WO2009064622A2 - Procede de production d'un hydrocarbure - Google Patents

Procede de production d'un hydrocarbure Download PDF

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Publication number
WO2009064622A2
WO2009064622A2 PCT/US2008/081916 US2008081916W WO2009064622A2 WO 2009064622 A2 WO2009064622 A2 WO 2009064622A2 US 2008081916 W US2008081916 W US 2008081916W WO 2009064622 A2 WO2009064622 A2 WO 2009064622A2
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Prior art keywords
alkane
reactive
adamantane
dimethylbutane
activating catalyst
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PCT/US2008/081916
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English (en)
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WO2009064622A3 (fr
Inventor
Jay Alan Labinger
John Glenn Sunley
Nilay Hazari
Enrique Iglesia
Valerie Jean Scott
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California Institute Of Technology
Bp P.L.C.
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Publication of WO2009064622A2 publication Critical patent/WO2009064622A2/fr
Publication of WO2009064622A3 publication Critical patent/WO2009064622A3/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
    • C07C2/86—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
    • 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
    • C07C2/865—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 ether
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/06—Halogens; Compounds thereof
    • C07C2527/125—Compounds comprising a halogen and scandium, yttrium, aluminium, gallium, indium or thallium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/06—Halogens; Compounds thereof
    • C07C2527/128—Compounds comprising a halogen and an iron group metal or a platinum group metal
    • C07C2527/13—Platinum group metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/06—Halogens; Compounds thereof
    • C07C2527/138—Compounds comprising a halogen and an alkaline earth metal, magnesium, beryllium, zinc, cadmium or mercury

Definitions

  • This invention relates to a process for preparing hydrocarbons and in particular to a process for alkane homologation from methanol and/or dimethyl ether.
  • Hydrocarbons may be produced by homologation of methanol and/or dimethyl ether.
  • US4059626 describes a process for the production of triptane (2,2,3- trimethylbutane) comprising contacting methanol, dimethyl ether or mixtures thereof with zinc bromide.
  • US4059627 describes a process for the production of triptane from methanol, dimethyl ether or mixtures thereof using zinc iodide.
  • WO02070440 relates to a continuous or semi-continuous process for the production of triptane and/or thptene from methanol and/or dimethyl ether in which co-produced water is removed from the reactor as the reaction proceeds.
  • WO05023733 relates to a process for the production of branched chain hydrocarbons which comprises reacting methanol and/or dimethyl ether with a catalyst comprising indium halide.
  • WO06023516 relates to a process for the production of branched chain hydrocarbons which comprises reacting methanol and/or dimethyl ether with a catalyst comprising a metal halide selected from rhodium halide, iridium halide and combinations thereof.
  • a process for the production of a hydrocarbon which process comprises contacting, in a reactor, a reactive alkane; a methylating agent; an optional diamondoid modifier and an activating catalyst, thereby generating a hydrocarbon product having a greater number of carbon atoms than the reactive alkane.
  • Generating a "heavier” product from a "lighter” reactant is important for many processes.
  • the reactive alkane can be generated by a reactive alkane precursor that generates the reactive alkane by, for example, a pyrolysis reaction, a cracking reaction, an isomerization reaction, or a combination thereof.
  • the reactive alkane can have from four to twenty carbon atoms.
  • the reactive alkane there are from four to fifteen carbons in the reactive alkane. In one embodiment, there are from four to six carbon atoms in the reactive alkane. In one embodiment, there are from 4 to 10 carbons in the reactive alkane. In one embodiment, the reactive alkane contains a tertiary carbon. In one embodiment, the reactive alkane is generated from a reactive alkane precursor. In one embodiment the reactive alkane precursor has from 4 to 10 carbons. In one embodiment, the reactive alkane precursor has at least one tertiary carbon and from 8 to 20 total carbon atoms.
  • the reactive alkane is non-cyclic. In one embodiment, the reactive alkane contains a tertiary carbon and is non-cyclic. In one embodiment, the homologation reaction is carried out in more than one step, for example, a reactive alkane or reactive alkane precursor, optional diamondoid modifier and activating catalyst can be pre-reacted for a period of time, then a methylating agent can be added.
  • Suitable conditions for the process of the present invention are described for example in International Publication Nos. WO02070440, WO05023733 and WO06023516 the contents of which are incorporated by reference.
  • the present methods provide both continuous and semi-continuous processes for the production of hydrocarbons.
  • the process of the present invention is carried out at a temperature greater than 100 degrees Celsius.
  • the process of the present invention is carried out at a temperature selected over the range of 100 degrees Celsius to 450 degrees Celsius, and more preferably for some applications at a temperature selected over the range of 150 degrees Celsius to 350 degrees Celsius.
