JP6216658B2 - Catalyst for hydrorefining of vacuum gas oil and method for producing the same - Google Patents

Description

  The present invention relates to a hydrorefining catalyst for vacuum gas oil for removing sulfur and nitrogen in vacuum gas oil in the presence of hydrogen and a method for producing the same.

At present, the quality regulation of sulfur content in fuel oil is being strengthened from the viewpoint of environmental protection. In particular, the sulfur content in gasoline and light oil is strictly regulated. For this reason, the development of a catalyst exhibiting high desulfurization performance in order to meet this regulation is in progress.
In recent years, liquid fuels have been required to further reduce the sulfur content. In response to this requirement, fuel oil manufacturers have regulations on gasoline with a sulfur content of 10 ppm or less, so fuel oil manufacturers have studied various clean fuel production methods, such as measures to improve catalysts and increase facilities. .
As hydrorefining catalysts, catalysts in which an active metal such as molybdenum or cobalt is supported on a carrier such as alumina are widely used. Among these, titania supports are known to exhibit high desulfurization performance compared to alumina supports, and hydrorefining catalysts using titania supports are also expected to be a catalyst that can meet these requirements.
However, titania generally has a small specific surface area and tends to have low thermal stability at high temperatures. For the purpose of solving this problem, porous titania obtained by adding a particle growth inhibitor that suppresses particle growth at the time of firing to hydrous or hydrogel of hydrous titanium oxide or a dried product thereof, followed by drying and firing. Has been developed (for example, Patent Document 1). However, when only this porous titania is used as a carrier, there is a problem that the catalyst becomes expensive.
Therefore, a hydrorefining catalyst using an alumina-titania support prepared by supporting a water-soluble titania compound on an alumina support has also been developed (for example, Patent Document 2). However, although the hydrorefining catalyst can be reduced in price, since the titania can be supported only by the water absorption rate of the carrier, the catalyst performance tends to be lowered.
A hydrorefining catalyst using an alumina-titania support prepared by highly dispersing titania in alumina by mixing titania during alumina preparation has also been developed (for example, Patent Document 3). However, this carrier can highly disperse titania in alumina. However, as the titania content increases, the specific surface area decreases and the titania aggregates, so that the sharpness of the pore distribution deteriorates and the performance of the catalyst decreases. There was a tendency to decrease.
Furthermore, a carrier containing aluminum-silicon-phosphorus-boron has been developed as a hydrorefining catalyst using a carrier containing four kinds of elements (Patent Document 4). However, a larger pore volume is required.
Furthermore, a hydrorefining catalyst in which a metal component is supported on a support containing four elements of aluminum-silicon-titanium-phosphorus is disclosed (Patent Document 5). However, silicon is derived from zeolite, and is a carrier obtained by kneading zeolite into a hydrate containing aluminum, titanium and phosphorus, and a carrier having a larger pore volume has been demanded.

JP 2008-304686 A JP 2005-262173 A Japanese Patent Laid-Open No. 10-118495 JP 2010-221117 A JP 2013-027847 A

  An object of the present invention is to provide a catalyst for hydrorefining vacuum gas oil that uses an inorganic composite oxide carrier containing aluminum, silicon, titanium, and phosphorus and that exhibits low desulfurization and denitrification performance, and a method for producing the same. And

As a result of intensive studies on the above problems, the present inventors have completed the present invention.
That is, the present invention has the following configuration.

[1] A catalyst for hydrorefining vacuum gas oil comprising an inorganic composite oxide carrier containing aluminum, silicon, titanium and phosphorus, and at least one metal component selected from Group VIA and Group VIII of the periodic table The carrier has (a) aluminum content of 70 to 85% by mass in terms of aluminum oxide (Al ₂ O ₃ ) based on the total amount of the carrier, and (b) the weight of SiO ₂ / Al ₂ O ₃ . A catalyst for hydrorefining of vacuum gas oil, wherein the ratio is 0.08 to 0.17, and the weight ratio of (c) P ₂ O ₅ / TiO ₂ is 0.3 to 1.2.

  [2] The catalyst for hydrorefining vacuum gas oil according to [1] above, wherein the carrier has an average pore diameter (PD) measured by a mercury intrusion method in the range of 70 to 110 mm.

  [3] In the pore distribution measured by the mercury intrusion method of the carrier, the ratio of the pore volume (PVp) of the average pore diameter (PD) ± 30% of the pore diameter (PVp) to the total pore volume (PVo) (PVp / PVo ) Is 76% or more, the catalyst for hydrorefining of vacuum gas oil according to the above [1] or [2].

[4] The hydrorefining catalyst for vacuum gas oil according to any one of the above [1] to [3], wherein the support has a specific surface area of 350 to 500 m ² / g.

  [5] Any one of the above [1] to [4], wherein the pore volume (PV) measured by the pore filling method of the carrier is in the range of 0.70 to 1.0 ml / g. A catalyst for hydrorefining vacuum gas oil as described in 1.

  [6] The reduced pressure according to any one of [1] to [5], wherein the metal component selected from Group VIA and Group VIII of the periodic table is selected from molybdenum, tungsten, cobalt, and nickel. Catalyst for hydrorefining of light oil.

[7] A catalyst for hydrorefining reduced pressure gas oil in which molybdenum, cobalt and nickel are supported on the carrier, wherein (d) the content of molybdenum is 15 to 25% by mass in terms of molybdenum oxide (MoO ₃ ) (E) The content of cobalt is 2.0 to 5.0 mass% in terms of cobalt oxide (CoO), and (f) the content of nickel is 0.5 to 3 in terms of nickel oxide (NiO). The hydrorefining catalyst for vacuum gas oil according to any one of the above [1] to [6], which is 0.0% by mass (provided that the hydrorefining catalyst is 100% by mass).

