Title of Invention	"A HYDROPROCESSING PROCESS"
Abstract	The hydrotreating process of the invention is charactenzea by contacting an oil to be treated comprising a petroleum hydrocarbon fraction that includes fractions with boiling points of 300°C and higher and has a sulfur content of 0.5-4.5 wt%, and an animal or vegetable-derived fat or oil component with an oxygen content of 0.3-13 wt%, with a catalyst comprising one or more metals selected from among elements of Group 6A and Group 8 of the Periodic Table and a porous inorganic oxide containing at least aluminum oxide, in the presence of hydrogen.

Title of Invention

"A HYDROPROCESSING PROCESS"

Abstract

The hydrotreating process of the invention is charactenzea by contacting an oil to be treated comprising a petroleum hydrocarbon fraction that includes fractions with boiling points of 300°C and higher and has a sulfur content of 0.5-4.5 wt%, and an animal or vegetable-derived fat or oil component with an oxygen content of 0.3-13 wt%, with a catalyst comprising one or more metals selected from among elements of Group 6A and Group 8 of the Periodic Table and a porous inorganic oxide containing at least aluminum oxide, in the presence of hydrogen.

Full Text	DESCRIPTION Hydrorefming Process and Hydrorefined Oil Technical Field [0001] The present invention relates to a hydrotreating process, and more specifically it relates to a hydrotreating process for oil to be treated that contains fat and oil components derived from animal and vegetable oils. The invention further relates to a hydrotreated oil produced by the aforementioned hydrotreating process. Background Art [0002] Effective utilization of biomass energy is a topic of increasing interest, as a strategy for preventing global warming. Notably, plant-derived biomass energy is "carbon neutral" because it allows effective utilization of the hydrocarbons converted from carbon dioxide by photosynthesis during the process of plant growth so that, considering natural life cycles, it does not contribute to increased carbon dioxide in the atmosphere. [0003] Utilization of this type of biomass energy has also been extensively researched in the field of transportation fuels. For example, if fuels produced from animal and vegetable oils could be used as diesel fuels, the synergistic effect obtained with the high energy efficiency of a diesel engine would be expected to contribute substantially to carbon dioxide emission reduction. Known diesel fuels utilizing fat and oil components derived from animal or vegetable oils include fatty acid methyl ester oils. Fatty acid methyl ester oils are produced by alkali-mediated transesterification with methanol on a triglyceride structure, which is the general structure for fat and oil components derived from animal and vegetable oils. However, as described in Patent document 1 mentioned below, the process of producing fatty acid methyl ester oils necessitates treatment of the glycerin by-product, or requires cost and energy for purification of the product oil. [Patent document 1]: Japanese Unexamined Patent Publication No. 2005-154647 Disclosure of the Invention Problem to be Solved by the Invention [0004] Other problems, in addition to those mentioned above, are associated with the use of animal and vegetable-derived fat and oil components or fuels produced using them as starting materials, for diesel fuels. First, animal and vegetable-derived fat and oil components generally have oxygen atoms in the molecule, and the oxygen can adversely affect the engine materials. Moreover, it is generally difficult to remove oxygen to extremely low concentrations. Also, when an animal or vegetable-derived fat or oil component is used in combination with a petroleum hydrocarbon fraction, current technology has not allowed sufficient reduction of both oxygen in the fat and oil component and sulfur in the petroleum hydrocarbon fraction. [0005] It is therefore an object of the present invention to provide a hydrotreating process that can economically and very effectively produce hydrotreated oil having adequately reduced oxygen and sulfur contents, when applied to an oil to be treated which contains an animal or vegetable-derived fat or oil component and a petroleum hydrocarbon fraction. It is another object of the invention to provide a hydrotreated oil obtained by the aforementioned hydrotreating process. Means for Solving the Problem [0006] The hydrotreating process of the invention is characterized by contacting an oil to be treated comprising a petroleum hydrocarbon fraction including fractions with boiling points of 300°C and higher and having a sulfur content of 0.5-4.5 wt%, and an animal or vegetable-derived fat or oil component with an oxygen content of 0.3-13 wt%, with a catalyst comprising one or more metals selected from among elements of Group 6A and Group 8 of the Periodic Table and a porous inorganic oxide containing at least aluminum oxide, in the presence of hydrogen. [0007] The hydrotreating process of the invention can stably maintain deoxygenation activity and desulfurization activity during hydrotreating. This is because the hydrotreating is carried out by contacting a prescribed catalyst with a mixture of an animal or vegetable-derived fat or oil component containing 0.3-13 wt% oxygen and a petroleum-based hydrocarbon having the properties described above, as the oil to be treated. [0008] For the hydrotreating process of the invention, the proportion of compounds with a triglyceride structure in the animal and vegetable-derived fat and oil components is preferably 80 mol% or greater. This will allow reduction in the energy required for processing of the starting materials. Also, the petroleum hydrocarbon fraction preferably has a nitrogen content of 400-1800 ppm by weight, and a basic nitrogen content of 180-600 ppm by weight. This will maintain stable long-term deoxygenation activity and desulfurization activity for hydrotreating. [0009] The porous inorganic oxide used for the invention preferably comprises one or more elements selected from among silicon, boron, phosphorus, titanium and zirconium, with aluminum oxide. The metals selected from among elements of Group 6A and Group 8 of the Periodic Table are preferably two or more metals selected from among cobalt, molybdenum, nickel and tungsten, with the metals being supported on the porous inorganic oxide. [0010] According to the invention, the oil to be treated and the catalyst are preferably contacted under conditions with a hydrogen pressure of 5-20 MPa, a liquid space velocity of 0.1-2.2 h"1 and a hydrogen/oil ratio of 300-1500 NL/L. [0011] The hydrotreated oil of the invention is produced by the hydrotreating process of the invention as described above. The hydrotreated oil may be suitably used, for example, as a stock oil for catalytic cracking or a stock oil for hydrocracking. [0012] The light oil fraction base for the invention is a hydrotreated oil according to the invention, and it contains a hydrotreated oil with a boiling point of 260-300°C. The sulfur content of the light oil fraction base is preferably no greater than 15 ppm by weight, and the oxygen content is preferably no greater than 0.5 wt%. [0013] The stock oil for catalytic cracking according to the invention contains a hydrotreated oil according to the invention, and has a sulfur content of no greater than 0.1 wt% and an oxygen content of no greater than 1 wt%. [0014] The stock oil for hydrocracking according to the invention contains a hydrotreated oil according to the invention, and has a sulfur content of no greater than 0.1 wt% and an oxygen content of no greater than 1 wt%. Effect of the Invention [0015] According to the invention there is provided a hydrotreating process that can economically and very effectively produce hydrotreated oil having both adequately reduced oxygen and sulfur contents, when applied to an oil to be treated which contains an animal or vegetable-derived fat or oil component and a petroleum hydrocarbon fraction. The invention further provides a hydrotreated oil obtained by the aforementioned hydrotreating process. Brief Description of the Drawings [0016] Fig. 1 is a flow chart showing an example of a preferred embodiment of a hydrotreating apparatus for a hydrotreating process according to the invention. Fig. 2 is a flow chart showing another example of a preferred embodiment of a hydrotreating apparatus for a hydrotreating process according to the invention. Explanations of Numerals [0017] 10,20,30: reaction column, 50: distillation column, 12,22,32: hydrotreating catalyst layer, 100,200: hydrotreating apparatus. Best Modes for Carrying Out the Invention [0018] Preferred modes of the invention will now be explained. [0019] According to the invention, the oil to be treated is a mixture of an animal or vegetable-derived fat or oil component having an oxygen content of 0.3-13 wt%, and a petroleum hydrocarbon fraction having a sulfur content of 0.5-4.5 wt% and including fractions with boiling points of 300°C and higher. The oil to be treated must be a hydrocarbon containing an animal or vegetable-derived fat or oil component. The concept of animal or vegetable-derived fat or oil components according to the invention encompasses not only naturally and artificially produced animal and vegetable oils, but also fat and oil components produced using such animal and vegetable fats and oils as starting materials. The fat and oil components used for the invention may also contain additives included to maintain and improve the quality and performance of various fat and oil products. [0020] As examples of animal and vegetable-derived fat and oil components there may be mentioned beef tallow, rapeseed oil, soybean oil, palm oil and the like. The animal or vegetable-derived fat and oil components according to the invention may be from any fats or oils, and may even be waste oil from use of the fats or oils. From the standpoint of carbon neutrality, however, they are preferably vegetable fats or oils, and from the viewpoint of fatty acid alkyl chain carbon number and reactivity, rapeseed oil, soybean oil and palm oil are more preferred. Any of the above-mentioned fats and oils may be used alone, or two or more thereof may be used in admixture. [0021] Animal and vegetable-derived fat and oil components have a general fatty acid triglyceride structure, but they may also include fat and oil components processed to other fatty acids or esters such as fatty acid methyl esters. However, since production of fatty acids or fatty acid esters from vegetable fats and oils generates carbon dioxide, the vegetable fats or oils are preferably composed mainly of components with a triglyceride structure, from the viewpoint of reducing carbon dioxide emission. According to the invention, the proportion of compounds with a triglyceride structure in the animal and vegetable-derived fat and oil components is preferably 80 mol% or greater, more preferably 85 mol% or greater and even more preferably 90 mol% or greater. [0022] The animal and vegetable-derived fat and oil components contain oxygen at 0.3-13 wt% based on the weight of the fat and oil components, but the oxygen content is preferably 0.3-12 wt% and more preferably 0.5-11 wt%. If the oxygen content is less than 0.3 wt% it will be difficult to stably maintain the deoxygenation activity and desulfurization activity. On the other hand, an oxygen content exceeding 13 wt% will create a need for equipment to treat the water by-product. In addition, excessive interaction between the water and catalyst carrier may lower the activity or reduce the catalyst strength. The oxygen content may be measured with an ordinary elemental analyzer, and for example, a sample may be converted to carbon monoxide on platinum-carbon, or it may be converted to carbon dioxide and then measurement performed using a thermal conductivity detector. [0023] The petroleum hydrocarbon fraction used may be a fraction obtained by an ordinary petroleum refining step. For example, a fraction corresponding to a prescribed boiling point range, obtained from an atmospheric distillation apparatus or vacuum distillation apparatus, may be used. Alternatively, the fraction corresponding to a prescribed boiling point range, obtained from a hydrodesulfurization, hydrocracking, residue hydrodesulfurization, fluidized catalytic cracking or the like, may be used. Fractions obtained from any of the above-mentioned apparatuses may be used alone, or two or more thereof may be used in admixture. [0024] The petroleum hydrocarbon fraction includes fractions with boiling points of 300°C and higher, but preferably it does not include heavy fractions with boiling points exceeding 700°C. If the petroleum hydrocarbon fraction does not include fractions with boiling points of 300°C and higher, it will be difficult to achieve a satisfactory yield due to excessive decomposition. On the other hand, if it includes heavy fractions with boiling points of higher than 700°C, catalyst-mediated deposition of carbon will accelerate due to the heavy components, thus tending to reduce the activity. The boiling point range according to the invention is the value measured according to the method described in JIS K 2254, "Distillation Test Method" or ASTM-D86. [0025] The petroleum hydrocarbon fraction has a sulfur content of 0.5-4.5 wt% based on the weight of the fraction, but the sulfur content is preferably 1.0-3.0 wt%. A sulfur content of less than 0.5 wt% will lead to imbalance between the deoxygenation and desulfurization reactions, and increase hydrogen consumption due to over-hydrogenation. On the other hand, a sulfur content of greater than 4.5 wt% will make it difficult to lower the sulfur content of the obtained hydrotreated oil to the prescribed level. The sulfur content according to the invention is the sulfur content by weight as measured according to the method described in JIS K 2541, "Sulfur Content Test Method" or ASTM-D5453. [0026] According to the invention, the nitrogen content of the petroleum hydrocarbon fraction is preferably within a prescribed range. This will maintain stable long-term deoxygenation activity and desulfurization activity. While the mechanism by which deoxygenation activity and desulfurization activity are stably maintained for prolonged periods when the nitrogen content is within the specified range is not understood in detail, it is conjectured that the nitrogen, oxygen and sulfur interact in such a manner that activity is maintained. The range for the nitrogen content in the petroleum hydrocarbon fraction is preferably 400-1800 ppm by weight, more preferably 400-1200 ppm by weight and even more preferably 400-800 ppm by weight. A nitrogen content