JP7570870B2 - Method for producing simulated equilibrium fluid catalytic cracking catalyst - Google Patents

Description

Article 30, paragraph 2 of the Patent Act applies [1] (1) Date of issue October 31, 2019 (2) Publication Invited lecture at the Yamagata Convention of the Japan Petroleum Society, 49th Petroleum and Petrochemical Symposium, Lecture Abstracts, Published by the Japan Petroleum Society, Public Interest Incorporated Association <References> Excerpts from the lecture abstracts at the 49th Petroleum and Petrochemical Symposium [2] (1) Date held (publication date) October 31, 2019 (2) Name and venue of the conference The Yamagata Convention of the Japan Petroleum Society, 49th Petroleum and Petrochemical Symposium (Dates: October 31 and November 1, 2019) 1-2-3 Futaba-cho, Yamagata City Yamagata Terrsa, Hall D <References> Summary and presentation program of the 49th Petroleum and Petrochemical Symposium Webpage Printout <References> Research presentation slides at the 49th Petroleum and Petrochemical Symposium

The present invention relates to a method for producing a simulated equilibrium fluid catalytic cracking catalyst.

Fluid catalytic cracking is a reaction in which feedstock oils, including heavy oil, are cracked by contacting them with a fluid catalytic cracking catalyst at high temperatures in a fluid catalytic cracking unit to obtain high-value-added cracked oils such as gasoline, kerosene, and diesel. As a fluid catalytic cracking catalyst, for example, a solid acid catalyst containing zeolite and activated alumina as its main components is used. In a fluid catalytic cracking reaction, the activity of the fluid catalytic cracking catalyst decreases due to the accumulation of coke produced by the reaction and the accumulation of metals contained in the feedstock oil.

The decrease in activity due to coke accumulation occurs when coke is produced during the fluid catalytic cracking reaction, covering the active sites of the fluid catalytic cracking catalyst and blocking the pores.

Therefore, in the fluid catalytic cracking unit, the fluid catalytic cracking catalyst on which the coke has accumulated is stripped with steam and then transferred to a regeneration tower, where the coke is burned off at high temperatures under air flow to regenerate the fluid catalytic cracking catalyst and reuse it in the reaction.

When heavy oil is used as the feedstock, metals such as nickel, vanadium, iron, and copper are present in large quantities in the heavy oil in the form of organometallic compounds (e.g., porphyrins), and these metals are demetalized by the fluid catalytic cracking catalyst and deposited on the fluid catalytic cracking catalyst, causing a decrease in activity due to metal deposition. In other words, as metals deposit on the fluid catalytic cracking catalyst, cracking activity decreases, making it virtually impossible to achieve the desired conversion rate. Furthermore, the amount of hydrogen and coke produced increases significantly, making it difficult to operate the fluid catalytic cracking unit. As a result, the yield of desirable liquid products decreases.

Of the above metals, vanadium in particular destroys the crystal structure of zeolite, the active component of fluid catalytic cracking catalysts, reducing cracking activity. Nickel also has dehydrogenation catalytic activity, which significantly increases hydrogen and coke, thereby reducing the cracking activity of the fluid catalytic cracking catalyst and making it difficult to operate the fluid catalytic cracking unit.

As mentioned above, fluid catalytic cracking catalysts whose activity has decreased due to coke accumulation can be regenerated in the fluid catalytic cracking unit by burning off the coke at high temperatures under air flow in the regeneration tower of the fluid catalytic cracking unit. On the other hand, it is virtually impossible to regenerate fluid catalytic cracking catalysts whose activity has decreased due to metal accumulation in the fluid catalytic cracking unit. For this reason, a method is used in which part of the fluid catalytic cracking catalyst with decreased activity is periodically or steadily removed and the required amount of new catalyst is added to maintain the activity of the fluid catalytic cracking catalyst in the fluid catalytic cracking unit. In this way, the fluid catalytic cracking catalyst in the fluid catalytic cracking unit is called an equilibrium catalyst because its activity is kept constant while it is added and removed.

Therefore, when evaluating the performance of a fluid catalytic cracking catalyst, it is necessary to evaluate the activity of the equilibrium catalyst, not the new catalyst. On the other hand, in order to obtain an equilibrium catalyst, the fluid catalytic cracking reaction must be carried out for a certain period of time while removing catalyst with reduced activity and introducing new catalyst. Therefore, a simple method for producing a simulated equilibrium fluid catalytic cracking catalyst is desired in order to evaluate the performance of a fluid catalytic cracking catalyst.

The Mitchell process is known as a method for producing a simulated equilibrium fluid catalytic cracking catalyst, and consists of a drying process for new catalyst, a process for impregnating the dried new catalyst with nickel and vanadium, a process for calcining the resulting impregnated body, and a process for steaming the resulting calcined body. On the other hand, although the Mitchell process is a simple method, in terms of performance, it is not possible to accurately reproduce the equilibrium catalyst of an actual machine.

Patent Document 1 describes that in an actual equilibrium catalyst, nickel is unevenly distributed in an egg shell shape, while vanadium is uniformly distributed. On the other hand, in a simulated equilibrium catalyst produced by the Mitchell method, both nickel and vanadium are uniformly distributed, and it is suggested that this difference in distribution affects activity.

Patent Document 1 describes a process for continuously supplying new catalyst from a catalyst tank, a heating/calcining/steaming process in which the supplied new catalyst and a metal-attached catalyst to which metal has been attached are introduced into a mixed atmosphere of air and high-temperature steam, the new catalyst and the metal-attached catalyst are heated to a predetermined temperature, and the new catalyst and the metal-attached catalyst are calcined and steamed, and a mixed catalyst consisting of the treated new catalyst and the metal-attached catalyst is continuously delivered, a transporting process in which the mixed catalyst is transported while being maintained in a high-temperature state, a cooling process in which the transported mixed catalyst is cooled to a predetermined cooling temperature, and a spray-like catalyst produced by atomizing a metal solution in which a metal or metal compound is dissolved in a solvent with an inert gas. The method for producing a simulated equilibrium fluid catalytic cracking catalyst is characterized in that it comprises a metal attachment process in which the above solution is attached to a mixed catalyst, heated, and the solvent is evaporated to continuously produce a metal-attached catalyst, and a stripping process in which an inert gas is introduced to strip the mixed catalyst, and the metal-attached catalyst obtained by separating the vapor of the solution attached to the mixed catalyst is continuously sent to a heating/calcining/steaming process, and new catalyst is introduced to the heating/calcining/steaming process while the new catalyst and the metal-attached catalyst are circulated between the heating/calcining/steaming process and the stripping process.

It has been disclosed that the simulated equilibrium fluid catalytic cracking catalyst produced by the above-mentioned production method has nickel unevenly distributed in an egg shell shape and vanadium evenly distributed, similar to the actual equilibrium catalyst, and can accurately reproduce the performance of the actual equilibrium catalyst.

Japanese Patent Application Publication No. 11-179192

As described above, although the Mitchell method is a simple method, in terms of performance, it is not possible to accurately reproduce the equilibrium catalyst of the actual plant. In particular, in the simulated equilibrium catalyst produced by the Mitchell method, nickel is uniformly distributed, so that the dehydrogenation catalytic activity of nickel is higher than that of the actual equilibrium catalyst, and the amount of coke produced is larger than that of the actual equilibrium catalyst.
In addition, although the simulated equilibrium fluid catalytic cracking catalyst produced by the production method described in Patent Document 1 can accurately reproduce the performance of an actual equilibrium catalyst, there are problems in that the process is complicated, and therefore dedicated equipment is required and production takes a long time.

The present invention has been made in consideration of the above circumstances, and aims to provide a method for producing a simulated equilibrium fluid catalytic cracking catalyst that can accurately reproduce the performance of a real equilibrium catalyst and can be produced in a simple process. In particular, the present invention aims to provide a method for producing a simulated equilibrium fluid catalytic cracking catalyst that can accurately reproduce the performance of a real equilibrium catalyst with respect to the amount of coke produced and can be produced in a simple process.

