JP2001205083A - Catalyst for hydrogenating aromatic compound in hydrocarbon oil and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a catalyst for hydrogenating an aromatic compound in a hydrocarbon oil containing a sulfur compound, etc., and provide a manufacturing method for the catalyst. SOLUTION: This catalyst for hydrogenating an aromatic compound in a hydrocarbon oil comprises a catalyst carrier oxide consisting of silica/magnesia and at least one selected from a platinum metal group, and is porously molded. In addition, the carrier is molded after adding silica-magnesia hydrate powder obtained by pulverizing a silica-magnesia hydrate gel containing 25-50 wt.% of magnesia in terms of oxide to the hydrate gel and further, kneading the hydrate gel with the hydrate powder. Then, the mixture is dried and baked to obtain the carrier. The catalyst is manufactured by carrying at least one of a metallic salt solution selected from the platinum metal group and drying/ baking it or by adding the hydrate powder made up of the silica magnesia obtained by pulverizing the gel and at least one of the metallic salt solution selected from the platinum metal group and kneading/molding and further, baking the molding after drying.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst for hydrotreating an aromatic compound in a hydrocarbon oil, and more particularly to a hydrocracking method for hydrotreating an aromatic hydrocarbon compound contained in a hydrocarbon oil. The present invention relates to a hydrotreating catalyst having a low ratio of, a high resistance to poisoning of sulfur compounds and the like, and a high hydrogenation activity, and a method for producing the same.

[0002]

2. Description of the Related Art Diesel oil, which is the fuel oil of conventional diesel engines, is obtained by subjecting a straight-run gas oil fraction having a specific boiling point obtained by atmospheric distillation of crude oil to hydrodesulfurization and denitrification. It is prepared by blending a light oil fraction consisting mainly of a light oil and a light oil fraction obtained by vacuum distillation. However, the gas oil fraction contains only a limited amount in the crude oil, and the crude oil is becoming heavier year by year. Therefore, the amount of the straight gas oil fraction in the crude oil tends to decrease. Therefore, heavy oil is cracked or hydrocracked / desulfurized to convert it into a gas oil fraction. In addition, light oil demand is expected to increase with the increase in diesel engines, and it is expected that the supply of light oil will run short in the near future.

[0003] One way to address the shortage of straight gas oil fractions obtained from crude oil and to meet the increasing demand for gas oils is to increase the production of blended oils blended with the straight gas oil fraction. Therefore, light cracked gas oil having a specific boiling point range obtained from a catalytic cracking unit has been receiving attention as a raw material oil for a new blended oil for gas oil. However, since light cracked gas oil contains many aromatic hydrocarbon components, blending it with a straight-run gas oil fraction with the same properties increases the content of aromatic hydrocarbon compounds and increases the cetane number of the blended gas oil. descend. Particulates in the exhaust gas of diesel engines are fine particulate air pollutants generated by incomplete combustion of some of the aromatic hydrocarbon compounds, and pose a problem from the standpoint of environmental conservation. It is expected that laws will be enacted to further reduce the content of aromatic hydrocarbon compounds. Therefore, in order to use lightly cracked light oil as a blended oil, it is desirable to reduce the content of aromatic hydrocarbon compounds by subjecting lightly cracked light oil to catalytic hydrogenation.

[0004] Although light cracked gas oil has a lower content of sulfur compounds than straight-run gas oil fractions, hydrogen sulfide generated by hydrotreating them inhibits the hydrogenation reaction of aromatic hydrocarbon compounds. Poisoning of active points on the catalyst may cause deterioration of the activity. Conditions for hydrotreating light cracked gas oil include high hydrogenation activity and aromatic resistance to aromatic hydrocarbon compounds, and It is important to have desulfurization performance. Among the hydrotreating catalysts, catalysts in which a noble metal of Group VIII of the periodic table is supported on a carrier such as alumina are generally powerful catalysts with high hydrogenation activity, but are poisoned by sulfur compounds in hydrocarbon oils. As a result, there is a disadvantage that it is deactivated early. In order to remedy this drawback, attempts have been made to carry out hydrotreatment using a catalyst containing zeolite or the like in a carrier. However, zeolites are highly active catalysts for hydrocracking reactions.However, if hydrocracking reactions occur simultaneously in the hydrotreatment of the target light cracked gas oil, the yield of the gas oil fraction decreases. It is necessary to suppress the hydrocracking activity.

JP-A-64-66292 discloses that a noble metal belonging to Group VIII of the periodic table is supported on a Y-type zeolite having a unit cell length of 24.20 to 24.30 angstroms and a silica / alumina ratio of at least 25. There is disclosed a method for performing a hydrotreating process using a prepared catalyst. However, in this method, the catalyst is poisoned by sulfur compounds contained in the feedstock oil, the hydrogenation activity of the aromatic compounds is still insufficient, and the hydrocracking reaction occurs to lower the yield of the produced oil. Had the disadvantage of doing so.

Japanese Patent Application Laid-Open No. 8-283746 discloses that
Disclosed are a catalyst in which a group VIII metal of the periodic table is supported on a carrier made of a crystalline clay mineral containing silicon and magnesium as a main component, and a hydrotreating method using the catalyst. However, this method has the effect of suppressing hydrocracking and increasing the yield of product oil, but the hydrogenation activity of aromatic compounds is still insufficient, and the feedstock oil containing low concentrations of sulfur compounds etc. Although its hydrogenation activity is good, it does not disclose any effect of hydrotreating aromatic compounds of a feedstock oil containing a high concentration of sulfur compounds.

Further, Japanese Patent Application Laid-Open No. Hei 8-509999 discloses a catalyst in which a group VIII metal of the periodic table is supported on a crystalline non-layered aluminosilicate having pores having a diameter larger than 1.3 nm, and the catalyst is used. A hydrotreating method is disclosed. However, in this method, although the yield of the produced oil and the hydrogenation activity of the aromatic compound are increased with respect to the raw material oil having extremely low sulfur compounds, the sulfur compound is contained at a high concentration. There is no description on the effect of hydrotreating aromatic compounds in the feedstock.

[0008]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to hydrotreat a hydrocarbon oil containing a sulfur compound or the like, particularly a light oil fraction. It has high resistance to sulfur compounds and the like suitable for reducing the content of aromatic compounds, has high hydrogenation activity, and has high performance in the yield of product oil, and further simplifies the catalyst production process. An object of the present invention is to provide a catalyst for hydrotreating an aromatic compound in a hydrocarbon oil and a method for producing the same.

