TW200904778A - Process for producing sec-butylbenzene - Google Patents

Abstract

A process for producing sec-butylbenzene comprises reacting benzene with at least one linear butene under alkylation conditions and in the presence of a catalyst comprising at least one molecular sieve 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 to produce an alkylation product comprising sec-butylbenzene. Prior to the reacting, the catalyst is contacted with water under conditions to improve the sec-butylbenzene selectivity of the catalyst.

Description

200904778 IX. INSTRUCTIONS OF THE INVENTION · FIELD OF THE INVENTION The present invention relates to a process for preparing a second butylbenzene, and a process for converting the butylbenzene to phenol and methyl ethyl ketone. [Prior Art] Phenol and methyl ethyl ketone are important products in the chemical industry. By way of example, phenol can be used in the manufacture of phenolic resins, bisphenol A, ε-caprolactam, adipic acid, alkylphenols and plasticizers, while methyl ethyl ketone can be used as a paint, solvent and lubricant. Dewaxing. The most common route for the manufacture of methyl ethyl ketone is by dehydrogenating a second butanol (SBA) which is produced by catalyzing hydration of butyl sulphonate. For example, a commercial scale SBA manufacturing line that reacts butene with sulfuric acid has been implemented for many years by gas/liquid extraction. Recently, the most common route for the production of phenol is the Hock method. This is a three-step process in which the first step comprises alkylating benzene with propylene to produce cumene, followed by oxidizing the cumene to the corresponding hydroperoxide, and then breaking the hydroperoxide to produce a molar amount. Phenol and acetone. However, the world demand for phenol is growing faster than the demand for acetone. In addition, the cost of propylene may increase relative to butenes. This is because propylene is gradually being reduced. Therefore, a method of using butene instead of propylene as a feed for the production of phenol and co-forming a non-acetone methyl ethyl ketone may be an attractive alternative route. It is known that phenol and methyl ethyl ketone can be produced by a modification of the Hock method, in which a total of -5,047,047,78 is produced, wherein the second butylbenzene is oxidized to obtain a second-butylbenzene hydroperoxide, and the The oxide is decomposed into the desired phenol and methyl ethyl ketone. A description of this method is disclosed in Process Economics Report No. 22B, pages 113-421 and 261-263, under the heading "Phenol"

Stanford Reserch Institute was published in December 1977. The second butylbenzene can be produced by alkylating benzene with n-butene on acid contact coal. Thus, International Patent Publication No. WO 06/158,826 discloses an integrated process for the manufacture of phenol and methyl ethyl ketone in which a feed comprising benzene and a C4 alkylating agent is combined with a yS-containing zeolite under alkylation conditions. Or contacting the coal of the MCM-22 family of molecular sieves to produce an alkylated effluent containing the second butylbenzene. The second butylbenzene is then oxidized to produce a hydroperoxide, and the hydroperoxide is cleaved to produce the desired phenol and methyl ethyl ketone. Traditionally, zeolites of the cerium or MCM-22 family are molecular sieves. By reacting an aqueous mixture of ceria source or other tetravalent metal oxide, alumina source or other trivalent metal oxide and a priming reagent (usually a nitrogen-containing organic base) at elevated temperatures for several hours to several days until Manufactured by obtaining a crystalline product. By way of example, in the alkylation process described in WO 06/158,826, the crystalline product is separated from the residue of the synthesis mixture and subjected to various finishing steps such as extrusion, ion exchange and calcination prior to use as a coal touch. . In general, the final step in the preparation of the coal strike is a calcination step or a drying step of at least 13 ° C to 220 ° C in the presence of an inert gas to remove water adsorbed during storage. Therefore, the molecular sieve coal is typically very dry when used as a coal touch in the manufacturing process of the second butylbenzene. -6- 200904778 When molecular sieves such as zeolite 3 and MCM-2 2 are used in the manufacture of second butyl benzene, there is usually a line out time, followed immediately by the start, during which time Coal produces high amounts of dialkylated and trialkylated products. Depending on how the coal is made and calcined, the second butylbenzene selectivity will vary considerably during startup and during steady state manufacturing. Although the polyalkylated product can be converted back to the second butylbenzene by transalkylation, this adds an extra step, thus maximizing the monoalkylation selectivity during startup and steady state conditions. There is a great interest in chemistry. According to the present invention, it has been found that the second butylbenzene selectivity of the MC Μ 2 2 family species during startup and steady state conditions can be improved by using molecular sieves for the alkylation process to produce the second butyl group. Prior to benzene, the molecular sieve is contacted with water in vapor or liquid form. Although the reasons for increasing the selectivity are not fully understood, the 29 Si MAS NMR data suggests that contact with water promotes the re-insertion of the A1 into the tetrahedral framework of the zeolite and/or mitigates earlier steps in the manufacture of the zeolite (especially calcination and/or dehydration). The local geometric strain caused by it. If the selectivity is not taken into account, it has been found that this enhancement can be maintained even after the zeolite is dried at about 15 ° C after the water contacting step and before the alkylation process. U.S. Patent No. 4,46, 475, the disclosure of which is incorporated herein incorporated by reference in its entirety the entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire portion The catalytic activity conditions and the mixture of zeolite and alumina are contacted with an aqueous liquid medium (typically water) at a temperature of from about 1 °C to about 370 °C. U.S. Patent No. 5,077,445 discloses a process for the preparation of a benzene based base (particularly ethylene 200904778 benzene) wherein the process comprises contacting an olefin having from 2 to 6 carbon atoms and liquid benzene with a catenary under alkylation conditions. The contact coal contains a hydrated synthetic porous crystalline MC Μ 2 2 substance. When the crystalline substance is first contacted with the benzene and the olefin, the hydrated crystalline substance contains at least 1 part by weight of liquid water contained in the pore space of the crystalline substance. Wherein the alkylation conditions comprise a combination of temperature and pressure sufficient to maintain the benzene and the water in a liquid state, wherein the hydrated crystalline material is at least 1 in the pore space by placing the crystalline material in liquid water 0% by weight of water is hydrated at the time. It is said that the presence of water inhibits the polyalkylation reaction, thus minimizing the formation of unwanted by-products, especially those having 9 or more carbon atoms. SUMMARY OF THE INVENTION In one aspect, the present invention is directed to a method of making a second butylbenzene comprising benzene and at least under alkylation conditions and in the presence of a catalyst comprising at least one MCM-22 family molecular sieve A C4 alkylating agent reacts to form an alkylated product containing a second butylbenzene, wherein prior to the reaction, the catalyst is in contact with water under conditions which increase the selectivity of the second butylbenzene of the catalyst contact. In another aspect, the invention relates to the use of a catalyst comprising at least one molecular sieve of the MCM-2 2 family in a process for the manufacture of a second butylbenzene, the method of making benzene and at least one under alkylation conditions The C4 alkylating agent is reacted, wherein the molecular sieve has been contacted with water prior to use to increase the second butylbenzene selectivity of the coal. -8 _ 200904778 In a preferred embodiment, as required by the process of the present invention, the second butylbenzene selectivity of the coal contacted with water is the same as that of other processes using the same reactants, coal and process conditions. The second butylbenzene selectivity obtained by contacting the coal with water is at least 1% by weight, preferably at least 2% by weight, and even at least 3% by weight. Conventionally, the contact with water is carried out under conditions including a temperature of at least 〇c. Contact with water is preferably at least 0. 