U.S. patent application number 10/221786 was filed with the patent office on 2003-08-07 for fuel oil for use both in internal combustion in engine and fuel cell.
Invention is credited to Akimoto, Takashi, Hirano, Hiroshi, IIzuka, Masashi.
Application Number | 20030145514 10/221786 |
Document ID | / |
Family ID | 18598307 |
Filed Date | 2003-08-07 |
United States Patent
Application |
20030145514 |
Kind Code |
A1 |
Akimoto, Takashi ; et
al. |
August 7, 2003 |
Fuel oil for use both in internal combustion in engine and fuel
cell
Abstract
A fuel oil for use both in an internal combustion engine and in
a fuel cell containing 50% by volume or more of an alkylate
gasoline, and, optionally, 1 to 50% by volume of isopentane, 1 to
12% by volume of a hydrocarbon having 4 carbon atoms, 7% by volume
or less of an oxygen-containing compound, and 1 to 30% by volume of
a desulfurized light naphtha; and a fuel oil for use both in an
internal combustion engine and in a fuel cell containing 10 to 60%
by volume of a desulfurized light naphtha, 40 to 90% by volume of a
benzene-free reformed gasoline and 0 to 10% by volume of a
hydrocarbon having 4 carbon atoms. Each of the above fuel oils is a
fuel oil for a fuel cell which can produce hydrogen with good
efficiency, has no adverse effect on reforming catalysts and
electrodes for a fuel cell, and is reduced in deactivation of
reforming catalysts and the like, and a fuel oil for an internal
combustion engine which has a high octane number and can be used
without causing knocking or the like.
Inventors: |
Akimoto, Takashi; (Chiba,
JP) ; IIzuka, Masashi; (Chiba, JP) ; Hirano,
Hiroshi; (Chiba, JP) |
Correspondence
Address: |
OBLON, SPIVAK, MCCLELLAND, MAIER & NEUSTADT, P.C.
1940 DUKE STREET
ALEXANDRIA
VA
22314
US
|
Family ID: |
18598307 |
Appl. No.: |
10/221786 |
Filed: |
September 17, 2002 |
PCT Filed: |
March 23, 2001 |
PCT NO: |
PCT/JP01/02331 |
Current U.S.
Class: |
44/447 ;
44/449 |
Current CPC
Class: |
H01M 8/0612 20130101;
Y02E 60/50 20130101; C10L 1/02 20130101; C10L 1/06 20130101; C10L
1/023 20130101 |
Class at
Publication: |
44/447 ;
44/449 |
International
Class: |
C10L 001/18 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 23, 2000 |
JP |
2000-81357 |
Claims
1. A fuel oil for use both in an internal combustion engine and in
a fuel cell containing 50% by volume or more of an alkylate
gasoline.
2. The fuel oil according to claim 1 further containing 1 to 50% by
volume of isopentane.
3. The fuel oil according to claim 1 further containing 1 to 12% by
volume of a hydrocarbon compound having 4 carbon atoms.
4. The fuel oil according to claim 2 further containing 1 to 12% by
volume of a hydrocarbon compound having 4 carbon atoms.
5. The fuel oil according to claim 1 containing 50% by volume or
more of the alkylate gasoline, 1 to 50% by volume of isopentane, 1
to 10% by volume of a hydrocarbon compound having 4 carbon atoms
and 7% by volume or less of an oxygen-containing compound.
6. The fuel oil according to any of claims 1 to 5, further
containing 1 to 30% by volume of a desulfurized light naphtha.
7. The fuel oil according to claim 5 wherein the oxygen-containing
compound is at least one selected from methyl tertiary butyl ether,
ethyl tertiary butyl ether and tertiary amyl methyl ether.
8. The fuel oil according to claim 1 having a research octane
number of 89 or more and a vapor pressure of 44 to 93 kPa.
9. A fuel oil for use both in an internal combustion engine and in
a fuel cell containing 10 to 60% by volume of a desulfurized light
naphtha and 40 to 90% by volume of a benzene-free reformed
gasoline.
10. The fuel oil according to claim 9 further containing 10% by
volume or less of a hydrocarbon compound having 4 carbon atoms.
11. The fuel oil according to claim 9 having a research octane
number of 89 or more and a vapor pressure of 44 to 93 kPa.
