JP2017113715A - Hydrogen treatment catalyst and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hydrogen treatment catalyst or the like excellent in demetalizing performance and de-asphaltene performance.SOLUTION: A hydrogenation treatment catalyst uses an alumina-phosphorous carrier, has specific surface area of 100 m/g or more, whole pore volume of 0.80 to 1.50 ml/g, maximum value of pore distribution in a range of pore diameter of 10 to 30 nm, percentage of pore volume in a range of pore diameter ±2 nm at the maximum value to pore volume in a range of pore diameter 5 to 100 nm of 0.40 or less, pressure resistance strength of 10 N/mm or more, contains phosphorous of 0.4 to 10.0 mass% in terms of POconcentration, in which hydrogenation active metal is a metal selected from group 6A metal and group 8 metal in the periodic table, content of sulfur in terms of SOconcentration of 1.0 mass% or less and ratio of absorbance of spectrum peak corresponding to a basic OH group to absorbance of spectrum peak corresponding to an acidic OH group measured by FT-IR is in a range of 0.15 to 0.50.SELECTED DRAWING: Figure 1

Description

The present invention relates to the technical field of a hydrotreating catalyst for removing sulfur content in hydrocarbon oil in the presence of hydrogen.
The present invention relates to a hydrotreating catalyst and a method for producing the same, and more particularly, to a hydrotreating catalyst used for hydrotreating heavy hydrocarbon oil such as residual oil containing metal contaminants such as vanadium and nickel and the like. It relates to a manufacturing method.

In the pretreatment process of heavy hydrocarbon oil, deasphalten performance is required in addition to high demetallization performance and desulfurization performance. Asphaltenes are abundant in heavy oil and have a large molecular weight and a large amount of metal. Therefore, it is necessary to perform hydrogenation when highly demetallizing. In addition, if the asphaltene in the raw material oil cannot be sufficiently hydrotreated in the heavy hydrocarbon oil hydrotreating process, a base material containing a large amount of dry sludge in the produced oil is obtained. Since a base material containing a large amount of dry sludge has low storage stability and causes various troubles, it is important to highly hydrotreat asphaltenes in the feedstock.
In order to hydrotreat asphaltenes having a large molecular weight, catalysts having large pores and bimodal catalysts having two pore distribution peaks have been developed so far. In recent years, further improvement in performance has been demanded in order to cope with further heaviness of raw material oil and to reduce the burden of R-FCC (Residual-Fluid Catalytic Cracking) treatment after the hydrotreating process.

  For example, Patent Document 1 discloses a catalyst having high demetalization performance and desulfurization performance by using a bimodal type catalyst having mesopores in the range of 7 to 20 nm and macropores in the range of 300 to 800 nm.

JP 2006-181562 A

  In the technique described in Patent Document 1, a catalyst having high demetalization performance and desulfurization performance can be developed by using a bimodal type hydrotreating catalyst, but the deasphaltenization performance is not sufficient. The hydrotreating catalyst has mesopores in the range of 7 to 20 nm and macropores in the range of 300 to 800 nm. In general, the deasphalten performance is not significantly improved unless the catalyst pores exceed 20 nm. Therefore, even if macropores are present, mesopores, which are the main reaction pores, were not effective for the deasphaltenic reaction.

  In the technique described in Patent Document 1, a catalyst having macropores is obtained by adding an easily decomposable substance to a kneaded product during the preparation of a carrier, and baking and removing it. However, in this preparation method, a large amount of easily decomposable substances are used, and it is necessary to remove the easily decomposable substances by firing.

  An object of the present invention is to provide a hydrotreating catalyst having excellent demetalization performance and deasphaltening performance, and a simple and highly productive method for producing the catalyst.

A first invention is a hydroprocessing catalyst in which a hydrogenation active metal is supported on an alumina-phosphorus carrier,
(1) The specific surface area is 100 m ² / g or more,
(2) The total pore volume measured by the mercury intrusion method is 0.80 to 1.50 ml / g,
(3) having a maximum value of pore distribution in a pore diameter range of 10 to 30 nm,
(4) The ratio (ΔPV / PVme) of the pore volume (ΔPV) in the range of ± 2 nm of the pore diameter at the maximum value to the pore volume (PVme) in the range of the pore diameter of 5 to 100 nm is 0.40. And
(5) The pressure strength is 10 N / mm or more,
(6) phosphorus containing 0.4 to 10.0 wt% as _P 2 _{O 5} concentration equivalent amount in the catalyst total amount
(7) The hydrogenation active metal is a metal selected from Group 6A metal and Group 8 metal of the Periodic Table,
(8) The sulfur content is 1.0% by mass or less in terms of SO ₄ concentration in terms of the total amount of the catalyst,
(9) The alumina-phosphorus carrier is a basic OH group with respect to absorbance Sa of a spectral peak in the wave number range of 3673 to 3678 cm ⁻¹ corresponding to an acidic OH group measured by a transmission Fourier transform infrared spectrophotometer. The ratio Sb / Sa of absorbance Sb of spectral peaks in the wave number range of 3770 to 3774 cm ⁻¹ corresponding to is in the range of 0.15 to 0.50.

The first invention may have the following features.
(I) The group 6A metal of the periodic table is at least one metal of chromium, molybdenum, and tungsten, and the group 8 metal of the periodic table is at least one metal of iron, nickel, and cobalt. Be.
(Ii) The phosphorus content in the alumina-phosphorus carrier is 0.5 to 7.0% by mass in terms of P ₂ O ₅ concentration in terms of the total amount of carrier.
(Iii) The hydrogenation active metal is contained in an amount of 1 to 30% by mass as an oxide concentration conversion amount based on the total amount of the catalyst.
(Iv) Do not have the maximum value of the pore distribution in the range of the pore diameter of 100 to 1000 nm.
(V) Or having a second maximum value of pore distribution in a pore diameter range of 100 to 1000 nm. At this time, the ratio (PVma / PVme) of the pore volume (PVma) in the range of pore diameters of 100 to 1000 nm and the pore volume (PVme) in the range of pore diameters of 5 to 100 nm is 0.1-0. Be in the range of 5.
The second invention is a heavy hydrocarbon oil hydrotreating method using the hydrotreating catalyst described above.

