JP4493997B2 - Hydrodesulfurization catalyst for hydrocarbon oil and method for producing the same - Google Patents

Description

  The present invention relates to a vacuum gas oil fraction (hereinafter referred to as VGO) by an indirect desulfurization apparatus, an atmospheric residual oil fraction (hereinafter referred to as AR) or a vacuum residual oil fraction (hereinafter referred to as VR) by a direct desulfurization apparatus. The present invention relates to a hydrodesulfurization catalyst for hydrocarbon oil that can be used for hydrodesulfurization of hydrocarbons and can remove sulfur compounds in the heavy oil fraction with high efficiency over a long period of time, and a method for producing the hydrodesulfurization catalyst. .

A large amount of sulfur compounds are contained in heavy oils such as AR obtained by treating crude oil with an atmospheric distillation apparatus and VGO, VR obtained by further treating AR with a vacuum distillation apparatus.
When these heavy oils are used as fuel without being desulfurized, a large amount of sulfur oxide (SOx) is discharged into the atmosphere, which causes environmental destruction.

  Therefore, conventionally, hydrodesulfurization treatment of heavy oil fractions by indirect desulfurization equipment and direct desulfurization equipment has been incorporated as one of the processes for producing various petroleum products from crude oil, and sulfur compounds can be removed. Hydrodesulfurization catalysts aimed at removing sulfur compounds from heavy oils have molybdenum, tungsten, group 8 cobalt, and nickel as active manifestation components in the periodic table, group 6, and alumina, magnesia. Those supported on an inorganic oxide carrier such as silica and titania have been developed.

  However, in heavy oil, there are macromolecules containing asphaltenes that impede hydrodesulfurization reactions or organometallic compounds that reduce catalytic activity (such as nickel and vanadium). It is difficult to maintain vitality for a long time.

  For this reason, in order to hydrotreat heavy oil with high efficiency, research on the high desulfurization performance and long life of hydrodesulfurization catalysts has been actively conducted. In order to suppress catalyst deterioration (metal deterioration) from nickel and vanadium for the purpose of extending the life of the catalyst, it can be generally achieved by increasing the pore volume and pore diameter of the catalyst. However, when the pore volume and pore diameter are increased, the surface area is reduced, and as a result, the desulfurization performance is lowered.

On the other hand, some proposals have been made on methods for improving the hydrodesulfurization performance of a catalyst. For example, in Patent Document 1 (Japanese Patent Laid-Open No. 58-146445) and the like, zeolite is added to an alumina support to improve hydrodesulfurization performance. However, the addition of zeolite tends to increase the production of coke, which is another degradation factor, due to its acid nature. Non-Patent Document 1 (Journal of cata1ysis 128, 559-568 (1991)) reports that desulfurization performance is improved when P is supported. However, when P is supported, the pore volume of the catalyst is reduced, which tends to cause rapid metal deterioration.
JP 58-146445 A Journal of cata1ysis 128, 559-568 (1991)

  An object of the present invention is to provide a catalyst so that sulfur compounds in heavy oil fractions can be removed with high efficiency over a long period in hydrodesulfurization treatment such as VGO by indirect desulfurization equipment and AR by direct desulfurization equipment. An object of the present invention is to provide a hydrodesulfurization catalyst for hydrocarbon oil that is less deteriorated and excellent in hydrodesulfurization performance, and further to provide a method for producing the hydrodesulfurization catalyst.

According to the present invention, a manufacturing method and a catalyst for catalytic following configuration is provided, the problems are solved.
1. P atom content is expressed in terms of oxide based on the support, and P atom-containing alumina having a content of 0.1 to 8% by mass is used as the support .
8-25% by mass of at least one metal selected from Group 6 of the Periodic Table, expressed in terms of oxide based on the catalyst, and at least one metal selected from Group 8 of the Periodic Table 1 to 8% by mass of each catalyst is expressed in terms of oxide based on the catalyst, and the P atom-containing alumina carrier is supported on the P-atom-containing alumina carrier, and the specific surface area is 180 to 330 m ² / g. The total pore volume is 0.4 to 0.7 m1 / g, the average pore diameter is 7 to 14 nm, and the pore diameter is in the range of average pore diameter ± 1.5 nm. a method of manufacturing a hydrodesulfurization catalyst that accounts for 50-90% of the coal hydrocarbon oil,
A P-atom-containing alumina carrier is prepared by a kneading method in which an aqueous solution of a P-atom compound is added and kneaded in an alumina gel,
The P atom-containing alumina carrier is impregnated with a solution containing a compound containing at least one selected from Group 8 metals of the periodic table and a compound containing at least one selected from Group 6 metals of the periodic table And then calcining at 600 to 700 ° C. in an air atmosphere for 1 to 10 hours, to produce a hydrocarbon oil hydrodesulfurization catalyst .
2. 2. The hydrocarbon according to 1 above, wherein the metal of Group 6 of the periodic table is at least one of molybdenum and tungsten, and the metal of Group 8 of the periodic table is at least one of cobalt and nickel A method for producing a hydrodesulfurization catalyst for oil .
3. A hydrodesulfurization catalyst for hydrocarbon oils produced by the method according to 1 or 2 above.

