JP2018103120A - Metal scavenger, method for producing metal scavenger, and fluid catalytic cracking catalyst - Google Patents

Abstract

An object of the present invention is to capture and immobilize vanadium, which is one of poisoning elements of a fluid catalytic cracking catalyst used in the catalytic cracking reaction process of hydrocarbon oil, to suppress deterioration of the fluid catalytic cracking catalyst and to have high catalytic activity. To provide a metal scavenger capable of maintaining
An oxide of a Group 2 element, which is a first metal component such as magnesium or calcium having a vanadium trapping function, is supported on a support made of titanium oxide, and further to the first metal component. A metal scavenger is constituted by supporting a rare earth metal oxide, which is a second metal component such as lanthanum or cerium, which serves as a promoter. The content of the first metal component is 20 to 80% by mass in terms of oxide with respect to 100% by mass of the support, and the content of the second metal component is in terms of oxide with respect to 100% by mass of the support. It is 20-80 mass%.
[Selection figure] None

Description

  The present invention relates to a technical field for capturing and fixing vanadium which is one of poisoning elements of a fluid catalytic cracking catalyst in a catalytic cracking reaction process.

  A fluid catalytic cracking catalyst used in a fluid catalytic cracking (FCC) process of a feedstock oil (hydrocarbon oil), for example, atmospheric distillation residue oil, contains zeolite which is a solid acid. Furthermore, the fluid catalytic cracking catalyst is added with a matrix component, for example, silica alumina having a cracking activity of hydrocarbon oil, for the purpose of providing abrasion resistance when used in a fluid state.

  Although the raw material oil contains vanadium, which is one of the metal elements, as an impurity, vanadium forms vanadic acid in the atmosphere in the regeneration tower for regenerating the fluid catalytic cracking catalyst. It is known to cause crystal destruction and activity reduction of zeolite. For this reason, a technique of incorporating a constituent having the ability to capture vanadium, which is a poisoning element of the fluid catalytic cracking catalyst, into the catalyst, or a technique of mixing the constituent with the base catalyst as an additive is employed.

  Patent Document 1 describes an additive obtained by precipitating a rare earth element such as lanthanum or neodymium as an oxalate as an additive to be added to a fluid catalytic cracking catalyst. This additive tends to form coarse particles during precipitation of the rare earth element, and when the rare earth element on the surface of the oxalate functions as a trap for vanadium, the utilization rate of the rare earth element precipitated as the oxalate is low. There is a problem.

Patent Document 2 discloses a combination of MgO—Al ₂ O ₃ spinel and La / Nd oxide as a metal passivating composition used to passivate a metal that reduces the activity of a fluid catalytic cracking catalyst. Is described. However, this composition has a low vanadium scavenging ability, which is inferior to that of the additive described in Patent Document 1, for example, and the spinel structure has high crystallinity. There is concern about deterioration of wear.

JP-A-6-136369 Japanese National Patent Publication No. 11-505280

  The object of the present invention is to capture and immobilize vanadium which is one of poisoning elements of a fluid catalytic cracking catalyst used in the catalytic cracking reaction process of hydrocarbon oil, and to suppress deterioration of the fluid catalytic cracking catalyst. An object of the present invention is to provide a metal scavenger capable of maintaining high catalytic activity and a method for producing the metal scavenger. Still another object of the present invention is to provide a fluid catalytic cracking catalyst containing a metal scavenger.

The metal scavenger of the present invention is
A carrier made of titanium oxide;
An oxide of a Group 2 element which is a first metal component supported on the carrier;
And a rare earth metal oxide which is a second metal component supported on the carrier.
The first metal component is, for example, at least one of magnesium and calcium, and the second metal component is, for example, at least one of lanthanum and cerium.
The method for producing the metal scavenger of the present invention comprises:
Obtaining a titanium oxide slurry;
Using the titanium oxide slurry to obtain a metal scavenger precursor in which a first metal component and a second metal component are supported on a titanium oxide support;
Drying the metal scavenger precursor, and further baking to obtain a metal scavenger.
Further, the fluid catalytic cracking catalyst of the present invention contains the metal scavenger of the present invention, a zeolite, an alumina binder, and a viscosity mineral component, and optionally contains an additive having an active matrix component and the like. May be.

  In the present invention, as a metal scavenger, an oxide of a group 2 element which is a first metal component such as magnesium or calcium having a vanadium scavenging function is supported on the surface of a support made of titanium oxide, For example, a rare earth metal oxide, which is a second metal component such as lanthanum or cerium, which serves as a promoter for one metal component is supported. For this reason, the deterioration of the fluid catalytic cracking catalyst can be suppressed, and each oxide used can be used effectively. In other words, the utilization factor of each oxide is high, and the amount of each oxide used is suppressed. Can do.

Hereinafter, preferred embodiments of the present invention will be described in detail.
[About metal scavenger]
The metal scavenger of the present invention is constituted by supporting a metal oxide having a vanadium (V) scavenging function on the surface of a support made of titanium oxide (TiO ₂ ).
<Carrier>
The carrier used in the present invention is made of titanium oxide (titania). By using titanium oxide as the carrier of the metal scavenger, the scavenger carrying the metal component on the titania carrier is more thermally stable than the other scavengers carried on the carrier made of silicon and / or alumina. There is an advantage that the transition is difficult to occur, the interaction with the oxide having a vanadium (V) trapping function is strong, and the metal component is easily dispersed on the surface of the support.
The scavenger preferably has an average particle size in the range of 1 to 30 μm, and more preferably in the range of 5 to 25 μm. In addition, particle diameter evaluation was measured by the dry micromesh sieve method, and 50 mass% value was made into the average particle diameter. If the average particle size is excessively smaller than 1 μm, the metal capturing efficiency is lowered, and if it is excessively larger than 30 μm, the wear resistance and strength of the metal capturing agent are decreased.