[8] A method for producing a catalyst for hydrorefining vacuum gas oil according to any one of [1] to [7],
(1) A mixed aqueous solution of a titanium mineral acid salt and an acidic aluminum salt is added to a basic aluminum salt aqueous solution containing phosphate ions and silicate ions so that the pH becomes 6.5 to 9.5, and aluminum, A first step of obtaining a hydrate of a composite oxide of silicon, titanium and phosphorus;
(2) a second step of obtaining a carrier by sequentially washing, molding, drying and baking the hydrate;
(3) a third step in which an impregnating solution containing at least one metal component selected from Group VIA and Group VIII of the periodic table is contacted to obtain a metal-supported carrier; and (4) contacting with the impregnating solution. A fourth step of drying the resulting metal-supported carrier and further calcining it to obtain a hydrorefining catalyst;
A process for producing a catalyst for hydrorefining vacuum gas oil, characterized by comprising:

  The catalyst for hydrorefining vacuum gas oil of the present invention is excellent in desulfurization and denitrification activities.

2 is a distribution diagram of carrier a pores in Example 1. FIG.

  Hereinafter, the present invention will be described in detail.

  The hydrorefining catalyst for vacuum gas oil of the present invention is selected from Group VIA and Group VIII of the Periodic Table as an inorganic composite oxide support containing aluminum, silicon, titanium and phosphorus (hereinafter also simply referred to as support). The catalyst for hydrorefining (hereinafter also simply referred to as catalyst) carrying at least one metal component.

  The inorganic composite oxide carrier according to the present invention contains aluminum, silicon, titanium and phosphorus. The contents of aluminum, silicon, titanium and phosphorus in the support are as follows. In addition, all content is content when the whole support | carrier is 100 mass%.

The content of aluminum in the support is in the range of 70 to 85% by mass, preferably in the range of 72 to 83% by mass in terms of aluminum oxide (Al ₂ O ₃ ). When the oxide-equivalent aluminum content is less than 70% by mass, the catalyst tends to deteriorate, and when it exceeds 85% by mass, the surface area tends to decrease and the desulfurization and denitrification activities tend to decrease.

The silicon content in the carrier is preferably 5.6 to 14.5% by mass, more preferably 6.0 to 12.0% by mass in terms of silicon oxide (SiO ₂ ). If the silicon content in terms of oxide is less than 5.6% by mass or more than 14.5% by mass, molybdenum aggregates and desulfurization activity and denitrification activity tend to decrease.

The titanium content in the carrier, titanium oxide is preferably (TiO ₂₎ is 4.0 to 15.0 mass% in terms of, and more preferably 5.0 to 12.0 wt%. If the titanium content in terms of oxide is less than 4.0% by mass, sufficient desulfurization and denitrogenation activity cannot be obtained, and if it exceeds 15.0% by mass, the titanium oxide aggregates and the surface area decreases, thereby desulfurizing. The activity tends to decrease.

The phosphorus content in the carrier is preferably 2.0 to 7.0% by mass and more preferably 3.0 to 6.0% by mass in terms of phosphorus oxide (P ₂ O ₅ ). If the phosphorus content in terms of oxide is less than 2.0% by mass or exceeds 7.0% by mass, the pore distribution becomes broad and the desulfurization activity tends to decrease.

The weight ratio (SiO ₂ / Al ₂ O ₃ ) of the aluminum content (as oxide) and silicon content (as oxide) in the support is 0.08 to 0.17, preferably 0.09. ~ 0.16. When SiO ₂ / Al ₂ O ₃ is less than 0.08, the specific surface area of the support decreases and desulfurization activity decreases, and when it exceeds 0.17, the pore distribution becomes broad and desulfurization activity decreases. Absent.

The weight ratio (P ₂ O ₅ / TiO ₂ ) of the titanium content (as oxide) and phosphorus content (as oxide) in the support is 0.3 to 1.2, preferably 0.4. It is -1.0, More preferably, it is 0.5-0.9. When P ₂ O ₅ / TiO ₂ is less than 0.3 or exceeds 1.2, the pore distribution becomes broad and the desulfurization activity decreases, which is not preferable.

  The average pore diameter (PD) measured by the mercury intrusion method of the inorganic composite oxide carrier according to the present invention is preferably 70 to 110 mm, more preferably 75 to 100 mm. If the average pore diameter (PD) is less than 70 mm, the metal component is difficult to impregnate and is not practical. On the other hand, if it is larger than 110 mm, the catalyst strength may be lowered, which is not preferable.

  Moreover, in the pore distribution measured by the mercury intrusion method, the ratio (PVp / PVo) of the pore volume (PVp) of the average pore diameter (PD) ± 30% to the total pore volume (PVo) is 76%. The above is preferable, 78% or more is more preferable, and 80% or more is more preferable. When PVp / PVo is less than 76%, the average pore distribution is broad, which may lead to a decrease in specific surface area and may deteriorate the desulfurization activity.

  In the present invention, the pore diameter and pore distribution are also measured by the mercury intrusion method, and the pore diameter is a value calculated using a mercury surface tension of 480 dyne / cm and a contact angle of 150 °. Further, the total pore volume (PVo) in the present invention is a total value of pore volumes of pores having a pore diameter that can be measured by a mercury intrusion method.

Measured specific surface area by the BET method of the inorganic composite oxide support according to the present invention (SA) is preferably from ^{350~500m 2 / g, 370~480m 2 /} g is more preferable. If the specific surface area (SA) is less than 350 m ² / g, the metal components are likely to aggregate and the desulfurization performance may be lowered, which is not preferable. On the other hand, if it exceeds 500 m ² / g, desulfurization activity tends to decrease, such being undesirable.

