WO2009139313A1 - Procédé pour la fabrication d'huile hydrocarbonée - Google Patents

Procédé pour la fabrication d'huile hydrocarbonée Download PDF

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Publication number
WO2009139313A1
WO2009139313A1 PCT/JP2009/058573 JP2009058573W WO2009139313A1 WO 2009139313 A1 WO2009139313 A1 WO 2009139313A1 JP 2009058573 W JP2009058573 W JP 2009058573W WO 2009139313 A1 WO2009139313 A1 WO 2009139313A1
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Prior art keywords
oil
fraction
hydrocarbon oil
hydrocarbon
catalyst
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PCT/JP2009/058573
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English (en)
Japanese (ja)
Inventor
辰雄 濱松
成 小山
秀樹 尾野
靖敏 井口
英 壱岐
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新日本石油株式会社
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Priority to JP2009519944A priority Critical patent/JP5588171B2/ja
Publication of WO2009139313A1 publication Critical patent/WO2009139313A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the present invention relates to a method for producing a hydrocarbon oil.
  • biomass energy derived from plants can effectively use carbon immobilized from carbon dioxide in the atmosphere by photosynthesis during the growth process of plants, so it does not lead to an increase in carbon dioxide in the atmosphere from the viewpoint of the life cycle, so-called It has the property of being carbon neutral.
  • fatty acid methyl ester oils (abbreviated as “FAME” from the acronym of Fatty Acid Methyl Ester) are generally known.
  • FAME is produced by subjecting triglyceride, which is a general structure of animal and vegetable oils, to transesterification with methanol by the action of an alkali catalyst or the like.
  • FAME has two oxygen atoms in one molecule, so it has an extremely high oxygen content as a fuel. Even when blended with conventional diesel fuel derived from petroleum, this oxygen content is still in the engine. There is also a problem that adverse effects on materials are concerned.
  • the reaction of hydrodeoxygenating feedstock containing oxygenated hydrocarbon compounds derived from animals and plants in the presence of a hydrogenation catalyst is an exothermic reaction, and it is necessary to improve the heat resistance of the reactor against an increase in reaction temperature.
  • There is a problem such as increase in the temperature, side reaction at high temperature and occurrence of runaway reaction at high temperature, and it is necessary to suppress the temperature rise.
  • a method of installing a cooling device in the reactor to remove reaction heat or a method of diluting the raw material with an inert substance (diluent) is employed.
  • the former method makes the reactor very expensive.
  • the latter method in order to obtain a sufficient heat generation suppressing effect, it is necessary to use a large amount of an inert substance, and there is a limitation that an excessively large apparatus is required.
  • hydrodeoxygenate feedstock containing oxygenated hydrocarbon compounds derived from animals and plants in the presence of hydrogenation catalysts. Unless the heat of reaction can be effectively recovered as energy, the emission of carbon dioxide corresponding to that energy cannot be reduced.
  • the present invention has been made in view of the above-described problems of the prior art, and is capable of producing hydrocarbon oil that can suppress the amount of heat generated by the reaction to suppress energy loss and reduce the amount of diluent used. It aims to provide a method.
  • the present invention provides a raw material oil containing an oxygen-containing hydrocarbon compound derived from animal and vegetable oils in the presence of hydrogen, and two kinds selected from aluminum, silicon, zirconium, boron, titanium and magnesium.
  • a porous inorganic oxide comprising the above elements, and a catalyst containing one or more metals selected from Group 6A and Group 8 elements of the periodic table supported on the porous inorganic oxide; And a hydrogen pressure treatment at a hydrogen pressure of 1 MPa or more and less than 6 MPa, and removing hydrogen, hydrogen sulfide, carbon dioxide and water from the material to be treated to obtain a hydrocarbon oil, A part of the hydrocarbon oil obtained through the above process is recycled to supply 0.5 to 5 times by mass with respect to the oxygen-containing hydrocarbon compound, and the oxygen-containing hydrocarbon compound Characterized in that it contains and a sulfur-containing hydrocarbon compound of from 1 to 50 ppm by mass of sulfur atoms terms and to provide a method for manufacturing a hydrocarbon oil.
  • the hydrodeoxygenation reaction of the oxygen-containing hydrocarbon compound derived from the animal and plant oil proceeds to produce hydrocarbons.
  • the “hydrodeoxygenation reaction” in the present invention means a reaction in which oxygen atoms constituting the oxygen-containing hydrocarbon compound are removed and hydrogen is added to the cleaved portion.
  • oxygen-containing groups such as ester groups and carboxyl groups, respectively, but oxygen atoms contained in these oxygen-containing groups are removed by hydrodeoxygenation reaction, and oxygen-containing hydrocarbons. The compound is converted to a hydrocarbon.
  • the first reaction pathway is a decarboxylation pathway in which oxygen-containing groups such as fatty acid triglycerides are eliminated as carbon dioxide as they are, and oxygen atoms are removed as carbon dioxide.
  • the second reaction route is a hydrogenation route that is reduced via an aldehyde or alcohol while maintaining the number of carbon atoms such as fatty acid triglyceride. In this case, oxygen atoms are converted to water. When these reactions proceed in parallel, hydrocarbons, water, and carbon dioxide are generated.
  • the reaction scheme of hydrodeoxygenation taking the case of an alkyl ester of stearic acid as an example is shown in the following formulas (1) and (2).
