CN103848709A

CN103848709A - Dehydrogenation process

Info

Publication number: CN103848709A
Application number: CN201310629539.9A
Authority: CN
Inventors: 陈诞仁; C·L·贝克; H·奈尔; F·M·贝尼特斯; C·M·史密斯
Original assignee: Exxon Chemical Patents Inc
Current assignee: ExxonMobil Chemical Patents Inc
Priority date: 2012-11-30
Filing date: 2013-11-29
Publication date: 2014-06-11
Also published as: WO2014085112A1; KR20150063489A; SG11201502981QA; KR101745220B1; EP2925709A1

Abstract

Disclosed is a process for dehydrogenating a hydrocarbon with a dehydrogenation catalyst. The method includes a step of activating a catalyst precursor in a H2-containing atmosphere. A particularly advantageous activation process includes heating the catalyst precursor to a temperature ranging from 400 DEG C to 600 DEG C. The process is particularly advantageous for dehydrogenating cyclohexane to prepare benzene.

Description

Method of dehydrogenating

The cross reference of related application

Present patent application relates to that on March 28th, 2011 submits to and name is called the U.S. Provisional Patent Application number 61/468 of " method of dehydrogenating ", 298, submit to on December 17th, 2010 and name is called the U.S. Patent Application Serial Number 13/512 of " method of dehydrogenating ", 805, the full content of two pieces of applications is incorporated herein by reference.

Technical field

The present invention relates to for by saturated cyclic hydrocarbon as hexanaphthene and/or methylcyclopentane, particularly at benzene to the hexanaphthene producing in the hydroalkylation process of phenylcyclohexane and the method for methylcyclopentane dehydrogenation.

Background technology

Phenylcyclohexane can be produced by the method for hydroalkylation or reductive alkylation by benzene.In the method, the heating under catalyzer exists by benzene and hydrogen, makes benzene experience partial hydrogenation to produce reaction intermediate as tetrahydrobenzene, and described tetrahydrobenzene is then by the alkylation of described benzene parent material.Therefore, U.S. Patent number 4,094,918 and 4,177,165 disclose the hydroalkylation of aromatic hydrocarbon on catalyzer, and described catalyzer comprises zeolite and the palladium promotor of crossing with nickel and RE-treated.Similarly, U.S. Patent number 4,122,125 and 4,206,082 discloses the application as aromatics hydroalkylation catalyzer of the ruthenium that loads on the zeolite that RE-treated crosses and nickel compound.The zeolite adopting in these art methods is X zeolite and Y.In addition, U.S. Patent number 5,053,571 rutheniums of suggestion working loads in zeolite beta and nickel are as aromatics hydroalkylation catalyzer.But, the problems that run into about these suggestions early of the hydroalkylation of benzene are, selectivity to phenylcyclohexane is low, particularly low and produce a large amount of undesired by products, particularly hexanaphthene and methylcyclopentane to the selectivity of phenylcyclohexane under feasible benzene transformation efficiency economically.

Recently, U.S. Patent number 6,037,513 is open, and in the hydroalkylation of benzene, phenylcyclohexane selectivity can be by making benzene and hydrogen and comprising at least one hydrogenation metal and contact to improve with the dual-function catalyst of the molecular sieve of MCM-22 type.Hydrogenation metal is preferably selected from palladium, ruthenium, nickel, cobalt and their mixture, and contact procedure is at the temperature of 50 ℃-350 ℃, the pressure of 100kPa-7000kPa, the benzene of 0.01-100 and hydrogen mol ratio and 0.01hr ^-1-100hr ^-1weight hourly space velocity (WHSV) under carry out.Described ' 513 patents openly arrive, and then obtained phenylcyclohexane can be oxidized to corresponding hydroperoxide, and described superoxide can be broken down into phenol and the pimelinketone of hope.

A shortcoming of the method is that it produces impurity as hexanaphthene and methylcyclopentane.These impurity have represented the loss of valuable benzene charging.And unless be removed, these impurity can be inclined in system to be accumulated, substitute thus the generation of benzene and the undesirable by product of increase.Therefore the major issue that, phenylcyclohexane is faced as the commercial applications of phenol precursor is to remove hexanaphthene and methylcyclopentane impurity.

U.S. Patent number 7,579,511 have advised a solution to this problem, described patent has been described the method for preparing phenylcyclohexane, wherein benzene experiences hydroalkylation under the first catalyzer exists, to form the first effluent composition that contains phenylcyclohexane, hexanaphthene, methylcyclopentane and unreacted benzene.Then this first effluent composition is separated into rich hexanaphthene/methylcyclopentane composition, rich benzene composition and rich phenylcyclohexane composition, and described rich hexanaphthene/methylcyclopentane composition is contacted with the second dehydrogenation catalyst of low acidity, at least a portion of hexanaphthene is changed into benzene and at least a portion of methylcyclopentane is changed into the paraffins of straight chain and/or side chain and forms the second outflow compositions.Then rich benzene composition and second can be flowed out to compositions and be recycled to hydroalkylation step.But a problem of the method is that hexanaphthene has the boiling point similar to the boiling point of benzene with methylcyclopentane, make that they are difficult by conventional fractionation by distillation.

In International Patent Publication No. W WO2009/131769, advised another solution, wherein benzene experiences hydroalkylation under the first catalyzer exists, to produce the first effluent composition that contains phenylcyclohexane, hexanaphthene and unreacted benzene.Then the C that first effluent composition is separated into rich phenylcyclohexane composition and comprises hexanaphthene and benzene ₆product composition.Then by C ₆at least a portion of product composition contacts with the second catalyzer under dehydrogenation condition, produce the second outflow compositions at least a portion of hexanaphthene is changed into benzo, this the second outflow compositions comprises benzene and hydrogen, and it can be recycled to described hydroalkylation step.

Be disclosed in U.S. Patent number 7,579,511 and WO2009/131769 in described two kinds of methods all depend on and use the dehydrogenation catalyst that comprises group VIII metal on as aluminum oxide, silicon oxide, titanium oxide, zirconium white, gac and their combination at porous inorganic carrier.But in practice, such dehydrogenation catalyst only has limited activity for the conversion of hexanaphthene and/or methylcyclopentane, and may experience in some cases aging fast.Therefore need the improved catalyzer for remove hexanaphthene and methylcyclopentane from the benzene circulation composition adopting at benzene hydrogenation alkylation.The conversion of hexanaphthene is even more important, because the boiling point of its boiling point and benzene differs in 1 ℃.The conversion of methylcyclopentane also wishes, but important not as hexanaphthene, approaches 9 ℃ poor because have between the boiling point of methylcyclopentane and benzene.

Recently, have been found that the catalyzer that contains at least one dehydrogenation metal (for example platinum or palladium) and the 1st family or group II metal promotor (being basic metal or alkaline-earth metal) can be used to hexanaphthene and/or methylcyclopentane dehydrogenation.The method is for example described in the PCT application number PCT/US2010/061041 submitting on December 17th, 2010.But, have further improved cyclohexane conversion and/or optionally dehydrogenation catalyst need.

Summary of the invention

Have now found that, the activation step of dehydrogenation catalyst can significantly improve the performance of catalyzer.

A first aspect of the present invention relates to method of dehydrogenating, and the method comprises:

(1A) provide catalyst precursor, this catalyst precursor comprises (i) inorganic carrier and (ii) the first metal that is selected from periodic table of elements 6-10 family metal of 0.01wt%-10.0wt%, the gross weight meter based on described catalyst precursor;

(1B) by containing H ₂in atmosphere, at 300 ℃-600 ℃, the preferably catalyst precursor time of at least 15 minutes described in the Temperature Treatment within the scope of 420 ℃-550 ℃, obtain the dehydrogenation catalyst of activation; With

(1C) the first composition that makes to comprise hexanaphthene contacts in dehydrogenation reactor with the dehydrogenation catalyst of described activation under dehydrogenation condition, obtains products of dehydrogenation reactions at least a portion of described hexanaphthene is changed into benzo.

A second aspect of the present invention relates to the method for preparing phenol and/or pimelinketone, and the method comprises:

(2A) use the method for first aspect to produce phenylcyclohexane;

(2B) at least a portion that is oxidized described phenylcyclohexane is to obtain the oxidation reaction product that comprises phenylcyclohexane hydroperoxide; With

(2C) make at least a portion cracking of described phenylcyclohexane hydroperoxide, to produce the cleavage reaction product that comprises phenol and pimelinketone.