  • the process of the present invention is carried out at a temperature selected over the range of 150 to 250 degrees Celsius.
  • the process of the present invention is carried out at a temperature selected over the range of 160 to 220 degrees Celsius.
  • the process of the present invention is carried out at a temperature selected over the range of 170 to 210 degrees Celsius.
  • the process of the present invention is carried out at a temperature selected above 200 degrees Celsius.
  • the process of the present invention is carried out at a temperature selected above 220 degrees Celsius. It is understood that the temperature ranges exemplified are not intended to limit the useful temperature range.
  • Activating catalysts useful in the present methods include indium halide or a mixture of indium halide and other metal halides such as zinc halide, rhodium halide and iridium halide.
  • Other activating catalysts useful in the present methods include zinc halide or a mixture of zinc halide and other metal halides such as indium halide, rhodium halide and iridium halide.
  • Other activating catalysts useful in the present methods include catalysts that can activate the alkane and cause methylation.
  • Lewis acids or Br ⁇ nsted acids may be used as activating catalysts, alone or in combination with other activating catalysts, such as those catalysts described herein and known to the art.
  • the catalyst compounds useful in the present invention may be present in a solvated or dissolved form comprising one or more cations and ions, such as metal cations and halogen anions, may be present in the form of a metal salt, or may be present in both a solvated or dissolved form and in the form of a metal salt.
  • Metal halide catalysts used herein may be completely dissolved or may be provided in solid and dissolved states. The metal halide may be directly introduced into the reactor or may be formed in-situ by reaction of a metal source and halide source.
  • the metal halide of the present methods is selected from the group consisting of: zinc halide, iridium halide, rhodium halide, indium halide or any combinations of these.
  • the metal halide catalyst of the present methods is selected from the group consisting of: ZnI 2 , ZnBr 2 , ZnCI 2 , InI 3 , InBr 3 , InCI 3 , RhI 3 , RhBr 3 , RhCI 3 , IrI 3 , IrBr 3 , IrCI 3 or any combinations of these.
  • selection of the composition of the metal halide provides a means of selectively adjusting the branching and product distribution(s) of the hydrocarbons generated using the present methods.
  • the catalyst comprising metal halide may be maintained in an active form and in an effective concentration in the reactor by recycling to the reactor, halide compounds, such as for example hydrogen iodide and/or methyl iodide from downstream product recovery stage(s), such as described in WO02070440.
  • halide compounds such as for example hydrogen iodide and/or methyl iodide from downstream product recovery stage(s), such as described in WO02070440.
  • additional feedstock components include hydrocarbons, halogenated hydrocarbons and oxygenated hydrocarbons, especially olefins, dienes, alcohols and ethers.
  • the additional feedstock components may be straight chain, branched chain or cyclic compounds (including heterocyclic compounds and aromatic compounds).
  • any additional feedstock component in the reactor may be incorporated in the products of the reaction.
  • the methods of the present invention may further include the step of providing one or more additional feedstock components to the reactor.
  • initiators refers to an additive that causes a chemical reaction or series of chemical reactions to take place and/or enhances the rate of a chemical reaction or series of chemical reactions.
  • an initiator causes a reaction to take place in the liquid phase that otherwise requires the presence of a solid phase or mixed phase.
  • Suitable initiators are preferably one or more compounds having at least 2 carbon atoms selected from alcohols, ethers, olefins and dienes.
  • Preferred initiator compounds are olefins, alcohols, alkanes, and ethers, preferably having 2 to 8 carbon atoms.
  • Alkanes containing at least one tertiary carbon atom, (such as 2,3-dimethylbutane), may be used as initiators for the reaction.
  • Some examples of initiator compounds are 2- methyl-2-butene, 2,4,4-thmethylpent-2-ene, ethanol, isopropanol, methyl tert-butyl ether, 2,3-dimethylbutane, hexamethylbenzene and pentamethylbenzene.
  • the methods of the present invention may further include the step of providing one or more initiators to the reactor.
  • initiators selected from one or more of hydrogen halides and alkyl halides of 1 to 8 carbon atoms. Methyl halides and/or hydrogen halides are generally preferred. For the production of branched chain hydrocarbons from dimethyl ether (DME), methyl halides are especially preferred initiators.
  • the halide of the initiator is the same element as the halide of the metal halide catalyst.
  • methyl substituted compounds especially methyl substituted compounds selected from the group consisting of aliphatic cyclic compounds, aliphatic heterocyclic compounds, aromatic compounds, heteroaromatic compounds and mixtures thereof.
