbenzene can be any commercially available benzene feed, but preferably the benzene has a purity level of at least 99 wt%.
  • the C 4 alkylating agent comprises at least one linear butene, namely butene-1, butene-2 or a mixture thereof.
  • the alkylating agent can also be an olefinic C 4 hydrocarbon mixture containing linear butenes, such as can be obtained by steam cracking of ethane, propane, butane, LPG and light naphthas, catalytic cracking of naphthas and other refinery feedstocks and by conversion of oxygenates, such as methanol, to lower olefins.
  • C 4 hydrocarbon mixtures are generally available in any refinery employing steam cracking to produce olefins; a crude steam cracked butene stream, Raffinate-1 (the product of remaining after solvent extraction or hydrogenation to remove butadiene from the crude steam cracked butene stream) and Raffinate-2 (the product remaining after removal of butadiene and isobutene from the crude steam cracked butene stream).
  • Raffinate-1 the product of remaining after solvent extraction or hydrogenation to remove butadiene from the crude steam cracked butene stream
  • Raffinate-2 the product remaining after removal of butadiene and isobutene from the crude steam cracked butene stream.
  • these streams have compositions within the weight ranges indicated in Table 1 below.
  • refinery mixed C 4 streams such as those obtained by catalytic cracking of naphthas and other refinery feedstocks, typically have the following composition:
  • C 4 hydrocarbon fractions obtained from the conversion of oxygenates, such as methanol, to lower olefins more typically have the following composition: Propylene - 0-1 wt%
  • any one or any mixture of the above C 4 hydrocarbon mixtures can be used in the present alkylation process.
  • these mixtures typically contain components, such as isobutene and butadiene, which can be deleterious to the alkylation process.
  • the normal alkylation product of isobutene with benzene is tert-butylbenzene which, as previously stated, acts as an inhibitor to the subsequent oxidation step.
  • these mixtures preferably are subjected to butadiene removal and isobutene removal.
  • isobutene can be removed by selective dimerization or reaction with methanol to produce MTBE, whereas butadiene can be removed by extraction or selective hydrogenation to butene-1.
  • the C 4 alkylating agent employed in the present process contains less than 1 wt% iso-butene and less than 0.1 wt% butadiene.
  • C 4 hydrocarbon mixtures typically contain other impurities which could be detrimental to the alkylation process.
  • refinery C 4 hydrocarbon streams typically contain nitrogen and sulfur impurities
  • C 4 hydrocarbon streams obtained by oxygenate conversion process typically contain unreacted oxygenates and water.
  • these mixtures may also be subjected to one or more of sulfur removal, nitrogen removal and oxygenate removal, in addition to butadiene removal and isobutene removal. Removal of sulfur, nitrogen, oxygenate impurities is conveniently effected by one or a combination of caustic treatment, water washing, distillation, adsorption using molecular sieves and/or membrane separation. Water is also typically removed by adsorption.
  • the total feed to the alkylation step of the present process 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.
  • the alkylation catalyst used in the present process is a crystalline molecular sieve of the MCM-22 family.
  • MCM-22 family material includes one or more of:
  • 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;
  • MCM-22 • molecular sieves made by any regular or random 2-dimensional or 3- dimensional combination of unit cells having the MWW framework topology.
  • Molecular sieves of the MCM-22 family include those molecular sieves having 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 are obtained by standard techniques using the K-alpha doublet of copper as incident radiation and a diffractometer equipped with a scintillation counter and associated computer as the collection system.
  • Materials of the MCM-22 family include MCM-22 (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.
  • the alkylation catalyst can include the molecular sieve in unbound or self-bound form or, more preferably, the molecular sieve can be combined in a conventional manner with an oxide binder, preferably alumina, such that the final alkylation catalyst contains between about 50 and about 90 wt%, for example between about 60 and about 80 wt%, of the molecular sieve, with the remainder being the binder.
