1
DESCRIPTION
CATALYST FOR FLUID CATALYTIC CRACKING OF HYDROCARBON OIL AND
METHOD FOR FLUID CATALYTIC CRACKING OF HYDROCARBON OIL WITH
THE SAME
Technical Field
[0001]
The present invention relates to a catalyst for fluid
catalytic cracking of hydrocarbon oil with which gasoline and
a gas oil fraction can be obtained in high yields and a high
degree of bottom cracking and a low coke yield are attained,
and to a method for fluid catalytic cracking of hydrocarbon
oil with it.
Background Art
[0002]
In fluid catalytic cracking of hydrocarbon oil,
catalysts for fluid catalytic cracking containing a silicabased
binder, such as silica sol, as a binding agent have
been developed so far for the purpose of obtaining gasoline
in a high yield and attaining a low coke yield (e.g., see PTL
1). However, catalysts for fluid catalytic cracking that
contain a silica-based binder have been required to attain a
higher degree of bottom cracking.
2
[0003]
And, in order to obtain gasoline and a kerosene/light
oil fraction (a kerosene fraction and a light oil fraction,
or light cycle oil; hereinafter, also referred to as "LCO")
and to improve the degree of bottom cracking, in other words,
to reduce the yield of a heavy fraction (heavy cycle oil;
hereinafter, also referred to as ''HCO"), catalysts for fluid
catalytic cracking containing an aluminum-compound binder,
such as basic aluminum chloride, as a binding agent are also
under development (e.g., see PTL 2). However, catalysts for
fluid catalytic cracking that contain an alumina-compound
binder have been required to produce coke in a lower yield.
[0004]
Incidentally, fluid catalytic cracking apparatus (fullscale
apparatus) is usually used with any catalyst for fluid
catalytic cracking that may be changed to provide any
intended formulation of resultant oil (e.g., "a high
proportion of gasoline," "a high proportion of light cycle
oil," and so forth). Also, different kinds of raw material
oil provide different formulations of resultant oil, and thus
the catalyst for fluid catalytic cracking is usually changed
to provide any intended formulation of resultant oil. When
the catalyst is changed, the following cases are possible:
(1) A catalyst containing a silica-based binder is changed to
3
one that contains a different silica-based binder; (2) A
catalyst containing an aluminum-compound binder is changed to
one that contains a different aluminum-compound binder; (3) a
catalyst containing a silica-based binder is changed to one
that contains an aluminum-compound binder; and (4) a catalyst
containing an aluminum-compound binder is changed to one that
contains a silica-based binder. Here, when a catalyst is
changed, some volume of a first catalyst is first taken out
of the apparatus, and then the same volume of a second
catalyst is put into the apparatus. In this case, the inside
of the fluid catalytic cracking apparatus is subjected to a
gradual change in the mixing proportion (mass proportion) of
the first catalyst to the second catalyst, and finally the
content inside the apparatus, the first catalyst, is replaced
with the second catalyst. This has involved changes in
catalytic activity, conversion rate, gasoline yield, and some
other conditions; however, it has believed that these changes
are attributable to a newly added catalyst or operating
conditions of the apparatus.
[0005]
As for additive catalysts (added catalysts), which are
added to a catalyst for fluid catalytic cracking, these are
intended for supplementing the performance of the catalyst
for fluid catalytic cracking (e.g., removal of NOx, removal
4
of SOx, resistance against metal, improvement of octane
number, degree of bottom cracking, and so forth), not for
obtaining gasoline and a gas oil fraction in high yields or
attaining a high degree of bottom cracking and a low coke
yield.
Citation List
Patent Literature
[0006]
PTL 1: Japanese Unexamined Patent Application
Publication No. 2007-748
PTL 2: Japanese Unexamined Patent Application
Publication No. 2006-142273
Summary of Invention
Technical Problem
[0007]
However, known catalysts for fluid catalytic cracking
have had a problem that none of available ones satisfies all
of a high gasoline yield, a high yield of a gas oil fraction,
a low coke yield, and a high degree of bottom cracking.
[0008]
Made under these circumstances, the present invention
aims to provide a catalyst for fluid catalytic cracking of
hydrocarbon oil with which gasoline and a gas oil fraction
can be obtained in high yields and a high degree of bottom
5
cracking and a low coke yield are attained, and a method for
fluid catalytic cracking of hydrocarbon oil with it.
Solution to Problem
[0009]
More specifically, the gist of the present invention is
as follows:
[1] A catalyst for fluid catalytic cracking of
hydrocarbon oil, comprising Catalyst Composition A that
comprises zeolite and 10 to 30 % by mass of a silica-based
binder as a binding agent and Catalyst Composition B that
comprises zeolite and 10 to 30 % by mass of an aluminumcompound
binder as a binding agent, mixed therein in any mass
proportion in the range of 10:90 to 90:10 (WA:W8 ), provided
that WA is the mass of the catalyst composition A and W8 is
the mass of the catalyst composition B.
[2] The catalyst for fluid catalytic cracking of
hydrocarbon oil according to [ 1] , wherein each of Catalyst
Composition A and Catalyst Composition B has a K value as
expressed by the following formula (1), which is equal to or
higher than 1.
[0010]
K value = Conversion rate/ ( 100-Conversion rate) ... ( 1)
where the conversion rate is expressed by the following
formula (2);
6
[0011]
Conversion rate (% by mass) = (a-b) /a x 100 ... (2)
where the symbol "a" represents the mass of raw material
oil, and "b" represents the total mass of light cycle oil and
heavy cycle oil.
[ 3] The catalyst for fluid catalytic cracking of
hydrocarbon oil according to [1] or [2], wherein, when the K
values for Catalyst Composition A and for Catalyst
Composition B are expressed as "KA" and "K8 " respectively, the
ratio of KA: K8 is in the range as shown in the following
formula (3);
[0012]
KA:Ka=l:0.5 to 1:1.5 ... (3)
[ 4] The catalyst for fluid catalytic cracking of
hydrocarbon oil according to any of [1] to [3], wherein, when
the K value for the above catalyst is expressed as "Krn", the
Krn is greater than the K value for Catalyst Composition A (KA)
and the K value for Catalyst Composition B (K8 ).
[5] The catalyst for fluid catalytic cracking of
hydrocarbon oil according to any of [1] to [4], wherein a
gasoline yield by use of the above catalyst, when it is
expressed as "Grn", is greater than a gasoline yield by use of
Catalyst Composition A, when it is expressed as "GA" and a
gasoline yield by use of Catalyst Composition B, when it is
7
expressed as "Gs"·
[ 6] The catalyst for fluid catalytic cracking of
hydrocarbon oil according to any of [1] to [5], wherein the
above silica-based binder is one or more of the binding
agent(s) selected from the group consisting of a silica sol,
a water glass, and an acidic liquid of silicic acid.
[7] The catalyst for fluid catalytic cracking of
hydrocarbon oil according to any of [1] to [6], wherein the
aluminum-compound binder is one or more of the binding
agent(s) selected from the group consisting of the following
compound (a) to (c);
(a) Basic aluminum chloride,
(b) Aluminum biphosphate,
(c) Alumina sol.
[8] The catalyst for fluid catalytic cracking of
hydrocarbon oil according to any of [1] to [7], wherein the
zeolite has a crystal structure selected from the group
consisting of FAU type (faujasite type), MFI type, CHA type,
and MOR type, or a mixture thereof and is contained in
Catalyst Composition A and Catalyst Composition B in the
range of 15 to 60 % by mass respectively on a catalyst basis.
[9] The catalyst for fluid catalytic cracking of
hydrocarbon oil according to [8], wherein the zeolite, when
it has a crystal structure of the FAU type, is any one of
8
hydrogen Y-type zeolite (HY), ultrastable Y-type zeolite
(USY), rare-earth exchanged Y-type zeolite (REY), and rareearth
exchanged ultrastable Y-type zeolite (REUSY).
