JP4818163B2 - Alumina support, hydrodemetallation catalyst using the same, and production method thereof - Google Patents

Description

  The present invention relates to a catalyst for hydrotreating hydrocarbon oils, particularly heavy hydrocarbon oils, and in particular, an alumina carrier having a large pore volume and high strength, and hydrodemetallation using the same. The present invention relates to catalysts and methods for producing them.

  Conventionally, hydrodemetallation catalysts are prepared by neutralizing an aluminum salt with a neutralizing agent to prepare an alumina hydrate, washing the resulting alumina hydrate, heating and extruding to produce an alumina support. However, the alumina carrier is produced by supporting an active metal component (see, for example, Patent Documents 1 to 4). Here, as an aluminum salt used as a raw material of alumina hydrate, for example, aluminum sulfate, aluminum nitrate, aluminum chloride, aluminum acetate, basic aluminum sulfate, basic aluminum nitrate, basic aluminum chloride, basic aluminum acetate, etc. Acid aluminum salts and basic aluminum salts such as sodium aluminate and potassium aluminate. Further, as the neutralizing agent, a water-soluble substance that reacts with the above-described aluminum salt to form a precipitate of alumina hydrate (alumina hydrate) is used. For example, when acidic aluminum salts are used, basic substances such as sodium aluminate, potassium aluminate, sodium hydroxide, and ammonia are used. When basic aluminum salts are used, aluminum sulfate, nitric acid are used. Acidic substances such as aluminum, aluminum chloride, sulfuric acid, nitric acid, hydrochloric acid and acetic acid are used.

Patent Document 1 is obtained by adding an aqueous sodium aluminate solution and an aqueous aluminum sulfate solution while keeping the pH at 8 while circulating an aqueous slurry of pH 8 containing seed alumina hydrate, and mixing them. The operation of returning the obtained aqueous slurry containing alumina hydrate to the aqueous slurry is repeated to prepare alumina hydrate, and the obtained alumina hydrate is washed, heat-kneaded and extruded to produce an alumina carrier. A method is disclosed.
Patent Document 2 discloses a method for producing an alumina carrier by washing, heating and extruding an alumina hydrate produced by alternately adding an aluminum nitrate solution and a sodium aluminate solution to water. It is disclosed.
Further, Patent Documents 3 and 4 disclose a method for producing an alumina carrier by washing, heating and extruding an alumina hydrate obtained by simultaneously mixing water with sodium aluminate and aluminum sulfate. It is disclosed.

Japanese Patent No. 3755826 JP-A-8-89805 JP 2002-363576 A WO2003 / 066215

  However, a hydrodemetallation catalyst in which an active metal component is supported on an alumina support produced by a conventional method has a total pore volume of 1.2 ml / g or less (substantially less than 1.1 ml / g). Since it is small, the metal removal (demetallization) performance is low, and there is a problem that an efficient metal removal treatment cannot be performed. In addition, when the total pore volume of the conventional hydrodemetallation catalyst is larger than 1.2 ml / g, the strength (for example, pressure strength, wear strength, etc.) is lowered, which is not practical. It was.

  The present invention has been made in view of such circumstances, and an object thereof is to provide an alumina carrier having a large pore volume and high strength, a hydrodemetallation catalyst using the same, and a method for producing them. .

The alumina carrier according to the present invention that meets the above object has the following properties (a) to (f).
(A) The total pore volume (PV _T ) measured by the mercury intrusion method exceeds 1.2 ml / g and is 2.0 ml / g or less.
(B) The ratio (PV _L / PV _T ) of the pore volume (PV _L ) of pores having a pore diameter of 100 nm or more to the total pore volume (PV _T ) measured by the mercury intrusion method is 0.12 to 0. 35.
(C) A first pore group (P ₁ ) having a pore distribution peak in a pore diameter range of 5 to 100 nm and a second pore group (P ₁ ) having a pore distribution peak in a pore diameter range of 500 to 10,000 nm ₂ ) and a pore volume (PV _P1 ) occupied by pores having a pore diameter in the range of 5 to 100 nm of the _first pore group (P ₁ ). Is 0.9 ml / g or more, and the pore volume (PV _P2 ) occupied by pores having a diameter of 5 to 100 nm of the _second pore group (P ₂ ) is 0.1 ml / g or more.
(D) Specific surface area (SA) is 150 m ² / g or more.
(E) The pressure strength (Crushing Strength, CS) is 7 N / mm or more.
(F) The abrasion strength (Abrasion Rate, AR) is 0.5% or less.
The hydrodemetallation catalyst according to the present invention that meets the above-mentioned object has an active metal component supported on the alumina support of the present invention. In addition, even if an active metal component is supported on the alumina carrier of the present invention, the physical properties (a) to (f) of the alumina carrier are not substantially changed.
In the hydrodemetallation catalyst according to the present invention, the active metal component is at least one metal selected from Group 6A metals and Group 8 metals of the periodic table.