A third invention is a method for producing a hydrotreating catalyst in which a hydrogenation active metal is supported on an alumina-phosphorus carrier,
(1) While stirring an acidic aluminum salt aqueous solution whose pH is adjusted to 2.0 to 5.0, a basic aluminum salt aqueous solution is added so that the pH becomes 7.5 to 10.0 to hydrate alumina. A first step of obtaining an object,
(2) a second step of obtaining alumina-phosphorous hydrate by adding phosphorus to the alumina hydrate washed and removed with 20 to 50 times the amount of pure water with respect to the alumina solid mass of the alumina hydrate; ,
(3) a third step of sequentially aging, kneading, molding, drying, and firing the alumina-phosphorous hydrate to obtain an alumina-phosphorus carrier;
(4) a fourth step of supporting a metal selected from the group 6A metal and the group 8 metal on the carrier on the periodic table;
It is a manufacturing method of the hydrotreating catalyst characterized by having.

The third aspect of the invention may include the following features.
(I) In the second step, phosphorus is added to the alumina hydrate so as to be 3.0 to 7.0% by mass as a P ₂ O ₅ concentration conversion amount based on the total amount of the carrier.
(Ii) In the second step, phosphorus is added to the alumina hydrate so as to be 0.5 to 2.5% by mass as a P ₂ O ₅ concentration conversion amount based on the total amount of the carrier.
(Iii) The temperature of the pure water used for washing in the second step is in the range of 50 to 70 ° C.
(Iv) In the third step, the aging of the alumina-phosphorus hydrate is performed in a pH range of 7.0 to 9.0.

According to the hydrotreating catalyst of the present invention, excellent properties in demetalization performance and deasphaltenation performance are exhibited. Therefore, it is particularly effective as a hydroprocessing catalyst for heavy hydrocarbon oils.
Moreover, the method for producing the hydrotreating catalyst of the present invention is simple, has high productivity, and is advantageous in terms of production cost.

It is a transmission type Fourier-transform infrared spectrophotometer measurement result of support | carrier a, d, and f. 2 is an integral type and differential type pore distribution map of the hydrotreating catalyst A. FIG. 3 is an integral type and differential type pore distribution map of the hydrotreating catalyst B. FIG.

The present invention is a hydrocarbon oil hydrotreating catalyst (hereinafter referred to as “the present catalyst”) using an alumina-phosphorus support, and the embodiment of the present catalyst and the production method thereof will be described in detail below.
<Contains phosphorus and SO ₄ >
The catalyst contains phosphorus in an amount of 0.4 to 10.0% by mass in terms of P ₂ O ₅ concentration in terms of the total amount of catalyst. If the phosphorus content is less than 0.4% by mass, the catalyst strength (abrasion resistance) decreases, which is not preferable. If the phosphorus content exceeds 10.0% by mass, the specific surface area of the catalyst decreases, which is not preferable. Phosphorus is preferably contained in the catalyst in an amount of 0.5 to 10.0% by mass, more preferably 1.0 to 8.0% by mass, and further preferably 2.0 to 7.0% by mass. preferable.

However, it is preferable that phosphorus is contained in the alumina-phosphorus carrier constituting this catalyst in an amount of 0.5 to 7.0% by mass in terms of P ₂ O ₅ concentration based on the total amount of the carrier, and 1.0 to 6.0%. More preferably, it is contained in an amount of 1.5% to 5.5% by mass.
If the phosphorus content in the carrier is less than 0.5% by mass, the catalyst strength may decrease. Moreover, it may be difficult to have a wide pore distribution in the pore diameter range of 5 to 100 nm, which is the object of the present invention. On the other hand, if the phosphorus content in the support exceeds 7.0% by mass, the pore volume in the range of pore diameters of 100 to 1000 nm becomes too large, and the catalyst strength may decrease. Furthermore, there is a possibility that the catalyst bulk density is lowered and the catalyst performance is also lowered.
Note that the phosphorus content on the basis of the total amount of catalyst in the hydrotreating catalyst may increase with respect to the phosphorus content on the basis of the total amount of carrier in the alumina-phosphorus carrier. The reason for this is that an impregnation solution of hydrogenation active metal is prepared using a solution containing phosphoric acid in the step of supporting the hydrogenation active metal on the alumina-phosphorus carrier (fourth step described later), and hydrogen is obtained by the impregnation method. An example in which the content of phosphorus increases when the activated metal is supported.

Further, the amount of residual SO ₄ in the carrier is preferably 1% by mass or less, and more preferably 0.5% by mass or less. If the amount of residual SO ₄ exceeds 1% by mass, the catalyst strength may decrease.