[10] The catalyst for fluid catalytic cracking of
hydrocarbon oil according to any of [1] to [9], wherein
Catalyst Composition A and Catalyst Composition B further
comprise, besides the zeolite and the binding agent, a clay
mineral.
[ 11] A method for fluid catalytic cracking of
hydrocarbon oil, with use of the above catalyst according to
any of [1] to [10].
[ 12] The method for fluid catalytic cracking of
hydrocarbon oil according to [ 11] , wherein the hydrocarbon
oil comprises a residual oil.
[13] The method for fluid catalytic cracking of
hydrocarbon oil according to [12], wherein the hydrocarbon
oil comprises vanadium and nickel being equal to or more than
0.5 ppm by mass for each.
[ 14] The method for fluid catalytic cracking of
hydrocarbon oil according to any of [11] to [13], wherein the
above catalyst comprises vanadium and nickel being equal to
or more than 300 ppm by mass for each.
Advantageous Effects of Invention
[0013]
9
A catalyst for fluid catalytic cracking of hydrocarbon
oil according to the present invention comprises two catalyst
compositions for cracking of different kinds of oil, more
specifically, Catalyst Composition A comprising a silicabased
binder and Catalyst Composition B comprising an
aluminum-compound binder, mixed therein. This means that 1n
fluid catalytic cracking of hydrocarbon oil, oil cracked by
one of the catalyst compositions can be further cracked by
the other catalyst composition, and thus oil left after
cracking is lighter than ever; as a result, gasoline and a
gas oil fraction can be obtained in high yields, coke is
produced in a low yield, and the degree of bottom cracking
can be high enough to prevent the formation of heavy cycle
oil.
[0014]
In particular, when the raw material oil is heavy oil,
which contains large amounts of vanadium, nickel, and other
metals poisonous to catalysts, alumina contained in Catalyst
Composition B, which comprises an alumina-compound binder,
binds to these poisonous metals to detoxify them, and thus
Catalyst Composition A, which comprises a silica-based binder,
becomes unlikely to be poisoned by the poisoning metals; as a
result, a high gasoline yield and a high yield of a gas oil
fraction as well as a high degree of bottom cracking are
10
achieved while the high gasoline yield and a low coke yield
are maintained.
Brief Description of Drawings
[0015]
[Fig. 1] Fig. 1 is a plot of K values obtained for an
example of the present invention.
[Fig. 2] Fig. 2 is a plot of gasoline yields obtained
for an example of the present invention.
Description of Embodiments
[0016]
A catalyst for fluid catalytic cracking of hydrocarbon
oil according to an embodiment of the present invention
comprises Catalyst Composition A that comprises zeolite and
10 to 30 % by mass of a silica-based binder as a binding
agent and Catalyst Composition B that comprises zeolite and
10 to 30 % by mass of an aluminum-compound binder as a
binding agent, mixed therein in any mass proportion in the
range of 10:90 to 90:10 (WA:W8 ), provided that WA is the mass
of Catalyst Composition A and W8 is the mass of Catalyst
Composition B. The following details the individual catalyst
compositions.
[0017]
Incidentally, fluid catalytic cracking apparatus (fullscale
apparatus) sometimes reaches the above-mentioned mass
11
proportion during the change from a catalyst comprising a
silica-based binder to one that comprises an aluminumcompound
binder and vise versa because of gradual addition of
the replacing catalyst. However, this is not the case in the
present invention because a catalyst mixture having a fixed
mass proportion is continuously added and thus the mass
proportion of catalyst compounds in the apparatus is kept
constant.
[0018]
Also, the catalyst used in the present invention is a
mixture of catalyst compositions each comprising a different
binder. These catalyst compositions are intended for
initiating fluid catalytic cracking and thus are different
from additive catalysts (added catalysts), which are added to
a catalyst for fluid catalytic cracking to supplement the
catalyst's performance.
[Catalyst Composition A]
Catalyst Composition A comprises, for example, 15 to
60 % by mass, preferably 20 to 50 % by mass of zeolite, 10 to
30 % by mass, preferably, 15 to 25 % by mass of a silicabased
binder as a binding agent, and inorganic oxides other
than zeolite as the balance.
<>
The silica-based binder can be any one of or two or more
12
of silica sol, water glass (sodium silicate), and silicic
acid liquid. And, silica sol can be produced from water
glass. For example, silica sol comprising Si02 at a
concentration in the range of 10 to 15 % by mass can be
prepared by adding water glass comprising Si02 at a
concentration in the range of 12 to 23 % by mass and sulfuric
acid having a concentration in the range of 20 to 30 % by
mass simultaneously and continuously.
<>
The zeolite used here can be any kind of zeolite
commonly used in a catalyst for catalytic cracking of
hydrocarbon oil, for example, any one of or two or more of
FAU type (faujasite type; e.g., Y-type zeolite, X-type
zeolite, and so forth), MFI type (e.g., ZSM-5, TS-1, and so
forth), CHA type (Examples are chabasite, SAP0-34, and so
forth), and MOR type (e.g., mordenite, Ca-Q, and so forth).
The FAU type is particularly preferable. Faujasite-type
zeolite includes hydrogen Y-type zeolite (HY), ultrastable Ytype
zeolite (USY), rare-earth exchanged Y-type zeolite (REY),
and rare-earth exchanged ultrastable Y-type zeolite (REUSY).
The latter two types of zeolite can be obtained by making HY
and USY carry rare-earth metals by ion exchange or some other
means.
[0019]
13
When the content ratio of zeolite to Catalyst
Composition A is lower than 15 % by mass, the cracking
activity is often low. When it exceeds 60 % by mass, the
bulk density is often high, leading to a decreased strength.
<>
The inorganic oxides can be, besides kaolin and other
clay minerals, activated alumina, porous silica, rare-earth
metal compounds, and metal capture agents (metal-trapping
agents).
[0020]
Any rare-earth metal oxide may be contained in Catalyst
Composition A, in the form of RE20 3 , at a content ratio in the
range of 0.5 to 2.0 % by mass. Rare-earth metals used here
include cerium (Ce), lanthanum (La), praseodium (Pr), and
neodymium (Nd), and Catalyst Composition A may carry any one
of or two or more of these as metal oxides.
[0021]
The following describes an example of the manufacturing
method of Catalyst Composition A. First, kaolin, porous
silica powder, and activated alumina are added to silica sol
mentioned above (an example of the silica-based binder), and
then slurry of ultrastable Y-type zeolite (USY) prepared with
20 to 30 % by mass sulfuric acid to have pH in the range of 3
to 5; in this way, a slurry mixture is prepared. This slurry
14
mixture is spray-dried to form spherical particles. The
obtained spherical particles are washed, brought into contact
with an aqueous solution of a rare earth metal (RE) chloride
for ion exchange for the content ratio of RE203 to be in the
range of 0.5 to 2.0 % by mass, and then dried; in this way,
Catalyst Composition A is obtained. The average particle
diameter of Catalyst Composition A obtained is not
particularly limited as long as the composition can be mixed
with Catalyst Composition B described later; however, it is
on the order of 60 to 70 ~-
[Catalyst Compound B]
Catalyst Composition B comprises, for example, 15 to
60 % by mass, preferably 20 to 50 % by mass of zeolite, 10 to
30 % by mass, preferably 15 to 25 % by mass of an aluminumcompound
binder as a binding agent, and inorganic oxides
other than zeolite as the balance.
<>
The aluminum-compound binder can be (a) basic aluminum
chloride, (b) aluminum biphosphate, or (c) alumina sol. A
solution obtained by dissolving any kind of or two or more
kinds of crystalline alumina, such as gibbsite, bayerrite,
and boehmite, in an acid solution may be used as the
aluminum-compound binder instead.
