WO2020086275A1 - Procédés de formation de dérivés de benzène para-substitués - Google Patents

Procédés de formation de dérivés de benzène para-substitués Download PDF

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WO2020086275A1
WO2020086275A1 PCT/US2019/055360 US2019055360W WO2020086275A1 WO 2020086275 A1 WO2020086275 A1 WO 2020086275A1 US 2019055360 W US2019055360 W US 2019055360W WO 2020086275 A1 WO2020086275 A1 WO 2020086275A1
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hydrocarbyl
alcohol
substituted
formula
ring
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Kun Wang
Jonathan E. Mitchell
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Exxonmobil Chemical Patents Inc.
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
    • 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
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • 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
    • C07C5/373—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation
    • C07C5/393—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation with cyclisation to an aromatic six-membered ring, e.g. dehydrogenation of n-hexane to benzene
    • C07C5/41—Catalytic processes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides

Definitions

  • This disclosure relates to processes for producing para-substituted benzene derivatives.
  • this disclosure relates to processes for producing para- substituted benzene derivatives by oxidative coupling of olefins using peroxides.
  • the processes in this disclosure are useful in, e.g., producing p-xylene and products upgraded from hydrocarbons such as light paraffins.
  • Para- substituted benzene derivatives such as para-xylene, also called p- xylene, are important petrochemical building blocks, otherwise known as chemical feedstocks.
  • p-xylene is a useful component used in the production of terephthalic acid (an intermediate in the manufacture of synthetic fibers) for polyesters, such as polyethylene terephthalate which can be used as flexible packaging.
  • terephthalic acid an intermediate in the manufacture of synthetic fibers
  • polyesters such as polyethylene terephthalate which can be used as flexible packaging.
  • Worldwide production capacity of p-xylene is about 40 MTA (million tons per year), and the continually increasing demand for purified terephthalic acid (PTA) in polyester production processes is projected to provide a corresponding demand to the p-xylene market.
  • PTA purified terephthalic acid
  • the major driver for the p-xylene market is the high demand for PET, low cost and superior physical properties of PET, as compared to natural fibers.
  • demand for flexible packaging in general is expected to grow continuously as major retail chains demand greater product protection and longer shelf life for various products.
  • p-Xylene can be produced by catalytic reforming petroleum naphtha to form BTX aromatics (benzene, toluene and xylene isomers) extracted from the catalytic reformate.
  • BTX aromatics benzene, toluene and xylene isomers
  • p-xylene can be produced via toluene disproportionation or toluene alkylation with methanol. Regardless of the method of production, p-xylene is then separated out in a series of distillation, adsorption, crystallization and reaction processes from other Cx aromatic isomers, such as meta-xylene, ortho-xylene, and ethylbenzene.
  • the melting point of p-xylene is the highest among such series of isomers, but simple crystallization does not allow easy purification due to the formation of eutectic mixtures. Consequently, current technologies for p-xylene production are energy intensive, and p-xylene separation and purification are a major cost factor in the production of p-xylene. Hence, alternative methods to selectively produce p-xylene are still needed.
  • a dihydrocarbyl peroxide e.g., a dialkyl peroxide
  • olefins can successfully undergo oxidative coupling reactions to form dienes that can be converted into para-substituted benzene derivatives via dehydrocyclization in the presence of a catalyst.
  • the oxidative coupling reaction produces an alcohol as a byproduct.
  • the dihydrocarbyl peroxide can be produced from coupling a hydrocarbyl hydroperoxide (e.g., an alkyl hydroperoxide) and an alcohol, which, in turn, can be produced from the oxidation of an alkane.
  • isobutylene can couple in the presence of dihydrocarbyl peroxide such as di-ieri-butyl peroxide to form 2,5-dimethyl- l,5-hexadiene, which can be converted into p-xylene at high selectivity in the presence of a dehydrocyclization catalyst.
  • dihydrocarbyl peroxide such as di-ieri-butyl peroxide
  • Tert- butyl alcohol is produced as a byproduct.
  • the di-feri-butyl peroxide can be obtained through coupling of feri-butyl hydroperoxide and feri-butyl alcohol, which can be produced from, e.g., aerobic oxidation of isobutane.
  • feri-butyl hydroperoxide and feri-butyl alcohol which can be produced from, e.g., aerobic oxidation of isobutane.
  • feri-butyl alcohol which can be produced from, e.g., aerobic oxidation of isobutane.
  • this disclosure provides a process for forming a para- substituted benzene derivative includes introducing a first olefin to a dihydrocarbyl peroxide to form a first alcohol and a second olefin that is a polyene. The process includes cyclizing the second olefin to form the para- substituted benzene derivative.
  • a process for forming a para- substituted benzene derivative includes introducing a first olefin to a dihydrocarbyl peroxide to form a first alcohol and a second olefin that is a polyene.
  • the process includes cyclizing the second olefin to form the para-substituted benzene derivative.
  • the process includes introducing a hydrocarbyl hydroperoxide to the first alcohol or a second alcohol to form the dihydrocarbyl peroxide.
  • a process for forming a para- substituted benzene derivative includes introducing a first olefin to a dihydrocarbyl peroxide to form a first alcohol and a second olefin that is a polyene.
  • the process includes cyclizing the second olefin to form the para-substituted benzene derivative.
  • the process includes oxidizing a first feed stream comprising a branched hydrocarbon to form the hydrocarbyl hydroperoxide and the first alcohol or the second alcohol.
  • a process for forming a para- substituted benzene derivative includes introducing a first olefin to a dihydrocarbyl peroxide to form a first alcohol and a second olefin that is a polyene.
  • the process includes cyclizing the second olefin to form the para-substituted benzene derivative.
  • the process includes introducing the first alcohol or second alcohol to a catalyst to form the first olefin.
  • a second aspect of this disclosure provides a process for making p-xylene, the process comprising the following steps: (I) reacting a dihydrocarbyl peroxide with isobutylene to obtain 2,5-dimethyl-l,5-hexadiene and a first alcohol; and (II) converting 2, 5-dimethyl- l,5-hexadiene to obtain p-xylene.
  • the dihydrocarbyl peroxide in step (I) is provided by the following steps: (III) oxidizing a branched hydrocarbon to obtain a hydroperoxide and a second alcohol; and (IV) coupling the hydroperoxide and the second alcohol in the presence of a catalyst to obtain the dihydrocarbyl peroxide.
  • the dihydrocarbyl peroxide comprises di-ieri-butyl peroxide
  • the first alcohol comprises / ⁇ ?/7 - butyl alcohol.
  • FIG. 1 is a schematic diagram showing an exemplary process of this disclosure for producing para-substituted benzene derivatives by upgrading hydrocarbons, according to one embodiment.
  • FIG. 2 is a schematic diagram showing an exemplary process of this disclosure for producing p-xylene by upgrading hydrocarbons, according to one embodiment.
  • a process is described as comprising at least one“step.” It should be understood that each step is an action or operation that may be carried out once or multiple times in the process, in a continuous or discontinuous fashion. Unless specified to the contrary or the context clearly indicates otherwise, multiple steps in a process may be conducted sequentially in the order as they are listed, with or without overlapping with one or more other step, or in any other order, as the case may be. In addition, one or more or even all steps may be conducted simultaneously with regard to the same or different batch of material.
  • a second step may be carried out simultaneously with respect to an intermediate material resulting from treating the raw materials fed into the process at an earlier time in the first step.
  • the steps are conducted in the order described.
  • indefinite article“a” or“an” shall mean“at least one” unless specified to the contrary or the context clearly indicates otherwise.
  • embodiments using“an ether” include embodiments where one, two or more ethers are used, unless specified to the contrary or the context clearly indicates that only one ether is used.
  • i- C4 is iso-butane
  • TBHP is ieri-butyl hydroperoxide
  • TBA is ieri-butanol or ieri-BuOH
  • DTBP is di-feri-butyl peroxide
  • RT room temperature (and is 23°C unless otherwise indicated)
  • kPag is kilopascal gauge
  • psig pound-force per square inch gauge
  • psia pounds per square inch absolute
  • WHSV weight hourly space velocity
  • GC Gas Chromatography.
  • An“olefin,” alternatively referred to as“alkene,” is a linear, branched, or cyclic compound of carbon and hydrogen having at least one carbon-carbon double bond.
  • substituted means that a hydrogen atom in the compound or group in question has been replaced with a group or atom other than hydrogen.
  • the replacing group or atom is called a substituent.
  • Substituents can be, e.g., a substituted or unsubstituted hydrocarbyl group, a heteroatom, a heteroatom-containing group, and the like.
  • a“substituted hydrocarbyl” is a group derived from a hydrocarbyl group made of carbon and hydrogen by substituting at least one hydrogen in the hydrocarbyl group with a non hydrogen atom or group.
  • a heteroatom can be nitrogen, sulfur, oxygen, halogen, etc.
  • hydrocarbyl “hydrocarbyl group,” or“hydrocarbyl radical” interchangeably mean a group consisting of carbon and hydrogen atoms.
  • hydrocarbyl radical is defined to be C1-C100 radicals, that may be linear, branched, or cyclic, and when cyclic, aromatic or non-aromatic.
  • branched hydrocarbon means a hydrocarbon comprising at least 4 carbon atoms and at least one carbon atom connecting to three carbon atoms.
  • alkyl is an alkyl comprising at least one cyclic carbon chain.
  • An“acyclic alkyl’ is an alkyl free of any cyclic carbon chain therein.
  • A“linear alkyl” is an acyclic alkyl having a single unsubstituted straight carbon chain.
  • A“branched alkyl” is an acyclic alkyl comprising at least two carbon chains and at least one carbon atom connecting to three carbon atoms.
  • alkyl groups can include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, .vec-butyl, ieri-butyl, pentyl, iso-amyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and the like including their substituted analogues.