Scavenger, the ratio was measured by the BET method surface area (SA) is preferably in the range of 5 to 100 m ² / g, it is preferably in the range of more 20~70m ² / g. When the specific surface area is excessively smaller than 5 m ² / g, the oxide is likely to aggregate and the metal capture efficiency is lowered. On the other hand, when the specific surface area is excessively larger than 100 m ² / g, the strength as a scavenger is reduced and the shape retention as the scavenger is lowered.
The pore volume of the scavenger is measured by a pore filling method of water, and is preferably in the range of 0.10 to 0.40 ml / g, more preferably 0.35 or less, More preferably, it is the following. If it is excessively smaller than 0.10 ml / g, the metal trapping efficiency is lowered, and if it is excessively larger than 0.40 ml / g, there is a possibility that the strength when used as a catalyst cannot be obtained. The pore volume represents the volume of pores having a pore diameter of 41 mm or more.

<Metal oxide>
As a metal component to be supported on the titania support, an oxide of a Group 2 element which is a first metal component or a precursor thereof, and an oxide of a rare earth metal which is a second metal component or a precursor thereof. Supported. When the precursor is supported on the titania carrier, the precursor becomes an oxide by performing heat treatment.
The first metal component may be Mg, Ca, or both Mg and Ca. The content (supported amount) of the first metal component needs to be 20 to 80% by mass in terms of oxide with respect to 100% by mass (part by mass) of the titania support.
If the content of the first metal component is excessively less than 20% by mass in terms of oxide, the metal scavenging ability necessary for the reaction may not be ensured. If it is excessively greater than 80% by mass, the metal component aggregates. There is a risk that dispersibility may be hindered.

  The second metal component may be La or Ce, or may be both La and Ce. The content (supported amount) of the second metal component needs to be 20 to 80% by mass in terms of oxide with respect to 100% by mass of the titania support. The second metal component acts as a co-catalyst with respect to the first metal component, and the content of the first metal component / second metal component is in the range of 0.25 to 4.0 in terms of oxide. It is necessary to be. When less than 0.25, it becomes difficult for the first metal component and the second metal component, which are active metal components, to maintain an appropriate structure, and when the content exceeds 4.0 in terms of oxide, Aggregation of metal components is likely to proceed, resulting in a decrease in catalyst performance.

[Method for producing metal scavenger]
As an example of the method for producing a metal scavenger according to the present invention,
(1) obtaining a titanium oxide slurry;
(2) a second step of obtaining a metal scavenger precursor having the first metal component and the second metal component supported on a titanium oxide support using the titanium oxide slurry;
(3) A third step of drying the precursor and further baking to obtain a metal scavenger. Hereinafter, each step will be described.

<First step: step of obtaining a titania slurry>
Prepare a titania slurry of hydrated titanium oxide gel or sol. The gel of hydrated titanium oxide can be obtained by adding an alkali to an aqueous solution of a titanium salt such as titanium chloride or titanium sulfate, and neutralizing and washing. The hydrated titanium oxide sol can be obtained by passing an aqueous solution of titanium salt through an ion exchange resin to remove anions or hydrolyzing titanium alkoxide. The specific surface area of the hydrated titanium oxide particles in the gel or sol obtained at this time is preferably 150 m ² / g or more, preferably 155 m ² / g or more.
The hydrated titanium oxide here is a generic name for titania slurry containing hydrated titanium oxide or titanium hydroxide (titanium hydroxide) or hydrous titanic acid obtained by the above method.

<Second Step: Step of Mixing Titania Slurry and Two Metal Components to Obtain a Mixed Slurry> Impregnation liquid or two types obtained by dissolving two metal components in the slurry obtained in the first step The impregnating liquid obtained by simultaneously adding the metal components is stirred and mixed.
The mixing condition is usually 20 to 90 ° C., preferably 25 to 80 ° C., and kept at a temperature of ± 5 ° C., preferably ± 2 ° C., more preferably ± 1 ° C. of the temperature of this solution. The aqueous solution is usually 5 to 20 minutes, preferably 7 to 15 minutes, so that the pH is 3.0 to 10.0, preferably 3.5 to 9.5, more preferably 3.5 to 9.0. During the addition, a precipitate is formed to obtain a hydrate slurry.

<Third step>
The carrier carrying the metal component obtained by contacting with the impregnation liquid in the second step is 100 to 600 ° C., preferably 110 to 600 ° C., more preferably 400 to 600 ° C., preferably 0.5 to 10 hours, preferably The metal scavenger of the present invention is produced by drying and / or baking heat treatment in 1 to 8 hours.
Drying may be a dryer or spray drying. Spray drying is more practical. The spray drying conditions are preferably performed within the following conditions.
Specifically, the slurry obtained in the second step is filled in a slurry storage tank of a spray dryer, and the slurry is sprayed into a drying chamber in which an air flow (for example, air) adjusted to 230 ° C. in the range of 150 to 450 ° C. flows. By doing so, spray-dried particles are obtained. Although the temperature of the airflow is lowered by spray drying of the slurry, the temperature at the outlet of the drying chamber is maintained at, for example, 130 ° C in the range of 110 to 350 ° C using a heater or the like.
Furthermore, when performing a baking process, in detail, the said spray-dried particle is baked in the air atmosphere adjusted to 600 degreeC of the range of 300-700 degreeC. If the calcination temperature is excessively lower than 300 ° C, the operability due to residual moisture may be deteriorated, and the metal loading state may be difficult to be uniform. If the calcination temperature is excessively higher than 700 ° C, the metal agglomerates and maintains the dispersion. Is not preferable because there is a possibility that it may not be expected.
In order to adjust the particle size of the metal scavenger of the present application, it may be appropriately pulverized after firing.

  Moreover, the manufacturing method of a metal capture agent is not restricted to the above-mentioned method, You may carry out as follows. First, a titanium oxide powder is dissolved in pure water and stirred to obtain a titanium oxide slurry. The slurry is spray-dried and granulated to obtain a carrier made of titanium oxide. Next, the carrier is impregnated with an impregnating liquid containing the first oxide and the second oxide. As the impregnation method, for example, a pore filling method or a vacuum impregnation method is used. The carrier impregnated with the impregnating liquid is dried, and further fired at 400 to 600 ° C. for 0.5 to 10 hours to obtain a metal scavenger.

