U.S. patent application number 13/391891 was filed with the patent office on 2012-08-09 for aviation fuel oil composition.
This patent application is currently assigned to JX NIPPON OIL & ENERGY CORPORATION. Invention is credited to Akira Koyama.
Application Number | 20120198757 13/391891 |
Document ID | / |
Family ID | 43628088 |
Filed Date | 2012-08-09 |
United States Patent
Application |
20120198757 |
Kind Code |
A1 |
Koyama; Akira |
August 9, 2012 |
AVIATION FUEL OIL COMPOSITION
Abstract
To provide an aviation fuel oil composition which has excellent
life cycle characteristics and achieves excellent specific fuel
consumption. The aviation fuel oil composition according to the
present invention includes: a first base which is a fraction having
a boiling range of 140 to 280.degree. C. obtained through a step of
hydrotreating a first feedstock containing a sulfur-containing
hydrocarbon compound and an oxygen-containing hydrocarbon compound
derived from an animal or vegetable oil and fat or a second
feedstock which is an oil blend of the first feedstock and a
petroleum-based base obtained by refining a crude oil; and a second
base which is a fraction having a boiling range of 140 to
280.degree. C. obtained from a heavy oil cracking apparatus.
Inventors: |
Koyama; Akira; (Chiyoda-ku,
JP) |
Assignee: |
JX NIPPON OIL & ENERGY
CORPORATION
Tokyo
JP
|
Family ID: |
43628088 |
Appl. No.: |
13/391891 |
Filed: |
August 30, 2010 |
PCT Filed: |
August 30, 2010 |
PCT NO: |
PCT/JP2010/064700 |
371 Date: |
April 25, 2012 |
Current U.S.
Class: |
44/307 |
Current CPC
Class: |
Y02P 30/20 20151101;
B01J 21/12 20130101; C10L 2230/22 20130101; B01J 23/42 20130101;
C10G 2300/80 20130101; C10L 1/2283 20130101; B01J 27/19 20130101;
C10G 45/58 20130101; C10L 1/2235 20130101; C10L 2200/0407 20130101;
Y02P 30/00 20151101; C10L 2200/043 20130101; B01J 29/064 20130101;
C10G 2300/301 20130101; C10G 2400/08 20130101; C10L 2270/04
20130101; C10G 3/48 20130101; C10G 2300/308 20130101; C10L 1/19
20130101; C10G 2300/1033 20130101; B01J 37/0009 20130101; C10G
45/02 20130101; Y02P 30/10 20151101; C10G 3/46 20130101; C10L 1/04
20130101; B01J 23/38 20130101; B01J 35/023 20130101; C10G 2300/1014
20130101; C10G 65/043 20130101; B01J 37/0201 20130101; C10G 3/50
20130101; C10G 2300/4018 20130101; C10G 2300/1018 20130101; C10G
3/49 20130101; C10G 2300/202 20130101; B01J 23/70 20130101 |
Class at
Publication: |
44/307 |
International
Class: |
C10L 1/10 20060101
C10L001/10 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 31, 2009 |
JP |
2009-200695 |
Claims
1. An aviation fuel oil composition comprising: a first base which
is a fraction having a boiling range of 140 to 280.degree. C.
obtained through a step of hydrotreating a first raw oil feedstock
containing a sulfur-containing hydrocarbon compound and an
oxygen-containing hydrocarbon compound derived from an animal or
vegetable oil and fat or a second feedstock which is an oil blend
of the first feedstock and a petroleum-based base obtained by
refining a crude oil; and a second base which is a fraction having
a boiling range of 140 to 280.degree. C. obtained from a heavy oil
cracking apparatus.
2. The aviation fuel oil composition according to claim 1, wherein
the second base has a density at 15.degree. C. of 800 kg/m.sup.3 or
more and 840 kg/m.sup.3 or less.
3. The aviation fuel oil composition according to claim 1, wherein
the first base is obtained through the step of hydrotreating the
first or second feedstock in the presence of hydrogen under the
conditions of a hydrogen pressure of 2 to 13 MPa, a liquid hourly
space velocity of 0.1 to 3.0 h.sup.-1 and a hydrogen/oil ratio of
150 to 1500 NL/L, and a reaction temperature of 150 to 480.degree.
C. by using a catalyst prepared by supporting one or more metals
selected from elements of groups 6A and 8 of the periodic table on
a support formed of a porous inorganic oxide composed of two or
more elements selected from aluminum, silicon, zirconium, boron,
titanium, and magnesium.
4. The aviation fuel oil composition according to claim 1, wherein
the first base is obtained through a step of further isomerizing a
hydrogenated oil obtained through the step of hydrotreating the
first or second feedstock in the presence of hydrogen under
conditions of a hydrogen pressure of 2 to 13 MPa, a liquid hourly
space velocity of 0.1 to 3.0 and a hydrogen/oil ratio of 250 to
1500 NL/L, and a reaction temperature of 150 to 380.degree. C. by
using a catalyst prepared by supporting a metal selected from
elements of group 8 of the periodic table on a support formed of a
porous inorganic oxide composed of a substance selected from
aluminum, silicon, zirconium, boron, titanium, magnesium, and
zeolite.
5. The aviation fuel oil composition according to claim 1, further
comprising an aviation fuel oil base obtained by refining a crude
oil, a synthetic aviation fuel oil base, or a third base which is a
mixture thereof.
6. The aviation fuel oil composition according to claim 1, further
comprising one or more additives selected from an antioxidant, an
antistatic, a metal deactivator, and an anti-icing agent.
7. The aviation fuel oil composition according to claim 1,
satisfying standard values of JIS K2209 "Aviation Turbine Fuels".
Description
TECHNICAL FIELD
[0001] The present invention relates to an aviation fuel oil
composition.
BACKGROUND ART
[0002] Attention is paid to the effective utilization of biomass
energy as a preventive measure against global warming. Above all,
since biomass energy derived from vegetables can effectively use
carbon fixed from carbon dioxide in the atmosphere by
photosynthesis during the growth process of vegetables, it has a
property which is so-called carbon neutral and may not contribute
to the increase in carbon dioxide in the atmosphere from the
viewpoint of the life cycle. In addition, from the viewpoint of
depletion of petroleum resources and steep rise in crude oil
prices, biomass fuel is expected be very promising as an
alternative energy to petroleum.
[0003] The utilization of such biomass energy has been variously
studied even in the field of a transportation fuel. For example, if
a fuel derived from an animal or vegetable oil can be used as a
diesel fuel, the fuel is expected to play an effective role in the
emission reduction of carbon dioxide by the synergistic effect with
a high energy efficiency of a diesel engine. As a diesel fuel using
an animal or vegetable oil, a fatty acid methyl ester oil
(abbreviated as "FAME" from the initial characters of Fatty Acid
Methyl Ester) is generally known. FAME is manufactured by
subjecting a triglyceride, which is a general structure of animal
and vegetable oils, to ester exchange reaction with methanol by the
action of an alkali catalyst and the like. The FAME has been
studied to be used not only for a diesel fuel but also for an
aviation fuel oil, what is called a jet fuel. An airplane is
significantly influenced by the recent steep rise in crude oil
prices because a huge amount of fuel is used. Under these
circumstances, biomass fuel has attracted attention as an important
item which assumes the role not only as a preventive measure
against global warming but also as an alternative fuel to
petroleum. Currently, in a plurality of airline companies, the
mixing use of FAME and a petroleum-based jet fuel has been
tentatively implemented.
[0004] However, as described in the following Patent document 1, in
the step of manufacturing FAME, problems have been indicated that a
by-product glycerin is required to be treated, or cost and energy
are required for the cleaning of a produced oil or the like.
[0005] In addition, FAME has points of concern about
low-temperature performance or oxidation stability. Especially in
an aviation fuel, since the aviation fuel is exposed to an
extremely low temperature during flying at a high altitude, highly
strict standards for low-temperature performance are established,
and in case of using FAME, it is the present situation that the use
of mixing with a petroleum-based fuel has to be implemented and the
mixing amount has to be a low concentration. Further, regarding the
oxidation stability, the addition of an antioxidant is defined as
aviation fuel specifications, however, in view of the stability as
a base, as with the low-temperature performance, the mixing ratio
has to be limited to a low concentration.
