JP2007313409A - Hydrocracking catalyst composition and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrocracking catalyst composition which exhibits high hydrocracking activity and increases the yield of middle distillates such as kerosene and gas oil when used for hydrocracking heavy hydrocarbon oil and to provide a method for manufacturing the hydrocracking catalyst composition. <P>SOLUTION: The hydrocracking catalyst composition is manufactured by depositing a hydrogenating metal component on a carrier consisting of a porous inorganic oxide and realuminated Y-type zeolite having 24.25-24.52 Å unit lattice constant (UD), ≥95% crystallinity, ≥500 m<SP>2</SP>/g specific surface area, a group of pores having a specified pore diameter range and ≥60 atom% ratio of 4-coordinated aluminum atom to the total aluminum atoms in the zeolite. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a hydrocracking catalyst composition for hydrocarbon oils, particularly heavy hydrocarbon oils, and a method for producing the same, and more particularly, from an aluminum reinserted Y-zeolite having specific properties and a porous inorganic oxide. The present invention relates to a hydrocracking catalyst composition in which a metal hydride component is supported on a carrier and a method for producing the same.

Conventionally, since Y-type zeolite (hereinafter sometimes referred to as faujasite-type zeolite) is a solid acid having acid properties, it is used as a solid acid catalyst such as a catalytic cracking catalyst or hydrocracking catalyst for hydrocarbon oils. ing. In particular, in hydrocracking heavy hydrocarbon oils, ultrastable Y-type zeolite that has been dealuminated to improve diffusion of heavy hydrocarbons to solid acid sites is preferably used. Dealuminated ultra-stable Y-type zeolite has a smaller unit cell constant than synthetic Y-type zeolite, and has a high caiban ratio (SiO ₂ / Al ₂ O ₃ molar ratio), so it has high hydrothermal stability and its pore distribution is It has a feature that the pore volume (mesopore volume) in the pore diameter range of 20 to 600 mm is larger than that of the synthetic Y-type zeolite.

  Further, the acid properties of the Y-type zeolite vary depending on the caivan ratio, and the dealuminated ultra-stable Y-type zeolite has a higher caiban ratio than the synthetic Y-type zeolite. As a Y-type zeolite used for hydrocracking hydrocarbon oil, a zeolite having a large mesopore volume and a large amount of solid acid is desired.

Japanese Patent Application Laid-Open No. 9-108572 (Patent Document 1) discloses a hydrocracking catalyst in which an active metal component is supported on a support composed of a faujasite type zeolite and a porous inorganic oxide. _A hydrocracking catalyst having a ₂ O content in the range of 0.5% by weight or less and a ratio of tetracoordinate aluminum atoms forming the zeolite skeleton larger than a specific value has high cracking activity, It is described that the yield is high.

  Japanese Patent Application Laid-Open No. 2002-255537 (Patent Document 2) discloses a novel zeolite having a high mesopore content that provides an excellent solid acid catalyst. The novel zeolite has an atomic ratio [Al] / [Si] of aluminum to silicon in the range of 0.01 to 0.2, and a mesopore volume ratio of 30 to 50% having a pore diameter of 50 to 1000 mm. A zeolite having a high mesopore content, wherein the mesopore volume is 0.14 cc / g or more, and the ratio of tetracoordinated aluminum atoms to all aluminum atoms is 25 atom% or more. is there. As a method for producing the new zeolite, USY zeolite having a high mesopore content (ultrastable Y-type zeolite) as a raw material is immersed in an aqueous solution of sodium aluminate and reacted to insert aluminum atoms into the framework of the zeolite. As the method and the reaction conditions, the aluminum concentration in the aqueous solution is 0.03 to 0.1 mol / L, the pH of the aqueous solution is 11 to 12, the reaction temperature is 10 to 40 ° C., and the reaction time is 1 to It is described that it is 200 hours.

  However, in this method, since the raw material USY is treated with an alkaline aqueous solution having a pH of 11 to 12, the crystal structure is destroyed, and the resulting zeolite has a problem of low crystallinity. Therefore, when the zeolite is used for hydrocracking hydrocarbon oil, there is a problem that the amount of the solid acid of the zeolite which is a catalytic active point is small and high cracking activity cannot be obtained.

JP-A-9-108572 JP 2002-255537 A

  The object of the present invention is to solve the above-mentioned problems and to be used for hydrocracking of hydrocarbon oils, particularly heavy hydrocarbon oils such as deasphalted oil (hereinafter sometimes abbreviated as DAO). Hydrocracking of hydrocarbon oils using aluminum reinserted Y-zeolite with specific properties that show high cracking activity and excellent effects such as high yield of middle distillates such as kerosene and light oil The object is to provide a catalyst composition and a method for producing the same.

  As a result of intensive studies to achieve the above-mentioned object, the present inventors have made a hydrocracking catalyst composition using an aluminum reinserted Y-type zeolite having specific properties with improved acid properties and pore structure. The product has been found to exhibit an excellent effect in hydrocracking of hydrocarbon oils such as DAO, and has completed the present invention.

That is, the first of the present invention is a hydrogenation in which a metal hydride component is supported on a carrier comprising an aluminum reinserted Y-type zeolite having the following properties (a) to (i) and a porous inorganic oxide. The present invention relates to a cracking catalyst composition.
(A) Unit cell constant (UD) is 24.25 to 24.52Å
(B) Crystallinity of 95% or more (c) Specific surface area of 500 m ² / g or more (d) Total pore volume (PVt) of a pore group having pores having a pore diameter of 600 mm or less is 0.45. ~ 0.70ml / g
(E) The pore volume (PVm) of the pore group having pores in the range of pore diameters of 100 to 600 mm is 0.10 to 0.40 ml / g.
(F) The pore volume (PVs) of the pore group having pores having a pore diameter in the range of 35 to 50 mm is 0.03 to 0.15 ml / g.
(G) The ratio of tetracoordinated aluminum atoms to all aluminum atoms in the zeolite is 60 atomic% or more.

