# Patent

## Title
Methyl-substituted biphenyl compounds, their production and their use in the manufacture of plasticizers

## Abstract

In a process for producing methyl-substituted biphenyl compounds, a feed comprising at least one aromatic hydrocarbon selected from the group consisting of toluene, xylene and mixtures thereof is contacted with hydrogen in the presence of a hydroalkylation catalyst under conditions effective to produce a hydroalkylation reaction product comprising (methylcyclohexyl)toluenes and/or (dimethylcyclohexyl)xylenes. At least part of the hydroalkylation reaction product is then dehydrogenated in the presence of a dehydrogenation catalyst under conditions effective to produce a dehydrogenation reaction product comprising a mixture of methyl-substituted biphenyl compounds.

## Background
PRIORITY
This application claims the benefit of and priority to Provisional Application No. 61/781,129, filed Mar. 14, 2013.


FIELD
The disclosure relates to methyl-substituted biphenyl compounds, their production and their use in the manufacture of plasticizers.
BACKGROUND
Plasticizers are incorporated into a resin (usually a plastic or elastomer) to increase the flexibility, workability, or distensibility of the resin. The largest use of plasticizers is in the production of “plasticized” or flexible polyvinyl chloride (PVC) products. Typical uses of plasticized PVC include films, sheets, tubing, coated fabrics, wire and cable insulation and jacketing, toys, flooring materials such as vinyl sheet flooring or vinyl floor tiles, adhesives, sealants, inks, and medical products such as blood bags and tubing, and the like.
Other polymer systems that use small amounts of plasticizers include polyvinyl butyral, acrylic polymers, nylon, polyolefins, polyurethanes, and certain fluoroplastics. Plasticizers can also be used with rubber (although often these materials fall under the definition of extenders for rubber rather than plasticizers). A listing of the major plasticizers and their compatibilities with different polymer systems is provided in “Plasticizers,” A. D. Godwin, in Applied Polymer Science 21st Century, edited by C. D. Craver and C. E. Carraher, Elsevier (2000); pp. 157-175.
The most important chemical class of plasticizers is phthalic acid esters, which accounted for about 84% worldwide of PVC plasticizer usage in 2009.
Others are esters based on cyclohexanoic acid. In the late 1990's and early 2000's, various compositions based on cyclohexanoate, cyclohexanedioates, and cyclohexanepolyoate esters were said to be useful for a range of goods from semi-rigid to highly flexible materials. See, for instance, WO 99,32427, WO 2004/046078, WO 2003/029339, U.S. Patent Publication No. 2006-0247461, and U.S. Pat. No. 7,297,738.
Others also include esters based on benzoic acid (see, for instance, U.S. Pat. No. 6,740,254) and polyketones, such as described in U.S. Pat. No. 6,777,514; and U.S. Patent Publication No. 2008-0242895. Epoxidized soybean oil, which has much longer alkyl groups (C16 to C18), has been tried as a plasticizer, but is generally used as a PVC stabilizer. Stabilizers are used in much lower concentrations than plasticizers. US Patent Publication No. 2010-0159177 discloses triglycerides with a total carbon number of the triester groups between 20 and 25, produced by esterification of glycerol with a combination of acids derived from the hydroformylation and subsequent oxidation of C3 to C9 olefins, having excellent compatibility with a wide variety of resins and that can be made with a high throughput.
For example, in an article entitled “Esters of diphenic acid and their plasticizing properties”, Kulev et al., Izvestiya Tomskogo Politekhnicheskogo Instituta (1961) 111, disclose that diisoamyl diphenate, bis(2-ethylhexyl)diphenate and mixed heptyl, octyl and nonyl diphenates can be prepared by esterification of diphenic acid, and allege that the resultant esters are useful as plasticizers for vinyl chloride. Similarly, in an article entitled “Synthesis of dialkyl diphenates and their properties”, Shioda et al., Yuki Gosei Kagaku Kyokaishi (1959), 17, disclose that dialkyl diphenates of C1 to C8 alcohols, said to be useful as plasticizers for poly(vinyl chloride), can be formed by converting diphenic acid to diphenic anhydride and esterifying the diphenic anhydride. However, since these processes involve esterification of diphenic acid or anhydride, they necessarily result in 2,2′-substituted diesters of diphenic acid. Generally, such diesters having substitution on the 2-carbons have proven to be too volatile for use as plasticizers.
An alternative method of producing dialkyl diphenate esters having an increased proportion of the less volatile 3,3′, 3,4′ and 4,4′ diesters has now been developed. In particular, it has been found that dimethylbiphenyl compounds containing significant amounts of the 3,3′-dimethyl, the 3,4′-dimethyl and the 4,4′-dimethyl isomers can be economically produced by hydroalkylation of toluene and/or xylene followed by dehydrogenation of the resulting (methylcyclohexyl)toluene and/or (dimethylcyclohexyl)xylene product. The resultant mixture can be used as a precursor in the production of biphenylester-based plasticizers by, for example, oxidizing the methyl-substituted biphenyl compounds to convert at least one of the methyl groups to a carboxylic acid group and then esterifying the carboxylic acid group with an alcohol, such as an oxo alcohol. In addition, depending on the catalyst employed, the hydroalkylation reaction exhibits low selectivity to fully saturated compounds, which are difficult to dehydrogenate to biphenyls, and low selectivity to heavies, which must be removed resulting in yield loss.
SUMMARY
In one aspect, the present disclosure is directed to a process for producing methyl-substituted biphenyl compounds, the process comprising:
(a) contacting a feed comprising at least one aromatic hydrocarbon selected from the group consisting of toluene, xylene and mixtures thereof with hydrogen in the presence of a hydroalkylation catalyst under conditions effective to produce a hydroalkylation reaction product comprising (methylcyclohexyl)toluenes and/or (dimethylcyclohexyl)xylenes; and
(b) dehydrogenating at least part of the hydroalkylation reaction product in the presence of a dehydrogenation catalyst under conditions effective to produce a dehydrogenation reaction product comprising a mixture of methyl-substituted biphenyl compounds.
In another aspect, the present disclosure is directed to a process for producing biphenyl esters, the process comprising:
(a) contacting a feed comprising at least one aromatic hydrocarbon selected from the group consisting of toluene, xylene and mixtures thereof with hydrogen in the presence of a hydroalkylation catalyst under conditions effective to produce a hydroalkylation reaction product comprising (methylcyclohexyl)toluenes and/or (dimethylcyclohexyl)xylenes;
(b) dehydrogenating at least part of the hydroalkylation reaction product in the presence of a dehydrogenation catalyst under conditions effective to produce a dehydrogenation reaction product comprising a mixture of methyl-substituted biphenyl compounds;
(c) contacting at least part of the dehydrogenation reaction product with an oxidizing gas under conditions effective to convert at least part of the methyl-substituted biphenyl compounds to biphenyl carboxylic acids; and
(d) reacting the biphenyl carboxylic acids with one or more C4 to C14 alcohols under conditions effective to produce biphenyl esters.
In one embodiment, the hydroalkylation catalyst comprises an acidic component and a hydrogenation component. The acidic component may comprise a molecular sieve, such as a molecular sieve selected from the group consisting of BEA, FAU and MTW structure type molecular sieves, molecular sieves of the MCM-22 family and mixtures thereof. In one embodiment, the acidic component comprises a molecular sieve of the MCM-22 family.
In yet another aspect, the present disclosure is directed to a process for producing (methylcyclohexyl)toluene, the process comprising:
(a) contacting a feed comprising toluene with hydrogen in the presence of a hydroalkylation catalyst under conditions effective to produce a hydroalkylation reaction product comprising (methylcyclohexyl)toluene, wherein the hydroalkylation catalyst comprises a molecular sieve of the MCM-22 family and a hydrogenation metal.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a bar graph comparing the amount of di(methylcyclohexyl)toluenes produced in the hydroalkylation of toluene over the catalysts of Examples 1 to 4.
FIG. 2 is a graph of toluene conversion against time on stream (TOS) in the hydroalkylation of toluene over the Pd-MCM-49 catalyst of Example 1.
FIG. 3 is a graph of toluene conversion against time on stream (TOS) in the hydroalkylation of toluene over the Pd-beta catalyst of Example 2.
FIG. 4 is a graph of toluene conversion against time on stream (TOS) in the hydroalkylation of toluene over the Pd—Y catalyst of Example 3.
FIG. 5 is a graph of toluene conversion against time on stream (TOS) in the hydroalkylation of toluene over the Pd—WO3/ZrO2 catalyst of Example 4.
FIG. 6 is a bar graph comparing the reaction effluents produced by the non-selective dehydrogenation of the hydroalkylation products of Examples 1 and 2.