Description
TECHNICAL FIELD
[0001] This invention relates to a fuel oil usable both in an
internal combustion engine and in a fuel cell, and, in more detail,
relates to a fuel oil which comprises petroleum hydrocarbon
fractions such as a gasoline fraction and is usable both in an
internal combustion engine and in a fuel cell.
[0002] BACKGROUND ART
[0003] Fuel for a fuel cell is generally hydrogen, and it is
proposed to use, as the hydrogen, hydrogen gas itself, hydrogen
obtained by reforming or decomposing methanol or the like, hydrogen
obtained from a town gas containing as a main component methane
being gaseous at ordinary temperature and at ordinary pressure, or
from an LPG or the like containing propane as a main component, or
hydrogen from other sources.
[0004] However, when hydrogen gas is used as such, handling of the
gas is hard since it is itself a gas. Methanol has problems that
its energy density is low, it is expensive, supply equipment is not
provided, etc. Town gas and LPG have problems that their use is
regionally limited, it is hard to handle them, etc., and especially
when they are used as a fuel for a fuel cell for transportation
such as automobiles, there is practically a big problem.
[0005] In recent years, fuel cell powered vehicles equipped as a
power source with a fuel cell having high energy efficiency and
being low in loads on environment have gotten to draw attention,
and development of a fuel cell to be used therein is desired. On
the other hand, gasoline which has hitherto been used as a fuel for
an internal combustion engine in automobiles, etc. and petroleum
hydrocarbon fractions composing gasoline have advantages that they
are usually liquid, have a high energy density, etc., and they are
considered to be effectively utilizable in a fuel cell. Further, as
to such gasoline fractions, their supply system, etc. is
sufficiently provided.
DISCLOSURE OF INVENTION
[0006] However, despite the above findings, it is practically hard
to change all of an internal combustion engine having hitherto been
used in automobiles, etc. to a fuel cell engine all at once, and at
the transitional period, it is desired to use a fuel oil usable
both in an internal combustion engine and in a fuel cell. There are
also problems that in comparison with methanol, etc., gasoline
fractions are not easy to reform due to deactivation of the
reforming catalyst with coke or poisoning of the catalyst, and the
life of the catalyst is comparatively short. Thus, if a fuel oil
generally used in an internal combustion engine is used as such in
a fuel cell, problems as mentioned above arise, and on the other
hand, if a fuel oil developed for a fuel cell is used in an
internal combustion engine, problems of knocking, etc. arise, and
in either case, simple diversion thereof was difficult.
[0007] The invention was made for solving the above problems.
Namely, the invention aim is to provide a fuel oil usable for both
an internal combustion engine and a fuel cell which can efficiently
produce hydrogen, has no adverse effect on a reforming catalyst and
the electrodes of the fuel cell and less causes deactivation of a
reforming catalyst when the fuel oil is used as a fuel oil for the
fuel cell, and it has a high octane number and can effectively be
used without causing knocking, etc. when it is used as a fuel oil
for an internal combustion engine of an automobile.
[0008] The present inventors have intensely studied for solving the
above problems, and as a result, they found that the above aim
could be achieved by using a gasoline fraction of particular
composition and properties as a fuel oil. The invention was
completed based on the finding. Namely, the invention relates
to
[0009] (1) A fuel oil for usable both in an internal combustion
engine and in a fuel cell containing 50% by volume or more of an
alkylate gasoline (Fuel oil 1), and
[0010] (2) A fuel oil for usable both in an internal combustion
engine and in a fuel cell containing 10 to 60% by volume of a
desulfurized light naphtha and 40 to 90% by volume of a
benzene-free reformed gasoline (Fuel oil 2).
BEST MODE FOR CARRYING OUT THE INVENTION
[0011] The invention is in more detail described below.
[0012] The invention relates, first, to a fuel oil for usable both
in an internal combustion engine and in a fuel cell containing 50%
by volume or more of an alkylate gasoline (Fuel oil 1). The
alkylate gasoline means alkylated gasoline obtained by alkylation
reaction, rich in isoparaffin having a high octane number and not
containing aromatic components and olefin fractions.
[0013] In the invention alkylate gasoline having an octane number
of 90 to 100, preferably of about 96 is used. Such alkylate
gasoline can be obtained by introducing an alkyl group into
hydrocarbon fractions such as isoparaffin and aromatic fractions,
and as a catalyst used then, there can be mentioned an acid
catalyst such as sulfuric acid or hydrofluoric acid, a solid acid
catalyst such as synthetic zeolite or solid phosphoric acid,
etc.
