KR101745220B1 - Dehydrogenation process - Google Patents

Abstract

There is disclosed a process for dehydrogenating a hydrocarbon with a dehydrogenation catalyst comprising the step of activating a catalyst precursor in an H ₂ -containing atmosphere. A particularly advantageous activation method comprises heating the catalyst precursor to a temperature in the range of 400 to 600 占 폚. The process of the present invention is particularly advantageous for preparing benzene by dehydrogenating cyclohexane.

Description

[0001] DEHYDROGENATION PROCESS [0002]

The present invention relates to a process for the dehydrogenation of cyclohexane and / or methylcyclopentane produced during the hydroalkytation of saturated cyclic hydrocarbons such as cyclohexane and / or methylcyclopentane, especially benzene, to cyclohexylbenzene.

Priority claim

The present application claims priority to U.S. Provisional Patent Application No. 61 / 732,118 filed on November 30, 2012, and European Patent Application No. 13154527.9 filed on March 2, 2013, Quot; is hereby incorporated by reference.

Cross reference of related application

This application claims the benefit of US Provisional Patent Application No. 61 / 468,298 filed on Mar. 28, 2011, entitled "Dehydrogenation Method" and U.S. Patent Application No. 13 / 512,805 filed on December 17, 2010 Quot; dehydrogenation "), both of which are incorporated herein by reference in their entirety.

Cyclohexylbenzene may be produced from benzene by hydroalkylation or by a reductive alkylation process. In this process, benzene is heated with hydrogen in the presence of a catalyst to partially hydrogenate the benzene to produce a reactive intermediate such as cyclohexene, which in turn alkylates the benzene starting material. Thus, U.S. Pat. Nos. 4,094,918 and 4,177,165 disclose hydroalkylation of aromatic hydrocarbons over catalysts comprising nickel- and rare earth-treated zeolites and palladium promoters. Similarly, U.S. Patent Nos. 4,122,125 and 4,206,082 disclose the use of ruthenium and nickel compounds supported on rare earth-treated zeolites as catalysts for aromatic hydroalkylation. The zeolites used in this prior art process are zeolites X and Y. No. 5,053,571 also proposes the use of ruthenium and nickel compounds supported on zeolite beta as an aromatic hydroalkylation catalyst. However, these earlier proposals for the hydroalkylation of benzene have shown that low selectivity for cyclohexylbenzene (especially at economically available benzene conversion) and the formation of large amounts of undesired by-products, especially cyclohexane and methylcyclopentane I had a problem.

More recently, U.S. Patent No. 6,037,513 discloses that the cyclohexylbenzene selectivity in the hydroalkylation of benzene is contacted with hydrogen in the presence of a bifunctional catalyst comprising at least one hydrogenated metal and a molecular sieve of the MCM-22 family And the like. The hydrogenation metal is preferably selected from palladium, ruthenium, nickel, cobalt and mixtures thereof and the contacting step is carried out at a temperature of about 50 to 350 DEG C, at a pressure of about 100 to 7000 kPa, at a pressure of about 0.01 to 100, And a weight hourly space velocity (WHSV) of about 0.01 to 100 hr < ^-1 >. U.S. Patent No. 6,037,513 discloses that the resulting cyclohexylbenzene can then be oxidized to the corresponding hydroperoxide and the hydroperoxide can be cleaved with the desired phenol and cyclohexanone.

One disadvantage of this process is that the process produces impurities such as cyclohexane and methylcyclopentane. These impurities represent a loss of valuable benzene feed. Moreover, if not removed, these impurities will tend to build up in the system, thereby displacing benzene and increasing the production of unwanted byproducts. Thus, a major problem faced by commercial applications of cyclohexylbenzene as a phenolic precursor is the removal of cyclohexane and methylcyclopentane impurities.

One solution to this problem is proposed in U.S. Patent No. 7,579,511, which involves hydroalkylating benzene in the presence of a first catalyst to form a solution containing cyclohexylbenzene, cyclohexane, methylcyclopentane, and unreacted benzene A method of forming cyclohexylbenzene by forming a first effluent composition is described. The first effluent composition is then separated into a cyclohexane / methylcyclopentane-rich composition, a benzene-rich composition and a cyclohexylbenzene-rich composition, and the cyclohexane / methylcyclopentane- Contacting the dehydrogenation catalyst such that at least a portion of the cyclohexane is converted to benzene and at least a portion of the methylcyclopentane is converted to linear and / or branched paraffins to form a second effluent composition. The benzene-rich composition and the second effluent composition may then be recycled to the hydroalkylation step. However, one problem with this process is that cyclohexane and methylcyclopentane have boiling points similar to those of benzene, making them difficult to separate by conventional distillation methods.

Another solution is proposed in International Patent Publication No. WO2009 / 131769 wherein hydroglycation of benzene in the presence of a first catalyst produces a first effluent composition containing cyclohexylbenzene, cyclohexane and unreacted benzene . The first effluent composition is then separated into a cyclohexylbenzene-rich composition, and a C ₆ product composition comprising cyclohexane and benzene. At least a portion of the C ₆ product composition is then contacted with a second catalyst under dehydrogenation conditions to convert at least a portion of the cyclohexane to benzene to produce a second effluent composition comprising benzene and hydrogen, Lt; / RTI >

All of the processes disclosed in U.S. Patent No. 7,579,511 and WO 2009/131769 are directed to a process for preparing a dehydrogenation catalyst comprising a Group VIII metal on a porous inorganic support such as aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, activated carbon, Related to use. In practice, however, such dehydrogenation catalysts have only limited activity for the conversion of cyclohexane and / or methylcyclopentane and, in some cases, can undergo rapid aging. Thus, there is a need for improved catalysts for the removal of cyclohexane and methylcyclopentane from benzene recycle compositions used in benzene hydroalkylation processes. The conversion of cyclohexane is particularly important since the boiling point of cyclohexane is within 1 캜 of the boiling point of benzene. Conversion of methylcyclopentane is also preferred, but the boiling point of methylcyclopentane and benzene is less important than cyclohexane because there is a difference of almost 9 ° C.

More recently, at least one dehydrogenation metal (e.g., platinum or palladium) and a Group 1 or 2 metal promoter (i.e., an alkali metal or an alkaline earth metal) are used to dehydrogenate cyclohexane and / or methylcyclopentane . This process is described, for example, in PCT Patent Application No. PCT / US2010 / 061041 (filed on December 17, 2010). However, there is a need for a dehydrogenation catalyst having improved cyclohexane conversion and / or selectivity.

In the present invention, it has been found that the step of activating the dehydrogenation catalyst can significantly improve the performance of the catalyst.

A first aspect of the present invention relates to a dehydrogenation process,

(1A) providing a catalyst precursor comprising a first metal selected from among metals of Groups 6 to 10 of the Periodic Table of Elements (i) from 0.01 to 10.0 wt%, based on the total weight of (i) the inorganic support and (ii) the catalyst precursor;

(1B) obtaining an activated dehydrogenation catalyst by treating the catalyst precursor in an H ₂ -containing atmosphere for at least 15 minutes at a temperature ranging from 300 to 600 ° C, preferably from 420 to 550 ° C; And

Contacting the first composition comprising cyclohexane under dehydrogenation conditions in a (1C) dehydrogenation reactor with an activated dehydrogenation catalyst to convert at least a portion of the cyclohexane to benzene and obtain a dehydrogenation reaction product

.

A second aspect of the present invention relates to a process for the production of phenol and / or cyclohexanone,

(2A) producing cyclohexylbenzene using the method of the first aspect;

(2B) oxidizing at least a portion of the cyclohexylbenzene to obtain an oxidation reaction product comprising cyclohexylbenzene hydroperoxide; And

(2C) truncating at least a portion of the cyclohexylbenzene hydroperoxide to produce a cleavage reaction product comprising phenol and cyclohexanone

.

The method of the present disclosure has at least one of the following advantages: First , the catalyst precursor is activated by heating the dehydrogenation catalyst precursor at elevated temperature in a hydrogen-containing atmosphere before introducing the catalyst precursor into the dehydrogenation reaction, And an activated catalyst with selectivity. Second , by heating the catalyst precursor to an activation temperature higher than 400 캜 during the activation, it is surprisingly possible to obtain a catalyst with improved conversion without sacrificing selectivity.

