WO2018044592A1 - Production de néopentane - Google Patents

Production de néopentane Download PDF

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Publication number
WO2018044592A1
WO2018044592A1 PCT/US2017/047586 US2017047586W WO2018044592A1 WO 2018044592 A1 WO2018044592 A1 WO 2018044592A1 US 2017047586 W US2017047586 W US 2017047586W WO 2018044592 A1 WO2018044592 A1 WO 2018044592A1
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Prior art keywords
demethylation
neopentane
catalyst
neohexane
neoheptane
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PCT/US2017/047586
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WO2018044592A8 (fr
Inventor
Kun Wang
Lorenzo C. Decaul
Michele L. PACCAGNINI
Etienne Mazoyer
James R. Lattner
Helge Jaensch
Ali A. Kheir
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Exxonmobil Chemical Patents Inc.
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Priority to US16/324,722 priority Critical patent/US10487023B2/en
Publication of WO2018044592A1 publication Critical patent/WO2018044592A1/fr
Publication of WO2018044592A8 publication Critical patent/WO2018044592A8/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/08—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule
    • C07C4/10—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule from acyclic hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/464—Rhodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/468—Iridium
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/638—Pore volume more than 1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
    • C07C5/2767—Changing the number of side-chains
    • C07C5/277—Catalytic processes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/04—Purification; Separation; Use of additives by distillation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
    • C10G45/62—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing platinum group metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
    • C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C07C2521/08—Silica
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/44—Palladium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/46—Ruthenium, rhodium, osmium or iridium

Definitions

  • the present invention relates to methods of producing neopentane and uses thereof.
  • Neopentane is a unique nonpolar hydrocarbon molecule that has found industrial use in the form of an inert condensing agent for gas-phase reactions. See, for instance, US 6,262,192.
  • Other potential industrial uses for neopentane include use as a heat removal agent, a blowing agent, and a gasoline blend component due to its relatively high octane numbers. For instance, neopentane has a Research Octane Number (RON) of 85.5 and a Motor Octane Number (MON) of 80.2.
  • neopentane may be synthesized by hydrogenation of neopentanoic acid under high pressure and at high temperature, e.g., as described in US 4,593,147, such processes are expensive due to the neopentanoic acid feedstock and suffer from a combination of demanding reaction conditions and low selectivity.
  • the present invention relates to novel processes that address the need for the production of neopentane at high yield, under mild reaction conditions, and utilizing readily available feedstock.
  • the present invention relates to a process for producing neopentane comprising isomerizing C6-C7 paraffins to produce neohexane or neoheptane, followed by demethylating the neohexane or neoheptane to produce a product comprising at least 40 wt% neopentane.
  • the C6-C7 paraffins can be provided in a C4-C7 paraffinic feed stream, preferably a light virgin naphtha stream.
  • the Figure is a diagram of a process of neopentane.
  • neopentane Described herein are processes for producing neopentane. As discussed below, the processes involve the demethylation of neohexane and/or neoheptane, preferably via contacting the neohexane or neoheptane with hydrogen in the presence of a catalyst.
  • the neohexane and/or neoheptane can be provided by isomerization, preferably catalytic isomerization, of C6-C7 paraffins.
  • the C6-C7 paraffins are provided in a C4-C7 paraffinic feed stream, such as a light virgin naphtha stream.
  • the processes described herein enable the production of neopentane in quantities of greater than about 5 kg/hr, preferably greater than about 500 kg/hr, preferably greater than about 5000 kg/hr, and preferably greater than about 35000 kg/hr.
  • the indefinite article “a” or “an” shall mean “at least one” unless specified to the contrary or the context clearly indicates otherwise.
  • embodiments using “a fractionation column” include embodiments where one, two or more fractionation columns are used, unless specified to the contrary or the context clearly indicates that only one fractionation column is used.
  • a C12+ component should be interpreted to include one, two or more C12+ components unless specified or indicated by the context to mean only one specific C12+ component.
