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WO2009099848A2 - Procédé de production de bio-éthers/essence propres utilisant de l'éthanol - Google Patents

Procédé de production de bio-éthers/essence propres utilisant de l'éthanol Download PDF

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Publication number
WO2009099848A2
WO2009099848A2 PCT/US2009/032310 US2009032310W WO2009099848A2 WO 2009099848 A2 WO2009099848 A2 WO 2009099848A2 US 2009032310 W US2009032310 W US 2009032310W WO 2009099848 A2 WO2009099848 A2 WO 2009099848A2
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Prior art keywords
fuel
ethanol
gasoline
blendstock
olefins
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PCT/US2009/032310
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English (en)
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WO2009099848A3 (fr
Inventor
Yi-Gang Xiong
Kerry L. Rock
Arvids Judzis
Mitchell E. Loescher
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Catalytic Distillation Technologies
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Application filed by Catalytic Distillation Technologies filed Critical Catalytic Distillation Technologies
Priority to JP2010545115A priority Critical patent/JP2011511132A/ja
Priority to BRPI0906609A priority patent/BRPI0906609A8/pt
Publication of WO2009099848A2 publication Critical patent/WO2009099848A2/fr
Publication of WO2009099848A3 publication Critical patent/WO2009099848A3/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
    • C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C10L1/023—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for spark ignition
    • 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
    • C10G2300/30—Physical properties of feedstocks or products
    • 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
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/305—Octane number, e.g. motor octane number [MON], research octane number [RON]

Definitions

  • Embodiments disclosed herein relate generally to processes for using renewable resources, such as ethanol, as a fuel component.
  • embodiments disclosed herein relate to a fuel composition comprising alkanes, olefins, ethanol and ethyl ethers. More specifically, embodiments disclosed herein relate to various processes for chemical and splash blending of ethanol with a gasoline fraction.
  • ethanol is supplied to the refinery itself and covalently bonded to the base gasoline.
  • U.S. Patent No. 5,633,416 and others describe a process in which a Ci to C 4 alcohol is reacted with etherifiable olefins in a gasoline subgrade.
  • ethanol may be reacted with isobutylene to form ethyl tertiary butyl ether (ETBE).
  • ETBE ethyl tertiary butyl ether
  • a major benefit to the use of either chemical or splash blending is the boost in octane quality. Adding to the need for more unleaded octane quality is the growing demand for premium fuel.
  • the blending values for various oxygenates in typical unleaded gasoline are given in Table 1. As can be seen, the octane value ((Research Octane Number (RON) + Motor Octane Number (M0N))/2) for ethanol and ETBE are in the range from 109-113.
  • ethanol is a blending agent not commonly manufactured at the refinery site; as described in the '987 patent, blending sites are typically remote from the refinery (i.e., the ethanol produced in the Midwest, close to the corn supply, must be combined with the gasoline produced on the Gulf Coast).
  • ethanol-hydrocarbon blending requires the elimination of water from the refinery or blending site tank farm and product delivery system as ethanol is completely miscible in water. Also, marketing of ethanol blends are typically restricted as they are not accepted by all oil companies. Even further, pipelines may not accept ethanol blends due to the potential for water and the associated corrosion. Environmentally, ethanol may increase volatile organic chemical (VOC) emissions and does not reduce toxics and NO x emissions as effectively as ethers such as ETBE.
  • VOC volatile organic chemical
  • the resulting RVP-adjusted ethanol blend typically has a lower octane value, due to the removal of C 4 and C 5 compounds such that the blend meets RVP specifications, partially offset by the higher octane value of ethanol.
  • the D86 T5 and TlO values for the RVP- adjusted blend are also much higher due to the removal of the C 4 and C 5 compounds.
  • the removal of C 4 and C 5 compounds may also result in a decrease in available gasoline volume.
  • embodiments disclosed herein relate to a fuel or fuel blendstock comprising ethanol, ethyl ethers, olefins, and alkanes.
  • the fuel or fuel blendstock of claim 1 wherein the fuel or fuel blendstock may have an octane number greater than 92 (RON + M0N)/2).
  • the fuel or fuel blendstock may have a Reid vapor pressure less than 7.2 psi.
  • embodiments disclosed herein relate to a process for the production of a fuel, the process including: contacting ethanol and at least one gasoline fraction including alkanes and olefins in the presence of a catalyst to form a fuel mixture including ethyl ethers, alkanes, unreacted olefins, and unreacted ethanol; and recovering the fuel mixture for use as a gasoline or gasoline blendstock without separation of the ethanol from the fuel mixture.
