JP2005290219A - Hydrocarbon oil for hydrogen production, and hydrogen production system - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrocarbon oil for high-efficiency hydrogen production with the durability of the hydrogen production system less affected in the presence of reforming catalyst deterioration. <P>SOLUTION: The hydrocarbon oil for hydrogen production for use in a reformer-equipped hydrogen production system contains a hydrocarbon base obtained by treating a specified hydrocarbon mixture in a specified process, and has a flash point of ≥40°C, an initial boiling point of ≥145°C but ≤170°C, a 50 vol% distillation point of ≥180°C but ≤220°C, a 95 vol% distillation point of ≥220°C but ≤260°C, a sulfur content of ≤0.5 mass ppm, a smoke point of ≥26 mm, an aromatic content of ≤10 vol%, and a oxidation point of ≥210°C. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a hydrocarbon oil for hydrogen production and a hydrogen production system.

In recent years, due to the growing sense of crisis about the global environment in the future, development of an energy supply system that is friendly to the earth has been demanded. From the viewpoint of high energy efficiency and clean exhaust gas, fuel such as fuel cells and hydrogen engines can be used as fuel. The system is in the limelight. In particular, as a method for supplying hydrogen to the fuel cell, in addition to a method of directly supplying hydrogen in the form of compression or liquefaction, a supply method by reforming of an oxygen-containing fuel such as methanol and hydrocarbons such as naphtha and kerosene. Is known (see, for example, Non-Patent Document 1). Among these, the method of supplying hydrogen directly has an advantage that it can be used as a fuel as it is, but it has a problem in storability and mountability when used in a vehicle or the like because it is a gas at room temperature. Methanol is relatively easy to produce hydrogen by reforming in the system, but has low energy efficiency per weight and is toxic and corrosive, so that it is difficult to handle and store. On the other hand, the production of hydrogen by reforming hydrocarbons such as naphtha and kerosene has attracted attention due to the fact that the existing fuel supply infrastructure can be used and the total energy efficiency is high. Such hydrocarbons require a reforming step for hydrogen generation, but there are problems with the durability of the reforming system, and high hydrogen generation efficiency may not be obtained.
Masaki Ikematsu, “Engine Technology”, Sankaidosha, January 2001, Vol. 3, No. 1, p. 35

  In view of such circumstances, an object of the present invention is to provide a hydrocarbon oil for hydrogen production and a hydrogen production system excellent in durability of a reformer.

As a result of intensive studies, the present inventors have found that a hydrocarbon oil having a specific property obtained by treating a specific raw material in a specific process can solve the above problems, and has completed the present invention.
That is, the present invention has an initial boiling point of 140 to 180 ° C., a 90% by volume distillation temperature of 200 to 270 ° C., an aromatic content of 20% by volume or less, and a linear saturated hydrocarbon content of 25% by mass or more, It is obtained through the following steps (1) to (4) using a hydrocarbon mixture having a straight-chain saturated hydrocarbon content of 10 to 15 carbon atoms and a sulfur content of 300 mass ppm or less as a raw material oil. Containing a hydrocarbon base material, having a flash point of 40 ° C. or higher, an initial boiling point of 145 ° C. or higher and 170 ° C. or lower, a 50 vol% distillation temperature of 180 ° C. or higher and 220 ° C. or lower, and a 95 vol% distillation temperature of 220 ° C. A reformer characterized by having a sulfur content of 0.5 mass ppm or less, a smoke point of 26 mm or more, an aromatic content of 10 vol% or less, and an oxidation start temperature of 210 ° C or more. For hydrogen production of hydrogen production system Reduction on hydrocarbon oils.
Step (1): The raw material oil is prepared under the conditions of 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 , and a hydrogen / hydrocarbon capacity ratio of 0.15 to 0.6. Step of hydrodesulfurization treatment with a catalyst containing any one selected from -W, Ni-Mo, Co-Mo, Co-W, and Ni-Co-Mo Step (2): obtained in step (1) Step of stripping 1 to 35% by volume of light component from hydrodesulfurized oil Step (3): After stripping light component, linearized with zeolite under conditions of temperature 150 ° C to 250 ° C and pressure 1 to 5 MPa Step of extracting and removing 10% by volume or more of saturated hydrocarbon Step (4): Step of mixing the hydrocarbon mixture obtained in step (3) and 60% by volume or more of the light portion stripped in step (2)

  The present invention also provides a mixed gas of the hydrocarbon oil and steam described above in the presence of a reforming catalyst containing a Group VIII element of the periodic table as an active metal, a reaction temperature of 400 to 1000 ° C., water and hydrocarbon. The present invention relates to a hydrogen production system including a steam reforming reformer that obtains a product containing hydrogen as a main component by reacting at an oil mixing ratio (S / C) of 1 to 5 mol / mol.

