• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    METHOD OF MANUFACTURING C8+ COMPOUND, METHOD OF MANUFACTURING A FUEL PRODUCT, JET FUEL COMPOSITION, DIESEL FUEL COMPOSITION AND HEAVY OIL COMPOSITION The present invention provides methods, reactor systems and catalysts for the conversion of biomass and raw materials. raw materials derived from biomass to C~ 8~+ hydrocarbons with the use of heterogeneous catalysts. The product stream can be separated and further processed for use in chemical applications, either as a pure fuel or a blending component in jet fuel and diesel fuel, or with heavy oils for fuel oil and/or lubricant applications.
    公开号:BR112013019898B1
    申请号:R112013019898-2
    申请日:2012-02-07
    公开日:2021-05-25
    发明作者:Paul Blommel；Brice Dally；Warren Lyman；Randy Cortright
    申请人:Virent, Inc；
    IPC主号:
    专利说明:

    CROSS REFERENCE TO RELATED ORDERS
    This order claims the benefit of provisional order no. US 61/440,249 filed February 7, 2011. FIELD OF TECHNIQUE
    The present invention is directed to methods, catalysts and reactor systems for the production of jet fuel, diesel and heavy oil from biomass and raw materials derived from biomass using heterogeneous catalysts. FUNDAMENTALS OF THE INVENTION
    Considerable attention has been paid to the development of new technologies for supplying energy from resources other than fossil fuels. Biomass is a resource that looks promising as a fossil fuel alternative. As opposed to fossil fuel, biomass is also renewable.
    One type of biomass is plant biomass. Plant biomass is the most abundant source of carbohydrate in the world due to the lignocellulosic materials in its cell walls. Plant cell walls are divided into two sections, the primary cell walls and the secondary cell walls. The primary cell wall provides structure for cell expansion and is composed of major polysaccharides (cellulose, pectin and hemicellulose) and glycoproteins. The secondary cell wall, which is produced after the cell has terminated growth, also contains polysaccharides and is reinforced through polymeric lignin covalently crosslinked to hemicellulose. Cellulose includes high molecular weight polymers formed from tightly bound glucose monomers, while hemicellulose includes shorter polymers formed from various sugars. Lignin includes phenylpropanoic acid moieties polymerized into a complex three-dimensional structure. In general, the composition of lignocellulosic biomass is approximately 40 to 50% cellulose, 20 to 25% hemicellulose and 25 to 35% lignin, by weight percent.
    Most transport vehicles, boats, trains, planes and automobiles, require high energy density provided by propulsion and/or internal combustion engines. These engines require clean combustion fuels which are generally in liquid form or, to a lesser extent, compressed gases. Liquid fuels are more portable due to their high energy density and pumpability, which makes handling easier. This is why most fuels are liquid.
    Biomass currently provides the only renewable alternative to liquid transport fuel. Except for nuclear and wind applications, and for most solar resources, biomass is capable of being converted into a liquid form. Unfortunately, progress in developing new technologies for the production of liquid biofuels has been slow, especially for liquid fuel products suitable for heavy fuel oil, diesel and jet applications. Although a variety of diesel and jet fuels can be produced from biomass resources such as biodiesel, Fischer-Tropsch diesel, and palm oil and jatropha jet fuels, these fuels are often limited in their use due to their respective characteristics. The production of these fuels also tends to be expensive and poses questions regarding net carbon savings.
    Biodiesel, for example, can be made from vegetable oil, animal fats, residual vegetable oils, microalgae oils or recycled restaurant fats, and is produced through a process in which organically derived oils are combined with alcohol (ethanol or methanol) in the presence of a catalyst to form ethyl or methyl esters. Biomass derived ethyl or methyl esters can then be blended with conventional diesel fuel or used as a pure fuel (100% biodiesel). Biodiesel is also expensive to manufacture and poses several problems in its use and combustion. For example, biodiesel is not suitable for use at lower temperatures and requires special handling to prevent gelling at cold temperatures. Biodiesel also tends to provide higher nitrogen oxide emissions and cannot be transported in petroleum pipelines.
    Biomass can also be gasified to produce a synthesis gas composed primarily of carbon monoxide and hydrogen, also called synthesis gas or synthesis biogas. Synthesis gas produced today is used directly to generate heat and energy, but many types of biofuels can be derived from synthesis gas. The hydrogen can be recovered from synthesis gas, or the synthesis gas can be catalytically converted to methanol. With the use of Fischer-Tropsch catalysts, the gas can also be converted to a liquid stream with properties similar to diesel fuel. These processes are energy and capital intensive, and are limited by the availability of biomass in adequate volumes for the scale needed to be commercially effective.
    The above technologies are also ineffective and do not make use of the plant's carbohydrate material or require the total destruction and reassembly of its 5 carbon backbone. Bioreform processes have recently been developed to overcome these problems and provide liquid fuels and chemicals derived from the cellulose, hemicellulose and lignin found in plant cell walls. For example, cellulose and hemicellulose can be used as feedstocks for various bioreforming processes, which include aqueous phase reforming (APR) processes and hydrodeoxygenation (HDO) catalytic reforming processes which, when integrated with hydrogenation, can convert cellulose and hemicellulose to hydrogen and 15 hydrocarbons, which include liquid fuels and other chemicals. APR and HDO methods and techniques are described in patents no. U.S. 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 20 Oxygenated Hydrocarbons"); patent n-. U.S. 6,953,873 (to Cortright et al., and entitled "Low-Temperature Hydrocarbon Production from Oxygenated Hydrocarbons"); and patents no. U.S. 7,767,867 and 7.989,664 and application no. U.S. 2011/0306804 (all to Cortright, and entitled "Methods and Systems for 25 Generating Polyols"). A number of APR and HDO methods and techniques are described in the US patents. U.S. 8,053,615; 8,017,818 and 7,977,517 and patent application no., U.S. serial 13/163,439; 13/171,715; 13/163,142 and 13/157,247 (all to Cortright and Blommel, and entitled "Synthesis of Liquid Fuels and 30 Chemicals from Oxygenated Hydrocarbons"); patent application no. U.S. 2009/0211942 (to Cortright, and entitled "Catalysts and Methods for Reforming Oxygenated Compounds"); patent application no. U.S. 2010/0076233 (to Cortright et al., and entitled "Synthesis of Liquid Fuels from Biomass"); international patent application no. PCT/US2008/056330 (to Cortright and Blommel, and entitled "Synthesis of Liquid Fuels and Chemicals from Oxygenated Hydrocarbons"); and co-pending international patent application of the same applicant no. PCT/US2006/048030 (to Cortright et al., and entitled "Catalyst and Methods for Reforming Oxygenated Compounds"), all of which are incorporated herein by reference. Additional techniques for converting cellulose, hemicellulose and lignin to feedstocks usable for the above APR and HDO processes are described in patent application no. U.S. serial 13/339,720 (to Qiao et al., and entitled "Solvolysis of Biomass Using Solvent from a Bioforming Process"); patent application no. U.S. serial 13/339,661 (to Qiao et al., and entitled "Organo-Catalytic Biomass Deconstruction"); patent application no. U.S. serial 13/339,553 (to Qiao et al., and entitled "Catalytic Biomass Deconstruction"); and patent application no. serial U.S. 13/339,994 (to Qiao et al., and entitled "Reductive Biomass Liquefaction").
    One of the keys to commercializing the above technologies is to further refine processes to maximize product yield and extend catalyst life. Also of interest is the ability to adapt reactions to produce specific products of high demand or greater commercial value. Consequently, a more refined process is needed for converting biomass and biomass-derived raw materials to a greater amount of heavier hydrocarbons useful in diesel and jet fuels, or as heavy oils for fuel oil and/or lubricant applications . SUMMARY
    The invention provides methods for making Cg+ compounds. The method generally involves providing a reactant stream comprising a first reactant and a second reactant and catalytically reacting the reactant stream with hydrogen in the presence of an acidic condensation catalyst to produce a product stream comprising water and a plurality of Cg+ compounds. The first reactant comprises one or more molecules that have a general formula CxHyOz and an average oxygen to carbon ratio of the first reactant between 0.2 and 1.0, ex = 2 to 12 carbon atoms and z = 1 to 12 oxygen atoms . The second reactant comprises one or more molecules that have a general formula CpHrOs and an average second reactant oxygen to carbon ratio of 0.2 or less, and p = 2 to 7 carbon atoms and s = 0 to 1 oxygen atom. The number of carbon atoms in the reactant flow from the first reactant is greater than 10% of the total carbon atoms in the reactant flow, and the number of carbon atoms in the reactant flow from the second reactant is greater than than 10% of the total carbon atoms in the reactant flow. The product stream comprises water and a plurality of Cg+ compounds selected from the group consisting of Cg+ alkanes, Cg+ alkenes, Cg+ cycloalkanes, C8+ cycloalkenes, C8+ alcohols, Cg+ ketones, an aryl, a fused aryl, an oxygenated aryl, a oxygenated fused aryl, and a mixture thereof. The acid condensation catalyst comprises an acid support or a heterogeneous acid catalyst comprising a metal selected from the group consisting of Pd, Pt, Cu, Co, Ru, Cr, Ni, Ag, an alloy thereof, and a combination thereof. of the same.
    One aspect of the invention is the catalytic material. In one embodiment, the acid support is selected from the group consisting of an aluminosilicate, a tungsten aluminosilicate, a silica-alumina phosphate, an aluminum phosphate, an amorphous silica alumina, an acidic alumina, an alumina phosphate, an alumina tungsten, a zirconia, a tungsten zirconia, a tungsten silica, a tungsten titania, a tungsten phosphate, niobia, an acid-modified resin, a zeolite, a heteropolyacid, a tungstenated heteropolyacid, and combinations thereof. The heterogeneous acid catalyst may further comprise a support selected from the group consisting of carbon, silica, alumina, zirconia, titania, vanadia, kieselguhr, hydroxyapatite, chromia, niobia, mixtures thereof, and combinations thereof. In another embodiment, the acid condensation catalyst additionally comprises a modifier selected from the group consisting of Cu, Ag, Au, Ru, Pd, Ni, Co, Ga, In, Cr, Mo, W, Sn, Nb , Ti, Zr, Ge, P, Al, alloys thereof, and combinations thereof. In certain embodiments, the acid condensation catalyst comprises ZSM-5 or tungsten zirconia. The acid condensation catalyst may additionally comprise Pd or Cu.
    Another aspect of the invention is the composition of reagent streams. In one embodiment, the second reactant has an average oxygen to molecule ratio of 1 to 4, and the first reactant has an average oxygen to molecule ratio of 1.5 or less. In another embodiment, the second reagent has a boiling point of less than 210°C. In yet another embodiment, the reagent flow additionally includes water.
    The product stream further comprises one or more C7- compounds which have 2 to 7 carbon atoms and 0 to 1 oxygen atom, and a portion of the product stream may be recycled to form part of the second reactant.
    The method may further comprise the following steps: (1) removing water from the product stream before recycling part of the product stream to form part second reactant; (2) catalytically reacting at least a portion of the product stream in the presence of a finishing catalyst; or (3) supplying hydrogen, water and a water-soluble oxygenated hydrocarbon comprising a C2+Oi+ hydrocarbon, and catalytically reacting the oxygenated hydrocarbon with the hydrogen in the presence of a deoxygenation catalyst to produce the first reactant.
    The deoxygenation catalyst is capable of converting the first stream of reactant to oxygenates. In one embodiment, the deoxygenation catalyst comprises a support and an element selected from the group consisting of Re, Cu, Fe, Ru, Ir, Co, Rh, Pt, Pd, Ni, W, Os, Mo, Ag, Au, a league of them, and a combination of them. The support can be selected from the group consisting of a carbon, silica, alumina, zirconia, titania, vanadia, heteropolyacid, kieselguhr, hydroxyapatite, chromia, zeolite, and mixtures thereof. In one embodiment, the support is selected from the group consisting of tungsten zirconia, tungsten-modified zirconia, tungsten-modified alpha-alumina, or tungsten-modified theta-alumina.
    The water-soluble oxygenated hydrocarbon may be selected from the group consisting of a starch, a carbohydrate, a polysaccharide, a disaccharide, a monosaccharide, a sugar, a sugar alcohol, an aldopentose, an aldohexose, a ketotetrose, a ketopentose , a ketohexose, a hemicellulose, a cellulosic derivative, a lignocellulosic derivative, and a polyol.
    Hydrogen can be in situ generated H2, external H2 or recycled H2. In one embodiment, hydrogen can be generated in situ by reacting catalytically in a liquid phase or vapor phase of an aqueous feedstock solution comprising water and an oxygenated hydrocarbon in the presence of a phase reforming catalyst aqueous at a reforming temperature and reforming pressure.
    Another aspect of the invention is a method of manufacturing Cg+ compounds by: (i) providing a reagent stream comprising water, a first reagent and a second reagent; and (ii) catalytically reacting the reactant stream with hydrogen in the presence of an acidic condensation catalyst to produce a product stream comprising water and a plurality of C8+ compounds. The first reactant may comprise one or more molecules having a general formula CxHyOz and an average oxygen to carbon ratio of the first reactant between 0.2 and 1.0, ex = 2 to 12 carbon atoms and z = 1 to 12 carbon atoms. oxygen. The second reactant may comprise one or more molecules having a general formula CpHrOs and an average oxygen to carbon ratio of the second reactant of 0.2 or less, and p = 2 to 7 carbon atoms and s = 0 to 1 oxygen atom. The number of carbon atoms in the reactant flow from the first reactant is greater than 10% of the total carbon atoms in the reactant flow, and the number of carbon atoms in the reactant flow from the second reactant is greater than than 10% of the total carbon atoms in the reactant flow. The C8+ compounds are selected from the group consisting of a C8+ alkane, a C8+ alkene, a Cs+ cycloalkane, a C8+ cycloalkene, a Ca+ alcohol, a Cg+ ketone, an aryl, a fused aryl, an oxygenated aryl, a fused aryl oxygenated, and a mixture thereof. The acid condensation catalyst comprises an acid support or a heterogeneous acid catalyst comprising a metal selected from the group consisting of Pd, Pt, Cu, Co, Ru, Cr, Ni, Ag, an alloy thereof, and a combination thereof. of the same.
    In one embodiment, the method further includes providing hydrogen, water and a water-soluble oxygenated hydrocarbon comprising a C2+Oi+ hydrocarbon, and catalytically reacting the oxygenated hydrocarbon with hydrogen in the presence of a deoxygenation catalyst to produce the first reagent.
    The deoxygenation catalyst is capable of converting the first stream of reactant to oxygenates. In one embodiment, the deoxygenation catalyst comprises a support and an element selected from the group consisting of Re, Cu, Fe, Ru, Ir, Co, Rh, Pt, Pd, Ni, W, Os, Mo, Ag, Au, a league of them, and a combination of them. The support can be selected from the group consisting of a carbon, silica, alumina, zirconia, titania, vanadia, heteropolyacid, kieselguhr, hydroxyapatite, chromia, zeolite and mixtures thereof. In one embodiment, the support is selected from the group consisting of tungsten zirconia, tungsten-modified zirconia, tungsten-modified alpha-alumina, or tungsten-modified theta-alumina.
    The water-soluble oxygenated hydrocarbon can be selected from the group consisting of a starch, a carbohydrate, a polysaccharide, a disaccharide, a monosaccharide, a sugar, a sugar alcohol, an aldopentose, an aldohexose, a ketotetrose, a ketopentose , a ketohexose, a hemicellulose, a cellulosic derivative, a lignocellulosic derivative, and a polyol.
