KR101701578B1 - Improved liquid phase alkylation process - Google Patents

Abstract

The present invention relates to a process for the preparation of monoalkylated aromatic compounds comprising contacting an alkylatable aromatic compound with an alkylating agent under effective alkylation conditions in the presence of the catalyst composition, 56 crystals and binders produced by the seeded synthesis process such that the weight ratio of crystal / binder in the catalyst composition is from 20/80 to about 80/20.

Description

[0001] IMPROVED LIQUID PHASE ALKYLATION PROCESS [0002]

Cross-reference to related application

This application claims the benefit of US Provisional Application No. 61 / 535,632, filed September 16, 2011, EP 11188529.9 filed November 10, 2011, and International Application No. PCT / US2012 / 51181, filed August 16, The disclosures of which are incorporated herein by reference in their entirety.

The present invention relates to an improved process for the preparation of alkylaromatics, for example ethylbenzene, cumene and sec-butylbenzene.

Among the alkylaromatics produced advantageously by the improved process of the present invention, ethylbenzene and cumene are important raw material chemicals that are used industrially, for example, for the production of styrene monomers and the simultaneous production of phenol and acetone, respectively. In fact, the usual route for the production of phenol is to produce cumene by alkylation of benzene with propylene, then oxidation of cumene with the corresponding hydroperoxide, followed by hydroperoxide decomposition to yield equimolar amounts of phenol and acetone The process comprising the steps of: Ethylbenzene can be produced by a number of different chemical processes. One process that has achieved a significant degree of commercial success is the vapor phase alkylation of used benzene with ethylene in the presence of a solid, acidic ZSM-5 zeolite catalyst. Examples of such ethylbenzene manufacturing processes are described in U.S. Patent Nos. 3,751,504 (Keown), 4,547,605 (Kresge) and 4,016,218 (Haag).

Another process that has achieved significant commercial success is a liquid phase process for the production of ethylbenzene from benzene and ethylene because it operates at a lower temperature than the vapor phase counterpart and tends to produce lower yields of byproducts. For example, U.S. Patent No. 4,891,458 (Innes) describes the liquid phase synthesis of ethylbenzene using zeolite beta, while U.S. Patent No. 5,334,795 (Chu) describes the use of MCM-22 in the liquid phase synthesis of ethylbenzene . The latter patent teaches the use of a catalyst comprising MCM-22 crystalline material and a binder in a ratio of crystal / binder of about 1/99 to about 90/10.

Cumene has been commercially produced for several years by liquid phase alkylation of benzene with propylene over Friedel-Craft catalysts, especially solid phosphoric acid or aluminum chloride. More recently, however, zeolitic catalyst systems have been found to be more active and selective for the propylation of benzene to cumene. For example, U.S. Patent No. 4,992,606 (Kushnerick) describes the use of MCM-22 in liquid phase alkylation of benzene with propylene.

Other publications disclose the use of a catalyst comprising a crystalline zeolite and a binder to convert a feedstock comprising an alkylatable aromatic compound and an alkylating agent at least under partial liquid phase conversion conditions to an alkyl aromatic conversion product. Examples thereof include U.S. Publication No. 2005/0197517 Al (Cheng), which shows the use of catalyst crystallizer / binder ratios of 65/35 and 100/0; U.S. Publication No. 2002 / 0137977A1 (Hendriksen), which shows the use of a catalytic crystal / binder ratio of 100/0, bearing in mind the perceived negative impact of the binder on selectivity; US Publication No. 2004/0138051A1, which describes the use of a catalyst comprising a microporous zeolite embedded in a mesoporous support having a zeolite / support ratio of less than 1/99 to more than 99/1, preferably 3/97 to 90/10, (Shan); WO 2006/002805 (Spano), which teaches the use of a catalyst crystal / binder ratio of 20/80 to 95/5, for example 55/45; U.S. Patent No. 6,376,730 (Jan), which describes the use of 70/30 and 83/17 stacked catalyst crystal / binder; EP 0847802B1 showing the use of a catalyst crystal / binder ratio of 50/50 to 95/5, preferably 70/30 to 90/10; And U. S. Patent No. 5,600, 050 (Huang) indicating the use of a catalyst comprising 30-70 wt% H-beta zeolite, 0.5-10 wt% halogen and balance alumina binder.

Conventional alkylation methods for preparing alkylaromatics such as ethylbenzene and cumene produce essentially monoalkylated products as well as polyalkylated species in nature. Thus, polyalkylated species can be recycled to an alkylation reactor or, more often, polyalkylated species can be fed to a separate transalkylation reactor to transalkylate polyalkylated species using additional aromatic feeds, such as benzene, It is customary to produce alkylation products such as ethylbenzene or cumene. Examples of catalysts that have been used for alkylation of aromatic species such as alkylation of benzene with ethylene or propylene and transalkylation of polyalkylated species such as polyethylbenzene and polyisopropylbenzene are disclosed in U.S. Patent No. 5,557,024 to Cheng And MCM-49, MCM-22, PSH-3, SSZ-25, zeolite X, zeolite Y, zeolite beta, acid dealuminated mordenite and TEA-mordenite. Transalkylation in TEA-mordenite in the form of small crystals (< 0.5 microns) is also disclosed in U.S. Patent No. 6,984,764.

When the alkylation step is carried out in a liquid phase, it is also preferred to carry out the transalkylation step under liquid phase conditions. However, the liquid phase process adds to the increased requirement for catalysts in the transalkylation stage, which must operate at relatively low temperatures to convert the bulk polyalkylated species into additional monoalkylated products without creating particularly undesired by-products. This has proven to be a significant problem in the case of cumene manufacture where existing catalysts lack the desired activity or result in the production of significant amounts of by-products such as ethylbenzene and n-propylbenzene.

The catalysts for converting a feedstock comprising an alkylatable aromatic compound and an alkylating agent into an alkylaromatic conversion product under at least partial liquid phase conversion conditions in the art are selected from the group consisting of a crystal / binder of 1/99, for example 5/95 to 100/0 Although it is suggested to be composed of nonporous crystalline aluminosilicates and binders, commercially available catalysts, i.e. those found commercially useful for this purpose, are porous crystalline aluminosilicates of the ratio of 65/35 or 80/20 crystal / . Finding a commercially acceptable catalyst for this process carried out under at least partial liquid phase conversion conditions that increase mono selectivity, i.e., produce less di- or polyalkyl product, allows capacity expansion in existing plants, Lower capital costs in grassroots plants as a result of lower aromatics / alkylating agent ratios.

U.S. Patent Application Publication No. 2011/0178353 (Clark et al.) Includes a porous crystalline material such as crystalline aluminosilicate ("crystalline") and a binder in a crystal / binder ratio of about 20/80 to about 60/40 A liquid or partial liquid phase alkylation process for the production of an alkylaromatic which is carried out in the presence of a particular catalyst to produce a unique combination of activity and important mono selectivity. Suitable catalysts disclosed include MCM-22 family materials.

MCM-22 family molecular sieves have been found useful in various hydrocarbon conversion processes. Examples of MCM-22 family molecular sieves include MCM-22, MCM-49, MCM-56, ITQ-1, ITQ-2, PSH-3, SSZ-25, ERB-1, UZM-8 and UZM- . In particular, MCM-56 is a laminated oxide material rather than a three-dimensional ordered zeolite, wherein each layer in MCM-56 is porous and has a skeletal structure closely related to MCM-22 and other MCM-22 family materials .

U.S. Provisional Application No. 61 / 535,632 (Johnson et al.), Filed September 12, 2011, which is incorporated herein by reference in its entirety, incorporates MCM-56 seed crystals into an initial reaction mixture to form a high quality porous seeded- An improved process for the preparation of crystalline MCM-56 materials is disclosed. The invention also relates to seeded-MCM-56 materials prepared by the improved process, to catalyst compositions comprising them and to their use in a process for the catalytic conversion of hydrocarbon compounds.

According to the present invention, a seeded-MCM-56 crystalline aluminosilicate in combination with a binder in a crystal / binder weight ratio of about 20/80 to about 80/20, preferably about 40/60 to about 60/40, Has been found to produce a unique combination of activity and important mono selectivity in a liquid phase or partial liquid phase alkylation process to produce alkyl aromatics.

Summary of the Invention

According to the present invention there is provided a process for the preparation of an alkylatable aromatic compound having at least partial liquid phase conversion under at least partial liquid phase conversion conditions in the presence of a specific catalyst comprising a porous crystalline material such as crystalline aluminosilicate and a binder with a ratio of crystal / binder of about 20/80 to about 60/40. An improved process for converting a feedstock comprising a compound and an alkylating agent into a desired alkylaromatic conversion product is provided. According to one embodiment of the present invention there is provided a process for selectively producing certain monoalkylated aromatic compounds comprising contacting an alkylatable aromatic compound with an alkylating agent under at least partial liquid phase conditions in the presence of a catalyst composition, The catalyst composition comprises a porous crystalline material, such as crystalline aluminosilicate and a binder, in a weight ratio of crystal / binder of from about 20/80 to about 60/40. Another embodiment of the present invention is a process for the preparation of benzenes by reacting benzene with an alkylating agent under alkylation conditions in the presence of an alkylating catalyst comprising a porous crystalline material such as crystalline aluminosilicate and a binder with a ratio of crystal / binder of from about 20/80 to about 60/40. &Lt; RTI ID = 0.0 &gt; 1, &lt; / RTI &gt;

Catalysts for use in the process of the present invention may be, for example, crystalline molecular sieves having the structure of zeolite beta or X-rays containing a d-distance maximum at 12.4 ± 0.25, 6.9 ± 0.15, 3.57 ± 0.07 and 3.42 ± 0.07 Å, And may have a diffraction pattern. More specifically, the catalyst for use herein may comprise a crystalline molecular sieve having the structure of beta, MCM-22 family material, such as MCM-22 or mixtures thereof.