Further features and advantages of the invention will be apparent from the description and the claims, as well as the appended drawings. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are intended to provide an overview or spirit of the disclosure to further understand the nature and characteristics of the claimed invention.

Figures 1 and 2 are charts showing the conversion and selectivity of cyclohexane to benzene, respectively, using two different catalysts activated by two different procedures in accordance with the embodiments of the present disclosure.

In this disclosure, a method is described as comprising one or more "steps ". It should be understood that each step is an act or operation that may be performed one or more times in a continuous or discontinuous manner in the method. Unless otherwise stated or unless the context clearly indicates otherwise, each step in the method may be performed sequentially, in the order described, or in any other order, if possible, without overlapping or overlapping with one or more other steps . In addition, one or more, or even all, steps may be performed simultaneously for the same or different batches of materials. For example, in a continuous method, the first step in the method is performed on the raw material initially supplied only at the beginning of the method, and the second step is performed at a later time in the first step, ≪ / RTI > can be carried out simultaneously on the resulting intermediate material. Preferably, the steps are performed in the order described.

Unless otherwise stated, all numbers expressing quantities in this disclosure are to be understood as being modified in all instances by the term "about ". It is also to be understood that the exact numerical values used in the specification and the claims form a specific embodiment. Efforts have been made to ensure the accuracy of the data in the embodiments. However, it should be understood that any measurement data implicitly contains a certain level of error due to the limitations of the techniques and equipment used to perform the measurements.

The phrase "a" or "an" as used herein means "one or more" unless the context clearly dictates otherwise. Accordingly, embodiments employing "hydrogenated metals" may be practiced using one, two or more different types of hydrogenated metals, unless explicitly stated otherwise or where the context clearly indicates that only one type of hydrogenation metal is used .

As used herein, "wt%" refers to percent by weight, "vol%" refers to percent by volume, "mol%" refers to percent by mol, "ppm" Quot; ppm weight "and" ppm by weight "are used interchangeably to mean ppm by weight. All "ppm" as used herein is ppm by weight unless otherwise specified. All concentrations herein are expressed relative to the total amount of the composition in question. All ranges set forth herein should include both endpoints as two specific embodiments, unless otherwise specified or indicated.

As used herein, the general term "dicyclohexylbenzene" includes, collectively, 1,2-dicyclohexylbenzene, 1,3-dicyclohexylbenzene, and 1,4-dicyclohexylbenzene Unless explicitly stated to mean only one or two of the above). The term "cyclohexylbenzene" means cyclohexylbenzene monosubstituted in use in its singular form.

In this disclosure, the composition of the precursor of the catalyst and the catalyst is expressed on the basis of the dry ingredients. If the catalytic material can carry water at various levels, such water is not taken into account in its composition. The catalytic material or precursor thereof may be processed and / or used in conjunction with a small amount of water contained therein, and the activated catalyst may be dried (up to 5% by weight, 3 wt% or less, or 1 wt% or less, or 0.5 wt% or less, or 0.1 wt% or less). In the present disclosure, the amounts of the first, second and third metals in the catalyst and its precursor are expressed on the basis of the elemental metals regardless of their oxidation state. All amounts of Pt, Pd, Sn, K, Na, Ni, Co and other metals of Groups 1, 2, 6-10 and 14 metals in these catalytic materials are therefore such that they are present in the material in question, Although they may be present in all or in part in the form of complexes and small metals. For example, a catalyst composition consisting of 1.9 g of tin chloride (1 g of tin) supported on 98 g of silicon dioxide and 22.29 g of tetraamine platinum hydroxide solution (4.486 wt% of Pt) 1.0 wt% tin and 1.0 wt% Pt based on the total amount. In addition, the composition of the precursor of the catalyst is expressed as the final composition of the activated catalyst prepared therefrom. Those skilled in the art of catalyst formulations can construct starting materials such as salts, solutions, oxides, etc. to achieve the final target chemical composition of the activated catalyst. For example, in this disclosure, a catalyst precursor comprising 1.0 wt.% Pt, 1.0 wt.% Sn, and 98 wt.% Silica can be used as the final catalyst comprising the amount of platinum, tin and silica means a precursor containing starting material such as one or more of the desired amount of _{PtO 2, Pt, SnO 2,} SnO, SnCl 4, SnCl 2 , such as to turn.

The term "MCM-22 type material" (or "MCM-22 type material" or "MCM-22 type molecular sieve" or "MCM-22 type zeolite") as used herein includes one or more of the following:

Molecular sieves made from conventional first degree crystalline building block unit cells with a MWW skeletal topology are a spatial arrangement of atoms describing a crystal structure when tiled into a three dimensional space. This crystal structure is disclosed in Atlas of Zeolite Framework Types, "Fifth edition, 2001, which is incorporated herein by reference in its entirety);

- molecular sieves made from conventional second crystalline building blocks, wherein the MWW skeletal topology unit cells are tiled in two dimensions to form a single unit cell thickness, preferably a single c-unit cell thickness;

- Molecular sieves made from conventional second crystalline building blocks, which are layers of one or more unit cell thicknesses, wherein a layer of more than one unit cell thickness is formed by laminating, packing or bonding two or more single layers of one unit cell thickness The molecular sieves made (this second determination can also be made by stacking the building blocks in a regular manner, in an irregular manner, in a random manner, or any combination thereof), and

- molecular sieves made by any regular or random two-dimensional or three-dimensional combination of unit cells with MWW skeletal topology.

The molecular sieve of the MCM-22 type comprises molecular sieves having an X-ray diffraction pattern comprising d-spacing maximums at 12.4 + -0.25, 6.9 + -0.15, 3.57 + 0.07 and 3.42 + 0.07A. The X-ray diffraction data used to characterize the material is obtained by standard techniques using a K-alpha doublet of copper as incident radiation and a diffractometer equipped with an associated computer which is a scintillation counter and a collection system.

Materials of the MCM-22 type include MCM-22 (disclosed in U.S. Patent No. 4,954,325), PSH-3 (disclosed in U.S. Patent No. 4,439,409), SSZ-25 (disclosed in U.S. Patent No. 4,826,667) ITQ-1 (disclosed in European Patent No. 0293032), ITQ-1 (disclosed in U.S. Patent No. 6,077,498), ITQ-2 (disclosed in International Patent Publication No. WO 97/17290), MCM-36 (Disclosed in U.S. Patent No. 5,250,277), MCM-49 (disclosed in U.S. Patent No. 5,236,575), and MCM-56 (disclosed in U.S. Patent No. 5,362,697). Other molecular sieves such as UZM-8 (disclosed in U.S. Patent No. 6,756,030) can be used for the purposes of the present disclosure, also with or without the molecular sieve of MCM-22 type. Preferably the molecular sieve is selected from (a) MCM-49, (b) MCM-56, and (c) isotypes of MCM-49 and MCM-56, such as ITQ-2.

The dehydrogenation catalyst used in the dehydrogenation reaction comprises (i) an inorganic support, (ii) a first metal selected from Groups 6-10 of the Periodic Table of the Elements, optionally (iii) a second metal selected from Group 14 of the Periodic Table of Elements, and And optionally (iv) a third metal selected from Group 1 and Group 2 of the Periodic Table of the Elements. For example, the dehydrogenation catalyst may comprise both a first metal and a second metal, but essentially does not contain a third metal. Examples of such catalysts are described, for example, in WO2012 / 134552, the relevant portions of which are incorporated herein by reference. Alternatively, the dehydrogenation catalyst may comprise both a first metal and a third metal, but essentially does not contain a second metal. Examples of such catalysts are described, for example, in WO2011 / 096998, the relevant portions of which are incorporated herein by reference. In addition, the dehydrogenation catalyst used in the process of the present disclosure may also comprise first, second and third metals simultaneously. As used herein, the numbering scheme for the families of the Periodic Table of Elements disclosed herein is described in Hawley's Condensed Chemical Dictionary (14 ^th Edition), by Richard J. Lewis].

The catalyst used in the process of the present disclosure comprises a first metal selected from Group 6 to Group 10 of the Periodic Table of the Elements, for example platinum and / or palladium. Typically, the metal selected from group 6 to group 10 of the Periodic Table of Elements is present in an amount ranging from Fm1 to Fm2% by weight, wherein Fm1 is 0.01, 0.02, 0.03, 0.05, 0.08, 0.10, 0.30, 0.50, 0.80, 1.00, Fm2 may be 10.0, 9.50, 9.00, 8.50, 8.00, 7.50, 7.00, 6.50, 6.00, 5.50, 5.00, 4.50, 4.00, 3.50, 3.00, 2.50, 2.00, 1.50, or 1.00, where Fm1 < Fm2.

