KR101115663B1 - Hydrocarbon oil for hydrogen production and hydrogen production system - Google Patents

Abstract

As a hydrocarbon oil for hydrogen production in a hydrogen production system where the reforming efficiency is less deteriorated and coke hardly occurs in a catalyst present in the reformer, a flash point of 40 ° C. or more, sulfur content of 0.3 mass ppm or less, aromatic content of 20% by volume or less, naphthene powder 20 To 50 vol.%, Initial boiling point range from 150 to 210 ° C, 90 vol.% Distillation temperature, 220 to 255 ° C, proportion of 13 carbon atoms, 10 to 30% by mass, 43 ° C, peroxide after 13 weeks of storage test up to 2 mg / kg There is provided a hydrocarbon oil for hydrogen production of a hydrogen production system, which satisfies simultaneously.

Hydrogen Production, Hydrocarbon Oil, Hydrodesulfurization, Hydrogen Production System

Description

Hydrogen Oil for Hydrogen Production and Hydrogen Production System {HYDROCARBON OIL FOR HYDROGEN PRODUCTION AND HYDROGEN PRODUCTION SYSTEM}

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

In recent years, as the sense of crisis on the global environment is heightened, development of an energy supply system that is easy for the earth is required, and since the energy efficiency is high and the exhaust gas is clean, hydrogen such as fuel cells and hydrogen engines is used. Fueled systems are in the limelight. Among these, as a supply method of hydrogen to a fuel cell, besides a method of directly supplying hydrogen in the form of compression or liquefaction, a supply method by reforming an oxygen fuel such as methanol and hydrocarbons such as naphtha and kerosene is known. There is (for example, refer nonpatent literature 1). Among these, the method of directly supplying hydrogen has the advantage that it can be used as a fuel as it is, but there is a problem in the storage storage of the gas at room temperature and the mountability when used in a vehicle or the like. In addition, methanol is relatively easy to produce hydrogen by reforming in the system, but has low energy efficiency per weight, is toxic and corrosive, and thus has difficulty in handling and storage. Meanwhile, the production of hydrogen by reforming hydrocarbons such as naphtha and kerosene has attracted attention due to the fact that existing fuel supply infrastructure can be used, and that the overall energy efficiency is high. It is generally known that the sulfur content contained in these hydrocarbons deteriorates the performance of catalysts or fuel cells, particularly solid polymer fuel cells, used in reforming processes for generating hydrogen. Therefore, in the production of hydrogen provided in the fuel cell system, a desulfurization step and a reforming step of the trace sulfur contained in the hydrocarbon are required. However, depending on the type of hydrocarbon, reforming efficiency may be suppressed or coking may occur in the catalyst in the reforming apparatus, which may adversely affect the system.

(Non-Patent Document 1) Masaki Ikematsu, "Engine Technology", Sanhae Company, January 2001, Vol. 3, No. 1, p.35

[Initiation of invention]

In view of such a situation, it is an object of the present invention to provide a hydrocarbon oil for producing hydrogen, which has little deterioration in reforming efficiency and is hard to cause coking to occur in the catalyst in the reformer.

The present inventors have completed the present invention by finding that the hydrocarbon mixture having a specific property can solve the above problems as a result of intensive studies.

That is, the 1st aspect of this invention has a flash point of 40 degreeC or more, sulfur content 0.3 mass ppm or less, aromatic content 20 volume% or less, naphthene powder 20-50 volume%, initial boiling point 150-210 degreeC, distillation temperature of 90 volume%. It relates to a hydrocarbon oil for hydrogen production in a hydrogen production system, characterized in that the peroxide after the storage test for 10 to 30 mass%, 43 ° C, and 13 weeks of storage in the range of 220 to 255 ° C, and 13 carbon atoms simultaneously satisfies 2 mg / kg or less.

The present invention also relates to a hydrogen production system characterized by using the hydrocarbon oil described above as a hydrocarbon oil for hydrogen production in a hydrogen production system containing a desulfurizer and a reformer.