<Supporting of hydrogenation active metal>
In the catalyst of the present invention, a metal selected from Group 6A metal and Group 8 metal of the periodic table is supported on a support as a hydrogenation active metal. The supported amount of the hydrogenation active metal is preferably in the range of 1 to 30% by mass in terms of oxide concentration based on the total amount of the catalyst. When the supported amount of the hydrogenation active metal is 1% by mass or more, the effect of the present invention can be further exhibited. In addition, it is preferable that the amount of the hydrogenation active metal supported is 30% by mass or less because demetalization (demetal selectivity) and catalyst activity stability can be maintained, and production costs can be further reduced. As the Group 6A metal, chromium, molybdenum and tungsten are preferable, and as the Group 8 metal, iron, nickel and cobalt are preferable.
For the Group 6A metals in the periodic table, the supported amount is preferably in the range of 1 to 20% by mass, more preferably in the range of 3 to 15% by mass as the oxide concentration conversion amount. Regarding the Group 8 metal of the periodic table, the supported amount preferable as the oxide concentration conversion amount is in the range of 0.1 to 10% by mass, more preferably in the range of 0.3 to 5% by mass.

<Specific surface area>
The specific surface area of the catalyst is 100 m ² / g or more. When the specific surface area is less than 100 m ² / g, the effect on the demetalization performance is small, but the desulfurization reaction rate tends to decrease greatly. The specific surface area is desirably in the range of 150 to 250 m ² / g. Even when the specific surface area exceeds 250 m ² / g, the effect of the present invention is not so much improved, but rather the demetallation (demetallation selectivity) tends to be lowered, and the stability of the catalytic activity may be lowered. There is. The specific surface area in the present invention is a value measured by the BET (Brunauer-Emmett-Teller) method.

<Pore volume>
The total pore volume of the catalyst is in the range of 0.80 to 1.50 ml / g. When the total pore volume is less than 0.80 ml / g, the demetallization life tends to be shortened, and when it is greater than 1.50 ml / g, the catalyst strength decreases. The total pore volume is preferably in the range of 0.85 to 1.40 ml / g, and more preferably in the range of 0.90 to 1.30 ml / g. The total pore volume in the present invention means a pore volume having a pore diameter in the range of 3 to 10,000 nm.
The pore diameter, pore volume and pore distribution in the present invention are measured by mercury porosimetry, and the pore diameter is a value calculated using a mercury surface tension of 480 dyne / cm and a contact angle of 150 °. It is.

<Pore volume distribution>
The pore distribution of the present catalyst has a maximum value in the range of the pore diameter of 10 to 30 nm. If the maximum value is in the range of pore diameter less than 10 nm, the demetalization performance is significantly reduced. On the other hand, if the maximum value is in the range exceeding pore diameter of 30 nm, the desulfurization performance tends to decrease, which is not preferable. . The range of the preferable pore diameter in which this maximum value exists is 12 to 25 nm, and more preferably 15 to 20 nm.

  In the pore distribution of this catalyst, the ratio of the pore volume (ΔPV) in the range of ± 2 nm of the pore diameter at the maximum value to the pore volume (PVme) in the range of pore diameter of 5 to 100 nm (ΔPV) / PVme) is 0.40 or less. If ΔPV / PVme exceeds 0.40, the reactivity with the asphaltene molecule is lowered, and the demetalization performance and the deasphalten performance are lowered, which is not preferable.

Here, by controlling the amount of phosphorus added to the phosphorus-alumina support, a catalyst having a second maximum value in the pore distribution in the pore diameter range of 100 to 1000 nm can be obtained. A phosphorus-alumina carrier obtained by adding a phosphorus source corresponding to the content of 3.0 to 7.0% by mass of phosphorus as a P ₂ O ₅ concentration conversion amount based on the total amount of the carrier to the raw material, The pore size distribution in the diameter range has a second maximum value. When the pore distribution has the second maximum value, the deasphaltening and demetallizing performance can be enhanced. On the other hand, when the phosphorus content is in the range of 0.5 to 2.5% by mass, the second maximum value is hardly formed.
Further, in the catalyst having the second maximum value, the pore volume (PVma) in the pore diameter range of 100 to 1000 nm including the second maximum value and the maximum value of the pore distribution in the range of 10 to 30 nm are obtained. When the ratio (PVma / PVme) to the pore volume (PVme) in the range of 5 to 100 nm including the pore diameter is in the range of 0.1 to 0.5, the above-described effects can be further exhibited. However, if PVma / PVme exceeds 0.5, the catalyst strength may decrease.
In addition to these, by combining a catalyst having the second maximum value in the pore distribution and a catalyst not having the second maximum value (for example, mixing two kinds of catalysts), deasphaltening and demetalization performance And a catalyst system having both desulfurization selectivity.

<Abrasion strength>
The wear strength of the catalyst of the present invention is 0.5% or less. When the wear strength of the catalyst exceeds 0.5%, cracking and powdering are likely to occur even during regeneration of the catalyst after use. The wear strength is a value measured by ASTM (American Society for Testing and Materials) D4058-81.

<Pressure strength>
The pressure resistance of the catalyst is 10 N / mm or more. If the pressure strength is less than 10 N / mm, the catalyst is easily broken when it is filled with the catalyst, which may cause drift or pressure loss during the reaction. For this reason, the pressure strength must be 10 N / mm or more. The pressure strength is also referred to as crush strength, and the pressure strength in the present invention is a value measured with a Kiyama-type hardness meter.

<Acid OH group and basic OH group contained in carrier>
The support of the catalyst of the present invention corresponds to a basic OH group with respect to absorbance Sa of a spectral peak in a wave number range of 3673 to 3678 cm ⁻¹ corresponding to an acidic OH group measured by a transmission type Fourier transform infrared spectrophotometer. The ratio Sb / Sa of the absorbance Sb of the spectral peak in the wave number range of 3770 to 3774 cm ⁻¹ is in the range of 0.15 to 0.50. More preferably, it is in the range of 0.40 to 0.50. The active metal is known to have different dispersibility depending on the characteristics of the surface of the alumina support. By optimizing the ratio of the acidic OH group and the basic OH group in this way with respect to the OH groups on the surface of the support, In combination with the support being an alumina-phosphorus support, high dispersibility is obtained for the hydrogenated active metal and high desulfurization performance is obtained. FIG. 1 shows a support of the catalyst of the present invention (supports a, d, and f shown in Examples) having a wave number range of 3673 to 3678 cm ⁻¹ corresponding to acidic OH groups and 3770 to 3774 cm ⁻ corresponding to basic OH groups. An example of a light absorption spectrum including a wave number range of ¹ will be shown.