Alternatively or additionally, the catalyst used in the process of the present disclosure may comprise (i) 2.0 wt% or less, or 1.0 wt% or less, or 0.5 wt% or less, or 0.1 wt% or less And (ii) cobalt at a concentration of 2.0 wt% or less, or 1.0 wt% or less, or 0.5 wt% or less, or 0.1 wt% or less. Preferably, the catalyst composition is free or substantially free of ruthenium, rhodium, lead, and / or germanium, and / or any other active element component.

While not wishing to be bound by any particular theory, the first metal in the activated catalyst is a major component responsible for the dehydrogenation function of the catalyst. Under suitable dehydrogenation conditions, especially at the preferred temperatures described in more detail below, cyclic hydrocarbons, especially saturated compounds, such as cyclohexane, can be activated upon contact with the first metal, undergoing dehydrogenation reactions to form unsaturated Lt; / RTI &gt; It is also believed that at least a portion of the first metal of the activated catalyst used in the dehydrogenation process of the present disclosure should be in elemental form in order to impart a desired degree of dehydrogenation activity. Thus, when used in the dehydrogenation process, the activated catalyst comprises at least x% of the first metal in elemental form, where x is 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 98, 99, or even 99.5. It is also highly desirable that during the entire dehydrogenation reaction according to the present disclosure, at least the major portion of the first metal in the catalyst is maintained in the elemental state. In an environment rich in hydrogen gas, for example, in a typical dehydrogenation reactor in normal operation, such conditions can be met. For example, the second metal, Group 14 metal, is present in an amount ranging from Sm1 to Sm2 weight percent, based on the total weight of the dehydrogenation catalyst, to the activated dehydrogenation catalyst used in the dehydrogenation process of the present disclosure, Sm1 may be 0.01, 0.02, 0.03, 0.05, 0.08, 0.10, 0.30, 0.50, 0.80, 1.00, 1.50, 2.00, 2.50, 3.00, 3.50, 4.00, 4.50, or 5.00, Sm2 may be 10.0, 9.50, 9.00 , 8.50, 8.00, 7.50, 7.00, 6.50, 6.00, 5.50, 5.00, 4.50, 4.00, 3.50, 3.00, 2.50, 2.00, 1.50, or 1.00, with Sm1 <Sm2. Preferably, the Group 14 metal is tin.

The ratio (for example, Pt / Sn ratio) of the metal selected from Group 6 to Group 10 of the Periodic Table of the Elements to the metal selected from Group 14 of the Periodic Table of Elements in the catalyst may range from Rt1 to Rt2, , Rt2 may be 400, 350, 300, 250, 200, 150, or 100, and may be, for example, 0.3, 0.4, 0.5, 0.8, 1.0, 2.0, 3.0, 4.0, 5.0, 8.0, 10.0, 15.0, 20.0, 100, 90.0, 80.0, 70.0, 60.0, 50.0, where Rt1 < Rt2. The preferred range of the ratio is 2.5 to 400, 2.7 to 200, and 3.0 to 100.

Preferably, the activated catalyst used in the process of the present disclosure comprises a third metal which is at least one of Group 1 and Group 2 of the Periodic Table of the Elements. The third metal is present in an amount ranging from Tm1 to Tm2 weight percent wherein Tm1 can be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.5, 2.0, 2.5, Tm may be 5.0, 4.5, 4.0, 3.5, 3.0, 2.5, 2.0, 1.5, 1.0, with Tm1 < Tm2. For example, the third metal may comprise a metal of a Group 1 element of the Periodic Table of the Elements, such as potassium, cesium and rubidium, preferably potassium. Alternatively, the third metal may comprise one or more Group 2 elements of the Periodic Table of Elements, such as beryllium, calcium, magnesium, strontium, barium and radium, preferably calcium and magnesium. Because of the high chemical activity of the Group 1 and Group 2 elements of the Periodic Table of the Elements, the third metal in the catalyst used in the process of the present disclosure is predominantly in an oxidation state, such as +1, +2, Oxides, salts, sulfides, hydrides and the like.

Although the composition of the catalyst is expressed as an elemental metal with respect to the first metal, the second metal and the third metal, it is preferred that the first metal, the second metal and the third metal are not purely elemental metals, It will be appreciated that other forms may be used, such as salts, oxides, chlorides, hydrides, sulfides, carbonates, and the like.

The activated dehydrogenation catalyst used in the dehydrogenation process of the present disclosure further comprises an inorganic support. For example, the dehydrogenation catalyst support may comprise one or more of silica, alumina, silicate, aluminosilicate, zirconia, carbon or carbon nanotubes. Alternatively, the support may comprise at least one of inorganic oxides, such as silicon dioxide, titanium dioxide, and zirconium dioxide. The support may or may not include a binder. The impurities which may be present in the catalyst support are, for example, sodium salts, for example sodium silicate, which may be present in any range from 0.01 to 2% by weight. Suitable silica supports are described, for example, in PCT publication WO / 2007084440 A1 (filed January 12, 2007, entitled &quot; Silica Carrier &quot;), which is incorporated herein by reference.

The dehydrogenation catalyst may comprise a silica support having a pore volume and a median pore diameter as measured by mercury intrusion porosimetry as described by ASTM Standard Test Method D4284. The silica support may have a surface area as measured by ASTM D3663. The pore volume may range from about 0.2 cc / gram to about 3.0 cc / gram. The mesopore diameter is in the range of about 10 angstroms to about 2000 angstroms, or 20 to 500 angstroms, and the surface area (m ² / grams) is in the range of 10 to 1000 m ² / gram or 20 to 500 m ² / gram. The support may or may not include a binder.

For example, the dehydrogenation catalyst precursor may be impregnated, for example by impregnation, to a first metal or precursor thereof, a second metal or precursor thereof, and / or a third metal or precursor thereof in a liquid medium (e.g., water) And optionally, one or more liquid compositions comprising an inorganic base component or a precursor, either sequentially or simultaneously. An inorganic dispersant may be added to each liquid carrier to help uniformly apply the metal component (s) to the support. Suitable organic dispersants include amino alcohols and amino acids, such as arginine. For example, the organic dispersant may be present in the liquid composition in an amount ranging from 1.0 to 20% by weight of the liquid composition.

The catalyst may comprise a first metal and a second metal but is essentially free of a third metal and the catalyst precursor may be selected from the group consisting of a sequential impregnation of a second metal precursor &Lt; / RTI &gt;

After treatment with the liquid composition, the inorganic support is heated at one or more stages, generally at a temperature of from 100 to 700 캜 for 0.5 to 50 hours to remove (a) the removal of the liquid carrier, (b) , And (c) decomposition of the organic dispersant. The heating may be performed in an oxidizing atmosphere, for example, air. Thus, a catalyst precursor is obtained.

The catalyst precursor may include the first metal in one or more oxidation states, for example in the form of elements, salts, oxides, and the like. When the catalyst precursor is prepared by sintering in air or other O ₂ -containing atmosphere, at least some of the first metal, optional second and third metals are present in oxidized form. For example, where the catalyst comprises Pt and Sn and a silica support, the precursor is prepared by impregnating the silica support with a solution of Pt salt and Sn salt, followed by drying and sintering in air, wherein the catalyst precursor is typically Pt At least a part of SnO _{2 in} the form of PtO ₂ and a part of Sn in the form of SnO ₂ .

