CA1139787A - Method for producing 3-alkylphenols and 1,3- dihydroxybenzene - Google Patents

Abstract

ABSTRACT

This invention describes a four-step process for preparing 3-alkylphenols and 1,3-dihydroxybenzene comprising the alkylation of benzene or a monoalkyl-benzene followed by the selectove reaction of the 1,4-isomer of the alkylation product in the presence of a specified type of shape selective zeolite to obtain the 1,3-isomer in excess of equilibrium. Subsequent oxidation and acid catalyzed rearrangement results in a significant yeild of 1,3-dihydroxybenzene or 3-alkyl-phenol.

F-COO?(0026 ? ?27)

Description

~3~ 7 This in~ention relates to the production of aromatic alcohols1 and in particular to the selective production of 3-alkylphenols and 1,3-dihydroxybenzene.
The present invention provides a process for the production of hydroxybenzene compounds having sub-qtituents in the 1 and 3 positions on the benzene ring which comprise~ (A) alkylating an aromatic compound with an alkylating agent to produce an isomeric mixture o~
dialkylbenzene compounds; (B) contacting the isomeric mixture of dialkylbenzene compounds at a temperature of from 150C. to 800C. and a pressure of from 1 x 104 N/m2 to 1 x 107 N/m2 in the presence of a shape selective zeolite catalyst characterized by a constraint index of from 1 to 12 and by silica to alumina ratio of at least 12 to selectively react the 1,4-dialkyl i~omer of the dialkylbenzene oompounds to obtain a reaction mixture enriched with respect to the 1,3-dialkyl isomer, (C) oxidizirg the material enriched with respect to the 1,3-dialkylbenzene isomer to obtain the hydroperoxide thereof and (D) rearranging the hydroperoxide in the presence of an inorganic acid or ion exchange resin to yield a 1,3-disubstituted benzene having at least one hydroxy substituent thereon.
The present invention further provides that the alkylation of the aromatic compound may be carried at a temperature of from 100C. to 400C. and a pressure of from 1 x 105 N/m2 to 4 x 1 o6 N/m2 in the presence of a zeolite alkylation catalyst characterized by a silica to alumina ratlo of at least 12 and a constraint index of 1 to 12.

~ C~.

,:
,:
:

3~7~

The organic compound phenol has found many important industrial and medical applications over the years. It is ~aluable both as an intarmediate in the manufacture of other compounds and as a useful material in it~ own right. Moderr. manufacturing processes are described in detail in the monograph by A. Dierichs and R. Kubicka, Phenole und Basen, Vorkommen und Gewinnung I

(Akademie Verlag, Berlin, 1958).
3-Methylphenol is presently used in disinfectants, fumigants, photographic developers and explosives. Its potential as a phenolic resin for adhesives and other industrial products is large, particularly in view of some o~ the unique characteristics of this partlcular derivative of phenol, e.g., it is approximately three times more reactive than the parent phenol and has increased toughness, moisture resistance and reduced brittleness, all o~ which are very desirable properties. However, a major drawback to widened industrial applications for this compound has been its relatively high cost of manufacture. Japanese Patent No. 8929 (1955) to Maesawa and Kurakano describes a process for obtaining this compound from coal tar.
Its preparation from toluene is disclosed by Toland in U.S. Patent No. 2,760,991~ Another process, involving oxidation of o- or p-toluic acid, is described by Kaeding et al. in Ind. Eng. Chem. 53, 805 (1961).
However, separation of ths 3-methyl compound (bp 202C) from the mixed product stream, a necessary step in the heretofore practiced synthetic processes, is at best a very difficult and expensive undertaking.
1,3-Dihydroxybenzene has, like phenol, found numerous uses in both the medical and industrial areas as an intermediate in the synthesis of other materials and also as a useful substance by itself. A common ~ ~ 3~

method for manufacturing this useful compound has been by fusing 1,3-benzenedisulfonic acid with excess sodium hydroxide.
The process of the present invention provides a novel and useful route ~or the manufacture of both 3-alkylphenols and 1,3-dihydroxybenzene in substantially higher yields than obtained heretofore~ The present process is basically a four step process ~or producing the desired hydroxylated aromatic compound ~rom readily available raw materials such as benzene or alkylated benzene compounds. The first and 3econd 3tep3 in the process involve the production of the 1,3-dialkyl isomer of the benzene compound in high yield. Steps three and four comprise the oxidation of at least one of the alkyl substituents on the benzene rin~ followed by acid catalyzed rearrangement to produce the desired aromatic hydroxy compound and an alkyl ketone by-product.
The general reaction scheme eomprises:

Step (1) R ACH2~HA' ACH=CHA alkylat ~ ~ R

ACH2CHA' ACH2,CHA' ~ R R

L3978'7 Step (2) _ ective crackin~ ~ +
zeolite catalyst ACH2CHA' R
~+~

Step (3?

Ol-OH

ACH2CHA ' A-CH2-~-A ' ~ ~ 2 oxidati Step (4) O-OH

A-CH2-C,-A' ~ il ~ rearrangcment~ ~ ACH2CA~

where: R = alkyl h _ hydrogen or alkyl A'= hydrogen or alkyl , ,, . ' ' :

:~ ~L3~J~t7 The alkylation reaction, Equation (1), may be carried out in the presence of any known alkylation catalyst, many of which are conventionally classified as Lewis Acids and Bronsted Acids. When a known, conventional alkylation catalyst is utilized, the reactants are brought into contact therewith under conditions of temperature and pressure appropriate to that catalyst. In a particularly preferred embodiment, the alkylation catalyst comprises a novel type of crystalline zeolite catalyst characterized by a silica to alumina mole ratio of at least about 12 and a constraint index, as hereinafter defined, ~ithin the approximate range of 1 to 12. In such preferred embodiment, the olefin and aromatic compounds are brought into contact with the zeolite, most pre~erably the crystalline zeolite ZSM-5 or zeolite ZSM-12, at a temperature within the approximate range of from 100C
to 400C and a pressure of from 1 x 105 N/m2 to 4 x 1 o6 N/m2, preferably at 200C to 350C.
The selective cracking step to remove the undesirable 1,4-isomer, Equation (2), is accomplished by contacting, under selective cracking conditions, the isomeric mixture resulting from the foregoing alkylation step with a specified type of shape selective cry~talline zeolite catalyst having a silica to alumina ratio and constraint index as set out above, whereupon the 1,4-dialkylbenzene is selectively cracked or transalkylated to leave a product enriched in the 1,2-and 1,3-dialkyl isomers. The preferred selective cracking conditions comprise a temperature within the approximate range o~ about 100C to 500C and a pressure of approximately 1 x 104 N/m2 to 1 x 1 o6 N/m2 ~0.1 to 10 atmospheres). The preferred crystalline zeolite catalysts for this ~tep are ZSM-5, ZSM-11 and ZSM-23.

~3~3'~ '7 The last two steps of the synthesis consist of an oxidation, Equation (3), and an acid catalyzed rearrangement, Equation (4), which are analogous to the known commercial proceqs for the production of phenol (i.e., where R=H).
The four component steps of the process are discussed separately more fully belowO It ~ust be realized, of cou~se~ that the process of the pre~ent invention comprises the sum total of' its steps.

Step l - Alkylation of the aromatic compoun~:

R~ AC~CHA' ACN=CHA' alkylation~
catalyst ACH2CHA' ACH~CHA' ~ R
where: R = alkyl R
A = hydrogen or alkyl A'= hydrogen or alkyl.