  • such compounds may comprise methylbenzenes such as hexamethylbenzene and/or pentamethylbenzene.
  • At least one reaction product of the process of the present invention is a hydrocarbon having a greater number of carbon atoms than the reactive alkane.
  • a reaction product is a hydrocarbon with seven carbon atoms, for example triptane (2,2,3-thmethylbutane) and/or or triptene (2,3,3-thmethylbut-1 -ene).
  • a reaction product is an alkane.
  • a reaction product is triptane.
  • the reaction products comprise a branched alkane or combination of branched alkanes.
  • a reaction product is a branched alkane or combination of branched alkanes.
  • the reaction products of the present methods comprise one or more C 6 alkanes, C 7 alkanes, and Cs alkanes.
  • a reaction product of the present methods is one or more C 6 alkanes, C 7 alkanes, and Cs alkanes.
  • the reaction products of the present methods comprise one or more of xylene, trimethylbenzene, tetramethylbenzene, pentamethylbenzene, hexamethylbenzene, 2,4-dimethylpentane, 2-methylhexane, 3-methylhexane, and /so-butane.
  • a reaction product of the present methods is one or more of xylene, trimethylbenzene, tetramethylbenzene, pentamethylbenzene, hexamethylbenzene, 2,4-dimethylpentane, 2-methylhexane, 3-methylhexane, and /so-butane.
  • Hydrocarbon reaction products of the present methods may be present in one or more liquid and/or vapor phases.
  • reaction products of the present methods comprise first and second liquid phases, wherein the first liquid phase is a hydrophilic phase comprising water, methanol, dimethyl ether or any combinations of these, and wherein the second liquid phase is a hydrophobic phase comprising one or more hydrocarbons, such as, triptane and/or thptene.
  • Water produced in the process of the present invention is preferably removed from the reactor.
  • An embodiment of the present invention further comprises the step of removing water from the reactor, for example by addition of a drying agent or by physical separation means.
  • the reaction of the present invention is usually performed at elevated pressure for example 2 to 100 barG, preferably 5 to 80 barG, more preferably at a pressure of 10 to 80 barG.
  • the reaction can be conducted under autogeneous pressure.
  • the reaction can be carried out under air.
  • the reaction can be carried out using one or more gases inert to the reaction. Gases inert to the reaction are known to one of ordinary skill in the art. Some examples of gases inert to the reaction include nitrogen, argon, helium and carbon dioxide. Blends of hydrogen with gases inert to the reaction may be used. A mixture of hydrogen and carbon monoxide may be used, such as described in WO02070440, the contents of which are incorporated by reference.
  • the reaction can be carried out using mixtures of gases, including air and one or more gases inert to the reaction.
  • the process of the present invention may be performed as a batch or as a continuous process.
  • reactants may be introduced continuously, together or separately, into the reactor and the hydrocarbon product may be continuously removed from the reactor.
  • the reactive alkane is added to or continuously introduced in the reaction.
  • the reactive alkane is not generated solely from methanol and/or dimethyl ether condensation reactions.
  • the hydrocarbon product may be removed from the reactor in a batch or continuous process together with the catalyst and water, these being separated from the hydrocarbon product and other products of the reaction, if present, and recycled to the reactor. Unreacted reactants may also be separated from the hydrocarbon product and recycled to the reactor.
  • the process of the present invention is performed in a reactor which is suitably an adiabatic reactor or a reactor with heat-removal mechanism(s) such as cooling coils which may remove, for example, up to 20 % of the heat of reaction.
  • a reactor which is suitably an adiabatic reactor or a reactor with heat-removal mechanism(s) such as cooling coils which may remove, for example, up to 20 % of the heat of reaction.
  • Figure 1 shows thptane yield as a function of mmol 2.3-dimethylbutane used.
  • Figure 2 shows the MS patterns for the GC fractions of 2,3-dimethylbutane using 13 C-labeled MeOH.
  • Figure 3 shows the MS patterns for the GC fractions of triptane using R elabeled MeOH.
  • Figure 4 shows triptane yield and triptane selectivity as a function of reaction time.
  • Figure 5 shows the combined yield of 2-methyl and 3-methylpentane as a function of time.
  • diamondoid modifier relates to one or more hydrogen- and carbon-containing compounds having a caged framework of carbon-carbon bonds which generally resemble part of the crystal structure of diamond.
  • Diamondoid modifiers include lower diamondoids such as adamantane, diamantane, and triamantane; and higher diamondoids such as tetramantane and other compounds with higher numbers of carbons having the diamondoid structure. Mixtures of different diamondoid modifiers may be used. Diamondoid modifiers also include isomers of tetramantane, isomers of pentamantane and isomers of decamantane.