In the process of the present disclosure, the catalyst precursor is treated with an activating step prior to use in the dehydrogenation reaction. The activation involves heating the catalyst precursor in a reducing atmosphere comprising H ₂ at elevated temperature. The reducing atmosphere may be pure hydrogen or another reducing or inert gas such as a mixture of N ₂ , CH ₄ , C ₂ H ₅ , other hydrocarbons, etc. and hydrogen. Preferably, prior to contact with the catalyst precursor, the H ₂ -containing atmosphere used in the activation step is a substantially dry stream of gas containing H ₂ O in aa% by volume or less, where aa is 5.0, 4.0, 3.0 , 2.0, 1.0, 0.8, 0.5, 0.3, 0.1, 0.05, 0.01, 0.005, 0.001, 0.0005, or even 0.0001. The dried H ₂ stream can act to heat the catalyst precursor and dry the precursor before significant reduction occurs and to purge the H ₂ O (if present) produced during the reduction. Upon contact with hydrogen at high temperature, the first metal is reduced to an at least partially lower oxidation state, advantageously an elemental state, if present in a higher oxidation state than the elemental form. For example, PtO ₂ and PdO can be reduced to Pt and Pd by H ₂ at elevated temperatures. The second metal can also be reduced to a lower oxidation state or element state by hydrogen and / or other components in the activation atmosphere in the activation step if it is present in a higher oxidation state than the element form. However, a third metal, such as K, Na, Ca or the like, of Group 1 or Group 2 metals of the Periodic Table of the Elements, when present in the catalyst, may be present in the oxide, salt or part of the composite (e.g., Or ceramic material) in the activated catalyst is predominantly present in a higher oxidation state than the elemental form.

During the activation step, the catalyst precursor may be heated from a lower temperature (e.g., room temperature) to the target activation temperature. As used herein, "activation temperature" means the highest temperature at which the catalyst precursor is exposed for at least 3 minutes (or at least 5 minutes, or at least 10 minutes, or at least 15 minutes, or at least 20 minutes) during activation. It is highly desirable for the catalyst precursor to be surrounded by a H ₂ -containing atmosphere during the heating step. The temperature heating rate of the catalyst precursor may range from HR1 ° C / min to HR2 ° C / min, where HR1 may be 2, 4, 5, 6, 8, 10, 12, 14, , 40, 35, 34, 32, 30, 28, 26, 25, 24, 22, 20, When the temperature is relatively low (less than 100 ° C), the reduction of the first and / or second and / or third metal (s) may be slow and insignificant. The higher the temperature of the catalyst precursor, the higher the rate of the reduction reaction. Thus, it is preferred that the highest temperature at which the catalyst precursor is exposed (and thus reached) during activation is above &lt; RTI ID = 0.0 &gt; T1 C, &lt; / RTI &gt; where T1 is 300, 320, 340, 350, 360, 380, 400, 420, 440, have. It is highly desirable that the catalyst precursor be maintained for at least an activation period of D1 minutes within the temperature range of Tact-20 DEG C to Tact, wherein Tact is the activation temperature and D1 is 10, 15, 20, 25, 30, 45, 60 , 75, 90, 120, 150, 180, 240, 300, 360, 420, 480, 540, 600, 660, 720, 780, 840, However, it has been found that an excessively high activation temperature and a too long temperature maintenance period around the maximum temperature can be detrimental to the performance of the activated catalyst. While not wishing to be bound by any particular theory, it is believed that the first and second metals in elemental form can be fluidized on the surface of the inorganic support at very high temperatures and coagulate to form large crystals, thereby reducing the number of available sites on the activated catalyst &Lt; / RTI &gt; Accordingly, it is preferable that the activation temperature at which the catalyst precursor is exposed in the activation step is not more than T2 ° C, where T2 is 650, 640, 630, 620, 610, 600, 590, 580, 570, 560, 550, 540, , 510, and even 500. During the heating step and the temperature maintenance period, the catalyst precursor is preferably exposed to the H ₂ -containing atmosphere for at least b% of the time, where b is 50, 60, 70, 80, 90, 95, 98, 100%. If the catalyst precursor is not surrounded by an H ₂ -containing atmosphere, it is highly desirable to be surrounded by another reducing or inert atmosphere, such as CH ₄ , N ₂ , and mixtures thereof.

Surprisingly, an activation temperature in the range from 300 to 600 ° C is particularly advantageous, especially for catalysts comprising Pt and / or Pd as the first metal and a second metal such as Sn. The data show that cyclohexane dehydrogenation using catalysts activated at such high temperatures represents a significantly higher conversion of cyclohexane to benzene without sacrificing selectivity. Thus, preferably, the catalyst precursor containing Pt and Sn is activated at an activation temperature in the range Ta1 to Ta2, where Ta1 and Ta2 are independently selected from the group consisting of 300, 310, 320, 330, 340, 350, 360, 550, 560, 570, 580, 590, or 600, and may be, for example, Ta1 < Ta2.

At the end of the temperature holding period around the activation temperature, it is preferred that at least y% of all the first and second metals in the catalyst precursor are reduced to the desired oxidation state, for example elemental, where y is 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 98, 99, 99.5, 99.8, or even 99.9. When the catalyst comprises Pt and / or Pd, it is preferred that at least y% of Pt and / or Pd is reduced to elemental Pt and Pd at the end of the temperature holding period. When the catalyst comprises Sn, it is preferred that at least z% of Sn in Sn is reduced to elemental Sn at the end of the temperature holding period, where z is 40, 45, 50, 55, 60, 65, , 80, 85, 90, 95, 98, or even 99.

At the end of the temperature maintenance period, the catalyst precursor is converted primarily and preferably substantially all to the activated catalyst. At this stage, the activated catalyst may be at a temperature higher or lower than or substantially equal to the operating temperature of the activated catalyst in the dehydrogenation process. The catalyst can then be added to the dehydrogenation reaction after further heating or cooling as required. However, it is highly desirable that the activated catalyst be protected from oxidation prior to use. To this end, during the period (if any) between the activation termination and the onset of the dehydrogenation reaction, the activated catalyst is preferably protected by an H ₂ -containing or inert atmosphere which is the same as or different from the atmosphere used in the activation step. It is particularly advantageous to carry out the activation step and the dehydrogenation step in the same reactor to eliminate the necessity and the resulting complexity of transferring the activated catalyst to the dehydrogenation reactor.

The activated dehydrogenation catalyst can have an oxygen uptake value (ocv) of greater than 1% ocv, where ocv1 can be 5, 8, 12, 15, 18, 20, 22, 25, 28, or 30. As used herein, the oxygenated chemical absorption value (ocv) of a particular catalyst is a measure of the metal dispersion on the catalyst and is defined as follows:

ocv = (amount of oxygen absorbed by the catalyst (mol)) / (amount of dehydrogenation catalyst contained in the catalyst (mol)) x 100%

Herein, the oxygen chemical absorption value is measured using a Micromeritics ASAP 2010 physisorption analyzer as follows. About 0.3 to 0.5 g of the catalyst is placed in the micrometric device. Under helium flow, the catalyst is maintained at ambient temperature (18 [deg.] C) at 250 [deg.] C at a rate of 10 [deg.] C / min for 5 minutes. After 5 minutes, the sample is placed under vacuum at 250 DEG C for 30 minutes. After 30 minutes in the vacuum, the sample is cooled to 35 占 폚 at 20 占 폚 / min and held for 5 minutes. Oxygen and hydrogen are isothermally collected at 0.50 to 760 mmHg at 35 [deg.] C. The linear portion of this curve is extrapolated to 0 atmospheres to obtain a total (i.e., combined) adsorption uptake.

Preferably, the alpha value of the dehydrogenation catalyst is 0 to 10, and 0 to 5, and 0 to 1. The alpha value of the support is a rough indicator of the catalytic cracking activity of the catalyst compared to the standard catalyst. The alpha test provides the relative rate constant of the test catalyst (rate of n-hexane conversion per unit volume of catalyst per unit time) to the standard catalyst taken as alpha of 1 (rate constant = 0.016 s- ¹ ). The alpha test is described in U. S. Patent No. 3,354, 078 and J. < RTI ID = 0.0 &gt; Catalysis, 4, 527 (1965); 6, 278 (1966); And 61, 395 (1980), which is used as a reference for the contents of the test. The experimental conditions of the test used to determine the alpha value referred to herein are described in J. Catalysis, 61, 395 (1980), which is incorporated herein by reference. Alternatively, the alpha value may range from valpha1 to valpha2, and valpha1 may be in the range of 0.0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9,1,2,3,4,5,6,7,8 , 9, and 10, and valpha2 may be 200, 175, 150, 125, 100, 90, 80, 70, 60, 50, 40, 30, 20, 10, 5, 1.9, 1.8, 1.7, 1.6, 1.5 , 1.4, 1.3, 1.2, 1.1, 1, 0.9, 0.8, 0.7, 0.6, and 0.5, with valpha1 <valpha2.