    Another aspect of the present invention is a method of making Cg+ compounds comprising: (i) providing a reagent stream comprising a first reagent and a second reagent; (ii) catalytically reacting the reactant stream with hydrogen in the presence of an acidic condensation catalyst to produce a product stream comprising water, a plurality of C7_ compounds and a plurality of C8+ compounds; (iii) separating a part of the C7- compounds from the product stream to provide a recycle stream and (iv) recycling the recycle stream 5 to form at least in part the second reactant.
    The first reactant may comprise one or more molecules having a general formula CxHyOz and an average oxygen to carbon ratio of the first reactant between 0.2 and 1.0, ex = 2 to 12 carbon atoms and z = 1 to 12 carbon atoms. 10 oxygen. The second reactant may comprise one or more molecules having a general formula CpHrOs and an average oxygen to carbon ratio of the second reactant of 0.2 or less, and p = 2 to 7 carbon atoms and s = 0 to 1 oxygen atom. The number of carbon atoms in the reactant stream 15 from the first reactant is greater than 10% of the total carbon atoms in the reactant stream, and the number of carbon atoms in the reactant stream from the second reactant is greater than 10% of the total carbon atoms in the reactant flow. The C7_ compounds are selected from the group consisting of a C7-alkane, a C7-alkene, a C7-cycloalkane, a C7-cycloalkene, a C7-alcohol, a C7-ketone, a C7-aryl, and mixtures thereof. The C8+ compounds are selected from the group consisting of a C8+ alkane, a C8+ alkene, a C8+ cycloalkane, a C8+ cycloalkene, a C8+ alcohol, a C8+ ketone, an aryl, a fused aryl, an oxygenated aryl, an aryl oxygenated fused, and a mixture thereof. The acid condensation catalyst comprises an acid support or a heterogeneous acid catalyst comprising a metal selected from the group consisting of Pd, Pt, Cu, Co, Ru, Cr, Ni, Ag, an alloy thereof, and a combination of them.
    In one embodiment, the acid support is selected from the group consisting of an aluminosilicate, a tungsten aluminosilicate, a silica-alumina phosphate, an aluminum phosphate, an amorphous silica alumina, an acidic alumina, an alumina phosphate, an alumina tungsten, a zirconia, a tungsten zirconia, a tungsten silica, a tungsten titania, a tungsten phosphate, niobia, an acid-modified resin, a zeolite, a heteropolyacid, a tungstenated heteropolyacid, and combinations thereof. The heterogeneous acid catalyst may further comprise a support selected from the group consisting of carbon, silica, alumina, zirconia, titania, vanadia, kieselguhr, hydroxyapatite, chromia, niobia, mixtures thereof, and combinations thereof. The acid condensation catalyst further comprises a modifier selected from the group consisting of Cu, Ag, Au, Ru, Pd, Ni, Co, Ga, In, Cr, Mo, W, Sn, Nb, Ti, Zr , Ge, P, Al, alloys thereof, and combinations thereof.
    In one embodiment, the acid condensation catalyst comprises ZSM-5 or tungsten zirconia. The acid condensation catalyst may additionally comprise Pd or Cu.
    In another embodiment, the second reactant has an average oxygen to molecule ratio of 1 to 4, and the first reactant has an average oxygen to molecule ratio of 1.5 or less. In yet another embodiment, the recycle stream has a boiling point of less than 210°C.
    Another aspect of the invention is a method of manufacturing a fuel product comprising: (i) providing a reactant flow comprising a first reactant and a second reactant; (ii) catalytically reacting the reactant stream with hydrogen in the presence of an acidic condensation catalyst to produce a product stream comprising water, a plurality of C7- compounds and a plurality of C8+ compounds; (iii) separating at least a portion of the C8+ compounds from the product stream, (iv) catalytically reacting the separated C8+ compounds in the presence of a finishing catalyst to produce a fuel product.
    The first reactant may comprise one or more molecules having a general formula CxHyOz and an average oxygen to carbon ratio of the first reactant between 0.2 and 1.0, ex = 2 to 2 carbon atoms and z = 1 to 12 oxygen atoms. The second reactant may comprise one or more molecules having a general formula CpHrOs and an average oxygen to carbon ratio of the second reactant of 0.2 or less, and p = 2 to 7 carbon atoms and s = 0 to 1 oxygen atom. The number of carbon atoms in the reactant stream from the first reactant is greater than 10% of the total carbon atoms in the reactant stream, and the number of carbon atoms in the reactant stream from the second reactant is greater than than 10% of the total carbon atoms in the reactant flow. The C7_ compounds are selected from the group consisting of a C7-alkane, a C7-alkene, a C7-cycloalkane, a C7-cycloalkene, a C7-alcohol, a C7-ketone, a C7-aryl, and mixtures thereof. The C8+ compounds are selected from the group consisting of a C8+ alkane, a C8+ alkene, a C8+ cycloalkane, a C8+ cycloalkene, a C8+ alcohol, a C8+ ketone, an aryl, a fused aryl, an oxygenated aryl, a fused aryl oxygenated, and a mixture thereof. The acid condensation catalyst comprises an acid support or a heterogeneous acid catalyst comprising a metal selected from the group consisting of Pd, Pt, Cu, Co, Ru, Cr, Ni, Ag, an alloy thereof, and a combination thereof. of the same.
    In one embodiment, the method further comprises a step of separating the fuel product to provide a C8-i4 fraction comprising a plurality of hydrocarbons having 8 to 14 carbon atoms, a C12-24 fraction comprising a plurality of hydrocarbons that have 12 to 24 carbon atoms, and a C25+ moiety that comprises a plurality of hydrocarbons that have 25 or more carbon atoms. In another embodiment, the C3-14 fraction is blended to provide a jet fuel, or the C12-24 fraction is blended to provide a diesel fuel, or the C25+ fraction is blended to provide a heavy oil.
    Other aspects of the invention include a jet fuel composition, a diesel fuel composition, and a heavy oil composition comprising a fuel product produced by the above method.
    DESCRIPTION OF THE DRAWINGS Figure 1 is a flow diagram illustrating a reactor system for catalytically converting biomass to C8+ compounds in accordance with the present invention. Figure 2 is a flow diagram illustrating a reactor system for catalytically converting biomass to C8+ compounds in accordance with the present invention. Figure 3 is a flow diagram illustrating a reactor system for catalytically converting biomass to C8+ compounds in accordance with the present invention. Figure 4 is a flowchart illustrating a reactor system for catalytically converting biomass to C8+ compounds in accordance with the present invention. Figure 5 is a flow diagram illustrating a reactor system for catalytically converting biomass to C8+ compounds in accordance with the present invention. Figure 6 is a graph showing the carbon number distribution for the product stream of example 20. Figure 7 is a graph showing a normal boiling point curve for both the first reactant and the second reactant. Figure 8 is an illustration of various chemical pathways believed to be involved in the production of C8+ compounds in accordance with the present invention. DETAILED DESCRIPTION OF THE INVENTION
    The present invention provides methods, reactor systems and catalysts for converting biomass and biomass-derived feedstocks to C8+ hydrocarbons using heterogeneous catalysts. The resulting product stream includes C8+ alkanes, C8+ alkenes, C8+ cycloalkanes, C8+ cycloalkenes, aryls, fused aryls, and mixtures thereof. The product stream can also include C8+ alcohols, C8+ ketones, oxygenated aryls, and oxygenated fused aryls. The product stream can be separated and further processed for use in chemical applications or as a pure fuel or blending component in jet and diesel fuels or as heavy oils for fuel oil and/or lubricant applications. The general conversion process can take place separately in different reactors or together in a single reactor, and usually takes place in a steady state as part of a continuous process.
    The invention generally involves catalytically reacting a reactant stream containing a first reactant and a second reactant with hydrogen in the presence of an acidic condensation catalyst at a suitable condensation temperature and condensation pressure to produce a water-containing product stream. and C8+ compounds. In one embodiment, the reagent flow also includes water. In another embodiment, a portion of the product stream is recycled to the feed stream to provide the second reactant. In yet another embodiment, the product stream is further processed in a finishing step to produce a fuel product suitable for use as a pure fuel or as a blending component for jet, diesel or heavy oil applications. In yet another embodiment, the fuel product is blended with other hydrocarbons to provide a final jet fuel, diesel fuel or heavy oil product.
    The reagent stream can originate from any source, but is preferably derived from biomass or a raw material derived from biomass using any known method. Such methods include fermentation technologies using enzymes or microorganisms, Fischer-Tropsch reactions to produce C2-10 alpha alcohols 6 other oxygenates, and pyrolysis technologies to produce alcohols from oil, among others. In one embodiment, the reactant flow is produced using a catalytic bioreform technology, such as an APR and/or HDO catalytic process.
    Hydrogen can be generated in situ using aqueous phase reform (in situ generated H2 or APR H2), or a combination of APR H2, external H2 and/or recycled H2, or simply external H2 or recycled H2. The term "external H2" refers to hydrogen that does not originate from the feedstock but is added to the reactor system from an external source. The term "recycled H2" refers to unconsumed hydrogen, which is is collected and then recycled back to the reactor system for further use.External H2 and recycled H2 can also be collectively or individually referred to as “Supplemental H2.” In general, supplemental H2 can be added to purposes of supplementing hydrogen from APR, to increase the reaction pressure within the system, or to increase the molar ratio of hydrogen to carbon and/or oxygen in order to optimize the production yield of certain types of reaction product.
    A surprising aspect of the invention is the fact that the inventors are able to increase the production yield of C8+ compounds with the use of the acidic condensation catalysts described above and a reactant flow that includes a first reactant having an oxygen to ratio. average carbon between 0.2 and 1.0, and a second reagent that has an average oxygen to carbon ratio of 0.2 or less, in the presence of water. Without being bound by any particular theory, it is believed that the unique combination of the first and second reactants in the reactant flow helps to control the effects of water in the system and drives the reaction to produce the longer chain C8+ compounds. Specifically, it is believed that combining the reactants has the effect of increasing the reaction partial pressure for the reactants, while decreasing the water partial pressure. The resulting product stream tends to have a higher yield of C8+ compounds as compared to systems that do not involve a second reagent as described herein.
    The first reagent includes one or more oxygenates that have a general formula CxHyOz, with x representing 2 to 12 carbon atoms and z representing 1 to 12 oxygen atoms. Collectively, the average oxygen to carbon ratio of the oxygenates in the first reactant should be about 0.2 to 1.0, calculated as the total number of oxygen atoms (z) in the oxygenates of the first reactant divided by the total number of atoms of carbon (x) in the oxygenates of the first reagent. Alternatively, the first reactant can have an average oxygen content per molecule of about 1 to 4, calculated as the total number of oxygen atoms (z) in the oxygenates of the first reactant divided by the total number of molecules of the oxygenates in the first reactant. The total number of carbon atoms per molecule, oxygen atoms per molecule, and total molecules in the first reagent can be measured using any number of common knowledge methods, which include (1) gas chromatography (GC) speciation, chromatography high performance liquid (HPLC) and other methods known in the art and (2) determination of total oxygen, carbon and water content by elemental analysis. Oxygen present in water, carbon dioxide, or carbon monoxide is excluded from the determination of the oxygen to carbon ratio of the reactant.
    Examples of oxygenates in the first reactant include, without limitation, oxygenated hydrocarbons that have 1 to 4 oxygen atoms (for example, mono-, di-, tri- and tetra-oxygenated hydrocarbons). Monooxygenated hydrocarbons typically include alcohols, ketones, aldehydes, cyclic ethers, furans and pyrans, while dioxygenated hydrocarbons typically include diols, hydroxy ketones, lactones, furfuryl alcohols, pyranyl alcohols and carboxylic acids. Alcohols may include, without limitation, cyclic, branched, linear, secondary or primary C2+ alcohols such as ethanol, n-propyl alcohol, isopropyl alcohol, 1-butanol, 2-butanol, 2-methyl-1-propanol (alcohol isobutyl), 2-methyl-2-propanol (tert-butyl alcohol), 1-pentanol, 2-pentanol, 3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, cyclohexanol, 2-methyl- cyclopentanonol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, and isomers thereof. Ketones may include, without limitation, hydroxyketones, cyclic ketones, diketones, acetone, propanone, 2-oxopropanal, butanone, butane-2,3-dione, 3-hydroxybutan-2-one, 2-pentanone, 3-pentanone, cyclopentanone, pentane-2,3-dione, pentane-2,4-dione, 2-hexanone, 3-hexanone, cyclohexanone, 2-methyl-cyclopentanone, heptanone, octanone, nonanone, decanone, undecanone, dodecanone, methylglyoxal, butanedione, pentanedione, diketohexane, and isomers thereof. Aldehydes may include, without limitation, hydroxyaldehydes, acetaldehyde, propionaldehyde, 2-hydroxy-propionaldehyde, butyraldehyde, 2-hydroxypropionaldehyde, 3-hydroxypropionaldehyde, 2-methyl-propanal, pentanal, hexanal, heptanal, octanal, nonal, decanal, undecanal, dodecanal, and isomers thereof. Carboxylic acids may include, without limitation, formic acid, acetic acid, propionic acid, butanoic acid, isobutyric acid, pentanoic acid, hexanoic acid, heptanoic acid, isomers and derivatives thereof, which include hydroxylated derivatives such as 2-hydroxybutanoic acid and lactic acid. Diols can include, without limitation, ethylene glycol, propylene glycol, 1,3-propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, undecanediol, dodecanediol, and isomers thereof. Triols can include, without limitation, glycerol, 1,1,1 tris(hydroxymethyl)ethane (trimethylolethane), trimethylolpropane, hexanetriol, and isomers thereof. Cyclic ethers include, without limitation, tetrahydrofuran, 2-methyl-tetrahydrofuran, 2,5-dimethyl-tetrahydrofuran, 2-ethyl-tetrahydrofuran, 3-hydroxytetrahydrofuran, tetrahydro-3-furanol, tetrahydro-2-furoic acid, dihydro-5 -(hydroxymethyl)-2(3H)-furanone, 1-(2-furyl)ethanol, tetrahydropyran, 2-methyltetrahydropyran, and isomers thereof. Furans include, without limitation, furfural, furan, dihydrofuran, 2-furan methanol, 2-methyl furan2-ethyl furan, hydroxylmethylfurfural, 2,5-dimethyl furan, 5-hydroxymethyl-1-2(5H)-furanone, dihydro-5- (hydroxymethyl)-2(3H)-furanone, tetrahydrofurfuryl alcohol, hydroxymethyltetrahydrofurfural.
    The second reagent includes one or more hydrocarbons and/or oxygenated hydrocarbons that have a general formula CpHrOs, with g representing 2 to 7 carbon atoms and s representing 0 to 1 oxygen atom. When the second reactant is derived from a recycle stream as described below, the second reactant may also contain residual oxygenated hydrocarbons that contain 2 oxygen atoms. Collectively, the average oxygen to carbon ratio of the second reactant should be less than 0.2, calculated as the total number of oxygen atoms(s) in the second reactant's oxygenated hydrocarbons divided by the total number of carbon atoms (jo) in the hydrocarbons and oxygenated hydrocarbons of the second reagent. Alternatively, the second reactant may have an average oxygen per molecule ratio of less than 1.5, calculated as the total number of oxygen atoms(s) in the second reactant's oxygenated hydrocarbons divided by the total number of hydrocarbon and hydrocarbon molecules oxygenated in the second reagent. The second reagent can also be characterized as having an average normal boiling point of less than 210°C, less than 200°C or less than 190°C.
