 oxygenated hydrocarbon deoxygenation method
专利摘要:
A catalyst, method for creating a catalyst, a method of oxygenated hydrocarbon sesoxygenation, a system for producing fuel and a system for producing fuel from bio-oils are one or more aspects and / or one or more modalities of catalysts, catalyst preparation methods, deoxygenation methods and fuel production methods. 公开号:BR112013014687B1 申请号:R112013014687-7 申请日:2011-12-16 公开日:2019-02-05 发明作者:Thien Duyen Thi NGUYEN；Krishniah Parimi 申请人:Energia Technologies, Inc.； IPC主号:
专利说明:
METHOD OF DEOXYGENATION OF OXYGENED HYDROCARBONS CROSS REFERENCE TO RELATED ORDERS This patent application claims the benefit of US Patent Application S / N 61 / 424,043, dossier No. ETI003, entitled “CATALYSTS, METHODS OF PREPARATION OF CATALYST, METHODS OF DEOXYGENATION, AND METHODS OF FUEL PRODUCTION, by Thien Duyen Thi NGUYEN and Krishniah PARIMI, deposited on 12/16/2010. This patent application relates to US Patent Application dossier No. ETI004US1, entitled “CATALYSTS AND METHODS OF PREPARATION OF CATALYST, by Thien Duyen Thi NGUYEN and Krishniah PARIMI, filed on 12/16/2011, and to the Patent Application US dossier number ETI-004US2, entitled “METHODS OF DEOXYGENATION AND METHODS OF FUEL PRODUCTION, by Thien Duyen Thi NGUYEN and Krishniah PARIMI, filed on 12/16/2011. The content of all such applications and / or patents is incorporated into this document in its entirety as a reference for all purposes. BACKGROUND Catalysts are widely used in a variety of industrial processes. Due to the diversity of types of processes, there are many types of catalysts. The present inventors have made one or more findings regarding catalysts, methods of creating catalysts, and methods of using catalysts. An example of one of the areas in which these findings may be applicable is the use of renewable raw materials for the production of transport fuels, such as for clean energy technologies that seek to use bio-oils to replace petroleum raw materials for 2/61 fuels. Bio-oils are advantageous raw fuel raw materials since they are easy to obtain and therefore allow fuel cost stabilization and provide energy autonomy. Bio-oils are a renewable resource with significant environmental benefits. First, organic nitrogen and sulfur compounds occur much less in bio-oil raw materials compared to petroleum fuels, so less harmful NO X and SO X emissions will be produced when biofuels are used. Second, CO 2 emissions during the use of biofuels are offset by plants that need CO 2 to grow, therefore they are commonly referred to as carbon neutral. There is a need for improved catalysts, improved methods of preparing catalysts, deoxygenation methods, and / or processes for applications such as, but not limited to, fuel production from renewable raw materials. SUMMARY One or more aspects of this invention belong to catalysts. One aspect of the invention is a catalyst. According to one embodiment, the catalyst comprises a porous substrate and a catalytically effective metallic coating deposited without electricity having a nanoscale thickness. Another aspect of the invention is a method for creating a catalyst. According to one embodiment, the method comprises providing a porous substrate, providing a solution comprising a metal for deposition without electricity (ELD), mixing the substrate with the solution, controlling the temperature of the mixture of the substrate and the solution, and raising the temperature while adding a reducing agent incrementally or continuously so as to cause deposition without 3/61 controlled electricity of the metal as a catalytically active stable nanoscale coating of the substrate. Another aspect of the invention is a method of deoxygenation. According to a modality for deoxygenation of oxygenated hydrocarbons, the method comprises providing a catalyst comprising a porous substrate and a catalytically effective metal nanoscale coating deposited without electricity on the substrate and placing the catalyst in contact with the oxygenated hydrocarbons and hydrogen in order to perform hydrogenation and deoxygenation, and deoxygenation is performed preferably by decarbonylation and decarboxylation through hydrodeoxygenation. Another aspect of the invention is a system for producing fuel from raw materials, such as bio-oil. According to one embodiment, the system comprises a deoxygenation stage, the deoxygenation stage comprises at least one deoxygenation reactor chamber and a catalyst, and the catalyst comprises a porous substrate and a metallic coating deposited without electricity that has a thickness of nanoscale. The system additionally comprises an isomerization and hydrocracking stage which comprises at least one reactor isomerization and hydrocracking it is a catalyst isomerization and hydrocracking . 0 stage of isomerization and hydrocracking is configured To receive the Hydrocarbons liquids of the stage deoxygenation and hydrogen. The isomerization and hydrocracking stage operates under conditions to convert the liquid hydrocarbons from the deoxygenation stage into gasoline, diesel fuel, and / or jet / jet fuel. It should be understood that the invention is not limited in its application to the details of construction and the provisions of the 4/61 components shown in the description below. The invention is capable of other modalities or of being practiced or executed in several ways. In addition, it should be understood that the phraseology and terminology used in this document are for purposes of description and should not be understood as limiting. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is an enlarged image of a catalyst according to an embodiment of the present invention. Figure 1-1 is a typical Arrhenius plan for one or more embodiments of the present invention. 1-2 Figure 1-2 is a graph showing a composition of Camelina oil. Figure 1-3 are gas chromatography data of the deoxygenated liquid product according to one or more embodiments of the present invention. Figure 2 is a flow chart according to one or more embodiments of the present invention. Figure 3 is a flow chart for an example according to one or more embodiments of the present invention. Figure 4 is a flow chart according to one or more embodiments of the present invention. Figure 5 is a flow chart according to one or more embodiments of the present invention. Those skilled in the art will realize that elements in the Figures are illustrated for the sake of simplicity and clarity and were not necessarily drawn to scale. For example, the dimensions of some of the elements in the Figures can be exaggerated in relation to other elements to help improve the understanding of the modalities of the present invention. DESCRIPTION For the terms defined below, these definitions should apply, unless a different definition is 5/61 given in the claims or elsewhere in this specification. All numerical values are defined in this document as being modified by the term about, whether explicitly indicated or not. The term about generally refers to a range of numbers that a person of ordinary skill in the art would consider equivalent to the value quoted to produce substantially the same properties, function, result, etc. A numerical range indicated by a low value and a high value is defined by covering all numbers included within the numerical range and all sub-ranges included within the numerical range. As an example, the range 10 to 15 includes, but is not limited to, 10, 10.1, 10.47, 11, 11.75 to 12.2, 12.5, 13 to 13.8, 14, 14.025 , and 15. The term nanoscale is defined as having at least one dimension less than 100 nanometers. The term porous substrate is defined as a pore structure that results in an equivalent surface area for the porous substrate in the range of 50 to 1,500 square meters per gram (m 2 / g) of the porous substrate, as measured by a technique such as Brunauer Emmett Teller (BET) technique or an analogous technique. In other words, the porosity of the substrate is specified by the equivalent surface area for the porous substrate. Information on the basics of deposition without electricity is available in the scientific and patent literature. The following documents are incorporated into this document in its entirety, for all purposes, for reference: M. Paunovic and M. Schlesinger Fundamentals of Electrochemical Deposition, Second Edition, John Wiley & Sons Incorporated, Pennington, New Jersey, 2006; and U.S. Patent No. 7,514,353. One aspect of the present invention encompasses a catalyst. Another aspect of the invention encompasses methods of creating catalysts. Another aspect of the invention covers 6/61 methods of using catalysts for applications such as, but not limited to, deoxygenation of compounds. Another aspect of the invention encompasses methods of creating carbon-based fuels such as, but not limited to, jet fuel, gasoline, and diesel fuel using raw materials derived from sources such as, but not limited to, plants and other renewable sources. CATALYSTS One aspect of the present invention is a catalyst such as to promote one or more chemical reactions. Catalysts according to one or more embodiments of the present invention comprise a porous substrate and one or more metals dispersed in and / or within the substrate, including surfaces that form the pores of the substrate. The metal is or can be produced to be catalytically active. According to an embodiment of the present invention, metal is a catalytically effective metallic coating deposited without electricity that has a nanoscale thickness. This means that, for one or more embodiments of the present invention, the metal is deposited electrochemically by deposition without electricity. According to an embodiment of the present invention, the porous substrate has an equivalent surface area of 50 to 1,500 m 2 / g. According to one or more other embodiments of the present invention, the porous substrate has an equivalent surface area in the range of 50 to 100 m 2 / g. According to one or more other embodiments of the present invention, the porous substrate has an equivalent surface area in the range of 100 to 300 m 2 / g. According to one or more other embodiments of the present invention, the porous substrate has an equivalent surface area in the range of 300 to 900 m 2 / g. According to one or more other embodiments of the present invention, the porous substrate has a surface area 7/61 equivalent in the 900 to 1,500 m 2 / g range. A variety of substrates can be used for one or more embodiments of the present invention. Examples of suitable substrates for embodiments of the present invention include, but are not limited to, activated carbon, carbon foam, alumina, metal foam, silica-alumina, silica, zeolites, titania, zirconia, magnesia, chromium, monoliths, or combinations of the same. Optionally, substrates for one or more embodiments of the present invention can be granular or pelletized. According to one or more embodiments of the present invention, the substrates have low levels of impurities that could interfere with the activity of the catalysts. For example, activated carbon substrates are preferably low in metal and low in ash for some embodiments of the present invention. The impurity levels of some activated carbons can be reduced by acid washing the substrate before preparing the catalyst. According to one or more embodiments of the present invention, the substrate has pores of 0.2 nm to 10 nm in width. According to another embodiment of the present invention, the substrate has pores from 0.2 nm to 10 nm wide and the catalytic metal is present in the pores. The catalyst is substantially stable during the preparation processes, during the activation processes, if applicable, and for long periods of use as a catalyst. For one or more embodiments of the present invention, the substrates are porous. According to one or more embodiments of the present invention, the catalyst comprises one or more metals such as, but not limited to, palladium (Pd), nickel (Ni), chromium (Cr), molybdenum (Mo), tungsten (W) , iron (Fe), ruthenium (Ru), osmium (Os), cobalt (Co), rhodium (Rh), iridium (Ir), platinum 8/61 (Pt), zinc (Zn), silver (Ag), copper (Cu), gold (Au), or mixtures thereof. Optionally, the catalyst can be configured as a single metal catalyst, as a bimetallic catalyst, or as a trimetallic catalyst. For embodiments of the present invention that have two or more metals, optionally the metals can be mixed to form an alloy, such as palladium and nickel in an alloy. Alternatively, the elements can be present as substantially pure elements. According to an embodiment of the present invention, the metal comprises palladium formed as nanoscale palladium deposited on substrate surfaces including, but not limited to, pore surfaces. Metals other than palladium can be used in catalytic materials for one or more embodiments of the present invention. Substrates for one or more embodiments of the present invention include activated carbon, such as coconut activated carbon. According to one or more embodiments of the present invention, the metal is deposited without electricity with the use of deposition processes without electricity, so that the metal is substantially free of deposition impurities without electrical current. In one or more embodiments of the present invention, metal deposition is deposition without electricity carried out with reducing agents such as, but not limited to, hydrazine, aldehydes, carboxylic acids with up to 6 carbon atoms, or mixtures thereof. According to an embodiment of the present invention, the deposition of metal is carried out with hydrazine added incrementally or continuously during deposition, so that the input of the reducing agent is distributed. According to an embodiment of the present invention, the loading of the metal is less than 15% by weight. According to another embodiment of the present invention, charging the 9/61 metal is less than 5% by weight. According to yet another embodiment of the present metal loading it is less than 1% by weight. According to one or more modalities of the present catalyst, it is catalytically active for deoxygenation of molecules such as oxygenated hydrocarbons. An exceptional and unexpected property of catalysts according to one or more embodiments of the present invention is that one or more of the catalysts are catalytically active for preferential deoxygenation and decarboxylation via hydrodesoxygenation decarbonylation. preferential deoxygenation by decarbonylation decarboxylation by hydrodeoxygenation is defined as greater than or equal to 60% oxygen is removed from the oxygenated hydrocarbon as carbon dioxide and carbon monoxide and less than or equal to 40% of oxygen is removed as water in all deoxygenation levels. According to another embodiment of the present invention, the catalyst is catalytically active so as to be capable of preferential deoxygenation by decarbonylation and decarboxylation through hydrodeoxygenation of alcohols, ethers, aldehydes, ketones, carboxylic acids, phenolics, esters, or mixtures thereof by decarbonylation and decarboxylation through hydrodeoxygenation. Catalysts according to one or more embodiments of the present invention are capable of preferential hydrogenation