In addition, the present invention uses a catalyst comprising (1) mixing a vaporized hydrocarbon oil with water vapor as a reformer and containing a group VIII element of the periodic table as the active metal, and the reaction temperature is in the range of 400 to 1000 캜. A steam reforming reformer having a mixing ratio (S / C) of water and hydrocarbon oil of 1 to 5 mol / mol or (2) heating and vaporizing hydrocarbon oil is mixed with steam and air, and the periodic table contains a group VIII element as an active metal. The reaction temperature is 400 to 1000 ° C., the mixing ratio (S / C) of water and hydrocarbon oil is 0.5 mol / mol, and the mixing ratio (O ₂ / C) of oxygen and hydrocarbon oil is 0.1. The present invention relates to a hydrogen production system as described above, wherein any one of the self-heat reforming reformers is in the range of 0.5 mol / mol.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The flash point of the hydrogen-producing hydrocarbon oil of the present invention (hereinafter referred to as the hydrocarbon oil of the present invention) should be 40 ° C or higher, preferably 42 ° C or higher, and more preferably 45 ° C or higher from the viewpoint of flammability and ease of handling.

In addition, a flash point here is the value measured according to JISK2265 "crude oil and a petroleum product-flash point test method."

The sulfur content of the hydrocarbon oil according to the present invention should be 0.3 mass ppm or less in terms of desulfurization rate, durability of the desulfurization catalyst, durability of the reforming catalyst, reduction of reforming reactivity, and hydrogen generation amount per carbon dioxide generation, and preferably 0.2 mass ppm or less.

Here, sulfur content is the value of sulfur content measured according to ASTMD4045-96 "Standard Test Method for Sulfur in Petroleum Products by Hydrogenolysis and Rateometric Colorimetry".

The aromatic content of the hydrocarbon oil according to the present invention is 20% by volume or less from the viewpoint of suppression of lowering the desulfurization rate, lowering the durability of the desulfurization catalyst, lowering the durability of the reforming catalyst, lowering the reforming reactivity, and lowering the amount of hydrogen generated per carbon dioxide generation. It should be 10% by volume or less.

In addition, the aromatic content here is the value of aromatic hydrocarbon content measured by the fluorescent indicator adsorption method of JISK2536 "Petroleum products-hydrocarbon type test method."

The naphthenic hydrocarbon content of the hydrocarbon oil according to the present invention should be 20% by volume or more, preferably 30% by volume or more, and more preferably 40% by volume or more from the viewpoint of suppressing the reduction in the amount of hydrogen generated per carbon dioxide generation. On the other hand, it should be 50 vol% or less from the viewpoint of lowering the desulfurization rate, lowering the durability of the desulfurization catalyst, lowering the durability of the reforming catalyst, and lowering the reforming reactivity.

In addition, content of a naphthenic hydrocarbon here is measured by the method based on ASTMD2425 "Test Method for Instrumental Determination of Carbon, Hydrogen, and Nitrogen in Petroleum Products and Lubricants).

The proportion of hydrocarbons having 13 carbon atoms in the hydrocarbon oil according to the present invention should be 10% by mass or more, preferably 13% by mass or more, more preferably 15% by mass or more, from the viewpoint of the amount of hydrogen generated per weight and the amount of hydrogen generated per carbon dioxide generated. desirable. On the other hand, it should be 30 mass% or less from a viewpoint of the deterioration of reforming efficiency, and suppressing coking to the catalyst in a reformer, and 20 mass% or less is more preferable.

Here, a hydrocarbon content of 13 carbon atoms is a value (mass%) measured using GC-FID. That is, a methyl silicon capillary column (ULTRAALLOY-1, 0.25 mm φ, 30 m) is used as a column, helium is used as a carrier gas, and a hydrogen ion detector (FID) is used as a detector, and a carrier gas flow rate of 1.0 ml / min, Split ratio 1:79, sample injection temperature 280 degreeC, column temperature raising conditions 50 degreeC (5 minutes) → (5 degreeC / min) → 280 degreeC (10 minutes), The number of carbons by chromatography measured on the conditions of a detector temperature of 300 degreeC It is the value which performed area integration of 13 hydrocarbons.

