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    Abstract Method for Converting Biomass to Chemicals and Fuels Derived from Biomass, Chemical Composition, Gasoline Composition, Kerosene Composition, and Diesel Composition The present invention provides methods, reactor systems and catalysts for converting biomass into fuels in a continuous process. and chemicals. The invention includes methods for converting water-insoluble components of biomass such as hemicellulose, cellulose and lignin to volatile c2 + o1-2 oxygenates such as alcohols, ketones, cyclic ethers, esters, carboxylic acids, aldehydes and mixtures thereof. In certain applications, volatile c2 + o1-2 oxygenates may be collected and used as a final chemical or used in downstream processes to produce liquid fuels, chemicals and other products.
    公开号:BR112013029901B1
    申请号:R112013029901-0
    申请日:2012-05-23
    公开日:2019-10-15
    发明作者:Ming Qiao；Elizabeth M. Woods；Paul Myren；Randy D. Cortright；John Kania
    申请人:Virent, Inc.；
    IPC主号:
    专利说明:

    The present invention is directed to catalysts and methods for converting biomass into liquid fuels and chemicals.
    BACKGROUND OF THE INVENTION
    The rising cost of fossil fuel and environmental concerns have sparked worldwide interest in the development of alternatives to petroleum-based fuels, chemicals and other products. Biomass materials are a possible renewable alternative to petroleum-based fuels and chemicals.
    Lignocellulosic biomass includes three main components. Cellulose, a primary sugar source for the bioconversion process, includes high molecular weight polymers formed from tightly bound glucose monomers. Hemicellulose, a secondary sugar source, includes shorter polymers formed from various sugars. Lignin includes chemical portions of phenylpropanoic acid polymerized in a complex three-dimensional structure. The composition
    2/92 resulting from lignocellulosic biomass is approximately 40 to 50% cellulose, 20 to 25% hemicellulose and 25 to 35% lignin, in percentage by weight.
    There are very few cost-effective processes for effectively converting cellulose, hemicellulose and lignin into more suitable components for producing fuels, chemicals and other products. This is generally due to the fact that each of lignin, cellulose and hemicellulose requires different processing conditions, such as temperature, pressure, catalysts, reaction time, etc., in order to effectively break its polymeric structure. Because of this distinction, most processes are only able to convert specific fractions of the biomass, such as cellulose and hemicellulose, leaving the remaining fractions behind for further processing or alternative uses.
    The extraction with hot water of hemicellulose from biomass, for example, has been well documented. The sugars produced by extraction with hot water are, however, unstable at high temperatures, leading to unwanted decomposition products. Therefore, the temperature of the water used for hot water extraction is limited, which can reduce the efficiency of hot water extraction.
    Studies have also shown that it is possible to convert microcrystalline cellulose (MCC) to polyols using hot compressed water and a hydrogenation catalyst (Fukuoka & Dhepe, 2006; Luo et al., 2007; and Yan et al., 2006). Typical hydrogenation catalysts include ruthenium or platinum supported on carbon or aluminum oxide. However, these studies also show that only low levels of MCC are converted with these catalysts and the selectivity towards the desired sugar alcohols is low.
    3/92
    APR and HDO are catalytic reform processes that have recently been shown to be promising technologies for generating hydrogen, oxygen, hydrocarbons, fuels and chemicals from oxygenated compounds derived from a wide array of biomass. Oxygenated hydrocarbons include starches, mono- and polysaccharides, sugars, sugar alcohols, etc. Various APR methods and techniques are described in US Patent Nos . : 6,699,457; 6,964,757; 6,964,758; and 7,618,612 (all to Cortright et al., and entitled LowTemperature Hydrogen Production from Oxygenated Hydrocarbons ”); :: US Patent No. 6,953,873 (. Everyone to Cortright et al and entitled Low-Temperature Hydrocarbon Production from Oxygenated Hydrocarbons "); :: US Patent Nos 7,767,867; 7,989,664; and Patent Publication n :: US 2011/0306804 (to Cortright and entitled Methods and Systems for Generating Polyols ”). Various APR methods and techniques are described in , and HDO :: US Patent Nos 8,053,615; 8,017,818; 7,977,517; and Patent Publications n :: US 2011/0257448; 2011/0245543; 2011/0257416; and 2011/0245542 (all to Cortright and Blommel and entitled Synthesis of Liquid Fuels and Chemicals from Oxygenated Hydrocarbons ”); Patent Publication n :: US 2009/0211942 (Cortright and entitled Catalysts and Methods for Reforming Oxygenated Compounds ”); Patent Publication No. US 2010/0076233 ( a . Cortright et al and entitled Synthesis of Liquid Fuels from Biomass "); International Patent Application No. PCT / US2008 / 056330 (to Cortright and Blommel entitled Synthesis of Liquid Fuels and Chemicals from Oxygenated Hydrocarbons "); and International Patent Application No copending commonly owned PCT / US2006 / 048030 (to Cortright et al., entitled Catalyst and Methods for Reforming Oxygenated Compounds "), all of which are incorporated herein by reference.
    A disadvantage of catalytic technologies is that
    4/92 possible negative effects of water, contaminants and other waste products on catalyst performance. For example, the components of ash (for example, calcium, aluminum, potassium, sodium, magnesium, ammonium, chloride, sulfate, sulfite, thiol, silica, copper, iron, phosphate, carbonate and phosphorus), colored bodies (for example, terpenoids, stilbenes and flavonoids), proteinaceous materials and other inorganic or organic biomass conversion products can interact with the catalyst to severely limit its activity. More complex polysaccharides, such as raw cellulose and hemicellulose, as well as lignin and its complex breakdown products, have also proved difficult to convert due to their size and inability to interact with the catalyst. Thus, a process for generating fuels and chemicals and other hydrocarbons and oxygenated hydrocarbons from more complex biomass components could be beneficial. It could also be beneficial to improve the effectiveness of such a process to minimize the number of reaction steps, and thus reactors, needed to carry out the conversion process.
    SUMMARY
    The invention provides methods for producing chemicals and fuels derived from biomass. The method generally involves: (1) providing a biomass feed stream comprising a solvent and a biomass component comprising cellulose, hemicellulose or lignin; (2) catalytically reacting the biomass feed stream with hydrogen and a deconstruction catalyst at a deconstruction temperature and a deconstruction pressure to produce a product stream comprising a vapor phase, a liquid phase and a solid phase, in that the vapor phase comprises one or more volatile C2 + O1-2 oxygenates, wherein the liquid phase comprises
    5/92 water and one or more oxygenated hydrocarbons C 2+ O 2+ and where the solid phase comprises extractants; (3) separate the volatile C 2+ O 1-2 oxygenates from the liquid and solid phases; and (4) reacting the volatile C2 + O1-2 oxygenates catalytically in the presence of a condensation catalyst at a condensing temperature and condensing pressure to produce a C4 + compound comprising a member selected from the group consisting of C4 + alcohol , C4 + ketone, C4 + alkane, C4 + alkene, C5 + cycloalkane, C5 + cycloalkene, aryl, fused aryl and a mixture thereof. In one embodiment, the deconstruction temperature is between about 120 ° C to 350 ° C. In another embodiment, the deconstruction pressure is between about 2.06 MPa (300 psi) to 17.23 MPa (2,500 psi).
    One aspect of the invention is the composition of the solvent. In one embodiment, the solvent includes one or more members selected from the group consisting of water, oxygenated C 2+ O 2+ hydrocarbons generated in situ, recycled oxygenated C2 + O2 + hydrocarbons, biohazard solvents, organic solvents, organic acids and a mixture of them.
    In another modality, the biomass component comprises at least one selected member of the group that includes recycled fibers, crop residues of corn, bagasse, yellow millet, miscellaneous, sorghum, wood, wood waste, agricultural waste, algae and urban waste.
    The deconstruction catalyst may comprise an acid or basic support, or a support and a member selected from the group consisting of Ru, Co, Rh, Pd, Ni, Mo and alloys thereof. In another embodiment, the deconstruction catalyst may also comprise a selected member
    from the group consisting of Pt, Re, Faith, Go, Cu, Mn, Cr, Mo, B, W, V, Nb, Ta, Ti, Zr, Y, There, Sc, Zn, CD, Ag, Au, Sn, Ge, P, Al, Ga, In, Tl and alloys From themselves. In yet another
    6/92 modality, the support comprises a member selected from the group consisting of a nitride, carbon, silica, alumina, zirconia, titania, vanádia, ceria, boron nitride, heteropoly acid, diatomite, hydroxypatite, zinc oxide, chromium , zeolites, tungstated zirconia, titania-zirconia, sulfated zirconia, phosphate zirconia, acid alumina, silica-alumina, sulfated alumina, phosphate alumina and mixtures thereof. In an additional embodiment, the support is modified by treating the support with a modifier selected from the group consisting of tungsten, titania, sulfate, phosphate or silica.
    Another aspect of the invention is a solid phase. In one embodiment, the solid phase further comprises the deconstruction catalyst. In another modality, the deconstruction catalyst is separated from the liquid phase; washed in one or more washing medium; regenerated in the presence of oxygen or hydrogen, at a regeneration pressure and a regeneration temperature at which carbonaceous deposits are removed from the deconstruction catalyst; and then reintroduced to react with the biomass feed stream.
    In one embodiment, the washing medium comprises a liquid selected from the group consisting of water, an acid, the base, a chelating agent, alcohols, ketones, cyclic ethers, hydroxy ketones, aromatics, alkanes and combinations thereof. In another embodiment, washing the deconstruction catalyst comprises a first step of washing the deconstruction catalysts with a first washing solvent and a second step of washing the deconstruction catalyst with a second washing solvent. In another embodiment, the first washing solvent comprises a liquid selected from the group consisting of water, an acid, a base, a chelating agent and combinations thereof and the second washing solvent
    7/92 comprises a liquid selected from the group consisting of alcohols, ketones, cyclic ethers, hydroxy ketones, aromatics, alkanes and combinations thereof. In another embodiment, the first washing solvent comprises a liquid selected from the group consisting of alcohols, ketones, cyclic ethers, hydroxy ketones, aromatics, alkanes and combinations thereof and the second washing solvent comprises a liquid selected from group consisting of water, an acid, a base, a chelating agent and combinations thereof.
    In one embodiment, the deconstruction catalyst is regenerated at a temperature in the range of about 120 ° C to about 450 ° C and is adjusted at a rate of about 20 ° C per hour to about 60 ° C per hour . In another embodiment, the regeneration of the deconstruction catalyst further comprises providing a gas stream comprising an inert gas and oxygen, the inert gas is supplied at a gas flow between 600 to 1,200 ml of gas / ml of catalyst per hour and the oxygen is supplied at a concentration of 0.5 to 10% of the gas stream. In another modality, regeneration results in the removal of more than 90% of the carbonaceous deposits from the deconstruction catalyst.
    The catalytic reaction of volatile C2 + O1-2 oxygenates occurs in the presence of a condensation catalyst. In one embodiment, the condensation catalyst comprises a metal
    selected from of the group consisting of Cu, Ag, Au, Pt, Ni, Faith, Co, Ru, Zn, CD, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, The, a league From even if a combination From themselves.
    In another embodiment, the condensation catalyst further comprises a modifier selected from the group consisting of Ce, La, Y, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, P, B, Bi and a combination of them. In another modality, the condensation catalyst comprises a member selected from
    8/92 from the group consisting of acidic alumina, aluminum phosphate, silica-alumina phosphate, amorphous silica-alumina, sulfated alumina, theta-alumina, aluminosilicate, zeolites, zirconia, sulfated zirconia, tungsten zirconia, titaniazirconia, zirconia phosphate, tungsten carbide, molybdenum carbide, titania, sulfated carbon, phosphate carbon, phosphate silica, phosphate alumina, acid resin, heteropoly acid, inorganic acid, and a combination thereof.
    The catalytic reaction of volatile C 2+ O 1-2 oxygen in the presence of a condensation catalyst produces a C 4+ compound. In one embodiment, the compound C 4+ is benzene, toluene or xylene.
    The biomass feed stream is reacted catalytically with the deconstruction catalyst in the presence of hydrogen. In one embodiment, hydrogen is selected from the group consisting of external hydrogen, recycled hydrogen or hydrogen generated in situ. In another modality, the hydrogen generated in situ is derived from oxygenated hydrocarbons C2 + O2 +.
    The invention also provides a method for generating a product mixture that comprises two or more C4 + compounds. The method generally involves: (1) providing a biomass feed stream comprising a solvent and a biomass component comprising cellulose, hemicellulose or lignin; (2) catalytically reacting the biomass feed stream with hydrogen and a deconstruction catalyst at a deconstruction temperature and a deconstruction pressure to produce a product stream comprising a vapor phase, a liquid phase and a solid phase, in that the vapor phase comprises one or more volatile C2 + O1-2 oxygenates, where the liquid phase comprises water and one or more oxygenated C2 + O2 + hydrocarbons and where the
    9/92 solid phase comprises extractants; (3) separate the volatile C 2+ O 1-2 oxygenates from the liquid and solid phases; (4) reacting catalytically volatile C 2+ O 1-2 oxygenates in the presence of a condensation catalyst at a condensing temperature and condensing pressure to produce a product mixture comprising two or more C4 + compounds selected from the group that consists of a C4 + alcohol, a C4 + ketone, a C4 + alkane, a C4 + alkene, a C5 + cycloalkane, a C5 + cycloalkene, an aryl and a fused aryl; and (5) distilling the product mixture to provide a composition selected from the group consisting of an aromatic fraction, a gasoline fraction, a kerosene fraction and a diesel fraction.
    In one embodiment, the aromatic fraction comprises benzene, toluene or xylene. In another modality, the gasoline fraction has a final boiling point in the range of 150 ° C to 220 ° C, a density at 15 ° C in the range of 700 to 890 kg / m 3 , a RON in the range of 80 to 110 and a MON in the range of 70 to 100. In another modality, the kerosene fraction has an initial boiling point in the range of 120 ° C to 215 ° C, a final boiling point in the range of 220 ° C to 320 ° C, a density at 15 ° C in the range of 700 to 890 kg / m 3 , a freezing point of -40 ° C or less, a smoke point of at least 18 mm, and a viscosity at -20 ° C in range from 1 to 10 mm 2 / s (1 to 10 cSt). And in another mode, the diesel fraction has a T95 in the range of 220 ° C to 380 ° C, a flash point in the range of 30 ° C to 70 ° C, a density at 15 ° C in the range of 700 to 900 kg / m 3 and a viscosity at 40 ° C in the range of 0.5 to 6 mm2 / s (0.5 to 6 cSt).
    The invention also provides a method for generating C 4+ compounds from a biomass feed stream comprising cellulose, hemicellulose and lignin. The method generally involves: (1) providing a supply current of
    10/92 biomass comprising a solvent and a biomass component, wherein the solvent comprises one or more members selected from the group consisting of water, oxygenated hydrocarbons C 2+ O 2+ generated in situ, oxygenated hydrocarbons C2 + O2 + recycled materials, biohazard solvents, organic solvents, organic acids and a mixture thereof and in which the biomass component comprises cellulose, hemicellulose and lignin; (2) catalytically reacting the biomass feed stream with hydrogen and a deconstruction catalyst at a deconstruction temperature and a deconstruction pressure to produce a product stream comprising a vapor phase, a liquid phase and a solid phase, in that the vapor phase comprises one or more volatile C2 + O1-2 oxygenates, where the liquid phase comprises water and one or more oxygenated C2 + O2 + hydrocarbons, where the solid phase comprises extractants and where the deconstruction catalyst comprises a support and a first member selected from the group consisting of Ru, Co, Rh, Pd, Ni, Mo and alloys thereof and at least one additional member selected from the group consisting of Pt, Re, Fe, Ir, Cu, Mn, Cr, Mo, B, W, V, Nb, Ta, Ti, Zr, Y, La, Sc, Zn, Cd, Ag, Au, Sn, Ge, P, Al, Ga, In, Tl, and alloys thereof; (3) separate the volatile C2 + O1-2 oxygenates from the liquid and solid phases; and (4) reacting catalytically volatile C 2+ O 1 2 oxygenates in the presence of a condensation catalyst at a condensing temperature and condensing pressure to produce a C4 + compound comprising a member
    selected from the group consisting of alcohol C4 +, ketone C4 +, C4 + alkane, C4 + alkene, cycloalkane C5 +, cycloalkene C5 +, aryl, arila fused and a mixture From themselves.Other aspects gives invention include: (1) an
    11/92 chemical composition comprising a C 4+ compound derived from any of the foregoing methods; (2) a chemical composition comprising a C 4+ compound derived from any of the foregoing methods, wherein the C 4+ compound is benzene, toluene or xylene; (3) a chemical composition that comprises a fraction of gasoline derived from any of the previous methods; (4) a chemical composition comprising a fraction of kerosene derived from any of the foregoing methods; and (5) a chemical composition comprising a fraction of diesel derived from any of the previous methods.
    DESCRIPTION OF THE DRAWINGS
    Figure 1 is a flow chart illustrating an embodiment of the present invention.
    Figure 2 is an illustration of an exemplary reaction path for the conversion of biomass according to the present invention.
    Figure 3 is a graph that provides data for converting a biomass feed stream containing microcrystalline cellulose (MCC) according to the present invention.
    Figures 4a and 4b are graphs that provide the most abundant aqueous product speciation and distribution of the identified aqueous product, respectively, from the conversion of a biomass feed stream containing MCC according to the present invention.
    Figure 5 is a graph that provides the distribution of aqueous oxygenate identified from the conversion of a biomass feed stream containing MCC according to the present invention.
    Figure 6 is a graph showing the distribution of the condensable organic vapor phase derived from the conversion of a biomass feed stream containing MCC of
    12/92 according to the present invention.
    Figure 7 is a graph illustrating the analysis of non-condensable aqueous products from the conversion of a biomass feed stream containing MCC according to the present invention.
    Figure 8 is a graph that provides data for converting a biomass feed stream containing pine wood according to the present invention.
    Figures 9a and 9b are graphs that provide the most abundant aqueous product speciation and the distribution of the identified aqueous product, respectively, from the conversion of a biomass feed stream containing pine wood according to the present invention.
    Figure 10 is a graph that provides the distribution of aqueous oxygen identified by converting a biomass feed stream containing pine wood according to the present invention.
    Figure 11 is a graph illustrating the analysis of non-condensable aqueous products from the conversion of a biomass feed stream containing pine wood according to the present invention.
    Figure 12 is a process flow chart that illustrates one of several configurations for conducting the condensation reactions according to the present invention.
    Figure 13 is a graph that provides product yields from the conversion of volatile C2 + O1-2 oxygenates over a Pd: Ag condensation catalyst.
    Figure 14 is a graph that provides the distillation curve for the gasoline fraction derived from the conversion of volatile C2 + O1-2 oxygenates over a Pd: Ag condensation catalyst.
    Figure 15 is a graph that provides the distillation curve for the kerosene fraction derived from the
    13/92 conversion of volatile C 2+ O 1 _ 2 oxygenates over a Pd: Ag.
    Figure 16 is a graph that provides the distillation curve for the fraction of diesel derived from the conversion of volatile C 2+ O 1-2 oxygenates over a Pd: Ag condensation catalyst.
    Figure 17 is a graph that provides the total organic carbon (TOC) in the liquid phase from the conversion of a biomass feed stream containing crop residues of recycled corn according to the present invention.
    Figure 18 is a graph that provides the distribution of identified aqueous product of the volatile and background product from the conversion of a biomass feed stream containing crop residues of recycled corn according to the present invention.
    Figure 19 is a graph that provides the TOC from the conversion of a biomass feed stream containing crop residues of corn recycled in accordance with the present invention.
    Figure 20 is a graph which provides the distribution of the identified aqueous product of the volatile and background products from the conversion of a biomass feed stream containing corn residues with liquid phase recycling according to the present invention.
    Figure 21 is a graph that provides the most abundant aqueous product speciation from the conversion of a biomass feed stream that contains corn remnants with liquid phase recycling according to the present invention.
    Figure 22 is a graph that provides identified condensable organic products present in the vapor phase from the deconstruction of a
    14/92 biomass feed containing maize crop remnants according to the present invention.
    Figure 23 is a graph that provides the distribution of aqueous product identified from the deconstruction of a biomass feed stream containing MCC under two different processing conditions according to the present invention.
    Figure 24 is a graph that provides the most abundant aqueous product speciation from the deconstruction of a biomass feed stream containing MCC under two different processing conditions according to the present invention.
    Figure 25 is a flow chart illustrating an embodiment of the present invention.
