JP6643810B2 - Hydrotreating catalyst for hydrocarbon oil, method for producing the same, and hydrotreating method - Google Patents

Description

  The present invention relates to a hydrotreating catalyst for removing a sulfur content in a hydrocarbon oil in the presence of hydrogen, a method for producing the same, and a hydrotreating method.

  In the hydrogenation treatment, the reaction proceeds at a high temperature and a high pressure using a catalyst. However, by lowering the reaction conditions to a low temperature and a low pressure, the economical efficiency of the process is increased. Therefore, it is desired that the activity of the catalyst is high. The public knowledge about the reduction temperature of molybdenum is as follows.

  R. L. According to Cordero, it is described that the reduction temperature of molybdenum under a hydrogen stream of a catalyst in which molybdenum is supported on alumina or silica varies greatly depending on the type and composition of the carrier. However, nickel or cobalt as a co-catalyst is not added, and it is hard to say that it is a practical catalyst. In addition, since the relationship between this property and the desulfurization activity is not mentioned, the optimum reduction temperature of the catalyst is not mentioned.

  J. Escobar et al. Have two reduction peak temperatures of 384 to 403 ° C. and 539 to 576 ° C. belonging to molybdenum under a hydrogen gas flow of an unfired catalyst supporting nickel, molybdenum, and phosphorus on an alumina support. It was revealed that the peak was larger than the former. However, although knowledge about the reduction peak temperature of the unfired catalyst is described, the catalyst of the calcined product is not mentioned, and the relationship between the reduction peak temperature of molybdenum on the composite oxide and the reduction profile and the desulfurization activity is described. It has not been.

Patent Literature 1 discloses that a sulfide catalyst containing a base metal element selected from Groups 8 to 10 of the periodic table such as nickel, cobalt, molybdenum, and tungsten includes a group 8 to 10 group of the periodic table such as rhodium, palladium, and platinum. It has been reported that by adding a selected noble metal, high hydrotreating performance is exhibited by utilizing spillover hydrogen. In addition, it is described that the behavior of the catalyst component serving as a reaction active point undergoing reduction has a close relationship with the catalytic activity of the hydrogenation treatment, and it is desirable that the reduction peak temperature of the catalyst under a hydrogen stream be 500 ° C. or lower. Have been. However, the use of a precious metal is not desirable in terms of a higher catalyst price and a depletion of global resources as compared with a base metal.
Although the findings referring to the reduction temperature of molybdenum as described above have been reported, no catalyst has been proposed that is inexpensive, has excellent desulfurization performance, and can be easily regenerated.

JP 2002-210362 A

R. L. Cordero et al., Applied Catalysis, 74, 125-136 (1991). J. Escobar et al., Applied Catalysis B: Environmental, 88, 564-575 (2009).

  An object of the present invention is to provide a hydrotreating catalyst for a hydrocarbon oil, which has excellent desulfurization activity and can regenerate a high-performance catalyst, and a method for producing the same. Another object of the present invention is to provide a method for hydrotreating a hydrocarbon oil, which can remove a sulfur content in the hydrocarbon oil at a high removal rate.

Hydrocarbon treatment catalyst for hydrocarbon oil of the present invention,
(1) As an active metal component, a first metal component that is at least one of molybdenum and tungsten and a second metal component that is at least one of cobalt and nickel are provided on the inorganic oxide support. Carried,
(2) The content of the first metal component is 15 to 30 parts by mass in terms of oxide with respect to 100 parts by mass of the catalyst, and the content of the second metal component is 100 parts by mass of the catalyst. And 3 to 7 parts by mass in terms of oxide, and carbon derived from an organic acid is 2.0 parts by mass or less on an element basis with respect to 100 parts by mass of the catalyst.
(3) The specific surface area of the catalyst is 140 to 350 m ² / g, the average pore diameter of the catalyst measured by a mercury intrusion method is 50 to 130 °,
(4) The peak temperature of desorbed water up to 450 ° C. based on the temperature-reduction method of the catalyst is less than 5.0% and the peak temperature of desorbed water is less than 412.0 ° C. The amount of adsorption is 8.0 ml / g or more;
It is characterized by the following.