In order to solve the above problems, the present invention has the following aspects.
[1] A method for producing a catalytic cracking catalyst comprising: an impregnation step in which a first liquid containing a nickel compound and a first solvent and a second liquid containing a second solvent are impregnated into a fluid catalytic cracking catalyst, and then removing the first and second solvents to obtain an impregnated body; a calcination step in which the impregnated body is calcined at 500 to 800 ° C to obtain a calcined body; and a steam treatment step in which a gas containing water vapor is contacted with the calcined body, the combination of the first liquid and the second liquid being selected so that the distance (Ra) of the Hansen solubility parameters of the first liquid and the second liquid is a predetermined value; and the steam treatment step is performed by subjecting a first gas containing a reducing gas and 30 to 70% by volume of water vapor to a temperature of 700 to 900 ° C., a GHSV of 300 to 700 h. and, after the reducing steam treatment, an oxidizing steam treatment in which a second gas containing an oxidizing gas and 30 to 70 volume % of steam is contacted with the calcined body under conditions of a temperature of 700 to 900°C and a ^GHSV of 300 to 700 h ^-1 .
[2] The method for producing a simulated equilibrium fluid catalytic cracking catalyst according to [1], wherein the ratio of the reducing gas contained in the first gas is 1 to 5 volume %.
[3] The method for producing a simulated equilibrium fluid catalytic cracking catalyst according to [1] or [2], wherein the ratio of the oxidizing gas contained in the second gas is 5 to 20 volume %.
[4] The method for producing a simulated equilibrium fluid catalytic cracking catalyst according to any one of [1] to [3], wherein the cycle is carried out 20 to 50 times.
[5] The method for producing a simulated equilibrium fluid catalytic cracking catalyst according to any one of [1] to [4], wherein the reducing steam treatment is carried out for a total of 3 to 9 hours.
[6] The method for producing a simulated equilibrium fluid catalytic cracking catalyst according to any one of [1] to [5], wherein the oxidative steam treatment is carried out for a total of 3 to 9 hours.
[7] The method for producing a simulated equilibrium fluid catalytic cracking catalyst according to any one of [1] to [6], wherein the second gas contains 1000 to 4000 ppm by volume of sulfur dioxide.
[8] The method for producing a simulated equilibrium fluid catalytic cracking catalyst according to any one of [1] to [7], wherein the Ra is 10 MPa ^1/2 or more.
[9] The method for producing a simulated equilibrium fluid catalytic cracking catalyst according to any one of [1] to [8], wherein the second liquid has a relative energy difference (RED) based on Hansen solubility parameters with respect to the first liquid that is greater than 1.
[10] The method for producing a simulated equilibrium fluid catalytic cracking catalyst according to any one of [1] to [9], wherein the first liquid is impregnated after the second liquid is impregnated.

According to the present invention, it is possible to provide a method for producing a simulated equilibrium fluid catalytic cracking catalyst that can accurately reproduce the performance of a real equilibrium catalyst and can be produced in a simple process. In particular, it is possible to provide a method for producing a simulated equilibrium fluid catalytic cracking catalyst that can accurately reproduce the performance of a real equilibrium catalyst with respect to the amount of coke produced and can be produced in a simple process.

FIG. 1 is a schematic diagram showing how to determine the Hansen solubility parameter and the interaction radius. FIG. 2 is a schematic diagram showing the distance between the Hansen solubility parameter of a first liquid and the Hansen solubility parameter of a second liquid; 1 is a graph showing the distribution of nickel element obtained by EPMA analysis of catalyst A of Example 1. FIG. 2 is a mapping diagram of nickel element obtained by EPMA analysis of catalyst A in Example 1. 1 is a graph showing the distribution of nickel element obtained by EPMA analysis of catalyst C of Comparative Example 1. FIG. 2 is a mapping diagram of nickel element obtained by EPMA analysis of catalyst C of Comparative Example 1.

The following describes in detail the embodiments of the present invention. However, the following description is merely an example of the embodiments of the present invention, and the present invention is not limited to these contents, and can be modified and implemented within the scope of the gist of the invention.

In this specification, the term "solvent" refers to a substance that is in a liquid state at normal pressure (101,325 Pa) and 20°C and is composed of one compound that does not contain any metal element.
In this specification, the term "boiling point" means the boiling point at normal pressure (101,325 Pa).
In this specification, the "total pore volume" can be measured by mercury intrusion porosimetry.
In this specification, the distribution of metal components in the depth direction of the simulated equilibrium fluid catalytic cracking catalyst can be analyzed by electron probe microanalyzer (EPMA).
In this specification, "fluid catalytic cracking catalyst" means a new catalyst of a fluid catalytic cracking catalyst, and "simulated equilibrium fluid catalytic cracking new catalyst" means a fluid catalytic cracking catalyst that imitates the equilibrium catalyst of the fluid catalytic cracking catalyst produced by the production method of the present invention.

The method for producing a simulated equilibrium fluid catalytic cracking catalyst (hereinafter also simply referred to as a "simulated equilibrium catalyst") of this embodiment (hereinafter also simply referred to as a "catalyst production method") includes an impregnation step of impregnating a fluid catalytic cracking catalyst with a first liquid containing a nickel compound and a first solvent, and a second liquid containing a second solvent, and then removing the first solvent and the second solvent to obtain an impregnated body, a calcination step of calcining the impregnated body at 500 to 800°C to obtain a calcined body, and a steam treatment step of contacting the calcined body with a gas containing water vapor. A combination of the first liquid and the second liquid is selected so that the distance (Ra) between the Hansen solubility parameters of the first liquid and the second liquid is a predetermined value. The steam treatment step is a reducing steam treatment in which a first gas containing a reducing gas and 30 to 70% by volume of steam is brought into contact with the fired body under conditions of a temperature of 700 to 900°C and a GHSV of 300 to 700h ^- 1, and after the reducing steam treatment, a second gas containing an oxidizing gas and 30 to 70% by volume of steam is brought into contact with the fired body under conditions of a temperature of 700 to 900°C and a GHSV of 300 to 700h ^-1 . This cycle is performed at least once.
Each step will be explained below.

<Impregnation process>
In the impregnation step of the present embodiment, a first liquid containing a nickel compound and a first solvent and a second liquid containing a second solvent are impregnated into a fluid catalytic cracking catalyst, and then the first solvent and the second solvent are removed to obtain an impregnated body. A combination of the first liquid and the second liquid is selected so that the distance (Ra) between the Hansen solubility parameters of the first liquid and the second liquid is a predetermined value.

<Hansen Solubility Parameters>
Hansen solubility parameters (hereinafter simply referred to as "HSP") are based on the idea that two substances with similar intermolecular interactions are likely to dissolve in each other. HSP is composed of energy (δd) derived from intermolecular dispersion forces, energy (δp) derived from intermolecular dipole interactions, and energy (δh) derived from intermolecular hydrogen bonds. These three parameters can be regarded as coordinates in a three-dimensional space (Hansen space).

The HSP value of an evaluation sample having an unknown HSP value can be calculated by the following method.
In the Hansen solubility parameter space specified by plotting the HSP values (δd _m , δp _m , δh _m ) in a three-dimensional space, a number of pure substances (substances consisting of one type of compound) having known HPS values are plotted, and the Hansen sphere is specified based on the presence or absence of the solubility of the evaluation sample in the pure substances, and the HSP value of the evaluation sample is calculated by determining the central value of the Hansen sphere (Hansen sphere method).
The HSP value of the evaluation sample can also be calculated from information on the average molecular structure by using the atomic group contribution method.
In both the Hansen Solubility Parameters in Practice (HSPiP) and the group contribution method, the HSP value of the evaluation sample can be calculated using, for example, computer software Hansen Solubility Parameters in Practice (HSPiP).
In the case of the Hansen ball method, the evaluation sample may be a pure substance or a mixture.

