WO2010129238A1 - Désulfuration et désazotation avec des liquides ioniques et des systèmes d'ions métalliques - Google Patents

Désulfuration et désazotation avec des liquides ioniques et des systèmes d'ions métalliques Download PDF

Info

Publication number
WO2010129238A1
WO2010129238A1 PCT/US2010/032473 US2010032473W WO2010129238A1 WO 2010129238 A1 WO2010129238 A1 WO 2010129238A1 US 2010032473 W US2010032473 W US 2010032473W WO 2010129238 A1 WO2010129238 A1 WO 2010129238A1
Authority
WO
WIPO (PCT)
Prior art keywords
stream
contaminant
hydrocarbon
metal
sulfur
Prior art date
Application number
PCT/US2010/032473
Other languages
English (en)
Inventor
Ryszad A. Wolny
Original Assignee
Saudi Arabian Oil Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Saudi Arabian Oil Company filed Critical Saudi Arabian Oil Company
Publication of WO2010129238A1 publication Critical patent/WO2010129238A1/fr

Links

Classifications

    • 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
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
    • 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
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
    • C10G21/12—Organic compounds only
    • C10G21/16—Oxygen-containing compounds
    • 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
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
    • C10G21/12—Organic compounds only
    • C10G21/18—Halogen-containing compounds
    • 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
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
    • C10G21/12—Organic compounds only
    • C10G21/20—Nitrogen-containing compounds
    • 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
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
    • C10G21/12—Organic compounds only
    • C10G21/22—Compounds containing sulfur, selenium, or tellurium
    • 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
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
    • C10G21/12—Organic compounds only
    • C10G21/24—Phosphorus-containing compounds