[0014] Fuel oil 1 of the invention contains the alkylate gasoline
in an amount of 50% by volume or more, preferably 50 to 95% by
volume, more preferably 50 to 90% by volume, particularly
preferably 50 to 80% by volume. When the content of the alkylate
gasoline is less than 50% by volume, the octane number is low and
knocking sometimes takes place when used as a fuel for an internal
combustion engine. When the content is more than 95% by volume,
there is a possibility that startability gets poor when used as a
fuel for an internal combustion engine.
[0015] Fuel oil 1 of the invention preferably contains, in addition
to the alkylate gasoline, isopentane in an amount of 1 to 50% by
volume. When the content of isopentane is less than 1% by volume,
the effect by the addition is sometimes not exerted. When it is
more than 50% by volume, in use as a fuel for an internal
combustion engine, there sometimes arises a case where knocking is
caused due to lowering of the octane number or a case where a vapor
lock phenomenon is caused due to too high vapor pressure. Such
isopentane can be separated by distilling a hydrocarbon oil at
ordinary pressure, and in the invention, isopentane having an
octane number of 85 to 95, preferably of about 90, and having a
vapor pressure of 130 to 170 kPa, preferably of about 150 kPa is
preferably used.
[0016] Fuel oil 1 of the invention preferably further contains a
hydrocarbon compound having 4 carbon atoms in an amount of 1 to 12%
by volume. As the hydrocarbon compound having 4 carbon atoms, there
can be mentioned butane, n-butene, isobutene, etc., and as them
ones obtained according to a process conventional in the field can
appropriately be used. When the content of the hydrocarbon compound
is less than 1% by volume, the effect by the addition is sometimes
not exerted, and when the content is more than 12% by volume, there
sometimes arises a case where a vapor lock phenomenon is caused due
to too high vapor pressure, when the fuel oil is used as a fuel for
an internal combustion engine.
[0017] Fuel oil 1 of the invention preferably further contains an
oxygen-containing compound in an amount of 7% by volume or less. As
the oxygen-containing compound, MTBE (methyl t-butyl ether), ETBE
(ethyl t-butyl ether), TAME (t-amyl methyl ether), etc. can
preferably be mentioned from the viewpoint of their handling,
prices, etc.
[0018] In the invention, by adding the oxygen-containing compound,
effects that the octane number is heightened and the reforming
reaction gets to progress easily can be obtained. When the content
is more than 7% by volume, in use as a fuel for an internal
combustion engine, there sometimes arises a case where the fuel oil
has adverse effects on a three-way catalyst for cleaning the
exhaust gas and NOx in the exhaust gas is increased. From this
standpoint, it is preferred that Fuel oil 1 of the invention
contains the oxygen-containing compound in an amount of 1 to 7% by
volume.
[0019] Fuel oil 1 of the invention preferably further contains
desulfurized light naphtha in an amount of 1 to 30% by volume. The
desulfurized light naphtha means light naphtha composed of normal
paraffin, isoparaffin, naphthene, etc. having 4 to 7 carbon atoms
and usually obtained by fractionally distilling crude oil into
light naphtha in an atmospheric distillation plant and
desulfurizing the light naphtha in a naphtha-desulfurizing
apparatus, or by fractionally distilling crude oil into full range
naphtha in an atmospheric distillation plant, desulfurizing the
full range naphtha in a naphtha-desulfurizing apparatus and
fractionally distilling it into light naphtha. When the content of
the desulfurized light naphtha is less than 1% by volume, the
effect of the addition is sometimes not exerted, and when the
content is more than 30% by volume, the octane number gets low and
knocking sometimes occurs in use as a fuel for an internal
combustion engine.
[0020] The sulfur content of the desulfurized light naphtha is
usually 5 ppm by weight or less, preferably 1 ppm by weight or
less, more preferably 0.1 ppm by weight or less.
[0021] In the invention, it is preferred to use, as the
desulfurized light naphtha, an isomerized desulfurized light
naphtha having a ratio of isoparaffin to normal paraffin of 1 or
more, preferably 1.5 or more, more preferably 2.5 or more. As such
isomerized desulfurized light naphtha, one obtained by isomerizing
a desulfurized light naphtha according to a process usually used in
the art, for example according to a process of passing a
desulfurized light naphtha through a platinum catalyst such as a
platinum carried on alumina catalyst, a platinum carried on zeolite
catalyst or a platinum carried on a strongly acidic carrier
catalyst, can be used.