The present invention also provides a mixture of the hydrocarbon oil, water vapor and air described above in the presence of a reforming catalyst containing a Group VIII element of the periodic table as an active metal, a reaction temperature of 400 to 1000 ° C., water and carbonization. By reacting at a mixing ratio of hydrogen oil (S / C) of 0.5 to 5 mol / mol and a mixing ratio of oxygen and hydrocarbon oil (O ₂ / C) of 0.1 to 0.5 mol / mol. The present invention relates to a hydrogen production system including a self-thermal reforming reformer that obtains a product containing hydrogen as a main component.

Hereinafter, the present invention will be described in detail.
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 treating a specific hydrocarbon mixture as a raw material oil and treating it in a specific process. It is.

  The hydrocarbon mixture used as the feedstock has an initial boiling point of 140 to 180 ° C., a 90% by volume distillation temperature of 200 to 270 ° C., an aromatic content of 20% by volume or less, and a linear saturated hydrocarbon content of 25 mass. % Or more, the linear saturated hydrocarbon content of 10 to 15 carbon atoms must be 20 mass% or more, and the sulfur content must be 300 mass ppm or less. Preferably, the initial boiling point is 150 to 170 ° C., the 90 vol% distillation temperature is 225 to 245 ° C., the aromatic content is 15 vol% or less, the linear saturated hydrocarbon content is 35 vol% or more, and the number of carbon atoms is 10 The linear saturated hydrocarbon content of -15 is 25% by volume or more, and the sulfur content is 200 ppm by mass or less. If the properties of the raw material oil are outside the above range, it is difficult to obtain the hydrocarbon oil of the present invention, which is not preferable.

Here, the initial boiling point and the 90 vol% distillation temperature are JIS K2254 "Petroleum products-Distillation test method-Atmospheric pressure distillation test method", and the aromatic content is JIS K2536 "Petroleum products-Hydrocarbon type test". Values measured by the fluorescent indicator adsorption method of method, linear saturated hydrocarbon content, and linear saturated hydrocarbon content of 10 to 15 carbon atoms are values (mass%) measured using GC-FID. It is. That is, a capillary column of methyl silicon (ULTRAALLOY-1) is used for the column, helium is used for the carrier gas, a hydrogen ion detector (FID) is used for the detector, a column length of 30 m, a carrier gas flow rate of 1.0 mL / min, and a splitting. It is a value measured under the conditions of ratio 1:79, sample injection temperature 360 ° C., column temperature rising condition 140 ° C. → (8 ° C./min)→355° C., detector temperature 360 ° C.
The sulfur content is a value measured according to JIS K 2541 “Crude oil and petroleum products—sulfur content test method”.

The raw material oil is processed in the following steps (1) to (4).
In step (1), the raw material oil is subjected to a reaction temperature of 250 to 310 ° C., a hydrogen pressure of 5 to 10 MPa, LHSV of 0.5 to 3.0 h ⁻¹ , and a hydrogen / hydrocarbon capacity ratio of 0.15 to 0.6. Then, the hydrodesulfurization treatment is performed with a catalyst containing any one selected from Ni-W, Ni-Mo, Co-Mo, Co-W, and Ni-Co-Mo.
The reaction temperature of the hydrodesulfurization treatment is 250 to 310 ° C, preferably 280 to 305 ° C. When the reaction temperature is less than 250 ° C., a sufficient hydrodesulfurization reaction rate cannot be obtained. On the other hand, when the reaction temperature 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 to 2 h ⁻¹ . A lower LHSV is advantageous for the reaction, but if it is less than 0.5 h ⁻¹ , a very large reaction column volume is required.
The hydrogen / hydrocarbon capacity ratio is 0.15 to 0.6, preferably 0.2 to 0.4.
When the hydrogen pressure is less than 5 MPa and when the hydrogen / hydrocarbon capacity ratio is less than 0.15, the effect of promoting the desulfurization reaction or the hydrogenation reaction becomes insufficient. In addition, when the hydrogen pressure exceeds 10 MPa and the hydrogen / hydrocarbon capacity ratio exceeds 0.6, the apparatus cost increases.

The catalyst used for the hydrodesulfurization treatment needs to contain any one selected from Ni—W, Ni—Mo, Co—Mo, Co—W, and Ni—Co—Mo as an active metal of the catalyst. . The active metal is preferably used by being supported on a porous carrier. An inorganic oxide is preferably used as the porous carrier. Specific examples of the inorganic oxide include alumina, titania, zirconia, boria, silica, and zeolite. Among these, at least one of titania, zirconia, boria, silica, and zeolite and an alumina is used. It is suitably used in the present invention. The amount of the above-mentioned active metal supported is not particularly limited, but the total amount of metal oxide is preferably 20 to 35% by mass with respect to the catalyst mass.
The catalyst is preferably used after presulfiding with hydrogen and a sulfur compound. In general, a gas containing hydrogen and a sulfur compound is circulated, and heat of 200 ° C. or higher is given in accordance with a predetermined procedure to presulfurize the active metal on the catalyst and develop hydrogenation and desulfurization activities.

