JP2013027839A - Method of manufacturing hydrogenation catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing a hydrogenation catalyst, in which the hydrogenation catalyst with a more excellent desulfurization activity is manufactured more conveniently and industrially.SOLUTION: The method of manufacturing the hydrogenation catalyst includes: a first process in which at least one or more active metal components chosen from the periodic table group 6 and the group 8 to group 10 are supported on a carrier to obtain an active metal carrier; a second process in which the active metal carrier is impregnated with a chelating agent-containing aqueous solution including a chelating agent and moisture to obtain an impregnated carrier; a third process in which the impregnated carrier is aged at 80 to 150°C while keeping the liquid amount[mass%] of the chelating agent-containing aqueous solution contained, as calculated by the following Formula (1):{(W2-W1)/W1}×100, at ≥50% to obtain an aging carrier; and a fourth process in which the aging carrier is dried at ≤300°C. In the Formula (1), W1 is the mass after drying the aging carrier after the end of the third process at 500°C and W2 is the mass of the aging carrier at the third process end.

Description

  The present invention relates to a method for easily and industrially producing a hydrotreating catalyst having more excellent desulfurization activity.

  In the oil refining process, a large amount of hydrotreating catalyst is used for the purpose of removing impurities such as sulfur and nitrogen in the feedstock. However, in recent years when environmental conservation is required on a global scale, the regulation of sulfur content in refined fuel oil has become more stringent worldwide. In particular, as a further reduction of harmful substances contained in automobile exhaust gas, reduction of sulfur in light oil is regarded as a major issue. This is because noble metals, basic oxides, and the like used as the catalyst material of the exhaust gas treatment device are easily poisoned by sulfur. For this reason, in Japan, sulfur-free liquid fuels such as light oil and gasoline have been reduced to a sulfur content of 10 ppm or less, and accordingly, high-performance catalysts with high desulfurization performance have been developed for hydrotreating catalysts. It has been broken.

Conventionally, a hydrotreating catalyst has a porous inorganic oxide support such as alumina, silica, alumina-boria, zeolite, etc., a periodic table group 6 metal such as molybdenum and tungsten, and / or a periodic table such as cobalt and nickel. The impregnation solution containing an active metal component such as a Group 8 metal was brought into contact (impregnated), then dried and fired, and the support was loaded with the active metal. This hydrotreating catalyst is used after being sulfurized.
However, this manufacturing method has a problem that active metal aggregation occurs in the firing step and the sulfidation step, that is, the dispersibility of the active metal is deteriorated and the desulfurization activity is lowered.
Therefore, by adding a chelating agent to the impregnating solution, the aggregation of the active metal is suppressed, and the active metal supported on the carrier is highly dispersed to improve the desulfurization performance (for example, Patent Documents 1 to 3). reference).

JP 2004-344725 A JP 2004-344754 A JP-A-2005-873

However, in the market, there is a demand for hydrotreating catalysts with higher desulfurization performance and smaller degradation of catalytic reaction, and development of production methods that avoid high costs for commercial productivity. Yes.
In this invention, the manufacturing method of the hydrotreating catalyst which manufactures the hydrotreating catalyst more excellent in desulfurization activity more simply and industrially is provided.

According to a first aspect of the present invention, there is provided an active metal carrier by supporting at least one active metal component selected from Group 6, Group 8 to Group 10 (above, IUPAC notation, the same shall apply hereinafter) on the carrier. A first step to obtain;
A second step of impregnating the active metal carrier with a chelating agent-containing aqueous solution containing a chelating agent and moisture to obtain an impregnated carrier;
The impregnated carrier obtained in the second step is aged at 80 ° C. or higher and 150 ° C. or lower while maintaining the content of the chelating agent-containing aqueous solution calculated by the following formula (1) at 50% or higher. A third step of obtaining an aged carrier,
And a fourth step of obtaining the hydrotreating catalyst by drying the aged support obtained in the third step at 300 ° C. or lower.
Liquid content [% by mass] = {(W2−W1) / W1} × 100 (1)
However, W1 is the mass after drying the aged carrier after completion of the third step at 500 ° C., and W2 is the mass of the aged carrier at the end of the third step.

The second invention is characterized in that the third step is performed in a range of 0.10 to 0.51 MPa (1 to 5 atm).
In a third invention, in place of the first step, in the second step, the chelating agent-containing aqueous solution contains at least one active metal component selected from Groups 6 and 8 to 10 of the periodic table. Is added.

4th invention is the manufacturing method of the hydroprocessing catalyst which re-disperses the active metal component carry | supported by the hydroprocessing catalyst before use, and improves activity,
A first step of impregnating a hydrotreatment catalyst before use with a chelating agent-containing aqueous solution containing a chelating agent and moisture to obtain an impregnated catalyst;
The impregnation catalyst obtained in the first step is aged at 80 ° C. or higher and 150 ° C. or lower while maintaining the liquid content of the chelating agent-containing aqueous solution calculated by the following formula (2) at 50% or higher. A second step of obtaining an aging catalyst;
And a third step of obtaining an improved catalyst by drying the aged catalyst obtained in the second step at 300 ° C. or less, and a liquid content [mass%] = { (W4-W3) / W3} × 100 (2)
However, W3 is a mass after drying the aged catalyst after completion | finish of a 2nd process at 500 degreeC, and W4 is a mass of the aged catalyst at the end of a 2nd process.

The fifth invention is characterized in that the second step is performed in a range of 0.10 to 0.51 MPa (1 to 5 atm).
A sixth invention is characterized in that, in the first step, at least one active metal component selected from Groups 6 and 8 to 10 of the periodic table is added to the chelating agent-containing aqueous solution. To do.
The seventh invention is characterized in that the active metal component is selected from Group 8 to Group 10 of the periodic table, and the addition amount thereof is 1% by mass or less of the improved catalyst in terms of oxide.
The eighth invention is characterized in that, in the first step, a calcined catalyst obtained by calcining a hydrotreatment catalyst before use at a temperature exceeding 300 ° C. is used.

  In the present invention, after bringing the chelating agent and water into contact with each other, aging is performed at 80 to 150 ° C. where sufficient water exists and can be maintained. The performance can be further improved, and the performance degradation of the catalytic reaction can be further reduced. Moreover, it is only necessary to provide an aging step controlled to a predetermined temperature and a predetermined amount of water after the impregnation step, and further, a treatment with a shorter aging time than that of the prior art is possible, so that a high-performance catalyst can be produced at a low cost. I can do it.

It is the plot figure which showed the change of NO adsorption amount when changing aging temperature. It is the plot figure which showed the change of relative desulfurization activity when changing aging temperature. It is the plot figure which showed the change of NO adsorption amount when changing the pressure at the time of ageing | curing | ripening. It is the plot figure which showed the change of the relative desulfurization activity when changing the pressure at the time of ageing | curing | ripening.

[Hydroprocessing catalyst]
The hydrotreating catalyst for hydrocarbon oil to which the present invention is applied is a desulfurization or desulfurization catalyst by contacting light oil or heavy oil that is hydrocarbon oil with hydrogen in the presence of the catalyst under a high temperature and high pressure atmosphere. It is a general hydroprocessing catalyst that promotes reactions such as denitrification, demetalization and hydrocracking. Examples of light oil include naphtha, kerosene, light gas oil (LGO), heavy gas oil (HGO), vacuum gas oil (Vacuum Gas Oil, VGO), etc. Examples of heavy oil Examples thereof include atmospheric residual oil (Atmospheric Residue, AR) and vacuum residual oil (Vacuum Residue, VR).