In the second aspect of the present invention, the aluminum reinserted Y-type zeolite is
(H) Pore volume (PVm) of a pore group having pores having a pore diameter in the range of 100 to 600 と and total pore volume (PVt) of a pore group having pores having a pore diameter of 600 Å or less The ratio (PVm / PVt) of 0.30 or more,
(I) Pore volume (PVm) of a pore group having pores having a pore diameter in the range of 100 to 600 と and pore volume of a pore group having pores having a pore diameter in the range of 35 to 50 （( PVs) ratio (PVm / PVs) is 2.5 or more,
The present invention relates to a hydrocracking catalyst composition characterized by having the following properties:

A third aspect of the present invention is that the aluminum reinserted Y-type zeolite is
(J) The present invention relates to a hydrocracking catalyst composition characterized in that the spectrum measured by a Fourier transform infrared spectrometer (FT-IR) has peaks at a position of 3630 cm ^{-1 and} a position of 3550 cm ^-1 .

4th of this invention is related with the manufacturing method of the said hydrocracking catalyst composition characterized by including the process of following (k)-(n).
(K) A step of preparing an ultra-stable Y-type zeolite (USY) having a unit cell constant (UD) in the range of 24.24 to 24.52 し て by heat-treating in a water vapor atmosphere after ammonium ion exchange of the Y-type zeolite. ,
(L) The ultra-stable Y-type zeolite (USY) is acid-treated within a pH range of 0.1 to 3.0 to remove aluminum in the skeleton structure, and then filtered and washed to obtain a dealuminated Y-type zeolite. Preparing the step,
(M) The dealuminated Y-type zeolite is suspended in an aqueous ammonium salt solution, the pH of the suspension is adjusted to a range of 4 to 7, and then the pH-adjusted suspension is adjusted to 10 at a temperature of 100 to 200 ° C. A step of heat treatment for 60 hours, followed by filtration, washing and drying to obtain an aluminum reinserted Y-type zeolite;
(N) A step of supporting a metal hydride component on a carrier obtained by mixing the aluminum reinserted Y-type zeolite and a precursor of a porous inorganic oxide, molding the resultant into a desired shape, drying and firing,

  5th of this invention is related with the manufacturing method characterized by the ammonium salt aqueous solution being ammonium acetate salt aqueous solution in the said (m) process.

(1) The hydrotreating catalyst composition of the present invention uses aluminum reinserted Y-type zeolite having specific properties. The aluminum reinserted Y-type zeolite is a Y-type zeolite having a high degree of crystallinity in which aluminum is reinserted into the framework structure of the dealuminated Y-type zeolite. It is presumed that the aluminum reinserted into the framework structure is mainly reinserted into the outer surface framework structure of the Y-type zeolite. For this reason, in the aluminum reinserted Y-type zeolite, more aluminum is present in the outer surface skeleton structure than in the inner skeleton structure, so the amount of solid acid sites on the outer surface of the Y-type zeolite is reduced by the dealumination treatment Y. More than type zeolite.
(2) The aluminum reinserted Y-type zeolite has a large total pore volume (PVt), a pore volume (PVm) of a pore group having pores in the range of pore diameters of 100 to 600 mm, and the like. Diffusion of reaction raw materials such as quality hydrocarbon oil to solid acid sites is good.

(3) Since the reinserted aluminum is uniformly dispersed on the outer surface of the pore, the aluminum reinserted Y-type zeolite leads to hydrogen transfer reaction (bimolecular reaction) that leads to coke formation, LPG, and naphtha formation. Overdecomposition reaction hardly occurs.
(4) The hydrotreating catalyst composition of the present invention is used for hydrocracking of hydrocarbon oils such as DAO, exhibits high cracking activity, and has a high yield of middle distillates such as kerosene and light oil. In addition, it exhibits excellent effects such as low coke generation ability and long catalyst life.

Hydrocracking Catalyst Composition In the present invention, the aluminum reinserted Y-type zeolite means a Y-type zeolite in which aluminum is reinserted into the framework structure of the dealuminated Y-type zeolite. The properties of the aluminum reinserted Y-type zeolite of the present invention will be described below.

(A) Unit cell constant (UD)
The unit cell constant (UD) of the aluminum reinserted Y-type zeolite is in the range of 24.25 to 24.52Å. The Y-type zeolite having a unit cell constant (UD) of less than 24.25 が has a high SiO ₂ / Al ₂ O ₃ molar ratio in the skeleton structure and a small amount of solid acid sites that are decomposition active sites of hydrocarbon oil. Therefore, the hydrocracking catalyst composition using the zeolite tends to decrease the cracking activity. Further, since the Y-type zeolite having a unit cell constant (UD) larger than 24.52 が has poor hydrothermal stability, the hydrocracking catalyst composition using the zeolite is not suitable for the zeolite during the hydrocracking reaction. The crystal structure is broken and the decomposition activity is reduced.
The unit cell constant (UD) of the aluminum reinserted Y-type zeolite in the present invention is preferably in the range of 24.28 to 24.40Å, more preferably 24.30 to 24.38Å.

(B) Crystallinity The crystallinity of the aluminum reinserted Y-type zeolite needs to be 95% or more. When the crystallinity is lower than 95%, the hydrocracking catalyst composition using the zeolite cannot obtain the desired effect. The crystallinity of the zeolite is preferably in the range of 100 to 150%. The crystallinity was determined by determining the total peak height (H) of the (331), (511), (440), (533), and (642) planes of X-ray diffraction, and using a commercially available Y-type zeolite ( The total peak height (Ho) of the same surface was determined with a crystallinity of 100 (Union Carbide SK-40) as 100, and was calculated according to the following equation.
Crystallinity = H / Ho × 100 (%)

(C) Specific surface area The specific surface area of the aluminum reinserted Y-type zeolite (measured by the BET method by nitrogen adsorption) needs to be 500 m ² / g or more. When the zeolite specific surface area is smaller than 500 m ² / g, the hydrocracking catalyst composition using the zeolite cannot obtain the desired effect because there are few solid acid sites effective for the hydrocracking reaction. The specific surface area of the zeolite is desirably in the range of 550 to 800 m ² / g.

