method to provide a biomass conversion system, and, biomass conversion system

专利摘要:
METHOD FOR PROVIDING A BIOMASS CONVERSION SYSTEM AND BIOMASS CONVERSION SYSTEM. When processing cellulosic biomass, it may be desirable for a digestion unit to operate without being completely depressurized for the purposes of process efficiency. Methods for the processing of cellulosic biomass may comprise providing a biomass conversion system comprising a pressurization zone and a digestion unit that are operatively connected to each other; provide cellulosic biomass in a first pressure; introducing at least a portion of the cellulosic biomass into the pressurization zone and pressurizing the pressurization zone to a second pressure greater than the first pressure; after pressurizing the pressurization zone, transfer at least a portion of the cellulosic biomass from the pressurization zone to the digestion unit, which are at a third pressure that are less than or equal to the second pressure but greater than the first pressure; and digesting at least a portion of the cellulosic biomass in the digestion unit to produce a hydrolyzate comprising soluble carbohydrates.
公开号:BR112014014640B1
申请号:R112014014640-3
申请日:2011-12-20
公开日:2021-03-02
发明作者:Joseph Broun Powell；Thomas Lamar Flowers；Juben Nemchand Chheda
申请人:Shell Internationale Research Maatschappij B.V.；
IPC主号:

专利说明:

