WO2009145311A1

WO2009145311A1 - Catalyst for fluid catalytic cracking of hydrocarbon oil and method of fluid catalytic cracking of hydrocarbon oil with the same

Info

Publication number: WO2009145311A1
Application number: PCT/JP2009/059887
Authority: WO
Inventors: 松本　広; 誠二郎野中; 福田　盛男; 小松　通郎
Original assignee: 日揮触媒化成株式会社
Priority date: 2008-05-30
Filing date: 2009-05-29
Publication date: 2009-12-03
Also published as: KR20110007622A; AU2009252242A1; AU2009252242B2; TW201004706A; SG2014012801A; TWI465288B; MY153881A; JP5628027B2; JPWO2009145311A1; KR101566185B1

Abstract

A catalyst for the fluid catalytic cracking of hydrocarbon oils is provided with which gasoline and a gas oil fraction can be obtained in high yield and a high degree of bottom cracking and a low coke yield are attained. A catalyst composition (A) comprising a zeolite and 10-30 mass% silica-based binder was mixed with a catalyst composition (B) comprising a zeolite and 10-30 mass% aluminum-compound binder, in a mass proportion (W_A:W_B) of from 10:90 to 90:10, provided that W_A is the mass of the catalyst composition (A) and W_B is the mass of the catalyst composition (B).

Description

Fluid catalytic cracking catalyst of hydrocarbon oil and fluid catalytic cracking method of hydrocarbon oil using the same

The present invention provides a fluid catalytic cracking catalyst for hydrocarbon oils having a high bottom resolution and a low coke yield, as well as fluid catalytic cracking of hydrocarbon oils using the same, in which gasoline and light oil fractions are obtained in high yield. Regarding the method.

In the past, fluidized catalytic cracking of hydrocarbon oils has been developed in order to obtain gasoline in high yield and lower the yield of coke, and fluid catalytic cracking catalysts using silica-based binders such as silica sol as binders have been developed. (For example, refer to Patent Document 1). However, a fluid catalytic cracking catalyst using a silica-based binder has been required to have higher bottom decomposability.

Also, gasoline and kerosene fraction (kerose fraction and diesel fraction. Light Cycle Oil; hereinafter referred to as “LCO”) can be obtained in high yield and the bottom resolution is increased, that is, heavy fraction In order to achieve a low yield of (Heavy Cycle Oil; hereinafter also referred to as “HCO”), fluid catalytic cracking catalysts using an alumina compound binder such as basic aluminum chloride as a binder have been developed (for example, patents) Reference 2). However, in a fluid catalytic cracking catalyst using an alumina compound binder, it has been required to make coke a lower yield.

Here, in the fluid catalytic cracking device (actual device), the fluid catalytic cracking catalyst is used so that the resulting product oil has the desired composition (for example, “more gasoline”, “more kerosene fraction”, etc.). I was switching and using it. Moreover, since the composition of the resulting product oil changes when the raw material oil is changed, the fluid catalytic cracking catalyst has been switched so as to obtain the desired composition of the resulting product oil. In that case, (1) When switching from a catalyst containing a silica-based binder to a catalyst containing another silica-based binder, (2) When switching from a catalyst containing an aluminum compound binder to a catalyst containing another aluminum compound binder, 3) When switching from a catalyst containing a silica-based binder to a catalyst containing an aluminum compound binder, (4) sometimes switching from a catalyst containing an aluminum compound binder to a catalyst containing a silica-based binder. Here, when switching the catalyst, first, a part of the first catalyst in the apparatus is taken out, and then the second catalyst having the same amount as that taken out is put into the apparatus. In this case, in the fluid catalytic cracking apparatus, the mixing ratio (mass ratio) of the first catalyst and the second catalyst gradually changes, and finally the inside of the apparatus is changed from the first catalyst to the second catalyst. It was replaced with. At that time, there were changes in catalyst activity, conversion rate, gasoline yield, etc., but it was thought to be due to newly added catalyst or due to operating conditions of the apparatus.

In addition, there are additive catalysts (added catalysts) that are added to the fluid catalytic cracking catalyst. These supplement the fluid catalytic cracking catalyst performance (eg, NOx removal, SOx removal, metal resistance, octane number improvement, bottom resolution, etc.). However, the gasoline and diesel oil fractions were obtained in high yields, and did not satisfy high bottom resolution and low coke yields.

JP 2007-748 A JP 2006-142273 A

However, the conventional fluid catalytic cracking catalyst has a problem that a catalyst satisfying any of high gasoline yield, high light oil fraction yield, low coke yield, and high bottom cracking rate has not been developed.

The present invention has been made in view of such circumstances, and a gasoline and gas oil fraction can be obtained in a high yield, a high bottom cracking, and a fluid catalytic cracking catalyst for hydrocarbon oil having a low coke yield, and It aims at providing the fluid catalytic cracking method of the used hydrocarbon oil.

That is, the gist of the present invention is as follows.
[1] A catalyst composition comprising a catalyst composition A containing 10 to 30% by mass of a silica-based binder as zeolite and a binder, and a catalyst composition B containing 10 to 30% by mass of an aluminum compound binder as a binder. The mass of the product A is W _A , the mass of the catalyst composition B is W _B , and the mass ratio (W _A : W _B ) is mixed at an arbitrary ratio within the range of 10:90 to 90:10. A fluid catalytic cracking catalyst for hydrocarbon oils.
[2] The catalyst composition A and the catalyst composition B have a K value represented by the following formula (1) (each K value is represented by “K _A ” and “K _B ”) of 1 or more. The fluid catalytic cracking catalyst for hydrocarbon oils according to [1].

K = conversion / (100−conversion) (1)
In addition, a conversion rate is shown by following formula (2).