Activated dehydrogenation catalysts prepared using the methods of this disclosure can be used to dehydrogenate a first composition comprising any dehydrogenatable hydrocarbon material, such as those containing cyclic hydrocarbon compounds. 88, the first composition is a cyclic hydrocarbon compound such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclododecane, cyclodecane, cyclododecane and derivatives thereof Lt; / RTI &gt; derivatives). The first composition may comprise C1 to C2 weight percent saturated cyclic hydrocarbons such as cyclohexane wherein C1 and C2 are independently 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 40.0, 45.0, 50.0, 55.0, 60.0, 70.0, 75.0, 80.0, 85.0, 90.0, 95.0, 98.0, 0.9, 1.0, 3.0, 5.0, 8.0, 10.0, 15.0, 20.0, 25.0, 30.0, With the proviso that C1 &lt; C2, where% is based on the total weight of the first composition in contact with the activated catalyst.

When the first composition comprises a six-membered cyclic hydrocarbon such as cyclohexane, it may further comprise one or more 5-membered cyclic hydrocarbons (for example, at a concentration ranging from C3 to C4% by weight based on the total weight of the first composition) C 3 and C 4 are independently selected from the group consisting of 0.01, 0.03, 0.05, 0.08, 0.10, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.60, 0.70, 0.80, 0.90, 1.00, 1.50, 2.00, 2.50, 3.00, 3.50, 4.00, 4.50, 5.00, with C3 <C4.

The first composition may further comprise a non-dehydrogenatable component, such as an aromatic hydrocarbon, in a concentration ranging from C5 to C6% by weight based on the total weight of the first composition, wherein C5 and C6 are independently 5, 8, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90 or 95; The aromatic hydrocarbons may be, for example, benzene. The aromatic hydrocarbons may be the same as the products of the dehydrogenation process using the activated dehydrogenation catalyst of the present disclosure. The non-dehydrogenatable component in the first composition can act as a thermal carrier required to maintain the dehydrogenation reaction at the desired temperature and reaction rate.

Conditions suitable for the dehydrogenation steps include a weight hourly space velocity of the pressure and 0.2hr ^-1 to 50 hr ^-1 in the temperature, atmospheric pressure to about 100 to about 7000 kPa- kkPa- gauge gauge (kPag) of 100 to 1000 ℃.

Preferably, the temperature of the dehydrogenation process may range from Td1 to Td2 C, where Td1 may be 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, , 950, 900, 850, 800, 750, 700, 650, 600, or 550, with Td1 <Td2.

Preferably, the pressure of the dehydrogenation process may be from P1 kPa to P2 kPa, where P1 and P2 are independently 0, 100, 150, 200, 250, 300, 350, 400, 450, 500, 600, 700, 800, 900, 1000, 1500, 2000, 2500, 3000, 4000, 5000, 6000,

The reactor structure used in the dehydrogenation process may comprise one or more stationary bed reactors containing a solid catalyst with dehydrogenation function. The perpass conversion of a saturated cyclic hydrocarbon (e. G., Cyclohexane) using the present catalyst may be at least con% where con is 70, 75, 80, 85, 90, 95, or even 98 Lt; / RTI &gt; The reaction is endothermic. Typically, the temperature of the reaction mixture drops across the catalyst bed due to the endothermic effect. External heat may be supplied to the reactants in the reactor via one or more heat exchangers to maintain the temperature of the reactants in a desired range. The temperature of the reaction composition is lowered over each catalyst bed and then raised by the heat exchanger. Preferably, from 1 to 5 beds are used, and a temperature drop of 30 to 100 DEG C occurs across each bed. Preferably, the last bed in the series is conducted at a higher outlet temperature than the first bed in the series.

The method may be used with any composition comprising a saturated cyclic hydrocarbon (e. G., Cyclohexane) and optionally a 5-membered cyclic compound (e. G., Methylcyclopentane) Phenol &lt; / RTI &gt; In such an integrated process, the benzene may be initially alkylated by cyclohexene in the presence of, for example, an acid catalyst (e. G., Zeolite beta or MCM-22 type molecular sieves) Is converted to cyclohexylbenzene by hydrogenation of biphenyl after oxidative coupling of benzene. In practice, however, cyclohexylbenzene is generally prepared by contacting benzene with hydrogen in the presence of a hydroalkylation catalyst under hydroalkylation conditions, whereby benzene undergoes the following reaction (1) to produce cyclohexylbenzene (CHB):

The hydroalkylation reaction can be carried out in a wide range of reactor structures, for example, a fixed bed, slurry reactor, and / or catalytic distillation column. In addition, the hydroalkylation reaction may be carried out in a single reaction zone or in a plurality of reaction zones, where at least hydrogen is introduced into the reaction. Suitable reaction temperatures are from 100 to 400 ° C, for example from 125 to 250 ° C, and suitable reaction pressures (gauge) are from 100 to 7,000 kPa, for example from 500 to 5,000 kPa. Suitable values for the molar ratio of hydrogen to benzene are from 0.15: 1 to 15: 1, for example from 0.4: 1 to 4: 1, for example from 0.4: 1 to 0.9: 1.

The catalyst used in the hydroalkylation reaction is generally a bifunctional catalyst comprising the above-described MCM-22 type molecular sieve and hydrogenated metal.

Although any known hydrogenation metal may be used in the hydroalkylation catalyst, suitable metals include palladium, ruthenium, nickel, zinc, tin and cobalt, and palladium is particularly advantageous. The amount of hydrogenation metal present in the catalyst may range from 0.05 wt% to 10 wt%, e.g., from 0.1 wt% to 5.0 wt% of the catalyst. When the molecular sieve of the MCM-22 type is aluminosilicate, the amount of hydrogenation metal present is such that the molar ratio of aluminum in the molecular sieve to hydrogenated metal is from 1.5 to 1500, for example from 75 to 750, for example from 100 to 300 .

The hydrogenated metal may be supported directly on the MCM-22 type molecular sieve, for example by impregnation or ion exchange. Preferably, at least 50 wt.%, For example at least 75 wt.%, Generally at least substantially all of the hydrogenated metal is supported on the inorganic oxide which is separate from the molecular sieve but forms a complex with it. In particular, by supporting the hydrogenation metal on the inorganic oxide, the activity of the catalyst and its selectivity to the desired products such as cyclohexylbenzene and dicyclohexylbenzene are increased, as compared to an equivalent catalyst wherein the hydrogenation metal is supported on the molecular sieve Is confirmed.

The inorganic oxides used in such composite hydrocarbylation catalysts are not limited to narrow ranges, as long as they are stable and inert under the conditions of the hydroalkylation reaction. Suitable inorganic oxides include oxides of Groups 2, 4, 13 and 14 of the Periodic Table of the Elements, such as alumina, titania and / or zirconia.

The metal hydride may be deposited on the inorganic oxide, for example, by impregnation before the metal-containing inorganic oxide forms a complex with the molecular sieve. Typically, the catalyst composite is prepared by co-pelletizing the mixture of molecular sieve and metal-containing inorganic oxide at high pressure (typically about 350 to about 350,000 kPa), or optionally with a separate binder, Lt; / RTI &gt; is produced by co-extrusion which presses the slurry of the metal oxide and the metal-containing inorganic oxide through a die. If desired, additional hydrogenation metal may be subsequently deposited on the resulting catalyst composite. Alternatively, the molecular sieve, inorganic oxide and optional binder may be complexed and formed into pellets, for example by extrusion, and then impregnated with one or more dispersions, e. G., Solutions containing one or more of the metals.

The catalyst may comprise a binder. Suitable binder materials include synthetic or naturally occurring materials, as well as inorganic materials such as clay, silica and / or metal oxides. The latter may be naturally occurring or it may be in the form of a gel-like precipitate or gel, including mixtures of silica and metal oxides. Naturally occurring clays that can be used as binders include those of the montmorillonite series and the kaolin series, and these series are commonly found in Dixie, McNamee, Georgia and Florida, Clay or kaolin and subbentonites known as other clays wherein the major mineral component is halosite, kaolinite, dickite, nacrite or anoxocite. These clays can be used in the originally mined raw material state or initially treated with calcination, acid treatment or chemical modification. Suitable metal oxide binders include silica, alumina, zirconia, titania, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica- beryllium, silica- Silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia.