  • the reaction scheme represented by the formula (1) corresponds to the first reaction path
  • the reaction scheme represented by the formula (2) corresponds to the second reaction path.
  • R represents an alkyl group.
  • a raw material oil containing an oxygen-containing hydrocarbon compound derived from an animal or vegetable oil is hydrotreated, the material to be treated and / or carbonized obtained in the above-described step is subjected to the raw material oil.
  • Recycled oil which is a part of hydrogen oil, and sulfur-containing hydrocarbon compounds are contained in specific amounts, and by adopting the above-mentioned specific catalyst and reaction conditions, reaction among the two hydrodeoxygenation reactions
  • the proportion of the first reaction path with lower heat can be increased.
  • the amount of heat generated by the reaction can be suppressed, and the amount of diluent used can be reduced.
  • the hydrocarbon oil obtained in the above step is fractionated into a light fraction, a middle fraction and a heavy fraction, and the cut temperature of the light fraction and the middle fraction is 100 to 200 ° C.
  • the cut temperature of the middle fraction and the heavy fraction is preferably 300 to 400 ° C.
  • hydrocarbon oil obtained in the above step or the middle fraction fractionated from the hydrocarbon oil isomerization.
  • the hydrocarbon oil obtained in the above step or the middle distillate fractionated from the hydrocarbon oil is subjected to isomerization treatment, and the obtained isomerized oil is mixed with a light fraction, a middle fraction and a heavy fraction. It is preferable that the cut temperature of the light fraction and the middle fraction is 100 to 200 ° C., and the cut temperature of the middle fraction and the heavy fraction is 300 to 400 ° C.
  • the recycled oil contains a part of the hydrocarbon oil.
  • a part of the middle fraction fractionated from hydrocarbon oil a part of the middle fraction fractionated from hydrocarbon oil or hydrocarbon oil, a part of the isomerization treatment, or a hydrocarbon oil or hydrocarbon It is preferable to contain a portion of the middle distillate fraction obtained by isomerization of the middle distillate fraction from the oil.
  • oxygen-containing hydrocarbon compound contained in the raw material oil is preferably one or more compounds selected from fatty acids and fatty acid esters, and more preferably triglycerides of fatty acids.
  • the catalyst used for the hydrotreatment has a pore volume of 0.30 to 0.85 ml / g by nitrogen adsorption BET method, an average pore diameter of 5 to 11 nm, and has a total pore volume of It is preferable that the proportion of the pore volume derived from pores having a pore diameter of 3 nm or less is 35% by volume or less.
  • porous inorganic oxide contained in the catalyst preferably contains a phosphorus element.
  • a method for producing a hydrocarbon oil capable of suppressing the amount of heat generated by a reaction to suppress energy loss and reducing the amount of diluent used.
  • a raw material oil containing an oxygen-containing compound derived from animal and vegetable oils, a specific recycled oil, and a sulfur-containing hydrocarbon compound is used.
  • an aliphatic hydrocarbon compound corresponding to the recycled oil may be prepared in advance, and the hydrocarbon compound contained in the feed oil may be subjected to the hydrotreatment.
  • the oxygen-containing compounds derived from animal and vegetable oils oil and fat components derived from animal and vegetable oils and derivatives thereof are preferable because decarboxylation reaction easily occurs.
  • the oil and fat component maintains and improves the performance of natural and artificially produced and manufactured animal and vegetable oils and animal and vegetable oil components and / or components derived and produced from these oils and fats and these oil and fat products.
  • the component added for the purpose of making it included is included.
  • the derivative of the fat and oil component includes a component that is by-produced in the process of producing the fat and oil product and a component that is intentionally processed into a derivative.
  • Examples of the fat and oil components derived from animal and vegetable oils include beef tallow, corn oil, rapeseed oil, soybean oil, and palm oil.
  • any fats and oils derived from animal and vegetable oils may be used, and waste oil after using these fats and oils may be used.
  • vegetable oils and fats are preferable from the viewpoint of carbon neutral, and rapeseed oil, soybean oil, and palm oil are more preferable from the viewpoint of the number of fatty acid alkyl chain carbons and their reactivity.
  • Derivatives of fat and oil components derived from animal and vegetable oils may include components processed into ester bodies such as fatty acids constituting the fatty acid triglycerides of the fat and oil components and methyl esters thereof.
  • fatty acids constituting these fatty acid triglycerides include butyric acid (C 3 H 7 COOH) and caproic acid (C 5 H 11 COOH), which are fatty acids having no unsaturated bond in the molecular structure called saturated fatty acid.
  • Caprylic acid (C 7 H 15 COOH), capric acid (C 9 H 19 COOH), lauric acid (C 11 H 23 COOH), myristic acid (C 13 H 27 COOH), palmitic acid (C 15 H 31 COOH) , Stearic acid (C 17 H 35 COOH), and oleic acid (C 17 H 33 COOH), linoleic acid (C 17 H 31 COOH), linolenic acid (C), which are unsaturated fatty acids having one or more unsaturated bonds 17 H 29 COOH), ricinolenic acid (C 17 H 32 (OH) COOH) and the like.
  • Recycled oil plays a role in suppressing temperature rise due to reaction heat in hydroprocessing.
  • the recycled oil a part of hydrocarbon oil (distilled oil) obtained by removing hydrogen, hydrogen sulfide, carbon dioxide and water from the material to be processed obtained by hydroprocessing is recycled to the raw material oil. Supplied.
