JP7710352B2 - Zeolite, method for producing said zeolite, and catalyst containing said zeolite - Google Patents

Description

The present invention relates to a zeolite suitable for use as a catalyst component or adsorbent in the oil refining and petrochemical fields, a method for producing the same, and a catalyst using the zeolite.

In recent years, the oil refining industry has seen an increase in the use of heavy hydrocarbon oils such as residual oil as feedstock for catalytic cracking. In particular, there is a demand for catalysts that can be used in the catalytic cracking of heavy hydrocarbon oils such as residual oil, that have metal resistance to vanadium and nickel, are excellent at decomposing residual oil, produce less hydrogen and coke, and produce a high yield of gasoline and kerosene fraction (LCO).

Solutions to these problems have been proposed to some extent through process improvements and the development of fluid catalytic cracking catalysts (hereinafter simply referred to as FCC catalysts).

Patent Document 1 discloses a catalytic cracking catalyst characterized in that the silica-alumina ratio of faujasite-type zeolite is 6 or more, the amount of Na ₂ O is in the range of 0.5 wt % or less, and the number of aluminum atoms (four-coordinated) in the framework is 25 or more. It is reported that the catalytic cracking catalyst disclosed in Patent Document 1 has a stable crystal structure even when subjected to high-temperature steam treatment, does not lose the essential catalytic cracking reaction activity of zeolite, and has excellent hydrothermal resistance.

Patent Document 2 discloses ultrastable Y-type zeolite (USY zeolite) in which the pore volume is controlled to a pore diameter range of 3.5 to 5 nm. It is reported that the ultrastable Y-type zeolite described in Patent Document 2 has a unit lattice constant (UD) of 24.55 Å or less, a SiO ₂ /Al ₂ O ₃ (molar ratio) of 8 or more, a specific surface area of 400 to 900 m ² /g, and a crystallinity of 95% or more, and can be used for hydrocracking of hydrocarbon oils such as diesel and residual oil.

Furthermore, Patent Document 3 discloses a Y-type zeolite in which aluminum has been reinserted into the framework structure of dealuminated Y-type zeolite. The Y-type zeolite disclosed in Patent Document 3 is characterized by a unit lattice constant (UD) of 24.25 to 24.60 Å, a certain degree of crystallinity, specific surface area, and pore size, and a proportion of aluminum atoms (four-coordinated) in the framework of 60% or more, and is reported to exhibit excellent performance.

Patent Document 4 discloses a method for producing a high octane gasoline fraction by contacting a highly aromatic hydrocarbon oil feedstock with a hydrocracking catalyst to obtain a high octane gasoline fraction. The hydrocracking catalyst disclosed in Patent Document 4 is a catalyst using a refractory carrier containing a specific ultrastable Y-type zeolite, and is characterized in that the unit lattice parameter (UD) of the UYS zeolite is 24.40 Å or less, the _{SiO2 / Al2O3} (molar ratio) is 25 or more, and the crystallinity is 50% or more. Patent Document 4 reports that UYS zeolite is effective as a hydrocracking catalyst for producing a gasoline fraction.

Patent Document 5 discloses a faujasite-type zeolite and a catalyst for catalytic cracking of hydrocarbons containing the faujasite-type zeolite. Patent Document 5 reports a catalytic cracking catalyst characterized in that the faujasite-type zeolite has a SiO ₂ /Al ₂ O ₃ (molar ratio) of 4 to 8, a peak area ratio of extraframework (six-coordinated) aluminum to intraframework (four-coordinated) aluminum in solid-state NMR of 0.4 to 1.0, and a lattice constant in the range of 24.40 to 24.65 Å.

Japanese Patent Application Publication No. 09-038499 JP 2003-095643 A JP 2006-150183 A JP 2010-215736 A JP 2012-140287 A

In the future, the content of vanadium and nickel, which are poisonous substances contained in residual oil, is expected to increase further, and there is a demand for fluid catalytic cracking catalysts that can maintain residual oil cracking activity even under such circumstances. The problem with the conventional fluid catalytic cracking catalysts mentioned above is that they are unable to achieve sufficient activity.

The object of the present invention is to provide a zeolite suitable for use as a catalyst component or adsorbent in the petroleum refining and petrochemical fields, a method for producing said zeolite, and a catalyst containing said zeolite. In particular, the present invention provides a zeolite suitable for use as a fluid catalytic cracking catalyst.