(D) Total pore volume (PVt) of a pore group having pores having a pore diameter of 600 mm or less
The aluminum reinserted Y-type zeolite has a total pore volume (PVt) of a pore group having pores having a pore diameter of 600 mm or less in the range of 0.45 to 0.70 ml / g. When the total pore volume (PVt) is less than 0.45 ml / g, the hydrocracking catalyst composition using the zeolite does not have the desired effect, and the total pore volume (PVt) If it exceeds 0.70 ml / g, the crystallinity of the zeolite may decrease. The total pore volume (PVt) is preferably in the range of 0.50 to 0.65 ml / g.
The pore volume in the pore group within the pore diameter range of the present invention was determined from the pore distribution calculated by the BJH method from the nitrogen adsorption isotherm.

(E) Pore volume (PVm) of pore groups having pores in the range of pore diameters of 100 to 600 mm
The aluminum reinserted Y-type zeolite has a pore volume (PVm) of a pore group having pores in the pore diameter range of 100 to 600 mm in the range of 0.10 to 0.40 ml / g. When the pore volume (PVm) is less than 0.10 ml / g, the hydrocracking catalyst composition using the zeolite is not a heavy hydrocarbon oil because the diffusion effect of the heavy hydrocarbon oil is not sufficient. Decomposition is not performed sufficiently and a desired effect cannot be obtained. Further, when the pore volume (PVm) is larger than 0.40 ml / g, the crystallinity of the zeolite may be lowered, and the hydrocracking catalyst composition using the zeolite cannot obtain the desired effect. There is. The pore volume (PVm) is preferably in the range of 0.15 to 0.35 ml / g.

(F) Pore volume (PVs) of pore groups having pores having a pore diameter in the range of 35 to 50 mm
The aluminum reinserted Y-type zeolite has a pore volume (PVs) of a pore group having pores in the pore diameter range of 35 to 50 mm in the range of 0.03 to 0.15 ml / g. When the pore volume (PVs) is smaller than 0.03 ml / g, the decomposition of heavy hydrocarbon oil into kerosene fraction tends to decrease, and the pore volume (PVs) is 0.15 ml. When it is larger than / g, the sequential decomposition reaction proceeds and the generation of gas and coke tends to increase. The pore volume (PVs) of the pores is preferably in the range of 0.05 to 0.10 ml / g.

(G) Ratio of tetracoordinated aluminum atoms to all aluminum atoms in the zeolite The aluminum atoms constituting the skeleton structure of the Y-type zeolite are tetracoordinated, and the aluminum atoms outside the skeleton structure of the zeolite are present in sixcoordinates. .
The ratio of the tetracoordinated aluminum atom to the total aluminum atoms (tetracoordinated aluminum atom + 6-coordinated aluminum atom) in the aluminum reinserted Y-type zeolite needs to be 60 atomic% or more. When the proportion of tetracoordinated aluminum atoms is smaller than 60 atomic%, there is little aluminum reinserted into the framework structure of the Y-type zeolite, and the hydrocracking catalyst composition using the zeolite is capable of decomposing heavy hydrocarbon oil. In this respect, the desired effect cannot be obtained. Since it is presumed that the aluminum reinserted into the framework structure is reinserted into the outer surface framework structure of the zeolite, the amount of solid acid sites on the outer surface of the zeolite is large, and the solid acid sites are It is expected to contribute to the resolution of heavy hydrocarbon oils.

The ratio of tetracoordinated aluminum atoms to the total aluminum atoms in the zeolite of the aluminum reinserted Y-type zeolite is preferably in the range of 70 to 100 atomic%. The proportion of tetracoordinated aluminum atoms in the zeolite was determined from 27Al MAS NMR spectrum measured with a nuclear magnetic resonance apparatus (NMR) VXR-400 manufactured by VARIAN. That is, the ratio of tetracoordinated aluminum atoms is expressed by the following formula from the ratio of the peak area (A) existing at a chemical shift of −30 to 18 ppm and the peak area (B) existing at a chemical shift of 20 to 100 ppm in a solid Al-NMR spectrum. I asked for it.
Ratio of tetracoordinated aluminum atoms = (B) / (A + B) × 100 (%)

The aluminum reinserted Y-type zeolite of the present invention desirably has the following properties (h) and (i) in addition to the above properties.
(H) (PVm / PVt) ratio The aluminum reinserted Y-type zeolite of the present invention has a pore volume (PVm) and a pore diameter of pore groups having pores in the range of the above-mentioned pore diameters of 100 to 600 mm. The ratio (PVm / PVt) to the total pore volume (PVt) of a pore group having pores of 600 mm or less is preferably 0.30 or more. When the (PVm / PVt) ratio is smaller than 0.30, the diffusion of heavy hydrocarbon oil is deteriorated, and the hydrocracking catalyst composition using the zeolite has reduced heavy hydrocarbon oil resolution. There is. The (PVm / PVt) ratio is more preferably in the range of 0.30 to 0.50.

