Modified zeolite, method for producing said zeolite, and catalyst containing said zeolite

Abstract

To provide a modified zeolite suitable for catalysts, for example, a fluid catalytic cracking catalyst.SOLUTION: A modified zeolite has following characteristics. (a) It is a faujasite zeolite. (b) As measured for alumina by solid NMR, a peak area ratio between a peak area (P4Al) of spectrum of 4-coordinated Al and a peak area (P6Al) of spectrum of 6-coordinated Al, (P6Al) / (P4Al), is 0.10-0.40. (c) As measured by ammonia temperature-programmed desorption method (NH3-TPD method), the amount of ammonia desorption is 1.0-2.5 mmol / g. (d) It is supported on aluminosilicate. There is also provided a catalyst including the modified zeolite. There is also provided a production method that includes subjecting zeolite to acid treatment in the presence of ammonium salt for solid-liquid separation, to obtain filtrate and zeolite cake; flocculating the filtrate to obtain dissolved aluminosilicate cake, which is mixed with the zeolite cake into a modified zeolite.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a modified zeolite suitable for use as a catalyst component or adsorbent in the fields of petroleum refining and petrochemicals, a method for producing the same, and a catalyst using the modified zeolite. [Background technology]

[0002] In recent years, the petroleum refining industry has increasingly used residual oil and other heavy hydrocarbon oils as feedstock for catalytic cracking. In particular, there is a demand for catalysts that are resistant to metals such as vanadium and nickel, have excellent residual oil decomposition capabilities, produce little hydrogen and coke, and produce high yields of gasoline and kerosene fraction (LCO).

[0003] Solutions to these problems have been proposed to some extent through improvements in the process and the development of fluid catalytic cracking catalysts.

[0004] Patent Document 1 describes a fluid catalytic cracking catalyst that is excellent in cracking activity, gasoline selectivity, hydrothermal stability, and resistance to metal poisoning by coating zeolite with a single metal oxide such as alumina, zirconia, magnesia, or titania.

[0005] Furthermore, Patent Documents 2 to 6 disclose techniques relating to modified zeolites, catalytic cracking catalysts containing the zeolites, and methods for producing the same. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 58-112051 [Patent Document 2] Japanese Patent Application Publication No. 60-046916 [Patent Document 3] Japanese Patent Application Publication No. 60-046917 [Patent Document 4] Japanese Patent Application Publication No. 04-187514 [Patent Document 5] Japanese Unexamined Patent Publication No. 159219 / 1983 [Patent Document 6] Japanese Patent Publication No. 2020-019694 Summary of the Invention [Problem to be solved by the invention]

[0007] In the future, the contents of vanadium and nickel, which are poisonous substances contained in residual oil, are likely to increase further, and there is a demand for fluid catalytic cracking catalysts that can maintain residual oil cracking activity even under such circumstances.However, the conventional fluid catalytic cracking catalysts mentioned above have the problem of not being able to obtain sufficient activity.

[0008] The present invention aims to provide a modified zeolite suitable for use as a catalyst component or adsorbent in the fields of petroleum refining and petrochemicals, a method for producing the zeolite, and a catalyst containing the zeolite, particularly a modified zeolite suitable for use as a fluid catalytic cracking catalyst. [Means for solving the problem]

[0009] With this technical background in mind, the inventors have conducted extensive research into improving fluid catalytic cracking catalysts that are excellent in the cracking ability of heavy fractions (bottoms). As a result, they have found that fluid catalytic cracking catalysts including those characterized by a modified zeolite supported on an aluminosilicate exhibit heavy fraction (bottoms) cracking ability that is significantly superior in hydrothermal stability and resistance to metal poisoning, and have thus completed the present invention.

[0010] The modified zeolite according to the present invention is It has the following characteristics (a) to (d). (a) Faujasite-type zeolite. (b) The peak area of ​​the tetrahedral Al spectrum measured by solid-state NMR of alumina (P 4Al ) and the peak area of ​​the spectrum of hexacoordinated Al (P 6Al ) and the peak area ratio (P 6Al) / (P 4Al ) is in the range of 0.10 to 0.40. (c) The amount of ammonia desorption measured by ammonia temperature programmed desorption spectroscopy (NH3-TPD method) is in the range of 1.0 to 2.5 mmol / g. (d) Supported on aluminosilicate.

[0011] The modified zeolite according to the present invention is as follows: (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.