  • the recycled oil preferably contains a part of the hydrocarbon oil. Furthermore, a part of middle fraction fractionated from hydrocarbon oil, a part of isomerized portion of middle fraction fractionated from hydrocarbon oil or hydrocarbon oil, or hydrocarbon oil or hydrocarbon oil It is preferable to contain a part of the middle distillate fraction obtained from the isomerization treatment of the middle distillate fraction obtained from 1). When these components are recycled to the feedstock, it is preferable to cool the components.
  • the content of recycled oil in the feedstock oil is 0.5 to 5 times the mass of oxygen-containing hydrocarbon compounds derived from animal and vegetable oils, and the ratio is determined within the above range according to the maximum operating temperature of the reactor. It is done. Assuming that the specific heat of the two is the same, if the two are mixed one-on-one, the temperature rise will be half that when the substance derived from animal and vegetable oils is reacted alone. If it exists, it is because the reaction heat can fully be reduced. If the content of the recycled oil is larger than 5 times the mass of the oxygen-containing hydrocarbon compound, the concentration of the oxygen-containing hydrocarbon compound is lowered and the reactivity is lowered, and the flow rate of the piping is increased and the load is increased. Increase. On the other hand, when the content of the recycled oil is lower than 0.5 times the mass of the oxygen-containing hydrocarbon compound, the temperature rise cannot be sufficiently suppressed.
  • the mixing method of the raw material oil and the recycled oil is not particularly limited.
  • the raw material oil may be mixed in advance and the mixture may be introduced into the reactor of the hydrotreating apparatus, or when the raw material oil is introduced into the reactor, the reactor You may supply in the front
  • a plurality of reactors can be connected in series and introduced between the reactors, or the catalyst layer can be divided and introduced between the catalyst layers in a single reactor.
  • the sulfur-containing hydrocarbon compound plays a role of improving the deoxygenation activity in the hydrotreatment.
  • limit especially as a sulfur-containing hydrocarbon compound Specifically, sulfide, disulfide, polysulfide, thiol, thiophene, benzothiophene, dibenzothiophene, these derivatives, etc. are mentioned.
  • the sulfur-containing hydrocarbon compound contained in the feedstock oil may be a single compound or a mixture of two or more. Furthermore, you may add the petroleum-type hydrocarbon fraction containing a sulfur content to raw material oil.
  • a fraction obtained in a general petroleum refining process can be used.
  • a fraction corresponding to a predetermined boiling range obtained from an atmospheric distillation apparatus or a vacuum distillation apparatus, or obtained from a hydrodesulfurization apparatus, a hydrocracking apparatus, a residual oil direct desulfurization apparatus, a fluid catalytic cracking apparatus, etc.
  • a fraction corresponding to a predetermined boiling range may be used.
  • the content of the sulfur-containing hydrocarbon compound is required to be 1 to 50 ppm by mass, preferably 5 to 30 ppm by mass, more preferably 10 to 10 ppm in terms of sulfur atom with respect to the oxygen-containing hydrocarbon compound derived from animal and vegetable oils. 20 ppm by mass.
  • the content is less than 1 ppm by mass in terms of sulfur atom, it tends to be difficult to stably maintain the deoxygenation activity.
  • it exceeds 50 ppm by mass the sulfur content in the light gas discharged in the hydrotreating process will increase, and the sulfur content in the oil to be treated or hydrocarbon oil will tend to increase.
  • the sulfur content in the present invention means the mass content of the sulfur content measured according to the method described in JIS K 2541 “Sulfur Content Test Method” or ASTM-5453.
  • the recycle oil and the sulfur-containing hydrocarbon compound may be added to the feedstock oil at the same time or separately, but after the recycle oil is added to the feedstock oil, the sulfur-containing compound may be further added.
  • the sulfur-containing hydrocarbon compound may be mixed in advance with a mixed oil of raw material oil and recycled oil, and the mixture may be introduced into the reactor of the hydrotreating apparatus, or the mixed oil of raw material oil and recycled oil may be reacted. When it is introduced into the reactor, it may be supplied before the reactor.
  • Hydrolysis treatment In the hydrogenation treatment according to the present invention, a porous inorganic oxide comprising two or more elements selected from aluminum, silicon, zirconium, boron, titanium and magnesium, and the porous inorganic oxide are supported. In addition, a catalyst containing one or more metals selected from Group 6A and Group 8 elements of the periodic table is used.
  • a porous inorganic oxide comprising two or more selected from aluminum, silicon, zirconium, boron, titanium and magnesium as described above is used.
  • the porous inorganic oxide is preferably at least two selected from aluminum, silicon, zirconium, boron, titanium and magnesium from the viewpoint that the deoxygenation activity and desulfurization activity can be further improved.
  • Aluminum and other elements And an inorganic oxide (a composite oxide of aluminum oxide and another oxide) is more preferable.
  • the aluminum content is preferably 1 to 97% by mass, more preferably 10 to 97% by mass in terms of alumina, based on the total amount of the porous inorganic oxide. %, More preferably 20 to 95% by mass.
  • the aluminum content is less than 1% by mass in terms of alumina, physical properties such as carrier acid properties are not suitable, and sufficient deoxidation activity and desulfurization activity tend not to be exhibited.
  • the aluminum content exceeds 97% by mass in terms of alumina, the catalyst surface area becomes insufficient and the activity tends to decrease.
  • the method for introducing silicon, zirconium, boron, titanium and magnesium, which are carrier constituent elements other than aluminum, is not particularly limited, and a solution containing these elements may be used as a raw material.