  The hydrodesulfurized oil in step (1) strips (removes) light components (generally, boiling point of 200 ° C. or lower) as step (2). It is 1-35 volume% on the basis of hydrodesulfurization process oil, Preferably it is 10-35 volume%, More preferably, it is 20-35 volume%. When stripping is not performed or when the strip amount is not sufficient, the load of the subsequent straight-chain saturated hydrocarbon removing device increases and the purification efficiency decreases. Further, when the strip amount is excessive (over 35% by volume), the time required for strip processing increases.

In step (3), the hydrodesulfurized oil from step (1) is stripped (removed) of light components in step (2), and then straightened with zeolite under conditions of 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 chain saturated hydrocarbons.
The extraction temperature for the removal of the linear saturated hydrocarbon is 150 to 250 ° C, preferably 180 to 200 ° C. When the extraction temperature is less than 150 ° C., a sufficient removal rate of linear saturated hydrocarbon cannot be obtained. On the other hand, when it exceeds 250 degreeC, the removal efficiency of a linear saturated hydrocarbon will fall. Moreover, the pressure at this time is 1-5 MPa, Preferably it is 1.5-3 MPa. If the pressure is less than 1.5 MPa, a sufficient removal rate of linear saturated hydrocarbons cannot be obtained. On the other hand, if it exceeds 3 MPa, a sufficient removal rate of linear saturated hydrocarbons cannot be obtained. The zeolite used for the removal of the linear saturated hydrocarbon is not particularly limited, but generally, A-type zeolite is used, and among these, the molecular sieve 5A is preferable. Under the above conditions, it is necessary to extract and remove linear saturated hydrocarbons by 10 volume% or more, preferably 20 volume% or more.

  In the step (4), the hydrocarbon mixture obtained by extracting and removing 10% by volume or more of the linear saturated hydrocarbon in the step (3) is mixed with the light component stripped in the step (2). The mixing amount of the light component stripped in the step (2) is 60% by volume or more, and preferably 70% by volume or more.

  The hydrocarbon oil for hydrogen production of the present invention comprises a hydrocarbon base material obtained by treating the above-mentioned raw material oil in steps (1) to (4), and is a hydrocarbon oil having the following specific properties. is there.

The flash point of the hydrocarbon oil for hydrogen production of the present invention (hereinafter also referred to as the hydrocarbon oil of the present invention) needs to be 40 ° C. or higher from the viewpoint of flammability and ease of handling, and 42 ° C. or higher. Is preferable, and 45 degreeC or more is more preferable.
The flash point here is a value measured by JIS K2265 “Crude oil and petroleum products—flash point test method”.

  The lower limit of the initial boiling point (IBP) of the hydrocarbon oil of the present invention needs to be 145 ° C. or higher, preferably 150 ° C. or higher. On the other hand, the upper limit needs to be 170 ° C. or lower, preferably 165 ° C. or lower, more preferably 160 ° C. or lower, and further preferably 155 ° C. or lower. If the IBP is lower than 145 ° C., it is not preferable from the viewpoints of flammability, increased evaporation gas (THC), and handleability.

  The lower limit of the 50 vol% distillation temperature (T50) of the hydrocarbon oil of the present invention is required to be 180 ° C or higher, preferably 185 ° C or higher, and more preferably 190 ° C or higher. On the other hand, the upper limit needs to be 220 ° C. or lower, preferably 215 ° C. or lower, and 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 generated are not preferable, and if it exceeds 220 ° C., it is not preferable because the start time of the hydrogen production system is deteriorated.

  The lower limit of the 95 vol% distillation temperature (T95) of the hydrocarbon oil of the present invention needs to be 220 ° C. or higher, preferably 225 ° C. or higher, and more preferably 230 ° C. or higher. On the other hand, the upper limit needs to be 260 ° C. or less, preferably 255 ° C. or less, and more preferably 250 ° C. or less. When T95 is lower than 220 ° C., the amount of hydrogen generated per weight and the amount of hydrogen generated per carbon dioxide generated decrease, which is not preferable. When the temperature exceeds 260 ° C., THC in the exhaust gas increases, which is not preferable.