Conversion (mass%) = (ab) / a × 100 (2)
Here, a is the mass of the raw material oil, and b is the total mass of the kerosene oil fraction and the heavy fraction.
[3] The fluid catalytic cracking catalyst for hydrocarbon oils according to [1] or [2], wherein the K values of the catalyst composition A and the catalyst composition B have a relationship represented by the following formula (3).

K _A : K _B = 1: 0.5 to 1: 1.5 (3)
[4] The K value (K _m ) of the fluid catalytic cracking catalyst is higher than the K value (K _A ) of the catalyst composition _A and the K value (K _B ) of the catalyst composition B. [1] A fluid catalytic cracking catalyst for hydrocarbon oils according to any one of [3].
[5] Gasoline yield G _m of fluid catalytic cracking catalyst, and wherein the higher than the gasoline yield G _B gasoline yield G _A and the catalyst composition B of the catalyst composition A [1] ~ [4 ] The fluid catalytic cracking catalyst of any hydrocarbon oil.
[6] Fluid catalytic cracking of the hydrocarbon oil according to any one of [1] to [5], wherein the silica-based binder is one or more of silica sol, water glass, and silicic acid liquid catalyst.
[7] The fluid contact of the hydrocarbon oil according to any one of [1] to [6], wherein the aluminum compound binder is at least one selected from the group consisting of the following (a) to (c): Cracking catalyst.
(A) Basic aluminum chloride.
(B) Aluminum biphosphate.
(C) Alumina sol.
[8] The zeolite contained in the catalyst composition A and the catalyst composition B is one or more of FAU type (faujasite type), MFI type, CHA type, and MOR type, and Any one of [1] to [7], wherein the catalyst composition A and the catalyst composition B each contain the zeolite in a range of 15 to 60% by mass on the basis of the catalyst composition. Fluid catalytic cracking catalyst of hydrocarbon oil.
[9] The FAU type zeolite includes hydrogen type Y zeolite (HY), ultrastabilized Y type zeolite (USY), rare earth exchanged Y type zeolite (REY), and rare earth exchanged superstabilized Y type zeolite (REUSY). [8] The fluid catalytic cracking catalyst for hydrocarbon oils according to [8].
[10] The fluid contact of the hydrocarbon oil according to any one of [1] to [9], wherein the catalyst composition A and the catalyst composition B contain a clay mineral in addition to the zeolite and the binder Cracking catalyst.
[11] A method for fluid catalytic cracking of hydrocarbon oil, wherein the fluid catalytic cracking catalyst for hydrocarbon oil according to any one of [1] to [10] is used.
[12] The fluid catalytic cracking method of hydrocarbon oil according to [11], wherein the hydrocarbon oil includes a residual oil.
[13] The fluid catalytic cracking method of hydrocarbon oil according to [12], wherein the hydrocarbon oil contains 0.5 ppm or more of vanadium and nickel.
[14] The fluid catalytic cracking method for hydrocarbon oils according to any one of [11] to [13], wherein the fluid catalytic cracking catalyst contains 300 ppm or more of vanadium and nickel, respectively.

In the fluid catalytic cracking catalyst for hydrocarbon oils of the present invention, two kinds of catalyst compositions having different oils that can be decomposed, that is, a catalyst composition A containing a silica-based binder and a catalyst composition B containing an aluminum compound binder, As a result, when hydrocracking hydrocarbon oil by fluid catalytic cracking, the oil decomposed by one catalyst composition can be decomposed by the other catalyst composition. In addition, gasoline and light oil fractions can be obtained in high yield, coke can be obtained in low yield, and bottom resolution can be increased, that is, production of heavy fractions can be suppressed.

In particular, when the raw material oil is a heavy oil containing a large amount of poisoning metals such as vanadium and nickel, the alumina contained in the catalyst composition B containing the alumina compound binder is combined with the poisoning metals and detoxified. As a result, the catalyst composition A containing the silica-based binder is not easily poisoned by the poisoning metal, and the high gasoline yield and the high light oil fraction yield and the high gasoline yield and the low coke yield are maintained. It is understood that it becomes high bottom decomposition.

It is a graph of K value which concerns on one Example of this invention. It is a graph of the gasoline yield which concerns on one Example of this invention.

The hydrocarbon oil fluid catalytic cracking catalyst according to one embodiment of the present invention includes a catalyst composition A containing 10 to 30% by mass of a silica-based binder as a zeolite and a binder, and 10 to 30% by mass as a zeolite and a binder. % Of the aluminum compound binder, the mass of the catalyst composition A is W _A , the mass of the catalyst composition B is W _B , and the mass ratio (W _A : W _B ) is 10:90 to It is a mixture within the range of 90:10. Hereinafter, each catalyst composition will be described in detail.

In the fluid catalytic cracking device (actual device), when the catalyst is switched from the catalyst containing the silica-based binder to the catalyst containing the aluminum compound binder or vice versa, the other catalyst is gradually added. The mass ratio may be different, but the present invention is different in that a catalyst mixed at a predetermined mass ratio is always added, and the mass ratio of the catalyst composition in the apparatus is kept constant.

Further, the catalyst of the present invention is a mixture of catalyst compositions having different binders, which are subjected to fluid catalytic cracking, and an additive catalyst (added catalyst added to supplement the performance of fluid catalytic cracking catalyst) ) Is different.
[Catalyst composition A]
The catalyst composition A is, for example, 15 to 60% by mass of zeolite, preferably 20 to 50% by mass, 10 to 30% by mass of silica-based binder as a binder, preferably 15 to 25% by mass, and the rest excludes zeolite. Contains inorganic oxides.
<Silica-based binder>
As the silica-based binder, one or more of silica sol, water glass (sodium silicate), and silicate liquid can be used. Silica sol can be prepared from water glass. For example, a silica sol having a SiO ₂ concentration of 10 to 15% by mass is prepared by simultaneously adding water glass having a SiO ₂ concentration of 12 to 23% by mass and sulfuric acid having a concentration of 20 to 30% by mass simultaneously. Can do.
<< Zeolite >>
Here, as the zeolite, it is possible to use a zeolite that is usually used as a catalytic cracking catalyst for hydrocarbon oils. For example, FAU type (faujasite type. For example, Y type zeolite, X type zeolite, etc.) One or more of MFI type (for example, ZSM-5, TS-1 etc.), CHA type (for example, chabasite, SAPO-34 etc.) and MOR type (for example, mordenite, Ca-Q etc.) In particular, the FAU type is preferable. The faujasite-type zeolite includes hydrogen-type Y zeolite (HY), ultra-stabilized Y-type zeolite (USY), and rare earth-exchanged Y-type zeolite (REY) in which rare earth metals are supported on HY and USY, respectively, by ion exchange. ), Rare earth exchange ultra-stabilized Y-type zeolite (REUSY).