  • alkenyl means a straight-chain, branched-chain, or cyclic hydrocarbyl group having one or more carbon-carbon double bonds therein. These alkenyl radicals may be optionally substituted. Examples of suitable alkenyl radicals can include ethenyl, propenyl, allyl, l,4-butadienyl cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloctenyl, and the like, including their substituted analogues.
  • alkoxy or“alkoxy group” means a group having a structure R- 0-, wherein R is an alkyl.
  • the term“Cn” compound or group, wherein n is a positive integer means a compound or a group comprising carbon atoms therein at the number of n.
  • a “Cm to Cn” alkyl means an alkyl group comprising carbon atoms therein at a number in a range from m to n.
  • a C1-C3 alkyl means methyl, ethyl, n-propyl, or 1- methylethyl-.
  • the term“Cn+” compound or group, wherein n is a positive integer means a compound or a group comprising carbon atoms therein at the number of equal to or greater than n.
  • the term“Cn-” compound or group, wherein n is a positive integer means a compound or a group comprising carbon atoms therein at the number of equal to or lower than n.
  • hydroperoxide means a compound having a formula R-O-OH, wherein R is a substituted or unsubstituted hydrocarbyl group.
  • peroxide means a compound having a formula R-O-O-R’, wherein R and R’ are independently each a substituted or unsubstituted hydrocarbyl group.
  • alkyl, alkenyl, alkoxide, or aryl group without specifying a particular isomer (e.g., butyl) expressly discloses all isomers (e.g., n-butyl, iso-butyl, sec-butyl, and ieri-butyl).
  • para-substituted benzene derivative means a compound comprising a benzene ring that is substituted at any two carbon atoms in the ring spaced by two carbon atoms in between.
  • a para-substituted benzene derivative comprises at least two substituents on the benzene ring which, if one of them is on the “1” position on the benzene ring, another is on the“4” position.
  • a para-substituted benzene derivative may comprise three, four, five, or six substituents on the benzene ring.
  • para- substituted benzene derivatives include, p- xylene, 1, 4-diethylbenzene, l,2,4-trimethylbenzene, l,2,3,4-tetramethylbenzene, and the like.
  • the catalyst may be described as a catalyst precursor, a pre-catalyst compound, or a catalyst compound, and these terms are used interchangeably.
  • conversion refers to the degree to which a given reactant in a particular reaction (e.g., dehydration, coupling, etc.) is converted to products.
  • 100% conversion of an ether refers to complete consumption of the ether
  • 0% conversion of the ether refers to no measurable reaction of the ether.
  • the term“selectivity” refers to the degree to which a particular reaction forms a specific product, rather than another product.
  • 50% selectivity for iso-pentylene means that 50% of the products formed are iso-amylene (also referred to as 2-methyl-2-butene), and 100% selectivity for iso-amylene means that 100% of the product formed is iso-amylene.
  • the selectivity is based on the product formed, regardless of the conversion of the particular reaction.
  • the selectivity for a given product produced from a given reactant can be defined as weight percent (wt%) of that product relative to the total weight of the products formed from the given reactant in the reaction.
  • dehydration refers to a chemical reaction that converts an alcohol into its corresponding alkene and water.
  • dehydration of isobutanol produces isobutylene and water.
  • dimerization and “dimerizing” refer to oligomerization processes in which two activated molecules, the same (e.g., two isobutylene molecules) or similar to each other (e.g., a isobutylene molecule and a 2-methyl-pent- l-ene molecule) in chemical structure, can be combined with or without the assistance of a catalyst (a dimerization catalyst or oligomerization catalyst, as described herein) to form a larger molecule comprising all atoms from the reactant molecules (such as diisobutylene or 2,2,4-trimethylpentenes).
  • a catalyst a dimerization catalyst or oligomerization catalyst, as described herein
  • oligomerization can be used to refer to a“dimerization” reaction, unless the formation of oligomers other than dimers is expressly or implicitly indicated.
  • aromatization refers to processes in which non-aromatic hydrocarbon starting materials, such as alkenes or alkanes, are converted into one or more aromatic compounds (e.g., p-xylene) in the presence of a suitable catalyst by, e.g., dehydrocyclization.
  • Dehydrocyclization refers to a reaction in which an acyclic alkane, or an alkene, is converted into a (substituted or unsubstituted) aromatic hydrocarbon via dehydrogenation and cyclization steps, optionally in the presence of a suitable dehydrocyclization catalyst.
  • This disclosure provides processes for producing para-substituted benzene derivatives, such as para-substituted benzene derivatives, by oxidative coupling of olefins using dihydrocarbyl peroxides produced by upgrading branched hydrocarbons.
  • Processes include oxidizing a branched hydrocarbyl (e.g., a C4-C5 branched hydrocarbyl), such as a branched hydrocarbon, to form an oxidized products that can include one or more hydrocarbyl hydroperoxides and/or alcohol.
  • Processes can include introducing the oxidized products to a catalyst to form a dihydrocarbyl peroxide.
  • Processes can include introducing the oxidized products to a catalyst to form an olefin.
  • Processes can include introducing the olefin to the dihydrocarbyl peroxide to form a diene and reform at least a portion of the oxidized products.
  • Processes can further include dehydro-cyclizing the diene in the presence of a catalyst to form a para- substituted benzene derivative (e.g., an aromatic hydrocarbon).
  • the alcohol from the oxidized products and/or the alcohol formed during the diene formation can be recovered, or dehydrated to an iso-olefin, or used as a high-octane gasoline blend.
  • a process includes oxidizing a branched hydrocarbon, such as isobutane, to form an oxidized products that can include a hydrocarbyl hydroperoxide and/or an alcohol such as ieri-butanol (also referred to as /e/7-BuOH or TBA).
  • the alcohol can be optionally dehydrated to an olefin (e.g., iso butylene).
  • the olefin can be introduced to a dihydrocarbyl peroxide to form a diene and an alcohol byproduct.
  • Processes can include introducing the diene to a catalyst to form p-xylene.
  • the alcohol byproduct(s) can be recycled to the olefin formation stage or the peroxide formation stage.
  • Such recycling system of the alcohol to the corresponding olefin provides manufacturers with competitive and economic advantages such as reducing energy consumption and waste disposal, sustaining use of resources, and increasing cost-efficiency by minimizing the production expenditure.
  • FIG. 1 illustrates a process for producing p-xylene according to at least one embodiment of this disclosure.
  • a branched hydrocarbon feedstock is supplied by line 1 to an oxidation reactor 2.
  • a branched hydrocarbon feedstock is a branched hydrocarbon represented by Formula (F-I) (Scheme 1) including one or more C 2 to C20 alkanes (such as Ci to C15 alkane, such as Ci to C10 alkane, such as one or more of methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, and isomers thereof).
  • C 2 to C20 alkanes such as Ci to C15 alkane, such as Ci to C10 alkane, such as one or more of methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, and isomers thereof.
  • a branched hydrocarbon represented by Formula (F-I) can be an iso-butane, iso-pentane, iso hexane, iso-heptane, iso-octane, iso-nonane, iso-decane, or a mixture thereof.
  • R 1 , R 2 , and R 3 are methyl, such as the branched hydrocarbon is iso butane (i-C 4 ).
  • R 1 , R 2 , and R 3 in Formulas (F-I), (F-II), and (F-III) are independently each a substituted or unsubstituted hydrocarbyl, preferably an alkyl, more preferably a linear or branched alkyl, still more preferably a linear alkyl.
  • Such substituted or unsubstituted hydrocarbyl groups may have 1 to 20 carbons, such as 1 to 15 carbons, such as 1 to 10 carbons, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and isomers thereof; and
  • Adjacent R groups (R 1 and R 2 , and/or R 2 and R 3 , and/or R 3 and R 1 ) and/or substituents in Formulas (F-I), (F-II), and (F-III) may be joined to form a substituted hydrocarbyl, unsubstituted hydrocarbyl, aromatic or non-aromatic ring, unsubstituted heterocyclic ring or substituted heterocyclic ring, where the ring has 5, 6, 7, or 8 ring carbon atoms and where substitutions on the ring can join to form additional rings.
  • a feed comprising the branched hydrocarbon (e.g., i-C 4 , 1-C5, i-Ce, etc.) can be introduced to an oxidation reactor 2 via line 3, where an oxidizing agent is fed via line 1.
  • the efficiency of the oxidation reaction can be improved as the oxidizing agent can be broadly and widely distributed within the reactor.
  • the oxidizing agent can be introduced into a batch, semi-batch, or continuous, for example, fixed bed or fluid bed, reactor in a number of different ways, such as via a single injection point, several injection points, or even via a sparger arrangement.
  • the oxidizing agent can be dispersed into the reactor either through nozzles that are flush to the reactor vessel or through an internal distribution network.
  • the number of nozzles flush to the reactor can be one, a few or many.
  • the oxidizing agent can be introduced into a reactor through an internal distributor.
  • the internal distributor may be a single injection point, a few injection points or many injection points.
  • the distributor may contain arteries branching off of one or more common headers, and additional sub-arteries may branch off of each artery to form a network of arteries.
  • the arteries may be designed to have a uniform diameter, either the same or different diameter as the common headers, or be tapered in various diameters and different lengths.
  • Along each common header or artery there may be one or several or many nozzles to introduce the oxidizing agent.
  • the size and length of these nozzles may be similar or different depending on the required distribution of the oxidizing agent into the reactor.
  • the internal distributor, arteries, and nozzles may be insulated if used in a fluid bed or fixed bed reactor. The decision to insulate or not can change the metallurgical requirements, which can range from carbon steel or to stainless steels or to titanium or other suitable types of alloys.
  • Oxidation of branched hydrocarbons represented by Formula (F-I) in accordance with the present process can be performed with any suitable oxidizing agent.