At least one or more during method of the present invention has the following advantages.The first, by before catalyst precursor is put into dehydrogenation reaction at hydrogeneous atmosphere Heating Dehydrogenation catalyst precursor at elevated temperatures, can activate described catalyst precursor with obtain have high conversion and optionally activate catalyzer.The second, by heating described catalyst precursor to higher than the activation temperature of 400 ℃ in reactivation process, can obtain surprisingly having improved transformation efficiency and do not sacrifice optionally catalyzer.

Other feature and advantage of the present invention will be set forth in detailed description and claims and accompanying drawing.Be appreciated that aforementioned general description and following detailed description are only illustrations of the present invention, and intention is provided for understanding general status or the framework of claimed character of the present invention and feature.

Brief description of drawings

Fig. 1 and 2 be show respectively use by according to the hexanaphthene of two kinds of different catalysts of two kinds of embodiment in the present invention different operations activation to the transformation efficiency of benzene and chart optionally.

Describe in detail

In the present invention, method is described to comprise at least one " step ".Should be appreciated that, each step is a kind of behavior or operation, and it can be carried out one or many in continuous or discrete mode in described method.Unless regulation or context clearly indicate in addition on the contrary, the order that each step in method can be listed according to them is carried out in succession, be with or without with one or more other steps overlapping, or allow in the situation that with any other order carry out.In addition, one or more or even can carry out with regard to the material of identical or different batch in steps simultaneously.For example, in continuous processing, first step in method is with regard in being just fed to the raw material of initial stage of the method and carrying out, and the intermediary material that second step can just be obtained by the raw material of processing the method that is fed in first step early time is carried out simultaneously.Preferably, described step is carried out according to listed order.

Except as otherwise noted, all numerals of the amount of indicating should be understood to be modified by term " about " in all cases in the present invention.Be also to be understood that the accurate numerical value using has formed specific embodiment in specification sheets and claims.Endeavour to ensure the accuracy of data in embodiment.But, should be appreciated that, owing to measuring the limitation of adopted technology and equipment, the data of any mensuration contain the error of certain level inherently.

Indefinite article used herein " one (a) " or " a kind of (an) " should refer to " at least one (kinds) ", unless stipulated on the contrary or context clearly indicates in addition.Therefore, use the embodiment of " hydrogenation metal " to comprise wherein to use embodiments a kind of, two kinds or more kinds of dissimilar hydrogenation metal, unless regulation or context clearly indicate the hydrogenation metal that only uses a type on the contrary.

" wt% " used herein refers to weight percentage, " vol% " refers to percent by volume, " mol% " refers to molecular fraction, and " ppm " refers to parts-per-million, and " ppm wt " and " wppm " is used in reference to the parts-per-million based on weight interchangeably.All " ppm " used herein is ppm by weight, unless specified otherwise herein.The total amount of the composition of all concentration based on discussed represents in this article.The all scopes that represent in this article should comprise that two end points are as two specific embodiments, unless stipulated on the contrary or indicated.

Generic term used herein " dicyclohexyl benzene " is included in 1 in set, 2-dicyclohexyl benzene, 1,3-dicyclohexyl benzene and Isosorbide-5-Nitrae-dicyclohexyl benzene, unless clearly indicate refer in them only one or both.In the time using with singulative, term phenylcyclohexane refers to mono-substituted phenylcyclohexane.

In the present invention, the composition of the precursor of catalyzer and catalyzer represents based on dry component.Can carry secretly at catalystic material in the degree of water in various degree, in its composition, not consider such water.Although catalystic material or their precursor can be in the case of having processed the water being included on a small quantity wherein and/or using, the catalyzer of preferred described activation when be placed according to time in the application in method of dehydrogenating of the present invention be do (for example there is 5.0wt% at the most, or 3.0wt% at the most, or 1.0wt% at the most, or 0.5wt% at the most, or the water-content of 0.1wt% at the most).In the present invention, the amount of first, second, and third metal in catalyzer and its precursor represents based on elemental metals, oxidation state that let it be.Therefore, all amounts of Pt, Pd in these catalystic materials, Sn, K, Na, Ni, Co and other 1,2,6-10 and 14 family's metals represent on simple substance basis, even if they can for example be present in the material of being discussed with the form of salt, oxide compound, title complex and elemental metals whole or in part.For example, with the tin and the 1.0wt%Pt that load on catalyst composition prepared by 1.9 grams of chlorination pink salts (1.0 grams of tin) on 98 grams of silicon-dioxide and 22.29 grams of hydroxide four ammino platinum solution (4.486wt%Pt) and contain 1.0wt%, based on the gross weight meter of described catalyst composition that is dry component.Further, the composition of the precursor of catalyzer represents with the final composition of deactivated catalyst prepared therefrom.The those of ordinary skill of catalyzer preparation field can batch treatment parent material as salt, solution, oxide compound etc., to realize the ultimate aim chemical constitution of catalyzer of described activation.For example, in the present invention, the catalyst precursor that comprises 1.0wt%Pt, 1.0wt%Sn and 98.0wt% silicon-dioxide refers to that the parent material that comprises desirable amount is as PtO ₂, Pt, SnO ₂, SnO, SnCl ₄, SnCl ₂deng in one or more precursor, it will be converted to the final catalyzer that comprises platinum, tin and silicon-dioxide with above-mentioned amount in the time of activation.

Term used herein " MCM-22 types of material " (or " material of MCM-22 type " or " molecular sieve of MCM-22 type " or " MCM-22 type zeolite ") comprises with lower one or more:

The molecular sieve being made up of the first common degree crystal structure piece (building block) structure cell, described structure cell has MWW matrix topology.Structure cell is the spatial disposition of atom, if piled up in three-dimensional space, this spatial disposition is described crystalline structure." Atlas of Zeolite Framework Types ", the 5th edition, 2001(is all incorporated herein by reference it) in such crystalline structure has been discussed;

The molecular sieve being formed by common the second degree tectonic block, described the second degree tectonic block is the 2-dimension tiling of such MWW matrix topology structure cell, forms the individual layer of a structure cell thickness (a hopefully c-structure cell thickness);

The molecular sieve being formed by common the second degree tectonic block, described the second degree tectonic block is the layer of one or more than one structure cell thickness, the layer of wherein said more than one structure cell thickness by stacking, fill or the individual layer of at least two structure cell thickness of combination forms.The second degree the stacking of tectonic block like this can be by regular mode, irregular mode, random fashion or its any combination; With

Tie up by thering is any rule of structure cell of MWW matrix topology or random 2-dimension or 3-the molecular sieve constituting.

The molecular sieve of MCM-22 type comprises having and comprises with 12.4 ± 0.25, those of the peaked X-ray diffractogram of d spacing of 6.9 ± 0.15,3.57 ± 0.07 and 3.42 ± 0.07 dusts.By standard technique (the K-α two-wire that for example uses copper as incident ray and scintillometer is housed and associated computer as the technology of the diffractometer of gathering system) obtain the X ray diffracting data for exosyndrome material.

The material of MCM-22 type comprises that MCM-22 (is described in U.S. Patent number 4, 954, in 325), PSH-3 (is described in U.S. Patent number 4, 439, in 409), SSZ-25 (is described in U.S. Patent number 4, 826, in 667), ERB-1 (being described in european patent number 0293032), ITQ-1 (is described in U.S. Patent number 6, 077, in 498), ITQ-2 (being described in International Patent Publication No. W WO97/17290), MCM-36 (is described in U.S. Patent number 5, 250, in 277), MCM-49 (is described in U.S. Patent number 5, 236, in 575) and MCM-56 (be described in U.S. Patent number 5, 362, in 697).For realizing object of the present invention, other molecular sieve also can be used separately or together with described MCM-22 types of molecules sieve as UZM-8 (be described in U.S. Patent number 6,756,030 in).Hopefully, described molecular screening is from (a) MCM-49; (b) MCM-56; (c) isotype of MCM-49 and MCM-56 (isotype), for example ITQ-2.

