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    • 专利摘要:
    ZEOLITICAL CATALYTIC CONVERSION OF ALCOHOLS TO HYDROCARBONS. A method of converting an alcohol to a hydrocarbon, the method comprising contacting said alcohol with a metal-loaded zeolite catalyst at a temperature of at least 100°C and up to 550°C, wherein said alcohol can be produced by a In the fermentation process, said metal is a positively charged metal ion, and said metal charged zeolite catalyst is catalytically active to convert said alcohol to said hydrocarbon.
    公开号:BR112013032184B1
    申请号:R112013032184-9
    申请日:2012-06-14
    公开日:2021-05-25
    发明作者:Chaitanya K. Narula；Brian H. Davison；Martin Keller
    申请人:Ut-Battelle, Llc；
    IPC主号:
    专利说明:

    Cross reference to related order
    [001]This application claims the priority benefit of U.S. Provisional Application 61/497,256, filed on June 15, 2011. government support
    [002]This invention was made with government support under Commencement Contract No. DE-AC05-00OR22725 awarded by the U.S. Department of Energy. The government has certain rights in the invention. field of invention
    [003] Generally, the present invention relates to the catalytic conversion of alcohols to hydrocarbon, and more particularly, to zeolite-based catalytic methods for such conversion. Background of the invention
    [004] The conversion of alcohols to hydrocarbons is generally not commercially possible. In fact, most commercial alcohols are produced from hydrocarbons. Alcohol-to-hydrocarbon conversion is also prohibitive due to the significant cost requirements of current conversion processes. Consequently, alcohol obtained by natural means (eg, by fermentation from biomass) would be a significantly more cost-effective feedstock.
    [005] However, a major obstacle in applying current conversion methodology to biomass-produced alcohols (ie, bioalcohols) is the high water concentration (and concomitant low alcohol concentrations) typically found in fermentation streams produced in refineries from biomass-to-alcohol. Current alcohol-to-hydrocarbon conversion processes are generally incapable or highly ineffective in providing such conversion to such dilute alcohol at high water concentrations. Instead, current alcohol-to-hydrocarbon conversion processes generally require pure alcohol (ie, in the significant absence of water). Furthermore, the concentration and/or distillation of alcohol from a fermentation stream to accommodate current technologies would be highly energy intensive, and thus would largely offset the gains made in the low initial cost of using a bioalcohol in large part. Invention Summary
    [006] The invention is directed to a method for catalytically converting an alcohol into a hydrocarbon, in which the catalytic conversion is carried out without requiring the alcohol to be purified or concentrated prior to the conversion reaction. For example, by methods described herein, effective conversion can be carried out in dilute aqueous solutions of an alcohol, as found, for example, in the fermentation stream of a biomass fermentation reactor. In particular embodiments, the method includes contacting an alcohol (or mixture of alcohols) with a metal-loaded zeolite catalyst at a temperature of at least 100°C and up to 550°C, where the alcohol can be (i.e., e.g. capable of being, or is) produced by a fermentation process, the metal is a positively charged metal ion, and the metal-charged zeolite catalyst is catalytically active to convert the alcohol or mixture thereof to a hydrocarbon or hydrocarbon mixture. . Brief description of the drawings
    [007] FIG. 1. Graph comparing hydrocarbon distribution between pure ethanol (A) and 10% ethanol in water (B) after catalytic conversion to Cu-ZSM-5 at 400°C. The compounds are (from left to right, identified by arrows) water, acetaldehyde, isobutene, 2-butene, acetone, 1,2-dimethyl-4-ethynyl-benzene, 2-butanone, benzene, toluene, 1,3-dimethylbenzene , p-xylene, naphthalene, and phenol.
    [008] FIG. 2. Graph showing the hydrocarbon distribution in the 10% ethanol product stream after catalytic conversion to Cu-ZSM-5 at 400°C to 12.5h-1 LHSV. The compounds are (from left to right, identified by arrows) water, acetaldehyde, isobutane, 2-butene, acetone, 2-methylbutene, 2-methyl-2-butene, cis-1,2-dimethylcyclopropene, cyclopentane, 3.3 -dimethylcyclobutene, benzene, 4,4-dimethylcyclobutane, toluene, 1,3-dimethylbenzene, 1-ethyl-3-methylbenzene, 1,2,4-trimethylbenzene, and 1-ethyl-4-methyl-benzene.
    [009] FIGS. 3A, 3B. Graph that plots the conversion of ethanol to hydrocarbons as a function of temperature at an LHSV of 2.93 h-1 (FIG. 3A) and as a function of LHSV at 275°C (FIG. 3B) for V catalyst -ZSM-5.
    [0010] FIGS. 4A, 4B. Graph plotting carbon distribution in raw material from produced mixture (FIG. 4A) and raw material from jet fuel/diesel mixture obtained by fractional collection (FIG. 4B) for V-ZSM-5 catalyst. Detailed description of the invention
    [0011] In the conversion method described here, an alcohol is catalytically converted to a hydrocarbon by contacting the alcohol with a metal-loaded zeolite catalyst under conditions (particularly temperature and choice of catalyst) suitable to carry out said conversion. As used herein, the term "alcohol" is intended to include a single alcohol or a mixture of two or more alcohols, and the term "hydrocarbon" is also intended to include a single hydrocarbon compound or a mixture of two or more hydrocarbon compounds.
    [0012] The alcohol considered here is primarily that which can be produced by a fermentation process (ie, a bioalcohol). Most notable examples of bioalcohols considered here include ethanol, butanol and isobutanol. In different embodiments, the alcohol can be ethanol, or butanol, or isobutanol, or a combination thereof, as commonly found in fermentation streams. In particular embodiments, alcohol is an aqueous solution of alcohol (i.e., alcohol is a component of an aqueous solution), as found in fermentation streams. In fermentation streams, the alcohol is typically at a concentration of no more than about 20% (vol/vol), 15%, 10%, or 5%. In some embodiments, a fermentation stream is contacted directly with the catalyst (typically, after filtration removes solids) to effect the conversion of alcohol in the fermentation stream. In other embodiments, the fermentation stream is concentrated in alcohol (eg, at least or up to 30%, 40%, or 50%) before contacting the fermentation stream with the catalyst. In still other embodiments, the alcohol in the fermentation stream is selectively removed from the fermentation stream, such as by distillation, to produce a substantially pure form of alcohol as the feedstock (e.g., a concentration of at least 90% or 95% alcohol). In still other embodiments, the alcohol is completely dehydrated to 100% alcohol before contacting the catalyst.