When the content of the zeolite with respect to the catalyst composition A is less than 15% by mass, the decomposition activity tends to be low, and when it exceeds 60% by mass, the bulk density tends to be high and the strength tends to be low.
<Inorganic oxide>
As inorganic oxides, activated alumina, porous silica, rare earth metal compounds, and metal scavengers (metal trapping agents) can be used in addition to clay minerals such as kaolin.

The rare earth metal oxide may be contained in the catalyst composition A so as to be 0.5 to 2.0 mass% as RE ₂ O ₃ . Here, examples of the rare earth metal include cerium (Ce), lanthanum (La), praseodymium (Pr), neodymium (Nd), and the like, and these can be supported alone or as two or more metal oxides. .

An example of the manufacturing method of the catalyst composition A is shown below. First, ultra-stabilized Y-type zeolite (USY) prepared by adding kaolin, porous silica powder, and activated alumina to the silica sol (an example of a silica-based binder) and adjusting the pH to 3 to 5 with 20 to 30% by mass sulfuric acid. Add the slurry to prepare a mixed slurry. The mixed slurry is spray-dried to obtain spherical particles. The obtained spherical particles were washed, further contacted with an aqueous solution of rare earth metal (Rare Earth.RE) chloride, and subjected to ion exchange so that RE ₂ O ₃ was 0.5 to 2.0% by mass, Dry to obtain catalyst composition A. The average particle size of the obtained catalyst composition A is not particularly limited as long as it can be mixed with the catalyst composition B described later, but is about 60 to 70 μm.
[Catalyst composition B]
The catalyst composition B is, for example, 15 to 60% by mass of zeolite, preferably 20 to 50% by mass, 10 to 30% by mass of an aluminum compound binder as a binder, preferably 15 to 25% by mass, and the rest excludes zeolite. Contains inorganic oxides.
《Aluminum compound binder》
Examples of the aluminum compound binder include (a) basic aluminum chloride, (b) aluminum biphosphate, and (c) alumina sol. Moreover, as an aluminum compound binder, the solution which melt | dissolved any 1 or 2 or more of crystalline aluminas, such as a dibsite, a bayerite, and a boehmite, in an acid solution can also be used.

Here, basic aluminum chloride is represented by Formula 4.

[Al ₂ (OH) _n Cl _6-n ] _m (4)
(However, 0 <n <6, 1 ≦ m ≦ 10, preferably 4.8 ≦ n ≦ 5.3, 3 ≦ m ≦ 7, where m represents a natural number.)
The heavy aluminum phosphate is also called aluminum dihydrogen phosphate or primary aluminum phosphate, and is represented by Al (H ₂ PO ₄ ) ₃ . The alumina sol can be produced, for example, by adjusting the pH of pseudo boehmite type alumina with an acid.
<< Zeolite and inorganic oxide >>
About the zeolite and inorganic oxide which are used for the catalyst composition B, the thing similar to the above-mentioned catalyst composition A can be used, About those content, it can prepare similarly to the catalyst composition A.

An example of the manufacturing method of the catalyst composition B is shown below. First, for example, kaolin, activated alumina, and USY slurry are added to a basic aluminum chloride solution (an example of an aluminum compound binder) having an Al ₂ O ₃ concentration of 20 to 25% by mass, and the slurry concentration is 35 to 45%. A mixed slurry is prepared. The mixed slurry is spray-dried to obtain spherical particles. The spherical particles are washed, further contacted with a rare earth metal chloride aqueous solution to perform ion exchange so that the RE ₂ O ₃ content is 0.5 to 2.0% by mass, and then dried to obtain a catalyst composition B. The average particle diameter of the obtained catalyst composition B is not particularly limited, but is about 60 to 70 μm.
[Fluid catalytic cracking catalyst]
Fluid catalytic cracking catalyst of the present invention, a catalyst composition A and the catalyst composition B, the weight of the catalyst composition A and W _A, the weight of the catalyst composition B as W _B, the mass ratio (W _A: W _B ) was mixed within the range of 10:90 to 90:10, and when the mass ratio of each catalyst composition was outside the predetermined range, each catalyst composition was used alone for fluid catalytic cracking. The difference from the case becomes small, and it becomes difficult to obtain a clear effect. The mixing ratio (mass ratio) of the catalyst composition A and the catalyst composition B is such that the cracked product (particularly gasoline, LCO) obtained by cracking hydrocarbon oil with the present fluid catalytic cracking catalyst has a desired composition. (Yield) should be determined.
[Fluid catalytic cracking method]
In fluid catalytic cracking using the fluid catalytic cracking catalyst of the present invention, the usual fluid catalytic cracking conditions of hydrocarbon oil can be employed, and for example, the conditions described below can be suitably employed.