Field of invention
[0001] The present description generally refers to the processing of cellulosic biomass, and, more specifically, to biomass conversion systems and methods that allow cellulosic biomass solids to be added to a digestion unit operating at pressures high levels of 30 bar (3 mPa) or more. Rationale
[0002] Significant attention has been paid to the development of alternative energy sources to fossil fuels. An alternative fossil fuel that has significant potential is biomass, particularly cellulosic biomass such as, for example, plant biomass. As used here, the term "biomass" will refer to living or recently living biological material. Complex organic molecules within biomass can be extracted and broken down into simpler organic molecules, which can subsequently be processed through known chemical transformations into industrial chemicals or fuel mixtures (ie, a biofuel). Despite the potential of biomass in this regard, particularly plant biomass, a cost and energy efficient process that allows the conversion of biomass to such materials has yet to be carried out.
[0003] Cellulosic biomass is the most abundant carbohydrate source in the world due to the lignocellulosic materials located within the cell walls of higher plants. Plant cell walls are divided into two sections: primary cell walls and secondary cell walls. The primary cell wall provides structural support for cell expansion and contains 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 crosslinked polymeric lignin covalently to hemicellulose. Hemicellulose and pectin are typically found in abundance, but cellulose is the predominant polysaccharide and the most abundant source of carbohydrates. Collectively, these materials will be referred to here as "cellulosic biomass."
[0004] Plants can store carbohydrates in forms such as, for example, sugars, gums, celluloses, lignocelluloses, and / or hemicelluloses. Any of these materials can represent a raw material for conversion to industrial chemicals or fuel mixtures. Carbohydrates can include monosaccharides and / or polysaccharides. As used herein, the term "monosaccharide" refers to hydroxy aldehydes or hydroxy ketones that cannot be further hydrolyzed to simpler carbohydrates. Examples of monosaccharides can include, for example, dextrose, glucose, fructose, and galactose. As used herein, the term "polysaccharide" refers to saccharides comprising two or more monosaccharides linked together by a glycosidic bond. Examples of polysaccharides can include, for example, 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. This energy can be released when carbohydrates are oxidized to generate carbon dioxide and water.
[0005] Despite its promise, the development and implementation of biofuel-based technology has been slow. Several reasons exist for this slow development. Ideally, a biofuel can be compatible with existing engine technology and have the ability to be distributed through the existing transport infrastructure. Current industrial processes for the formation of biofuel are limited to the fermentation of sugars and gums for ethanol, which competes with these materials as a food source. In addition, ethanol has a low energy density when used as a fuel. Although some compounds that have the potential to serve as fuel can be produced from biomass sources (eg, ethanol, methanol, biodiesel, Fischer-Tropsch diesel, and gaseous fuels such as hydrogen and methane), these fuels they generally require new distribution infrastructure and / or engine technologies to accommodate their physical characteristics. As noted above, an industrial scale process that can convert biomass into fuel mixtures in a cost and energy efficient manner that is similar to fossil fuels has yet to be developed. summary
[0006] The present description in general refers to the processing of cellulosic biomass, and, more specifically, to biomass conversion systems and methods that allow cellulosic biomass solids to be added to a digestion unit operating at pressures high levels of 30 bar (3 mPa) or more.
[0007] In some embodiments, the present invention provides a method comprising: providing a biomass conversion system comprising a pressurization zone and a digestion unit that are operatively connected to each other; provide a cellulosic biomass in a first pressure; introducing at least a portion of the cellulosic biomass into the pressurization zone and then pressurizing the pressurization zone to a second pressure that is greater than the first pressure; after pressurizing the pressurization zone, transfer at least a portion of the cellulosic biomass from the pressurization zone to the digestion unit, which is at a third pressure that is less than or equal to the second pressure but greater than the first pressure; and digesting at least a portion of the cellulosic biomass in the digestion unit to produce a hydrolyzate comprising soluble carbohydrates within a liquor phase.
[0008] In some embodiments, the present invention provides a method comprising: providing a biomass conversion system comprising a pressurization zone and a digestion unit that are operatively connected to each other; provide a cellulosic biomass; introducing at least a portion of the cellulosic biomass into the pressurization zone and then pressurizing the pressurization zone, at least in part, with a liquor phase comprising an organic solvent; after pressurizing the pressurization zone, transfer at least a portion of the cellulosic biomass from the pressurization zone to the digestion unit, where the digestion unit is at a pressure that is less than or equal to the pressure of the pressurization; and digesting at least 90% of the cellulosic biomass, on a dry basis, to produce a hydrolyzate comprising soluble carbohydrates within a liquor phase.
[0009] In some embodiments, the present invention provides a biomass conversion system comprising: a loading mechanism, a pressurization zone, and a digestion unit that are operatively connected to each other in a sequential series; a fluid circulation circuit that establishes fluid communication between an inlet and an outlet of the digestion unit; and a fluid transport line that establishes fluid communication between the fluid circulation circuit and the pressurization zone; wherein the pressurization zone and the digestion unit are operatively connected to each other in such a way that at least a portion of a cellulosic biomass in the pressurization zone can be transferred to the digestion unit while the digestion unit is operating at a pressure of at least 30 bar (3 mPa).
[00010] The features and advantages of the present invention will be readily apparent to one skilled in the art from reading the description of the preferred embodiments which follow. Brief Description of Drawings
[00011] The following figures are included to illustrate certain aspects of the present description, and should not be seen as exclusive embodiments. The subject described is capable of considerable modifications, alterations, combinations and equivalents in form and function, as will occur to an expert in the art and the benefit of this description.
[00012] FIGURE 1 shows a schematic view of an illustrative embodiment of a biomass conversion system that allows a digestion unit in it to be loaded semi-continuously with the biomass while operating at high pressures.
[00013] FIGURE 2 shows a schematic view of another illustrative embodiment of a biomass conversion system that allows a digestion unit to be loaded in a semi-continuous manner with the biomass while operating at high pressures.
[00014] FIGURE 3 shows a schematic view of an illustrative embodiment of a biomass conversion system that allows a digestion unit to be continuously loaded with biomass while operating at high pressures.
[00015] FIGURE 4 shows a schematic view of another illustrative embodiment of a biomass conversion system that allows a digestion unit to be continuously loaded with biomass while operating at high pressures.
[00016] FIGURE 5 shows a schematic view of another illustrative embodiment of a biomass conversion system that allows a digestion unit in it to be loaded semi-continuously with the biomass while operating at high pressures.
[00017] FIGURE 6 shows a schematic view of an illustrative biomass conversion system that has a combined pressurization zone / digestion unit. Detailed Description
[00018] The present description generally refers to the processing of cellulosic biomass, and, more specifically, to biomass conversion systems and methods that allow cellulosic biomass solids to be added to a digestion unit operating at pressures high levels of 30 bar (3 mPa) or more.
[00019] Unless otherwise specified here, it is to be understood that the use of the term "biomass" in the description that follows refers to "cellulosic biomass solids." Solids can be of any size, conformation or shape. Cellulosic biomass solids can be natively present in any of these sizes, conformations or solid forms or can be further processed before digestion in the embodiments described here. Cellulosic biomass solids can be present in a slurry form in the embodiments described here.
[00020] In the practice of the present embodiments, any type of biomass source can be used. Suitable sources of cellulosic biomass may include, for example, forest waste, agricultural waste, herbaceous material, municipal solid waste, recycled and waste paper, pulp and paper-making waste, and any combination thereof. Thus, in some embodiments, a suitable cellulosic biomass may include, for example, corn straw, straw, bagasse, miscant, sorghum residue, grasses, bamboo, water hyacinth, hardwood, hardwood chips, hardwood pulp, coniferous wood, coniferous wood chips, coniferous wood pulp, and any combination thereof. Leaves, roots, seeds, stems, and the like can be used as a source of cellulosic biomass. Common sources of cellulosic biomass can include, for example, agricultural residues (for example, corn stalks, straw, seed husks, sugarcane remnants, nut shells, and the like), wood materials (for example , wood or bark, sawdust, wooden bar, mill waste, and the like), municipal waste (for example, waste paper, yard cuttings or debris, and the like), and energy crops (for example, poplars, willows, grasses, alfalfa, prairie bluestream, corn, soybeans, and the like). Cellulosic biomass can be chosen based on considerations such as, for example, cellulose and / or hemicellulose content, lignin content, growing season / time, transportation cost / growth location, growth costs, collection costs, and the like.
[00021] When biomass is converted into industrial chemicals and fuel mixtures, the complex organic molecules in it need to be broken down into simpler molecules, which can be transformed into other compounds. For cellulosic biomass, the first step in this process is the production of soluble carbohydrates, typically by digestion. Digestion of cellulosic biomass can be conducted using an acid or a base in a process similar to that of Kraft at low temperatures and pressures to produce a biomass pulp. These types of digestion processes are commonly used in the pulp and paper industry. According to the embodiments described here, the digestion rate of cellulosic biomass can be accelerated in the presence of a digestion solvent at elevated pressures and temperatures that keeps the digestion solvent in a liquid state above its normal boiling point. In various embodiments, the digesting solvent can contain an organic solvent, particularly an organic solvent generated on site, which can provide particular advantages, as described hereinafter.
[00022] When a digestion solvent is used at higher pressures and temperatures, the digestion process can become quite energy intensive. If the energy input requirements for the digestion process become too great, the economic viability of cellulosic biomass as a raw material can be jeopardized. That is, if the energy input needed to digest cellulosic biomass is very large, the processing costs can be higher than the current value of the product being generated. In order to keep processing costs low, the amount of heat added externally to the digestion process must be kept as low as possible while achieving as high a conversion as possible of cellulosic biomass into soluble carbohydrates.
[00023] A particular problem with the previous high temperature / pressure digestion approach is that it can be difficult to add cellulosic biomass to a digestion unit that operates at a high pressure. One reason for this difficulty is that cellulosic biomass, particularly wood, can be somewhat rigid and difficult to compress even a pressure seal plug during transfer. The addition of biomass to the pressurized digestion unit is necessary in order to keep the digestion unit operating continuously. If the digestion unit needs to be at least partially depressurized and cooled to add more biomass, it can result in costly process downtime. In addition, when the digestion unit needs to be cooled and at least partially depressurized, bringing the digestion unit back to its normal pressure and temperature can add considerably to the energy input requirements of the process. This inefficiency of energy input can impair the viability of biomass as a raw material.
[00024] The present description provides systems and methods that allow cellulosic biomass to be efficiently digested to form soluble carbohydrates, which can subsequently be converted through one or more catalytic reduction reactions (for example, hydrogenolysis and / or hydrogenation) for reaction products comprising oxygenated intermediates that can be further processed to higher hydrocarbons. Higher hydrocarbons can be useful in the formation of industrial chemicals and transport fuels (i.e., a biofuel), including, for example, synthetic gasoline, diesel fuels, jet fuels, and the like. As used here, the term "biofuel" will refer to any transport fuel formed from a biological source.
[00025] As used here, the term "soluble carbohydrates" refers to monosaccharides or polysaccharides that are solubilized in a digestion process. As used herein, the term "oxygenated intermediates" refers to alcohols, polyols, ketones, aldehydes, and mixtures thereof that are produced from a catalytic reduction reaction (for example, hydrogenolysis and / or hydrogenation) of soluble carbohydrates . As used herein, the term "higher hydrocarbons" refers to hydrocarbons having an oxygen to carbon ratio of less than that of at least one component of the biomass source from which they are produced. As used herein, the term "hydrocarbon" refers to an organic compound comprising primarily hydrogen and carbon, although heteroatoms such as oxygen, nitrogen, sulfur, and / or phosphorus may be present in some embodiments. Thus, the term "hydrocarbon" also encompasses compounds substituted by hetero atoms that contain carbon, hydrogen, and oxygen, for example.
[00026] Illustrative carbohydrates that may be present in cellulosic biomass may include, for example, sugars, sugar alcohols, celluloses, lignocelluloses, hemicelluloses, and any combination thereof. Once soluble carbohydrates have been removed from the biomass matrix through a digestion process according to the embodiments described here, the soluble carbohydrates can be transformed into a reaction product comprising oxygenated intermediates through a catalytic reduction reaction. . Until the soluble carbohydrates are transformed by the catalytic reduction reaction, they are very reactive and can be subjected to degradation under digestion conditions. For example, soluble carbohydrates can degrade into insoluble by-products such as, for example, caramel and other heavy degradation end products that cannot be readily transformed through additional reactions to a biofuel. Such degradation products can also be harmful to the equipment used in the processing of biomass. Thus, in some embodiments, soluble carbohydrates and a digesting solvent are circulated in a fluid circulation circuit to remove them from digestion conditions and convert them to less reactive oxygenated intermediates through a catalytic reduction reaction.
[00027] In some embodiments, the oxygenated intermediates can be further transformed into a biofuel using any combination of additional hydrogenolysis reactions, hydrogenation reactions, condensation reactions, isomerization reactions, oligomerization reactions, hydrotreatment reactions, alkylation, and the like. In some embodiments, at least a portion of the oxygenated intermediates can be recirculated to the digestion unit to comprise at least a portion of the digestion solvent. The recirculation of at least a portion of the oxygenated intermediates to the digestion unit can also be particularly advantageous in terms of process efficiency and thermal integration.
[00028] As noted earlier, a significant problem for the processing of cellulosic biomass is the development of a mechanism and process by which a pressurized digestion unit can be supplied in a continuous or semi-continuous manner with fresh biomass. Without the ability to introduce fresh biomass to a pressurized digestion unit, depressurization and cooling of the digestion unit can occur during the addition of fresh biomass, significantly reducing the cost and energy efficiency of the conversion process. As used here, the term "continuous addition" and grammatical equivalents thereof will refer to a process in which biomass is added to a digestion unit in an uninterrupted manner without completely depressurizing the digestion unit. As used here, the term "semi-continuous addition" and grammatical equivalents thereof will refer to a discontinuous but necessary addition of biomass to a digestion unit without completely depressurizing the digestion unit. The ability to feed a pressurized digestion unit continuously or semi-continuously can be advantageous in terms of cost and time savings. In addition, the introduction of fresh biomass may occur more frequently than would otherwise be possible.
[00029] The development of a mechanism and a process by which biomass solids can be loaded into a pressurized digestion unit is not a simple matter. As has been seen, it may be desirable to soak or infiltrate the biomass solids with a digestion solvent, particularly a digestion solvent containing an organic solvent, before introducing the biomass into the digestion unit. In some cases, soaking the biomass with a digesting solvent can make it easier to pressurize the biomass when it is introduced into the digestion unit. In some cases, soaking the biomass with a digesting solvent can decrease the biomass's propensity to float in the digestion unit. Floating biomass in the digestion unit can result in inefficient digestion and make it difficult to introduce additional biomass into the digestion unit. In addition, the floating biomass can make it difficult to achieve pressure isolation from the digestion unit. For example, floating biomass can make it difficult to close a valve by providing pressure isolation for the digestion unit. As is described later here, the present embodiments can overcome many of these obstacles encountered in loading biomass into a pressurized digestion unit. Advantages of particular embodiments will be discussed in further detail here below, with reference to the drawings.
[00030] A main advantage of the biomass conversion system described here is that the systems are designed to favor a high conversion of biomass into soluble carbohydrates, which can be subsequently processed into a biofuel. The biomass conversion system and associated methods described here should be distinguished from those in the cellulose and paper industry, where the objective is to partially collect digested wood pulp, instead of obtaining as much soluble carbohydrates as possible. In some embodiments, at least 60% of the cellulosic biomass, on a dry basis, can be digested into a hydrolyzate comprising soluble carbohydrates. In other embodiments, at least 90% of the cellulosic biomass, on a dry basis, can be digested into a hydrolyzate comprising soluble carbohydrates. The design of the present systems can allow such high conversion rates by minimizing the formation of degradation products during the processing of biomass.
[00031] In some embodiments, the biomass conversion systems described here may allow the digestion unit to operate continuously at high pressures. For example, in some embodiments, the digestion unit can be operated at a pressure of at least 30 bar (3 mPa) while biomass is being added to it. In some embodiments, a biomass conversion system may comprise a loading mechanism, a pressurization zone, and a digestion unit that are operatively connected to each other in a sequential series; a fluid circulation circuit that establishes fluid communication between an inlet and an outlet of the digestion unit; and a fluid transport line that establishes fluid communication between the fluid circulation circuit and the pressurization zone; wherein the pressurization zone and the digestion unit are operatively connected to each other in such a way that at least a portion of a cellulosic biomass in the pressurization zone can be transferred to the digestion unit while the digestion unit is operating at a pressure of at least 30 bar (3 mPa).
[00032] In some embodiments, methods described here may comprise: providing a biomass conversion system comprising a pressurization zone and a digestion unit that are operatively connected to each other; provide a cellulosic biomass in a first pressure; introducing at least a portion of the cellulosic biomass into the pressurization zone and then pressurizing the pressurization zone to a second pressure that is greater than the first pressure; after pressurizing the pressurization zone, transfer at least a portion of the cellulosic biomass from the pressurization zone to the digestion unit, which is at a third pressure that is less than or equal to the second pressure, but greater than first pressure; and digesting at least a portion of the cellulosic biomass in the digestion unit to produce a hydrolyzate comprising soluble carbohydrates within a liquor phase.
[00033] In some embodiments, methods described here may comprise: providing a biomass conversion system comprising a pressurization zone and a digestion unit that are operatively connected to each other; provide a cellulosic biomass; introducing at least a portion of the cellulosic biomass into the pressurization zone and then pressurizing the pressurization zone, at least in part, with a liquor phase comprising an organic solvent; after pressurizing the pressurization zone, transfer at least a portion of the cellulosic biomass from the pressurization zone to the digestion unit, where the digestion unit is at a pressure that is less than or equal to the pressure of the pressurization; and digesting at least 90% of the cellulosic biomass, on a dry basis, to produce a hydrolyzate comprising soluble carbohydrates within a liquor phase.
