JP2003073677A - Fuel oil composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fuel oil composition for fuel cells which can efficiently produce hydrogen, does not badly affect a modification catalyst and a fuel cell electrode, and the fuel oil composition for internal combustion engines and for fuel cells which, even when used for automotive internal combustion engines, has a high octane number and can be used without causing knocking. SOLUTION: The fuel oil composition contains 5 vol.% or lower 4C hydrocarbon component, 10-40 vol.% 5C paraffin component, 15 vol.% or lower 5C olefin component, 5 vol.% or lower 5C naphthene component, 10 vol.% or lower aromatic component, and 5 wt.ppm or lower sulfur and has a Reid vapor pressure of 60 kPa or lower. Or the fuel composition contains 5 vol.% or lower 4C hydrocarbon component, 10-30 vol.% 5C paraffin component, 10 vol.% or lower 5C olefin component, 10 vol.% or lower aromatic component, and 5 wt.ppm or lower sulfur and has a Reid vapor pressure of 60 kPa or lower and a research octane number of 66 or higher.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fuel oil composition for producing hydrogen used in a fuel cell, and more specifically, it is composed of petroleum hydrocarbon such as gasoline fraction and can be used as an internal combustion engine. The present invention relates to a fuel oil composition for fuel cells.

[0002]

2. Description of the Related Art Generally, hydrogen is used as a fuel for a fuel cell. As such hydrogen, hydrogen gas used as it is, hydrogen obtained by reforming or decomposing methanol or the like, or It has been proposed to use hydrogen obtained from city gas containing methane as a main component and LPG containing propane as a main component which are gaseous at room temperature and atmospheric pressure. However, when hydrogen gas is used as it is, it is difficult to handle because it is a gas itself, and in the case of methanol, there are problems such as low energy density, high cost, and lack of infrastructure. Yes, city gas and LP
G has problems that its use is limited locally and that it is difficult to handle. Especially, when G is used as a fuel for a fuel cell for transportation such as automobiles, there is a large practical problem. 2. Description of the Related Art In recent years, a fuel cell vehicle using a fuel cell having high energy efficiency and a low environmental load as a power source has been attracting attention, and development of a fuel cell to be used for the fuel cell vehicle is required. On the other hand, gasoline or a petroleum hydrocarbon fraction constituting the same, which has been conventionally used as a fuel for an internal combustion engine of an automobile or the like, has an advantage that it is usually a liquid and has a high energy density. It is thought that it can be effectively used for batteries. The infrastructure for such gasoline fractions is currently well developed.

[0003]

However, the gasoline fraction is not easily reformed as compared with methanol or the like due to coke deterioration of the catalyst or poisoning of the catalyst.
There is also a problem that the life of the reforming catalyst is relatively short. Further, in spite of the above knowledge, it is practically difficult to switch all the internal combustion engine engines conventionally used in automobiles etc. to the fuel cell engine at one time, and in the transition period, the internal combustion engine and the fuel cell It is desirable to use fuel oil that can be shared by both parties. When the fuel oil generally used in the internal combustion engine is used in the fuel cell, the above-mentioned problems occur, while when the fuel oil developed for the fuel cell is used in the internal combustion engine,
Practically unfavorable problems such as knocking occur,
In any case, these simple diversions were difficult. The present invention has been made to solve the above problems.
That is, the present invention provides a fuel oil composition for a fuel cell, which can efficiently produce hydrogen, and which does not adversely affect the reforming catalyst and the fuel cell electrode and causes less deterioration of the reforming catalyst and the like. It is in. Further, an object of the present invention is to provide a fuel oil composition for both internal combustion engine and fuel cell, which has a high octane number even when used as a fuel oil for an internal combustion engine of an automobile and can be effectively used without causing knocking or the like. The purpose is to do.

