JPH0555188B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a zeolite-containing composition and a hydrocracking catalyst using the same, and more particularly to a zeolite-containing composition and a hydrocracking catalyst suitable for treating petroleum, particularly heavy residual oil. In recent years, there has been a worldwide trend for crude oil to become heavier, and at the same time, the demand structure for oil has changed, resulting in a shortage of light oil and a surplus of heavy oil. Therefore, many technologies have been developed to crack down heavy oil and convert it into light oil such as naphtha, kerosene, and diesel oil. Among these, hydroprocessing technologies such as hydrocracking and hydrorefining are considered to be very promising because they yield high-quality light oil. In this case, zeolite-based catalysts are widely used. Zeolites, especially faujasite-type zeolites, have relatively large pore diameters of about 10 Å for zeolites, have high decomposition activity, and can bring relatively large molecules close to the active site, so they are used as catalysts for catalytic cracking. Large molecules such as residual oil cannot approach the active sites present within the pores of the zeolite. In addition, the phodiasite type zeolite has the drawback of being weak against heat and water, and therefore has the essential drawback of not being a good catalyst for heavy residual oils and the like. In order to overcome these drawbacks, it has been proposed to use dealuminated Y-type zeolite.
43782, Japanese Patent Application Laid-Open No. 1983-101003), this zeolite is resistant to heat and ammonia, and the pore size is relatively increased, so a considerable improvement in initial activity was observed. . However, when heavy residual oil is used as a feedstock, asphaltene and metals contained in the feedstock accumulate and the pores become clogged over time, and the diffusion of reactants into the catalyst is suppressed. It has not yet been possible to overcome the drawback that the active species inside the catalyst remain unused and the activity decreases. In the hydrogenation treatment of heavy oil, various measures have been taken to prevent such deterioration of activity due to pore clogging. For example, in a catalyst made of alumina and/or silica and a metal from Group B and Group of the Periodic Table, the volume of pores of 100 to 1000 Å is 10% or more,
It is said that 10 to 30% of the pore volume of 1000 Å is preferable for decomposing heavy oil (Special Publication Publication No. 1973-
40683). JP-A-57-12832 proposes a catalyst having a bimodal pore distribution containing a catalytic cracking catalyst in a carrier in order to further improve the cracking activity. However, in the former case, sufficient activity cannot be obtained because the acidity of the carrier is insufficient, and in the latter case, the catalytic cracking catalyst microspheres themselves are large, approximately 10 to 100 μm, and have acidic active sites in the microspheres themselves. There are some shortcomings, such as the lack of progress in improving the passageway. That is, according to the research conducted by the present inventors, it has been found that it is important that large diameter pores (macropores) are formed of zeolite. It is known that the active sites that primarily function in decomposing high molecular weight substances contained in heavy residual oil into light fractions are located at acidic sites. In a typical catalyst without macropores (zeolite + Al ₂ O ₃ ), pores are blocked by metal or coke, making it impossible for reactants to reach the zeolite surface, which is an active site. Furthermore, even if the catalysts and supports have macropores, the desired activity cannot be obtained unless the zeolite surface is exposed in the pores. Ta. Therefore, the inventor of the present invention conducted extensive research to find a catalyst that satisfies these demands, efficiently cracking heavy oil into light fractions, and simultaneously performing desulfurization, reforming, hydrogenation, demetalization, denitrification, etc. To do this, simply change the pore distribution to 2
It is not enough to just have one peak (maximum value), but it is necessary for the zeolite to have macropores.
It was discovered that this problem could be solved by binding with a binder, and based on this, the present invention was completed. That is, the present invention has a pore diameter of 500 Å.