The peroxide value after the 43 ° C., 13-week storage test of the hydrocarbon oil according to the present invention should be 2 mg / kg or less and 1 mg / kg or less from the viewpoint of minimizing the deterioration of the reforming efficiency and suppressing the occurrence of coking of the catalyst present in the reforming unit. Is preferred, with 0 mg / kg being most preferred.

In addition, the peroxide value after 43 degreeC and the storage test for 13 weeks here is inject | poured 400 ml of samples to the 500 ml Pyrex bottle (air hole holding), and after storing for 13 weeks at 43 degreeC, it is JPI-5S-46-96 "of kerosene. Peroxide is the value measured according to "Test Method."

The initial boiling point (IBP) of the hydrocarbon oil according to the present invention should be at least 150 ° C, preferably at least 160 ° C, more preferably at least 170 ° C, in view of flammability, increase in evaporation gas (THC), and handleability. On the other hand, in view of deterioration of reforming efficiency and occurrence of coking of the catalyst present in the reforming apparatus, it should be 210 ° C or less, preferably 200 ° C or less, and more preferably 190 ° C or less.

The 90 vol% distillation temperature (T90) of the hydrocarbon oil according to the present invention should be at least 220 ° C, more preferably at least 230 ° C, in view of the amount of hydrogen generated per weight, the amount of hydrogen generated per carbon dioxide generated. On the other hand, it should be 255 degrees C or less from a viewpoint of the deterioration of reforming efficiency, and the occurrence of coking of the catalyst which exists in a reforming apparatus, and 240 degrees C or less is more preferable.

There is no particular limitation on the distillation properties other than IBP and T90 of the hydrocarbon oil according to the present invention, but the following are preferable.

It is preferable that it is 160 degreeC or more from a viewpoint of flammability and evaporation gas (THC) generation | generation, and, as for 10 volume% distillation temperature T10, 180 degreeC or more is more preferable. On the other hand, from the viewpoint of deterioration of the startup time of the hydrogen production system, 210 ° C or less is preferable, and 205 ° C or less is more preferable.

The 50 vol% distillation temperature (T50) is preferably 180 ° C or higher, more preferably 190 ° C or higher, and most preferably 200 ° C or higher, in view of the hydrogen generation amount per weight and the hydrogen generation amount per carbon dioxide generation amount. On the other hand, from the viewpoint of deterioration of the startup time of the hydrogen production system, 220 ° C or less is preferable, and 215 ° C or less is more preferable.

The 95 vol% distillation temperature (T95) is preferably 190 ° C or higher, more preferably 210 ° C or higher, and most preferably 220 ° C or higher, in view of the hydrogen generation amount per weight and the hydrogen generation amount per carbon dioxide generation amount. On the other hand, from the viewpoint of deterioration of the startup time of the hydrogen production system, 270 ° C. or less is preferable, 260 ° C. or less is more preferable, and 250 ° C. or less is most preferable.

The end point EP is preferably 200 ° C or more, more preferably 220 ° C or more, and most preferably 240 ° C or more, in view of the amount of hydrogen generated per weight and the amount of generated hydrogen per carbon dioxide generated. On the other hand, from the viewpoint of deterioration of the startup time of the hydrogen production system, 280 ° C or less is preferable, 270 ° C or less is more preferable, and 260 ° C or less is most preferable.

In addition, IBP, T10, T50, T90, T95, and EP here are the values measured according to JISK2254 "Petroleum products-distillation test method-atmospheric distillation test method."

Although there is no restriction | limiting in particular about the olefin content of hydrocarbon oil which concerns on this invention, It is preferable that it is 1 volume% or less from a viewpoint of little deterioration of a reforming catalyst, long initial performance, good storage stability, etc., and 0.5 volume% The following is more preferable, and 0.1 volume% or less is the most preferable.

There is no restriction on the saturation of hydrocarbon oil according to the present invention, but from the viewpoint of high hydrogen generation per weight, high hydrogen generation per carbon dioxide generation, low THC in exhaust gas, short system startup time, etc. It is preferable that it is 80 volume% or more, and 90 volume% or more is more preferable.

