WO2015183802A1 - Procédés de valorisation de flux d'hydrocarbures contaminés - Google Patents

Procédés de valorisation de flux d'hydrocarbures contaminés Download PDF

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Publication number
WO2015183802A1
WO2015183802A1 PCT/US2015/032417 US2015032417W WO2015183802A1 WO 2015183802 A1 WO2015183802 A1 WO 2015183802A1 US 2015032417 W US2015032417 W US 2015032417W WO 2015183802 A1 WO2015183802 A1 WO 2015183802A1
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WIPO (PCT)
Prior art keywords
heteroatom
oxidized
caustic
groups
selectivity promoter
Prior art date
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PCT/US2015/032417
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English (en)
Inventor
Kyle E. Litz
Jennifer VREELAND
Jonathan P. Rankin
Mark N. Rossetti
Tracey M. Jordan
Trent A. Mccaskill
Erica H. SHIPLEY
Sarah M. CLICKNER
Original Assignee
Auterra, Inc.
Cenovus Energy Inc.
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Priority claimed from US14/287,916 external-priority patent/US9206359B2/en
Application filed by Auterra, Inc., Cenovus Energy Inc. filed Critical Auterra, Inc.
Priority to CA2949973A priority Critical patent/CA2949973A1/fr
Publication of WO2015183802A1 publication Critical patent/WO2015183802A1/fr

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    • 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
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/20—Organic compounds not containing metal atoms
    • C10G29/22—Organic compounds not containing metal atoms containing oxygen as the only hetero atom
    • 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
    • C10G19/00—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
    • C10G19/08—Recovery of used refining agents
    • 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
    • C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
    • C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
    • C10G53/12—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one alkaline treatment step
    • 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
    • C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
    • C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
    • C10G53/14—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one oxidation step

Definitions

  • heteroatom contaminants including, but not limited to, sulfur, nitrogen, phosphorus, nickel, vanadium, and iron and acidic oxygenates in quantities that negatively impact the refinery processing of the crude oil fractions.
  • Light crude oils or condensates contain heteroatoms in concentrations as low as 0.001 wt %.
  • heavy crude oils contain heteroatoms as high as 5-7 wt %.
  • the heteroatom content of crude oil increases with increasing boiling point and the heteroatom content increases with decreasing API gravity.
  • heteroatom contaminants appear in hydrocarbon streams in both oxidized and unoxidized form.
  • sulfur can appear in oxidized form as, for example, a sulfoxide, sulfone, or sulfonate, or in unoxidized form as, for example, a thiophene.
  • Naturally occurring hydrocarbon streams include both oxidized and unoxidized heteroatoms, including both oxidized and unoxidized forms of sulfur.
  • the oxidized heteroatom content of a hydrocarbon stream may also be increased through artificial processes.
  • Figure 1 describes a table of available oxidation states for organic heteroatom compounds.
  • Sulfur is widely recognized as the most egregious heteroatom contaminant as a result of the environmental hazard caused by its release into the environment after combustion. It is believed, sulfur oxides from combustion (known collectively as SO x emissions) contribute to the formation of acid rain and also to the reduction of the efficiency of catalytic converters in automobiles. Furthermore, sulfur compounds are thought to ultimately increase the particulate content of combustion products. Nitrogen, phosphorus, and other heteroatom contaminants present similar environmental risks.
  • HDS hydrodesulfurization
  • Refiners typically use catalytic hydrodesulfurizing (“HDS", commonly referred to as “hydrotreating”) methods to lower the sulfur content of hydrocarbon fuels, decrease the total acid number, and increase the API gravity.
  • HDS catalytic hydrodesulfurizing
  • a hydrocarbon stream that is derived from petroleum distillation is treated in a reactor that operates at temperatures ranging between 575 and 750 °F. (about 300 to about 400 °C), a hydrogen pressure that ranges between 430 to 14,500 psi (3000 to 10,000 kPa or 30 to 100 atmospheres) and hourly space velocities ranging between 0.5 and 4 h 1 .
  • Dibenzothiophenes in the feed react with hydrogen when in contact with a catalyst arranged in a fixed bed that comprises metal sulfides from groups VI and VIII (e.g., cobalt and molybdenum sulfides or nickel and molybdenum sulfides) supported on alumina. Because of the operating conditions and the use of hydrogen, these methods can be costly both in capital investment and operating costs.
  • groups VI and VIII e.g., cobalt and molybdenum sulfides or nickel and molybdenum sulfides
  • HDS or hydrotreating may provide a treated product in compliance with the current strict sulfur level targets.
  • sterically hindered refractory sulfur compounds such as substituted dibenzothiophenes
  • the process is not without issues. For example, it is particularly difficult to eliminate traces of sulfur using such catalytic processes when the sulfur is contained in molecules such as dibenzothiophene with alkyl substituents in position 4-, or 4- and 6-positions of the parent ring.
  • One attempt at solving the problem discussed above includes selectively desulfurizing dibenzothiophenes contained in the hydrocarbon stream by oxidizing the dibenzothiophenes into a sulfone in the presence of an oxidizing agent, followed by optionally separating the sulfone compounds from the rest of the hydrocarbon stream and further reacting the sulfones with a caustic to remove the sulfur moiety from the hydrocarbon fragment.
  • Oxidation has been found to be beneficial because oxidized sulfur compounds can be removed using a variety of separation processes that rely on the altered chemical properties such as the solubility, volatility, and reactivity of the sulfone compounds.
  • An important consideration in employing oxidation is chemical selectivity. Selective oxidation of sulfur heteroatom moieties without oxidizing the plethora of olefins and benzylic hydrocarbons found in crude oils, refinery intermediates, and refinery products remains a significant challenge.
  • One selective sulfoxidation method and system is disclosed in International Publication Number WO 2009/120238 Al, to Litz et al.
  • the catalyst of the above-mentioned international publication number is further capable of oxidizing additional heteroatoms, including, but not limited to nitrogen and phosphorus found as naturally abundant contaminants in crude oils, refinery intermediates, and refinery products as organic heteroatom-containing compounds.