In light of this technical background, the inventors conducted extensive research into improving fluid catalytic cracking catalysts (hereinafter simply referred to as "FCC catalysts") that have excellent cracking properties for heavy fractions (bottoms), and discovered that fluid catalytic cracking catalysts containing specific faujasite-type zeolites exhibit heavy fraction (bottoms) cracking properties that are significantly superior in hydrothermal stability and resistance to metal poisoning, leading to the completion of the present invention.

The zeolite according to the present invention is
It has the following characteristics (a) to (c).
(a) Faujasite-type zeolite.
(b) The peak area ratio (P _6Al )/(P 4Al ) of the peak area of the spectrum of tetracoordinated Al (P _4Al ) to the peak area of the spectrum of hexacoordinated Al (P _6Al ) measured by solid-state NMR of _alumina is in the range of 0.20 to 0.40.
(c) The amount of ammonia desorption measured by ammonia temperature programmed desorption spectrometry (NH ₃ -TPD method) is in the range of 1.0 to 2.5 mmol/g.

In addition, the zeolite according to the present invention is
(A) the faujasite-type zeolite is ultra-stable Y-type zeolite (USY);
(A) the faujasite-type zeolite has a zeolite lattice constant in the range of 24.40 to 24.60 Å;
This is thought to be a more preferable solution.

Further, a method for producing a zeolite according to the present invention is a method for producing any one of the above zeolites, comprising the steps of:
(1) a first step of preparing a zeolite;
(2) a second step of treating the zeolite with an acid in the presence of an ammonium salt, followed by solid-liquid separation to obtain a zeolite cake;
(3) a third step of obtaining zeolite from the zeolite cake;
It includes.

The catalyst according to the present invention contains any of the above zeolites.

As described above, the zeolite obtained by the present invention and the method for producing the same can be used as a catalyst, particularly as a fluid catalytic cracking catalyst, to provide a fluid catalytic cracking catalyst that has excellent cracking ability for heavy fractions (bottoms), high cracking activity, produces little hydrogen, gas, and coke, produces gasoline and kerosene fractions in high yields, and has excellent hydrothermal stability and resistance to metal poisoning. The zeolite of the present invention can also be used as a catalyst component for use in oil refining and the petrochemical field, or as an adsorbent.

The zeolite of the present invention was first developed for use as a fluid catalytic cracking catalyst.

As catalysts for fluid catalytic cracking (FCC) of hydrocarbons, catalytic compositions have been known that use a porous inorganic oxide, such as silica-alumina, silica-zirconia, silica-magnesia, or even silica-clay, as a matrix in which fine zeolite is dispersed. However, in general, with this type of catalytic composition, there is a risk that the pores of the zeolite will be encapsulated by the matrix components, particularly the silica components in the matrix, and if this encapsulation occurs, there is a risk that the performance of the catalyst will be significantly reduced.

<Zeolite>
The present invention provides a fluid catalytic cracking catalyst having excellent cracking activity, gasoline selectivity, hydrothermal stability and metal poisoning resistance by using zeolite dispersed in a matrix. That is, the FCC catalyst of the present invention contains a specific faujasite-type zeolite in a dispersed state.

The zeolite used in the present invention is a faujasite-type zeolite, and ultra-stable Y-type zeolite (USY) is particularly suitable because of its excellent hydrothermal resistance.

The USY zeolite of the present invention contains a specific ratio of 6-coordinated Al atoms in addition to 4-coordinated Al atoms in the framework. The inventors define the ratio of such 4-coordinated Al atoms and 6-coordinated Al atoms as the ratio of peak areas using solid-state NMR.

That is, the peak area ratio ( _P6Al )/(P4Al) of the peak area of the spectrum of tetracoordinated Al (P4Al) to the peak area of the spectrum of hexacoordinated Al ( _P6Al ) measured by solid-state NMR of the _alumina in the USY _zeolite of the present invention must be in the range of 0.20 to 0.40. If the peak area ratio is smaller than the lower limit of the ratio, the metal resistance and hydrothermal resistance may be insufficient, whereas if the peak area ratio exceeds the upper limit, this means that there is a small amount of tetracoordinated Al (Al atoms in the framework), and the activity may be insufficient.