A method for determining the central values of the Hansen sphere, that is, the HSP values (δd _m , δp _m , δh _m ), will be described with reference to FIG.
First, the HSP values of about 15 to 30 pure substances having known HSP values are plotted in the three-dimensional space (coordinate axes being the dispersion force term δd, the dipole-dipole force term δp, and the hydrogen bond force term δh) illustrated in FIG.
At this time, for example, pure substances that show solubility in the evaluation sample are indicated by a circle, and pure substances that do not show solubility in the evaluation sample are indicated by a cross, as shown in Figure 1. Next, based on the plotted solubilities of the evaluation samples, the phantom sphere that includes the pure substances that show solubility (indicated by a circle in Figure 1) and does not include the pure substances that do not show solubility (indicated by a cross in Figure 1) and has the smallest radius is determined as the Hansen sphere S (shown as a sphere in Figure 1).
The radius of the Hansen sphere S (the minimum radius) is the interaction radius _R0 that dissolves the pure substance shown by the circle in the figure and indicates compatibility, and the central values (δd _m , δp _m , δh _m ) of the obtained Hansen sphere S are the HSP values of the evaluation sample.
The HSP values of the above pure substances used to determine the Hansen sphere are, for example, a dispersion term δd of about 10 to 25 MPa ^1/2 , a dipole-dipole term δp of about 0 to 20 MPa ^1/2 , and a hydrogen bond term δh of about 0 to 20 MPa ^1/2 .
In addition, since solubility depends on temperature, when determining the Hansen ball, it is preferable to carry out the solubility test at a temperature at which the evaluation sample actually dissolves.

When the evaluation sample is a mixture of two or more substances, the HSP value of the mixture may be determined by the method described above, or may be determined as a weighted average of the HSP values of the substances constituting the mixture as described below.
A mixture L is composed of substances _L1 to _Lz , and the content ratios of substances _L1 to _Lz to the total volume of all substances before mixing are V( _L1 ) to V( _Lz ), respectively. If the HSP values of substances _L1 to _Lz are [δd( _L1 ), δp( _L1 ), δh( _L1 )] to [δd( _Lz ), δp( _Lz ), δh( _Lz )], respectively, the HSP values of the mixture, [δd(L), δp(L), δh(L)], can be calculated by the following formulas 3 to 5.

2 is a schematic diagram showing the distance between the HSP values of the first liquid and the second liquid in this embodiment. When the HSP values of the first liquid are ( _δd1 , _δp1 , _δh1 ) and the HSP values of the second liquid are ( _δd2 , _δp2 , _δh2 ), the distance between the HSP values (hereinafter also simply referred to as "Ra") can be calculated by the following formula 1.
Ra={4×(δd ₁ - δd ₂ ) ² + (δp ₁ - δp ₂ ) ² + (δh ₁ - δh ₂ ) ² } ^0.5 Equation 1

In this embodiment, the distribution of the nickel component derived from the nickel compound contained in the first liquid in the depth direction of the simulated equilibrium catalyst can be controlled by setting the Ra of the first liquid and the second liquid to a predetermined value. The nickel component derived from the nickel compound contained in the first liquid can be unevenly distributed in the depth direction as the Ra value increases (i.e., can be unevenly distributed outside the FCC catalyst), and the smaller the Ra value, the more gradual the distribution can be formed.
In the case where the nickel component derived from the nickel compound contained in the first liquid is unevenly distributed in the depth direction of the FCC catalyst, Ra is preferably 10 MPa ^1/2 or more, more preferably 12 MPa ^1/2 or more, and even more preferably 14 MPa ^1/2 or more. When Ra is equal to or more than the lower limit, it becomes easier to control the distribution of the nickel component in the depth direction of the obtained simulated equilibrium catalyst. Note that since the value of Ra varies greatly depending on the nickel compound and solvent (first solvent, second solvent) used, there is no upper limit, but it is often substantially about 30 or less.

In this embodiment, it is preferred that the relative energy difference of the second liquid with respect to the first liquid is greater than 1 based on the Hansen solubility parameters.
The relative energy difference (hereinafter, also simply referred to as "RED") of the second liquid to the first liquid based on the Hansen solubility parameters can be calculated by the following formula 2, where the interaction radius of the first liquid is _R0 .
RED=Ra/R ₀ formula 2

In this embodiment, RED is preferably greater than 1. When RED is greater than 1, it becomes easier to control the depth distribution of the nickel component derived from the nickel compound in the resulting simulated equilibrium catalyst. Note that since the value of RED varies greatly depending on the nickel compound and solvent (first solvent, second solvent) used, there is no upper limit, but in practice it is often about 10 or less.

The first liquid, second liquid, and fluid catalytic cracking catalyst used in the catalyst manufacturing method of this embodiment are described below.

<First Liquid>
In the present embodiment, the first liquid contains a nickel compound and a first solvent. More specifically, the first liquid is a solution in which the nickel compound is dissolved in the first solvent. The nickel compound and the first solvent contained in the first liquid will be described below.

The form of the nickel compound contained in the first liquid may be appropriately selected depending on the solubility in the first solvent, the second liquid used, and the desired Ra and RED, and examples include inorganic salts such as chlorides, sulfides, nitrates, and carbonates, organic salts such as oxalates, acetylacetonate salts, dimethylglyoxime salts, ethylenediamine acetate salts, and carboxylate salts, or chelate compounds, carbonyl compounds, cyclopentadienyl compounds, ammine complexes, alkoxide compounds, and alkyl compounds.
Examples of such nickel compounds include nickel octylate, nickel naphthenate, etc. The octyl group in nickel octylate may be a linear octyl group (n-octyl group) or a branched octyl group, and among these, nickel 2-ethylhexanoate is preferred.

A single nickel compound may be used, or two or more types may be used in combination.

The first liquid may contain other metal compounds in addition to the nickel compound. Examples of other metal compounds include metals contained in the feedstock oil for the fluid catalytic cracking reaction, such as vanadium, iron, sodium, zinc, aluminum, barium, calcium, magnesium, phosphorus, lead, molybdenum, chromium, cadmium, arsenic, selenium, and silicon. Of these, vanadium is preferably included because it contributes greatly to the decrease in activity of the fluid catalytic cracking catalyst.

The form of the metal compound other than nickel contained in the first liquid may be appropriately selected depending on the solubility in the first solvent, the second liquid used, and the desired Ra and RED, and examples include inorganic salts such as chlorides, sulfides, nitrates, and carbonates, organic salts such as oxalates, acetylacetonate salts, dimethylglyoxime salts, ethylenediamine acetate salts, and carboxylate salts, or chelate compounds, carbonyl compounds, cyclopentadienyl compounds, ammine complexes, alkoxide compounds, and alkyl compounds.
Examples of such metal compounds other than nickel include metal octylate compounds, metal naphthenate compounds, etc. When a vanadium compound is used as the metal compound other than nickel, examples include vanadium octylate and vanadium naphthenate. The octyl group in vanadium octylate may be a linear octyl group (n-octyl group) or a branched octyl group, and among these, vanadium 2-ethylhexanoate is preferred.

When a vanadium compound is used as the metal compound other than nickel, one type of vanadium compound may be used alone, or two or more types may be used in combination.

The first solvent may be appropriately selected depending on the solubility of the nickel compound and the metal compound other than nickel, the second liquid to be used, the target Ra and RED, etc., and examples thereof include water and organic solvents.
Examples of the organic solvent include esters such as methyl formate, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, and pentyl acetate; ketones such as acetone, diisobutyl ketone, ethyl methyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, γ-butyrolactone, and N-methyl-2-pyrrolidone; ethers such as diethyl ether, methyl tert-butyl ether, diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole, and phenetole; ethers such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, 1-pentanol, 2-methyl-2-butanol, methoxypropanol, diacetone alcohol, cyclohexanol, 2-fluoroethanol, 2,2,2- Examples of the solvent include alcohols such as trifluoroethanol and 2,2,3,3-tetrafluoro-1-propanol; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate and triethylene glycol dimethyl ether; organic solvents having an amide group such as N,N-dimethylformamide, acetamide and N,N-dimethylacetamide; organic solvents having a nitrile group such as acetonitrile, isobutyronitrile, propionitrile and methoxyacetonitrile; organic solvents having a carbonate group such as ethylene carbonate and propylene carbonate; halogenated hydrocarbons such as methylene chloride and chloroform; and hydrocarbons such as n-pentane, cyclohexane, n-hexane, 1-octadecene, benzene, toluene, xylene and 2,2,4-trimethylpentane.
Among these, toluene and xylene are preferable as the solvent.