[Fluid catalytic cracking catalyst]
The catalyst of the present invention contains 10 to 50% by mass of zeolite, 5 to 30% by mass of an alumina binder, 10 to 40% by mass of a clay mineral component, and further contains 10% by mass of a metal scavenger. The catalytic cracking treatment using the catalyst is carried out under a high-temperature and high-pressure condition in a hydrogen atmosphere after filling the catalyst in a fixed bed reactor.

<Alumina binder>
The catalyst of the present invention contains an alumina binder. As a raw material of the alumina binder, for example, basic aluminum chloride ([Al ₂ (OH) _n Cl _6-n ] _m (where 0 <n <6, m ≦ 10)) is used. Basic aluminum chloride decomposes at a relatively low temperature of about 200 to 450 ° C. in the presence of aluminum contained in zeolite and the like and cations such as sodium and potassium. As a result, it is considered that a part of basic aluminum chloride is decomposed and a site where a decomposition product such as aluminum hydroxide exists is formed in the vicinity of the zeolite. Furthermore, an alumina binder (alumina) is formed by baking the decomposed basic aluminum chloride at a temperature in the range of 300 to 600 ° C. At this time, when the decomposition product in the vicinity of the zeolite is calcined to become an alumina binder, relatively many mesopores having a pore diameter in the range of 4 nm or more and 50 nm or less are formed, which may increase the specific surface area of the catalyst of the present invention. Presumed to be possible. On the other hand, it has also been confirmed that the formation of macropores having a pore diameter larger than 50 nm and 1000 nm or less, which is a factor for reducing the wear resistance, is suppressed.

In the catalyst of the present invention, the alumina binder is detected as alumina in the matrix component. The alumina binder constitutes a part of the matrix component and is added for the purpose of binding the zeolite and the matrix component.
The catalyst of the present invention contains an alumina binder in an amount of 5 to 30% by mass, preferably 5 to 25% by mass, more preferably 10 to 20% by mass. When the content of the alumina binder is less than 5% by mass, the bulk density becomes too low or the wear resistance becomes insufficient. On the other hand, when the content of the alumina binder is more than 30% by mass, the excessive binder component causes pore clogging and the like, and the activity becomes insufficient.

<Zeolite>
The catalyst of the present invention includes zeolite (crystalline alumina silicate). The zeolite is not particularly limited as long as it has a catalytic cracking activity for hydrocarbon feedstock in a catalytic cracking process, particularly a fluid catalytic cracking process. For example, one or two or more types of zeolites selected from faujasite zeolite, ZSM zeolite, β zeolite, mordenite zeolite, and natural zeolite can be included. Preferably, the catalyst of the present invention includes a USY type (Ultra-Stable Y-Type) which is a synthetic faujasite zeolite.

  The catalyst of the present invention contains 10 to 50% by mass, preferably 15 to 45% by mass, more preferably 20 to 40% by mass of zeolite. When the content of zeolite is less than 10% by mass, the activity becomes insufficient because of the small amount of zeolite. On the other hand, if the content of the zeolite is more than 50% by mass, the activity is too high and it is excessively decomposed, and the selectivity may be lowered. Also, since the content of matrix components other than zeolite is reduced, the bulk density is reduced. Becomes too low or wear resistance becomes insufficient, and when used as a fluid catalyst, it becomes a factor that easily powders and scatters.

<Clay mineral component>
As the clay mineral component, kaolin, halloysite or the like is used, and kaolin is preferably selected.
<Additives>
The fluid catalytic cracking catalyst of the present invention may contain additives in addition to the above-mentioned metal scavenger, zeolite, alumina binder, and clay mineral component. Examples of the additive include an active matrix component, a component that increases the octane number and increases the lower olefin component, and the like.

Examples of the active matrix component include substances having a solid acid such as activated alumina, silica-alumina, silica-magnesia, alumina-magnesia, silica-magnesia-alumina.
In the catalyst of the present invention, the active matrix component is contained in an amount of 1 to 30% by mass, preferably 5 to 25% by mass, and more preferably 5 to 20% by mass. If the content of the active matrix component is less than 1% by mass, a sufficient coarse resolution in the matrix cannot be obtained, and the active surface is adversely affected, and the bulk density is reduced and the wear resistance and fluidity are deteriorated. Is concerned. On the other hand, when the content of the active matrix component is more than 30% by mass, the content of zeolite as the main active component is lowered, and the decomposition activity may be insufficient.

  In the catalyst of the present invention, the clay mineral is contained in an amount of 10 to 40% by mass, preferably 15 to 40% by mass, and more preferably 20 to 35% by mass. When the clay mineral content is less than 10% by mass, the pore structure is maintained and the catalyst shape is deteriorated. Wear resistance and fluidity become insufficient. On the other hand, if the content of clay mineral is more than 40% by mass, the content of zeolite, which is the main active ingredient, becomes low, and the decomposition activity may become insufficient.

  In the catalyst of the present invention, the metal scavenger is contained up to 10% by mass. If it exceeds 10% by mass, the physical properties will be adversely affected, and excessive active metal components may cause adverse effects on the active surface such as zeolite poisoning, which is not preferable.

<Average particle size>
The particle size distribution of the catalyst sample was measured with a laser diffraction / scattering particle size distribution measuring apparatus (LA-950V2) manufactured by Horiba, Ltd. Specifically, the sample was put into a solvent (water) so that the light transmittance was in the range of 70 to 95%, and the measurement was performed at a circulation rate of 2.8 L / min, an ultrasonic wave of 3 min, and the number of repetitions of 30. The median diameter (D50) is adopted as the average particle diameter, and the average particle diameter of the fluid catalytic cracking catalyst of the present invention is preferably 40 to 90 μm, and more preferably 50 to 80 μm.

<Specific surface area (SA)>
The catalyst of the present invention needs to have a specific surface area measured by the BET (Brunauer-Emmett-Teller) method in the range of 180 to 320 m ² / g. If the specific surface area is smaller than 180 m ² / g, the catalytic cracking reaction may not be sufficiently advanced in a short contact time in a fluid catalytic cracking process or the like. On the other hand, when it is larger than 320 m ² / g, sufficient strength cannot be obtained as a fluid catalyst.