    [0013] As used herein, the term "about" generally indicates within ±0.5%, 1%, 2%, 5%, or up to ±10% of the stated value. For example, a concentration of about 20% generally indicates in its broadest sense 20 ± 2%, which indicates 18 - 22%. Furthermore, the term "about" may indicate a measurement error (ie, by limitations in the measurement method), or alternatively, a variation or average in a physical characteristic of a group.
    [0014] Although a wide variety of hydrocarbon product can be produced by the present method, the hydrocarbon considered primarily here is typically saturated, and more particularly, in the class of alkanes which may be straight-chain or branched, or a mixture thereof, particularly when the hydrocarbon product is to be used as a fuel. Alkanes particularly desired herein include those containing at least four, five, or six carbon atoms, and up to twelve, fourteen, sixteen, seventeen, eighteen, or twenty carbon atoms. Some examples of straight chain alkanes include n-butane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, n-tridecane, n- tetradecane, n-pentadecane, n-hexadecane, n-heptadecane, n-octadecane, n-nonadecane, and n-eicosane. Some examples of branched chain alkanes include isobutane, isopentane, neopentane, isohexane, 3-methylpentane, 2,3-dimethylbutane, 2,2-dimethylbutane, 2-methylhexane, 3-methylhexane, 2,2-dimethylpentane, 2,3- dimethylpentane, 2,4-dimethylpentane, 3,3-dimethylpentane, 2-methylheptane, and 2,2,4-trimethylpentane (isooctane). Some other hydrocarbon products that can be produced by the present method include olefins (i.e., alkenes, such as, for example, ethylene, propylene, n-butene and/or isobutene) and aromatics (for example, naphthalene, benzene, toluene and/or xylenes).
    [0015] The hydrocarbon product particularly considered here is a mixture of hydrocarbon compounds useful as a fuel or as a blended raw material in fuel. The mixture of hydrocarbon compounds produced herein preferably substantially corresponds (e.g., in composition and/or properties) to a known petrochemical fuel, such as petroleum, or a petroleum fractional distillate. Some examples of petrochemical fuels include gasoline, kerosene, diesel, and jet propellant (eg, JP-8). As hydrocarbon fuel grades in current use, the mixture of hydrocarbon compounds produced herein may, in some embodiments, be predominantly or exclusively composed of alkanes, alkenes, aromatics, or a mixture thereof. Although aromatics (particularly benzene) may be present in the hydrocarbon mixture, their presence can be minimized to adhere to current fuel standards. The crude hydrocarbon product, produced by the method immediately described, is typically fractionated by distillation into different grades of fuel, each of which is known to be within a certain range of the boiling point. A particular advantage of the present method is its ability to produce such fuel grades in the significant absence of contaminants (eg mercaptans) normally required to be removed during petroleum refining processes. Furthermore, by proper adjustment of catalyst and process conditions, a select distribution of hydrocarbon can be obtained.
    [0016] Depending on the final composition of the hydrocarbon product, the product can be directed to a variety of applications, including, for example, as precursors for plastics, polymers and fine chemicals. The process described here can advantageously produce a range of hydrocarbon products that differ in any of a variety of characteristics, such as molecular weight (ie, hydrocarbon weight distribution), degree of saturation or unsaturation (e.g. , alkane to alkene ratio), and level of branched or cyclic isomers. The process provides this level of versatility by appropriately selecting, for example, catalyst composition (eg, catalytic metal), catalyst amount (eg, catalyst to alcohol precursor ratio), process temperature, and flow rate (eg LHSV).
    [0017] In the process, a suitable reaction temperature is employed during the contact of the alcohol with the catalyst. Generally, the reaction temperature is at least 100°C and up to 550°C. In different embodiments, the reaction is precisely at or about, for example, 100°C, 125°C, 150°C, 175°C, 200°C, 225°C, 250°C, 275°C, 300°C , 325°C, 350°C, 375°C, 400°C, 425°C, 450°C, 475°C, 500°C, 525°C, or 550°C, or a temperature within a bound range by any two of the foregoing exemplary temperatures (for example, 100°C - 550°C, 200°C - 550°C, 300°C - 550°C, 400°C - 550°C, 450°C - 550°C , 100°C - 500°C, 200°C - 500°C, 300°C - 500°C, 350°C - 500°C, 400°C - 500°C, 450°C - 500°C, 100 °C - 450°C, 200°C - 450°C, 300°C - 450°C, 350°C - 450°C, 400°C - 450°C, 100°C - 425°C, 200°C - 425°C, 300°C - 425°C, 350°C - 425°C, 375°C - 425°C, 400°C - 425°C, 100°C - 400°C, 200°C - 400 °C, 300 °C - 400 °C, 350 °C - 400 °C, and 375°C - 400 °C).
    [0018] Generally, an ambient (ie, normal atmospheric) pressure of about 1 atm is used in the method described here. However, in some modalities, an elevated pressure or reduced pressure may be used. For example, in some embodiments, the pressure can be raised, for example, 1.5, 2, 3, 4, or 5 atm, or reduced to, for example, 0.5, 0.2, or 0.1 atm .
    [0019] The catalyst and reactor can have any of the designs known in the art to catalytically treat a fluid or gas at elevated temperatures, such as a fluidized bed reactor. The process can be in a continuous or batch mode. In particular embodiments, alcohol is injected into a heated reactor such that the alcohol is rapidly volatilized into gas, and the gas passed through the catalyst. In some embodiments, the reactor design includes a boiler unit and a reactor unit if the fermentation stream is directly used as a feedstock without purification. The boiler unit is generally not needed if the fermentation stream is distilled to concentrate ethanol because the distillation process removes dissolved solids in the fermentation streams. The boiler unit volatilizes the liquid feed raw material into gases prior to entering the reactor unit and retains dissolved solids.
    [0020] In some embodiments, the conversion method described above is integrated with a fermentation process, in which the fermentation process produces the alcohol used as a feedstock for the conversion process. Being "integrated" means that alcohol produced in a fermentation zone or apparatus is shipped and processed in a conversion zone or apparatus (which carries out the conversion process described above). Preferably to minimize production costs, the fermentation process is in sufficient close proximity to the conversion zone or apparatus, or includes appropriate channels to transfer the produced alcohol to the conversion zone or apparatus, thereby not requiring transporting the alcohol to be shipped. . In particular embodiments, the fermentation stream produced in the fermentation apparatus is transferred directly to the conversion apparatus, usually with removal of solids from the raw stream (usually by filtration or sedimentation) before the stream contacts the catalyst.