Here, the total pore volume (PV _T ) of the alumina support in the present invention is a pore having a pore diameter measurable by a mercury intrusion method (substantially all pores, for example, a pore diameter of about 3 Is a total value of pore volumes in the range of 10000 nm. Further, the measurement result of the pore volume by the mercury intrusion method shows the relationship between the pore diameter of the alumina support (hereinafter also referred to simply as “pore diameter”) and the differential pore volume. The differential type pore distribution diagram (pore distribution), the integral type pore distribution diagram representing the relationship between the pore diameter of the alumina support and the cumulative pore volume, and the like are obtained. The alumina carrier of the present invention has a first pore group having a pore distribution peak (first peak) in a pore diameter range of 5 to 100 nm and a pore diameter of 500 to 10,000 nm in a differential pore distribution diagram. And a second pore group having a pore distribution peak (second peak) in the range (see FIG. 1). The alumina support of the present invention preferably has a bimodal pore structure having only the first pore group and the second pore group. In addition, in the pore diameter range of 5 to 100 nm and the pore diameter range of 500 to 10000 nm, it is preferable that each peak is one by one, but when there are two or more peaks within the range of each pore diameter, The largest in each pore diameter range is referred to as a first peak and a second peak, respectively. In addition to the first peak and the second peak, the differential pore distribution map may have a pore distribution peak outside the range of the pore diameter described above.

In the method for producing an alumina carrier according to the present invention that meets the above object, an aqueous solution of basic aluminum chloride is added to an aqueous solution of basic aluminum chloride within 5 minutes while stirring the aqueous solution adjusted to pH 10 to 14. A first step of adding to be 0,
While maintaining the mixed solution obtained in the first step within the range of pH 6.5 to 10.0, an aqueous solution of sodium aluminate and an aqueous solution of basic aluminum chloride are further added to the mixed solution over 10 minutes to 2 hours. A second step of simultaneously adding with stirring to obtain alumina hydrate;
A third step of sequentially obtaining the alumina hydrate by washing, aging, spray drying, kneading, molding, drying, and firing the alumina hydrate.
Here, the groundwater is an aqueous solution initially stored in the container.
The method for producing a hydrodemetallation catalyst according to the present invention in accordance with the above object comprises at least one selected from Group 6A metals and Group 8 metals in the periodic table in the alumina carrier produced by the method for producing an alumina carrier of the invention. Supports one or more active metal components.

The hydrodemetallation catalyst according to one embodiment of the present invention is obtained by supporting an active metal component on the alumina support of the present invention. The active metal component is at least one metal selected from Group 6A metals (eg, molybdenum, tungsten, etc.) and Group 8 metals (eg, nickel, cobalt, palladium, platinum, etc.) of the periodic table. Preferably, these two or more types are used in combination. More preferably, the hydrodemetallation catalyst may also include both the Group 6A metal and Group 8 metal of the periodic table as active metal components. In addition, the supported amount of each active metal component is preferably in the range of 0.5 to 20% by mass as an oxide with respect to the hydrodemetallation catalyst (hereinafter also referred to as “catalyst standard”), and 1 to 15% by mass. % Range is more preferred.
Here, in the present invention, the Group 6A metal and Group 8 metal of the periodic table are, for example, “Periodic Table of Periodic Period of Elements” published in the reversion of “Iwanami Riken Dictionary 4th Edition” (Iwanami Shoten, published in 1987) "Group" refers to Group 6A metal and Group 8 metal, respectively, and corresponds to Groups 6 and 8 to 10 of the 18-general long-periodic periodic table (IUPAC, 1990 recommendation). .

  The alumina carrier of the present invention has the following properties (a) to (f). Each will be described in detail below.

(A) The total pore volume (PV _T ) measured by the mercury intrusion method exceeds 1.2 ml / g and is 2.0 ml / g or less.
When the total pore volume (PV _T ) of the alumina support is 1.2 ml / g or less, the life of the metallization activity of the resulting hydrodemetallation catalyst tends to be short, and exceeds 2.0 ml / g. And the strength of the resulting hydrodemetallation catalyst is weakened. The total pore volume (PV _T ) is preferably 1.3 to 1.6 ml / g. As described above, the total pore volume (PV _T ) in the present invention is a total value of pore volumes having pore diameters that can be measured by a mercury intrusion method. In the present invention, the pore diameter, the pore volume, and the pore distribution are also measured by mercury porosimetry, and the pore diameter uses a mercury surface tension of 480 dyne / cm and a contact angle of 150 °. This is the calculated value.