5 hours. More preferably, the temperature of contact with water is between about 10 ° C and about 50 °. (In the range. More preferably, the time of contact with water is from about 2 hours to about 24 hours. In a specific embodiment, the contact with water is between -80 and -120 ppm of tetramethyl decane (TMS) ( More particularly, the TMS ranges from -90 to -100'-94 to -100 or about -98 Ppm. The chemical shift range is sufficient to substantially change the amplitude or width of at least one peak in the 29Si MAS NMR spectrum of the catalyst. In one embodiment, the catalyst is in contact with liquid water. In another embodiment, the catalyst is in contact with water vapor. Conventionally, the catalyst is after contact with water and at the Drying before the reaction. For example, the drying temperature may range from about 100 ° C to about 200 ° C. Preferably, the drying is carried out for about 1 hour to about 5 hours. Conventionally, the C4 alkylating agent comprises a straight a chain butene, such as butene-1, butene-2, or a mixture thereof. Preferably, the linear butene is in a total molar ratio of from about 1 to about 20 inclusive of benzene to butene ( Adding to the method under the alkylation conditions of from about 3 to about 1 Torr, preferably from about 4 to about 9, preferably -9-200904778, conventionally, The alkylation conditions also include a temperature of about 6 (TC to about 260 ° C, and/or a pressure of 7000 kPa or less, and/or a weight space velocity of the feed per hour based on the C4 alkylating agent (WHSV) ) is from about 0 · 1 to 50 hr · 1. In a specific embodiment, the reaction is carried out under at least a portion of the liquid phase. Typically, the MCM-22 family molecular sieve has at 12. 4±0. 25, 6. 9±0. 15, 3·57±0·07 and 3. 42±0. The 07 angstrom has an X-ray diffraction pattern with the largest d-spacing. Conventionally, the molecular sieve system is selected from the group consisting of MCM-22, PSH-3, SSZ-25, ERB-1, IT Q-1, IT Q-2, MC Μ - 3 6 , MC Μ - 4 9 , MCM-56 , UZM-8, and a mixture of them. In a specific embodiment, the process of the present invention further comprises oxidizing the second butylbenzene to form a hydroperoxide, and cleavage of the hydroperoxide to produce phenol and methyl ethyl ketone. Accordingly, in another preferred aspect, the method of the present invention is directed to a method of making phenol and methyl ethyl ketone, the method comprising: (a) contacting a catalyst comprising at least one MCM-22 family molecular sieve with water (b) after (a), reacting benzene with at least one linear butene in the presence of the alkylation conditions and the catalyst to form an alkylated effluent containing the second butylbenzene; (b) oxidizing the second butylbenzene to form a hydroperoxide; and (d) cleavage of the hydroperoxide from (c) to produce phenol and methyl-10-10,047,7878-ethyl ethyl ketone, which is conventionally known Oxidation [Step (C) of the above preferred viewpoint] is carried out in the presence of a catalyst, for example, a catalyst selected from the group consisting of: (i) a keto-based (hydroxyl) bridged tetranuclear metal complex containing manganese, (Π) a keto (hydroxy) bridged tetranuclear metal complex having a mixed metal core, one of which is a divalent metal selected from the group consisting of Zn, Cu' Fe, Co, Ni, Μη and The mixture, and another metal, is a trivalent metal selected from the group consisting of In, Fe, Μη, Ga, Α1, and mixtures thereof, (iii) either alone or in freedom N-hydroxy substituted cyclic quinone imine in the presence of a base initiator, and (iv) N,N',N"-trihydroxyisocyanuric acid alone or in the presence of a free radical initiator. In one embodiment, the oxidation catalyst is a heterogeneous catalyst. Conventionally, the oxidation system is at a temperature of from about 70 ° C to about 200 ° C, and / or from about 50 to about 2000 kPa (0. It is conventionally carried out under a pressure of 5 to 20 atm. The fracture [step (d) of the above preferred viewpoint] is carried out in the presence of a catalyst. The catalyst can be a homogeneous or heterogeneous phase catalyst. In a specific embodiment, the catalyst is a homogeneous catalyst such as sulfuric acid. Conventionally, the fracture is at a temperature of from about 40 ° C to about 12 (TC, and/or a pressure of from about 100 to about 2 500 kPa, and/or an hourly liquid space based on the hydroperoxide). The speed (LHSV) is from about 0. 1 to about 1000 hr · 1. [Embodiment] The present invention relates to the presence of a catalyst containing M CM-2 2 zeolite in the presence of a catalyst - 11 - 200904778 to make benzene and c4 A method for producing a second butylbenzene by reacting an alkylating agent, wherein the zeolite is completed before being treated with water. In particular, the present invention is characterized in that the MC Μ - 2 2 family zeolite is subjected to water treatment to increase the startup period and This finding based on the selectivity of the second butylbenzene in steady state conditions is surprising. Even though the water treated zeolite is subjected to a subsequent drying step, this enhancement can be maintained, but others have been known to be active. The zeolite of the alkylation catalyst does not exhibit this improvement. In addition to improving the selectivity of the second butylbenzene, it has been found that water treatment can also reduce butene oligomers and poly-polymers produced as by-products in the alkylation step. The amount of butylbenzene. When the second butyl benzene is intended for phenol and methyl b The reduction of oligomer formation (not a problem in lower olefin feeds such as ethylene) is particularly important in the manufacture of ketones. In the manufacture of phenol and methyl ethyl ketone, the first butyl benzene is initially produced. Oxidation to the corresponding hydroperoxide, and then the resulting hydroperoxide is cleaved to produce the desired phenol and methyl ethyl hydrazine (ΜΕΚ). Therefore, the oxidation of the second butyl benzene to impurities (especially butene The presence of the polymer) is very sensitive, so any alkylation process that increases the production of the second butylbenzene and reduces the production of butene oligomers provides significant advantages throughout the phenol/ruthenium manufacturing stage. The benzene used in the alkylation step to produce the second butylbenzene can be any commercial benzene feed, but preferably the benzene has a purity of at least 99% by weight. The 〇C4 alkylating agent comprises at least one linear butene. , that is, butene-1-12-200904778, butene-2, or a mixture thereof. The alkylating agent may also be a mixture of olefinic C4 hydrocarbons containing linear butenes, such as those which can be ethane, Propane, butane, LPG and light naphtha vapour The winners are those who obtain catalytic cracking of naphtha and other refinery feeds, and are obtained by converting oxygenates such as methanol to lower olefins. For example, the following C4 hydrocarbon mixtures are usually Any refinery that utilizes steam cracking to produce olefins: crude steam cracked butene stream, raffinate-1 (solvent or hydrogenation to remove butadiene from the crude steam cracked butene stream) The product) and raffinate-2 (products remaining after removal of butadiene and isobutylene from the crude steam cracked butene stream). Generally, these streams have compositions within the weight ranges shown in Table 1 below. Table 1 Component crude raffinate 1 Raffinate 2 Solvent extraction hydrogenation solvent extraction hydrogenated butadiene 30-85 % 0-2 % 0-2 % 0-1 % 0-1 % C4 Acetylene 0-15 % 0-0. 5 % 0-0. 5 % 0-0. 5 % 0-0. 5 % Butene-1 1-30 % 20-50 % 50-95 % 25-75 % 75-95 % Butene-2 1-15 % 10-30 % 0-20 % 15-40 % 0-20 % Isobutylene 0-30 % 0-55 % 0-35 % 0-5 % 0-5 % n-butane 0-10 % 0-55 % 0-10 % 0-55 % 0-10 % _ Isobutane 0- 1 % 0-1 % 0-1 % 0-2 % 0-2 % A mixed C4 stream from other refineries, such as those obtained by catalytic cracking of naphtha and other refinery feeds, typically has the following Composition: • 13- 200904778 Propylene = 0-2 wt% Propane = 0-2 wt% Butadiene = 0 - 5 wt% Butene-1 = 5-20 wt% Butene-2 =1 0-50 wt% Isobutylene = 5 - 2 5 wt% isobutane = 10-45 wt% n-butane = 5 - 2 5 wt% More typically 'c4 hydrocarbon fraction obtained from converting an oxygen-containing compound such as methanol to a lower olefin Has the following composition: propylene = 0 -1% by weight 垸 垸 = 0-0. 