of less than 400 ppm by weight will tend to make it difficult to maintain stable deoxygenation and desulfurization activity. If the nitrogen content is greater than 1800 ppm by weight, the nitrogen will interfere with the active site of the catalyst, tending to prevent sufficient deoxygenation and desulfurization activity from being achieved. [0027] According to the invention, the basic nitrogen content of the petroleum hydrocarbon fraction is also preferably within a prescribed range. This will maintain stable long-term deoxygenation activity and desulfurization activity. The range for the basic nitrogen content in the petroleum hydrocarbon fraction is preferably 180-600 ppm by weight, more preferably 180-500 ppm by weight and even more preferably 180-400 ppm by weight. If the basic nitrogen content is less than 180 ppm by weight, the oxidation site on the catalyst will become destabilized, tending to lower the deoxygenation and desulfurization activity. If the basic nitrogen content is greater than 600 ppm by weight, the basic nitrogen will interfere with the active site of the catalyst, tending to prevent sufficient deoxygenation and desulfurization activity from being achieved. [0028] The nitrogen content is the value measured according to the method described in JIS K 2609, "Crude Oil and Petroleum Products -Nitrogen Content Test Method". The basic nitrogen content can be determined by titration using an perchloric acid-acetic acid solution or the like, and for example, it may be determined according to the method described in UOP 269-70T. [0029] There are no particular restrictions on the mixing ratio of the animal or vegetable-derived fat or oil component and the petroleum hydrocarbon fraction in the oil to be treated, but the mixing ratio of the animal or vegetable-derived fat or oil component with respect to the total volume of the oil to be treated is preferably no greater than 80 vol%, more preferably no greater than 60 vol% and even more preferably no greater than 40 vol%. If the mixing ratio of the animal or vegetable-derived fat or oil component exceeds 80 vol%, the amount of water by-product will increase, tending to lower the deoxygenation activity and desulfurization activity. From the viewpoint of stably maintaining the deoxygenation and desulfurization activity, the mixing ratio of the animal or vegetable-derived fat or oil component with respect to the total volume of the oil to be treated is preferably at least 1 vol%, more preferably at least 5 vol% and even more preferably at least 10 vol%. [0030] The hydrotreating conditions are preferably a hydrogen pressure of 5-20 MPa, a liquid space velocity (LHSV) of 0.1-2.2 h"1 and a hydrogen/oil ratio (hydrogen-to-oil ratio) of 300-1500 NL/L, more preferably a hydrogen pressure of 5.5-18 MPa, a space velocity of 0.2-2.0 h"1, and a hydrogen/oil ratio of 300-1500 NL/L, and even more preferably a hydrogen pressure of 6-15 MPa, a space velocity of 0.3-1.5 h"1 and a hydrogen/oil ratio of 350-1000 NL/L. These conditions are all factors affecting the reactivity, and for example, if the hydrogen pressure and hydrogen/oil ratio are not above the lower limits mentioned above, the reactivity may be reduced or the activity may rapidly decrease. On the other hand, if the hydrogen pressure and hydrogen/oil ratio are not below the upper limits mentioned above, it may be necessary to incur extra expense for a compressor or other equipment. A lower liquid space velocity will tend to favor the reaction, but if it is below the lower limit mentioned above it will become necessary to provide a reactor with a very large internal volume and extra expense for equipment may be necessary, while if the liquid space velocity exceeds the upper limit mentioned above, the reaction may not proceed to a sufficient degree. [0031] The form of reactor used may be a fixed bed system. Specifically, the system employed may be in a form with hydrogen in a countercurrent or cocurrent flow with respect to the oil to be treated. An ordinary type of reactor, such as a gas-liquid cocurrent flow system reactor wherein the oil to be treated and hydrogen circulate from the top down, may be employed. The reactor may be a single one or a combination of different reactors. For example, a construction may be employed wherein the interior of one reactor is partitioned into a plurality of reaction beds, or a plurality of reactors may be used as a system with a combination of countercurrent and cocurrent flows. [0032] The hydrotreated oil which has been hydrotreated in the reactor is then subjected to gas-liquid separation and rectification steps for fractionation into hydrotreated oil comprising the prescribed fractions. For example, the hydrotreated oil may be fractionated into a light oil fraction or residual fraction and then, if necessary, fractionated into gas, a naphtha fraction and a kerosene fraction. Reaction of the oxygen and sulfur in the oil to be treated may generate water or hydrogen sulfide. In order to remove such by-products, gas-liquid separation equipment or other by-product gas removal equipment may be installed between a plurality of reactors or product recovery means. [0033] Hydrogen gas is usually introduced through the inlet port of the first reactor together with the oil to be treated either before or after the heating furnace, but hydrogen gas may also be introduced between catalytic beds or between multiple reactors, in order to control the temperature in the reactor while maintaining hydrogen pressure throughout the entire reactor. Hydrogen introduced in this manner is generally referred to as "quench hydrogen". The proportion of quench hydrogen with respect to hydrogen gas introduced together with the oil to be treated is preferably 10-60 vol% and more preferably 15-50 vol%. If the proportion of quench hydrogen is less than 10 vol% the reaction may not proceed sufficiently at the reaction site in the subsequent steps, and if the proportion of quench hydrogen is greater than 60 vol%, the reaction may not proceed sufficiently near the reaction inlet port. [0034] The reaction temperature may be set as desired according to the intended degree of desulfurization. The average temperature of the reactor as a whole will generally be in the range of 330-480°C, but it is preferably set in the range of 350-450°C and more preferably 360-430°C. If the average temperature of the reactor as a whole is below 330°C the reaction may not proceed sufficiently, while if it is above 480°C, catalyst-mediated deposition of carbon will accelerate as a result of polycondensation reaction, thus tending to reduce the activity. [0035] The active metal of the hydrotreating catalyst is at least one type of metal selected from among elements of Group 6A and Group 8 of the Periodic Table, but among these elements, it is preferably two or more metals selected from among cobalt, molybdenum, nickel and tungsten. As an example of a preferred combination, there may be mentioned cobalt-molybdenum, nickel-molybdenum, nickel-cobalt-molybdenum and nickel-tungsten. More preferred combinations are nickel-molybdenum, nickel-cobalt-molybdenum and nickel-tungsten. These metals are converted to sulfides for use during the hydrotreating. [0036] The carrier used for the hydrotreating catalyst may be a porous inorganic oxide, and particularly preferred for use are porous inorganic oxides composed mainly of aluminum oxide. The porous inorganic oxide is a complex oxide including one or more elements selected from among silicon, boron, phosphorus, titanium and zirconium, as components other than aluminum. The total content of components other than aluminum oxide is preferably 1-80 wt% and more preferably 2-70 wt% based on the carrier weight. If the total content of components other than aluminum oxide is less than 1 wt%, the catalyst surface area may be insufficient and the activity may be reduced. On the other hand, if the total content of components other than aluminum oxide exceeds 80 wt%, the carrier will be excessively acidic and the activity may be reduced due to coke production. When phosphorus is included as a constituent component of the carrier, its content (based on the carrier weight) is preferably 1-8 wt% and more preferably 2-5 wt% as oxides. [0037] There are no particular restrictions on the method by which silicon, boron, phosphorus, titanium and zirconium, as constituent components of the carrier in addition to aluminum oxide, are introduced into the carrier, and a solution containing the elements may be used as the starting material. For example, silicon may be used in the form of silicon, water glass, silica sol or the like. Boron may be used as boric acid or the like. Phosphorus may be used in the form of phosphoric acid or an alkali metal salt of phosphoric acid. Titanium may be used as titanium sulfide, titanium tetrachloride or various alkoxide salts. Zirconium may be used as zirconium sulfate or various alkoxide salts. [0038] The starting materials for the constituent components of the carrier other than aluminum oxide are preferably added during a step prior to firing of the carrier. For example, after adding the starting materials beforehand to an aluminum aqueous solution, an aluminum hydroxide gel containing the constituent components may be prepared therefrom, or the starting materials may be added to a prepared aluminum hydroxide gel. Alternatively, the starting materials may be added in a step in which water or an acidic aqueous solution is added to and kneaded with a commercially available aluminum oxide intermediate or boehmite powder. In this case, the aluminum oxide and starting materials for the constituent components of the carrier are preferably combined during the stage of preparing the aluminum hydroxide gel. While the mechanism by which the constituent components of the carrier other than aluminum oxide exhibit their effect is not fully understood, it is conjectured that they form complex oxides with aluminum, which results in increased carrier surface area and interaction with the active metal, thereby affecting the activity. [0039] The preferred ranges for the contents (loading weights) of active metals based on the catalyst weight are as follows. The range for the total loading weight of tungsten and molybdenum is preferably 12-35 wt% and more preferably 15-30 wt% as oxides. A total loading weight of tungsten and molybdenum of less than 12 wt% will tend to result in fewer active sites and prevent sufficient activity from being obtained. On the other hand, at greater than 35 wt% the metals will fail to efficiently disperse, also tending to result in insufficient activity. The range for the total loading weight of cobalt and nickel is preferably 1.5-18 wt% and more preferably 2-15 wt% as oxides. If the total loading weight of cobalt and nickel is less than 1.5 wt%, a sufficient cocatalyst effect may not be achieved and the activity may thus be reduced. On the other hand, at greater than 10 wt% the metals will fail to efficiently disperse, also tending to result in insufficient activity. [0040] There are no particular restrictions on the method of adding the active metals to the catalyst, and any publicly known method used for production of ordinary desulfurization catalysts may be applied. A method of impregnating the catalyst carrier with a solution containing salts of the active metals will usually be appropriate. Other suitable methods include the equilibrium adsorption, pore filling and incipient wetness methods. For example, the pore filling method involves first measuring the pore volume of the carrier and then impregnating it with an equal volume of the metal salt solution. The impregnation method is not particularly restricted, and may be a method that is suitable for the metal loading weight and the physical properties of the catalyst carrier. [0041] There is no restriction on the number of different hydrotreating catalysts used for the invention. For example, a single type of catalyst may be used alone, or a plurality of catalysts with different active metals or carrier constituent components may be used. As examples of suitable combinations when using a plurality of different catalysts, there may be mentioned using a catalyst containing cobalt-molybdenum after a catalyst containing nickel-molybdenum, using a catalyst containing nickel-cobalt-molybdenum after a catalyst containing nickel-molybdenum, using a catalyst containing nickel-cobalt-molybdenum after a catalyst containing nickel-tungsten and using a catalyst containing cobalt-molybdenum after a catalyst containing nickel-cobalt-molybdenum. A nickel-molybdenum catalyst may also be combined before and/or after these combinations. [0042] When using a combination of catalysts with different carrier components, a catalyst with an aluminum oxide content in the range of 80-99 wt% may be used after a catalyst with an aluminum oxide content of 30 wt% or greater and less than 80 wt% based on the total carrier weight. [0043] In addition, a guard catalyst, demetallizing catalyst or inert filler may be used if necessary in addition to the hydrotreating catalyst, for the purpose of trapping the scale portion flowing in with the oil to be treated, or supporting the hydrotreating catalyst in separated sections of the catalyst bed. These may be used either alone or in combinations. [0044] When a hydrotreated oil produced according to the invention is used as a light oil fraction base, the hydrotreated oil contains at least a fraction with a boiling point of 260-300°C, preferably with a sulfur content of no greater than 15 ppm by weight and an oxygen content of no greater than 0.5 wt%, and more preferably a sulfur content of no greater than 12 ppm by weight and an oxygen content of no greater than 0.3 wt%. If the sulfur and oxygen contents are above the aforementioned upper limits, this may adversely affect the filter or catalyst used in the diesel engine exhaust gas treatment apparatus, as well as the other materials of the engine. [0045] The hydrotreated oil described above may be used alone as a diesel light oil or heavy oil base, but it may instead be used as a diesel light oil or heavy oil base blended with other components of bases or the like. Other bases to be combined may include a light oil fraction and/or kerosene oil fraction obtained by an ordinary petroleum refining step, or the residual fraction obtained by the hydrotreating process of the invention. Also, a "synthetic gas" composed of hydrogen and carbon monoxide may be used as the starting material, blended with a synthetic light oil or synthetic kerosene oil obtained by a Fischer-Tropsch reaction or the like. These synthetic light oils or synthetic kerosene oils are characterized