[00034] In some embodiments, biomass conversion systems may additionally comprise a loading mechanism that is operatively connected to the pressurization zone. Any type of loading mechanism capable of dropping or transporting cellulosic biomass can be used in the present embodiments. Suitable loading mechanisms may include, for example, conveyor belts, vibrating tube conveyors, the screw feeder, compartment dispenser, and the like. It should be recognized that in some embodiments, the loading mechanism can be omitted. For example, in some embodiments, the addition of cellulosic biomass to the pressurization zone can occur manually. In some embodiments, cellulosic biomass can be supplied and introduced to the pressurization zone at the same time. That is, a loading mechanism does not necessarily need to be used.
[00035] In some embodiments, the digestion unit can be, for example, a pressure vessel made of carbon steel, stainless steel, or a similar alloy. In some embodiments, a single digestion unit can be used. In other embodiments, multiple digestion units that operate in series, in parallel or any combination thereof can be used. In some embodiments, digestion can be conducted in a pressurized digestion unit that operates continuously. However, in other embodiments, digestion can be conducted in batch mode. Suitable digestion units may include, for example. q FkiguVqt "RCPFKC ™" * XqguV-Alpine Industrienlagenbau GmbH, Linz, Austria), the "DEFIBRATOR" Digester (Sunds Defibrator AB Corporation, Stockholm, Sweden), the M&D Digestor (Messing & Durkee) (Bauer Brothers Company, Springfield, Ohio , USA) and the KAMYR Digestor (Andritz Inc., Glens Falls, New York, USA). In some embodiments, the biomass can be at least partially immersed in the digestion unit. In other embodiments, the digestion unit can be operated as a drip bed or stack type digestion unit. Agitated contact and fluidized bed digestion units can also be used in some embodiments. Suitable digestion unit designs may include, for example, fluidized bed, agitated tank, countercurrent or competitor digestion units.
[00036] In general, digestion can be conducted in a liquor phase. In some embodiments, the liquor phase may comprise a digesting solvent that comprises water. In some embodiments, the liquor phase may additionally comprise an organic solvent. In some embodiments, the organic solvent may comprise oxygenated intermediates produced from a catalytic reduction reaction of soluble carbohydrates. For example, in some embodiments, a digesting solvent may comprise oxygenated intermediates produced through a hydrogenolysis reaction of soluble carbohydrates. In some embodiments, bioethanol can be added to the water as a starting digest solvent, with a solvent comprising oxygenated intermediates being produced next. Any other organic solvent that is miscible with water can also be used as a starting digest solvent if desired. In general, a sufficient amount of liquor phase is present in the digestion process such that the surface of the biomass remains wet. The amount of liquor phase can be additionally chosen to maintain a sufficiently high concentration of soluble carbohydrates to achieve a high desirable reaction rate during the subsequent catalytic reduction, but not so high that degradation becomes problematic. In some embodiments, the concentration of soluble carbohydrates can be kept below 5% by weight of the liquor phase to minimize degradation. However, it must be recognized that higher concentrations can be used in some embodiments. In some embodiments, organic acids such as, for example, acetic acid, oxalic acid, acetylsalisilic acid, and acetylsalisilic acid can be included in the liquor phase as an acidic promoter of the digestion process.
[00037] In some embodiments, prior to digestion, cellulosic biomass can be washed and / or reduced in size (for example, by cutting, crushing, peeling, and the like) to achieve a desired quality and size to be digested . The operations can remove substances that interfere with additional chemical transformation of soluble carbohydrates and / or improve the penetration of the digesting solvent into the biomass. In some embodiments, washing may take place inside the digestion unit prior to pressurization. In other embodiments, washing can take place before the biomass is positioned in the digestion unit.
[00038] In some embodiments, the digesting solvent may comprise oxygenated intermediates from an organic solvent generated on site. As used here, the term "organic solvent generated on site" refers to the reaction product produced from a catalytic reduction reaction of soluble carbohydrates, where the catalytic reduction reaction takes place in a catalytic reduction reactor unit coupled to the system conversion of biomass. In some embodiments, the organic solvent generated at the site can comprise at least one alcohol, ketone, or polyol. In alternative embodiments, the digesting solvent can be at least partially supplied from an external source. For example, in one embodiment, bioethanol can be used to supplement the organic solvent generated at the site. In some embodiments, the digesting solvent can be separated, stored or selectively injected into the digestion unit in order to maintain a desired concentration of soluble carbohydrates.
[00039] In some embodiments, digestion can occur over a period of time at elevated pressures and temperatures. In some embodiments, digestion can occur at a temperature ranging from 100 ° C to 240 ° C for a period of time. In some embodiments, the time period can vary between 0.25 hours and 24 hours. In some embodiments, digestion to produce soluble carbohydrates can occur at a pressure ranging from 1 bar (absolute) (0.1 mPa abs.) To 100 bar (10 mPa).
[00040] In various embodiments, suitable biomass digestion techniques may include, for example, acid digestion, alkaline digestion, enzymatic digestion, and digestion using hot water.
[00041] Several factors can influence the digestion process. In some embodiments, hemicellulose can be extracted from biomass at temperatures below 160 ° C to produce a predominantly C5 carbohydrate fraction. At increasing temperatures, this fraction of C5 carbohydrate can be thermally degraded. Therefore, it may be advantageous to convert carbohydrates C5 and / or C6 and / or other sugar intermediates into more stable intermediates such as sugar alcohols, alcohols, and polyols. By reacting soluble carbohydrates in a catalytic reduction reactor unit and recycling at least a portion of the reaction product to the digestion unit, the concentration of oxygenated intermediates can be increased to commercially viable concentrations while the concentration of soluble carbohydrates is maintained low.
[00042] In some embodiments, cellulose digestion can start above 160 ° C, with solubilization becoming complete at temperatures around 190 ° C, aided by organic acids (eg carboxylic acids) formed from degradation partial of carbohydrate components. Some lignins can be solubilized before cellulose, while other lignins can persist at higher temperatures. These lignins can optionally be removed at a later time. The digestion temperature can be chosen so that carbohydrates are solubilized while limiting the formation of degradation products.
[00043] In some embodiments, a plurality of digestion units can be used. In such embodiments, the biomass can first be introduced into a digestion unit operating at 160 ° C or below to solubilize C5 carbohydrates and some lignin without substantially degrading these products. The remaining biomass can then exist for the first digestion unit and move on to a second digestion unit. The second digestion unit can be used to solubilize C6 carbohydrates at a higher temperature. In another embodiment, a series of digestion units can be used with an increasing temperature profile so that a desired carbohydrate fraction is solubilized in each.
[00044] In some embodiments, cellulosic biomass within the pressurization zone can be pressurized, at least in part, by introducing at least a portion of the liquor phase into the pressurization zone. In some embodiments, the cellulosic biomass within the pressurization zone can be pressurized, at least in part, by introducing a gas into the pressurization zone. In some embodiments, the pressurization zone can be pressurized by adding at least a portion of the liquor phase, followed by a gas, to the pressurization zone. In some embodiments, the liquor phase may comprise an organic solvent, such as an organic solvent generated on site. In some embodiments, the solvent generated at the site can be transferred from the digestion unit to the pressurization zone. In some or other embodiments, the organic solvent generated at the site can be transferred from a surge vessel within a fluid circulation line in fluid communication with an outlet from the digestion unit.
[00045] Some embodiments of the present description will now be described with reference to the drawings. In some embodiments, the biomass conversion systems depicted in the drawings may allow the biomass solids to be loaded in a continuous or semi-continuous manner into a pressurized digestion unit, thereby allowing the biomass processing to take place in a manner substantially uninterrupted. Batch processing can also be used, however. In some embodiments, biomass conversion systems are capable of such continuous or semi-continuous addition while the digestion unit is operating at a pressure of 30 bar (3 mPa) or greater, more typically at a pressure of 70 bar (7 mPa) or greater. In some embodiments, after transferring the biomass to the digestion unit, the digestion unit can be at a pressure of 30 bar (3 mPa) or greater.
[00046] FIGURE 1 shows a schematic view of an illustrative embodiment of a biomass conversion system that allows a digestion unit in it to be loaded semi-continuously with the biomass while operating at high pressures. As shown in FIGURE 1, the biomass conversion system 1 contains a digestion unit 2, which is operatively connected with the pressurization zone 4 and the loading container 6 in sequential series. The pressurization zone 4 contains the pressure vessel 5. The valves 8 and 8 'allow the pressure vessel 5 and the digestion unit 2 to be isolated from each other and pressurized. In some embodiments, pressurization of the pressure vessel 5 can occur using a liquor phase transferred from the digestion unit 2, which is provided by line 10. In some or other embodiments, the pressure vessel 5 they can occur using a liquor phase transferred from the optional surge vessel 3 through line 7. The liquor phase can contain the digesting solvent, soluble carbohydrates, and / or a reaction product produced from the soluble carbohydrates. The use of lines 7 and 10 is optional, and others can also be used to pressurize pressure vessel 5 including, for example, an external liquid or gas. However, it should be noted that the use of a liquor phase from the digestion unit 2 to affect pressurization can be advantageous, since it reduces the need to heat the biomass after the addition and results in less temperature variation when transferred. subsequently to the digestion unit. The optional fluid circulation circuit 11 can also be present to transfer the liquor phase from one portion of the digestion unit to another. The fluid circulation circuit 11 can also be used, as needed, to obtain a desired temperature profile in the digestion unit so that high rates of optimal digestion are achieved.
[00047] The biomass conversion system 1 also includes the fluid circulation circuit 12, which can circulate a hydrolyzate produced in the digestion unit 2 to the catalytic reduction reactor unit 14. The direction of the fluid flow within the circuit fluid flow rate 12 is indicated by the arrows. The catalytic reduction reactor unit 14 can transform soluble carbohydrates in the hydrolyzate into a reaction product comprising oxygenated intermediates. For example, in one embodiment, the hydrolyzate can be at least partially converted to oxygenated intermediates through contact with hydrogen in a catalytic hydrogenolysis reaction, for example. The reaction product can subsequently be recirculated to the digestion unit 2 via the fluid circulation circuit 12 and / or removed by the withdrawal line 16 for further processing for a biofuel. For example, subsequent processing steps may include additional catalytic reduction reactions (for example, hydrogenolysis reactions, hydrogenation reactions, hydrotreatment reactions such as hydrodesulfurization and hydrodesnitrification, and the like), condensation reactions, isomerization reactions, dehydration, oligomerization reactions, alkylation reactions, and the like to remove at least a portion of the oxygenated functionalities and, optionally, other functionalities from the reaction product in order to prepare a biofuel having desired properties.
[00048] In the embodiment shown in FIGURE 1, the fluid circulation circuit 12 and the digestion unit 2 are configured such that countercurrent flow is established within the digestion unit. Although it may be advantageous to establish the countercurrent flow within the digestion unit 2, there is no requirement to do this. For example, concurrent flow can be established by connecting the fluid circulation circuit 12 closest to the top of the digestion unit 2. The circulation of a liquor phase within the fluid circulation circuit 12 may be desirable, since the high reactivity of soluble carbohydrates to produce unwanted heavy final by-products can be reduced by catalytic reduction in the catalytic reduction reactor unit 14. From a thermal management point of view, it may also be desirable to recirculate the reaction product within the fluid circulation 12 to the digestion unit 2. For example, the digestion process is endothermic such that heat needs to be added, while the catalytic reduction reaction that takes place in the catalytic reduction reactor unit 14 is exothermic. The liquor phase within the fluid circulation circuit 12 can return this heat, which can otherwise be wasted, to the digestion unit 2, thereby reducing the need to supply heat from external sources. This can improve the overall energy efficiency of the biomass conversion process and makes the process more economically viable for the formation of a biofuel.
[00049] In the operation of the biomass conversion system of FIGURE 1, the biomass can be introduced into the pressurization container 5. Next, the pressurization container 5 can be pressurized to a pressure greater than or equal to that of the pressure unit. digestion 2. In some embodiments, the pressurization vessel 2 can be at least partially pressurized with the liquor phase from the digestion unit 2 and / or surge vessel 3. Since there is a need to introduce additional biomass for the digestion unit 2, the valve 8 'can be opened, and the pressure differential can direct the biomass to the digestion unit 2 without a pressure drop being experienced in the digestion unit. This can allow the digestion unit to continue its uninterrupted operation. Then, the valve 8 'can be closed again to keep the digestion unit 2 in pressure isolation, and the pressure vessel 5 can be at least partially depressurized and then refilled.
[00050] FIGURE 2 shows a schematic view of another illustrative embodiment of a biomass conversion system that allows a digestion unit in it to be loaded semi-continuously with the biomass while operating at high pressures. The biomass conversion system 20 shown in FIGURE 2 contains a digestion unit 22, the loading vessel 26, the fluid circulation circuit 32, the catalytic reduction reactor unit 34, the withdrawal line 36 and the optional line 31, which operate in a similar manner to similar elements described with reference to FIGURE 1. While the pressurization zone 4 of FIGURE 1 contains a pressure vessel 5, the pressurization zone 24 of FIGURE 2 contains pressure vessels 25 and 25 ', which are separated by valve 28 ". Valves 28 and 28' perform similar functions as in the embodiment of FIGURE 1. In some embodiments, lines 30 and 30 'can be used to provide a liquor phase from of the digestion unit 22 for both pressure vessels 25 or 25 '. Similarly, in some embodiments, lines 27 and 27' can be used to deliver a liquor phase from the optional surge container 23 to both you pressure vessels 25 or 25 '. Optionally, pressurization can also take place with a liquid or gas added externally. The externally added liquid or gas can be separated from or in addition to the liquor phase introduced from the digestion unit 22 or outbreak container 23.
[00051] The biomass conversion system shown in FIGURE 2 can be operated in a manner similar to that described for FIGURE 1, with the exception of how the biomass is introduced into the pressurization zone and the pressurization zone is pressurized. In one embodiment, the pressurization zone 24 can be pressurized in stages, for example, by increasing the pressure in each pressurization vessel. In one embodiment, the biomass can be positioned in the pressure vessel 25, which can then be pressurized to a first pressure. In an alternative embodiment, multiple pressure zones can be present in a single pressure vessel. Next, the biomass can be transferred through the pressure-assisted transfer to the pressure vessel 25 ', which can then be pressurized to a second pressure that is greater than or equal to that in which the digestion unit 22 is operating. In one embodiment, the pressure in the pressure vessel 25 may be less than that in the pressure vessel 25 ', such that the pressure is "high" after each transfer. Facilitating the introduction of biomass solids into a digestion unit with this type of pressure rise can be advantageous where it is difficult or unnecessary to pressurize the entire pressurization zone. In another embodiment, the pressure in the pressure vessels 25 and 25 'may be substantially the same, and the pressure vessel 25 may simply be a biomass retention area ready for transfer to the pressure vessel 25'. That is, then there is no need for a pressure increase to occur in the pressure vessel 25 '. Once the biomass has been transformed from the pressure vessel 25, it can be at least partially depressurized and biomass loading continued once more. It should be recognized that although FIGURE 2 represented only two pressure vessels, any number can be used in accordance with the following embodiments.
[00052] In another embodiment, both pressure vessels 25 and 25 'can contain biomass and be pressurized at a pressure greater than or equal to that in digestion unit 22. In this embodiment, at least a portion of the biomass in the pressure vessel 25 ', can be transferred to the digestion unit 22, as described above, while the biomass in the pressure vessel 25 remains available to be transferred subsequently to the pressure vessel 25' and then to the digestion unit 22. Once the pressure vessel 25 has been emptied of biomass, it can be at least partially depressurized and replenished with fresh biomass.
[00053] In some embodiments, the pressurization zone can be configured such that the biomass can be added continuously to the pressurized digestion unit. Various biomass conversion systems that are capable of adding continuous biomass to a pressurized digestion unit are described in further detail below.
[00054] FIGURE 3 shows a schematic view of an illustrative embodiment of a biomass conversion system that allows a digestion unit to be continuously loaded with biomass while operating at high pressures. As the biomass conversion system depicted in FIGURE 1, the biomass conversion system 40 contains a digestion unit 42, the loading container 46, the fluid circulation circuit 52, the catalytic reduction reactor unit 54, the withdrawal line 56, and optional line 51.
[00055] As shown in FIGURE 3, the pressurization zone 44 contains plug forming feeders 43 and 43 'connected in series with the optional holding container 53 arranged between them. Lines 50 and 50 'can be used to supply a liquor phase from the digestion unit 42 to plug forming feeders 43 or 43', respectively. The lines from the surge container 57 can also provide a liquor phase for plug forming feeders 43 and 43 ', although these lines have not been shown for the purposes of clarity in FIGURE 3. In general, any type of Plug-forming mechanical power system can be used. As shown in FIGURE 3, plug forming feeders 43 and 43 'are screw feeders. In alternative embodiments, a piston driven feeder can be used for one or both plug forming feeders.
[00056] In the operation of the biomass conversion system 40, the biomass inside the loading container 46 can be supplied to the plug forming feeder 43, which can at least partially increase the pressure of the biomass. For example, plug forming feeder 43 can establish a fluid plug comprising biomass that increases the pressure of the system. The biomass can then be transferred to the holding container 53, which can maintain the biomass in a state of high pressure before it is transferred to the plug forming feeder 43 'and subsequently introduced to the digestion unit 42. In a embodiment, plug forming feeder 43 can establish a pressure greater than or equal to the pressure in the digestion unit 42, and plug forming feeder 43 'can maintain or increase that pressure. In another embodiment, the plug forming feeder 43 can establish a pressure below that of the digestion unit 42, and plug forming feeder 43 'can further increase the pressure such that it is greater than or equal to that of the unit digestion 42. As noted above, the use of plug forming feeders 43 and 43 'can allow the unit to be introduced into the digestion unit 42 in a substantially continuous manner. The batch addition of biomass can also be used, if desired. Although FIGURE 3 represented only two plug forming feeders that operate in series, it must be recognized that any number can be used. Likewise, the number of holding containers can also be greater than one.
[00057] Instead of arranging plug forming feeders in series, as shown in FIGURE 3, plug forming feeders, in other embodiments, can be arranged in parallel with each other and operated in a reciprocal manner. FIGURE 4 shows a schematic view of another illustrative embodiment of a biomass conversion system that allows a digestion unit to be continuously loaded with biomass while operating at high pressures. The batch addition of biomass can also be used, if desired. The biomass conversion system shown in FIGURE 4 is similar to that shown in FIGURE 3, except that plug forming feeders 43 and 43 'are arranged in parallel in FIGURE 4 and the holding container 53 has been omitted. Other elements in FIGURE 4 are identical to those described for FIGURE 3 and will not be properly described further.