Definitions

  • This invention generally relates to the field of the upgrading of hydrocarbons.
  • the invention is directed to a process for the improved removal of sulfur and nitrogen from petroleum based hydrocarbon feeds.
  • Gasoline is typically produced as a blend of multiple components, from refining processes that use a variety of equipment, such as for example, distillation columns, catalytic crackers (FCC), hydro-crackers, and cokers.
  • the sulfur content of the gasoline component from an FCC can be as high as 1000 to 5000 ppm, thus requiring extensive treatment to meet the current regulations by reducing the sulfur content to an acceptable level for use in automobile engines.
  • FCC feed is pre-treated prior to being supplied to the FCC unit, or the gasoline component from the FCC is treated before being used as a fuel.
  • Conventional pre-treatment of an FCC feed can include hydrotreating of the feed to reduce the content of sulfur, nitrogen and metals, hydrofinishing all or a portion of the FCC naphtha, and hydrotreating the straight run kerosene and distillate, coker distillate and light cycle oil.
  • Post treatment processes can include hydrotreating all or a portion of an FCC naphtha, and hydrotreatment of the straight run kerosene and distillate, coker distillate and FCC light cycle oil.
  • products from straight run distillation columns can be hydrotreated to reduce the sulfur, nitrogen and metal content in finished products.
  • Aliphatic organosulfur compounds are typically highly reactive in conventional hydrotreating processes, and in general, are completely removed from fuels and feedstocks with little difficulty.
  • aromatic sulfur compounds which can include thiophenes, dibenzothiophenes and alkylated dibenzothiophenes, are generally more difficult to remove over traditional hydrodesulfurization catalysts.
  • the present invention described herein can achieve sulfur removal of nearly 100% yield of the original feed stream. Additionally, the processes described herein typically do not create light compounds, which can increase the vapor pressure of the effluent. Because the methods described herein are not a hydrotreating technique, high hydrogen consumption, hydrogen purity, and the associated operating costs are not an issue.
  • a method for upgrading a hydrocarbon feed having one or more contaminants includes the steps of: contacting the hydrocarbon feed with an extracting stream, the extracting stream including at least one metal salt and at least one ionic liquid, to create a mixed stream.
  • the metal ion of the metal salt binds with at least one contaminant contained in the feed stream, such that a significant amount of the at least one contaminant is removed from the hydrocarbon feed and bound to the metal.
  • the mixed stream is separated into a contaminant-lean hydrocarbon stream and a contaminant-rich stream; and the contaminant-lean hydrocarbon stream is collected as a product stream.
  • the ionic liquid includes an ion selected from the group consisting of an imidazolium ion, a pyridinium ion, an ammonium ion and a phosphonium ion.
  • the cation of the ionic liquid is selected from 1-butyl- 4-methylpyridinium ion and l-butyl-3-methylimidazolium ion.
  • the metal salt can be a salt of a Group IB, HB, VIB, or VIIIB metal.
  • the metal salt is a salt of copper, nickel, zinc, cobalt, molybdenum, silver or palladium.
  • the metal salt a salt of copper(II) or palladium(II).
  • the method further includes the steps of: supplying the contaminant-lean hydrocarbon stream to a distillation column; separating the contaminant- lean hydrocarbon stream into a vapor stream and a liquid stream; and collecting the vapor stream as a purified product stream.
  • the method further includes: supplying the contaminant-lean hydrocarbon stream to a phase separator to remove a residual extracting stream, and combining the residual extracting stream with the contaminant-rich stream; wherein the phase separator is positioned downstream of the contacting step and upstream of the distillation column.
  • the method further includes: supplying the contaminant-lean hydrocarbon stream to a phase separator to remove a residual extracting stream, and combining the residual extracting stream with the contaminant-rich stream; wherein the phase separator is positioned downstream of the contacting step and upstream of the distillation column.
  • the method further includes recycling the liquid stream to the extraction stream.
  • a process for upgrading of a hydrocarbon feed wherein the hydrocarbon feed includes one or more contaminants.
  • the process includes the steps of: mixing the hydrocarbon feed and an adsorbent containing solution in a mixing vessel, wherein the adsorbent containing solution includes at least one ionic liquid and at least one metal salt; and wherein during the step of mixing the hydrocarbon feed and the adsorbent containing solution, the metal ion of the metal salt can bind to and remove one or more contaminants present in the hydrocarbon feed.
  • the method further includues separating the mixture into a contaminant-lean hydrocarbon product stream and a contaminant-rich stream; and supplying the contaminant-lean hydrocarbon stream to a first distillation column and separating residual extracting solution to produce a hydrocarbon product stream having a reduced contaminant concentration relative to the hydrocarbon feed stream.
  • the contaminant-rich stream is supplied to a second distillation column to produce a top stream and a bottom stream, wherein the top stream includes a contaminant-rich stream and the bottom stream includes ionic liquid.
  • the process includes recycling the ionic liquid to the mixing vessel.
  • the ionic liquid includes an ion selected from the group consisting of an imidazolium ion, a pyridinium ion, an ammonium ion and a phosphonium ion.
  • the metal salt can be a salt of a Group IB, HB, VIB, or VIIIB metal, preferably selected from copper, nickel, zinc, cobalt, molybdenum, silver or palladium.
  • the at least one contaminant in the hydrocarbon feed stream includes sulfur containing compounds. In other embodiments, the at least one contaminant in the hydrocarbon feed stream includes nitrogen containing compounds.
  • Figure 1 depicts a schematic of one embodiment of a process of producing desulfurized and/or denitrogenated hydrocarbons according to one of the invention.
  • Figure 2 is an expanded stacked chromatogram showing an untreated Arabian Light fraction 400-600 0 F (top), an Arabian Light fraction 400-600 0 F treated with l-ethyl-3- methylimidazolium tosylate/copper mixture (second from top), an Arabian Light fraction
  • Figure 3 is an expanded stacked chromatogram for an untreated Arabian Light fraction 400-600 0 F (top) and an Arabian Light fraction 400-600 0 F treated with l-ethyl-3- methylimidazolium tosylate/copper mixture (bottom).
  • Figure 4 is an expanded stacked chromatogram for an untreated Arabian Light fraction 400-600 0 F (top) and an Arabian Light fraction 400-600 0 F treated with l-butyl-4- methylpyridinium tetrafluoroborate/copper mixture (bottom).
  • Figure 5 is an expanded stacked chromatogram for an untreated Arabian Light fraction 400-600 0 F (top) and an Arabian Light fraction 400-600 0 F treated with l-butyl-3- methylimidazolium octyl sulfate/copper mixture (bottom).
  • Figure 6 is an expanded stacked chromatogram showing an untreated Arabian Light fraction 400-600 0 F (top), an Arabian Light fraction 400-600 0 F treated with l-ethyl-3- methylimidazolium tosylate/palladium mixture (second from top), an Arabian Light fraction
  • Figure 7 is an expanded stacked chromatogram for an untreated Arabian Light fraction 400-600 0 F (top) and an Arabian Light fraction 400-600 0 F treated with l-ethyl-3- methylimidazolium tosylate/ palladium mixture (bottom).
  • Figure 8 is an expanded stacked chromatogram for an untreated Arabian Light fraction 400-600 0 F (top) and an Arabian Light fraction 400-600 0 F treated with l-butyl-4- methylpyridinium tetrafluoroborate/ palladium mixture (bottom).
  • Figure 9 is an expanded stacked chromatogram for an untreated Arabian Light fraction 400-600 0 F (top) and an Arabian Light fraction 400-600 0 F treated with l-butyl-3- methylimidazolium octyl sulfate/ palladium mixture (bottom).
  • Methods for the removal of contaminants from petroleum based hydrocarbon feeds are provided. Specifically, a solution operable as an extracting media for the selective removal of sulfur and/or nitrogen, and a method for the same, are provided.
  • the extracting media also called the extracting stream, can include an ionic liquid and a metal salt.
  • the terms “adsorption” and “complexation” are used to describe the complexation of metal ions with sulfur and/or nitrogen species.
  • adsorbent is used to describe the sulfur or nitrogen complexing metal ions, alone or dissolved, suspended or dispersed in ionic liquids.