[0004]

Means for Solving the Problems As a result of earnest research in view of the above problems, the present inventors can achieve the above object of the present invention by using a gasoline fraction having a specific composition and properties as fuel oil. Found. The present invention has been completed based on such findings. That is, the present invention provides (1) a hydrocarbon component having 4 carbon atoms of 5% by volume or less,
Paraffin content of 10 to 40% by volume, C5 olefin content of 15% or less, C5 naphthene content of 5% or less, aromatic content of 10% or less, and sulfur content of 5 ppm by weight or less. A fuel oil composition containing a Reid vapor pressure of 60 kPa or less, and (2) a hydrocarbon component having 4 carbon atoms of 5% by volume or less, a paraffin component having 5 carbon atoms of 10 to 30% by volume, and having 5 carbon atoms. Contains 10% by volume or less of olefins, 5% or less by volume of naphthenes having 5 carbon atoms, 10% by volume or less of aromatics, 5 ppm by weight or less of sulfur, and has a Reid vapor pressure of 60 kPa or less and a research method octane number Is 66
The present invention relates to the above fuel oil composition.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. According to the present invention, hydrocarbons having 4 carbon atoms are 5% by volume or less, paraffins having 5 carbon atoms are 10 to 40% by volume, olefins having 5 carbon atoms are 15% by volume or less, and naphthenes having 5 carbon atoms are 5% by volume. Volume% or less, aromatic content is 10 volume% or less, sulfur content is 5 ppm by weight or less, and Reid vapor pressure is 60.
It relates to a fuel oil composition (fuel oil 1) having a kPa or less.

In the fuel oil 1 of the present invention, examples of the hydrocarbon component having 4 carbon atoms include butane, n-butene, is
Examples thereof include o-butene, and those obtained by a usual method in the field can be appropriately used. Moreover, as the paraffin component having 5 carbon atoms, for example,
Examples of the olefin component having 5 carbon atoms include n-pentane and iso-pentane. For example, 2-methyl-2-
Examples thereof include butene and t-2-pentene, and examples of the naphthene component having 5 carbon atoms include cyclopentane. Furthermore, examples of the aromatic component include benzene, toluene, xylene, ethylbenzene and the like.

In the present invention, if the content of each component is within the above range, the above effects of the present invention can be effectively exhibited. Particularly, the hydrocarbon compound having 4 carbon atoms is 3% by volume.
Hereinafter, it is preferable that the paraffin having 5 carbon atoms is 10 to 35% by volume, the olefin content having 5 carbon atoms is 15% by volume or less, and the naphthene content having 5 carbon atoms is 5% by volume or less. In particular,
It is preferable that the olefin component having 5 carbon atoms is within the above range, because deterioration of the reforming catalyst and partial oxidation catalyst due to sulfur poisoning of the catalyst can be improved. Further, the aromatic content is preferably 10% by volume or less from the viewpoint of being advantageous for the reforming reaction. Further, the sulfur content is 5 ppm by weight or less, further 1 weight pp
m or less, a reforming catalyst due to sulfur poisoning of the catalyst,
It is preferable in that the deterioration of the partial oxidation catalyst can be improved. The fuel oil 1 of the present invention preferably has a Reid vapor pressure of 60 kPa or less, and further 44 to 60 kPa from the viewpoints of reducing evaporative emission, durability of the tank, and suppression of release of hydrocarbons to the atmosphere. .

In the present invention, the hydrocarbon content having 4 carbon atoms is 5% by volume or less, the paraffin content having 5 carbon atoms is 10 to 30% by volume, the olefin content having 5 carbon atoms is 10% by volume or less, and the carbon number is 5%. Of which the naphthene content is 5% by volume or less, the aromatic content is 10% by volume or less, the sulfur content is 5 ppm by weight or less, and the Reed vapor pressure is 60 kPa or less, and the research octane number is 66.
The present invention relates to the above fuel oil composition (fuel oil 2). The fuel oil 2 can be advantageously used not only as fuel oil for fuel cells but also as fuel oil for internal combustion engines because of its high octane number. Regarding the above fuel oil 2, the same hydrocarbon content as C4, paraffin content of C5, olefin content of C5, naphthene content of C5 and aromatic content are the same as those of the fuel oil 1. I can name it.