  The carrier constituting the hydrotreating catalyst is composed of an inorganic oxide, such as alumina, silica, titania, silica-alumina, alumina-titania, alumina-zirconia, alumina-boria, phosphorus-alumina, silica-alumina. -Boria, phosphorus-alumina-boria, phosphorus-alumina-silica, silica-alumina-titania, silica-alumina-zirconia and the like can be exemplified.

  As the active metal component supported on the carrier, at least one active metal component is selected from Groups 6 and 8 to 10 of the periodic table (hereinafter referred to as IUPAC notation, the same applies hereinafter), and more preferably At least one active metal component is selected from at least one group of Table 6 and Groups 8 to 10 of the periodic table. Examples of the active metal component of Group 6 of the periodic table include molybdenum (Mo), tungsten (W), chromium (Cr), etc., and examples of the active metal component of Groups 8 to 10 of the periodic table include nickel (Ni), Examples include cobalt (Co). In addition to these active metal components, other elements such as phosphorus and boron may be added as appropriate. The type of active metal component selected and the amount of the active metal component selected are appropriately set according to the type of hydrocarbon oil to be treated and the process conditions.

<Method for producing first hydrotreating catalyst>
[First step: loading step]
In this step, at least one active metal component selected from Groups 6 and 8 to 10 of the periodic table is supported on the above-described support to obtain an active metal support.
The supporting method of the active metal component is not limited to a special method, but usually various supporting methods such as a solid phase mixing method, a liquid phase mixing method, a coprecipitation method, a soaking method, and a reverse micelle method. Can be adopted.
For example, when carrying by the impregnation method, a solution of the active metal component alone or a compound containing the active metal component (for example, a metal salt, a metal oxide, or a metal hydroxide) on the carrier, Impregnation is performed by a method such as an adsorption method, an equilibrium adsorption method, a pore filling method, an incipient wetness method, an evaporation to dryness method, or a spray method.
The mixture of the carrier obtained by each of the above loading methods and the raw material of the active metal component is dried at room temperature to less than 300 ° C. in the air or in an inert atmosphere. Further, the mixture may be fired by heating the mixture before or after drying in the air or in an inert atmosphere. When firing at 300 ° C. or higher, the dispersibility of the active metal component may be reduced as compared with drying alone.

[Second step: impregnation step]
In this step, the active metal carrier is impregnated with a chelating agent-containing aqueous solution containing a chelating agent and moisture to obtain an impregnated carrier. The chelating agent forms a coordinate bond with the active metal, plays a role of supporting the active metal in a highly dispersed state on the support and maintaining the state.
Examples of the chelating agent include gluconic acid, malic acid, citric acid, tartaric acid, and oxalic acid. A sufficient amount of the chelating agent that can be coordinated to the active metal component to be treated is added. Considering the aging temperature described later and ease of penetration into the pores, the chelating agent is preferably brought into contact with the active metal carrier in the form of an aqueous solution containing water as a solvent. The mixing ratio of the chelating agent and water varies depending on the viscosity of the aqueous solution. For example, as a liquid viscosity target, a kinematic viscosity is adjusted to a range of 20 mm ² / S (cSt) or less with a capillary viscometer.

Further, the step of supporting the active metal component on the carrier in advance in the first step is omitted, and the active metal component is added to the chelating agent-containing aqueous solution, whereby the active metal component is added to the carrier in the second step. It may be supported. In this case, the chelating agent-containing aqueous solution contains fine particle sols of metals of Group 6 of the periodic table (molybdenum, tungsten, chromium, etc.), metals of Groups 8-10 of the periodic table (nickel, cobalt, etc.) A metal salt, a metal complex salt, or the like as a raw material of the active metal component is added.
In addition, various additives such as inorganic phosphoric acid such as phosphoric acid, ammonium dihydrogen phosphate and diammonium hydrogen phosphate, monosaccharides such as glucose, sucrose and maltose, disaccharides and polysaccharides are added to the chelating agent-containing aqueous solution. May be added.

  As a method for impregnating the chelating agent-containing aqueous solution with the active metal carrier, various impregnation methods such as an adsorption method, a pore filling method, a minimum wetting method, and an evaporation to dryness method are employed. For example, when the subsequent third step (aging step) is performed in a saturated vapor pressure atmosphere of the chelating agent-containing aqueous solution, the amount of the chelating agent-containing aqueous solution impregnated in the active metal carrier is a predetermined amount of the chelating agent-containing aqueous solution described later. It is preferable to impregnate the chelating agent-containing aqueous solution in an amount larger than the predetermined amount so that the remaining on the surface of the active metal carrier. This liquid content is the volume of the container for executing the aging process, the amount of evaporation of the chelating agent-containing aqueous solution under the temperature and pressure conditions in the container, and the amount of the chelating agent-containing aqueous solution that should remain on the active metal carrier at this time. The total amount can be determined.

[Third step: Aging step]
In this step, the liquid content of the chelating agent-containing aqueous solution brought into contact with the active metal carrier in the second step is kept at 80 ° C. or higher and 150 ° C. while maintaining a state of 50% or higher calculated by the following formula (1). Aged below.
Liquid content [% by mass] = {(W2−W1) / W1} × 100 (1)
However, W1 is the mass of the catalyst after drying the hydrotreating catalyst after completion of the third step at 500 ° C., and W2 is the mass of the catalyst at the end of the third step.
In this step, the active metal carrier impregnated with the chelating agent-containing aqueous solution is heated, and ripening is performed in a state where the chelating agent-containing aqueous solution remains on the surface, so that a heating mechanism such as an autoclave is provided. It can be carried out in a closed container. By aging in the state where the chelating agent remains on the surface of the active metal carrier, sufficient time is ensured to disperse the active metal component to be treated, and aging is performed under heating conditions. By performing, aging time can be shortened compared with the case where heating is not performed.
When the aging temperature is lower than 80 ° C., even if the chelation reaction occurs, a very slow and long treatment time is required and the productivity is likely to be lowered. Moreover, when the temperature at the time of aging exceeds 150 degreeC, possibility that a chelating agent will decompose | disassemble or change will become high, aggregation of an active metal will occur at the time of an aging process, and the maintenance management of a moisture content will become difficult. The aging temperature is preferably 95 ° C. or higher and 140 ° C. or lower, more preferably 100 ° C. or higher and 130 ° C. or lower.

The active metal component is dispersed by the action of the chelating agent during the aging process, so that a highly active hydrotreating catalyst can be produced, and the active points of the catalyst during the sulfidation treatment before use and the catalyst use It is possible to suppress the quantitative change of.
The above formula (1) indicates the ratio of the mass of the chelating agent-containing aqueous solution present in the catalyst at the end of ripening to the mass of the hydrotreating catalyst after completion of the third step, and this value is large. This shows that the amount of the chelating agent aqueous solution remaining on the surface of the hydrotreating catalyst during the aging period is large. When the liquid content represented by the formula (1) is less than 50% by mass, the amount of the chelating agent present in the treatment catalyst is not sufficient, and the active metal component to be treated is sufficient even if the aging time is prolonged. Cannot be dispersed. On the other hand, when the liquid content exceeds 95% by mass, the active metal component bonded to the chelating agent flows out into the aqueous chelating agent solution, making it difficult to advance the dispersion of the active metal component on the active metal carrier. turn into. For this reason, the liquid content of the chelating agent aqueous solution represented by the formula (1) is in the range of 50 to 95% by mass, preferably in the range of 50 to 85% by mass, and more preferably in the range of 50 to 75% by mass. Set to
In addition, the method of maintaining the liquid content of the chelating agent aqueous solution at 50% by mass or more is not limited to the case where the inside of the sealed container is a saturated vapor pressure atmosphere of the chelating agent aqueous solution. For example, a liquid replenishment mechanism may be provided in an open container having a heating mechanism so that the chelating agent aqueous solution and moisture are supplied so that the liquid content is maintained.