DETAILED DESCRIPTION OF THE EMBODIMENTS
The present disclosure relates to the production of methyl substituted biphenyl compounds by the catalytic hydroalkylation of toluene and/or xylene followed by dehydrogenation of at least part of the hydroalkylation reaction product. Depending on the catalyst employed in the hydroalkylation reaction, the hydroalkylation process is selective to the production of the desired (methylcyclohexyl)toluenes and/or (dimethylcyclohexyl)xylenes without excessive production of heavies and fully saturated rings. In addition, the dimethylbiphenyl product of the dehydrogenation reaction contains significant amounts of the 3,3′-dimethyl, the 3,4′-dimethyl and the 4,4′-dimethyl compounds making the product an attractive precursor in the production of biphenylester-based plasticizers.
Hydroalkylation of Toluene and/or Xylene
Hydroalkylation is a two-stage catalytic reaction in which an aromatic compound is partially hydrogenated to produce a cyclic olefin, which then reacts, in situ, with the aromatic compound to produce a cycloalkylaromatic product. In the present process, the aromatic compound comprises toluene and/or xylene and the cycloalkylaromatic product comprises a mixture of (methylcyclohexyl)toluene and/or (dimethylcyclohexyl)xylene isomers. In the case of toluene, the desired reaction may be summarized as follows:




Among the competing reactions is further hydrogenation of the cyclic olefin intermediate and/or the cycloalkylaromatic product to produce fully saturated rings. In the case of toluene as the hydroalkylation feed, further hydrogenation can produce methylcyclohexane and dimethylbicyclohexane compounds. Although these by-products can be converted back to feed (toluene) and to the product ((methylcyclohexyl)toluene and dimethylbiphenyl) via dehydrogenation, this involves an endothermic reaction requiring high temperatures (>375° C.) to obtain high conversion. This not only makes the reaction costly but can also lead to further by-product formation and hence yield loss. It is therefore desirable to employ a hydroalkylation catalyst that exhibits low selectivity towards the production of fully saturated rings.
Another competing reaction is dialkylation in which the (methylcyclohexyl)toluene product reacts with further methylcyclohexene to produce di(methylcyclohexyl)toluene. Again this by-product can be converted back to (methylcyclohexyl)toluene, in this case by transalkylation. However, this process requires the use of an acid catalyst at temperatures above 160° C. and can lead to the production of additional by-products, such as di(methylcyclopentyl)toluenes, cyclohexylxylenes and cyclohexylbenzene. It is therefore desirable to employ a hydroalkylation catalyst that exhibits low selectivity towards di(methylcyclohexyl)toluene and other heavy by-products.
The catalyst employed in the hydroalkylation reaction is a bifunctional catalyst comprising a hydrogenation component and a solid acid alkylation component, typically a molecular sieve. The catalyst may also include a binder 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 silica and metal oxides. Naturally occurring clays which can be used as a binder include those of the montmorillonite and kaolin families, which families include the subbentonites and the kaolins commonly known as Dixie, McNamee, Ga. 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. Suitable metal oxide binders include silica, alumina, zirconia, titania, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia.
Any known hydrogenation metal or compound thereof can be employed as the hydrogenation component of the catalyst, although suitable metals include palladium, ruthenium, nickel, zinc, tin, and cobalt, with palladium being particularly advantageous. In certain embodiments, the amount of hydrogenation metal present in the catalyst is between about 0.05 and about 10 wt %, such as between about 0.1 and about 5 wt %, of the catalyst.
In one embodiment, the solid acid alkylation component comprises a large pore molecular sieve having a Constraint Index (as defined in U.S. Pat. No. 4,016,218) less than 2. Suitable large pore molecular sieves include zeolite beta, zeolite Y, Ultrastable Y (USY), Dealuminized Y (Deal Y), mordenite, ZSM-3, ZSM-4, ZSM-18, and ZSM-20. Zeolite ZSM-14 is described in U.S. Pat. No. 3,923,636. Zeolite ZSM-20 is described in U.S. Pat. No. 3,972,983. Zeolite Beta is described in U.S. Pat. No. 3,308,069, and Re. No. 28,341. Low sodium Ultrastable Y molecular sieve (USY) is described in U.S. Pat. Nos. 3,293,192 and 3,449,070. Dealuminized Y zeolite (Deal Y) may be prepared by the method found in U.S. Pat. No. 3,442,795. Zeolite UHP-Y is described in U.S. Pat. No. 4,401,556. Mordenite is a naturally occurring material but is also available in synthetic forms, such as TEA-mordenite (i.e., synthetic mordenite prepared from a reaction mixture comprising a tetraethylammonium directing agent). TEA-mordenite is disclosed in U.S. Pat. Nos. 3,766,093 and 3,894,104.
In another, more preferred embodiment, the solid acid alkylation component comprises a molecular sieve of the MCM-22 family. The term “MCM-22 family material” (or “material of the MCM-22 family” or “molecular sieve of the MCM-22 family”), as used herein, includes one or more of:

    
    
        molecular sieves made from a common first degree crystalline building block unit cell, which unit cell has the MWW framework topology. (A unit cell is a spatial arrangement of atoms which if tiled in three-dimensional space describes the crystal structure. Such crystal structures are discussed in the “Atlas of Zeolite Framework Types”, Fifth edition, 2001, the entire content of which is incorporated as reference);
        molecular sieves made from a common second degree building block, being a 2-dimensional tiling of such MWW framework topology unit cells, forming a monolayer of one unit cell thickness, preferably one c-unit cell thickness;
        molecular sieves made from common second degree building blocks, being layers of one or more than one unit cell thickness, wherein the layer of more than one unit cell thickness is made from stacking, packing, or binding at least two monolayers of one unit cell thickness. The stacking of such second degree building blocks can be in a regular fashion, an irregular fashion, a random fashion, or any combination thereof; and
        molecular sieves made by any regular or random 2-dimensional or 3-dimensional combination of unit cells having the MWW framework topology.
    
    


Molecular sieves of MCM-22 family generally have an X-ray diffraction pattern including d-spacing maxima at 12.4±0.25, 6.9±0.15, 3.57±0.07 and 3.42±0.07 Angstrom. The X-ray diffraction data used to characterize the material are obtained by standard techniques using the K-alpha doublet of copper as the incident radiation and a diffractometer equipped with a scintillation counter and associated computer as the collection system. Molecular sieves of MCM-22 family include MCM-22 (described in U.S. Pat. No. 4,954,325), PSH-3 (described in U.S. Pat. No. 4,439,409), SSZ-25 (described in U.S. Pat. No. 4,826,667), ERB-1 (described in European Patent No. 0293032), ITQ-1 (described in U.S. Pat. No. 6,077,498), ITQ-2 (described in International Patent Publication No. WO97/17290), MCM-36 (described in U.S. Pat. No. 5,250,277), MCM-49 (described in U.S. Pat. No. 5,236,575), MCM-56 (described in U.S. Pat. No. 5,362,697) and mixtures thereof.
In addition to the toluene and/or xylene and hydrogen, a diluent, which is substantially inert under hydroalkylation conditions, may be included in the feed to the hydroalkylation reaction. In certain embodiments, the diluent is a hydrocarbon, in which the desired cycloalkylaromatic product is soluble, such as a straight chain paraffinic hydrocarbon, a branched chain paraffinic hydrocarbon, and/or a cyclic paraffinic hydrocarbon. Examples of suitable diluents are decane and cyclohexane. Although the amount of diluent is not narrowly defined, desirably the diluent is added in an amount such that the weight ratio of the diluent to the aromatic compound is at least 1:100; for example at least 1:10, but no more than 10:1, desirably no more than 4:1.
In one embodiment, the aromatic feed to the hydroalkylation reaction also includes benzene and/or one or more alkylbenzenes different from toluene and xylene. Suitable alkylbenzenes may have one or more alkyl groups with up to 4 carbon atoms and include, by way of example, ethylbenzene, cumene, and unseparated C6-C8 or C7-C8 or C7-C9 streams.
The hydroalkylation reaction can be conducted in a wide range of reactor configurations including fixed bed, slurry reactors, and/or catalytic distillation towers. In addition, the hydroalkylation reaction can be conducted in a single reaction zone or in a plurality of reaction zones, in which at least the hydrogen is introduced to the reaction in stages. Suitable reaction temperatures are between about 100° C. and about 400° C., such as between about 125° C. and about 250° C., while suitable reaction pressures are between about 100 and about 7,000 kPa, such as between about 500 and about 5,000 kPa. The molar ratio of hydrogen to aromatic feed is typically from about 0.15:1 to about 15:1.
In the present process, it is found that MCM-22 family molecular sieves are particularly active and stable catalysts for the hydroalkylation of toluene or xylene. In addition, catalysts containing MCM-22 family molecular sieves exhibit improved selectivity to the 3,3′-dimethyl, the 3,4′-dimethyl, the 4,3′-dimethyl and the 4,4′-dimethyl isomers in the hydroalkylation product, while at the same time reducing the formation of fully saturated and heavy by-products. For example, using an MCM-22 family molecular sieve with a toluene feed, it is found that the hydroalkylation reaction product may comprise:

    
    
        at least 60 wt %, such as at least 70 wt %, for example at least 80 wt % of the 3,3,3,4,4,3 and 4,4-isomers of (methylcyclohexyl)toluene based on the total weight of all the (methylcyclohexyl)toluene isomers;
        less than 30 wt % of methylcyclohexane and less than 2% of dimethylbicyclohexane compounds; and
        less than 1 wt % of compounds containing in excess of 14 carbon atoms.
    
    


Similarly, with a xylene feed, the hydroalkylation reaction product may comprise less than 1 wt % of compounds containing in excess of 16 carbon atoms.
By way of illustration, the 3,3, 3,4 4,3 and 4,4-isomers of (methylcyclohexyl)toluene are illustrated in formulas F1 to F4, respectively:




In contrast, when the methyl group is located in the 1-position (quaternary carbon) on the cyclohexyl ring, ring isomerization can occur forming (dimethylcyclopentyl)toluene and (ethylcyclopentyl)toluene which, on dehydrogenation, will generate diene by-products which are difficult to separate from the desired product and will also inhibit the subsequent oxidation reaction. In the oxidation and esterification steps, different isomers have different reactivity. Thus, para-isomers are more reactive than meta-isomers which are more reactive than ortho-isomers. Also in the dehydrogenation step, the presence of a methyl group in the 2 position on either the cyclohexyl or phenyl ring is a precursor for the formation of fluorene and methyl fluorene. Fluorene is difficult to separate from the dimethylbiphenyl product and causes problems in the oxidation step and also in the plasticizers performance. It is therefore advantageous to minimize the formation of isomers which have a methyl group in the ortho, 2 and benzylic positions.
Dehydrogenation of Hydroalkylation Product
The major components of the hydroalkylation reaction effluent are (methylcyclohexyl)toluenes and/or (dimethylcyclohexyl)xylenes, unreacted aromatic feed (toluene and/or xylene) and fully saturated single ring by-products (methylcyclohexane and dimethylcyclohexane). The unreacted feed and light by-products can readily be removed from the reaction effluent by, for example, distillation. The unreacted feed can then be recycled to the hydroalkylation reactor, while the saturated by-products can be dehydrogenated to produce additional recyclable feed.
The remainder of the hydroalkylation reaction effluent, composed mainly of (methylcyclohexyl)toluenes and/or (dimethylcyclohexyl)xylenes, is then dehydrogenated to produce the corresponding methyl-substituted biphenyl compounds. The dehydrogenation is conveniently conducted at a temperature from about 200° C. to about 600° C. and a pressure from about 100 kPa to about 3550 kPa (atmospheric to about 500 psig) in the presence of dehydrogenation catalyst. A suitable dehydrogenation catalyst comprises one or more elements or compounds thereof selected from Group 10 of the Periodic Table of Elements, for example platinum, on a support, such as silica, alumina or carbon nanotubes. In one embodiment, the Group 10 element is present in amount from 0.1 to 5 wt % of the catalyst. In some cases, the dehydrogenation catalyst may also include tin or a tin compound to improve the selectivity to the desired methyl-substituted biphenyl product. In one embodiment, the tin is present in amount from 0.05 to 2.5 wt % of the catalyst.
As used herein, the numbering scheme for the Periodic Table Groups is as disclosed in Chemical and Engineering News, 63(5), 27 (1985).
Particularly using an MCM-22 family-based catalyst for the upstream hydroalkylation reaction, the product of the dehydrogenation step comprises methyl-substituted biphenyl compounds in which the concentration of the 3,3-, 3,4- and 4,4-dimethyl isomers is at least 50 wt %, such as at least 60 wt %, for example at least 70 wt % based on the total weight of methyl-substituted biphenyl isomers. In addition, the product may contain less than 10 wt %, such as less than 5 wt %, for example less than 3 wt % of methyl biphenyl compounds and less than 5 wt %, such as less than 3 wt %, for example less than 1 wt % of fluorene and methyl fluorenes combined.
Production of Biphenyl Esters
The methyl-substituted biphenyl compounds produced by the dehydrogenation reaction can readily be converted ester plasticizers by a process comprising oxidation to produce the corresponding carboxylic acids followed by esterification with an alcohol.
The oxidation can be performed by any process known in the art, such as by reacting the methyl-substituted biphenyl compounds with an oxidant, such as oxygen, ozone or air, or any other oxygen source, such as hydrogen peroxide, in the presence of a catalyst at temperatures from 30° C. to 300° C., such as from 60° C. to 200° C. Suitable catalysts comprise Co or Mn or a combination of both metals.
The resulting carboxylic acids can then be esterified to produce biphenyl ester plasticizers by reaction with one or more C4 to C14 alcohols. Suitable esterification conditions are well-known in the art and include, but are not limited to, temperatures of 0-300° C. and the presence or absence of homogeneous or heterogeneous esterification catalysts, such as Lewis or Bronsted acid catalysts. Suitable alcohols are “oxo-alcohols”, by which is meant an organic alcohol, or mixture of organic alcohols, which is prepared by hydroformylating an olefin, followed by hydrogenation to form the alcohols. Typically, the olefin is formed by light olefin oligomerization over heterogeneous acid catalysts, which olefins are readily available from refinery processing operations. The reaction results in mixtures of longer-chain, branched olefins, which subsequently form longer chain, branched alcohols, as described in U.S. Pat. No. 6,274,756, incorporated herein by reference in its entirety. Another source of olefins used in the OXO process are through the oligomerization of ethylene, producing mixtures of predominately straight chain alcohols with lesser amounts of lightly branched alcohols.
The biphenyl ester plasticizers of the present application find use in a number of different polymers, such as vinyl chloride resins, polyesters, polyurethanes, ethylene-vinyl acetate copolymers, rubbers, poly(meth)acrylics and mixtures thereof.
The invention will now be more particularly described with reference to the accompanying drawings and the following non-limiting Examples.
Example 1: Synthesis of 0.3% Pd/MCM-49 Catalyst
80 parts MCM-49 zeolite crystals are combined with 20 parts pseudoboehmite alumina, on a calcined dry weight basis. The MCM-49 and pseudoboehmite alumina dry powder is placed in a muller and mixed for about 10 to 30 minutes. Sufficient water and 0.05% polyvinyl alcohol is added to the MCM-49 and alumina during the mixing process to produce an extrudable paste. The extrudable paste is formed into a 1/20 inch (0.13 cm) quadrulobe extrudate using an extruder and the resulting extrudate is dried at a temperature ranging from 250° F. to 325° F. (120° C. to 163° C.). After drying, the dried extrudate is heated to 1000° F. (538° C.) under flowing nitrogen. The extrudate is then cooled to ambient temperature and humidified with saturated air or steam.