    [0021] In some modalities, the fermentation process is carried out in an autonomous fermentation apparatus, that is, where saccharides, produced elsewhere, are loaded into the fermentation apparatus to produce alcohol. In other embodiments, the fermentation process is part of a larger biomass reactor apparatus, that is, where the biomass is broken down into fermentable saccharides, which are then processed in a fermentation zone. Biomass reactors and fermentation apparatus are well known in the art. Biomass often refers to lignocellulosic matter (ie, plant material), such as wood, grass, leaves, paper, corn husks, sugarcane, bagasse, and walnut husks. Generally, biomass-to-ethanol conversion is accomplished by 1) pre-treating the biomass under well-known conditions to release lignin and hemicellulose material from the cellulosic material, 2) by breaking the cellulosic material into fermentable saccharide material by the action of a cellulase enzyme, and 3) by fermenting the saccharide material, typically by the action of a fermenting organism, such as suitable yeast.
    [0022] In other embodiments, alcohol is produced from a more direct sugar source, such as a plant-based source of sugars, such as sugar cane or a grain starch (such as corn starch ). Ethanol production through corn starch (ie, cornstarch ethanol) and through sugarcane (ie, sugarcane ethanol) currently represents some of the largest commercial production methods. of ethanol. Integration of the present conversion process with any of these large scale ethanol production methods is contemplated here.
    [0023] The conversion catalyst used here includes a portion of zeolite and a metal charged in the zeolite. A zeolite considered herein can be any of the porous aluminosilicate structures known in the art that are stable under high temperature conditions, i.e., at least 100°C, 150°C, 200°C, 250°C, 300°C, and higher temperatures up to, for example, 500°C, 550°C, 600°C, 650°C, 700°C, 750°C, 800°C, 850°C, or 900°C. In particular embodiments, a zeolite is stable from at least 100°C and up to 700°C. Typically, a zeolite is ordered to have a crystalline or part-crystalline structure. A zeolite can generally be described as a three-dimensional structure that contains silicate (SiO2 or SiO4) and aluminate (Al2O3 or AlO4) units that are interconnected (ie, cross-linked) by sharing oxygen atoms.
    [0024] Zeolite may be microporous (ie, pore size less than 2 µm), mesoporous (ie, pore size within 2-50 µm, or a sub-range thereof), or a combination thereof. In various embodiments, the zeolite material is completely or substantially microporous. Being completely or substantially microporous, the pore volume due to the micropores can be, for example, 100%, or at least 95%, 96%, 97%, 98%, 99%, or 99.5%, with the volume of remaining pore being due to mesopores, or in some embodiments, macropores (pore size greater than 50 µm). In other embodiments, the zeolite material is completely or substantially mesoporous. Being completely or substantially mesoporous, the pore volume due to mesopores can be, for example, 100%, or at least 95%, 96%, 97%, 98%, 99%, or 99.5%, with the volume of remaining pore which is due to micropores, or in some embodiments, macropores. In still other embodiments, the zeolite material contains an abundance of micropores and mesopores. Containing an abundance of micropores and mesopores, the pore volume due to mesopores can be, for example, up to at least or precisely 50%, 60%, 70%, 80%, or 90%, with the pore volume balance being due to micropores, or vice versa.
    [0025] In various embodiments, a zeolite is an MFI-type zeolite, MEL-type zeolite, MTW-type zeolite, MCM-type zeolite, BEA-type zeolite, kaolin, or a faujasite-type zeolite. Some particular examples of zeolites include the ZSM class of zeolites (eg ZSM-5, ZSM-8, ZSM-11, ZSM-12, ZSM-15, ZSM-23, ZSM-35, ZSM-38, ZSM-48 ), zeolite X, zeolite Y, zeolite beta, and the MCM class of zeolites (eg, MCM-22 and MCM-49). The compositions, structures, and properties of these zeolites are well known in the art, and have been described in detail, as found in, for example, US Patents 4,721,609, 4,596,704, 3,702,886, 7,459,413, and 4,427,789 , the contents of which are incorporated herein by reference in their entirety.
    [0026] The zeolite can have any suitable silica-to-aluminium ratio (i.e. SiO2/Al2O3 or "Si/Al"). For example, in various embodiments, a zeolite may have an Si/Al ratio of precisely at least less than or even 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 120, 150, or 200, or an Si/Al ratio within a range bound by any two of the preceding values. In particular embodiments, a zeolite has a Si/Al ratio of 1 to 45.
    [0027] In particular embodiments, a zeolite is ZSM-5. ZSM-5 belongs to the pentasil-containing class of zeolites, all of which are considered in the same way here. In particular embodiments, a ZSM-5 zeolite is represented by the formula NanAlnSi96-nO192.16H2O, where 0 < n < 27.
    [0028] Typically, a zeolite contains an amount of cationic species. As is well known in the art, the amount of cationic species is generally proportional to the amount of aluminum in the zeolite. This is because the replacement of silicon atoms with lower valent aluminum atoms requires the presence of countercations to establish a charge balance. Some examples of cationic species include hydrogen ions (H+), alkali metal ions, alkaline earth metal ions, and main group metal ions. Some examples of alkali metal ions that can be included in the zeolite include lithium (Li+), sodium (Na+), potassium (K+), rubidium (Rb+), and cesium (Cs+). Some examples of alkaline earth metal ions that can be included in the zeolite include (Be2+), magnesium (Mg2+), calcium (Ca2+), strontium (Sr2+), and barium (Ba2+). Some examples of main group metal ions that can be included in the zeolite include boron (B3+), gallium (Ga3+), indium (In3+), and arsenic (As3+). In some embodiments, a combination of cationic species is included. Cationic species can be in a trace amount (for example, not more than 0.01 or 0.001%), or alternatively, in a significant amount (for example, above 0.01%, and up to, for example, 0 , 0.1, 0.5, 1, 2, 3, 4, or 5% by weight of the zeolite). In some embodiments, any one or more of the above classes or specific examples of cationic species are excluded from the zeolite.
    [0029] The zeolite described above is loaded with an amount of metal. The metal loaded in the zeolite is selected such that a resulting metal loaded zeolite is catalytically active, under conditions mentioned above, to convert an alcohol to a hydrocarbon. Typically, the metal considered here is in the form of positively charged metal ions (ie, metal cations). For example, metal cations can be monovalent, divalent, trivalent, tetravalent, pentavalent, or hexavalent. In some embodiments, the metal is (or includes) alkali metal ions. In other embodiments, the metal is (or includes) alkaline earth metal ions. In other embodiments, the metal is (or includes) a transition metal, such as one or more of the first, second, or third transition metal in the series. Some preferred transition metals include copper, iron, zinc, titanium, vanadium, and cadmium. Copper ions can be cuprous (Cu+1) or cupric (Cu+2) in nature, and iron atoms can be ferrous (Fe+2) or ferric (Fe+3) in nature. Vanadium ions can be in any of their known oxidation states, for example, V+2, V+3, V+4, and V+5. In other embodiments, the metal is (or includes) a catalytically active headgroup metal, such as gallium or indium. A single metal or a combination of metals can be loaded into the zeolite. In other embodiments, any one or more metals described above are excluded from the zeolite.