As the feedstock used for the catalytic cracking, a normal hydrocarbon feedstock such as hydrodesulfurization vacuum distillation gas oil (DSVGO) or vacuum distillation gas oil (VGO) can be used, and further, atmospheric distillation residue oil. (AR), vacuum distillation residue oil (VR), desulfurization atmospheric distillation residue oil (DSAR), desulfurization vacuum distillation residue oil (DSVR), deasphaltenic oil (DAO), and other residual oils can be used. A single material or a mixture thereof can be used. In the fluid catalytic cracking catalyst of the present invention, a residual oil containing 0.5 ppm or more of nickel and vanadium can be treated, and a residual oil catalytic cracking apparatus (Resid FCC) that uses the residual oil alone as a raw material oil. RFCC). Here, when a conventional fluid catalytic cracking catalyst is used in RFCC, nickel and vanadium in the residual oil adhere to the catalyst and the activity is reduced. However, in the fluid catalytic cracking catalyst of the present invention, vanadium and nickel are Even if the residual oils containing 0.5 ppm or more are treated, excellent catalyst performance can be maintained. Further, the fluid catalytic cracking catalyst of the present invention can maintain the catalytic performance even when vanadium and nickel are contained in an amount of 300 ppm or more. The upper limits of vanadium and nickel contained in the fluid catalytic cracking catalyst of the present invention are each about 10000 ppm.

Further, the reaction temperature when catalytically cracking the above hydrocarbon feedstock is preferably in the range of 470 to 550 ° C., and the reaction pressure is generally in the range of about 1 to 3 kg / cm ² . The mass ratio 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 .
<< K value >>
K value is the mass of kerosene oil fraction (LCO) and heavy oil fraction (HCO), which are fractions higher than the boiling point of gasoline (about 30-220 ° C) by catalytic cracking of the feedstock oil by the method described above. And the conversion rate can be obtained from the mass of the raw material oil by the equation (2) and can be obtained from the conversion rate by the equation (1).

K = conversion / (100−conversion) (1)
Conversion (mass%) = (ab) / a × 100 (2)
However, a is the mass of raw material oil, b is the total mass of a kerosene oil fraction and a heavy fraction.

Here, the K values (K _A and K _B ) of the catalyst composition A and the catalyst composition B are 1 or more (that is, conversion rate 50% or more), preferably 1.5 or more (that is, conversion rate 60%). Above, more preferably 2.3 or more (that is, conversion 70% or more). When the K value of the catalyst composition A and the catalyst composition B is less than 1 (that is, the conversion rate is less than 50%), the yield of gasoline or LCO is low, which is not practical.

Further, the catalyst composition K values of A and catalyst composition B K _A: K _B is 1: 0.5 to 1: 1.5, preferably 1: 0.8-1: 1.2, more preferably 1: 0.9 to 1: 1.1 is preferable. _{_{Here, K A: K B <1}} : 0.5 in the case and K _A: K _B> 1: In the case of 1.5, since the difference in K values of both the catalyst composition is too high, K _A and it is difficult to exceed K _B.

Further, the K value (K _m ) of the fluid catalytic cracking catalyst is preferably higher than the K value (K _A ) of the catalyst composition _A and the K value (K _B ) of the catalyst composition B.
<< Gasoline yield G >>
Gasoline yield G _m of fluid catalytic cracking catalyst is higher is preferred than the gasoline yield G _B gasoline yield G _A and the catalyst composition B of the catalyst composition A. Here, the gasoline yield is calculated from the mass of gasoline obtained by catalytically cracking the feedstock by the above-described method and the mass of the feedstock.

Further, the fluid catalytic cracking catalyst of the present invention tends to have a higher LCO yield than that of the catalyst composition A and the catalyst composition B alone, and conversely, the hydrogen yield, the C1 + C2 yield, the LPG yield. , HCO yield, and coke yield tend to be low. That is, the fluid catalytic cracking catalyst of the present invention tends to increase the yield of liquid fuel such as gasoline and LCO as compared with the catalyst composition A and the catalyst composition B alone, but gas, heavy oil, coke, etc. Yield tends to be low.

[Preparation of silica binder]
"Catalyst composition A _1"
2941 g of water glass having a SiO ₂ concentration of 17% by mass and 1059 g of sulfuric acid having a concentration of 25% by mass are continuously added simultaneously to prepare 4000 g of silica sol (an example of a silica-based binder) having a SiO ₂ concentration of 12.5% by mass. did. 800 g of kaolin, 175 g of porous silica powder, and 250 g of activated alumina are added to this silica sol on a dry basis, and 800 g of ultra-stabilized Y-type zeolite (USY) slurry adjusted to pH 3.9 with 25% by mass sulfuric acid is added and mixed. A slurry was prepared. This mixed slurry was spray-dried to obtain spherical particles having an average particle size of 60 μm.

The obtained spherical particles were washed, and further contacted with an aqueous solution of rare earth metal (Rare Earth.RE) chloride (including cerium and lanthanum chlorides, the same applies hereinafter) to give 1.0% by mass as RE ₂ O _3. After ion exchange so as to be, the catalyst composition A ₁ was prepared by drying with a dryer at 135 ° C.

The composition of the catalyst composition A ₁ is 20% by mass of SiO ₂ derived from silica sol, 32% by mass of kaolin, 7% by mass of SiO ₂ derived from porous silica powder, 10% by mass of activated alumina, and 30% by mass of USY. Met. Here, Table 1 shows properties of the catalyst composition A ₁ .
"Catalyst composition A _2"
2941 g of water glass having a SiO ₂ concentration of 17% by mass and 1059 g of sulfuric acid having a concentration of 25% by mass are continuously added simultaneously to prepare 4000 g of silica sol (an example of a silica-based binder) having a SiO ₂ concentration of 12.5% by mass. did. To this silica sol, 800 g of kaolin, 175 g of porous silica powder, and 250 g of activated alumina were added on a dry basis, and 800 g of ultra-stabilized REY zeolite (REUSY) slurry prepared to pH 3.9 with 25% by mass sulfuric acid as Y zeolite. Was added to prepare a mixed slurry. This mixed slurry was spray-dried to obtain spherical particles having an average particle size of 60 μm.