[0022]
15
Here, basic aluminum chloride is expressed by Formula 4.
[0023]
[Alz(OH)nC16-nJm (4)
(where, O>
Zeolite and inorganic oxides that can be used for
Catalyst Composition B are the same as those for Catalyst
Composition A described above and can be prepared in the same
content ratios as those for Catalyst Composition A.
[0024]
The following describes an example of the manufacturing
method of Catalyst Composition B. First, kaolin, activated
alumina, and USY slurry are added to, for example, a solution
of basic aluminum chloride with an Al20 3 concentration in the
range of 20 to 25 % by mass; in this way, a slurry mixture is
prepared with a slurry concentration in the range of 35 to
45%. This slurry mixture is spray-dried to form spherical
particles. These spherical particles are washed, brought
16
into contact with a solution of a rare earth metal chloride
for ion exchange for the content ratio of RE203 to be in the
range of 0.5 to 2.0 % by mass, and then dried; in this way,
Catalyst Composition B is obtained. The average particle
diameter of Catalyst Composition B obtained is not
particularly limited; however, it is on the order of 60 to 70
~m.
[Catalyst for Fluid Catalytic Cracking]
A catalyst for fluid catalytic cracking according to the
present invention is a mixture obtained by mixing Catalyst
Composition A and Catalyst Composition B in any mass
proportion in the range of 10:90 to 90:10 (WA:W8 ), provided
that WA is the mass of Catalyst Composition A and W8 is the
mass of Catalyst Composition B. When the mass proportion of
the catalyst compositions deviates from the specified range,
the difference from the case where the catalyst compositions
are individually used for fluid catalytic cracking is small,
and thus an explicit advantage is unlikely to be obtained.
Note that the mixing proportion (mass proportion) of Catalyst
Composition A and Catalyst Composition B is preferably
determined in such a manner that the cracking products
obtained by cracking of hydrocarbon oil using this catalyst
for fluid catalytic cracking (in particular, gasoline and
LCO) can have intended formulations (yields).
17
[Method for Fluid Catalytic Cracking]
Fluid catalytic cracking based on a catalyst for fluid
catalytic cracking according to the present invention can be
performed under ordinary conditions for fluid catalytic
cracking of hydrocarbon oil. For example, the conditions
described below can be suitably used.
[0025]
The raw material oil for catalytic cracking can be
ordinary raw material hydrocarbon oil, for example, hydro
desulfurized vacuum gas oil (DSVGO) or vacuum gas oil (VGO),
or residual oil such as residual oil of atmospheric
distillation (AR) , residual oil of vacuum distillation (VR) ,
desulfurized residual oil of atmospheric distillation (DSAR),
desulfurized residual oil of vacuum distillation (DSVR), and
deasphaltened oil (DAO). These kinds of oil can be used
alone or in combination thereof. A catalyst for fluid
catalytic cracking according to the present invention can
process any residual oil that contains nickel and vanadium at
a content ratio equal to or higher than 0.5 ppm by mass each,
and can be used with apparatus for fluid catalytic cracking
of residual oil (Resid FCC, or RFCC), which involves the use
of residual oil alone. Note here that when a known catalyst
for fluid catalytic cracking is used with RFCC, nickel and
vanadium contained in residual oil adhere to the catalyst and
18
reduce the activity of it; however, with a catalyst for fluid
catalytic cracking according to the present invention, even
processing of any residual oil that contains vanadium and
nickel at a content ratio equal to or higher than 0.5 ppm by
mass each would not affect the excellent catalytic
performance of the catalyst. Furthermore, a catalyst for
fluid catalytic cracking according to the present invention
keeps its catalytic performance even when it contains
vanadium and nickel at a content ratio equal to or higher
than 300 ppm by mass each. The maximum acceptable limit of
vanadium and nickel contained in a catalyst for fluid
catalytic cracking according to the present invention is
about 10000 ppm by mass each.
[0026]
As for reaction temperature for catalytic cracking of
the above-mentioned raw material hydrocarbon oil, a
temperature in the range of 470 to 550°C is suitably used.
As for reaction pressure, a pressure on the order of 1 to 3
kg/cm2 is usually preferable. The mass proportion of
catalyst/oil (catalyst/oil ratio) is preferably in the range
of 2.5 to 7.0, and the contact time is preferably in the
range of 10 to 60 hr-1
•
<>
The K value can be determined in the following way: Raw
19
material oil is catalytically cracked by the method described
above, the fractions having a boiling point higher than that
of gasoline (on the order of 30 to 220°C), or light cycle oil
(LCO) and heavy cycle oil (HCO), are weighed, the conversion
rate is determined from the mass of the raw material oil and
the total mass of LCO and HCO by Formula (2), and then the K
value is determined from the conversion rate by Formula (1).
[0027]
K value = Conversion rate/ (100-Conversion rate) ... (1)
Conversion rate ( % by rna s s ) = (a-b) I a x 1 0 0 ... ( 2 )
where the symbol "a" represents the mass of raw material
oil, and "bu represents the total mass of light cycle oil and
heavy cycle oil.
[0028]
Here, the K values for Catalyst Composition A and
Catalyst Composition B (KA and K8 , respectively) are at least
1 (conversion rate: ~50%), preferably equal to or higher than
1.5 (conversion rate: ~60%), and more preferably equal to or
higher than 2.3 (conversion rate: ~70%). Any K value for
Catalyst Composition A or Catalyst Composition B being less
than 1 (conversion rate: <50%) results in low yields of
gasoline and LCO and thus is impractical.
[0029]
Also, the K values for Catalyst Composition A and
20
Catalyst Composition B follow a relationship of KA:KB in the
range of 1:0.5 to 1:1.5, preferably 1:0.8 to 1:1.2, and more
preferably 1:0.9 to 1:1.1. In the case where KA:KB is
1:<0.5(lower than 0.5) or KA:KB is 1:>1.5(higher than 1.5),
the difference in K value between the two catalyst
compositions is too great, and thus it is difficult to exceed
KA and ~-
[0030]
Additionally, the K value for the catalyst for fluid
catalytic cracking (Km) is. preferably greater than the K
value for Catalyst Composition A (KA) and the K value for
Catalyst Composition B (KB).
<>
The gasoline yield for the catalyst for fluid catalytic
cracking, Gm, is preferably greater than the gasoline yield
for Catalyst Composition A, GA, and the gasoline yield for
Catalyst Composition B, GB. The gasoline yield mentioned here
is calculated from the mass of gasoline obtained by catalytic
cracking of raw material performed by the method described
above and the mass of the raw material oil.
[0031]
In addition, a catalyst for fluid catalytic cracking
according to the present invention often provides LCO in a
higher yield, and hydrogen, Cl+C2, LPG, HCO, and coke in
21
lower yields than Catalyst Composition A or Catalyst
Composition B used alone does. In other words, the use of a
catalyst for fluid catalytic cracking according to the
present invention, when compared with the use of Catalyst
Composition A or Catalyst Composition B alone, often
increases the yields of liquid fuels, such as gasoline and
LCO, but decreases the yields of gas, heavy oil, coke, and so
forth.
EXAMPLES
[0032]
[Production of Silica-based Binders]
<>
Silica sol comprising Si02 at a concentration of 12.5 %
by mass (an example of the silica-based binder) was prepared
with a weight of 4000 g by adding 2941 g of water glass
comprising Si02 at a concentration of 17 % by mass and 1059 g
of sulfuric acid having a concentration of 25 % by mass
simultaneously and continuously. To this silica sol, 800 g
of kaolin, 175 g of porous silica powder, and 250 g of
activated alumina, the weights on a dry weight basis, were
added, and then 800 g of slurry of ultrastable Y-type zeolite
(USY) prepared with 25 % by mass sulfuric acid to have pH of
3.9 was added; in this way, a slurry mixture was prepared.