    [0030] The metal loading can be any suitable amount, but is generally not more than about 2.5%, where the loading is expressed as the amount of metal by weight of the zeolite. In different embodiments, the metal loading is precisely at least less than, or even, for example, 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0, 06%, 0.07%, 0.08%, 0.09%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1, 6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, or 2.5%, or a metal loading within a range bound by any two of the preceding values.
    [0031] In further aspects of the invention, the zeolite catalyst may include at least one trivalent metal ion in addition to one or more metals described above. As used herein, the term "trivalent metal ion" is defined as a trivalent metal ion other than aluminum (Al+3). Without wishing to be bound by any theory, it is believed that the trivalent metal is embedded in the zeolite structure. More specifically, the incorporated trivalent metal ion is believed to be bonded in the zeolite to an appropriate number of oxygen atoms, that is, as a metal oxide unit containing the metal cation connected to the structure via oxygen bridges. . In some embodiments, the presence of a trivalent metal ion in combination with one or more other catalytically active metal ions can cause a different combined effect than the cumulative effect of these ions when used alone. The effect primarily considered here is on the resulting catalyst's ability to convert alcohols to hydrocarbons.
    [0032] In some embodiments, only one type of trivalent metal ion apart from aluminum is incorporated into the zeolite. In other embodiments, at least two types of trivalent metal ions apart from aluminum are incorporated into the zeolite. In still other embodiments, at least three types of trivalent metal ions apart from aluminum are incorporated into the zeolite. In still other embodiments, precisely two or three types of trivalent metal ions apart from aluminum are incorporated in the zeolite.
    [0033] Each of the trivalent metal ions can be included in any suitable amount, such as precisely at least less than, or up to, for example, 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, or 2.5%, or an amount within a range bound by any two of the preceding values. Alternatively, the total of trivalent metal ions (other than Al) can be limited to any of the foregoing values. In some embodiments, one or more specific types, or all, trivalent metal ions other than Al are excluded from the catalyst.
    [0034] In a first set of embodiments, at least one trivalent metal ion is selected from trivalent transition metal ions. The one or more transition metals may be selected from any or a select portion of the following types of transition metals: elements from Groups IIIB (group Sc), IVB (group Ti), VB (group V), VIB (Cr group), VIIB (Mn group), VIIIB (Fe and Co groups) from the Periodic Table of the Elements. Some examples of trivalent transition metal ions include Sc+3, Y+3, V+3, Nb+3, Cr+3, Fe+3, and Co+3. In other embodiments, the trivalent metal ion excludes all transition metal ions, or alternatively excludes any one, two or more specific classes or examples of transition metal ions given above. In particular embodiments, trivalent transition metal ions include Sc+3, or Fe+3, or a combination thereof.
    [0035] In a second set of embodiments, at least one trivalent metal ion is selected from trivalent main group metal ions. The one or more main group metals may be selected from any or a select portion of Group IIIA (group B) and/or group VA (group N) elements of the Periodic Table, other than aluminum . Some examples of trivalent main group metal ions include Ga+3, In+3, As+3, Sb+3, and Bi+3. In other embodiments, the trivalent metal ion excludes all non-aluminium main group metal ions, or alternatively excludes any one, two or more specific classes or examples of main group metal ions given above. In particular embodiments, the trivalent main group metal ions include at least In3+.
    [0036] In a third set of embodiments, at least one trivalent metal ion is selected from trivalent lanthanide metal ions. Some examples of trivalent lanthanide metal ions considered here include La+3, Ce+3, Pr+3, Nd+3, Sm+3, Eu+3, Gd+3, Tb+3, Dy+3, Ho+ 3, Er+3, Tm+3, Yb+3, and Lu+3. In particular embodiments, the trivalent lanthanide metal ion is selected from one or a combination of La+3, Ce+3, Pr+3, and Nd+3. In further particular embodiments, the trivalent lanthanide metal ion is or includes La+3. In other embodiments, the trivalent metal ion excludes all lanthanide metal ions, or alternatively, excludes any one, two or more specific classes or examples of lanthanide metal ions provided above.
    [0037] In a fourth set of embodiments, the catalyst includes at least two trivalent metal ions selected from trivalent transition metal ions. Some combinations of trivalent transition metal ions considered here include Sc+3 in combination with one or more other trivalent transition metal ions, or Fe+3 in combination with one or more other trivalent transition metal ions, or Y+ 3 in combination with one or more other trivalent transition metal ions, or V+3 in combination with one or more other trivalent transition metal ions.
    [0038] In a fifth set of embodiments, the catalyst includes at least two trivalent metal ions selected from trivalent main group metal ions. Some combinations of trivalent main group metal ions considered here include In+3 in combination with one or more other trivalent main group metal ions, or Ga+3 in combination with one or more other trivalent main group metal ions, or As+3 in combination with one or more other trivalent main group metal ions.
    [0039] In a sixth set of embodiments, the catalyst includes at least two trivalent metal ions selected from trivalent lanthanide metal ions. Some combinations of trivalent lanthanide metal ions considered herein include La+3 in combination with one or more other trivalent lanthanide metal ions, or Ce+3 in combination with one or more other trivalent lanthanide metal ions, or Pr+ 3 in combination with one or more other trivalent lanthanide metal ions, or Nd+3 in combination with one or more other trivalent lanthanide metal ions.
    [0040] In a seventh set of embodiments, the catalyst includes at least one trivalent transition metal ion and at least one trivalent lanthanide metal ion. For example, in particular embodiments, at least one trivalent metal ion is selected from Sc+3, Fe+3, V+3, and/or Y+3, and another trivalent metal ion is selected from La +3, Ce+3, Pr+3, and/or Nd+3.
    [0041] In an eighth set of embodiments, the catalyst includes at least one trivalent transition metal ion and at least one trivalent headgroup metal ion. For example, in particular embodiments, at least one trivalent metal ion is selected from Sc+3, Fe+3, V+3, and/or Y+3, and another trivalent metal ion is selected from In +3, Ga+3, and/or In+3.
    [0042] In a ninth set of embodiments, the catalyst includes at least one trivalent headgroup metal ion and at least one trivalent lanthanide metal ion. For example, in particular embodiments, at least one trivalent metal ion is selected from In+3, Ga+3, and/or In+3, and another trivalent metal ion is selected from La+3, Ce +3, Pr+3, and/or Nd+3.