In another embodiment, the present invention provides a process for preparing a feed comprising a benzene under at least partial liquid phase conversion conditions in the presence of a seeded MCM-56 crystal / binder composition having a crystal / binder ratio of at least about 20/80 to about 60/40 To a process for the selective conversion of benzene to ethylbenzene, comprising contacting the raw material with ethylene.

In another embodiment, the present invention provides a process for the selective alkylation of benzene with ethylene to produce ethylbenzene,

i) A process for producing a synthetic porous crystalline MCM-56 material by a process comprising the steps of a), b), c) and d)

a) a first reaction mixture containing an alkali metal or alkaline earth metal (M) cation, an oxide of a trivalent element X, an oxide of a tetravalent element Y and water, in the following ranges: YO ₂ / X ₂ O ₃ = 5 to 35, H ₂ O / YO ₂ = 10 to 70, OH ^- / YO ₂ = 0.05 to 0.20, M / YO ₂ = 0.05 to 3.0, and further comprising a zeolite seed crystal in an amount of not less than 0.05% by weight and not more than 5% by weight based on the weight of the first reaction mixture ;

b) To the reaction mixture of step a) is added the derivatizing agent R in the following range: R / YO ₂ Producing a second reaction mixture having said derivatizing agent R with respect to a molar ratio falling within the range of 0.08 to 0.3;

c) crystallizing the second reaction mixture of step b) at a temperature of from about 90 占 폚 to about 175 占 폚 and for a time of less than 90 h to form a seeded MCM-56 material as identified by X-ray diffraction And producing less than 10% by weight of non-MCM-56 impurity crystals based on the total weight of the MCM-56 crystals in the second reaction mixture;

d) separating and recovering at least a portion of the crystals of the seeded MCM-56 material from the resulting mixture of step c), wherein the crystals of the seeded MCM-56 material are selected from the group consisting of X- Diffraction pattern;

<Table 1>

(ii) combining the seeded MCM-56 crystals with a binder at a crystal / binder weight ratio of from about 20/80 to about 80/20 to produce a catalyst composition; And

(iii) a temperature of about 0 to about 500 ℃ ℃, about 20 to about 25,000 kPa-a pressure of from about 0.1: 1 to about 50: the molar ratio of benzene to ethylene of from about 0.1 to about 1 and 500 h ^-1 ethylene Contacting a feedstock containing benzene and ethylene in said at least partial liquid phase with said catalyst composition under catalytic alkylation conditions comprising a feed weight hourly space velocity (WHSV)

To a method comprising the steps of:

Brief Description of Drawings

Figure 1 shows the results of a comparison of the diisopropylbenzene / isopropylbenzene selectivity (vertical axis) versus Versal 300 alumina combined with 1 (non-seeded MCM-56, out-of-seeded MCM-56 and in situ seeded MCM- / 20 "quadrulobe extrudate (abscissa). &Lt; tb &gt; &lt; TABLE &gt;

Figure 2 shows a 1/20 &lt; RTI ID = 0.0 &gt; 1/2 "&lt; / RTI &gt; ratio of triisopropylbenzene / isopropylbenzene selectivity (vertical axis) versus Versal 300 alumina for non-seeded MCM-56, out of seeded MCM- (Abscissa) of the MCM-56 in the four-leaf extrudate.

Figure 3 shows the activity (as a second order rate constant k2 x 1,000) (vertical axis) for unseeded MCM-56, out-of-seeded MCM-56 and in situ seeded MCM-56 1/20 "Shows the plot of the ratio of MCM-56 in the four-leaf extrudate (abscissa).

FIG. 4 is a graph showing the selectivity of diisopropylbenzene / triisopropylbenzene versus (vertical axis) versus U.S.Val 300 alumina for non-seeded MCM-56, out-of-seeded MCM-56 and in situ seeded MCM- "Shows the plot of the ratio of MCM-56 in the four-leaf extrudate (abscissa).

Figure 5 shows plots of diethylbenzene / ethylbenzene selectivity (vertical axis) vs. ethylene conversion (abscissa) for the method of Examples 16.1-16.5.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to an improved process for the preparation of monoalkylated aromatic compounds, in particular ethylbenzene, cumene and sec-butylbenzene, by liquid or partial liquid phase alkylation of alkylatable aromatic compounds, in particular benzene. More specifically, the process of the present invention is carried out in a process comprising the steps of: from about 20/80 to about 80/20 or from about 20/80 to about 60/40, preferably from about 20/80 to about 40/60, A catalytic composition comprising a porous crystalline material such as crystalline aluminosilicate and a binder at a crystal / binder weight ratio of from 40/60 to about 60/40 is used.

The process for preparing the catalysts necessary for use in the present invention is described below and is hereby incorporated by reference in its entirety, for example, only by adjusting the compounding or extrusion of the final catalyst to include a crystal / binder ratio of from about 20/80 to about 60/40. Quot ;, which is incorporated herein by reference. This is within the ability of one skilled in the art of catalyst manufacture. For example, US Pat. No. 4,954,325 discloses crystalline MCM-22 and catalysts comprising it, US Pat. No. 5,236,575 describes crystalline MCM-49 and catalysts comprising it, US Pat. No. 5,362,697 and US Pat. No. 5,557,024 discloses crystalline MCM-56 and catalysts comprising it. The particular crystalline material may be blended or extruded with the binder to form the required catalyst for use herein, wherein the final catalyst product is present in an amount of from about 20/80 to about 60/40 or from about 20/80 to about 80/20, Care must be taken to include a crystal / binder ratio of from about 40/60 to about 80/20 or even more preferably from about 40/60 to about 60/40.

The term " ex situ seeded " as used herein refers to a method of introducing a zeolite seed into a zeolite synthesis reactor in which the zeolite seed is added to the reactor in its as-synthesized state do.

The term " in situ seeded " as used herein refers to a process in which a zeolite seed is introduced into a zeolite synthesis reactor in which the residual zeolite seed in the reactor from the previous zeolite crystallization remains as it is synthesized Quot;

It should be understood that the term "aromatic" in the context of an alkylatable aromatic compound which may be useful as a feedstock herein is contemplated to be within the skill in the art. This includes alkyl substituted and unsubstituted mononuclear and polynuclear compounds. Compounds having aromatic properties with heteroatoms are also useful unless they act as catalyst poisons under selected reaction conditions.

Substituted aromatic compounds that can be alkylated herein should have at least one hydrogen atom directly bonded to the aromatic nucleus. The aromatic ring may be substituted with one or more alkyl, aryl, alkaryl, alkoxy, aryloxy, cycloalkyl, halide, and / or other groups that do not interfere with the alkylation reaction.

Suitable aromatic compounds include benzene, naphthalene, anthracene, naphthacene, perylene, coronene, and phenanthrene, with benzene being preferred.

Generally, alkyl groups that may be present as substituents in aromatic compounds contain 1 to about 22 carbon atoms, typically about 1 to 8 carbon atoms, most usually about 1 to 4 carbon atoms.

Suitable alkyl substituted aromatic compounds include, but are not limited to, toluene, xylene, isopropylbenzene, n-propylbenzene, alpha -methylnaphthalene, ethylbenzene, mesitylene, duren, cymene, butylbenzene, Diethylbenzene, p-diethylbenzene, isoamylbenzene, isohexylbenzene, pentaethylbenzene, pentamethylbenzene; 1,2,3,4-tetraethylbenzene; 1,2,3,5-tetramethylbenzene; 1,2,4-triethylbenzene; 1,2,3-trimethylbenzene, m-butyltoluene; p-butyltoluene; 3,5-diethyltoluene; o-ethyltoluene; p-ethyltoluene; m-propyltoluene; 4-ethyl-m-xylene; Dimethylnaphthalene; Ethyl naphthalene; 2,3-dimethyl anthracene; 9-ethyl anthracene; 2-methyl anthracene; o-methyl anthracene; 9,10-dimethylphenanthrene; And 3-methyl-phenanthrene. Alkylaromatic compounds having larger molecular weights can also be used as starting materials and are produced by alkylation of aromatic organic compounds such as aromatic organic compounds using olefin oligomers. Such products are often referred to in the art as alkylates and include hexylbenzene, nonylbenzene, dodecylbenzene, pentadecylbenzene, hexyltoluene, nonyltoluene, dodecyltoluene, and pentadecyltoluene. Often the alkylate is obtained as a high boiling fraction in which the size of the alkyl group bonded to the aromatic nucleus is varied from about C ₆ to about C ₁₂ . When cumene or ethylbenzene is the desired product, the process of the present invention yields acceptable byproducts, such as xylene. The xylene produced in such a case may be less than about 500 ppm.