The alkylation reaction is carried out by contacting the aromatic and olefinic compounds with an alkylation catalyst, which may be any of the con-ventional alkylation catalysts loosely classified as Lewis and ~ronsted acids. The conventional alkylation catalysts utilized herein may be any conventional catalyst designed to promote the alkylation of aromatic compounds with olefins. Such conventional catalysts include those which may be broadly defined as being ' ' ~:L39'7~37 Lewis and Bronsted acids. A partial l~sting of material~ known to catalyze alkylation of aromatics, which is not intended to be comprehensive of all the catalytic materials utilizable herein, would include:
AlCl3; AlCl3-HCl; AlCl3-H~0; AlBr3; FeCl3; SnCl4; TiCl4;
ZrCl4; BF3-Et20; PFs; H2S04; CH3S03H; ~mberlyst-15 ~ion exchange resin); P20s; H3P04/kieselguhr; SiO2-Al203;
BF3-Al203 and EtAlCl2-H20. A more complete expcsition of alkylation catalysts utilizable in the alkylation step o~ the present proces3, along with dlscussion of ~uitable reaction parameters ~or each, may be found in the treatise by G. A. Olah entitled Friedel-Crafts and Related Reaotions, Vol. II (published by Interscience, t963). Broadly speaking, ~uch catalyst~ will promote the alkylatior, reaction at temperatures ranging from -50C to ~200C and pressures of from ~ x 10-4 N/m2 to 1 o6 N~m2 (0~5-10 atm.) and greater. Preferred reaction conditions include temperaSures from 0C to 150C and ambient pressure.
In a particularly preferred embodiment, the alkylation catalyst utilized herein comprises a specific and novel type crystalline zeolite catalyst having unusual alkylation properties. This zeolite catalyst is characterized by a silica to alumina ratio of at least about 12 and a con traint index, as hereinafter more fully defined t Of from about 1 to about 12. Appropriate reaction conditions include a zeolite catalyst bed temperature between approximately 100C and 400C and a preqsure o~ from about 105 N/m2 to about 4 x 106 N~m2, 3~ although temperatures of between about 200C and 350C
and operating pressures between about 106 and 3.5 x 106 N/m2 are preferred. The reactants are most frequently paqsed across the catalyst 9 whioh comprises a bed of particulate material containing a crystalline zeolite catalyst as hereinafter defined, as a continuous strea~
at a feed weight hourly space velocity (WHSV) of between , , ., * Trademark , 3~37~7 about 1 and about 100. The latter WHSV is based upon the weight of the catalyst compositions, i~e~, the total weight of acti~e catalyst and binder therefor. Contact between the reactanis and the catalyst bed is preferably carried out at a WHSV of from 5 to 12.
The crystalline zeolites utilized herein are members of a novel class of zeolites which exhibits unusual properties. Although these zeolites have unusually low alumina contents, i.e., high silica to alumina ratios, they are very active even when the silica to alumina ratio exceeds 30. The activity is surprising since catalytic activity is generally attributed to framework aluminum atoms and/or cations associated with these aluminum atoms. These zeolites retain their crystallinity for long periods in spite of the presence o~ qteam at high temperature which induces irreversible collapse o~ the framework of other æeolites, e.g., of the X and A type. Furthermore, carbonaceous deposits, when formed, may be removed by controlled burning at higher than usual te~peratures to restore activity. These zeoliteq, used as catalysts, generally have low coke-~orming activity and therefore are conducive to long times on stream between regenerations by burning with oxygen-containing gas such as air.
An important characteristic of the crystal structure of this class o~ zeolites is that it provides constrained access to and egress from the intracrystalline free space by virtue of having an effective pore size intermediate between the small pore Linde A and the large pore Linde X, i.e., the pore windows of the structure have about a size such as would be provided by 10-membered rings of silicon and alumlnum atomq interconnected by oxygen atoms. It is to be understood, of course, that these rings are those formed by the regular disposition of the tetrahedra making up ~L3~
g the anionic framework of the crystalline zeolite, the oxyger atoms themselves being bonded to the silicon or aluminum atoms at the centers of the tetrahedra.
Briefly, the preferred type zeolites useful in this invention possess, in combination: a silica to alumina mole ratio of at least about 12 and a structure providing constrained access to the intracrystalline free space.
The silica to alumina ratio referred to may be determined by conventional analysis. This ratio is meant to repre3ent, as closely as possible, the ratio in the rigid anionic framework of the zeolite crystal and to exclude aluminum in the binder or in cationic or other form within the channels. Although zeolites with a silica to alumina ratio of at least 12 are useful, it is preferred to use zeolites having higher ratios of at least about 300 Such zeolites, after activation, acquire an intracrystalline sorption capacity for normal hexane which is greater than that for water, i.e., they exhibit "hydrophobic" properties. It is believed that this hydrophobic character is advantageous in the present invention.
The zeolites useful in this invention have an effective pore size such as to freely sorb nor~al hexane. In addition, the structure must provide constrained access to larger molecules. It is sometimes possible to judge from a known crystal structure whether Auch constrained access exists. For example, if the only pore windows in a crystal are formed by 8-membered rings of silicon and aluminum atoms, then access by molecules of larger cross-section than hexane is excluded and the zeolite is not of the desired type.
Windows of 10-membered rings are preferred, although in some instances excess puckering of the rings or pore blockage may render these zeolites ineffective~
Although it is thought that twelve-membered rings ~3L3~7l~7 --10-- , usually do not offer sufficient constraint to produce advantageous conversions~ it is noted that the puckered 12-ring structure of TMA offretite shows constrained access. Other 12-ring structures may exist which may be operative and it is not the intention to ~udge the usefulness herein of a particular ~eolite merely from theoretical structural considerations.
Rather than attempt to judge from cryqtal structure whether or not a zeolite possesses the necessary constrained access to molecules larger than normal paraffins, a simple determination o~ the "Constraint Index", as herein defined, may be made by pas~ing continuously a mixture of an equal weight of hexane and 3-methylpentane over a small samplel approximately one gram or less, of the zeolite at atmospheric pressure according to the following procedure. A sample of the zeolite, in the form of pellets or extrudate, is crushed to a particle si~e about that of coarse sand and mounted in a glass tube.
Prior to testing, the zeolite is treated with a stream of air at 540C for at least 15 minutes. The zeolite is then flushed with helium and the temperature adjusted to between 290C and 510C to give an overall corversion between 10% and 60~. The mixture of hydrocarbons is passed at 1 liquid hourly space velocity (i.e., 1 volume of liquid hydrocarbon per volume of zeolite per hour) over the zeolite with a helium dilution to give a helium to total hydrocarbon mole ratio of 4:1. After 20 minutes on stream, a sample of the effluent is taken and analyzed, most conveniently by gas chromatography, to determine the fraction remaining ~nchanged for each of the two hydrocarbons.

--1,1.-- , The "Constraint Index" is calculated as followY:
onstraint Index =~ o(fraction of hexane remai log10 (fraction of 3~-methylpentane remaining) The Constraint Index approximates the ratio of the cracking rate constants for the two hydrocarbons.
Zeolites suitable for the present invention are those having a Constraint Index of 1 to 12. Constraint Index (CI) values for some typical zeolites are:

Zeolite C~I.
ZSM 5 8.3 ZSM-11 8.7 ZSM-23 9.1 ZSM-35 4.5 TMA* Offretite 3.7 Beta 0.6 ZSM-4 0.5 H-Zeolon (mordenite) 0.4 REY 0.4 Amorphous Siliea-Alumina 0.6 Erionite 38 ~Tetramethylammonium The above-described Constraint Index is an important and even critical definition of those zeolites which are useful in the instant invention. The very nature of this parameter and the recited technique by which it is determined, however, admit of the possibility that a given zeolite can be tested under somewhat different conditions and thereby have different 7~'7 Constraint Indices. Constraint Index seems to vary somewhat with severity of operation (conversion) and the presence or absence of binders. Therefore, it will be appreciated that it may be possible to so select te~t conditions to establish more than one value in the range of 1 to 12 for the Constraint Index of a particular zeolite. Such a zeolite exhibits the constrained access as herein defined and is to be regarded as having a Constraint Index of 1 to 12. Also contemplated herein as having a Constraint Index of 1 to 12 and therefore within the scope of the novel class of highly siliceous zeolites are those zeolites which, when tested under two or more sets of conditions within the above specified ranges of temperature and conversion, produce a value of the Constraint Index slightly less than 1, e.g., 0.9, or somewhat greater than 12, e.g.~ 14 or 15, with at least one other value of 1 to 12. Thus, it should be understood that the Constraint Index value as uqed herein is an inclusive rather than an exclusive value.
That is, a zeolite when tested by any combination of conditions within the testing definition set forth hereinabove to have a Constraint Index of 1 to 12 i~
intended to be included in the instant catalyst definition regardle~s that the same identical zeolite tested under other defined conditions may give a Constraint Index value outside of the 1 to 12 range.
The class of zeolites defined herein is exemplified by ZSM-5, ZSM-11, ZSM 12, ZSM-23, ZSM-35, ZSM-38, and other similar materials. ZSM-5 is more particularly described in U.S. Patent No. 3,702,886, ZSM-11 in U~S. Patent No. 3,709,979, ZSM-12 in U.S.
Patent No. 3,832,449, ZSM-23 in U.S. Patent No.
4,076,842, ZSM-35 in U.S. Patent No. 4,016,245 and ZSM-38 in U.S. Patent No. 4,046,859.