  • wt% means percentage by weight
  • vol% means percentage by volume
  • mol% means percentage by mole
  • ppm means parts per million
  • ppm wt and wppm are used interchangeably to mean parts per million on a weight basis. All “ppm” as used herein are ppm by weight unless specified otherwise. All concentrations herein are expressed on the basis of the total amount of the composition in question. Thus, the concentrations of the various components of the first feedstock are expressed based on the total weight of the first feedstock. All ranges expressed herein should include both end points as two specific embodiments unless specified or indicated to the contrary.
  • hydrocarbon refers to molecules or segments of molecules containing primarily hydrogen and carbon atoms.
  • C n hydrocarbon wherein n is a positive integer, e.g., 1, 2, 3, 4, etc., means a hydrocarbon having n number of carbon atom(s) per molecule.
  • C n + hydrocarbon wherein n is a positive integer, e.g., 1, 2, 3, 4, etc., as used herein, means a hydrocarbon having at least n number of carbon atom(s) per molecule.
  • olefin refers to any unsaturated hydrocarbon having the formula CnEhn and containing one carbon-carbon double bond, wherein C is a carbon atom, H is a hydrogen atom, and n is the number of carbon atoms in the olefin.
  • alkane or “paraffin” refers to any saturated hydrocarbon having the formula C n H2 n +2, wherein C is a carbon atom, H is a hydrogen atom, and n is the number of carbon atoms in the alkane.
  • "normal” paraffins signified by the prefix “n” are linear, straight-chain paraffins.
  • “isoparaffins” signified by the prefix “i-,” are branched paraffins.
  • a "primary carbon atom” refers to a carbon atom neighboring one carbon atom
  • “secondary carbon atom” refers to a carbon atom neighboring two carbon atoms
  • “tertiary carbon atom” refers to a carbon atom neighboring three carbon atoms
  • “quaternary carbon atom” refers to a carbon atom neighboring four carbon atoms.
  • neo signifies a hydrocarbon containing a quaternary carbon atom.
  • neopentane refers to a compound of the formula C5H12 and containing a quaternary carbon atom, otherwise known as 2,2-dimethylpropane.
  • Lewis acid refers to a molecule, species, ion, or radical that is electron deficient and, therefore, is capable of accepting a pair of electrons from a donor species.
  • neohexane and/or neoheptane is formed in the present invention by the isomerization of Ce paraffins (e.g., n-hexane, i-hexane, or 2,3-dimethylbutane) and/or C7 paraffins, (e.g., n-heptane, i-heptane, 2,4-dimethylpentane, or 2,3-dimethylpentane) preferably via contacting the C6-C7 paraffins with hydrogen in the presence of a catalyst.
  • the C6-C7 paraffins are provided in a C4-C7 paraffinic feed stream.
  • Suitable C4-C7 paraffinic feed streams include substantially pure normal paraffin streams having from 4 to 7 carbon atoms or a mixture of such substantially pure normal paraffins, light natural gasoline, light virgin naphtha, light straight run naphtha, gas oil condensate, light raffinates, light reformate, light hydrocarbons, and straight run distillates having distillation end points of about 98°C (210°F) and containing substantial quantities of C4-C7 paraffins.
  • the C4-C7 paraffinic feed stream preferably comprises a light virgin naphtha stream.
  • the C4-C7 paraffinic feed stream comprises about 50 wt% or more of C4-C7 paraffinic hydrocarbons, such as from about 50 wt% to about 90 wt% or from about 70 wt% to about 80 wt% by weight of the paraffinic feed.
  • the C4-C7 paraffins are primarily linear aliphatics.
  • naphthenes cycloaliphatic hydrocarbons
  • the C4-C7 paraffinic feed stream may also comprise: up to about 10 wt% of olefinic hydrocarbons, such as from about 1 wt% to about 5 wt%; and up to about 20 wt% of Cs + hydrocarbons, such as from about 5 wt% to about 15 wt%, each by weight of the paraffinic feed (100 wt%).