  • top is used to describe the portion of a process stream which is collected from the top of a vessel during a fractionating process.
  • bottoms is used to describe the portion of a process stream which collects in the bottom of a vessel during a fractionating process.
  • Group IB metal As used herein, the terms "Group IB metal”, “Group HB metal”, “Group VIB metal” and “Group VIIIB metal” are used to describe elements from Group IB, Group HB, Group
  • the hydrocarbon feed can be any petroleum based feed stream that includes sulfur and/or nitrogen.
  • the feed stream can include gas oils, kerosenes, cat naphtha, diesel, vacuum gas oils, and the like.
  • the hydrocarbon feed employed in the method described herein have been previously treated by one or more processes designed to remove at least a portion of the sulfur and/or nitrogen present in the feed stream.
  • Sulfur species present in the feed stream can be present as aliphatic organosulfur compounds (sulfides) and both substituted and unsubstituted thiophenes, benzothiophenes, dibenzothiophenes and higher thiophene ring systems.
  • the hydrocarbon feed is free of mercaptans and hydrogen sulfide, as both mercaptans and hydrogen sulfide can react with free metal ion to form metal mercaptides and metal sulfides, respectively.
  • the mercaptans and hydrogen sulfide are preferably removed from the hydrocarbon feed stream prior to the contacting step.
  • Nitrogen species which can be present in the petroleum based feed can include pyrroles, carbazoles, benzocarbazoles, and higher nitrogen containing ring analogs, in addition to basic nitrogen containing compounds and polyhetero compounds.
  • the nitrogen containing compound can be acidic, basic or neutral. Frequently, nitrogen containing species are present in naphtha, kerosene and gas oil fractions of petroleum based feeds.
  • Ionic liquids are organic salts, which can be liquids at room temperature. Because of their ionic nature, ionic liquids are frequently very good solvents for ionic or polar compounds.
  • Ionic liquids without metals have been previously used for extractive desulfurization, wherein sulfur is removed from petroleum based hydrocarbon feeds at ambient conditions.
  • Ionic liquids containing metal functionality can be used for deep desulfurization of diesel fuel.
  • diesel is desulfurized by hydrotreatment, which can eliminate aliphatic and cyclic sulfur compounds.
  • hydrotreatment can eliminate aliphatic and cyclic sulfur compounds.
  • dibenzothiophenes and alkyl-substituted dibenzothiophenes are removed by this process.
  • the use of ionic liquids removes aliphatic and cyclic compounds but also these difficult sulfur compounds, this being defined as deep desulfurization.
  • Ionic liquids have a variety of desirable properties, including but not limited to, low melting temperature, extremely low vapor pressure, high temperature stability, high heat capacity, high density, high thermal conductivity, and non-flammability. Additionally, because of the many variations in composition that are possible, ionic liquids can be fine- tuned to have specific desired properties based upon the large number of cation and anion combinations that are possible. For several years, ionic liquids have been specifically studied as potential replacements for conventional organic solvents which are frequently toxic, flammable and/or volatile. [0044] Ionic liquids include a cation and an anion.
  • Cations of ionic liquids generally include a combination of substituted and unsubstituted organic cations having nitrogen or phosphorous.
  • the ionic liquid includes an imidizolium ion, a pyridinium ion, a pyrrolium, a quaternary ammonium ion, or a phosphonium ion.
  • Exemplary cations useful in the invention include, but are not limited to, alkyl-imidizolium anions (for example, l-butyl-3-methyl-imidazolium l-octyl-3-methylimidazolium, ethyl-3-methyl-l-imidazolium, hexy 1-3 -methyl- 1- imidazolium, or butyl-3-dimethyl-l,2-imidazolium) or alkoxy-imidizolium salts (for example, l-Hexyloxyrnethyl-3-methyl-imidazolium or 1 -hexy loxymethy 1-3 -methyl- imidazolium), alkyl-pyridinium salts (for example, N-butyl-N-methylpyrrolidinium, N- butylpyridinium, N-ethylpyridinium, or pyridinium), quaternary ammonium (for example, trimethylphenyl-ammoni
  • the anions can include a variety of alkyl substituents (e.g., methyl, ethyl, butyl, etc.).
  • exemplary inorganic anions can include, but are not limited to, halo or alkyl-sulfates, halo or alkyl-sulfonates, halides, hydroxide, perchlorate, borates, halo- borates, nitrates, sulfates, p hosphates, acetates, haloacetates, triflate (i.e., CF 3 SO 3 " ), bis(trifyl)imide [(CF 3 SO 2 ) 2 N ⁇ " ], halo-aluminates, tetrafluoroborate, halo-phosphates, halo- antimonates halo-sulfonates, alkyl sulfonates (for example, methyl sulfonate), halo-al
  • Exemplary salts that can be used include, but are not limited to, l-ethyl-3- methylimidazolium tosylate, N-butyl-pyridinium hexafluorophosphate, l-butyl-4- methylpyradinium hexafluorophosphate, l-butyl-4-methylpyradinium tetrafluoroborate, N- ethyl-pyridinium tetrafluoroborate, pyridinium fluorosulfonate, l-butyl-3-methyl- imidazolium tetrafluoroborate, l-butyl-3-methyl-imidazolium octyl sulfate, l-butyl-3-methyl- imidazolium bis-trifluoromethane-sulfonyl amide, triethylsulfonium bis-trifluorornethane- sulfonyl amide,
  • the ionic liquids can be dried under reduced pressure to remove water prior to use.
  • Most ionic liquids are hygroscopic, and in certain instances, the presence of water can change their properties. In certain instances, the presence of water can negatively effect the removal of sulfur, nitrogen and/or other contaminants. Thus, in certain embodiments, substantially all water is removed.
  • ionic liquids show selectivity for the separation of aromatic hydrocarbons from a mixture of aromatic and non-aromatic hydrocarbons. Cation choice can also play a role in selectivity during separations.
  • substituted pyridinium ions have more aromatic character than imidazolium based ionic liquids, and thus may exhibit higher aromatic selectivity than imidazolium based ionic liquids.
  • ionic liquids based on alkyl imidazolium ions having shorter alkyl chains can be favorable for aromatic/aliphatic selectivity.
  • ionic liquids having short chain alkyl imidazolium ions can show improved removal of aromatic sulfur species from hydrocarbon feeds.
  • the ionic liquids can be mixed with one or more metal salt to form an extracting media.
  • the metal ion of the metal salt is capable of bonding to sulfur and nitrogen species.
  • the metal salt can include a metal selected from Groups IB, HB, VIB and VIIIB of the periodic table.
  • the metal salt can include one or more of copper, nickel, zinc, cobalt, molybdenum, silver and palladium.
  • the metal salt can include copper(II).
  • the metal salt can include palladium(II).
  • Anions for the metal salt can include any organic or inorganic anion.
  • the metals present in the metal salts can form complexes with sulfur and/or nitrogen containing compounds present in hydrocarbon feeds by coordinating to the free electron pair present in sulfur and nitrogen. Copper, nickel, zinc, cobalt, molybdenum, silver and palladium are believed to be particularly effective in coordinating to the various aromatic and non-aromatic sulfur compounds.
  • Extraction of sulfur and/or nitrogen with an extracting media that includes an ionic liquid and a metal salt can be accomplished at any temperature at which the ionic salt is present as a liquid.
  • the extraction can occur at a temperature of greater than 0 0 C.
  • the extraction can occur at room temperature.
  • the extraction occurs at a temperature between O 0 C and 100 0 C.
  • the extraction temperature is lower than the decomposition temperature of the metal-sulfur complex or the metal-nitrogen complex.
  • the process for removing sulfur and/or nitrogen from hydrocarbon feed streams includes the steps of contacting a hydrocarbon stream that includes one or more contaminants (e.g., sulfur and/or nitrogen containing compounds) in a mixing vessel with an extracting media or extracting stream that can include at least one ionic liquid and at least one metal salt.
  • the extracting media can include two or more metal salts.
  • the extracting media can include two or more ionic liquids.
  • the extracting media can include two or more ionic solvents and two or more metal salts.
  • the extracting media consists of an ionic liquid and a metal salt.
  • concentration of the metal salt in the ionic liquid is maximized to maximize the efficiency of the process.
  • a saturated solution of the metal salt and ionic liquid is preferred.
  • solutions having lower concentrations of the metal salt can also be used for the desulfurization and denitrogenation of hydrocarbon feed streams.
  • the extracting media can be in the form of a suspension of the metal salt in an ionic liquid.
