A coke production additive, a method for producing the additive, and a method for producing a fluid catalytic cracking catalyst composition containing the additive.

Abstract

To provide an additive for coke production that yields sufficient coke and facilitates a smooth catalytic cracking process, and a method for producing the same.SOLUTION: An additive for coke production includes metal oxide with a nickel component supported on a lanthanum phosphate component. The lanthanum phosphate component is an oxide including lanthanum and phosphorus, with a molar ratio of lanthanum to phosphorus ranging from 0.8 / 1.2 to 1.2 / 0.8. The nickel component is fixed in the additive for coke production in the range of 0.1-10 mass% in terms of nickel.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a coke-producing additive, a method for producing the additive, and a fluid catalytic cracking catalyst composition containing the additive. More specifically, the present invention relates to a technique for increasing the amount of coke produced by adding a coke-producing additive to a fluid catalytic cracking catalyst. [Background technology]

[0002] A fluid catalytic cracking (FCR) in the petroleum refining process uses the heat of combustion of coke deposited on a FCR catalyst as reaction heat, balancing the heat to obtain the desired oil product without external heating. However, if a light, easily decomposable oil with low levels of residual coal and heavy metals is used as the raw material for the oil product, a coke shortage will occur on the FCR catalyst. Furthermore, a decrease in the amount of raw material processed by the FCR will also result in a coke shortage, which may make it difficult to operate the apparatus. Therefore, it is necessary to generate an appropriate amount of coke.

[0003] Generally, fluid catalytic cracking catalysts are required to exhibit high performance in various aspects, such as having a high cracking capacity for heavy hydrocarbon oils, including atmospheric distillation residues (hereinafter also referred to as "bottom resolution"), and producing a small amount of coke precipitate on the catalyst surface. In this regard, conventional fluid catalytic cracking of heavy hydrocarbon oils has been developed with the aim of lowering the yield of coke and increasing the yield of gasoline and middle distillates (diesel fuel and kerosene) (high liquid yield).

[0004] However, in recent years there has been a growing call for the reduction of greenhouse gases (GHGs) such as carbon dioxide, and the trend towards energy transition from fuel oil is progressing. As a result, the amount of petroleum refined will gradually decrease in the future, and the petroleum refining process is also undergoing changes. This requires catalyst development that differs from conventional fluid catalytic cracking catalysts aimed at suppressing coke formation.

[0005] As conventional fluid catalytic cracking catalysts, Patent Documents 1 and 2 disclose catalysts containing zeolites that include rare earth metals, which exhibit low coke yield and excellent selectivity for gasoline, liquefied petroleum gas, or middle distillates.

[0006] Furthermore, Patent Documents 3 and 4 disclose additives for fluid catalytic cracking catalysts that suppress coke formation, improve the cracking efficiency of heavy oil fractions, and enhance the desulfurization effect. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Publication No. 2020-142229 [Patent Document 2] Japanese Patent Publication No. 2020-032350 [Patent Document 3] Japanese Patent Publication No. 2011-147933 [Patent Document 4] Japanese Patent Publication No. 2005-262160 [Overview of the project] [Problems that the invention aims to solve]

[0008] However, the fluid catalytic cracking catalysts disclosed in Patent Documents 1 to 4, which use zeolites containing rare earth metals as a catalytic component, are merely fluid catalytic cracking catalysts for hydrocarbon oils that are effective in suppressing coke formation and have excellent selectivity (high liquid yield and low gas). The fluid catalytic cracking catalysts disclosed in Patent Documents 1 to 4, which use zeolites containing rare earth metals as a catalytic component, do not generate an appropriate amount of coke to continuously maintain the fluid catalytic cracking reaction in response to the coke shortage that occurs as the processing volume of raw material oil decreases.

[0009] Currently, due to environmental concerns, there is a demand for reducing greenhouse gas (GHG) emissions, and the trend is toward a gradual decline in petroleum refining. In the future, as petroleum refining decreases, it is expected that in the fluid catalytic cracking reaction of heavy hydrocarbon oils, it will become necessary to produce an appropriate amount of coke to prevent the heat balance from being unbalanced and the operation of the fluid catalytic cracking unit from becoming difficult due to the suppression of coke production as in the past.