  • silicon, silicon, water glass, silica sol, etc. for boron, boric acid, etc., for phosphorus, phosphoric acid and alkali metal salts of phosphoric acid, etc., for titanium, titanium sulfide, titanium tetrachloride and various alkoxide salts, etc.
  • zirconium zirconium sulfate and various alkoxide salts can be used.
  • the porous inorganic oxide preferably contains phosphorus as a constituent element.
  • the phosphorus content is preferably 0.1 to 10% by mass, more preferably 0.5 to 7% by mass, and further preferably 2 to 6% by mass, based on the total amount of the porous inorganic oxide.
  • the phosphorus content is less than 0.1% by mass, sufficient deoxygenation activity and desulfurization activity tend not to be exhibited, and when it exceeds 10% by mass, excessive decomposition proceeds and the target hydrocarbon Oil yield may be reduced.
  • the raw materials of the carrier constituents other than the above-described aluminum oxide in a step prior to the firing of the carrier.
  • the aluminum hydroxide gel containing these structural components may be prepared, and the said raw material may be added with respect to the prepared aluminum hydroxide gel.
  • the above raw materials may be added in a step of adding water or an acidic aqueous solution to a commercially available aluminum oxide intermediate or boehmite powder and kneading them, but it is more preferable to coexist at the stage of preparing aluminum hydroxide gel.
  • the mechanism of the effect of the carrier constituents other than aluminum oxide has not necessarily been elucidated, it is presumed that it forms a complex oxide state with aluminum, which increases the surface area of the carrier and interacts with the active metal. It is considered that the activity is affected by producing the action.
  • the porous inorganic oxide as the carrier carries one or more metals selected from Group 6A and Group 8 elements of the periodic table.
  • these metals it is preferable to use a combination of two or more metals selected from cobalt, molybdenum, nickel and tungsten.
  • suitable combinations include cobalt-molybdenum, nickel-molybdenum, nickel-cobalt-molybdenum, and nickel-tungsten. Of these, combinations of nickel-molybdenum, nickel-cobalt-molybdenum and nickel-tungsten are more preferred.
  • these metals are used after being converted to a sulfide state.
  • the total supported amount of tungsten and molybdenum is preferably 12 to 35% by mass, more preferably 15 to 30% by mass in terms of oxide. If the total supported amount of tungsten and molybdenum is less than 12% by mass, the active sites tend to decrease and sufficient activity cannot be obtained. On the other hand, if it exceeds 35% by mass, the metal is not effectively dispersed and sufficient activity tends not to be obtained.
  • the range of the total supported amount of cobalt and nickel is preferably 1.0 to 15% by mass, more preferably 1.5 to 12% by mass in terms of oxide.
  • the method of incorporating these active metals into the catalyst is not particularly limited, and a known method applied when producing a normal desulfurization catalyst can be used.
  • a method of impregnating a catalyst carrier with a solution containing a salt of an active metal is preferably employed.
  • an equilibrium adsorption method, a pore-filling method, an incident-wetness method, and the like are also preferably employed.
  • the pore-filling method is a method in which the pore volume of a support is measured in advance and impregnated with a metal salt solution having the same volume.
  • the impregnation method is not particularly limited, and it can be impregnated by an appropriate method according to the amount of metal supported and the physical properties of the catalyst carrier.
  • the number of types of hydrotreating catalyst to be used is not particularly limited.
  • one type of catalyst may be used alone, or a plurality of catalysts having different active metal species and carrier components may be used.
  • a catalyst containing cobalt-molybdenum after the catalyst containing nickel-molybdenum, and nickel-cobalt-molybdenum after the catalyst containing nickel-molybdenum are used.
  • a catalyst containing nickel-cobalt-molybdenum after the catalyst containing nickel-tungsten, and a catalyst containing cobalt-molybdenum after the catalyst containing nickel-cobalt-molybdenum may be further combined before and / or after these combinations.
  • the content of aluminum oxide is included in the subsequent stage of the catalyst having an aluminum oxide content of 30% by mass or more and less than 80% by mass based on the total mass of the support.
  • a catalyst having an amount in the range of 80 to 99% by mass may be used.
  • Each catalyst used in the present invention can be used after being presulfided in the same manner as a general hydrodesulfurization catalyst.
  • a hydrocarbon oil or petroleum hydrocarbon oil obtained by the process of the present invention to which a sulfur-containing hydrocarbon compound is added heat at 200 ° C. or higher is given in accordance with a predetermined procedure under hydrogen pressure conditions. .
  • the active metal on the catalyst becomes sulfided and exhibits activity.
  • limit especially as a sulfur-containing hydrocarbon compound Specifically, sulfide, disulfide, polysulfide, thiol, thiophene, benzothiophene, dibenzothiophene, these derivatives, etc. are mentioned.
  • These sulfur-containing hydrocarbon compounds may be a single compound or a mixture of two or more. Further, a petroleum hydrocarbon fraction containing a sulfur content may be used directly.
  • the preliminary sulfidation may be performed in the same reactor as the hydrodeoxygenation reaction, or a catalyst that has been subjected to a sulfurization treatment in advance, or a catalyst that has been activated by a sulfur-containing, oxygen-containing, or nitrogen-containing organic solvent. Can also be used.
  • a guard catalyst and a demetallizing catalyst are provided for the purpose of trapping the scale that flows along with the feedstock as needed and supporting the hydrotreating catalyst at the separation part of the catalyst bed.
