Zeolite, method for producing the zeolite, and catalyst containing the zeolite

Abstract

To provide a zeolite suitable for catalysts, for example, a fluid catalytic cracking catalyst.SOLUTION: A zeolite for a fluid catalytic cracking catalyst 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 0.20-0.40. (c) As measured by ammonia temperature-programmed desorption method (NH3-TPD method), the amount of ammonia desorption is 1.0-2.5 mmol / g. There is also provided a catalyst including the 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 zeolite cake; and obtaining zeolite from the zeolite cake.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a zeolite suitable for use as a constituent component of a catalyst used in the petroleum refining and petrochemical fields and an adsorbent, a method for producing the same, and a catalyst using the zeolite.

Background Art

[0002] In recent years, in the petroleum refining industry, the use of heavy hydrocarbon oils such as residual oils as feedstocks for catalytic cracking has been increasing. In particular, a catalyst that is used for the catalytic cracking of heavy hydrocarbon oils such as residual oils, has metal resistance to vanadium and nickel, is excellent in the decomposition ability of residual oils, produces a small amount of hydrogen, coke, etc., and has a high yield of gasoline and light cycle oil (LCO) fractions is required.

[0003] Regarding these problems, some solutions have been proposed by improvements in the process aspect and the development of fluid catalytic cracking catalysts (hereinafter, also simply referred to as FCC catalysts).

[0004] Patent Document 1 discloses a catalytic cracking catalyst characterized in that the cage ratio of faujasite-type zeolite is 6 or more, the amount of Na2O is in the range of 0.5 wt% or less, and the number of aluminum atoms in the framework (4-coordination) is 25 or more. It has been reported that the catalytic cracking catalyst disclosed in Patent Document 1 has a stable crystal structure even when subjected to high-temperature steam treatment, and the essential catalytic cracking reaction activity of the zeolite is not impaired, and it has excellent hydrothermal resistance.

[0005] Further, Patent Document 2 discloses a ultrastable Y-type zeolite (USY zeolite) in which the pore volume in the range of pore diameters of 3.5 to 5 nm is controlled. The ultrastable Y-type zeolite described in Patent Document 2 has a unit cell constant (UD) of 24.55 Å or less, a SiO2 / Al2O3 (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 it has been reported that it can be used for the hydrocracking of hydrocarbon oils such as light oil and residual oil.

[0006] Furthermore, Patent Document 3 discloses a Y-type zeolite in which aluminum is reinserted into the framework structure of a dealuminated Y-type zeolite. The Y-type zeolite disclosed in Patent Document 3 has a unit cell constant (UD) of 24.25 to 24.60 Å, a certain crystallinity, specific surface area, and pore diameter, and is characterized in that the proportion of aluminum atoms (coordinated 4) in the framework is 60% or more, and it has been reported to exhibit excellent performance.

[0007] Patent Document 4 discloses a method for producing a high-octane gasoline fraction by bringing a high-aromatic hydrocarbon oil raw material into contact with a hydrocracking catalyst to obtain a high-octane gasoline fraction. The hydrocracking catalyst disclosed in Patent Document 4 is a catalyst using a carrier containing a specific ultra-stable Y-type zeolite on a refractory carrier, and is characterized in that the unit cell constant (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 for the production of gasoline fractions as a hydrocracking catalyst.

[0008] Patent Document 5 discloses a faujasite-type zeolite and a hydrocarbon catalytic cracking catalyst containing the faujasite-type zeolite. Patent Document 5 reports a catalytic cracking catalyst characterized in that the SiO2 / Al2O3 (molar ratio) of the faujasite-type zeolite is 4 to 8, the peak area ratio of extra-framework (coordinated 6) aluminum to framework (coordinated 4) aluminum in solid NMR is 0.4 to 1.0, and the lattice constant is in the range of 24.40 to 24.65 Å.

Prior Art Documents

Patent Documents

[0009]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

[0010] In the future, the contents of vanadium and nickel, which are poisonous substances contained in residual oil, are likely to increase, and there is a demand for a fluid catalytic cracking catalyst that maintains the cracking activity of residual oil even under such circumstances. The conventional fluid catalytic cracking catalysts have a problem in that they cannot obtain sufficient activity.

