WO2016099893A1 - Production et utilisation de mélanges d'isomères dialkylbiphényliques - Google Patents

Production et utilisation de mélanges d'isomères dialkylbiphényliques Download PDF

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WO2016099893A1
WO2016099893A1 PCT/US2015/063491 US2015063491W WO2016099893A1 WO 2016099893 A1 WO2016099893 A1 WO 2016099893A1 US 2015063491 W US2015063491 W US 2015063491W WO 2016099893 A1 WO2016099893 A1 WO 2016099893A1
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isomers
product
dimethylbiphenyl
contacting
fraction
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PCT/US2015/063491
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Michael Salciccioli
Jihad M. Dakka
Emiel De Smit
Neeraj Sangar
Scott J. WEIGEL
Sumathy RAMAN
Terry E. Helton
Lorenzo C. Decaul
Christine N. Elia
Chuansheng Bai
Ranjita Ghose
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Exxonmobil Chemical Patents Inc.
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Priority to EP15870658.0A priority Critical patent/EP3233769A4/fr
Priority to CN201580068725.7A priority patent/CN107001184A/zh
Publication of WO2016099893A1 publication Critical patent/WO2016099893A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/74—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition with simultaneous hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
    • C07C5/2729—Changing the branching point of an open chain or the point of substitution on a ring
    • C07C5/2732—Catalytic processes
    • C07C5/2737—Catalytic processes with crystalline alumino-silicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
    • C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
    • C07C2/864—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an alcohol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/367—Formation of an aromatic six-membered ring from an existing six-membered ring, e.g. dehydrogenation of ethylcyclohexane to ethylbenzene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C07C2521/04—Alumina
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65

Definitions

  • This invention relates to a production and use of dialkylbiphenyl isomers and, in particular, to a process for preparing a mixture of dimethylbiphenyl isomers, having an increased concentration of the 3,3' , 3,4' and 4,4' isomers, and to use of the resultant mixture in the production of polyesters and placticizers.
  • DMBP Dimethylbiphenyl
  • other dialkylbiphenyls are useful intermediates in the production of a variety of commercially valuable products, including polyesters and plasticizers for PVC and other polymer compositions.
  • DMBP can readily be converted to an ester plasticizer by a process comprising oxidation of the DMBP to produce the corresponding mono- or dicarboxylic acid followed by esterification with a long chain alcohol.
  • 2,X' DMBP where X' is 2' , 3' and 4' isomers in the product since, for example, diphenate esters having substitution on the 2-carbons tend to be too volatile for use as plasticizers.
  • 4,4'-diphenyl-dicarboxylic acid is a potential precursor, either alone or as a modifier for polyethylene terephthalate (PET), in the production of polyester fibers, engineering plastics, liquid crystal polymers for electronic and mechanical devices, and films with high heat resistance and strength.
  • PET polyethylene terephthalate
  • Homopolyesters of 4,4'-biphenyl dicarboxylic acid (BDA) and various aliphatic diols have been disclosed in the literature.
  • Ezard discloses homopolyesters of 4,4'-biphenyl dicarboxylic acid and ethylene glycol.
  • Meurisse et al. disclose homopolyesters made from 4,4'-biphenyl dicarboxylic acid and a number of diols including ethylene glycol, 1,4-butanediol and 1,6-hexanediol.
  • Homopolyesters of 4,4'-biphenyl dicarboxylic acid and ethylene glycol are also disclosed in, for example, U.S. Patent Nos. 3,842,040 and 3,842,041.
  • Copolyesters of 4,4' -biphenyl dicarboxylic acid with mixtures of aliphatic diols are also disclosed in the literature, see for example, in U.S. Patent No. 2,976,266.
  • U.S. Patent No. 4,959,450 Morris et al. disclose copolyesters from 4,4' -biphenyl dicarboxylic acid and mixtures of 1 ,4-cyclohexanedimethanol and 1,6-hexanediol.
  • Copolyesters of 4,4 '-biphenyl dicarboxylic acid and terephthalic acid with certain aliphatic diols are also disclosed in the literature, for example, in the Journal of Polymer Science, Polym. Letters, 20, 109 (1982) by Krigbaum et al.