[0022] As a fuel oil used for both an internal combustion engine
and a fuel cell in the invention, there can be mentioned, apart
from the above Fuel oil 1, Fuel oil 2 containing 10 to 60% by
volume of a desulfurized light naphtha and 40 to 90% by volume of a
benzene-free reformed gasoline, and, optionally, 10% by volume or
less of a hydrocarbon compound having 4 carbon atoms.
[0023] As to the desulfurized light naphtha and the hydrocarbon
compound having 4 carbon atoms, the same desulfurized light naphtha
and the hydrocarbon compound having 4 as used in Fuel oil 1 are
used. As to the contents, when the content of the desulfurized
light naphtha in Fuel oil 2 is less than 10% by volume, there
sometimes arises a case where the content of aromatic compounds is
increased and, in use as a fuel for a fuel cell, the reforming
reaction gets disadvantageous. When the content is more than 60% by
volume, there sometimes arises a case where the octane number
becomes low and, in use as a fuel for an internal combustion
engine, knocking occurs. By adding the hydrocarbon compound having
4 carbon atoms, in use as a fuel for an internal combustion engine,
the effects that the vapor pressure is increased and the
startability is heightened can be obtained. When the content is
more than 10% by volume, there sometimes arises a case where a
vapor lock phenomenon occurs due to too high vapor pressure.
[0024] The above Fuel oil 2 contains 40 to 90% by volume of the
benzene-free reformed gasoline. The reformed gasoline means a
gasoline obtained by thermally reforming or catalytically reforming
a direct distillation gasoline generally having a low octane
number, and in the invention, one having an octane number of 95 to
100 is preferably used. As a catalyst used in the catalytic
reforming, there can, for example, be mentioned a platinum
catalyst, etc. The benzene-free reformed gasoline means a gasoline
obtained by removing benzene from the reformed gasoline through
distillation or the like.
[0025] As processes for producing the benzene-free reformed
gasoline, various processes can be mentioned, but the following one
is preferred.
[0026] (1) In the first fractionating tower, from the top part, a
low-boiling fraction containing saturated hydrocarbons having 5
carbon atoms as a main component is separated from the reformed
gasoline (top temperature 73 to 83.degree. C., top pressure 3 to 4
kg/cm.sup.2 G).
[0027] (2) The fraction withdrawn from the bottom part of the first
fractionating tower is introduced into the second fractionating
tower, and from the top part a medium-boiling fraction containing
benzene and saturated hydrocarbons having 6 and 7 carbon atoms of a
low octane number as main components is withdrawn, and at the same
time, from the bottom part a high-boiling fraction containing
aromatic hydrocarbons having 7 to 10 carbon atoms of a high octane
number as main components is withdrawn (top temperature 95 to
105.degree. C., top pressure 1.3 to 2.3 kg/cm.sup.2 G).
[0028] (3) The above low-boiling fraction and high-boiling fraction
are mixed to give a benzene-free reformed gasoline.
[0029] According to this process, it is, usually, possible to
reduce the content of benzene in the reformed gasoline being 4 to
10% by volume up to 0 to 0.5% by volume, which is advantageous for
the reforming reaction, and in addition, since the fraction having
a low octane number is removed together with benzene as the
medium-boiling fraction, it is possible to heighten the octane
number, which is desirable in use for an internal combustion
engine.
[0030] As further processes for reducing the amount of benzene in
the reformed gasoline, there can, for example, be mentioned (1)
modification of operating condition of the catalytic reforming
apparatus, (2) a process of removing the C.sub.6 fraction in
desulfurized heavy naphtha as a raw material by distillation, (3) a
process of removing the benzene fraction from the reformed gasoline
by distillation, (4) a process of hydrogenating the benzene
fraction in the reformed gasoline, by a catalytic reaction, to
convert it to cyclohexane, etc. and then introducing them into an
isomerizing apparatus where they are isomerized into isomers having
a high octane number, (5) a process of alkylating the benzene
fraction in the reformed gasoline, by a catalytic reaction, to
convert it to alkylated aromatic compounds having a high octane
number, and (6) a process of alkylating the benzene fraction
removed and separated by the above process (2) with an off-gas from
a FCC (fluidized catalytic cracker) containing a large amount of
ethylene, etc to convert the benzene fraction to alkylated aromatic
compounds having a high octane number, etc.