    The second reagent will generally include alkanes, alkenes, mono-oxygenated hydrocarbons (such as alcohols, ketones, aldehydes, cyclic ethers), as well as residual oxygen compounds capable of being volatilized based on temperature, total pressure and concentration of compounds (such as various diols and carboxylic acids). Examples of second reagent compounds include, without limitation, the C7- compounds listed below.
    The second reagent can be supplied from any source, but is preferably derived from biomass or a raw material derived from biomass. For example, although a feedstock derived from biomass is preferred, it is noted that all or a portion of the second reactant can originate from fossil fuel-based compounds such as natural gas or petroleum. All or part of the second reagent can also originate from any one or more fermentation technologies, gasification technologies, Fischer-Tropsch reactions, or pyrolysis technologies, among others. It is preferred that at least a portion of the second reagent is derived from the product stream and recycled to be combined with the first reagent to provide at least a portion of the reagent stream.
    When a part of the second reagent is derived from the product stream, the product stream is separated into a first part which contains the desired Cg+ compounds and a second part which contains the compounds to be recycled 15 and used as a part of the second reagent.
    Alternatively, the product stream can first be separated into a water fraction and an organic fraction, with the organic fraction then separated into a first part that contains the desired C8+ compounds and a second part that contains the compounds to be recycled. and used as a part of the second reagent. Processes for separating liquid mixtures into their fractions or component parts are common knowledge in the art, and often involve the use of a separating unit, such as one or more distillation columns, phase separators, extractors, purifiers , between others.
    In one embodiment, the separation step includes one or more distillation columns designed to facilitate the separation of the C8+ compounds from the product stream or, alternatively, the separation from the product stream of the second part containing the compounds a recycled and used as a part of the second reagent. The distillation will generally be operated at a temperature, pressure, reflux ratio, and with a suitable equipment design, to recover the second part as a suspended product that conforms to the boiling point characteristics described above. The first part, which contains the Cg+ compounds, and with a higher mean boiling point profile than the second part, will be taken as a high boiling bottom product that can be further processed to effect further separations.
    The composition of the reagent stream will depend on the concentration of water (if any), the first reagent and the second reagent in the reagent stream. In one embodiment, the second reactant mass flow rate is adjusted such that the mass ratio of the second reactant to the first reactant is greater than 5%, or greater than 10%, or greater than 20% , or greater than 30%. Alternatively, the first reactant and second reactant can be combined in such a way that the oxygen mass fraction in the combined reactant flow is at least 10% less, 20% less, 30% less or 40% less than the oxygen fraction. oxygen mass in the first reagent alone.
    The condensation reaction is carried out using catalytic materials that exhibit acidic activity. These materials can be augmented by the addition of a metal to allow molecular hydrogen activation for the hydrogenation/dehydrogenation reactions. Without being bound by any specific theory, the reactions are generally believed to consist of a series of steps shown schematically in Figure 8. The steps involve the removal of oxygen, formation of carbon-carbon bonds to form larger carbon-containing species. , cyclization reactions and hydrogenation reactions. Oxygen removal steps include: (a) dehydrating alcohols to form alkenes; (b) hydrogenolysis of alcohols; (c) hydrogenation of carbonyls to alcohols followed by dehydration; and (d) ketonization of organic acids. Within the condensation system, oxygen removal steps allow the processing of compounds that contain 1, 2, 3, 4, 5 5 or 6 oxygen atoms. Carbon-carbon bond formation to create larger carbon-containing species occurs through: (a) oligomerization of alkenes; (b) aldol condensation to form α-hydroxy ketones or α-hydroxy aldehydes; (c) hydrogenation of the conjugated enones to form ketones or aldehydes, which can participate in additional condensation reactions or convert to alcohols or hydrocarbons; (d) Prins reactions between alkenes and aldehydes; and (e) ketonization of organic acids. Acid catalyzed pathways to form cyclic compounds 15 include: (a) intramolecular aldol condensations; and (b) dehydration of cyclic ethers to form dienes with subsequent reaction of the diene with an alkene through a Diel-Alder condensation. Finally, alkenes can be hydrogenated via hydride transfer and/or via a hydrogenation pathway that uses metals added to acidic materials.
    The acid condensation catalyst may consist of an acid support or a heterogeneous acid catalyst comprising a support and an active metal, such as Pd, Pt, Cu, 25 Co, Ru, Cr, Ni, Ag, alloys thereof, or combinations thereof. of the same. The acid condensation catalyst may include, without limitation, aluminosilicates, tungsten aluminosilicates, silica-alumina phosphates (SAPOs), aluminum phosphates (ALPO), amorphous silica alumina (ASA), acidic alumina, phosphated alumina, tungsten alumina, zirconia , tungsten zirconia, tungsten silica, tungsten titanium, tungsten phosphates, acid-modified resins, heteropolyacids, tungsten heteropolyacids, silica, alumina, zirconia, titania, tungsten, niobia, zeolites, mixtures thereof, and combinations thereof. The acid condensation catalyst may include the above alone or in combination with a modifier or metal such as Re, Cu, Fe, Ru, Ir, Co, Rh, Pt, Pd, Ni, W, Os, Mo, Ag, Au, leagues thereof, and combinations thereof.
    The acid condensation catalyst may be self-supporting (i.e., the catalyst does not need another material to serve as a support), or it may require a separate support suitable for suspending the catalyst in the reactant flow, such as any of the supports described. further below, which include supports containing carbon, silica, alumina, zirconia, titania, vanadia, kieselguhr, hydroxyapatite, chromia, mixtures thereof, and combinations thereof. In some embodiments, particularly when the acid condensation catalyst is a powder, the catalyst system may include a binder to aid in forming the catalyst into a desired catalyst format. Applicable binders include, without limitation, alumina, clay, silica, zinc aluminate, aluminum phosphate and zirconia. A number of forming processes can be employed to produce the catalyst which include extrusion, pelletizing, oil dripping or other known processes. After drying, this material is calcined at a temperature suitable for the formation of the catalytically active phase, which usually requires temperatures above 400°C.
    The acid condensation catalyst can include one or more zeolite structures that comprise silica-alumina cage-like structures. Zeolites are crystalline microporous materials with a well-defined pore structure. Zeolites also contain active sites, usually acidic sites, which can be generated in the zeolite structure, whose strength and concentration can be adapted for particular applications. The structure of the zeolite or particular zeolites can also be altered to produce different amounts of different hydrocarbon species in the product mixture. For example, the zeolite catalyst can be structured to produce a product mixture that contains varying amounts of cyclic hydrocarbons. Ga, In, Zn, Fe, Mo, Ag, Au, Ni, P, Sc, Y, Ta and lanthanides can also be exchanged over zeolites to provide a zeolite catalyst that has a particular desired activity. Metal functionality can be provided by metals 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. Consequently, "zeolites" not only refer to microporous crystalline aluminosilicate, but also to microporous crystalline metal-containing aluminosilicate structures, such as galloaluminosilicates and gallosilicates.
    The acid condensation catalyst may also consist of a difunctional pentasyl zeolite catalyst which includes at least one metallic element from the group of Re, Cu, Fe, Ru, Ir, Co, Rh, Pt, Pd, Ni, W, Os , Mo, Ag, Au, Sn, alloys and combinations thereof, or a modifier from the group of Ga, In, Zn, Fe, Mo, Au, Ag, Y, Sc, Ni, P, Ta, lanthanides, and combinations thereof. Zeolite preferably has dehydrogenation sites and strong acids, and can be used with reagent streams that contain an oxygenated hydrocarbon at a temperature below 500”C.
    Bifunctional pentasil zeolite can have a crystal structure of the ZSM-5, ZSM-8 or ZSM-11 type which consists of a large number of 5-membered oxygen-containing rings, ie, pentasil rings. Zeolite with structure of the ZSM-5 type is a particularly preferred catalyst. The bifunctional pentasyl zeolite catalyst may consist of ZSM-5 type zeolites modified with Ga and/or In, such as H-ZSM-5 impregnated with Ga and/or In, H-ZSM-5 exchanged with Ga and/or In, H-gallosilicate of structure of the ZSM-5 type and H-5 galloaluminosilicate of structure of the ZSM-5 type. The bifunctional pentasil zeolite of the ZSM-5 type may contain aluminum and/or tetrahedral gallium present in the structure or cross-linking of zeolite and gallium or indium octahedral. The octahedral sites are not present in the zeolite structure, but are present in the zeolite channels in a position close to the zeolite protonic acid sites, which are attributed to the presence of aluminum and tetrahedral gallium in the zeolite. Structured or tetrahedral Al and/or Ga is believed to be responsible for the acidic function of zeolite, and octahedral or non-structured 15 Ga e/or In is believed to be responsible for the dehydrogenation function of zeolite.
    Examples of other suitable zeolite catalysts include ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35 and ZSM-48. ZSM-5 zeolite, and the conventional preparation thereof, is described in patent no. U.S. 3,702,886; Re. 29,948 (highly siliceous ZSM-5); 4,100,262 and 4,139,600, all incorporated herein by reference. Zeolite ZSM-11, and the conventional preparation thereof, is described in patent no. U.S. 3,709,979, which is also incorporated herein by reference. ZSM-12 zeolite, and the conventional preparation thereof, is described in patent no. U.S. 3,832,449, incorporated herein by reference. Zeolite ZSM-23, and the conventional preparation thereof, is described in patent no. U.S. 4,076,842, incorporated herein by reference. ZSM-35 zeolite, and the conventional preparation thereof, is described in patent no. U.S. 4,016,245, incorporated herein by reference. Another preparation of ZSM-35 is described in patent no. U.S. 4,107,195, the disclosure of which is incorporated herein by reference. ZSM-48, and the conventional preparation thereof, is shown by patent no. U.S. 4,375,573, incorporated herein by reference. Other examples of zeolite catalysts are described in patent no. U.S. 5,019,663 and patent no. U.S. 7,022,888, also incorporated herein by reference.
    Alternatively, solid acid catalysts such as alumina modified with phosphates, chloride, silica and other acidic oxides could be used as an acid condensation catalyst in the practice of the present invention. Sulphated zirconia or tungsten zirconia can also provide the necessary acidity. In one embodiment, the acid condensation catalyst consists of tungsten zirconia modified to have at least one metallic element from the group of Re, Cu, Fe, Ru, Ir, Co, Rh, Pt, Pd, Ni, W, Os, Mo, Ag, Au, alloys and combinations thereof.
    The acidic condensation catalyst can also consist of a resin capable of serving as an acidic support (eg supports that have low isoelectric points) which is capable of catalyzing condensation reactions. Heteropolyacids consist of a class of solid phase acids exemplified by species such as H3+xPMoi2-xVx04o, H4SIW12O40, H3PW12O40 and H6P2WI8O62- Heteropolyacids also have a well-defined site structure, the most common of which is the Keggin structure tungsten-based.
    The specific C8+ compounds produced will depend on several factors including, without limitation, the composition of the reagent flow, the type of oxygenates in the first reagent, the hydrocarbons and oxygenated hydrocarbons in the second reagent, the concentration of water, the condensing temperature, the condensing pressure, the catalyst reactivity and the flow rate of the reactant flow as this affects the space velocity (the mass/volume of reactant per catalyst unit per unit time), hourly space velocity per gas (GHSV ) and hourly space velocity by weight (WHSV). It is preferred that the reactant stream is contacted with the acid condensation catalyst in a WHSV which is suitable to produce the desired hydrocarbon products. The WHSV is preferably at least about 0.1 grams of oxygenate in the reactant flow per hour, more preferably the WHSV is between about 0.1 to 40.0 g/gh, which includes a WHSV of about 0.2, 0.4, 0.6, 0.8, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20 , 25, 30, 35 g/gh, and increments in between.
    Condensing pressure and temperature conditions can be selected to most favorably produce the desired products in the vapor phase or in a mixed phase that has both a liquid and a vapor phase. In general, the condensation reaction should be conducted at a temperature and pressure where the thermodynamics of the reactions are favorable. For example, the minimum pressure required to maintain a portion of the reactant flow in the liquid phase will vary with the reaction temperature. As temperatures increase, higher pressures will generally be required to maintain reagent flow in the liquid phase. Any pressure above that required to keep the raw material in the liquid phase (ie, vapor phase) is also an adequate operating pressure. For vapor phase reactions, the reaction should be conducted at a condensing temperature, where the vapor pressure of the oxygenated hydrocarbon compound is at least about 0.1 atm (and preferably a considerably greater amount) , and the thermodynamics of the reactions are favorable.
    In general, the condensing temperature should be greater than 100°C, 150°C, 180°C or 200°C, and less than 400°C, 370°C or 350°C. The reaction pressure should be greater than 72 psig, 125 psig, 200 psig, 300 psig, 365 psig or 500 psig, and less than 2000 psig, 1800 psig, 1700 psig or 1500 psig. In one embodiment, the condensing temperature is between about 100°C and 400°C, between about 150°C and 370°C, or between about 180°C and 300°C. In another embodiment, the deoxygenation pressure is between about 72 and 2000 psig, between about 200 and 1800 psig, between about 300 and 1700 psig, or between about 500 and 1500 psig.
    Variation of the above factors, as well as others, will generally result in a modification to the specific composition and yields of the Cg+ compounds. For example, varying the temperature and/or pressure of the reactor system, or particular catalyst formulations, can result in the production of more Cg+ alcohols and/or ketones rather than C8+ hydrocarbons. Varying the temperature and/or pressure of the reactor system, or particular catalyst formulations, can also result in the production of C7- compounds that can be recycled and used as the second reactant or used for liquid fuels (eg gasoline) or chemicals directly or after further processing.
    C8+ product compounds may contain high levels of alkenes, alcohols and/or ketones, which may be undesirable in certain fuel applications or which lead to coking or deposits in combustion engines, or other undesirable combustion products. In such an event, C8+ compounds can be optionally hydrogenated to reduce ketones to alcohols and hydrocarbons, and unsaturated alcohols and hydrocarbons to alkanes, cycloalkanes, and aryls, thus forming a more desirable hydrocarbon product that has low levels of alkenes , alcohols or ketones.
    The C8+ composite product can also undergo a finishing step. The finishing step will generally consist of a hydrotreating reaction which removes a portion of the remaining carbon-carbon double bonds, carbonyl, hydroxyl, acid, ester and ether groups. In such an event, any one of several hydrotreating catalysts described can be used. Such catalysts may include any one or more of the following metals, Cu, Ni, Fe, Co, Mo, W, Ru, Pd, Rh, Pt, Ir, alloys or combinations thereof, alone or with promoters such as Au, Ag, Cr, Zn, Mn, Sn, Cu, Bi, and alloys thereof can be used in various loads ranging from about 0.01 to about 20% by weight on a support. , as described above.
    In general, the finishing step is performed at finishing temperatures between about 80°C to 400°C, and finishing pressures in the range of about 100 psig to 2000 psig. The finishing step can be conducted in the vapor phase or liquid phase, and can use in situ generated H2, external H2, recycled H2 or combinations thereof as required.
    Other factors, such as the concentration of unwanted water or oxygenates, can also affect the composition and yield of Cg+ compounds. In such an event, the process can include a dewatering step that removes some of the water after condensation or a separation unit for removing unwanted oxygenates. For example, a separator unit, such as a phase separator, extractor, purifier or distillation column, can be installed after the condensation step in order to remove some of the water from the product stream. A separation unit can also be installed to remove specific oxygenates for recycling and use as the first reactant or as a supplement to the first reactant and/or oxygenated hydrocarbons and hydrocarbons for use as the second reactant or as a supplement to the second reactant .
