METHOD FOR PRODUCING TOP HYDROCARBONS

专利摘要:
method for producing superior hydrocarbons. one method comprises providing a carbohydrate; reacting the carbohydrate directly with hydrogen in the presence of a hydrogenolysis catalyst to produce a reaction product comprising a polyol; and then processing at least a portion of the reaction product to form a fuel mixture.
公开号:BR112012015979B1
申请号:R112012015979-8
申请日:2010-12-20
公开日:2019-05-07
发明作者:Juben Nemchand CHHEDA；Kimberly Ann Johnson；Joseph Broun Powell
申请人:Shell Internationale Research Maatschappij B.V.；
IPC主号:

专利说明:

“METHOD TO PRODUCE SUPERIOR HYDROCARBONS” Field of the invention [0001] The invention relates to the production of superior hydrocarbons suitable for use in the transportation of fuels and industrial chemicals from biobased feed loads.
Fundamentals of the invention [0002] A significant amount of effort has been put into developing new methods and systems for providing energy from sources other than fossil fuels. Biobased feed loads are a resource that shows promise as an alternative renewable source of hydrocarbons to produce fuels and chemicals.
[0003] Biobased feed loads including carbohydrates and "biomass" are materials derived from biological materials. One type of biomass is cellulosic biomass. Cellulosic biomass is the most abundant source of carbohydrates in the world due to the lignocellulosic materials composing the cell walls. The ability to convert biomass to fuels, chemicals, energy and other materials is expected to strengthen the economy, minimize dependence on oil and gas sources, reduce air and water pollution, and decrease the net rate of carbon dioxide production.
[0004] There are many challenges to overcome in the development processes of converting carbohydrates to higher hydrocarbons suitable for use in fuels for means of transport. For example, the processes used are expensive and complex making it difficult to compete with the use of traditional sources such as fossil fuels. The publication of US patent application No. 2007/0142633 (Yao ET AL.) Refers to a process for converting carbohydrates into higher hydrocarbons. An ion exchange resin is provided to convert carbohydrates into useful reaction products. The reaction products are hydrogenated, and then
Petition 870180151558, of 11/14/2018, p. 8/58 / 46 contacted with a zeolite containing catalyst to form higher hydrocarbons. The conversion of carbohydrates to higher hydrocarbons in this system results in increased loss of desired hydrocarbon products due to the formation of unwanted by-products, such as coke, carbon dioxide, and carbon monoxide. So another challenge to promote and sustain the use of biomass is the need to eliminate the formation of undesirable by-products such as carbon monoxide, carbon dioxide, and coke. Another challenge is to complete the conversion of carbohydrates to higher hydrocarbons in a limited number of stages, to obtain high returns with minimal capital investment.
[0005] Current methods for converting sugars into fuel proceed through a biological route, such as fermentation with yeast, to ethanol. However, ethanol does not have a high energy density when compared to fuels for standard means of transport. Currently, there is a need to create liquid biofuels with a higher energy density than ethanol, which can make use of the existing fuel infrastructure. In addition, what is needed is a method and system that provides efficiency and high throughput for the production of superior hydrocarbons suitable for use as fuels for transporting chemicals from biobased feeds while avoiding or minimizing the production of unwanted by-products.
Summary of the invention [0006] An embodiment of the invention comprises a method comprising providing a carbohydrate; reacting the carbohydrate directly with a hydrogen in the presence of a hydrogenolysis catalyst to produce a reaction product comprising a polyol; and then process at least a portion of a reaction product to form a fuel mixture.
[0007] Another embodiment of the invention comprises a method
Petition 870180151558, of 11/14/2018, p. 9/58 / 46 comprising providing a biobased power load source; treating the biobased feed load to form a carbohydrate; reacting the carbohydrate in a hydrogenolysis reaction to produce reaction products comprising an alcohol, a polyol, and a higher polyol; through the hydrogenation reaction to produce reaction products comprising an alcohol and a polyol; and processing at least a portion of the reaction products to form a fuel mixture.
[0008] Yet another embodiment of the invention comprises a method comprising providing a biobased power supply source; treat the biobased feed load to form a carbohydrate; reacting the carbohydrate in a hydrogenolysis reaction to produce reaction products comprising an alcohol, a polyol, and a higher polyol; recycling the upper polyol through the hydrogenation reaction to produce reaction products comprising an alcohol and a polyol; and processing at least a portion of the reaction products to form a fuel mixture.
[0009] Yet another embodiment of the invention comprises a system comprising a first vessel for receiving a carbohydrate and producing a hydrogenated product; a second vessel for receiving the hydrogenated product and producing an alcohol and a polyol; and a processing reactor for reacting alcohol and polyol in the presence of a catalyst to produce a fuel mixture.
[00010] The characteristics and advantages of the invention will become apparent to those skilled in the art. While numerous changes can be made by those skilled in the art, changes are within the spirit of the invention.
Brief description of the drawings [00011] These drawings illustrate certain aspects of the modalities of the invention, and should not be used to limit or define the invention.
[00012] Figure 1 schematically illustrates a flow diagram
Petition 870180151558, of 11/14/2018, p. 10/58 / 46 block of an embodiment of a superior hydrocarbon production process of this invention.
[00013] Figure 2 schematically illustrates a block flow diagram of another embodiment of the higher hydrocarbon production process of the invention.
[00014] Figure 3 schematically illustrates a block flow diagram of another embodiment of a higher hydrocarbon production process of this invention.
Detailed description of the invention [00015] This invention relates to methods and systems for producing high hydrocarbons from biobased feed charges, such as carbohydrates, which include sugar, sugar alcohols, cellulose, lignocellulose, hemicellulose, lignocellulosic biomass, and any combination thereof, to form superior hydrocarbons suitable for use in fuels for means of transport in industrial chemicals, while minimizing the formation of unwanted by-products such as coke, carbon dioxide, and carbon monoxide. The superior hydrocarbons produced are useful in forming fuels for transportation, such as synthetic gasoline, diesel fuel, and aviation fuel as well as chemicals. As used herein, the term "higher hydrocarbons" refers to hydrocarbons having a lower oxygen-to-carbon ratio than at least one component of the bio-fed feed charge. As used herein the term "hydrocarbon" refers to an organic compound comprising primarily hydrogen and carbon atoms, which are also unsubstituted hydrocarbons. In certain embodiments, the hydrocarbons of the invention also comprise heteroatoms (for example oxygen or sulfur) and thus, the term "hydrocarbon" can also include substituted hydrocarbons.
[00016] One embodiment of a process 100 described in the invention is
Petition 870180151558, of 11/14/2018, p. 11/58 / 46 illustrated in fig 1. Alternative modalities are illustrated in figures 2-3. In the embodiment shown in fig 1, a solution of the feed load comprising water-soluble carbohydrate 102 is catalytically reacted with hydrogen in a hydrogenolysis reaction 106 to produce desired reaction products. The reaction products are further reacted catalytically in the processing reaction 110 to produce a higher hydrocarbon stream 112. Higher hydrocarbon stream 112 can be mixed in a downstream process with additional streams to create fuels or chemicals. Suitable reaction products may include, but are not limited to, alcohols, polyols, aldehydes, ketones, other oxygenated intermediates, and any combination thereof. Suitable processing reactions include, but are not limited to, condensation reactions, oligomerization reaction, hydrogenation reaction, and any combination thereof.
[00017] In the embodiment shown in fig 2, a feed-load solution comprising water-soluble carbohydrate 102 is catalytically reacted with hydrogen in a hydrogenation reaction 104 and / or hydrogenolysis reaction 106 to produce desired reaction products. The reaction products are then passed through optional separation devices 108, and the suitable alcohols or polyols are further catalytically reacted in processing reaction 110 to produce a higher hydrocarbon stream 112. Higher hydrocarbon stream 112 can be mixed in one process downstream with additional currents to create fuels or chemicals. Suitable reaction products may include, but are not limited to, alcohols, polyols, aldehydes, ketones, other oxygenated intermediates, and any combinations thereof. Higher polyols can be recycled via hydrogenolysis reaction 106 through recycle stream 114 to produce additional suitable alcohol and polyol reaction products. As used herein, the term “polyol
Petition 870180151558, of 11/14/2018, p. Upper 12/58 / 46 ”refers to a polyol with an oxygen to carbon ratio of 0.5 or more. Suitable process reactions include, but are not limited to, condensation reactions, oligomerization reaction, hydrogenation reaction, and any combination thereof.
[00018] In the embodiment shown in fig 3, a feed-load solution comprising water-soluble carbohydrate 102 is optionally hydrolyzed through the hydrolysis reaction 114 and further catalytically reacted with hydrogen in a hydrogenolysis reaction 106 to produce desired reaction products. The reaction products are then passed through an optional separation device 108, and suitable alcohols or polyols are further catalytically reacted in the processing reaction 110 to produce a higher hydrocarbon stream 112. Higher hydrocarbon stream 112 can be mixed in one downstream process with additional streams to create additional fuels or chemicals. Suitable reaction products may include, but are not limited to, alcohols, polyols, aldehydes, ketones, other oxygenated intermediates, and any combination thereof. Higher polyols can be recycled back through the hydrogenolysis reaction 106 through the recycle stream 114 to produce alcohol reaction products and additional suitable polyol. As used herein, the term "upper polyol" refers to a polyol with an oxygen to carbon ratio of 0.5 or more. Suitable processing reactions include, but are not limited to, condensation reactions, oligomerization reaction, hydrogenation reaction, and any combination thereof.
[00019] In certain embodiments, the hydrolysis reaction, hydrogenation reaction, hydrogenolysis reaction, and processing reactions described in the present invention could be conducted in a single step.
[00020] In one embodiment, the reactions described below are carried out in any suitable design system, including systems comprising reactors and vessels of continuous flow, batch, semi-batch,
Petition 870180151558, of 11/14/2018, p. 13/58 / 46 or multi-system. One or more reactions can be carried out in an individual vessel and the process is not limited to separation reaction vessels for each reaction. In one embodiment, the invention uses a fixed or fluidized catalytic bed system. Preferably, the invention is practiced using a steady-state continuous flow system.
[00021] The methods and systems of the invention have the advantage of converting biobased feed charges, optionally without any additional rich purification steps to form higher energy density product of lower oxygen / carbon rate including higher alkanes, olefins, and aromatics. The invention also reduces the amount of unwanted by-products, thereby improving the overall yield of carbohydrates from conversion to higher hydrocarbons. Another advantage of the present invention includes the use of similar catalysts for multiple reaction steps, offering the potential to combine reactions when desired. An additional advantage of the present invention provides the combination or elimination of the steps required to convert biobased feed loads to fuel, thereby reducing capital costs.