[0031] When the content of the reformed gasoline in Fuel oil 2 is
less than 40% by volume, the octane number is lowered and knocking
sometimes takes place in use as a fuel for an internal combustion
engine, and when the content is more than 90% by volume, the
content of aromatic compounds increases, and the reforming reaction
sometimes become disadvantageous in use as a fuel for a fuel
cell.
[0032] It is preferred that any of Fuel oils 1 and 2 for use both
in an internal combustion engine and in a fuel cell of the
invention has a research octane number of 89 or more. When the
research octane number is less than 89, knocking sometimes occurs
in use as a fuel for an internal combustion engine.
[0033] It is also preferred that any of Fuel oils 1 and 2 for use
both in an internal combustion engine and in a fuel cell of the
invention has a vapor pressure of 44 to 93 kPa. When the vapor
pressure is less than 44 kPa, the startability of the engine
sometimes gets poor in use as a fuel for an internal combustion
engine, and when it is more than 93 kPa, a vapor lock phenomenon
sometimes takes place due to too high vapor pressure.
[0034] The fuel oil of the invention can be used both in an
internal combustion engine and in a fuel cell. Namely, when used in
an internal combustion engine, the fuel oil has a high octane
number and can be used effectively without causing knocking, and
when it is used in a fuel cell, it can produce hydrogen
efficiently, and has no adverse effect on the reforming catalyst
and the electrodes of the fuel cell and thus deactivation of the
reforming catalyst, etc. can be reduced.
[0035] Particularly, the fuel oil of the invention has
characteristics that the purity of hydrogen produced therefrom is
high, lowering of the partial pressure of hydrogen is small, etc.,
and is, therefore, suitable for production of hydrogen for a fuel
cell.
[0036] For producing hydrogen from the fuel oil, the fuel oil is
first desulfurized according to necessity. As the desulfurization
method, a hydrodesulfurization method is usually used. The
hydrodesulfurization is carried out under a pressure of from
ordinary pressure to 5 MPa at a temperature of 200 to 400.degree.
C. using a hydrodesulfurizing catalyst such as Co--Mo/alumina or
Ni--Mo/alumina and an adsorbent of hydrogen sulfide such as ZnO.
Then, the desulfurized fuel oil is subjected to steam reforming
and/or partial oxidation. According to the invention, a fuel oil
free of carbon deposition on the steam reforming catalyst, etc. and
capable of efficiently producing hydrogen can be obtained.
[0037] There is no particular limitation about the process of steam
reforming, but, usually, the steam reforming is usually carried out
as follows.
[0038] First, on a steam reforming catalyst to be used, there is no
particular limitation, but as the metal to be carried, there can be
mentioned Ni, zirconium or a noble metal such as ruthenium (Ru),
rhodium (Rh) and platinum (Pt). These metals to be carried can be
used alone or in a combination of two or more.
[0039] Among the above metals to be carried, Ru is particularly
desirable, and Ru has a large effect in inhibition of carbon
deposition during the steam reforming reaction. The amount of Ru to
be carried is preferably 0.05 to 20% by weight, more preferably
0.05 to 15% by weight, based on the weight of the carrier. When the
amount is less than 0.05% by weight, the activity of the steam
reforming reaction is sometimes extremely lowered, and when the
amount is more than 20% by weight, remarkable increase of the
activity is hard to obtain.
[0040] As a specific example of combination of metals to be
carried, a combination of Ru and zirconium can be mentioned. Ru and
zirconium can be carried together or separately on a carrier. The
amount of zirconium to be carried is preferably 0.5 to 20% by
weight, more preferably 0.5 to 15% by weight, in terms of
ZrO.sub.2, based on the weight of the carrier. In the case of this
combination of metals to be carried, it is preferred to further add
cobalt and/or magnesium. The amount of cobalt to be added is
preferably 0.01 to 30, more preferably 0.1 to 30, as an atomic
ratio of cobalt/ruthenium, and the amount of magnesium to be added
is preferably 0.5 to 20% by weight, more preferably 0.5 to 15% by
weight, in terms of magnesia (MgO).