by containing virtually no aromatic components, being composed mainly of saturated hydrocarbons, and having high cetane numbers. The process for production of a synthetic gas may be any publicly known process and is not particularly restricted. [0046] The residual fraction obtained by the hydrotreating process of the invention has a sulfur content of no greater than 0.1 wt% and an oxygen content of no greater than 1 wt%, and may therefore be used as a low-sulfur heavy base. The residual fraction is also suitable as a stock oil for catalytic cracking. By supplying such a low-sulfur residual fraction to a catalytic cracker, it is possible to produce low-sulfur gasoline bases or other fuel oil bases. The residual fraction may also be used as a stock oil for hydrocracking. By supplying such a residual fraction to a hydrocracker, it is possible to achieve improved cracking activity and higher quality properties for each fraction of the product oil. [0047] A hydrotreating apparatus used for the hydrotreating process of the invention will now be described. Fig. 1 is a flow chart showing an example of a hydrotreating apparatus suitable for carrying out the hydrotreating process of the invention. The reaction column 10 of the hydrotreating apparatus 100 shown in Fig. 1 is a fixed bed reaction column, and a hydrotreating catalyst layer 12 is provided inside it. At the top of the reaction column 10 there is connected a line L1 for supply of the oil to be treated into the reaction column 10, while a line L2 is connected upstream from the connection of line L1 with the reaction column 10 for supply of hydrogen. Also, at the bottom of the reaction column 10 there is connected a line L3 for removal of reaction product from the reaction column 10, with the other end of the line L3 connected to an ordinary pressure distilling apparatus 40. [0048] The distilling apparatus 40 is used for fractionation of the reaction product obtained by reaction in the reaction column 10 into separate fractions with specific boiling point ranges. The distilling apparatus 40 accomplishes fractionation into, for example, a gas fraction, naphtha fraction, kerosene fraction, light oil fraction and wax fraction. Each fraction fractionated in the distilling apparatus 40 is transported to subsequent processes by lines (L4-L8) connected to the distilling apparatus 40. [0049] Fig. 2 is a flow chart showing another example of a hydrotreating apparatus suitable for carrying out the hydrotreating process of the invention. The hydrotreating apparatus 200 shown in Fig. 2 has the same construction as the hydrotreating apparatus 100, except that instead of the reaction column 10 of the hydrotreating apparatus 100 there are provided two reaction columns 20 and 30 connected in series via a transport line L9. A line L2a is connected upstream from the connection of line L9 with the reaction column 30 for supply of hydrogen. [0050] At the hydrotreating apparatus 200, the interior of the reaction column 20 includes a hydrotreating catalyst layer 22, and the interior of the reaction column 30 includes a hydrotreating catalyst layer 32. The hydrotreating catalysts of the hydrotreating catalyst layer 22 and hydrotreating catalyst layer 32 may be the same or different. The hydrotreating treatment is carried out by these two reaction columns 20,30. Examples [0051] The present invention will now be explained in greater detail through examples and comparative examples, with the understanding that the invention is in no way limited to these examples. [0052] (Catalyst preparation) After adding 18.0 g of water glass No.3 to 3000 g of a 5 wt% sodium aluminate aqueous solution in a vessel, the mixture was adjusted to a vessel content temperature of 65°C. Separately, 6.0 g of phosphoric acid (85% concentration) was added to 3000 g of an aluminum sulfate aqueous solution (2.5 wt% concentration) in a different vessel, and the mixture was adjusted to a vessel content temperature of 65°C. The solution containing the sodium aluminate and water glass was then added dropwise to the solution containing aluminum sulfate and phosphoric acid. The end point was defined as the time at which the pH of the mixture reached 7.0, and the obtained slurry product was filtered through a filter to obtain a cake-like slurry. [0053] The cake-like slurry was transferred to a vessel equipped with a reflux condenser, and then 150 ml of distilled water and 10 g of a 27% ammonia water solution were added and the mixture was heated and stirred at 80°C for 24 hours. Next, the slurry was placed in a kneader and heated to above 80°C, and kneading was performed while removing the moisture to obtain a clay-like kneaded blend. The obtained kneaded blend was extruded into a 1.5 mm diameter cylinder form using an extruder, and after drying at 110°C for 1 hour, it was fired at 550°C to obtain a molded carrier. [0054] After placing 50 g of the obtained molded carrier into a round-bottomed flask, an impregnating solution containing 14.8 g of molybdenum trioxide, 25.8 g of nickel(II) nitrate hexahydrate, 2.9 g of phosphoric acid (85% concentration) and 4.0 g of malic acid was poured into the flask while deairing with a rotary evaporator. The impregnated sample was dried at 120°C for 1 hour and then fired at 550°C to obtain catalyst A. The physical properties of the prepared catalyst A are shown in Table 1. [0055] After adding 300 g of water glass No.3 to 3000 g of a 5 wt% sodium aluminate aqueous solution in a vessel, the mixture was adjusted to a vessel content temperature of 65°C. Separately, 3000 g of an aluminum sulfate aqueous solution (2.5 wt% concentration) was prepared in a different vessel, and the mixture was adjusted to a vessel content temperature of 65°C. The solution containing the sodium aluminate and water glass was then added dropwise to the obtained aluminum sulfate aqueous solution. The end point was defined as the time at which the pH of the mixture reached 7.0, and the obtained slurry product was filtered through a filter to obtain a cake-like slurry. [0056] The cake-like slurry was transferred to a vessel equipped with a reflux condenser, and then 150 ml of distilled water and 10 g of a 27% ammonia water solution were added and the mixture was heated and stirred at 80°C for 24 hours. The slurry was then placed in a kneader and heated to above 80°C, and kneading was performed while removing the moisture to obtain a clay-like kneaded blend. The obtained kneaded blend was extruded into a 1.5 mm diameter cylinder form using an extruder, and after drying at 110°C for 1 hour, it was fired at 550°C to obtain a molded carrier. [0057] After placing 50 g of the obtained molded carrier into a round-bottomed flask, an impregnating solution containing 16.1 g of ammonium paratungstate pentahydrate, 52.4 g of nickel(II) nitrate hexahydrate and 2.0 g of phosphoric acid (85% concentration) was poured into the flask while deairing with a rotary evaporator. The impregnated sample was dried at 120°C for 1 hour, and then fired at 550°C to obtain catalyst B. The physical properties of the prepared catalyst B are shown in Table 1. [0058] After placing 50 g of the molded carrier used to prepare catalyst A into a round-bottomed flask, an impregnating solution containing 14.8 g of molybdenum trioxide, 7.6 g of nickel(II) nitrate hexahydrate, 2.9 g of phosphoric acid (85% concentration) and 4.0 g of malic acid was poured into the flask while deairing with a rotary evaporator. The impregnated sample was dried at 120°C for 1 hour, and then fired at 550°C to obtain catalyst C. The physical properties of the prepared catalyst C are shown in Table 1. [Table 1] (Table Removed) [0059] (Example 1) An apparatus having the same construction as the hydrotreating apparatus 200 shown in Fig. 2 was used for hydrotreating of an oil to be treated. A first reaction tube (inner diameter: 20 mm) packed with catalyst A (50 ml) and a second reaction tube (inner diameter: 20 mm) packed with the same catalyst A (50 ml) were installed in series in a fixed bed flow type reactor. Next, straight-run light oil (3 wt% sulfur content) containing added dimethyl disulfide was used for pre-sulfurization of the catalyst for 4 hours under conditions with a catalyst layer average temperature of 300°C, a hydrogen partial pressure of 6 MPa, LHSV = 1 h-1 and a hydrogen/oil ratio of 200 NL/L. [0060] After pre-sulfurization, hydrotreating was carried out using a blended oil as an oil to be treated comprising the palm oil specified below and a Middle East vacuum light oil fraction in a volume ratio of 20:80 (hereinafter referred to as "blended oil 1"). Palm oil: 15°C density = 0.916 g/ml, oxygen content =11.4 wt%; Middle East vacuum light oil fraction: 15°C density = 0.919 g/ml, sulfur content = 2.41 wt%, nitrogen content = 610 ppm by weight, basic nitrogen content = 240 ppm by weight, initial boiling point = 285°C, end point = 540°C. [0061] The blended oil 1 and hydrogen were introduced into the reactor from the first reaction tube end in a manner causing the treated fluid to pass through the first reaction tube and second reaction tube in that order. The hydrotreating conditions were a reaction temperature of 390°C in the first and second reaction tubes, 7.0 MPa pressure, LHSV = 0.6 h" . The volume ratio (quench hydrogen proportion) of hydrogen gas introduced between the first reaction tube and second reaction tube was 20 vol% of the total hydrogen introduced, and the hydrogen/oil ratio was 430 NL/L as determined based on the total hydrogen introduced. The reaction conditions are shown in Table 2, and the test results are shown in Table 3. [0062] (Example 2) Hydrotreating was carried out in the same manner as Example 1, except that a first reaction tube (inner diameter: 20 mm) packed with catalyst A (50 ml) and a second reaction tube (inner diameter: 20 mm) packed with catalyst C (50 ml) were installed in series in a fixed bed flow type reactor. The reaction conditions are shown in Table 2, and the test results are shown in Table 3. [0063] (Example 3) Hydrotreating was carried out in the same manner as Example 1, except that a first reaction tube (inner diameter: 20 mm) packed with catalyst B (30 ml) and a second reaction tube (inner diameter: 20 mm) packed with catalyst C (70 ml) were installed in series in a fixed bed flow type reactor. The reaction conditions are shown in Table 2, and the test results are shown in Table 3. [0064] (Example 4) Hydrotreating was carried out in the same manner as Example 1, except that the oil to be treated was a blended oil comprising the palm oil used in Example 1 and the vacuum light oil fraction specified below in a volume ratio of 20:80 (hereinafter, "blended oil 2"). The reaction conditions are shown in Table 2, and the test results are shown in Table 3. Vacuum light oil fraction: 15°C density = 0.910 g/ml, sulfur content = 2.10 wt%, nitrogen content = 360 ppm by weight, basic nitrogen content = 140 ppm by weight, initial boiling point = 270°C, end point = 536°C. [0065] (Example 5) Hydrotreating was carried out in the same manner as Example 3, except that the total Volume of hydrogen gas was introduced together with the oil to be treated (quench hydrogen proportion = 0%) without introduction between the first reaction tube and second reaction tube. The reaction conditions are shown in Table 2, and the test results are shown in Table 3. [0066] (Comparative Example 1) Hydrotreating was carried out in the same manner as Example 1, except that the oil to be treated was not a blended oil, but consisted only of the Middle East vacuum light oil fraction used in Example 1. The reaction conditions are shown in Table 2, and the test results are shown in Table 3. [Table 2] [Table 3] (Table Removed) Industrial Applicability [0067] According to the invention there is provided a hydrotreating process which allows economical and highly efficient production of hydrotreated oil with satisfactorily reduced oxygen and sulfur contents, when the oil to be treated comprises an animal or vegetable-derived fat or oil component and a petroleum hydrocarbon fraction. The invention also provides a hydrotreated oil obtained by the hydrotreating process. CLAIMS 1. A hydrotreating process characterized by contacting an oil to be treated comprising a petroleum hydrocarbon fraction including fractions with boiling points of 300°C and higher and having a sulfur content of 0.5-4.5 wt%, and an animal or vegetable-derived fat or oil component with an oxygen content of 0.3-13 wt%, with a catalyst comprising one or more metals selected from among elements of Group 6A and Group 8 of the Periodic Table and a porous inorganic oxide containing at least aluminum oxide, in the presence of hydrogen. 2. A hydrotreating process according to claim 1, wherein the proportion of compounds with a triglyceride structure among the fat and oil components is 80 mol?/o or greater. 3. A hydrotreating process according to claim 1 or 2, wherein the petroleum hydrocarbon fraction contains nitrogen at 400-1800 ppm by weight. 4. A hydrotreating process according to any one of claims 1 to 3, wherein the petroleum hydrocarbon fraction contains basic nitrogen at 180-600 ppm by weight. 5. A hydrotreating process according to any one of claims 1 to 4, wherein the porous inorganic oxide comprises aluminum oxide and one or more elements selected from among silicon, boron, phosphorus, titanium and zirconium, and the metal consists of two or more metals selected from among cobalt, molybdenum, nickel and tungsten, with the metal supported on the porous inorganic oxide. 6. A hydrotreating process according to any one of claims 1 to 5, wherein the oil to be treated and the catalyst are contacted under conditions with a hydrogen pressure of 5-20 MPa, a liquid space velocity of 0.1-2.2 h-1 and a hydrogen/oil ratio of 300-1500 NL/L. 7. A hydrotreated oil which is produced by a hydrotreating process according to any one of claims 1 to 6. 8. A light oil fraction base comprising a hydrotreated oil according to claim 7, wherein the hydrotreated oil has a boiling point of 260-300°C. 9. A right oil fraction base according to claim 8, wherein the light oil fraction base has a sulfur content of no greater than 15 ppm by weight and an oxygen content of no greater than 0.5 wt%. 10. A stock oil for catalytic cracking comprising a hydrotreated oil according to claim 7, wherein the stock oil for catalytic cracking has a sulfur content of no greater than 0.1 wt% and an oxygen content of no greater than 1 wt%. 11. A stock oil for hydrocracking comprising a hydrotreated oil according to claim 7, wherein the stock oil for hydrocracking has a sulfur content of no greater than 0.1 wt% and an oxygen content of no greater than 1 wt%.