[0012] Further, a method for producing a modified zeolite according to the present invention is a method for producing any of the above modified zeolites, comprising: (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 filtrate containing dissolved aluminosilicates and a zeolite cake; (3) a third step of adding a flocculant to the filtrate to obtain a dissolved aluminosilicate cake; (4) a fourth step of mixing the dissolved aluminosilicate cake and the zeolite cake to obtain a modified zeolite; It includes:

[0013] In addition, in the method for producing a modified zeolite according to the present invention, it is considered that a more preferable solution can be achieved by setting the mixing ratio of the dissolved aluminosilicate cake to the sum of the dissolved aluminosilicate cake and the zeolite cake in the fourth step to 0.1 to 10% by mass.

[0014] The catalyst according to the present invention contains any of the modified zeolites described above. [Effects of the Invention]

[0015] As described above, the modified zeolite obtained by the present invention and its production method can provide a fluid catalytic cracking catalyst, which, when used in a catalyst, particularly a fluid catalytic cracking catalyst, has excellent cracking ability for heavy fractions (bottoms), high cracking activity, low production of hydrogen, gas, and coke, high yields of gasoline and kerosene fractions, and excellent hydrothermal stability and resistance to metal poisoning. Furthermore, the modified zeolite of the present invention can be used, for example, as a catalyst component for use in oil refining and petrochemical fields, or as an adsorbent. DETAILED DESCRIPTION OF THE INVENTION

[0016] The modified zeolite of the present invention was first developed for use as a fluid catalytic cracking catalyst.

[0017] As catalysts for fluid catalytic cracking (FCC) of hydrocarbons, catalytic compositions have been known which contain fine zeolite dispersed in a matrix of porous inorganic oxides, such as silica-alumina, silica-zirconia, silica-magnesia, or even silica-clay. However, in general, this type of catalytic composition has the risk of the zeolite pores being encapsulated by the matrix components, particularly the silica components in the matrix, and this encapsulation can significantly reduce the catalytic performance.

[0018] <Modified zeolite> The present invention provides a fluid catalytic cracking catalyst that exhibits excellent cracking activity, gasoline selectivity, hydrothermal stability, and metal poisoning resistance by utilizing a modified zeolite dispersed in a matrix. That is, the FCC catalyst of the present invention contains a modified zeolite supported on an aluminosilicate in a dispersed state. In the present invention, "supported" includes the case where the modified zeolite is attached to the surface or mixed in close proximity.

[0019] The zeolite used in the present invention is a faujasite-type zeolite, and in particular, ultra-stable Y-type zeolite (USY) is preferred because of its excellent hydrothermal resistance.

[0020] The USY zeolite of the present invention contains a specific ratio of hexacoordinated Al atoms in addition to tetracoordinated Al atoms in the framework. The inventors define the ratio of tetracoordinated Al atoms to hexacoordinated Al atoms as the ratio of peak areas measured using solid-state NMR.

[0021] That is, the peak area (P 4Al ) and the peak area of ​​the spectrum of hexacoordinated Al (P 6Al ) and the peak area ratio (P 6Al ) / (P 4Al ) must be in the range of 0.10 to 0.40. If the peak area ratio is below the lower limit of the above ratio, 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 tetrahedral Al (Al atoms in the framework), and activity may be insufficient.

[0022] In the present invention, the coordination state of aluminum present in zeolite was measured using a solid-state high-resolution NMR (Nuclear Magnetic Resonance) device (Agilent: VNS-600). 27 Al MAS (Magic Angle Spinning) NMR spectroscopy was performed at room temperature under the following conditions: resonance frequency 156.29 MHz, spin speed 20 kHz, waiting time 0.1 sec, and accumulation count 128. Prior to the measurement, the sample was placed in a desiccator containing saturated NH4Cl vapor for at least 24 hours to allow sufficient water absorption. Aluminum nitrate nonahydrate (Al(NO3)3·9H2O) was used as the external standard.

[0023] The composition of the zeolite was analyzed by the glass bead method using an X-ray fluorescence analyzer (MagiX PRO, manufactured by PHILIPS). The lattice constant of the zeolite was measured using a powder X-ray diffractometer (RINT-2100 manufactured by Rigaku Corporation). The lattice constant was calculated using Cu-Kα radiation 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. A lattice constant within this range results in a large solid acidity and high activity. If the lattice constant is too high, the hydrothermal resistance, metal resistance, etc. may be insufficient, while if the lattice constant is too low, the solid acidity may be small and the activity may be insufficient.