Next, a preferred embodiment for producing the catalyst of the present invention will be described.
<Method for producing alumina-phosphorus carrier>
(First step)
An acidic aluminum salt was added to the floor water, and the aqueous solution of the aluminum aluminum salt prepared to have an Al ₂ O ₃ content of, for example, 0.1 to 2.0 mass% and pH 2.0 to 5.0 was stirred while the temperature of the solution was increased. Is heated to, for example, 50 to 80 ° C. The acidic aluminum salt may be a water-soluble salt, and examples thereof include aluminum sulfate, aluminum chloride, aluminum acetate, aluminum nitrate, etc., and 0.5 to 20% by mass in terms of Al ₂ O ₃ , preferably 2 It is desirable to use an aqueous solution containing 10 mass%.
Next, while stirring this acidic aluminum salt aqueous solution, an aqueous solution of a basic aluminum salt is added, for example, for 30 to 200 minutes, preferably 60 to 180 minutes, so that the pH becomes 7 to 10, thereby obtaining an alumina hydrate. Examples of the basic aluminum salt include sodium aluminate and potassium aluminate, and it is desirable to use an aqueous solution containing 2 to 30% by mass, preferably 10 to 25% by mass in terms of Al ₂ O ₃ .

(Second step)
Next, the obtained alumina hydrate is washed with pure water at 50 to 70 ° C., preferably 55 to 65 ° C. to remove impurities (by-product salts) such as sodium and sulfate radicals, thereby obtaining a washed cake. The alumina hydrate is preferably washed with 20 to 50 times the amount of pure water relative to the solid mass of the alumina to remove by-product salts. Further, pure water is added to the washing cake to prepare an Al ₂ O ₃ concentration of 5 to 18% by mass, preferably 7 to 15% by mass, and then phosphorus is added to the alumina hydrate to obtain alumina. -Get phosphorus hydrate. Phosphorus is preferably added so that the carrier contains 0.5 to 7.0% by mass as P ₂ O ₅ concentration, more preferably 1.0 to 6.0% by mass, and more preferably 1.5 to 5%. More preferably, the content is 5% by mass. As the phosphorus source, phosphoric acid compounds such as phosphoric acid, phosphorous acid, ammonia phosphate, potassium phosphate, and sodium phosphate can be used.

(Third step)
Alumina-phosphorus hydrate obtained in the second step is aged in an aging tank with a reflux at 30 ° C. or higher, preferably 80-100 ° C., for example, for 1-10 hours, preferably 2-5 hours. . The pH during aging is preferably within the range of 7.0 to 9.0. Next, the obtained aged product is kneaded by heating, for example, into a kneaded product that can be molded, then molded into a desired shape by extrusion molding or the like, dried, and 0.5 to 400-800 ° C. Calcination for 10 hours to obtain an alumina-phosphorus carrier.

(4th process)
By using the alumina-phosphorus support obtained in the third step, a metal selected from each of Group 6A metal and Group 8 metal of the periodic table is supported by conventional means. A hydrotreating catalyst can be produced. As such a metal raw material, for example, a metal compound such as nickel nitrate, nickel carbonate, cobalt nitrate, cobalt carbonate, molybdenum trioxide, ammonium molybdate, and ammonium paratungstate is used. It is carried on a carrier by a known method. The carrier after supporting the metal is usually calcined at 400 to 600 ° C. for 0.5 to 5 hours to be a hydroprocessing catalyst of the present invention.

Here, as described above, in the second step in the method for producing an alumina-phosphorus carrier, phosphorus is added to the carrier so that the concentration of P ₂ O ₅ is 3.0 to 7.0% by mass based on the total amount of the carrier. Thus, a catalyst having a second maximum value in the pore distribution in the pore diameter range of 100 to 1000 nm can be obtained. This catalyst can enhance the deasphaltene and demetallization performance.
On the other hand, in the second step in the method for producing an alumina-phosphorus carrier, by adding phosphorus to the carrier so that the P ₂ O ₅ concentration is 0.5 to 2.5% by mass based on the total amount of the carrier, the pore diameter A catalyst having no second maximum value in the pore distribution in the range of 100 to 1000 nm can be obtained. This catalyst is excellent in desulfurization selectivity.
In addition, the above-mentioned parameters (specific surface area, maximum volume in front, maximum value of pore distribution with pore diameter of 10 to 30 nm, value of ΔPV / PVme, pressure strength) in the present catalyst basically depend on the amount of phosphorus added. Although it can be controlled, details will be described in the embodiment.

The hydrotreating catalyst of the present invention is used for hydrotreating heavy hydrocarbon oils such as residual oil containing metal contaminants such as vanadium and nickel, and adopts existing hydrotreating equipment and operating conditions thereof. Can do. When the example of the said operating conditions is given, the hydrogenation process of the said heavy hydrocarbon oil will be carried out in the presence of hydrogen under conditions of a temperature of 350 to 450 ° C., a pressure of 3 to 20 MPa, and a liquid space velocity of 0.1 to 3 hr ^−1. This is a treatment for contacting with a catalyst.
In addition, since the production of the catalyst of the present invention is simple, for example, by adding an easily decomposable substance in the mixture of alumina hydrate to form a bimodal type pore size distribution, productivity is improved. This is also advantageous in terms of manufacturing cost.