[00058] The configuration shown in FIGURE 4 can be particularly advantageous if the biomass is not able to be compressed into a mechanical plug seal to feed to a higher pressure. In the embodiment shown in FIGURE 4, a feeder can be loaded at a lower pressure, while the parallel feeder can be pre-pressurized to the required delivery pressure after loading. In operation the biomass conversion system of FIGURE 4, the biomass can be supplied to a first screw feeder, pressurized, and transferred to the digestion unit. While the biomass in the first screw feeder is being transferred to the digestion unit, the second screw feeder can be loaded with biomass and pressurized, such that when the first screw feeder is empty, the biomass introduction can continue to break. of the second screw feeder. The empty screw feeder can then be at least partially depressurized, replenished with biomass, and pressurized again to continue the addition process again. Although FIGURE 4 represented only two screw feeders that operate in parallel, it must be recognized that any number can be used.
[00059] In yet another alternative configuration, a single feeder (for example, a screw feeder or piston driven feeder) can be used for the semi-continuous addition of biomass to a pressurized digestion unit. FIGURE 5 shows a schematic view of another illustrative embodiment of a biomass conversion system that allows a digestion unit in it to be loaded semi-continuously with the biomass while operating at high pressures. In operation the biomass conversion system of FIGURE 5, the feeder 43 can be loaded with the biomass and pressurized, and then the biomass can be transferred to the digestion unit 42. Once the biomass is transferred, the feeder 43 can be at least partially depressurized, recharged with biomass, and pressurized again for use when the addition of more biomass is required. Other elements in FIGURE 5 are identical to those described for FIGURE 3 and will not be properly described further.
[00060] Several advantages can be realized using the systems described above for loading the biomass into a pressurized digestion unit. An advantage is that through the use of a liquor phase from the digestion unit and / or a surge vessel in fluid communication with the digestion unit to pressurize the pressurization zone, better thermal integration can be achieved. If a gas or external solvent is used for pressurization, it may be necessary to heat the biomass in the pressurization zone prior to introduction to the digestion unit; otherwise, significant temperature variations in the digestion unit can occur, thus resulting in process inefficiency in any case. The use of liquor phase from the digestion unit can decrease the residence time of the liquor phase in the digestion unit, thereby reducing the propensity for degradation of soluble carbohydrates within the digestion unit. The degradation of soluble carbohydrates can also be reduced by circulating the liquor phase through the fluid circulation circuit and reacting the soluble carbohydrates to produce oxygenated intermediates in a catalytic reduction reaction unit, as previously described.
[00061] In the various embodiments described here above, the pressure of the digestion unit can be maintained at a pressure of at least 30 bar (3 mPa) to maintain a satisfactory rate of digestion. In some embodiments, the digestion unit can be maintained at a pressure ranging between 30 bar (3 mPa) and 430 bar (43 mPa). In some embodiments, the digestion unit can be maintained at a pressure ranging from 50 bar (5 mPa) to 330 bar (33 mPa). In some embodiments, the digestion unit can be maintained at a pressure ranging between 70 bar (7 mPa) and 130 bar (13 mPa). In some embodiments, the digestion unit can be maintained at a pressure ranging from 30 bar (3 mPa) to 130 bar (13 mPa). It must be recognized that when the biomass is transferred to the digestion unit from the pressurization zone, the pressure will be equalized between the two. Unless the pressures of the digestion unit and the pressurization zone are the same, there will be at least some pressure change in the digestion unit when biomass is introduced into the digestion unit. According to the embodiments described above, the pressure of the digestion unit can either remain the same or increase, since the pressurization zone is at a pressure greater than or equal to the operating pressure of the digestion unit when biomass is transferred. Of course, in some embodiments, the pressure of the digestion unit can be adjusted after biomass transfer, if desired.
[00062] In some embodiments, the digestion unit may have its pressure decreased slightly from its normal operating pressure before introducing the biomass from the pressurization zone. In some embodiments, the digestion unit may have its pressure decreased to a pressure that is at least 75% of its normal operating pressure, and the biomass from the pressurization zone can then be introduced. In such embodiments, the digestion unit will experience an increase in pressure when biomass is introduced. In some embodiments, this pressure increase can return the digestion unit to its normal operating pressure. In other embodiments, additional pressure adjustment may occur after introducing the biomass into the digestion unit.
[00063] In alternative embodiments of the present description, the digestion unit can be operated at a higher pressure than the container that holds the biomass to transfer to the digestion unit. In the description that follows, the pressurization zone of the biomass conversion system can be incorporated within the digestion unit, such that a portion of the digestion unit serves a dual digestion and pressure loading role. In such embodiments, at least half of the digestion unit can be operated continuously at high pressure, and the remainder of the digestion unit can serve the dual roles of biomass loading and digestion. The portion of the digestion unit that serves a double role can rotate between a high pressure for digesting biomass and a lower pressure for loading biomass.
[00064] In a refinery, tower heights are limited to 200 feet due to aviation restrictions. As a height restriction refers to the present embodiments, lastly, there is a limitation in the amount of biomass that can be processed in the digestion unit at any time. That is, in the embodiments described here, the digestion unit can be made only at a certain height in order to satisfy overall height requirements. In practice, the height of the digestion unit is even less, in the embodiments described above, since the pressurization zone and the loading container must also be accommodated at the height of the tower. If a greater amount of the tower height can be used for active digestion, instead of pressurization and periodic loading, greater biomass yield can be achieved. The embodiments described here below can achieve this advantage, while maintaining several of the advantages described above above. In particular, the embodiments described here below combine the functions of digestion and pressurization in a portion of the digestion unit to achieve the above advantage.
[00065] In some embodiments, a biomass conversion system can comprise a first digestion unit and a second digestion unit that are operatively connected to each other; a pressure isolating mechanism between the first digestion unit and the second digestion unit; a fluid circulation circuit that establishes fluid communication between an outlet of the first digestion unit and an input of the second digestion unit; and a bypass line that establishes fluid communication between an outlet of the second digestion unit and the fluid circulation circuit.
[00066] Any type of suitable pressure isolation mechanism can be used in the present embodiments and can be envisioned by a person skilled in the art. Suitable pressure isolating mechanisms may include, for example, ball valves, gate valves, slide gate valves, knife gate valves, trunnion valves, flanges, and the like.
[00067] A primary advantage of these biomass conversion systems is that the pressure can be maintained continuously in the second digestion unit, while the first digestion unit plays a dual role in digesting biomass and introducing biomass into the second digestion unit. With the first digestion unit serving this double purpose, a higher percentage of the overall tower height can be used for digestion, thereby increasing process efficiency. In some embodiments, the second digestion unit may be greater than or equal in size with the first digestion unit.
[00068] In some embodiments, biomass conversion systems may additionally comprise at least one catalytic reduction reactor unit within the fluid circulation circuit. In some embodiments, the catalytic reduction reactor unit may comprise at least one catalyst that is capable of activating molecular hydrogen. The further description of such catalysts is provided here below.
[00069] In some embodiments, the biomass conversion systems may additionally comprise at least one surge container in fluid communication with an outlet from the first digestion unit and located within the fluid circulation circuit. In some embodiments, the surge vessel may be located between the first digestion unit and the catalytic reduction reactor unit.
[00070] In some embodiments, biomass conversion systems may additionally comprise a loading mechanism operatively coupled with the first digestion unit. Suitable loading mechanisms have been described in greater detail here above.
[00071] In some embodiments, cellulosic biomass can be processed in the following ways using the previous biomass conversion systems.
[00072] In some embodiments, methods for the processing of cellulosic biomass may comprise providing the biomass conversion system comprising: a first digestion unit and a second digestion unit that are operatively connected to each other; a fluid circulation circuit that establishes fluid communication between an outlet of the first digestion unit and an input of the second digestion unit; and a bypass line that establishes fluid communication between an outlet of the second digestion unit and the fluid circulation circuit; digest at least partially a cellulosic biomass in, optionally, the first digestion unit and the second digestion unit, thereby forming a hydrolyzate comprising soluble carbohydrates within a liquor phase; isolating the first digestion unit from the second digestion unit and then at least partially depressurizing the first digestion unit; after depressurizing the first digestion unit at least partially and while digestion continues in the second digestion unit, load the first digestion unit with cellulosic biomass, and pressurize the first digestion unit again to a pressure of less than or equal to a pressure on the second digestion unit; and after re-pressurizing the first digestion unit, transfer at least a portion of the cellulosic biomass from the first digestion unit to the second digestion unit.
[00073] In some embodiments, methods for the processing of cellulosic biomass may comprise at least partially digesting a cellulosic biomass contained in, optionally, a first digestion unit and a second digestion unit to produce a hydrolyzate comprising soluble carbohydrates in one liquor phase, the first digestion unit and the second digestion unit being operatively connected to each other; circulating the liquor phase of the first digestion unit to the second digestion unit through a fluid circulation circuit that establishes fluid communication between an outlet of the first digestion unit and an inlet of the second digestion unit; isolating the first digestion unit from the second digestion unit, such that the liquor phase continues to flow through the second digestion unit into the fluid circulation circuit through a bypass line that establishes fluid communication between an outlet of the second unit digestion and fluid circulation circuit; while hydrolysis continues in the second digestion unit, add cellulosic biomass to the first digestion unit and pressurize the first digestion unit to a pressure that is less than or equal to a pressure in the second digestion unit; equalize the pressure between the first digestion unit and the second digestion unit; and transferring at least a portion of the cellulosic biomass from the first digestion unit to the second digestion unit.
[00074] In some embodiments, after adding cellulosic biomass to the second digestion unit, the methods may further comprise continuing to digest cellulosic biomass in at least the second digestion unit at a pressure of at least 30 bar (3 mPa). In some embodiments, at least 60% of the cellulosic biomass, on a dry basis, can be digested to produce a hydrolyzate comprising soluble carbohydrates. In some embodiments, at least 90% of the cellulosic biomass, on a dry basis, can be digested to produce a hydrolyzate comprising soluble carbohydrates.
[00075] FIGURE 6 shows a schematic view of an illustrative biomass conversion system that has a combined pressurization zone / digestion unit. The biomass conversion system 100 shown in FIGURE 6 contains the loading container 102, the digestion unit 104 and the digestion unit 106, connected together in sequential series. The digestion unit 104 is separated from the loading container 102 by the valve 114, and from the digestion unit 106 by the valve 116. The digestion unit 104 is connected to the fluid circulation circuit 110 which establishes fluid communication between an outlet of the digestion unit 104 and an inlet of the digestion unit 106. When the valve 116 is closed, the digestion units 104 and 106 are isolated from each other, although a liquor phase can continue to circulate within the circulation circuit of fluid 110 through the bypass line 112.
[00076] Within the fluid circulation circuit 110 there can be at least one catalytic reduction reactor unit 120 which can convert a hydrolyzate produced in digestion units 104 and 106 to a reaction product, which can subsequently be converted into a biofuel . In one embodiment, the catalytic reduction reactor unit 120 can perform a hydrogenolysis reaction. The reaction product from the catalytic reduction reactor unit 120 can be recirculated to the digestion unit 106 and / or removed from the fluid circulation circuit 110 via the withdrawal line 122 and further processed, for example, to a biofuel.
[00077] In some embodiments, the fluid circulation circuit 110 can be configured such that a fluid in it can enter the digestion unit 106 with countercurrent flow. It should be recognized, however, that the fluid circulation circuit 110 can connect with the digestion unit 106 such that any type of flow configuration can be established. Optional line 140 can circulate the liquor phase from a first location to a second location in the digestion unit 106.
[00078] In some embodiments, biomass conversion systems may additionally contain a surge vessel with the fluid circulation circuit. As shown in FIGURE 6, the surge vessel 130 may be located within the fluid circulation circuit 110 between the digestion unit 104 and the catalytic reactor unit 120. Among the reasons that someone may include an surge vessel in the system Conversion of biomass is to regulate flow rates within the fluid circulation circuit 110 that occur as a result of pressure variations within the system. These pressure variations can occur during the operation of the system as biomass is added, as discussed in more detail hereinafter.
[00079] In the embodiment shown in FIGURE 6, the digestion unit 104 can serve a dual function in allowing the digestion unit 106 to be loaded with biomass, while operating as a digestion unit when not being used for loading digestion unit 106. That is, digestion unit 104 combines the functions of a pressurization zone and a portion of the digestion unit. When not being loaded, digestion units 104 and 106 can effectively function as a single larger digestion unit. As previously described, this dual function of the digestion unit 104 allows a greater amount of the height of the biomass conversion system 100 to be used for digestion purposes, which can allow greater amounts of biomass to be processed at one time.
[00080] In some embodiments, the biomass conversion system shown in FIGURE 6 can be operated as in the sequence. The biomass can be positioned in digestion units 104 and 106, and the digestion process can be initiated in the presence of a digestion solvent. A hydrolyzate produced from biomass can be circulated through the fluid circulation circuit 110 and at least partially converted to a reaction product in the catalytic reduction reactor unit 120, and at least a portion of the reaction product can then be recirculated for the digestion unit 106. In some embodiments, the liquor phase that enters the digestion unit 106 may enter such that countercurrent flow is established for the purposes of heat management. While digestion is taking place, valve 116 is open such that the liquor phase flows through both digestion units 104 and 106, which effectively function as a single major digestion unit.
[00081] When it is desired to add more biomass to the digestion unit 106, the valve 116 can be closed such that the circulating liquor phase no longer enters the digestion unit 104, but instead passes from the digestion unit 106 directly to the fluid circulation circuit 110 by the bypass line 112. That is, the digestion units 104 and 106 can have the pressures isolated from each other. Once valve 116 has been closed, digestion unit 104 can be at least partially depressurized while digestion unit 106 remains at its normal high operating pressure (e.g., 30 bar (3 mPa) or greater).
[00082] It should be noted that the decision to add more biomass to the digestion unit 106 can occur in response to several different triggers. In some embodiments, the addition may occur periodically at fixed time points. In some embodiments, the addition may occur manually in response to operator input. In most other embodiments, the addition can occur in response to a sensor within the second digestion unit. For example, in some embodiments, when an amount of biomass within the digestion unit 106 falls below a predetermined level, valve 116 can be closed to initiate the introduction of additional biomass.
[00083] Once the digestion unit 104 has been at least partially depressurized, additional biomass can be added to a digestion unit 104 via the loading container 102. At this point, valve 114 can be closed again and the digestion 104 can be pressurized again. A liquor phase can be introduced into the biomass into the digestion unit 104 prior to pressurization. In some embodiments, the liquor phase can come from the digestion unit 106 via line 132. In other embodiments, the liquor phase can come from an external source. As described above, pressurizing the biomass in the digestion unit 104 can have several process advantages that can result in more efficient digestion. In some embodiments, a gas can be used to further pressurize the digestion unit 104. In some embodiments, the digestion unit 104 can be pressurized to a pressure up to that in which the digestion unit 106 is operating. That is, when used for loading, the digestion unit 104 is typically maintained at a pressure of less than or equal to that of the operating pressure of the digestion unit 106.
[00084] Once the digestion unit 104 has been pressurized for an appropriate length of time (for example, to infiltrate the biomass with the liquor phase), valve 116 can be opened again. In embodiments in which the digestion unit 106 is at a higher pressure than the digestion unit 104 there will be an increase in the fluid level from the digestion unit 106 to the digestion unit 104 as the pressure equalizes between the units digestion. Once the pressure equalizes, at least a portion of the biomass in the digestion unit 104 can fall into the digestion unit 106 can replenish what has been consumed by the digestion that is taking place. At this point, fluid circulation can continue between digestion unit 104, digestion unit 106 and fluid circulation circuit 110, with bypass line 112 which is no longer used to maintain fluid circulation. In this way, digestion can continue in digestion unit 106 without interruption or depressurization. Again, this is a highly advantageous aspect for an efficient conversion in cost and energy from biomass to a biofuel.
[00085] When an increase in fluid occurs from digestion unit 106 to digestion unit 104, there may be a variance in flow in the fluid circulation circuit 110. Flow variances of this type can make system control difficult , and can sometimes be detrimental to the downstream catalytic reactor units. In this regard, it is advantageous to include the surge container 130 within the fluid circulation circuit 110. The inclusion of the surge container 130 can stabilize the flow within the fluid circulation circuit 110 primarily by retaining the flow variance into the flow container. outbreak 130 before reaching catalytic reduction reactor unit 120.
[00086] In the various embodiments described here, the digestion unit can typically be maintained at a pressure of at least 30 bar (3 mPa) to ensure that digestion occurs at a desired rate. In some embodiments, the digestion unit can be maintained at a pressure ranging between 30 bar (3 mPa) and 430 bar (43 mPa). In some embodiments, the digestion unit can be maintained at a pressure ranging from 50 bar (5 mPa) to 330 bar (33 mPa). In some embodiments, the digestion unit can be maintained at a pressure ranging between 70 bar (7 mPa) and 130 bar (13 mPa). In most other embodiments, the digestion unit can be maintained at a pressure ranging between 30 bar (3 mPa) and 130 bar (13 mPa). It should be noted that the previous pressures refer to the pressures at which digestion occurs. That is, the previous pressures refer to the normal operating pressures for the digestion unit. In more particular embodiments, the second digestion can be maintained at a pressure of at least 30 bar (3 mPa), or at least 50 bar (5 mPa), or at least 70 bar (7 mPa).
[00087] In embodiments in which a pressurization zone is used to introduce biomass into the digestion unit, the pressurization zone is generally pressurized to a pressure greater than or equal to that of the digestion unit, once that biomass was introduced into the pressurization zone. In this pressure differential, the biomass can undergo a pressure-assisted transfer to the digestion unit when the pressure is equalized.