Furthermore, as shown in the examples described later, by performing aging at 0.10 to 0.51 MPa (1 to 5 atm), the quantitative change in the active point of the catalyst during sulfidation before use and during use of the catalyst Can be further suppressed. This is because the chelation reaction between the chelating agent and the active metal species is promoted by adjusting the pressure at the time of aging to the range of 0.10 to 0.51 MPa, and the active metal aggregates and the high-temperature, high-pressure atmosphere It is thought that the contact of the lower water molecules may promote the melting of the active metal aggregates and the complex metal complexation reaction comprising each active metal component and a chelating agent. As a result, the state of dispersion and reconstitution of the active metal is further improved, the dispersibility of the active metal is improved, and the rechelation is promoted, whereby the change of the active site is suppressed. The pressure during aging is in the range of 0.10 to 0.51 MPa (1 to 5 atm), preferably in the range of 0.12 to 0.46 MPa (1.2 to 4.5 atm), more preferably 0.15 to 0.51 MPa. It is set in the range of 0.41 MPa (1.5 to 4.0 atm).
The aging is performed for 0.25 to 8 hours, preferably 0.5 to 5 hours under the above-described temperature, liquid content, and pressure conditions.
The active metal carrier which has been aged in this way and has the active metal component dispersed therein is taken out of the sealed container and subjected to the next drying treatment.

[Fourth step: drying step]
In this step, a hydrotreating catalyst is obtained by drying the hydrotreating catalyst that has been aged in a state where the chelating agent aqueous solution is sufficiently present on the catalyst surface at 300 ° C. or lower.
The active metal carrier that has been aged is heated in a gas having a low water content, for example, by heating in the chelating agent aqueous solution remaining on the active metal carrier after aging, such as in the surface of the carrier or in the pores. A drying process for evaporating the water is performed. The drying process may be performed under conditions sufficient to evaporate water remaining on the surface of the hydrotreating catalyst. The drying treatment is performed for a time sufficient to evaporate moisture within a temperature range of, for example, room temperature to 300 ° C. or less, preferably room temperature to 270 ° C. or less, more preferably room temperature to 250 ° C. or less. The atmosphere in which the drying process is performed may be an oxygen-containing atmosphere such as an air atmosphere, or an inert gas atmosphere that does not contain oxygen gas. In some cases, the active metal component on the hydrotreating catalyst produced by finishing the drying treatment is supported while being coordinated with the chelating agent, or the chelating agent is decomposed by the drying treatment. In some cases, it is supported in a metal state. Further, when dried in an oxygen-containing atmosphere, a part of the active metal component may be oxidized.
The hydrotreating catalyst produced through the first to fourth steps described above is filled in a reaction tower of a hydrocarbon oil hydrotreating apparatus, and sulfiding treatment for sulfiding an active metal component on a support. Is done.

  The method for producing a hydrotreating catalyst of the present embodiment has the following effects. After bringing the solution containing the chelating agent into contact with the carrier carrying the active metal component in the first step (second step), the liquid content of this solution is kept at 50% or more of the catalyst mass, Aging under temperature conditions (third step) promotes dispersion of the active metal component and chelation of the active metal component. As a result, it is possible to produce with a shorter aging time than a conventional hydrotreating catalyst produced using the same additive, and the quantity of active sites of the catalyst during sulfidation treatment before use and when using the catalyst. It is possible to increase stability while suppressing changes.

<Method for producing second hydrotreating catalyst>
The hydrotreating catalyst (hydrotreating catalyst before use) calcined at a temperature of 300 ° C. or higher after the active metal component is supported decreases the dispersibility of the active metal component, thereby reducing the catalyst performance. There is a case. Therefore, the hydrotreating catalyst before use is aged in contact with a chelating agent-containing aqueous solution containing a chelating agent and water to disperse the active metal component and thereby the activity of the hydrotreating catalyst (improved catalyst). Can be improved.

[First step: Impregnation step]
The hydrotreating catalyst before use is impregnated with a chelating agent-containing aqueous solution containing a chelating agent and moisture to obtain an impregnated catalyst.
However, when adding a metal salt or metal complex salt as a raw material for these active metals, a fine particle sol of Group 6 metal of the periodic table, Group 8 to Group 10 metal of the periodic table in this aqueous solution, The following points are different from the manufacturing method of the first hydrotreating catalyst.
That is, the active metal supported on the hydrotreating catalyst is mainly composed of a periodic table group 6 metal functioning as a main component of the hydroprocessing, and a periodic table group 8 to 10 metal functioning as a co-catalyst. And forms an active structure. When such a catalyst is calcined at a temperature of 300 ° C. or higher, the presence state may change due to aggregation or desorption even if all or part of the active metal species is slight. In such a case, by adding the metals of Group 8 to Group 10 of the periodic table and their raw materials, these metals can be newly supported on the hydroprocessing catalyst to supplement the structure of the active structure. good. However, if the amount of newly added active metal is too large, aggregation of the newly added active metal itself tends to occur. As a result, re-dispersion and reconfiguration of the active metal of Group 6 of the periodic table, which is the original purpose, is hindered, and an ideal re-dispersed state and active metal structure may not be obtained. Therefore, the amount of the newly added periodic table Group 8 to Group 10 active metal is 1 mass% or less, more preferably 0.5 mass% or less of the mass of the hydrotreating catalyst. Good.
However, the active metal added to the aqueous solution of the chelating agent is not limited to the case where an active metal of Group 8 to Group 10 of the periodic table is added as a co-catalyst. It goes without saying that active metals of both Group 6 and Groups 8 to 10 may be added. In this case as well, the concentration of the newly added active metal is preferably 1% by mass or less, more preferably 0.5% by mass or less of the hydrotreating catalyst.
In this case, the aqueous solution of the chelating agent also includes inorganic phosphoric acid such as phosphoric acid, ammonium dihydrogen phosphate and diammonium hydrogen phosphate, monosaccharides such as glucose, sucrose and maltose, disaccharides and polysaccharides. Various additives may be added.
Here, in the first step, a calcined catalyst obtained by calcining the hydrotreated catalyst before use at 300 ° C. or higher may be used instead of the hydrotreated catalyst before use.

[Second step: Aging step]
In the second step, the impregnated catalyst is aged to obtain an aged catalyst in the same manner as in the third step of the method for producing the first hydrotreating catalyst.
[Third step: drying step]
In the third step, in the same manner as in the fourth step of the method for producing the first hydrotreating catalyst, an aged catalyst is aged to obtain an improved catalyst (improved hydrotreating catalyst).
The improved catalyst produced through the first to third steps described above is charged in a reaction tower of a hydrocarbon oil hydrotreating apparatus, and is subjected to a sulfiding treatment for sulfiding an active metal component on a support. Is called.