In the present invention, the coordination state of aluminum present in the zeolite was measured using a solid-state high-resolution NMR (Nuclear Magnetic Resonance) device (Agilent: VNS-600). ^27Al MAS (Magic Angle Spinning) NMR spectrum measurement was performed at room temperature under the conditions of a resonance frequency of 156.29 MHz, a spin speed of 20 kHz, a waiting time of 0.1 sec, and an accumulation number of 128 times. Note that before the measurement, the sample was placed in a desiccator containing NH ₄ Cl saturated water vapor for 24 hours or more to allow sufficient water adsorption. In addition, aluminum nitrate nonahydrate (Al(NO ₃ ) _{3.9H 2} O) was used as an external standard.

The composition of the zeolite was analyzed by a glass bead method using a fluorescent X-ray analyzer (MagiX PRO, manufactured by PHILIPS).
The lattice constant of the zeolite was measured using a powder X-ray diffractometer (Rigaku Corporation: RINT-2100). Using Cu-Kα radiation, the lattice constant was calculated under conditions of a tube voltage of 30 kV and a tube current of 14 mA. The lattice constant of the USY zeolite of the present invention is preferably in the range of 24.40 to 24.60 Å. If the lattice constant is in this range, the solid acid amount is large and the activity is high. If the lattice constant is too high, the hydrothermal resistance, metal resistance, etc. may be insufficient, and if the lattice constant is too low, the solid acid amount may be small and the activity may be insufficient.

The specific surface area was measured by measuring the amount of adsorption and desorption of _N2 on a sample powder that had been pretreated at 500°C for 1 hour in an inert gas atmosphere using MacSorb-1220 manufactured by Mountech Co., Ltd. The specific surface area was calculated from the amount of desorption of _N2 obtained based on the BET single point method.

The amount of ammonia desorption was measured by ammonia temperature programmed desorption method (NH ₃ -TPD method). That is, using BELCAT-B (registered trademark) manufactured by Microtrackbell, 0.2 g of sample was placed in a measurement cell, and exhaust treatment was performed at 500°C for 1 hour, after which the temperature was increased to 100°C, and ammonia gas was introduced and adsorbed at 100°C for 0.5 hours. Next, exhaust treatment was performed again at 100°C for 0.5 hours, and then the amount of ammonia desorbed with the increase in temperature was measured while increasing the temperature from 100°C to 700°C at 10°C per minute under a flow of He gas at 50 ml per minute. The amount of ammonia desorption must be in the range of 1.0 to 2.5 mmol/g. If the amount of ammonia desorption is less than the lower limit, the cracking activity is insufficient, while if it exceeds the upper limit, the amount of coke produced increases and gasoline selectivity may decrease.

In addition to the above-mentioned fluid catalytic cracking applications, the zeolite of the present invention can be used, for example, as a catalyst component for catalytic cracking and hydrotreating in the petroleum refining and petrochemical fields, as a molecular sieve, or as an adsorbent for separating organic substances in the gas or liquid phase.

<Method of manufacturing zeolite>
(1) First step of preparing zeolite As the NaY type zeolite, a conventionally known NaY type zeolite can be used. The SiO ₂ /Al ₂ O ₃ molar ratio of the NaY type zeolite used in the present invention is preferably in the range of 3 to 6, more preferably 4 to 6.

Ammonium ion exchange is performed by dispersing NaY zeolite in an aqueous ammonium salt solution to obtain NH ₄ Y zeolite. Ion exchange can be performed by a conventional method. The amount of ammonium salt used is preferably 0.6 to 3 moles, more preferably 1 to 2 moles, per mole of NaY zeolite (Na ₂ O.Al ₂ O _{3.nSiO 2} : n is the SiO ₂ /Al ₂ O ₃ molar ratio). If the amount of ammonium salt used is small, the desired ion exchange rate cannot be achieved, and the amount of Na remaining increases, which may significantly reduce the crystallinity of NH ₄ Y zeolite in the next step or later. There is no particular limit to the temperature during ion exchange, but it is preferably in the range of room temperature to 100°C, more preferably 50 to 95°C.

NH ₄ Y-type zeolite can be heat-treated at 550 to 750° C. by a conventionally known method. For example, a muffle furnace, a rotary kiln, etc. can be used. Steam may be supplied during heating, or NH ₄ Y-type zeolite that has already contained moisture may be used. By heat-treating in the presence of steam, the lattice constant can be adjusted.