The obtained spherical particles were washed and then dried with a dryer at 135 ° C. to prepare catalyst composition A ₂ . Here, the properties of the catalyst composition A ₂ in Table 1.
"Catalyst composition A _3"
800 g of kaolin, 175 g of porous silica powder, and 250 g of activated alumina were added to 2941 g of water glass (an example of a silica-based binder) having a SiO ₂ concentration of 17% by mass, and further adjusted to pH 3.9 with 25% by mass sulfuric acid. 800 g of ultra-stabilized REY-type zeolite (REUSY) slurry was added as a Y-type zeolite to prepare a mixed slurry. This mixed slurry was spray-dried to obtain spherical particles having an average particle size of 60 μm.

The obtained spherical particles were washed and then dried with a dryer at 135 ° C. to prepare catalyst composition A ₃ . Here, the properties of the composition of the catalyst composition A ₃ in Table 1.

The specific surface area was measured by the BET method, and the bulk specific gravity was measured by the UOP method 254-65. Further, the weight loss by firing indicates the weight reduced when firing at 1000 ° C. for 1 hour. (The same applies hereinafter)
[Preparation of aluminum compound binder]
"Catalyst composition B _1"
A mixed slurry in which 840 g of kaolin, 260 g of activated alumina, and 640 g of USY slurry are added to 1201 g of a basic aluminum chloride solution (an example of an aluminum compound binder) having an Al ₂ O ₃ concentration of 23.3 mass%, and the slurry concentration is 41%. Was prepared. This mixed slurry was spray-dried to obtain spherical particles having an average particle size of 60 μm. The spherical particles were washed and further contacted with an aqueous rare earth metal chloride solution to exchange ions so that the RE ₂ O ₃ was 1.0% by mass. Prepared. The composition of the obtained catalyst composition B ₁ was 14% by mass of Al ₂ O ₃ derived from the basic aluminum chloride solution, 41% by mass of kaolin, 13% by mass of activated alumina, and 32% by mass of USY. Also shows the properties of the catalyst composition B ₁ in Table 2.
"Catalyst composition B _2"
To 1201 g of a basic aluminum chloride solution (an example of an aluminum compound binder) having an Al ₂ O ₃ concentration of 23.3 mass%, 840 g of kaolin, 260 g of activated alumina, and 640 g of REUSY slurry as Y-type zeolite are added, and the slurry concentration is 43. % Mixed slurry was prepared. This mixed slurry was spray-dried to obtain spherical particles having an average particle size of 60 μm. After washing the spherical particles, to prepare a catalyst composition B ₂ and dried at 135 ° C. The dryer. Here, the properties of the catalyst composition B ₂ in Table 2.
"Catalyst composition B _3"
An alumina sol (an example of an aluminum compound binder) was prepared by adding pH 3.0 to 63% nitric acid in 2400 g of an aqueous pseudoboehmite type alumina (Catapal-A manufactured by Sasol) having an Al ₂ O ₃ concentration of 12.5% by mass. 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 to prepare a mixed slurry having a slurry concentration of 43%. This mixed slurry was spray-dried to obtain spherical particles having an average particle size of 60 μm. The spherical particles were calcined at 600 ° C. with an electric furnace to prepare catalyst composition B ₃ . Here, the properties of the catalyst composition B ₃ in Table 2.
"Catalyst composition B _4"
To 1723 g of 17.4 mass% aluminum biphosphate solution (an example of an aluminum compound binder), 840 g of kaolin, 260 g of activated alumina, and 640 g of REUSY slurry as Y-type zeolite are added, and a mixed slurry having a slurry concentration of 43% is obtained. Prepared. This mixed slurry was spray-dried to obtain spherical particles having an average particle size of 60 μm. The spherical particles were calcined at 600 ° C. in an electric furnace to prepare catalyst composition B ₄ . Here, the properties of the catalyst composition B ₄ in Table 2.

<< Experimental example 1: A ₁ -B ₁ >>
(Example 1: Catalyst 1)
Catalyst composition A ₁ and catalyst composition B ₁ were mixed so that the mass ratio was 70:30 on a dry basis to prepare fluid catalytic cracking catalyst 1.
(Example 2: Catalyst 2)
Catalyst composition A ₁ and catalyst composition B ₁ were mixed so that the mass ratio was 50:50 on a dry basis to prepare fluid catalytic cracking catalyst 2.
(Example 3: Catalyst 3)
Catalyst composition A ₁ and catalyst composition B ₁ were mixed so that the mass ratio was 30:70 on a dry basis to prepare fluid catalytic cracking catalyst 3.
(Comparative Example 1: Catalyst 4)
The catalyst composition A ₁ was fluidized catalytic cracking catalyst 4.
(Comparative Example 2: Catalyst 5)
The catalyst composition B ₁ was designated as fluid catalytic cracking catalyst 5.
(Test Example 1)
The fluid catalytic cracking catalysts 1 to 5 were subjected to catalytic cracking reaction tests using the pilot reaction test apparatus (manufactured by ARCO) under the same feedstock and the same reaction conditions. The pilot reaction test apparatus is a circulating fluidized bed in which a catalyst circulates in the apparatus and alternately repeats reaction and catalyst regeneration, and imitates a fluid catalytic cracking apparatus used on a commercial scale. (The following examples are also the same)
First, before the reaction test, cyclic metal deposition is performed so that the fluid catalytic cracking catalysts 1 to 5 contain 4000 mass ppm of vanadium octylate as V and 2000 mass ppm of nickel octylate as Ni on a mass basis. Pretreatment was performed by (cyclic metal deposition. CMD) method. Here, the CMD method refers to impregnating a small amount of vanadium and nickel into a fluid catalytic cracking catalyst and regenerating the fluid catalytic cracking catalyst at a high temperature, so that vanadium and nickel are added to the fluid catalytic cracking catalyst at a target concentration. This is a method of repeatedly oxidizing and reducing at a high temperature of 400 to 800 ° C. after being deposited until it becomes, and imitating a fluid catalytic cracking apparatus used on a commercial scale. (The following examples are also the same)
Here, fluid catalytic cracking was performed under the reaction conditions shown in Table 3. The reaction results are shown in Table 4, FIG. 1 and FIG. Here, in Table 4, the calculated values of the catalysts 1 to 3 are based on the reaction test results of the catalyst 4 (that is, the catalyst composition A ₁ only) and the catalyst 5 (that is, the catalyst composition B ₁ only). It is calculated (weighted average) based on the mixing ratio of each catalyst (the same applies to the following examples). However, each K value was calculated from the conversion rate.

