JPS6148979B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a catalyst for hydrocracking hydrocarbons. Generally, a catalyst in which a hydrogenation metal component is supported on a solid acid is used for hydrogenolysis of hydrocarbon oil.
This type of catalyst is generally divided into two types, one of which is called an amorphous type and the other one is called a zeolite type. Amorphous catalysts include solid acidic non-crystalline porous materials, such as silica-alumina, on which Group and B metals are supported; It includes activated zeolite or silicalite type zeolite, which supports a metal hydride component. Since these two types of catalysts have different properties, they can be used depending on the purpose of use. Zeolite catalysts have the advantage of higher decomposition activity than amorphous catalysts. In addition, since amorphous catalysts are easily poisoned by basic nitrogen,
While it is necessary to denitrify feedstock oil in advance, zeolite catalysts can perform hydrocracking without denitrification, except for oils with an extremely high nitrogen content. Furthermore, since the zeolite catalyst has resistance to coke precipitation, it is possible to apply a lower hydrogen pressure than an amorphous catalyst. However, even zeolites with such excellent properties have major drawbacks depending on the purpose of use. Because of the high cracking activity of zeolite, the cracked products undergo secondary cracking, resulting in a high production rate of gas and naphtha, making it unsuitable for processes aimed at obtaining middle distillates. In recent years, demand for petroleum products has been decreasing for LPG and naphtha, and increasing for kerosene. The decline in demand for LPG and naphtha is due to increased production of cheap natural gas. On the other hand, the increase in demand for kerosene and diesel fuel is not only due to the potential increase in energy consumption, but also to a large extent due to the increasing quality of fuel that has accompanied the advancement of industry and lifestyle. On the other hand, the oil produced is becoming heavier year by year, and the yield of middle distillates tends to decrease. Therefore, the conversion of heavy oil into middle distillates is becoming an important issue for the time being. SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a catalyst for hydrocracking hydrocarbons that can crack heavy oil with good selectivity and improve the yield of middle distillates. As a result of intensive research aimed at achieving this purpose, the present inventors have found that a hydrogenation catalyst containing Y-type zeolite with an average particle size of 0.3 μm or less as a cracking active component can be suitable for that purpose. This led to the completion of the present invention. That is, according to the present invention, the average grain size of the crystals is 0.3
Provided is a catalyst for hydrocracking of hydrocarbons, comprising a carrier composed of a Y-type zeolite of μm or less and a porous inorganic oxide, and a hydrogenation metal component supported on the carrier. . In the catalyst of the present invention, the average particle size of crystals is 0.3μ as a carrier component that is active in decomposing hydrocarbons.
It is characterized by containing Y-type zeolite of m or less. The average particle size of Y-type zeolite crystals commonly used as a catalyst carrier is usually 2 μm or more, but even if such a crystal is used, the intended purpose cannot be achieved. The Y zeolite crystals used in the present invention with an average particle size (hereinafter simply referred to as average particle size) of 0.3 μm or less have a higher activity and a higher middle distillate yield than conventional ones. Provide a catalyst. The reason why Y-type zeolite with an average particle size of 0.3 μm or less has higher activity as a hydrocracking catalyst and higher selectivity for middle distillates than Y-type zeolite with an average particle size of 2 μm or more is due to the acid strength of both ( This seems to be due to the difference in the distribution of H ₀ ). According to the research conducted by the present inventors, it was found that there is a good correlation between the average particle size of Y-type zeolite and the acid strength distribution. In particular, the acid strength of Y type zeolite with an average particle size of 0.3 μm or less is lower than that of Y type zeolite with an average particle size of 2 μm or more.
Compared to that of type zeolites, the acid strength of type Y zeolites with an average particle size of less than 0.3 μm is relatively low. This makes it difficult for secondary cracking to occur during hydrocracking of hydrocarbons,
It is presumed that this increases the selectivity of the middle distillate. The acid strength distribution of Y-type zeolite varies greatly depending on the type of ions that exchange Na ions and the degree of substitution. The higher the ion exchange rate (degree of substitution), the higher the amount of acid and the higher the acid strength. Furthermore, the acid strength of those substituted with H ⁺ is greater than those substituted with La〓, Ca〓, etc. Figure 1 shows 97% of each of the Y-type zeolite with an average particle size of 0.25 μm used in the present invention and the commercially available Y-type zeolite with an average particle size of 2 μm or more.
