WO2005095554A1 - 水素製造用炭化水素油および水素製造システム - Google Patents
水素製造用炭化水素油および水素製造システム Download PDFInfo
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- WO2005095554A1 WO2005095554A1 PCT/JP2005/006706 JP2005006706W WO2005095554A1 WO 2005095554 A1 WO2005095554 A1 WO 2005095554A1 JP 2005006706 W JP2005006706 W JP 2005006706W WO 2005095554 A1 WO2005095554 A1 WO 2005095554A1
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
- C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
- C01B3/26—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/06—Integration with other chemical processes
- C01B2203/066—Integration with other chemical processes with fuel cells
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1247—Higher hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1258—Pre-treatment of the feed
- C01B2203/1264—Catalytic pre-treatment of the feed
- C01B2203/127—Catalytic desulfurisation
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- the present invention relates to a hydrocarbon oil for hydrogen production and a hydrogen production system. [Background technology]
- Fuel cells hydrogen Hydrogen-fueled systems such as rice fields are in the limelight, among which hydrogen is supplied directly to the fuel cell by compression or liquefaction, as well as methanol.
- oxygen-containing fuel such as naphtha, kerosene, and other hydrocarbons by reforming hydrocarbons
- Non-Patent Document 1 Although it has the advantage of being able to be used as a gas, it has problems in storage properties because it is a gas at room temperature, and in its mountability when used in vehicles, etc.
- Methanol is used to convert hydrogen by reforming in the system.
- Such hydrocarbons require a reforming process for hydrogen generation, but there are problems with the durability of the reforming system and high hydrogen generation efficiency may not be obtained. It was.
- carbon monoxide, carbon dioxide, methane, etc. are included in the reformed gas in addition to hydrogen. It is known that carbon monoxide in the reformed gas is a catalyst poison that lowers the performance of a catalyst contained in an electrode used in a fuel cell, particularly a polymer electrolyte fuel cell. For this reason, carbon monoxide purifiers are installed in fuel cells that use hydrocarbons, especially in hydrogen production systems for polymer electrolyte fuel cells. However, depending on the type of hydrocarbon, the amount of carbon monoxide generated in the reformed gas was large, and high hydrogen generation efficiency could not be obtained.
- Non-Patent Document 1 Masao Ikematsu, “Engine Technology”, Sankaidosha, 2001
- the present invention provides a stable and high desulfurization rate, excellent durability of the reformer, a low amount of carbon monoxide generated in the reformed gas, and high hydrogen generation efficiency.
- the purpose is to provide a production hydrocarbon oil and hydrogen production system.
- the present inventors have found that a hydrocarbon oil having a specific property obtained by treating a specific raw material in a specific step can solve the above problems, and have completed the present invention. That is, in the first aspect of the present invention, the initial boiling point is 140 to 180 ° C., 90% by volume, the distillation temperature is 200 to 270 ° C., and the aromatic content is 20% by volume.
- the content of the linear saturated hydrocarbon is 25 mass. /.
- a hydrocarbon mixture having a linear saturated hydrocarbon content of 10 to 15 carbon atoms of 20% by mass or more and a sulfur content of 300% by mass or less is used as a raw material oil, and the following step (1) (3) containing a hydrocarbon base material, having an initial boiling point of 160 ° C. or more and 200 ° C. or less, and a 50% by volume distillation temperature of 200 ° C.
- Step (2) Stripping 1 to 35% by volume of light components from the hydrodesulfurized oil obtained in Step (1)
- Step (3) After stripping the light components, extracting and removing 10% by volume or more of the linear saturated hydrocarbon with zeolite under the conditions of a temperature of 150 to 250 ° C and a pressure of 1 to 5 MPa.
- the second is that the initial boiling point is 140 to 180 ° C, the 90% by volume distillation temperature is 200 to 270 ° C, the aromatic content is 20% by volume or less, and the linear saturated hydrocarbon content is 25% by mass or more.
- the resulting hydrocarbon base material contains a 95% by volume distillation temperature of 240 ° C or less, a difference between the 95% by volume distillation temperature and the initial boiling point of 50 ° C or less, and a sulfur content of 0.5%.
- Mass ppm or less, molar ratio of carbon to hydrogen: 1.95 or more, naphthene content: 40% by volume or more, aromatics: 10% by volume or less, oxidation start temperature: 210 ° C or more It features relating to hydrogen production hydrocarbon oil of the hydrogen production system disposed at least carbon monoxide purifier to.
- Step (1) Feedstock oil, a reaction temperature two hundred and fifty to three hundred ten ° C, the hydrogen pressure 5 ⁇ 1 OMP a, LHSV 0. 5 ⁇ 3 0 h 1, hydrogen Z hydrocarbon volume ratio 0.1 5-0 6 Hydrodesulfurization treatment with a catalyst selected from Ni-W, Ni-Mo, Co-Mo, Co-W, and Ni-Co-Mo under the following conditions: Process
- Step (2) Step of stripping 1 to 35% by volume of light components from the hydrodesulfurized oil obtained in Step (1)
- Step (3) After stripping the light components, extracting and removing 10% by volume or more of linear saturated hydrocarbons by zeolite under the conditions of a temperature of 150 to 250 ° C and a pressure of 1 to 5 MPa.
- Step (4) fractionate the hydrocarbon oil from which the straight-chain saturated hydrocarbon has been extracted and removed in step (3)
- the initial boiling point is 140 to 180 ° C.
- the 90% by volume distillation temperature is 200 to 270 ° C.
- the aromatic content is 20% by volume or less
- the linear saturated hydrocarbon is contained.
- a hydrocarbon mixture having an amount of 25% by mass or more, a straight-chain saturated hydrocarbon having 10 to 15 carbon atoms of 20% by mass or more, and a sulfur content of 300% by mass or less is used as a raw material oil in the following step ( 1) to (3) and (5) containing a hydrocarbon base material, flash point of 40 ° C or higher, initial boiling point of 145 ° C or higher, 170 ° C or lower, 50% by volume Distillation temperature: 180 ° C to 220 ° C, 95% by volume Distillation temperature: 220 ° C to 260 ° C, Sulfur content 0.5 mass ppm or less, Smoke point 26 mm or more, Aromatic
- the present invention relates to a hydrocarbon oil for hydrogen production in a hydrogen production system having at least a reformer, wherein the content is 10% by volume or less and the oxidation start temperature is 210 ° C. or more.
- Step (1) Feed oil at a reaction temperature of 250 to 310 ° C, hydrogen pressure of 5 to 1 OMPa, LHSV of 0.5 to 3.0 h— 1 , hydrogen / hydrocarbon capacity ratio of 0.15 to 0 Under the conditions of 6, hydrogenation with a catalyst containing one selected from Ni—W, Ni—Mo, Co—Mo, Co—W, and Ni_Co—Mo power Desulfurization process
- Step (2) Step of stripping 1 to 35% by volume of light components from the hydrodesulfurized oil obtained in Step (1)
- Step (3) After stripping the light components, extracting and removing 10% by volume or more of linear saturated hydrocarbons with zeolite under conditions of a temperature of 150 to 250 ° C and a pressure of 1 to 5 MPa.
