FORM 2
THE PATENTS ACT, 1970
(39 of 1970)
& The Patent Rules, 2003
COMPLETE SPECIFICATION
1.TITLE OF THE INVENTION:
FLUID CATALYTIC CRACKING CATALYST FOR HYDROCARBON OIL
2. APPLICANT:
Name: JGC CATALYSTS AND CHEMICALS LTD.
Nationality: Japan
Address: 580, Horikawa-cho, Saiwai-ku, Kawasaki-shi, Kanagawa 2120013, Japan.
3. PREAMBLE TO THE DESCRIPTION:
The following specification particularly describes the invention and the manner in which
it is to be performed:

Description
Technical Field
[0001] The present invention relates to a fluid catalytic cracking catalyst for
hydrocarbon oil that is excellent in selectivity in terms of a high liquid yield, low
gas content, etc. and also effective in reducing coke formation and enhancing
heavy oil cracking performance.
Background Art
[0002] Generally, catalytic cracking catalysts are demanded to deliver high
performance from various perspectives, such as that the ability of cracking heavy
hydrocarbon oil, including reduced crude, (also called a "bottom cracking
capability") is high and that the amount of coke depositing on the catalyst surface
is small. In this regard, methods for fluid catalytic cracking of hydrocarbon oil
have been hitherto proposed that, for example, use a blend of two different types
of catalysts to reduce the coke yield and increase the yields of gasoline and
middle distillates (light oil and kerosene) etc. (achieve high liquid yields).
[0003] For example, Patent Literature 1 discloses a cracking catalyst used for
fluid catalytic cracking of hydrocarbon oil that is composed of two types of
catalysts physically blended at a ratio of 1:9 to 9:1. One catalyst is a zeolitecontaining
cracking catalyst, and the other catalyst is a catalyst that has a higher
25 average pore volume in a pore diameter range of 20 to 200 Å (2 to 20 nm) than
the one catalyst does in the same pore diameter range and that contains no M41S
substances.
[0004] Patent Literature 2 discloses a fluid catalytic cracking catalyst for
hydrocarbon oil that is a blend of two or more types of catalysts each containing
a zeolite and an inorganic oxide matrix that is composed of active matrix
components and inactive matrix components. This fluid catalytic cracking
catalyst for hydrocarbon oil is characterized in that each catalyst contains a
different amount of zeolite.
[0005] Patent Literature 3 discloses a fluid catalytic cracking catalyst that is
composed of two catalysts, one containing a zeolite and 10 to 30 mass% of a
silica-based binder as a binding agent and the other containing a zeolite and 10 to
mass% of an aluminum compound binder as a binding agent, 5 blended at a
mass ratio within a range of 10:90 to 90:10. Therefore, the catalyst is excellent
in coke reduction and the bottom (heavy distillate) cracking capability.
[0006] Patent Literature 4 discloses a hydrocarbon catalytic cracking catalyst
that is a blend of a catalyst (a) containing a faujasite-type zeolite (A) having a
lattice constant within a range of 2.435 to 2.455 nm, matrix components, and a
rare earth; and a catalyst (b) containing a faujasite-type zeolite (B) having a
lattice constant within a range of 2.445 to 2.462 nm, matrix components,
phosphorus, and magnesium. Accordingly, the catalyst contains only a small
amount of rare-earth oxide and yet has excellent hydrothermal stability and a
high residual oil (bottom) cracking capability as well as is excellent in selectivity
(high liquid yield, low gas content, and low coke content).
Citation List
Patent Literature
[0007] Patent Literature 1: JP-A-2004-528963
Patent Literature 2: JP-A-2010-110698
Patent Literature 3: WO 2009/145311
Patent Literature 4: JP-A-2014-36934
Summary of Invention
Technical Problem
[0008] The problem, however, is that in reality these conventional fluid
catalytic cracking catalysts cannot achieve a satisfactory low coke content. For
example, the fluid catalytic cracking catalysts described in Patent Literatures 1 to
3 do not always prove fully effective. As to the fluid catalytic cracking catalyst
described in Patent Literature 4, which is a blend of zeolites with different lattice
constants, blending the catalysts may not be effective depending on the hydrogen
transfer reaction activities of the catalysts to be blended. Moreover, since one
of the catalysts contains no rare earths, the hydrothermal resistance is low and a
sufficient catalytic activity cannot be produced.
[0009] Having been contrived in view of the circumstances surrounding the
conventional materials, the present invention aims to provide a fluid catalytic
cracking catalyst for hydrocarbon oil that is effective in reducing coke formation
and excellent in selectivity (product yields 5 of gasoline etc.).
Solution to Problem
[0010] Against this technical background, the present inventors worked
vigorously on a solution to the above-described problems, and as a result, found
that blending catalysts each having a different hydrogen transfer reaction activity
or a specific pore distribution (pore size and pore volume distribution) can reduce
coke formation and increase the yields of high-value-added products, which led
us to develop the present invention.
[0011] The present invention developed to solve the problems and achieve
the above object is as follows: First, a fluid catalytic cracking catalyst for
hydrocarbon oil excellent in product yield of the present invention is a fluid
catalytic cracking catalyst for hydrocarbon oil that is a blend of two types of
fluid catalytic cracking catalysts each of which has a different hydrogen transfer
reaction activity or has a pore distribution within a specific range after being
pseudo-equilibrated. One catalyst is a catalyst containing a zeolite and matrix
components, and the other catalyst is a catalyst containing a zeolite and matrix
components, at least one of which is different from the zeolite or the matrix
components of the one catalyst. The fluid catalytic cracking catalyst is
composed of the one catalyst and the other catalyst blended at a mass ratio within
a range of 10:90 to 90:10.
[0012] In the fluid catalytic cracking catalyst for hydrocarbon oil of the
present invention that is a blend of two types of fluid catalytic cracking catalysts
each having a different hydrogen transfer reaction activity, the following
specifications can be considered as a preferred possible solution:
one catalyst is a catalyst (1) containing a faujasite-type zeolite (A)
having a lattice constant within a range of 2.435 to 2.459 nm, matrix
components, and a rare earth; the other catalyst is a catalyst (2) containing a
faujasite-type zeolite (B) having a lattice constant within a range of 2.440 to
2.478 nm, matrix components, and a rare earth; and the hydrogen transfer
reaction activity of the catalyst (1) is lower than the hydrogen transfer reaction
activity of the catalyst (2).
[0013] In the fluid catalytic cracking catalyst for hydrocarbon oil according
to the present invention, the following specifications can be considered 5 as a more
preferred possible solution:
(i) A difference between the catalyst (1) and the catalyst (2) in an
(iC4/C4=) ratio (where iC4 and C4= represent the masses of isobutane and
butene, respectively, generated in a test that evaluates performance in fluid
catalytic cracking of hydrocarbon oil) that is an index of the hydrogen transfer
reaction activity is within a range of 0.10 to 0.85;
(ii) The catalyst (1) contains 15 to 60 mass% of the faujasite-type
zeolite (A) based on the catalyst composition, and the catalyst (2) contains 15 to
60 mass% of the faujasite-type zeolite (B) based on the catalyst composition; and
(iii) The catalyst (1) contains 0.5 to 2.0 mass% of the rare earth as
RE2O3 based on the catalyst composition, and the catalyst (2) contains 0.5 to 12
mass% of the rare earth as RE2O3 based on the catalyst composition.
[0014] In the fluid catalytic cracking catalyst for hydrocarbon oil of the
present invention that is a blend of two types of fluid catalytic cracking catalysts,
the following specifications can be considered as a preferred possible solution:
one catalyst is a catalyst (3) that has, after being pseudo-equilibrated,
a pore distribution in which a ratio (PV1/PV2) of a volume (PV1) of pores
having a pore size not smaller than 4 nm nor larger than 50 nm to a volume
(PV2) of pores having a pore size larger than 50 nm is lower than 0.8; the other
catalyst is a catalyst (4) that has, after being pseudo-equilibrated, a pore
distribution in which (a) a ratio (PV1/PV2) of a volume (PV1) of pores having a
pore size not smaller than 4 nm nor larger than 50 nm to a volume (PV2) of pores
having a pore size larger than 50 nm is not lower than 0.8, and (b) a ratio
(PV4/PV3) of a volume (PV4) of pores having a pore size not smaller than 30 nm
nor larger than 100 nm to a volume (PV3) of pores having a pore size larger than
4 nm is lower than 0.2; and the fluid catalytic cracking catalyst is composed of
the catalyst (3) and the catalyst (4) blended at a ratio of 100 parts by mass of the
former to 10 to 200 parts by mass of the latter.
[0015] In the fluid catalytic cracking catalyst for hydrocarbon oil according
to the present invention, the following specifications can be considered as a more
preferred possible solution:
(iv) The catalyst (3) contains a zeolite and a silica-5 based binder as a
binding agent, and contains 15 to 60 mass% of the zeolite and 5 to 30 mass% of
the silica-based binder based on the catalyst composition, and the catalyst (4)
contains a zeolite and an aluminum compound binder as a binding agent, and
contains 15 to 60 mass% of the zeolite and 5 to 30 mass% of the aluminum
compound binder based on the catalyst composition;
(v) the silica-based binder is one or more than one of silica sol, water
glass, and an acidic silicate solution;
(vi) the aluminum compound binder contains one type selected from
the following (a) to (c): (a) basic aluminum chloride, (b) aluminum biphosphate,
and (c) alumina sol;
(vii) the zeolites contained in the catalyst (3) and the catalyst (4) are
of one or more than one of the following types: FAU (faujasite), MFI, CHA, and
MOR;
(viii) the FAU-type zeolite is one of a hydrogen Y-type zeolite (HY),
an ultra-stable Y-type zeolite (USY), a rare-earth-exchanged Y-type zeolite
(REY), and a rare-earth-exchanged ultra-stable Y-type zeolite (REUSY); and
(ix) The catalyst (3) and the catalyst (4) contain clay mineral other
than the zeolite and the binding agent.
[0016] Second, the fluid catalytic cracking catalyst for hydrocarbon oil
excellent in the heavy oil cracking performance of the present invention is a fluid
catalytic cracking catalyst for hydrocarbon oil that is used by being blended with
other catalyst. This fluid catalytic cracking catalyst has, after being pseudoequilibrated,
a pore distribution in which: (a) a ratio (PV1/PV2) of a volume
(PV1) of pores having a pore size not smaller than 4 nm nor larger than 50 nm to
30 a volume (PV2) of pores having a pore size larger than 50 nm is not lower than
0.8; and (b) a ratio (PV4/PV3) of a volume (PV4) of pores having a pore size not
smaller than 30 nm nor larger than 100 nm to a volume (PV3) of pores having a
pore size larger than 4 nm is lower than 0.2.
