JP2005290221A - Hydrocarbon oil for producing hydrogen of system for producing hydrogen and fuel for burner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrocarbon oil reformable as a raw material for producing the hydrogen in a system for producing the hydrogen using a burner as a heat source at a relatively low temperature and reducing the burner load and reducing the NOx emission as a fuel for the burner of the system for producing the hydrogen. <P>SOLUTION: The hydrocarbon oil has ≥40°C flash point, ≥145 to ≤195°C initial boiling point, ≤220°C 95 vol% distillation temperature, ≥+25 Saybolt color, ≤1 corrosiveness to a copper strip, ≤0.5 mass ppm of sulfur content, ≤25 mass% of the component ratio of 13C hydrocarbons and ≥1.95 molar ratio of hydrogen element to carbon element. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a hydrocarbon oil for hydrogen production in a hydrogen production system mainly using a burner as a heat supply source and a fuel for a burner used in the 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 are passed through a hydrogen production system with a reforming process for hydrogen generation. In the hydrogen production system, a chemical reaction is involved in the hydrocarbon reforming process, and thus a reaction heat source is required. In the case of a fuel cell hydrogen production system, especially as a heat source for a hydrogen production system from hydrocarbons, the use of electricity is made as low as possible, and the heat from a burner that uses hydrocarbon compounds as fuel is mainly used. It is preferable when considering the efficiency of the manufacturing system. However, when a general hydrocarbon compound is used as a burner heat source, the amount of NOx discharged from the burner is not necessarily low enough, which may not be preferable for a fuel cell system aimed at reducing the load on the global environment. there were. In addition, it is necessary to have separate tanks for hydrocarbons for hydrogen production and fuel for burners in the hydrogen production system, resulting in problems in system space.
Masaki Ikematsu, “Engine Technology”, Sankaidosha, January 2001, Vol. 3, No. 1, p. 35

  In view of such a situation, the present invention can reduce reformer load as a fuel for a hydrogen production system that can be reformed at a relatively low temperature as a raw material for hydrogen production in a hydrogen production system and the main heat source is a burner, and It aims at providing the hydrocarbon oil which can reduce NOx discharge | emission amount.

As a result of intensive studies, the present inventors have found that a hydrocarbon oil having specific properties can solve the above problems, and have completed the present invention.
That is, the present invention has a flash point of 40 ° C. or higher, an initial boiling point of 145 ° C. or higher and 195 ° C. or lower, a 95% vol. A burner is mainly used as a heat source, characterized in that the component ratio of hydrocarbon of 13 mass ppm or less, carbon number 13 is 25 mass% or less, and the molar ratio of hydrogen element to carbon element is 1.95 or more. The present invention relates to a hydrocarbon oil for hydrogen production in a hydrogen production system.
Moreover, it is desirable to use the hydrocarbon oil for hydrogen production of the present invention as a fuel for a burner that is a heat supply source of a hydrogen production system.

Hereinafter, the present invention will be described in detail.
The flash point of the hydrocarbon oil for hydrogen production used in the hydrogen production system of the present invention (hereinafter also referred to as the hydrocarbon oil of the present invention) is 40 ° C. or higher from the viewpoint of flammability and ease of handling. is necessary.
On the other hand, from the viewpoint of reducing the burner load and reducing NOx emission, it is preferably 70 ° C. or lower, more preferably 50 ° C. or lower, and most preferably 45 ° C. or lower.
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 is required to be 145 ° C. or higher from the viewpoints of flammability, increased evaporation gas (THC), and handling properties. On the other hand, the upper limit is required to be 195 ° C. or less from the viewpoint of reducing the burner load and NOx emission, 180 ° C. or less is preferable, 165 ° C. or less is more preferable, and 155 ° C. or less is more preferable.

  The upper limit of the 95 vol% distillation temperature (T95) of the hydrocarbon oil of the present invention is required to be 220 ° C. or less, preferably 210 ° C. or less, from the viewpoint of reducing the burner load and reducing NOx emission. 200 ° C. or lower is more preferable, and 190 ° C. or lower is most preferable. On the other hand, from the viewpoint of the hydrogen generation amount per weight and the hydrogen generation amount per carbon dioxide generation amount, it is preferably 170 ° C. or higher, and more preferably 180 ° C. or higher.