[0024] The specific surface area was measured by measuring the amount of adsorption and desorption of N2 on a sample powder that had been pretreated in an inert gas atmosphere at 500°C for 1 hour using a MacSorb-1220 manufactured by Mountech Co., Ltd. The specific surface area was calculated from the amount of desorption of N2 obtained using the BET single-point method.

[0025] The amount of ammonia desorption was measured by ammonia temperature-programmed desorption (NH3-TPD) method. Specifically, a BELCAT-B (registered trademark) manufactured by Microtrackbell was used. 0.2 g of sample was placed in the measurement cell, and evacuation treatment was performed at 500°C for 1 hour. The temperature was then raised to 100°C, and ammonia gas was introduced and adsorbed at 100°C for 0.5 hours. Next, evacuation treatment was performed again at 100°C for 0.5 hours. After that, the amount of ammonia desorbed was measured while the temperature was increased from 100°C to 700°C at a rate of 10°C per minute under a He gas flow of 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 below the lower limit, the cracking activity will be insufficient. On the other hand, if the amount of ammonia desorption is above the upper limit, the amount of coke produced will increase, potentially reducing gasoline selectivity.

[0026] In addition to the above-mentioned fluid catalytic cracking applications, the modified zeolite of the present invention can also be used 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.

[0027] <Method for producing modified zeolite> (1) First step: preparing zeolite As the NaY-type zeolite, any conventionally known NaY-type zeolite can be used. The SiO2 / Al2O3 molar ratio of the NaY-type zeolite used in the present invention is preferably in the range of 3-6, more preferably 4-6.

[0028] Ammonium ion exchange involves dispersing NaY-type zeolite in an aqueous ammonium salt solution to obtain NH4Y-type zeolite. Ion exchange can be performed using a conventionally known method. The amount of ammonium salt used is preferably 0.6 to 3 moles, more preferably 1 to 2 moles, per mole of NaY-type zeolite (Na2O·Al2O3·nSiO2:n is the SiO2 / Al2O3 molar ratio). If the amount of ammonium salt used is too small, the desired ion exchange rate cannot be achieved, and the amount of residual Na increases, which can significantly reduce crystallinity in subsequent steps. The temperature during ion exchange is not particularly limited, but is preferably in the range of room temperature to 100°C, more preferably 50 to 95°C.

[0029] NH4Y-type zeolite can be heat-treated at 550 to 750°C by a conventionally known method. For example, a muffle furnace, a rotary kiln, or the like can be used. Steam may be supplied during heating, or NH4Y-type zeolite that has already been moistened may be used. By heat-treating in the presence of steam, the lattice constant can be adjusted.

[0030] (2) A second step in which zeolite is treated with an acid in the presence of an ammonium salt, followed by solid-liquid separation to obtain a filtrate containing dissolved aluminosilicate and 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 extra-framework aluminum. The acid solution used in this step is a solution containing an acid, and includes conventionally known inorganic acids such as sulfuric acid, hydrochloric acid, and nitric acid. Furthermore, organic acids such as citric acid and acetic acid may also be used as long as they are capable of removing extra-framework aluminum.

[0031] The acid solution in this step may contain a salt containing ammonium ions. In this way, when acid treatment is performed using an acid solution containing ammonium ions, Na, which is the counter cation of aluminum, is added. + becomes more easily removed.

[0032] After the acid treatment, the acid solution and the zeolite can be subjected to solid-liquid separation by a method such as filtration 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 treatment such as suspending the separated zeolite again in water or pouring warm water over the filter cloth.

[0033] (3) The third step is to add a flocculant to the filtrate to obtain a dissolved aluminosilicate cake. Furthermore, since the filtrate contains dissolved aluminosilicate, it is preferable to flocculate and recover the solids from the standpoints of yield, performance, etc. A flocculant is added to the filtrate, and a precipitate containing dissolved aluminosilicate is obtained from the filtrate. The recovered dissolved aluminosilicate is subjected to solid-liquid separation by a method such as filtration, and then resuspended in water or washed by pouring warm water over the filter cloth to obtain a dissolved aluminosilicate cake. Furthermore, when obtaining the dissolved aluminosilicate cake, a device for concentrating and settling the slurry, such as a thickener, may be used.

[0034] 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 both may be used in combination. At least one of cationic, anionic, nonionic, and amphoteric organic polymer flocculants can be used.