    Cg+ Compounds The present invention allows for the production of a higher yield of C8+ compounds due to the unique combination of the first and second reagents in the reagent flow. In one embodiment, the yield of C8+ compounds in the product stream is greater than 40%, greater than 50%, greater than 60%, or greater than 75% of the carbon yield for the product stream. In another modality, the yield of C8+ compounds in the heavy part of the product flow is greater than 60%, greater than 70%, greater than 80%, greater than 90% or greater than 95% of the carbon in the part heavy flow of product. In yet another modality, the yield of C8+ compounds in the product flow is more than 10%, more than 25%, more than 50%, more than 75%, more than 100%, more than 150% or more than 200% greater than the practice of the invention, without the inclusion of a second reagent stream.
    The condensation reactions result in the production of C8+ alkanes, C8+ alkenes, C8+ cycloalkanes, C8+ cycloalkenes, C8+ aryls, fused aryls, C8+ alcohols, C8+ ketones, C8+ oxygenated aryls, oxygenated fused aryls, and mixtures thereof. C8+ alkanes and C8+ alkenes have 8 or more carbon atoms, and can be straight-chain or branched alkanes or alkenes. C8+ alkanes and C8+ alkenes can also include fractions containing compounds C8, C9, C10, Cu, C12, C13, C14 (Ca-14 fraction), or compounds C12, C13, C14, C15, C18, C17, Cys, Cig , C20, C21, C22, C23, C24 (C12-24 fraction), or more than 25 carbon atoms (C25+ fraction), with the C8-i4 fraction directed to jet fuels, the C12-24 fraction directed to fuel diesel, and the C25+ fraction intended for heavy oils and other industrial applications. Examples of various C8+ alkanes and C8+ alkenes include, without limitation, octane, octene, 2,2,4,-trimethylpentane, 2,3-dimethyl hexane, 2,3,4-trimethylpentane, 2,3-dimethylpentane , nonane, nonene, decane, decene, undecane, undecene, dodecane, dodecene, 5 tridecane, tridecene, tetradecane, tetradecene, pentadecane, pentadecene, hexadecane, hexadecane, heptyldecane, heptyldecene, octyldecane, octyldecane, noctyldecene uneicosane, uneicosene, doeicosan, doeicosene, trieicosan, trieicosene, tetraeicosane, tetraeicosene, and isomers thereof.
    C8+ cycloalkanes and C8+ cycloalkenes have 8 or more carbon atoms and can be unsubstituted, monosubstituted or multisubstituted. In the case of monosubstituted and multisubstituted compounds, substituted group 15 may include a branched C3+ alkyl, a straight chain C3+ alkyl, a branched C3+ alkylene, a straight chain C2+ alkylene, a straight chain C2+ alkyne, a phenyl, or a combination of the same. In one embodiment, at least one of the substituted groups includes a branched C3+ alkyl, a straight-chain C3+ alkyl, a branched C3+ alkylene, a straight-chain C2+ alkylene, a straight-chain C2+ alkyne, a phenyl, or a combination thereof. . Examples of desirable C8+ cycloalkanes and C8+ cycloalkenes include, without limitation, ethyl-cyclopentane, ethyl-cyclopentene, ethyl-cyclohexane, ethyl-cyclohexene, and isomers thereof.
    The C8+ aryls will generally consist of an aromatic hydrocarbon in an unsubstituted (phenyl), monosubstituted or multisubstituted form. In the case of mono- 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. Examples of various C8+ aryls include, without limitation, xylene (dimethylbenzene), ethyl benzene, for xylene, meta xylene, ortho xylene, C9 aromatics (such as trimethyl benzene, methyl ethyl benzene, propyl benzene), and C10 aromatics (such as as, diethylbenzene, tetramethylbenzene, dimethyl ethylbenzene), etc.
    Fused aryls will generally consist of bicyclic and polycyclic aromatic hydrocarbons, in an unsubstituted, monosubstituted or multisubstituted form. In the case of monosubstituted and multisubstituted compounds, the substituted group can include a branched C3+ alkyl, a straight chain C3+ 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 isomers thereof.
    C8+ alcohols can also be straight-chain, branched or cyclic, and have 8 or more carbon atoms. In general, C8+ alcohols can consist of a compound according to a formula RX-OH, wherein R1 is a member selected from the group consisting of a branched C8+ alkyl, a straight chain C8+ alkyl, a branched C8+ alkylene , a straight chain C8+ alkylene, a substituted C8+ cycloalkane, an unsubstituted C8+ cycloalkane, a substituted C8+ cycloalkene, an unsubstituted C8+ cycloalkene, an aryl, a phenyl, and combinations thereof. Examples of desirable C8+ alcohols include, without limitation, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptyldecanol, octyldecanol, nonyldecanol, eicosanol, uneicosanol, doeicosanol, isanol and even trieicosanols.
    C8+ ketones can also be straight-chain, branched or cyclic, and have 8 or more carbon atoms. In general, the C8+ ketone can consist of a compound according to the formula
    R4 wherein R3 and R4 are independently a member selected from the group consisting of a branched C3+ alkyl, a straight-chain C3+ alkyl, a branched C34-alkylene, a straight-chain C2+ alkylene, a substituted Cs+ cycloalkane, an unsubstituted C8+ cycloalkane, a substituted Cs+ cycloalkene, an unsubstituted C8+ cycloalkene, an aryl, a phenyl, and a combination thereof. Examples of desirable Cg+ ketones include, without limitation, octanone, nonanone, decanone, undecanone, dodecanone, tridecanone, tetradecanone, pentadecanone, hexadecanone, heptyldecanone, octyldecanone, nonyldecanone, eicosanone, uneicosanone, tetraeicosanone, and same isoeicosanone.
    Oxygenated C8+ aryls will generally consist of an aromatic hydrocarbon (in an unsubstituted (phenyl), mono- or multi-substituted form) that has one or more oxygen atoms. Examples of oxygenated C8+ aryls include, without limitation, C8+ alkyl substituted phenols, alkyl substituted indanones, alkyl substituted benzoic acids, alkyl substituted aryl alcohols, alkyl substituted aryl aldehydes, terephthalic acid, isophthalic acid.
    Oxygenated fused aryls will generally consist of bicyclic and polycyclic aromatic hydrocarbons (in an unsubstituted, monosubstituted or multisubstituted form) that have one or more oxygen atoms. Examples of oxygenated fused aryls include, without limitation, alkyl substituted naphthols, alkyl substituted naphthalenic acids, alkyl substituted naphthalene alcohols, alkyl substituted naphthalenic aldehydes, and 2,6 naphthalenedicarboxylic acid.
    The above moderate fractions (Cg-Cn) can be separated for jet fuel, while the C12-C24 fraction can be separated for diesel fuel and the heavier fraction (C25+) separated for use as a heavy or cracked oil to produce additional gasoline and/or diesel fractions. C8+ compounds can also be used as industrial chemicals, as an intermediate or a final product. For example, C9 aromatics and fused aryls such as naphthalene, tetrahydronaphthalene, decahydronaphthalene and anthracene can be used as solvents in industrial processes. Compounds C7-
    The condensation reactions will also result in the production of C7- alkanes, C7- alkenes, C7- cycloalkanes, C7- cycloalkenes, C7- alcohols, C7- ketones, C7- aryls and mixtures thereof. It is preferred that compounds C7- are of the type suitable for use as the second reagent or as a supplement to the second reagent. Consequently, in one embodiment, the C7- compounds can be separated from the product stream and recycled for use as the second reagent. In another embodiment, a portion of the C7- compounds can be separated from the product stream and used as a gasoline or as a blending component for gasoline, or in other industrial applications.
    In general, C7-alkanes and C7-alkenes have from 4 to 7 carbon atoms (C4-7 alkanes and C4-7 alkenes) and can consist of straight-chain, branched or cyclic alkanes or alkenes. Examples of various C7-alkanes and C7-alkenes include, without limitation, butane, isobutane, butene, isobutene, pentane, pentene, 2-methylbutane, hexane, hexene, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2 ,3-dimethylbutane, cyclohexane, heptane, heptene, methyl-cyclohexane and isomers thereof.
    C7-alcohols can also be cyclic, branched or straight-chain and have 7 or fewer carbon atoms. In general, the C7-alcohols may consist of a compound according to the formula R5-OH, wherein R5 is an element selected from the group consisting of a branched C7-alkyl, a straight-chain C7-alkyl, a C7-alkylene branched, a straight-chain C7-alkylene, a C7-substituted cycloalkane, an unsubstituted C7-cycloalkane, a substituted C7-cycloalkene, an unsubstituted C7-cycloalkene, a C7-aryl, a C7-phenyl and combinations thereof. Examples of desirable C7 alcohols include, without limitation, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, isobutanol, tert-butyl alcohol, pentanol, hexanol, heptanol, and isomers thereof.
    The C7-' ketones can also be cyclic, branched or straight-chain and have 7 or fewer carbon atoms. In general, the C7-ketone may consist of a compound according to the formula R3=0 wherein R3 is an element selected from the group consisting of a branched C3-7 alkyl, a straight chain C3-7 alkyl, a branched C3_7 alkylene, a straight chain C3_7 alkylene, a substituted C5 cycloalkane, cyclopentane, methyl-cyclopentane, cyclohexane, and combinations thereof. Examples of desirable C7 ketones include, without limitation, acetone, butanone, 2-pentanone, 3-pentanone, 3-methyl-butan-2-one, 2-hexanone, 3-hexanone, 3-methyl-pentyl-2-one , 4-methyl-pentyl-2-one, 2-methyl-pentyl-3-one, 2-heptanone, 3-heptanone, 4-heptanone, cyclopentanone, methyl-cyclopentanone, 2-methyl-cyclopentanone, 3-methyl-cyclopentanone , cyclohexanone, and isomers thereof.
    The C7 aryls will generally consist of an aromatic hydrocarbon having 6 or 7 carbon atoms, and an unsubstituted (phenyl), monosubstituted or multisubstituted form. Examples of various aryls include benzene and toluene.
    C7 cycloalkanes and C7 cycloalkenes have 5, 6 or 7 carbon atoms and can be unsubstituted, monosubstituted or multisubstituted. In the case of monosubstituted and multisubstituted compounds, the substituted group can include a straight chain C 1-2 alkyl, a straight chain C 2 alkylene, a straight chain C 2 alkyne, or a combination thereof. Examples of desirable C7-cycloalkanes and C7-cycloalkenes include, without limitation, cyclopentane, cyclopentene, cyclohexane, cyclohexene, methyl-cyclopentane, methyl-cyclopentene, ethyl-cyclopentane, ethyl-cyclopentene, and isomers thereof.
    Raw materials derived from biomass
    For use herein, the term "biomass" refers to, without limitation, organic materials produced by plants (such as leaves, roots, seeds and stems), and animal and microbial metabolic waste. Common biomass sources include: (1) agricultural residues, which include crop residues from corn, straw, seed husks, sugarcane leftovers, bagasse, walnut husks, cotton gin garbage, and manure from cattle , poultry and pigs; (2) wood materials, which include wood or tree bark, sawdust, log butcher, and mill debris; (3) urban solid waste, which includes recycled paper, used paper and organic waste; and (4) crops for energy production, which include poplar, willow, grass, miscanthus, sorghum, alfalfa, bluegrass, corn, soybean, and the like. The term also refers to the primary building blocks of those mentioned above, namely, lignin, cellulose, hemicellulose and carbohydrates such as saccharides, sugars and starches, among others. For use herein, the term "bioreform" refers to, without limitation, processes for catalytically converting biomass and other carbohydrates to lower molecular weight hydrocarbons and oxygen compounds such as alcohols, ketones, cyclic ethers, esters, acids carboxylics, aldehydes, diols and other polyols, with the use of aqueous phase reform, hydrogenation, hydrogenolysis, hydrodeoxygenation and/or other conversion processes that involve the use of heterogeneous catalysts. Bioreform also includes the further catalytic conversion of such lower molecular weight oxygenated compounds to C4+ compounds.
    For use herein, the term "biomass-derived feedstock" refers to, without limitation, materials that originate from biomass and that have use as a feedstock in one or more bioreform processes. It is preferred that the biomass-derived feedstock is derived from material of recent biological origin such that the age of the compounds, or fractions containing the compounds, is less than 100 years old, preferably less than 40 years of age, and more preferably less than 20 years of age, as calculated from the carbon-14 concentration of the raw material. Common biomass-derived raw materials include lignin and lignocellulosic derivatives, cellulose and cellulosic derivatives, hemicellulose and hemicellulosic derivatives, carbohydrates, starches, monosaccharides, disaccharides, polysaccharides, sugars, sugar alcohols, alditols, polyols, and mixtures thereof. It is preferred that the biomass-derived raw material includes a sugar such as glucose, fructose, sucrose, maltose, lactose, mannose or xylose, or a sugar alcohol such as arabitol, erythritol, glycerol, isomalto, lactitol, malitol , mannitol, sorbitol, xylitol, arabitol, glycol, and other oxygenated hydrocarbons. "Oxygenated hydrocarbons" refers to hydrocarbon compounds having the general formula C^H^Od, where a represents two or more carbon atoms and d represents at least one oxygen atom (collectively, referred to herein as C2+ hydrocarbons hi+) . It is preferred that the oxygenated hydrocarbon has 2 to 12 carbon atoms (C2-12O1-11) hydrocarbon, and more preferably, 2 to 6 carbon atoms (C2-6O1-6 hydrocarbon) • The oxygenated hydrocarbon may also have a ratio of oxygen to carbon that is in a range from 0.07 to 1.0, which includes ratios of 0.08, 0.09, 0.10, 0.16, 0.20, 0.25, 0.3, 0.33, 0.4, 0.5, 0.6, 0.7, 0.75, 0.8, 0.9, and other ratios in between. Additional non-limiting examples of oxygenated hydrocarbons include various alcohols, ketones, aldehydes, furans, hydroxy carboxylic acids, carboxylic acids, diols and triols. 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, isobutanol, pentanol, cyclopentanol, hexanol, cyclohexanol, 2-methyl-cyclopentanonol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, and isomers thereof. Ketones may include, without limitation, hydroxyketones, cyclic ketones, diketones, acetone, propanone, 2-oxopropanal, butanone, butane-2,3-dione, 3-hydroxybutan-2-one, pentanone, cyclopentanone, pentane-2,3 - dione, pentane-2,4-dione, hexanone, cyclohexanone, 2-methyl-cyclopentanone, heptanone, octanone, nonanone, decanone, undecanone, dodecanone, methylglyoxal, butanedione, pentanedione, diketohexane, and isomers thereof. Aldehydes can include, without limitation, hydroxyaldehydes, acetaldehyde, propionaldehyde, butyraldehyde, pentanal, hexanal, heptanal, octanal, nonal, decanal, undecanal, dodecanal, and isomers thereof. Carboxylic acids may include, without limitation, formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, and isomers and derivatives thereof, which include hydroxylated derivatives such as 2-hydroxybutanoic acid and lactic. Diols can include, without limitation, ethylene glycol, propylene glycol, 1,3-propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, undecanediol, dodecanediol, and isomers thereof. Triols can include, without limitation, glycerol, 1,1,1 tris(hydroxymethyl)ethane (trimethylolethane), trimethylolpropane, hexanetriol, and isomers thereof. Cyclic ethers, furans and furfurals include, without limitation, furan, tetrahydrofuran, dihydrofuran, 2-furan methanol, 2-methyl-tetrahydrofuran, 2,5-dimethyl-tetrahydrofuran, 2-methyl furan, 2-ethyl-tetrahydrofuran, 2- ethyl furan, hydroxylmethylfurfural, 3-hydroxytetrahydrofuran, tetrahydro-3-furanol, 2,5-dimethyl furan, 5-hydroxymethyl-2(5H)-furanone, dihydro-5-(hydroxymethyl)-2(3H)-furanone, tetrahydro acid -2-furoic, dihydro-5-(hydroxymethyl)-2(3H)-furanone, tetrahydrofurfuryl alcohol, 1-(2-furyl)ethanol, hydroxymethyltetrahydrofurfural, and isomers thereof.