- Step (5) The hydrocarbon obtained in Step (3) or the hydrocarbon obtained in Step (4) is fractionated with the hydrocarbon obtained in Step (3).
- a step of mixing 60% by volume or more of the light component stripped in the fourth step of the present invention is to mix the first hydrocarbon oil of the present invention with a reaction pressure (absolute pressure) IMPa of a desulfurization reactor, Hydrogen equipped with a desulfurization reactor for desulfurization by controlling the maximum temperature of the desulfurization catalyst layer in the range of the initial boiling point of hydrocarbon oil-50 ° C to the initial boiling point of hydrocarbon oil + 100 ° C Related to manufacturing system.
- a fifth aspect of the present invention is that a reformed gas obtained by reforming the second hydrocarbon oil of the present invention and water
- the reaction temperature is adjusted to 100 to 6 in the presence of a catalyst containing an active metal containing one or more elements selected from Groups IB, IIB, VI, and VIII of the Periodic Table by mixing steam.
- Water gas shift reactor for obtaining carbon dioxide and hydrogen as products from carbon monoxide and water vapor at a temperature of 00 ° C and a ratio of water to carbon monoxide in reformed gas of 1 to 80 mol / mol It relates to a hydrogen production system.
- a sixth aspect of the present invention is directed to a sixth aspect of the present invention, in which a mixed gas of the third hydrocarbon oil and the steam of the third aspect of the present invention is used in the presence of a reforming catalyst containing a Group VIII element of the periodic table as an active metal, at a reaction temperature of 400 to 1
- a seventh aspect of the present invention is to provide a mixed gas of the third hydrocarbon oil, steam and air of the present invention in the presence of a reforming catalyst containing a Group VIII element of the periodic table as an active metal, at a reaction temperature of 400. 1100 ° (: The reaction is carried out at a mixing ratio of water and hydrocarbon oil of 0.5 to 5 mol Z mol and a mixing ratio of oxygen and hydrocarbon oil of 0.1 to 0.5 mol Z mol. Accordingly, the present invention relates to a hydrogen production system equipped with an autothermal reformer for obtaining a product containing hydrogen as a main component.
- An eighth aspect of the present invention relates to the above-described hydrogen production system, comprising a desulfurization reactor, a reformer, and a carbon monoxide purifier.
- a desulfurization reactor comprising a desulfurization reactor, a reformer, and a carbon monoxide purifier.
- the hydrocarbon oil for hydrogen production of the present invention is a hydrocarbon oil having a specific property, comprising a hydrocarbon base material obtained by using a specific hydrocarbon mixture as a raw material oil and treating it in a specific step. It is.
- the hydrocarbon mixture used as the starting material oil has an initial boiling point of 140-180 ° C, 90% by volume, a distillation temperature of 200-270 ° C, and an aromatic content of 20% by volume. % Or less, straight-chain saturated hydrocarbon content is 25% by mass or more, straight-chain saturated hydrocarbon having 10 to 15 carbon atoms is 20% by mass or more, and sulfur content is 300% by mass or less. It is necessary to be.
- the initial boiling point is 150-170 ° C
- 90 vol% distilling temperature is 222-245 ° C
- the aromatic content is 15 vol% or less
- linear saturation Hydrocarbon content is 35% by volume or more, linear saturated hydrocarbons having 10 to 15 carbon atoms is 25% by volume or more, and sulfur content is 20% by volume. 0 mass p pm or less. If the properties of the feed oil are out of the above range, it is not preferable because the hydrocarbon oil of the present invention is difficult to obtain.
- the initial boiling point and 90% by volume distillation temperature are based on JIS K2254 “Petroleum product one distillation test method-Normal pressure distillation test method”, and the aromatic content is JIS K253 6 “Petroleum product one hydrocarbon type
- the values measured by the fluorescent indicator adsorption method, the content of straight-chain saturated hydrocarbons, and the content of straight-chain saturated hydrocarbons having 10 to 15 carbon atoms in “Test method” are the values measured using GC-FID (mass %).
- a methyl silicon capillary column (ULTRAALLOY-1) is used as the column
- helium is used as the carrier gas
- FID hydrogen ion detector
- step (1) the feedstock is subjected to a reaction temperature of 250 to 310 ° C, a hydrogen pressure of 5 to 10 MPa, an LHSV of 0.5 to 3.0 h- 1 , a hydrogen Z hydrocarbon volume ratio of 0. Hydrogenation with a catalyst containing any one selected from Ni-W, Ni-Mo, Co-Mo, Co-W, and Ni-Co_Mo under the conditions of 15 to 0.6
- the desulfurization treatment is performed, and the reaction temperature of the hydrodesulfurization treatment is from 250 to 310 ° C, and preferably from 28 to 300 ° C. If the reaction temperature is lower than 250 ° C, a sufficient hydrodesulfurization reaction rate cannot be obtained, while if it exceeds 310 ° C, the hydrodesulfurization reaction becomes insufficient in terms of reaction equilibrium.
- the hydrogen pressure in the hydrodesulfurization treatment is 5 to 10 MPa, preferably 7 to 9 MPa.
- the LHSV in the hydrodesulfurization treatment is 0.5 to 3.0 h- 1 , preferably 1-2 h- 1 .
- LHSV Although it is advantageous for as low reaction, the case of less than 0. 5 h one 1 requires a very large reactor volumes.
- the hydrogen / hydrocarbon capacity ratio is 0.15 to 0.6, preferably 0.2 to 0.6. 0.4.
- the catalyst used in the hydrodesulfurization treatment contains any active metal selected from Ni-W, Ni-Mo, Co_Mo, Co-W, and Ni-Co-Mo. It is necessary.
- the active metal is preferably used by being supported on a porous carrier.
- an inorganic oxide is preferably used as the porous carrier.
- the inorganic oxide include alumina, titania, zirconia, polya, silica, and zeolite.Of these, at least one of titania, zirconia, polya, silica, and zeolite is composed of alumina.
- the amount of the active metal to be supported is not particularly limited, but is preferably 20 to 35% by mass in total of the metal oxide based on the total amount of the catalyst.
- the catalyst is preferably used after pre-sulfidation treatment with hydrogen and sulfur compounds.
- a gas containing hydrogen and sulfur compounds is circulated, and the active metal on the catalyst is pre-sulfided by applying heat of 200 ° C or more according to a predetermined procedure, and hydrogenation and desulfurization activities are exhibited. Will be.
- step (2) light components (generally a boiling point of 200 ° C or less) are stripped (removed) from the hydrodesulfurized oil obtained in step (1).
- the strip amount is 1 to 35% by volume, preferably 10 to 35% by volume, and more preferably 20 to 35% by volume, based on the hydrodesulfurized oil.
- step (3) the hydrocarbon oil from which the light components have been stripped (removed) in step (2) is subjected to a temperature of 150 ° C to 250 ° C and a pressure of 1 to 5 MPa. Extract and remove 10% by volume or more of straight-chain saturated hydrocarbons with zeolite.
- the extraction temperature for the removal of linear saturated hydrocarbons is 150 ° (: ⁇ 250 ° C, preferably 180-200 ° C.