[0041] On the other hand, as the carrier of the catalyst used in
the steam reforming, an inorganic oxide is used, and there can,
specifically, be mentioned alumina, silica, zirconia and magnesia
and a mixture thereof. Particularly preferred among them are
alumina and zirconia.
[0042] As a preferred embodiment of the steam reforming catalyst,
there can be mentioned a catalyst comprising zirconia having
carried Ru thereon. This zirconia can be zirconia itself
(ZrO.sub.2) or a stabilized zirconia containing a stabilizing
component such as magnesia. As the stabilized zirconia, ones
containing magnesia, yttria, ceria or the like are suitable.
[0043] As another preferred embodiment of the steam reforming
catalyst, there can be mentioned a catalyst comprising an alumina
carrier having carried Ru and zirconium thereon, or Ru, zirconium
and further cobalt and/or magnesium thereon. As the alumina,
.alpha.-alumina particularly excellent in heat resistance and
mechanical strength is preferred.
[0044] In the production of hydrogen, it is preferred to carry out
the steam reforming in such a condition that the S/C (mole ratio),
which is a ratio of steam (S) to carbon (C) derived from the fuel
oil, is 2 to 5, particularly 2 to 4. When the steam reforming is
carried out at such a condition the S/C (mole ratio) is as high as
more than 5, heat loss is large since there arises a need to
produce excess steam, and the efficiency of hydrogen production is
sometimes lowered. When S/C is less than 2, the amount of hydrogen
produced is sometimes lowered.
[0045] In the production of hydrogen, it is preferred to carry out
the steam reforming in the condition of maintaining the temperature
of the inlet of the steam reforming catalyst layer at 630.degree.
C. or less.
[0046] Since the temperature of the inlet of the steam reforming
catalyst layer tends to rise due to the addition of oxygen, it is
necessary to control the temperature. When the inlet temperature is
more than 630.degree. C., there can be a case where thermal
decomposition of the raw material hydrocarbon is accelerated, and
carbon via radicals formed is deposited on the catalyst or the wall
of reactor tubes to make the running hard.
[0047] The temperature of the outlet of the catalyst layer is not
particularly limited, but preferably 650 to 800.degree. C. When the
temperature of the outlet of the catalyst layer is less than
650.degree. C., the amount of hydrogen produced is not sufficient,
and for carrying out the reaction at a temperature more than
800.degree. C., the reactor sometimes needs to be made of highly
heat resistant materials, which is not desirable in view of
economical efficiency.
[0048] In the production of hydrogen, the reaction pressure is
preferably from ordinary pressure to 3 MPa, more preferably from
ordinary pressure to 1 MPa. The flow rate of the fuel oil is
preferably 0.1 to 100 h.sup.-1 in terms of LHSV.
[0049] As to the production of hydrogen, also when the fuel oil is
used in such a case where hydrogen is produced in a combination of
the steam reforming and partial oxidation, hydrogen can be produced
efficiently.
[0050] The partial oxidation is carried out at a reaction pressure
of from ordinary pressure to 5 MPa, a reaction temperature of 400
to 1,100.degree. C., an oxygen/carbon ratio of 0.2 to 0.8 and an
LHSV of 0.1 to 100 h.sup.-1 using a catalyst comprising a heat
resistant oxide having carried a noble metal such as preferably
ruthenium, nickel or the like thereon. When steam is added, a S/C
ratio of 0.4 to 4 is adopted.
[0051] In the above process of production of hydrogen, since CO
obtained by the steam reforming adversely influences the hydrogen
formation, it is preferred to remove the CO by a reaction to
convert it to CO.sub.2.
[0052] As described above in detail, according to the invention,
there can be provided a fuel oil for use both in an internal
combustion engine and in a fuel cell, which can produce hydrogen
with good efficiency, has no adverse effect on a reforming catalyst
and electrodes for a fuel cell, and is reduced in deactivation of
the reforming catalyst, etc., and which has a high octane number
and can be used without causing knocking, etc when it is also used
as a fuel oil for an internal combustion engine.
[0053] The invention is further specifically described by examples,
but the invention is not limited at all by these examples.
EXAMPLES 1 to 9 AND COMPARATIVE EXAMPLES 1 to 3
[0054] Fuel oils having compositions and properties shown in Table
1 were prepared, and the research octane number and vapor pressure
of each of them were measured according to JIS K2280 and JIS K2258,
respectively. An experiment of production of hydrogen as shown
below was carried out using each of them, and a coking test of the
catalysts after the reaction is carried. The results are shown in
Table 1.