The distillation properties of the hydrocarbon oil of the present invention other than IBP, T50, and T95 are not particularly limited, but the 10 vol% distillation temperature (T10) is preferably 160 ° C or higher and 190 ° C or lower. Since flammability becomes high and evaporative gas (THC) is easily generated, 165 ° C. or higher is more preferable, and 170 ° C. or higher is more preferable. On the other hand, 185 ° C. or lower is more preferable, and 180 ° C. or lower is more preferable because of the deterioration of the start time of the hydrogen production system.
The 90 vol% distillation temperature (T90) is preferably 210 ° C or higher and 255 ° C or lower. Since the hydrogen generation amount per weight and the hydrogen generation amount per carbon dioxide generation amount are reduced, 220 ° C. or higher is more preferable, and 230 ° C. or higher is more preferable. On the other hand, since THC in exhaust gas increases, 245 ° C. or lower is more preferable, and 240 ° C. or lower is further preferable.
The end point (EP) is preferably 230 ° C. or higher and 280 ° C. or lower. Since the hydrogen generation amount per weight and the hydrogen generation amount per carbon dioxide generation amount are decreased, 240 ° C. or higher is more preferable, and 245 ° C. or higher is further preferable. On the other hand, since THC in exhaust gas increases, 270 ° C. or lower is more preferable, and 260 ° C. or lower is further preferable.
Here, IBP, T10, T50, T90, T95, and EP are values measured according to JIS K2254 “Petroleum products—Distillation test method—Atmospheric pressure distillation test method”.

The sulfur content of the hydrocarbon oil of the present invention is 0.5 mass in terms of the desulfurization rate, the durability of the desulfurization catalyst, the durability of the reforming catalyst, the reduction in reforming reactivity, and the amount of hydrogen generated per carbon dioxide generation. It is necessary to be not more than ppm, preferably not more than 0.3 mass ppm, more preferably not more than 0.2 mass ppm.
Here, the sulfur content is a value measured by ASTM D 4045-96 “Standard Test Method for Sulfur in Petroleum Products by Hydrogenolysis and Rateometric Colorimetry”.

  The smoke point of the hydrocarbon oil of the present invention has a large amount of hydrogen generation per weight, a large amount of hydrogen generation per carbon dioxide generation amount, a low THC in exhaust gas, and a short system start-up time. Further, since the deterioration of the reforming catalyst is small and the initial performance can be maintained for a long time, the thickness is required to be 26 mm or more, preferably 27 mm or more, and more preferably 28 mm or more.

  The aromatic content of the hydrocarbon oil of the present invention includes a large amount of hydrogen generation per weight, a large amount of hydrogen generation per carbon dioxide generation amount, a small amount of THC in the exhaust gas, and a short system startup time. In view of the fact that the deterioration of the reforming catalyst is small and the initial performance can be sustained for a long time, it is necessary to be 10% by volume or less, and preferably 8% by volume or less.

  There is no limitation on the olefin content of the hydrocarbon oil of the present invention, but there is a large amount of hydrogen generation per weight, a large amount of hydrogen generation per carbon dioxide generation amount, a small amount of THC in the exhaust gas, From the viewpoints of short system start-up time, low deterioration of the reforming catalyst and sustaining initial performance for a long time, and good storage stability, it is preferably 5% by volume or less, more preferably 1% by volume or less. More preferably, it is 0.5 volume% or less.

There is no restriction on the saturated hydrocarbon content (total amount of saturated and naphthene) of the hydrocarbon oil of the present invention, but there is a large amount of hydrogen generated per weight and a large amount of hydrogen generated per carbon dioxide generated. From the viewpoints of low THC in the exhaust gas and short system start-up time, it is preferably 85% by volume or more, more preferably 90% by volume or more, and most preferably 95% by volume or more.
The above-mentioned aromatic content, olefin content, and saturated hydrocarbon content are values measured by the fluorescent indicator adsorption method of JIS K2536 “Petroleum products-hydrocarbon type test method”.

There is no limitation on the naphthenic hydrocarbon content of the hydrocarbon oil of the present invention, but when the naphthenic hydrocarbon content decreases, the desulfurization rate decreases, the desulfurization catalyst durability decreases, and the reforming catalyst durability increases. From the viewpoint of suppression such as reduction in property, reduction in reforming reactivity, reduction in hydrogen generation amount per carbon dioxide generation amount, it is preferably 30% by volume or more, more preferably 40% by volume or more, and 45% by volume or more. Further preferred.
The content of naphthenic hydrocarbon referred to here is measured by a method based on ASTM D2425 (Standard Test Method for Hydrocarbon Types in Middle Distillates by Mass Spectrometry).