" ' , The specific zeolites described, when prepared in the presenae of organic cations, are substantially catalytically inactive, possibly because the intracrystalline free space is occupied by organic cations from the forming solution. They may be activated by heating in an inert atmosphere at 540C for one hour, for example, followed by base exchange with ammonium salts followed by calcination at ~40C in airO
The pre~ence of organic cations in the forming solution may not be absolutely e~sential to the formation of this type zeolite; however, the presence of these cations does appear to favor the formation of this special class of zeolite. More generally, it is desirable to activate this type catalyst by base exchange with ammonium salts followed by calcination in air at about 540C for from about 15 minutes to about 24 hourq.
Natural zeolites may sometimes be converted to this type zeolite catalyst by various activation procedures and other treatments such as base exchange, steaming, alumina extraction and calcination, in combination~. Natural minerals which may be so treated include ferrierite, brewsterite, stilbite, dachiardite, epistilbite, heulandite, and clinoptilolite. The preferred crystalline zeolite~ are ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, and ZSM-38, with ZSM-5 and ZSM 12 being particularly preferred for the alkylation reaction of Step (1).
In a preferred aspect of this invention, the zeolites selected are those having a crystal framework density, in the dry hydrogen form, of not less than about 1.6 grams per cubic centimeter. It has been found that zeolites which satisfy all three of these criteria are most desired for several reasons. When hydrocarbon products or by-products are catalytically formed, for example, such zeolites tend to maximize the production of gasoline boiling range hydrocarbon products.

3 ~ 7 Therefore, the preferred zeolite~ of this invention are those having a Constraint Index as defined above of about 1 to about 12, a silica to alumina ratio of at least about 12 and a dried crystal density of not less than about 1.6 grams per cubic centimeter. The dry density for known structures may be calculated ~rom the number o~f silicon plus aluminum atoms per tOOO cubic Angstroms, as given, e.g., on Page 19 of the article on Zeolite Structure by W. M. Meier in "Proceedings of the Conference on Molecular Sieves, London, April 1967", published by the Society of Chemicàl Industry, London, 1968.
When the crystal structure is unknown, the crystal framework density may be determined by classical pyknometer techniques. For example, it may be determined by immersing the dry hydrogen form of the zeolite in an organic solvent which i~ not sorbed by the crystal. Or, the crystal density may be determined by mercury poro~imetry, since mercury will fill the interstices between crystals but will not penetrate the intracrystalline free space. It is possible that the unusual sustaired activity and stability of this class of zeolites is associated with its high crystal anionic framework density of not less than about 1.6 grams per cubic centimeter. This high density must necessarily be associated with a relatively small amount of free space within the crystal, which might be expected to result in more stable structures. This free space, however, is important as the locus of catalytic activity.
Crystal framework densities of some typical zeolites, including some which are not within the purview of this invention, are:

Void Framework Zeolite Volume Density _ Ferrierite 0.28 cc/cc 1.76 g/cc Mordenite .28 1.7 ZSM-5, -11 .29 1.79 ZSM-12 1.8 ZSM-23 2.0 Dachiardite .32 1.72 7. .32 1.61 Clinoptilolite .34 1.71 Laumontite .34 1.77 ZSM-4 (Omega) .38 1.65 Heulandite .39 1.69 p .41 1.57 Offretite .40 1.55 Levynite .40 1.54 Erionite .35 1.51 Gmelinite .44 1.46 Chabazite .47 1.45 A .5 1.3 Y .48 1.27 When synthesized in the alkali metal form, the zeolite is conveniently converted to the hydrogen form, generally by intermediate formation of the ammQnium form as a result of ammonium exchange and calcination of the ammonium form to yield the hydrogen form. In addition to the hydrogen form, other form.s of the zeolite wherein the original alkali metal has beep reduced to less than about 1.5 percent by weight may be used. Thus, the original alkali metal of the zeolite may be replaced by ~3 -16~

ion exchanse with other suitable ions of Groups IB to VIII of the Periodic Table, including, by way o~
example, nickel, copper, zinc, palladium, calcium or rare earth mstals.
In practicing the de~ired conversion process, it may be desirable to incorporate the above described crystalline zeolite in another material resistant to the temperature and other conditions employed in the process. Such matrix materials include ~ynthetic or naturally occurring Aubstances as well as inorganic materials such as clay, silica and/or metal oxides. The latter may be either naturally occurring or in the form of gelatinous precipitates or gels including mixtures of ~ilica and metal oxides. Naturally occurring clays which can be composited with the zeolite include those of the montmorillonite and kaolin families, which families include the sub-bentonites and the kaolins commonly known as Dixie, McNamee-Georgia and Florida clays or others in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite or anauxite.
Such clays can be used in the raw state as originally mined or initially subjected to calcination, acid treatment or chemical modification.
In addition to the ~oregoing materials, the zeolites employed herein may be composited with a porous matrix material, such as alumina, silica alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-berylia, silica-titania as well as ternary compositions, such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesla-zirconia. The matrix may be in the form of a cogel. The relative proportions of zeolite component and inorganic oxide gel matrix on an anhydrous basis may vary widely with the zeolite content ranging ..

~ ~ 3 from between about 1 to about g9 percent by weight and more usually in the range of about 5 to about 80 percent by weight o~ the dry composite.
The starting material in the Step (1) (alkylation) reaction is a monoalkylbenzene or benzene.
The choice of precisely which monoalkylbenzene compound to use as starting material is determined primar~ly by the desired end-product. For in tance: if one ~ishes to produce 3-methylphenol (m-cresol), the appropriate starting material would be ~ethylbenzene (toluene), while ethylbenzene would ultimately produce 3-ethyl~
phenol. Any monoalkylbenzene wherein the alkyl substituent contains from 1 to 20 carbon atoms is ~uitable ~or the purposes o~ the present proce~s, although for the manufacture of 3-alkylphenols the most pre~erred alkyl substituents are those having from 1 to 7 carbon atoms. As a general proposition, the followlng relationships of alkyl substituents on the benzene ring will be o~ value in choosing appropriate reactantq ~or the preqent process:
relative ease of dealkylation: (Step 2) -I_R > -IH > -~H2 > -CH3 R R
relative eaqe of oxidation: (Step 3) ~CH ~ -~H2 CH3 -~-R
R

J~

.. .