[0011] The object of the present invention is to provide a zeolite suitable for use as a catalyst component or adsorbent in the fields of petroleum refining and petrochemicals, a method for producing said zeolite, and a catalyst containing said zeolite, particularly a zeolite suitable for use as a fluid catalytic cracking catalyst. [Means for solving the problem]

[0012] Under such technical background, the inventors have conducted intensive research into improving a fluid catalytic cracking catalyst (hereinafter, also simply referred to as "FCC catalyst") having excellent cracking ability for heavy fractions (bottoms), and as a result, have discovered that a fluid catalytic cracking catalyst containing a specific faujasite-type zeolite exhibits heavy fraction (bottoms) cracking ability that is remarkably excellent in hydrothermal stability and resistance to metal poisoning, thereby completing the present invention.

[0013] The zeolite according to the present invention is It has the following characteristics (a) to (c). (a) Faujasite-type zeolite. (b) The peak area of the spectrum of 4-coordinated Al measured by solid-state NMR of alumina (P 4Al ) and the peak area of the spectrum of 6-coordinated Al (P 6Al ) and the peak area ratio (P 6Al ) / (P 4Al ) is in the range of 0.20 to 0.40. (c) The amount of ammonia desorbed measured by the ammonia temperature-programmed desorption method (NH3-TPD method) is in the range of 1.0 to 2.5 mmol / g.

[0014] Regarding the zeolite according to the present invention, (a) The faujasite-type zeolite is ultrastable Y-type zeolite (USY). (i) The faujasite-type zeolite has a lattice constant of zeolite in the range of 24.40 to 24.60 Å. etc. can be considered as more preferable solution means.

[0015] Further, the method for producing zeolite according to the present invention is a method for producing any of the above zeolites, (1) A first step of preparing zeolite, (2) A second step of obtaining a zeolite cake by subjecting the zeolite to acid treatment in the presence of an ammonium salt and then performing solid-liquid separation. (3) A third step of obtaining zeolite from the zeolite cake. It includes these.

[0016] Further, the catalyst according to the present invention contains any of the above zeolites.

Effect of the Invention

[0017] As described above, according to the zeolite and its production method obtained in the present invention, when used as a catalyst, particularly as a fluid catalytic cracking catalyst, it has excellent decomposability of heavy fractions (bottoms), high decomposition activity, and moreover, less generation of hydrogen, gas, and coke, and gasoline and kerosene fractions can be obtained in high yields, and a fluid catalytic cracking catalyst excellent in hydrothermal stability and metal poisoning resistance can be provided. Further, the zeolite of the present invention can be used, for example, as a constituent component of a catalyst used in the petroleum refining and petrochemical fields, and also as an adsorbent.

Embodiment for Carrying Out the Invention

[0018] The zeolite of the present invention was first developed for use as a fluid catalytic cracking catalyst.

[0019] As a fluid catalytic cracking (FCC) catalyst for hydrocarbons, a catalyst composition is conventionally known in which a porous inorganic oxide such as silica-alumina, silica-zirconia, silica-magnesia, or further silica-clay is used as a matrix and fine zeolite is dispersed and contained therein. However, generally, in this type of catalyst composition, the pores of the zeolite may be encapsulated by the matrix component, particularly by the silica component in the matrix, and when this encapsulation occurs, the performance as a catalyst may be significantly reduced.

[0020] <Zeolite> The present invention provides a fluid catalytic cracking catalyst excellent in cracking activity, gasoline selectivity, hydrothermal stability, and metal poisoning resistance by the zeolite dispersed in the matrix. That is, the FCC catalyst according to the present invention contains a specific faujasite-type zeolite in a dispersed state.

[0021] The zeolite used in the present invention is a faujasite-type zeolite, and particularly, ultrastable Y-type zeolite (USY) is suitable because of its excellent hydrothermal stability.

[0022] The USY zeolite of the present invention contains 6-coordinate Al atoms at a specific ratio together with 4-coordinate Al atoms in the framework. The present inventors define the ratio of such 4-coordinate Al atoms and 6-coordinate Al atoms by the ratio of the peak areas using solid-state NMR.