The hydroalkylation step is highly selective for cyclohexylbenzene, but the effluent from the hydroalkylation reaction generally contains unreacted benzene feed, some dialkylated product, and other by-products, especially cyclohexane and methylcyclopentane something to do. In practice, typical selectivities for cyclohexane and methylcyclopentane in the hydroalkylation reaction are 1 to 25 wt% and 0.1 to 2.0 wt%, respectively.

The dehydrogenation reaction may be performed on all or a portion of the effluent of the hydroalkylation step.

Alternatively, the hydroalkylation reaction effluent is separated into at least (i) the C ₆ -rich composition and (ii) the remaining amount of the hydroalkylation reaction effluent. When the composition is described as being "abundant" (eg, C ₆ -rich, benzene-rich or hydrogen-rich) in a particular species, it is preferred that the weight percent of the species specified in the composition is added to the feed composition . The "C ₆ " species generally refers to any species containing six carbon atoms.

Considering similar boiling points of benzene, cyclohexane and methylcyclopentane, it is difficult to separate these substances by distillation. Thus, a C ₆ -rich composition comprising benzene, cyclohexane and methylcyclopentane can be separated by distillation from the hydroalkylation reaction effluent. This C ₆ -rich composition is then treated with the dehydrogenation process described above to convert the cyclohexane in the composition to benzene and at least a portion of the methylcyclopentane is converted to linear and / or branched paraffins, such as 2-methylpentane, 3 -Methylpentane, n-hexane and other hydrocarbon components such as isohexane, C ₅ aliphatic and C ₁ to C ₄ aliphatic. The dehydrogenation product composition is then fed to an additional separation system, typically an additional distillation column, to divide the dehydrogenation product composition into a benzene-rich stream and a benzene-depleted stream. The benzene-rich stream is then recycled to the hydroalkylation stage, and the benzene-deficient stream can be used as fuel for the process. If the composition is described as being "deficient" for a particular species (e.g., benzene-deficient), it means that the weight percent of the specified species in the composition is insufficient relative to the feed composition do.

After separation of the C ₆ -rich composition, the remaining hydroalkylation effluent is fed to a second distillation column to separate the monocyclohexylbenzene product (e.g., cyclohexylbenzene) from any dicyclohexylbenzene and other heavy materials . Depending on the amount of dicyclohexylbenzene present in the reaction effluent, it may be desirable to transalkylate the dicyclohexylbenzene with the additional benzene to maximize the production of the desired monoalkylated species.

The transalkylation with additional benzene can be carried out in a transalkylation reactor separate from the hydroalkylation reactor using suitable transalkylation catalysts such as molecular sieves of the MCM-22 type, zeolite beta, MCM-68 (see U.S. Patent No. 6,014,018 ), Zeolite Y, zeolite USY, and mordenite. The macropore molecular sieve may have an average pore size of 7 Å or more, for example, 7 to 12 Å. The transalkylation reaction is typically carried out at a temperature of 100 to 300 占 폚, a pressure of 800 to 3500 kPa, a weight hourly space velocity of 1 to 10 hr &lt; ^-1 &gt; for the total feed and a ratio of benzene / dicyclohexylbenzene Lt; RTI ID = 0.0 &gt; at least &lt; / RTI &gt; partly liquid phase conditions. The transalkylation reaction effluent may then be recycled to the second distillation column to recover the additional monocyclohexylbenzene produced in the transalkylation reaction.

After separation at the second distillation column, cyclohexylbenzene can be converted to phenol and cyclohexanone by a process similar to the Hock process. In this process, cyclohexylbenzene is initially oxidized to the corresponding hydroperoxide. This is achieved by introducing an oxygen-containing gas, for example air, into the cyclohexylbenzene-containing liquid phase. Unlike the Hawk process, atmospheric air oxidation of cyclohexylbenzene under the absence of a catalyst is very slow and usually performs oxidation in the presence of a catalyst.

Suitable catalysts for the cyclohexylbenzene oxidation step are the N-hydroxy substituted cyclic imides described in U.S. Patent No. 6,720,462, which is incorporated herein by reference, examples of which include N-hydroxyphthalimide, 4-amino-N -Hydroxyphthalimide, tetrachloro-N-hydroxyphthalimide, N-hydroxyhetermide, N &lt; RTI ID = 0.0 &gt; N-hydroxytrimellitimide, N-hydroxybenzene-1,2,4-tricarboximide, N, N'-dihydroxy (pyromellitic acid diimide), N , N'-dihydroxy (benzophenone-3,3 ', 4,4'-tetracarboxylic acid diimide), N-hydroxymaleimide, pyridine-2,3-dicarboximide, N- Imide, N-hydroxy (tartaric acid imide), N-hydroxy-5-norbornene-2,3-dicarboximide, exo-N-hydroxy -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-hydroxy-cis-cyclohexane-1,2-dicarboximide, N- Cis-4-cyclohexene-1,2-dicarboximide, N-hydroxynaphthalimide sodium salt or N-hydroxy-o-benzenedisulfonimide. Preferably, the catalyst is N-hydroxyphthalimide. Another suitable catalyst is N, N ', N "-trihydroxyisocyanurate.

These materials can be used alone or in the presence of free radical initiators and can be used as a liquid homogeneous catalyst or supported on a solid support to provide an inhomogeneous catalyst. Typically, the N-hydroxy substituted cyclic imide or N, N ', N "-trihydroxyisocyanuric acid is present in an amount of from 0.0001% to 15% by weight, such as from 0.001% to 5.0% by weight of cyclohexylbenzene It is used in quantities.

Suitable conditions for the oxidation step include a temperature of from 70 占 폚 to 200 占 폚, for example from 90 占 폚 to 130 占 폚 and / or a pressure of from 50 to 10,000 kPa. Any oxygen-containing gas, preferably air, can be used as the oxidizing agent. The reaction can be carried out in a graft reactor or a continuous-flow reactor. Basic buffers may be added to react with acidic by-products that may be formed during oxidation. In addition, an aqueous phase which can aid in the dissolution of a basic compound, for example sodium carbonate, may be introduced.

Another reaction step in the conversion of cyclohexylbenzene to phenol and cyclohexanone is a reaction at a temperature of 20 ° C to 150 ° C, for example 40 ° C to 120 ° C, and a pressure of 50 to 2,500 kPa, for example 100 to 1000 kPa Lt; RTI ID = 0.0 &gt; cyclohexylbenzene &lt; / RTI &gt; hydroperoxide, which is conveniently carried out by contacting the catalyst with hydroperoxide in liquid phase at a pressure of from about &lt; RTI ID = Cyclohexylbenzene hydroperoxide is preferably diluted in an organic solvent which is inert to the cleavage reaction, such as methyl ethyl ketone, cyclohexanone, phenol or cyclohexylbenzene to aid in heat removal. The cleavage reaction may conveniently be carried out in a catalytic distillation unit.

The catalyst used during the cutting step may be a homogeneous catalyst or an inhomogeneous catalyst.

Suitable homogenous cleavage catalysts include sulfuric acid, perchloric acid, phosphoric acid, hydrochloric acid and p-toluenesulfonic acid. Ferric chloride, boron trifluoride, sulfur dioxide and sulfur trioxide are effective homogenous cleavage catalysts. A preferred homogeneous cleavage catalyst is sulfuric acid and the preferred concentration is in the range of 0.05 to 0.5% by weight. In the case of a homogeneous acid catalyst, a neutralization step is preferably carried out after the cleavage step. This neutralization step typically involves contacting with a basic component and subsequently removing the salt-concentrated aqueous phase by decanting or distillation.

Suitable heterogeneous catalysts for use in the cleavage of cyclohexylbenzene hydroperoxide include clays, such as the acidic montmorillonite silica-alumina clays described in U.S. Patent No. 4,870,217, or the fuels described in WO2012 / 145031 And includes self-site molecular sieves.

The effluent from the cleavage reaction comprises substantially equimolar amounts of phenol and cyclohexanone, and on demand, the cyclohexanone can be sold or dehydrogenated with additional phenol. Any suitable dehydrogenation catalyst, such as the dehydrogenation catalysts described herein, or modifications thereof, may be used in this reaction. Suitable conditions for the dehydrogenation step are a temperature of 250 ° C to 50 ° C and a pressure of 0.01 to 20 atmospheres (1 to 2030 kPa), for example a temperature of 300 to 45 ° C and a pressure of 1 to 3 atmospheres (100 to 300 kPa) Pressure.

