WO2013188144A1 - Methods for upgrading of contaminated hydrocarbon streams - Google Patents

Methods for upgrading of contaminated hydrocarbon streams Download PDF

Info

Publication number
WO2013188144A1
WO2013188144A1 PCT/US2013/043843 US2013043843W WO2013188144A1 WO 2013188144 A1 WO2013188144 A1 WO 2013188144A1 US 2013043843 W US2013043843 W US 2013043843W WO 2013188144 A1 WO2013188144 A1 WO 2013188144A1
Authority
WO
WIPO (PCT)
Prior art keywords
heteroatom
caustic
selectivity promoter
hydrocarbon feed
containing hydrocarbon
Prior art date
Application number
PCT/US2013/043843
Other languages
English (en)
French (fr)
Inventor
Jonathan P. Rankin
Jennifer L. Vreeland
Kyle E. Litz
Tracey M. Jordan
Mark N. Rossetti
Eric H. BURNETT
Trent A. MCCASKILL
Original Assignee
Auterra, Inc.
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
Priority claimed from US13/493,240 external-priority patent/US8894843B2/en
Application filed by Auterra, Inc. filed Critical Auterra, Inc.
Priority to MX2014014432A priority Critical patent/MX2014014432A/es
Priority to RU2014152661A priority patent/RU2014152661A/ru
Priority to CA2868851A priority patent/CA2868851C/en
Priority to BR112014025592A priority patent/BR112014025592A2/pt
Priority to CN201380015161.1A priority patent/CN104395435A/zh
Priority to EP13803981.3A priority patent/EP2859066A4/en
Publication of WO2013188144A1 publication Critical patent/WO2013188144A1/en

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
    • C10G19/00—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
    • 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
    • C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
    • 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
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/80—Additives

