JP2011511132A - Method for producing clean gasoline and bioether using ethanol - Google Patents

Abstract

  The fuel or fuel blend substrate includes ethanol, ethyl ether, olefins, and alkanes. In some embodiments, the fuel or fuel blend substrate of claim 1 has an octane number greater than 92 × (RON + MON) / 2. In some embodiments, the fuel or fuel blend substrate may have a lead vapor pressure of less than 7.2 psi. Even in the process for producing fuel, the process involves contacting ethanol with at least one gasoline fraction containing an alkane and an olefin in the presence of a catalyst to produce ethyl ether, alkane, unreacted olefin, unreacted ethanol. And a step of recovering a fuel mixture for use as a gasoline blend base or gasoline without separating ethanol from the fuel mixture.

Description

  Embodiments described herein generally relate to manufacturing methods that use renewable resources, such as ethanol, as a fuel component. In other aspects, embodiments described herein relate to fuel compositions comprising alkanes, olefins, ethanol, and ethyl ether. More specifically, the embodiments described herein relate to various manufacturing methods for chemical mixing and splash mixing of ethanol containing gasoline fractions.

  Fuel producers feel the pressure to use renewable resources as a gasoline blend base is increasing. Ethanol is often cited as a main example of such a raw material. Of all the renewable components that are readily manufacturable, ethanol is most suitable for use in gasoline. In fact, the engine can be designed to run on pure ethanol by making changes to the fuel system.

  For the economy as a whole, the use of ethanol has the potential to increase energy self-sufficiency. This is due to the fact that raw materials (agricultural carbohydrates) can be produced in almost any place where food can be grown. In addition, this manufacturing system provides the additional economic benefit of allocating the economic benefits associated with transportation to rural areas.

  The simplest way to incorporate ethanol into gasoline is mixing or splash mixing. Such a process is disclosed, for example, in US Pat. No. 6,258,987 ('987). Various subgrades of gasoline such as catalyzed naphtha, reformate, virgin naphtha, isomerate, alkylate, etc. are mixed with the desired amount of alcohol at the mixing site. The mixing site is preferably (1) geographically close to the area where gasoline is distributed and (2) geographically distant from where the subgrade is prepared. The resulting mixture is transferred to a suitable storage location, such as a storage tank, or an element of a distribution system such as a pipeline, railroad, oil transport truck or cargo ship.

Another method of incorporating ethanol is chemical mixing. In this case, ethanol is supplied to the refiner and covalently bonded to the base gasoline. For example, US Pat. No. 5,633,416, etc. discloses a process in which C ₁ -C ₄ alcohols react with etherizable olefins in gasoline subgrades. For example, ethanol may react with isobutylene to produce ethyl tertiary butyl ether (ETBE).

The main advantage of using chemical or splash mixing is to increase the octane number. In addition to higher lead-free octane requirements, there is a growing demand for premium fuels. Various blending values are used to add oxygen into the typical unleaded gasoline shown in Table 1. As can be seen, the octane value ((research octane number (RON) + motor octane number (MON)) / 2) for ethanol and ETBE is in the range of 109-113.

  Although the use of ethanol as a feedstock for splash mixing has many benefits, the motor fuel industry, including the oil industry, general transportation pipelines, and automobile manufacturers, has easily accepted the incorporation of ethanol into gasoline. Absent. As described in the '987 patent, the basic problem that prevents ethanol from being accepted at the place where the refinery is operating and at the market stage is that ethanol, a mixed material, is generally not produced at the refinery. And that the mixing site is generally far from the refinery (ie, the ethanol produced in the Midwest close to where corn is fed must be mixed with gasoline produced in the Gulf Coast. ).

  In addition, because ethanol is completely hydratable, hydrocarbon ethanol mixing requires the removal of water from refinery or mixing site tank farms and product shipping systems. Also, the market for ethanol blends is generally limited because hydrocarbon ethanol blends are not accepted by all petroleum companies. In addition, the pipeline may not accept the ethanol mixture due to the possibility of moisture or moisture-related corrosion. In terms of the environment, ethanol can increase the emission of volatile organic compounds (VOCs) and cannot effectively reduce the emission of harmful substances and nitrided oxides like ethers such as ETBE.