and deoxygenation of triglycerides by decarbonylation and decarboxylation through hydrodeoxygenation. According to another embodiment of the present invention, the metal comprises palladium, the substrate has pores of 0.2 nm to 10 nm in width with the metal present in it, and the catalyst is active for deoxygenation of triglycerides. According to another embodiment of the present invention, the 10/61 catalyst is catalytically active for preferential hydrogenation and deoxygenation of triglycerides by decarbonylation and decarboxylation through hydrodeoxygenation, so that the ratio of odd carbon number molecules to even carbon number molecules in the deoxygenated product is about 6: 1 . This reason is typically less than one for other deoxygenation technologies. Another embodiment of the present invention is a catalyst for deoxygenating bio-oils for fuel production. The catalyst comprises a substrate comprising activated carbon in granular form ranging in size from 0.5 mm to 3 mm. The substrate has pores from 0.2 nm to 10 nm wide. The catalyst comprises a catalytically effective nickel or palladium coating deposited without electricity having a nanoscale thickness arranged on the pore surfaces. The loading of palladium or nickel into the catalyst is less than about 2% by weight. Optionally, the metal comprises palladium grains about 15 nanometers wide. One or more embodiments of the present invention comprise a catalyst produced by one or more of the catalyst synthesis processes provided in the present description. More specifically, one or more embodiments of the present invention encompass a process product. One or more methods of preparing catalysts, according to embodiments of the present invention, produce catalysts that have unique properties such as, but not limited to, morphology, particle size, particle distribution, and chemical reactivity. Catalysts according to one or more embodiments of the present invention can be produced using the exemplary processes set out below. Catalysts 11/61 according to one or more modalities of the present invention are produced with the use of deposition processes without electricity that include one or more steps such as, but not limited to, improving bath stabilization, distributing the introduction of reducing agent , and raise the temperature of the galvanizing bath. According to one or more embodiments of the present invention, the distributed introduction of the reducing agent is coupled with the rise in temperature. One or more embodiments of the present invention is the first instance of electroless deposition of activated carbon nanoscale palladium coatings. The catalyst is stable and effective for reactions such as deoxygenation. Prior to one or more embodiments of the present invention, the present inventors were not aware of electroplating without palladium electricity as demonstrated on granular carbon substrates or other high porosity substrates. With the use of deposition without electricity according to one or more embodiments of the present invention, catalyst deoxygenation is produced with suitable distribution and particle size of palladium in the substrate pore structure to allow effective deoxygenation of bio-oils even in very low metal loading. These results are exceptional and unexpected. Catalysts produced according to one or more embodiments of the present invention have adequate palladium distribution within the pore structure of the substrate to allow high catalytic activities under low metal loading. The deposition of palladium on a substrate according to one or more embodiments of the present invention can be achieved in a shorter time compared to conventional deposition methods, such as incipient moisture impregnation. 12/61 Reference is now made to Figure 1, in which an enlarged image of a catalyst according to an embodiment of the present invention is shown. The surface is enlarged 100,000 X. The catalyst comprises an activated carbon substrate and a palladium coating deposited without electricity using an exemplary process presented below. A group of particles was vacuum encapsulated in epoxy and then sectioned using standard metallographic materials and procedures. The resulting sectioned samples were then examined, first by conventional scanning electron microscopy (SEM). The first examination suggested that there was extensive penetration into and deposition of palladium. The second SEM Field Emission exam showed that almost all internal surfaces were coated with palladium. Palladium was present on islands that sometimes coalesce, but are still often discontinuous. The islands vary widely in size, but appear to consist of grains about 15 nm across. The islands were also present on the deep inner surface of the particles. Catalysts according to one or more embodiments of the present invention have been tested. The catalyst had 0.5% to 5% palladium loading. The catalyst showed very little catalytic metal loading effect on deoxygenation activity (see Table 1). As shown in Figure 1-1, the catalyst has been shown to be very active for deoxygenation activity with an activation energy of around 54 kcal / g-mol for Cameline oil deoxygenation. Activation energy is typical of hydrocracking catalysts based on active zeolite. For one or more embodiments of the present invention, the combination of active metal-specific substrate appears to promote the decarbonylation of vegetable oils rather than hydroxydeoxygenation in removing oxygen from the molecule of 13/61 oil. This is highly advantageous in the process model for applications such as converting vegetable oils into biofuels, and is an exceptional and unexpected result. When oxygen is removed as carbon oxides, the product molecule will have one less carbon. For example, a C18 molecule will become C17. The Camelina oil, as shown in Figure 1-2, has molecules C16, C18, C20, C22, and C24, all in even numbers. Figure 1-3 is a gas chromatography (GC) trace showing the composition of deoxygenated product produced according to one or more embodiments of the present invention. As gas chromatography shows, odd-numbered carbon atoms dominate to the point that the ratio of odd and even numbered atoms is about 6 to 1. In contrast to the results obtained using the modalities of the present invention, the data reported by other processes show that the ratio of carbon samples from even to odd number is in the range of 0 to 1. METHOD FOR CREATING CATALYSTS Another aspect of the invention is a method for creating a catalyst. Reference is now made to Figure 2, in which a flow chart for the synthesis of catalysts according to one or more embodiments of the present invention is shown. According to one embodiment, the method comprises 12 providing a porous substrate and 14 providing a solution comprising a metal for deposition without electricity. The method further comprises 16 mixing the substrate with the solution and 18 controlling the temperature of the mixture of the substrate and the solution. In addition, the method comprises raising the temperature of the mixture while adding a reducing agent incrementally or continuously to cause deposition without controlled electricity of the metal as a catalytically active nanoscale coating of the substrate. Controlled deposition includes controlling the metal deposition rate and 14/61 control of the location of the deposited metal. According to one or more embodiments of the present invention, the deposition rate is controlled by the distributed addition of the reducing agent in combination with the controlled elevation of the temperature, in order to allow the mass transfer rate to allow the more complete distribution of the metal through the porous substrate for metal deposition. According to one or more embodiments of the present invention, the reducing agent is added continuously or incrementally over most or all of the metal-free deposition duration. According to an embodiment of the present invention, the method includes the use of a porous substrate that has a surface area equivalent to 50 to 1,500 m 2 / g. According to one or more other embodiments of the present invention, the porous substrate has an equivalent surface area in the range of 50 to 100 m 2 / g. According to one or more other embodiments of the present invention, the porous substrate has an equivalent surface area in the range of 100 to 300 m 2 / g. According to one or more other embodiments of the present invention, the porous substrate has an equivalent surface area in the range of 300 to 900 m 2 / g. According to one or more other embodiments of the present invention, the porous substrate has an equivalent surface area in the range of 900 to 1500 m 2 / g. A variety of substrates can be used for catalyst breeding methods according to one or more embodiments of the present invention. Examples of suitable substrates for embodiments of the present invention include, but are not limited to, activated carbon, carbon foam, alumina, metal foam, silica, silica-alumina, zeolites, titania, zirconia, magnesia, chromium, monoliths, or combinations thereof. Optionally, substrates for one or Further embodiments of the present invention can be granular or pelletized. According to one or more embodiments of the present invention, the method includes the use of a substrate that has pores of 0.2 nm to 10 nm in width. According to another embodiment of the present invention, the method includes depositing metal in substrate pores of 0.2 nm to 10 nm wide. According to one or more embodiments of the present invention, the method comprises deposition without electricity of one or more metals such as, but not limited to, palladium, nickel, chromium, molybdenum, tungsten, iron, ruthenium, osmium ,. cobalt, rhodium, iridium, platinum, zinc, silver, copper, gold, or mixtures thereof. Optionally, the catalyst can be produced as a single metal catalyst, as a bimetallic catalyst, or as a trimetallic catalyst. For embodiments of the present invention that have two or more metals, the metals can optionally be mixed to form an alloy, or the elements can be present as substantially pure elements. The deposition of two or more metals can be carried out as codeposition or as sequential deposition of metals. In accordance with an embodiment of the present invention, the method comprises deposition without electricity of palladium formed as nanoscale palladium deposited on substrate surfaces including, but not limited to, pore surfaces. According to one or more embodiments of the present invention, the metal is deposited without electricity with the use of deposition processes without electricity, so that the metal is substantially free of deposition impurities without electrical current. In one or more embodiments of the present invention, the method deposited the metal without electricity with the use of reducing agents such as, but not limited to, 16/61 hydrazine, aldehydes, carboxylic acids with up to 6 carbon atoms, or mixtures thereof. According to a modality of this invention, the method comprises the addition in hydrazine from mode increment or continuous during The deposition, of mode that the input of the agent reducer is distributed in big part or all the duration of deposition. According to an embodiment of the present invention, the method includes deposition without electricity to carry out a metal loading of less than 15% by weight. According to another embodiment of the present invention, the method includes deposition without electricity to carry out a metal loading of less than 5% by weight. According to yet another embodiment of the present invention, the method includes deposition without electricity to carry out a metal loading of less than 1% by weight. According to one or more embodiments of the present invention, the method further comprises sensitizing the substrate before deposition without electricity, but without, however, exposing the substrate to a sensitizing solution, exposing the substrate to a solution comprising a metal dissolved, and / or expose the substrate to a tin chloride solution. According to one or more embodiments of the present invention, the method further comprises activating the substrate prior to deposition without electricity, but without, however, exposing the substrate to an activation solution, exposing the substrate to a solution comprising a metal dissolved, and / or expose the substrate to a palladium chloride solution. According to one or more embodiments of the present invention, the method further comprises sensitizing the substrate before deposition without electricity by exposing the substrate to a solution of tin chloride followed by 17/61 substrate activation by exposing the substrate to a palladium chloride solution. According to one or more embodiments of the present invention, the method uses a substrate comprising activated carbon, carbon foam, alumina, metal foam, silicaalumina, silica, zeolites, titania, zirconia, magnesia, chromium, monoliths, or combinations of deposits, without electrical current, the metal comprising chromium, molybdenum, tungsten, iron, ruthenium, osmium, cobalt, rhodium, iridium, platinum, zinc, copper, gold, silver, or mixtures thereof with the use of a reducing agent that it comprises hydrazine, aldehydes, carboxylic acids having 1 to 6 carbon atoms, or mixtures thereof. According to one or more embodiments of the present invention, the method comprises providing a substrate comprising granular activated carbon, exposing the substrate to a solution of tin chloride in order to sensitize the activated carbon to deposition without electricity, and exposing the substrate to a palladium chloride solution in order to activate the activated carbon for deposition without electricity. The method also includes providing a palladium solution for deposition without electricity and mixing the substrate with the solution. The method further includes controlling the temperature of the mixture of the substrate and the solution, and raising the temperature while adding hydrazine incrementally or continuously, so as to cause palladium to be deposited without controlled electricity as a catalytically active coating of the activated carbon nanoscale. According to one or more embodiments of the present invention, the method comprises providing a substrate comprising granular activated carbon, exposing the substrate to a tin chloride solution in order to sensitize granular activated carbon for deposition without electricity, and exposing the 18/61 substrate to a palladium chloride solution in order to activate the granular activated carbon for deposition without electricity. The method also includes providing a nickel solution for deposition without electricity and mixing the substrate with the solution. The method further includes controlling the temperature of the mixture of the substrate and the solution, and raising the temperature while adding hydrazine incrementally or continuously, in order to cause the deposition without controlled electricity of the nickel as a catalytically active nanoscale coating of the activated carbon. Example 1: Preparation of Catalyst - Palladium on Activated Carbon Figure 3 shows a flow chart of the steps to prepare the catalysts of the present