(B) The ratio (PV _L / PV _T ) of the pore volume (PV _L ) of pores having a pore diameter of 100 nm or more to the total pore volume (PV _T ) measured by the mercury intrusion method is 0.12 to 0. A point that is 35.
When the pore volume ratio (PV _L / PV _T ) of the alumina support is less than 0.12, the ratio of pores having a pore diameter of 100 nm or more is small, so that the fineness of the hydrodemetallation catalyst obtained is small. In the pores, the diffusion of oil deteriorates and the demetalization activity decreases, and when it exceeds 0.35, the strength of the hydrodemetallation catalyst obtained is weak because the proportion of pores having a pore diameter of 100 nm or more is large. Become. The pore volume ratio (PV _L / PV _T ) is preferably 0.15 to 0.30.

(C-1) A first pore group (P ₁ ) having a pore distribution peak in a pore diameter range of 5 to 100 nm and a second pore group having a pore distribution peak in a pore diameter range of 500 to 10,000 nm (P ₂₎ and a point having pores of at least two pore groups.
The alumina support of the present invention has a pore distribution peak in the pore diameter range of 5 to 100 nm, preferably in the range of 5 to 50 nm in the differential pore distribution obtained by the mercury intrusion method, and is a hydrotreating catalyst. Has a _first pore group (P ₁ ) in which a desulfurization reaction mainly occurs and a pore distribution peak in a pore diameter range of 500 to 10000 nm, preferably in a range of 500 to 5000 nm. And a second pore group (P ₂ ) in which. Therefore, the hydrodemetallation catalyst produced from the alumina support of the present invention has high demetallation activity and high desulfurization activity. Here, the hydrodemetallation catalyst has a desulfurization activity because if the peak of the pore distribution in the _first pore group (P ₁ ) of the alumina support to be used is less than 5 nm in pore diameter, the diffusion of the reaction oil becomes worse. If the peak of the pore distribution exceeds the pore diameter of 100 nm, the demetallation reaction occurs and the metal is deposited in the pores, so that the desulfurization activity tends to decrease. Further, in the hydrodemetallation catalyst, when the peak of the pore distribution in the _second pore group (P ₂ ) of the alumina support to be used is less than 500 nm in pore diameter, decomposition of asphaltene having a large molecular weight does not occur sufficiently. Therefore, the metal removal activity tends to decrease, and when the pore distribution peak exceeds the pore diameter of 10,000 nm, the strength becomes weak. Furthermore, the alumina support of the present invention preferably has a bimodal pore structure having only the first pore group and the second pore group.

(C-2) The pore volume (PV _P1 ) occupied by pores in the pore diameter range of 5 to 100 nm of the _first pore group (P ₁ ) is 0.9 ml / g or more, preferably 1.0 ml / g or more. (The upper limit is substantially about 1.6 ml / g), and the pore volume (PV _P2 ) occupied by pores in the pore diameter range of 5 to 100 nm of the _second pore group (P ₂ ) is The point is 0.1 ml / g or more, preferably 0.15 ml / g or more (the upper limit is substantially about 0.6 ml / g).
When the pore volume (PV _P1 ) occupied by pores having a pore diameter in the range of 5 to 100 nm of the _first pore group (P ₁ ) of the alumina support is less than 0.9 ml / g, the resulting hydrodemetallation The catalyst tends to decrease the desulfurization activity as the metal is deposited in the pores and closes the pores, shortens the life, and the pores of the _second pore group (P ₂ ) of the alumina support. When the pore volume (PV _P2 ) occupied by pores having a diameter in the range of 5 to 100 nm is less than 0.1 ml / g, the resulting hydrodemetallation catalyst sufficiently causes diffusion and decomposition of asphaltenes having a large molecular weight. Since it is difficult, the metal removal activity tends to decrease.

(D) The specific surface area (SA) is 150 m ² / g or more.
When the specific surface area (SA) of the alumina support is less than 150 m ² / g, the resulting hydrodemetallation catalyst has a small effect on the demetallation activity, but has a large effect on the desulfurization activity and has a high desulfurization activity. When it exceeds 220 m ² / g, the number of the first pore groups increases, so that the resulting hydrodemetallation catalyst tends to have a shorter life and a lower demetalization activity. . The specific surface area (SA) is preferably 170 to 220 m ² / g. The specific surface area is a value measured by the BET method.

(E) The pressure strength (CS) is 7 N / mm or more.
When the compressive strength (CS) of the alumina support is less than 7 N / mm, the resulting hydrodemetallation catalyst is easily broken during filling, resulting in drift and pressure loss during the reaction. The pressure strength (CS) is preferably 10 N / mm or more. The upper limit value of the substantial compressive strength (CS) is 60 N / mm. The pressure strength is also called crushing strength, and is a value measured with a Kiya-type hardness meter in the present embodiment.