%La substitution product acid strength distribution is shown. In addition, in this specification, the amount of acid sites with an intensity of H ₀ < +3.3 is defined as the total acid amount, and H ₀
The amount of acid sites with an intensity of <-8.2 is called the amount of strong acid. As can be seen by comparing the acid strength distribution curve-1 of Y-type zeolite with an average particle size of 0.25 μm and the acid strength distribution curve-2 of a commercially available Y-type zeolite with an average particle size of 2 μm or more, the total acid content of both is While they are almost equal, the amount of strong acid is considerably smaller in the zeolite used in the present invention. Figure 2 shows the total acid content (H ₀ < +3.3) (curve -
1) and the total amount of strong acid (H ₀ <-8.2) (curve-2),
A graph plotted against the average particle size of zeolite is shown. As is clear from the measurement results shown in this graph, the average particle diameter has little effect on the total amount of acid, but it has a large effect on the amount of strong acid. Regarding Y-type zeolite, the reason why the acid strength of fine-grained zeolites is lower than that of larger-sized particles is still not clearly elucidated, but zeolite crystals with small-sized particles have a higher crystallinity. This is thought to be due to the fact that the degree of crystallinity is lower than that of particles with a large particle size. In Y-type zeolite, there is no significant difference in physical properties between those with an average particle size of 0.3 μm or less and those with an average particle size of 2 μm or more. For example, when measuring the surface area by the BET method, the surface area of the former is 650 ~ 750 m ² /g, while that of the latter is 700-800 m ² /g,
The two are almost equal, and the peak positions in X-ray diffraction completely match. However, when comparing the two, there is a slight difference in the peak intensity of X-ray diffraction between the two, and the peak intensity of the former is 70% or less than that of the latter, so the crystallinity of the former is It is shown that the crystallinity is slightly lower than that of the latter. However, this does not mean that the fine Y-type zeolite contains amorphous silica or silica alumina. For example, when observing an electron micrograph of Y-type zeolite with an average particle size of 0.1 μm, no amorphous substance other than zeolite particles is found. Furthermore, the absence of such amorphous substances in the zeolite particles is also suggested by the measured values of the total acid amount shown in FIG. That is, as can be seen from FIG. 2, the total acid content of Y-type zeolite with an average particle size of 0.1 μm is approximately equal to the total acid content of Y-type zeolite with an average particle size of 2 μm or more. In contrast,
As is well known, the total acid content of amorphous silica alumina is about 0.5 to 0.55 meq/g, and La-Y
This is much smaller than the total acid content of type zeolite, which is 2.5meq/g. Therefore, if simple amorphous silica alumina exists in the fine zeolite particles, the total acid content of Y-type zeolite with an average particle size of 0.3 μm or less will be much smaller than that of Y-type zeolite with an average particle size of 2 μm or more. It should be. However, this fact cannot be accepted. Therefore, Y-type zeolite with an average particle size of 0.3 μm or less is basically a zeolite, but because its crystal structure is incomplete, Y-type zeolite with an average particle size of 2 μm or more
It is thought that even if the specific surface area and total acid content are the same as those of the type zeolite, there is a difference in the acid strength distribution. As is clear from the above, the fine particle Y-type zeolite used in the present invention is a Y-type zeolite produced under reaction conditions that insufficiently produce Y-type zeolite, in other words, an amorphous material. It is fundamentally different from Y-type zeolite, which contains carbon dioxide, and Y-type zeolite, which has a low ion exchange rate. Such conventional zeolites are undesirable because they have a decrease in strong acid sites as well as a decrease in specific surface area and total acid content, resulting in a decrease in decomposition activity. Furthermore, the reason why Y-type zeolite with an average particle size of 0.3 μm or less shows higher decomposition activity than Y-type zeolite with an average particle size of 2 μm or more has not been clearly elucidated, but it is speculated as follows. That is, Y