  • Figure 1 describes a table of available oxidation states for organic heteroatom compounds.
  • heteroatom oxidation lies in the fate of the oxidized organic heteroatom compounds produced. If the oxidized organic heteroatom compounds are hydrotreated, they may be converted back to the original heteroatom compounds thereby regenerating the original problem.
  • the feed heteroatom content may be likely to be in the range of 0% to 10% by weight heteroatom.
  • Heteroatoms on average, comprise about 15 wt % of substituted and unsubstituted organic heteroatom molecules. Therefore, up to 67 wt % of the oil may be removed as oxidized organic heteroatom extract if not removed from the organic molecules.
  • oxidized organic heteroatom oil For a typical refinery processing 40,000 barrels per day of crude oil, up to 27,000 barrels per day of oxidized organic heteroatom oil will be generated, which is believed to be too much to dispose conventionally as a waste product. Further, the disposal of oxidized organic heteroatom oil also wastes valuable hydrocarbons, which could theoretically be recycled if an efficient process were available.
  • the present disclosure is directed to systems and methods for upgrading hydrocarbon streams by decreasing the content of undesired heteroatom contaminants, including, but not limited to, sulfur, nitrogen, phosphorus, nickel, vanadium, iron.
  • Figure 1 is a graphic representation of the various oxidation states of certain heteroatoms, in accordance with embodiments of the present disclosure.
  • Figure 2 is a generic process flow diagram of an embodiment of an oxidized heteroatom cleavage process, in accordance with embodiments of the present disclosure.
  • Figure 3 is a more detailed process flow diagram of an embodiment of an oxidized heteroatom cleavage process followed by recovery of caustic and selectivity promoter byproduct, in accordance with embodiments of the present disclosure.
  • Figure 4 is an alternative detailed process flow diagram of an embodiment of a combination oxidized-heteroatom-containing hydrocarbon extraction followed by oxidized heteroatom cleavage, in accordance with embodiments of the present invention.
  • Figure 5 is a generic process flow diagram of an embodiment of a combination heteroatom oxidation process followed by oxidized heteroatom cleavage, in accordance with embodiments of the present disclosure.
  • Figure 6A is a more detailed process flow diagram of an embodiment of a combination heteroatom oxidation process followed by oxidized heteroatom cleavage, in accordance with embodiments of the present disclosure.
  • Figure 6B is an alternative more detailed process flow diagram of an embodiment of a combination heteroatom oxidation process followed by oxidized heteroatom cleavage, in accordance with embodiments of the present disclosure.
  • Figure 7 is an even more detailed process flow diagram of an embodiment of a combination heteroatom oxidation process followed by oxidized heteroatom cleavage, in accordance with embodiments of the present disclosure.
  • Figure 8 is an alternative even more detailed process flow diagram of an embodiment of a combination heteroatom oxidation process followed by oxidized heteroatom cleavage, in accordance with embodiments of the present disclosure.
  • Figure 9 illustrates various decomposition modes for dibenzothiophene sulfone.
  • promoted-caustic visbreaker means a heated reactor that contains a caustic and a selectivity promoter that react with oxidized heteroatoms to remove sulfur, nickel, vanadium, iron and other heteroatoms, increase API gravity and decrease total acid number.
  • contaminated hydrocarbon stream is a mixture of hydrocarbons containing heteroatom constituents.
  • Heteroatoms is intended to include all elements other than carbon and hydrogen.
  • sulfoxidation is a reaction or conversion, whether or not catalytic, that produces sulfoxide or organo-sulfoxide, sulfone or organo-sulfone, sulfonate or organo-sulfonate, or sulfonic acid or organo-sulfonic acid compounds (and/or mixtures thereof) from organosulfur compounds.
  • a sulfone is a chemical compound containing a sulfonyl functional group attached to two carbon atoms. The central hexavalent sulfur atom is double bonded to each of two oxygen atoms and has a single bond to each of two carbon atoms, usually in two separate hydrocarbon substituents.
  • R and R' are the organic groups which may be hydrogen or an organic compound (which may be further substituted) including, but not limited to, straight, branched and cyclic alkyl groups; straight, branched and cyclic alkenyl groups; and aromatic or polycyclic aromatic groups.
  • Further substituents where R is an organic may include hydroxide groups, carbonyl groups, aldehyde groups, ether groups, carboxylic acid and carboxylate groups, phenol or phenolate groups, alkoxide groups, amine groups, imine groups, cyano groups, thiol or thiolate groups, thioether groups, disulfide groups, sulfate groups, and phosphate groups.
  • a sulfoxide is a chemical compound containing a sulfinyl (SO) functional group attached to two carbon atoms. It is a polar functional group.
  • Sulfoxides are the oxidized derivatives sulfides.
  • R is an organic
  • substituents where R is an organic may include hydroxide groups, carbonyl groups, aldehyde groups, ether groups, carboxylic acid and carboxylate groups, phenol or phenolate groups, alkoxide groups, amine groups, imine groups, cyano groups, thiol or thiolate groups, thioether groups, disulfide groups, sulfate groups, and phosphate groups.
  • the bond between the sulfur and oxygen atoms is intermediate of a dative bond and a polarized double bond.
  • a sulfonate is a salt or ester of a sulfonic acid. It contains the functional group R-S0 2 0-.
  • the R groups may be any of the R groups described in reference to the sulfoxides above.
  • a reaction or conversion of nitrogen may also occur, whether or not catalytic, that produces an amine oxide, a nitroso compound, a nitrate, or a nitro compound.
  • Amine oxide is also known as amine-N-oxide and N-oxide, is a chemical compound that contains the functional group R 3 N + -0 ⁇ an N-0 bond with three additional hydrogen and/or hydrocarbon side chains attached to N.
  • the R groups may be organic groups which may be hydrogen or an organic compound (which may be further substituted) including, but not limited to, straight, branched and cyclic alkyl groups; straight, branched and cyclic alkenyl groups; and aromatic or polycyclic aromatic groups.