    [0043] In a tenth set of embodiments, the catalyst includes at least three trivalent metal ions. The at least three trivalent metal ions can be selected from trivalent transition metal ions, trivalent main group metal ions, and/or trivalent lanthanide metal ions.
    [0044] In particular embodiments, one, two, three, or more trivalent metal ions are selected from Sc+3, Fe+3, V+3, Y+3, La+3, Ce+3, Pr+ 3, Nd+3, In+3, and/or Ga+3. In more particular embodiments, one, two, three, or more trivalent metal ions are selected from Sc+3, Fe+3, V+3, La+3, and/or In+3.
    [0045] The zeolite catalyst described above is typically not covered with a metal-containing film or layer. However, the present invention also contemplates the zeolite catalyst described above covered with a metal-containing film or layer as long as the film or layer does not substantially prevent the catalyst from functioning effectively as a conversion catalyst, as intended herein. Being covered, the film or layer resides on the surface of the zeolite. In some embodiments, the zeolite surface refers only to the outer surface (ie, as defined by the outer contour area of the zeolite catalyst), while in other embodiments, the zeolite surface refers to or includes inner surfaces of the zeolite, such as the surfaces within pores or channels of the zeolite. The metal-containing film or layer can serve, for example, to adjust the physical characteristics of the catalyst, catalytic efficiency, or catalytic selectivity. Some examples of metal-containing surfaces include the oxides and/or sulfides of alkali metals, alkaline earth metals, and divalent main group or transition metals, provided such surface metals are non-contaminating to the hydrocarbon product and not harmful to the process of conversion.
    [0046] The catalyst described herein can be synthesized by any suitable method known in the art. The method considered here should preferably incorporate the metal ions homogeneously into the zeolite. The zeolite can be a single type of zeolite, or a combination of different zeolite materials.
    [0047] In particular embodiments, the catalyst described here is prepared by first impregnating the zeolite with the metals to be loaded. The impregnation step can be achieved, for example, by treating a zeolite with one or more solutions containing salts of the metals to be loaded. By treating a zeolite with the metal-containing solution, the metal-containing solution is contacted with a zeolite such that the solution is absorbed into the zeolite, preferably in the entire volume of the zeolite. Typically, by preparing the metal-loaded zeolite catalyst (eg, Cu-ZSM5 or V-ZSM-5), the acidic zeolite form (ie, H-ZSM5) or its ammonium salt (eg, NH4 -ZSM-5) is used as a starting material where an exchange with metal ions (eg copper ions) is performed. The details of such metal exchange processes are well known in the art.
    [0048] In one embodiment, the impregnation step is achieved by treating a zeolite with a solution containing all the metals to be loaded. In another embodiment, the impregnation step is achieved by treating a zeolite with two or more solutions, the different solutions containing different metals or combinations of metals. Each treatment of the zeolite with an impregnation solution corresponds to a separate impregnation step. Typically, when more than one impregnation step is employed, a drying and/or thermal treatment step is employed between the impregnation steps.
    [0049] The metal impregnation solution contains at least one or more metal ions to be loaded into the zeolite, as well as a liquid vehicle to distribute the metal ions into the zeolite. Metal ions are usually in the form of metal salts. Preferably, the metal salts are completely dissolved in the liquid vehicle. The metal salt contains one or more metal ions in ionic association with one or more counteranions. Any one or more of the metal ions described above can serve as the metal ion portion. The counteranion can be selected from, for example, halides (F-, Cl-, Br-, or I-), carboxylates (for example, formate, acetate, propionate, or butyrate), sulfate, nitrate, phosphate , chlorate, bromate, iodate, hydroxide, β-diketonate (eg, acetylacetonate), and dicarboxylates (eg, oxalate, malonate, or succinate).
    [0050] In particular embodiments, the catalyst is prepared by forming a slurry containing zeolite powder and the metals to be incorporated. The resulting mud is dried and burned to form a powder. The powder is then combined with organic and/or inorganic binders and wet mixed to form a paste. The resulting paste can be formed into any desired shape, for example, by extrusion into stick, honeycomb, or pinion shaped structures. The extruded structures are then dried and fired to form the final catalyst. In other embodiments, the zeolite powder, metals, and binders are all combined together to form a paste which is then extruded and fired.
    [0051] After impregnating the zeolite, a metal-laden zeolite is typically dried and/or subjected to a heat treatment step (eg a firing or calcining step). The heat treatment step functions to permanently incorporate the saturated metals into the zeolite, for example, by replacing Al+3 and/or Si+4 and forming metal oxide bonds within the zeolite material. In different embodiments, the heat treatment step can be carried out at a temperature of at least 100°C, 150°C, 200°C, 250°C, 300°C, 350°C, 400°C, 450°C, 500°C, 550°C, 600°C, 650°C, 700°C, 750°C or 800°C, or within a range in this particular, for a time period of, for example, 15 minutes, 30 minutes, 1 hour, 2 hours, 6 hours, 12 hours, 24 hours, 30 hours, 36 hours or 48 hours, or within a range in this particular. In some particular embodiments, the heat treatment step is conducted at a temperature of at least 500°C for a time period of at least two hours. In some embodiments, the heat treatment step includes a step of raising the temperature from a lower temperature to a higher temperature, and/or from a higher temperature to a lower temperature. For example, the heat treatment step can include a lift stage from 100-700°C, or vice versa, at a rate of 1, 2, 5 or 10°C/min.
    [0052] Generally, one or more heat treatment step(s) to produce the metal-loaded zeolite catalyst is (are) conducted under normal atmospheric pressure. However, in some modalities a high pressure (eg above 1 atm and up to 2, 5 or 10 atm) is employed, while in other modalities a reduced pressure (eg below 1, 0, 5 or 0.2 atm) is employed. In addition, although the heat treatment steps are generally conducted under a normal air atmosphere, in some embodiments an atmosphere of high oxygen, reduced oxygen, or an inert atmosphere is used. Some gases that may be included in the process atmosphere include, for example, oxygen, nitrogen, helium, argon, carbon dioxide, and mixtures thereof.
    [0053] Due to the provision of a more descriptive example, a Cu-ZSM-5 catalyst can be prepared as follows: 2.664 g of copper acetate hydrate (i.e. Cu(OAc)2^6H2O) is dissolved in 600 mL deionized water (0.015M), followed by addition of 10.005 g of H-ZSM-5 zeolite. The suspension is kept stirring for about two hours at 50°C. Cu-ZSM-5 (blue in color) is collected by filtration after cooling, washed with deionized water, and calcined in air at about 500°C (10°C/min) for four hours.