In the case of type zeolite, it has extremely small pores of around 10 Å, so the reactant reacts mostly near the surface of the zeolite particle, and inside the particle, small molecules can be decomposed so that they can fully diffuse within the 10 Å pores. It should only contribute to On the other hand, in the case of the microparticles used in the present invention, their decomposition activity is higher than that of particles with an average particle size of 2 μm or more. The reason why fine Y-type zeolite has enhanced decomposition activity is thought to be that by reducing the particle size, the outer surface area available for reaction increases, which increases the decomposition rate of hydrocarbons. The catalyst for hydrocracking hydrocarbons according to the present invention comprises:
It has a structure in which a metal hydride component is supported on a carrier made of Y-type zeolite porous inorganic oxide with an average particle size of 0.3 μm or less. Porous inorganic oxides include silica, diatomaceous earth,
Non-solid acid materials such as clay and solid acid materials such as silica-alumina are included, whereas the former only serves as a forming aid or diluent;
The latter also serves as a catalytic component that undertakes the hydrogenation and decomposition of large hydrocarbon molecules that are difficult to decompose with zeolites. However, in both cases, it is essential that the material be porous in order to allow sufficient diffusion of the reactant molecules. The catalyst carrier used in the present invention can be obtained by mixing the Y-type zeolite and an inorganic oxide. In this case, the zeolite is preliminarily mixed with ammonium ions, It is preferable to perform ion exchange with a rare earth element such as La or Ce. Ion exchange of zeolite can be performed on a hydrous gel of zeolite that has been washed, or it can be performed on a hydrous gel that has just been calcined. The inorganic oxide to be mixed with the zeolite is preferably in the form of a hydrous gel, and the mixture of the hydrous gel and the zeolite is adjusted to the required water content and then formed into granules,
It is molded into a desired shape and size, such as a pellet shape.
The dimensions of the catalyst of the present invention are not particularly limited; for example,
The average particle diameter is 0.5 to 3 mm. As the hydrogenation metal component in the catalyst of the present invention, a known one that has been conventionally applied to this type of hydrogenation catalyst is applied, and usually a group metal and/or group B metal of the periodic table is used, preferably a metal of group 3 and/or group B of the periodic table. , Group B metals, especially palladium, are most suitable;
Combinations of group metals (eg Cr, Mo, W) and iron group metals (Fe, Co, Ni) are also preferred. In the case of group metals, it is preferable to support them on Y-type zeolite in advance when preparing the catalyst. In the catalyst of the present invention, when the content of the heat-resistant inorganic oxide, which is one of the components of the carrier, is 30% by weight or less, the group metal is formed into a mixture of the Y-type zeolite and the inorganic oxide and calcined. Even when the catalyst is supported on the carrier obtained by the above process, it exhibits the same effect as a catalyst produced using a Y-type zeolite on which a group metal has been supported in advance. In the catalyst of the present invention, the amount of group metal supported is 0.2 to 5% by weight, preferably 0.5 to 2% by weight, in terms of metal. When a combination of group B metal and iron group metal is used as a hydrogenation metal component, the amount of the group B metal supported in the catalyst is 4
-20% by weight, preferably 6-12% by weight, and iron group metals from 1-10% by weight, preferably 2-6% by weight.