  • R is an organic
  • R groups may include hydroxide groups, carbonyl groups, aldehyde groups, ether groups, carboxylic acid and carboxylate groups, phenol or phenolate groups, alkoxide groups, amine groups, imine groups, cyano groups, thiol or thiolate groups, thioether groups, disulfide groups, sulfate groups, and phosphate groups.
  • the R groups may also be attached to each other by means of a chemical bond.
  • the R group may be any of the R groups described above in reference to amine oxide.
  • Nitrate is a polyatomic ion with the molecular formula NO 3 .
  • the R group may be any of the R groups described above in reference to amine oxide.
  • Nitro compounds are organic compounds that contain one or more nitro functional groups (-NO 2 ).
  • the R group may be any of the R groups described above in reference to amine oxide.
  • the invention provides a method of upgrading an oxidized- heteroatom-containing hydrocarbon feed by removing oxidized heteroatom contaminants, the method comprising: contacting at least one of sulfone, sulfoxide, sulfonate, sulfonic acid and combinations thereof in the oxidized-heteroatom-containing hydrocarbon feed with at least one caustic and at least one selectivity promoter to form a first intermediate stream; and removing the oxidized-heteroatom contaminants from the first intermediate stream.
  • the oxidized-heteroatom- containing hydrocarbon feed may include one or both of naturally occurring oxidized heteroatoms and artificially created oxidized heteroatoms.
  • the invention provides a method of upgrading an oxidized-heteroatom-containing hydrocarbon feed by removing oxidized-heteroatom
  • the method comprising: contacting at least one of sulfone, sulfoxide, sulfonate, sulfonic acid and combinations thereof in the oxidized-heteroatom-containing hydrocarbon feed with at least one caustic and at least one selectivity promoter to form a first intermediate stream; removing the oxidized-heteroatom contaminants from the first intermediate stream; and recovering the at least one caustic and at least one selectivity promoter for reuse.
  • the oxidized- heteroatom-containing hydrocarbon feed may include one or both of naturally occurring oxidized heteroatoms and artificially created oxidized heteroatoms.
  • the invention provides a method of upgrading an oxidized-heteroatom-containing hydrocarbon feed by removing oxidized heteroatom
  • the method comprising: extracting at least one of sulfone, sulfoxide, sulfonate, sulfonic acid and combinations thereof from the oxidized-heteroatom-containing hydrocarbon feed to form a first intermediate stream; contacting the first intermediate stream with at least one caustic and at least one selectivity promoter to form a second intermediate stream; and removing the oxidized-heteroatom contaminants from the second intermediate stream.
  • the oxidized- heteroatom-containing hydrocarbon feed may include one or both of naturally occurring oxidized heteroatoms and artificially created oxidized heteroatoms.
  • the invention provides a method of upgrading a heteroatom-containing hydrocarbon feed by removing heteroatom contaminants, the method comprising: contacting the heteroatom-containing feed with an oxidant to oxidize at least a portion of the heteroatom contaminants to form a first intermediate stream; contacting the first intermediate stream with at least one caustic and at least one selectivity promoter to form a second intermediate stream; separating a substantially heteroatom-free hydrocarbon product from the second intermediate stream.
  • the oxidant may be used in the presence of a catalyst.
  • the invention provides a method of upgrading a heteroatom-containing hydrocarbon feed by removing heteroatom contaminants, the method comprising:
  • the invention provides a method of upgrading a heteroatom-containing hydrocarbon feed by removing heteroatom contaminants, the method comprising oxidizing dibenzothiophenes to sulfones, reacting the sulfones with caustic and a selectivity promoter, and separating a substantially heteroatom-free hydrocarbon product for fuel.
  • the oxidation reaction may be carried out at a temperature of about 20°C to about 120°C, at a pressure of about 0.5 atmospheres to about 10 atmospheres, with a contact time of about 2 minutes to about 180 minutes.
  • the oxidant employed may be any oxidant which, optionally in the presence of a catalyst, oxidizes heteroatoms in the heteroatom-containing hydrocarbon feed, for example, but not limited to, hydrogen peroxide, peracetic acid, benzyl hydroperoxide, ethylbenzene hydroperoxide, cumyl hydroperoxide, sodium hypochlorite, oxygen, air, etc, and more presently preferably an oxidant which does not oxidize the heteroatom-free hydrocarbons in the contaminated hydrocarbon feed.
  • the catalyst employed therein may be any catalyst capable of utilizing an oxidant to oxidize heteroatoms in the heteroatom-containing hydrocarbon feed
  • Suitable catalysts include, but are not limited to, catalyst compositions represented by the formula M m O m (OR) n , where M is a metal complex, such as, for example, titanium or any metal, including, but not limited to, rhenium, tungsten or other transition metals alone or in combination that causes the chemical conversion of the sulfur species, as described herein.
  • M is a metal complex, such as, for example, titanium or any metal, including, but not limited to, rhenium, tungsten or other transition metals alone or in combination that causes the chemical conversion of the sulfur species, as described herein.
  • R is carbon group having at least 3 carbon atoms, where at each occurrence R may individually be a substituted alkyl group containing at least one OH group, a substituted cycloalkyl group containing at least one OH group, a substituted cycloalkylalkyl group containing at least one OH group, a substituted heterocyclyl group containing at least one OH group, or a heterocyclylalkyl containing at least one OH group.
  • the subscripts m and n may each independently be integers between about 1 and about 8.
  • R may be substituted with halogens such as F, CI, Br, and I.
  • the metal alkoxide comprises bis(glycerol)oxotitanium(IV)), where M is Ti, m is 1, n is 2, and R is a glycerol group.
  • metal alkoxides include bis(ethyleneglycol)oxotitanium (IV),
  • Suitable catalysts include, but are not limited to, catalyst compositions prepared by the reaction of Q-R-Q' with a bis(polyol)oxotitanium(IV) catalyst, wherein Q and Q' each independently comprise an isocyanate, anhydride, sulfonyl halide, benzyl halide, carboxylic acid halide, phosphoryl acid halide, silyl chloride, or any chemical functionality capable of reacting with the -OH pendant group of the catalyst, and wherein R comprises a linking group.