  • the amount and type of the binder is selected such that the catalyst has a cumulative pore volume in the 2 to 8 nanometer range, as measured by nitrogen porosimetry, of greater than 0.04 cc/gm, such as greater than 0.07 cc/gm, for example greater than 0.10 cc/gm.
  • the alkylation catalyst employed in the present process is formulated, generally by extrusion, into particles having a surface to volume ratio of at least 80 inch " 1 and conveniently less than 200 inch “1 , such as from about 100 inch "1 to about 150 inch “ 1 .
  • This can readily be achieved by controlling the particle size of the catalyst or by using a shaped catalyst particle, such as the grooved cylindrical extrudate described in U.S. Patent No. 4,328,130 or a hollow or solid polylobal extrudate as described in U.S. Patent No. 4,441,990, the entire contents of both of which are incorporated herein by reference.
  • a cylindrical catalyst particle having a diameter of 1/32 inch (0.8 mm) and a length of 3/32 inch (2.4 mm) has a surface to volume ratio of 141
  • a quadrulobal solid extrudate having the external shape disclosed in Figure 4 of U.S. Patent No. 4,441,990 and having a maximum cross-sectional dimension of 1/16 inch (1.6 mm) and a length of 3/16 inch (4.8 mm) has a surface to volume ratio of 128.
  • a hollow tubular extrudate having an external diameter of 1/10 inch (2.5 mm), an internal diameter of 1/30 inch (0.8 mm) and a length of 3/10 inch (7.6 mm) has a surface to volume ratio of 136.
  • the MCM-22 family catalyst Prior to use in the present alkylation process, the MCM-22 family catalyst, either in bound or unbound form, may be contacted with water, either in liquid or vapor form, under conditions to improve its sec-butylbenzene selectivity.
  • the conditions of the water contacting are not closely controlled, improvement in sec-butylbenzene selectivity can generally be achieved by contacting the zeolite with water at temperature of at least 0 0 C, such as from about 1O 0 C to about 50 0 C, for a time of at least 0.5 hour, for example for a time of about 2 hours to about 24 hours.
  • the water contacting is conducted so as to increase the weight of the catalyst by 30 to 75 wt% based on the initial weight of the zeolite.
  • the water contacting promotes re-insertion of Al into the tetrahedral framework of the zeolite and/or a relaxation of the local geometric strains that are induced by earlier steps in the zeolite production, particularly calcination and/or dehydration.
  • the water contacting seems to be accompanied by increases in the amplitude or width of at least one of the peaks in the 29 Si MAS NMR spectrum of the zeolite in the chemical shift range of -80 to -120 ppm from tetramethylsilane (TMS).
  • the MCM-22 family zeolite may be used directly as an alkylation catalyst for the production of sec-butylbenzene.
  • the zeolite can be dried in air or an inert gas, such as nitrogen, such as at a temperature of about 100 0 C to about 200 0 C for a time of about 1 hour to about 5 hours. Surprisingly, it is found that this drying step does not significantly detract from the improvement in sec-butylbenzene selectivity produced by the water contacting step.
  • the alkylation process is conducted such that the organic reactants, i.e., the alkylatable aromatic compound and the alkylating agent, are brought into contact with the alkylation catalyst described above under effective alkylation conditions controlled so as to maximize the conversion to sec-butylbenzene and minimize the formation of butene oligomers.
  • a large stoichiometric excess of benzene is fed to the alkylation reaction and the local concentration of the alkylating agent is reduced preferably by staged addition of the alkylating agent. This is conveniently achieved by providing the alkylation catalyst in a plurality of fixed bed reaction zones connected in series.
  • the alkylation reaction can be conducted in a catalytic distillation reactor, with the alkylating agent being fed to the reactor continuously or in stages over the course of the reaction.
  • the total amounts of benzene and alkylating agent fed to reaction should be such that the overall molar ratio of benzene to alkylating agent is from about 1 to about 20, preferably about 3 to about 10, more preferably about 4 to about 9.