    [0054] The Cu-ZSM-5 precursor produced can also then be impregnated with another metal, such as iron. For example, Cu-Fe-ZSM-5 can be produced as follows: 5 g of Cu-ZSM-5 are suspended in an aqueous solution of 25 ml of 0.015M Fe(NO3)3, degassed with N2, and stirring is carried out. kept for about two hours at about 80°C. A brown solid is obtained after filtration, leaving a clear, colorless filtrate. The product is then calcined in air at about 500°C (2°C/min) for about two hours. The resulting Cu-Fe-ZSM-5 catalyst typically contains about 2.4% Cu and 0.3% Fe. Numerous other metals can be loaded into the zeolite by similar means to produce a variety of different metal loaded catalysts .
    [0055] Generally, the zeolite catalyst described herein is in the form of a powder. In a first set of embodiments, at least a portion, or all particles of the powder, are less than one micron in size (ie, nano-sized particles). The nanosize particles can have a particle size precisely of at least up to, or less than, for example, 1, 2, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100 , 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900 or 950 nanometers (nm), or a particle size within a range bounded by any two of the above values. In a second set of embodiments, at least a portion or all of the powder particles are at or above 1 micron in size. Microsize particles can have a particle size precisely of at least up to, or less than, for example, 1, 2, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90 or 100 microns (μm), or a particle size within a range bounded by any two of the above values. In some embodiments, single crystals or catalyst grains correspond to any of the sizes given above, while in other embodiments, catalyst crystals or grains are agglomerated to provide agglomerated crystallites or grains having any of the above exemplary dimensions.
    [0056] In other embodiments, the zeolite catalyst may be in the form of a film, a coating or a multiplicity of films or coatings. The thicknesses of the coatings or multiplicity of coatings can be, for example, 1, 2, 5, 10, 50 or 100 microns, or a range thereof, or thicknesses of up to 100 microns. In still other embodiments, the zeolite catalyst is in the form of a non-particulate (i.e., continuous) filler solid. In still other embodiments, the zeolite catalyst can be fibrous or in the form of a mesh.
    [0057] The catalyst likewise may be mixed with or attached to a support material suitable for operation in a catalytic converter. The support material can be a powder (e.g. having any of the above particle sizes), granular (e.g. 0.5mm or larger particle size), a filler material such as a flux-type honeycomb monolith total, a plate or multi-plate structure, or corrugated metal sheets. If a honeycomb structure is used, the honeycomb structure can contain any suitable cell density. For example, the honeycomb structure can be 100, 200, 300, 400, 500, 600, 700, 800 or 900 cells per square inch (cells/in2) (or from 62-140 cells/cm2) or larger. The support material is generally constructed of a refractory composition, such as those containing cordierite, mullite, alumina (eg, α-, β- or y-alumina) or zirconia, or a combination thereof. Honeycomb structures, in particular, are described in detail in, for example, U.S. Patents 5,314,665, 7,442,425 and 7,438,868, the contents of which are incorporated herein by reference in their entirety. When corrugated or other types of metal sheets are used, these can be laid in layers, one over the other with catalyst material supported over the sheets, such that passageways remain allowing the flow of fluid containing alcohol. Layered blades can be similarly formed into a structure, such as a cylinder, by winding the blades.
    [0058] In particular embodiments, the zeolite catalyst is or includes a pentasil-type composition loaded with any of the suitable metals described above. In more specific embodiments, the zeolite catalyst is, or includes, for example, copper-loaded ZSM5 (i.e., Cu-ZSM5), Fe-ZSM5, Cu,Fe-ZSM5, or a mixture of Cu-ZSM5 and Fe- ZSM5. In other embodiments, the zeolite catalyst is, or includes, for example, Cu-La-ZSM5, Fe-La-ZSM5, Fe-Cu-La-ZSM5, Cu-Sc-ZSM5 or Cu-In-ZSM5.
    [0059] The examples have been presented below for the purpose of illustration and to describe certain specific embodiments of the invention. However, the scope of this invention is not to be limited in any way by the examples presented herein. EXAMPLE 1 Cu-ZSM5 Catalyst Preparation
    [0060]NH4-ZSM-5 was purchased from Zeolyst International (CBV-2314) with a SiO2/Al2O3 ratio of 23 and used as received. Calcination of NH4-ZSM-5 at 500°C for four hours provided H-ZSM-5 in quantitative yield. A 2.664 g sample of commercially available Cu(OOCCH3)2.H2O was dissolved in 600 mL of deionized water to prepare a 22 mole solution. A 10.0 g sample of H-ZSM-5 was added to the copper acetate solution, and the suspension stirred at 50°C for two hours. A blue colored solid was collected by filtration after cooling and washed with deionized water, dried and calcined in air at 500°C for four hours to obtain Cu-ZSM-5. Elemental analysis shows 2.76% Cu and 3.31% Al in the sample. EXAMPLE 2 Fe-ZSM-5 Catalyst Preparation
    [0061] A 12 g sample of H-ZSM-5 was suspended in an aqueous solution of Fe(NO3)3 at 0.02 M degassed. The suspension was stirred at room temperature for 24 hours. A light pink solid was collected by filtration and washed with deionized water, dried, and calcined in air at 550°C for four hours to obtain 9.98 g of Fe-ZSM-5. Elemental analysis shows 776 ppm iron. EXAMPLE 3 CuFe-ZSM-5 Catalyst Preparation
    [0062] A 5 g sample of Cu-ZSM-5 was suspended in an aqueous solution of 25 mL of Fe(NO3)3 at 0.015 M, degassed with N2, and was kept under stirring for two hours at 80°C. A brown solid was collected from the reaction mixture by filtration while rejecting a clear, colorless filtrate. The powder was calcined in air at 500°C (2°C/min) for two hours to obtain a pale yellow powder of CuFe-ZSM-5. Elemental analyses: 2.39% Cu; 0.40% Fe; Al 2.97%. EXAMPLE 4 V-ZSM-5 Catalyst Preparation
    The starting material of NH4+-ZSM-5 (SiO2/Al2O3 = 23), as commercially obtained, was exchanged for ion with V(III)Cl3 in aqueous solution. Specifically, a 0.050 M solution of V(III)Cl3 was made by first dissolving 2.5 g of V(III)Cl3 in 320 mL of distilled water. Then 12.17 g of NH4+-ZSM-5 were added to the aqueous solution and heated to 80oC. After stirring for eight hours, the heterogeneous mixture was vacuum filtered, and the filtrate discarded. The initial solid product of light blue V-ZSM-5 was then calcined at 500°C for four hours, which resulted in a final light yellow solid product. EXAMPLE 5 Alcohol-to-Hydrocarbon Conversion Performance Using Cu-ZSM-5 Catalyst
    [0064] A catalytic reactor was charged with 1.0 g of Cu-ZSM-5 powder and heated at 500°C for four hours under a flow of dry helium. The catalyst was cooled to 400°C and 10% aqueous ethanol was introduced into the reactor using a syringe pump at a rate of 6.8 mL/hour. This corresponds to a net hourly space velocity (LHSV) of 2.5 h-1. Post-catalyst emissions were collected in a U-shaped tube immersed in liquid nitrogen. On heating the contents of the U-shaped tube, an aqueous emulsion was obtained. A sample of this emulsion was injected into a Gas Chromatography Mass Spectrometer (GCMS). The trace obtained from the GCMS is shown in FIG. 1(B). This is compared in FIG. 1 (A) with the emulsion trace obtained when pure ethanol was injected into the reactor charged with Cu-ZSM-5. A GCMS trace comparison of 10% aqueous and pure ethanol shows that aqueous dilution has no effect on the conversion or distribution of the product when the reaction is conducted under the conditions described above.