  • the R linking group is selected from the group consisting of alkyl groups (including linear, branched, saturated, unsaturated, cyclic, and substituted alkyl groups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the like can be present in the alkyl group), typically with from 1 to about 22 carbon atoms, preferably with from 1 to about 12 carbon atoms, and more preferably with from 1 to about 7 carbon atoms, although the number of carbon atoms can be outside of these ranges, aryl groups (including substituted aryl groups), typically with from about 6 to about 30 carbon atoms, preferably with from about 6 to about 15 carbon atoms, and more preferably with from about 6 to about 12 carbon atoms, although the number of carbon atoms can be outside of these ranges, arylalkyl groups (including substituted arylalkyl groups), typically with from about 7 to about 30 carbon atoms, preferably with from about 7 to about 15 carbon atoms, and more
  • the solvent used in extracting the oxidized heteroatoms from the oxidized heteroatom-containing hydrocarbon stream may be any solvent with relatively low solubility in oil but relatively high solubility of oxidized heteroatom- containing hydrocarbons, including, but not limited to, acetone, methanol, ethanol, ethyl lactate, N-methylpyrollidone, dimethylacetamide, dimethylformamide, gamma-butyrolactone, dimethyl sulfoxide, propylene carbonate, acetonitrile, acetic acid, sulfuric acid, liquid sulfur dioxide, etc, which is capable of extracting the oxidized heteroatoms from the heteroatom containing hydrocarbon stream and producing a substantially oxidized-heteroatom-free hydrocarbon product
  • the caustic of the present invention may be any compound which exhibits basic properties including, but not limited to, metal hydroxides and sulfides, such as alkali metal hydroxides and sulfides, including, but not limited to, LiOH, NaOH, KOH and Na 2 S; alkali earth metal hydroxides, such as Ca(OH) 2 , Mg(OH) 2 and Ba(OH); carbonate salts, such as alkali metal carbonates, including, but not limited to, Na 2 C0 3 and K 2 C0 3; alkali earth metal carbonates, such as CaC0 3 , MgC0 3 and BaC0 3 ; phosphate salts, including, but not limited to, alkali metal phosphates, such as sodium pyrophosphate, potassium pyrophosphate, sodium tripolyphosphate and potassium tripolyphosphate; and alkali earth metal phosphates, such as calcium
  • silicate salts such as, alkali metal silicates, such as sodium silicate and potassium silicate, and alkali earth metal silicates, such as calcium silicate, magnesium silicate and barium silicate, organic alkali compounds expressed by the general formula : R-E n M m Q m l , where R is hydrogen or an organic compound (which may be further substituted) including, but not limited to, straight, branched and cyclic alkyl groups; straight, branched and cyclic alkenyl groups; and aromatic or polycyclic aromatic groups.
  • R is an organic
  • R may include hydroxide groups, carbonyl groups, aldehyde groups, ether groups, carboxylic acid and carboxylate groups, phenol or phenolate groups, alkoxide groups, amine groups, imine groups, cyano groups, thiol or thiolate groups, thioether groups, disulfide groups, sulfate groups, and phosphate groups.
  • alkali metals such as Li, Na, and K
  • alkali earth metals such as Mg and Ca
  • transition metals such as Zn, and Cu.
  • Q may be the same as E n -R or an atom with a negative charge such as Br-, C1-, I, or an anionic group that supports the charge balance of the cation M m ' including but not limited to, hydroxide, cyanide, cyanate, and carboxylates.
  • Examples of the straight or branched alkyl groups may include methyl, ethyl, n- , i-, sec- and t-butyl, octyl, 2-ethylhexyl and octadecyl.
  • Examples of the straight or branched alkenyl groups may include vinyl, propenyl, allyl and butenyl.
  • Examples of the cyclic alkyl and cyclic alkenyl groups may include cyclohexyl, cyclopentyl, and cyclohexene.
  • aromatic or polycyclic aromatic groups may include aryl groups, such as phenyl, naphthyl, andanthracenyl; aralkyl groups, such as benzyl and phenethyl; alkylaryl groups, such as methylphenyl, ethylphenyl, nonylphenyl, methylnaphthyl and ethylnaphthyl.
  • Preferred caustic compounds are alkali metal hydroxides and sulfides, such as NaOH, KOH, Na 2 S, and/or mixtures thereof.
  • the caustic may be in the molten phase.
  • Presently preferred molten phase caustics include, but are not limited to, eutectic mixtures of the inorganic hydroxides with melting points less than 350°C, such as, for example, a 51 mole % NaOH / 49 mole % KOH eutectic mixture which melts at about 170°C.
  • the caustic may be supported on an inorganic support, including, but not limited to, oxides, inert or active, such as, for example, a porous support, such as talc or inorganic oxides.
  • an inorganic support including, but not limited to, oxides, inert or active, such as, for example, a porous support, such as talc or inorganic oxides.
  • Suitable inorganic oxides include, but are not limited to, oxides of elements of groups IB, II-A and II-B, III-A and II-B, IV-A and IV-B, V-A and V-B, VI-B, of the Periodic Table of the Elements.
  • oxides preferred as supports include copper oxides, silicon dioxide, aluminum oxide, and/or mixed oxides of copper, silicon and aluminum.
  • Other suitable inorganic oxides which may be used alone or in combination with the abovementioned preferred oxide supports may be, for example, MgO, Zr0 2 , T1O2, CaO and/or mixtures thereof.
  • the support materials used may have a specific surface area in the range from 10 to 1000 m 2 /g, a pore volume in the range from 0.1 to 5 ml/g and a mean particle size of from 0.1 to 10 cm. Preference may be given to supports having a specific surface area in the range from 0.5 to 500 m 2 /g, a pore volume in the range from 0.5 to 3.5 ml/g and a mean particle size in the range from 0.5 to 3 cm. Particular preference may be given to supports having a specific surface area in the range from 200 to 400 m 2 /g, and a pore volume in the range from 0.8 to 3.0 ml/g.