In the present invention, if the content of each component is within the above range, the effects of the present invention can be effectively exhibited. In particular, hydrocarbons having 4 carbon atoms are 5% by volume or less, paraffin components having 5 carbon atoms are 15 to 25% by volume, olefin components having 5 carbon atoms are 6% by volume or less, and naphthene components having 5 carbon atoms are 2% by volume. The aromatic content is preferably 10% by volume or less. The sulfur content is preferably 5 ppm by weight or less, more preferably 1 ppm by weight or less. In particular, if the hydrocarbon having 4 carbon atoms is within the above range, it is possible to obtain the effect of increasing the vapor pressure when used as a fuel for an internal combustion engine and improving the startability of the engine. Is not too high to cause the vapor lock phenomenon. In addition, it is preferable that the paraffin component having 5 carbon atoms, the olefin component, and the naphthene component are all within the above ranges because the octane number required as the fuel for the internal combustion engine can be maintained. In particular, it is preferable that the paraffin component having 5 carbon atoms is within the above range because knocking and the like can be suppressed when used as a fuel for an internal combustion engine. Further, if the aromatic content is within the above range, it is advantageous for the reforming reaction, and if the sulfur content is within the above range, deterioration of the reforming catalyst and partial oxidation catalyst due to sulfur poisoning of the catalyst may occur. It is preferable because it can be improved.

Further, the fuel oil 2 of the present invention has a Reid vapor pressure of 60 kPa or less, preferably 44 to 60 kPa, so that the amount of vaporized gas can be reduced, and as a result, when used as a fuel for an internal combustion engine, Is preferable in terms of durability of the tank, suppression of release of hydrocarbons to the atmosphere, and the like. The fuel oil 2 of the present invention has a research octane number of 66 or more. Research octane number 6
When it is 6 or more, knocking does not occur when used as a fuel for an internal combustion engine, which is practically advantageous. From this point, the research octane number is 80 or more, and further 89
The above is preferable. From the above points, the fuel oil 2 of the present invention can be used for both internal combustion engines and fuel cells. That is, when used for an internal combustion engine,
It has a high octane number and can be advantageously used without causing knocking, etc. Even when used for fuel cells, hydrogen can be efficiently produced, and it has an adverse effect on the reforming catalyst and fuel cell electrodes. It is possible to reduce deterioration of the reforming catalyst and the like.

Examples of the base material used for preparing the fuel oil of the present invention include desulfurized light naphtha (DLN),
Low vapor pressure DLN, isomerized DLN, low vapor pressure / isomerized DL
N, light cracked gasoline (LFG), desulfurization LFG, desulfurization
Low vapor pressure LFG, desulfurization / hydrogenation LFG, alkylate gasoline (ALG), desulfurization heavy naphtha (DHN) and the like can be used. Here, desulfurization light naphtha (DLN) is composed of C _{4 to} C ₇ normal paraffins, isoparaffins, naphthenes, etc. Normally, crude oil is fractionated as light naphtha by an atmospheric distillation device and desulfurized by a naphtha desulfurization device. Alternatively, the crude naphtha is obtained by fractionating the crude oil as a full-range naphtha in an atmospheric distillation device, desulfurizing it in a naphtha desulfurizing device, and then distilling the light naphtha. The low vapor pressure DLN is obtained by removing a light fraction of DLN with a splitter or the like, and the isomerized DLN is, for example, a platinum-supported alumina-based catalyst, a platinum-supported zeolite catalyst, a platinum-supported strongly acidic carrier. It refers to the one obtained by isomerizing by a method such as passing a desulfurized light naphtha through a platinum catalyst such as a catalyst. What is low vapor pressure / isomerized DLN?
It is obtained by performing both the low vapor pressure treatment and the isomerization treatment.