(I) (PVm / PVs) ratio The aluminum reinserted Y-type zeolite of the present invention has a pore volume (PVm) and a pore diameter of a pore group having pores in the above-described range of pore diameters of 100 to 600 mm. The pore volume (PVs) ratio (PVm / PVs) of the pore group having pores in the range of 35 to 50 mm is preferably 2.5 or more. When the (PVm / PVs) ratio is less than 2.5, the heavy hydrocarbon oil resolution may be lowered. The (PVm / PVs) ratio is more preferably in the range of 2.5 to 4.50.
In addition, since the existence ratio of the pore volume occupied by pore groups having pores in the range of other pore diameters of 0 to 35 mm and 50 to 100 mm is very small, it affects the decomposition activity of these pore groups. The impact is small.

The aluminum reinserted Y-type zeolite of the present invention more preferably has the following property (j).
(J) Peak value of spectrum measured by Fourier transform infrared spectrometer (FT-IR) There are 16-sided α-cage and 8-sided β-cage at the location of aluminum atoms constituting the framework structure of Y-type zeolite. In the FT-IR spectrum, the former shows an absorption peak at 3630 cm ⁻¹ and the latter has an absorption peak at 3550 cm ⁻¹ .
In the hydrocracking catalyst for heavy hydrocarbon oils using the aluminum-inserted Y-type zeolite of the present invention as the cracking active component, it is preferable that aluminum is reinserted into both the α cage and the β cage. It is preferable that the amount of aluminum atoms present in both cages is present in a well-balanced manner, and in order to obtain excellent decomposition activity, the peak at the position of 3630 cm ⁻¹ (α) and the peak at the position of 3550 cm ⁻¹ (β) It is desirable that the area ratio (α / β) is in the range of 5/1 to 1/5, preferably 2/1 to 1/2.

The abundance ratio of aluminum in the α cage and β cage was determined from an FT-IR spectrum measured using a transmission type Fourier transform infrared spectrometer (JIR-7000, manufactured by JEOL Ltd.). Area ratio (α / β) was determined from the ratio of the peak (beta) the area of the position of the peak (alpha) area and 3500～3600Cm ^-1 spectrum 3600～3700Cm ^-1 as measured by FT-IR.

  The catalyst carrier constituting the hydrocracking catalyst composition of the present invention consists of zeolite and other porous inorganic oxides as in the conventional hydrocracking catalyst composition. Therefore, as the porous inorganic oxide, those usually used in hydrocracking catalyst compositions can be used. For example, alumina, silica, titania, silica-alumina, alumina-titania, alumina-zirconia, alumina-boria, phosphorus-alumina, silica-alumina-boria, phosphorus-alumina-boria, phosphorus-alumina-silica, silica-alumina- Examples include titania and silica-alumina-zirconia. In particular, porous inorganic oxides mainly composed of alumina are suitable.

  In addition, as a metal hydride component (also referred to as an active metal component) constituting the hydrocracking catalyst composition of the present invention, a known metal component conventionally used for this type of hydrocracking can be used. For example, a metal component of Group 8 and / or Group 6A of the periodic table can be mentioned. Examples of preferable metal components include a group 6A molybdenum, a combination of tungsten and group 8 cobalt, nickel, and a metal component of white metal.

In the hydrocracking catalyst composition of the present invention, the content of the above-mentioned aluminum reinserted Y-type zeolite can be changed as desired, but it is usually 5 to 80 wt% based on the support (the porous inorganic oxide is 95%). ˜20 wt%), preferably 20 to 70 wt% (porous inorganic oxide is 80 to 30 wt%).
In addition, the amount of the metal hydride component in the hydrocracking catalyst composition may be within the range used in ordinary hydrocracking catalyst compositions, preferably as oxides such as molybdenum, tungsten, cobalt, and nickel. It is in the range of 5 to 30 wt%, and the metal component of the white metal is in the range of 0.01 to 2 wt% as the metal.

Method for Producing Hydrocracking Catalyst Composition Next, a method for producing the hydrocracking catalyst composition of the present invention will be described.
The hydrocracking catalyst composition of the present invention is produced by the following steps (k) to (n).
(K) A step of preparing an ultra-stable Y-type zeolite (USY) having a unit cell constant (UD) in the range of 24.24 to 24.52 し て by heat-treating in a water vapor atmosphere after ammonium ion exchange of the Y-type zeolite. Y-type zeolite (Na-Y) synthesized by a well-known method is exchanged with ammonium ions by an ordinary method to obtain ammonium-exchanged Y-type zeolite (NH ₄ -Y). The ammonium ion exchange rate is preferably 80% or more. The ammonium-exchanged Y-type zeolite is heat-treated in a water vapor atmosphere by a well-known method to liberate a part of the aluminum constituting the skeletal structure to form extra-framework aluminum, and the unit cell constant (UD) is 24.24. An ultrastable Y-type zeolite (USY) in the range of ˜24.52Å is prepared.

(L) The ultrastable Y-type zeolite is acid-treated within a pH range of 0.1 to 3.0 to remove aluminum in the framework structure, and then filtered and washed to prepare a dealuminated Y-type zeolite. Step The dealumination treatment is performed by, for example, suspending the ultrastable Y-type zeolite (USY) in pure water, heating and stirring the suspension as required, and adding an aqueous acid solution such as nitric acid, sulfuric acid or hydrochloric acid to the suspension. Then, by adjusting the suspension pH to a range of 0.1 to 3.0 and treating with acid, the aluminum outside the framework released from the framework structure is dealuminated. Subsequently, it is filtered and washed by a usual method, and dried if desired to prepare a dealuminated Y-type zeolite.

  When the pH value of the zeolite suspension is lower than 0.1, the crystal structure of the zeolite may be broken. Further, when the pH value of the zeolite suspension is higher than 3.0, dealumination from the framework structure may not occur. The preferred pH value of the zeolite suspension is in the range of 0.5 to 2.0. Such dealuminated Y-type zeolite still contains 6-coordinated aluminum outside the framework.