This slurry mixture was spray-dried to form spherical
22
particles having an average particle diameter of 60 ~-
[0033]
The obtained spherical particles were washed, brought
into contact with an aqueous solution of a rare earth metal
(RE) chloride (this solution contained chlorides of cerium
and lanthanum; the same applies hereinafter) for ion exchange
for the content ratio of RE20 3 to be 1.0 % by mass, and then
dried in an oven at 135°C. In this way, Catalyst Composition
A1 was prepared.
[0034]
The formulation of Catalyst Composition A1 was as
follows: Si02 of silica sol origin: 20 % by mass; kaolin:
32 % by mass; Si02 of porous silica powder origin: 7 % by
mass; activated alumina: 10 % by mass; USY: 30 % by mass.
The properties of Catalyst Composition A1 are shown in Table
1 .
<>
Silica sol comprising Si02 at a concentration of 12.5 %
by mass (an example of the silica-based binder) was prepared
with a weight of 4000 g by adding 2941 g of water glass
comprising Si02 at a concentration of 17 % by mass and 1059 g
of sulfuric acid having a concentration of 25 % by mass
simultaneously and continuously. To this silica sol, 800 g
of kaolin, 175 g of porous silica powder, and 250 g of
23
activated alumina, the weights on a dry weight basis, were
added, and then 800 g of slurry of RE ultrastable Y-type
zeolite (REUSY) prepared with 25 % by mass sulfuric acid to
have pH of 3.9 was added as Y-type zeolite; in this way, a
slurry mixture was prepared. This slurry mixture was spraydried
to form spherical particles having an average particle
diameter of 60 ~-
[0035]
The obtained spherical particles were washed and then
dried in an oven at 135°C. In this way, Catalyst Composition
A2 was prepared. The properties of Catalyst Composition A2
are shown in Table 1.
<>
To 2941 g of water glass comprising Si02 at a
concentration of 17 %by mass (an example of the silica-based
binder), 800 g of kaolin, 175 g of porous silica powder, and
250 g of activated alumina, the weights on a dry weight basis,
were added, and then 800 g of slurry of RE ultrastable Y-type
zeolite (REUSY) prepared with 25 % by mass sulfuric acid to
have pH of 3.9 as Y-type zeolite was added; in this way, a
slurry mixture was prepared. This slurry mixture was spraydried
to form spherical particles having an average particle
diameter of 60 ~m.
[0036]
24
The obtained spherical particles were washed and then
dried in an oven at 135°C. In this way, Catalyst Composition
A3 was prepared. The properties of Catalyst Composition A3
are shown in Table 1.
[0037]
[Table 1]
Table 1
Composition Composition Composition
A1 A2 A3
Zeolite USY REUSY REUSY
Binder Silica sol Silica sol Water glass
Chemical properties
Loss on carcination %by mass 13.6 12.6 14.6
Al203 %by mass 30.4 28.8 28.0
RE203 %by mass 0.99 3.70 3.78
Na20 %by mass 0.13 0.15 0.23
so4 %by mass 0.23 0.32 0.36
Physical properties
Specific surface area m2/g_ 259 263 238
Bulk specific gravity g/m 0.73 0.65 0.67
[0038]
Note that the specific surface area and the bulk
specific gravity were measured by the BET method and UOP
Method 254-65, respectively. And, the loss on carcination
represents a decrease in mass observed after carcination at
1000°C for one hour. (The same applies hereinafter.)
[Production of Aluminum-compound Binders]
<>
To 1201 g of a basic aluminum chloride solution
25
comprising Al20 3 at a concentration of 23.3 %by mass (an
example of the aluminum-compound binder), 840 g of kaolin,
260 g of activated alumina, and 640 g of USY slurry were
added; in this way, a slurry mixture was prepared with a
slurry concentration of 41%. This slurry mixture was spraydried
to form spherical particles having an average particle
diameter of 60 ~- These spherical particles were washed,
brought into contact with an aqueous solution of a rare earth
metal chloride for ion exchange for the content ratio of RE20 3
to be 1.0 % by mass, and then dried in an oven at 135°C. In
this way, Catalyst Composition B1 was prepared. The
formulation of Catalyst Composition B1 obtained was as
follows: Al20 3 of basic aluminum chloride solution origin:
14 % by mass; kaolin: 41 % by mass; activated alumina: 13 %
by mass; USY: 32 % by mass. The properties of Catalyst
Composition B1 are shown in Table 2.
<>
To 1201 g of a basic aluminum chloride solution
comprising Al20 3 at a concentration of 23.3 % by mass (an
example of the aluminum-compound binder), 840 g of kaolin,
260 g of activated alumina, and 640 g of REUSY slurry as Ytype
zeolite were added; in this way, a slurry mixture was
prepared with a slurry concentration of 43%. This slurry
mixture was spray-dried to form spherical particles having an
26
average particle diameter of 60 ~- These spherical
particles were washed and then dried in an oven at 135°C. In
this way, Catalyst Composition B2 was prepared. The
properties of Catalyst Composition B2 are shown in Table 2.
<>
Alumina sol (an example of the aluminum-compound binder)
was prepared by adding 63% nitric acid to 2400 g of an
aqueous solution of pseudoboehmite-type alumina (Catapal-A, a
product from Sasol) comprising Al20 3 at a concentration of
12.5 % by mass until pH was 3.0. To this alumina sol, 840 g
of kaolin, 260 g of activated alumina, and 640 g of REUSY
slurry as Y-type zeolite were added; in this way, a slurry
mixture was prepared with a slurry concentration of 43%.
This slurry mixture was spray-dried to form spherical
particles having an average particle diameter of 60 ~-
These spherical particles were carcinated in an electric
furnace at 600°C. In this way, Catalyst Composition B3 was
prepared. The properties of Catalyst Composition B3 are shown
in Table 2.
<>
To 1723 g of a 17.4 % by mass aluminum biphosphate
solution (an example of the aluminum-compound binder), 840 g
of kaolin, 260 g of activated alumina, and 640 g of REUSY
slurry as Y-type zeolite were added; in this way, a slurry
27
mixture was prepared with a slurry concentration of 43%.
This slurry mixture was spray-dried to form spherical
particles having an average particle diameter of 60 ~-
These spherical particles were carcinated in an electric
furnace at 600°C. In this way, Catalyst Composition B4 was
prepared. The properties of Catalyst Composition B4 are shown
in Table 2.
[0039]
[Table 2]
Table 2
Composition Composition Composition Composition
B1 Bz B3 B4
Zeolite USY REUSY REUSY REUSY
Binder ACH ACH Alumina sol
Aluminum
biohosphate
Chemical properties
Loss on carcination mass% 17.3 14.3 3.7 4.4
Al20 3 mass% 4 9. 7 40.2 40.4 39.8
RE 20 3 mass% 0. 97 3. 7 9 3.81 3.17
NazO mass% 0.26 0.15 0.18 0.17
so4 mass% 2. 64 2.33 0.03 0.08
Physical properties
Specific surface area mz/q 261 274 283 156
Bulk specific qravity q/m 0.73 0.78 0.67 0.56
[0040]
(Example 1: Catalyst 1)
Catalyst Composition A1 and Catalyst Composition B1 were
mixed in a mass proportion of 70:30 on a dry weight basis to
form Catalyst for Fluid Catalytic Cracking 1.
(Example 2: Catalyst 2)
28
Catalyst Composition A1 and Catalyst Composition B1 were
mixed in a mass proportion of 50:50 on a dry weight basis to
form Catalyst for Fluid Catalytic Cracking 2.
(Example 3: Catalyst 3)
Catalyst Composition A1 and Catalyst Composition B1 were
mixed in a mass proportion of 30:70 on a dry weight basis to
form Catalyst for Fluid Catalytic Cracking 3.
(Comparative Example 1: Catalyst 4)
Catalyst Composition A1 was used as Catalyst for Fluid
Catalytic Cracking 4.