  • Figure 1 is a simplified process flow diagram for producing a fuel or fuel component containing chemically blended and splash blended ethanol, according to an embodiment disclosed herein.
  • Figure 2 is a simplified process flow diagram for producing a fuel containing chemically blended and splash blended ethanol, according to an embodiment disclosed herein.
  • Figure 3 is a simplified process flow diagram for producing a fuel containing chemically blended and splash blended ethanol, according to another embodiment disclosed herein.
  • embodiments disclosed herein relate to processes for using renewable resources, such as ethanol, as a fuel component.
  • embodiments disclosed herein relate to a fuel composition comprising alkanes, olefins, ethanol and ethyl ethers. More specifically, embodiments disclosed herein relate to various processes for chemical and splash blending of ethanol with a gasoline fraction.
  • ethanol and a gasoline fraction, comprising olefins are contacted in the presence of an etherification catalyst to form a fuel mixture comprising ethyl ethers, alkanes, unreacted olefins, and unreacted ethanol.
  • the fuel mixture may then be recovered for use as a gasoline or gasoline blendstock without separation of the ethanol from the fuel mixture.
  • the contacting with the etherification catalyst may occur in at least one of a catalytic distillation column and a fixed-bed etherification reactor.
  • a gasoline fraction includes (1) individual refinery streams suitable for use as a blend stock for gasoline, and/or (2) a blended gasoline stream formed by blending two or more streams, each of which are suitable for use as a gasoline blend stock.
  • a suitable gasoline blend stock when blended with other refinery streams, produces a combined stream which meets the requirements for gasoline, which are well documented in Federal and State regulations.
  • the feeds to the processes disclosed herein may include one or more petroleum fractions which boil in the gasoline boiling range, including FCC gasoline, coker pentane/hexane, coker naphtha, FCC naphtha, straight run gasoline, and mixtures containing two or more of these streams.
  • Such gasoline blending streams typically have a normal boiling point within the range of 0°C and 26O 0 C, as determined by an ASTM D86 distillation.
  • Feeds of this type include light naphthas typically having a boiling range of about C 6 to 165°C (330°F); full range naphthas, typically having a boiling range of about C 5 to 215°C (420°F), heavier naphtha fractions boiling in the range of about 125°C to 210°C (260°F to 412 0 F), or heavy gasoline fractions boiling at, or at least within, the range of about 165 0 C to 260 0 C (330 0 F to 500 0 F), preferably about 165°C to 210°C.
  • a gasoline fuel will distill over the range of from about room temperature to 260 0 C (500 0 F).
  • these streams may be treated to remove sulfur, nitrogen, and other undesired components.
  • Gasoline fractions for use in embodiments of the etherification process described herein may include C 3 to C 9 and higher hydrocarbons.
  • refinery streams are usually separated by fractional distillation.
  • a light naphtha cut is one such refinery stream, and because such a cut often contains compounds that are very close in boiling points, the separations are not precise.
  • a C 5 stream for instance, may include C 4 S and up to C 8 S and higher.
  • gasoline fractions may include a C 4 cut, which may include C 3 to C 5 or higher hydrocarbons (i.e., C 6+ ). In other embodiments, gasoline fractions may include a C 5 cut, which may include C 4 to C 8 or higher hydrocarbons, including olefins.
  • gasoline fractions may include a C 6 cut, which may include C 4 to C 9 or higher hydrocarbons, including olefins.
  • gasoline fractions may include mixtures of one or more of C 4 , C 5 , C 6 , and C 7+ hydrocarbons, where the mixture includes olefinic compounds.
  • the above described streams may include C 4 to C 7 streams, gasoline fractions, FCC gasoline, coker gasoline, and other refinery streams having similar properties.
  • Saturated compounds included in the above described gasoline fractions may include various isomers of butane, various isomers of pentane, and various isomers of hexane, among others, for example.
  • Olefinic compounds included in the above described gasoline fractions may include isobutylene and other butene isomers, various isomers of pentene, various isomers of hexene, and various isomers of heptene, among others, for example.
  • the gasoline fractions may be derived from any source, and may include a concentration of 1 to 45 weight percent etherifiable isoolefins; a concentration of 10 to 30 weight percent isoolefins in other embodiments; and a concentration of 15 to 25 weight percent isoolefins in yet other embodiments.