[0023] That is, the peak area (P 4Al ) of the spectrum of 4-coordinate Al measured by solid-state NMR of alumina in the USY zeolite of the present invention and the peak area (P 6Al ) of the spectrum of 6-coordinate Al, and the peak area ratio (P 6Al ) / (P 4Al) is required to 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. If the peak area ratio exceeds the upper limit, it means that there are few 4-coordinate Al (Al atoms in the framework), and the activity may be insufficient.

[0024] In the present invention, the coordination state of aluminum present in the zeolite was determined using a solid high-resolution NMR (Nuclear Magnetic Resonance) apparatus (manufactured by Agilent Technologies: VNS-600). 27 Al 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 rate of 20 kHz, a waiting time of 0.1 sec, and an integration number of 128 times. Before the measurement, the sample was placed in a desiccator containing saturated water vapor of NH4Cl for 24 hours or more to sufficiently adsorb water. Aluminum nitrate nonahydrate (Al(NO3)3·9H2O) was used as an external standard.

[0025] The composition analysis of the zeolite was measured by the glass bead method using a fluorescent X-ray analyzer (manufactured by PHILIPS: MagiX PRO). The lattice constant of the zeolite was measured using a powder X-ray diffractometer (manufactured by Rigaku: RINT-2100). Using Cu-Kα rays, the lattice constant was calculated under the 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 within this range, the amount of solid acid is large and the activity is high. If the lattice constant is too high, the hydrothermal resistance, metal resistance, etc. may be insufficient. If the lattice constant is too low, the amount of solid acid decreases and the activity may be insufficient.

[0026] The specific surface area was measured for the sample powder pretreated at 500 °C for 1 hour in an inert gas atmosphere. The adsorption amount and desorption amount of N2 were measured using MacSorb-1220 manufactured by Mountech. The specific surface area was calculated based on the BET one-point method from the obtained desorption amount of N2.

[0027] The ammonia desorption amount was measured by the ammonia temperature-programmed desorption method (NH3-TPD method). That is, using BELCAT-B (registered trademark) manufactured by MicrotracBEL, 0.2 g of the sample was placed in the measurement cell, degassed at 500 °C for 1 hour, then the temperature was set to 100 °C, and ammonia gas was introduced and adsorbed at 100 °C for 0.5 hour. Next, after degassing again at 100 °C for 0.5 hour, while flowing He gas at 50 ml per minute, the amount of ammonia desorbed as the temperature increased from 100 °C to 700 °C at a rate of 10 °C per minute was measured. The ammonia desorption amount needs to be in the range of 1.0 to 2.5 mmol / g. When the ammonia desorption amount is less than the lower limit, the decomposition activity is insufficient. On the other hand, when it exceeds the upper limit, the amount of coke generated increases, and the gasoline selectivity may decrease.

[0028] In addition to the above fluid catalytic cracking applications, the zeolite of the present invention can be used, for example, as a constituent component of a catalyst used in catalytic cracking and hydrotreating in the petroleum refining and petrochemical fields, and also as an adsorbent for separating organic substances in molecular sieves or in the gas phase or liquid phase.

[0029] <Method for producing zeolite> (1) First step of preparing zeolite As the NaY-type zeolite, a 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 to 6, more preferably 4 to 6.

[0030] Ammonium ion exchange is carried out by dispersing NaY-type zeolite in an aqueous ammonium salt solution to obtain NH4Y-type zeolite. Ion exchange can be carried out by 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, where n is the SiO2 / Al2O3 molar ratio). If the amount of ammonium salt used is small, a predetermined ion exchange rate cannot be achieved, and the residual amount of Na increases, which may significantly reduce the crystallinity of NH4Y-type zeolite 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.

[0031] 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, etc. can be used. Also, steam may be supplied during heating, or NH4Y-type zeolite containing moisture in advance may be used. By heat-treating in the presence of steam, the lattice constant can be adjusted.

[0032] (2) A second step of obtaining a zeolite cake by subjecting zeolite to acid treatment in the presence of an ammonium salt and then performing solid-liquid separation The heat-treated zeolite can be treated with an acid solution in the temperature range of 40 to 100 °C for the purpose of removing extra-framework 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. Also, organic acids such as citric acid and acetic acid may be used as long as they can remove extra-framework aluminum.