[00088] In embodiments, in which two or more digestion units are connected together and one of the digestion units is used twice to digest and introduce the biomass to the other digestion unit, the pressure in the digestion unit used to pressurize it is typically maintained at a pressure that is less than or equal to that of the other digestion unit. As noted above, in this pressure differential, the liquor and biomass being digested in the second digestion unit will peak at the first digestion unit when the valve between them is opened. After the pressure equalizes, at least a portion of the biomass and the liquor phase in the first digestion unit can then be transferred by gravity drop to the second digestion unit. At this point, the biomass level in the second digestion unit will have been restored, without requiring a return of the second digestion unit to atmospheric pressure for loading, and digestion can then continue in both digestion units.
[00089] In some embodiments, the methods described here may additionally comprise converting the hydrolyzate to a biofuel. In some embodiments, the conversion of the hydrolyzate to a biofuel can begin with a catalytic hydrogenolysis reaction to transform soluble carbohydrates produced from digestion into a reaction product comprising oxygenated intermediates, as described above. As described above and represented in FIGURES 1 to 6, the reaction product can be recirculated to the digestion unit to further assist in the digestion process. In some embodiments, the reaction product can be further transformed by any number of additional catalytic reform reactions including, for example, additional catalytic reduction reactions (e.g., hydrogenolysis reactions, hydrogenation reactions, hydrotreatment reactions, and the like), condensation reactions, isomerization reactions, desulfurization reactions, dehydration reactions, oligomerization reactions, alkylation reactions, and the like. A description of the initial hydrogenolysis reaction of the additional catalytic reform reactions is described hereinafter.
[00090] Several processes are known to perform hydrogenolysis of carbohydrates. A suitable method includes contacting a hydrogen-stable carbohydrate or hydroxyl intermediate, optionally mixed with a diluent gas, and a hydrogenolysis catalyst under conditions effective to form a reaction product comprising oxygenated intermediates such as, for example, smaller molecules or polyols. As used herein, the term "smallest 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 one embodiment, the reaction products can include smaller molecules such as, for example, polyols and alcohols. This aspect of hydrogenolysis implies the rupture of carbon - carbon bonds.
[00091] In one embodiment, a soluble carbohydrate can be converted to relatively stable oxygenated intermediates such as, for example, propylene glycol, ethylene glycol, and glycerol using a hydrogenolysis reaction in the presence of a catalyst that is capable of activating the molecular hydrogen. Suitable catalysts can include, for example, Cr, Mo, W, Re, Mn, Cu, Cd, Fe, Co, Ni, Pt, Pd, Rh, Ru, Ir, Os, and alloys or any combination thereof, either alone or with promoters such as Au, Ag, Cr, Zn, Mn, Sn, Bi, B, O, and alloys or any combination thereof. In some embodiments, catalysts and promoters may allow hydrogenolysis and hydrogenation reactions to occur at the same time or in succession, such as the hydrogenation of a carbonyl group to form an alcohol. The catalyst may also include a carbonaceous pyropolymer catalyst containing transition metals (for example, chromium, molybdenum, tungsten, rhenium, manganese, copper, and cadmium) or Group VIII metals (for example, iron, cobalt, nickel, platinum, palladium, rhodium, ruthenium, iridium, and osmium). In certain embodiments, the catalyst can include any of the above metals combined with an alkaline earth metal oxide or adhered to a catalytically active support. In certain embodiments, the catalyst described in the hydrogenolysis reaction can include a catalyst support.
[00092] The conditions for which the hydrogenolysis reaction is carried out will vary based on the type of biomass starting material and the desired products (for example, gasoline or diesel), for example. A person skilled in the art, with the benefit of this description, will recognize the conditions suitable for use to carry out the reaction. In general, the hydrogenolysis reaction can be conducted at temperatures in the range of 110 ° C to 300 ° C, and preferably from 170 ° C to 300 ° C, and even more preferably from 180 ° C to 290 ° C .
[00093] In one embodiment, the hydrogenolysis reaction can be conducted under alkaline conditions, preferably at a pH of 8 to 13, and even more preferably at a pH of 10 to 12. In one embodiment, the reaction of hydrogenolysis can be conducted at a pressure ranging between 1 bar (absolute) (0.1 mPa abs.) and 150 bar (15 mPa), and preferably at a pressure ranging between 15 bar (1.5 mPa) and 140 bar (14 mPa), and even more preferably at a pressure ranging between 50 bar (5 mPa) and 110 bar (11 mPa).
[00094] The hydrogen used in the hydrogenolysis reaction can include external hydrogen, recycled hydrogen, hydrogen generated on site, or any combination thereof.
[00095] In some embodiments, the reaction products of the hydrogenolysis reaction may comprise greater than 25% per mole, or alternatively, greater than 30% per mole of polyols, which can result in greater conversion for a biofuel in a subsequent processing reaction.
[00096] In some embodiments, hydrogenolysis can be conducted under acidic or neutral conditions, as necessary to accelerate hydrolysis reactions in addition to the hydrogenolysis reaction. For example, hydrolysis of oligomeric carbohydrates can be combined with hydrogenation to produce sugar alcohols, which can undergo hydrogenolysis.
[00097] A second aspect of hydrogenolysis involves the disruption of -OH bonds such as: RC (H) 2-OH + H2 -> RCH3 + H20. This reaction is also called "hydrodeoxygenation," and can occur in parallel with the hydrogenolysis of C - C bond disruption. Diols can be converted to mono - oxygenated through this reaction. As the severity of the reaction is increased with increased temperature or increased contact time with the catalyst, the concentration of polyols and diols in relation to mono-oxygenates may decrease as a result of hydrodeoxygenation. The selectivity for C-C against C - OH bonding hydrogenolysis will vary with the type of catalyst and the formulation. Complete deoxygenation to alkanes can also occur, but in general, it is undesirable if the intention is to produce mono-oxygenates or diols and polyols that can be condensed or oligomerized to higher molecular weight compounds in a subsequent processing step. Typically, it is desirable to send only mono-oxygenates or diols for subsequent processing steps, as larger polyols can lead to excessive coke formation during condensation or oligomerization. Alkanes, in contrast, are essentially non-reactive and cannot be readily combined to produce larger molecular compounds.
[00098] Once oxygenated intermediates have been formed through a hydrogenolysis reaction, a portion of the reaction product can be recirculated to the digestion unit to serve as an internally generated digestion solvent. Another portion of the reaction product can be removed and subsequently processed by additional reform reactions to form a biofuel. Before being subjected to additional reform reactions, the oxygenated intermediates can optionally be separated into different components. Suitable separations can include, for example, phase separation, solvent extraction columns, extractors, filters, distillations and the like. In some embodiments, a separation of lignin from the oxygenated intermediates before the reaction product is subsequently further processed or recirculated to the digestion unit.
[00099] Oxygenated intermediates can be processed to produce a fuel mixture in one or more processing reactions. In one embodiment, a condensation reaction can be used in conjunction with other reactions to generate a fuel mixture and can be catalyzed by a catalyst comprising an acid, a base, or both. In general, without being limited to any particular theory, it is believed that basic condensation reactions can involve a series of steps involving: (1) an optional dehydrogenation reaction; (2) an optional dehydration reaction that can be catalyzed by acid; (3) an aldolic condensation reaction; (4) an optional ketonation reaction; (5) an optional furan ring opening reaction; (6) hydrogenation of the resulting condensation products to form the _> C4 hydrocarbon; and (7) any combination thereof. Acid-catalyzed condensations in a similar way can lead to optional hydrogenation or dehydrogenation reactions, dehydration, and oligomerization reactions. Additional polishing reactions can also be used to conform the product to a specific fuel standard, including reactions conducted in the presence of hydrogen and the hydrogenation catalyst to remove functional groups from the final fuel product. In some embodiments, an alkaline catalyst, a catalyst having both an acid functional and an alkaline functional site, and optionally comprising a metal function, can also be used to carry out the condensation reaction.
[000100] In some embodiments, an aldolic condensation reaction can be used to produce a fuel mixture that meets the requirements for a diesel fuel or jet fuel. Traditional diesel fuels are petroleum distillates rich in paraffinic hydrocarbons. They have boiling ranges as wide as 187 ° C to 417 ° C, which are suitable for combustion in a compression ignition engine, such as a diesel engine vehicle. The American Society of Testing and Materials (ASTM, in Portuguese: American Society of Tests and Materials) establishes the degree of diesel according to the boiling range, along with ranges that are allowed for other fluid 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 that satisfies ASTM D975 can be defined as diesel fuel.
[000101] The present description also provides methods for producing jet fuel. Jet fuel is clear to pale in color. The most common fuel is a paraffin / unleaded oil based fuel classified as Airplane A-1, which is produced to a set of international standard specifications. Jet fuel is a mixture of a large number of different hydrocarbons, possibly as much 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. Aviation fuel of the kerosene type (including Jet A and Jet A-1) has a carbon number distribution between C8 and C16. Aviation fuel of the naphtha or wide-cut type (including Jet B) typically has a carbon number distribution between C5 and C15. A fuel mixture that satisfies ASTM D1655 can be defined as jet fuel.
[000102] In certain embodiments, both Airplanes (Jet A and Jet B) contain various additives. Useful additives include, but are not limited to, antioxidants, antistatic agents, corrosion inhibitors, and fuel system freeze inhibiting agents (FSII). Antioxidants prevent gum formation and are commonly based on alkylated phenols, for example, AO-30, AO-31, or AO-37. Antistatic agents dissipate static electricity and prevent the formation of sparks. Stadis 450 with dinonyl naphthyl sulfonic acid (DIN NSA) as the active ingredient, is an example. Corrosion inhibitors (for example, DCI-4A) are used for civil and military fuels, and DCI-6A is used for military fuels. FSII agents include, for example, Di-EGM E.
[000103] In some embodiments, the oxygenated intermediates may comprise a carbonyl-containing compound that can take part in a base-catalyzed condensation reaction. In some embodiments, an optional dehydrogenation reaction can be used to increase the amount of carbonyl-containing compounds in the oxygenated intermediate stream to be used as a feed for the condensation reaction. In these embodiments, the oxygenated intermediates and / or a portion of the biocomposite-based feed charge stream can be dehydrogenated in the presence of a catalyst.
[000104] In some embodiments, a dehydrogenation catalyst may be preferred for an oxygenated intermediate stream comprising alcohols, diols, and triols. In general, alcohols cannot participate in aldolic condensation directly. The hydroxyl group or groups present can be converted to carbonyls (for example, aldehydes, ketones, etc.) in order to participate in an aldolic condensation reaction. A dehydrogenation catalyst can be included to effect the dehydrogenation of any alcohols, diols, or polyols present to form ketones and aldehydes. The dehydration catalyst is typically formed from the same metals as used for hydrogenation, hydrogenolysis, or aqueous phase reform. These catalysts are described in more detail above. The performance of dehydrogenation can be improved by removing or consuming hydrogen as it forms during the reaction. The dehydrogenation step can be carried out as a separate reaction step before an aldolic condensation reaction, or a dehydrogenation reaction can be carried out in concert with the aldolic condensation reaction. For concert dehydrogenation and aldolic condensation reactions, the dehydrogenation and aldolic condensation functions can occur on the same catalyst. For example, a metal hydrogenation / dehydrogenation functionality may be present in the catalyst comprising an alkaline functionality.
[000105] The dehydrogenation reaction can result in the production of a compound containing carbonyl. Suitable carbonyl-containing compounds can include, but are not limited to, any compound comprising a carbonyl functional group that can form carbon dioxide species or can react in a condensation reaction with carbon dioxide species. In one embodiment, a carbonyl-containing compound may include, but is not limited to, ketones, aldehydes, furfural, hydroxy carboxylic acids, and, carboxylic acids. Ketones may include, without limitation, hydroxy ketones, cyclic ketones, diketones, acetone, propanone, 2-oxopropanal, butanone, butane-2,3-dione, 3-hydroxybutane-2-one, pentanone, circuitopentanone, pentane-2,3- diona, pentane-2,4-dione, hexanone, circuitexanone, 2-methyl-circuitopentanone, heptanone, octanone, nonanone, decanone, undecanone, dodecanone, methylglyoxal, butanedione, pentanedione, dichetohexane, dihydroxyacetone, and isomers of the same . Aldehydes may include, without limitation, hydroxyaldehydes, acetaldehyde, glyceraldehyde, 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-hydroxyacid and lactic acid. Furfurals may include, without limitation, hydroxylmethylfurfural, 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. In one embodiment, a dehydrogenation reaction can result in the production of a carbonyl-containing compound that is combined with the oxygenated intermediates to become a part of the oxygenated intermediates fed into the condensation reaction.
[000106] In one embodiment, an acid catalyst can be used to optionally dehydrate at least a portion of the oxygenated intermediate stream. Acid catalysts suitable for use in the dehydration reaction may include, but are not limited to, mineral acids (eg, HCl, H2S04), solid acids (eg, zeolites, ion exchange kingdoms) and acid salts (eg, LaCI3). Additional acid catalysts may include, without limitation, zeolites, carbides, nitrides, zirconia, alumina, silica, aluminosilicates, phosphates, titanium oxides, zinc oxides, vanadium oxides, lanthanum oxides, yttrium oxides, scandium oxides, oxides of scandium, oxides magnesium, cerium oxides, barium oxides, calcium oxides, hydroxides, heteropoly acids, inorganic acids, acid modified resins, base modified resins, and any combination thereof. In some embodiments, the dehydration catalyst can also include a modifier. Suitable modifiers can include, for example, La, Y, Sc, P, B, Bi, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, and any combination thereof. The modifiers may be useful, inter alia, to perform a hydrogenation / dehydrogenation reaction in concert with the dehydration reaction. In some embodiments, the dehydration catalyst can also include a metal. Suitable metals may include, for example, Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, The, alloys, and any combination thereof. The dehydration catalyst can be self-supporting, supported on an inert support or resin, or it can be dissolved in solution.
[000107] In some embodiments, the dehydration reaction can occur in the vapor phase. In other embodiments, the dehydration reaction can occur in the liquid phase. For liquid dehydration reactions, an aqueous solution can be used to carry out the reaction. In one embodiment, other solvents in addition to water, can be used to form the aqueous solution. For example, water-soluble organic solvents may be present. Suitable solvents may include, but are not limited to, hydroxymethylfurfural (HMF), dimethylsulfoxide (DMSO), 1-methyl-n-pyrrolidone (NM P), and any combination thereof. Other suitable aprotic solvents can also be used alone or in combination with any of these solvents.
[000108] In one embodiment, the processing reactions may comprise an optional ketonation reaction. A ketonization reaction can increase the number of functional ketone groups within at least a portion of the oxygenated intermediates. For example, an alcohol can be converted to the ketone in a ketone reaction. Ketonation can be performed in the presence of an alkaline catalyst. Any of the alkaline catalysts described above as the basic component of the aldolic condensation reaction can be used to carry out a ketonization reaction. Suitable reaction conditions are known to a person skilled in the art and generally correspond to the reaction conditions listed above with respect to the aldolic condensation reaction. The ketonization reaction can be carried out as a separate reaction step, or it can be carried out in concert with the aldolic condensation reaction. The inclusion of a basic functional site in the aldolic condensation catalyst can result in concerted aldolic condensation and ketonization reactions.
[000109] In one embodiment, the processing reactions may comprise an optional furan ring opening reaction. A furan ring opening reaction can result in the conversion of at least a portion of any oxygenated intermediates comprising a furan ring to compounds that are more reactive in an aldolic condensation reaction. A furan ring opening reaction can be carried out in the presence of an acid catalyst. Any of the acid catalysts described above as the acid component of the aldolic condensation reaction can be used to effect a furan ring opening reaction. Suitable reaction conditions are known to a person skilled in the art and generally correspond to the reaction conditions listed above with respect to the aldolic condensation reaction. The furan ring opening reaction can be carried out as a separate reaction step, or it can be carried out in concert with the aldolic condensation reaction. The inclusion of an acidic functional site in the aldolic condensation catalyst can result in furan ring opening and concerted aldolic condensation reactions. Such an embodiment can be advantageous since any furan ring can be opened in the presence of an acidic functionality and reacted in an aldolic condensation reaction using an alkaline functionality. Such a concert reaction scheme can allow the production of a greater amount of higher hydrocarbons to be formed for a given oxygenated intermediate feed.
[000110] In one embodiment, the production of a compound greater than or equal to C4 can occur by condensation, which can include the aldolic condensation of the oxygenated intermediates in the presence of a condensation catalyst. Aldolic condensation generally involves carbon - carbon coupling between two compounds, at least one of which may contain a carbonyl group, to form a larger organic molecule. For example, acetone can react with hydroxymethylfurfural to form a C9 species, which subsequently can react with another hydroxymethylfurfural molecule to form a C15 species. In various embodiments, the reaction is commonly carried out in the presence of a condensation catalyst. The condensation reaction can be carried out in the vapor phase or in the liquid phase. In one embodiment, the reaction can take place at a temperature ranging from 7 ° C to 377 ° C depending on the reactivity of the carbonyl group.
[000111] The condensation catalyst in general will be a catalyst capable of forming longer chain compounds linking two molecules through a new carbon - carbon bond, such as an alkaline catalyst, a multifunctional catalyst having both acid and base functionality, or any type of catalyst that also comprises an optional metal functionality. In one embodiment, the multifunctional catalyst can be a catalyst having both a strong acid functionality and a strong base functionality. In one embodiment, aldol catalysts can comprise Li, Na, K, Cs, B, Rb, Mg, Ca, Sr, Si, Ba, Al, Zn, Ce, La, Y, Sc, Y, Zr, Ti , hydrotalcite, zinc aluminate, phosphate, base treated aluminosilicate zeolite, an alkaline resin, alkaline nitride, alloys or any combination thereof. In one embodiment, the alkaline catalyst can also comprise an oxide of Ti, Zr, V, Nb, Ta, Mo, Cr, W, Mn, Re, Al, Ga, In, Co, Ni, Si, Cu, Zn , Sn, Cd, Mg, P, Fe, or any combination thereof. In one embodiment, the condensation catalyst comprises mixed alkaline oxide catalysts. Suitable alkaline oxide catalysts mixed together can comprise a combination of magnesium, zirconium, and oxygen, which can comprise, without limitation: Si - Mg - O, Mg - Ti - O, Y - Mg - O, Y --Zr-- O, Ti - Zr - O, Ce - Zr - O, Ce - Mg - O, Ca - Zr - O, La - Zr - O, B-- Zr - O, La - Ti - O, B - Ti - O, and any combinations thereof. Different atomic ratios of Mg / Zr or combinations of various other elements that make up the mixed oxide catalyst can be used ranging from 0.01 to 50. In one embodiment, the condensation catalyst can additionally include a metal or alloys comprising metals, such as Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Bi, Pb, Os, alloys and combinations thereof. Such metals may be preferred when a dehydrogenation reaction must be performed in concert with the aldolic condensation reaction. In one embodiment, preferred Group IA materials may include Li, Na, K, Cs and Rb. In one embodiment, preferred Group IIA materials may include Mg, Ca, Sr and Ba. In one embodiment, Group IIB preferred materials may include Zn and Cd. In one embodiment, Group IIIB preferred materials may include Y and La. Alkaline resins can include resins that exhibit alkaline functionality. The alkaline catalyst can be self-supporting or adhered to any of the additional supports described below, including supports containing carbon, silica, alumina, zirconia, titania, vanádia, ceria, nitride, boron nitride, heteropoly acids, alloys and mixtures thereof.