Another serious problem associated with splash ethanol mixing is related to gasoline volatility. For example, in the southern American continent, refineries must reduce gasoline summer-grade lead vapor pressure (RVP) to about 0.8 psi to 7.2 psi. As shown in Table 1, ethanol has a much higher Reed vapor pressure than ETBE. Therefore, when producing a special gasoline subgrade or gasoline blend base material by mixing ethanol, it is preferable to splash-mix ethanol in the final stage. This is a special low RVP feed material that is splash mixed so that the ethanol reaches 10 volume percent, and an ethanol mixed fuel having a specific RVP can be obtained. By removing the C ₄ and C ₅ compounds to conform to the RVP specification, ethanol mixture RVP is adjusted is generally have a low octane number, it is partially offset by the higher ethanol octane. By removing the C ₄ and C ₅ compounds, the T5 and T10 values of D86 of the RVP adjusted mixture are also higher. Also, removing C ₄ and C ₅ compounds results in a reduction in available gasoline volume.

It is also necessary to prepare a discharge destination for the removed C ₄ and C ₅ compounds. This requires additional large equipment at the refinery and the promotion of recycling and reprocessing of these compounds. The economic incentive to absorb 1 gallon of butane in gasoline is typically 10-20 cents, depending on the topography and season. Butane has an octane number of 92, which is as attractive as the above. Butane as a gasoline composition has several higher blend numbers than unleaded regular gasoline (usually 87-89). Incentives about C ₅ compounds is similar. Chemical mixing provides a means to recover some octane number in C ₄ compounds such as butane or isobutylene.

Therefore, there is a need for a manufacturing method that uses renewable resources such as ethanol. The process should provide a gasoline mixture with improved octane quality. The manufacturing method provides a destination for C ₄ and C ₅ compounds that are typically removed to provide an RVP “room” for ethanol.

  In one aspect, embodiments disclosed herein relate to a fuel or fuel blend substrate comprising ethanol, ethyl ether, olefins, and alkanes. In some embodiments, the fuel or fuel blend substrate of claim 1 may have an octane number greater than 92 ((RON + MON) / 2). In other examples, the fuel or fuel blend substrate may have a lead vapor pressure of less than 7.2 psi.

  In another aspect, embodiments disclosed herein relate to a method of manufacturing a fuel. The production method comprises contacting a ethanol fraction with at least one gasoline fraction containing alkane and olefin in the presence of a catalyst to produce a fuel mixture containing ethyl ether, alkane, unreacted olefin and unreacted ethanol; Recovering the fuel mixture for use as a gasoline or gasoline blend substrate without separating the ethanol from the fuel mixture.

  Other aspects and advantages will be apparent from the following description and the additional claims.

  FIG. 1 schematically illustrates a manufacturing flow chart for manufacturing a fuel or fuel component comprising ethanol that has been chemically mixed and splash mixed according to embodiments disclosed herein.

  FIG. 2 schematically illustrates a manufacturing flow chart for manufacturing a fuel that includes chemically mixed and splash mixed ethanol in accordance with embodiments disclosed herein.

  FIG. 3 schematically illustrates a manufacturing flow chart for producing a fuel that includes chemically mixed and splash mixed ethanol in accordance with another embodiment disclosed herein.

  In one aspect, embodiments disclosed herein relate to a manufacturing method for using a renewable feedstock such as ethanol as a fuel component. In other aspects, embodiments disclosed herein relate to fuel compositions comprising alkanes, olefins, ethanol, ethyl ether. More specifically, the embodiments disclosed herein relate to various manufacturing processes for chemically mixing and splash mixing ethanol into gasoline fractions.

  In some embodiments, ethanol and an olefin-containing gasoline fraction are contacted in the presence of an etherification catalyst to produce a fuel mixture comprising ethyl ether, alkane, unreacted olefin, unreacted ethanol. To do. The fuel mixture may then be recovered for use as a gasoline or a blended gasoline base where ethanol is not separated from the fuel mixture. Contact with the etherification catalyst may occur in at least one of a catalytic distillation column and a fixed bed ether reactor.