A reformate containing a mixture of benzene, toluene and / or xylene constitutes a particularly useful feed for the alkylation process of the present invention.

Alkylating agents that may be useful in the process of the present invention are generally alkylatable aromatic compounds, preferably any aliphatic or aromatic &lt; RTI ID = 0.0 &gt; organoaluminum &lt; / RTI &gt; having an alkylated aliphatic group capable of reacting with an alkylating group having from 1 to 5 carbon atoms &Lt; / RTI &gt; Examples of suitable alkylating agents include olefins such as ethylene, propylene, butene and pentene; Alcohols (including monoalcohols, diols, tri alcohols and the like) such as methanol, ethanol, propanol, butanol and pentanol; Aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde and n-valer aldehyde; And halogenated alkyls such as methyl chloride, ethyl chloride, propyl chloride, butyl chloride and pentyl chloride.

Mixtures of light olefins are useful as alkylating agents in the alkylation process of the present invention. Thus, various refinery streams, such as gas plant off-gas containing fuel gas, ethylene, propylene, etc., naphtha cracking off-gas containing light olefins, refined FCC propane / propylene stream, Mixtures of propylene, butene and / or pentene are alkylating agents useful herein. For example, a typical FCC light olefin stream has the composition in Table 3A below:

<Table 3A>

The reaction products obtainable from the process of the present invention include cumene from the reaction of benzene with ethylene, benzene from the reaction of benzene and propylene, ethyl toluene from the reaction of toluene with ethylene, cymene from the reaction of toluene and propylene, and Sec-butylbenzene from the reaction of benzene and n-butene. A particularly preferred process of the present invention relates to the preparation of cumene by alkylation of benzene with propylene and the preparation of ethylbenzene by alkylation of benzene with ethylene.

The reactants for the improved process of the present invention may be partly or completely liquid and may be knit, i.e. without intentional mixing or dilution with other materials, or they may be diluted with a carrier gas or diluent, such as hydrogen or nitrogen, Lt; / RTI &gt;

The improved alkylation process of the present invention allows the reactants, i.e. alkylatable aromatic compounds and alkylating agents, to be contacted with the catalyst of the present invention in an appropriate reaction zone, for example under effective alkylation conditions in a flow reactor containing a stationary phase of the catalyst composition . Such conditions include a temperature of from about 0 캜 to about 500 캜, preferably from about 10 캜 to about 260 캜, a pressure of from about 0.2 to about 25,000 kPa-a, preferably from about 100 to about 5,500 kPa-a, 1 to about 50: 1, preferably from about 0.5: 1 to about 10: 1, and an alkylating agent of from about 0.1 to 500 hr ^-1 , preferably from about 0.5 to about 100 hr ^-1 , (WHSV) &lt; / RTI &gt; based on the feed weight.

When ethylene is used to alkylate benzene to produce ethylbenzene, the alkylation reaction is preferably carried out at least partially under liquid phase conditions such that at least a portion of the benzene is in a liquid phase during the alkylation reaction. Suitable conditions include a temperature of from about 150 ° C to about 300 ° C, more preferably from about 170 ° C to about 260 ° C, a pressure of about 20,400 kPa-a, more preferably from about 2,000 kPa-a to about 5,500 kPa-a, (WHSV) based on an ethylene alkylating agent of from about 0.1 to about 20 h ^-1 , more preferably from about 0.5 to about 6 h ^-1 , and from about 0.5: 1 to about 30: 1, 1: 1 to about 10: 1 alkylation reactor.

When propylene is used to alkylate benzene to produce cumene, the reaction may also be carried out at a temperature of about 250 ° C or less, preferably about 150 ° C or less, such as about 10 ° C to about 125 ° C, about 25,000 kPa-a or less, For example, a pressure of from about 100 to about 3,000 kPa-a; (WHSV) based on propylene alkylating agent of from about 0.1 h ^-1 to about 250 h ^-1 , preferably from about 1 h ^-1 to about 50 h ^-1 , and a weight hourly space velocity (WHSV) of from about 0.5: 1 to about 30: 1, More preferably from about 1: 1 to about 10: 1, in a molar ratio of benzene to propylene in an alkylation reactor.

Butylbenzene, for example sec-butylbenzene, is produced by alkylating benzene with butene, for example n-butene, the reaction is also carried out at a temperature of about 250 ° C or lower, preferably about 150 ° C or lower, A pressure of from about 0.1 h ^-1 to about 250 h ^-1 , preferably from about 1 h ^{-1 to} about 1 h ^-1 , at a temperature of from about 10 ° C to about 125 ° C, at a pressure of about 25,000 kPa-a or less, to a weight hourly space velocity based on the butene alkylating agent of from about 50 h ^-1 (WHSV), and about 0.5: 1 to about 30: 1, more preferably from about 1: benzene in the alkylation reactor from 1: 1 to about 10 Butene under the conditions of at least partly liquid phase.

The crystalline portion of the catalyst for use in the present invention may comprise a crystalline molecular sieve having the structure of zeolite beta (described in U.S. Patent No. 3,308,069) or MCM-22 family material. The catalyst may be used in an amount of from about 20/80 to about 80/20 or from about 20/80 to about 40/60, preferably from about 20/80 to about 40/60, or even more preferably from about 40/60 to about 60 / Should contain a crystalline molecular sieve combined in a conventional manner with an oxide binder as described in detail below at a weight ratio of 40 crystal / binder.

For certain applications of the catalyst, the average particle size of the crystalline molecular sieve component may be from about 0.05 to about 200 microns, for example from 20 to about 200 microns.

As used herein, the term "MCM-22 family material" (or "MCM-22 family material" or "MCM-22 family molecular sieve") includes:

(i) Molecular sieves generated as a common first degree crystalline building block "unit cell with MWW skeletal topology &quot;. To describe a crystal as described in the Atlas of Zeolite Framework Types , Fifth edition, 2001, the entire disclosure of which is incorporated herein by reference, a unit cell is a spatial alignment of tiled atoms within a three-dimensional space .

(ii) a common second degree building block of the MWW skeletal type unit cell, which forms a "single layer thickness of one unit cell", preferably one c-unit cell thickness, itself;

(iii) a molecular sieve produced from a common second degree building block, "a layer of one or more unit cell thicknesses," wherein a layer of more than one unit cell thickness comprises a unit cell having an MWW framework topology Is formed by stacking, packing or combining two or more monolayers having a unit cell thickness. The stacking of such second degree building blocks may be a regular, irregular, random or any combination thereof; or

(iv) molecular sieves generated by any rule or random two-dimensional or three-dimensional combination of unit cells with MWW skeletal topology.

The MCM-22 family material is characterized by having an X-ray diffraction pattern comprising a d-distance maximum at 12.4 ± 0.25, 3.57 ± 0.07 and 3.42 ± 0.07 Å (as calcined or synthesized). The MCM-22 family material is also characterized by having an X-ray diffraction pattern comprising a d-distance maximum at 12.4 + -0.25, 6.9 + -0.15, 3.57 + -0.07 and 3.42 + 0.07A (as calcined or synthesized) . The X-ray diffraction data used to characterize the molecular sieve is obtained by standard techniques using a connected computer as the incident radiation, a K-alpha double line of copper, a diffractometer equipped with a scintillation counter, and a collection system. Materials belonging to 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) , ITQ-2 (described in International Patent Publication No. WO 97/17290), ITQ-1 (described in US Patent No. 6,077,498), ERB-1 (described in European Patent No. 0293032) (Described in U.S. Patent No. 5,236,575), MCM-56 (described in U.S. Patent No. 5,362,697), MCM-36 (described in International Patent Publication No. WO2005118476) And UZM-8 (described in U.S. Patent No. 6,756,030). The entire disclosure of these patents is incorporated herein by reference.

The MCM-22 family molecular sieve described above is distinguished from conventional macropore zeolite alkylation catalysts such as mordenite, and the MCM-22 material has a 12-ring surface pocket that is not in communication with the 10- .

The zeolite material designated as the MWW topology by IZA-SC is a multilayer material with two pore systems resulting from the presence of both 10 and 12 membered rings. The Atlas of Zeolite Framework Types classifies differently named substances into five classes with the same topology of MCM-22, ERB-1, ITQ-1, PSH-3 and SSZ-25.

MCM-22 family molecular sieves have been found useful in various hydrocarbon conversion processes. Examples of MCM-22 family molecular sieves include MCM-22, MCM-49, MCM-56, ITQ-1, PSH-3, SSZ-25 and ERB-1. Such molecular sieves are useful for the alkylation of aromatic compounds. For example, U.S. Patent No. 6,936,744 discloses a monoalkylated aromatic compound comprising contacting a polyalkylated aromatic compound with an alkylatable aromatic compound under at least partial liquid phase conditions and in the presence of a transalkylation catalyst to produce a monoalkylated aromatic compound, Wherein the transalkylation catalyst comprises a mixture of two or more different crystalline molecular sieves wherein each molecular sieve has a molecular weight of 12.4 + - 0.25, 6.9 + - 0.15, 3.57 + - 0.07 and 3.42 + 0.07 zeolite beta, zeolite Y, and mordenite, having an X-ray diffraction pattern including a maximum d-distance value.