[0017] In the fluid catalytic cracking catalyst for hydrocarbon oil according
to the present invention, the following specifications can be considered as a more
preferred possible solution:
(x) The catalyst contains a zeolite and an aluminum 5 compound binder
as a binding agent, and contains 15 to 60 mass% of the zeolite and 5 to 30 mass%
of the aluminum compound binder based on the catalyst composition;
(xi) The aluminum compound binder contains one type selected from
the following (a) to (c): (a) basic aluminum chloride, (b) aluminum biphosphate,
and (c) alumina sol;
(xii) The zeolite contained in the catalyst is of one or more than one
of the following types: FAU (faujasite), MFI, CHA, and MOR;
(xiii) The FAU-type zeolite is one of a hydrogen Y-type zeolite (HY),
an ultra-stable Y-type zeolite (USY), a rare-earth-exchanged Y-type zeolite
(REY), and a rare-earth-exchanged ultra-stable Y-type zeolite (REUSY); and
(xiv) The catalyst contains clay mineral other than the zeolite and the
binding agent.
Advantageous Effects of Invention
[0018] As has been described above, the fluid catalytic cracking catalyst for
hydrocarbon oil of the present invention is a blend of two types of fluid catalytic
cracking catalysts each of which has a different hydrogen transfer reaction
activity or has a pore distribution within a specific range after being pseudoequilibrated,
whereby a fluid catalytic cracking catalyst for hydrocarbon oil that
can reduce the coke yield and has excellent selectivity (product yields of gasoline
etc.) can be provided. Selecting a catalyst excellent in the heavy oil cracking
performance as one catalyst can further enhance the heavy oil cracking
performance.

Brief Description of Drawings
[0019]
FIG. 1 is a graph showing how blend ratios of catalysts according to
one embodiment of the present invention influence a coke yield.
FIG. 2 is a graph showing how the blend ratios of the catalysts
according to the embodiment influence a gasoline yield.
FIG. 3 is a graph showing how the blend ratios of the catalysts
according to the embodiment influence an HCO + coke yield.
FIG. 4 is a graph showing one example of distributions of a pore size
and a log-differentiated pore volume dVp/dlogd of catalysts according 5 to another
embodiment of the present invention.
FIG. 5 is a graph showing how pore size and pore volume
distributions (PV1/PV2) of the catalysts according to the other embodiment
influence cracking of hydrocarbon oil.
FIG. 6 is a graph showing how pore size and pore volume
distributions (PV4/PV3) of the catalysts according to the other embodiment
influence the crude oil cracking performance of a catalyst blend.
FIG. 7 is a graph showing how the blend ratio of the catalysts
according to the other embodiment influences a gasoline + LPG yield.
FIG. 8 is a view showing how the blend ratio of the catalysts
according to the other embodiment influences a coke + HCO yield.
Description of Embodiment
[0020] The fluid catalytic cracking catalyst for hydrocarbon oil according to
the present invention (hereinafter referred to simply as "the subject catalyst") is
prepared by blending two types of fluid catalytic cracking catalysts each of
which has a different hydrogen transfer reaction activity or has a pore
distribution within a specific range after being pseudo-equilibrated. In the
following, each catalyst will be described in detail. Both catalysts need to
function as a fluid catalytic cracking catalyst for hydrocarbon oil. First, items
that apply commonly to both catalysts will be described.
[0021]
Each catalyst of the present invention contains a zeolite and matrix
components.
[Matrix Components]
30 The matrix components constituting part of the subject catalyst refer
to components other than a zeolite component. As such matrix components,
hitherto commonly known inorganic oxides and inorganic compounds, such as
silica, alumina, silica-alumina, aluminum phosphate, silica-magnesia, aluminamagnesia,
and silica-magnesia-alumina, can be used. The matrix components
also include materials called a binding agent, a filler, and a metal scavenger.
[0022] Specifically, hitherto commonly known inorganic oxides and
inorganic compounds derived from silica gel, silica sol, silica 5 hydrosol, alumina
gel, alumina sol, silica-alumina gel, silica-alumina sol, an aluminum phosphate
compound, etc. can be used. Among them, silica sol, silica hydrosol, alumina
sol, silica-alumina sol, an aluminum phosphate compound, etc. can be suitably
used, because these materials function also as a carrier (base material) or a
binding agent of a faujasite-type zeolite and serve to produce a hydrocarbon
catalytic cracking catalyst that is excellent in catalytic activity, abrasion
resistance, etc. as well as in residual oil cracking activity, metal resistance, etc.
[0023] [Binding Agent]
As a binding agent (binder component), a silica-based binder, such as
silica sol, or an aluminum compound binder, such as basic aluminum chloride,
can be used. As the silica-based binder of these binders, other than silica sol,
colloidal silica of sodium type, lithium type, acid type, etc. can also be used.
Among them, silica sol is suitable. As the aluminum compound binder, other
than basic aluminum chloride, particles obtained by dissolving an aluminum
biphosphate solution, gibbsite, bayerite, boehmite, bentonite, crystalline alumina,
etc. in an acid solution; boehmite gel; particles obtained by dispersing amorphous
alumina gel in an aqueous solution; and alumina sol can also be used. These
materials can be used alone, in a blended form, or as a composite material.
[0024] The content of the binding agent is preferably 5 to 30 mass%. The
content is more preferably 10 to 25 mass%. This is because if the content of the
binding agent is lower than 5 mass%, the catalytic cracking activity increases but
sufficient strength against attrition (abrasion) of the catalytic may not be
maintained. On the other hand, if the content is higher than 30 mass%, a
sufficient catalytic cracking activity may not be produced.
[0025] [Filler]
As a filler, clay mineral, such as kaolin, bentonite, kaolinite,
halloysite, and montmorillonite, can be contained. The subject catalyst can
contain 15 to 45 mass% of clay mineral as a filler. This is because if the content
of clay mineral is lower than 15 mass%, excessive coke formation occurs due to
the large amount of active components and the catalyst may fail to deliver
sufficient performance. On the other hand, if the content exceeds 45 mass%, the
amount of solid acid in the catalyst may become so small 5 that the catalytic
activity decreases.
[0026] [Metal Scavenger]
As the metal scavenger, alumina particles, phosphorus-alumina
particles, crystalline calcium aluminate, sepiolite, barium titanate, calcium
10 stannate, strontium titanate, manganese oxide, magnesia, magnesia-alumina,
calcium carbonate, etc. can be used. As the raw material of the metal
scavenger, a precursor material, such as boehmite that becomes alumina etc. by
baked in an oxidizing atmosphere, can be used. When the subject catalyst
contains a metal scavenger, the content is desirably within a range of 0.1 to 10
mass% and more preferably within a range of 0.1 to 5 mass%.
[0027]
When the performance of a fluid catalytic cracking catalyst for
hydrocarbon oil is evaluated using a reactor in a laboratory, a treatment called
pseudo-equilibration is performed as a preliminary treatment. Pseudo20
equilibration is a treatment in which metal, such as V or Ni, is supported in a
fluid catalytic cracking catalyst and the catalyst is subjected to a steaming
treatment to thereby reduce the catalytic activity to a level equivalent to that of
an equilibrium catalyst. Reproducing the properties of an equilibrium catalyst
by this pseudo-equilibration treatment is important for evaluating the catalytic
activity with higher accuracy.
[0028]
The specific surface area of the pseudo-equilibrated catalyst is
measured by the BET method using, for example, Macsorb HM model-1200
manufactured by Mountech Co. The specific surface area of the matrix
components is obtained by measuring a nitrogen adsorption isotherm using, for
example, BELSORP-mini II manufactured by MicrotracBEL, and plotting a Vavs-
t graph based on the obtained adsorption-side isotherm. The specific surface
area of the zeolite component can be obtained by subtracting the specific surface
area of the matrix components from the total specific surface area. In the
present invention, the specific surface area (SA) of the entire catalyst is
preferably within a range of 100 to 250 m2/g. The specific surface area of the
matrix components is preferably not smaller than 30 m2/g and 5 more preferably
not smaller than 50 m2/g.
[0029] First Embodiment
The subject catalyst according to a first embodiment of the present
invention that is a blend of two types of fluid catalytic cracking catalysts each
having a different hydrogen transfer reaction activity will be described. In
particular, it is preferable that one catalyst be a catalyst (1) containing a
predetermined faujasite-type zeolite (A), matrix components, and a rare earth;
that the other catalyst be a catalyst (2) containing a predetermined faujasite-type
zeolite (B), matrix components, and a rare earth; and that the hydrogen transfer
reaction activity of the catalyst (1) be lower than the hydrogen transfer reaction
activity of the catalyst (2). In the following, this embodiment will be described
in detail.
[0030]
The catalyst (1) constituting this embodiment contains a
predetermined faujasite-type zeolite (A), matrix components, and a rare earth,
and this catalyst itself also functions as a fluid catalytic cracking catalyst for
hydrocarbon oil. Each of these components will be described in detail below.
[0031] [Faujasite-Type Zeolite (A)]
A faujasite-type zeolite is a zeolite having a skeleton composed of
SiO2 and Al2O3. The mole ratio (MS)/(MA) between the mole numbers (MS) and
(MA) of SiO2 and Al2O3, respectively, that compose the skeleton is preferably
within a range of 5 to 20 and more preferably within a range of 6 to 15. When
the mole ratio (MS)/(MA) is within this range, the hydrothermal resistance (the
ratio of catalytic activity maintained after the catalyst is subjected to a
30 regeneration treatment at high temperature) becomes higher, and the catalytic
activity and the gasoline selectivity also becomes higher.
[0032] If the mole ratio (MS)/(MA) is low, the hydrothermal resistance, the
12
catalytic activity, and the gasoline selectivity may become insufficient. In this
case, in a fluid catalytic cracking process in which carbonaceous matter having
deposited on the catalyst after cracking reactions is combusted and removed in a
regeneration tower to regenerate the catalyst, the catalyst reaches a high
temperature due to the heat of combustion and, as the carbonaceous 5 matter
contains hydrogen, water is generated. As a result, the catalyst is
hydrothermally processed at high temperature, and the crystallinity of the zeolite
is known to decrease in the process. On the other hand, if the mole ratio
(MS)/(MA) is too high, the hydrothermal resistance becomes high but the catalytic
10 activity may become insufficient, probably due to a reduced number of active
sites.
[0033] The lattice constant (UCS) of the faujasite-type zeolite (A) is 2.435 to
2.459 nm and preferably 2.440 to 2.450 nm. When the lattice constant is within
such a range, the gasoline selectivity become extremely high. If the lattice
15 constant is too low, the catalytic activity may become insufficient. On the other
hand, if the lattice constant is too high, the hydrothermal resistance and the metal
resistance may become insufficient. The above-mentioned lattice constant can
be obtained by measuring the spacing between diffraction planes (553) and (642)
of the zeolite obtained by the X-ray diffraction method using anatase TiO2 as a
20 standard substance.
[0034] As such a faujasite-type zeolite (A), an NH4 Y zeolite obtained by
performing NH4 ion exchange on an Na Y-type zeolite can be preferably used,
and an ultra-stable Y-type zeolite (USY) obtained by performing a hydrothermal
treatment on an NH4 Y-type zeolite is especially preferable.