5 wt% butadiene = 0-1 wt% butyrate - 1 = 10-40 wt% butene-2 = 50-85 wt% isobutadiene = 〇 -1 〇 wt% positive - + isobutane = 0 -10% by weight Any one or any mixture of the above c4 hydrocarbon mixtures can be used in the alkylation process of the present invention. In addition to linear butenes and butanes, these mixtures typically contain components such as isobutylene and butadiene which are detrimental to the alkylation procedure. By way of example, the normal alkylation product of isobutylene and benzene is a third butylbenzene which, as previously described, acts as an inhibitor of the subsequent oxidation step of -14 - 200904778. Thus, the alkylation step is preferably subjected to butadiene removal and isobutene dealkylation by selective dimerization or reaction with methanol, while butadiene can be preferably extracted or selectively hydrogenated. The c4 alkylating agent butene used in the invention is less than 〇.  1% butadiene. In addition to other hydrocarbon components, commercial c4 has other impurities that are detrimental to the alkylation process. The decanted hydrocarbon stream typically contains nitrogen and sulfur impurities, while the c4 hydrocarbon stream obtained from oxygen typically contains unreacted, and may be carried out in addition to butadiene and mixtures prior to the alkylation step. Secondary sulfur removal, material removal. Sulfur, nitrogen, oxygenate impurity treatment, water treatment, distillation, one of molecular sieves, or a combination thereof. Typically, the hydrazine is conveniently fed to the alkylation step of the invention at a ppm of 100 ppm, such as less than 500 ppm > for example less than/or the total feed typically contains less than 100 ppm, such as less than 3 ppm sulfur; And/or the total feed ppm, such as less than 1 ppm, such as less than 〇.  1 ppm, although less preferred, a viable alkylating agent and a C3 alkylating agent (such as an alkylating agent for the alkylation process of the propylene invention), such a mixture is removed. For example, The isobutylene is formed by removing the MTBE and removing the dilute-1. The oxygen-containing compound containing less than 1% of the mixture of isohydrocarbons typically contains hydrazine, the conversion of the c4 compound of the refinery, and water. Except for isobutylene, this nitrogen removal And the total amount of oxygen-containing oxides which are conventionally removed by adsorption by harsh adsorption and/or membrane fractions contains less than 100 ppm of water; and, if less than 30 ppm 'typically contains less than 1 〇 Nitrogen. Using a mixture of C4 as described above as a mixture of the present alkylation step -15-200904778 cumene and second butylbenzene. The resulting mixture can then be treated by oxidation and cleavage to produce a mixture of acetone and MEK and phenol. Preferably, the molar ratio of acetone to phenol is 〇 in order to meet the requirements for bisphenol-A production.  5 : 1. The alkylation catalyst used in the present invention is a crystalline molecular sieve of the MCM-22 family. As used herein, "MCM-22 family material" (or "MCM-22 family material" or "MCM-22 family molecular sieve" or "MCM-22 family zeolite") includes one or more of the following: A molecular sieve prepared by a common first-order crystalline structure unit wafer having a structural topology of MWW. (The unit cell is a spatial arrangement of atoms, which is laid out in a three-dimensional space to describe the crystal structure. Such crystal structure is disclosed in ''Atlas of Zeolite Framework Types", Fifth edition, 200 1, all of which will be included in this article. for reference); .  The molecular sieve prepared by the common second-stage structural unit is a two-dimensional space of the topological unit of such MWW architecture, and forms a single layer of unit crystal thickness, preferably a c-unit wafer thickness. • A molecular shop made from a common %-level structure unit, a layer of one or more unit cell thicknesses, wherein the layer of one or more unit cell thicknesses is self-stacked, densely bonded, or combined with at least two Manufactured in a single layer of one unit wafer thickness. The stack of such second-level structural units may be in a regular manner, an irregular manner, a random manner, or any combination thereof; and • a unit cell having a MWW architecture topology via any regular or random 2 degree-space Or a molecular sieve prepared by a combination of 3 degrees and space. MCM-22 family molecular sieves include those with a 4±0. 25, -16- 200904778 6,9±0. 15, 3. 5 7±0·07 and 3. 42±0. 07 angstroms have a d-spacing maximum X-ray diffraction pattern of molecular sieves. The X-ray diffraction data used to characterize the material was obtained using standard techniques and using copper Κ-α double 値 as the radiation for the incident radiation and equipped with a flash counter and connected to the computer as a collection system. MCM-22 family materials include MCM-22 (disclosed in U.S. Patent No. 4,954,325), PSH-3 (published in U.S. Patent No. 4,439,409), SSZ-25 (published in U.S. Patent No. 4,826,667), and ERB-1 (disclosed in European Patent) 〇 293 032), ITQ-1 (disclosed in U.S. Patent No. 6,077,498), ITQ-2 (disclosed in International Patent Publication No. WO 9 7/17290), MCM-36C disclosed in U.S. Patent No. 5,250,277, and MCM-49 ( It is disclosed in U.S. Patent No. 5,23,5,5,5, the disclosure of U.S. Patent No. 5,362,697, the disclosure of U.S. The preferred alkylation catalysts of the MCM-22 family of molecular sieves have found that the MCM-22 family of molecular sieves has a high selectivity for the manufacture of second butylbenzene when compared to other butylbenzene isomers. Preferably, the molecular sieve is selected from the group consisting of (a) MCM-49, (b) MCM-56 and (c) MCM-49 and MCM-56, such as ITQ-2. The alkylation catalyst can comprise a molecular sieve in an unbound or self-bound form, or alternatively, the molecular sieve can be combined with an oxide binder (e.g., alumina) in a conventional manner such that the final alkylation catalyst is compared Preferably, the ground contains 2 to 8 % by weight of mesh. In one embodiment, the catalyst is unbonded and has a superior crush strength than the catalyst formulated with the adhesive -17-200904778. Such a catalyst is suitably prepared by a vapor phase crystallization method, particularly a vapor phase crystallization method which prevents the caustic agent used in the synthesis mixture from remaining in the zeolite catalyst when vapor phase crystallization occurs. The MCM-22 family zeolite in bound or uncombined form is contacted with water in liquid or vapor form prior to use in the alkylation process of the present invention under conditions which promote the selectivity of the second butylbenzene of the zeolite. Although the conditions of contact with water are not precisely controlled, the increase in the selectivity of the second butylbenzene can usually be achieved by contacting the zeolite with at least 〇°c (e.g., about 1 〇. (: to about 5 〇r) of water. Preferably, the contacting is carried out for at least 〇 5 hours, for example from about 2 hours to about 24 hours. Typically, the contact with water is such that the catalyst weight is increased by 20 to 80% by weight based on the initial weight of the zeolite, More preferably, from 25 to 80% by weight, more preferably from 30 to 75% by weight, such as from 40 to 60% by weight. Although the reason for increasing the selectivity is not entirely clear, it is believed that contact with water promotes trivalent metals (usually aluminum). Reinserting into the tetrahedral framework of the zeolite and/or alleviating local geometric strains caused by earlier steps in the manufacture of the zeolite (especially calcination and/or dehydration). As a result, the contact with water appears to be accompanied by tetramethyl decane. (TMS) increases the amplitude or width of at least one peak in the 29Si MAS NMR spectrum of the zeolite in the range of -80 to -120 ppm chemical shift. In particular, contact with water appears to increase the 29Si MAS NMR spectrum of the zeolite at -90 to -100 