DESCRIPTION
CATALYST FOR PRODUCING MONOCYCLIC AROMATIC HYDROCARBONS,
AND METHOD FOR PRODUCING MONOCYCLIC AROMATIC
HYDROCARBONS
TECHNICAL FIELD
[0001]
The present invention relates to a catalyst for producing monocyclic aromatic
hydrocarbons and a method for producing monocyclic aromatic hydrocarbons that are
used for producing monocyclic aromatic hydrocarbons fi-om an oil containing a large
amount of polycyclic aromatic hydrocarbons.
Priority is claimed on Japanese Patent Application No. 2009-176656, filed July
29, 2009, the content of which is incorporated herein by reference.
BACKGROUND ART
[0002]
Light cycle oil (hereinafter also referred to as LCO), which is a cracked gas oil
produced in a fluid catalytic cracking, contains a large amount of polycyclic aromatic
hydrocarbons, and has been used as a gas oil or a heating oil. However, in recent years,
investigations have been conducted into the possibilities of obtaining, from LCO,
monocyclic aromatic hydrocarbons of 6 to 8 carbon number (such as benzene, toluene,
xylene and ethylbenzene), which can be used as high-octane gasoline base stocks or
petrochemical feedstocks, and offer significant added value.
2
For example, Patent Documents 1 to 3 propose methods that use zeohte catalysts
to produce monocyclic aromatic hydrocarbons from the polycyclic aromatic
hydrocarbons contained in large amounts within LCO and the like.
However, in the production of monocyclic aromatic hydrocarbons of 6 to 8
carbon number using the catalysts disclosed in Patent Documents 1 to 3, the yield of
monocyclic aromatic hydrocarbons of 6 to 8 carbon number during the initial stages of
reaction were not entirely satisfactory. Further, the steady-state yield of monocyclic
aromatic hydrocarbons of 6 to 8 carbon number has also tended to be low.
[0003]
When monocyclic aromatic hydrocarbons are produced from a heavy feedstock
oil containing polycyclic aromatic hydrocarbons, large amounts of carbon matter are
deposited on the catalyst, causing a rapid deterioration in the catalytic activity, and
therefore a catalyst regeneration process that removes this carbon matter must be
performed frequently. Further, in those cases where a circulating fluidized bed is
employed, which is a process in which the reaction and catalyst regeneration are repeated
in an efficient manner, the temperature for the catalyst regeneration must be set to a
higher temperature than the reaction temperature, resulting in a particularly severe
temperature envirormient for the catalyst.
Under these types of severe conditions, if a zeolite catalyst is used as the catalyst,
then the catalyst tends to suffer from hydrothermal degradation, causing a reduction in
the steady-state yield of the monocyclic aromatic hydrocarbons, and therefore
improvements in the hydrothermal stability of the catalyst are required. However, the
zeolite catalysts disclosed in Patent Documents 1 to 3 employ no measures to improve
the hydrothermal stability, and offer very little practical usability.
3
[0004]
Examples of known methods for improving the hydrothermal stabihty include a
method that uses a zeolite having a high Si/Al ratio, a method in which the catalyst is
subjected to a preliminary hydrothermal treatment to stabilize the catalyst, such as USY
zeolite, a method in which phosphorus is added to a zeolite, a method in which a rare
earth metal is added to a zeolite, and a method that involves improving the structuredirecting
agent used during the synthesis of a zeolite.
Of these methods, the addition of phosphorus not only improves the hydrothermal
stability, but also provides other known effects such as an improvement in selectivity due
to suppression of carbon matter deposition during fluid catalytic cracking, and an
improvement in the abrasion resistance of the binder. Accordingly, this method is
frequently applied to catalysts used in catalytic cracking reactions.
Examples of catalytic cracking catalysts prepared by adding phosphorus to a
zeolite include those disclosed in Patent Documents 4 to 6.
Namely, Patent Document 4 discloses a method for producing olefins fi-om
naphtha using a catalyst containing ZSM-5 to which has been added phosphorus, as well
as gallium, germanium and/or tin. Li Patent Document 4, phosphorus is added for the
purposes of suppressing the production of methane and aromatics in order to enhance the
selectivity for olefin production, and ensuring a high degree of activity even for a short
contact time, thereby improving the yield of olefins.
Patent Document 5 discloses a method for producing olefins in a high yield from
heavy hydrocarbons by using a catalyst prepared by supporting phosphorus on ZSM-5
containing zirconi\im and a rare earth element, and a catalyst containing a USY zeolite,
an REY zeolite, kaolin, silica and alumina.
4
Patent Document 6 discloses a method for producing ethylene and propylene in a
high yield by transforming hydrocarbons using a catalyst containing ZSM-5 having
phosphorus and a transition metal element support thereon.
[0005]
As mentioned above, the addition of phosphorus to zeolites has been disclosed in
Patent Documents 4 to 6, but in each of these documents, the main purpose was
improvement of the olefin yield, and monocyclic aromatic hydrocarbons of 6 to 8 carbon
number were not able to be produced at high yield. For example. Table 2 in Patent
Document 6 discloses the yields for olefins (ethylene and propylene) and BTX (benzene,
toluene and xylene), and whereas the yield for the olefins was 40% by mass, the yield for
BTX was a low value of approximately 6% by mass.
Accordmgly, a catalyst for producing monocyclic aromatic hydrocarbons that is
capable of producing monocyclic aromatic hydrocarbons of 6 to 8 carbon number in a
high yield from a feedstock oil containing polycyclic aromatic hydrocarbons, not only
during the initial reaction but also under steady-state conditions, is not currently known.
DOCUMENTS OF RELATED ART
PATENT DOCUMENTS
[0006]
[Patent Document 1]
Japanese Unexamined Patent Application, First Publication No. Hei 3-2128
[Patent Document 2]
Japanese Unexamined Patent Application, First Publication No. Hei 3-52993
[Patent Document 3]
5'
Japanese Unexamined Patent Application, First Publication No. Hei 3-26791
[Patent Document 4]
Published Japanese Translation No. 2002-525380 of PCT
[Patent Document 5]
Japanese Unexamined Patent Application, First*Publication No. 2007-190520
[Patent Document 6]
Published Japanese Translation No. 2007-530266 of PCT
SUMMARY OF INVENTION
PROBLEMS TO BE SOLVED BY THE INVENTION
[0007]
An object of the present invention is to provide a catalyst for producing
monocyclic aromatic hydrocarbons and a method for producing monocyclic aromatic
hydrocarbons that are capable of producing monocyclic aromatic hydrocarbons of 6 to 8
carbon number in a high yield from a feedstock oil containing polycyclic aromatic
hydrocarbons, not only during the initial reaction but also under steady-state conditions.
MEANS TO SOLVE THE PROBLEMS
[0008]
[1] A catalyst for producing monocyclic aromatic hydrocarbons, used for producing
monocyclic aromatic hydrocarbons of 6 to 8 carbon number from a feedstock oil having
a 10 volume % distillation temperature of at least 140°C and an end point temperature of
not more than 400°C, wherein
6
the catalyst contains a crystalline aluminosilicate, gallium and/or zinc, and
phosphorus, the molar ratio between silicon and aluminum (Si/Al ratio) in the crystalline
aluminosilicate is not more than 100, the molar ratio between the phosphorus supported
on the crystalline aluminosilicate and the aluminum of the crystalline aluminosilicate
(P/Al ratio) is not less than 0.01 and not more than 1.0, and the amount of gallium and/or
zinc is not more than 1.2% by mass based on the mass of the crystalline aluminosilicate.
[2] The catalyst for producing monocyclic aromatic hydrocarbons according to [1],
wherein the amount of phosphorus is within a range from 0.1 to 10% by mass based on
the total mass of the catalyst, and the amount of gallium and/or zinc contained within the
catalyst is not more than 2% by mass based on the total mass of the catalyst.