  The pore volume (PV) measured by the pore filling method of the inorganic composite oxide carrier according to the present invention is preferably 0.70 to 1.0 ml / g, and preferably 0.75 to 0.95 ml / g. More preferred. When the pore volume (PV) is less than 0.70 ml / g, the desulfurization activity is lowered, and the desulfurization performance may be deteriorated. On the other hand, if it exceeds 1.0 ml / g, the catalyst strength may decrease, which is not preferable.

  The metal component supported on the inorganic composite oxide support according to the present invention is at least one metal selected from Group VIA (IUPAC Group 6) and Group VIII (Group IUPAC Group 8 to Group 10) of the periodic table. It is.

As the metal component of Group VIA of the periodic table, molybdenum and tungsten are preferable, and molybdenum is more preferable.
As the metal component of Group VIII of the periodic table, cobalt and nickel are preferably used.

The content of the metal component of Group VIA of the periodic table in the catalyst is preferably 10 to 28% by mass, and more preferably 15 to 25% by mass in terms of oxide based on the total amount of the catalyst.
The content of the metal component of Group VIII of the periodic table in the catalyst is preferably 0.2 to 10 mass%, more preferably 1 to 8 mass%, more preferably 2 to 6 mass%, based on the total amount of the catalyst and in terms of oxide. More preferred is mass%.

  The total content of the metal components selected from Group VIA and Group VIII of the periodic table in the catalyst is preferably in the range of 1 to 35% by mass, and in the range of 10 to 33% by mass in terms of oxide based on the total amount of the catalyst. More preferably, the range of 15-30 mass% is further more preferable.

When molybdenum or tungsten is supported, the molybdenum or tungsten content in the catalyst is preferably 10 to 28% by mass in terms of the total amount of the catalyst, in terms of molybdenum oxide (MoO ₃ ) or tungsten oxide (WO ₃ ). More preferably, it is 15-25 mass%, More preferably, it is 17-23 mass%. If the molybdenum or tungsten content in terms of oxide is less than 10% by mass or exceeds 28% by mass, the desulfurization activity and denitrification activity tend to decrease rapidly, which is not practical.

  When cobalt is supported, the cobalt content in the catalyst is preferably 1.0 to 6.0% by mass, more preferably 2.0 to 5%, based on the total amount of the catalyst, in terms of cobalt oxide (CoO). It is 0.0 mass%, More preferably, it is 2.0-4.0 mass%. If the cobalt content in terms of oxide is less than 1.0% by mass, the desulfurization activity tends to decrease, and if it exceeds 6.0% by mass, the desulfurization activity is not improved.

  When nickel is supported, the nickel content in the catalyst is preferably 0.2 to 4.0% by mass, more preferably 0.5 to 3% in terms of the total amount of the catalyst, in terms of nickel oxide (NiO). 0.0% by mass. When the nickel content in terms of oxide is less than 0.2% by mass, the denitrification activity decreases greatly, and when it exceeds 4.0% by mass, the desulfurization activity decreases.

The catalyst of the present invention is most preferably a hydrorefining catalyst in which molybdenum, cobalt and nickel are supported on the inorganic composite oxide support described above, and the supported amount of each metal component at that time is based on the total amount of the catalyst. The content of (d) molybdenum is 15 to 25% by mass in terms of molybdenum oxide (MoO ₃ ), and the content of (e) cobalt is 2.0 to 5.0 in terms of cobalt oxide (CoO). It is preferable that content of mass% and (f) nickel is 0.5-3.0 mass% in conversion of nickel oxide (NiO).

  There is no restriction | limiting in particular as a raw material of a metal component, A nitrate, carbonate, an oxide, etc. can be used widely. Specifically, nickel nitrate, nickel carbonate, cobalt nitrate, cobalt carbonate, molybdenum trioxide, ammonium molybdate and the like are preferably used.

The hydrorefining catalyst of the present invention can be suitably used for, for example, gasoline, kerosene, light oil, vacuum light oil, and the like. Among these, it is suitably applied to vacuum gas oil because it has a high nitrogen content and the effects of the present invention are particularly exerted. The hydrodesulfurization treatment using the catalyst is carried out under a high-temperature and high-pressure condition in a hydrogen atmosphere by filling the catalyst in a fixed bed reactor.
The vacuum gas oil is a fraction containing 70% by mass or more of a fraction having a boiling point of 340 to 550 ° C. when the atmospheric distillation residue in petroleum refining is treated with a vacuum distillation apparatus. The oil to be treated by atmospheric distillation is not particularly limited, and examples thereof include petroleum crude oil, synthetic crude oil derived from oil sand, coal liquefied oil, bitumen reformed oil, and the like.

  Next, the manufacturing method of the hydrorefining catalyst of the vacuum gas oil of this invention is demonstrated.

The method for producing a hydrorefining catalyst for vacuum gas oil according to the present invention comprises a first step of obtaining a hydrate of an inorganic composite oxide, and the inorganic hydrate by sequentially washing, molding, drying and firing the hydrate. A second step of obtaining a carrier; and a step of contacting the inorganic composite oxide carrier with an impregnating solution containing at least one metal component selected from Group VIA and Group VIII of the periodic table to obtain a metal-supported carrier. 3 steps, and a fourth step of preparing the hydrorefining catalyst by drying the carrier carrying the metal obtained in the third step and further calcining it.
Hereinafter, each process will be described.