After the humidification, the extrudate is ion exchanged with 0.5 to 1 N ammonium nitrate solution. The ammonium nitrate solution ion exchange is repeated. The ammonium nitrate exchanged extrudate is then washed with deionized water to remove residual nitrate prior to calcination in air. After washing the wet extrudate, it is dried. The exchanged and dried extrudate is then calcined in a nitrogen/air mixture to a temperature 1000° F. (538° C.). Afterwards, the calcined extrudate is cooled to room temperature. The 80% MCM-49, 20% Al2O3 extrudate was incipient wetness impregnated with a palladium (II) chloride solution (target: 0.30% Pd) and then dried overnight at 121° C. The dried catalyst was calcined in air at the following conditions: 5 volumes air per volume catalyst per minute, ramp from ambient to 538° C. at 1° C./min and hold for 3 hours.
Example 2: Synthesis of 0.3% Pd/Beta Catalyst
80 parts beta zeolite crystals are combined with 20 parts pseudoboehmite alumina, on a calcined dry weight basis. The beta and pseudoboehmite are mixed in a muller for about 15 to 60 minutes. Sufficient water and 1.0% nitric acid is added during the mixing process to produce an extrudable paste. The extrudable paste is formed into a 1/20 inch quadrulobe extrudate using an extruder. After extrusion, the 1/20th inch quadrulobe extrudate is dried at a temperature ranging from 250° F. to 325° F. (120° C. to 163° C.). After drying, the dried extrudate is heated to 1000° F. (538° C.) under flowing nitrogen and then calcined in air at a temperature of 1000° F. (538° C.). Afterwards, the calcined extrudate is cooled to room temperature. The 80% Beta, 20% Al2O3 extrudate was incipient wetness impregnated with a tetraammine palladium (II) nitrate solution (target: 0.30% Pd) and then dried overnight at 121° C. The dried catalyst was calcined in air at the following conditions: 5 volumes air per volume catalyst per minute, ramp from ambient to 538° C. at 1° C./min and hold for 3 hours.
Example 3: Synthesis of 0.3% Pd/USY Catalyst
80 parts Zeolyst CBV-720 ultrastable Y zeolite crystals are combined with 20 parts pseudoboehmite alumina on a calcined dry weight basis. The USY and pseudoboehmite are mixed for about 15 to 60 minutes. Sufficient water and 1.0% nitric acid is added during the mixing process to produce an extrudable paste. The extrudable paste is formed into a 1/20 inch quadrulobe extrudate using an extruder. After extrusion, the 1/20th inch quadrulobe extrudate is dried at a temperature ranging from 250° F. to 325° F. (120° C. to 163° C.). After drying, the dried extrudate is heated to 1000° F. (538° C.) under flowing nitrogen and then calcined in air at a temperature of 1000° F. (538° C.). The 80% CBV-720 USY, 20% Al2O3 extrudate was incipient wetness impregnated with a palladium (II) chloride solution (target: 0.30% Pd) and then dried overnight at 121° C. The dried catalyst was calcined in air at the following conditions: 5 volumes air per volume catalyst per minute, ramp from ambient to 538° C. at 1° C./min and hold for 3 hours.
Example 4: Synthesis of 0.3% Pd/W—Zr Catalyst
A WO3/ZrO2 extrudate (11.5% W, balance Zr) 1/16′′ cylinder was obtained from Magnesium Elektron in the form of a 1/16 inch (0.16 cm) diameter extrudate. The WO3/ZrO2 extrudate was calcined in air for 3 hours at 538° C. On cooling, the calcined extrudate was incipient wetness impregnated with a palladium (II) chloride solution (target: 0.30% Pd) and then dried overnight at 121° C. The dried catalyst was calcined in air at the following conditions: 5 volumes air per volume catalyst per minute, ramp from ambient to 538° C. at 1° C./min and hold for 3 hours.
Example 5: Hydroalkylation Catalyst Testing
Each of the catalyst of Examples 1 to 4 was then tested in the hydroalkylation of a toluene feed using the reactor and process described below.
The reactor comprised a stainless steel tube having an outside diameter of: 3⁄8 inch (0.95 cm), a length of 20.5 inch (52 cm) and a wall thickness of 0.35 inch (0.9 cm). A piece of stainless steel tubing having a length of 83⁄4 inch (22 cm) and an outside diameter of: 3⁄8 inch (0.95 cm) and a similar length of 1⁄4 inch (0.6 cm) tubing of were used in the bottom of the reactor (one inside of the other) as a spacer to position and support the catalyst in the isothermal zone of the furnace. A 1⁄4 inch (0.6 cm) plug of glass wool was placed on top of the spacer to keep the catalyst in place. A 1⁄8 inch (0.3 cm) stainless steel thermo-well was placed in the catalyst bed to monitor temperature throughout the catalyst bed using a movable thermocouple.
The catalyst was sized to 20/40 sieve mesh or cut to 1:1 length to diameter ratio, dispersed with quartz chips (20/40 mesh) then loaded into the reactor from the top to a volume of 5.5 cc. The catalyst bed typically was 15 cm. in length. The remaining void space at the top of the reactor was filled with quartz chips, with a 1⁄4 plug of glass wool placed on top of the catalyst bed being used to separate quartz chips from the catalyst. The reactor was installed in a furnace with the catalyst bed in the middle of the furnace at a pre-marked isothermal zone. The reactor was then pressure and leak tested typically at 300 psig (2170 kPa).
The catalyst was pre-conditioned in situ by heating to 25° C. to 240° C. with H2 flow at 100 cc/min and holding for 12 hours. A 500 cc ISCO syringe pump was used to introduce a chemical grade toluene feed to the reactor. The feed was pumped through a vaporizer before flowing through heated lines to the reactor. A Brooks mass flow controller was used to set the hydrogen flow rate. A Grove “Mity Mite” back pressure controller was used to control the reactor pressure typically at 150 psig (1135 kPa). GC analyses were taken to verify feed composition. The feed was then pumped through the catalyst bed held at the reaction temperature of 120° C. to 180° C. at a WHSV of 2 and a pressure of 15-200 psig (204-1480 kPa). The liquid products exiting the reactor flowed through heated lines routed to two collection pots in series, the first pot being heated to 60° C. and the second pot cooled with chilled coolant to about 10° C. Material balances were taken at 12 to 24 hrs intervals. Samples were taken and diluted with 50% ethanol for analysis. An Agilent 7890 gas chromatograph with FID detector was used for the analysis. The non-condensable gas products were routed to an on line HP 5890 GC.
The analysis is done on an Agilent 7890 GC with 150 vial sample tray.
Inlet Temp: 220° C.
Detector Temp: 240° C. (Col+make up=constant)
Temp Program Initial temp 120° C. hold for 15 min., ramp at 2° C./min to 180° C., hold 15 min; ramp at 3° C./min. to 220° C. and hold till end.
Column Flow: 2.25 ml/min. (27 cm/sec); Split mode, Split ratio 100:1
Injector: Auto sampler (0.2 n1).
Column Parameters:
Two columns joined to make 120 Meters (coupled with Agilent ultimate union, deactivated.
Column # Front end: Supelco β-Dex 120; 60 m×0.25 mm×0.25 μm film joined to
Column #2 back end: γ-Dex 325: 60 m×0.25 mm×0.25 μm film.
The results of the hydroalkylation testing are summarized in FIGS. 1 to 4 and Table 1.