The K values in Table 4 are shown in FIG. 1, and the gasoline yield is shown in FIG. In FIG. 1 and FIG. 2, “■” indicates an actually measured value, and ● indicates a “calculated value”.
As shown in Table 4, with respect to each calculated value, the catalysts 1 to 3 obtained “gasoline” and “LCO” in high yields, and “HCO” and “coke” obtained low yields. . Further, as shown in FIG. 1, when the catalyst composition A ₁ is 10 to 40% by mass (ie, when W _A : W _B = 10: 90 to 40:60), the K value (K _m ) of the catalyst 1 is K value of the catalyst composition a ₁ (K _a) and a K value of the catalyst composition B ₁ (K _B) is higher than. From FIG. 2, when the catalyst composition A1 is 10 to 90% by mass (that is, when W _A : W _B = 10: 90 to 90:10), the gasoline yield of the catalyst 1 is the catalyst composition A ₁ and The gasoline yield of each of the catalyst compositions B ₁ is higher.

However,
Conversion (mass%) = (ab) / a × 100
a: Mass of feed oil b: Total mass of kerosene oil fraction (LCO) and heavy fraction (HCO) K value = conversion rate / (100-conversion rate)
・ Hydrogen (mass%) = c / a × 100
c: Mass of hydrogen in the generated gas C1 + C2 (mass%) = d / a × 100
d: Mass of C1 (methane) and C2 (ethane, ethylene) in the product gas LPG (liquefied petroleum gas, mass%) = e / a × 100
e: Mass of propane, propylene, butane, and butylene in the product gas. Gasoline (mass%) = f / a × 100
f: Mass of gasoline (boiling range: boiling point of C5 (butane) (20 ° C.) to 204 ° C.) in the produced oil) LCO (mass%) = g / a × 100
g: Mass of light cycle oil (boiling point range: 204 to 343 ° C.) in the product oil HCO (mass%) = h / a × 100
h: Mass of heavy cycle oil (boiling point range: 343 ° C. or higher) in the product oil Coke (mass%) = i / a × 100
i: Coke mass deposited on catalyst mixture The same applies to the following examples.
<< Experimental example 2: A ₂ -B ₂ >>
(Example 4: Catalyst 6)
Catalyst composition A ₂ and catalyst composition B ₂ were mixed so that the mass ratio was 70:30 on a dry basis to prepare fluid catalytic cracking catalyst 6.
(Example 5: Catalyst 7)
Catalyst composition A ₂ and catalyst composition B ₂ were mixed so that the mass ratio was 50:50 on a dry basis to prepare fluid catalytic cracking catalyst 7.
(Example 6: Catalyst 8)
Catalyst composition A ₂ and catalyst composition B ₂ were mixed so that the mass ratio was 30:70 on a dry basis to prepare fluid catalytic cracking catalyst 8.
(Comparative Example 3: Catalyst 9)
The catalyst composition A ₂ was fluid catalytic cracking catalyst 9.
(Comparative Example 4: Catalyst 10)
The catalyst composition B ₂ was fluid catalytic cracking catalyst 10.
(Test Example 2)
The fluid catalytic cracking catalysts 6 to 10 were subjected to fluid catalytic cracking in the same manner as in Test Example 1. Table 5 shows the reaction results. As shown in Table 5, with respect to each calculated value, the catalysts 6 to 8 obtained “gasoline” and “LPG” in high yields, and “HCO” and “coke” obtained low yields. .

<< Experimental Example 3: A ₂ -B ₃ >>
(Example 7: Catalyst 11)
The catalyst composition A ₂ and the catalyst composition B ₃ were mixed so that the mass ratio was 70:30 on a dry basis to prepare a fluid catalytic cracking catalyst 11.
(Example 8: Catalyst 12)
Catalyst composition A ₂ and catalyst composition B ₃ were mixed so that the mass ratio was 50:50 on a dry basis to prepare fluid catalytic cracking catalyst 12.
(Example 9: Catalyst 13)
Catalyst composition A ₂ and catalyst composition B ₃ were mixed so that the mass ratio was 30:70 on a dry basis to prepare fluid catalytic cracking catalyst 13.
(Comparative Example 5: Catalyst 14)
The catalyst composition B ₃ was used as the fluid catalytic cracking catalyst 14.
(Test Example 3)
The fluid catalytic cracking catalysts 9 and 11 to 14 were subjected to fluid catalytic cracking in the same manner as in Test Example 1. Table 6 shows the reaction results. As shown in Table 6, with respect to each calculated value, the catalysts 11 to 13 can obtain “addition rate”, “LPG”, and “gasoline” in high yield, and have low “HCO” and “coke”. Yield.