[00022] Advantages of the specific modalities will be described in more detail below.
[00023] An embodiment of the invention comprises a method comprising providing a carbohydrate, reacting the carbohydrate directly with hydrogen in the presence of a hydrogenolysis catalyst to produce a reaction product comprising a polyol; and then process at least a portion of the reaction product to form a fuel mixture.
[00024] Carbohydrates are more abundant, naturally occurring biomolecules. Plant material stores carbohydrates in both sugars, starches, celluloses, lignocelluloses, hemicelluloses, and any combination thereof. In one embodiment, carbohydrates include monosaccharide,
Petition 870180151558, of 11/14/2018, p. 14/58 / 46 polysaccharides or mixtures of monosaccharides and polysaccharides. As used herein, the term "monosaccharide" refers to hydroxyaldehydes or hydroxy ketones, which cannot be hydrolyzed into smaller units. Examples of monosaccharides include, but are not limited to, dextrose, glucose, fructose and galactose.
[00025] As used herein, the term "polysaccharide" refers to saccharides comprising two or more monosaccharide units. Examples of polysaccharides include, but are not limited to, sucrose, maltose, cellobiosis, cellulose and lactose. Carbohydrates are produced during photosynthesis, a process in which carbon dioxide is converted to organic compounds as a way of storing energy. Carbohydrates are highly reactive compounds that can be easily oxidized to generate energy, carbon dioxide, and water. The presence of oxygen in the molecular structure of carbohydrates contributes to the reactivity of the compound. Water-soluble carbohydrates react with hydrogen on catalyst (s) to generate polyol and sugar alcohols, either by hydrogenation, hydrogenolysis or both.
[00026] In the embodiment shown in fig 1, the carbohydrates are optionally passed through the hydrogenation reaction and then a hydrogenolysis reaction to form suitable reaction products comprising alcohols and polyols for the 110 condensation reaction. hydrogenation reaction is optional and the hydrogenolysis reaction alone is sufficient to form appropriate polyol and alcohol compounds. In another embodiment of the invention, carbohydrates are passed through the hydrogenolysis vessel before being passed through the hydrogenation vessel (thus hydrogenolysis reaction 106 and hydrogenation reaction 104 are reversed in the order shown in fig 1). Yet another embodiment of the invention, the hydrogenation and hydrogenolysis reactions take place in the same vessel to generate polyols and alcohols to be fed into the
Petition 870180151558, of 11/14/2018, p. 15/58 / 46 condensation reaction. In a final embodiment, a separation step (removal of water) could be carried out before the hydrogenolysis reaction. [00027] Carbohydrates can originate from any suitable source. In one embodiment, carbohydrates can be fed to the process which are derived from organic sources (for example, sugars and starches from corn and sugar cane). In another modality, carbohydrates are derived from biobased feed loads. Biobased feed loads can include biomass. As used here, the term "biomass" means organic materials produced by plants (for example, leaves, roots, seeds and stems), and microbial and metabolic metabolic wastes. Common sources of biomass include: agricultural residues (for example, corn stalks, straw, seed husks, sugarcane residues, bagasse, nutshells, and manure from livestock, poultry and pigs); wood materials (for example wood or bark, sawdust, board waste and mill waste); municipal waste, (for example, paper waste and farm sample); and energy collection, (eg poplar, willow, switchgrass, alfalfa, blue pasture, corn and soy). The term "biomass" also refers to the primary building blocks of all of the above, including, but not limited to, saccharides, lignins, celluloses, hemicelluloses and starches. Carbohydrates useful in the invention include, but are not limited to, carbohydrates that can be converted to hydrocarbons under suitable reaction conditions. Suitable carbohydrates in the invention include any water-soluble carbohydrate or an organic solvent having one or more carbon atoms and at least one oxygen atom. Carbohydrates can also have an oxygen to carbon ratio of 0.5: 1 to 1:12.
[00028] In one embodiment of the invention the biobased feed charge is optionally first hydrolyzed in a liquid medium such as an aqueous solution to obtain an intermediate carbohydrate stream for use in the process. These various biomass hydrolysis
Petition 870180151558, of 11/14/2018, p. Suitable 16/58 / 46 include, but are not limited to, water hydrolysis, alkaline hydrolysis, enzymatic hydrolysis, and hydrolysis using compressed hot water. In certain embodiments, the hydrolysis reaction can occur at a temperature between 100 ° C and 250 ° C and a pressure between 1 atm and 100 atm. In modalities including strong acid and enzymatic hydrolysis, the hydrolysis reaction can at temperatures as low as room temperature and pressure from 1 atm to 100 atm. In some embodiments, the hydrolysis reaction may comprise a hydrolysis catalyst (e.g., metal or acid catalyst) to assist in the hydrolysis reaction. The hydrolysis catalyst can be any catalyst capable of carrying out a hydrolysis reaction. For example, suitable hydrolysis catalysts include, but are not limited to, acid catalysts, basic catalysts, and metal catalysts. Acid catalysts can include organic acids such as acetic acid, formic acid, and levunilic acid. In one embodiment, the acid catalyst can be generated as a by-product during hydrogenation and / or hydrogenolysis reactions. In certain embodiments, the hydrolysis of biobased feed charges can occur in conjunction with the hydrogenation and / or hydrogenolysis reactions.
[00029] In such embodiments, a co-catalyst or catalytic support can be added to hydrogenation and / or hydrogenolysis reactions to facilitate the hydrolysis reaction.
[00030] Several factors affect the conversion of the feed load based on the hydrolysis reaction. In some embodiments, hemicellulose can be extracted from the feed charge based on an aqueous fluid and hydrolyzed at temperatures below 160 ° C to produce a fraction of C5 carbohydrate. By increasing temperatures, this fraction of C5 can be thermally degraded. It is therefore advantageous to convert C5, C6, or other intermediate sugars directly into more stable intermediates such as sugar alcohols. Recycling oxygenated intermediates from hydrogenation and / or hydrogenolysis reactions and perform biomass hydrolysis
Petition 870180151558, of 11/14/2018, p. 17/58 / 46 additional with this recycled liquid, the concentration of the active oxygenated intermediates can increase to commercially viable concentrations without dilution of water. Typically, a concentration of at least 2%, or 5% or preferably more than 8% of organic intermediates in water, may be suitable for a viable process.
[00031] This can be determined by sampling the intermediate current at the outlet of the hydrolysis reaction and using an appropriate technique such as chromatography to identify the concentration of total organics. The oxygenated intermediate stream has a potential fuel formed, as described below.
[00032] Cellulose extraction starts above 160 ° C, with solubilization and hydrolysis becoming complete at temperatures around 190 ° C, aided by organic acids (for example, carboxylic acids) formed from partial degradation of carbohydrate components. Some lignins can be solubilized before cellulose, while other lignins can persist at high temperatures. Organic solvents generated in situ, which may comprise a portion of oxygenated intermediates, including, but not limited to, light alcohols and polyols, can aid in the solubilization and extraction of lignin in other components.
[00033] At temperatures ranging from 250 ° C to 275 ° C, carbohydrates can degrade through a series of complex self-compensation reactions to form caramelans, which are considered degradation products that are difficult to convert into fuel products. In general, some degradation reactions can be expected with aqueous reaction conditions on application of temperature, since water will not completely suppress oligomerization and polymerization reactions.
[00034] The temperature of the hydrolysis reaction can be chosen so that the maximum amount of extractable carbohydrates are hydrolyzed and extracted as carbohydrates from the biobased feed charge.
Petition 870180151558, of 11/14/2018, p. 18/58 / 46 while limiting the formation of degradation products. In some embodiments, a plurality of reaction vessels can be used to carry out the hydrolysis reaction. These vessels can have any design capable of carrying out a hydrolysis reaction. Suitable reaction vessel designs may include, but are not limited to, co-current, counter-current, agitated tank, or fluidized bed reactors. In this embodiment, the biobased feed charge can first be introduced into a reaction vessel operating at approximately 160 ° C. At this temperature, hemicellulose can be hydrolyzed to extract the C5 carbohydrate and some lignin without degrading these products. The remaining biobased solid feed charge can then leave the first reaction vessel and move to a second reaction vessel. The second reaction vessel can be operated between 160 ° C and 250 ° C so that cellulose is still hydrolyzed to form C6 carbohydrates. The remaining biobased solid feed charge can then leave the second reactor as a waste stream while the intermediate stream of the second reactor can be cooled and combined with the intermediate stream from the first reaction vessel. The combined output stream can then pass to the hydrogenation and / or hydrogenolysis reactors.
[00035] In another embodiment, a series of reaction vessels can be used with an increasing temperature profile so that a desired carbohydrate fraction is extracted in each vessel. The outlet of each vessel can then be cooled before combining the streams, or the streams can be individually fed to the hydrogenation and / or hydrogenolysis reaction to convert the intermediate carbohydrate streams to one or more oxygenated intermediate streams.
[00036] In another embodiment, the hydrolysis reaction can occur in a single vessel. This vessel can have any design capable of carrying out a hydrolysis reaction. Suitable reactor vessel designs may include, but are not limited to, co-current, counter-current, agitated tank, or bed reactors
Petition 870180151558, of 11/14/2018, p. 19/58 / 46 fluidized. In some embodiments, a designed countercurrent reactor is used in which the biobased feed charge flows countercurrently into the aqueous stream, which may comprise a solvent generated in situ. In this embodiment, a temperature profile can exist within the reactor vessel so that the temperature within the hydrolysis reaction medium at or near the biobased feed charge inlet is approximately 160 ° C and the temperature near the outlet of the biobased feed is approximately 200 ° C to 250 ° C. The temperature profile can be obtained by introducing an aqueous fluid comprising a solvent generated in situ above 200 ° C to 250 ° C near the outlet of the biobased feed charge while simultaneously introducing a biobased feed charge at 160 ° C or any less. The specific inlet temperature of the aqueous fluid and the biobased feed load will be determined based on the heat balance between two streams. The resulting temperature profile can be useful for the hydrolysis and extraction of cellulose, lignin, and hemicellulose without substantial production of degradation products.
[00037] Other means can be used to establish an appropriate temperature profile for the reaction of hydrolysis and extraction of cellulose and hemicellulose along with other components such as lignin without substantially producing degradation products. For example, internal heat exchange structures can be used within one or more reaction vessels to maintain a desired temperature profile for the hydrolysis reaction. Other structures as could be known to a person skilled in the art can also be used.