TABLE 1







Toluene
Selectivity
Selectivity




conver-
to methyl-
to dimethylbi-


Example
Catalyst
sion
cyclohexane
(cyclohexane)







1
0.3% Pd-MCM49
37%
23%
1.40%


2
0.3% Pd/Beta
40%
65%
1.60%


3
0.3% Pd/Y
80%
75%
3.70%


4
0.3% WO3/ZrO2
13%
35%
1.75%









As can be seen from Table 1, although the Pd/MCM-49 catalyst is less active than the Pd/Y catalyst, it has much lower selectivity towards the production of the fully saturated by-products, methylcyclohexane and dimethylbi(cyclohexane) than either Pd/Y or Pd/beta. In addition, the data shown in FIG. 1 clearly demonstrate that Pd/MCM-49 provides the lowest yield loss, less than 1 wt % of total converted feed, to dialkylate products. The data shown in FIGS. 2 to 5 demonstrate that Pd/MCM-49 has improved stability and catalyst life as compared with the other catalysts tested. It is believed that the stability is related to the formation of heavies which remain on the surface of the catalyst and react further to create coke which prevents the access to the acid and hydrogenation sites.
Example 6: Dehydrogenation of Methylcyclohexyltoluene
The same reactor, catalyst and analytical configuration as described above was used to perform dehydrogenation tests on the conversion products produced in Example 5 from the Pd/MCM-49 and Pd/beta catalysts of Examples 1 and 2, except each dehydrogenation catalyst was pre-conditioned in situ by heating to 375° C. to 460° C. with H2 flow at 100 cc/min and holding for 2 hours. In addition, in the dehydrogenation tests the catalyst bed was held at the reaction temperature of 375° C. to 460° C. at a WHSV of 2 and a pressure of 100 psig (790 kPa).
In a first set of tests, the dehydrogenation was conducted at a temperature of 425° C. using a selective dehydrogenation catalyst comprising bimetallic catalyst e.g., Pt/Sn, on a support. The results of the tests are summarized in Table 2 below:









TABLE 2






MCM-49 HA product
Beta HA product



over selective
over selective



dehydrogenation
dehydrogenation



catalyst
catalyst

















3-methyl biphenyl
0.70%
2.47%


4-methyl biphenyl
0.79%
4.98%


2,2 dimethyl biphenyl
1.21%
1.04%


2,3 dimethyl biphenyl
9.52%
8.42%


2,4 dimethyl biphenyl
13.14%
12.64%


3,3 dimethyl biphenyl
15.98%
13.21%


3,4 dimethyl biphenyl
39.64%
36.26%


4,4 dimethyl biphenyl
18.76%
18.19%


fluorene
0.00%
0.93%


methyl fluorenes
0.26%
1.87%









In a second set of tests, the dehydrogenation was conducted at a temperature of 425° C. using a non-selective dehydrogenation catalyst comprising Pt on a support. The results of the tests are summarized in FIG. 6.
The data clearly shows that dehydrogenation of the MCM-49 hydroalkylation products provides less mono methyl biphenyl, less of the 2′,3 and 2′,4 dimethyl biphenyl isomers which are the precursor for the formation of fluorene and methyl fluorene and much less the fluorene and methyl fluorene as compared with dehydrogenation of the zeolite beta hydroalkylation products.
While various embodiments have been described, it is to be understood that further embodiments will be apparent to those skilled in the art and that such embodiments are to be considered within the purview and scope of the appended claims.
All documents described herein are incorporated by reference herein, including any priority documents and/or testing procedures to the extent they are not inconsistent with this text, provided however that any priority document not named in the initially filed application or filing documents is NOT incorporated by reference herein. As is apparent from the foregoing general description and the specific embodiments, while forms of the invention have been illustrated and described, various modifications can be made without departing from the spirit and scope of the invention. Accordingly, it is not intended that the invention be limited thereby. Likewise, the term “comprising” is considered synonymous with the term “including” for purposes of Australian law. Likewise whenever a composition, an element or a group of elements is preceded with the transitional phrase “comprising”, it is understood that we also contemplate the same composition or group of elements with transitional phrases “consisting essentially of,” “consisting of”, “selected from the group of consisting of,” or “is” preceding the recitation of the composition, element, or elements and vice versa.

## Claims

1. A process for producing methyl-substituted biphenyl compounds, the process comprising:
(a) contacting an aromatic feed comprising toluene with hydrogen in the presence of a hydroalkylation catalyst under conditions effective to produce a hydroalkylation reaction product comprising:
i) (methylcyclohexyl)toluenes;
ii) at least 60 wt % of 3,3′-, 3,4′-, 4,3′- and 4,4′-isomers of (methylcyclohexyl)toluene based on the total weight of all the (methylcyclohexyl)toluene isomers;
iii) less than 30 wt % of methylcyclohexane; and

(b) dehydrogenating at least part of the hydroalkylation reaction product in the presence of a dehydrogenation catalyst under conditions effective to produce a dehydrogenation reaction product comprising a mixture of methyl-substituted biphenyl compounds,
wherein the hydroalkylation catalyst comprises an acidic component and a hydrogenation component, wherein the hydrogenation component comprises palladium, and where the acidic component comprises an MCM-22 family molecular sieve.

2. The process of claim 1, wherein the conditions in the contacting (a) include a temperature from about 100° C. to about 400° C. and a pressure from about 100 to about 7,000 kPa.

3. The process of claim 1, wherein the molar ratio of hydrogen to aromatic feed supplied to the contacting (a) is from about 0.15:1 to about 15:1.

4. The process of claim 1, wherein the hydroalkylation reaction product comprises less than 2% of dimethylbi(cyclohexane) compounds.

5. The process of claim 1, wherein the hydroalkylation reaction product comprises less than 1 wt % of compounds containing in excess of 14 carbon atoms.

6. The process of claim 1, wherein the feed further comprises benzene and/or at least one alkylbenzene different from toluene.

7. The process of claim 1, wherein the dehydrogenation catalyst comprises an element or compound thereof selected from Group 10 of the Periodic Table of Elements.

8. The process of claim 1, wherein the dehydrogenation conditions in (b) include a temperature from about 200° C. to about 600° C. and a pressure from about 100 kPa to about 3550 kPa.