    Figure 26 is a process flow chart illustrating one of several process configurations for conducting condensation reactions to produce aromatics in accordance with the present invention.
    Figure 27 is a graph that provides the distribution of number of carbons for aromatics produced from the deconstruction of a biomass feed stream containing MCC according to the present invention.
    Figure 28 is a graph that provides conversion data for three biomass feed streams according to the present invention.
    Figure 29 is a graph that provides the distribution of the aqueous product identified for the conversion of a biomass feed stream containing pine wood under different conditions according to the present invention.
    Figure 30 is a graph that provides the distribution of aqueous product identified for the conversion of a biomass feed stream that contains maize crop remnants under different conditions according to
    15/92 the present invention.
    Figure 31 is a graph that provides the distribution of the aqueous product identified for the conversion of a biomass feed stream containing bagasse under different conditions according to the present invention.
    Figure 32 is a graph that provides representative condensable organic products present in the vapor phase from the deconstruction of a biomass feed stream according to the present invention.
    Figure 33 is a graph that provides conversion data for a biomass feed stream containing bagasse with the use of various deconstruction catalysts according to the present invention.
    Figure 34 is a graph that provides the distribution of the aqueous liquid phase product identified for the deconstruction of a biomass feed stream containing bagasse with the use of various deconstruction catalysts according to the present invention.
    Figure 35 is a graph that provides the distribution of the identified aqueous condensable product present in the vapor phase for the deconstruction of a biomass feed stream containing bagasse with the use of various deconstruction catalysts according to the present invention.
    Figure 36 is a graph that provides the distribution of representative aqueous condensable product present in the vapor phase from the deconstruction of a bagasse containing biomass feed stream using various deconstruction catalysts according to the present invention.
    DETAILED DESCRIPTION OF THE INVENTION
    The present invention relates to methods, reactor systems and catalysts for converting biomass into
    16/92 liquid fuels and chemicals in a batch and / or continuous process. The invention includes methods for converting both water-insoluble and water-soluble components of biomass into volatile oxygenated hydrocarbons, such as C2 + O1-2 alcohols, ketones, cyclic ethers, esters, carboxylic acids, aldehydes and mixtures thereof. In certain applications, volatile oxygenated hydrocarbons can be collected and used as a final chemical, or used in downstream processes to produce liquid fuels, chemicals and other products.
    As used in this document, the term biomass refers to, without limitation, organic materials produced by plants (for example, wood, leaves, roots, seeds, stems, etc.) and microbial and animal metabolic waste. Common sources of biomass include: (1) agricultural residues, such as corn stalks, straw, seed husks, leftover sugar cane, bagasse, nut shells and livestock manure, poultry and pigs; (2) wood materials, such as wood or cork, sawdust, pieces of wood and ground cuts; (3) urban waste, such as used paper and garden clippings; (4) energy crops, such as poplar, willows, yellow millet, miscellaneous, sorghum, alfalfa, blue pasture, corn, soybeans and the like; (5) residual solids from industrial processes, such as lignin from pulp processes, acid hydrolysis or enzymatic hydrolysis; and (6) algae-derived biomass, including carbohydrates and lipids from microalgae (for example, Botryococcus braunii, Chlorella, Dunaliella tertiolecta, Gracilaria, Pleurochyrsis carterae and Sargassum) and macroalgae (for example, seagrass). The term refers to the primary building blocks of the previous one, that is, lignin, cellulose, hemicellulose and carbohydrates, such as saccharides, sugars and starches, among others.
    As used herein, the term
    17/92 bioreactor refers to, without limitation, processes for catalytically converting biomass into hydrocarbons of lower molecular weight and oxygenated compounds, such as alcohols, ketones, cyclic ethers, esters, carboxylic acids, aldehydes, diols and other polyols, with the use of heterogeneous catalysts. Biorformation also includes the additional catalytic conversion of such oxygenated compounds of lower molecular weight to C4 + compounds.
    The deconstruction catalysts used in this document demonstrate increased tolerance to conditions and species that are typically deleterious to catalytic activity. These species may include ash components (for example, calcium, aluminum, potassium, sodium, magnesium, ammonium, chloride, sulfate, sulfite, thiol, silica, copper, iron, phosphate, carbonate and phosphorus), colored bodies (for example, terpenoids, stilbenes and flavonoids), proteinaceous materials and other inorganic or organic products. In combination with the solvents and reactor conditions described in this document, deconstruction catalysts also demonstrate increased activity for converting more complex polysaccharides, such as raw cellulose and hemicellulose, as well as lignin and their complex degradation products.
    In the present invention, the main components of biomass (lignin, cellulose and hemicellulose) are converted into volatile oxygenated hydrocarbons (referred to in this document as volatile oxygenates and / or C2 + O1-2 oxygenates) with the use of hydrogen, a solvent and a heterogeneous deconstruction catalyst in a continuous process. An exemplary embodiment of the present invention is illustrated in Figure 1. A biomass feed stream is created by combining solid biomass that has been cut, fragmented, pressed, crushed or processed to a size
    18/92 suitable for conversion, with a solvent (eg water, oxygenated C 2+ O 2+ hydrocarbons generated in situ, recycled oxygenated C 2+ O 2+ hydrocarbons, bio-reform solvents, organic solvents, organic acids and mixtures of themselves). The supply current is then passed through a reactor in which it reacts with hydrogen and the deconstruction catalyst at a deconstruction temperature and a deconstruction pressure to cause a reaction that converts all or at least a portion of the lignin, cellulose and hemicellulose into the biomass. in a product stream that includes a vapor phase that contains one or more volatile oxygenates, a liquid phase that contains a solution or mixture of oxygenated hydrocarbons, and a solid phase that contains extractants and, in certain applications, unreacted and sub- reacted and / or deconstruction catalyst.
    Alternatively, a biomass feed stream is created by adding solid biomass that has been cut, fragmented, pressed, crushed or processed in a size suitable for conversion, to a reactor that contains a solvent, that is, in a non-paste form. fluid. The solvent (eg water, oxygenated C2 + O2 + hydrocarbons generated in situ, recycled oxygenated C2 + O2 + hydrocarbons, bio-reform solvents, organic solvents, organic acids or mixtures thereof) interacts with the solid biomass, thus making it accessible for solid biomass. the reaction with hydrogen and the deconstruction catalyst at a deconstruction temperature and a deconstruction pressure. The reaction converts all or at least a portion of the lignin, cellulose and hemicellulose in the biomass into a product stream that includes a vapor phase that contains one or more volatile oxinates, a liquid phase that contains a solution or mixture of C2 + O2 + hydrocarbons oxygenated (a portion of which serves as the solvent) and a solid phase containing
    19/92 extractants and, in certain applications, unreacted or underreacted biomass and / or the deconstruction catalyst.
    In a liquefaction reactor, as shown in Figure 1, the biomass (for example, solid biomass or biomass slurry) is initially deconstructed to produce a solution and / or mixture of oxygenated hydrocarbons, such as hemicellulose, cellulose, polysaccharides, oligosaccharides , sugars, sugar alcohols, sugar degradation products, depolymerized lignin compounds and the like. As these components are exposed to the deconstruction and hydrogen catalyst, the oxygen content of the compounds is reduced (see Figure 2) to supply both volatile oxygen and oxygenated C2 + O2 + hydrocarbons. The oxygenated hydrocarbons C 2+ O 2+ form a solvent generated in situ inside the reactor which, in turn: 1) accentuates the deconstruction of biomass, 2) improves the solubility of deconstructed biomass components - particularly components derived from lignin - to facilitate the reaction with the catalyst and 3) it is further deoxygenated to produce the desired volatile oxinates. The volatile oxygenates then leave the deconstruction reactor as a condensable vapor product for further processing or use in industrial chemicals. Residual oxygenated hydrocarbons can also leave the deconstruction reactor as a liquid phase and be recycled back to the reactor for further conversion and / or use as a solvent or separated for further processing or use as industrial chemicals.
    The composition of the product stream phases will vary depending on the process conditions and the particular type of biomass raw material used. The vapor phase will generally contain volatile oxygen, hydrogen,
    20/92 carbon monoxide, carbon dioxide and light alkanes. As used herein, volatile oxygenates refer to oxygenated hydrocarbons that have a relative volatility (a) to 1-hexanol greater than 0.03 based on pure components at 250 ° C. Volatile oxygenates will generally include monooxygenated hydrocarbons and oxygenated hydrocarbons (collectively referred to herein as C2 + O1-2 oxygenates), as well as residual oxygenated compounds that can be volatilized based on temperature, total pressure and concentration of the compounds. Monooxygenated hydrocarbons in general refer to hydrocarbon compounds that have 2 or more carbon atoms and 1 oxygen atom (referred to herein as C2 + O1 hydrocarbons), such as alcohols, ketones, aldehydes, ethers, cyclic ethers and furans. Dioxigenated hydrocarbons in general refer to hydrocarbon compounds that have 2 or more carbon atoms and 2 oxygen atoms (referred to herein as C2 + O2 hydrocarbons) and may include, without limitation, diols, dioxinated ketones and organic acids . Residual oxygenated compounds can include components that contain three or more oxygen atoms, such as glycerol, which are volatilized due to processing conditions and their concentration in the reaction stream.
    Volatile oxygenates will generally have more than 2 or more than 3 carbon atoms and less than 10 or less than 6 carbon atoms. Preferably, volatile oxygenates have 2 to 10 carbon atoms or 2 to 6 carbon atoms or 3 to 6 carbon atoms. Volatile oxygenates that are alcohols may include, without limitation, primary, secondary, linear, branched or cyclic C2 + alcohols, such as ethanol, n-propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, butanol, pentanol,
    21/92 cyclopentanol, hexanol, cyclohexanol, methyl-cyclohexanol, ethyl-cyclohexanol, propyl-cyclohexanol, 2-methylcyclopentanonol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol and isomers thereof. Alcohols can also include phenols and phenols substituted by alkyl, such as methyl, ethyl and propyl phenols and ortho, meta, para-cresols. Volatile ketone oxygenates can include, without limitation, cyclic ketones, aromatic ketones, acetone, propanone, butanone, pentanone, cyclopentanone, hexanone, cyclohexanone, acetophenone, 2-methyl-cyclopentanone, heptanone, octanone, nonanone, decanone, undecan, undecan, undecan and isomers thereof, as well as oxygenated ketones, such as hydroxy ketones, diketones, butane-2,3dione, 3-hydroxybutan-2-one, pentane-2,3-dione, pentane-2,4dione, 2-oxopropanal, methylglyoxal, butanedione, pentanedione, dicetohexane and isomers thereof. Aldehydes may include, without limitation, pentanal, acetaldehyde, hydroxyaldehydes, propionaldehyde, butyraldehyde, hexanal, heptanal, octanal, nonal, decanal, undecanal, dodecanal and isomers thereof. Ethers may include, without limitation, ethers, such as diethyl ether, diisopropyl ether, 2-ethylhexyl ether, methyl ethyl ether, ethyl propyl ether and methyl propyl ether. Cyclic ethers may include, without limitation, tetrahydrofuran, 2-methyl-tetrahydrofuran, 2,5-dimethyl-tetrahydrofuran, 2-ethyl-tetrahydrofuran, and isomers thereof, as well as dioxigenicated cyclic ethers, such as 3-hydroxytetrahydrofuran, tetrahydro-3- furanol, tetrahydrofurfuryl alcohol, 1- (2-furyl) ethanol, furan, dihydrofuran, 2-furan methanol, 2-methyl furan, 2-ethyl furan, 2,5-dimethyl furan and isomers thereof. Light carboxylic acids can include, without limitation, formic acid, acetic acid and propionic acid. Volatile oxygenates can also include small amounts of the acids
    22/92 heavy organics, diols, triols, phenols, cresols and other polyols referred to in the following paragraph, to the extent that they are volatilized to the vapor phase due to the particular processing conditions, their concentrations within the reaction stream and azeotropic behavior.
    The liquid phase will generally include water and oxygenated C2 + O2 + hydrocarbons not volatilized to the vapor phase, such as lignin derivatives, disaccharides, monosaccharides, sugars, sugar alcohols, alditols, heavy organic acids, phenols, cresols and diols, triols and other heavy polyols. As used herein, oxygenated hydrocarbons C2 + O2 + generally refer to oxygenated hydrocarbons that have 2 or more carbon atoms and 2 or more oxygen atoms and that have a relative volatility (a) with respect to 1-hexanol less than 0.03 based on pure components at 250 ° C. Oxygenated C2 + O2 + hydrocarbons may also include small amounts of C2 + O2 hydrocarbons, to the extent that C2 + O2 hydrocarbons are not volatilized to the vapor phase due to particular processing conditions, their concentrations within the reaction stream and azeotropic behavior . Preferably, C 2+ O 2+ oxygenated hydrocarbons have 2 to 6 carbon atoms or 2 to 12 carbon atoms. C2 + O2 + oxygenated hydrocarbons can also have 2 or more carbon atoms, 6 or more carbon atoms, 18 or more carbon atoms, or 24 or more carbon atoms, depending on the processing conditions and their concentration in the reaction stream . Exemplary C2 + O2 hydrocarbon species that can be present in both liquid and vapor phases include hydroxyacetone, ethylene glycol, propylene glycol and organic acids (e.g., acetic acid, propionic acid, lactic acid, etc.).
    C2 + O2 + oxygenated hydrocarbons will generally be
    23/92 soluble in water and / or a solvent, but may also include compounds that are insoluble in water. In one embodiment, C2 + O2 + oxygenated hydrocarbons include sugars, sugar alcohols, sugar breakdown products, starch, saccharides and other polyhydric alcohols. Preferably, C2 + O2 + oxygenated hydrocarbons include a sugar, such as glucose, fructose, sucrose, maltose, lactose, mannose or xylose or a sugar alcohol, such as arabitol, erythritol, glycerol, isomalt, lactitol, maltitol, mannitol, sorbitol , xylitol, arabitol or glycol. In other embodiments, oxygenated C2 + O2 + hydrocarbons may also include esters, heavy carboxylic acids, diols and other polyols. Organic acids can include, without limitation, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, isomers and derivatives thereof, including hydroxylated derivatives, such as 2-hydroxybutanoic acid and lactic acid. Diols may include, but are not limited to, ethylene glycol, propylene glycol, 1,3-propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, undecanediol, dodecanediol, benzene dihydroxide, dihydroxines, the same, dihydroxines, dihydrochlorides, dihydroxines, and the same resins. isomers thereof. Triols may include, without limitation, glycerol, 1,1,1 tris (hydroxymethyl) -ethane (trimethylolethane), trimethylolpropane, hexanethiol and isomers thereof. Other trioxigenates may include, but are not limited to, tetrahydro-2-furoic acid, hydroxymethyltetrahydrofurfural, hydroxymethylfurfural, dihydro5- (hydroxymethyl) -2 (3H) -furanone, 5-hydroxymethyl-2 (5H) furanone, dihydro-5- (hydroxymethyl) - 2 (3H) -furanone and isomers thereof. The liquid phase can also include volatile oxygenates, including any of the alcohols, ketones, aldehydes, carboxylic acids, ethers and cyclic ethers mentioned above, to the extent that they are present in the phase
    Net 24/92.
    The solid phase will generally include extractants and unreacted or underreacted biomass and, in certain applications, the deconstruction catalyst. Extractants will typically include ash components, such as calcium, aluminum, potassium, sodium, magnesium, chloride, sulfates, sulfites, thiols, silica, copper, iron, phosphates and phosphorus, as well as colored bodies (for example, terpenoids, stilbenes, flavonoids), proteinaceous materials and other inorganic products. The subreacted biomass will typically include partially reacted biomass and other heavy lignin, cellulose and hemicellulose derivatives not easily solubilized or maintained in a liquid phase, such as heavy polysaccharides, starches and other longer chain oxygenated hydrocarbons.
    Volatile oxygenates can undergo condensation reactions to form either straight chain compounds with a higher carbon number, or branched chain compounds, or cyclic compounds. The resulting compounds can be hydrocarbons or hydrocarbons that contain oxygen, the oxygen from which can be removed by reacting with hydrogen on a catalyst. The resulting condensed products include C4 + alcohols, C4 + ketones, C4 + alkanes, C4 + alkenes, C5 + cycloalkanes, C5 + cycloalkanes, aryls, fused aryls and mixtures thereof. Mixtures can be
    fractionated and/ or merged to to produce at mixtures appropriate in molecules typically used in gasoline, fuel in jet, fuel diesel or in Law Suit
    industrial chemicals.
    After conversion on the deconstruction catalyst, the product stream passes through one or more separation steps to separate the vapor, liquid and solid phase components. Various separation techniques are
    25/92 known in the art and can be used. Such techniques may include, without limitation, gravitational settlement techniques, cyclone separation techniques, simulated moving bed technology, distillation, filtration, etc. In one embodiment, the reactor system may include an outlet for the capture and removal of the vapor phase and a second outlet for the collection and removal of the liquid and solid phase components. In another embodiment, the product stream can be directed to a phase separator to allow simultaneous separation of each phase from the product stream. In any application, the liquid and solid phase can be directed to a settling tank configured to allow a bottom portion containing solid materials (eg, catalyst, extractants and unreacted or underreacted materials) to be separated from a portion top-liquid phase containing a significant fraction of C2 + O2 + oxygenated hydrocarbons. In certain embodiments, a portion of the liquid phase can also be maintained in the bottom portion to assist movement of the solid materials through additional processing steps or recycled to the biomass feed stream for use as a solvent to assist in deconstructing the biomass.
    In certain embodiments, the liquid phase may also require further processing to separate the aqueous phase products from organic phase products, such as lignin-based hydrocarbons which are not suitable for further conversion. The liquid phase can also have the water removed or purified further before being introduced into additional processing steps. The processes of water removal and purification are known in the art and can include techniques such as distillation, filtration, etc.
    In one embodiment, a solution resulting from
    26/92 oxygenated hydrocarbons C 2+ O 2+ is collected for further processing in a bioreformation process or, alternatively, used as a raw material for other conversion processes, including the production of fuels and chemicals using technologies enzymatic and fermentation. For example, water-soluble carbohydrates, such as starch, monosaccharides, disaccharides, polysaccharides, sugars and sugar alcohols and water-soluble derivatives of lignin, hemicellulose and cellulose are suitable for use in bioreformation processes, such as those described in Patents n US 6,699,457; 6,964,757; 6,964,758; and 7,618,612 (all to Cortright et al., and entitled Low-Temperature Hydrogen Production from Oxygenated Hydrocarbons ”); US Patent No. 6,953,873 :: ( a . Cortright et al and entitled LowTemperature Hydrocarbon Production from Oxygenated Hydrocarbons "); :: US Patent Nos 7,767,867; 7,989,664; and Patent Publication n :: US 2011/0306804 (to Cortright and entitled Methods and Systems for Generating Polyols ”); Patents No. :: 8,053,615; 8,017,818; 7,977,517; and U.S. Patent Publication No. US 2011/0257448; 2011/0245543; 2011/0257416; and 2011/0245542 (all to Cortright and Blommel and entitled Synthesis of Liquid Fuels and Chemicals from Oxygenated Hydrocarbons ”); Patent Publication No. US 2009/0211942 (to Cortright and entitled Catalysts and Methods for Reforming Oxygenated Compounds "); Patent Publication No. US 2010/0076233 ( a . Cortright et al and entitled Synthesis of Liquid Fuels from Biomass "); International Patent Application No. PCT / US2008 / 056330 (to Cortright and Blommel entitled Synthesis of Liquid Fuels and Chemicals from Oxygenated Hydrocarbons "); and Copending Commonly Owned International Patent Application n :: PCT / US2006 / 048030 (a Cortright et al. and entitled Catalyst and Methods for Reforming Oxygenated Compounds ”), all of which are incorporated herein
    27/92 reference title. Alternatively, the liquid phase can be recycled and combined in the biomass feed stream for further conversion.
    Biomass Deconstruction
    To produce the desired products, the biomass feed stream is reacted with hydrogen over a heterogeneous deconstruction catalyst under effective temperature and pressure conditions to convert lignin, cellulose, hemicellulose and its derivatives, when recycled or reactively generated in the feed stream. , in a product stream containing volatile C2 + O1-2 oxygenates in a gas phase and a solution of oxygenated C2 + O2 + hydrocarbons. The specific products produced will depend on several factors including the composition of the feed stream, reaction temperature, reaction pressure, water and / or solvent concentration, hydrogen concentration, catalyst reactivity and the feed stream flow rate as affects the spatial velocity (mass / volume of reagent per unit of catalyst per unit of time time), gaseous hourly space velocity (GHSV), net hourly space velocity (LHSV) and mass hourly space velocity (WHSV). For example, the vapor phase can also include small amounts of other compounds (for example, glycerol, heavy organic acids, butane diols, butane triols, etc.) due to the processing conditions and their concentration.