    The experiment was similarly conducted with a 12.5 h-1 LHSV for aqueous ethanol. As shown by FIG. 2, identical results were obtained in terms of quantitative conversion and product distribution. The wide peak between 2.5 and 12.5 minutes is due to water. Peaks appearing after 12.5 minutes were identified to be due to acetaldehyde, isobutane, 2-butene, acetone, 2-methylbutene, 2-methyl-2-butene, cis-1,2-dimethylcyclopropene, cyclopentane, 3.3 - dimethylcyclobutene, benzene, 4,4-dimethylcyclobutane, toluene, 1,3-dimethylbenzene, 1-ethyl-3-methylbenzene, 1,2,4-trimethylbenzene, and 1-ethyl-4-methyl-benzene. EXAMPLE 6 Alcohol-to-Hydrocarbon Conversion Performance Using V-ZSM-5 Catalyst
    [0066] A catalytic reactor was charged with 1.0 g of V-ZSM-5 powder and heated at 500°C for four hours under a flow of dry helium. The catalyst was cooled to 200°C, and pure ethanol was introduced into the reactor using a syringe pump at 5.0 mL/hour. This corresponds to an LHSV of 2.93 h-1. Post-catalyst emissions were analyzed by gas chromatography by on-line gas chromatography gradually increasing the temperature to 450°C. Data are shown in Figs. 3A and 3B. The results show that a reaction temperature of 275°C is ideal in this example for minimizing the ethylene by-product (designated as "C2") with negligible CO, which suggests a minimal level of product decomposition on the catalyst surface. The conversion of ethanol at 275°C as a function of space velocity was similarly monitored, and an LHSV of 2.93 h-1 was determined to be ideal for the same reasons.
    [0067]Catalytic emissions were collected in a cold trap immersed in liquid nitrogen. On heating, the hydrocarbon layer and aqueous layer were separated. As can be elucidated from the carbon distribution plot shown in FIG. 4A, the hydrocarbon produced from ethanol (designated as "C3-C16") was found to be a mixture of about 2.47% paraffins, 10.5% iso-paraffins, 9.65% olefins , 3.11% of naphthalenes, and 74.26% of aromatics. The average molecular weight of the hydrocarbon mixture was found to be 97.86, the average specific gravity 0.823, total hydrogen 10.5, and the carbon to hydrogen ratio 8.47. The calculated search and engine octane numbers were found to be 107.6 and 93.3 respectively. Fractional collection allowed the collection of blended raw materials at 160-300 °C suitable for blending with diesel or jet fuel. The carbon distribution is shown in FIG. 4B. The average molecular weight of the hydrocarbon mixture was found to be 129.97, the average specific gravity 0.88, total hydrogen 9.4, and the carbon to hydrogen ratio 9.63.
    [0068]The machine tests were conducted on a modified Sturman variable valve actuation machine with a ported fuel injection that can be heated using a direct injection gasoline supply system without consuming the test fuel. Test fuel or certification gasoline was then introduced, and performance data recorded, such as cylinder pressure and heat release rate as a function of crank angle, recorded. The parameters used for operating the machine on the present blended raw material were found to be identical to the parameters for operating the machine using certification gasoline.
    [0069] While it has been shown and described what is currently considered to be preferred embodiments of the invention, those skilled in the art may make various changes and modifications that remain within the scope of the invention defined by the appended claims.
    权利要求:
    Claims (24)
    [0001]
    1. Method of converting an alcohol to a hydrocarbon, CHARACTERIZED in that it comprises contacting said alcohol, as a component of an aqueous solution at a concentration of not more than about 20%, with a metal-laden zeolite catalyst. a temperature of at least 100°C and up to 550°C, wherein said alcohol can be produced by a fermentation process and is selected from ethanol, butanol, isobutanol, or a combination thereof, said metal is an ion of positively charged metal that is not a third line transition metal, and said metal-charged zeolite catalyst is catalytically active to convert said alcohol to said hydrocarbon.
    [0002]
    2. Method according to claim 1, CHARACTERIZED by the fact that said alcohol is comprised of ethanol.
    [0003]
    3. Method according to claim 1, CHARACTERIZED by the fact that said alcohol is a component of an aqueous solution in a concentration of no more than about 10%.
    [0004]
    4. Method according to claim 1, CHARACTERIZED by the fact that said alcohol is produced by a fermentation process, and optionally i) wherein said alcohol is a component of a fermentation stream when in contact with said metal-loaded zeolite catalyst, ii) wherein said fermentation process produces said alcohol from a biomass source, the biomass source optionally being comprised of lignocellulosic matter, or iii) wherein said fermentation process produces said alcohol from a plant-based source of sugars.
    [0005]
    5. Method according to claim 1, CHARACTERIZED by the fact that said temperature is at least 200°C and up to 500°C, wherein said temperature is at least 350°C and up to 500°C, wherein said temperature is at least 350°C and up to 450°C, or wherein said temperature is at least 375°C and up to 425°C.
    [0006]
    6. Method according to claim 1, CHARACTERIZED by the fact that said metal is selected from alkali metal, alkaline earth metal, copper, iron, vanadium, zinc, titanium, cadmium, gallium, indium, and combinations thereof, or wherein said metal is selected from copper, iron, and vanadium.
    [0007]
    7. The method of claim 1, CHARACTERIZED in that said zeolite is comprised of a pentasil zeolite, optionally wherein said pentasil zeolite is comprised of ZSM5.
    [0008]
    8. The method of claim 1, CHARACTERIZED by the fact that said metal-loaded zeolite catalyst is comprised of Cu-ZSM5, or V-ZSM5.