example. Steps 101 to 104 constitute substrate preparation and are described as follows: Step 101: 14 grams of coconut activated carbon (CAC) in granular form with size in the range of 1.6 mm to 0.8 mm were measured with the use analytical balance. Step 102: The CAC was placed on an aluminum weighing plate and placed in a vacuum oven. The oven temperature was raised and maintained at 125 ° C. The CAC was cooked for 12 hours. Step 103: Nitrogen gas was vented inside the vacuum oven to reach atmospheric pressure. The CAC sample was taken from the oven and immediately weighed on the analytical balance to obtain the actual CAC weight without hydration. Step 104: The CAC sample was placed in a glass beaker with a magnetic stirrer and mixed with 50 ml of 0.2 N HCl acid for 30 minutes. The CAC sample was filtered from the acidic solution. Steps 105 to 108 constitute substrate sensitization and activation and are described as follows: Step 105: In the sensitization glass beaker, 125 ml of 0.2N HCl was mixed with 0.125 g of SnC12 until the particles 19/61 are completely dissolved using the magnetic stirrer. In the activation glass beaker, 125 ml of 0.2 N HCl was mixed with 0.01125 g of PdC12 until the particles were completely dissolved using the magnetic stirrer. The CAC sample was placed in the sensitization beaker and mixed for 5 minutes. The CAC sample was filtered from the sensitization solution. Step 106: The CAC sample was mixed in 500 ml of deionized H 2 O (DI) for 10 minutes. The CAC sample was filtered from H 2 O DI. Step 107: The CAC sample was placed in the activation beaker and mixed for 5 minutes. The CAC sample was filtered from the activation solution. Step 108: The CAC sample was mixed in 500 ml of deionized H 2 O (DI) for 10 minutes. The CAC sample was filtered from H 2 O DI. Steps 109 to 112 constitute Pd plating on an activated carbon substrate and are described as follows: Step 109: In a glass beaker for plating solution, 70 ml of 28% NH 4 OH, 30 ml of H 2 DI, 0.54 g of PdCl 2 , and 4 g of Na 2 EDTA were mixed with a magnetic stirrer until the galvanizing solution was completely dissolved. The temperature of the Rotovap water bath (Rotary Evaporator) was raised to 40 ° C; 0.1 ml of 35% N 2 H 4 was added to the galvanizing solution and mixed. The galvanizing solution was combined with the CAC sample in a flask attached to the Rotovap water bath. The rotation was adjusted to homogeneously distribute the CAC in the galvanizing solution. After 10 minutes, a drop of N 2 H 4 was added to the plating solution and the temperature was raised to 45 ° C while the plating solution and CAC were continuously mixed. After 20 minutes, a drop of N 2 H 4 was added to the plating solution and the temperature was 20/61 increased to 50 ° C while the plating solution and CAC were continuously mixed. After 30 minutes, the rotovap rpm was reduced to zero, the water heating bath was deactivated and the galvanizing bottle was removed. The CAC with deposited Pd was filtered from the galvanizing solution. Step 110: The CAC sample was mixed in 500 ml of deionized H 2 O (Dl) for 30 minutes. The deposited Pd CAC sample was filtered from H 2 O Dl. The deposited Pd CAC sample was mixed in 500 ml of deionized H 2 O Dl for 30 minutes. The deposited Pd CAC sample was filtered from H 2 O Dl. Step 111: The deposited Pd CAC was placed in an aluminum weighing plate and placed in a vacuum oven. The vacuum pump was activated and a 63.5 cm (25 inch) Hg vacuum was maintained in the vacuum oven. The oven temperature was raised and maintained at 125 ° C. The deposited Pd CAC was baked for 12 hours. Step 112: Nitrogen gas was vented to the vacuum oven until atmospheric pressure was reached. The deposited Pd CAC sample was taken from the oven and immediately weighed on the analytical balance to obtain the actual Pd CAC weight deposited without hydration. The weight difference between step 112 and step 103 represents the amount of Pd deposited on 14 grams of coconut activated carbon. Methods of creating catalysts according to one or more embodiments of the present invention may comprise the use of other granular, pelleted, or structured substrates derived from ceramics or metal. Methods according to one or more embodiments of the present invention can comprise the use of a structured substrate such as monolith or metal foam for various applications. Example 2: Preparation of Catalyst - Palladium on Alumina Extruded gamma alumina substrate material was 21/61 crushed with the use of a ceramic mortar and pestle and sieved to obtain particles in the size range from 1.6 mm to 0.8 mm. An analytical balance was used to measure 14 grams of this gamma alumina substrate. Gamma alumina was baked in a vacuum oven for 12 hours and the dry weight of the gamma alumina substrate was obtained from the analytical balance. Gamma alumina was hydrated when exposed to steam for 2 hours to minimize decrepitation of gamma alumina prior to the sensitization step. In the sensitizing glass beaker, 125 ml of 0.2N HCl was mixed with 0.125 g of SnC12 until the particles were completely dissolved using a magnetic stirrer. In the sensitization glass beaker, 125 ml of 0.2N HCl was mixed with 0.01125 g of PdC12 until the particles were completely dissolved using a magnetic stirrer. The sample gamma alumina was placed in a beaker awareness and mixed per 5 minutes. The sample in gamma alumina was filtered The from solution in awareness. The sample of gamma alumina was mixed in 500 ml of H2O Dl for 2 minutes. The gamma alumina sample was filtered from H 2 O Dl. The gamma alumina sample was placed in an activation beaker and mixed for 5 minutes. The gamma alumina sample was filtered from the activation solution. The gamma alumina sample was mixed in 500 ml of deionized H 2 O Dl for 2 minutes. The gamma alumina sample was filtered from H 2 O Dl. Gamma alumina was placed back in the sensitization beaker and mixed for 5 minutes, filtered, and rinsed in H 2 O Dl for 2 minutes and filtered. Gamma alumina was placed back in the sensitization beaker and mixed for 5 minutes, filtered, and rinsed in H 2 O Dl for 2 minutes and extracted by filtration. In a glass beaker for galvanizing solution, 22/61 ml of 28% NH 4 OH, 30 ml of H 2 O Dl, 0.54 g of PdCl 2 , and 4 g of Na 2 EDTA were mixed until the galvanizing solution was completely dissolved. The water bath temperature of Rotovap Buchi was raised to 40 ° C. 0.1 ml of 35% N 2 H 4 was added to the galvanizing solution and mixed well. The galvanizing solution and gamma alumina sample was combined in a flask and fixed to the water bath in the Rotovap Buchi. The rotation was adjusted to homogeneously distribute the gamma alumina in the galvanizing solution. After 10 minutes, a drop of N 2 H 4 was added to the plating solution and the temperature was raised to 45 ° C while the plating solution and gamma alumina were continuously mixed. After 5 minutes, the rotovap rpm was reduced to zero, the water heating bath was deactivated, and the galvanizing bottle was removed. The deposited Pd gamma alumina was filtered from the galvanizing solution. The sample of deposited Pd gamma alumina was mixed in 500 ml of deionized H 2 O (Di) for 10 minutes. The deposited Pd gamma alumina sample was filtered from H 2 O DI. The deposited gamma Pd alumina was placed on an aluminum weighing plate and placed in a vacuum oven. The vacuum pump was activated and a 63.5 cm (25 inch) Hg vacuum was maintained in the vacuum oven. The oven temperature was raised and maintained at 125 ° C. The deposited gamma Pd alumina was baked for 12 hours. Nitrogen gas was vented to the vacuum oven to reach atmospheric pressure. The sample of deposited Pd gamma alumina was taken from the oven and immediately weighed on the analytical balance to obtain the real weight of the deposited Pd gamma alumina without hydration. The difference in weight before and after Pd plating represents the amount of Pd deposited in 14 grams of gamma alumina. Example 3: Preparation of Catalyst - Nickel in 23/61 Activated Carbon Twenty-two grams of coconut activated carbon in granular form with size ranging from 1.6 mm to 0.8 mm were measured using an analytical balance. The CAC was placed on an aluminum weighing plate and placed in a vacuum oven. The vacuum pump was activated and a 63.5 cm (25 inch) Hg vacuum was maintained in the vacuum oven. The oven temperature was raised and maintained at 125 ° C. The CAC was cooked for 12 hours. Nitrogen gas was vented to the vacuum oven to reach atmospheric pressure. The CAC sample was taken from the oven and immediately weighed on the analytical balance to obtain the actual CAC weight without hydration. The CAC sample was placed in a glass beaker with a magnetic stirrer and mixed with 60 ml of 0.2 N HCl acid for 5 minutes. The CAC sample was filtered from the acidic solution. The above rinse was repeated 4 more times, each time with new 60 ml of 0.2 N HCl. In the sensitizing glass beaker, 185 ml of 0.2N HCl was mixed with 0.375 g of SnCl 2 until the particles were completely dissolved. In the activation glass beaker, 185 ml of 0.2N HCl was mixed with 0.0341 g of PdCl 2 until the particles were completely dissolved using a magnetic stirrer. The CAC sample was placed in a sensitization beaker and mixed for 5 minutes. The CAC sample was filtered from the sensitization solution. The CAC sample was mixed in 500 ml of deionized H 2 O (Di) for 5 minutes. The CAC sample was filtered from H 2 O DI. The CAC sample was placed in an activation beaker and mixed for 5 minutes. The CAC sample was filtered from the activation solution. The CAC sample was mixed in 500 ml of deionized H 2 O (DI) for 10 minutes. The CAC sample was filtered from H 2 0 DI. 24/61 In a glass beaker for plating solution, 53 ml of 28% NH 4 OH, 90 ml of H 2 O DI, 0.8102 g of NiCl 2 , and 6 g of Na 2 EDTA were mixed until the plating solution be completely dissolved. The temperature of a water bath in a 1,000 ml beaker was raised to 60 ° C using an IKA hot plate. 0.1 ml of 35% N 2 H 4 was added to the galvanizing solution and mixed well. The CAC sample was placed in a 250 ml beaker and the 250 ml beaker was suspended in the IKA water bath controlled using rubber spacers on top of the water bath beaker. The mixture for the water bath was achieved with the magnetic stirrer. The mixture for the galvanizing beaker was achieved with an IKA suspended stirrer equipped with a rod and propellers lined with Teflon (a marine propeller and a turbine propeller). The galvanizing beaker also contains 3 Teflon baffles fixed together and oriented 120 degrees apart. The galvanizing solution was poured into a 250 ml beaker containing the CAC sample. The rpm of the IKA mixer was adjusted in the range of 200 to 400 in order to homogeneously distribute the CAC in the galvanizing solution. After 10 minutes, a drop of N 2 H 4 was added to the galvanizing solution and the temperature was raised to 65 ° C, while the galvanizing solution and CAC were continuously mixed. After 13 minutes, a drop of N 2 H 4 was added to the plating solution and the temperature was raised to 70 ° C, while the plating solution and CAC were continuously mixed. After 10 minutes, a drop of N 2 H 4 was added to the galvanizing solution and the temperature was increased to 75 ° C, while the galvanizing solution and CAC were continuously mixed. After 14 minutes, a drop of N 2 H 4 was added to the 25/61 galvanizing and the temperature was increased to 79 ° C, while the galvanizing solution and CAC were continuously mixed. After 5 minutes, a drop of N 2 H 4 was added to the galvanizing solution and the temperature was increased to 79.5 ° C, while the galvanizing solution and CAC were continuously mixed. After 5 minutes, a drop of N 2 H 4 was added to the galvanizing solution and the temperature was increased to 80 ° C while the galvanizing solution and CAC were continuously mixed. After 5 minutes, a drop of N 2 H 4 was added to the galvanizing solution and the temperature was increased to 82 ° C while the galvanizing solution and CAC were continuously mixed. After 5 minutes, the rpm was reduced to zero, the water heating bath was deactivated, and the galvanizing bottle was removed. The deposited Ni CAC was filtered from the galvanizing solution. The CAC sample was mixed in 100 ml of deionized H 2 O (Dl) 'for 5 minutes. The deposited Ni CAC sample was filtered from H 2 O Dl. A 100 ml water rinse was repeated as many times as necessary until the pH of the rinse solution reached 7. The deposited Ni CAC sample was filtered from H 2 0 Dl. Deposited Ni CAC was placed on an aluminum weighing plate and placed in a vacuum oven. The vacuum pump was activated and a 63.5 cm (25 inch) Hg vacuum was maintained in the vacuum oven. The oven temperature was raised and maintained at 125 ° C. The deposited Ni CAC was baked for 12 hours. Nitrogen gas was vented to the vacuum oven to reach atmospheric pressure. The deposited Ni CAC sample was taken from the oven and immediately weighed on the analytical balance to obtain the actual Ni CAC weight deposited without hydration. The difference in weight before and after 26/61 galvanizing step represents the amount of Ni deposited in 22 grams of coconut activated carbon. DEOXYGENATION METHODS Another aspect of the invention is a method of deoxygenation. Deoxygenation can occur through three mechanisms, which include hydroxydeoxygenation, where oxygen is most often removed as H 2 0, decarbonylation, where oxygen is most often removed as CO, and decarboxylation, where oxygen is mostly sometimes removed as CO 2 . Conventional hydroprocessing methods and catalyst used in deoxygenation will result in high hydrogen consumption and high water production. One or more embodiments of the present invention comprise with the use of one or more catalysts, as described above. The selected catalyst is suitable for applications such as, but not limited to, hydrogenation, and deoxygenation of oxygenated hydrocarbons as components of bio-oils. According to one or more embodiments of the present invention, catalysts have properties, so that low or minimal formation of undesirable by-products occurs. Optionally, one or more embodiments of the present invention comprise the use of granular catalysts with low metal loading; the catalysts are effective for reactions like, but without limit yourself The, hydrogenation and deoxygenation of organic materials like, but without limiting yourself to, bio-oils. An or more modalities gives present invention include the use on one reactor with O granular catalyst on a compressed base, the reactor and the compressed base are arranged to operate in continuous multiphase flow mode. According to an embodiment of the present invention for deoxygenating hydrocarbons, the method comprises 27/61 provide a catalyst comprising a porous substrate and a catalytically effective nanoscale metallic coating deposited without electricity on the substrate. The method also includes putting the catalyst in contact with the oxygenated hydrocarbons and hydrogen in order to perform hydrogenation and deoxygenation, with deoxygenation being carried out preferably by decarbonylation and decarboxylation through hydrodeoxygenation. According to an embodiment of the present invention, the