[0033] A salt containing ammonium ions may be added to the acid solution in this step. Thus, when acid treatment is carried out using an acid solution containing ammonium ions, Na, which is the counter cation of aluminum, + is more easily removed.

[0034] The acid solution and the zeolite after acid treatment can be separated into solid and liquid by methods such as filtration to obtain a zeolite cake. At this time, since components derived from the acid solution may remain in the separated zeolite, it is preferable to perform a washing process such as suspending the separated zeolite in water again or applying warm water on a filter cloth.

[0035] In addition, since the filtrate contains dissolved aluminosilicate, from the viewpoints of yield and performance, etc., the solid content may be aggregated and recovered. An aggregating agent is added to the filtrate to obtain a precipitate containing dissolved aluminosilicate from the filtrate. The recovered dissolved aluminosilicate is separated into solid and liquid by methods such as filtration, and then a washing process such as suspending it in water again or applying warm water on a filter cloth is performed to obtain a dissolved aluminosilicate cake. Also, when obtaining the dissolved aluminosilicate cake, a device for concentrating and sedimenting a slurry such as a thickener may be used. For example, using a thickener as an actual machine, the filtrate added with an aggregating agent can be concentrated and sedimented, and directly mixed with a filtration device such as an Oliver filter and washed.

[0036] As the aggregating agent, inorganic aggregating agents such as polyaluminum chloride and ferric polysulfate, and organic polymer aggregating agents such as polyacrylate-based and polyacrylamide-based are preferable, and both may be used in combination. As the organic polymer aggregating agent, at least one type of cationic, anionic, nonionic, or amphoteric can be used.

[0037] (3) The third step of obtaining zeolite from the zeolite cake The zeolite cake can be dried in the temperature range of 80 °C or higher and 400 °C or lower to obtain zeolite. Further, if necessary, this zeolite may be calcined in an air atmosphere in the temperature range of 400 °C or higher and 900 °C or lower.

[0038] As a catalyst containing the zeolite of the present invention, a fluid catalytic cracking catalyst will be described as an example. - Fluid catalytic cracking catalyst - The fluid catalytic cracking catalyst according to the present invention includes a matrix containing a binder component containing silica or alumina and the zeolite prepared above (hereinafter also simply referred to as zeolite), and an additive containing at least one selected from activated alumina and a metal scavenger, and may further contain a rare earth metal oxide. These zeolites are used in a form ion-exchanged with cations selected from hydrogen, ammonium, and polyvalent metals, in the same manner as when used in ordinary catalytic cracking catalysts.

[0039] As the precursor of the rare earth metal oxide in the present invention, generally commercially available rare earth metal carbonates, hydrochlorides, nitrates, oxalates, etc. can be used.

[0040] The fluid catalytic cracking catalyst according to the present invention uses a porous inorganic oxide matrix in the same manner as an ordinary catalytic cracking catalyst. For the porous inorganic oxide matrix, silicates 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. Further, as additives, clay minerals such as kaolin, halloysite, and montmorillonite, activated alumina, matrices having solid acids such as silica-alumina, silica-magnesia, alumina-magnesia, silica-magnesia-alumina, and metal scavengers such as manganese dioxide, calcium aluminate, aluminum hydroxide, and rare earth metal oxides (for example, lanthanum carbonate, etc.) can be used in combination.

[0041] 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 above-mentioned zeolite is preferably contained in the range of 5 to 50% by mass, more preferably 10 to 40% by mass, based on the catalyst. When the above-mentioned rare earth metal oxide is included, the content in terms of oxide conversion (RE2O3) is 0.5% by mass or more, preferably 0.8% by mass or more, more preferably 1.0% by mass or more, based on the catalyst, and at most 20% by mass or less, preferably 18% by mass or less, more preferably 15% by mass or less, and it is desirable that they are uniformly dispersed in the above-mentioned porous inorganic oxide matrix.