8~
-1~

Applying these relationships to the ~anufacture of an exemplary 3-alkylphenol, e,g. 3-methylphenol, it can be seen that a preferred combination of ~tarting materials might be methyl benzene and propylene to give a product of the Step (1) alkylation reaction comprising:

H / CH3- ~-CH3 Using the above relationships, it will be clear that the methyl group will remain firmly ~ixed (i.e. will not dealkylate or oxidize) during the subsequent prooess steps except under the most severe of conditions. During the Step (2) reaction9 ~hich is more fully described hereinafter, the p~ isopropyl group will crack off of the ring relatively eaqily while the meta-isopropyl group will remain and be easily and selecti~ely oxidized to the hydroperoxide (Step (3)).
Monoalkyl benzenes having larger primary or secondary alkyI substituents, i.e. those having ~rom 3 to 5 carbon atom~, are Particularl~ suitable for the production of 1,3-dihydroxybenzene (resorcinol;
1,3-benzenediol). Theqe larger primary or secondary alkyl substituents are more eaqily oxidized in Steps ~3) and (4) of the in~tant process than are the smaller alkyl groups, although it should be borne in mind that any alkyl substituent, regardless of its size, can be oxidized by the reactlon of Steps (3) and (4) if the reaction conditions are of sufficient ~everity and the reaction permitted to proceed long enough. If the desired end product is 1,3-dihydroxybenzene, the most preferred starting material would be isopropylbenzene, ~ ~ 3 _~9_ which is then alkylated to produce diisopropylbenzene for subsequent oxidation to the desired dihydroxy compound. Similarly, if one wishes to start with benzene, the operating parameters of Step (1) may then be chosen to produce the dialkyl adduot (e.g.
diisopropylbenzene) which will subsequently yield the desired 1,3-dihydroxybenzene.
The olefinic component which comprises the alkylating agent o~ the reaction mixture of Step (1) may be any unsaturated hydrocarbon having from 2 to 20 carbon atoms and at least one olefinic linkage in the molecule. The double bond may be terminal, or it may be internal. Suitable alkylating agents include ethylene, propylene, butene (any isomer), pentene (any isomer), and cyclohexene. Also, compound~ which will, in the presence of the alkylation oatalysts defined herein, generate molecules having unsaturated carbon atoms suitable for the alkylation reaction are usable in the instant process. Compounds capable o~ generating unsaturated carbon atoms, for example are methanol, -ethanol, isopropyl alcohol, isopropyl ether, and cyclohexyl chloride.

Step 2 - Seleotive Cracking:

ACH2~HA' ACH~CHA' ~' ~ - R zeolite > ~ R
~ catalyst ACH2CHA ' (mixed isomers) where: R = alkyl A - hydrogen or alkyl A'= hydrogen or alkyl L3~ 7 Step (2) of the process comprises conkacting the reaction product of Step (1) with a particular crystalline zeolite catalyst, as herein defined, under suitable conversion or transalkylation conditions so as to selectively react (and thereby remove) the undesirable 1,4-isomer of the alkylated aromatic compound. As in Step (1), the instant reaction may be carried out in any of a number of physical process configurations, but the preferred embodiment comprises conducting the reaction in a fixed bed catalyst zone.
The term "suitable conver~ion or transalkylation conditions" is meant to describe those conditions of temperature, pressure and duration of contact between the reactants and zeolitic catalyst which will result in the selective reaction of 1,4-isomer of the alkylated aromatic constituent of the reaction feed mixture, in general (but not necessarily exclusive) preference to the 1,2--isomer or the 1,3 isomer thereof. It is contemplated that such conditions shall include a catalyst bed temperature of between approximately 100C and 500C, operating pressures of from about 104 N/m2 to about 1 o6 N/m2 (about 0O1 to 10 atmospheres) and WHSV of about 0.1 to about 50. Preferred conditions include a temperature of from about 300QC to about 450C, pressure between about 5 x 104 N/m2 to 5 x 105 N/m2 (0.5 to 5 atmospheres) and WHSV of about Q.5 to 5.
The crystalline zeolite catalysts of Step (2) are the same as those defined previously in regard to Step (1) and, as in Step (1), the preferred catalysts include those designated as ZSM-5j ZSM-11, ZSM-12, ZSM-23, ZSM-35 and ZSM-38. The crystalline zeolites ZSM-5, ZSM-11 and ZSM-23 are particularly preferred for the reaction of Step (2).

~39~7 In addition, for the purposes of Step (2), the crystalline zeolites employed may be modified prior to use by combining therewith a small amount, generally in the range o~ about 0.5 to about 40 weight percent, of a preferably difficultly reducible oxide, such as the oxides of phosphorus, boron or magnesiu~ or combinations thereo~ and also oxides of antimony. Modification of the zeolite with the desired oxide or oxide~ can readily be effected by contacting the zeolite with a solution of an appropriate compound of the elamert to be introduced, followed by drying and calcining to convert the compound to its 02ide form.
Representative phosphorus-containing compounds which may be used include derivatives of groups represented by PX3, RPX2, R2PX, R3P, X3P0, (X0)3P0, (X0)3P, R3P=0, R3P=S, RP02, RPS2, RP(O)(OX)2, RP(S)(SX)2, R2P(O)OX, R2P(S)SX, RP(OX)2, RP(SX)2, ROP(OX)2, RSP(SX)2, (RS)2PSP(SR)2, and (R0)2POP(OR)2, where R is an alkyl or aryl, such as a phenyl radical and X is hydrogen, R, or halide. These compounds include primary phosphines, RPH2, secondary phosphines, R2PH and tertiary phosphines, R3P, such as butyl phosphine; the tertiary phosphine oxides R3P0, such as tributyl-phosphine oxide, the tertiary phosphine sulfides, R3PS, the primary phosphonic acids, RP(O)(OX)2, and secondary phosphonic acids, R2P(O)OX, such as benzene phosphonic acid; the corresponding sulfur derivatives such as RP(S)(SX)2 and R2P(S)SX, the esters of the phosphonic acids such as diethyl phosphonate, (R0)2P(O)H, dialkyl alkyl phosphonates, (R0)2P(O)R, and alkyl dialkyl-phosphinates, (RO)P(O)R2; phosphinous acids, R2POX, such as diethylphosphinous acid, pri~ary, (RO)P(OX)2, qecondary, (R0)2POX, and tertiary; (R0)3P, phosphites;
and esters thereof such as the monopropyl ester, alkyl dialkylphosphonites, (RO)PR2, and dialkyl alkylphosphinite, (R0)2PR esters. Corresponding sulfur ~3~ 3t~ I

deri~atives may also be employed including (RS)2P(S)H, (FIS)2P(S)R, (RS)P(S)R2, R2PSX, (RS)P(SX)2, (RS)2PSX, (RS)3P, tRS)PR2 and (RS)2PR. Examples o~ phosphite esters include trimethylphosphite, triethylphosphite, diisopropylphosphite, butylpho~Dhite; and pyrophosphite.s such as tetraethylpyrophosphite. Tbe alkyl groups in the mentioned compounds contalD one to four car~on atoms.
Other suitable phosphorus-containing compounds ~O include the phosphorus halides such as phosphorus trichloride, bromide, and iodide, alkyl phosphorodi-chloridites, (RO)PC12, dialkyl pho phorochloridites, (RO)2PX, dialkylphosphinochloridites, R2P~l, alkyl alkylphosphonochloridates, (RO)(R)P(O)Cl, dialkyl phosphinochloridates, R2P(O)Cl and RP(O)C12. Applicable corresponding sulfur derivative~ include (RS)PC12, (RS)2PX, (RS)(R)P(S)Cl and R2P(S)Cl.
Preferred phosphorus~containing compounds include diphenyl phosphine chloride, trimethylpho~phite and phosphorus trichloride, phoc~horic acid, phenyl phosphine oxychloride, trimethylphosphite, diphenyl phosphinous acid, diphenyl phosphinic acid, diethylchlorothiophosphate, methyl acid pho~phate and other alcohol-P20s reaction products.
Representative magnesium-containing com-pounds include magnesium acetate, magnesium nitrate, magnesium benzoate, magne~ium propionate, magnesium

2-ethylhexoate, magnesium carbonate, magnesium formate, magnesium oxalate, magnesium amide, magnesium bromide, ~o magnesium hydride, magnesium lactate, magnesium laurate, magnesium oleate, magne~ium palmitate, magnesium salicylate, magnesium stearate and magnesium sulfide.
Representative boron-containing compounds include boric acid, trimethylborate, boron hydride, boron oxide, boron sulfide, butylboron dimethoxide, butylboronic acid, dimethylboric anhydride, , ... .