  • the hydrocarbon stream and extracting media are combined in a mixing vessel, to which they can be supplied in a counter-current flow.
  • the reaction between the extracting media and the sulfur and/or nitrogen containing compounds is relatively quick, thus, in certain embodiments, long contact and/or residence times are not required for substantial removal of sulfur and/or nitrogen.
  • the mixing vessel can include trays or baffles which are designed to increase the contact between the hydrocarbon feed stream and the extracting media.
  • the mixing vessel can include mechanical stirring means or other means of mixing the contents to ensure adequate mixing between the extracting media and the hydrocarbon stream.
  • the hydrocarbon stream and extracting media are contacted for up to one hour. More preferably, the hydrocarbon stream and extracting media are contacted for less than 30 minutes. Even more preferably, the hydrocarbon stream and the extracting media are contacted for less than 15 minutes.
  • the extraction is preferably conducted at a temperature of between 0 0 C and 100 0 C.
  • the temperature is ambient temperature.
  • the complexation equilibrium between the sulfur compound and the metal ion is temperature sensitive, and extraction of sulfur compounds is favored at lower temperatures.
  • the extraction process is performed at the lowest temperature possible, while still maintaining good fluid flow and good fluid mixing. In certain preferred embodiments, the extraction is performed at room temperature.
  • the ratio of the hydrocarbon feed to the extracting media can be between about 0.1 :1 and about 100:1. In certain embodiments, the ratio can be between about 0.25:1 and about 50:1. In preferred embodiments, the ratio of the hydrocarbon feed to extracting media is between about 0.5:1 and about 10:1.
  • the hydrocarbon is supplied to the mixing vessel as a gas.
  • the hydrocarbon feed stream is supplied to the mixing vessel as a liquid.
  • the metal ion in the extracting media form complexes with the free electron pair of sulfur and/or nitrogen present in the hydrocarbon feed stream.
  • the metal-sulfur complex and/or metal-nitrogen complex are preferably soluble in the ionic liquid, thus allowing the complexes to be easily removed from the mixing vessel.
  • the metal-sulfur complex and/or metal-nitrogen complex can be removed from the mixing vessel as a bottom stream.
  • FIG. 1 which demonstrates a process for the removal of sulfur and nitrogen from a hydrocarbon feed stream based on liquid-liquid extraction, combined with distillation, to recover a contaminant-free petroleum stream from residual extracting media, and a contaminant-containing petroleum stream from the extracting media.
  • petroleum stream refers to hydrocarbons derived from natural or synthetic crude oil.
  • the petroleum stream preferably has a final boiling point temperature lower than the decomposition temperature of the extracting media phase.
  • petroleum stream is preferably substantially free of hydrogen sulfide and mercaptans.
  • a petroleum stream feed is delivered from the feed tank 12 via line 14 to the bottom of the counter current extraction column 16.
  • the extracting media is delivered via line 18, from the recycle tank 21, to the top of the counter current extraction column 16.
  • the flow through the counter current extraction column is gravity assisted due to the difference between the gravity of the feed and the extracting media.
  • pumps can be connected to the petroleum feed line 14 and the extracting media line 18 to control the respective velocities through the counter current extraction column 16.
  • a contaminant-free petroleum stream 20 is collected from the top of the counter current extraction column 16 in optional first settling tank 22.
  • the contaminant-rich petroleum stream 24 containing sulfur and/or nitrogen dissolved in the extracting media may be drawn from the bottom of the counter current extraction column into optional second settling tank 26, to facilitate separation of the contaminant-free petroleum from residual the extracting media.
  • the extracting media may include at least one ionic liquid and at least one metal salt.
  • the first and second settling tanks 22 and 26 can, in certain embodiments, be integrated into a single unit with counter current extraction column 16.
  • the contaminant-free petroleum stream 30 is directed from optional first settling tank 22 to first distillation column 32, to separate entrained and dissolved extracting media in the contaminant free petroleum stream into an extracting media stream 39.
  • the bottom stream 39 from the first distillation column 32 which includes ionic extracting media, is returned to the extracting media recycle tank 21.
  • a purified contaminant-free petroleum stream 34 is collected in the tank 36, or may optionally be supplied to an integrated plant process.
  • a contaminant-rich petroleum stream 38 is directed from settling tank 26 to second distillation column 40, to recover sulfur and nitrogen contaminants that were present in the petroleum stream feed.
  • the contaminant-rich petroleum stream 42 collected from the top of the second distillation column 40 is delivered to tank 44 via line 42.
  • the extracting media recovered from the second distillation column 40 is returned to the extracting media recycle tank 21 via line 46.
  • the extracting media recovered in the extracting media recycle tank 21 can be resupplied to the process via line 18.
  • fresh extracting media can be supplied to the counter current extraction column 16, instead of or in combination with the recycled extracting media from recycle tank 21.
  • the process for the removal of sulfur and/or nitrogen from petroleum stream using ionic liquid/metal ion (extracting media) can include other separation methods based on membrane, supported membrane, solvent extraction, and adsorption schemes, and the like.
  • both the mixing and separation steps are performed in the same vessel. This is due, in part, to the fact that the extracting media is denser than the hydrocarbon feed stream, thus allowing for a counter-current flow to be designed and used.
  • the extracting media is preferably supplied to the top of the mixing vessel and the less dense hydrocarbon supplied to the bottom of the mixing vessel.
  • Gravity separation can facilitate recovery of a sulfur and/or nitrogen lean hydrocarbon stream from the upper section of the vessel and a sulfur and/or nitrogen rich stream, which includes extracting media, from the lower section of the vessel.
  • a second vessel such as for example, a settling tank, can be used to receive the mixture from the mixing vessel and for separation into a sulfur and/or nitrogen lean stream and a stream that includes sulfur and/or nitrogen compounds.
  • hydrocarbons in the sulfur and/or nitrogen-lean stream and hydrocarbons present in the sulfur and/or nitrogen-rich stream can be recovered in two separate distillation processes.
  • a first distillation column can be supplied with the sulfur and/or nitrogen-lean hydrocarbon stream to produce a hydrocarbon product stream of increased purity relative to the initial feed. Residual extracting media that can be present in the sulfur and/or nitrogen lean hydrocarbon stream can be removed as a bottom stream from the first distillation column.
  • the separation of the residual extracting media from the sulfur and/or nitrogen lean hydrocarbon stream can be accomplished by solvent extraction, membrane separation, or a combination of solvent extraction and membrane separation.
  • the sulfur and/or nitrogen-rich stream can be supplied from the mixing vessel to a second distillation column.
  • the sulfur and/or nitrogen-rich stream can include extracting media, and sulfur and nitrogen components dissolved in the extracting media and residual hydrocarbon feed. Elevated temperatures applied during a distillation process can decompose complexes formed between the metal ions and sulfur and/or nitrogen compounds.
  • the second distillation column can be operated to produce a top stream that primarily includes sulfur and nitrogen containing compounds and a bottom stream that can include the extracting media.
  • the extracting media has a very low vapor pressure (particularly in comparison to the hydrocarbon streams), thus separation by distillation can be employed.
  • distillation temperatures i.e., the final boiling point of the hydrocarbon feed
  • separation of the extracting media from the sulfur and/or nitrogen rich hydrocarbon stream can be achieved by flash distillation.
  • the separation of the residual hydrocarbons from the extracting media carried out by the second distillation column can be accomplished by solvent extraction, membrane separation, or a combination of solvent extraction and membrane separation.
