JPH0117415B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a catalyst effective for the hydrodesulfurization of petroleum-based heavy hydrocarbon oil (hereinafter referred to as heavy oil), and more specifically to a catalyst that can maintain stable catalytic activity for a long period of time. The present invention relates to a hydrodesulfurization catalyst that has a pore distribution and a special shape that can minimize pressure loss, which greatly affects operating costs. Azuma, who is one of the co-inventors of the present invention, previously worked with three other co-researchers to elucidate the relationship between the pore distribution, activity, and life of heavy oil hydrodesulfurization catalysts. Developed a new hydrodesulfurization catalyst that is active and has a long life (Patent Application No. 99055/1983
No. 27036) (see application). This new catalyst is composed of porous alumina and a hydrogenation component supported on it, and its feature is that the pore distribution of the catalyst satisfies both conditions (a) and (b) below. It is in. (a) Pore distribution conditions measured by nitrogen gas adsorption method The average diameter of pores with a pore diameter in the range of 0 to 600 Å is 100 to 130 Å, and the volume of pores with a pore diameter of 90 to 140 Å the sum is at least 70% of the total volume of pores with pore diameters between 0 and 600 Å
and the total volume of pores with a pore diameter of 0 to 60 Å is 10% or less of the total volume of pores with a pore diameter of 0 to 600 Å. (b) Pore distribution conditions measured by mercury porosimetry Pore diameter is in the range of 62 to 600 Å, average diameter is 90 to 130 Å, and volume of pores with average diameter ± 10 Å The total accounts for at least 60% of the pore volume between 62 and 600 Å, with an average diameter +
The total volume of pores with a pore diameter of 10 Å or more is 62
~600 Å is less than 10% of the pore volume. Regarding the pore distribution conditions specified above, the nitrogen gas adsorption method is described in Journal of the American Chemical Society, Vol. 73, p. 373 (1951).
Adopt the described method and use CALRO for mercury intrusion method.
A mercury intrusion type pore distribution measuring machine model 220 manufactured by ERBA is used, and conditions of a contact angle of 130° and a surface tension of 473 dyn/cm ² are adopted. Catalysts with the above-mentioned pore distribution characteristics have a narrow pore distribution with an average pore diameter in the range of 90 to 130 Å, and almost all pores are cylindrical, so they come into contact with heavy oil. Even under these conditions, asphaltene or asphalt components do not enter the pores. Therefore, this catalyst has relatively little precipitation of heavy metals and carbonaceous matter, and the life of the catalyst can be extended accordingly. Further, although this catalyst does not allow the intrusion of asphaltene or asphalt components, it can draw relatively long sulfur compounds and nitrogen compounds into the pores, so it has the advantage of maintaining a high level of hydrodesulfurization activity. By the way, in the case of a heterogeneous catalytic reaction, the larger the surface area per unit weight of the catalyst particles, the better. In other words, the smaller the size of the catalyst particles, the more advantageous it is for the catalytic reaction. However, if the catalyst particles are made smaller, the packing porosity of the reaction column will inevitably decrease and the pressure drop (hereinafter referred to as ΔP) within the reaction column will increase. There are certain limits. Under these circumstances, cylindrical or spherical catalysts with a diameter of about 1 to 1/50 inch have been widely used for the hydrodesulfurization of heavy oil. However, when hydrodesulfurizing heavy oil on a commercial scale, heavy oil with high molecular weight and high viscosity is poured into a reaction tower packed with as much as 100 tons of catalyst while flowing a large amount of hydrogen. Because of the reaction, ΔP inevitably becomes large. In addition, since the reaction tower is a high-pressure vessel, there is a limit to increasing the diameter of the reaction tower. Therefore, the reaction tower for hydrodesulfurization usually has a small diameter/height ratio, which is also a cause of increasing ΔP in the reaction tower. As is well known, there is a close relationship between ΔP and operating cost in the reaction tower, and an increase in ΔP significantly increases the operating cost of the hydrodesulfurization equipment. Therefore ΔP
The size of ΔP is extremely important for actual operation, but as long as a hydrodesulfurization catalyst with the shape and dimensions described above is used, one must be prepared for a considerable ΔP. The present inventors focused on the characteristics that the hydrodesulfurization catalyst according to the invention of Japanese Patent Application No. 53-99055 introduced earlier has high activity and long life. In order to propose a catalyst that can further reduce this, we have completed the present invention by repeatedly studying the shape and dimensions of the catalyst while taking into consideration the hydrodesulfurization activity. Therefore, the hydrodesulfurization catalyst for heavy oil according to the present invention is a hydrodesulfurization catalyst containing porous alumina and a hydrogenation component supported thereon. Around a circle whose cross section is 0.4 to 5 mm in diameter, there are 3 to 3 squares of equal diameter equiangularly placed from the center of the circle.