Specific examples of the present invention are listed below, but do not limit the scope of the present invention.
The inorganic oxide carrier contains 80 to 100 parts by mass of aluminum in terms of alumina based on 100 parts by mass of the inorganic oxide carrier.
The inorganic oxide carrier corresponds to at least one of the following (1) to (3).
(1) It contains 5.0 parts by mass or less of phosphorus in terms of phosphoric acid with respect to 100 parts by mass of the inorganic oxide carrier.
(2) Titanium is contained in an amount of 20.0 parts by mass or less based on 100 parts by mass of the inorganic oxide carrier.
(3) Silicon is contained in an amount of 2.0 parts by mass or less in terms of silica with respect to 100 parts by mass of the inorganic oxide carrier.

The active metal component contains molybdenum and cobalt, and further contains at least one of nickel, copper, magnesium and zinc in terms of oxide in an amount of 0 to 3.0 parts by mass with respect to 100 parts by mass of the catalyst.
The catalyst has a maximum peak temperature of desorbed water of up to 900 ° C. based on a temperature-reduction method of 415 ° C. or lower.

The method for producing a catalyst for hydrotreating hydrocarbon oil of the present invention,
(1) a step of preparing an inorganic oxide carrier containing aluminum;
(2) preparing an impregnation liquid containing a first metal component that is at least one of molybdenum and tungsten, a second metal component that is at least one of cobalt and nickel, and an organic acid; Supporting a metal component and a second metal component on the inorganic oxide carrier,
(3) A hydrotreating catalyst obtained by heat-treating the inorganic oxide carrier carrying the first metal component and the second metal component obtained in the step (2) at a temperature of 100 to 600 ° C. Obtaining a
It is characterized by having.

The hydrocarbon oil hydrotreating method of the present invention is characterized in that, in the presence of a hydrotreating catalyst, the hydrogen partial pressure is 3 to 8 MPa, the temperature is 300 to 420 ° C., and the liquid hourly space velocity is 0.3 to 5 hr ⁻¹ . and performing hydrotreating a hydrocarbon oil.

It has been reported that by introducing a noble metal into a usual desulfurization catalyst, the reduction temperature is lowered and the activity is improved. However, there are many problems when the noble metal is industrialized due to its high cost and depletion. Therefore, in the present invention, by appropriately managing the reduction temperature of the catalyst while maintaining a high NO adsorption amount, the sulfuration treatment is sufficiently advanced, and the active metal is highly dispersed and easily regenerated. Can be obtained.
Further, according to the method for producing a catalyst for hydrotreating hydrocarbon oil of the present invention, the peak temperature of reduction of the catalyst by hydrogen of the present catalyst (the peak temperature of desorbed water based on the temperature raising reduction method).
By controlling the sulfur content, the sulfuration treatment can be sufficiently advanced, and a high-performance catalyst in which the active metal is highly dispersed can be prepared, and a hydrotreating catalyst excellent in desulfurization activity can be produced.
Further, by using the hydrocarbon oil hydrotreating catalyst of the present invention, a method for hydrodesulfurizing a hydrocarbon oil having high desulfurization activity can be provided.

It is a graph which shows an example (example) of an analysis result of the peak temperature of desorption water by a temperature-reduction reduction method. 4 is a graph showing an example (comparative example) of the analysis result of the peak temperature of desorbed water by a temperature-reduction method.

Hereinafter, preferred embodiments of the present invention will be described in detail.
[Catalyst for hydrotreating hydrocarbon oils]
The catalyst for hydrotreating hydrocarbon oil of the present invention comprises an inorganic oxide carrier containing, for example, aluminum and an active metal component, and has predetermined properties. Hereinafter, the properties of the inorganic oxide carrier, the active metal component, and the catalyst will be described in detail.

<Inorganic oxide carrier>
Examples of the inorganic oxide carrier constituting the hydrotreating catalyst include known carriers used for this type of catalyst, which are composed of various inorganic substances. As the inorganic carrier or the inorganic component constituting the inorganic carrier, for example, various kinds of composite oxides comprising alumina or a composite oxide of alumina and at least one selected from silica, phosphorus, boria, titania, zirconia, magnesia, and the like Can be mentioned. In other words, the composite oxide contains aluminum and at least one or more elements selected from titanium, silicon, phosphorus, zirconium, magnesium and boron.