  As used herein, a gasoline fraction may be (1) a separate refinery stream suitable for use as a blend base for gasoline, and / or (2) a gasoline blend base. A mixed gasoline stream formed by mixing two or more streams suitable for use. A suitable gasoline blend substrate produces a combined stream when mixed with other refinery streams. The combined stream meets the gasoline standards detailed in federal and state regulations.

The raw material of the production method disclosed in the present specification may include a plurality of petroleum raw materials boiling in the boiling range of gasoline. The plurality of petroleum feedstocks include FCC gasoline, coker pentane / hexane, coker naphtha, FCC naphtha, straight run gasoline, and complex mixtures of these streams. Such gasoline mixed streams typically have normal boiling points in the range of 0 ° C. and 260 ° C. as specified in ASTM D86 refining. This type of feedstock is a light naphtha with a C ₆ boiling range typically up to 165 ° C. (330 ° F.), a full range naphtha with a C ₅ boiling range typically up to 215 ° C. (420 ° F.), boiling range Is a heavy naphtha fraction having a boiling point range of about 165 ° C to 260 ° C (330 ° F to 500 ° F), preferably about 165 ° C to 210 ° C. Contains a heavy gasoline fraction. In general, gasoline fuel distills above the range of about room temperature to 260 ° C (500 ° F). In some embodiments, these streams may be processed to remove sulfur, nitrogen and other undesirable components.

Gasoline fraction used in embodiments of the etherification process disclosed herein may include hydrocarbons and higher hydrocarbons than that of C ₃ -C _9. For example, refinery streams are typically separated by fractional distillation. Light naphtha cuts are one such refinery stream, and such cuts contain components with very close boiling points, so separation is not accurate. Light naphtha cut at a refinery is useful as a raw material for isoolefin (for example, iC ₅ =, iC ₆ = compound) to form ether by reaction with ethanol. For example, C ₅ stream may include a and more than that intended to C ₄ species and C ₈ species. These compounds may be saturated (alkanes), unsaturated (monoolefins including isoolefins), polyunsaturated (eg diolefins). Furthermore, the compounds may be any or all of the various isomers of the individual compounds. Such compounds can easily include 150-200 compounds. Other hydrocarbon streams with C ₄ -C ₉ carbon atoms may be used in the embodiments disclosed herein.

In some embodiments, gasoline fractions may include a C ₄ cut. The C ₄ cut may include C _{3 to} C ₅ or higher order hydrocarbons (ie, C ₆₊ ). In other embodiments, gasoline fractions may include a C ₅ cut. C ₅ cut, it may include higher order hydrocarbons than containing C ₄ -C ₈ or an olefin. In other embodiments, gasoline fractions may include a C ₆ cut. C ₆ cuts may include higher order hydrocarbons than containing C ₄ -C _9, or olefins. In other various embodiments, the gasoline fraction may include a mixture of one or more of C _{4 to} C _{7 +} hydrocarbons. The mixture may contain an olefin compound. The streams described above may include C _{4 to} C ₇ streams, gasoline fractions, FCC gasoline, coker gasoline, and other refinery streams having similar properties.

  The saturated compound contained in the above gasoline fraction may contain, for example, various isomers of butane, various isomers of pentane, and various isomers of hexane, among other isomers. The above-mentioned olefin compound containing a gasoline fraction includes, for example, isobutylene and other butene isomers, pentene isomers, hexene isomers, heptene isomers, among other isomers. May contain. In some embodiments, the gasoline fraction may be extracted from various feedstocks, may comprise 1 to 45 weight percent of etherealable isoolefins, and 10 to 30 weight percent of isoolefins of other embodiments. It may contain percent, and may contain 15 to 25 percent by weight of yet another embodiment of isoolefin.