  • U.S. Patent No. 5,138,022 discloses copolyesters of 3,4' biphenyl dicarboxylic acid and optionally 4,4' -biphenyl dicarboxylic acid, and certain aliphatic diols, like ethylene glycol, 1,4-butanediol, and 1 ,4- cyclohexanedimethanol.
  • dimethyl biphenyl may be produced by hydroalkylation of toluene followed by dehydrogenation of the resulting (methylcyclohexyl)toluene (MCHT).
  • the isomer distribution of dialkyl-substituted biphenyl compounds can be modified by reaction in the presence of an acid catalyst, particularly a solid phase acid catalyst, such as a molecular sieve. Also by suitable selection of the catalyst and the reaction conditions, the isomerization reaction can be conducted with little or no cracking of the dialkyl-substituted biphenyl species and with low conversion of unreacted MCHT and other cycloalkyl-containing compounds that may be present in the isomerization feed.
  • an acid catalyst particularly a solid phase acid catalyst, such as a molecular sieve.
  • the isomerization reaction can be conducted with little or no cracking of the dialkyl-substituted biphenyl species and with low conversion of unreacted MCHT and other cycloalkyl-containing compounds that may be present in the isomerization feed.
  • the invention resides in a process for converting at least one isomer of a dialkyl-substituted biphenyl compound into at least one different isomer, the process comprising contacting a feed comprising the dialkyl-substituted biphenyl compound isomer with an acid catalyst under isomerization conditions.
  • the invention resides in a process for producing 3,3' , 3,4' and/or 4,4' dialkylbiphenyl compounds, the process comprising:
  • the invention resides in a process for producing 3,3' , 3,4' and/or
  • This invention also relates to a process for producing 3,3' , 3,4' and/or 4,4' dimethylbiphenyl compounds, the process comprising:
  • (d3) supplying at least part of the second fraction as at least part of a feed to an isomerization process comprising contacting the feed comprising one or more 2,X' dimethylbiphenyl isomers with an acid catalyst under isomerization conditions effective to convert at least some of the 2,X' dimethylbiphenyl isomers into one or more 3,3' , 3,4' and 4,4' dimethylbiphenyl isomers and produce an isomerization effluent.
  • This invention also relates to a process for producing 3,3' , 3,4' and/or 4,4' dimethylbiphenyl compounds, the process comprising:
  • This invention also relates to a process for producing 3,3', 3,4' and/or 4,4' dimethylbiphenyl compounds, the process comprising:
  • (f5) optionally, separating the first fraction into a third fraction enriched in one target isomer selected from 3,3', 3,4' and 4,4' dimethylbiphenyl and a fourth fraction depleted in said target isomer;
  • Figure 1 is a graph showing the calculated equilibrium distribution of dimethylbiphenyl isomers over a temperature range from 20 to 750°C.
  • Figures 2(a) and (b) are bar graphs comparing the feed and product compositions for the different catalysts used in the DMPB isomerization experiments of Examples 1 to 13.
  • Figure 3 is a bar graph showing the normalized weight % of >C13 species in the reactor effluent of the DMBP isomerization experiments of Examples 14 and 15.
  • Figures 4(a) to (e) are bar graphs showing the normalized weight % of >C13 species in the reactor effluent of the DMBP isomerization experiments of Examples 16 to 21.
  • Figure 5 is a graph of o-xylene conversion against temperature and time on stream for the o-xylene isomerization experiments of Examples 22 to 25.
  • Figure 6 is a graph of p-xylene selectivity against temperature and time on stream for the o-xylene isomerization experiments of Examples 22 to 25.
  • Figure 7 is a graph of p-xylene approach to equilibrium against temperature and time on stream for the o-xylene isomerization experiments of Examples 22 to 25.
  • Figure 8 is a graph summarizing the performance of the o-xylene isomerization catalysts tested in Examples 22 to 25 at temperatures of 165, 190, 210 and 230°C.
  • Described herein is a process for isomerizing dialkylbiphenyl compounds.