[0042] If the content of the zeolite 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 is too high, and the production of hydrogen, gas, and coke increases, resulting in a possible decrease in gasoline yield. Also, if the content of the precursor of the rare earth metal oxide is less than 0.5% by mass as RE2O3, the desired effect cannot be obtained. On the other hand, if it is more than 20% by mass, the attrition resistance (Attr.Res.) of the catalyst composition may decrease. In the fluid catalytic cracking catalyst, it is desirable that the above-mentioned porous inorganic oxide matrix is contained in the range of 30 to 90% by mass, preferably 30 to 85% by mass. It should be noted that each component of the catalyst composition is determined within its respective range so that the total is 100% by mass.

[0043] - Method for producing fluid catalytic cracking catalyst - As a method for producing the above-mentioned fluid catalytic cracking catalyst, a method will be described by taking as an example a method in which a mixture slurry obtained by adding the zeolite to basic aluminum chloride, which is the above-mentioned porous inorganic oxide matrix precursor, and uniformly dispersing it is spray-dried and washed in the following steps. When a silica-based binder is used, the conditions may be different, and in that case, it will be described in parentheses.

[0044] <Mixed slurry acquisition step> A step of obtaining a mixed slurry including a matrix containing a binder component and zeolite, and an additive including at least one selected from activated alumina and a metal scavenger is defined as a mixed slurry obtaining step. The mixed slurry obtained here is preferably adjusted so that the solid content concentration is in the range of 25 to 50% by mass in order to be suitable for the subsequent spray drying step. If the solid content concentration is less than 25% by mass, the bulk density of the catalyst decreases and the abrasion resistance deteriorates. If it exceeds 50% by mass, spray drying may become difficult due to an increase in the viscosity of the mixed slurry.

[0045] <Precursor obtaining step> A 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 defined as a precursor obtaining step. The conditions for spray drying 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 after washing the catalyst, and the abrasion resistance deteriorates. On the other hand, if it exceeds 250 °C, although the particle shape after washing can be maintained, the drying speed becomes fast, so cracks and the like are likely to occur in the catalyst particles, and conversely, the abrasion resistance may deteriorate.

[0046] <Washing cake 1 obtaining step> A step of suspending the precursor of the fluid catalytic cracking catalyst obtained in the precursor obtaining step in an aqueous solution at 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) and at 40 to 70 °C, then performing filtration, and if necessary, further washing with warm water and performing filtration to obtain washing cake 1 is defined as a washing 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 hydrogen carbonate, and sodium hydroxide, and it is preferably adjusted so that the pH of the aqueous solution is within the desired range before use. In the case of sodium hydroxide, it is preferably used in combination with ammonium sulfate.

[0047] If the temperature of the aqueous solution is lower than 40°C, the amount of residual chlorine derived from the binder component increases, increasing the likelihood of corrosion of the fluidized catalytic cracking apparatus. On the other hand, if the temperature is higher than 70°C, hydrolysis of the binder component is likely to occur, and the abrasion resistance may deteriorate. (When using a silica-based binder, the temperature of the aqueous solution during washing does not need to be particularly limited, but it is preferably carried out in the range of 50 to 70°C.)

[0048] Furthermore, from the viewpoints of solubility impurities and filterability, 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 by mass ratio.

[0049] <Washing cake 2 acquisition step> The step of drying the washing cake 1 obtained in the washing cake 1 acquisition step to obtain a washing cake 2 is defined as the washing cake 2 acquisition step. Before drying, it is preferably suspended in water, and then, if necessary, an aqueous solution containing a RE2O3 precursor of a rare earth element is added and stirred, followed by filtration and further washing with warm water.

[0050] <Heating and drying step> The step of heating the washing cake 2 obtained in the washing cake 2 acquisition step in a general manner such as a dryer, muffle furnace, rotary kiln, etc. in the temperature range of 80 to 600°C to obtain the fluidized catalytic cracking catalyst of the present invention is defined as the heating and drying step. Also, it may be carried out under arbitrary conditions such as air or steam. If the temperature is less than 80°C, drying may be insufficient and the physical properties and performance of the catalyst during use may deteriorate. On the other hand, if the temperature exceeds 600°C, the performance may decrease due to aggregation of the active components etc.