  • suitable oxidizing agents can be, but are not limited to, air, oxygen gas (0 2 ), 9-azabicyclo[3.3.1 ]nonane N-oxyl (AJBNO), acetone, acrylonitrile, ammonium cerium (IV) nitrate, ammonium peroxydisulfate, 2-azaadamantane N-oxyl, 9-azanoradamantane N-oxyl, 1,4-benzoquinone, benzaldehyde, benzoyl peroxide, bleach, N-bromosaccharin, N-bromosuccmimide,
  • the oxidizing agent is air, or Oi (gas).
  • An oxidation reaction can be performed at a temperature from 100°C to 200°C, such as from 110°C to 190°C, such as from 120°C to 180°C, such as from 130°C to 170°C; a pressure of from 300 psig to 800 psig, such as from 400 psig to 700 psig, such as from 500 psig to 600 psig; a residence time of from 1 hour to 48 hours, such as from 2 hours to 24 hours, such as from 4 hours to 20 hours, such as from 6 hours to 10 hours.
  • an oxidation reaction is performed at a weight hourly space velocity (WHSV) from 0.01 hr 1 to 100 hr 1 , such as from 0.02 hr 1 to 50 hr 1 , such as from 0.02 hr 1 to 10 hr 1 .
  • WHSV weight hourly space velocity
  • R 1 , R 2 , and R 3 are all methyl.
  • isobutane of Formula (F-I) is oxidized by, e.g., air, to form /c/7- butyl hydroperoxide of Formula (F-II) and icrt-butyl alcohol of Formula
  • the oxidation of a branched hydrocarbon represented by Formula (F-I) results in the formation of one or more oxidized product(s).
  • the oxidized products are a hydrocarbyl hydroperoxide, such as a hydrocarbyl hydroperoxide represented by Formula (F-II), and an alcohol, such as an alcohol represented by Formula (F-III).
  • R 1 , R 2 , and R 3 are independently each a hydrocarbyl and substituted hydrocarbyl, and adjacent R groups (R 1 and R 2 , and/or R 2 and R 3 , and/or R 3 and R 1 ) and/or substituents in Formulas (F-I), (F-II), and (F-III) may be joined to form a substituted hydrocarbyl, hydrocarbyl, aromatic or non-aromatic ring, unsubstituted heterocyclic ring or substituted heterocyclic ring, where the ring has 5, 6, 7, or 8 ring carbon atoms and where substitutions on the ring can join to form additional rings.
  • Such substituted or unsubstituted hydrocarbyl groups may have 1 to 20 carbons, such as 1 to 15 carbons, such as 1 to 10 carbons.
  • a hydrocarbyl group can be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, or isomers thereof.
  • the oxidized products represented by Formulas (F-II) and (F-III) are introduced to reactor 6 via line 4. Unreacted branched hydrocarbons remaining in the oxidized products stream can be separated from the said oxidized products stream and further recycled back to the oxidation reactor 2 via line 5.
  • a reactor 6 where a dihydrocarbyl peroxide represented by Formula (F-IV) is formed over an acid catalyst (e.g., AmberlystTM, acidic clay) (Scheme 2).
  • exemplary configuration for reactor 6 can be a reactive distillation reactor/column where water can be continuously removed as an overhead by-product via line 7.
  • R 1 , R 2 , and R 3 in Formulas (F-II) and (F-IV) are independently each a substituted or unsubstituted hydrocarbyl, preferably alkyl, more preferably linear alkyl or branched alkyl, still more preferably linear alkyl.
  • R 1 , R 2 , and R 3 are the same.
  • Such substituted or unsubstituted hydrocarbyl groups for R 1 , R 2 , and R 3 may have 1 to 20 carbons, such as 1 to 15 carbons, such as 1 to 10 carbons, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and isomers thereof; preferably methyl, ethyl, and n-propyl;
  • Adjacent R groups (R 1 and R 2 , and/or R 2 and R 3 , and/or R 3 and R 1 ) and/or substituents in Formulas (F-I), (F-II), and (F-IV) may be joined to form a substituted hydrocarbyl, hydrocarbyl, aromatic or non-aromatic ring, unsubstituted heterocyclic ring or substituted heterocyclic ring, where the ring has 5, 6, 7, or 8 ring carbon atoms and where substitutions on the ring can join to form additional rings;
  • R 1 , R 2 , and R 3 of Formulas (F-III) and (F-IV) are independently each a substituted or unsubstituted hydrocarbyl, preferably an alkyl, more preferably a linear or branched alkyl, still more preferably a linear alkyl.
  • R 1 , R 2 , and R 3 are the same.
  • Such substituted or unsubstituted hydrocarbyl groups for R 1 , R 2 , and R 3 may have 1 to 20 carbons, such as 1 to 15 carbons, such as 1 to 10 carbons, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and isomers thereof.
  • R 1 in Formula (F-II) and R 1’ are the same
  • R 2 in Formula (F-II) and R 2’ are the same
  • R 3 in Formula (F-II) and R 3’ are the same. More preferably R 1 , R 2 , R 3 , R 1’ , R 2’ , and R 3’ are all the same group; and
  • Adjacent R groups (R r and R 2’ , and/or R 2’ and R 3’ , and/or R 3’ and R 1’ ) of Formula (F- IV) may be joined to form a substituted hydrocarbyl, hydrocarbyl, aromatic or non aromatic ring, unsubstituted heterocyclic ring or substituted heterocyclic ring, where the ring has 5, 6, 7, or 8 ring carbon atoms and where substitutions on the ring can join to form additional rings.
  • Suitable examples of the conversion of a hydrocarbyl hydroperoxide (F-II) and an alcohol (F-III) to dihydrocarbyl peroxide (F-IV) using an acid catalyst such as an inorganic heteropoly- and/or isopoly-acid catalyst, are described in U.S. Pat. No. 5,288,919 and U.S. Pat. No. 7,034,189, each incorporated herein by reference.
  • Any suitable acid catalyst can be used for the conversion of the hydrocarbyl hydroperoxide (F-II) and the alcohol (F-III) to the dihydrocarbyl peroxide (F-IV).
  • any suitable acid catalyst can be, but are not limited to, AmberlystTM resin, NafionTM resin, aluminosilicates, acidic clay, zeolites (natural or synthetic), silicoaluminophosphates (SAPO), heteropoly acids, acidic oxides such as tungsten oxide on zirconia, molybdenum oxide on zirconia, sulfated zirconia, liquid acids such as sulfuric acid, or acidic ionic liquids.
  • AmberlystTM resin AmberlystTM resin
  • NafionTM resin AmberlystTM resin
  • aluminosilicates aluminosilicates
  • acidic clay zeolites (natural or synthetic)
  • SAPO silicoaluminophosphates
  • SAPO silicoaluminophosphates
  • heteropoly acids acidic oxides such as tungsten oxide on zirconia, molybdenum oxide on zirconia, sulfated zirconia
  • Conditions for the production of the dialkyl-peroxide (F-IV) in reactor 6 can be a temperature from 50°C to 200°C, such as from 60°C to l50°C, such as from 80°C to l20°C; and/or a residence time of from 0.01 hour to 24 hours, such as from 0.1 hours to 20 hours, such as from 0.5 hours to 10 hours.
  • the catalytic conversion of the hydrocarbyl hydroperoxide (F-II) and the alcohol (F-III) to the dihydrocarbyl peroxide (F-IV) is performed at a weight hourly space velocity (WHSV) from 0.01 hr 1 to 100 hr 1 , such as from 0.02hr _1 to 50 hr 1 , such as from 0.02 hr 1 to 10 hr 1 .
  • the hydrocarbyl hydroperoxide (F-II) to alcohol (F-III) mole ratio can be in the range of from 0.5 to 2, such as from 0.8 to 1.5, such as from 0.9 to 1.1.
  • the pressure of the reaction is held at appropriate ranges to ensure that the reaction occurs substantially in a liquid phase, for example, from 0 psig to 300 psig, such as from 5 psig to 100 psig, such as from 15 psig to 50 psig.
  • a reaction that occurs substantially in a liquid phase provides substantial mixing of the reactants and prevents fouling or clogging of a reactor and/or lines of the reactor.
  • the reaction can be performed with or without a solvent.
  • Suitable solvents may include hydrocarbons having a carbon number (e.g., number of carbons in the molecule) of greater than 3, such as paraffins, naphthenes, or aromatics, or a mixture thereof.
  • any unreacted branched hydrocarbons (F-I) from the oxidation can be used as solvent for the dihydrocarbyl peroxide synthesis.
  • the dihydrocarbyl peroxide represented by Formula (F-IV) is then sent via line 8 to a reactor 9 where the production of the corresponding dienes (such as dienes represented by Formula (F-VI)) and alcohols (such as alcohols represented by Formula (F-III)) occurs in the presence of an olefin (F-V).
  • dienes such as dienes represented by Formula (F-VI)
  • alcohols such as alcohols represented by Formula (F-III)
  • R 1 , R 2 , R 3 , R 1 , R 2 , and R 3 are all methyl.
  • ieri-butyl hydroperoxide of Formula (F-II) reacts with ieri-butyl alcohol of Formula (F-III) in the presence of a catalyst such as an acid to produce di-ieri-butyl peroxide and water.
  • Processes of this disclosure include introducing an olefin represented by Formula (F-V) to a dihydrocarbyl peroxide represented by Formula (F-IV) to form a polyene (such as a diene) represented by Formula (F-VI), and reforming at least a portion of the oxidized products (e.g., alcohol) (Scheme 3).
  • Such process for polyene production in which dihydrocarbyl peroxide (F-IV) is used to initiate a coupling of an olefin (F-V), such as a radical coupling reaction, can be referred to as a dehydro dimerization process where two molecules of an olefin (F-V) can react with a dihydrocarbyl peroxide (F-IV) to form a dimer (e.g., a diene) (F-VI) while the hydrogen is transferred to dihydrocarbyl peroxide converting the peroxide to alcohol.