25 [0035] The content (CZA) of the faujasite-type zeolite (A) in the catalyst (1)
as solid matter (mainly SiO2 and Al2O3) is preferably within a range of 15 to 60
mass% and further within a range of 15 to 40 mass%. If the content of the
faujasite-type zeolite (A) as solid matter is lower than 15 mass%, the catalytic
activity may become insufficient due to the low content of the zeolite. If the
30 content of the faujasite-type zeolite (A) as solid matter exceeds 60 mass%, the
catalytic activity becomes so high that excessive cracking may occur and the
selectivity may decrease. Moreover, as the content of the matrix components
13
other than the zeolite decreases, the abrasion resistance becomes insufficient, so
that the catalyst may easily pulverize and scatter when used as a fluid catalytic
cracking catalyst. While the replenish amount of the catalyst can be increased
to make up for this, it is economically problematic.
[0036] [5 Matrix Components]
The matrix components constituting part of the catalyst (1) refer to
components other than the faujasite-type zeolite (A), and suitably include the
above-described binding agent, filler, and metal scavenger that are common in
the subject catalyst.
10 [0037] The catalyst (1) preferably contains active alumina. In this case, the
content of active alumina as solid matter (Al2O3) is preferably within a range of 1
to 30 mass% and further within a range of 2 to 20 mass%. When the catalyst (1)
contains active alumina within this range, the catalyst (1) becomes highly
effective in enhancing the gasoline selectivity as well as excellent in residual oil
15 cracking activity and metal resistance.
[0038] The content of the matrix components in the catalyst (1) as solid matter
is preferably within a range of 40 to 85 mass% and further within a range of 50 to
80 mass%.
[0039] If the content of the matrix components as solid matter is low, the ratio
20 of the faujasite-type zeolite (A) may become so high that, while the catalytic
activity increases, the bulk density becomes too low or the abrasion resistance,
fluidity, etc. may become insufficient, making the catalyst (1) impractical as a
hydrocarbon catalytic cracking catalyst, especially as a hydrocarbon fluid
catalytic cracking catalyst. On the other hand, if the content of the matrix
25 components as solid matter is too high, the ratio of the faujasite-type zeolite (A)
that is a main active component becomes low, so that the cracking activity may
become insufficient.
[0040] [Rare Earth]
The catalyst (1) further contains a rare earth as a component. The
30 content (CREA) of the rare earth is preferably 0.5 to 2.0 mass% and more
preferably 1.0 to 2.0 mass% as RE2O3 based on the catalyst composition. By
containing a rare earth, the catalyst can become excellent in cracking activity and
14
selectivity of gasoline etc. Examples of the rare earth include a rare earth metal,
such as lanthanum, cerium, and neodymium, and a mixture of these metals.
Usually, a rare-earth mixture consisting mainly of lanthanum and cerium is used.
The rare earth may be introduced by ion exchange after catalyst particles are
manufactured, or ion exchange with the rare earth may be 5 performed on the
faujasite-type zeolite (A) in advance.
[0041] If the content of the rare earth is low, the cracking activity,
selectivity, hydrothermal resistance, metal resistance, etc. may become
insufficient. In the present invention, an upper limit of the content of the rare
10 earth is specified so as to compose the catalyst (1) as a catalyst having a low
hydrogen transfer reaction activity as will be described later.
[0042]
One example of a preferred manufacturing method of the catalyst (1)
will be shown below.
15 1. Preparation Step
The aforementioned silica sol (one example of the silica-based
binder), kaolin, and active alumina powder are added to a liquid for forming
slurry (e.g., pure water), and further slurry of an ultra-stable Y-type zeolite with
its pH adjusted to 3.9 by sulfuric acid is added to this liquid. Thus, a slurry
20 mixture is prepared. A composition of additives that is ascertained in advance
to produce a predetermined hydrogen transfer reaction activity is used.
[0043]
2. Spray-Drying, Cleaning, and Drying Steps
The slurry mixture is spray-dried to obtain spherical particles. The
25 obtained spherical particles are cleaned and then brought into contact with an
aqueous solution of rare earth metal (RE) chloride. After ion exchange is
performed so as to achieve 0.5 to 2.0 mass% as RE2O3, the particles are dried.
Thus, the catalyst (1) is obtained. The average particle size of the obtained
catalyst (1) is not particularly limited as long as it is within such a range that the
30 catalyst (1) can be blended with the catalyst (2) to be described later. However,
from the perspective of the effects of the present invention, the average particle
size is preferably within a range of 40 to 100 m and further within a range of 50
15
to 80 m.
[0044]
The catalyst (2) constituting this embodiment is a catalyst containing
a predetermined faujasite-type zeolite (B), matrix components, and a rare earth,
and this catalyst itself also functions as a fluid catalytic cracking 5 catalyst for
hydrocarbon oil. Each of these components will be described in detail below.
[0045] [Faujasite-Type Zeolite (B)]
The lattice constant (UCS) of the faujasite-type zeolite (B)
constituting part of the catalyst (2) is characterized by being within a range of
10 2.440 to 2.478 nm. A preferable range of the lattice constant is 2.447 to 2.460
nm. When the lattice constant is within such a range, the gasoline selectivity
becomes extremely high. If the lattice constant is too low, the catalytic activity
may become insufficient. On the other hand, if the lattice constant is too high,
the hydrothermal resistance and the metal resistance may become insufficient.
15 Other characteristics, including a preferred structure, are exactly the same as
those of the faujasite-type zeolite (A) constituting part of the catalyst (1).
[0046] As such a faujasite-type zeolite (B), an NH4 Y-type zeolite obtained
by performing NH4 ion exchange on an Na Y-type zeolite can be preferably used,
and an ultra-stable Y-type zeolite (USY) obtained by performing a hydrothermal
20 treatment on an NH4 Y-type zeolite is especially preferable. Alternatively, the
faujasite-type zeolite (B) may be a rare-earth-exchanged Y-type zeolite (REY) or
a rare-earth-exchanged ultra-stable Y-type zeolite (REUSY) obtained by
supporting a rare earth metal by ion exchange etc.
[0047] The content (CZB) of the faujasite-type zeolite (B) in the catalyst (2) as
25 solid matter (mainly SiO2 and Al2O3) is preferably within a range of 15 to 60
mass% and further within a range of 15 to 40 mass%. If the content of the
faujasite-type zeolite (B) as solid matter is lower than 10 mass%, the catalytic
activity may become insufficient due to the low content of the zeolite. If the
content of the faujasite-type zeolite (B) as solid matter exceeds 50 mass%, the
30 catalytic activity may become so high that excessive cracking may occur and the
selectivity may decrease. Moreover, as the content of the matrix components
other than the zeolite decreases, the abrasion resistance becomes insufficient, so
16
that the catalyst may easily pulverize and scatter when used as a fluid catalyst.
While the refill amount of the catalyst can be increased to make up for this, it is
economically problematic.
[0048] [Matrix Components]
As the matrix components, basically the same 5 components as the
matrix components constituting part of the catalyst (1) are preferably used.
[0049] The content of the matrix components in the catalyst (2) as solid matter
is preferably within a range of 40 to 85 mass% and further within a range of 50 to
80 mass% based on the catalyst composition.
10 [0050] If the content of the matrix components as solid matter is low, the ratio
of the faujasite-type zeolite (B) may become so high that, while the catalytic
activity increases, the bulk density becomes too low or the abrasion resistance,
fluidity, etc. become insufficient, making the catalyst impractical as a
hydrocarbon catalytic cracking catalyst, especially as a hydrocarbon fluid
15 catalytic cracking catalyst. On the other hand, if the content of the matrix
components as solid matter is too high, the ratio of the faujasite-type zeolite (B)
that is a main active component becomes low, so that the cracking activity may
become insufficient.
[0051] [Rare Earth]
20 The catalyst (2) further contains a rare earth as a component. The
content (CREB) of the rare earth is preferably 0.5 to 12 mass% and more
preferably 2.5 to 4.0 mass% as RE2O3 based on the catalyst composition. By
containing a rare earth, the catalyst can become excellent in cracking activity and
selectivity of gasoline etc. Examples of the rare earth include rare earth metals,
25 such as lanthanum, cerium, and neodymium, and a mixture of these metals.
Usually, a rare-earth mixture consisting mainly of lanthanum and cerium is used.
[0052] If the content of the rare earth is low, the cracking activity, selectivity,
hydrothermal resistance, metal resistance, etc. may become insufficient. In the
present invention, to compose the catalyst (2) as a catalyst having a high
30 hydrogen transfer reaction activity as will be described later, it is preferable that
the catalyst (2) has a higher content of the rare earth than the catalyst (1).
[0053]
17
One example of a manufacturing method of the catalyst (2) will be
shown below.
1. Preparation Step
An aqueous solution of the aforementioned basic aluminum chloride
(one example of the aluminum compound binder) is diluted 5 with pure water.
Kaolin, active alumina powder, and slurry of a rare-earth-exchanged ultra-stable
Y-type zeolite are added to this solution, and the resulting solution is thoroughly
stirred. Thus, a slurry mixture is prepared. A composition of additives that is
ascertained in advance to produce a predetermined hydrogen transfer reaction
10 activity is used.
[0054] 2. Spray-Drying, Baking, Cleaning, and Drying Steps
The above-described prepared slurry is spray-dried to obtain spherical
particles. Then, the obtained dry powder of the spherical particles is baked,
suspended in warm water, filtered to dehydrate, poured with warm water, and
15 further dried. Thus, the catalyst (2) is obtained. The average particle size of
the obtained catalyst (2) is not particularly limited as long as it is within such a
range that the catalyst (2) can be blended with the catalyst (1). However, from
the perspective of the effects of the present invention, the average particle size is
preferably within a range of 40 to 100 m and further within a range of 50 to 80
20 m.
[0055]
The hydrocarbon catalytic cracking catalyst according to this
embodiment can be manufactured by blending the above-mentioned catalyst (1)
and catalyst (2). A commonly known method can be used as the method of
25 blending these catalysts. The mass blend ratio ((1)/ (2)) of the catalyst (1) and
the catalyst (2) is preferably within a range of 10/90 to 90/10 and more
preferably within a range of 30/70 to 70/30. When the mass blend ratio of the
catalyst (1) and the catalyst (2) is within this range, greater effects of the present
invention can be exerted. In particular, excellent selectivity is exhibited at the
30 ratio of 50/50. While the subject catalyst is a blend of the above-mentioned
specific two types of catalysts, it can also be used by being blended with other
components as long as the effects of the present invention are not undermined.