[0051] The fluidized catalytic cracking catalyst of the present invention can be used in the conventional hydrocarbon oil fluidized catalytic cracking method, and the conventional fluidized catalytic cracking conditions can be adopted. Also, the catalyst composition of the present invention can be used for the fluidized catalytic cracking of any conventional hydrocarbon oil feedstock oil, but it has excellent hydrothermal resistance and is particularly preferably used for the fluidized catalytic cracking of heavy hydrocarbon oils containing nickel, vanadium, etc.

[0052] In addition to the above fluid catalytic cracking catalyst, the zeolite of the present invention can also be suitably used as a catalyst for petroleum refining such as hydrocracking and isomerization, a catalyst for petrochemical synthesis such as xylene, ethylbenzene, and cumene, and a catalyst for fine chemicals synthesis.

Example

[0053] Examples are shown below to specifically describe this example, but the present invention is not limited by these examples. (Example 1) · Preparation of ultrastable Y-type zeolite No.1 As the NaY-type zeolite, one with a SiO2 / Al2O3 (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% by mass in terms of Na2O was used. 50.0 kg of the NaY-type zeolite was added to 500 L of warm 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 then filtered. The solid obtained by filtration was washed with warm 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 warm water at 60 °C, and further washed with 500 L of water at 60 °C to obtain a washed cake. The obtained washed cake was dried at 130 °C for 20 hours to obtain a Y-type zeolite (NH4Y) in which about 65% by mass of the Na contained in the NaY-type zeolite was ion-exchanged with ammonium ions (NH4 + ). The Na content of this NH4Y-type zeolite was 4.5% by mass in terms of Na2O (first step).

[0054] 40 kg of this NH4Y-type zeolite was calcined at 670 °C for 1 hour in a saturated steam atmosphere. The obtained calcined powder was added to 400 L of warm water at 60 °C, adjusted to pH 2.5 - 4.5 with 25% sulfuric acid, then 49.0 kg of ammonium sulfate was added, and the mixture was stirred at 90 °C for 1 hour. The obtained slurry was filtered and then washed with 200 L of warm water at 60 °C to obtain a washed cake (1) (second step). The obtained washed cake (1) was added to 400 L of warm water at 60°C and stirred at 60°C for 10 minutes. The obtained slurry was filtered and then washed with 200 L of warm water at 60°C to obtain a washed cake (2). Then, the washed cake (2) was dried at 130°C for 20 hours to obtain zeolite No. 1 of ultrastable Y type (hereinafter referred to as "USY") (third step). The properties of zeolite No. 1 of USY are shown in Table 1. In this example, although the step of using a flocculant was carried out with the intention of improving the yield, it has been confirmed that when the flocculant is not used, although a decrease in the yield is observed, the physical properties of the obtained zeolite are almost the same.

[0055] · Preparation of fluid catalytic cracking catalyst No. 1 For the fluid catalytic cracking catalyst, zeolite No. 1 of USY that had been further calcined at 830°C for 30 minutes was 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 continuously added simultaneously 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 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 prepare a mixed slurry. This mixed slurry was spray-dried as droplets in a spray dryer with an inlet temperature of 250°C and an outlet temperature of 150°C to obtain dry particles with an average particle size of 70 μm. The obtained spray-dried particles were suspended in 10 times the mass of warm water (60°C) and dehydrated and filtered. Then, after spraying 10 times the mass of warm water (60°C), they were further suspended and contacted with an aqueous solution of rare earth metal (including chlorides of cerium and lanthanum) chlorides, and ion-exchanged treatment was carried out so that it became 2.0% by mass as RE2O3. Then, the cake was recovered and dried in a dryer maintained at an atmospheric temperature of 150°C for 10 hours 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.

[0056] (Example 2) · Preparation of Ultra-Stable 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 NH4Y-type zeolite obtained in Example 1 was calcined at 590 °C for 1 hour in a saturated steam atmosphere. 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.

[0057] (Example 3) · Preparation of Ultra-Stable 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 NH4Y-type zeolite obtained in Example 1 was calcined at 695 °C for 1 hour in a saturated steam atmosphere. 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.

[0058] (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.

[0059] (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 obtained calcined powder was added to 400 L of warm water at 60 °C, adjusted to pH 2.5 - 4.5 with 25% sulfuric acid, then 49.0 kg of ammonium sulfate was added, and the mixture was stirred at 90 °C for 1 hour. The obtained slurry was filtered, then washed with 200 L of warm water at 60 °C to obtain a washed cake (4). Next, the washed cake (4) was 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 A 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.