In particular, the molecular sieve used in the alkylation process of the present invention comprises MCM-56 crystals produced by a process wherein the synthesis mixture comprises a zeolite crystal, in particular a seed of MCM-56 crystal. A suitable method is disclosed in U.S. Provisional Application No. 61 / 535,632 (Johnson et al.), Filed September 16, 2011, which is hereby incorporated by reference in its entirety. The crystals thus produced are characterized in that they are seeded MCM-56 crystals.

The seeded MCM-56 crystals are characterized by an X-ray diffraction pattern as disclosed in U.S. Patent Nos. 5,362,697 and 5,827,491, each of which is incorporated herein by reference.

The X-ray diffraction patterns disclosed in U.S. Patent Nos. 5,362,697 and 5,827,491 are presented in the following Table 1 (as synthesized) and Table 2 (as calcined). In the following Tables 1 and 2, the intensity is defined for the d-distance line at 12.4 A.

<Table 1>

<Table 2>

The X-ray diffraction data were collected using a Scintag diffractometer equipped with a germanium solid state detector using copper K-alpha radiation. Diffraction data were recorded by step-scan at 2 [theta] of 0.02 [deg.], Where [theta] is the Bragg angle and the counting time for each step is 10 seconds. I-I _{0, which} is the relative strength of the line, is one-hundredth the intensity of the strongest line, and the profile fitting routine (or 2 The second derivative algorithm). Strength does not compensate for Lorentz and polarization effects. Relative strengths are given in terms of abbreviation vs = very strong (60-100), s = strong (40-60), m = medium (20-40) and w = weak (0-20). It should be understood that the diffraction data presented as a single line for this sample can consist of a plurality of overlapping lines under certain conditions, such as differences in crystallographic change, which may appear as broken or partially broken lines. Typically, the crystallographic change may include a change in crystal symmetry and / or a small change in unit cell variable without a change in the structure. These small effects, including changes in relative strength, can occur as a result of cation content, skeletal composition, properties and degree of pore filling and differences in thermal and / or hydrothermal history.

The process for the preparation of seeded MCM-56 crystals

a) an alkali metal or alkaline earth metal (M) cation, for example sodium or potassium cations, oxides of trivalent elements X, for example oxides of aluminum, oxides of quaternary elements Y, Preferably having a composition with respect to the molar ratio of oxides selected, preferably within the range of Table 3B below, as a first reaction mixture containing at least 30% by weight of solid YO ₂ and water, 1 zeolite seeds in an amount of not less than 0.05% by weight or not less than 0.10% by weight or not less than 0.50% by weight or not less than 1.0% by weight and not more than 5% by weight, for example, not less than 1% Preparing a first reaction mixture further comprising a crystal, preferably an MCM-56 seed crystal,

<Table 3B>

YO ₂ / X ₂ O ₃ = 5 to 35, for example, 15 to 20

H ₂ O / YO ₂ = 10 to 70, for example, 15 to 20

OH ^- / YO ₂ = 0.05 to 0.20, such as 0.1 to 0.15

M / YO ₂ = 0.05 to 3.0, for example 0.11 to 0.15;

b) to the reaction mixture of step a) is added an initiator R, for example hexamethyleneimine (HMI), preferably in the following range: R / YO ₂ Forming a second reaction mixture having said derivatizing agent R with respect to a molar ratio within the range of from 0.08 to 0.3, for example from 0.1 to 0.2;

c) heating the second reaction mixture of step b) to a temperature of from about 90 캜 to about 175 캜, preferably from about 90 캜 to less than 160 캜, such as from about 125 캜 to about 175 캜, , Under conditions of less than 40 h, for example from about 20 to about 75 h, at a stirring rate of from about 40 to about 250 rpm, preferably from about 40 to about 100 rpm and confirmed by X-ray diffraction 56 mass% of the MCM-56 material and less than or equal to about 5% by weight, based on the total weight of the MCM-56 crystal in the second reaction mixture, of non-MCM-56 impurities Crystalline material, such as crystalline MCM-22 family material (defined below), such as MCM-49 material or ferrierite, kenate, or mixtures thereof; And

d) separating and recovering at least a portion of the crystals of the MCM-56 material from the mixture of step c) to produce the as-synthesized MCM-56 material, wherein the crystals of the as-synthesized MCM- Which is characterized by the X-ray diffraction pattern shown in Table 1 above

.

The second reaction mixture of step b) has a solids content of greater than or equal to 12 wt%, or greater than or equal to 15 wt%, or greater than or equal to 18 wt%, or greater than or equal to 20 wt%, or greater than or equal to 30 wt% and less than or equal to 40 wt% Or less than 50 wt% or less than 60 wt%. Preferably, the solids content of the second reaction mixture of step b) is less than 30% by weight based on the weight of the second reaction mixture.

In order to achieve the first reaction mixture composition required of the improved process of the present invention, some selective threshold changes must be made in the process for producing the MCM-56 material compared to the conventional practice. Except for the addition of, for example, caustic NaOH, except that it is, for example, as a component of sodium aluminate. In addition, the organic derivatizing agent is added to the first reaction mixture to a first reaction mixture that is not added during its production, but only a controlled amount of organic inducing agent that has been reduced to a near stoichiometric amount, resulting in a second reaction mixture. Further, the zeolite seed crystals, preferably the zeolite seed crystals of the MCM-22 family material, more preferably the zeolite seed crystals of the MCM-56, can be prepared in such a manner that the amount of the seed crystals, based on the total amount of the first reaction mixture, Is added to the first reaction mixture in an amount of 0.05 wt% or more, or 0.10 wt% or more, or 0.50 wt% or more, or 1.0 wt% or more to 5 wt% or less, for example, 1 wt% or more to 3 wt% or less. Surprisingly, the addition of MCM-56 seed crystals to the first reaction mixture required for this improved process does not accelerate the production of impurities as would normally be expected in such crystallization procedures.

The improved method of the present invention advantageously stabilizes and extends the crystallization window in step c) of the process in order to prevent the formation of impurities such as MCM-49 material; Reducing the organic loading in the crystallization step c), which reduces costs, and in particular the significant cost in commercial MCM-56 manufacture; The crystallization rate is accelerated in step c) to greatly improve the throughput. Additionally, intentional addition of the preferred MCM-56 seed crystals reverses the normally expected effect of accelerating the crystallization of impurities caused by residual particles in the crystallizer. This is particularly important in commercial manufacture. In an improved method, seeding does not accelerate the introduction of impurities.

In the improved process of the present invention, the source of YO ₂ is solid YO _2, for example It should be a solid YO ₂ of at least about 30% by weight. If the YO ₂ is silica, the silica source containing at least about 30 wt.% Solid silica, e.g., Current Shipper Nat (Sipernat) ^® (precipitated spray dried silica containing about 90 wt.% Silica) or a high thread (HiSil ) &Lt; / RTI &gt; (a precipitated hydrated silica having a particle size of about 0.02 microns and containing about 4.5 wt.% Combined H ₂ O, about 6 wt.% Free H ₂ O and about 87 wt.% Silica of hydration) (Ultrasil) assists in the formation of crystalline MCM-56 from the second reaction mixture under the required synthesis conditions. Thus, preferably the YO _2, for example, the silica source is from about 30% by weight or more of solid YO _2, e.g., silica, and more preferably about 40% by weight or more of solid YO _2, for example, containing silica.

The organic derivatizing agent R can be selected from the group consisting of cycloalkylamines, azacycloalkanes, diazacycloalkanes, and combinations thereof, wherein the alkyl comprises from 5 to 8 carbon atoms. Non-limiting examples of R include cyclopentylamine, cyclohexylamine, cycloheptylamine, hexamethyleneimine (HMI), heptamethyleneimine, homopiperazine, and combinations thereof.

It should be noted that the reaction mixture component may be provided by more than one source. The reaction mixture may be produced batchwise or continuously.

It is preferred that step c) crystallization of the second reaction mixture in the process of the present invention is carried out in a suitable reactor vessel, for example a polypropylene vessel or a Teflon lined or autoclave in stainless steel, under stirring conditions. However, it is within the scope of the present invention to conduct crystallization under static conditions.

A useful range of conditions for crystallization in the present method is a high quality determination of the MCM-56 material, as determined by X-ray diffraction, and a high quality determination of the 10 &lt; RTI ID = 0.0 &gt; Deg.] C to about 175 [deg.] C, preferably less than about 90 [deg.] C to less than 160 [deg.] C, such as from about 125 [deg.] C to about A temperature of 175 DEG C and a time of less than 90 h, preferably less than 40 h, such as from about 20 to about 75 h, preferably from about 40 to about 250 rpm, more preferably from about 40 to about 100 rpm Speed. The crystals of the as-synthesized MCM-56 material are then separated and recovered from the resulting liquid mixture in step d).