The boiling point of the first solvent is not particularly limited, but is preferably 50 to 150°C, more preferably 70 to 130°C, and even more preferably 80 to 110°C. If the boiling point of the first solvent is equal to or higher than the lower limit of the above range, the first solvent will remain in the pores of the fluid catalytic cracking catalyst for a certain period of time after the first liquid is impregnated into the fluid catalytic cracking catalyst. If the boiling point of the first solvent is equal to or lower than the upper limit of the above range, the first solvent can be easily removed when removing the first solvent as described below.

The first solvent may be used alone or in combination of two or more types.

<Second Liquid>
In this embodiment, the second liquid contains a second solvent. It is preferable that the second liquid does not contain a nickel compound. The second liquid may contain a metal compound other than nickel. The second solvent contained in the second liquid will be described below.

The second solvent may be appropriately selected depending on the solubility of the metal compound other than nickel (when the second liquid contains a metal compound other than nickel), the first liquid used, and the target Ra or RED, etc., but examples include water and organic solvents. As the organic solvent, the organic solvents described for the first solvent can be used.

The second solvent may be used alone or in combination of two or more types.

The second liquid may contain a metal compound other than nickel.
As the metal compound other than nickel, the metal compounds other than nickel described in relation to the first liquid can be used.
The form of the metal compound other than nickel may be appropriately selected from the forms already described for the metal compound other than nickel contained in the first liquid depending on the solubility in the second solvent, the first liquid used, and the desired Ra and RED, etc.

(Vanadium Support)
When the first liquid and the second liquid do not contain a vanadium compound, vanadium may be supported by impregnating the vanadium compound by an impregnation method known in the art. Impregnation of the vanadium compound may be performed on any of the fluid catalytic cracking catalyst, the impregnated body, and the calcined body described below.
As described above, nickel has a dehydrogenation catalytic activity and therefore has a large effect on the amount of coke produced. On the other hand, vanadium destroys the crystal structure of zeolite, which is an active component of fluid catalytic cracking catalysts, and reduces cracking activity. The reduction in cracking activity caused by the destruction of the crystal structure of zeolite in the actual equilibrium catalyst can be reproduced by adjusting the conditions of the steam treatment step described below. Therefore, in the present invention, vanadium may be contained in the first liquid, may be contained in the second liquid, or may be supported separately from the first liquid and the second liquid.

(Nickel and vanadium loading amount)
The supported amounts of nickel and vanadium may be appropriately set based on the nickel and vanadium contents obtained by elemental analysis of the target simulated equilibrium catalyst. The supported amount of nickel is usually 0.05 to 1 mass %, and the supported amount of vanadium is usually 0.05 to 1 mass %.

<Fluid catalytic cracking catalyst>
In this embodiment, the fluid catalytic cracking catalyst can be any fluid catalytic cracking catalyst known in the art without limitation. The fluid catalytic cracking catalyst preferably contains zeolite.

The zeolite contained in the fluid catalytic cracking catalyst is not particularly limited, but examples include zeolites having a sodalite cage structure, β zeolites, and ZSM-5 type zeolites, and among these, it is preferable to include zeolites having a sodalite cage structure. The content of zeolites relative to the total mass of the fluid catalytic cracking catalyst is preferably 25 to 45 mass%, more preferably 28 to 42 mass%, and even more preferably 30 to 40 mass%.

In this specification, a zeolite having a sodalite cage structure means a zeolite having a sodalite cage structure, i.e., a tetradecahedral crystal structure defined by four-membered rings or six-membered rings, in which the vertices of a three-dimensional regular octahedral crystal structure formed by aluminum and silicon tetrahedrons as basic units and sharing the oxygen at the vertices with aluminum or silicon, is cut off, and which has voids formed by tetradecahedral crystal structures, defined by four-membered rings or six-membered rings, and which has various pore structures, skeletal densities, and channel structures due to changes in the locations and methods in which the sodalite cages are bonded to each other.

The zeolite having the sodalite cage structure may be one or more selected from sodalite, A-type zeolite, EMT, X-type zeolite, Y-type zeolite, stabilized Y-type zeolite, etc., and is preferably stabilized Y-type zeolite.

Stabilized Y-type zeolite is synthesized using Y-type zeolite as a starting material, and is more resistant to deterioration in crystallinity than Y-type zeolite. In general, it is produced by subjecting Y-type zeolite to steam treatment at high temperature several times, and then, if necessary, treating it with a mineral acid such as hydrochloric acid, a base such as sodium hydroxide, a salt such as calcium fluoride, or a chelating agent such as ethylenediaminetetraacetic acid.
The stabilized Y-type zeolite obtained by the above method can be used in a form in which it has been ion-exchanged with a cation selected from hydrogen, ammonium, or a polyvalent metal. Also, as the stabilized Y-type zeolite, a heat shock crystalline aluminosilicate zeolite (see Japanese Patent No. 2544317) having superior stability can be used.

The fluid catalytic cracking catalyst of the present embodiment preferably further contains a binder, a clay mineral, and the like.
An example of the binder is silica sol. By using silica sol, the moldability of the fluid catalytic cracking catalyst when granulating is improved, and it is possible to easily form the catalyst into a spherical shape. In addition, the fluidity and abrasion resistance of the fluid catalytic cracking catalyst after granulation can be easily improved. The content of the binder relative to the total mass of the fluid catalytic cracking catalyst is preferably 15 to 35 mass%, more preferably 18 to 32 mass%, and even more preferably 20 to 30 mass%.

Examples of clay minerals include montmorillonite, kaolinite, halloysite, bentonite, attapulgite, bauxite, etc. In addition, in the fluid catalytic cracking catalyst of this embodiment, known oxide fine particles used in ordinary fluid catalytic cracking catalysts, such as silica, silica-alumina (excluding the above-mentioned zeolites), alumina, silica-magnesia, alumina-magnesia, phosphorus-alumina, silica-zirconia, and silica-magnesia-alumina, can be used in combination with the above clay minerals.
The sum of the contents of the clay mineral and the oxide relative to the total mass of the fluid catalytic cracking catalyst is preferably 35 to 55 mass %, more preferably 38 to 52 mass %, and even more preferably 40 to 50 mass %.
The content of the clay mineral relative to the total mass of the fluid catalytic cracking catalyst is preferably 25 to 50 mass %, more preferably 30 to 45 mass %, and even more preferably 32 to 42 mass %.

The fluid catalytic cracking catalyst of this embodiment may also contain a zeolite stability improver. The zeolite stability improver has the function of suppressing the collapse of zeolite crystals. Examples of zeolite stability improvers include phosphorus-based zeolite stability improvers such as phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, aluminum monophosphate, and other water-soluble phosphates, and rare earth metal-based zeolite stability improvers such as scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, dysprosium, and holmium. When the fluid catalytic cracking catalyst contains a zeolite stability improver, the content ratio of the zeolite stability improver to the total mass of the fluid catalytic cracking catalyst is preferably 0.1 to 5 mass%.

The specific surface area of the fluid catalytic cracking catalyst of this embodiment is preferably 500 to 850 m ² /g, more preferably 600 to 850 m ² /g. The total pore volume of the fluid catalytic cracking catalyst of this embodiment is preferably 0.05 to 0.20 mL/g, more preferably 0.08 to 0.15 mL/g.

The fluid catalytic cracking catalyst is granulated to a certain size and then used in the fluid catalytic cracking reaction. The particle size of the fluid catalytic cracking catalyst is not particularly limited as long as it is a particle size that can be used in a normal fluid catalytic cracking reaction, but the particle size is preferably in the range of 20 to 150 μm.
The particle size of the fluid catalytic cracking catalyst can be measured, for example, by using a micro-type electromagnetic vibration sieve, Model M-2, manufactured by Tsutsui Rikagaku Kikai Co., Ltd.

<Impregnation method>
Examples of the impregnation method include the "evaporation to dryness method" in which the fluid catalytic cracking catalyst is immersed in an impregnation liquid in excess of the maximum amount of solution (solvent) that the catalyst can hold, and then dried to support the supported components, the "equilibrium adsorption method" in which the fluid catalytic cracking catalyst is immersed in an impregnation liquid in excess of the maximum amount of solution (solvent) that the catalyst can hold, and then the supported components are supported by solid-liquid separation such as filtration, and the pore filling method (Incipient Wetness method) in which the fluid catalytic cracking catalyst is impregnated with an impregnation liquid of approximately the same volume as the maximum amount of solution (solvent) that the catalyst can hold, and then dried to support the supported components. The maximum amount of solution (solvent) that the catalyst can hold may be the total pore volume of the fluid catalytic cracking catalyst.
In this embodiment, the pore filling method is preferred from the viewpoint of easily adjusting the volume ratio between the first liquid and the second liquid filled in the pores of the fluid catalytic cracking catalyst.