  • a dehydro dimerization process where two molecules of an olefin (F-V) can react with a dihydrocarbyl peroxide (F-IV) to form a dimer (e.g., a diene) (F-VI) while the hydrogen is transferred to dihydrocarbyl peroxide converting the peroxide to alcohol.
  • R 1 , R 2 , and R 3 in Formulas (F-IV), and (F-III) are independently each a substituted or unsubstituted hydrocarbyl, preferably an alkyl, more preferably a linear or branched alkyl, still more preferably a linear alkyl.
  • R 1 , R 2 , and R 3 are the same.
  • Such substituted or unsubstituted hydrocarbyl groups for R 1 , R 2 , and R 3 may have 1 to 20 carbons, such as 1 to 15 carbons, such as 1 to 10 carbons, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and isomers thereof; preferably methyl, ethyl, and n-propyl;
  • Adjacent R groups (R 1 and R 2 , and/or R 2 and R 3 , and/or R 3 and R 1 ) and/or substituents in Formulas (F-IV) and (F-III) may be joined to form a substituted hydrocarbyl, hydrocarbyl, aromatic or non-aromatic ring, unsubstituted heterocyclic ring or substituted heterocyclic ring, where the ring has 5, 6, 7, or 8 ring carbon atoms and where substitutions on the ring can join to form additional rings;
  • R 1 , R 2 , and R 3 in Formulas (F-III) and (F-IV) are independently each a substituted or unsubstituted hydrocarbyl, preferably an alkyl, more preferably a linear or branched alkyl, still more preferably a linear alkyl.
  • R 1 , R 2 , and R 3 are the same.
  • Such substituted or unsubstituted hydrocarbyl groups for R 1’ , R 2’ , and R 3’ may have 1 to 20 carbons, such as 1 to 15 carbons, such as 1 to 10 carbons, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and isomers thereof.
  • R 1 in Formula (F-IV) and R 1’ are the same
  • R 2 in Formula (F-IV) and R 2’ are the same
  • R 3 in Formula (F-IV) and R 3 are the same. More preferably R 1 , R 2 , R 3 , R 1 , R 2 , and R 3’ are all the same group; and
  • Adjacent R groups (R r and R 2’ , and/or R 2’ and R 3’ , and/or R 3’ and R 1’ ) and/or substituents in Formulas (F-III) and (F-IV) may be joined to form a substituted hydrocarbyl, unsubstituted hydrocarbyl, aromatic or non-aromatic ring, unsubstituted heterocyclic ring or substituted heterocyclic ring, where the ring has 5, 6, 7, or 8 ring carbon atoms and where substitutions on the ring can join to form additional rings;
  • R 1 and R 2 in Formula (F-V) are independently each a hydrogen, Ci to C19 hydrocarbyl, or Ci to C19 substituted hydrocarbyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and isomers thereof);
  • R 1 , R 5 , and R 6 in Formula (F-VI) are independently each a hydrogen, Ci to C19 hydrocarbyl, or Ci to C19 substituted hydrocarbyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and isomers thereof);
  • R 3 and R 4 in Formulas (F-V) and (F-VI) are independently each a hydrogen, Ci to C19 hydrocarbyl, or Ci to C19 substituted hydrocarbyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and isomers thereof), and where at least one of R 3 or R 4 is hydrogen.
  • R 1 , R 3 and R 4 in Formula (F-VI) are independently each a hydrogen, Ci to C19 hydrocarbyl, or Ci to C19 substituted hydrocarbyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and isomers thereof), and where at least one of R 3 or R 4 is hydrogen.
  • Adjacent R groups (R 1 and R 2 , and/or R 2 and R 3 , R 3 and R 1 , and R 6 and R 1 ) and/or substituents in Formulas (F-IV) and (F-VI) may be joined to form a substituted hydrocarbyl, hydrocarbyl, aromatic or non-aromatic ring, unsubstituted heterocyclic ring or substituted heterocyclic ring, where the ring has 5, 6, 7, or 8 ring carbon atoms and where substitutions on the ring can join to form additional rings.
  • Adjacent R groups (R 1 and R 2 , and/or R 2 and R 3 , R 3 and R 1 , R 1 and R 5 , R 5 and R 6 ) and/or substituents in Formulas (F-III), (F-IV), (F-V), and (F-VI) may be joined to form a substituted hydrocarbyl, hydrocarbyl, aromatic or non-aromatic ring, unsubstituted heterocyclic ring or substituted heterocyclic ring, where the ring has 5, 6, 7, or 8 ring carbon atoms and where substitutions on the ring can join to form additional rings.
  • a dihydrocarbyl peroxide represented by Formula (F-IV) is introduced to a reactor (e.g., a coupling reactor) 9 via line 8.
  • An olefin represented by Formula (F-V) can be introduced to the reactor 9 via line 12 as a co-feed or separately from the dihydrocarbyl peroxide (F-IV) stream, either continuously or in batch mode or in semi-batch mode.
  • the olefin represented by Formula (F-V) can be introduced into reactor 9 in a number of different ways, such as via a single injection point, several injection points, or even via a sparger arrangement.
  • the olefin represented by Formula (F-V) can be dispersed into the reactor 9 either through nozzles that are flush to the reactor vessel or through an internal distribution network.
  • the number of nozzles flush to the reactor 9 can be one, a few or many.
  • the olefin represented by Formula (F-V) can be introduced into a reactor 9, for example, through an internal distributor.
  • the internal distributor may be a single injection point, a few injection points or many injection points.
  • the distributor may contain arteries branching off of one or more common headers, and additional sub- arteries may branch off of each artery to form a network of arteries.
  • the arteries may be designed to have a uniform diameter, either the same or different diameter as the common headers, or be tapered in various diameters and different lengths.
  • the size and length of such nozzles may be similar or different depending on the required distribution of the olefin represented by Formula (F-V) into the reactor.
  • the internal distributor, arteries, and nozzles may be insulated.
  • Processes for making diene(s) represented by Formula (F-VI) and alcohol(s) represented by Formula (F-III) via a coupling reaction of olefin(s) represented by Formula (F-V) and dihydrocarbyl peroxide(s) represented by Formula (F-IV) can be performed at a temperature from l00°C to 200°C, such as from H0°C to l90°C, such as from l20°C to l80°C, such as from l30°C to l70°C (e.g., 170°C), at a temperature rate of 2°C/minute for example; a pressure of from 100 psig to 1,500 psig, such as from 500 psig to 1,200 psig, such as any suitable pressure to ensure that the feed remains in a liquid phase; and/or a residence time of from 1 hour to 48 hours, such as from 2 hours to 24 hours, such as from 4 hours to 16 hours.
  • the coupling reaction of the dihydrocarbyl peroxide (F-IV) and the olefin (F-V) is performed at a weight hourly space velocity (WHSV) from 0.01 hr 1 to 100 hr ⁇ such as from 0.02 hr 1 to 50 hr 1 , such as from 0.02 hr 1 to 10 hr 1 .
  • WHSV weight hourly space velocity
  • a conversion of dihydrocarbyl peroxide(s) represented by Formula (F-V) is achieved in the reactor 9.
  • the resulting reaction products i.e., diene (F-VI) and alcohol (F-III)
  • by-products e.g., ketone(s); C9 + aromatics
  • unreacted olefins F-
  • V) are sent to one or more separation unit(s) (not shown) via line 10 for separation/fractionation, and optional recycling processes.
  • the oxidation process of branched hydrocarbons can provide a hydroperoxide to alcohol ratio above 1; and there is incentive to obtain higher ratios, e.g. more hydroperoxide means a more efficient process.
  • the ratio hydroperoxide to alcohol is typically greater than 1, recycling of the alcohol becomes advantageous to completely utilize the hydroperoxide for diperoxide synthesis.
  • the alcohol (F-III) can be obtained from any suitable fermentation process of biomass, such as a fermentation process of biomass using microorganisms capable of producing alcohol (e.g., iso-butanol) as described in U.S. Pub. No. 2011/0087000 Al.
  • Suitable biomass, biomass materials, or biomass components include but are not limited to, wood, wood residues, forest debris, sawdust, slash bark, scrap lumber, manure, thinnings, forest cullings, begasse, com fiber, corn stover, empty fruit bunches, fronds, palm fronds, flax, straw, low-ash straw, energy crops, palm oil, non- food-based biomass materials, crop residue, slash, pre-commercial thinnings, urban wood and yard wastes, tree residue, annual covercrops, switchgrass, mill residues, miscanthus, animal manure (dry and/or wet), cellulosic containing components, cellulosic components of separated yard waste, cellulosic components of separated food waste, cellulosic components of separated municipal solid waste, or combinations thereof.
  • Suitable cellulosic biomass may include biomass derived from or containing cellulosic materials.
  • a mixture of reaction products i.e., diene (F-
  • unreacted olefins can be recycled back to the coupling reactor 9 via line 11, while the remaining products are fractionated in order to separate by-products, alcohol (F-III), diene (F-VI), and high octane gasoline, as well as jet-range hydrocarbons.
  • Heavier coupling products in the C9 + range such as high octane gasoline ( ⁇ Ci 2 ) or distillate (C12 + ), are diverted to a fuels pool.
  • the alcohol (F-III) from a primary fractionator can be recycled, when needed, either fully or partially to reactor 9 for the formation of dihydrocarbyl peroxides (F-IV). Accordingly, an excess of alcohol (F-III) can be converted to a corresponding ether by reacting with an alcohol (such as methanol or ethanol).
  • the etherification can be performed either in a single process or by a two-step process where the alcohol (F-III) (e.g., TBA) can be first converted to an olefin (e.g., iso-butylene) followed by the reaction with the said alcohol.