(Comparative Example 2: Catalyst 5)
Catalyst Composition B1 was used as Catalyst for Fluid
Catalytic Cracking 5.
(Test 1)
With Catalysts for Fluid Catalytic Cracking 1 to 5,
catalytic cracking reaction test was performed using a pilot
reaction test unit (a product from ARCO) with the same raw
material oil and under the same reaction conditions. The
pilot reaction test unit, which had a circulation moving bed
for the circulation of a catalyst inside and alternately
repeated reaction and catalyst regeneration, was a simulator
of apparatus for fluid catalytic cracking in commercial use.
(The same also applies to the examples described below.)
First, prior to the reaction test, Catalysts for Fluid
29
Catalytic Cracking 1 to 5 were pretreated by the cyclic metal
deposition (CMD) method in such a manner that they should
each contain vanadium octylate and nickel octylate at, on a
mass basis, 4000 ppm by mass in terms of vanadium and 2000
ppm by mass in terms of nickel, respectively. Here, the CMD
method is a method in which impregnation of a catalyst for
fluid catalytic cracking with small amounts of vanadium and
nickel and subsequent regeneration of the catalyst for fluid
catalytic cracking at a high temperature are repeated until
vanadium and nickel depositions reach a target concentration
in the catalyst for fluid catalytic cracking, and then
oxidation and reduction are repeated at a high temperature in
the range of 400 to 800°C; this method is a simulator of
apparatus for fluid catalytic cracking in commercial use.
(The same also applies to the examples described below.)
The fluid catalytic cracking mentioned here was
performed under the reaction conditions shown in Table 3.
Table 4 and Figs. 1 and 2 show the results of reaction. In
Table 4, the calculations for Catalysts 1 to 3 were derived
(by the weighed average method) from the result of reaction
test for Catalyst 4 (i.e., Catalyst Composition A1 only),
that for Catalyst 5 (i.e., Catalyst Composition B1 only), and
the mixing proportion of catalysts. (The same also applies
to the examples described below.) Note that the K values
30
were calculated from the conversion rates.
[0041]
The K values and gasoline yields shown in Table 4 are
plotted in Figs. 1 and 2, respectively. Note that in Figs. 1
and 2, the symbol "•" represents measurements, and •
represents "calculations." As shown in Table 4, with
Catalysts 1 to 3, "Gasoline'' and "LCO" were obtained in high
yields, and "HCO" and "Coke" were in low yields, compared
with the calculations. In Fig. 1, examples with a mass
proportion of Catalyst Composition A1 in the range of 10 to
40 % by mass (in other words, the ratio WA:W8 in the range of
10:90 to 40:60) provided a K value for Catalyst 1 (Km) higher
than those for Catalyst Composition A1 (KA) and Catalyst
Composition B1 (Ks). In Fig. 2, examples with a mass
proportion of Catalyst Composition A1 in the range of 10 to
90 % by mass (in other words, the ratio WA:W8 in the range of
10:90 to 90:10) provided a gasoline yield for Catalyst 1
higher than each of those for Catalyst Composition A1 and
Catalyst Composition B1 •
[0042]
[Table 3]
31'
Table 3
Reaction temperature 520°C
Regeneration temperature 670°C
Raw material oil Desulfurized Atmosphere residual
oil(DSAR)
Nickel content 2 ppm by mass
Vanadium content 2 ppm by mass
Catalyst/Oil ratio 7 9-
0 by mass/% by mass
32
[0043]
[Table 4]
Table 4
Catalyst 1 Catalyst 2 Catalyst 3 Catalyst 4 Catalyst 5 I
'
Catalyst
Composition 70 50 30 100 0
Al
Catalyst
Composition 30 50 70 0 100
81
Measurement Calculation Measurement Calculation Measurement Calculation Measurement Measurement
Conversion %
rate
72.9 72.6 73.2 72.8 73.5 73.0 72.2 73.4
K value 2.69 2.64 2.73 2.68 2. 77 2.71 2.60 2.76
Hydrogen % 0.51 0.54 0.51 0.55 0.52 0.55 0.53 0.56
Cl+C2 % 2.3 2.4 2.3 2.4 2.3 2.4 2.3 2.5
LPG % 13.3 13.6 13.2 13.6 13.2 13.5 13.7 13.4
Gasoline % 52.9 50.8 52.3 51.0 52.5 51.2 50.6 51.4
LCO % 18.6 18.5 18.7 18.6 18.8 18.7 18.3 18.8 .
HCO % 8.5 9.0 8.1 8.7 7.7 8.3 9.5 7.8
Coke % 4. 8 5.2 4. 8 5.3 4.9 5.4 5.0 5.5
33
[0044]
Note the following:
-Conversion rate (%by mass)=(a-b)/a x 100
a: Mass of raw material oil
b: Total mass of light cycle oil (LCO) and heavy cycle
oil (HCO)
- K value=Conversion rate/(100-Conversion rate)
- Hydrogen (% by mass)=c/a x 100
c: Mass of hydrogen in the gas produced
- C1+C2 (% by mass)=d/a x 100
d: Mass of C1 (methane) and C2 (ethane and ethylene) in
the gas produced
- LPG (liquefied petroleum gas; % by mass)=e/a x 100
e: Mass of propane, propylene, butane, and butylene in
the gas produced
- Gasoline (% by mass)=f/a x 100
f: Mass of gasoline (boiling point range: the boiling
point of CS (butane) (20°C) to 204°C) in the oil produced
- LCO (% by mass)=g/a x 100
g: Mass of light cycle oil (boiling point range: 204 to
343°C) in the oil produced
- HCO (% by mass)=h/a x 100
h: Mass of heavy cycle oil (boiling point range: ~343°C)
in the oil produced
34
- Coke (% by mass)=i/a x 100
i: Mass of coke precipitated on the catalyst mixture
The same also applies to the examples described below.
<>
(Example 4: Catalyst 6)
Catalyst Composition A2 and Catalyst Composition B2 were
mixed in a mass proportion of 70:30 on a dry weight basis to
form Catalyst for Fluid Catalytic Cracking 6.
(Example 5: Catalyst 7)
Catalyst Composition A2 and Catalyst Composition B2 were
mixed in a mass proportion of 50:50 on a dry weight basis to
form Catalyst for Fluid Catalytic Cracking 7.
(Example 6: Catalyst 8)
Catalyst Composition A2 and Catalyst Composition B2 were
mixed in a mass proportion of 30:70 on a dry weight basis to
form Catalyst for Fluid Catalytic Cracking 8.
(Comparative Example 3: Catalyst 9)
Catalyst Composition A2 was used as Catalyst for Fluid
Catalytic Cracking 9.
(Comparative Example 4: Catalyst 10)
Catalyst Composition B2 was used as Catalyst for Fluid
Catalytic Cracking 10.
(Test 2)
With Catalysts for Fluid Catalytic Cracking 6 to 10,
35
fluid catalytic cracking was performed as in Test 1. Table 5
shows the results of reaction. As shown in Table 5, with
Catalysts 6 to 8, "Gasoline" and "LPG" were obtained in high
yields, and "HCO" and "Coke" were in low yields, compared
with the calculations.