[Measurement method]
As will be described later, for the hydrotreating catalyst in each of the examples and comparative examples of the present invention, numerical values relating to the content, specific surface area, and properties of the components are measured, but a method for performing these measurements is described. deep.
<Measurement method of content of carrier component (alumina, silica, phosphorus oxide, titania) and metal component (molybdenum, cobalt, nickel, copper, magnesium, phosphorus)>
3 g of a measurement sample was collected in a zirconia ball with a lid having a capacity of 30 ml, heated (200 ° C., 20 minutes), fired (700 ° C., 5 minutes), then added with ₂ g of Na ₂ O ₂ and 1 g of NaOH for 15 minutes. Melted. Further, 25 ml of H ₂ SO ₄ and 200 ml of water were added and dissolved, and then diluted to 500 ml with pure water to prepare a sample. About the obtained sample, ICP (Inductively Coupled Plasma) emission analyzer (Shimadzu Corporation make, ICPS-8100, analysis software ICPS-8000) was used, and the content of each component was converted into an oxide conversion standard (Al ₂ (O ₃ , SiO ₂ , P ₂ O ₅ , TiO ₂ , MoO ₃ , NiO, CoO, MgO, CuO).

<Method for measuring specific surface area>
About 30 ml of a measurement sample was collected in a magnetic crucible (B-2 type), heated at 300 ° C. for 2 hours, then placed in a desiccator and cooled to room temperature to obtain a measurement sample. Next, 1 g of this sample was taken, and the specific surface area (m ² / g) of the sample was measured by the BET method using a fully automatic surface area measuring device (manufactured by Yuasa Ionics Co., Ltd., Multisorb 12 type).
<Measurement method of crushing strength>
For the crushing strength, as a pretreatment, 40 samples or more of a length of 4 mm or more from a sample fired at 500 ° C. for 1 hour and cooled with a desiccator to a kiyama type hardness meter (compressor 3.18 mm). The load when crushed and crushed was obtained and calculated by the following formula.
Crushing strength (N / mm) = S × 9.807 / L × n
Here, S is the total pressure load (kg), L is the diameter of the compressor (3.18 mm), and n is the number of measurements.

  EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited thereto.

[Example 1]
Pour 35.2 kg of pure water into a tank equipped with a circulation line with two chemical addition ports, add 13.0 kg of an aqueous aluminum sulfate solution (concentration 7% by mass as Al ₂ O ₃ ) with stirring, and heat to 70 ° C. It was circulated warm. The pH of the aqueous alumina solution at this time was 2.3. Next, 9.5 kg of a sodium aluminate aqueous solution (concentration of 22% by mass as Al ₂ O ₃ ) was added in 180 minutes while maintaining the temperature at 70 ° C. while stirring and circulating to obtain alumina hydrate. The pH after the addition was 9.5. Next, the obtained alumina hydrate (nitrate radical (by-product salt) content: about 7 g in 100 g of alumina solid content) was added to 100 L of pure water at 60 ° C. (33 times the alumina solid mass in the alumina hydrate). ) To remove impurities such as sodium to obtain a washed cake. After adding pure water to the washing cake and preparing so that the Al ₂ O ₃ concentration becomes 8% by mass, 256 g of phosphoric acid (a concentration of 62% by mass as P ₂ O ₅ ) is added to the alumina hydrate, Aging was carried out at 95 ° C. for 3 hours in an aging tank equipped with a refluxer to obtain alumina-phosphorus hydrate. The pH during aging was 7.4. The slurry after completion of aging was dehydrated and concentrated and kneaded to a predetermined moisture content while kneading with a double-arm kneader equipped with a steam jacket. The obtained kneaded product was extruded and formed into a 1.7 mm four-leaf type column by an extruder. The obtained alumina molded article was dried at 110 ° C. for 12 hours and then calcined at 680 ° C. for 3 hours to obtain an alumina-phosphorus carrier a. As for support a, phosphorus is 5% by mass in terms of P ₂ O ₅ concentration, aluminum is 94.8% by mass in terms of Al ₂ O ₃ concentration, and sulfate is 0.2% by mass in terms of SO ₄ (both based on the total amount of support) ) Contained. FIG. 1 shows the results of measurement of the transmission type Fourier transform infrared spectrophotometer (manufactured by JASCO Corporation, FT-IR-6100) of the carrier a. The absorbance Sa of the spectral peak in the wave number range of 3673 to 3678 cm ⁻¹ corresponding to the acidic OH group in the carrier a is 0.061, and the absorbance of the spectral peak in the wave number range of 3770 to 3774 cm ⁻¹ corresponding to the basic OH group. Sb was 0.294, and the ratio Sb / Sa was 0.21.

After 26.6 g of molybdenum oxide and 9.7 g of nickel carbonate were suspended in 400 ml of ion-exchanged water, this suspension was subjected to appropriate refluxing so as not to reduce the liquid volume, and then heated at 95 ° C. for 5 hours. Then, 13.3 g of malic acid was added and dissolved to prepare an impregnation solution. This impregnating solution is spray impregnated into 500 g of carrier a, dried at 250 ° C., and further calcined in an electric furnace at 550 ° C. for 1 hour to be hydrotreated catalyst A (hereinafter also simply referred to as “catalyst A”). The same applies to the following examples). The metal component of the catalyst A was 5% by mass (based on the total amount of catalyst) of MoO _{3 and} 1% by mass (based on the total amount of catalyst) of NiO. Properties of catalyst A are shown in Table 1. Catalyst A contained 4.8% by mass of phosphorus in terms of P ₂ O ₅ concentration and 0.2% by mass of sulfate groups in terms of SO ₄ (both based on the total amount of catalyst). FIG. 2 shows integral (solid line) and differential (broken line) pore distribution diagrams of the hydrotreating catalyst A, respectively. In addition, the compressive strength was measured based on the Kiya-type hardness meter (made by Fujiwara Seisakusho).