ppm chemical position The resolution of a peak in the shift range, which is absent or unresolved in the zeolite without water treatment. In this relationship, all references to the NMR chemical shift number in this patent specification are Based on the displacement of the reference peak of the decane (TMS) of 200,904,778. After the water treatment, the 'MCM-22 family zeolite can be directly used as the alkylation catalyst for butylbenzene. Or, after contact with water, Before the catalyst, this zeolite can also be dried in air or an inert gas (such as nitrogen, for example, at about 1 ° C to about 200 ° C for about 1 hour. It is surprisingly found that this drying step There is no significant increase in the selectivity of the second butylbenzene produced by the water contacting step. The alkylation process is an alkylation of the aromatic compound and the alkylating agent under effective alkylation conditions. In contact with the above-mentioned catalyst, the effective alkylation condition is to control the conversion of the benzene to a maximum 値 and to achieve the formation of the butene oligomer, which is a large amount of stoichiometry. Excess benzene is fed to the alkylation' and Preferably, the concentration of the alkylation moiety is reduced by the addition of an alkylating agent in stages. This is conveniently accomplished by providing a plurality of fixed beds in series. Then, most or all of the benzene is fed. In the first part, however, the laboratory reagent is divided into several equal or different aliquots and each is fed into a different reaction zone. Alternatively, the alkylation reaction is carried out in a chemical distillation reactor and the alkylation is carried out. The reagent is fed to the reactor either continuously or in stages. In both cases, the total amount of benzene and alkylating agent fed therein is conveniently such that the total molar ratio of benzene to alkylation is about 1 Preferably, it is from about 3 to about 1 Torr, preferably about 9. Further, the alkylation conditions conveniently include a temperature of from about 60 ° C to about ° C (e.g., about i 〇 (TC to about 200) °C), and / or pressure is the second to the alkyl gas) to about 5 to reduce the cause, the hospitalized dibutyl is small. The reaction zone of the reaction zone of the specific reaction medium may be further reacted to 4 to about 260 3 7000 -19-200904778 kPa or less (e.g., about 1000 to about 3500 kPa) of the reactor reagent during the process, and/or to C4. The alkylation reagent-based hourly weight space velocity (WHSV) is about 〇. 1 to about 50 hr·1 (for example, about 1 to about 10 hr·1). The reactants may be in the vapor phase or in part or all of the liquid phase and may be pure, that is, not intentionally mixed or diluted with other materials, or the reactants may be diluted by means of a carrier gas or The agent (such as hydrogen or nitrogen) is contacted with the zeolite catalyst. Preferably, the reactant is at least a portion of the liquid phase. The alkylation step of the process of the invention was found to be highly selective for the second butylbenzene using the catalyst and alkylation conditions described above. In particular, it has been found that the alkylation product typically contains at least 93% by weight (preferably at least 95% by weight) of the second butylbenzene, and/or at about 0. Between 01% by weight and about 1% by weight (about 5% by weight of 〇·〇) and about 0. Between 8 wt%, preferably a butene oligomer, and/or less than 0. 5 wt% isobutylbenzene. Although the alkylation step is highly selective for the second butylbenzene, the effluent from the alkylation reaction typically contains certain polyalkylated products, as well as unreacted aromatic feeds and desired monoalkanes. Base material. Unreacted aromatic feed is typically recovered by distillation and recycled to the alkylation reactor. The bottoms product from the benzene distillation will be further distilled to separate the monoalkylated product from any polyalkylated product and other heavy components. Depending on the amount of polyalkylated product present in the alkylation reaction effluent, it may be desirable to transalkylate the polyalkylated product with additional benzene to produce the desired monoalkylated material. to reach maximum. Transalkylation with additional benzene is typically carried out in a transalkylation reactor other than an alkylation reactor and in a suitable transalkylation catalyst (eg -20-200904778 MCM-22 family molecular decoration) , /5 zeolite, MCM-68 (refer to U.S. Patent No. 6,014,018), zeolite Y or mordenite). The MCM_22 family of molecular sieves includes MCM-22 (disclosed in U.S. Patent No. 4,954,325), PSH-3 (disclosed in U.S. Patent No. 4,439,409), SSZ-25 (not disclosed in U.S. Patent No. 4,826,667), and ERB-1 (disclosed in European Patent No. 0293) 03 No. 2), ITQ-1 (disclosed in U.S. Patent No. 6,077,498), ITQ-2 (disclosed in International Patent Publication No. WO97/17290), MCM-36C disclosed in U.S. Patent No. 5,250,277, and MCM-49 (disclosed in U.S. Patent No. 5,236,575, issued to U.S. Patent No. 5,362,697, issued to U.S. Pat. The transalkylation reaction is typically carried out under at least a portion of the liquid phase conditions, suitably including a temperature of from 1 to 30 ° C, and/or a pressure of from 1,000 to about 7,000 kPa, and/or The total feed meter has an hourly weight space velocity of from 1 to 50 hr·1, and/or a benzene/polyalkylated benzene weight ratio of from 1 to 10. Oxidation of the second butylbenzene In order to convert the second butylbenzene to phenol and methyl ethyl ketone, the second butylbenzene is initially oxidized to the corresponding hydroperoxide. This can be achieved by introducing an oxygen-containing gas such as air into the liquid phase containing the second butylbenzene. Unlike cumene, atmospheric pressure air oxidation of dibutyl benzene is very difficult to achieve in the absence of a catalyst. For example, dibutylbenzene cannot be oxidized at 110 ° C and atmospheric pressure, whereas cumene oxidizes well under the same conditions. At higher temperatures, the atmospheric pressure of the second butylbenzene is increased from 21 to 200904778; however, 'higher temperatures also produce significant amounts of unwanted by-products. The increase in reaction rate and selectivity can be achieved by the oxidation of the dibutylbenzene in the presence of a catalyst. A suitable second butyl benzene catalyst comprises a water soluble chelating compound wherein the multi bud ligand is coordinated to at least one metal from cobalt, nickel, manganese, copper, and iron (refer to U.S. Patent No. 4,013,725) ). More preferably, a heterogeneous catalyst is used. Suitable heterogeneous phase catalysts are disclosed in U.S. Patent No. 5,1,8,9, 594, wherein the catalyst is a keto (hydroxy) bridged tetranuclear manganese complex, and U.S. Patent No. 5,922,920, wherein The catalyst comprises a keto (hydroxy) bridged tetranuclear metal complex having a mixed metal core, one metal of the core being selected from the group consisting of Zn, Cu, Fe, Co, Ni, 二η divalent metals and mixtures thereof And another metal is a trivalent metal selected from the group consisting of In, Fe, Mn, Ga, and ruthenium 1, and a mixture thereof. The entire disclosure of this patent is incorporated herein by reference. Other suitable catalysts for the second butyl benzene oxidation step are N-hydroxy substituted cyclic quinone imines, which are disclosed in U.S. Patent No. 6,720,462, the disclosure of which is incorporated herein by reference, for example, N- hydroxy phthal Yttrium imine, 4-amino-N-hydroxyphthalimide, 3-amino-N-hydroxyphthalimide, tetrabromo-N-hydroxyphthalimide, tetrachloro Base-N-methionimide, N-hydroxyhetimide, N-hydroxyhimimide, N-hydroxytrimellitimide, N-based benzene-1,2,4-13 Yttrium imine, hydrazine, Ν'-dihydroxy (pyromodiimide), hydrazine, Ν'-dihydroxy (benzophenone-3,3',4,4') bisquinodiimine), Ν-hydroxymaleimide, -22- 200904778 pyridine-2,3-diimine, N-hydroxysuccinimide, N-carbyl (tartarium imine), N-hydroxy-5-origin Borneene- 2,3-diimine, external N-hydroxy-7-oxybicyclo[2. 2. 1] Glycine-5-ene-2,3-diimine, N-hydroxy-cis-cyclohexane-1,2-diimine, N-hydroxy-cis- 4-cyclohexyl-1 , 2-diimine, N-naphthyridinium sodium or N-hydroxy-o-phenylenedisulfonimide. Preferably, the catalyst is N-hydroxyphenylenediamine. Another suitable catalyst is N, N', N"-trihydroxyisocyanuric acid. These materials can be used alone or in the presence of a free radical initiator, and can be used as a liquid phase, a homogeneous catalyst or supported on The solid carrier is supplied as a heterogeneous catalyst. Suitable conditions for the second butyl benzene oxidation step include a temperature between about 70 ° C and about 200 ° C (eg, about 90 ° C to about 1). 