method has a decarbonylation to decarboxylation ratio of about 6: 1. In other words, the method includes generating 6 times more carbon monoxide than carbon dioxide for deoxygenation. These results are extraordinary compared to the results of other processes. Others reported that primary oxygen removal is by producing carbon dioxide and / or water. Unlike the embodiments of the present invention, other processes appear to have low carbon monoxide production. The results of the present invention are even more extraordinary since the high levels of carbon monoxide production occur even with the use of palladium as the metal for the catalyst. Palladium is well known to those of ordinary skill in the art as being particularly susceptible to carbon monoxide poisoning. Experimental results obtained using the modalities of the present invention show that the palladium catalyst maintained its catalytic activity even in the presence of carbon monoxide at partial pressures as high as 0.1 megapascals for tested periods of operation as long as 100 hours. Deoxygenation processes according to methods of the present invention may include the use of a variety of substrates for the catalyst. Examples of substrates Suitable for embodiments of the present invention include, but are not limited to, activated carbon, carbon foam, alumina, metal foam, silica, silica-alumina, zeolites, titania, zirconia, magnesia, chromium, monoliths, or combinations of the same. Optionally, substrates for one or more embodiments of the present invention can be granular or pelletized. According to one or more embodiments of the present invention, the deoxygenation process uses a substrate that has pores of 0.2 nm to 10 nm in width. According to another embodiment of the present invention, the substrate has pores of 0.2 nm to 10 nm in width and the metal is present in the pores. According to one or more embodiments of the present invention, the catalyst used for the deoxygenation process comprises one or more metals such as, but not limited to, palladium, nickel, chromium, molybdenum, tungsten, iron, ruthenium, osmium, cobalt, rhodium, iridium, platinum, zinc, silver, copper, gold, or mixtures thereof. Optionally, the catalyst can be configured as a single metal catalyst, as a bimetallic catalyst, or as a trimetallic catalyst. For embodiments of the present invention that have two or more metals, the metals can optionally be mixed to form an alloy, or the elements can be present as substantially pure elements. According to an embodiment of the present invention, the metal comprises palladium formed as nanoscale palladium deposited on substrate surfaces including, but not limited to, pore surfaces. Metals other than palladium can be used in catalytic materials for one or more embodiments of the present invention. Substrates for one or more embodiments of the present invention include activated carbon, such as coconut activated carbon. 29/61 According to one or more embodiments of the present invention, the metal is deposited without electricity with the use of deposition processes without electricity, so that the metal is substantially free of deposition impurities without electrical current. In one or more embodiments of the present invention, metal deposition is deposition without electricity carried out with reducing agents such as, but not limited to, hydrazine, aldehydes, carboxylic acids with up to 6 carbon atoms, or mixtures thereof. According to an embodiment of the present invention, metal deposition is carried out with hydrazine added incrementally or continuously during deposition, so that the reducing agent input is distributed. According to an embodiment of the present invention, the loading of the metal is less than 15% by weight. According to another embodiment of the present invention, the loading of the metal is less than 5% by weight. According to yet another embodiment of the present invention, the loading of the metal is less than 1% by weight. According to one or more embodiments of the present invention, the catalyst is catalytically active for deoxygenating molecules such as oxygenated hydrocarbons. An exceptional and unexpected property of the catalyst according to one or more embodiments of the present invention is that the catalyst is catalytically active for preferential deoxygenation by decarbonylation and decarboxylation by hydrodeoxygenation. Preferential deoxygenation by decarbonylation and decarboxylation through hydrodeoxygenation is defined as greater than or equal to 60% oxygen is removed from the oxygenated hydrocarbon as carbon dioxide and carbon monoxide and less than or equal to 40% of oxygen is removed as water. According to another modality of this 30/61 invention, the catalyst is catalytically active so as to be capable of preferential deoxygenation by decarbonylation and decarboxylation through hydrodeoxygenation of alcohols, ethers, aldehydes, ketones, carboxylic, phenolic acids, esters, or mixtures thereof by decarbonylation and decarboxylation through hydrodesoxygenation. Catalysts according to one or more embodiments of the present invention are capable of preferential hydrogenation and deoxygenation of triglycerides by decarbonylation and decarboxylation through hydrodeoxygenation. According to another embodiment of the present invention, the activation energy for deoxygenation is about 54 kcal / g-mol for Camelina oil. According to another embodiment of the present invention, the metal comprises palladium, the substrate has pores of 0.2 nm to 10 nm wide with the metal present in it, and the catalyst is active for deoxygenation of triglycerides. According to another embodiment of the present invention, the catalyst is catalytically active for preferential hydrogenation and deoxygenation of triglycerides by decarbonylation and decarboxylation through hydrodeoxygenation, so that the ratio of odd carbon number molecules to even carbon number molecules in the product deoxygenated is about 6: 1. Another embodiment of the present invention is a catalyst for deoxygenating bio-oils for fuel production. The catalyst comprises a substrate comprising activated carbon in granular form ranging in size from 0.5 mm to 3 mm. The substrate has pores of 0.2 nm to 10 nm wide. The catalyst comprises a catalytically effective nickel or palladium coating deposited without electricity that has a nanoscale thickness arranged on the pore surfaces. Loading palladium or nickel 31/61 for the catalyst is less than about 2% by weight. Optionally, the metal comprises palladium grains about 15 nanometers wide. According to another embodiment of the present invention, the metal coating of the catalyst is palladium and the deoxygenation method is performed with the catalyst exposed to partial pressure of carbon monoxide up to about 0.1 megapascals. As an option for one or more embodiments of the present invention, the oxygenated hydrocarbons 10 comprise triglycerides, the substrate is activated carbon, and the metal comprises palladium. The method additionally includes placing the catalyst in contact with the oxygenated hydrocarbons and hydrogen, in order to preferentially perform deoxygenation by decarbonylation and decarboxylation by hydrodeoxygenation. Deoxygenation is performed at temperatures in the range of 300 ° C to 400 ° C and pressures in the range of 1.5 megapascals to 15 megapascals. A deoxygenation method according to another embodiment of the present invention, hydrocarbons comprise triglycerides, the substrate comprises activated carbon, carbon foam, alumina, metal foam, silicaalumina, silica, zeolites, titania, zirconia, magnesia, chromium, monoliths, or combinations thereof. The metal is selected from the group consisting of chromium, molybdenum, tungsten, iron, ruthenium, osmium, cobalt, nickel, rhodium, iridium, palladium, platinum, zinc, gold, silver, copper, or mixtures thereof, and put the catalyst in contact with oxygenated hydrocarbons and hydrogen in order to • preferably perform deoxygenation by decarbonylation, and decarboxylation by hydrodeoxygenation is carried out at temperatures in the range of 300 ° C to 400 ° C and pressures in the range of 1, 5 megapascals to 15 32/61 megapascals. Optionally, the catalyst has a metal loading of less than or equal to about 2% with deoxygenation efficiency greater than about 90%, or the catalyst has a metal loading of less than or equal to about 1% with efficiency deoxygenation greater than about 90%. For one or more embodiments of the present invention, the method includes the use of an hourly hourly space velocity of 0.2 to 2.5. THE velocity j space ceso hourly in hour is calculated as the flow rate in mass of supply divided by mass of the catalyst.Example 4 : Deoxygenation With the use of Palladium in Activated Carbon Using methods according to one or more embodiments of the present invention, catalysts were produced with different Pd metal fillers on coconut activated carbon. The catalysts were placed in a compressed base reactor with the same operating parameters that process Camelina oil in continuous multiphase flow mode. The results that were obtained were exceptional and unexpected in relation to the low metal loading and high percentage of deoxygenation. Table 1 shows that high deoxygenation can be achieved with low metal loading: TABLE 1 Palladium loading weight) (% inDeoxygenation (%) 0.5 86 1.2 91 3.0 87 5.2 84 In another experiment with the use of catalysts according to one or more embodiments of the present invention, catalysts with a 5% weight average metal loading 33/61 were produced and loaded in a compressed base reactor to process Camelina oil in continuous operation for 100 hours of operation. Prolonged deoxygenation activity was observed over the duration of continuous operation. palladium catalyst prepared according to one or more embodiments of the present invention can have significant cost advantages that can be acquired with the use of lower metal loading to perform deoxygenation of bio-oils. Catalysts according to one or more embodiments of the present invention, when used to perform the deoxygenation reaction, did not show any obstruction or coking problem for an entire 500 hour continuous run in a compressed base reactor. Catalysts according to one or more embodiments of the present invention achieve deoxygenation primarily through decarbonylation chemistry, as evidenced by the CO content in the reactor's gas outlet composition. Experimental work was carried out with the use of a fixed flow reactor of continuous flow according to one or more modalities of the present invention. The reactor was a reactor with an internal diameter of 0.77 cm (0.305 inches), 25.4 cm (10 inches) in length with pre-heating and post-heating zones. The reactor volume was 12 cc with a catalyst weight of 6.13 g. Experiments were performed and results were obtained for a range of conditions. Some of the varied parameters were temperature, pressure, and space velocity. The ranges covered and results were: Temperature range 300 to 400 ° C Pressure 1.72 to 6.89 mPa (250 to 1,000 psig) Hourly weight space speed (WHSV) 0.5 to 2.5 Conversion 20 to 95% 34/61 Deoxygenation methods according to one or more embodiments of the present invention comprise the use of finely dispersed material palladium catalyst on activated carbon, which can be prepared as described above. According to one or more modalities, the method uses the fine pore structure of the activated carbon. The method uses relatively higher temperatures to effectively hydrogenate and divide the supply molecules so that the fragments have easy access to the fine pore structure of the substrate. The inventors have also used one or more modalities of the present invention under test for 100 hours of continuous flow operation for deoxygenation of Camelina oil, and have shown that prolonged catalyst activity was achieved in smooth reactor operation with no evidence of obstruction or coking. In contrast, other deoxygenation technologies have been reported to produce high levels of aromatics and unsaturated, resulting in coking and obstruction of the deoxygenation reactor in continuous flow operation mode. The method of preparing the catalysts, like the method described above, allows the penetration of nanocrystalline palladium into micropores of 0.4 to 2 nanometers. The small pore volume offers the largest surface area for reactions. Methods according to one or more embodiments of the present invention have shown that a high concentration of palladium is not required in the catalysts, which is a result that is unexpected and exceptional and may be the result of having deposited the palladium perhaps substantially as a nanoscale coating. . As stated above, catalysts that have 0.5% to 5% palladium loading have been tested. The catalyst showed very little effect of catalytic metal loading on deoxygenation activity (see 35/61 Table 1). For one or more embodiments of the present invention, the active metal-specific substrate combination appears to promote the decarbonylation of oils, such as vegetable oils, preferably hydroxydeoxygenation in removing oxygen from the oil molecule. This is highly advantageous in the process model for applications such as converting vegetable oils into biofuels, and is an exceptional and unexpected result. When oxygen is removed as carbon oxides, the product molecule will have one less carbon. For example, the C18 molecule will become C17. The supply molecule, as shown in Figure 1-2, has molecules C16, C18, C20, C22, and C24, all in even numbers. Figure 1-3 is a gas chromatography trace showing the deoxygenated product composition produced according to one or more embodiments of the present invention. As gas chromatography shows, odd-numbered carbon atoms dominate to the point that the ratio of odd and even numbered atoms is about 6 to 1. In contrast to the results obtained using the modalities of the present invention, data reported for other processes show that the ratio of carbon samples from even to odd number is in the range of 0 to 1. As hydroxydeoxygenation is suppressed, hydrogen consumption will be minimized and less water will be produced in the reactor. High hydrogen consumption negatively affects the operating cost demand on hydrogen in most refineries lacks the plant and also puts an existing refinery in new. Adequate hydrogen supply and the construction of a new hydrogen plant for repair are usually cost prohibitive. In such situations, a process that does not consume large amounts of hydrogen offers many economic and logistical advantages to a refiner who plans to produce biofuels with existing refinery infrastructure. 