[0010] Therefore, an object of the present invention is to provide a coke-generating additive and a method for producing the same, which generates an appropriate amount of coke and facilitates the catalytic cracking process, in order to prevent the operation of the fluid catalytic cracking apparatus from becoming difficult due to an imbalance in heat balance caused by suppressing the amount of coke generated. Furthermore, another object of the present invention is to provide a fluid catalytic cracking catalyst composition containing the coke-generating additive. [Means for solving the problem]

[0011] Against this technical backdrop, the inventors diligently studied to solve the above problems and discovered that a coke-generating additive could be obtained that would produce an appropriate amount of coke and facilitate the fluid catalytic cracking process of heavy hydrocarbon oils, leading to the development of the present invention.

[0012] The present invention, developed to solve the aforementioned problems and achieve the above objectives, is as follows. Specifically, the present invention is a coke-making additive comprising a metal oxide in which a nickel component is supported on a lanthanum phosphate component, wherein the lanthanum phosphate component is an oxide containing lanthanum and phosphorus, with a lanthanum / phosphorus molar ratio in the range of 0.8 / 1.2 to 1.2 / 0.8, and the nickel component is fixed in the coke-making additive in the range of 0.1 to 10% by mass in terms of nickel.

[0013] Furthermore, regarding the above-mentioned coke production additive according to the present invention, (1) It further contains a binder component, the binder component being present in the coke production additive in an amount of 5 to 20% by mass in terms of oxides. (2) The above coke-making additive has an average particle size in the range of 50 to 90 μm and a specific surface area of ​​30 to 200 m². 2 A more preferable solution would be to have a pore volume within the range of 0.05 to 0.50 ml / g.

[0014] Secondly, the present invention proposes a method for producing a coke-making additive, comprising: a first step of mixing an aqueous solution containing lanthanum with an aqueous solution containing phosphate ions to obtain a mixed slurry; a second step of filtering and washing away solid components from the mixed slurry to obtain a washed cake; a third step of redispersing the washed cake in water, adding an aqueous solution containing nickel, and then spray-drying it to obtain a spray-dried product; and a fourth step of heat-treating the spray-dried product to obtain a coke-making additive.

[0015] Furthermore, the present invention provides, thirdly, a fluid catalytic cracking catalyst composition characterized by comprising any of the above-mentioned coke-producing additives and a fluid catalytic cracking catalyst.

[0016] Furthermore, regarding the above-mentioned coke production additive according to the present invention, (3) A more preferable solution would be for the coke-generating additive contained in the above-mentioned fluid catalytic cracking catalyst composition to be in the range of 1.0 to 15.0% by mass. [Effects of the Invention]

[0017] According to the additive for coke production of the present invention, in the catalytic cracking reaction process using VGO-FCC or HC-BTM with a reduced petroleum refining amount as a raw material, the amount of coke production can be suppressed, so that an appropriate amount of coke can be produced to prevent the heat balance from being disrupted and the operation of the fluid catalytic cracking (FCC) unit from becoming difficult. Furthermore, according to the fluid catalytic cracking catalyst composition of the present invention in which the additive is added to the fluid catalytic cracking catalyst, in the catalytic cracking reaction process using VGO-FCC or HC-BTM as a raw material, the amount of coke production can be increased to prevent the operation of the fluid catalytic cracking unit from becoming difficult. Therefore, according to the fluid catalytic cracking catalyst composition of the present invention, by increasing the calorific value, the heat balance can be adjusted, contributing to the stable operation of the fluid catalytic cracking (FCC) unit.

Embodiments for Carrying out the Invention

[0018] Hereinafter, preferred embodiments of the present invention will be described in detail. [Additive for Coke Production] The additive for coke production of the present invention is composed of a metal oxide in which a nickel component is supported on lanthanum phosphate. Hereinafter, each component contained in the additive for coke production of the present invention will be described.