  • the present invention provides a process for the production of a mixture of dialkylbiphenyl isomers in which the amount of the 3,3', 3,4' and 4,4' -dialkylbiphenyl isomers is maximized and the amount of the 2,X' dialkylbiphenyl isomers (where X' is 2', 3' and/or 4') is minimized.
  • each alkyl group is a methyl moiety and the process is directed to converting 2,X' dimethylbiphenyl compounds to 3,3', 3,4' and 4,4' dimethylbiphenyl compounds useful as precursors in the manufacture of polyesters and biphenyl ester plasticizers.
  • Figure 1 is a graph showing the equilibrium distribution of the different isomers of dimethylbiphenyl shown in formulas (I) to (VI) at various temperatures from 0 to 750°C based on thermochemical calculations assuming ideal gas-like behavior for the molecules. It will be seen that, at all temperatures within the range investigated, the most prevalent isomers are 3,3' and 3,4' dimethylbiphenyl, which are generally present in an amount from 30 to 55 wt and 25 to 35 wt , respectively, of the total isomer concentration. However, in all cases, significant quantities of all the other isomers are shown to be present, with the amount of 2,X' dimethylbiphenyl isomers typically ranging from 10 to 30 wt of the total isomer concentration.
  • a desirable isomer is 4,4' dimethylbiphenyl. It will be seen from Figure 1 that 4,4' dimethylbiphenyl is normally present in amounts less than 15 wt of the total isomer concentration, demonstrating the importance of a process for converting the 2,X' dimethylbiphenyl isomers to the preferred 3,3' , 3,4' and 4,4'-isomers.
  • the present process comprises contacting a feed comprising one or more 2,X' dialkylbiphenyl isomers as shown in formulas (IV) to (VI) with an acid catalyst under isomerization conditions effective to convert at least some of the 2,X' dialkylbiphenyl isomers in the feed to one or more 3,3', 3,4' and 4,4' dialkylbiphenyl isomers as shown in formulas (I) to (III) and thereby produce an isomerization product.
  • the feed comprises a dialkylbiphenyl isomer mixture which is deficient in one or more of the 3,3', 3,4' and 4,4' isomers as a result of at least one prior separation step.
  • selective crystallization can be employed to recover at least part of the 4,4' dimethylbiphenyl isomer by virtue of its higher melting point than the other dimethylbiphenyl isomers.
  • Table 1 which summarizes the normal boiling points and temperatures of fusion of various dimethylbiphenyl isomers
  • other separation steps such as distillation, can be used to recover one or more of the 3,3', 3,4' and 4,4' dialkylbiphenyl isomers in the feed.
  • distillation or additional selective crystallization can be used to recover at least part of the 3,3' and 3,4'.
  • any acid catalyst can be used to effect isomerization of the dialkylbiphenyl compounds in the feed to the present process.
  • the catalyst is a heterogeneous solid acid catalyst, such as a metal oxide, a clay or, more preferably, a molecular sieve.
  • Particularly suitable molecular sieves are those having a Constraint Index (as defined in U.S. Patent No. 4,016,218) less than 2, especially molecular sieves selected from the group consisting of BEA, FAU and MOR structure type molecular sieves and mixtures thereof.
  • the conditions used to effect isomerization of the dialkylbiphenyl-containing feed according to the present process are not closely controlled, but suitably include a temperature from 100°C to 450°C, such as 100°C to 250°C and a pressure from 2 to 7,000 kPa-a, such as from 100 to 2000 kPa-a. In some embodiments, it may be desirable to select the temperature and pressure such as to maintain the dialkylbiphenyl components of the feed substantially in the liquid phase since this may reduce carbon losses resulting from cracking.
  • any dialkylbiphenyl-containing feed can be used in the present process but, in one embodiment, the feed comprises a mixture of dimethylbiphenyl isomers produced from toluene by a combination of hydroalkylation followed by dehydrogenation.
  • the toluene is initially converted to (methylcyclohexyl)toluenes over a hydroalkylation catalyst according to the following reaction:
  • 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, alumina, 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, 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.
  • 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 hydroalkylation catalyst, although suitable metals include palladium, ruthenium, nickel, zinc, tin, cobalt, silver, gold, platinum and compounds and mixtures thereof, with palladium being particularly advantageous.