  • Diamondoid modifiers used herein may be optionally substituted with various substituents known in the art such as independently one or more C1 -C6 alkyl groups, one or more amino groups, one or more alkyl groups terminated with an amino group, one or more alkyl groups terminated by a carboxylic acid group; and other suitable substituents as long as the diamondoid modifier remains functional as described herein.
  • the amount of diamondoid modifier used may be any suitable amount as discussed herein and easily determinable by one of ordinary skill in the art. Some suitable amounts of diamondoid modifiers include between 1 -15 mol percent as compared to the amount of reactive alkane.
  • between 1 -10 mol percent of diamondoid modifier is used as compared to the amount of reactive alkane. In one embodiment, between 0.05-15 mol percent of diamondoid modifier is used as compared to the amount of reactive alkane.
  • the molar ratio of the reactive alkane to methylating agent is selected over the range of 0.1 :1 to 10:1. In one embodiment, the molar ratio of the diamondoid modifier to the reactive alkane is selected over the range of 0.001 :1 to 0.1 :1. In one embodiment, the molar ratio of the diamondoid modifier to the methylating agent is selected over the range of 0.001 :1 to 0.1 :1.
  • the diamondoid modifier to the activating catalyst is selected over the range of 0.005:1 to 0.1 :1. In one embodiment, the molar ratio of the diamondoid modifier to the total concentration of reactive alkane and methylating agent is selected over the range of 0.0005:1 to 0.05:1. In one embodiment, the molar ratio of the diamondoid modifier to the total concentration of reactive alkane, methylating agent and activating catalyst is selected over the range of 0.0001 :1 to 0.05:1. In one embodiment, the molar ratio of the total concentration of reactive alkane and methylating agent to activating catalyst is selected over the range of 0.1 :1 to 10:1. In one embodiment, the diamondoid modifier is provided at a purity equal to or greater than 95%.
  • the zinc halide is fully dissolved in the reaction mixture.
  • a zinc halide catalyst is used in the homologation of 2,3- dimethylbutane (DMB) with methanol in the presence of adamantane, the zinc halide is fully dissolved in the reaction mixture.
  • DMB 2,3- dimethylbutane
  • the methylating agentalkane mole ratio of greater than 1 :1 is used. In an embodiment when a zinc halide is used in the alkane homologation reaction, the methylating agentalkane mole ratio of greater than 3:1 is used. In an embodiment when a zinc halide catalyst is used in the homologation of 2,3-dimethylbutane (DMB) with methanol in the presence of adamantane, a methanol:DMB mole ratio of greater than 1 :1 is used. In an embodiment when a zinc halide catalyst is used in the homologation of 2,3-dimethylbutane (DMB) with methanol in the presence of adamantane, a methanol:DMB mole ratio of 3:1 ratio is used
  • the methylating agentalkane mole ratio of greater than 1 :1 is used. In an embodiment when an indium halide is used in the alkane homologation reaction, the methylating agentalkane mole ratio of greater than 3:1 is used. In an embodiment when an indium halide catalyst is used in the homologation of 2,3-dimethylbutane (DMB) with methanol in the presence of adamantane, a methanol:DMB mole ratio of greater than 1 :1 is used. In an embodiment when an indium halide catalyst is used in the homologation of 2,3-dimethylbutane (DMB) with methanol in the presence of adamantane, a methanol:DMB mole ratio of 3:1 ratio is used
  • a carbocation of the diamondoid modifier has higher stability than carbocations of the reactive alkane or methylated products thereof.
  • An example is illustrated in Scheme 1 below where adamantane is the diamondoid modifier and 2,3-dimethylbutane is the reactive alkane.
  • the diamondoid modifier may reduce the probability of unwanted by-products from side reactions by hydride ion donation.
  • activating catalyst is a catalyst that activates a tertiary carbon to form a carbocation, and also activates the methylating agent to cause methylation of the reactive alkane.
  • the activating catalyst can be one or more catalysts.
  • a "reactive alkane” is an alkane that reacts with the methylating agent and activating catalyst to produce a product having a greater number of carbon atoms than the reactive alkane.
  • the reactive alkane contains at least one tertiary carbon atom.
  • Reactive alkanes can be produced by reactive alkane precursors through one or more of isomehzation, pyrolysis, and cracking reactions, for example.
  • a reactive alkane precursor such as isooctane can undergo a cracking reaction to form a reactive alkane. This cracking reaction can occur in the reactor.