It is. Since solid acids tend to produce coke at least in large amounts, it is necessary to add hydrogenation metal. In the case of a catalyst that uses a solid acid substance as a porous inorganic oxide, in addition to the zeolite component, it is essential that this solid acid substance also supports a hydrogenation metal component to impart hydrogenation ability. As the hydrogenation metal component, a combination of a group B metal and an iron group metal is preferably employed. When supporting a hydrogenation metal component on a catalyst carrier,
As described above, the metal hydride component can be supported only on the zeolite component or on both the zeolite component and the inorganic oxide component. As a method for supporting the metal hydride component on an airless oxide component, there is a method in which it is mixed in advance into a hydrogel of an inorganic oxide by a known method such as coprecipitation or gel mixing, or a method in which it is mixed in a hydrogel of an inorganic oxide in advance by a method such as co-precipitation or gel mixing. A metal hydride component can be supported on the catalyst carrier obtained by molding and firing the mixture by a known catalyst supporting method such as an impregnation method or an adsorption method. In the catalyst of the present invention, the inorganic oxide used as one component of the catalyst carrier is porous, and specific examples of such materials include, for example:
Examples include silica alumina, silica titania, alumina, alumina titania, alumina zirconia, silica magnesia, silica zirconia, alumina-phosphorus pentoxide, and alumina boria. In the present invention, among these inorganic oxides, it is particularly preferable to use silica alumina, alumina titania, and alumina zirconia. Furthermore, when using these inorganic oxides as catalyst supports, it is important to adjust the pore size to a range suitable for the reactants.
For example, it is preferable to use petroleum raw materials with a lower boiling point than vacuum gas oil, coal liquefied oil, shale oil, etc., with an average pore size (diameter) of 100 to 200 Å, and residual oils such as vapor distillation residue oil and vacuum distillation residue. 150~300Å
It is preferable to use one having an average pore size of . Note that these numerical values are values that take into account that the reactant is effectively diffused into the catalyst. In the catalyst of the present invention, the ratio of the zeolite component and the inorganic oxide component constituting the catalyst carrier can be appropriately changed depending on the type of inorganic oxide, the type of target hydrocarbon, etc. but,
When the inorganic oxide is a solid acid substance, generally the total amount of zeolite and inorganic oxide is
The zeolite component is preferably in the range of 10 to 50% by weight, and if the inorganic oxide is a non-solid acid substance, the zeolite component is in the range of 10 to 90% by weight, preferably 50 to 90% by weight. It is better to As mentioned above, the zeolite component used as a carrier component in the present invention is Y
This type of zeolite is disclosed in, for example, Japanese Patent Publication No. 57-8049 and Japanese Patent Application Laid-Open No. 55-90417.
It is possible to manufacture it according to the publication. In addition, the present inventors, apart from those known methods,
In particular, we have developed a method suitable for producing Y-type zeolite with an average particle size of 0.3 μm or less. That is, the present inventors have found that by using NaCl as a nucleation promoter and employing a low-temperature synthesis reaction, it is possible to produce microcrystalline Y-type zeolite that meets the purpose of the present invention. In this case, the reaction temperature is preferably 30 to 70°C, and if it is lower than 30°C, the induction period will exceed 500 hours, which is not preferable. Addition of NaCl has the effect of shortening the time required for nucleation in the hydrothermal synthesis reaction and reducing the size of the produced crystal particles.
The amount of NaCl added is preferably selected in the range of 2 to 10% by weight based on the mother liquor for zeolite synthesis (reaction raw material mixture). For example, when comparing the results when NaCl is added and when NaCl is not added,
The average particle size of the Y-type zeolite obtained when 5% by weight is added is reduced to about 1/2 to 1/3 of the average particle size of the Y-type zeolite obtained when it is not added.
This effect of NaCl is thought to be due to its salting out effect, but similar salts, e.g.
When compared with Na ₂ SO ₄ , MgCl ₂ , KCl, etc., NaCl shows the most excellent effect. The composition of the raw material mother liquor is not much different from the known mother liquor composition necessary for producing Y-type zeolite. For example, when using an aqueous colloidal silica sol as the main source of silica, the preferred raw material mother liquor composition (molar ratio) is as follows. be. _Na2O /SiO2 _{0.4-0.6 SiO2} / _{Al2O3 7-20 H2O} / _Na2O 20-50 Note that the mother liquor composition does not include the value of NaCl. The hydrocarbon oils treated using the catalyst of the present invention mainly have a boiling point of 300°C or higher, such as vacuum gas oil, deasphalted oil, atmospheric residual oil, vacuum residual oil, shale oil, and tarside oil. ,
Includes coal liquefied oil, FCC cycle stock, etc. The activity and life of the catalyst of the present invention can be further enhanced by demetallizing and denitrifying these hydrocarbon oils prior to treatment with the catalyst of the present invention. When hydrocracking hydrocarbon oil using the catalyst of the present invention, the reaction temperature is generally 320 to 480°C.
