method for providing a biobased feed load

专利摘要:
METHODS TO PROVIDE A BIOBASE-BASED AND BIOBASE-BASED POWER LOAD. One method comprises a biobased feed load; contacting the feed charge biobased with a solvent in a hydrolysis reaction to form an intermediate stream comprising carbohydrates; contacting the intermediate stream with an APR catalyst to form a plurality of oxygenated intermediates, wherein a first portion of the oxygenated intermediates are recycled to form the solvent; and processing at least a second portion of the oxygenated intermediates to form a fuel mixture.
公开号:BR112012016143B1
申请号:R112012016143-1
申请日:2010-12-20
公开日:2021-03-09
发明作者:Juben Nemchand Chheda；Joseph Broun Powell
申请人:Shell Internationale Research Maatschappij B.V；
IPC主号:

专利说明:

Field of the Invention
[001] A significant amount of attention has been placed on the development of new technologies to provide energy from resources other than fossil fuels. Biomass is a resource that shows promise as a fossil fuel alternative. Unlike fossil fuels, biomass is also renewable. Fundamentals of the Invention
[002] Biomass can be useful as a source of renewable fuels. One type of biomass is the biomass of the plant. Plant biomass is the most abundant carbohydrate source in the world due to the lignocellulosic materials that make up the cell walls of higher plants. Plant cell walls are divided into two sections, the primary cell walls and secondary cell walls. The primary cell wall provides structure for cell expansion and is composed of three main polysaccharides (cellulose, pectin, and hemicellulose) and a group of glycoproteins. The secondary cell wall, which is produced after the cell has finished growing, also contains polysaccharides and is reinforced by covalently cross-linked polymeric lignin for hemicellulose. Hemicellulose and pectin are usually found in abundance, but cellulose is the predominant polysaccharide and the most abundant source of carbohydrates.
[003] Most transport vehicles require high power density provided by internal combustion, and / or propulsion engines. These engines require clean-burning fuels that are usually in liquid form or, to a lesser extent, compressed gases. Liquid fuels are more portable due to their high energy density and their ability to be pumped, which makes handling easier.
[004] Currently, biobased feed cargo such as abiomass offers the only renewable alternative for transporting liquid fuel. Unfortunately, progress in the development of new technologies for the production of liquid biofuels has been slow in development, especially for liquid fuel products that fit within the current infrastructure. Although a variety of fuels can be produced from biomass resources, such as methanol, ethanol, biodiesel, Fischer-Tropsch diesel, and gaseous fuels, such as hydrogen and methane, these fuels require both new distribution technologies and / or combustion techniques suitable for their characteristics. The production of these fuels also tends to be expensive and raise questions about their net carbon savings.
[005] Carbohydrates are the most abundant, naturally occurring biomolecules. Plant materials store carbohydrates, either as sugars, starches, celluloses, lignocelluloses, hemicelluloses, and any combination thereof. In one embodiment, carbohydrates include monosaccharides, polysaccharides or mixtures of monosaccharides and polysaccharides. As used herein, the term "monosaccharides" refers to hydroxy aldehydes or hydroxy ketones that cannot be hydrolyzed to smaller units. Examples of monosaccharides include, but are not limited to, dextrose, glucose, fructose and galactose. As used herein, the term "polysaccharides" refers to saccharides that comprise two or more units of monosaccharides. Examples of polysaccharides include, but are not limited to, cellulose, sucrose, maltose, cellobiose, and lactose. Carbohydrates are produced during photosynthesis, a process in which carbon dioxide is converted to organic compounds as a way of storing energy. Carbohydrates are highly reactive compounds that can be easily oxidized to generate energy, carbon dioxide, and water. The presence of oxygen in the molecular structure of carbohydrates contributes to the reactivity of the compound. Water-soluble carbohydrates react with hydrogen on the catalyst (s) to generate polyols and sugar alcohols, either by hydrogenation, hydrogenolysis or both.
[006] Published application US No. 20080216391 to Cortright et al. Describes a process for converting carbohydrates to higher hydrocarbons, passing carbohydrates through a hydrogenation reaction followed by an aqueous phase reforming process ("APR"). The hydrogenation reaction produces polyhydric alcohols that can withstand the conditions present in the APR reaction. Further processing in an APR reaction and a condensation reaction can produce a superior hydrocarbon for use as a fuel. APR is currently limited to feed loads, including sugars or starches, which compete with the use of these materials for food resulting in a limited supply. There is a need to directly process biobased feed loads, including "biomass", or lignocellulosic feed loads, into liquid fuels. Summary of the Invention
[007] An embodiment of the present invention comprises providing a biobased feed load; contacting the feed charge biobased with a solvent in a hydrolysis reaction to form an intermediate stream comprising carbohydrates; contacting the intermediate stream with an APR catalyst to form a plurality of oxygenated intermediates, wherein a first portion of the oxygenated intermediates is recycled to form the solvent; and processing at least a second portion of the oxygenated intermediates to form a fuel mixture.
[008] Another embodiment of the present invention comprises a method which comprises providing a biobased feed load; contacting the biobased feed charge with a hydrolysis catalyst and a solvent to form an intermediate stream comprising carbohydrates; contacting at least a portion of the intermediate stream with a hydrogenolysis catalyst in the presence of the first hydrogen source to form at least some hydrogenolysis reaction products; contacting at least a portion of the intermediate stream with a hydrogenation catalyst in the presence of the second hydrogen source to form at least some products of the hydrogenation reaction; contacting at least a portion of the intermediate stream with an APR catalyst to form a product of the APR reaction; wherein at least a portion of the hydrogenolysis reaction products, at least a portion of the hydrogenation reaction products, and at least a portion of the APR reaction products are combined to form a plurality of oxygenated intermediates, wherein a first portion oxygenated intermediates are recycled to form the solvent; and processing at least a second portion of the oxygenated intermediates to form a fuel mixture.
[009] Yet another embodiment of the present invention comprises a system comprising an operation of the hydrolysis reactor under hydrolysis conditions to receive a biobased feed charge and a solvent and to discharge an intermediate stream comprising a carbohydrate; an APR reactor comprising an APR catalyst to receive the intermediate stream and discharging an oxygenated intermediate stream, in which a first portion of the oxygenated intermediate stream is recycled to the hydrolysis reactor as the solvent, and a fuel processing reactor to receive a second portion of the oxygenated intermediate stream and discharging a fuel mixture.
[0010] The characteristics and advantages of the invention will be evident to those skilled in the art. Although numerous changes can be made by those skilled in the art, such changes are within the spirit of the invention. Brief Description of Drawings
[0011] These drawings illustrate certain aspects of some of the embodiments of the invention, and should not be used to limit or define the invention.
[0012] Figure 1 schematically illustrates a block diagram of an embodiment of a superior hydrocarbon production process of the present invention. Detailed Description of the Invention
[0013] The invention relates to the production of superior hydrocarbons suitable for use in transporting fuels and industrial chemicals from biobased feed loads, such as biomass, carbohydrates, which include sugars, sugar alcohols, celluloses, lignocelluloses, hemicelluloses, and any combination thereof. The superior hydrocarbons produced are useful in the formation of transport fuels, such as synthetic gasoline, diesel fuel, and jet fuel, as well as industrial chemicals. As used herein, the term "higher hydrocarbons" refers to hydrocarbons having an oxygen to carbon ratio less than oxygen to carbon ratio of at least one component of the biobased feed charge. As used herein, the term "hydrocarbon" refers to an organic compound that mainly comprises hydrogen and carbon atoms, which is also an unsubstituted hydrocarbon. In certain embodiments, the hydrocarbons of the invention also comprise heteroatoms (i.e., oxygen or sulfur) and therefore the term "hydrocarbon" can also include substituted hydrocarbons.
[0014] The methods and systems of the invention have an advantage of converting a crude biobased feed charge through hydrolysis and APR reactions to form an oxygenated intermediate stream comprising polyols, alcohols, ketones, aldehydes, and other mono- reaction oxygenates that can be fed directly into a condensation reactor to form superior hydrocarbons, which results in increased conversion and conversion efficiency and minimizes the formation of undesirable by-products, such as carmelins. Although not intended to be limited by theory, it is believed that by controlling the concentration of carbohydrates fed to an APR process, carbohydrate degradation under APR conditions can be minimized. Another advantage is that the invention provides methods that reduce the amount of undesirable by-products, thus improving the total yield of products in relation to the carbohydrates extracted from the biobased feed load. The invention reduces both the degradation products formed by extracting carbohydrates from biomass and, through subsequent processing in an APR reaction, the amount of coke formed in the transformation reactions to form a fuel mixture. In some embodiments, the oxygenated intermediates produced in the APR reaction are recycled in the process and system to form the solvent generated in situ, which is used in the digestion process of biobased feed cargo. This recycling saves costs and can increase the amount of carbohydrates extracted from the biobased feed load. In addition, by controlling the degradation of carbohydrates in the APR process, the hydrogenation reaction can be conducted together with the APR reaction at temperatures ranging from 175 ° C to 275 ° C. As a result, a selective hydrogenation reaction can be avoided, and the potential for fuel formation of the biobased feed charge fed to the process can be increased. This process and reaction scheme described here also results in savings in capital costs and savings in operating costs of the process. Advantages of specific embodiments will be described in more detail below.
[0015] In some embodiments, the invention provides methods that comprise: providing a biobased feed load; contacting the feed charge biobased with a solvent in a hydrolysis reaction to form an intermediate stream comprising carbohydrates; contacting the intermediate stream with an APR catalyst to form a plurality of oxygenated intermediates, wherein a first portion of the oxygenated intermediates is recycled to form the solvent; and processing at least a second portion of the oxygenated intermediates to form a fuel mixture.
[0016] Figure 1 shows an embodiment of a method of the present invention in which the hydrolysis of a biobased feed charge takes place in hydrolysis reaction 114 to produce an intermediate stream comprising carbohydrates 116, the intermediate stream 116 is fed for a reaction of APR 122 and then output current 124 (and, optionally 128) are fed to a condensation reaction 130 to produce higher hydrocarbons.
[0017] In some embodiments, the reactions described below are carried out in any suitable design system, including systems comprising batch, semi-batch or multi-system direct current and reactor vessels. One or more reactions can take place in an individual vessel and the process is not limited to separate reaction vessels for each reaction. In some embodiments, the system of the invention uses a fluidized catalytic bed system. Preferably, the invention is practiced using a steady-state steady-state system.
[0018] As used herein, the term "biobased feed load" means organic materials produced by plants (for example, leaves, roots, seeds and stems), and microbial and animal metabolic waste. Biobased feed loads can include biomass. Common sources of biomass include: agricultural waste (for example, corn stalks, straw, seed husks, cane remains, bagasse, nut shells, and livestock manure, poultry and pigs), wood materials (for example, wood or tree bark, sawdust, residues and factory scrap); solid urban waste (for example, paper waste and yard cuts), and energy crops (for example, poplars, willows, grass clippings, alfalfa, blue pasture, soybeans, corn). The term "biomass" also refers to the primary building blocks of all of the above, including, but not limited to, saccharides, lignins, celluloses, hemicelluloses, and starches. Biobased feed loads can be a source of carbohydrates.
[0019] Fig. 1 shows an embodiment of the present invention for converting biobased feed load into fuel products. In this embodiment, a biobased feed charge 112 is introduced for a hydrolysis reaction 114, along with a recycling stream 118. The recycling stream 118 can comprise a number of components, including solvents generated in situ, which may be useful in the solvation of sugars and lignins from the biobased feed load during the hydrolysis reaction. The term "in situ" as used herein refers to a component that is produced within the total process, is not limited to a particular reactor for production or use and is therefore synonymous with a component generated in the process . Solvents generated in situ may comprise oxygenated intermediates. The hydrolysis reaction can comprise a hydrolysis catalyst (for example, a metal or acid catalyst) to assist in the hydrolysis reaction. The reaction conditions in the hydrolysis reaction can vary within the reaction media so that a temperature gradient exists within the reaction medium, allowing hemicellulose to be extracted at a lower temperature than cellulose. For example, the reaction means may comprise an increasing temperature gradient from the biobased feed charge 112. Non-extractable solids can be removed from the reaction as an output stream 120. The intermediate carbohydrate stream 116 is a stream intermediate, which can comprise hydrolyzed biomass in the form of carbohydrates. The composition of the carbohydrate intermediate stream 116 may vary and may comprise a number of different compounds. Preferably, carbohydrates have 2 to 12 carbon atoms, and even more preferably 2 to 6 carbon atoms. Carbohydrates can also have an oxygen to carbon ratio of 0.5: 1 to 1: 1.2.
[0020] Several factors affect the conversion of the feed load based on the hydrolysis reaction. In some embodiments, hemicellulose can be extracted from the feed charge based on an aqueous fluid solution and hydrolyzed at temperatures below 160 ° C to produce a fraction of C5 carbohydrate. At increasing temperatures, this C5 fraction can be thermally degraded. Therefore, it is advantageous to convert C5, C6, or other sugar intermediates directly to more stable intermediates, such as sugar alcohols. Even these intermediates can further degrade, so that running the APR reaction to convert them to polyols such as glycerol, ethylene glycol, propylene glycol, and mono-oxygenates is preferred to increase process yields. By recycling the oxygenated intermediates from the APR reaction and performing the hydrolysis of the additional biomass with this recycled liquid, the concentration of active oxygenated intermediates can be increased to commercially viable concentrations without dilution with water. Typically, a concentration of at least 2%, or 5% or preferably greater than 8% of organic intermediates in water, may be suitable for a viable process. This can be determined by sampling the intermediate current at the outlet of the hydrolysis reaction and using an appropriate technique, such as chromatography to identify the concentration of total organic compounds. The oxygenated intermediate current has the potential to form fuel o, as described below.
[0021] Cellulose extraction starts above 160 ° C, with solubilization and hydrolysis becoming complete at temperatures of around 190 ° C, aided by organic acids (for example, carboxylic acids) formed from partial degradation of the components of carbohydrates. Some lignins can be solubilized before cellulose, while other lignins can persist at higher temperatures. Organic solvents generated IN SITU may comprise a portion of the oxygenated intermediates, including, but not limited to, alcohols and light polyols, which may assist in the solubilization and extraction of lignin and other components.
[0022] Temperatures ranging from about 125 ° C to 275 ° C, carbohydrates can degrade through a series of complex self-condensing reactions to form caramelans, which are considered degradation products that are difficult to convert to fuel. In general, some degradation reactions can be expected with the aqueous reaction conditions by applying temperature, since water will not completely suppress oligomerization and polymerization reactions.
[0023] In some embodiments of the invention, the biobased feed charge is hydrolyzed in a liquid medium, such an aqueous solution to obtain an intermediate stream of carbohydrates for use in the process. There are several suitable hydrolysis reaction methods for biobased feed charge, including, but limited to, acid hydrolysis, alkaline hydrolysis, enzymatic hydrolysis, catalytic hydrolysis, and hydrolysis using compressed hot water. In certain embodiments, the hydrolysis reaction can take place at a temperature between 100 ° C and 250 ° C and the pressure between 1 atm and 100 atm. In embodiments, including strong acid and enzymatic hydrolysis, the hydrolysis reaction can occur at temperatures as low as room temperature and pressure between 1 atm and 100 atm. In some embodiments, the hydrolysis reaction may comprise a hydrolysis catalyst (for example, a metal or acid catalyst) to assist in the hydrolysis reaction. The catalyst can be any catalyst capable of carrying out a hydrolysis reaction. For example, suitable catalysts may include, but are not limited to, acid catalysts, basic catalysts, metal catalysts and any combination thereof. Acid catalysts can include organic acids such as acetic, formic, levulinic acid and any combination thereof. In one embodiment, the acid catalyst can be generated in the APR reaction and comprise a component of the oxygenated intermediate stream.
[0024] In some embodiments, the aqueous solution may contain a solvent generated IN SITU. The solvent generated IN SITU generally comprises at least one alcohol or polyol capable of solvating one or more products of the hydrolysis reaction or other components of the biobased feed charge. For example, an alcohol can be useful for solvating lignin from a biomass feed charge for use within the process. The solvent generated IN SITU can also include one or more organic acids. In some embodiments, organic acid can act as a catalyst in the hydrolysis of the biobased feed charge. Each solvent component generated IN SITU can be supplied by an external source or can be generated within the process and recycled to the hydrolysis reactor. For example, a portion of the oxygenated intermediates produced in the APR reaction can be separated in the separation phase for use as the solvent generated IN SITU in the hydrolysis reaction. In one embodiment, the solvent generated IN SITU can be separated, stored, and selectively injected into the recycling stream in order to maintain a desired concentration in the recycling stream.