(F) Abrasion strength (AR) is 0.5% or less.
When the wear strength (AR) of the alumina support exceeds 0.5%, the resulting hydrodemetallation catalyst is likely to be pulverized during filling, resulting in drift and pressure loss during the reaction (during use). The wear strength (AR) is preferably 0.3% or less, and more preferably 0.1% or less. The lower limit value of the substantial wear strength (AR) is 0.01%. The wear strength is also referred to as the wear strength powdering rate, and is a value measured in accordance with ASTM method (American Testing Association method) D4058-81 in this embodiment.

Next, an alumina carrier and a method for producing a hydrodemetallation catalyst using the same will be described.
The alumina carrier of the present invention is, for example, an aqueous solution (basic acid chloride) of basic aluminum chloride represented by the following formula (1) while stirring the groundwater adjusted to pH 10-14 initially stored in the container. Are added so that the pH becomes 6.5 to 10.0 within 5 minutes, and further to the mixed solution obtained, an aqueous solution of sodium aluminate, potassium aluminate or the like and an aqueous solution of basic aluminum chloride In the range of pH 6.5 to 10.0, while stirring simultaneously for 10 minutes to 2 hours, the alumina hydrate obtained is washed, matured, spray dried, kneaded, It can be produced by molding, drying and firing.
[Al ₂ (OH) _n Cl _6-n ] _m (1)
(However, 0 <n <6, 1 ≦ m ≦ 10, preferably 4.8 ≦ n ≦ 5.3, 3 ≦ m ≦ 7, where m represents a natural number.)
The hydrodemetallation catalyst of the present invention can be produced by supporting at least one active metal component selected from Group 6A metal and Group 8 metal of the periodic table on the above-described alumina support. . Hereinafter, each step will be described in detail.

(First step)
First, an aqueous solution containing 0.05 to 0.15 mass% sodium aluminate and 0.001 to 0.003 mass% sodium gluconate as Al ₂ O ₃ was adjusted to pH 10 to 14, and The liquid temperature is heated to 50 to 70 ° C., preferably 55 to 65 ° C., and the groundwater is prepared. Here, sodium gluconate has an effect of suppressing hydrolysis of sodium aluminate, and is added to improve the stability of sodium aluminate .
The groundwater may be a basic aqueous solution (alkaline aqueous solution) having a pH of 10 to 14, and may be an aqueous solution containing sodium hydroxide, potassium hydroxide, ammonia or the like. In order to facilitate the formation of pseudo-boehmite seeds in the addition of an aqueous solution of basic aluminum chloride to the aqueous solution, sodium aluminate serving as the alumina source is added to the groundwater, and the pH of the groundwater is 10. to to 14.

Next, while stirring the groundwater, an aqueous solution of basic aluminum chloride (for example, containing 22 to 24% by mass as Al ₂ O ₃ ) is within 5 minutes, preferably about pH 6.5 to 10 in about 1 to 3 minutes. 0.0, preferably pH 7.0-9.0, to neutralize the groundwater. Thereby, pseudo boehmite seeds are formed in the mixed solution. In addition, when adding an aqueous solution of basic aluminum chloride, if the groundwater is higher than pH 10.0 for more than 5 minutes, a bayerite crystal form of alumina hydrate is produced. This is not preferable because the strength is lowered.

(Second step)
In the mixed solution obtained in the first step, an aqueous solution of sodium aluminate (I) (for example, preferably containing 21 to 23% by mass as Al ₂ O ₃ ) and an aqueous solution of basic aluminum chloride (B) (for example, preferably the _Al as 2 _{O 3} containing 22 to 24 wt%) are added simultaneously with stirring over a period of 10 minutes to 2 hours. At this time, the addition amount of the aqueous solution of sodium aluminate and the aqueous solution of basic aluminum chloride is appropriately adjusted (it is preferable to mix approximately the same chemical equivalent although it varies depending on the concentration of each aqueous solution). The solution is added while maintaining pH 6.5 to 10.0, preferably pH 7.0 to 9.0. Thereby, the pseudo boehmite seed formed in the first step is grown, and a slurry (suspension) of alumina hydrate having a pseudo boehmite structure is obtained. In this case, the liquid temperature of the mixed solution is preferably maintained at 50 to 70 ° C, preferably 55 to 65 ° C. Further, after the addition of the aqueous solution of sodium aluminate and the aqueous solution of basic aluminum chloride is stopped, stirring is preferably continued for 10 minutes to 2 hours as desired to obtain a uniform alumina hydrate.

(Third step-washing operation)
Next, the obtained slurry is washed with pure water at 50 to 70 ° C., preferably 55 to 65 ° C. to remove impurities such as sodium and hydrochloric acid radicals, thereby obtaining a washed cake.
(3rd step-ripening operation)
Furthermore, pure water is added to the washed cake, and the Al ₂ O ₃ concentration (that is, “concentration as Al ₂ O ₃ ”, hereinafter the same) is 5 to 13% by mass, preferably 7 to 11% by mass. %, And then adjusted to pH 9-12, preferably pH 10-11, with aqueous ammonia to obtain a prepared slurry. The prepared slurry is aged in an aging tank equipped with a reflux at 80 ° C. or higher, preferably 90 to 100 ° C., and 5 to 20 hours, preferably 8 to 15 hours to obtain an aged slurry.