The oxidation start temperature of the hydrocarbon oil of the present invention needs to be 210 ° C. or higher, preferably 212 ° C. or higher, and more preferably 215 ° C. or higher. When the oxidation start temperature is less than 210 ° C., it is not preferable from the viewpoint of deterioration in durability of the hydrogen production apparatus due to coking of the reforming catalyst.
The oxidation start temperature here is measured using a high-pressure differential scanning calorimeter (hereinafter referred to as “high-pressure DSC”). More specifically, the sample is introduced into a DSC pressure cell (for example, manufactured by Metradred), and the sample is heated from 30 ° C. to 500 ° C. at a rate of 20 ° C./minute in an air atmosphere of 4 MPa. A correlation curve with temperature is obtained. The oxidation start temperature is determined based on the exothermic peak that appears first in the correlation curve.
FIG. 1 is a graph showing an example of a correlation curve between a calorific value and temperature measured using a high-pressure DSC, and shows a measurement result of hydrocarbon oil B described later. In FIG. 1, the vertical axis represents the amount of heat generated, and the horizontal axis represents the temperature. FIG. 2 is a graph showing a differential curve of the curve shown in FIG. In FIG. 1, a straight line l ₁ indicates a tangent at a point where the amount of heat generation per unit time is maximum (a point corresponding to the point B in FIG. 2). Further, l _{2 in} FIG. 1 indicates a tangent at the start point of heat generation (a point at which the curve rises). The temperature corresponding to the intersection A between l ₁ and l ₂ is the oxidation start temperature defined in the present invention.

  As the hydrocarbon oil for hydrogen production of the present invention, a hydrocarbon base material obtained through the above-described steps (1) to (4) can be used. In addition, other hydrogen production base materials can be appropriately mixed with the hydrocarbon base material as long as the above properties are maintained. The blending ratio of other base materials that can be mixed is preferably 20% by volume or less, more preferably 15% by volume or less, and still more preferably 10% by volume or less, based on the total amount of hydrocarbon oil. If the content of the other substrate exceeds 20% by volume, it is not preferable in terms of a decrease in the conversion rate to a reformed gas rich in hydrogen at the beginning of operation and a change in the conversion rate after 100 hours of operation.

The hydrocarbon oil of the present invention is used as a raw material for a hydrogen production system including a steam reforming reformer or an autothermal reforming reformer described later. The reformer is a device for reforming hydrocarbons to obtain hydrogen, and by using the hydrocarbon oil of the present invention, the reformer can be further improved in durability, and as a hydrogen production system. Improves durability.
That is, the hydrogen production system of the present invention is as follows.

(1) Mixing of water and hydrocarbon oil at a reaction temperature of 400 to 1000 ° C. in the presence of a reforming catalyst containing a group VIII element of the periodic table as an active metal. A hydrogen production system comprising a steam reforming reformer that obtains a product containing hydrogen as a main component by reacting at a ratio (S / C) of 1 to 5 mol / mol.

(2) A mixture gas of hydrocarbon oil, water vapor 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, reaction temperature of 400 to 1000 ° C., water and hydrocarbon oil By reacting at a mixing ratio (S / C) of 0.5 to 5 mol / mol and a mixing ratio of oxygen and hydrocarbon oil (O ₂ / C) of 0.1 to 0.5 mol / mol, hydrogen is reacted. A hydrogen production system including a self-thermal reforming reformer that obtains a product having a main component.

In the “mixing ratio of water and hydrocarbon oil (S / C)” in the present invention, S means the number of moles of water (molecule), and C means the number of moles of carbon in the hydrocarbon oil (molecule). . Accordingly, an example of how to obtain the “mixing ratio of water and hydrocarbon oil (S / C)” will be described. Water (molecule): 6 mol, and hydrocarbon oil to ethane (C ₂ H ₆ ): 1 When moles are used, the mixing ratio (S / C) of water and hydrocarbon oil is ethane, which is a hydrocarbon oil: The number of moles of carbon in 1 mole is 2 moles, so “S / C = 6 moles”. / 2 mol = 3 ”.
Similarly, in the “mixing ratio of oxygen and hydrocarbon oil (O ₂ / C)” referred to in the present invention, O ₂ is the number of moles of oxygen (molecules), and C is the carbon in the hydrocarbon oil (molecules). It means the number of moles. Accordingly, an example of how to obtain the “mixing ratio of oxygen and hydrocarbon oil (O ₂ / C)” will be described. Oxygen (molecules): 0.6 mol, ethane (C ₂ H ₆ ) When 1 mol is used, the mixing ratio of oxygen and hydrocarbon oil (O ₂ / C) is ethane, which is a hydrocarbon oil. Since the number of moles of carbon in 1 mol is 2 mol, “O ₂ /C=0.6 mol / 2 mol = 0.3 ”.