Another embodiment of the improved process is a process for the preparation of the second step of step b) before crystallization step c) at a temperature of from about 0.5 to about 48 h, for example from about 0.5 to about 24 h, And aging the reaction mixture. Preferably, the second reaction mixture is shaken, for example, at 50 rpm for less than 48 h while stirring at room temperature.

Catalysts comprising the seeded MCM-56 material so produced can be used to effect conversion in a chemical reaction and include contacting the alkylatable aromatic compound under an at least partial liquid phase condition in the presence of a catalyst with an alkylating agent , And is particularly useful in a process for selectively producing a desired monoalkylated aromatic compound. Thus, another embodiment of the present invention is an improved alkylation process comprising high quality seeded MCM-56 prepared by the improved process of the present invention for use in a process for the selective production of products comprising monoalkylated benzene Wherein the process comprises reacting benzene with an alkylating agent such as ethylene or propylene under alkylation conditions in the presence of the alkylation catalyst to form the product. When using the catalyst of the present invention as an alkylation catalyst to effect alkylation of an alkylatable aromatic compound, the alkylating agent may comprise an alkylated aliphatic group having from 1 to 5 carbon atoms. The alkylating agent may be, for example, ethylene or propylene, and the alkylatable aromatic compound may in this case be suitably benzene.

In one or more embodiments of the method for the selective production of monoalkylated benzene, the product may further comprise the production of a dialkylated benzene and a trialkylated benzene which may be generated. In such cases, the weight ratio of trialkylated benzene to the dealkylated benzene is in the range of 0.02 to 0.16 or 0.4 to 0.16 or 0.08 to 0.12.

The MCM-56 thus prepared can be used as a catalyst component for carrying out the hydrocarbon compound conversion and can be prepared by reacting an optionally selected alkylation reagent, such as ethylbenzene or cumene, optionally in contact with ethylene or propylene under at least partial liquid phase conditions Lt; RTI ID = 0.0 &gt; as &lt; / RTI &gt;

The catalyst for use in the alkylation process of the present invention will comprise an inorganic oxide material matrix or binder. Such matrix or binder materials include synthetic or natural materials as well as inorganic materials such as clay, silica and / or metal oxides. The latter may be natural or may be in the form of a gel-like precipitate or gel comprising a mixture of silica and metal oxides. Natural clays that can be complexed with inorganic oxide materials include sub-bentonites commonly known as Dixie, McNamee, Georgia, and Florida clays, and montmorillonite including kaolin And kaolin series, or the main mineral component is haloisite, kaolinite, dickite, nacrite or anoxsite. The clay may be used in its originally mined state, or initially treated with calcination, acid treatment or chemical modification.

Specific useful catalyst matrix or binder materials used herein include silica, alumina, zirconia, titania, silica-alumina, silica-magnesia, silica-zirconia, silica-tori, silica- beryllium, silica- Silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia. The matrix may be in the form of a cogel. Mixtures of these components may also be used.

In the inventive process for producing ethylbenzene from benzene and ethylene, the relative ratio of seeded MCM-56 crystals and binder or matrix is from about 20/80 to about 80/20, preferably from about 40/60 to about 80 / 20 &lt; / RTI &gt; or even about 40/60 to 60/40 crystal / binder.

In the process of the present invention, the alkylation reactor effluent may contain excess aromatic feed, monoalkylated product, polyalkylated product and various impurities. The aromatic feed is recovered by distillation and recycled to the alkylation reactor. Generally, a small bleeding is taken from the recycle stream to remove unreacted impurities from the loop. The bottom product from the distillation may be further distilled to separate the monoalkylated product from the polyalkylated product and other heavy products.

The polyalkylated product separated from the alkylation reactor effluent can react with further aromatic feeds on a suitable transalkylation catalyst in a separate transalkylation reactor separate from the alkylation reactor. The transalkylation catalyst is a zeolite beta, zeolite Y, mordenite or MCM-22 family material with an X-ray diffraction pattern containing maximum d-distances at 12.4 ± 0.25, 6.9 ± 0.15, 3.57 ± 0.07 and 3.42 ± 0.07 Å &Lt; / RTI &gt; or mixtures thereof.

The X-ray diffraction data used to characterize the catalyst structure is obtained by a standard technique using K-alpha doublets of copper as incident radiation and a diffractometer equipped with a computer connected as a scintillation counter and collector. Examples of the substance having the X-ray diffraction line include MCM-22 (described in US Patent No. 4,954,325), PSH-3 (described in US Patent No. 4,439,409), SSZ-25 (US Patent No. 4,826,667 ITQ-1 (described in U.S. Patent No. 6,077,498), ITQ-2 (described in U.S. Patent No. 6,231,751), ITQ-1 (described in European Patent No. 0293032) (Described in U.S. Pat. No. 5,236,575) and MCM-56 (described in U.S. Pat. No. 5,362,697), as disclosed in WO 2005-118476, MCM-36 ), And MCM-22 is particularly preferable.

Zeolite beta is disclosed in U.S. Patent No. 3,308,069. Zeolite Y and mordenite are natural but also have one of their synthetic forms, such as Ultrastable Y (USY) disclosed in U.S. Patent No. 3,449,070, rare-earth exchanged Y (REY) disclosed in U.S. Patent No. 4,415,438, And TEA-mordenite disclosed in U.S. Patent Nos. 3,766,093 and 3,894,104 (i.e., synthetic mordenite produced from a reaction mixture comprising a tetraethylammonium inducing agent). However, in the case of TEA-mordenite for use in transalkylation catalysts, the specific synthetic methods described in the reported patents are mordenite products of predominantly large crystals, larger in size than 1 micron and typically about 5 to 10 microns . It has been found that the synthesis is regulated so that the average crystal size of the resultant TEA-mordenite is less than 0.5 microns to produce a transalkylation catalyst with substantially improved activity for liquid phase aromatic transalkylation.

The small crystals TEA-mordenite required for transalkylation can be produced by crystallization from a synthesis mixture having a molar composition within the range of Table 3C below:

<Table 3C>

The crystallization of the small crystalline TEA-mordenite from such a synthesis mixture is carried out at a temperature of from 90 DEG C to 200 DEG C for a period of from 6 to 180 h.

Example

Non-limiting examples of the invention, including improved alkylation mechanisms, are described with reference to the following experiments. In these experiments, the catalytic reactivity was determined by the following procedure.

Experiment

A 300 ml Parr batch reactor equipped with stir bar and stationary catalyst basket was used for activity and selectivity measurements. The reaction vessel was equipped with two removable vessels for the introduction of benzene and propylene, respectively.

Feed pretreatment

benzene

Benzene was obtained from commercial sources. Benzene was prepared by mixing 500 cc of molecular sieve 13X followed by 500 cc of molecular sieve 5A and then 1,000 cc Selexsorb CD followed by 500 cc of 80 wt% MCM-49 and 20 wt% Al ₂ O ₃ (2 L Hoke vessel). All feed pretreatments were dried for 12 h in an oven at 260 ° C prior to use.

Propylene

Propylene was obtained from a commercial specialty gas supplier and was polymer grade. Propylene was passed through a 300 ml vessel containing the pretreatment material in the following order:

a. 150 ml molecular sieve 5A

b. 150 ml Celsius sorb CD

Both guard-bed materials were dried in an oven at 260 캜 for 12 hours prior to use.

nitrogen

Nitrogen was of very high purity grade and was obtained from commercial specialty gas suppliers. Nitrogen was passed through a 300 ml vessel containing the pretreatment material in the following order.

a. 150 ml molecular sieve 5A

b. 150 ml Celsius sorb CD

Both guard-layer materials were dried for 12 h in an oven at &lt; RTI ID = 0.0 &gt; 260 C &lt; / RTI &gt;

Catalyst manufacturing and loading

A sample of 2 g of catalyst was dried in an oven at 260 &lt; 0 &gt; C for 2 h in air. The catalyst was removed from the oven and immediately weighed 1 g of catalyst. After lining the bottom of the basket using a quartz chip, 0.5 or 1.0 g of catalyst was loaded in the basket on top of the first layer of quartz. The quartz chips were then placed on top of the catalyst. The basket containing the catalyst and quartz chips was placed in an oven at 260 &lt; 0 &gt; C overnight in air for about 16 h.

The basket containing the catalyst and the quartz chips was removed from the oven, immediately placed in the reactor, and the reactor immediately assembled.

Test sequence

The reactor temperature was set at 170 占 폚 and rinsed with ultra-high purity nitrogen of 100 sccm (standard cubic centimeters) for 2 h. After the reactor was flushed with nitrogen for 2 h, the reactor temperature was reduced to 130 캜, the nitrogen flush was stopped, and the reactor vents were closed. A quantity of 156.1 g benzene was placed in a 300 ml mobile vessel and run in a closed system. The benzene vessel was pressurized with ultrahigh purity nitrogen to 2,169 kPa-a (300 psig) and the benzene was transferred to the reactor. The shaker speed was set at 500 rpm and the reactor was allowed to equilibrate for 1 h. Thereafter, a 75 ml hopper moving vessel was charged with 28.1 g of liquid propylene, connected to the reaction vessel, and connected with 2,169 kPa-a (300 psig) ultrahigh purity nitrogen. After the 1 h benzene agitation time had elapsed, the propylene was transferred from the kettle vessel to the reactor. A 2,169 kPa-a (300 psig) nitrogen feed connected to the propylene vessel was maintained and opened to the reactor during the entire run to maintain constant reaction pressure during the test. A liquid product sample was taken at 30, 60, 90, 120 and 180 minutes after addition of propylene.