[0019] <Lanthanum Phosphate Component> The lanthanum phosphate used in the present invention is obtained from a water-soluble compound containing lanthanum and phosphoric acid or a phosphate, and the molar ratio of lanthanum (La) to phosphorus (P) is preferably in the range of 0.8:1.2 to 1.2:0.8. If the molar ratio of lanthanum (La) to phosphorus (P) is within the above range, it satisfies the physical properties required as an additive and is preferable because it effectively contributes to coke production. Examples of the water-soluble compound containing lanthanum include inorganic salts such as lanthanum halides, carbonates, sulfates, nitrates, and hydroxides, and organic acid salts such as citrate, acetate, and acetylacetonate salts. Examples of phosphoric acid or phosphates include phosphoric acid and phosphates such as sodium phosphate and potassium phosphate.

[0020] <Nickel content> The nickel component used in this invention is a nickel oxide precursor, and can be an inorganic salt such as nickel halide, carbonate, sulfate, nitrate, or hydroxide, or an organic salt such as citrate, acetate, or acetylacetonate. The nickel component is preferably present in the coke-making additive at a concentration of 0.1 to 10% by mass in terms of nickel. A concentration of 0.1% by mass or more in terms of nickel is preferable because it allows for a moderate dehydrogenation reaction during the reaction, thereby promoting coke formation. On the other hand, a concentration of 10% by mass or less in terms of nickel is preferable because it reduces the likelihood of reactions that hinder coke formation, such as hydrogenation reactions.

[0021] The coke-forming additive of the present invention preferably has an average particle size in the range of 50 to 90 μm. The average particle size can be evaluated by the laser diffraction / scattering particle size distribution measurement described below. If the average particle size is excessively smaller than 50 μm, the metal capture efficiency will decrease, while if it is excessively larger than 90 μm, the wear resistance and strength of the coke-forming additive may decrease.

[0022] The coke production additive of the present invention has a specific surface area (SA) of 30 to 200 m² as measured by the BET method. 2 It is preferable that the range is within / g. The specific surface area of ​​the coke-forming additive is 30m². 2 If the specific surface area is excessively small compared to / g, the reactivity decreases and the effect as an additive diminishes. On the other hand, if the specific surface area is 200m² 2 If the amount is excessively large compared to / g, the strength of the coke-forming additive will decrease, and the shape retention of the coke-forming additive may be reduced. The specific surface area of ​​the coke-forming additive is 40-150m². 2 It is more preferable that the range is within / g.

[0023] The coke-making additive of the present invention preferably has a bulk density (ABD) of 0.70 g / ml or higher. If the bulk density is lower than 0.70 g / ml, the abrasion resistance will be insufficient, and when used as a fluid catalyst, it may easily pulverize and cause the catalyst to scatter, making it unsuitable for practical use. On the other hand, the upper limit of the bulk density is determined by the density of the composition, but if the bulk density is higher than 1.50 g / ml, there is a risk that catalyst circulation within the apparatus will become impossible. The bulk density can be measured, for example, by measuring the weight of the coke-making additive using a 25 ml cylinder and calculating the bulk density from the weight per unit volume.

[0024] The coke-forming additive of the present invention may further contain a binder component. Examples of binder components included in the coke-forming additive include alumina sol and monoaluminum phosphate. The binder component is preferably included in the coke-forming additive in an amount of 5 to 20% by mass in terms of oxide. A binder component content of 5% by mass or more is preferable because it makes it easier to maintain the physical properties required for the additive, and a content of 20% by mass or less is preferable because it minimizes the reduction in coke-forming function.

[0025] [Regarding the manufacturing method of additives for coke production] One example of a method for producing a coke-making additive according to the present invention is: (I) A first step of mixing an aqueous solution containing lanthanum with an aqueous solution containing phosphate ions to obtain a mixed slurry, (II) A second step of filtering and washing the solid components from the mixed slurry to obtain a washed cake, (III) A third step in which the washed cake is redispersed in water, an aqueous solution containing nickel is added, and then the mixture is spray-dried to obtain a spray-dried product. (IV) A fourth step of heat-treating the spray-dried product to obtain an additive for coke production. Below, we will describe each step included in the method for producing the coke-making additive of the present invention.