30 ° C), and a pressure of about 50 to about 2000 kPa (about 0. 5 to about 20 atmospheres). Alkaline buffer can also be added to react with acidic by-products that may form during oxidation. The aqueous phase is introduced to help dissolve the basic compound, such as sodium carbonate. The single pass conversion in the oxidation step is preferably maintained below 50% to minimize the formation of by-products. The oxidation reaction is carried out in a catalytic distillation unit. It is desirable to carry out 'and the second butylbenzene hydroperoxide formed can be concentrated by distilling off unreacted second butylbenzene before the cleavage step." Hydroperoxide cleavage in the second butyl benzene The final step in conversion to phenol and methyl ethyl ketone comprises a second butyl group Hydrogen peroxide cleavage by a pressure of from about 20t -23 to 200904778 to about 15 Torr: a temperature (e.g., about 4 ° C to about 120 ° C), and a pressure of about 50 to about 2500 kPa (e.g., about 100 to about 1000 kPa), and/or hydroperoxide based hourly liquid space velocity (LHSV) of about 0. From 1 to about 100 h^1 (preferably from about 1 to about 50 hr·1) is conveniently achieved by contacting the hydroperoxide with a catalyst in the liquid phase. The second butyl benzene hydroperoxide is preferably diluted in an organic solvent inert to the cleavage reaction (e.g., methyl ethyl ketone, phenol or second butyl benzene) to assist in heat removal. The cleavage reaction is conveniently carried out in a catalytic distillation unit. The coal used in the fracture step may be a homogeneous coal or a heterogeneous coal. Suitable homogeneous phase breaking catalysts include sulfuric acid, perchloric acid, phosphoric acid, hydrochloric acid and p-benzenesulfonic acid. Ferric chloride, boron trifluoride, sulfur dioxide and sulfur trioxide are also effective homogeneous fracture catalysts. A preferred homogeneous phase breaking catalyst is sulfuric acid. Suitable heterogeneous fracture catalysts for the cleavage of the second butyl benzene hydroperoxide include smectite clays such as the acidic smectite ceria-alumina clay disclosed in U.S. Patent 4,870,271. The entire disclosure of this patent is incorporated herein by reference. The following examples are based on illustrative purposes and do not limit the scope of the invention. Example 1 (Comparative) The production of a second butylbenzene from a MCM-49/V3 00 catalyst dried at 150 ° C will have a nominal composition of 80. 9% by weight of zeolite and 20% by weight of Versal 3 00 (V3 00) alumina (fresh MCM-22 catalyst sample) extruded into a diameter of 1. 3 mm (1/20 inch) of the four-lobed (-24-200904778 quadralobe) form and cut into 1. 3 mm (1/20 inch) length. Will be 0. 38 grams of the catalyst was diluted to 3 cubic centimeters with sand and mounted to an outer diameter of 4. 76 mm (3/16 inch) isothermal, downstream fixed bed tubular reactor. The catalyst was dried at 1 〇 ° C and 101 kPa (l atm) at a flow rate of 1 〇〇 cubic centimeter per minute for 2 hours. Nitrogen gas was turned off and benzene was fed into the reactor at 60 cubic centimeters per hour until the reactor pressure reached 2170 kPa (300 psig). Then, reduce the benzene flow to 7. 63 cubic centimeters per hour and adjust the temperature to 16 (TC. in 2. 57 cubic centimeters per hour or 4. 2 WHSV, 2-butene feed was introduced from the syringe pump (57. 1% cis-butene, 37. 8% trans-butene, 2. 5% n-butene, 0. 8% isobutylene and 1-butene 'and 1.8% other substances). The molar ratio of the feed benzene/butene was maintained at 3:1 throughout the run. The liquid product was collected in a cold trap at 160 ° C and 2 1 70 kPa (300 psig) and analyzed off-line. The butene conversion was determined by measuring unreacted butene relative to the feed butene. At 160 ° C, 2170 kPa (300 psig), and 3: 1 benzene / butene molar ratio, based on butene 14. 4, 25. 2, then 4. 2 WHSV collects additional data. The second butylbenzene (s-BB) selectivity versus production time is shown in Figure 1. The production time of the dibutylbenzene (Di-BB) / S-BB ratio is shown in Figure 2. Representative data at 85% and 97% butene conversion are shown in Tables 2 and 3, respectively. Example 2 Preparation of second butylbenzene from a wet MCM-49/V3 00 catalyst. 38 g aliquots of the same MCM-49 -25-200904778 catalyst as described in Example 1 (cut into 1. The 3 mm (1/2 0 inch) length is weighed into the sample pan. Place the disk with the catalyst into the collection tray in the bottom water-containing dryer. There is no direct contact between the catalyst and the liquid water. Leave the catalyst in a closed desiccator until overnight. The final weight of the catalyst is 〇·51 grams. The entire amount of wet catalyst was mounted in the reactor using the same procedure as described in Example 1, but without the catalyst drying step. The benzene was fed into the reactor at 6 〇 cubic centimeters per hour until the reactor pressure reached 2170 kPa (300 psig) and the reactor temperature reached 16 〇 ° C (5 degrees c/min). Then, reduce the benzene flow to 7. 63 cubic centimeters per hour’ and at 2. 57 cubic centimeters per hour or 4. 2 WHSV, the same 2-butene feed as used in Example 1 was introduced. The molar ratio of the feed benzene/butene was maintained at 3:1 throughout the run. Additional data were collected at 16 (TC, 2l7 kPa (300 psig), and 3:1 benzene/butene molar ratio, based on butene-based 12.6, 25·2' followed by 4·4 WHSV. s-BB The selectivity versus production time is shown in Figure 1. The D i - BB / s - BB ratio versus production time is shown in Figure 2 ° After the linear output, the representative data at 85% and 97% butene conversion are shown separately. In Table 2 and Table 3. -26- 200904778 Table 2. Comparison of MCM-49 performance at 85% butene conversion Dry catalyst (Example 1) Moist catalyst (Example 2) Production days 3. 9 4. 0 4. 1 7. 9 8. 0 8. 1 benzene WHSV, h-1 105. 0 105. 0 105. 0 105. 0 105. 0 105. 0 Butene WHSV^1 25. 2 25. 2 25. 2 25. 2 25. 2 25. 2 Butene conversion, % 84. 6 83. 3 83. 5 87. 4 84. 3 85. 1 product selectivity, weight % isobutane 0. 001 0. 001 0. 001 0. 000 0. 000 0. 000 isobutylene+1-butene 0. 411 0. 413 0. 416 0. 280 0. 373 0. 310 c5-c7 0. 079 0. 077 0. 066 0. 061 0. 105 0. 057 1. 285 1. 332 1. 255 0. 969 1. 083 1. 031 C9-11 0. 047 0. 059 0. 058 0. 034 0. 032 0. 032 Ci2=+Ci〇-Cii aromatic 0. 106 0. 095 0. 103 0. 077 0. 072 0. 078 compound Ci3,15 0. 085 0. 091 0. 092 0. 076 0. 066 0. 069 cumene 0. 022 0. 021 0. 021 0. 025 0. 023 0. 023 Tert-butylbenzene 0. 031 0. 029 0. 029 0. 039 0. 032 0. 032 isobutylbenzene* 0. 000 0. 000 0. 000 0. 000 0. 000 0. 000 second butylbenzene 91. 203 90. 969 90. 955 94. 137 94. 080 94. 027 n-butylbenzene 0. 007 0. 011 0. 008 0. 007 0. 011 0. 010 Dibutylbenzene 6. 418 6. 588 6. 682 4. 101 3. 973 4. 174 Tributylbenzene 0. 291 0. 304 0. 303 0. 181 0. 140 0. 150 heavy parts 0. 014 0. 010 0. 011 0. 014 0. 011 0. 005 Total 100. 0 100. 0 100. 0 100. 0 100. 0 100. 0 s-BB purity, % t-BB/all BB, % 0. 034 0. 032 0. 032 0. 042 0. 034 0. 034 i-BB"All BB,% 0. 000 0. 000 0. 000 0. 000 0. 000 0. 000 s-BB/all BB, % 99. 959 99. 957 99. 960 99. 951 99. 955 99. 955 n-BB/all BB, % 0. 007 0. 012 0. 008 0. 007 0. 011 0. 011 Total 100. 0 100. 0 100. 0 100. 0 100. 0 100. 0 Di-BB/s-BB weight ratio 7. 0 7. 2 7. 3 4. 4 4. twenty four. 4, % First-order rate constant IX 1 46 49 All samples were collected at 160 ° C, 2170 kPa (300 psig), and 3:1 benzene / butene molar ratio. *All isobutylbenzene in butylbenzene is less than 0. 5% is not detected by the GC used. -27- 200904778 Table 3. Comparison of MCM-49 performance at 97% butene conversion Dry catalyst (Example 1) Moist catalyst (Example 2) Production days 4. 8 5. 8 6. 8 8. 8 9. 8 10. 8 benzene WHSV, h_1 17. 5 17. 5 17. 5 17. 5 17. 5 17. 5 Butene WHSVV 4. twenty four. twenty four. twenty four. twenty four. twenty four. 2 Butene conversion, 96. 7 96. 5 96. 7 96. 7 96. 4 96. 5 product selectivity, isobutane 0. 001 0. 001 0. 001 0. 001 0. 001 0. 001 isobutylene+1- 0. 000 0. 000 0. 000 0. 000 0. 000 0. 000 c5-c7 0. 063 0. 061 0. 060 0. 057 0. 055 0. 047 c8= 0. 715 0. 691 0. 690 0. 469 0. 458 0. 501 C9-11 0. 033 0. 050 0. 054 0. 016 0. 025 0. 