The distillation properties of the hydrocarbon oil of the present invention other than IBP and T95 are not particularly limited, but are preferably as follows.
The 10 vol% distillation temperature (T10) is preferably 145 ° C or higher and 210 ° C or lower. From the viewpoint of flammability and generation of evaporated gas (THC), 150 ° C. or higher is more preferable. On the other hand, 190 degreeC or less is more preferable and 160 degreeC or less is further more preferable from the reason for the start time deterioration of a hydrogen production system.
The 50 vol% distillation temperature (T50) is preferably 150 ° C or higher and 210 ° C or lower. From the viewpoint of the hydrogen generation amount per weight and the hydrogen generation amount per carbon dioxide generation amount, 160 ° C. or higher is more preferable, and 165 ° C. or higher is more preferable. On the other hand, from the viewpoint of reducing the burner load and reducing NOx emissions, 190 ° C. or lower is more preferable, 180 ° C. or lower is more preferable, and 170 ° C. or lower is most preferable.

The 90 vol% distillation temperature (T90) is preferably 160 ° C or higher and 215 ° C or lower. From the viewpoint of the hydrogen generation amount per weight and the hydrogen generation amount per carbon dioxide generation amount, 170 ° C. or higher is more preferable, and 175 ° C. or higher is more preferable. On the other hand, from the viewpoint of reducing the burner load and reducing NOx emission, 210 ° C. or lower is more preferable, 200 ° C. or lower is further preferable, and 190 ° C. or lower is most preferable.
The end point (EP) is preferably 170 ° C. or higher and 230 ° C. or lower. From the viewpoint of the hydrogen generation amount per weight and the hydrogen generation amount per carbon dioxide generation amount, 180 ° C. or higher is more preferable, and 190 ° C. or higher is more preferable. On the other hand, from the viewpoint of increasing THC in the exhaust gas, 220 ° C. or lower is more preferable, and 200 ° C. or lower is more 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 Saybolt color of the hydrocarbon oil of the present invention needs to be +25 or more from the viewpoint of system durability, preferably +29 or more, and more preferably +30 or more.
The Saebold color here is a value measured by the Saebold color test method in JIS K2580 “Petroleum products-color test method”.

The copper plate corrosion of the hydrocarbon oil of the present invention needs to be 1 or less from the viewpoint of ensuring the durability of the reformed portion, and 1a is preferable.
The copper plate corrosion here is a value measured by JIS K2513 "Petroleum products-Copper plate corrosion test method".

The sulfur content of the hydrocarbon oil of the present invention is 0.5 mass from the viewpoint 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 generation per carbon dioxide generation amount. 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 component ratio of the hydrocarbon having 13 carbon atoms in the hydrocarbon oil of the present invention needs to be 25% by mass or less from the viewpoints of durability of the desulfurization catalyst, durability of the reforming catalyst, and reduction of reforming reactivity. 10 mass% or less is preferable, 5 mass% or less is more preferable, and 1 mass% or less is the most preferable.
Here, the component ratio of the hydrocarbon having 13 carbon atoms is a value (mass%) measured using GC-FID. That is, a capillary column of methyl silicon (ULTRAALLOY-1, 0.25 mmφ, 30 m) is used for the column, helium is used for the carrier gas, a hydrogen ion detector (FID) is used for the detector, and a carrier gas flow rate of 1.0 mL / min. , Chromatograph measured under the following conditions: split ratio 1:79, sample injection temperature 280 ° C., column temperature rise condition 50 ° C. (5 minutes) → (5 ° C./min)→280° C. (10 minutes), detector temperature 300 ° C. Thus, the value is obtained by performing area integration of hydrocarbons having 13 carbon atoms.

The molar ratio (H / C) between the hydrogen element and the carbon element of the hydrocarbon oil of the present invention is 1.95 or more from the viewpoint of the low generation amount of carbon monoxide and the high hydrogen generation efficiency. Necessary and 2.0 or more is preferable.
In addition, the molar ratio (C / H) of carbon to hydrogen of the hydrocarbon oil here is a value measured by a method based on ASTM D 5291-01 (Standard Test Method for Hydrocarbon Types in Middle Distillates by Mass Spectrometry). .

  There is no limitation on the aromatic 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 low THC in the exhaust gas, 20% by volume or less is preferable, and 8% by volume or less is more preferable from the viewpoint that the system start-up time is short, the deterioration of the reforming catalyst is small, and the initial performance can be sustained for a long time.