Zeolites with a maximum pore distribution of 10 to 90% by weight (excluding faujasite iron-containing zeolites) and 90 to 10% by weight of inorganic oxides
A composition comprising: a pore distribution of the composition;
It has maximum values in the range of 50 to 500 Å and 500 to 10,000 Å, and the pore volume of 50 to 500 Å is 30% or more of the pore volume of 50 to 10,000 Å, and 500 Å
~10000Å pore volume is 50~10000Å pore volume
10% or more and a total pore volume of 0.3 cm ³ /g or more, and the composition supports Group B and Group metals of the periodic table. The present invention also provides a hydrocracking catalyst characterized by the following. In this specification, for convenience, pores with a size of 0 to 50 Å are referred to as micropores, pores with a size of 50 to 500 Å are referred to as mesopores, and pores with a size of 500 to 10,000 Å are referred to as macropores. The composition of the present invention is composed of a zeolite and an inorganic oxide, and among these, there are various types of zeolite except for a faujasite-type iron-containing zeolite, but preferably a faujasite-type or Y-type zeolite. It is. In addition, this zeolite has a pore diameter of 500 Å or more, especially 500 to 10,000.
It is necessary that the pore distribution has a maximum value (peak) in the range of 0.2 cm 3 /g, more preferably this peak has a pore volume of 0.2 cm ³ /g or more, particularly 0.4 cm ³ /g or more. It is something that Such zeolites can be prepared by various methods, but one example is a zeolite with a Na ₂ O content of about 0.5% by weight.
NH ₄ Y-type zeolite is held at 550 to 900°C in a rotary kiln or autoclave for about 1 to 5 hours and steamed, then treated with an aqueous nitric acid solution, washed with water, dried, and then heated at about 400°C for 1 to 5 hours.
Obtained by firing for 5 hours. The zeolite obtained in this way has a diameter of 500Å
It has pores, that is, macropores, which suppress decomposition and a decrease in hydrogenation activity. The reason for this is not clear, but it is speculated that the active sites are exposed on the internal surface of the macropores, and for this reason, even if a portion is contaminated by residual oil with a large molecular weight, the pores are large and the pores are closed. It is thought that the entire lifespan will be extended because the entire area will not be blocked. Therefore, it is necessary that macropores exist in the zeolite; for example, macropores created by bonding inorganic oxides such as alumina particles cannot achieve the desired effects of the present invention. On the other hand, the inorganic oxide maintains the physical strength of the composition and provides an appropriate pore distribution and pore volume, and various types of inorganic oxides can be used as long as they are suitable for this purpose. For example, hydrous oxides such as batemite gel, alumina sol, and silica-alumina gel are preferably used. Silicates and magnesium hydroxide can also be used. The mixing ratio of zeolite and inorganic oxide in the composition of the present invention may be within a range that gives the composition a predetermined pore distribution and pore volume as well as appropriate physical strength; The content may be appropriately selected within the range of 90 to 10% by weight and inorganic oxide. The composition of the present invention comprising the above zeolite and inorganic oxide has a pore size in the range of 50 to 500 Å and a pore size in the range of 50 to 500 Å.
It is necessary that the pore distribution has a peak in each range of 10,000 Å. 500~
As mentioned above, the peak at the 10,000 Å pore, or macropore, is mainly due to the zeolite itself, but the peak at the 50 to 500 Å pore, or mesopore, is due to the zeolite. It may be based on an inorganic oxide. The pore volume in this mesopore is
It provides the high surface area necessary to obtain high-level activities such as denitrification. As mentioned above, the mesopores may be made of either zeolite or inorganic oxide, but it is desirable to change the mesopores as appropriate depending on the intended use of the composition. In other words,
When this composition is used as a catalyst or catalyst support for the production of relatively light substances such as naphtha and kerosene, there is little need for mesopores made of zeolite, and inorganic materials such as alumina particles that are thought to affect the properties of the produced oil are small. It may be formed of an oxide. However, in view of recent energy saving and low cost, when aiming at low hydrogen consumption and high middle distillate yield, it is preferable that a part of the mesopores be formed of zeolite. Formation of mesopores with zeolites is possible by various methods. For example, by self-teaming NH ₄ Y-type zeolite containing 0.1 wt% Na ₂ O at 680° C. for 3 hours, a zeolite having mesopores with a total capacity of 10% can be produced. In addition, in the composition of the present invention, the above-mentioned macropores and mesopores must be distributed to such an extent that their respective functions can be fully exhibited.
It is more than 30% of the pore volume of 10000 Å, and the volume of macropores, that is, pores of 500 to 10000 Å, is 50 to
It is necessary that the pore volume is 10% or more of the pore volume of 10,000 Å. Furthermore, the composition of the present invention also has high demetalization activity, but in order to reduce poisoning by these accumulated metals, the total pore volume must be 0.3 cm ³ /g.