[3] The catalyst for producing monocyclic aromatic hydrocarbons according to [1] or
[2], wherein the crystalline aluminosilicate is a pentasil-type zeolite.
[4] The catalyst for producing monocyclic aromatic hydrocarbons according to any
one of [1] to [3], wherein the crystalline aluminosilicate is an MFI-type zeolite.
[5] The catalyst for producing monocyclic aromatic hydrocarbons according to any
one of [1] to [4], wherein the molar ratio between the phosphorus supported on the
crystalline aluminosilicate and the aluminum of the crystalline aluminosilicate (P/Al
ratio) is not more than 0.5.
[6] The catalyst for producing monocyclic aromatic hydrocarbons according to any
one of [1] to [5], wherein the amount of gallium and/or zinc is not more than 1.0% by
mass based on the mass of the crystalline aluminosilicate.
[7] A method for producing monocyclic aromatic hydrocarbons of 6 to 8 carbon
number, the method including bringing a feedstock oil having a 10 volume % distillation
temperature of at least 140°C and an end point temperature of not more than 400°C into
7
contact with the catalyst for producing monocyclic aromatic hydrocarbons according to
any one of [1] to [5].
[8] A method for producing monocyclic aromatic hydrocarbons of 6 to 8 carbon
niimber, the method including bringing a feedstock oil having a 10 volume % distillation
temperature of at least 140°C and a 90 volume % distillation temperature of not more
than 350°C into contact with the catalyst for producing monocyclic aromatic
hydrocarbons according to any one of [1] to [5].
[9] The method for producing monocyclic aromatic hydrocarbons of 6 to 8 carbon
number according to [7] or [8], wherein a cracked gas oil produced in a fluid catalytic
cracking is used as the feedstock oil.
[10] The method for producing monocyclic aromatic hydrocarbons of 6 to 8 carbon
number according to any one of [7] to [9], wherein the feedstock oil is brought into
contact with the catalyst for producing monocyclic aromatic hydrocarbons in a fluidized
bed reactor.
EFFECT OF THE INVENTION
[0009]
The catalyst for producing monocyclic aromatic hydrocarbons and the method for
producing monocyclic aromatic hydrocarbons of 6 to 8 carbon number according to the
present invention enable the production of monocyclic aromatic hydrocarbons of 6 to 8
carbon atoms in a high yield from a feedstock oil containing polycyclic aromatic
hydrocarbons. Moreover, the yield of monocyclic aromatic hydrocarbons of 6 to 8
carbon number is high even under steady-state conditions.
8
DESCRIPTION OF EMBODIMENTS
[0010]
(Catalyst for producing monocyclic aromatic hydrocarbons)
The catalyst for producing monocyclic aromatic hydrocarbons according to the
present invention (hereinafter often referred to as "the catalyst") is used for producing
monocyclic aromatic hydrocarbons of 6 to 8 carbon number (hereinafter often
abbreviated as "monocyclic aromatic hydrocarbons") from a feedstock oil containing
polycyclic aromatic hydrocarbons, and contains a crystalline aluminosilicate, gallium
and/or zinc, and phosphorus.
[0011]
[Crystalline aluminosilicate]
Although there are no particular limitations on the crystalline aluminosilicate,
medium pore size zeolites such as zeolites with MFI, MEL, TON, MTT, MRE, PER,
AEL and EUO type crystal structures are preferred, and in terms of maximizing the yield
of monocyclic aromatic hydrocarbons, pentasil-type zeolites are more preferred, and
zeolites with MPI-type and/or MEL-type crystal structures are particularly desirable.
MFI-type and MEL-type zeolites are included within the conventional zeolite
structures published by The Structure Commission of the International Zeolite
Association (Atlas of Zeolite Structure Types, W. M. Meiyer and D. H. Olson (1978),
distributed by Polycrystal Book Service, Pittsburgh, PA (USA).
The amount of the crystalline aluminosilicate within the catalyst, relative to a
value of 100% for the entire catalyst, is preferably within a range from 10 to 95% by
mass, more preferably from 20 to 80% by mass, and still more preferably from 25 to
70% by mass. Provided the amount of the crystalline aluminosilicate is not less than
9
10% by mass and not more than 95% by mass, a satisfactorily high level of catalytic
activity can be achieved.
[0012]
In the crystalline aluminosilicate, the molar ratio between silicon and aluminum
(Si/Al ratio) is not more than 100, and is preferably not more than 50. If the Si/Al ratio
of the crystalline aluminosilicate exceeds 100, then the yield of monocyclic aromatic
hydrocarbons tends to decrease.
Further, in terms of maximizing the yield of monocyclic aromatic hydrocarbons,
the Si/Al ratio of the crystalline aluminosilicate is preferably at least 10.
[0013]
[Gallium]
Examples of the form of the gallium contained within the catalyst of the present
invention include catalysts in which the gallium is incorporated within the lattice
framework of the crystalline aluminosilicate (crystalline aluminogallosilicates), catalysts
in which gallium is supported on the crystalline aluminosilicate (gallium-supporting
crystalline aluminosilicates), and catalysts including both of these forms.
A crystalline aluminogallosilicate has a structure in which Si04, AIO4 and Ga04
structures adopt tetrahedral coordination within the framework. A crystalline
aluminogallosilicate can be obtained, for example, by gel crystallization via
hydrothermal synthesis, by a method in which gallium is inserted into the lattice
framework of a crystalline aluminosilicate, or by a method in which aluminiim is inserted
into the lattice framework of a crystalline gallosilicate.
A gallium-supporting crystalline alxrminosilicate can be obtained by supporting
gallium on a crystalline aluminosilicate using a conventional method such as an ion10
exchange method or impregnation method. There are no particular limitations on the
gallium source used in these methods, and examples include gallium salts such as
gallium nitrate and gallium chloride, and gallium oxide.
[0014]
The amount of gallium within the catalyst of the present invention, relative to a
value of 100% for the total mass of the crystalline aluminosilicate, is typically not more
than 1.2% by mass, preferably not more than 1.0% by mass, still more preferably not
more than 0.8%) by mass, and most preferably not more than 0.5%) by mass. If the
amount of gallium exceeds 1.2%) by mass, then the yield of monocyclic aromatic
hydrocarbons tends to decrease.
Further, the amount of gallium within the catalyst of the present invention,
relative to a value of 100%) for the total mass of the crystalline aluminosilicate, is
preferably not less than 0.01%) by mass, and more preferably 0.1%) by mass or greater. If
the amount of gallium is less than 0.01%) by mass, then the yield of monocyclic aromatic
hydrocarbons may decrease.
[0015]
[Zinc]
Examples of the form of the zinc contained within the catalyst of the present
invention include catalysts in which the zinc is incorporated within the lattice framework
of the crystalline aluminosilicate (crystalline aluminozincosilicates), catalysts in which
zinc is supported on the crystalline aluminosilicate (zinc-supporting crystalline
aluminosilicates), and catalysts including both of these forms.
A crystalline aluminozincosilicate has a structure in which Si04, AIO4 and Zn04
structures exist within the framework. A crystalline aluminozincosilicate can be
11
obtained, for example, by gel crystallization via hydrothermal synthesis, by a method in
which zinc is inserted into the lattice framework of a crystalline aluminosilicate, or by a
method in which aluminum is inserted into the lattice framework of a crystalline
zmcosilicate.
A zinc-supporting crystalline aluminosilicate can be obtained by supporting zinc
on a crystalline aluminosilicate using a conventional method such as an ion-exchange
method or impregnation method. There are no particular limitations on the zinc source
used in these methods, and examples include zinc salts such as zinc nitrate and zinc
chloride, and zinc oxide.