<Pore volume (PV)>
The fluid catalytic cracking catalyst of the present invention has a pore volume (PV) of 0.25 to 0.45 ml / g, preferably 0.26 to 0.35 ml / g in the whole pore diameter range measured by a pore filling method of water. Within the range of g. If the pore volume is less than 0.25 ml / g, sufficient catalytic decomposition activity may not be obtained. In addition, as described above, in the present invention in which the pore volume ratio of the macropores is suppressed within a predetermined range, it is difficult to manufacture the pore volume exceeding 0.45 ml / g.

<Bulk density (ABD)>
A method for measuring the bulk density (ABD) will be described. The weight of the fluid catalytic cracking catalyst was measured using a 25 ml cylinder, and the bulk density was calculated from the weight per unit volume. As a result, the bulk density has a lower limit of 0.68. When the bulk density is lower than 0.68, the wear resistance becomes insufficient, and when used as a fluid catalyst, it becomes a factor that easily powders and scatters.

[Production method of fluid catalytic cracking catalyst]
The fluid catalytic cracking catalyst of the present invention adjusts a slurry containing, for example, a zeolite (crystalline alumina silicate), an alumina binder, a clay mineral component, the additive described above, and the metal scavenger of the present invention, The powder obtained by spray drying is obtained by firing the powder obtained by spray drying, for example, at 400 to 600 ° C. in a muffle furnace for 0.5 to 10 hours.

[Example 1]
<Preparation of metal scavenger T1>
897 g of 28 mass% titanium tetrachloride aqueous solution was diluted with 1638 g of pure water. This diluted titanium tetrachloride aqueous solution was added to 230 g of ammonia water having a concentration of 15% by mass and hydrolyzed to prepare a titania hydrogel. By washing and filtering this gel, 1400 g of titania gel having a TiO ₂ concentration of 18% by mass (250 g as TiO ₂ ) was obtained. 2513 g of pure water was added to 1400 g of this titania gel to obtain a 6% by mass titania hydrogel slurry as TiO ₂ .
954 g of magnesium nitrate hexahydrate (manufactured by Wako Pure Chemical Industries) and 266 g of lanthanum nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) are dissolved in 1500 g of pure water, and the solid content concentration (MgO + La ₂ O ₃ ) is 9% by mass. 220 g of mixed solution was obtained. This solution was added to the titania gel slurry and stirred for 15 minutes. The raw material slurry was used as droplets, and spray drying was performed with a spray dryer having an inlet temperature of 200 to 230 ° C and an outlet temperature of 130 ° C. The sample after spray drying was fired at 600 ° C. for 3 hours to obtain a metal scavenger T1.

<Vanadium capturing ability confirmation test of metal scavenger T1>
3 g of 38% by mass of vanadium sulfate was dissolved in 3 g of pure water to obtain an about 19% by mass vanadium sulfate aqueous solution in terms of V ₂ O ₅ . 21 g of a metal scavenger T1 having a solid content concentration of 21% is weighed and impregnated with a vanadium sulfate solution in this metal scavenger T1 to obtain a metal scavenger carrying 5% by mass as V ₂ O _5. It was. 6 g of this V ₂ O ₅ impregnated metal scavenger was mixed with 33 g of zeolite powder to form granules, and then calcined at 780 ° C. for 13 hours in a 100% steam atmosphere. Specific surface area (SA), unit cell constant (UD), and Y-cont were measured for samples before and after firing under steam conditions, and the retention after firing under steam conditions for each physical property value was calculated by the following equation.
Retention rate = (measured value after firing) / (measured value before firing) × 100
For measurement of the unit cell constant, a powder X-ray diffractometer (manufactured by Rigaku Corporation: RINT-2200, Bruker X D8 ADVANCE) was used. Using a Cu—Kα ray, the lattice constant was calculated under the conditions of a tube voltage of 30 kV and a tube current of 20 mA, and obtained according to ASTM D3942-97.

Regarding Y-cont, the total peak height (H) of (331), (511), (440), (533), (642) and (555) planes was determined by X-ray diffraction, and commercially available on the basis. The total peak height (H ₀ ) was similarly determined for forjasite type zeolite (manufactured by Union Carbide, SK-40), and determined by the following formula.
Y-cont. = H / H ₀ × 100 (%)
<Preparation of fluid catalytic cracking catalyst (1) containing metal scavenger T1>
429 g of a basic aluminum chloride aqueous solution having a concentration of 24% by mass and 551 g of pure water were mixed and stirred. Next, 1320 g of a 30% strength by weight zeolite slurry is added to the mixed solution, and 414 g of kaolin as a clay mineral component, 203 g of active alumina as an active matrix component, and 14 g of a metal scavenger T1 are sequentially added as additives. A slurry was obtained. Dispersion treatment was performed using a homogenizer, and the obtained raw material slurry had a solid content concentration of 35% and a pH of 4.4.
The raw material slurry was used as droplets and spray drying was performed with a spray dryer having an inlet temperature of 250 ° C. and an outlet temperature of 150 ° C. to obtain spherical particles having an average particle diameter of 65 μm. The spray-dried particles were fired in an electric furnace at 450 ° C. for 1 hour in an air atmosphere to obtain fired particles.

300 g of the obtained fired particles were added to 1500 g of pure water at 60 ° C. and stirred for 5 minutes. The pH of this slurry was 3.6. After suction filtration, the filtration residue was washed with 1500 g of pure water at 60 ° C. to obtain a washed particle cake (1).
After mixing and resuspending 1500 g of pure water at 60 ° C. and the washed particle cake (1), 30.5 g of ammonium sulfate was added and stirred for 20 minutes. After suction filtration, the filtration residue was washed with 1500 g of pure water at 60 ° C. to obtain a washed particle cake (1 ′).
After mixing and resuspending 1500 g of pure water at 60 ° C. and the washed particle cake (1 ′), 29 g of 22% by mass lanthanum chloride aqueous solution, which is a polyvalent cation source for ion exchange of zeolite, was added, and 20 Stir for minutes. After suction filtration, the filtration residue particles were washed with 1500 g of pure water at 60 ° C. After performing this operation twice, the filtration residue particles were dried at 135 ° C. for 2 hours to obtain a fluid catalytic cracking catalyst (1).