<First step>
In the first step, a basic aluminum salt aqueous solution containing phosphate ions (this is an alkaline aqueous solution) and a mixed aqueous solution of a titanium mineral acid salt and an acidic aluminum salt (this is an acidic aqueous solution), It is a step of obtaining an inorganic composite oxide hydrate by mixing so that the pH is 6.5 to 9.5, preferably 6.5 to 8.5, and more preferably 6.8 to 8.0. . At this time, any one of the aqueous solutions contains silicate ions.
That is, in this step, (1) a case where a mixed aqueous solution of a titanium mineral acid salt and an acidic aluminum salt is added to a basic aluminum salt aqueous solution containing phosphate ions and silicate ions, and (2) a base containing phosphate ions In some cases, a mixed aqueous solution of a titanium mineral acid salt and an acidic aluminum salt containing a silicate ion is added to the aqueous solution of the basic aluminum salt.

  In order to prepare a carrier having a high silicon oxide content as in the present invention, when mixing silicate ions in an aluminum salt, the solubility of silicate ions decreases and the silicate ions tend to aggregate, There is a possibility that it is difficult to obtain a carrier in which silicon is uniformly dispersed. Therefore, by adding phosphate ions and / or titanium mineral salts, it is possible to suppress the aggregation of silicate ions, maintain a uniform dispersion state, and to prepare a carrier with a high silicon oxide content. It becomes.

Here, in the case of (1), basic or neutral silicate ions contained in the basic aluminum salt aqueous solution can be used. As the basic silicate ion source, a silicate compound that generates silicate ions in water such as sodium silicate can be used.
On the other hand, in the case of (2), the silicate ion contained in the mixed solution of the titanium mineral acid salt and the acidic aluminum salt aqueous solution can be acidic or neutral. As the acidic silicate ion source, a silicate compound that generates silicate ions in water such as silicic acid can be used.

  Further, as the basic aluminum salt, sodium aluminate, potassium aluminate or the like is preferably used. Further, as the acidic aluminum salt, aluminum sulfate, aluminum chloride, aluminum nitrate and the like are preferably used, and as the titanium mineral acid salt, titanium tetrachloride, titanium trichloride, titanium sulfate, titanyl sulfate, titanium nitrate and the like are exemplified. In particular, titanium sulfate and titanyl sulfate are preferably used because they are inexpensive. Further, the phosphate source contained in the basic aluminum salt aqueous solution includes phosphite ions, and phosphorous in water such as ammonia phosphate, potassium phosphate, sodium phosphate, phosphoric acid and phosphorous acid. Phosphate compounds that generate acid ions can be used.

  In the present invention, an inorganic composite oxide hydrate may be obtained by either of the methods (1) and (2), but (1) is preferred from the viewpoint of diluting the silicate compound. .

  When the inorganic composite oxide hydrate is obtained by the method (1), first, an aqueous silicate solution is mixed with an aqueous basic aluminum salt solution in the presence of phosphate ions. Then, a mixed aqueous solution of titanium mineral acid salt and acidic aluminum salt is added to this so that the pH becomes 6.5 to 9.5, preferably 6.5 to 8.5, more preferably 6.8 to 8.0. By mixing, an inorganic composite oxide hydrate containing aluminum, silicon, titanium and phosphorus can be obtained.

For example, a basic aluminum salt aqueous solution containing a predetermined amount of phosphate ions is put into a tank equipped with a stirrer, a silicate aqueous solution is added, and the temperature is usually kept at 40 to 90 ° C., preferably 50 to 70 ° C. Then, the pH of the mixed aqueous solution of a predetermined amount of titanium mineral acid salt and acidic aluminum salt aqueous solution heated to a temperature of ± 5 ° C., preferably ± 2 ° C., more preferably ± 1 ° C. of this solution is 6.5-9. 5, preferably from 6.5 to 8.5, more preferably from 6.5 to 8.0, usually in 5 to 20 minutes, preferably 7 to 15 minutes, to form a precipitate and hydrate A slurry of the product is obtained.
Here, the addition of the mixed aqueous solution to the basic aluminum salt aqueous solution is preferably 15 minutes or less because undesirable crystals such as bayerite and gibbsite may be generated in addition to pseudoboehmite as time goes on. More preferably less than a minute. Bayerite and gibbsite are not preferred because their specific surface area decreases when fired.

<Second step>
The inorganic composite oxide hydrate slurry obtained in the first step is aged if desired, and then washed to remove by-product salts to obtain a hydrate slurry containing aluminum, silicon, titanium and phosphorus. . The obtained hydrate slurry is further heat-aged if desired, and then, by conventional means, for example, heat-kneaded to obtain a moldable kneaded product, and then molded into a desired shape by extrusion molding or the like. In general, after drying at 70 to 150 ° C., preferably 90 to 130 ° C., it is further calcined at 400 to 800 ° C., preferably 450 to 600 ° C., for 0.5 to 10 hours, preferably 2 to 5 hours. An inorganic composite oxide support containing silicon, titanium and phosphorus is obtained.

<Third step>
The impregnating liquid containing at least one metal component selected from Group VIA and Group VIII of the periodic table is brought into contact with the obtained inorganic composite oxide support containing aluminum, silicon, titanium and phosphorus.

As the raw material for the metal component, for example, molybdenum trioxide, ammonium molybdate, ammonium metatungstate, ammonium paratungstate, tungsten trioxide, nickel nitrate, nickel carbonate, cobalt nitrate, cobalt carbonate and the like are preferably used.
It is preferable that the impregnating solution is made to have a pH of 4 or less using an acid to dissolve the metal component. When pH exceeds 4, it exists in the tendency for the stability of the metal component which melt | dissolves to fall and to precipitate.

  As the solvent for the metal component, either one or both of a phosphorus compound and a chelating agent may be used.