(Pore filling method)
In the pore filling method, it is preferable to sequentially impregnate the catalyst with the first liquid and the second liquid separately as impregnation liquids, and it is preferable to impregnate the catalyst with the second liquid and then with the first liquid. A specific impregnation procedure in such a pore filling method includes a method in which the fluid catalytic cracking catalyst is impregnated with the second liquid to obtain an impregnation precursor, and the impregnation precursor is further impregnated with the first liquid.

According to the method, it is possible to obtain a simulated equilibrium fluidized catalytic cracking catalyst having an egg shell type structure in which the nickel compound contained in the first liquid is supported on the outer layer of the fluidized catalytic cracking catalyst. In the method, the fluidized catalytic cracking catalyst is first impregnated with the second liquid to obtain an impregnated precursor 1. It is believed that when the impregnated precursor is then further impregnated with the first liquid, an impregnated precursor 2 is obtained in which the second liquid is present inside the fluidized catalytic cracking catalyst and the first liquid is present outside the fluidized catalytic cracking catalyst.
It is believed that when the first solvent and the second solvent are removed from this impregnated precursor 2, an impregnated body is obtained in which the nickel compound contained in the first liquid is supported as it is on the outside of the fluid catalytic cracking catalyst.

In the above method, the volume ratio of the first liquid to the second liquid (volume of the first liquid:volume of the second liquid) is not particularly limited, but is preferably, for example, 1:99 to 30:70, more preferably 5:95 to 25:75, and even more preferably 8:92 to 20:80.

In the above method, the ratio of the total volume of the first liquid and the second liquid to the maximum amount of solution (solvent) that can be held by the fluid catalytic cracking catalyst is preferably 90 to 110%, more preferably 93 to 105%, and even more preferably 95 to 100%.

In the above method, the ratio of the volume of the first liquid to the maximum amount of solution (solvent) that can be held by the fluid catalytic cracking catalyst is preferably 5 to 30%, more preferably 7 to 25%, and even more preferably 9 to 20%.

In the above method, the ratio of the volume of the second liquid to the maximum amount of solution (solvent) that can be held by the fluid catalytic cracking catalyst is preferably 70 to 105%, more preferably 75 to 98%, and even more preferably 80 to 91%.

The fluid catalytic cracking catalyst of this embodiment is made of fine particles, so the solution (solvent) is absorbed between the particles. Therefore, the maximum amount of solution (solvent) that the fluid catalytic cracking catalyst can hold is 8 to 12 times the total pore volume of the fluid catalytic cracking catalyst.

<Method of removing solvent>
The first and second solvents are removed from the impregnated precursor 2 obtained by the above impregnation method to obtain an impregnated body. Drying may be performed at normal pressure or reduced pressure. The drying temperature may be appropriately selected taking into consideration the boiling point of the solvent to be removed at the pressure at which the solvent is dried, and is preferably in the range of -10 to 30°C, and more preferably in the range of -5 to 20°C, of the boiling point of the solvent with the highest boiling point among the first and second solvents. When drying is performed at the above drying temperature, the drying time may be short, such as 0.5 to 1 hour, or long, such as 12 to 24 hours.
The drying temperature is, for example, 80 to 120°C, and may be 90 to 110°C.

<Baking process>
In the calcination step of this embodiment, the impregnated body is calcined at 500 to 800° C. to obtain a calcined body. Calcination is preferably carried out in an atmosphere of a gas containing an oxidizing gas such as oxygen. The calcination temperature is 500 to 800° C., preferably 550 to 750° C., and more preferably 600 to 700° C. When the calcination temperature is within the above range, the supported metal can be converted to an oxide while suppressing the collapse of the zeolite due to calcination.

<Steam treatment process>
In the water vapor treatment step of this embodiment, the calcined body is contacted with a gas containing water vapor. The water vapor treatment step is a reducing water vapor treatment in which a first gas containing a reducing gas and 30 to 70% by volume of water vapor is contacted with the calcined body under conditions of a temperature of 700 to 900°C and a GHSV of 300 to 700h ^{- 1, and after the reducing water vapor treatment, a second gas containing an oxidizing gas and 30 to 70% by volume of water vapor is contacted with the calcined body under conditions of a temperature of 700 to 900°C and a GHSV of 300 to 700h-1} . A cycle including the following is performed at least once.

In the fluid catalytic cracking reaction, the feedstock oil is vaporized and the reactor is filled with reducing gas, hydrocarbon gas, creating a reducing atmosphere inside the reactor. In addition, the regeneration tower is oxidized because the coke accumulated on the fluid catalytic cracking catalyst is burned. The steam treatment process of this embodiment is thought to mimic the above atmosphere of an actual machine, so that the state of the supported metals such as nickel approaches that of an actual equilibrium catalyst. In particular, it is thought that the degree of sintering of nickel, which has dehydrogenation catalytic activity (nickel particle size), can be made to approach that of an actual equilibrium catalyst. As a result, it is thought that a simulated equilibrium catalyst with activity equivalent to that of an actual equilibrium catalyst can be obtained. In particular, it is thought that a simulated equilibrium catalyst with the same amount of coke production as that of an actual equilibrium catalyst can be obtained.

The method of the steam treatment step is not particularly limited as long as the effects of the present invention are obtained, but for example, the steam treatment step can be carried out by filling the sintered body in a treatment device and circulating the first gas, the second gas, etc. The sintered body filled in the treatment device may be in a fixed bed, a fluidized bed, or a moving bed. Of these, a fluidized bed is preferable.

(Reducing steam treatment)
The reducing steam treatment is a treatment in which a first gas containing a reducing gas and 30 to 70 volume % of steam is brought into contact with the calcined body under conditions of a temperature of 700 to 900° C. and a GHSV of 300 to 700 h ⁻¹ .

The content of water vapor in the first gas is 30 to 70% by volume, preferably 35 to 65% by volume, and more preferably 40 to 60% by volume. When the content of water vapor is within the above range, the situation becomes similar to the regeneration atmosphere of the actual machine, and a simulated equilibrium catalyst with activity equivalent to that of the actual equilibrium catalyst is obtained.

The reducing gas is not particularly limited as long as the effects of the present application can be obtained, but examples include hydrocarbons such as methane, propane, propylene, butane, and butene, hydrogen, and carbon monoxide, and unsaturated hydrocarbons such as propylene and butene are preferred. The content of the reducing gas in the first gas is preferably 1 to 5 volume %, more preferably 1.5 to 4 volume %, and even more preferably 2 to 4 volume %. When the content of the reducing gas is within the above range, the state of the supported metal such as nickel approaches that of the actual equilibrium catalyst, and a simulated equilibrium catalyst having the same activity as the actual equilibrium catalyst can be obtained.

One type of reducing gas may be used alone, or two or more types may be used in combination.

The first gas may contain a gas other than water vapor and a reducing gas, and examples of such a gas include an inert gas such as helium, nitrogen, argon, etc. The content ratio of the inert gas may be appropriately set so that the first gas is 100% by volume, corresponding to the content ratio of the water vapor and the reducing gas described above.
It is preferable that the first gas does not substantially contain an oxidizing gas, which will be described later. "Substantially not containing an oxidizing gas" means that the content of the oxidizing gas in the first gas is 0.1% by volume or less.

One type of inert gas may be used alone, or two or more types may be used in combination.

The gas hourly space velocity (GHSV) of the first gas relative to the calcined body is 300 to 700 h ⁻¹ , preferably 350 to 650 h ⁻¹ , and more preferably 400 to 600 h ⁻¹ . If the GHSV of the first gas relative to the calcined body is within the above range, when the treatment is performed in a fluidized bed, the calcined body in the treatment device is in a completely fluidized state, and a sufficient amount of the first gas is supplied to the calcined body, making it easier to obtain a reduction effect on the supported metal such as nickel.
The GHSV can be obtained from the volume of the fired body filled in the treatment device and the flow rate of the first gas.