  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 low THC in the exhaust gas, 5% by volume or less is preferable, 1% by volume or less is more preferable, from the viewpoint that the system start-up time is short, the deterioration of the reforming catalyst is small and the initial performance can be sustained for a long time, and the storage stability is good. 5% by volume or less is more preferable, and 0.1% by volume or less is most preferable.

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. In view of low THC in the exhaust gas and short system startup time, 80% by volume or more is preferable, and 90% by volume or more is more preferable.
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”.

  Although there is no restriction | limiting about the manufacturing method of the hydrocarbon oil used by this invention, The hydrocarbon oil of (1) and (2) shown below is desirable and the hydrocarbon oil of (1) is more desirable.

(1): Initial boiling point is 140 to 180 ° C., 90% by volume distillation temperature is 200 to 270, aromatic content is 20% by volume or less, linear saturated hydrocarbon content is 25% by mass or more, and carbon number is 10 A hydrocarbon mixture having a linear saturated hydrocarbon content of -15 to 20 mass% and a sulfur content of 300 massppm or less as a raw material oil, a reaction temperature of 250 to 310 ° C, a hydrogen pressure of 5 to 10 MPa, LHSV 0.5 -3.0h ^-1 , containing any of Ni-W, Ni-Mo, Co-Mo, Co-W, Ni-Co-Mo under conditions of hydrogen / hydrocarbon capacity ratio of 0.15-0.6 Hydrocarbon oil mainly composed of a base material at 140 ° C. to 230 ° C. obtained by a distillation operation from a hydrocarbon mixture that has been subjected to hydrodesulfurization treatment with a catalyst to be used.

  (2): Hydrodesulfurized kerosene obtained by hydrorefining straight run kerosene obtained from crude oil atmospheric distillation equipment, straight run heavy oil and residual oil obtained from atmospheric distillation equipment using a vacuum distillation equipment Hydrocracked kerosene obtained by hydrorefining a vacuum gas oil fraction obtained by treatment, hydrocracked kerosene obtained by hydrocracking a vacuum gas oil fraction, obtained by catalytic cracking of a vacuum gas oil fraction or desulfurized heavy oil Catalytic cracking kerosene, pyrolysis kerosene obtained by pyrolyzing straight-run heavy oil, hydrodesulfurized kerosene obtained by hydrotreating pyrolysis kerosene, hydrodesulfurization obtained by hydrotreating residual oil Extraction of ultra low sulfur kerosene, straight run kerosene, hydrodesulfurized kerosene or hydrorefined kerosene obtained by deep hydrotreating kerosene, straight run kerosene and / or hydrorefined kerosene in the presence of a hydrogenation catalyst Denormalized water, which is the residue after removing paraffin Substrates such as kerosene fraction of synthetic oil and / or hydrocracked product thereof obtained by FT (Fischer-Tropsch) synthesis after cracking fin kerosene, natural gas, coal, asphalt, etc. into carbon monoxide and hydrogen Hydrocarbon oil consisting of

The hydrorefining conditions for the substrate are not particularly limited as long as the hydrocarbon oil having the predetermined properties of the present invention can be obtained, but the reaction temperature is 100 to 350 ° C. in the presence of a hydrogenation catalyst, It is preferable that the hydrogen pressure is 1 to 10 MPa, the LHSV is 0.1 to 10 h ⁻¹ , and the hydrogen / oil ratio is 10 to 500 NL / L.

The hydrogenation catalyst is not particularly limited, and examples thereof include a hydrogenation active metal 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. Preferably used.
The active metal of the catalyst used for the hydrotreatment is preferably at least one metal selected from Group 6 and Group 8 metals of the Periodic Table. More preferably, it is at least one selected from Ru, Rd, Ir, Pd, Pt, Ni, Co, Mo and W. The active metal may be a combination of these metals, for example, Pt-Pd, Pt-Rh, Pt-Ru, Ir-Pd, Ir-Rh, Ir-Ru, Pt-Pd-Rh, Pt-Rh-Ru. , Ir-Pd-Rh, Ir-Rh-Ru, Co-Mo, Ni-Mo, Ni-W, and the like can be employed.