[0006] On the other hand, attention is paid to the production
technique in which animal and vegetable oils and fats are used as
raw materials and these raw materials are reacted at high
temperature and high pressure in the presence of hydrogen and a
catalyst to obtain a hydrocarbon. Since the hydrocarbon obtained by
this technique is different from FAME, contains no oxygen or
unsaturated bonds and has properties equivalent to those of a
petroleum-based hydrocarbon fuel, it can be used at a higher
concentration than FAME. However, the hydrocarbon by these
techniques generally has a low density, and it was a point of
concern that even in case of using for an aviation fuel, the
density is reduced when mixed at a high concentration, resulting in
degradation of fuel efficiency.
CITATION LIST
Patent Literature
[0007] [Patent document 1] Japanese Patent Laid-Open No.
2005-154647
SUMMARY OF INVENTION
Technical Problem
[0008] In light of the above circumstances, it is an object of the
present invention to provide an aviation fuel oil composition which
has excellent life-cycle characteristics and achieves excellent
specific fuel consumption.
Solution to Problem
[0009] In order to solve the above problems, the present invention
provides an aviation fuel oil composition comprising a first base
which is a fraction having a boiling range of 140 to 280.degree. C.
obtained through a step of hydrotreating a first feedstock
containing a sulfur-containing hydrocarbon compound and an
oxygen-containing hydrocarbon compound derived from an animal or
vegetable oil and fat or a second feedstock which is an oil blend
of the first feedstock and a petroleum-based base obtained by
refining a crude oil, and a second base which is a fraction having
a boiling range of 140 to 280.degree. C. obtained from a heavy oil
cracking apparatus.
[0010] The second base preferably has a density at 15.degree. C. of
800 kg/m.sup.3 or more and 840 kg/m.sup.3 or less.
[0011] In addition, the first base is preferably obtained through a
step of hydrotreating the first or second feedstock in the presence
of hydrogen under the conditions of a hydrogen pressure of 2 to 13
MPa, a liquid hourly space velocity of 0.1 to 3.0 h.sup.-1, a
hydrogen/oil ratio of 150 to 1500 NL/L, and a reaction temperature
of 150 to 480.degree. C. by using a catalyst prepared by supporting
one or more metals selected from elements of groups 6A and 8 of the
periodic table on a support formed of a porous inorganic oxide
composed of two or more elements selected from aluminum, silicon,
zirconium, boron, titanium, and magnesium.
[0012] Further, the first base is preferably obtained through a
step of further isomerizing a hydrogenated oil obtained through the
step of hydrotreating the first or second feedstock in the presence
of hydrogen under the conditions of a hydrogen pressure of 2 to 13
MPa, a liquid hourly space velocity of 0.1 to 3.0 h.sup.-1, a
hydrogen/oil ratio of 250 to 1500 NL/L, and a reaction temperature
of 150 to 380.degree. C. by using a catalyst prepared by supporting
a metal selected from elements of group 8 of the periodic table on
a support formed of a porous inorganic oxide composed of a
substance selected from aluminum, silicon, zirconium, boron,
titanium, magnesium, and zeolite.
[0013] The aviation fuel oil composition of the present invention
may further contain an aviation fuel oil base obtained by refining
a crude oil, a synthetic aviation fuel oil base, or a third base
which is a mixture thereof.
[0014] In addition, the aviation fuel oil composition of the
present invention may further contain one or more additives
selected from an antioxidant, an antistatic, a metal deactivator,
and an anti-icing agent.
[0015] Further, the aviation fuel oil composition of the present
invention preferably satisfies standard values of JIS K2209
"Aviation Turbine Fuels".
Advantageous Effects of Invention
[0016] The present invention can satisfy both excellent life-cycle
characteristics obtained from carbon neutral properties and
excellent specific fuel consumption, and provides an
environment-friendly aviation fuel oil composition which
contributes to primary energy diversification.
DESCRIPTION OF EMBODIMENTS
[0017] Hereinafter, preferred embodiments of the present invention
will be described in detail.
[0018] In the present invention, there is used a feedstock (first
feedstock) containing a sulfur-containing hydrocarbon compound and
an oxygen-containing hydrocarbon compound derived from an animal or
vegetable oil and fat or a feedstock (second feedstock) containing
the first feedstock and a petroleum-based base obtained by refining
a crude oil. In addition, in the following description, the first
and the second feedstock are collectively called a "feedstock"
depending on the situation.
[0019] Examples of animal and vegetable oils and fats include, for
example, beef fat, rapeseed oil, camelina oil, soybean oil, palm
oil, and oils and fats or hydrocarbons produced by specific
microalgae. The specific microalgae mean algae which transform part
of nutrients in the body into forms of hydrocarbons or oils and
fats. Examples of the specific microalgae include, for example,
Chlorella, Scenedesmus, Spirulina, Euglena, Botryococcas braunii
and Pseudochoricystis ellipsoidea. It is known that Chlorella,
Scenedesmus, Spirulina and Euglena produce oils and fats and
Botryococcas braunii and Pseudochoricystis ellipsoidea produce a
hydrocarbon. As the animal and vegetable oils and fats in the
present invention, any oils and fats may be used and waste oils
after using these oils and fats may be used. In addition, there may
be used wax esters extracted from microalgae or free fatty acids
which are by-products produced by refining oils and fats. That is,
the animal and vegetable oils and fats related to the present
invention include waste oils of the oils and fats, wax esters
extracted from microalgae and free fatty acids which are by-product
produced by refining oils and fats. From the viewpoint of carbon
neutral, oils and fats derived from vegetables are preferable, and
from the viewpoint of the yield of kerosene fraction after
hydrotreatment, preferred are oils and fats which have a high
composition ratio (fatty acid composition) of each fatty acid group
having 10 to 14 carbon atoms in the fatty acid carbon chain.
Considering this point of view, the vegetable fats and oils include
coconut oil, perm, kernel oil and camelina oil, and oils and fats
produced by specific microalgae include oils and fats produced by
Euglena. In addition, the above oils and fats may be used alone or
may be used by mixing two or more kinds.
[0020] Further, the fatty acid composition is a value determined by
testing a methyl ester, which is prepared according to Standard
Methods for the Analysis of Fats, Oils and Related materials
(established by japan Oil Chemists' Society) (1991) "2.4.20.2-91
Preparation Method of fatty Acid Methyl Ester (Boron
Trifluoride-Methanl Method)", according to Standard Methods for the
Analysis of Fats, Oils and Related Materials (established by Japan
Oil Chemists' Society) (1993) "2.4.21.3-77 Fatty Acid Composition
(FID Temperature Programmed Gas Chromatograph Method)" using a
temperature programmed gas chromatograph equipped with a flame
ionization detector (FID), and is referred to as a composition
ratio (mass %) of each fatty acid group constituting the oils and
fats.
[0021] The sulfur-containing hydrocarbon compound incorporated in a
feedstock is not particularly limited, but specific examples
thereof include sulfide, disulfide, polysulfide, thiol, thiophen,
benzothiophene, dibenzothiophene and a derivative thereof. The
sulfur-containing hydrocarbon compound contained in a feedstock may
be a single compound or may be a mixture of two or more kinds. In
addition, a petroleum hydrocarbon fraction containing a sulfur
content may be used as the sulfur-containing hydrocarbon
compound.
[0022] The sulfur content contained in a feedstock is preferably 1
to 50 mass ppm, more preferably 5 to 30 mass ppm and further more
preferably 10 to 20 mass ppm in terms of sulfur atom based on the
total amount of the feedstock. If the content in terms of sulfur
atom is less than 1 mass ppm, it tends to become difficult to
stably maintain the deoxygenation activity. On the other hand, if
the content in terms of sulfur atom exceeds 50 mass ppm, the sulfur
concentration in a light gas discharged in the hydrorefining step
is increased and the sulfur content contained in the hydrorefined
oil tends to be increased, and in case of using as a fuel for a
diesel engine or the like, there is a concern about an adverse
effect on an engine exhaust purification apparatus. In addition,
the sulfur content in the present invention means the sulfur
content by mass determined according to JIS K 2541 "Determination
of Sulfur Content" or the method described in ASTM-5453.
[0023] The sulfur-containing hydrocarbon compound incorporated in a
feedstock is preliminarily mixed with an oxygen-containing
hydrocarbon compound derived from an animal or vegetable oil and
fat and then the mixture may be introduced into a reactor of a
hydrorefining apparatus, or may be supplied at the earlier stage of
the reactor when the oxygen-containing hydrocarbon compound derived
from an animal or vegetable oil and fat is introduced into the
reactor.