- the removal rate of hydrocarbons cannot be obtained on the other hand, if the temperature exceeds 250 ° C, the efficiency of removing saturated Naugagu hydrocarbons decreases, and the pressure at this time is 1 to 5 MPa, preferably 1.5 If the pressure is less than IMPa, a sufficient removal rate of linear saturated hydrocarbons cannot be obtained, whereas if the pressure exceeds 5 MPa, a sufficient removal rate of linear saturated hydrocarbons can be obtained.
- the zeolite used for removing the linear saturated hydrocarbon is not particularly limited, but generally A-type zeolite is used, among which molecular sieve 5A is preferable. It is preferable to extract and remove hydrogen by 10% by volume or more, preferably 20% by volume or more.
- the hydrocarbon oil (I) of the invention is a hydrocarbon oil having the following specific properties, comprising the above-mentioned starting material oil and a hydrocarbon base material obtained through steps (1) to (3). .
- the lower limit of the initial boiling point (I BP) of the hydrocarbon oil (I) of the present invention must be 160 ° C or higher, and preferably 170 ° C or higher, in order to obtain a stable and high desulfurization rate. 180 ° C or higher is more preferable.
- the upper limit needs to be 200 ° C or lower, and preferably 190 ° C or lower, from the viewpoint of the startability of the desulfurization system.
- the lower limit of the 50% by volume distilling temperature (T50) of the hydrocarbon oil (I) of the present invention must be 200 ° C or higher in order to obtain a stable and high desulfurization rate. Above is preferable, and 210 ° C. or higher is more preferable. On the other hand, the upper limit needs to be 220 ° C or lower from the viewpoint of the desirability of the desulfurization system.
- the lower limit of the 90% by volume distillation temperature (T 90) of the hydrocarbon oil (I) of the present invention must be 220 ° C. or higher, and 225 ° C. or lower. Above is preferable, and 230 ° C or more is more preferable.
- the upper limit needs to be 245 ° C or lower, and preferably 240 ° C or lower, because the hydrocarbon component in the reformed gas at the time of the reforming reaction increases.
- the distillation properties of the hydrocarbon oil (I) of the present invention other than IBP, T50 and ⁇ 90 are not particularly limited, but the 10% by volume distillation temperature ( ⁇ 10) is from 170 ° C to 220 ° C. Is preferred.
- the lower limit of T 10 is 1 8 because evaporation gas (THC) is likely to be generated. It is more preferably 0 ° C or higher, further preferably 190 ° C or higher, and most preferably 195 ° C or higher.
- the temperature is preferably 210 ° C or lower, more preferably 200 ° C or lower.
- the end point (EP) is preferably from 230 ° C to 280 ° C.
- the temperature is preferably 240 ° C or higher, more preferably 250 ° C or higher.
- the temperature is preferably 270 ° C or lower, more preferably 260 ° C or lower.
- IBP, T10, ⁇ 50, ⁇ 90 and EP are JISK2
- the aromatic content of the hydrocarbon oil (I) of the present invention must be 10% by volume or less from the viewpoint of a decrease in the desulfurization rate and a decrease in the durability of the desulfurization system, and is 8 volumes. / 0 or less is preferred.
- the olefin content of the hydrocarbon oil (I) of the present invention is not particularly limited, but is preferably 5% by volume or less, more preferably 1% by volume or less, from the viewpoint of the durability of the desulfurization system. Most preferably, 1% by volume or less.
- the saturated content of the hydrocarbon oil (I) of the present invention is not particularly limited, but is preferably 85% by volume or more, more preferably 90% by volume or more, in view of the short start-up time of the desulfurization system.
- the aromatic content, olefin content and saturated content described above are the aromatic content, olefin content, and saturated hydrocarbon content measured by the fluorescent indicator adsorption method of JISK 2536 “Petroleum product-hydrocarbon type test method”. The value of the quantity.
- the sulfur content of the hydrocarbon oil (I) of the present invention must be 0.5 mass ppm or less in view of the desulfurization rate and the durability of the desulfurization catalyst, and is preferably 0.3 mass ppm or less. Preferably, 0.2 quality * ppm or less is more preferable.
- the sulfur content is a value measured by ASTM D4045-96 "Standard Test Method for Sulfur in Petroleum Products by Hydrogenolysis and Rateometric ColorimetryJ. (See comments on page 5.)
- the naphthene content of the hydrocarbon oil (I) of the present invention needs to be 40% by volume or more from the viewpoint of reducing the desulfurization rate and suppressing the decrease in the durability of the desulfurization catalyst. preferable.
- the naphthene content here refers to the content of naphthenic hydrocarbons measured by a method in accordance with ASTM D2425 (Test Method for Instrumental Determination of Carbon, Hydrogen, and Nitrogen in Petroleum Products and Lubricants). It is about quantity.
- the oxidation start temperature of the hydrocarbon oil (I) of the present invention needs to be 210 ° C. or higher, preferably 212 ° C. or higher, more preferably 215 ° C. or higher. . If the oxidation start temperature is lower than 210 ° C., it is not preferable because the durability of the desulfurization system deteriorates due to coking of the catalyst.
- the oxidation start temperature in the present invention is measured by using a high-pressure differential scanning calorimeter (hereinafter, referred to as “high-pressure DSC”). More specifically, the sample is introduced into a DSC pressurized cell (for example, manufactured by Metrado Red), and the sample is subjected to 20 ° C / min from 30 ° C to 500 ° C under an air atmosphere of 4 MPa. As a result, a correlation curve between the calorific value and the temperature is obtained. The oxidation start temperature is determined based on the force and the exothermic peak that appears first in the correlation curve.
- high-pressure DSC high-pressure differential scanning calorimeter
- Fig. 1 is a graph showing an example of a correlation curve between the calorific value and the temperature measured using a high-pressure DSC, and shows the measurement results for a hydrocarbon oil (I-A) described later.
- the vertical axis is the calorific value
- the horizontal axis is the temperature.
- FIG. 2 is a graph showing a derivative curve of the curve shown in FIG.
- the straight line 1 shows the tangent at the point where the heat generation per unit time is the maximum (point corresponding to point B in FIG. 2).
- 1 2 in Figure 1 illustrates a tangent line at the start of the heating (point curve rises).
- the temperature corresponding to the intersection A between 1 and 12 is the oxidation start temperature specified in the present invention.
- the component ratio of the hydrocarbon having 13 carbon atoms in the hydrocarbon oil (I) of the present invention is 20 mass from the viewpoint of the durability of the desulfurization system. / 0 or more, preferably 25% by mass or more.
- the number 1 3 in hydrocarbon content of carbon is a value (mass 0/0) which is determined using GC-FID.
- the column is a methyl silicon capillary column (ULTRAAL LOY-1, 0.25 mm ⁇ , 30 m)
- the carrier gas is Using a hydrogen ion detector (FID) as the detector, the carrier gas flow rate is 1.
- the split ratio is 1:79
- the sample injection temperature is 280 ° C
- the column temperature is 50 ° C (5 minutes) ⁇ (5 ° C / min) ⁇ 280 ° C (10 minutes)
- a hydrocarbon base material obtained through the aforementioned steps (1) to (3) can be used.