The following examples will be more specifically described with reference to the following non-limiting examples and the accompanying drawings.

Example

In this embodiment, a catalyst precursor comprising Pt as the first metal and Sn as the second metal and SiO ₂ as the inorganic support and essentially free of the third metal is activated in the presence of a flowing H ₂ stream at various temperatures And then tested for activity in the dehydrogenation of cyclohexane under the same nominally identical dehydrogenation conditions in a tubular downflow reactor. Methods for preparing catalyst precursors are disclosed in WO2012 / 134552, the contents of which are incorporated herein by reference in their entirety.

Procedure A : The catalyst was activated by raising the temperature from room temperature to 400 캜 at a rate of 40 캜 / hour and keeping the catalyst at the final temperature for 2 hours. The activation was carried out at 100 psig (689 kPa gauge) with pure hydrogen.

Procedure B : The catalyst was activated by raising the temperature to 400 &lt; 0 &gt; C at a rate of 15 [deg.] C / hour from room temperature. The catalyst was further activated by raising the temperature from 400 캜 to 520 캜 at a rate of 5 캜 / hour and keeping the catalyst at the final temperature for 8 hours. The activation was also performed at 100 psig (689 kPa gauge) with pure hydrogen.

Upon activation, the catalysts were then passed through a feed stream comprising 420 psig, 109 psig (752 kPa gauge) and H ₂ / hydrocarbon (100 g) in a feed comprising 10 wt% cyclohexane, 1 wt% methylcyclopentane, and 89 wt% And tested at a molar ratio of 4. The main results of the activation study are summarized in Figures 1 and 2 where 101 represents the results for the catalyst prepared according to Procedure A and 103 the results for the catalyst prepared according to Procedure B.

As can be seen in Figure 1, the catalytic activity was almost doubled when the catalyst was activated using Procedure B as compared to Procedure A. As can be seen in Figure 2, the improved activity was achieved without loss in selectivity.

Thus, from these examples it is evident that a higher temperature activation temperature of greater than 400 ° C is more advantageous than less than 400 ° C.

While the invention has been described and illustrated with reference to specific embodiments, those skilled in the art will appreciate that the invention may provide variations not necessarily illustrated herein. For this reason, only the appended claims should be referred to in order to determine the true scope of the invention.

The contents of all references cited herein are incorporated by reference in their entirety.

Non-limiting embodiments of the method of the present disclosure include:

E1. As a dehydrogenation method,

(1A) providing a catalyst precursor comprising (i) an inorganic support, and (ii) 0.01 to 10.0 wt% based on the total weight of the catalyst precursor, a first metal selected from Group 6 to Group 10 metals of the Periodic Table of Elements;

(1B) obtaining an activated dehydrogenation catalyst by treating the catalyst precursor in an H ₂ -containing atmosphere for at least 15 minutes at a temperature ranging from 300 to 600 ° C, preferably from 420 to 550 ° C; And

Contacting the first composition comprising cyclohexane with an activated dehydrogenation catalyst under dehydrogenation conditions in a (1C) dehydrogenation reactor to convert at least a portion of the cyclohexane to benzene and obtain a dehydrogenation reaction product

&Lt; / RTI &gt;

E2. In E1, the temperature of step (1B) ranges from 420 to 550 占 폚.

E3. In E1 or E2, the first composition in step (1C)

(1Ba) contacting a hydroalkylation catalyst with a benzene and hydrogen under hydroalkylation conditions to form a hydroalkylation reaction mixture comprising cyclohexylbenzene, cyclohexane, methylcyclopentane, and benzene; And

(1Bb) From the hydroalkylation reaction mixture, (i) a first composition wherein at least one of benzene and cyclohexane has a higher concentration than cyclohexylbenzene, and (ii) a first composition wherein cyclohexylbenzene has a higher concentration than benzene and cyclohexane Lt; RTI ID = 0.0 &gt;

&Lt; / RTI &gt;

E4. In any one of E1 to E3,

(1D) recycling at least a portion of the benzene in the dehydrogenation reaction product to the step (1Ba)

&Lt; / RTI &gt;

E5. The method according to any one of E1 to E4, wherein the inorganic support of the catalyst precursor in step (1A) comprises at least one of silica, alumina, aluminosilicate, oxides of Group 3 to Group 5 metals, carbon and carbon nanotubes of the Periodic Table of Elements. Way.

E6. The method according to any one of E1 to E5, wherein at least a part of the first metal in the catalyst precursor in step (1A) is in an oxidation state higher than zero.

E7. The method according to any one of E1 to E6, wherein the first metal comprises Pt and / or Pd.

E8. In any one of E1 to E7, the catalyst precursor is additionally,

(iii) 0.05 to 5.0% by weight of a second metal selected from group 14 of the Periodic Table of Elements, and

(iv) 0.05 to 10.0% by weight of a third metal selected from Groups 1 and 2 of the Periodic Table of the Elements

&Lt; / RTI &gt;

E9. The method of E8, wherein the second metal comprises Ge, Sn and / or Pb, and the third metal comprises Na and / or K.

E10. The method according to any one of E1 to E9, wherein, upon completion of step (1B), at least 98 wt% of the first metal in the activated catalyst is in the elemental state, based on the weight of the first metal.

E11. The method according to any one of E1 to E10, wherein, in step (1B), the H ₂ -containing atmosphere comprises at least 90 wt% hydrogen.

E12. The method according to any one of E1 to E11, wherein step (1B) comprises treating the catalyst precursor in a flow stream of an H ₂ -containing atmosphere to a temperature in the range of from 300 to 600 ° C.

E13. The method according to any one of E1 to E12, wherein the H ₂ -containing atmosphere in step (1B) has a benzene concentration of 1 wt% or less based on the total weight of the H ₂ -containing atmosphere.

E14. The method according to any one of E1 to E13, wherein the first composition further comprises hydrogen in step (1C) and the H ₂ -containing atmosphere in step (1B) is the first composition.

E15. The method according to any one of E1 to E14, wherein after step (1B) and before step (1C), the activated dehydrogenation catalyst is protected by an O ₂ -free protective atmosphere.

E16. Method according to E15, the protective atmosphere includes at least one of H ₂ and CH _4,.

E17. The method according to any one of E1 to E16, wherein step (1B) comprises heating the catalyst precursor for at least 15 minutes at a temperature in the range of 450 to 550 占 폚.

E18. The method according to any one of E1 to E17, wherein step (1B) is carried out at a first heating rate in the range of from 2 to 30 占 폚 / min at a temperature of less than 400 占 폚 and / or from 1 to 15 占 폚 / min &Lt; / RTI &gt; and heating the catalyst precursor at a second heating rate of at least about &lt; RTI ID = 0.0 &

E19. In any one of E1 to E18, step (1A)

(1A-1) an inorganic support,

(1A-2) impregnating the inorganic support with a solution of a salt of the first metal to obtain an impregnated support,

(1A-3) Sintering the impregnated support at a temperature in the range of 500 to 1000 ° C

&Lt; / RTI &gt;

E20. The process according to any one of E1 to E19, wherein step (1B) and step (1C) are all carried out in a dehydrogenation reactor.

E21. The method according to any one of E1 to E19, wherein, in step (1Ba), the first composition further comprises benzene and hydrogen.

E22. The method of any one of E1 to E21, wherein in step (1C), the first composition comprises 0.01 to 5.0% by weight, based on the total weight of the first composition, of methylcyclopentane and at least a portion of the methylcyclopentane is paraffin / RTI &gt;

E23. The method according to any one of E1 to E22, wherein, in step (1C), the dehydrogenation conditions comprise a temperature in the range of 300 to 600 占 폚.