  • An isomerization reaction of an alkane can also be used to form a reactive alkane. If a desired product is thptane and/or another branched hydrocarbon, then isomerization of a reactive alkane precursor is preferably performed ex situ to prevent isomerization of triptane or other branched hydrocarbon product.
  • homologation means a reaction in which that the number of carbons in the product is greater than the number of carbons in the reactant.
  • contacting means bringing materials in sufficient physical contact so that the desired reaction can occur.
  • methylating agent is one or more of methanol or a methanol derivative such as dimethyl ether.
  • a methanol derivative generally is a substance that can produce methanol or a substance that functions similarly to methanol in the reaction, for example when hydrolyzed.
  • Examples of methanol derivatives include methyl ethers such as dimethyl ether.
  • One or more methyl halides may also be used in the reactions described herein.
  • Alkyl groups include straight-chain, branched and cyclic alkyl groups. Alkyl groups include those having from 1 to 30 carbon atoms. Alkyl groups include small alkyl groups having 1 to 3 carbon atoms. Alkyl groups include medium length alkyl groups having from 4-10 carbon atoms. Alkyl groups include long alkyl groups having more than 10 carbon atoms, particularly those having 10-30 carbon atoms. Cyclic alkyl groups include those having one or more rings. Cyclic alkyl groups include those having a 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-member carbon ring and particularly those having a 3-, 4-, 5-, 6-, or 7-member ring.
  • the carbon rings in cyclic alkyl groups can also carry alkyl groups.
  • Cyclic alkyl groups can include bicyclic and tricyclic alkyl groups.
  • Alkyl groups are optionally substituted.
  • Substituted alkyl groups include among others those which are substituted with aryl groups, which in turn can be optionally substituted.
  • alkyl groups include methyl, ethyl, n- propyl, iso-propyl, cyclopropyl, n-butyl, s-butyl, t-butyl, cyclobutyl, n-pentyl, branched-pentyl, cyclopentyl, n-hexyl, branched hexyl, and cyclohexyl groups, all of which are optionally substituted.
  • Substituted alkyl groups include fully halogenated or semihalogenated alkyl groups, such as alkyl groups having one or more hydrogens replaced with one or more fluorine atoms, chlorine atoms, bromine atoms and/or iodine atoms.
  • Substituted alkyl groups include fully fluohnated or semifluorinated alkyl groups, such as alkyl groups having one or more hydrogens replaced with one or more fluorine atoms.
  • An alkoxyl group is an alkyl group linked to oxygen and can be represented by the formula R-O.
  • Alkenyl groups include straight-chain, branched and cyclic alkenyl groups. Alkenyl groups include those having 1 , 2 or more double bonds and those in which two or more of the double bonds are conjugated double bonds. Alkenyl groups include those having from 2 to 20 carbon atoms. Alkenyl groups include small alkenyl groups having 2 to 3 carbon atoms. Alkenyl groups include medium length alkenyl groups having from 4-10 carbon atoms. Alkenyl groups include long alkenyl groups having more than 10 carbon atoms, particularly those having 10-20 carbon atoms. Cyclic alkenyl groups include those having one or more rings.
  • Cyclic alkenyl groups include those in which a double bond is in the ring or in an alkenyl group attached to a ring. Cyclic alkenyl groups include those having a 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-member carbon ring and particularly those having a 3-, 4-, 5-, 6- or 7- member ring. The carbon rings in cyclic alkenyl groups can also carry alkyl groups. Cyclic alkenyl groups can include bicyclic and tricyclic alkyl groups. Alkenyl groups are optionally substituted. Substituted alkenyl groups include among others those which are substituted with alkyl or aryl groups, which groups in turn can be optionally substituted.
  • alkenyl groups include ethenyl, prop-1 -enyl, prop-2-enyl, cycloprop-1 -enyl, but-1-enyl, but-2-enyl, cyclobut-1 -enyl, cyclobut-2-enyl, pent-1 - enyl, pent-2-enyl, branched pentenyl, cyclopent-1 -enyl, hex-1 -enyl, branched hexenyl, cyclohexenyl, all of which are optionally substituted.
  • Substituted alkenyl groups include fully halogenated or semihalogenated alkenyl groups, such as alkenyl groups having one or more hydrogens replaced with one or more fluorine atoms, chlorine atoms, bromine atoms and/or iodine atoms.
  • Substituted alkenyl groups include fully fluorinated or semifluorinated alkenyl groups, such as alkenyl groups having one or more hydrogens replaced with one or more fluorine atoms.
  • Aryl groups include groups having one or more 5- or 6-member aromatic or heteroaromatic rings.
  • Aryl groups can contain one or more fused aromatic rings.
  • Heteroaromatic rings can include one or more N, O, or S atoms in the ring.