  The method for improving the hydrotreating catalyst before use according to this embodiment has the following effects. After contacting the hydrotreating catalyst before use with the chelating agent-containing aqueous solution (first step), aging under a temperature condition of 80 to 150 ° C. while maintaining the liquid content of this solution at 50% or more of the catalyst mass Therefore (second step), redispersion of the active metal component and chelation of the active metal component are promoted. As a result, it is possible to improve the activity in a shorter aging time than when using the same additive to improve the activity, and suppress the quantitative change in the active point of the catalyst during sulfidation before use and when using the catalyst. Stability can be increased.

<Example 1: Hydrotreating catalyst a>
(1) Preparation of carrier
In a 1 L beaker, 90.9 g of 22% by mass sodium aluminate aqueous solution in terms of Al ₂ O ₃ concentration is added, and ion-exchanged water is added to 400 g, and further, 2.2 g of 26% by mass sodium gluconate solution is added to this solution. In addition, the mixture was heated to 60 ° C. with stirring to obtain a 5% by mass aqueous sodium aluminate solution in terms of Al ₂ O ₃ concentration. Separately, 138.6 g of a 7% by mass aluminum sulfate aqueous solution in terms of Al ₂ O ₃ concentration was placed in a 500 ml container, and warm water at 60 ° C. was added to obtain 400 g of a 2.5% by mass aluminum sulfate aqueous solution.
Next, the aqueous aluminum sulfate solution was added to the aqueous sodium aluminate solution at a constant rate (40 ml / min) so that the pH became 7.1 in 10 minutes. The obtained suspension slurry was aged at 60 ° C. for 1 hour with stirring. The suspension slurry was 10% by mass in terms of Al ₂ O ₃ concentration.
The suspension slurry after aging was dehydrated and washed with 1.5 L of hot water at 60 ° C. to obtain a cake slurry. Next, ion-exchanged water was added to the cake-like slurry so as to be 10% by mass in terms of Al ₂ O ₃ concentration, and the mixture was aged at 95 ° C. for 10 hours while stirring. The slurry after completion of aging was heated while kneading with a double-arm kneader with a steam jacket, concentrated to a predetermined moisture content (45% by mass), then the heating was stopped, and the mixture was further kneaded for 30 minutes. The obtained kneaded product was molded into a 1.8 mm cylindrical shape with an extrusion molding machine and then dried at 110 ° C. The dried pellets were fired in an electric furnace at a temperature of 550 ° C. for 3 hours to obtain a γ-alumina carrier that is a porous inorganic oxide. The carrier had a surface area of 195 m ² / g and a pore volume of 0.80 cm ³ / g.
(2) Preparation of impregnation solution
In a 200 ml beaker, 150 ml of ion exchange water and 29.1 g of molybdenum trioxide [manufactured by Taiyo Mining Co., Ltd .: 99.9% as MoO ₃ ] were added and stirred at 95 ° C. for 10 hours. Next, 11.8 g of cobalt carbonate [manufactured by Tanaka Chemical Laboratory Co., Ltd .: 61.1% as CoO] was added and stirred at 95 ° C. for 5 hours. 13.5 g [malic acid / cobalt = 1/1 (mol / mol)] of malic acid [manufactured by Fuso Chemical Industry Co., Ltd .: 99.9%] was added to this mixture and stirred at the same temperature for 5 hours. The resulting solution was concentrated to 80 ml to obtain an impregnation solution.

[First step: loading step]
The prepared alumina carrier was impregnated with the above impregnation solution by a pore filling method. Subsequently, the obtained mixture of the support and the raw material of the active metal component was dried at 110 ° C. for 2 hours in the atmosphere and further fired at 550 ° C. in the atmosphere to obtain an active metal carrier a.
[Second step: impregnation step]
46.4 g of 50% gluconic acid aqueous solution (gluconic acid / molybdenum = 0.8 / 1 [mol / mol]) as a chelating agent-containing aqueous solution is added to 100 g of active metal carrier a, and impregnated until the pore volume is saturated. An impregnated carrier a was obtained.
[Third step: Aging step]
The impregnated carrier a was mixed and aged for 2 hours in an airtight container (autoclave) in a saturated steam atmosphere at a temperature of 110 ° C. and a pressure of 0.10 MPa (1 atm) to obtain an aged carrier a after aging.
After completion of the third step, a part of the aged carrier a was taken out and its mass (W2) was measured to be 15.61 g. The mass (W1) of the catalyst dried at 500 ° C. was 9.94 g. It was. Here, from formula (1), the liquid content of the gluconic acid aqueous solution in the aging carrier a was 57% by mass.
Liquid content [% by mass] = {(W2−W1) / W1} × 100 (1)
[Fourth step: drying step]
Next, drying was performed in air at a temperature of about 150 ° C. for about 2 hours to obtain a hydrotreating catalyst a. Table 1 shows properties of the hydrotreating catalyst a.

<Example 2: Hydrotreating catalyst b>
The hydrotreated catalyst was treated in the same manner as in Example 1 except that the impregnated carrier a after completion of the second step was dried after standing for 30 minutes in a room temperature atmosphere to adjust the moisture, and then performing the third step. b was obtained. Here, the liquid content of the gluconic acid aqueous solution of the aging carrier b was 50% by mass. Table 1 shows properties of the hydrotreating catalyst b.

<Examples 3 to 7: hydrotreating catalysts c to g>
In the third step, hydrotreating catalysts c to g were obtained in the same manner as in Example 1 except that the aging temperatures were 80 ° C., 90 ° C., 100 ° C., 120 ° C., and 140 ° C., respectively. Here, the liquid content of the gluconic acid aqueous solution of the aging carriers c to g was 60% by mass, 58% by mass, 57% by mass, 54% by mass, and 51% by mass, respectively. Table 1 shows properties of the hydrotreating catalysts c to g.

<Example 8: Hydrotreating catalyst h>
A hydrotreating catalyst h was obtained in the same manner as in Example 1 except that the aging temperature was 80 ° C. and the aging time was 8 hours. The liquid content of the gluconic acid aqueous solution in the aging carrier h was 55% by mass. Table 1 shows properties of the hydrotreating catalyst h.

<Example 9: Hydrotreating catalyst i>
A hydrotreating catalyst i was obtained in the same manner as in Example 1 except that the aging temperature was 90 ° C. and the aging time was 5 hours. The liquid content of the gluconic acid aqueous solution in the aging carrier i was 58% by mass. Table 1 shows properties of the hydrotreating catalyst i.

<Examples 10 to 16: hydrotreating catalysts j to p>
In the third step, the pressure conditions during aging were 0.08 MPa (0.8 atm), 0.12 MPa (1.2 atm), 0.18 MPa (1.8 atm), 0.22 MPa (2.2 atm), and 0, respectively. Hydrotreating catalysts j to p were obtained in the same manner as in Example 1 except that the pressure was .25 MPa (2.5 atm), 0.43 MPa (4.2 atm), and 0.62 MPa (6.1 atm). Here, the liquid contents of the gluconic acid aqueous solution in the aging carriers j to p were 53 mass%, 56 mass%, 56 mass%, 61 mass%, 52 mass%, 54 mass%, and 57 mass%, respectively. Table 1 shows properties of the hydrotreating catalysts j to p.