[0016]
The amount of zinc within the catalyst of the present invention, relative to a value
of 100% for the total mass of the crystalline aluminosilicate, is typically not more than
1.2% by mass, preferably not more than 1.0% by mass, still more preferably not more
than 0.8% by mass, and most preferably not more than 0.7%) by mass. If the amount of
zinc exceeds 1.2%) by mass, then the yield of monocyclic aromatic hydrocarbons tends to
decrease.
Further, the amount of zinc, relative to a value of 100%) for the total mass of the
crystalline aluminosilicate, is preferably not less than 0.0l%o by mass, and more
preferably 0.1%) by mass or greater. If the amount of zinc is less than 0.01%) by mass,
then the yield of monocyclic aromatic hydrocarbons may decrease.
[0017]
The catalyst of the present invention may be a catalyst that contains either one of
gallium or zinc, or a catalyst that contains both gallium and zinc. Further, the catalyst
may also contain one or more other metals in addition to the gallium and/or zinc.
12
[0018]
[Phosphorus]
The molar ratio between the phosphorus supported on the crystalline
aluminosilicate and the aluminiim contained within the crystalline aluminosilicate (P/Al
ratio) is not more than 1.0, and is preferably 0.5 or less. If the P/Al ratio exceeds 1.0,
then the yield of monocyclic aromatic hydrocarbons tends to decrease.
Further, the P/Al ratio is typically at least 0.01. If the P/Al ratio is less than 0.01,
then the steady-state yield of monocyclic aromatic hydrocarbons may decrease, which is
undesirable.
[0019]
There axe no particular limitations on the method used for incorporating the
phosphorus within the catalyst of the present invention, and examples include methods in
which an ion-exchange method or impregnation method or the like is used to support
phosphorus on a crystalline aluminosilicate, crystalline aluminogallosilicate or crystalline
aluminozincosilicate, methods in which a phosphorus compound is added during
synthesis of the zeolite, thereby substituting a portion of the internal framework of the
crystalline aluminosilicate with phosphorus, and methods in which a crystallization
promoter containing phosphorus is used during synthesis of the zeolite. Although there
are no particular limitations on the phosphate ion-containing aqueous solution used
during the above methods, a solution prepared by dissolving phosphoric acid,
diammonium hydrogen phosphate, ammonium dihydrogen phosphate or another watersoluble
phosphate salt in water at an arbitrary concentration can be used particularly
favorably.
[0020]
13
The catalyst of the present invention can be obtained by calcining (at a
calcination temperature of 300 to 900°C) an above-mentioned phosphorus-supporting
crystalline aluminogallosilicate or crystalline aluminozincosilicate, or a crystalline
aluminosilicate having gallium/zinc and phosphorus supported thereon.
[0021]
[Form]
The catalyst of the present invention is used in the form of a powder, granules or
pellets or the like, depending on the reaction format. For example, a powder is used in
the case of a fluidized bed, whereas granules or pellets are used in the case of a fixed bed.
The average particle size of the catalyst used in a fluidized bed is preferably within a
range from 30 to 180 p,m, and more preferably from 50 to 100 |j.m. Further, the bulk
density of the catalyst used in a fluidized bed is preferably within a range from 0.4 to 1.8
g/cc, and more preferably from 0.5 to 1.0 g/cc.
The average particle size describes the particle size at which the particle size
distribution obtained by classification using sieves reaches 50% by mass, whereas the
bulk density refers to the value measured using the method prescribed in JIS R 9301-2-3.
In order to obtain a catalyst in granular or pellet form, if necessary, an inert oxide
may be added to the catalyst as a binder or the like, with the resulting mixture then
molded using any of various molding apparatus.
[0022]
In those cases where the catalyst of the present invention contains an inorganic
oxide such as a binder, a compound that contains phosphorus may also be used as the
binder.
14
Further, in those cases where the catalyst contains an inorganic oxide such as a
binder, the catalyst may be produced by mixing the binder and the crystalline
aluminosilicate, and subsequently adding the gallium and/or zinc and the phosphorus, or
by mixing the binder and the gallium- and/or zinc-supporting crystalline aluminosilicate,
or mixing the binder and the crystalline aluminogallosilicate and/or crystalline
aluminozincosilicate, and subsequently adding the phosphorus.
In those cases where the catalyst contains an inorganic oxide such as a binder, the
amount of phosphorus relative to the total mass of the catalyst is preferably within a
range from 0.1 to 10% by mass. Further, the lower limit for this range is more preferably
at least 0.2% by mass, whereas the upper limit is more preferably not more than 5.0%) by
mass, and still more preferably not more than 2.0%) by mass. By ensuring that the
amount of phosphorus is at least 0.1% by mass of the total mass of the catalyst,
deterioration over time in the yield of the monocyclic aromatic hydrocarbons can be
prevented. On the other hand, ensuring that the amount of phosphorus is not more than
10% by mass means that the yield of the monocyclic aromatic hydrocarbons can be
increased.
Further, in those cases where the catalyst contains an inorganic oxide such as a
binder, the amount of gallium and/or zinc relative to the total mass of the catalyst is
preferably not more than 1% by mass, more preferably not more than 1.5% by mass, and
still more preferably not more than 1.2%o by mass. If the amount of gallium and/or zinc
exceeds 2% by mass based on the total mass of the catalyst, then the yield of monocyclic
aromatic hydrocarbons tends to decrease, which is undesirable.
[0023]
(Method for producing monocyclic aromatic hydrocarbons)
15
The method for producing monocycUc aromatic hydrocarbons according to the
present invention involves bringing a feedstock oil into contact with the abovementioned
catalyst to effect reaction.
In this reaction, saturated hydrocarbons function as hydrogen donor sources, and
a hydrogen transfer reaction from the saturated hydrocarbons is used to convert
polycyclic aromatic hydrocarbons into monocyclic aromatic hydrocarbons.
[0024]
[Feedstock oil]
The feedstock oil used in the present invention is preferably either an oil having a
10 volume % distillation temperature of at least 140°C and an end point temperature of
not more than 400°C, or an oil having a 10 volume % distillation temperature of at least
140°C and a 90 volume % distillation temperature of not more than 360°C. With an oil
having a 10 volume % distillation temperature of less than 140°C, the reaction involves
production of BTX from light compounds, which is outside the scope of the present
invention, and therefore the 10 volume % distillation temperature is preferably at least
140°C, and more preferably 150°C or higher. Further, if an oil having an end point
temperature exceeding 400°C is used, then not only is the yield of monocyclic aromatic
hydrocarbons low, but the amount of coke deposition on the catalyst also tends to
increase, causing a more rapid deterioration in the catalytic activity, and therefore the end
point temperature of the feedstock oil is preferably not more than 400°C, and more
preferably 380°C or lower. Furthermore, if a feedstock oil having a 90 volume %
distillation temperature that exceeds 360°C is used, then the amount of coke deposition
on the catalyst tends to increase, causing a more rapid deterioration in the catalytic
16
activity, and therefore the 90 volume % distillation temperature for the feedstock oil is
preferably not more than 360°C, and more preferably 350°C or lower.
In this description, the 10 volume % distillation temperature, the 90 volume %
distillation temperature and the end point temperature refer to values measured in
accordance with the methods prescribed in JIS K 2254 "Petroleum products -
determination of distillation characteristics".
Examples of feedstock oils having a 10 volume % distillation temperature of at
least 140°C and an end point temperature of not more than 400°C, or feedstock oils
having a 10 volume % distillation temperature of at least 140°C and a 90 volume %
distillation temperature of not more than 360°C include cracked gas oil (LCO) produced
in a fluid catalj^tic cracking, coal liquefaction oil, hydrocracked oil from heavy oils,
straight-run kerosene, straight-run gas oil, coker kerosene, coker gas oil, and
hydrocracked oil from oil sands.
Further, if the feedstock oil contains a very large amount of polycyclic aromatic
hydrocarbons, then the yield of monocyclic aromatic hydrocarbons of 6 to 8 carbon
number tends to decrease, and therefore the amount of polycyclic aromatic hydrocarbons
(the polycyclic aromatic content) within the feedstock oil is preferably not more than 50
volume %, and more preferably 30 volume % or less.