[00038] Each reactor vessel of the invention preferably includes an inlet and an outlet adapted to remove the product stream from the vessel or reactor. In some embodiments, the vessel in which the hydrolysis reaction or some portion of the hydrolysis reaction occurs may include additional outlets
Petition 870180151558, of 11/14/2018, p. 20/58 / 46 to allow the removal of portions of the reaction stream to help maximize the desired product formation. Suitable reactor designs may include, but are not limited to, a retromix reactor (eg agitated tank, bubble column, and / or jet mix reactor) can be employed if the viscosity and characteristics of the digested biobased feed charge and liquid reaction medium is sufficient to operate in a regime where solids from the feed charges are suspended in an excess liquid phase (as opposed to a stacked pile digester).
[00039] It is understood that in one embodiment, the biomass does not need to be hydrolyzed as the biomass containing carbohydrate may already be suitable in the aqueous form (for example crude cane juice concentrate) to convert the biobased feed load to higher hydrocarbons.
[00040] In an embodiment of the invention, the intermediate carbohydrate stream produced by the hydrolysis reaction can be partially deoxygenated. In another embodiment of the invention, the biobased feed charge can be completely de-oxygenated. Deoxygenation reactions form desired products, including, but not limited to, polyols, alcohols, ketones, aldehydes, and hydroxy carboxylic acids or carboxylic acids for use in subsequent condensation reactions. In general, without being limited to any particular theory, deoxygenation reactions involve the combination of several different reaction paths, including without limitation: hydrogenolysis reactions, hydrogenation, consecutive hydrogenolysis, consecutive hydrogenolysis-hydrogenation, and combined hydrogenolysis-hydrogenolysis, resulting at least partial removal of oxygen from the carbohydrate to produce reaction products that can be easily converted to higher hydrocarbons by the condensation reaction.
[00041] In one embodiment of the invention, a hydrolyzed, substantially hydrolyzed carbohydrate derived from unhydrolyzed biomass is
Petition 870180151558, of 11/14/2018, p. 21/58 / 46 converted to its corresponding alcohol derived through a hydrogenation reaction in a hydrogenation reaction vessel (such as hydrogenation reactor 104 in fig 1).
[00042] Carbohydrates, intermediates oxygenated from the hydrolysis reaction, or both can happen in a hydrogenation reaction to saturate one or more unsaturated bonds. Various processes are suitable for hydrogenating carbohydrates, oxygenated intermediates, or both. One method includes contacting the feed stream with hydrogen or hydrogen mixed with a suitable gas and catalyst under conditions sufficient to cause a hydrogenation reaction to form a hydrogenated product. The hydrogenation catalyst can generally include metals of group VIII and metals of group VI. Examples of such catalysts include, but are not limited to, Cu, Re, Ni, Fe, Co, Ru, Pd, Rh, Pt, Os, Ir, and alloys or any combination thereof, either alone or with promoters such as W, Mo , Au, Ag, Cr, Zn, Mn Sn, B, P, Bi, and alloys or any combination thereof. Another effective hydrogenation catalyst material includes either nickel or ruthenium supported by rhenium. In one embodiment, the hydrogenation catalyst also includes any of the supports, depending on the desired functionality of the catalyst. Hydrogenation catalysts can be prepared by prepared methods known to those skilled in the art.
[00043] In one embodiment, the hydrogenation catalyst includes a supported Group VIII metal catalyst and a metal sponge material (eg sponge nickel catalyst). Raney Nickel provides an example of an activated sponge nickel catalyst suitable for use in this invention. In one embodiment, the hydronation reaction in the invention is carried out using a catalyst comprising an aluminum rhenium catalyst or a nickel modified tungsten catalyst. An example of a suitable catalyst for the hydrogenation reaction of
Petition 870180151558, of 11/14/2018, p. 22/58 / 46 invention is a carbon-supported rhenium-nickel catalyst.
[00044] In one embodiment, a suitable Raney nickel catalyst can be prepared to treat an alloy of approximately equal amounts by weight of nickel and aluminum with an aqueous alkali solution, for example containing about 25% by weight of sodium hydroxide. Aluminum is selectively dissolved by the aqueous alkali solution resulting in a sponge-shaped material comprising mainly nickel with smaller amounts of aluminum. The initial alloy includes promoter metals (i.e., molybdenum or chromium) in an amount such that 1 to 2% by weight remains on the sponge-shaped nickel catalyst. In another embodiment, the hydrogenation catalyst is prepared using a solution of ruthenium (III) nitrosyl nitrate, ruthenium (III) chloride in water to impregnate a suitable support material. The solution is then dried to form a solid having a water content of less than 1% by weight. The solid is then reduced to atmospheric pressure in a hydrogen stream at 300 ° C (uncalcined) or 400 ° C (calcined) in a rotary ball oven for 4 hours. After cooling and processing the inert catalyst with nitrogen, 5% by volume of the oxygen in nitrogen is passed over the catalyst for 2 hours.
[00045] In certain embodiments, the described catalyst includes a catalyst support. The catalyst support stabilizes and supports the catalyst. The type of supported catalyst used depends on the chosen catalyst and the reaction conditions. Suitable supports for the invention include, but are not limited to, carbon, silica, silica-alumina, zirconia, titania, ceria, vanadia, nitride, heteropoly acids, hydroxyapatite, zinc oxide, chromium, zeolites, carbon nanotubes, carbon fulurence and any combination of them.
[00046] The catalysts used in this invention can be prepared using conventional methods known to those skilled in the art.
Petition 870180151558, of 11/14/2018, p. 23/58 / 46
Suitable methods may include, but are not limited to, incipient wetting techniques, evaporative impregnation, chemical vapor deposition, reactive coating, magnetron spraying and the like.
[00047] The conditions for carrying out the hydrogenation reaction will vary based on the type of the starting material and the desired products. One of ordinary skill in the art, with the benefit of this description, will recognize the appropriate reaction conditions. In general, the hydrogenation reaction is conducted at temperatures of 40 ° C to 250 ° C, and preferably at 90 ° C to 200 ° C, and more preferably from 100 ° C to 150 ° C. In one embodiment, the hydrogenation reaction is conducted at pressures from 500kPa to 14000kPa.
[00048] In some embodiments, a plurality of reaction vessels can be used to perform the hydrogenation reaction. These stages may be able to carry out a hydrogenation reaction without producing unwanted by-products while minimizing degradation of desired products. In the modality, the hydrogenation reaction can occur in two or more stages. In this embodiment, the biobased feed load can first be introduced in a first reaction stage operating at a temperature between 40 ° C and 90 ° C. The products can then be exposed to a second reaction stage operating at a temperature between 80 ° C to 120 ° C.
[00049] The remaining products can then be exposed to a third stage operating at a temperature between 100 ° C and 175 ° C.
[00050] In one embodiment, the hydrogen used in the hydrogenation reaction of the current invention can include external hydrogen, recycled hydrogen, hydrogen generated in situ and any combination thereof. As used herein, the term "external hydrogen" refers to hydrogen that does not originate from the reaction of the biobased feed charge itself, but is preferably added to the system from another source.
[00051] In one embodiment, the invention comprises a system
Petition 870180151558, of 11/14/2018, p. 24/58 / 46 having a first vessel to receive a carbohydrate and producing a hydrogenated product. Each vessel of the invention preferably includes an inlet and an outlet adapted to remove the product stream from the vessel or reactor. In one embodiment, vessels and reactors include additional outlets to allow removal of portions of the reagent stream to help minimize the formation of the desired product, and to allow for the collection and recycling of by-products for use in other parts of the system.
[00052] In one embodiment, the system of the invention includes elements that allow for the separation of the intermediate current into different components to promote the desired products being fed in the desired reactions. For example, a suitable separator unit includes, but is not limited to, a phase separator, a fractionation current, extractor, or distillation column.
[00053] In an embodiment of the invention, it is desired to convert the carbohydrates and oxygenated intermediates from the hydrolysis reaction and hydrogenation reaction to a smaller molecule that will be more readily converted to the desired higher hydrocarbons. A suitable method for this conversion is through the hydrogenolysis reaction.
[00054] Several processes are known to perform hydrogenolysis of carbohydrates. A suitable method includes contacting a carbohydrate or oxygenated intermediate with hydrogen or hydrogen mixed with a suitable gas and a hydrogenolysis catalyst in a hydrogenolysis reaction under conditions sufficient to form a reaction product comprising smaller molecules or polyols. As used herein, the term "smaller molecules or polyols" includes any molecule that has a lower molecular weight, which may include fewer carbon atoms or oxygen atoms than the initial carbohydrate. In one embodiment, the reaction products include smaller molecules that include polyols and alcohols. Some of those skilled in the art might be able to choose the
Petition 870180151558, of 11/14/2018, p. 25/58 / 46 appropriate method by which it performs the hydrogenolysis reaction.
[00055] In one embodiment, a 5 and / or 6-carbon carbohydrate molecule can be converted to propylene glycol, ethylene glycol, and glycerol using hydrogenolysis reaction in the presence of a hydrogenolysis catalyst. The hydrogenolysis catalyst can include Cr, Mo, W, Re, Mn, Cu, Cd, Fe, Ni, Pt, Pd, Rh, Ru, Ir, Os and alloys or combinations thereof, either alone or with promoters such as Au , Ag, Cr, Zn, Mn, Sn, Bi, B, O, and alloys or any combination thereof. The hydrogenolysis catalyst may also include a carbonaceous pyropolymer catalyst containing transition metals (for example chromium, molybdenum, tungsten, rhenium, manganese, copper, cadmium) or group VIII metals (for example iron, cobalt, nickel, platinum, palladium , rhodium, ruthenium, iridium, and osmium). In certain embodiments, the hydrogenolysis 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 as described above for the hydrogenation reaction.
[00056] The conditions for which the hydrogenolysis reaction is carried out will vary based on the type of starting material and desired products. A person skilled in the art, with the benefit of the description, will recognize the appropriate conditions for carrying out the reaction. In general, the hydrogenolysis reaction is conducted at temperatures of 110 ° C to 300 ° C, and preferably at 170 ° C to 220 ° C, and more preferably at 180 ° C to 225 ° C. In one embodiment, the hydrogenolysis reaction is conducted under basic conditions, preferably at a pH of 8 to 13, and even more preferably at a pH of 10 to 12. In one embodiment, the hydrogenolysis reaction is conducted at pressures in the range between 60kPa and 16500kPa, and preferably in the range between 1700kPa and 14000kPa, and even more preferably between 4800kPa and 11000kPa.