Example 2 (TiO ₂ / MgO / La ₂ O ₃ = 50/10/40)
<Preparation of metal scavenger T2>
By the same procedure as in Example 1, a 6% by mass titania hydrogel slurry was obtained as TiO ₂ . 289 g of magnesium nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) and 532 g of lanthanum nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) are dissolved in 1899 g of pure water, and the solid content concentration (MgO + La ₂ O ₃ ) is 9 mass%. 2720 g of a mixed solution was obtained. This solution was added to the titania gel slurry and stirred for 15 minutes. The raw material slurry was used as droplets, and spray drying was performed with a spray dryer having an inlet temperature of 200 to 230 ° C and an outlet temperature of 130 ° C. The sample after spray drying was fired at 600 ° C. for 3 hours to obtain a metal scavenger T2.

<Vanadium scavenging ability confirmation test of metal scavenger T2>
A scavenging ability test was performed on the prepared metal scavenger T2 in the same procedure as the vanadium scavenging ability confirmation test of the metal scavenger of Example 1.

Example 3 (TiO ₂ / MgO / La ₂ O ₃ = 50/40/10)
<Preparation of metal scavenger T3>
By the same procedure as in Example 1, a 6% by mass titania hydrogel slurry was obtained as TiO ₂ . Magnesium nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) 1163 g, lanthanum nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) 133 g are dissolved in pure water 1424 g, and a solid content concentration (MgO + La ₂ O ₃ ) 9 mass% mixed solution 2720 g was obtained. This solution was added to the titania gel slurry and stirred for 15 minutes. The raw material slurry was used as droplets, and spray drying was performed with a spray dryer having an inlet temperature of 200 to 230 ° C and an outlet temperature of 130 ° C. The sample after spray drying was fired at 600 ° C. for 3 hours to obtain a metal scavenger T3.

<Vanadium scavenging ability confirmation test of metal scavenger T3>
A scavenging ability test was performed on the prepared metal scavenger T3 in the same procedure as the vanadium scavenging ability confirmation test of the metal scavenger of Example 1.

[Example 4] (Metal scavenger MgO is changed to CaO)
<Preparation of metal scavenger T4>
By the same procedure as in Example 1, a 6% by mass titania hydrogel slurry was obtained as TiO ₂ . 632 g of calcium nitrate tetrahydrate (manufactured by Wako Pure Chemical Industries, Ltd.), 266 g of lanthanum nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) are dissolved in 182.3 g of pure water, and the solid content concentration (CaO + La ₂ O ₃ ) is 9% by mass. 2720 g of a mixed solution was obtained. This solution was added to the titania gel slurry and stirred for 15 minutes. The raw material slurry was used as droplets, and spray drying was performed with a spray dryer having an inlet temperature of 200 to 230 ° C and an outlet temperature of 130 ° C. The sample after spray drying was fired at 600 ° C. for 3 hours to obtain a metal scavenger T4.

<Vanadium scavenging ability confirmation test of metal scavenger T4>
A scavenging ability test was performed on the prepared metal scavenger T4 in the same procedure as the vanadium scavenging ability confirmation test of the metal scavenger of Example 1.
In addition, since the result similar to MgO type | system | group was obtained by the vanadium capture | acquisition ability test, the catalyst containing the said metal scavenger T4 is not prepared.

[Example 5] (Metal scavenger La ₂ O ₃ is changed to Ce ₂ O ₃ )
<Preparation of metal scavenger T5>
By the same procedure as in Example 1, a 6% by mass titania hydrogel slurry was obtained as TiO ₂ . Magnesium nitrate tetrahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) 954 g, cerium nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) 199 g was dissolved in 1568 g of pure water, and a solid content concentration (MgO + Ce ₂ O ₃ ) 9 mass% mixed solution 2720 g was obtained. This solution was added to the titania gel slurry and stirred for 15 minutes. The raw material slurry was used as droplets, and spray drying was performed with a spray dryer having an inlet temperature of 200 to 230 ° C and an outlet temperature of 130 ° C. The sample after spray drying was fired at 600 ° C. for 3 hours to obtain a metal scavenger T5.

<Vanadium scavenging ability confirmation test of metal scavenger T5>
A scavenging ability test was performed on the prepared metal scavenger T5 in the same procedure as the vanadium scavenging ability confirmation test of the metal scavenger of Example 1.
Note that the vanadium scavenging capacity test, since La ₂ O ₃ system and similar results were obtained, the catalyst containing the metal scavenger T5 is not prepared.

[Example 6]
<Preparation of fluid catalytic cracking catalyst (2) containing 1% by mass of metal scavenger T1>
429 g of a 24% by mass basic aluminum chloride aqueous solution and 550 g of pure water were mixed and stirred. Next, 1320 g of 30% by mass zeolite slurry was added to the mixed solution, and 418 g of kaolin as a clay mineral, 203 g of active alumina as an active matrix, and 11 g of a metal scavenger (T1) were sequentially added as additives. Obtained. Dispersion treatment was performed using a homogenizer, and the obtained raw material slurry had a solid content concentration of 35% by mass and a pH of 4.4.
The raw material slurry was used as droplets, and spray drying was performed with a spray dryer having an inlet temperature of 250 ° C. and an outlet temperature of 150 ° C. to obtain spherical particles having an average particle diameter of 65 μm. The spray-dried particles were fired in an electric furnace in an air atmosphere at 450 ° C. for 1 hour to obtain fired particles.