025 Cl2=+Cl〇-Cll 0. 102 0. 152 0. 130 0. 101 0. 113 0. 113 C13-15 0. 101 0. 215 0. 101 0. 105 0. 076 0. 130 cumene 0. 028 0. 030 0. 030 0. 034 0. 036 0. 035 Third butylbenzene 0. 062 0. 067 0. 065 0. 080 0. 086 0. 084 isobutylbenzene* 0. 000 0. 000 0. 000 0. 000 0. 000 0. 000 second butylbenzene 92. 311 92. 075 92. 213 94. 837 94. 949 94. 524 n-butylbenzene 0. 007 0. 011 0. 011 0. 008 0. 009 0. 008 Dibutylbenzene 5. 933 5. 910 6. 029 4. 046 3. 966 4. 273 Tributylbenzene 0. 475 0. 575 0. 426 0. 239 0. 220 0. 251 heavy weight 0. 170 0. 161 0. 188 0. 005 0. 005 0. 009 Total 100. 0 100. 0 100. 0 100. 0 100. 0 100. 0 second butylbenzene t-BB/all BB,% 0. 068 0. 073 0. 071 0. 084 0. 091 0. 088 i-BB*/all BB, % 0. 000 0. 000 0. 000 0. 000 0. 000 0. 000 s-BB/all BB, % 99. 925 99. 915 99. 917 99. 908 99. 900 99. 903 n-BB/all BB, % 0. 008 0. 012 0. 012 0. 008 0. 009 0. 008 total, % 100. 0 100. 0 100. 0 100. 0 100. 0 100. 0 Di-BB/s-BB Repeat 6. 4 6. 4 6. 5 4. 3 4. twenty four. 5 Primary rate 46 49 All samples were collected at 160 ° C, 2170 kPa (300 psig), and 3: 1 benzene / butene molar ratio. *All isobutylbenzene in butylbenzene is less than 0. 5% is not detected by the GC used. -28- 200904778 Referring to Figure 1, it can be seen that the drying catalyst of Example 1 achieved 90% selectivity for s-BB at startup and gradually increased the selectivity to 92% under steady state operation. In contrast, the wet catalyst of Example 2 produced a 94% selectivity s-BB immediately after start-up and maintained at 94-95% throughout the run. Referring to Figure 2, it can be seen that the drying catalyst of Example 1 produced twice the di-BB of the wet catalyst of Example 2 at startup, and the di-BB of Example 1 was higher than 2 in steady state operation. weight%. Therefore, the use of moisture-free MCM-49 eliminates the need for a higher di-BB on-line output and an additional 2% s-BB selectivity during steady state operation. Table 2 shows that at 85% butene conversion, the wet catalyst produces an additional 3% s-BB (94% vs. 91%) and less butene oligomers when compared to dry MCM-49. Polybutylbenzenes. The first order rate constant (see bottom of Table 2, which is based on butene conversion) indicates that the moisture effect has no effect on the activity of the catalyst. In fact, the wet catalyst has a slightly higher rate constant than the dry catalyst. Similarly, Table 3 shows that at 9 7 % butene conversion, the wet catalyst produced an additional 3% s-BB (95% vs 92%) and less butene oligomerization when compared to dry MCM-49. , polybutylbenzenes and heavy parts. The wet action apparently improves the catalytic activity, eliminates on-line output, reduces by-product formation, and increases s-BB selectivity. Example 3 (Comparative) The production of second butylbenzene from a MCM-49/V300 catalyst which was not dried or wet was carried out by the same procedure as described in Example 1 using a 1/2 gram aliquot such as -29-200904778. The same MCM-49 catalyst as described in Example 1 was cut into 1. 3 mm (1/2 0 inch) length is mounted in the reactor. Use a catalyst that is not dry. At 60 cubic centimeters per hour, benzene was fed to the reactor until the pressure reached 2170 kPa (300 psig) and the reactor temperature reached 160 ° C (5 degrees C/min). Then, reduce the benzene flow to 7. 63 cubic centimeters per hour. at 2. 57 cubic centimeters per hour or 8. 0 2-butene was introduced under WHSV. Data were collected at 1 60 ° C, 2170 kPa (300 psig), and 3: 1 benzene / butene molar ratio. A 95% butene conversion was observed at 8 WHSV, a conversion of buttene at 24 WHSV of 73%, and a conversion of 48% at 48 WHSV. The one-step rate constant is 51 based on the butene conversion. The s-BB selectivity versus production time is shown in Figure 3a. The Di- ratio versus production time is shown in Figure 3b. For comparison, the data for Examples 1 and 2 are also included. These data show that the MCM-49 catalyst is dry or not, providing a lower s-BB selectivity and a higher di-BB selectivity than the wet version. Example 4 Preparation of second butylbenzene from water-soaked MCM-49/V3 00 catalyst. Soak in deionized water at room temperature. 20 g aliquots of the same MCM-49 catalyst as described in Example 1 (cut into 1. 3 mm (1/20 inch) length) for 1 hour and then air dried to room temperature overnight. The last weight of the catalyst is 0. 26 grams. The entire amount of catalyst was mounted in the reactor using the same procedure as described in Example 1. The catalyst can be used without further drying. The benzene was fed to the reactor at 60 cubic centimeters per hour until the pressure reached -30-200904778 2170 kPa (300 psig) and the reactor temperature reached 160t: (the slope was 5 degrees C/min). Then, reduce the benzene flow to 7. 63 cubic centimeters per hour. at 2. 2-butene was introduced at 57 cubic centimeters per hour or 8 WHSV. Data were collected at 160 °C, 2170 kP a (300 psig), and 3:1 benzene/butene molar ratio. A conversion of 97% butene was achieved at 8 WHSV, a conversion of butene at 24 WHSV of 83%, and a conversion of 48% at 48 WHSV. The one-step rate constant based on the benzene conversion rate is 45 1Γ1. The s-BB selectivity versus production time is shown in Figure 4a. The Di-BB/s-BB ratio versus production time is shown in Figure 4b. For comparison, the data of Examples 1 to 3 are also included. These data show that water soaking is also as effective as wet treatment in upgrading MCM-49 to achieve high s-BB selectivity and low di-BB selectivity. Example 5 Preparation of a second butylbenzene from a MCM-49/V300 catalyst wetted and then dried. The same procedure as described in Example 2 was used to make the same MCM as described in Example 1 in the same manner as in Example 1. 49 catalyst (cut into 1 . 3 mm (1/2 0 inch) length) wet. The final weight of the catalyst after dampening is 〇 3〇 gram. The entire amount of moisture catalyst was mounted in the reactor using the same procedure as described in Example 1. The catalyst was dried for 2 hours at a flow rate of 1 〇〇 LL square centimeters per minute at 15 Torr and 1 〇 1 kPa (i atm). Nitrogen was turned off and at 60 cubic centimeters per hour, benzene was fed to the reactor until the pressure reached 2 170 kPa (300 psig). The reactor temperature was adjusted to 16 〇t and the -31 - 200904778 benzene flow was reduced to 7·63 cubic centimeters per hour. at 2. 57 cubic centimeters per hour or 8 WHSV, introducing 2 - butyl. Data were collected at 16 〇t, 217 〇 kpa (300 psig), and 3: 1 benzene/butene molar ratio. 95% butyl conversion at 8 WHS V was achieved at 24 WHS v butene conversion of 8〇%, and at 48 WHSV butene conversion was 66%. Based on the butene conversion rate, the first-order rate constant is 42 h·1. The S_BB selection rate versus production time is shown in Figure 5a. The Di-BB/s-ββ ratio versus production time is shown in Figure 5b. For comparison, the data of Examples 1 to 4 are also included. These data show that although this wet catalyst was dried at 15 〇 before start-up, its s-BB selectivity remained high and di_BB remained low. Table 4 compares the catalyst properties of Examples 1 to 5 under 92-97% butene conversion and steady state conditions. When compared to untreated MCM-49, the wet/water treatment produced an additional 3% S_BB (95% vs. 92%) and less butene oligomers, dibutylbenzenes, tributylbenzene Class and heavy weight. The moist action apparently improves the catalytic activity, eliminating the on-line output, reducing by-product formation, and increasing the s-BB selectivity. -32- 200904778 Table 4.  Comparison of MCM-4 9/V3 00 performance Example 3 1 2 5 4 Processing te «Μ,, te Wet moist water At 15 (drying under TC Μ j\\\ There are Μ production days 4. 9 6. 8 10. 8 1. 8 2. 8 benzene WHSV, hf1 32. 8 17. 4 17. 5 33. 0 33. 1 Butene WHSV, h-1 7. 9 4. twenty four. 2 7. 9 7. 9 Butene conversion, % 92. 4 96. 7 96. 5 94. 2 96. 4 product selectivity, weight% isobutane 0. 001 0. 001 0. 001 0. 001 0. 001 isobutylene+1-butene 0. 023 0. 000 0. 000 0. 039 0. 000 c5-c7 0. 099 0. 093 0. 079 0. 066 0. 056 c8= 0. 755 0. 690 0. 501 0. 413 0. 500 C9-11 0. 050 0. 054 0. 025 0. 051 0. 025 aromatic compound 0. 115 0. 130 0. 113 0. 114 0. 090 Cl3_15 0. 055 0. 101 0. 130 0. 095 0. 100 cumene 0. 023 0. 030 0. 035 0. 022 0. 026 Tert-butylbenzene 0. 042 0. 065 0. 084 0. 083 0. 051 isobutylbenzene* 0. 000 0. 000 0. 000 0. 000 0. 000 second butylbenzene 91. 682 92. 183 94. 493 94. 377 94. 430 n-butylbenzene 0. 006 0. 011 0. 008 0. 014 0. 006 Dibutylbenzene 6. 