The dehydrogenation catalyst adopting in dehydrogenation reaction comprises (i) inorganic carrier; (ii) be selected from the first metal of periodic table of elements 6-10 family; Optionally (iii) is selected from the second metal of the periodic table of elements the 14th family; Optionally (iv) is selected from the 3rd metal of the periodic table of elements the 1st and 2 families.For example, dehydrogenation catalyst can comprise the first metal and the second metal the two, but do not basically contain the 3rd metal.The example of such catalyzer is for example described in WO2012/134552, and the relevant portion of the document is incorporated herein by reference.Alternatively, dehydrogenation catalyst can comprise first and the 3rd metal the two, but do not basically contain the second metal.The example of such catalyzer is for example described in WO2011/096998, and the relevant portion of the document is introduced to text as a reference.It is also possible that the dehydrogenation catalyst using in the method for the invention comprises first, second, and third metal simultaneously.Used herein, be the new annotation providing on the interior front cover of Hawley ' s Condensed Chemical Dictionary (the 14th edition) of Richard J.Lewis in the numbering plan of periodictable family of elements disclosed herein.

The catalyzer using in the method for the invention comprises the first metal that is selected from periodic table of elements 6-10 family, for example platinum and/or palladium.Conventionally, the metal that is selected from periodic table of elements 6-10 family exists with the amount within the scope of Fm1wt%-Fm2wt%, and wherein Fm1 can 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; With Fm2 can 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, condition is Fm1<Fm2.

Alternatively or additionally, the catalyzer using in the method for the invention can comprise (i) nickel, and its concentration is 2.0wt% at the most, or 1.0wt% at the most, or 0.5wt% at the most, or 0.1wt% nickel at the most; (ii) cobalt, its concentration is 2.0wt% at the most, or 1.0wt% at the most, or 0.5wt% at the most, or 0.1wt% at the most, the gross weight meter of percentage ratio based on described catalyzer.Preferably, catalyst composition does not contain or does not basically contain ruthenium, rhodium, lead and/or germanium, and/or any other active element component.

Do not wish by concrete theoretical constraint, it is believed that the first metal in the catalyzer of activation is the main ingredient of being responsible for the dehydrogenation functionality of catalyzer.Under suitable dehydrogenation condition, at the temperature of the hope being especially discussed in more detail below, cyclic hydrocarbon especially saturated compound, as hexanaphthene can be activated when with the first metallic contact, experiences dehydrogenation reaction, and changes into undersaturated compound as benzene.At least a portion that also it is believed that the first metal of the deactivated catalyst using in method of dehydrogenating of the present invention should be simple substance form, to give the dehydrogenation activity level of hope.Therefore, in the time using in method of dehydrogenating, the catalyzer of activation comprises at least the first metal that is simple substance form of x% wishes, wherein x can be 50,55,60,65,70,75,80,85,90,95,98,99 or even 99.5.It is also highly to wish that at least most of maintenance of the first metal in whole dehydrogenation reaction process according to the present invention in catalyzer is simple substance state.Therein hydrogen be enrich environment in, for example, in the general dehydrogenation reactor of normal running, such condition can be satisfied.For example, the second metal (the 14th family's metal) is present in the amount within the scope of Sm1wt%-Sm2wt% in the dehydrogenation catalyst of the activation using in method of dehydrogenating of the present invention, gross weight meter based on described dehydrogenation catalyst, wherein Sm1 can 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; With Sm2 can 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, condition is Sm1<Sm2.Preferably, described the 14th family's metal is tin.

In catalyzer, the metal that is selected from periodic table of elements 6-10 family for example, with the ratio (Pt/Sn ratio) of the metal that is selected from the periodic table of elements the 14th family can be in the scope of Rt1-Rt2, wherein Rt1 can be 0.1,0.2,0.3,0.4,0.5,0.8,1.0,2.0,3.0,4.0,5.0,8.0,10.0,15.0,20.0,30.0,40.0,50.0, and Rt2 can be 400,350,300,250,200,150,100,90.0,80.0,70.0,60.0,50.0, condition is Rt1<Rt2.The preferred scope of described ratio is: 2.5-400,2.7-200 and 3.0-100.

Preferably, the catalyzer of the activation using in the method for the invention comprises the 3rd metal, and it is one or more metals of the periodic table of elements the 1st family and the 2nd family.The 3rd metal exists with the amount within the scope of Tm1wt%-Tm2wt%, and wherein Tm1 can be 0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1.0,1.5,2.0,2.5,3.0; With Tm2 can be 5.0,4.5,4.0,3.5,3.0,2.5,2.0,1.5,1.0, as long as Tm1<Tm2.For example, the metal that the 3rd metal can containing element periodictable the 1st family's element, for example potassium, caesium and rubidium; Preferably potassium.Alternatively, the 3rd metal can comprise the element of at least one periodic table of elements the 2nd family, for example beryllium, calcium, magnesium, strontium, barium and radium; Preferably calcium and magnesium.Consider the high chemically reactive of the 1st and 2 family's elements in the periodic table of elements, the 3rd metal most probable of the catalyzer using is in the method for the invention with higher than 0, and for example+1 ,+2 etc. oxidation state exists with the form of oxide compound, salt, sulfide, hydride etc.

Will be appreciated that, the first metal, the second metal and the 3rd metal may not be elemental metals purely, but can for example be at least in part another kind of form, such as salt, oxide compound, muriate, hydride, sulfide, carbonate etc., even if the composition of catalyzer represents with elemental metals for first, second, and third metal.

The dehydrogenation catalyst of the activation using in method of dehydrogenating of the present invention also comprises inorganic carrier.For example, catalysis dehydrogenation agent carrier can comprise one or more in silicon-dioxide, aluminum oxide, silicate, aluminosilicate, zirconium white, carbon or carbon nanotube.Alternatively, carrier can comprise inorganic oxide, for example, in silicon-dioxide, titanium dioxide and zirconium dioxide one or more.Carrier can comprise or not comprise binding agent.The impurity may reside in support of the catalyst is that for example sodium salt is as water glass, and it can exist with any amount within the scope of 0.01wt%-2wt%.Suitable silica supports is for example described in that on January 12nd, 2007 submits to and name is called in the PCT publication No. WO/2007084440A1 of " silica supports ", and this application is incorporated herein by reference for this object.

Dehydrogenation catalyst can comprise have by ASTM standard testing D4284 describe pressure mercury porosimetry measure pore volume and the silica supports of mean pore sizes.Silica supports can have the surface-area of measuring by ASTM D3663.Pore volume can be in the scope of 3.0cc/ gram of about 0.2cc/ Ke-Yue.Mean pore sizes is in the scope of approximately 10 Ai-Yue 2000 dusts, or in the scope of 20 dust-500 dusts; And surface-area (m ²/ gram) at 10-1000m ²/ gram scope in, or at 20-500m ²/ gram scope in.Carrier can comprise or can not comprise binding agent.

For example, one or more liquid compositions that dehydrogenation catalyst precursor can comprise by being used in the first metal or its precursor, the second metal or its precursor and/or the 3rd metal or its precursor and optional mineral alkali component or precursor in liquid vehicle (as water) in succession or are simultaneously processed carrier (for example, by dipping) and are prepared.Organic dispersing agent can be added in each liquid vehicle and with help, one or more metal components are uniformly applied on carrier.Suitable organic dispersing agent comprises amino alcohol and amino acid (for example arginine).For example, organic dispersing agent can be present in described liquid composition with the amount between 1.0wt% and the 20wt% of described liquid composition.

Catalyzer can comprise the first metal and the second metal, but do not basically contain the 3rd metal, and catalyst precursor can flood by order (wherein the second metal precursor being applied on carrier before described 6-10 family metal component) and prepares.

After processing with liquid composition, can be in one or more stages, conventionally the temperature heating inorganic carrier time of 0.5-50 hour of 100 ℃-700 ℃, to carry out one or more in following operation: (a) remove liquid vehicle; (b) metal component is converted into the form of catalytic activity; (c) organic dispersing agent is decomposed.Described heating can be carried out in oxidizing atmosphere (as air).Therefore obtain catalyst precursor.