[0035] (4) The fourth step is to mix the dissolved aluminosilicate cake with the zeolite cake to obtain a modified zeolite. The recovered dissolved aluminosilicate cake is mixed with the previously separated zeolite cake to obtain a zeolite mixture. The zeolite mixture can be dried at a temperature in the range of 80° C. to 400° C. to obtain a modified zeolite. If necessary, the zeolite can be calcined in the air at a temperature in the range of 400° C. to 900° C. The mixing ratio of the dissolved aluminosilicate cake to the total of the dissolved aluminosilicate cake and the zeolite cake is preferably 0.1 to 10% by mass. If the ratio is less than the lower limit, the effect of supporting the zeolite on the aluminosilicate cannot be obtained. On the other hand, if the ratio is more than the upper limit, the effect will saturate and filterability during washing may be impaired.

[0036] The catalyst containing the modified zeolite of the present invention will be described taking a fluid catalytic cracking catalyst as an example. - Fluid catalytic cracking catalyst - The fluid catalytic cracking catalyst of the present invention comprises a matrix containing a binder component containing silica or alumina and the modified zeolite (hereinafter simply referred to as zeolite) prepared as described above, and an additive containing at least one selected from activated alumina and a metal scavenger, and may further contain a rare earth metal oxide. This zeolite is used in a form ion-exchanged with a cation selected from hydrogen, ammonium, and a polyvalent metal, as in the case of use in a conventional catalytic cracking catalyst.

[0037] As the precursor of the rare earth metal oxide in the present invention, commercially available carbonates, hydrochlorides, nitrates, oxalates, etc. of rare earth metals can be used.

[0038] The fluid catalytic cracking catalyst of the present invention uses a porous inorganic oxide matrix, similar to conventional catalytic cracking catalysts. The porous inorganic oxide matrix can be made of silicate such as sodium silicate, silica-based binders such as silica sol, or alumina-based binders such as basic aluminum chloride, alumina sol, or alumina gel. Additives that can be used in combination include clay minerals such as kaolin, halloysite, and montmorillonite; matrices containing solid acids such as activated alumina, silica-alumina, silica-magnesia, alumina-magnesia, and silica-magnesia-alumina; and metal scavengers such as manganese dioxide, calcium aluminate, aluminum hydroxide, and rare earth metal oxides (e.g., lanthanum carbonate).

[0039] 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. The fluid catalytic cracking catalyst preferably contains the zeolite in an amount of 5 to 50 mass%, more preferably 10 to 40 mass%, based on the catalyst. Furthermore, when the rare earth metal oxide is contained, it is 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 (RE2O3) based on the catalyst, and up to 20 mass% or less, preferably 18 mass% or less, more preferably 15 mass% or less, and is desirably uniformly dispersed in the porous inorganic oxide matrix.

[0040] If the zeolite content is less than 5% by mass, the cracking activity of the resulting catalyst may be low. On the other hand, 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. Furthermore, if the content of the rare earth metal oxide precursor is less than 0.5% by mass (RE2O3), the desired effect may not be achieved. On the other hand, if it is more than 20% by mass, the attrition resistance (Attr.Res.) of the catalyst composition may decrease. Furthermore, the fluid catalytic cracking catalyst preferably contains the porous inorganic oxide matrix in a range of 30 to 90% by mass, preferably 30 to 85% by mass. The respective components of the catalyst composition are determined within their respective ranges so that the total amount adds up to 100% by mass.

[0041] - Fluid catalytic cracking catalyst manufacturing method - The production method of the fluid catalytic cracking catalyst is described below by taking as an example a method in which the zeolite is added to basic aluminum chloride, which is the porous inorganic oxide matrix precursor, and uniformly dispersed in the resulting mixture slurry, followed by spray drying and washing in the following steps: When a silica-based binder is used, the conditions may be different, and in such cases they will be described in parentheses.

[0042] <Mixed slurry obtaining process> 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 the mixed slurry obtaining step. The mixed slurry obtained here is preferably adjusted to have a solids concentration in the range of 25 to 50% by mass so that it is suitable for the subsequent spray drying step. If the solids concentration is less than 25% by mass, the bulk density of the catalyst may decrease and the attrition resistance may deteriorate, while if it exceeds 50% by mass, the viscosity of the mixed slurry may increase, making spray drying difficult.