The temperature of the reducing steam treatment is 700 to 900° C., preferably 750 to 850° C., and more preferably 770 to 800° C. When the temperature of the reducing steam treatment is within the above range, a simulated equilibrium catalyst having activity equivalent to that of an actual equilibrium catalyst can be obtained.
The pressure during the reducing steam treatment is not particularly limited as long as the effects of the present invention can be obtained, but may be, for example, 0.05 to 0.15 MPa, or 0.2 to 0.5 MPa.

(Oxidizing Steam Treatment)
The oxidizing steam treatment is a treatment in which, after the reducing steam treatment, an oxidizing gas and a second gas containing 30 to 70 volume% water vapor are contacted with the calcined body under conditions of a temperature of 700 to 900 ° C. and a GHSV of 300 to 700 h ^-1 .

The content of water vapor in the second gas is 30 to 70% by volume, preferably 35 to 65% by volume, and more preferably 40 to 60% by volume. When the content of water vapor is within the above range, the situation becomes similar to the regeneration atmosphere of the actual machine, and a simulated equilibrium catalyst with activity equivalent to that of the actual equilibrium catalyst is obtained.

The oxidizing gas is not particularly limited as long as it can obtain the effects of the present application, but examples include oxygen, ozone, nitrogen dioxide, sulfur dioxide, chlorine dioxide, etc., with oxygen and sulfur dioxide being preferred. The content of the oxidizing gas in the second gas is preferably 5 to 20 volume %, more preferably 7 to 15 volume %, and even more preferably 8 to 13 volume %. When the content of the oxidizing gas is within the above range, the state of the supported metal such as nickel approaches that of the actual equilibrium catalyst, and a simulated equilibrium catalyst having the same activity as the actual equilibrium catalyst can be obtained.

One type of oxidizing gas may be used alone, or two or more types may be used in combination.

The second gas preferably contains sulfur dioxide. The content of sulfur dioxide in the second gas is preferably 1000 to 4000 ppm by volume, more preferably 1200 to 3000 ppm by volume, and even more preferably 1500 to 2500 ppm by volume. When the content of sulfur dioxide is within the above range, the state of the supported metal such as nickel approaches that of an actual equilibrium catalyst, and a simulated equilibrium catalyst having activity equivalent to that of an actual equilibrium catalyst can be obtained.

The second gas may contain a gas other than water vapor and an oxidizing gas, and examples of such a gas include inert gases such as helium, nitrogen, argon, etc. The content ratio of the inert gas may be appropriately set so that the second gas is 100% by volume, corresponding to the content ratios of the water vapor and the oxidizing gas described above.
It is preferable that the second gas does not substantially contain the above-mentioned reducing gas. "Substantially not containing a reducing gas" means that the content of the reducing gas in the first gas is 0.1 volume % or less.

One type of inert gas may be used alone, or two or more types may be used in combination.

The GHSV of the second gas relative to the calcined body is 300 to 700 h ⁻¹ , preferably 350 to 650 h ⁻¹ , and more preferably 400 to 600 h ⁻¹ . If the GHSV of the second gas relative to the calcined body is within the above range, when the treatment is performed in a fluidized bed, the calcined body in the treatment device is in a completely fluidized state, and a sufficient amount of the second gas is supplied to the calcined body, making it easier to obtain an oxidation effect on the supported metal such as nickel.

The temperature of the oxidative steam treatment is 700 to 900° C., preferably 750 to 850° C., and more preferably 770 to 800° C. When the temperature of the oxidative steam treatment is within the above range, the state of the supported metal such as nickel approaches that of the actual equilibrium catalyst, and a simulated equilibrium catalyst having activity equivalent to that of the actual equilibrium catalyst can be obtained.
The pressure during the oxidizing steam treatment is not particularly limited as long as the effects of the present invention are obtained, but may be, for example, 0.05 to 0.15 MPa, or 0.2 to 0.5 MPa.

(Inert steam treatment)
The steam treatment step of this embodiment may include an inert steam treatment in which an inert gas and a third gas containing 30 to 70 volume% steam are brought into contact with the fired body under conditions of a temperature of 700 to 900° C. and a GHSV of 300 to 700 h ⁻¹ before or after the reducing steam treatment and/or before or after the oxidizing steam treatment.

The water vapor content in the third gas is preferably 30 to 70% by volume, more preferably 35 to 65% by volume, and even more preferably 40 to 60% by volume.

The inert gas is not particularly limited as long as it can provide the effects of the present application, but examples include inert gases such as helium, nitrogen, and argon. The content of the inert gas may be appropriately set so that the third gas is 100% by volume, corresponding to the content of water vapor described above.

One type of inert gas may be used alone, or two or more types may be used in combination.

It is preferable that the third gas is substantially free of the above-mentioned reducing gas and oxidizing gas. Substantially free of reducing gas and oxidizing gas means that the total content of reducing gas and oxidizing gas in the third gas is 0.1 volume % or less.

The GHSV of the third gas relative to the calcined body is preferably 300 to 700 h ⁻¹ , more preferably 350 to 650 h ⁻¹ , and even more preferably 400 to 600 h ⁻¹ . If the GHSV of the third gas relative to the calcined body is within the above range, when the treatment is performed in a fluidized bed, the calcined body in the treatment device is in a completely fluidized state, and a sufficient amount of the third gas is supplied to the calcined body, thereby making it possible to remove reducing gas and/or oxidizing gas remaining in the reactor.

The temperature of the inert steam treatment is preferably 700 to 900° C., more preferably 750 to 850° C., and even more preferably 770 to 800° C. When the temperature of the inert steam treatment is within the above range, the state of the supported metal such as nickel approaches that of the actual equilibrium catalyst, and a simulated equilibrium catalyst having activity equivalent to that of the actual equilibrium catalyst can be obtained.
The pressure during the inert water vapor treatment is not particularly limited as long as the effects of the present invention are obtained, but may be, for example, 0.05 to 0.15 MPa, or 0.2 to 0.5 MPa.

The inert steam treatment is preferably carried out between the reducing steam treatment and the oxidizing steam treatment. For example, by carrying out the inert steam treatment after the reducing steam treatment and before the oxidizing steam treatment, the reducing gas contained in the first gas can be removed from within the treatment device before the oxidizing steam treatment is started. In this case, the content of the reducing gas relative to the volume of the total gas within the treatment device when the oxidizing steam treatment is started is preferably 0.1% by volume or less.

The inert steam treatment may be performed between the cycles. For example, by performing the inert steam treatment after the oxidizing steam treatment and before the reducing steam treatment, the oxidizing gas contained in the second gas can be removed from within the treatment device before the reducing steam treatment is started. In this case, the content of the oxidizing gas relative to the volume of the total gas within the treatment device when the reducing steam treatment is started is preferably 0.1% by volume or less.

(cycle)
In this specification, the cycle includes a reducing steam treatment and an oxidizing steam treatment performed after the reducing steam treatment. Specifically, the cycle includes one reducing steam treatment and one oxidizing steam treatment performed after the reducing steam treatment. Note that when an inert steam treatment is performed between a plurality of reducing steam treatments (reducing steam treatment → inert steam treatment → reducing steam treatment), it is counted as one reducing steam treatment. Similarly, when an inert steam treatment is performed between a plurality of oxidizing steam treatments (oxidizing steam treatment → inert steam treatment → oxidizing steam treatment), it is counted as one oxidizing steam treatment. Also, as described above, an inert steam treatment may be performed between the reducing steam treatment and the oxidizing steam treatment.

The cycle is preferably performed 20 to 50 times, more preferably 25 to 45 times, and even more preferably 30 to 40 times. If the number of cycles is within the above range, the state of the supported metal such as nickel approaches that of the actual equilibrium catalyst, and a simulated equilibrium catalyst with activity equivalent to that of the actual equilibrium catalyst can be obtained.

In the steam treatment step, the reducing steam treatment is preferably performed for a total of 3 to 9 hours, more preferably 4 to 8 hours, and even more preferably 5 to 7 hours. If the total reducing steam treatment is within the above range, the state of the supported metals such as nickel approaches that of the actual equilibrium catalyst, and a simulated equilibrium catalyst with activity equivalent to that of the actual equilibrium catalyst can be obtained.