If the pore volume is small, the activity will be low and the life span will be shortened. The zeolite-containing composition of the present invention having the above-mentioned properties is excellent as a catalyst for catalytic cracking of heavy oil or its carrier, and is also effective in hydrotreating. Furthermore, the hydrocracking catalyst of the present invention can be obtained by using the above-mentioned zeolite-containing composition as a carrier and supporting an active metal thereon. As the active metal, any metal commonly used in hydrogenolysis can be used, but it is preferable to use metals from Group B and Group B of the periodic table in combination. Here B
The group metal is preferably tungsten or molybdenum, and the group metal is preferably nickel or cobalt. In addition, group B metals,
Each of the metals in the group may be used alone, or a mixture of a plurality of metals may be used. There is no particular restriction on the amount of the metal that is the active ingredient supported, and it may be adjusted as appropriate depending on various conditions, but usually the metal of Group B of the periodic table accounts for 3 to 24% of the total catalyst, preferably 8%. ~20% by weight and, for group metals, of the total catalyst.
It should be between 0.7 and 20%, preferably between 1.5 and 8% by weight. Carrier for the above active ingredient (zeolite-containing composition)
In order to support the particles, known methods such as coprecipitation method and impregnation method may be used. The composition and catalyst of the present invention are particularly suitable for the hydrocracking of heavy oils, and examples of target heavy oils include atmospheric distillation residues of crude oil, vacuum distillation residues, and vacuum heavy oils. Examples include high quality light oil, catalytic cracking residue oil, visbreaking oil, tar sand oil, and sierre oil. When hydrotreating heavy oil using the composition or catalyst of the present invention, a wide range of reaction conditions can be employed, including reaction conditions conventionally employed in hydrotreating such as hydrocracking. However, the reaction temperature is usually 350-450℃ and the reaction pressure is 20-200Kg/
cm ² , hydrogen/raw oil ratio 500 to 2000Nm ³ −H ₂ /Kl−
Oil, liquid hourly space velocity (LHSV) 0.1 to 1.0hr ^-1 ,
Furthermore, hydrogen with a purity of 75 mol% or higher is used. According to the above conditions, the hydrotreatment proceeds efficiently at a high conversion rate, and a large amount of hydrotreated oil can be obtained. Furthermore, the proportion of middle distillates such as kerosene and gas oil in the resulting hydrotreated oil is extremely high, making it a highly valuable product. Furthermore, the catalyst of the present invention used here has high activity against heavy oil and at the same time has an extremely long life, so that hydrogenation treatment can be carried out continuously over a long period of time. As described above, the composition and catalyst of the present invention can efficiently perform hydrotreating of heavy oil such as hydrocracking, hydrorefining, hydrodesulfurization, hydrodemetalization, and hydrodenitrogenation. Therefore, it can be effectively used in the field of oil refining. Example (1) Production of carrier NH ₄ Y-type zeolite 1400 with Na ₂ O content of 0.45%
g was maintained at 680° C. for 3 hours in a rotary kiln to perform self-steaming. After cooling, it was brought into contact with a 0.1 N nitric acid aqueous solution of No. 14 for 2 hours, then filtered, washed with water, dried, and then calcined at 450°C. This is called zeolite A. The pore distribution of zeolite A is shown in FIG. The pore distribution of this zeolite A has a pore volume in the range of 50 to 500 Å.
The pore volume was 0.1 cm ³ /g (14% of the total), and the pore volume in the range of 500 to 10000 Å was 0.6 ^{cm 3} /g (86% of the total).
Next, add alumina to this zeolite A.
Add boehmite gel in an amount of 40wt%,
The mixture was kneaded, molded, and fired at 600°C to obtain carrier A.