  • concentration of the olefinic hydrocarbons and Cs + hydrocarbons is minimized to reduce hydrogen consumption and inhibit undesired cracking reactions.
  • the C4-C7 paraffinic feed is pretreated to remove aromatics and sulfur.
  • the pretreated C4-C7 paraffinic feed contains no more than a maximum of about 0.1 wt% of aromatics and no more than a maximum of about 0.001 wt% sulfur based on the weight of paraffinic feed.
  • the C4-C7 paraffinic feed may be further pretreated to remove Cs+ hydrocarbons.
  • a catalyst Any catalyst suitable for paraffin isomerization, whether homogeneous or heterogeneous, may be used.
  • Preferred catalysts are of two types: Lewis acids and Afunctional catalysts.
  • Suitable Lewis acids include aluminum and boron halides (e.g., boron trifluoride, aluminum chloride, and chlorided alumina), strong acids (e.g., hydrochloric acid, hydrofluoric acid), and mixtures thereof (e.g., aluminum chloride and hydrochloric acid).
  • Suitable Afunctional catalysts generally comprise a transition metal component and a solid acid component.
  • Suitable transition metal components include Pd, Pt, Rh, Ru, Os, Ir, Au, Ag, Cu, Ni, Co, Fe, and Re, combinations thereof, compounds thereof, and mixtures of compounds thereof, with Pt being particularly preferred.
  • Suitable solid acid components include zeolites, amorphous aluminosilicates, acidic metal oxides or mixed metal oxides, solid phosphoric acid, and mixtures thereof.
  • Non- limiting examples of such zeolites include those of the MFI framework type (e.g., ZSM-5), zeolite beta, mordenite, faujasite, and those of the MWW family (e.g., MCM-22, -49, or -56), especially those such zeolites having a high silicon to aluminum ratio (Si/Al) , conveniently greater than 20 : 1 , such as 50 : 1 or 100 : 1.
  • Non- limiting examples of acidic metal oxides or mixed metal oxides includes tungsten oxides (WO x ), molybdenum oxide (MoOx), mixed oxides such as WO x /Zr0 2 , WO x /Ce0 2 , MoO x /Zr0 2 , MoO x /Ce0 2 , and sulfated zirconia.
  • tungsten oxides WO x
  • MoOx molybdenum oxide
  • mixed oxides such as WO x /Zr0 2 , WO x /Ce0 2 , MoO x /Zr0 2 , MoO x /Ce0 2 , and sulfated zirconia.
  • the isomerization reaction can be conducted in a wide range of reactor configurations including fixed bed (single or in series), slurry reactors, and/or catalytic distillation towers.
  • the isomerization reaction can be conducted in a single reaction zone or in a plurality of reaction zones.
  • Suitable reaction temperatures are generally below about 300°C to thermodynamically favor the production of neohexane and neoheptane, such as from about 25 °C to 300°C, or from about 50°C to about 250°C, or from about 100°C to about 250°C.
  • the reaction pressure is maintained so that the C4-C7 paraffinic feed remains in gas form within the reactor.
  • suitable reaction pressures are from about 100 kPa absolute and about 10000 kPa absolute (e.g., from about 15 psia to about 15000 psia), such as between about 500 kPa absolute and about 5000 kPa absolute.
  • the isomerization is conducted at a hydrogen partial pressure of less than about 5000 kPa absolute, preferably less than about 2500 kPa absolute, and preferably less than about 1000 kPa absolute (e.g., preferably less than about 750 psia absolute, preferably less than about 370 psia absolute or preferably less than about 150 psia absolute).
  • the major components of the isomerization reaction effluent are generally neohexane and/or neoheptane, unreacted normal paraffin components of the C4-C7 paraffinic feed, non-neo C4-C7 branched paraffins (e.g., i-pentane, i-hexane, i-heptane, 2,4- dimethylpentane, and 2,3-dimethylpentane), and C3- hydrocarbon components obtained as a result of side cracking reactions.