  In the hydrodesulfurization treatment of various heavy oil fractions, by using the hydrodesulfurization catalyst of the hydrocarbon oil of the present invention that has little catalyst deterioration and high hydrodesulfurization performance, Sulfur compounds can be removed with high efficiency over a long period of time.

Hereinafter, the hydrodesulfurization catalyst for hydrocarbon oil of the present invention (hereinafter also simply referred to as “hydrodesulfurization catalyst” or “catalyst”) and the production method thereof will be described in detail. First, the manufacturing method will be described.
The catalyst of the present invention uses an alumina support containing a specific amount of P atoms as a support. This P-atom-containing alumina carrier can be prepared by a kneading method, a coprecipitation method, or the like, and is not particularly limited. However, the P-atom-containing alumina support depends on the kneading method in that a catalyst with little catalyst deterioration and high hydrodesulfurization performance can be obtained. Is preferred. That is, it is preferable to prepare a P atom-containing alumina support by adding an aqueous solution of a P atom compound to an alumina gel and kneading at the time of producing a P atom-containing alumina support. Excellent results are obtained.
Furthermore, the catalyst of the present invention includes a compound containing at least one selected from Group 8 metals of the Periodic Table and a compound containing at least one selected from Group 6 metals of the Periodic Table on the P atom-containing alumina support. It is prepared by impregnating and supporting a solution containing After impregnation, it is preferably fired at 400 to 700 ° C. in an air atmosphere for 1 to 10 hours.

The P atom content in the P atom-containing alumina carrier is 0.1 to 8% by mass, preferably 1 to 5% by mass in the P atom-containing alumina carrier, expressed in terms of oxide based on the carrier. . When the P atom content is in the above range, a catalyst capable of removing sulfur compounds in heavy oil with high efficiency over a long period of time can be obtained.
Here, with respect to the content of P atoms, “display in terms of oxide based on the support” means that the mass of all metal species contained in the support is calculated as the oxide of each metal, and is based on the total mass It means the proportion of the oxide mass of P. Aluminum was determined as a trivalent metal and phosphorus as a pentavalent metal.
Various compounds can be used as a raw material for P atoms of the P atom-containing alumina support used in the catalyst of the present invention. Specific examples include orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, and tetraphosphoric acid, but orthophosphoric acid is preferred.

  In order to obtain a P atom-containing alumina support, first, an alumina gel is produced. The manufacturing method of an alumina gel is not specifically limited, A normal method can be employ | adopted. That is, by neutralizing a water-soluble aluminum compound such as aluminum sulfate, nitrate or chloride with a base such as ammonia, or neutralizing an alkali metal aluminate with an acidic aluminum salt or acid, etc. An alumina gel is obtained.

  A normal alumina carrier can be produced by a general process such as aging, washing, dehydration drying, molding, drying, and firing of alumina gel. The P-atom-containing alumina carrier used in the catalyst of the present invention is preferably produced by adding a kneading step for adding and kneading an aqueous solution of a P-atom compound to alumina gel before the molding step.

  In order to obtain a carrier having structural properties suitable as a catalyst carrier, the pH when making an alumina gel by adding a precipitating agent or a neutralizing agent, the concentration, time, temperature, etc. of these agents may be adjusted as appropriate. For example, the specific surface area increases if the pH during gel formation is on the acidic side. In the present invention, it is preferable that the pH is about 4 to 8 and the temperature is about 15 to 90 ° C.