36/61 Another disadvantage of a process that consumes considerable amounts of hydrogen is the reactor temperature control. Hydrogen, when consumed, releases a significant amount of heat and this needs to be effectively removed for the plant's safety and proper operation. One or more embodiments of the present invention results in about 60 to 65% of oxygen removed as carbon oxides with only about one third about to produce water. This is an unexpected and extraordinary result for one or more embodiments of the present invention. One or more embodiments of the present invention comprises the use of a space velocity reactor which may be greater than in a typical hydroprocessing unit commonly used in oil refining. Processes according to one or more embodiments of the present invention use modest temperatures and modest hydrogen pressure. According to an embodiment of the present invention, the process includes the use of a conventional downward-flow fixed-base reactor. The option of using a fixed base reactor makes the process easy to carry out on larger scales. Preferred embodiments of the present invention do not use a solvent during deoxygenation processes. Example 5: Deoxygenation Using Palladium in Alumina Catalyst Refined Camelina oil was the raw material used in a deoxygenation reactor according to one or more modalities of the present invention. Deoxygenation experiments were carried out in a multi-phase compressed base reactor with continuous downward flow. In this example, 6.1 grams of 0.5 wt% Pd in a gamma alumina catalyst according to one or more 37/61 the present invention was loaded into a stainless steel reactor. The reactor was 0.775 cm (0.305 inch) in diameter and 25.4 cm (10 inches) long with pre-heating and post-heating zones. The reactor volume was 12 cc. The heat for the reactor was supplied by a temperature controlled furnace with 3 zones with heat equalization blocks. The supply of Camelina oil was pumped at a rate of 0.1 cc / min to the reactor. Liquid and gaseous products that left the reactor were collected in a separator. Back pressure regulators kept the system operating at 3.45 mPa (500 psig). The Pd in the gamma alumina catalyst was reduced under hydrogen at 250 ° C for 2 hours to activate the catalyst. The reactor temperature was raised from 250 ° C to 350 ° C within 60 minutes. The supply of liquid Camelina oil was then pumped into the reactor at a rate of 0.1 cc / min. The rate of hydrogen gas supply to the reactor was 70 cc / min. The reactor temperature was maintained at 350 ° C and the reactor was run for 10 hours. The gas product of the reactor was analyzed using gas chromatography. The gaseous product of the main reagent observed in addition to H 2 was CO. The paraffinic wax product was separated from the water by gravity. The elemental analysis was performed on the paraffinic wax product to determine the oxygen content of the deoxygenated product. Elemental oxygen analysis showed that approximately 96% oxygen had been removed from the original Camelina oil supply. Example 6 - Deoxygenation Using Nickel in Activated Carbon Catalyst Refined Camelina oil was the raw material used in a micro deoxygenation unit according to one or more modalities of the present invention. Deoxygenation experiments were performed in a base reactor 38/61 compressed multiphase continuous downflow. In this example, 6.1 grams of 0.9 wt% Ni on activated carbon catalyst according to one or more embodiments of the present invention was loaded into a stainless steel reactor. The reactor was 0.775 cm (0.305 inch) in diameter and 25.4 cm (10 inches) long with pre-heating and post-heating zones. The reactor volume was 12 cc. Heat for the reactor was supplied by a temperature controlled furnace in three zones with heat equalization blocks. Liquid and gaseous products leaving the reactor were collected in a separator. Back pressure regulators kept the system pressure in operation at 6.89 mPa (1,000 psig). The Ni in the activated carbon catalyst was reduced in hydrogen at 250 ° C for 2 hours to activate the catalyst. The Ni catalyst was used in the form of uncoated metal rather than as a form of sulfite that is typical for the hydroprocessing industry. The reactor temperature was raised from 250 ° C to 360 ° C within 60 minutes. The supply of liquid Camelina oil was then pumped into the reactor at a rate of 0.1 cc / min. The rate of hydrogen gas supply to the reactor was 168 cc / min. The reactor temperature was maintained at 360 ° C and the reactor was run for 13 hours. The gas product of the reactor was analyzed using gas chromatography. The main reagent gas product observed in addition to H2 was CO. The paraffin wax product was separated from the water by gravity. Elementary analysis was performed on the paraffin wax product to determine the oxygen content of the deoxygenated product. Elemental oxygen analysis showed that approximately 87% oxygen had been removed from the original Camelina oil supply. Catalysts according to one or more embodiments of the present invention promote decarbonylation and 39/61 decarboxylation instead of hydroxydeoxygenation. The process consumes considerably less hydrogen for one or more possible benefits such as, but not limited to, favorable process savings, use of existing refinery infrastructure to produce synthetic biofuels, and an easier reactor model. In addition, one or more processes according to the modalities of the present invention comprise a high yield of distillable fuels with low or minimal production of unwanted by-products. Deoxygenation reactors, according to the modalities of the present invention, comprise one or more of compressed base configuration with multiphase downflow, continuous flow operation capability, and the absence of extracts or process-derived or foreign solvents. FUEL PRODUCTION METHODS A part of the process of producing synthetic biofuels from bio sources is deoxygenation. Deoxygenation can occur by three mechanisms, which include hydroxydeoxygenation, where oxygen is most often removed as H 2 O, decarbonylation, where oxygen is most often removed as CO, and decarboxylation, where oxygen is most times removed as CO 2 . In other words, the processing of bio-oils that. have a different chemistry than conventional petroleum oils have one or more problems that are overcome by one or more embodiments of the present invention. Although embodiments of the present invention can effectively convert any type of bio-oils and / or other suitable raw materials, one or more of the following examples provide data for deoxygenation of inedible bio-oils. Examples of non-edible bio-oils include Tungue, Jojoba, Jatropha, Camelina sativa, Tall, Crambe, Castor, Industrial rape seed, Cuphea, Lesquerella, and 40/61 others. Advances in genetic engineering offer the possibilities for bio-oils to be extracted from oilseed crops that are hardy, drought-tolerant, pest-resistant, and can be grown on marginal soil to provide high oil content. Alternatively, bio-oils can also be extracted from algae and other genetically modified biological systems. The estimated bio oil content of these sources can range from 25% by weight to 50% by weight. Reference is now made to Figure 4 in which a schematic diagram of a system 300 is shown for the production of fuels such as gasoline, diesel fuel, and jet fuel from sources such as, but not limited to, renewable raw materials. The system 300 comprises a deoxygenation stage 310 which comprises at least one deoxygenation reactor chamber 315 and a catalyst 320 contained in the deoxygenation reactor chamber 315. The catalyst 320 comprises a porous substrate and a metallic coating deposited without electricity that has a nanoscale thickness. The catalyst 320 according to one or more embodiments of the present invention is essentially the same as the catalysts described earlier in the present description. As an option for one or more embodiments of the present invention, at least one deoxygenation reactor chamber 315 and catalyst 320 are configured as a compressed base reactor to operate in continuous multiphase flow mode with hydrogen as a reagent. According to an embodiment of the present invention, the porous catalyst substrate 320 has a surface area equivalent to 50 to 1,500 m 2 / g. According to one or more other embodiments of the present invention, the porous catalyst substrate 320 has a surface area 41/61 equivalent in the range of 50 to 100 m 2 / g. According to one or more other embodiments of the present invention, the porous catalyst substrate 320 has an equivalent surface area in the range of 100 to 300 m 2 / g. According to one or more other embodiments of the present invention, the porous catalyst substrate 320 has an equivalent surface area in the range of 300 to 900 m 2 / g. According to one or more other embodiments of the present invention, the porous catalyst substrate 320 has an equivalent surface area in the range of 900 to 1,500 m 2 / g. A variety of substrates can be used for catalyst 320. Examples of suitable substrates for catalyst 320 include, but are not limited to, activated carbon, carbon foam, alumina, metal foam, silica, silica-alumina, zeolites, titania, zirconia, magnesia, chromium, monoliths, or combinations thereof. Optionally, catalyst substrates 320 can be granular or pelletized. According to one or more embodiments of the present invention, the catalyst substrate 320 has pores of 0.2 nm to 10 nm in width. According to another embodiment of the present invention, the catalyst substrate 320 has pores of 0.2 nm to 10 nm in width and the metal is present in the pores. According to one or more embodiments of the present invention, catalyst 320 comprises one or more metals such as, but not limited to, palladium (Pd), nickel (Ni), chromium (Cr), molybdenum (Mo), tungsten (W ), iron (Fe), ruthenium (Ru), osmium (Os), cobalt (Co), rhodium (Rh), iridium (Ir), platinum (Pt), zinc (Zn), silver (Ag), copper (Cu ), gold (Au), or mixtures thereof. Optionally, catalyst 320 can be configured as a single metal catalyst, as a bimetallic catalyst, or as a trimetallic catalyst. 42/61 For embodiments of the present invention in which there are two or more metals, the metals can be optionally mixed so that they form an alloy, such as palladium and nickel in an alloy. Alternatively, the elements can be present as substantially pure elements. According to an embodiment of the present invention, the metal comprises palladium formed as nanoscale palladium deposited on substrate surfaces including, but not limited to, pore surfaces. Metals other than palladium can be used in catalytic materials for one or more embodiments of the present invention. Substrates for one or more embodiments of the present invention include activated carbon, such as coconut activated carbon. According to one or more embodiments of the present invention, the metal is deposited without electricity with the use of deposition processes without electricity, so that the metal is substantially free of deposition impurities without electrical current. In one or more embodiments of the present invention, metal deposition is deposition without electricity carried out with reducing agents such as, but not limited to, hydrazine, aldehydes, carboxylic acids with up to 6 carbon atoms, or mixtures thereof. According to an embodiment of the present invention, metal deposition is carried out with hydrazine added incrementally or continuously during deposition, so that the reducing agent input is distributed. According to an embodiment of the present invention, the loading of the metal is less than 15% by weight. According to another embodiment of the present invention, the loading of the metal is less than 5% by weight. According to yet another embodiment of the present invention, the loading of the metal is less than 1% by weight. According to one or more modalities of this 43/61 invention, catalyst 320 is catalytically active for deoxygenation of molecules such as oxygenated hydrocarbons. An exceptional and unexpected property of catalyst 320 according to one or more embodiments of the present invention is that the catalyst is catalytically active for preferential deoxygenation by decarbonylation and decarboxylation by hydrodeoxygenation. Preferential deoxygenation by decarbonylation and decarboxylation through hydrodeoxygenation is defined as greater than or equal to 60% oxygen is removed from the oxygenated hydrocarbon as carbon dioxide and carbon monoxide and less than or equal to 40% of oxygen is removed as water. According to another embodiment of the present invention, catalyst 320 is catalytically active so as to be capable of preferential deoxygenation by decarbonylation and decarboxylation through hydrodeoxygenation of alcohols, ethers, aldehydes, ketones, carboxylic acids, phenolics, esters, or mixtures thereof by decarbonylation and decarboxylation through hydrodeoxygenation. The catalyst 320 according to one or more embodiments of the present invention is capable of preferential hydrogenation and deoxygenation of triglycerides by decarbonylation and decarboxylation through hydrodeoxygenation. According to another embodiment of the present invention, the activation energy for deoxygenation is about 54 kcal / g-mol for Camelina oil, when using 320 catalysts. According to another embodiment of the present invention, the catalyst metal 320 comprises palladium, the substrate has pores from 0.2 nm to 10 nm wide with the metal present in it, and the catalyst is active for deoxygenation of triglycerides. According to another embodiment of the present invention, catalyst 320 is catalytically active for preferential hydrogenation and deoxygenation of triglycerides 44/61 by decarbonylation and decarboxylation through hydrodeoxygenation, so that the ratio of odd carbon number molecules to even carbon number molecules in the deoxygenated product is about 6: 1. . Another embodiment of the present invention is a catalyst for deoxygenating bio-oils for fuel production. The catalyst 320 comprises a substrate comprising activated carbon in granular form ranging in size from 0.5 mm to 3 mm. The substrate has pores from 0.2 nm to 10 nm wide. Catalyst 320 comprises a catalytically effective nickel or palladium coating deposited without electricity that has a nanoscale thickness arranged on the pore surfaces. The loading of palladium or nickel into catalyst 320 is less than about 2% by weight. Optionally, catalyst 320 comprises palladium grains about 15 nanometers wide. As an option for one or more embodiments of the present invention, the system 300 further comprises a three-phase separator configured to receive effluent from the deoxygenation stage 310 and to separate water, liquid hydrocarbons, and gases from the effluent in separate streams. According to one or more embodiments of the present invention, system 300 further comprises an isomerization and hydrocracking stage 350 that comprises at least one isomerization and hydrocracking reactor 355 and an isomerization and hydrocracking catalyst 360. The isomerization and hydrocracking stage 350 it is configured to receive the liquid hydrocarbons from the 310 and hydrogen deoxygenation stage. The isomerization and hydrocracking stage 350 operates under conditions to convert liquid hydrocarbons from deoxygenation stage 310 into gasoline, diesel fuel, and / or 45/61 aviation / jet. More specifically, the isomerization and hydrocracking stage 350 is configured to operate at temperatures and pressures to perform the conversion of hydrocarbons to fuels. 