[0009]

Means for Solving the Problems According to the present invention, as a result of intensive studies to solve the above-mentioned problems and to achieve the above-mentioned objects, carbonization by using a catalyst containing silica-magnesia as the main component has been carried out. The present invention has found a catalyst having a high hydrogenation reaction activity suitable for reducing the content of aromatic compounds in hydrogen oil, a high resistance to sulfur compounds and the like, and a high production oil yield and a method for producing the same. It was completed.

That is, the catalyst for hydrotreating an aromatic compound in a hydrocarbon oil according to the first embodiment of the present invention comprises an oxide composed of silica-magnesia and a noble metal of Group VIII of the periodic table as an active component. Wherein the magnesia content of the silica-magnesia oxide is less than or equal to one or more selected from the group consisting of: 25 to 5 in conversion
0% by weight, and the oxide composed of silica and magnesia contains no inorganic oxide components other than silica and magnesia, and has a total pore volume of 0.1 to 10 measured by a mercury intrusion method. In the range of 0.5 ml / g,
It has pore characteristics in which the pore volume of 100 nm or more is in the range of 0.1 to 0.25 ml / g, and the pore volume of 2000 nm or more is in the range of 0.05 to 0.2 ml / g, 250m by nitrogen gas adsorption BET method
² / g or more, and the addition amount of the Group VIII noble metal in the periodic table to the silica-magnesia oxide is 0.1% in terms of metal element.
~ 2% by weight.

A method for producing a catalyst for hydrotreating an aromatic compound in a hydrocarbon oil according to a second embodiment of the present invention comprises:
It is characterized in that one or more metal salt solutions selected from noble metals of Group VIII of the periodic table are supported as active components on an oxide catalyst carrier composed of silica-magnesia, and dried and calcined. The silica-magnesia hydrate gel containing 25 to 50% by weight of magnesia in terms of oxide is mixed with silica-magnesia hydrate powder obtained by pulverizing the gel and kneaded. Molded, dried and calcined silica obtained by baking and containing no inorganic oxide components other than magnesia-Oxide catalyst carrier consisting of magnesia, selected from the noble metals of Group VIII of the Periodic Table as active components One or two or more metal salt solutions are supported, dried and calcined, and the pore characteristics of the solution are in the range of 0.1 to 0.5 ml / g as measured by a mercury intrusion method. 100 nm or less Pore volume of 0.1 to 0.25
And the pore volume of 2000 nm or more is in the range of 0.05 to 0.2 ml / g.
And a specific surface area of 250 measured by a nitrogen gas adsorption BET method.
It is characterized in that a catalyst containing no inorganic oxide component other than silica and magnesia having m ² / g or more was prepared.

Further, according to a third embodiment of the present invention, there is provided a method for producing a catalyst for hydrotreating an aromatic compound in a hydrocarbon oil, comprising the steps of: preparing a hydrate comprising silica-magnesia as an active ingredient; One or more metal salt solutions selected from group noble metals are kneaded, dried and calcined, and silica containing 25 to 50% by weight of magnesia in terms of oxide. -A magnesia hydrate gel, a silica-magnesia hydrate powder obtained by pulverizing the gel, and a solution of one or more metal salts selected from noble metals of Group VIII of the Periodic Table. And knead with
Kneaded, molded, dried and fired, and the pore characteristics of which were measured by a mercury intrusion method to a total pore volume of 0.1 to 0.5.
And the pore volume of 100 nm or more is in the range of 0.1 to 0.25 ml / g.
Inorganic oxide components other than silica and magnesia having a pore volume of 000 nm or more in a range of 0.05 to 0.2 ml / g and a specific surface area of 250 m ² / g or more measured by a nitrogen gas adsorption BET method. It is characterized in that a catalyst containing no catalyst is prepared.

In the second and third embodiments of the present invention, the oxide of silica-magnesia may be selected from one or two selected from the group VIII noble metals of the periodic table.
It is characterized by adding 0.1 to 2% by weight of a metal salt solution of at least one kind in terms of a metal element, drying and firing.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION A silica-magnesia oxide according to the present invention and one or more selected from noble metals of Group VIII of the Periodic Table as active ingredients, and a porous material The hydrotreating catalyst formed in
In summary, it is manufactured by the following two steps. That is, an oxide catalyst carrier comprising silica-magnesia is used, and the gel is powdered into a silica-magnesia hydrate gel having a magnesia content in the range of 25 to 50% by weight in terms of oxide. Silica-magnesia hydrate powder is added, kneaded, molded, dried and calcined, and an oxide catalyst carrier comprising silica-magnesia containing no inorganic oxide components other than magnesia. And one or more metal salt solutions selected from the Group VIII noble metals of the periodic table as active ingredients, dried, and fired.

[0015] A silica-magnesia hydrate gel obtained by pulverizing the gel into a silica-magnesia hydrate gel having a magnesia content of 25 to 50% by weight in terms of oxide in terms of oxides. Hydrate powder and one or two or more metal salt solutions selected from Group VIII noble metals of the periodic table are added, kneaded with a kneader equipped with a heating jacket, kneaded and molded. And baking after drying. In the above two steps, as a method for producing a silica-magnesia hydrate gel and a silica-magnesia hydrate powder having a magnesia content in the range of 25 to 50% by weight in terms of oxide, a general method is used. For example, an aqueous solution of sodium silicate and an aqueous solution of magnesium chloride in an amount ranging from 25 to 50% by weight as MgO when converted to an oxide. Is mixed, hydrolyzed, and the resulting silica-magnesia hydrate slurry is filtered, washed, and filtered to produce a silica-magnesia hydrate gel. Further, after adding water to the silica-magnesia hydrate gel to form a paste, spray drying, freeze drying, or drying the silica-magnesia hydrate gel,
By crushing, a silica-magnesia hydrate powder having an average particle size in the range of 5 to 20 μm can be produced.