Catalyst precursor can comprise the first metal that is one or more oxidation state, for example, be the form of simple substance, salt, oxide compound etc.Pass through to contain O at air or other at catalyst precursor ₂in situation prepared by the calcining step in atmosphere, at least a portion of the first metal, optional second and the 3rd metal is the form of oxidation.For example, if catalyzer comprises Pt and Sn and silica supports, and precursor is by with Pt salt and Sn salt solution impregnation silica supports, is then dried and calcines and prepare in air, and catalyst precursor conventionally will comprise at least a portion and be PtO so ₂pt and at least a portion of form be SnO ₂the Sn of form.

In the method for the invention, in catalyst precursor is used in to dehydrogenation reaction before, make its experience activation step.Activation is included in and comprises H ₂reducing atmosphere in raise temperature heatable catalyst precursor.Reducing atmosphere can be pure hydrogen, or hydrogen and other reduction or rare gas element are as N ₂, CH ₄, C ₂h ₅, other hydrocarbon etc. mixture.Preferably, before contact catalyst precursor, for the H that contains of activation step ₂atmosphere is the gas stream being substantially dried, and it comprises H with the level that is no more than aa vol% ₂o, wherein aa can be 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.Dry H ₂logistics can play heatable catalyst precursor, dried precursor and blow away the H producing in reduction process before significant reduction occurs ₂o(is if any) effect.While at high temperature contact with hydrogen, the first metal (if being the oxidation state higher than simple substance) is by being reduced at least in part lower oxidation state, advantageously to simple substance state.For example, PtO ₂with PdO can be by H ₂be reduced at elevated temperatures Pt and Pd.The second metal (if being the oxidation state higher than simple substance) also can be reduced to lower oxidation state or simple substance state by the hydrogen in activation phenomenon and/or other component in activation step.But, if be present in catalyzer, for the periodic table of elements the 1st or 2 family's metals still in the oxidation state higher than simple substance, are oxide compound, salt or matrix material as the glass forming with inorganic carrier material or the form of the part of stupalith as the 3rd metal of K, Na, Ca etc. most probable in the catalyzer of activation.

In the process of activation step, catalyst precursor can be heated to target activation temperature from lower temperature (as room temperature)." activation temperature " used herein refers to that catalyst precursor is exposed to the top temperature of its at least 3 minutes (or at least 5 minutes, or at least 10 minutes, or at least 15 minutes, or at least 20 minutes) in reactivation process.In the process of heating steps, catalyst precursor is contained H ₂it is highly to wish that atmosphere is surrounded.The temperature heating rate of catalyst precursor can be in the scope of HR1 ℃/min-HR2 ℃/min, wherein HR1 can be 2,4,5,6,8,10,12,14,15, and HR2 can be 50,45,40,35,34,32,30,28,26,25,24,22,20 or 18.In the time that temperature is relatively low, for example, during lower than 100 ℃, first and/or second and/or the reduction of the 3rd metal may be slow in insignificant.The temperature of catalyst precursor is higher, and the speed of reduction reaction is higher.Therefore, (with the therefore reaching) top temperature of wishing that catalyst precursor exposes in activation step process is not less than T1 ℃, and wherein T1 can be 300,320,340,350,360,380,400,420,440,450.Highly wish that catalyst precursor is maintained in the temperature range from Tact-20 ℃ to Tact at least activation time length of D1 minute, wherein Tact is activation temperature, and D1 can be 10,15,20,25,30,45,60,75,90,120,150,180,240,300,360,420,480,540,600,660,720,780,840 or even 900.But, find, too high activation temperature and near maximum temperature the performance of the oversize temperature hold-time catalyzer to activation may be harmful to.Do not wish, by specifically theoretical constraint, to it is believed that the first and second metals that are simple substance form can move at very high temperature on the surface of inorganic carrier, agglomeration, to form large crystal, reduces the number in effective site on the catalyzer activating thus.Therefore, wish that catalyst precursor is exposed to activation temperature in activation step not higher than T2 ℃, wherein T2 can be 650,640,630,620,610,600,590,580,570,560,550,540,530,520,510 and even 500.Wish in heating steps and temperature hold-time catalyst precursor the be exposed to hydrogen atmosphere b% of time at least, wherein b can be 50,60,70,80,90,95,98 or even 100%.If when and catalyst precursor not by containing H ₂atmosphere is surrounded, highly wish it by other reduction or inert atmosphere as CH ₄, N ₂with their encirclement such as mixture.

Find in surprising mode, the activation temperature within the scope of 300 ℃-600 ℃ is particularly advantageous.Data presentation, is used the cyclohexane dehydrogenation of those catalyzer that activate under such high temperature to confirm that very high hexanaphthene is to benzene transformation efficiency, all selectivity of all not sacrificing.Therefore, preferably, the catalyst precursor that under activation temperature within the scope of Ta1 ℃-Ta2 ℃, activation contains Pt and Sn, wherein Ta1 and Ta2 can be 300,310,320,330,340,350,360,370,380,390,400,410,420,430,440,450,460,470,480,490,500,510,520,530,540,550,560,570,580,590 or 600 independently, as long as Ta1<Ta2.Although said temperature scope is all available for all useful catalyzer and is favourable, they are particularly preferred be applied to comprise Pt and/or Pd as the first metal and Sn as in bimetallic those catalyzer.

When near temperature hold-time activation temperature finishes, wish that at least y% of all the first and second metals in catalyst precursor has been reduced to the oxidation state of hope, for example simple substance state, wherein y can be 50,55,60,65,70,75,80,85,90,95,98,99,99.5,99.8 or even 99.9.In the situation that catalyzer comprises Pt and/or Pd, wish that at least the Pt of y% and/or Pd are reduced to simple substance Pt and Pd in the time that temperature hold-time finishes.In the situation that catalyzer comprises Sn, wish in the time that temperature hold-time finishes at least the Sn of z% be reduced to simple substance Sn, wherein z can be 40,45,50,55,60,65,70,75,80,85,90,95,98 or even 99.

In the time that temperature keeps step to finish, catalyst precursor major part is converted to the catalyzer of activation, and is preferably substantially all converted to the catalyzer of activation.In this stage, the catalyzer of activation can in higher or lower than or be substantially equal to the use temperature of catalyzer in method of dehydrogenating of activation.When needed correspondingly further heating or cooling after, then catalyzer can be put into described dehydrogenation reaction.Under any circumstance, highly wish that the catalyzer activating is protected with not oxidized before use., complete and the gap (if any) of dehydrogenation reaction between starting in activation for this reason, wish by with the atmosphere adopting in activation step identical or different containing H ₂the catalyzer of atmosphere or inert atmosphere protection activation.In same reactor, carry out activation step and dehydrogenation step is particularly advantageous, this has eliminated the catalyzer of activation has been transferred to the needs of dehydrogenation reactor and the complicacy causing.

The dehydrogenation catalyst of activation can have the oxygen chemisorption value (ocv) that is greater than ocv1%, and wherein ocv can be 5,8,12,15,18,20,22,25,28 or 30.As used in this article, the oxygen chemisorption value (ocv) of special catalyst is the measuring of metal dispersion on catalyzer, and is defined as:

The oxygen chemisorption value of mentioning is herein used Micrometrics ASAP2010 physisorption analyser to measure as follows.About 0.3-0.5 gram catalyzer is put into Micromeritrics instrument.Under mobile helium, catalyzer is warmed up to 250 ℃ and keep 5 minutes with the speed of 10 ℃/min from envrionment temperature (18 ℃).After 5 minutes, this sample is placed 30 minutes at 250 ℃ under vacuum.After 30 minutes vacuum, sample is cooled to 35 ℃ and keep 5 minutes with the speed of 20 ℃/min.35 ℃ 0.50 and 760mm Hg between collect oxygen and hydrogen thermoisopleth with increment.The linear portion of this curve is extrapolated to zero pressure, provides total (merging) absorption picked-up.