<Example 17: Hydrotreating catalyst q>
A hydrotreating catalyst q was obtained in the same manner as in Example 1 except that the pressure condition during aging was 0.25 MPa (2.5 atm) and the aging time was 1 hour. The liquid content of the gluconic acid aqueous solution in the aging carrier q was 55% by mass. Table 1 shows properties of the hydrotreating catalyst q.

<Example 18: Hydrotreating catalyst r>
In the same manner as in Example 1, except that 0.82 g of 61.1% by mass of cobalt carbonate corresponding to 0.5% by mass of the hydrotreating catalyst in terms of cobalt oxide was added to the gluconic acid aqueous solution. Thus, a hydrotreating catalyst r was obtained. The liquid content of the gluconic acid aqueous solution in the aging carrier r was 56% by mass. Table 1 shows properties of the hydrotreating catalyst r.

<Example 19: Hydrotreating catalyst s>
In the same manner as in Example 1, except that 1.64 g of 61.1% by mass of cobalt carbonate corresponding to 1.0% by mass of the hydrotreating catalyst in terms of cobalt oxide was added to the gluconic acid aqueous solution. Thus, a hydrotreating catalyst s was obtained. The liquid content of the gluconic acid aqueous solution in the aging support was 53% by mass. Table 1 shows properties of the hydrotreating catalyst s.

<Example 20: Hydrotreating catalyst t>
In the same manner as in Example 1 except that 2.45 g of 61.1% by mass of cobalt carbonate corresponding to 1.5% by mass of the hydrotreating catalyst in terms of cobalt oxide was added to the gluconic acid aqueous solution. Thus, a hydrotreating catalyst t was obtained. The liquid content of the gluconic acid aqueous solution in the aging carrier t was 53% by mass. Table 1 shows properties of the hydrotreating catalyst t.

<Example 21: Hydrotreating catalyst u>
In the same manner as in Example 1, except that 0.91 g of 55.0% by mass of nickel oxide corresponding to 0.5% by mass of the hydrotreating catalyst in terms of nickel oxide was added to the gluconic acid aqueous solution. Thus, a hydrotreating catalyst u was obtained. The liquid content of the gluconic acid aqueous solution in the aging carrier u was 57% by mass. Table 1 shows properties of the hydrotreating catalyst u.

<Example 22: Hydrotreating catalyst v>
In the same manner as in Example 1 except that 1.82 g of 55.0% by mass of nickel oxide corresponding to 1.0% by mass of the hydrotreating catalyst in terms of nickel oxide was added to the gluconic acid aqueous solution. Thus, a hydrotreating catalyst v was obtained. The liquid content of the gluconic acid aqueous solution in the aging carrier v was 57% by mass. Table 1 shows properties of the hydrotreating catalyst v.

<Example 23: Hydrotreating catalyst w>
In the same manner as in Example 1 except that 2.74 g of 55.0% by mass of nickel oxide corresponding to 1.5% by mass of the hydrotreating catalyst in terms of nickel oxide was added to the gluconic acid aqueous solution. Thus, a hydrotreating catalyst w was obtained. The liquid content of the gluconic acid aqueous solution in the aging carrier w was 54% by mass. Table 1 shows properties of the hydrotreating catalyst w.

<Comparative Example 1: Hydrotreating catalyst x>
A hydrotreating catalyst x was obtained in the same manner as in Example 1 except that the impregnated carrier a was dried without being aged (that is, not passed through the third step). Table 1 shows properties of the hydrotreating catalyst x.

<Comparative Example 2: Hydrotreating catalyst y>
A hydrotreating catalyst y was obtained in the same manner as in Example 1 except that the aging temperature was 60 ° C. The liquid content of the gluconic acid aqueous solution in the aging carrier y was 59% by mass. Table 1 shows properties of the hydrotreating catalyst y.

<Comparative Example 3: Hydrotreating catalyst z>
A hydrotreating catalyst was obtained in the same manner as in Example 1 except that the aging temperature was 70 ° C. The liquid content of the gluconic acid aqueous solution in the aging support z was 58% by mass. Table 1 shows properties of the hydrotreating catalyst z.

<Comparative Example 4: Hydrotreating catalyst a1>
A hydrotreating catalyst a1 was obtained in the same manner as in Example 1 except that the aging temperature was 160 ° C. The liquid content of the aqueous gluconic acid solution in the aging carrier a1 was 51% by mass. Table 1 shows properties of the hydrotreating catalyst a1.

<Comparative Example 5: Hydrotreating catalyst a2>
A hydrotreating catalyst a2 was obtained in the same manner as in Example 1 except that the aging temperature was 60 ° C. and the aging time was 8 hours. The liquid content of the gluconic acid aqueous solution in the aging carrier a2 was 53% by mass. Table 1 shows properties of the hydrotreating catalyst a2.

<Comparative Example 6: Hydrotreating catalyst a3>
A hydrotreating catalyst a3 was obtained in the same manner as in Example 1 except that the aging temperature was 70 ° C. and the aging time was 10 hours. The liquid content of the gluconic acid aqueous solution in the aging carrier a3 was 51% by mass. Table 1 shows properties of the hydrotreating catalyst a3.

<Comparative Example 7: Hydrotreating catalyst a4>
A hydrotreating catalyst a4 was obtained in the same manner as in Example 1 except that the impregnated catalyst before the aging step was allowed to stand for 60 minutes in a room temperature atmosphere and then dried. The liquid content of the gluconic acid aqueous solution in the aging carrier a4 was 43% by mass. Table 1 shows properties of the hydrotreating catalyst a4.

[Test Example 1: Stability evaluation test]
About 0.02 g of the hydrotreating catalyst to be evaluated, pulverized to 60 mesh or less, was filled in a quartz cell, heated to 400 ° C., and 5% hydrogen sulfide / 95% hydrogen by volume gas. Was circulated at a flow rate of 0.2 L / min to perform sulfurization treatment. The amount of change in the reaction active site accompanying the change in the treatment time was measured by changing the sulfurization treatment time to 1 hour and 5 hours.
The amount of reaction active sites of each catalyst was measured by a NO adsorption amount measurement method in which nitrogen monoxide was adsorbed on the reaction active sites and the amount of adsorption was measured. The NO adsorption amount is measured using a fully automatic catalytic gas adsorption amount measuring device (manufactured by Okura Riken). A mixed gas of He and NO (NO concentration 10% by volume) is applied to the hydrotreating catalyst subjected to the sulfidation treatment under the above conditions. It introduce | transduced with the pulse and measured the NO molecule adsorption amount per 1g of hydrotreating catalysts. Based on the measured NO molecule adsorption amount, the NO adsorption amount change rate [%] was calculated based on the following equation (3). It can be evaluated that the smaller the rate of change is, the more highly stable the hydrotreating catalyst is that the performance degradation of the catalytic reaction under high temperature and high pressure atmosphere in which the catalyst is actually used is small.
NO adsorption amount change rate [%] = {(A5-A1) / A1} × 100 (3)
However, A1 is the NO adsorption amount in the hydrotreating catalyst subjected to sulfiding treatment at 400 ° C. for 1 hour, and A5 is the NO adsorption amount in the hydrotreating catalyst subjected to sulfiding treatment at 400 ° C. for 5 hours. is there.