  The hydrocarbon oil of the present invention is used as a raw material for hydrogen production and as a fuel for burners in a hydrogen production system using a main heat source as a burner. By using the hydrocarbon oil of the present invention, reforming can be performed at a relatively low temperature in the hydrogen production system, and the burner load and the NOx emission amount can be reduced.

  Examples of the burner used in the hydrogen production system of the present invention include a spray burner and an evaporation burner. In addition to these burners, a surface burner using catalytic combustion that reduces NOx emissions can also be used.

  Examples of hydrogen production systems with burners include (1) a system consisting of a desulfurizer, reformer, and carbon monoxide purifier, and (2) a desulfurizer, reformer, desulfurizer (re-desulfurization), and monoxide. And a system comprising a carbon purifier and (3) a system comprising a reformer, a desulfurizer and a carbon monoxide purifier. The combination of the hydrogen production system which arrange | positioned the burner is not specifically limited to the system of said (1)-(3).

Examples of the desulfurizer, reformer, and carbon monoxide purifier include the following.
The desulfurizer is an apparatus for removing sulfur content in hydrocarbon oil. As the desulfurizer that can be used in the hydrogen production system of the present invention, for example, a copper-zinc system, a nickel system, etc. are used as a catalyst. Examples of conditions include a desulfurizer that performs a desulfurization treatment at a reaction temperature of 20 to 300 ° C., LHSV of 0.1 to 10 h ⁻¹ , and a reaction pressure of less than 1 MPa.

  The reformer is a device for reforming hydrocarbon oil to obtain hydrogen, and the following reformer is used in order to maximize the performance of the reformer with the hydrocarbon oil of the present invention. It is preferable to do.

(1) Mixing heat-vaporized hydrocarbon oil and water vapor, using a catalyst containing a group 8 element of the periodic table as an active metal, and reaction conditions include a reaction temperature of 400 to 1000 ° C., water and hydrocarbon oil A steam reforming reformer that obtains a product mainly composed of hydrogen by reacting at a mixing ratio (S / C) of 1 to 5 mol / mol.

(2) Mixing heated and vaporized hydrocarbon oil with water vapor and air, using a catalyst containing Group 8 element of the periodic table as an active metal, reaction conditions are 400 to 1000 ° C., water and hydrocarbon By reacting the mixing ratio of oil (S / C) at 0.5 to 5 mol / mol and the mixing ratio of oxygen and hydrocarbon oil (O ₂ / C) at 0.1 to 0.5 mol / mol, A self-thermal reforming reformer that obtains a hydrogen-based product.

In the “mixing ratio of water and hydrocarbon oil (S / C)” mentioned here, 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 here, O ₂ is the number of moles of oxygen (molecule), and C is the mole of carbon in the hydrocarbon oil (molecule). Means number. 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 ”.

  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 the carbon monoxide purifier that can be used in the hydrogen production system of the present invention include the following examples.

(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 are produced from carbon monoxide and water vapor under reaction conditions of reaction pressure of less than 1 MPa and a molar ratio of water and carbon monoxide in the reformed gas of 0.5 to 3.0 mol / mol Water gas shift reactor obtained as a product.

(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 to air to carbon dioxide by reaction conditions of reaction pressure of less than 1 MPa and a molar ratio of air to carbon monoxide in the reformed gas of 0.5 to 3.0 mol / mol. Selective oxidation reactor to convert.

  The hydrocarbon oil of the present invention can be reformed at a relatively low temperature as a raw material for hydrogen production in a hydrogen production system, and can also reduce burner load and NOx emissions as fuel for a burner in a hydrogen production system. Can do. For this reason, the hydrogen production system does not need to have two separate tanks, ie, a hydrogen production raw material tank and a burner fuel tank, and the system space efficiency is excellent.

  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 1-3 and Comparative Examples 1-2]
The hydrocarbon oils of the present invention (hydrocarbon oils A to C) and comparative hydrocarbon oils (hydrocarbon oils D and E) were produced by the methods described below. Their general properties are shown in Table 1.