300 g of the obtained fired particles were added to 1500 g of pure water at 60 ° C. and stirred for 5 minutes. The pH of this slurry was 3.6. After suction filtration, the filter residue was washed with 1500 g of pure water at 60 ° C. to obtain a washed particle cake (2).
After mixing and resuspending 1500 g of pure water at 60 ° C. and the washed particle cake (2), 30.5 g of ammonium sulfate was added and stirred for 20 minutes. After suction filtration, the filtration residue was washed with 1500 g of pure water at 60 ° C. to obtain a washed particle cake (2).
After mixing and resuspending 1500 g of pure water at 60 ° C. and the washed particle cake (2), 29 g of 22% by mass lanthanum chloride aqueous solution as a polyvalent cation source was added and stirred for 20 minutes. After suction filtration, the filtration residue particles were washed with 1500 g of pure water at 60 ° C. After performing this operation twice, the filtration residue particles were dried at 135 ° C. for 2 hours to obtain a fluid catalytic cracking catalyst (2).

[Example 7]
<Preparation of fluid catalytic cracking catalyst (3) containing 10% by mass of metal scavenger T1>
429 g of a 24 mass% basic aluminum chloride aqueous solution and 563 g of pure water were mixed and stirred. Next, 1320 g of 30% by mass zeolite slurry was added to the mixed solution, and 307 g of kaolin as a clay mineral, 203 g of active alumina as an active matrix, and 109 g of a metal scavenger (T1) were sequentially added as additives. Got. Dispersion treatment was performed using a homogenizer, and the resulting raw material slurry had a solid content concentration of 35 mass% and a pH of 4.4.
The raw material slurry was used as droplets, and spray drying was performed with a spray dryer having an inlet temperature of 250 ° C. and an outlet temperature of 150 ° C. to obtain spherical particles having an average particle diameter of 65 μm. The spray-dried particles were fired in an electric furnace in an air atmosphere at 450 ° C. for 1 hour to obtain fired particles.

300 g of the obtained fired particles were added to 1500 g of pure water at 60 ° C. and stirred for 5 minutes. The pH of this slurry was 3.6. After suction filtration, the filter residue was washed with 1500 g of pure water at 60 ° C. to obtain a washed particle cake (1).
After mixing and resuspending 1500 g of pure water at 60 ° C. and the washed particle cake (3), 30.5 g of ammonium sulfate was added and stirred for 20 minutes. After suction filtration, the filtration residue was washed with 1500 g of pure water at 60 ° C. to obtain a washed particle cake (3).
After mixing and resuspending 1500 g of pure water at 60 ° C. and the washed particle cake (3), 29 g of 22% by mass lanthanum chloride aqueous solution as a polyvalent cation source was added and stirred for 20 minutes. After suction filtration, the filtration residue particles were washed with 1500 g of pure water at 60 ° C. After performing this operation twice, the filtration residue particles were dried at 135 ° C. for 2 hours to obtain a fluid catalytic cracking catalyst (3).

[Reference Example 1]
<Preparation of fluid catalytic cracking catalyst (3) containing 15% by mass of metal scavenger T1>
429 g of 24 mass% basic aluminum chloride aqueous solution and 570 g of pure water were mixed and stirred. Next, 1320 g of 30% by mass zeolite slurry was added to this mixed solution, and 2456 g of kaolin as a clay mineral, 203 g of active alumina as an active matrix, and 163 g of a metal scavenger (T1) were sequentially added as additives. Got. Dispersion treatment was performed using a homogenizer, and the obtained raw material slurry had a solid content concentration of 35% by mass and a pH of 4.4.
The raw material slurry was used as droplets, and spray drying was performed with a spray dryer having an inlet temperature of 250 ° C. and an outlet temperature of 150 ° C. to obtain spherical particles having an average particle diameter of 65 μm. The spray-dried particles were calcined in an electric furnace at 450 ° C. for 1 hour in an air atmosphere to obtain calcined particles.

300 g of the obtained fired particles were added to 1500 g of pure water at 60 ° C. and stirred for 5 minutes. The pH of this slurry was 3.6. After suction filtration, the residue was washed with 1500 g of pure water at 60 ° C. to obtain a washed particle cake (4).
After mixing and resuspending 1500 g of pure water at 60 ° C. and the washed particle cake (4), 30.5 g of ammonium sulfate was added and stirred for 20 minutes. After suction filtration, the filtration residue was washed with 1500 g of pure water at 60 ° C. to obtain a washed particle cake (4).
After mixing and resuspending 1500 g of pure water at 60 ° C. and the washing particle cake (4), 29 g of 22% by mass lanthanum chloride aqueous solution as a polyvalent cation source was added and stirred for 20 minutes. After suction filtration, the filtration residue particles were washed with 1500 g of pure water at 60 ° C. After performing this operation twice, the filtration residue particles were dried at 135 ° C. for 2 hours to obtain a fluid catalytic cracking catalyst (R2).
Since ABD (bulk density) was lower than 0.68, performance evaluation was not performed because it could not withstand actual use.

[Comparative Example 1]
<Measurement of physical properties when zeolite is impregnated with V ₂ O ₅ >
As V ₂ O ₅ , 1 g of 38% by mass of vanadium sulfate was dissolved in 1 g of pure water to obtain an approximately 19% by mass (V ₂ O ₅ ) vanadium sulfate aqueous solution. By weighing 52 g of zeolite having a solid content concentration of 91% by mass and impregnating with a vanadium sulfate solution, a zeolite carrying 1% by mass as V ₂ O ₅ was obtained. This sample was granulated and then calcined at 780 ° C. for 13 hours in a 100% steam atmosphere. SA (specific surface area), unit cell constant (UD) of the sample before and after firing under steam conditions, Y-cont. Was measured, and the retention after firing under steam conditions in each measurement was calculated.

[Comparative Example 2] (TiO ₂ / MgO = 50/50)
<Preparation of metal scavenger RT1>
By the same procedure as in Example 1, a 6% by mass titania hydrogel slurry was obtained as TiO ₂ . 1454 g of magnesium nitrate tetrahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 1267 g of pure water to obtain 2720 g of a 9% by mass solution as MgO. This solution was added to the titania gel slurry and stirred for 15 minutes. The raw material slurry was used as droplets and spray-dried by a spray dryer having an inlet temperature of 200 to 220 ° C and an outlet temperature of 130 ° C. The sample after spray drying was fired at 600 ° C. for 3 hours to obtain a metal scavenger RT1.
<Vanadium scavenging ability confirmation test of metal scavenger RT1>
With respect to the prepared metal scavenger RT1, a scavenging ability test was performed in the same procedure as the vanadium scavenging ability confirmation test of the metal scavenger of Example 1.