18
[0056] Second Embodiment
Next, the subject catalyst of a second embodiment of the present
invention that is a blend of two types of catalysts each having a different pore
size and pore volume distribution after being pseudo-equilibrated will be
described. In particular, it is preferable that one catalyst 5 be a catalyst (3)
having, after being pseudo-equilibrated, a pore distribution in which a ratio
(PV1/PV2) of a volume (PV1) of pores having a pore size not smaller than 4 nm
nor larger than 50 nm to a volume (PV2) of pores having a pore size larger than
50 nm is lower than 0.8; that the other catalyst be a catalyst (4) having, after
10 being pseudo-equilibrated, a pore distribution in which (a) a ratio (PV1/PV2) of a
volume (PV1) of pores having a pore size not smaller than 4 nm nor larger than
50 nm to a volume (PV2) of pores having a pore size larger than 50 nm is not
lower than 0.8, and (b) a ratio (PV4/PV3) of a volume (PV4) of pores having a
pore size not smaller than 30 nm nor larger than 100 nm to a volume (PV3) of
15 pores having a pore size larger than 4 nm is lower than 0.2; and that the fluid
catalytic cracking catalyst be composed of the catalyst (3) and the catalyst (4)
blended at a ratio of 100 parts by mass of the former to 10 to 200 parts by mass
of the latter. In the following, this embodiment will be described in detail.
[0057]
20 [Zeolite]
As the zeolite used in this embodiment, a zeolite that is usually used
for catalytic cracking catalysts for hydrocarbon oil can be commonly used. For
example, the zeolite is of one or more than one of the following types: FAU
(faujasite type; e.g., a Y-type zeolite, an X-type zeolite, etc.), MFI (e.g., ZSM-5,
25 TS-1, etc.), CHA (e.g., chabazite, SAPO-34, etc.), and MOR (e.g., mordenite,
Ca-Q, etc.), and especially the FAU type is suitable. Examples of faujasite-type
zeolites include a hydrogen Y-type zeolite (HY), an ultra-stable Y-type zeolite
(USY), and a rare-earth-exchanged Y-type zeolite (REY) and a rare-earthexchanged
ultra-stable Y-type zeolite (REUSY) obtained by supporting a rare
30 earth metal in HY and USY, respectively, by ion exchange etc. In this
embodiment, the content of the zeolite is preferably 15 to 60 mass% and more
preferably 20 to 50 mass%. The content is even more preferably 20 to 40
19
mass%. This is because if the content of the zeolite relative to the catalyst is
lower than 15%, the catalytic cracking activity tends to decrease, while if the
content exceeds 60 mass%, the catalytic cracking activity becomes so high that
the amount of coke deposits increases, and moreover, the bulk density increases
and the strength 5 decreases.
[0058] In this embodiment, a zeolite obtained by ion exchange of a rare earth
metal (RE) may be contained. As the rare earth metal, for example, cerium
(Ce), lanthanum (La), praseodymium (Pr), and neodymium (Nd) can be used.
These metals may be used alone or as a metal oxide of two or more types of
10 metals. These metals may be ones obtained by performing ion exchange on a
zeolite, because containing a rare earth metal enhances the hydrothermal
resistance of a zeolite. In this embodiment, when a rare earth metal is used, it is
contained so as to account for 10.0 mass% or less and preferably account for 0.5
to 5.0 mass% as RE2O3. Here, addition of RE2O3 is adjusted such that the
15 RE2O3/zeolite mass ratio becomes constant in the catalyst.
[0059]
The pore size and pore volume distribution of the pseudo-equilibrated
catalyst is measured by the mercury intrusion technique. The pore size and pore
volume distribution are measured using, for example, PoreMaster-60GT
20 manufactured by Quantachrome Instruments as a measurement device. The
pore size is a value calculated using a surface tension of mercury of 480 dyne/cm
and a contact angle of 150. The pore volume (PVn) in each pore size range is
an integrated value of volumes of pores in each pore diameter range measured by
the mercury intrusion technique. In the present invention, the total pore volume
25 (PV) of the catalyst is preferably not smaller than 0.15 ml/g and more preferably
within a range of 0.20 to 0.40 ml/g.
[0060] FIG. 4 shows one example of pore size and pore volume distributions of
catalysts measured by the above-described test. The pore size (nm) and a logdifferentiated
pore volume dVp/dlogd are plotted on the abscissa and the
30 ordinate, respectively. Based on an example to be described later, c1 represents
one example of the distribution of the catalyst (3); d1 represents one example of
the distribution of the catalyst (4); and R1 represents one example of the
20
distribution of a catalyst of a comparative example in which PV4/PV3 exceeds
0.2.
[0061] A desired cracking reaction activity may not be produced when the
specific surface area of the fluid catalytic cracking catalyst is too small and the
total pore volume is too small. From the perspective of increasing 5 the specific
surface area, it is preferable that there be a large number of small-size pores.
However, pore sizes smaller than 4 nm contribute little to catalytic cracking of
the heavy oil, and therefore pore sizes not smaller than 4 nm are preferable. In
catalytic cracking of hydrocarbon oil, from the viewpoint of reactions for
10 reducing the coke yield, pores of the catalyst having a pore diameter larger than
10 nm are desirable, as they improve the diffusibility of reactants. On the other
hand, it is desirable that there be a smaller number of pores having a pore
diameter larger than 1000 nm, as they may reduce the abrasion resistance of the
catalyst.
15 [0062]
The catalyst (3) is a main constituent element of the fluid catalytic
cracking catalyst according to this embodiment. The characteristics etc. of the
catalyst (3) will be described below.
[0063] [Pore Distribution]
20 After being pseudo-equilibrated, the catalyst (3) has a pore
distribution (pore size and pore volume distribution) in which a ratio (PV1/PV2)
of a volume (PV1) of mesopores having a pore size not smaller than 4 nm nor
larger than 50 nm to a volume (PV2) of macropores having a pore size larger
than 50 nm is lower than 0.8. This pore structure reduces coke formation.
25 (PV1/PV2) of 0.8 or higher is not preferable, as it diminishes the coke formation
reducing effect. If (PV1/PV2) is low, i.e., the catalyst has a large amount of
macropores, a decrease in abrasion resistance is feared. Therefore, (PV1/PV2)
is preferably within a range of 0.4 to 0.7.
[0064] [Components]
30 From the perspective of reducing coke formation, a silica-based
binder alone or a binder composed predominantly of a silica-based binder is
preferable as the binding agent of the matrix components. The silica-based
21
binder is added for the purpose of enhancing the abrasion resistance of the
catalyst (3) of this embodiment and for the purpose of adjusting the amount of
solid acid and the acid strength in the catalyst (3).
[0065]
One example of a preferred manufacturing method of 5 the catalyst (3)
will be shown below.
1. Preparation Step
The aforementioned silica sol (one example of the silica-based
binder), kaolin, and active alumina powder are added to a liquid for forming
10 slurry (e.g., pure water), and further slurry of an ultra-stable Y-type zeolite with
its pH adjusted to 3.9 by sulfuric acid is added to this liquid. Thus, a slurry
mixture is prepared. A composition of additives that is ascertained in advance
to produce the above-described pore distribution is used.
[0066] 2. Spray-Drying, Cleaning, and Drying Steps
15 The slurry mixture is spray-dried to obtain spherical particles. The
obtained spherical particles are cleaned and then brought into contact with an
aqueous solution of rare earth metal (RE) chloride. After ion exchange is
performed so as to achieve 0.5 to 5.0 mass% as RE2O3, the particles are dried.
Thus, the catalyst (3) is obtained. The average particle size of the obtained
20 catalyst (3) is not particularly limited as long as it is within such a range that the
catalyst (3) can be blended with the catalyst (4) to be described later. However,
the average particle size should be about 50 to 100 m.
[0067]
The catalyst (4) is a fluid catalytic cracking catalyst for hydrocarbon
25 oil that is excellent in the heavy oil cracking performance and constitutes the
core of the present invention, and exhibits its effects by being blended with the
catalyst (1). The characteristics of the catalyst (4) will be described below.
[0068] [Pore Distribution]
After being pseudo-equilibrated, the catalyst (4) has a pore size and
30 pore volume distribution in which: (a) a ratio (PV1/PV2) of a volume (PV1) of
mesopores having a pore size not smaller than 4 nm nor larger than 50 nm to a
volume (PV2) of macropores having a pore size larger than 50 nm is not lower
22
than 0.8; and (b) a ratio (PV4/PV3) of a volume (PV4) of pores having a pore
size not smaller than 30 nm nor larger than 100 nm to a volume (PV3) of pores
having a pore size larger than 4 nm is lower than 0.2. This pore structure
imparts a high heavy distillate cracking capability to the catalyst (4). This is
because if (PV1/PV2) is lower than 0.8, the heavy distillate cracking 5 capability
becomes insufficient. If (PV1/PV2) is too high, coke formation may increase,
and therefore the ratio is desirably not higher than 3.0. If (PV4/PV3) is not
lower than 0.2, the catalyst (4) has an insufficient heavy distillate cracking
capability when blended with the catalyst (A). While a lower limit of
10 (PV4/PV3) is not particularly specified, this ratio is hardly likely to become
lower than 0.03, as it is attributable to the sizes of components contained in the
catalyst. It is preferable that (PV1/PV2) be within a range of 1.2 to 2.8 and that
(PV4/PV3) be within a range of 0.08 to 0.15.
[0069] While the reason why the catalyst blended with the catalyst (3) has the
15 high heavy oil cracking performance when the volume of pores having a pore
size not smaller than 30 nm nor larger than 100 nm is reduced is not clear, the
present inventors consider as follows.
[0070] When the catalyst has many pores that are not smaller than 30 nm nor
larger than 100 nm, light cycle oil (LCO) distillates etc. that are intermediate
20 products are more likely to diffuse into particles of the catalyst (4). Therefore,
when the catalyst (4) is blended with the catalyst (3), the intermediate products,
such as LCO distillates, generated by cracking of heavier oil, such as heavy cycle
oil (HCO), are less likely to diffuse from particles (catalyst (4)) to particles
(catalyst (3)), so that the catalyst blend cannot produce a sufficient effect.
25 [0071] [Components]
From the perspective of cracking heavy distillates, an aluminum
compound binder alone, or a binder composed predominantly of an aluminum
compound binder is preferable as the binder component. As the raw material of
the aluminum compound binder, for example, basic aluminum chloride
30 ([Al2(OH)nCl6n]m (where 0 < n < 6 and m  10) can be used. Basic aluminum
chloride dissolves at a relatively low temperature of about 200 to 450C in the
presence of aluminum and cations, such as sodium and potassium, contained in a
23
zeolite etc. As a result, part of the basic aluminum chloride dissolves, and a site
where decomposition products, such as aluminum hydroxide, are present seems
to be formed near the zeolite. Further, an alumina binder (alumina) is formed
by baking the dissolved basic aluminum chloride at a temperature within a range
of 300 to 600C. In this case, when the decomposition products 5 near the zeolite
are baked and the basic aluminum chloride becomes an alumina binder, a
relatively large amount of mesopores having a pore size not smaller than 4 nm
nor larger than 50 nm is formed, which is presumed to increase the specific
surface area of the catalyst (B) according to the present invention. On the other
10 hand, it is also confirmed that formation of macropores having a pore size larger
than 50 nm but not larger than 1000 nm, which reduce the abrasion resistance, is
reduced.
[0072] As the specific surface area of the zeolite component according to the
above-described measurement, 60 to 100 m2/g is preferable from the viewpoint
15 of cracking heavy distillates.
[0073]
One example of a manufacturing method of the catalyst (4) will be
shown below.