(Manufacture of hydrocarbon oils A to E)
Hydrocarbon oil A: A hydrocarbon mixture obtained from a kerosene fraction having a sulfur content of 300 ppm by mass or less is used as a raw material oil, and is subjected to a hydrodesulfurization treatment. A fraction of ˜195 ° C. was separated to obtain hydrocarbon oil A.
Hydrocarbon oil B: A kerosene fraction obtained by subjecting a Middle Eastern crude oil to an atmospheric distillation apparatus is highly hydrorefined, and then a fraction of 150 ° C. to 200 ° C. is separated by a distillation operation to obtain hydrocarbon oil B did.
Hydrocarbon oil C: A hydrocarbon mixture of a kerosene fraction having a sulfur content of 300 mass ppm or less is used as a raw material oil, and a hydrocarbon oil obtained through a hydrodesulfurization process is subjected to a distillation operation to 150 ° C. to 200 ° C. After separating and removing the fraction at 0 ° C., hydrocarbon oil C was obtained by separating a fraction at 190 ° C. to 230 ° C. by a distillation operation from the hydrocarbon oil from which the linear saturated hydrocarbon was extracted and separated by zeolite.
Hydrocarbon oil D: 150 ° C. to 200 ° C. by distillation operation from hydrocarbon oil obtained through a hydrodesulfurization treatment using a hydrocarbon mixture of a kerosene fraction having a sulfur content of 300 ppm by mass or less as a raw material oil Then, a fraction at 245 ° C. to 270 ° C. was separated by distillation from the hydrocarbon oil from which the linear saturated hydrocarbon was extracted and separated by zeolite.
Hydrocarbon oil E: A kerosene fraction obtained by subjecting Middle Eastern crude oil to an atmospheric distillation apparatus is highly hydrorefined, and then a fraction of 150 ° C. to 265 ° C. is separated by a distillation operation to obtain hydrocarbon oil E and did.

(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”.

H / C refers to the molar ratio of hydrogen element to carbon element measured by a method in accordance with ASTM D5291-01 (Standard Test Method for Hydrocarbon Types in Middle Distillates by Mass Spectrometry).
The Saybolt color refers to the Saybolt color measured by the Saybolt color test method in JIS K2580 “Petroleum products-color test method”.
Copper plate corrosion refers to copper plate corrosion measured by JIS K2513 "Petroleum products-Copper plate corrosion test method".

The component ratio of the hydrocarbon having 13 carbon atoms is a value (mass%) measured using GC-FID, and the column is a methyl silicon capillary column (ULTRAALLOY-1, 0.25 mmφ, 30 m), carrier gas. Helium is used for the detector, and a hydrogen ion detector (FID) is used for the detector, the carrier gas flow rate is 1.0 mL / min, the split ratio is 1:79, the sample injection temperature is 280 ° C., and the column temperature rising condition is 50 ° C. (5 minutes). → (5 ° C./min)→ 280 ° C. (10 minutes) Indicates a value obtained by performing area integration of a hydrocarbon having 13 carbon atoms from a chromatograph measured under the conditions of a detector temperature of 300 ° C.
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.

Next, each obtained hydrocarbon oil was evaluated using the following two hydrocarbon oil reforming systems.
(1) Steam reforming reforming system Hydrocarbon oil and water desulfurized to a sulfur content of less than 0.1 ppm by mass with a desulfurizer filled with a nickel-based adsorptive desulfurization catalyst are vaporized by heating, and filled with a precious metal catalyst. Then, it was led to a reformer maintained at a predetermined temperature, and a reformed gas rich in hydrogen content was generated. The temperature of the reformer was set to the lowest temperature at which reforming was completely performed (the lowest temperature at which the reformed gas did not contain hydrocarbon oil).
The reformed gas was then led to a carbon monoxide purifier. The carbon monoxide purifier is divided into two parts, a front stage and a rear stage. In the former stage, the reformed gas is passed through a reactor filled with a copper-zinc catalyst together with water vapor, and in the latter stage, the reformed gas is passed through a reactor filled with a noble metal catalyst together with air. Carbon monoxide was converted to carbon dioxide. The operating conditions were set so that the hydrogen amount was 10 L / min and the CO concentration was 10 ppm by volume at the carbon monoxide purifier outlet.
The heat sources required for the hydrocarbon oil and water vaporizers, desulfurizers, reformers and carbon monoxide purifiers are the hydrocarbon oils of the present invention (hydrocarbon oils A to C) and the comparative hydrocarbon oils ( A spray-type burner using hydrocarbon oils D and E) was supplied in each vessel. The amount of air for the burner was set so that the oxygen concentration in the combustion exhaust gas was 8% by volume.
The operating conditions of each reactor are as follows.
<Desulfurizer> Reaction temperature: 200 ° C
<Reformer> LHSV: 1 h ⁻¹ , H ₂ O / C molar ratio: 3 mol / mol <Carbon monoxide purifier first stage> Reaction temperature: 230 ° C., H ₂ O / CO molar ratio: 5 mol / mol
< _Second stage of carbon monoxide purifier> Reaction temperature: 110 ° C., O ₂ / CO molar ratio: 1.5 mol / mol A steam reforming reforming system evaluation flow is shown in FIG.