  Specific examples of the composite oxide include, for example, silica alumina, zeolite, alumina titania, alumina phosphorus, alumina boria, alumina magnesia, alumina zirconia, alumina titania silica, and the like, but are not limited thereto. . The properties and shape of the inorganic oxide carrier are appropriately selected according to various conditions such as the type and composition of the metal component to be supported and the use of the catalyst.

  For example, in order to effectively support the active metal component in a highly dispersed state on a carrier and sufficiently secure catalytic activity, a porous carrier is usually used, and relatively small pores having a pore diameter of 500 ° or less are used. Those having are preferably used. Further, in order to control physical properties such as mechanical strength and heat resistance of the carrier or the catalyst, an appropriate binder component or an additive may be contained when the carrier or the catalyst is formed.

Examples of the inorganic oxide carrier (hereinafter, also simply referred to as “carrier”) used in the catalyst for hydrotreating hydrocarbon oil according to the present invention include, for example, aluminum oxide alone or a composite of aluminum and silicon, phosphorus or titanium. The content of aluminum and the like when an oxide is used is described. The aluminum content in the carrier, aluminum oxide _(Al 2 _{O 3)} (aluminum oxide _(Al 2 _{O 3)} 80 parts by mass or more in terms of per 100 parts by mass of the carrier) of 80% or more in terms of the preferred. If the content of aluminum in terms of oxide is less than 80% by mass, the catalyst tends to deteriorate quickly.

Content of silicon in the carrier, silicon oxide (SiO ₂₎ 2.0 wt% in terms of the following (a silicon oxide with respect to 100 parts by weight of carrier (SiO ₂₎ to 2.0 parts by mass basis)) of Preferably, when the silicon content is excessively large, silica aggregates and the pore distribution of the carrier becomes broad, so that the desulfurization activity and the denitrification activity tend to decrease.

The content of titanium in the carrier, titanium oxide (TiO ₂₎ 20.0% by weight in terms of the following (titanium oxide with respect to 100 parts by weight of carrier (TiO ₂₎ 20.0 parts by mass or less in terms) are preferred . If the titanium content in terms of oxide is excessively large, the pore distribution of the carrier becomes broad and the desulfurization activity tends to decrease.

The content of phosphorus in the carrier is 5.0% by mass or less in terms of phosphor oxide (P ₂ O ₅ ) (5.0 parts by mass or less in terms of phosphor oxide (P ₂ O ₅ ) per 100 parts by mass of carrier). Is preferred. If the phosphorus content is excessively large, the pore distribution of the carrier tends to be broad and the desulfurization performance tends to decrease.

<Active metal component>
On the inorganic oxide support, a first metal component, for example, molybdenum, and a second metal component, for example, cobalt, are supported as active metal components.
The first metal component may be tungsten instead of molybdenum, or may be both molybdenum and tungsten. The content (loading amount) of the first metal component needs to be 15 to 30% by mass in terms of oxide on a catalyst basis (15 to 30 parts by mass in terms of oxide with respect to 100 parts by mass of catalyst). It is.

  If the content of the first metal component is excessively smaller than 15% by mass in terms of oxide, the desulfurization activity required for the reaction may not be secured. If the content is more than 30% by mass, the metal component is likely to aggregate. And dispersibility may be impaired.

  The second metal component may be nickel instead of cobalt, or both cobalt and nickel. The content (loading amount) of the second metal component is required to be 3 to 7% by mass in terms of oxide on a catalyst basis (15 to 30 parts by mass in terms of oxide with respect to 100 parts by mass of the catalyst). It is. The second metal component acts as a cocatalyst with respect to the first metal component, and when the content is less than 3% by mass in terms of oxide, the first metal component and the second metal component that are active metal components. However, it becomes difficult to maintain an appropriate structure, and if the content exceeds 7% by mass in terms of oxides, the aggregation of the active metal component is apt to proceed, and the catalytic performance decreases.