Arrange six circles and measure the distance from the center of the center circle to the center of the equiangular circle from 1/4 to the diameter of the center circle.
3/4, and the diameter of the equiangular circle is approximately equal to that of the central circle, and the height of the column with this petal-shaped cross section is in the range of 2 to 15 mm, and The catalyst is characterized in that the pore distribution measured by the nitrogen gas adsorption method and the pore distribution measured by the mercury intrusion method satisfy both conditions (a) and (b) above, respectively. That is, the catalyst of the present invention is distinguished from conventional hydrodesulfurization catalysts in that it has a specific pore distribution,
It is distinguished from the hydrodesulfurization catalyst of the invention in Japanese Patent Application No. 53-99055 in that its shape is a columnar body with a special petal-like cross section. First, the geometrical features of the catalyst according to the present invention will be explained below with reference to the drawings. Figures a and b in Fig. 1 each show an example of a petal-shaped cross section of the catalyst according to the present invention, and the petal-shaped cross section is arranged around a central circle in four equal-diameter circles equiangularly from the center. The diagram shows a case in which the image is constructed by arranging circles. In Figure 1 a, the distance between the center of the central circle and the centers of the surrounding circles equiangular is 1/4 of the diameter of the central circle, and in b, the distance is 1/4 of the diameter of the central circle. For 3/4, the distance between the centers of the central circle and the surrounding circles can be arbitrarily selected within the above range. In addition, in the example shown in Fig. 1, the number of surrounding circles is 4, and the surrounding circles and the center circle have the same diameter, but in the present invention, the number of surrounding circles is 3 to 6.
The diameters of the surrounding circle and the center circle do not necessarily have to be the same as long as they are approximately equal. Here, "approximately equal" means that the difference in diameter between the two circles is ±20%. The hydrodesulfurization catalyst of the present invention, which is a columnar body with a special petal-shaped cross section as described above, is usually manufactured by molding porous alumina into a desired shape and supporting the hydrogenation component on the catalyst. be done. Therefore, in producing the catalyst, porous alumina used as a catalyst carrier must be molded into the special shape contemplated by the present invention. However, since such a carrier can be molded simply by processing a die of an ordinary extrusion molding machine into a desired shape, a significant increase in cost does not occur. Extruded alumina is typically air-dried overnight at 110°C.
It is fired at 550°C for 3 hours to become a catalyst carrier. Next, a hydrogenation component is supported on the catalyst carrier, and the hydrogenation component and its supporting means used here are well known, and can be employed in the present invention. For example, a method in which ammonia water and water are added to ammonium paramolybdate, impregnated into a carrier, dried once, then impregnated with an aqueous solution containing cobalt nitrate and nickel nitrate, dried, and fired at 550°C. can be adopted. In this case, the supported amount of each hydrogenation component is 10wt% as NiO.