[0043] <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 spray drying conditions in this step are preferably such that the spray outlet temperature is 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 abrasion resistance deteriorates. On the other hand, if the outlet temperature exceeds 250°C, although the particle shape after washing can be maintained, the drying speed increases, making the catalyst particles more susceptible to cracking, and this may actually worsen abrasion resistance.

[0044] <Washed cake 1 acquisition process> 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 suspension is further washed with hot water and filtered to obtain a washed cake 1, which is referred to as a washed cake 1 obtaining step. The aqueous solution used for suspension in this step is preferably an aqueous solution containing sodium salts of sodium carbonate, sodium bicarbonate, or sodium hydroxide, and is preferably used after adjusting the pH of the aqueous solution to fall within a desired range. In the case of sodium hydroxide, it is preferable to use ammonium sulfate simultaneously.

[0045] 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 the temperature is higher than 70°C, hydrolysis of the binder component may occur more easily, which may result in a deterioration in abrasion resistance. (When a silica-based binder is used, the temperature of the aqueous solution during washing does not need to be particularly limited, but it is preferably in the range of 50 to 70°C.) Furthermore, the ratio of the solid content of the precursor to the aqueous solution during washing is preferably in the range of solid content / aqueous solution=1 / 3 to 1 / 15 in terms of soluble impurities and filterability.

[0046] <Washed cake 2 acquisition process> The step of obtaining washed cake 2 is a step of drying the washed cake 1 obtained in the step of obtaining washed cake 1 to obtain washed cake 2. Before drying, it is preferable to suspend the cake in water, add an aqueous solution containing a RE2O3 precursor of a rare earth element, stir the mixture, filter, and further wash the mixture with warm water.

[0047] <Heat drying process> The heated drying step is a 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 at a temperature in the range of 80 to 600°C using a conventional method such as a dryer, muffle furnace, or rotary kiln. The heated drying step may also be carried out under any conditions, such as air or steam. If the temperature is lower than 80°C, the drying may be insufficient, which may result in deterioration of the physical properties and performance of the catalyst during use. On the other hand, if the temperature exceeds 600°C, the performance may be reduced due to aggregation of the active components.

[0048] 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 employed. Furthermore, the catalyst composition of the present invention can be used in the fluid catalytic cracking of any conventional hydrocarbon oil feedstock, but has excellent hydrothermal resistance and is particularly suitable for the fluid catalytic cracking of heavy hydrocarbon oils containing nickel, vanadium, etc.

[0049] The modified 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 petroleum refining such as hydrocracking and isomerization, a catalyst for petrochemical synthesis of xylene, ethylbenzene, cumene, etc., and a catalyst for synthesizing fine chemicals. [Example]

[0050] 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-stable Y-type modified zeolite No. 1 As a NaY-type zeolite, the SiO2 / Al2O3 (molar ratio) is 5.2, the lattice constant is 2.466 nm, and the specific surface area is 720 m 2The NaY zeolite was used, which had a Na content of 13.0 mass% in terms of Na2O. 50.0 kg of NaY 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 prepared by dissolving 14.0 kg of ammonium sulfate 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 obtained was dried at 130°C for 20 hours, and approximately 65 mass% of the Na contained in the NaY zeolite was converted to ammonium ions (NH4 + The Na content of this NH4Y zeolite was 4.5% by mass in terms of Na2O. (First Step) 40 kg of this NH4Y-type zeolite was calcined at 670°C for 1 hour in a saturated steam atmosphere. The resulting calcined powder was added to 400 L of 60°C hot water, and the pH was adjusted to 2.5 to 4.5 with 25% sulfuric acid. 49.0 kg of ammonium sulfate was then added and stirred at 90°C for 1 hour. The resulting slurry was filtered and then washed with 200 L of 60°C hot water to obtain a washed cake (1). (Second Step) The filtrate was then collected and 0.1% by weight of a polymer flocculant (Himoc MX-2100, manufactured by Hymo Corporation) was added to the filtrate to a solution concentration of 6 ppm. After stirring for 10 minutes, the resulting precipitate was filtered and washed with 200 L of warm water to obtain a washed cake (2). (Third Step) The resulting washed cake (1) and washed cake (2) were mixed in a mass ratio of 99:1, added to 400 L of 60°C hot water, and stirred at 60°C for 10 minutes. The resulting slurry was filtered and then washed with 200 L of 60°C hot water to obtain washed cake (3). The washed cake (3) was then dried at 130°C for 20 hours to obtain ultra-stable Y-type (hereinafter referred to as "USY") modified zeolite No. 1. (Fourth step) The properties of the USY modified zeolite No. 1 are shown in Table 1.