In addition, the olefin content and saturated content mentioned above are the value of the olefin content and saturated hydrocarbon content measured by the fluorescent indicator adsorption method of JISK2536 "petroleum product-hydrocarbon type test method."

The hydrocarbon oil according to the present invention can be preferably used as a hydrocarbon oil for hydrogen production in a hydrogen production system having at least a reformer such as a desulfurizer and a steam reforming type or a self-heat reforming type described below. By using the hydrocarbon oil according to the present invention in the hydrogen production system, deterioration of the reforming efficiency of the reformer can be suppressed and coking of the catalyst present in the reformer can be suppressed.

The desulfurization unit is a device for removing sulfur content in hydrocarbon oil. In the present invention, copper-zinc-based, nickel-based, etc. are used as a catalyst, and the reaction conditions are 20 to 300 ° C., LHSV 0.1 to 10 h ⁻¹ , and reaction pressure below 1 MPa as reaction conditions. A desulfurizer for carrying out desulfurization treatment may be preferably used.

The reformer is an apparatus for obtaining hydrogen by reforming hydrocarbon oil, and in the present invention, it is preferable that the reformer is as follows.

(1) Mixing ratio of water and hydrocarbon oil at a reaction temperature of 400 to 1000 ° C., in the presence of a reforming catalyst containing a mixed gas of hydrocarbon oil and water vapor according to the present invention as an active metal with a periodic table group 8 element. Steam reformer to obtain a product containing hydrogen as a main component by reacting 1) at 1 to 5 mol / mol.

(2) Mixing ratio of water and hydrocarbon oil at a reaction temperature of 400 to 1000 ° C., in the presence of a reforming catalyst containing a mixed gas of hydrocarbon oil, water vapor and air according to the present invention as an active metal with a periodic table group 8 element. A self-heat reforming reformer which obtains a product containing hydrogen as a main component by reacting / C) with 0.5 to 5 mol / mol and mixing ratio of oxygen and hydrocarbon oil (O ₂ / C) to 0.1 to 0.5 mol / mol.

In addition, in the "mixing ratio (S / C) of water and hydrocarbon oil" as used in the present invention, S means the number of moles of water (molecule), C means the number of moles of carbon in the hydrocarbon oil (molecule). Thus, for example, a method of obtaining the "mixing ratio (S / C) of water and hydrocarbon oil" will be described. When water (molecular): 6 moles and hydrocarbon oil ethane (C ₂ H ₆ ): 1 mole are used. The mixing ratio (S / C) of water and hydrocarbon oil is "S / C = 6 mol / 2 mol = 3" because the number of carbon moles in 1 mole of ethane: hydrocarbons is hydrocarbon oil.

Similarly, in the "mixing ratio of oxygen and hydrocarbon oil (O ₂ / C)" in the present invention, O ₂ means the mole number of oxygen (molecule), C means the mole number of carbon in the hydrocarbon oil (molecule). do. Thus, for example, a method for obtaining the "mixing ratio of oxygen and hydrocarbon oil (O ₂ / C)" will be described, for example, when oxygen (molecular): 0.6 mole and hydrocarbon oil ethane (C ₂ H ₆ ): 1 mole are used. The mixing ratio (O ₂ / C) of oxygen and hydrocarbon oil is “O ₂ /C=0.6 mol / 2 mol = 0.3” because the number of carbon moles in 1 mole of ethane: hydrocarbons is hydrocarbon oil.

The active metal of the catalyst used in the steam reforming reformer is preferably ruthenium, rhodium, platinum or the like from the viewpoint of reforming reactivity for obtaining hydrogen from the hydrocarbon oil according to the present invention, among which ruthenium and rhodium are particularly preferable. . The reaction temperature is preferably 400 ° C or higher, more preferably 500 ° C or higher, more preferably 1000 ° C or lower, and even more preferably 800 ° C or lower from the viewpoint of suppressing the amount of coking on the catalyst. The mixing ratio (S / C) of water and hydrocarbon oil is preferably 1 mol / mol or more, more preferably 2 mol / mol or more, more preferably 5 mol / mol or less from the viewpoint of reformer efficiency in view of suppressing the amount of coking generated on the catalyst. Is preferable, and 4 mol / mol or less is more preferable.