[0026] <First step: A step of mixing an aqueous solution containing lanthanum with an aqueous solution containing phosphate ions to obtain a mixed slurry.> The present invention relates to a method for producing a coke-making additive, which includes a first step of mixing an aqueous solution containing lanthanum with an aqueous solution containing phosphate ions to obtain a mixed slurry. In the first step, a lanthanum-phosphate mixed slurry is prepared by first mixing the aqueous solution containing lanthanum with the aqueous solution containing phosphate ions. As components to be included in the aqueous solution containing lanthanum, for example, inorganic salts such as lanthanum halides, carbonates, sulfates, nitrates, and hydroxides, or organic salts such as citrates, acetates, and acetylacetonates can be used.

[0027] Next, as the phosphate ion-containing component in the aqueous solution containing phosphate ions, for example, phosphates such as phosphoric acid, sodium phosphate, and potassium phosphate can be used.

[0028] When mixing an aqueous solution containing lanthanum with an aqueous solution containing phosphate ions, it is preferable that the molar ratio of lanthanum (La) to phosphorus (P) be in the range of 0.8:1.2 to 1.2:0.8. A molar ratio of lanthanum (La) to phosphorus (P) within this range is preferable because it allows for the maintenance of the specific surface area necessary for coke production and satisfies the required physical properties as a coke production additive.

[0029] When preparing a mixed slurry by mixing an aqueous solution containing lanthanum and an aqueous solution containing phosphate ions, the pH of the mixed slurry solution consisting of the aqueous solution containing lanthanum and the aqueous solution containing phosphate ions may be adjusted as needed, or the temperature of the mixed slurry solution may be raised to promote the reaction. Specifically, the mixing conditions are as follows: The mixed slurry solution is heated to 20-90°C, preferably 25-80°C and maintained therein. An aqueous solution containing a metal component, heated to ±5°C, preferably ±2°C, more preferably ±1°C above the temperature of this solution, is continuously added over a period of 5-20 minutes, preferably 7-15 minutes, to form a precipitate and obtain a mixed slurry.

[0030] <Second step: Filtering and washing the solid components from the mixed slurry to obtain a washed cake> The present invention relates to a method for producing a coke-making additive, which includes a second step of filtering and washing the solid components from a mixed slurry to obtain a washing cake. In the second step, the solid components contained in the mixed slurry obtained in the first step are filtered off by filtration or the like, and then the solid components obtained after filtering are washed to obtain a washing cake. In the second step, water may be used to wash the mixed slurry, or hot water may be used.

[0031] <Third step: After redispersing the washed cake in water to obtain a redispersed slurry, an aqueous solution containing nickel is added, and then the product is spray-dried to obtain a spray-dried product.> The present invention provides a method for producing a coke-making additive, which includes a third step of redispersing a washed cake in water, adding an aqueous solution containing nickel, and then spray-drying to obtain a spray-dried product. In the third step, first, the washing cake obtained in the second step is redispersed in water to obtain a redispersed slurry. Here, the solid content concentration in the redispersed slurry obtained by redispersing the washing cake is preferably in the range of 15 to 45% by mass. Next, an aqueous solution containing nickel is added to the obtained redispersed slurry. Here, it is preferable that the nickel added to the redispersed slurry as an aqueous solution containing nickel is adjusted to be in the range of 0.1 to 10.0% by mass in terms of nickel in the coke production additive.

[0032] Furthermore, an aqueous solution containing nickel is added to the obtained redispersion slurry and mixed to allow the solid components in the redispersion slurry to react sufficiently with the nickel. The redispersion slurry-nickel mixed solution, to which the aqueous solution containing nickel has been added, is spray-dried. By spray-drying the redispersion slurry-nickel mixed solution, a spray-dried product, which is a precursor of the coke production additive, is obtained. The spray-drying conditions used in the third step are adjusted as appropriate so that the inlet temperature to the spray dryer is in the range of 200 to 500°C and the outlet temperature is in the range of 80 to 180°C, and the average particle size of the spray-dried product is in the range of 50 to 100 μm.

[0033] <Fourth step: Heat treatment of the spray-dried product to obtain an additive for coke production> The present invention relates to a method for producing a coke-making additive, which includes a fourth step of filtering and washing the solid components from a mixed slurry to obtain a washed cake. In the fourth step, the spray-dried product obtained in the third step is heat-treated to obtain the coke-making additive. Heat treatment means drying and baking. The heat treatment temperature is appropriately set in the range of 110 to 800°C for 0.5 to 24 hours to obtain the target product, the coke-making additive.