  • ethers resulting in processes disclosed herein may include tertiary-amyl, tertiary- butyl, tertiary-hexyl ethers, and tertiary-heptyl ethers.
  • the typical feed stream will consist of a mixture of C 4 isomers comprising isobutane, isobutylene, normal butane, 1 -butene and 2-butene.
  • the feed stream components will include 3 -methyl- 1 -butene, isopentane, 1 -pentene, 2-methyl- 1 -butene, normal pentane, trans-2-pentene, cis-2-pentene, neopentane, and 2-methyl- 2-butene in a typical distribution of isomers.
  • the most common sources for the feed streams for these processes are light cracked hydrocarbon streams from an FCC unit or a C 4 stream from a steam cracker after butadiene extraction.
  • the gasoline fraction fed to the etherification reactor may include isoamylene, which may include both the reactive isomers (2-methyl-l-butene and 2-methyl-2-butene) and unreactive isomer (3 -methyl- 1-butene ).
  • a gasoline fraction containing isoolefins may be mixed with ethanol, which may be from a biological or petrochemical origin.
  • the ethanol is from a biological origin, such as ethanol produced from corn or other agricultural products.
  • an diluent containing ethyl ethers may also be mixed with the gasoline fraction and the ethanol, such as a recycle stream containing a portion of the product from the etherification reactor.
  • the isoolefins and ethanol in the resulting mixture may be reacted over a suitable etherification catalyst to form ethyl ethers.
  • a suitable etherification catalyst to form ethyl ethers.
  • the mixture may be contacted with a sulfuric acid macroporous ion exchange resin acid-form in a suitable reactor to react ethanol and isobutylene to form ethyl ethers with high selectivity to ethers and low yield to isoolefin dimers.
  • Etherification catalysts are described in more detail below.
  • the etherification reactor effluent includes the ethyl ethers, unreacted isoolefins, and unreacted ethanol, among other components.
  • the effluent may then be recovered for use as a fuel or a fuel blending stock, without the need to separate the ethanol from the fuel mixture.
  • a downflow boiling point reactor for example, at least a portion of the reactor effluent may be recycled to provide the ether-containing diluent and reactor temperature control.
  • the etherification reactor effluent may then be recovered for use as a fuel or a fuel blendstock.
  • the etherification reactor effluent may be recovered, stored if necessary, and transported for use as a fuel.
  • the etherification reactor effluent may be splash blended with ethanol or other gasoline fractions, where the resulting splash blend may be stored and transported for use as a fuel.
  • the gasoline fraction is transported to a blending site which is: geographically proximate to the area in which the finished alcohol- containing gasoline is to be distributed for use as a fuel and geographically distant from the place where the gasoline fraction is prepared.
  • the etherification of a portion of the olefins may then occur at the blending site.
  • the reactor effluent, containing ethanol and ethyl ethers, may then be used as a fuel or a fuel blendstock.
  • the fuel containing ethanol and ethyl ethers may then be prepared by admixture with a desired amount of alcohol or other gasoline fractions at said blending site.
  • isoolefins and alcohols may be reacted to form ethers.
  • ethers formed in embodiments disclosed herein may include: ethyl tertiary butyl alcohol (ETBE), the reaction product of isobutylene and ethanol; tertiary amyl ethyl ether (TAEE), the reaction product of isoamylenes and ethanol; and tertiary hexyl ethyl ether (THEE), the reaction product of various C 6 isoolefins with ethanol; among others.
  • ETBE ethyl tertiary butyl alcohol
  • TAEE tertiary amyl ethyl ether
  • THEE tertiary hexyl ethyl ether
  • Gasoline fraction 10 containing isoolefins may be fed to a distillation column reactor 12.
  • the feed location of gasoline fraction 10 may be above, below, or intermediate to a catalyst containing region 14.
  • Isoolefins contained in hydrocarbon stream 10 may react with ethanol, fed via stream 15, in catalyst containing region 14 to produce ethers.
  • Distillation column reactor 12 may include a reboiler 16 and an overhead system 17, each providing for control of the liquid and vapor traffic in distillation column reactor 12.
  • Distillation column reactor system 5 may be operated in a manner such that at least a portion of the unreacted ethanol exits distillation column reactor 12, along with heavier hydrocarbons contained in hydrocarbon stream 10 and the ethers formed due to reaction of the olefins and the alcohols, in bottoms stream 18.