  • the alkylation conditions conveniently include a temperature of from about 6O 0 C to about 260 0 C, for example between about 100 0 C and about 200 0 C, a pressure of 7000 kPa or less, for example from about 1000 to about 3500 kPa, and a weight hourly space velocity (WHSV) based on C 4 alkylating agent of between about 0.1 and about 50 hr "1 , for example between about 1 and about 10 hr "1 .
  • the alkylation conditions are selected so that benzene is at least partially in the liquid phase.
  • the alkylation step of the process of the invention is highly selective to sec-butylbenzene.
  • the alkylation product generally comprises at least 93 wt%, preferably at least 95 wt%, sec-butylbenzene, between about 0.01 wt% and about 1 wt%, preferably between about 0.05 wt% and about 0.8 wt% of butene oligomers, and less than 0.5 wt% of isobutylbenzene.
  • the alkylation step is highly selective towards sec- butylbenzene
  • the effluent from the alkylation reaction will normally contain some polyalkylated products, as well as unreacted aromatic feed and the desired monoalkylated species.
  • the unreacted aromatic feed is normally recovered by distillation and recycled to the alkylation reactor.
  • the bottoms from the benzene distillation are further distilled to separate monoalkylated product from any polyalkylated products and other heavies.
  • Transalkylation with additional benzene is typically effected in a transalkylation reactor, separate from the alkylation 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.
  • a suitable transalkylation catalyst such as a molecular sieve of the MCM-22 family include MCM-22 (described in U.S. Patent No. 4,954,325), PSH-3 (described in U.S. Patent No. 4,439,409), SSZ-25 (described in U.S. Patent No. 4,826,667), ERB-I (described in European Patent No.
  • ITQ-I (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
  • mixtures thereof described in U.S. Patent No. 6,756,030
  • the transalkylation reaction is typically conducted under at least partial liquid phase conditions, which suitably include a temperature of 100 to 300 0 C, a pressure of 1000 to 7000 kPa, a weight hourly ssppaaccee vveelloocciittyy ooff 11 ttoo .50 hr "1 on total feed, and a benzene/polyalkylated benzene weight ratio of 1 to 10.
  • the sec-butylbenzene is initially oxidized to the corresponding hydroperoxide. This is accomplished by introducing an oxygen-containing gas, such as air, into a liquid phase containing the sec-butylbenzene.
  • an oxygen-containing gas such as air
  • atmospheric air oxidation of sec-butylbenzene in the absence of a catalyst is very difficult to achieve. For example, at 110 0 C and at atmospheric pressure, sec- butylbenzene is not oxidized, while cumene oxidizes very well under the same conditions. At higher temperature, the rate of atmospheric air oxidation of sec- butylbenzene improves; however, higher temperatures also produce significant levels of undesired by-products.
  • Suitable sec-butylbenzene catalysts include a water-soluble chelate compound in which multidentate ligands are coordinated to at least one metal from cobalt, nickel, manganese, copper, and iron (See U.S. Patent No. 4,013,725). More preferably, a heterogeneous catalyst is used. Suitable heterogeneous catalysts are described in U.S. Patent No. 5,183,945, wherein the catalyst is an oxo (hydroxo) bridged tetranuclear manganese complex and in U.S. Patent No.
  • the catalyst comprises an oxo (hydroxo) bridged tetranuclear metal complex having a mixed metal core, one metal of the core being a divalent metal selected from Zn, Cu, Fe, Co, Ni, Mn and mixtures thereof and another metal being a trivalent metal selected from In, Fe, Mn, Ga, Al and mixtures thereof.
  • oxo hydroxo
  • N-hydroxy substituted cyclic imides described in U.S. Patent No. 6,720,462 and incorporated herein by reference, 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-hydroxymaleimide, pyridine-2,3-dicarboximide, N-hydroxys
  • Suitable conditions for the sec-butylbenzene oxidation step include a temperature of about 70 0 C to about 200 0 C, such as about 90 0 C to about 130 0 C, and a pressure of about 0.5 to about 20 atmospheres (50 to 2000 kPa).