  • the selectivity promoter of the present invention may be any organic compound having at least one acidic proton.
  • the selectivity promoter has a pKa value (as measured in DMSO) in the range of from about 9 to about 32, preferably in the range of from about 18 to about 32.
  • Examples of the selectivity promoter include, but are not limited to, hydroxyl-functional organic compounds; straight, branched, or cyclic amines having at least one H substituent; and/or mixtures thereof.
  • the selectivity promoter may further include crown ethers.
  • Suitable hydroxyl-functional organic compounds include, but are not limited to: (i) straight-, branched-, or cyclic-alkyl alcohols (which may be further substituted) such as methanol, ethanol, isopropanol, ethylhexanol, cyclohexanol, ethanolamine, di-, and tri- ethanolamine, mono- and di-methylaminoethanol; including -diols such as ethylene glycol, propylene glycol, 1,3 -propanediol, and 1,2-cyclohexanediol; and -polyols, such as glycerol, erythritol, xylitol, sorbitol, etc; -monosaccharides, such as glucose, fructose, galactose, etc; - disaccharides, such as sucrose, lactose, and maltose; -polysaccharides
  • Examples of straight or branched alkyls may include: methyl, ethyl, n-, i-, sec- and t-butyl, octyl, 2-ethylhexyl and octadecyl.
  • Examples of the straight or branched alkenyls may include: vinyl, propenyl, allyl and butenyl.
  • Examples of the cyclic-alkyls may include: cyclohexyl, and cyclopentyl.
  • aryls, aralkyls and polycyclics include: aryls, such as phenyl, naphthyl, anthracenyl; aralkyls, such as benzyl and phenethyl; alkylaryl, such as methylphenyl, ethylphenyl, nonylphenyl, methylnaphthyl and ethylnaphthyl.
  • Suitable amines include, but are not limited to, straight-, branched-, and cyclic- amines having at least one H substituent, which may be further substituted, including, but not limited to, mono-, or di-substituted amines, such as methylamine, ethylamine, 2- ethylhexylamine, piperazine, 1,2-diaminoethane and/or mixtures thereof.
  • Suitable crown ethers which may be further substituted, include, but are not limited to, 18-crown-6, 15-crown-5, etc; and/or mixtures thereof.
  • Preferred selectivity promoters are ethylene glycol, propylene glycol, triethanolamine, and/or mixtures thereof.
  • the selectivity promoter is believed to decrease the likelihood of oxygenated byproduct formation as a result of the oxidized heteroatom removal.
  • the at least one caustic and the at least one selectivity promoter may be different components. In another embodiment of the present invention the at least one caustic and the at least one selectivity promoter may be the same component. When the at least one caustic and the at least one selectivity promoter are the same component they may be referred to as a caustic selectivity promoter. Moreover, a suitable caustic selectivity promoter may possess the properties of both the at least one caustic and the at least one selectivity promoter. That is, combinations of caustics with selectivity promoters may react (in situ or a priori) to form a caustic selectivity promoter which has the properties of both a caustic and a selectivity promoter.
  • the caustic selectivity promoter may react with the oxidized heteroatom- containing compounds, such as dibenzothiophene sulfoxides, dibenzothiophene sulfones, and/or mixtures thereof, to produce substantially non-oxygenated hydrocarbon products, such as biphenyls.
  • the oxidized heteroatom- containing compounds such as dibenzothiophene sulfoxides, dibenzothiophene sulfones, and/or mixtures thereof.
  • Non-limiting examples of caustic selectivity promoters include, but are not limited to, sodium ascorbate, sodium erythorbate, sodium gluconate, 4-hydroxyphenyl glycol, sodium salts of starch or cellulose, potassium salts of starch or cellulose, sodium salts of chitan or chitosan, potassium salts of chitan or chitosan, sodium glycolate, glyceraldehyde sodium salt, 1- thio-beta-D-glucose sodium salt, and/or mixtures thereof.
  • the caustic such as sodium hydroxide and/or potassium hydroxide and the selectivity promoter, such as ethylene glycol
  • the caustic may react in situ or prior to contacting with the oxidized heteroatom-containing hydrocarbon feed, to form water and a caustic selectivity promoter, such as the sodium or potassium salt of ethylene glycol.
  • a caustic selectivity promoter such as the sodium or potassium salt of ethylene glycol.
  • the step of contacting may be any process that leads to transformation of the reactants or reagents from one set of chemical substance to another at various temperatures, reaction rates and chemical concentrations.
  • the promoted-caustic visbreaker reaction may take place at a temperature in the range of from about 150°C to about 350°C, at a pressure in the range of from about 0 psig to about 2000 psig, with a contact time in the range of from about 2 minutes to about 180 minutes.
  • the reaction mechanism is believed to include a solvolysis reaction; particularly alcoholysis when the selectivity promoter is an alcohol, and amino lysis when the selectivity promoter is an amine; without the selectivity promoter of the present invention, the reaction mechanism may involve hydrolysis which leads to the undesirable formation of substantially oxygenated product.
  • the mole ratio of caustic to selectivity promoter is in the range of from about 10: 1 to about 1 : 10, preferably the mole ratio of caustic to selectivity promoter is in the range of from about 3: 1 to about 1 :3, and more preferably the mole ratio of caustic to selectivity promoter is in the range of from about 2: 1 to about 1 :2.
  • the mole ratio of caustic and selectivity promoter to oxidized heteroatom in the heteroatom-containing hydrocarbon feed oil is in the range of from about 100: 1 to about 1 : 1, preferably the mole ratio of caustic and selectivity promoter to oxidized heteroatom in the heteroatom-containing hydrocarbon feed oil is in the range of from about 10: 1 to about 1 : 1, and more preferably the mole ratio of caustic and selectivity promoter to oxidized heteroatom in the heteroatom-containing hydrocarbon feed oil is in the range of from about 3 : 1 to about 1 : 1.
  • Separation of the heavy caustic phase from the light oil phase may be by gravity.
  • caustic and selectivity promoter may be removed according to known methods by those skilled in the art.