  • Heteroaromatic rings can include those with one, two or three N, those with one or two O, and those with one or two S, or combinations of one or two or three N, O or S.
  • Aryl groups are optionally substituted.
  • Substituted aryl groups include among others those which are substituted with alkyl or alkenyl groups, which groups in turn can be optionally substituted.
  • aryl groups include phenyl groups, biphenyl groups, pyridinyl groups, and naphthyl groups, all of which are optionally substituted.
  • Substituted aryl groups include fully halogenated or semihalogenated aryl groups, such as aryl groups having one or more hydrogens replaced with one or more fluorine atoms, chlorine atoms, bromine atoms and/or iodine atoms.
  • Substituted aryl groups include fully fluorinated or semifluorinated aryl groups, such as aryl groups having one or more hydrogens replaced with one or more fluorine atoms.
  • the tube was then sealed using a Teflon Kontes valve.
  • InI 3 was weighed out in a dry box, all other chemicals were added in air and the reaction was performed under an atmosphere of air. This mixture was stirred to give a colorless or light yellow solution, which contained two phases.
  • the tube was then dipped into a preheated oil bath at 200 0 C, and was heated and stirred for 2 hours, after which time it was cooled to room temperature to give two layers. The top layer is colorless and the bottom one is brown with some precipitates.
  • This mixture was chilled in ice water and a solution of cyclohexane in chloroform was added (1 ml, 30.01 mg cyclohexane in CHCI 3 ) and then water (1.0 ml).
  • Example 1 using 6.2 mmol of 2,3-dimethylbutane, 49 mg of triptane were obtained (averages of two runs) and 387 mg of 2,3-dimethylbutane were recovered, which corresponds to a yield of 17% based on all converted carbon atoms.
  • Example 2 using 0.76 mmol of 2,3-dimethylbutane, 32 mg of triptane were obtained (averages of two runs) and 52 mg of 2,3-dimethylbutane were recovered, which corresponds to a yield of 15% based on all converted carbon atoms.
  • Example 3 using 1.52 mmol of 2,3-dimethylbutane, 33 mg of triptane were obtained (averages of two runs) and 85 mg of 2,3-dimethylbutane were recovered, which corresponds to a yield of 15% based on all converted carbon atoms.
  • Example 4 3.04 mmol of 2,3- dimethylbutane, 40 mg of triptane were obtained (averages of two runs) and 186 mg of 2,3-dimethylbutane were recovered, which corresponds to a yield of 16% based on all converted carbon atoms.
  • Example 5 12.4 mmol of 2,3-dimethylbutane, 75 mg of triptane were obtained (averages of two runs) and 841 mg of 2,3-dimethylbutane were recovered, which corresponds to a yield of 18% based on all converted carbon atoms.
  • the organic layer was extracted and analyzed by gas chromatography (GC) and found to contain 60 mg triptane (average of two runs) and the recovered yield of 2,3-dimethylbutane was 311 mg. This corresponds to a yield of triptane of 19% based on all converted carbon atoms.
  • the total yield of tetramethylbenzene (TMB) was 3 mg (combined isomers), while the total yield of PMB was 1 mg. No detectable quantity of HMB was observed.
  • Example 7 under the same reaction conditions as Example 6 for a one hour reaction, 62 mg of triptane were obtained and 309 mg of 2,3-dimethylbutane were recovered, corresponding to a yield of 20% based on all converted carbon atoms. The selectivity for the conversion of 2,3-dimethylbutane to triptane was 24%.
  • Example 8 under the same reaction conditions as Example 6 for a thirty minute reaction, 64 mg of triptane were obtained and 354 mg of 2,3-dimethylbutane were recovered, corresponding to a yield of 24% based on all converted carbon atoms.
  • Example 10 same reaction conditions as Example 8 with heating at 190 0 C; Example 11 was heated at 180 0 C; Example 12 was heated at 170 0 C; Example 13 was heated at 160 0 C; Example 14 was heated at 150 0 C; and Example 15 was heated at 140 0 C.
  • Table 3 summarizes the triptane yield in mg, recovered yield of 2,3-dimethylbutane in mg, the triptane yield based on total converted carbon and selectivity for the formation of triptane from 2,3-dimethylbutane. Table 3
  • Example 16 instead of using 2,3-dimethylbutane as the feedstock, isopentane was utilized, under similar reaction conditions to Example 1. Initially, the reaction mixture contained 4.13 mmol of InI 3 , 4.38 mmol of isopentane and 12.4 mmol of MeOH. A yield of 35 mg for triptane was obtained and 252 mg of isopentane were recovered, corresponding to a yield of 14% based on all converted carbon atoms.