(Third step-spray drying operation)
The obtained aging slurry is subjected to, for example, a spray dryer in which the inlet temperature is 280 to 550 ° C, preferably 350 to 500 ° C, and the outlet temperature is adjusted to 150 to 280 ° C, preferably 200 to 250 ° C. Spray drying is performed to obtain alumina powder. When this alumina powder is heated at 1000 ° C. for 1 hour, the loss on ignition (ignition loss, loss of ignition. Hereinafter, also simply referred to as “loss on ignition”) is preferably 15 to 20% by mass. Here, if the amount of the ignition source of the alumina powder is less than 15% by mass, the particle strength of the alumina powder becomes too high, the moldability of the kneaded product is deteriorated in the subsequent process, and the strength of the obtained molded product is lowered. is there. When the ignition loss of the alumina powder exceeds 20% by mass, the pore structure having a large pore diameter formed in the alumina powder disappears during the kneading, and the second pore group ( P ₂ ) may decrease, and the pore volume (PV _P2 ) of the second pore group may be smaller than 0.1 ml / g. The spray-dried alumina powder contains, for example, 0.3 to 1.2% by mass of adhering water and 15.5 to 16.5% by mass of crystal water, and Al ₂ O ₃ · 1.05-1 .25H ₂ O.

(Third step-kneading operation)
After adding pure water to the obtained alumina powder so that the Al ₂ O ₃ concentration is 20 to 40% by mass, preferably 25 to 35% by mass, the kneader is used for 3 to 20 minutes, preferably 5 to 10 minutes. Knead to a degree to obtain a koji. Here, if the kneading time is less than 3 minutes, the moldability deteriorates in the next molding operation, and the strength of the resulting alumina carrier decreases. If it exceeds 20 minutes, the pore volume of the second pore group (PV _P2 ) may be smaller than 0.1 ml / g.
(Third step-molding operation)
The obtained kneaded product is extruded and molded into a 1.8 mm four-leaf column by an extrusion molding machine to obtain a molded product. In addition, a molded object can be shape | molded in shapes, such as a three-leaf type | mold column shape and a cylinder, besides the four-leaf type | mold column shape, The magnitude | size is not limited, either.
(Third step—dry baking operation)
The molded product is dried at, for example, 100 to 150 ° C., preferably 120 to 140 ° C. and for 10 to 20 hours, preferably 15 to 18 hours, and then further 500 to 800 ° C., preferably 600 to 700 ° C. And calcining for 30 minutes to 2 hours, preferably 45 to 90 minutes, to obtain an alumina support.

(4th process)
In the obtained alumina carrier, as active metal components, for example, molybdenum oxide and nickel carbonate are 1 to 4% by mass as molybdenum oxide (MoO ₃ ) and 0.4 to 0.7% by mass as nickel oxide (NiO), respectively. % Of the active metal-containing aqueous solution containing 2% to 5% by mass of molybdenum oxide (MoO ₃ ) on an alumina support on a catalyst basis by a pore filling method, a dipping method, an equilibrium adsorption method, or the like, preferably 3 -4 mass%, and after impregnation as nickel oxide (NiO) 0.5-0.9 mass%, preferably 0.6-0.8 mass%, preferably from room temperature to 300 ° C. with a dryer Is dried at an elevated temperature from room temperature to 270 ° C., more preferably from room temperature to 250 ° C., and further from 400 to 700 ° C., preferably from 500 to 6 in air. 0 ° C., and 30 minutes to 2 hours, preferably calcined 45-90 minutes, to produce a hydrodemetallization catalyst. Here, the pore filling method is to prepare an active metal-containing aqueous solution in an amount corresponding to the total pore volume of the alumina carrier weighed in advance, and this active metal-containing aqueous solution is degassed under reduced pressure. In this method, the active metal component is impregnated in the pores by being taken into the pores.
In the hydrodemetallation catalyst and the method for producing the same of the present invention, molybdenum and nickel are typically used as active metal components, but combinations other than molybdenum and nickel, or periodic table group 6A metal and One selected from Group 8 metals may be used.

  In the hydrodemetallation catalyst of the present invention, the active metal component is present on an alumina support having a large total pore volume and having pore distribution peaks in the pore diameter range of 5 to 100 nm and the pore diameter range of 500 to 10,000 nm. Is supported, it has high demetallation activity and desulfurization activity, and can be suitably used for hydroprocessing heavy hydrocarbon oils such as residual oils containing metal contaminants such as vanadium and nickel. Moreover, since the hydrodemetallation catalyst of the present invention is produced from a high-strength alumina support, it has strength that can be used industrially.