Other embodiments disclosed herein can be widely applied to the production of various ethers from many different gasoline fractions. The main ether obtained by the production method disclosed in the present specification may contain a tertiary amyl group, a tertiary butyl group, a tertiary hexyl ether group, or a tertiary heptyl ether group. In the etherification process, which is one of the productions of butyl ether, a typical feed stream is composed of a mixture of C ₄ isomers including isobutane, isobutylene, normal butane, 1 butene and 2 butene. In one step of amyl ether production, the feed stream components are composed of a typical distribution of isomers: 3-methyl-1-butene, isopentane, 1-pentene, 2-methyl-1-butene, normal pentane, trans May contain 2-pentene, cis-2-pentene, neopentane, 2-methyl-2-butene. While various feeds can provide such gasoline fractions, the most common feed for these process feed streams is the light cracked hydrocarbons from the FCC unit or C from the cracked stream after butadiene extraction. _{There are 4} streams. In one embodiment, the gasoline fraction fed to the ether reactor is divided into reactive isomers (2-methyl-1-butene and 2-methyl-2-butene) and non-reactive isomers (3-methyl-1 -Bene) may contain isoamylene.

  The gasoline fraction containing the isoolefin may be mixed with ethanol. The ethanol may be biological or petroleum derived. The ethanol is preferably biologically derived, such as ethanol produced from corn or other crops. In other embodiments, a diluent comprising ethyl ether may be mixed with the gasoline fraction and ethanol. The ethanol may be like a recycle stream containing a portion of the product from the ether reactor.

  To produce ethyl ether, a mixture obtained from isoolefin and ethanol may be reacted over a suitable etherification catalyst. For example, the mixture can be contacted with macroporous ion exchange resin acid sulfuric acid in a suitable reactor to react ethanol and isobutylene, and is highly selective for ethanol and low yield for isoolefin duplexes. High yields of ethyl ether may be produced. The etherification catalyst will be described in more detail below.

  The waste liquid of the ether reaction apparatus contains ethyl ether, unreacted isoolefin, and unreacted ethanol together with other components. The effluent may then be recovered for use as a fuel or fuel blend substrate without separating the ethanol from the fuel mixture. For example, when using a downflow boiling point reactor, at least a portion of the effluent from the reactor is reused to provide ether containing diluent and temperature control of the reactor. May be.

  The ether reactor effluent may then be recovered for use as a fuel or fuel blend substrate. For example, ether reactor effluent may be recovered, stored if necessary, and transported for use as fuel. In other embodiments, the ether reactor effluent may be splash mixed into ethanol or other gasoline fractions. The splash mixed result may be stored and transported for use as a fuel.

  In some embodiments, the gasoline fraction is a mixing site that is geographically close to where the final alcohol-containing gasoline is distributed for use as fuel and geographically remote from where the gasoline fraction is prepared. Be transported to. The etherification of a part of the olefin may then be performed at the mixing site. The reactor effluent containing ethanol and ethyl ether may then be used as a fuel or fuel blend substrate. For example, a fuel containing ethanol and ethyl ether may then be prepared at the mixing site with a mixture containing the desired amount of alcohol or other gasoline fraction.

As described above, the isoolefin and alcohol may react to produce ether. Examples of ether formation in the embodiments disclosed herein include, among others, ethyl tertiary butyl alcohol (ETBE), reaction product of isobutylene and ethanol, tertiary amyl ethyl ether (TAEE), reaction of isoamylene and ethanol. the product, tert-hexyl ether (THEE), may comprise the reaction product of various C ₆ isoolefins with ethanol.

  First, referring to FIG. 1, a distillation column reactor system 5 will be described according to some embodiments disclosed herein. A gasoline fraction 10 containing isoolefin is fed to a distillation column reactor 12. The supply position of the gasoline fraction 10 may be the upper part, the lower part, or the middle of the catalyst-containing region 14. The isoolefin contained in the hydrocarbon stream 10 reacts with the ethanol fed in stream 15 in the catalyst-containing region 14 to produce ether. The distillation column reactor 12 has a reboiler 16 and an overhead system 17, each controlling the flow of liquid and gas within the distillation column reactor 12.

  The distillation column reactor system 5 includes at least a portion of the unreacted ethanol present in the distillation column reactor 12 together with heavy hydrocarbons contained in the ether and hydrocarbon stream 10 produced by the reaction of olefin and alcohol. , Controlled to exit to the lower stream 18. Light hydrocarbons containing alkanes and some unreacted olefins may be concentrated in the overhead system 17 and recovered in the upper stream 20 or may be refluxed to the top of the distillation column reactor 12 via line 21. And may be reused.