  • the etherification reaction can be carried out in a fixed-bed reactor or a catalytic distillation reactor where an acid catalyst can be employed.
  • suitable acid catalysts may include, but are not limited to, resins such as DowexTM, AmberlystTM, NafionTM, sulfuric acid, sulfonic acid, phosphoric acid (neat or solid-supported on silica, alumina, or clay), acidic clay, aluminosilicate, zeolite, silicoaluminophosphate, acidic oxides such as tungsten oxide on zirconia, molybdenum oxide on zirconia, sulfuated zirconia, acidic ionic liquids; Lewis acids such as aluminum chloride or boron trifluoride.
  • the etherification reaction can be suitably carried out at a temperature of l00°C to 400°C, such as from l50°C to 350°C, and a pressure of 700 kPag to 3450 kPag (100 psig to 500 psig), such as 1,000 kPag to 2760 kPag (150 psig to 400 psig).
  • the alcohol (F-III) recovered from a fractionator can also be used as a chemical product or fuel blend, or can be dehydrated giving olefin (F-V), such as an iso-olefin (Scheme 4).
  • Dehydration can be carried out in a dehydration unit 17, such as a vapor phase unit, at a temperature of from l50°C to 450°C, such as from 200°C to 350°C and/or a pressure of from 700 kPag to 3450 kPag (100 psig to 500 psig), such as 1,000 KPag to 2,070 kPag (150 psig to 300 psig) in fixed-bed or slurry reactors.
  • An acidic catalyst can be used, such as those described above for the etherification reaction. Water is separated from the product stream via line 18.
  • R 1 , R 2 , and R 3 in Formula (F-III) are independently each a substituted or unsubstituted hydrocarbyl.
  • Hydrocarbyl groups may have 1 to 20 carbons, such as 1 to 15 carbons, such as 1 to 10 carbons, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and isomers thereof.
  • Adjacent R groups (R 1 and R 2 , R 2 and R 3 , and/or R 3 and R 1 ) and/or substituents in Formula (F-III) may be joined to form a substituted hydrocarbyl, hydrocarbyl, aromatic or non-aromatic ring, unsubstituted heterocyclic ring or substituted heterocyclic ring, where the ring has 5, 6, 7, or 8 ring carbon atoms and where substitutions on the ring can join to form additional rings.
  • R 1 , R 2 , R 3 , and R 4 in Formula (F-V) are independently each a substituted or unsubstituted hydrocarbyl, wherein at least one of R 3 and R 4 is hydrogen.
  • Hydrocarbyl groups may have 1 to 20 carbons, such as 1 to 15 carbons, such as 1 to 10 carbons, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and isomers thereof.
  • Adjacent R groups (R 1 and R 2 , R 3 and R 1 , R 3 and R 4 , and/or R 2 and R 4 ) and/or substituents in Formula (F-V) may be joined to form a substituted hydrocarbyl, hydrocarbyl, aromatic or non-aromatic ring, unsubstituted heterocyclic ring or substituted heterocyclic ring, where the ring has 5, 6, 7, or 8 ring carbon atoms and where substitutions on the ring can join to form additional rings.
  • the olefin (F-V), such as an iso-olefin, formed after the alcohol (F-III) dehydration can be used as a chemical intermediate for the production of polymers, rubber, or hydrocarbon resins.
  • the iso-olefins can be converted to gasoline, kero-jet, diesel, and lubricant range products via oligomerization.
  • the oligomerization can be performed in either slurry or fixed-bed reactors using an acid catalyst such as those described above for the etherification reaction.
  • the oligomerization reaction can be carried out at a temperature of from 0°C to 350°C, such as 0°C to l00°C, such as from 0°C to 50°C, and/or a pressure of from 10 psig to 2000 psig, such as 50 psig to 1000 psig.
  • the olefin (F-V) formed after the alcohol (F-III) dehydration can be converted to higher molecular weight products such as gasoline, kero-jet, or diesel via alkylation.
  • Alkylation can be carried out using an acid catalyst such as sulfuric acid, hydrofluoric acid, or zeolites in the faujasite (FAU), mordenite (MOR), MFI, or MWW families.
  • the olefin (F-V) can be fed with a branched hydrocarbon (such as iso-butane or iso-pentane) at a branched hydrocarbon/olefin ratio of 1.2 to 50, such as 1.5 to 20, such as 5 to 10.
  • the reaction temperature may be maintained appropriately depending on the catalyst used (e.g., 0°C to 5°C for sulfuric acid or HF; l0°C to 200°C for solid catalysts such as zeolites).
  • the unreacted alcohol (F-III) obtained after separation from the olefin (F-V) (e.g., by liquid-liquid or gas-liquid separation) can be further dehydrated in additional dehydration reactors, and the resulting olefin product(s) (such as olefin (F-V)) can be added to the feedstock for the dimerization process in the reactor 9 to form the diene (F-VI).
  • Such recycling system of the alcohol to the corresponding olefin provides manufacturers with competitive and economic advantages such as reducing energy consumption and waste disposal, sustaining use of resources, and increasing cost- efficiency by minimizing the production expenditure.
  • natural gas liquids, liquid petroleum gas, and refinery light gas such as light virgin naphtha (LVN) or light catalytic naphtha (LCN) can also be upgraded using processes of this disclosure.
  • LNN light virgin naphtha
  • LPN light catalytic naphtha
  • diene (F-VI) formed in the reactor 9 is sent to a dehydro-cyclization (DHC) reactor 20 via line 15, where it is cyclized and dehydrogenated to a substituted or unsubstituted para-substituted benzene derivative represented by Formula (F-VII) (Scheme 5).
  • the para-substituted benzene derivative (F-VII) such as an aromatic compound, can be recovered via line 22.
  • Examples of para-substituted benzene derivatives represented by Formula (F-VII) can be para- substituted phenyl compounds, such as p-xylene.
  • the stream including the diene (F-VI) in line 15 may include diluent gases, such as nitrogen, argon, and/or methane.
  • R 1 and R 1’ in Formulas (F-VI) and (F-vii) are independently each a substituted or unsubstituted hydrocarbyl.
  • Hydrocarbyl groups may have 1 to 19 carbons, such as 1 to 15 carbons, such as 1 to 10 carbons, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and isomers thereof.
  • R 3 , R 4 , R 5 , and R 6 in Formulas (F-VI) and (F-VII) are independently each a hydrogen, Ci to C19 hydrocarbyl, or Ci to C19 substituted hydrocarbyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and isomers thereof), and where at least one of R 3 or R 4 is hydrogen.
  • R 3 and R 4 in Formulas (F-VI) and (F-VII) are independently each a hydrogen, Ci to C19 hydrocarbyl, or Ci to C19 substituted hydrocarbyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and isomers thereof), and where at least one of R 3 or R 4 is hydrogen.
  • Suitable DHC catalysts may include supported noble metals such as Pt, Pd, Rh, Ir, Ru on silica, alumina, titania, or zirconia. Such noble metals can also be alloyed with Sn, Cu, or Ag.
  • effective DHC catalysts include transition metal oxides such as chromium oxide, molybdenum oxide, tungsten oxide, vanadium oxide, niobium oxide, rhenium oxide, iron oxide, cobalt oxide, nickel oxide, or mixed oxides comprising the afore mentioned, in bulk or supported on alumina or silica.
  • one or more of the DHC process(es) can each be carried out in two or more reactors (connected either in series or in parallel), so that during operation of the process, particular reactors can be bypassed (or taken "offline") to allow maintenance (e.g., catalyst regeneration) to be carried out on the bypassed reactor, while still permitting the process to continue in the remaining operational reactors.
  • a DHC process can be carried out in two reactors connected in series (whereby the product of the dimerization process (e.g., the diene (F-VI)) is the feedstock for the first DHC reactor 20, and the product of the first DHC reactor 20 is the feedstock for the second DHC reactor (not shown)).
  • the first DHC reactor 20 can be bypassed using the appropriate piping and valves such that the product of the DHC process is now the feedstock for the second dehydrocyclization reactor (not shown).
  • bypassing one of the reactors may simply entail closing the feed and product lines of the desired reactor.
  • alumina and silica based catalysts and reactor configurations may be used to prepare aromatics (e.g., para- substituted phenyl compounds) from low molecular weight hydrocarbons.
  • suitable catalysts may include bismuth, lead, or antimony oxides (U.S. Pat. No. 3,644,550 and U.S. Pat. No. 3,830,866), chromium treated alumina (U.S. Pat. No. 3,836,603 and U.S. Pat. No. 6,600,081), rhenium treated alumina (U.S. Pat. No. 4,229,320) and platinum treated zeolites (WO 2005/065393 A2).
  • a non-limiting list of such catalysts includes mixtures of chromia-alumina and bismuth oxide (e.g., bismuth oxide prepared by the thermal decomposition of bismuth compounds such as bismuth nitrate, bismuth carbonate, bismuth hydroxide, bismuth acetate, etc.; and chromia-alumina prepared by impregnating alumina particles with a chromium composition to provide particles containing at least 2 mol%, such as 10 mol%, such as 15 mol%, such as 20 mol%, such as 25 mol%, such as 30 mol%, such as 35 mol%, such as 40 mol%, such as 45 mol%, such as 50 mol% chromia, optionally including a promoter such as potassium, sodium, or silicon, and optionally including a diluent such as silicon carbide, alpha-alumina, zirconium oxide, etc.); bismuth oxide, lead oxide or antimony oxide in combination with supported platinum, supported
  • the DHC catalyst is selected from, for example, chromium-oxide treated alumina, platinum- and tin-containing zeolites and alumina, or cobalt- and molybdenum-containing alumina.
  • the DHC catalyst can be a commercial catalyst based on chromium oxide on an alumina support.