Below, 10wt% or less as CoO, 5~ as MoO ₃
It is allowed to be less than 30wt%. In this way, a columnar catalyst with a desired petal-like cross section is obtained. In addition to these morphological characteristics, the hydrodesulfurization catalyst of the present invention has the following pore distribution when the hydrogenation component is added. Both conditions (a) and (b) must be satisfied. (a) Pore distribution conditions measured by nitrogen gas adsorption method The average diameter of pores with a pore diameter in the range of 0 to 600 Å is 100 to 130 Å, and the volume of pores with a pore diameter of 90 to 140 Å the sum is at least 70% of the total volume of pores with pore diameters between 0 and 600 Å
and the total volume of pores with a pore diameter of 0 to 60 Å is 10% or less of the total volume of pores with a pore diameter of 0 to 600 Å. (b) Pore distribution conditions measured by mercury porosimetry Pore diameter is in the range of 62 to 600 Å, average diameter is 90 to 130 Å, and volume of pores with average diameter ± 10 Å The total accounts for at least 60% of the pore volume between 62 and 600 Å, with an average diameter +
The total volume of pores with a pore diameter of 10 Å or more is 62
~600 Å is less than 10% of the pore volume. Here, the pore distribution of the nitrogen gas adsorption method was determined from the nitrogen adsorption isotherm described in Journal of the American Chemical Society, Vol. 73, p. 373 (1951), and In the law
Using CALRO ERBA's mercury intrusion type pore distribution analyzer model 220, the contact angle was 130° and the surface tension was measured.
The condition of 473dyn/ ^cm2 is adopted. In addition, the average diameter of pores is 50% of the pore volume determined from the pore distribution curve.
The diameter is equivalent to . The hydrodesulfurization catalyst of the present invention can be prepared by supporting an alumina carrier with a predetermined amount of hydrogenation component, for example, by an impregnation method. Porous alumina that satisfies both pore distribution conditions is preferred. (a) Pore distribution conditions measured by nitrogen gas adsorption method The average diameter of pores with a pore diameter in the range of 0 to 600 Å is 100 to 130 Å, and the volume of pores with a pore diameter of 90 to 140 Å The total volume of pores with a pore diameter of 0 to 600 Å is greater than or equal to 65% of the total volume of pores with a pore diameter of 0 to 600 Å, and the total volume of pores with a pore diameter of 0 to 600 Å is Not more than 15% of the total pore volume. (b) Pore distribution conditions measured by mercury porosimetry Pore diameter is in the range of 62 to 600 Å, average diameter is 80 to 125 Å, and volume of pores with average diameter ± 10 Å 65% or more of the pore volume with a total of 62 to 600 Å, and the total volume of pores with a pore diameter of average diameter + 10 Å or more is 62 to 600
It is less than 10% of the pore volume of Å. The porous alumina carrier as described above is made of alumina hydrate obtained by a normal neutralization reaction between a basic aluminum salt aqueous solution and an acidic substance aqueous solution, or a basic substance aqueous solution and an acidic substance aqueous solution. It can be obtained by heating and ripening in the presence of an organic base compound. However, the method for preparing the catalyst according to the present invention is not limited to the method described above, and as long as the pore distribution of the catalyst finally obtained satisfies the conditions specified in the present invention, for example, porous alumina It is also possible to adopt a method of kneading the precursor and the hydrogenation component and molding it into a desired shape. Due to its special pore distribution, the hydrodesulfurization catalyst of the present invention maintains stable catalytic activity for a long period of time when used for hydrodesulfurization of heavy oil, and because it has unique shape characteristics. Compared to conventional catalysts, this catalyst exhibits the special effect of being able to reduce ΔP within the reaction tower. Next, the catalyst of the present invention will be explained in more detail with reference to Examples, and the performance of the catalyst will be demonstrated through test examples. Example 1 A sodium aluminate solution with a concentration of 5.0 wt% as alumina was heated to 60°C, an aqueous gluconic acid solution was added as a stabilizer, and then heated to 60°C with a concentration of 2.5 wt% as alumina. Add aluminum sulfate solution for about 10 minutes to adjust the pH of the prepared slurry.
It was set to 7.0. This alumina blend slurry was washed to obtain alumina hydrate. A small amount of ammonia water and urea were added to this alumina hydrate to adjust the pH to 10.5, and the alumina concentration of the alumina hydrate was adjusted to 9%. This slurry of alumina hydrate was heated and stirred at 95°C for 15 hours, and then heated and further heated in a kneader to obtain a plastic hydrate. This mixture was extruded into the following nine shapes. (1) Cylindrical body; 1/50″φ, 1/32″φ, 1/16″φ,
1/12″φ; These are A, B, C, and D, respectively.
shall be. (2) A column with a four-lobed cross section as shown in Figure 2; around a central circle with a diameter of 0.5 mm, there are four circles (diameter 0.5 mm) approximately equiangular from the center O.