- another base material can be appropriately mixed with the hydrocarbon base material as long as the above properties are maintained.
- the mixing ratio of the other base materials that can be mixed is preferably 20% by volume or less, more preferably 15% by volume or less, and more preferably 10% by volume or less based on the total amount of the hydrocarbon oil. Preferred. If the content of the other base material exceeds 20% by volume, it is not preferable from the viewpoint of deteriorating the durability of the desulfurization catalyst.
- the hydrocarbon mixture from which the straight-chain saturated hydrocarbons have been extracted and removed in the step (3) is fractionated by a distillation operation.
- the cut point in the fractionation is that the hydrocarbon base material generated by this operation has a 95% by volume distillation temperature of 240 ° C or less, and the difference between the 95% by volume distillation temperature and the initial boiling point is 50 ° C. Control to be below C. It is desirable to install a hydrogenation unit before distillation to reduce the aromatic content of the product.
- the hydrocarbon oil for hydrogen production ( ⁇ ) of the present invention is a hydrocarbon having the following specific properties, comprising the above-mentioned starting material oil and a hydrocarbon base obtained through steps (1) to (4). Oil.
- the upper limit of the 95% by volume distilling temperature (T 95) of the hydrocarbon oil ( ⁇ ) of the present invention is determined from the viewpoint of low carbon monoxide generation in reformed gas and high hydrogen generation efficiency. It is necessary to be not more than ° C, preferably not more than 220 ° C, and more preferably not more than 180 ° C.
- the difference between the 95% by volume distillation temperature (T 95) and the initial boiling point (I BP) of the hydrocarbon oil ( ⁇ ) of the present invention is due to the low carbon monoxide generation amount in the reformed gas and the hydrogen generation efficiency From the viewpoint of height, the temperature must be 50 ° C or lower, preferably 40 ° C or lower, more preferably 15 ° C or lower. Further, the distillation properties of the hydrocarbon oil ( ⁇ ) other than T95 of the present invention are not particularly limited, but it is necessary for the IBP so that the difference between T95 and IBP satisfies the above-mentioned specific range.
- IBP is preferably 145 ° C or higher, more preferably 150 ° C or higher, and most preferably 155 ° C or higher, from the viewpoints of flammability, increase in evaporative gas (THC), and handleability.
- the temperature is preferably 220 ° C. or lower, more preferably 205 ° C. or lower, and most preferably 170 ° C. or lower.
- the 10% by volume distillation temperature (T 10) is preferably from 150 ° C to 220 ° C. From the viewpoint of flammability and an increase in evaporative gas (THC), the temperature is more preferably at least 155 ° C, and even more preferably at least 160 ° C. On the other hand, from the viewpoint of deteriorating the start-up time of the hydrogen production system, the temperature is preferably 210 ° C or lower, and more preferably 180 ° C or lower.
- the 50% by volume distillation temperature (T 50) is preferably from 150 ° C to 220 ° C. From the viewpoint of the amount of hydrogen generated per weight and the amount of hydrogen generated per carbon dioxide generated, the temperature is more preferably 155 ° C or higher, and further preferably 160 ° C or higher. On the other hand, the temperature is more preferably 210 ° C. or lower, and further preferably 180 ° C. or lower, from the viewpoint of deterioration of the starting time of the hydrogen production system.
- the 90% by volume distillation temperature (T90) is preferably from 160 ° C to 250 ° C. From the viewpoint of the amount of hydrogen generated per weight and the amount of hydrogen generated per carbon dioxide generated, the temperature is more preferably 165 ° C or higher, and further preferably 170 ° C or higher. On the other hand, from the viewpoint of an increase in THC in the exhaust gas, the temperature is more preferably 220 ° C or lower, and further preferably 180 ° C or lower.
- the end point (EP) is preferably from 160 ° C to 260 ° C.
- the temperature is more preferably 170 ° C or higher, and further preferably 180 ° C or higher.
- the temperature is more preferably 230 ° C or lower, and further preferably 210 ° C or lower.
- ⁇ ⁇ ⁇ , ⁇ 10, ⁇ 50, ⁇ 90, ⁇ 95, and ⁇ ⁇ are J
- the sulfur content of the hydrocarbon oil ( ⁇ ) of the present invention depends on the desulfurization rate, the durability of the desulfurization catalyst, the durability of the reforming catalyst, the lowering of the reforming reactivity, and the amount of hydrogen generated per carbon dioxide generated. Therefore, it is necessary to be 0.5 mass ppm or less, preferably 0.3 mass ppm or less, more preferably 0.15 mass ppm or less.
- the sulfur content is a value measured by ASTM D4045-96 “Standard Test Method for Sulfur in Petroleum Products by Hydrogenolysis and Rateometric ColorimetryJ”.
- the hydrocarbon oil (II) of the present invention requires that the molar ratio of carbon to hydrogen (CZH) in the hydrocarbon oil be 1.95 or more. From the viewpoint of the small amount of carbon monoxide generated in the reformed gas and the high hydrogen generation efficiency, 2.00 or more is preferable, and 2.05 or more is more preferable.
- the molar ratio of carbon to hydrogen in hydrocarbon oil (CZH) is measured by a method based on ASTM D 5291-01 (Standard Test Method for Hydrocarbon Types in Middle Distillates by Mass Spectrometry). Value.
- the naphthene content of the hydrocarbon oil ( ⁇ ) of the present invention is determined to be lower in desulfurization rate, lower in durability of desulfurization catalyst, lower in durability of reforming catalyst, lower in reforming reactivity, lower in carbon monoxide purification catalyst. It is necessary to be at least 40% by volume, preferably at least 45% by volume, from the viewpoint of suppressing the reduction of the durability of carbon dioxide, the reduction of the carbon monoxide removal rate, and the reduction of the amount of hydrogen generated per amount of carbon dioxide generated. , 50% by volume or more is more preferable.
- the naphthenic content referred to here is the naphthenic hydrocarbon content measured by a method based on ASTM D 2425 (Test Method for Instrumental Determination of arbon, Hydrogen, and Nitrogen in Petroleum Products and Lubricants). Say.
- the aromatic hydrocarbon content of the hydrocarbon oil (II) of the present invention is as follows: decrease in desulfurization rate, decrease in durability of desulfurization catalyst, decrease in durability of reforming catalyst, decrease in reforming reactivity, reduction in monoxide. It is necessary to be 10% by volume or less from the viewpoint of suppressing the reduction of the durability of the carbon purification catalyst, the reduction rate of carbon monoxide, the reduction of the amount of hydrogen generated per amount of carbon dioxide, etc., and 5% by volume. Or less, more preferably 3% by volume or less, still more preferably 1% by volume or less, and even more preferably 0.5% by volume or less.
- the olefin content of the hydrocarbon oil ( ⁇ ) of the present invention is preferably 5% by volume or less, more preferably 1% by volume or less, and 0.3% by volume, from the viewpoints of low deterioration of the quality catalyst, long-lasting initial performance and good storage stability. The following are most preferred.