[0024] In addition, the petroleum-based base, which is obtained by
refining a crude oil and contained in the second raw material,
includes a faction obtained by the atmospheric or vacuum
distillation of a crude oil or a fraction obtained by reactions
such as hydro desulfurization, hydrocracking, fluid catalytic
cracking and catalytic reforming of a crude oil. One or two or more
of these fractions may be incorporated in a feedstock. Further, the
petroleum-based base obtained by refining a crude oil may be a
compound derived from chemical products or a synthetic oil obtained
through a Fischer-Tropsch reaction.
[0025] In the second feedstock, the content ratio of the
petroleum-based base obtained by refining a crude oil or the like
is not particularly limited, but is preferably 20 to 70 vol % and
more preferably 30 to 60 vol %.
[0026] The second base related to the present invention is a
fraction having a boiling range of 140 to 280.degree. C. obtained
through a step of hydrotreating a feedstock (the first or second
feedstock).
[0027] The hydrotreatment preferably includes the following
hydrotreatment step. The hydrotreatment step related to the present
invention is preferably carried out under the conditions of a
hydrogen pressure of 2 to 13 MPa, a liquid hourly space velocity of
0.1 to 3.0 h.sup.-1, and a hydrogen/oil ratio of 150 to 1500 NL/L,
more preferably a hydrogen pressure of 2 to 13 MPa, a liquid hourly
space velocity of 0.1 to 3.0 h.sup.-1, and a hydrogen/oil ratio of
150 to 1500 NL/L, and further more preferably a hydrogen pressure
of 3 to 10.5 MPa, a liquid hourly space velocity of 0.25 to 1.0
h.sup.-1, and a hydrogen/oil ratio of 300 to 1000 NL/L. Each of
these conditions is a factor having an influence on the reaction
activity, for example, if the hydrogen pressure and the
hydrogen/oil ratio are less than the lower limits, the reactivity
tends to reduce or the activity tends to reduce rapidly, and if the
hydrogen pressure and the hydrogen/oil ratio exceed the upper
limits, an enormous equipment investment for a compressor or the
like may be required. Lower liquid hourly space velocity tends to
be more advantageous for the reactions. However, if the liquid
hourly space velocity is less than the lower limits, an extremely
large reaction tower volume is required and an enormous equipment
investment tends to be required. On the other hand, if the liquid
hourly space velocity exceeds the upper limits, the reaction may
not tend to proceed sufficiently.
[0028] The reaction temperature can be arbitrarily set in order to
obtain the intended cracking rate of the feedstock heavy fraction
or the intended fraction yield. The average temperature of the
whole reactor is generally in the range of 150 to 480.degree. C.,
preferably 200 to 400.degree. C. and more preferably 260 to
360.degree. C. If the reaction temperature is less than 150.degree.
C., the reaction would not proceed sufficiently, and if the
reaction temperature exceeds 480.degree. C., cracking excessively
proceeds and the liquid product yield tends to be decreased.
[0029] As the hydrotreating catalyst, there may be used a catalyst
in which a metal selected from elements of groups 6A and 8 of the
periodic table is supported on a support formed of a porous
inorganic oxide composed of two or more elements selected from
aluminum, silicon, zirconium, boron, titanium, and magnesium.
[0030] As the support for the hydrotreating catalyst, there is used
a porous inorganic oxide comprised of two or more elements selected
from aluminum, silicon, zirconium, boron, titanium and magnesium.
The support is generally a porous inorganic oxide containing
aluminum, and the other constituent components of the support
include silica, zirconia, boria, titania and magnesia. Preferred is
a composite oxide containing alumina and at least one or more
selected from the other constituent components. In addition, as a
component other than these, phosphorus may be contained. The total
content of the components other than alumina is preferably 1 to 20
wt % and more preferably 2 to 15 wt %. If the total content of the
components other than alumina is less than 1 wt %, a sufficient
catalyst surface area cannot be obtained and the activity may be
reduced. On the other hand, the total content exceeds 20 wt %, the
acidity of the support is increased and the activity may be reduced
by the formation of coke. When phosphorus is contained as a support
constituent component, the content is preferably 1 to 5 wt % and
more preferably 2 to 3.5 wt % in terms of the oxide.
[0031] There is no particular restriction on a raw material which
is a precursor of silica, zirconia, boria, titania and magnesia
which are support constituent components other than alumina, and a
general solution containing silicon, zirconium, boron, titanium or
magnesium may be used. For example, for silicon, silica acid, water
glass, and a silica sol may be used. For titanium, titanium
sulfate, titanium tetrachloride and various lakeside salts thereof
may be used. For zirconium, zirconium sulfate and various alkoxide
salts thereof may be used. For boron, boric acid may be used. For
magnesium, magnesium nitrate may be used. For phosphorus,
phosphoric acid and alkali metal salts thereof may be used.
[0032] Preferred is a method in which the raw materials of the
support constituent components other than alumina are added at any
stage prior to calcination of the support. For example, the raw
materials is preliminarily added to an aluminum aqueous solution
and then an aluminum hydroxide gel containing these constituent
components may be prepared, or the raw materials may be added to
the aluminum hydroxide gel prepared. Alternatively, the raw
materials may be added in a step in which water or an acid aqueous
solution is added to a commercially available alumina intermediate
or boehmite powder and the resulting mixture is kneaded, but more
preferred is a method in which the raw materials are allowed to
coexist at the step of preparing an aluminum hydroxide gel.
Although the mechanism exhibiting advantageous effects of these
support constituent components other than alumina has not been
elucidated, it is assumed that these components form a composite
oxide state together with aluminum. It is thus presumed that this
increases the surface area of the support and causes some
interaction with the active metals, thereby giving influences to
the activity of the catalyst.
[0033] The active metals of the hydrotreating catalyst include at
least one metal selected from metals of groups 6A and 8 of the
periodic table and preferably include two or more metals selected
from groups 6A and 8 of the periodic table. Examples of these
metals include, for example, Co--Mo, Ni--Mo, Ni--Co--Mo and Ni--W.
In carrying out the hydrotreatment, these metals are used after
converting to a sulfide state.
[0034] As the content of the active metals, for example, the total
amount supported of W and Mo is preferably 12 to 35 wt % and more
preferably 15 to 30 wt % in terms of the oxide, based on the
catalyst weight. If the total amount supported of W and Mo is less
than 12 wt %, the catalytic activity would be reduced because the
number of active sites is reduced. If the total amount supported
exceeds 35 wt %, the metals fail to disperse effectively, possibly
leading to a reduction in catalytic activity. In addition, the
total amount supported of Co and Ni is preferably 1.5 to 10 wt %
and more preferably 2 to 8 wt %, in terms of the oxide, based on
the catalyst weight. If the total amount supported of Co and Ni is
less than 1.5 wt %, a sufficient cocatalytic effect cannot be
obtained, possibly leading to a reduction in catalytic activity. If
the total amount supported is more than 10 wt %, the metals fail to
disperse effectively, possibly leading to a reduction in catalytic
activity.
[0035] In any of the hydrotreating catalysts, there is no
particular restriction on the method of supporting the active
metals on a support, and any conventional method for producing a
usual desulfurization catalyst may be employed. A method is
preferably employed in which a catalyst support is impregnated with
a solution containing salts of the active metals. Alternatively, an
equilibrium adsorption method, a pore-filling method, or an
incipient-wetness method is also preferably used. For example, the
pore-filling method is a method in which the pore volume of a
support is measured in advance and then the support is impregnated
with the same volume of a metal salt solution as the pore volume.
There is no particular restriction on the method of impregnating
the support with a solution. Therefore, any suitable method may be
used depending on the amount of the metals to be supported and
physical properties of the support.
[0036] The type of the hydrotreatment reactor may be a fixed-bed
system. That is, hydrogen may be supplied in counterflow or
parallel flow with respect to the feedstock. When a plurality of
reactors are provided, counterflow and parallel flow may be
combined. The supply system of the feedstock is generally downflow
and a gas-liquid concurrent flow system may be employed. Further,
the reactors may be used alone or in combination with a plurality
of them, and there may be employed a structure in which the inside
of the reactor is divided into a plurality of catalyst beds. In the
present invention, the hydrotreated oil hydrotreated in the reactor
is fractionated into predetermined fractions through gas-liquid
separation and rectification. At this time, in order to remove
by-product gases such as water, carbon monoxide, carbon dioxide and
hydrogen sulfide which are generated accompanied by the reaction, a
gas-liquid separation apparatus or other by-product gas removal
apparatus may be installed between the plurality of reactors or in
the product recovering step. Preferable examples of an apparatus to
remove a by-product include a high-pressure separator.