The silica raw material used for producing the silica-magnesia hydrate gel includes water-soluble salts such as No. 1 sodium silicate solution, No. 2 sodium silicate solution, No. 3 sodium silicate solution and silicon tetrachloride solution. And magnesia raw materials include magnesium chloride,
And water-soluble salts such as magnesium sulfate, magnesium nitrate, and magnesium acetate. Further, the drying temperature for the preparation of the catalyst carrier and the drying temperature after kneading are not particularly limited as long as the obtained catalyst carrier or catalyst is uniformly dried, and from the viewpoint of efficiency and simplicity, 80 to 120. It may be dried at a temperature in the range of ° C., and similarly, the firing temperature may be in the range of 400 to 600 ° C., because the oxide state does not occur below 400 ° C.
On the other hand, if it is calcined at a temperature exceeding 600 ° C., the specific surface area of the obtained catalyst will be significantly reduced. In the present invention, the silica and magnesia-free oxide containing no inorganic oxide components other than silica and magnesia are the silica and magnesia hydrate other than the trace inorganic substances contained in the raw materials used in producing the hydrate. The matrix does not contain an inorganic oxide component such as alumina, titania, zirconia, silica-alumina, zeolite, and clay mineral as a matrix. This is because the activity and the desulfurization / denitrification activity are reduced.

Next, the above steps will be described in detail. First, when producing a hydrotreating catalyst by the above steps, the silica-magnesia hydrate powder is added to a silica-magnesia hydrate gel. , Kneading the plasticized product obtained into a desired shape, drying and drying
Calcination is usually performed at 00 ° C. for 2 hours to prepare an oxide catalyst carrier comprising silica-magnesia. Here, the reason for adding the silica-magnesia hydrate powder to the silica-magnesia hydrate gel is that silica-magnesia hydrate powder formed of a primary particle in a network structure is used.
By adding silica-magnesia hydrate powder of secondary particles or more formed by aggregation and aggregation of primary particles to magnesia hydrate gel, it can be formed into a porous material having pores of 100 nm or more. This is because it becomes possible to satisfy the range of the pore characteristics described below of the obtained catalyst. Then, one or two or more selected from the Group VIII noble metals of the periodic table as active ingredients are added to the catalyst carrier prepared as described above in an amount of 0.1 to 2% by weight in terms of metal element per catalyst weight. And then fired after drying.

The metal salt solution of the noble metal of Group VIII of the Periodic Table used in the above may be any water-soluble salt such as nitrate, chloride, acetate, ammine complex, etc. As a loading method, it is convenient to carry out the loading by a typical impregnation method among known catalyst preparation methods such as an ion exchange method, an impregnation method, and a gas phase method. After the loading, the active component is immobilized on the catalyst carrier. Drying and baking. The drying temperature at this time is not particularly limited as long as the obtained catalyst is uniformly dried, and may be dried at a temperature in the range of 80 to 120 ° C. in the same manner as described above from the viewpoint of efficiency and simplicity. The calcination temperature is usually 350 to 600 ° C., preferably 400 ° C., since the carried active component may change due to aggregation or phase change.
It is preferable to set the temperature in the range of -500 ° C.

On the other hand, when the hydrotreating catalyst is produced by the above-mentioned process, the silica-magnesia hydrate gel is mixed with the silica-magnesia hydrate powder in an amount of 0.1 to 2 in terms of a metal element. A plasticized product obtained by adding one or more metal salt solutions selected from noble metals of Group VIII of the Periodic Table as an active ingredient so as to contain the same by weight and kneading the resulting mixture into a desired shape. And dried to 400-600
Firing at 2 ° C. for usually 2 hours. Here, the reason why the silica-magnesia hydrate powder is added to the silica-magnesia hydrate gel is that the primary particles are agglomerated in the silica-magnesia hydrate gel formed of a primary particle in a network structure as described above. ,
By adding silica-magnesia hydrate powder of secondary particles or more formed by aggregation, it becomes possible to form a porous material having pores of 100 nm or more,
This is because the range of the pore characteristics described below of the obtained catalyst can be satisfied.

The metal salt solution of a noble metal of Group VIII of the periodic table used in the above may be any water-soluble salt such as nitrate, chloride, acetate, ammine complex and the like. In any case, the amount of the silica-magnesia hydrate powder to be added varies depending on the method for producing the silica-magnesia hydrate powder.For example, silica-magnesia hydrate gel is dried and pulverized silica. If magnesia hydrate powder is used, it is preferably added in the range of 20 to 70% by weight in terms of oxide. The reason for adding one or more selected from the Group VIII noble metals of the periodic table as an active ingredient so as to be supported or contained in an amount of 0.1 to 2% by weight in terms of a metal element is as follows. If the amount of the active metal is less than 0.1% by weight, the effect due to the active metal is insufficient to exhibit the effect. On the other hand, if the amount exceeds 2% by weight, further improvement in the catalytic activity can be obtained. Because you can't.

The shape of the hydrotreating catalyst of the present invention can be appropriately selected from desired shapes such as cylindrical, three-lobe, four-lobe and spherical. The pore characteristics of the hydrotreating catalyst according to the present invention thus obtained have a total pore volume in the range of 0.1 to 0.5 ml / g as measured by a mercury intrusion method and a pore size of 100 nm. The above pore volume is 0.1 to 0.1.
25 ml / g, the pore volume of 2000 nm or more is 0.05-0.2 ml / g, preferably the total pore volume is 0.15-0.3 ml / g. , The pore volume of 100 nm or more is in the range of 0.1 to 0.2 ml / g;
The pore volume of 0 nm or more is 0.05 to 0.15 ml / g, and the specific surface area measured by the nitrogen gas adsorption BET method is 250 m ² / g or more.

When the pore characteristics of the catalyst are less than the lower limit of the range, the reactants cannot penetrate into the fine pores of silica-magnesia, and the effect of the hydrogenation activity of the catalyst cannot be obtained. If it exceeds the value, the mechanical strength of the catalyst is remarkably reduced, and the characteristics as an industrial catalyst are lost. The mechanical strength of the industrial catalyst depends on the size and shape of the catalyst, but generally needs to be about 1.5 kg / mm for a 1.5 mm cylindrical one. The reason why the specific surface area measured by the nitrogen gas adsorption BET method is 250 m ² / g or more is that if the effective specific surface area of the catalyst is less than 250 m ² / g, the internal surface area of the pores decreases, and consequently the active metal This is because the degree of dispersion of the catalyst decreases and the catalytic reaction does not proceed efficiently.