(2) A second step of treating the zeolite with an acid in the presence of an ammonium salt, followed by solid-liquid separation to obtain a zeolite cake. The heat-treated zeolite can be treated with an acid solution at a temperature in the range of 40 to 100° C. in order to remove extraskeletal aluminum. The acid solution in this step is a solution containing an acid, and includes conventionally known inorganic acids such as sulfuric acid, hydrochloric acid, and nitric acid. In addition, organic acids such as citric acid and acetic acid may be used as long as they are capable of removing extraskeletal aluminum.

The acid solution in this step may contain a salt containing ammonium ions. When the acid treatment is carried out using an acid solution containing ammonium ions, Na ⁺ , which is a counter cation of aluminum, is more easily removed.

After the acid treatment, the acid solution and zeolite can be separated into solid and liquid by filtration or other methods to obtain a zeolite cake. Since the separated zeolite may contain residual components derived from the acid solution, it is preferable to perform a washing process such as suspending the separated zeolite again in water or pouring warm water over the filter cloth.

In addition, since the filtrate contains dissolved aluminosilicate, the solids may be aggregated and collected from the viewpoint of yield, performance, etc. A flocculant is added to the filtrate, and a precipitate containing dissolved aluminosilicate is obtained from the filtrate. The collected dissolved aluminosilicate is subjected to solid-liquid separation by a method such as filtration, and then suspended again in water or washed by pouring hot water over the filter cloth to obtain a dissolved aluminosilicate cake. In addition, when obtaining the dissolved aluminosilicate cake, a device for concentrating and settling a slurry such as a thickener may be used. For example, a thickener may be used as the actual device, and the filtrate to which a flocculant has been added is concentrated and settled, and the concentrated and settled filtrate can be mixed as is in a filtration device such as an Oliver filter and washed.

The flocculant is preferably an inorganic flocculant such as polyaluminum chloride or polyferric sulfate, or an organic polymer flocculant such as a polyacrylic acid ester or polyacrylamide, or a combination of the two may be used. At least one of the following organic polymer flocculants may be used: cationic, anionic, nonionic, or amphoteric.

(3) A third step of obtaining zeolite from the zeolite cake The zeolite cake can be dried at a temperature in the range of 80° C. to 400° C. to obtain zeolite. Furthermore, the zeolite may be calcined at a temperature in the range of 400° C. to 900° C. in the air as required.

A fluid catalytic cracking catalyst will be taken as an example of the catalyst containing the zeolite of the present invention.
- Fluid catalytic cracking catalyst -
The fluid catalytic cracking catalyst according to the present invention comprises a matrix containing a binder component containing silica or alumina and the above-prepared zeolite (hereinafter also simply referred to as zeolite), and an additive containing at least one selected from activated alumina and a metal capture agent, and may further contain a rare earth metal oxide. These zeolites are used in a form ion-exchanged with a cation selected from hydrogen, ammonium and polyvalent metals, as in the case of being used in ordinary catalytic cracking catalysts.

As the precursor of the rare earth metal oxide in the present invention, commercially available rare earth metal carbonates, hydrochlorides, nitrates, oxalates, etc. can be used.

The fluid catalytic cracking catalyst according to the present invention uses a porous inorganic oxide matrix, as in the case of a normal catalytic cracking catalyst. For the porous inorganic oxide matrix, silicate such as sodium silicate, silica-based binders such as silica sol, and alumina-based binders such as basic aluminum chloride, alumina sol, and alumina gel can be used. In addition, as additives, clay minerals such as kaolin, halloysite, and montmorillonite, matrices having solid acids such as activated alumina, silica-alumina, silica-magnesia, alumina-magnesia, and silica-magnesia-alumina, and metal capture agents such as manganese dioxide, calcium aluminate, aluminum hydroxide, and rare earth metal oxides (e.g., lanthanum carbonate) can be used in combination.

The fluid catalytic cracking catalyst of the present invention is characterized in that the zeolite and preferably the rare earth metal oxide are dispersed in the porous inorganic oxide matrix. In the fluid catalytic cracking catalyst, the zeolite is preferably contained in an amount of 5 to 50 mass%, more preferably 10 to 40 mass%, based on the catalyst. When the rare earth metal oxide is contained, it is preferably contained in an amount of 0.5 mass% or more, preferably 0.8 mass% or more, more preferably 1.0 mass% or more, calculated as oxide (RE ₂ O ₃ ) based on the catalyst, and is preferably contained in an amount of up to 20 mass%, preferably up to 18 mass%, more preferably up to 15 mass%, and is uniformly dispersed in the porous inorganic oxide matrix.