[Test Example 2: Hydrogenation activity evaluation test]
An aromatic hydrocarbon oil containing sulfur and nitrogen compounds was treated with the hydrotreating catalyst to be evaluated, and its hydrodesulfurization activity was evaluated. The hydrotreated catalyst was pulverized and sieved to 26-60 mesh, and 0.25 g was taken out from it and charged into a reactor (SUS316) having an outer diameter of 1/4 inch. Thereafter, the catalyst was heated to 360 ° C., and 5% by volume of hydrogen sulfide / 95% of hydrogen was passed at a flow rate of 0.2 L / min, and sulfidation treatment (preliminary sulfidation) was performed for 6 hours.
The hydrotreating catalyst after the sulfidation treatment was subjected to 4,6-dimethyldibenzothiophene (equivalent to 1000 mass ppm as a sulfur content) / n-butylamine (mass 20 ppm as a nitrogen content) / tetralin (30% by volume) / n-dodecane ( The mixed oil mixed with about 70% by volume was passed through a catalyst layer heated to a reaction temperature of 320 ° C. together with hydrogen gas to perform a hydrogenation treatment. The reaction conditions were a reaction pressure of 4.0 MPa, a mass space velocity of 16 h ⁻¹ , and a hydrogen / feed oil ratio of 500 Nm ³ / m ³ .
The sulfur content in the product oil obtained by this hydrotreating is measured by the ultraviolet fluorescence method (Mitsubishi Chemical, TS-100V), and the hydrotreating activity (desulfurization activity) is calculated based on the decreased amount. did. The hydrotreating activity was calculated from the following formula (4) as a relative value to the desulfurization activity of the hydrotreating catalyst x (Comparative Example 1) (hereinafter referred to as relative desulfurization activity). If this relative desulfurization activity was 110% or more, it was judged that a good hydrotreating catalyst was obtained as a catalyst.
Relative desulfurization activity (%) of hydrotreating catalyst = (Da / Df) × 100 (4)
However, Da is a sulfur content reduction amount of the mixed oil processed using the manufactured hydroprocessing catalyst, and Df is a sulfur content reduction of the mixed oil processed using the hydroprocessing catalyst x (Comparative Example 1). Rate.

In the examples where the relative desulfurization activity was measured, a result exceeding 110% was obtained, and a sufficient activity improvement result was obtained. On the other hand, the relative desulfurization activity of the comparative example is in a range of 101 to 105% that is practically required, and is lower than the relative desulfurization activity of the examples.
Here, the aging time and the aging pressure were constant (2 hours, 0.10 MPa (1 atm)), and the aging temperature was changed, and the stability during high-temperature treatment for Examples 1, 3 to 7, and Comparative Examples 2 to 4 was changed. The change of (absolute value of NO adsorption amount change rate) is shown by a rhombus plot in FIG. Is shown in a diamond plot. According to these figures, it can be seen that the stability of the hydrotreating catalyst subjected to the activity improvement treatment has a downward trend line with respect to the aging temperature, and the desulfurization activity has a upward trend line. . And in the range of aging temperature of 100-140 degreeC, relative desulfurization activity exceeds 120%, NO adsorption amount change rate is also less than 10%, and it can be said that the highly active and stable activity improvement result was obtained.

On the other hand, in Example 3 (aging temperature 80 ° C.), when the aging time was 2 hours, a relative desulfurization activity exceeding 120% was not obtained, but in Example 8 (aging temperature 80 ° C.), the aging time was reduced. By extending to 8 hours, a relative desulfurization activity of 121% is obtained, and the stability during high temperature treatment is also improved. Even when the aging temperature is 90 ° C., it is considered that the same result can be obtained by extending the aging time. For example, if a relative desulfurization activity of 110% or more is obtained within 10 hours of aging time, for example, an activity improving process having good stability is performed in a sufficiently short time even compared to Patent Document 6. Can be evaluated.
Moreover, according to the comparative example 7, in the comparative example 7 in which the liquid content of the gluconic acid aqueous solution measured after the aging is less than 50% by mass (43% by mass), the change rate of the NO adsorption amount is also 10%. It is much higher and the relative desulfurization activity is as low as 100%.

Next, the aging temperature and the aging time were constant (110 ° C., 2 hours), and the pressures during the aging were changed, and the conditions under the assumption of the sulfidation treatment and the catalytic reaction of Examples 1 to 10-16 were used. 3 shows the quantitative change in the active sites of the catalyst (absolute value of the NO adsorption amount change rate) in the form of a rhombus plot in FIG. 3, and the desulfurization activity (relative desulfurization activity) of Examples 1, 10, 11, and 14-16. The change is shown as a diamond plot in FIG. According to these figures, the amount of active sites adsorbed by NO of the hydrotreating catalyst that has been subjected to the activity improvement treatment has a downward trend line with respect to the pressure during aging, and the desulfurization activity has increased upward. It can be seen that the trend line is drawn. And when the pressure at the time of aging is in the range of 0.10 to 0.43 MPa (1 to 4.2 atm), the relative desulfurization activity exceeds 110%, the NO adsorption amount change rate is also less than 10%, and high activity. It can be said that a stable activity improvement result was obtained.
Finally, in Examples 18 to 20 in which a cobalt raw material was added as an active metal component and Examples 21 to 23 in which a nickel raw material was added, 0.5 to 1.0% by mass in terms of oxide in any active metal component When the active metal component in the range was added, the NO adsorption amount change rate was less than 10%. In Examples 19 and 21, the relative desulfurization activity exceeds 120%. On the other hand, when the addition amount of the active metal component was 1.5% by mass, the NO adsorption amount change rate exceeded 10%, and the relative desulfurization activity was less than 120%.
Further, according to the result of Example 2 prepared so that the liquid content after aging was 50% by mass, the NO adsorption amount change rate (absolute value) was less than 10%, and the relative desulfurization activity was 127%. It was. As a result, it was confirmed that when the liquid content after aging was 50% by mass or more, a regeneration result satisfying the target values of the NO adsorption amount change rate (absolute value) and the relative desulfurization activity was obtained.

<Example 24: Hydrotreating catalyst A>
[First step: Impregnation step]
The hydrotreating catalyst x (Comparative Example 1) was calcined at 550 ° C. in the atmosphere at a calcining catalyst (hydrotreating catalyst before use) 100 g, and as a chelating agent-containing aqueous solution 46.4 g of 50% gluconic acid aqueous solution (gluconic acid / molybdenum) = 0.8 / 1 [mol / mol]) was added and impregnation was performed until the pore volume was saturated, and impregnation catalyst A was obtained.
[Second step: Aging step]
The impregnated catalyst A was mixed and aged for 2 hours in a closed vessel (autoclave) in a saturated steam atmosphere at a temperature of 110 ° C. and a pressure of 0.10 MPa (1 atm) to obtain an aged catalyst A.
A part of the aging catalyst A was taken out after completion of the second step, and its mass (W4) was measured to be 15.85 g. The mass (W3) of the catalyst dried at 500 ° C. was 9.97 g. . Here, from formula (1), the liquid content of the gluconic acid aqueous solution in the aging catalyst A was 59% by mass.
Liquid content [% by mass] = {(W4−W3) / W3} × 100 (2)
[Third step: drying step]
Next, drying was carried out in air at a temperature of about 150 ° C. for about 2 hours to obtain a hydrotreating catalyst (improved catalyst) A. Table 2 shows properties of the hydrotreating catalyst A.

<Example 25: Hydrotreating catalyst B>
The impregnated catalyst A was allowed to stand for 30 minutes in a room temperature atmosphere and dried to adjust the moisture, and then the hydrogenation catalyst B was obtained in the same manner as in Example 24 except that the second step was performed. Here, the liquid content of the gluconic acid aqueous solution of the aging catalyst B was 50% by mass. Table 2 shows the properties and the like of the hydrotreating catalyst B.