As the active metal of the catalyst used in the self-heat reforming reformer, ruthenium, rhodium, platinum, etc. are preferable from the viewpoint of reforming reactivity for obtaining hydrogen from the hydrocarbon oil according to the present invention, among which ruthenium, rhodium is particularly preferable. Do. The reaction temperature is preferably 400 ° C or higher, more preferably 500 ° C or higher, more preferably 1000 ° C or lower, and even more preferably 800 ° C or lower from the viewpoint 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, and more preferably 5 mol / mol or less from the viewpoint of reformer efficiency in view of suppressing the amount of coking generated on the catalyst. Is preferable, and 3 mol / mol or less is more preferable. The mixing ratio (O ₂ / C) of oxygen and hydrocarbon oil is preferably 0.1 mol / mol or more, more preferably 0.2 mol / mol or more, and more preferably 0.5 mol / mol from the viewpoint of suppressing the amount of coking generated on the catalyst. The following is preferable and 0.4 mol / mol or less is more preferable.

Hydrogen production systems in which the hydrocarbon oil according to the invention can be used are preferably provided with other mechanisms, in combination with desulfurizers, reformers. There are no particular limitations on the other mechanism combined with the reformer, but for example, a carbon monoxide purifier may be mentioned. Examples of the arrangement include (a) a desulfurizer, a reformer, a carbon monoxide purifier, and (b) a desulfurizer, a reformer? Examples thereof include desulfurization (resulfurization), carbon monoxide purifiers, and (c) reformers, desulfurization, and carbon monoxide purifiers.

The carbon monoxide purifier performs removal of carbon monoxide contained in the gas produced in the reformer and becomes a catalyst poison of the fuel cell. Examples of the carbon monoxide purifier include the following.

(1) a reforming gas obtained from a reformer and steam vaporized by heating are mixed, and copper, zinc, platinum, ruthenium, rhodium, etc. are used as a catalyst, reaction temperature 200-500 degreeC, gas space velocity 1000-10000h <^-1> , A water gas shift reactor which obtains carbon dioxide and hydrogen from carbon monoxide and water vapor as a product under reaction conditions of a reaction pressure of 0.5 to 3.0 mol / mol of carbon monoxide in water and reformed gas of less than 1 MPa.

(2) The reforming gas obtained from the reformer is mixed with compressed air, and copper, nickel, platinum, ruthenium, rhodium, and the like are used as a catalyst, and the reaction temperature is 100 to 300 ° C., the gas space velocity is 1000 to 10000 h ⁻¹ , and the reaction pressure. A selective oxidation reactor for converting carbon monoxide into carbon dioxide in carbon monoxide and air under a reaction condition of less than 1 MPa and a ratio of 0.5 to 3.0 mol / mol of carbon monoxide in air and reformed gas.

[Industrial Availability]

The hydrocarbon oil of the present invention is suitable as a hydrocarbon oil for hydrogen production because the amount of coke deposition of the reforming catalyst after long time operation is small and the change in conversion rate is small.

Best Mode for Carrying Out the Invention

Hereinafter, although an Example and a comparative example are given and this invention is concretely demonstrated, this invention is not limited to these examples.

<< Examples 1 to 5 and Comparative Examples 1 to 3 >>

Hydrocarbon oils A to G were prepared according to the method described below. Their general characteristics are shown in Table 1.

Hydrocarbon oil A is a hydrocarbon mixture of kerosene fraction having a sulfur content of 300 mass ppm or less as a raw material oil, and is separated from a hydrocarbon oil of 150 ° C. to 200 ° C. by distillation from a hydrocarbon oil obtained through a step of hydrodesulfurization. It is hydrocarbon oil which extracted and removed a part of linear saturated hydrocarbon by zeolite after removal.

Hydrocarbon oil B is a zeolite having a sulfur content of 300 mass ppm or less by using a hydrocarbon mixture of kerosene fraction as a raw material oil, from the hydrocarbon oil obtained through the step of hydrodesulfurization treatment to remove the oil of 150 ℃ to 200 ℃ by distillation operation, and then zeolite Hydrocarbon oil which extracted a part of furnace linear saturated hydrocarbon and the kerosene fraction in 150 degreeC-200 degreeC removed by the distillation operation first are mixed.