[0037] Hydrogen gas is generally introduced from the inlet of the
first reactor, accompanied by the feedstock before or after passing
through a heating furnace. Alternatively, hydrogen gas may be
introduced into between the catalyst beds or between the plurality
of reactors for the purposes of controlling the temperature in the
reactors and maintaining the hydrogen pressure over the whole
reactors as widely as possible. Hydrogen to be introduced in such a
manner is referred to as quench hydrogen. The ratio of the
quenching hydrogen to the hydrogen introduced accompanied by the
feedstock is preferably from 10 to 60 vol % and more preferably
from 15 to 50 vol %. The ratio of less than 10 vol % would cause a
tendency that the reaction at reaction sites in the subsequent
stages may not proceed sufficiently. The ratio of more than 60 vol
% would cause a tendency that the reaction near the inlet of the
reactor may not proceed sufficiently.
[0038] In the method of producing the aviation fuel oil base of the
present invention, in order to suppress the heat generation amount
in the hydrotreatment reactor in hydrotreating the feedstock, a
specific amount of a recycled oil may be incorporated into the
feedstock. The content of the recycled oil is preferably 0.5- to
5-fold by mass based on the oxygen-containing hydrocarbon compound
derived from an animal or vegetable oil and fat, and the ratio can
be optionally determined within the above range depending on the
maximum use temperature of the hydrotretment reactor. For this
reason, if it is assumed that both oils have the same specific
heat, the reaction heat may be sufficiently reduced if the content
of both oils is within the above range, because if both oils are
mixed at a ratio of 1 to 1, the temperature increase becomes half
that of the case where a substance derived from an animal or
vegetable oil and fat is reacted singly. In addition, if the
content of the recycled oil is higher than 5-fold by mass of the
oxygen-containing hydrocarbon compound, the concentration of the
oxygen-containing hydrocarbon compound is reduced and thus the
reactivity is reduced, and in addition, the flow rate of pipes and
the like is increased and thus the load is increased. On the other
hand, if the content of the recycled oil is lower than 0.5-fold by
mass of the oxygen-containing hydrocarbon compound, the temperature
increase may not be sufficiently suppressed.
[0039] The method of mixing of the feedstock and the recycled oil
is not particularly limited, but for example, both oils are mixed
in advance and the mixture may be introduced into a reactor of a
hydrotreatment apparatus, or when a feedstock is introduced into
the reactor, the feedstock may be supplied at the previous stage of
the reactor. Further, it is possible that a plurality of reactors
are connected in series and then the feedstock is introduced
between the reactors, or the catalyst layer is divided in a single
reactor and then the feedstock is introduced between the catalyst
layers.
[0040] In addition, the recycled oil preferably contains a part of
a hydrotreated oil obtained by removing by-product gases such as
water, carbon monoxide, carbon dioxide and hydrogen sulfide which
are generated after hydrotreating the feedstock. In addition, the
recycled oil preferably contains a part of products obtained by
isomerizing each of a light fraction, an intermediate fraction and
a heavy fraction which are fractionated from the feedstock, or
preferably contains a part of an intermediate fraction which is
fractionated from a product obtained by further isomerizing the
hydrotreated oil.
[0041] In the hydrotreatment of the present invention, there is
preferably included a step of further isomerizing the hydrotreated
oil obtained by the above hydrotreating step.
[0042] The sulfur content contained in the hydrotreated oil which
is an isomerized feedstock is preferably 1 mass ppm or less and
more preferably 0.5 ppm. If the sulfur content exceeds 1 mass ppm,
the isomerization tends to be prevented. In addition to this, for
the same reason, the reaction gas containing hydrogen, which is
introduced together with the hydrogenated oil, is required to have
a sufficiently low sulfur concentration, and has a sulfur
concentration of preferably 1 ppm by volume or less and more
preferably 0.5 ppm by volume or less.
[0043] The isomerization step is carried out under the conditions
of a hydrogen pressure of 2 to 13 MPa, a liquid hourly space
velocity of desirably 0.1 to 3.0 h.sup.-1, and a hydrogen/oil ratio
of 250 to 1500 NL/L, more desirably a hydrogen pressure of 2.5 to
10 MPa, a liquid hourly space velocity of 0.5 to 2.0 h.sup.-1, and
a hydrogen/oil ratio of 380 to 1200 NL/L, and further desirably a
hydrogen pressure of 3 to 8 MPa, a liquid hourly space velocity of
0.8 to 1.8 h.sup.-1, and a hydrogen/oil ratio of 350 to 1000 NL/L,
in the presence of hydrogen. Each of these conditions is a factor
having an influence on the reaction activity, for example, if the
hydrogen pressure and the hydrogen/oil ratio are less than the
lower limits, the reactivity tends to reduce or the activity tends
to reduce rapidly, and if the hydrogen pressure and the
hydrogen/oil ratio exceed the upper limits, an enormous equipment
investment for a compressor or the like may be required. Lower
liquid hourly space velocity tends to be more advantageous for the
reactions. However, if the liquid hourly space velocity is less
than the lower limits, an extremely large reaction tower volume is
required and an enormous equipment investment tends to be required.
On the other hand, if the liquid hourly space velocity exceeds the
upper limits, the reaction does not tend to sufficiently
proceed.
[0044] The reaction temperature in the isomerization step can be
arbitrarily set in order to obtain the intended cracking rate of
the feedstock heavy fraction or the intended fraction yield, but is
in the range of preferably 150 to 380.degree. C., more preferably
240 to 380.degree. C. and especially preferably 250 to 365.degree.
C. If the reaction temperature is lower than 150.degree. C., the
hydroisomerization reaction would not proceed sufficiently, and if
the reaction temperature exceeds 380.degree. C., excessive cracking
or other side reactions proceed, possibly leading to a reduction in
the liquid product yield.
[0045] As a catalyst for isomerization, there may be used a
catalyst prepared by supporting one or more metals selected from
elements of group 8 of the periodic table on a support formed of a
porous inorganic oxide composed of substances selected from
aluminum, silicon, zirconium, boron, titanium, magnesium, and
zeolite.
[0046] Examples of the porous inorganic oxide used as a support of
the isomerization catalyst include alumina, titania, zirconia,
boria, silica or zeolite, and in the present invention, of these,
preferred is one composed of alumina and at least one of titania,
zirconia, boria, silica and zeolite. The production method is not
particularly limited, but an optional preparation method may be
employed by using raw materials in the form of various sols
corresponding to each element or a salt compound. Furthermore, the
support may be prepared by once preparing a composite hydroxide or
a composite oxide such as silica-alumina, silica-zirconia,
alumina-titania, silica-titania and alumina-boria and then adding
the composite hydroxide or composite oxide in form of an alumina
gel or other hydroxides, or in the forms an appropriate solution,
at a given step of the preparation step. The proportion of alumina
to the other oxides may be at any ratio based on the support, but
the content of alumina is preferably 90 mass % or less, more
preferably 60 mass % or less, further more preferably 40 mass % or
less, and preferably 10 mass % or more, more preferably 20 mass %
or more.
[0047] Zeolite is a crystalline alumino silicate. Examples of the
crystalline alumino silicate include faujasite, pentasil and
mordenite. There may be used ones ultrastabilized by a specific
hydrothermal treatment and/or acid treatment, or zeolites whose
alumina content is adjusted. Preferred zeolites are those of
faujasite and mordenite types, and particularly preferred zeolites
are those of Y and beta types. The zeolites of Y type are
preferably ultrastabilized. The zeolite ultrastabilized by a
hydrothermal treatment have an intrinsic micro porous structure,
so-called micro pores of 20 .ANG. or less as well as newly formed
pores in the range of 20 to 100 .ANG.. The hydrothermal treatment
may be carried out under known conditions.
[0048] As the active metal of the isomerization catalyst, there are
used one or more metals selected from elements of group 8 of the
periodic table. Among these metals, preferably used are one or more
metals selected from Pd, Pt, Rh, Ir, Au and Ni, and more preferably
used is a combination thereof. Examples of the preferred
combination include, for example, Pd--Pt, Pd--Ir, Pd--Rh, Pd--Au,
Pd--Ni, Pt--Rh, Pt--Ir, Pt--Au, Pt--Ni, Rh--Ir, Rh--Au, Rh--Ni,
Ir--Au, Ir--Ni, Au--Ni, Pd--Pt--Rh, Pd--Pt--Ir and Pt--Pd--Ni.