Alkylate gasoline (ALG) generally means an alkylated gasoline obtained by an alkylation reaction, and is rich in isoparaffin having a high octane number and does not contain an aromatic component or an olefinic fraction. Further, desulfurized heavy naphtha (DHN) means a petroleum hydrocarbon fraction composed of C _{6 to} C ₁₀ normal paraffins, isoparaffins, naphthenes, etc. Usually, crude oil is converted into heavy naphtha by an atmospheric distillation apparatus. It is obtained by fractional distillation and desulfurization by a naphtha desulfurization apparatus, or by fractionating crude oil as a full range naphtha by an atmospheric distillation apparatus, desulfurizing by a naphtha desulfurization apparatus, and then distilling heavy naphtha. Further, light cracked gasoline (LFG) is a light fraction of catalytically cracked gasoline obtained by cracking with a solid acid catalyst by a conventionally known catalytic cracking method, particularly a fluid catalytic cracking method. As this LFG, a desulfurized product (desulfurized LFG) may be used if necessary. Desulfurization LFG
Is obtained by passing LFG through an adsorbing desulfurizing agent such as Ni-based. Desulfurization / low vapor pressure LFG means desulfurization L
The light portion of FG is obtained by removing the light portion with a splitter or the like. Desulfurization / hydrogenation LFG is obtained by passing LFG through a Co-Mo / alumina, Ni-Mo / alumina catalyst or the like. Say something.

The fuel oil composition of the present invention can be prepared by appropriately combining the above base materials.
Isomerized DLN 30-60% by volume, DHN 30-60
It can be obtained by a method such as mixing volume% and ALG. The fuel oil 2 can be obtained by, for example, mixing low vapor pressure / isomerized DLN in an amount of 30 to 70% by volume, DHN in an amount of 30 to 40% by volume, and ALG. The fuel oil of the present invention is suitable for the production of hydrogen for fuel cells, since it has characteristics such as high purity of hydrogen produced thereby and a small decrease in hydrogen partial pressure. In order to generate hydrogen from the fuel oil, the fuel oil is first desulfurized as needed. As the desulfurization method, an adsorption desulfurization method or a hydrodesulfurization method is usually used. The adsorptive desulfurization method uses an adsorbent containing Ni as a main component, and is at room temperature to 200 ° C. and normal pressure to 5 M.
It is carried out under the condition of Pa. The hydrodesulfurization method uses Co-Mo /
Using a hydrodesulfurization catalyst such as alumina or Ni-Mo / alumina and a hydrogen sulfide adsorbent such as ZnO, at atmospheric pressure to 5
It is performed under a pressure of MPa and a temperature of 200 to 400 ° C.
Then desulfurized fuel oil is steam reformed, partially oxidized and / or
Alternatively, perform auto thermal reforming (ATR).
According to the present invention, it is possible to obtain a fuel oil capable of efficiently producing hydrogen without carbon deposition on a steam reforming catalyst or the like.

The steam reforming method is not particularly limited,
Usually, the following method is used. First, the steam reforming catalyst used in this hydrogen production method is not particularly limited, but Ni, zirconium or ruthenium (Ru), rhodium (Rh), platinum (Pt) can be used as the supported metal.
Those using precious metals such as. These supported metals may be used alone or in combination of two or more. Among the above-mentioned supported metals, Ru is particularly desirable and has a great effect of suppressing carbon precipitation during the steam reforming reaction. The supported amount of Ru is 0.05 to 20 based on the carrier.
%, And more preferably 0.05 to 15% by weight.
If the supported amount is less than 0.05% by weight, the activity of the steam reforming reaction may be extremely lowered, and if it exceeds 20% by weight, it is difficult to obtain a significant increase in the activity.

Further, as a specific example of the combination of the supported metals, there may be mentioned one in which Ru and zirconium are supported. Ru and zirconium may be loaded simultaneously or separately. The content of zirconium is 0.5 to 20% by weight based on the carrier, converted to ZrO ₂ , and further,
0.5 to 15% by weight is preferable. In the case of this type of supported metal, those to which cobalt and / or magnesium are further added are preferable. Here, the content of cobalt is an atomic ratio of cobalt / ruthenium of 0.
01 to 30, more preferably 0.1 to 30, and the content of magnesium is 0.1 in terms of magnesia (MgO).
5 to 20% by weight, more preferably 0.5 to 15% by weight are suitable. On the other hand, an inorganic oxide is used as a carrier of a catalyst used for steam reforming, and specific examples thereof include alumina, silica, zirconia, magnesia and a mixture thereof. Of these, alumina and zirconia are particularly preferable.