    Biomass can be originally supplied in its native form, pelleted or reduced to a size suitable for processing, such as by cutting, fragmenting or grinding to a size that allows minimal contact with the deconstruction catalyst or movement through the reactor system. Biomass can also be pre-treated or washed in water or solvent to remove all or a portion of the
    28/92 ash, lignin or any unwanted components contained in the biomass or in the biomass stream. Washing may include extraction with hot water or any one or more biological, enzymatic or thermochemical processes, such as enzymatic hydrolysis, acid hydrolysis or organosolv type applications.
    The deconstruction catalyst is a heterologous catalyst that has one or more materials that can catalyze a reaction between hydrogen and lignin, cellulose, hemicellulose and their derivatives to produce the desired water-soluble oxygen compounds. The heterologous catalyst may include, without limitation, acid-modified resins, acid-modified supports, base-modified resins, base-modified supports, tungsten carbide and / or one or more of Ru, Co, Rh, Pd, Ni, Mo . The catalyst may also include these elements alone or combined with one or more Fe, Ir, Pt, Re, Cu, Mn, Cr, Mo, B, W, V, Nb, Ta, Ti, Zr, Y, La, Sc, Zn, Cd, Ag, Au, Sn, Ge, P, Al, Ga, In, Tl, alloys thereof and combinations thereof. In one embodiment, the catalyst includes Ru, Co, Rh, Pd, Ni, or Mo and at least one member selected from W, B, Pt, Pd, Sn, Ag, Au, Rh, Co, Re and Mo.
    Resins will generally include basic or acidic supports (for example, supports that have low isoelectric points) that can catalyze biomass liquefaction reactions, followed by hydrogenation reactions in the presence of H2, leading to carbon atoms that are not bonded to atoms of oxygen. A class of acid supports includes heteropoly acids, solid phase acids exemplified by such species as H 3 + x PMo i2- xV x O 40 , H 4 SiW 12 O 40 , H 3 PW 12 O 40 and H6P 2 W 18 O 62 . Heteropoly acids also have a well-defined local structure, the most common of which is the tungsten-based Keggin structure. Basic resins can include
    29/92 supports that exhibit basic functionality. Examples of acidic and basic resins include Amberlyst resins 15Wet, 15Dry, 16Wet, 31Wet, 33, 35Wet, 35Dry, 39Wet, 70, CH10, CH28, Amberlyst resins A21, A23, A24 and A26 OH and Amberjet 4200 resins Cl, Amberlite IRA 400 Cl, Amberlite IRA 410 Cl, Amberlite IRC76, Amberlite IRC747, Amberlite IRC748, Ambersep GT74, Ambersep 820U Cl, produced by Rohm Haas.
    The catalyst is self-sufficient or includes a support material. The support may contain any or more of nitride, carbon, silica, alumina, acid alumina, silica-alumina, theta-alumina, sulfated alumina, phosphate alumina, zirconia, sulphate zirconia, phosphate zirconia, titania-zirconia, tungsten zirconia, titania , tungsten, vanadium, ceria, zinc oxide, chromium, boron nitride, heteropoly acids, diatomite, hydroxypatite and mixtures thereof. Nanoporous supports such as zeolites, carbon nanotubes or carbon fullerene can also be used. Preferred supports are carbon, alumina, phosphate zirconia, m-ZrO2, and W-ZrO2. In one embodiment, the deconstruction catalyst includes Ni: Mo, Pd: Mo, Rh: Mo, Pd: Ag or Co: Mo in a m-ZrO2 support. In another embodiment, the catalyst includes Ru, Ru: Pt, Ru: Pd, Pd: Ag or Ru: Pt: Sn in a support of W-ZrO2 or carbon. The support can also serve as a functional catalyst, as in the case of acidic or basic resins or supports that have acidic or basic functionality.
    The deconstruction catalyst can be designed and configured to function as a fixed bed within a reactor or mixed with the feed stream as in a slurry reactor. In one embodiment, the catalyst is formed in a honeycombed monolith design so that the biomass feed stream, be it a biomass slurry, solid phase slurry or a liquid / solid phase slurry, can flow through the catalyst. In
    In another embodiment, the catalyst includes a magnetic element, such as Fe or Co, so that the catalyst can be easily separated from the resulting biomass product stream. In yet another embodiment, the deconstruction catalyst is a metallic sponge material, such as a spongy nickel catalyst.
    Activated spongy nickel catalysts (eg Raney nickel) are a well-known class of materials effective for various reactions. Raney's nickel catalyst is typically prepared by treating an alloy of approximately equal amounts by weight of nickel and aluminum with an aqueous alkaline solution, for example, which contains about 25% by weight of sodium hydroxide. Aluminum is selectively dissolved by the aqueous alkaline solution leaving particles that have a sponge construction and are predominantly composed of nickel with a small amount of aluminum. Promoter metals, such as those described above, can be included in the initial alloy in an amount so that about 1 to 5%, by weight, remains on the spongy nickel catalyst.
    The deconstruction process can be batch or continuous. In one embodiment, the deconstruction process is a continuous process that uses one or more reactors of continuous agitation tank in parallel or in series. The deconstruction temperature will generally be greater than 120 ° C, or 150 ° C, or 185 ° C, or 200 ° C, or 250 ° C, or 270 ° C, and less than 350 ° C, or 325 ° C, or 310 ° C, or 300 ° C. In one embodiment, the deconstruction temperature is between about 120 ° C and 350 ° C, or between about 150 ° C and 325 ° C, or between about 200 ° C and 310 ° C, or between about 250 ° C and 300 ° C, or between about 270 ° C and 300 ° C. The deconstruction pressure will generally be greater than 2.06 MPa (300 psi), or 2.59 MPa (375 psi), or 3.28 MPa (475 psi), or 4.14 MPa (600 psi), or 5, 17
    31/92
    MPa (750 psi), or 6.89 MPa (1,000 psi), and less than 17.23 MPa (2,500 psi), or 16.5 MPa (2400 psi), or 14.8 MPa (2,150 psi), or 13 , 1 MPa (1,900 psi), or 12.1 MPa (1,750 psi), or 10.3 MPa (1,500 psi). In one embodiment, the deconstruction pressure is between about 2.06 MPa (300 psi) and 17.23 MPa (2,500 psi), or between about 2.06 MPa (300 psi) and 10.3 MPa (1,500 psi) ), or between about 6.89 MPa (1,000 psi) and 10.3 MPa (1,500 psi). In one embodiment, deconstruction occurs in the form of stages so that the deconstruction temperature and deconstruction pressure can be varied at each stage (for example, a deconstruction temperature and first stage pressure between about 150 ° C and 325 ° C ° C and between about 2.06 MPa (300 psi) and 12.4 MPa (1,800 psi), respectively, and a second stage deconstruction temperature and pressure between about 200 ° C and 300 ° C and about 5 , 52 MPa (800 psi) and 10.3 MPa (1500 psi), respectively). Collectively, the temperature and pressure conditions must be such that a significant portion of the volatile C2 + O12 oxygenates are in the vapor phase, while a significant portion of the water and less volatile C 2+ O 2+ oxygenates (eg more heavy metals, trioxigenates and other polyoxygenates, etc.) and other lignin, hemicellulose and cellulose derivatives (for example, sugars, sugar alcohols, saccharides, starches, etc.) are kept in the liquid and / or solid phase.
    In general, the reaction should be conducted under conditions where the residence time of the feed stream over the catalyst is appropriate to generate volatile C2 + O1-2 oxygenates in a gas phase. For example, the WHSV for the reaction can be at least about 0.1 gram of biomass per gram of catalyst per hour, and more preferably about 0.1 to 40.0 g / g hour, including a WHSV of about 0.25, 0.5, 0.75, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1, 9,
    32/92
    2, 0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3, 2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4, 4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 6, 7, 8, 9, 10, 11 , 12, 13 , 14, 15, 20 , 25, 30, 35, 40 g / g hour, and reasons in between
    (including 0.83, 0.84, 0.85, 1.71, 1.72, 1.73, etc.).
    Preferably, the biomass feed stream contacts the catalyst for approximately 5 minutes to 6 hours.
    The present invention has the ability to effectively convert biomass components to lower molecular weight oxygenated hydrocarbons due to the presence of hydrogen in the system. Hydrogen facilitates the reaction and the conversion process through immediate reaction with the various reaction intermediates and the catalyst to produce products that are more stable and less subject to degradation. Hydrogen can be generated in situ using aqueous phase reform (H 2 or H 2 of APR generated in situ), either in the biomass deconstruction reactor or in downstream processes that use soluble oxygenated C2 + O2 + hydrocarbons water from the liquid phase as a raw material, or a combination of APR H2, external H2 or recycled H2, or just simply external H2 or recycled H2. The term external H 2 ”s refers to a hydrogen that does not come from the biomass solution, but is added to the reactor system from an external source. The term recycled H 2 ”refers to an unconsumed hydrogen that is collected and then recycled back into the reactor system for further use. External H2 and recycled H2 can be called, collectively or individually, as additional H 2 ”. In general, the amount of H2 added should maintain the reaction pressure within the system at the desired levels, or increase the molar ratio of hydrogen to carbon and / or oxygen in order to
    33/92 to intensify the production yield of certain types of reaction product.
    The deconstruction process may also include the introduction of supplementary materials to the feed stream to assist with the deconstruction of biomass or to increase the yields of the conversion process. Supplementary yield enhancing materials may include: unreacted or overreacted materials recycled from the solid phase of the product stream; oxygenated C 2+ O 2+ hydrocarbons from the liquid phase; and / or solvents from downstream processes or other processes. Supplementary materials may also include conventional raw material streams (for example, starches, syrups, carbohydrates and sugars), which can also be readily converted to the desired volatile C2 + O1-2 oxygenates or liquid phase products.
    Another supplementary material may include a pressurized gas stream (for example, hydrogen, inert gas or product gas) which is subjected to a waste wash through the biomass and the catalyst during the deconstruction process. Waste washing is used to remove desired products from the reactor to prevent unwanted side reactions (for example, degradation reactions).
    Supplementary materials may also include solvents that assist in the deconstruction process. Solvent-based applications are well known in the art. Organosolv type processes use organic solvents such as ionic liquids, acetone, ethanol, 4-methyl-2-pentanone and solvent mixtures, to fractionate lignocellulosic biomass in cellulose, hemicellulose and lignin streams (Paszner 1984; Muurinen 2000; and Bozell 1998). Strong acid processes use concentrated hydrochloric acid,
    34/92 phosphoric acid, sulfuric acid or other strong organic acids as the depolymerization agent, whereas weak acid processes involve the use of diluted strong acids, acetic acid, oxalic acid, hydrofluoric acid or other weak acids such as the solvent. Enzymatic processes have also recently gained prominence, and include the use of enzymes as a biocatalyst to de-crystallize the structure of biomass and allow additional hydrolysis to usable raw materials. In one example, supplementary materials include acetone, glyconic acid, acetic acid, H 2 SO 4 or H 3 PO 4 . In another example, supplementary materials include an aqueous solution and water-soluble oxygenated hydrocarbons, and solvents derived from a biorformation process, such as those described in US Patent Nos. 7,767,867; 7,989,664; and in Patent Application n :: US 2011/0306804, all to Cortright, and entitled Methods and Systems for Generating Polyols ”.
    Condensation
    The volatile C 2+ O 1-2 oxygen produced can be collected and used in industrial applications, or converted to C 4+ compounds through condensation reactions catalyzed by a condensation catalyst. Without being limited to any specific theories, condensation reactions are generally believed to consist of a series of steps involving: (a) dehydration of oxygenates to alkenes; (b) the oligomerization of the alkenes; (c) cracking reactions; (d) the cyclization of larger alkenes to form aromatics; (e) the isomerization of alkane; (f) hydrogen transfer reactions to form alkanes. The reactions may also consist of a series of steps involving: (1) condensation of aldol to form a βhydroxy ketone or a β-hydroxyaldehyde; (2) the dehydration of β-hydroxyketone or β-hydroxyaldehyde to form an enone
    35/92 conjugate; (3) the hydrogenation of the enone conjugated to form a ketone or an aldehyde, which can participate in additional condensation or conversion reactions to an alcohol or hydrocarbon; and (4) the hydrogenation of carbonyls to alcohols, or vice versa. Other condensation reactions can occur in parallel, including condensation of aldol, reactions of prins, ketonation of acids, and condensation of Diels-Alder.
    The condensation catalyst will generally be a catalyst that has the ability to form longer chain compounds by linking two species that contain oxygen through a new carbon-carbon bond, and converting the compound resulting to a hydrocarbon, alcohol or ketone. The condensation catalyst may include, without limitation, carbides, nitrides, zirconia, alumina, silica, aluminosilicates, phosphates, zeolites, titanium oxides, zinc oxides, vanadium oxides, lanthanum oxides, yttrium oxides, scandium oxides, magnesium oxides, cerium oxides, barium oxides, calcium oxides, hydroxides, heteropoly acids, inorganic acids, acid modified resins, base modified resins and combinations thereof. The condensation catalyst can include the above types alone or in combination with a modifier, such as Ce, La, Y, Sc, P, B, Bi, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba and combinations thereof. The condensation catalyst can also include a metal, such as Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, alloys and combinations thereof, to provide metallic functionality.
    The condensation catalyst may be self-sufficient (that is, the catalyst does not need any other material to serve as a support), or it may require a suitable separate support to suspend the catalyst in the
    36/92 reagent stream. Particularly beneficial supports include alumina, silica and zirconia. In other embodiments, particularly when the condensation catalyst is a powder, the catalyst system can include a binder to assist in forming the catalyst in a desirable catalyst format. Applicable forming processes include extrusion, pelletizing, oil dripping or other known processes. Zinc oxide, alumina and a peptizing agent can also be mixed and extruded to produce a formed material. After drying, this material is calcined at an appropriate temperature for the formation of the catalytically active phase, which normally requires temperatures above 350 ° C. Other catalyst supports may include those described in further detail below.
    In one embodiment, the condensation reaction is carried out using a catalyst that has acidic functionality. Acid catalysts may include, without limitation, aluminosilicates (zeolites), silicaalumina phosphates (SAPO), aluminum phosphates (ALPO), amorphous silica alumina, zirconia, sulfated zirconia, tungsten zirconia, tungsten carbide, molybdenum carbide, titania , acid alumina, phosphate alumina, phosphate silica, sulfate carbons, phosphate carbons, acid resins, heteropoly acids, inorganic acids and combinations thereof. In one embodiment, the catalyst may further include a modifier, such as Ce, La, Y, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, P, B, Bi and combinations thereof. The catalyst can also be modified by adding a metal, such as Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Rh, Zn, Ga, In, Pd, Ir, Re, Mn, Cr , Mo, W, Sn, Os, alloys and combinations thereof, to provide metallic functionality, and / or sulfides and oxides of Ti, Zr, V, Nb, Ta, Mo, Cr, W, Mn, Re, Al, Ga , In,
    37/92
    Fe, Co, Ir, Ni, Si, Cu, Zn, Sn, P and combinations thereof. It was found that tungsted zirconia is a particularly useful catalyst for the present process, especially when modified with Cu, Pd, Ag, Pt, Ru, Ni, Sn and combinations thereof. The acid catalyst may be homogeneous, self-sufficient or adhered to any of the supports described further below, including supports containing carbon, silica, alumina, zirconia, titania, vanádia, ceria, heteropoly acids, alloys and mixtures thereof.
    For example, the condensation catalyst can be a zeolite catalyst. The term zeolite, as used in this document, refers not only to microporous crystalline aluminosilicate, but also to aluminosilicate structures that contain microporous crystalline metal, such as gallaluminosilicates and galossilicates. In such cases, In, Zn, Fe, Mo, Ag, Au, Ni, P, Y, Ta and latanids can be interchanged to zeolites to provide the desired activity. Metallic functionality can be provided by metals such as Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, alloys and combinations thereof.
    Examples of suitable zeolite catalysts include ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35 and ZSM48. The ZSM-5 zeolite, and the conventional preparation thereof, is described in US Patent Nos. 3,702,886; Re. 29,948 (highly siliceous ZSM-5); 4,100,262 and 4,139,600, all of which are incorporated herein by reference. Zeolite ZSM-11 and the conventional preparation thereof, is described in US Patent No. 3,709,979 which is also incorporated herein by reference. Zeolite ZSM-12 and the conventional preparation thereof, is described in US Patent No. 3832.449 :: incorporated in
    38/92 this document as a reference. The ZSM-23 zeolite, and the conventional preparation thereof, is described in Patent No. :: US 4,076,842, incorporated herein by reference. The ZSM-35 zeolite, and the conventional preparation thereof, is described in Patent No. :: US 4,016,245, incorporated herein by reference. Another preparation of ZSM-35 is described in US Patent No. :: 4,107,195, the disclosure of which is incorporated herein by reference. The ZSM-48, and the conventional preparation thereof, is taught through Patent n :: US 4,375,573, incorporated by reference in this document. Other examples of zeolite catalysts are described in US Patent No. 5,019,663 and :: Pat :: US 7,022,888, also incorporated herein by reference. In one embodiment, the condensation catalyst is a ZSM-5 zeolite modified with Cu, Pd, Ag, Pt, Ru, Ni, Sn, or combinations thereof.
    As described in US Patent No. 7022.888 ::, the condensation catalyst can be a zeolite catalyst of the pentasil type bifunctional comprising at least one metallic element from the group Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, alloys and combinations thereof, or a modifier from the group of In, Zn, Fe, Mo, Au, Ag, Y, Sc, Ni, P, Ta, latanids and combinations thereof. The zeolite preferably has strong acidic sites, and can be used with reagent streams that contain an oxygenated hydrocarbon at a temperature below 580 ° C. The bifunctional pentasil-type zeolite can have a crystal structure of the type ZSM-5, ZSM- 8 or ZSM-11 which consist of a large number of 5-membered oxygen rings (ie, pentasil rings). Zeolite with a structure of the type ZSM-5 is a particularly preferred catalyst.
    39/92
    The condensation catalyst can include one or more zeolite structures that comprise structures similar to silica-alumina cages. Zeolites are crystalline microporous materials with well-defined pore structures. Zeolites contain active sites, usually acid sites, that can be generated in the zeolite framework. The strength and concentration of the active sites can be customized for particular applications. Examples of suitable zeolites for condensing secondary alcohols and alkanes may comprise aluminosilicates, optionally modified with cations such as Ga, In, Zn, Mo and mixtures of such cations, as described, for example, in US Patent No. 3,702 ::. 886, which is incorporated by reference in this document. As recognized in the art, the structure of the particular zeolite or zeolites can be altered to provide different amounts of various hydrocarbon species in the product mixture. Depending on the structure of the zeolite catalyst, the product mixture may contain various amounts of aromatic and cyclic hydrocarbons.
    Alternatively, solid acid catalysts such as phosphate modified alumina, chloride, silica and other acidic oxides can be used in the practice of the present invention. In addition, sulfated zirconia, phosphate zirconia, titania-zirconia or tungsted zirconia can provide the necessary acidity. Re and Pt / Re catalysts are also useful to promote the condensation of oxygen to C5 + hydrocarbons and / or C5 + monooxygenates. Re is acidic enough to promote acid-catalyzed condensation. Acidity can also be added to activated carbon by adding sulfates or phosphates.
    The specific C4 + compounds produced will depend on several factors, including, without limitation, the
    40/92 type of volatile C 2+ O 1 _ 2 oxygenates in the reagent stream, the condensing temperature, the condensing pressure, the reactivity of the catalyst and the flow rate of the reagent stream as it affects the spatial speed, GHSV, LHSV and WHSV. Preferably, the reagent stream is contacted with the condensation catalyst at a WHSV that is suitable for producing the desired hydrocarbon products. WHSV is preferably at least about 0.1 grams of volatile C 2+ O 1-2 1-2 in the reagent stream per gram of catalyst per hour, more preferably WHSV is between about 0.1 to 10.0 g / g hour, including a WHSV of about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 g / g hour, and increments between these.