Among these, more preferred combinations are Pd--Pt, Pd--Ni,
Pt--Ni, Pd--Ir, Pt--Rh, Pt--Ir, Rh--Ir, Pd--Pt--Rh, Pd--Pt--Ni and
Pd--Pt--Ir, and especially preferred combinations are Pd--Pt,
Pd--Ni, Pt--Ni, Pd--Ir, Pt--Ir, Pd--Pt--Ni and Pd--Pt--Ir.
[0049] The total content of the active metals is preferably 0.1 to
2 mass %, more preferably 0.2 to 1.5 mass % and further more
preferably 0.5 to 1.3 mass %, in terms of metal, on the basis of
the catalyst mass. If the total amount supported of metals is less
than 0.1 mass %, the number of active sites is reduced, leading to
a tendency that a sufficient activity may not be obtained. On the
other hand, if the total amount supported of metals exceeds 2 mass
%, the metals fail to disperse effectively, leading to a tendency
that a sufficient activity may not be obtained.
[0050] In any of the isomerization catalysts, there is no
particular restriction on the method of supporting the active
metals on a support, and any conventional method for producing a
usual desulfurization catalyst may be employed. There is preferably
employed a method in which a catalyst support is impregnated with a
solution containing salts of the active metals. Alternatively,
there is also preferably employed an equilibrium adsorption method,
a pore-filling method, or an incipient-wetness method. For example,
the pore-filling method is a method in which the pore volume of a
support is measured in advance, and then the support is impregnated
with the same volume of a metal salt solution. There is no
particular restriction on the method of impregnating the support
with a solution. Therefore, any suitable method may be used
depending on the amount of the metals to be supported and physical
properties of the support.
[0051] The isomerization catalyst used in the present invention is
preferably used for the reaction after the active metals contained
in the catalyst are subjected to reduction treatment. The reduction
conditions are not particularly limited, but the active metals are
reduced at a temperature of 200 to 400.degree. C., preferably 240
to 380.degree. C. under a hydrogen stream. If the reduction
temperature is less than 200.degree. C., the active metals are not
reduced sufficiently and thus the catalyst may not exert
hydrodeoxidization and hydroisomerization activities. If the
reduction temperature exceeds 400.degree. C., agglomeration of the
active metals proceeds and thus similarly the catalyst may not
exert hydrodeoxidization and hydroisomerization activities.
[0052] The type of the isomerization reactor may be a fixed-bed
system. That is, hydrogen may be supplied in counterflow or
parallel flow with respect to the feedstock. When a plurality of
reactors are provided, counterflow and parallel flow may be
combined. The supply system of the feedstock is generally downflow
and a gas-liquid concurrent flow system may be employed. Further,
the reactors may be used alone or in combination with a plurality
of them, and there may be employed a structure in which the inside
of the reactor is divided into a plurality of catalyst beds.
[0053] Hydrogen gas is generally introduced from the inlet of the
first reactor, accompanied by the feedstock before or after passing
through a heating furnace. Alternatively, hydrogen gas may be
introduced into between the catalyst beds or between the plurality
of reactors for the purposes of controlling the temperature in the
reactors and maintaining the hydrogen pressure over the whole
reactors. Hydrogen to be introduced in such a manner is referred to
as quench hydrogen. The ratio of the quenching hydrogen to the
hydrogen introduced, accompanying by the feedstock is preferably
from 10 to 60 vol % and more preferably from 15 to 50 vol %. The
ratio of less than 10 vol % would cause a tendency that the
reaction at reaction sites in the subsequent stages may not proceed
sufficiently. The ratio of more than 60 vol % would cause a
tendency that the reaction near the inlet of the reactor may not
proceed sufficiently.
[0054] The isomerized oil obtained after the isomerization step may
be fractionated into a plurality of fractions in a rectification
column, where necessary. For example, the isomerized oil may be
fractionated into a light fraction such as a gas and a naphtha
fraction, an intermediate fraction such as kerosene and a gas oil
fraction, and a heavy fraction such as a residue fraction. In this
case, the cut temperature between the light fraction and the
intermediate fraction is preferably 100 to 200.degree. C., more
preferably 120 to 180.degree. C. and further more preferably 120 to
160.degree. C. and still further more preferably 130 to 150.degree.
C. The cut temperature between the intermediate fraction and the
heavy fraction is preferably 250 to 360.degree. C., more preferably
250 to 320.degree. C., further more preferably 250 to 300.degree.
C. and still further more preferably 250 to 280.degree. C. Hydrogen
may be produced by modifying a part of the light hydrocarbon
fraction to be produced in a steam reforming apparatus. The
hydrogen thus produced has a property which is so-called carbon
neutral and can reduce the environmental load because the raw
materials used for steam reforming are hydrocarbons derived from
biomass. In addition, the intermediate fraction obtained by
fractionating the isomerized oil can be suitably used as an
aviation fuel oil base.
[0055] Further, the second base contained in the aviation fuel oil
composition of the present invention is a fraction having a boiling
range of 140 to 280.degree. C. which is obtained from the heavy oil
cracking apparatus. As the heavy oil cracking apparatus, there may
used common apparatuses such as a fluid catalytic cracking
apparatus using an atmospheric residue from an atmospheric
distillation apparatus or a vacuum residue from a vacuum
distillation apparatus as a raw material, a hydrocracking apparatus
using a vacuum residue from a vacuum distillation apparatus as a
raw material or a thermal cracking apparatus, and an aviation fuel
fraction produced by these apparatuses has a density at 15.degree.
C. of preferably 800 kg/m.sup.3 or more and 840 kg/m.sup.3 or less,
more preferably 810 kg/m.sup.3 or more and 840 kg/m.sup.3 or less
and further preferably 820 kg/m.sup.3 or more and 840 kg/m.sup.3 or
less. If the aviation fuel fraction has a density of less than 800
kg/m.sup.3, it is not preferable because the aviation fuel fraction
has no effect for preventing the reduction in density in case of
mixing with the hydrotreated oil of the animal or vegetable oil and
fat. In addition, if the aviation fuel fraction has a density
exceeding 840 kg/m.sup.3, it is also not preferable because the
combustibility is reduced due to the increase in the aromatic
content. Further, in JIS K2209 "Aviation Turbine Fuels", 0.8398
kg/cm.sup.3 (839.8 kg/m.sup.3) is defined as the upper limit of the
density specification.
[0056] The aviation fuel oil base related to the present invention
may contain only the first base and second base, but may further
contain, as a third base, an aviation fuel oil base obtained by
refining a crude oil, a synthetic aviation fuel oil base, or a
mixture thereof. The third base includes a synthetic aviation fuel
oil base obtained through a Fischer-Tropsch reaction by using an
aviation fuel oil fraction obtained by a general petroleum refining
step and a synthetic gas composed of hydrogen and carbon monoxide
as raw materials. The synthetic aviation fuel oil base is
characterized in that it contains almost no aromatic content, is
mainly composed of a saturated hydrocarbon, and has a high smoke
point. In addition, the production method of the synthetic gas is
not particularly limited and a well-known method may be
employed.
[0057] Further, the aviation fuel oil composition of the present
invention may further contain various additives added to a
conventional aviation fuel oil. As the additives, preferred are one
or more additives selected from an antioxidant, an antistatic, a
metal deactivator, and an anti-icing agent.
[0058] As the antioxidant, in order to prevent the generation of
gum in the aviation fuel oil, there may be added a mixture of 75%
or more of N,N-diisopropylparaphenylene diamine and
2,6-di-tertiary-butylphenol and 25% or less of tertiary and
tritertiary butylphenol, a mixture of 72% or more of
2,4-dimethyl-6-tertiary-butylphenol and 28% or less of monomethyl
and dimethyl tertiary butylphenol, a mixture of 55% or more of
2,4-dimethyl-6-tertiary-butylphenol and 45% or less of tertiary and
ditertiary butylphenol, 2,6-ditertiarybutyl-4-methylphenol, and the
like, as long as not exceeding 24.0
[0059] As the antistatic, in order to prevent the accumulation of
static electricity caused by the friction with the inside wall of
the pipe when the aviation fuel oil flows inside the fuel piping
system at a high speed and to increase electrical conductivity,
STADIS 450 produced by Octel or the like may be added, as long as
not exceeding 3.0 mg/l.