  As the active metal of the catalyst used in the steam reforming reformer, ruthenium, rhodium, platinum and the like are preferable, and ruthenium and rhodium are particularly preferable in terms of reforming reactivity for obtaining hydrogen from the hydrocarbon compound. In addition, the reaction temperature is preferably 400 ° C. or higher, more preferably 500 ° C. or higher in terms of reforming reactivity, 1000 ° C. or lower is preferable, and 800 ° C. or lower is more preferable in terms of suppressing the amount of coking on the catalyst. The mixing ratio of water and hydrocarbon oil (S / C) is preferably 1 mol / mol or more, more preferably 2 mol / mol or more from the viewpoint of suppressing the amount of coking on the catalyst, and 5 mol from the viewpoint of reformer efficiency. / Mol or less is preferable, and 4 mol / mol or less is more preferable.

The active metal of the catalyst used in the autothermal reforming reformer is preferably ruthenium, rhodium, platinum or the like in terms of reforming reactivity for obtaining hydrogen from a hydrocarbon compound, and particularly preferably ruthenium or rhodium. In addition, the reaction temperature is preferably 400 ° C. or higher, more preferably 500 ° C. or higher in terms of reforming reactivity, 1000 ° C. or lower is preferable, and 800 ° C. or lower is more preferable in terms of suppressing the amount of coking on the catalyst. 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 on the catalyst, and from the viewpoint of reformer efficiency. 5 mol / mol or less is preferable and 3 mol / mol or less is more preferable. The mixing ratio of oxygen and hydrocarbon oil (O ₂ / C) is preferably 0.1 mol / mol or more, more preferably 0.2 mol / mol or more in terms of reforming reactivity, and the amount of coking on the catalyst is suppressed. In this respect, 0.5 mol / mol or less is preferable, and 0.4 mol / mol or less is more preferable.

  In the hydrogen production system of the present invention, it is preferable to provide other equipment in combination with the reformer. The other equipment combined with the reformer is not particularly limited, and examples thereof include a desulfurizer, a carbon monoxide purifier, and the like, for example, (a) Desulfurizer / reformer. , Carbon monoxide purifier, (b) desulfurizer, reformer, desulfurizer (re-desulfurization), carbon monoxide purifier, (c) reformer, desulfurizer, carbon monoxide purifier, etc. Can do.

A desulfurizer is an apparatus for removing sulfur content in hydrocarbon oil. In the present invention, a copper-zinc system, a nickel system, or the like is used as a catalyst, a reaction temperature is 20 to 300 ° C., and an LHSV is 0.1 to 0.1. Examples thereof include a desulfurizer that performs desulfurization treatment at 10 h ⁻¹ and a reaction pressure of less than 1 MPa.

The carbon monoxide purifier removes carbon monoxide, which is contained in the gas generated by the reformer and becomes the catalyst poison of the fuel cell. Examples of carbon monoxide purifiers include the following.
(1) The reformed gas obtained from the reformer is mixed with steam vaporized by heating, and copper, zinc, platinum, ruthenium, rhodium or the like is used as a catalyst, the reaction temperature is 200 to 500 ° C., and the gas space velocity is 1000 to 10,000 h. ^-1 , carbon dioxide and hydrogen from carbon monoxide and water vapor as a product under reaction conditions of reaction pressure of less than 1 MPa and a ratio of water and carbon monoxide in the reformed gas of 0.5 to 3.0 mol / mol Obtain water gas shift reactor.
(2) The reformed gas obtained from the reformer and compressed air are mixed, and copper, nickel, platinum, ruthenium, rhodium, etc. are used as a catalyst, the reaction temperature is 100 to 300 ° C., and the gas space velocity is 1000 to 10,000 h ^{−. 1.} Carbon monoxide is converted from carbon monoxide and air to carbon dioxide under reaction conditions of reaction pressure of less than 1 MPa and a ratio of air to carbon monoxide in the reformed gas of 0.5 to 3.0 mol / mol. Selective oxidation reactor.

  The hydrocarbon oil for hydrogen production of the present invention is suitable as a hydrocarbon oil for hydrogen production because it has high reforming efficiency and can maintain the performance of the reformer for a long time.

  Hereinafter, the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited to these examples.

[Examples 1 to 5 and Comparative Examples 1 to 3]
Hydrocarbon substrates (1) to (5) were produced under the conditions shown in Table 1. Hydrocarbon base materials (1) to (5) are blended to produce hydrocarbon oils A to E. Table 2 shows the properties thereof.