  • i-pentane i-hexane
  • i-heptane 2,4- dimethylpentane
  • 2,3-dimethylpentane 2,3-dimethylpentane
  • the unreacted feed components, C4-C7 isoparaffins, and C3- hydrocarbon components can be readily removed from the reaction effluent by, for example, distillation.
  • the remainder of the isomerization reaction effluent mainly composed of neohexane and/or neoheptane, can be demethylated to produce neopentane.
  • the separated isomerization reaction effluent comprises greater than about 80 wt% neohexane and/or neoheptane, or greater than about 90 wt% neohexane and/or neoheptane, or greater than about 95 wt% neohexane and/or neoheptane, or greater than about 99 wt% neohexane and/or neoheptane, such as from about 90 wt% to about 100 wt% neohexane and/or neoheptane, or from about 95 wt%, to about 99 wt% neohexane and/or neoheptane.
  • the demethylation is conducted via demethylation by contacting the neohexane and/or neoheptane with hydrogen in the presence of a catalyst.
  • the desired demethylation of the neohexane and/or neoheptane may be summarized in the following reaction scheme:
  • R is H for neohexane and CH3 for neoheptane.
  • the desired demethylation occurs at the secondary (2°) carbon of the neohexane or neoheptane. Competing demethylation can occur at the quaternary (4°) carbon.
  • demethylation at the quaternary (4°) carbon in the present processes is minimized to prevent a loss of neopentane yield.
  • the demethylation reaction can be conducted in a wide range of reactor configurations including fixed bed (single or in series), slurry reactors, and/or catalytic distillation towers. In addition, the demethylation reaction can be conducted in a single reaction zone or in a plurality of reaction zones.
  • the demethylation is conveniently conducted at a temperature from about 200°C to about 500°C, such as from about 300°C to about 400°C and a pressure from about 100 kPa absolute to about 10000 kPa absolute (e.g., atmospheric to about 1500 psia), such as from about 300 kPa absolute to about 8000 kPa absolute, in the presence of a catalyst.
  • the demethylation is conducted at a hydrogen partial pressure of from about 50 kPa absolute to about 3500 kPa absolute (e.g., from about 7 psia to about 500 psia).
  • the demethylation is conducted at a hydrogen partial pressure of less than about 2500 kP absolute a, preferably less than about 2200 kPa absolute, and preferably less than about 1000 kPa absolute (e.g., preferably less than about 350 psia, or preferably less than about 150 psia).
  • the demethylation may be conveniently conducted under conditions comprising one or more of the following: a temperature from about 220°C to about 300°C; a pressure from about 15 psig to about 200 psig (e.g., from about 205 kPa absolute to about 1400 kPa absolute); and a hydrogen to hydrocarbon molar ratio from about 1: 1 to about 14: 1.
  • the catalyst employed in the demethylation comprises a transition metal component.
  • suitable transition metal components include Fe, Co, Ni, Rh, Ir, Ru, Pt, and Pd, combinations thereof, compounds thereof, and mixtures of compounds thereof, with Ni being particularly advantageous.
  • the transition metal component contains transition metal as a single component.
  • the transition metal component may contain a transition metal combined with an additional metal to form a binary or ternary alloy.
  • suitable additional metals include Cu, Au, Ag, Sn, Zn, Re, combinations thereof, compounds thereof, and mixtures of compounds thereof.
  • the amount of the transition metal component present in the catalyst is from about 0.05 wt% to about 60.0 wt%, such as from about 0.10 wt% to about 50.0 wt%, of the total weight of the catalyst.
  • the transition metal component is supported on a non-acidic support material.
  • suitable support materials include silica, theta- alumina, clay, pentasil, aluminophosphate, carbon, titania, zirconia, and mixtures thereof.
  • the acidity of the catalyst employed in the demethylation is minimized to inhibit undesired cracking reactions.