[000112] In one embodiment, the condensation catalyst can be derived from the combination of MgO and Al2O3 to form a hydrotalcite material. Another preferred material contains ZnO and Al2O3 in the form of a zinc aluminate spinel. Another preferred material is a combination of ZnO, Al2O3, and CuO. Each of these materials may also contain an additional metal function provided by a Group VIIIB metal, such as Pd or Pt. Such metals may be preferred when a dehydrogenation reaction is to be performed in concert with the aldolic condensation reaction. In one embodiment, the alkaline catalyst can be a metal oxide containing Cu, Ni, Zn, V, Zr, or mixtures thereof. In another embodiment, the alkaline catalyst can be a zinc aluminate metal containing Pt, Pd Cu, Ni, or mixtures thereof.
[000113] In some embodiments, a base-catalyzed condensation reaction can be carried out using a condensation catalyst with both an acidic functionality and an alkaline functionality. The aldolic condensation acid catalyst may comprise hydrotalcite, zinc aluminate, phosphate, Li, Na, K, Cs, B, Rb, Mg, Si, Ca, Sr, Ba, Al, Ce, La, Sc, Y, Zr, Ti, Zn, Cr, or any combination thereof. In additional embodiments, the acid-alkaline catalyst can also include one or more oxides from the group of Ti, Zr, V, Nb, Ta, Mo, Cr, W, Mn, Re, Al, Ga, In, Fe , Co, Ir, Ni, Si, Cu, Zn, Sn, Cd, P, and combinations thereof. In one embodiment, the acid - alkaline catalyst may include a metal function provided by Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re , Mn, Cr, Mo, W, Sn, Os, alloys or combinations thereof. In one embodiment, the catalyst additionally includes Zn, Cd or phosphate. In one embodiment, the condensation catalyst can be a metal oxide containing Pd, Pt, Cu or Ni, and even more preferably a zirconium or aluminum metal oxide containing Mg and Cu, Pt, Pd or Ni. The acid - alkaline catalyst can also include a hydroxyapatite (PAH) combined with any one or more of the above metals. The acid - alkaline catalyst can be self-supporting or adhered to any of the additional supports described below, including supports containing carbon, silica, alumina, zirconia, titania, vanádia, ceria, nitride, boron nitride, heteropoly acids, alloys and mixtures thereof.
[000114] In one embodiment, the condensation catalyst can also include zeolites and other microporous supports that contain Group IA compounds, such as Li, NA, K, Cs and Rb. Preferably, the Group IA material may be present in an amount of less than that necessary to neutralize the acidic nature of the support. A metal function can also be provided by adding metals from Group VIIIB, or Cu, Ga, In, Zn or Sn. In one embodiment, the condensation catalyst can be derived from the combination of MgO and Al2O3 to form a hydrotalcite material. Another preferred material can contain a combination of MgO and ZrO2, or a combination of ZnO and Al2O3. Each of these materials may also contain an additional metal function provided by copper or a Group VIIIB metal, such as Ni, Pd, Pt, or combinations of the above.
[000115] The condensation catalyst can be self-supporting (that is, the catalyst does not need any other material to serve as a support), or it may need a separate support suitable for suspending the catalyst in the reagent stream. An exemplary support is silica, especially silica having a large surface area (greater than 100 square meters per gram), obtained by solgel synthesis, precipitation, or steaming. In other embodiments, particularly when the condensation catalyst is a powder, the catalyst system can include a binder to assist in the formation of the catalyst in a desirable catalyst form. Applicable forming processes may include extrusion, globule formation, oil dripping, or other known processes. Zinc oxide, alumina, and a peptizing agent can also be mixed and extruded to produce a formed material. After drying, this material can be calcined at an appropriate temperature for the formation of the catalytically active phase. Other catalyst supports as known to a person skilled in the art can also be used.
[000116] In some embodiments, the dehydration catalyst, a dehydrogenation catalyst, and the condensation catalyst can be present in the same reactor that the reaction conditions overlap to some degree. In these embodiments, a dehydration reaction and / or a dehydrogenation reaction can occur substantially simultaneously with the condensation reaction. In some embodiments, a catalyst may comprise active sites for a dehydration reaction and / or a dehydrogenation reaction in addition to a condensation reaction. For example, a catalyst can comprise active metals for a dehydration reaction and / or a dehydrogenation reaction together with a condensation reaction at separate sites in the catalyst or in the alloys. Suitable active elements can comprise any of those listed above with respect to the dehydration catalyst, the dehydrogenation catalyst, and the condensation catalyst. Alternatively, a physical mixture of dehydration, dehydrogenation, and condensation catalysts can be employed. While it is not intended to be limited in theory, it is believed that using a condensation catalyst comprising a metal and / or an acidic functionality can assist in pushing the limited equilibrium aldolic condensation reaction to the end. Advantageously, this can be used to perform multiple condensation reactions with dehydration and / or dehydrogenation of the intermediates, in order to form (through condensation, dehydration, and / or dehydrogenation) higher molecular weight oligomers as desired to produce diesel fuel or jet.
[000117] The compounds greater than or equal to specific C4 produced in the condensation reaction may depend on several factors, including, without limitation, the type of oxygenated intermediates in the reagent stream, condensation temperature, condensation pressure, the reactivity of the catalyst, and the flow of the reagent stream.
[000118] In general, the condensation reaction can be carried out at a temperature at which the proposed reaction thermodynamics is favorable. For liquid condensed phase reactions, the pressure inside the reactor must be sufficient to maintain at least a portion of the reactants in the condensed liquid phase at the reactor inlet. For vapor phase reactions, the reaction must be carried out at a temperature where the vapor pressure of the oxygenates is at least 0.1 bar (0.01 mPa), and the reaction thermodynamics is favorable. The condensation temperature will vary depending on the specific oxygenated intermediates used, but, in general, it can vary between 75 ° C and 500 ° C for reactions occurring in the vapor phase, and more preferably it varies between 125 ° C and 450 ° C. For liquid phase reactions, the condensation temperature can vary between 5 ° C and 475 ° C, and the condensation pressure can vary between 0.01 bar (0.001 mPa) and 100 bar (10 mPa). Preferably, the condensation temperature can vary between 15 ° C and 300 ° C, or between 15 ° C and 250 ° C.
[000119] Varying the above factors, as well as others, will generally result in a modification to the specific composition and yields of the compounds greater than or equal to C4. For example, varying the temperature and / or pressure of the reactor system, or the particular catalyst formulations, can result in the production of alcohols greater than or equal to C4 and / or ketones instead of hydrocarbons greater than or equal to C4. The hydrocarbon product greater than or equal to C4 can also contain a variety of olefins, and alkanes of various sizes (typically branched alkanes). Depending on the condensation catalyst used, the hydrocarbon product may also include aromatic and cyclic hydrocarbon compounds. The hydrocarbon product greater than or equal to C4 may also contain undesirably high levels of olefins, which can lead to the formation of coke or deposits in combustion engines, or other undesirable hydrocarbon products. In such cases, hydrocarbons can optionally be hydrogenated to reduce ketones to alcohols and hydrocarbons, while alcohols and olefinic hydrocarbons can be reduced to alkanes, thereby forming a more desirable hydrocarbon product having reduced levels of olefins, aromatics or alcohols.
[000120] Condensation reactions can be carried out in any suitable design reactor, including continuous flow, batch, semi-stacked or multi-system reactors, without limitation as to design, size, geometry, flow rates, and the like. The reactor system can also use a fluidized catalytic bed system, an oscillating bed system, fixed bed system, a moving bed system, or a combination of the above. In some embodiments, two-phase (eg, liquid-liquid) and three-phase (eg, liquid-liquid-solid) reactors can be used to perform the condensation reactions.
[000121] In a continuous flow system, the reactor system can include an optional dehydrogenation bed adapted to produce dehydrogenated oxygenated intermediates, an optional dehydration bed adapted to produce dehydrated oxygenated intermediates, and a condensation bed adapted to produce larger compounds or equal to C4 from the oxygenated intermediates. The dehydrogenation bed can be configured to receive the reagent stream and produce the desired oxygenated intermediates, which can have an increase in the amount of compounds containing carbonyl. The dehydration bed can be configured to receive the reagent stream and produce the desired oxygenated intermediates. The condensation bed can be configured to receive the oxygenated intermediates for contact with the condensation catalyst and the production of the desired compounds greater than or equal to C4. For systems with one or more finishing steps, an additional reaction bed to conduct the finishing process or processes may be included after the condensation bed.
[000122] In one embodiment, the optional dehydration reaction, the optional dehydrogenation reaction, the optional ketonation reaction, the optional ring opening reaction, and the condensation reaction catalyst beds can be positioned within the same reactor vessel or in separate reactor vessels in fluid communication with each other. Each reactor vessel can preferably include an outlet adapted to remove the product stream from the reactor vessel. For systems with one or more finishing steps, the finishing reaction bed or beds may be inside the same reactor vessel together with the condensation bed or in a separate reactor vessel in fluid communication with the reactor vessel having the condensation bed.
[000123] In one embodiment, the reactor system may also include additional outlets to allow removal of portions from the reagent stream to further advance or direct the reaction to the desired reaction products, and to allow for collection and recycling reaction by-products for use in other portions of the system. In one embodiment, the reactor system may also include additional inputs to allow the introduction of supplementary materials to further advance or direct the reaction to the desired reaction products, and to allow recycling of reaction by-products for use in other reactions.
[000124] In one embodiment, the reactor system can also include elements which allow the separation of the reagent stream into different components that can find use in different reaction schemes or simply to promote the desired reactions. For example, a separator unit, such as a phase separator, extractor, purifier or distillation column, can be installed prior to the condensation step to remove water from the reagent stream for the purposes of advancing the condensation reaction to favor the production of superior hydrocarbons. In one embodiment, a separation unit can be installed to remove specific intermediates to allow for the production of a desired product stream containing hydrocarbons within a particular carbon number range, or for use as reaction products or in other systems or processes.
[000125] The condensation reaction can produce a wide range of compounds with carbon numbers ranging from C4 or C30 or greater. Exemplary compounds may include, for example, alkanes greater than or equal to C4, alkenes greater than or equal to C4, cycloalkanes greater than or equal to C5, cycloalkenes greater than or equal to C5, aryls, fused aryl groups, alcohols greater than or equal to C4, ketones greater than or equal to C4, and mixtures thereof. Alkanes greater than or equal to C4 and alkenes greater than or equal to C4 may vary from 4 to 30 carbon atoms (i.e., C4 to C30 alkanes and C4 to C30 alkenes) and may be straight chain alkanes or alkenes or branched. Alkanes greater than or equal to C4 and alkenes greater than or equal to C4 may also include fractions of alkanes and alkenes from C7 to C14, C12 to C24, respectively, with the fraction of C7 to C14 directed to jet fuel mixtures, and to fraction of C12 to C24 directed to diesel fuel mixtures and other industrial applications. Examples of various alkanes greater than or equal to C4 and alkenes greater than or equal to C4 may include, without limitation, butane, butene, pentane, pentene, 2-methylbutane, hexane, hexene, 2-methylpentane, 3-methylpentane, 2,2- dimethylbutane, 2,3-dimethylbutane, heptane, heptane, octane, octene, 2,2,4, -trimethylpentane, 2,3-dimethyl hexane, 2,3,4-trimethylpentane, 2,3-dimethylpentane, nonane, nonene, dean, decene, undecane, undecene, dodecane, dodecene, tridecane, tridecene, tetradecane, tetradecene, pentadecane, pentadecene, hexadecane, hexadecene, heptydecane, heptydecene, octydecane, octildecene, nonildicos, unildicos, eildyne, nonildicos, and doeicosene, trieicosane, trieicosene, tetraeicosane, tetraeicosene, and isomers thereof.
[000126] Cycloalkanes greater than or equal to C5 and cycloalkenes greater than or equal to C5 may have from 5 to 30 carbon atoms and may be unsubstituted, monosubstituted or polysubstituted. In the case of monosubstituted and polysubstituted compounds, the substituted group may include a alkyl greater than or equal to branched C3, an alkyl greater than or equal to branched C1, an alkylene greater than or equal to C3, an alkylene greater than or equal to branched C1, an alkylene greater than or equal to straight chain C2, an aryl group, or a combination thereof. In one embodiment, at least one of the substituted groups can include a C3 to C12 alkyl, a straight chain C1 to C12 alkyl, a branched C3 to C12 alkylene, a straight chain C1 to C12 alkylene, a straight chain C2 to C12 alkylene, an aryl group, or a combination thereof. In yet another embodiment, at least one of the substituted groups can include a branched C3 to C4 alkyl, a straight chain C1 to C4 alkyl, a branched C3 to C4 alkylene, a straight chain C1 to C4 alkylene , a straight chain C2 to C4 alkylene, an aryl group, or any combination thereof. Examples of desirable cycloalkanes greater than or equal to C5 and cycloalkenes greater than or equal to C5 may include, without limitation, cyclopentane, cyclopentene, cyclohexane, cyclohexene, methylcyclopentane, methylcyclopentene, ethylcyclopentane, ethylcyclopentene, ethylcyclohexane, ethylene cycle and hexane .
[000127] The aryl groups contain an aromatic hydrocarbon in both an unsubstituted form (phenyl), monosubstituted and polysubstituted. In the case of monosubstituted and polysubstituted compounds, the substituted group may include a branched C3 greater or equal, a straight chain C1 greater or equal, a branched C3 greater or equal, a C2 greater than or equal to alkylene straight chain, a phenyl group, or a combination thereof. In one embodiment, at least one of the substituted groups can include a C3 to C12 alkyl, a straight chain C1 to C12 alkyl, a C3 to C12 alkylene, a straight chain C2 to C12 alkylene, a group phenyl, or any combination thereof. In yet another embodiment, at least one of the substituted groups can include a branched C3 to C4 alkyl, a straight chain C1 to C4 alkyl, a branched C3 to C4 alkylene, a straight chain C2 to C4 alkylene , a phenyl group, or any combination thereof. Examples of various aryl compounds can include, without limitation, benzene, toluene, xylene (dimethylbenzene), ethyl benzene, para-xylene, meta-xylene, ortho-xylene, and C9 aromatics.
[000128] Fused aryl groups contain bicyclic or polycyclic aromatic hydrocarbons, either in an unsubstituted, monosubstituted or polysubstituted form. In the case of monosubstituted and polysubstituted compounds, the substituted group may include an alkyl greater than or equal to C3, an alkyl greater than or equal to straight chain C1, an alkylene greater than or equal to branched C3, an alkylene greater than or equal to C2 chain linear, a phenyl group, or a combination thereof. In another embodiment, at least one of the substituted groups can include a branched C3 to C4 alkyl, a straight chain C1 to C4 alkyl, a branched C3 to C4 alkylene, a straight chain C2 to C4 alkylene, a phenyl group, or any combination thereof. Examples of various fused aryl groups can include, without limitation, naphthalene, anthracene, tetrahydronaphthalene, and decahydronaphthalene, indane, indene, and isomers thereof.
[000129] Moderate fractions such as C7 to C14 can be separated for jet fuel, while heavier fractions, such as C12 to C24, can be separated for diesel use. The heavier fractions can be used as lubricants or broken to produce additional gasoline and / or diesel fractions. Compounds greater than or equal to C4 can also find use as industrial chemicals, either as an intermediate or as a final product. For example, the aryl toluene, xylene, ethylbenzene, para-xylene, meta-xylene, and ortho-xylene groups can find use as chemical intermediates for the production of plastics and other products. Meanwhile, aromatic C9 and fused aryl groups, such as naphthalene, anthracene, tetrahydronaphthalene, and decahydronaphthalene, may find use as solvents in industrial processes.
[000130] In one embodiment, additional processes can be used to treat the fuel mixture to remove certain components or to further conform the fuel mixture to a diesel fuel or jet fuel standard. Suitable techniques may include hydrotreating to reduce the amount of or remove any remaining oxygen, sulfur, or nitrogen in the fuel mixture. The conditions for hydrotreating a hydrocarbon stream are known to a person skilled in the art.
[000131] In one embodiment, hydrogenation can be carried out in place of or after the hydrotreating process to saturate at least part of the olefinic bonds. In some embodiments, a hydrogenation reaction can be carried out in concert with the aldolic condensation reaction by including a metal group function with the aldolic condensation catalyst. 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 of the fuel mixture stream can be carried out according to known procedures, both with the continuous method and with the batch method. A hydrogenation reaction can be used to remove remaining carbonyl groups and / or remaining hydroxyl groups. In such cases, any of the hydrogenation catalysts described above can be used. In general, the finishing step can be carried out at finishing temperatures that vary between 80 ° C and 250 ° C, and finishing procedures can vary between 5 bar (0.5 mPa) and 150 bar (5 mPa). In one embodiment, the finishing step can be carried out in the vapor phase or in the liquid phase, and the use, external hydrogen, recycled hydrogen, or combinations thereof, as needed.
[000132] In one embodiment, isomerization can be used to treat the fuel mixture to introduce a desired degree of branching or other shape selectivity for at least some components in the fuel mixture. It may also be useful to remove any impurities before the hydrocarbons are contacted with the isomerization catalyst. The isomerization step can comprise 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 can be carried out in a countercurrent manner in a unit upstream of the isomerization catalyst, in which the gas and liquid are contacted with each other, or before the current isomerization reactor in a separate extraction unit using a countercurrent principle.
[000133] After the optional extraction step the fuel mixture can be passed to a reactive isomerization unit comprising one or more catalyst beds. The catalyst beds of the isomerization unit can operate either concurrently or countercurrently. In the isomerization unit, the pressure can vary between 20 bar (2 mPa) to 150 bar (15 mPa), preferably between 20 bar (2 mPa) to 100 bar (10 mPa), the temperature ranging between 195 ° C and 500 ° C, preferably between 300 ° C and 400 ° C. In the isomerization unit, any isomerization catalyst known in the art can be used. In some embodiments, suitable isomerization catalysts may contain molecular sieves and / or a Group VII metal and / or a carrier. In one embodiment, the isomerization catalyst can contain SAPO-11 or SAPO41 or ZSM-22 or ZSM-23 or ferrierite and Pt, Pd or Ni and Al2O3 or SiO2. Typical isomerization catalysts are, for example, Pt / SAPO-11 / Al2O3, Pt / ZSM-22 / Al2O3, Pt / ZSM-23 / Al2O3 and Pt / SAPO-11 / SiO2.
[000134] Other factors, such as the concentration of water or unwanted oxygenated intermediates, can also affect the composition and yield of compounds greater than or equal to C4, as well as the activity and stability of the condensation catalyst. In such cases, the process may include a water removal step that removes a portion of the water prior to the condensation reaction and / or the optional dehydration reaction, or a separation unit for removing unwanted oxygenated intermediates. For example, a separator unit, such as a phase separator, extractor, purifier or distillation column, can be installed before the condensation reactor in order to remove a portion of the water from the reagent stream containing the oxygenated intermediates. A separation unit can also be installed to remove specific oxygenated intermediates to allow the production of a desired product stream containing hydrocarbons within a particular carbon band, or for use as reaction products or in other systems or processes.
[000135] Thus, in one embodiment, the fuel mixture produced by the processes described here is a hydrocarbon mixture that meets the requirements for jet fuel (for example, it conforms to ASTM D1655). In another embodiment, the product of the processes described here is a hydrocarbon mixture that comprises a fuel mixture that meets the requirements for a diesel fuel (for example, it conforms to ASTM D975).