  • 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.
  • the solid acid alkylation component comprises a large pore molecular sieve having a Constraint Index (as defined in U.S. Patent 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- 4 is described in U.S. Patent No. 4,021,447.
  • Zeolite ZSM-20 is described in U.S. Patent No. 3,972,983.
  • Zeolite Beta is described in U.S. Patent Nos. 3,308,069, and Re. No.
  • Low sodium Ultrastable Y molecular sieve (USY) is described in U.S. Patent Nos. 3,293,192 and 3,449,070.
  • Dealuminized Y zeolite (Deal Y) may be prepared by the method found in U.S. Patent No. 3,442,795.
  • Zeolite UHP-Y is described in U.S. Patent 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. Patent Nos. 3,766,093 and 3,894,104.
  • Preferred large pore molecular sieves for use as the solid acid alkylation component of the hydroalkylation catalyst comprise molecular sieves of the BEA and FAU structure type.
  • the solid acid alkylation component comprises a molecular sieve of the MCM-22 family.
  • MCM-22 family material includes one or more of:
  • 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;
  • 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. Patent No.
  • a diluent which is substantially inert under hydroalkylation conditions, may be included in the feed to the hydroalkylation reaction.
  • 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.
  • suitable diluents are decane and cyclohexane.
  • 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.
  • the hydroalkylation reaction can be conducted in a wide range of reactor configurations including fixed bed, slurry reactors, and/or catalytic distillation towers.
  • 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, such as toluene is typically from about 0.15: 1 to about 15: 1.
  • MCM-22 family molecular sieves are particularly active and stable catalysts for the hydroalkylation of toluene.
  • 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.
  • the hydroalkylation reaction product may comprise:
  • the hydroalkylation reaction product may also contain significant amounts of residual toluene, for example up to 50 wt , such as up to 90 wt , typically from 60 to 80 wt of residual toluene based on the total weight of the hydroalkylation reaction product.
  • the major components of the hydroalkylation reaction effluent are (methylcyclohexyl)toluenes, residual toluene and fully saturated single ring by-product (methylcyclohexane).
  • the residual toluene and light by-products can readily be removed from the reaction effluent by, for example, distillation.
  • the residual toluene 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, is then dehydrogenated to convert the (methylcyclohexyl)toluenes to 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 and/or palladium, on a support, such as silica, alumina or carbon nanotubes.
  • the Group 10 element (such as platinum) is present in amount from 0.1 to 5 wt of the catalyst.
  • the dehydrogenation catalyst may also include tin or a tin compound to improve the selectivity to the desired methyl- substituted biphenyl product.
  • the tin is present in an amount from 0.05 to 2.5 wt of the catalyst.
  • the product of the dehydrogenation reaction comprises a mixture of dimethylbiphenyl isomers together with co-produced hydrogen, and up to 90 wt , more typically from 0 to 30 wt , residual (methylcyclohexyl)toluenes.
  • the dehydrogenation product may contain residual toluene, as well as by-products, such as methylcyclohexane, dimethylcyclohexylbenzene, and C15+ heavy hydrocarbons in addition to the target dimethylbiphenyl isomers.
  • the raw dehydrogenation product prior to any separation of the dimethylbiphenyl isomers, is subjected to a rough cut separation to remove at least part of the residues and by-products with significantly different boiling points from the dimethylbiphenyl isomers.
  • the hydrogen by-product can be removed and recycled to the hydroalkylation and/or dehydrogenation steps, while residual toluene and methylcyclohexane by-product can be removed and recycled to the hydroalkylation step.
  • part of the heavy (C15+) components can be removed in the rough cut separation and can be recovered for use as a fuel or can be reacted with toluene over a transalkylation catalyst to convert some of the dialkylate to additional (methylcyclohexyl)toluene.
  • a suitable rough cut separation can be achieved by distillation.
  • the H 2 and C7 components can be stripped from the C12+ components without reflux.
  • the remaining dehydrogenation product is subjected to one or more DMPB separation steps, in which the product is separated into at least a first stream rich in one or more of the 3,3', 3,4' and 4,4' dimethylbiphenyl isomers and at least one second stream comprising one or more 2,X' (where X' is 2' , 3', or 4') dimethylbiphenyl isomers.