9. A process for producing biphenyl esters, the process comprising:
(a) contacting an aromatic feed comprising toluene with hydrogen in the presence of a hydroalkylation catalyst under conditions effective to produce a hydroalkylation reaction product comprising:
a) (methylcyclohexyl)toluenes;
b) at least 60 wt % of 3,3′-, 3,4′-, 4,3′- and 4,4′-isomers of (methylcyclohexyl)toluene based on the total weight of all the (methylcyclohexyl)toluene isomers;
c) less than 30 wt % of methylcyclohexane; and
(b) dehydrogenating at least part of the hydroalkylation reaction product in the presence of a dehydrogenation catalyst under conditions effective to produce a dehydrogenation reaction product comprising a mixture of methyl-substituted biphenyl compounds,
wherein the hydroalkylation catalyst comprises an acidic component and a hydrogenation component, wherein the hydrogenation component comprises palladium, and where the acidic component comprises an MCM-22 family molecular sieve;
(c) contacting at least part of the dehydrogenation reaction product with an oxidant under conditions effective to convert at least part of the methyl-substituted biphenyl compounds to biphenyl carboxylic acids; and
(d) reacting the biphenyl carboxylic acids with one or more C4 to C14 alcohols under conditions effective to produce biphenyl esters.

10. The process of claim 9, wherein the conditions in (a) include a temperature from about 100° C. to about 400° C. and a pressure from about 100 to about 7,000 kPa.

11. The process of claim 9, wherein the molar ratio of hydrogen to aromatic feed supplied to the hydroalkylating step (a) is from about 0.15:1 to about 15:1.

12. The process of claim 9, wherein the dehydrogenation catalyst comprises an element or compound thereof selected from Group 10 of the Periodic Table of Elements.

13. The process of claim 9, wherein the dehydrogenation conditions in (b) include a temperature from about 200° C. to about 600° C. and a pressure from about 100 kPa to about 3550 kPa.

14. A process for producing (methylcyclohexyl)toluene, the process comprising:
(a) contacting a feed comprising toluene with hydrogen in the presence of a hydroalkylation catalyst under conditions effective to produce a hydroalkylation reaction product comprising (methylcyclohexyl)toluene, wherein the hydroalkylation catalyst comprises a molecular sieve of the MCM-22 family and a hydrogenation metal, wherein the hydrogenation metal is
wherein the hydroalkylation reaction product comprises: at least 60 wt % of 3,3′-, 3,4′-, 4,3′- and 4,4′-isomers of (methylcyclohexyl)toluene based on the total weight of all the (methylcyclohexyl)toluene isomers and less than 30 wt % of methylcyclohexane.

15. The process of claim 1, wherein unreacted aromatic feed is removed from the hydroalkylation reaction product of step a) and recycled back to the hydroalkylation of step a).

16. The process of claim 1, wherein toluene feed is removed from the hydroalkylation reaction product of step a) and recycled back to the hydroalkylation of step a).

17. The process of claim 1 wherein fully saturated single ring by-products in the hydroalkylation reaction product of step a) are dehydrogenated to produce recyclable feed that is recycled back to the hydroalkylation of step a).

18. The process of claim 1 wherein methylcyclohexane in the hydroalkylation reaction product of step a) are dehydrogenated to produce recyclable feed that is recycled back to the hydroalkylation of step a).

19. The process of claim 1, wherein unreacted aromatic feed is removed from the hydroalkylation reaction product of step a) and recycled back to the hydroalkylation of step a), and wherein fully saturated single ring by-products in the hydroalkylation reaction product of step a) are dehydrogenated to produce recyclable feed that is recycled back to the hydroalkylation of step a).

20. The process of claim 1, wherein toluene feed is removed from the hydroalkylation reaction product of step a) and recycled back to the hydroalkylation of step a), and wherein methylcyclohexane in the hydroalkylation reaction product of step a) are dehydrogenated to produce recyclable feed that is recycled back to the hydroalkylation of step a).

21. The process of claim 9, wherein unreacted aromatic feed is removed from the hydroalkylation reaction product of step a) and recycled back to the hydroalkylation of step a), and wherein fully saturated single ring by-products in the hydroalkylation reaction product of step a) are dehydrogenated to produce recyclable feed that is recycled back to the hydroalkylation of step a).

22. The process of claim 9, wherein toluene feed is removed from the hydroalkylation reaction product of step a) and recycled back to the hydroalkylation of step a), and wherein methylcyclohexane in the hydroalkylation reaction product of step a) are dehydrogenated to produce recyclable feed that is recycled back to the hydroalkylation of step a).

23. The process of claim 1, wherein the dehydrogenation catalyst comprises one or more elements selected from Group 10 and tin or a tin compound.

24. The process of claim 1, wherein the dehydrogenation catalyst comprises platinum and tin or a tin compound.

25. The process of claim 23, wherein the Group 10 element is present at 0.1 to 5 wt % of the catalyst and the tin is present at from 0.05 to 2.5 wt % of the catalyst.

26. The process of claim 9, wherein the dehydrogenation catalyst comprises one or more elements selected from Group 10 and tin or a tin compound.

27. The process of claim 9, wherein the dehydrogenation catalyst comprises platinum and tin or a tin compound.

28. The process of claim 27, wherein the Group 10 element is present at 0.1 to 5 wt % of the catalyst and the tin is present at from 0.05 to 2.5 wt % of the catalyst.

29. The process of claim 1, wherein the dehydrogenation catalyst comprises one or more elements or compounds thereof selected from Group 10 on a support comprising silica, alumina or carbon nanotubes.

30. The process of claim 9, wherein the dehydrogenation catalyst comprises one or more elements or compounds thereof selected from Group 10 on a support comprising silica, alumina or carbon nanotubes.

31. The process of claim 29, wherein the support comprises alumina.

32. The process of claim 30, wherein the support comprises alumina.

33. The process of claim 31, wherein the dehydrogenation catalyst further comprises tin or a tin compound.

34. The process of claim 32, wherein the dehydrogenation catalyst further comprises tin or a tin compound.

35. The process of claim 33, wherein the Group 10 element is platinum.

36. The process of claim 34, wherein the Group 10 element is platinum.