[Example 2]
In Example 1, an alumina-phosphorus carrier b was obtained in the same manner as in Example 1 except that 99.4 g of phosphoric acid to be added was added. The pH during aging was 8.5. As for the carrier b, phosphorus is ₂ % by mass in terms of P ₂ O ₅ concentration, aluminum is 97.8% by mass in terms of Al ₂ O ₃ concentration, and sulfate is 0.2% by mass in terms of SO ₄ (both based on the total amount of the carrier) ) Contained. The absorbance Sa of the spectrum peak corresponding to the acidic OH group in the carrier b was 0.274, the absorbance Sb of the spectrum peak corresponding to the basic OH group was 0.106, and the ratio Sb / Sa thereof was 0.38. It was. Catalyst B was obtained in the same manner as in Example 1 using carrier b. Properties of catalyst B are shown in Table 1. Catalyst B contained 1.9% by mass of phosphorus in terms of P ₂ O ₅ and 0.2% by mass of sulfate in terms of SO ₄ (both based on the total amount of catalyst). FIG. 3 shows integral distribution (solid line) and differential (broken line) pore distribution diagrams of the hydrotreating catalyst B, respectively.

[Example 3]
In Example 1, an alumina-phosphorus carrier c was obtained in the same manner as in Example 1 except that 150.7 g of phosphoric acid to be added was added. The pH during aging was 8.1. As for the support c, phosphorus is 3% by mass in terms of P ₂ O ₅ concentration, aluminum is 96.8% by mass in terms of Al ₂ O ₃ concentration, and sulfate is 0.2% by mass in terms of SO ₄ (both based on the total amount of support) ) Contained. The absorbance Sa of the spectral peak corresponding to the acidic OH group in the carrier c was 0.307, the absorbance Sb of the spectral peak corresponding to the basic OH group was 0.092, and the ratio Sb / Sa thereof was 0.30. It was. Catalyst C was obtained in the same manner as in Example 1 using carrier c. The properties of catalyst C are shown in Table 1. Catalyst C contained 2.9% by mass of phosphorus in terms of P ₂ O ₅ concentration and 0.2% by mass of sulfate groups in terms of SO ₄ (both based on the total amount of catalyst).

[Comparative Example 1]
In Example 1, the alumina support | carrier d was obtained like Example 1 except not adding phosphoric acid. The pH during aging was 9.5. The carrier d contained 0.2% by mass of sulfate radicals in terms of SO ₄ and 99.8% by mass of aluminum in terms of Al ₂ O ₃ concentration (both based on the total amount of the carrier). The absorbance Sa of the spectral peak corresponding to the acidic OH group in the carrier d is 0.171, the absorbance Sb of the spectral peak corresponding to the basic OH group is 0.090, and the ratio Sb / Sa thereof is 0.53. It was. Catalyst D was obtained in the same manner as in Example 1 using carrier d. Properties of catalyst D are shown in Table 1. Catalyst D contained phosphorus in an amount of 0% by mass in terms of P ₂ O ₅ concentration and sulfate group in an amount of 0.2% by mass in terms of SO ₄ (both based on the total amount of catalyst). Moreover, the transmission Fourier transform infrared spectrophotometer (JASCO Corporation make, FT-IR-6100) measurement result of the support | carrier d is shown in FIG.

[Comparative Example 2]
In Example 1, an alumina-phosphorous carrier e was obtained in the same manner as in Example 1 except that 9.8 g of phosphoric acid to be added was added. The pH during aging was 9.3. As for support e, phosphorus is 0.2% by mass in terms of P ₂ O ₅ concentration, aluminum is 99.6% by mass in terms of Al ₂ O ₃ concentration, and sulfate is 0.2% by mass in terms of SO ₄ (both are carriers) The total amount) was contained. The absorbance Sa of the spectral peak corresponding to the acidic OH group in the carrier e is 0.182, the absorbance Sb of the spectral peak corresponding to the basic OH group is 0.093, and the ratio Sb / Sa thereof is 0.51. It was. Catalyst E was obtained in the same manner as in Example 1 using carrier e. Properties of catalyst E are shown in Table 1. Catalyst E contained 0.2% by mass of phosphorus in terms of P ₂ O ₅ concentration and 0.2% by mass of sulfate radicals in terms of SO ₄ (both based on the total amount of catalyst).

[Comparative Example 3]
In Example 1, an alumina-phosphorus carrier f was obtained in the same manner as in Example 1 except that 481.8 g of phosphoric acid to be added was added. The pH during aging was 5.6. As for support f, phosphorus is 9% by mass in terms of P ₂ O ₅ concentration, aluminum is 90.8% by mass in terms of Al ₂ O ₃ concentration, and sulfate is 0.2% by mass in terms of SO ₄ (both based on the total amount of support) ) Contained. The absorbance Sa of the spectral peak corresponding to the acidic OH group in the carrier f is 0.471, the absorbance Sb of the spectral peak corresponding to the basic OH group is 0.062, and the ratio Sb / Sa thereof is 0.13. It was. Catalyst F was obtained in the same manner as in Example 1 using carrier f. Properties of catalyst F are shown in Table 1. Catalyst F contained 8.6% by mass of phosphorus in terms of P ₂ O ₅ concentration and 0.2% by mass of sulfate group in terms of SO ₄ (both based on the total amount of catalyst). Moreover, the transmission Fourier transform infrared spectrophotometer (JASCO Corporation make, FT-IR-6100) measurement result of the support | carrier f is shown in FIG.