[0051] Preparation of fluid catalytic cracking catalyst No. 1 For the fluid catalytic cracking catalyst, USY modified zeolite No. 1 was further calcined at 830°C for 30 minutes and used. To this, water glass (No. 3 water glass adjusted to 17.5% by mass in terms of SiO2) and sulfuric acid (adjusted to a concentration of 25% by mass) were simultaneously and continuously added to prepare a silica hydrosol containing 12.5% ​​by mass of SiO2. To 4000 g of this silica hydrosol, 891.4 g of kaolin (solid content: 85.54% by mass), 580.3 g of activated alumina powder (solid content: 84% by mass), and 2272.7 g of USY zeolite slurry (solid content: 33% by mass) whose pH had been adjusted to 3.9 with sulfuric acid were added to prepare a mixed slurry. This mixed slurry was transformed into droplets and spray-dried in a spray dryer with an inlet temperature of 250°C and an outlet temperature of 150°C, yielding dried particles with an average particle size of 70 μm. The resulting spray-dried particles were suspended in 10 times the mass of hot water (60°C) and dehydrated by filtration. Next, 10 times the mass of hot water (60°C) was poured over the particles, and the particles were further suspended and contacted with an aqueous solution of rare earth metal chlorides (including cerium and lanthanum chlorides) to perform ion exchange treatment to a concentration of 2.0 mass% RE2O3. The cake was then recovered and dried for 10 hours in a dryer maintained at an ambient temperature of 150°C, yielding fluid catalytic cracking catalyst No. 1. The catalyst composition and catalytic properties of fluid catalytic cracking catalyst No. 1 are shown in Table 2.

[0052] Example 2 Preparation of ultra-stable Y-type modified zeolite No. 2 Except for mixing the washed cake (1) and the washed cake (2) in a ratio of 97:3, the same procedure as in Example 1 was repeated to obtain USY modified zeolite No. 2. The properties of USY modified 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 modified USY zeolite No. 2 was used as the USY zeolite. The catalyst composition and properties of fluid catalytic cracking catalyst No. 2 are shown in Table 2.

[0053] Example 3 Preparation of ultra-stable Y-type modified zeolite No. 3 Except for mixing the washed cake (1) and the washed cake (2) in a ratio of 94:6, the same procedure as in Example 1 was repeated to obtain USY modified zeolite No. 3. The properties of USY modified 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 modified USY zeolite No. 3 was used as the USY zeolite. The catalyst composition and properties of fluid catalytic cracking catalyst No. 3 are shown in Table 2.

[0054] Example 4 Preparation of ultra-stable Y-type modified zeolite No. 4 Except for mixing the washed cake (1) and the washed cake (2) in a ratio of 92:8, the same procedure as in Example 1 was repeated to obtain USY modified zeolite No. 4. The properties of USY modified zeolite No. 4 are shown in Table 1. Preparation of fluid catalytic cracking catalyst No. 4 Fluid catalytic cracking catalyst No. 4 was obtained in the same manner as in Example 1, except that modified USY zeolite No. 4 was used as the USY zeolite. The catalyst composition and properties of fluid catalytic cracking catalyst No. 4 are shown in Table 2.

[0055] (Comparative Example 1) Preparation of ultra-stable Y-type modified zeolite No. R1 The washed cake (1) obtained in Example 1 was dried at 130°C for 20 hours to obtain USY modified zeolite No. R1. The properties of USY modified 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 modified USY zeolite No. R1 was used as the USY zeolite. The catalyst composition and properties of fluid catalytic cracking catalyst No. R1 are shown in Table 2.

[0056] (Comparative Example 2) Preparation of ultra-stable Y-type zeolite No. R2 40 kg of the NH4Y-type zeolite obtained in Example 1 was calcined at 500°C for 1 hour in a saturated steam atmosphere. The resulting calcined powder 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. 49.0 kg of ammonium sulfate was then added and stirred at 90°C for 1 hour. The resulting slurry was filtered and washed with 200 L of hot water at 60°C to obtain washed cake (4). The washed cake (4) was then dried at 130°C for 20 hours to obtain USY zeolite No. R2. The properties of 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 1-1, except that USY zeolite No. R2 was used as the USY zeolite. The catalyst composition and properties of fluid catalytic cracking catalyst No. R2 are shown in Table 2.