As the phosphorus compound, orthophosphoric acid (hereinafter also simply referred to as “phosphoric acid”), ammonium dihydrogen phosphate, diammonium hydrogen phosphate, trimetaphosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, and more preferably, Orthophosphoric acid can be used.
In the hydrorefining catalyst, the phosphorus compound is preferably contained in an amount of 3 to 25 parts by mass, and in the range of 5 to 15 parts by mass, in terms of oxide, with respect to 100 parts by mass of molybdenum oxide. Is more preferable. If the content of the phosphorus compound exceeds 25 parts by mass in terms of oxides with respect to molybdenum oxide, the performance of the presulfided hydrorefining catalyst tends to deteriorate, and if it is less than 3 parts by mass, the impregnating solution is stable. It is not preferable because the properties deteriorate.

Examples of the chelating agent include citric acid, malic acid, tartaric acid, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), polyethylene glycol (PEG), and tetraethylene glycol (TEG). Malic acid is preferably used.
When using a chelating agent, it is preferable to contain 35-75 mass parts with respect to 100 mass parts of molybdenum oxides, and it is more preferable to contain in the range of 55-65 mass parts. Here, when the chelating agent exceeds 75 parts by mass with respect to molybdenum, the viscosity of the impregnating liquid containing the metal component increases, which makes the impregnation step in production difficult. This is not preferable because the stability of the catalyst tends to deteriorate and the catalyst performance tends to decrease.

  The method for incorporating the metal component, phosphorus compound or further chelating agent into the carrier is not particularly limited, and known methods such as impregnation method (equilibrium adsorption method, pore filling method, initial wetting method, etc.), ion exchange method and the like. This method can be used. Here, the impregnation method is a method in which a support is impregnated with an impregnation liquid containing an active metal and then dried. In the impregnation method, it is preferable to simultaneously carry the metal component. If the metals are separately supported, the desulfurization activity or denitrification activity may be insufficient.

<4th process>
The carrier carrying the metal component in the third step is dried at 110 to 250 ° C., and further calcined at 400 to 600 ° C., preferably 450 to 550 ° C., for 0.5 to 10 hours, preferably 2 to 5 hours. The hydrodesulfurization catalyst of the present invention is produced. Here, when the firing temperature exceeds 600 ° C., aggregation of the metal component supported on the carrier occurs, and the desulfurization activity tends to decrease, which is not preferable.

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

[Measurement method of catalyst component content]
3 g of a measurement sample was collected in a zirconia ball with a lid having a capacity of 30 ml, dried (200 ° C., 20 minutes), calcined (700 ° C., 5 minutes), ₂ g of sodium peroxide (Na ₂ O ₂ ) and sodium hydroxide 1 g of (NaOH) was added and melted for 15 minutes. Further, 25 ml of sulfuric acid (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, the content of each component was converted into an oxide conversion standard (Al ₂ O ₃ , SiO ₂ , TiO) using an ICP device (manufactured by Shimadzu Corporation, ICPS-8100, analysis software ICPS-8000). ₂ , P ₂ O ₅ , MoO ₃ , NiO, CoO).

[Example 1: Preparation of hydrodesulfurization catalyst a]
A tank with a steam jacket with a capacity of 100 L is charged with 4.65 kg of 22 mass% sodium aluminate aqueous solution (manufactured by JGC Catalysts & Chemicals Co., Ltd.) in terms of Al ₂ O ₃ concentration, diluted with 43 kg of ion-exchanged water, P ₂ O ₅ concentration of 2.5 wt% of trisodium phosphate in terms of (Yoneyama Kagaku _(Co.); P 2 _{O 5} concentration of 19% by weight) is added with stirring a solution 4.0 kg. Thereafter, 4.0 kg of a 5 mass% sodium silicate solution (manufactured by AGC S-Tech Co., Ltd .; SiO ₂ concentration 24 mass%) in terms of SiO ₂ concentration was added with stirring and heated to 60 ° C. Aqueous aluminum salt solution was prepared.
Also, an aluminum aluminum salt aqueous solution obtained by diluting 7.97 kg of an aluminum sulfate aqueous solution (manufactured by JGC Catalysts and Chemicals Co., Ltd.) with 7 kg of ion-exchanged water in terms of Al ₂ O ₃ concentration, and 33 mass in terms of TiO ₂ concentration. % Of titanyl sulfate (manufactured by Teika Co., Ltd.) (0.36 kg) was mixed with an aqueous solution of titanium mineral acid salt dissolved in 2.0 kg of ion exchange water, and heated to 60 ° C. to prepare a mixed aqueous solution. Add a mixed aqueous solution to a tank containing a basic aqueous aluminum salt solution at a constant rate using a roller pump until the pH is 7.2 (addition time: 10 minutes), and contain aluminum, silicon, titanium, and phosphorus. Hydrate slurry a was prepared.

The obtained hydrate slurry a was aged at 60 ° C. for 1 hour with stirring, dehydrated using a flat plate filter, and further washed with 150 L of a 0.3 mass% aqueous ammonia solution. The cake-like slurry after washing was diluted with ion-exchanged water so as to be 6.0% by mass in terms of Al ₂ O ₃ concentration, and then the pH was adjusted to 10.0 with 15% by mass ammonia water. This was transferred to an aging tank equipped with a reflux machine and aged at 95 ° C. for 10 hours with stirring. 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 material was molded into a cylindrical shape having a diameter of 1.8 mm by an extrusion molding machine and dried at 110 ° C. The dried molded product was baked in an electric furnace at a temperature of 550 ° C. for 3 hours to obtain an inorganic composite oxide carrier a (hereinafter also simply referred to as carrier a. The same applies to the following examples).