[000136] In another embodiment, a fuel mixture comprising hydrocarbon gasoline (i.e., a gasoline fuel) can be produced. "Gasoline hydrocarbons" refer to hydrocarbons predominantly comprising hydrocarbons from C5 to C9, for example, hydrocarbons from C6 to C8, and having a boiling point range from 32 ° C (90 ° F) to 204 ° C (400 ° F). Gasoline hydrocarbons may include, but are not limited to, straight racing gasoline, naphtha, thermally catalyzed or fluidized cracked gasoline, VB gasoline, and coke gasoline. The hydrocarbon content of gasoline is determined by the ASTM D2887 Method.
[000137] In yet another embodiment, olefins greater than or equal to C2 can be produced by catalytically reacting oxygenated intermediates in the presence of the dehydration catalyst at a dehydration temperature and dehydration pressure to produce a reaction stream comprising olefins greater than or equal to C2. Olefins greater than or equal to C2 may comprise straight or branched chain hydrocarbons containing one or more carbon - carbon double bonds. In general, olefins greater than or equal to C2 may contain from 2 to 8 carbon atoms, and more preferably from 3 to 5 carbon atoms. In one embodiment, the olefins can comprise propylene, butylene, pentylene, isomers of the above, and mixtures of any two or more of the above. In another embodiment, olefins greater than or equal to C2 may include olefins greater than or equal to C4 produced by catalytically reacting a portion of the olefins greater than or equal to C2 on an olefin isomerization catalyst.
[000138] The dehydration catalyst can comprise a member selected from the group consisting of acid alumina, aluminum phosphate, silica phosphate - alumina, silica - amorphous alumina, aluminum silicate, zirconia, sulfated zirconia, zirconia with tungsten, carbide tungsten, molybdenum carbide, titania, sulfated carbon, phosphate carbon, phosphate silica, phosphate alumina, acid resin, heteropoly acid, inorganic acid, and a combination of any two or more of the above. In one embodiment, the dehydration catalyst may further comprise a modifier selected from the group consisting of Ce, Y, Sc, La, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, P , B, Bi, and a combination of any two or more of the above. In another embodiment, the dehydration catalyst may additionally comprise an oxide of an element, the element selected from the group consisting of Ti, Zr, V, Nb, Ta, Mo, Cr, W, Mn, Re, Al , Ga, In, Fe, Co, Ir, Ni, Si, Cu, Zn, Sn, Cd, P, and a combination of any two or more of the above. In yet another embodiment, the dehydration catalyst may additionally comprise a metal selected from the group consisting of Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, a league of any two or more of the above, and a combination of any two or more of the above.
[000139] In yet another embodiment, the dehydration catalyst can comprise an aluminosilicate zeolite. In some embodiments, the dehydration catalyst may additionally comprise a modifier selected from the group consisting of Ga, In, Zn, Fe, Mo, Ag, Au, Ni, P, Sc, Y, Ta, a lanthanide, and a combination of any two or more of the above. In some embodiments, the dehydration catalyst may additionally comprise a metal selected from the group consisting of Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd , Ir, Re, Mn, Cr, Mo, W, Sn, Os, a league of any two or more of the above, and a combination of any two or more of the above.
[000140] In another embodiment, the dehydration catalyst can comprise an aluminosilicate zeolite that contains a bifunctional pentasil ring. In some embodiments, the dehydration catalyst may additionally comprise a modifier selected from the group consisting of Ga, In, Zn, Fe, Mo, Ag, Au, Ni, P, Sc, Y, Ta, a lanthanide, and a combination of any two or more of the above. In some embodiments, the dehydration catalyst may additionally comprise a metal selected from the group consisting of Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd , Ir, Re, Mn, Cr, Mo, W, Sn, Os, a league of any two or more of the above, and a combination of any two or more of the above.
[000141] The dehydration reaction can be conducted at a temperature and pressure where the thermodynamics are favorable. In general, the reaction can be carried out in the vapor phase, in the liquid phase, or a combination of both. In one embodiment, the dehydration temperature can vary between 100 ° C and 500 ° C, and the dehydration pressure can vary between 1 bar (absolute) (0.1 mPa abs.) And 60 bar (6 mPa). In another embodiment, the dehydration temperature can vary between 125 ° C and 450 ° C. In some embodiments, the dehydration temperature can vary between 150 ° C and 350 ° C, and the dehydration pressure can vary between 5 bar (0.5 mPa) and 50 bar (5 mPa). In yet another embodiment, the dehydration temperature can vary between 175 ° C and 325 ° C.
[000142] Paraffins greater than or equal to C6 are produced through the catalytic reaction of olefins greater than C2 with a stream of isoparaffins greater than or equal to C4 in the presence of an alkylation catalyst at an alkylation temperature and an alkylation pressure for produce a product stream comprising paraffins greater than or equal to C6. Isoparaffins greater than or equal to C4 may include alkanes and cycloalkanes having 4 to 7 carbon atoms, such as isobutane, isopentane, naphthenes, and higher homologues having a tertiary carbon atom (for example, 2-methylbutane and 2,4-dimethylpentane ), isomers of the above, and mixtures of any two or more of the above. In one embodiment, the stream of isoparaffins greater than or equal to C4 may comprise internally generated isoparaffins greater than or equal to C4, isoparaffins greater than or equal to C4, isoparaffins greater than or equal to recycled C4, or combinations of any two or more of previous ones.
[000143] Paraffins greater than or equal to C6 may be branched paraffins, but may also include normal paraffins. In one version, paraffins greater than or equal to C6 may comprise a member selected from the group consisting of a C6 to C10 alkane, a branched C6 alkane, a branched C7 alkane, a branched C8 alkane, a branched C9 alkane, a branched C10 alkane, or a mixture of any two or more of the above. In one version, paraffins greater than or equal to C6 may include, for example, dimethylbutane, 2,2-dimethylbutane, 2,3-dimethylbutane, methylpentane, 2-methylpentane, 3-methylpentane, dimethylpentane, 2,3-dimethylpentane, 2 , 4-dimethylpentane, methylhexane, 2,3-dimethylhexane, 2,3,4-trimethylpentane, 2,2,4-trimethylpentane, 2,2,3-trimethylpentane, 2,3,3-trimethylpentane, dimethyl -hexane, or mixtures of any two or more of the above.
[000144] The alkylation catalyst can comprise a member selected from the group of sulfuric acid, hydrofluoric acid, aluminum chloride, boron trifluoride, solid phosphoric acid, chlorinated alumina, acid alumina, aluminum phosphate, silica phosphate - alumina , amorphous silica - aluminosilicate, aluminosilicate zeolite, zirconia, sulfated zirconia, tungsten zirconia, tungsten carbide, molybdenum carbide, titania, sulfated carbon, phosphate carbon, phosphate silica, phosphate alumina, acidic, inorganic acid, heteropoli , and a combination of any two or more of the above. The alkylation catalyst can also include a mixture of a mineral acid with a Friedel-Crafts metal halide, such as aluminum bromide, and other proton donors.
[000145] In one embodiment, the alkylation catalyst can comprise an aluminosilicate zeolite. In some embodiments, the alkylation catalyst may further comprise a modifier selected from the group consisting of Ga, In, Zn, Fe, Mo, Ag, Au, Ni, P, Sc, Y, Ta, a lanthanide, and a combination of any two or more of the above. In some embodiments, the alkylation catalyst may additionally comprise a metal selected from the group consisting of Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd , Ir, Re, Mn, Cr, Mo, W, Sn, Os, a league of any two or more of the above, and a combination of any two or more of the above.
[000146] In another embodiment, the alkylation catalyst can comprise an aluminosilicate zeolite that contains a bifunctional pentasil ring. In some embodiments, the alkylation catalyst may further comprise a modifier selected from the group consisting of Ga, In, Zn, Fe, Mo, Ag, Au, Ni, P, Sc, Y, Ta, a lanthanide, and a combination of any two or more of the above. In some embodiments, the alkylation catalyst may additionally comprise a metal selected from the group consisting of Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd , Ir, Re, Mn, Cr, Mo, W, Sn, Os, a league of any two or more of the above, and a combination of any two or more of the above. In one version, the dehydration catalyst and the alkylation catalyst can be atomically identical.
[000147] The alkylation reaction can be conducted at a temperature where the thermodynamics are favorable. In general, the alkylation temperature can vary between -20 ° C and 300 ° C, and the alkylation pressure can vary between 1 bar (absolute) (0.1 mPa abs.) And 80 bar (8 mPa). In some embodiments, the alkylation temperature can vary between 100 ° C and 300 ° C. In another version, the alkylation temperature can vary between 0 ° C and 100 ° C. In additional embodiments, the alkylation temperature can vary between 0 ° C and 50 ° C. In further other embodiments, the alkylation temperature can vary between 70 ° C and 250 ° C, and the alkylation pressure can vary between 5 bar (0.5 mPa) and 80 bar (8 mPa). In one embodiment, the alkylation catalyst can comprise a mineral acid or a strong acid. In another embodiment, the alkylation catalyst can comprise a zeolite and the alkylation temperature can be greater than 100 ° C.
[000148] In one embodiment, an olefinic oligomerization reaction can be conducted. The oligomerization reaction can be carried out in any suitable reactor configuration. Suitable configurations may include, but are not limited to, batch reactors, semi-stack reactors, or continuous reactor designs such as, for example, fluidized bed reactors with external regeneration vessels. Reactor designs may include, but are not limited to, tubular reactors, fixed bed reactors, or any other type of reactor suitable for carrying out the oligomerization reaction. In one embodiment, a continuous oligomerization process for the production of jet fuel boiling range diesel and hydrocarbons can be carried out using an oligomerization reactor to contact an olefin feed stream comprising short chain olefins having a length of chain of 2 to 8 carbon atoms with a zeolite catalyst under high temperature and pressure in order to convert the short chain olefins to a fuel mixture in the diesel boiling range. The oligomerization reactor can be operated at relatively high pressures from 20 bar (2 mPa) to 100 bar (10 mPa), and temperatures ranging between 150 ° C and 300 ° C, preferably between 200 ° C to 250 ° C.
[000149] 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 that meets 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 can be used to generate a fuel mixture comprising hydrocarbons from C12 to C24 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 together with the diesel fraction and can be used either as a paraffin for lighting, as a jet fuel mixture component in conventional synthetic or raw derived jet fuels, or as a reagent ( especially the fraction of C10 to C13) in the process to produce LAB (Linear Alkyl Benzene). The naphtha fraction, after hydroprocessing, can be routed to a thermal cracker for the production of ethylene and propylene or routed to a catalytic cracker to produce ethylene, propylene, and gasoline.
[000150] Additional processes can be used to treat the fuel mixture to remove certain components or to further conform the fuel mixture to a diesel fuel or jet fuel standard. Appropriate techniques may include hydrotreating to remove any remaining oxygen, sulfur, or nitrogen in the fuel mixture. Hydrogenation can be carried out after the hydrotreating process to saturate at least part of the 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). A hydrogenation step of the fuel mixture stream can be carried out according to known procedures, in a continuous and batch manner.
[000151] To facilitate a better understanding of the present invention, the following examples of preferred embodiments are given. In no case should the following examples be read to limit, or to define, the scope of the invention. EXAMPLES
[000152] Example 1: Effects of Solvent Impregnation and Factors Affecting the Transfer of Various Types of Cellulosic Biomass. Example 1A: 1.5 grams of mixed coniferous wood chips (14% moisture), sized for nominal 8 mm x 4 mm x 3 mm chips, were dripped into a 2.5 cm layer of mixed aqueous / organic solvent (25% 2-propanol and 20% ethanol in deionized water) in a 21-mm 8-dramatic flask. Approximately 50% of the chips dropped to the bottom of the flask, while the remaining 50% floated on the surface despite the mixture breaking the surface tension. When the water was substituted for the mixed organic / aqueous solvent, similar results were obtained. Example IB: Example 1A was repeated, except 3.5 grams of coniferous wood chips were added to the 8 dram flask, and the solvent was added next to obtain a 2.6 cm layer of aqueous / organic solvent mixed in the flask . The contents were mixed and allowed to rest. Approximately 60% of the wood chips remained at the bottom of the jar, and approximately 40% floated to the top surface. Example 1C: Example IB was repeated, except 2.0 grams of similarly sized pine chips (34.3% moisture) were used. Approximately 75% of the chips remained at the bottom of the flask, and approximately 25% floated on the surface. Example 1D: 6.55 grams of coniferous wood chips having the dimensions of Example 1A were loaded into a 1 inch diameter 90% pressure vessel filled with 33 grams of an aqueous / organic solvent (25% 2-propanol and 20% ethanol in deionized water). The container is pressurized to 50 psi with N2 for 30 minutes and then to 200 psi with N2 for 30 minutes. The pressure was then vented, and the contents were moved to a beaker. The solvent was then decanted to recover the solvent-impregnated wood chips. 2.18 grams of the solvent-impregnated wood chips were added to the freshly mixed organic / aqueous solvent as in Example 1A. All the wood chips immediately sank to the bottom of the jar. Example 1E: A 1 inch diameter tube was filled with 2.5 inches of the nominal 8 mm x 6 mm x 3 mm coniferous wood chips. This provides a nominal 3: 1 tube-to-particle aspect ratio. The opening of a ball valve with an inch of bottom does not cause wood chips to fall out of the vertical retaining tube. Pressurizing the tube with 50 psi of N2 and then 200 psi of N2 resulted in the release of gas pressure when the ball valve was opened, but no chips were dislodged from the tube. The addition of 30.4 grams of an aqueous / organic solvent (25% 2-propanol and 20% ethanol in deionized water) resulted in a swelling of the splinter layer from 2.5 to 2.87 inches. The opening of the spherical valve displaced 27 grams of liquid from the bed, but only 5 wood chips were displaced. The application of a mechanical vibrator to the tube allowed the complete dislodging of all the lacquers contained, despite being wet with the solvent. Example 1F: Example 1E was repeated with a glass tube with a nominal 101 mm diameter and wood chips (14% humidity) having a maximum length of 9.5 mm nominal. This provides a nominal tube-to-particle aspect ratio of more than 9.5. All splinters fell immediately from the tube by releasing a bottom sliding valve. Similar results were obtained when the chips were not wetted with the mixed aqueous / organic solvent.
[000153] The previous results demonstrate the beneficial effects of impregnation of pressurized solvent on wood chips. In the absence of pressurized solvent impregnation, a substantial fraction of the wood chips will float in the solvent when loaded into a digestion unit. In a tube to particle aspect ratio of 3: 1, the connection between the wood chips prevents their transfer. In an aspect ratio of 9.5: 1, bonding is avoided, and both solvent-impregnated and non-wetted wood chips can be transferred. Where the connection prevents the transfer of wood chips, mechanical vibration can be used to facilitate the transfer of solvent-impregnated wood chips.
[000154] Example 2: Catalytic Reduction of Sorbitol. The catalytic reduction of 20 grams of 50% by weight sorbitol solution was examined in a 75 milliliter Parr5000 reactor operated at 240 ° C under 75 bar (7.5 mPa) of H2 pressure, in the presence of 0.35 grams of Pt / zirconia catalyst with 1.9% modified with rhenium at a Re: Pt ratio of 3.75: 1. The reaction was continued for 18 hours, before sampling the reaction mixture using a gas chromatographic mass spectrometry (GC-MS) method using an ID DB-7 column fg 82 oo rqt 2.54 oo fg 3 μo fg thickness, with a 50: 1 split ratio, helium flow of 2 ml / min, and column heating maintained at 40 ° C for 8 minutes, followed by an elevation to 285 ° C at 10 ° C / min., and a retention time of 53.5 minutes. The GC-MS results indicate a conversion greater than 90% of sorbitol to mono-oxygenates and by-products of organic acid, as evidenced by a drop from neutral pH to 2.7. The reaction product comprises 20.3% ethanol by weight, 25.4% 1-propanol and 2-propanol by weight, and 2.5% dimethyl ketone (acetone) by weight. The presence of acetic acid was confirmed using an HPLC method using a Bio-Rad Aminex HPX-87H column (300 mm x 7.8 mm) operated at 0.6 ml / min. of a 5 mM sulfuric acid in a mobile aqueous phase, at a temperature of 30 ° C, a run time of 70 minutes, and both RI and UV detectors (320 nm).
[000155] Example 3: On-site digestion in a pressurization vessel. Example 3A: A pressure vessel was constructed from 316 stainless steel tubing 1 foot long by 1/2 inch in diameter and heated through an electric band heater (Gaumer Company, Inc.). The pressure vessel was packaged with 4.19 grams of small 1/8 inch by 1/4 inch by 3 mm pine wood chips (moisture content = 14% as determined by overnight drying in a vacuum oven at 85 ° C). A solvent mixture comprising 20 wt% 2-propanol, 25 wt% ethanol, 2 wt% dimethyl ketone, and 2 wt% acetic acid in deionized water was prepared to mimic the reaction mixture obtained in Example 2. The mixed organic / aqueous solvent had a pH of 2.7. The solvent mixture was fed to a digestion unit via an HPLC pump (Eldex).
[000156] The pressure vessel and a receiving vessel were pressurized to 70 bar (7 mPa) by charging with a liquid solvent feed followed by the addition of hydrogen from a 90 bar (9 mPa) supply source. The container and contents were heated to 180 ° C before establishing a flow rate of 0.20 ml / min of simulated digestion solvent. The contact with the solvent was continued for 16.9 hours at an hourly space velocity with an average weight of 3.35 grams of feed per gram of dry wood per hour (g / g of wood / hour). The hydrolysed product from digestion was collected in an outbreak container also previously pressurized to 70 bar (7 mPa) through the addition of H2. Controlling the back pressure in the pressure vessel and the surge vessel allows the pressure to be set at 70 bar (7 mPa) during the test procedure. The analysis of undigested wood at the end of the run indicated 39.6% dissolution and digestion of the original wood load.
[000157] Example 3B: Example 3A was repeated at a pressure vessel digestion temperature of 200 ° C, with an hourly spatial speed by weight for the solvent feed of 1.02 g / g wood / hour, and a digestion contact time of 6 hours. The analysis of undigested wood indicated only 29.1% of digestion of the original wood load.
[000158] Example 3C: Example 3A was repeated at a temperature of 240 ° C, with an hourly space velocity by weight of 1.79 g / g of wood / hour, and a digestion contact time of 5.6 hours. 1N KOH was added to buffer the solvent feed to a pH of 5.4. No wood solids were observed at the end of digestion. This result indicates that 100% dissolution and digestion is possible at a temperature of 240 ° C, despite buffering to a more neutral pH value compared to the more acidic feed solvent used for Examples 3A and 3B and a reduction by one digestion time for less than 6 hours.
[000159] Example 3D: Example 3A was repeated at a temperature of 210 ° C, with an hourly space velocity by weight of 1.27 g / g of wood / hour, and a digestion contact time of 7.1 hours. Despite the increase in contact time over Example 3C, only 65% of the wood load was digested.
[000160] Example 3E: Example 3A was repeated at a temperature of 190 ° C, with an hourly space velocity by weight of 1.66 g / g of wood / hour, for a contact time of 6.8 hours. Only 19% of the wood load was digested, despite the increase in flow compared to Example 3D.
[000161] Therefore, the present invention is well adapted to achieve the mentioned objectives and advantages as well as those that are inherent to it. The particular embodiments described above are illustrative only, as the present invention can be modified and practiced in different but equivalent ways for those skilled in the art having the benefit of the teachings here. In addition, no limitation is intended to the construction or design details shown here, other than what has been described in the claims below. It is therefore evident that the particular illustrative embodiments described above can be altered, combined or modified and all such variations are considered within the scope and spirit of the present invention. The invention described here in an illustrative manner can be practiced properly in the absence of any element that is not specifically described here and / or any optional element described here. While compositions and methods are described in terms of "comprising," "containing," or "including" various components or steps, compositions and methods can also "consist essentially of" or "consist of" the various components or steps . All of the numbers and ranges described above may vary by some. Whenever a numerical range with a lower limit and an upper limit is described, any number and any included range that falls within the range is specifically described. In particular, the entire range of values (of the form, "from a to b," or, equivalently, "from approximately a to b," or, equivalently, "from approximately a - b ") described here must be understood to define the entire number and range encompassed within the broadest range of values. In addition, the terms in the claims have their common and simple meaning unless it is explicitly and clearly defined otherwise by the depositor. In addition, the indefinite articles "one" or "one", as used in the claims, are defined here to mean one or more than one of the element they introduce. If there is any conflict in the use of a word or term in this specification and one or more patents or other documents, definitions that are consistent with this specification must be adopted.