In this description, the polycyclic aromatic content describes the combined total
of the amount of bicyclic aromatic hydrocarbons (the bicyclic aromatic content) and the
amount of tricyclic and higher aromatic hydrocarbons (the tricyclic and higher aromatic
content) measured in accordance with JPI-5S-49 "Petroleum Products -Determination of
Hydrocarbon Types - High Performance Liquid Chromatography".
[0025]
17
[Reaction format]
Examples of the reaction format used for bringing the feedstock oil into contact
with the catalyst for reaction include fixed beds, moving beds and fluidized beds. In the
present invention, because a heavy oil fraction is used as the feedstock, a fluidized bed is
preferred as it enables the coke fraction adhered to the catalyst to be removed in a
continuous manner and enables the reaction to proceed in a stable manner. A continuous
regeneration-type fluidized bed, in which the catalyst is circulated between the reactor
and a regenerator, thereby continuously repeating a reaction-regeneration cycle, is
particularly desirable. The feedstock oil that makes contact with the catalyst is
preferably in a gaseous state. Further, the feedstock may be diluted with a gas if required.
Fiirthermore, in those cases where unreacted feedstock occurs, this may be recycled as
required.
[0026]
[Reaction temperature]
Although there are no particular limitations on the reaction temperature during
contact of the feedstock oil with the catalyst for reaction, a reaction temperature of 350 to
700°C is preferred. In terms of achieving satisfactory reactivity, the lower limit is more
preferably 450°C or higher. On the other hand, an upper limit temperature of not more
than 650°C is preferable, as it is not only more advantageous from an energy perspective,
but also enables ready regeneration of the catalyst.
[0027]
[Reaction pressure]
The reaction pressure during contact of the feedstock oil with the catalyst for
reaction is preferably not more than 1.0 MPaG. Provided the reaction pressure is not
18
more than 1.0 MPaG, the generation of by-product light gases can be prevented, and the
pressure resistance required for the reaction apparatus can be lowered.
[0028]
[Contact time]
There are no particular limitations on the contact time between the feedstock oil
and the catalyst, provided the desired reaction proceeds satisfactorily, but in terms of the
gas transit time across the catalyst, a time of 1 to 300 seconds is preferred. The lower
limit for this time is more preferably at least 5 seconds, and the upper limit is more
preferably 150 seconds or less. Provided the contact time is at least 1 second, a reliable
reaction can be achieved, whereas provided the contact time is not more than 300
seconds, deposition of carbon matter on the catalyst due to coking or the like can be
suppressed. Further, the amount of light gas generated by cracking can also be
suppressed.
[0029]
In the method for producing monocyclic aromatic hydrocarbons according to the
present invention, hydrogen transfer occurs from saturated hydrocarbons to the
polycyclic aromatic hydrocarbons, and the polycyclic aromatic hydrocarbons undergo
partial hydrogenation and ring opening, yielding monocyclic aromatic hydrocarbons.
In the present invention, the yield of monocyclic aromatic hydrocarbons in the
initial reaction is preferably at least 25% by mass, more preferably at least 30% by mass,
and still more preferably 35% by mass or greater.
Further, the steady-state yield of monocyclic aromatic hydrocarbons is preferably
at least 20% by mass, more preferably at least 25% by mass, and still more preferably
30% by mass or greater.
19
If the yield of monocyclic aromatic hydrocarbons during the initial reaction is
less than 25% by mass, or the steady-state yield of monocyclic aromatic hydrocarbons is
less than 20% by mass, then the concentration of monocyclic aromatic hydrocarbons
within the reaction product is low, and the efficiency with which those compounds can
be recovered tends to deteriorate.
[0030]
In the above-mentioned production method of the present invention, because the
catalyst described above is used, monocyclic aromatic hydrocarbons can be produced in
a high yield, both during the initial reaction and under steady-state conditions.
EXAMPLES
[0031]
The present invention is described in more detail below based on a series of
examples and comparative examples, but the present invention is in no way limited by
these examples.
[0032]

(Catalyst preparation example 1)
120 g of a proton-type crystalline aluminosilicate having an MFI structure and a
silicon/aluminum molar ratio (Si/Al ratio) of 15 was impregnated with 120 g of a 1.15%
by mass aqueous solution of gallium nitrate octahydrate in order to support 0.2% by mass
of gallium on the aluminosilicate (based on a value of 100%o for the total mass of the
crystalline aluminosilicate), and the resulting product was then dried at 120°C.
20
Subsequently, the product was calcined for 3 hours at 780°C under a stream of air,
yielding a gallium-supporting crystalline aluminosilicate.
Subsequently, 30 g of the obtained gallium-supporting crystalline aluminosilicate
was impregnated with 30 g of a 3.20% by mass aqueous solution of diammonium
hydrogen phosphate, and the resulting product was then dried at 120°C. Subsequently,
the product was calcined for 3 hours at 780°C imder a stream of air, yielding a catalyst
containing the crystalline aluminosilicate, gallium and phosphorus.
Tablet molding was performed by applying a pressure of 39.2 MPa (400 kgf) to
the obtained catalyst, and the resulting tablets were subjected to coarse crushing and then
classified using a 20 to 28 mesh size, thus yielding a granular catalyst 1 (hereinafter
referred to as the "granulated catalyst 1"). The Si/Al ratio within the granulated catalyst
1 was 15, the molar ratio between phosphorus and aluminum (P/Al ratio) was 0.23, and
the amount of gallium (based on a value of 100% for the total mass of the crystalline
aluminosilicate) was 0.2% by mass.
[0033]
(Catalyst preparation example 2)
With the exception of preparing a gallium-supporting crystalline aluminosilicate
using a proton-type crystalline aluminosilicate having an MFI structure and a
silicon/aluminum molar ratio (Si/Al ratio) of 35, and then impregnating 30 g of the thus
obtained gallium-supporting crystalline aluminosiUcate with 30 g of a 1.40% by mass
aqueous solution of diammonium hydrogen phosphate, a granular catalyst 2 (hereinafter
referred to as the "granulated catalyst 2") was obtained in the same manner as that
described in Catalyst preparation example 1. The Si/Al ratio within the granulated
catalyst 2 was 35, the molar ratio between phosphorus and aluminum (P/Al ratio) was
21
0.23, and the amount of gallium (based on a value of 100% for the total mass of the
crystalline aluminosilicate) was 0.2% by mass.
[0034]
(Catalyst preparation example 3)
With the exception of preparing a gallium-supporting crystalline aluminosilicate
using a proton-type crystalline aluminosilicate having an MFI structure and a
silicon/aluminum molar ratio (Si/Al ratio) of 50, and then impregnating 30 g of the thus
obtained gallium-supporting crystalline aluminosilicate with 30 g of a 1.00% by mass
aqueous solution of diammonium hydrogen phosphate, a granular catalyst 3 (hereinafter
referred to as the "granulated catalyst 3") was obtained in the same manner as that
described in Catalyst preparation example 1. The Si/Al ratio within the granulated
catalyst 3 was 50, the molar ratio between phosphorus and aluminum (P/Al ratio) was
0.23, and the amount of gallium (based on a value of 100% for the total mass of the
crystalline aluminosilicate) was 0.2% by mass.
[0035]
(Catalyst preparation example 4)
With the exception of preparing a gallium-supporting crystalline aluminosilicate
using a proton-type crystalline aluminosilicate having an MFI structure and a
silicon/aluminimi molar ratio (Si/Al ratio) of 100, and then impregnating 30 g of the thus
obtained gallium-supporting crystalline aluminosilicate with 30 g of a 0.50% by mass
aqueous solution of diammonium hydrogen phosphate, a granular catalyst 4 (hereinafter
referred to as the "granulated catalyst 4") was obtained in the same manner as that
described in Catalyst preparation example 1. The Si/Al ratio within the granulated
catalyst 4 was 100, the molar ratio between phosphorus and aluminum (P/Al ratio) was
22
0.23, and the amount of gallium (based on a value of 100% for the total mass of the
crystalline aluminosilicate) was 0.2% by mass.