  • the light oil phase product has a lower density and viscosity than the untreated, contaminated feed.
  • the heavy caustic phase density is generally in the range of from about 1.0 to about 3.0 g/mL and the light product oil phase density is generally in the range of from about 0.7 to about 1.1 g/mL.
  • the treated stream contains substantial oxygenated by-products.
  • the method of the present invention produces less than about 70% oxygenated by-products, preferably less than about 40% oxygenated by-products, and more preferably less than about 20% oxygenated by-products in the treated stream. This beneficial effect is more clearly demonstrated in the non-limiting examples below.
  • oxidized heteroatom byproducts have been observed as a result of the oxidized heteroatom cleavage process.
  • the cleavage of oxidized sulfur from oxidized-heteroatom-containing hydrocarbons has been observed to result in the formation of a number of oxidized heteroatom byproducts including, for example, sulfite and sulfate.
  • an oxidized-heteroatom-containing hydrocarbon feed 250 is reacted with a caustic (e.g., sodium hydroxide, potassium hydroxide, eutectic mixtures thereof etc.) and a selectivity promoter 256 in reactor 251 to produce a biphasic first intermediate stream 252.
  • First intermediate stream 252 is transferred to product separator 253 where oxidized heteroatom byproducts 255 are removed.
  • a hydrocarbon product with reduced oxidized heteroatom content 254 is obtained.
  • an oxidized-heteroatom-containing hydrocarbon feed 270 is reacted with a caustic and a selectivity promoter 278 in reactor 271 to produce a biphasic first intermediate stream 272.
  • First intermediate stream 272 is then sent to a product separator 273 where caustic, selectivity promoter and oxidized heteroatom byproduct 275 are removed from the hydrocarbon stream.
  • oxidized heteroatom byproduct 276 may be subsequently removed from the caustic and selectivity promoter 278 in recovery vessel 277, allowing for reuse of the caustic and selectivity promoter.
  • a hydrocarbon product with reduced oxidized heteroatom content 274 is obtained.
  • an oxidized-heteroatom-containing hydrocarbon feed 210 is contacted with a solvent 212 in product separator 21 1 to produce first intermediate stream 214 and substantially oxidized heteroatom- free hydrocarbon product stream 213.
  • First intermediate stream 214 comprises an oxidized-heteroatom-contaminated hydrocarbon stream with an increased oxidized-heteroatom concentration.
  • First intermediate stream 214 is then sent to solvent extraction vessel 215 where solvent extract 225 is removed to produce second intermediate stream 216.
  • Second intermediate stream 216 may be reacted with caustic and selectivity promoter 224 in reactor vessel 217 to produce a biphasic third intermediate stream 218.
  • Third intermediate stream 218 is transferred to second product separator 219 from which a
  • hydrocarbon product with reduced oxidized heteroatom content 220 is obtained.
  • the denser phase 221 containing the selectivity promoter and caustic and oxidized heteroatom byproducts may be transferred to a recovery vessel 223 in which the selectivity promoter and caustic 224 may be recovered to reactor 217 and the oxidized heteroatom-containing byproduct 222 may be sent to a recovery area for further processing, as would be understood by those skilled in the art.
  • a heteroatom-containing hydrocarbon feed 10 may be combined with an oxidant 11 and subjected to an oxidizing process in an oxidizer vessel 12 in order to meet current and future environmental standards.
  • the oxidizer vessel 12 may optionally contain a catalyst or promoter (not shown).
  • a first intermediate stream 13 may be generated.
  • the first intermediate stream 13 may be reacted with caustic (e.g., sodium hydroxide, potassium hydroxide, eutectic mixtures thereof etc.) and a selectivity promoter 24 to produce a biphasic second intermediate stream 16.
  • caustic e.g., sodium hydroxide, potassium hydroxide, eutectic mixtures thereof etc.
  • Second intermediate stream 16 may be transferred to a product separator 18 from which a substantially heteroatom-free hydrocarbon product 20 may be recovered from the light phase.
  • the denser phase 21 containing the selectivity promoter and caustic and oxidized heteroatom by-products may be transferred to a recovery vessel 22 in which the selectivity promoter and caustic 24 may be recovered and recycled to reactor 14 and the oxidized heteroatom-containing byproduct 26 may be sent to a recovery area for further processing, as would be understood by those skilled in the art.
  • a heteroatom- containing hydrocarbon feed 30 may be combined with a hydroperoxide 32 in a catalytic oxidizer 34 thereby oxidizing the heteroatoms yielding a first intermediate stream 36.
  • First intermediate stream 36 may be fed to a by-product separator 38 from which the hydroperoxide by-product may be recovered and recycled for reuse in catalytic oxidizer 34 (as would be understood by those skilled in the art) yielding a second intermediate stream 39.
  • the second intermediate stream 39 may be reacted with a selectivity promoter and caustic feed 42 in promoted-caustic visbreaker 40 producing a third intermediate biphasic stream 44 that may be separated in product separator 46 to produce a substantially heteroatom-free hydrocarbon product 48 from the light phase.
  • the dense phase 49 from product separator 46 may be transferred to heteroatom by-product separator 50 from which a oxidized heteroatom-containing byproduct stream 52 and selectivity promoter and caustic feed 42 may be independently recovered, as would be known by those skilled in the art.
  • the heteroatom- containing hydrocarbon feed 30 may be combined with hydroperoxide 32 and contacted with a catalyst in catalytic oxidizer 34 yielding first intermediate stream 60 which may be transferred to a promoted- caustic visbreaker 40 where it reacts with selectivity promoter and caustic feed 42 producing a biphasic second intermediate stream 62.
  • Second intermediate stream 62 may be transferred to a product separator 38 from which a substantially heteroatom-free hydrocarbon product stream 48 may be removed as the light phase and transported to storage or commercial use.
  • the byproduct separator 54 may separate the dense phase 64 into two streams: an oxidizied heteroatom-containing by-product stream 52 (which may be transported to storage or commercial use) and a by-product mixture stream 66 containing the selectivity promoter, caustic, and hydroperoxide by-products for recovery and recycle, as would be known by those skilled in the art.