  • a basic buffering agent may be added to react with acidic by-products that may form during the oxidation, hi addition, an aqueous phase may be introduced to help dissolve basic compounds, such as sodium carbonate.
  • the per-pass conversion in the oxidation step is preferably kept below 50%, to minimize formation of byproducts.
  • the oxidation reaction is conveniently conducted in a catalytic distillation unit and the sec-butylbenzene hydroperoxide produced may be concentrated by distilling off unreacted sec-butylbenzene prior to the cleavage step.
  • the final step in the conversion of the sec-butylbenzene into phenol and methyl ethyl ketone involves cleavage of the sec-butylbenzene hydroperoxide, which is conveniently effected by contacting the hydroperoxide with a catalyst in the liquid phase at a temperature of about 20 0 C to about 15O 0 C, such as about 4O 0 C to about 12O 0 C, a pressure of about 50 to about 2500 kPa, such as about 100 to about 1000 kPa and a liquid hourly space velocity (LHSV) based on the hydroperoxide of about 0.1 to about 100 hr "1 , preferably about 1 to about 50 hr "1 .
  • LHSV liquid hourly space velocity
  • the sec-butylbenzene hydroperoxide is preferably diluted in an organic solvent inert to the cleavage reaction, such as methyl ethyl ketone, phenol or sec- butylbenzene, to assist in heat removal.
  • the cleavage reaction is conveniently conducted in a catalytic distillation unit.
  • 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.
  • a suitable heterogeneous catalyst for use in the cleavage of sec-butylbenzene hydroperoxide includes a smectite clay, such as an acidic montmorillonite silica-alumina clay, as described in U.S. Patent No. 4,870,217, the entire disclosure of which is incorporated herein by reference.
  • catalyst performance is defined by reference to the kinetic rate constant which is determined by assuming first- order reaction kinetics.
  • kinetic rate constant which is determined by assuming first- order reaction kinetics.
  • reference is directed to "Heterogeneous Reactions: Analysis, Examples, and Reactor Design, Vol. 2: Fluid-Fluid-Solid Reactions” by L. K. Doraiswamy and M. M. Sharma, John Wiley & Sons, New York (1994) and to "Chemical Reaction Engineering” by O. Levenspiel, Wiley Eastern Limited, New Delhi (1972).
  • One gram of the sized catalyst was used for alkylation of benzene with 2-butene in a fixed-bed reactor.
  • the catalyst was diluted with sand to 3 cc and loaded into an isothermal, down-flow, fixed-bed, tubular reactor having an outside diameter of 4.76 mm (3/16").
  • the catalyst was dried for 2 hours at 150 0 C and 1 atm with 100 cc/min flowing nitrogen. Nitrogen was turned off and benzene was fed to the reactor at 60 cc/hr until reactor pressure reached 300 psig (2170 kPa). Benzene flow was then reduced to 7.63 cc/hr and temperature was adjusted to 16O 0 C.
  • Example 2 The same startup procedure described in Example 1 was followed. Data were collected at 4, 12, and 4 WHSV on butene at 160 0 C, 300 psig (2170 kPa), and 3: 1 benzene/butene molar ratio. First-order rate constant based on butene conversion and total catalyst weight was 24.7 hr "1 for this catalyst. Representative data at 95% butene conversions after lineout are shown in Table 2.
  • the resultant sized catalyst had a surface to volume ratio of 120 inch "1 .
  • a 0.8 g aliquot of this sized MCM-49 catalyst was used for alkylation of benzene with 2- butene in a fixed-bed reactor.
  • the catalyst was diluted with sand to 3 cc and loaded into an isothermal, down-flow, fixed-bed, tubular reactor having an outside diameter of 4.76 mm (3/16").