  • Inert packing may be used. In addition, these can be used individually or in combination.
  • the pore volume of the catalyst used in the present invention by nitrogen adsorption BET method is preferably 0.30 to 0.85 ml / g, and more preferably 0.45 to 0.80 ml / g.
  • the pore volume is less than 0.30 ml / g, the dispersibility of the supported metal becomes insufficient, and there is a concern that the active site is verified.
  • the pore volume exceeds 0.85 ml / g, the catalyst strength becomes insufficient, and the catalyst may be pulverized or crushed during use.
  • the average pore diameter of the catalyst obtained by the above measuring method is preferably 5 to 11 nm, and more preferably 6 to 9 nm. If the average pore diameter is less than 5 nm, the reaction substrate may not sufficiently diffuse into the pores, and the reactivity may be reduced. On the other hand, if the average pore diameter exceeds 11 nm, the pore surface area decreases, and the activity may be insufficient.
  • the ratio of the pore volume derived from pores having a pore diameter of 3 nm or less to the total pore volume is 35 volumes in order to maintain effective catalyst pores and exhibit sufficient activity. % Or less is preferable.
  • the hydrogen pressure when the above-mentioned raw material oil and catalyst are brought into contact with each other in the presence of hydrogen needs to be 1 MPa or more and less than 6 MPa, and preferably 2 to 4 MPa. If the hydrogen pressure is 6 MPa or more, the ratio of decarboxylation reaction and dehydration reaction is constant, but if it is less than 6 MPa, the decarboxylation ratio increases as the pressure decreases, and the effect of suppressing the amount of heat generated by the reaction appears. To do. However, when the hydrogen pressure is less than 1 MPa, the reactivity tends to decrease or the activity tends to decrease rapidly.
  • the flow rate of the substance derived from animal and vegetable oils per hour with respect to the catalyst is preferably 0.5 to 5 times, more preferably 0.7 to 3 times.
  • the selectivity of the decarboxylation reaction increases as the amount of the substance derived from the animal and vegetable oil per hour with respect to the catalyst increases.
  • reducing the flow rate causes an increase in the amount of catalyst, that is, an increase in the size of the reactor, so it is realistic to make it 0.5 times or more.
  • the hydrogen oil ratio (hydrogen / oil ratio) in the hydrotreatment is preferably in the range of 100 to 1500 NL / L, more preferably in the range of 200 to 1200 NL / L, and in the range of 250 to 1000 NL / L. Is particularly preferred.
  • the hydrogen oil ratio exceeds the above upper limit, the effect of increasing the ratio of decarboxylation reaction at the hydrogen pressure is inhibited.
  • the hydrogen oil ratio is below the lower limit, there is a possibility that sufficient hydrogenation reaction does not proceed.
  • the reaction temperature in the hydrogenation treatment is preferably in the range of 180 to 390 ° C, more preferably in the range of 200 to 380 ° C, and particularly preferably in the range of 250 to 365 ° C.
  • the reaction temperature is lower than 180 ° C., sufficient hydrogenation reaction does not proceed, and when it is higher than 390 ° C., excessive decomposition, polymerization of raw material oil, and other side reactions may proceed.
  • the fixed bed system can be adopted as the reactor type. That is, hydrogen can adopt either a countercurrent or a cocurrent flow with respect to the feedstock. Moreover, it is good also as a form which combined the countercurrent and the parallel flow using several reactors. As a general format, it is a down flow, and a gas-liquid twin parallel flow format can be adopted. Moreover, the reactor may be used alone or in combination, and a structure in which one reactor is divided into a plurality of catalyst beds may be adopted.
  • the oil to be treated that has been hydrotreated in the reactor is fractionated into a hydrotreated oil containing a predetermined fraction through a gas-liquid separation process, a rectification process, and the like.
  • By-products such as water, carbon monoxide, carbon dioxide, and hydrogen sulfide may be generated with the reaction of oxygen and sulfur contained in the feedstock oil. It is necessary to install gas-liquid separation equipment and other by-product gas removal devices in the recovery process to remove these by-products.
  • a high-pressure separator or the like can be preferably exemplified.
  • the spilled oil after removing the by-products may be fractionated into multiple fractions in a rectifying tower as necessary.
  • it may be fractionated into light fractions such as gas and naphtha fractions, middle fractions such as kerosene and light oil fractions, and heavy fractions such as residue fractions.
  • the cut temperature of the light fraction and the middle fraction is preferably 100 to 200 ° C, more preferably 120 to 180 ° C, and further preferably 140 to 160 ° C.
  • the cut temperature of the middle fraction and the heavy fraction is preferably 300 to 400 ° C, more preferably 300 to 380 ° C, and further preferably 300 to 360 ° C.
  • hydrogen can be manufactured by reforming a part of such a light hydrocarbon fraction to be produced in a steam reformer.
  • the hydrogen produced in this way has a characteristic of carbon neutral because the raw material used for steam reforming is a biomass-derived hydrocarbon, and can reduce the burden on the environment.
  • hydrogen gas is introduced from the inlet of the first reactor in association with the feed oil before or after passing through the heating furnace, but separately from this, the temperature in the reactor is controlled, Hydrogen gas may be introduced from between the catalyst beds or between a plurality of reactors for the purpose of maintaining the hydrogen pressure throughout the reactor.