[0060] As the metal deactivator, in order to prevent that the free
metal components contained in the aviation fuel oil are reacted to
make the fuel unstable, N,N-disalicylidene-1,2-propanediamine or
the like may be added, as long as not exceeding 5.7 mg/l.
[0061] As the anti-icing agent, in order to prevent that a small
amount of water contained in the aviation fuel oil is frozen to
block the pipe, there may be added ethylene glycol monoethyl ether
or the like in the range of 0.1 to 0.15 vol %.
[0062] As the aviation fuel oil composition of the present
invention, there may be further arbitrarily added an optional
additive such as antistatic, a corrosion inhibition agent and a
bactericidal agent without departing from the scope of the present
invention.
[0063] The aviation fuel oil composition of the present invention
preferably satisfies the standard values of JIS K2209 "Aviation
Turbine Fuels".
[0064] From the viewpoint of the specific fuel consumption, the
aviation fuel oil composition of the present invention has a
density at 15.degree. C. of preferably 775 kg/m.sup.3 or more and
more preferably 780 kg/m.sup.3 or more. On the other hand, from the
viewpoint of the combustibility, the aviation fuel oil composition
has a density at 15.degree. C. of preferably 839 kg/m.sup.3 or
less, more probably 830 kg/m.sup.3 or less and further more
preferably 820 kg/m.sup.3 or less. In addition, the density at
15.degree. C. referred herein denotes a value measured according to
JIS K2249 "Crude Oil and Petroleum Products--Determination of
density and petroleum measurement tables based on reference
temperature (15.degree. C.)".
[0065] From the viewpoint of the evaporation characteristics, as
the distillation properties of the aviation fuel oil composition of
the present invention, a 10 vol % distillation temperature is
preferably 204.degree. C. or less and more preferably 200.degree.
C. or less. From the viewpoint of the burning characteristics
(burning out characteristics), the end point is preferably
300.degree. C. or less and more preferably 290.degree. C. or less
and further more preferably 280.degree. C. or less. In addition,
the distillation properties referred herein denotes a value
measured according to JIS K2254 Petroleum Products--Determination
of distillation characteristics".
[0066] From the viewpoint of the prevention of defects caused by
precipitate formation in the fuel introduction system, the existent
gum content of the aviation fuel oil composition of the present
invention is preferably 7 mg/100 ml or less, more preferably 5
mg/100 ml or less and further more preferably 3 mg/100 ml or
less.
[0067] In addition, the existent gum content referred herein
denotes a value measured according to JIS K2261 "Motor gasoline and
aviation fuels--Determination of existent gum".
[0068] From the viewpoint of the specific fuel consumption, the net
heat of combustion of the aviation fuel oil composition of the
present invention is 42.8 MJ/kg or more and more preferably 45
MJ/kg or more. In addition, the net heating value used herein
denotes a value measured according to JIS K2279 "Crude Oil and
petroleum products--Determination of heat of combustion".
[0069] From the viewpoint of achieving the flowability of the fuel
pipe and the uniform fuel injection, the kinematic viscosity at
-20.degree. C. of the aviation fuel oil composition of the present
invention is preferably 8 mm.sup.2/s or less, more preferably 7
mm.sup.2/s or less and further more preferably 5 mm.sup.2/s or
less. In addition, the kinematic viscosity referred herein denotes
a value measured according to JIS K2283 "Crude petroleum and
petroleum products--Determination of kinematic viscosity".
[0070] From the viewpoint of the corrosive properties of the fuel
tank and pipe, the copper strip corrosion of the aviation fuel oil
composition of the present invention is preferably 1 or less. The
copper strip corrosion referred herein denotes a value measured
according to JIS K2513 "Petroleum Products--Corrosiveness to
copper-Copper strip test".
[0071] From the view point of the combustibility (prevention of
soot generation), the aromatic content of the aviation fuel oil
composition of the present invention is preferably 25 vol % and
more preferably 20 vol %. The aromatic content referred herein
denotes a value measured according to JIS K2536 "Liquid petroleum
products--Testing method of components (Fluorescent Indicator
Adsorption Method)".
[0072] From the view point of the combustibility (prevention of
soot generation), the smoke point of the aviation fuel oil
composition of the present invention is preferably 25 mm or more,
more preferably 27 mm or more and further more preferably 30 mm or
more. In addition, the smoke point referred herein denotes a value
measured according to JIS K2537 "Petroleum products--Kerosine and
aviation turbine fuels--Determination of smoke point".
[0073] From the viewpoint of the corrosiveness, the sulfur content
of the aviation fuel oil composition of the present invention is
preferably 0.3 mass % or less, more preferably 0.2 mass % or less
and further more preferably 0.1 mass % or less. In addition, from
the viewpoint of the corrosiveness, the mercaptan sulfur content is
preferably 0.003 mass % or less, more preferably 0.002 mass % or
less and further more preferably 0.001 mass % or less. Further, the
sulfur content referred herein is a value measured according to JIS
K2541 "Crude Oil and Petroleum Products--Determination of sulfur
content", and the mercaptan sulfur content referred herein is a
value measured according to JIS K2276 "Determination of mercaptan
sulfur in light and middle distillates fuels (Potentiometric
Method)".
[0074] From the viewpoint of the safety, the flash point of the
aviation fuel oil composition of the present invention is
preferably 38.degree. C. or more, more preferably 40.degree. C. or
more and further more preferably 45.degree. C. or more. The flash
point referred herein denotes a value measured according to JIS
K2265 "Crude Oil and Petroleum Products--Determination of flash
point--Tag Closed Cup Method".
[0075] From the viewpoint of the corrosiveness, the total acid
value of the aviation fuel oil composition of the present invention
is preferably 0.1 mg KOH/g or less, more preferably 0.08 mg KOH/g
or less and further more preferably 0.05 mg KOH/g or less. In
addition, the total acid value referred herein denotes a value
measured according to JIS K2276 "Petroleum Products--Aviation Fuels
Test Method--Determination of the Total Acid Value".
[0076] From the viewpoint of the prevention of the fuel supply
reduction due to the fuel freezing under the exposure to a low
temperature during flying, the freezing point of the aviation fuel
oil composition of the present invention is preferably -47.degree.
C. or less, more preferably -48.degree. C. or less and further more
preferable -50.degree. C. or less. In addition, the freezing point
referred herein denotes a value measured according to JIS K 2276
"Determination of the freezing point of aviation fuels".
[0077] From the viewpoint of the prevention of fuel filter blockage
due to the precipitate formation during exposure to a high
temperature, the thermal stability of the aviation fuel oil
composition of the present invention is preferably that the filter
pressure drop is 10.1 kPa or less and the preheat tube deposit
rating is less than 3 in Method A, and the filter pressure drop e
is 3.3 kPa or less and the preheat tube deposit rating is less than
3 in Method B. In addition, the thermal stability referred herein
denotes a value measured according to JIS K2276 "Determination of
thermal oxidation stability of gas turbine fuels--JETOT method
Method A, Method B".
[0078] In order to prevent trouble due to the precipitation of a
dissolution water during exposure to a low temperature, the water
solubility of the aviation fuel oil composition of the present
invention is preferably that the separation state is 2 or less and
the interface state is 1 b or less. In addition, the water
solubility referred herein denotes a value measured according to
JIS K2276 "Determination of the water reaction of aviation
fules".
[0079] The aviation fuel oil base and aviation fuel oil composition
of the present invention, which contains an environment-friendly
base produced using an animal or vegetable oil and fat as a raw
material, are excellent in all of the combustibility, oxidation
stability and life cycle CO.sub.2 emission characteristics.
EXAMPLES
[0080] Hereinafter, the present invention will be described more
specifically based on Examples, but the present invention is not
limited by these examples.
[0081] (Preparation of Catalyst)
<Catalyst A>
[0082] A mixture was obtained by adding 18.0 g of sodium silicate
solution No. 3 to 3000 g of a sodium aluminate aqueous solution
having a concentration of 5 mass %, and the mixture was placed in a
vessel kept at a temperature of 65.degree. C. On the other hand, in
a separate vessel kept at a temperature of 65.degree. C., a
solution was prepared by adding 6.0 g of phosphoric acid
(concentration: 85%) to 3000 g of an aluminum sulfate aqueous
solution having a concentration of 2.5 mass %, and to the resulting
solution was added dropwise the solution containing sodium
aluminate. The addition of the solution was stopped when the
mixture solution reached pH 7.0. The resulting slurry product was
filtered off to obtain a slurry in a cake form.