The pore distribution of carrier A was as follows: pore volume in the range of 50 to 500 Å, 0.28 cm ³ /g (56% of the total), 500 to 10000 Å
The pore volume was 0.22 cm ³ /g (44% of the total). (2) Preparation of catalyst and hydrogenation treatment 1400 g of the above carrier A was impregnated with an aqueous solution of nickel nitrate and ammonium metatungstate so that the oxides were 4.25 wt% of nickel and 17.0 wt% of tungsten, dried, and calcined at 550°C. Catalyst A was obtained (NiO4.25wt%,
_WO3 17wt%). Atmospheric distillation residue oil of Kuwait crude oil was added to a reaction tube filled with 1000 ml of catalyst A at a reaction temperature.
The reaction was carried out at 400°C, LHSV 0.3hr ^-1 and pressure 135Kg/cm ² G. The results are shown in Table 1. Even after 4000 hours, it showed almost the same activity as at the start. Comparative Example After steaming the same NH ₄ Y zeolite as in the example, the cake was treated with nitric acid, filtered and washed with water, and then kneaded with boehmite gel so that the weight ratio of zeolite and alumina was 4:1, and mixed with an appropriate amount of water. was added to form a slurry, and then made into microscopic oblate spheres with an average size of 50 microns using a spray dryer, and fired at 500°C for 3 hours. The pore distribution of this microoblate is shown in FIG. The pore distribution of microoblates is 50 to 500 Å
Pore volume in the range of 0.25 cm ³ /g (83.3% of the total),
The pore volume was 0.05 cm ³ /g (16.7% of the total) in the range of 500 to 10,000 Å. Next, boehmite gel was added to the micro oblate spheres so that the final alumina weight ratio was 40 wt%, kneaded, and molded.
Carrier B was obtained by firing at 600°C. The pore distribution of carrier B showed almost the same bimodal pore distribution as carrier A. The pore distribution of carrier B is shown in FIG. The pore distribution of this carrier B has a pore volume in the range of 50 to 500 Å.
The pore volume was 0.50 cm ³ /g (71% of the total), and the pore volume in the range of 500 to 10000 Å was 0.20 ^{cm 3} /g (29% of the total).
Thereafter, Catalyst B was produced in exactly the same manner as in the Example, and was used for hydrogenation treatment. The results are shown in Table 1. In the case of catalyst B, the activity decreased significantly after 2000 hours, and operation could not be continued.

【table】

[Table] Sulfur content ^* : Sulfur content in kerosene fraction

[Brief explanation of the drawing]

Figure 1 shows the pore distribution of zeolite A prepared in the example, Figure 2 shows the pore distribution of carrier A prepared in the example, and Figure 3 shows the pore distribution of the microoblates prepared in the comparative example. Figure 4 shows the pore distribution of carrier B prepared in comparative examples. In the figure, the horizontal axis shows the pore diameter D, and the vertical axis shows the rate of change in the logarithm of pore volume/pore diameter, that is, ΔV/ΔlogD.

Claims (1)

[Scope of Claims] 1. A zeolite having a maximum pore distribution with a pore diameter of 500 Å or more (excluding faujasite iron-containing zeolite) consisting of 10 to 90% by weight and 90 to 10% by weight of an inorganic oxide. The composition has a pore distribution ranging from 50 to 500 Å and from 500 to 500 Å.
Each has a maximum value in the range of 10,000 Å, and the pore volume of 50 to 500 Å is more than 30% of the pore volume of 50 to 10,000 Å, and the pore volume of 500 to 10,000 Å is 50 to
A zeolite-containing composition characterized in that the pore volume is 10% or more of the pore volume of 10,000 Å, and the total pore volume is 0.3 cm ³ /g or more. 2. A composition consisting of 10 to 90% by weight of a zeolite (excluding faujasite iron-containing zeolite) having a maximum pore distribution with a pore diameter of 500 Å or more and 90 to 10% by weight of an inorganic oxide, The pore distribution of the composition ranges from 50 to 500 Å and from 500 to 500 Å.
Each has a maximum value in the range of 10,000 Å, and the pore volume of 50 to 500 Å is more than 30% of the pore volume of 50 to 10,000 Å, and the pore volume of 500 to 10,000 Å is 50 to
Hydrogenation characterized in that a metal of group B or group of the periodic table is supported on a zeolite-containing composition having a pore volume of 10000 Å or more and a total pore volume of 0.3 cm ³ /g or more. Catalyst for decomposition.