Further, in the method for producing an alumina carrier of the present invention, an aqueous solution of basic aluminum chloride is added so that the pH becomes 6.5 to 10.0 within 5 minutes while stirring the groundwater adjusted to pH 10 to 14. Then, while maintaining the obtained mixed solution within the range of pH 6.5 to 10.0, while further stirring the aqueous solution of sodium aluminate and the basic aluminum chloride in the mixed solution over 10 minutes to 2 hours at the same time. As a result, it is possible to obtain an alumina hydrate having a pseudo boehmite structure, and this alumina hydrate is washed, matured, spray dried, kneaded, molded, dried, and fired sequentially, so that the pore volume is large. Moreover, a high-strength alumina support can be produced.
Furthermore, in the method for producing a hydrotreating catalyst of the present invention, at least one active metal component selected from Group 6A metals and Group 8 metals of the periodic table is supported on the alumina support of the present invention. A long-life hydrodemetallation catalyst can be produced.

  The alumina carrier and the hydrodemetallation catalyst A were produced by applying the alumina carrier and the hydrodemetallation catalyst production method using the same according to one embodiment of the present invention. Furthermore, the metal removal activity of the produced hydrodemetallation catalyst A was measured.

Example 1
140.6 kg of pure water was put (stored) in a tank provided with a 200 L capacity stirring blade and a steam heating device, and the water temperature was heated to 60 ° C. by the steam heating device. Furthermore, while stirring pure water in the tank with a stirring blade, 0.6 kg of sodium aluminate aqueous solution (containing 22% by mass, that is, 0.13 kg as Al ₂ O ₃ ), 2.6 g of sodium gluconate, Was added while maintaining the liquid temperature at 60 ° C., and an aqueous solution of sodium aluminate having an Al ₂ O ₃ concentration of 0.09 mass% was prepared as the groundwater. At this time, the groundwater was pH 10.5.
Next, 1.89 kg of basic aluminum chloride aqueous solution (containing 23 mass% as Al ₂ O ₃ , that is, containing 0.43 kg) is added over 2 minutes while stirring the groundwater, and the pseudo boehmite seed is added. Followed by 5.7 kg of aqueous sodium aluminate solution (containing 22% by weight, ie 1.25 kg as Al ₂ O ₃ ), and 18.2 kg of basic aluminum chloride aqueous solution (as Al ₂ O ₃ , 23 mass%, that is, 4.19 kg inclusive) was added simultaneously over 30 minutes while maintaining the liquid temperature at 60 ± 1 ° C., and pseudoboehmite by coprecipitation. The particles were grown and stirred for an additional hour to obtain a uniform slurry of alumina hydrate.
The basic aluminum chloride aqueous solution is made from basic aluminum chloride represented by [Al ₂ (OH) ₅ Cl ₁ ] ₅ .

The obtained slurry was washed, impurities such as sodium and hydrochloric acid radicals adhering to the slurry were removed, and 67.0 kg of washing cake (9.0 mass% as Al ₂ O ₃ , that is, containing 6.0 kg) )
3.6 kg of pure water was added to 67.0 kg of washing cake, adjusted to 8.5% by mass as Al ₂ O ₃ , adjusted to pH 10.5 with 15% by mass of ammonia water, In an aging tank with agitation at 95 ° C. for 10 hours with stirring to obtain 75.8 kg of aging slurry.
The obtained aging slurry was spray-dried with a spray dryer ODT-27 type manufactured by Okawahara Koki Co., Ltd. having an inlet temperature of 460 ° C. and an outlet temperature of 220 ° C. to obtain 7.19 kg of alumina powder. Got. Alumina powder is loss on ignition 16.5% at 1000 ° C., adhesive moisture 0.3 wt%, crystal water are contained 16.2 _{wt%, Al 2 O 3 · 1.12H} 2 Expressed as O.
Further, 2.25 kg of pure water was added to 1.20 kg of alumina powder to adjust the Al ₂ O ₃ concentration to 29% by mass, and then a kneader (manufactured by Toshin Co., Ltd., double-arm kneader TK5-3 type) was used. Knead for 6 minutes to obtain a kneaded product. This kneaded product was extruded and molded into a 1.8 mm four-leaf column by an extrusion molding machine (Auger type extruder DE-75 manufactured by Honda Iron Works Co., Ltd.) to obtain a molded product. The obtained molded product was dried at 110 ° C. for 16 hours and then calcined at 650 ° C. for 1 hour to obtain an alumina carrier.