360 isomerization and hydrocracking catalyst can be one or more commercially available catalysts for hydrocracking and isomerization. According to one or more embodiments of the present invention, the deoxygenation stage 310 comprises two or more deoxygenation reactor chambers 315, each containing catalyst 320. The two or more deoxygenation reactor chambers 315 are connected in series (not shown in Figure 4). According to one or more embodiments of the present invention, the deoxygenation stage 310 comprises two or more deoxygenation reactor chambers 315, each containing catalyst 320 or a mixture of catalysts. The two or more deoxygenation reactor chambers 315 are connected in series and the system 300 further comprises a separator system to remove carbon monoxide, light gases, carbon dioxide, and water from the effluent stream that connects the two or more chambers. deoxygenation reactor 315 between the two or more deoxygenation reaction chambers (additional reaction chambers and separator not shown in Figure 4). According to another embodiment of the present invention, the system. 300 further comprises a product separation stage 370 configured to receive products from the isomerization and hydrocracking stage 350 and to separate the products into diesel fuel, gasoline, and / or jet / jet fuel. System 300 additionally comprises a separator 375 comprising more than one separation stage to separate hydrogen from the isomerization stage 46/61 hydrocracking 350 effluent to recycle back to hydrocracking isomerization stage 350. Reference is now made to Figure 5, in which a system 400 is shown for the production of fuel from raw materials such as renewable raw materials such as, but not limited to, bio-oils and other oxygenated hydrocarbons. System 400 comprises a deoxygenation stage 310, a three-phase separator 335, an isomerization and hydrocracking stage 350, a product separation stage 370, and a separator 375, all substantially the same and configured as described above for system 300. The system 400 further comprises a separator 410 configured to receive gases from the three-phase separator 335 and to separate hydrogen from carbon monoxide, carbon dioxide, and light gases. The separator 410 is connected to supply hydrogen to the deoxygenation stage 310 or to the hydrocracking stage 350. The system 400 additionally comprises a water vapor switching stage and a steam reformer 420 connected in order to receive carbon monoxide, CO 2 , and light gases from separator 410 and light gases from product separation stage 370. The water vapor switching stage and steam reformer 420 produce hydrogen from the gases they receive using 'switching' reactions water vapor and / or reformer and supplies the hydrogen for the deoxygenation stage 310 and / or the isomerization and hydrocracking stage 350. According to another embodiment of the present invention, the system 400 comprises a three-phase separator 335 configured to receive effluent from the deoxygenation stage and to separate water, liquid hydrocarbons, and gases from the effluent in separate streams; and a second separator 410 and switching / reformer stage 420 to produce hydrogen 47/61 of carbon monoxide and light gases. In one or more alternative embodiments of systems according to the present invention, the deoxygenation stage comprises two or more deoxygenation reactor chambers connected in series and a separator to remove carbon monoxide, carbon dioxide, water, and light gases from the current between the two or more deoxygenation reaction chambers. Another separator is used to separate hydrogen from carbon monoxide, carbon dioxide, and light gases. A switching reformer / reactor is included to produce hydrogen from carbon monoxide and light gases. According to one or more embodiments of the present invention, a basic process is to deoxygen naturally occurring algae oil or inedible bio-oils to produce corresponding alkanes and further treat them to produce descriptive report biofuels. The treatment process involves hydrocracking and isomerization. One or more embodiments of the present invention include a two-stage process, the first of which involves deoxygenation of the oil using catalysts and operating conditions, according to one or more embodiments of the present invention, to suppress the formation of water . The second stage of the process comprises hydroprocessing the first stage product in a second stage reactor. The total liquid and gas mixture of the first reactor stage is cooled and vaporized to remove gases and light liquid products, if any. The three-phase separator also removes any water produced in the first stage deoxygenation reactor to prevent degradation of the second stage catalyst. Hydrogen supply gas in the first stage reactor is operated in single-pass mode. THE 48/61 gas mixture from the three-phase separator will contain large amounts of CO and hydrogen in addition to CO2 and other light hydrocarbon product gases. The CO to CO2 ratio of the gas mixture of the first stage product is significantly higher than that reported in the literature by others. Thus, as an option for one or more embodiments of the present invention, this gas mixture can be used as a source for the generation of hydrogen or used to produce the necessary process heat. Optionally, the product gas from the first stage after removing water and other heavy condensables (if any) can be further processed to separate hydrogen from CO, CO 2 , and light hydrocarbons. The recovered hydrogen can The current containing some then be returned to hydrogen, CO, CO2, the reactor. Light hydrocarbon gases can be switching reactions from gas produced to pass and water and reformed by steam to can be used as a replacement to produce hydrogen that both the first and the second stage reactors. If desired, the light hydrocarbon gas stream can be supplemented by adding some light liquid products from the process, in order to meet the total hydrogen replacement requirement for the process. Another option would be to use separate CO, CO 2 , and light hydrocarbon gas streams for combustion in a furnace to provide the process heat needed by the unit. In this operating mode, a single recycle gas stream and a recycled gas compressor can be used for both stages for further simplification of the general flow scheme. The liquid product of the first deoxygenation reactor will be primarily a mixture of normal chain paraffins with a low melting point. These are mixed with a fresh stream of hydrogen from 49/61 recycling and passed through another fixed base reactor to drive. isomerization and mild hydrocracking reactions. The product of the second stage reactor will have components. hydrocarbon boiling temperatures in the range of gasoline, jet, and diesel. A suitable commercially available hydroprocessing catalyst that provides these functions is housed in the second stage reactor. According to one or more embodiments of the present invention, the first deoxygenation reactor uses deoxygenation catalyst, according to one or more embodiments of the present invention, produced by processes according to one or more embodiments of the present invention. The deoxygenation process uses process conditions according to one or more embodiments of the present invention. The liquid product of the first stage conversion, according to one or more modalities of the present invention, was analyzed with the use of GC / MS and a trace for the liquid product of Camelina oil deoxygenation is shown in Figure 1-3. The GC trace showed that the paraffinic product contains primarily paraffins with a chain length that is one carbon less than the original fatty acid composition when compared to Figure 1-2. The results indicate that the liquid product is primarily a paraffinic product and also indicate that deoxygenation is, in most cases, achieved through the production of CO and CO2 instead of water. The ratio of even-numbered to odd carbon samples in the first stage liquid product is an indicator of the predominant mechanism for deoxygenation: decarbonylation, decarboxylation, or hydroxydeoxygenation. The biggest reason indicates that the most prevalent mechanism is the decarbonylation or decarboxylation mechanism (producing carbon oxides instead of water). Experimental results 50/61 for embodiments of the present invention show that this ratio is about 6 in the liquid product; however, in other deoxygenation technologies, the ratio is typically less than 1. A low ratio is an indication that large amounts of water are produced by hydroxydeoxygenation, and the process consumes large amounts of hydrogen. The CO to CO 2 ratio obtained with the use of deoxygenation catalyst and processes according to one or more embodiments of the present invention is approximately 6, which indicates that deoxygenation for embodiments of the present invention is primarily as decarbonylation. For other deoxygenation technologies, the CO to CO 2 ratio is 0 to 2. The higher CO content in the product and gas mixture has advantages for use as a fuel and for the generation of hydrogen. Hydroprocessing units and associated catalysts according to one or more embodiments of the present invention are exclusive, at least in part, due to their ability to selectively convert different types of bio-oils into aviation fuels and other transport fuels with characteristics performance comparable to conventional petroleum-based products. Long chain alkanes resulting from the deoxygenation of oils can be cracked in the presence of hydrogen and catalysts to produce jet biofuel (boiling temperature range 118 to 314 ° C) diesel biofuel (boiling temperature range 262 a 407 ° C). In addition, the alkane chain can be isomerized to produce branched hydrocarbons. With the appropriate commercial hydroprocessing catalyst, the product can be customized by controlling the degree of cracking isomerization to produce designer biodiesel bio-jet fuels with specific desirable properties. 51/61 One embodiment of the present invention is a process for producing diesel and aviation fuels from bio-renewable raw materials. The bio-specific raw materials are vegetable oils and bio-oils derived from cellulose. Pyrolysis, liquefaction, or microbial media can be used to produce bio-oils from cellulosic materials, such as wood chips, agricultural waste, or municipal waste. Whether it is a vintage oil or an oil derived from cellulosic material, the oil must pass through a pre-treatment step to rid it of contaminants and potential catalyst poisons. In the case of vintage oils, the pre-treatment step may consist only of acid washing steps and treatment with an ion exchange material. In the case of oil derived from cellulosic raw materials, extensive pre-treatment steps are necessary to improve its processing capacity. They must undergo significant improvement to remove contaminants and to improve stability. These oils, whether derived from vintage oils or cellulosic bio-oils, consist of oxygen in significant amounts in addition to carbon and hydrogen in its constituent molecule. The process described here consists of steps to remove this oxygen. In the case of vintage oils, once oxygen is removed and the triglyceride backbone is broken down, the resulting molecule is a normal chain paraffin. Paraffin is additionally subjected to additional processing steps to yield a biofuel to meet all transport fuel specifications. The process for converting renewable raw materials such as crop oils, therefore, consists of two process steps: removal of oxygen and 52/61 isomerization / soft cracking to produce the final biofuel product. The first step is to break the triglyceride backbone, hydrogenate to saturate the molecule, and remove oxygen (deoxygenation) from the oil molecule. Deoxygenation is a catalytic reaction in the presence of a catalyst and hydrogen. Hydrogen is a reagent. The catalyst is loaded into a fixed-base, continuous-flow reactor. The hydrogen gas and the bio-oil raw material are mixed together before the reactor, heated to the reaction temperature in a supply furnace, and reacted in the fixed-flow reactor. A catalyst, such as that according to one or more embodiments of the present invention, is charged into the reactor and preferably removes oxygen by decarbonylation and decarboxylation instead of hydroxydeoxygenation. Decarbonylation produces carbon monoxide, decarboxylation produces carbon dioxide, and hydroxydeoxygenation produces water. It is preferable to remove oxygen by decarbonylation or decarboxylation instead of hydroxydeoxygenation. Hydroxydeoxygenation consumes greater amounts of hydrogen. Higher hydrogen consumption negatively affects the process economy. The higher consumption of hydrogen in the reactor also releases heat that needs to be removed for temperature control in the reactor. This would require a special model of the reactor interior, adding to the cost and complexity of the process. Cold hydrogen gas is used to temper the reaction / product mixture between catalyst bases in a multi-base reactor. Increased water generation in the reactor can also cause damage to the integrity and mechanical strength of the catalyst under certain conditions. The catalyst, according to one or more 53/61 embodiments of the present invention, used in the process preferentially removes oxygen by decarboxylation decarbonylation mechanism instead of hydroxydeoxygenation mechanism, thus producing CO and CO 2 instead of water. Table 2 shows results of a typical execution: TABLE 2 PARAMETER Temperature (° C) 380 380 Pressure (mPa (psig)) 3.45 (500) 3.45 (500) WHSV (1 / hr) 2.5 0.82 Hydrogen Supply 2878 9582 (SCFB) PRODUCTS CO / CO 2 (% by weight) 8.78 9.96 Water (% by weight) 2.57 2.79 Integral net product 88.65 87.25 (% by weight) Deoxygenation (% in 80.2 90.6 Weight) and reactor gas The total liquid mixture is cooled and vaporized to remove light liquids, if any. The gases and liquid product products will be primarily a mixture of normal chain paraffins with a low melting point. These are mixed with a fresh stream of recycle hydrogen and passed through another fixed-base reactor to conduct isomerization and mild hydrocracking reactions. A suitable catalyst that provides these functions is housed in this reactor. product of this reactor will have hydrocarbon components that boil in the temperatures of gasoline, jet, and diesel ranges. In mild isomerization and hydrocracking, normal paraffins of 15 to 23 carbon atoms are subjected 54/61 cracking and branching in the presence of hydrogen. These types of reactions allow the conversion of normal paraffins to fuels in the specification that boil predominantly in the boiling range of diesel and jet. The gas and liquid mixture of the effluent second stage reactor is vaporized and the gas mixture that contains, in most cases, hydrogen rich gas is cleaned and recycled to the front end of the reactor for reuse. The hydrogen consumed in both the first and the second state reactors is refilled by the addition of replacement hydrogen. The liquid stream separated from the gaseous stream is distilled to yield the required jet and diesel fuel in addition to other gases and light liquids that are discarded or used as in any conventional refinery. Light liquid products can be light paraffins that result from mild hydrocracking that occurs in the second stage reactor. . The process produces hydrocarbon liquid to meet all required diesel and aviation fuel specifications. Jet product and diesel product yield from unit supply oil is maximized with lower production of lighter hydrocarbons in the process. With less light hydrocarbons and less water produced in the process, the requirement for hydrogen replacement will generally be less. Hydrogen is a reagent in the process for converting bio raw materials into biofuels for descriptive reporting. The levels of hydrogen consumption have a significant impact on the overall process economy. The first stage recycle hydrogen gas can be operated in single-pass mode. The single-pass recycling hydrogen gas will contain large amounts of CO and hydrogen in addition to CO 2 and other 55/61 gases of light hydrocarbon product. This gas mixture can be a good source for generating hydrogen or producing the necessary process heat. Optionally, the unit can be operated in recycle gas mode by continuously removing CO, CO 2 , and some light gases from a separation unit downstream of the three-phase separator. CO and light gases can be used to produce the hydrogen needed for the process through steam reforming and water vapor switching reactions. In addition, other bio raw materials, such as cellulose (wood chips, corn husks, agricultural waste, etc.) can be used to produce hydrogen. These bio raw materials are steam reformed in a separate unit to produce hydrogen. Steam reforming (gasification) produces production gas that consists, in most cases, of hydrogen and carbon oxides in addition to many contaminants. The gas needs to be cleaned before it can be subjected to a water-gas switching reaction to produce hydrogen, which can then be used in the process to convert crop oils and other bio-oils into descriptive report biofuels. One or more embodiments of the present invention comprise the use of at least one crop oil such as, but not limited to, algae or microbial oil, canola oil, corn oil, jatropha oil, cameline oil, rapeseed, mantle oil, and combinations thereof. One or more embodiments of the present invention further include the options of co-substituting or mixing with a component derived from fossil fuels, depolymerization of waste plastics, synthetic, or catalytic, chemical or thermal oils derived from petrochemical or chemical processes. 