- the saturated hydrocarbon content of the hydrocarbon oil ( ⁇ ) of the present invention is not limited at all, but the amount of hydrogen generated per weight, the amount of hydrogen generated per carbon dioxide, and the amount of exhaust gas From the viewpoints of low THC and short system startup time, 85% by volume or more is preferable, 90% by volume or more is more preferable, and 95% by volume or more is most preferable.
- the above-mentioned aromatic content, olefin content, and saturated hydrocarbon content are values measured by the fluorescent indicator adsorption method of JIS K 253 “Petroleum products—one hydrocarbon type test method”.
- the oxidation start temperature of the hydrocarbon oil ( ⁇ ) of the present invention needs to be 210 ° C. or higher, preferably 212 ° C. or higher, more preferably 215 ° C. or higher. . If the oxidation start temperature is lower than 210 ° C., it is not preferable because the coking of the reforming catalyst deteriorates the durability of the hydrogen production apparatus.
- hydrocarbon oil (II) for hydrogen production of the present invention a hydrocarbon base material obtained through the aforementioned steps (1) to (4) can be used. Further, other hydrocarbon-producing substrates may be appropriately mixed with the hydrocarbon substrate as long as the above properties are maintained.
- the mixing ratio of other base materials that can be mixed is preferably 20% by volume or less, more preferably 15% by volume or less, and more preferably 10% by volume or less based on the total amount of the hydrocarbon oil. More preferred. If the content of the other base material exceeds 20% by volume, the amount of hydrogen generated per weight decreases, and the amount of carbon dioxide generated per hydrogen generation is undesirably increased.
- step (5) the hydrocarbon obtained in the step (3) or the hydrocarbon obtained in the step (4) Then, 60% by volume or more, preferably 70% by volume or more, of the light components stripped in step (2) is mixed.
- the hydrocarbon oil ( ⁇ ) for hydrogen production of the present invention contains a hydrocarbon base obtained by subjecting the above-mentioned starting material oil to the steps (1) to (3) and (5). Specificity It is a hydrocarbon oil having a shape.
- the flash point of the hydrocarbon oil (m) of the present invention must be 4 ° C or higher, preferably 42 ° C or higher, more preferably 45 ° C or higher, from the viewpoints of flammability and easy handling. Better.
- the flash point here is a value measured by JIS K 2265 "Crude oil and petroleum products-Flash point test method”.
- the lower limit of the initial boiling point (I BP) of the hydrocarbon oil (II) of the present invention needs to be 145 ° C or higher, preferably 150 ° C or higher.
- the upper limit needs to be 170 ° C. or lower, preferably 165 ° C. or lower, more preferably 160 ° C. or lower, and even more preferably 150 ° C. or lower. If I BP is lower than 145 ° C, it is not preferable from the viewpoint of flammability, increase in evaporative gas (THC), and handleability. If I BP exceeds 165 ° C, it is not preferable because the start-up time of the hydrogen production system deteriorates.
- the lower limit of the 50% by volume distillation temperature (T 50) of the hydrocarbon oil (m) of the present invention needs to be 18 ° C. or higher, preferably 185 ° C. or higher, and more preferably 190 ° C. or higher. More preferred.
- the upper limit needs to be 220 ° C or lower, preferably 215 ° C or lower, more preferably 210 ° C or lower. If T50 is lower than 180 ° C, the amount of hydrogen generated per weight and the amount of hydrogen generated per carbon dioxide decrease, which is not preferable.If it exceeds 220 ° C, it is preferable because the start-up time of the hydrogen production system deteriorates. Absent.
- the lower limit of the 95% by volume distillation temperature (T95) of the hydrocarbon oil ( ⁇ ) of the present invention needs to be 220 ° C or higher, preferably 225 ° C or higher, more preferably 230 ° C or higher. Good.
- the upper limit needs to be 260 ° C or lower, preferably 255 ° C or lower, and more preferably 250 ° C or lower. If T95 is lower than 220 ° C, the amount of hydrogen generated per weight and the amount of hydrogen generated per carbon dioxide decrease, which is not preferable.If it exceeds 260 ° C, THC in exhaust gas increases, which is not preferable. .
- the distillation properties of the hydrocarbon oil ( ⁇ ) of the present invention other than IBP, T50 and ⁇ 95 are not particularly limited, but the 10% by volume distillation temperature ( ⁇ 10) is from 160 ° C to 190 ° C. preferable.
- the temperature is more preferably 165 ° C or more, and further preferably 170 ° C or more, because the flammability is increased and evaporative gas (THC) is easily generated.
- the temperature is preferably 185 ° C or less, more preferably 180 ° C or less, because of the deterioration of the start-up time of the hydrogen production system.
- the 90% by volume distillation temperature (T 90) is preferably from 210 ° C to 255 ° C.
- the temperature is preferably 245 ° C or lower, and more preferably 240 ° C or lower.
- the end point (EP) is preferably from 230 ° C to 280 ° C. 240 ° C. or higher is more preferable, and 245 ° C. or higher is more preferable because the amount of hydrogen generation per weight and the amount of hydrogen generation per carbon dioxide generation decrease.
- the temperature is preferably 270 ° C or lower, more preferably 260 ° C or lower.
- ⁇ ⁇ , ⁇ 10, ⁇ 50, ⁇ 90, ⁇ 95, and ⁇ ⁇ ⁇ are the values measured by JIS ⁇ 2254 ⁇ Petroleum products-one distillation test method-normal pressure distillation test method ''. .
- the sulfur content of the hydrocarbon oil (m) of the present invention is 0 from the viewpoint of the desulfurization rate, the durability of the desulfurization catalyst, the durability of the reforming catalyst, the decrease in the reforming reactivity, and the amount of hydrogen generated per carbon dioxide generated. It is necessary to be not more than 5 mass ppm, preferably not more than 0.3 mass ppm, more preferably not more than 0.2 mass ppm.
- the sulfur content is a value measured by ASTM D4045-96 “Standard Test Method for Sulfur in Petroleum Products by Hydrogenesis and Rateometric ColorimetryJ”.
- the smoke point of the hydrocarbon oil (m) of the present invention is that the amount of hydrogen generated per weight is large, the amount of hydrogen generated per carbon dioxide is large, the THC in exhaust gas is small, 26 mm or more is necessary, 27 mm or more is preferable, and 28 mm or more is more preferable because the starting time is short, the deterioration of the reforming catalyst is small, and the initial performance can be maintained for a long time.
- the smoke point is a value measured by JIS K2537 "Test method for petroleum products-kerosene and aviation turbine fuel oil-smoke point".
- the aromatic content of the hydrocarbon oil ( ⁇ ) of the present invention is that the amount of hydrogen generated per weight is large, the amount of hydrogen generated per carbon dioxide is large, the THC in exhaust gas is small, From the viewpoint that the system startup time is short, the deterioration of the reforming catalyst is small, and the initial performance can be maintained for a long time, the content must be 10% by volume or less. % By volume or less is preferred.
- the olefin content of the hydrocarbon oil (m) of the present invention there is no limitation on the olefin content of the hydrocarbon oil (m) of the present invention.
- the amount of hydrogen generated per weight is large, the amount of hydrogen generated per carbon dioxide is large, and the THC in the exhaust gas is high.