  • the hydrogen thus introduced is generally called quench hydrogen.
  • the ratio of quench hydrogen to hydrogen gas introduced along with the feedstock is preferably 10 to 60% by volume, and more preferably 15 to 50% by volume. If the rate of quench hydrogen is less than 10 volumes, the reaction at the subsequent reaction site tends not to proceed sufficiently. If the rate of quench hydrogen exceeds 60% by volume, the reaction near the reactor inlet does not proceed sufficiently. Tend.
  • the hydrocarbon oil produced by the present invention when used as a light oil fraction base, it contains a fraction having a boiling point of at least 260 to 300 ° C., a sulfur content of 15 mass ppm or less, and an oxygen content.
  • the content of is preferably 0.5 mass% or less, more preferably the sulfur content is 12 mass ppm or less, and the oxygen content is 0.3 mass% or less.
  • the isomerization reaction zone may be composed of a single catalyst bed or a plurality of catalyst beds.
  • the catalyst beds may be installed separately in a single reactor, or a plurality of reactors are arranged in series or in parallel, A catalyst bed may be installed in each reactor.
  • a fixed bed system As the reactor type in the isomerization reaction zone, a fixed bed system can be adopted. That is, hydrogen can adopt either a countercurrent or a parallel flow type with respect to the oil to be treated. Moreover, it is good also as a form which combined the countercurrent and the parallel flow using several reactors. As a general format, it is a down flow, and a gas-liquid twin parallel flow format can be adopted. Moreover, the reactor may be used alone or in combination, and a structure in which one reactor is divided into a plurality of catalyst beds may be adopted.
  • the isomerization catalyst is not particularly limited as long as it has hydroisomerization activity, but is a porous inorganic oxide comprising two or more elements selected from aluminum, silicon, zirconium, boron, titanium and magnesium. And a catalyst containing at least one metal element selected from Group VIII elements of the Periodic Table supported on the porous inorganic oxide are preferably used.
  • the support for the isomerization catalyst is preferably at least two selected from aluminum, silicon, zirconium, boron, titanium and magnesium from the viewpoint of further improving the hydroisomerization activity.
  • An inorganic oxide a composite oxide of aluminum oxide and another oxide is more preferable.
  • the porous inorganic oxide includes at least two elements selected from aluminum, silicon, zirconium, and titanium.
  • the porous inorganic oxide may be either amorphous or crystalline, and zeolite can also be used.
  • zeolite it is preferable to use zeolite having a crystal structure such as FAU, BEA, MOR, MFI, MEL, MWW, TON, AEL, MTT among the structure codes defined by the International Zeolite Society.
  • the metal supported on the isomerization catalyst is preferably one or more metals selected from Group VIII elements of the periodic table, and among these, Pt, Pd, Ru, Rh, Au, Ir, Ni, Co It is more preferably one or more metals selected from the group consisting of Pt, Rd, Ru, and Ni.
  • These active metals may be a combination of two or more kinds of metals, and examples thereof include Pt—Pd, Pt—Ru, Pt—Rh, Pt—Au, and Pt—Ir.
  • the method of incorporating these active metals into the catalyst is not particularly limited, and a known method applied when producing an ordinary hydrogenation catalyst can be used.
  • a method of impregnating a catalyst carrier with a solution containing a salt of an active metal is preferably employed.
  • an equilibrium adsorption method, a pore-filling method, an incident-wetness method, and the like are also preferably employed.
  • the pore-filling method is a method in which the pore volume of a support is measured in advance and impregnated with a metal salt solution having the same volume.
  • the impregnation method is not particularly limited, and it can be impregnated by an appropriate method according to the amount of metal supported and the physical properties of the catalyst carrier.
  • These metals can be used as an impregnation solution by dissolving a metal source in the form of nitrate, sulfate or complex in an aqueous solution or an appropriate organic solvent.
  • the sulfur content contained in the isomerization feedstock is preferably 1 ppm by mass or less, more preferably 0.5 ppm by mass. If the sulfur content exceeds 1 mass ppm, the progress of hydroisomerization in the first step may be hindered. In addition, for the same reason, it is necessary for the reaction gas containing hydrogen introduced together with the isomerization raw material oil to have a sufficiently low sulfur content concentration, preferably 1 ppm by volume or less, More preferably, the volume is not more than ppm.
  • the reaction conditions in the isomerization step are preferably a hydrogen pressure of 1 to 10 MPa, a liquid space velocity (LHSV) of 0.1 to 3.0 h-1, and a hydrogen oil ratio (hydrogen / oil ratio) of 100 to 1500 NL / L. More preferably a hydrogen pressure of 2 to 8 MPa, a liquid space velocity of 0.2 to 2.5 h-1, and a hydrogen oil ratio of 200 to 1200 NL / L; still more preferably a hydrogen pressure of 2.5 to 8 MPa, a space velocity of 0. .2 to 2.0 h-1, hydrogen oil ratio 250 to 1000 NL / L. These conditions are factors that influence the reaction activity of the catalyst.
  • the reaction temperature in the isomerization step is preferably in the range of 220 to 390 ° C, more preferably in the range of 240 to 380 ° C, and particularly preferably in the range of 250 to 365 ° C.
  • the reaction temperature is lower than 220 ° C., sufficient hydroisomerization reaction does not proceed, and when it is higher than 390 ° C., excessive decomposition or other side reaction may proceed.