Petition 870180151558, of 11/14/2018, p. 26/58 / 46 [00057] The hydrogen used in the hydrogenolysis reaction of the current invention can include external hydrogen, recycled hydrogen, hydrogen generated in situ, and any combination thereof.
[00058] In one embodiment, the use of the hydrogenolysis reaction can produce less carbon dioxide and a greater amount of polyols than a reaction that results in reforming the reagents. For example, reform can be illustrated by the formation of isopropanol (i.e., IPA, or 2-propanol) from sorbitol;
[00059] Alternatively, in the presence of hydrogen, polyols and monooxygenates such as IPa can be formed by hydrogenolysis, where hydrogen is consumed preferably produced:
C ₆ Hi ₄ O ₆ + 3H ₂ 2H ₂ O + 2C ₃ H ₈ O ₂ ; dHR = +81 J / gmol (Eq. 2)
CeHuOe + 5H ₂ 4H ₂ O + 2C ₃ H ₈ O; dHR = -339 J / gmol (Eq. 3) [00060] As a result of differences in reaction conditions (for example, temperatures below 250 ° C), the products of the hydrogenolysis reaction can comprise more than 25 mol% , or alternatively, more than 30 mol%, of polyols, which can result in a greater conversion in processing reactions. In addition, the use of a hydrolysis reaction more than a reaction running under reforming conditions can result in less than 20 mol%, or alternatively less than 30 mol% of carbon dioxide production.
[00061] In one embodiment, the invention comprises a system having a second vessel to receive the hydrogenated product and convert it to an alcohol or polyol. In certain embodiments, the hydrogenation and hydrogenolysis catalysts are the same and can exist in the same bed in the same vessel. Each vessel of the invention preferably includes an inlet and an outlet adapted to remove the product stream from the vessel or reactor. In one embodiment, vessels and reactors include additional outlets to allow
Petition 870180151558, of 11/14/2018, p. 27/58 / 46 removal of portions of the reagent stream to help maximize the formation of the desired product, and allow the collection and recycling of by-products for use in other portions of the system.
[00062] In a separate embodiment, hydrogenolysis is conducted under neutral or acidic conditions, as necessary to accelerate hydrolysis reactions in addition to hydrogenolysis.
[00063] In an embodiment of the invention, a separator is installed before the condensation reaction in favor of the production of the upper hydrocarbons separating the upper polyols from the polyols and alcohols. In such an embodiment, the upper polyols and unconverted feed are recycled back through the hydrogenolysis vessel with the help of an additional outlet, while the other reaction products are sent to the condensation reactor.
[00064] In some embodiments, the oxygenated intermediates are converted to a fuel mixture that can be used as a fuel additive through hydrogenation of the oxygenated intermediates. Various processes are suitable for hydrogenating the oxygenated intermediates. One method includes contacting the feed stream with hydrogen or hydrogen mixed with a suitable gas and catalyst under conditions sufficient to cause a hydrogenation reaction to form a hydrogenated product. Suitable catalysts and reaction conditions are described above.
[00065] Hydrogenation of oxygenated intermediates can produce one or more alcohols, polyols, or saturated hydrocarbons. The alcohols produced in the invention have 2 to 30 carbon atoms. In some embodiments, alcohols are cyclical. In another embodiment, alcohols are branched. In other embodiments, alcohols are straight-chain. Alcohols suitable for the invention include, but are not limited to, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol,
Petition 870180151558, of 11/14/2018, p. 28/58 / 46 dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptydecanol, octyldecanol, nonildecanol, eicosanol, uneicosanol, doeicosanol, trieicosanol, tetraeicosanol, and some isomers thereof.
[00066] Alcohols, polyols, and / or saturated hydrocarbons can be used as a fuel mixture additive in means of transport or other fuels. In addition, the products can be sold as commodity chemicals for additional uses known to one skilled in the art.
[00067] In some embodiments, the oxygenated intermediates discussed above can be converted to higher hydrocarbons through a condensation reaction in a condensation reactor (shown schematically as condensation reaction 110 in figure 1). In such an embodiment, condensation of the oxygenated intermediates occurs in the presence of a catalyst capable of forming higher hydrocarbons. While not intended to be limited in theory, it is believed that the production of higher hydrocarbons proceeds through a gradual addition reaction including the formation of a carbon-carbon, or carbon-oxygen bond. The resulting reaction products include any number of compounds having these portions, as described in more detail below.
[00068] In some embodiments, the output current containing at least a portion of the oxygenated intermediates can pass on to a condensation reaction. The condensation reaction can comprise a variety of catalysts for condensing one or more oxygenated intermediates to higher hydrocarbons. Higher hydrocarbons can comprise a fuel product. The fuel products produced by the condensation reactor represent the product stream from the global process in a hydrocarbon stream. In one embodiment, the oxygen-to-carbon ratio of hydrocarbons produced through the condensation reaction is less than 0.5
Petition 870180151558, of 11/14/2018, p. 29/58 / 46 alternatively less than 0.4, or preferably less than 0.3. [00069] In certain embodiments, suitable condensation catalysts include an acid catalyst, a base catalyst, or an acid / base catalyst. As used herein, the term "acid / base catalyst" refers to a catalyst that has both an acidic and basic functionality or functional sites. In one embodiment, the condensation catalyst may include, without limitation, zeolite, carbides, nitrides, zirconia, alumina, silica, aluminosilicate, phosphate, titanium oxides, zinc oxides, vanadium oxides, lanthanum oxides, yttrium oxides, oxides scandium, magnesium oxides, cerium oxides, barium oxides, calcium oxides, hydroxides, heteropoly acids, inorganic acids, acid-modified resins, base-modified resins, and any combination thereof. In one embodiment, the condensation catalyst can also include a modifier. Suitable modifiers include La, Y, Sc, P, B Bi, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, and any combination thereof. In one embodiment, the condensation catalyst can also include a metal. Suitable metals include Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, alloys and any combination thereof.
[00070] In certain embodiments, the catalyst described in the condensation reaction can include a catalyst support as described above for the hydrogenation reaction. In certain embodiments, the condensation catalyst is self-sustaining. As used herein, the term “self-sustaining” means that the catalyst does not need another material to serve as a support. In another embodiment, the condensation catalyst is used in conjunction with a separate suitable support to suspend the catalyst. In one embodiment, the condensation catalyst support is silica.
[00071] The conditions under which the condensation reaction is carried out will vary based on the type of starting material and the desired products.
Petition 870180151558, of 11/14/2018, p. 30/58 / 46
A common person skilled in the art, with the benefit of this description, will recognize the appropriate conditions for using and carrying out the reaction. In one embodiment, the condensation reaction is carried out at a temperature where the thermodynamics for the purpose of the reaction is favorable. The temperature for the condensation reaction will vary depending on the specific starting polyol or alcohol. In one embodiment, the temperature for the condensation reaction is in the range of 80 ° C to 500 ° C, and preferably 125 ° C to 450 ° C, and more preferably 175 ° C to 400 ° C. In one embodiment, the condensation reaction is conducted at pressures generally in the range of 0kPa to 9000kPa, and preferably in the range of 0kPa to 7000kPa, and even more preferably between 0kPa and 5000kPa.
[00072] In one embodiment, the invention comprises a system having a condensation reactor for reacting alcohol and polyols products from the hydrogenation and hydrogenolysis reaction in the presence of the condensation catalyst to produce at least some higher fuel forming hydrocarbons. In certain embodiments, the hydrogenation and hydrogenolysis catalysts are the same and can exist in the same bed in the same vessel. Each reactor of the invention preferably includes an inlet and an outlet adapted to remove the product stream from the reactor. In one embodiment, the reactors include additional outlets to allow removal of portions of the reagent stream to help maximize the formation of the desired product, and to allow collection and recycling of by-products for use in other portions of the system.
[00073] The higher hydrocarbons formed by the invention can include a wide range of compounds depending on the reaction conditions and the composition of the oxygenated intermediates fed to the reaction. Exemplarily higher hydrocarbons include, but are not limited to, straight or branched chain alkanes having 4 to 30 carbon atoms, straight or branched chain alkanes having 4 to 30 carbon atoms,
Petition 870180151558, of 11/14/2018, p. 31/58 / 46 cycloalkanes which have 5 to 30 carbon atoms, cycloalkenes which have 5 to 30 carbon atoms, aryl, fused aryl, alcohols, and ketones. Suitable alkanes include, but are not limited to, butane, pentane, pentene, 2-methylbutane, hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, heptane, heptene, octane, octene, 2,2,4 -trimethylpentane, 2,3dimethylhexane, 2,3,4-trimethylpentane, 2,3-dimethylpentane, nonane, nonene, decane, decene, undecane, undecene, dodecane, dodecene, tridecane, tridecene, tetradecane, tetradecene, pentadecane, pentadecane, pentadecane, pentadecane, pentadecane , nonildecene, eicosane, eicosene, uneicosene, doeicosane, doeicosene, triecosane, trieicosene, tetraeicosane, tetraeicosene, and isomers thereof. [00074] In one embodiment, cycloalkanes and cycloalkenes are not replaced. In another modality, cycloalkanes and cycloalkenes are monosubstituted. In another modality, cycloalkanes and cycloalkenes are multi-substituted. In the embodiment comprising the substituted cycloalkanes and cycloalkenes, the substituted groups include, without limitation, a branched or straight chain alkyl having 1 to 12 carbon atoms, a branched or straight chain alkylene having 1 to 12 carbon atoms, a phenyl, and any combination thereof. Suitable cycloalkanes and cycloalkenes include, but are not limited to, cyclopentane, cyclopentene, cyclohexane, cyclohexene, methyl-cyclopentane, methyl-cyclopentene, ethyl-cyclopentane, ethylcyclopentene, ethyl-cyclohexane, ethyl-cyclohexene, isomers and any combination thereof.
[00075] In one embodiment, the arils formed are not replaced. In other modalities, the arils formed are mono-substituted or multi-substituted. In the embodiment comprising substituted aryls, the substituted group includes, without limitation, a straight or branched chain alkyl having 1 to 12 carbon atoms, a straight or branched chain alkylene having 1 to 12 carbon atoms, a phenyl, and any combination thereof. Aryls suitable for the invention include, but are not limited to, benzene,
Petition 870180151558, of 11/14/2018, p. 32/58 / 46 toluene, xylene, ethylbenzene, para-xylene, meta-xylene, and any combination thereof.
[00076] The alcohols produced in the invention have 2 to 30 carbon atoms. In one embodiment, alcohols are cyclical. In another embodiment, alcohols are branched. In another modality, alcohols are in a straight chain. Alcohols suitable for the invention include, but are not limited to, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptydecanol, octyldecanol, nonildecanol, eicosanol, uneicosanol, doeicos trieicosanol, tetraeicosanol, and isomers thereof.