If the content of the zeolite is less than 5% by mass, the cracking activity of the resulting catalyst may be low, while if it is more than 50% by mass, the cracking activity may be too high, resulting in increased production of hydrogen, gas, and coke, resulting in a low gasoline yield. If the content of the rare earth metal oxide precursor is less than 0.5% by mass as RE ₂ O _3, the desired effect may not be obtained, while if it is more than 20% by mass, the wear resistance (Attr.Res.) of the catalyst composition may decrease. In addition, the fluid catalytic cracking catalyst preferably contains the porous inorganic oxide matrix in the range of 30 to 90% by mass, preferably 30 to 85% by mass. Each component of the catalyst composition is determined within its respective range so that the total is 100% by mass.

- Manufacturing method of fluid catalytic cracking catalyst -
The above-mentioned fluid catalytic cracking catalyst is produced by adding the above-mentioned zeolite to basic aluminum chloride, which is the above-mentioned porous inorganic oxide matrix precursor, and dispersing the mixture in a uniform manner, followed by spray drying and washing in the following steps. When a silica-based binder is used, the conditions may be different, and in that case, they will be described in parentheses.

<Mixed slurry obtaining step>
The step of obtaining a mixed slurry containing a matrix including a binder component and zeolite, and an additive including at least one selected from activated alumina and a metal capture agent is referred to as a mixed slurry obtaining step.
The mixed slurry obtained here is preferably adjusted to have a solid content in the range of 25 to 50% by mass in order to be suitable for the subsequent spray drying step. If the solid content is less than 25% by mass, the bulk density of the catalyst decreases and the abrasion resistance deteriorates, whereas if it exceeds 50% by mass, the viscosity of the mixed slurry increases, making spray drying difficult.

<Precursor acquisition process>
The step of obtaining a precursor of a fluid catalytic cracking catalyst by spray-drying the mixed slurry obtained in the mixed slurry obtaining step is referred to as a precursor obtaining step.
The conditions for spray drying in this step are preferably a spray outlet temperature in the range of 200 to 250° C. (when a silica-based binder is used, the outlet temperature is 155 to 215° C.) If the outlet temperature is less than 200° C., it becomes difficult to maintain the particle shape of the catalyst after washing, and the abrasion resistance deteriorates, while if the outlet temperature exceeds 250° C., although the particle shape after washing can be maintained, the drying speed becomes faster, making the catalyst particles more susceptible to cracking, and the abrasion resistance may worsen instead.

<Process for obtaining washed cake 1>
The fluid catalytic cracking catalyst precursor obtained in the precursor obtaining step is suspended in an aqueous solution having a pH in the range of 5.5 to 7.5 (when a silica-based binder is used, the pH is 2.5 to 3.5) at 40 to 70° C., and then filtered. If necessary, the resulting mixture is further washed with hot water and filtered to obtain a washed cake 1. This process is referred to as a washed cake 1 obtaining step.
The aqueous solution used for the suspension in this step is preferably an aqueous solution containing a sodium salt such as sodium carbonate, sodium hydrogen carbonate, or sodium hydroxide, and is preferably used after adjusting the pH of the aqueous solution to be within a desired range. In addition, in the case of sodium hydroxide, it is preferable to use ammonium sulfate simultaneously.

If the temperature of the aqueous solution is lower than 40°C, the amount of residual chlorine derived from the binder component increases, which may corrode the fluid catalytic cracking unit, while if it is higher than 70°C, hydrolysis of the binder component may occur more easily, which may worsen the wear resistance. (When using a silica-based binder, the temperature of the aqueous solution during washing does not need to be particularly limited, but it is preferable to wash in the range of 50 to 70°C.)

Furthermore, from the viewpoint of soluble impurities and filterability, it is preferable that the ratio of the solid content of the precursor to the aqueous solution during washing is in the range of solid content/aqueous solution = 1/3 to 1/15 by mass.