E24. As a method for producing phenol and / or cyclohexanone,

(2A) producing cyclohexylbenzene according to any one of E3 to E23,

(2B) oxidizing at least a portion of the cyclohexylbenzene to obtain an oxidation reaction product comprising cyclohexylbenzene hydroperoxide, and

(2C) truncating at least a portion of the cyclohexylbenzene hydroperoxide to produce a cleavage reaction product comprising phenol and cyclohexanone

&Lt; / RTI &gt;

E25. As a dehydrogenation method,

(3A) providing a catalyst precursor comprising (i) an inorganic support, and (ii) a first metal selected from Group 6 to Group 10 metals of the Periodic Table of Elements from 0.05 to 10.0 wt%, based on the total weight of the catalyst precursor;

(3B) obtaining the activated catalyst by treating the catalyst precursor in an H ₂ -containing atmosphere at a temperature ranging from 300 to 600 ° C for at least 15 minutes; And

(3C) contacting a first composition comprising at least 0.1% by weight, based on the total weight of the composition, of a saturated cyclic hydrocarbon, with the activated catalyst under dehydrogenation conditions to form at least a portion of the saturated cyclic hydrocarbon with an unsaturated cyclic hydrocarbon &Lt; / RTI &gt;

&Lt; / RTI &gt;

E26. In E25, the inorganic support of the catalyst precursor comprises at least one of silica, alumina, aluminosilicate, and oxides of Group 3 to Group 5 metals of the Periodic Table of Elements.

E27. E25 or E26, wherein at least a portion of the first metal in the catalyst precursor is in an oxidized state above zero.

E28. The method according to any one of E25 to E27, wherein the first metal comprises Pt and / or Pd.

E29. The catalyst precursor according to any one of E25 to E28,

(iii) 0.05 to 5.0% by weight of a second metal selected from group 14 of the Periodic Table of Elements, and

(iv) 0.05 to 10.0% by weight of a third metal selected from Groups 1 and 2 of the Periodic Table of the Elements

&Lt; / RTI &gt;

E30. The method of E29, wherein the second metal comprises Ge, Sn and / or Pb, and the third metal comprises Na and / or K.

E31. The method according to any one of E25 to E30, wherein, upon completion of step (3B), at least 98 wt% of the first metal in the activated catalyst is in the elemental state, based on the weight of the first metal.

E32. The method according to any one of E25 to E31, wherein the H ₂ -containing atmosphere has a benzene concentration of 1% by weight or less based on the total weight of the H ₂ -containing atmosphere.

E33. The method according to any one of E25 to E32, wherein the first composition further comprises hydrogen in step (1Bb) and the H ₂ -containing atmosphere in step (1B) is the first composition.

E34. The method according to any one of E25 to E33, wherein after step (1B) and before step (1C), the activated dehydrogenation catalyst is protected by an O ₂ -free protective atmosphere.

E35. Method according to E34, the protective atmosphere includes at least one of H ₂ and CH _4,.

E36. The method according to any one of E25 to E35, wherein step (3B) comprises treating the catalyst precursor in a flow stream of an H ₂ -containing atmosphere at a temperature in the range of from 300 to 600 ° C.

E37. The method according to any one of E25 to E36, wherein step (3B) comprises heating the catalyst precursor for at least 15 minutes at a temperature in the range of 450 to 550 占 폚.

E38. The method according to any one of E25 to E37, wherein step (3B) is carried out at a first heating rate in the range of 2 to 30 占 폚 / min at a temperature of less than 400 占 폚 and / or in a range of 1 to 15 占 폚 / min &Lt; / RTI &gt; and heating the catalyst precursor at a second heating rate of at least about &lt; RTI ID = 0.0 &

E39. In any one of E25 to E38, step (3A)

(3A-1) &lt; / RTI &gt; inorganic support,

(3A-2) impregnating the inorganic support with a solution of a salt of the first metal to obtain an impregnated support,

(3A-3) sintering the impregnated support at a temperature in the range of 500 to 1000 ° C

&Lt; / RTI &gt;

E40. The method according to any one of E25 to E39, wherein step (3B) and step (3C) are carried out in the same vessel.

E41. In E40, between step (3B) and step (3C), the activated catalyst is protected from oxygen exposure.

E42. The method according to any one of E25 to E41, wherein, in step (3C), the composition comprises cyclohexane, benzene and hydrogen, and at least a portion of the cyclohexane is converted to benzene.

E43. The method according to any one of E25 to E42, wherein, in step (3C), the composition comprises methylcyclopentane and at least a portion of the methylcyclopentane is converted to paraffin.

E44. The process according to any one of E25 to E43, wherein, in step (3C), the dehydrogenation conditions comprise a temperature in the range of 300 to 600 占 폚.

E45. The method according to any one of E25 to E44, wherein the first metal is Pt and / or Pd.

Claims (20)

(1A) providing a catalyst precursor comprising (i) an inorganic support, and (ii) 0.01 to 10.0 wt%, based on the total weight of the catalyst precursor, of a first metal selected from Group 6-10 metals of the Periodic Table of Elements;
(1B) obtaining an activated dehydrogenation catalyst by treating the catalyst precursor in an H ₂ -containing atmosphere at a temperature ranging from 450 to 550 ° C for at least 480 minutes; And
Contacting the first composition comprising cyclohexane with an activated dehydrogenation catalyst under dehydrogenation conditions in a (1C) dehydrogenation reactor to convert at least a portion of the cyclohexane to benzene and obtain a dehydrogenation reaction product
&Lt; / RTI &gt; The method according to claim 1,
The first composition in step (1C)
(1Ba) contacting a hydroalkylation catalyst with benzene and hydrogen under hydroalkylation conditions to form a hydroalkylation reaction mixture comprising cyclohexylbenzene, cyclohexane, methylcyclopentane, and benzene; And
(1Bb) From the hydroalkylation reaction mixture, (i) a first composition wherein at least one of benzene and cyclohexane has a higher concentration than cyclohexylbenzene, and (ii) a first composition wherein cyclohexylbenzene has a higher concentration than benzene and cyclohexane Lt; RTI ID = 0.0 &gt;
&Lt; / RTI &gt; 3. The method of claim 2,
(1D) recycling at least a portion of the benzene in the dehydrogenation reaction product to the step (1Ba)
&Lt; / RTI &gt; 4. The method according to any one of claims 1 to 3,
In addition to the catalyst precursor,
(iii) 0.01 to 5.0% by weight of a second metal selected from Group 14 of the Periodic Table of Elements, and
(iv) 0.01 to 10.0% by weight of a third metal selected from Group 1 and Group 2 metals of the Periodic Table of the Elements
&Lt; / RTI &gt; 5. The method of claim 4,
Wherein the second metal comprises Sn, and wherein the third metal comprises K. 4. The method according to any one of claims 1 to 3,
Wherein in step (1B) the H ₂ -containing atmosphere comprises at least 90 wt% hydrogen. 4. The method according to any one of claims 1 to 3,
Wherein step (1B) comprises treating the catalyst precursor in a flow stream of an H ₂ -containing atmosphere. 4. The method according to any one of claims 1 to 3,
Wherein the H ₂ -containing atmosphere in step (1B) has a benzene concentration of 1 wt% or less based on the total weight of the H ₂ -containing atmosphere. The method according to claim 2 or 3,
Wherein the first composition further comprises hydrogen in step (1Bb) and the H ₂ -containing atmosphere in step (1B) is a first composition. 4. The method according to any one of claims 1 to 3,
Prior to step (1C) after step (1B), the activated dehydrogenation catalyst is protected by an O ₂ -free protective atmosphere. 4. The method according to any one of claims 1 to 3,
Step 1A is
(1A-1) an inorganic support,
(1A-2) impregnating the inorganic support with a solution of a salt of the first metal to obtain an impregnated support,
(1A-3) Sintering the impregnated support at a temperature in the range of 300 to 1000 ° C
&Lt; / RTI &gt; 4. The method according to any one of claims 1 to 3,
Wherein step (1B) and step (1C) are all carried out in a dehydrogenation reactor. The method according to claim 2 or 3,
In step (1Ba), the first composition comprises benzene and hydrogen. 4. The method according to any one of claims 1 to 3,
In step (1C), the first composition comprises 0.01 to 5.0% by weight methylcyclopentane based on the total weight of the first composition, and at least a portion of the methylcyclopentane is converted to paraffin. (2A) producing cyclohexylbenzene from the second composition obtained in step (1Bb) according to the method of claim 2,
(2B) oxidizing at least a portion of the cyclohexylbenzene to obtain an oxidation reaction product comprising cyclohexylbenzene hydroperoxide, and
(2C) truncating at least a portion of the cyclohexylbenzene hydroperoxide to produce a cleavage reaction product comprising phenol and cyclohexanone
&Lt; / RTI &gt; and / or cyclohexanone. delete delete delete delete delete

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