(2) Self-thermal reforming reforming system Hydrocarbon oil and water desulfurized to a sulfur content of less than 0.1 mass ppm by a desulfurizer filled with a nickel-based adsorptive desulfurization catalyst are vaporized by heating, and preheated air and precious metal system The catalyst was charged and led to a reformer maintained at a predetermined temperature to generate a reformed gas rich in hydrogen. The temperature of the reformer was set to the lowest temperature at which reforming was completely performed (the lowest temperature at which the reformed gas did not contain hydrocarbon oil).
The reformed gas was then led to a carbon monoxide purifier. The carbon monoxide purifier is divided into two parts, a front stage and a rear stage. In the former stage, the reformed gas is passed through a reactor filled with a copper-zinc catalyst together with water vapor, and in the latter stage, the reformed gas is passed through a reactor filled with a noble metal catalyst together with air. Carbon monoxide was converted to carbon dioxide. The operating conditions were set so that the hydrogen amount was 10 L / min and the CO concentration was 10 ppm by volume at the carbon monoxide purifier outlet.
The heat sources required for the hydrocarbon oil and water vaporizers, desulfurizers, reformers and carbon monoxide purifiers are the hydrocarbon oils of the present invention (hydrocarbon oils A to C) and the comparative hydrocarbon oils ( A spray-type burner using hydrocarbon oils D and E) was supplied in each vessel. The amount of air for the burner was set so that the oxygen concentration in the combustion exhaust gas was 8% by volume.
The operating conditions of each reactor are as follows.
<Desulfurizer> Reaction temperature: 200 ° C
<Reformer> LHSV: 1 h ⁻¹ , H ₂ O / C molar ratio: 2 mol / mol,
O ₂ / C molar ratio: 0.3 mol / mol <carbon monoxide purifier first stage> reaction temperature: 230 ° C., H ₂ O / CO ratio: 5 mol / mol <carbon monoxide purifier latter stage> reaction temperature: 110 ° C, O ₂ / CO ratio: 1.5 mol / mol An autothermal reforming reforming system evaluation flow is shown in FIG.

(3) Evaluation The NOx emission amount by hydrocarbon oil when the above two hydrocarbon oil reforming systems were used was evaluated by the following method.
After the adjustment of each reactor was completed so that the hydrocarbon oil was completely reformed in the reformer and the hydrogen amount was 10 L / min and the CO concentration was 10 vol ppm at the carbon monoxide purifier outlet, The NOx emissions in each hydrocarbon oil were compared by connecting the burner combustion exhaust gas lines in the reactor and vaporizers to one line and measuring the NOx emissions.
The above evaluation results are shown in Table 2. In addition, the increase / decrease comparison in two reforming systems performed the relative comparison by making NOx discharge | emission amount of the comparative example 1 into 100.0.
As a result, it can be seen that the hydrocarbon oils of Examples 1 to 3 are reduced in the amount of NOx discharged from the hydrogen production system as compared with the hydrocarbon oils of Comparative Examples 1 and 2.

It is an evaluation flowchart of a steam reforming type reformer. It is an evaluation flowchart of a self-heat reforming type reformer.

Claims (2)

  Flash point is 40 ° C or higher, initial boiling point is 145 ° C or higher and 195 ° C or lower, 95% by volume distillation temperature is 220 ° C or lower, Saybolt color +25 or higher, copper plate corrosion is 1 or lower, sulfur content is 0.5 mass ppm or lower, Hydrogen production of a hydrogen production system mainly using a burner as a heat source, wherein the component ratio of hydrocarbons having 13 carbon atoms is 25% by mass or less and the molar ratio of hydrogen element to carbon element is 1.95 or more Hydrocarbon oil for use. The hydrocarbon oil according to claim 1, wherein the hydrocarbon oil is used as a fuel for a burner which is a heat supply source of a hydrogen production system.

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