<Process for obtaining washed cake 2>
The step of obtaining a washed cake 2 is a step of drying the washed cake 1 obtained in the step of obtaining a washed cake 1 to obtain a washed cake 2. Before drying, it is preferable to suspend the washed cake ₁ in water, add an aqueous solution containing a _RE2O3 precursor of a rare earth element as necessary, stir the suspension, filter, and further wash the suspension with hot water.

<Heat drying process>
The step of obtaining the fluid catalytic cracking catalyst of the present invention by heating the washed cake 2 obtained in the washed cake 2 obtaining step in a temperature range of 80 to 600°C by a general method such as a dryer, a muffle furnace, or a rotary kiln is referred to as the heat drying step. The heat drying step may be performed under any conditions such as air or steam. If the temperature is less than 80°C, the drying may be insufficient, and the physical properties and performance of the catalyst during use may be deteriorated, whereas if the temperature exceeds 600°C, the performance may be reduced due to aggregation of the active components.

The fluid catalytic cracking catalyst of the present invention can be used in conventional fluid catalytic cracking of hydrocarbon oils, and conventional fluid catalytic cracking conditions can be adopted. In addition, the catalyst composition of the present invention can be used in the fluid catalytic cracking of any conventional hydrocarbon oil feedstock oil, but has excellent hydrothermal resistance and is particularly suitable for use in the fluid catalytic cracking of heavy hydrocarbon oils containing nickel, vanadium, etc.

The zeolite of the present invention can be suitably used not only as the above-mentioned fluid catalytic cracking catalyst, but also as a catalyst for oil refining such as hydrocracking and isomerization, a catalyst for the petrochemical synthesis of xylene, ethylbenzene, cumene, etc., and a catalyst for the synthesis of fine chemicals.

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.
Example 1
- Preparation of ultra-stabilized Y-type zeolite No. 1 As the NaY-type zeolite, one having a SiO ₂ /Al ₂ O ₃ (molar ratio) of 5.2, a lattice constant of 2.466 nm, a specific surface area of 720 m ² /g, and a Na content of 13.0 mass% in terms of Na ₂ O was used. 50.0 kg of NaY-type zeolite was added to 500 L of hot water at 60 ° C., and 14.0 kg of ammonium sulfate was further added to obtain a suspension. This suspension was stirred at 70 ° C. for 1 hour and filtered. The solid obtained by filtration was washed with hot water at 60 ° C. Next, this solid was washed with an ammonium sulfate solution in which 14.0 kg of ammonium sulfate was dissolved in 500 L of hot water at 60 ° C., and further washed with 500 L of water at 60 ° C. to obtain a washed cake. The washed cake was dried at 130° C. for 20 hours to obtain Y-type zeolite (NH ₄ Y) in which about 65% by mass of the Na contained in the NaY-type zeolite was ion-exchanged with ammonium ions (NH ₄ ⁺ ). The Na content of this NH ₄ Y-type zeolite was 4.5% by mass in terms of Na ₂ O (first step).

40 kg of this NH ₄ Y-type zeolite was calcined in a saturated steam atmosphere at 670° C. for 1 hour. The calcined powder obtained was added to 400 L of hot water at 60° C., and the pH was adjusted to 2.5 to 4.5 with 25% sulfuric acid. Then, 49.0 kg of ammonium sulfate was added and stirred for 1 hour at 90° C. The resulting slurry was filtered and then washed with 200 L of hot water at 60° C. to obtain a washed cake (1) (second step).
The obtained washed cake (1) was added to 400 L of hot water at 60° C. and stirred at 60° C. for 10 minutes. The obtained slurry was filtered and then washed with 200 L of hot water at 60° C. to obtain washed cake (2). Next, the washed cake (2) was dried at 130° C. for 20 hours to obtain ultra-stable Y-type (hereinafter referred to as “USY”) zeolite No. 1 (third step). The properties of USY zeolite No. 1 are shown in Table 1.
In this example, a flocculant was used in the process with the intention of improving the yield. However, when a flocculant is not used, a decrease in yield is observed, but it has been confirmed that there is almost no difference in the physical properties of the obtained zeolite.