    Biomass-derived feedstock can be produced by any known method. Such methods include deconstruction technologies using enzymes or microorganisms, Fischer-Tropsch reactions to produce C2-10 alpha alcohols, fermentation technologies using enzymes or microorganisms, and pyrolysis technologies to produce alcohols from oil, among others. In one embodiment, the biomass-derived feedstock is produced using a catalytic reforming technology such as that described in patents no. U.S. 7,767,867 and 7.989,664 and application no. U.S. 2011/0306804 (all to Cortright, and entitled "Methods and Systems for Generating Polyols"); patents no.22. U.S. 8,053,615; 8,017,818; and 7,977,517 (all Cortright and Blommel, and entitled "Synthesis of Liquid Fuels and Chemicals from Oxygenated Hydrocarbons"); patent application no. U.S. 2009/0211942 (to Cortright, and entitled "Catalysts and Methods for Reforming Oxygenated Compounds"); patent application no. U.S. 2010/0076233 (to Cortright et al., and entitled "Synthesis of Liquid Fuels from Biomass"); and international patent application no. PCT/US2008/056330 (to Cortright and Blommel, and entitled "Synthesis of Liquid Fuels and Chemicals from Oxygenated Hydrocarbons").
    Production of Oxygenates The first reagent stream can be provided by reacting an aqueous feedstock solution containing water and one or more water-soluble oxygenated hydrocarbons with hydrogen over a catalytic material to produce a first reagent stream containing water and oxygenates. Hydrogen can be generated in situ using aqueous phase reforming (APR H2), or a combination of APR H2, external H2 or recycled H2, or simply external H2 or recycled H2.
    In processes using H2 from APR, oxygenates are prepared by catalytically reacting a first part of the aqueous raw material solution containing water and the water-soluble oxygenated hydrocarbons in the presence of an APR catalyst at a temperature of reforming and reforming pressure to produce the APR H2 and catalytically reacting the APR H2 (and recycled H2 and/or external H2) with a second part of the raw material solution in the presence of a deoxygenation catalyst in a deoxygenation temperature and deoxygenation pressure to produce the desired oxygenates for the first reagent stream. In systems using recycled H2 or external H2 as a hydrogen source, oxygenates are simply prepared by catalytically reacting recycled H2 and/or external H2 with the aqueous feedstock solution in the presence of the deoxygenation catalyst in the deoxygenation temperatures and pressures.
    The deoxygenation catalyst preferably consists of EMU a heterogeneous catalyst having one or more active materials capable of catalyzing a reaction between hydrogen and the oxygenated hydrocarbon to remove one or more of the oxygen atoms from the oxygenated hydrocarbon to produce alcohols, ketones , aldehydes, cyclic ethers, carboxylic acids, hydroxy carboxylic acids, diols and triols. In general, the heterogeneous deoxygenation catalyst will have both an active metal function and an acidic function to achieve the aforementioned. For example, acid supports primarily catalyze the dehydration reactions of oxygenated compounds. Hydrogenation reactions then take place on the metal catalyst in the presence of H2, producing carbon atoms that are not bonded to oxygen atoms. The bifunctional dehydration/hydrogenation pathway consumes H2 and leads to the subsequent formation of various polyols, diols, ketones, aldehydes, alcohols, carboxylic acids, hydroxy carboxylic acids and cyclic ethers such as furans and pyrans. In one embodiment, the deoxygenation catalyst is atomically identical to the acidic condensation catalyst.
    Active materials may include, without limitation, Cu, Re, Fe, Ru, Ir, Co, Rh, Pt, Pd, Ni, W, Os, Mo, Ag, Au, alloys thereof, and combinations thereof, adhered to a support. The deoxygenation catalyst can include these elements alone or in combination with one or more Mn, Cr, Mo, W, V, Nb, Ta, Ti, Zr, Y, La, Sc, Zn, Cd, Ag, Au, Sn, Ge, P, Al, Ga, In, Tl, Ce, and combinations thereof. In one embodiment, the deoxygenation catalyst includes Pt, Pd, Ru, Re, Ni, W or Mo. In yet another embodiment, the deoxygenation catalyst includes Sn, W, Mo, Ag, Fe and/or Re and at least one transition metal selected from Ni, Pd, Pt and Ru.
    In another embodiment, the catalyst includes Fe, Re and at least I
    Cu or a Group VIIIB transition metal. In yet another embodiment, the deoxygenation catalyst includes Pd alloyed or mixed with Cu or Ag and supported on an acid support. In yet another embodiment, the deoxygenation catalyst includes Pd alloyed or mixed with a Group VIB metal supported on an acid support. In yet another embodiment, the deoxygenation catalyst includes Pd alloyed or mixed with a Group VIB metal and a Group IVA metal on an acidic support. The support can consist of any one of a number of supports, which include a support having carbon, silica, alumina, zirconia, titania, tungsten, vanadia, chromia, zeolites, heteropolyacids, kieselguhr, hydroxyapatite, and mixtures thereof.
    The deoxygenation catalyst can also include an acid support modified or constructed to provide the desired functionality. Heteropolyacids are a class of solid-phase acids exemplified by such species as H3+xPMθi2_xVxO40, H4SIW12O40, H3PW12O40 6 H6P2W18O62. Heteropolyacids are solid-phase acids that have a well-defined local structure, the most common of which is the tungsten-based Keggin structure. Other examples may include, without limitation, tungsten zirconia, tungsten-modified zirconia, tungsten-modified alpha-alumina, or tungsten-modified theta-alumina.
    The charge of the first element (ie Cu, Re, Fe, Ru, Ir, Co, Rh, Pt, Pd, Ni, W, Os, Mo, Ag, Au, alloys and combinations thereof) is in the range of 0.25% by weight to 25% by weight on carbon, with percentages by weight of 0.10% and 0.05% increments therebetween, such as 1.00%, 1.10%, 1, 15%, 2.00%, 2.50%, 5.00%, 10.00%, 12.50%, 15.00% and 20.00%. The preferred atomic ratio of the second element (ie, Mn, Cr, Mo, W, V, Nb, Ta, Ti, Zr, Y, La, Sc, Zn, Cd, Ag, Au, Sn, Ge, P, Al , Ga, In, Tl, Ce, and combinations thereof) is in the range of 0.25 to 1 to 10 to 1, which includes any ratios between them, such as 0.50, 1.00, 2.50 , 5.00 and 7.50 to 1. If the catalyst is adhered to a support, the combination of catalyst and support is from 0.25% by weight to 10% by weight of the primary element.
    To produce oxygenates, the oxygenated hydrocarbon is combined with water to provide an aqueous feedstock solution that has an effective concentration to cause the formation of the desired reaction products. The ratio of water to carbon on a molar basis is preferably from about 0.5:1 to about 100:1, which includes ratios such as 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 15:1, 25:1, 50:1 75:1, 100:1, and any reasons between them. The raw material solution can also be characterized as a solution that has at least 1.0 percent by weight (% by weight) of the total solution as an oxygenated hydrocarbon. For example, the solution can include one or more oxygenated hydrocarbons, with the total concentration of oxygenated hydrocarbons in the solution being at least about 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60 %, 70%, 80% or greater by weight, which includes any percentages in between, and depending on the oxygenated hydrocarbons used. In one embodiment, the raw material solution includes at least about 10%, 20%, 30%, 40%, 50% or 60% of a sugar, such as glucose, fructose, sucrose or xylose, or a sugar alcohol. sugar, such as sorbitol, mannitol, glycerol or xylitol, by weight. Water to carbon ratios and percentages outside the ranges indicated above are also included. It is preferred that the equilibrium of the raw material solution is water. In some embodiments, the feedstock solution consists essentially of water, one or more oxygenated hydrocarbons, and optionally one or more feedstock modifiers described herein, such as alkali or acid hydroxides or alkali or alkaline earth salts . The raw material solution can also include oxygenated hydrocarbons recycled from the reactor system. The raw material solution may also contain negligible amounts of hydrogen, preferably less than about 1.5 moles of hydrogen per mole of raw material.
    The raw material solution is reacted with hydrogen in the presence of the deoxygenation catalyst under conditions of deoxygenation temperature and pressure and hourly space velocity by weight effective to produce the desired oxygenates. The specific oxygenates produced will depend on several factors, which include the raw material solution, reaction temperature, reaction pressure, water concentration, hydrogen concentration, catalyst reactivity, and material solution flow rate. press as it affects space velocity, GHSV and WHSV. For example, an increase in the flow rate, and thus a reduction in feedstock exposure to catalysts over time, will limit the extent of reactions that can occur, thus causing increased yield for diols and triols. higher level, with a reduction in ketone and alcohol yields.
    The deoxygenation pressure and temperature are preferably selected to maintain at least some of the raw material in the liquid phase at the reactor inlet. It is recognized, however, that temperature and pressure conditions can also be selected to more favorably produce the desired products in the vapor phase or in a mixed phase that has both a liquid and a vapor phase. In general, the reaction should be conducted under process conditions where the thermodynamics of the proposed reaction are favorable. For example, the minimum pressure required to keep some of the raw material in the liquid phase will likely vary with reaction temperature. As temperatures increase, higher pressures will generally be required to keep the raw material in the liquid phase, if desired. Pressures above that required to keep the raw material in the liquid phase (ie, vapor phase) are also suitable operating conditions.
    In general, the deoxygenation temperature should be greater than 120°C, 150°C, 180°C or 200°C, and less than 325°C, 300°C, 280°C, 260°C, 240° C or 220°C. The reaction pressure should be greater than 200 psig, 365 psig, 500 psig or 600 psig, and less than 2500 psig, 2250 psig, 2000 psig, 1800 psig, 1500 psig, 1200 psig, 1000 psig or 725 psig. In one embodiment, the deoxygenation temperature is between about 150°C and 300°C, between about 200°C and 280°C, between about 220°C and 260°C, or between about 150°C and 260 °C. In another modality, the deoxygenation pressure is between about 365 and
    2500 psig, between about 500 and 2000 psig, between about 600 and 1800 psig, or between about 365 and 1500 psig.
    A condensed liquid phase method can also be performed using a modifier that increases the activity and/or stability of the catalyst system. For example, alkaline or earth alkaline salts can be added to optimize the system. Examples of suitable water-soluble salts include one or more selected from the group consisting of an alkali or alkaline earth metal hydroxide, carbonate, nitrate or chloride salt. For example, adding alkaline (basic) salts to provide a pH from about pH 4.0 to about pH 10.0 can improve the hydrogen selectivity of reforming reactions. It is preferred that the water and oxygenated hydrocarbon are reacted at a suitable pH from about 1.0 to about 10.0, which includes pH values in 0.1 and 0.05 increments therebetween, and more preferably, at a pH of from about 4.0 to about 10.0. Generally, the modifier is added to the stock solution in an amount in the range from about 0. 1% to about 10% by weight, as compared to the total weight of the catalyst system used, although amounts outside this range are included in the present invention.
    In general, the reaction should be conducted under conditions where the residence time of the raw material solution on the catalyst is adequate to generate the desired products. For example, the WHSV for the reaction can be at least about 0.1 gram of oxygenated hydrocarbon per gram of catalyst per hour, and more preferably, the WHSV is about 0.1 to 40.0 g/gh , which includes 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, 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/gh, and ratios between them (which include 0.83, 0.85, 0.85, 1.71, 1.72, 1.73, etc. .).
    The hydrogen used in the deoxygenation reaction can be in-situ generated H2, external H2 or recycled H2. The amount (moles) of external H2 or recycled H2 introduced into the raw material is between 0 to 100%, 0 to 95%, 0 to 90%, 0 to 85%, 0 to 80%, 0 to 75%, 0 to 70%, 0 to 65%, 0 to 60%, 0 to 55%, 0 to 50%, 0 to 45%, 0 to 40%, 0 to 35%, 0 to 30%, 0 to 25%, 0 to 20%, 0 to 15%, 0 to 10%, 0 to 5%, 0 to 2% or 0 to 1% of the total number of moles of oxygenated hydrocarbon(s) in the raw material, which includes all intervals between them. When the raw material solution, or any part thereof, is reacted with APR hydrogen and external H2 or recycled H2, the molar ratio of APR hydrogen to external H2 (or recycled H2) is at least 1:100, 1: 50, 1:20; 1:15, 1:10, 1:5; 1:3, 1:2, 1:1, 2:1, 3:1, 5:1, 10:1, 15:1, 20:1, 50:1, 100:1 and ratios between them (which include 4:1, 6:1, 7:1, 8:1, 9:1, 11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1, 18 :1 and 19:1, and vice versa).
    In-situ Hydrogen Production An advantage of the present invention is that it allows the production and use of H2 generated in-situ. APR H2 is produced from the feedstock under aqueous phase reforming conditions with the use of an aqueous phase reforming catalyst (APR catalyst). The APR catalyst preferably consists of a heterogeneous catalyst capable of catalyzing the reaction of water and oxygenated hydrocarbons to form H2 under the conditions described below. In one embodiment, the APR catalyst includes a support and at least one of Fe, Ru, Ir, Co, Rh, Pt, Pd, Ni, alloys and combinations thereof. The APR catalyst can also include at least one additional material from Group VIIIB, Group VIIB, Group VIB, Group VB, Group IVB, Group IIB, Group IB, Group IVA or Group VA metals, such as Cu, B, Mn , Re, Cr, Mo, Bi, W, V, Nb, Ta, Ti, Zr, Y, La, Sc, Zn, Cd, Ag, Au, Sn, Ge, P, Al, Ga, In, Tl, Ce , alloys and combinations thereof. Preferred Group VIIB metal includes Re, Mn, or combinations thereof. Preferred Group VIB metals include Cr, Mo, W, or a combination thereof. Preferred Group VIIIB metals include Pt, Rh, Ru, Pd, Ni, or combinations thereof. Supports can include any of the catalyst supports described below, depending on the desired activity of the catalyst system. The APR catalyst can also be atomically identical to the deoxygenation catalyst or combined to form a single catalyst. The combined APR/deoxygenation catalyst may also be atomically identical to the acid condensation catalyst. For example, the deoxygenation and APR catalyst can include Pt alloyed or mixed with Ni, Ru, Cu, Fe, Rh, Re, alloys and combinations thereof. The APR catalyst and deoxygenation catalyst may also include Ru alloyed or mixed with Ge, Bi, B, Ni, Sn, Cu, Fe, Rh, Pt, alloys and combinations thereof. The APR catalyst and deoxygenation catalyst may also include Pd alloyed or mixed with Ni, Ag, Au, Sn, Cu, Mo, Fe, Rh, Pt, alloys and combinations thereof. The APR catalyst can also include Ni alloyed or mixed with Sn, Ge, Bi, B, Cu, Re, Ru, Fe, alloys and combinations thereof. The preferred loading of the primary Group VIIIB metal is in the range of 0.25% by weight to 25% by weight on carbon, with percentages by weight of 0.10% and 0.05% increments therebetween, such as 1.00%, 1.10%, 1.15%, 2.00%, 2.50%, 5.00%, 10.00%, 12.50%, 15.00% and 20.00%. The preferred atomic ratio of the second material is in the range of 0.25 to 1 to 10 to 1, which includes the ratios between them, such as 0.50, 1.00, 2.50, 5.00 and 7, 50 to 1.