[0034] Furthermore, the method for producing the coke-making additive of the present invention may further include a grinding step after the fourth step to appropriately grind the coke-making additive after firing in order to adjust the particle size of the obtained coke-making additive.

[0035] [Regarding fluid catalytic cracking catalyst compositions] The fluid catalytic cracking catalyst composition of the present invention is characterized by comprising the above-mentioned coke-generating additive and a fluid catalytic cracking catalyst. In other words, the fluid catalytic cracking catalyst composition of the present invention means a blend of the fluid catalytic cracking catalyst and the coke-generating additive of the present invention. That is, the fluid catalytic cracking catalyst composition of the present invention (hereinafter referred to as "the catalyst composition of the present invention") has the above-mentioned coke-generating additive as an essential component, and other components include a zeolite component which is a fluid catalytic cracking catalyst, a binder component (silica-based binder or alumina-based binder), and a clay mineral component. The following describes each component included in the catalyst composition of the present invention.

[0036] <Fluid catalytic cracking catalyst> The fluid catalytic cracking treatment of crude oil or residual oil using the catalyst composition of the present invention is carried out under high temperature and high pressure conditions in a hydrogen atmosphere by filling a fixed-bed reactor with the catalyst composition. As the fluid catalytic cracking catalyst included in the catalyst composition of the present invention, a conventionally known fluid catalytic cracking catalyst (a general CVZ series fluid catalytic cracking catalyst provided by JGC Catalysts & Chemicals Ltd.) can be used.

[0037] <Contents of additives used in coke production> The catalyst composition of the present invention preferably contains the coke-forming additive of the present invention in an amount of 1.0 to 15.0% by mass. If the coke-forming additive is less than 1.0% by mass, it may not be possible to obtain the full effect of the additive, which is undesirable. On the other hand, if the coke-forming additive exceeds 15.0% by mass, the catalytic activity may decrease due to the dilution effect, which may lead to a decrease in the coke yield itself, which is also undesirable.

[0038] <Specific surface area (SA)> The catalyst composition according to the present invention has a specific surface area (SA) of 30 to 150 m² as measured by the BET (Brunauer-Emmett-Teller) method. 2 It is preferable that the range is within / g. The specific surface area is 30m². 2 If the value is less than / g, there is a risk that the catalytic cracking reaction may not proceed sufficiently with a short contact time in processes such as the fluid catalytic cracking process of heavy hydrocarbon oils. On the other hand, 150m 2 If the value is greater than / g, the catalyst composition containing the fluid catalytic cracking catalyst may not be able to obtain sufficient strength.

[0039] <Average particle size of additives and catalysts used in coke production> The coke-forming additive and fluid catalytic cracking catalyst contained in the catalyst composition according to the present invention have a predetermined average particle size. The particle size distribution of each sample, which is the coke-forming additive and the fluid catalytic cracking catalyst, can be measured using a laser diffraction / scattering particle size distribution analyzer (LA-950V2) manufactured by Horiba, Ltd. Specifically, the sample is placed in a solvent (water) so that the light transmittance is in the range of 70 to 95%, and the measurement can be performed with a circulation speed of 2.8 L / min, ultrasonic treatment for 3 min, and 30 repetitions. The median diameter (D50) is adopted as the average particle size, and the average particle size of the coke-forming additive and fluid catalytic cracking catalyst contained in the catalyst composition according to the present invention is preferably 40 to 100 μm, and more preferably 50 to 90 μm.

[0040] <Pore Volume (PV)> The coke production additive according to the present invention preferably has a pore volume (PV) of 0.05 to 0.50 ml / g, more preferably 0.10 to 0.45 ml / g, over the entire pore diameter range as measured by the pore-filling method of water. When used as a fluid catalytic cracking catalyst, if the pore volume is less than 0.05 ml / g, sufficient catalytic cracking activity may not be obtained. On the other hand, if the pore volume exceeds 0.50 ml / g, the catalyst strength may decrease.