  • the desulfurization and denitrogenation methods, as disclosed herein, are effective to reduce the sulfur and/or nitrogen content of the hydrocarbon feed stream by at least 10%, 25%, 50%, 75% or 90%.
  • the desulfurization and denitrogenation methods disclosed herein can reduce the sulfur and nitrogen content of a hydrocarbon feed stream by at least 95%. In instances of sufficient contact time between the hydrocarbon stream and the extracting media, essentially 100% of the sulfur and nitrogen containing species can be removed.
  • a hydrocarbon stream that includes sulfur and/or nitrogen can be contacted with the extracting media having at least one ionic liquid and at least one metal salt to produce a hydrocarbon steam having a sulfur content of less then 100 ppm, 50 ppm, 30 ppm, 20 ppm or 10 ppm.
  • the resulting hydrocarbon stream may have a sulfur content of less than 5 ppm.
  • the hydrocarbon feed stream can be contacted with the extracting media multiple times.
  • the extraction method can also include the step of regenerating the ionic liquid by removing the sulfur compounds.
  • the step of removing the sulfur compound from the ionic liquid can include heating the ionic liquid to vaporize the sulfur compound, extraction of the sulfur compound from the ionic liquid with another solvent, gas stripping, vaporization at a reduced pressure, and combinations of the foregoing techniques.
  • the process can include one or more other separation techniques, such as for example, the use of membranes, supported membranes, solvent extraction, adsorption schemes, and the like.
  • Examples 1-3 are directed to ionic liquid/metal salt extracting media combinations for the desulfurization of petroleum hydrocarbons.
  • One mass unit of l-butyl-4-methylpyridinium tetrafluoroborate was mixed with 0.2 mass units of palladium(II) nitrate hydrate at room temperature.
  • the mixture was contacted with a gas oil fraction at a ratio of 4:6 (extracting media to gas oil fraction), followed by vigorous mixing for approximately 2 minutes.
  • the gas oil fraction consists of a 1 :1 ratio by volume of Arabian Light crude having boiling points of 400-500 0 F and 500-600 0 F and a sulfur content of 9,639 ppm.
  • Examples 4-9 were prepared and tested for a variety of properties.
  • a sample was prepared by combining l-ethyl-3-methylimidazolium tosylate and palladium(II) nitrate hydrate in a 5:1 ratio.
  • a sample was prepared by combining l-butyl-4-methylpyridinium tetrafluoroborate and copper(II) nitrate hemipentahydrate in a 5:1 ratio.
  • a sample was prepared by combining l-butyl-3-methylimidazolium octyl sulfate and palladium(II) nitrate in a 5:1 ratio.
  • a sample was prepared by combining l-ethyl-3-methylimidazolium tosylate and copper(II) nitrate hemipentahydrate in a 5:1 ratio.
  • a sample was prepared by combining l-butyl-4-methylpyridinium tetrafluoroborate and palladium(II) nitrate in a 5:1 ratio.
  • a sample was prepared by combining l-butyl-3-methylimidazolium octyl sulfate and copper(II) nitrate hemipentahydrate in a 5:1 ratio.
  • metal solubility in the ionic liquid was tested by combining the ionic liquid and metal salt in a vial in a 5:1 weight ratio.
  • the samples were heated to approximately 80 0 C and cooled to room temperature to induce solubility.
  • l-butyl-4-methylpyridiniurn tetrafluoroborate demonstrated the highest solubility for both copper(II) nitrate and palladium(II) nitrate.
  • the palladium and copper metals exhibited solubility of between 2 weight% and 20 weight%.
  • palladium(II) nitrate hydrate exhibited greater solubility in the ionic liquid than copper(II) nitrate hemipentahydrate. Tests were not conducted to determine if palladium(II) nitrate was soluble in an amount greater than 20% by weight.
  • PFPD PFPD
  • injector temperature 300 0 C
  • split mode of 1/80 or 1/50
  • injection volume between 0.2 and 1 ⁇ L
  • Column Parameters column length of 30m, having a 0.25 mm ID and a 250 ⁇ m film
  • initial column temperature of 4O 0 C ramp to 300 0 C at a rate of 10°C/min; hold time at 300 0 C for 5 min.
  • pressure of 17 psi column flow rate of 1.2 mL/min at 4O 0 C
  • Detector Parameters temperature 300 0 C; hydrogen flow rate of 35 mL/min and air flow rate of 400 mL/min.
  • Benzothiophene was used as the internal standard due to the low concentration that occurs naturally relative to the alkylated benzothiophene species and lower boiling point.
  • the palladium metal salt achieved higher desulfurization than copper in the ionic solvent.
  • palladium in l-butyl-4- methylpyridinium tetrafluoroborate removed 2.3 times more sulfur than copper in the same solvent.
  • the desulfurization capacity of the ionic liquid/metal salt solutions increases in those systems where the solubility of the metal salt is higher, and in those solutions that tend to form strong charge transfer complexes.
  • stacked chromatograms are provided for the desulfurization of an Arabian Light fraction (400-600 0 F) gas oil by extraction with ionic liquid/copper metal salt extracting media. From top to bottom the figure provides the chromatogram for untreated gas oil and, gas oil extracted with l-ethyl-3-methylimidazolium tosylate/copper mixture (third from bottom), l-butyl-4-methylpyridinium tetrafluoroborate/copper mixture (second from bottom), and l-butyl-3-methylimidazolium octyl sulfate/copper mixture (bottom).
  • Figures 3, 4 and 5 Individual chromatograms for each of ionic liquid/copper metal salt examples 5, 7 and 9 are provided in Figures 3, 4 and 5, respectively.
  • Figure 3 corresponds to Example 5 and provides a comparison of the chromatogram of an untreated gas oil with the chromatogram of a gas oil fraction extracted with l-ethyl-3-methylimidazolium tosylate/copper mixture.
  • Figure 4 corresponds to Example 7 and provides a comparison for the chromatogram of an untreated gas oil with the chromatogram of a gas oil fraction extracted with l-butyl-4-methylpyridinium tetrafluoroborate/copper mixture.
  • Figure 5 corresponds to Example 9 and provides a comparison of the chromatogram of an untreated gas oil and the chromatogram of a gas oil that has been extracted with l-butyl-3-methylimidazolium octyl sulfate/copper mixture. Comparing the relative peak intensity for components having a retention time above and below 18 minutes (relating to dibenzothiphenes and benzothiophenes, respectively) demonstrates that each of the ionic liquid/metal salt systems from Examples 5, 7 and 9 have higher selectivity to removal of dibenzothiophenes than benzothiophenes.
  • stacked chromatograms are provided for the desulfurization of an Arabian Light fraction (400-600 0 F) gas oil by extraction with ionic liquid/palladium metal salt extracting media. From top to bottom the figure provides the chromatogram for untreated gas oil and, gas oil extracted with l-ethyl-3-methylimidazolium tosylate/palladium mixture (third from bottom), l-butyl-4-methylpyridinium tetrafluoroborate/palladium mixture (second from bottom), and l-butyl-3-methylimidazolium octyl sulfate/palladium mixture (bottom).
  • Figures 7, 8 and 9 Individual chromatograms for each of the ionic liquid/palladium metal salt provided in Examples 4, 6 and 8 are provided in Figures 7, 8 and 9, respectively.
  • Figure 7 corresponds to Example 4 and provides a comparison of the chromatogram of an untreated gas oil with the chromatogram of a gas oil extracted with l-ethyl-3-methylimidazolium tosylate/palladium mixture.
  • Figure 8 corresponds to Example 6 and provides a comparison of the chromatogram of an untreated gas oil and the chromatogram of a gas oil extracted with l-butyl-4-methylpyridinium tetrafluoroborate/palladium mixture.
  • Figure 9 corresponds to Example 8 and provides a comparison of the chromatogram of an untreated gas oil and the chromatogram of a gas oil extracted with l-butyl-3-methylimidazoliurn octyl sulfate/palladium mixture.
  • the ionic liquid/palladium systems show higher selectivity to removal of dibenzothiophenes than benzothiophenes.
  • Gas oil feed is 1 : 1 mixtures by weight of two separate cuts from Arabian Light crude (a 400°F - 500 0 F fraction, and a 500°F - 600 0 F fraction).
  • the terms about and approximately should be interpreted to include any values which are within 5% of the recited value.
  • recitation of the term about and approximately with respect to a range of values should be interpreted to include both the upper and lower end of the recited range.
  • optional or optionally means that the subsequently described event or circumstances may or may not occur.
  • the description includes instances where the event or circumstance occurs and instances where it does not occur.
  • Ranges may be expressed herein as from about one particular value, and/or to about another particular value. When such a range is expressed, it is to be understood that another embodiment is from the one particular value and/or to the other particular value, along with all combinations within said range.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