权利要求:
Claims (20)
[0001]
1. Method for providing a biomass conversion system, characterized by the fact that it comprises: providing a biomass conversion system comprising a pressurization zone (4) and a digestion unit (2) that are operatively connected to each other ; provide a cellulosic biomass in a first pressure; introducing at least a portion of the cellulosic biomass into the pressurization zone and then pressurizing the pressurization zone to a second pressure that is greater than the first pressure; after pressurizing the pressurization zone, transfer at least a portion of the cellulosic biomass from the pressurization zone to the digestion unit, which is at a third pressure that is less than or equal to the second pressure but greater than the first pressure; and digesting at least a portion of the cellulosic biomass in the digestion unit to produce a hydrolyzate comprising soluble carbohydrates within a liquor phase.
[0002]
2. Method of providing a biomass conversion system, characterized by the fact that it comprises: providing a biomass conversion system comprising a pressurization zone (4) and a digestion unit (2) that are operatively connected to each other; provide a cellulosic biomass; introducing at least a portion of the cellulosic biomass into the pressurization zone and then pressurizing the pressurization zone, at least in part, with a liquor phase comprising an organic solvent; after pressurizing the pressurization zone, transfer at least a portion of the cellulosic biomass from the pressurization zone to the digestion unit, where the digestion unit is at a pressure that is less than or equal to the pressure of the zone pressurization; and digesting at least 90% of the cellulosic biomass, on a dry basis, to produce a hydrolyzate comprising soluble carbohydrates within a liquor phase.
[0003]
Method according to either of claims 1 or 2, characterized in that the step of providing a cellulosic biomass and the step of introducing at least a portion of the cellulosic biomass occur at the same time.
[0004]
Method according to claim 1, characterized in that it further comprises: before transferring at least a portion of the cellulosic biomass, reduce the pressure in the digestion unit to a fourth pressure which is at least 75% of the third pressure.
[0005]
Method according to any one of claims 1 to 4, characterized in that the step of introducing at least a portion of the cellulosic biomass into the pressurization zone comprises a technique or an apparatus selected from the group consisting of a feeder screw, a conveyor, a compartment dispenser, manual addition, and any combination thereof.
[0006]
Method according to any one of claims 1 to 5, characterized in that after transferring at least a portion of the cellulosic biomass, the digestion unit is at a pressure of at least 30 bar (3 mPa).
[0007]
Method according to any one of claims 1 to 6, characterized in that it additionally comprises: converting the hydrolyzate into a biofuel.
[0008]
Method according to any one of claims 1 to 7, characterized in that at least 60% of the cellulosic biomass, preferably at least 90% of the cellulosic biomass, on a dry basis, is digested to produce the hydrolyzate.
[0009]
Method according to any one of claims 1 to 8, characterized in that the third pressure is in the range of from 30 bar (3 mPa) to 430 bar (43 mPa), preferably from 50 bar ( 5 mPa) at 330 bar (33 mPa), more preferably from 70 bar (7 mPa) at 130 bar (13 mPa).
[0010]
Method according to any one of claims 1 to 9, characterized in that the step of pressurizing occurs, at least in part, by introducing at least a portion of the liquor phase and optionally a gas into the pressurization zone .
[0011]
Method according to any one of claims 1 or 3 to 10, characterized in that the liquor phase comprises an organic solvent.
[0012]
Method according to any one of claims 1 to 11, characterized in that it further comprises: recirculating at least a portion of a reaction product produced from the hydrolyzate back to the digestion unit.
[0013]
13. Biomass conversion system characterized by the fact that it comprises: a loading mechanism, a pressurization zone, and a digestion unit (2) that are operatively connected to each other in sequential series; a fluid circulation circuit (12) that establishes fluid communication between an inlet and an outlet of the digestion unit; and a fluid transport line that establishes fluid communication between the fluid circulation circuit and the pressurization zone; wherein the pressurization zone and the digestion unit are operatively connected to each other in such a way that at least a portion of a cellulosic biomass in the pressurization zone can be transferred to the digestion unit while the digestion unit is operating at a pressure of at least 30 bar (3 mPa).
[0014]
14. Biomass conversion system according to claim 13, characterized by the fact that it additionally comprises: a surge vessel located within the fluid circulation circuit (12) and in fluid communication with an outlet of the digestion unit (2 ).
[0015]
15. Biomass conversion system according to either of claims 13 or 14, characterized in that it additionally comprises: at least one catalytic reduction reactor unit (14) located within the fluid circulation circuit and in fluid communication with an outlet from the digestion unit.
[0016]
16. Biomass conversion system according to claim 15, characterized in that the at least one catalytic reduction reactor unit (14) contains at least one catalyst capable of activating molecular hydrogen.
[0017]
17. Biomass conversion system according to any one of claims 13 to 16, characterized in that the fluid circulation circuit and the digestion unit are configured to establish the countercurrent flow in the digestion unit.
[0018]
18. Biomass conversion system according to any one of claims 13 to 17, characterized in that the pressurization zone (4) comprises at least one pressure vessel.
[0019]
19. Biomass conversion system according to any one of claims 13 to 18, characterized in that the pressurization zone comprises multiple screw feeders that operate in parallel; each screw feeder can be loaded and pressurized separately.
[0020]
20. Biomass conversion system according to any one of claims 13 to 18, characterized in that the pressurization zone comprises multiple screw feeders that operate in series; where each screw feeder can sequentially raise the pressure in the pressurization zone.

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同族专利:

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公开号 | 公开日

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CN104160041A|2014-11-19|

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US8945243B2|2015-02-03|

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US20150132201A1|2015-05-14|

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EP2791368B1|2015-09-30|

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US20130152457A1|2013-06-20|

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PL2791368T3|2016-03-31|

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CA2859320A1|2013-06-20|

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US9421512B2|2016-08-23|

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BR112014014640A2|2017-06-13|

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CN104160041B|2016-08-24|

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AU2011383244A1|2014-06-19|

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EP2791368A1|2014-10-22|

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WO2013089798A1|2013-06-20|

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AU2011383244B2|2015-09-10|

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法律状态:
2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2020-08-11| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|

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2020-12-15| B09A| Decision: intention to grant|

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2021-03-02| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 20/12/2011, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201161576664P| true| 2011-12-16|2011-12-16|

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US61/5766,664|2011-12-16|

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PCT/US2011/066227|WO2013089798A1|2011-12-16|2011-12-20|Systems capable of adding cellulosic biomass to a digestion unit operating at high pressures and associated methods for cellulosic biomass processing|

---