Preferably, the α value of dehydrogenation catalyst is 0-10,0-5 and 0-1.Compared with standard catalyst, the α value of carrier is the approximate indication of the catalytic cracking activity of catalyzer.Alpha test provides the relative rate constant (speed/catalyst volume/unit time of hexane conversion) of detecting catalyst with respect to standard catalyst, and described standard catalyst is taken as α value (rate constant=0.016s of 1 ^-1).Alpha test is described in U.S. Patent number 3,354, and 078 and J.Catalysis, 4,527 (1965); 6,278 (1966); In 61,395 (1980), for the described document of description reference of described test.Experiment condition for the test of measuring the α value that this specification sheets mentions comprises the steady temperature of 538 ℃, and J.Catalysis, the changeable flows of detailed descriptions in 61,395 (1980).Alternatively, α value can be in the scope of v α 1 to v α 2, and wherein v α 1 can be 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; With v α 2 can 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, as long as v α 1<v α 2.

Use the dehydrogenation catalyst of activation prepared by method of the present invention can be used to the first composition that comprises any hydrocarbon material that can dehydrogenation as contained those dehydrogenations of cyclic hydrocarbon compound.Preferably, the first composition comprises cyclic hydrocarbon compound, for example cyclopropane, tetramethylene, pentamethylene, hexanaphthene, suberane, cyclooctane, cyclododecane, cyclodecane, ring undecane and their derivative (for example alkylating derivative).The first composition can comprise the saturated cyclic hydrocarbon (for example hexanaphthene) of C1wt%-C2wt%, wherein C1 and C2 can be 0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1.0,3.0,5.0,8.0,10.0,15.0,20.0,25.0,30.0,35.0,40.0,45.0,50.0,55.0,60.0,70.0,75.0,80.0,85.0,90.0,95.0,98.0 independently, as long as C1<C2, wherein the gross weight meter of the first composition of the catalyzer of percentage ratio based on the described activation of contact.

In the situation that the first composition comprises six-membered cyclic hydrocarbon as hexanaphthene, it can further comprise one or more five-ring cyclic hydrocarbon (for example pentamethylene with the concentration within the scope of C3wt%-C4wt%, methylcyclopentane, ethyl cyclopentane etc.), gross weight meter based on described the first composition, wherein C3 and C4 can be 0.01 independently, 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, as long as C3<C4.

The first composition can be further with the concentration within the scope of C5wt%-C6wt% comprise can not dehydrogenation component, for example aromatic hydrocarbon, gross weight meter based on described the first composition, wherein C5 and C6 can be 5,8,10,15,20,25,30,35,40,45,50,55,60,65,70,75,80,85,90 or 95 independently, as long as C5<C6.Aromatic hydrocarbon can be for example benzene.Aromatic hydrocarbon can be identical with the product of the method for dehydrogenating of use activation dehydrogenation catalyst of the present invention.In the first composition can not dehydrogenation component can be as maintaining temperature and the speed of reaction needed thermal barrier of dehydrogenation reaction in hope.

The suitable condition of dehydrogenation step comprises the temperature of 100 ℃-1000 ℃, the atmosphere pressures of 100kPa gauge pressure-7000kPa gauge pressure (kPag), and 0.2hr ^-1-50hr ^-1weight hourly space velocity.

Preferably, the temperature of method of dehydrogenating can be Td1 ℃-Td2 ℃, and wherein Td1 can be 100,150,200,250,300,350,400,450,500,550,600; With Td2 can be 1000,950,900,850,800,750,700,650,600 or 550, as long as Td1<Td2.

Preferably, the pressure of method of dehydrogenating can be P1kPa (gauge pressure)-P2kPa (gauge pressure), and wherein P1 and P2 can be 0,100,150,200,250,300,350,400,450,500,600,700,800,900,1000,1500,2000,2500,3000,4000,5000,6000 or 7000 independently.

Structure of reactor for method of dehydrogenating can comprise the one or more fixed-bed reactor that contain the solid catalyst with dehydrogenation functionality.Using the per pass conversion of the saturated cyclic hydrocarbon (for example hexanaphthene) of catalyzer of the present invention can be con% at least, and wherein con can be 70,75,80,85,90,95 or even 98.Reaction is absorbed heat.Conventionally,, due to endothermic effect, the temperature of reaction mixture declines when through catalyst bed.Can outside heat be supplied to the reactant in reactor by one or more interchanger, to keep the temperature of reactant in the scope of hope.The temperature of response composite declines and is then raise by interchanger when through each catalyst bed.Preferably, use 1-5 bed, during wherein through each catalyst bed, temperature declines 30 ℃-100 ℃.Preferably, last in series moved under the temperature out of first height of bed than in series.

Although the inventive method can for example, for example, be used with comprising saturated cyclic hydrocarbon (hexanaphthene) and optionally comprise together with any composition of 5-membered ring compounds (methylcyclopentane), described method can be used as the part of benzene to the integrated approach of phenol conversion especially.In such integrated approach, first by any routine techniques (be included in acid catalyst as zeolite beta or MCM-22 types of molecules sieve exist under with tetrahydrobenzene by benzene alkylation, or by benzene oxidative coupling being become to biphenyl then by biphenyl hydrogenation) benzene is changed into phenylcyclohexane.But, in practice, generally produce by the following method phenylcyclohexane: benzene is contacted under hydroalkylation condition with hydrogen under hydroalkylation catalyzer exists, and benzene experiences following reaction (1) and produces phenylcyclohexane (CHB) thus:

Hydroalkylation can carry out in the reactor configuration of wide region (comprising fixed bed, slurry-phase reactor and/or catalytic distillation tower).In addition, hydroalkylation can carry out or carry out in multiple reaction zones in single reaction district, wherein introduces by stages reaction to major general's hydrogen.Suitable temperature of reaction is 100 ℃-400 ℃, for example, be 125 ℃-250 ℃, and suitable reaction pressure (gauge pressure) is 100-7 simultaneously, and 000kPa, for example, be 500kPa-5,000kPa.The desired value of the mol ratio of hydrogen and benzene between 0.15:1 and 15:1, for example, between 0.4:1 and 4:1, for example 0.4 and 0.9:1 between.

The catalyzer adopting in hydroalkylation normally comprises the molecular sieve of above-described MCM-22 type and the dual-function catalyst of hydrogenation metal.

Any known hydrogenation metal can be used in hydroalkylation catalyzer, although suitable metal comprises palladium, ruthenium, nickel, zinc, tin and cobalt, wherein palladium is particularly advantageous.The amount of the hydrogenation metal existing in catalyzer can be in the scope of the 0.05wt%-10wt% of described catalyzer, for example, in the scope of 0.1wt%-5.0wt%.In the situation that MCM-22 types of molecules sieve is aluminosilicate, the amount of hydrogenation metal is the mol ratio that makes aluminium in molecular sieve and hydrogenation metal is preferably 1.5 to 1500, for example 75 to 750, for example 100 to 300.

Hydrogenation metal can be by for example flooding or ion-exchange directly loads on MCM-22 types of molecules sieve.Preferably, at least 50wt%, for example 75wt% at least, and conventionally substantially whole hydrogenation metal be loaded on molecular sieving but with the compound inorganic oxide of molecular sieve on.Especially, find, by hydrogenation metal is loaded on inorganic oxide, be loaded on the catalyzer of equal value on molecular sieve with hydrogenation metal wherein compared with, the activity of catalyzer and its increase as the selectivity of phenylcyclohexane and dicyclohexyl benzene the product of hope.

The inorganic oxide using in so compound hydroalkylation catalyzer is not limited by narrow, and condition is that it is stable and inertia under the condition of hydroalkylation.Suitable inorganic oxide comprise the periodic table of elements the 2nd, 4, the oxide compound of 13 and 14 families, for example aluminum oxide, titanium dioxide and/or zirconium dioxide.

Hydrogenation metal can be deposited on inorganic oxide, for example, by dipping, then by compound to metallic inorganic oxide and molecular sieve.Conventionally, by common granulation (wherein by the mixture of molecular sieve and metallic inorganic oxide at high pressure (conventionally 350kPa-350,000kPa) lower formation pellet), or carry out Kaolinite Preparation of Catalyst matrix material by coextrusion (slurry of wherein forcing to make molecular sieve and metallic inorganic oxide, optionally passes through die head together with independent binding agent).If necessary, additional hydrogenation metal can be deposited on the catalyst composite of gained subsequently.Alternatively, molecular sieve, inorganic oxide and optional binding agent can be by compound and by for example extruding formation pellet, then by containing one or more one or more dispersions in described metal as solution impregnation pellet.