After the gel is formed, it is aged, washed away with impurities, and dehydrated. The aging is carried out at pH 4 to 9 and about 15 to 90 ° C. for about 1 to 25 hours from the viewpoint of easy removal of impurities from the aging alumina gel and maintaining the surface area of the alumina gel at an appropriate size. It is preferable.
The dehydration drying is performed by adjusting the water content without applying heat to the alumina gel. For example, it is dehydrated and dried by a method such as natural filtration at about 15 to 90 ° C. and about 0.01 to 2 MPa, suction filtration, pressure filtration, etc., and the water content after dehydration drying is about 60 to 90% by mass. It is preferable to do so. By adjusting the water content without applying extra heat to the alumina gel, the surface structure of the support can be controlled and the hydrodesulfurization activity of the catalyst can be improved.

  The carrier is formed after dehydration and drying. The molding method is not particularly limited, and a general method such as extrusion molding, tableting molding, or granulation in oil can be used. The pore volume and pore distribution, which are structural physical properties of the carrier, can also be controlled by adjusting the pressure and speed during molding.

  The shape of the carrier is preferably a cylindrical, trilobal, quadrilobal, dumbbell, or ring-shaped pellet in consideration of the distribution of the heavy oil fraction catalyst layer. A shape with a small pressure loss (pressure difference) is selected. Similarly, the pellet diameter is desirably in the range of 1/10 to 1/36 inch so that the pressure loss does not increase before and after the catalyst layer under the reaction conditions. In addition, a pellet diameter is represented by the long diameter of the cross section of the thickest part except what the shape of a pellet is a cylinder.

  After forming, the P-atom-containing alumina carrier used in the present invention can be obtained by drying at room temperature to about 150 ° C. for about 3 to 24 hours and subsequently firing at about 300 to 800 ° C. for about 3 to 24 hours.

  The catalyst of the present invention carries at least one metal selected from Group 6 and at least one metal selected from Group 8.

As the Group 6 metal described above, chromium, molybdenum, or tungsten is used, but molybdenum or tungsten is preferable. These Group 6 metals can be used in combination of two or more. Various compounds of these Group 6 metals can be used.
Specific examples of the molybdenum compound include molybdenum oxide, ammonium molybdate, molybdenum condensed acid salt, etc., but molybdenum oxide, ammonium molybdenate, and molybdophosphoric acid are preferable.
Specific examples of the tungsten compound include tungsten oxide, ammonium tungstate, and tungsten condensed acid salt. Tungsten oxide, ammonium tungstate, and tungstophosphoric acid are preferable.
These compounds can be used alone or in combination of two or more. Of course, a molybdenum compound and a tungsten compound can be used in combination.

The group 8 metal is preferably nickel or cobalt. Moreover, nickel and cobalt can also be used together. Various compounds of these Group 8 metals can be used.
Specific examples of the nickel compound include nickel nitrate, nickel sulfate, nickel carbonate, nickel acetate, nickel oxalate, nickel chloride and the like, and nickel nitrate, nickel carbonate, and nickel acetate are preferable.
Specific examples of the cobalt compound include cobalt nitrate, cobalt sulfate, cobalt carbonate, cobalt acetate, cobalt oxalate, and cobalt chloride, with cobalt nitrate, cobalt carbonate, and cobalt acetate being preferred.
These compounds can be used alone or in combination of two or more. Of course, a nickel compound and a cobalt compound can be used in combination.

  In addition to the Group 6 metal and Group 8 metal described above, P atoms may be further added to improve the dispersibility of the active metal. Various compounds can be used as the P atom compound. Specific examples include orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, and tetraphosphoric acid, but orthophosphoric acid is preferred.

  Similarly, in addition to the Group 6 metal and Group 8 metal described above, an organic acid may be added in order to improve the water solubility of the active metal. Various organic acids can be used. Specific examples include acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, tricarballylic acid, glycolic acid , Lactic acid, gluconic acid, pyruvic acid, citric acid monohydrate, anhydrous citric acid, isocitric acid, alloisocitric acid, malic acid, tartaric acid, etc., but anhydrous citric acid, isocitric acid, citric acid monohydrate preferable.

  The amount of the Group 6 metal supported is 8 to 25% by mass, preferably 10 to 22% by mass, and particularly preferably 10 to 20% by mass in terms of oxide based on the catalyst. The amount of the Group 8 metal supported is 1 to 8% by mass, preferably 2 to 5% by mass, expressed in terms of oxide based on the catalyst.