- 5% by volume or less preferably 1% by volume, from the viewpoints that the amount of the catalyst is small, the system startup time is short, the deterioration of the reforming catalyst is small, the initial performance can be maintained for a long time, and the storage stability is good.
- the lower limit is more preferably 0.5% by volume or less.
- the saturated hydrocarbon content (total amount of saturated and naphthenic components) of the hydrocarbon oil (m) of the present invention is not limited at all, but the amount of hydrogen generated per weight is large, and the amount of hydrogen per carbon dioxide generated is large. From the viewpoints of a large amount of generation, a small amount of THC in the exhaust gas, and a short system startup time, it is preferably 85% by volume or more, more preferably 90% by volume or more, and 95% by volume or more. The above is most preferred.
- the above-mentioned aromatic content, olefin content, and saturated hydrocarbon content are values measured by the fluorescent indicator adsorption method of JIS K 253 “Petroleum products—one hydrocarbon type test method”.
- the hydrocarbon oil of the present invention (the naphthenic hydrocarbon content of mo is not limited at all. However, when the content of the naphthenic hydrocarbon decreases, the desulfurization rate decreases, the durability of the desulfurization catalyst decreases, and the reforming catalyst decreases. It is preferably at least 30% by volume, more preferably at least 40% by volume, from the viewpoint of suppressing the reduction of the durability of the steel, the reduction of the reforming reactivity, and the reduction of the amount of hydrogen generated per amount of carbon dioxide. It is more preferably at least 45% by volume.
- the content of the naphthenic hydrocarbon is measured by a method based on ASTM D2425 (Standard Test Method for Hydrocarbon Types in Middle Distillates by Mass Spectrometry).
- the oxidation initiation temperature of the hydrocarbon oil (II) of the present invention needs to be 210 ° C. or higher, preferably 212 ° C. or higher, more preferably 215 ° C. or higher. If the oxidation start temperature is lower than 210 ° C., it is not preferable in that the coking of the reforming catalyst deteriorates the durability of the hydrogen production apparatus.
- hydrocarbon oil (II) of the present invention a hydrocarbon base material obtained through the aforementioned steps (1) to (3) and (5) can be used. Further, another hydrocarbon-producing base material may be appropriately mixed with the hydrocarbon base material within a range in which the above properties are maintained. You can also.
- the mixing ratio of the other base materials that can be mixed is preferably 20% by volume or less, more preferably 15% by volume / 0 or less, and more preferably 10% by volume or less, based on the total amount of the hydrocarbon oil. Is more preferable. If the content of the other base material exceeds 20% by volume, it is not preferable in terms of a decrease in the conversion to a hydrogen-rich reformed gas at the beginning of the operation and a change in the conversion after the operation for 100 hours.
- the hydrocarbon oils (I) to (m) of the present invention are each suitably used as a hydrocarbon oil for hydrogen production for a hydrogen production system.
- a system including at least one device such as a desulfurization reactor, a reformer, and a carbon monoxide purifier is preferable.
- a desulfurization reactor, a reformer, Carbon monoxide purifier (b) desulfurization reactor ⁇ reformer ⁇ desulfurization reactor (re-desulfurization) ⁇ carbon monoxide purifier, (c) reformer ⁇ desulfurization reactor ⁇ carbon monoxide purifier
- a deployed system is preferably employed. However, it is not limited to this example.
- the desulfurization reactor (hereinafter, referred to as desulfurizer) used in the hydrogen production system of the present invention is a device for removing the sulfur content in hydrocarbon oil, and specifically, as a catalyst, a copper-zinc system or a nickele system is used. , Molybdenum, nickel-molybdenum, copanoletomolybdenum, cobalt-nickel-molybdenum, and the like.
- the catalyst is preferably a copper-zinc catalyst or a nickel catalyst.
- the reaction conditions must be such that the maximum temperature of the catalyst layer is controlled within the range from the initial boiling point temperature of hydrocarbon oil of 150 ° C to the initial boiling point temperature of hydrocarbon oil + 100 ° C. It is.
- the maximum temperature of the catalyst layer is preferably at least 30 ° C of the initial boiling point of hydrocarbon oil from the viewpoint of desulfurization performance, and the initial boiling point of hydrocarbon oil + 90 ° from the viewpoint of the durability of the desulfurization catalyst. ° C or lower, more preferably the initial boiling point temperature of the hydrocarbon oil +80 ° C or lower.
- LHSV is from the point of impact on the size of the desulfurizer, 0. LH 1 or more preferably, 0.
- the reaction pressure is preferably less than IMPa, more preferably 0.1 IMPa or less, in terms of installation of a stationary fuel cell in a home or commercial area.
- the desulfurization operation is preferably carried out so that the sulfur content of the hydrocarbon oil is preferably 0.1 mass ppm or less, more preferably 0.05 mass ppm or less.
- the reformer is a device for reforming hydrocarbon oil to obtain hydrogen, and specific examples include, but are not limited to, the following.
- the steam reforming reformer mixes heated and vaporized hydrocarbon oil with steam, and uses a Group VIII element of the periodic table as an active metal as a catalyst to obtain a product containing hydrogen as a main component. It is a reformer.
- the active metal of the catalyst used in the steam reforming type reformer is preferably ruthenium, rhodium, platinum or the like, particularly preferably ruthenium or rhodium, from the viewpoint of reforming reactivity for obtaining hydrogen from a hydrocarbon compound.
- the reaction temperature is preferably at least 400 ° C from the viewpoint of reforming reactivity, more preferably at least 500 ° C, and is preferably at most 1,000 ° C from the viewpoint of suppressing the amount of coking generated on the catalyst. The following are more preferred.
- the mixing ratio (SZC) of water and hydrocarbon oil is preferably 1 mol / mol or more, more preferably 2 mol / mol or more, from the viewpoint of suppressing the amount of coking generated on the catalyst, and 5 mol Z from the viewpoint of reformer efficiency. Mol or less, more preferably 4 mol or less Z mol.
- the autothermal reforming type reformer mixes heated and vaporized hydrocarbon oil with steam and air, and uses a Group VIII element of the periodic table as an active metal as a catalyst to obtain a product containing hydrogen as a main component. It is a reformer.
- the active metal of the catalyst used in the autothermal reforming reformer is preferably ruthenium, rhodium, platinum or the like, particularly preferably ruthenium or rhodium, in view of the reforming reactivity for obtaining hydrogen from a hydrocarbon compound.
- the reaction temperature is preferably at least 400 ° C from the viewpoint of reforming reactivity, more preferably at least 500 ° C, and is preferably at most 1,000 ° C from the viewpoint of suppressing the amount of coking generated on the catalyst. The following are more preferred.
- the mixing ratio (S / C) of water and hydrocarbon oil is preferably 0.5 mol / mol or more, more preferably 1 mol / mol or more, from the viewpoint of suppressing the amount of coking generated on the catalyst, and from the viewpoint of reformer efficiency. It is preferably 5 mol Z or less, more preferably 3 mol or less.
- the mixing ratio (o 2 Zc) of hydrogen and hydrocarbon oil is preferably 0.1 mol / mol or more, more preferably 0.2 mol mol or more, from the viewpoint of reforming reactivity. In this respect, the amount is preferably 0.5 mol mol or less, more preferably 0.4 mol / mol or less.