  As shown, ethanol is fed to the distillation column reactor 12 along with the hydrocarbon stream 10. Alternatively, ethanol may be fed elsewhere on the distillation column reactor 12, including feed points at the top or bottom of the hydrocarbon feed stream 10. By selecting the azeotrope produced by ethanol and various hydrocarbons, as well as the control conditions, ethanol may be present in both the lower stream 18 and the upper stream 20. The chemically mixed and splash mixed ethanol containing stream 18 is then used as a fuel or fuel substrate, typically without separating the ethanol.

  In other embodiments, additional ethanol may be added to the distillation column reactor system above the location where the gasoline fraction is fed. Ethanol may be added at several points at the top of the column, for example, at the top of the etherification catalyst zone, within the etherification catalyst zone, and at the bottom of the etherification catalyst zone. By this aspect, the concentration of ethanol at various locations on the column can be increased or controlled to a desired level.

  In some embodiments, the hydrocarbon and alcohol feed is passed through a fixed bed ether reactor and at least a portion of the feed is converted to ether. US Pat. Nos. 5,003,124 and 4,950,803 disclose liquid phase processes for etherification and oligomerization of C4 or C5 isoolefins and alcohols in a boiling point fixed bed reactor. ing. The boiling point fixed bed reactor is controlled at a pressure that maintains the reaction mixture in direct contact with the catalytic distillation reactor at its boiling point. The fixed bed reactor may be a single layer reactor, a fixed bed boiling point reactor, or a combination of them, as in a liquid phase or gas phase reactor. In some embodiments, the fixed bed boiling point reactor may be operated in a pulse flow manner.

  In some embodiments, the effluent from the fixed bed reactor is used directly as a fuel or fuel blend substrate. In other embodiments, the effluent from the reactor is then further processed in a catalytic distillation reactor system where the control described above takes place.

  In other embodiments, the gasoline fraction supplied to the etherification reactor may be processed prior to being supplied to the catalytic distillation reactor system. For example, various gasoline fractions may be subjected to hydrogenation, selective hydrogenation of dienes and / or acetylene, hydrodesulfurization, hydrodenitrogenation, other treatments known to those skilled in the art, and the like.

  With reference to FIG. 2, according to an embodiment disclosed in the present specification, a manufacturing process of an ethanol-containing fuel will be described based on a simple flowchart. Individual gasoline fractions or gasoline blend bases pass through input lines 41, 42, 43, 44, 45, 46, respectively. Although six input lines are shown in FIG. 2, the number of input lines may be more than six or less than six. Each of the input lines 41-46 is discharged into a mixing vessel 47 where the blend substrate is mixed to produce a subgrade blend. The subgrade blend is then converted to a fuel containing ethyl ether and ethanol, or a standard fuel blend substrate, by reacting and / or mixing with the desired amount of ethanol fed to reactor 35 from line 37. . If necessary, it may be recycled through the flow line 38 back to the reactor inlet.

  The fuel or fuel blend substrate recovered from the reactor 35 via the discharge line 48 can be stored in a suitable storage location such as a drainage tank or in a distribution system element such as a pipeline, railroad, oil transport truck or cargo ship ( (Not shown). If necessary, additional splash mixed ethanol or other gasoline blend base may be added through line 39. In order to control the final composition of the fuel, such as ethanol concentration, oxygen content, lead vapor pressure, octane number and other suitable characteristics, within the desired specifications, each of the input lines 37, 39, 41-46 A weighing device may be attached.

  Although shown in FIG. 2 as feeding a mixture of various gasoline blend bases to an etherification reactor, the etherification reactor may be utilized to etherify a particular fraction. Thereafter, as shown in FIG. 3, the remaining fraction may be mixed with an etherified gasoline blend base to achieve the desired fuel specification. In FIG. 3, the same reference numerals are used for similar configurations.