In the following examples, the selectivity is the weight ratio of the recovered product diisopropylbenzene (DIPB / IPB) to the product isopropylbenzene recovered after the conversion of propylene reaches 99 +%. The activity of all embodiments is determined by calculating the second-order rate constant for the batch reactor using mathematical techniques known to those skilled in the art.

Example 1

16 parts of water and 45% sodium aluminate solution _{(22% Al 2 O 3,} 19.5% Na 2 O) 1 part were placed in an autoclave reactor. The solution was shaken at 60 rpm for 1 to 24 h at room temperature. Then, 3.14 parts of SiO ₂ (Ultrasil (Ultrasil) -VN3PM- modified search, are known to Shipper Nat 320C, available from Phoenix, EVO (Evoniks) was gussa (Degussa) to the previous available) and 0.02 parts of MCM-56 seed (Dry cake) was added to form the first reaction mixture. The reactor was sealed and the pressure tested. Thereafter, 0.53 parts of hexamethyleneimine (HMI as 100% organic matter) was added to the reactor to form a second reaction mixture. The second reaction mixture was shaken at 50 rpm for less than 48 h at ambient temperature. The reactor was then heated from 50 rpm to 151 캜 and the contents allowed to crystallize for 28 h to form a mixture. The resulting mixture consisted of MCM-56 and less than 10% by weight of impurities as determined by X-ray diffraction. The reactor was cooled to 127 DEG C and the organics were removed by HMI / water azeotropic distillation, i. E. By "flashed treatment" The flash-treated solvent ("condensate") was combined with additional unused HMI for subsequent batches for recycling. The reactor was cooled and the product was discharged. The degree of crystallization was confirmed by BET surface area. Blending details and results for Example 1 are reported in Tables 4 and 5 below.

Example 1.1

16 parts of water, 1 part of 45% sodium aluminate solution (22% Al ₂ O ₃ , 19.5% Na ₂ O), 3.13 parts of SiO ₂ (Sipernat 320C), 0.02 parts of MCM-56 seed and 0.53 parts of hexamethyleneimine HMI as 100% organic material) was placed in an autoclave reactor. The reactor was sealed and pressure tested. The resulting solution was shaken at room temperature for less than 48 h at 250 rpm. The autoclave was then heated to 150 DEG C at 250 rpm, allowing the contents to react for 72 h. At this time, it was confirmed by X-ray diffraction that the product was amorphous. The reactor was cooled to 127 DEG C and the organics were removed by HMI / water azeotropic distillation, i. E. By "flashing" The reactor was cooled and the product was discharged. The degree of crystallization was confirmed by BET surface area. Blending details and results for Example 1.1 are reported in Tables 4 and 5 below.

Example 1.2

16 parts of water, 1 part of 45% sodium aluminate solution (22% Al ₂ O ₃ , 19.5% Na ₂ O), 3.14 parts of SiO ₂ (Sipernat 320C) and 0.02 parts of MCM-56 seed (dry cake) After the first reaction mixture was formed in the reactor, 0.53 parts of hexamethyleneimine (HMI as 100% organic matter) was added to the reactor to form a second reaction mixture. The reactor was sealed and pressure tested. The second reaction mixture was shaken at room temperature for less than 48 h at 250 rpm. The reactor was heated to 150 DEG C at 250 rpm and the contents allowed to crystallize for 72 h to form a mixture. The resulting mixture consisted of MCM-56 and less than 10% by weight of impurities as determined by X-ray diffraction. The reactor was cooled to 127 DEG C and the organics were removed by HMI / water azeotropic distillation, i. E. By "flashing" The reactor was cooled and the product was discharged. For some crystals, the degree of crystallinity was confirmed by BET surface area. Blending details and results for Example 1.2 are reported in Tables 4 and 5 below.

Example 2

16 parts of water and 45% sodium aluminate solution _{(22% Al 2 O 3,} 19.5% Na 2 O) 1 part were placed in an autoclave reactor. The solution was shaken at 60 rpm for 1 to 24 h at room temperature. Thereafter, 3.14 parts of SiO ₂ (Sipernat 320C) and 0.02 parts of MCM-56 seed (dry cake) were added to form the first reaction mixture. The reactor was sealed and pressure tested. Then, 0.53 parts of hexamethyleneimine (HMI as 100% organic matter) was added to the reactor to form a second reaction mixture. The second reaction mixture was shaken at 50 rpm for less than 48 h at ambient temperature. The reactor was sealed, heated to 141.5 캜 at 50 rpm, and the contents allowed to crystallize for 36 h to form a mixture. The resulting mixture consisted of MCM-56 and less than 10% by weight of impurities as determined by X-ray diffraction. The reactor was cooled to 127 DEG C and the organics were removed by HMI / water azeotropic distillation, i. E. By "flashing" The flash-treated solvent ("condensate") was combined with additional unused HMI for subsequent batches for recycling. The reactor was cooled and the product was discharged. The degree of crystallization was confirmed by BET surface area. Blending details and results for Example 2 are reported in Tables 4 and 5 below.

Example 3

To 0.02 part of the MCM-56 seed in the as-synthesized state remaining in the reactor from the previous MCM-56 crystallization in the autoclave reactor, 0.72 part of water and 1 part of 5% sodium aluminate solution (USALCO) a solution of the initial 22% Al ₂ O ₃ and _{19.5% Na 2 2.9% Al 2} O 3 and 1.8% Na ₂ O as a by adding water to obtain a dilution of the bar from the O) was added. The solution was shaken at 60 rpm for 1 to 24 h at room temperature. Thereafter, 0.31 part of SiO ₂ (Sipperat 320C) was added to form the first reaction mixture. The reactor was sealed and pressure tested. Thereafter, 0.053 parts of hexamethyleneimine (HMI as 100% organic matter) was added to the reactor to form a second reaction mixture. The second reaction mixture was shaken at 60 rpm for less than 48 h at ambient temperature. The reactor was sealed, heated to &lt; RTI ID = 0.0 &gt; 148.5 C &lt; / RTI &gt; at 60 rpm and allowed to crystallize for 36 h to form a mixture. The resulting mixture consisted of MCM-56 and less than 10% by weight of impurities as determined by X-ray diffraction. The reactor was cooled to 127 DEG C and the organics were removed by HMI / water azeotropic distillation, i. E. By "flashing" The flash-treated solvent ("condensate") was combined with additional unused HMI for subsequent batches for recycling. The reactor was cooled and the product was discharged. The degree of crystallization was confirmed by BET surface area. Blending details and results for Example 3 are reported in Tables 4 and 5 below.

Example 3.1

1 part of 5% sodium aluminate (initial 22% Al ₂ O ₃ and 19.5% Na ₂ O to 2.9% Al ₂ O ₃ and 1.8% Na ₂ O, available from Katsurco in 0.702 parts water in an autoclave reactor Solution obtained as diluted with additional water) was added. The solution was shaken at 60 rpm for 1 to 24 h at room temperature. Then, the first reaction mixture with no seed crystal was formed by the addition of 0.31 parts of SiO ₂ (Shipper Nat 320C). The reactor was sealed and pressure tested. Thereafter, 0.053 parts of hexamethyleneimine (HMI as 100% organic matter) was added to the reactor to form a second reaction mixture. The second reaction mixture was shaken at 60 rpm for less than 48 h at ambient temperature. The reactor was sealed, heated to &lt; RTI ID = 0.0 &gt; 148.5 C &lt; / RTI &gt; at 60 rpm and allowed to crystallize for 61 h. MCM-56 was confirmed by X-ray diffraction. The reactor was cooled to 127 DEG C and the organics were removed by HMI / water azeotropic distillation, i. E. By "flashing" The flash-treated solvent ("condensate") was combined with additional unused HMI for subsequent batches for recycling. The reactor was cooled and the product was discharged. The degree of crystallization was confirmed by BET surface area. Blending details and results for Example 3.1 are reported in Tables 4 and 5 below.

Example 4

To about 0.02 part of MCM-56 as it is in the synthesized state remaining in the reactor from the previous MCM-56 crystallization in the autoclave reactor, 0.72 part of water and 1 part of 5% alumina (initial 22% Al ₂ O ₃ and 19.5 % Solution from Na ₂ O to 2.9% Al ₂ O ₃ and 1.8% Na ₂ O with additional water). The solution was shaken at 60 rpm for 1 to 24 h at room temperature. Then, the first reaction mixture is formed by the addition of 0.32 parts of SiO ₂ (Shipper Nat 320C). The reactor was sealed and pressure tested. Thereafter, 0.17 parts of hexamethyleneimine (HMI as 100% organic matter) was added to the reactor to form a second reaction mixture. The second reaction mixture was shaken at 60 rpm for less than 48 h at ambient temperature. The reactor was sealed and heated to 141.5 ° C at 60 rpm, allowing the contents to crystallize for 33 h, at which time the crystallization ceased due to the mixture not proceeding to complete crystallization. The reactor was cooled to 127 DEG C and the organics were removed by HMI / water azeotropic distillation, i. E. By "flashing" The reactor was cooled and the product was discharged. The degree of crystallization was confirmed by BET surface area. Blending details and results for Example 4 are reported in Tables 4 and 5 below.