Catalyzer can comprise binding agent.Suitable binder material comprises synthetic or naturally occurring material and inorganic materials, for example clay, silicon-dioxide and/or metal oxide.The latter can be naturally occurring, or is the gelatinous precipitate of the mixture that comprises silicon-dioxide and metal oxide or the form of gel.The naturally occurring clay that can be used as binding agent comprises those of polynite and kaolin families, described family comprises the kaolin that becomes wilkinite and be commonly called Dixie, McNamee, Georgia and Florida clay, or wherein essential mineral composition is other clay of halloysite, kaolinite, dickite, nakrite or anauxite.Such clay can use by the raw state of original exploitation, or first experiences calcining, acid treatment or chemical modification.Suitable metal oxide binding agent comprises that silicon-dioxide, aluminum oxide, zirconium dioxide, titanium dioxide, silica-alumina, silica-magnesia, silicon-dioxide-zirconium dioxide, silica-thorium oxide, silica-beryllia, silica-titania and ternary composition are as silica-alumina-Thorotrast, silica-alumina-zirconium dioxide, silica-alumina-magnesium oxide and silica-magnesia-zirconium dioxide.

Although hydroalkylation step is high selectivity to phenylcyclohexane, the effluent of hydroalkylation will contain unreacted benzene charging conventionally, the product of some dialkyl group and other by product, especially hexanaphthene and methylcyclopentane.In fact in hydroalkylation, be, respectively 1-25wt% and 0.1-2.0wt% to the typical selectivity of hexanaphthene and methylcyclopentane.

Dehydrogenation reaction can be carried out all or part of output of hydroalkylation step.

Alternatively, hydroalkylation effluent is separated at least: (i) rich C6 composition; (ii) rest part of hydroalkylation effluent.For example, in the time that composition is described to the material (rich C6, rich benzene or rich hydrogen) of " richness " appointment, it refers to that the wt% of designated substance in composition is enrichment with respect to feed composition (inputting thing)." C ₆" material refers to any material that contains 6 carbon atoms generally.

In view of the similar boiling point of benzene, hexanaphthene and methylcyclopentane, so be difficult to by distillation these material separation.Therefore, can be by distill to separate the rich C that comprises benzene, hexanaphthene and methylcyclopentane from hydroalkylation effluent ₆composition.Then can make this rich C ₆composition experiences above-mentioned method of dehydrogenating, make at least a portion of the hexanaphthene in composition be converted to benzo and make at least a portion of methylcyclopentane be converted to the paraffins of straight chain and/or side chain, for example 2-methylpentane, 3-methylpentane, normal hexane and other hydrocarbon component are as isohexane, C ₅aliphatic cpd and C ₁-C ₄aliphatic cpd.Then dehydrogenation product composition can be fed to another separation system, be generally another distillation tower, dehydrogenation product composition is separated into rich benzene logistics and poor benzene logistics.Then rich benzene logistics can be recycled to hydroalkylation step, and poor benzene logistics can be used as the fuel for described method.For example, in the time that the composition about specific species is described to " poor " (poor benzene), the wt% that it refers in composition middle finger earnest kind is poor for feed composition (putting into the material in reactor).

At rich C ₆after the separation of composition, the rest part of hydroalkylation effluent can be fed to second column, for example, so that monocycle hexyl benzene product (phenylcyclohexane) is separated with any dicyclohexyl benzene and other heavy constituent.Depend on the amount of the dicyclohexyl benzene existing in reaction effluent, dicyclohexyl benzene and additional benzene carry out transalkylation reaction so that the generation of required monoalkylation material maximizes may wish.

Can in the transalkylation reactor separating with hydroalkylation device, (comprise that large pore molecular sieve is if the molecular sieve of MCM-22 type, zeolite beta, MCM-68 are (referring to U.S. Patent number 6 at suitable transalkylation catalyst with the transalkylation reaction of additional benzene, 014,018), zeolite Y, zeolite USY and mordenite are interior) on carry out.Large pore molecular sieve can have at least 7 dusts, for example the mean pore size of 7 dust-12 dusts.Transalkylation reaction carries out conventionally under the condition of at least part of liquid phase, and the condition of described at least part of liquid phase comprises the temperature of 100-300 ℃ suitably, and the pressure of 800kPa-3500kPa, based on combined feed total feed meter 1hr ^-1-10hr ^-1weight hourly space velocity, and benzene/dicyclohexyl benzene weight ratio of 1:1-5:1.Then transalkylation reaction effluent can be sent back to second column, to be recovered in the additional monocycle hexyl benzene product producing in transalkylation reaction.

After separation in second column, can be by phenylcyclohexane being changed into phenol and pimelinketone with the similar method of Hock method.In the method, first phenylcyclohexane is oxidized to corresponding hydroperoxide.This is by introducing oxygen-containing gas (as air) in the liquid phase that contains phenylcyclohexane and complete.Different from Hock method, because the oxidation of the atmospheric air of phenylcyclohexane is very slow in the situation that there is no catalyzer, therefore oxidation is carried out conventionally under catalyzer exists.

Be U.S. Patent number 6,720 for the suitable catalyzer of phenylcyclohexane oxidation step, 462(is incorporated herein by reference this patent for this object) in the cyclic imide that replaces of the N-hydroxyl described, for example HP, 4-amino-HP, 3-amino-HP, tetrabromo-HP, tetrachloro-HP, N-hydroxy chloride bacterium imide (N-hydroxyhetimide), N-hydroxyl cdear imide (N-hydroxyhimimide), N-hydroxytrimesic acid imide (N-hydroxytrimellitimide), N-hydroxybenzene-1, the sour imide of 2,4-tri-, N, N'-dihydroxyl (Pyromellitic Acid imide), N, N'-dihydroxyl (BP-3,3', 4,4'-tetracarboxylic imide), N-hydroxyl maleimide, pyridine-2,3-dicarboximide, N-hydroxy-succinamide, N-hydroxyl (tartrimide), N-hydroxyl-5-norbornylene-2,3-dicarboximide, outward-N-hydroxyl-7-oxabicyclo [2.2.1] heptan-5-alkene-2,3-dicarboximide, N-hydroxyl-cis-hexanaphthene-1,2-dicarboximide, N-hydroxyl-cis-4-tetrahydrobenzene-1,2-dicarboximide, N-hydroxyl naphthyl methylene imide sodium salt or N-hydroxyl-adjacent benzene disulfonyl imines.Preferably, catalyzer is HP.Another kind of suitable catalyzer is N, N', N " trihydroxy-tricarbimide.

These materials can use separately or use under radical initiator exists, and can be used as liquid phase homogeneous catalyst, or can be loaded on solid carrier so that heterogeneous catalyst to be provided.Conventionally, with the 0.0001wt%-15wt% of phenylcyclohexane, cyclic imide or N that the amount of for example 0.001wt%-5.0wt% is used described N-hydroxyl to replace, N', N " trihydroxy-tricarbimide.

Suitable condition for oxidation step comprises 70 ℃-200 ℃, for example temperature and the 50kPa-10 of 90 ℃-130 ℃, the pressure of 000kPa.Any oxygen-containing gas, preferably air, can be used as oxygenant.Reaction can be carried out in batch reactor or continuous flow reactor.Can add ealkaline buffer, to react with the acidic by-products that may form in oxidising process.In addition, can introduce water, this water can help dissolve basic compounds as sodium carbonate.

Phenylcyclohexane comprises the cracking of phenylcyclohexane hydrogen peroxide thing to another reactions steps in the conversion of phenol and pimelinketone, its easily by make hydroperoxide and catalyzer in liquid phase at 20 ℃-150 ℃, for example temperature and the 50kPa-2 of 40 ℃-120 ℃, 500kPa, for example, under the gauge pressure of 100kPa-1000kPa, contact is carried out.Preferably phenylcyclohexane hydrogen peroxide thing is diluted in the organic solvent (as methyl ethyl ketone, pimelinketone, phenol or phenylcyclohexane) to cracking reactionlessness to help heat extraction.Scission reaction can be carried out easily in catalytic distillation device.

Catalyzer for cleavage step can be homogeneous catalyst or heterogeneous catalyst.