(M) Suspending the dealuminated Y-type zeolite in an aqueous ammonium salt solution, adjusting the pH of the suspension to a range of 4 to 7, and then adjusting the pH-adjusted suspension at a temperature of 100 to 200 ° C. Step of heat treatment for 10 to 60 hours, followed by filtration and washing to obtain aluminum reinserted Y-type zeolite When the pH value of the suspension obtained by suspending the dealuminated Y-type zeolite in an aqueous ammonium salt solution is less than pH 4 No re-insertion of aluminum into the framework structure occurs, and when the pH is higher than 7, the crystallinity of the zeolite tends to decrease. A preferred pH of the suspension is in the range of 4.5 to 6.5.
As said ammonium salt, an inorganic acid ammonium salt and an organic acid ammonium salt can be used, Ammonium nitrate, ammonium sulfate, ammonium hydrochloride, ammonium acetate, etc. are illustrated.

Next, the pH-adjusted suspension is heated in an autoclave at a temperature of 100 to 200 ° C. for 10 to 60 hours. When the processing temperature is lower than 100 ° C., reinsertion of aluminum into the skeletal structure may not occur, and even when the processing temperature is higher than 200 ° C., the amount of aluminum reinserted into the skeletal structure is 200 ° C. It is not economical because it is not different from the case of. A preferred treatment temperature is in the range of 130-170 ° C.
When the heat treatment time is shorter than 10 hours, reinsertion of aluminum into the skeletal structure may not occur, and the amount of aluminum reinserted into the skeleton structure even when the heat treatment time exceeds 60 hours Is not economical because it is the same as 60 hours. A preferable heat treatment time is 20 to 50 hours.

Since the dealuminated Y-type zeolite contains 6-coordinated non-framework aluminum, the heat treatment causes the extra-framework aluminum to be reinserted. After the heat treatment, filtration, washing and drying are performed to obtain an aluminum reinserted Y-type zeolite.
In the production method, dealuminated Y-type zeolite is suspended in an aqueous ammonium salt solution having a pH of 4 to 7, so that there is no decrease in the crystallinity of USY, and heating is carried out at a temperature of 100 to 200 ° C. for 10 to 60 hours. For the treatment, aluminum outside the zeolite skeleton is easily reinserted, and a Y-type zeolite having the aforementioned pore structure is obtained.

  In this step (m), when an aluminum acetate aqueous solution is used as the ammonium salt aqueous solution and aluminum is reinserted into the framework structure, the 16-sided α cage and octahedron constituting the framework structure of the Y-type zeolite are obtained. This is particularly preferable because aluminum is reinserted in both cages of the β cage and the amount of aluminum atoms present in both cages is present in a balanced manner.

(N) A step of mixing a metal hydride component on a carrier obtained by mixing the aluminum reinserted Y-type zeolite and a precursor of a porous inorganic oxide, molding the resultant into a desired shape, drying and firing, The hydrocracking catalyst composition can be obtained by, for example, mixing the aluminum reinserted Y-type zeolite and a porous inorganic oxide precursor, forming the desired shape into a desired shape, drying and firing. A metal hydride component solution is supported on a supported carrier by a conventional impregnation method, dried and fired. Further, the aluminum reinserted Y-type zeolite and a porous inorganic oxide precursor are mixed with a metal hydride component, formed into a desired shape, dried, and fired.

Here, the precursor of the porous inorganic oxide refers to a series of substances in the previous stage that is mixed with other catalyst composition components to become the porous inorganic oxide constituting the hydrocracking catalyst. The porous inorganic oxide itself can be used as long as it can be mixed with other catalyst composition components and molded into a desired shape.
For calcination of the support and the hydrocracking catalyst composition, the conventional calcination conditions for this type of catalyst composition are applied, and a range of 400 to 650 ° C. is desirable.

The catalyst composition for hydroprocessing of the present invention can be applied with the processing conditions used for hydrocracking of normal hydrocarbon oils. Generally, the reaction temperature is 300 to 500 ° C., the hydrogen pressure is 4 to 30 MPa, the liquid space. Processing conditions in the range of speed 0.1 to 10 hr ⁻¹ are employed.

The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to these examples.

Reference Example 1 (Preparation of USY-5)

20 kg of NaY-type zeolite (Na—Y) having the properties shown in Table 1 and the ²⁷ Al MAS NMR spectrum shown in FIG. 1 was suspended in 200 liters of hot water at 60 ° C. 5.7 kg of 1 molar ammonium sulfate was added to the zeolite, and the mixture was stirred at 70 ° C. for 1 hour for ion exchange. Thereafter, the solution was filtered and washed. After ion exchange with a solution obtained by dissolving 5.7 kg of ammonium sulfate in 40 liters of hot water at 60 ° C., the solution was filtered and washed with 200 liters of pure water at 60 ° C. Then dried at 130 ° C. 20 hours, subjected to grinding to obtain a 65% ion-exchanged NH ₄ -Y-zeolite (NH4 ⁶⁵ Y).

Next, this Y-type zeolite (NH ₄ ⁶⁵ Y) was calcined in a saturated steam atmosphere at 660 ° C. for 1 hour using a rotary steaming device to obtain H-Y type zeolite (HY-5). This HY-5 was suspended in 200 liters of warm water at 60 ° C. Next, 17 kg of 3 mol times ammonium sulfate was added to the zeolite, and the mixture was stirred at 90 ° C. for 1 hour for ion exchange, filtered, and washed with 200 liters of pure water at 60 ° C. Then, it was dried at 130 ° C. for 20 hours and pulverized to obtain 85% ion-exchanged Y-type zeolite (NH ₄ ⁸⁵ Y). This NH ₄ ⁸⁵ Y was calcined in a saturated steam atmosphere at 700 ° C. for 1 hour with a rotary steaming device, and about 17 kg of ultrastable Y-type zeolite (USY-5) was obtained.