[Comparative Example 3] (TiO ₂ / La ₂ O ₃ = 50/50)
<Preparation of metal scavenger RT2>
By the same procedure as in Example 1, a 6% by mass titania hydrogel slurry was obtained as TiO ₂ . 665 g of lanthanum nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 2055 g of pure water to obtain 2720 g of a 9% by mass solution as La ₂ O ₃ . This solution was added to the titania gel slurry and stirred for 15 minutes. The raw material slurry was used as droplets and spray-dried by a spray dryer having an inlet temperature of 200 to 220 ° C and an outlet temperature of 130 ° C. The sample after spray drying was fired at 600 ° C. for 3 hours to obtain a metal scavenger RT2.
<Vanadium scavenging ability confirmation test of metal scavenger RT1>
A scavenging ability test was performed on the prepared metal scavenger RT2 in the same procedure as the vanadium scavenging ability confirmation test of the metal scavenger of Example 1.

[Comparative Example 4]
<Preparation of fluid catalytic cracking catalyst R1 containing no metal scavenger>
In accordance with the catalyst preparation method of Example 1, trial production was performed in a system in which the metal scavenger was not added to the prepared slurry, and a fluid catalytic cracking catalyst (R1) was obtained.

[Comparative Example 5]
<Preparation of known metal scavenger RT3>
As an existing metal scavenger, an additive reported in JP-A-6-136369 was prepared by the preparation method described in the publication (according to Example 5 of the publication). A specific preparation method is as follows.
An oxalic acid solution (18% by mass) was prepared by adding 41 g of oxalic acid per 193 g of H ₂ O and heated to 45 ° C. Next, 94 g of rare earth hydrate containing 22% by mass of La ₂ O ₃ was mixed with 233.6 g of this oxalic acid solution. 5g MgO was added to adjust the pH of the mixture to 4.0. The oxalate / MgO slurry thus obtained is added to the metakaolin / aluminum sol binder slurry reacted with acid (solid content 22% by weight), then the slurry is spray dried at 177 ° C. and 1 at 593 ° C. Metal scavenger RT3 was prepared by air calcined for hours.

<Vanadium scavenging ability confirmation test of metal scavenger RT3>
A scavenging ability test was performed on the prepared known metal scavenger RT3 in the same procedure as the vanadium scavenging ability confirmation test of the metal scavenger of Example 1.
<Preparation of fluid catalytic catalyst R3 containing metal scavenger RT3>
A fluid catalytic catalyst (R3) was obtained by the same procedure as the catalyst preparation method of Example 1 for the fluid catalytic cracking catalyst to which the prepared known metal scavenger RT3 was added.

[Comparative Example 6]
<Preparation of known metal scavenger RT4>
As an existing metal scavenger, an additive reported in JP-A-6-134297 was prepared by the preparation method described in the publication (according to Example 1 of the publication). A specific preparation method is as follows.
One acidic stream and one basic stream are fed simultaneously to a high speed mixing pump reactor with multiple ports and in 1000 g of heel water in a reaction kettle kept at 38-40 ° C. with good agitation A coprecipitation test was performed by precipitating a viscous product stream. The acidic feed stream contained 164 g MgO and 103 g La-rich rare earth oxide, all in nitrate form in a total volume of 2460 ml. The basic feed stream had a sodium aluminate solution with 164 g Al ₂ O ₃ along with 80 g of 50 wt% sodium hydroxide solution in a total volume of 2460 ml. These two streams were fed at an equal rate of 100 ml / min, but stream No. with 16 wt% sodium hydroxide. The feed rate of 3 was adjusted to control the pH of the slurry in the reaction kettle to 9.4-9.5. The slurry was aged for 15 minutes under these conditions and the slurry was immediately vacuum filtered after making sure that the pH was 9.5 at the end of aging. The filter cake is then homogenized using a high shear mixer, once dry dried (Drais milled), rehomogenized and spray dried.

A 100 g portion of the resulting microspheres was slurried once in 250 g of room temperature 3 tap water for 3 minutes, then washed once with another 250 g of room temperature tap water and filtered. After drying overnight in a 115 ° C. oven, the material was air calcined at 704 ° C. for 2 hours. This sample was designated as a known metal scavenger RT4.
<Vanadium scavenging ability confirmation test of metal scavenger RT4>
With respect to the prepared known metal scavenger RT4, a scavenging ability test was performed in the same procedure as the vanadium scavenging ability confirmation test of the metal scavenger of Example 1.

[Composition and properties of metal scavenger and catalyst]
Table 1 shows the compositions and physical property values of the metal scavengers of the above Examples and Comparative Examples.
Table 2 shows the composition and physical property values of the fluid catalytic cracking catalysts 1 to 3 according to the above examples and the fluid catalytic cracking catalysts R1 to R3 of the comparative example. In Table 2, PAC is an alumina binder.

[バナジウム（Ｖ）の捕捉能確認試験結果]
上述の実施例及び比較例の金属捕捉剤について行ったバナジウム捕捉能確認試験及び金属捕捉剤を含まない場合のバナジウム捕捉能確認試験の結果を表３に示す。

[Vanadium (V) capture ability confirmation test results]
Table 3 shows the results of the vanadium scavenging ability confirmation test and the vanadium scavenging ability confirmation test in the case where the metal scavenger is not included, which was performed on the metal scavengers of the above-described Examples and Comparative Examples.