[0057] (Comparative Example 3) Preparation of ultra-stable Y-type zeolite No. R3 As in Example 1, 40 kg of NH4Y-type zeolite was calcined in a saturated steam atmosphere at 670°C for 1 hour. The resulting calcined powder was added to 400 L of 60°C hot water, 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 60°C hot water. This solid was then dried at 130°C for 20 hours. The resulting dried powder was calcined in a saturated steam atmosphere at 750°C for 2 hours 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 1-1, except that USY zeolite No. R3 was used as the USY zeolite. However, it was used without additional calcination at 830°C for 30 minutes. The catalyst composition and catalytic properties of fluid catalytic cracking catalyst No. R3 are shown in Table 2.

[0058] [Catalytic activity evaluation test] The catalyst performance evaluation tests for each of the invention examples and comparative catalysts were performed using the Advanced Cracking Evaluation Micro Activity Test (ACE-MAT). However, before these performance evaluation tests, the catalysts obtained as described above were pre-calcined at an ambient temperature of 600°C for 2 hours. Then, predetermined amounts of nickel octylate and vanadium octylate were deposited on the calcined catalyst particles. The catalysts were then dried at an ambient temperature of 110°C and calcined at an ambient temperature of 600°C for 1.5 hours. After that, the catalysts were subjected to heat treatment in various steam atmospheres to perform a pseudo-equilibrium treatment. The pretreatment conditions are shown in Table 3. Condition No. S1 was used as the standard, while Condition No. S2, in which nickel and vanadium were deposited, and Condition No. S3, in which the steaming calcination temperature was increased, were used.

[0059] The operating conditions for the activity evaluation test were as follows: Feedstock: Desulfurized atmospheric residue (DSAR) of crude oil + desulfurized vacuum gas oil (DSVGO) (50+50) Catalyst / oil mass ratio (C / O): 5.00 Reaction temperature: 520℃ 1) Conversion rate = 100 - (LCO + HCO) 2) Boiling point range of gasoline: 30~216℃ 3) Boiling point range of LCO: 216-343°C (LCO: Light Cycle Oil) 4) Boiling point range of HCO: 343°C+ (HCO: Heavy Cycle Oil)

[0060] The results of the metal resistance test for the catalyst against nickel and vanadium are shown in Table 4. All of the inventive examples had higher conversion rates and gasoline yields after metal treatment than the comparative examples, and the retention rate of conversion was also high, so they can be evaluated as catalysts with excellent metal resistance. The results of the hydrothermal resistance test for the catalysts are shown in Table 5. In all of the invention examples, the conversion rate was maintained 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.

[0061] [Table 1]

[0062]

Table 2

[0063]

Table 3

[0064]

Table 4

[0065]

Table 5

Claims

1. A faujasite-type modified zeolite in which the zeolite is supported on an aluminosilicate, The peak area of ​​the spectrum of tetrahedral Al measured by solid-state NMR of alumina (P ４Ａｌ ) and the peak area of ​​the spectrum of hexacoordinated Al (P ６Ａｌ ) and the peak area ratio (P ６Ａｌ ) / (P ４Ａｌ ) is in the range of 0.10 to 0.40, Ammonia temperature-programmed desorption (NH ３ - The amount of ammonia desorption measured by the TPD method is in the range of 1.0 to 2.5 mmol / g. Modified zeolite.

2. The modified zeolite according to claim 1, characterized in that the lattice constant is in the range of 24.40 to 24.60 Å.

3. A method for producing NH 4 Y-type zeolite by suspending NaY-type zeolite having a SiO 2 / Al 2 O 3 molar ratio of 3 to 6 in an ammonium salt aqueous solution; a second step of obtaining zeolite by heat-treating the NH 4 Y-type zeolite at 550 to 750°C; a third step of treating the zeolite with an acid in the presence of an ammonium salt and obtaining a filtrate containing dissolved aluminosilicate and a zeolite cake by solid-liquid separation; a fourth step of adding a flocculant to the filtrate to obtain a dissolved aluminosilicate cake; a fifth step of mixing the dissolved aluminosilicate cake with the zeolite cake to obtain a modified zeolite.

4. The method for producing a modified zeolite according to claim 3, wherein in the fifth step, the mixing ratio of the dissolved aluminosilicate cake to the zeolite cake is 0.1 to 10% by mass.

5. A catalyst comprising the modified zeolite according to claim 1 or 2.

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