The active ingredient used in the present invention is ruthenium, rhodium, palladium or platinum, preferably palladium or platinum, selected from the noble metals of Group VIII of the periodic table. These noble metals may be used alone or in combination, and it is particularly preferable to use a mixture of palladium and platinum. In the present invention, the reason for setting the content of magnesia in the oxide of silica-magnesia in the range of 25 to 50% by weight in terms of oxide is that outside this range, the amount of solid acid of silica-magnesia decreases and / or Alternatively, it is presumed that the amount of the solid base is increased, so that a sufficient function as the hydrotreating catalyst, which is the object of the present invention, cannot be exhibited.

The hydrotreating catalyst according to the present invention thus obtained has a high hydrogenation activity for aromatic hydrocarbon compounds contained in hydrocarbon oil and is excellent in poisoning of sulfur compounds and the like. ing. It is presumed that such an effect is because the catalyst according to the present invention has a specific pore structure and a high specific surface area, so that the intended reaction is efficiently promoted.

[0025]

EXAMPLES Hereinafter, specific examples of the present invention will be described in detail along with examples and comparative examples. However, the present invention is not limited to the scope of the embodiments. [Example 1] (Preparation of catalyst carrier) 25 liters of water and 16450 ml of 5.3 wt% magnesium chloride solution as MgO were placed in a 100 liter stainless steel reactor equipped with a stirrer. After heating and maintaining the mixture at 60 ° C. and stirring, a total of 17500 ml of a 9.2% by weight sodium silicate solution was added dropwise as SiO ₂ while stirring, and 7200 ml of a 20% by weight sodium hydroxide solution were further added. A silica-magnesia hydrate slurry having a pH of 10.8 was obtained.

Next, after aging the slurry for 30 minutes,
Na ₂ O as a 35.1 wt% including silica as MgO filtering and washing to until 0.2 wt% or less - to give magnesia hydrate gel. Next, a part of the silica-magnesia hydrate gel was dried at a temperature of 110 ° C. for 15 hours and pulverized to obtain a silica-magnesia hydrate powder having an average particle diameter of 10 μm. And the silica-magnesia hydrate gel 118
4 g (180 g as SiO ₂ -MgO) and 208 g of silica-magnesia hydrate powder (180 g as SiO ₂ -MgO) are kneaded in a kneader equipped with a heating jacket until sufficiently plasticized, and then the plasticized product is extruded. After molding at a temperature of 110 ° C. for 15 hours, the mixture was fired at 600 ° C. for 2 hours in an electric furnace to prepare a silica-magnesia catalyst support 1 ′ having a diameter of 1.2 mm.

(Preparation of catalyst) 5.51 g of a tetraammineplatinum nitrate solution containing 5.5% by weight of Pt and 15.04 g of a tetraammine palladium nitrate solution containing 4.7% by weight of Pd were thoroughly mixed and mixed. 100 g of the silica-magnesia catalyst support 1 ′ was charged with 100 g of the impregnating liquid whose volume was adjusted with water so as to have a liquid volume corresponding to the water absorption of the support.
After aging, dried at a temperature of 110 ° C. for 15 hours,
It was calcined at 500 ° C. for 2 hours in an electric furnace to obtain Catalyst 1 (Example 1). The amount of active metal carried in the obtained catalyst 1 was 0.3% by weight as Pt and 0.7% by weight as Pd. The obtained catalyst 1 is shown in Table 1 below for the pore characteristics determined by the mercury intrusion method, the specific surface area determined by the BET method by nitrogen gas adsorption, and the composition of the catalyst 1.

(Evaluation of Catalyst Performance) Example 1 Obtained
Using a fixed bed flow reactor with a catalyst loading of 15 ml, the catalyst 1 of No. 1 had a sulfur concentration of 519 ppm, a nitrogen concentration of 101 ppm, total aromatics: 30.3% by weight, and polycyclic aromatics: 6.1% by weight. The reaction conditions were as follows: reaction pressure: 5.0 Mpa, hydrogen / oil ratio: 600 N
1 / l, liquid hourly space velocity (LHSV): 2.0 hr ⁻¹ , reaction temperature: 320 ° C., dearomatization ratio in treated oil 50 hours after the start of the reaction, naphtha fraction, desulfurization / denitrification reaction The activity was determined and the results are shown in Table 2 below.

[Examples 2 and 3] (Preparation of catalyst carrier) In the preparation of the catalyst carrier of Example 1, the amount of silica-magnesia hydrate powder added to the silica-magnesia hydrate gel was calculated in terms of oxide. With 2 each
Catalyst carrier 2 'and catalyst carrier 3' were prepared in the same manner as in the preparation of the catalyst carrier of Example 1 except that the amounts were changed to 5% by weight and 60% by weight.

(Preparation of Catalyst) Catalyst 2 (Example 2) and Catalyst 3 were prepared in the same manner as in the preparation of the catalyst of Example 1 except that the thus obtained catalyst carriers 2 'and 3' were used.
(Example 3) was obtained. The pore characteristics of the catalysts 2 and 3 obtained by the mercury intrusion method and BE by nitrogen gas adsorption
The specific surface area and the composition of the catalyst determined by the T adsorption method are shown in Table 1 below.

(Evaluation of Catalyst Performance) Each evaluation of the catalysts 2 and 3 was carried out in the same manner as the performance evaluation of the catalyst of Example 1, and the results are shown in Table 2 below.

[0032] [Examples 4 and 5] In the preparation of the catalyst carrier (catalyst preparation of the support) Example 1, SiO dropping amount of sodium silicate solution 9.2% strength by weight as SiO ₂ to be dropped into the reaction vessel ₂ Catalyst carrier 4 'and catalyst carrier 5' were prepared in the same manner as in the preparation of the catalyst carrier of Example 1 except that the catalyst carrier was changed to 75% by weight and 50% by weight.

(Preparation of Catalyst) Catalyst 4 (Example 4) and Catalyst 5 were prepared in the same manner as in the preparation of the catalyst of Example 1 except that the catalyst carriers 4 'and 5' thus obtained were used.
(Example 5) was obtained. The pore characteristics of the catalysts 4 and 5 obtained by the mercury intrusion method and BE by nitrogen gas adsorption
The specific surface area and the composition of the catalyst determined by the T adsorption method are shown in Table 1 below.

(Evaluation of Performance of Catalyst) Each evaluation of the catalysts 4 and 5 was performed in the same manner as in the performance evaluation of the catalyst of Example 1.
The results are shown in Table 2 below.