3~

hexamethylborazine, phenylboric acid, triethylborane, tetramethylammonium borohydride, triphenyl boron, and allylborate.
Antimony oxide may also be employed as a modifying component. The antimony oxide is present as Sb203 alone or in admixture with other antimony oxides with or without met~llic antimony or other antimony compounds being present. In all instances, regardless of the particular state of oxidation of the antimony, its content with respect to the zeolite is computed as if it were present as Sb203. Antimony derivatives which may be used include: the hydride SbH3; the halides SbX3, SbXs (X = F, Cl, Br, I); organic alkyl aDd aryl stibines and their oxides R3Sb, RsSb, RxSb=O (R - alkyl or aryl); halogen derivatives RSbX2, R2SbX, RSbX4, R2SbX3, R3SbX2, R4SbX; the acids H3SbO3, HSbO2, HSb(OH)6; organic acids such as RSbU(OH)2, ~2SbO-OH, all with R and X defined as above noted. Also included are organic ethers such as R2SbOSbR2; esters and alcoholates such as Sb(OOCCH3)3, Sb(OC4Hg)3, Sb(OC2Hs)3, Sb(OCH3)3;
and antimonyl salts as (SbO)S04, (SbO)N03, K(sbO)C4H406, NaSbO2 3H20 The zeolite to be modified is contacted with an appropriate compound of the element to be introduced.
Where the treating compound is a liquid, it may be used with or without a solvent. Any solvent relatively inert with respect to the treating compound and the zeolite may be employed. Suitable solvents include water and aliphatic, aromatic or alcoholic liquids. Where the treating compound is in the gaseous phase, it can be used by itself or in admixture with a gaseous diluent relatively inert to the treating co~pound and the zeolite, such as air or nitrogen or with an organic solvent such as octane or toluene.

~ ~L3g'~
-2~

Prior to reaching the zeolite with the treating compound, the zeolite may be dried. Drying can be effected in the presence of air. Elevated temperatures may be employed. However, the temperature should not be such that the crystal structure of the æeolite i5 destroyed.
Heating of the modified catalyst subsequent to preparation and prior to use is also preferred. The heating can be carried out in the presence of oxygen, for example, air. Heating can be at a temperature of about 150C. However, higher temperatures, e.g. up to 500C. are preferred. Heating is generally carried out for 1-5 hours but may be extended to 24 hours or longer.
While heating temperatures above 500C. can be employed, they are generally not necessary. At temperatures of about 1000C., the crystal structure of the zeolite tends to deteriorate.
The amount of modifier incorporated with the zeolite should be at least about 0.25 percent by weight.
However, it is preferred that the amount of modifier be at least about 1 percent by weight when the same is combined with a binder, e.g. 35 weight percent of alumina. The amount of modifiers can be as high as 25 percent by weight or ~ore depending on the amount and type of binder present. Preferably the amount of phosphorus, boron or magnesium oxide added to the zeolite i9 between 0.5 and 15 percent by weight.
Generally, the amount of Sb203 in the composite catalyst will be from 6 to 40 weight percent and preferably from 10 to 35 weight percent.
In some instances, it may be desirable to modify the crystalline zeolite by combining therewith two or more of the specified oxides. Thus, the zeolite may be modified by prior combination therewith of oxides o~ phosphorus and boron, oxides of phosphorus and magnesium or oxides of magnesium and boron. When such ~3~3~
-2~

modification technique is employed, the oxides may be deposited on the zeolite either sequentially or from a solution containing suitable compounds of the elements, the oxides of which are to be combined with the zeolite.
The amounts of oxides present in such instance are in the same range as specified above for the individual oxides, with the overall added oxide content being between 0.5 and about 40 weight percent.
Still another modifying treatm~nt entails steaming of the zeolite by contact with an atmosphere containing from 5 to 100 percent steam at a temperature of from 250 to 1000C for a period of between 0.25 and 100 hours and under pressures ranging from sub-atmospheric to several hundred atmospheres to reduce the alpha value thereof to less than 500, and preferably less than 20, but greater than zero.
Another modifying treatment involves precoking of the catalyst to deposit a ooating of between 2 and 75 and preferably between 15 and 75 weight percent of coke thereon. Precoking can be accomplished by contacting the catalyst with a hydrocarbon charge, e.g. toluene, under high severity conditions or alternatively at a reduced hydrogen to hydrocarbon concentration, i.e. 0 to 1 mole ratio of hydrogen to hydrocarbon, for a sufficient time to deposit the desired amount of coke thereon.
It is al~o contemplated that a combination of steaming and precoking of the catalyst under the above conditions may be employed to suitably modify the crystalline aluminosilicate zeolite catalyst.

3 ~ ~

Steps 3 and 4 - Oxidation and Rearrangement:

p OH
ACH2~HA ' A-CE~2~;-A

R ~ 2 oxidation~ ~ -R

~ rearrangememt OH O
~R + ACH2CA ' where: R = alkyl A = hydrogen or alkyl A' = hydrogen or alkyl The production of 3-alkylphenols and 1,3-dihydroxybenzene from the dialkylbenzene product9 of the above-described reactions iS analogous to the well-known process for the manufacture of phenol from isopropyl-benzene~ i.e., oxidation of one or both of the alkyl substituents to the corresponding hydroperoxide (Step 3) followed by acid cleavage of the peroxide to yield the aromatic alcohol and a dialkyl ketone (Step 4).
Reaction conditions ~or oxidation and rearrangement are similar to conditions for the commercial isopropylbenzene/phenol process. The oxidation reaction may be conveniently carried out either in batch or continUoUs operation at 75C up to 130C and at pressures ranging Up to about 106 N/m2 (10 atm.). An appropriate base~ preferably in aqueous solution~ iS used to maintain the pH of the reaction mixture at 7 to 9 to prevent decomposition of the ~ 3~7~ ~

hydroperoxide~ It is also desirable to add a radical initiator to the reaction mix to optimize the conversion rate and selectivity to the desired hydroperoxide.
Suitable radical initiators are well-known and the most preferable would be an organic hydroperoxide, particularly the 3ame aromatic hydroperoxide which is the desired product of the reaction. However, numerous other conventional radical initiators may suitably be employed (e.g., ~etal oxide catalysts MnO2)0 The source ,o o~ oxygen for the formation o~ the hydroperoxide is normally an oxygen-containing gas (e,g., pure 2 or air) which i3 brought into contact with the organic reactants ~y convenient means, such as by continuously bubbling the gas through the reaction mixture under reaction conditions.
After formation of the hydroperoxide, it i~
cleaved and rearranged to the aromatic alcohol by bringing it into contact with an inorganic acid, such as H2S04, preferably at elevated temperature. Alterna-tively, the hydroperoxide, in a suitable solvent, may be converted to the aromatic aloohol by ~ean~ of a cation exchange resin.
Prior to carrying out the rearrangement, it is pre~erable that the hydroperoxide be separated from the crude reactior, product mix, thereby enabling one to maximize the efficiency of the cleavage reaction and al~o to recycle the unreacted startir,g materials to increase the yield and e~ficiency of the hydro-peroxidation step. One suitable method o~ reco~ering the hydroperoxide would be by crystallization from the 3o crude product mix, but the preferred method comprises extraction with an aqueous base te.g., NaOH) followed by treatment of the salt with C02 to regenerate the hydroperoxide.

3~ 8~

Recycling of the unreacted starting materials, particularly after extraction of the hydroperoxide product, is preferred, espeoially in continuous operations. However, such recycling may result in an accumulation of essentially inert by-products which will act as diluents and thereby prove detrimental to the reaction. It is therefore of benefit to minimize the accumulation of undesirable by-products by withdrawing a portion of the recycle prior to return~ng it to the oxidation reactor. Another method of preventing or minimizing accumulation of by-products would be to conduct the oxidation process in a cascade consisting of several reactors.
Any or all of the component steps o~ the process of this invention may be carried out as a batch-type, semi continuous or continuous operation utilizing a fixed, fluidized or moving bed catalyst system. A preferred embodiment entails use of a fluidized catalyst zone wherein the reactants are passed concurrently or countercurrently through a moving fluidized bed of the catalyst. The fluidized bed a~ter use is conducted to a regeneration zone wherein coke is burned from the catalyst in an oxygen-containing atmosphere, e.g., air, at an elevated temperature, after which the regenerated catalyst is recycled to the con-version zone for further contact ~ith the aromatic reactants.
The process may be carried out in a system wherein the reactants are in either the liquid or the vapor state, and the mixture of olefinic and aromatic compounds may be substantially pure (i.e., contain no ~ubstantial quantity of hydrocarbon material other than the mixture of the olefinic and aromatic materials) or may contain substantial amounts of other hydrocarbon materials. The latter situation would exist when some or all of the feed stream for the instant process also , . ~

e3'~
-2~

comprises the e~luent stream of an earlier up~tream process, ~or instance a proce~s for the Commercial manufacture of olefinic or aromatic compound~. Al~o, the feed stream for the process of this invention may contain other inert materials as diluentq or solvents.
Suitable diluents include hydrogen, carbon dioxide, methane, ethane, propane and cyclohexane.
The following examples illustrate the process oP this invention.