    The condensation reaction must be carried out at a temperature and pressure at which the proposed reaction thermodynamics is favorable. In general, the reaction should be carried out at a temperature where the vapor pressure of volatile C 2+ O 1-2 oxygen is at least about 0.01 MPa (0.1 atm) (and preferably much higher) . The condensation temperature will vary depending on the specific composition of the volatile C 2+ O 1-2 oxygenates. The condensing temperature will be
    usually greater than 80 ° C, or 125 ° C, or 175 ° C, or 200 ° C, or 225 ° C, or 250 ° C, and smaller what 500 ° C, or 450 ° C, or 425 ° C, or 375 ° C, or 325 ° C, or 275 ° C. In an modality , a
    condensation temperature is between about 80 ° C to 500 ° C, or between about 125 ° C to 450 ° C, or between about 250 ° C to 425 ° C. Condensing pressure will generally be greater than 0 KPa (0 psig), or 68.94 KPa (10 psig), or 689.47 KPa (100 psig), or 1,378, 95 KPa (200 psig), and less than 8,273, 70 KPA (1,200 psig), or 7,584.23 (1,100 psig), or 6,894.75 KPa (1,000 psig), or 6,205.28 KPa (900 psig), or 4,826.33 KPa (700 psig). In one embodiment, the condensing pressure is greater than about 0.01 MPa (0.1 atm), or between about 0 and
    41/92
    8,273.70 KPA (0 and 1,200 psig), or between about 0 and 6,894.75 (0 and 1,000 psig).
    The variation of the above factors, as well as others, will generally result in a modification to the specific composition and yields of the C 4+ compounds. For example, changing the temperature and / or pressure of the reactor system, or of the particular catalyst formulations, can result in the production of C4 + alcohols and / or ketones instead of C4 + hydrocarbons. The C4 + hydrocarbon product can also contain a variety of alkenes, and alkanes of various sizes (including both normal and branched alkanes). Depending on the condensation catalyst used, the hydrocarbon product can also include cyclic and aromatic hydrocarbon compounds. The C4 + hydrocarbon product may also contain undesirably high levels of alkenes, which can lead to the formation of coke or deposits in combustion engine mechanisms, or other undesirable hydrocarbon products. In such an event, the hydrocarbon molecules produced can optionally be hydrogenated to reduce ketones to alcohols and hydrocarbons, while alcohols and unsaturated hydrocarbons can be reduced to alkanes, cyclic alkanes, and aromatics, thereby forming a hydrocarbon product. more desirable that it has low levels of alkenes, aromatics or alcohols.
    The finalization step will generally involve a hydrogenation reaction that removes the remaining oxygen from the hydrocarbons, including the removal of oxygen from carbonyls, hydroxyls, furans, acids, esters, phenols. Various processes and catalysts are known for the hydrogenation of oxygenated compounds. Typical catalysts include a support with any or more of the following metals, Cu, Ni, Fe, Co, Ru, Pd, Rh, Pt, Ir, Os, alloys or
    42/92 combinations thereof, alone or with promoters such as Au, Ag, Cr, Zn, Mn, Sn, Cu, Bi and their alloys. The above metals and promoters can be used in various fillers ranging from about 0.01 to about 20%, by weight, on any of the supports described below.
    In general, the finishing step is carried out at finishing temperatures between about 200 ° C to 450 ° C, and finishing pressures in the range of about 689.47 KPa to 13,789.51 KPa (100 psig to 2,000 psig). The finishing step may be conducted in the vapor phase or liquid phase, and can use in situ generated H2, external H2, recycled H2 , or combinations thereof, as needed.
    Other factors, such as the presence of unwanted water or oxygen, can also affect the composition and yield of C4 + compounds, as well as the activity and stability of the condensation catalyst. In such an event, the process can include a dehydration step that removes a portion of the water prior to condensation, or a separation unit for removing unwanted oxygen. For example, a separator unit, such as a phase separator, a flash mode separator, an extractor, a purifier or a distillation column, can be installed before the condensation step in order to remove a portion of the water from the stream of reagent containing volatile C2 + O1-2 oxygenates. A separation unit can also be installed to remove specific oxygenates to allow the production of a desired product stream that contains hydrocarbons within a particular range of carbon, or for use as end products or in other systems or processes.
    The effectiveness of the condensation catalyst can also be influenced by the presence of small amounts of heavier volatilized dioxigenates and trioxigenates for
    43/92 the gas phase due to the processing conditions and their concentration in the reaction stream. Such compounds typically have a relative volatility (a) to a 1-hexanol of less than 0.03 based on pure components at 250 ° C, but can be volatilized at minimum concentrations, lower pressures and higher temperatures during reaction of deconstruction. They are also known to lead to the formation of coke and the rapid deactivation of catalysts in condensation reactions. An advantage of the present invention is that such compounds are minimized in the reaction stream and, so far, the process conditions and the catalysts used for the condensation reactions allow their conversion to usable final products without significant coke formation and / or deactivation of the condensation catalyst.
    C 4+ compounds
    The practice of the present invention results in the production of C4 + alkanes, C4 + alkenes, C5 + cycloalkanes, C5 + cycloalkanes, aryls, fused aryls, C4 + alcohols, C4 + ketones, C4 + furans and mixtures thereof. C4 + alkanes and C4 + alkenes have 4 to 30 carbon atoms (C4-30 alkanes and C4-30 alkanes) and can be branched or straight chain alkanes or alkenes. C4 + alkanes and C4 + alkanes may also include fractions of alkanes and C 4-9 , C 7-14 , C 12-24 alkenes, respectively, with the C4-9 fraction targeting gasoline, the C 7-16 fraction targeting jet fuel, and the C11-24 fraction targeting diesel fuel and other industrial applications. Examples of various C4 + alkanes and C4 + alkenes include, without limitation, butane, butene, pentane, pentene, 2-methylbutane, hexane, hexene, 2-methylpentane, 3methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, heptane, heptene , octane, octene, 2,2,4, -trimethylpentane, 2,3-dimethyl hexane, 2,3,4-trimethylpentane, 2,3-dimethylpentane, nonane,
    44/92 nonene, dean, decene, undecane, undecene, dodecane, dodecene, tridecane, tridecene, tetradecane, tetradecene, pentadecane, pentadecene, hexadecane, hexadecene, heptydecane, heptydecene, octildecane, octydene and non-dildosene, non-dyethene and non-dyethene, , uneicosene, doeicosane, doeicosene, trieicosane, trieicosene, tetraeicosane, tetraeicosene and isomers thereof.
    C5 + cycloalkanes and C5 + cycloalkanes have 5 to 30 carbon atoms and can be unsubstituted, monosubstituted or multi-substituted. In the case of monosubstituted and multi-substituted compounds, the substituted group may include a branched C3 + alkyl, a straight chain C1 + alkyl, a branched C3 + alkylene, a straight chain C2 + alkylene, a phenyl or a combination thereof. In one embodiment, at least one of the substituted groups includes branched C 3-12 alkyl, straight chain C 1-12 alkyl, branched C3-12 alkylene, straight chain C1-12 alkylene, C2-12 alkylene straight chain, a phenyl or a combination thereof. In yet another embodiment, at least one of the substituted groups includes a branched C3-4 alkyl, a straight chain C1-4 alkyl, a branched C3-4 alkylene, a straight chain C1-4 alkylene, a C2-4 alkylene straight-chain, a phenyl or a combination thereof. Examples of desired C5 + cycloalkanes and C5 + cycloalkenes include, without limitation, cyclopentane, cyclopentene, cyclohexane, cyclohexene, methylcyclopentane, methylcyclopentene, ethylcyclopentane, ethylcyclopentene, ethylcyclohexane, ethylcyclohexane, propylcyclohexane, propylcyclohexane, propyl , pentyl-cyclopentane, pentylcyclohexane, hexyl-cyclopentane, hexyl-cyclohexane and isomers thereof.
    Aryls will generally consist of an aromatic hydrocarbon in an unsubstituted form
    45/92 (phenyl), monosubstituted or multisubstituted. In the case of monosubstituted and multi-substituted compounds, the substituted group may include a branched C 3+ alkyl, a straight chain C 1+ alkyl, a branched C 3+ alkylene, a branched chain C 2+ alkylene, a phenyl or a combination thereof. In one embodiment, at least one of the substituted groups includes branched C3-12 alkyl, straight chain C1-12 alkyl, branched C3-12 alkylene, straight chain C2-12 alkylene, phenyl or a combination thereof . In yet another embodiment, at least one of the substituted groups includes a branched C3-4 alkyl, a straight chain C1-4 alkyl, a straight chain C3-4 alkylene, a straight chain C2-4 alkylene, a phenyl or a combination of them. Examples of various aryls include, without limitation, benzene, toluene, xylene (dimethylbenzene), ethyl benzene, for xylene, meta xylene, ortho xylene, C9 + aromatics, butyl benzene, pentyl benzene, hexyl benzene, heptyl benzene, octyl benzene, nonyl benzene , decyl benzene, undecyl benzene and isomers thereof.
    The fused aryls will generally consist of polycyclic and bicyclic aromatic hydrocarbons, in unsubstituted, monosubstituted, or multisubstituted form. In the case of monosubstituted and multi-substituted compounds, the substituted group can include a branched C3 + alkyl, a straight chain C1 + alkyl, a branched C3 + alkylene, a straight chain C2 + alkylene, a phenyl or a combination thereof. In another embodiment, at least one of the substituted groups includes a branched C3-4 alkyl, a straight chain C1-4 alkyl, a branched C3-4 alkylene, a straight chain C2-4 alkylene, a phenyl or a combination thereof . Examples of various fused aryls include, without limitation, naphthalene, anthracene, tetrahydronaphthalene and decahydronaphthalene, indane, indene and
    46/92 isomers thereof.
    C 4+ alcohols can also be cyclic, branched or straight chain, and have 4 to 30 carbon atoms. In general, C4 + alcohols can be a compound according to the formula R 1 -OH, where R 1 is a member selected from the group consisting of branched C4 + alkyl, straight chain C4 + alkyl, C4 + alkylene of straight chain, straight chain C4 + alkylene, substituted C5 + cycloalkane, unsubstituted C5 + cycloalkane, substituted C5 + cycloalkene, unsubstituted C5 + cycloalkene, aryl, phenyl and combinations thereof. Examples of desired C 4+ alcohols include, but are not limited to, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptydecanol, octyldecanol, nonildecanol, eicosanol, unicosicos, doeicosanol, trieicosanol, tetraeicosanol and isomers thereof.
    C4 + ketones can also be cyclic, branched or straight chain, and have 4 to 30 carbon atoms. In general, the C4 + ketone can be a compound according to the formula
    R 3
    R 4 where R 3 and R 4 are independently a member selected from the group consisting of a branched C 3+ alkyl, a straight chain C 1+ alkyl, a straight chain C 3 + alkylene, a straight chain C 2 + alkylene, a substituted C5 + cycloalkane, an unsubstituted C5 + cycloalkane, a substituted C5 + cycloalkene, an unsubstituted C5 + cycloalkene, an aryl, a phenyl and a combination thereof. Examples of desirable C 4+ ketones include, without limitation, butanone, pentanone, hexanone, heptanone,
    47/92 octanone, nonanone, decanone, undecanone, dodecanone, tridecanone, tetradecanone, pentadecanone, hexadecanone, heptydecanone, octyldecanone, nonildecanone, eicosanone, uneicosanone, doeicosanone, trieicosanone, triamicosanone and trieticosanoone, tetraicosanone and tetraicosanone.
    The lighter fractions of the above examples, primarily C4-C12, can be separated for gasoline use. Moderate fractions, such as C 7 -C 16 , can be separated for jet fuel, while heavier fractions, ie, C11-C24, can be separated for diesel use. The lighter fractions can be used as lubricants or cracked to produce additional diesel and / or gasoline fractions. C4 + compounds can also find use as industrial chemical substances, either as an intermediate product or as a final product. For example, aryls toluene, xylene, ethyl benzene, for xylene, meta xylene, ortho xylene can find use as chemical intermediates for the product of plastics and other products. Meanwhile, C9 + aromatics and fused aryls, such as naphthalene, anthracene, tetrahydronaphthalene and decahydronaphthalene, can find use as solvents in industrial processes.
    Catalyst Supports
    In various embodiments above, the catalyst systems include a suitable support for suspending the catalyst in the biomass feed stream, in the biomass slurry or in the reagent stream. The support must be one that provides a suitable platform for the chosen catalyst and the reaction conditions. The support can take any form that is stable under the conditions chosen to function at the desired levels, and specifically stable in aqueous raw material solutions. Such supports include, without limitation, carbon, silica, alumina, silica-alumina, alumina
    48/92 acidic, sulfated alumina, phosphate alumina, zirconia, tungstated zirconia, titania-zirconia, sulfated zirconia, phosphate zirconia, titania, ceria, vanadium, nitride, boron nitride, heteropoly acids, hydroxypatite, zinc oxide, chromium and mixtures themselves. Nanoporous supports such as zeolites, carbon nanotubes or carbon fullerene can also be used.
    A particularly preferred catalyst support is carbon, especially carbon supports that have relatively high surface areas (greater than 100 square meters per gram). Such carbons include activated carbon (granulated, powdered or pelletized), fibers, felts or activated carbon fabric, carbon nanotubes or nanocorns, carbon fullerene, high surface area carbon wells, carbon foams (reticulated carbon foams) ) and carbon blocks. Carbon can be produced through steam or chemical activation of peat, wood, lignite, coal, coconut shells, olive stones and oil-based carbon. Another preferred support is granulated activated carbon produced from coconuts.
    Another preferred catalyst support is zirconia. Zirconia can be produced through precipitation of zirconia hydroxide from zirconium salts, through sol-gel processing or any other method. Zirconia is preferably present in a crystalline form achieved by calcining the precursor material at temperatures above 400 ° C and can include both monocyclic and tetragonal crystalline phases. A modifying agent can be added to enhance the textural or catalytic properties of zirconia. Such modifying agents include, without limitation, sulfate, tungstate, phosphate, titania, silica and Group IIIB metal oxides, especially Ce, La or Y.
    49/92 modality, the deconstruction catalyst consists of Pd: Ag in a tungsted zirconia support.
    Another preferred catalyst support is titania. Titania can be produced through precipitation from titanium salts, through solgel processing or any other method. Titania is preferably present in a crystalline form and can include both crystalline phases of rutile and anatase. A modifying agent can be added to enhance the textural or catalytic properties of titania. Such modifying agents include, without limitation, sulfate, silica and Group IIIB metal oxides, especially Ce, La or Y.
    Yet another preferred catalyst support is a transitional alumina, preferably theta-alumina. Theta-alumina can be produced by precipitation of aluminum salts, through sol-gel processing, or any other method. Preferably, the support would be manufactured by peptizing a suitable aluminum hydroxide, preferably bohemian or false bohemite, with nitric acid in the presence of an organic binder, preferably hydroxyethyl cellulose. After forming, the support must then be calcined to a final temperature between 900 to 1,200 ° C, preferably greater than 1,000 ° C. A modifying agent can be added to improve the textural or catalytic properties of alumina. Such modifying agents include, without limitation, sulfate, silica, Fe, Ce, La, Cu, Co, Mo, or W.
    The support can also be treated or modified to enhance its properties. For example, the support can be treated, as by surface modification, to modify molecular portions of the surface, such as hydrogen and hydroxyl. The hydrogen and hydroxyl groups
    50/92 surface can cause local pH variations that affect catalytic efficiency. The support can also be modified, for example, by treating it with sulfates, phosphates, tungstenioates, silanes, lanthanides, alkaline compounds or alkaline earth compounds. For carbon supports, the carbon can be pre-treated with steam, oxygen (from the air), inorganic acids or hydrogen peroxide to provide more surface oxygen sites. The preferential pretreatment would be for the use of both oxygen and hydrogen peroxide. The pretreated carbon can also be modified by the addition of Group IVB and Group VB oxides. It is preferable to use oxides of W, Ti, V, Zr and mixtures thereof.
    Catalyst systems, either alone or mixed, can be prepared using conventional methods known to those in the art. Such methods include incipient humidification, evaporative impregnation, chemical vapor deposition, wash coating, magnetron sputtering techniques, and the like. The method chosen to manufacture the catalyst is not particularly crucial to the function of the invention, with the proviso that different catalysts will yield different results, depending on considerations such as general surface area, porosity, etc.
    Catalyst regeneration
    During deconstruction, carbonaceous deposits are formed on the deconstruction catalyst surface through minor side reactions from biomass and other generated products. As these deposits accumulate, access to catalytic sites on the surface becomes restricted and the performance of the catalyst decreases, resulting in less conversion and yields the desired products.
    To regenerate the deconstruction catalyst, the
    51/92 solid phase is further divided by separating the catalyst from the extractants and materials reacted or subreacted using a washing medium. The washing medium can be any medium capable of washing unreacted species from the catalyst and reactor system. Such a washing medium can include any one of several liquid media, such as water, alcohols, ketones, chelating agents, acids, or other oxygenated hydrocarbons, either alone or in combination with any of the foregoing, and which does not include materials known to be poisons for the catalyst in use (for example, sulfur). The washing step may include either emerging from the catalyst for a period of time (for example, 5 or more minutes), flushing with the washing medium, or a combination of both, and at a temperature that does not cause the medium to liquid washing or unreacted species switch to the gas phase. The washing step can also involve multiple flushing activities, which include one or more initial washes with an organic solvent, followed by one or more washes with water, or vice versa, until the deconstruction catalyst is free of extractants and others unwanted materials. In one embodiment, the temperature is kept below about 100 ° C during the washing step.
    In certain applications, the deconstruction catalyst may still be in a mixture with unreacted or underreacted biomass after washing, thereby requiring additional separation. In general, the deconstruction catalyst will tend to be denser than biomass and can be readily separated using a variety of techniques, including cyclone separation, centrifugation, and gravitational settlement, among others.
    The deconstruction catalyst is then dried at a temperature and pressure sufficient to remove any water
    52/92 of the catalyst (eg 120 ° C and at atmospheric pressure). Once dry, the temperature in the reactor is raised at a rate of about 20 ° C per hour to about 60 ° C per hour, and is maintained at a temperature between about 300 ° C and about 450 ° C. At temperatures between about 120 ° C and about 150 ° C, the C-O and C-C bonds in the carbonaceous deposits are broken and CO2 and CO are released from the catalyst and collected in a downstream phase separator or removed in the gas phase. As temperatures continue to rise to around 450 ° C, C-C bonding hydrogenolysis predominates. Throughout the regeneration and cooling process, a gas flow of 600 to 1200 ml gas / ml catalyst per hour (GHSV) of inert gas (eg nitrogen) and 0.5 to 10% oxygen is maintained.
    During deconstruction catalyst regeneration, carbon dioxide and small amounts of carbon monoxide are emitted as a regeneration stream. Finally, the level of carbon dioxide in the regeneration stream decreases as the regeneration progresses, providing an effective means of monitoring the state of the regeneration. Based on this trend, to obtain maximum performance return, regeneration is continued until the CO2 content of the regeneration stream is below an indicative amount of successful regeneration.
    The deconstruction catalyst is considered to be completely regenerated when sufficient carbonaceous deposits have been removed so that deconstruction can be continued. This usually occurs when the CO2 expelled during regeneration decreases to an insignificant amount. In a preferred embodiment, the deconstruction catalyst is considered to be regenerated when the amount of CO2 in the regeneration stream is less than 4,000 ppm, more preferably less than 2,000 ppm, and more
    53/92 preferably less than 1,000 ppm. to ensure that maximum regeneration is achieved, the deconstruction catalyst may need to be regenerated at its highest temperature for up to 16 hours.
    The accumulation of CO2 during regeneration can be used to calculate the total grams of carbon removed per gram of catalyst. When regeneration is performed to maximize system performance, the amount of carbon per gram of catalyst can be used to determine the average deposit rate for the carbonaceous species as well as to provide some predictive information on the duration between regenerations assuming conditions Similar operating methods are used.
    Alternatively, reductive regeneration can be used to remove the carbon-containing species from the catalyst surface. Reductive catalyst regeneration can be completed by heating the catalyst in the presence of hydrogen, resulting in the production of alkanes (eg CH4, C2H6, C3H8, C4H10, C5H12, C s H14, etc.). Similar to the oxidative regeneration described above, measuring the amount of alkanes emitted is an effective means of monitoring the state of regeneration,
    Extractants
    In addition to lignin, cellulose and hemicellulose, biomass includes ash components, such as calcium, aluminum, potassium, sodium, magnesium, chloride, sulfates, sulfites, thiol, silica, copper, iron, phosphates, and matches, as well as bodies with color (for example, terpenoids, stilbenes, flavonoids), proteinaceous materials and other inorganic products not susceptible to downstream conversion processes like those contemplated in this document. In the practice of the present invention, such materials, as well as unreacted and subreacted lignin, cellulose and
    54/92 hemicellulose, will often be present in the product stream as a solid material and removed as part of the catalytic washing process. Finally, lignin, ash and other extractants can be purged from the system and used in other processes. For example, lignin can be burned to provide process heat, while protein material can be used for animal feed or other products. Unreacted or underreacted cellulose and hemicellulose can be recycled to the biomass feed stream and processed until they are completely reacted.