[00077] The ketones produced in the invention have 2 to 30 carbon atoms. In one embodiment, ketones are cyclical. In another embodiment, ketones are branched. In another modality, ketones are in a straight chain. Ketones suitable for the invention include, but are not limited to, butanone, pentanone, hexanone, heptanone, octanone, nonanone, decanone, undcanone, dodecanone, tridecanone, tetradecanone, pentadecanone, hexadecanone, heptildecanone, octildecone, unildonone, nonildane, eildan , trieicosanone, tetraeicosanone, and isomers thereof.
[00078] In one embodiment, the condensation reaction can produce a fuel mixture comprising gasoline hydrocarbons (ie gasoline fuel). “Gasoline hydrocarbons” refers to hydrocarbons comprising predominantly C5-9 hydrocarbons, for example C6-8 hydrocarbons, and having a boiling point range of 32 ° C (90 ° F) to about 204 ° C (400 ° F ). Gasoline hydrocarbons include, but are not limited to, light distillation gasoline, naphtha, catalytically and thermally cracked or fluidized gasoline, VB gasoline, and coke gasoline.
[00079] Hydrocarbon content of gasoline is determined by Method ASTM D2887.
[00080] In this mode, the condensation reaction can be carried out
Petition 870180151558, of 11/14/2018, p. 33/58 / 46 at a temperature where the thermodynamics for the purpose of the reaction is favorable for the formation of C5-9 hydrocarbons. The temperature for the condensation reaction will generally be in the range of 275 ° C to 500 ° C, and preferably 300 ° C to 450 ° C, and more preferably 325 ° C to 400 ° C. The condensation reaction can be conducted at pressures in the range between 0kPa to 9000kPa, and preferably in the range between 0kPa and 7000kPa, and more preferably 0kPa and 5000kPa.
[00081] The resulting gasoline hydrocarbons can be subjected to additional processes to treat the fuel mixture to remove certain components or further conform the fuel mixture to a gasoline fuel standard. Suitable techniques may include hydrotreating to remove any remaining oxygen, sulfur or nitrogen in the fuel mixture. Hydrogenation can be performed after the hydrotreating process to saturate at least some olefin bonds. Such hydrogenation can be carried out to conform the fuel mixture to a specific fuel pattern (for example, a gasoline fuel pattern). The hydrogenation step of the fuel mixture stream can be carried out according to known procedures, either with a continuous or batch method. In particular, it can be affected by the hydrogen supply at a pressure ranging from 5 bar to 20 bar and at a temperature ranging from 50 ° C to 150 ° C and reacting for a time ranging from 2 to 20 hours in the presence of a catalyst. hydrogenation such as a supported palladium or platinum, for example, 5% by weight of palladium or platinum on the activated carbon.
[00082] Isomerization can be used to treat the fuel mixture to introduce a desired degree of branching or otherwise selectively to at least some components in the fuel mixture. It may be useful to remove any impurities before the hydrocarbon is contacted with the isomerization catalyst. The isomerization step
Petition 870180151558, of 11/14/2018, p. 34/58 / 46 comprises an optional extraction step, in which the fuel mixture of the oligomerization reaction can be purified by extraction with water vapor or a suitable gas such as light hydrocarbon, nitrogen, or hydrogen. The optional extraction step is performed countercurrently in a unit upstream of the isomerization catalyst, in which the gas and liquid are contacted with each other, or rather the current isomerization reactor in a separate extraction unit using the countercurrent principle.
[00083] After the optional extraction step the fuel mixture can be passed to a reactive isomerization unit comprising one or more catalytic beds. The catalytic beds of the isomerization step can operate either in a co-current or counter-current manner. In the isomerization step, the pressure can vary from 20 bar to 150 bar, preferably in the range of 20 bar to 100 bar, the temperature being between 200 ° C and 500 ° C, preferably between 300 ° C and 400 ° C. In the isomerization step, any isomerization catalyst known in the art can be used. Suitable isomerization catalysts can contain group VII molecular sieve and / or metal and / or a carrier. In one embodiment, the isomerization catalyst contains SAPO-11 or SAPO41 or ZSM-22 or ZSM-23 or ferrite and Pt, Pd, or Ni, and AlTl · or SiO2, Pt / ZSM-23 / AEO3 and Pt / SAPO- 11 / SiO2.
[00084] Thus, in the modality, the fuel mixture produced by the processes described here is a hydrocarbon mixture that meets the requirements for a gasoline fuel (that is, according to ASTM D2887).
[00085] In one embodiment, the condensation reaction can produce a fuel mixture meeting the requirements for diesel fuel or aviation fuel. Traditional diesel fuels are petroleum distillates rich in paraffinic hydrocarbons.
Petition 870180151558, of 11/14/2018, p. 35/58 / 46
They have boiling ranges as wide as 370 ° F to 780 ° F (187 ° C to 415 ° 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) establishes the diesel grade according to the boiling range, along with possible ranges of other fuel properties, such as cetane number, fog point, flash point, viscosity, aniline point, sulfur content, water content, ash content, copper strip corrosion, and carbon residue. Thus, any fuel mixture found in the ASTM D975 can be defined as diesel fuel.
[00086] The present invention can also provide methods for producing jet fuel. Jet fuel is transparent to slightly colored. The most common fuel is an unleaded / paraffin based oil classified as A-1 Aircraft, which is produced to an internationally standardized set of specifications. Jet fuel is a mixture of a large number of different hydrocarbons, possibly as many as a thousand or more. The range of their sizes (molecular weights or carbon numbers) is restricted by product requirements, for example, freezing point or smoke point.
[00087] Aircraft fuel of the kerosene type (including Jet A and Jet A-1) has a carbon number distribution between about C8 and C16. Aircraft fuel of the Nafta type or wide cut (including Jet B) typically has a carbon number distribution between about C5 and C15. A fuel mixture found in ASTM D1655 can be defined as jet fuel.
[00088] Both aircraft (Jet A and Jet B) can contain a number of additives. Useful additives include, but are not limited to, antioxidants, antistatic agents, corrosion inhibitors, and fuel system ice inhibiting agents (FSII). Antioxidants avoid resin and are usually
Petition 870180151558, of 11/14/2018, p. 36/58 / 46 based on alkylated phenols, for example, AO-30, AO-31, or AO-37. Antistatic agents dissipate static electricity and prevent sparks. Stadis 450 with dinonylnaphthylsulfonic acid (DINNSA) as the active ingredient, is an example. Corrosion inhibitors, for example DCI-4a are used for civil or military fuels and DCI-6a is used for military fuels. FSII agents include, for example, Di-EFME.
[00089] Mixing fuels meeting the requirements for a diesel fuel (eg ASTM D975) or jet fuel (eg ASTM D1655) can be produced using the methods of the present invention. In one embodiment, the method for producing a diesel fuel mixture comprises: providing a biobased feed load; contacting the biobased feed charge with a catalyst and solvent to form an intermediate stream comprising carbohydrates; contacting the intermediate stream with an APR catalyst to form a plurality of oxygenated intermediates, wherein a first portion of the oxygenated intermediates are recycled to form the solvent; contacting an oxygenated intermediate stream with a condensation catalyst to produce an olefin stream; contacting the olefin stream with an oligomerization catalyst to produce superior hydrocarbons, in which the upper hydrocarbons can meet the definition of a diesel fuel or jet fuel.
[00090] In this mode, the condensation reaction can be carried out at a temperature where the thermodynamics for the proposed reaction is favorable for the formation of olefins with a carbon number ranging from C2 to Cg. The temperature for the condensation reaction will generally be in the range of 80 ° C to 275 ° C, and preferably 100 ° C to 250 ° C, and more preferably 150 ° C to 200 ° C. The condensation reaction can be conducted at pressures in the range of 0kPa to 9000kPa, and preferably in the range of 0kPa to 7000kPa, and even more preferably from 0kPa to 5000kPa.
Petition 870180151558, of 11/14/2018, p. 37/58 / 46
The olefin products produced from the condensation reaction can further be processed to form a fuel mixture meeting the standard for a diesel fuel or jet fuel. In one embodiment, the olefin products can be contacted with an oligomerization catalyst to produce a fuel mixture. The products of an olefin oligomerization reaction can primarily include linear oligomerization olefins or mixtures of olefins, paraffins, cycloalkanes and aromatics. The product spectrum is influenced by both reaction conditions and the nature of the catalyst. The oligomerization of olefins over an acid catalyst (eg zeolite) is influenced by many factors including thermodynamics, kinetics and diffusion limitations, and selectivity reactions by shape and side.
[00091] Without claiming to be limiting by theory, it is believed that a number of reaction mechanisms are responsible for distributing the final product of the olefin reaction to form a fuel mixture. For example, it is believed that the acid-catalyzed oligomerization of olefins occurs through a carbocationic mechanism resulting in a sequential chain growth. Molecular weight growth occurs by condensing either olefin to a single higher olefin. Olefins also undergo double bonding and skeletal isomerization. In addition to oligomerization, any of the two olefins can react to disproportionate to two olefins of two different carbon numbers, intermediate yield or "nonoligomer" olefins. This can tend to randomize the molecular weight distribution of the product without significantly changing its average carbon number. Olefin cracking can also occur simultaneously with oligomerization and disproportionation. Olefin can undergo cyclization and hydrogen transfer reactions leading to the formation of cyclolefins, alkyl aromatics and paraffins in which they have been called joint polymerization.
Petition 870180151558, of 11/14/2018, p. 38/58 / 46 [00092] In practice, the kinetics of oligomerization, disproportionation, and cracking reactions can determine the distribution of the olefin product under process conditions. At high temperatures or low pressures, thermodynamics triggers the reaction products to be distributed in the light olefin range where low temperature and high pressures tend to favor higher molecular weight olefins. At low temperature, mainly pure oligomers are formed with most of the product being trimers and tetramers. With an increase in temperature, more disproportionation and cracking, and thus, the olefin distribution can be slowed down. At moderate temperatures, the product can essentially be random and medium carbon number can be maximized. In addition to other thermodynamic considerations, the reactivity of the olefins decreases with an increase in the number of carbon due to diffusion limitations within the pore system of the catalyst and the lower probability of coincident reaction centralizes the molecules colliding for a biomolecular reaction.
[00093] In some embodiments, the olefinic feed stream may be pre-treated to remove any oxygenated or oxygen atoms that may be present in the intermediate olefin stream. The removal of oxygen from the olefin stream can occur by various methods known in the art, for example hydrotreating to remove any excess oxygen, sulfur or nitrogen.