  • the acidity of the catalyst is reduced via impregnation with an alkali metal compound, preferably an alkali metal hydroxide, nitrate, carbonate, bicarbonate, or oxide, such as sodium oxide, e.g., Na20.
  • the amount of the alkali metal compound present in the catalyst is from about 0.05 wt% to about 1.0 wt%, such as from about 0.1 wt% to about 0.5 wt%, of the total weight of the catalyst.
  • the neohexane and/or neoheptane conversion during the demethylation step is greater than 80%, preferably greater than 90%, preferably greater than 95%, and preferably greater than 99%, such as from 80% to 99% or 90 to 99%.
  • the product of the demethylation step generally comprises neopentane and C 4 - hydrocarbon components (e.g., methane, ethane, and propane).
  • the product of the demethylation step comprises: at least about 40 wt%, preferably at least about 50 wt%, preferably at least about 60 wt%, and ideally at least about 70 wt% of neopentane, such as from about 40 wt% to about 70 wt% or from about 50 wt% to about 65 wt%; less than about 50 wt%, preferably less than about 40 wt%, and preferably less than about 30 wt% of C 4 - hydrocarbon components such as from about 30 wt% to about 50 wt% or from about 35 wt% to about 45 wt%; and less than about 5 wt%, preferably less than about 1 wt%, and ideally less than about 0.5 wt% of non-neopentane C 5 hydrocarbon components, such as from about 0 wt% to about 1 wt% or from about 2 wt% to about 5 wt%.
  • the demethylation of neohexane and/or neoheptane exhibits high single-pass yields of neopentane.
  • the single -pass yield of neopentane in the demethylation of neohexane and/or neoheptane may be greater than about 40 wt%, preferably greater than about 50 wt%, and ideally greater than about 60 wt%.
  • the demethylation step can be conveniently conducted in the absence of recycle, i.e., without recycling any portion of the demethylation product.
  • conducting the demethylation step without recycle provides several process advantages, such as increasing process reliability and reducing operating costs.
  • the light C 4 - hydrocarbon components can be readily removed from the demethylation product by, for example, distillation, thereby yielding a purified neopentane product stream.
  • the purified neopentane product stream comprises greater than about 80 wt% neopentane, or greater than about 90 wt% neopentane, or greater than about 95 wt% neopentane, or greater than about 99 wt% neopentane, such as from about 80 wt% to about 99 wt% neopentane, or from about 85 wt%, to about 95 wt% neopentane.
  • the present inventive process will now be more particularly described with reference to the Figure.
  • the Figure illustrates one aspect of the present inventive process, in which a C 4 - C 7 paraffinic feed stream is fed to an isomerization reactor to produce an isomerization product, after which neohexane and/or neoheptane is separated and demethylated.
  • the invention is not limited to this aspect, and this description is not meant to foreclose other aspects within the broader scope of the invention.
  • a C 4 -C 7 paraffinic feed stream 101 and a hydrogen stream 102 are fed to an isomerization reactor 103 to produce an isomerization effluent 104 comprising neohexane and/or neo-heptane, unreacted C 4 -C 7 normal paraffins (e.g., n-pentane, n-hexane, and n-heptane), non-neo C 4 -C 7 branched paraffins (e.g., i-pentane, i-hexane, i-heptane, 2,4- dimethylpentane, and 2,3-dimethylpentane), and C 3 - hydrocarbon components obtained from cracking reactions.
  • C 4 -C 7 normal paraffins e.g., n-pentane, n-hexane, and n-heptane
  • the isomerization effluent is then fed to a separator 105, e.g., a distillation column, to separate a light fraction 106 comprising C 5 - hydrocarbons and a heavy fraction 107 comprising non-neo C 6 -C 7 hydrocarbon isomers from the isomerization effluent.
  • the resulting obtained fraction 108 is mainly composed of neohexane and/or neoheptane.
  • the light fraction 106 may be used for fuel or mogas (not shown).
  • the heavy fraction 107 can be recycled to isomerization reactor 103.