  • Example 17 Incorporating ZnI 2 into the reaction mixture [0070]
  • Example 17 - Instead of using only InI 3 , a reaction was performed following the procedure outlined for Example 1 , using 2.82 mmol of InI 3 , 0.94 mmol Of ZnI 2 , 12.4 mmol of MeOH and 6.2 mmol of 2,3-dimethylbutane. The yield of triptane was 45 mg and 452 mg of 2,3-dimethylbutane were recovered. This corresponds to a triptane yield of 17% based on total carbon converted.
  • a reaction was performed using 8.42 mmol of DME, 8.42 mmol of 2,3- dimethylbutane and 4.13 mmol of InI 3 .
  • the reaction was heated for 2 hours at 200 degrees Celsius.
  • the yield of triptane was 86 mg and the recovered yield of 2,3- dimethylbutane was 374 mg. This corresponds to a total converted carbon yield of 14.45%.
  • Table 4 compares the yield and selectivity of reactions performed in the presence and absence of adamantane.
  • the triptane yield is based on total converted carbon, while the triptane selectivity is based on the formation of triptane from 2,3- dimethylbutane.
  • This effect may occur because adamantane suppresses the isomehzation of both 2,3-dimethylbutane and triptane and also greatly reduces cracking side reactions which result in the formation of iso- butane and iso-pentane.
  • EXAMPLE 20 C6 and C7 isomehzation and cracking in the presence and absence of adamantane
  • Table 5 compares the extent of Ce and C 7 isomerization and cracking in alkane homologation reactions with and without adamantane.
  • Table 5 Comparison of ratios of side products to starting material and triptane for homologation in the presence and absence of adamantane.
  • adamantane after activation of 2,3-dimethylbutane to generate a carbocation (the mechanism of which is unknown) adamantane basically functions in a "repair” mechanism, capturing the isomeric carbocation before it can undergo skeletal rearrangement and returning it to the parent 2,3-dimethylbutane pool.
  • This is shown schematically in Scheme 1. It is possible that adamantane could also transfer H " to the tertiary 2,3-dimethylbutyl carbocation, which at first would seem to be chain-inhibitory, but that should be reversible: the resulting adamantyl cation could take H " back from another molecule of 2,3-dimethylbutane and start a new chain.
  • GC indicates that the reaction is catalytic in adamantane (the yield of adamantane by GC is 90-100%).
  • the yield of adamantane by GC is 90-100%.
  • the adamantyl carbocation is unlikely to undergo side reactions because isomehzation or cracking reactions require the formation of less stable secondary cations or stehcally hindered alkenes. Therefore, the adamantyl carbocation is likely to abstract H " from another alkane, to regenerate adamantane and another reactive carbocation.
  • the loading of adamantane was varied between 1 -11 mol% (relative to 2,3-dimethylbutane) and this had almost no effect on the triptane yield or selectivity.
  • MeOH appears to be converted to other products without effecting iso-pentane, as the triptane yield decreases when the amount of MeOH is increased but the triptane selectivity (a measure of selectivity of the conversion of iso-pentane to triptane) remains almost constant.
  • Iso-butane is also produced as a volatile and unreactive waste product in oil refineries and thus the homologation of iso-butane with MeOH was also investigated. A series of reactions using a number of different ratios of MeOH to isobutane were performed. The results of these reactions are summarized in Table 7. Table 7: Summary of homologation reactions between MeOH and iso-butane catalyzed by InI 3 . 3
  • Table 7 shows that some triptane and 2,3-dimethylbutane are formed from the homologation of isobutane with MeOH.
  • iso-pentane which is presumably formed from the methylation of isobutylene, which is formed by deprotonation of the tertiary iso-butyl carbocation.
  • the formation of triptane and 2,3-dimethylbutane from iso-pentane probably follows the path described earlier.
  • 2,3- dimethylpentane Under the reaction conditions, 2,3- dimethylpentane is unstable and undergoes both isomerization and cracking reactions to form some of the other products observed. Isomerization of 2,3- dimethylpentane results in other C 7 alkanes, while products such as iso-butane and iso-pentane form from cracking (these cracking products are also probably formed from the C 6 and C 8 alkanes present).
  • the reaction is not as selective as the methylation of 2,3-dimethylbutane to triptane because both 2-methylpentane and 2,3-dimethylpentane are more likely to undergo isomehzation reactions than 2,3- dimethylbutane or triptane.
  • Table 10 Summary of product distribution from isomerization of hexane in the presence and absence of adamantane. a Unless otherwise stated all quantities are in milligrams.