<Examples 26 to 30: hydrotreating catalysts C to G>
In the second step, hydrotreating catalysts C to G were obtained in the same manner as in Example 24 except that the aging temperatures were 80 ° C., 90 ° C., 100 ° C., 120 ° C., and 140 ° C., respectively. Here, the liquid contents of the gluconic acid aqueous solution of the aging catalysts C to G were 54 mass%, 59 mass%, 58 mass%, 54 mass%, and 56 mass%, respectively. Table 2 shows the properties and the like of the hydrotreating catalysts C to G.

<Example 31: Hydrotreating catalyst H>
A hydrotreating catalyst H was obtained in the same manner as in Example 24 except that the aging temperature was 80 ° C. and the aging time was 8 hours. The liquid content of the gluconic acid aqueous solution in the aging catalyst H was 58 mass%. Table 2 shows the properties and the like of the hydrotreating catalyst H.

<Example 32: Hydrotreating catalyst I>
A hydrotreating catalyst I was obtained in the same manner as in Example 24 except that the aging temperature was 90 ° C. and the aging time was 5 hours. The liquid content of the gluconic acid aqueous solution in the aging catalyst I was 59% by mass. Table 2 shows properties of the hydrotreating catalyst I.

<Examples 33 to 39: Hydrotreating catalysts J to P>
In the third step, the pressure conditions during aging were 0.08 MPa (0.8 atm), 0.12 MPa (1.2 atm), 0.18 MPa (1.8 atm), 0.22 MPa (2.2 atm), and 0, respectively. Hydrotreatment catalysts J to P were obtained in the same manner as in Example 24 except that the pressure was set to .25 MPa (2.5 atm), 0.43 MPa (4.2 atm), and 0.62 MPa (6.1 atm). Here, the liquid contents of the gluconic acid aqueous solution in the aging catalysts J to P were 55% by mass, 60% by mass, 56% by mass, 55% by mass, 57% by mass, 54% by mass, and 58% by mass, respectively. Table 2 shows properties of the hydrotreating catalysts J to P.

<Example 40: Hydrotreating catalyst Q>
A hydrotreating catalyst Q was obtained in the same manner as in Example 24 except that the pressure condition during aging was 0.25 MPa (2.5 atm) and the aging time was 1 hour. The liquid content of the gluconic acid aqueous solution in the aging catalyst Q was 59% by mass. Table 2 shows properties of the hydrotreating catalyst Q.

<Example 41: Hydrotreating catalyst R>
In the same manner as in Example 24, except that 0.82 g of 61.1% by mass of cobalt carbonate corresponding to 0.5% by mass of the hydrotreating catalyst in terms of cobalt oxide was added to the gluconic acid aqueous solution. Thus, a hydrotreating catalyst R was obtained. The liquid content of the gluconic acid aqueous solution in the aging catalyst R was 55% by mass. Table 2 shows the properties and the like of the hydrotreating catalyst R.

<Example 42: Hydrotreating catalyst S>
In the same manner as in Example 24 except that 1.64 g of 61.1% by mass of cobalt carbonate corresponding to 1.0% by mass of the hydrotreating catalyst in terms of cobalt oxide was added to the aqueous gluconic acid solution. Thus, a hydrotreating catalyst S was obtained. The liquid content of the gluconic acid aqueous solution in the aging catalyst S was 56 mass%. Table 2 shows the properties and the like of the hydrotreating catalyst S.

<Example 43: Hydrotreating catalyst T>
In the same manner as in Example 24, except that 2.45 g of 61.1% by mass of cobalt carbonate corresponding to 1.5% by mass of the hydrotreating catalyst in terms of cobalt oxide was added to the gluconic acid aqueous solution. Thus, a hydrotreating catalyst T was obtained. The liquid content of the gluconic acid aqueous solution in the aging catalyst T was 57% by mass. Table 2 shows properties of the hydrotreating catalyst T.

<Example 44: Hydrotreating catalyst U>
In the same manner as in Example 24 except that 0.91 g of 55.0% by mass of nickel oxide corresponding to 0.5% by mass of the hydrotreating catalyst in terms of nickel oxide was added to the gluconic acid aqueous solution. Thus, a hydrotreating catalyst U was obtained. The liquid content of the gluconic acid aqueous solution in the aging catalyst U was 58 mass%. Table 2 shows properties of the hydrotreating catalyst U.

<Example 45: Hydrotreating catalyst V>
In the same manner as in Example 24 except that 1.82 g of 55.0% by mass of nickel oxide corresponding to 1.0% by mass of the hydrotreating catalyst in terms of nickel oxide was added to the gluconic acid aqueous solution. Thus, a hydrotreating catalyst V was obtained. The liquid content of the gluconic acid aqueous solution in the aging catalyst V was 55% by mass. Table 2 shows the properties and the like of the hydrotreating catalyst V.

<Example 46: Hydrotreating catalyst W>
In the same manner as in Example 24 except that 2.74 g of 55.0% by mass of nickel oxide corresponding to 1.5% by mass of the hydrotreating catalyst in terms of nickel oxide was added to the gluconic acid aqueous solution. Thus, a hydrotreating catalyst W was obtained. The liquid content of the gluconic acid aqueous solution in the aging catalyst W was 54 mass%. Table 2 shows properties of the hydrotreating catalyst W.

<Comparative Example 8: Hydrotreating catalyst X>
A hydrotreatment catalyst X was obtained in the same manner as in Example 24 except that drying was started immediately without aging the hydrogenation catalyst impregnated with the gluconic acid aqueous solution. Table 2 shows properties of the hydrotreating catalyst X.

<Comparative Example 9: Hydrotreating catalyst Y>
A hydrotreating catalyst Y was obtained in the same manner as in Example 24 except that the aging temperature was 60 ° C. The liquid content of the gluconic acid aqueous solution in the aging catalyst Y was 61% by mass. Table 2 shows the properties and the like of the hydrotreating catalyst Y.

<Comparative Example 10: Hydrotreating catalyst Z>
A hydrotreating catalyst Z was obtained in the same manner as in Example 24 except that the aging temperature was 70 ° C. The liquid content of the gluconic acid aqueous solution in the aging catalyst Z was 57% by mass. Table 2 shows properties of the hydrotreating catalyst Z.

<Comparative Example 11: Hydrotreating catalyst A1>
A hydrotreating catalyst A1 was obtained in the same manner as in Example 24 except that the aging temperature was 160 ° C. The liquid content of the gluconic acid aqueous solution in the aging catalyst A1 was 58% by mass. Table 2 shows properties of the hydrotreating catalyst A1.

<Comparative Example 12: Hydrotreating catalyst A2>
A hydrotreating catalyst A2 was obtained in the same manner as in Example 24 except that the aging temperature was 60 ° C. and the aging time was 8 hours. The liquid content of the gluconic acid aqueous solution in the aging catalyst A2 was 52% by mass. Table 2 shows properties of the hydrotreating catalyst A2.

<Comparative Example 13: Hydrotreating catalyst A3>
A hydrotreating catalyst A3 was obtained in the same manner as in Example 24 except that the aging temperature was 70 ° C. and the aging time was 10 hours. The liquid content of the gluconic acid aqueous solution in the aging catalyst A3 was 51% by mass. Table 2 shows properties of the hydrotreating catalyst A3.