  • Fraction 108 and a hydrogen stream 109 are then introduced to a demethylation reactor 110 to produce a demethylation effluent 111 comprising neopentane and C 4 - hydrocarbons.
  • the demethylation effluent 111 is then fed to a separator 112 e.g., a distillation column, to separate a light fraction 113 comprising C 4 - hydrocarbons from the demethylation effluent 111.
  • the resulting obtained fraction 114 is mainly composed of neopentane.
  • the light fraction 113 can be used for fuel (not shown).
  • Neopentane produced in accordance with the present invention is useful as a blowing agent for the production of foamed polymers and possesses several properties (e.g., a boiling point of 9.5°C and a freezing point of -16.6°C) making it useful as a heat removal agent and/or as an inert condensing agent (ICA) in gas phase polymerization process, such as gas phase polymerization processes for the production of polyethylene.
  • ICA inert condensing agent
  • Neopentane produced in accordance with this invention also exhibits high octane numbers and is therefore useful as a gasoline blend component.
  • a 1.5%Rh/Si02 catalyst was prepared by incipient wetness impregnation.
  • Silica gel (DavisilTM 646, Sigma-Aldrich) was calcined by heating at a rate of 10°C/min to 700°C and holding at 700°C for 15 hours, then cooled to 50°C and held at temperature overnight.
  • the pore volume of the calcined silica was determined to be 1.34 cc/g.
  • the calcined silica (10 g) was then impregnated with a solution of rhodium (III) chloride hydrate (0.39 g) dissolved in 13.4 mL water to give an Rh loading of 1.5 wt%.
  • the resultant product was transferred to a ceramic dish, calcined by heating at a rate of 10°C/min to 250°C and holding at 250°C for 10 hours, then cooled to 50°C and held at temperature overnight.
  • a 1.5%Ir/Si02 catalyst was prepared by incipient wetness impregnation.
  • Silica gel (DavisilTM 646, Sigma-Aldrich) was calcined by heating at a rate of 10°C/min to 700°C and holding at 700°C for 15 hours, then cooled to 50°C and held at temperature overnight. The pore volume of the calcined silica was determined to be 1.34 cc/g.
  • An aqueous solution of iridium (III) chloride was prepared by adding 0.28 g of iridium (III) chloride hydrate to 13.4 mL water, followed by adding 5 drops of concentrated HC1. The resulting mixture was then stirred and heated until the metal salt completely dissolved.
  • a neohexane feed was demethylated in the presence of each of the catalyst of Example 1, the catalyst of Example 2, and a 1.5%Pd/Si02 catalyst using a down-flow, tubular, fixed bed reactor and process described below.
  • Catalytic reactions were performed using a down-flow, tubular, fixed-bed reactor equipped with two 100-mL ISCO pumps and various gas feeds.
  • the liquid feed was delivered via the ISCO pumps, mixed with gas feed through a heated section for vaporization before entering the reactor (3/8 in O.D. x 16 3/4 in x 0.028 in wall stainless steel tube) (1 cm x 43 cm x .07 cm).
  • Catalyst (0.25 - 2 g loading) was pelletized and sized to 20-40 mesh, diluted with quartz chips to a total volume of 5 mL and loaded in the isothermal zone of the reactor. A piece of 1 ⁇ 4 in (0.6 cm) O.D.
  • the catalyst was first purged with N2 and then heated to 300°C-500°C at a ramp rate of 3°C/min under flowing 3 ⁇ 4 (100 cc/min) and held 2-A h for reduction. After reduction, the reactor was cooled down to the operating temperature. The liquid feed was then introduced and H2 flow rate adjusted accordingly at the desired operating pressure.
  • a Ni/Si0 2 catalyst 64 wt% Ni powder on silica, obtained from Strem Chemicals, Inc. was pelletized, crushed, sieved (40-20 mesh, 840 to 400 ⁇ ), and loaded into each of the unit modules along with SiC diluent.
  • the catalyst loading amount was varied depending on the desired WHSV of the isooctane feed.