STEP (1~ - ALKYLATION

Example 1 A mixture of toluene and ethylene was passed over microcrystalline HZSM-5 zeolite catalyst at 350C
and atmospheric pressure. Two runs were made wherein the molar ~eed ratios o~ the toluene to ethylene were 5 and 7.6 respectively. Alkylation occurred to produce a mixture of ethyltoluene isomers as shown in Table I.

s~

-3~

TABLE I
TOLUENE ALKYLATION WITH ETHYLENE
Catalyst: microcrystalline HZSM-5 Temperature: 3S0C
Pressure: atmospheric Ccnditions-.

WHSV: Toluene 7~0 10.5 C2H4 0.4 0.4 Molar Feed Ratio:
Toluene/C2H4 5 7.6 Conversion, Wt. %

Toluene 18.5 13.0 C2~4 91.4 90.5 Selectivity to products, wt.~

~_ra-Ethyltoluene27.2 28.8 meta-Ethyltoluene53.4 56.5 ortho-Ethyltoluene 13.4 12.0 other aromatics4.7 1.2 light gas 1.3 1.5 ao .o l oo .o `
~ . ~
'" : .

It is seen that, although the major product is the meta-isomer ~b.p. 161.3C), substantial amounts of the para-isomer (bop~ 1 62~0C) have also been produced.
It is evident that the close boiling points of these isomers would make it virtually impossible to make an acceptable separation by distillation. Howe~er, by selective cracking (i.e., Step 2), the para-isomer may be preferentially dealkylated (cracked) ~o produce toluene and light olefins leaving a mixture containing ortho and meta ethyltoluenes.

Example 2 A sample of microcrys~alline HZSM-5 was steamed for a period of 6 hours a~ 600C. A mixture comprising ethylene and toluene was passed over the catalyst at 350C and atmospheric pressure, with WHSV of 6.96 (toluene) and 0.54 (e~hylene). The products are summarized in Table II.

.

.~ , . ..

~ 3~

TABLE II

TOLUENE ALKYLATION WITH ETHYLENE

Catalyst: microcrystalline HZSM-5, steamed for 6 hours at 600C.

Temperature: 350C

Pressure: atmospheric Conditions WMSV: Toluene 6.96 C2H4 0.54 Conversion Wt. %

Toluene 11.1 C2H4 74.6 Selectivity to products, Wt. %

para-Ethyltoluene 40.3 meta-Ethyltoluene 58.8 ortho-Ethyltoluene O
Other aromatics 0.5 ~ight gas 0.4 100.0' ~ ~ , L39 ~ 7 -33~

The reaction produced primarily meta and ~ara-ethyltoluenes. By steaming the catalyst, the production of the ortho-isomer was suppressed to below the detection level (i.e., <0.1%). By selective cracking, it will be possible to now convert the para-isomer to its lower boiling fragmerlts, thereby permitting a separation of substantially pure meta-ethyltoluene by a relatively simple distillation.

Example 3:

The alkylation of toluene with ethylene was carried out at 300C and atmospheric pressure over HZSM-12 zeolite catalyst. The reactants, at a mole ratio of toluene to ethylene of 7/1, were passed over the oatalyst at a feed WHSV of 6. Approximately 60% of the ethylene was converted to alkylation product, with a 90% selectivity to ethyltoluene. The isomer distribution was 40%
ortho-ethyltoluene, 38~ meta-ethyltoluene and 22%
para ethyltoluene.

Example 4:

Using the HZSM-12 catalyst of Example 3~
toluene was alkylated with propylene (mole ratio = 7/1) at 250C and 500 p5ig. The feed WHSV was 6. Conversion of the alkylating agent (propylene) was in excess of 95 wt. % and the reaction was approximately g5~ selective to isopropyltoluene. Isomer distribution was 6%
ortho-isopropyltoluene, 62% meta-isopropyltoluene and 32% para isopropyltoluene.

~L~.39 d 8 7 Example 5:

Again using HZSM-12 zeolite as the alkylation catalyst, toluene was reacted with a mixture of 1-butene and 2-butene at 200C, The reaction was carried out at 300 psig and WHSV of 6, the reactants being at a mole ratio (toluene to butenes) of 7/1. At this temperature the butene conv~rsion was greater than 95~ to sec-butyltoluene, with isomer distribution being 40 meta and 60% para with no indication of the ortho isomer. This isomer ratio was reversed by increasing the reactor temperature to approximately 235C.

Ex a~p l e 6:

Temperature effect on the reaction was studied by alkylating toluene with propylene at 200, 230 and 26QC over HZSM-12 zeolite catalyst. In all cases the pressure was 500 psig with a molar feed ratio of 6.25/1 toluene/propylene. The feed rate for toluene was WHSV
5~7 and for propylene with WHSV was 0,4.
The propylene conversion at 230-240C
averaged 90-95% during a five day run. The selectivity to isopropyltoluene was 95~ throughout the temperature range. The effect of temperature on isomer distribution is seen in Table III.

3~7 -3~

o H

~; :g ~ ,~r~ ~ 00 ~ O
0 5 S-~
're ~ ~ ta o~
~r~ ~ ~J
~1 ~
H ~: ~
H ~ ~,1 ~ l o e~i, ~d oo ~) r' 1:~ a~ _o~
p:;~1 .~ ~ ~D ~ .
~ '::~
~ O
~ ~1 ~ .~
o o cl ~ ~ ~
E~ tn S ~ co ~_1 O ,_ C~l ~ O O O
t~ O ~ ~O
~ ~ C`

E~

Example 7:

A mix~ure comprising ethylbenzene and ethylene (~ole ratio = 4/1) was passed over a microcrystalline HZSM-5 zeolite catalyst at 250C and at 350C. The feed rates for each of the respective components of the feed stream were a IIHSV of 7.2 for the ethylbenzene and 0.5 for the ethylene in both runs. An alkylation reaction took place to produce a mixture of diethylbenzene isomers as shown in Table IVI

' .
:' '7~'~

TABLE IV

AL~YLATION OF ETHYLBENZENE WITH ETHYLENE

Catalyst: microcrystalline ~ZSM-5 zeolite Feed WHSV:
Ethylbenzene 7.2 Ethylene 0.5 Temperature,C 250 300 Conversion Wt %
7 ~

Ethylbenzene 20.3 31.0 Ethylene 85.7 81.2 Selectivity to Prod~cts, Wt.%

ortho-Diethylbenzene3.3 2.4 meta-Diethylbenzene46.7 56.1 para-Diethylbenzene27.5 27.8 Other aromatics 17.9 13.4 Light gas 4.6 0.3 - ~;13~
_ 4 -3~

It is evident from the close boiling points of the ethylbenzene isomers (ortho 183.4C; meta 181.1C;
para 183.8C) in the product stream that the conventional method o~ separation (i.e., fractional distillation) would not be praotical. However, by selective cracking the para-isomer may be preferentially dealkylated to produce lower boiling components which will thereafter permit isolation of the remaining ortho and meta-isomers.