  Here, with respect to the amount of metal supported, “display in terms of oxide based on the catalyst” means that the mass of all metal species contained in the catalyst is calculated as the oxide of each metal, It means the ratio of metal oxide mass. Aluminum was determined as a trivalent metal, a Group 6 metal as a hexavalent metal, and a Group 8 metal as a divalent metal.

  The metal mass was measured by dissolving the catalyst in a mixed acid and then analyzing by ICP spectroscopy (inductively coupled high-frequency plasma spectroscopy).

In the catalyst of the present invention, various preparation methods such as an impregnation method, a coprecipitation method, a kneading method, a deposition method, and an ion exchange method can be adopted as a method for supporting the Group 6 metal and Group 8 metal.
Particularly preferred is a method of supporting by an impregnation method, but when a plurality of active metals are supported, they may be impregnated simultaneously or individually. When impregnating individually, the order of impregnation is not particularly limited, but it is preferable to support the Group 8 metal after supporting the Group 6 metal.

  After supporting the metal, drying and firing are performed. The conditions for the drying method are not particularly limited, and for example, the usual conditions employed in these methods are employed, such as ordinary air drying, hot air drying, and heat drying. After drying, firing is performed using an electric furnace, a muffle furnace, or the like under an air flow. The firing temperature is preferably 400 to 700 ° C, more preferably 500 to 700 ° C, and particularly preferably 600 to 700 ° C.

Next, the physical properties of the surface of the catalyst of the present invention will be described.
180-330 m < ² > / g is preferable and, as for the specific surface area measured by the nitrogen adsorption method (BET method) in the catalyst of this invention, 200-310 m < ² > / g is more preferable. When the specific surface area is in the above range, it is easy to achieve high dispersion of desulfurization active sites, and the pore diameter and pore volume are also appropriate, so that the reaction substrate (sulfur compound) has excellent diffusibility in the pores. Occurrence of metal deterioration is suppressed.

  The pore volume measured by the mercury intrusion method in the catalyst of the present invention is preferably 0.4 to 0.7 ml / g, more preferably 0.5 ml / g to 0.7 ml / g. When the pore volume is in the above range, it is easy to achieve high dispersion of desulfurization active sites, excellent diffusibility of the reaction substrate (sulfur compound) in the pores, and the occurrence of metal deterioration is suppressed.

  The average pore diameter measured by the mercury intrusion method in the catalyst of the present invention is preferably 7 to 14 nm, and more preferably 8.5 to 14 nm. When the average pore diameter is in the above range, it is easy to achieve high dispersion of the desulfurization active sites, high desulfurization performance is obtained, and the diffusibility of the reaction substrate (sulfur compound) in the pores is excellent, and metal degradation Occurrence is suppressed.

  From the viewpoint of desulfurization performance, the pore volume in the range of average pore diameter ± 1.5 nm measured by the mercury intrusion method in the catalyst of the present invention is preferably 50 to 90% of the total pore volume, 60 to 90% is more preferable.

  The specific surface area was measured by the BET method using a surface area measuring apparatus (Bell Soap 28) manufactured by Nippon Bell Co., Ltd. after vacuum degassing the catalyst at 400 ° C. for 1 hour. The pore volume and average pore diameter were as follows: the catalyst was vacuum degassed at 400 ° C. for 1 hour, then using Shimadzu Corporation (AUTOPORE-9220), contact angle: 130 °, surface tension: 470 dyne / cm The measurement was performed.

  In order to perform the catalytic hydrotreating of heavy oil using the hydrodesulfurization catalyst of the present invention, for example, the catalyst of the present invention is charged into a reactor such as an indirect desulfurization apparatus or a direct desulfurization apparatus, and the raw material is supplied to the reactor. By introducing heavy oil as oil, desulfurization treatment can be performed under conditions of high temperature and high pressure hydrogen partial pressure. A preferred embodiment is a so-called fixed bed flow reaction system. The catalyst is maintained in the reactor as a fixed bed, a preliminary sulfidation treatment is performed, and most of the supported metal components are converted to sulfides, and then the feedstock is passed downward from above the fixed bed. The catalyst may be charged in a single reactor or in each of a plurality of reactors connected in series. In particular, when the feedstock is AR or VR, the feedstock contains a high concentration of metal such as nickel and vanadium, so a catalyst layer having a demetallizing function is combined in the previous stage (upper layer) of the desulfurization catalyst layer. It is particularly preferred to use a multistage reactor

As described above, when performing heavy oil hydrotreating, the catalyst of the present invention has less catalyst deterioration and better desulfurization performance than conventional catalysts. Can be produced.
The catalyst of the present invention can be used as a hydrotreating catalyst for other hydrocarbon oils in addition to the VGO fraction, the AR fraction and the VR fraction.

  EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[Preparation of catalyst]
Reference example 1
An orthophosphoric acid aqueous solution was added to the alumina gel to prepare a P atom-containing alumina support A having properties of P ₂ O ₅ content (support conversion): 3.6% by mass and surface area: 273 m ² / g.
On the other hand, 8.76 g of ammonium molybdate and 9.27 g of nickel nitrate were added to 40 g of ion-exchanged water, and citric acid was added until further dissolved to prepare a metal aqueous solution. All of this aqueous solution was dropped onto 50 g of P-atom-containing alumina carrier A, allowed to stand at room temperature for 1 hour, air-dried, and then fired at 500 ° C. in an air stream using a muffle furnace to obtain catalyst e . It was.

Reference Example 2
Ammonium molybdate 8.76 g and nickel nitrate 9.27 g were added to 40 g of ion-exchanged water, and citric acid was added until further dissolved to prepare an aqueous metal solution. All of this aqueous solution was dropped onto 50 g of the P-atom-containing alumina carrier A used in Reference Example 1, and then allowed to stand at room temperature for 1 hour, air-dried, and then fired at 450 ° C. in an air stream using a muffle furnace. And catalyst f was obtained.

Example 3
Ammonium molybdate 8.76 g and nickel nitrate 9.27 g were added to 40 g of ion-exchanged water, and citric acid was added until further dissolved to prepare an aqueous metal solution. All of this aqueous solution was added dropwise to 50 g of the P-atom-containing alumina support A used in Reference Example 1, and then allowed to stand at room temperature for 1 hour, air-dried, and then fired at 650 ° C. in an air stream using a muffle furnace. And catalyst C was obtained.

Example 4
A P-atom-containing alumina carrier B having the same properties as the P-atom-containing alumina carrier A, except that an orthophosphoric acid aqueous solution was added to the alumina gel to make the P ₂ O ₅ content (support equivalent): 1.2% by mass. Prepared. On the other hand, 8.76 g of ammonium molybdate and 9.27 g of nickel nitrate were added to 40 g of ion-exchanged water, and citric acid was added until further dissolved to prepare a metal aqueous solution. All of this aqueous solution was dropped onto 50 g of P-atom-containing alumina carrier B, allowed to stand at room temperature for 1 hour, air-dried, and then calcined at 650 ° C. in an air stream using a muffle furnace to obtain catalyst D. It was.

Example 5
A P-atom-containing alumina carrier C having the same properties as the P-atom-containing alumina carrier A except that an aqueous orthophosphoric acid solution was added to the alumina gel to make the P ₂ O ₅ content (support equivalent): 2.4% by mass. Prepared. On the other hand, 8.76 g of ammonium molybdate and 9.27 g of nickel nitrate were added to 40 g of ion-exchanged water, and citric acid was added until further dissolved to prepare a metal aqueous solution. All of this aqueous solution was dropped onto 50 g of P-atom-containing alumina support C, allowed to stand at room temperature for 1 hour, air-dried, and calcined at 650 ° C. in an air stream using a muffle furnace to obtain catalyst E. It was.

Example 6
An orthophosphoric acid aqueous solution was added to the alumina gel to prepare a P atom-containing alumina support D having properties of P ₂ O ₅ content (support conversion): 3.6% by mass and surface area: 350 m 2 / g. On the other hand, 8.76 g of ammonium molybdate and 9.27 g of nickel nitrate were added to 40 g of ion-exchanged water, and citric acid was added until further dissolved to prepare a metal aqueous solution. All of this aqueous solution was dropped onto 50 g of P-containing alumina carrier D, allowed to stand at room temperature for 1 hour, air-dried, and then calcined at 650 ° C. in an air stream using a muffle furnace to obtain catalyst F. .