  • the hydrogen gas introduced into the reaction zone together with the isomerization feedstock is introduced from the reaction zone inlet along with the feedstock upstream or downstream of the heating furnace for raising the temperature to a predetermined reaction temperature.
  • hydrogen gas is introduced between the catalyst beds and between the reactors in order to control the temperature in the reaction zone and maintain the hydrogen pressure throughout the reaction zone. (Quenched hydrogen).
  • any or a combination of product oil, unreacted oil, intermediate reaction oil and the like may be combined and introduced partially from the reaction zone inlet, the catalyst bed, between the plurality of reactors, or the like. Thereby, the reaction temperature can be controlled, and an excessive decomposition reaction or reaction runaway due to an increase in the reaction temperature can be avoided.
  • the product oil after the isomerization treatment may be fractionated into a plurality of fractions in a rectifying column as necessary.
  • it may be fractionated into light fractions such as gas and naphtha fractions, middle fractions such as kerosene and light oil fractions, and heavy fractions such as residue fractions.
  • the cut temperature of the light fraction and the middle fraction is preferably 100 to 200 ° C, more preferably 120 to 180 ° C, and further preferably 140 to 160 ° C.
  • the cut temperature of the middle fraction and the heavy fraction is preferably 300 to 400 ° C, more preferably 300 to 380 ° C, and further preferably 300 to 360 ° C.
  • hydrogen can be manufactured by reforming a part of such a light hydrocarbon fraction to be produced in a steam reformer.
  • the hydrogen produced in this way has a characteristic of carbon neutral because the raw material used for steam reforming is a biomass-derived hydrocarbon, and can reduce the burden on the environment.
  • the product oil obtained in the isomerization step contains a branched hydrocarbon compound.
  • the content of the branched hydrocarbon compound is preferably 5 to 90%, more preferably 10 to 80%, and more preferably 20 to 60% in terms of the weight ratio with respect to the total product oil. Particularly preferred.
  • the content of the branched hydrocarbon compound is lower than the lower limit, the effect of improving low-temperature fluidity is low, and when it is higher than the upper limit, the cracking reaction as a side reaction proceeds excessively, and the intended light oil fraction yield Decreases.
  • the hydrocarbon oil and its isomerized oil produced according to the present invention can be suitably used particularly as a diesel light oil or heavy oil base material.
  • the hydrocarbon oil according to the present invention may be used alone as a diesel light oil or heavy oil base material, but can be used as a diesel light oil or a heavy base material mixed with components such as other base materials.
  • a light oil fraction and / or kerosene fraction obtained in a general petroleum refining process and a residual fraction obtained by the production method of the present invention can be mixed.
  • a synthetic light oil or a kerosene obtained through a Fischer-Tropsch reaction or the like using so-called synthesis gas composed of hydrogen and carbon monoxide as a raw material can be mixed.
  • These synthetic light oils and kerosene are characterized by containing almost no aromatic content, having a saturated hydrocarbon as a main component, and a high cetane number.
  • a well-known method can be used as a manufacturing method of synthesis gas, and it is not specifically limited.
  • the residual fraction obtained by the production method of the present invention has a sulfur content of 0.1% by mass or less and an oxygen content of 1% by mass or less, and is used as a low sulfur heavy substrate. be able to.
  • the residual fraction is suitable as a feedstock for catalytic cracking.
  • a gasoline base material and other fuel oil base materials with little sulfur content can be manufactured by using the residue fraction of a low sulfur level for a catalytic cracking apparatus.
  • the residual fraction can be used as a feedstock for hydrocracking. By providing such a residual fraction to a hydrocracking apparatus, it is possible to improve the cracking activity and to improve the quality of each product oil fraction.
  • the cake-like slurry was transferred to a container equipped with a reflux condenser, 150 ml of distilled water and 10 g of 27% aqueous ammonia solution were added, and the mixture was heated and stirred at 75 ° C. for 20 hours.
  • the slurry was put in a kneading apparatus and heated to 80 ° C. or higher and kneaded while removing moisture to obtain a clay-like kneaded product.
  • the obtained kneaded material was extruded into a shape of a cylinder having a diameter of 1.5 mm by an extrusion molding machine, dried at 110 ° C. for 1 hour, and then fired at 550 ° C. to obtain a molded carrier.
  • a commercially available silica alumina carrier N632HN manufactured by JGC Chemical Co., Ltd.
  • Example 1 A reaction tube (inner diameter 20 mm) filled with catalyst A (100 ml) was attached to a fixed bed flow type reactor. Thereafter, using straight-run gas oil (sulfur content: 3% by mass) to which dimethyl disulfide has been added, the catalyst layer average temperature is 300 ° C., the hydrogen partial pressure is 6 MPa, the liquid space velocity is 1 h ⁇ 1 , and the hydrogen / oil ratio is 200 NL / L. The catalyst was presulfided for 4 hours.
  • straight-run gas oil sulfur content: 3% by mass
  • the hydrorefining conditions were a reaction tube inlet temperature of 180 ° C., a hydrogen pressure of 3 MPa, a liquid space velocity of 0.5 h ⁇ 1 , and a hydrogen / oil ratio of 500 NL / L.
  • the treated oil after hydrorefining was introduced into a high-pressure separator, and hydrogen, hydrogen sulfide, carbon dioxide and water were removed from the treated oil.
  • the spilled oil after introduction of the high-pressure separator was guided to a rectification column, and fractionated into a light fraction having a boiling point range of less than 150 ° C, an intermediate fraction having a boiling point of 150 to 350 ° C, and a heavy fraction having a temperature exceeding 350 ° C.