La présente invention porte sur un procédé de désulfuration et de désazotation de charges hydrocarbonées à base de pétrole, avec un mélange d'au moins un liquide ionique et d'au moins un sel métallique (18). Les hydrocarbures (14) en phase liquide ou gazeuse sont mis en contact (16) avec le mélange pour permettre une complexation des espèces sulfurées et azotées qui sont présentes dans le courant traité (36).
PCT/US2010/032473 2009-04-27 2010-04-27 Désulfuration et désazotation avec des liquides ioniques et des systèmes d'ions métalliques WO2010129238A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US12/430,696 2009-04-27
US12/430,696 US20100270211A1 (en) 2009-04-27 2009-04-27 Desulfurization and denitrogenation with ionic liquids and metal ion systems

Publications (1)

Publication Number Publication Date
WO2010129238A1 true WO2010129238A1 (fr) 2010-11-11

Family

ID=42617392

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2010/032473 WO2010129238A1 (fr) 2009-04-27 2010-04-27 Désulfuration et désazotation avec des liquides ioniques et des systèmes d'ions métalliques

Country Status (2)

Country Link
US (1) US20100270211A1 (fr)
WO (1) WO2010129238A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107033951A (zh) * 2017-06-26 2017-08-11 徐州洁诚环保科技有限公司 一种脱除燃料油中氮化物的方法