Hydrocarbon oil C is obtained by highly hydrodesulfurizing the kerosene fraction obtained by treating Middle Eastern crude oil in an atmospheric distillation apparatus, and then separating the fraction of 150 ° C to 270 ° C by distillation.

Hydrocarbon oil D is obtained by hydrodesulfurizing the kerosene fraction obtained by treating Middle Eastern crude oil in an atmospheric distillation apparatus, and then performing hydrorefining.

Hydrocarbon oil E is obtained by ring-opening most of the aromatics by hydrodesulfurizing the kerosene fraction obtained by treating Middle Eastern crude oil in an atmospheric distillation apparatus and then performing hydrorefining.

Hydrocarbon oil F is obtained by highly hydrodesulfurizing the kerosene fraction obtained by treating southern crude oil in an atmospheric distillation apparatus, and then separating the fraction of 150 ° C to 250 ° C by distillation.

Hydrocarbon oil G is 150-200 degreeC oil fraction obtained by the distillation operation from the hydrocarbon oil obtained through the process of hydrodesulfurization process using the hydrocarbon mixture of kerosene fraction whose sulfur content is 300 mass ppm or less as raw material oil.

(Measurement)

General properties of hydrocarbon oils A to G were measured by the following test methods.

Density represents the density measured according to JIS K2249 "Density test method and density, mass, capacity conversion table of crude oil and petroleum products".

Flash point represents the flash point measured according to JIS K2265 "Crude oil and petroleum products-flash point test method".

Distillation properties (IBP, T10, T50, T90, T95, EP) are all measured according to JIS K 2254 "Petroleum products-Distillation test method-Atmospheric distillation test method".

Sulfur content represents the sulfur content measured according to ASTM D4045-96 "Standard Test Method for Sulfur in Petroleum Products by Hydrogenolysis and Rateometric Colorimetry".

Aromatic powder and olefin powder represent aromatic content and olefin content as measured by the fluorescent indicator adsorption method of JIS K2536 "Petroleum products-hydrocarbon type test method."

Naphthene powder represents naphthenic hydrocarbon content measured by the method based on ASTMD2425 (Standard Test Method for Hydrocarbon Types in Middle Distillates by Mass Spectrometry).

Peroxide value after 43 ℃, 13 weeks storage test 400ml in 500ml capped Pyrex bottle (with air holes) and stored for 13 weeks at 43 ℃, JPI-5S-46-96 "peroxide value test method of kerosene "Represents the value measured.

The proportion of hydrocarbons having 13 carbon atoms is measured by GC-FID (mass%), methylsilicone capillary column (ULTRAALLOY-1, 0.25mm φ, 30m) as column, helium as carrier gas, Hydrogen ion detector (FID) was used as a detector, and carrier gas flow rate 1.0 ml / min, split ratio 1:79, sample injection temperature 280 degreeC, column temperature raising conditions 50 degreeC (5 minutes) → (5 degreeC / min) → The value calculated | required by performing area integration of 13 carbon number hydrocarbons by the chromatography measured by 280 degreeC (10 minutes) and detector temperature 300 degreeC conditions is shown.

The obtained hydrocarbon oils A-G were evaluated as follows according to the evaluation flowchart shown to FIG. 1 and FIG.

In addition, a hydrocarbon preheater, a steam generator, and the air preheater were set to 300 degreeC, respectively.

(1) steam reforming evaluation

A flow chart of steam reforming assessment is shown in FIG. 1. After passing the hydrocarbon oil through a desulfurization unit filled with a desulfurization catalyst (nickel-based, φ2 mm, filled amount 100 ml), the hydrocarbon oil and water were evaporated by electric heating, respectively, and the reforming catalyst (ruthenium-based, φ2 mm, filled amount 5 ml) was filled with electricity. A reforming gas rich in hydrogen was generated by introducing into a reforming reaction tube maintained at a predetermined temperature by a heater.

First, the desulfurization reaction and the reforming reaction were carried out in the following reaction condition S1.