- o 2 is the number of moles of oxygen (molecule)
- C is the number of moles of carbon in hydrocarbon oil (molecule). Therefore, the method of obtaining the “mixing ratio of oxygen and hydrocarbon oil (o 2 / c)” will be described by giving an example.
- ethane (C 2 H 6 ): 1 mole is used as the oil
- the carbon monoxide purifier is contained in the gas generated in the reformer, and is a catalyst poison for fuel cells. The following are examples of carbon monoxide purifiers.
- the water gas shift reactor mixes the reformed gas obtained from the reformer with steam that has been heated and vaporized, and serves as a catalyst selected from the group IB, IIB, IV, and VIH of the periodic table. Or a reactor that uses two or more elements to obtain carbon dioxide and hydrogen as products from carbon monoxide and water vapor.
- the active metal of the catalyst used in the water gas shift reactor is preferably copper, zinc, chromium, iron, platinum, ruthenium, rhodium, or the like, and more preferably copper, zinc, or platinum.
- the reaction temperature is preferably 100 ° C. or higher in terms of reactivity, more preferably 200 ° C. or higher, and is preferably 60 ° C. from the viewpoint of suppressing coke deposition on the shift catalyst.
- the temperature is preferably 0 ° C or lower, more preferably 500 ° C or lower.
- the ratio of water and carbon monoxide in the reformed gas is preferably 1 mol Z mol or more, more preferably 2 mol mol or more, from the viewpoint of stably performing the reaction. Mol / mol or less is preferable, and 10 mol / mol or less is more preferable.
- the selective oxidation reactor mixes the reformed gas obtained from the reformer with compressed air, uses copper, nickel, platinum, ruthenium, rhodium, etc. as a catalyst, and has a reaction temperature of 100 to 300 ° C. , Gas space velocity 1 00 0 ⁇ :! OOOO h Reaction pressure Less than IMP a, ratio of air to carbon monoxide in reformed gas 0.5-3.0 mol Z mol, from carbon monoxide and air to carbon dioxide It is a reactor for conversion. Since the hydrocarbon oil (I) of the present invention is excellent in desulfurization performance, it is preferably used as a hydrocarbon oil for hydrogen production for a hydrogen production system provided with a desulfurization reactor. Therefore, in the hydrogen production system using the hydrocarbon oil (I) of the present invention, it is necessary to arrange at least a desulfurization reactor.
- the hydrocarbon oil (II) of the present invention can reduce the generation of carbon monoxide in the reformed gas, the hydrogen production using the above-described carbon monoxide purifier, particularly the water gas shift reactor, is provided. Hydrogen production efficiency can be increased by being used as a hydrocarbon oil for hydrogen production in systems. Therefore, it is necessary to arrange at least a carbon monoxide purifier in the hydrogen production system using the hydrocarbon oil (II) of the present invention.
- the hydrocarbon oil (II) of the present invention is suitably used as a raw material for a hydrogen production system having the steam reformer or the autothermal reformer described above.
- the reformer is a device for reforming hydrocarbons to obtain hydrogen, and by using the hydrocarbon oil (m) of the present invention, the durability of the reformer can be further improved, and as a result, hydrogen can be obtained.
- the durability of the manufacturing system is improved. Therefore, it is necessary to arrange at least a reformer in the hydrogen production system using the hydrocarbon oil (II) of the present invention. [Industrial applicability]
- the hydrocarbon oil for hydrogen production of the present invention can obtain a stable and high desulfurization rate.
- the reforming efficiency is high, and the performance of the reformer can be maintained for a long time.
- the amount of carbon monoxide generated in the reformed gas is suppressed and the hydrogen generation efficiency is high, it is suitable as a hydrocarbon oil for hydrogen production.
- the general properties of the hydrocarbon oil were measured by the following test methods.
- Density refers to the density measured by JIS K 2249 “Density test method for crude oil and petroleum products, as well as density / mass / volume conversion table”.
- Flash point refers to the flash point measured by JIS K 2265 “Crude oil and petroleum products-Flash point test method”.
- the sulfur content refers to the sulfur content measured by ASTM D4045-96 “Standard Test Method for Sulfur in Petroleum Products by Hydrogenolysis and Rateometric ColorimetryJ”.
- the aromatic, olefin and saturated components are the aromatic content, olefin content, and saturated hydrocarbon content measured by the fluorescent indicator adsorption method of JIS K2536 “Testing Methods for Hydrocarbons of Petroleum Products”. Refers to the content (including naphthenic hydrocarbons).
- the naphthene content refers to the naphthenic hydrocarbon content measured by a method based on ASTM D2425 (Standard Test Method for Hydrocarbon Types in Middle Distillates by Mass Spectrometry).
- Oxidation onset temperature refers to the temperature measured using a high-pressure differential scanning calorimeter, as described above.
- the ratio of the component of the hydrocarbon having 13 carbon atoms refers to a value measured by GC-FID according to the gas chromatography method described above.
- Smoke point refers to the smoke point measured in accordance with JIS K2 537 “Petroleum products – kerosene and aviation turbine fuel oil – smoke point test method”.
- Hydrocarbon substrates (I-1) to (I-13) were manufactured under the conditions shown in Table 1, and the hydrocarbon substrates (1-1) to (I-13) were blended and shown in Table 2. Hydrocarbon oils (I-A) to (I-D) were produced. Table 2 shows the properties.
- hydrocarbon oils (I-A) to (I-D) were evaluated by the desulfurization evaluation device shown in FIG.
- Hydrocarbon oil was introduced by a pump into a reaction tube filled with a desulfurization catalyst (nickel-based, (i »2 mm, filled at 50 niL)).
- a desulfurization catalyst nickel-based, (i »2 mm, filled at 50 niL)
- the sulfur content of the hydrocarbon oil after desulfurization was measured under the reaction condition ⁇ S>, and the desulfurization rate was calculated.
- the reactor was operated under the reaction condition ⁇ A> for 200 hours, returned to the reaction condition S again, the sulfur content of the hydrocarbon oil after desulfurization was measured, and the desulfurization rate was calculated. Then, the change in the desulfurization rate before and after the operation for 200 hours was compared.
- the catalyst layer maximum temperature initial boiling point temperature one 1 0 ° C of a hydrocarbon oil, LHS V: lh one 1, reaction pressure (absolute pressure): 0. 05MP a
- Catalyst bed maximum temperature Initial boiling point temperature of hydrocarbon oil + 11 o ° c,
- Hydrocarbon substrates ( ⁇ _1) to ( ⁇ -5) were manufactured under the conditions shown in Table 4. Hydrocarbon oils ( ⁇ _ ⁇ ) to ( ⁇ - ⁇ ) are produced by blending hydrocarbon base materials ( ⁇ -1) to ( ⁇ -5), and their properties are shown in Table 5.
- hydrocarbon oils ( ⁇ - ⁇ ) to ( ⁇ - ⁇ ) are shown in the evaluation flowcharts shown in FIGS. 4 and 5 (evaluation apparatuses 1 and 2 including a reformer and a carbon monoxide purifier). ) was evaluated as follows.