Example 6 (Preparation of catalyst) In the preparation of the catalyst of Example 1, the catalyst carrier 1 'of Example 1 was used as the catalyst carrier, and the type of the metal salt solution of the active ingredient was changed to hexachloroplatinum. Catalyst 6 (Example 6) was obtained by the same procedure as in the preparation of the catalyst of Example 1 except that the acid was replaced with palladium nitrate. Table 1 below shows the pore characteristics of the catalyst 6 obtained by the mercury intrusion method, the specific surface area determined by the BET adsorption method using nitrogen gas adsorption, and the composition of the catalyst.

(Evaluation of Catalyst Performance) Each evaluation of the catalyst 6 was performed in the same manner as in the performance evaluation of the catalyst of Example 1, and the results are shown in Table 2 below.

[Example 7] (Preparation of catalyst carrier) In the preparation of the catalyst carrier of Example 1, water was added to a part of the silica-magnesia hydrate gel to form a slurry, followed by spray drying. A catalyst carrier 7 'was prepared in the same manner as in the preparation of the catalyst carrier of Example 1, except that the silica-magnesia hydrate powder was used.

(Preparation of catalyst) Catalyst 7 (Example 7) was obtained by the same procedure as in the preparation of the catalyst of Example 1 except that the catalyst carrier 7 'thus obtained was used. The pore characteristics of the catalyst 7 obtained by the mercury intrusion method, the specific surface area obtained by the BET adsorption method using nitrogen gas adsorption, and the composition of the catalyst are shown in Table 1 below.

(Evaluation of Catalyst Performance) Each evaluation of the catalyst 7 was carried out in the same manner as in the evaluation of the performance of the catalyst of Example 1, and the results are shown in Table 2 below.

[Examples 8 and 9] (Preparation of catalyst) In the preparation of the catalyst of Example 1, the catalyst carrier 3 'of Example 3 was used as the catalyst carrier, and the amount of active metal supported was 0 as Pt. The catalyst was prepared in the same manner as in the preparation of the catalyst of Example 1, except that the catalyst was changed so as to be 0.15% by weight, 0.35% by weight as Pd, 0.6% by weight as Pt, and 1.40% by weight as Pd. 8
(Example 8) and a catalyst 9 (Example 9) were obtained. Table 1 below shows the pore characteristics of the catalysts 8 and 9 obtained by the mercury intrusion method, the specific surface area obtained by the BET adsorption method using nitrogen gas adsorption, and the composition of the catalyst.

(Evaluation of Catalyst Performance) Each of the catalysts 8 and 9 was evaluated in the same manner as the performance evaluation of the catalyst of Example 1, and the results are shown in Table 2 below.

Comparative Examples 1 and 2 (Preparation of Catalyst Carrier) In the preparation of the catalyst carrier of Example 1, the amount of silica-magnesia hydrate powder added to the silica-magnesia hydrate gel was calculated in terms of oxide. And each one
The catalyst carrier 10 'and the catalyst carrier 1 were prepared in the same manner as in the preparation of the catalyst carrier of Example 1 except that the carrier was replaced with 0% by weight and 80% by weight.
1 'was prepared.

(Preparation of catalyst) The catalyst 10 (Comparative Example 1) was prepared in the same manner as in the preparation of the catalyst of Example 1 except that the catalyst carriers 10 'and 11' thus obtained were used.
Catalyst 11 (Comparative Example 2) was obtained. Catalysts 10 and 11 obtained
Table 1 below shows the pore characteristics determined by the mercury intrusion method, the specific surface area determined by the BET adsorption method using nitrogen gas adsorption, and the composition of the catalyst.

(Evaluation of Catalyst Performance) Each evaluation of the catalysts 10 and 11 was carried out in the same manner as in the performance evaluation of the catalyst of Example 1.
The results are shown in Table 2 below.

[Comparative Example 3] (Preparation of catalyst carrier) The catalyst carrier 12 'was prepared in the same manner as in the preparation of the catalyst carrier of Example 1, except that the calcination temperature was changed to 750 ° C. Was prepared.

(Preparation of Catalyst) Catalyst 12 (Comparative Example 3) was obtained in the same manner as in the preparation of the catalyst of Example 1, except that the obtained catalyst carrier 12 'was used. The resulting catalyst 12
Table 1 below shows the pore characteristics determined by the mercury intrusion method, the specific surface area determined by the BET adsorption method using nitrogen gas adsorption, and the composition of the catalyst.

(Evaluation of Performance of Catalyst) Performance evaluation was performed in the same manner as the performance evaluation of the catalyst of Example 1, and the results are shown in Table 2 below.

Comparative Examples 4 and 5 (Preparation of Catalyst Carrier) In the preparation of the catalyst carrier of Example 1, the amount of the 9.2 wt% sodium silicate solution added dropwise to the reaction vessel was changed to SiO _{2. A} catalyst carrier 13 'and a catalyst carrier 14' were prepared in the same manner as in the preparation of the catalyst carrier of Example 1, except that 85% by weight and 40% by weight of Compound No. 2 were produced.

(Preparation of catalyst) The resulting catalyst carrier 13 ',
Catalyst 13 (Comparative Example 4) and Catalyst 14 (Comparative Example 5) were obtained in the same procedure as in the preparation of the catalyst of Example 1 except that 14 'was used. The pore characteristics of the catalysts 13 and 14 obtained by the mercury intrusion method and the BET by nitrogen gas adsorption
The specific surface area and the composition of the catalyst determined by the adsorption method are shown in Table 1 below.

(Evaluation of Performance of Catalyst) Performance evaluation was performed in the same manner as in the performance evaluation of the catalyst of Example 1, and the results are shown in Table 2 below.

Comparative Example 6 (Preparation of Catalyst Carrier) In the preparation of the catalyst carrier of Comparative Example 1, 50% by weight of silica-magnesia hydrate powder was added to silica-magnesia hydrate gel in terms of oxide. A catalyst support 15 'was prepared in the same manner as in the preparation of the catalyst support of Example 1, except that 5% by weight of an alumina hydrate powder manufactured by Condia Co., Ltd. were added in terms of oxide.