Carrier a is 79% by mass in terms of Al ₂ O ₃ , aluminum is 10% by mass in terms of SiO ₂ , titanium is 6% by mass in terms of TiO ₂ , and phosphorus is ₅ % in terms of P ₂ O ₅ , based on the total amount of carrier. It was contained by mass%.
The carrier a was subjected to pore distribution measurement using a pore distribution measuring device PoleMaster by the mercury intrusion method manufactured by Quantachrome (the same applies to the following examples). The result is shown in FIG. From the average pore distribution of the carrier, the ratio (PVp / PVo) of the pore diameter (PVp) of the pore diameter of ± 30% of the average pore diameter (PD) to the total pore volume (PVo) is calculated. The PVp / PVo value was 86%. Table 1 shows the properties of the carrier a.

Next, 294 g of molybdenum trioxide (manufactured by Climax Co., Ltd .; MoO ₃ concentration 99 mass%), 84 g of cobalt carbonate (manufactured by Tanaka Chemical Laboratory Co., Ltd .; CoO concentration 61 mass%), and nickel carbonate (Jodo Chemical) Kogyo Co., Ltd. (NiO concentration: 55% by mass) (36 g) was suspended in 400 ml of ion-exchanged water, and this suspension was heated at 95 ° C. for 5 hours with an appropriate refluxing device so that the liquid volume did not decrease. After that, 57 g of phosphoric acid (manufactured by Kanto Chemical Co., Inc .; P ₂ O ₅ concentration 62 mass%) and 49 g of nitric acid (manufactured by Kanto Chemical Co., Ltd .; nitric acid concentration 60 mass%) were added and dissolved to prepare an impregnation solution. did. The impregnating solution is spray impregnated on 1000 g of support a, dried at 250 ° C., and further calcined in an electric furnace at 550 ° C. for 1 hour to be hydrodesulfurized catalyst a (hereinafter also simply referred to as “catalyst a”. The same applies to the examples of the above.
The content of the metal component of the catalyst a is 21.0% by mass of MoO ₃ , 3.6% by mass of CoO, 1.4% by mass of NiO, and 2.5% by mass of P ₂ O _{5 based on the} total amount of the catalyst. Met. Table 1 shows the properties of the catalyst a.

[Example 2: Preparation of hydrodesulfurization catalyst b]
In the carrier preparation, the same preparation as that of the carrier a was performed except that 4.86 kg of an aqueous sodium aluminate solution, 2.8 kg of a sodium silicate solution, 8.15 kg of an aqueous aluminum sulfate solution, and 15 kg of ion-exchanged water for diluting aluminum sulfate were used. A carrier b was obtained.
Carrier b is based on the total amount of carrier, aluminum is 82% by mass in terms of Al ₂ O ₃ , silicon is 7% by mass in terms of SiO ₂ , titanium is 6% by mass in terms of TiO ₂ , and phosphorus is ₅ % in terms of P ₂ O 5. It was contained by mass%.
Next, using the same impregnating solution as in Example 1, catalyst b was produced from carrier b.
Table 1 shows the properties of the carrier b and the catalyst b.

[Example 3: Preparation of hydrodesulfurization catalyst c]
In the carrier preparation, the same preparation as carrier a except that 4.50 kg of sodium aluminate aqueous solution, 42 kg of ion-exchanged water for diluting sodium aluminate aqueous solution, 4.8 kg of sodium silicate solution, and 7.84 kg of aluminum sulfate aqueous solution were used. To obtain a carrier c.
The carrier c is based on the total amount of the carrier. Aluminum is 77% by mass in terms of Al ₂ O ₃ , silicon is 12% by mass in terms of SiO ₂ , titanium is 6% by mass in terms of TiO ₂ , and phosphorus is ₅ % in terms of P ₂ O 5. It was contained by mass%.
Next, using the same impregnating solution as in Example 1, a catalyst c was produced from the carrier c.
Table 1 shows the properties of the carrier c and the catalyst c.

[Example 4: Preparation of hydrodesulfurization catalyst d]
In the carrier preparation, the same as carrier a, except that 4.86 kg of sodium aluminate aqueous solution, 44 kg of ion exchange water for diluting sodium aluminate aqueous solution, 2.4 kg of trisodium phosphate solution, and 7.87 kg of aluminum sulfate aqueous solution were used. Preparation was carried out to obtain carrier d.
The carrier d is based on the total amount of the carrier. Aluminum is 81% by mass in terms of Al ₂ O ₃ , silicon is 10% by mass in terms of SiO ₂ , titanium is 6% by mass in terms of TiO ₂ , and phosphorus is 3% in terms of P ₂ O _5. It was contained by mass%.
Next, the catalyst d was produced from the carrier d using the same impregnation solution as in Example 1.
Table 1 shows the properties of the carrier d and the catalyst d.

[Example 5: Preparation of hydrodesulfurization catalyst e]
In the carrier preparation, 4.53 kg of sodium aluminate aqueous solution, 44 kg of ion exchange water for diluting sodium aluminate aqueous solution, 7.18 kg of aluminum sulfate aqueous solution, 13 kg of ion exchange water for diluting aluminum sulfate, 0.61 kg of titanyl sulfate, and titanyl sulfate A carrier e was obtained in the same manner as the carrier a except that 3.39 kg of ion-exchanged water to be dissolved was used.
Carrier e is 75% by mass in terms of Al ₂ O ₃ , aluminum is 10% by mass in terms of SiO ₂ , titanium is 10% by mass in terms of TiO ₂ , and phosphorus is ₅ % in terms of P ₂ O ₅ , based on the total amount of carrier. It was contained by mass%.
Next, a catalyst e was produced from the carrier e using the same impregnating solution as in Example 1.
Table 1 shows the properties of the carrier e and the catalyst e.