  • the second stream will also typically contain most of the unreacted MCHT and most of the dimethylcyclohexylbenzene by-product in the raw dimethylbiphenyl product.
  • the second stream may also contain some or all of the 3,3' dimethylbiphenyl isomer present in the dehydrogenation product.
  • Suitable processes for effecting the DMPB separation include fractional crystallization and/or distillation operating below or, more preferably at, atmospheric pressure.
  • DMPB 2,X' -dimethylbiphenyl
  • the DMPB feed to the present isomerization process is derived from benzene by initially converting the benzene to biphenyl.
  • benzene can be converted directly to biphenyl by reaction with oxygen over an oxidative coupling catalyst as follows:
  • benzene can be converted to biphenyl by hydroalkylation to cyclohexylbe
  • the benzene hydroalkylation can be conducted in the same manner as described above for the hydroalkylation of toluene, while the dehydrogenation of the cyclohexylbenzene can be conducted in the same manner as described above for the dehydrogenation of (methylcyclohexyl)toluene.
  • the biphenyl product of the oxidative coupling step or the hydroalkylation/dehydrogenation sequence is then methylated, for example with methanol, to produce dimethylbiphenyl.
  • Any known alkylation catalyst can be used for the methylation reaction, such as an intermediate pore molecular sieve having a Constraint Index (as defined in U.S. Patent No. 4,016,218) of 3 to 12, for example ZSM-5.
  • the composition of the methylated product will depend on the catalyst and conditions employed in the methylation reaction, but inevitably will comprise a mixture of the different isomers of dimethylbiphenyl at or near the equilibrium distribution shown in Figure 1.
  • the methylated product is initially subjected to one or more separation steps to recover part or all of the 3,3' , 3,4' and 4,4' dimethylbiphenyl isomers, before the remaining 2,X' DMPB enriched fraction is supplied to the isomerization process of the present invention.
  • the isomerization process of the invention can be used to convert part or all of the 3,3' , 3,4' and 4,4' isomer components, in addition to the 2,X' isomer components, of the DMPB feed.
  • the DMPB feed may be initially separated into a first fraction comprising one or more 3,3', 3,4' and 4,4' dimethylbiphenyl isomers and a second fraction comprising one or more 2,X' dimethylbiphenyl isomers.
  • the first fraction is then further separated into a third fraction enriched in one target isomer selected from 3,3', 3,4' and 4,4' dimethylbiphenyl and a fourth fraction depleted in the target isomer.
  • the second and fourth fractions can then be supplied to separate or the same isomerization reactor where the relevant fraction(s) are contacted with a solid acid catalyst under isomerization conditions.
  • this invention relates to:
  • a process for converting at least one isomer of a dialkyl- substituted biphenyl compound into at least one different isomer comprising contacting a feed comprising the dialkyl-substituted biphenyl compound isomer with an acid catalyst under isomerization conditions.
  • dialkyl-substituted biphenyl compound comprises dimethylbiphenyl.
  • a process for producing 3,3', 3,4' and/or 4,4' dialkylbiphenyl compounds comprising:
  • dialkylbiphenyl isomers comprise dimethylbiphenyl isomers.
  • hydroalkylation catalyst comprises an acidic component and a hydrogenation component.
  • the acidic component of the hydroalkylation catalyst comprises a molecular sieve, preferably a molecular sieve selected from the group consisting of BEA and FAU structure type molecular sieves, molecular sieves of the MCM- 22 family and mixtures thereof.
  • a process for producing 3,3', 3,4' and/or 4,4' dimethylbiphenyl compounds comprising:
  • the acidic component of the hydroalkylation catalyst comprises a molecular sieve, preferably a molecular sieve selected from the group consisting of BEA and FAU structure type molecular sieves, molecular sieves of the MCM- 22 family and mixtures thereof.
  • (d3) supplying at least part of the second fraction as at least part of a feed to an isomerization process comprising contacting the feed comprising one or more 2,X' dimethylbiphenyl isomers with an acid catalyst under isomerization conditions effective to convert at least some of the 2,X' dimethylbiphenyl isomers into one or more 3,3', 3,4' and 4,4' dimethylbiphenyl isomers and produce an isomerization effluent.