36
[0045]
[Table 5]
Table 5
Catalyst 6 Catalyst 7 Catalyst 8 Catalyst 9 Catalyst 10
Catalyst
Composition 70 50 30 100 0
A2
Catalyst
Composition 30 50 70 0 100
B2
Measurement Calculation Measurement Calculation Measurement Calculation Measurement Measurement
Conversio
% 77.7 n rate 77.5 78.6 78.2 79.2 78.9 76.4 79.9
K value 3.48 3.43 3.67 3.58 3.81 3.73 3.24 3.98
Hydrogen % 0.35 0.36 0.35 0.37 0 .. 36 0.37 0.35 0.38
Cl+C2 % 2.3 2.3 2.4 2.4 2.4 2.4 2.3 2.4
LPG % 18.8 18.7 19.0 18.8 19.0 18.9 18.5 19.1
Gasoline % 47.8 47.5 48.2 47.8 48.5 48.1 47.0 48.5
LCO % 13.4 13.3 13.4 13.4 13.4 13.4 13.3 13.4
HCO % 8.9 9.2 8.0 8.5 7.4 7.8 10.3 6.7
Coke % 8.4 8.6 _8_._6 ---- 8.9 8.9 9.1 8.2 9.5
[0046]
<>
(Example 7: Catalyst 11)
37
Catalyst Composition A2 and Catalyst Composition B3 were
mixed in a mass proportion of 70:30 on a dry weight basis to
form Catalyst for Fluid Catalytic Cracking 11.
(Example 8: Catalyst 12)
Catalyst Composition A2 and Catalyst Composition B3 were
mixed in a mass proportion of 50:50 on a dry weight basis to
form Catalyst for Fluid Catalytic Cracking 12.
(Example 9: Catalyst 13)
Catalyst Composition A2 and Catalyst Composition B3 were
mixed in a mass proportion of 30:70 on a dry weight basis to
form Catalyst for Fluid Catalytic Cracking 13.
(Comparative Example 5: Catalyst 14)
Catalyst Composition B3 was used as Catalyst for Fluid
Catalytic Cracking 14.
(Test 3)
With Catalysts for Fluid Catalytic Cracking 9 and 11 to
14, fluid catalytic cracking was performed as in Test 1.
Table 6 shows the results of reaction. As shown in Table 6,
with Catalysts 11 to 13, "Conversion rate," "Gasoline," and
"LPG" were obtained in high yields, and "HCO" and "Coke" were
in low yields, compared with the calculations.
38
[0047]
[Table 6]
Table 6
Catalyst 11 Catalyst 12 Catalyst 13 Catalyst 9 Catalyst 14 I
Catalyst I
Composition 70 50 30 100 0
A2
Catalyst '
Composition 30 50 70 0 100
83
Measurement Calculation Measurement Calculation Measurement Calculation Measurement Measurement
Conversio
n rate % 77.6 77.2 78.0 77.7 78.5 78.2 76.4 78.9
K value 3. 4 6 3.38 3.55 3.47 3.65 3.58 3.24 3.74
Hydrogen % 0.35 0.36 0.35 0.36 0.36 0.36 0.35 0.37
Cl+C2 % 2.3 2.3 2.4 2.4 2.4 2.4 2.3 2.4
LPG % 18.9 18.9 19.0 18.9 19.0 18.9 18.8 19.0
Gasoline % 47.8 47.3 48.0 47.6 48.1 47.8 47.0 48.1
LCO % 13.4 13.3 13.4 13.4 13.4 13.4 13.3 13.4
HCO % 9.0 9.5 8.6 9.0 8.1 8.5 10.3 7.7
Coke % 8.2 8. 4 8.3 8.6 8.6 8. 8 8.2 9.0
[0048]
<>
(Example 10: Catalyst 15)
39
Catalyst Composition A2 and Catalyst Composition B4 were
mixed in a mass proportion of 70:30 on a dry weight basis to
form Catalyst for Fluid Catalytic Cracking 15.
(Example 11: Catalyst 16)
Catalyst Composition A2 and Catalyst Composition B4 were
mixed in a mass proportion of 50:50 on a dry weight basis to
form Catalyst for Fluid Catalytic Cracking 16.
(Example 12: Catalyst 17)
Catalyst Composition A2 and Catalyst Composition B4 were
mixed in a mass proportion of 30:70 on a dry weight basis to
form Catalyst for Fluid Catalytic Cracking 17.
(Comparative Example 6: Catalyst 18)
Catalyst Composition B4 was used as Catalyst for Fluid
Catalytic Cracking 18.
(Test 4)
With Catalysts for Fluid Catalytic Cracking 9 and 15 to
18, fluid catalytic cracking was performed as in Test 1.
Table 7 shows the results of reaction. As shown in Table 7,
with Catalysts 15 to 17, "Additive rate," "Gasoline," and
"LPG" were obtained in high yields, and "Hydrogen," "C1+C2,"
"LCO," "HCO," and "Coke" were in low yields, compared with
40
the calculations.
41
[0049]
[Table 7]
Table 7
Catalyst 15 Catalyst 16 Catalyst 17 Catalyst 9 Catalyst 18
Catalyst
Composition 70 50 30 100 0
Az
Catalyst
Composition 30 50 70 0 100
84
Measurement Calculation Measurement Calculation Measurement Calculation Measurement Measurement
Conversion %
rate 73.7 62.5 72.0 53.3 50.6 44.0 76.4 30.1
K value 2.80 1. 67 2.57 1.14 1. 02 0.79 3.24 0.43
Hydrogen % 0.34 0.36 0.33 0.36 0.35 0.36 0.35 0.37 I
Cl+C2 % 2.0 2.1 1.8 2.0 1.7 1.8 2.3 1.6 I
LPG % 16.9 13.9 15.7 10.8 9.3 7.7 18.5 3.0
Gasoline % 46.9 37.9 47.2 31.8 31. 4 25.7 47.0 16.6
LCO % 14.3 15.1 14.8 16.3 17.1 17.4 13.3 19.2
HCO % 12.0 22.4 13.2 30.5 32.3 38.6 10.3 50.7
Coke % 7.5 8.3 6.9 8.4 7.8 8.4 8.2 8.5
[0050]
<>
(Example 13: Catalyst 19)
42
Catalyst Composition A3 and Catalyst Composition B2 were
mixed in a mass proportion of 70:30 on a dry weight basis to
form Catalyst for Fluid Catalytic Cracking 19.
(Example 14: Catalyst 20)
Catalyst Composition A3 and Catalyst Composition B2 were
mixed in a mass proportion of 50:50 on a dry weight basis to
form Catalyst for Fluid Catalytic Cracking 20.
(Example 15: Catalyst 21)
Catalyst Composition A3 and Catalyst Composition B2 were
mixed in a mass proportion of 30:70 on a dry weight basis to
form Catalyst for Fluid Catalytic Cracking 21.
(Comparative Example 7: Catalyst 22)
Catalyst Composition A3 was used as Catalyst for Fluid
Catalytic Cracking 22.
(Test 5)
With Catalysts for Fluid Catalytic Cracking 10 and 19 to
22, fluid catalytic cracking was performed as in Test 1. As
shown in Table 8, with Catalysts 19 to 21, "Gasoline" and
"LCO" were obtained in high yields, and "HCO" and "Coke" were
in low yields, compared with the calculations.
43
[0051]
[Table 8]
Table 8
Catalyst 19 Catalyst 20 Catalyst 21 Catalyst 22 Catalyst 10
Catalyst
Composition 70 50 30 100 0
A3
Catalyst
Composition 30 50 70 0 100
82
Measurement Calculation Measurement Calculation Measurement Calculation Measurement Measurement
Conversio
n rate % 73.9 73.0 78.3 75.0 79.0 77.0 70.1 79.9
K value 2.83 2.71 3.61 3.00 3.76 3.34 2.34 3.98
Hydrogen % 0.33 0.34 0.34 0.35 0.36 0.36 0.32 0.38
Cl+C2 % 2.3 2.3 2.3 2.3 2.3 2.3 2.2 2.4
LPG % 17.8 17.4 19.2 17.9 19.0 18.4 16.6 19.1
Gasoline % 44.7 44.0 47.4 45.3 47.8 46.6 42.1 48.5
LCO % 13.2 13.1 13.2 13.2 13.2 13.3 12.9 13.4 I
HCO % 12.9 13.9 8.5 11.9 7.8 9.8 17.0 6.7 I
Coke % 8.8 9.0 9.0 9.2 9.2 9.3 8.8 9.5
44
[0052]
<>
(Comparative Example 16: Catalyst 23)
Catalyst Composition A3 and Catalyst Composition B3 were
mixed in a mass proportion of 70:30 on a dry weight basis to
form Catalyst for Fluid Catalytic Cracking 23.