1. Preparation Step
20 An aqueous solution of the aforementioned basic aluminum chloride
(one example of the aluminum compound binder) is diluted with pure water.
Kaolin, active alumina powder, and slurry of an ultra-stable Y-type zeolite are
added to this solution, and after the resulting solution is thoroughly stirred, a
lanthanum chloride solution is added. Thus, a slurry mixture is prepared. A
25 composition of additives that is ascertained in advance to produce the abovedescribed
pore distribution is used.
[0074] 2. Spray-Drying, Baking, Cleaning, and Drying Steps
The slurry mixture is spray-dried to obtain spherical particles. Then,
the obtained dry powder of the spherical particles is baked, suspended in warm
30 water, filtered to dehydrate, poured with warm water, and further dried. Thus,
the catalyst (4) is obtained. The average particle size of the obtained catalyst
(4) is not particularly limited as long as it is within such a range that the catalyst
24
(4) can be blended with the catalyst (3). However, the average particle size
should be about 50 to 100 m.
[0075]
The fluid catalytic cracking catalyst according to this embodiment is
manufactured by first adjusting two types of catalysts each 5 having a different
pore size and pore volume distribution that have been pseudo-equilibrated, and
then blending these catalysts by a commonly known method. The fluid catalytic
cracking catalyst of this embodiment thus obtained is a catalyst composed of the
catalyst (3) and the catalyst (4) blended at a ratio of 100 parts by mass of the
10 former to 10 to 200 parts by mass of the latter. If the blend amount of the
catalyst (4) is smaller than 10 parts by mass relative to 100 parts by mass of the
catalyst (3), the heavy distillate cracking capability becomes insufficient and the
gasoline + LPG yield does not increase. On the other hand, if the blend amount
exceeds 200 parts by mass, the coke formation reducing effect of the catalyst (3)
15 diminishes and the gasoline + LPG yield decreases. Therefore, the catalyst (3)
and the catalyst (4) are blended at a ratio of 100 parts by mass of the former to 10
to 200 parts by mass of the latter. It is preferable that the catalyst (3) and the
catalyst (4) be blended at a ratio of 100 parts by mass of the former to 40 to 100
parts by mass of the latter. The blend ratio (mass ratio) of the catalyst (3) and
20 the catalyst (4) should be determined such that decomposition products
(especially gasoline and LPG) obtained by cracking hydrocarbon oil by the
subject fluid catalytic cracking catalyst have a desired composition (yield).
[0076]
For a fluid catalytic cracking method using the fluid catalytic cracking
25 catalyst according to the present invention, usual conditions for fluid catalytic
cracking of hydrocarbon oil can be used, and for example, the following
conditions are suitable.
[0077] As the raw oil used for catalytic cracking, usual hydrocarbon raw oil,
for example, hydrodesulfurized vacuum gas oil (DSVGO) and vacuum gas oil
30 (VGO) can be used. In addition, residual oil, such as atmospheric distillation
residue (AR), vacuum distillation residue (VR), desulfurized atmospheric
distillation residue (DSAR), desulfurized vacuum distillation residue (DSVR), or
25
deasphaltene oil (DAO), can also be used. These oils can be used alone or as a
blend of oils. The fluid catalytic cracking catalyst according to the present
invention can also treat residual oil containing 0.5 ppm or more each of nickel
and vanadium, and can also be used for residual oil catalytic cracking devices
(Resid FCC; RFCC) that use residual oil alone as raw 5 oil. Here, when a
conventional fluid catalytic cracking catalyst is used in an RFCC, nickel and
vanadium contained in residual oil adhere to the catalyst and reduce the catalytic
activity. However, the fluid catalytic cracking catalyst of the present invention
can maintain excellent catalytic performance even when treating residual oil that
10 contains 0.5 ppm or more each of vanadium and nickel. Moreover, the fluid
catalytic cracking catalyst of the present invention can maintain the catalytic
performance even when the content of each of vanadium and nickel is 300 ppm
or higher. An upper limit of the content of each of vanadium and nickel in the
fluid catalytic cracking catalyst of the present invention is about 10000 ppm.
15 [0078] For catalytic cracking of the above-mentioned hydrocarbon raw oil, a
reaction temperature within a range of 470 to 550C is suitably used, and a
reaction pressure within a range of about 1 to 3 kg/cm2 is generally suitable.
The catalyst/oil mass ratio (catalyst/oil ratio) is preferably within a range of 2.5
to 9.0, and the contact time is preferably within a range of 10 to 60 hr1.
20 [0079] [Hydrogen Transfer Reaction Activity: Isobutane/Butene (iC4/C4=)
Ratio]
In the present invention, a performance evaluation test of catalysts
with the same raw oil and the same reaction conditions is performed using
advanced cracking evaluationmicro activity test (ACEMAT), and the
25 performance is evaluated based on an (iC4/C4=) ratio that is the ratio between
the mass of isobutane and the mass of butene, which are decomposition products,
as an index of the hydrogen transfer reaction activity of catalysts. If the
difference in the (iC4/C4=) ratio between the catalyst (1) and the catalyst (2) is
within a range of 0.10 to 0.85, a low coke ratio and a low HCO yield are
30 achieved. On the other hand, if the difference is smaller than the lower limit,
the HCO yield may become high even when the coke ratio is the same. If the
difference is larger than the upper limit, the cracking activity may become too
26
low.
[0080] [(Gasoline + LPG Yield) G]
For example, it is preferable that a (gasoline + LPG yield) GM of the
fluid catalytic cracking catalyst that is a blend of the catalyst (3) and the catalyst
(4) be higher than a (gasoline + LPG yield) GA of the catalyst (5 3) and a (gasoline
+ LPG yield) GB of the catalyst (4). Here, the (gasoline + LPG yield) GM is
calculated from (mass of gasoline + mass of LPG) obtained by performing
catalytic cracking of raw oil by the above-described method, and the mass of the
raw oil.
10 Examples
[0081] In the following, the present invention will be described in further detail
using examples. However, the present invention is in no way limited by these
examples.
Manufacturing Example 1
15
a. Preparation Step
2941 g of water glass (SiO2 concentration: 17 mass%) and 1059 g of
sulfuric acid (sulfuric acid concentration: 25 mass%) are added simultaneously
and continuously to prepare 4000 g of silica sol (one example of the silica-based
20 binder) with an SiO2 concentration of 12.5 mass%. To this silica sol, 893 g of
kaolin (solid matter concentration: 84 mass%) and 309 g of active alumina
powder (solid matter: 81 mass%) are added, and further 3030 g of slurry of an
ultra-stable Y-type zeolite (UCS: 2.443 nm, solid matter concentration: 33
mass%) with its pH adjusted to 3.9 by sulfuric acid is added. Thus, a slurry
25 mixture is prepared.
[0082] b. Spray-Drying, Cleaning, and Drying Steps
The slurry mixture is turned into droplets and spray-dried by a spray
dryer having an inlet temperature of 230C and an outlet temperature of 130C to
obtain spherical particles with an average particle size of 70 m. The obtained
30 spray-dried particles are suspended in 10 times their amount by mass of warm
water (60C) and filtered to dehydrate. Then, the particles are poured with 10
times their amount by mass of warm water (60C), further suspended, brought
27
into contact with an aqueous solution of rare earth metal (RE) chloride
(containing chlorides of cerium and lanthanum), and ion exchange is performed
so as to achieve 1.1 mass% as RE2O3. Thereafter, the catalyst particles are
dried by a drier at an atmospheric temperature of 135C. Thus, a catalyst a1 is
5 obtained.
[0083] c. Specific Surface Area
The above-mentioned specific surface area measurement is performed
on the catalyst a1 that had been pseudo-equilibrated, and the area is found to be
223 m2/g. The surface area of the matrix components is 31 m2/g and the
10 specific surface area of the zeolite component is 192 m2/g.
[0084]
a. Preparation Step
2941 g of water glass (SiO2 concentration: 17 mass%) and 1059 g of
sulfuric acid (sulfuric acid concentration: 25 mass%) are added simultaneously
15 and continuously to prepare 4000 g of silica sol (one example of the silica-based
binder) with an SiO2 concentration of 12.5 mass%. To this silica sol, 1042 g of
kaolin (solid matter concentration: 84 mass%) and 309 g of active alumina
powder (solid matter: 81 mass%) are added, and further 2652 g of slurry of an
ultra-stable Y-type zeolite (UCS: 2.458 nm, solid matter concentration: 33
20 mass%) with its pH adjusted to 3.9 by sulfuric acid is added. Thus, a slurry
mixture is prepared.
[0085] b. Spray-Drying, Cleaning, and Drying Steps
The slurry mixture is turned into droplets and spray-dried by a spray
dryer having an inlet temperature of 230C and an outlet temperature of 130C to
25 obtain spherical particles with an average particle size of 70 m. The obtained
spray-dried particles are suspended in 10 times their amount by mass of warm
water (60C) and filtered to dehydrate. Then, the particles are poured with 10
times their amount by mass of warm water (60C), further suspended, brought
into contact with an aqueous solution of rare earth metal (RE) chloride
30 (containing chlorides of cerium and lanthanum), and ion exchange is performed
so as to achieve 1.1 mass% as RE2O3. Thereafter, the catalyst particles are
dried by a drier at an atmospheric temperature of 135C. Thus, a catalyst a2 is
28
obtained.
[0086] c. Specific Surface Area
The above-mentioned specific surface area measurement is performed
on the catalyst a2 that had been pseudo-equilibrated, and the area is found to be
181 m2/g. The surface area of the matrix components is 5 149 m2/g and the
specific surface area of the zeolite component is 32 m2/g.
[0087]
a. Preparation Step
447 g of an aqueous solution containing 23.5 mass% of basic
10 aluminum chloride and 1075 g of pure water are mixed. Then, while this mixed
solution is thoroughly stirred, 530 g of kaolin (solid matter concentration: 84
mass%), 247 g of active alumina powder (solid matter concentration: 81 mass%),
and 294 g of powder of an RE-exchanged ultra-stable Y-type zeolite (RE2O3:
11.2 mass%, UCS: 2.460 nm, solid matter concentration: 85 mass%) are
15 sequentially added. Then, the resulting solution is thoroughly stirred to obtain a
slurry mixture. The obtained slurry mixture is subjected to a dispersion
treatment using a homogenizer, which resulted in a solid matter concentration of
38 mass%.
[0088] b. Spray-Drying, Baking, Cleaning, and Drying Steps
20 The slurry mixture thus obtained is turned into droplets and spraydried
by a spray dryer having an inlet temperature of 230C and an outlet
temperature of 130C to obtain spherical particles with an average particle size of
70 m. This dry powder is baked in an electric furnace in an air atmosphere at
400C for an hour, and then the baked product is suspended in 10 times its
25 amount by mass of warm water (60C) and filtered to dehydrate. Further, the
product is poured with 10 times its amount by mass of warm water (60C), and
the cake is collected and dried for 10 hours in a drier with an atmospheric
temperature kept at 140C. Thus, a catalyst b1 is obtained.