[0083] The slurry in a cake form was transferred into a vessel
equipped with a reflux condenser, and to the vessel were added 150
ml of distilled water and 10 g of a 27% ammonia aqueous solution,
followed by heating and stirring at 75.degree. C. for 20 hours. The
slurry was placed in a kneading apparatus and kneaded while heating
at 80.degree. C. or higher to remove moisture, thereby obtaining a
clay-like kneaded product. The resulting kneaded product was
extruded by an extruder into a cylindrical shape having a diameter
of 1.5 mm, followed by drying at 110.degree. C. for one hour and
then calcining at 550.degree. C. to obtain a extruded support.
[0084] Into an eggplant-type flask were placed 50 g of the
resulting extruded support, followed by pouring an impregnation
solution containing 17.3 g of molybdenum trioxide, 13.2 g of nickel
(II) nitrate hexahydrate, 3.9 g of phosphoric acid (concentration:
85%) and 4.0 g of malic acid while deaerating with a rotary
evaporator. The impregnated sample was dried at 120.degree. C. for
one hour and then calcined at 550.degree. C. to obtain a catalyst
A. The physical properties of the catalyst A are shown in Table
1.
<Catalyst B>
[0085] Into an eggplant-type flask was placed 50 g of a
silica-alumina support having a silica/alumina ratio (mass ratio)
of 70:30, followed by pouring an aqueous solution of
tetraammineplatinum (II) chloride while deaerating with a rotary
evaporator. The impregnated sample was dried at 110.degree. C. and
then calcined at 350.degree. C. to obtain a catalyst B. In the
catalyst B, the amount supported of platinum was 0.5 mass % based
on the total amount of the catalyst. The physical properties of the
catalyst B are shown in Table 1.
Example 1
[0086] A feedstock A was prepared by adding dimethylsulfide to a
vegetable fat and oil 1 so that the sulfur content (in terms of
sulfur atom) is 10 mass ppm. The feedstock A was hydrotreated using
the catalyst A shown in Table 1 under the condition a shown in
Table 3. The hydrotreated oil was isomerized using the catalyst B
shown in Table 1 under the condition b shown in Table 3. A fraction
having a boiling range of 140 to 280.degree. C. obtained from the
isomerized oil after isomerization was used as a base 1. The
properties of the base 1 are shown in Table 4. An aviation fuel oil
composition 1 was prepared by mixing the base 1 with 30 vol % of a
catalytic cracking kerosene having the properties shown in Table 2
obtained from a fluid catalytic cracking apparatus.
Example 2
[0087] A feedstock B was prepared by adding dimethylsulfide to a
vegetable fat and oil 2 having the properties shown in Table 2 so
that the sulfur content (in terms of sulfur atom) is 10 mass ppm.
The feedstock B was hydrotreated using the catalyst A shown in
Table 1 under the condition c shown in Table 3. A fraction having a
boiling range of 140 to 280.degree. C. obtained from the
hydrotreated oil was isomerized using the catalyst B shown in Table
1 under the condition b shown in Table 3. The isomerizing oil after
isomerization was cut by distillation into a fraction having a
boiling range of 140 to 280.degree. C. to obtain a base 2. The
properties of the base 2 are shown in Table 4. An aviation fuel oil
composition 2 was prepared by mixing the base 2 with 30 vol % of a
hydrocracked kerosene having the properties shown in Table 2
obtained from a heavy oil hydrocracking apparatus.
Example 3
[0088] An aviation fuel oil composition 3 was prepared by mixing
the aviation fuel oil composition 2 described in Example 2 with 30
vol % of a petroleum-based aviation fuel oil base having the
properties shown in Table 2 obtained by refining a crude oil.
Comparative Example 1
[0089] Table 4 shows the properties of a fatty acid alkyl ester
obtained by esterifying the vegetable oil and fat 1 having the
properties shown in Table 2. These fatty acid alkyl esters are
methyl ester compounds obtained by the reaction with methanol, and
here, an ester exchange reaction was employed in which the oil and
fat was directly reacted with an alkyl alcohol by stirring for
approximately one hour at 70.degree. C. in the presence of an
alkali catalyst (sodium methylate) to obtain an ester compound. An
aviation fuel oil composition 4 was prepared by mixing the fatty
acid methyl ester compounds with 30 vol % of the catalytic cracking
kerosene described in Example 1.
Comparative Example 2
[0090] An aviation fuel oil composition 5 was prepared by mixing 70
vol % of the base 1 described in Example 1 and 30 vol % of a
petroleum-based aviation fuel oil base having the properties shown
in Table 2 obtained by refining a crude oil.
Comparative Example 3
[0091] A conventional representative commercially available
petroleum-based aviation fuel oil base was prepared as an aviation
fuel oil of Example 3.
[0092] In addition, in any of Examples 1 to 3 and Comparative
Examples 1 and 2, the following additives were added.
Antioxidant (2,6-ditertiary-butyl-phenol) 20 mass ppm (based on the
total amount of the fuel composition) Antistatic (STADIS 450) 2.0
mg/L (based on the total amount of the fuel composition)
[0093] (General Properties of Feedstock, Aviation Fuel Oil Base,
and Aviation Fuel Oil)
[0094] The general properties of the feedstock, aviation fuel oil
base and aviation fuel oil shown in Tables 2, 4 and 5 are values
measured by the following methods.
[0095] The density at 15.degree. C. (density @15.degree. C.) means
a value measured according to JIS K2249 "Crude Oil and Petroleum
Products--Determination of density and petroleum measurement tables
based on reference temperature (15.degree. C.)"
[0096] The kinematic viscosity at 30.degree. C. means a value
measured according to JIS K2283 "Crude petroleum and petroleum
products--Determination of kinematic viscosity".
[0097] Elemental analysis C (mass %) and P (mass %) means a value
measured according to ASTM D 5291 "Standard Test Methods for
Instrumental Determination of Carbon, Hydrogen and Nitrogen in
Petroleum Products and Lubricants".
[0098] The oxygen content means a value measured according to
UOP649-74 "Total Oxygen in Organic Materials by Pyrolysis-Gas
Chromatographic Technique" or the like.
[0099] The sulfur content means a value measured according to JIS
K2541 "Crude Oil and Petroleum Products--Determination of sulfur
content"
[0100] The acid value means a value measured according to JIS K2501
"Petroleum products and lublicants--Determination of neutralization
nunber".
[0101] The composition ratio of fatty acid groups in oil and fat
means a value determined according to the above-described Standard
Methods for the Analysis of Fats, Oils and Related Materials
(established by Japan Oil Chemists' Society) (1993) "2.4.21.3-77
Fatty Acid Composition (FID Temperature Programmed Gas
Chromatograph Method)".
[0102] The flash point means a value determined according to JIS
K2265 "Crude Oil and Petroleum Products--Determination of flash
point--Tag Closed Cup Method".
[0103] The distillation property is a value measured according to
JIS K2254 Petroleum Products--Determination of distillation
characteristics".
[0104] The aromatic content means a value measured according to JIS
K2536 "Liquid petroleum products--Testing method of components
(Fluorescent Indicator Adsorption Method)".
[0105] The total acid value is a value measured according to JIS
2276 "Petroleum Products--Aviation Fuels Test Method--Determination
of the Total Acid Value"
[0106] The freezing point means a value measured according to HS
2276 "Petroleum Products--Aviation Fuels Test Method--Determination
of the freezing point of aviation fuels"
[0107] The smoke point means a value measured according to JIS
K2537 "Petroleum products--Kerosine and aviation turbine
fuels--Determination of smoke point".
[0108] The thermal stability means a value measured according to
JIS K2276 "Petroleum Products--Determination of thermal oxidation
stability of gas turbine fuels--JETOT method Method A, Method
B".
[0109] The net heat of combustion means a value measured according
to JIS K2279 "Crude Oil and petroleum products--Determination of
heat of combustion".
[0110] The fuel consumption refers to a heating value per unit
volume and means a value calculated by multiplying the net heat of
combustion by the density.
[0111] (Life Cycle Characteristics)
[0112] The life cycle characteristics (life cycle CO.sub.2
calculation) described in the present Example were calculated by
the following method.