Families Citing this family (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MX2008006731A (es) * 2008-05-26 2009-11-26 Mexicano Inst Petrol Liquidos ionicos en la desulfuracion de hidrocarburos y procedimiento de obtencion.
WO2011002745A1 (fr) * 2009-07-01 2011-01-06 Saudi Arabian Oil Company Désulfuration membranaire d'hydrocarbures liquides au moyen d'un système de contacteur membranaire à liquide d'extraction et procédé
US20120190905A1 (en) * 2009-09-25 2012-07-26 Dow Global Technologies Llc Olefin selective membrane comprising an ionic liquid and a complexing agent
US8580107B2 (en) * 2009-12-30 2013-11-12 Uop Llc Process for removing sulfur from vacuum gas oil
US8608950B2 (en) * 2009-12-30 2013-12-17 Uop Llc Process for removing metals from resid
US8608949B2 (en) * 2009-12-30 2013-12-17 Uop Llc Process for removing metals from vacuum gas oil
US8608943B2 (en) * 2009-12-30 2013-12-17 Uop Llc Process for removing nitrogen from vacuum gas oil
US8608952B2 (en) * 2009-12-30 2013-12-17 Uop Llc Process for de-acidifying hydrocarbons
US8608951B2 (en) * 2009-12-30 2013-12-17 Uop Llc Process for removing metals from crude oil
US8888993B2 (en) 2010-07-30 2014-11-18 Chevron U.S.A. Inc. Treatment of a hydrocarbon feed
CN102212383B (zh) * 2010-12-13 2013-12-18 扬州大学 离子液体用于油品脱硫的方法
US20120302813A1 (en) * 2011-05-27 2012-11-29 Uop Llc Processes and apparatuses for producing a substantially linear paraffin product
MX2011007922A (es) * 2011-07-27 2013-02-07 Mexicano Inst Petrol Desnitrogenacion de hidrocarburos mediante extraccion liquido-liquido empleando liquidos ionicos.
US8574426B2 (en) * 2011-12-15 2013-11-05 Uop Llc Extraction of polycyclic aromatic compounds from petroleum feedstocks using ionic liquids
US8574427B2 (en) * 2011-12-15 2013-11-05 Uop Llc Process for removing refractory nitrogen compounds from vacuum gas oil
US9068127B2 (en) * 2012-06-29 2015-06-30 Uop Llc Process for removing sulfur compounds from vacuum gas oil
US9783747B2 (en) 2013-06-27 2017-10-10 Uop Llc Process for desulfurization of naphtha using ionic liquids
US9328295B2 (en) 2013-09-27 2016-05-03 Uop Llc Extract recycle in a hydrocarbon decontamination process
CN103602348B (zh) * 2013-10-17 2015-07-08 上海交通大学 汽油萃取-还原脱硫的方法
RU2541315C1 (ru) * 2013-10-18 2015-02-10 Мария Владимировна Нефедьева Способ очистки жидких моторных топлив от серосодержащих соединений
US10751675B2 (en) 2014-11-10 2020-08-25 Eme Finance Ltd. Device for mixing water and diesel oil, apparatus and process for producing a water/diesel oil micro-emulsion
US9574139B2 (en) 2014-11-24 2017-02-21 Uop Llc Contaminant removal from hydrocarbon streams with lewis acidic ionic liquids
US9475997B2 (en) 2014-11-24 2016-10-25 Uop Llc Contaminant removal from hydrocarbon streams with carbenium pseudo ionic liquids
US20170007993A1 (en) 2015-07-08 2017-01-12 Chevron U.S.A. Inc. Sulfur-contaminated ionic liquid catalyzed alklyation
IT201600132801A1 (it) 2016-12-30 2018-06-30 Eme International Ltd Apparato e processo per produrre liquido derivante da biomassa, biocarburante e biomateriale
ES2930552T3 (es) * 2017-02-10 2022-12-16 Topsoe As Un método para el hidroprocesamiento de fuentes renovables
US11499101B2 (en) * 2017-11-28 2022-11-15 Khalifa University of Science and Technology Mercury capture from hydrocarbon fluids using deep eutectic solvents
US11124692B2 (en) 2017-12-08 2021-09-21 Baker Hughes Holdings Llc Methods of using ionic liquid based asphaltene inhibitors
EA202091413A1 (ru) 2018-07-11 2020-09-24 Бейкер Хьюз Холдингз Ллк Скважинные ингибиторы асфальтенов на основе ионной жидкости и способы их применения
IT201900013212A1 (it) * 2019-07-29 2021-01-29 Eme Global Biofuel Tech S A Composizione, processo e apparecchiatura per rimuovere lo zolfo da una frazione raffinata di greggio
KR102398989B1 (ko) 2020-04-01 2022-05-18 한국기초과학지원연구원 탄화수소 유분으로부터 황화합물을 제거하는 방법
CN113322094B (zh) * 2021-05-24 2023-06-09 江苏大学 一种反应型萃取脱硫脱氮及高附加值产物回收的工艺
CN116943408B (zh) * 2023-06-30 2024-01-30 江苏创新石化有限公司 一种位阻胺复合脱硫剂及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002034863A1 (fr) * 2000-10-26 2002-05-02 Chevron U.S.A. Inc. Elimination de mercaptans de flux d'hydrocarbures a l'aide de liquides ioniques
WO2003040264A1 (fr) * 2001-11-06 2003-05-15 Extractica, Llc Procede d'extraction de composes organo-sulfureux a partir d'hydrocarbures a l'aide de liquides ioniques
FR2861084A1 (fr) * 2003-10-15 2005-04-22 Arkema Procede d'elimination de composes benzothiopheniques contenus dans un melange d'hydrocarbures