    Liquid fuels and chemicals
    The C4 + compounds derived from the practice of the present invention as described above can be fractionated and used in liquid fuels, such as gasoline, jet fuel (kerosene) or diesel fuel. C4 + compounds can also be fractionated and used in chemical processes, such as those common to the petrochemical industry. For example, the product stream of the present invention can be fractionated to collect xylenes for use in the production of phthalic acid, polyethylene terephthalate (PET) and, finally, renewable plastics or solvents. Benzene can also be collected and processed to produce renewable polystyrenes, polycarbonates, polyurethane, epoxy resins, phenolic resins, and nylon. Toluene can be collected and processed to produce toluene disocyanate, and finally, renewable solvents, polyurethane foam or TNT, among others.
    In one embodiment, the C4 + compounds derived from the practice of the present invention are separated into various distillation fractions by any means known to liquid fuel compositions. In such applications, the product stream that has at least one C4 + compound derived from the process as described above is preferably separated
    55/92 in more than one distillation fraction, in which at least one of the distillation fractions is a lighter, moderate or heavy fraction. The lighter fractions, primarily C4 to C 9 , that is, C4, C 5 , C6, C7, C8, and C 9 , can be separated for gasoline use. The moderate fractions, primarily C7 to C14, that is, C7, C8, C9, C10, C11, C12 C13, and C14, can be separated for use as kerosene, for example, for use in jet aircraft fuel. The heavier fractions, primarily C12-C24, that is, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22, C23, θ C24, can be separated for diesel fuel use. The heavier fractions, C 25+ and C 30+ , that is, C 25 , C 26 , C 27 , C 28 , C 29 , C 30 , C 31 , C 32 , C 33 , C 34 , C 35 , etc. ., can be used as lubricants, fuel oils, or can be cracked to produce additional fractions for use in gasoline, kerosene and / or diesel fractions.
    Due to the fact that C 4+ compounds are derived from biomass, the age of the compounds, or fractions that contain the compounds, is less than 100 years, preferably less than 40 years, more preferably less than 20 years , as calculated from the component's carbon 14 concentration.
    The lightest fractions that have at least one biomass-derived C4 + compound have one or more of the following properties (LF-i to LF-vi):
    (LF-i) a final boiling point in the range of 150 to 220 ° C, more preferably in the range of 160 to 210 ° C;
    (LF-ii) a density at 15 ° C in the range of 700 to 890 kg / m 3 , more preferably in the range of 720 to 800 kg / m 3 ;
    (LF-iii) a sulfur content of a maximum of 5 mg / kg, more preferably a maximum of 1 mg / kg;
    (LF-iv) an oxygen content of a maximum of 3.5% in
    56/92 weight, more preferably at most 3.0% by weight, typically at most 2.7% by weight, and most typically at most 0.5%;
    (LF-v) a RON on banner in 80 to 110, more preferably in the range of 90 to 100; (LF-vi) a MON in banner in 70 to 100, more preferably in the range of 80 to 90. On such case, the fraction more Light has properties
    which are in accordance with each of the properties detailed in LF-i to LF-vi above, most conveniently with each of the preferred values for each of the properties detailed in LF-i to LF-vi above.
    Moderate fractions that have at least one biomass-derived C4 + compound have one or more of the following properties (MF-i to MF-vix):
    (MF-i) an initial boiling point in the range of 120 to 215 ° C, more preferably in the range of 130 to 205 ° C;
    (MF-ii) a final boiling point in the range of 220 to 320 ° C, more preferably in the range of 230 to 300 ° C;
    (MF-iii) a density at 15 ° C in the range of 700 to 890 kg / m 3 , more preferably in the range of 730 to 840 kg / m 3 ;
    (MF-iv) a sulfur content of a maximum of 0.1% by weight, more preferably a maximum of 0.01% by weight;
    (MF-v) a total aromatic content of at most 30% by vol., More preferably at most 25% by vol., Even more preferably at most 20% by vol., Most preferably at most 15% by vol .;
    (MF-vi) a freezing point of -40 ° C or less, more preferably at least -47 ° C or less;
    (MF-vii) a smoke point of at least 18 mm,
    57/92 more preferably at least 19 mm, even more preferably at least 25 mm;
    (MF-viii) a viscosity at -20 ° C in the range of 1 to 10 cSt, more preferably in the range of 2 to 8 cSt .;
    (MF-vix) a specific energy content in the range of 40 to 47 MJ / kg, more preferably in the range of 42 to 46 MJ / kg.
    In such a case, the moderate fraction has properties that are in accordance with each of the properties detailed in MF-i to MF-vix above, most conveniently with each of the preferred values for each of the properties detailed in MF-i to MF- vix above.
    The heaviest fraction that has at least one C4 + compound derived from biomass has one or more of the following properties (HF-i to HF-vi):
    (HF-i) a T95 in the 220 to 380 ° C, more preferably in the range of 260 to 360 ° C; (HF-ii) a flash point in the range 30 to 70 ° C, more preferably in the range of 33 to 60 ° C; (HF-iii) a density at 15 ° C in range in 700 to
    900 kg / m 3 , more preferably in the range of 750 to 850 kg / m 3 ;
    (HF-iv) a sulfur content of a maximum of 5 mg / kg, more preferably a maximum of 1 mg / kg;
    (HF-v) an oxygen content of a maximum of 10% by weight, more preferably a maximum of 8% by weight;
    (HF-vi) a viscosity at 40 ° C in the range of 0.5 to 6 cSt, more preferably in the range of 1 to 5 cSt.
    In this case, the heavier fraction has properties that are in accordance with each of the properties detailed in HF-i to HF-vi above, more conveniently with each of the preferred values for each of the properties detailed in HF-i to HF- saw above.
    58/92
    In liquid fuel applications, the fraction can be used as a pure fuel product or used as a blend component derived from biomass for a final liquid fuel composition. Accordingly, the present invention includes a liquid fuel composition that contains one or more of the lightest fractions, the moderate fractions or heavy fractions described above, as a blend component derived from biomass.
    The volume of the biomass-derived blend component in the liquid fuel composition must be at least 0.1% by volume, based on the total volume of the liquid fuel composition. For example, the amount of the biomass-derived blend component present in the liquid fuel composition must conform to one or more of the parameters (i) to (xx) listed below:
    (i) fur any less 0.5% in vol. (ii) fur any less 1% by vol. (iii) by any less 1.5% in vol. (iv) fur any less 2% by vol. (v) fur any less 2.5% in vol. (saw) fur any less 3% by vol. (vii) by any less 3.5% in vol. (viii) at least 4% in vol (ix) fur any less 4.5% in vol.
    (x) at least 5 vol%.
    (xi) a maximum of 99.5% by vol.
    (xii) maximum 99% by vol.
    (xiii) maximum 98% vol.
    (xiv) at most 97% by vol.
    (xv) maximum 96% vol.
    (xvi) maximum 95% vol.
    (xvii) maximum 90% by vol.
    (xviii) maximum 85% by vol.
    59/92 (xix) maximum 80% by vol.
    (xx) maximum 75% by vol.
    The amount of the biomass-derived blend component present in the liquid fuel composition of the present invention is in accordance with a parameter selected from (i) to (x) above, and a parameter selected from (xi) to (xx) above.
    For gasoline compositions according to the present invention, the amount of the biomass-derived blend component present in the gasoline composition will be in the range of 0.1 to 60% by volume, 0.5 to 55% by volume. or 1 to 50% by vol.
    For diesel fuel compositions according to the present invention, the amount of the biomass-derived blend component present in the diesel fuel composition will be in the range of 0.1 to 60% by volume, 0.5 to 55% by volume . or 1 to 50% by vol.
    For the kerosene compositions according to the present invention, the amount of the biomass-derived blend component present in the kerosene composition will be in the range of 0.1 to 90% by volume, 0.5 to 85% by volume. or 1 to 80% by vol., such as in the range of 0.1 to 60% by vol., 0.5 to 55% by vol. or 1 to 50% by vol.
    The liquid fuel composition of the present invention is typically selected from a gasoline, kerosene or diesel fuel composition. If the liquid fuel composition is a gasoline composition, then the gasoline composition has an initial boiling point in the range of 15 ° C to 70 ° C (IP123), a final boiling point of a maximum of 230 ° C (IP123) ), a RON in the range of 85 to 110 (ASTM D2699) and a MON in the range of 75 to 100 (ASTM D2700).
    If the liquid fuel composition is a kerosene composition, then the kerosene composition has
    60/92 an initial boiling point in the range of 110 to 180 ° C, a final boiling point in the range of 200 to 320 ° C and a viscosity at -20 ° C in the range of 0.8 to 10 mm 2 / s (ASTM D445).
    If the liquid fuel composition is a diesel fuel composition, then the diesel fuel composition has an initial boiling point in the range of 130 ° C to 230 ° C (IP123), a final boiling point of a maximum of 410 ° C (IP123) and a cetane number in the range 35 to 120 (ASTM D613).
    Preferably, the liquid fuel composition of the present invention further comprises one or more fuel additives.
    Gasoline compositions
    The gasoline composition according to the present invention typically comprises mixtures of hydrocarbons that boil in the range of 15 to 230 ° C, more typically in the range of 25 to 230 ° C (EN-ISO 3405). The initial boiling point of the gasoline compositions according to the present invention is in the range of 15 to 70 ° C (IP123), preferably in the range of 20 to 60 ° C, more preferably in the range of 25 to 50 ° C. The final boiling point of the gasoline compositions according to the present invention is a maximum of 230 ° C, preferably a maximum of 220 ° C, more preferably a maximum of 210 ° C. The ideal ranges and distillation curves that typically vary according to the climate and season.
    In addition to the biomass-derived blend component, the hydrocarbons in the gasoline composition can be derived by any means known in the art, conveniently, the hydrocarbons can be derived in any known manner from direct distillation gasoline, synthetically produced aromatic hydrocarbon mixtures, hydrocarbons thermally or catalytically cracked, hydrocracked oil fractions,
    61/92 catalytically reformed hydrocarbons or mixtures thereof.
    The search octane number (RON) of the gasoline compositions according to the present invention is in the range of 85 to 110 (ASTM D2699). Preferably, the RON of the gasoline composition will be at least 90, for example, in the range of 90 to 110, more preferably at least 91, for example, in the range of 91 to 105, even more preferably at least 92, for example, in the range of 92 to 103, even more preferably at least 93, for example, in the range of 93 to 102, and most preferably at least 94, for example, in the range of 94 to 100.
    The engine octane number (MON) of the gasoline compositions according to the present invention is in the range of 75 to 100 (ASTM D2699). Preferably, the MON of the gasoline composition will be at least 80, for example, in the range of 80 to 100, more preferably at least 81, for example, in the range of 81 to 95, even more preferably at least 82, for example, in the range of 82 to 93, even more preferably at least 83, for example, in the range of 83 to 92, and most preferably at least 84, for example, in the range of 84 to 90.
    Typically, gasoline compositions comprise a mixture of components selected from one or more of the following groups: saturated hydrocarbons, olefinic hydrocarbons, aromatic hydrocarbons, and oxygenated hydrocarbons. Conveniently, the gasoline composition can comprise a mixture of saturated hydrocarbons, olefinic hydrocarbons, aromatic hydrocarbons, and, optionally, oxygenated hydrocarbons.
    Typically, the olefinic hydrocarbon content of the gasoline composition is in the range of 0 to 40% by volume based on gasoline (ASTM D1319); preferably, the content of
    62/92 olefin hydrocarbon of the gasoline composition is in the range of 0 to 30% by volume based on the gasoline composition, more preferably, the olefinic hydrocarbon content of the gasoline composition is in the range of 0 to 20% by volume with based on gasoline composition.
    Typically, the aromatic hydrocarbon content of the gasoline composition is in the range of 0 to 70% by volume based on gasoline (ASTM D1319), for example, the aromatic hydrocarbon content of the gasoline composition is in the range of 10 to 60% by volume based on the composition of gasoline; preferably, the aromatic hydrocarbon content of the gasoline composition is in the range of 0 to 50% by volume based on the gasoline composition, for example, the aromatic hydrocarbon content of the gasoline composition is in the range of 10 to 50% by volume based on the composition of gasoline.
    The benzene content of the gasoline composition is a maximum of 10% by volume, more preferably a maximum of 5% by volume, especially a maximum of 1% by volume based on the composition of gasoline.
    The gasoline composition preferably has a low or ultra-low sulfur content, for example, at most 1000 ppmw (parts per million by weight), preferably not more than 500 ppmw, more preferably not more than 100, even more preferably not more than 50 and more preferably not more than 10 ppmw.
    The gasoline composition also preferably has a low total lead content, such as a maximum of 0.005 g / l, being more preferably lead free, with lead free compounds added to it (i.e. lead free).
    When the gasoline composition comprises oxygenated hydrocarbons, at least a portion of
    63/92 non-oxygenated hydrocarbons will be replaced by oxygenated hydrocarbons. The oxygen content of gasoline can be up to 30% by weight (EN 1601) based on the composition of gasoline. For example, the oxygen content of gasoline can be up to 25% by weight, preferably up to 10% by weight. Conveniently, the oxygen concentration will have a selected minimum concentration of any of 0, 0.2, 0.4, 0.6, 0.8, 1.0, and 1.2% by weight, and a selected maximum concentration of any of 5, 4.5, 4.0, 3.5, 3.0, and 2.7% by weight.
    Examples of oxygenated hydrocarbons that can be incorporated into gasoline, in addition to oxygenated hydrocarbons that may be present in the biomass-derived blend component, include alcohols, ethers, esters, ketones, aldehydes, carboxylic acids and their derivatives, and heterocyclic compounds that contain oxygen. Preferably, the incorporated oxygenated hydrocarbons are selected from alcohols (such as methanol, ethanol, propanol, iso-propanol, butanol, tert-butanol and iso-butanol), ethers (preferably ethers containing 5 or more carbon atoms per molecule, per example, methyl tert-butyl ether) and esters (preferably esters containing 5 or more carbon atoms per molecule); a particularly preferred oxygenated hydrocarbon is ethanol derived from biomass.
    When oxygenated hydrocarbons are present in the gasoline composition, the amount of oxygenated hydrocarbons in the gasoline composition can vary over a wide range. For example, gasolines that comprise a major portion of oxygenated hydrocarbons are currently and commercially available in countries such as Brazil and the U.S., for example, E85, as well as gasoline that comprises a smaller proportion of oxygenated hydrocarbons, for example, E10 and E5. Therefore,
    64/92 the amount of oxygenated hydrocarbons present in the gasoline composition is preferably selected from one of the following quantities: up to 85% by volume; up to 65% by volume; up to 30% by volume; up to 20% by volume; up to 15% by volume; and up to 10% by volume, depending on the desired final formulation of gasoline. Conveniently, the gasoline composition can contain at least 0.5, 1.0 or 2.0% by volume of oxygenated hydrocarbons.
    Examples of suitable gasoline compositions include gasolines that have an olefinic hydrocarbon content of 0 to 20% by volume (ASTM D1319), an oxygen content of 0 to 5% by weight (EN 1601), an aromatic hydrocarbon content of 0 to 50% by volume (ASTM D1319) and a benzene content of a maximum of 1% by volume.
    Although not crucial to the present invention, the gasoline compositions of the present invention can conveniently and additionally include one or more fuel additives. The concentration and nature of the fuel additive (s) that can be included in the gasoline composition of the present invention are not crucial. Non-limiting examples of suitable types of fuel additives that can be included in the gasoline composition of the present invention include antioxidants, corrosion inhibitors, detergents, turbidity inhibiting agents, anti-knock additives, metal deactivators, valve seat recession protecting compounds , dyes, friction modifiers, carrier fluids, thinners and markers. Examples of such suitable additives are generally described in U.S. Patent Document 5,855,629.
    Fuel additives can also be mixed with one or more diluents or carrier fluids, to form an additive concentrate, the additive concentrate can then be added by mixing with the
    65/92 gasoline of the present invention. The concentration (of active matter) of any additives present in the gasoline composition of the present invention is preferably up to 1
    per percent in Weight, more preferably in range 5 to 1000 ppmw, in form advantageous in the range of 75 to 300 ppmw, such how 95 to 150 ppmw.
    Alternatively, the gasoline composition of the present invention can be aviation gasoline. If the gasoline composition is aviation gasoline then, depending on the aviation gasoline grade, the Low Mixture Engine Octane Number will be at least 80 (ASTM D2700) and the Rich Mixture Octane Number will be at least 87 (ASTM D 909), or the low-mix engine octane number will be at least 99.5 (ASTM D2700) and the performance number will be at least 130 (ASTM D 909). In addition, if the gasoline composition is aviation gasoline then the vapor pressure (Reid method) at 37.8 ° C will be in the range of 38.0 to 49.0 kPa (ASTM D323), the final boiling point will be maximum 170 ° C (ASTM D 86), and the lead content of tetraethyl will be maximum 0.85 gPb / l.
    Kerosene fuel compositions
    The kerosene fuel compositions of the present invention are used in aviation engines, such as jet engines or overhead diesel engines, but also in any other suitable source of power or light. In addition to the biomass-derived blend component, the kerosene fuel composition may comprise a mixture of two or more different fuel components, and / or be added as described below.
    Kerosene fuel compositions will typically have boiling points within the range of 80 to 320 ° C, preferably in the range of 110 to 320 ° C, more preferably in the range of 130 to 300 ° C, depending on the
    66/92 grade and use. They will typically have a density of 775 to 845 kg / m 3 , preferably 780 to 830 kg / m 3 , at 15 ° C (for example, ASTM D4502 or IP 365). They will typically have an initial boiling point in the range of 80 to 150 ° C, preferably in the range of 110 to 150 ° C, and a final boiling point in the range of 200 to 320 ° C. Its kinematic viscosity at -20 ° C (ASTM D445) is typically in the range of 0.8 to 10 mm 2 / s, preferably from 1.2 to 8.0 mm 2 / s.
    The kerosene fuel composition of the present invention preferably contains not more than 3000 ppmw sulfur, more preferably not more than 2000 ppmw, or not more than 1000 ppmw, or not more than 500 ppmw sulfur.
    The kerosene fuel composition or its components can be additive (containing additives) or non-additive (free of additives). If it is added, for example, at the refinery or at later stages of fuel distribution, it will have smaller quantities of one or more additives selected, for example, antistatic agents (eg STADIS ™ 450 (eg OCtel)), antioxidants (for example, substituted tertiary butyl phenols), metal deactivating additives (for example, N, N'-disalicylidene 1,2-propanediamine), fuel system freezing inhibiting additives (for example, diethylene glycol monomethyl ether), additives corrosion inhibitors / lubricity enhancers (eg, APOLLO ™ PRI 19 (eg. Apollo), DCI 4A (eg. OCtel), NALCO ™ 5403 (eg. Nalco)), or thermal stability enhancement additives (eg example, APA 101 ™, (ex. Shell)) that pass international civilian and / or fuel specifications for military jet aircraft.
    The kerosene fuel composition of
    The present invention is particularly applicable where the kerosene fuel composition is used or intended for use in a jet engine. Unless otherwise stated, the concentration (of active matter) of each such additional component in the additive kerosene fuel composition is at the levels required or permitted in the international jet fuel specifications. In the above, the quantities (concentrations,% by vol., Ppmw,% by weight) of components are of active material, that is, exclusive of volatile solvent / diluent materials, unless otherwise stipulated in the relevant specification.
    Diesel Fuel Compositions
    The diesel fuel composition according to the present invention typically includes boiling hydrocarbon mixtures in the range of 130 to 410 ° C, more typically in the range of 150 to 400 ° C. The initial boiling point of the diesel fuel compositions according to the present invention is in the range of 130 to 230 ° C (IP123), preferably in the range of 140 to 220 ° C, more preferably in the range of 150 to 210 ° C. The final boiling point of the diesel fuel compositions according to the present invention is at most 410 ° C, preferably at most 405 ° C, more preferably at most 400 ° C.
    In addition to the biomass-derived mixing component, the diesel fuel composition may comprise a mixture of two or more different diesel fuel components and / or be added as described below.