[0036]
(Catalyst preparation example 5)
With the exception of preparing a gallium-supporting crystalline aluminosilicate
using a proton-type crystalline aluminosilicate having an MFI structure and a
silicon/aluminum molar ratio (Si/Al ratio) of 200, and then impregnating 30 g of the thus
obtained gallium-supporting crystalline aluminosilicate with 30 g of a 0.27% by mass
aqueous solution of diammonium hydrogen phosphate, a granular catalyst 5 (hereinafter
referred to as the "granulated catalyst 5") was obtained in the same manner as that
described in Catalyst preparation example 1. The Si/Al ratio within the granulated
catalyst 5 was 200, the molar ratio between phosphorus and aluminum (P/Al ratio) was
0.23, and the amount of gallium (based on a value of 100%) for the total mass of the
crystalline aluminosilicate) was 0.2% by mass.
[0037]
(Catalyst preparation example 6)
With the exception of impregnating 120 g of the proton-type crystalline
aluminosilicate with 120 g of a 2.30% by mass aqueous solution of gallium nitrate
octahydrate in order to support 0.4% by mass of gallium on the aluminosilicate (based on
a value of 100%) for the total mass of the crystalline aluminosilicate), a granular catalyst
6 (hereinafter referred to as the "granulated catalyst 6") was obtained in the same manner
as that described in Catalyst preparation example 1. The Si/Al ratio within the
granulated catalyst 6 was 15, the molar ratio between phosphorus and aluminum (P/Al
23
ratio) was 0.23, and the amount of gallium (based on a value of 100% for the total mass
of the crystalline aluminosilicate) was 0.4% by mass.
[0038]
(Catalyst preparation example 7)
With the exception of impregnating 120 g of the proton-type crystalline
aluminosilicate with 120 g of a 4.03%) by mass aqueous solution of gallium nitrate
octahydrate in order to support 0.7%) by mass of gallium on the aluminosilicate (based on
a value of 100% for the total mass of the crystalline aluminosilicate), a granular catalyst
7 (hereinafter referred to as the "granulated catalyst 7") was obtained in the same marmer
as that described in Catalyst preparation example 1. The Si/Al ratio within the
granulated catalyst 7 was 15, the molar ratio between phosphorus and alviminum (P/Al
ratio) was 0.23, and the amount of gallium (based on a value of 100% for the total mass
of the crystalline aluminosilicate) was 0.7%) by mass.
[0039]
(Catalyst preparation example 8)
With the exception of impregnating 120 g of the proton-type crystalline
aluminosilicate with 120 g of a 5.75%) by mass aqueous solution of gallium nitrate
octahydrate in order to support 1.0% by mass of gallium on the aluminosilicate (based on
a value of 100% for the total mass of the crystalline aluminosilicate), a granular catalyst
8 (hereinafter referred to as the "granulated catalyst 8") was obtained in the same manner
as that described in Catalyst preparation example 1. The Si/Al ratio within the
granulated catalyst 8 was 15, the molar ratio between phosphorus and aluminum (P/Al
ratio) was 0.23, and the amount of gallium (based on a value of 100%o for the total mass
of the crystalline aluminosilicate) was 1.0%) by mass.
24
[0040]
(Catalyst preparation example 9)
With the exception of impregnating 120 g of the proton-type crystalline
aluminosilicate with 120 g of a 8.63% by mass aqueous solution of gallium nitrate
octahydrate in order to support 1.5% by mass of gallium on the aluminosilicate (based on
a value of 100% for the total mass of the crystalline aluminosilicate), a granular catalyst
9 (hereinafter referred to as the "granulated catalyst 9") was obtained in the same maimer
as that described in Catalyst preparation example 1. The Si/Al ratio within the
granulated catalyst 9 was 15, the molar ratio between phosphorus and aluminum (P/Al
ratio) was 0.23, and the amoimt of gallium (based on a value of 100% for the total mass
of the crystalline aluminosilicate) was 1.5% by mass.
[0041]
(Catalyst preparation example 10)
120 g of a proton-type crystalline aluminosilicate having an MFI structure and a
sihcon/aluminum molar ratio (Si/Al ratio) of 35 was impregnated with 120 g of a 1.15%)
by mass aqueous solution of gallium nitrate octahydrate in order to support 0.2%) by mass
of gallium on the aluminosilicate (based on a value of 100% for the total mass of the
crystalline aluminosilicate), and the resulting product was then dried at 120°C.
Subsequently, the product was calcined for 3 hours at 780°C under a stream of air,
yielding a gallium-supporting crystalline aluminosilicate.
Tablet molding was then performed by applying a pressure of 39.2 MPa (400 kgf)
to the obtained catalyst, and the resulting tablets were subjected to coarse crushing and
then classified using a 20 to 28 mesh size, thus yielding a granular catalyst 10
(hereinafter referred to as the "granulated catalyst 10"). The Si/Al ratio within the
25
granulated catalyst 10 was 35, the molar ratio between phosphorus and aluminum (P/Al
+
ratio) was 0, and the amount of gallium (based on a value of 100% for the total mass of
the crystalline aluminosilicate) was 0.2% by mass.
[0042]
(Catalyst preparation example 11)
120 g of a proton-type crystalline aluminosilicate having an MFI structure and a
silicon/aluminum molar ratio (Si/Al ratio) of 35 was impregnated with 120 g of a 1.15%
by mass aqueous solution of gallium nitrate octahydrate in order to support 0.2% by mass
of gallium on the aluminosilicate (based on a value of 100% for the total mass of the
crystalline aluminosilicate), and the resulting product was then dried at 120°C.
Subsequently, the product was calcined for 3 hours at 780°C under a stream of air,
yielding a gallium-supporting crystalline aluminosilicate.
Subsequently, 30 g of the obtained gallium-supporting crystalline aluminosilicate
was impregnated with 30 g of a 0.37% by mass aqueous solution of diammonium
hydrogen phosphate, and the resulting product was then dried at 120°C. Subsequently,
the product was calcined for 3 hours at 780°C under a stream of air, yielding a catalyst
containing the crystalline aluminosilicate, gallium and phosphorus.
Tablet molding was performed by applymg a pressure of 39.2 MPa (400 kgf) to
the obtained catalyst, and the resulting tablets were subjected to coarse crushing and then
classified usmg a 20 to 28 mesh size, thus yielding a granular catalyst 11 (hereinafter
referred to as the "granulated catalyst 11"). The Si/Al ratio within the granulated catalyst
11 was 35, the molar ratio between phosphorus and aluminum (P/Al ratio) was 0.06, and
the amount of gallium (based on a value of 100% for the total mass of the crystalline
aluminosilicate) was 0.2% by mass.
26
[0043]
(Catalyst preparation example 12)
With the exception of impregnating the gallium-supporting crystalline
aluminosilicate with 30 g of a 5.47% by mass aqueous solution of diammonium
hydrogen phosphate, a granular catalyst 12 (hereinafter referred to as the "granulated
catalyst 12") was obtained in the same manner as that described in Catalyst preparation
example 11. The Si/Al ratio within the granulated catalyst 12 was 35, the molar ratio
between phosphorus and aluminum (P/Al ratio) was 0.90, and the amount of gallium
(based on a value of 100% for the total mass of the crystalline aluminosilicate) was 0.2%
by mass.