<< Experimental Example 4: A ₂ -B ₄ >>
(Example 10: Catalyst 15)
Catalyst composition A ₂ and catalyst composition B ₄ were mixed so that the mass ratio was 70:30 on a dry basis to prepare fluid catalytic cracking catalyst 15.
(Example 11: Catalyst 16)
Catalyst composition A ₂ and catalyst composition B ₄ were mixed so that the mass ratio was 50:50 on a dry basis to prepare fluid catalytic cracking catalyst 16.
(Example 12: Catalyst 17)
Catalyst composition A ₂ and catalyst composition B ₄ were mixed so that the mass ratio was 30:70 on a dry basis to prepare fluid catalytic cracking catalyst 17.
(Comparative Example 6: Catalyst 18)
The catalyst composition B ₄ was used as the fluid catalytic cracking catalyst 18.
(Test Example 4)
The fluid catalytic cracking catalysts 9 and 15 to 18 were subjected to fluid catalytic cracking in the same manner as in Test Example 1. Table 6 shows the reaction results. As shown in Table 7, for the catalysts 15 to 17, “addition rate”, “LPG” and “gasoline” were obtained in high yield for each calculated value, and “hydrogen”, “C1 + C2”, “ “LCO”, “HCO” and “Coke” resulted in low yields.

<< Experimental Example 5: A ₃ -B ₂ >>
(Example 13: Catalyst 19)
Catalyst composition A ₃ and catalyst composition B ₂ were mixed so that the mass ratio was 70:30 on a dry basis to prepare fluid catalytic cracking catalyst 19.
(Example 14: Catalyst 20)
Catalyst composition A ₃ and catalyst composition B ₂ were mixed so that the mass ratio was 50:50 on a dry basis to prepare fluid catalytic cracking catalyst 20.
(Example 15: Catalyst 21)
Catalyst composition A ₃ and catalyst composition B ₂ were mixed so that the mass ratio was 30:70 on a dry basis to prepare fluid catalytic cracking catalyst 21.
(Comparative Example 7: Catalyst 22)
The catalyst composition A ₃ was used as a fluid catalytic cracking catalyst 22.
(Test Example 5)
The fluid catalytic cracking catalysts 10 and 19 to 22 were subjected to fluid catalytic cracking in the same manner as in Test Example 1. As shown in Table 8, in the catalysts 19 to 21, “gasoline” and “LCO” were obtained in high yield and “HCO” and “coke” were low in yield for each calculated value. .

<< Experiment 6: A ₃ -B ₃ >>
(Comparative Example 16: Catalyst 23)
Catalyst composition A ₃ and catalyst composition B ₃ were mixed so that the mass ratio was 70:30 on a dry basis to prepare fluid catalytic cracking catalyst 23.
(Example 17: Catalyst 24)
A catalyst composition A ₃ and the catalyst composition B _3, the mass ratio on a dry basis are mixed so that the ratio of 50:50 to prepare a fluid catalytic cracking catalyst 24.
(Example 18: Catalyst 25)
Catalyst composition A ₃ and catalyst composition B ₃ were mixed so that the mass ratio was 30:70 on a dry basis to prepare fluid catalytic cracking catalyst 25.
(Test Example 6)
The fluid catalytic cracking catalysts 14 and 22 and 23 to 25 were subjected to fluid catalytic cracking in the same manner as in Test Example 1. Table 9 shows the reaction results. As shown in Table 9, in the catalysts 23 to 25, “gasoline” and “LCO” were obtained in a high yield and “HCO” and “coke” were obtained in a low yield for each calculated value. .

<< Experimental Example 7: A ₃ -B ₄ >>
(Example 19: Catalyst 26)
Catalyst composition A ₃ and catalyst composition B ₄ were mixed so that the mass ratio was 70:30 on a dry basis to prepare fluid catalytic cracking catalyst 26.
(Example 20: Catalyst 27)
Catalyst composition A ₃ and catalyst composition B ₄ were mixed so that the mass ratio was 50:50 on a dry basis to prepare fluid catalytic cracking catalyst 27.
(Example 21: Catalyst 28)
A catalyst composition A ₃ and the catalyst composition B _4, the mass ratio on a dry basis are mixed so that the 30:70, to prepare a fluid catalytic cracking catalyst 28.
(Test Example 7)
The fluid catalytic cracking catalysts 18 and 22 and 26 to 28 were subjected to fluid catalytic cracking in the same manner as in Test Example 1. Table 10 shows the reaction results. As shown in Table 10, with respect to the calculated values, the catalysts 26 to 28 obtained “gasoline” and “LCO” in high yields, and “HCO” and “coke” in low yields. .

<< Experiment 8: A ₂ -A ₃ >>
(Comparative Example 8: Catalyst 29)
The catalyst composition A ₂ and the catalyst composition A ₃ were mixed so that the mass ratio was 70:30 on a dry basis to prepare a fluid catalytic cracking catalyst 26.
(Comparative Example 9: Catalyst 30)
Catalyst composition A ₂ and catalyst composition A ₃ were mixed so that the mass ratio was 50:50 on a dry basis to prepare fluid catalytic cracking catalyst 27.
(Comparative Example 10: Catalyst 31)
The catalyst composition A ₂ and the catalyst composition A ₃ were mixed so that the mass ratio was 30:70 on a dry basis to prepare a fluid catalytic cracking catalyst 28.
(Test Example 8)
The fluid catalytic cracking catalysts 9 and 22 and 29 to 31 were subjected to fluid catalytic cracking in the same manner as in Test Example 1. Table 11 shows the reaction results. As shown in Table 11, the measured values and calculated values of “gasoline”, “LCO”, “HCO” and “coke” of the catalysts 29 to 31 were almost equal.