A column with an average height of 3.3 mm and a petal-shaped cross section with distances between the centers A, B, C, D, and O of each circle being 0.33 mm (0.5 mm x 2/3). Let this be E. (3) A columnar body with a petal-like cross section (see Figure 3); (i) A central circle with a diameter of 0.5 mm and its center O.
Three circles of equal diameter are equiangular from (0.5
mm), and the centers of each circle are A, B, C and O.
The distance between each is 0.375mm (0.5mm x 3/4)
The average height is 3.3mm with a petal-shaped cross section.
column body. Let this be F. (ii) The distances between centers A, B, C and O are respectively
0.250mm (0.5mm×2/4), and the average height is
The column has the same shape as F above except that it is 2.9mm.
Let this be G. (iii) The distances between centers A, B, C and O are respectively
If it is 0.420mm (0.5mm×5/6), the above F
A column with the same shape as . Let this be H. (iv) The distance between centers A, B, C and O is 0.1 mm (0.5
mm x 1/5) and has the same shape as F above except that the average height is 3.0 mm. Let this be I. (4) Powder: This is designated as J. Once extruded into a cylindrical shape with a diameter of 1/8", this is crushed and sieved to a particle size of 100 to 120μ. These 10 types of extrusion molded products A to I and powder and granule J ( Among these, two types (F and G) corresponding to the present invention were air-dried at 110°C for one day and night, and then heated to 550°C.
It was baked for 3 hours. The pore volume of each of the porous alumina carriers obtained as measured by nitrogen gas adsorption method was 0.70 ml/g, and the average diameter of pores with a pore diameter in the range of 0 to 600 Å was 105 Å. The total volume of pores with a pore diameter of ~140 Å is 71.4% of the total volume of pores with a pore diameter of 0 to 600 Å, and the total volume of pores with a pore diameter of 0 to 60 Å is , 4.3% of the total volume of pores with pore diameters from 0 to 600 Å.
The pore distribution of these carriers measured by mercury porosimetry shows that the average diameter of pores in the range of 62 to 600 Å is 90 Å, and the volume of pores with a pore diameter of ±10 Å is The total is 76.5% of the pore volume between 62 and 600 Å, and the total volume of pores with a pore diameter greater than or equal to the average diameter + 10 Å is 76.5% of the pore volume between 62 and 600 Å.
It was 4.4%. A solution was prepared by adding 639 g of 15 wt% aqueous ammonia to 755 g of ammonium paramolybdate, and further adding 2330 g of water to make the amount of impregnating liquid sufficient for the total pore volume, and impregnating 5 kg of the above-mentioned fired carrier with this solution. I let it happen. The dried product was then air-dried at 110° C. overnight, impregnated with an aqueous solution containing 275 g of cobalt nitrate and 165 g of nickel nitrate, and dried. After that
The catalyst was fired at 550°C for 1 hour in a Matsufuru furnace.
These catalysts A to J all contain MoO ₃ , NiO and
Contains 12.0, 0.8 and 1.3 wt% hydrogenated components as CoO, respectively. The average diameter of pores in the range of 0 to 600 Å, determined by the nitrogen adsorption method, of these catalysts A to I is 105 Å, and the pore volume of pores with a pore diameter of 90 to 140 Å is the same as that of pores with a pore diameter of 0 to 600 Å. of pore volume
74.5%, and the pore volume with a pore diameter of 0 to 60 Å is
It was 1.0% of the pore volume with a pore diameter of 0 to 600 Å. In addition, the pore distribution of this catalyst determined by mercury intrusion method shows that the average pore diameter is in the range of 62 to 600 Å.