Definitions

  • the present disclosure is directed to systems and methods for upgrading crude oil, refinery intermediate streams, and refinery products to substantially decrease the content of undesired heteroatom contaminants, including, but not limited to, sulfur, nitrogen, phosphorus, nickel, vanadium, iron, with the added benefit of decreasing the total acid number and increasing the API gravity.
  • a heteroatom contaminated hydrocarbon feed stream is subjected to heteroatom oxidizing conditions to produce an oxidized-heteroatom-containing hydrocarbon intermediate stream and then contacting said stream with a selectivity promoter and caustic thereby removing the heteroatom contaminants from the hydrocarbon stream and thereby increasing the API gravity and decreasing the total acid number relative to the initial contaminated hydrocarbon feed stream.
  • 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.
  • 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. 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 of conventionally as a waste product. Further, the disposal of oxidized organic heteroatom oil wastes valuable hydrocarbons, which could theoretically be recycled if an efficient process were available.
  • the present invention relates to a method of upgrading a heteroatom-containing hydrocarbon feed by removing heteroatom contaminants, the method comprising: contacting the heteroatom-containing hydrocarbon feed with at least one oxidant and at least one immiscible acid; contacting the oxidized heteroatom-containing hydrocarbon feed with at least one caustic and at least one selectivity promoter; and removing the heteroatom contaminants from the heteroatom-containing hydrocarbon feed.
  • the oxidant may be used in the presence of a catalyst.
  • the invention further provides a method of upgrading a heteroatom-containing hydrocarbon feed by removing heteroatom contaminants, the method comprising: contacting the heteroatom-containing hydrocarbon 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 oxidant and at least one immiscible acid to oxidize at least a portion of any remaining heteroatom contaminants to form a second intermediate stream, contacting the second intermediate stream with at least one caustic and at least one selectivity promoter, said at least one selectivity promoter comprising an organic compound having at least one acidic proton, to form a third intermediate stream; separating a substantially heteroatom- free hydrocarbon product from the third intermediate stream; recovering the at least one caustic and at least one selectivity promoter from the second intermediate stream; and recycling the recovered at least one caustic and at least one selectivity promoter.
  • the invention still further provides a method of upgrading a heteroatom-containing hydrocarbon feed by removing heteroatom contaminants, the method comprising oxidizing
  • dibenzothiophenes in the heteroatom-containing feed to sulfones contacting the sulfones under oxidizing biphasic conditions with an immiscible acid and an oxidant to remove at least a portion of the heteroatom contaminants, then reacting the sulfones with caustic and a selectivity promoter, and separating a substantially heteroatom-free hydrocarbon product for fuel.
  • 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 a combination heteroatom oxidation process followed by heteroatom cleavage, in accordance with embodiments of the present disclosure.
  • Figure 3A is a more detailed process flow diagram of an embodiment of a combination heteroatom oxidation process followed by heteroatom cleavage, in accordance with embodiments of the present disclosure.
  • Figure 3B is an alternative more detailed process flow diagram of an embodiment of a combination heteroatom oxidation process followed by heteroatom cleavage, in accordance with embodiments of the present disclosure.
  • Figure 4 is an even more detailed process flow diagram of an embodiment of a combination heteroatom oxidation process followed by heteroatom cleavage, in accordance with embodiments of the present disclosure.
  • Figure 5 is an alternative even more detailed process flow diagram of an embodiment of a combination heteroatom oxidation process followed by heteroatom cleavage, in accordance with embodiments of the present disclosure.
  • biphasic means a chemical system that contains two separate and distinct immiscible chemical phases.
  • 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.
  • Oxidation may be carried out in a single step using at least one oxidant, optionally in the presence of a catalyst, and at least one immiscible acid.
  • the reaction mixture will be biphasic, comprising a hydrocarbon oil phase, and an acid phase.
  • the purpose of the immiscible acid and oxidant treatment is to remove a portion of the heteroatom contaminants from the feed. Upon being oxidized by the immiscible acid and oxidant, these heteroatoms will become soluble in the acid phase, and be subsequently removed.
  • oxidation may also be carried out in two steps; an initial oxidation using at least one oxidant, optionally in the presence of a catalyst, followed by a secondary oxidation using at least one oxidant, optionally in the presence of a catalyst, and at least one immiscible acid.
  • the oxidant and the optional catalyst in each step may be the same or different.
  • the initial oxidation step is more selective towards sulfur and/or nitrogen-containing heteroatom contaminants, although other heteroatom contaminants may be oxidized.
  • the secondary oxidation step is more selective towards oxidizing other heteroatom contaminants, such as metal- containing heteroatom containing contaminants.
  • the oxidation reaction(s) 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
  • metal alkoxides include bis(ethyleneglycol)oxotitanium (IV), bis(erythritol)oxotitanium (IV), and bis(sorbitol)oxotitanium (IV), as disclosed in International Publication Number WO 2009/120238 Al, to Litz et al.
  • 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 immiscible acid used may be any acid which is insoluble in the hydrocarbon oil phase.
  • Suitable immiscible acids may include, but are not limited to, carboxylic acids, sulfuric acid, hydrochloric acid, and mixtures thereof, with or without varying amounts of water as a diluent.
  • Suitable carboxylic acids may include, but are not limited to, formic acid, acetic acid, propionic acid, butyric acid, lactic acid, benzoic acid, and the like, and mixtures thereof, with or without varying amounts of water as a diluent.
  • the solvent used in extracting the heteroatom-containing hydrocarbon stream after the oxidation reaction 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, and liquid sulfur dioxide, which is capable of extracting the heteroatoms from the heteroatom containing hydrocarbon stream and producing a substantially 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 pyrophosphate, magnesium pyrophosphate, barium pyrophosphate, calcium tripo
  • 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 , Ti0 2, 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 (log of the acid dissociation constant) value, as measured in DMSO (dimethylsulfoxide), 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 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.
  • 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 selectivity promoter such as ethylene glycol
  • a caustic selectivity promoter such as the sodium or potassium salt of ethylene glycol.
  • an excess molar ratio of selectivity promoter hydroxyl groups to caustic cations is preferred for conversion and selectivity.
  • 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 sol vo lysis reaction; particularly alcoholysis when the selectivity promoter is an alcohol, and aminolysis 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 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 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 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.
  • suitable methods include, but are not limited to, solvent extraction of the caustic or oil phases, such as by washing with water, centrifugation, distillation, vortex separation, and membrane separation and combinations thereof. Trace quantities of 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.
  • 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 oxidation promoter (not shown).
  • intermediate stream 13 After subjecting a hydrocarbon stream to oxidation conditions in oxidizer vessel 12, thereby oxidizing at least a portion of the heteroatom compounds (e.g., oxidizing dibenzothiophenes to sulfones), intermediate stream 13 may be generated.
  • the intermediate stream 13 may be combined with an oxidant 7 and an immiscible acid and subjected to an oxidizing process in acid treatment reactor 8, thereby oxidizing a further portion of the heteroatom compounds (e.g., oxidizing metalloporphyrins to generate porphyrins and metal salts), generating intermediate stream 9 and metal-containing acidic byproduct stream 79.
  • the intermediate stream 9 may be reacted with caustic (e.g., sodium hydroxide, potassium hydroxide, eutectic mixtures thereof etc.) and a selectivity promoter 24 in reactor 14 to produce a biphasic intermediate stream 16.
  • caustic e.g., sodium hydroxide, potassium hydroxide, eute
  • 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 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 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 intermediate stream 36.
  • Intermediate stream 36 may be fed to a byproduct 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 intermediate stream 39.
  • the intermediate stream 39 may be reacted with an oxidant 7 and an immiscible acid feed 77 in acid treatment column 71 producing intermediate stream 73 from the hydrocarbon phase and intermediate stream 75 from the acid phase.
  • Intermediate stream 75 may be fed to a solvent recovery unit 81 from which the acid 77 may be recovered and recycled for reuse in acid treatment column 71 producing a metal-containing by-product stream 79.
  • the intermediate stream 73 may be reacted with a selectivity promoter and caustic feed 42 in promoted-caustic visbreaker 40 producing 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 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 intermediate stream 36 which may be reacted with an oxidant 7 and an immiscible acid feed 77 in acid treatment column 71 producing intermediate stream 73 from the hydrocarbon phase and intermediate stream 75 from the acid phase.
  • Intermediate stream 75 may be fed to a solvent recovery unit 81 from which the acid 77 may be recovered and recycled for reuse in acid treatment column 71 producing a metal-containing by-product stream 79.
  • Intermediate stream 73 may be transferred to a promoted-caustic visbreaker 40 where it reacts with selectivity promoter and caustic feed 42 producing a biphasic intermediate stream 62.
  • 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: a 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 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 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 intermediate stream 74.
  • Stream 74 may be fed to solvent recovery 76 from which solvent 78 may be recovered and recycled to product separator 46, producing intermediate stream 80.
  • Intermediate stream 80 may be reacted with an oxidant 7 and an immiscible acid feed 77 in acid treatment column 71 producing intermediate stream 73 from the hydrocarbon phase and intermediate stream 75 from the acid phase.
  • Intermediate stream 75 may be fed to a solvent recovery unit 81 from which the acid 77 may be recovered and recycled for reuse in acid treatment column 71 producing a metal-containing by-product stream 79.
  • Intermediate stream 73 may be treated in the promoted-caustic visbreaker 40 containing selectivity promoter and caustic feed 42 producing a biphasic 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 a 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 intermediate stream 92.
  • Stream 92 may be transferred to catalyst separator 94 from which 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 intermediate stream 80.
  • Intermediate stream 80 may be reacted with an oxidant 7 and an immiscible acid feed 77 in acid treatment column 71 producing intermediate stream 73 from the hydrocarbon phase and intermediate stream 75 from the acid phase.
  • Intermediate stream 75 may be fed to a solvent recovery unit 81 from which the acid 77 may be recovered and recycled for reuse in acid treatment column 71 producing a metal-containing by-product stream 79.
  • Stream 73 may be treated in the promoted-caustic visbreaker 40 containing selectivity promoter and caustic feed 42 producing biphasic 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 a 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.
  • a dimethyl sulfoxide (DMSO) solution of co-monomer e.g. 4,4'-bisphenol A dianhydride (BP AD A)
  • BP AD A 4,4'-bisphenol A dianhydride
  • 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 biphasic mixture is then separated by gravity to produce a second intermediate stream of a light phase comprising substantially heteroatom-decreased light atmospheric gas oil, and a heavy phase by-product stream comprising essentially acetic acid, oxidant, and heteroatom- containing salts.
  • the second intermediate stream is vacuum distilled at -25 in Hg to remove and recover a low boiling distillate comprising cumene, cumyl alcohol, alpha-methylstyrene, acetophenone, and residual acetic acid from a heavy second intermediate stream.
  • the heavy second intermediate stream essentially comprises light atmospheric gas oil with oxidized heteroatom compounds.
  • 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%o
  • nickel removal is greater than 50%o
  • iron removal is greater than 50%o 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.