<< Experimental Example 9: B ₂ -B ₃ >>
(Comparative Example 11: Catalyst 32)
Catalyst composition B ₂ and catalyst composition B ₃ were mixed so that the mass ratio was 70:30 on a dry basis to prepare fluid catalytic cracking catalyst 26.
(Comparative Example 12: Catalyst 33)
Catalyst composition B ₂ and catalyst composition B ₃ were mixed so that the mass ratio was 50:50 on a dry basis to prepare fluid catalytic cracking catalyst 27.
(Comparative Example 13: Catalyst 34)
Catalyst composition B ₂ and catalyst composition B ₃ were mixed so that the mass ratio was 30:70 on a dry basis to prepare fluid catalytic cracking catalyst 28.
(Test Example 9)
The fluid catalytic cracking catalysts 10 and 14 and 32 to 34 were subjected to fluid catalytic cracking in the same manner as in Test Example 1. Table 12 shows the reaction results. As shown in Table 12, the measured values and calculated values of “gasoline”, “LCO”, “HCO” and “coke” of the catalysts 32 to 34 were almost equal.

As described above, the fluid catalytic cracking catalyst obtained by mixing the catalyst composition A containing the silica-based binder according to the present invention and the catalyst composition B containing the aluminum compound binder in a mass ratio of 10:90 to 90:10 is as follows. A catalyst comprising a catalyst composition A alone, a catalyst comprising a catalyst composition B alone, a catalyst composition comprising two silica-based binders, and a catalyst composition comprising two aluminum compound binders. Compared to the calculated values of any of the catalysts prepared, “gasoline” and “LPG” are obtained in high yield, and “HCO” and “coke” tend to be in low yield. This is because the alumina contained in the catalyst composition B containing the alumina compound binder is combined with the poisoned metal such as vanadium or nickel to be detoxified, so that the catalyst composition A containing the silica-based binder is made of the poisoned metal. It becomes difficult to be poisoned, and it is understood that high gasoline yield and high light oil fraction yield and high bottom cracking are obtained while maintaining high gasoline yield and low coke yield.

The present invention is not limited to the above-described embodiment, and can be changed without changing the gist of the present invention. For example, some or all of the above-described embodiments and modifications are possible. When the fluid catalytic cracking catalyst of the present invention is constituted by combining these, the scope of the right of the present invention is also included.

For example, in the above embodiment, a fluid catalytic cracking catalyst is produced by combining one type of catalyst composition A containing a silica-based binder and one type of catalyst composition B containing an aluminum compound binder. You may comprise a fluid catalytic cracking catalyst combining the thing A and / or the catalyst composition B as 2 or more types.

Claims

Catalyst composition A containing 10-30% by weight of silica-based binder as zeolite and binder, and Catalyst composition B containing 10-30% by weight of aluminum compound binder as zeolite and binder, Flow of hydrocarbon oil, characterized in that the mass is W A , the mass of catalyst composition B is W B , and the mass ratio (W A : W B ) is mixed within the range of 10:90 to 90:10 Catalytic cracking catalyst.
The catalyst composition A and the catalyst composition B have a K value represented by the following formula (1) (each K value is represented by “K A ” and “K B ”) of 1 or more. The fluid catalytic cracking catalyst of hydrocarbon oil according to claim 1.
K = conversion / (100−conversion) (1)
In addition, a conversion rate is shown by following formula (2).
Conversion (mass%) = (ab) / a × 100 (2)
Here, a is the mass of the raw material oil, and b is the total mass of the kerosene oil fraction and the heavy fraction.
3. The fluid catalytic cracking catalyst for hydrocarbon oil according to claim 2, wherein the K values of the catalyst composition A and the catalyst composition B have a relationship represented by the following formula (3).
K A : K B = 1: 0.5 to 1: 1.5 (3)
Wherein represents a K value of fluid catalytic cracking catalyst (expressed in K m), and wherein the higher than K value of the catalyst composition A (K A) and a K value of the catalyst composition B (K B) The fluid catalytic cracking catalyst for hydrocarbon oil according to any one of claims 1 to 3.
Gasoline yield fluid catalytic cracking catalyst (represented by G m) is higher than the gasoline yield (expressed in G A) and gasoline yield of the catalyst composition B of the catalyst composition A (represented by G B) The fluid catalytic cracking catalyst for hydrocarbon oils according to any one of claims 1 to 4.
The fluid catalytic cracking catalyst according to any one of claims 1 to 5, wherein the silica-based binder is one or more of silica sol, water glass, and acidic silicate liquid.
The fluid catalytic cracking catalyst according to any one of claims 1 to 6, wherein the aluminum compound binder is at least one selected from the group consisting of the following (a) to (c).
(A) Basic aluminum chloride.
(B) Aluminum biphosphate.
(C) Alumina sol.
The zeolite contained in the catalyst composition A and the catalyst composition B is one or more of FAU type (faujasite type), MFI type, CHA type, and MOR type, and The catalyst composition A and the catalyst composition B contain the zeolite in a range of 15 to 60% by mass on the basis of the catalyst composition, respectively. Fluid catalytic cracking catalyst for hydrocarbon oils.
The FAU type zeolite is any one of hydrogen type Y zeolite (HY), ultra-stabilized Y type zeolite (USY), rare earth exchanged Y type zeolite (REY), and rare earth exchanged super stabilized Y type zeolite (REUSY). The fluid catalytic cracking catalyst for hydrocarbon oil according to claim 8, wherein the catalyst is fluid catalytic cracking catalyst.
The fluid catalytic cracking catalyst for hydrocarbon oil according to any one of claims 1 to 9, wherein the catalyst composition A and the catalyst composition B contain clay minerals in addition to the zeolite and the binder. .
A fluid catalytic cracking method for hydrocarbon oil, characterized in that the fluid catalytic cracking catalyst for hydrocarbon oil according to any one of claims 1 to 10 is used.
12. The fluid catalytic cracking method of hydrocarbon oil according to claim 11, wherein the hydrocarbon oil contains residual oil.
The fluid catalytic cracking method for hydrocarbon oil according to claim 12, wherein the hydrocarbon oil contains 0.5 ppm or more of vanadium and nickel, respectively.
14. The fluid catalytic cracking method for hydrocarbon oil according to claim 11, wherein the fluid catalytic cracking catalyst contains 300 ppm or more of vanadium and nickel, respectively.