    [0009]
    9. Method according to claim 1, CHARACTERIZED by the fact that said hydrocarbon is a mixture of hydrocarbon compounds, wherein said mixture is useful as a fuel or as a raw material component of a fuel mixture .
    [0010]
    10. Method according to claim 9, CHARACTERIZED by the fact that said mixture of hydrocarbon compounds is comprised of hydrocarbon compounds containing at least four carbon atoms.
    [0011]
    11. Method according to claim 9, CHARACTERIZED by the fact that said mixture of hydrocarbon compounds substantially corresponds to a petrochemical fraction, optionally wherein said petrochemical fraction substantially corresponds to a fuel selected from gasoline, kerosene, diesel, and jet propellant, or optionally wherein said method further comprises distilling said mixture of hydrocarbon compounds to obtain a fraction of said mixture of hydrocarbon compounds.
    [0012]
    12. Method according to claim 1, CHARACTERIZED by the fact that said method is integrated with a fermentation process, wherein said fermentation process produces said alcohol as a component of a fermentation stream, and said fermentation stream is contacted with said metal-loaded zeolite catalyst.
    [0013]
    13. Method according to claim 1, CHARACTERIZED by the fact that said method is integrated with a biomass reactor that includes a fermentation process, wherein said fermentation process produces said alcohol as a component of a stream of fermentation, and said fermentation stream is contacted with said metal loaded zeolite catalyst.
    [0014]
    14. Method according to claim 1, CHARACTERIZED by the fact that said alcohol is produced from a source of biomass, optionally wherein said source of biomass is comprised of lignocellulosic matter, or optionally wherein said source of biomass is comprised of starch or sugar.
    [0015]
    15. Method according to claim 1, CHARACTERIZED by the fact that the alcohol is comprised of n-butanol or isobutanol.
    [0016]
    16. Method according to claim 1, CHARACTERIZED by the fact that said catalyst is a zeolite catalyst loaded with vanadium.
    [0017]
    17. Method for converting an alcohol into a hydrocarbon product comprising not more than 20% of C2 hydrocarbon compounds, CHARACTERIZED in that it comprises contacting said alcohol with a vanadium-loaded ZSM-5 zeolite catalyst at a flue temperature minus 250 °C and up to 350 °C and at a net hourly space velocity of up to 5 h-1, where said alcohol can be produced by a fermentation process and is selected from ethanol, butanol, isobutanol, or a combination thereof and is a component of an aqueous solution at a concentration of no more than about 20%.
    [0018]
    18. Method according to claim 17, CHARACTERIZED by the fact that said alcohol comprises ethanol.
    [0019]
    19. Method according to claim 17, CHARACTERIZED by the fact that said concentration is no more than about 10%.
    [0020]
    20. Method according to claim 17, CHARACTERIZED by the fact that said alcohol is produced by a fermentation process.
    [0021]
    21. Method for converting an alcohol into a mixture of hydrocarbon compounds useful as a fuel or as a raw material component of a fuel mixture, CHARACTERIZED in that it comprises contacting said alcohol with a charged zeolite catalyst with metal at a temperature of at least 100 °C and up to 550 °C, wherein said alcohol can be produced by a fermentation process and is selected from the group consisting of ethanol, butanol, isobutanol, and combinations thereof and is a component of an aqueous solution at a concentration of not more than about 20%, said metal is a positively charged metal ion, and said metal charged zeolite catalyst is catalytically active to convert said alcohol to said mixture of hydrocarbon compounds, wherein said mixture of hydrocarbon compounds contains hydrocarbon compounds containing at least four carbon atoms, and at least a portion of said hydrocarbon compounds containing at least four carbon atoms are alkanes, wherein said mixture of hydrocarbon compounds substantially corresponds to a fuel selected from gasoline, kerosene, diesel, and jet propellant.
    [0022]
    22. Method according to claim 21, CHARACTERIZED by the fact that said alcohol comprises ethanol.
    [0023]
    23. Method according to claim 21, CHARACTERIZED by the fact that said concentration is no more than about 10%.
    [0024]
    24. Method according to claim 21, CHARACTERIZED by the fact that said alcohol is produced by a fermentation process.
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    同族专利:
    公开号 | 公开日
    US20140100404A1|2014-04-10|
    MX348336B|2017-06-07|
    BR112013032184A2|2019-09-24|
    US9938467B2|2018-04-10|
    CN103827058B|2016-08-17|
    US20180187091A1|2018-07-05|
    EP2720990A4|2014-12-24|
    MX2013014804A|2014-06-04|
    WO2012174205A1|2012-12-20|
    EP2720990A1|2014-04-23|
    US20140273146A1|2014-09-18|
    CN103827058A|2014-05-28|
    US9533921B2|2017-01-03|
    CA2839399C|2021-03-23|
    EP2720990B1|2018-03-07|
    HUE037515T2|2018-09-28|
    US20170066974A1|2017-03-09|
    CA2839399A1|2012-12-20|
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    法律状态:
    2019-10-01| B08F| Application fees: application dismissed [chapter 8.6 patent gazette]|
    2019-12-10| B08G| Application fees: restoration [chapter 8.7 patent gazette]|
    2019-12-17| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2020-04-22| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-10-13| B15I| Others concerning applications: loss of priority|Free format text: PERDA DA PRIORIDADE US 61/497,256 DE 15/06/2011 REIVINDICADA NO PCT/US2012/042399 POR NAO ENVIO DE DOCUMENTO COMPROBATORIO DE CESSAO DA MESMA CONFORME AS DISPOSICOES PREVISTAS NA LEI 9.279 DE 14/05/1996 (LPI) ART. 166O, ITEM 27 DO ATO NORMATIVO 128/1997, ART. 28 DA RESOLUCAO INPI-PR 77/2013 E ART 3O DA IN 179 DE 21/02/2017 UMA VEZ QUE DEPOSITANTE CONSTANTE DA PETICAO DE REQUERIMENTO DO PEDIDO PCT E DISTINTO DAQUELE QUE DEPOSITOU A PRIORIDADE REIVINDICADA. |
    2020-11-17| B150| Others concerning applications: publication cancelled|Free format text: ANULADA A PUBLICACAO CODIGO 15.9 NA RPI NO 2597 DE 13/10/2020 POR TER SIDO INDEVIDA. |
    2021-03-23| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-05-25| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 14/06/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201161497256P| true| 2011-06-15|2011-06-15|
    US61/497,256|2011-06-15|
    PCT/US2012/042399|WO2012174205A1|2011-06-15|2012-06-14|Zeolitic catalytic conversion of alcohols to hydrocarbons|
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