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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)
PCT/US2013/043843 2012-06-11 2013-06-03 Methods for upgrading of contaminated hydrocarbon streams WO2013188144A1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
MX2014014432A MX2014014432A (es) 2012-06-11 2013-06-03 Metodos para el enriquecimiento de corrientes de hidrocarburo contaminadas.
RU2014152661A RU2014152661A (ru) 2012-06-11 2013-06-03 Способы облагораживания содержащих примеси углеводородных потоков
CA2868851A CA2868851C (en) 2012-06-11 2013-06-03 Methods for upgrading of contaminated hydrocarbon streams
BR112014025592A BR112014025592A2 (pt) 2012-06-11 2013-06-03 métodos para aprimoramento de correntes de hidrocarbonetos contaminadas
CN201380015161.1A CN104395435A (zh) 2012-06-11 2013-06-03 改质受污染烃流的方法
EP13803981.3A EP2859066A4 (en) 2012-06-11 2013-06-03 METHOD FOR PROCESSING CONTAMINATED HYDROCARBON STREAMS

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US13/493,240 2012-06-11
US13/493,240 US8894843B2 (en) 2008-03-26 2012-06-11 Methods for upgrading of contaminated hydrocarbon streams

Publications (1)

Publication Number Publication Date
WO2013188144A1 true WO2013188144A1 (en) 2013-12-19

Family

ID=49758626

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2013/043843 WO2013188144A1 (en) 2012-06-11 2013-06-03 Methods for upgrading of contaminated hydrocarbon streams