[Example 6: Preparation of hydrodesulfurization catalyst f]
In the carrier preparation, 4.75 kg of sodium aluminate aqueous solution, 44 kg of ion-exchanged water for diluting the sodium aluminate aqueous solution, 5 mass% of silicic acid in terms of SiO ₂ concentration (manufactured by JGC Catalysts & Chemicals Co., Ltd.) instead of sodium silicate solution ; SiO ₂ concentration of 13 mass%) 1.08 kg, an aqueous aluminum sulfate solution 7.56Kg, deionized water 14kg diluting aluminum sulfate, titanyl sulfate 0.61 kg, for the use of ion-exchange water 3.39kg dissolving titanyl sulfate A carrier f was obtained in the same manner as in the carrier a except for the above.
The carrier f is 78% by mass in terms of Al ₂ O ₃ , 7% by mass in terms of SiO ₂ , 10% by mass in terms of TiO ₂ , and 5% in terms of P ₂ O ₅ , based on the total amount of carrier. It was contained by mass%.
Next, using the same impregnating solution as in Example 1, a catalyst f was produced from the carrier f.
Table 1 shows the properties of the carrier f and the catalyst f.

[Comparative Example 1: Preparation of hydrodesulfurization catalyst g]
In the carrier preparation, 4.83 kg of sodium aluminate aqueous solution, 39 kg of ion exchange water for diluting sodium aluminate aqueous solution, 8.0 kg of trisodium phosphate solution, 0.8 kg of sodium silicate solution, 9.68 kg of aqueous aluminum sulfate solution, aluminum sulfate Was prepared in the same manner as carrier a except that 17 kg of ion-exchanged water for diluting water, 0.06 kg of titanyl sulfate, and 0.34 kg of ion-exchanged water for dissolving titanyl sulfate were used.
The carrier g is based on the total amount of the carrier, and aluminum is 87% by mass in terms of Al ₂ O ₃ , silicon is 2% by mass in terms of SiO ₂ , titanium is 1% by mass in terms of TiO ₂ , and phosphorus is 10% in terms of P ₂ O _5. It was contained by mass%.
Next, catalyst g was produced from carrier g using the same impregnating solution as in Example 1.
Table 1 shows the properties of the carrier g and the catalyst g.

[Comparative Example 2: Preparation of hydrodesulfurization catalyst h]
In preparing the carrier, 3.93 kg of sodium aluminate aqueous solution, 41 kg of ion exchange water for diluting the sodium aluminate aqueous solution, 8.0 kg of sodium silicate solution, 7.35 kg of aluminum sulfate aqueous solution, and 13 kg of ion exchange water for diluting aluminum sulfate are used. A carrier h was obtained in the same manner as in the carrier a except that the carrier h was prepared.
The carrier h is based on the total amount of the carrier, aluminum is 69% by mass in terms of Al ₂ O ₃ , silicon is 20% by mass in terms of SiO ₂ , titanium is 6% by mass in terms of TiO ₂ , and phosphorus is ₅ % in terms of P ₂ O 5. It was contained by mass%.
Next, a catalyst h was produced from the carrier h using the same impregnation liquid as in Example 1.
Table 1 shows the properties of the carrier h and the catalyst h.

[Comparative Example 3: Preparation of hydrodesulfurization catalyst i]
In the carrier preparation, 3.90 kg of sodium aluminate aqueous solution, 37 kg of ion exchange water for diluting sodium aluminate aqueous solution, 9.6 kg of trisodium phosphate solution, 8.30 kg of aluminum sulfate aqueous solution, and 15 kg of ion exchange water for diluting aluminum sulfate. A carrier i was obtained in the same manner as in the carrier a except that it was used.
Carrier i is based on the total amount of carrier, aluminum is 72 mass% in terms of Al ₂ O ₃ , silicon is 10 mass% in terms of SiO ₂ , titanium is 6 mass% in terms of TiO ₂ , and phosphorus is 12 mass in terms of P ₂ O _5. It was contained by mass%.
Next, catalyst i was produced from carrier i using the same impregnating solution as in Example 1.
Table 1 shows the properties of the carrier i and the catalyst i.

[Comparative Example 4: Preparation of hydrodesulfurization catalyst j]
In the carrier preparation, 4.65 kg of sodium aluminate aqueous solution, 41 kg of ion exchange water for diluting the sodium aluminate aqueous solution, 4.8 kg of sodium silicate solution, 8.83 kg of aluminum sulfate aqueous solution, 16 kg of ion exchange water for diluting aluminum sulfate, sulfuric acid A carrier j was obtained in the same manner as the carrier a except that 0.06 kg of titanyl and 0.34 kg of ion-exchanged water in which titanyl sulfate was dissolved were used.
Carrier j is based on the total amount of carrier, aluminum is 82% by mass in terms of Al ₂ O ₃ , silicon is 12% by mass in terms of SiO ₂ , titanium is 1% by mass in terms of TiO ₂ , and phosphorus is ₅ % in terms of P ₂ O 5. It was contained by mass%.
Next, using the same impregnation solution as in Example 1, catalyst j was produced from carrier j.
Table 1 shows the properties of the carrier j and the catalyst j.

[Comparative Example 5: Preparation of hydrodesulfurization catalyst k]
In preparing the carrier, 4.61 kg of sodium aluminate aqueous solution, 39 kg of ion exchange water for diluting the sodium aluminate aqueous solution, 7.2 kg of trisodium phosphate solution, 2.8 kg of sodium silicate solution, 9.52 kg of aqueous aluminum sulfate solution, aluminum sulfate The carrier k was prepared in the same manner as the carrier a, except that 17 kg of ion-exchanged water for diluting was used and no ion-exchanged water for dissolving titanyl sulfate and titanyl sulfate was used.
The carrier k is based on the total amount of the carrier. Aluminum is 84% by mass in terms of Al ₂ O ₃ , silicon is 7% by mass in terms of SiO ₂ , titanium is 0% by mass in terms of TiO ₂ , and phosphorus is 9% in terms of P ₂ O _5. It was contained by mass%.
Next, a catalyst k was produced from the carrier k using the same impregnation liquid as in Example 1.
Table 1 shows the properties of the carrier k and the catalyst k.