[0025] The temperature of the hydrolysis reaction can be selected so that the maximum amount of extractable carbohydrates are hydrolyzed and extracted as carbohydrates from the biobased feed load while limiting the formation of degradation products. In some embodiments, a plurality of reactor vessels can be used to carry out the hydrolysis reaction. These vessels can have any design capable of carrying out a hydrolysis reaction. Suitable reactor vessel models may include, but are not limited to, co-current, counter-current, agitated, or fluidized bed reactors. In this embodiment, the biobased feed charge can first be introduced into a reactor vessel operating at approximately 160 ° C. At this temperature, hemicellulose can be hydrolyzed to extract C5 carbohydrates and some lignins without degrading these products. The remaining biobased feed charge solids can then leave the first reactor vessel and move to a second reactor vessel. The second vessel can be operated between 160 ° C and 250 ° C so that the cellulose is further hydrolyzed to form C6 carbohydrates. The remaining biobased feed load solids can then leave the second reactor as a waste stream, while the intermediate stream of the second reactor can be cooled and combined with the intermediate stream from the first reactor vessel. The combined output current can then pass to the APR reactor. In another embodiment, a series of reactor vessels can be used with an increasing temperature profile so that a desired carbohydrate fraction is extracted in each vessel. The outlet of each vessel can then be cooled before combining the streams, or the streams can be individually fed to the APR reaction to convert the intermediate carbohydrate streams to one or more oxygenated intermediate streams.
[0026] In another embodiment, the hydrolysis reaction, as shown in figure 1, can take place in a single vessel. This vessel can have any design capable of carrying out a hydrolysis reaction. Suitable reactor vessel models may include, but are not limited to, co-current, counter-current, agitated, or fluidized bed reactors. In some embodiments, a countercurrent reactor design is used in which the biomass flows countercurrent to the aqueous stream, which may comprise a solvent generated IN SITU. In this embodiment, a temperature profile can exist within the reactor vessel so that the temperature within the hydrolysis reaction media at or near the biobased feed charge inlet is approximately 160 ° C and the temperature near the outlet of the biobased feed load is approximately 200 ° C to 250 ° C. The temperature profile can be obtained by introducing an aqueous fluid comprising a solvent generated IN SITU above 200 ° C to 250 ° C near the outlet of the biobased feed load, while simultaneously introducing a biobased feed load to 160 ° C or below. The specific inlet temperature of the aqueous fluid and the biobased feed load will be determined based on a heat balance between the two streams. The resulting temperature profile can be useful for the hydrolysis and extraction of cellulose, lignin, and hemicellulose, without the substantial production of degradation products.
[0027] Other means can be used to establish an appropriate temperature profile for the reaction of hydrolysis and extraction of cellulose and hemicellulose, together with other components, such as lignin without substantially the production of degradation products. For example, internal heat exchange structures can be used within one or more reaction vessels to maintain a desired temperature profile for the hydrolysis reaction. Other structures as would be known to a person skilled in the art can also be used.
[0028] Each reactor vessel of the invention preferably includes an inlet and an outlet adapted to remove the product stream from the vessel or reactor. In some embodiments, the vessel in which the hydrolysis reaction or some portion of the hydrolysis reaction occurs may include additional outlets to allow removal of portions of the reagent stream to help maximize the formation of the desired product. Suitable reactor models may include, but are not limited to, a retrromixing reactor (for example, a stirred tank, a bubble column, and / or a mixed jet reactor) can be employed, if the viscosity and characteristics of the partially digested biobased feed charge and liquid reaction media is sufficient to operate in a regime where the solids in the biobased feed charge are suspended in an excess liquid phase (as opposed to a stacked pile digester).
[0029] The relative composition of the various carbohydrate components in the carbohydrate intermediate stream in the methods of the present invention affects the formation of undesirable by-products such as coke in the APR reaction. In particular, a low concentration of carbohydrates in the intermediate stream can affect the formation of undesirable by-products. In preferred embodiments, it is desirable to have a concentration of no more than 5% easily degradable carbohydrates or heavy final precursors in the intermediate stream, while maintaining a total concentration of organic intermediates, which includes oxygenated intermediates (for example, mono-oxygenated and / or diols), concentration as high as possible through the use of the recycling concept.
[0030] In some embodiments of the invention, carbohydrates in the carbohydrate intermediate stream produced by the hydrolysis reaction are partially deoxygenated by the addition of hydrogen or another suitable catalyst for the hydrolysis reactor.
[0031] APR converts polyhydric alcohols to aldehydes, which react on a catalyst with water to form hydrogen, carbon dioxide, and oxygenated intermediates, which comprise smaller polyhydric alcohols. Polyhydric alcohols can further react through a series of deoxygenation reactions to form additional oxygenated intermediates that can produce higher hydrocarbons through a condensation reaction.
[0032] Referring again to figure 1, according to an embodiment, the intermediate stream of carbohydrate 116 from the hydrolysis reaction 114 can be passed to an APR reaction to produce oxygenated intermediates. Intermediate carbohydrate stream 116 can comprise C5 and C6 carbohydrates that can be reacted in the APR reaction. For embodiments comprising thermocatalytic APR, oxygenated intermediates, such as sugar alcohols, sugar polyols, carboxylic acids, and furans can be converted to fuels. The APR reaction can comprise an APR catalyst, to assist in the reactions that take place. The APR reaction conditions can be such that an APR reaction can take place, along with a hydrogenation reaction, a hydrogenolysis reaction, or both, like many of the reaction conditions that overlap or are complementary. The various reactions can result in the formation of one or more oxygenated intermediate currents 124 ,. As used herein, an "oxygenated intermediate" can include one or more polyols, alcohols, ketones, or any other hydrocarbon having at least one oxygen atom.
[0033] In some embodiments, APR catalysts can be a heterogeneous catalyst capable of catalyzing a reaction between hydrogen and carbohydrate, oxygenated intermediate, or both, to remove one or more oxygen atoms to produce alcohols and polyols to be fed to the condensation reactor. The APR catalyst can generally include Cu, Re, Ni, Fe, Co, Ru, Pd, Rh, Pt, Os, Ir, and alloys or any combination thereof, either alone or with promoters, such as W, Mo, Au, Ag, Cr, Zn, Mn, Sn, B, P, Bi, and alloys or any combination thereof. Other effective APR catalyst materials include supported nickel or rhenium modified ruthenium. In some embodiments, the APR catalyst also includes any of the supports, depending on the desired functionality of the catalyst. APR catalysts can be prepared by methods known to those of ordinary skill in the art. In some embodiments the APR catalyst includes a Group VIII supported metal catalyst and a metal sponge material (e.g., a sponge nickel catalyst). Raney Nickel provides an example of an activated sponge nickel catalyst suitable for use in the present invention. In some embodiments, the APR reaction in the invention is carried out using a catalyst comprising a nickel-nickel catalyst or a modified tungsten-nickel catalyst. An example of a suitable catalyst for the APR reaction of the invention is a nickel-rhenium catalyst supported on carbon.
[0034] In some embodiments, a suitable Raney nickel catalyst can be prepared by treating an alloy of approximately equal amounts by weight of nickel and aluminum with an aqueous alkaline solution, for example, containing about 25% by weight of hydroxide hydroxide. sodium. Aluminum is selectively dissolved by the aqueous alkaline solution, resulting in a sponge-shaped material comprising mainly of nickel with smaller amounts of aluminum. The initial alloy includes promoter metals (i.e., molybdenum or chromium) in an amount such that 1 to 2% by weight remains in the formed sponge nickel catalyst. In another embodiment, the APR catalyst is prepared using a solution of ruthenium (III) nitrosyl nitrate, ruthenium (III) chloride in water to impregnate a suitable support material. The solution is then dried to form a solid with a water content of less than 1% by weight. The solid is then reduced, at atmospheric pressure, in a hydrogen stream at 300 ° C (not calcined) or 400 ° C (calcined), in a rotary ball oven for 4 hours. After cooling and making the catalyst inert with nitrogen, 5% by volume of oxygen in nitrogen is passed over the catalyst for 2 hours.
[0035] In certain embodiments, the APR catalyst may include a catalyst support. The catalyst support stabilizes and supports the catalyst. The type of catalyst support used depends on the catalyst selected and the reaction conditions. Suitable supports for the invention include, but are not limited to, carbon, silica, silica-alumina, zirconia, titania, ceria, vanadium, nitride, boron nitride, heteropoly acids, hydroxyapatite, zinc oxide, chromium, zeolites, carbon nanotubes , carbon fullerene and any combination thereof.
[0036] The conditions for which to perform the APR reaction will vary according to the type of starting material and the desired products. In general, the APR reaction is conducted at temperatures of 80 ° C to 300 ° C, and preferably at 120 ° C to 300 ° C, and more preferably at 200 ° C to 280 ° C. In some embodiments, the APR reaction is conducted at pressures from 500 kPa to 14,000 kPa.
[0037] The APR 124 product stream may comprise APR products that include oxygenated intermediates. As used herein, "oxygenated intermediates" generally refers to hydrocarbon compounds with 1 or more carbon atoms and between 1 and 3 oxygen atoms (referred to herein as C1 + O1-3 hydrocarbons), such as alcohols, ketones, aldehydes, furans, hydroxy carboxylic acids, carboxylic acids, diols and triols. Preferably, the oxygenated intermediates have 1 to 6 carbon atoms, or 2 to 6 carbon atoms, or 3 to 6 carbon atoms. Alcohols may include, without limitation, primary, secondary, linear, branched or cyclic C1 + alcohols, such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, butanol, pentanol, cyclopentanol, hexanol, cyclohexanol, 2 -methyl-cyclopentanonol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, and isomers thereof. Ketones can include, without limitation, hydroxy ketones, cyclic ketones, diketones, acetone, propanone, 2-oxopropanal, butanone, butane-2,3-dione, 3-hydroxybutane-2-one, pentanone, cyclopentanone, pentane-2,3 -dione, pentane-2,4-dione, hexanone, cyclohexanone, 2-methyl-cyclopentanone, heptanone, octanone, nonanone, decanone, undecanone, dodecanone, methylglioxal, butanedione, pentanedione, dicetohexane, and isomers thereof. Aldehydes may include, without limitation, hydroxyaldehydes, acetaldehyde, propionaldehyde, butyraldehyde, pentanal, hexanal, heptanal, octanal, nonal, decanal, undecanal, dodecanal, and isomers thereof. Carboxylic acids can include, without limitation, formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, isomers and derivatives thereof, including hydroxylated derivatives such as 2-hydroxybutanoic and lactic acid . The diols may include, without limitation, ethylene glycol, propylene glycol, 1,3-propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, undecanediol, dodecanediol, and isomers thereof. Triols may include, without limitation, glycerol, 1,1,1 tris (hydroxymethyl) - ethane- (trimethylolethane), trimethylolpropane, hexanotriol, and isomers thereof. Furans and furfurals include, without limitation, furan, tetrahydrofuran, dihydrofuran, 2-furan methanol, 2-methyl-tetrahydrofuran, 2,5-dimethyl-tetrahydrofuran, 2-methyl furan, 2-ethyl-tetra- hydrofuran, 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-2-furoic acid, dihydro-5- (hydroxymethyl) -2 (3H) -furanone, tetrahydrofurfuryl alcohol, 1- (2-furyl) ethanol, hydroxymethyltetrahydrofurfural, and isomers thereof.
[0038] The oxygenated intermediate current can generally be distinguished as comprising the components corresponding to the formula: CnOm, where n = 1-6 and m = 1 to 6, and m <n. Other elements, such as hydrogen, may also be present in these molecules. Additional components that may be present in the APR product stream may include hydrogen and other gases such as carbon dioxide. These components can be separated from the oxygenated intermediates or they can be fed into the condensation reaction for removal after the condensation reaction.
[0039] In a preferred embodiment, hydrogenation and hydrogenolysis takes place in the APR reactor, because the same catalysts and conditions are applicable to all three reactions. The hydrogenation and hydrogenolysis reactions are discussed in more detail below. These reactions can optionally be used in the methods of the invention, either separately from APR or together with APR. A person skilled in the art, with the benefit of this disclosure, would know which conditions to choose to maximize the desired product of hydrogenation, hydrogenolysis, and the APR reactions. The inclusion of all three reactions in a single reaction step can have the advantage of intensifying the process and reducing costs over a process in which the three reactions are carried out in separate vessels. Additional process equipment may be present to move product streams between reactors in specific embodiments. For example, pumps can be used to pass a fluid product stream between reactor vessels when multiple vessels are used.
[0040] In some embodiments of the invention, it is optionally desirable to convert the carbohydrates and oxygenated intermediates of the hydrolysis reaction and APR reaction into smaller molecules. A suitable method for this conversion is through a hydrogenolysis reaction.
[0041] Various processes are known for carrying out hydrogenolysis. A suitable method includes contacting a carbohydrate or intermediate oxygenated with hydrogen or hydrogen mixed with a suitable gas and a hydrogenolysis catalyst in a hydrogenolysis reaction under conditions sufficient to form a reaction product comprising smaller molecules or polyols. As used herein, the term "smaller molecules or polyols" includes any molecule that has a lower molecular weight, which may include fewer carbon atoms or oxygen atoms, than the starting carbohydrate. In some embodiments, the reaction products include smaller molecules that include polyols and alcohols. Someone of ordinary skill in the art would be able to choose the appropriate method for carrying out the hydrogenolysis reaction.
[0042] In some embodiments, a 5 and / or 6 carbon carbohydrate molecule can be converted to propylene glycol, ethylene glycol, and glycerol using a hydrogenolysis reaction in the presence of a hydrogenolysis catalyst. The hydrogenolysis catalyst can include the same catalysts discussed above in relation to the APR catalyst In certain embodiments, the catalyst described in the hydrogenolysis reaction can include a catalyst support, as described above for the APR catalyst.
[0043] The conditions for which to carry out the hydrogenolysis reaction will vary according to the type of starting material and the desired products. One of the technicians on the subject, with the benefit of this disclosure, will recognize the appropriate conditions to use to carry out the reaction. In general, the hydrogenolysis reaction can be conducted at temperatures of 110 ° C to 300 ° C, and preferably at 170 ° C to 220 ° C, and more preferably at 200 ° C to 225 ° C. In some embodiments, the The hydrogenolysis reaction is carried out under basic conditions, preferably at a pH of 8 to 13, and even more preferably at a pH of 10 to 12. In some embodiments, the hydrogenolysis reaction is carried out at pressures in the range between 60 kPa and 16,500 kPa, and preferably in a range between 1700 kPa and 14,000 kPa, and even more preferably between 4800 kPa and 11,000 kPa. In certain embodiments, the conditions described in the hydrogenolysis reaction will be the same as described above for the APR and hydrogenation reaction as long as the reaction can take place in the same reactor.
[0044] Carbohydrates, oxygenated intermediates, or both can take place in a hydrogenation reaction to saturate one or more unsaturated bonds. Various processes are suitable for hydrogenation of carbohydrates, oxygenated intermediates, or both. One method includes contacting the feed stream with hydrogen or hydrogen mixed with a suitable gas and catalyst under conditions sufficient to produce a hydrogenation reaction to form a hydrogenated product. In some embodiments, suitable hydrogenation catalysts can be selected from the list of APR catalysts provided above.
[0045] The conditions under which to carry out the hydrogenation reaction will vary according to the type of starting material and the desired products. One of those skilled in the art, with the benefit of this disclosure, will recognize the appropriate reaction conditions. In general, the hydrogenation reaction is conducted at temperatures of 80 ° C to 250 ° C, and preferably at 90 ° C to 200 ° C, and more preferably at 100 ° C to 150 ° C. In some embodiments, the hydrogenolysis reaction is carried out at pressures from 500 kPa to 14,000 kPa. In some embodiments, the conditions of this reaction correspond to those for the APR reaction.
[0046] The hydrogen used in the hydrogenation reaction of the present invention can include external hydrogen, recycled hydrogen, hydrogen generated IN SITU, and any combination thereof. As used herein, the term "external hydrogen" refers to hydrogen that does not come from the same biobased feed charge reaction, but is added to the system from another source.
[0047] In some embodiments, the APR, hydrogenation and hydrogenolysis catalysts are the same and can exist on the same bed in the same reactor vessel. Each reactor vessel of the invention preferably includes an inlet and an outlet adapted to remove the product stream from the vessel or reactor. In some embodiments, vessels and reactors include additional outlets to allow removal of portions of the reagent stream to help maximize the formation of the desired product, and to allow the collection and recycling of by-products for use in other portions of the system.
[0048] In some embodiments, in the APR reaction, oxygenated intermediates can be produced by catalytically reacting carbohydrates, in the presence of an APR catalyst, at a reforming temperature and reforming pressure to produce hydrogen and catalytically reacting the hydrogen produced with a portion of carbohydrates on a hydrogenation / hydrogenolysis catalyst and deoxygenation pressure and temperature to produce the desired oxygenated intermediates. In certain embodiments, the hydrogen used can be supplied entirely from an external source or supplemented by an external source. In another embodiment, the oxygenated intermediates can also include recycled oxygenated intermediates.
[0049] Without pretending to be limited by theory, reactions comprising conversion of feed load based on APR can be expressed as: Biomass hydrolysis (B) ^ sugar: rs = konB (Eq. 1) Sugar degradation ^ ends of heavy = -kdS2 (Eq. 2). Sugar hydrogenation ^ to sugar alcohol (A): rs = -knWHPH2S (Eq. 3) Sugar alcohol (A) APR ^ desired products: rA = ^ RWRA (Eq. 4 )
[0050] Oxygenated intermediates, which comprise sugar alcohols, have been thought to be more stable under APR reaction conditions than carbohydrates such as sugars, such that higher concentrations of oxygenated intermediates can be tolerated in the reaction mixture without excessive formation of degradation products. Although the stability has slightly improved for oxygenated intermediates, the residence time of liquid phases at APR temperatures in relation to the APR catalytic contact time can be minimized, in order to decrease the yield losses for degradation products. A consideration in the process design is to react the carbohydrates to the desired oxygenated intermediates (Eq. 3), and continue to the desired reaction products (Eq. 4), as soon as they are formed by hydrolysis (Eq. 1) and before the Eq. 2 carbohydrate degradation reaction can occur. Another consideration includes the reaction conditions of the carbohydrates involved. Hemicellulose C5 carbohydrates are extracted at temperatures of around 160 ° C, while C6 carbohydrates are extracted after cellulose hydrolysis at temperatures above 160 ° C, which could result in the rapid degradation of C5 carbohydrates. Adding reactions that involve the formation or consumption of S carbohydrates and solving for steady-state concentration gives:
whereas the degradation products in relation to the yield of desired intermediates is given by:

[0051] Although only theoretical, Eq. 6 tends to indicate that to reduce the loss of yield for degradation products, the carbohydrate concentration (ie, S) must be minimized, and hydrogenation activity must be maximized through, for example, For example, increasing the constant rate k H by adding more active catalyst, or having a higher PH2 pressure of H2, or increasing the concentration of catalyst present (WH) in relation to the residence time in the free liquid for homogeneous reaction. Eq. 5 teaches that the carbohydrate concentration can be minimized by limiting the rate of kOH hydrolysis and maximizing the rate of hydrogenation or the rate of APR.
[0052] The oxygenated intermediate current 124 can then pass from the APR reaction to an optional separation phase 126, which produces oxygenated intermediate current 128. In some embodiments, the optional separation phase 126 includes elements that allow the separation of the intermediates oxygenated in different components. In some embodiments of the present invention, the separation phase 126 can receive the oxygenated intermediate stream 124 from the APR reaction and separate the various components into two or more streams. For example, a suitable separator may include, but is not limited to, a phase separator, extraction column, extractor, or distillation column. In some embodiments, a separator is installed before the condensation reaction to favor the production of higher hydrocarbons, separating the higher polyols from the oxygenated intermediates. In such an embodiment, the higher polyols are recycled back through hydrolysis reactor 114, while the other oxygenated intermediates are passed on to the condensation reaction. In addition, an output stream from the separation phase 118 that contains a portion of the oxygenated intermediates can act as the solvent generated IN SITU, when recycled to the hydrolysis reactor 114. In one embodiment, the separation phase 126 can also be used to remove some or all of the lignin from the oxygenated intermediate stream. The lignin can be passed out of the separation phase as a separate stream, for example, as output stream 134.
[0053] In some embodiments, the oxygenated intermediates are converted to a fuel mixture that can be used as a fuel additive through hydrogenation of the oxygenated intermediates. Several processes are suitable for the hydrogenation of oxygenated intermediates. One method includes contacting the feed stream with hydrogen or hydrogen mixed with a suitable gas and catalyst under conditions sufficient to carry out a hydrogenation reaction to form a hydrogenated product. Suitable catalysts and reaction conditions are described above.
[0054] The hydrogenation of oxygenated intermediates can produce one or more saturated alcohols, polyols, or hydrocarbons. The alcohols produced in the invention have from 2 to 30 carbon atoms. In some embodiments, alcohols are cyclic. In another embodiment, the alcohols are branched. In another embodiment, alcohols are straight-chained. Alcohols suitable for the present invention include, but are not limited to, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptydecanol, octyldecanol, nonildecanol, eicosanol, uneicosanol, doeicosanol, trieicosanol, tetraeicosanol, and isomers thereof.
[0055] Saturated alcohols, polyols, and / or hydrocarbons can be used as a fuel mixture additive in transportation or other fuels. In addition, the products can be sold as a chemical for other uses known to a person skilled in the art.
[0056] In some other embodiments, the oxygenated intermediates discussed above can be converted to higher hydrocarbons by means of a condensation reaction shown schematically as condensation reaction 130 in figure 1. In one embodiment, the upper hydrocarbons can be part of a fuel mixture for use as a transport fuel. In such an embodiment, condensation of the oxygenated intermediates occurs in the presence of a catalyst capable of forming higher hydrocarbons. Although not intended to be limited by theory, it is believed that the production of higher hydrocarbons proceeds through a step-by-step addition reaction, including the formation of a carbon-carbon bond, or carbon-oxygen. The products resulting from the reaction include any number of compounds that contain these portions, as described in more detail below.
[0057] Referring to figure 1, in some embodiments, an output current 128 containing at least a portion of the oxygenated intermediates can pass to a condensation reaction. The condensation reaction can comprise a variety of condensation catalysts to condense one or more oxygenated intermediates to higher hydrocarbons. Higher hydrocarbons can comprise a combustible product. The combustible products produced by the condensation reactor represent the product stream from the total hydrocarbon stream total process 110. In one embodiment, the oxygen-to-carbon ratio of the superior hydrocarbons produced through the condensation reaction is less than 0 , 5, alternatively, less than 0.4, or preferably less than 0.3.
[0058] In the embodiment shown in figure 1, the carbohydrates extracted from the biobased feed charge using a hydrolysis reaction are passed through an APR reactor to form oxygenated intermediates suitable for the condensation reaction in the condensation reactor 130. In an embodiment, the biobased feed load can be
[0059] In certain embodiments, suitable condensation catalysts include an acid catalyst, a basic catalyst, or an acid / basic catalyst. As used herein, the term "acid / base catalyst" refers to a catalyst that has both an acid and base functionality or functional sites. In some embodiments, the condensation catalyst may include, without limitation, zeolites, carbides, nitrides, zirconia, alumina, silica, aluminosilicates, phosphates, titanium oxides, zinc oxides, vanadium oxides, lanthanum oxides, yttrium oxides, oxides scandium, magnesium oxides, cerium oxides, barium oxides, calcium oxides, hydroxides, heteropoly acids, inorganic acids, modified acid resins, modified base resins, and any combination thereof. In some embodiments, the condensation catalyst can also include a modifier. Suitable modifiers include La, Y, Sc, P, B, Bi, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, and any combination thereof. In some embodiments, the condensation catalyst can also include a metal. Suitable metals include Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, alloys, and any combination of them.
[0060] In certain embodiments, the catalyst described in the condensation reaction can include a catalyst support, as described above for the hydrogenation reaction. In certain embodiments, the condensation catalyst is self-supporting. As used herein, the term “self-sustaining” means that the catalyst does not need any other material to serve as a support. In another embodiment, the condensation catalyst to be used in conjunction with a separate support suitable for suspending the catalyst. In some embodiments, the condensation catalyst support is silica.
[0061] The conditions under which to carry out the condensation reaction will vary according to the type of starting material and the desired products. One of the technicians in the subject, with the benefit of this disclosure, will recognize the conditions suitable for use to carry out the reaction. In some embodiments, the condensation reaction is carried out at a temperature at which the thermodynamics for the proposed reaction are favorable. The temperature for the condensation reaction will vary depending on the specific starting polyol or alcohol. In some embodiments, the temperature for the condensation reaction is in the range of 80 ° C to 500 ° C, and preferably 125 ° C to 450 ° C, and more preferably 125 ° C to 250 ° C. In some embodiments, the condensation reaction is conducted at pressures in the range of 0 kPa to 9,000 kPa, and preferably in the range of 0 kPa to 7,000 kPa, and even more preferably between 0 kPa and 5,000 kPa.
[0062] In some embodiments, the invention comprises a system that has a condensation reactor for the reaction of the APR product stream, in the presence of a condensation catalyst to produce at least some higher hydrocarbons forming fuel. Each reactor of the invention preferably includes an inlet and an outlet adapted to remove the product stream from the reactor. In some embodiments, the reactors include additional outlets to allow removal of portions of the reagent stream to help maximize the formation of the desired product, and to allow the collection and recycling of by-products for use in other portions of the system.
[0063] In higher hydrocarbons formed by the invention may include a wide variety of compounds depending on the reaction conditions and the composition of the oxygenated intermediates fed into the reaction. Examples of higher hydrocarbons include, but are not limited to, alkanes, branched or straight chain having 4 to 30 carbon atoms, branched chain alkenes having 4 to 30 carbon atoms, cycloalkanes having 5 to 30 carbon atoms, cycloalkenes that have 5 to 30 carbon atoms, aryls, fused aryls, alcohols, and ketones. Suitable alkanes include, but are not limited to, butane, pentane, pentene, 2-methylbutane, hexane, hexene, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethyl heptane, heptene, octane, octene , 2,2,4-trimethylpentane, 2,3-dimethylhexane, 2,3,4-trimethylpentane, 2,3-dimethylpentane, nonane, nonene, decane, decene, undecane, undecene, dodecane, dodecene, tridecane, tridecene, tetradecane , tetradecene, pentadecane, pentadecene, ninildecane, nocildecene, eicosane, eicosene, uneidosane, uneicosene, doeicosane, doeicosene, trieicosane, trieicosene, tetraeicosane, tetraeicosene, and isomers thereof.
[0064] In some embodiments, cycloalkanes and cycloalkenes are not substituted. In another embodiment, cycloalkanes and cycloalkenes are mono-substituted. In yet another embodiment, cycloalkanes and cycloalkenes are multi-substituted. In embodiments comprising substituted cycloalkanes and cycloalkenes, the substituted group includes, without limitation, a straight or branched chain alkyl having 1 to 12 carbon atoms, a straight or branched chain alkylene having 1 to 12 carbon atoms, a phenyl and any combination thereof. Suitable cycloalkanes and cycloalkenes include, but are not limited to, cyclopentane, cyclopentene, cyclohexane, cyclohexene, methylcyclopentane, methylcyclopentene, ethylcyclopentane, ethylcyclopentene, ethylcyclohexane, ethylcyclohexane, ethylcyclohexane hexene, isomers and any combination thereof.
[0065] In some embodiments, the aryls formed are not replaced. In another embodiment, the aryls formed are mono-substituted. In embodiments comprising the substituted aryls, the substituted group includes, without limitation, a straight or branched chain alkyl having 1 to 12 carbon atoms, a straight or branched chain alkylene having 1 to 12 carbon atoms, a phenyl group , and combinations thereof. Suitable aryls for the invention include, but are not limited to, benzene, toluene, xylene, ethylbenzene, para-xylene, meta-xylene, and any combination thereof.
[0066] The alcohols produced in the invention have from 2 to 30 carbon atoms. In some embodiments, alcohols are cyclic. In another embodiment, the alcohols are branched. In another embodiment, alcohols are straight-chained. Alcohols suitable for the invention include, but are not limited to, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptydecanol, octyldecanol, nonildecanol, eicosanol, uneicosanol, doeicosanol, doeicos , trieicosanol, tetraeicosanol, and isomers thereof.
[0067] The ketones produced in the invention have from 2 to 30 carbon atoms. In some embodiments, ketones are cyclical. In another embodiment, the ketones are branched. In another embodiment, the ketones are straight-chain. Suitable ketones for the present invention include, but are not limited to, butanone, pentanone, hexanone, heptanone, octanone, nonanone, decanone, undecanone, dodecanone, tridecanone, tetradecanone, pentadecanone, hexadecanone, heptildecanone, octildecanone, non-dicosanone, and octyldecanone, non-dicosane, and doeicosanone, trieicosanone, tetraeicosanone, and isomers thereof.
[0068] In one embodiment, the condensation reaction can produce a fuel mixture that comprises a gasoline fuel. “Gasoline fuel” refers to a hydrocarbon mixture predominantly comprising C5-9 hydrocarbons, for example, C6-8 hydrocarbons, and having a boiling point range between 32 ° C (90 ° F) to about 204 ° C (400 ° F). A gasoline fuel includes, but is not limited to, direct distillation gasoline, naphtha, fluidized or thermally catalytically cracked gasoline, VB gasoline, and Coker gasoline. The hydrocarbon content of a gasoline fuel is determined by the ASTM Method D2887.
[0069] In this embodiment, the condensation reaction can be carried out at a temperature at which the thermodynamics for the proposed reaction are favorable for the formation of C5-9 hydrocarbons. The temperature for the condensation reaction will generally be in the range of 275 ° C to 500 ° C, and preferably from 300 ° C to 450 ° C, and more preferably from 325 ° C to 400 ° C. The condensation reaction can be conducted at pressures in the range of 0 kPa to 9,000 kPa, and preferably in the range of 0 kPa to 7,000 kPa, and even more preferably between 0 kPa and 5,000 kPa.