(Preparation of catalyst) A catalyst 15 (Comparative Example 6) was obtained in the same procedure as in the preparation of the catalyst of Example 1, except that the obtained catalyst carrier 15 'was used. Catalyst 15 obtained
Table 1 below shows the pore characteristics determined by the mercury intrusion method, the specific surface area determined by the BET adsorption method using nitrogen gas adsorption, and the composition of the catalyst.

(Evaluation of the performance of the catalyst) The performance was evaluated in the same manner as that of the catalyst of Example 1, and the results are shown in Table 2 below.

[0054]

[Table 1]

[0055]

[Table 2] As can be seen from Tables 1 and 2 above, the catalysts 1 to 9 of Examples 1 to 9 are all within the scope of the present invention with respect to the silica-magnesia composition of the catalyst, the pore characteristics of the catalyst, the specific surface area and the amount of active metal carried. Was satisfied, and high dearomatic activity and high desulfurization / denitrification activity were confirmed.

On the other hand, the catalysts 10 and 1 of Comparative Examples 1 and 2
1 indicates that the silica-magnesia composition of the catalyst, the specific surface area of the catalyst, and the amount of active metal supported are within the scope of the present invention, but the total pore volume, 100 nm, 2000 nm, which is the pore characteristic of the catalyst.
a catalyst with a small or large pore volume of nm,
The dearomatization activity and desulfurization / denitrification activity showed low values.

Next, the catalyst 12 of Comparative Example 3 is a catalyst having a small specific surface area of the catalyst, although the silica-magnesia composition of the catalyst, the pore characteristics of the catalyst and the amount of active metal supported are within the scope of the present invention. The aromatic activity and the desulfurization / denitrification activities showed low values. Further, the catalysts 13 and 14 of Comparative Examples 4 and 5 have the silica-magnesia composition of the catalyst outside the range of the present invention, although the pore characteristics and the specific surface area of the catalyst and the amount of active metal supported fall within the range of the present invention. It was a catalyst and showed low values of dearomatic activity and desulfurization / denitrification activity.

Further, the catalyst 15 of Comparative Example 6 is a catalyst in which alumina is contained in the catalyst, although the pore characteristics and specific surface area of the catalyst and the amount of active metal supported are within the scope of the present invention. Activity and desulfurization / denitrification activities showed low values. It was also apparent that hydrocracking was suppressed by using the silica-magnesia produced by the silica-magnesia hydrolysis method of the present invention as a raw material, since the amount of naphtha fraction in the treated oil was small.

Example 10 (Preparation of catalyst) A silica-magnesia hydrate gel and a silica-magnesia hydrate powder were obtained in the same procedure as in Example 1. And the obtained silica-magnesia hydrate gel 11
84 g (180 g as SiO ₂ -MgO), 208 g of silica-magnesia hydrate powder (180 g as SiO ₂ -MgO), 19.84 g of a tetraammineplatinum nitrate solution containing 5.5% by weight as Pt, and 4 g as Pd 5% by weight of tetraammine palladium nitrate containing 0.7% by weight
4.14 g was kneaded in a kneader equipped with a heating jacket until it was sufficiently plasticized, then the plasticized product was molded by an extruder, dried at a temperature of 110 ° C. for 15 hours, and then heated at 500 ° C. for 2 hours in an electric furnace. By calcining, a silica-magnesia catalyst 16 (Example 10) having a diameter of 1.2 mm was obtained. About the obtained catalyst 16, the following Table 3 shows the pore characteristics determined by the mercury intrusion method, the specific surface area determined by the BET adsorption method using nitrogen gas adsorption, and the catalyst composition as in Example 1.
Shown in

(Evaluation of the performance of the catalyst) The performance was evaluated in the same manner as in the evaluation of the catalyst of Example 1, and the results are shown in Table 4 below.

Examples 11 and 12 (Preparation of catalyst) In the preparation of the catalyst of Example 10, the amount of silica-magnesia hydrate powder added to the silica-magnesia hydrate gel was calculated in terms of oxides. Catalyst 17 (Example 11) and Catalyst 18 (Example 12) were prepared by the same procedure as in the preparation of the catalyst of Example 10, except that the weight was changed to 30% by weight and 60% by weight. The resulting catalyst 17,
Regarding No. 18, the pore characteristics determined by the mercury intrusion method, the specific surface area determined by the BET adsorption method using nitrogen gas adsorption, and the catalyst composition are also shown in Table 3 below.

(Evaluation of the performance of the catalyst) The performance was evaluated in the same manner as in the performance evaluation of the catalyst of Example 1, and the results are shown in Table 4 below.

[0063] In preparation of the catalyst of Example 13, 14] (Preparation of Catalyst) Example 10, the drop amount of sodium silicate solution 9.2% strength by weight as SiO ₂ to be dropped into the reaction vessel as respective SiO ₂ Catalyst 19 (Example 13) and Catalyst 20 (Example 14) were obtained by the same procedure as in the preparation of the catalyst of Example 10 except that the production was changed to 75% by weight and 50% by weight. Table 3 below shows the pore characteristics of the catalysts 19 and 20 obtained by the mercury intrusion method, the specific surface area and the catalyst composition obtained by the BET adsorption method using nitrogen gas adsorption.

(Evaluation of Performance of Catalyst) Performance evaluation was performed in the same manner as the performance evaluation of the catalyst of Example 1, and the results are shown in Table 4 below.

[Example 15] (Preparation of catalyst) In the preparation of the catalyst of Example 10, the type of the metal salt solution of the active ingredient to which silica-magnesia hydrate gel and silica-magnesia hydrate powder were added was changed. Example 1 except that xachloroplatinic acid and palladium nitrate were replaced
Catalyst 21 (Example 1)
5) was prepared. The obtained catalyst 21 is shown in Table 3 below for the pore characteristics determined by the mercury intrusion method, the specific surface area determined by the BET adsorption method using nitrogen gas adsorption, and the catalyst composition.

(Evaluation of Performance of Catalyst) Performance evaluation was performed in the same manner as the performance evaluation of the catalyst of Example 1, and the results are shown in Table 4 below.

[Example 16] (Preparation of catalyst) In the preparation of the catalyst of Example 10, silica was obtained by adding water to a part of the silica-magnesia hydrate gel to form a slurry, followed by spray drying. Catalyst 22 (Example 16) was prepared in the same manner as in the preparation of the catalyst in Example 10, except that magnesia hydrate powder was used.
Table 3 below shows the pore characteristics of the obtained catalyst 22 obtained by the mercury intrusion method, the specific surface area obtained by the BET adsorption method using nitrogen gas adsorption, and the catalyst composition.