At 94 Å, 76.5% of the total pore volume was occupied by 94±10 Å pores, and the volume of pores larger than 104 Å was 7.5% of the total pore volume. Comparative Example 1 A gluconic acid aqueous solution was added as a stabilizer to a sodium aluminate aqueous solution with a concentration of 5.0 wt% as alumina, and then an aluminum sulfate solution with a concentration of 2.5 wt% as alumina was added at room temperature to obtain an alumina blend slurry. . The alumina hydrate obtained by washing this alumina blend slurry was heated and kneaded in a kneader to obtain a plastic kneaded product. This kneaded product was molded into the same shape as the carrier used for Catalyst G and fired to obtain a porous alumina carrier. Catalyst K was prepared by supporting the same kind and amount of hydrogenation components on this carrier in the same manner as in Example 1. The pore volume of the alumina support used for Catalyst K was 0.62 ml/g, measured by nitrogen gas adsorption method, and the pore volume was 0.62 ml/g.
The average diameter of pores in the range of 600 Å is 80 Å, the pore volume of pore diameters 90-140 Å is 33.9% of the pore volume of 0-600 Å, and the pore volume of 0-60 Å is 0
~600 Å was 16.1% of the pore volume. In addition, the pore distribution of this carrier by mercury intrusion method is as follows:
The average diameter ranges from 62 to 600 Å, with an average diameter of 65 Å and 62 to 600 Å.
The volume occupied by 75 Å pores is 88.8% of the pore volume between 62 and 600 Å, and the pore volume above 75 Å is
It was 11.1% of the pore volume between 62 and 600 Å. The average diameter of 0-600 Å pores determined by the nitrogen gas adsorption method of catalyst K itself is 81 Å, and the pore volume of pores with a diameter of 90-140 Å is 27% of the pore volume of 0-600 Å. , the pore volume of 0-60 Å is 0-600
It was 3.0% of the pore volume of Å. In addition, the average diameter of pores in the range of 62 to 600 Å determined by mercury intrusion method is 71 Å, and the volume occupied by pores with an average diameter of 71 ± 10 Å is 85% of the volume of pores in the range of 62 to 600 Å. ,
The pore volume of 81 Å or more is the same as that of the pore volume of 62 to 600 Å.
It was 11.5%. This catalyst K has a pore structure similar to that of catalyst G, but
The average pore diameter of the catalyst is 81 Å, which is smaller than Catalyst G. Comparative Example 2 A small amount of 15 was added to commercially available alumina powder (boehmite).
% ammonia water and water were added and kneaded by heating in a kneader to obtain a plastic kneaded product. This mixture was molded into the same shape as the carrier used for catalyst F and fired.
A porous alumina carrier was obtained. Example 1
Catalyst L was prepared by supporting hydrogenation components of the same type and amount in the same manner as in Example 1. The pore volume of the alumina support used in Catalyst L measured by nitrogen gas adsorption method was 0.65 ml/g, which was 0 to 0.
The average diameter of the pores in the 600 Å range is 146 Å;
The pore volume with a pore diameter of 90-140 Å is 28.5% of the pore volume with a pore diameter of 0-600 Å, and the pore volume with a pore diameter of 0-60 Å is 0.
~600 Å was 6.2% of the pore volume. In addition, the average diameter of pores in the range of 62 to 600 Å determined by mercury intrusion method is 135 Å, and the volume occupied by pores with an average diameter of ±10 Å is 73.3% of the pore volume of 62 to 600 Å.
and the volume of a pore with a diameter of 145 Å or more is 62
~600 Å was 15% of the pore volume. On the other hand, 0 determined by the nitrogen gas adsorption method of the catalyst L itself
The average diameter of ~600 Å pores is 147 Å, and the pore diameter
The pore volume between 90 and 140 Å is the same as that between 0 and 600 Å.
23.5%, and the pore volume from 0 to 60 Å is 0 to 600 Å
It was 0% of the pore volume. In addition, the average diameter of the pores in the range of 62 to 600 Å determined by mercury intrusion method was 144
Å, and the volume occupied by pores with an average diameter of ±10 Å is 60% of the pore volume between 62 and 600 Å, and the volume occupied by pores with an average diameter of ±10 Å is
The pore volume of 154 Å or more is smaller than that of 62 to 600 Å.
It was 20%. Most of the pores of this catalyst L are concentrated around 150 Å, which makes the average pore diameter of the catalyst of the present invention approximately 40 Å.