Preparation of Fluid Catalytic Cracking Catalyst No. 1 For the fluid catalytic cracking catalyst, USY zeolite No. 1 was further calcined at 830° C. for 30 minutes and used.
Water glass (No. 3 water glass adjusted to 17.5% by mass in terms of SiO ₂ ) and sulfuric acid (adjusted to a concentration of 25% by mass) were added simultaneously and continuously to prepare a silica hydrosol containing 12.5% by mass of SiO _2. 891.4 g of kaolin (solid content concentration: 85.54% by mass), 580.3 g of activated alumina powder (solid content concentration: 84% by mass), and 2272.7 g of USY zeolite slurry (solid content concentration: 33% by mass) whose pH was adjusted to 3.9 with sulfuric acid were added to 4000 g of this silica hydrosol to prepare a mixed slurry.
The mixed slurry was made into droplets and spray-dried in a spray dryer with an inlet temperature of 250°C and an outlet temperature of 150°C, to obtain dried particles with an average particle size of 70 μm. The obtained spray-dried particles were suspended in 10 times the amount of hot water (60°C) by mass and dehydrated and filtered. Next, 10 times the amount of hot water (60°C) was poured on the mixture, and the mixture was further suspended and contacted with an aqueous solution of rare earth metal chlorides (including chlorides of cerium and lanthanum) to perform ion exchange treatment so that the RE ₂ O ₃ content was 2.0 mass%, and then the cake was collected and dried for 10 hours in a dryer maintained at an atmospheric temperature of 150°C to obtain fluid catalytic cracking catalyst No. 1. The catalyst composition and catalyst properties of fluid catalytic cracking catalyst No. 1 are shown in Table 2.

Example 2
Preparation of Ultrastable Y-Type Zeolite No. 2 USY zeolite No. 2 was obtained in the same manner as in Example 1, except that 40 kg of the NH ₄ Y-type zeolite obtained in Example 1 was calcined in a saturated steam atmosphere at 590° C. for 1 hour. The properties of USY zeolite No. 2 are shown in Table 1.
Preparation of Fluid Catalytic Cracking Catalyst No. 2 Fluid catalytic cracking catalyst No. 2 was obtained in the same manner as in Example 1, except that USY zeolite No. 2 was used as the USY zeolite. The catalyst composition and catalyst properties of fluid catalytic cracking catalyst No. 2 are shown in Table 2.

Example 3
Preparation of Ultrastable Y-Type Zeolite No. 3 USY zeolite No. 3 was obtained in the same manner as in Example 1, except that 40 kg of the NH ₄ Y-type zeolite obtained in Example 1 was calcined in a saturated steam atmosphere at 695° C. for 1 hour. The properties of USY zeolite No. 3 are shown in Table 1.
Preparation of Fluid Catalytic Cracking Catalyst No. 3 Fluid catalytic cracking catalyst No. 3 was obtained in the same manner as in Example 1, except that USY zeolite No. 3 was used as the USY zeolite. The catalyst composition and catalyst properties of fluid catalytic cracking catalyst No. 3 are shown in Table 2.

(Comparative Example 1)
Preparation of Ultra-stable Y-type Zeolite No. R1 The washed cake (1) obtained in Example 1 was dried at 130° C. for 20 hours to obtain USY Zeolite No. R1. The properties of USY Zeolite No. R1 are shown in Table 1.
Preparation of Fluid Catalytic Cracking Catalyst No. R1 Fluid catalytic cracking catalyst No. R1 was obtained in the same manner as in Example 1, except that USY zeolite No. R1 was used as the USY zeolite. The catalyst composition and catalyst properties of fluid catalytic cracking catalyst No. R1 are shown in Table 2.

(Comparative Example 2)
Preparation of ultra-stable Y-type zeolite No. R2 40 kg of NH ₄ Y-type zeolite obtained in Example 1 was calcined at 500°C for 1 hour in a saturated steam atmosphere. The calcined powder obtained was added to 400 L of hot water at 60°C, and the pH was adjusted to 2.5 to 4.5 with 25% sulfuric acid. Then, 49.0 kg of ammonium sulfate was added and stirred at 90°C for 1 hour. The resulting slurry was filtered and then washed with 200 L of hot water at 60°C to obtain a washed cake (4). The washed cake (4) was then dried at 130°C for 20 hours to obtain a USY zeolite No. R2. The properties of the USY zeolite No. R2 are shown in Table 1.
Preparation of Fluid Catalytic Cracking Catalyst No. R2 Fluid catalytic cracking catalyst No. R2 was obtained in the same manner as in Example 1, except that USY zeolite No. R2 was used as the USY zeolite. The catalyst composition and catalyst properties of fluid catalytic cracking catalyst No. R2 are shown in Table 2.