[Comparative Example 4]
In Example 1, after adding the sodium aluminate aqueous solution to the aluminum sulfate aqueous solution, the pH of the obtained alumina hydrate was 8.5 L, and 60 L of pure water at 60 ° C. (the amount of solid alumina in the alumina hydrate was 50%). Alumina-phosphorus carrier g was obtained in the same manner as in Example 1 except that it was washed with 17 times the amount. The pH during aging was 6.8. As for carrier g, phosphorus is 5% by mass in terms of P ₂ O ₅ concentration, aluminum is 93.7% by mass in terms of Al ₂ O ₃ concentration, and sulfate is 1.3% by mass in terms of SO ₄ (both based on the total amount of carrier) ) Contained. The absorbance Sa of the spectral peak corresponding to the acidic OH group in the carrier g was 0.293, the absorbance Sb of the spectral peak corresponding to the basic OH group was 0.059, and the ratio Sb / Sa thereof was 0.20. It was. Catalyst G was obtained in the same manner as in Example 1 using carrier g. Properties of catalyst G are shown in Table 1. Catalyst G contained 4.8% by mass of phosphorus in terms of P ₂ O ₅ concentration and 1.2% by mass of sulfate group in terms of SO ₄ (both based on the total amount of catalyst).

[Comparative Example 5]
In Example 1, an alumina-phosphorus carrier h was obtained in the same manner as in Example 1 except that the pH after adding the sodium aluminate aqueous solution to the aluminum sulfate aqueous solution was 7.0. The pH during aging was 6.5. As for carrier h, phosphorus is 5% by mass in terms of P ₂ O ₅ concentration, aluminum is 92.4% by mass in terms of Al ₂ O ₃ concentration, and sulfate is 2.7% by mass in terms of SO ₄ (both based on the total amount of carrier) ) Contained. The absorbance Sa of the spectral peak corresponding to the acidic OH group in the carrier h was 0.291, the absorbance Sb of the spectral peak corresponding to the basic OH group was 0.057, and the ratio Sb / Sa thereof was 0.20. It was. Catalyst H was obtained in the same manner as in Example 1 using carrier h. Properties of catalyst H are shown in Table 1. Catalyst H contained 4.8% by mass of phosphorus in terms of P ₂ O ₅ and 2.5% by mass of sulfate in terms of SO ₄ (both based on the total amount of catalyst).

[Comparative Example 6]
In Example 2, an alumina-phosphorus carrier i was obtained in the same manner as in Example 2 except that 15% by mass of ammonia water was added so that the pH during aging was 10.0. As for support i, phosphorus is ₂ % by mass in terms of P ₂ O ₅ concentration, aluminum is 97.8% by mass in terms of Al ₂ O ₃ concentration, and sulfate is 0.2% by mass in terms of SO ₄ (both based on the total amount of support) ) Contained. The absorbance Sa of the spectral peak corresponding to the acidic OH group in the carrier i was 0.179, the absorbance Sb of the spectral peak corresponding to the basic OH group was 0.092, and the ratio Sb / Sa thereof was 0.51. It was. Catalyst I was obtained in the same manner as in Example 1 using carrier i. Properties of catalyst I are shown in Table 1.

[Catalyst activity evaluation test]
With respect to the catalysts A to C of Examples 1 to 3 and the catalysts D to I of Comparative Examples 1 to 6 subjected to preliminary sulfidation using hydrogen and hydrogen sulfide, hydrogen was used under the conditions shown below using a fixed bed type microreactor. The chemical demetalization activity, desulfurization activity, and deasphalten activity were investigated.
Reaction conditions;
Catalyst filling amount: 400ml
Reaction pressure: 13.5 MPa
Liquid hourly space velocity (LHSV): 1.0hr ^-l
Hydrogen / oil ratio (H ₂ / HC): 800 Nm ³ / kl
Reaction temperature: 370 ° C
Moreover, the normal pressure residual oil of the following property was used for raw material oil.
Raw oil properties;
Density (15 ° C.): 0.9761 g / cm ³
Asphaltene content: 3.4% by mass
Sulfur content: 4.143% by mass
Metal (Ni + V) content: 80.5% by mass
The hydrodemetalization activity, desulfurization activity, and deasphaltenic activity were expressed as demetallation rate, desulfurization rate, and deasphaltenation rate, and the values are shown in Table 1.
Note that the metal removal rate was determined by the following equation.
Demetalization rate = (Metal concentration in raw oil−Metal concentration in hydrotreated oil / Metal concentration in raw oil) × 100
Moreover, the desulfurization rate was calculated | required by following Formula.
Desulfurization rate = (sulfur concentration in feedstock-sulfur concentration in hydrotreated product oil / sulfur concentration in feedstock) × 100
The deasphalten rate was determined by the following formula.
Deasphaltenation rate = (Asphaltene concentration in the raw material oil−Asphaltene concentration in the hydrotreated oil / Asphaltene concentration in the raw material oil) × 100