Example 8:

Ethylbenzene was alkylated with propylene with 90% selectivity to isopropyl ethylbenzene (41~ para, 59%
meta and ortho)O The reaction was carried out at 200C
and atmospheric pressure, with an ethylbenzene/propylene mole ratio of 7/1 and a feed WHSV of 11 over 4.6 grams of HZSM-12 catalyst. The conversion of the alkylating agent was in excess of 95%.

Example 9 At 200C and atmospheric pressure, i~opropylbenzene (cumene) was alkylated with propylene utilizing 4.6 grams of HZSM-t2 catalyst. At a WHSV of 11 and a 7/1 mole ratio oP isopropylbenzene~propylene, greater than 95% of the propylene was converted with 95%
selectivity to dii~opropylbenzene. The isomer distribution was 60% para- and 40% meta. Increasing the reactor temperature to 235C resulted in a reversal of the meta/~ isomer ratio of 61/39. The ortho isomer was not found.

, . i . , ~3~ 7 -3~

Example 10:

In another reaction, analogous to Examples 4 and 6, toluene was alkylated with propylene at 240~ and 500 psig. The catalyst was HZSM-12 zeolite and the feed WHSV and mole ratio (toluene/propylene) were 5.06/0.40 and 5.83/1, respectively.
The reactlon resulted in a 15.9 mole ~
conversion of the toluene ~theoretical maximum = 17.2~) and a propylene conver~ion of 98.3-99.9 mole %.
Selectivity to isopropyltoluene was 91.9~ (based on toluene) with an iso~er distribution of 5.3% ortho, 63.8% meta and 30.8X R~

Step (2) Selective Crack~

Example 11:
.., : An isomeric mixture of isopropyltoluenes (mole ratio para/meta/ortho = 0.45/1.00/0.06) was brought into contact with a ZSM-5 zeolite catalyst which had been .~ prepared according to U.S. Patent No. 3,702,886 and steamed for one hour at 600C. The reactor was at 350C
and ambient pressure and the feed WHSV for the respective isomers was 1.50/3.36/0.20. The material balance for the reactants and product3 is given in Table V.

3~3~7~7 Q) ~ ~ O 0~ ~ O O ~
:~ ~ o ~- o ~r ~ . - o o ~ o ~r ~ ~ o J O V ~ O V

E-~ ~
J O

p, H
~ ~ E~l I ~ O
5~ ~: 0 3 ~ ~3 C~
~ ~ _ ~ ~ O
:a OOO~O~O OOOOOOOO
E-~ ~ ~D
J
J
C~

C ~: ~
~1 _I O
O O ~
~ ~ ~ ~ +
N C~ Cl. O O

1:~ C ~ O ~, C D Cl. C~ O
~/ O Oo~ C) o a~ a):~ o7 u~ H ~rl C~. C ~:: . H H I ~
e a~ I o ~a o O ~ ~ ~ C O J ~
m E~ ~a ~; O ¢ g ~

, : ' :

3~7~'7 From the data, it can be seen that all of the p~ isomer has been reacted to produce primarily toluene and olefins. The meta-isomer has remained substantially unreacted, with only 2.2% having been converted, while 36.5g of the ortho-isomer has been oracked.

Example 12:

A diisopropylbenzene (DIPB) mixture containing 68.9 wt. ~ meta isomer and 23.2 wt. % para isomer was passed over 4.0 grams of ZSM-5 zeolite catalyst in a quartz microreactor at a feed weight hourly space velocity (WHSV) of 4.3 and at temperatures of 300C to 400C. The results are shown in Table VI.

o . t-- ~ ~ ~ ~ a~
~ .
o 01 tn ~ N
O t~

~ O CJ~
æ .. ~ .... .
o ~ u~ a~ o ~ .
~ U~
;~ In C~
J
O
O o L~ J J a~
H o ~ 1 L~ o o I-t 1_~ O r~
:~
~ O
;: ~¢ æ
C~
'I;
~;
. ~ C~
.- C~ ~ ~ Ll'~ 5 00 .: ~ ~ I . . I I ~ .
~ Dq ~ ~ O ~ ~r H
E-~ a C) ~3 ~
: V~
:
.
.,~ ~
o .
.^ ~ . a~
U~
0 3 O m :E: 5 N ~
~ C H
C Q . ~ ~
1 ~ ~ ~ ~ I c J~ ~ ~ ~ C C ~ r~
0rl E3 ~I H a)~) Cl. I
O ~ ~ C~ :~ O~q 0 ,~ a)o 0 ~ ~~ 0 ~ ~a ~ O co ~ C~ a E3E J~ S, 1~ O C E~
0 a~ a)o ~ a~ t~ ~ J~
C.) ~ E-~ C_) O 1~3 Q. H O ~

3g~78~7 ~43-As can be seen, at 400C the aromatic e~fluent from the reactor contained 72O0 wt. % meta-DIPB and 3.1 wt. % para-DIPB. Thus the relative proportion of meta isomer in the DIPB has been increased from 74.8% to 95.9% by selecti~e cracking o~ the ~ isomer, yielding benzene as the major cracking product.
.

Example 13:

A mixture containing 52.0~ meta-ethyltoluene (ET), 47.5 wt. % para-ET and 0.5 wt. ~ ortho-ET was contacted with 4.0 grams of the Mg-P modified ZSM-5 catalyst in a flow microreactor at 430 500C and WHSV
of 0.9-6.2. The results are shown in Table VII.

.35~ ~ 8 ;i~
-44~

~ ~ ~ a: ~ <~I r C~ O
o ~o ~ o o ~ In cs~ o o~
t~

oc O ~o o CJ~
~ o ~ ~ o ~ ~ t~
:~
o E~

E~
H ~ O O ~ ~ r ~ ~
D O
æ
l:q H
E~ ~:

H oo Ll~ O Lt~ O
E-~ ~ I ~ I I I I o I
a>
~3 Q) U~

O
U~ O
Q) ~ ~ O O
~,~ 0 C C ~ O
C~ ~ c a~ a) :s ~1 0 3 0 ~ ~
0 ~ ~t 1~1 0 ~:: S
C ~ O O
O C O , O O ~) ~ 1 S..... O ~rl N D rl ~
.. :5 ~ ~ ~ ~ ~ ! C
a ~ s '1 ~ ~''I
O N :I H ~ ~ 1 ~-1 0 O ~ ~1 ~ ~ I I O
D~ ~ Q. tl~ a> o ~ ~ t~ .c ~ o ~ v~ e ~ ~ ~ ~ e o ~ ~ ~ ~ ,, C~ ~1 3 C.) O ~:L ~3 O ~:

, ~ :

' :'.
:: `
~ ' - ..

3~3'7~7

-4~

It is shown that the ~ meta isomer in ethyltoluene, at 500C and WHSV of 602 was increased from 52~ in the original feed to 89~ in the reactor effluent by selective cracking of the ~ isQmer.

Example 14 A mixture comprising 66.2 wt. ~
1-i3Opropyl-3-methylbenzene (meta~cymene3, 29.8 wt. %
1-isopropyl-4-methylbenzene (para-cymene), and 4.0 wt~ ~
1-isopropyl-2--methylbenzene (ortho-cymene~ was contacted with 4 grams of HZSM-11 catalyst which had been steamed at 600C for 3 hours at atmospheric pressure. The results are summarized in Table VIII.

TABLE VIII

SELECTIVE CRACKING OF CYMENES

Catalyst: HZSM-11 Feed~tock Temperature, C - 310 WHS~ 4 3 Composition, wt %
Toluene - 36.90 ortho-Cymene l~.0 4.53 meta-Cymene 66.2 39.27 para-Cymene 29.8 1.62 AromatiC C10 3.51 Other aromatics - 5.07 C2H4 _ 0 93 C3H6 ~ 1.6 C4Hg ~ 4.46 Other light gases - 2.28 % meta in Cymene 66.2 86.5 ' - - ., ~- ~

~ 39 7 ~

It is again seen from the above results that the para-i~omer has been selectively reduced with corresponding enrichment of the ortho- and meta-isomers in the cymene product fraction.