  • the DHC reaction is carried out below or slightly above atmospheric pressure, for example at pressures ranging from 1 pounds per square inch absolute (psia) to 20 psia, such as 5 psia to 15 psia, such as 8 psia to 12 psia.
  • psia pounds per square inch absolute
  • the DHC process can be carried out in reactor 20 at a temperature of from 400°C to 600°C, such as from 425°C to 575°C, such as from 450°C to 550°C, such as from 475°C to 525°C; and/or at WHSV values of from 0.5 hr 1 to 5 hr 1 , such as from 1 hr 1 to 4 hr 1 , such as from 2 hr 1 to 3 hr 1 .
  • the DHC reaction is operated at conversions ranging from 20% to 50%, and provides a selectivity to para- substituted benzene derivatives (F-VII) (e.g., percentage of xylene products such as p- xylene) greater than 75%.
  • F-VII para- substituted benzene derivatives
  • the para-substituted benzene derivative selectivity is 75% or greater, such as 80% or greater, such as 85% or greater, such as 90% or greater, such as 95% or greater, such as 99% or greater.
  • processes of this disclosure provide an alternative process to selectively produce para-substituted phenyl compounds (such as p-xylene).
  • both the conversion and selectivity of the DHC reaction for para-substituted phenyl compounds can be enhanced by adding diluents to the feedstock, such as hydrogen, nitrogen, argon, and methane.
  • diluents such as hydrogen, nitrogen, argon, and methane.
  • Unreacted iso-olefins e.g., isobutylene from the dimerization reaction in reactor 9
  • the selectivity of a dimerization reaction process is improved by carrying out the dimerization under low conversion conditions, such that the product from the dimerization reaction contains significant amounts of unreacted iso-olefin (e.g., isobutylene), a portion of which can be recycled back to the dimerization reaction feedstock, and/or a portion of which can be present in the DHC reaction feedstock.
  • iso-olefin or iso-praffins (F-I)
  • Any iso-olefin (or iso-praffins (F-I)) remaining in the product of the DHC reaction can then be recycled back into the dimerization feedstock for radical coupling (e.g., in reactor 9) and/or into the DHC feedstock (e.g., reactor 20).
  • the conversion of polyenes (F-VI) into aromatic compounds (F-VII) can be a net oxidation reaction that releases hydrogen from the aliphatic hydrocarbons present in the reaction mixture. If no oxygen is present, hydrogen gas is a co-product, and light alkanes such as methane and ethane may be by-products. If oxygen is present, the hydrogen is converted into water.
  • a DHC reaction process of this disclosure is carried out in the relative absence of oxygen (although trace levels of oxygen may be present due to leaks in the reactor system, and/or the feedstock for the DHC reaction process may have trace contamination with oxygen).
  • the hydrogen and light hydrocarbons produced as a by-product of the DHC reaction are themselves valuable compounds that can be removed and used for other chemical processes (e.g., hydrogenation of alkene by-products, for example Cx alkenes) to produce alkanes suitable for use as renewable fuels or renewable fuel additives (e.g., isooctane), etc.).
  • Such light hydrocarbon compounds can be collected and used throughout a refinery.
  • Such hydrogen also reacts with iso-olefins (such as isobutylene and diisobutylene) to produce branched hydrocarbons (such as isobutane and isooctane) which can be recycled to use as diluents for dimerization or feedstock for DHC to form iso-olefins by dehydrogenation of branched hydrocarbons and para-substituted phenyl compounds by dehydrocyclization of branched hydrocarbons.
  • the mixture of hydrogen and light hydrocarbons produced from a DHC reaction can be used for hydrogenation without further purification, or the light hydrocarbons can be removed (either essentially completely or a portion thereof) to provide relatively pure or higher purity hydrogen prior to the hydrogenation reaction.
  • FIG. 2 illustrates a process for producing p-xylene according to at least one embodiment of this disclosure.
  • a branched hydrocarbon feedstock is an iso-butane feedstock supplied by line 31 to an oxidation reactor 32.
  • a feed comprising iso-butane (i-C 4 ) can be introduced to an oxidation reactor 32 via line 33, where an oxidizing agent is fed via line 31.
  • the efficiency of the oxidation reaction can be improved as the oxidizing agent can be broadly and widely distributed within the reactor.
  • the oxidizing agent can be introduced into a batch, semi batch, or continuous, for example, fixed bed or fluid bed, reactor in a number of different ways, such as via a single injection point, several injection points, or even via a sparger arrangement.
  • the oxidizing agent can be dispersed into the reactor either through nozzles that are flush to the reactor vessel or through an internal distribution network. The number of nozzles flush to the reactor can be one, a few or many.
  • the oxidizing agent can be introduced into a reactor through an internal distributor.
  • the internal distributor may be a single injection point, a few injection points or many injection points.
  • the distributor may contain arteries branching off of one or more common headers, and additional sub- arteries may branch off of each artery to form a network of arteries.
  • the arteries may be designed to have a uniform diameter, either the same or different diameter as the common headers, or be tapered in various diameters and different lengths.
  • Along each common header or artery there may be one or several or many nozzles to introduce the oxidizing agent. The size and length of these nozzles may be similar or different depending on the required distribution of the oxidizing agent into the reactor.
  • the internal distributor, arteries, and nozzles may be insulated if used in a fluid bed or fixed bed reactor.
  • the decision to insulate or not can change the metallurgical requirements, which can range from carbon steel or to stainless steels or to titanium or other suitable types of alloys.
  • Oxidation of i-C 4 in accordance with this disclosure can be performed with any suitable oxidizing agent, as described above.
  • the oxidizing agent is air or O2 (gas).
  • the oxidation reaction of i-C 4 can be performed at a temperature from l00°C to 200°C, such as from H0°C to l90°C, such as from l20°C to l80°C, such as from l30°C to l70°C; a pressure of from 300 psig to 800 psig, such as from 400 psig to 700 psig, such as from 500 psig to 600 psig; and/or a residence time of from 1 hour to 48 hours, such as from 2 hours to 24 hours, such as from 4 hours to 20 hours, such as from 6 hours to 10 hours.
  • the oxidation reaction is performed at a weight hourly space velocity (WHSV) from 0.01 hr 1 to 100 hr 1 , such as from 0.02 hr 1 to 50 hr 1 , such as from 0.02 hr 1 to 10 hr 1 .
  • WHSV weight hourly space velocity
  • i-C 4 results in the formation of the corresponding feri-butyl hydroperoxide (TBHP) and /c /7-butyl alcohol (TBA).
  • TBHP feri-butyl hydroperoxide
  • TBA /c /7-butyl alcohol
  • the oxidized products TBHP and TBA are introduced to reactor 36 via line 34. Unreacted i-C 4 remaining in the oxidized product stream can be separated from TBHP and TBA stream and recycled to the oxidation reactor 32 via line 35.
  • the oxidation mixture including TBHP and TBA is sent via line 34 to a reactor 36 where di-t-butyl peroxide (DTBP) is formed over an acid catalyst (e.g., AmberlystTM, acidic clay).
  • DTBP di-t-butyl peroxide
  • An exemplary configuration for reactor 36 can be a reactive distillation reactor/column where water can be continuously removed as overhead by product via line 37.
  • Suitable conditions for the production of DTBP include a temperature from 50°C to 200°C, such as from 60°C to l50°C, such as from 80°C to l20°C; and/or a residence time of from 0.01 hour to 24 hours, such as from 0.1 hours to 20 hours, such as from 0.5 hours to 10 hours, such as from 1 hours to 5 hours.
  • the conversion of TBHP and TBA to DTBP is performed at a weight hourly space velocity (WHSV) from 0.01 hr 1 to 100 hr 1 , such as from 0.02 hr 1 to 50 hr 1 , such as from 0.02 hr 1 to 10 hr 1 .
  • WHSV weight hourly space velocity
  • the TBHP and TBA mole ratio is in the range of from 0.5 to 2, such as from 0.8 to 1.5, such as from 0.9 to 1.1.
  • the pressure of the reaction is performed at appropriate ranges to ensure that the reaction occurs substantially in a liquid phase, for example, from 0 psig to 300 psig, such as from 5 psig to 100 psig, such as from 15 psig to 50 psig.
  • the reaction can be performed with or without a solvent.
  • Suitable solvents may include, but are not limited to, hydrocarbons having a carbon number greater than 3, such as paraffins, naphthenes, aromatics, or a mixture thereof. Conveniently, any unreacted i-C 4 can be used as solvent.
  • the DTBP is then sent via line 38 to a coupling reactor 39, such as a radical coupling reactor, in order to convert isobutylene into 2,5-dimethyl-l,5-hexadiene (precursor of p-xylene) via a dimerization process, such as a coupling process (e.g., radical coupling).
  • a coupling process e.g., radical coupling.
  • the isobutylene can be sourced from, e.g., petroleum refining processes, ethane cracking, conversion from ethylene, dehydrogenation of isobutane, or dehydration of isobutanol as described below, and the like.
  • DTBP is introduced to a reactor (e.g., a coupling reactor) 39 via line 38.
  • Isobutylene can be introduced to the reactor (e.g., a coupling reactor) 39 via line 42 either continuously or in batch mode or in semi-batch mode.
  • isobutylene can be introduced into reactor 39, as a co-feed or separately from DTBP stream, in a number of different ways, such as via a single injection point, several injection points, or even via a sparger arrangement.
  • Isobutylene can be dispersed into the reactor 39 either through nozzles that are flush to the reactor vessel or through an internal distribution network. The number of nozzles flush to the reactor 39 can be one, a few, or many.
  • isobutylene can be introduced into the reactor 39, for example, through an internal distributor.
  • the internal distributor may be a single injection point, a few injection points or many injection points.
  • the distributor may contain arteries branching off of one or more common headers, and additional sub-arteries may branch off of each artery to form a network of arteries.