表３から分かるように、Ｖ_２Ｏ_５が存在する状態でＹ型ゼオライトに対し、スチーム処理による加速被毒試験を行うと、Ｙ型ゼオライトの結晶の崩壊の程度が大きく、また比表面積も小さくなっており、金属捕捉剤Ｔ１を含まないＹ型ゼオライト（比較例１）については、前記結晶及び比表面積の保持率がおよそ２６％とかなり小さくなっている。これに対して金属捕捉剤Ｔ１〜Ｔ５(実施例１〜５)を含む系については、結晶および比表面積の保持率が４０％以上であり、金属捕捉剤Ｔ１を含む試料では、４３％となっている。一方、比較例２、３、５、６で作成した金属捕捉剤を含む試料を用いた場合は、金属捕捉剤を含まない場合（比較例１）に比べると保持率は高いが、金属捕捉剤Ｔ１〜Ｔ５よりは、保持率が劣ることが分かる。この結果から、本発明の金属捕捉剤は、流動接触分解触媒に用いられるＹ型ゼオライトについてバナジウムによる劣化を抑えることができる効果が大きいことが分かる。

As can be seen from Table 3, when an accelerated poisoning test by steam treatment is performed on the Y-type zeolite in the presence of V ₂ O ₅ , the degree of crystal disintegration of the Y-type zeolite is large and the specific surface area is also small. In the case of the Y-type zeolite (Comparative Example 1) that does not contain the metal scavenger T1, the retention rate of the crystal and the specific surface area is as small as about 26%. On the other hand, for the system containing the metal scavengers T1 to T5 (Examples 1 to 5), the retention ratio of crystals and specific surface area is 40% or more, and 43% for the sample containing the metal scavenger T1. ing. On the other hand, when the sample containing the metal scavenger prepared in Comparative Examples 2, 3, 5, and 6 was used, the retention rate was higher than that in the case of not containing the metal scavenger (Comparative Example 1). It can be seen that the retention rate is inferior to T1 to T5. From this result, it can be seen that the metal scavenger of the present invention has a great effect of suppressing the deterioration due to vanadium in the Y-type zeolite used for the fluid catalytic cracking catalyst.

[Catalyst performance evaluation test]
About the catalyst of each above-mentioned Example and a comparative example, the performance evaluation test of the catalyst was done on the same crude oil and the same reaction conditions using ACE-MAT (Advanced Cracking Evaluation-Micro Activity Test). The results of the catalyst performance evaluation test are shown in Table 4 (in the case of C / O = 3.75).

ただし、これらの性能評価試験を行う前に、各触媒の表面に、予めニッケルおよびバナジウムをそれぞれ１０００質量ｐｐｍ（ニッケルの質量を触媒の質量で除算している）および２０００質量ｐｐｍ（バナジウムの質量を触媒の質量で除算している）沈着させ、次いでスチーミングして擬平衡化処理を行った。具体的には、各触媒を予め６００℃で２時間焼成した後、所定量のナフテン酸ニッケル、およびナフテン酸バナジウムのトルエン溶液を吸収させ、次いで１１０℃で乾燥後、６００℃で１．５時間焼成し、次いで７８０℃で１３時間スチーム処理を行った。

However, before carrying out these performance evaluation tests, nickel and vanadium were each preliminarily 1000 ppm by mass (the nickel mass was divided by the mass of the catalyst) and 2000 ppm by mass (the vanadium mass). (Divided by the mass of the catalyst) and then steamed to give a quasi-equilibrium treatment. Specifically, after each catalyst was calcined at 600 ° C. for 2 hours in advance, a predetermined amount of nickel naphthenate and a vanadium naphthenate toluene solution were absorbed, then dried at 110 ° C., and then at 600 ° C. for 1.5 hours. After baking, steam treatment was performed at 780 ° C. for 13 hours.

The operating conditions in the performance evaluation test are as follows.
Feedstock: Crude oil desulfurized atmospheric residue oil (DSAR) + Desulfurized vacuum gas oil (DSVGO) (50 + 50)
Catalyst / oil mass ratio (C / O): 3.75
Reaction temperature: 520 ° C
1) Conversion rate = 100− (LCO + HCO + CLO)
2) The mass ratio of catalyst / oil was measured at 3.75, and each yield at the same conversion rate (= 73% by mass) was interpolated.
3) Boiling point range of gasoline: 30-216 ° C
4) Boiling range of LCO: 216 to 343 ° C. (LCO: Light Cycle Oil)
5) Boiling range of HCO and CLO: 343 ° C. + (HCO: Heavy Cycle Oil, CLO: Clarified Oil)
[Evaluation results]
According to the activity evaluation results, compared with the samples of Comparative Examples 4 and 5 (catalysts R1 and R3), the samples of Examples 1, 6, and 7 (catalysts 1, 2, and 3) have a higher conversion rate, so that It turns out that it is excellent. Even when viewed at the same conversion rate, the gasoline yield is high, but the dry gas and Coke selectivity is low, indicating that the catalyst is excellent in metal resistance.

Claims (10)

A carrier made of titanium oxide;
An oxide of a Group 2 element which is a first metal component supported on the carrier;
And a rare earth metal oxide as a second metal component supported on the carrier. Metal scavenger
The average particle size is in the range of 1-30 μm,
The specific surface area is in the range of 5 to 100 m ² / g,
The metal scavenger according to claim 1, wherein the pore volume is in the range of 0.1 to 0.4 ml / g.   The metal scavenger according to claim 1 or 2, wherein the first metal component is at least one of magnesium and calcium.   4. The metal scavenger according to claim 3, wherein the content of the first metal component supported on the carrier is 20 to 80% by mass in terms of oxide with respect to 100% by mass of the carrier. .   The metal scavenger according to any one of claims 1 to 4, wherein the second metal component is at least one of lanthanum and cerium.   The metal scavenger according to claim 5, wherein the content of the second metal component supported on the carrier is 20 to 80% by mass in terms of oxide with respect to 100% by mass of the carrier.   The metal scavenger according to any one of claims 1 to 6, wherein the content ratio of the first metal component to the second metal component is 0.25 to 4.0 in terms of oxide. . Obtaining a titanium oxide slurry;
Using the titanium oxide slurry to obtain a metal scavenger precursor in which a first metal component and a second metal component are supported on a titanium oxide support;
Drying the metal scavenger precursor, and further baking to obtain a metal scavenger.   A fluid catalytic cracking catalyst comprising the metal scavenger according to any one of claims 1 to 8, a zeolite, an alumina binder, and a viscosity mineral component.   The fluid catalytic cracking catalyst according to claim 9, further comprising an additive having an active matrix component.