[0070] The resulting gasoline fuel mixture can be subjected to additional processes to treat the fuel mixture to remove certain components or further conform the fuel mixture to a gasoline fuel standard. Suitable techniques may include hydrotreating to remove any oxygen, sulfur, or nitrogen remaining in the fuel mixture. Hydrogenation can be carried out after the hydrotreating process to saturate at least some olefinic bonds. Such hydrogenation can be carried out to conform the fuel mixture to a specific fuel pattern (for example, a gasoline fuel pattern). The hydrogenation step of the fuel mixture stream can be carried out according to known procedures, or with a continuous or batch method. In particular, it can be carried out by feeding hydrogen at a pressure ranging from 5 bar (0.5 MPa) to 20 bar (2 MPa) and at a temperature ranging from 50 ° C to 150 ° C and reacting for a time ranging from 2 to 20 hours in the presence of a hydrogenation catalyst such as a supported palladium or platinum, for example 5% by weight of palladium or platinum on activated carbon.
[0071] Isomerization can be used to treat the fuel mixture to introduce a desired degree of branching or otherwise selectively for at least some components in the fuel mixture. It may be useful to remove any impurities before the hydrocarbons are contacted with the isomerization catalyst. The isomerization step comprises an optional extraction step, in which the fuel mixture from the oligomerization reaction can be purified by extraction with water vapor or a suitable gas, such as light hydrocarbon, nitrogen or hydrogen. The optional extraction step is carried out in counter-current in a unit upstream of the isomerization catalyst, where the gas and liquid are contacted with each other, or before the effective isomerization reactor in a separate extraction unit using the principle counter-current.
[0072] After the optional step of extracting the fuel mixture, it can be passed to a reactive isomerization unit that comprises one or more catalyst bed (s). The catalyst beds of the isomerization step can work either in co-current or counter-current form. In the isomerization step, the pressure can vary from 20 bar (2 MPa) to 150 bar (15 MPa), preferably in the range of 20 bar (2 MPa) to 100 bar (10 MPa), the temperature being between 200 ° C and 500 ° C, preferably between 300 ° C and 400 ° C. In the isomerization step, any isomerization catalysts known in the art can be used. Suitable isomerization catalysts can contain molecular sieve and / or a Group VII metal and / or a vehicle. In one embodiment, the isomerization catalyst contains SAPO-11 or SAP041 or ZSM-22 or ZSM-23 or ferrierite and Pt, Pd or Ni and Al2O3 or Si02. Typical isomerization catalysts are, for example, Pt / SAPO-11 / Al2O3, Pt / ZSM-22 / Al2O3, Pt / ZSM-23 / Al2O3 and Pt / SAPO-11 / SiO2.
[0073] Thus, in one embodiment, the fuel mixture produced by the processes described here is a mixture of hydrocarbons that meets the requirements for a gasoline fuel (that is, it complies with ASTM D2887).
[0074] In one embodiment, the condensation reaction can produce a fuel mixture that meets the requirements for a diesel fuel or jet fuel. Fuel for traditional diesel engines are petroleum distillates rich in paraffinic hydrocarbons. They have boiling ranges as wide as 205.5 ° C to 433.3 ° C (370 ° F to 780 ° F), which are suitable for combustion in a compression ignition engine, such as a diesel engine vehicle. . The American Society for Testing and Materials (ASTM), establishes the degree of diesel according to the boiling variation, together with permissible ranges of other fuel properties, such as cetane number, fog point, flash point, viscosity , aniline point, sulfur content, water content, ash content, copper strip corrosion, and carbon residue. Thus, any fuel mixture according to ASTM D975 can be defined as diesel fuel.
[0075] The present invention also provides methods for producing jet fuel. Jet fuel is transparent to straw-colored. The most common fuel is an unleaded / paraffin oil based fuel classified as Al Airplane, which is produced to an internationally standardized set of specifications. Jet fuel is a mixture of a large number of different hydrocarbons, possibly as many as a thousand or more. The range of their sizes (molecular weights or carbon numbers) is restricted by the requirements for the product, for example, freezing point or smoke point. Kerosene-type aviation fuel (including Jet A and Jet A-l) has a carbon number distribution between about C8 and C16. Wide-cut naphtha aviation fuel (including Jet B) typically has a carbon number distribution between about C5 and C15. A fuel mixture according to ASTM D1655 can be defined as jet fuel.
[0076] Both planes (Jet A and Jet B) can contain a number of additives. Useful additives include, but are not limited to, antioxidants, antistatic agents, corrosion inhibitors, fuel system ice inhibiting agents (FSII). Antioxidants prevent gum formation and are generally based on alkylated phenols, for example, AO-30, AO-31, or AO-37. Antistatic agents dissipate static electricity and prevent sparks. Stadis 450 with dinonylnaphthylsulfonic acid (DINNSA) as the active ingredient, is an example. Corrosion inhibitors, for example, DCI-4A is used for civil and military fuels and DCI-6A is used for military fuels. FSII agents include, for example, di-EGME.
[0077] A fuel mixture that meets the requirements for a diesel fuel (for example, ASTM D975) or a jet fuel (for example, ASTM D1655) can be produced using the methods of the present invention. In one embodiment, a method for producing a diesel fuel mixture may comprise: providing a biobased feed load; contacting the biobased feed charge with a catalyst and solvent to form an intermediate stream comprising carbohydrates; contacting the intermediate stream with an APR catalyst to form a plurality of oxygenated intermediates, wherein a first portion of the oxygenated intermediates are recycled to form the solvent; contacting an oxygenated intermediate stream with a condensation catalyst to produce an olefin stream; contacting the olefin stream with an oligomerization catalyst to produce higher hydrocarbons, where the higher hydrocarbons can meet the definition of a diesel fuel or jet fuel.
[0078] In this embodiment, the condensation reaction can be carried out at a temperature at which the thermodynamics for the proposed reaction are favorable for the formation of olefins with a carbon number ranging from C2 to C8. The temperature for the condensation reaction will generally be in the range of 80 ° C to 275 ° C, and preferably 100 ° C to 250 ° C, and more preferably 150 ° C to 200 ° C. The condensation reaction can be conducted at pressures in the range between 0 kPa to 9,000 kPa, and preferably in the range between 0 kPa and 7,000 kPa, and even more preferably between 0 kPa and 5,000 kPa. The olefin products produced will generally comprise one or more unsaturated bonds.
[0079] The olefin products produced from the condensation reaction can be further processed to form a fuel mixture according to the standard for diesel fuel or jet fuel. In one embodiment, the olefin products can be contacted with an oligomerization catalyst to produce a fuel mixture. The products of an olefin oligomerization reaction can mainly include olefins from linear oligomerization or mixtures of olefins, paraffins, cycloalkanes and aromatics. The product spectrum is influenced by the conditions of both reactions and the nature of the catalyst. The oligomerization of olefins with an acid catalyst (for example, a zeolite) is influenced by several factors, including thermodynamics, kinetic and diffusion limitations, and selectivity and side shape reactions.
[0080] Without claiming to be limited by theory, it is believed that a number of reaction mechanisms are responsible for distributing the final olefin reaction product to form a fuel mixture. For example, it is believed that the acid-catalyzed oligomerization of olefins occurs through a carbocationic mechanism resulting in a growth of the sequential chain. Molecular weight growth occurs by condensing any two olefins to a single larger olefin. Olefins also undergo double bonding and isomerization of the skeleton. In addition to oligomerization, any two olefins can react to disproportionate to two olefins of two different carbon numbers, obtaining intermediate or "non-oligomer olefins". This can randomly tend to the product's molecular weight distribution without significantly changing its average carbon number. Olefin cracking can also occur simultaneously with oligomerization and disproportionate. Olefins can be subjected to cyclization and hydrogen transfer reactions, leading to the formation of cycloolefins, alkyl aromatics and paraffins, in which it has been called joint polymerization.
[0081] In practice, the kinetics of oligomerization, disproportionate, and cracking reactions can determine the distribution of the olefin product under process conditions. At high temperature or low pressure, thermodynamics leads the reaction products to be distributed in the light olefin range, while low temperature and high pressure tends to favor higher molecular weight olefins. At low temperature, mostly pure oligomers are formed with most of the product being trimer and tetramer. With the increase in temperature, more disproportionate and cracking and, therefore, randomization of the olefin distribution may occur. At moderate temperatures, the product can essentially be random and the average number of carbon can be maximized. In addition to other thermodynamic considerations, the reactivity of olefins decreases with an increase in the number of carbon, due to diffusion limitations within the catalyst pore system and the lower probability of coincident reaction centers of the collision molecules for a bimolecular reaction.
[0082] In some embodiments, the olefin feed stream may be pretreated to remove any oxygenated compounds or oxygen atoms that may be present in the olefin intermediate stream. The removal of oxygenated compounds from the olefinic stream can occur by various methods known in the art, for example, with hydrotreating to remove any excess oxygen, sulfur, or nitrogen.
[0083] The oligomerization catalyst with which the olefin feed stream is contacted can be an acid catalyst, including, but not limited to, a zeolite including a selective form or types of ZSM-5 pentasil zeolite. A specific zeolite can have selectivity in a way that can be used to form a higher hydrocarbon that does not contain excessively branched hydrocarbons. For example, the acid catalyst can comprise a pentacil zeolite with a Si02 / A12O3 ratio ranging from about 30 to about 1,000 in the form of hydrogen or sodium. Other zeolites with medium-sized pores (for example, ZSM-12, -23) can also produce oligomers with a low degree of branching due to the “shape selectivity” phenomenon. Other acid catalysts may include, but are not limited to, amorphous acid materials (silicoalumin), large pore zeolites, cation exchange resins and supported acids (eg, phosphoric acid).
[0084] In one embodiment, an olefinic oligomerization reaction can be performed in any suitable reactor configuration. Suitable configurations include, but are not limited to, batch reactors, semi-batch reactors, or continuous reactor models, such as fluidized bed reactors with external regeneration vessels. Reactor models may include, but are not limited to, tubular reactors, fixed bed reactors, or any type of reactor of another material suitable for carrying out the oligomerization reaction. In one embodiment, a continuous oligomerization process for the production of hydrocarbon fuels for diesel engines and boiling range aviation can be carried out using an oligomerization reactor to contact an olefin feed stream comprising short chain olefins with a chain length of 2 to 8 carbon atoms with a zeolite catalyst at elevated temperature and pressure, in order to convert short chain olefins for fuel mixing in the boiling range of diesel. The oligomerization reactor can be operated at relatively high pressures of about 20 to 100 bar (2 MPa to 10 MPa), and at a temperature between 150 ° C and 300 ° C, preferably 200 ° C to 250 ° C, with a zeolitic oligomerization catalyst.
[0085] The reactor model may also comprise a catalyst regenerator for receiving deactivated or spent catalyst from the oligomerization reactor. The catalyst regenerator for catalyst regeneration can operate at relatively low pressures from 1 to 5 bar (0.5 MPa), typically from 1 to 2 bar (0.1 to 0.2 MPa) and at temperatures of around 500 ° C to 1000 ° C, typically 500 ° C to 550 ° C, to burn out the coke or hydrocarbon encrustations from the catalyst. Air or oxygen can be introduced into the catalyst regenerator to allow any coke, carbon, or other deposits on the deactivated catalyst to be oxidized, thereby regenerating the catalyst for later use in the reaction process.
[0086] In one embodiment, the regeneration reactor receives the deactivated catalyst from the oligomerization reactor. The deactivated catalyst can be removed using known means for removing a catalyst from a reactor vessel. In one embodiment, the deactivated catalyst can be removed from the oligomerization reactor using a pressure reduction system to take the catalyst from the relatively high operating pressure of the oligomerization reactor down to the relatively low operating pressure of the regenerator. of catalyst. The pressure reduction system may include a blocking funnel and a disengaging funnel, as is known to a person skilled in the art to isolate the high pressure of the reactor from the low pressure of the catalyst regenerator.
[0087] Once the catalyst has been regenerated, the regenerated catalyst can be transferred to the oligomerization reactor using known means for transporting a catalyst to a reactor vessel. In one embodiment, the regenerated catalyst can be transported to the inlet of the oligomerization reactor using a pressurization system to increase the pressure of the regenerated catalyst, before introducing the regenerated catalyst into the oligomerization reactor. The pressurization system may include a regenerated catalyst current control system that is configured for safe catalyst operation, a blocking funnel, and increasing pressure means, for example, a Venturi compressor, a mechanical compressor, or the like, to introduce the pressurized regenerated catalyst stream into the oligomerization reactor.