[00094] The oligomerization catalyst with which the olefinic feed stream is contacted can be an acid catalyst including, but not limited to, zeolite, including the selective form or types of zeolite pentasil ZSM-5. A specific zeolite can be selectively shaped that can be used to form a higher hydrocarbon that does not contain excessively branched hydrocarbons. For example, the acid catalyst can comprise a pentacil zeolite with a SiO2 / Al2O3 ratio
Petition 870180151558, of 11/14/2018, p. 39/58 / 46 ranging from 30 to about 1000 in the form of hydrogen or sodium. Other zeolites with medium pores (for example, ZSM-12, -23) can also produce oligomers with a small degree of branching due to the “shape selectivity” phenomenon. Other acid catalysts may include, but are not limited to, amorphous acid materials (silica-alumina), large pore zeolites, ion exchange resins, and supported acids (for example phosphoric acids).
[00095] In one embodiment, an olefinic oligomerization reaction can be performed in any suitable reactor configuration. Suitable configurations include, but are not limited to, batch reactor designs, semi-batch reactors, or continuous reactors such as 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 diesel and jet fuel hydrocarbon boiling range can be performed using an oligomerization reactor to contact an olefinic feed stream comprising small chains of olefins having a chain length of 2 to 8 carbon atoms with a zeolite catalyst under high temperatures and pressures in order to convert short chain olefins to a fuel mixture in the diesel boiling range. The oligomerization reactor can be employed at relatively high pressures of about 20 to 100 bar, and at temperatures between 150 ° C and 300 ° C, preferably about 200 ° C to 250 ° C with a zeolitic oligomerization catalyst.
[00096] The reactor design may also comprise a catalyst regenerator to receive deactivated or spent catalyst from the oligomerization reactor. The catalyst regenerator for catalyst regeneration can operate at relatively low pressures of 1 to 5 bar,
Petition 870180151558, of 11/14/2018, p. 40/58 / 46 typically 1 to 2 bar and at temperatures of about 500 to 1000 ^o C, typically 500 ° C to 550 ° C, to burn coke or hydrocarbons encrusting the catalyst. Air or oxygen can be introduced into the catalyst regenerator to allow any coke, carbon or other deposits in the deactivated catalysts to be oxidized, thus regenerating the catalyst for further use in the production process.
[00097] In one embodiment, the regeneration reactor receives the deactivated catalyst from the oligomerization reactor. The deactivated catalyst can be removed using known means to remove the catalyst from a reaction vessel. In one embodiment, the deactivated catalyst can be removed from the oligomerization reactor using a pressure reduction system to bring the catalyst from the relatively high operating pressure of the oligomerization reactor to the relatively low operator pressure of the catalyst regenerator. The pressure reduction system may include a locking hopper and a release hopper, as known to one skilled in the art to isolate the reactor reactor high pressure from the catalyst regenerator low pressure.
[00098] Once the catalyst has been regenerated, the regenerative catalyst can be transferred to the oligomerization reactor using known means to transport a catalyst to a reaction vessel. In one embodiment, the regenerated catalyst can be transported to the inlet of the oligomerization reactor using a pressure system to increase the pressure of the regenerated catalyst before introducing the regenerated catalyst into the oligomerization reactor. The pressure system may include a regenerated catalyst flow control system that is configured to ensure its operation, a locking hopper, and a means to increase the pressure, for example, a Venturi compressor, a mechanical compressor, or to introduce the regenerated catalyst stream
Petition 870180151558, of 11/14/2018, p. 41/58 / 46 pressurized in the oligomerization reactor.
[00099] The resulting oligomerization stream results in a fuel mixture that can be a wide variety of products including products comprising C5 to C24 hydrocarbons. Additional processing can be used to obtain a fuel mixture meeting a desired pattern. An additional separation step can be used to generate a fuel mixture with a narrower range of carbon numbers. In one embodiment, a separation process such as a distillation process is used to generate a fuel mixture comprising C12 to C24 hydrocarbons for further processing. The remaining hydrocarbons can be used to produce a fuel mixture for gasoline, recycled to the oligomerization reactor, or used in additional processes. For example, a kerosene fraction can be derived along with the diesel fraction and can also be used as a luminous paraffin, as a jet fuel mixture component in conventional crude or synthetic derived jet fuels, or as reagents ( especially fraction C10-13) in the process to produce LAB (linear alkylbenzene). The naphtha fraction after hydroprocessing can be routed to a thermal fractionator for the production of ethylene and propylene or routed as it is to a catalytic fractionator to produce ethylene, propylene, and gasoline.
[000100] Additional processes can be used to treat the fuel mixture to remove certain components or even according to the fuel mixture for a standard diesel or jet fuel. Suitable techniques may include hydrotreating to remove any oxygen, sulfur or nitrogen remaining in the fuel mixture. Hydrogenation can be performed after the hydrotreating process to saturate at least some olefinic bonds. Such hydrogenation can be carried out to conform the fuel mixture to a
Petition 870180151558, of 11/14/2018, p. 42/58 / 46 specific fuel (for example a diesel fuel standard or a jet fuel standard). The hydrogenation step of the fuel mixture stream can be carried out according to known procedures, either with the continuous or batch method. In particular it can be affected by the feed hydrogen at a pressure ranging from 5 to 20 bar and a temperature ranging from 50 ° C to 150 ° C and reacting for a time ranging from 2 to 20 hours in the presence of a hydrogenation catalyst such as a supported palladium or platinum, for example, 5% by weight of palladium or platinum on activated carbon.
[000101] 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 be useful to remove any impurities before the hydrocarbons are contacted with the isomerization catalyst. The isomerization step comprises an optional extraction step, in which the fuel mixture of the oligomerization reaction can be purified by extraction with water vapor or suitable gas such as light hydrocarbon, nitrogen or hydrogen. The optional extraction step is carried out countercurrently 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 the countercurrent principle .
[000102] After the optional extraction step, the fuel mixture can be passed to a reactive isomerization unit comprising one or more catalytic beds. The catalytic beds of the isomerization step can operate either in a co-current or counter-current manner. In the isomerization step, the pressure can vary from 20 bar to 50 bar, preferably in the range of 20 bar to 100 bar, the temperature being between 200 ° C and 500 ° C preferably between 300 ° C and 400 ° C. In the isomerization stage, any
Petition 870180151558, of 11/14/2018, p. 43/58 / 46 isomerization catalyst known in the art can be used. Suitable isomerization catalysts can contain molecular sieves and / or a Group VII metal and / or a carrier. In one embodiment, the isomerization catalyst contains SAPO-11 or SAPO41 or ZSM-22 or ZSM-23 or ferrite 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-1 / SiOz.
[000103] Thus, in one embodiment, the fuel mixture produced by the processes described here is a hydrocarbon mixture that meets the requirements for jet fuel (that is, according to ASTM D1655). In another embodiment, the product of the process described here is a hydrocarbon mixture that comprises a fuel mixture, we meet the requirements for a diesel fuel (ie according to ASTM D975).
[000104] To facilitate a better understanding of the present invention, the following examples of certain aspects of the modalities are given. In no way should the following examples limit, or define the entire scope of the invention.
EXAMPLES
Examples 1-14
Hydrogenolysis and batch aqueous phase reform [000105] By treating an aqueous hydrocarbon mixture, carbohydrates can be "reformed" under appropriate conditions to produce hydrogen, as illustrated by the formation of isopropanol (ie IPA or 2-propanol) from sorbitol in Eq 1 shown above. Alternatively, in the presence of hydrogen, polyols, and mono-oxygenates such as IPA can be formed by hydrogenolysis, where hydrogen is consumed preferably produced, as shown in Eqs 2 and 3 above.
[000106] For hydrogenolysis paths where a hydrogen source
Petition 870180151558, of 11/14/2018, p. 44/58 / 46 is available (for example refinery outlet gas, or direct H2 production through renewable or non-fossil energy), biofuel yields can be increased by preventing the loss of carbon based on CO2. The current process provides optimized conditions to produce polyols such as propylene glycol (PG) through Eq 2 rather than loss of yield to CO2 through the “reform reaction” in Eq 1 for those cases where an H2 source from energy solar or nuclear with capture and storage of CO2 in a centralized location, and use of that hydrogen to increase the yields of biofuels through the reactions shown in Eq 2 and Eq 3.
[000107] To test this concept, a series of reactions were conducted in 100 ml mixing reactors with gas induction impellers with discharge tube (Series Parr 4590). The reactors were loaded with 60 g of liquid comprising 15, 30 or 50% by weight of sorbitol in deionized water. Sorbitol is the sugar alcohol formed from the hydrogenation of glucose, or hydrogenolysis and combined hydrogenation of sucrose, and is representative of an intermediate biobased feed charge that can be readily formed from sugar cane, corn starch, or from the biomass hydrogenolysis. The reactor was charged with one gram of a hydrogenolysis or reforming catalyst, comprising a group VIII metal in the support. A batch reaction time of 20 hours under these conditions corresponds to a spatial speed of weight per hour (galling / g-catalyst / h) of about 3, for a comparable continuous flow reactor. A 0.5 micron sintered metal filter attached to an immersion tube allowed liquid samples to be taken through the course of the reaction.
[000108] For example # 1-12, the reactor was preloaded with H2 to obtain a nominal pressure of 6000kPa after heating up to the reaction conditions. For example # 13 and # 14, nitrogen was added at 3000kPa before
Petition 870180151558, of 11/14/2018, p. 45/58 / 46 start.
[000109] Samples were analyzed by an HPLC method based on the combined size and ion exclusion chromatography, to determine unreacted sorbitol, and the amount of C3 and minor polyols formed: glycerol (gly), ethylene glycol (EG), and 1,2-propylene glycol (PG).
[000110] Additional GC analyzes through a DB-5 column of moderate polarity were conducted to assess formation of C6 and lighter oxygenated intermediates (ketones, aldehydes and alcohols). A separate CG equipped with thermal conductivity and flame ionization (FID) detectors for analysis of refinery gas, were used to detect H2, CO2 and C1-C5 light alkanes.