[0041] <Bulk density (ABD)> The method for measuring the bulk density (ABD) of the coke-making additive according to the present invention involves measuring the weight of the coke-making additive using a 25 ml cylinder and calculating the bulk density from the weight per unit volume. It is preferable that the bulk density be at least 0.70 g / ml. If the bulk density is lower than 0.70 g / ml, the abrasion resistance will be insufficient, and when used as a fluid catalytic cracking catalyst, it may easily pulverize, potentially causing the catalyst to scatter. [Examples]

[0042] (Example 1) [Preparation of additives for coke production] 1722 g of lanthanum chloride aqueous solution (La2O3 equivalent concentration: 20.2 mass%) was diluted with 1722 g of deionized water, heated to 60°C, and then 246 g of phosphoric acid (P2O5 equivalent concentration: 61.6 mass%) was added. After thorough stirring, aqueous ammonia was added to adjust the pH to 6.3. Furthermore, the lanthanum-phosphoric acid mixed slurry solution was heated to 90°C, held for 30 minutes, and then cooled to obtain a mixed slurry.

[0043] The obtained mixed slurry was filtered through filter paper, washed with 10 L of ion-exchanged water by spraying, and the obtained solid was recovered as a washing cake. Next, the washing cake was diluted with ion-exchanged water to a LaPO4 concentration of 30% by mass, and further nickel nitrate was added to the slurry to a Ni content of 0.8% by mass, and spray drying was carried out with a spray dryer at an inlet temperature of 240 °C and an outlet temperature of 130 °C to obtain a spray-dried product. The obtained spray-dried product was calcined at 600 °C for 2 hours to obtain an additive (1) for coke formation. The properties of the additive (1) for coke formation obtained in Example 1 are shown in Table 1.

[0044] [FCC catalyst composition containing additive (1) for coke formation] The obtained additive (1) for coke formation was mixed with an FCC catalyst (manufactured by JGC Catalysts & Chemicals Ltd., CVZ catalyst) to 10% by mass. The obtained fluid catalytic cracking catalyst composition was subjected to a performance evaluation test of the catalyst composition under the same crude oil and the same reaction conditions using ACE-MAT (Advanced Cracking Evaluation-Micro Activity Test). However, before conducting these performance evaluation tests, a steam treatment was carried out at 780 °C for 13 hours for the purpose of simulating the state of being hydrothermally deteriorated in a catalyst regeneration tower in advance.

[0045] [Performance evaluation test (catalytic activity) of FCC catalyst composition] The reaction conditions and the like in the performance evaluation test of the FCC catalyst composition containing the additive (1) for coke formation obtained in Example 1 are as follows. The results of the performance evaluation test of the above catalyst composition are shown in Table 2. Feedstock: 脱硫減圧軽油(DSVGO)100 mass% Reaction temperature: 520 °C Space velocity (WHSV) based on catalyst mass: 8 h -1 Catalyst / oil ratio (hereinafter referred to as "C / O"): 5.0 (mass% / mass%) 1) Conversion rate: 100 - (LCO; HCO + CLO) (mass%) 2) Yield: Ratio of each product when C / O = 5.0 (mass%) 3) Boiling point range of gasoline: 30~216℃ (Gasoline) 4) Boiling point range of LCO: 216~343℃ (LCO: Light Cycle Oil) 5) Boiling point range of HCO + CLO: 343°C+ (HCO: Heavy Cycle Oil, CLO: Clarified Oil) 6) LPG (Liquid Petroleum Gas) 7) Dry Gas: Methane, ethane, and ethylene 8) Propylene: Included in LPG.

[0046] (Comparative Example 1) The coke-producing additive (1) obtained in Example 1 was not mixed with a conventionally known fluid catalytic cracking catalyst, and the same performance evaluation test was performed using only the FCC catalyst described in Example 1 (manufactured by JGC Catalysts & Chemicals Co., Ltd., CVZ catalyst). The results of the performance evaluation test of the catalyst composition are shown in Table 2.

[0047] [Preparation of additive (R1)] (Comparative Example 2) After preparing [Example 1: Additive 1] described in Japanese Patent Publication No. 2011-147933, the additive (R1) was obtained by impregnating it with an aqueous nickel nitrate solution so that the Ni content was 1.0% by mass, drying it at 120°C, and then holding it at 600°C for 2 hours.