  • Homologation of alkanes can also be catalyzed with Zn halides, such as ZnI 2 .
  • Table 11 shows results for several ZnI 2 catalyzed methanol conversion carried out at 230 0 C. Most notably, in contrast to the behavior at 200 0 C, DMB initiates reaction, resulting in approximately the same triptane yield as a reaction initiated with 1 PrOH (although this reaction was allowed to react longer, the results are comparable, because in each case MeOH/DME has been completely consumed, and we have shown that alkanes do not significantly react further); and essentially no olefins are detected. The average triptane yield, 45 mg, is lower than the triptyls yield obtained for an otherwise similar reaction at 200 0 C (60 mg).
  • AII reactions contained 7.52 mmol of ZnI 2 and 24.7 mmol of methanol. No triptene was detected.
  • the ZnI 2 catalyst can be completely dissolved, and (in the presence of AdH, which as noted above substantially improves yield and selectivity in the Inl 3 -system) gives triptane yields much higher than can be accounted for by the methanol alone: the average yield (Entries 2-4 of Table 12) is about 68 mg, vs. 54 mg obtained for a comparable reaction using twice as much methanol, with AdH but without DMB (data not shown).
  • the following labelling study was performed to demonstrate the incorporation of DMB into triptane: ZnI 2 (4.13 mmol) was predissolved in labelled methanol (12.4 mmol).
  • any isotope of such atom is intended to be included.
  • Specific names of compounds are intended to be exemplary, as it is known that one of ordinary skill in the art can name the same compounds differently. Every formulation or combination of components described or exemplified herein can be used to practice the invention, unless otherwise stated.
  • a range is given in the specification, for example, a temperature range, a time range, or a composition range, all intermediate ranges and subranges, as well as all individual values included in the ranges given are intended to be included in the disclosure.
  • ionizable groups groups from which a proton can be removed (e.g., -COOH) or added (e.g., amines) or which can be quaternized (e.g., amines)]. All possible ionic forms of such molecules and salts thereof are intended to be included individually in the disclosure herein.
  • salts of the compounds herein one of ordinary skill in the art can select from among a wide variety of available countehons those that are appropriate for preparation of salts of this invention for a given application. In specific applications, the selection of a given anion or cation for preparation of a salt may result in increased or decreased solubility of that salt.

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Abstract

L'invention concerne un procédé d'homologation d'alcanes consistant à mettre en contact : un alcane réactif; un agent de méthylation; un modificateur diamantoïde facultatif; et un catalyseur d'activation, de sorte à générer un produit hydrocarbure contenant un plus grand nombre d'atomes de carbone que l'alcane réactif.
PCT/US2008/081916 2007-11-13 2008-10-31 Procede de production d'un hydrocarbure WO2009064622A2 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102702107A (zh) * 2012-06-27 2012-10-03 中国农业大学 一种含二硝基三氟甲苯结构的氨基酸衍生物及其制备方法和应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2456584A (en) * 1946-11-18 1948-12-14 Socony Vacuum Oil Co Inc Conversion of dimethyl ether
GB634602A (en) * 1946-09-03 1950-03-22 Bataafsche Petroleum Catalytic isomerisation of solid hydrocarbons
WO2002070440A1 (fr) * 2001-03-02 2002-09-12 Bp Oil International Limited Procede et dispositif permettant la preparation de triptane et/ou de triptene
WO2005023733A2 (fr) * 2003-09-03 2005-03-17 Bp Oil International Limited Procede de preparation d'hydrocarbures a chaine ramifiee

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB634602A (en) * 1946-09-03 1950-03-22 Bataafsche Petroleum Catalytic isomerisation of solid hydrocarbons
US2456584A (en) * 1946-11-18 1948-12-14 Socony Vacuum Oil Co Inc Conversion of dimethyl ether
WO2002070440A1 (fr) * 2001-03-02 2002-09-12 Bp Oil International Limited Procede et dispositif permettant la preparation de triptane et/ou de triptene
WO2005023733A2 (fr) * 2003-09-03 2005-03-17 Bp Oil International Limited Procede de preparation d'hydrocarbures a chaine ramifiee

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
BERCAW AND CO: JOURNAL OF ORGANIC CHEMISTRY, vol. 71, 2006, pages 8907-8917, XP002529820 cited in the application *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102702107A (zh) * 2012-06-27 2012-10-03 中国农业大学 一种含二硝基三氟甲苯结构的氨基酸衍生物及其制备方法和应用
CN102702107B (zh) * 2012-06-27 2014-09-10 中国农业大学 一种含二硝基三氟甲苯结构的氨基酸衍生物及其制备方法和应用

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