  • the arteries may be designed to have a uniform diameter, either the same or different diameter as the common headers, or be tapered in various diameters and different lengths.
  • Along each common header or artery there may be one or several or many nozzles to introduce the olefin. The size and length of such nozzles may be similar or different depending on the required distribution of isobutylene into the reactor.
  • the internal distributor, arteries, and nozzles may be insulated.
  • Processes for 2,5-dimethyl-l,5-hexadiene formation can be performed at a temperature from l00°C to 200°C, such as from H0°C to l90°C, such as from l20°C to l80°C, such as from l30°C to l70°C (e.g., l70°C), at a temperature rate of 2°C/minute for example; a pressure of from 100 psig to 1,500 psig, such as from 500 psig to 1,200 psig, such as any suitable pressure to ensure that the feed remains in a liquid phase; and/or a residence time of from 1 hour to 48 hours, such as from 2 hours to 24 hours, such as from 4 hours to 16 hours.
  • the coupling reaction is performed at a weight hourly space velocity (WHSV) from 0.01 hr 1 to 100 hr 1 , such as from 0.02 hr 1 to 50 hr 1 , such as from 0.02 hr 1 to 10 hr 1 .
  • WHSV weight hourly space velocity
  • a conversion of DTBP is achieved in the reactor 39.
  • the isobutylene coupling products in the carbon number ranged of from 8 to 32 can be formed.
  • the coupling of isobutylene to form 2, 5-dimethyl- l,5-hexadiene can be obtained with 2,5- dimethyl- 1 -hexene at a molar ratio of 2,5-dimethyl-l,5-hexadiene to 2,5-dimethyl- 1- hexene of from 2 to 6, such as 4.
  • the reaction is regioselective, which provides the formation of p-xylene in higher yield.
  • reaction products e.g., 2,5-dimethyl-l,5-hexadiene and iso butanol
  • by-products e.g., acetone; C 9+ aromatics
  • unreacted isobutylene can be sent to one or more separation unit(s) (not shown) via line 40 for separation/fractionation, and recycling processes.
  • iso-butanol can be obtained from any suitable fermentation process of biomass, such as a fermentation process of biomass using microorganism capable of producing alcohol (e.g., iso-butanol) as described in U.S. Pub. No. 2011/0087000 Al.
  • Suitable biomass, biomass materials, or biomass components include but are not limited to, wood, wood residues, forest debris, sawdust, slash bark, scrap lumber, manure, thinnings, forest cullings, begasse, com fiber, com stover, empty fruit bunches, fronds, palm fronds, flax, straw, low-ash straw, energy crops, palm oil, non-food-based biomass materials, crop residue, slash, pre-commercial thinnings, urban wood and yard wastes, tree residue, annual covercrops, switchgrass, mill residues, miscanthus, animal manure (dry and/or wet), cellulosic containing components, cellulosic components of separated yard waste, cellulosic components of separated food waste, cellulosic components of separated municipal solid waste, or combinations thereof.
  • Suitable cellulosic biomass may include biomass derived from or containing cellulosic materials.
  • a mixture of reaction products e.g., 2,5- dimethyl- 1,5 -hexadiene recovered from line 45, and iso-butanol recovered from line 43
  • by-products e.g., acetone recovered from line 44; C9 + aromatics recovered from line 46
  • unreacted isobutylene from the coupling reactor 39 are sent to one or more separation unit(s) (not shown), such as one or more suitable column(s) and/or one or more suitable fractionator(s), via line 40 for separation/fractionation, and further recyclization processes.
  • unreacted isobutylene can be recycled to the coupling reactor 39 via line 41, while the remaining products are fractionated in order to separate by-products, iso-butanol, 2,5-dimethyl-l,5-hexadiene, and high octane gasoline, as well as jet-range hydrocarbons. Heavier coupling products in the C9 + range are diverted to the fuels pool such as high octane gasoline ( ⁇ Ci 2 ) or distillate (C12 + ).
  • the iso-butanol from a fractionator can be recycled, when needed, either fully or partially to reactor 36 for the formation of DTBP (not shown). Accordingly, an excess of iso-butanol can be converted to a corresponding ether by reacting with an alcohol (such as methanol or ethanol).
  • the etherification can be performed either in a single process or by a two-stage process where the iso-butanol can be first converted to iso-butylene followed by reaction with the alcohol.
  • the etherification reaction can be carried out in a fixed-bed reactor or a catalytic distillation reactor where an acid catalyst can be employed.
  • suitable acid catalysts may include resins such as DowexTM, AmberlystTM, NafionTM, sulfuric acid, sulfonic acid, phosphoric acid (neat or solid- supported on silica, alumina, or clay), acidic clay, aluminosilicate, zeolite, silicoaluminophosphate, acidic oxides such as tungsten oxide on zirconia, molybdenum oxide on zirconia, sulfuated zirconia, acidic ionic liquids; Lewis acids such as aluminum chloride or boron trifluoride.
  • resins such as DowexTM, AmberlystTM, NafionTM, sulfuric acid, sulfonic acid, phosphoric acid (neat or solid- supported on silica, alumina, or clay), acidic clay, aluminosilicate, zeolite, silicoaluminophosphate, acidic oxides such as tungsten oxide on zirconia, molybdenum
  • the etherification reaction can be suitably carried out at a temperature of l00°C to 400°C, such as from l50°C to 350°C, and/or a pressure of 700 kPag to 3450 kPag (100 psig to 500 psig), such as 1,000 kPag to 2760 kPag (150 psig to 400 psig).
  • the iso-butanol recovered from a fractionator can also be used as a chemical product, fuel blend, or dehydrated giving iso-butylene.
  • Dehydration can be carried out in a dehydration unit 47, such as a vapor phase unit, at a temperature of from l50°C to 450°C, such as from 200°C to 350°C and/or a pressure of from 700 KPag to 3450 kPag (100 psig to 500 psig), such as 1,000 KPag to 2,070 kPag (150 psig to 300 psig) in fixed-bed or slurry reactors.
  • An acidic catalyst can be used, such as those described above for the etherification reaction. Water is separated from the product stream and recovered via line 48.
  • the iso-butylene formed from the iso-butanol dehydration can be used as a chemical intermediate for the production of polymers, rubber, or hydrocarbon resins.
  • the iso-butylene can be converted to gasoline, kero-jet, diesel, and lubricant range products via oligomerization.
  • the oligomerization can be performed in either slurry or fixed-bed reactors using an acid catalyst such as those described above for the etherification reaction.
  • the oligomerization reaction can be carried out at a temperature of from 0°C to 350°C, such as 0°C to l00°C, such as from 0°C to 50°C, and/or a pressure of from 10 psig to 2000 psig, such as 50 psig to 1000 psig.
  • the iso-butylene formed after the iso-butanol dehydration can be converted to higher molecular weight products such as gasoline, kero-jet, or diesel via alkylation (not shown).
  • Alkylation can be carried out using an acid catalyst such as sulfuric acid, hydrofluoric acid, or zeolites in the faujasite (FAU), mordenite (MOR), MFI, or MWW families.
  • the iso-olefin can be fed with a branched hydrocarbon such as iso-butane or iso-pentane with a branched hydrocarbon/olefin (i/o) ratio of 1.2 to 50, such as 1.5 to 20, such as 5 to 10.
  • the reaction temperature may be maintained appropriately depending on the catalyst used (e.g., 0°C to 5°C with sulfuric acid or HF; l0°C to 200°C with solid catalysts such as zeolites).
  • the catalyst used e.g., 0°C to 5°C with sulfuric acid or HF; l0°C to 200°C with solid catalysts such as zeolites.
  • at least a portion of the unreacted iso-butanol obtained after separation from the iso-butylene, such as the iso-butylene (e.g., by liquid-liquid or gas-liquid separation) can be further dehydrated in additional dehydration reactors, and the resulting olefin product(s), such as iso butylene, added to the feedstock for the dimerization process in the reactor 39 to form the 2, 5-dimethyl- l,5-hexadiene.
  • Such recycling system of the iso-butanol to the corresponding iso-butylene provides a crucial
  • 2,5-dimethyl-l,5-hexadiene formed in the reactor 39 is sent to a dehydro-cyclization (DHC) reactor 50 via line 45, where it is cyclized and dehydrogenated to p-xylene.
  • P-xylene can be recovered via line 52.
  • DHC methods are described in The Oxidation of Isobutylene to p-Xylene over Bismuth Oxide-based Catalysts, Mireya R. Goldwasser and David L. Trimm, J. appl. Chem. Biotechnol., 1978, 28, pages 733 to 739, and U.S. Pub. No.
  • the stream including 2, 5-dimethyl- l,5-hexadiene in line 45 may include diluent gases, such as nitrogen, argon, and/or methane.
  • Suitable DHC catalysts may include supported noble metals such as Pt, Pd, Rh, Ir, Ru on silica, alumina, titania, or zirconia. Such noble metals can also be alloyed with Sn, Cu, or Ag.
  • effective DHC catalysts include transition metal oxides such as chromium oxide, molybdenum oxide, tungsten oxide, vanadium oxide, niobium oxide, rhenium oxide, iron oxide, cobalt oxide, nickel oxide, or mixed oxides comprising the afore mentioned, in bulk or supported on alumina or silica.
  • one or more of the DHC process(es) can each be carried out in two or more reactors (connected either in series or in parallel), so that during operation of a process, particular reactors can be bypassed (or taken "offline") to allow maintenance (e.g., catalyst regeneration) to be performed on the bypassed reactor, while still permitting the process to continue in the remaining operational reactors.
  • the DHC process could be carried out in two reactors connected in series (whereby 2,5-dimethyl-l,5-hexadiene is the feedstock for the first DHC reactor 50, and the product of the first DHC reactor 50 is the feedstock for the second DHC reactor (not shown)).