Full Text

DESCRIPTION
Hydrorefming Process and Hydrorefined Oil Technical Field
[0001] The present invention relates to a hydrotreating process, and more specifically it relates to a hydrotreating process for oil to be treated that contains fat and oil components derived from animal and vegetable oils. The invention further relates to a hydrotreated oil produced by the aforementioned hydrotreating process. Background Art
[0002] Effective utilization of biomass energy is a topic of increasing interest, as a strategy for preventing global warming. Notably, plant-derived biomass energy is "carbon neutral" because it allows effective utilization of the hydrocarbons converted from carbon dioxide by photosynthesis during the process of plant growth so that, considering natural life cycles, it does not contribute to increased carbon dioxide in the atmosphere.
[0003] Utilization of this type of biomass energy has also been extensively researched in the field of transportation fuels. For example, if fuels produced from animal and vegetable oils could be used as diesel fuels, the synergistic effect obtained with the high energy efficiency of a diesel engine would be expected to contribute substantially to carbon dioxide emission reduction. Known diesel fuels utilizing fat and oil components derived from animal or vegetable oils include fatty acid methyl ester oils. Fatty acid methyl ester oils are produced by alkali-mediated transesterification with methanol on a triglyceride structure, which is the general structure for fat and oil
components derived from animal and vegetable oils. However, as described in Patent document 1 mentioned below, the process of producing fatty acid methyl ester oils necessitates treatment of the glycerin by-product, or requires cost and energy for purification of the product oil.
[Patent document 1]: Japanese Unexamined Patent Publication No. 2005-154647
Disclosure of the Invention Problem to be Solved by the Invention
[0004] Other problems, in addition to those mentioned above, are associated with the use of animal and vegetable-derived fat and oil components or fuels produced using them as starting materials, for diesel fuels. First, animal and vegetable-derived fat and oil components generally have oxygen atoms in the molecule, and the oxygen can adversely affect the engine materials. Moreover, it is generally difficult to remove oxygen to extremely low concentrations. Also, when an animal or vegetable-derived fat or oil component is used in combination with a petroleum hydrocarbon fraction, current technology has not allowed sufficient reduction of both oxygen in the fat and oil component and sulfur in the petroleum hydrocarbon fraction. [0005] It is therefore an object of the present invention to provide a hydrotreating process that can economically and very effectively produce hydrotreated oil having adequately reduced oxygen and sulfur contents, when applied to an oil to be treated which contains an animal or vegetable-derived fat or oil component and a petroleum hydrocarbon fraction. It is another object of the invention to provide a hydrotreated
oil obtained by the aforementioned hydrotreating process. Means for Solving the Problem
[0006] The hydrotreating process of the invention is characterized by contacting an oil to be treated comprising a petroleum hydrocarbon fraction including fractions with boiling points of 300°C and higher and having a sulfur content of 0.5-4.5 wt%, and an animal or vegetable-derived fat or oil component with an oxygen content of 0.3-13 wt%, with a catalyst comprising one or more metals selected from among elements of Group 6A and Group 8 of the Periodic Table and a porous inorganic oxide containing at least aluminum oxide, in the presence of hydrogen.
[0007] The hydrotreating process of the invention can stably maintain deoxygenation activity and desulfurization activity during hydrotreating. This is because the hydrotreating is carried out by contacting a prescribed catalyst with a mixture of an animal or vegetable-derived fat or oil component containing 0.3-13 wt% oxygen and a petroleum-based hydrocarbon having the properties described above, as the oil to be treated.
[0008] For the hydrotreating process of the invention, the proportion of compounds with a triglyceride structure in the animal and vegetable-derived fat and oil components is preferably 80 mol% or greater. This will allow reduction in the energy required for processing of the starting materials. Also, the petroleum hydrocarbon fraction preferably has a nitrogen content of 400-1800 ppm by weight, and a basic nitrogen content of 180-600 ppm by weight. This will maintain stable long-term deoxygenation activity and desulfurization activity for
hydrotreating.
[0009] The porous inorganic oxide used for the invention preferably
comprises one or more elements selected from among silicon, boron,
phosphorus, titanium and zirconium, with aluminum oxide. The
metals selected from among elements of Group 6A and Group 8 of the
Periodic Table are preferably two or more metals selected from among
cobalt, molybdenum, nickel and tungsten, with the metals being
supported on the porous inorganic oxide.
[0010] According to the invention, the oil to be treated and the catalyst
are preferably contacted under conditions with a hydrogen pressure of
5-20 MPa, a liquid space velocity of 0.1-2.2 h"1 and a hydrogen/oil ratio
of 300-1500 NL/L.
[0011] The hydrotreated oil of the invention is produced by the
hydrotreating process of the invention as described above. The
hydrotreated oil may be suitably used, for example, as a stock oil for
catalytic cracking or a stock oil for hydrocracking.
[0012] The light oil fraction base for the invention is a hydrotreated oil
according to the invention, and it contains a hydrotreated oil with a
boiling point of 260-300°C. The sulfur content of the light oil fraction
base is preferably no greater than 15 ppm by weight, and the oxygen
content is preferably no greater than 0.5 wt%.
[0013] The stock oil for catalytic cracking according to the invention
contains a hydrotreated oil according to the invention, and has a sulfur
content of no greater than 0.1 wt% and an oxygen content of no greater
than 1 wt%.
[0014] The stock oil for hydrocracking according to the invention
contains a hydrotreated oil according to the invention, and has a sulfur content of no greater than 0.1 wt% and an oxygen content of no greater than 1 wt%. Effect of the Invention
[0015] According to the invention there is provided a hydrotreating process that can economically and very effectively produce hydrotreated oil having both adequately reduced oxygen and sulfur contents, when applied to an oil to be treated which contains an animal or vegetable-derived fat or oil component and a petroleum hydrocarbon fraction. The invention further provides a hydrotreated oil obtained by the aforementioned hydrotreating process. Brief Description of the Drawings
[0016] Fig. 1 is a flow chart showing an example of a preferred embodiment of a hydrotreating apparatus for a hydrotreating process according to the invention.
Fig. 2 is a flow chart showing another example of a preferred embodiment of a hydrotreating apparatus for a hydrotreating process according to the invention. Explanations of Numerals
[0017] 10,20,30: reaction column, 50: distillation column, 12,22,32: hydrotreating catalyst layer, 100,200: hydrotreating apparatus. Best Modes for Carrying Out the Invention [0018] Preferred modes of the invention will now be explained. [0019] According to the invention, the oil to be treated is a mixture of an animal or vegetable-derived fat or oil component having an oxygen content of 0.3-13 wt%, and a petroleum hydrocarbon fraction having a
sulfur content of 0.5-4.5 wt% and including fractions with boiling points of 300°C and higher. The oil to be treated must be a hydrocarbon containing an animal or vegetable-derived fat or oil component. The concept of animal or vegetable-derived fat or oil components according to the invention encompasses not only naturally and artificially produced animal and vegetable oils, but also fat and oil components produced using such animal and vegetable fats and oils as starting materials. The fat and oil components used for the invention may also contain additives included to maintain and improve the quality and performance of various fat and oil products.
[0020] As examples of animal and vegetable-derived fat and oil components there may be mentioned beef tallow, rapeseed oil, soybean oil, palm oil and the like. The animal or vegetable-derived fat and oil components according to the invention may be from any fats or oils, and may even be waste oil from use of the fats or oils. From the standpoint of carbon neutrality, however, they are preferably vegetable fats or oils, and from the viewpoint of fatty acid alkyl chain carbon number and reactivity, rapeseed oil, soybean oil and palm oil are more preferred. Any of the above-mentioned fats and oils may be used alone, or two or more thereof may be used in admixture.
[0021] Animal and vegetable-derived fat and oil components have a general fatty acid triglyceride structure, but they may also include fat and oil components processed to other fatty acids or esters such as fatty acid methyl esters. However, since production of fatty acids or fatty acid esters from vegetable fats and oils generates carbon dioxide, the vegetable fats or oils are preferably composed mainly of components
with a triglyceride structure, from the viewpoint of reducing carbon dioxide emission. According to the invention, the proportion of compounds with a triglyceride structure in the animal and vegetable-derived fat and oil components is preferably 80 mol% or greater, more preferably 85 mol% or greater and even more preferably 90 mol% or greater.
[0022] The animal and vegetable-derived fat and oil components contain oxygen at 0.3-13 wt% based on the weight of the fat and oil components, but the oxygen content is preferably 0.3-12 wt% and more preferably 0.5-11 wt%. If the oxygen content is less than 0.3 wt% it will be difficult to stably maintain the deoxygenation activity and desulfurization activity. On the other hand, an oxygen content exceeding 13 wt% will create a need for equipment to treat the water by-product. In addition, excessive interaction between the water and catalyst carrier may lower the activity or reduce the catalyst strength. The oxygen content may be measured with an ordinary elemental analyzer, and for example, a sample may be converted to carbon monoxide on platinum-carbon, or it may be converted to carbon dioxide and then measurement performed using a thermal conductivity detector. [0023] The petroleum hydrocarbon fraction used may be a fraction obtained by an ordinary petroleum refining step. For example, a fraction corresponding to a prescribed boiling point range, obtained from an atmospheric distillation apparatus or vacuum distillation apparatus, may be used. Alternatively, the fraction corresponding to a prescribed boiling point range, obtained from a hydrodesulfurization, hydrocracking, residue hydrodesulfurization, fluidized catalytic
cracking or the like, may be used. Fractions obtained from any of the above-mentioned apparatuses may be used alone, or two or more thereof may be used in admixture.