  • the heteroatom-containing hydrocarbon feed 30 may be mixed with a hydroperoxide feed 32 and may be reacted with a catalyst or promoter (not shown) in the catalytic oxidizer 34 producing a first intermediate stream 36.
  • Stream 36 may be transferred to a by-product separator 38 from which the hydroperoxide by-product 37 may be separated producing a second intermediate stream 70.
  • Stream 70 may be extracted by solvent 78 in product separator 46 (e.g. a liquid-liquid extraction column) from which a substantially heteroatom-free hydrocarbon product 72 may be withdrawn resulting in a third intermediate stream 74.
  • product separator 46 e.g. a liquid-liquid extraction column
  • Stream 74 may be fed to solvent recovery 76 from which solvent 78 may be recovered and recycled to product separator 46, producing a fourth intermediate stream 80.
  • Stream 80 may be treated in the promoted-caustic visbreaker 40 containing selectivity promoter and caustic feed 42 producing a biphasic fifth intermediate stream 82.
  • the two phases of stream 82 may be separated in product separator 84 as a light phase 48 and a dense phase 86.
  • the light phase 48 may comprise a substantially heteroatom-free hydrocarbon product that may be shipped to storage or commercial use.
  • the dense phase 86 may be transferred to a heteroatom by-product separator 88 from which an oxidized heteroatom- containing byproduct stream 52 may be separated from resulting in a stream 42 containing a selectivity promoter and caustic that may be recovered and recycled for reuse in the promoted- caustic visbreaker 40, as would be understood by those skilled in the art.
  • the heteroatom- containing hydrocarbon feed 30 may be fed to a catalytic oxidizer 34 where it may be reacted with catalyst stream 90 in the catalytic oxidizer 34 producing a first intermediate stream 92.
  • Stream 92 may be transferred to catalyst separator 94 from which a second intermediate stream 70 and a depleted catalyst stream 96 may be separated.
  • Stream 96 may be fed to catalyst regenerator 98 for regeneration by oxidant feed 100 producing catalyst stream 90 and an oxidant by-product stream 102.
  • Oxidant by-product stream 102 may be optionally recovered, recycled, and reused as would be understood by those skilled in the art.
  • Stream 70 may be extracted by solvent 78 in product separator 46 (e.g.
  • Stream 74 may be fed to solvent recovery 76 from which solvent 78 may be recovered and recycled to product separator 46, producing a fourth intermediate stream 80.
  • Stream 80 may be treated in the promoted-caustic visbreaker 40 containing selectivity promoter and caustic feed 42 producing a biphasic fifth intermediate stream 82.
  • the two phases of stream 82 may be separated in product separator 84 as a light phase 48 and a dense phase 86.
  • the light phase 48 may comprise a substantially heteroatom-free hydrocarbon product that may be shipped to storage or commercial use.
  • the dense phase 86 may be transferred to a heteroatom by-product separator 88 from which an oxidized heteroatom-containing byproduct stream 52 may be separated from resulting in a stream 42 containing a selectivity promoter and caustic that may be recovered and recycled for reuse in the promoted-caustic visbreaker 40, as would be understood by those skilled in the art.
  • Figure 9 illustrates how the selectively of the reaction of the present disclosure is improved to form more valuable products.
  • Dibenzothiophene sulfone was chosen as a model sulfur compound because most of the sulfur in an average diesel fuel is in the form of substituted or unsubstituted dibenzothiophene.
  • Equation (1) illustrates how hydroxide attacks the sulfur atom of dibenzothiophene sulfone (A), forming biphenyl-2-sulfonate (B).
  • Equation (2) illustrates how hydroxide may attack B at the carbon atom adjacent to the sulfur atom, forming biphenyl-2-ol (C) and sulfite salts (D).
  • Equation (3) illustrates how hydroxide may attack the sulfur atom of B to form biphenyl (E) and sulfate salts (F).
  • Equation (4) illustrates how, in the presence of a primary alcohol, including, but not limited to, methanol, methoxide ions generated in-situ may attack the carbon atom, forming ether compounds, such as 2- methoxybiphenyl (G).
  • Equation (5) illustrates the reaction of dibenzothiophene sulfone with alkoxides alone, not in the presence of hydroxide, as taught by Aida et al, to form biphenyl-2- methoxy-2'-sulfinate salt (H), which may be substantially soluble in the caustic.
  • aqueous or molten hydroxide without the presently disclosed selectivity promoter will cause reaction (1) to occur, followed predominantly by reaction (2).
  • reaction (1) occurs, followed predominantly by reaction (3).
  • reaction (1) occurs, followed predominantly by reaction (4).
  • the hydrogen atoms that become attached to biphenyl come from hydroxide.
  • the ultimate source of the hydrogen atoms added to the biphenyl may be water.
  • a dimethyl sulfoxide (DMSO) solution of co-monomer e.g. 4,4'-bisphenol A dianhydride (BPADA)
  • BPADA 4,4'-bisphenol A dianhydride
  • a DMSO solution of the titanyl e.g. bis(glycerol)oxotitanium(IV)
  • the solution is cooled to room temperature, and the polymer product is precipitated with excess acetone.
  • the polymeric precipitate is collected by vacuum filtration and is dried.
  • the yield of precipitated polymeric titanyl catalyst is greater than 90%.
  • a blend of bonding agent (Kynar®), optional inert filler (silica or alumina), and the polymeric titanyl catalyst is prepared in a solid mixer or blender. The blended mixture is then extruded or pelletized by compression producing uniform catalyst pellets with hardness test strength preferably greater than 2 kp.
  • the second intermediate stream is then fed into a heated reactor wherein it combines with a feed stream containing caustic and ethylene glycol (the combined liquid residence time is 1.0 hr "1 ) to produce a biphasic mixture that exits the reactor.
  • the biphasic mixture is then separated by gravity to produce a light phase product comprising essentially heteroatom-free LAGO and a heavy phase by-product stream comprising essentially caustic, ethylene glycol, and heteroatom- containing salts.