397 6. 027 4. 271 4. 536 4. 538 Tributylbenzene 0. 440 0. 426 0. 251 0. 158 0. 166 heavy weight 0. 312 0. 188 0. 009 0. 030 0. 011 Total 100. 0 100. 0 100. 0 100. 0 100. 0 second butyl (BB) t-BB/all BB, % 0. 045 0. 071 0. 088 0. 088 0. 054 i-BB"All BB,% 0. 000 0. 000 0. 000 0. 000 0. 000 s-BB/all BB, % 99. 948 99. 917 99. 903 99. 897 99. 939 n-BB/all BB, % 0. 007 0. 012 0. 008 0. 015 0. 007 total, % 100. 0 100. 0 100. 0 100. 0 100. 0 Di-BB/s-BB weight ratio, % 7. 0 6. 5 4. 5 4. 8 4. 8 Primary rate constants 9 1 52 46 49 42 45 All samples were collected at 160 ° C, 2170 kPa (300 psig), and 3: 1 benzene / butene molar ratio. *All isobutylbenzene in butylbenzene is less than 0. 5% is not detected by the GC used. -33 200904778 Example 6 (Comparative) Production of a second butylbenzene from a dried MCM-49/Condea catalyst A fresh MCM-49 having a nominal chemical composition of 80% by weight zeolite and 20% by weight Condea alumina The catalyst sample was extruded into a quadlolobe of diameter I-3 mm (1/2 inch) and cut into 1. 3 mm (1/20 inch) length. Will be 0. 40 grams of the catalyst was diluted to 3 cubic centimeters with sand and mounted at an outer diameter of 4. 76 mm (3/16 inch) isothermal, downstream fixed bed tubular reactor. The catalyst was dried at 150 ° C and 101 kPa (l atm) at a flow rate of 100 cubic centimeters per minute for 2 hours. Nitrogen was turned off and benzene was fed into the reactor at 60 cubic centimeters per hour until the reactor pressure reached 2170 kPa (300 psig). Then, the reactor temperature was adjusted to 160 ° C and the benzene flow was reduced to 7. 63 cubic centimeters per hour. at 2. The 2-butene feed was introduced at 57 cubic centimeters per hour or 4 WHSV. The molar ratio of benzene/butene fed during the entire run was 3:1. The s-BB selectivity versus production time is shown in Figure 6a. The Di-BB/s-BB ratio versus production time is shown in Figure 6b. Example 7 Preparation of a second butylbenzene using a moist MCM-49/Condea catalyst The same procedure as described in Example 2 was used to make 0. 20 gram aliquots The same MCM-49/Condea catalyst as in Example 6 was wet. The final weight of the catalyst after damp is 〇.  3 5 grams. The entire amount of wet catalyst was mounted in the reactor using the same procedure as described in Example 1. Use the catalyst without drying. At 60 cubic centimeters per hour, benzene was fed to the reactor until the pressure reached -34-200904778 to 2170 kPa (300 psig) and the reactor temperature reached 160 °C (5 degrees C/min). Reduce benzene flow to 7. 63 cubic centimeters per hour. at 2. 57 cubic centimeters per hour or 8. 0 WHSV 'Introduced 2-butene. The benzene/butene molar ratio was 3:1 throughout the run. The s-BB selectivity versus production time is shown in Figure 6a. The Di-BB/s-BB ratio versus production time is shown in Figure 6b. Referring to Figures 6a and 6b, the data shows that the MCM-49/Condea catalyst has a very low s-BB selectivity and a very high di-BB selectivity before moisture treatment. Daxie took 2 weeks to finally reach steady state performance. Compared to the moist MCM-49/Versal 3 00 catalyst shown in Example 2, the s-BB selectivity after the wet treatment was significantly increased to 94-95 %. Table 5 compares the catalyst properties of Examples 6 and 7 at 95-98% butene conversion. When compared to dry catalysts, the wet form produces an additional 6% s-BB (95% vs. 89%), making by-products (including butene oligomers, dibutylbenzenes, and tributylbenzene) Reduction to half, the production of cumene and heavy fractions is reduced to zero, and the formation of t-BB and n-BB is significantly reduced. The moist action apparently modifies the catalytic activity, eliminates on-line output, reduces by-product formation, and significantly increases the s-B B selectivity. -35- 200904778 Table 5.  Comparison of MCM-49/Condea Performance Dry Catalyst (Example 6) Moist Catalyst (Example 7) Example # 7 8 9 7 8 9 Production Days 7. 1 8. 1 9. 1 6. 8 7. 8 8. 8 benzene WHSV,!^1 16. 7 16. 7 16. 7 33. 2 33. 2 33. 2 Butene WHSV,!!·1 4. 0 4. 0 4. 0 8. 0 8. 0 8. 0 Butene conversion, % 95. 4 95. 3 96. 3 97. 7 95. 9 96. 4 product selectivity, Wt% isobutane 0. 005 0. 006 0. 005 0. 000 0. 000 0. 000 isobutylene+1-butene 0. 000 0. 000 0. 000 0. 000 0. 000 0. 000 c5-c7 0. 101 0. 115 0. 109 0. 046 0. 099 0. 064 c8= 1. 154 1. 225 1. 374 0. 571 0. 606 0. 671 C9-11 0. 091 0. 088 0. 098 0. 018 0. 007 0. 038 c12=+c10-c„ Aromatization 0. 283 0. 276 0. 272 0. 074 0. 074 0. 052 Compound Ci3_15 0. 373 0. 327 0. 320 0. 076 0. 084 0. 060 cumene 0. 290 0. 288 0. 286 0. 000 0. 020 0. 000 third butylbenzene 0. 164 0. 158 0. 146 0. 047 0. 045 0. 042 isobutylbenzene* 0. 000 0. 000 0. 000 0. 000 0. 000 0. 000 second butylbenzene 88. 096 88. 644 89. 005 94. 828 94. 725 95. 031 n-butylbenzene 0. 019 0. 017 0. 025 0. 002 0. 001 0. 000 dibutyl benzene 8. 583 8. 124 7. 597 4. 280 4. 291 4. 002 Tributylbenzene 0. 767 0. 669 0. 599 0. 059 0. 049 0. 039 Heavy part 0. 075 0. 063 0. 163 0. 000 0. 000 0. 001 Total 100. 0 100. 0 100. 0 100. 0 100. 0 100. 0 Second butylbenzene (BB) purity t-BB/all BB,0/〇 0. 185 0. 178 0. 164 0. 049 0. 047 0. 044 i-BB*/all BB, % 0. 000 0. 000 0. 000 0. 000 0. 000 0. 000 s-BB/all BB, % 99. 794 99. 803 99. 808 99. 949 99. 952 99. 956 n-BB/all BB, % 0. 021 0. 019 0. 028 0. 002 0. 001 0. 000 total, % 100. 0 100. 0 100. 0 100. 0 100. 0 100. 0 Di-BB/s-BB weight ratio 9. 7 9. 2 8. 5 4. 5 4. 5 4. 2,% All samples are at 16 0. . 2 1 70 kPa (3 OOpsig), and 3:1 benzene / butene molar ratio collected. *All isobutylbenzene in butylbenzene is less than 0. 5% is not detected by the GC used. -36- 200904778 Example 8 Comparison of Catalysts via 29Si MAS NMR The characteristics of the 150 T:dried and wet catalysts described in Examples 1 and 2 were further depicted separately by 29 Si MAS NMR. The 29Si MAS NMR data for these two materials are shown in Figure 7. These 29Si MAS NMR data clearly show differences in structural changes after dehydration or hydration. In particular, the 29 Si MAS NMR spectrum of the wet catalyst described in Example 2 is exhibited in the range of -90 to -100 ppm chemical shift of TMS (more specifically, in the chemical shift range of about -94 to -100 ppm). A peak, and the high point indicated by this peak is near -9 8 ppm of TMS. This peak is usually indistinguishable in the spectrum of the dry catalyst of Example 1. Differences in NMR spectra reflect changes in the local environment of Si, such as bond angles and nearest neighbor populations, depending on the degree of hydration. These data suggest that wetting the sample promotes A1 reinsertion into the tetrahedral framework and/or mitigates local geometric strain caused by dehydration. These subtle structural changes can indicate the increased activity and selectivity of the hydration catalyst. Example 9 (Comparative) Production of a second butylbenzene from a dry and hydrated 0/alumina catalyst. A fresh zeolite-free catalyst having a nominal chemical composition of 65% by weight of zeolite and 35% by weight of Versal 300 alumina. Squeeze into a diameter of 1. A 4 mm (1/20 inch) quadralobe form and cut to a length of 2 mm. Using the procedure of Example 1 in the alkylation of the benzene of Example 1 with the 2-butene feed -37-200904778, a sample of the θ zeolite catalyst was used in the catalyst with benzene and butene feed. The catalyst was dried under flowing nitrogen at U0 cubic centimeters per minute for 2 hours at 150 ° C and 101 kPa (1 atm) prior to contact. The molar ratio of the feed benzene/butene was maintained at 3:1' throughout the run and the liquid product was collected in a cold trap at 160 ° (: and 2170 kPa (300 psig) and analyzed off-line. The results are summarized in Table 6. Using the procedure of Example 2, another sample of the 3 zeolite catalyst was used in the densification of the benzene and 2-butene feed of Example 1, in contact with the benzene and butene feed. The catalyst was previously allowed to damp overnight in a closed desiccator. The molar ratio of benzene/butene fed during the entire run was again maintained at 3:1 and was cold at 160 ° C and 2170 kPa (3 〇 0 psig). The liquid product was collected in the trap and analyzed offline. The results are also summarized in Table 6. -38- 200904778 Table 6.  /3 Zeolite performance comparison Dry catalyst Humidity catalyst Production days 0. 83 1. 83 2. 83 0. 79 1. 79 2. 79 benzene WHSVV 33. 2 33. 2 33. 2 33. 0 33. 0 33. 0 Butene WHSV^1 8. 0 8. 0 8. 0 7. 9 7. 9 7. 9 Butene conversion, % 91. 