(Example 17: Catalyst 24)
Catalyst Composition A3 and Catalyst Composition B3 were
mixed in a mass proportion of 50:50 on a dry weight basis to
form Catalyst for Fluid Catalytic Cracking 24.
(Example 18: Catalyst 25)
Catalyst Composition A3 and Catalyst Composition B3 were
mixed in a mass proportion of 30:70 on a dry weight basis to
form Catalyst for Fluid Catalytic Cracking 25.
(Test 6)
With Catalysts for Fluid Catalytic Cracking 14, 22, and
23 to 25, fluid catalytic cracking was performed as in Test 1.
Table 9 shows the results of reaction. As shown in Table 9,
with Catalysts 23 to 25, "Gasoline" and "LCO" were obtained
in high yields, and "HCO" and "Coke" were in low yields,
compared with the calculations.
45
[0053]
[Table 9]
Table 9
Catalyst 23 Catalyst 24 Catalyst 25 Catalyst 22 Catalyst 14
Catalyst
Composition 70 50 30 100 0
A3
Catalyst
Composition 30 50 70 0 100
B3
Measurement Calculation Measurement Calculation Measurement Calculation Measurement Measurement '
Conversion %
rate
73.2 72.7 75.4 74.5 76.8 76.3 70.1 78.9
K value 2.73 2.67 3.07 2. 92 3.31 3.21 2.34 3.74
Hydrogen % 0.33 0.34 0.34 0.35 0.35 0.36 0.32 0.37
C1+C2 % 2.3 2.3 2.3 2.3 2.3 2.3 2.2 2.4
LPG % 17.3 17.3 18.1 17.8 18.5 18.3 16.6 19.0
Gasoline % 44.4 43.9 45.8 45.1 46.8 46.3 42.1 48.1 !
LCO % 13.0 13.1 13.2 13.2 13.3 13.3 12.9 13.4
HCO % 13.8 14.2 11.4 12.4 9.9 10.5 17.0 7.7
Coke % 8. 8 8.9 8. 8 8.9 8.8 8. 9 8.8 9.0
[0054]
<>
(Example 19: Catalyst 26)
46
Catalyst Composition A3 and Catalyst Composition B4 were
mixed in a mass proportion of 70:30 on a dry weight basis to
form Catalyst for Fluid Catalytic Cracking 26.
(Example 20: Catalyst 27)
Catalyst Composition A3 and Catalyst Composition B4 were
mixed in a mass proportion of 50:50 on a dry weight basis to
form Catalyst for Fluid Catalytic Cracking 27.
(Example 21: Catalyst 28)
Catalyst Composition A3 and Catalyst Composition B4 were
mixed in a mass proportion of 30:70 on a dry weight basis to
form Catalyst for Fluid Catalytic Cracking 28.
(Test 7)
With Catalysts for Fluid Catalytic Cracking 18, 22, and
26 to 28, fluid catalytic cracking was performed as in Test 1.
Table 10 shows the results of reaction. As shown in Table 10,
with Catalysts 26 to 28, "Gasoline" and "LCO" were obtained
in high yields, and "HCO" and "Coke" were in low yields,
compared with the calculations.
47
[0055)
[Table 10]
Table 10
Catalyst 26 Catalyst 27 Catalyst 28 Catalyst 22 Catalyst 18
Catalyst
Composition 70 50 30 100 0
A3
Catalyst
Composition 30 50 70 0 100
B4
Measurement Calculation Measurement Calculation Measurement Calculation Measurement Measurement
Conversio
n rate % 67.2 58.1 65.0 50.1 47.5 42.1 70.1 30.1
K value 2.05 1. 39 1. 86 1. 00 0.90 0.73 2.34 0.43
Hydrogen % 0.31 0.34 0.31 0.35 0.33 0.36 0.32 0.37
Cl+C2 % 2.0 2.0 1.9 1.9 1.7 1.8 2.2 1.6
LPG % 15.1 12.5 13.8 9.8 8.4 7.1 16.6 3.0
Gasoline % 41.5 34.5 41.3 29.4 29.0 24.3 42.1 16.6
LCO % 14.0 14.8 14.8 16.1 17.0 17.3 12.9 19.2
HCO % 18.8 27.1 20.2 33.9 35.5 40.6 17.0 50.7
Coke % 8.2 $.7 7.6 8.7 8.0 8.6 8.8 8.5
48
[0056]
<>
(Comparative Example 8: Catalyst 29)
Catalyst Composition A2 and Catalyst Composition A3 were
mixed in a mass proportion of 70:30 on a dry weight basis to
form Catalyst for Fluid Catalytic Cracking 29.
(Comparative Example 9: Catalyst 30)
Catalyst Composition A2 and Catalyst Composition A3 were
mixed in a mass proportion of 50:50 on a dry weight basis to
form Catalyst for Fluid Catalytic Cracking 30.
(Comparative Example 10: Catalyst 31)
Catalyst Composition A2 and Catalyst Composition A3 were
mixed in a mass proportion of 30:70 on a dry weight basis to
form Catalyst for Fluid Catalytic Cracking 31.
(Test 8)
With Catalysts for Fluid Catalytic Cracking 9, 22, and
29 to 31, fluid catalytic cracking was performed as in Test 1.
Table 11 shows the results of reaction. As shown in Table 11,
Catalysts 29 to 31 resulted in measurements similar to the
calculations for the yields of "Gasoline," "LCO," "HCO," and
"Coke."
49
[0057]
[Table 11]
Table 11
Catalyst 29 Catalyst 30 Catalyst 31 Catalyst 9 Catalyst 22
Catalyst
Composition 70 50 30 100 0
Az
Catalyst
Composition 30 50 70 0 100
A3
Measurement Calculation Measurement Calculation Measurement Calculation Measurement Measurement
Conversio
n rate
% 7407 74o5 73o4 73o3 7201 7200 7 6 0 4 70o1
K value 2095 2 0 92 2o76 2o74 2o58 2o57 3o24 2034
Hydrogen % Oo34 Oo34 Oo33 Oo34 Oo33 Oo33 Oo35 Oo32
Cl+C2 % 2o3 2o3 2o3 2o3 202 202 2o3 202
LPG % 17 0 9 1709 17 0 5 17o6 17 0 4 17 0 2 18o5 16o6
Gasoline % 45o6 4505 44o8 44o6 43o5 43o6 47o0 42o1
LCO % 13o2 13o2 13o 0 13o1 13o0 13o0 13o3 12o9
HCO % 1201 1203 13o6 1307 14o9 15o0 10o3 17o0
Coke % 8o5 8o4 8 0 4 8o5 8o6 8o6 8o2 8o8
50
[0058]
<>
(Comparative Example 11: Catalyst 32)
Catalyst Composition B2 and Catalyst Composition B3 were
mixed in a mass proportion of 70:30 on a dry weight basis to
form Catalyst for Fluid Catalytic Cracking 32.
(Comparative Example 12: Catalyst 33)
Catalyst Composition B2 and Catalyst Composition B3 were
mixed in a mass proportion of 50:50 on a dry weight basis to
form Catalyst for Fluid Catalytic Cracking 33.
(Comparative Example 13: Catalyst 34)
Catalyst Composition B2 and Catalyst Composition B3 were
mixed in a mass proportion of 30:70 on a dry weight basis to
form Catalyst for Fluid Catalytic Cracking 34.
(Test 9)
With Catalysts for Fluid Catalytic Cracking 10, 14, and
32 to 34, fluid catalytic cracking was performed as in Test 1.