Properties of the obtained alumina carrier, that is, the total pore volume (PV _T ), the ratio of the pore volume (PV _L ) of pores having a pore diameter of 100 nm or more to the total pore volume (PV _T ) (PV _L / PV _T ), pore volume (PV _P1 ) occupied by pores having a pore diameter range of 5 to 100 nm in the _first pore group (P ₁ ), pore diameter 500 to 10,000 nm in the second pore group (P ₂ ). Pore volume (PV _P2 ), specific surface area (SA), pressure strength (CS), wear strength (AR), average pore diameter, apparent bulk density (ABD), compression bulk The density (compacted bulk density, CBD) was measured by the method described above, and the results are shown in Table 1. FIG. 1 (a) shows an integral pore distribution diagram showing the relationship between the pore diameter of the alumina support and the cumulative pore volume, and FIG. 1 (b) shows the pore diameter and differential pores of the alumina support. The differential type pore distribution map showing the relationship with the volume is shown.
As shown in FIG. 1 (b), the obtained alumina support has a pore distribution first in the range of pore diameters of 5 to 100 nm (about 20 nm) and pore diameters of 500 to 10,000 nm (about 1400 nm). It has a bimodal pore structure having a peak and a second peak.

400 g of the obtained alumina carrier was weighed and added to the pore filling method (in this method, an active metal-containing aqueous solution in an amount corresponding to the total pore volume of the weighed alumina carrier was mixed with the alumina carrier, and the pressure was reduced. In this method, the active metal component is impregnated into the pores by incorporating the aqueous solution into the pores of the alumina carrier.) The molybdenum which is a Group 6A metal of the periodic table and the nickel which is a Group 8 metal are each oxidized. As a product, it was supported so as to be 3.3% by mass and 0.7% by mass based on the catalyst. Here, since the pore volume (PV _T ) of the alumina carrier is 1.44 ml / g from Table 1, the total pore volume of 400 g of the alumina carrier is 576 ml (1.44 ml / g × 400 g). Then, 576 ml of an active metal-containing aqueous solution having the same amount as the total pore volume of the alumina support was prepared. This active metal-containing aqueous solution was obtained by suspending 13.7 g of molybdenum trioxide (2.4% by mass) and 4.6 g of nickel carbonate (0.8% by mass) in 551 g of warm water (95 ° C.). After sealing and stirring at 95 ° C. for 5 hours, 2.5 times (7.1 g) malic acid of nickel oxide (NiO, 2.8 g) with nickel carbonate as an oxide was added, and molybdenum oxide was added. And nickel carbonate was completely dissolved.
400 g of an alumina carrier is put into a blender (mixer), and the pressure is reduced (here, −60 cmHg) while the blender is stopped, and deaerated for 10 minutes. Further, 576 ml of the active metal-containing aqueous solution was added while rotating the blender in a degassed state, and then allowed to stand for 30 minutes while rotating under normal pressure, and the alumina support was impregnated with molybdenum and nickel. The temperature is dried from room temperature to 250 ° C. using a rotary dryer, and further calcined in the air at 550 ° C. for 1 hour to form molybdenum and nickel as oxides in an amount of 3.3% by mass and 0.00%, respectively. A 7% by weight supported hydrodemetallation catalyst A was prepared. Table 1 shows the properties of the hydrodemetallation catalyst A. 2 (a) and 2 (b) show integral and differential pore distribution diagrams of the hydrodemetallation catalyst A, respectively.

(Comparative Example 1)
Comparative Example 1 is different from Example 1 in that conventionally used aluminum sulfate is used instead of basic aluminum chloride. Specifically, 141.2 kg (Al ₂ Add 0.94 kg of aluminum sulfate aqueous solution (7 mass% as Al ₂ O ₃ , ie, 0.07 kg) over 2 minutes to 0.09 mass% as O ₃ , ie, 0.13 kg. Subsequently, 20.8 kg of sodium aluminate aqueous solution (containing 22% by mass as Al ₂ O ₃ , that is, 4.58 kg) and 32.6 kg of aluminum sulfate aqueous solution (7% by mass as Al ₂ O ₃ , that is, , 2.28 kg) was added at the same time over 30 minutes while maintaining the liquid temperature at 60 ± 1 ° C. and stirring for 1 hour. The point which manufactures the hydroprocessing catalyst B from the slurry of a mina hydrate is different from Example 1. FIG. Table 1 shows the properties of the hydrodemetallation catalyst B.

(Comparative Example 2)
Comparative Example 2 is different from Example 1 in that the hydrotreating catalyst C was produced from a dehydrated cake obtained by dehydrating the aging slurry obtained in Example 1 instead of spray drying. Specifically, first, the ripened slurry was dehydrated with a vacuum filter to obtain a dehydrated cake. After the dehydrated cake was kneaded with a kneader for 45 minutes, the resulting kneaded product was extruded into a 1.8 mm four-leaf type column with an extruder, and the resulting molded product was dried at 110 ° C. for 16 hours. Further, it was calcined at 650 ° C. for 1 hour to obtain an alumina carrier. Hydrogen thus obtained was supported on the obtained alumina support so that molybdenum, which is a Group 6A metal of the periodic table, and nickel, which is a Group 8 metal, were used as oxides in amounts of 3.3% by mass and 0.7% by mass, respectively. A metallization catalyst C was prepared. Table 1 shows the properties of the hydrodemetallation catalyst C.