[0088] The resulting oligomerization stream results in a fuel mixture that can have a wide variety of products including products comprising C5 to C24 hydrocarbons. Additional processing can be used to obtain a fuel mixture meeting a desired standard. An initial separation step can be used to generate a fuel mixture with a narrower range of carbon numbers. In one embodiment, a separation process, such as a distillation process, is used to generate a fuel mixture comprising C12 to C24 hydrocarbons for further processing. The remaining hydrocarbons can be used to produce a fuel mixture for gasoline, recycled to the oligomerization reactor, or used in additional processes. For example, a kerosene fraction can be derived, along with the diesel fraction, and can be used as a lighting paraffin, as a jet fuel mixture component in conventional crude or synthetic derived jet fuels, or as a reagent (especially fraction C10-C13) in the process to produce LAB (Linear Alkyl Benzene). The naphtha fraction after hydroprocessing can be sent to a thermal cracker for the production of ethylene and propylene or sent as it is to a catalytic cracker for the production of ethylene, propylene and gasoline.
[0089] Additional processes can be used to treat the fuel mixture to remove certain components or further conform the fuel mixture to a diesel or jet fuel standard. Suitable techniques may include hydrotreating to remove any oxygen, sulfur, or nitrogen remaining in the fuel mixture. Hydrogenation can be carried out after the hydrotreating process to saturate at least some olefinic bonds. Such hydrogenation can be carried out to conform the fuel mixture to a specific fuel pattern (for example, a diesel fuel pattern or a jet fuel pattern). The hydrogenation step of the fuel mixture stream can be carried out according to known procedures, either with the continuous or batch method. In particular, it can be carried out by feeding hydrogen at a pressure ranging from 5 bar (0.5 MPa) to 20 bar (2 MPa) and at a temperature ranging from 50 ° C to 150 ° C and reacting for a time ranging from 2 to 20 hours in the presence of a hydrogenation catalyst such as a supported palladium or platinum catalyst, for example 5% by weight of palladium or platinum on activated carbon.
[0090] Isomerization can be used to treat the fuel mixture to introduce a desired degree of branching or other form of selectivity for at least some components in the fuel mixture. It can be useful to remove any impurities before the hydrocarbons are contacted with the isomerization catalyst. The isomerization step comprises an optional extraction step, in which the fuel mixture from the oligomerization reaction can be purified by extraction with water vapor or a suitable gas, such as light hydrocarbons, nitrogen or hydrogen. The optional extraction step is carried out in the form of counter-current in a unit upstream of the isomerization catalyst, in which the gas and liquid are contacted with each other, or before the effective isomerization reactor of a separate extraction unit. using counter-current principle.
[0091] After the optional extraction step the fuel mixture can be passed to a reactive isomerization unit that comprises one or more catalyst bed (s). The catalyst beds of the isomerization step can operate either in co-current or counter-current form. In the isomerization step, the pressure can vary from 20 bar to 150 bar (2 MPa to 15 MPa), preferably in the range of 20 bar to 100 bar (2 MPa to 10 MPa), the temperature being between 200 ° C and 500 ° C, preferably between 300 ° C and 400 ° C. In the isomerization step, any isomerization catalysts known in the art can be used. Suitable isomerization catalysts can contain molecular sieves and / or a Group VII metal and / or a vehicle. In one embodiment, the isomerization catalyst contains SAPO-11 or SAP041 or ZSM-22 or ZSM-23 or ferrierite and Pt, Pd or Ni and A12O3 or SiO2. Typical isomerization catalysts are, for example, Pt / SAPO-11 / Al2O3, Pt / ZSM-22 / Al2O3, Pt / ZSM-23 / Al2O3e Pt / SAPO-11 / SiO2.
[0092] Thus, in one embodiment, the fuel mixture produced by the processes described here is a hydrocarbon mixture that meets the requirements for jet fuel (that is, it complies with ASTM D1655). In another embodiment, the product of the processes described herein is a mixture of hydrocarbons which comprises a fuel mixture that satisfies the requirements for a diesel fuel (that is, it complies with ASTM D975).
[0093] Methods and systems for the production of higher hydrocarbons and / or a fuel mixture from biobased feed loads may have an increased relative fuel efficiency compared to other processes for converting biobased feed loads. As used herein, the term "relative fuel yield" takes into account the percentage of carbon atoms that are extracted as carbohydrates, exclusive of lignins, from a biobased feed charge that are present in the higher hydrocarbons produced as a product on a molar basis. The relative fuel yield is relative to the yield obtained from feeding an amount of sorbitol equivalent to the total amount of carbohydrates extracted from the feed charge based on a carbon base for the processing reaction. The relative fuel yield can be calculated by dividing the total amount of carbon present in the upper hydrocarbons formed from the process by the total amount of carbon present in the upper hydrocarbons obtained from the sorbitol feed in the processing reaction. The total mass of carbon in the upper hydrocarbons can be directly measured at the output of the fuel processing reaction (for example, the hydrogenation reaction, the condensation reaction, the oligomerization reaction) or at any point where the upper hydrocarbons are ready to get out of the process.
[0094] In an embodiment of the present invention, the relative fuel efficiency of the current process can be greater than other biobased feed charge conversion processes. Without wishing to be limited by theory, it is believed that the use of a multi-temperature hydrolysis reaction process, together with the direct APR of the extracted compounds allows a higher percentage of biobased feed load to be converted into higher hydrocarbons, while limits the formation of degradation products. In one embodiment, the relative fuel efficiency of the process can be greater than or equal to 60%, or, alternatively, greater than or equal to 70%.
[0095] To facilitate a better understanding of the present invention, the following examples of certain aspects of some embodiments are given. In no way should the following examples be read to limit, or define, the entire scope of the invention. EXAMPLES Aqueous phase reform experiments
[0096] Direct aqueous phase reforming (APR) experiments were conducted in 100 ml reactors stirred with suction tube induction gas impeller (Parr series 4590). Reaction tests for reforming the direct biobased feed load involved filling the reactor with 60 grams of solvent (deionized water, or a mixture of DI water and isopropanol (IPA), and 3 - 3.5 grams of biobased feed load comprising biomass (bagasse, or pine sawdust)). One gram (1) of acetic acid was optionally loaded to facilitate hydrolysis of the biomass.
[0097] The bagasse was ground through a 1 mm grid. Dehulled, dried Loblolly pine was milled through a mixer (Thomas Scientific) and sieved to less than 30 mesh. Fraction of dry solids was determined by vacuum drying at 80 ° C - 82 ° C. One gram of aqueous phase of reforming catalyst (5% Pt / C catalyst reduced to 50% moisture, or 1.9% powdered Pt / Al2 O3) was loaded into the reactor, which was loaded with 600 psi (4.1 MPa) of hydrogen or nitrogen. To minimize hydrolyzate degradation for heavy end products, each reactor was typically heated with a one hour step temperature sequence at 160 ° C, 190 ° C, 225 ° C, and finally 250 ° C, before leaving for the entire the night to the final set point,
[0098] Comparison tests were also performed with glucose or sorbitol fed directly to the reaction in place of biomass, to simulate and quantify the conversion of hydrolyzate from model to APR intermediates. Glucose is one of the sugars readily leached from biomass in hot water, while sorbitol is readily formed through glucose hydrogenation, where platinum or other catalysts capable of hydrogenation are present.
[0099] A batch reaction time of 20 hours under these conditions corresponds to an hourly space velocity in weight (g- feed / g-catalyst / h) of about 3, by a comparable direct current reactor. A 0.5 micron sintered metal filter attached to an immersion tube allowed liquid samples to be taken over the course of the reaction, without loss of biomass or catalyst.
[00100] The samples were analyzed by an HPLC method based on the size and combined ion exclusion chromatography, to determine unreacted sorbitol, and the amount of C3 and minor polyols formed: glycerol (Gly), ethylene glycol (EG) , and 1,2-propylene glycol (PG). Additional GC analysis through a moderate DB-5 column polarity was performed to assess the formation of C6 and lighter oxygenates (ketones, aldehydes, alcohols). A separate GC equipped with thermal conductivity and flame ionization (FID) detectors for refinery gas analysis was used for the detection of H2, CO2, and light C1-C5 alkanes. GC mass spec was used to characterize mixtures of selected APR reaction products. Table 1 lists the compounds identified in the aqueous phase after reforming sorbitol in the aqueous phase.
[00101] While oxygenates formed during APR can be mixed with the fuel, condensation on a strong acid catalyst produces a direct mixture suitable for gasoline. Zeolite ZSM-5 provides a rich blend of aromatics. Effectiveness of the initial APR step can be assessed by passing the APR reaction product over ZSM-5, to characterize the performance of components in the gasoline range. These tests were conducted through a pulse micro-reactor formed through a GC injector package of 0.05 grams of ZSM-5 acid condensation catalyst, and maintained at 375 ° C. A microliter of the APR reactor product was injected into the catalyst bed, to examine the formation of liquid fuel products. The catalytic injector insert was followed by GC Restek Rtx-1701 and DB-5 capillarity columns in series, to solve hydrocarbon and aromatic reaction components through the analysis of the programmed temperature.
[00102] A flame ionization sensitive mass detector (FID) was used for analysis to characterize the yields, such that the GC areas for the aromatic hydrocarbon and alkane products of the condensation step, can be related to the amount of carbon loaded as “feed” for the reform phase of the aqueous phase. A comparison run (example 3) was performed with 25% by weight of sorbitol as the feed for APR, where sorbitol represents the completely hydrolyzed and hydrogenated C6 sugar that can be extracted from the biomass. Total mass of alkane products and liquid aromatics formed through acid condensation following the APR reaction with sorbitol as a feed, as indicated by the total area of the FID response, in relation to the% by weight of C loaded as a sorbitol feed, was a fuel / bio-carbon efficiency value of 1.0 is assigned. Fuel yields per% by weight of C loaded as food were also calculated from the FID response of the pulse condensation micro-reactor, for runs and using biomass as feed. Examples 1 to 3 Direct aqueous phase reform of bagasse
[00103] APR batch reactions with bagasse as food, and with a comparison of 25% sorbitol as food, were performed as described above. 1.7% acetic acid was added to simulate the catalysis of hydrolysis by recycling acid. Products formed from this concentration of acetic acid were subtracted from the formation of the total product, to calculate the net production of liquid fuels from bagasse.
[00104] For Example 1, the yield of liquid fuel products (per unit% by weight of C) was observed to increase when the temperature was increased in phase form through the sequence of 160, 190, and 225 ° C. An additional increase in temperature with heating over night to allow for a slight decrease in the yield by carbon fed. Total bagasse yields were calculated as 82% of yield / C, obtained with the model compound of sorbitol as food (example 3). This compares favorably with the hydrolyzable fraction of 77% dry bagasse, which contains 20% lignin and 3% ash. Thus, results indicate that all the sugar precursors present in the bagasse were hydrolyzed, and selectively converted to liquid biofuel.
[00105] Example 2 examined the yields for a similar experiment in which the hydrolysis of hot water plus acetic acid was conducted first, without the combined presence of APR Pt / C catalyst. While a small yield / C was obtained by following thermal contact at 225 ° C in example 2A, the yield obtained from acid condensation decreased after additional heating at 250 ° C, in the absence of catalyst (Example 2B). Pt / C catalyst was then added to the resulting liquid, for example 2C, to effect the reforming of the hydrolyzate aqueous phase from the initial heating step. The yields / C were lower than those obtained from the 1.7% acetic acid added as a hydrolysis catalyst, when the resulting liquid was pulsed over ZSM-5 condensation catalyst.
[00106] This result shows the critical importance of APR reaction combined with biomass hydrolysis. In the absence of reform of the combined aqueous phase, the hydrolyzate undergoes irreversible degradation (presumably for heavy end products), and cannot be reverted to liquid fuels over subsequent APR and condensation.