[0024] The petroleum hydrocarbon fraction includes fractions with boiling points of 300°C and higher, but preferably it does not include heavy fractions with boiling points exceeding 700°C. If the petroleum hydrocarbon fraction does not include fractions with boiling points of 300°C and higher, it will be difficult to achieve a satisfactory yield due to excessive decomposition. On the other hand, if it includes heavy fractions with boiling points of higher than 700°C, catalyst-mediated deposition of carbon will accelerate due to the heavy components, thus tending to reduce the activity. The boiling point range according to the invention is the value measured according to the method described in JIS K 2254, "Distillation Test Method" or ASTM-D86. [0025] The petroleum hydrocarbon fraction has a sulfur content of 0.5-4.5 wt% based on the weight of the fraction, but the sulfur content is preferably 1.0-3.0 wt%. A sulfur content of less than 0.5 wt% will lead to imbalance between the deoxygenation and desulfurization reactions, and increase hydrogen consumption due to over-hydrogenation. On the other hand, a sulfur content of greater than 4.5 wt% will make it difficult to lower the sulfur content of the obtained hydrotreated oil to the prescribed level. The sulfur content according to the invention is the sulfur content by weight as measured according to the method described in JIS K 2541, "Sulfur Content Test Method" or ASTM-D5453. [0026] According to the invention, the nitrogen content of the
petroleum hydrocarbon fraction is preferably within a prescribed range.
This will maintain stable long-term deoxygenation activity and
desulfurization activity. While the mechanism by which
deoxygenation activity and desulfurization activity are stably maintained for prolonged periods when the nitrogen content is within the specified range is not understood in detail, it is conjectured that the nitrogen, oxygen and sulfur interact in such a manner that activity is maintained. The range for the nitrogen content in the petroleum hydrocarbon fraction is preferably 400-1800 ppm by weight, more preferably 400-1200 ppm by weight and even more preferably 400-800 ppm by weight. A nitrogen content of less than 400 ppm by weight will tend to make it difficult to maintain stable deoxygenation and desulfurization activity. If the nitrogen content is greater than 1800 ppm by weight, the nitrogen will interfere with the active site of the catalyst, tending to prevent sufficient deoxygenation and desulfurization activity from being achieved.
[0027] According to the invention, the basic nitrogen content of the petroleum hydrocarbon fraction is also preferably within a prescribed range. This will maintain stable long-term deoxygenation activity and desulfurization activity. The range for the basic nitrogen content in the petroleum hydrocarbon fraction is preferably 180-600 ppm by weight, more preferably 180-500 ppm by weight and even more preferably 180-400 ppm by weight. If the basic nitrogen content is less than 180 ppm by weight, the oxidation site on the catalyst will become destabilized, tending to lower the deoxygenation and desulfurization activity. If the basic nitrogen content is greater than 600 ppm by weight, the basic
nitrogen will interfere with the active site of the catalyst, tending to prevent sufficient deoxygenation and desulfurization activity from being achieved.
[0028] The nitrogen content is the value measured according to the method described in JIS K 2609, "Crude Oil and Petroleum Products -Nitrogen Content Test Method". The basic nitrogen content can be determined by titration using an perchloric acid-acetic acid solution or the like, and for example, it may be determined according to the method described in UOP 269-70T.
[0029] There are no particular restrictions on the mixing ratio of the animal or vegetable-derived fat or oil component and the petroleum hydrocarbon fraction in the oil to be treated, but the mixing ratio of the animal or vegetable-derived fat or oil component with respect to the total volume of the oil to be treated is preferably no greater than 80 vol%, more preferably no greater than 60 vol% and even more preferably no greater than 40 vol%. If the mixing ratio of the animal or vegetable-derived fat or oil component exceeds 80 vol%, the amount of water by-product will increase, tending to lower the deoxygenation activity and desulfurization activity. From the viewpoint of stably maintaining the deoxygenation and desulfurization activity, the mixing ratio of the animal or vegetable-derived fat or oil component with respect to the total volume of the oil to be treated is preferably at least 1 vol%, more preferably at least 5 vol% and even more preferably at least 10 vol%.
[0030] The hydrotreating conditions are preferably a hydrogen pressure of 5-20 MPa, a liquid space velocity (LHSV) of 0.1-2.2 h"1 and
a hydrogen/oil ratio (hydrogen-to-oil ratio) of 300-1500 NL/L, more preferably a hydrogen pressure of 5.5-18 MPa, a space velocity of 0.2-2.0 h"1, and a hydrogen/oil ratio of 300-1500 NL/L, and even more preferably a hydrogen pressure of 6-15 MPa, a space velocity of 0.3-1.5 h"1 and a hydrogen/oil ratio of 350-1000 NL/L. These conditions are all factors affecting the reactivity, and for example, if the hydrogen pressure and hydrogen/oil ratio are not above the lower limits mentioned above, the reactivity may be reduced or the activity may rapidly decrease. On the other hand, if the hydrogen pressure and hydrogen/oil ratio are not below the upper limits mentioned above, it may be necessary to incur extra expense for a compressor or other equipment. A lower liquid space velocity will tend to favor the reaction, but if it is below the lower limit mentioned above it will become necessary to provide a reactor with a very large internal volume and extra expense for equipment may be necessary, while if the liquid space velocity exceeds the upper limit mentioned above, the reaction may not proceed to a sufficient degree.
[0031] The form of reactor used may be a fixed bed system. Specifically, the system employed may be in a form with hydrogen in a countercurrent or cocurrent flow with respect to the oil to be treated. An ordinary type of reactor, such as a gas-liquid cocurrent flow system reactor wherein the oil to be treated and hydrogen circulate from the top down, may be employed. The reactor may be a single one or a combination of different reactors. For example, a construction may be employed wherein the interior of one reactor is partitioned into a plurality of reaction beds, or a plurality of reactors may be used as a
system with a combination of countercurrent and cocurrent flows. [0032] The hydrotreated oil which has been hydrotreated in the reactor is then subjected to gas-liquid separation and rectification steps for fractionation into hydrotreated oil comprising the prescribed fractions. For example, the hydrotreated oil may be fractionated into a light oil fraction or residual fraction and then, if necessary, fractionated into gas, a naphtha fraction and a kerosene fraction. Reaction of the oxygen and sulfur in the oil to be treated may generate water or hydrogen sulfide. In order to remove such by-products, gas-liquid separation equipment or other by-product gas removal equipment may be installed between a plurality of reactors or product recovery means.
[0033] Hydrogen gas is usually introduced through the inlet port of the first reactor together with the oil to be treated either before or after the heating furnace, but hydrogen gas may also be introduced between catalytic beds or between multiple reactors, in order to control the temperature in the reactor while maintaining hydrogen pressure throughout the entire reactor. Hydrogen introduced in this manner is generally referred to as "quench hydrogen". The proportion of quench hydrogen with respect to hydrogen gas introduced together with the oil to be treated is preferably 10-60 vol% and more preferably 15-50 vol%. If the proportion of quench hydrogen is less than 10 vol% the reaction may not proceed sufficiently at the reaction site in the subsequent steps, and if the proportion of quench hydrogen is greater than 60 vol%, the reaction may not proceed sufficiently near the reaction inlet port. [0034] The reaction temperature may be set as desired according to the intended degree of desulfurization. The average temperature of the
reactor as a whole will generally be in the range of 330-480°C, but it is preferably set in the range of 350-450°C and more preferably 360-430°C. If the average temperature of the reactor as a whole is below 330°C the reaction may not proceed sufficiently, while if it is above 480°C, catalyst-mediated deposition of carbon will accelerate as a result of polycondensation reaction, thus tending to reduce the activity. [0035] The active metal of the hydrotreating catalyst is at least one type of metal selected from among elements of Group 6A and Group 8 of the Periodic Table, but among these elements, it is preferably two or more metals selected from among cobalt, molybdenum, nickel and tungsten. As an example of a preferred combination, there may be mentioned cobalt-molybdenum, nickel-molybdenum, nickel-cobalt-molybdenum and nickel-tungsten. More preferred combinations are nickel-molybdenum, nickel-cobalt-molybdenum and nickel-tungsten. These metals are converted to sulfides for use during the hydrotreating. [0036] The carrier used for the hydrotreating catalyst may be a porous inorganic oxide, and particularly preferred for use are porous inorganic oxides composed mainly of aluminum oxide. The porous inorganic oxide is a complex oxide including one or more elements selected from among silicon, boron, phosphorus, titanium and zirconium, as components other than aluminum. The total content of components other than aluminum oxide is preferably 1-80 wt% and more preferably 2-70 wt% based on the carrier weight. If the total content of components other than aluminum oxide is less than 1 wt%, the catalyst surface area may be insufficient and the activity may be reduced. On the other hand, if the total content of components other than aluminum
oxide exceeds 80 wt%, the carrier will be excessively acidic and the activity may be reduced due to coke production. When phosphorus is included as a constituent component of the carrier, its content (based on the carrier weight) is preferably 1-8 wt% and more preferably 2-5 wt% as oxides.
[0037] There are no particular restrictions on the method by which silicon, boron, phosphorus, titanium and zirconium, as constituent components of the carrier in addition to aluminum oxide, are introduced into the carrier, and a solution containing the elements may be used as the starting material. For example, silicon may be used in the form of silicon, water glass, silica sol or the like. Boron may be used as boric acid or the like. Phosphorus may be used in the form of phosphoric acid or an alkali metal salt of phosphoric acid. Titanium may be used as titanium sulfide, titanium tetrachloride or various alkoxide salts. Zirconium may be used as zirconium sulfate or various alkoxide salts. [0038] The starting materials for the constituent components of the carrier other than aluminum oxide are preferably added during a step prior to firing of the carrier. For example, after adding the starting materials beforehand to an aluminum aqueous solution, an aluminum hydroxide gel containing the constituent components may be prepared therefrom, or the starting materials may be added to a prepared aluminum hydroxide gel. Alternatively, the starting materials may be added in a step in which water or an acidic aqueous solution is added to and kneaded with a commercially available aluminum oxide intermediate or boehmite powder. In this case, the aluminum oxide and starting materials for the constituent components of the carrier are