Country Status (7)

Country Link
EP (1) EP2859066A4 (pt)
CN (1) CN104395435A (pt)
BR (1) BR112014025592A2 (pt)
CA (1) CA2868851C (pt)
MX (1) MX2014014432A (pt)
RU (1) RU2014152661A (pt)
WO (1) WO2013188144A1 (pt)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9061273B2 (en) 2008-03-26 2015-06-23 Auterra, Inc. Sulfoxidation catalysts and methods and systems of using same
US9206359B2 (en) 2008-03-26 2015-12-08 Auterra, Inc. Methods for upgrading of contaminated hydrocarbon streams
US9512151B2 (en) 2007-05-03 2016-12-06 Auterra, Inc. Product containing monomer and polymers of titanyls and methods for making same
US9828557B2 (en) 2010-09-22 2017-11-28 Auterra, Inc. Reaction system, methods and products therefrom
US10246647B2 (en) 2015-03-26 2019-04-02 Auterra, Inc. Adsorbents and methods of use
US10450516B2 (en) 2016-03-08 2019-10-22 Auterra, Inc. Catalytic caustic desulfonylation

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090065399A1 (en) * 2007-09-07 2009-03-12 Kocal Joseph A Removal of sulfur-containing compounds from liquid hydrocarbon streams

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2566788C (en) * 2004-05-14 2011-06-21 Exxonmobil Research And Engineering Company Inhibitor enhanced thermal upgrading of heavy oils
US8197671B2 (en) * 2008-03-26 2012-06-12 Auterra, Inc. Methods for upgrading of contaminated hydrocarbon streams
US8241490B2 (en) * 2008-03-26 2012-08-14 Auterra, Inc. Methods for upgrading of contaminated hydrocarbon streams

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090065399A1 (en) * 2007-09-07 2009-03-12 Kocal Joseph A Removal of sulfur-containing compounds from liquid hydrocarbon streams

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP2859066A4 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9512151B2 (en) 2007-05-03 2016-12-06 Auterra, Inc. Product containing monomer and polymers of titanyls and methods for making same
US9061273B2 (en) 2008-03-26 2015-06-23 Auterra, Inc. Sulfoxidation catalysts and methods and systems of using same
US9206359B2 (en) 2008-03-26 2015-12-08 Auterra, Inc. Methods for upgrading of contaminated hydrocarbon streams
US9828557B2 (en) 2010-09-22 2017-11-28 Auterra, Inc. Reaction system, methods and products therefrom
US10246647B2 (en) 2015-03-26 2019-04-02 Auterra, Inc. Adsorbents and methods of use
US10450516B2 (en) 2016-03-08 2019-10-22 Auterra, Inc. Catalytic caustic desulfonylation
US11008522B2 (en) 2016-03-08 2021-05-18 Auterra, Inc. Catalytic caustic desulfonylation

Also Published As

Publication number Publication date
BR112014025592A2 (pt) 2017-07-04
MX2014014432A (es) 2015-02-04
CA2868851A1 (en) 2013-12-19
CA2868851C (en) 2021-05-04
RU2014152661A (ru) 2016-07-27
EP2859066A1 (en) 2015-04-15
EP2859066A4 (en) 2016-04-13
CN104395435A (zh) 2015-03-04

Similar Documents

Publication Publication Date Title
US8241490B2 (en) Methods for upgrading of contaminated hydrocarbon streams
US8197671B2 (en) Methods for upgrading of contaminated hydrocarbon streams
US8894843B2 (en) Methods for upgrading of contaminated hydrocarbon streams
US8764973B2 (en) Methods for upgrading of contaminated hydrocarbon streams
CA2879626C (en) Methods for upgrading of contaminated hydrocarbon streams
CA2868851C (en) Methods for upgrading of contaminated hydrocarbon streams
US9206359B2 (en) Methods for upgrading of contaminated hydrocarbon streams
US8877013B2 (en) Reaction system and products therefrom
US9889430B2 (en) Solid base catalyst compositions useful in removal of oxidized sulfur compounds and method for making solid base catalyst compositions
US9828557B2 (en) Reaction system, methods and products therefrom
JP2014528974A5 (ja) スルホン分解と統合される酸化的脱硫の方法
WO2015183802A1 (en) Methods for upgrading of contaminated hydrocarbon streams

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: 13803981

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
ENP Entry into the national phase

Ref document number: 2868851

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: MX/A/2014/014432

Country of ref document: MX

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: P1371/2014

Country of ref document: AE

REEP Request for entry into the european phase

Ref document number: 2013803981

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2015/0016.1

Country of ref document: KZ

ENP Entry into the national phase

Ref document number: 2014152661

Country of ref document: RU

Kind code of ref document: A

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112014025592

Country of ref document: BR

ENP Entry into the national phase

Ref document number: 112014025592

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20141014