[0089] c. Specific Surface Area
30 The above-mentioned specific surface area measurement is performed
on the catalyst b1 that had been pseudo-equilibrated, and the area is found to be
167 m2/g. The surface area of the matrix components is 90 m2/g and the
29
specific surface area of the zeolite component is calculated to be 77 m2/g.
[0090]
a. Preparation Step
This step is performed in the same manner as the preparation step of
the catalyst b1, except that the zeolite powder is changed 5 to powder of an REexchanged
ultra-stable Y-type zeolite (RE2O3: 18.2 mass%, UCS: 2.476 nm, solid
matter concentration: 85 mass%).
[0091] b. Spray-Drying, Baking, Cleaning, and Drying Steps
The same spray-drying, baking, cleaning, and drying steps as those of
10 the catalyst b1 are performed to obtain a catalyst b2.
[0092] c. Specific Surface Area
The above-mentioned specific surface area measurement is performed
on the catalyst b2 that has been pseudo-equilibrated, and the area is found to be
159 m2/g. The surface area of the matrix components is 86 m2/g and the
15 specific surface area of the zeolite component is calculated to be 73 m2/g.
[0093]
a. Preparation Step
This step is performed in the same manner as the preparation step of
the catalyst a1.
20 [0094] b. Spray-Drying, Baking, Cleaning, and Drying Steps
The same steps as those of the catalyst a1, except that ion exchange is
performed so as to achieve 2.5 mass% as RE2O3, are performed to obtain a
catalyst b3.
[0095] c. Specific Surface Area
25 The above-mentioned specific surface area measurement is performed
on the catalyst b3 that had been pseudo-equilibrated, and the area is found to be
217 m2/g. The surface area of the matrix components is 29 m2/g and the
specific surface area of the zeolite component is calculated to be 188 m2/g.
[0096]
30 The obtained catalyst a1 and catalyst b1 are blended at a ratio of 50
parts by mass as solid matter of the former to 50 parts by mass as solid matter of
the latter. Thus, a catalyst blend a1b1 according to the first embodiment of the
30
present invention is obtained.

The obtained catalyst a1 and catalyst b2 are blended at a ratio of 50
parts by mass as solid matter of the former to 50 parts by mass as solid matter of
the latter. Thus, a catalyst blend a1b2 according to the first 5 embodiment of the
present invention is obtained.

The obtained catalyst a2 and catalyst b1 are blended at a ratio of 50
parts by mass as solid matter of the former to 50 parts by mass as solid matter of
10 the latter. Thus, a catalyst blend a2b1 according to the first embodiment of the
present invention is obtained.

The obtained catalyst a1 and catalyst b3 are blended at a ratio of 50
parts by mass as solid matter of the former to 50 parts by mass as solid matter of
15 the latter. Thus, a catalyst blend a1b3 according to the first embodiment of the
present invention is obtained.
[0097] Comparative Example

The obtained catalyst b3 and catalyst b1 are blended at a ratio of 50
20 parts by mass as solid matter of the former to 50 parts by mass as solid matter of
the latter. Thus, a catalyst blend b3b1 of a comparative example is obtained.
[0098] [Catalytic Activity Evaluation Test]

A catalytic performance evaluation test with the same raw oil and the
25 same reaction conditions is performed using ACEMAT for each single catalyst
and each catalyst blend according to the above-described manufacturing
example. Before evaluation, all the catalysts and catalyst blends are subjected
to a pseudo-equilibration treatment by being held at 790C for 13 hours under a
100% water vapor condition.
30 The operation conditions for the performance evaluation test are as
follows:
Reaction temperature: 520C
31
Regeneration temperature: 700C
Raw oil: Hydrodesulfurized vacuum gas oil (DSVGO) 100%
Catalyst/oil ratio: 3.75 and 5.00 mass%/mass%, where
- Conversion ratio (mass%) = (A  B)/A  100
A: 5 Mass of raw oil
B: Mass of distillates of 216C or higher in
produced oil
- Hydrogen (mass%) = C/A  100
C: Mass of hydrogen in produced gas
10 - C1 + C2 (mass%) = D/A  100
D: Masses of C1 (methane) and C2 (ethane and
ethylene) in produced gas
- LPG (liquefied petroleum gas, mass%) = E/A  100
E: Masses of propane, propene, butane, and
15 butene in produced gas
- Gasoline (mass%) = F/A  100
F: Mass of gasoline (boiling point range: C5 to
216C) in produced oil
- LCO (mass%) = G/A  100
20 G: Mass of light cycle oil (boiling point range:
216 to 343C) in produced oil
- HCO (mass%) = H/A  100
H: Mass of heavy cycle oil (boiling point
range: 343C or higher) in produced oil
25 - Coke (mass%) = I/A  100
I: Mass of coke having deposited on a catalyst
blend
- (iC4/C4=) ratio = mass of isobutane / mass of butene
[0099] Table 1 shows the results of the catalytic activity evaluation test of the
30 single catalysts a1, a2, b1, b2, and b3 prepared as described above. The
(iC4/C4=) ratio in Table 1 represents the mass of isobutane/the mass of butene
at the catalyst/oil ratio of 3.75.
32
[0100] Table 1
Single catalyst
a1
Single catalyst
a2
Single catalyst
a3
Single catalyst
b1
Single catalyst
b3
(iC4/C4=) ratio 0.55 0.64 0.80 0.82 1.30
Conversion ratio (mass%) (C/O = 5.00)(mass%) 76.50 76.73 78.61 80.48 81.00
Yield at the same conversion ratio (77%)
Hydrogen (mass%)
C1 + C2 (mass%)
LPG(mass%)
Gasoline (mass%)
LCO (mass%)
HCO(mass)
Coke (mass%)
0.07
1.64
20.49
52.18
14.96
8.04
2.62
0.06
1.53
20.53
51.54
14.72
8.19
3.44
0.05
1.58
18.86
53.82
14.94
8.06
2.69
0.10
1.53
18.78
53.65
16.06
6.94
2.93
0.07
1.54
18.53
54.55
15.54
7.46
2.30
33
[0101] Table 2 shows the results of the catalytic activity evaluation test of the
catalyst blend a1b1 (mass ratio of a1:b1 = 50:50), the catalyst blend a1b2 (mass
ratio of a1:b2 = 50:50), the catalyst blend a2b1 (mass ratio of a2:b1 = 50:50), and
the catalyst blend a1b3 (mass ratio of a1:b3 = 50:50) according to the first
embodiment of the present invention prepared as described 5 above, and the
catalyst blend b3b1 (mass ratio of b3:b1 = 50:50) of the comparative example
prepared as described above. As shown next to one another in Table 2, the
differences in (iC4/C4=) ratio between the single catalysts of the catalyst blends
according to the first embodiment of the present invention are 0.18 to 0.75, while
10 the difference in (iC4/C4=) ratio between the single catalysts b3 and b1 of the
catalyst blend b3b1 of the comparative example is 0.02 and thus almost nonexistent.
34
[0102] Table 2
a1b1 a1b2 a2b1 a1a3 a3b1
Blend composition ratio 50:50 50:50 50:50 50:50 50:50
Difference in (iC4/C4=) ratio 0.26 0.75 0.18 0.25 0.02
Conversion ratio (C/O = 5.00) (mass%) 79.19 80.11 79.12 78.34 79.35
Yield at the same conversion ratio (77%)
Hydrogen (mass%)
C1 +C2 (mass%)
LPG (mass%)
Gasoline (mass%)
LCO (mass%)
HCO (mass%)
Coke (mass%)
0.09
1.55
18.99
53.66
15.59
7.41
2.71
0.09
1.55
18.92
54.10
14.94
8.06
2.34
0.07
1.49
19.30
53.29
15.76
7.24
2.84
0.07
1.58
19.06
53.83
14.87
8.13
2.46
0.07
1.56
18.95
53.44
15.41
7.59
2.98
Remarks
Invention
Example
Invention
Example
Invention
Example
Invention
Example
Comparative
Example
35
[0103] These test results are organized and shown in FIG. 1, FIG. 2, and FIG.
3. FIG. 1 shows relationships between the blend ratios of the catalyst blends
and the coke yield. The abscissa represents the percentage of the ratio of one
catalyst of each catalyst blend that has a higher hydrogen 5 transfer reaction
activity. All the catalyst blends of the examples of the present invention have a
downward convex curve, which shows that blending equal amounts of catalysts
results in a lower coke yield than the arithmetic means of the single catalysts.
By contrast, the catalyst blend b3b1 of the comparative example has an upward
10 convex curve, which shows that blending the catalysts results in a higher coke
yield than the yields of the single catalysts. Like FIG. 1, FIG. 2 is a graph with
the blend ratio and the gasoline yield plotted on the abscissa and the ordinate,
respectively. All the catalyst blends of the examples of the present invention
have an upward convex curve, which shows that the gasoline yield is higher than
15 the arithmetic means of the single catalysts. By contrast, the catalyst blend
b3b1 of the comparative example has a downward convex curve, which shows
that blending the catalysts results in a lower gasoline yield than the yields of the
single catalysts. Like FIG. 1, FIG. 3 is a graph with the blend ratio and the
HCO + coke yield plotted on the abscissa and the ordinate, respectively. All the
20 catalyst blends of the examples of the present invention, except for the catalyst
blend a2b1, have a downward convex curve, which shows that both heavy oil
cracking and low coke level are achieved. The catalyst blend of the
comparative example has an upward convex curve, and no improvement by
blending is seen. A possible reason why the catalyst blend a2b1 has no effect of
25 blending on the heavy oil cracking is that the difference in hydrogen transfer
reaction activity is too large.
[0104] Manufacturing Example 2

a. Preparation Step
30 2941 g of water glass (SiO2 concentration: 17 mass%) and 1059 g of
sulfuric acid (sulfuric acid concentration: 25 mass%) are added simultaneously
and continuously to prepare 4000 g of silica sol (one example of the silica-based
36
binder) with an SiO2 concentration of 12.5 mass%. To this silica sol, 893 g of
kaolin (solid matter concentration: 84 mass%) and 556 g of active alumina
powder (solid matter: 81 mass%) are added, and further 2424 g of slurry of an
ultra-stable Y-type zeolite (solid matter concentration: 33 mass%) with its pH
adjusted to 3.9 by sulfuric acid is added. Thus, a slurry mixture 5 is prepared.
[0105] b. Spray-Drying, Cleaning, and Drying Steps
The slurry mixture is turned into droplets and spray-dried by a spray
dryer having an inlet temperature of 230C and an outlet temperature of 130C to
obtain spherical particles with an average particle size of 70 m. The obtained
10 spray-dried particles are suspended in 10 times their amount by mass of warm
water (60C) and filtered to dehydrate. Then, the particles are poured with 10
times their amount by mass of warm water (60C), further suspended, brought
into contact with an aqueous solution of rare earth metal (RE) chloride
(containing chlorides of cerium and lanthanum), and ion exchange is performed
15 so as to achieve 2.1 mass% as RE2O3. Thereafter, the catalyst particles are
dried by a drier at an atmospheric temperature of 135C. Thus, a catalyst c1 is
obtained.