[00107] Table 2 shows the selectivity for alkanes and aromatics following condensation on ZSM-5, for the examples in table 1. The mixture is considered suitable for mixing with gasoline.

[00108] Characterization of the intermediates formed from the APR step of example 3a is given in table 3. APR of sugar or alcohol sugar results in a large number of mono-, di-, and tri-oxygenated compounds, including acids carboxylic acids, which cause a drop in pH to about 3.5-4.0. These acids can catalyze the hydrolysis of biomass, on recycling the reaction mixture.

Examples 4-12
[00109] Table 4 shows direct biomass of APR and hydrogenation experiments with bagasse as a feed load. Acetic acid and isopropanol (IP A) were added to simulate bioforming intermediates that are known to assist in biomass hydrolysis and solubilization. At the end of these experiments, the reaction mixture was filtered over Whatman # 2 filter paper to recover catalyst and undigested bagasse, from which a percentage of "digested" can be calculated. As used herein, "digested" means soluble enough to pass through Whatman # 2 filter paper after cooling to room temperature.
[00110] The minimum “digested” bagasse was 70.9%, and in many cases, the digested bagasse approached 100%. The filtered samples were not analyzed for ash content for the current experiments. The extent to which the addition of acetic acid may have solubilized salts such as acetate is unknown. Certainly, digestion greater than 70% indicates the solubilization of lignin, which IPA was expected to be added as an initial solvent. Light alcohols capable of solubilizing lignins were also generated during APR of sugars or sugar alcohols.


[00111] Both ruthenium hydrogenation catalyst and APR platinum catalysts were used. For ruthenium, the expected route is one of hydrogenation of hydrolyzed biomass to form sugar alcohols at temperatures below 200 ° C, and even more hydrogenolysis to form polyols such as ethylene glycol (EG or MEG for "mono"), propylene glycol (PG or MPG), glycerol, or even isosorbide through dehydration. For APR, the reaction products were reformed by platinum to give smaller molecular weight species liable to condensation of liquid hydrocarbon fuels. Where IPA was added at 50%, solutions remained crystalline with a yellow color for weeks of storage. Where IPA was not added, the solutions flocculate and precipitate over a period of time (days). The black precipitate formed at the bottom of the sample vials as it was more dense than water. All solutions that were sampled via the immersion tube with a 5 micron filter. The addition of IPA, acetic acid, and catalyst generally increased the extent of digestion per unit time. Very high digestion was carried out through the use of catalyst together with acetic acid, or with a combination of IPA / acetic acid without catalyst.
[00112] Therefore, the invention is well adapted to achieve the mentioned purposes and advantages, as well as those that are inherent. The particular embodiments disclosed above are illustrative only, as the invention can be modified and practiced in different ways, but equivalent ways evident to those skilled in the art having the benefit of the teachings here. In addition, without limitation they are intended for the details of construction or design shown here, except as described in the claims below. Therefore, it is evident that the particular illustrative embodiments described above can be altered or modified and all variations are considered within the scope and spirit of the invention. While compositions and methods are described in terms of "comprising", "containing", or "including" various components or steps, compositions and methods may also "essentially consist of, or" consist of "various components and steps. All figures and variations described above may vary by a certain amount. Whenever a numerical range with a lower limit and an upper limit is disclosed, any number and any variation included falling within the variation is specifically disclosed. In particular, the entire range of values (of the form, “from about aa to b”, or, equivalently, “from approximately a to b,” or, equivalently, “from approximately to ab”) disclosed herein is to be understood as established for each number and range encompassed within a broader range of values. In addition, the terms of the claims have their clear and ordinary meaning, unless otherwise explicitly and clearly defined by the patent holder. In addition, the indefinite articles "a" mean one or more of the element that it introduces. If there is any conflict in the uses of a word or term in this report and one or more patents or other documents that may be incorporated herein by reference, definitions that are consistent with this report must be adopted. Example 13
[00113] The 100 ml batch reactor was loaded with 28.28 grams of isopropanol (IPA), 28.41 grams of deionized water, 1.018 grams of acetic acid, 0.995 grams of Pt / C catalyst 5% APR, and 3,478 grams of 1 micron of ground bagasse of 4.7% moisture. The reactor was heated with stirring to 175 ° C, 200 ° C, 225 ° C, and finally 250 ° C for 1.5 hour increments, before leaving overnight (23 hours in total). Samples of liquid phase and gas were taken, before cooling to add an additional amount of pine sawdust (3.51, 3.20, 2.99, and 2.95 grams), for 4 additional cycles. Cumulative addition after five cycles corresponded to 21.1% by weight of adding solids to the final reactor mixture. Staging the addition of biomass solids, a sludge of moderate viscosity with free liquid was maintained.
[00114] Recovery of undigested solids by filtration indicated that 94% of the bagasse's dry solids had been converted to liquid products and / or solubilized in the reaction mixture. A GC analysis of both the oil and aqueous phases indicated an estimated 11% by weight of the liquid product formation in relation to a maximum expected value of 9.1% based on the carbon content of the loaded feed. The observed liquid products were more volatile than sorbitol, the basis of GC retention times. The experience demonstrates the ability to solubilize and reform biomass via direct APR, to obtain intermediate concentrations in excess of 5% by weight, as required for economical processing in subsequent condensation reactions. Example 14
[00115] The 100 ml batch reactor was loaded with 30.182 g of isopropanol (IPA) and 30.069 grams of deionized water. 1.0515 grams of acetic acid were added as a simulated recycle hydrolysis catalyst. 1.0505 grams of 5% Pt / C APR (50% wet) were also loaded. 3.53 grams of Loblolly pine (<30 mesh, 18% humidity) was loaded for an initial cycle, along with 87 kPa of H2. The reactor was heated with stirring to 175 ° C, 200 ° C, 225 ° C, and finally 250 ° C for 1.5 hour increments, before leaving overnight (23 hours in total). The liquid phase and gas samples were taken before cooling to add an additional amount of pine sawdust (3.47, 3.48, 3.50, and 3.51 grams), for an additional 4 cycles. Cumulative addition after five cycles corresponded to 22.9% by weight of dry solids added to the final reactor mixture. Staging the addition of biomass solids, a sludge of moderate viscosity with free liquid was maintained.
[00116] Recovery of undigested solids by filtration indicated that 78% of dry pine solids had been converted to liquid products. An analysis by CG of the liquid phase found that 5.9% by weight of liquid products formed with retention times shorter than that of sorbitol, in relation to a maximum of 7.6% by weight possible from carbon present in the food, the this conversion. These results show an ability to hydrolyze and reform softwood (pine) to liquid (oxygenated) fuels, to obtain a concentration greater than 5 percent by weight, as desired for separation and use as a fuel additive, or for economical processing additional through condensation for liquid fuels.