℃, preferably 360-450℃, hydrogen pressure is 40
-300Kg/ ^cm2 , preferably 60-200Kg/ ^cm2 , and the contact time is usually 0.1-300Kg/cm2 as liquid hourly space velocity.
10hr ^-1 . Such reaction conditions are appropriately selected depending on the type of raw material oil and the desired conversion rate and selectivity. The higher the boiling point range of the feedstock oil and the higher the content of Conradson carbon and nitrogen, the lower the reactivity, so a higher reaction temperature and lower liquid hourly space velocity are applied. Next, in the following, we will discuss the production of Y-type zeolite with an average particle size of 0.3 μm or less, an example of catalyst production using the same, and a comparison between hydrocracking using the catalyst of the present invention and hydrocracking using a conventional catalyst. show. Note that methods for measuring various physical properties in this specification are additionally described below. () X-ray diffraction In order to confirm the formation of Y-type zeolite, an X-ray diffraction apparatus manufactured by Rigaku Denki Co., Ltd. was used. The conditions of use are as follows. Target Cu filter Fe Voltage 30KV Current 15mA cfs 1000c/s Time constant 1sec Chart speed 2cm/min Scanning speed 2°/min () Measurement of crystallinity 2θ= of commercially available Y-type zeolite (SK-40)
The X-ray intensity of the peak at 6° was set as 100, and the ratio of the X-ray intensity of the peak at the same position of the prototype zeolite to this was taken as the crystallinity of the zeolite. () Average particle size The average particle size was determined from an electron micrograph of the sample. Video photographs with a direct magnification of 1,000 times and a photographic magnification of 50,000 times were obtained for several fields of view, 200 particles were randomly selected from the images, their diameters were measured, and the weight average was taken as the average particle diameter.
For sample preparation, for the prototype zeolite, the zeolite was washed and separated from the zeolite mother liquor and dispersed in pure water using ultrasonic waves without drying.
For commercially available zeolite for comparison, fine powder was mixed with epoxy resin, and this was cut into ultra-thin sections of about 500 Å using a microtome cutter. This was used as a sample for measurement. () Specific surface area measurement Surface area measuring device SA- manufactured by Shibata Rigaku Kikai Seisakusho
1000 was used. The sample was dried in advance at 250°C to a constant weight, then weighed, left to cool in a N ₂ stream at 300°C, and then subjected to measurement. () Acid strength distribution A method called the modified Benecy method was used.
For details, please refer to "New Experimental Chemistry Course" published by Maruzen Co., Ltd.
16, page 211. The sample is prepared in advance.
It was pulverized to 300 mesh or less, dried at 250°C for one day and night, and then used for measurement. As indicators, PKa=3.3, +1.5, -2.4, -5.6, -, respectively.
P-dimethylaminoazobenzene, phenylazodiphenylamine, P-dimethylaminoazobenzene with a color change point at 8.2
-Nitrodiphenylamine, benzylideneacetophenone, and anthraquinone were used, respectively. Reference example 1 560 parts of colloidal silica (Snowtex 30) manufactured by Nissan Chemical Co., Ltd. containing 30% by weight of SiO ₂ and Na ₂ O
30% by weight, _{Al2O3 45.2} % by weight, _H2O 24.8% by weight
including. A solution prepared by dissolving 31.7 parts of commercially available sodium aluminate, 122.4 parts of sodium hydroxide, and 78 parts of sodium chloride in 203 parts of deionized water and 30% by weight of
560 parts of colloidal silica (Snowdex 30) manufactured by Nissan Chemical Co., Ltd. containing SiO ₂ was mixed at room temperature for 30 minutes. The molecular composition of the produced sol (zeolite mother liquor) is as follows. 12Na ₂ O・1.00Al ₂ O ₃・20SiO ₂・239H ₂ O・9.5NaCl This sol was placed in a cooling container and left at 10°C for 3 days and nights, and then reacted at 90°C for 250 hours.