56/61 One or more embodiments of the present invention further include the generation of a gaseous stream that can be used to generate the necessary process heat in a substantially high temperature conversion process. This modality additionally improves the economy of the process. Example 7: Synthesis of Jet Fuel / Aviation of Bio-oils With the Use of Nano-coated Palladium on Activated Carbon Deoxygenation Catalyst Refined Camelina oil was the raw material used in a deoxygenation reactor according to one or more modalities of the present invention. Deoxygenation experiments were performed on a multiphase compressed base with continuous downward flow. Eleven grams of 1.72% by weight of nanocovered Pd on activated carbon catalyst according to one or more embodiments of the present invention was loaded into a stainless steel reactor. The reactor was 0.775 cm (0.305 inch) in diameter and 45.72 cm (18 inches) in length with pre-heating and post-heating zones. The reactor volume was 22 cubic centimeters. Heat for the reactor was supplied by a temperature controlled furnace in three zones with heat equalization blocks. The Camelina oil supply rate to the reactor was 0.1 cc / min. Liquid and gaseous products leaving the reactor were collected in a separator. Back pressure regulators kept the system pressure in operation at 6.89 mPa (1,000 psig). The catalyst was reduced with hydrogen at 250 ° C for 2 hours first. The reactor temperature was raised from 250 ° C to 360 ° C within 60 minutes. The liquid Camelina oil was pumped into the reactor at a rate of 0.1 cc / min. The rate of hydrogen gas supply to the reactor was 135 cc / min. The reactor temperature was maintained at 360 ° C and the 57/61 reactor was run for 24 hours. The gas product of the reactor was analyzed using a GC. The gaseous product of the main reagent observed in addition to H 2 was CO. The paraffin wax product was collected and separated from the water by gravity. Paraffin wax from the deoxygenation reactor was fed into an isomerization / cracking reactor. isomerization and cracking reactor used a standard commercially available catalyst. The paraffin wax supply line was maintained at 40 ° C to ensure that the wax was properly pumped into the isomerization / cracking reactor. The isomerization / cracking experiment was carried out in a multi-phase compressed base reactor with continuous downward flow. A commercially available isomerization catalyst totaling 3.8 grams was loaded into the stainless steel reactor. The reactor was 0.775 cm (0.305 inch) in diameter and 12.7 cm (5 inches) long with preheating and post-heating zones. The reactor volume was 6 cc. Heat for the reactor was supplied by a temperature controlled furnace in three zones with heat equalization blocks. A pump was used to pump the supply of paraffin wax at a rate of 0.1 cc / min in the reactor. Liquid and gaseous products leaving the reactor were collected in a separator. Back pressure regulators kept the system pressure in operation at 6.89 mPa (1,000 psig). The isomerization / cracking catalyst was reduced with hydrogen at 260 ° C for 2 hours first. Ά reactor temperature was lowered to 232 ° C. The liquid paraffinic supply was then pumped into the reactor at a rate of 0.1 cc / min. The rate of hydrogen gas supply to the reactor was 83 cc / min. The reactor temperature was 58/61 raised to and maintained at 360 ° C and the reactor was run for 20 hours. All liquid product was collected from the reactor and analyzed using simulated D-2887 distillation. The simulated distillation analysis showed 80% by volume of jet fuel in the boiling range of 244F-597F was produced. Example 8: Fuel Synthesis Dieses of Bio oils Using Nano-coated Palladium in Activated Carbon Deoxygenation Catalyst Refined Camelina oil was the raw material used in a deoxygenation reactor according to one or more modalities of the present invention. Deoxygenation experiments were carried out in a multi-phase compressed base reactor with continuous downward flow. Eleven grams of 1.72% by weight of nanocovered Pd on activated carbon catalyst according to one or more embodiments of the present invention was loaded into a stainless steel reactor. The reactor was 0.775 cm (0.305 inch) in diameter and 45.72 cm (18 inches) in length with pre-heating and post-heating zones. The reactor volume was 22 cc. Heat for the reactor was supplied by a temperature controlled furnace in three zones with heat equalization blocks. A pump was used to pump the supply of Camelina oil at 0.1 cc / min to the reactor. Liquid and gaseous products leaving the reactor were collected in a separator. Back pressure regulators kept the system pressure in operation at 6.89 mPa (1,000 psig). The catalyst was reduced with hydrogen at 250 ° C for 2 hours. The reactor temperature was raised from 250 ° C to 360 ° C within 60 minutes. The liquid Camelina oil was pumped into the reactor at a rate of 0.1 cc / min. The rate of hydrogen gas supply to the reactor was 135 cc / min. The reactor temperature was maintained at 360 ° C and the 59/61 reactor was run for 24 hours. | The reactor gas product was analyzed using a | GC. The main reactant gas product observed beyond H 2 was CO. The paraffin wax product was collected and separated from the water by gravity. | Paraffin wax from the deoxygenation reactor was fed into an isomerization / cracking reactor. The paraffin wax supply line was maintained at 40 ° C to ensure that the wax was properly pumped into the isomerization / cracking reactor. The isomerization / cracking experiment was carried out in a multiphase compressed base reactor with continuous flow. A commercially available isomerization catalyst totaling 3.8 grams was loaded into the stainless steel reactor. | The reactor was 0.775 cm (0.305 inch) in diameter and 12.7 cm (5 inches) long with pre-heating and post-heating zones. The reactor volume was 6 Heat for the reactor was supplied by a temperature controlled furnace in three zones with heat equalization blocks. A pump was used to pump a supply of paraffin wax into 0.1 cc / min for the reactor. Liquid and gaseous products leaving the reactor were collected in a separator. Back pressure regulators kept the system pressure in operation The isomerization / cracking catalyst was reduced with hydrogen at 260 ° C for 2 hours. The reactor temperature was lowered to 232 ° [C. The liquid paraffinic supply was then pumped into the [reactor at a rate of 0.1 cc / min. The rate of supply of 'hydrogen gas to the reactor was 83 cc / min. The reactor temperature was raised to and maintained at 325 ° C and the reactor was run for 20 hours. All liquid product was collected from the reactor and analyzed with the 60/61 use of simulated distillation D-2887. The simulated distillation analysis showed 84% by volume of diesel fuel in the boiling range of 504F-765F was produced. Methods according to one or more embodiments of the present invention can also comprise depositing palladium to produce palladium membranes for hydrogen separation. Methods according to one or more embodiments of the present invention may also comprise depositing palladium and / or other nanoscale coatings of metals on zeolite, alumina, or silica-alumina substrates to produce catalyst for hydrocarbon fuel hydrocracking applications. In the preceding specification, the invention was described with reference to specific modalities; however, a person of ordinary skill in the art will understand that various modifications and alterations can be made without departing from the scope of the present invention, as set out in the claims below. Consequently, the specification should be understood in an illustrative rather than a restrictive sense, and all such modifications are intended to be included within the scope of the present invention. Benefits, other advantages, and solutions to problems have been described above in relation to specific modalities; however, the benefits, advantages, solutions to problems, and any element (s) that may cause any benefit, advantage, or solution or cause it to become more pronounced should not be understood as a critical, required, or essential resource or element. any or all of the claims. As used herein, the terms comprise, which comprises, includes, including, has, has, at least one of, or any other variation of 61/61 are intended to cover non-exclusive inclusion. For example, a process, method, article or device that comprises a list of elements is not necessarily limited to just those elements, but may include other 5 elements not expressly listed or inherent in such a process, method, article or device. In addition, unless expressly stated otherwise, it either refers to one or inclusive and not one or exclusive. For example, a condition A or B is satisfied by any of the following: A 10 is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present) , and both A and B are true (or present).
权利要求:
Claims (3) [1] 1. METHOD OF DEOXYGENATION OF OXYGENED HYDROCARBONS, the method being characterized by understanding: provide a catalyst comprising a substrate porous and a metallic coating nanoscale catalytically deposited effective without electricity at the substrate; put on the catalyst in contact the oxygenated hydrocarbons and hydrogen in order to perform hydrogenation and deoxygenation in which deoxygenation is preferably carried out by decarbonylation and decarboxylation through hydrodeoxygenation. [2] 2/3 titania, zirconia, magnesia, chromia, zeolites or combinations thereof. 9. METHOD, according to claim 1, characterized in that the catalyst is catalytically active for preferential hydrogenation and deoxygenation of triglycerides by decarbonylation and decarboxylation through hydrodeoxygenation. 10. METHOD, according to claim 1, characterized in that the catalyst is catalytically active for preferential deoxygenation of alcohols, ethers, aldehydes, ketones, carboxylic acids, esters, phenolics or mixtures thereof by decarbonylation and decarboxylation through hydrodeoxygenation. 11. METHOD according to claim 1, characterized in that it further comprises the maintenance of partial pressure of carbon monoxide up to about 0.1 megapascals (15 psi) in which the metal comprises palladium. 12. METHOD, according to claim 1, characterized in that the deoxygenation of triglycerides is by decarbonylation and decarboxylation through hydrodeoxygenation, so that the ratio of odd to even carbon number in the deoxygenated product is about 6: 1. 13. METHOD, according to claim 1, characterized in that the hydrocarbons comprise triglycerides, the carbon substrate is activated carbon, the metal comprises palladium and the contact of the catalyst with the hydrocarbons and hydrogen in order to preferably perform deoxygenation by decarbonylation and decarboxylation through hydrodeoxygenation is carried out at temperatures in the range of 300 ° C to 400 ° C and pressures in the range of 1.5 megapascals to 15 megapascals. 14. METHOD, according to claim 1, characterized in that the hydrocarbons comprise 2. METHOD according to claim 1, characterized in that the decarbonylation to decarboxylation ratio is about 6: 1. METHOD according to claim 1, characterized in that the metal comprises palladium. METHOD according to claim 1, characterized in that the metal comprises nickel. 5. METHOD, according to claim 1, characterized in that the metal comprises chromium, molybdenum, tungsten, iron, ruthenium, osmium, cobalt, rhodium, iridium, platinum, zinc, silver, gold, copper or mixtures thereof. 6. METHOD, according to claim 1, characterized in that the substrate is activated carbon. METHOD, according to claim 1, characterized in that the porous substrate comprises carbon foam, alumina, silica-alumina, metal foam, silica, zeolites, titania, zirconia, magnesia, chromium, monoliths or combinations thereof. METHOD, according to claim 1, characterized in that the porous substrate is granular and comprises activated carbon, alumina, silica-alumina, silica, [3] 3/3 triglycerides, the substrate comprises activated carbon, carbon foam, alumina, metal foam, silica-alumina, silica, zeolites, titania, zirconia, magnesia, chromium, monoliths or combinations thereof, the metal is selected from group consisting of chromium, molybdenum, tungsten, iron, ruthenium, osmium, cobalt, nickel, rhodium, iridium, palladium, platinum, zinc, gold, silver, copper or mixtures of the same contact of the catalyst with hydrogen hydrocarbons in order to carry out preferably deoxygenation by decarbonylation and decarboxylation by hydrodeoxygenation is carried out at temperatures in the range of 300 ° C to 400 ° C and pressures in the range 1.5 megapascals to 15 megapascals. 15. METHOD, according with The claim 1, featured per the catalyst has one metal loading less than or equal to fence in 2% effectively in deoxygenation bigger that about 90% . 16. METHOD, according with The claim 1, featured per the catalyst has one metal loading less than or equal to fence in 1%1% effectively in deoxygenation bigger that about 90% . 17. METHOD, according with The claim 1, featured per space speed hour weight in hour is 0.2 to 2.5.