    A preferred catalyst composition is further achieved by the addition of Group IIIB oxides and associated rare earth oxides. In such an event, the preferred components would be lanthanum oxides or cerium. The preferred atomic ratio of Group IIIB compounds to primary Group VIIIB metals is in the range of 0.25 to 1 to 10 to 1, which include the ratios between them, such as 0.50, 1.00, 2 .50, 5.00 and 7.50 for 1.
    Another preferred catalyst composition is one containing platinum and rhenium. The preferred atomic ratio of Pt to Re is in the range of 0.25 to 1 to 10 to 1, which include ratios between them, such as 0.50, 1.00, 2.50, 5.00 and 7, 00 to 1. The preferred Pt loading is in the range of 0.25% by weight to 5.0% by weight, with percentages by weight of 0.10% and 0.05% therebetween, such as 0.35%, 0.45%, 0.75%, 1.10%, 1.15%, 2.00%, 2.50%, 3.0% and 4.0%.
    It is preferred that the APR catalyst and the deoxygenation catalyst are of the same atomic formulation. Catalysts can also be of different formulations. The catalysts can also consist of a single catalyst with both APR and deoxygenation functionality provided by the combination of the APR materials and deoxygenation materials described above. In such an event, the preferred atomic ratio of APR catalyst to deoxygenation catalyst is in the range of 5:1 to 1:5, such as, without limitation, 4.5:1, 4.0:1, 3.5 :1, 3.0:1, 2.5:1, 2.0:1, 1.5:1, 1:1, 1:1.5, 1:2.0, 1:2.5, 1 :3.0, 1:3.5, 1:4.0, 1:4.5, and any amounts in between.
    Similar to deoxygenation reactions, temperature and pressure conditions are preferably selected to keep at least some of the raw material in the liquid phase at the reactor inlet. Reform pressure and temperature conditions can also be selected to more favorably produce the desired products in the vapor phase or in a mixed phase that has both a liquid and a vapor phase. In general, the APR reaction should be conducted at a temperature where thermodynamics are favorable. For example, the minimum pressure required to keep some of the raw material in the liquid phase will vary with the reaction temperature. As temperatures increase, greater pressures will generally be required to keep the raw material in the liquid phase. Any pressure above that required to keep the raw material in the liquid phase (ie, vapor phase) is also a suitable operating pressure. For vapor phase reactions, the reaction should be conducted at a reforming temperature where the vapor pressure of the oxygenated hydrocarbon compound is at least about 0.1 atm (and preferably a considerably greater amount), and the thermodynamics of the reaction are favorable. The temperature will vary depending on the specific oxygenated hydrocarbon compound used, but is generally in the range from about 100°C to 450°C, or from about 100°C to 300°C, for reactions that occur in the vapor phase. For liquid phase reactions, the reforming temperature can be from about 80°C to 400°C and the reforming pressure from about 72 psig to 1300 psig.
    In one embodiment, the reform temperature is between about 100°C and 400°C, between about 120°C and 300°C, between about 200°C and 280°C, or between about 150°C and 270 °C. The reform pressure is preferably between about 72 and 1300 psig, between about 72 and 1200 psig, between about 145 and 1200 psig, between about 200 and 725 psig, between about 365 and 700 psig or between about 365 and 700 psig. about 600 and 650 psig.
    In modalities where the APR catalyst and the deoxygenation catalyst are combined in a single catalyst, or the reactions are conducted simultaneously in a single reactor, the reforming temperature and deoxygenation temperature can be in the range of about 100°C to 325° C, about 120°C to 300°C or about 200°C to 280°C, and the reforming pressure and deoxygenation pressure can be in the range of about 200 psig to 1500 psig, about 200 psig to 1200 psig or about 200 psig to 725 psig.
    A condensed liquid phase method can also be performed using a modifier that increases the activity and/or stability of the APR catalyst system. It is preferred that the water and oxygenated hydrocarbon are reacted at a suitable pH from about 1.0 to 10.0, or at a pH from about 4.0 to 10.0, which includes increments of pH value of 0.1 and 0.05 between them. Generally, the modifier is added to the raw material solution in an amount ranging from about 0.1% to about 10% by weight, as compared to the total weight of the catalyst system used, although amounts outside this range are included in the present invention.
    Alkali or alkaline earth salts can also be added to the raw material solution to optimize the proportion of hydrogen in the reaction products. Examples of water-soluble salts include one or more selected from the group consisting of an alkaline earth metal hydroxide or alkaline base, carbonate, nitrate or chloride salt. For example, adding alkaline (basic) salts to provide a pH of about pH 4.0 to about pH 10.0 can improve the hydrogen selectivity of reforming reactions.
    The addition of acidic compounds can also provide increased selectivity for the desired reaction products in the hydrogenation reactions described below. It is preferred that the water-soluble acid is selected from the group consisting of nitrate, phosphate, sulfate, chloride salts and mixtures thereof. If an acid modifier is used, it is preferred that it be present in an amount sufficient to reduce the pH of the aqueous feed stream to between about pH 1.0 and about pH 4.0. Lowering the pH of a feed stream in this way can increase the proportion of oxygenates in the final reaction products.
    In general, the reaction should be conducted under conditions where the residence time of the raw material solution on the APR catalyst is adequate to generate a sufficient amount of APR hydrogen to react with a second part of the raw material solution on the catalyst of deoxygenation to provide the desired oxygenates. For example, the WHSV for the reaction can be at least about 0.1 gram of oxygenated hydrocarbon per gram of APR catalyst, and preferably between about 1.0 to 40.0 grams of oxygenated hydrocarbon per gram of catalyst APR, and more preferably, between about 0.5 to 8.0 grams of oxygenated hydrocarbon per gram of APR catalyst. In terms of scale-up production, after startup, the APR reactor system should consist of a process controlled so that reactions proceed in steady state equilibrium.
    Reactor system The reactions described in this document can be carried out in any suitable design reactor, including continuous flow, batch, semi-batch or multi-system reactors, without limitation regarding design, size, geometry, flow rates, etc. The reactor system may also utilize a fluidized catalytic bed system, a swing bed system, a fixed bed system, a moving bed system or a combination of those mentioned above. It is preferred that the present invention be practiced using a continuous flow system in steady state equilibrium.
    In a continuous flow system, the reactor system includes at least one reforming bed adapted to receive an aqueous raw material solution to produce hydrogen, a deoxygenation bed adapted to produce oxygenates from hydrogen and a portion of the solution of raw material, and a bed of condensation adapted to produce Cg+ compounds from hydrogen, oxygenates and a part of a second reagent. The reforming bed is configured to place the aqueous feedstock solution in a vapor phase or liquid phase in contact with the APR catalyst to provide hydrogen in a reactant stream. The deoxygenation bed is configured to receive for contacting a portion of the aqueous raw material with hydrogen and the deoxygenation catalyst to produce water and the desired oxygenates. The condensation bed is configured to receive a reactant stream that contains water and oxygenates as a first reactant and second reactant and then contacting the reactant stream with hydrogen and the acidic condensation catalyst to produce a stream of product containing the desired C8+ compounds. For systems that do not involve an APR hydrogen production step, the reforming bed can be removed. For systems that do not involve a hydrogen or oxygenate production step, the reforming and deoxygenation beds can be removed. Due to the fact that the APR catalyst, deoxygenation catalyst and condensation catalyst can also be atomically identical, the catalysts can exist as the same bed. For systems with a finishing step, an additional reaction bed to drive the finishing process can be added after the condensation bed. For systems that involve a recycle stream providing the second reactant, an additional separation system to separate the water and recycle stream from the desired Ce+ compounds can be included after the condensation bed. The water separation unit and the recycle stream separation unit can consist of separate systems or be combined into a single separation system.
    In systems that produce both hydrogen and oxygenates, the deoxygenation bed may be positioned within the same reactor vessel along with the reforming bed or in a second reactor vessel in communication with a first reactor vessel having the reforming bed. The condensing bed may be within the same reactor vessel together with the reforming or deoxygenation bed or in a separate reactor vessel in communication with the reactor vessel having the deoxygenation bed. Each reactor vessel preferably includes an outlet adapted to remove product stream from the reactor vessel. For systems with a finishing step, the finishing reaction bed can be either within the same reactor vessel along with the condensing bed or in a separate reactor vessel in communication with the reactor vessel having the condensing bed.
    The reactor system may also include additional outlets to allow removal of parts of the product stream to further advance or direct the reaction to the desired reaction products, and to allow for the collection and recycling of the C7- products for use as the second reagent or other reaction by-products for use in other parts of the system. The reactor system may also include additional inlets to allow the introduction of supplementary materials to further advance or direct the reaction to the desired reaction products, and to allow recycling of the C7_ products for use as the second or other reactant. reaction by-products for use in the process. For example, the system can be designed such that excess hydrogen is produced over the APR catalyst, with a portion of the excess hydrogen removed and reintroduced downstream of the condensation reaction or condensation product finish to reach the desired Cg+ compounds. Alternatively, the system can be designed such that excess hydrogen is produced over the APR catalyst, with a portion of the excess hydrogen removed and used in other upstream processes, such as feedstock pretreatment processes. and hydrogenation or hydrogenolysis reactions. The reactor system can also include elements that allow the separation of the reactant flow into different components that can find use in different reaction schemes or to simply promote the desired reactions. For example, a separator unit, such as a phase separator, extractor, purifier or distillation column, can be installed after the condensation step to remove water from the product stream for the purposes of aiding in the separation of Cg+ compounds from the C7- compounds and collecting the C7_ compounds for use as a part of the second reagent. A separator unit can also be installed prior to the condensation step to remove water from the reactant stream for the purposes of advancing the condensation reaction to favor the production of the desired hydrocarbons. 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 carbon range or for use as end products or in other systems or processes.
    EXAMPLES Illustrative Reactor Systems Example 1 Figure 1 shows a process diagram illustrating a reactor system useful in the practice of the present invention. A first reagent stream that contains water and oxygenated intermediates, such as alcohols, ketones, cyclic ethers, organic acids, or other polyoxygenated compounds, is provided by stream 202. The first reagent stream is combined with hydrogen 301 and a second stream of reagent 408 which contains light hydrocarbons and monooxygenated hydrocarbons derived from the process. The combined reactant stream is directed through condensing reactor 204 where the reactants catalytically react with an acidic condensing catalyst at a condensing temperature and condensing pressure to form product stream 206 which contains primarily hydrocarbons, mono-oxygenated hydrocarbons and Water. The chain length of hydrocarbons and mono-oxygenated hydrocarbons varies from C3-C30 depending on the extent of condensation. Product stream 206 is sent to a separation unit 400 (light recycling column) to produce a heavy fraction 411 that contains Cg+ hydrocarbons and oxygenated hydrocarbons, and a lighter fraction 402 that contains water and C7- hydrocarbons and oxygenated hydrocarbons . The lighter fraction 402 is separated from the heavy fraction and directed to a three-phase separator 410 to provide a gas phase 404 flow predominantly of hydrogen, carbon dioxide and smaller amounts of light hydrocarbons, an aqueous phase 412, composed of water and low levels of organic compounds, and a suspended organic phase 407 . Organic phase 407 is split into three streams to provide (1) reflux back to the column, stream 406, (2) liquid product, stream 407, and (3) recycle stream 408, which is then recycled to provide the second reagent. In this configuration, the recycle stream will generally include residual alkenes and oxygenates that can be further condensed to Ce+ compounds, and alkanes that are non-reactive, but provide advantages for increasing the yield of Cg+ compounds in the system. Example 2 Figure 2 shows a process diagram illustrating another reactor system useful in the practice of the present invention. The configuration is similar to the system described in Example 1, but it also includes an optional second condensing reactor in series. In this embodiment, the additional condensing reactor (as well as other additional reactors) provides additional flexibility to the system — to allow the use of larger amounts of catalyst, to provide temperature variations across reactors, or to employ different catalyst formulations. Example 3 Figure 3 shows a process diagram illustrating another reactor system useful in the practice of the present invention. The configuration can use the same condensing reactor system as described in Examples 1 or 2 above, but also includes an optional APR/HDO reactor 104 to generate water and the first reagent, and an optional water separation unit such as a aqueous separator or three-phase separator, for reducing the water content of the reagent stream. Example 4 Figure 4 shows a process diagram illustrating another reactor system useful in the practice of the present invention. The setup is similar to Example 3 but includes an additional APR 120 reactor for in situ hydrogen production for use in the reactor system. In its operation, the reactor converts aqueous feed stream 111 which contains water and water-soluble oxygenated hydrocarbons to a mixture of hydrogen, CO and CO2 as a primary product. Hydrogen can be used to supply hydrogen consumed in the APR/HDO 104 reactor and/or 304 condensing reactor. Example 5 Figure 5 shows a process diagram illustrating another reactor system useful in the practice of the present invention. The setup is similar to Example 3, except that no aqueous separator is used. In this configuration, organic product APR/HDO (stream 105) or aqueous product APR/HDO (stream 106) can be fed to the condensing reactor independently, or combined such that all liquid products are fed forward to the condensing reactor. condensation. The aqueous product stream 106 can also be recycled back to the APR/HDO reactor as described by the recycle stream 107. The condensing section can be practiced as described in Examples 1 or 2. Analysis Techniques Example 6
    The product streams from the examples described below were analyzed as set out below. 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 100% bound dimethyl polysiloxane stationary phase. The relative concentrations of individual components were estimated by peak integration and dividing by the sum of the peak areas for an entire chromatogram. Compounds 5 were identified by comparing standard retention times and/or comparing mass spectra to a compiled mass spectral database. The gas phase compositions were determined by means of gas chromatography with a thermal conductivity detector and flame ionization detectors or mass spectrometry for other gas phase components. The aqueous fraction was analyzed by gas chromatography with and without a derivation of the organic components using a flame ionization detector. Product yields are represented by the 15 feed carbon present in each product fraction. The hourly space velocity by weight (WHSV) was defined as the weight of the feed introduced into the system per weight of catalyst per hour, and based on the weight of the oxygenated hydrocarbon feeds only, excluding the water present in the feed. APR, Deoxygenation and Condensation Example 7 A combined APR/deoxygenation catalyst was prepared by dissolving hexachloroplatinic acid and perrenic acid in water and then adding the mixture to a monocyclic zirconia catalyst support (NorPro Saint-Gobain, product code SZ31164, with particle sizes restricted to those that were kept in a 14 mesh sieve after passing through a 10 mesh sieve) 30 using incipient moisture techniques to direct a platinum load of 1, 8% and a 6.3% rhenium charge on the catalyst after subsequent decomposition of the metal precursors. The preparation was dried overnight in a vacuum oven and subsequently calcined in a flowing air stream at 400°C. Example 8 Corn syrup (43 DE) was converted to an oxygenate stream (first reactant) using the APR/deoxygenation catalyst described in Example 7. Corn syrup was mixed with water to provide a stock solution. Aqueous raw which has a 60% concentration of 43DE corn syrup in water. The APR/deoxygenation reaction was performed using a 2.54 centimeter (one inch) outside diameter tube reactor, and the analysis was completed as described in Example 6. The WHSV and reaction conditions were as described in Table 1 below. The reaction resulted in an oxygenate product stream that contains an organic phase, aqueous phase and gas phase. The composition of the organic phase is shown in Table 1. The total monooxygenates included alcohols, ketones, tetrahydrofurans and cyclic monooxygenates. Cyclic monooxygenates have included compounds in which the ring does not include oxygen, such as cyclopentanone and cyclohexanone. Table 1 Conversion of Corn Syrup through APR/Deoxygenation Catalyst

    Example 9 An acid 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 restricted particle sizes those that were maintained in a 60 mesh sieve after passing through an 18 mesh sieve) using an incipient wetness technique to direct a 10% copper charge into the catalyst after subsequent decomposition of the metal precursors. The preparation was dried overnight in a vacuum oven at 100°C and subsequently calcined in a flowing air stream at 400°C. Example 10
    The oxygenate stream described in Example 8 was used as a first reactant and fed over the condensation catalyst described in Example 9 using the process configuration illustrated in Figure 1. The WHSV, reaction conditions and light recycling ratio (ratio of second reagent) were as described in Table 2 below. The study was conducted using a 2.54 centimeter (one inch) outside diameter tube reactor, with the condensing catalyst reduced to 400°C under the flow of hydrogen prior to use. The H2 co-feed, light recycle ratio and heavy fraction yield were based on the first reagent stream 202 produced by the APR/HDO system described in Example 8.