权利要求:
Claims (16)
[0001]
1. Method for providing a biobased feed load, characterized by the fact that it comprises: providing a biobased feed load; contacting the feed charge biobased with a solvent in a hydrolysis reaction to form an intermediate stream comprising carbohydrates; contacting the intermediate stream with an aqueous phase reforming catalyst to form a plurality of oxygenated intermediates, wherein a first portion of the oxygenated intermediates are recycled to form the solvent; and processing at least a second portion of the oxygenated intermediates to form a fuel mixture.
[0002]
Method according to claim 1, characterized in that the fuel mixture comprises at least one composition selected from a fuel additive, a gasoline fuel, a diesel fuel, or a jet fuel.
[0003]
Method according to claim 1, characterized in that the processing of at least a second portion of the oxygenated intermediates comprises contacting at least a second portion of the oxygenated intermediates with a hydrogenation catalyst to form the fuel mixture.
[0004]
Method according to any one of claims 1 to 3, characterized in that the fuel mixture comprises at least one additive selected from the group consisting of: a saturated alcohol, a saturated polyol, and a saturated hydrocarbon.
[0005]
Method according to claim 1, characterized in that the processing of at least a second portion of the oxygenated intermediates comprises contacting at least a second portion of the oxygenated intermediates with a condensation catalyst to form the fuel mixture, wherein the fuel mixture comprises a gasoline fuel.
[0006]
Method according to claim 1, characterized in that the processing of at least a second portion of the oxygenated intermediates comprises contacting at least a second portion of the oxygenated intermediates with an acid catalyst to form at least some olefins; and contacting the olefins with an oligomerization catalyst to form the fuel mixture.
[0007]
Method according to any one of claims 1 to 6, characterized by the fact that and the formation of the upper hydrocarbons from the biobased feed charge has a ratio of liquid fuel in relation to at least 70%.
[0008]
Method according to any one of claims 1 to 7, characterized in that the intermediate carbohydrate stream has a carbohydrate content of less than 5% at the exit of the hydrolysis reaction.
[0009]
Method according to any one of claims 1 to 8, characterized in that the intermediate stream has a total organic content on a weight basis, and in which the total organic content of the intermediate stream is greater than 2%.
[0010]
Method according to claim 1, characterized in that it additionally comprises contacting the biobased feed charge with a hydrolysis catalyst in the hydrolysis reaction, wherein the hydrolysis catalyst comprises at least one catalyst selected from the group consisting of from: an acid catalyst, a basic catalyst, a metal catalyst, acetic acid, formic acid, and levulinic acid, and in any combination thereof.
[0011]
11. Method according to claim 1, characterized by the fact that it comprises: providing a biobased feed load; contacting the biobased feed charge with a hydrolysis catalyst and a solvent to form an intermediate stream comprising carbohydrates; contacting at least a portion of the intermediate stream with a hydrogenolysis catalyst in the presence of the first hydrogen source to form at least some hydrogenolysis reaction products; contacting at least a portion of the intermediate stream with a hydrogenation catalyst in the presence of the second hydrogen source to form at least some products of the hydrogenation reaction; contacting at least a portion of the intermediate stream with an aqueous phase reforming catalyst to form a product of the aqueous phase reforming reaction; wherein at least a portion of the hydrogenolysis reaction products, at least a portion of the hydrogenation reaction products, and at least a portion of the aqueous phase reform reaction products are combined to form a plurality of oxygenated intermediates, wherein a first portion of the oxygenated intermediates are recycled to form the solvent; and processing at least a second portion of the oxygenated intermediates to form a fuel mixture.
[0012]
12. Method according to claim 11, characterized in that the products of the aqueous phase reform reaction comprise hydrogen, and in which hydrogen is the first source of hydrogen, the second source of hydrogen, or both.
[0013]
Method according to claim 11, characterized in that the hydrogenolysis catalyst, the hydrogenation catalyst, and the aqueous phase reforming catalyst are the same catalyst.
[0014]
Method according to any one of claims 11 to 13, characterized in that the processing of at least a second portion of the oxygenated intermediates comprises contacting at least a second portion of the oxygenated intermediates with a hydrogenation catalyst to form the fuel mixture, wherein the fuel mixture comprises a fuel additive.
[0015]
Method according to any one of claims 11 to 13, characterized in that the processing of at least a second portion of the oxygenated intermediates comprises contacting at least a second portion of the oxygenated intermediates with a condensation catalyst to form the fuel mixture, wherein the fuel mixture comprises a gasoline fuel.
[0016]
Method according to any one of claims 11 to 13, characterized in that the processing of at least a second portion of the oxygenated intermediates comprises contacting at least a second portion of the oxygenated intermediates with an acid catalyst to form at least some olefins; and contacting the olefins with an oligomerization catalyst to form the fuel mixture, wherein the fuel mixture comprises at least one fuel selected from the group consisting of a diesel fuel, a jet fuel, and any combination thereof.

类似技术:

---

公开号 | 公开日 | 专利标题

---

BR112012016143B1|2021-03-09|method for providing a biobased feed load

---

US9944869B2|2018-04-17|Synthesis of liquid fuels and chemicals from oxygenated hydrocarbons

---

US9493719B2|2016-11-15|Biofuels via hydrogenolysis-condensation

---

US9428704B2|2016-08-30|Direct aqueous phase reforming and aldol condensation to form bio-based fuels

---

EP2061860B1|2013-12-18|Synthesis of liquid fuels and chemicals from oxygenated hydrocarbons

---

BR112014014640B1|2021-03-02|method to provide a biomass conversion system, and, biomass conversion system

---

ES2847303T3|2021-08-02|Method and systems for the preparation of distillate fuels from biomass

同族专利:

---

公开号 | 公开日

---

CA2785012A1|2011-07-07|

---

AU2010336999B2|2014-03-27|

---

BR112012016143B8|2021-04-20|

---

CA2785012C|2018-02-20|

---

CN102712851B|2015-02-25|

---

EP2519606A1|2012-11-07|

---

US9447349B2|2016-09-20|

---

CN102712851A|2012-10-03|

---

WO2011082000A1|2011-07-07|

---

BR112012016143A2|2020-07-28|

---

AU2010336999A1|2012-07-19|

---

US20110154722A1|2011-06-30|

---

US20130199085A1|2013-08-08|

---

PL2519606T3|2018-11-30|

---

EP2519606B1|2018-07-04|

---

US9303226B2|2016-04-05|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

US4013734A|1973-12-14|1977-03-22|Exxon Research And Engineering Company|Novel catalyst and its use for steam hydroconversion and dealkylation processes|

---

US4174976A|1978-03-08|1979-11-20|Purdue Research Foundation|Acid hydrolysis of cellulose to yield glucose|

---

US4223001A|1978-06-20|1980-09-16|Allied Chemical Corporation|Production of hydrogen from carbon monoxide and water|

---

US4401823A|1981-05-18|1983-08-30|Uop Inc.|Hydrogenolysis of polyhydroxylated compounds|

---

US4382150A|1982-01-19|1983-05-03|Uop Inc.|Method for hydrogenating aqueous solutions of carbohydrates|

---

US4487980A|1982-01-19|1984-12-11|Uop Inc.|Method for hydrogenating aqueous solutions of carbohydrates|

---

US4380679A|1982-04-12|1983-04-19|Uop Inc.|Hydrogenation of saccharides|

---

US4380680A|1982-05-21|1983-04-19|Uop Inc.|Method for hydrogenating aqueous solutions of carbohydrates|

---

US4541836A|1982-12-09|1985-09-17|Union Carbide Corporation|Fuel compositions|

---

US4456779A|1983-04-26|1984-06-26|Mobil Oil Corporation|Catalytic conversion of olefins to higher hydrocarbons|

---

US4503274A|1983-08-08|1985-03-05|Uop Inc.|Ruthenium hydrogenation catalyst with increased activity|

---

US4554260A|1984-07-13|1985-11-19|Exxon Research & Engineering Co.|Two stage process for improving the catalyst life of zeolites in the synthesis of lower olefins from alcohols and their ether derivatives|

---

AU576030B2|1984-12-31|1988-08-11|Mobil Oil Corporation|Process for producing high boiling jet fuel|

---

US4543435A|1985-01-17|1985-09-24|Mobil Oil Corporation|Multistage process for converting oxygenates to liquid hydrocarbons with ethene recycle|

---

GB8511587D0|1985-05-08|1985-06-12|Shell Int Research|Producing hydrocarbon-containing liquids|

---

US5019135A|1987-10-13|1991-05-28|Battelle Memorial Institute|Method for the catalytic conversion of lignocellulosic materials|

---

US5001292A|1987-12-08|1991-03-19|Mobil Oil Corporation|Ether and hydrocarbon production|

---

US4885421A|1987-12-08|1989-12-05|Harandi Mohsen N|Multistage reactor system for production of fuels|

---

US4919896A|1987-12-28|1990-04-24|Mobil Oil Corporation|Multistage catalytic reactor system for production of heavy hydrocarbons|

---

US4828812A|1987-12-29|1989-05-09|Mobil Oil Corporation|Titanosilicates of enhanced ion exchange capacity and their preparation|

---

US5180868A|1988-06-20|1993-01-19|Battelle Memorial Institute|Method of upgrading oils containing hydroxyaromatic hydrocarbon compounds to highly aromatic gasoline|

---

US4935568A|1988-12-05|1990-06-19|Mobil Oil Corporation|Multistage process for oxygenate conversion to hydrocarbons|

---

US5130101A|1989-04-28|1992-07-14|Mobil Oil Corporation|Reactor system for conversion of alcohols to ether-rich gasoline|

---

US5105044A|1989-12-29|1992-04-14|Mobil Oil Corp.|Catalyst and process for upgrading methane to higher hydrocarbons|

---

US5238898A|1989-12-29|1993-08-24|Mobil Oil Corp.|Catalyst and process for upgrading methane to higher hydrocarbons|

---

US5180681A|1990-03-15|1993-01-19|North Carolina State University|Method of making high current, high voltage breakdown field effect transistor|

---

US5177279A|1990-10-23|1993-01-05|Mobil Oil Corporation|Integrated process for converting methanol to gasoline and distillates|

---

US5139002A|1990-10-30|1992-08-18|Hydrogen Consultants, Inc.|Special purpose blends of hydrogen and natural gas|

---

US5344849A|1990-10-31|1994-09-06|Canada Chemical Corporation|Catalytic process for the production of hydrocarbons|

---

US5095159A|1990-11-21|1992-03-10|Mobil Oil Corporation|Ether and hydrocarbon production|

---

JPH08501115A|1992-06-05|1996-02-06|バッテル・メモリアル・インスティチュート|Method for catalytically converting organic materials to product gases|

---

JP2874550B2|1994-04-21|1999-03-24|日本電気株式会社|Semiconductor integrated circuit device|

---

WO1995030825A1|1994-05-04|1995-11-16|University Of Central Florida|Hydrogen-natural gas motor fuel|

---

US5666923A|1994-05-04|1997-09-16|University Of Central Florida|Hydrogen enriched natural gas as a motor fuel with variable air fuel ratio and fuel mixture ratio control|

---

JP2671944B2|1994-08-25|1997-11-05|工業技術院長|Method for producing hydrogen from cellulosic biomass|