[000111] Results of hydrogenolysis experiments conducted at 210 ° C to 220 ° C were shown in table 1. Comparative aqueous phase reform experiments (APR) under N2 at 245-260 ° C are given in table 2. For these tables , "% By weight of total polyols" is the sum of unreacted sorbitol, plus EG, EO, and glycerol. Selectivity of EG, PG, and glycerol is defined as the percentage by weight of these formed species, divided by the percentage by weight of reacted sorbitol. For example, 13 to 2.6% and molar yield from liquid N2 production was observed, corresponding to a final H2 atmosphere of 110kPa. A similar H2 atmosphere was present at the end of the example experiment 14 (109kPa), from the sorbitol reform. In addition to polyols, a group of C1-C6 ketones, alcohols, and carboxylic acids were also detected by analysis of GCMS (specific mass) of APR and hydrogenolysis products (Table 3).
[000112] As one skilled in the art should know, examples 13 and 14 show that at high temperatures (260 ° C), few polyols remain in the APR reaction mixture. When the temperature is lowered from 260 ° C to 245 ° C under APR conditions, the selectivity for C2-C3 polyols (EG, EP, glycerol) is increased, but remains lower than
Petition 870180151558, of 11/14/2018, p. 46/58 / 46
10% on the supported platinum catalyst. An additional reduction in temperature from 210 ° C to 220 ° C and the use of non-precious nickel, ruthenium, and cobalt catalysts leads to an increase in selectivity (25-70%) for C2-C3 polyol “hydrogenolysis” products (Examples 1-12). Increased selectivity for hydrogenolysis or polyol products (example 12) where a sorbitol diluted 15% in water solution is fed to the reactor with respect to standard reaction conditions of 50% sorbitol. Without claiming to be limited by theory, it is believed that this can be explained by the degradation of sorbitol occurring in reaction orders greater than one, such that high concentrations lead to non-selective by-products. The selectivity of C2-C3 hydrogenolysis polyols decreases with time, while the conversion of sorbitol is increased, which is also indicative of an additional reaction of sorbitol intermediates. However, it was possible to obtain conversion greater than 90% of sorbitol, while maintaining at least 25% selectivity for polyols EG, PG, and C2-C3 hydrogenolysis glycerol.
Petition 870180151558, of 11/14/2018, p. 47/58 / 46
Batch hydrogenolysis experiments
Table 1
Ex# Catalyst Gas Temp. [degrees C] Final pH Time hours Sorbitol% by weight Glycerol% by weight EG% by weight PG% by weight polyols% by total weight HG prod / sorbitol EG + PG + Gly selectivityNi / SiO2-1 H2 220 3.85 0.00 50.00 0.00 0.00 0.00 50.00 0.00 AT1.00 27.48 9.58 2.32 3.43 42.81 0.56 68.1%3.20 16.48 8.37 3.43 7.56 35.84 1.17 57.7%7.40 3.22 4.45 3.24 14.98 25.89 7.04 48.5%18.10 0.04 0.51 1.74 15.64 17.93 437.50 35.8% 2 5% Ru / C H2 210 3.71 0.00 50.00 0.00 0.00 0.00 50.00 0.00 AT1.00 37.67 4.80 1.20 1.50 45.17 0.20 60.8%3.30 27.47 7.68 2.42 4.44 42.01 0.53 64.6%7.40 24.76 6.86 2.62 5.45 39.69 0.60 59.2%19.00 19.48 5.17 2.13 5.58 32.36 0.66 42.2%19.10 16.88 4.47 1.83 5.08 28.26 0.67 34.4% 3 5% Ru / C H2 220 3.95 0.00 50.00 0.00s 0.00 0.00 50.00 0.00 AT1.00 33.42 5.37 2.01 3.02 43.82 0.31 62.7%2.80 27.29 5.35 2.68 4.46 39.77 0.46 55.0%5.90 24.42 4.66 2.62 4.95 • 36.66 0.50 47.8%19.00 15.65 3.01 1.81 5.12 25.59 0.63 28.9% 4 Ni / SiO2-1 H2 210 3.78 0.00 50.00 0.00 0.00 0.00 50.00 0.00 AT1.05 33.21 7.65 1.79 1.28 , 43.92 0.32 63.8%3.08 19.61 12.19s 3.05 4.57 39.42 1.01 65.2%8.22 8.24 8.91 3.96 10.64 31.74 2.85 56.3%20.10 0.24 2.61 3.09 17.10 23.04 96.00 45.8% 5 Raney Co H2 210 3.8 0.00 50.00 0.00 0.00 0.00 50.00 0.00 AT2724 1.00 40.14 2.01 0.75 1.26 44.16 0.10 40.8%2.90 34.77 2.99 1.24 2.49 41.49 0.19 44.1%7.50 27.38 3.27 1.51 4.02 36.18 0.32 38.9%25.00 19.63 2.75s 1.50 5.25 29.13 0.48 31.3% 6 5% Ru / C H2 210 3.68 0.00 50.00 0.00 0.00 0.00 50.00 0.00 AT1.00 39.16 3.76 0.75 0.75 44.43 0.13 48.6%3.50 30.42 5.94 1.48 2.47 40.31 0.33 50.5%7.33 27.81 5.63 1.88 3.29 38.60 0.39 48.6%22.50 21.02 4.12 1.60 3.66 30.40 0.45 32.4% 7 Ni / SiO2-1 H2 210 3.96 0.00 50.00 0.00 0.00 0.00 50.00 0.00 AT1.00 34.41 5.74s 1.57 0.78 42.50 0.24 51.9%2.70 19.97 9.93 2.98 4.97 37.85 0.90 59.5%7.70 11.09 8.03 3.89 10.36 33.37 2.01 57.3%18.70 0.05 0.75 2.50 17.99 21.29 425.00 42.5% 8 Ni / SiO2-1 H2 210 4.82 0.00 50.00 0.00 0.00 0.00 50.00 0.00 AT0.00 48.04 0.00 0.00 0.00 48.04 0.00 0.0%2.50 23.69 7.48 2.99 5.49 39.66 0.67 60.7%7.70 12.50 6.71s 3.73 9.94 32.88 1.63 54.4%22.80 2.14 3.24 3.49 15.95 24.82 10.58 47.4% 9 Ni5249P H2 220 5.31 0.00 50.00 0.00 0.00 0.00 50.00 0.00 AT2.05 33.11 1.18 2.16 5.51 41.97 0.27 52.4%7.10 16.85 1.39 3.98 10.93 33.15 0.97 49.2%23.60 0.79 0.58 3.84 17.29 22.50 27.56 44.1% 10 5% Ru / C H2 210 4.1 0.00 50.00 0.00 0.00 0.00 50.00 0.00 AT1.25 37.17 1.00 1.39 2.99 42.55 0.14 41.9%5.92 28.60 2.39 2.59 6.98 40.56 0.42 55.9%19.60 17.09 2.71 3.70 11.54 35.04 1.05 54.5% 11 Ni / SiO2-1 H2 210 7.56 0.00 50.00 0.00 0.00 0.00 50.00 0.00 AT2.00 30.13 0.92 1.93 4.58 37.56 0.25 37.4%6.75 13.21 0.61 3.65 9.52 26.99 1.04 37.4%25.00 0.72 0.00 2.94 12.26 15.92 21.13 30.8% 12 Ni / SiO2-2 H2 215 AT 0 15.00 0.00 0.00 0.00 15.00 0.00 AT1.5 4.00 1.37 1.25 4.60 11.22 1.81 65.6%3 1.09 1.82 2.09 5.27 10.27 8.42 66.0%5.5 0.11 2.15 3.04 4.79 10.09 90.73 67.0%
Ni / SiÜ2-1 = 64% Nickel; Ni / SiO2-2 = 53-58% by weight of Ni Table 2
Batch APR experiments
Ex# Catalyst Gas Temp. [degrees C] Final pH Time hours Sorbitol% by weight Glycerol% by weight EG% by weight PG% by weight polyols% by total weight HG prod /sorbitol EG + PG + Gly selectivity 13 1 9%Pt / Al2O3 N2 260 3.6 0.00 30.00 0.00 0.00 0.00 30.00 0.00 AT1.00 27.23 0.00 0.00 0.00 27.23 0.00 0.0%3.00 10.84 0.00 0.00 0.20 11.04 0.02 1.1%5.50 1.57 0.00 0.10 0.20 1.87 0.19 1.1% 14 1 9%Pt / Al2O3 N2 245 AT 0.00 15.00 0.00 0.00 0.00 15.00 0.00 AT 20 0.67 1.04 0.00 0.23 1.94 1.89 8.9%
Petition 870180151558, of 11/14/2018, p. 48/58 / 46
1.9% Pt / Al2O3 modified catalyst 2: 1 Re / Pt
Table 3
Components formed in APR and hydrogenolysis
Propionaldehyde Acetone 2,5-dimethyltetrahydrofuran Tetrahydrofuran + Vinyl format Methanol Isopropyl acetate + 2-butanone Tetrahydropyran Isopropyl alcohol Ethanol 2-pentanone and 3-pentanone 2-butanol n-propanol 3-hexanone 2-hexanone 2-methylcyclopentanone 3-hexanol 1-pentanol dihydro-2-methyl-3 (2H) -Furanone 3-hydroxy-2-butanone 2-methyl-1-pentanol Ethyl lactate 1-hexanol 1-hydroxy-2-butanone Acetic Acid 2,5-hexanedione Propionic acid 2,3-butanediol + isobutyric acid Propylene glycol Ethylene glycol Valeric acid Hexanoic acid Glycerol Isosorbide 2,5-dimethyltetrahydrofuran 2,3-butanediol + isobutyric acid
Examples 15-24
Hydrogenolysis acid condensation and APR products in a catalytic pulse micro-reactor [000113] A GC injector was loaded with 0.05 grams of ZSM-5 acid condensation catalyst, and maintained at 375 ° C. A microliter of a carbohydrate / water mixture was injected into the catalyst bed, to examine the formation of liquid fuel products. The inserted catalytic injector was followed by the capillary CG columns RestecRtx-1701 and DB-5 in series, to solve components of the hydrocarbon and aromatic reaction through the analysis programmed by temperature.
Petition 870180151558, of 11/14/2018, p. 49/58 / 46 [000114] Mixtures of pure EG, EP, glycerol, sorbitol and IPA components were prepared to examine plausible yields of liquid biofuels through condensation on ZSM-5. Unconverted mass largely corresponds to deposition of coke (requiring burning through regeneration), or loss to light gases.
[000115] The extent of product formation for fixed sample injection volume was measured by integrating the area under the GC's FID response, and dividing by the effective weight fraction of sorbitol required to prepare the mixture. For sorbitol, this was the weight fraction of the sorbitol itself. For isopropanol (IPA), the stoichiometry of the APR reaction (1) was assumed, while PG was assumed formed through hydrogenolysis by equation (2). In this way, a relative gasoline yield per unit quantity of sorbitol fed to an APR or initial hydrogenolysis step, could be evaluated for model compounds, as a reporter in Examples 15-20 in Table 4. Reported yields are the sum of all components; yields of components to select cases reported in Table 5, showing disaggregations for alkanes, olefins, benzenes, toluenes, xylenes, and other aromatics.