[0048] [FCC catalyst composition containing additive (R1)] Instead of the coke-generating additive (1) obtained in Example 1, the obtained additive (R1) was mixed with the FCC catalyst (CVZ catalyst, manufactured by JGC Catalysts & Chemicals Co., Ltd.) at a concentration of 10% by mass. The performance evaluation test of the FCC catalyst composition of Comparative Example 2 was carried out in the same manner as in Example 1. The results of the performance evaluation test of the FCC catalyst composition of Comparative Example 2 are shown in Table 2.

[0049] [Table 1]

[0050] (Example 2) In Example 1, 1722 g of an aqueous lanthanum chloride solution (La2O3 concentration: 20.2% by mass) was diluted with 1722 g of deionized water, heated to 60°C, and then 222 g of phosphoric acid (P2O5 concentration: 61.6% by mass) was added. After thorough stirring, ammonia water was added to adjust the pH to 6.3. The process was carried out similarly to obtain coke production additive (2). The properties of coke production additive (2) obtained in Example 2 are shown in Table 1. Furthermore, the results of the performance evaluation test of the FCC catalyst composition containing coke production additive (2) are shown in Table 2.

[0051] (Example 3) In Example 1, 1722 g of an aqueous lanthanum chloride solution (La2O3 concentration: 20.2% by mass) was diluted with 1722 g of deionized water, heated to 60°C, and then 285 g of phosphoric acid (P2O5 concentration: 61.6% by mass) was added. After thorough stirring, ammonia water was added to adjust the pH to 6.8. The procedure was carried out similarly to obtain coke production additive (3). The properties of coke production additive (3) obtained in Example 3 are shown in Table 1. Furthermore, the results of the performance evaluation test of the FCC catalyst composition containing coke production additive (3) are shown in Table 2.

[0052] (Example 4) In Example 1, the same procedure was followed except that the Ni content was adjusted to 7.5% by mass to obtain coke-forming additive (4). The properties of coke-forming additive (4) obtained in Example 4 are shown in Table 1. Furthermore, the results of the performance evaluation test of the FCC catalyst composition containing coke-forming additive (4) are shown in Table 2.

[0053] [Table 2]

[0054] [Results of catalyst activity evaluation] According to the catalyst activity evaluation results, the catalysts prepared in Examples 1-4 showed higher coke yields at the same C / O ratio compared to Comparative Examples 1 and 2, confirming their contribution to increasing coke yield. [Industrial applicability]

[0055] As described above, the coke-generating additive according to the present invention has a high coke-generating ratio and wear resistance, making it suitable for use in fluid catalytic cracking catalysts to decompose hydrocarbon oils, thereby generating an appropriate amount of coke and continuously maintaining the fluid catalytic cracking reaction.

Claims

1. It contains a metal oxide in which a nickel component is supported on a lanthanum phosphate component. The oxide is such that the lanthanum / phosphorus molar ratio of the lanthanum phosphate component is 0.8 / 1.2 to 1.2 / 0.

8. A coke-forming additive used in a fluid catalytic cracking catalyst, characterized by containing the aforementioned nickel component in an amount of 0.1 to 10% by mass in terms of nickel.

2. A method for producing a coke-making additive used in a fluid catalytic cracking catalyst, The process involves mixing an aqueous solution containing lanthanum and an aqueous solution containing phosphate ions so that the lanthanum / phosphorus molar ratio is in the range of 0.8 / 1.2 to 1.2 / 0.8 to obtain a mixed slurry. The process involves filtering and washing away the solid components from the aforementioned mixed slurry to obtain a washed cake. The process involves redispersing the aforementioned washing cake in water, adding an aqueous solution containing nickel so that the nickel component content in the coke-making additive is 0.1 to 10% by mass in terms of nickel, and then spray-drying to obtain a spray-dried product. The process involves heat-treating the spray-dried product to obtain an additive for coke production, A method for manufacturing a coke-making additive that includes the following:

3. A method for producing a fluid catalytic cracking catalyst composition, comprising the step of mixing a coke-making additive according to claim 1 with a fluid catalytic cracking catalyst.

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