Table 12 shows the results of reaction. As shown in Table 12,
Catalysts 32 to 34 resulted in measurements similar to the
calculations for the yields of "Gasoline," "LCO," "HCO," and
"Coke."
51
[0059]
[Table 12]
Table 12
Catalyst 32 Catalyst 33 Catalyst 34 Catalyst 10 Catalyst 14
Catalyst
Composition 70 50 30 100 0
B2
Catalyst
Composition 30 50 70 0 100
B3
Measurement Calculation Measurement Calculation Measurement Calculation Measurement Measurement
Conversio
%
n rate
7 9. 7 79.6 79.4 7 9. 4 79.3 79.2 79.9 78.9
K value 3.93 3.90 3.85 3.85 3.83 3.81 3.98 3.74 I
Hydrogen % 0.38 0.38 0.37 0.38 0.37 0.37 0.38 0.37
C1+C2 % 2.4 2.4 2.4 2.4 2.4 2.4 2.4 2.4 I
LPG % 19.1 19.1 19.1 19.1 19.0 19.0 19.1 19.0
Gasoline % 48.4 48.4 48.2 48.3 48.3 48.2 48.5 48.1
LCO % 13.4 13.4 13.4 13.4 13.4 13.4 13.4 l3. 4
HCO % 6.9 7.0 7.2 7.2 7.3 7.4 6.7 7.7
-Coke % 9.4 9.4 9.3 9.3 9.2 9.2 9.5 9.0 ~-- - -- - --
52
[0060]
Therefore, the present invention, namely, a catalyst for
fluid catalytic cracking comprising Catalyst Composition A
that comprises a silica-based binder and Catalyst Composition
B that comprises an aluminum-compound binder mixed therein in
any mass proportion in the range of 10:90 to 90:10, provides
"Gasoline" and "LPG" in higher yields and "HCO" and "Coke" in
lower yields than the calculations to a greater extent than
any catalyst based only on Catalyst Composition A, any
catalyst based only on Catalyst Composition B, any catalyst
as a mixture of two catalyst compositions comprising a
silica-based binder, and any catalyst as a mixture of two
catalyst compositions comprising an aluminum-compound binder.
This can be understood as follows: alumina contained in
Catalyst Composition B, which comprises an alumina-compound
binder, binds to metals poisonous to catalysts, such as
vanadium and nickel, to detoxify them, and thus Catalyst
Composition A, which comprises a silica-based binder, becomes
unlikely to be poisoned by these poisonous metals; as a
result, a high gasoline yield and a high yield of a gas oil
fraction as well as a high degree of bottom cracking are
achieved while the high gasoline yield and a low coke yield
are maintained.
[0061]
53
The present invention is not limited to the embodiment
described above and can be modified within the gist of the
present invention. For example, any catalyst for fluid
catalytic cracking according to the present invention
constituted as a combination of some or all of the
embodiments described above or modifications is also included
in what is claimed by the present invention.
[0062]
In the examples above, a kind of Catalyst Composition A,
which comprises a silica-based binder, and a kind of Catalyst
Composition B, which comprises an aluminum-compound binder
are combined to produce a catalyst for fluid catalytic
cracking; however, for example, two or more kinds of Catalyst
Composition A and/or Catalyst Composition B may be combined
to constitute a catalyst for fluid catalytic cracking,
respectively.

54
CLAIMS
[Claim 1]
A catalyst for fluid catalytic cracking of hydrocarbon
oil, comprising a catalyst composition A that comprises
zeolite and 10 to 30 % by mass of a silica-based binder as a
binding agent and a catalyst composition B that comprises
zeolite and 10 to 30 % by mass of an aluminum-compound binder
as a binding agent, mixed therein in any mass proportion in
the range of 10:90 to 90:10 (WA:WB), provided that WA is the
mass of the catalyst composition A and WB is the mass of the
catalyst composition B.
[Claim 2]
The catalyst for fluid catalytic cracking of hydrocarbon
oil according to Claim 1, wherein each of the catalyst
composition A and the catalyst composition B has a K value as
expressed by the following formula (1), which is equal to or
higher than 1.
K value = Conversion rate/ (100-Conversion rate) ... (1)
where the conversion rate is expressed by the following
formula (2);
Conversion rate (% by mass) = (a-b) /a x 100 ... (2)
where the symbol "a" represents the mass of raw material
oil, and "b" represents the total mass of light cycle oil and
heavy cycle oil.
55
[Claim 3]
The catalyst for fluid catalytic cracking of hydrocarbon
oil according to Claim 2, wherein, when the K values for the
catalyst composition A and for the catalyst composition B are
expressed as "KA" and "K8 " respectively, the ratio of KA:K8 is
in the range as shown in the following formula (3);
KA: K8 = 1: 0. 5 to 1: 1. 5 ( 3)
[Claim 4]
The catalyst for fluid catalytic cracking of hydrocarbon
oil according to any of Claims 1 to 3, wherein, when the K
value for the above catalyst is expressed as "Km", the Km is
greater than the K value for the catalyst composition A (KA)
and the K value for the catalyst composition B (K8 ).
[Claim 5]
The catalyst for fluid catalytic cracking of hydrocarbon
oil according to any of Claims 1 to 4, wherein a gasoline
yield by use of the above catalyst, when it is expressed as
"Gm", is greater than a gasoline yield by use of the catalyst
composition A, when it is expressed as "GA" and a gasoline
yield by use of the catalyst composition B, when it is
expressed as "GB"·
[Claim 6]
The catalyst for fluid catalytic cracking of hydrocarbon
oil according to any of Claims 1 to 5, wherein the above
56
silica-based binder is one or more of the binding agent ( s)
selected from the group consisting of a silica sol, a water
glass, and an acidic liquid of silicic acid.
[Claim 7]
The catalyst for fluid catalytic cracking of hydrocarbon
oil according to any of Claims 1 to 6, wherein the aluminumcompound
binder is one or more of the binding agent(s)
selected from the group consisting of the following compound
(a) to (c);
(a) Basic aluminum chloride,
(b) Aluminum biphosphate,
(c) Alumina sol.
[Claim 8]
The catalyst for fluid catalytic cracking of hydrocarbon
oil according to any of Claims 1 to 7, wherein the zeolite
has a crystal structure selected from the group consisting of
FAU type (faujasite type), MFI type, CHA type, and MOR type,
or a mixture thereof and is contained in the catalyst
composition A and the catalyst composition B in the range of
15 to 60 % by mass respectively on a catalyst basis.
[Claim 9]
The catalyst for fluid catalytic cracking of hydrocarbon
oil according to Claim 8, wherein the zeolite, when it has a
crystal structure of the FAU type, is any one of hydrogen Y57
type zeolite (HY), ultrastable Y-type zeolite (USY), rareearth
exchanged Y-type zeolite (REY),
exchanged ultrastable Y-type zeolite (REUSY).
[Claim 10]
and rare-earth
The catalyst for fluid catalytic cracking of hydrocarbon
oil according to any of Claims 1 to 9, wherein the catalyst
composition A and the catalyst composition B further comprise,
besides the zeolite and the binding agent, a clay mineral.
[Claim 11]
A method for fluid catalytic cracking of hydrocarbon oil,
with use of the above catalyst according ·to any of Claims 1
to 10.
[Claim 12]
The method for fluid catalytic cracking of hydrocarbon
oil according to Claim 11, wherein the hydrocarbon oil
comprises a residual oil.
[Claim 13]
The method for fluid catalytic cracking of hydrocarbon
oil according to Claim 12, wherein the hydrocarbon oil
comprises vanadium and nickel being equal to or more than 0.5
ppm by mass for each.
[Claim 14]
The method for fluid catalytic cracking of hydrocarbon
oil according to any of Claims 11 to 13, wherein the above
58
catalyst comprises vanadium and nickel being equal to or more
than 300 ppm by mass for each.