  • a process for producing 3,3', 3,4' and/or 4,4' dimethylbiphenyl compounds comprising:
  • This invention further relates to:
  • a process for converting at least one isomer of a dialkyl- substituted biphenyl compound into at least one different isomer comprising contacting a feed comprising the dialkyl-substituted biphenyl compound isomer with an acid catalyst under isomerization conditions.
  • dialkyl-substituted biphenyl compound comprises dimethylbiphenyl.
  • a process for producing 3,3', 3,4' and/or 4,4' dialkylbiphenyl compounds comprising:
  • dialkylbiphenyl isomers comprise dimethylbiphenyl isomers.
  • the hydroalkylation catalyst comprises a molecular sieve selected from the group consisting of BEA and FAU structure type molecular sieves, molecular sieves of the MCM-22 family and mixtures thereof.
  • a process for producing 3,3', 3,4' and/or 4,4' dimethylbiphenyl compounds comprising:
  • hydroalkylation catalyst comprises a molecular sieve selected from the group consisting of BEA and FAU structure type molecular sieves, molecular sieves of the MCM-22 family and mixtures thereof.
  • hydroalkylation catalyst comprises a molecular sieve of the MCM-22 family.
  • hydrogenation component of the hydroalkylation catalyst is selected from the group consisting of palladium, ruthenium, nickel, zinc, tin, cobalt, silver, gold, platinum and compounds and mixtures thereof.
  • a process for producing 3,3', 3,4' and/or 4,4' dimethylbiphenyl compounds comprising:
  • (d3) supplying at least part of the second fraction as at least part of a feed to an isomerization process comprising contacting the feed comprising one or more 2,X' dimethylbiphenyl isomers with an acid catalyst under isomerization conditions effective to convert at least some of the 2,X' dimethylbiphenyl isomers into one or more 3,3', 3,4' and 4,4' dimethylbiphenyl isomers and produce an isomerization effluent.
  • a process for producing 3,3', 3,4' and/or 4,4' dimethylbiphenyl compounds comprising:
  • (c4) supplying at least part of the second fraction as at least part of a feed to an isomerization process comprising contacting the feed comprising one or more 2,X' dimethylbiphenyl isomers with an acid catalyst under isomerization conditions effective to convert at least some of the 2,X' dimethylbiphenyl isomers into one or more 3,3', 3,4' and 4,4' dimethylbiphenyl isomers and produce an isomerization effluent.
  • a process for producing 3,3', 3,4' and/or 4,4' dimethylbiphenyl compounds comprising:
  • (f5) optionally, separating the first fraction into a third fraction enriched in one target isomer selected from 3,3', 3,4' and 4,4' dimethylbiphenyl and a fourth fraction depleted in said target isomer;
  • samples were analyzed on an Agilent 7890 Gas Chromatograph equipped with FID detector and an automatic liquid sampler (ALS). Typical injection size was about 0.2 ⁇ 1.
  • the columns used were from Supelco of the Dex type. A Gamma Dex column was joined together with a Beta Dex column to give a total length of 120 m (60 m for each type). The internal diameter of the columns was 0.25mm.
  • the GC was operated in constant flow mode with an initial pressure of about 78 psi and column flow of about 3.0ml/min using helium as carrier gas. The following oven procedure was used:
  • the catalyst of Example 11 was prepared by incipient wetness impregnation of RT-225 AI2O 3 extrudates with surface area of 306 m 2 /g, pore volume of 0.85 cm /g, and pore size of 73 A with boric acid.
  • boric acid H 3 BO 3 was dissolved in 25g of water.
  • the boric acid solution volume was adjusted to 43.2 ml with water, which was about 95% of the water absorption capacity of 50g of the AI2O 3 .
  • the boron containing catalyst was dried at 250°F (121 °C) in air for 14 hr. It was then calcined in air at 1000°F (538°C) for 4 hrs.
  • Catalyst extrudates were crushed to 20/40 mesh loaded in quantities ranging from 0.25-2g (to vary corresponding weight based space velocity) after being diluted up to 4g in crushed quartz.