<Comparative Example 14: Hydrotreating catalyst A4>
A hydrotreating catalyst A4 was obtained in the same manner as in Example 24 except that the impregnated catalyst before the aging step was left to stand for 60 minutes in a room temperature atmosphere and then dried. Table 2 shows properties of the hydrotreating catalyst A4.

  Table 2 shows the results of the stability evaluation test and the hydrotreating activity evaluation test described above for Catalyst A to Catalyst Z and Catalyst A1 to Catalyst A4.

In Examples 24-46, the result that relative desulfurization activity exceeded 110% was obtained, and the sufficient activity improvement result was obtained. On the other hand, the relative desulfurization activity of the comparative example is in the range of 100 to 105% that is practically required, and is lower than the relative desulfurization activity of the examples.
Here, the aging time and the aging pressure were constant (2 hours, 0.10 MPa (1 atm)), and stability at the time of high temperature treatment for Examples 24, 26 to 30 and Comparative Examples 9 to 11 in which the aging temperature was changed. The change in (absolute value of NO adsorption amount change rate) is shown by a circle plot in FIG. 1, and the change in desulfurization activity (relative desulfurization activity) for Examples 24, 26, 28, 30 and Comparative Example 9 is shown in FIG. Shown as a circle plot. According to these figures, it can be seen that the stability of the hydrotreating catalyst subjected to the activity improvement treatment has a downward trend line with respect to the aging temperature, and the desulfurization activity has a upward trend line. . And in the range of aging temperature of 100-140 degreeC, relative desulfurization activity exceeds 120%, NO adsorption amount change rate is also less than 10%, and it can be said that the highly active and stable activity improvement result was obtained.

On the other hand, in Example 26 (aging temperature 80 ° C.), when the aging time was 2 hours, a relative desulfurization activity exceeding 120% was not obtained, but in Example 31 (aging temperature 80 ° C.), the aging time was reduced. By extending to 8 hours, a relative desulfurization activity of 120% is obtained, and the stability during high temperature treatment is also improved. Even when the aging temperature is 90 ° C., it is considered that the same result can be obtained by extending the aging time. For example, if a relative desulfurization activity of 110% or more is obtained within 10 hours of aging time, it can be evaluated that the activity improving treatment having good stability is performed in a sufficiently short time.
Further, in Comparative Example 14, the liquid content of the gluconic acid aqueous solution measured after aging was less than 50% by mass (44% by mass), the rate of change in the NO adsorption amount greatly exceeded 10%, and the relative desulfurization activity was also high. It is as low as 102%.

Next, the aging temperature and the aging time were constant (110 ° C., 2 hours), and the conditions under the assumption of sulfidation treatment and catalytic reaction during use of Examples 24, 33 to 39 in which the pressure during aging was changed 3 shows the quantitative change (the absolute value of the NO adsorption amount change rate) of the catalyst in FIG. 3 as a circle plot, and the desulfurization activity (relative desulfurization activity) for Examples 24, 33, 34, and 37-39. ) Is shown as a circle plot in FIG. According to these, the amount of active sites adsorbed NO of the hydrotreating catalyst that has been subjected to the activity improving treatment draws a downward trend line with respect to the pressure at the time of aging, and the desulfurization activity tends to protrude upward. You can see that it draws a line. And when the pressure at the time of aging is in the range of 0.10 to 0.42 MPa (1 to 4.2 atm), the relative desulfurization activity exceeds 110%, the NO adsorption amount change rate is also less than 10%, and high activity. It can be said that a stable activity improvement result was obtained.
Finally, in Examples 41 to 43 in which a cobalt raw material was added as an active metal component and Examples 44 to 46 in which a nickel raw material was added, 0.5 to 1.0% by mass in terms of oxide in any active metal component When the active metal component in the range was added, the NO adsorption amount change rate was less than 10%. In Examples 41 and 45, the relative desulfurization activity exceeds 120%. On the other hand, when the addition amount of the active metal component was 1.5% by mass, the NO adsorption amount change rate exceeded 10%, and the relative desulfurization activity was less than 120%.
Further, in Example 25 prepared so that the liquid content after aging was 50% by mass, the NO adsorption amount change rate (absolute value) was less than 10%, and the relative desulfurization activity was 123%. As a result, it was confirmed that when the liquid content after aging was 50% by mass or more, a regeneration result satisfying the target values of the NO adsorption amount change rate (absolute value) and the relative desulfurization activity was obtained.

Claims (8)

A first step of obtaining an active metal carrier by supporting at least one active metal component selected from Group 6, Group 8 to Group 10 of the periodic table on the carrier;
A second step of impregnating the active metal carrier with a chelating agent-containing aqueous solution containing a chelating agent and moisture to obtain an impregnated carrier;
The impregnated carrier is aged at 80 ° C. or higher and 150 ° C. or lower while maintaining the liquid content of the chelating agent-containing aqueous solution calculated by the following formula (1) at 50% or higher. 3 steps,
And a fourth step of drying the aging support at 300 ° C. or lower to obtain a hydrotreating catalyst, and a method for producing a hydrotreating catalyst.
Liquid content [% by mass] = {(W2−W1) / W1} × 100 (1)
However, W1 is the mass after drying the aged carrier after completion of the third step at 500 ° C., and W2 is the mass of the aged carrier at the end of the third step.   The method for producing a hydroprocessing catalyst according to claim 1, wherein the third step is performed in a range of 0.10 to 0.51 MPa.   Instead of the first step, in the second step, at least one active metal component selected from Groups 6 and 8 to 10 of the periodic table is added to the chelating agent-containing aqueous solution. The method for producing a hydrotreating catalyst according to claim 1 or 2. A method for producing a hydrotreating catalyst, wherein the active metal component supported on the hydrotreating catalyst before use is redispersed to improve the activity,
A first step of impregnating a hydrotreatment catalyst before use with a chelating agent-containing aqueous solution containing a chelating agent and moisture to obtain an impregnated catalyst;
Second step of obtaining an aged catalyst by aging the impregnated catalyst at 80 ° C. or higher and 150 ° C. or lower while maintaining the liquid content of the chelating agent-containing aqueous solution calculated by the following formula (2) at 50% or higher. When,
And a third step of drying the aged catalyst at 300 ° C. or lower to obtain an improved catalyst, and a method for producing a hydrotreating catalyst.
Liquid content [% by mass] = {(W4−W3) / W3} × 100 (2)
However, W3 is a mass after drying the aged catalyst after completion | finish of a 2nd process at 500 degreeC, and W4 is a mass of the aged catalyst at the end of a 2nd process.   The method for producing a hydrotreating catalyst according to claim 4, wherein the second step is performed in a range of 0.10 to 0.51 MPa.   The said 1st process WHEREIN: At least 1 or more active metal component chosen from the periodic table 6th group and 8th group-10th group is added to the said chelating agent containing aqueous solution. The manufacturing method of the hydrotreating catalyst as described in 1 above.   The hydrometallurgy treatment according to claim 6, wherein the active metal component is selected from Groups 8 to 10 of the periodic table, and its addition amount is 1% by mass or less of the improved catalyst in terms of oxide. A method for producing a catalyst.   In the said 1st process, the calcination catalyst which baked the hydroprocessing catalyst before use in advance at the temperature exceeding 300 degreeC is used, The manufacture of the hydroprocessing catalyst in any one of Claims 4-7 characterized by the above-mentioned. Method.

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