Reference Example 2 (Preparation of USY-15)

  After weighing 5.0 kg of USY-5 of Reference Example 1 and suspending in 50 liters of pure water at 60 ° C., 8.5 kg of 25% sulfuric acid was gradually added to the suspension, and then stirred at 70 ° C. for 1 hour. Most of the extra-framework aluminum was dissolved. The pH of the suspension at this time was 0.29. Thereafter, this was filtered, washed with 50 liters of pure water at 60 ° C., and dried at 130 ° C. for 20 hours to obtain about 4.2 kg of ultrastable Y-type zeolite (USY-15). The properties of the zeolite are shown in Table 1.

Reference Example 3 (Preparation of USY-15AC)

  0.50 kg of USY-15 of Reference Example 2 and 0.35 kg of ammonium sulfate were weighed and suspended in 3.65 kg of pure water. The pH of this suspension was 5.1. This suspension was set in a 5-liter autoclave and stirred at 150 ° C. for 48 hours. Thereafter, the mixture was filtered, washed with 10 liters of pure water at 60 ° C., and dried at 130 ° C. for 20 hours to prepare about 0.45 kg of aluminum reinserted Y-type zeolite. The same operation was performed three times to prepare about 1.3 kg of aluminum reinserted Y-type zeolite (USY-15AC). The properties of the zeolite are shown in Table 1. In this operation, hexacoordinate aluminum (extra-framework aluminum) that is released from the framework structure of the zeolite and remains in the zeolite is reinserted into the framework structure, and an aluminum reinserted Y-type zeolite is obtained.

Reference Example 4 (Preparation of USY-30)

12 kg of USY-5 of Reference Example 1 was weighed, suspended in 120 liters of pure water at 60 ° C., 29.3 kg of 25% sulfuric acid was gradually added to the suspension, and then stirred at 70 ° C. for 1 hour to remove from the skeleton. Aluminum was dissolved. The pH of the suspension at this time was 0.23. Thereafter, this was filtered, washed with 120 liters of pure water at 60 ° C., and dried at 130 ° C. for 20 hours to prepare about 9 kg of ultrastable Y-type zeolite (USY-30). The properties of the zeolite are shown in Table 1, and the ²⁷ AlMAS NMR spectrum is shown in FIG.
In the ²⁷ AlMAS NMR spectrum of USY-30 in FIG. 2, the presence of hexacoordinate Al (0 ppm) shows that there is aluminum outside the skeleton.

Reference Example 5 (Preparation of USY-30AC)

  USY-30 of Reference Example 4 was weighed in 0.50 kg and 0.35 kg of ammonium sulfate and suspended in 3.65 kg of pure water. The pH of this suspension was 5.1. This suspension was set in a 5-liter autoclave and stirred at 150 ° C. for 48 hours. Thereafter, the mixture was filtered, washed with 10 liters of pure water at 60 ° C., and dried at 130 ° C. for 20 hours to prepare about 0.45 kg of aluminum reinserted Y-type zeolite. The same operation was performed three times to prepare about 1.3 kg of aluminum reinserted Y-type zeolite (USY-30AC).

The properties of the zeolite are shown in Table 1, and the ²⁷ AlMAS NMR spectrum is shown in FIG.
As is clear from FIG. 2, the peak of 6-coordinated Al (0 ppm) indicating the presence of aluminum outside the framework is reduced in USY-30AC, compared to USY-30, and tetracoordinated Al (60 ppm) indicating the framework-structured aluminum. ) Peak is increasing. This indicates that in USY-30AC, aluminum outside the framework was reinserted into the framework of the Y-type zeolite.

Reference Example 6 (Preparation of Al.USY-30AC)

  0.50 kg of (USY-30) of Reference Example 4 and 0.26 kg of ammonium acetate were weighed and suspended in 3.50 kg of pure water. The pH of this suspension was 6.1. This suspension was set in a 5-liter autoclave and stirred at 150 ° C. for 48 hours. Thereafter, the mixture was filtered, washed with 10 liters of pure water at 60 ° C., and dried at 130 ° C. for 20 hours to prepare about 0.45 kg of aluminum reinserted Y-type zeolite. The same operation was performed three times to prepare about 1.3 kg of aluminum reinserted Y-type zeolite (Al.USY-30AC).

The properties of the zeolite are shown in Table 1, and FIG. 3 shows the FT-IR spectrum of a transmission type Fourier transform infrared spectrometer (JIR-7000, manufactured by JEOL Ltd.).
As apparent from FIG. 3, the treated zeolite with ammonium acetate, a peak derived from the β cage crosslinked hydroxyl group of α cage and 3550 cm ^-1 of 3630Cm ^-1 was clearly observed.
The peak area ratio (α / β) of the α cage of 3630 cm ^{−1 and} the β cage of 3550 cm ⁻¹ in NH ₄ ⁸⁵ Y is 3.67 / 1. The peak area ratio (α / β) of USY-30AC was 1.15 / 1. This indicates that by using ammonium acetate, Al atoms were reinserted in a 4-coordinate state into the framework structure of USY zeolite.

Reference Example 7 (Preparation of USY-30-AlNaO2)

USY-30 of Reference Example 4 was weighed in 0.50 kg and 0.41 kg of 22% -Al ₂ O ₃ sodium aluminate and suspended in 3.65 kg of pure water. The pH of this suspension was 11.2. The suspension was stirred at a temperature of 15 ° C. for 90 hours. Thereafter, the mixture is filtered, ion-exchanged with 10 liters of pure water at 60 ° C. dissolved with 0.87 kg of ammonium sulfate, washed again with 10 liters of pure water at 60 ° C., dried at 130 ° C. for 20 hours, and treated with sodium aluminate Y About 0.45 kg of type zeolite was prepared. The same operation was performed three times to prepare about 1.3 kg of sodium aluminate-treated Y-type zeolite (USY-30-AlNaO ₂ ). The properties of the zeolite are shown in Table 1.