Suitable homogeneous cleavage catalyst comprises sulfuric acid, perchloric acid, phosphoric acid, spirit of salt and tosic acid.Iron(ic) chloride, boron trifluoride, sulfurous gas and sulphur trioxide are also effective homogeneous cleavage catalyst.Preferred homogeneous cleavage catalyst is sulfuric acid, and preferred concentration is in the scope of 0.05wt%-0.5wt%.For homogeneous acid catalyst, preferably after cleavage step, carry out neutralization procedure.Such neutralization procedure generally includes with basic component and contacts, and removes rich salt face subsequently by decantation or distillation.

Comprise clay for the suitable heterogeneous catalyst of phenylcyclohexane hydroperoxide cracking, for example U.S. Patent number 4,870, the acid polynite silica-alumina clay of describing in 217, or the faujasite molecular sieve of describing in WO2012/145031.

The effluent of scission reaction comprises phenol and pimelinketone with equimolar amount substantially, and depends on needs, pimelinketone can be sold and maybe can be dehydrogenated to additional phenol.Any suitable dehydrogenation catalyst can be used to this reaction, for example variant of dehydrogenation catalyst described herein and catalyzer.Suitable condition for dehydrogenation step comprises the temperature of 250 ℃-500 ℃ and the pressure of 0.01atm-20atm (1kPa-2030kPa), for example pressure of the temperature of 300 ℃-450 ℃ and 1atm-3atm (100kPa-300kPa).

Now with reference to following non-limiting example and accompanying drawing, the present invention is more specifically described.

Embodiment

In an embodiment, will comprise Pt as the first metal, Sn is as the second metal, SiO ₂as inorganic carrier, and the catalyst precursor that does not basically contain the 3rd metal under differing temps at mobile H ₂there is lower activation in logistics, and then under the identical dehydrogenation condition of nominal, in tubular type downflow reactors, tests its activity in cyclohexane dehydrogenation.The method of Kaolinite Preparation of Catalyst precursor is disclosed in WO2012/134552, and the content of this application is incorporated herein by reference.

Operation A: rise to 400 ℃ and catalyzer is kept coming for 2 hours deactivated catalyst in described outlet temperature from room temperature by the speed with 40 ℃/h.Activation adopts pure hydrogen to carry out at 100psig (689kPa gauge pressure).

Process B: rise to 400 ℃ by the speed with 15 ℃/h from room temperature and carry out deactivated catalyst.Rise to 520 ℃ and catalyzer is kept under outlet temperature within 8 hours, further activate described catalyzer by the speed with 5 ℃/h from 400 ℃.Activation also adopts pure hydrogen to carry out at 100psig (689kPa gauge pressure).

In when activation, adopt the charging that comprises 10wt% hexanaphthene, 1wt% methylcyclopentane and the 89wt% benzene H in 420 ℃, 109psig (752kPa gauge pressure) and 4 ₂detecting catalyst under/hydrocarbon mol ratio.In Fig. 1 and Fig. 2, sum up the key results from Study of Activation, wherein 101 results that represent the catalyzer of preparing according to operation A, and 103 represent the result of the catalyzer of preparing according to process B.

As can see from Figure 1, compared with operation A, while using process B deactivated catalyst, catalyst activity approaches double.As can see from Figure 2, in situation, realize described improved activity not losing optionally.

Therefore, know from these embodiment are clear, 400 ℃ of above higher activation temperatures can be more favourable than 400 ℃ of following temperature.

Although with reference to specific embodiment, invention has been described and illustrate, and those skilled in the art will appreciate that, the present invention itself will amplify out many variants that needn't illustrate in this article.Therefore, so, with reference to should be only determining that according to appended claims true scope of the present invention makes.

The content of all reference of quoting is herein incorporated herein by reference.

The non-limiting embodiments of the inventive method comprises:

E1. method of dehydrogenating, the method comprises:

(1A) provide catalyst precursor, it comprises (i) inorganic carrier and (ii) the first metal that is selected from periodic table of elements 6-10 family metal of 0.05wt%-10.0wt%, the gross weight meter of percentage ratio based on described catalyst precursor;

(1B) by containing H ₂the catalyst precursor time of at least 15 minutes described in Temperature Treatment in atmosphere within the scope of 300 ℃-600 ℃, obtain the dehydrogenation catalyst activating; With

(1C) the first composition is contacted in dehydrogenation reactor under dehydrogenation condition with the dehydrogenation catalyst of described activation, obtain products of dehydrogenation reactions at least a portion of hexanaphthene is changed into benzo.

The method of E2.E1, wherein the temperature of step (1B) is in the scope of 420 ℃-550 ℃.

The method of E3.E1 or E2, wherein described the first composition in step (1C) obtains by following steps:

(1Ba) benzene is contacted under hydroalkylation condition with hydroalkylation catalyzer with hydrogen, to form the hydroalkylation mixture that comprises phenylcyclohexane, hexanaphthene, methylcyclopentane and benzene; With

(1Bb) obtained by least a portion of described hydroalkylation mixture: (i) the first composition, in its benzene and hexanaphthene, the concentration of at least one is higher than the concentration of phenylcyclohexane; (ii) the second composition, the concentration of its phenylcyclohexane is higher than the concentration of benzene and hexanaphthene.

The method of any in E4.E1-E3, further comprises:

(1D) at least a portion of the benzene in described products of dehydrogenation reactions is recycled to step (1Ba).

The method of any in E5.E1-E4, wherein the inorganic carrier of the described catalyst precursor in step (1A) comprises at least one in following: oxide compound, carbon and the carbon nanotube of the 3-5 family metal of silicon-dioxide, aluminum oxide, aluminosilicate, the periodic table of elements.

The method of any in E6.E1-E5, wherein at least a portion of the first metal described in the described catalyst precursor in step (1A) is in the oxidation state higher than zero.

The method of any in E7.E1-E6, wherein said the first metal comprises Pt and/or Pd.

The method of any in E8.E1-E7, wherein said catalyst precursor also comprises at least one in following: (iii) the second metal that is selected from the periodic table of elements the 14th family of 0.05wt%-5.0wt%; (iv) the 3rd metal that is selected from the periodic table of elements the 1st and 2 family's metals of 0.05wt%-10.0wt%.

The method of E9.E8, wherein said the second metal comprises Ge, Sn and/or Pb, and described the 3rd metal comprises Na and/or K.

The method of any in E10.E1-E9, in the catalyzer activating described in wherein in the time that step (1B) completes, at least described the first metal of 98wt% is simple substance state, the gross weight meter of percentage ratio based on described the first metal.

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

The method of any in E12.E1-E11, wherein step (1B) is included in the H that contains that the temperature within the scope of 300 ℃-600 ℃ is flowing ₂in atmosphere logistics, process described catalyst precursor.

The method of any in E13.E1-E12, the wherein described H that contains in step (1B) ₂atmosphere has the benzene concentration of 1wt% at the most, based on the described H that contains ₂the gross weight meter of atmosphere.

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

The method of any in E15.E1-E14, wherein in step (1B) afterwards but in step (1C) before, by not containing O ₂protective atmosphere protect the dehydrogenation catalyst of described activation.

The method of E16.E15, wherein said protective atmosphere comprises H ₂and CH ₄in at least one.

The method of any in E17.E1-E16, the temperature that wherein step (1B) is included within the scope of 450 ℃-550 ℃ heats described catalyst precursor at least 15 minutes.

The method of any in E18.E1-E17, wherein step (1B) is included in 400 ℃ of following temperature and heats described catalyst precursor with the first heating rate in the scope of 2 ℃-30 ℃/min, and/or heats described catalyst precursor with the second heating rate in the scope of 1 ℃-15 ℃/min in the temperature range of 400 ℃-600 ℃.

The method of any in E19.E1-E18, wherein step (1A) comprising:

(1A-1) provide described inorganic carrier;

(1A-2) with inorganic carrier described in the solution impregnation of the salt of described the first metal, to obtain impregnated carrier; Subsequently

(1A-3) the described impregnated carrier of the calcining of the temperature within the scope of 500 ℃-1000 ℃.

The method of any in E20.E1-E19, wherein step (1B) and (1C) all carry out in described dehydrogenation reactor.

The method of any in E21.E1-E19, wherein, in step (1Ba), described the first composition also comprises benzene and hydrogen.