  • the catalyst was dried for 2 hours at 150 0 C and 1 atm with 100 cc/min flowing nitrogen. Nitrogen was turned off and benzene was fed to the reactor at 60 cc/hr until reactor pressure reached 300 psig (2170 kPa). Benzene flow was then reduced to 7.63 cc/hr and temperature was adjusted to 16O 0 C.
  • 2-Butene feed 48.66% cis-butene, 51.07% trans-butene, 0.05% n-butane, 0.21% isobutene and 1-butene, and 0.01% others was introduced from a syringe pump at 2.57 cc/hr or 2.0 WHSV.
  • Feed benzene/butene molar ratio was 3:1. Liquid products were collected in a cold-trap and analyzed off line. Butene conversion was determined by measuring unreacted butene relative to feed butene. Data were collected at 2.0 then 6.0 WHSV on butene at 160 0 C, 300 psig (2170 kPa), and 3:1 benzene/butene molar ratio. First-order rate constant based on butene conversion and total catalyst weight was 6.4 hr "1 for this catalyst. Representative data at 94% butene conversions are shown in Table 3.
  • the resultant sized catalyst had a surface to volume ratio of 120 inch "1 .
  • a 0.4 g aliquot of this sized MCM-49 catalyst was used for alkylation of benzene with 2- butene in a fixed-bed reactor. The same startup procedure described in Example 3 was followed.
  • the resultant sized catalyst had a surface to volume ratio of 120 inch "1 .
  • a 0.4 g aliquot of this sized MCM-49 catalyst was used for alkylation of benzene with 2- butene in a fixed-bed reactor. The same startup procedure described in Example 3 was followed.
  • the resultant sized catalyst had a surface to volume ratio of 120 inch "1 .
  • a 0.38 g aliquot of this sized MCM-49 catalyst was used for alkylation of benzene with 2- butene in a fixed-bed reactor. The same startup procedure described in Example 3 was followed.
  • Catalyst cumulative pore volume data in the 2-8 nm range (meso pore range) obtained from N 2 porosimetry are also shown at the bottom of Table 3.
  • Figure 1 plots s-BB selectivity vs. the cumulative pore volume in the 2- 8 nm range
  • Figure 2 plots byproduct selectivity vs. the cumulative pore volume in the 2-8 nm range. From these results it will be seen that catalysts with 20%, 40%, and 60% MCM-49 had sufficient alumina binder and high mesoporosity (0.18 - 0.29 cc/g) and achieved 94% s-BB selectivity with DiBB level below 4%.
  • the 80% MCM-49 catalyst had reduced content of alumina binder and reduced mesoporosity range (0.12 cc/g) achieved reduced s-BB selectivity of 92% and increased DiBB selectivity of 6%.
  • the above results suggest that the 20%, 40% and 100% MCM-49 formulations are less preferred for s-BB production.
  • the data show that high binder mesoporosity is important for MCM-49 catalysts to achieve high s-BB selectivity.
  • preferred catalyst formulation for MCM-49 type catalysts can be obtained by using binders, such as alumina, characterized by the presence of sufficient mesoporosity.
  • binders such as alumina, characterized by the presence of sufficient mesoporosity.
  • Such binders would provide mesoporosity higher than 0.04 cc/g as measured by N 2 porosimetry.
  • Example 5 The catalyst described in Example 5 was humidified at room temperature with 100% humidity. A 0.40 g sample of the catalyst (cut to 1/20 inch length as well) was weighed into a sample tray. The tray with the catalyst was placed on a holding-tray inside a desiccator, which contained water at bottom. There was no direct contact between the catalyst and liquid water. The catalyst was left in the closed desiccator overnight. The final weight of the catalyst was 0.65 g. The entire amount was loaded to the reactor with the same procedure described in Example 1. The catalyst was used without drying. Benzene was fed to the reactor at 60 cc/hr until reactor pressure reached 300 psig (2170 kPa) and reactor temperature reached 160 0 C (ramped at 5°C/min).