[0113] The life cycle CO.sub.2 was calculated separately as the
CO.sub.2 generated accompanied by the flying (combustion of fuels)
of an airplane using aviation fuels and as CO.sub.2 generated from
crude oil drilling to fuel feeding in the fuel production.
[0114] The CO.sub.2 generated accompanied by combustion
(hereinafter referred to as "Tank to Wheel CO.sub.2" was converted
into the emissions per unit heating value using the value defined
by Ministry of the Environment (jet fuel: 2.5 kg-CO.sub.2/L) and
used. In addition, the CO.sub.2 generated from drilling to fuel
feeding (hereinafter referred to as "Well to Tank CO.sub.2") was
calculated as the total CO.sub.2 emissions during the sequence from
the drilling of raw materials and crude oil resources through
transportation, processing and delivery to pumping to a vehicle's
gas tank. In addition, in calculating "Well to Tank CO.sub.2", the
calculation was carried out in consideration of the carbon dioxide
emissions shown in the following (1B) to (5B). As the data required
for the calculation, the oil refinery operation performance data
possessed by the present inventors was used.
(1B) Carbon dioxide emissions accompanied by the use of fuel for
facilities such as various treatment apparatuses and boilers (2B)
Carbon dioxide emissions accompanied by reforming reaction in a
hydrogen producing apparatus, in the treatment using hydrogen (3B)
Carbon dioxide emissions accompanied by catalyst regeneration when
the regeneration is carried out through an apparatus involving
continuous catalyst regeneration of a catalytic cracking apparatus
or the like (4B) Carbon dioxide emissions when an aviation fuel oil
composition was produced or shipped at Yokohama, delivered Yokohama
to Sendai, and pumped to a vehicle's gas tank in Sendai (5B) Carbon
dioxide emissions if animal and vegetable oils and fats and
components derived from animal and vegetable oils and fats are
obtained from Malaysia and the surrounding regions and an aviation
fuel oil composition is produced in Yokohama
[0115] In addition, if animal and vegetable oils and fats and
components derived from animal and vegetable oils and fats are
used, in the so-called Kyoto Protocol, a rule is applied in which
carbon dioxide emissions resulting from the combustion of these
fuels are not calculated as emissions. In this calculation, this
rule was applied to "Tank to Wheel CO.sub.2" generated during
combustion.
[0116] As is clear from Table 5, an aviation fuel oil, which
contains an aviation fuel oil base obtained by hydrotreating raw
materials derived from animal and vegetable oils and fats, has
general properties including fuel consumption equivalent to those
of a representative petroleum-based aviation fuel oil, whereas the
aviation fuel oil has excellent life cycle characteristics and is a
new aviation fuel oil alternative to petroleum which contributes to
the prevention of global warming.
TABLE-US-00001 TABLE 1 Catalyst A Catalyst B Content
Al.sub.2O.sub.3 (mass %, based on support mass) 91.2 30 Content
SiO.sub.2 (mass %, based on support mass) 4.8 70 Content
P.sub.2O.sub.5 (mass %, based on support mass) 4.0 0 Content
MoO.sub.3 (mass %, based on catalyst mass) 24.0 0 Content NiO (mass
%, based on catalyst mass) 2.6 0 Content Pt (mass %, based on
catalyst mass) 0 0.5 Pore Volume (ml/g) 0.75 0.47 Average Pore
Diameter (nm) 7.0 5.2 Ratio of Pore Volume derived from Pores
having a 22 39 pore diameter of 3 nm or less to Total Pore Volume
(% by volume)
TABLE-US-00002 TABLE 2 Vegetable Vegetable Petroleum- Catalytic Oil
and Fat 1 Oil and Fat based Aviation Hydrocracked Cracked (coconut
oil) 2 (palm oil) Fuel oil Base Kerosene Kerosene Density at
15.degree. C. (kg/m.sup.3) 900 916 792 821 830 Kinematic Viscosity
at 30.degree. C. (mm.sup.2/s) -- -- 1.4 1.6 1.1 Elemental Analysis
C (mass %) 77.0 77.3 85.4 85.8 86.2 H (mass %) 12.6 12.0 14.5 14.1
13.7 Distillation T10 (.degree. C.) -- -- 168.0 177.0 149.0
Characteristics T50 (.degree. C.) -- -- 197.5 209.0 184.5 T90
(.degree. C.) -- -- 244.0 246.5 227.0 Aromatic Content (% by
volume) -- -- 17 24 21 Oxygen Content (% by mass) 11.5 10.6 <0.1
<0.1 <0.1 Sulfur Content (ppm by mass) <1 <1 3 2 190
Acid Value (mg KOH/g) 0.10 0.07 0.00 0.00 0.00 Component Ratio
Butyric Acid 0 0 -- -- -- (mass %) of Fatty Group (C3) Acid Groups
in Oil Caproic Acid 0 0 -- -- -- and Fat (number of Group (C5)
carbon atoms in Caprylic Acid 4 0 -- -- -- fatty acid carbon Group
(C7) chain in Capric Acid 4 0 -- -- -- Parentheses) Group (C9)
Lauric Acid 49 0 -- -- -- Group (C11) Myristic Acid 17 1 -- -- --
Group (C13) Palmitic Acid 9 44 -- -- -- Group (C14) Stearic Acid 3
5 -- -- -- Group (C16) Oleic Acid 7 39 -- -- -- Group (C17)
Linoleic Acid 2 10 -- -- -- Group (C17) Linolenic Acid 0 0 -- -- --
Group (C17)
TABLE-US-00003 TABLE 3 Condition Condition Condition a b c Recycled
Amount fold by mass 1 -- 1 Reaction Temperature .degree. C. 280 340
360 (Average temperature of Catalyst Layer) Hydrogen Pressure MPa 6
3 10 LHSV h.sup.-1 1.0 1.0 0.5 With or Without Yes -- Yes Quenching
Addition Amount of ppm by mass 10 -- 10 Sulfur-Containing
Hydrocarbon Compound (to Feedstock)
TABLE-US-00004 TABLE 4 Fatty Acid Base 1 Base 2 Alkyl (Hydrotreated
(Hydrotreated Ester of Oil of Oil of Vegetable Vegetable Oils
Vegetable Oils Oils and Fats 1) and Fats 2) and Fats 1 Density at
15.degree. C. kg/m.sup.3 750 780 874 Flash Point .degree. C. 85 75
181 distillation T10 .degree. C. 202.0 149.5 335.0 Character- T50
.degree. C. 225.0 168.0 354.0 istic T90 .degree. C. 238.0 254.0
359.0 EP .degree. C. 258.0 273.5 -- Sulfur Content ppm by <1
<1 <1 mass Aromatic Content % by 0 0 0 volume Total Acid
Value mg 0.00 0.00 0.00 KOH/g Freezing .degree. C. -47 -40 15.0
Point .degree. C.
TABLE-US-00005 TABLE 5 Comp. Comp. Comp. Ex. 1 Ex. 2 Ex. 3 Ex. 1
Ex. 2 Ex. 3 Density at 15.degree. C. kg/m.sup.3 774 792 792 861 763
788 Flash Point .degree. C. 71 66 61 93 68 46 Distillation T10
.degree. C. 173.5 152.0 170.0 179.5 170.5 166.5 Characteristics T50
.degree. C. 200.0 177.5 198.5 280.5 210.0 191.5 T90 .degree. C.
228.0 245.0 230.5 340.5 231.5 231.5 EP .degree. C. 255.0 270.0
251.0 355.0 250.0 251.5 Sulfur Content ppm by mass 58 1 2 55 3 4
Aromatic Content % by volume 7 8 11 8 6 17 Net Heat of Combustion
J/g 43860 43660 43570 42880 43510 43400 Total Acid Value mg KOH/g
0.00 0.00 0.00 0.25 0.01 0.01 Freezing Point .degree. C. -49 -48
-50 -12 -47 -49 Smoke Point mm 38 40 32 25 40 25 Thermal Filer
Pressure Kpa 1 1 1 28 1 1 Oxidation Drop Stability Tube Deposits 1b
1b 1b 3 1b 1b Rating Fuel Consumption (Calorific kJ/L 33950 34580
34500 36920 33200 34200 Value per unit volume) Life Cycle
Characteristics g-CO.sub.2/MJ 68.0 65.2 61.0 68.8 65.0 81.3
(WtW--CO.sub.2 emissions)
* * * * *