[0055] Experiment of Production of Hydrogen
[0056] Two fixed bed flow-type reactors were connected, and
desulfurization was carried out in the first reactor and steam
reforming was carried out in the second reactor, under the
following conditions, respectively.
[0057] (First Reactor)
[0058] Desulfurization
[0059] Catalyst: Co--Mo (the first part)/ZnO (the latter part)
[0060] Condition: ordinary pressure, temperature 330.degree. C.,
LHSV=1.3 h.sup.-1
[0061] (Second Reactor)
[0062] Reforming
[0063] Catalyst: Water (20% by weight) was added to .alpha.-alumina
powder, and the mixture was mixed and compression molded by a
kneader to give columnar moldings of diameter 5 mm and length 5 mm.
The moldings were dried at 200.degree. C. for 3 hours, and calcined
at 1,280.degree. C. for 26 hours to obtain an alumina carrier.
Separately, 0.66 g of ruthenium trichloride (RuCl.sub.3/nH.sub.2O)
(containing 38% of Ru), 2.47 g of cobalt nitrate (Co(NO.sub.3)
36H.sub.2O) and 6.36 g of magnesium nitrate
(Mg(NO.sub.3).26H.sub.2O) were added to an aqueous solution of
zirconium oxychloride (ZrO(OH)Cl) (2.5 g in terms of ZrO.sub.2),
and the mixture was stirred until they were dissolved. The whole
amount of the solution was 10 cc. This solution was impregnated
into 50 g of the alumina carrier (pore filling method), and then
the impregnated carrier was dried at 120.degree. C. for 5 hours,
calcined at 500.degree. C. for 2 hours and adjusted in a particle
size to from 16 to 32 mesh. The catalyst obtained contains, based
on the weight of the carrier, 0.5% by weight of Ru, 5% by weight of
Zr in terms of zirconia, 1.0% by weight of Co and 2% by weight of
Mg in terms of magnesia.
[0064] Condition: Steam/carbon ratio 1.5, LHSV of the raw material
oil=2.5 h.sup.-1, ordinary pressure, the temperature of the inlet
of the catalyst layer 500.degree. C., the temperature of the outlet
of the catalyst layer 700.degree. C.
[0065] After the above reaction was carried out for consecutive 100
hours, the catalyst of the second reactor was withdrawn, and the
proportion of carbon deposition on the catalyst was measured and
calculated as follows.
Proportion of carbon deposition (%)=the length of the part where
carbon was deposited/the length of the whole catalyst
1 TABLE I 1 Composition (% by volume) C4HC Iso- DLN PG FG Alkylate
*1 pentane *2 MTBE *3 *4 Example 1 59 -- 41 -- -- -- -- Example 2
93 7 -- -- -- -- -- Example 3 93 3 4 -- -- -- -- Example 4 93 5 --
-- 2 -- -- Example 5 90 5 1 -- 4 -- -- Example 6 75 1 -- 23 1 -- --
Example 7 51 1 25 20 3 -- -- Example 8 -- -- -- 14 -- 86 -- Example
9 -- 3 -- 38 -- 59 -- Com. exam. 1 28 2 -- 70 -- -- -- Com. exam. 2
18 2 -- 70 -- 10 -- Com. exam. 3 30 5 -- -- -- 30 35 *1:
Hydrocarbon compound having 4 carbon atoms *2: Desulfurized light
naphtha *3: Benzene-free reformed gasoline *4: Gasoline obtained by
catalytic cracking
[0066]
2 TABLE I 2 Proportion of RVP carbon deposition RON (kPa) (%)
Example 1 93 80 1 Example 2 96 50 2 Example 3 96 45 2 Example 4 96
45 2 Example 5 96 46 2 Example 6 89 47 1 Example 7 89 78 1 Example
8 98 63 1 Example 9 89 80 1 Com. exam. 1 75 80 1 Com. exam. 2 76 80
1 Com. exam. 3 97 80 10
INDUSTRIAL APPLICABILITY
[0067] The fuel oil of the invention is suitable as a fuel oil
usable both in an internal combustion engine and in a fuel cell,
and in detail, since it comprises petroleum hydrocarbon fractions
such as the gasoline fraction, it is suitable as a fuel oil usable
both in an internal combustion engine and in a fuel cell.
* * * * *