  • Benzene flow was then reduced to 7.63 cc/hr.
  • the same 2-butene feed was introduced at 2.57 cc/hr or 4 WHSV.
  • Feed benzene/butene molar ratio was maintained at 3:1 for the entire run.
  • Data were collected at 4, 12, 26, then 4 WHSV on butene at 160 0 C, 300 psig (2170 kPa), and 3:1 benzene/butene molar ratio. Representative data at 97% butene conversion after lineout are shown in Table 4.
  • Example 8 The humidification and testing procedure of Example 8 was followed using catalyst described in Example 6. Data were collected at 4.2, 12.6, 25.2, then 4.2 WHSV on butene at 160°C, 300 psig (2170 kPa), and 3:1 benzene/butene molar ratio. Representative data at 97% butene conversion after lineout are shown in Table 4.
  • Example 8 The humidification and testing procedure of Example 8 was followed using catalysts described in Example 7. Data were collected at 8, 24, then 36 WHSV on butene at 160 0 C, 300 psig (2170 kPa), and 3:1 benzene/butene molar ratio. Representative data at 91% butene conversion are shown in Table 4. Table 4
  • a further 0.38 g sample of the sized catalyst from Example 6 was humidified overnight at room temperature with 100% humidity using water.
  • the catalyst was weighed into a sample tray.
  • the tray with the catalyst was placed on a holding-tray inside a desiccator which contained water at bottom. There was no direct contact between the catalyst and liquid water.
  • the catalyst was left in the closed desiccator overnight.
  • the final weight of the catalyst was 0.50 g.
  • the entire amount was loaded into the reactor using the same procedure described in Example 1.
  • the catalyst was used without drying. Benzene was fed to the reactor at 60 cc/hr until the reactor pressure reached 300 psig (2170 kPa) and the reactor temperature reached 160 0 C (ramped at 5°C/min).
  • Benzene flow was then reduced to 7.63 cc/hr.
  • the same 2-butene feed used in Example 1 was introduced at 2.57 cc/hr or 4.2 WHSV.
  • Data were collected at 4.2, 12.6, 25.2, then 4.2 WHSV on butene at 160 0 C, 300 psig (2170 kPa), and 3:1 benzene/butene molar ratio.
  • First- order rate constant based on butene conversion and total catalyst weight was 48.9 hr "1 for this catalyst. Representative data at 97% butene conversions after lineout are shown in Table 5.
  • a fresh MCM-49 catalyst with a nominal composition of 80% MCM- 49 crystal and 20% silica as binder was extruded with silica into 1/20 inch quadrulobe form. This extrudate was then pre-calcined in nitrogen at 51O 0 C, ammonium exchanged with ammonium nitrate to remove sodium, and calcined in air-nitrogen mixture at 538°C. The extrudate was cut to 1/20 inch length. A 0.20 g of the sized catalyst was humidified overnight at room temperature with 100% humidity using water. The final weight of the catalyst was 0.28 g. The entire amount was loaded to the reactor with the same procedure described in Example 1. The same startup procedure described in Example 11 was followed.
  • a fresh MCM-49 catalyst with a nominal composition of 80% MCM- 49 crystal and 20% P25 titania as binder was extruded into 1/20 inch quadrulobe form. This extrudate was then pre-calcined in nitrogen at 510 0 C, ammonium exchanged with ammonium nitrate to remove sodium, and calcined in air-nitrogen mixture at 538°C. The extrudate was cut to 1/20 inch length. A 0.20 g of the sized catalyst was humidified overnight at room temperature with 100% humidity using water. The final weight of the catalyst was 0.26 g. The entire amount was loaded to the reactor with the same procedure described in Example 1. The same startup procedure described in Example 11 was followed.