[000116] As should be evident to a person skilled in the art, the results for examples # 15 and # 16 indicate that the aqueous phase reforming the isopropanol (IPA) yield through reaction results # 1 in an increase in yield by more than than twice, in relation to the pulsating sorbitol precursor, despite the loss of 50% of carbon as CO2. This is only true that IPA was pulsed as a 16.5% by weight solution, or a 50% by weight solution, in deionized water.
[000117] Hydrogenolysis to form glycerol (example # 18) gives a lower yield (twice better than sorbitol), but hydrogenolysis to form EG or PG (examples # 19 and # 20) given higher yields than the corresponding APR reaction for form IPA, for the study of compounds
Petition 870180151558, of 11/14/2018, p. 50/58 / 46 models.
[000118] Pulses of the current reactor product from the APR “stage 1” or hydrogenolysis experiments were injected for examples # 21023 from table 4. Yield from the pulsation of the batch reaction product from example # 13 of APR given an excess yield of 2.74 above the sorbitol baseline, for example # 21. Pulsed hydrogenolysis product forms examples # 10 and # 8 given even high yields, for examples # 22 and # 23. These results demonstrate the potential for high yields through hydrogenolysis followed by acid condensation, with APR ratio followed by acid condensation.
[000119] The conclusions were substantially through analysis of yield loss of CO2 and light alkanes, which were only 2.7% of total carbon for example # 10, but approximately 10% of the total carbon for examples APR # 13 and # 14 .
Table 4
Gasoline formation through acid-catalyzed condensation of APR product or hydrogenolysis: ZSM-5 pulse microreactor at 370 ° C
Ex# Type Injected mixture CG area: Gasoline / g-sorbitol yield 15 Power model 50% sorbitol1.00 16 Power model 50% IPA2.95 17 Power model 16.5% IPA2.47 18 Power model 50% Glycerol2.03 19 Power model 50% EG4.15 20 Power model 50% PG5.47 21 Stage 1 prod APR Ex. # 132.74 22 Stage 1 prod HG Ex # 102.79 23 Stage 1 prod HG Ex # 83.15 24 Stage 1 prod Direct biomass HG 2.04 Table 5 Direct HG from APR HG Biomass Ex # 13 Ex # 8 Ex # 24 Component % by weight % by weight % by weight Alcanos 20.24 24.4 56.85 Olefins 4.08 4.12 2.19 Benzene 10.11 6.59 13.54 Toluene 21.36 25.88 14.97 Ethylbenzene 0.41 ss 0.19 0.22 Xylene 13.3 18.79 3.33 Trimethylbenzene 6.28 4.57 1.71 Naphthalene 16.02 14.66 4.73 Others 8.2 0.8 2.46 Known Total 91.8 99.2 97.54
Petition 870180151558, of 11/14/2018, p. 51/58 / 46
Example 24
Direct biomass hydrogenolysis [000120] For example # 24, 3.59 grams of sugarcane bagasse solids (5% moisture) were added directly to the hydrogenolysis reactor with 60.1 grams of deionized water, to demonstrate combined hydrolysis of biomass with hydrogenolysis of the resulting hydrolyzate. 0.924 grams of Ni / SiO2-1 catalyst were used, for reaction conducted with 5300kPa of H2. Temperatures were aged for 2.5 hours at 170 ° C, 2.5 hours at 190 ° C, and 22 hours at 210 ° C, to allow hydrolyzable C5 sugars more readily to be extracted and hydrotreated at a low temperature, to avoid degradation of heavy extremities. Results were reported as an example 24 in table 4, and for the composition data in Table # 5. Yields were twice that of direct sorbitol feed for acid condensation, despite the fact that a substantial portion (up to 30%) of lignin bagasse, which is not expected to be converted under the conditions tested.
[000121] The results show an ability to convert biomass to liquid biofuels (for example gasoline) by direct hydrogenolysis, followed by acid condensation.
[000122] Thus, the invention is well adapted to reach the ends and advantages mentioned as well as those that are inherent here. The particular modalities described above are only illustrative, as the invention can be modified and practiced in different but apparent equivalent ways to those skilled in the art having the benefit of the teachings shown here. In addition, no limitation is intended for the details of the construction or design shown here, other than as described in the claims above. It is thus evident that the particular illustrative modalities described above can be altered or modified and all such considerations and methods are described in terms of
Petition 870180151558, of 11/14/2018, p. 52/58 / 46 “understand” and “contain” or “include” several components or stages, the compositions and methods can also “consist essentially of” or “consist of” various components and stages. All 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 falling within the range is specifically described. In particular, the entire range of values (of the form (from about aa to b, "or equivalent," from about a to b, "or, equivalently," from about ab ") described here is to be is to be understood for adjust every number and range encompassed within the broadest range of values. Also, the terms of the claims have their full, common meaning unless otherwise explicitly and clearly defined by the patent holder. In addition, the indefinite articles "one" or “one”, as used in the claims, are defined here to mean one or more of the element it introduces. If there is any conflict in the use of a word or term in this specification and one more or patent or other documents that may be incorporated here as a reference, definitions that are consistent with this specification should be adopted.

权利要求:
Claims (15)
[1]
1. Method for producing superior hydrocarbons characterized by the fact that it comprises:
contacting a solid biomass feed load comprising hydrogen lignins and a hydrogenolysis catalyst in a reaction vessel to produce a reaction product comprising one or more polyols in an amount greater than 25 mole%;
wherein at least a portion of the solid biomass feed load is converted to provide a carbohydrate in a hydrolysis reaction;
reacting the carbohydrate directly with hydrogen in the presence of a hydrogenolysis catalyst to produce a reaction product comprising a polyol; wherein the hydrolysis reaction and the hydrogenolysis reaction are conducted in a single step; and processing at least a portion of the reaction product to form a fuel mixture; wherein processing at least a portion of the reaction product comprises contacting at least a portion of the reaction product comprising one or more polyols in an amount greater than 25 mole% with a condensation catalyst to form one or more higher hydrocarbons comprising at least one of the following: an alkane with 4 to 30 carbon atoms, an alkene with 4 to 30 carbon atoms, a cycloalkane with 5 to 30 carbon atoms, a cycloalkene with 5 to 30 carbon atoms, an aryl, an alcohol with at least 4 carbon atoms and a ketone with at least 4 carbon atoms.
[2]
2. Method according to the claim1, characterized by the fact that the carbohydrate is reacted directly with a hydrogen in the presence of a hydrogenation catalyst before hydrogenolysis.
Petition 870180151558, of 11/14/2018, p. 54/58
2/4
[3]
Method according to claim 2, characterized by the fact that the hydrogenolysis catalyst and the hydrogenation catalyst are present in the same vessel as the reactor.
[4]
Method according to claim 2 or 3, characterized in that the hydrogenolysis catalyst and the hydrogenation catalyst are the same catalyst.
[5]
Method according to any one of claims 1 to
4, characterized by the fact that the fuel mixture comprises at least a composition selected from a fuel additive, a gasoline fuel, a diesel fuel or an aviation fuel.
[6]
A method according to any one of claims 1 to
5, characterized in that the processing of at least a portion of the reaction product comprises contacting at least a portion of the reaction product with a condensation catalyst to form the fuel mixture in which the fuel mixture comprises a gasoline fuel .
[7]
Method according to any one of claims 1 to
5, characterized by the fact that processing at least a portion of the reaction product comprises contacting at least a portion of the reaction product with a hydrogenation catalyst to form the fuel mixture.
[8]
Method according to any one of claims 1 to
5, characterized in that the processing of at least a portion of the reaction product comprises contacting at least a portion of the reaction product with an acid catalyst to form at least some olefins, and contacting the olefins with an oligomerization catalyst to form the fuel mixture.
[9]
9. Method for producing superior hydrocarbons
Petition 870180151558, of 11/14/2018, p. 55/58
3/4 characterized by the fact that it comprises:
providing a biobased feed charge source for a reaction vessel by treating a biobased feed charge source comprising lignin in the reaction vessel;
treating the biobased feed load so as to form a carbohydrate by a hydrolysis reaction;
in said reaction vessel, after the formation of the carbohydrate, reacting the carbohydrate with hydrogen in a hydrogenolysis reaction to produce reaction products comprising an alcohol, a polyol, and a higher polyol with an oxygen to carbon of 0.5 or more; wherein the hydrolysis reaction and the hydrogenolysis reaction are conducted in a single step;
recycling the upper polyol through the hydrogenation reaction to produce reaction products comprising an alcohol and a polyol; and processing at least a portion of the reaction products to form a fuel mixture.
[10]
A method according to claim 9, characterized in that treating the biobased feed charge to form a carbohydrate comprises contacting at least a portion of the biobased feed charge with a hydrolysis catalyst.
[11]
Method according to claim 10, characterized in that the hydrolysis catalyst comprises at least one catalyst selected from the group consisting of: an acid catalyst, a base catalyst, a metal catalyst, an acetic acid, formic acid, acid levulinic, and any combination thereof.
[12]
Method according to any one of claims 9 to 11, characterized in that the carbohydrate is reacted directly with a hydrogen in the presence of a hydrogenation catalyst before hydrogenolysis.
Petition 870180151558, of 11/14/2018, p. 56/58
4/4
[13]
Method according to any one of claims 9 to 11, characterized in that the processing of at least a portion of the reaction products comprises contacting at least a portion of the reaction products with a condensation catalyst to form the mixture of fuel, wherein the fuel mixture comprises a gasoline fuel.
[14]
Method according to any one of claims 9 to 11, characterized in that the processing of at least a portion of the reaction products comprises contacting at least a portion of the reaction products with a hydrogenation catalyst to form a fuel mixture .
[15]
Method according to any one of claims 9 to 11, characterized in that the processing of at least a portion of the reaction products comprises contacting at least a portion of the reaction products with an acid catalyst to form at least some olefins , and contacting the olefins with an oligomerization catalyst to form the fuel mixture.

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法律状态:
2018-08-21| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

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2019-02-26| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2019-05-07| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 20/12/2010, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 20/12/2010, 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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US29156709P| true| 2009-12-31|2009-12-31|

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US61/291567|2009-12-31|

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PCT/US2010/061248|WO2011082001A1|2009-12-31|2010-12-20|Biofuels via hydrogenolysis-condensation|

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