[0044]
(Catalyst preparation example 13)
With the exception of impregnating the gallium-supporting crystalline
aluminosilicate with 30 g of a 7.30% by mass aqueous solution of diammonium
hydrogen phosphate, a granular catalyst 13 (hereinafter referred to as the "granulated
catalyst 13") was obtained in the same manner as that described in Catalyst preparation
example 11. The Si/Al ratio within the granulated catalyst 13 was 35, the molar ratio
between phosphorus and aluminum (P/Al ratio) was 1.20, and the amount of gallium
(based on a value of 100% for the total mass of the crystalline aluminosilicate) was 0.2%
by mass.
[0045]
(Catalyst preparation example 14)
A mixed solution containing 106 g of sodium silicate (J Sodium SiUcate No. 3,
SiOi: 28 to 30% by mass, Na: 9 to 10% by mass, remainder: water, manufactured by
27
Nippon Chemical Industrial Co., Ltd.) and pure water was added dropwise to a dilute
sulfuric acid solution to prepare a silica sol aqueous solution (SiOi concentration: 10.2%).
Meanwhile, distilled water was added to 20.4 g of the catalyst prepared in Catalyst
preparation example 6 containing a crystalline aluminosilicate, gallium and phosphorus
to prepare a zeolite slurry. The zeolite slurry was mixed with 300 g of the silica sol
aqueous solution, and the resulting slurry was spray dried at 250°C, yielding a
spherically shaped catalyst. Subsequently, the catalyst was calcined for 3 hours at 600°C,
yielding a powdered catalyst 1 (hereinafter referred to as the "powdered catalyst 1").
With respect to the crystalline aluminosilicate within the powdered catalyst 1
excluding the binder, the Si/Al ratio was 15, the molar ratio between phosphorus and
aluminum (P/Al ratio) was 0.23, and the amount of gallium (based on a value of 100%
for the total mass of the crystalline aluminosilicate) was 0.4% by mass.
[0046]
(Catalyst preparation example 15)
With the exception of using the catalyst synthesized in Catalyst preparation
example 8, containing a crystalline aluminosilicate, gallium and phosphorus, a powdered
catalyst 2 (hereinafter referred to as the "powdered catalyst 2") was obtained in the same
manner as that described in Catalyst preparation example 14.
With respect to the crystalline aluminosilicate within the powdered catalyst 1
excluding the binder, the Si/Al ratio was 15, the molar ratio between phosphorus and
aluminum (P/Al ratio) was 0.23, and the amount of gallium (based on a value of 100%
for the total mass of the crystalline aluminosilicate) was 1.0% by mass.
[0047]
(Catalyst preparation example 16)
28
With the exception of using the catalyst synthesized in Catalyst preparation
example 10, containing a crystalluie aluminosilicate and gallium, a powdered catalyst 3
(hereinafter referred to as the "powdered catalyst 3") was obtained in the same manner as
that described in Catalyst preparation example 14.
With respect to the crystalline aluminosilicate within the powdered catalyst 1
excluding the binder, the Si/Al ratio was 35, the molar ratio between phosphorus and
aluminum (P/Al ratio) was 0.0, and the amount of gallium (based on a value of 100% for
the total mass of the crystalline aluminosilicate) was 0.2% by mass.
[0048]
(Catalyst preparation example 17)
With the exception of using the catalyst synthesized in Catalyst preparation
example 2, containing a crystalline aluminosilicate, gallium and phosphorus, a powdered
catalyst 4 (hereinafter referred to as the "powdered catalyst 4") was obtained in the same
maimer as that described in Catalyst preparation example 14.
With respect to the crystalline aluminosilicate within the powdered catalyst 1
excluding the binder, the Si/Al ratio was 35, the molar ratio between phosphorus and
aluminum (P/Al ratio) was 0.23, and the amount of gallium (based on a value of 100%)
for the total mass of the crystalline aluminosilicate) was 0.2%o by mass.
[0049]
(Catalyst preparation example 18)
With the exception of using the catalyst synthesized in Catalyst preparation
example 13, containing a crystalline aluminosilicate, gallium and phosphorus, a
powdered catalyst 5 (hereinafter referred to as the "powdered catalyst 5") was obtained in
the same maimer as that described in Catalyst preparation example 14.
29
With respect to the crystalUne aluminosihcate within the powdered catalyst 1
excluding the binder, the Si/Al ratio was 35, the molar ratio between phosphorus and
aluminum (P/Al ratio) was 1.2, and the amount of gallium (based on a value of 100% for
the total mass of the crystalline aluminosihcate) was 0.2% by mass.
[0050]
(Catalyst preparation example 19)
With the exception of impregnating 120 g of the proton-type crystalline
aluminosihcate having an MFI structure and a silicon/aluminum molar ratio (Si/Al ratio)
of 15 with 120 g of a 0.91%) by mass aqueous solution of zinc nitrate hexahydrate in
order to support 0.2%) by mass of zinc on the aluminosihcate (based on a value of 100%)
for the total mass of the crystalline aluminosihcate), a granular catalyst 14 (hereinafter
referred to as the "granulated catalyst 14") was obtained in the same manner as that
described in Catalyst preparation example 1. The Si/Al ratio within the granulated
catalyst 14 was 15, the molar ratio between phosphorus and aluminum (P/Al ratio) was
0.23, and the amount of zinc (based on a value of 100%) for the total mass of the
crystalline aluminosihcate) was 0.2%) by mass.
[0051]
(Catalyst preparation example 20)
With the exception of impregnating 120 g of the proton-type crystalline
aluminosihcate with 120 g of a 1.82%) by mass aqueous solution of zinc nitrate
hexahydrate in order to support 0.4%) by mass of zinc on the aluminosihcate (based on a
value of 100%) for the total mass of the crystalline aluminosihcate), a granular catalyst 15
(hereinafter referred to as the "granulated catalyst 15") was obtained in the same manner
as that described in Catalyst preparation example 6. The Si/Al ratio within the
30
granulated catalyst 15 was 15, the molar ratio between phosphorus and aluminum (P/Al
ratio) was 0.23, and the amount of zinc (based on a value of 100% for the total mass of
the crystalline aluminosilicate) was 0.4% by mass.
[0052]
(Catalyst preparation example 21)
With the exception of impregnating 120 g of the proton-type crystalline
aluminosilicate with 120 g of a 3.19% by mass aqueous solution of zinc nitrate
hexahydrate in order to support 0.7% by mass of zinc on the aluminosilicate (based on a
value of 100%) for the total mass of the crystalline aluminosilicate), a granular catalyst 16
(hereinafter referred to as the "granulated catalyst 16") was obtained in the same manner
as that described in Catalyst preparation example 7. The Si/Al ratio within the
granulated catalyst 16 was 15, the molar ratio between phosphorus and aluminum (P/Al
ratio) was 0.23, and the amount of zinc (based on a value of 100% for the total mass of
the crystalline aluminosilicate) was 0.7%) by mass.
[0053]
(Catalyst preparation example 22)
With the exception of impregnating 120 g of the proton-type crystalline
aluminosilicate with 120 g of a 4.55%o by mass aqueous solution of zinc nitrate
hexahydrate in order to support 1.0%) by mass of zinc on the aluminosilicate (based on a
value of 100% for the total mass of the crystalline aluminosilicate), a granular catalyst 17
(hereinafter referred to as the "granulated catalyst 17") was obtained in the same maimer
as that described in Catalyst preparation example 8. The Si/Al ratio within the
granulated catalyst 17 was 15, the molar ratio between phosphorus and aluminum (P/Al
31
ratio) was 0.23, and the amount of zinc (based on a value of 100% for the total mass of
the crystalline aluminosilicate) was 1.0% by mass.