Example 15:

A feedstock containing 68.13 wt % 1-isopropyl-3-methylbenzene (meta-cymene), 27~54 wt ~ opropyl-4-methylbenzene (para-cymene), and 4~25 wt % 1-iso-propyl-2-methylbenzene (ortho-cymene) was passed through a catalyst bed of 1.0 gram of ZSM-23 zeolite catalyst in a flow rector at 300-400C and WHSV of 3.8. The products are shown in Table IX. In all runs, the meta isomer has been enriched relative to the ortho and isomers.

~L~L3~3 .
o ~ o ~ o 3 U`~

tn ~1 a- N
U~ O C~ ~ ~ ~ I O
Il~
~:
~ ~
X ~ ~ 1 3 H æ o c~ 3 3 ~ O
~: O ~O
. 1 c~ ~n m d E~ C~
P
~ ~0 L~
_~ ~ ~ ~ U~ _ E-:l 1 3 C N

o a~ 1 rr~ ~ ~
c~ C,~ ~0 a~ ~ c O ~ C~
.. ~o ~ a) ~ o 0 E o O ~ C
~ ~ ~ e e ~
3 S... u~ ~ ~ C 51 1 1 Q) ee ~ ~ ~ ~ E

E~ ~C O ~ ~ ~1 ~

. ' ~ , ' ' ':' :'~ ' . ~ , . .
:
, , 3~ 7 -4~

STEP t 3 ) - ûXIDATION

Example 16.

An isopropyltoluene mixture compri~ing 6~
ortho-isopropyltoluene and 92~ ~eta-isopropyltoluene (0%
_ .
p~ isomer and 2% other compounds) was prepared by ~elective cracklng (Step 2) ~ollowed by distillation.
E~ual volume~ of the freshly di~tilled i.~opropyltoluene and 2.5% aqueous NaHC03 were added to a one ~iter autoclave. Oxygen was bubbled through the reactor at 11 liter~ per hour, while the autoclave was maintained at 120-125C and 100 psi. A sample was periodically withdrawn ~or analysi3 of hydroperoxide formation. When no initiator was added to the reaction mixture, less than 3% meta~isopropyltoluene hydroperoxide was formed a~ter 10 hours of oxidation. When a small ~mount o~
isopropylbenæene hydroperoxide (total weight 0.8%) was added as an initiator, oxidation took place ~moothly.
The change in composition of the rea ~ Onl mixture with time is shown in Table X.

39'~

TABLE X

Products from Oxidation of meta-Isopropyltoluene Reaction time: O l hr.5 hrs.
Product Composition, %
meta-Isopropyltoluene89.7 87.7 69.4 ortho-Isopropyltoluene5.8 6.3 5.6 Other compounds in starting mixture 3.1 3.2 2.7 - 0.2 2.0 ~ _ 0,3 2.2 Isopropylbenzene hydroperoxide 0.8 0.7 0.3 meta-Isopropyltoluene hydroperoxide - 1.1 15.2 Other by-products - - 1.7 .

g7~'7 ~ ~ .

As can be ~een, the coneentration of the ortho-isopropyltoluene remained ~ubstantially constant during the oxidation. After 5 1/2 hours of oxidation, con~ersion of meta-isopropyltoluene was 25S and ~electi~ity to meta-isopropyltoluene hydroperoxide was 75~. This example demonstrates the ~elective oxidation of meta-i~opropyltoluene in a mixture containing both meta and ortho isomers.

STEP (4) - REARRANGEME~T
_ Example 17~

A 25 ml ~olution containing approximately 26%
meta-isopropyltoluene hydroperoxide was prepared by oxidat$on of meta-isopropyltoluene (Example 16). To this 901ution, 0, 5 ml of concentrated H2S04 was added dropwiQe to catalyze the rearrangement of the meta-isopropyltoluene to 3~methylphenol. The reaotion mixture was then heated to 65C for 1/2 hour. The product spectrum is shown in Table XI. As will be seen, the conver~ion of the meta hydroperoxide was complete.
No ortho-i~opropyltoluene was converted during the oxidation and rearrangement steps into 2-methylphenol.

~LiL39~ 7 -52~

TABLE XI
Rearrangement of meta-Isopropyltoluene Hydroperoxide Starting MaterialProduct Acetone 0 9~1 Light ends 1.3 1.5 meta-I30propyltoluene 47.2 43.7 ortho-Isopropyltoluene 5.6 4.8 ~eta-I~opropyltoluene hydroperoxide 26.0 0 3-Methylphenol 0 14.4 CO ~ 4 4 4.3 /~\
B.1 0 ~ 0 3.8 Other 7.2 l8.5 .

.

,

Claims (16)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. In the process for the production of hydroxybenzene compounds having substituents in the l and 3 positions on the benzene ring, said process comprising: (a) alkylation of an aromatic compound with an alkylating agent to produce an isomeric mixture of dialkylbenzene compounds; (b) separation of the iso-mers of said dialkylbenzene compounds to obtain a material en-riched with respect to the 1,3-dialkylbenzene isomer; (c) oxida-tion of said material enriched with respect to said 1,3-dialkyl-benzene isomer with oxygen to yield the hydroperoxide thereof;
and (d) acid catalyzed rearrangement of said hydroperoxide by contacting the hydroperoxide with an inorganic acid or a cation exchange resin to yield a 1,3-disubstituted benzene compound having at least one hydroxyl substituent thereon; the improve-ment comprising I. in alkylation step (a), carrying out said alkylation of said aromatic compound in the presence of a particular type of zeolite alkylation catalyst at a.
temperature of from about 100°C to about 400°C and a pressure of from about 105N/m2 to about 4Xl06 N/m2, said zeolite alkylation catalyst being characterized by a silica to alumina mole ratio of at least 12 and a constraint index within the approximate range of l to 12; and said improvement further comprising II. in the separation step (b) contacting said isomeric mixture of dialkylbenzene compounds with a shape selective zeolite catalyst at a temperature of be-tween about 150°C and about 800°C and a pressure of between about 104N/m2 and about 107N/m2, to selec-tively react the 1,4-dialkyl isomer of said dialkyl-benzene compounds, the reaction mixture thereby be-coming enriched with respect to the 1,3-dialkyl iso-mer thereof, said shape selective zeolite being characterized by a constraint index within the range from about l to about 12 and further by a silica to alumina ratio of at least 12.

2. The process of claim 1 (I) wherein said alkylation temperature is within the approximate range of 200°C to 300°C.

3. The process of claim 1 wherein the alkylating agent is propylene.

4. The process of claim 1 wherein said 1,3-disubstituted benzene compound having at least one hydroxyl substituent is 1,3-dihydroxybenzene.

5. The process of claim 1 wherein said 1,3-disubstituted benzene compound having at least one hydroxyl substituent is a 3-alkylphenol.

6. The process of claim 5 wherein said 3-alkylphenol is 3-methylphenol.

7. The process of claim 1 wherein said zeolite alkyla-tion catalyst is ZSM-5.

8. The process of claim 1 wherein said zeolite alkyla-tion catalyst is ZSM-12.

9. The process of claims 1, 7 or 8 wherein said zeolite alkylation catalyst is admixed with a binder therefor.

10. The process of claim 1 wherein said shape selective zeolite catalyst is ZSM-5.

11. The process of claim 1 wherein said shape selective zeolite catalyst is ZSM-11.

12. The process of claim 1 wherein said shape selective zeolite catalyst is ZSM-23.

13. The process of claims 1, 11 or 12 wherein said shape selective zeolite catalyst has undergone prior modifica-tion by combining therewith between about 0.5 and about 40 weight percent of at least one oxide selected from the group consisting of the oxides of phosphorus, antimony, boron and magnesium.

14. The process of claims 1, 11 or 12 wherein said shape selective zeolite catalyst is admixed with a binder there-for.

15. The process of claims 1, 10 or 11 wherein said shape selective zeolite catalyst has undergone prior modifica-tion by steaming at a temperature between about 250°C and about l000°C for a period of between about 0.5 and about 100 hours.

16. The process of claim 1 (II) wherein said tempera-ture is from about 250°C to about 550°C and said pressure is from about 2X104N/m2 and about 2.5X106N/m.