类似技术:
公开号 | 公开日 | 专利标题 BR112013014687B1|2019-02-05|oxygenated hydrocarbon deoxygenation method Li et al.2018|Heterogeneous sulfur-free hydrodeoxygenation catalysts for selectively upgrading the renewable bio-oils to second generation biofuels Xu et al.2017|Efficient hydrogenation of various renewable oils over Ru-HAP catalyst in water Kim et al.2017|Maximizing biojet fuel production from triglyceride: importance of the hydrocracking catalyst and separate deoxygenation/hydrocracking steps Wang et al.2012|From biomass to advanced bio-fuel by catalytic pyrolysis/hydro-processing: Hydrodeoxygenation of bio-oil derived from biomass catalytic pyrolysis Kumar et al.2021|Thermochemical production of bio-oil: A review of downstream processing technologies for bio-oil upgrading, production of hydrogen and high value-added products Li et al.2016|Hydrocracking of palm oil to jet biofuel over different zeolites WO2011025002A1|2011-03-03|Method for producing aviation fuel oil base, and aviation fuel oil composition Zhao et al.2014|Hydroconversion of methyl laurate as a model compound to hydrocarbons on bifunctional Ni2P/SAPO-11: Simultaneous comparison with the performance of Ni/SAPO-11 Li et al.2015|Recent advances for the production of hydrocarbon biofuel via deoxygenation progress Lee et al.2019|Efficient upgrading of pyrolysis bio-oil over Ni-based catalysts in supercritical ethanol Tan et al.2020|Prepared multifunctional catalyst Ni2P/Zr-SBA-15 and catalyzed Jatropha Oil to produce bio-aviation fuel Pongsiriyakul et al.2021|Effective Cu/Re promoted Ni-supported γ-Al2O3 catalyst for upgrading algae bio-crude oil produced by hydrothermal liquefaction Asiedu et al.2020|Catalytic transfer hydrogenation and characterization of flash hydrolyzed microalgae into hydrocarbon fuels production | Kaewmeesri et al.2021|Deoxygenations of palm oil-derived methyl esters over mono-And bimetallic NiCo catalysts Asiedu et al.2019|Kinetics and Optimization of Catalytic Transfer Hydrogenation of WCO Using 2-Propanol as a Hydrogen Donor over NiO x–MoO x–CoO x/Zeolite Xiao et al.2021|Hydrodeoxygenation of fatty acid methyl esters and simultaneous products isomerization over bimetallic Ni‐Co/SAPO‐11 catalysts US9315736B2|2016-04-19|Methods of fuel production Mäki-Arvela et al.2021|Hydroconversion of fatty acids and vegetable oils for production of jet fuels WO2015084893A1|2015-06-11|Methods of fuel production Ishihara et al.2021|Effects of Zn addition into ZSM-5 zeolite on dehydrocyclization-cracking of soybean oil using hierarchical zeolite-Al2O3 composite-supported Pt/NiMo sulfided catalysts Sun2017|Direct syngas-to-fuel: integration of Fischer-Tropsch synthesis and hydrocracking in micro-structured reactors Patil et al.2017|Catalytic hydrotreatment of jatropha oil over lanthanum hydroxide supported noble metals: effect of promotion with cerium Konwar et al.2020|Efficient hydrothermal deoxygenation of tall oil fatty acids into n-paraffinic hydrocarbons and alcohols in the presence of aqueous formic acid Mirzayanti et al.2019|Triglyceride of Kapok seed Oil to biofuel over a synthesised Cu-Mo supported HZSM-5 catalyst
同族专利:
公开号 | 公开日 WO2012083236A3|2012-10-26| AU2011343489A1|2013-08-01| CA2821753A1|2012-06-21| US20120157727A1|2012-06-21| US8524629B2|2013-09-03| EP2651557A4|2014-07-02| US8507400B2|2013-08-13| WO2012083236A2|2012-06-21| CN108465462A|2018-08-31| US20120157297A1|2012-06-21| US8236999B2|2012-08-07| US20120156109A1|2012-06-21| CN103459031A|2013-12-18| BR112013014687A2|2016-10-04| EP2651557A2|2013-10-23| CA2821753C|2019-04-16| AU2018203065A1|2018-05-24| US8597599B2|2013-12-03| AU2017202632A1|2017-05-11| US20120157299A1|2012-06-21|
引用文献:
公开号 | 申请日 | 公开日 | 申请人 | 专利标题 US3007941A|1959-12-31|1961-11-07|Du Pont|Decarbonylation of furfural| US3354059A|1964-08-12|1967-11-21|Ibm|Electrodeposition of nickel-iron magnetic alloy films| US3635761A|1970-05-05|1972-01-18|Mobil Oil Corp|Electroless deposition of metals| DE2100971B2|1971-01-11|1975-04-17|Langbein-Pfanhauser Werke Ag, 4040 Neuss|Process and bath for the production of micro-cracked chrome layers over intermediate layers| US4359406A|1977-06-17|1982-11-16|Exxon Research And Engineering Co.|Highly dispersed supported group VIII metal-phosphorus compounds, and highly dispersed, supported group VIII metal-arsenic and a process for making said compounds| US4415479A|1981-10-29|1983-11-15|Standard Oil Company |Palladium on carbon catalyst for purification of crude terephthalic acid| US4556492A|1983-12-16|1985-12-03|Ecolochem, Inc.|Deoxygenation process| US4695489A|1986-07-28|1987-09-22|General Electric Company|Electroless nickel plating composition and method| US4900618A|1986-11-07|1990-02-13|Monsanto Company|Oxidation-resistant metal coatings| US5203911A|1991-06-24|1993-04-20|Shipley Company Inc.|Controlled electroless plating| US5747410A|1992-07-03|1998-05-05|Kabushiki Kaisha Riken|Exhaust gas cleaner and method of cleaning exhaust gas| US5916840A|1994-07-01|1999-06-29|Monsanto Company|Process for preparing carboxylic acid salts and catalysts useful in such process| US6207128B1|1997-05-05|2001-03-27|Akzo Nobel N.V.|Method of producing a catalyst| ES2273394T3|1997-05-05|2007-05-01|Akzo Nobel N.V.|METHOD FOR PRODUCING A CATALYST BY NON-ELECTROLYTIC DEPOSITION OF ACTIVE METAL ON THE SUPPORT| EP1923395A1|1999-12-21|2008-05-21|Monsanto Technology, LLC|Use of supplemental promoter in conjuction with a carbon-supported, noble-metal-containing catalyst in liquid phase oxidation reactions| WO2001053005A1|2000-01-21|2001-07-26|Research Triangle Institute|Method for preparation of thermally and mechanically stable metal/porous substrate composite membranes| US6376708B1|2000-04-11|2002-04-23|Monsanto Technology Llc|Process and catalyst for dehydrogenating primary alcohols to make carboxylic acid salts| US6686308B2|2001-12-03|2004-02-03|3M Innovative Properties Company|Supported nanoparticle catalyst| US6899816B2|2002-04-03|2005-05-31|Applied Materials, Inc.|Electroless deposition method| US6956005B2|2002-06-28|2005-10-18|Monsanto Technology Llc|Use of tellurium in carbon-supported, noble metal-containing catalysts for liquid phase oxidation reactions| US7375053B2|2003-04-07|2008-05-20|W. R. Grace & Co.- Conn.|Nickel and cobalt plated sponge catalysts| WO2004095614A2|2003-04-18|2004-11-04|Ube Industries, Ltd.|Metal-supported porous carbon film, fuel cell electrode and fuel cell employing the electrode| US20050075243A1|2003-10-07|2005-04-07|Sud-Chemie, Inc.|Catalyst for dehydrogenation of hydrocarbons| US7625660B2|2003-12-26|2009-12-01|Hitachi Maxell, Ltd.|Fuel cell and membrane electrode assembly| AR051926A1|2004-09-15|2007-02-21|Monsanto Technology Llc|OXIDATION CATALYSTS, PROCEDURES FOR THE PREPARATION OF SUCH CATALYZERS AND PROCESS FOR THE ELABORATION OF N- GLYCINE OR A SALT OF THE SAME| US7491858B2|2005-01-14|2009-02-17|Fortum Oyj|Method for the manufacture of hydrocarbons| PT1681337E|2005-01-14|2010-12-24|Neste Oil Oyj|Method for the manufacture of hydrocarbons| TW200707640A|2005-03-18|2007-02-16|Applied Materials Inc|Contact metallization scheme using a barrier layer over a silicide layer| US20060264684A1|2005-05-19|2006-11-23|Petri John A|Production of diesel fuel from biorenewable feedstocks| US7511181B2|2006-05-02|2009-03-31|Uop Llc|Production of diesel fuel from biorenewable feedstocks| US8278492B2|2005-07-05|2012-10-02|Neste Oil Oyj|Process for the manufacture of diesel range hydrocarbons| EP1741692A1|2005-07-06|2007-01-10|BP Chemicals Limited|Process for the conversion of hydrocarbons to C2-oxygenates| US7314960B1|2006-09-28|2008-01-01|Yuan Ze University|Catalytic synthesis of oxygenate from alcohol| CN101595203A|2006-12-01|2009-12-02|北卡罗来纳州立大学|The method of conversion of biomass to fuel| CN101802263A|2007-09-13|2010-08-11|维罗西股份有限公司|porous electrolessly deposited coatings| US8039682B2|2008-03-17|2011-10-18|Uop Llc|Production of aviation fuel from renewable feedstocks| US8193399B2|2008-03-17|2012-06-05|Uop Llc|Production of diesel fuel and aviation fuel from renewable feedstocks| US8329967B2|2008-04-06|2012-12-11|Uop Llc|Production of blended fuel from renewable feedstocks| EP2268572B1|2008-04-23|2017-06-21|Her Majesty The Queen In Right Of Canada As Represented By The Minister Of Natural Resources Canada|Production of hydrogen from oxygenated hydrocarbons| US7960596B2|2008-07-24|2011-06-14|Chevron U.S.A. Inc.|Conversion of vegetable oils to base oils and transportation fuels| US8404613B2|2008-10-21|2013-03-26|Brookhaven Science Associates, Llc|Platinum-based electrocatalysts synthesized by depositing contiguous adlayers on carbon nanostructures| US20100300984A1|2009-05-27|2010-12-02|Kastner James R|Nanostructured Carbon Supported Catalysts, Methods Of Making, And Methods Of Use| US20110028773A1|2009-07-29|2011-02-03|Bala Subramaniam|Deoxygenation of Bio-Oils and Other Compounds to Hydrocarbons in Supercritical Media| KR101305072B1|2009-12-30|2013-09-11|제일모직주식회사|Carbon nanofiber-metal composite and method for preparing the same| US8389782B2|2010-08-31|2013-03-05|Chevron U.S.A. Inc.|Biofuel production through catalytic deoxygenation|AU2009320371B2|2008-11-26|2015-09-17|University Of North Dakota|Method for producing cyclic organic compounds from crop oils| US9315736B2|2010-12-16|2016-04-19|Energia Technologies, Inc.|Methods of fuel production| BR112013019652A2|2011-02-03|2019-09-24|Univ Louisville Res Found Inc|process for converting fatty acids to paraffinic linear hydrocarbons, process for producing branched paraffinic hydrocarbons from fatty acids and paraffinic hydrocarbon| IN2014CN02820A|2011-11-14|2015-07-03|Shell Int Research| US8927795B2|2012-05-18|2015-01-06|Uop Llc|Process for controlling the simultaneous production of diesel and jet fuel range paraffins by blending feedstocks| US9416321B2|2012-05-18|2016-08-16|Uop Llc|Separation process with modified enhanced hot separator system| WO2014026014A2|2012-08-08|2014-02-13|University Of Louisville Research Foundation, Inc.|Process for the production of hydrocarbons for fuels, solvents, and other hydrocarbon products| ITMI20121465A1|2012-09-03|2014-03-04|Eni Spa|METHOD TO CONVERT A CONVENTIONAL REFINERY OF MINERAL OILS IN A BIOFINERY| US8916739B2|2012-12-12|2014-12-23|Uop Llc|Methods and apparatuses for preparing normal paraffins and hydrocarbon product streams| KR101450089B1|2012-12-20|2014-10-15|한국과학기술연구원|method of manufacturing high carbon number saturated hydrocarbons from biomass comprising benzyl phenyl ethers using acid-metal complex catalyst| RU2524211C1|2013-06-24|2014-07-27|Александр Анатольевич Симонов|Catalyst system in thermolysis of heavy oil stock and oil extraction and refining wastes| CN103614155B|2013-09-11|2016-08-10|浙江工业大学|A kind of algae oil produces the preparation method of HC fuel| KR101591973B1|2014-06-23|2016-02-04|한진화학|Method for plating electroless of activated carbon| TWI680207B|2014-12-17|2019-12-21|德商德國艾托特克公司|Plating bath composition and method for electroless plating of palladium| CN105778976B|2014-12-25|2018-01-05|中国石油天然气股份有限公司|A kind of method that grease catalytic deoxidation prepares biodiesel| WO2017023838A1|2015-08-06|2017-02-09|Uop Llc|Process for reconfiguring existing treating units in a refinery| CN105526812B|2015-12-23|2017-09-26|山东大学|A kind of catalysis oxidation heat exchanger and its method of work| RU2652986C1|2016-12-28|2018-05-04|федеральное государственное автономное образовательное учреждение высшего образования "Московский физико-технический институт "|Catalyst and process for producing a fraction of aromatic and aliphatic hydrocarbons from vegetable oil| JP2020516639A|2017-04-12|2020-06-11|マジェンタ セラピューティクス インコーポレイテッドＭａｇｅｎｔａ Ｔｈｅｒａｐｅｕｔｉｃｓ， Ｉｎｃ．|Aryl hydrocarbon receptor antagonists and uses thereof| CN108187619A|2018-01-24|2018-06-22|中冶华天工程技术有限公司|The preparation method of EDTA modified magnetic activated carbon heavy metal-polluted soil renovation agents| US20210171844A1|2018-05-18|2021-06-10|Hibd Laboratory Association|Method for producing bio-jet fuel| CN108774542A|2018-07-04|2018-11-09|中国科学院广州能源研究所|A kind of method that mononuclear phenolic compound hydrogenation deoxidation prepares hydro carbons in Catalytic lignin depolymerization product| CN109647498A|2019-01-25|2019-04-19|浙江大学|A kind of molecular sieve carried Zn catalyst and its preparation method and application for bio-oil hydrogenation deoxidation| CN110624380B|2019-09-30|2022-02-18|江苏海默环保科技有限公司|Synergistic desulfurization and denitrification agent and preparation and application thereof|
法律状态:
2016-10-04| B15I| Others concerning applications: loss of priority|Free format text: PERDA DA PRIORIDADE US 61/424,043 REIVINDICADA NO PCT US11/065620 DE 16/12/2011, CONFORME AS DISPOSICOES PREVISTAS NA LEI 9.279 DE 14/05/1996 (LPI) ART. 167O, ITEM 28 DO ATO NORMATIVO 128/97 E NO ART. 29 DA RESOLUCAO INPI-PR 77/2013. ESTA PERDA SE DEU PELO FATO DE O DEPOSITANTE CONSTANTE DA PETICAO DE REQUERIMENTO DO PEDIDO PCT SER DISTINTO DAQUELES QUE DEPOSITARAM A PRIORIDADE REIVINDICADA E NAO APRESENTOU DOCUMENTO COMPROBATORIO DE CESSAO DENTRO DO PRAZO DE 60 DIAS A CONTAR DA DATA DA ENTRADA DA FASE NACIONAL, CONFORME AS DISPOSICOES PREVISTAS NA LEI 9.279 DE 14/05/1996 (LPI) ART. 166O, ITEM 27 DO ATO NORMATIVO 128/97 E NO ART. 28 DA RESOLUCAO INPI-PR 77/2013. | 2017-01-10| B12F| Other appeals [chapter 12.6 patent gazette]| 2018-03-27| B15K| Others concerning applications: alteration of classification|Ipc: B01J 8/04 (2006.01), B01J 19/24 (2006.01), B01J 23 | 2018-11-27| B09A| Decision: intention to grant [chapter 9.1 patent gazette]| 2019-02-05| 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 16/12/2011, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 16/12/2011, OBSERVADAS AS CONDICOES LEGAIS |
优先权:
[返回顶部]
申请号 | 申请日 | 专利标题 US42404310P| true| 2010-12-16|2010-12-16| US61/424,043|2010-12-16| PCT/US2011/065620|WO2012083236A2|2010-12-16|2011-12-16|Catalysts, methods of preparation of catalyst, methods of deoxygenation, and systems for fuel production| 相关专利
Sulfonates, polymers, resist compositions and patterning process
Washing machine
Washing machine
Device for fixture finishing and tension adjusting of membrane
Structure for Equipping Band in a Plane Cathode Ray Tube
Process for preparation of 7 alpha-carboxyl 9, 11-epoxy steroids and intermediates useful therein an
国家/地区
|