In the steam treatment step, the oxidative steam treatment is preferably carried out for a total of 3 to 9 hours, more preferably 4 to 8 hours, and even more preferably 5 to 7 hours. If the total oxidative steam treatment is within the above range, the state of the supported metals such as nickel approaches that of the actual equilibrium catalyst, and a simulated equilibrium catalyst with activity equivalent to that of the actual equilibrium catalyst can be obtained.

When comparing the activity of a real equilibrium catalyst with that of a simulated equilibrium catalyst, it is preferable to compare the conversion rate, the yield of dry gas consisting of hydrogen and hydrocarbons with 1-2 carbon atoms, the yield of LPG consisting of hydrocarbons with 3-4 carbon atoms, the yield of gasoline fraction, the yield of middle distillate (LCO), the yield of heavy distillate (SLO), and the yield of coke. In particular, it is preferable that the conversion rate of the simulated equilibrium catalyst, as well as the yield of hydrogen and the yield of coke, which have a significant impact on the operation of the fluid catalytic cracking reaction, are close to those of the real equilibrium catalyst.

The conversion rate, hydrogen yield, and coke yield can be adjusted by adjusting the conditions of the calcination step and the steam treatment step. Specifically, the conversion rate, hydrogen yield, and coke yield can be reduced by making the conditions of the calcination step and the steam treatment step more severe. Examples of making the conditions more severe include increasing the calcination temperature of the calcination step and increasing the number of cycles in the steam treatment step. Other examples include lengthening the total time for which the reducing steam treatment is performed, increasing the treatment temperature and the GHSV of the first gas, and increasing the concentration of water vapor in the first gas. Other examples include lengthening the total time for which the oxidizing steam treatment is performed, increasing the treatment temperature and the GHSV of the second gas, and increasing the concentration of water vapor in the second gas.

The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to the following examples.

The total pore volume of the fluid catalytic cracking catalyst was measured, the simulated equilibrated catalyst was analyzed by EPMA, and the activity of the simulated equilibrated catalyst was evaluated using the following methods.

(Measurement of total pore volume of fluid catalytic cracking catalyst)
The total pore volume of the fluid catalytic cracking catalyst was measured using a porosimeter (MICROMERITICS AUTO-PORE 9200, manufactured by Shimadzu Corporation) as a mercury intrusion device.

EPMA Analysis of Simulated Equilibrated Catalysts
The EPMA analysis of the simulated equilibrated catalyst was carried out using an electron probe microanalyzer (EPMA, JXA-8600MX, manufactured by JEOL Ltd.). The measurement conditions were an acceleration voltage of 15 kV, an incident current of 1×10 ⁻⁷ A, an interval between measurement points of 10 μm, and a counting time of 0.3 sec. The cross section of the measurement catalyst was prepared by embedding the catalyst in MMA (methyl methacrylate) and polishing it using a polishing device.
In the mapping diagrams of nickel element obtained from EPMA analysis (Fig. 4 and 6), the areas shown in yellow are the areas with the highest nickel concentration, followed by green and blue, in which the nickel concentration decreases. The areas shown in black are nickel-free.

<Calculation of HPS value, _R0, etc.>
For the first and second liquids described below, the Hansen ball was determined by the Hansen ball method using HSPiP, and the HSP value and _R0 were obtained. Similarly, for the above solvents, the Hansen ball was determined by the Hansen ball method using HSPiP, and the HSP value was obtained. The solubility when determining the Hansen ball was judged based on 25°C.

(Catalyst activity evaluation)
9 g of the simulated equilibrated catalyst produced in the Examples described below was packed into a fluid catalytic cracking apparatus. The feed oil was fed at 1.2 g/min, and the reaction was carried out at a reaction temperature of 500° C. and a regeneration temperature of 700° C. to obtain cracked oil. The cracked oil was analyzed by gas chromatography.
Specifically, the obtained cracked oil was analyzed by gas chromatographic distillation using an AC Simdis Analyzer manufactured by Agilent Technologies, and the product amounts of dry gas (hydrogen, hydrocarbons with 1 to 2 carbon atoms), LPG (hydrocarbons with 3 to 4 carbon atoms), gasoline fraction (boiling point 27 to 190 ° C), middle fraction (LCO: boiling point 190 ° C. to 350 ° C.), and heavy fraction (SLO: boiling point over 350 ° C.) were analyzed. In addition, the amount of coke produced was analyzed and calculated from the CO and CO ₂ concentrations in the regeneration tower. Furthermore, the components contained in the dry gas, LPG, and gasoline fraction were quantified by gas chromatography.
The conversion rate was calculated by: 100% - LCO yield (mass %) - SLO yield (mass %).
In Table 1, Cn represents a hydrocarbon having a carbon number of n.

[Production Example 1]
Silica sol (binder) 42.0 g (dry basis, _SiO2 equivalent) was diluted with 25% sulfuric acid and stirred to obtain an aqueous solution of silica sol. Distilled water was added to 76.0 g (dry basis) of stabilized Y-type zeolite to prepare a zeolite slurry. Kaolinite 71.4 g (dry basis) and alumina hydrate oxide 10 g (dry basis) were added to the above silica sol aqueous solution and mixed, and the above zeolite slurry was further added and stirred and mixed for 10 minutes using a disperser to obtain an aqueous slurry. The obtained aqueous slurry was spray-dried under conditions of an inlet temperature of 210 ° C and an outlet temperature of 140 ° C, and the obtained microspheres were used as a catalyst precursor. The catalyst precursor was ion-exchanged twice with 3 L of 5 mass % ammonium sulfate aqueous solution at 60 ° C, and then washed with 3 L of distilled water. The washed microspheres were then ion-exchanged with lanthanum nitrate aqueous solution for 15 minutes so that the lanthanum oxide content on a dry basis was 0.3 mass %, and then washed with 3 L of distilled water. Thereafter, the catalyst was dried overnight at 110° C. in a dryer to obtain a fluid catalytic cracking catalyst. The total pore volume of the fluid catalytic cracking catalyst was 0.09 mL/g.

[Reference Example 1]
A practical operation was carried out using the fluid catalytic cracking catalyst obtained in Production Example 1 to obtain a practical equilibrium catalyst. The activity of the obtained practical equilibrium catalyst was evaluated. The results are shown in Table 1.

[Example 1]
Nickel 2-ethylhexanoate was selected as the nickel compound, toluene (boiling point: 110.6°C) was selected as the first solvent, and vanadium 2-ethylhexanoate was selected as the metal compound other than nickel. A toluene solution having a nickel concentration of 6 mass% and a vanadium concentration of 2 mass% was used as the first liquid. The amounts of nickel and vanadium contained in the first liquid were adjusted to be the same as those of the above-mentioned actual equilibrium catalyst. 2,2,4-trimethylpentane (boiling point: 99°C) was used as the second liquid. The Ra of the first liquid and the second liquid was 15.9, and the RED of the second liquid relative to the first liquid was 1.99.
The maximum amount of solvent that the catalyst could retain was measured by immersing the first or second solvent in advance for the fluid catalytic cracking catalyst obtained in Production Example 1. The maximum amount of solvent was 0.86 mL/g-cat.
The fresh FCC catalyst was impregnated with the second liquid having a volume of 80% of the maximum solvent amount that the fluid catalytic cracking catalyst can hold, to obtain an impregnated precursor 1. The first liquid having a volume of 20% of the maximum solvent amount that the fluid catalytic cracking catalyst can hold was added to the impregnated precursor 1 while stirring, to thereby impregnate the catalyst, to obtain an impregnated precursor 2.
The obtained impregnated precursor 2 was dried at 110° C. for 0.5 hours to obtain an impregnated body, which was then calcined at 600° C. for 2 hours in an air atmosphere to obtain a calcined body 1.
The obtained calcined body 1 was subjected to 30 cycles of the steam treatment step, with the following cycle being one cycle, to obtain catalyst A. The EPMA analysis results of catalyst A are shown in Figures 3 and 4. As is clear from Figures 3 and 4, it was confirmed that nickel was distributed in the outer layer of the catalyst.
The activity of the obtained catalyst A was evaluated. The results are shown in Table 1.