  • Light hydrocarbons, including alkanes and some unreacted olefins may be condensed in the overhead system 17 and recovered in overheads stream 20 or recycled as reflux to the top of distillation column reactor 12 via line 21.
  • Ethanol may be fed to distillation column reactor 12 along with hydrocarbon stream 10, as illustrated, or may be fed to a different location on distillation column reactor 12, including stages above or below the feed point of hydrocarbon feed stream 10. Due to azeotropes that may form between ethanol and the various hydrocarbons, as well as the selected operating conditions, ethanol may be present in both bottoms stream 18 and overheads stream 20. Stream 18, containing chemically blended and splash blended ethanol, may then be used as a fuel or fuel blendstock, typically without separating the ethanol.
  • additional ethanol may be added to the distillation column reactor system at a location above that of the gasoline fraction feed.
  • ethanol may be added to one or more of the top of the column, above the etherification catalyst zone, within the etherification catalyst zone, or to a tray below the etherification catalyst zone. In this manner, the concentration of ethanol within various portions of the column may be increased or controlled to a desired level.
  • the hydrocarbon and alcohol feeds may be passed through a fixed-bed etherification reactor, converting at least a portion of the feed to ethers.
  • U.S. Patent Nos. 5,003,124 and 4,950,803 disclose a liquid phase process for the etherification and oligomerization of C 4 or C 5 isoolefins with alcohols in a boiling point fixed bed reactor that is controlled at a pressure to maintain the reaction mixture at its boiling point and which may be directly attached to a catalytic distillation reactor.
  • the fixed-bed reactor may be a single-phase reactor, such as a liquid or vapor phase reactor, a fixed-bed boiling point reactor, or a combination thereof.
  • the fixed-bed boiling point reactor may be operated in the pulse flow regime.
  • the effluent from the fixed bed reactor may be used directly as a fuel or fuel blendstock.
  • the effluent from the reactor may then be forwarded to a catalytic distillation reactor system for further processing, where the catalytic distillation reactor system is operated as described above.
  • the gasoline fraction fed to the etherification reactor may undergo processing steps prior to entry into the catalytic distillation reactor system.
  • various gasoline fractions may undergo hydrotreating, selective hydrogenation of dienes and/or acetylenes, hydrodesulfurization, hydrodenitrogenation, and other processes known to those skilled in the art.
  • FIG. 2 a simplified flow diagram for a process for producing ethanol-containing fuel, according to embodiments disclosed herein, is illustrated.
  • a separate gasoline fraction or blendstock is passed through each of input lines 41, 42, 43, 44, 45, and 46. Although six input lines are shown in Figure 2, it will be appreciated that a larger or smaller number of input lines may be used.
  • Each of input lines 41-46 discharges into blending chamber 47, in which the blendstocks are mixed to form a subgrade blend.
  • the subgrade blend may then be converted to an ethyl ether and ethanol-containing fuel or fuel blendstock of desired specifications by reacting and/or mixing with a desired amount of ethanol, fed via line 37, in reactor 35. Recycle, if necessary, may be returned to the reactor inlet via flow line 38.
  • the resulting fuel or fuel blendstock is recovered from reactor 35 via output line 48, and is passed to a suitable storage facility such as a holding tank or to an element of a distribution system (not shown), such as a pipeline, rail car, tanker truck or barge. If desired, additional splash blended ethanolor other gasoline blendstocks may be added via line 39.
  • a suitable storage facility such as a holding tank or to an element of a distribution system (not shown), such as a pipeline, rail car, tanker truck or barge.
  • a suitable storage facility such as a holding tank or to an element of a distribution system (not shown), such as a pipeline, rail car, tanker truck or barge.
  • a distribution system not shown
  • additional splash blended ethanolor other gasoline blendstocks may be added via line 39.
  • Each of the input lines 37, 39, 41-46 may be provided with an associated metering device to control the final composition of the fuel to within the desired specifications, such as ethanol concentration, oxygen content, Reid vapor pressure, octane number
  • the etherification reactor may be used to etherify a specific fraction. The remaining fractions may then be blended with the etherified gasoline blendstock to the desired fuel specifications, as illustrated in Figure 3, where like numerals represent like parts.
  • the octane number (motor octane, or (RON + M0N)/2) value of the fuels or fuel blendstocks resulting from the above described chemical and splash blending, according to embodiments disclosed herein, may be greater than 90.