(Property measurement)
The general properties of the hydrocarbon oils A to E were measured by the following test methods.
The density refers to a density measured according to JIS K 2249 “Determination method of density of crude oil and petroleum products and density / mass / capacity conversion table”.
The flash point refers to a flash point measured by JIS K 2265 “Crude oil and petroleum products—flash point test method”.
The distillation properties (IBP, T10, T50, T90, T95, EP) are all values measured according to JIS K 2254 “Petroleum products—Distillation test method—Atmospheric pressure distillation test method”.
Sulfur content refers to the sulfur content measured by ASTM D 4045-96 “Standard Test Method for Sulfur in Petroleum Products by Hydrogenolysis and Rateometric Colorimetry”.
The aromatic content, olefin content, and saturated content are the aromatic content, olefin content, saturated hydrocarbon (naphthenic carbonization) measured by the fluorescent indicator adsorption method of JIS K2536 “Petroleum products-hydrocarbon type test method”. (Including hydrogen) content.
The naphthene content refers to the naphthenic hydrocarbon content measured by a method in accordance with ASTM D2425 (Standard Test Method for Hydrocarbon Types in Middle Distillates by Mass Spectrometry).
As described above, the oxidation start temperature refers to a temperature measured using a high-pressure differential scanning calorimeter.
Smoke point refers to the smoke point measured by JIS K 2537 “Petroleum products—kerosene and aviation turbine fuel oil—smoke point test method”.

The obtained hydrocarbon oils A to E were evaluated as follows according to the evaluation flowcharts shown in FIGS. 3 and 4.
The hydrocarbon oil afterheater, the steam generator and the air afterheater are set to 300 ° C., respectively.

(1) Steam reforming evaluation A flowchart of steam reforming evaluation is shown in FIG. Hydrocarbon oil and water are vaporized by electric heating, respectively, and a reforming catalyst (ruthenium-based, φ2 mm, filling amount 5 mL) is filled and led to a reforming reaction tube maintained at a predetermined temperature with an electric heater, rich in hydrogen. A reformed gas was generated.
First, the reforming reaction was performed under the following reaction condition S1.
(Reaction condition S1)
LHSV: 0.5 h ⁻¹ , S / C: 3 mol / mol, catalyst layer outlet temperature: 650 ° C.
After obtaining the conversion rate under the reaction condition S1, oil was passed for 100 hours under the following reaction condition A1.
(Reaction condition A1)
LHSV: 5 h ⁻¹ , S / C: 3 mol / mol, catalyst layer outlet temperature: 650 ° C.
After the operation under the reaction condition A1, the reaction condition was returned to S1, the conversion rate was measured, and the change in conversion rate from the initial operation was calculated.
These evaluations were performed for hydrocarbon oils A to E, respectively. The results are shown in Table 3.

Further, as a comparative example of the reaction conditions, a reforming reaction was performed under the following reaction conditions S1 ′.
(Reaction condition S1 ′)
LHSV: 0.5 h ⁻¹ , S / C: 0.8 mol / mol, catalyst layer outlet temperature: 650 ° C.
After obtaining the conversion rate under the reaction condition S1 ′, oil was passed for 100 hours under the following reaction condition A1 ′.
(Reaction condition A1 ′)
LHSV: 5 h ⁻¹ , S / C: 0.8 mol / mol, catalyst layer outlet temperature: 650 ° C.
After the operation under the reaction condition A1 ′, the reaction condition was returned to S1 ′, the conversion rate was measured, and the change in conversion rate from the initial operation was calculated. The results are also shown in Table 3 as Comparative Example 4.

(2) Self-thermal reforming evaluation A flowchart of self-thermal reforming evaluation is shown in FIG. Hydrocarbon oil and water are vaporized by electric heating, charged with reforming catalyst (rhodium system, φ2mm, filling amount 5mL) together with preheated air, led to a reforming reaction tube maintained at a predetermined temperature with an electric heater, hydrogen A rich gas was generated.
First, the reforming reaction was performed under the following reaction condition S2.
(Reaction condition S2)
LHSV: 0.5 h ⁻¹ , S / C: 2 mol / mol, O ₂ / C: 0.25,
Catalyst layer outlet temperature: 650 ° C
After obtaining the conversion rate under the reaction condition S2, oil was passed for 100 hours under the following reaction condition A2.
(Reaction condition A2)
LHSV: 5 h ⁻¹ , S / C: 2 mol / mol, O ₂ / C: 0.25,
Catalyst layer outlet temperature: 650 ° C
After the operation under the reaction condition A2, the reaction condition was returned to S2, the conversion rate was measured, and the change in conversion rate from the initial operation was calculated.
These evaluations were performed for hydrocarbon oils A to E, respectively. The results are shown in Table 3.