This corresponds to a catalyst that has been moved to the larger side by Å. Test Example 1 Using the various catalysts obtained in Examples and Comparative Examples 1 and 2, atmospheric residual oil produced in Kuwait was hydrodesulfurized. The raw oil properties, test equipment, and test conditions are shown below. (1) Raw oil properties Specific gravity (15/4℃) 0.956 Sulfur content (wt%) 3.77 Nitrogen content (ppm) 2100 Asphaltene (wt%) 3.9 Vanadium (ppm) 48 Nickel (ppm) 14 (2) Test equipment Test The equipment used was of a fixed bed type, and the dimensions of the reaction tube were 27 mm in outer diameter and 19 mm in inner diameter.
φ, length 3m. Attach a thermocouple shell to the center of the reaction tube to measure the reaction temperature.
The average temperature of the catalyst layer was measured while moving the thermocouple inside this shell. Furthermore, the outside of the reaction tube was surrounded by a metal block for uniform heating, and a five-stage electric furnace was installed outside of the metal block to control the reaction temperature. (3) Test conditions (i) Sulfurization operation: 150g of catalyst was weighed and heated at 330°C under atmospheric pressure while flowing 830 times the volume of hydrogen (including 3% hydrogen sulfide) per hour.
A sulfiding treatment was carried out for 3 hours. (ii) Test conditions Reaction temperature (℃) 361 Reaction pressure (Kg/ ^cm2.G ) 150 LHSV (hr ^-1 ) 1.0 Hydrogen/hydrocarbon oil ( ^Nm3 /Kl) 830 Hydrogen concentration (mol%) 90 or more After 100 hours of break-in operation under certain conditions, 100
Activity comparisons were performed at ~110 hours. The desulfurization activity was determined as a value relative to the apparent reaction rate constant (quadratic equation) of the desulfurization reaction of catalyst B at 361° C. as 100. The results are shown in Table 1 and FIG. In addition, Table 1 shows the properties of each catalyst used and the packing density in the reaction tube.
Also listed. The average diameter of the catalysts E, F, G, H, I, and K corresponds to d shown in FIGS. 2 and 3, and the pressure resistance is a value measured from the direction of the arrow in FIGS. 2 and 3. Test Example 2 Using the same catalysts A to L as used in Test Example 1, the pressure loss due to gas and oil was actually measured under conditions simulating a reaction tower on an actual scale. The equipment and measurement conditions are as follows. Filling device dimensions Inner diameter 20.5mm, Outer diameter 32mm, Length 5000
mm Amount of catalyst used 1485ml (constant volume) Oil Commercial kerosene (specific gravity 15/4℃, 0.792, viscosity 1.2cst
(37.8℃) Flow rate 8.2/hr (equivalent to linear velocity 27 m/hr) Gas Commercially available nitrogen, flow rate 98/hr (equivalent to linear velocity 320 m/hr) When pressure loss ΔP when using catalyst B is 100 The relative ΔP values of each catalyst are shown in Table 1 and FIG.

【table】

[Table] To summarize the above test results, first, when the standard catalyst is B, from Fig. 4, cylindrical catalysts A, B,
It can be seen that desulfurization activity improves as the particle size becomes smaller for C and D. Further, crushed catalyst J and catalyst A, which have extremely small particle sizes, exhibit the same desulfurization activity. In other words, it can be said that catalyst A is used for the desulfurization reaction even inside the particles. Catalysts K and L have different alumina carriers and have different pore distributions, so their hydrodesulfurization activity is low. Catalyst E is similar to the catalyst of the present invention, but its activity is lower than that of catalyst B due to its inappropriate shape. The catalysts of the present invention, F and G, clearly belong to a different class of preferred activities. This is because the catalyst is an aggregate of cylindrical extrudates with a particle size of about 0.5 mmφ, and its shape is excellent. That is, as mentioned above, the shape of the aggregate of the present invention has a particle size that matches the characteristics of the catalyst, which is the cause of good activity, but it must not increase ΔP. Of course. However, as shown in Figure 5, this catalyst not only exhibits higher activity than standard catalyst B;
The results show that ΔP is also clearly low.