Y-type zeolite with a diameter of 0.14 μm was produced. After washing and drying, this Y-type zeolite had a crystallinity of 65% and a specific surface area of 660 m ² /g. 97% of this zeolite
The total acid content of the La substituted product is 2.42meq/g, and the strong acid content is 0.14
It was meq/g. Reference Example 2 A mother liquor sol containing no NaCl and having the following composition was prepared using the same reagents as in Reference Example 1, and stirred until it became homogeneous. 14.7Na ₂ O・Al ₂ O ₃・33.3SiO ₂・564H ₂ O After storing this sol in the freezer at 7℃ for 3 days and nights, it was placed in a sealed pirate tube and heated to 50℃.
The reaction mixture was placed in a hot water bath for 340 hours to crystallize. After crystallization, washing and filtration were repeated to obtain a cake. A portion of the cake was dried at 100°C and subjected to X-ray diffraction to confirm the formation of Y-type zeolite. The crystallinity of this Y-type zeolite is 58% and the specific surface area is 480m ² /
It was hot at g. Moreover, the average particle diameter measured by an electron microscope was 0.25 μm. The total amount of acid in the La substituted product is 2.6 mmol/g, and the amount of strong acid at H ₀ <-8.2 is 0.08 m
It was mol/g. Comparative Example 1 Similar to Example 1 of Japanese Patent Publication No. 36-1639,
_Na2O 30.0wt%, _{Al2O3 45.2wt} % and _H2O 24.8wt%
5 parts of sodium aluminate and caustic soda containing % by weight
22 parts were dissolved in 90 parts of deionized water. This solution
In addition to 124 parts of colloidal silica (Snowtex 30) containing 30.0% by weight of SiO ₂ , a mixture having the following composition was obtained. 13.6Na ₂ O: Al ₂ O ₃ : 28.2 SiO ₂ : 450H ₂ O Next, after stirring this mixture until it becomes homogeneous, the mixture is sealed in a glass autoflave and left at 100°C for 21 hours to crystallize. turned into After crystallization, filtration and washing were repeated to obtain a zeolite cake. Dry part of this cake at 100℃,
It was used for various measurements. This Y-type zeolite had a crystallinity of 103% and a specific surface area of 650 m ² /g. Furthermore, the average particle size determined by electron microscopy was 3.2 μm. In addition, the total acid content of the La substituted product is 2.5 mmol/g,
The amount of strong acid at H ₀ <-8.2 was 0.22 mmol/g. Example 1 Each of the zeolite cakes obtained in Reference Examples 1 and 2 and Comparative Example 1 was dispersed in a 10% by weight lanthanum nitrate solution of 5 times the amount of the cake, heated to 80°C, and left for 2 hours with stirring. did. Thereafter, this dispersion was washed and filtered. When this operation was repeated three times, the Na ₂ O content of each zeolite became 3% or less of that in the raw zeolite. Therefore, the ion exchange rate by La is 97% or more. These, 3
Colloidal silica (Snowtex-30) was added to the aqueous gel of the seed La-substituted zeolite to make a slurry containing added SiO ₂ at a ratio of 20 wt% to the zeolite. After thoroughly mixing with a high-speed stirrer for 2 hours, excess water was removed by drying. It was removed and molded into pellets with a diameter of 1.2 mm using a piston type extruder. The three types of pellets were dried at 120°C for 2 hours and then calcined at 550°C for 3 hours. These pellets were impregnated with an ammoniacal palladium solution, dried, and calcined to support 0.5% by weight of Pd on each pellet. These three types of catalysts using the Y-type zeolites of Reference Examples 1 and 2 and Comparative Example 1 as raw materials are named Reduced A, B, and R-1, respectively. Example 2 According to Example 1 of Japanese Patent Publication No. 57-44605,
A boehmite sol was made (this boehmite has a specific surface area of 320 m ² /g and a pore volume of 1.13 cc/g after firing).