  • Example 2 Hydrorefining was performed in the same manner as in Example 1 except that the hydrogen pressure was 5 MPa. The hydrorefining conditions are shown in Table 3, and the obtained results are shown in Table 4.
  • Example 3 Instead of recycling the middle distillate after fractional distillation, a portion of the treated oil from which by-products have been removed with a high-pressure separator is cooled to 40 ° C. with cooling water, and then recycled in an amount that is 1 times the mass of palm oil. Except for the above, hydrorefining was performed in the same manner as in Example 1. The hydrorefining conditions are shown in Table 3, and the obtained results are shown in Table 4.
  • Example 4 A second reaction tube (inner diameter: 20 mm) filled with catalyst B (50 mL) was connected to the fixed bed flow reactor of Example 1.
  • the catalyst B was subjected to reduction treatment for 6 hours under conditions of an average catalyst layer temperature of 320 ° C., a hydrogen pressure of 5 MPa, and a hydrogen gas amount of 83 ml / min.
  • the steps up to obtaining the middle distillate were the same as in Example 1.
  • the remaining middle distillate was recycled and the reaction tube (inner diameter 20 mm) filled with catalyst B (50 ml) was connected to a fixed bed flow reactor (isomerization unit). ) And subjected to isomerization treatment.
  • the catalyst B is subjected to a reduction treatment for 6 hours under conditions of an average catalyst layer temperature of 320 ° C., a hydrogen pressure of 5 MPa, and a hydrogen gas amount of 83 ml / min, and then the catalyst layer average temperature of 330 ° C. and a hydrogen pressure of Was isomerized under the conditions of 3 MPa, liquid hourly space velocity of 1 h ⁇ 1 , and hydrogen / oil ratio of 500 NL / L.
  • the oil after the isomerization treatment was further guided to the second rectification column and fractionated into a light fraction having a boiling point range of less than 150 ° C, an intermediate fraction having a boiling point of 150 to 350 ° C, and a heavy fraction having a temperature exceeding 350 ° C.
  • This second middle distillate is used as a light oil base material.
  • the hydrorefining conditions are shown in Table 3, and the obtained results are shown in Table 4. It can be seen that the isoparaffin ratio of the light oil base is increased and the pour point is lowered (low temperature performance can be improved) by the isomerization treatment.
  • Example 5 A second reaction tube (inner diameter 20 mm) filled with catalyst B (50 mL) was connected to the fixed bed flow reactor of Example 1. The catalyst B was subjected to reduction treatment for 6 hours under conditions of an average catalyst layer temperature of 320 ° C., a hydrogen pressure of 5 MPa, and a hydrogen gas amount of 83 ml / min.
  • the process until the removal of hydrogen, hydrogen sulfide, carbon dioxide and water from the treated oil with the high-pressure separator was the same as in Example 1, and the reaction tube (50 ml) filled with the spilled oil obtained from the high-pressure separator ( An inner diameter of 20 mm) was introduced into a fixed bed flow type reaction apparatus (isomerization apparatus) and subjected to isomerization treatment.
  • the catalyst B is subjected to a reduction treatment for 6 hours under conditions of an average catalyst layer temperature of 320 ° C., a hydrogen pressure of 5 MPa, and a hydrogen gas amount of 83 ml / min, and then the catalyst layer average temperature of 330 ° C.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

Selon l’invention, une huile hydrocarbonée est obtenue par hydrogénation d'une huile matière première contenant un composé hydrocarboné contenant de l'oxygène issu d'une huile animale/végétale et un catalyseur contenant un oxyde inorganique poreux contenant au moins deux éléments choisis parmi l'aluminium et similaire et un ou plusieurs métaux choisis parmi les éléments du groupe 6A et du groupe 8 du tableau périodique et supportés sur l'oxyde inorganique poreux, en présence d'hydrogène à une pression d'hydrogène non inférieure à 1 MPa mais inférieure à 6 MPa ; puis élimination de l'hydrogène et similaire du produit hydrogéné résultant. L'huile matière première contient une huile de recyclage qui est obtenue par introduction par recyclage d'une partie de l'huile hydrocarbonée obtenue dans l'étape précédente dans une quantité de 0,5-5 fois la masse du composé hydrocarboné contenant de l'oxygène et 1-50 ppm en masse d'un composé hydrocarboné contenant du soufre en termes d'atomes de soufre par rapport au composé hydrocarboné contenant de l'oxygène.
PCT/JP2009/058573 2008-05-14 2009-05-01 Procédé pour la fabrication d'huile hydrocarbonée WO2009139313A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007068796A2 (fr) * 2005-12-12 2007-06-21 Neste Oil Oyj Procede de production d'un compose d'hydrocarbure ramifie
JP2007308563A (ja) * 2006-05-17 2007-11-29 Nippon Oil Corp 水素化精製方法
JP2007308573A (ja) * 2006-05-17 2007-11-29 Nippon Oil Corp 軽油組成物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007068796A2 (fr) * 2005-12-12 2007-06-21 Neste Oil Oyj Procede de production d'un compose d'hydrocarbure ramifie
JP2007308563A (ja) * 2006-05-17 2007-11-29 Nippon Oil Corp 水素化精製方法
JP2007308573A (ja) * 2006-05-17 2007-11-29 Nippon Oil Corp 軽油組成物

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