One of the preferable embodiments of the steam reforming catalyst is a catalyst in which Ru is supported on zirconia. This zirconia may be a simple substance of zirconia (ZrO ₂ ) or a stabilized zirconia containing a stabilizing component such as magnesia. As the stabilized zirconia, those containing magnesia, yttria, ceria and the like are preferable. As another preferred embodiment of the steam reforming catalyst, R is
Examples of the catalyst include u and zirconium, or Ru and zirconium, and further cobalt and / or magnesium supported on an alumina carrier. As alumina, α-alumina, which is particularly excellent in heat resistance and mechanical strength, is preferable. Next, in the production of hydrogen, steam reforming is performed in a state where the ratio S / C (molar ratio) of steam (S) and carbon (C) derived from fuel oil is 2 to 5, and further 2 to 4. The method of carrying out is preferred. If steam reforming is performed in a state where the S / C (molar ratio) is high of 5 or more, excess steam needs to be produced, heat loss is large, and the efficiency of hydrogen production may decrease. If the S / C is less than 2, the amount of hydrogen generated may decrease.

Further, in the production of hydrogen, a method of carrying out steam reforming while maintaining the inlet temperature of the steam reforming catalyst layer at 630 ° C. or lower is preferable. Since the steam reforming catalyst layer inlet temperature tends to increase due to the addition of oxygen, it is necessary to control this. When the inlet temperature exceeds 630 ° C,
This is because the thermal decomposition of the raw material hydrocarbon is promoted and carbon may be deposited on the catalyst or the wall of the reaction tube via the generated radicals to make operation difficult. The catalyst layer outlet temperature is
Although not particularly limited, it is preferably carried out at 650 to 800 ° C. If the catalyst layer outlet temperature is lower than 650 ° C, the amount of hydrogen produced is not sufficient, and in order to react at a temperature higher than 800 ° C, the reactor may need to be made of a particularly heat resistant material.
This is because it is not preferable in terms of economy. In the production of hydrogen, the reaction pressure is normal pressure to 3 MPa, and further normal pressure to 1
It is preferably MPa. The flow rate of fuel oil is 0.1 to 100 h ⁻¹ in LHSV.

The partial oxidation reaction is preferably carried out under a catalyst in which a noble metal such as ruthenium or nickel is supported on a heat-resistant oxide, the reaction pressure is atmospheric pressure to 5 MPa, and the reaction temperature is 400 to 1
100 ° C., oxygen / carbon ratio 0.2 to 0.8, LHSV0.
It is carried out for ¹ to 100 h ^-1 . In the production method of the hydrogen, since the CO obtained by the steam reforming adversely affect the hydrogen generation, C this as CO ₂ by reaction
It is preferable to remove O. The autothermal reaction is a method that combines partial oxidation and steam reforming. The catalyst is
A catalyst in which a noble metal such as ruthenium or nickel is supported on a heat resistant oxide is used. It may be carried out with one kind of catalyst, but partial oxidation and steam reforming may be combined with different catalysts. The reaction pressure is atmospheric pressure to 5 MPa, the reaction temperature is 400 to 1100 ° C., the oxygen / carbon ratio is 0.4 to 0.6, the sulfur / carbon ratio is 0.5 to 2.0, and the LHSV is 0.1 to 100.
done at h ^-1 .

[0019]

EXAMPLES Next, the present invention will be described more specifically by way of examples, but the present invention is not limited to these examples. Examples 1 to 18 and Comparative Examples 1 to 3 Base materials having the compositions and properties shown in Table 1 were used in the blending ratios shown in Table 2 to prepare fuel oils having the compositions and properties shown in Table 3, The research octane number and the Reid vapor pressure, etc. of each are specified in JIS K2280 and JIS K
2258 and the like.