−Al ₂ O ₃ ). The La-substituted zeolite cake obtained in Example 2 and Comparative Example 1 was added to this boehmite sol with Al ₂ O ₃ :Y-type zeolite=50:
After mixing in a high-speed stirrer for 2 hours so that the concentration of the mixture was 50%, the mixture was filtered under pressure to obtain a dehydrated cake. These cakes were molded using a piston type extruder to a diameter of 1.2 mm.
It was formed into pellets. The two types of pellets are
After drying at 150°C for 8 hours, it was fired at 500°C for 3 hours. Next, each fired pellet was impregnated with an ammonia aqueous solution containing ammonium molybdate and nickel nitrate, dried and fired to support Ni and Mo. The thus obtained catalyst containing Y-type zeolite of Reference Example 1 is designated as C, and the catalyst containing Y-type zeolite of Comparative Example 1 is designated as R-2. Example 3 Using the catalysts A, B, and R-1 obtained above, a hydrocracking experiment of Gatsuchisaran vacuum gas oil was conducted.
Table 1 shows the properties of catalysts A, B, and R-1. In addition, the properties of Gatsuchi Saran vacuum light oil are shown in Table 2. Furthermore, the reaction conditions and the product distribution and conversion rate at the 700th hour of each operation are shown in Table 3. catalyst A,
Comparing the product distribution obtained using B with that of R-1, it is clearly seen that the gas and naphtha fractions are small and the kerosene fraction is large.

【table】 Table-2 Specific gravity (D15/4) 0.9200 Nitrogen content (wt%) 0.17 Sulfur content (wt%) 2.06 ASTM Distillation Test IBP 303 (℃) 5vol% 375 10 〃 384 30 〃 415 50 〃 448 70 〃 484 90 〃 531 EP〃564 191-343℃ fraction (wt%) 2.4 Distillate above 343℃ (wt%) 97.6

【table】

[Table] Example 4 Using the catalysts C and R-2 obtained in Example 2 above, Arabian Light atmospheric residual oil was hydrocracked. Table 4 shows the properties of catalysts C and R-2.
The properties of the Arabian Light atmospheric residual oil are shown in Table 5, and the reaction conditions, product distribution and conversion rate % at 700 hours after the start of operation are shown in Table 6. It can be seen that the product obtained by Catalyst C contains less gas and naphtha and more kerosene fraction than Catalyst R-2. The conversion rate of catalyst C is also higher than that of R-2. From these results, the effect of zeolite particle size can be clearly confirmed.

[Table] * Boehmite alumina
Table-5 Specific gravity (D15/4) 0.952 Viscosity (cp, 50℃) 142 Sulfur content (wt%) 2.9 Nitrogen content (wt%) 0.16 Vanadium content (wt-ppm) 29 Asphaltene content (wt%) 2.1 ASTM Distillation test IBPvol% 231 (℃) 5 〃 346 10 〃 356 30 〃 434 50 〃 500 70 〃 574 EP (74vol%) 579 191~343℃ fraction (wt%) 3.6 343~538℃ fraction (wt%) 45.8 Distillate above 538℃ (wt%) 50.6

【table】

【table】 [Brief explanation of the drawing]

Figure 1 shows the acid strength distribution curve of Y-type zeolite, and curve-1 is the average particle size of 0.25μ used in the present invention.
m and curve-2 respectively show the measurement results for commercially available average grains with a diameter of 2 μm or more. FIG. 2 shows the relationship between the average particle diameter of Y-type zeolite and the amount of acid, where curve-1 shows the measurement results of the total amount of acid and curve-2 shows the measurement results of the total amount of strong acid.

Claims (1)

[Claims] 1. A hydrocarbon hydrogen characterized by comprising a carrier composed of a Y-type zeolite with an average crystal grain size of 0.3 μm or less and a porous inorganic oxide, and a hydrogenation metal component supported on the carrier. Catalyst for chemical decomposition.