[Evaluation results]
From the results of Table 1, since the catalysts A to C in the present invention have a predetermined configuration, the values of the demetallation rate and the deasphaltenation rate are particularly higher than those of the catalysts D to F of Comparative Examples 1 to 3, It can be seen that the desulfurization activity is also high. Further, in the catalysts A and C (Examples 1 and 3) having the second maximum value of the pore distribution in the pore diameter range of 100 to 1000 nm, the demetallation ratio and the deasphalten ratio may be very high. Recognize. However, even if the second maximum value is merely within the predetermined range, the catalyst F of Comparative Example 3 that does not satisfy the other configuration of the present invention cannot achieve the above-described effects of the present invention. Moreover, since the comparative examples 4 and 5 differ from Example 1, since a sulfate radical will remove | deviate from the range prescribed | regulated by this invention, even if phosphorus content is the same as Example 1, pore diameter is 100-1000 nm. Since the ratio of the pore volume (PVma) in the range becomes high and PVma / PVme falls outside the range of 0.1 to 0.4, the pressure resistance of the catalyst is low and it is not suitable as a commercial catalyst. Further, even when an alumina-phosphorus carrier having a phosphorus content in the range of 0.5 to 7.0% by mass and a sulfate radical of 1.0% by mass or less in terms of SO ₄ is used, in Comparative Example 6, In the aging of the alumina-phosphorous hydrate in the third step, the pH is not performed within the range of 7.0 to 9.0. As a result, with respect to the pore volume (PVme) in the pore diameter range of 5 to 100 nm, the pore volume in the range of ± 2 nm of the pore diameter at the maximum value of the pore distribution in the pore diameter range of 10 to 30 nm. Since the ratio (ΔPV / PVme) occupied by (ΔPV) becomes high, the catalytic activity and the pressure strength are low.

Claims (13)

A hydrotreating catalyst having a hydrogenation active metal supported on an alumina-phosphorus carrier,
(1) The specific surface area is 100 m ² / g or more,
(2) The total pore volume measured by the mercury intrusion method is 0.80 to 1.50 ml / g,
(3) having a maximum value of pore distribution in a pore diameter range of 10 to 30 nm,
(4) The ratio (ΔPV / PVme) of the pore volume (ΔPV) in the range of ± 2 nm of the pore diameter at the maximum value to the pore volume (PVme) in the range of the pore diameter of 5 to 100 nm is 0.40. And
(5) The pressure strength is 10 N / mm or more,
(6) phosphorus containing 0.4 to 10.0 wt% as _P 2 _{O 5} concentration equivalent amount in the catalyst total amount
(7) The hydrogenation active metal is a metal selected from Group 6A metal and Group 8 metal of the Periodic Table,
(8) The sulfur content is 1.0% by mass or less in terms of SO ₄ concentration in terms of the total amount of the catalyst,
(9) The alumina-phosphorus carrier is a basic OH group with respect to absorbance Sa of a spectral peak in the wave number range of 3673 to 3678 cm ⁻¹ corresponding to an acidic OH group measured by a transmission Fourier transform infrared spectrophotometer. A ratio Sb / Sa of absorbance Sb of spectral peaks in the wave number range of 3770 to 3774 cm ⁻¹ corresponding to is in the range of 0.15 to 0.50.   The metal of group 6A of the periodic table is at least one metal of chromium, molybdenum and tungsten, and the metal of group 8 of the periodic table is at least one metal of iron, nickel and cobalt. The hydroprocessing catalyst according to claim 1. 3. The hydrotreatment according to claim 1, wherein a phosphorus content in the alumina-phosphorus carrier is 0.5 to 7.0 mass% as a P ₂ O ₅ concentration conversion amount based on the total amount of the carrier. catalyst.   4. The hydroprocessing catalyst according to claim 1, wherein the hydrogenation active metal is contained in an amount of 1 to 30% by mass in terms of oxide concentration based on the total amount of the catalyst.   The hydrotreating catalyst according to any one of claims 1 to 4, wherein the hydrotreating catalyst does not have a maximum value of pore distribution in a pore diameter range of 100 to 1000 nm.   5. The hydrotreating catalyst according to claim 1, having a second maximum value of pore distribution in a pore diameter range of 100 to 1000 nm.   The ratio (PVma / PVme) of the pore volume (PVma) in the range of the pore diameter of 100 to 1000 nm and the pore volume (PVme) in the range of the pore diameter of 5 to 100 nm is in the range of 0.1 to 0.4. The hydrotreating catalyst according to claim 6, wherein   A method for hydrotreating heavy hydrocarbon oil, wherein the hydrotreating catalyst according to any one of claims 1 to 7 is used. A method for producing a hydrotreating catalyst in which a hydrogenation active metal is supported on an alumina-phosphorus carrier,
(1) While stirring an acidic aluminum salt aqueous solution whose pH is adjusted to 2.0 to 5.0, a basic aluminum salt aqueous solution is added so that the pH becomes 7.5 to 10.0 to hydrate alumina. A first step of obtaining an object,
(2) a second step of obtaining alumina-phosphorous hydrate by adding phosphorus to the alumina hydrate washed and removed with 20 to 50 times the amount of pure water with respect to the alumina solid mass of the alumina hydrate; ,
(3) a third step of sequentially aging, kneading, molding, drying, and firing the alumina-phosphorous hydrate to obtain an alumina-phosphorus carrier;
(4) a fourth step of supporting a metal selected from the group 6A metal and the group 8 metal on the carrier on the periodic table;
A process for producing a hydrotreating catalyst, comprising: In the second step, phosphorus is added to the alumina hydrate so as to be 3.0 to 7.0% by mass as a P ₂ O ₅ concentration conversion amount based on the total amount of the carrier. Item 10. A method for producing a hydrotreating catalyst according to Item 9. The phosphorus is added to the alumina hydrate in the second step so as to be 0.5 to 2.5 mass% as a P ₂ O ₅ concentration conversion amount based on the total amount of the carrier. 9. A method for producing a hydrotreating catalyst according to 9.   The method for producing a hydrotreating catalyst according to any one of claims 9 to 11, wherein the temperature of pure water used for washing in the second step is in the range of 50 to 70 ° C.   The hydrogen according to any one of claims 9 to 11, wherein in the third step, the aging of the alumina-phosphorous hydrate is performed in a pH range of 7.0 to 9.0. Method for producing chemical treatment catalyst.

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