[Desulfurization and denitrification evaluation test]
Catalysts a to k were charged into a fixed bed reactor and pre-sulfided. Then, hydrorefining is performed by supplying vacuum gas oil (boiling range: 343 to 550 ° C., sulfur content: 2.71% by mass, nitrogen content: 0.079% by mass) to the fixed bed reactor at a rate of 200 ml / hour. It was. The reaction conditions at that time were a hydrogen partial pressure of 6 MPa, a liquid space velocity of 2.0 h ⁻¹ , a hydrogen / oil ratio of 2,500 scfb, and a reaction temperature of 340 ° C. or 360 ° C. Table 1 shows the results of the desulfurization rate and denitrogenation rate at each reaction temperature.
Here, the desulfurization rate is obtained by the formula [sulfur content removed by hydrorefining] / [sulfur content in vacuum gas oil] × 100 (%), and the denitrification rate is removed by hydrorefining. Nitrogen content] / [Nitrogen content in vacuum gas oil] × 100 (%).

As can be seen from Table 1, in Examples 1 to 6 using the hydrorefining catalysts a to f of the present invention, the sulfur content and nitrogen content of the vacuum gas oil could be removed to a high degree.
On the other hand, in the hydrorefining catalyst of Comparative Example 1, since the amount of silica in the carrier is small and the amount of phosphorus is large, the sharpness is deteriorated and the desulfurization rate and denitrification rate are low. Further, in Comparative Example 2 in which the amount of silica exceeded the claimed range, the sharpness of the pore distribution deteriorated, so the surface area decreased, and the desulfurization rate was particularly low. In Comparative Examples 3 and 4 in which the amount and balance of both additives are outside the scope of claims, both the desulfurization rate and the denitrification rate were low because the sharpness of the pore distribution deteriorated and the surface area was low. In Comparative Example 5 where no titanium was added, the desulfurization rate was low.

  The hydrorefining catalyst of the present invention is extremely useful industrially because it can be highly hydrorefined under reduced pressure gas oil and can be produced at low cost.

Claims (8)

A hydrorefining catalyst for vacuum gas oil comprising an inorganic composite oxide support containing aluminum, silicon, titanium and phosphorus, and at least one metal component selected from Group VIA and Group VIII of the periodic table, In the support, (a) the aluminum content is 70 to 85% by mass in terms of aluminum oxide (Al ₂ O ₃ ) based on the total amount of the support, and (b) the weight ratio of SiO ₂ / Al ₂ O ₃ is 0. 0.08 to 0.17, (c) Titanium content is 4.0 to 15.0 mass% in terms of titanium oxide (TiO ₂ ) based on the total amount of support, and phosphorus content is based on the total amount of support. Further, it is characterized in that it is 2.0 to 7.0 mass% in terms of phosphorus oxide (P ₂ O ₅ ), and the weight ratio of P ₂ O ₅ / TiO ₂ is in the range of 0.3 to 1.2. Catalyst for hydrorefining of vacuum gas oil.
  2. The catalyst for hydrorefining vacuum gas oil according to claim 1, wherein the carrier has an average pore diameter (PD) measured by a mercury intrusion method in the range of 70 to 110 mm. 3.   In the pore distribution measured by the mercury intrusion method of the carrier, the ratio (PVp / PVo) of the pore volume (PVp) of the average pore diameter (PD) ± 30% to the total pore volume (PVo) is 76%. The catalyst for hydrorefining of vacuum gas oil according to claim 1 or 2, wherein the catalyst is at least%. Vacuum gas oil hydrotreating catalyst according to claim 1, specific surface area of the carrier is characterized in that in the range of 350~500m 2 / ^g.   5. The vacuum gas oil according to claim 1, wherein the pore volume (PV) measured by a pore filling method of the carrier is in the range of 0.70 to 1.0 ml / g. Catalyst for hydrorefining.   6. The hydrorefining of vacuum gas oil according to claim 1, wherein the metal component selected from Group VIA and Group VIII of the periodic table is selected from molybdenum, tungsten, cobalt, and nickel. catalyst. A catalyst for hydrorefining of vacuum gas oil having molybdenum, cobalt and nickel supported on the carrier, wherein (d) the content of molybdenum is 15 to 25% by mass in terms of molybdenum oxide (MoO ₃ ), (e ) Cobalt content is 2.0 to 5.0 mass% in terms of cobalt oxide (CoO), and (f) Nickel content is 0.5 to 3.0 mass in terms of nickel oxide (NiO). % (However, the hydrorefining catalyst is 100 mass%). The hydrorefining catalyst for vacuum gas oil according to any one of claims 1 to 6, wherein A method for producing a catalyst for hydrorefining vacuum gas oil according to any one of claims 1 to 7,
(1) A mixed aqueous solution of a titanium mineral acid salt and an acidic aluminum salt is added to a basic aluminum salt aqueous solution containing phosphate ions and silicate ions so that the pH becomes 6.5 to 9.5, and aluminum, A first step of obtaining a hydrate of a composite oxide of silicon, titanium and phosphorus;
(2) a second step of obtaining a carrier by sequentially washing, molding, drying and baking the hydrate;
(3) a third step in which an impregnating solution containing at least one metal component selected from Group VIA and Group VIII of the periodic table is contacted to obtain a metal-supported carrier; and (4) contacting with the impregnating solution. A method for producing a hydrorefining catalyst for reduced pressure gas oil, comprising a fourth step of drying the obtained metal-supported carrier and further calcining to obtain a hydrorefining catalyst.

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