  • the octane number may be greater than 91; greater than 92 in other embodiments; greater than 93 in other embodiments; greater than 95 in other embodiments; greater than 98 in other embodiments; and greater than 100 in yet other embodiments.
  • the Reid Vapor Pressure of the fuels or fuel blendstocks resulting from the above described chemical and splash blending, according to embodiments disclosed herein may be less than 7.5 psi.
  • the Reid vapor pressure may be less than 7.2 psi; less than 7 psi in other embodiments; less than 6.9 psi in other embodiments; less than 6.8 psi in other embodiments; less than 6.7 psi in other embodiments; less than 6.6 psi in other embodiments; and less than 6.5 psi in yet other embodiments.
  • the oxygen content of the fuels or fuel blendstocks disclosed herein, including chemical and splash blended ethanol, may be similar to splash blended ethanol fuels.
  • the fuels and fuel blendstocks disclosed herein may have an oxygen content of at least 2 weight percent; at least 2.25 weight percent in other embodiments; at least 2.5 weight percent in other embodiments; at least 2.75 weight percent in other embodiments; at least 3.0 weight percent in other embodiments; at lest 3.25 weight percent in other embodiments; and at least 3.5 weight percent in yet other embodiments.
  • fuels and fuel blendstocks disclosed herein include both splash blended and chemically blended ethanol, where the chemically blended ethanol is in the form of ethers.
  • a total ethanol content in the fuel or fuel blendstock, inclusive of chemically blended ethanol in the fuel mixture, is at least 8 volume percent, at least 9 volume percent in other embodiments; at least 10 volume percent in other embodiments; at least 11 volume percent in other embodiments; at least 12 volume percent in other embodiments; and at least 15 volume percent in yet other embodiments.
  • any catalyst typically used in etherification processes may be used in embodiments disclosed herein.
  • Conventional cation exchange resins and/or zeolites may be used in various embodiments.
  • the resin may contain sulfonic acid groups and may be obtained by polymerization or copolymerization of aromatic vinyl compounds followed by sulfonation.
  • aromatic vinyl compounds suitable for preparing polymers of copolymers include: styrene, vinyl toluene, vinyl naphthalene, vinyl ethyl-benzene, methyl styrene, vinyl chlorobenzene and vinyl xylene.
  • the acid cation exchange resin may contain some 1.3 to 1.9 sulfonic acid groups per aromatic nucleus.
  • resins may be based on copolymers of aromatic monovinyl compounds with aromatic polyvinyl compounds in which the polyvinyl benzene content is from about 1 to 20 weight percent of the copolymer.
  • the ion exchange resin may have a granular size of about 0.15 to 1 mm in some embodiments.
  • perfluorosulfonic acid resins which are copolymers of sulfonyl fluorovinyl ethyl and fluorocarbon, may be used.
  • the catalysts useful in the etherification processes disclosed herein may contain a zeolite sometimes referred to as medium pore or ZSM-5 type.
  • the zeolite may be a medium pore shape selective acidic metallosilicate zeolite selected from the group consisting of ZSM-5, ZSM-I l, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-50, MCM-22, as well as larger pore zeolite Y and zeolite Beta.
  • the original cations associated with zeolites utilized herein may be replaced by a wide variety of other cations according to techniques well known in the art, e.g., by ion exchange.
  • Typical replacing cations include hydrogen, ammonium, alkyl ammonium, and metal cations, and their mixtures.
  • metal cations metals of Groups IB to VIIIA of the Periodic Table, including, by way of example, iron, nickel, cobalt, copper, zinc, palladium, calcium, chromium, tungsten, molybdenum, rare earth metals, etc. may be used. These metals may also be present in the form of their oxides.
  • etherif ⁇ cation catalysts for the isoalkene reactants include mineral acids such as sulfuric acid, boron trifluoride, phosphoric acid on kieselguhr, phosphorous-modified zeolites, heteropoly acids, and various sulfonated resins.
  • resin type catalysts may include the reaction products of phenolformaldehyde resins and sulfuric acid and sulfonated polystyrene resins including those crosslinked with divinylbenzene.
  • a particular etherification catalyst is a macroporous acid-form of a sulfonic ion exchange resin such as a sulfonated styrene-divinylbenzene resin, as described in U.S. Patent No. 2,922,822, having a degree of crosslinking of about 5 to 60%.