(One cycle in the steam treatment process)
A mixed gas (first gas) of 1.60% by volume of steam, 38% by volume of nitrogen, and 2% by volume of propylene was filled in a fluid catalytic cracking apparatus, and the calcined body 1 was subjected to a contact treatment for 10 minutes under the conditions of normal pressure, temperature of 770°C, and GHSV of 400 h ^-1 .
2. A mixed gas (third gas) of 60 volume % water vapor and 40 volume % nitrogen was filled in a fluid catalytic cracking apparatus, and the calcined body 1 was subjected to a contact treatment for 10 minutes under the conditions of normal pressure, temperature of 770° C., and GHSV of 400 h ⁻¹ .
A mixed gas (second gas) of 3.60 vol. % steam, 39.84 vol. % air, and 1600 vol. ppm sulfur dioxide was filled in a fluid catalytic cracking apparatus, and the calcined body 1 was subjected to a contact treatment for 10 minutes under conditions of normal pressure, temperature of 770°C, and GHSV of 400 h ^-1 .
A mixed gas (third gas) of 4.60% by volume of steam and 40% by volume of nitrogen was filled in a fluid catalytic cracking apparatus, and the calcined body 1 was subjected to a contact treatment for 10 minutes under the conditions of normal pressure, temperature of 770° C., and GHSV of 400 h ⁻¹ .

[Example 2]
In Example 1, the impregnated body was calcined at 700° C. for 24 hours in an air atmosphere instead of at 600° C. for 2 hours, to obtain calcined body 2.
The obtained calcined body 2 was subjected to 30 cycles of the steam treatment step in the same manner as in Example 1 to obtain a catalyst B. An EPMA analysis of the catalyst B confirmed that nickel was distributed in the outer layer of the catalyst.
The activity of the obtained catalyst B was evaluated. The results are shown in Table 1.

[Comparative Example 1]
An impregnation solution was prepared by diluting the first liquid prepared in Example 1 with cyclohexane. The fluidized catalytic cracking catalyst was impregnated with the impregnation solution having a volume of 100% of the maximum amount of solvent that the fluidized catalytic cracking catalyst could hold, to obtain an impregnation precursor 3. The amounts of nickel and vanadium contained in the first liquid were adjusted to be the same as those in the above-mentioned actual equilibrium catalyst.
The obtained impregnated precursor 3 was dried at 110° C. for 0.5 hour to obtain an impregnated body, which was then calcined at 600° C. for 2 hours in an air atmosphere to obtain a calcined body 3.
The calcined body 3, in which 100% by volume of steam was packed in a fluid catalytic cracking apparatus, was subjected to contact treatment for 3 hours under conditions of normal pressure, temperature of 800°C, and GHSV of 400 h ^-1 to obtain catalyst C. The EPMA analysis results of catalyst C are shown in Figures 5 and 6. As is clear from Figures 5 and 6, it was confirmed that nickel was uniformly distributed in the catalyst, as compared with the above-mentioned catalyst A.
The activity of the resulting catalyst C was evaluated. The results are shown in Table 1.

[Comparative Example 2]
A fired body 3 was obtained in the same manner as in Comparative Example 1.
The obtained calcined body 3 was subjected to 30 cycles of the steam treatment step in the same manner as in Example 1 to obtain catalyst D. EPMA analysis of catalyst D confirmed that nickel was uniformly distributed in the catalyst.
The activity of the obtained catalyst D was evaluated. The results are shown in Table 1.

[Comparative Example 3]
A fired body 1 was obtained in the same manner as in Example 1.
As in Comparative Example 1, the calcined body 1, in which 100% by volume of steam was packed in a fluid catalytic cracking apparatus, was contacted for 3 hours under conditions of normal pressure, temperature of 800°C, and GHSV of 400 h ^-1 to obtain catalyst E. EPMA analysis of catalyst E confirmed that nickel was distributed in the outer layer of the catalyst.
A fluid catalytic cracking reaction was carried out using the obtained catalyst E. The results are shown in Table 1.

In Examples 1 and 2, reaction results were obtained that were very close to those of the Reference Example, focusing on conversion rate, hydrogen yield, and coke yield. The conversion rates of Example 2 and the Reference Example differ by about 1%, but as mentioned above, by making the conditions of the steam treatment process milder, it is possible to adjust the conversion rate, and in that case, it is believed that the coke yield will also increase, so it is believed that the reaction results will be closer to those of the Reference Example, which uses an actual equilibrium catalyst.

In Comparative Examples 1 and 3, the reaction results differed from those of the Reference Example, mainly in terms of hydrogen yield and coke yield. In order to match the conversion rates of Comparative Examples 1 and 3 to that of the Reference Example, it is possible to make the conditions for the 100% by volume steam treatment milder, but in that case, it is thought that the coke yield would also increase, resulting in a further deviation from the coke yield of the Reference Example. Therefore, it was found that it is difficult to bring Comparative Examples 1 and 2 closer to the reaction results of the Reference Example in terms of coke yield.

In Comparative Example 2, the reaction results were different from those of the Reference Example, mainly in terms of the hydrogen yield. In order to match the conversion rate of Comparative Example 2 to that of the Reference Example, it is possible to make the conditions of the steam treatment process milder, but in that case, it is thought that the coke yield would also increase, resulting in a greater deviation from the coke yield of the Reference Example. In order to match the coke yield of Comparative Example 2 to that of the Reference Example, it is possible to make the conditions of the steam treatment process harsher, but as a result of the investigation by the inventors of the present application, it was found that in Comparative Example 2, the coke yield does not decrease even if the conditions of the steam treatment process are made harsh. It was presumed that this result was due to the fact that nickel is uniformly supported in the catalyst of Comparative Example 2, making nickel sintering less likely to occur. Therefore, it was found that it is difficult to bring Comparative Example 2 closer to the reaction results of the Reference Example in terms of coke yield.

Claims (7)

The method includes an impregnation step of impregnating a fluid catalytic cracking catalyst with a first liquid containing a nickel compound and a first solvent, and a second liquid containing a second solvent, and then removing the first solvent and the second solvent to obtain an impregnated body; a calcination step of calcining the impregnated body at 500 to 800°C to obtain a calcined body; and a steam treatment step of contacting the calcined body with a gas containing steam,
A combination of the first liquid and the second liquid is selected such that the distance (Ra) of the Hansen solubility parameters between the first liquid and the second liquid is 10 MPa ^1/2 or more, and the relative energy difference (RED) based on the Hansen solubility parameters of the second liquid relative to the first liquid is greater than 1;
The impregnation step includes impregnating the first liquid after impregnating the second liquid,
The steam treatment step is a reducing steam treatment in which a first gas containing a reducing gas and 30 to 70% by volume of steam is brought into contact with the calcined body under conditions of a temperature of 700 to 900°C and a GHSV of 300 to 700h ^{- 1, and an oxidizing steam treatment in which a second gas containing an oxidizing gas and 30 to 70% by volume of steam is brought into contact with the calcined body under conditions of a temperature of 700 to 900°C and a GHSV of 300 to 700h-} 1 after the reducing steam treatment. A method for producing a simulated equilibrium fluid catalytic cracking catalyst, comprising the steps of: The method for producing a simulated equilibrium fluid catalytic cracking catalyst according to claim 1, wherein the proportion of reducing gas contained in the first gas is 1 to 5 volume %. The method for producing a simulated equilibrium fluid catalytic cracking catalyst according to claim 1 or 2, wherein the proportion of the oxidizing gas contained in the second gas is 5 to 20% by volume. The method for producing a simulated equilibrium fluid catalytic cracking catalyst according to any one of claims 1 to 3, wherein the cycle is performed 20 to 50 times. The method for producing a simulated equilibrium fluid catalytic cracking catalyst according to any one of claims 1 to 4, wherein the reducing steam treatment is carried out for a total of 3 to 9 hours. The method for producing a simulated equilibrium fluid catalytic cracking catalyst according to any one of claims 1 to 5, wherein the oxidative steam treatment is carried out for a total of 3 to 9 hours. The method for producing a simulated equilibrium fluid catalytic cracking catalyst according to any one of claims 1 to 6, wherein the second gas contains 1000 to 4000 ppm by volume of sulfur dioxide.

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