Hydrogen Production Experiment Two fixed bed flow reactors were connected, desulfurization was performed in the first stage and steam reforming was performed in the second stage under the following conditions. (1st stage) Desulfurization Desulfurization agent: Ni-based adsorbent (containing Ni: 60 wt%) Conditions: Normal pressure, temperature 90 ° C., LHSV = 0.1 h ⁻¹ (2nd stage) Reforming catalyst: α-alumina powder Add 20% by weight of water,
Mixing and compression molding were performed with a kneader to obtain a cylindrical molded body having a diameter of 5 mm and a length of 5 mm. 128 after drying at 200 ℃ for 3 hours
It was calcined at 0 ° C. for 26 hours to obtain an alumina carrier. On the other hand, an aqueous solution of zirconium oxychloride (ZrO (OH) Cl) (2.5 g in terms of ZrO ₂ ) contains ruthenium trichloride (R
uCl ₃ / nH ₂ O) (Ru 38% content) 0.66 g,
Cobalt nitrate _{(Co (NO 3) 2 ·} 36H 2 O) 2.4
7g and magnesium nitrate _{(Mg (NO 3) 2 ·} 26H
₂ O) 6.36 g was added and stirred until dissolved. The total amount of solution was 10 cc. After impregnating 50 g of the above alumina carrier with this solution (Pore filling method), 120 ° C.
For 5 hours, calcination at 500 ° C for 2 hours, and then 16-
The particle size was adjusted to 32 mesh. This catalyst contains 0.5 wt% of Ru based on the carrier, 5 wt% of Zr in terms of zirconia, 1.0 wt% of Co, and 2 wt% of Mg in terms of magnesia. ATR conditions: steam / carbon ratio 1.2, oxygen / carbon ratio 0.
5, LHSV = 2.5 h ⁻¹ , normal pressure, reaction temperature 750 ° C. After the above reaction was continuously carried out for 100 hours, the second stage catalyst was taken out, and the carbon deposition rate on the catalyst was measured as follows. evaluated. Carbon deposition rate (%) = length of carbon deposited portion / total catalyst length ○: 5% or less ×: 20% or more

[0021]

[Table 1]

[0022]

[Table 2]

[0023]

[Table 3]

[0024]

[Table 4]

[0025]

[Table 5]

[0026]

[Table 6] * RON: Research method octane number * MON: Motor method octane number

[0027]

As described above in detail, according to the present invention, hydrogen can be efficiently produced, and the reforming catalyst,
Provided is a fuel oil composition for a fuel cell that does not deteriorate the reforming catalyst or the like without adversely affecting the fuel cell electrode, and has a high octane number when used as a fuel oil for an internal combustion engine of an automobile, It is possible to provide a fuel oil composition for internal combustion engines and fuel cells, which can be used without causing knocking or the like.

Claims (6)

[Claims] 1. A hydrocarbon content having 4 carbon atoms is 5% by volume or less,
10-40% by volume of paraffin having 5 carbon atoms, 5 carbon atoms
Containing 15% by volume or less of olefins, 5% by volume or less of naphthenes having 5 carbon atoms, 10% by volume or less of aromatics, and 5 ppm by weight or less of sulfur, and having a reed vapor pressure of 60 kP.
Fuel oil composition which is a or less. 2. The fuel oil composition according to claim 1, which is used for a fuel cell. 3. The hydrocarbon component having 4 carbon atoms is 5% by volume or less,
10 to 30% by volume of paraffins having 5 carbon atoms, 5 carbon atoms
Containing 10% by volume or less of olefins, 5% by volume or less of naphthenes having 5 carbon atoms, 10% by volume or less of aromatics, and 5 ppm by weight or less of sulfur, and having a reed vapor pressure of 60 kP.
A fuel oil composition having an a or less of a and a research octane number of 66 or more. 4. The fuel oil composition according to claim 3, which has a research octane number of 80 or more. 5. The fuel oil composition according to claim 3, which has a research octane number of 89 or more. 6. The fuel oil composition according to claim 3, which is used for both an internal combustion engine and a fuel cell.