Example 4.1

Into an autoclave reactor was added 1 part of 5% olfalcone (initial 22% Al ₂ O ₃ and 19.5% Na ₂ O to 2.9% Al ₂ O ₃ and 1.8% Na ₂ O, Solution) and 0.72 parts of water. Then 0.32 parts of SiO ₂ (Sipernat 320C) was added. The reactor was sealed and pressure tested. The solution was shaken at 60 rpm for 1 to 24 h at room temperature. Thereafter, 0.17 parts of hexamethyleneimine (HMI as 100% organic matter) was added to the reactor to form a second reaction mixture. The second reaction mixture was shaken at 60 rpm for less than 48 h at ambient temperature. The reactor was sealed, heated to 141.5 C at 60 rpm, and allowed to crystallize for 69 h. At this time, crystallization to MCM-56 was confirmed by X-ray diffraction, the reactor was cooled to 127 DEG C and the organics were removed by HMI / water azeotropic distillation, i. E. By "flashing" The reactor was cooled and the product was discharged. The degree of crystallization was confirmed by BET surface area. Blending details and results for Example 4.1 are reported in Tables 4 and 5 below.

Example 5

16 parts of water and 45% sodium aluminate solution _{(22% Al 2 O 3,} 19.5% Na 2 O) 1 part were placed in an autoclave reactor. The solution was shaken at 60-250 rpm for 1-24 h at room temperature. Then 3.43 parts of SiO ₂ (Sipernat 320C) was added to the reactor. The reactor was sealed and pressure tested. Thereafter, 0.53 parts of hexamethyleneimine (HMI as 100% organic matter) was added to the reactor to form a second reaction mixture. The second reaction mixture was shaken at 60 rpm for less than 48 h at ambient temperature. The reactor was sealed and heated to 60O &lt; 0 &gt; C at 60 rpm, allowing the contents to crystallize for 56 h. At this time, the crystallization to MCM-56 was as confirmed by X-ray diffraction, the reactor was cooled to 127 DEG C and the organics were removed by HMI / water azeotropic distillation, i. E. By "flashing" . The reactor was cooled and the product was discharged. The degree of crystallization was confirmed by BET surface area. Blending details and results for Example 5 are reported in Tables 4 and 5 below.

<Table 4>

<Table 5>

It is observed from Example 1.1 that the first reaction mixture without MCM-56 seed crystals needed to form the second reaction mixture even at higher shear and same temperature was not crystallized over 2.5 times the crystallization time of Example 1. [ Example 1.2 demonstrates that Example 1.1 is repeated to provide crystalline MCM-56, except that the first reaction mixture comprising the seed is used. Example 3 shows that the order of seed addition to the first reaction mixture did not adversely affect the results and that the MCM-56 seed could remain as synthesized. Compared to Example 3, Example 3.1 demonstrates that the crystallization is significantly slower without forming the first reaction mixture required for the process of the present invention. Compared to Example 4, Example 4.1 demonstrates that the crystallization is significantly slower without forming the first or second reaction mixture required for the process of the present invention.

Example 6

To combine the catalyst comprising the " off-seeded "MCM-56 prepared by the improved process of the present invention, 60 parts of the MCM-56 product (100% solids basis) recovered from Example 1 was mixed with 40 parts of UOP versat 300 ™ pseudoboehmite alumina (100% solids basis). The combined dry powders were placed on a laboratory scale Lancaster Muller and mixed for 30 minutes. Sufficient water was added during mixing to produce an extrudable paste. A 2 inch laboratory Bonnot extruder was used to form the extrudable paste into a 1/20 "four-leaf extrudate. The extrudate was dried overnight in an oven at 121 ° C. The extrudate dried at a rate of 2.4 ° C. per minute The extrudate was then cooled to room temperature and wetted with saturated air overnight. The wetted extrudate was added to 5 ml of 1 N ammonium nitrate per gram of catalyst &lt; RTI ID = 0.0 &gt; The ammonium-exchanged extrudate was then rinsed with 5 volumes of deionized water per volume of extrudate to remove residual nitrate. The washed extrudate was washed with water The extrudate was then calcined in a nitrogen / air mixture under the following conditions: The extrudate was heated from room temperature to 426 ° C in a 1% O ₂ /99% N ₂ mixture for 1 hour The temperature was increased to 482 DEG C at a rate of 28 DEG C per hour and maintained for an additional 3 hours at 482 DEG C. The temperature was increased to 482 DEG C at a heating rate of 28 DEG C and maintained at 426 DEG C for 3 hours. ₂ was a stepwise increase in in 7.6% O _2. the extrudate from _{482 ℃ 7.6% O 2 /92.4% N} 2 was maintained for a further 3 h in a stream. then, the temperature was increased to 1 hour at a temperature of 28 ℃ 534 ℃ was. the ratio of O ₂ was gradually increased to 12.6% O _2, the extrudates were maintained for 12 h at from 534 ℃ 12.6% O _2. then, they cool the extrudate to room temperature.

The catalyst comprising MCM-56 prepared in Example 6 was characterized by measuring sodium concentration and BET surface area as measured by inductively coupled plasma (ICP) by a conventional method. The alpha activity (nucleic acid degradation) was measured as described in U.S. Patent No. 3,354,078.

Examples 7, 8, 9, and 10

The three additional catalysts were composed of 60 wt% MCM-56 and 40 wt% alumina (Example 7), 80 wt% MCM-56 and 20 wt% alumina (Example 8) and 20 wt% Was prepared as in Example 6 except for MCM-56 and 80 wt% alumina (Example 9) and 65 wt% MCM-56 and 35 wt% alumina (Example 10). Catalysts comprising MCM-56 prepared in these examples were characterized by measuring alpha test activity (hexane decomposition), sodium concentration as measured by ICP, and BET surface area as commonly known in the patent literature.

Example 11

In a similar manner, a 60 wt% MCM-56, 40 wt% alumina catalyst was formulated according to Example 6 using the "in situ seeded" MCM-56 crystals made by Example 3.

Example 12

In a similar manner, a 100 wt% MCM-56, 0 wt% alumina catalyst was formulated according to Example 6 using the "non-seeded" MCM-56 crystals prepared according to Example 5.

Example 13

In a similar manner, an 80 wt% MCM-56, 20 wt% alumina catalyst was formulated according to Example 6 using "non-seeded" MCM-56 crystals prepared according to Example 5.

Example 14

In a similar manner, an 80 wt% MCM-56, 20 wt% alumina catalyst was formulated according to Example 6 using "non-seeded" MCM-56 crystals prepared according to Example 5. 0.05 wt% polyvinyl alcohol was used as the extrusion aid in the compounding process.

Example 15

To further test the catalysts of Examples 6 to 14, 0.5 g of extrudate catalyst was placed in a wire mesh screen basket with 12 g of quartz chips. The basket and contents were dried overnight (about 16 h) in an oven at 260 &lt; 0 &gt; C. Thereafter, the basket was placed in a 300 cc of parc autoclave. The autoclave was sealed and rinsed with flowing nitrogen to remove air. The autoclave was heated to 170 占 폚 and rinsed with nitrogen at 100 sccm for 2 h. The autoclave shaker was set at 500 rpm. 156.1 g of benzene were then transferred to the autoclave and the temperature was set at 130 DEG C for 1 h at a shaking speed of 500 rpm. After 1 h, 28.1 g of propylene was transferred to the autoclave using a 75 cc oven moving vessel. A constant head pressure was maintained in the autoclave using a nitrogen blanket. Liquid product samples were taken at 30, 60, 90, 120 and 180 minutes. Liquid samples were analyzed on an Agilent 5890 GC. The GC data was assigned to the second movement model. The secondary kinetic rate constant for the conversion of benzene and propylene was calculated with the ratio of diisopropylbenzene (DIPB) to cumene and triisopropylbenzene (TRIPB) to cumene at 3 h for the stream.

Table 6 and Figures 1, 2, 3, and 4 show the results of the "out-seeded" MCM-56 catalyst compositions (Examples 6-10), the "in situ" The physical and catalytic properties of the non-seeded "MCM-56 catalyst compositions (Examples 12-14) are summarized.

Figure 1 shows that the DIPB / IPB ratio is generally reduced as the MCM-56 content in the extrudate decreases from 100% to 20%. Figure 2 shows that when the MCM-56 content is less than 80 wt%, preferably less than 65 wt%, and most preferably less than 60 wt%, a heavy and / Lt; RTI ID = 0.0 &gt; (TRI-IPB) &lt; / RTI &gt; Figure 3 shows that even if the zeolite content is reduced from 100% to 20%, the second-order rate constant k ₂ for the alkylation of propylene with benzene can be maintained above 0.20. Figure 4 shows that the ratio of DIPB / TRI-IPB is relatively constant for a range of MCM-56 contents of 20 to 100% by weight. All "off-grid" seeded MCM-56 data in the figures are shown in the following table.