    A product stream was produced that contains a heavy fraction and a lighter fraction. The composition of the heavy fraction is shown in Table 3. Hydrocarbons describe compounds without oxygen and include alkanes, cycloalkanes, alkenes, cycloalkenes and aryls. Monooxygenates include alcohols, ketones, cyclic ethers and cyclic ketones. Cg+ compounds contain continuous carbon chain lengths of 8 or greater. The exception to this is the di-oxygenate category, which contains esters that do not have continuous carbon backbones. Esters would not retain their chain lengths if hydrogenated to a finished liquid fuel. The unclassified category contains compounds that are too heavy and/or co-elute with other compounds, preventing precise identification from the analysis technique. An estimation of the carbon number is made based on the boiling point and, in general, these compounds have continuous carbon chains.
    A significant part of the first reagent stream is converted to Cg+ compounds in the condensing reactor. As shown in Table 1 above, 99% of the carbon in the first reagent stream was contained in C7- compounds. As shown in Table 3, more than 94% of the heavy fraction in the product stream contained Cg+ compounds. As shown in Table 2, 42% of the feed carbon was captured in the weighed product. Table 2 Condensation of Oxygenates to Cg+ Compounds
    Table 3 5 Composition of heavy organic product
    Condensation with ZSM-5 Catalysts Example 11 An acidic condensation catalyst was prepared by dissolving an aqueous nickel nitrate solution and adding it to an alumina-bonded ZSM-5 zeolite preparation (SiO2:Al2O3 30 : 1, extruded 1/16" 5 tablets with particle sizes restricted to those that were kept in a 60 mesh sieve after passing through an 18 mesh sieve) using an aqueous nickel nitrate solution and an incipient wetness technique to direct a 1.0% nickel charge, by weight 10. The preparation was dried overnight in a vacuum oven and subsequently calcined in a flowing air stream at 400°C. A second metal was added by dissolving ruthenium nitrate in water and adding it to the catalyst using an incipient moisture technique to drive a ruthenium load of 0.5% by weight. another in a vacuum oven and subsequently calcined in a flowing air stream at 400°C. Example 12 20 An acid condensation catalyst was prepared by dissolving copper nitrate in water and then adding it to an alumina-bonded ZSM-5 zeolite preparation (SiO2:Al2C>3 30:1, extrudates 1 /16" tablets with particle sizes restricted to those that were held in a 25 mesh 60 mesh sieve after passing through an 18 mesh sieve) using an incipient wetness technique to direct a 5.0 copper load % by weight The preparation was dried overnight in a vacuum oven and subsequently calcined in a flowing air stream at 30 to 400°C Example 13 The oxygenate stream described in Example 8 was fed over the catalysts condensation compounds described in Examples 10 and 11, as well as an alumina-bonded ZSM-5 zeolite preparation (30:1 SiO2:Al2O3 30:1, extruded 1/16" tablets with particle sizes restricted to those that were kept in a 60 sieve mesh after passing through a pen 18 mesh). Conversion was conducted using the process configuration illustrated in Figure 2. The "main" and "secondary" reactors contained the catalyst formulations as listed in Table 4. Each catalyst was reduced to 400°C under flowing hydrogen prior to use. . The WHSV, reaction conditions and light recycling ratio (second reagent ratio) were as described in Table 4 below. The study was conducted using a 2.54 centimeter (one inch) outside diameter tube reactor, with the condensation catalysts reduced to 400°C under flowing hydrogen prior to use. The H2 co-feed, light recycling ratio and heavy fraction yield were based on the input feed into the first reagent stream 202. An organic heavy fraction was collected and analyzed as described in Example 6. Experiments B, C and D showed significant levels of condensation for a variety of metals impregnated in ZSM-5. Nickel/ruthenium, nonmetals, and copper catalysts were run in each combination, and resulted in a 70 to 71% yield of C8+ compounds in the heavy fraction of the product stream. The first reagent used as a raw material contained <1% Cg+ compounds at input. Table 4 Condensation of Oxygenates to C8+ Compounds

    The composition of the second reagent light recycle stream for Experiments B, C, and D is shown in Table 5. Most of the stream is composed of alkanes that are non-reactive, but provide advantages to increase the yield of Cg+ compounds in the system. Most of the hydrocarbons and oxygenated hydrocarbons in the stream are in the unwanted C-carbon range. Table 5 10 Light Organic Recycling Composition

    Example 14
    An acid condensation catalyst was prepared by dissolving an aqueous nickel nitrate solution and adding it to an alumina-bonded ZSM-zeolite preparation (30:1 SiO2:Al2O3 1/16" extruded tablets with sizes of particles restricted to those that have been kept in a 60 mesh sieve after passing through an 18 mesh sieve) using an incipient moisture technique 10 to direct a 1.0 wt% nickel load. was dried overnight in a vacuum oven and subsequently calcined in a flowing air stream at 400°C.
    An acid condensation catalyst was prepared by dissolving copper nitrate in water and adding it to an alumina-bonded mordenite preparation (H-form, extruded 1/16" tablets with particle sizes restricted to those that were kept in a 60 mesh sieve after passing through a 5 18 mesh sieve) using an incipient wetness technique to direct a 5.0 wt% copper load. The preparation was dried overnight in a vacuum furnace and subsequently calcined in a flowing air stream at 400°C. Example 16
    An acid condensation catalyst was prepared by dissolving copper nitrate in water and adding it to a tungsten zirconia catalyst support (NorPro Saint-Gobain, product code SZ31164, with particle sizes restricted to those that were retained. on a 60 mesh sieve after passing through an 18 mesh sieve) using an incipient wetness technique to direct a 5% copper charge onto the catalyst after subsequent decomposition of the metal precursors. The preparation was dried overnight in a vacuum oven at 100°C and subsequently calcined in a flowing air stream at 400°C. Example 17
    The oxygenate stream (first reactant) described in Example 8 was fed over the catalysts described in Examples 14, 15 and 16 using the process configuration illustrated in Figure 2. The same catalyst was installed in both the main and secondary reactors. , and reduced to 400°C under flowing hydrogen before use. The WHSV, reaction conditions and light recycling ratio (30 second reagent ratio) were as described in Table 6. The study was conducted using a tube reactor with an outer diameter of 2.54 centimeters (one inch) , with the condensation catalysts reduced to 400°C under flowing hydrogen before use. The H2 co-feed, the light recycle ratio and the heavy fraction yield were based on the input feed into the first reagent stream 202.
    An organic heavy fraction was collected and analyzed as described in Example 6. Table 7 shows organic product yields and composition. The component ratings are the same as those described in Example 10. Experiments E, F, and G show that a variety of acidic supports provide good yields for Cβ+ products. The ZSM-5, Mordenite and tungsten zirconia supports promoted condensation reactions, with ZSM-5 and tungsten zirconia performing best with a carbon yield of 68% and 70% of the feed carbon in the heavy product fraction, respectively. As shown in Table 7, 96% or more of the carbon in the heavy product can be found in the Ce+ compounds for each experiment. Table 6 Condensation of Oxygenates to Cg+ Compounds

    Table 7 Composition of heavy organic product
    5 Example 18
    The oxygenate stream described in Example 8 was fed over the catalysts described in Example 16 using the process configuration illustrated in Figure 2. Unlike the previous examples, the aqueous phase, which contained 23% of the feed carbon, was fed to the condensing reactor as well, shown as flow 106 in Figure 5. This makes the water content of the feed much higher. The WHSV, reaction conditions and light recycling ratio (second reagent ratio) were as described in Table 8 below. The study was conducted using a 2.54 centimeter (one inch) outside diameter tube reactor, with the condensation catalysts reduced to 400°C under flowing hydrogen prior to use. The H2 co-feed, light recycle ratio and heavy fraction yield were based on the first reagent stream 202 produced by the APR/HDO system described in Example 8.
    A heavy organic fraction was collected and analyzed as described in Example 6. Experiments Hei demonstrate the ability of light recycling of second reagent to alter Cg+ yield. By doubling the rate of the second reactant, the yield for the heavy product was increased by 11%, even though the absolute amount of water going to the condensation catalyst was equal, shown as a flow rate in Table 8. Table 8 Condensation from Oxygenates to Cg+ Carbon Chains

    Example 19 An APR/Deoxygenation/Condensation catalyst was prepared by dissolving palladium nitrate and silver nitrate in water and then adding the same to a tungsten zirconia catalyst support (NorPro Saint-Gobain, product code SZ61143 , with particle sizes restricted to those that were kept in a 60 mesh sieve after passing through a 16 mesh screen) using an incipient moisture technique to direct a 0.5% palladium load and a load of 0.5% silver on the catalyst after the subsequent decomposition of the metal precursors. The preparation was dried overnight in a vacuum oven and subsequently calcined in a flowing air stream at 400°C. Example 20
    The catalyst system mentioned in Example 19 was used to convert 43 DE corn syrup to oxygenated intermediates and then Cg+ compounds according to the present invention. The corn syrup was first mixed with water to first provide an aqueous raw material solution that has a 60% concentration of 43 DE corn syrup in water. The aqueous raw material was then directed to an APR/HDO reactor as illustrated in Figure 5, where it was reacted over the catalyst of example 19 to provide a first stream of reactant containing water and the desired oxygenates. The WHSV and reaction conditions were as described in Table 9. The study was conducted using a 2.54 centimeter (one inch) outside diameter tube reactor, with the catalysts reduced to 400°C under flowing hydrogen before of its use. Table 9 shows the composition of the organic and aqueous phases resulting from the first reagent flow. Total monooxygenates include alcohols, ketones, tetrahydrofurans and cyclic monooxygenates. Cyclic monooxygenates include compounds in which the ring does not include oxygen, such as cyclopentanone and cyclohexanone. The fraction of feed carbon contained within unknown components in the aqueous phase was determined as the carbon difference represented by known measured components and the total organic carbon. The gas phase products were not processed further. Table 9 Conversion of Corn Syrup through APR/Deoxygenation Catalyst


    The organic and aqueous phases were then processed as the first reagent in accordance with the present invention. This first reactant stream was combined with a light recycle of second reactant and fed onto a second catalyst bed containing the catalyst of example 19 configured for use as an acid condensation catalyst. The WHSV, reaction conditions and light cycle ratio (second reagent ratio) were as described in Table 10 below. The study was conducted using a 2.54 centimeter (one inch) outside diameter tube reactor, with the condensation catalysts reduced to 400°C under flowing hydrogen prior to use. The Ha co-feed, light recycle ratio and heavy fraction yield were based on the input feed into the first reagent stream 202.
    The heavy organic phase was collected and analyzed as described in Example 6. Table 11 shows the organic product yields and composition. The 5 J and K experiments demonstrate the importance of light second reagent recycling for the production of Cg+ products. With all other process conditions equal, experiment J only captured 39% of the feed carbon in the desired heavy product. With the recycle of light organic from the second 10 reagent (flow 408 in Figure 1), at a rate 1.6 times greater than the inlet feed rate (flow 202 in Figure 1), the product yield nearly doubled to 74 % carbon feed, while the absolute amount of water going to the condensation catalyst was the same, shown as a flow rate in Table 10. This same bed of catalyst was run with a similar feed for 11 consecutive days, and the yield for Cg+ products was stable over the duration of the experiment at 72 to 73% of the feed carbon. Table 10 Condensation of Oxygenates to C8+ Carbon Chains


    The composition of the heavy fraction of the product stream is shown in Table 11. In any one experiment, the product contained >93% of the carbon in continuous carbon chains of CΘ+, with Experiment L being 99.9% of Cg+. The carbon number distribution for all products arising from the acid condensation catalyst is shown in Figure 6. The K and L experiment with second reagent recycling showed an increase in the yield of Cg+ compounds and a decrease in the yield of C7 compounds - as compared to experiment J. Even after significant time in flux, experiment L showed improved production of Cg+ compounds, with more C15-24 generated and less C7- compared to experiment K. Table 11 Heavy Fraction Composition


    The composition of the light recycling of second reagent from experiment K and L is shown in Table 12. Most of the second reagent is composed of alkanes and cycloalkanes. These saturated hydrocarbons are primarily non-reactive on the catalyst, but provide advantages to increase the yield of Cg+ compounds in the system. Most of the flux is in the unwanted C7_ carbon band. Figure 7 shows a normal boiling point curve based on a simulated distillation gas chromatography method for both the light suspended and heavy product recycle stream for experiment L. Table 12 Light Organic Recycle Composition

    Example 21
    A reagent stream having isobutanol as the first reagent was converted to Cg+ compounds in accordance with the present invention using the reactor system described in Example 1, but with a three-phase separator as illustrated in Figures 2 and 5. In this In this case, the first reagent stream 202 contained pure isobutanol and the second reagent recycle stream 408 contained C4_ hydrocarbons. The acid condensation catalyst consisted of a tungsten zirconia support (NorPro Saint-Gobain, product code SZ31164, with particle sizes restricted to those maintained in a 14 mesh sieve). The reaction was conducted in an Inconel reactor having an internal diameter of 2.21 centimeters (0.87 inches), with a bed of catalyst charged to a length of 30.48 centimeters (12 inches). A thermowell with an OD of 0.476 centimeters (0.1875 inches) was placed in the centerline of the reactor.
    The catalyst bed was heated from 25°C to 310°C under an atmosphere of hydrogen. Once at temperature, the reactor was pressurized to 600 psig and then 100% isobutanol was fed into the reactor in a WHSV of 0.5 g isobutanol/g tungsten zirconia catalyst. To help with pressure control, 0.08 g of H2/g of isobutanol was fed into the process with the alcohol feedstock. Once steady state conditions were reached, an analysis of reaction products was completed. The gas products were analyzed by means of a gas chromatography equipped with a flame ionization detector, the aqueous phase products were analyzed for total carbon and the organic phase components were analyzed using a gas chromatography equipped with either flame ionization detector as well as mass spectrometry.