[0054]
(Catalyst preparation example 23)
With the exception of impregnating 120 g of the proton-type crystalline
aluminosilicate with 120 g of a 6.83% by mass aqueous solution of zinc nitrate
hexahydrate in order to support 1.5% by mass of zinc on the aluminosilicate (based on a
value of 100% for the total mass of the crystalline aluminosilicate), a granular catalyst 18
(hereinafter referred to as the "granulated catalyst 18") was obtained in the same manner
as that described in Catalyst preparation example 9. The Si/Al ratio within the
granulated catalyst 18 was 15, the molar ratio between phosphorus and aluminum (P/Al
ratio) was 0.23, and the amount of zinc (based on a value of 100%) for the total mass of
the crystalline aluminosilicate) was 1.5% by mass.
[0055]
(Catalyst preparation example 24)
18 g of fumed silica was impregnated with 30 g of a 13.4%) by mass aqueous
solution of gallium nitrate octahydrate, and the resulting product was dried at 120°C.
Subsequently, the product was calcined for 3 hours at 780°C under a stream of air,
yielding a gallium-supporting fumed silica.
18 g of this gallium-supporting fumed silica was impregnated with 50 g of a 30%i
by mass aqueous solution of diammonium hydrogen phosphate, and the resulting product
was dried at 120°C. Subsequently, the product was calcined for 3 hours at 780°C under a
stream of air, yielding a fumed sihca containing gallium (3.1%o by mass) and phosphorus
(16.4% by mass).
32
18 g of this fumed silica containing gallium and phosphorus was mixed with 12 g
of the catalyst prepared in Catalyst preparation example 1, the thus obtained catalyst was
subjected to tablet molding by applying a pressure of 39.2 MPa (400 kgf), and the
resulting tablets were subjected to coarse crushing and then classified using a 20 to 28
mesh size, thus yielding a granular catalyst 19 (hereinafter referred to as the "granulated
catalyst 19"). The Si/Al ratio of the crystalline aluminosilicate contained within the
granulated catalyst 19 was 15, the molar ratio between phosphorus and aluminum (P/Al
ratio) was 0.23, and the amount of gallium (based on a value of 100% for the total mass
of the crystalline aluminosilicate) was 0.2% by mass. Further, the amount of supported
gallium within the catalyst was 1.9% by mass, and the amount of supported phosphorus
was 9.8%) by mass.
[0056]

[Measurement of yield of monocyclic aromatic hydrocarbons during initial reaction:
Measurement 1]
The initial reaction catalytic activity of each of the obtained granulated catalysts 1
to 9 and 14 to 1$ was evaluated using the method outlined below.
Using a flow-type reaction apparatus in which the reactor had been charged with
the granulated catalyst (10 ml), a feedstock oil having the properties shown in Table 1
was brought into contact with the granulated catalyst and reacted under conditions
including a reaction temperature of 550°C and a reaction pressure of 0 MPaG. During
the reaction, nitrogen was introduced as a diluent so that the contact time between the
feedstock oil and the granulated catalyst was 7 seconds.
33
Reaction was continued under these conditions for 30 minutes to produce
monocyclic aromatic hydrocarbons of 6 to 8 carbon niimber, and a compositional
analysis of the products was performed using an FID gas chxomatograph coimected
directly to the reaction apparatus in order to measure the yield of monocyclic aromatic
hydrocarbons during the initial reaction. The measurement results obtained using the
granulated catalysts 1 to 9 are shown in Table 2. The measurement results
obtained using the granulated catalysts 14 to 18 are shown in Table 3.
[0057]
[Table 1]
Feedstock properties Analysis melhod
Density (Measurement tei3q>erat«re: IS'^C) g.^cm'' 0.906 JISK2249
Kinematic (Measurement temperature: 30°C} nim^/s 3.640 JISK2283
vrscosity
Initial boiling point "C 175.5
10 \'oIume % distillation temperature "C 224.5
Distillation 50 volume % distillation temperature "C 274.0 nSK2254
cnaractenstics f
90 volume % distillation temperature "C 349.5
End point tenqjerature "C 376.0
Saturated content volume % 35
Olefin content volume % 8
Compositional Total aromatic content volume % 57 r™--c. IA
I JPI-:>S-49
^^^^Jysis Monocyclic aromatic content volume "o 23
BicycHc aromatic content volume % 15
Tricyclic and highier aromatic content volume % 9
[0058]
[Table 2]
34
II I ^
o g fo H » o o o o o d o '-J —•
1^
t i I
'o E ' I- ^ M - g., r- 1- r- r-
6 ii J
•g S'; ^" '^ '=5 d d d d — — g
•2 I
I s jq - -. -; - fq ;q jq o i — ^ 1 i I
5 • - ;^ ?. i I ^ ^ ^ ^ f 'i
_^ ^ 11
— j CN fl -T V-J S5 r- <« C> (4- p
iJIfltttftlJ
i 1 1 ! 1 ^ ,
[0059]
35
[Table 3]
If
s ^
^ ^' o r-, - o
0 a f^i f^i <^ f^i fN
1 -2 I I
0^
^ I "o S IN T r-- O >A
g ^ O O O '-^ —^
i ^
i t I
5 c >i o d d o d
I £.
lit .1
i O S (^t -f r^ o . d d d - ^ J
•2 i
1 s R R fq R s
I 1 1
^ >/-i ^ r- oc ^ 3
:I t t t f t jl
rs fi,
™K ,-. O — ¥ ^ O ill
36
[0060]
[Measurement of yield of monocyclic aromatic hydrocarbons during initial reaction:
Measurement 2]
The initial reaction catalytic activity of the obtained powdered catalysts 1 and 2
was evaluated using the method outlined below.
Using a flow-type reaction apparatus in which the reactor had been charged with
the powdered catalyst (400 g), a feedstock oil having the properties shown in Table 1
was brought into contact with the powdered catalyst and reacted under conditions
including a reaction temperature of 550°C and a reaction pressure of 0.1 MPaG. For the
reaction, the powdered catalyst was packed in a reaction tube with a diameter of 60 mm.
During the reaction, nitrogen was introduced as a diluent so that the contact time between
the feedstock oil and the powdered catalyst was 10 seconds.
Reaction was continued under these conditions for 10 minutes to produce
monocyclic aromatic hydrocarbons of 6 to 8 carbon number, and the gaseous products,
the liquid products and the coke deposited on the catalyst were collected. A
compositional analysis of the gaseous products was performed using a micro-gas
chromatograph and an FID gas chromatograph cormected directly to the reaction
apparatus. A compositional analysis of the liquid products was performed using the FID
gas chromatograph. The amount of coke on the catalyst was calculated using a CO2
meter connected directly to the reaction apparatus. On the basis of these compositional
analyses, the yield of monocyclic aromatic hydrocarbons during the initial reaction was
measured. The measurement results are shown in Table 4.
[0061]
[Table 4]
37
! !
I | ! ?^ 5Q
'3 I
o II
Hi.,
17' J
•? S ^ o I
•jS g^ O ^ t3
£ I
I : s s I
E i I J ^n 11
- n 11
: - .. 2 I i^ttli
' 1111
; ::! 12 'o "S fill
. ^ ' I r ?^
[0062]
38
[Measurement of yield of monocyclic aromatic hydrocarbons under pseudo-steady state
conditions: Measurement 3]
The obtained granulated catalysts 2, 10 to 13 and 19 and the powdered catalysts 3
to 5 were each subjected to a hydrothermal treatment under conditions including a
treatment temperature of 650°C and a treatment time of 6 hours under a 100% by mass
steam atmosphere, thus effecting a simulated hydrothermal degradation that yielded
pseudo-steady state granulated catalysts 2, 10 to 13 and 19 and pseudo-steady state
powdered catalysts 3 to 5. By using these hydrothermally degraded catalysts, the yield
of monocyclic aromatic hydrocarbons under a pseudo-steady state was able to be
evaluated.
With the exception of using these pseudo-degraded catalysts instead of the
granulated catalysts, the same process as that described for measurement 1 was used to
react the feedstock oil and then perform a compositional analysis of the resulting
products to measure the yield of the monocyclic aromatic hydrocarbons. The
measurement results are shown in Table 5 and Table 7.