    Such diesel fuel compositions will contain one or more base fuels which may typically comprise diesel oil (s) of liquid hydrocarbon distillate, for example, petroleum oils. Such
    68/92 fuels will typically have boiling points within the range described above, depending on grade and usage. They will typically have a density of 750 to 1,000 kg / m 3 , preferably 780 to 860 kg / m 3 , at 15 ° C (for example, ASTM D4502 or IP 365) and a cetane number (ASTM D613) of 35 to 120, more preferably 40 to 85. They will typically have an initial boiling point in the range described above and a final boiling point of a maximum of 410 ° C, preferably a maximum of 405 ° C, more preferably a maximum of 400 ° C, with maximum preference in the range of 290 to 400 ° C. Their kinematic viscosity at 40 ° C (ASTM D445) can be suitably from 1.2 to 4.5 mm 2 / s.
    An example of a petroleum-derived diesel is a Swedish class 1 base fuel, which will have a density of 800 to 820 kg / m 3 at 15 ° C (SS-EN ISO 3675, SS-EN ISO 12185), a T95 of 320 ° C or lower (SS-EN ISO 3405) and a kinematic viscosity at 40 ° C (SS-EN ISO 3104) of 1.4 to 4.0 mm 2 / s, as defined by the Swedish national specification report EC1 .
    Optionally, fuels based on non-mineral oil, such as biofuels (different from the component that has at least one C4 + compound derivable from a water-soluble oxygenated hydrocarbon) or Fischer Tropsch derivative fuels, can also form or be present in the fuel diesel. Such Fischer Tropsch fuels can be derived, for example, from natural gas, natural gas liquids, shale oil or oil, shale oil or petroleum processing residues, coal or biomass.
    The diesel fuel composition preferably contains no more than 5,000 ppmw of sulfur, more preferably not more than 500 ppmw, or no more than 350 ppmw, or no more than 150 ppmw, or no more than
    69/92
    100 ppmw, or not more than 70 ppmw, or not more than 50 ppmw, or not more than 30 ppmw, or not more than 20 ppmw, or most preferably not more than 15 ppmw sulfur.
    The diesel fuel itself can be additive (containing additive) or non-additive (free of additive). If added, for example, at the refinery, it will contain smaller amounts of one or more selected additives, for example, antistatic agents, pipe drag reducers, flow enhancers (for example, vinyl acetate / ethylene copolymers or maleic anhydride / acrylate copolymers), lubricity additives, antioxidants and anti-wax agents.
    Diesel fuel typically also includes one or more fuel additives. Detergent-containing diesel fuel additives are known and commercially available. Such additives can be added to diesel fuels at levels designed to reduce, remove, or delay the build-up of engine deposits. Examples of detergents suitable for use in diesel fuel additives for the present purpose include polyolefin-substituted succinimides or polyamine succinimides, for example, polyisobutylene succinimides or polyisobutylene amine succinimides, aliphatic amines, Mannich bases or maleic amines and polyolefin anhydrides ( for example, polyisobutylene). Dispersing succinimide additives are described, for example, in GB-A960493, EP-A-0147240, EP-A-0482253, EP-A-0613938, EP-A0557516 and WO-A-98/42808. Polyolefin-substituted succinimides are referred to particularly as polyisobutylene succinimides.
    The diesel fuel additive mixture may contain components other than detergent. Examples are
    70/92 lubricity enhancers; turbidity reducing additives (for example, alkoxylated phenol formaldehyde polymers); antifoaming agents (for example, polyether modified polysiloxanes); ignition enhancers (cetane enhancers) (for example, 2-ethylhexyl nitrate (EHN), cyclohexyl nitrate, di tert-butyl peroxide and those disclosed in US-A 4208190 in column 2, row 27 to column 3, row 21 ); antioxidating agents (for example, a propane-1,2-diol semi-ester of tetrapropenyl succinic acid, or polyhydric alcohol esters of a succinic acid derivative, with the succinic acid derivative having at least one of the alpha-carbon atoms a substituted or unsubstituted aliphatic hydrocarbon group containing 20 to 500 carbon atoms (for example, polyisobutylene-substituted succinic acid diester pentaerythritol); corrosion inhibitors; reodorants; anti-wear additives; antioxidants (for example, phenolics such as 2,6-di-tert-butylphenol, or phenylenediamines such as N, N'-di-sec-butyl-p-phenylenediamine); metal deactivators; combustion enhancers; static sink additives; cold flow enhancers; and anti-wax agents.
    The diesel fuel additive mixture may contain a lubricity enhancer, especially when the diesel fuel composition has a low sulfur content (for example, 500 ppmw or less). In the additive diesel fuel composition, the lubricity enhancer is conveniently present in a concentration of less than 1,000 ppmw, preferably between 50 and 1,000 ppmw, more preferably between 70 and 1,000 ppmw. Suitable commercially available lubricity enhancers include ester and acid-based additives. Other lubricity enhancers are described in the patent literature, in
    71/92 in particular, in connection with their use in low sulfur diesel fuels, for example, in: The document by Danping Wei and HA Spikes, The Lubricity of Diesel Fuels ”, Wear, III (1986) 217 a 235; WO-A-95/33805 (describing cold flow enhancers to enhance the lubricity of low sulfur fuels); WO-A94 / 17160 (describing certain esters of a carboxylic acid and an alcohol in which the acid has 2 to 50 carbon atoms and the alcohol has 1 or more carbon atoms, particularly glycerol monooleate and diisodecyl adipate, as fuel additives for wear reduction in a diesel engine injection system); US-A-5490864 (describing certain dithiophosphoric diester-alcohols as anti-wear lubricity additives for low sulfur diesel fuels); and WO-A-98/01516 (describing certain aromatic alkyl compounds that have at least one carboxyl group attached to their aromatic nuclei, to impart anti-wear lubricity effects particularly on low sulfur diesel fuels).
    It may also be preferable for the diesel fuel composition to contain a defoaming agent, more preferably in combination with an anti-oxidation agent and / or a corrosion inhibitor and / or a lubricity enhancing additive.
    Unless otherwise indicated, the concentration (active matter) of each such additive component in the additive diesel fuel composition is preferably up to 10,000 ppmw, more preferably in the range of 0.1 to 1,000 ppmw, advantageously from 0.1 to 300 ppmw, such as from 0.1 to 150 ppmw.
    The concentration (of active matter) of any turbidity-reducing additive in the diesel fuel composition will preferably be in the range of 0.1 to 20 ppmw,
    72/92 more preferably from 1 to 15 ppmw, even more preferably from 1 to 10 ppmw, advantageously from 1 to 5 ppmw. The concentration (active matter) of any ignition enhancer present will preferably be 2,600 ppmw or less, more preferably 2,000 ppmw or less, conveniently 300 to 1,500 ppmw. The concentration (active matter) of any detergent in the diesel fuel composition will preferably be in the range of 5 to 1,500 ppmw, more preferably from 10 to 750 ppmw, with a maximum preference of 20 to 500 ppmw.
    In the case of a diesel fuel composition, for example, the fuel additive mixture will typically contain a detergent, optionally together with other components as described above, and a diesel fuel compatible diluent, which can be a mineral oil, a solvent such as those sold by Shell companies under the trademark SHELLSOL, a polar solvent such as an ester and, in particular, an alcohol, for example, hexanol, 2 ethylhexanol, decanol, isotridecanol and alcohol mixtures such as those sold by Shell companies under the trademark LINEVOL, especially LINEVOL 79 alcohol which is a mixture of C 7-9 primary alcohols, or a mixture of C 12-14 alcohol which is commercially available.
    The total content of the additives in the diesel fuel composition can suitably be between 0 and 10,000 ppmw and preferably below 5,000 ppmw. In the above, the quantities (concentrations,% of volume, ppmw,% by weight) of components are of active material, that is, exclusive of diluent materials / volatile solvents.
    The following examples are to be considered illustrative of various aspects of the invention and should not be construed as limiting the scope of the invention, which is defined by the appended claims.
    73/92
    EXAMPLES
    Example 1
    The product streams of the examples described below were analyzed as follows. The organic liquid phase was collected and analyzed using gas chromatography with mass spectrometry detection or flame ionization detection. Component separation was achieved using a column with a stationary 100% bound dimethyl polysiloxane phase. The relative concentrations of individual components were estimated through peak integration and dividing by the sum of the peak areas for an entire chromatogram. The compounds were identified by comparing standard retention times and / or comparing mass spectra to a compiled mass spectrum database. The vapor phase compositions, for non-condensable species, were determined by gas chromatography with a thermal conductivity detector and flame ionization or gas chromatography with a flame ionization detector or mass spectrometry detectors for other phase components of vapor (for example, condensable species of organic or aqueous phase). The liquid phase fraction was analyzed using gas chromatography with and without a derivatization of the organic components of the fraction using a flame ionization detector. Product yields are represented by the feed carbon present in each product fraction. The hourly space mass velocity (WHSV) was defined as the feed weight introduced into the system by weight of catalyst per hour, and based on the weight of the oxygenated hydrocarbon feed only, excluding the water present in the feed.
    Example 2
    A biomass feed stream that contains
    74/92
    10% (weight / v) of microcrystalline cellulose (MCC) in water was converted to a gas phase containing volatile C 2+ O 1-2 oxygenates and a liquid phase using modified palladium on tungsten zirconia oxide support. The conversion was carried out in a 300 ml Parr reactor at 260 ° C and 6.89 MPa (1,000 psi) of H 2 , with a reaction time of 15 minutes. The reaction included a 1: 3 catalyst: biomass ratio.
    The hydrogen residue washing and constant mixing at 800 rpm was used to increase the mixture and catalyst contact. The mixing occurred from the beginning of heating until the end of cooling. The constant residue washing allowed the volatile C2 + O1-2 oxygenates to be collected in the upper and separated from the residual aqueous products left in the reactor. Both the vapor phase and liquid phase products can be seen in Figures 3, 4a, 4b and 5. Figure 3, in particular, provides overall selectivity and conversion. The condensed vapor stream contained C 2+ O 1-2 oxygenates as shown in Figure 6 and Table 1 below. The products of non-condensable gas from the vapor stream were analyzed and can be seen in Figure 7.
    Table 1. MCC Organic Product Distribution
    Species % 1-HEXANOL 10.6 1-Octanol 2.6 CYCLOPENTANONE, 2-METHYL- 2.4 1-NONANOL 2.3 1-DECANOL 2.0 1-Pentanol 1.6 2-Nonanone 1.5 (6Z) -Nonen-1-ol 1.5 1-HEPTANOL 1.4
    75/92
    Cyclopentanomethanol 1.2 3-Cyclopentyl-1-propanol 1.2 1-Dodecanol 1.2 Phenol, 2,3-dimethyl- 1.0 2-Hexanone 1.0
    Through the use of residue washing and vapor phase sampling, the condensed volatile oxygenates consisted primarily of alcohols and other mono-oxygenates, leaving sugars and polyols in the liquid phase. As seen by the depletion of organic product in Table 1 and Figure 6, the organic stream collected with the vapor phase is primarily alcohols and ketones with some unidentified compounds. Carbon losses through the non-condensable gas stream are minimal as seen by the gas product analysis (Figure 7) which shows almost no carbon monoxide or dioxide.
    Example 3
    A biomass feed stream containing 12 to 17% (weight / v) of loblolly pine in water was converted to a gas phase containing volatile C2 + O1-2 oxygenates and a liquid phase using modified palladium on a support of tungstated zirconia oxide. The conversion was carried out in a 300 ml Parr reactor at 280 ° C and 6.89 MPa (1,000 psi) of H 2 , with a reaction time of 15 minutes. The reaction included a 1: 3 catalyst: biomass ratio.
    The hydrogen residue washing and constant mixing at 800 rpm was used to increase the mixture and the catalyst contact. The mixing occurred from the beginning of heating until the end of cooling. The constant residue washing allowed the volatile C 2+ O 1 _ 2 oxygenates to be collected in the upper and separated from the residual liquid phase products left in the reactor. Volatile oxygen
    76/92 collected were then condensed and analyzed. less volatile residual liquid phase products were collected after the reactor was cooled and analyzed in a similar way.
    The results of the analysis of both the vapor phase and liquid phase products are provided in Figures 8, 9a, 9b and 10. Figure 11 is an analysis of the non-condensable vapor phase products. The vapor phase contained volatile C 2+ O 1-2 oxygenates (both oxygenated mono- and dihydrocarbons), while the liquid phase portion consisted primarily of sugars. Minimal carbon losses through the non-condensable gas product were observed with lower levels of carbon dioxide and carbon monoxide in the analysis.
    Example 4THE Figure 12 shows a diagram of process what illustrates one system of exemplary reactor that is useful at practice gives reaction of condensation of this invention. The oxygenates volatile, such as C2 + alcohols O1-2, ketones,
    cyclic ethers, organic acids, or other polyoxygenated compounds, enter the system in stream 202 and are directed through the condensation reactor (in this case, a dehydration / oligomerization reactor). Hydrogen (either external, recycled, H 2 in situ, or a combination thereof) is coiled to the reactor in stream 301.
    The product stream from the condensation reactor is sent to the light removal column, where heavy and moderate hydrocarbons (for example, kerosene, diesel fuel and lubricants) are separated at the bottom to supply the 411 stream. The lightest components in the top are sent to a three-phase separator. A gas phase stream of predominantly carbon dioxide and hydrogen, with lower amounts of light hydrocarbons, is removed in stream 404. The phase
    77/92 liquid, composed of water and low levels of organic compounds, is removed in stream 412. A three-phase separator can also be used to remove the liquid phase upstream of the column. The upper organic phase is divided into three streams; (1) backflow to the column, stream 406, (2) the grid product, stream 407, (3) recycle back to the reactor system, stream 408. In certain embodiments, the recycle stream can be sent back to the condensation reactor. Residual alkenes and oxygenates can be further oligomerized to C3-C30 hydrocarbons (for example, C3, C4, C5, C6, C7, Ce, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C 20, C 21, C 22, C 23, C24, C 25, C 26, C 27, C 28, C 29 and C30
    a catalyst in condensation was prepared dissolving the nitrate in nickel in water and So adding up the mixture a an zeolite preparation ZSM-5 bound by alumina (SiO 2 : Al 2 O 3 30: 1, 1/8 ”extruded) how
    use of an incipient moisture technique to target a 1.0% by weight nickel loading. The preparation was dried overnight (for example, more than 4 hours, or 5 hours, or 6 hours, or 7 hours, or 8 hours and less than 16 hours, or 15 hours, or 14 hours, or 13 hours, or 12 hours, or 11 hours, or 10 hours) in a vacuum oven and subsequently calcined in a current stream of air at 400 ° C.
    Example 6
    A condensation catalyst was prepared by dissolving copper nitrate in water and then adding the mixture to a tungsten zirconia catalyst support (NorPro Saint-Gobain, Product code SZ31164, with particle sizes restricted to those that were kept on a screen of 60 mesh after passing through an 18 mesh screen) with the
    78/92 use of an incipient moisture technique to target a 10% copper load on the catalyst after the subsequent decomposition of the metal precursors. The preparation was dried overnight (for example, more than 4 hours, or 5 hours, or 6 hours, or 7 hours, or 8 hours, and less than 16 hours, or 15 hours, or 14 hours, or 13 hours , or hours, or 11 hours, or 10 hours) in a vacuum oven at 100 ° C and subsequently calcined in an air stream at 400 ° C.
    Example 7
    A condensation catalyst was prepared by dissolving palladium nitrate and silver nitrate in water and then adding the mixture to a tungsten zirconia catalyst support (NorPro Saint-Gobain, Product code SZ31164, with sizes of particles restricted to those that were kept on a 60 mesh screen after passing through an 18 mesh screen) using an incipient humidification technique to target a 0.5% palladium charge and a silver charge of 0.5% in the catalyst after the subsequent decomposition of the metal precursors. The preparation was dried overnight (for example, more than 4 hours, or 5 hours, or 6 hours, or 7 hours, or 8 hours, and less than 16 hours, or 15 hours, or 14 hours, or hours, or 12 hours, or 11 hours, or 10 hours) in a vacuum oven at 100 ° C and subsequently calcined in a stream of air flow at 400 ° C.
    Example 8
    A stream of volatile C2 + O1-2 oxygenates similar in composition to that produced in Example 2 and illustrated by Figure 6 was converted to a stream of C4 + hydrocarbon product using the condensation catalysts described in Examples 5 and 6. The composition of the intermediate current that is fed into the condensation reactor
    79/92 is described in Table 2, with 99% of all components having carbon chain lengths of six or less.
    Table 2 - Composition of Intermediate Current of
    Organic Phase
    Breakdown of Organic Phase Composition Alcanos % carbon in organic phase 15.0 Total Mono-Oxygenates % carbon in organic phase 75.7 Alcohols % carbon in organic phase 40.1 Ketones % carbon in organic phase 11.4 Cyclic ethers % carbon in organic phase 19.3 Cyclic mono-oxygenates % carbon in organic phase 5.0 Organic acids % carbon in organic phase 6.9 C6- Components % carbon in organic phase 99, 0
    The stream of volatile oxygenates was fed over the condensation catalyst using the process configuration described in Example 4. The catalyst was loaded as a packed bed with a height of 30.5 cm (12 ”) in a tube and shell reactor 2.54 cm (1 ”) in diameter. The reaction conditions are described in Table 3.
    The heavy liquid stream (411 in Figure 12) was collected and analyzed using the techniques listed in Example 1. Table 3 shows the composition and yields of organic product depending on the formulation of the catalyst. Non-condensed components are those components that do not require the formation of new carbon-carbon bonds to be produced from the given feed. For the sake of simplicity, all compounds containing six or less carbon atoms are considered to be non-condensing components (for example, C 1 , C 2 , C 3 , C 4 , C 5 , C6). The products
    80/92 of total condensation are those compounds that contain seven or more carbon atoms (for example, C7, C 8 , C 9 , C 10 , C 11 , C 12 , C13, C14, C15, C16, C17, C18, C19, C20, C21, C22, C23, C24, C25, C26,
    C27, C28, C29 and C30), which require the formation of new carbon-carbon bonds to be formed from the given raw material.
    The exception to this is the dioxigenate category, which are esters that lack a continuous carbon main chain. These compounds would not maintain their chain lengths if hydrogenated to a finished liquid fuel.
    The Unclassified category contains compounds that are too heavy for accurate identification using the analysis technique. An estimate of the number of carbon is made based on the boiling point, and in general these compounds have continuous carbon chains.
    Both catalysts show significant condensation taking place. The volatile oxygen stream contained 99% of non-condensing components, while the heavy liquid stream product 411 contains less than 4% in both cases. The resulting products can be hydrogenated using a water treatment catalyst to produce gasoline, kerosene and diesel fuels.
    Table 3 - Conversion of Volatile Oxionates to
    C7 + Carbon Chains
    Catalyst1% Ni/ ZSM-5 10% Cu /W-ZrO2 WHSV Feed weight / ( Catalyst weight h) 0.7 0.4 HydrogenAdded mol H2 / mol feed 0.2 0.2 Temperature ° C 300 300 Pressure MPa (Psig) 5.52 4.14 (600)
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    (800)Yield of Heavy Organic Phase (current 411) % carbon feed 69 42 Breakdown of Heavy Organic Phase Composition HydrocarbonsC6- % carbon in the organic phase 0.1 2.1 C6- Oxygenates % carbon in the organic phase 1.0 1.8 Components notCondensedTotals % carbon in the organic phase 1.1 3.9 HydrocarbonsC7 + % carbon in the organic phase 30.3 3.7 MonooxygenatesC7 + % carbon in the organic phase 9.1 24.9 C7 + Dioxigenates % carbon in the organic phase 4.2 1.1 UnclassifiedC7 + % carbon in the organic phase 55.3 66.3 Products fromCondensationTotals % carbon in the organic phase 98.9 96.1
    Example 9
    A stream of C 2+ O 1 _ 2 volatile oxygenates similar in composition to those produced in Examples 2 and 3 was converted to a stream of C 4+ hydrocarbon product using the condensation catalyst described in Example 7. Table 4 shows the composition of the intermediate current that is fed to the condensation reactor. All values are reported as a percentage by weight.
    Table 4 - Intermediate Current Composition
    Oxygenated
    Number of
    Carbons
    Others
    DioxiAgua Alcanos Ketones Alcohols Monooxy-Furans Diols Acids genatos genatos
    82/92
    0 60.9 1 0.1 2 0.1 0.4 0.4 3 0.6 0.30.7 0.3 0.4 4 0.3 0.2 0.1 0.7 0.3 0.4 5 0.8 0.5 0.1 1.3 0.40.1 60.1 0.8 1.2 4.7 5.7 4.3 0.2 0.2 > 70.1 1.4 2.0 1.3 0.2 1.8 THE current C 2+ O 1 oxygenates -2 volatile was powered on the condensation catalyst with the use of configuration of process described in the Example 4. The catalyst
    it was loaded as a packed bed 30.48 cm (12 inches) high in a 2.54 cm (1 inch) diameter housing and tube reactor. The reaction was carried out at 300 ° C and 6.21 MPa (900 psig) at a mass hourly space velocity of 0.4 hr -1 . A hydrogen coalimentation of 2.4 mol H2 / mol feed was used with a recycling: feed ratio of 1.7.