  • a quartz wool plug was used at the top and bottom of the catalyst bed to keep catalyst in place.
  • Two sets of four parallel reactors were placed in heated furnaces to control isothermal reaction temperature. Each reactor contained an internal thermocouple in the catalyst bed in a 1/8" thermowell. The reactors were topped off with the same quartz chips.
  • An ISCOTM syringe pump was used to introduce the feed to the reactor.
  • the feed was pumped through a vaporizer before being mixed in-line with H 2 and/or N 2 at a molar ratio of between 0 and 2 (gas to hydrocarbon liquid).
  • the products exiting the reactor were condensed and collected in intervals (1-2 samples per day per reactor) and analyzed offline by GC.
  • Example 14 0.5 g of catalyst was loaded in the reactor and the liquid flow rates corresponded to a space velocity of 3 hr 1 .
  • the liquid feed was a mixture of 35 wt 2,3' DMBP, 45 wt 2,4' DMBP and 10 wt MCHT diluted in 90% toluene.
  • a 1:1 molar co-feed of hydrogen to hydrocarbon was utilized and the reactor pressure was held at 100 psig.
  • Temperatures of 280°C and 300°C were tested and the results are shown in Figure 3.
  • Methylcyclohexane was included in the surrogate feed to assess the extent of the cracking side reaction and was used as an indicator for the expected extent of MCHT cracking in the case of DMBP / MCHT mixtures. Toluene was added to the feed to keep track of the toluene disproportionation activity of the catalysts.
  • the catalyst samples tested are listed in Table 5 below and all are the pure zeolite crystals, pelletized and crushed and sieved down to 0.4-0.6 mm particles.
  • the catalysts were subjected to another heat treatment in N 2 flow at 300°C for 24 h and the entire experiment was repeated.
  • the conversion and selectivity were measured by an on-line gas chromatograph, equipped with a high polarity FFAP column (50 m length, 0.32 mm ID, 0.50 ⁇ df).
  • Figures 5 and 6 show the observed o-xylene conversion and p-xylene selectivity as a function of temperature and time-on-stream for the catalysts listed in Table 5.
  • squares indicate data from 1 st run, circles indicate data from 2nd run, after regeneration in N 2 .
  • Tables 6 to 8 show the catalyst performance indicators averaged over the two runs for the experiments at 190, 210°C and 230°C, respectively, whereas Figure 8 summarizes the results over all four temperatures tested.
  • the H-USY and H-MCM-49 catalysts showed reduced performance as compared with the H-MOR and H-ZSM-5 materials.
  • the H- USY catalyst showed high o-xylene conversion but relatively high loss of MCH (cracking) and C9 heavies make, which would be undesirable in the DMBP / MCHT application.
  • the H-MCM-49 catalyst showed acceptable p-xylene selectivity but low activity over the range of experimental conditions tested.
  • compositions, an element or a group of elements are 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.

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  • Crystallography & Structural Chemistry (AREA)
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Abstract

L'invention concerne un procédé permettant de convertir au moins un isomère d'un composé biphényle substitué par un groupe dialkyle, comme au moins un isomère 2,X'dialkylbiphénylique (dans lequel X' représente 2 ', 3'et/ou 4 '), en au moins un isomère différent, isomère 3,3 ',3,4' et/ou 4,4'dialkylbiphénylique. Le procédé consiste à mettre en contact une charge d'alimentation comprenant l'isomère de composé de biphényle substitué par un groupe dialkyle avec un catalyseur acide dans des conditions d'isomérisation.
PCT/US2015/063491 2014-12-19 2015-12-02 Production et utilisation de mélanges d'isomères dialkylbiphényliques WO2016099893A1 (fr)

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EP15870658.0A EP3233769A4 (fr) 2014-12-19 2015-12-02 Production et utilisation de mélanges d'isomères dialkylbiphényliques
CN201580068725.7A CN107001184A (zh) 2014-12-19 2015-12-02 二烷基联苯异构体混合物的生产和用途

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EP3233769A4 (fr) 2018-01-24
CN107001184A (zh) 2017-08-01

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