  According to the embodiments disclosed herein, the octane number (motor octane number or ((RON) + (MON)) / 2) of the fuel or fuel blend base material obtained by chemical mixing and splash mixing described above. Is greater than 90. In other embodiments, the octane number is greater than 91, in other embodiments greater than 92, in other embodiments greater than 93, in other embodiments greater than 95, and in other embodiments greater than 98. And in other embodiments greater than 100.

  According to embodiments disclosed herein, the lead vapor pressure of the fuel or fuel blend substrate obtained by the chemical and splash mixing described above is less than 7.5 psi. In other embodiments, the lead vapor pressure is less than 7.2 psi, in other embodiments the lead vapor pressure is less than 7 psi, in other embodiments the lead vapor pressure is less than 6.9 psi, other embodiments The lead vapor pressure is less than 6.8 psi, in other embodiments the lead vapor pressure is less than 6.7 psi, in other embodiments the lead vapor pressure is less than 6.6 psi, and in other embodiments The lead vapor pressure is less than 6.5 psi.

  The oxygen content of the fuel or fuel blend substrate (including chemically mixed and splash mixed ethanol) disclosed herein is comparable to the splash mixed ethanol fuel. The fuel or fuel blend substrate disclosed herein has an oxygen concentration of at least 2 weight percent in some embodiments and an oxygen concentration of at least 2.25 weight percent in other embodiments. In embodiments, the oxygen concentration is at least 2.5 weight percent; in other embodiments, the oxygen concentration is at least 2.75 weight percent; in other embodiments, the oxygen concentration is at least 3.0 weight percent; In embodiments, the oxygen concentration is at least 3.25 weight percent, and in yet other embodiments the oxygen concentration is at least 3.5 weight percent.

  As noted above, the fuel or fuel blend substrate disclosed herein includes ethanol that is chemically mixed with splash mixing. Chemically mixed ethanol is an ether. The total ethanol content in the fuel or fuel blend substrate (including ethanol chemically mixed in the fuel mixture) is at least 8 volume percent, in other embodiments at least 9 volume percent, other embodiments At least 10 volume percent, in other embodiments at least 11 volume percent, in other embodiments at least 12 volume percent, and in yet other embodiments at least 15 volume percent.

  Etherification catalyst

  All of the typical catalysts used in the etherification process can be used in the embodiments disclosed herein. Conventional cation exchange resins and / or zeolites can be used in various embodiments. Thus, the resin may contain sulfonic acid groups and may be obtained by polymerization or copolymerization of an aromatic vinyl compound and subsequent sulfonation. Examples of aromatic vinyl compounds suitable for preparing the copolymer include styrene, vinyl toluene, vinyl naphthalene, vinyl ethyl benzene, methyl styrene, vinyl chlorobenzene, vinyl xylene. The acidic cation exchange resin may contain 1.3 to 1.9 sulfonic acid groups per aromatic nucleus. In some embodiments, the resin may be based on a copolymer of aromatic monovinyl compounds having a copolymer of aromatic polyvinyl compounds, wherein the amount of polyvinylbenzene is approximately 1 to 20 weight percent of the copolymer. is there. In some embodiments, the ion exchange resin may be approximately 0.15-1 mm in particle shape. In addition to the above resins, a perfluorosulfonic acid resin (a copolymer of sulfonylfluorovinylethyl and fluorocarbon) may be used.

  Catalysts useful for the etherification process disclosed herein may include zeolites, sometimes referred to as medium pores or ZSM-5 types. In other embodiments, the zeolite is ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-, having pore sizes comparable to Y-type zeolite and β-type zeolite. 50, medium pore selective acidic metallosilicate zeolite selected from the group of MCM-22. The original cation associated with the zeolite used herein may be replaced by various other cations, for example according to techniques known in the field of ion exchange. Typical cations that can be substituted include hydrogen, ammonium, alkylammonium, metal cations, and mixtures thereof. In the case of a metal cation, metals of Groups 1B to 8A of the periodic table, such as iron, nickel, cobalt, copper, zinc, palladium, calcium, chromium, tungsten, molybdenum, etc. can be used. These metals may be present in the form of oxides.