(Test example)
Hydrodemetallation catalyst A (Test Example 1), hydrodemetallation catalyst B (Comparative Test Example 1), or hydrodemetallation catalyst C (Comparative Test Example 2) is fixed bed microreactor (hydrotreating apparatus) The raw material oils shown in Table 2 were treated under the conditions shown in Table 3, and the demetallizing activity, desulfurizing activity, deasphaltenic activity, and decarburized carbon activity were measured. The results are shown in Table 4.
Here, the microreactor is as follows: (1) any one of hydrodemetallation catalyst A, hydrodemetallation catalyst B, and hydrotreating catalyst C, (2) demetallation catalyst D (catalyst chemical industry stock) Company DM5CQ), and (3) Desulfurization catalyst E (R25NQ made by Catalytic Chemical Industry Co., Ltd.), in order of 30% by volume, 29% by volume, and 41% by volume, respectively. did.

脱金属率＝（原料油中の金属濃度−生成油中の金属濃度）／原料油中の金属濃度×１００
脱硫率＝（原料油中の硫黄濃度−生成油中の硫黄濃度）／原料油中の硫黄濃度×１００

Demetalization rate = (metal concentration in the feedstock-metal concentration in the product oil) / metal concentration in the feedstock × 100
Desulfurization rate = (sulfur concentration in the feed oil−sulfur concentration in the product oil) / sulfur concentration in the feed oil × 100

  As shown in Table 1, the hydrodemetallation catalyst A of the present invention has a larger total pore volume and a pore volume of the first and second pore groups than the hydrodemetallation catalyst B, and It was high strength. In addition, although the hydrodemetallation catalyst A was slightly lower in strength than the hydrotreating catalyst C, the total pore volume and the pore volumes of the first and second pore groups were increased. Further, as shown in Table 4, the hydrodemetallation catalyst A has higher demetalization activity, deasphaltenic activity, and decarburization activity than the hydrodemetallation catalyst B and the hydrotreating catalyst C. The activity is also equivalent. From these results, it is understood that the hydrodemetallation catalyst A of the present invention is industrially useful.

  The present invention is not limited to the above-described embodiment, and can be changed without changing the gist of the present invention. For example, some or all of the above-described embodiments and modifications are possible. When the hydrodemetallation catalyst of the present invention and the method for producing the same are combined, the scope of right of the present invention is also included.

(A) is an integral-type pore distribution diagram of the alumina carrier of the present invention, and (b) is a differential pore-distribution diagram of the alumina carrier. (A) is an integral type pore distribution map of the hydrodemetallation catalyst A of the present invention, and (b) is a differential type pore distribution map of the hydrodemetallation catalyst A of the present invention.

Claims (4)

An alumina carrier having the following properties (a) to (f):
(A) The total pore volume measured by the mercury intrusion method exceeds 1.2 ml / g and is 2.0 ml / g or less.
(B) The ratio of the pore volume of pores having a pore diameter of 100 nm or more to the total pore volume measured by mercury porosimetry is 0.12 to 0.35.
(C) At least two fine pores, a first pore group having a pore distribution peak in the pore diameter range of 5 to 100 nm and a second pore group having a pore distribution peak in the pore diameter range of 500 to 10,000 nm. A pore volume comprised of pore groups, and the pore volume occupied by pores having a diameter of 5 to 100 nm in the first pore group is 0.9 ml / g or more, and the second pore group The pore volume occupied by pores having a pore diameter of 500 to 10,000 nm is 0.1 ml / g or more.
(D) The specific surface area is 150 m ² / g or more.
(E) The pressure strength is 7 N / mm or more.
(F) Abrasion strength is 0.5% or less. A hydrodemetallation catalyst comprising the alumina carrier according to claim 1 supporting at least one active metal component selected from Group 6A metal and Group 8 metal of the periodic table . a first step of adding an aqueous solution of basic aluminum chloride to the groundwater so that the pH becomes 6.5 to 10.0 within 5 minutes while stirring the groundwater adjusted to pH 10 to 14;
While maintaining the mixed solution obtained in the first step within the range of pH 6.5 to 10.0, an aqueous solution of sodium aluminate and an aqueous solution of basic aluminum chloride are further added to the mixed solution over 10 minutes to 2 hours. A second step of simultaneously adding with stirring to obtain alumina hydrate;
A method for producing an alumina carrier, comprising a third step of obtaining the alumina carrier by sequentially washing, aging, spray drying, kneading, molding, drying and firing the alumina hydrate. A method for producing a hydrodemetallation catalyst, comprising supporting at least one active metal component selected from Group 6A metal and Group 8 metal of the periodic table on the alumina support according to claim 1 .

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