preferably combined during the stage of preparing the aluminum hydroxide gel. While the mechanism by which the constituent components of the carrier other than aluminum oxide exhibit their effect is not fully understood, it is conjectured that they form complex oxides with aluminum, which results in increased carrier surface area and interaction with the active metal, thereby affecting the activity. [0039] The preferred ranges for the contents (loading weights) of active metals based on the catalyst weight are as follows. The range for the total loading weight of tungsten and molybdenum is preferably 12-35 wt% and more preferably 15-30 wt% as oxides. A total loading weight of tungsten and molybdenum of less than 12 wt% will tend to result in fewer active sites and prevent sufficient activity from being obtained. On the other hand, at greater than 35 wt% the metals will fail to efficiently disperse, also tending to result in insufficient activity. The range for the total loading weight of cobalt and nickel is preferably 1.5-18 wt% and more preferably 2-15 wt% as oxides. If the total loading weight of cobalt and nickel is less than 1.5 wt%, a sufficient cocatalyst effect may not be achieved and the activity may thus be reduced. On the other hand, at greater than 10 wt% the metals will fail to efficiently disperse, also tending to result in insufficient activity. [0040] There are no particular restrictions on the method of adding the active metals to the catalyst, and any publicly known method used for production of ordinary desulfurization catalysts may be applied. A method of impregnating the catalyst carrier with a solution containing salts of the active metals will usually be appropriate. Other suitable methods include the equilibrium adsorption, pore filling and incipient
wetness methods. For example, the pore filling method involves first measuring the pore volume of the carrier and then impregnating it with an equal volume of the metal salt solution. The impregnation method is not particularly restricted, and may be a method that is suitable for the metal loading weight and the physical properties of the catalyst carrier. [0041] There is no restriction on the number of different hydrotreating catalysts used for the invention. For example, a single type of catalyst may be used alone, or a plurality of catalysts with different active metals or carrier constituent components may be used. As examples of suitable combinations when using a plurality of different catalysts, there may be mentioned using a catalyst containing cobalt-molybdenum after a catalyst containing nickel-molybdenum, using a catalyst containing nickel-cobalt-molybdenum after a catalyst containing nickel-molybdenum, using a catalyst containing nickel-cobalt-molybdenum after a catalyst containing nickel-tungsten and using a catalyst containing cobalt-molybdenum after a catalyst containing nickel-cobalt-molybdenum. A nickel-molybdenum catalyst may also be combined before and/or after these combinations.
[0042] When using a combination of catalysts with different carrier components, a catalyst with an aluminum oxide content in the range of 80-99 wt% may be used after a catalyst with an aluminum oxide content of 30 wt% or greater and less than 80 wt% based on the total carrier weight.
[0043] In addition, a guard catalyst, demetallizing catalyst or inert filler may be used if necessary in addition to the hydrotreating catalyst, for the purpose of trapping the scale portion flowing in with the oil to be
treated, or supporting the hydrotreating catalyst in separated sections of the catalyst bed. These may be used either alone or in combinations. [0044] When a hydrotreated oil produced according to the invention is used as a light oil fraction base, the hydrotreated oil contains at least a fraction with a boiling point of 260-300°C, preferably with a sulfur content of no greater than 15 ppm by weight and an oxygen content of no greater than 0.5 wt%, and more preferably a sulfur content of no greater than 12 ppm by weight and an oxygen content of no greater than 0.3 wt%. If the sulfur and oxygen contents are above the aforementioned upper limits, this may adversely affect the filter or catalyst used in the diesel engine exhaust gas treatment apparatus, as well as the other materials of the engine.
[0045] The hydrotreated oil described above may be used alone as a diesel light oil or heavy oil base, but it may instead be used as a diesel light oil or heavy oil base blended with other components of bases or the like. Other bases to be combined may include a light oil fraction and/or kerosene oil fraction obtained by an ordinary petroleum refining step, or the residual fraction obtained by the hydrotreating process of the invention. Also, a "synthetic gas" composed of hydrogen and carbon monoxide may be used as the starting material, blended with a synthetic light oil or synthetic kerosene oil obtained by a Fischer-Tropsch reaction or the like. These synthetic light oils or synthetic kerosene oils are characterized by containing virtually no aromatic components, being composed mainly of saturated hydrocarbons, and having high cetane numbers. The process for production of a synthetic gas may be any publicly known process and is not particularly restricted.
[0046] The residual fraction obtained by the hydrotreating process of the invention has a sulfur content of no greater than 0.1 wt% and an oxygen content of no greater than 1 wt%, and may therefore be used as a low-sulfur heavy base. The residual fraction is also suitable as a stock oil for catalytic cracking. By supplying such a low-sulfur residual fraction to a catalytic cracker, it is possible to produce low-sulfur gasoline bases or other fuel oil bases. The residual fraction may also be used as a stock oil for hydrocracking. By supplying such a residual fraction to a hydrocracker, it is possible to achieve improved cracking activity and higher quality properties for each fraction of the product oil.
[0047] A hydrotreating apparatus used for the hydrotreating process of the invention will now be described. Fig. 1 is a flow chart showing an example of a hydrotreating apparatus suitable for carrying out the hydrotreating process of the invention. The reaction column 10 of the hydrotreating apparatus 100 shown in Fig. 1 is a fixed bed reaction column, and a hydrotreating catalyst layer 12 is provided inside it. At the top of the reaction column 10 there is connected a line L1 for supply of the oil to be treated into the reaction column 10, while a line L2 is connected upstream from the connection of line L1 with the reaction column 10 for supply of hydrogen. Also, at the bottom of the reaction column 10 there is connected a line L3 for removal of reaction product from the reaction column 10, with the other end of the line L3 connected to an ordinary pressure distilling apparatus 40. [0048] The distilling apparatus 40 is used for fractionation of the reaction product obtained by reaction in the reaction column 10 into
separate fractions with specific boiling point ranges. The distilling apparatus 40 accomplishes fractionation into, for example, a gas fraction, naphtha fraction, kerosene fraction, light oil fraction and wax fraction. Each fraction fractionated in the distilling apparatus 40 is transported to subsequent processes by lines (L4-L8) connected to the distilling apparatus 40.
[0049] Fig. 2 is a flow chart showing another example of a hydrotreating apparatus suitable for carrying out the hydrotreating process of the invention. The hydrotreating apparatus 200 shown in Fig. 2 has the same construction as the hydrotreating apparatus 100, except that instead of the reaction column 10 of the hydrotreating apparatus 100 there are provided two reaction columns 20 and 30 connected in series via a transport line L9. A line L2a is connected upstream from the connection of line L9 with the reaction column 30 for supply of hydrogen.
[0050] At the hydrotreating apparatus 200, the interior of the reaction column 20 includes a hydrotreating catalyst layer 22, and the interior of the reaction column 30 includes a hydrotreating catalyst layer 32. The hydrotreating catalysts of the hydrotreating catalyst layer 22 and hydrotreating catalyst layer 32 may be the same or different. The hydrotreating treatment is carried out by these two reaction columns 20,30. Examples
[0051] The present invention will now be explained in greater detail through examples and comparative examples, with the understanding that the invention is in no way limited to these examples.
[0052] (Catalyst preparation)
After adding 18.0 g of water glass No.3 to 3000 g of a 5 wt% sodium aluminate aqueous solution in a vessel, the mixture was adjusted to a vessel content temperature of 65°C. Separately, 6.0 g of phosphoric acid (85% concentration) was added to 3000 g of an aluminum sulfate aqueous solution (2.5 wt% concentration) in a different vessel, and the mixture was adjusted to a vessel content temperature of 65°C. The solution containing the sodium aluminate and water glass was then added dropwise to the solution containing aluminum sulfate and phosphoric acid. The end point was defined as the time at which the pH of the mixture reached 7.0, and the obtained slurry product was filtered through a filter to obtain a cake-like slurry. [0053] The cake-like slurry was transferred to a vessel equipped with a reflux condenser, and then 150 ml of distilled water and 10 g of a 27% ammonia water solution were added and the mixture was heated and stirred at 80°C for 24 hours. Next, the slurry was placed in a kneader and heated to above 80°C, and kneading was performed while removing the moisture to obtain a clay-like kneaded blend. The obtained kneaded blend was extruded into a 1.5 mm diameter cylinder form using an extruder, and after drying at 110°C for 1 hour, it was fired at 550°C to obtain a molded carrier.
[0054] After placing 50 g of the obtained molded carrier into a round-bottomed flask, an impregnating solution containing 14.8 g of molybdenum trioxide, 25.8 g of nickel(II) nitrate hexahydrate, 2.9 g of phosphoric acid (85% concentration) and 4.0 g of malic acid was poured
into the flask while deairing with a rotary evaporator. The impregnated sample was dried at 120°C for 1 hour and then fired at 550°C to obtain catalyst A. The physical properties of the prepared catalyst A are shown in Table 1. [0055]
After adding 300 g of water glass No.3 to 3000 g of a 5 wt% sodium aluminate aqueous solution in a vessel, the mixture was adjusted to a vessel content temperature of 65°C. Separately, 3000 g of an aluminum sulfate aqueous solution (2.5 wt% concentration) was prepared in a different vessel, and the mixture was adjusted to a vessel content temperature of 65°C. The solution containing the sodium aluminate and water glass was then added dropwise to the obtained aluminum sulfate aqueous solution. The end point was defined as the time at which the pH of the mixture reached 7.0, and the obtained slurry product was filtered through a filter to obtain a cake-like slurry. [0056] The cake-like slurry was transferred to a vessel equipped with a reflux condenser, and then 150 ml of distilled water and 10 g of a 27% ammonia water solution were added and the mixture was heated and stirred at 80°C for 24 hours. The slurry was then placed in a kneader and heated to above 80°C, and kneading was performed while removing the moisture to obtain a clay-like kneaded blend. The obtained kneaded blend was extruded into a 1.5 mm diameter cylinder form using an extruder, and after drying at 110°C for 1 hour, it was fired at 550°C to obtain a molded carrier.
[0057] After placing 50 g of the obtained molded carrier into a round-bottomed flask, an impregnating solution containing 16.1 g of
ammonium paratungstate pentahydrate, 52.4 g of nickel(II) nitrate
hexahydrate and 2.0 g of phosphoric acid (85% concentration) was
poured into the flask while deairing with a rotary evaporator. The
impregnated sample was dried at 120°C for 1 hour, and then fired at
550°C to obtain catalyst B. The physical properties of the prepared
catalyst B are shown in Table 1.
[0058]
After placing 50 g of the molded carrier used to prepare catalyst A into a
round-bottomed flask, an impregnating solution containing 14.8 g of
molybdenum trioxide, 7.6 g of nickel(II) nitrate hexahydrate, 2.9 g of
phosphoric acid (85% concentration) and 4.0 g of malic acid was poured
into the flask while deairing with a rotary evaporator. The
impregnated sample was dried at 120°C for 1 hour, and then fired at
550°C to obtain catalyst C. The physical properties of the prepared
catalyst C are shown in Table 1. [Table 1]