  • Specialized resins have been described in the art and include copolymers of sulfonyl fluorovinyl ether and fluorocarbons, as described in U.S. Patent No. 3,489,243.
  • Another specially prepared resin consists of SiO 2 -modified cation exchangers described in U.S. Patent No. 4,751,343.
  • the macroporous structure of a suitable resin is described in detail in U.S. Patent No. 5,012,031 as having a surface area of at least about 400 m /g, a pore volume of about 0.6 to 2.5 ml/g, and a mean pore diameter of 40 to 1000 Angstroms. It is contemplated that the subject process could be performed using a metal-containing resin which contains one or more metals from sub-groups VI, VII or VIII of the Periodic Table such as chromium, tungsten, palladium, nickel, chromium, platinum, or iron as described in U.S. Patent No. 4,330,679. Further information on suitable etherification catalysts may be obtained by reference to U.S. Patent Nos. 2,480,940, 2,922,822, and 4,270,929.
  • a catalytic distillation structure for use herein includes placing the cation exchange resin particles into a plurality of pockets in a cloth belt, which is supported in the distillation column reactor by open mesh knitted stainless steel wire by twisting the two together in a helical form. This allows the requisite flows and prevents loss of catalyst.
  • the cloth may be any material which is inert in the reaction, such as cotton, linen, fiber glass cloth, or TEFLON.
  • U.S. Patent Nos. 4,302,356, 4,443,559, and 5,730,843 disclose catalyst structures which are useful as distillation structures, and are incorporated herein by reference. Other suitable etherification catalysts are described in, for example, U.S. Patent Nos. 5,190,730, 5,231,234, 5,248,836, 5,292,964, 5,637,777, and 6,107,526, among others.
  • the gasoline blendstock was adjusted to make the blendstock suitable for ethanol splash blending by removal of lighter fuel components such that the final fuel will meet the RVP specifications.
  • the RON of the splash blended ethanol is lower than the base gasoline due to the removal of C 4 and C 5 compounds to meet the RVP specifications, which are high octane value components. This reduction is partially offset by the high octane value of ethanol.
  • the volume of available splash blended gasoline is also lower than the conventional gasoline because of the removal of the light fraction.
  • embodiments of the processes disclosed herein may provide for fuels and fuel blendstocks including both chemical and splash blended ethanol.
  • Processes disclosed herein may provide for a simplified etherification process, where the ethanol recovery section may be completely eliminated saving both capital and operating costs.
  • embodiments disclosed herein may provide for at least one of: an outlet for C 4 olefins; additional C 4 and C 5 hydrocarbons to be included in fuel compositions, effective use of ethanol in clean fuels while reducing automotive emissions; effectively reducing olefins in the gasoline at a profit. Additionally, processes disclosed herein may provide an alternative to ethanol splash blending.

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Abstract

L'invention concerne un carburant ou un mélange de carburants incluant de l'éthanol, des éthers diéthyliques, des oléfines et des alcanes. Dans certains modes de réalisation, le carburant ou le mélange de carburants de la revendication 1 peut présenter un indice d'octane supérieur à 92 (RON + M0N)/2). Dans d'autres modes de réalisation, le carburant ou le mélange de carburants peut présenter une pression de vapeur Reid inférieure à 7,2 psi. L'invention concerne également un procédé de production d'un carburant consistant à : mettre en contact de l'éthanol et au moins une fraction d'essence incluant des alcanes et des oléfines en présence d'un catalyseur pour former un mélange carburant incluant des éthers diéthyliques, des alcanes, des oléfines n'ayant pas réagi et de l'éthanol n'ayant pas réagi ; et à récupérer le mélange carburant pour l'utiliser en tant qu'essence ou essence de base sans séparer l'éthanol du mélange carburant.
PCT/US2009/032310 2008-02-04 2009-01-29 Procédé de production de bio-éthers/essence propres utilisant de l'éthanol WO2009099848A2 (fr)

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BRPI0906609A8 (pt) 2019-01-29
BRPI0906609A2 (pt) 2015-07-14
US20090193710A1 (en) 2009-08-06
JP2011511132A (ja) 2011-04-07
MY172108A (en) 2019-11-14
CN101503638B (zh) 2013-07-17
KR20100099340A (ko) 2010-09-10
US20130219777A1 (en) 2013-08-29
CN101503638A (zh) 2009-08-12
WO2009099848A3 (fr) 2009-10-29

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