The method of any in E22.E1-E21, wherein in step (1C), described the first composition comprises 0.01wt%-5.0wt% methylcyclopentane, the gross weight meter of percentage ratio based on described the first composition, and at least a portion of described methylcyclopentane is converted to paraffins.

The method of any in E23.E1-E22, wherein, in step (1C), described dehydrogenation condition is included in the temperature within the scope of 300 ℃-600 ℃.

E24. for the preparation of the method for phenol and/or pimelinketone, the method comprises:

(2A) produce phenylcyclohexane according to the method for any in E3-E23;

(2C) make at least a portion cracking of described phenylcyclohexane hydroperoxide to produce the cleavage reaction product that comprises phenol and pimelinketone.

E25. method of dehydrogenating, the method comprises:

(3A) provide catalyst precursor, it comprises (i) inorganic carrier and (ii) the first metal that is selected from periodic table of elements 6-10 family metal of 0.05wt%-10.0wt%, the gross weight meter of percentage ratio based on described catalyst precursor;

(3B) by containing H ₂described in Temperature Treatment in atmosphere within the scope of 300 ℃-600 ℃, catalyst precursor obtains the catalyzer of activation at least 15 minutes; With

(3C) make to comprise at least the first composition of the saturated cyclic hydrocarbon of 0.1wt% and the catalyzer of described activation contacts under dehydrogenation condition, become undersaturated cyclic hydrocarbon to transform at least a portion of described saturated cyclic hydrocarbon, the gross weight meter of percentage ratio based on described composition.

The method of E26.E25, the inorganic carrier of wherein said catalyst precursor comprises at least one in following: the oxide compound of silicon-dioxide, aluminum oxide, aluminosilicate and periodic table of elements 3-5 family metal.

The method of E27.E25 or E26, at least a portion of described the first metal in wherein said catalyst precursor is in the oxidation state higher than zero.

The method of any in E28.E25-E27, wherein said the first metal comprises Pt and/or Pd.

The method of any in E29.E25-E28, wherein said catalyst precursor also comprises at least one in following: (iii) the second metal that is selected from the periodic table of elements the 14th family of 0.05wt%-5.0wt%; (iv) the 3rd metal that is selected from the periodic table of elements the 1st and 2 family's metals of 0.05wt%-10.0wt%.

The method of E30.E29, wherein said the second metal comprises Ge, Sn and/or Pb, and described the 3rd metal comprises Na and/or K.

The method of any in E31.E25-E30, in the catalyzer activating described in wherein in the time that step (3B) completes, at least the first metal of 98wt% is simple substance state, the gross weight meter of percentage ratio based on described the first metal.

The method of any in E32.E25-E31, wherein said containing H ₂atmosphere has the benzene concentration of 1wt% at the most, based on the described H that contains ₂the gross weight meter of atmosphere.

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

The method of any in E34.E25-E33, wherein in step (1B) afterwards but in step (1C) before, by not containing O ₂protective atmosphere protect the dehydrogenation catalyst of described activation.

The method of E35.E34, wherein said protective atmosphere comprises H ₂and CH ₄in at least one.

The method of any in E36.E25-E35, wherein step (3B) is included in the H that contains that the temperature within the scope of 300 ℃-600 ℃ is flowing ₂in atmosphere logistics, process described catalyst precursor.

The method of any in E37.E25-E37, the temperature that wherein step (3B) is included within the scope of 450 ℃-550 ℃ heats described catalyst precursor at least 15 minutes.

The method of any in E38.E25-E37, wherein step (3B) is included in 400 ℃ of following temperature and heats described catalyst precursor with the first heating rate in the scope of 2 ℃-30 ℃/min, and/or heats described catalyst precursor with the second heating rate in the scope of 1 ℃-15 ℃/min in the temperature range of 400 ℃-600 ℃.

The method of any in E39.E25-E38, wherein step (3A) comprising:

(3A-1) provide described inorganic carrier;

(3A-2) with inorganic carrier described in the solution impregnation of the salt of described the first metal, to obtain impregnated carrier; Subsequently

(3A-3) the described impregnated carrier of the calcining of the temperature within the scope of 500 ℃-1000 ℃.

The method of any in E40.E25-E39, wherein step (3B) and (3C) carry out in same container.

The method of E41.E40, wherein, in step (3B) with (3C), protects the catalyzer of described activation so that it is not exposed to oxygen.

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

The method of any in E43.E25-E42, wherein, in step (3C), described composition comprises methylcyclopentane, and at least a portion of described methylcyclopentane is converted to paraffins.

The method of any in E44.E25-E43, wherein, in step (3C), described dehydrogenation condition is included in the temperature within the scope of 300 ℃-600 ℃.

The method of any in E45.E25-E44, wherein said the first metal is Pt and/or Pd.

Claims

1. method of dehydrogenating, the method comprises:

(1A) provide catalyst precursor, it comprises (i) inorganic carrier and (ii) the first metal that is selected from periodic table of elements 6-10 family metal of 0.01wt%-10.0wt%, the gross weight meter based on described catalyst precursor;

2. the process of claim 1 wherein that the temperature of step (1B) is in the scope of 420 ℃-550 ℃.

3. the process of claim 1 wherein that described the first composition in step (1C) obtains by following steps:

4. the method for claim 3, further comprises:

5. the method for any one in aforementioned claim, wherein said the first metal comprises Pt and/or Pd.

6. the method for any one in aforementioned claim 1-4, wherein at least a portion of the first metal described in the described catalyst precursor in step (1A) is in the oxidation state higher than zero.

7. the method for any one in aforementioned claim 1-4, wherein said catalyst precursor also comprises at least one in following: (iii) the second metal that is selected from the periodic table of elements the 14th family of 0.01wt%-5.0wt%; (iv) the 3rd metal that is selected from the periodic table of elements the 1st and 2 family's metals of 0.01wt%-10.0wt%.

8. the method for claim 7, wherein said the second metal comprises that Sn and described the 3rd metal comprise K.

9. the method for any one in aforementioned claim 1-4, wherein in step (1B), described containing H ₂atmosphere comprises at least hydrogen of 90wt%.

10. the method for any one in aforementioned claim 1-4, wherein step (1B) is included in the mobile H that contains ₂in atmosphere logistics, process described catalyst precursor.

The method of any one in 11. aforementioned claim 1-4, the wherein described H that contains in step (1B) ₂atmosphere has the benzene concentration of 1wt% at the most, based on the described H that contains ₂the gross weight meter of atmosphere.

The method of any one in 12. aforementioned claim 1-4, wherein also comprises hydrogen at the first composition described in step (1Bb), and described in step (1B), is containing H ₂atmosphere is described the first composition.

The method of any one in 13. aforementioned claim 1-4, wherein in step (1B) afterwards but in step (1C) before, by not containing O ₂protective atmosphere protect the dehydrogenation catalyst of described activation.

14. the method for claim 13, wherein said protective atmosphere comprises H ₂and CH ₄in at least one.

The method of any one in 15. aforementioned claim 1-4, wherein step (1A) comprising:

(1A-1) provide described inorganic carrier;

(1A-2) with inorganic carrier described in the solution impregnation of the salt of described the first metal, to obtain impregnated carrier; With

(1A-3) the described impregnated carrier of the calcining of the temperature within the scope of 300 ℃-1000 ℃.

The method of any one in 16. aforementioned claim 1-4, wherein step (1B) and (1C) all carry out in described dehydrogenation reactor.

The method of any one in 17. aforementioned claim 1-4, wherein, in step (1Bb), described the first composition comprises benzene and hydrogen.

The method of any one in 18. aforementioned claim 1-4, wherein in step (1C), described the first composition comprises 0.01wt%-5.0wt% methylcyclopentane, the gross weight meter based on described the first composition, and at least a portion of described methylcyclopentane is converted to paraffins.

The method of any one in 19. aforementioned claim 1-4, wherein, in step (1C), described dehydrogenation condition is included in the temperature within the scope of 300 ℃-600 ℃.

20. prepare the method for phenol and/or pimelinketone, and the method comprises:

(2A) described the second composition production phenylcyclohexane by acquisition in step (1Bb) according to the method for any one in aforementioned claim 3-19;

(2B) be oxidized at least a portion of described phenylcyclohexane, to obtain the oxidation reaction product that comprises phenylcyclohexane hydroperoxide; With