(Evaluation of Performance of Catalyst) Performance evaluation was performed in the same manner as the performance evaluation of the catalyst of Example 1, and the results are shown in Table 4 below.

[Examples 17 and 18] (Preparation of catalyst) In the preparation of the catalyst of Example 10, the amount of active metal added to the silica-magnesia hydrate gel and the silica-magnesia hydrate powder was 0 as Pt, respectively. .15
Catalyst 23 (Example 17) was prepared in the same manner as in the preparation of the catalyst of Example 10 except that the weight% and Pd were changed to 0.35% by weight, Pt to 0.6% by weight and Pd to 1.40% by weight. ) And catalyst 24 (Example 18). The obtained catalysts 23 and 24 are shown in Table 3 below together with the pore characteristics determined by the mercury intrusion method, the specific surface area determined by the BET adsorption method using nitrogen gas adsorption, and the catalyst composition.

(Evaluation of Performance of Catalyst) Performance evaluation was performed in the same manner as the performance evaluation of the catalyst of Example 1, and the results are shown in Table 4 below.

Comparative Examples 7 and 8 (Preparation of Catalyst) In the preparation of the catalyst of Example 10, the amount of silica-magnesia hydrate powder added to the silica-magnesia hydrate gel was calculated in terms of oxide. Catalyst 25 (Comparative Example 7) and Catalyst 26 (Comparative Example 8) were prepared in the same manner as in the preparation of the catalyst of Example 10, except that the amounts were changed to 10% by weight and 80% by weight. Table 3 below shows the pore characteristics of the catalysts 25 and 26 obtained by the mercury intrusion method, the specific surface area and the catalyst composition obtained by the BET adsorption method using nitrogen gas adsorption.

(Evaluation of Performance of Catalyst) Performance evaluation was performed in the same manner as the performance evaluation of the catalyst of Example 1, and the results are shown in Table 4 below.

[Comparative Example 9] (Preparation of catalyst) Catalyst 27 (Comparative Example) was prepared in the same manner as in the preparation of the catalyst of Example 10 except that the calcination temperature was changed to 750 ° C. 9) was prepared. Table 3 below shows the pore characteristics of the obtained catalyst 27 obtained by the mercury intrusion method, the specific surface area obtained by the BET adsorption method using nitrogen gas adsorption, and the catalyst composition.

(Evaluation of Performance of Catalyst) Performance evaluation was performed in the same manner as the performance evaluation of the catalyst of Example 1, and the results are shown in Table 4 below.

[0075] In the preparation of the catalysts of Comparative Examples 10 and 11] (Preparation of Catalyst) Example 10, the drop amount of sodium silicate solution 9.2% strength by weight as SiO ₂ to be dropped into the reaction vessel as respective SiO ₂ Catalyst 28 (Comparative Example 10) and Catalyst 29 (Comparative Example 11) were prepared by the same procedure as in the preparation of the catalyst of Example 10, except that the amounts were changed to 85% by weight and 40% by weight, respectively. Table 3 below shows the pore characteristics of the catalysts 28 and 29 obtained by the mercury intrusion method, the specific surface area and the catalyst composition obtained by the BET adsorption method using nitrogen gas adsorption.

(Evaluation of Performance of Catalyst) Performance evaluation was performed in the same manner as the performance evaluation of the catalyst of Example 1, and the results are shown in Table 4 below.

Comparative Example 12 (Preparation of Catalyst) Silica-magnesia hydrate gel obtained in the same manner as in the preparation of the catalyst of Comparative Example 7 was mixed with silica-magnesia hydrate powder and alumina hydrate manufactured by Condia. Example 10 except that powder was added at 5% by weight in terms of oxide.
Catalyst 30 (Comparative Example 12) was prepared in the same manner as in the preparation of the catalyst (1). For the obtained catalyst 30, the following Table 3 shows the pore characteristics determined by the mercury intrusion method, the specific surface area determined by the BET adsorption method using nitrogen gas adsorption, and the catalyst composition.
Are shown together.

(Evaluation of Catalyst Performance) Further, performance evaluation was performed in the same manner as in the performance evaluation of the catalyst of Example 1, and the results are shown in Table 4 below.

[0079]

[Table 3]

[0080]

[Table 4]

As can be seen from Tables 3 and 4, all of the catalysts 16 to 24 of Examples 10 to 18 were prepared according to the present invention with respect to the silica-magnesia composition, the pore characteristics of the catalyst, the specific surface area and the content of the active metal. Was satisfied, and high dearomatic activity and high desulfurization / denitrification activity were confirmed.

On the other hand, the catalysts 25 and 2 of Comparative Examples 7 and 8
No. 6 shows that the silica-magnesia composition, the specific surface area of the catalyst and the content of the active metal fall within the scope of the present invention, but the total pore volume, that is, the pore volume of 100 nm and 2000 nm, which are the pore characteristics of the catalyst, is small or large. It was a catalyst and showed low values of dearomatic activity and desulfurization / denitrification activity.
Next, the catalyst 27 of Comparative Example 9 is a catalyst having a small specific surface area, although the silica-magnesia composition and the pore characteristics and the content of the active metal of the catalyst fall within the scope of the present invention. -The denitrification activity showed a low value.

Further, the catalysts 2 of Comparative Examples 10 and 11
Nos. 8 and 29 are catalysts whose silica-magnesia composition is out of the range, although the pore characteristics and specific surface area of the catalyst and the amount of active metal supported are within the scope of the present invention. Showed a low value.

Further, the catalyst 30 of Comparative Example 12 is a catalyst containing alumina although the pore characteristics, specific surface area and active metal content of the catalyst fall within the scope of the present invention. And the desulfurization / denitrification activity showed a low value.

It is also clear that the use of silica-magnesia produced by the silica-magnesia hydrolysis method of the present invention as a raw material suppresses hydrocracking because the amount of naphtha fraction in the treated oil is small.