---

US5578647A|1994-12-20|1996-11-26|Board Of Regents, The University Of Texas System|Method of producing off-gas having a selected ratio of carbon monoxide to hydrogen|

---

US5837506A|1995-05-11|1998-11-17|The Trustee Of Dartmouth College|Continuous process for making ethanol|

---

US5787863A|1996-01-23|1998-08-04|Caterpillar Inc.|Fuel system having priming actuating fluid accumulator|

---

BR9600672A|1996-03-08|1997-12-30|Dedini S A Administracao E Par|Acid hydrolysis process of lignocellulosic material and hydrolysis reactor|

---

US6022419A|1996-09-30|2000-02-08|Midwest Research Institute|Hydrolysis and fractionation of lignocellulosic biomass|

---

US5861137A|1996-10-30|1999-01-19|Edlund; David J.|Steam reformer with internal hydrogen purification|

---

US5977013A|1996-12-19|1999-11-02|Battelle Memorial Institute|Catalyst and method for aqueous phase reactions|

---

US5916780A|1997-06-09|1999-06-29|Iogen Corporation|Pretreatment process for conversion of cellulose to fuel ethanol|

---

DE19725009C1|1997-06-13|1999-03-04|Dbb Fuel Cell Engines Gmbh|Process for treating a methanol reforming catalyst|

---

DE19725006C2|1997-06-13|1999-04-29|Dbb Fuel Cell Engines Gmbh|Methanol reforming reactor and treatment process for a catalyst therefor|

---

US6043392A|1997-06-30|2000-03-28|Texas A&M University System|Method for conversion of biomass to chemicals and fuels|

---

US5959167A|1997-08-25|1999-09-28|The University Of Utah Research Foundation|Process for conversion of lignin to reformulated hydrocarbon gasoline|

---

CN1502547A|1997-10-07|2004-06-09|Jfe控股公司|Catalyst for manufacturing hydrogen or synthesis gas and manufacturing method of hydrogen or synthesis gas|

---

DE69925052T2|1998-01-21|2006-03-02|Haldor Topsoe A/S|Process for producing hydrogen-rich gas|

---

JPH11217343A|1998-01-30|1999-08-10|Sangi Co Ltd|Synthesis of chemical industrial feedstock and high-octane fuel|

---

US6054041A|1998-05-06|2000-04-25|Exxon Research And Engineering Co.|Three stage cocurrent liquid and vapor hydroprocessing|

---

GR1003235B|1998-05-22|1999-10-13|Ξενοφων Βερυκιος|Process for the production of hydrogen and electricity generation by bio-ethanol reforming with the use of fuel cells and without emission of pollutants|

---

DE69927032T2|1998-06-09|2006-03-02|Idemitsu Kosan Co. Ltd.|METHOD FOR AUTOTHERMIC REFORMATION OF A HYDROCARBON INGREDIENT|

---

US6479428B1|1998-07-27|2002-11-12|Battelle Memorial Institute|Long life hydrocarbon conversion catalyst and method of making|

---

US6440895B1|1998-07-27|2002-08-27|Battelle Memorial Institute|Catalyst, method of making, and reactions using the catalyst|

---

US6172272B1|1998-08-21|2001-01-09|The University Of Utah|Process for conversion of lignin to reformulated, partially oxygenated gasoline|

---

US6207132B1|1998-12-04|2001-03-27|Chinese Petroleum Corporation|Process for producing high purity hydrogen|

---

US7273957B2|1999-05-04|2007-09-25|Catalytic Distillation Technologies|Process for the production of gasoline stocks|

---

EP1063011B1|1999-05-22|2001-12-12|OMG AG & Co. KG|Use of a catalyst for the steam reforming of methanol|

---

US20020020107A1|1999-07-02|2002-02-21|Bailey Brent K.|Low molecular weight compression ignition fuel|

---

US6372680B1|1999-07-27|2002-04-16|Phillips Petroleum Company|Catalyst system for converting oxygenated hydrocarbons to aromatics|

---

US6969506B2|1999-08-17|2005-11-29|Battelle Memorial Institute|Methods of conducting simultaneous exothermic and endothermic reactions|

---

US6570043B2|1999-09-03|2003-05-27|Battelle Memorial Institute|Converting sugars to sugar alcohols by aqueous phase catalytic hydrogenation|

---

US6235797B1|1999-09-03|2001-05-22|Battelle Memorial Institute|Ruthenium on rutile catalyst, catalytic system, and method for aqueous phase hydrogenations|

---

US6291725B1|2000-03-03|2001-09-18|Board Of Trustees Operating Michigan State University|Catalysts and process for hydrogenolysis of sugar alcohols to polyols|

---

US6508209B1|2000-04-03|2003-01-21|R. Kirk Collier, Jr.|Reformed natural gas for powering an internal combustion engine|

---

US6397790B1|2000-04-03|2002-06-04|R. Kirk Collier, Jr.|Octane enhanced natural gas for internal combustion engine|

---

US7029506B2|2000-04-14|2006-04-18|Jordan Frederick L|Organic cetane improver|

---

WO2002051779A2|2000-12-23|2002-07-04|Degussa Ag|Method for producing alcohols by hydrogenating carbonyl compounds|

---

US6765101B1|2001-05-01|2004-07-20|Union Carbide Chemicals & Plastics Technology Corporation|Synthesis of lower alkylene oxides and lower alkylene glycols from lower alkanes and/or lower alkenes|

---

DE10128203A1|2001-06-11|2002-12-12|Basf Ag|Production of sorbitol a ruthenium catalyst prepared by impregnation of an amorphous silicon dioxide support material and drying followed by immediate hydrogen reduction.|

---

US6670300B2|2001-06-18|2003-12-30|Battelle Memorial Institute|Textured catalysts, methods of making textured catalysts, and methods of catalyzing reactions conducted in hydrothermal conditions|

---

US6607707B2|2001-08-15|2003-08-19|Ovonic Battery Company, Inc.|Production of hydrogen from hydrocarbons and oxygenated hydrocarbons|

---

US20030115792A1|2001-10-05|2003-06-26|Shabtai Joseph S|Process for converting lignins into a high octane blending component|

---

US20030100807A1|2001-10-05|2003-05-29|Shabtai Joseph S|Process for converting lignins into a high octane additive|

---

US6841085B2|2001-10-23|2005-01-11|Battelle Memorial Institute|Hydrogenolysis of 6-carbon sugars and other organic compounds|

---

US6479713B1|2001-10-23|2002-11-12|Battelle Memorial Institute|Hydrogenolysis of 5-carbon sugars, sugar alcohols, and other methods and compositions for reactions involving hydrogen|

---

WO2003045841A1|2001-11-29|2003-06-05|Wisconsin Alumni Research Foundation|Low-temperature hydrogen production from oxygenated hydrocarbons|

---

US6699457B2|2001-11-29|2004-03-02|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|

---

US6739125B1|2002-11-13|2004-05-25|Collier Technologies, Inc.|Internal combustion engine with SCR and integrated ammonia production|

---

US7199250B2|2002-12-20|2007-04-03|Battelle Memorial Institute|Process for producing cyclic compounds|

---

US6982328B2|2003-03-03|2006-01-03|Archer Daniels Midland Company|Methods of producing compounds from plant material|

---

US20050203195A1|2003-08-05|2005-09-15|Yong Wang|Tailored Fischer-Tropsch synthesis product distribution|

---

FR2867464B1|2004-03-10|2006-06-09|Inst Francais Du Petrole|PROCESS FOR PRODUCING HIGH-PURITY HYDROGEN FROM ALCOHOLS COMPRISING AT LEAST TWO ATOMS OF CARBON|

---

CA2567708A1|2004-06-03|2005-12-22|Charles J. Rogers|Low temperature methods for hydrogen production|

---

US20060013759A1|2004-07-13|2006-01-19|Conocophillips Company|Systems and methods for hydrogen production|

---

WO2006119357A2|2005-05-02|2006-11-09|University Of Utah Research Foundation|Processes for catalytic conversion of lignin to liquid bio-fuels|

---

US7288685B2|2005-05-19|2007-10-30|Uop Llc|Production of olefins from biorenewable feedstocks|

---

US7678950B2|2005-12-16|2010-03-16|Conocophillips Company|Process for converting carbohydrates to hydrocarbons|

---

CN101346302B|2005-12-21|2013-07-10|维仁特公司|Catalysts and methods for reforming oxygenated compounds|

---

US7615652B2|2006-01-26|2009-11-10|Battelle Memorial Institute|Two-stage dehydration of sugars|

---

US7649099B2|2006-01-26|2010-01-19|Battelle Memorial Institute|Method of forming a dianhydrosugar alcohol|

---

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|

---

EP2061860B1|2007-03-08|2013-12-18|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|

---

US7972587B2|2006-09-01|2011-07-05|Georgia Tech Research Corporation|Hydrogen production from biomass|

---

US7425657B1|2007-06-06|2008-09-16|Battelle Memorial Institute|Palladium catalyzed hydrogenation of bio-oils and organic compounds|

---

US8143469B2|2007-06-11|2012-03-27|Neste Oil Oyj|Process for producing branched hydrocarbons|

---

CN101514349B|2008-02-21|2012-01-04|中国林业科学研究院亚热带林业研究所|Method for preparing fuel ethanol from bamboo fibers|

---

US8075642B2|2008-04-14|2011-12-13|Wisconsin Alumni Research Foundation|Single-reactor process for producing liquid-phase organic compounds from biomass|

---

US7931784B2|2008-04-30|2011-04-26|Xyleco, Inc.|Processing biomass and petroleum containing materials|

---

EP2331486A2|2008-08-27|2011-06-15|Virent Energy Systems Inc.|Synthesis of liquid fuels from biomass|

---

US8697924B2|2008-09-05|2014-04-15|Shell Oil Company|Liquid fuel compositions|

---

BR112012028663A2|2010-05-12|2016-08-16|Shell Int Research|method and system|US9447347B2|2009-12-31|2016-09-20|Shell Oil Company|Biofuels via hydrogenolysis-condensation|

---

KR101933726B1|2010-04-07|2018-12-28|리셀라 피티와이 엘티디|Methods for biofuel production|

---

BR112012028438A2|2010-05-12|2016-07-19|Shell Int Research|processes for liquefying a cellulosic material to synthesize a liquefied product, and for producing a biofuel component from a cellulosic material, product, and, biofuel|

---

BR112012028765A2|2010-05-12|2016-07-19|Shell Int Research|process for liquefying a cellulosic material|

---

BR112012028663A2|2010-05-12|2016-08-16|Shell Int Research|method and system|

---

EP2721125A1|2011-06-14|2014-04-23|Shell Internationale Research Maatschappij B.V.|Hydrothermal hydrocatalytic treatment of biomass|

---

EP2748282A1|2011-10-31|2014-07-02|Shell Internationale Research Maatschappij B.V.|Process to produce biofuels via organic phase thermal hydrocatalytic treatment of biomass|

---

US20130109603A1|2011-10-31|2013-05-02|Shell Oil Company|Fuel and engine oil composition and its use|

---

CA2873298C|2012-05-17|2016-04-26|Corey William RADTKE|Process for producing volatile organic compounds from biomass material|

---

WO2013173567A1|2012-05-17|2013-11-21|Shell Oil Company|Methods and systems for processing biomass material|

---

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|

---

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|

---

WO2014070579A1|2012-10-31|2014-05-08|Shell Oil Company|Methods for hydrothermal digestion of cellulosic biomass solids using a glycerol solvent system|

---

WO2014100303A2|2012-12-19|2014-06-26|Shell Oil Company|Recyclable buffer for the hydrothermal hydrocatalytic treatment of biomass|

---

ES2864749T3|2014-05-12|2021-10-14|Katholieke Univ Leuven K U Leuven R&D|Catalytic biphasic solvent process for direct production of light naphtha from raw materials containing carbohydrates|

---

DE102018215394A1|2018-09-11|2020-03-12|Rheinisch-Westfälische Technische Hochschule Aachen|Process for the chemical conversion of sugars or sugar alcohols to glycols|

法律状态:
2020-08-11| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

---

2020-08-18| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

---

2020-12-22| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

---

2021-03-09| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 10 (DEZ) ANOS CONTADOS A PARTIR DE 09/03/2021, OBSERVADAS AS CONDICOES LEGAIS. |

---

2021-04-20| B16C| Correction of notification of the grant|Free format text: REF. RPI 2618 DE 09/03/2021 QUANTO A PRIORIDADE UNIONISTA. |

优先权:

---

申请号 | 申请日 | 专利标题

---

US29157209P| true| 2009-12-31|2009-12-31|

---

US61/291,572|2009-12-31|

---

US61/291572|2009-12-31|

---

PCT/US2010/061246|WO2011082000A1|2009-12-31|2010-12-20|Direct aqueous phase reforming of bio-based feedstocks|

---