(Reaction condition S1)

<Desulfurization reaction> LHSV: 0.5h ^-1 , catalyst bed outlet temperature: 200 ° C

<Modification> LHSV: 0.5 h ^-1 , S / C: 3.5 mol / mol, catalyst bed outlet temperature: 650 ° C.

After the conversion ratio was determined under reaction condition S1, oil passage was performed for 100 hours under the next reaction condition A1.

(Reaction condition A1)

<Desulfurization reaction> LHSV: 5h ^-1 , catalyst bed outlet temperature: 230 ° C.

<Modification> LHSV: 5h ^-1 , S / C: 3.5 mol / mol, catalyst bed outlet temperature: 650 ° C

After the operation in the reaction condition A1, the reaction condition was returned to S1, and the conversion rate was measured to calculate a change from the conversion rate at the initial stage of operation.

These evaluations were carried out for hydrocarbon oils A to G, respectively. The results are shown in Table 2.

In addition, as a comparative example of the reaction conditions, the reforming reaction was performed under the following reaction condition S1 '.

(Reaction condition S1 ')

<Desulfurization reaction> LHSV: 0.5h ^-1 , catalyst bed outlet temperature: 200 ° C

<Modification> LHSV: 0.5h ^-1 , S / C: 0.8 mol / mol, catalyst bed outlet temperature: 650 ° C

After the conversion ratio was determined under reaction condition S1 ', oil passage was performed for 100 hours under the next reaction condition A1'.

(Reaction condition A1 ')

<Desulfurization reaction> LHSV: 5h ^-1 , catalyst bed outlet temperature: 230 ° C.

<Modification> LHSV: 5h ⁻¹ , S / C: 0.8 mol / mol, catalyst bed outlet temperature: 650 ° C.

After the operation in the reaction condition A1 ', the reaction condition was returned to S1' and the conversion rate was measured to calculate the change from the conversion rate at the initial stage of operation. The result was written together in Table 2 as a comparative example.

(2) self-heat modification evaluation

A flow chart of the self heat modification assessment is presented in FIG. 2. The hydrocarbon oil is passed through a desulfurization unit filled with a desulfurization catalyst (nickel type, φ2 mm, packed amount 100 ml), and then the hydrocarbon oil and water are evaporated by electric heating and reformed catalyst (rhodium based, φ2 mm, filled amount 5 ml) together with the preheated air. Was charged into a reforming reaction tube maintained at a predetermined temperature with an electric heater to generate a reformed gas rich in hydrogen.

First, the desulfurization reaction and the reforming reaction were carried out in the following reaction condition S2.

(Reaction condition S2)

<Desulfurization reaction> LHSV: 0.5h ^-1 , catalyst bed outlet temperature: 200 ° C

<Modification> LHSV: 0.5 h ^-1 , S / C: 2 mol / mol, O ₂ / C: 0.30, catalyst bed outlet temperature: 650 ° C

After the conversion ratio was determined under reaction condition S2, oil passage was performed for 100 hours under the next reaction condition A2.

(Reaction condition A2)

<Desulfurization reaction> LHSV: 5h ^-1 , catalyst bed outlet temperature: 230 ° C.

<Modification> LHSV: 5h ⁻¹ , S / C: 2 mol / mol, O ₂ / C: 0.30, catalyst bed outlet temperature: 650 ° C.

After the operation in the reaction condition A2, the reaction condition was returned to S2, and the conversion rate was measured to calculate a change from the conversion rate at the initial stage of operation.

These evaluations were carried out for hydrocarbon oils A to G, respectively. The results are shown in Table 2.

In addition, as a comparative example of the reaction conditions, desulfurization reaction and reforming reaction were performed under the following reaction conditions S2 '.

(Reaction condition S2 ')

<Desulfurization reaction> LHSV: 0.5h ^-1 , catalyst bed outlet temperature: 200 ° C

<Modification> LHSV: 0.5 h ^-1 , S / C: 0.3 mol / mol, O ₂ / C: 0.30, catalyst bed outlet temperature: 650 ° C

After the conversion ratio was determined under reaction condition S2 ', oil passage was performed for 100 hours under the next reaction condition A2'.