    Isobutanol was initially processed as a first reactant in the absence of a second reactant recycle stream to illustrate the impact of the second reactant. The results obtained are shown in Table 13. To demonstrate the recycling of light intermediates for use as a second reagent, the product stream 206 from Figure 1 was sent onward to a distillation column (light recycling column) to provide a light fraction containing C- _ compounds and a heavy fraction containing C8+ compounds. Before the product stream entered the column, a significant portion of the water in stream 206 was removed via a three-phase separator as illustrated in Figures 2 and 5. The packed 10-stage distillation column was pressurized to 150 psig and one temperature profile was imposed such that the top stage was at 75°C and the bottom stage was at 170°C. The product stream with water removed entered the column at stage three. A reflux ratio of 1.2 g reflux/g isobutanol feed entered the distillation column at stage 1. The recycle of suspended product for this example was set at 2.5 g recycle/g isobutanol. A pump increased the pressure of the recycle stream 408 back to 600 psig at the reactor inlet, where it entered the catalyst bed with the isobutanol first reactant stream. 0 accumulation of any C4 material. was managed by removing a stream of light fraction 407 from the top of the column at a rate of 0.2 g light purge/g isobutanol. The light fraction was taken as a part of the total suspended material, where the remaining part consisted of the recycling stream. A high boiling organic fraction containing C8+ compounds was removed in heavy fraction stream 411. The results obtained for the heavy fraction are shown in Table 14 and the 10 results obtained for the lighter fraction are shown in Table 15. Table 13. Carbon Distribution for Isobutanol Conversion without Second Reagent
    Table 14. Carbon Yield of Heavy Fraction with Second Reagent Recycling
    Table 15. Light Fraction Carbon Yield with 5 second reagent recycling

    权利要求:
    Claims (13)
    [0001]
    1. METHOD OF MANUFACTURING C8+ COMPOUNDS, characterized in that it comprises: (i) providing a first reagent flow comprising molecules having a general formula CxHyOz and an average oxygen to carbon ratio of the first reagent flow between 0.2 and 1 ,0 and where x = 2 to 12 carbon atoms and z = 1 to 12 oxygen atoms, (ii) add to the first reactant stream a separate second reactant stream to create a combined reactant stream comprising carbon atoms to the first and second reactant streams, the second reactant stream comprising molecules having a general formula CpHrOs and an average oxygen to carbon ratio of a second reactant stream of 0.2 or less and where p = 2 to 7 atoms carbon es = 0 to 1 oxygen atom, and the second reactant stream comprising a plurality of C7- compounds selected from the group consisting of alkanes, alkenes, cycloalkanes, cycloalkenes and aryls; and wherein of the total number of carbon atoms in the combined reactant stream more than 10% is from the first reactant stream, and greater than 10% is from the second reactant stream, and wherein the average oxygen to carbon ratio of the first reagent stream is greater than the average oxygen to carbon ratio of the second reagent stream; and (iii) catalytically reacting the combined reactant stream with hydrogen in the presence of an acidic condensation catalyst to produce a product stream comprising water, a plurality of C7- compounds selected from the group consisting of a C7 alkane -, a C7-alkene, a C7-cycloalkane, a C7-cycloalkene, a C7-alcohol, a C7-ketone, a C7-aryl and mixtures thereof, and a plurality of C8+ compounds selected from the group consisting of C8+ alkane , C8+ alkene, C8+ cycloalkane, C8+ cycloalkene, C8+ alcohol, C8+ ketone, an aryl, a fused aryl, an oxygenated aryl, an oxygenated fused aryl, and a mixture thereof, wherein the acid condensation catalyst comprises an acid support or a heterogeneous acid catalyst comprising a metal selected from the group consisting of Pd, Pt, Cu, Co, Ru, Cr, Ni, Ag, an alloy thereof, and a combination thereof; (iv) separating from the product stream one or more of a C12-24 fraction and a C25+ fraction; and (v) separating a portion of the C7- compounds from the product stream to provide a recycle stream, wherein water is removed from the product stream prior to recycling the portion of the C7- compounds; and (vi) recycling the recycle stream to form at least part of the second reactant stream.
    [0002]
    2. METHOD according to claim 1, characterized in that the acid support is selected from the group consisting of an aluminosilicate, a tungstenated aluminosilicate, a silica-alumina phosphate, an aluminum phosphate, an amorphous alumina silica, an alumina acid, an alumina phosphate, a tungsten alumina, a zirconia, a tungsten zirconia, a tungsten silica, a tungsten titania, a tungsten phosphate, niobia, an acid-modified resin, a zeolite, a heteropolyacid, a tungstenated heteropolyacid, and combinations of same; or the heterogeneous acid catalyst further comprises a support selected from the group consisting of carbon, silica, alumina, zirconia, titanium, vanadium, kieselguhr, hydroxyapatite, chromium, niobium, mixtures thereof, and combinations thereof; or the acid condensation catalyst further comprises a modifier selected from the group consisting of Cu, Ag, Au, Ru, Pd, Ni, Co, Ga, In, Cr, Mo, W, Sn, Nb, Ti, Zr, Ge, P, Al, alloys thereof, and combinations thereof; or the acidic condensation catalyst comprises ZSM-5 or tungsten zirconia, and wherein the acidic condensation catalyst further comprises Pd or Cu.
    [0003]
    3. METHOD, according to claim 1, characterized in that the second reactant has an average oxygen to molecule ratio of 1 to 4, and the first reactant flow has an average oxygen to molecule ratio of 1.5 or less.
    [0004]
    4. METHOD, according to claim 1, characterized in that the second reagent flow has a boiling point lower than 210°C; or the product stream further comprises one or more C7- compounds which have 2 to 7 carbon atoms and 0 to 1 oxygen atom, and wherein a part of the product stream is recycled to form at least part of the second reagent flow, the method further comprises the step of removing water from the product flow before recycling part of the product flow to form the second reagent in part; or the method further comprises the step of catalytically reacting at least a part of the product stream in the presence of a finishing catalyst.
    [0005]
    5. METHOD according to claim 1, characterized in that it further comprises: providing hydrogen, water and a water-soluble oxygenated hydrocarbon comprising a C2+O1+ hydrocarbon, and catalytically reacting the oxygenated hydrocarbon with hydrogen in the presence of a deoxygenation catalyst to produce the first reactant stream.
    [0006]
    6. METHOD according to claim 5, characterized in that the deoxygenation catalyst comprises a support and a member selected from the group consisting of Re, Cu, Fe, Ru, Ir, Co, Rh, Pt, Pd, Ni, W, Os, Mo, Ag, Au, and a combination thereof.
    [0007]
    7. METHOD according to claim 6, characterized in that the support comprises a member selected from the group consisting of a carbon, silica, alumina, zirconia, titanium, vanadium, heteropolyacid, kieselguhr, hydroxyapatite, chromium, zeolite, and mixtures thereof, and wherein the support is preferably selected from the group consisting of tungsten-modified zirconia, tungsten-modified zirconia, tungsten-modified alpha-alumina, or tungsten-modified teta-alumina.
    [0008]
    8. METHOD according to claim 5, characterized in that the water-soluble oxygenated hydrocarbon is selected from the group consisting of a starch, a carbohydrate, a polysaccharide, a disaccharide, a monosaccharide, a sugar, a sugar alcohol, an aldopentose, an aldohexose, a ketotetrose, a ketopentose, a ketohexose, a hemicellulose, a cellulosic derivative, a lignocellulosic derivative, and a polyol.
    [0009]
    9. METHOD according to claim 1, characterized in that the hydrogen comprises at least one of an in situ generated H2, external H2 or recycled H2, and in which the hydrogen preferably comprises hydrogen generated in situ by catalytically reacting in a liquid phase or vapor phase of an aqueous feedstock solution comprising water and an oxygenated hydrocarbon in the presence of an aqueous phase reforming catalyst at a reforming temperature and reforming pressure.
    [0010]
    10. METHOD according to any one of claims 1 and 5 to 8, characterized in that the combined flow of reagent additionally comprises water.
    [0011]
    11. METHOD, according to claim 1, characterized in that the recycling flow has a boiling point lower than 210°C.
    [0012]
    12. The METHOD of claim 1, which is a method for producing a fuel product, further comprising: (iii) separating at least a part of the C8+ compounds from the product stream, (iv) reacting from catalytic mode the C8+ compounds separated in the presence of a finishing catalyst to produce a fuel product.
    [0013]
    13. The METHOD of claim 12, further comprising a step of separating the fuel product to provide a C814 fraction comprising a plurality of hydrocarbons having 8 to 14 carbon atoms, the C12-24 fraction which comprises a plurality of hydrocarbons having 12 to 24 carbon atoms, and the C25+ fraction comprising a plurality of hydrocarbons having 25 or more carbon atoms, and preferably wherein the C8-14 fraction is mixed to provide a fuel of jet, or the C12-24 fraction is blended to provide a diesel fuel or the C25+ fraction is blended to provide a heavy oil.
    类似技术:
    公开号 | 公开日 | 专利标题
    US11130914B2|2021-09-28|Method and systems for making distillate fuels from biomass
    US9593054B2|2017-03-14|Production of distillate fuels from biomass-derived polyoxygenates
    US8877985B2|2014-11-04|Co-production of biofuels and glycols
    CA2677826C|2014-09-30|Synthesis of liquid fuels and chemicals from oxygenated hydrocarbons
    US8362307B2|2013-01-29|Synthesis of liquid fuels and chemicals from oxygenated hydrocarbons
    EP2720992B1|2015-07-29|Co-production of biofuels and glycols
    WO2011143392A1|2011-11-17|Process including hydrogenolysis of biomass followed by dehydrogenation and aldol condensation for producing alkanes
    同族专利:
    公开号 | 公开日
    ES2847303T3|2021-08-02|
    EP2673337A1|2013-12-18|
    CA2825720C|2018-12-18|
    MY171432A|2019-10-14|
    CN103403128A|2013-11-20|
    CN103403128B|2016-03-02|
    EP2673337B1|2020-12-02|
    AU2012214577B2|2016-11-24|
    WO2012109241A1|2012-08-16|
    US11130914B2|2021-09-28|
    US20200318014A1|2020-10-08|
    US20120198760A1|2012-08-09|
    PL2673337T3|2021-07-19|
    US10619106B2|2020-04-14|
    CA2825720A1|2012-08-16|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US4543435A|1985-01-17|1985-09-24|Mobil Oil Corporation|Multistage process for converting oxygenates to liquid hydrocarbons with ethene recycle|
    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|
    US7850841B2|2005-12-12|2010-12-14|Neste Oil Oyj|Process for producing a branched hydrocarbon base oil from a feedstock containing aldehyde and/or ketone|
    CN101346302B|2005-12-21|2013-07-10|维仁特公司|Catalysts and methods for reforming oxygenated compounds|
    CN101454076A|2006-04-13|2009-06-10|国际壳牌研究有限公司|Process for hydrogenating an aldehyde|
    EP2061860B1|2007-03-08|2013-12-18|Virent, Inc.|Synthesis of liquid fuels and chemicals from oxygenated hydrocarbons|
    EP2565176B1|2006-05-08|2015-08-19|Virent, Inc.|Methods for generating polyols|
    MY154790A|2007-03-08|2015-07-31|Virent Inc|Synthesis of liquid fuels and chemicals from oxygenated hydrocarbons|
    US7880049B2|2006-06-06|2011-02-01|Wisconsin Alumni Research Foundation|Production of liquid alkanes in the jet fuel range from biomass-derived carbohydrates|
    EP2331486A2|2008-08-27|2011-06-15|Virent Energy Systems Inc.|Synthesis of liquid fuels from biomass|
    KR101518742B1|2008-09-19|2015-05-11|삼성디스플레이 주식회사|Display device and driving method thereof|
    US8283506B2|2008-12-17|2012-10-09|Uop Llc|Production of fuel from renewable feedstocks using a finishing reactor|
    US8410326B2|2010-01-14|2013-04-02|Wisconsin Alumni Research Foundation|Integrated process and apparatus to produce hydrocarbons from aqueous solutions of lactones, hydroxy-carboxylic acids, alkene-carboxylic acids, and/or alcohols|
    CA2772257C|2010-04-27|2015-06-30|Yun BAO|Carbohydrates upgrading and hydrotreating to hydrocarbons|
    US9593054B2|2011-02-07|2017-03-14|Virent, Inc.|Production of distillate fuels from biomass-derived polyoxygenates|
    BR112013019898B1|2011-02-07|2021-05-25|Virent, Inc|c8+ compost manufacturing method|BR112013019898B1|2011-02-07|2021-05-25|Virent, Inc|c8+ compost manufacturing method|
    US9157040B2|2012-04-16|2015-10-13|The United States Of America As Represented By The Secretary Of The Navy|Renewable high density turbine and diesel fuels|
    US10131604B2|2012-08-15|2018-11-20|Virent, Inc.|Catalysts for hydrodeoxygenation of oxygenated hydrocarbons|
    US8946458B2|2012-08-15|2015-02-03|Virent, Inc.|Catalysts for hydrodeoxygenation of oxygenated hydrocarbons|
    WO2014070579A1|2012-10-31|2014-05-08|Shell Oil Company|Methods for hydrothermal digestion of cellulosic biomass solids using a glycerol solvent system|
    CA2889368A1|2012-10-31|2014-05-08|Shell Internationale Research Maatschappij B.V.|Methods and systems for distributing a slurry catalyst in cellulosic biomass solids|
    EP2914690B1|2012-10-31|2016-11-23|Shell Internationale Research Maatschappij B.V.|Method for processing lignin during hydrothermal digestion of cellulosic biomass solids|
    IN2015DN03057A|2012-10-31|2015-10-02|Shell Int Research|
    MX2015017980A|2013-07-02|2016-08-05|Ut-Battelle Llc|Catalytic conversion of alcohols having at least three carbon atoms to hydrocarbon blendstock.|
    WO2015010266A1|2013-07-24|2015-01-29|East China University Of Science And Technology|Methods for producing alkanes from biomass|
    CN104610998B|2013-12-19|2017-07-04|北京林业大学|A kind of method that biodiesel is prepared using flower-shaped nickel catalyst agent material|
    CN105092759A|2015-08-11|2015-11-25|苏州优谱德精密仪器科技有限公司|Gas-mass-combination analytical equipment for petrochemical industry|
    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|
    CN105062578A|2015-08-24|2015-11-18|安徽圣宝新能源科技有限公司|Novel modified alcohol-based fuel and preparation method thereof|
    WO2017112716A1|2015-12-21|2017-06-29|Shell Oil Company|Methods of providing higher quality liquid kerosene based-propulsion fuels|
    FR3052459B1|2016-06-13|2020-01-24|Bio-Think|MIXTURE FOR SUPPLYING A BOILER OR DIESEL ENGINE COMPRISING PARTICULAR ESTERS AND ALKANES|
    CN106190223B|2016-08-19|2018-10-23|中国科学技术大学|A kind of aliphatic acid, ester through hydrogenation prepare the method for long chain alkane and the catalyst for the method|
    WO2018071905A1|2016-10-14|2018-04-19|Gevo, Inc.|Conversion of mixtures of c2-c8 olefins to jet fuel and/or diesel fuel in high yield from bio-based alcohols|
    法律状态:
    2017-12-12| B15I| Others concerning applications: loss of priority|Free format text: PERDA DA PRIORIDADE US 61/440,249 DE 07/02/2011, CONFORME AS DISPOSICOES PREVISTAS NA LEI 9.279 DE 14/05/1996 (LPI) ART. 167O E NO ART. 28 DO ATO NORMATIVO 128/1997, POR NAO ATENDER AO DISPOSTO NO ART. 27 DO ATO NORMATIVO 128/1997, POIS NAO FOI APRESENTADA CESSAO DA REFERIDA PRIORIDADE, QUE POSSUI DEPOSITANTE DIFERENTE DO DEPOSITANTE DA FASE NACIONAL. |
    2018-02-27| B12F| Other appeals [chapter 12.6 patent gazette]|
    2019-05-21| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-07-16| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|
    2020-06-30| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2020-11-03| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2021-03-23| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-05-25| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 07/02/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201161440249P| true| 2011-02-07|2011-02-07|
    US61/440,249|2011-02-07|
    PCT/US2012/024144|WO2012109241A1|2011-02-07|2012-02-07|Method and systems for making distillate fuels from biomass|
    [返回顶部]