[0106] c. Pseudo-Equilibration Step
The catalyst c1 thus obtained is baked in advance at an atmospheric
20 temperature of 600C for two hours. Then, nickel octyl acid salt and vanadium
octyl acid salt are deposited on the baked catalyst particles, respectively in
amounts, as converted to metal amounts, of 1000 ppm (the mass of nickel is
divided by the mass of the catalyst) and 2000 ppm (the mass of vanadium is
divided by the mass of the catalyst). Then, the catalyst is dried at an
25 atmospheric temperature of 110C and baked at an atmospheric temperature of
600C for 1.5 hours. Thereafter, the catalyst is subjected to a steaming
treatment for 13 hours at an atmospheric temperature of 780C. Thus, the
pseudo-equilibrated catalyst c1 is obtained.
[0107] d. Measurement of Pore Size and Pore Volume Distribution
30 The pore size and pore volume distribution of the pseudo-equilibrated
catalyst c1 is measured by the above-mentioned mercury intrusion technique.
The pseudo-equilibrated catalyst c1 is baked at an atmospheric temperature of
37
600C for an hour before measurement. The total pore volume is 0.28 ml/g.
The ratio PV1/PV2 of the volume (PV1) of mesopores having a pore size not
smaller than 4 nm nor larger than 50 nm to the volume (PV2) of macropores
having a pore size larger than 50 nm is 0.56. FIG. 4 shows the distribution of a
log-differentiated pore volume dV/dlogd relative to the pore 5 size [nm] of the
pseudo-equilibrated catalyst c1.
[0108] e. Specific Surface Area
The above-mentioned specific surface area measurement is performed
on the pseudo-equilibrated catalyst c1, and the area is found to be 169 m2/g.
10 The surface area of the matrix components is 48 m2/g and the specific surface
area of the zeolite component is 121 m2/g.
[0109]
a. Preparation Step
531.9 g of an aqueous solution containing 23.5 mass% of basic
15 aluminum chloride and 1138.0 g of pure water are mixed. Then, while this
mixed solution is thoroughly stirred, 452.4 g of kaolin (solid matter
concentration: 84 mass%), 246.9 g of active alumina powder (solid matter
concentration: 81 mass%), and 333.3 g of powder of an ultra-stable Y-type
zeolite (solid matter concentration: 75 mass%) are sequentially added. Then,
20 154.6 g of a lanthanum chloride solution (La2O3 concentration: 29.1 mass%) is
added and the resulting solution is thoroughly stirred. Thus, a slurry mixture is
prepared. The obtained slurry mixture is subjected to a dispersion treatment
using a homogenizer, which results in a solid matter concentration of 35 mass%
and pH of 3.8.
25 [0110] b. Spray-Drying, Baking, Cleaning, and Drying Steps
The slurry mixture thus obtained is turned into droplets and spraydried
by a spray dryer having an inlet temperature of 230C and an outlet
temperature of 130C to obtain spherical particles with an average particle size of
70 m. This dry powder is baked in an electric furnace in an air atmosphere at
30 400C for an hour, and then the baked product is suspended in 10 times its
amount by mass of warm water (60C) and filtered to dehydrate. Further, the
product is poured with 10 times its amount by mass of warm water (60C), and
38
the cake is collected and dried for 10 hours in a drier with an atmospheric
temperature kept at 140C. Thus, a catalyst d1 is obtained.
[0111] c. Pseudo-Equilibration Step
The obtained catalyst d1 is subjected to a pseudo-equilibration
treatment using the same conditions as those of 5 the catalyst c1.
[0112] d. Measurement of Pore Size and Pore Volume Distribution
The pore size and pore volume distribution of the pseudo-equilibrated
catalyst d1 is measured by the above-mentioned mercury intrusion technique in
the same manner as the catalyst c1. The total pore volume is 0.39 ml/g. The
10 ratio PV1/PV2 of the volume (PV1) of mesopores having a pore size not smaller
than 4 nm nor larger than 50 nm to the volume (PV2) of macropores having a
pore size larger than 50 nm is 1.53. The ratio PV4/PV3 of the volume (PV4) of
pores having a pore size not smaller than 30 nm nor larger than 100 nm to the
volume (PV3) of pores having a pore size larger than 4 nm is 0.11. FIG. 4
15 shows the distribution of a log-differentiated pore volume dV/dlogd relative to
the pore size [nm] of the pseudo-equilibrated catalyst d1.
[0113] e. Specific Surface Area
The above-mentioned specific surface area measurement is performed
on the pseudo-equilibrated catalyst d1, and the area is found to be 166 m2/g.
20 The surface area of the matrix components is 90 m2/g and the specific surface
area of the zeolite component is calculated to be 76 m2/g.
[0114]
The obtained catalyst c1 and catalyst d1 are blended at a ratio of 100
parts by mass as solid matter of the former to 42.9 parts by mass and 100 parts by
25 mass as solid matter of the latter. Thus, a catalyst blend c1d1 according to the
second embodiment of the present invention is obtained.
[0115] Comparative Example

a. Preparation Step
30 531.9 g of an aqueous solution containing 23.5 mass% of basic
aluminum chloride and 299.3 g of pure water are mixed. Then, while this mixed
solution is thoroughly stirred, 452.4 g of kaolin (solid matter concentration: 84
39
mass%), 61.7 g of active alumina powder (solid matter concentration: 81
mass%), 1500 g of slurry of active alumina (boehmite gel slurry; solid matter
concentration: 10 mass%) with its pH adjusted to 3.1 by sulfuric acid in advance,
and 333.3 g of powder of an ultra-stable Y-type zeolite (solid matter
concentration: 75 mass%) are sequentially added. Then, 154.6 5 g of a lanthanum
chloride solution (La2O3 concentration: 29.1 mass%) is added and the resulting
solution is thoroughly stirred. Thus, a slurry mixture is obtained. The
obtained slurry mixture is subjected to a dispersion treatment using a
homogenizer, which results in a solid matter concentration of 30 mass% and pH
10 of 3.4.
[0116] b. Spray-Drying, Baking, Cleaning, and Drying Steps
The slurry mixture is turned into droplets and spray-dried by a spray
dryer having an inlet temperature of 230C and an outlet temperature of 130C to
obtain spherical particles with an average particle size of 68 m. This dry
15 powder is baked in an electric furnace in an air atmosphere at 400C for an hour,
and then the baked product is suspended in 10 times its amount by mass of warm
water (60C) and filtered to dehydrate. Further, the product is poured with 10
times its amount by mass of warm water (60C), and the cake is collected and
dried for 10 hours in a drier with an atmospheric temperature kept at 140C.
20 Thus, a catalyst R1 is obtained.
[0117] c. Pseudo-Equilibration Step
The obtained catalyst R1 is subjected to a pseudo-equilibration
treatment using the same conditions as those of the catalyst c1.
[0118] d. Measurement of Pore Size and Pore Volume Distribution
The pore size and pore volume distribution of the pseudo-equilibrated
catalyst R1 is measured by the above-described mercury intrusion technique, in
the same manner as the catalyst c1. The total pore volume is 0.31 ml/g. The
ratio PV1/PV2 of the volume (PV1) of mesopores having a pore size not smaller
than 4 nm nor larger than 50 nm to the volume (PV2) of macropores having a
pore size larger than 50 nm is 1.14. The ratio PV4/PV3 of the volume (PV4) of
pores having a pore size not smaller than 50 nm nor larger than 100 nm to the
volume (PV3) of pores having a pore size larger than 4 nm is 0.25. FIG. 4
shows the distribution of a log-differentiated pore volume dV/dlogd relative to
the pore size [nm] of the pseudo-equilibrated catalyst R1.
[0119] e. Specific Surface Area
The above-mentioned specific surface area measurement is performed
on the pseudo-equilibrated catalyst R1, and the area is found 5 to be 160 m2/g.
The surface area of the matrix components is 87 m2/g and the specific surface
area of the zeolite component is calculated to be 73 m2/g.
[0120]
The obtained catalyst c1 and catalyst R1 are blended at a ratio of 100
parts by mass as solid matter of the former to 42.9 parts by mass as solid matter
of the latter. Thus, a catalyst blend c1R1 of a comparative example is obtained.
[0121] [Catalytic Activity Evaluation Test]

A catalytic performance evaluation test with the same raw oil and the
same reaction conditions is performed using advanced cracking evaluationmicro
activity test (ACEMAT) for each of the single catalysts and the catalyst blends
according to the above-described manufacturing example and comparative
example. Before evaluation, all the catalysts and catalyst blends are subjected
to the above-described pseudo-equilibration treatment.
The operation conditions for the performance evaluation test are as
follows:
Reaction temperature: 520C
Regeneration temperature: 700C
Raw oil: Desulfurized atmospheric residual oil (DSAR) 50%:
hydrodesulfurized vacuum gas oil (DSVGO) 50%
Catalyst/oil ratio: 7 mass%/mass%, where
- Conversion ratio (mass%) = (A  B)/A  100
A: Weight of raw oil
B: Weight of distillates of 216C or higher in
produced oil
- Hydrogen (mass%) = C/A  100
C: Weight of hydrogen in produced gas
41
- C1 + C2 (mass%) = D/A  100
D: Weights of C1 (methane) and C2 (ethane
and ethylene) in produced gas
- LPG (liquefied petroleum gas, mass%) = E/A  100
E: Weights of propane, propylene, 5 butane, and
butylene in produced gas
- Gasoline (mass%) = F/A  100
F: Weight of gasoline (boiling point range: C5
to 216C) in produced oil
- LCO (mass%) = G/A  100
G: Weight of light cycle oil (boiling point
range: 216 to 343C) in produced oil
- HCO (mass%) = H/A  100
H: Weight of heavy cycle oil (boiling point
range: 343C or higher) in produced oil
- Coke (mass%) = I/A  100
I: Weight of coke having deposited on the
catalyst blend
[0122] Table 3 shows the results of the catalytic activity evaluation test of the
20 single catalysts c1, d1, and R1 prepared as described above.
[0123] Table 3
Single
catalyst c1
Single
catalyst d1
Single
catalyst R1
PV1/PV2 0.56 1.53 1.14
PV4/PV3 － 0.11 0.25
Conversion ratio (C/O = 5) (mass%) 75.2 77.3 76.9
Yield at the same conversion ratio
Hydrogen (mass%)
C1 + C2 (mass%)
LPG (mass%)
Gasoline (mass%)
LCO (mass%)
HCO (mass%)
Coke (mass%)
0.4
2.0
15.4
50.2
16.4
8.4
7.1
0.7
2.2
15.4
49.7
16.1
6.6
9.3
0.7
2.2
15.0
49.9
16.5
6.6
9.1
[0124] The results of Table 3 show that if (PV1/PV2) is lower than 0.8, the
coke yield becomes low and the HCO yield becomes high. If (PV1/PV2) is not
lower than 0.8, conversely the coke yield becomes high and the HCO yield
becomes low. FIG. 5 shows the results of Table 3 with (PV1/PV2) and the coke
and HCO yield plotted on the abscissa and the ordinate, 5 respectively.