Example 7
An orthophosphoric acid aqueous solution was added to the alumina gel to prepare a P atom-containing alumina support E having properties of P ₂ O ₅ content (support conversion): 3.6% by mass and surface area: 254 m ² / g. On the other hand, 8.76 g of ammonium molybdate and 9.27 g of nickel nitrate were added to 40 g of ion-exchanged water, and citric acid was added until further dissolved to prepare a metal aqueous solution. All of this aqueous solution was dropped onto 50 g of P-atom-containing alumina carrier E, allowed to stand at room temperature for 1 hour, air-dried, and then calcined at 650 ° C. in an air stream using a muffle furnace to obtain catalyst G. It was.

Comparative Example 1
P-free alumina support a having the same physical properties as P-atom-containing alumina support A was prepared. On the other hand, 8.76 g of ammonium molybdate and 9.27 g of nickel nitrate were added to 40 g of ion-exchanged water, and citric acid was added until further dissolved to prepare a metal aqueous solution. All of this aqueous solution was dropped onto 50 g of alumina carrier a, allowed to stand at room temperature for 1 hour, air-dried, and calcined at 500 ° C. in an air stream using a muffle furnace to obtain catalyst a.

Comparative Example 2
To 40 g of ion-exchanged water, 9.09 g of ammonium molybdate, 9.61 g of nickel nitrate and 3.01 g of orthophosphoric acid were added to prepare an aqueous metal solution. All of this aqueous solution was added dropwise to 50 g of the alumina carrier a used in Comparative Example 1, and then allowed to stand at room temperature for 1 hour, air-dried, and then calcined at 500 ° C. in an air stream using a muffle furnace. b was obtained.

Comparative Example 3
Ammonium molybdate 8.76 g and nickel nitrate 9.27 g were added to 40 g of ion-exchanged water, and citric acid was added until further dissolved to prepare an aqueous metal solution. All of this aqueous solution was added dropwise to 50 g of the P-atom-containing alumina carrier A used in Reference Example 1, and then allowed to stand at room temperature for 1 hour, air-dried, and then fired at 750 ° C. in an air stream using a muffle furnace. And catalyst c was obtained.

Comparative Example 4
An orthophosphoric acid aqueous solution was added to the alumina gel to prepare a P atom-containing alumina support c having properties of P ₂ O ₅ content (support conversion): 3.6% by mass and surface area: 232 m ² / g. On the other hand, 8.76 g of ammonium molybdate and 9.27 g of nickel nitrate were added to 40 g of ion-exchanged water, and citric acid was added until further dissolved to prepare a metal aqueous solution. All of this aqueous solution was dropped onto 50 g of P-atom-containing alumina support c, and then allowed to stand at room temperature for 1 hour, air-dried, and calcined at 650 ° C. in an air stream using a muffle furnace to obtain catalyst d. It was.

[Catalyst properties]
Table 1 shows the chemical properties, P addition method and calcination temperature of the catalysts obtained in Reference Examples 1 and 2, Examples 3 to 7 and Comparative Examples 1 to 4, and Table 2 shows the physical properties.

[Evaluation of hydrodesulfurization performance by AR]
Each catalyst ( C to G and a to f ) was packed in a fixed bed flow type apparatus. The preliminary sulfidation was performed by VGO at LHSV = 1.0 / h, hydrogen partial pressure = 10 MPa, and 370 ° C. for 12 hours. Thereafter, the desulfurization performance was continuously passed through AR (containing 3.51% by mass of sulfur, 23 ppm of nickel and 36 ppm of vanadium), reaction temperature = 380 ° C., hydrogen partial pressure = 10 MPa, LHSV = 0.4 / h, The reaction was carried out under the condition of hydrogen / oil ratio = 1000 m ³ / m ³ , the sulfur concentration contained in the product oil 100 days after the initial deterioration was settled, and the reaction rate constant was calculated by the following formula [Formula 1]. Asked.
The analysis of the sulfur concentration of the raw material oil and the product oil was obtained with an X-ray sulfur analyzer (RX-610SA) manufactured by Newly Corporation. In addition, it shows that the hydrodesulfurization activity of a catalyst is excellent, so that reaction rate constant is high.
The evaluation results of the catalysts C to G and a to f are shown in Table 3 as relative values when the reaction rate constant in the catalyst a is 100.
[Formula 1]
Reaction rate constant = [(1 / sulfur concentration of product oil) − (1 / sulfur concentration of feedstock oil)] × liquid space velocity

The catalyst of Reference Example 1 in which P atoms were added by the kneading method had hydrodesulfurization performance compared to the catalyst of Comparative Example 1 in which P was not added and the catalyst of Comparative Example 2 in which P atoms were added by the impregnation method. high.