In other embodiments, the etherification catalyst for the isoalkene reactant includes sulfuric acid, boron trifluoride, phosphoric acid over diatomaceous earth, phosphorus-modified zeolites, heteropolyacids, and various sulfonated resins. Contains inorganic acids such as. These resin-type catalysts may contain a reaction product obtained by crosslinking a phenol / formaldehyde resin, sulfuric acid, and a sulfonated polystyrene resin with divinylbenzene. Certain etherification catalysts are macroporous of sulfonate ion exchange resins, such as sulfonated styrene divinylbenzene resins having a degree of crosslinking of 5-60%, as described in US Pat. No. 2,922,822. Acid type. A special resin comprising a sulfonyl fluorovinyl ether and fluorocarbon copolymer is disclosed in US Pat. No. 3,489,243. Another specially prepared resin consists of a cation exchanger modified with SiO ₂ as disclosed in US Pat. No. 4,751,343. A suitable resin macroporous structure is described in detail in US Pat. No. 5,012,031. The suitable resin has a surface area of at least about 400 m ² / g, a pore volume of about 0.6 to 2.5 ml / g, and an average pore size of 40 to 1000 angstroms. is there. One or more metals from the Group 6-8 subgroup of the periodic table, such as chromium, tungsten, palladium, nickel, chromium, platinum, iron, as disclosed in US Pat. No. 4,330,679. The use of the containing metal-containing resin is considered to be performed in the main process. Further information regarding suitable etherification catalysts can be obtained by reference to U.S. Pat. Nos. 2,480,940, 2,922,822, 4,270,929.

  The catalytic distillation structure used in some embodiments includes disposing cation exchange resin particles in a plurality of pockets in the cross belt. The plurality of pockets in the cross belt are supported in the catalytic distillation column reactor by coarsely knitted stainless steel in which two of the stainless steel wires are twisted together in a spiral. Thereby, a required flow is ensured and the loss of the catalyst is suppressed. The cloth may be any material that is inert to the reaction, such as cotton, linen, fiberglass cloth, or Teflon. U.S. Pat. Nos. 4,302,356, 4,443,559, and 5,730,843 disclose catalyst structures useful for distillation structures and are incorporated herein by reference. Other particularly suitable etherification catalysts are, for example, U.S. Pat. Nos. 5,190,730, 5,231,234, 5,248,836, 5,292,964, 5,637. 777, No. 6,107,526.

  Example

A fuel produced using the process disclosed herein having a typical base gasoline, gasoline with a splash blend of ethanol with adjusted lead vapor pressure (RVP), and ethanol with a chemical blend and splash blend. Table 2 compares the three types of fuel characteristics. For comparison, the RVP of the three fuels was kept constant so that the influence on the octane number (RON) could be investigated, and the volume produced was assumed to be able to be produced per day by a typical process. Furthermore, for the fuel containing ethanol, the oxygen content of the mixture was suppressed to be equal.

For the RVP adjusted ethanol blend, the blend base was adjusted so that the gasoline blend base was suitable for ethanol splash mixing by removing light fuel components so that the final fuel met the RVP specification. The RON of splash mixed ethanol is lower than the base gasoline because it removes the C ₄ and C ₅ components, which are high octane components, to meet RVP standards. This decrease is partially offset by the high octane number of ethanol. The volume of effectively splash-mixed gasoline is also lower than conventional gasoline by removing light cuts.

Chemically mixed and splash mixed ethanol fuel is prepared by reacting most (~ 95%) of specific isobutane and reactive isoamylene to ethanol to produce ETBE and TAEE. In addition, some of the C ₆ isoolefin is also converted to C ₆ ethyl ether. Additional ethanol is then splash mixed and the base oxygen content is increased to 3.7 weight percent. Although the RON is slightly reduced compared to the RVP adjusted ethanol splash blend, the available gasoline volume is large. Furthermore, chemical mixing to produce ethers steadily reduces the olefin content of the final fuel. If the refinery is hydrotreating conventional base gasoline to reduce olefin content, the chemical mixing process may be able to reduce the required hydrotreatment. The combined use of a chemical mixing step with ethanol splash mixing provides significant gasoline volume and octane-point-barrels benefits compared to splash mixing alone.