[0125] Table 4 shows the results of the catalytic activity evaluation test of the
catalyst blend c1d1 (mass ratio of c1:d1 = 70:30 and 50:50) according to the
second embodiment of the present invention prepared as described above, and the
catalyst blend c1R1 (mass ratio of c1: R1 = 70:30) of the comparative example
prepared as described above.
[0126] Table 4
c1d1 c1d1 c1R1
Blend composition ratio 70:30 50:50 70:30
PV4/PV3 (d1 or R1) 0.11 0.11 0.25
Conversion ratio (C/O = 5) (mass%) 76.2 76.7 76.9
Yield at the same conversion ratio
Hydrogen (mass%)
C1 + C2 (mass%)
Gasoline + LPG (mass%)
LCO (mass%)
HCO (mass%)
Coke (mass%)
0.5
2.0
65.9
16.4
7.4
7.8
0.6
2.1
66.2
16.5
6.7
7.8
0.5
2.1
66.0
16.2
7.8
7.4
Remarks
Invention
Example
[0127] The results of Table 4 show that if the blend ratio with the catalyst c1
(70:30) is equal, the catalyst blend c1d1 using the catalyst d1 of which
(PV4/PV3) is not higher than 0.2 can further reduce the HCO yield, i.e., further
crack the heavy oil, than c1R1. FIG. 6 shows the results of Table 2, with
(PV4/PV3) plotted on the abscissa and the difference between 5 the HCO yield of
the catalyst blend calculated from the single catalysts and the measured HCO
yield plotted on the ordinate. It can be seen that (PV4/PV3) not higher than 0.2
makes the catalyst blend more effective in cracking heavy oil than the calculated
value and is therefore preferable.
[0128] FIG. 7 shows how the blend ratio of the catalysts c1 and d1 influences
the gasoline + LPG yield that are high-value-added products. It can be seen that
the catalyst blend has a higher gasoline + LPG yield that are high-value-added
products than the single catalysts, and that, in particular, the catalyst blend has a
high yield of high-value-added products (products) than the single catalysts if the
ratio of d1 to the entire catalyst blend is 9 mass% to 66 mass% (a ratio of 100
parts by mass of the catalyst c1 to 10 to 200 parts by mass of d1).
[0129] FIG. 8 shows how the blend ratio of the catalysts c1 and d1 influences
the coke + HCO yield. The catalyst blend has a clearly lower coke + HCO yield
than the single catalysts, and thus has high performance in converting heavy
distillates into gasoline and LPG that are high-value-added products.
[0130] As has been described above, the catalyst blends of the present
invention can particularly increase the yields of gasoline and LPG that are highvalue-
added products and can also reduce the coke yield while reducing heavy
distillates.

We Claim:
[Claim 1]
A fluid catalytic cracking catalyst for hydrocarbon oil excellent in
product yield that is a blend of two types of fluid catalytic 5 cracking catalysts
each of which has a different hydrogen transfer reaction activity or has a pore
distribution within a specific range after being pseudo-equilibrated, the fluid
catalytic cracking catalyst being characterized in that:
one catalyst is a catalyst containing a zeolite and matrix components;
the other catalyst is a catalyst containing a zeolite and matrix
components; and
the fluid catalytic cracking catalyst is composed of the one catalyst
and the other catalyst blended at a mass ratio within a range of 10:90 to 90:10.
[Claim 2]
The fluid catalytic cracking catalyst for hydrocarbon oil excellent in
product yield according to claim 1, wherein:
the fluid catalytic cracking catalyst for hydrocarbon oil is a blend of
two types of fluid catalytic cracking catalysts each of which has a different
hydrogen transfer reaction activity;
one catalyst is a catalyst (1) containing a faujasite-type zeolite (A)
having a lattice constant within a range of 2.435 to 2.459 nm, matrix
components, and a rare earth;
the other catalyst is a catalyst (2) containing a faujasite-type zeolite
(B) having a lattice constant within a range of 2.440 to 2.478 nm, matrix
components, and a rare earth; and
the hydrogen transfer reaction activity of the catalyst (1) is lower than
the hydrogen transfer reaction activity of the catalyst (2).
[Claim 3]
The fluid catalytic cracking catalyst for hydrocarbon oil excellent in
product yield according to claim 2, wherein
a difference between the one catalyst and the other catalyst in an
(iC4/C4=) ratio (where iC4 and C4= represent masses of isobutane and butene,
respectively, in a test that evaluates performance in fluid catalytic cracking of
hydrocarbon oil) that is an index of hydrogen transfer reaction activity is within a
range of 0.10 to 0.85.
[Claim 4]
The fluid catalytic cracking catalyst for hydrocarbon 5 oil excellent in
product yield according to claim 2 or 3, wherein
the catalyst (1) contains 15 to 60 mass% of the faujasite-type zeolite
(A) based on a catalyst composition, and the catalyst (2) contains 15 to 60 mass%
of the faujasite-type zeolite (B) based on a catalyst composition.
[Claim 5]
The fluid catalytic cracking catalyst for hydrocarbon oil excellent in
product yield according to any one of claims 2 to 4, wherein
the catalyst (1) contains 0.5 to 2.0 mass% of the rare earth as RE2O3
based on a catalyst composition, and the catalyst (2) contains 0.5 to 12 mass% of
the rare earth as RE2O3 based on a catalyst composition.
[Claim 6]
The fluid catalytic cracking catalyst for hydrocarbon oil excellent in
product yield according to claim 1, wherein:
the fluid catalytic cracking catalyst for hydrocarbon oil is a blend of
two types of fluid catalytic cracking catalysts;
one catalyst is a catalyst (3) that has, after being pseudo-equilibrated,
a pore distribution in which a ratio (PV1/PV2) of a volume (PV1) of pores
having a pore size not smaller than 4 nm nor larger than 50 nm to a volume
(PV2) of pores having a pore size larger than 50 nm is lower than 0.8;
the other catalyst is a catalyst (4) that has, after being pseudoequilibrated,
a pore distribution in which: (a) a ratio (PV1/PV2) of a volume
(PV1) of pores having a pore size not smaller than 4 nm nor larger than 50 nm to
a volume (PV2) of pores having a pore size larger than 50 nm is not lower than
0.8; and (b) a ratio (PV4/PV3) of a volume (PV4) of pores having a pore size notsmaller than 30 nm nor larger than 100 nm to a volume (PV3) of pores having a
pore size larger than 4 nm is lower than 0.2; and
the fluid catalytic cracking catalyst is composed of the catalyst (3)
and the catalyst (4) blended at a ratio of 100 parts by mass of the former to 10 to
200 parts by mass of the latter.
[Claim 7]
The fluid catalytic cracking catalyst for hydrocarbon oil excellent in
product yield according to 5 claim 6, wherein:
the catalyst (3) contains a zeolite and a silica-based binder as a
binding agent, and contains 15 to 60 mass% of the zeolite and 5 to 30 mass% of
the silica-based binder based on a catalyst composition; and
the catalyst (4) contains a zeolite and an aluminum compound binder
as a binding agent, and contains 15 to 60 mass% of the zeolite and 5 to 30 mass%
of the aluminum compound binder based on a catalyst composition.
[Claim 8]
The fluid catalytic cracking catalyst for hydrocarbon oil excellent in
product yield according to claim 7, wherein
the silica-based binder is one or more than one of silica sol, water
glass, and an acidic silicate solution.
[Claim 9]
The fluid catalytic cracking catalyst for hydrocarbon oil excellent in
product yield according to claim 7, wherein
the aluminum compound binder contains one type selected from the
following (a) to (c):
(a) basic aluminum chloride;
(b) aluminum biphosphate; and
(c) alumina sol.
25 [Claim 10]
The fluid catalytic cracking catalyst for hydrocarbon oil excellent in
product yield according to any one of claims 7 to 9, wherein
the zeolites contained in the catalyst (3) and the catalyst (4) are of one
or more than one of the following types: FAU (faujasite), MFI, CHA, and MOR.
[Claim 11]
The fluid catalytic cracking catalyst for hydrocarbon oil excellent in
product yield according to claim 10, wherein
the FAU-type zeolite is one of a hydrogen Y-type zeolite (HY), an
ultra-stable Y-type zeolite (USY), a rare-earth-exchanged Y-type zeolite (REY),
and a rare-earth-exchanged ultra-stable Y-type zeolite (REUSY).
[Claim 12]
The fluid catalytic cracking catalyst for hydrocarbon 5 oil excellent in
product yield according to any one of claims 7 to 11, wherein
the catalyst (3) and the catalyst (4) contain clay mineral other than the
zeolite and the binding agent.
[Claim 13]
A fluid catalytic cracking catalyst for hydrocarbon oil excellent in
heavy oil cracking performance that is used by being blended with other catalyst,
the fluid catalytic cracking catalyst being characterized by
having, after being pseudo-equilibrated, a pore distribution in which:
(a) a ratio (PV1/PV2) of a volume (PV1) of pores having a pore size
not smaller than 4 nm nor larger than 50 nm to a volume (PV2) of pores having a
pore size larger than 50 nm is not lower than 0.8; and
(b) a ratio (PV4/PV3) of a volume (PV4) of pores having a pore size
not smaller than 30 nm nor larger than 100 nm to a volume (PV3) of pores
having a pore size larger than 4 nm is lower than 0.2.
[Claim 14]
The fluid catalytic cracking catalyst for hydrocarbon oil excellent in
heavy oil cracking performance according to claim 13, wherein
the catalyst contains a zeolite and an aluminum compound binder as a
binding agent, and contains 15 to 60 mass% of the zeolite and 5 to 30 mass% of
the aluminum compound binder based on a catalyst composition.
[Claim 15]
The fluid catalytic cracking catalyst for hydrocarbon oil excellent in
heavy oil cracking performance according to claim 14, wherein
the aluminum compound binder contains one type selected from the
following (a) to (c):
(a) basic aluminum chloride;
(b) aluminum biphosphate; and
(c) alumina sol.
[Claim 16]
The fluid catalytic cracking catalyst for hydrocarbon oil excellent in
heavy oil cracking performance according to claim 14 or 15, wherein
the zeolite contained in the catalyst is of one or more 5 than one of the
following types: FAU (faujasite), MFI, CHA, and MOR.
[Claim 17]
The fluid catalytic cracking catalyst for hydrocarbon oil excellent in
heavy oil cracking performance according to claim 16, wherein
the FAU-type zeolite is one of a hydrogen Y-type zeolite (HY), an
ultra-stable Y-type zeolite (USY), a rare-earth-exchanged Y-type zeolite (REY),
and a rare-earth-exchanged ultra-stable Y-type zeolite (REUSY).
[Claim 18]
The fluid catalytic cracking catalyst for hydrocarbon oil excellent in
heavy oil cracking performance according to any one of claims 14 to 17, wherein
the catalyst contains clay mineral other than the zeolite and the
binding agent.