  • Example 7 The same catalyst described in Example 7 was used and the extrudate was cut to 1/20 inch length. A 0.20 g of the sized catalyst was humidified overnight at room temperature with 100% humidity using water. The final weight of the catalyst was 0.26 g. The entire amount was loaded to the reactor with the same procedure described in Example 1. The same startup procedure described in Example 11 was followed. Data were collected at 8, 24, then 8 WHSV on butene at 160 0 C, 300 psig (2170 kPa), and 3:1 benzene/butene molar ratio. First-order rate constant based on butene conversion and total catalyst weight was 36.8 hr "1 for this catalyst. Representative data at 93% butene conversions are shown in Table 5.
  • Catalysts with silica and titania binder had low mesoporosity (0.03 and 0.04 cc/g respectively), and provided much lower s-BB selectivity (86.7% and 88.1% respectively) and much higher DiBB make (9.3% and 9.1% respectively).
  • the catalyst with no binder (100% MCM-49) also had low mesoporosity (0.03 cc/g) and provided low s-BB selectivity (86.4%) and high DiBB make (10.8%).

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

Abstract

L'invention concerne un procédé de fabrication de sec-butylbenzène comportant la réaction du benzène avec au moins un agent alkylant en C4 dans des conditions d'alkylation et en présence d'un catalyseur d'alkylation particulaire comprenant de la zéolite bêta et/ou au moins un tamis moléculaire de la famille des MCM-22 pour obtenir un produit d'alkylation comprenant du sec-butylbenzène. Les conditions d'alkylation sont telles que le benzène se trouve au moins partiellement dans la phase liquide et les particules du catalyseur d'alkylation ont un rapport surface à volume d'au moins 80 pouces-1.
PCT/US2007/062043 2006-02-14 2007-02-13 Procédé de fabrication du sec-butylbenzène Ceased WO2007143239A2 (fr)

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PCT/EP2008/000664 WO2008098676A1 (fr) 2007-02-13 2008-01-25 Procédé de fabrication de sec-butylbenzène
TW097103312A TW200904778A (en) 2007-02-13 2008-01-29 Process for producing sec-butylbenzene

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008088659A2 (fr) 2007-01-16 2008-07-24 Exxonmobil Chemical Patents Inc. Composition catalytique et son utilisation dans l'alkylation de composés aromatiques
WO2009082464A1 (fr) * 2007-12-21 2009-07-02 Exxonmobil Research And Engineering Company Procédé pour produire un phénol et une méthyl éthyl cétone

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5149894A (en) * 1986-01-29 1992-09-22 Chevron Research And Technology Company Alkylation using zeolite SSZ-25
US5362697A (en) * 1993-04-26 1994-11-08 Mobil Oil Corp. Synthetic layered MCM-56, its synthesis and use
US7038100B2 (en) * 2001-04-30 2006-05-02 Exxonmobil Chemical Patents, Inc. Aromatics alkylation
US20020042548A1 (en) * 2001-07-11 2002-04-11 Dandekar Ajit B. Process for producing cumene

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008088659A2 (fr) 2007-01-16 2008-07-24 Exxonmobil Chemical Patents Inc. Composition catalytique et son utilisation dans l'alkylation de composés aromatiques
WO2008088659A3 (fr) * 2007-01-16 2009-03-26 Exxonmobil Chem Patents Inc Composition catalytique et son utilisation dans l'alkylation de composés aromatiques
US8492602B2 (en) 2007-01-16 2013-07-23 Exxonmobil Chemical Patents Inc. Catalyst composition and its use thereof in aromatics alkylation
US8703635B2 (en) 2007-01-16 2014-04-22 Exxonmobil Chemical Patents Inc. Catalyst composition and its use thereof in aromatics alkylation
WO2009082464A1 (fr) * 2007-12-21 2009-07-02 Exxonmobil Research And Engineering Company Procédé pour produire un phénol et une méthyl éthyl cétone
US7759524B2 (en) 2007-12-21 2010-07-20 Exxonmobil Research And Engineering Company Process for producing phenol and methyl ethyl ketone

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