(Table Removed)
[0059] (Example 1)
An apparatus having the same construction as the hydrotreating apparatus 200 shown in Fig. 2 was used for hydrotreating of an oil to be treated. A first reaction tube (inner diameter: 20 mm) packed with catalyst A (50 ml) and a second reaction tube (inner diameter: 20 mm)
packed with the same catalyst A (50 ml) were installed in series in a fixed bed flow type reactor. Next, straight-run light oil (3 wt% sulfur content) containing added dimethyl disulfide was used for pre-sulfurization of the catalyst for 4 hours under conditions with a catalyst layer average temperature of 300°C, a hydrogen partial pressure of 6 MPa, LHSV = 1 h-1 and a hydrogen/oil ratio of 200 NL/L. [0060] After pre-sulfurization, hydrotreating was carried out using a blended oil as an oil to be treated comprising the palm oil specified below and a Middle East vacuum light oil fraction in a volume ratio of 20:80 (hereinafter referred to as "blended oil 1"). Palm oil: 15°C density = 0.916 g/ml, oxygen content =11.4 wt%; Middle East vacuum light oil fraction: 15°C density = 0.919 g/ml, sulfur content = 2.41 wt%, nitrogen content = 610 ppm by weight, basic nitrogen content = 240 ppm by weight, initial boiling point = 285°C, end point = 540°C.
[0061] The blended oil 1 and hydrogen were introduced into the reactor from the first reaction tube end in a manner causing the treated fluid to pass through the first reaction tube and second reaction tube in that order. The hydrotreating conditions were a reaction temperature of 390°C in the first and second reaction tubes, 7.0 MPa pressure, LHSV = 0.6 h" . The volume ratio (quench hydrogen proportion) of hydrogen gas introduced between the first reaction tube and second reaction tube was 20 vol% of the total hydrogen introduced, and the hydrogen/oil ratio was 430 NL/L as determined based on the total hydrogen introduced. The reaction conditions are shown in Table 2, and the test results are shown in Table 3.
[0062] (Example 2)
Hydrotreating was carried out in the same manner as Example 1, except
that a first reaction tube (inner diameter: 20 mm) packed with catalyst A
(50 ml) and a second reaction tube (inner diameter: 20 mm) packed with
catalyst C (50 ml) were installed in series in a fixed bed flow type
reactor. The reaction conditions are shown in Table 2, and the test
results are shown in Table 3.
[0063] (Example 3)
Hydrotreating was carried out in the same manner as Example 1, except
that a first reaction tube (inner diameter: 20 mm) packed with catalyst B
(30 ml) and a second reaction tube (inner diameter: 20 mm) packed with
catalyst C (70 ml) were installed in series in a fixed bed flow type
reactor. The reaction conditions are shown in Table 2, and the test
results are shown in Table 3.
[0064] (Example 4)
Hydrotreating was carried out in the same manner as Example 1, except
that the oil to be treated was a blended oil comprising the palm oil used
in Example 1 and the vacuum light oil fraction specified below in a
volume ratio of 20:80 (hereinafter, "blended oil 2"). The reaction
conditions are shown in Table 2, and the test results are shown in Table
3.
Vacuum light oil fraction: 15°C density = 0.910 g/ml, sulfur content =
2.10 wt%, nitrogen content = 360 ppm by weight, basic nitrogen content
= 140 ppm by weight, initial boiling point = 270°C, end point = 536°C.
[0065] (Example 5)
Hydrotreating was carried out in the same manner as Example 3, except
that the total Volume of hydrogen gas was introduced together with the
oil to be treated (quench hydrogen proportion = 0%) without
introduction between the first reaction tube and second reaction tube.
The reaction conditions are shown in Table 2, and the test results are
shown in Table 3.
[0066] (Comparative Example 1)
Hydrotreating was carried out in the same manner as Example 1, except
that the oil to be treated was not a blended oil, but consisted only of the
Middle East vacuum light oil fraction used in Example 1. The reaction
conditions are shown in Table 2, and the test results are shown in Table
3.
[Table 2]