  As noted above, the process embodiments disclosed herein provide a fuel and fuel blend substrate comprising ethanol that has been subjected to both chemical and splash mixing. The process disclosed herein provides a simple etherification process. The process allows the ethanol recovery section to be omitted completely, saving investment and operating costs.

Embodiments disclosed herein, a discharge destination of the C ₄ olefins, ethanol clean fuel while reducing automobile exhaust by adding adding the C ₄ and C ₅ hydrocarbons in the fuel component It provides at least one of effective utilization and effective reduction of olefins in gasoline while benefiting. Furthermore, the process disclosed herein can provide an alternative to ethanol splash mixing.

The synergistic combination of chemical and splash mixing to mix ethanol into clean gasoline (with similar oxygen levels) will only maintain the economic, social and environmental benefits of using ethanol. Without increasing their profits. By using the process disclosed herein, a greater amount of gasoline can be provided, and more ethanol can be effectively utilized. Improved quality of the fuel, without having to re-treated with refinery can reduce the amount of C ₄ and C ₅ feed should not.

  While the octane number of the fuel is maintained, olefins can be greatly reduced without hydrotreating. Therefore, even in refineries that are driven by olefin processing, hydrogen consumption is zero. As a result, carbon dioxide produced by supplying hydrogen in the refinery can be reduced overall.

  While this disclosure includes a limited number of embodiments, those skilled in the art having the benefit of this disclosure can devise other embodiments that do not depart from the scope of this disclosure. Accordingly, the scope of the invention is limited only by the appended claims.

Claims (16)

  A fuel or fuel blend base material comprising ethanol, ethyl ether, olefin and alkane.   The fuel or fuel blend substrate of claim 1, wherein the fuel or fuel blend substrate has an octane number greater than 92 × (RON + MON) / 2.   The fuel or fuel blend substrate of claim 1, wherein the fuel or fuel blend substrate has a reed vapor pressure of less than 7.2 psi.   The fuel or fuel blend base according to claim 1, wherein the fuel or fuel blend base has an oxygen content of at least 3.5% by weight. Contacting the ethanol with at least one gasoline fraction containing alkane and olefin in the presence of a catalyst to produce a fuel mixture component comprising ethyl ether, alkane, unreacted olefin and unreacted ethanol;
A recovery step for recovering a fuel mixture for use as gasoline or a gasoline blend base without separating ethanol from the fuel mixture;
A method for producing a fuel comprising: The contact step includes
Supplying ethanol and a gasoline fraction containing isoolefin to a distillation column reactor system comprising at least one etherification reaction section;
Removing the fuel mixture from the bottom of the distillation column reactor system;
A fuel production method according to claim 5. The contact step includes
The method for producing a fuel according to claim 5, further comprising a step of supplying ethanol and a gasoline fraction containing isoolefin to a fixed bed reaction system including at least one etherification reaction section.   The method for producing fuel according to claim 5, further comprising a step of mixing ethanol and at least one of a second gasoline fraction having a fuel mixture.   The method for producing fuel according to claim 5, further comprising a step of transferring at least one of the ethanol and gasoline fractions to a site performing the contact step and the recovery step.   The method for producing fuel according to claim 5, wherein the transfer uses at least one of a pipeline, a railway, an oil transportation truck, and a cargo ship. The method for producing fuel according to claim 5, wherein the gasoline fraction has a C _{4 to} C ₉ alkane. The method for producing fuel according to claim 5, wherein the gasoline fraction has C _{4 to} C ₇ olefins.   The method for producing a fuel according to claim 5, wherein the ethyl ether has at least one of ethyl tertiary butyl ether, tertiary amyl ethyl ether, tertiary hexyl ethyl ether, and tertiary heptyl ethyl ether. Gasoline fraction, C ₄ cut, C ₅ cut, a manufacturing method of the fuel according to claim 5 having at least one of C ₆ cuts and light naphtha fractions.   6. The method of producing a fuel according to claim 5, wherein the fuel mixture has a reed vapor pressure of less than 7.2 psi.   The method for producing a fuel according to claim 5, wherein the oxygen content of the fuel mixture is at least 3.5% by mass.

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