(Comparative Example 3)
- Preparation of ultra-stable Y-type zeolite No. R3 As in Example 1, 40 kg of NH ₄ Y-type zeolite was calcined in a saturated steam atmosphere at 670 ° C for 1 hour. The calcined powder obtained was added to 400 L of hot water at 60 ° C, and then 49.0 kg of ammonium sulfate was added to obtain a suspension. This suspension was stirred at 90 ° C for 1 hour and filtered. The solid obtained by filtration was washed with 200 L of hot water at 60 ° C. Then, this solid was dried at 130 ° C for 20 hours. The obtained dried powder was calcined in a saturated steam atmosphere at 750 ° C for 2 hours under a steam atmosphere to obtain USY zeolite No. R3. The properties of USY zeolite No. R3 are shown in Table 1.
Preparation of Fluid Catalytic Cracking Catalyst No. R3 Fluid catalytic cracking catalyst No. R3 was obtained in the same manner as in Example 1, except that USY zeolite No. R3 was used as the USY zeolite. However, the catalyst was used without additional calcination at 830°C for 30 minutes. The catalyst composition and properties of fluid catalytic cracking catalyst No. R3 are shown in Table 2.

[Catalyst activity evaluation test]
For each of the catalysts of the invention examples and comparative examples, a catalyst performance evaluation test was performed using ACE-MAT (Advanced Cracking Evaluation Micro Activity Test). However, before performing these performance evaluation tests, the catalyst obtained as described above was previously calcined at an atmospheric temperature of 600°C for 2 hours. Thereafter, a predetermined amount of nickel octylate and vanadium octylate was deposited on the calcined catalyst particles. Next, the catalyst was dried at an atmospheric temperature of 110°C and calcined at an atmospheric temperature of 600°C for 1.5 hours, and then heat-treated in various water vapor atmospheres to perform a pseudo-equilibrium treatment of the catalyst. The pretreatment conditions are shown in Table 3. Condition No. S1 was used as the standard, and condition No. S2 in which nickel and vanadium were deposited and condition No. S3 in which the steaming calcination temperature was high were used.

The operating conditions in the activity evaluation test were as follows.
Feedstock: Desulfurized atmospheric residue of crude oil (DSAR) + desulfurized vacuum gas oil (DSVGO) (50+50)
Mass ratio of catalyst/through oil (C/O): 5.00
Reaction temperature: 520°C
1) Conversion rate = 100 - (LCO + HCO)
2) Boiling point range of gasoline: 30 to 216°C
3) Boiling point range of LCO: 216 to 343°C (LCO: Light Cycle Oil)
4) Boiling point range of HCO: 343°C+ (HCO: Heavy Cycle Oil)

The results of the metal resistance test for nickel and vanadium on the catalyst are shown in Table 4. All of the examples had higher conversion rates and gasoline yields after metal treatment than the comparative examples, and the retention rate of the conversion rate was high, so the catalysts can be evaluated as having excellent metal resistance.

The results of the hydrothermal resistance test of the catalyst are shown in Table 5. In all of the invention examples, the conversion rate remained higher than in the comparative examples even when the steaming calcination temperature was increased, and the catalysts can be evaluated as having excellent hydrothermal resistance.

Claims (4)

the peak area ratio (P _6Al )/(P _4Al ) of the peak area of the spectrum of tetracoordinated Al (P _4Al ) to the peak area of the spectrum of hexacoordinated Al (P _6Al ) measured by solid-state NMR of alumina is in the range of 0.20 to 0.40;
A faujasite-type zeolite having an ammonia desorption amount in the range of 1.0 to 2.5 mmol/g as measured by an ammonia temperature programmed desorption method (NH ₃ -TPD method). 2. The faujasite-type zeolite according to claim 1 , wherein the lattice constant is in the range of 24.40 to 24.60 Å. Providing a zeolite ;
a step of treating the zeolite with an acid in the presence of an ammonium salt , followed by solid- liquid separation to obtain a first zeolite cake ;
suspending the first zeolite cake in water to obtain a suspension;
subjecting the suspension to solid-liquid separation to obtain a second zeolite cake;
and drying the second zeolite cake at 80 to 400°C . A catalyst comprising the faujasite-type zeolite of claim 1 .