In Table 1 showing the properties of each zeolite, “SiO ₂ / Al ₂ O ₃ molar ratio” is the chemical analysis value, “Y-cont.” Is the crystallinity, “UD” is the unit cell constant, “SA” "Represents a specific surface area, respectively.

Comparative Example 1 (Preparation of catalyst A)

A 100 L tank with a steam jacket is charged with 12.88 kg of a 22 wt% sodium aluminate aqueous solution in terms of Al ₂ O ₃ concentration, and diluted with ion exchange water to 40 kg. In this solution, 0.22 kg of 26 wt% sodium gluconate is added and heated to 60 ° C. with stirring. In a 50 L container, 13.86 kg of an aluminum sulfate aqueous solution of 7 wt% in terms of Al ₂ O ₃ concentration was put, and diluted with hot water at 60 ° C. to make 40 kg.
Next, the aluminum sulfate solution was added to the sodium aluminate solution at a constant rate using a rotary pump, and the pH was adjusted to 7.1 after 10 minutes. The obtained alumina preparation slurry was aged at 60 ° C. for 1 hour with stirring.

The prepared slurry after aging was dehydrated with a flat plate filter and washed with 150 L of a 0.3 wt% aqueous ammonia solution. The washed cake-like slurry was diluted with ion-exchanged water to make the Al ₂ O ₃ concentration 10 wt%, and the pH of the slurry was adjusted to 10.5 using 15 wt% ammonia water.
The pH-adjusted slurry was transferred to an aging tank equipped with a reflux condenser and aged at 95 ° C. for 10 hours with stirring. After cooling, the mixture was dehydrated with a flat plate filter, concentrated to a predetermined moisture content with a double-arm kneader equipped with a steam jacket, and then cooled to prepare an alumina kneaded product (X).

1.0 kg of Al ₂ O ₃ was weighed from the alumina hydrate (X) corresponding to this inorganic oxide matrix precursor, and the ultrastable Y prepared in Reference Example 2 with a double-arm kneader equipped with a steam jacket. The mixture was mixed with 1.0 kg of type zeolite (USY-15), warmed and concentrated to a predetermined water content, and then cooled and kneaded for 10 minutes.
The obtained kneaded product was formed into a cylinder having a diameter of 1.8 mm by an extrusion molding machine and dried at 110 ° C. for 16 hours, and then the dried pellets were baked in an electric furnace at a temperature of 550 ° C. for 3 hours to obtain a carrier. .

On the other hand, 201.3 g of molybdenum trioxide and 90.4 g of nickel carbonate were placed in a 1 L container, 700 ml of ion-exchanged water was added, and the mixture was stirred and suspended. The suspension was aged at 95 ° C. for 5 hours so that the amount of the solution was not reduced. Thereafter, 141 g of citric acid was added to this suspension solution, and the suspension was dissolved to prepare a uniform impregnation solution.
The carrier was impregnated with the impregnation solution. In the impregnation method, 1000 g of the carrier is put into a rotary blender that can be degassed, and after deaeration with a vacuum pump, the amount of the impregnation solution is adjusted to match the water absorption rate of the carrier, and the blender is added while rotating. did.

After the addition of the solution, the vacuum pump was stopped and rotated at normal pressure for 20 minutes so that the impregnation solution sufficiently permeated into the carrier. Next, the impregnated sample was heated at 40 ° C. to 250 ° C. for 1 hour using a rotary dryer with a temperature raising program.
The dried product was placed in an electric furnace and calcined at 550 ° C. for 1 hour to prepare a hydrocracking catalyst (Catalyst A). Properties of catalyst A are shown in Table 2.

(Preparation of catalyst B)
1.0 kg of alumina kneaded product (X) prepared in Comparative Example 1 as Al ₂ O ₃ was weighed, and the aluminum reinserted Y-type zeolite prepared in Reference Example 3 with a double-arm kneader equipped with a steam jacket ( (USY-15AC) was mixed with 1.0 kg, warmed and concentrated to a predetermined amount of water, then cooled to kneaded for 10 minutes. Thereafter, a hydrocracking catalyst composition (Catalyst B) was prepared in the same manner as in Comparative Example 1. Properties of catalyst B are shown in Table 2.

Comparative Example 2 (Preparation of catalyst C)

  In Comparative Example 1, a hydrocracking catalyst composition (Catalyst C) was prepared in the same manner as in Comparative Example 1, except that 1.0 kg of the ultrastable Y-type zeolite (USY-30) prepared in Reference Example 4 was used. . Properties of catalyst C are shown in Table 2.

(Preparation of catalyst D)
In Comparative Example 1, a hydrocracking catalyst composition (Catalyst D) was prepared in the same manner as Comparative Example 1, except that 1.0 kg of the aluminum reinserted Y-type zeolite (USY-30AC) prepared in Reference Example 5 was used. did. Properties of catalyst D are shown in Table 2.

(Preparation of catalyst E)
In Comparative Example 1, the hydrocracking catalyst composition (Catalyst E) was the same as Comparative Example 1 except that 1.0 kg of the aluminum reinserted Y-type zeolite (Al.USY-30AC) prepared in Reference Example 6 was used. Was prepared. Properties of catalyst E are shown in Table 2.

Comparative Example 3 (Preparation of catalyst F)

  In Comparative Example 1, the hydrocracking catalyst composition (Catalyst F) was prepared in the same manner as in Comparative Example 1 except that 1.0 kg of the ultrastable Y-type zeolite (USY-30-AlNaO2) prepared in Reference Example 7 was used. Prepared. Properties of catalyst F are shown in Table 2.

In Table 2 showing the properties of the catalysts A to F, “SA” is the specific surface area, “Cr.Str.” Is the pressure resistance, “ABD” is the apparent bulk specific gravity, “CBD” is the close packed bulk specific gravity, “PV (H ₂ O) "is a total pore volume, expressed respectively.