(Reaction conditions A2 ')

<Desulfurization reaction> LHSV: 5h ^-1 , catalyst bed outlet temperature: 230 ° C.

<Modification> LHSV: 5h ^-1 , S / C: 0.3 mol / mol, O ₂ / C: 0.30, catalyst bed outlet temperature: 650 ° C

After the operation at the reaction condition A2 ', the reaction condition was returned to S2' and the conversion rate was measured to calculate the change from the conversion rate at the initial stage of operation. The result was written together in Table 2 as a comparative example.

In addition, the measurement of the conversion rate was performed as follows. Each reforming evaluation unit was provided with a gas meter capable of measuring the flow rate of the reformed gas generated at the reaction tube outlet line, and a gas chromatography capable of analyzing the composition of the reformed gas generated and unreacted hydrocarbon oil. The tank for supply of hydrocarbon oil and water was provided on the balance, and the supply amount to the reaction tube per hour was measured by this balance. The conversion rate of hydrocarbon oil was calculated from the analysis results of the hydrocarbon oil supply amount, the generation reformed gas flow rate, and the gas composition. The conversion rate is defined as follows.

% Conversion = amount of C1 (CO ₂ , CO and CH ₄ ) in the off-gas / amount of C in hydrocarbon oil supplied x 100

After passing through 100 hours and measuring a conversion rate, the amount of coke deposits in a reforming catalyst was measured.

The coke deposition analysis divides the separated catalyst layer into a total of three layers of upper and lower layers, and calculates the amount of carbon (mass%), respectively, according to JIS Z2615 "General rule for quantifying carbon in metal materials: infrared absorption method). The average value was calculated | required The coke deposition amount in each hydrocarbon oil was shown in Table 2 as a relative value when the value of the comparative example 1 was set to 100.

From the results shown in Table 2, when the hydrocarbon oil (Examples 1 to 5) of the present invention was used, not only the conversion was higher than that of the hydrocarbon oil and the apparatus conditions of the comparative example, but the conversion ratio could be stably maintained for a long time, It has also been found that coking occurs in the catalyst present in the reformer.

TABLE 1

Table 2

* 1: The conversion rate is a relative value when the conversion rate at the initial stage of operation of Comparative Example 1 is 100.0 in each modification evaluation.

※ 2: The coke deposition amount is a relative value when the value of Comparative Example 1 is 100.0.

1 is a flow chart of evaluation of a steam reforming reformer.

2 is a flow chart of evaluation of a magnetothermal reformer.

Claims (3)

Flash point 40 ° C or more, sulfur content 0.3 mass ppm or less, aromatic content 20% by volume or less, naphthene content 20-50% by volume, initial boiling point range 150-210 ° C, distillation temperature 220-255 ° C, 90 vol%, 13 carbon atoms A hydrocarbon oil for producing hydrogen in a hydrogen production system, characterized in that the peroxide after 10-30 mass%, 43 ° C, and 13 weeks storage test at the same time satisfies 2 mg / kg or less. In a hydrogen production system containing a desulfurizer and a reformer, a hydrogen production system using the hydrocarbon oil according to claim 1 as a hydrocarbon oil for hydrogen production. The catalyst according to claim 2, wherein as a reformer, (1) a hydrocarbon oil heated by vaporization is mixed with water vapor and a catalyst containing an element of Group VIII of the periodic table as an active metal is used, and the reaction temperature is in the range of 400 to 1000 캜. And a steam reforming reformer having a mixing ratio (S / C) of water and hydrocarbon oil of 1 to 5 mol / mol, or (2) heating and vaporizing hydrocarbon oil with steam and air, and the group VIII element of the periodic table as an active metal. It contains a catalyst, the reaction temperature ranges from 400 to 1000 ℃, the mixing ratio (S / C) of water and hydrocarbon oil is 0.5 mol / mol range and the mixing ratio (O ₂ / C) of oxygen and hydrocarbon oil Hydrogen production system, characterized in that using any one of the magnetic heat reforming reformer in the range of 0.1 to 0.5 mol / mol.

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