The catalyst of Example 3 is higher in hydrodesulfurization performance than the catalyst of Comparative Example 1, but among them, the catalyst of Example 3 that is calcined at 650 ° C. after metal loading is the highest.
The catalysts of Examples 3 to 5 have higher hydrodesulfurization performance than the catalyst of Comparative Example 1, and among them, the catalysts of Examples 3 and 5 are particularly high.
The catalyst of Example 6 and the catalyst of Example 7 in which P atoms were added by the kneading method and the physical properties of the catalyst were changed have higher hydrodesulfurization performance than the catalyst of Comparative Example 1.
The catalyst of Comparative Example 3 having a high calcination temperature after supporting the metal also has a small specific surface area of the catalyst and extremely low hydrodesulfurization performance.
The catalyst of Comparative Example 4 having a small pore distribution index has significantly lower hydrodesulfurization performance than the catalyst of Reference Example 1, and is lower than that of the catalyst of Comparative Example 1.

[Evaluation of hydrodesulfurization performance by VGO]
The hydrodesulfurization performance of the catalysts obtained in Reference Example 1 , Example 3, Comparative Example 1, and Comparative Example 2 was evaluated using VGO as the feedstock. First, preliminary sulfidation treatment was performed with light gas oil. Then, VGO (sulfur: 2.81 mass%, density: 0.9411 g / cm ³ @ 15 ° C.) was continuously passed through, reaction temperature = 360 ° C., hydrogen partial pressure = 4.9 MPa, LHSV = 0. The reaction was conducted under the conditions of 7 / h, hydrogen / oil ratio = 420 m ³ / m ³ , and the sulfur concentration contained in the product oil 500 hours after the initial deterioration settled was measured. A constant was obtained. The evaluation results are shown in Table 4 as relative values when the hydrodesulfurization activity of the catalyst of Comparative Example 1 is defined as 100.
[Formula 2]
Reaction rate constant = [(1 / sulfur concentration of product oil ^1/2 )-(1 / sulfur concentration of feedstock ^1/2 )] × liquid space velocity

  From Table 4, it can be seen that also in the hydrodesulfurization reaction of VGO, the catalyst of the present invention has high hydrodesulfurization performance, and in particular, the catalyst of Example 3 is extremely high.

Claims (3)

P atom content is expressed in terms of oxide based on the support, and P atom-containing alumina having a content of 0.1 to 8% by mass is used as the support .
8-25% by mass of at least one metal selected from Group 6 of the Periodic Table, expressed in terms of oxide based on the catalyst, and at least one metal selected from Group 8 of the Periodic Table 1 to 8% by mass of each catalyst is expressed in terms of oxide based on the catalyst, and the P atom-containing alumina carrier is supported on the P-atom-containing alumina carrier, and the specific surface area is 180 to 330 m ² / g. The total pore volume is 0.4 to 0.7 m1 / g, the average pore diameter is 7 to 14 nm, and the pore diameter is in the range of average pore diameter ± 1.5 nm. a method of manufacturing a hydrodesulfurization catalyst that accounts for 50-90% of the coal hydrocarbon oil,
A P-atom-containing alumina carrier is prepared by a kneading method in which an aqueous solution of a P-atom compound is added and kneaded in an alumina gel,
The P atom-containing alumina carrier is impregnated with a solution containing a compound containing at least one selected from Group 8 metals of the periodic table and a compound containing at least one selected from Group 6 metals of the periodic table And then calcining at 600 to 700 ° C. in an air atmosphere for 1 to 10 hours, to produce a hydrocarbon oil hydrodesulfurization catalyst .   The carbonization according to claim 1, wherein the metal of Group 6 of the periodic table is at least one of molybdenum and tungsten, and the metal of Group 8 of the periodic table is at least one of cobalt and nickel. A method for producing a hydrodesulfurization catalyst for hydrogen oil. A hydrodesulfurization catalyst for hydrocarbon oil produced by the method according to claim 1.