[0060] (Comparative Example 3) · Preparation of USY Zeolite No. R3 Similar to Example 1, 40 kg of NH4Y-type zeolite was calcined at 670 °C for 1 hour in a saturated steam atmosphere. The obtained calcined powder was added to 400 L of warm water at 60 °C, 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 warm water at 60 °C. Next, this solid was dried at 130 °C for 20 hours. The obtained dried powder was calcined at 750 °C for 2 hours in a saturated steam atmosphere and in 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 A 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, it was used without the additional calcination at 830 °C for 30 minutes. The catalyst composition and catalyst properties of fluid catalytic cracking catalyst No. R3 are shown in Table 2.

[0061] [Catalyst Activity Evaluation Test] For the catalysts of each inventive example and comparative example, a catalyst performance evaluation test was conducted using ACE-MAT (Advanced Cracking Evaluation Micro Activity Test). However, before conducting these performance evaluation tests, the catalyst obtained as described above was pre-fired at an ambient temperature of 600 °C for 2 hours. Thereafter, a predetermined amount of nickel octylate and vanadium octylate was deposited on the fired catalyst particles. Subsequently, it was dried at an ambient temperature of 110 °C, fired at an ambient temperature of 600 °C for 1.5 hours, and then heat-treated under various steam atmospheres to perform a pseudo-equilibration treatment of the catalyst. The pretreatment conditions are shown in Table 3. Conditions No. S1 was used as the standard, and Conditions No. S2 with nickel and vanadium deposited and Condition No. S3 with a high steaming firing temperature were used.

[0062] The operating conditions in the activity evaluation test are as follows. Feedstock oil: Desulfurized atmospheric residue (DSAR) + desulfurized vacuum gas oil (DSVGO) of crude oil (50 + 50) Mass ratio of catalyst to oil throughput (C / O): 5.00 Reaction temperature: 520 °C 1) Conversion rate = 100 - (LCO + HCO) 2) Boiling range of gasoline: 30 - 216 °C 3) Boiling range of LCO: 216 - 343 °C (LCO: Light Cycle Oil) 4) Boiling range of HCO: 343 °C + (HCO: Heavy Cycle Oil)

[0063] Table 4 shows the results of the metal resistance test for nickel and vanadium on the catalyst. In all examples, the conversion rate and gasoline yield after metal treatment are higher than those in the comparative examples, and the retention rate of the conversion rate is high. Therefore, it can be evaluated that the catalyst has excellent metal resistance.

[0064] Table 5 shows the results of the hydrothermal resistance test on the catalyst. In all inventive examples, the conversion rate is higher and retained than that in the comparative examples even when the steaming firing temperature is increased. Therefore, it can be evaluated that the catalyst has excellent hydrothermal resistance.

[0065]

Table 1

[0066]

Table 2

[0067]

Table 3

[0068]

Table 4

[0069]

Table 5

Claims

【Claim 1】 The peak area (P ４Ａｌ ) of the spectrum of four-coordinate Al measured by solid-state NMR of alumina and the peak area (P ６Ａｌ ) of the spectrum of six-coordinate Al, and the peak area ratio (P ６Ａｌ ) / (P ４Ａｌ ) are in the range of 0.20 to 0.40, A forger site type zeolite in which the ammonia desorption amount measured by the ammonia temperature-programmed desorption method (NH ３ -TPD method) is in the range of 1.0 to 2.5 mmol / g. **Claim 2**: The faujasite-type zeolite according to claim 1, wherein the lattice constant is in the range of 24.40 to 24.60 Å. **Claim 3**: A process for preparing a zeolite, a step of subjecting the zeolite to acid treatment in the presence of an ammonium salt and then performing solid-liquid separation to obtain a first zeolite cake; a step of suspending the first zeolite cake in water to obtain a suspension; a step of performing solid-liquid separation on the suspension to obtain a second zeolite cake; and a step of drying the second zeolite cake at 80 to 400 °C. A method for producing a faujasite-type zeolite, comprising these steps. **Claim 4**: A catalyst comprising the faujasite-type zeolite according to claim 1.

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