    Approximately 90% of the carbon that went through the process (for example, deconstruction and condensation) was converted to the organic phase. Approximately 75% were contained in the heavier chain fraction 411 and 15% were in the lighter chain fraction 407. Figure 13 shows that the carbon chain lengths of the products have been increased in relation to food. In general, these components have continuous main carbon structures and can be hydrogenated to form gasoline, kerosene and diesel fuels.
    Example 10
    The organic products of Example 9 were fed on a commercially available nickel hydrotreating catalyst to hydrogenate the remaining oxygen and alkenes. Both streams 407 and 411 were fed to the hydrotactor. The hydrotreating catalyst was loaded as a bed packed with 50.8
    83/92 cm (20 inches) tall in a 2.54 cm (1 inch) diameter housing and tube reactor with 1: 1 ratio silicon carbide. The reaction was carried out at 300 ° C, 5.52 MPa (800 psig), mass hourly space velocity of 1.0 hr -1 and a 4: 1 hydrogen coalimentation. The product produced was> 98% of fully saturated hydrocarbons.
    Example 11
    The hydrotreated product of Example 10 was fractionated using standard distillation techniques to produce a gasoline product. The sample had an initial boiling point of 48 ° C and an end point of 163 ° C as determined by the ASTM D86 method. The test distillation curve is shown in Figure 14. Approximately 20% of the hydrotreated material was contained in this product fraction.
    Example 12
    The hydrotreated product of Example 10 was fractionated using standard distillation techniques to produce a kerosene product. The sample had an initial boiling point of 163 ° C and an end point of 292 ° C as determined by the ASTM D86 method. The test distillation curve is shown in Figure 15. The sample had a flash point of 50 ° C as determined by the ASTM D56 method. Approximately 50% of the hydrotreated material was contained in this product fraction.
    Example 13
    The hydrotreated product of Example 10 was fractionated using standard distillation techniques to produce a diesel product. The sample had an initial boiling point of 167 ° C and an end point of 334 ° C as determined by the ASTM D86 method. The test distillation curve is shown in Figure 16. The sample had a
    84/92 inflammation of 56 ° C as determined by the ASTM D56 method. Approximately 60% of the hydrotreated material was contained in this fraction of product.
    Example 14
    A mixture of volatile C2 + O1-2 oxygenates similar to those produced in Examples 2 and 3 was converted into fuel and chemical products using a condensation catalyst according to the process of the present invention. Table 5 shows the carbon number distribution and component classification of the components contained within the mixture of volatile oxygenates fed to the condensation reactor.
    Table 5 - Oxygen Mixture Composition
    Powered by Condensation Reactors (% by weight)
    NumberinCarbons Others Water Alcanos Ketones Alcohols Monooxi- Dioxi- genomes Furans genomes Diols Acids 0 65.8 1 0.62 4.0 0.4 3 0.5 3.8 0.1 0.4 0.4 40.1 0.2 3.0 0.7 0.3 0.2 1.9 0.5 50.2 1.0 2.4 0.1 2.8 0.10.4 60.5 0.9 1.9 0.7 5.4 0.30.3
    The mixed volatile oxygen supply was converted to hydrocarbons using the catalyst described in Example 5 and two 2.54 cm (1 inch) OD downflow reactors connected in series, with each containing approximately 27 fixed catalyst beds , 94 cm (11 inches) in length. The process conditions are shown in Table 6. The products of this experiment were analyzed by methods described in Example 1. The components produced from this experiment were primarily hydrocarbons that have the general composition shown in Table 7.
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    Table 6 - Condensation Reactor Conditions
    Condition Units Catalyst Catalyst Weight Total g Feed Rateg / min TemperatureMain Reactor ° C Reactor TemperatureRange ° C PressureMPa (psig)
    Value
    1% Ni in ZSM-5 (SAR 30, 20% Al 2 O 3 Binder, 1 / 40.64 cm (16 inches) of Extrudates)
    147
    2.35
    361
    340
    0.52 (75)
    Table 7 - Breakdown of Condensation Reactor Output Composition
    % by weight of carbon Component Intermediate Feed Alcanos 34.9 Aromatic 53.6 Alkenos 7.1 Cycloalkanes 3.8 Dienos 0.6
    Example 15
    The product of Example 14 was distilled using well-known laboratory scale distillation equipment. As shown in Table 8, most of the product stream included compounds in the gasoline boiling range. The gasoline boiling range for this 10 experiment was described as having an initial boiling point of 28 ° C and a final boiling point of 176 ° C.
    Table 8 - Distribution of Acid Condensation Product after Fractionation of Gasoline Fraction
    Component % by weight offoodIntermediate Carbon ofin Weight% of WeightIntermediate Product Light Gas 18.1- Heavy organic 5.6- -
    86/92
    Gasoline 76.3 - Alcanos - - 28.5 Aromatic - - 61.2 Alkenos - - 4.5 Cycloalkanes - 5.1 Dienos - - 0.7
    The product of Example 14 was also distilled using distillation equipment on a well-known laboratory scale in such a way as to provide a product with a high content of C8 (A8) aromatics. The resulting product contained a total of 97.3% C 8 aromatics, including 14.4% by weight of ethylbenzene, 23.1% for xylene, 48.4% for meta xylene and 10.5% for ortho xylene. This material is similar in composition to a mixed C8 aromatic stream that is used as a raw material for the industrially practiced production of aromatic chemicals.
    Example 16
    A deconstruction catalyst containing 2% Pd, 2% Ru and 13.5% W in a monoclinic zirconia support was used for the deconstruction of maize crop remains. Water was used as the initial solvent followed by the recycling of oxygenated hydrocarbons C2 + O2 + residual from the liquid phase. A feed stream comprising 10% (w / v) of corn crop remains washed with water with a catalyst to biomass ratio of 1: 3 was fed to a reactor system operating at 250 ° C to 285 ° C and 6 55 MPa (950 psig) to 7.58 MPa (1,100 psig) H 2 . Fresh catalyst was used for the first two recycling cycles, after which the regenerated catalyst was used. The conditions of preparation and regeneration of catalyst are shown in Table 9.
    Table 9 - Preparation and Regeneration Catalyst
    Catalyst# FCC78 Calcination Reduction Passivation Regeneration
    87/92
    Fluent Gas Air H2 <3% O2 inN2 environment <3% O2 in N2 environment Temperature 400 ° C 350 ° C <35 ° C 450 ° C Elevation 1.6 ° C / min 2.7° C / min AT 1.25 ° C / min Immersion 6 hours 2 hours 2 hours 16 hours
    The recycling of the liquid phase fraction led to a steady increase in total organic carbon (TOC) in the liquid product stream by adding more biomass carbon to the solvent as shown in Figure 17. Figure 18 illustrates the changed product distribution during each recycling cycle in both background fractions and volatile C2 + O1-2 oxygenates. The volatile C2 + O1-2 oxygen fractions show a large amount of alcohols and ketones as well as short chain acids compared to the more oxygenated species left in the bottom fraction. The growing acidic trend is an accumulation of acetic acid from biomass, particularly hemicellulose, rather than a tendency to selectivity from the catalyst.
    Example 17 deconstruction containing 2% of a catalyst in Pd, 2% Ru and 13.5% in W on a zirconia holder monoclinic was used for the deconstruction of remains
    maize in a solvent derived from hydroxygenation (HDO) (60% (w / v) of corn syrup on a trimetallic catalyst), followed by recycling the residual liquid stream, that is, oxygenated hydrocarbons C2 + O2 + not collected through of the vapor phase sampling. A feed stream containing 10% (w / v) of corn crop remains washed with water with a catalyst to biomass ratio of 1: 3 was fed to a reactor system operating at 250 ° C to 285 ° C and 6 55 MPa (950 psig) to 7.58 MPa (1,100 psig) of H2. Fresh catalyst was used for the first two recycling cycles, followed by
    88/92 regeneration catalyst for cycles three and four. The catalyst was regenerated according to the conditions described in Table 9.
    Figure 19 illustrates the effect of aqueous recycling in TOC on the aqueous product stream. Figure 20 illustrates the effect of aqueous recycling on product distribution in both the volatile and bottom oxionate fractions, specifically the C2 + O1-2 oxygenates in the volatile fraction and the bottom diols and polyoxygenates (liquid phase used as the solvent for recycling). Figure 21 illustrates the product speciation of the aqueous phase that includes the specific compounds and the increase in TOC over time. A representative condensable vapor phase is shown in Figure 22.
    Example 18
    A deconstruction catalyst containing 2% Pd and 2% Ag in a tungsted zirconia support was used for the deconstruction of MCC. The reactor conditions were 10% (w / v) MCC in water, 1: 3 catalyst: MCC, 240 ° C to 285 ° C (Cycle 2 240 ° C to 275 ° C, Cycle 3 260 ° C to 285 ° C) and 6.55 MPa (950 psig) to 7.24 MPa (1,050 psig) of H2. Fresh catalyst was used for Cycle 2 with a combination of fresh catalyst and regenerated catalyst used for Cycle 3 in a 1: 1 ratio between fresh catalyst and regenerated catalyst. Product distribution and speciation are summarized in Figures 23 and 24, respectively.
    Example 19
    A biomass feed stream containing 10% (w / v) MCC in water was converted to a gas phase containing volatile C2 + O1-2 oxygenates and a liquid phase containing oxygenated C2 + O2 + hydrocarbons using a catalyst. deconstruction containing 2% Pd and 2% Ag in a tungsted monoclinic zirconia support. The reaction was performed in a system similar to the configuration illustrated in
    89/92
    Figure 25. The reactor was operated at a temperature of 240 ° C to 280 ° C and a pressure of 6.89 MPa (1,000 psig) with a residence time of 10 minutes. The reaction products were analyzed as described in Example 1. The carbon number distribution and component classification of the liquid product are summarized in Table 10.
    Table 10 - Mixture Feed Composition
    Oxygenates in the Condensation Reactor (% by weight)
    Number of Carbons Water Ketone Alcohol Furano Dioxigenate Polyoxygenate Diol Acid 0 94.4 1 0.0320.01 0.07 0.06 30.01 0.000.49 0.38 0.02 0.15 4 0.08 0.00 0.03 0.01 50.01 0.00 0.000.060.01 60.01 0.81 0.030.01 0.01 0.02 70.220.02 8 9 0.07
    The mixed oxygen supply was converted to hydrocarbons in a 1 / 5.08 cm (2 inch) downflow ID reactor loaded with the catalyst described in Example 5. The reactor system is illustrated in Figure 26. The reactor was operated at a temperature of 385 ° C, a pressure of 0.52 MPa (75 psig) and a WHSV of 0.2 hr 1 . The products of this experiment were analyzed using the methods described in Example 1. The products of the gas, organic and aqueous phase were recovered, resulting in approximately 90% of carbon conversion in the aqueous phase. The organic phase product contained 92.4% by weight of aromatic components, suitable for use as chemicals or a blendstock gasoline, with a carbon number distribution shown in Figure 27.
    Example 20
    90/92
    Three separate biomass feed streams (crop residues of maize, pine wood and sugar cane bagasse) have been converted into a gas phase containing volatile C 2+ O 1-2 oxygen and a liquid phase containing oxygenated C2 + O2 + hydrocarbons with the use of a deconstruction catalyst containing palladium, molybdenum and tin supported in tungsten zirconia in a stage two reactor system. A deconstruction solvent of similar composition to the residual liquid phase of Example 2 was used as a contact carrier between the biomass and deconstruction catalyst.
    Depending on the particle density size, 25 to 45 grams of biomass and 70 grams of deconstruction catalyst were loaded as packed beds at a height of 30.48 cm (12 inches) and a diameter of 2.54 cm (1 inch) . The first deconstruction reactor was operated with a temperature rise of 120 to 310 ° C and a pressure of 8.27 MPa (1,200 psi) to allow pressure-driven transfer to the second reactor, which was operated at 7.24 MPa ( 1,050 psi) and a temperature rise of 180 to 270 ° C. The deconstruction solvent was fed to the system at a rate of 2.9 g / min, resulting in a mass hourly space velocity (WHSV) of 3.9 to 6.9 g of solvent / g of biomass per hour (depending on the mass loaded) or 2.5 g of solvent / g of catalyst per hour. The hydrogen was coalimented at a rate of 1.9 mol / h.
    The steam, liquid and organic products of the second reactor were analyzed as described in Example
    1. The general conversion for the three biomass raw materials can be seen in Figure 28. A combined analysis of the product of the liquid phase and the condensed vapor phase can be seen in Figures 29, 30, and 31. The phase product unidentified liquid is typically a partially sugar species
    91/92 deoxygenated derived from cellulose and hemicellulose components; however, some products of deconstruction of lignin may also be present. A representative condensable vapor phase is shown in Figure 32. Standard cellulose and hemicellulose deoxygenation products, such as alcohols and cyclic ethers, are present in this product stream. Additionally, lignin deconstruction products are present in the form of substituted benzene components - products not seen in MCC deconstruction.
    Example 21
    A biomass feed stream containing 10% (w / v) bagasse in water was converted into a gas phase containing volatile C 2+ O 1-2 oxygenates and a liquid phase containing oxygenated C 2+ O 2+ hydrocarbons with use of modified nickel and palladium catalysts. The conversion was performed in a 500 ml Parr reactor at 150 to 280 ° C and
    6.96 MPa (1,010 psi) for a total of 100 minutes. A catalyst chosen from Table 11 was loaded into the reactor at a weight ratio of biomass and catalyst of 3: 1. The catalysts used are shown in Table 11.
    Table 11 - Deconstruction Catalyst Screening
    Metal Loading Support2% Pd, 2% Mo, 0.5% Sn Tungsted zirconia 5% Ni, 0.5% B Tungsted zirconia 5% Ni, 10% Mo, 0.5% B Tungsted zirconia 5% Ni, 2% Ru, 1% Re Tungsted zirconia
    The biomass feed stream was mixed at 800 rpm for the duration of the reaction to increase the mass and heat transfer throughout the entire mixture. A compressor was used to recycle approximately 2 l / min of the non-condensable gaseous product back to the reactor and extracted from the condensable vapor, while fresh hydrogen was
    92/92 fed at 200 ml / min. The reaction was quenched after 100 minutes and the products were analyzed by the methods described in Example 1. The conversion of raw material is shown in Figure 33. The compositions of the residual liquid phase 5 and the condensable vapor phase stream are shown in Figures 34 and 35, respectively.
    The residual liquid phase stream consisted mainly of sugars and polyols, while the condensed vapor phase stream consisted mainly of alcohols 10 and ketones that were volatilized during the reaction. The condensed vapor phase also contained an organic product shown in Figure 36. The speciation of this stream shows the reaction of cellulose and hemicellulose in alcohols and cyclic ethers. In addition, the product profile shows products for deconstructing lignin in substituted benzene compounds, components not seen when using pure cellulose or carbohydrate raw materials.
    权利要求:
    Claims (9)
    [1]
    1. METHOD FOR CONVERTING BIOMASS INTO CHEMICALS AND FUELS DERIVED FROM BIOMASS, the method being characterized by understanding:
    providing a biomass feed stream comprising a solvent and a solid biomass component comprising cellulose, hemicellulose or lignin;
    catalytically reacting the biomass feed stream with hydrogen and a deconstruction catalyst at a deconstruction temperature and a deconstruction pressure to produce a product stream comprising a vapor phase, a liquid phase and a solid phase, the phase being of vapor comprises one or more volatile C2 + O1-2 oxygenates, in which the oxygenates have a relative volatility α, relative to 1-hexanol, greater than 0.03 based on pure components at 250 ° C, the phase being liquid comprises water and one or more oxygenated hydrocarbons C2 + O2 +, whose oxygenated hydrocarbons have a relative volatility α, relative to 1-hexanol, less than 0.03 based on pure components at 250 ° C, and the solid phase comprises extractants ;
    separating the volatile C2 + O1-2 oxygenates from the liquid and solid phases; and directing the volatile C2 + O2 + oxygenate to a condensation step, the condensation step comprising catalytically reacting the volatile C2 + O1-2 oxygenates in the presence of a condensation catalyst at a condensing temperature and condensing pressure to produce a compound C4 + comprising a member selected from the group consisting of C4 + alcohol, C4 + ketone, C4 + alkane, C4 + alkene, C5 + cycloalkane, C5 + cycloalkene, aryl, fused aryl and a mixture thereof.
    [2]
    2. METHOD, according to claim 1,
    Petition 870190063717, of 07/08/2019, p. 9/19
    2/9 characterized by the solvent comprising one or more members selected from the group consisting of water, oxygenated hydrocarbons C2 + O2 + generated in situ,
    oxygenated hydrocarbons C2 + O2 + recycled, solvents in bioconversion, solvents organic, acids organic and an mix of me smos. 3. METHOD, according with the claim 1, featured by the stage solid to understand, additionally , O catalyst deconstruction. 4. METHOD, according with the claim 3,
    characterized by additionally understanding the steps of:
    separating the deconstruction catalyst from the liquid phase;
    washing the deconstruction catalyst in one or more washing means;
    regenerating the deconstruction catalyst in the presence of oxygen or hydrogen, at a regeneration pressure and regeneration temperature at which carbonaceous deposits are removed from the deconstruction catalyst; and reintroducing the deconstruction catalyst to react with the biomass feed stream.
    5. METHOD according to claim 1, characterized in that the solid biomass component comprises at least one member selected from the group that includes recycled fibers, crop residues of corn, bagasse, yellow millet, miscanto, sorghum, wood, wood residues, agricultural waste, algae and urban waste.
    6. METHOD according to claim 1, characterized in that the deconstruction catalyst comprises an acidic support or a basic support.
    7. METHOD, according to claim 1, characterized by the deconstruction catalyst comprising a support and a member selected from the group that
    Petition 870190063717, of 07/08/2019, p. 10/19
    [3]
    3/9 consists of Ru, Co, Rh, Pd, Ni, Mo and their alloys.
    8. METHOD, according to claim 7, characterized by the deconstruction catalyst further comprising a member selected from the group consisting of
    in Pt, Re, Faith, Go, Cu, Mn, Cr, Mo, B, W, V, Nb, Ta, Ti, Zr, Y, La, Sc, Zn, Cd, Ag, Au, Sn, Ge, P, Al, Ga, In, Tl and alloys From themselves. 9 . METHOD, in wake up with the claim 7,
    characterized by the support comprising a member selected from the group consisting of nitride, carbon, silica, alumina, zirconia, titania, vanádia, ceria, boron nitride, heteropoly acid, diatomite, hydroxypatite, zinc oxide, chromium, zeolites, tungsted zirconia , titania-zirconia, sulfated zirconia, phosphate zirconia, acid alumina, silica-alumina, sulfated alumina, phosphate alumina, tetaalumina and mixtures thereof.
    10. METHOD, according to claim 8, characterized in that the support is modified by treating the support with a modifier selected from the group consisting of tungsten, titania, sulfate, phosphate and silica.
    11. METHOD, according to claim 1, characterized in that the deconstruction temperature is in the range of 120 ° C to 350 ° C.
    12. METHOD, according to claim 1, characterized by the deconstruction pressure being in the range of 2.06 MPa (300 psi) to 17.23 MPa (2,500 psi).
    13. METHOD according to claim 4, characterized in that the washing medium comprises a liquid selected from the group consisting of water, an acid, a base, a chelating agent, alcohols, ketones, cyclic ethers, hydroxy ketones, aromatic products , alkanes and combinations thereof.
    14. METHOD, according to claim 4,
    Petition 870190063717, of 07/08/2019, p. 11/19
    [4]
    4/9 characterized by the step of washing the deconstruction catalyst comprising a first step of washing the deconstruction catalysts with a first washing solvent and a second step of washing the deconstruction catalyst with a second washing solvent.
    METHOD, according to claim 14, characterized in that the first washing solvent comprises a liquid selected from the group consisting of water, an acid, a base, a chelating agent and combinations thereof and the second washing solvent comprises a liquid selected from the group consisting of alcohols, ketones, cyclic ethers, hydroxy ketones, aromatics, alkanes and combinations thereof.
    16. METHOD according to claim 14, characterized in that the first washing solvent comprises a liquid selected from the group consisting of alcohols, ketones, cyclic ethers, hydroxy ketones, aromatics, alkanes and combinations thereof and the second washing solvent comprise a liquid selected from the group consisting of water, an acid, a base, a chelating agent and combinations thereof.