<Table 6>

Example 16

The MCM-56 zeolite was prepared using seeded zeolite synthesis as described in Example 1 above. The MCM-49 zeolite was also prepared using the seeds and blended with the catalyst as in Example 8. The catalyst comprising MCM-56 was formulated with the catalyst as in Examples 16-19. The combined catalysts were then placed in a test apparatus to determine the selectivity for diethylbenzene (DEB) by-products (as measured by the sum of diethylbenzene divided by ethylbenzene (EB)). The test apparatus comprises a supply system for supplying benzene (B) and ethylene (E); A mixing zone to ensure proper dissolution of ethylene in benzene; A heating element capable of maintaining a linear temperature profile of +/- 4 &lt; 0 &gt; C, an in-line sampling valve for automated sample collection, and a relative amount of hydrocarbon species present in the effluent Containing about 1 g of the catalyst as a diluent into a reactor with a small particle size of silicon carbide to ensure good flow distribution. The reactor also includes a 1/16 "internal thermocouple The internal temperature profile (5 points) was obtained. The temperature and pressure of the test were nominally set at 180 ° C at the inlet of the reactor bed and about 500 psig at the outlet of the reactor bed. The molar ratio of benzene to ethylene (B: E) was nominally set to 19. The total flow was controlled to achieve a conversion rate of less than 100%. Five different catalysts were tested and the results are presented in Examples 16.1 to 16.5. The conversion rate is the degree of ethylene conversion (divided by ethylene converted ethylene).

Example 16.1

In a comparative example, 80 wt% MCM-49, 20 wt% alumina binder material was tested for various conversion rates. The selectivity is shown in Fig. 5 and Table 7.

Example 16.2

40 wt% seeded MCM-56, 60 wt% alumina binder material was tested for various conversion rates. The selectivity is shown in Fig. 5 and Table 7.

Example 16.3

60 wt% seeded MCM-56, 40 wt% alumina binder material was tested for various conversion rates. The selectivity is shown in Fig. 5 and Table 7.

Example 16.4

80 wt% seeded MCM-56, 20 wt% alumina binder material was tested for various conversion rates. The selectivity is shown in Fig. 5 and Table 7.

Example 16.5

20 wt% seeded MCM-56, 80 wt% alumina binder material was tested for various conversion rates. The selectivity is shown in Fig. 5 and Table 7.

<Table 7>

Table 7 shows selectivities for the catalysts of each example at different conversion rate levels. The selectivity is the degree of agreement between DEB and EB products. Also, it is adjusted by inverse proportion of B: E ratio to ensure that the data is comparable.

Figure 5 shows a plot of ethylbenzene selectivity versus ethylene conversion for each example. From these plots, several important conclusions can be drawn:

The seeded MCM-56 has a much higher conversion rate than MCM-49;

By reducing the zeolite content, some activity is sacrificed but has the advantage of lower selectivity of DEB by-products. Operation with these catalysts reduces availability consumption, as lower distillation is required with lower DEB concentration.

- The advantage of a lower zeolite content is limited to a crystallite / binder weight range of less than 80/20 and greater than 20/80 because the conversion is too low at or below the level of 20/80 to be of no commercial utility &Lt; 10% compared to%).

All patents, patent applications, test procedures, priority documents, literature, publications, manuals and other documents cited herein are incorporated by reference to the extent such disclosure is not inconsistent with the present invention and for which such inclusion is permitted, .

Numerical lower limit and numerical upper limit are given in this specification, ranges from any lower limit to any upper limit are also included.

While the illustrative embodiments of the invention are described in terms of specificity, it will be understood that various other modifications will be apparent to and can be readily made by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, the scope of the appended claims is not intended to be limited to the embodiments and descriptions set forth herein; rather, the appended claims are to encompass within their scope all equivalents to those of ordinary skill in the art to which the invention pertains Should be regarded as encompassing all the features of patent novelty inherent in the present invention, including its features.

Claims (21)

A method for selectively alkylating benzene with an alkylating agent to produce monoalkylated benzene,
(i) A process for producing a synthetic porous crystalline MCM-56 material by a process comprising the following steps a), b), c) and d):
a) a first reaction mixture comprising an alkali metal or alkaline earth metal (M) cation, an oxide of a trivalent element X, an oxide of a tetravalent element Y, zeolite seed crystals and water, wherein the molar ratio of oxides , The first reaction mixture further comprising zeolite seed crystals in an amount of 0.05 wt% to 5 wt% based on the weight of the first reaction mixture,
YO ₂ / X ₂ O ₃ = 5 to 35
H ₂ O / YO ₂ = 10 to 70
OH ^- / YO ₂ = 0.05 to 0.20
M / YO ₂ = 0.05 to 3.0
b) adding an inducing agent R to the reaction mixture of step a) to produce a second reaction mixture containing said inducing agent R in a molar ratio within the range of R / YO ₂ = 0.08 to 0.3, Is selected from the group consisting of cyclopentylamine, cyclohexylamine, cycloheptylamine, hexamethyleneimine (HMI), heptamethyleneimine, homopiperazine, and combinations thereof,
c) crystallizing the second reaction mixture of step b) at a temperature of from 90 DEG C to 175 DEG C and for a time of less than 90 h to obtain a seeded, as product mixture, as confirmed by X- Producing a product mixture comprising crystals of MCM-56 material and less than 10% by weight of non-MCM-56 impurity crystals, based on the total weight of said MCM-56 crystals in said product mixture; and
d) separating and recovering at least a portion of the crystals of the seeded MCM-56 material from the product mixture of step c), wherein the crystals of the seeded MCM-56 material have an X-ray diffraction pattern .
<Table 1>

(ii) mixing the seeded MCM-56 crystal and the binder in a weight ratio of crystal / binder of 40/60 to 60/40 to produce a catalyst composition; And
(iii) contacting the feedstock containing said benzene and said alkylating agent with said catalyst composition under effective alkylation conditions to produce a product comprising said monoalkylated benzene, said alkylation conditions being carried out at a temperature of from 0 DEG C to 500 DEG C, which comprises 1 wherein the benzene to the feed weight hourly space velocity based on the alkylating agent and the molar ratio of 0.1 to 500 h ^-1 in the alkylating agent of (WHSV): pressure, 0.1 of 0.2 to 25,000 kPa-a: 1 to 50 fair
&Lt; / RTI &gt; delete 2. The process of claim 1, wherein the product of step (iii) further comprises a dealkylated benzene and a trialkylated benzene, wherein the weight ratio of trialkylated benzene to the dealkylated benzene is in the range of 0.08 to 0.12. The process of claim 1, wherein the alkylatable aromatic compound is benzene, the alkylating agent is ethylene, and the monoalkylated aromatic compound is ethylbenzene. The method of claim 1, wherein the alkylatable aromatic compound is benzene, the alkylating agent is propylene, and the monoalkylated aromatic compound is cumene. 2. The process of claim 1, wherein the amount of zeolite seed crystals in the first reaction mixture is 0.10 wt% to 3 wt%, based on the weight of the first reaction mixture. delete 2. The method of claim 1, wherein the derivatizing agent R comprises hexamethyleneimine (HMI), X comprises aluminum, and Y comprises silicon. The method of claim 1, wherein the mixture of step c) comprises no more than 5% by weight of non-MCM-56 impurities, based on the total weight of the MCM-56 crystals in the product mixture, Crystal. &Lt; / RTI &gt; The process of claim 1, wherein the first reaction mixture has a composition with respect to the molar ratio of oxides within the range of from 1% to 3% by weight, based on the weight of the first reaction mixture, of the first reaction mixture and the amount by further comprising a zeolite seed crystal, step b) is an HMI according to the mole ratio within the first by the addition of hexamethyleneimine (HMI) as the directing agent R to the first reaction mixture, HMI / YO ₂ = 0.1 to 0.2 range &Lt; / RTI &gt; comprising:
YO ₂ / X ₂ O ₃ = 15 to 20
H ₂ O / YO ₂ = 15 to 20
OH ^- / YO ₂ = 0.1 to 0.15
M / YO ₂ = 0.11 to 0.15. The process according to claim 1, wherein the conditions of the crystallization step c) comprise a time of from 20 to 75 h and a temperature of from 125 캜 to 175 캜. The method of claim 1, wherein the zeolite seed crystals exhibit an X-ray diffraction pattern for an MCM-22 family material. The method of claim 1, wherein the zeolite seed crystals exhibit the X-ray diffraction pattern for the MCM-56 crystals shown in Table 1 below:
<Table 1>

The process according to claim 1, wherein the second reaction mixture of step b) is aged at a temperature of from 25 to 75 캜 for a time of from 0.5 to 48 h before the crystallization step c). The method of claim 1, wherein the crystals of MCM-56 from step d) are calcined at a temperature of from 370 DEG C to 925 DEG C for a period of time from 1 minute to 20 hours to produce calcined MCM-56 crystals, wherein Wherein the calcined MCM-56 crystal has an X-ray diffraction pattern as shown in Table 2 below:
<Table 2>

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