  • the first DHC reactor 50 can be bypassed using the appropriate piping and valves such that the product of the DHC process is now the feedstock for the second dehydrocyclization reactor (not shown).
  • bypassing one of the reactors may simply involve closing the feed and product lines of the desired reactor.
  • alumina and silica based catalysts and reactor configurations may be used to prepare aromatics from low molecular weight hydrocarbons.
  • suitable catalysts may include bismuth, lead, or antimony oxides (U.S. Pat. No. 3,644,550 and U.S. Pat. No. 3,830,866), chromium treated alumina (U.S. Pat. No. 3,836,603 and U.S. Pat. No. 6,600,081), rhenium treated alumina (U.S. Pat. No. 4,229,320) and platinum treated zeolites (WO 2005/065393 A2).
  • a non-limiting list of such catalysts include mixtures of chromia- alumina and bismuth oxide (e.g., bismuth oxide prepared by the thermal decomposition of bismuth compounds such as bismuth nitrate, bismuth carbonate, bismuth hydroxide, bismuth acetate, etc.; and chromia-alumina prepared by impregnating alumina particles with a chromium composition to provide particles containing at least 2 mol%, such as 10 mol%, such as 15 mol%, such as 20 mol%, such as 25 mol%, such as 30 mol%, such as 35 mol%, such as 40 mol%, such as 45 mol%, such as 50 mol% chromia, optionally including a promoter such as potassium, sodium, or silicon, and optionally including a diluent such as silicon carbide, alpha- alumina, zirconium oxide, etc.); bismuth oxide, lead oxide or antimony oxide in combination with supported platinum
  • a DHC catalyst includes, for example, chromium-oxide treated alumina, platinum- and tin-containing zeolites and alumina, or cobalt- or molybdenum-containing alumina.
  • the DHC catalyst can be a commercial catalyst based on chromium oxide on an alumina support.
  • the DHC reaction is carried out below or slightly above atmospheric pressure, for example at pressures ranging from 1 psia to 20 psia, such as 5 psia to 15 psia, such as 8 psia to 12 psia.
  • a DHC process can be performed at a temperature value of from 400 °C to 600°C, such as from 425 °C to 575 °C, such as from450°C to 550°C, such as from 475°C to 525°C; and/or at WHSV values of from 0.5 hr 1 to 5 hr 1 , such as from 1 hr 1 to 4 hr ', such as from 2 hr 1 to 3 hr 1 .
  • the DHC reaction is performed at a conversion of diene to p-xylene of from 20% to 50%, and provides a selectivity to p-xylene (e.g., percentage of xylene products such as p-xylene) greater than 75%.
  • p-xylene selectivity is 75% or greater, such as 80% or greater, such as 85% or greater, such as 90% or greater, such as 95% or greater, such as 99% or greater.
  • both the conversion and selectivity of the DHC reaction for p- xylene can be enhanced by adding diluents to the feedstock, such as hydrogen, nitrogen, argon, and methane.
  • Unreacted isobutylene (such as unreacted isobutylene from the dimerization reaction in reactor 39) can also be used as an effective diluent to improve the p-xylene selectivity of the DHC reaction, and to help suppress cracking.
  • the selectivity of the dimerization reaction process is improved by carrying out the dimerization under low conversion conditions, such that the product from the dimerization reaction contains significant amounts of unreacted isobutylene, a portion of which can be recycled back to the dimerization reaction feedstock, and a portion of which is present in the DHC reaction feedstock. Any iso-butylene (or iso-butane) remaining in the product of the DHC reaction (i.e., p- xylene) can then be recycled into the dimerization feedstock and/or the DHC feedstock.
  • the conversion of 2, 5-dimethyl- l,5-hexadiene into p-xylene can be a net oxidation reaction that releases hydrogen from the aliphatic hydrocarbons present in the reaction mixture. If no oxygen is present, hydrogen gas is a co-product, and light alkanes such as methane and ethane may be by-products. If oxygen is present, the hydrogen is converted into water. In at least on embodiment, the DHC reaction process is carried out in the relative absence of oxygen (although trace levels of oxygen may be present due to leaks in the reactor system, and/or the feedstock for the DHC reaction process may have trace contamination with oxygen).
  • the hydrogen and light hydrocarbons produced as a by-products of the DHC reaction are themselves valuable compounds that can be removed and used for other chemical processes (e.g., hydrogenation of alkene by-products, for example Cx alkenes) to produce alkanes suitable for use as renewable fuels or renewable fuel additives (e.g., isooctane), etc.).
  • Such light hydrocarbon compounds can be collected and used throughout a refinery.
  • Such hydrogen may also react with isobutylene and diisobutylene to produce isobutane and isooctane, which can be recycled to use as diluents for dimerization (isobutane and isooctane) or feedstock for DHC to form iso-butylene by dehydrogenation of iso-butane and p-xylene by dehydrocyclization of iso-butane.
  • the mixture of hydrogen and light hydrocarbons produced from the DHC reaction can be used for hydrogenation without further purification, or the light hydrocarbons can be removed (either essentially completely or a portion thereof) to provide relatively pure or higher purity hydrogen prior to the hydrogenation reaction.
  • the DHC feedstock may include 1% to 100% of 2,2,4-trimethylpentene, 2,5-dimethlyhexene, 2,5-dimethylhexadiene, or a mixture thereof.
  • the DHC feedstock includes less than 50% 2,2,4-trimethylpentenes, 2,5- dimethlyhexenes, and/or 2,5-dimethylhexadienes to reduce or eliminate "coking" of the dehydrocyclization catalyst.
  • the dehydrocyclization feedstock may include 1% or greater, such as from 1% to 50% 2,2,4-trimethylpentenes, 2,5- dimethlyhexenes, 2,5-dimethylhexadienes, or a mixture thereof.
  • conversion can be obtained of iso-butane to 2,5-dimethyl-l,5-hexadiene, using molecular oxygen in a liquid phase, while iso butane is converted to ieri-butyl alcohol, which is itself an upgraded product from iso butane.
  • the resulting alcohol can be used as a high octane blend for gasoline (e.g. / ⁇ ?/7- butyl alcohol from iso butane and 2-methyl-2-butanol from iso-pentane).
  • the alcohols can be converted to olefins via dehydration (e.g., iso-butylene), or etherified with an alcohol, such as methanol or ethanol, to use as a gasoline blend (e.g., methyl /c/7 -butyl ether (MTBE) or ethyl icri-butyl ether (ETBE) from iso-butane).
  • dehydration e.g., iso-butylene
  • etherified with an alcohol such as methanol or ethanol
  • a gasoline blend e.g., methyl /c/7 -butyl ether (MTBE) or ethyl icri-butyl ether (ETBE) from iso-butane.
  • MTBE methyl /c/7 -butyl ether
  • ETBE ethyl icri-butyl ether
  • ranges from any lower limit may be combined with any upper limit to recite a range not explicitly recited, as well as, ranges from any lower limit may be combined with any other lower limit to recite a range not explicitly recited, in the same way, ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited.
  • ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited.
  • within a range includes every point or individual value between its end points even though not explicitly recited. Thus, every point or individual value may serve as its own lower or upper limit combined with any other point or individual value or any other lower or upper limit, to recite a range not explicitly recited.
  • 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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Abstract

La présente invention concerne des procédés de production de dérivés de benzène para-substitués, tels que le p-xylène, par couplage oxydatif d'oléfines à l'aide de peroxyde de dihydrocarbyle résultant de la valorisation d'hydrocarbures. Dans un mode de réalisation, un procédé de formation d'un dérivé de benzène para-substitué comprend la mise en présence d'une première oléfine et d'un peroxyde de dihydrocarbyle pour former un premier alcool et une seconde oléfine qui est un polyène. Le procédé comprend la cyclisation de la seconde oléfine pour former le dérivé de benzène para-substitué. Les procédés de la présente invention peuvent comprendre une ou plusieurs opérations parmi : la mise en présence d'un hydroperoxyde d'hydrocarbyle avec le premier alcool et/ou un second alcool pour former le peroxyde de dihydrocarbyle ; l'oxydation d'un premier flux d'alimentation comprenant un hydrocarbure ramifié pour former l'hydroperoxyde d'hydrocarbyle et le premier alcool et/ou le second alcool ; et la mise en présence du premier alcool et/ou du second alcool avec un catalyseur pour former la première oléfine.
PCT/US2019/055360 2018-10-22 2019-10-09 Procédés de formation de dérivés de benzène para-substitués WO2020086275A1 (fr)

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US3830866A (en) 1970-10-27 1974-08-20 Atlantic Richfield Co Process for the catalytic conversion of olefins to aromatics
US3836603A (en) 1973-03-29 1974-09-17 Atlantic Richfield Co Process for preparing para-xylene
US4229320A (en) 1979-01-22 1980-10-21 Shell Oil Company Catalyst for making para-xylene
US5288919A (en) 1993-05-13 1994-02-22 Arco Chemical Technology, L.P. Preparation of dialkyl peroxides
US6600081B2 (en) 2000-03-16 2003-07-29 Leo E. Manzer Process for the preparation of p-xylene
WO2005065393A2 (fr) 2003-12-30 2005-07-21 Saudi Basic Industries Corporation Procede d'aromatisation d'alcanes au moyen d'un catalyseur platine-zeolithe
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US20110087000A1 (en) 2009-10-06 2011-04-14 Gevo, Inc. Integrated Process to Selectively Convert Renewable Isobutanol to P-Xylene
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US3830866A (en) 1970-10-27 1974-08-20 Atlantic Richfield Co Process for the catalytic conversion of olefins to aromatics
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MIREYA R. GOLDWASSERDAVID L. TRIMM: "The Oxidation of Isobutylene to p-Xylene over Bismuth Oxide-based Catalysts", J. APPL. CHEM. BIOTECHNOL., vol. 28, 1978, pages 733 - 739

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