[0086]

As described above, by using the hydrotreating catalyst according to the present invention, the dearomatic activity for hydrogenating aromatic hydrocarbon compounds in hydrocarbon oil containing sulfur compounds and the like is high, It can hydrotreat a hydrocarbon oil having a low rate of hydrocracking and having excellent activity against sulfur compounds and nitrogen compounds.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C10G 45/52 C10G 45/52 // B01J 21/14 B01J 21/14 M 32/00 32/00 C07B 61 / 00 300 C07B 61/00 300 (72) Inventor Yuki Kanai 3-18-5, China, Ichikawa, Chiba Prefecture Sumitomo Metal Mining Co., Ltd. Central Research Laboratory (72) Inventor Eiji Yokozuka 3-18, China, Ichikawa, Chiba −5 Sumitomo Metal Mining Co., Ltd. Central Research Laboratory F-term (reference) 4G069 AA03 AA08 AA12 BA02A BA02B BA06A BA06B BA20A BA20B BB02A BB02B BC69A BC72B BC75A CC02 DA06 EA02Y EB18Y EC03X EC03Y EC06FB EC07Y EC18FB14 AA02 AC11 BA06 BA33 BA81 BC10 BC11 BC18 BE20 4H029 CA00 DA00 4H039 CA40 CB10

Claims (13)

[Claims] 1. A catalyst for hydrotreating an aromatic compound in a hydrocarbon oil, comprising: an oxide comprising silica-magnesia; and a noble metal selected from Group VIII noble metals of the Periodic Table as an active ingredient. A hydrotreating catalyst comprising a kind or two or more kinds and formed porous. 2. The aromatic compound in a hydrocarbon oil according to claim 1, wherein the content of magnesia in the silica-magnesia oxide is in the range of 25 to 50% by weight in terms of oxide. For hydrotreating. 3. The hydrogen of an aromatic compound in a hydrocarbon oil according to claim 1, wherein the oxide composed of silica and magnesia does not contain an inorganic oxide component other than silica and magnesia. Catalyst for chemical treatment. 4. The total pore volume measured by the mercury intrusion method is 0.
In the range of 1-0.5 ml / g, 100 nm
The above pore volume is in the range of 0.1 to 0.25 ml / g, and the pore volume of 2000 nm or more is 0.05 to
The catalyst for hydrotreating an aromatic compound in a hydrocarbon oil according to any one of claims 1 to 3, wherein the catalyst has pore characteristics in a range of 0.2 ml / g. 5. 250 m ² / g by nitrogen gas adsorption BET method
5. It has the above specific surface area.
The catalyst for hydrotreating an aromatic compound in a hydrocarbon oil according to any one of the above. 6. The addition amount of a noble metal of Group VIII of the Periodic Table to the oxide comprising silica-magnesia is 0.1 to 2% by weight in terms of a metal element.
The catalyst for hydrotreating an aromatic compound in a hydrocarbon oil according to any one of claims 1 to 5. 7. An oxide catalyst carrier comprising silica-magnesia, on which one or more metal salt solutions selected from noble metals of Group VIII of the periodic table as an active ingredient are supported,
A method for producing a catalyst for hydrotreating an aromatic compound in a hydrocarbon oil, comprising calcining after drying. 8. A silica-magnesia hydrate gel containing 25 to 50% by weight of magnesia in terms of oxides is mixed with powdered silica-magnesia hydrate powder obtained by powdering the gel, and the mixture is kneaded and molded. An oxide catalyst carrier comprising silica and magnesia containing no inorganic oxide components other than silica and magnesia obtained by drying and then firing is used as an active component. The method for producing a catalyst for hydrotreating an aromatic compound in a hydrocarbon oil according to claim 7, wherein one or more metal salt solutions are supported, dried and calcined. 9. A silica-magnesia hydrate gel containing 25 to 50% by weight of magnesia in terms of oxides is mixed with powdered silica-magnesia hydrate powder, and the mixture is kneaded and molded. An oxide catalyst carrier comprising silica and magnesia containing no inorganic oxide components other than silica and magnesia obtained by drying and then firing is used as an active component. One or two or more metal salt solutions are supported, dried and calcined, and the pore characteristics thereof are determined by a mercury porosimetry.
And the pore volume of 100 nm or more is in the range of 0.1 to 0.25 ml / g.
Inorganic oxide components other than silica and magnesia having a pore volume of 000 nm or more in a range of 0.05 to 0.2 ml / g and a specific surface area of 250 m ² / g or more measured by a nitrogen gas adsorption BET method. The method for producing a catalyst for hydrotreating an aromatic compound in a hydrocarbon oil according to claim 7 or 8, wherein a catalyst containing no hydrocarbon is prepared. 10. A method comprising kneading a hydrate comprising silica-magnesia with one or more metal salt solutions selected from noble metals of Group VIII of the Periodic Table as an active ingredient, drying and calcining. A method for producing a catalyst for hydrotreating an aromatic compound in a hydrocarbon oil. 11. A magnesia content of 2 in terms of oxide.
A silica-magnesia hydrate gel containing 5 to 50% by weight is prepared by adding silica-magnesia hydrate powder obtained by pulverizing the gel and a noble metal selected from Group VIII noble metals of the periodic table.
2. A seed or two or more kinds of metal salt solutions are added, kneaded, kneaded, molded, dried and fired.
0. The method for producing a catalyst for hydrotreating an aromatic compound in a hydrocarbon oil according to 0. 12. Magnesia is converted to an oxide in the range of 25 to 50.
Weight% of silica-magnesia hydrate gel, powdered silica-magnesia hydrate powder and one or two selected from the group VIII noble metals of the periodic table.
More than one kind of metal salt solution is added and kneaded, kneaded, molded, dried and fired, and the pore characteristics thereof are determined by mercury intrusion method. / G in the range of 0.1 to 0.25.
And the pore volume of 2000 nm or more is in the range of 0.05 to 0.2 ml / g.
And a specific surface area of 250 measured by a nitrogen gas adsorption BET method.
m 2 ^{/ g} or more and silica and non-magnesia inorganic oxide component, characterized in that to prepare a catalyst containing no claim 10 or 11, wherein the aromatic compound in hydrocarbon oil hydroprocessing catalyst Production method. 13. An oxide composed of silica and magnesia, wherein one or two or more metal salt solutions selected from Group VIII noble metals of the periodic table are converted to a metal element in an amount of 0.1 to 0.1%.
The method for producing a catalyst for hydrotreating an aromatic compound in a hydrocarbon oil according to any one of claims 7 to 12, wherein the catalyst is added, and dried and calcined.