  • the catalyst was pre-conditioned in situ by heating to 400°C with H 2 flow at 500 sccm/min at 30 psig (300 kPa absolute) and holding for 8 h.
  • the GC was operated in a ramped pressure and split mode using hydrogen as carrier gas and a split ratio of 100 to 1.
  • the initial pressure was set at 20 psi (140 kPa) and held for 1.5 min, and then ramped at 7 psi/min (50 kPa/min) to a final pressure of 50 psi (340 kPa).
  • the initial oven temperature was set at 35 °C and held for 2 min, and then ramped at 25°C/min to 250°C.
  • the total analysis time was about 10.6 min, which enabled an injection every 15 min and a corresponding analysis frequency of lh per pair of modules.
  • 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

L'invention concerne des procédés de production de néopentane. Les procédés concernent généralement la déméthylation de néohexane et/ou de néoheptane pour produire du néopentane. Le néohexane et/ou le néoheptane peuvent être obtenus par isomérisation de paraffines C 6 -C 7 .
PCT/US2017/047586 2016-08-29 2017-08-18 Production de néopentane WO2018044592A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10487023B2 (en) 2016-08-29 2019-11-26 Exxonmobil Chemical Patents Inc. Production of neopentane
US10626064B2 (en) 2018-05-30 2020-04-21 Exxonmobil Chemical Patents Inc. Processes to make neopentane using shell and tube reactors
US10654770B2 (en) 2016-08-29 2020-05-19 Exxonmobil Chemical Patents Inc. Production of neopentane
US10870610B2 (en) 2016-08-29 2020-12-22 Exxonmobil Chemical Patents Inc. Production of neopentane
US10994264B2 (en) 2018-05-30 2021-05-04 Exxonmobil Chemical Patents Inc. Catalysts and processes for making catalysts for producing neopentane

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2413691A (en) * 1941-08-11 1947-01-07 Shell Dev Process for the production of neohexane involving catalytic isomerization
US3755493A (en) * 1971-12-30 1973-08-28 Phillips Petroleum Co Normal paraffin isomerization with liquid phase asf5/hf catalyst
US3855346A (en) * 1972-01-28 1974-12-17 Phillips Petroleum Co Isomerization of paraffinic hydrocarbons with trifluoromethanesulfonic acid
US4940829A (en) * 1988-10-18 1990-07-10 Phillips Petroleum Company Hydrodemethylation of neohexane
US5146037A (en) * 1990-11-29 1992-09-08 Uop Isomerization with distillation and psa recycle streams

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2413691A (en) * 1941-08-11 1947-01-07 Shell Dev Process for the production of neohexane involving catalytic isomerization
US3755493A (en) * 1971-12-30 1973-08-28 Phillips Petroleum Co Normal paraffin isomerization with liquid phase asf5/hf catalyst
US3855346A (en) * 1972-01-28 1974-12-17 Phillips Petroleum Co Isomerization of paraffinic hydrocarbons with trifluoromethanesulfonic acid
US4940829A (en) * 1988-10-18 1990-07-10 Phillips Petroleum Company Hydrodemethylation of neohexane
US5146037A (en) * 1990-11-29 1992-09-08 Uop Isomerization with distillation and psa recycle streams

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10487023B2 (en) 2016-08-29 2019-11-26 Exxonmobil Chemical Patents Inc. Production of neopentane
US10654770B2 (en) 2016-08-29 2020-05-19 Exxonmobil Chemical Patents Inc. Production of neopentane
US10870610B2 (en) 2016-08-29 2020-12-22 Exxonmobil Chemical Patents Inc. Production of neopentane
US10626064B2 (en) 2018-05-30 2020-04-21 Exxonmobil Chemical Patents Inc. Processes to make neopentane using shell and tube reactors
US10994264B2 (en) 2018-05-30 2021-05-04 Exxonmobil Chemical Patents Inc. Catalysts and processes for making catalysts for producing neopentane

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