[Table 3]

(Table Removed)
Industrial Applicability
[0067] According to the invention there is provided a hydrotreating process which allows economical and highly efficient production of hydrotreated oil with satisfactorily reduced oxygen and sulfur contents, when the oil to be treated comprises an animal or vegetable-derived fat or oil component and a petroleum hydrocarbon fraction. The invention also provides a hydrotreated oil obtained by the hydrotreating process.

CLAIMS
1. A hydrotreating process characterized by contacting
an oil to be treated comprising a petroleum hydrocarbon fraction including fractions with boiling points of 300°C and higher and having a sulfur content of 0.5-4.5 wt%, and an animal or vegetable-derived fat or oil component with an oxygen content of 0.3-13 wt%, with a catalyst comprising one or more metals selected from among elements of Group 6A and Group 8 of the Periodic Table and a porous inorganic oxide containing at least aluminum oxide, in the presence of hydrogen.
2. A hydrotreating process according to claim 1,
wherein the proportion of compounds with a triglyceride structure among the fat and oil components is 80 mol?/o or greater.
3. A hydrotreating process according to claim 1 or 2,
wherein the petroleum hydrocarbon fraction contains nitrogen at 400-1800 ppm by weight.
4. A hydrotreating process according to any one of claims 1 to 3,
wherein the petroleum hydrocarbon fraction contains basic
nitrogen at 180-600 ppm by weight.
5. A hydrotreating process according to any one of claims 1 to 4,
wherein the porous inorganic oxide comprises aluminum oxide
and one or more elements selected from among silicon, boron, phosphorus, titanium and zirconium, and the metal consists of two or more metals selected from among cobalt, molybdenum, nickel and tungsten, with the metal supported on the porous inorganic oxide.
6. A hydrotreating process according to any one of claims 1 to 5,
wherein the oil to be treated and the catalyst are contacted under conditions with a hydrogen pressure of 5-20 MPa, a liquid space velocity of 0.1-2.2 h-1 and a hydrogen/oil ratio of 300-1500 NL/L.
7. A hydrotreated oil which is produced by a hydrotreating process according to any one of claims 1 to 6.
8. A light oil fraction base comprising a hydrotreated oil according to claim 7,
wherein the hydrotreated oil has a boiling point of 260-300°C.
9. A right oil fraction base according to claim 8,
wherein the light oil fraction base has a sulfur content of no greater than 15 ppm by weight and an oxygen content of no greater than 0.5 wt%.
10. A stock oil for catalytic cracking comprising a hydrotreated oil
according to claim 7,
wherein the stock oil for catalytic cracking has a sulfur content of no greater than 0.1 wt% and an oxygen content of no greater than 1 wt%.
11. A stock oil for hydrocracking comprising a hydrotreated oil
according to claim 7,
wherein the stock oil for hydrocracking has a sulfur content of no greater than 0.1 wt% and an oxygen content of no greater than 1 wt%.

Documents:

5036-delnp-2008-Abstract-(24-03-2014).pdf

5036-delnp-2008-abstract.pdf

5036-delnp-2008-Claims-(24-03-2014).pdf

5036-delnp-2008-claims.pdf

5036-delnp-2008-Correspondence Others-(03-12-2013).pdf

5036-delnp-2008-Correspondence Others-(04-04-2014).pdf

5036-delnp-2008-Correspondence Others-(24-03-2014).pdf

5036-delnp-2008-Correspondence Others-(27-06-2014).pdf

5036-delnp-2008-correspondence-others.pdf

5036-delnp-2008-description (complete).pdf

5036-delnp-2008-Drawings-(24-03-2014).pdf

5036-delnp-2008-drawings.pdf

5036-delnp-2008-form-1.pdf

5036-DELNP-2008-Form-18-(29-07-2009).pdf

5036-delnp-2008-Form-2-(04-04-2014).pdf

5036-delnp-2008-Form-2-(24-03-2014).pdf

5036-delnp-2008-form-2.pdf

5036-delnp-2008-Form-3-(03-12-2013).pdf

5036-delnp-2008-form-3.pdf

5036-delnp-2008-Form-5-(24-03-2014).pdf

5036-delnp-2008-form-5.pdf

5036-delnp-2008-pct-210.pdf

5036-delnp-2008-pct-304.pdf

5036-delnp-2008-pct-308.pdf

5036-delnp-2008-Petition-137-(04-04-2014).pdf

5036-delnp-2008-Petition-137-(24-03-2014).pdf

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Patent Number

262970

Indian Patent Application Number

5036/DELNP/2008

PG Journal Number

40/2014

Publication Date

03-Oct-2014

Grant Date

25-Sep-2014

Date of Filing

11-Jun-2008

Name of Patentee

JX NIPPON OIL & ENERGY CORPORATION

Applicant Address

3-12, NISHI-SHIMBASHI 1-CHOME, MINATO-KU, TOKYO 105-8412, JAPAN.

Inventors:

#	Inventor's Name	Inventor's Address
1	HIDESHI IKI,	C/O NIPPON OIL CORPORATION, 8, CHIDORI-CHO, NAKA-KU, YOKOHAMA-SHI, KANAGAWA 231-0815,JAPAN.
2	SHINYA TAKAHASHI	C/O NIPPON OIL CORPORATION, 8, CHIDORI-CHO, NAKA-KU, YOKOHAMA-SHI, KANAGAWA 231-0815,JAPAN.

PCT International Classification Number

C10G 3/00

PCT International Application Number

PCT/JP2006/323782

PCT International Filing date

2006-11-29

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	P2005-3471103	2005-11-30	Japan