- the difference between the two evaluation devices is the type of reformer.
- the evaluation conditions are as follows.
- the hydrocarbon oil preheater, steam generator and air preheater are each set at 300 ° C.
- the reaction temperature of the steam reformer is 650 ° C, LHS V: 1 h ⁇
- the reaction temperature of the autothermal reformer is 650 ° C
- LHSV 1 h ⁇ H 2 0 / C 2. 0 mol mol
- oxygen and the mixing ratios of hydrocarbon oil ( ⁇ 2 / C): was operated at 0.3 mole Z moles conditions.
- Example 3 to 5 and Comparative Examples 4 to 5 the reaction temperature was 250 ° C.
- Comparative Example 6 was operated under the conditions of a carbon monoxide ratio: 5 mol Z mol and a reaction temperature: 90 ° C., and a carbon monoxide ratio in water and reforming gas: 5 mol mol.
- Hydrocarbon oil and water which have been desulfurized in advance by a desulfurizer, are vaporized by electric heating, respectively, filled with a noble metal catalyst, and led to a reactor (reformer) maintained at a predetermined temperature by an electric heater. A reformed gas rich in hydrogen was generated. The water contained in the reformed gas was separated from the reformed gas by a gas-liquid separator using a cooling method.
- a reactor water gas shift reactor in which the reformed gas and a mixed gas to which a certain amount of steam was added to the co concentration in the reformed gas was maintained at a predetermined temperature by an electric heater filled with a copper-zinc catalyst. ) And converted carbon monoxide in the reformed gas to carbon dioxide.
- Hydrocarbon oil and water which have been desulfurized in advance by a desulfurizer, are vaporized by electric heating, respectively, and the mixture of heated air is filled with a noble metal catalyst and maintained at a predetermined temperature by an electric heater.
- a reactor that generated hydrogen-rich reformed gas.
- Water contained in the reformed gas was separated from the reformed gas by a gas-liquid separation tube using a cooling method.
- a reactor water gas shift reactor in which the reformed gas and a mixed gas to which a certain amount of steam was added to the co concentration in the reformed gas was maintained at a predetermined temperature by an electric heater filled with a copper-zinc catalyst.
- converted carbon monoxide in the reformed gas to carbon dioxide.
- a gas chromatograph capable of analyzing the gas composition and unreacted hydrocarbon oil was installed at the outlet line of the reformer and the outlet line of the water gas shift reactor of the evaluation devices 1 and 2.
- Hydrocarbon substrates ( ⁇ -1) to ( ⁇ _5) were manufactured under the conditions shown in Table 7. Hydrocarbon base materials (III-1) to (III-15) are blended to produce hydrocarbon oils (III-A) to (III [-E), and their properties are shown in Table 8.
- hydrocarbon oils ( ⁇ _ ⁇ ) to ( ⁇ - ⁇ ) were evaluated as follows in accordance with the evaluation flow charts shown in FIGS. 6 and 7.
- the hydrocarbon oil preheater, steam generator and air preheater are set at 300 ° C respectively.
- Fig. 6 shows a flowchart of the steam reforming evaluation. Hydrocarbon oil and water are vaporized by electric heating, respectively, filled with a reforming catalyst (ruthenium-based, ⁇ 2 ⁇ , filling volume 5 mL), and led to a reforming reaction tube maintained at a predetermined temperature by an electric heater, and hydrogen content is reduced. A rich reformed gas was generated.
- a reforming catalyst ruthenium-based, ⁇ 2 ⁇ , filling volume 5 mL
- FIG. 7 is a flowchart of the autothermal reforming evaluation.
- the hydrocarbon oil and water are vaporized by electric heating, and a reforming catalyst (rhodium, ⁇ 2 ⁇ , filling volume 5 mL) is filled together with the preheated air into a reforming reaction tube maintained at a predetermined temperature by an electric heater. Led to the generation of reformed gas rich in hydrogen.
- the conversion was measured as follows.
- Each reforming evaluation device is equipped with a gas flow meter that can measure the flow rate of reformed gas generated at the reaction tube outlet line, and a gas chromatography that can analyze the composition of generated reformed gas and analyze unreacted hydrocarbons. did.
- the tank for supplying hydrocarbon oil and water was installed on a balance, and the amount of supply to the reaction tube per hour was measured with the balance.
- the conversion rate of hydrocarbon oil was calculated from the analysis results of hydrocarbon oil supply amount, generated reformed gas flow rate and generated gas composition.
- the conversion rate is defined as follows.
- Substrate blend ratio Substrate (E-3) vol% 5
- Base material ((-5) vol% 100 Density @ 15 ° C g / cm 3 0.768 0.791 0.793 0.7503 0.7936 Flash point.
- Example 6 Example 7 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Hydrocarbon oil ⁇ - ⁇ m -B HI -C ⁇ — D m— ⁇ m -E
- the conversion rate is a relative value when the conversion rate in the initial operation of Comparative Example 7 was set to 100.0 in each reforming evaluation.
- FIG. 1 is a graph showing an example of a correlation curve between the calorific value of hydrocarbon oil and temperature measured using a high pressure differential scanning calorimeter.
- FIG. 2 is a graph showing a differential curve of the correlation curve shown in FIG.
- FIG. 3 is a flowchart of the evaluation system including the desulfurizer.
- Figure 4 is a flowchart of the evaluation system including the steam reforming reformer and the water gas shift reactor.
- Fig. 5 is a flow chart of the evaluation system including the autothermal reforming reformer and the water gas shift reactor.
- FIG. 6 is an evaluation flowchart of the steam reforming type reformer.
- Figure 7 is an evaluation flow chart of the autothermal reformer.
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WO2007063872A1 (ja) * | 2005-11-30 | 2007-06-07 | Nippon Oil Corporation | 水素の製造方法、改質ガソリンの製造方法及び芳香族炭化水素の製造方法 |
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JP2001089773A (ja) * | 1999-07-21 | 2001-04-03 | Idemitsu Kosan Co Ltd | 水素製造用原料油およびその製造方法 |
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2005
- 2005-03-30 KR KR1020067022416A patent/KR101163249B1/ko not_active IP Right Cessation
- 2005-03-30 WO PCT/JP2005/006706 patent/WO2005095554A1/ja active Application Filing
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JP2001089773A (ja) * | 1999-07-21 | 2001-04-03 | Idemitsu Kosan Co Ltd | 水素製造用原料油およびその製造方法 |
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JP2002080868A (ja) * | 2000-06-29 | 2002-03-22 | Nippon Mitsubishi Oil Corp | 燃料電池システム用燃料 |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007063872A1 (ja) * | 2005-11-30 | 2007-06-07 | Nippon Oil Corporation | 水素の製造方法、改質ガソリンの製造方法及び芳香族炭化水素の製造方法 |
JP2007153931A (ja) * | 2005-11-30 | 2007-06-21 | Nippon Oil Corp | 水素の製造方法、改質ガソリンの製造方法及び芳香族炭化水素の製造方法 |
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KR20060133063A (ko) | 2006-12-22 |
KR101163249B1 (ko) | 2012-07-05 |
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