    17. METHOD, according to claim 4, characterized in that the regeneration temperature is in the range of 120 ° C to 450 ° C and is adjusted at a rate of 20 ° C per hour to 60 ° C per hour.
    18. METHOD, according to the claim 4, featured through the regeneration of catalyst in deconstruction additionally understand , to provide an
    gas stream comprising an inert gas and oxygen, the inert gas being supplied at a gas flow of between 600 and 1,200 ml gas / ml of catalyst per hour and the oxygen supplied at a concentration of 0.5 to 10% of the gas stream.
    19. METHOD, according to claim 4,
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    [5]
    5/9 characterized by more than 90% of the carbonaceous deposits being removed from the deconstruction catalyst.
    20. METHOD, according to claim 1, characterized in that the condensation catalyst comprises a metal selected from the group consisting of Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In , Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, an alloy of them and a combination of them.
    21. METHOD, according to claim 20, characterized in that the condensation catalyst further comprises a modifier selected from the group consisting of Ce, La, Y, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, P, B, Bi and a combination of them.
    22. METHOD according to claim 1, characterized in that the condensation catalyst comprises a member selected from the group consisting of an acid alumina, aluminum phosphate, silica alumina phosphate, amorphous silica-alumina, sulfated alumina, tetaalumina, aluminosilicate , zeolites, zirconia, sulfated zirconia, tungsted zirconia, titania-zirconia, phosphate zirconia, tungsten carbide, molybdenum carbide, titania, sulfated carbon, phosphate carbon, phosphate silica, phosphate alumina, acid resin, heteropoly acid and an inorganic acid of the same.
    23. METHOD, according with the claim 1, featured with compound C4 + to be benzene, toluene or xylene. 24. METHOD, according with the claim 1, featured by hydrogen being selected from of
    group consisting of external hydrogen, recycled hydrogen and hydrogen generated in situ.
    25. METHOD, according to claim 24, characterized by the hydrogen generated in situ being derived from
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    [6]
    6/9 from C2 + O2 + oxygenated hydrocarbons.
    26. METHOD FOR CONVERTING BIOMASS INTO CHEMICALS AND FUELS DERIVED FROM BIOMASS, the method being characterized by understanding:
    providing a biomass feed stream comprising a solvent and a solid biomass component comprising cellulose, hemicellulose or lignin;
    catalytically reacting the biomass feed stream with hydrogen and a deconstruction catalyst at a deconstruction temperature and a deconstruction pressure to produce a product stream comprising a vapor phase, a liquid phase and a solid phase, the phase being of vapor comprises one or more volatile C2 + O1-2 oxygenates, in which the oxygenates have a relative volatility α, relative to 1-hexanol, greater than 0.03 based on pure components at 250 ° C, the phase being liquid comprises water and one or more oxygenated hydrocarbons C2 + O2 +, whose oxygenated hydrocarbons have a relative volatility α, relative to 1-hexanol, less than 0.03 based on pure components at 250 ° C, and the solid phase comprises extractants ;
    separating the volatile C2 + O1-2 oxygenates from the liquid and solid phases;
    direct the volatile C2 + O2 + oxygenate to a condensation step, the condensation step comprising catalytically reacting the volatile C2 + O1-2 oxygenates in the presence of a condensation catalyst at a condensing temperature and condensing pressure to produce a mixture of product comprising two or more C4 + compounds selected from the group consisting of a C4 + alcohol, a C4 + ketone, a C4 + alkane, a C4 + alkene, a C5 + cycloalkane, a C5 + cycloalkene, aryl and a fused aryl; and distill the product mixture to provide a
    Petition 870190063717, of 07/08/2019, p. 14/19
    [7]
    7/9 composition selected from the group consisting of an aromatic fraction, a fraction of gasoline, a fraction of kerosene and a fraction of diesel.
    27. METHOD according to claim 26, characterized by the aromatic fraction comprising benzene, toluene or xylene.
    28. METHOD, according to claim 26, characterized by the gasoline fraction having a final boiling point in the range of 150 ° C to 220 ° C, a density at 15 ° C in the range of 700 to 890 kg / m3, a RON in the 80 to 110 range and a MON in the 70 to 100 range.
    29. METHOD according to claim 26, characterized by the kerosene fraction having an initial boiling point in the range of 120 ° C to 215 ° C, a final boiling point in the range of 220 ° C to 320 ° C, an density at 15 ° C in the range of 700 to 890 kg / m3, a freezing point of -40 ° C or below, a smoke point of at least 18 mm and a viscosity at -20 ° C in the range of 1 to 10 mm 2 / s (1 to 10 cSt).
    30. METHOD according to claim 26, characterized by the fraction of diesel having a T95 in the range of 220 ° C to 380 ° C, a flash point in the range of 30 ° C to 70 ° C, a density at 15 ° C in the range 700 to 900 kg / m3 and a viscosity at 40 ° C in the range 0.5 to 6 mm2 / s (0.5 to 6 cSt).
    31. METHOD FOR CONVERTING BIOMASS INTO CHEMICALS AND FUELS DERIVED FROM BIOMASS, the method being characterized by understanding:
    supply a biomass feed stream comprising a solvent and a solid biomass component, the solvent comprising one or more members selected from the group consisting of water, oxygenated C2 + O2 + hydrocarbons generated in situ, oxygenated C2 + hydrocarbons Recycled O2 +, solvent
    Petition 870190063717, of 07/08/2019, p. 15/19
    [8]
    8/9 bioconversion, organic solvents, organic acids and a mixture of them and the biomass component comprises cellulose, hemicellulose and lignin;
    catalytically reacting the biomass feed stream with hydrogen and a deconstruction catalyst at a deconstruction temperature and a deconstruction pressure to produce a product stream comprising a vapor phase, a liquid phase and a solid phase, the phase being of vapor comprises one or more volatile C2 + O1-2 oxygenates, in which the oxygenates have a relative volatility α, relative to 1-hexanol, greater than 0.03 based on pure components at 250 ° C, the liquid phase comprises water and one or more oxygenated hydrocarbons C2 + O2 +, whose oxygenated hydrocarbons have a relative volatility α, relative to 1-hexanol, less than 0.03 based on pure components at 250 ° C, with the solid phase comprising extractants and the deconstruction catalyst comprises a support and a first member selected from the group consisting of Ru, Co, Rh, Pd, Ni, Mo and alloys thereof, and at least one selected member added al from the group consisting of Pt, Re, Fe, Ir, Cu, Mn, Cr, Mo, B, W, V, Nb, Ta, Ti, Zr, Y, La, Sc, Zn, Cd, Ag, Au, Sn, Ge, P, Al, Ga, In, Tl and their alloys;
    separate the volatile C2 + O1-2 oxygenates from the liquid and solid phase; and directing the volatile C2 + O2 + oxygenate to a condensation step, the condensation step comprising catalytically reacting the volatile C2 + O1-2 oxygenates in the presence of a condensation catalyst at a condensing temperature and condensing pressure to produce a compound C4 + comprising a member selected from the group consisting of C4 + alcohol, C4 + ketone, C4 + alkane, C4 + alkene, C5 + cycloalkane, C5 + cycloalkene, aryl, aryl
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    [9]
    9/9
    cast and a mixture of themselves.32. COMPOSITION CHEMISTRY, characterized per understand a compound C4 + derivative from anyone From methods as defined in Any of them of claims 1 to 31. 33. COMPOSITION CHEMISTRY, according The claim 32, characterized by the compound C4 + to be
    benzene, toluene or xylene.
    34. GASOLINE COMPOSITION, characterized by comprising a fraction of gasoline derived from any of the methods, as defined in any one of claims 1 to 28 or 31.
    35. KEROSENE COMPOSITION, characterized by comprising a fraction of kerosene derived from any one
    of the methods, according defined in Any of them of claims 1 to 27, 29 or 31. 36. COMPOSITION IN DIESEL, characterized per understand a fraction of diesel derived from anyone From methods as defined in Any of them of
    claims 1 to 26, 30 or 31.
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO2021119786A1|2019-12-20|2021-06-24|Petróleo Brasileiro S.A. - Petrobras|Selective process and catalysts for the production of renewable fuels and distillates of high molecular weight|US2220624A|1939-07-15|1940-11-05|Henry A Wallace|Process for the hydrogenation of lignin and waste pulp liquors and the products thereof|
    NL272563A|1960-12-16|
    US3702886A|1969-10-10|1972-11-14|Mobil Oil Corp|Crystalline zeolite zsm-5 and method of preparing the same|
    US3709979A|1970-04-23|1973-01-09|Mobil Oil Corp|Crystalline zeolite zsm-11|
    US3832449A|1971-03-18|1974-08-27|Mobil Oil Corp|Crystalline zeolite zsm{14 12|
    US4016245A|1973-09-04|1977-04-05|Mobil Oil Corporation|Crystalline zeolite and method of preparing same|
    US3941871A|1973-11-02|1976-03-02|Mobil Oil Corporation|Crystalline silicates and method of preparing the same|
    CA1064890A|1975-06-10|1979-10-23|Mae K. Rubin|Crystalline zeolite, synthesis and use thereof|
    US4107195A|1977-04-22|1978-08-15|Mobil Oil Corporation|Preparation of zeolite ZSM-35|
    US4208190A|1979-02-09|1980-06-17|Ethyl Corporation|Diesel fuels having anti-wear properties|
    US4375573A|1979-08-03|1983-03-01|Mobil Oil Corporation|Selective production and reaction of p-Disubstituted aromatics over zeolite ZSM-48|
    US4308411A|1980-08-28|1981-12-29|Occidental Research Corporation|Process for converting oxygenated hydrocarbons into hydrocarbons|
    CA1270642A|1983-12-30|1990-06-26|John Vincent Hanlon|Fuel compositions|
    US5019663A|1989-04-03|1991-05-28|Mobil Oil Corp.|Heat balanced paraffin upgrading with co-fed oxygenate|
    EP0482253A1|1990-10-23|1992-04-29|Ethyl Petroleum Additives Limited|Environmentally friendly fuel compositions and additives therefor|
    US5490864A|1991-08-02|1996-02-13|Texaco Inc.|Anti-wear lubricity additive for low-sulfur content diesel fuels|
    ES2090694T3|1991-09-13|1996-10-16|Chevron Chem Co|ADDITIVE COMPOSITIONS FOR FUELS CONTAINING POLYISOBUTENILSUCCINIMIDES.|
    GB9301119D0|1993-01-21|1993-03-10|Exxon Chemical Patents Inc|Fuel composition|
    GB9304350D0|1993-03-03|1993-04-21|Bp Chemicals Additives|Fuel and lubricating oil compositions|
    GB9411614D0|1994-06-09|1994-08-03|Exxon Chemical Patents Inc|Fuel oil compositions|
    DE4423095C2|1994-07-01|1996-05-30|Vdo Schindling|Tank insert that can be inserted into an opening of a fuel tank|
    TW477784B|1996-04-26|2002-03-01|Shell Int Research|Alkoxy acetic acid derivatives|
    TW449617B|1996-07-05|2001-08-11|Shell Int Research|Fuel oil compositions|
    EP0968259B1|1997-03-21|2002-08-28|Infineum Holdings BV|Fuel oil compositions|
    US6699457B2|2001-11-29|2004-03-02|Wisconsin Alumni Research Foundation|Low-temperature hydrogen production from oxygenated hydrocarbons|
    WO2003045841A1|2001-11-29|2003-06-05|Wisconsin Alumni Research Foundation|Low-temperature hydrogen production from oxygenated hydrocarbons|
    BRPI0309915B1|2002-05-10|2020-06-23|Wisconsin Alumni Research Foundation|METHOD OF PRODUCTION OF HYDROCARBONES FROM OXYGENED HYDROCARBONS|
    US7022888B2|2003-03-27|2006-04-04|Council Of Scientific And Industrial Research|Process for the simultaneous conversion of methane and organic oxygenate to C2 to C10 hydrocarbons|
    CN101346302B|2005-12-21|2013-07-10|维仁特公司|Catalysts and methods for reforming oxygenated compounds|
    MY154790A|2007-03-08|2015-07-31|Virent Inc|Synthesis of liquid fuels and chemicals from oxygenated hydrocarbons|
    EP2565176B1|2006-05-08|2015-08-19|Virent, Inc.|Methods for generating polyols|
    EP2061860B1|2007-03-08|2013-12-18|Virent, Inc.|Synthesis of liquid fuels and chemicals from oxygenated hydrocarbons|
    EP2331486A2|2008-08-27|2011-06-15|Virent Energy Systems Inc.|Synthesis of liquid fuels from biomass|
    US8697924B2|2008-09-05|2014-04-15|Shell Oil Company|Liquid fuel compositions|
    EP2403926B1|2009-03-05|2019-10-02|G4 Insights Inc.|Process for thermochemical conversion of biomass|
    US8492600B2|2009-04-07|2013-07-23|Gas Technology Institute|Hydropyrolysis of biomass for producing high quality fuels|
    US8148553B2|2009-06-23|2012-04-03|Wisconsin Alumni Research Foundation|Catalytic conversion of cellulose to liquid hydrocarbon fuels by progressive removal of oxygen to facilitate separation processes and achieve high selectivities|
    US20120172588A1|2010-12-30|2012-07-05|Ming Qiao|Catalytic biomass deconstruction|US20120172588A1|2010-12-30|2012-07-05|Ming Qiao|Catalytic biomass deconstruction|
    FR2987281A1|2012-02-27|2013-08-30|Synthopetrol|NEW TRIFUNCTIONAL BIMETALLIC CATALYSTS, PROCESS FOR THE PREPARATION THEREOF AND USE THEREOF|
    US20130232853A1|2012-03-09|2013-09-12|Thesis Chemistry, Llc|Method for selective production of biobased chemicals and biofuels from plant lignin|
    US9290423B2|2012-11-19|2016-03-22|Kior, Llc|Process of generating a renewable biofuel from a hydrotreated stream of condensed oxygenates|
    US9200209B2|2012-11-19|2015-12-01|Kior, Inc.|Process of generating a renewable biofuel from a hydrotreated stream of condensed oxygenates|
    EP2935520B1|2012-12-18|2020-05-20|ExxonMobil Research and Engineering Company|Process for making a lube basestock from renewable feeds|
    EP2935531B1|2012-12-18|2018-04-11|ExxonMobil Research and Engineering Company|Process for making lube base stocks from renewable feeds|
    SG2013096748A|2013-01-08|2014-08-28|Reliance Ind Ltd|System and method for preparing hydrocarbon blend from multiple component streams|
    FI125582B|2013-03-08|2015-12-15|Upm Kymmene Corp|Process for converting gaseous products|
    FR3004182B1|2013-04-09|2015-03-27|IFP Energies Nouvelles|PROCESS FOR TRANSFORMING LIGNOCELLULOSIC BIOMASSES TO MONO OR POLY-OXYGENIC MOLECULES|
    KR101436428B1|2013-05-15|2014-09-01|고려대학교 산학협력단|Method for biodiesel from sludge and equipment comprising the same|
    US9873836B2|2013-05-22|2018-01-23|Virent, Inc.|Process for converting biomass to aromatic hydrocarbons|
    US9873644B2|2013-05-22|2018-01-23|Virent, Inc.|Hydrogenation of carboxylic acids to increase yield of aromatics|
    US20150051427A1|2013-08-16|2015-02-19|Kior, Inc.|Integrated process for the production of renewable drop-in fuels|
    CN104560102B|2013-10-29|2016-05-18|中国石油化工股份有限公司|A kind of method that improves quality of bio-oil|
    CA2939866A1|2014-01-21|2015-07-30|Kior, Inc.|Process of reactivating a metal contaminated biomass conversion catalyst|
    EP3099762B1|2014-01-28|2019-10-02|Shell International Research Maatschappij B.V.|Conversion of biomass or residual waste material to biofuels|
    SG11201609659XA|2014-07-01|2017-01-27|Shell Int Research|Conversion of solid biomass into a liquid hydrocarbon material|
    US10174259B2|2014-07-01|2019-01-08|Shell Oil Company|Conversion of solid biomass into a liquid hydrocarbon material|
    CN106471099B|2014-07-01|2019-04-05|国际壳牌研究有限公司|Conversion of the solid biomass to liquid hydrocarbon material|
    US9382283B2|2014-08-01|2016-07-05|American Science And Technology Corporation|Oxygen assisted organosolv process, system and method for delignification of lignocellulosic materials and lignin recovery|
    FR3026407B1|2014-09-26|2016-10-28|Ifp Energies Now|METHOD FOR TRANSFORMING A LOAD COMPRISING A LIGNOCELLULOSIC BIOMASS USING AN ACIDIC HOMOGENEOUS CATALYST IN COMBINATION WITH A HETEROGENEOUS CATALYST COMPRISING A SPECIFIC SUPPORT|
    KR101771302B1|2015-02-06|2017-08-25|경희대학교 산학협력단|Process for preparing biopolyol using Tetraselmis sp.|
    EA201792115A1|2015-03-24|2018-04-30|Штудиенгезельшафт Коле Мбх|METHOD OF PRODUCING PETROLEUM PRODUCTS FROM PEAT, COCONIC FIBERS OR SUBSTITUTE SUBSTANCES|
    US9815747B2|2015-04-28|2017-11-14|Battelle Energy Alliance, Llc|Syngas conversion to a light alkene and related methods|
    WO2017209778A2|2015-08-13|2017-12-07|Virent, Inc.|Production of alternative gasoline fuels|
    WO2017025612A1|2015-08-13|2017-02-16|Shell Internationale Research Maatschappij B.V.|Fuel formulation|
    AU2016320326B2|2015-09-07|2019-05-02|Shell Internationale Research Maatschappij B.V.|Conversion of biomass into a liquid hydrocarbon material|
    CN108026451A|2015-09-25|2018-05-11|国际壳牌研究有限公司|Conversion of the biomass to methane|
    US10822546B2|2015-11-23|2020-11-03|Shell Oil Company|Conversion of biomass into a liquid hydrocarbon material|
    EP3380587A4|2015-11-23|2019-06-12|Inaeris Technologies, LLC|Process of upgrading light hydrocarbons and oxygenates produced during catalytic pyrolysis of biomass|
    CA3004679A1|2015-11-23|2017-06-01|Shell Internationale Research Maatschappij B.V.|Conversion of biomass into a liquid hydrocarbon material|
    WO2017112716A1|2015-12-21|2017-06-29|Shell Oil Company|Methods of providing higher quality liquid kerosene based-propulsion fuels|
    WO2017175733A1|2016-04-06|2017-10-12|宇部興産株式会社|Biomass solid fuel|
    WO2018015608A1|2016-07-19|2018-01-25|Upm-Kymmene Corporation|Process for converting lignocellulosic materials|
    CN109563423B|2016-07-26|2021-07-06|出光兴产株式会社|Gasoline composition and method for producing the same|
    US20180298294A1|2017-04-13|2018-10-18|Alliance For Sustainable Energy, Llc|Systems and methods for producing fuel intermediates|
    EP3699258A4|2017-10-16|2021-06-30|Nippon Soda Co., Ltd.|Method for manufacturing bio-liquid fuel|
    CN109705985A|2017-10-25|2019-05-03|中国科学院大连化学物理研究所|A kind of method that PET, PTT, PBT manufacture object are converted into aviation kerosine range cyclic hydrocarbon|
    CN110498424B|2018-05-16|2021-10-08|中国石油化工股份有限公司|Method for modifying Y molecular sieve|
    CN108949287B|2018-08-08|2021-01-22|桂林桂特板业有限公司|Method for improving biomass molding fuel ash melting temperature by using porous ceramic|
    CN110923001B|2019-11-25|2021-07-06|中国科学院广州能源研究所|Method for preparing special fuel with low freezing point, high density and high thermal stability by using lignocellulose biomass|
    CN111760554A|2020-08-12|2020-10-13|湖南三五二环保科技有限公司|Preparation method of carbon material for wastewater treatment, product and application thereof|
    法律状态:
    2018-12-11| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-04-09| B07A| Technical examination (opinion): publication of technical examination (opinion) [chapter 7.1 patent gazette]|
    2019-09-03| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2019-10-15| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 23/05/2012, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 23/05/2012, OBSERVADAS AS CONDICOES LEGAIS |
    优先权:
    申请号 | 申请日 | 专利标题
    US201161489135P| true| 2011-05-23|2011-05-23|
    US61/489,135|2011-05-23|
    PCT/US2012/039166|WO2012162403A1|2011-05-23|2012-05-23|Production of chemicals and fuels from biomass|
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