Further, with the exception of using the pseudo-degraded powdered catalysts
instead of the powdered catalysts, the same process as that described for measurement 2
was used to react the feedstock oil and then perform a compositional analysis of the
resulting products to measure the yield of the monocyclic aromatic hydrocarbons. The
measurement results are shown in Table 6.
[0063]
[Table 5]
39
| l
I *
I i
2. >, r.| v\ —< t-~ fN
m -a „ r-l r^, (N —
It
a I
t; >, O O O O O i I
•^ 1
c >> o o o — — g
if J
'S E rs M fs
"S IS E ^ o "
t- >, -^ O tN
03 T3 ,-H (^ -^
U 03
o to
^<°-> ^^A
O ^
*
o s
't; p oo oo 00
o •- o o o
c ^ o d d
i ^
_<
* ,—,
O P O 00 O
„ ^ O (N -*
§ ;^ d <5 ^
<
*
cd en o ^
'o 2 (N tN (N
•4-' >» d d d
<
_o
CO O (^ O
J;; o (N (N
"^ di S '-^
£; - .
_o
"S ml lol lol
t- ro| m| o-i]
r<^ •* lO
' O •(-> TS -^ t3 -^
(D w D ^ O CO
T3 >-. TJ '^ "O ^
+^ g 15 S "to 2 ea
^ 00 ta oo « Ml 'S
X^ (U o
CO ^ « ? m ^
cu, o cu o &. o
O. G. ex
. ^ *« -^ .> t^
ta i i ju ta ii
rag- & ia ga.
E E a. E
£ 5 I £ S
41
[0065]
[Table 7]
42
If t ^
I i ^
It
0 i
111
at I
1 t €
< I
I § i |
-5 I !
I „ 11
ih 11
1 11
5 1 11
I M
- s s
iU r ^'
[0066]
43

It is evident that examples 1 to 4, which used the granulated catalysts 1 to 4
respectively in which the Si/Al ratio within the crystalline aluminosilicate was not more
than 100, produced superior yields of monocyclic aromatic hydrocarbons than
comparative example 1 which had a Si/Al ratio of 200.
Further, it is also evident that example 1 and examples 5 to 7, in which the
amoxint of gallium was not more than 1.2% by mass, produced superior yields of
monocyclic aromatic hydrocarbons than comparative example 2 in which the amount of
gallium was 1.5% by mass.
Similarly, in those cases where zinc was included in the catalysts, it is evident
that examples 8 to 11, in which the amount of zinc was not more than 1.2% by mass,
produced superior yields of monocyclic aromatic hydrocarbons than comparative
example 3 in which the amount of zinc was 1.5% by mass.
Even in the case of the powdered catalysts, it is clear that examples 12 and 13
produced superior yields of monocyclic aromatic hydrocarbons than comparative
example 2.
Moreover, examples 14 to 16, which used the pseudo-steady state granulated
catalysts 2, 11 and 12 (pseudo-degraded catalysts 2, 11 and 12) in which the P/Al ratio
was within a range from 0.01 to 1.0, produced superior yields of monocyclic aromatic
hydrocarbons under steady state conditions than both comparative example 4, which
used the pseudo-steady state granulated catalyst 10 (pseudo-degraded catalyst 10) in
which the P/Al ratio was 0.00, and comparative example 5, which used the pseudosteady
state granulated catalyst 13 (pseudo-degraded catalyst 13) in which the P/Al ratio
was 1.20.
44
Furthermore, it is also evident that example 17, which used the pseudo-steady
state powdered catalyst 4 (pseudo-degraded powdered catalyst 4), produced a superior
yield of monocyclic aromatic hydrocarbons under steady state conditions than both
comparative example 6, which used the pseudo-steady state powdered catalyst 3
(pseudo-degraded powdered catalyst 3) in which the P/Al ratio was 0.00, and
comparative example 7, which used the pseudo-steady state powdered catalyst 5
(pseudo-degraded powdered catalyst 5) in which the P/Al ratio was 1.20.
In example 18, which used the granulated catalyst 19 containing an inorganic
oxide within the catalyst (pseudo-degraded catalyst 19), an improved result was
confirmed for the yield of monocyclic aromatic hydrocarbons under steady state
conditions.
From the above results, it was clear that by using a granulated catalyst or
powdered catalyst in which the Si/Al ratio within the crystalline aluminosilicate was not
more than 100, the P/Al ratio was not less than 0.01 and not more than 1.0, and the
amount of gallium was not more than 1.2% by mass, the yield of monocyclic aromatic
hydrocarbons could be increased, both during the initial reaction and under pseudosteady
state conditions.

' claims
1. A catalyst for producing monocyclic aromatic hydrocarbons, used for
producing monocyclic aromatic hydrocarbons of 6 to 8 carbon number from a feedstock
oil having a 10 volume % distillation temperature of at least 140°C and an end point
temperature of not more than 400°C, wherein
the catalyst comprises a crystalline aluminosilicate, gallium and/or zinc, and
phosphorus, a molar ratio between silicon and aluminum (Si/Al ratio) in the crystalline
aluminosilicate is not more than 100, a molar ratio between phosphorus supported on
the crystalline aluminosilicate and aluminum within the crystalline aluminosilicate
(P/Al ratio) is not less than 0.01 and not more than 1.0, and an amount of gallium and/or
zinc is not more than 1.2% by mass based on the mass of the crystalline aluminosilicate.
2. The catalyst for producing monocyclic aromatic hydrocarbons according to
claim 1, wherein an amount of phosphorus is within a range from 0.1 to 10% by mass
based on total mass of the catalyst, and an amount of gallium and/or zinc contained
within the catalyst is not more than 2% by mass based on total mass of the catalyst.
3. The catalyst for producing monocyclic aromatic hydrocarbons according to
claim 1 or 2, wherein the crystalline aluminosilicate is a pentasil-type zeolite.
4. The catalyst for producing monocyclic aromatic hydrocarbons according to
claim 1 anv..one of claims 1 to 3. wherein the crystalline aluminosilicate is an MFI-type
zeolite.
5. The catalyst for producing monocyclic aromatic hydrocarbons according to
claim 1 anv one of claims 1 to 4. wherein a molar ratio between phosphorus supported
on the crystalline aluminosiUcate and aluminum within the crystalline aluminosilicate
(P/Al ratio) is not more than 0.5.
6. The catalyst for producing monocyclic aromatic hydrocarbons according to
claim 1 any one of claims 1 to 5, wherein an amount of gallium and/or zinc is not more
than 1.0% by mass based on a mass of the crystalline aluminosilicate.
7. A method for producing monocyclic aromatic hydrocarbons of 6 to 8 carbon
number, the method comprising bringing a feedstock oil having a 10 volume %
distillation temperature of at least 140°C and an end point temperature of not more than
400°C into contact with the catalyst for producing monocyclic aromatic hydrocarbons
according to claim 1 any one of claims 1 to 5.
8. A method for producing monocyclic aromatic hydrocarbons of 6 to 8 carbon
number, the method including bringing a feedstock oil having a 10 volume %
distillation temperature of at least 140°C and a 90 volume % distillation temperature of
not more than 350°C into contact with the catalyst for producing monocyclic aromatic
hydrocarbons according to claim 1 any one of claims 1 to 5.
9. The method for producing monocyclic aromatic hydrocarbons of 6 to 8 carbon
number according to claim 7 or claim 8, wherein a cracked gas oil produced in a fluid
catalytic cracking is used as the feedstock oil.
10. The method for producing monocyclic aromatic hydrocarbons of 6 to 8 carbon
number according to claim 7 or claim 8 any one of claims 7 to 9, wherein the feedstock
oil is brought into contact with the catalyst for producing monocyclic aromatic
hydrocarbons in a fluidized bed reactor.
Dated this 10/01/2012