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4424121A (en) * 1982-07-30 1984-01-03 Occidental Research Corporation Selective removal of nitrogen-containing compounds from hydrocarbon mixtures
US5191153A (en) * 1989-12-26 1993-03-02 Phillips Petroleum Company Method for preparing olefin complexing reagents and use thereof
US5167797A (en) * 1990-12-07 1992-12-01 Exxon Chemical Company Inc. Removal of sulfur contaminants from hydrocarbons using n-halogeno compounds
JPH05202367A (ja) * 1991-10-15 1993-08-10 General Sekiyu Kk 抽出による軽油の脱硫および脱硝方法
GB9906829D0 (en) * 1999-03-24 1999-05-19 Univ Leicester Ionic liquids
US6274026B1 (en) * 1999-06-11 2001-08-14 Exxonmobil Research And Engineering Company Electrochemical oxidation of sulfur compounds in naphtha using ionic liquids
US6339182B1 (en) * 2000-06-20 2002-01-15 Chevron U.S.A. Inc. Separation of olefins from paraffins using ionic liquid solutions
GB0023708D0 (en) * 2000-09-27 2000-11-08 Scionix Ltd Hydrated salt mixtures
US6579343B2 (en) * 2001-03-30 2003-06-17 University Of Notre Dame Du Lac Purification of gas with liquid ionic compounds
US6841062B2 (en) * 2001-06-28 2005-01-11 Chevron U.S.A. Inc. Crude oil desulfurization
DE10155281A1 (de) * 2001-11-08 2003-06-05 Solvent Innovation Gmbh Verfahren zur Entfernung polarisierbarer Verunreinigungen aus Kohlenwasserstoffen und Kohlenwasserstoffgemischen durch Extraktion mit ionischen Flüssigkeiten
US6849774B2 (en) * 2001-12-31 2005-02-01 Chevron U.S.A. Inc. Separation of dienes from olefins using ionic liquids
FR2840916B1 (fr) * 2002-06-17 2004-08-20 Inst Francais Du Petrole Procede d'elimination des composes soufres et azotes de coupes hydrocarbonees
CA2400714A1 (fr) * 2002-08-28 2004-02-28 Nova Chemicals Corporation Utilisation de liquides ioniques pour separer des olefines, des diolefines et des composes aromatiques
RU2006126639A (ru) * 2003-12-22 2008-01-27 Шелл Интернэшнл Рисерч Маатсхаппий Б.В. (NL) Способ разделения олефинов и парафинов
US7303607B2 (en) * 2004-06-14 2007-12-04 Air Products And Chemicals, Inc. Liquid media containing Lewis acidic reactive compounds for storage and delivery of Lewis basic gases
FR2875235B1 (fr) * 2004-09-10 2006-11-24 Inst Francais Du Petrole Procede de separation des composes oxygenes contenus dans une charge hydrocarbonee, mettant en oeuvre un liquide ionique

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002034863A1 (fr) * 2000-10-26 2002-05-02 Chevron U.S.A. Inc. Elimination de mercaptans de flux d'hydrocarbures a l'aide de liquides ioniques
WO2003040264A1 (fr) * 2001-11-06 2003-05-15 Extractica, Llc Procede d'extraction de composes organo-sulfureux a partir d'hydrocarbures a l'aide de liquides ioniques
FR2861084A1 (fr) * 2003-10-15 2005-04-22 Arkema Procede d'elimination de composes benzothiopheniques contenus dans un melange d'hydrocarbures

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
CHEM. IND, vol. 68, 1996, pages 249 - 263
CHEM. REV., vol. 99, 1999, pages 2071 - 2084
CHEMICAL AND ENGINEERING NEWS, 30 March 1998 (1998-03-30), pages 32 - 37
FAN H F ET AL: "Experimental study on using ionic liquids to upgrade heavy oil", JOURNAL OF FUEL CHEMISTRY AND TECHNOLOGY,, vol. 35, no. 1, 1 February 2007 (2007-02-01), pages 32 - 35, XP022937052, ISSN: 1872-5813, [retrieved on 20070201] *
J MATER. CHEM., vol. 8, 1998, pages 2627 - 2636
J. CHEM. TECH. BIOTECHNOL., vol. 68, 1997, pages 351 - 356
J. PHYS. CONDENSED MATTER, vol. 5, no. 34B, 1993, pages B99 - BI06

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107033951A (zh) * 2017-06-26 2017-08-11 徐州洁诚环保科技有限公司 一种脱除燃料油中氮化物的方法

Also Published As

Publication number Publication date
US20100270211A1 (en) 2010-10-28

Similar Documents

Publication Publication Date Title
US20100270211A1 (en) Desulfurization and denitrogenation with ionic liquids and metal ion systems
CA2772429C (fr) Procede pour retirer des metaux de gazole sous vide
US8741128B2 (en) Integrated desulfurization and denitrification process including mild hydrotreating of aromatic-lean fraction and oxidation of aromatic-rich fraction
Ma et al. Determination of sulfur compounds in non-polar fraction of vacuum gas oil
US8758600B2 (en) Ionic liquid desulfurization process incorporated in a low pressure separator
US20090120841A1 (en) Methods of denitrogenating diesel fuel
KR20190104037A (ko) 이온성 액체 및 고체 흡착에 의한 재순환으로부터 중질 다핵 방향족화합물의 분리를 포함하는 수소첨가분해 공정 및 시스템
EP2831202B1 (fr) Procédé d'élimination de l'azote de courants de carburant avec des liquides ioniques à base de caprolactamium
Anugwom et al. Ionic liquid assisted extraction of nitrogen and sulphur-containing air pollutants from model oil and regeneration of the spent ionic liquid
EP1268710B1 (fr) Procede d'extraction de composes de soufre de flux d'hydrocarbures liquides et gazeux
US9890336B2 (en) Method and apparatus for the purification of a hydrocarbon-containing stream
KR101995703B1 (ko) 다핵 방향족 탄화수소, 헤테로사이클릭 화합물, 및 유기금속 화합물을 탄화수소 공급원료로부터 분리 및 추출하는 통합 시스템 및 방법
CA2772431C (fr) Procede pour retirer des metaux a partir de residu
JP2006160969A (ja) 灯軽油留分の精製方法及び灯軽油留分を精製する抽出溶剤
US8992767B2 (en) Ionic liquid desulfurization process incorporated in a contact vessel
Yao et al. Intensification of water on the extraction of pyridine from n-hexane using ionic liquid
US10190064B2 (en) Integrated process for simultaneous removal and value addition to the sulfur and aromatics compounds of gas oil
CN110564444A (zh) 一种采用离子液体作为萃取剂的汽油脱硫方法
JP2006089659A (ja) ナフサ留分の精製方法及びナフサ留分を精製する抽出溶剤
WO2015191372A1 (fr) Appareils et procédés pour le traitement de mercaptans

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10719673

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10719673

Country of ref document: EP

Kind code of ref document: A1