Further, as a comparative example of the reaction conditions, the reforming reaction was performed under the following reaction conditions S2 ′.
(Reaction condition S2 ′)
LHSV: 0.5 h ⁻¹ , S / C: 0.3 mol / mol, O ₂ / C: 0.25,
Catalyst layer outlet temperature: 650 ° C
After obtaining the conversion rate under the reaction condition S2 ′, oil was passed for 100 hours under the following reaction condition A2 ′.
(Reaction condition A2 ′)
LHSV: 5 h ⁻¹ , S / C: 0.3 mol / mol, O ₂ / C: 0.25,
Catalyst layer outlet temperature: 650 ° C
After the operation under the reaction condition A2 ′, the reaction condition was returned to S2 ′, the conversion was measured, and the change in conversion from the initial operation was calculated. The results are also shown in Table 3 as Comparative Example 4.

The conversion rate was measured as follows. In each reforming evaluation apparatus, a gas flow meter capable of measuring the flow rate of the reformed gas generated in the reaction tube outlet line and a gas chromatography capable of analyzing the generated reformed gas composition and unreacted hydrocarbons were installed. Hydrocarbon oil and water supply tanks were installed on a balance, and the amount of supply to the reaction tube per hour was measured with this balance. The conversion rate of the hydrocarbon oil was calculated from the analysis results of the hydrocarbon oil supply amount, the generated reformed gas flow rate and the generated gas composition. The conversion rate was defined as follows.
Conversion (%) = C1 (CO ₂ , CO and CH ₄ ) in the generated gas / C in the supplied hydrocarbon oil × 100

  From the results shown in Table 3, when the hydrocarbon oils of the present invention (Examples 1 and 2) were used, the conversion rate was higher than that of the hydrocarbon oil and the apparatus conditions of the comparative example, and the conversion rate. It can be seen that can be stably maintained for a long time.

It is a graph which shows an example of the correlation curve of the emitted-heat amount and temperature of a kerosene composition measured using a high-pressure differential scanning calorimeter. It is a graph which shows the differential curve of the correlation curve shown in FIG. It is an evaluation flowchart of a steam reforming type reformer. It is an evaluation flowchart of a self-heat reforming type reformer.

Claims (3)

The initial boiling point is 140 to 180 ° C., 90% by volume distillation temperature is 200 to 270 ° C., the aromatic content is 20% by volume or less, the linear saturated hydrocarbon content is 25% by mass or more, and the carbon number is 10 to 15 Containing a hydrocarbon base material obtained through the following steps (1) to (4) using a hydrocarbon mixture having a linear saturated hydrocarbon content of 20 mass% or more and a sulfur content of 300 mass ppm or less as a raw material oil The flash point is 40 ° C. or higher, the initial boiling point is 145 ° C. or higher and 170 ° C. or lower, the 50% by volume distillation temperature is 180 ° C. or higher and 220 ° C. or lower, and the 95% by volume distillation temperature is 220 ° C. or higher and 260 ° C. or lower. Hydrogen production system provided with a reformer having a sulfur content of 0.5 mass ppm or less, a smoke point of 26 mm or more, an aromatic content of 10 vol% or less, and an oxidation start temperature of 210 ° C. or more Hydrocarbon oil for hydrogen production.
Step (1): The raw material oil is prepared under the conditions of 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 , and a hydrogen / hydrocarbon capacity ratio of 0.15 to 0.6. Step of hydrodesulfurization treatment with a catalyst containing any one selected from -W, Ni-Mo, Co-Mo, Co-W, and Ni-Co-Mo Step (2): obtained in step (1) Step of stripping 1 to 35% by volume of light component from hydrodesulfurized oil Step (3): After stripping light component, linearized with zeolite under conditions of temperature 150 ° C to 250 ° C and pressure 1 to 5 MPa Step of extracting and removing 10% by volume or more of saturated hydrocarbon Step (4): Step of mixing the hydrocarbon mixture obtained in step (3) and 60% by volume or more of the light portion stripped in step (2)   The mixed gas of hydrocarbon oil and water vapor according to claim 1, in the presence of a reforming catalyst containing a Group VIII element of the periodic table as an active metal, a reaction temperature of 400 to 1000 ° C, a mixing ratio of water and hydrocarbon oil A hydrogen production system comprising a steam reforming reformer that obtains a product mainly composed of hydrogen by reacting (S / C) at 1 to 5 mol / mol. The mixed gas of the hydrocarbon oil, water vapor and air according to claim 1, in the presence of a reforming catalyst containing a group VIII element of the periodic table as an active metal, reaction temperature of 400 to 1000 ° C, mixing of water and hydrocarbon oil Hydrogen is mainly produced by reacting at a ratio (S / C) of 0.5 to 5 mol / mol and a mixing ratio of oxygen and hydrocarbon oil (O ₂ / C) of 0.1 to 0.5 mol / mol. A hydrogen production system comprising a self-thermal reforming reformer for obtaining a product as a component.

Images