21 60. 23 44. 64 82. 79 49. 49 41. 88 product selectivity, wt% isobutane 0. 004 0. 003 0. 000 0. 006 0. 000 0. 003 isobutylene+1-butene 0. 211 3. 478 9. 208 0. 812 6. 065 9. 301 c5-c7 0. 159 0. 250 0. 346 0. 139 0. 321 0. 398 Cg= 1. 039 8. 652 12. 575 2. 721 11. 460 12. 393 C9-11 0. 198 0. 670 0. 284 0. 445 0. 470 0. 341 C12=+C1()-C„Aromatic compounding 0. 226 0. 813 0. 271 0. 795 0. 352 0. 408 objects Ci3_15 0. 361 0. 088 0. 025 0. 587 0. 025 0. 021 cumene 0. 019 0. 000 0. 000 0. 024 0. 000 0. 002 third butylbenzene 0. 255 0. 077 0. 012 0. 288 0. 025 0. 010 isobutylbenzene* 0. 000 0. 000 0. 000 0. 000 0. 000 0. 000 second butylbenzene 85. 316 80. 627 74. 829 81. 370 76. 713 73. 999 n-butylbenzene 0. 006" 0. 017 0. 000 0. 093 0. 113 0. 000 dibutylbenzenes 10. 361 5. 052 2. 390 10. 974 4. 240 2. 902 Tributylbenzene 1. 174 0. 194 0. 011 1. 422 0. 114 0. 105 heavy parts 0. 672 0. 079 0. 049 0. 325 0. 103 0. 116 Total 100. 0 100. 0 100. 0 100. 0 100. 0 100. 0 s-BB purity, % t-BB/all BB, % 0. 298 0. 095 0. 016 0. 352 0. 033 0. 013 i-BBV all BB,% 0. 000 0. 000 0. 000 0. 000 0. 000 0. 000 s-BB/all BB, % 99. 696 99. 884 99. 984 99. 534 99. 821 99. 987 n-BB/all BB, % 0. 007 0. 021 0. 000 0. 113 0. 147 0. 000 total, % 100. 0 100. 0 100. 0 100. 0 100. 0 100. 0 Di-BB/s-BB weight ratio, % 12. 14 6. 27 3. 19 13. 49 5. 53 3. 92 All samples were collected at 16 (TC, 2 1 70 kPa (300 psig), and 3:1 benzene/butene molar ratio. * All butylbenzene in isobutylbenzene was less than 0. 5% is not detected by the GC used. -39- 200904778 It can be seen from the results in Table 6 that the 3:1 benzene/butene molar ratio used in the test, the dry and wet two zeolite catalysts are rapidly reduced throughout the oligomer formation. activation. Moreover, unlike the MCM-49 catalyst used in Examples 1 and 2, the moist action of the 0 zeolite catalyst did not result in an increase in the initial s-BB selectivity and a decrease in the initial di-BB selectivity. Conversely, when the dampening effect of the /3 zeolite catalyst is compared to the desired catalyst, a start-up results in a lower s-BB selectivity and a higher di-BB selectivity. Although the invention has been described with reference to the specific embodiments thereof, it is understood that the invention may be susceptible to variations that are not described herein. For this reason, in order to determine the true scope of the invention, reference should be made to the accompanying claims. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a graph showing the selectivity to the second butylbenzene of the dried MCM-49/V300 catalyst of Example 1 and the wet MCM-49/V3 00 catalyst of Example 2. It shows that the moist effect enhances the SBB selection rate. Figure 2 is a graph of the % by weight of dibutylbenzene to dibutylbenzene of the dried MCM-49/V3 00 catalyst of Example 1 and the wet MCM-49/V3 00 catalyst of Example 2 versus production time. It shows that the moist action reduces dialkylation. 3(a) and (b) are comparisons of the second butylbenzene selectivity of the MCM-49/V300 catalysts of Examples 1 to 3 and the weight % of dibutylbenzene to the second butylbenzene versus production time. Figure. 4(a) and (b) are the second butylbenzene selectivity of the catalyst and the weight % of the dibutylbenzene to the second butylbenzene of the MCM-49/V300-40-200904778 of Examples 1 to 4. Comparison chart of production time. 5(a) and (b) are comparisons of the second butylbenzene selectivity of the MCM-49/V300 catalysts of Examples 1 to 5 and the weight % of dibutylbenzene to the second butylbenzene versus production time. Figure. Figures 3(a), 4(a) and 5(a) show that the moist action enhances the SBB selectivity, while Figures 3(b), 4(b) and 5(b) show that the damp action reduces dialkylation. Figure 6 (a) and (b) are the comparison of the second butylbenzene selectivity of the MCM-49/Condea catalysts of Examples 6 and 7 and the weight % of dibutylbenzene to the second butylbenzene versus production time. Figure. Figure 6(a) shows that the wetness results in a better SBB selectivity than the dry catalyst when starting and after several turns of production. Figure 6(b) shows that the wet action resulted in a lower dialkylation than the dry catalyst obtained at startup and after several days of production. Figure 7 is a comparison of 29Si MAS NMR spectra of the dried MCM-49/V3 00 catalyst of Example 1 and the wet MCM-49/V3 00 catalyst of Example 2 over a chemical shift range of -70 to -140 ppm. -41 -

Claims (1)

200904778 X. Patent Application No. 1 A method for preparing a second butylbenzene, which comprises reacting benzene with at least one C4 alkane under alkylation conditions and in a catalyst containing at least one molecular group of MC Μ - 2 2 The catalyzed reagent reacts to form an alkylated product containing a second butyl benzene which is contacted with water prior to the reaction under conditions which enhance the selectivity of the second butylbenzene of the catalyst. 2. The method of claim 1, wherein the contact with water is carried out at a temperature comprising at least 0 °C. 3- The method of claim 2, wherein the temperature is in the range of 10 ° C to 50 ° C. 4. The method of claim 1, wherein the contact with the water is carried out at a time including at least 0.5 hours. 5. The method of claim 4, wherein the time is in the range of 2 to 24 hours. 6. The method of claim 1, wherein the contact with water is at least in the range of -80 to -120 ppm of tetramethyl decane (TMS) in the 29Si MAS NMR spectrum of the catalyst. It is carried out under conditions in which the amplitude or width of a peak changes. 7. The method of claim 1, wherein the catalyst is in contact with liquid water. 8. The method of claim 1, wherein the catalyst is in contact with water vapor. 9. The method of claim 1, wherein the catalyst is dried after contact with water and before the reaction. The method of claim 9 wherein the catalyst is the same as the method of claim 9. It is dried at a temperature ranging from loot to 200 ° C for a period ranging from 1 hour to 5 hours. II. The method of claim 1, wherein the second butylbenzene selectivity of the contact water catalyst is the second choice of the same catalyst that is not in contact with water for the same reactants and process conditions. The butylbenzene selectivity is at least 1% by weight. 12. The method of claim 11, wherein the second butylbenzene selectivity of the contact water catalyst is the same as that of the same catalyst that is not in contact with water for the same reactants and process conditions. The selectivity to dibutylbenzene is at least 2% by weight. 13. The method of claim 1, wherein the C 4 alkylating agent comprises a linear butene. The method of claim 13, wherein the linear butene comprises butene-1, butene-2, or a mixture thereof. 15. The method of claim 1, wherein the molecular sieve of the mcm_22 family has a maximum d-spacing at 12.4±0.25, 6.9±〇.15, 3.57±0·07, and 3.42±0_07 angstroms. _ ray diffraction diagram. 16. The method of claim i, wherein the molecular sieve is selected from the group consisting of MCM-22, PSH-3, SSZ-25, Eru, HQ", ITQ 2, MCM_49, MCM_56 'UZM_8, and mixtures thereof ο • The method of applying for the patent scope " page, wherein the base conditions of the hospital include the total molar ratio of benzene to & hospitalization reagent: 至: 1 to 2 〇: 1. -43-200904778 1 8. The method of claim 17, wherein the alkylation conditions also include a temperature of 6 (TC to 260 ° C, and/or a pressure of 7000 kPa or less, and/or The C4 alkylating agent-based feed has a weight space velocity per hour (WHSV) of from 0.1 to 50 hr·1. 19. The method of claim 1, further comprising oxidizing the second butylbenzene The hydroperoxide is formed, and the hydroperoxide is cleaved to produce phenol and methyl ethyl ketone. 20. The method of claim 19, wherein the oxidation of the second butyl benzene is in a catalyst 21. The method of claim 19, wherein the oxidation of the second butylbenzene is carried out in the presence of a homogeneous catalyst comprising an N-hydroxy substituted cyclic quinone imine. The method of claim 19, wherein the oxidation is carried out at a temperature of from 70 ° C to 200 ° C, and/or from 50 to 2000 kPa (0.5 to 2 Torr). The method of item 19, wherein the hydroperoxide is at a temperature of from 40 ° C to 120 ° C, / Or the pressure of 100 to 1000 kPa, and / or the hydroperoxide based on the liquid hourly space velocity (LHSV of) 1 to 50 hr · carried out at 1-44. -