(Activity evaluation)
Using the catalysts A to F of Comparative Examples 1, 2, and 3 and Examples 1, 2, and 3, a hydrocracking reaction was performed using DAO as a raw material in a fixed bed flow reactor. The decomposition rate and the middle distillate yield of kerosene / light oil were measured to evaluate the activity of the catalyst.
The reaction conditions and the properties of the raw material DAO are as follows.

Reaction conditions :
Liquid space velocity (hr ⁻¹ ) 0.26
Hydrogen / oil ratio (Nm ³ / kl) 1250
Hydrogen partial pressure (MPa) 13
Reaction temperature (° C) 370

Properties of DAO :
Specific gravity (g / ml) 0.9807
Sulfur content (wt%) 3.8
Nitrogen content (wppm) 2240

Table 3 shows the results of activity evaluation. Incidentally, decomposition rate and middle distillate yield ratio (kerosene, gas oil) is multiplied by the product oil to a distillation _{apparatus, C 1 ~C 4, C 5} ~145 ℃, 145~260 ℃, 260~375 ℃, 375~560 ℃ The content at 560 ° C. ⁺ was measured and evaluated.
That is, the decomposition rate (560 ° C. ⁺⁾ = - is [(560 ° C. in the feedstock ⁺ fraction 560 ° C. ⁺ fraction in the product oil) / feedstock oil of 560 ° C. ⁺ fraction] × 100 (%) .
Further, middle fraction yield = (145 to 375 ° C. fraction in the product oil / C _{1 to} 375 ° C. fraction in the product oil) × 100 (%).

Catalyst B (Example 1), Catalyst D (Example 2), and Catalyst E (Example 3) of the present invention are compared to Catalyst A (Comparative Example 1) and Catalyst C (Comparative Example 2) of the respective reference catalysts. Thus, it shows a high decomposition activity and a high yield of middle distillates such as kerosene and light oil.
In addition, the catalyst F (Comparative Example 3), which is a trial of Patent Document 2, has a low crystallinity (Y-cont.) Of zeolite, and therefore has a low decomposition activity.

2 is a ²⁷ Al MAS NMR spectrum diagram of Na—Y type zeolite used in Reference Example 1. FIG. FIG. 4 is a ²⁷ Al MAS NMR spectrum diagram of the ultrastable Y-type zeolite (USY-30) prepared in Reference Example 4 and the aluminum reinserted Y-type zeolite (USY-30AC) prepared in Reference Example 5. FIG. 6 is an FT-IR spectrum diagram of aluminum reinserted zeolite (Al.USY-30AC) and NH ₄ ⁸⁵ Y prepared in Reference Example 6.

Claims (5)

A hydrocracking catalyst composition obtained by supporting a hydrogenation metal component on a carrier comprising an aluminum reinserted Y-type zeolite having the following properties (a) to (g) and a porous inorganic oxide.
(A) Unit cell constant (UD) is 24.25 to 24.52Å
(B) Crystallinity of 95% or more (c) Specific surface area of 500 m ² / g or more (d) Total pore volume (PVt) of a pore group having pores having a pore diameter of 600 mm or less is 0.45. ~ 0.70ml / g
(E) The pore volume (PVm) of the pore group having pores in the range of pore diameters of 100 to 600 mm is 0.10 to 0.40 ml / g.
(F) The pore volume (PVs) of the pore group having pores having a pore diameter in the range of 35 to 50 mm is 0.03 to 0.15 ml / g.
(G) The ratio of tetracoordinated aluminum atoms to all aluminum atoms in the zeolite is 60 atomic% or more.
The aluminum reinserted Y-type zeolite is
(H) Pore volume (PVm) of a pore group having pores having a pore diameter in the range of 100 to 600 と and total pore volume (PVt) of a pore group having pores having a pore diameter of 600 Å or less The ratio (PVm / PVt) of 0.30 or more,
(I) Pore volume (PVm) of a pore group having pores having a pore diameter in the range of 100 to 600 と and pore volume of a pore group having pores having a pore diameter in the range of 35 to 50 （( PVs) ratio (PVm / PVs) is 2.5 or more,
2. The hydrocracking catalyst composition according to claim 1, which has the following properties.
The aluminum reinserted Y-type zeolite is
(J) The hydrogenolysis according to claim 1 or 2, wherein the spectrum measured by a Fourier transform infrared spectrometer (FT-IR) has peaks at a position of 3630 cm ^{-1 and} a position of 3550 cm ^-1. Catalyst composition.
The method for producing a hydrocracking catalyst composition according to any one of claims 1 to 3, comprising the following steps (k) to (n).
(K) A step of preparing an ultra-stable Y-type zeolite (USY) having a unit cell constant (UD) in the range of 24.24 to 24.52 し て by heat-treating in a water vapor atmosphere after ammonium ion exchange of the Y-type zeolite. ,
(L) The ultrastable Y-type zeolite is acid-treated within a pH range of 0.1 to 3.0 to remove aluminum in the framework structure, and then filtered and washed to prepare a dealuminated Y-type zeolite. Process,
(M) The dealuminated Y-type zeolite is suspended in an aqueous ammonium salt solution, the pH of the suspension is adjusted to a range of 4 to 7, and then the pH-adjusted suspension is adjusted to 10 at a temperature of 100 to 200 ° C. A step of heat treatment for 60 hours, followed by filtration, washing and drying to obtain an aluminum reinserted Y-type zeolite;
(N) A step of supporting a metal hydride component on a carrier obtained by mixing the aluminum reinserted Y-type zeolite and a precursor of a porous inorganic oxide, molding the resultant into a desired shape, drying and firing,
5. The method for producing a hydrocracking catalyst composition according to claim 4, wherein in the step (m), the aqueous ammonium salt solution is an aqueous ammonium acetate salt solution.

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