However, catalysts E, K, and L also show low ΔP, and in order to have both low ΔP and high activity, it is necessary not only to have the shape of the catalyst according to the present invention, but also to have the pores of the catalyst. It can be seen that the distribution must also be of the invention. Although catalysts H and I have petal-shaped cross sections, they are excluded from the scope of the present invention due to their dimensions. In other words, the catalyst H has a long distance between the central circle and the peripheral circle (5/6 of the diameter of the central circle) in the petal-shaped cross section.
The bulk specific gravity is too light, the catalyst strength is significantly reduced, and ΔP is too small or the activity is too low to be used as a practical catalyst. In addition, in Catalyst I, the centers of each circle are too concentrated, and the desirable characteristics of the present invention are not realized. Although this catalyst has high activity, it shows a high value of ΔP. Test Example 3 A long-term life test was conducted using Kuwait atmospheric residual oil under the conditions shown in Test Example 1 using Catalyst B and Catalyst F of the present invention. That is, LHSV=
The reaction temperature was controlled so that the sulfur content of the produced oil was 1.0 wt% under the following conditions: 1.0 hr ^-1 , hydrogen/hydrocarbon oil = 830 Nm ³ /Kl, reaction pressure = 150 Kg/cm ² , and hydrogen concentration = 90 mol%. The test results are shown in Figure 6.The results show that even though the physical properties of the catalyst are exactly the same, in order to significantly improve its performance, the particle size is reduced and all parts of the particle are used effectively. It can be seen that the catalyst of the present invention, which is made to have a longer catalyst life, has a clearly longer catalyst life.

[Brief explanation of drawings]

FIG. 1 is a cross-sectional view of a catalyst according to an embodiment of the present invention, FIG. 2 is a cross-sectional view of a conventional catalyst, FIG. 3 is a cross-sectional view of a catalyst according to another embodiment of the present invention, and FIG. 4 is a cross-sectional view of a catalyst according to another embodiment of the present invention. A graph showing the relationship between the average diameter of the catalyst and the relative value of desulfurization activity. Figure 5 is a graph showing the relationship between the average diameter of the catalyst and the relative value of ΔP. Figure 6 is a graph showing the relationship between the operating time and the rate of increase in reaction temperature. It is.

Claims (1)

[Claims] 1. In a hydrodesulfurization catalyst containing porous alumina and a hydrogenation component supported thereon, the catalyst is a column whose cross section is circular with a diameter of 0.4 to 5 mm. 3~ with equal diameter around the center equiangularly
Arrange six circles and measure the distance from the center of the center circle to the center of the equiangular circle from 1/4 to the diameter of the center circle.
3/4, and the diameter of the equiangular circle is approximately equal to that of the central circle, and the height of the column with this petal-shaped cross section is in the range of 2 to 15 mm, and The pore distribution of the above catalyst is as shown in (a) and (b) below.
A hydrodesulfurization catalyst for petroleum-based heavy hydrocarbon oil, characterized by satisfying both of the following conditions. (a) Pore distribution conditions measured by nitrogen gas adsorption method The average diameter of pores with a pore diameter in the range of 0 to 600 Å is 100 to 130 Å, and the volume of pores with a pore diameter of 90 to 140 Å the sum is at least 70% of the total volume of pores with a pore diameter between 0 and 600 Å
and the total volume of pores with a pore diameter of 0 to 60 Å is less than 10% of the total volume of pores with a pore diameter of 0 to 600 Å; (b) pores measured by mercury intrusion method; Pore distribution conditions The average diameter of pores with a pore diameter in the range of 62 to 600 Å is 90 to 130 Å, and the total volume of pores with a pore diameter of ±10 Å is 62 to 600 Å. Occupying at least 60%, average diameter +
The total volume of pores with a pore diameter of 10 Å or more is 62
~10% of the pore volume of ~600 Å, 2 The diameter of the equiangular circle is ±20 of the diameter of the central circle.
% of the catalyst according to claim 1. 3. The catalyst according to claim 1, wherein the hydrogenation component supported on porous alumina is an oxide of nickel, cobalt, and molybdenum. 4 The supported amount of oxides of nickel, cobalt and molybdenum is 10wt% or less as NiO, as CoO
The catalyst according to claim ₃ , which is 10 wt% and 5 to 30 wt% as MoO3.