  • Sulfur removal from the light phase product is greater than 50%
  • nitrogen removal is greater than 50%
  • vanadium removal is greater than 50%
  • nickel removal is greater than 50%
  • iron removal is greater than 50% when the samples are measured for elemental composition and compared against the LAGO feed composition.
  • the heavy phase by-product is further treated according to known methods to recover and recycle the caustic and ethylene glycol from the heteroatom by-products.
  • a mixture of dibenzothiophene sulfone in 1,2,3, 4-tetrahydronaphthalene is reacted with six molar equivalents of various alcohols, and six molar equivalents of sodium phenoxide monohydrate. Reactions are performed at 300°C for fifteen minutes. The products of the reaction are acidified with aqueous hydrochloric acid, and then extracted with
  • dichloromethane The dichloromethane extract is analyzed by HPLC to determine percent conversion of dibenzothiophene sulfone, and mole percent yield of biphenyl and ortho- phenylphenol. The results are given below in Table 2.
  • a mixture of dibenzothiophene sulfone in 1,2,3, 4-tetrahydronaphthalene is reacted with six molar equivalents of various alcohols, and six molar equivalents of a salt mixture comprising 57 mole % cesium acetate and 43 mole % potassium acetate. Reactions are performed at 300°C for fifteen minutes. The products of the reaction are acidified with aqueous hydrochloric acid, and then extracted with dichloromethane. The dichloromethane extract is analyzed by HPLC to determine percent conversion of dibenzothiophene sulfone, and mole percent yield of biphenyl and ortho-phenylphenol. The results are given below in Table 3.
  • a mixture of dibenzothiophene sulfone in 1,2,3, 4-tetrahydronaphthalene is reacted with six molar equivalents of ethylene glycol, and six molar equivalents of various nucleophiles.
  • Example 41 used the following molar equivalents to dibenzothiophene sulfone: 1.8 molar equivalents sodium hydroxide, 1.8 molar equivalents potassium hydroxide, 0.7 molar equivalents sodium sulfide nonahydrate and 3.5 molar equivalents ethylene glycol. Reactions are performed at 300°C for fifteen minutes. The products of the reaction are acidified with aqueous hydrochloric acid, and then extracted with dichloromethane. The dichloromethane extract is analyzed by HPLC to determine percent conversion of dibenzothiophene sulfone, and mole percent yield of biphenyl and ortho-phenylphenol. The results are given below in Table 4.
  • a mixture of an aromatic sulfone in 1,2,3,4-tetrahydronaphthalene is reacted with 3.5 molar equivalents of ethylene glycol, 1.8 molar equivalents of a sodium hydroxide, 1.8 molar equivalents of potassium hydroxide, and 0.7 molar equivalents of sodium sulfide nonahydrate. Reactions are performed at 275°C for sixty minutes. The products of the reaction are acidified with aqueous hydrochloric acid, and then extracted with dichloromethane. The dichloromethane extract is analyzed by HPLC to determine percent conversion of sulfone, and mole percent yield of organic products as compared to the initial moles of starting sulfone. The results are given below in Table 5.
  • a mixture of an aromatic sulfone in 1,2,3,4-tetrahydronaphthalene is reacted with six molar equivalents of propylene glycol, and six molar equivalents of sodium phenoxide monohydrate. Reactions are performed at 275°C for sixty minutes. The products of the reaction are acidified with aqueous hydrochloric acid, and then extracted with dichloromethane. The dichloromethane extract is analyzed by HPLC to determine percent conversion of sulfone, and mole percent yield of organic products as compared to the initial moles of starting sulfone. The results are given below in Table 6.
  • model nitrogen compounds e.g., pyridine, quinolone, isoquinoline
  • oxidation of model nitrogen compounds was carried out by first dissolving the compounds to a dilution of 3mg/g in 35% tert-butyl hydroperoxide in toluene. The samples were then heated in a water bath to 95°C. Once this temperature was reached, silica supported titanyl catalyst was added at a ratio of 1ml catalyst to lg oxidant. Lastly, the solutions were lightly agitated at 95 °C for a maximum of 4 hours, in which full conversion of nitrogen compound to N-oxide was observed.
  • model nitrogen compounds e.g., pyridine, quinolone, isoquinoline

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Abstract

L'invention concerne un procédé de valorisation d'une charge d'hydrocarbures contenant des hétéro-atomes par élimination des contaminants hétéro-atomiques oxydés. Le procédé comprend la mise en contact de la charge d'hydrocarbures contenant des hétéro-atomes oxydés avec un promoteur caustique et un promoteur de sélectivité, et l'élimination des contaminants hétéro-atomiques de la charge d'hydrocarbures contenant des hétéro-atomes.
PCT/US2015/032417 2014-05-27 2015-05-26 Procédés de valorisation de flux d'hydrocarbures contaminés WO2015183802A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7790021B2 (en) * 2007-09-07 2010-09-07 Uop Llc Removal of sulfur-containing compounds from liquid hydrocarbon streams
US20110031164A1 (en) * 2008-03-26 2011-02-10 Auterra Inc. Methods for upgrading of contaminated hydrocarbon streams
US20120285866A1 (en) * 2008-03-26 2012-11-15 Auterra, Inc. Methods for upgrading of contaminated hydrocarbon streams
US20130334103A1 (en) * 2010-12-15 2013-12-19 Saudi Arabian Oil Company Desulfurization of hydrocarbon feed using gaseous oxidant

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7790021B2 (en) * 2007-09-07 2010-09-07 Uop Llc Removal of sulfur-containing compounds from liquid hydrocarbon streams
US20110031164A1 (en) * 2008-03-26 2011-02-10 Auterra Inc. Methods for upgrading of contaminated hydrocarbon streams
US20120285866A1 (en) * 2008-03-26 2012-11-15 Auterra, Inc. Methods for upgrading of contaminated hydrocarbon streams
US20130334103A1 (en) * 2010-12-15 2013-12-19 Saudi Arabian Oil Company Desulfurization of hydrocarbon feed using gaseous oxidant

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