  Further, the content of carbon derived from an organic acid must be 2.0% by mass or less on an element basis on a catalyst basis (2.0 parts by mass or less on an element basis with respect to 100 parts by mass of the catalyst). When the active metal component is supported on the inorganic oxide carrier by the impregnation method, an organic acid is usually contained in the impregnating liquid, and therefore, the organic acid becomes a source of carbon supported on the inorganic oxide carrier. . By setting the carbon content to 2.0% by mass or less on an elemental basis, the activity at the time of catalyst regeneration becomes 80% or more when the desulfurization performance of a new unused catalyst (fresh catalyst) is 100%. can do. If the content of carbon is large, there is a concern that the active metal component may be aggregated by the calcination step during catalyst regeneration.

  Examples of the organic acid include citric acid, malic acid, gluconic acid, tartaric acid, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), and more preferably citric acid, malic acid, tartaric acid, gluconic acid, and the like. Is mentioned. In the case where an organic additive such as a saccharide (monosaccharide, disaccharide, polysaccharide, etc.) is used in addition to the organic acid, in this specification, the content of carbon derived from the organic acid means the content of the organic acid. And the content of carbon derived from both organic additives.

<Characteristics of catalyst>
The catalyst of the present invention needs to have a specific surface area (SA) measured by the BET method in the range of 140 to 350 m ² / g. If the specific surface area (SA) is smaller than 140 m ² / g, the metal component is liable to agglomerate and the desulfurization performance may be undesirably reduced. On the other hand, if it is larger than 350 m ² / g, the average pore diameter and the pore volume become small, and the desulfurization activity tends to decrease.

  Further, the average pore diameter needs to be 50 to 130 °. The average pore diameter is a value measured by a mercury intrusion method (mercury contact angle: 130 degrees, surface tension: 480 dyn / cm), and represents a pore diameter corresponding to 50% of the total pore volume. The pore volume indicates the volume of pores having a pore diameter of 41 ° or more. If the average pore diameter is smaller than 50 °, the desulfurization performance may decrease, and if the average pore diameter is larger than 130 °, the catalyst strength may decrease.

The catalyst of the present invention has an ignition loss (Ig Loss) of 5.0% or less. The ignition loss can be obtained by calculating by heating the catalyst at a high temperature as described in the item of the measuring method described below. In order to reduce the loss on ignition of the catalyst to 5.0% or less, it is necessary to spray and impregnate the inorganic oxide carrier with the impregnating liquid and then calcinate at a temperature of 300 ° C. or more, for example.
By making the ignition loss of the catalyst 5.0% or less, the activity at the time of catalyst regeneration can be 80% or more when the desulfurization performance of a new unused catalyst (fresh catalyst) is 100%. it can. When the ignition loss of the catalyst increases. There is a concern that the active metal component may be agglomerated by the firing step during catalyst regeneration.

  The catalyst of the present invention has a peak temperature of desorbed water (a temperature at which a peak of a desorption spectrum of water appears) of 415 ° C. or lower based on a catalyst temperature-reduction method up to 450 ° C. Specific examples of the temperature raising reduction method will be described later. Usually, the sulfidation treatment is carried out by molybdenum or the like under a hydrogen stream to molybdenum, and the reaction requires desorption of oxygen from molybdenum oxide. Since the desorption peak of water is a detection of the desorption of oxygen from molybdenum oxide as water, it is considered that there is a correlation between the progress of the sulfidation treatment and the reduction temperature of molybdenum. Therefore, it is considered that the sulfuration treatment of molybdenum can be sufficiently advanced by lowering the peak temperature of the desorbed water.

If the reduction temperature is too high, that is, if the peak temperature of the desorbed water is too high, the water weakly interacts with the inorganic oxide carrier, and there is a possibility that an active metal aggregate may be present. Get higher. Therefore, it is presumed that the sulfurization step does not proceed sufficiently. Therefore, it is necessary to lower the reduction temperature and reduce the interaction between water and the inorganic oxide carrier in order to highly disperse the active metal.
The desorbed water is mainly generated in the step of reducing molybdenum, and its peak temperature changes according to the carrier composition, the active metal composition, and the like. According to the knowledge of the present inventors, in order to reduce the peak temperature of desorption of water (peak temperature of desorption water) to 415 ° C. or lower, at least one of molybdenum and tungsten as active metal components is placed on the inorganic oxide support. On the other hand, one (one) must be 15 to 30% by mass in terms of oxide, and at least one (one) of cobalt and nickel needs to be 3 to 7% by mass in terms of oxide.

  In the catalyst of the present invention, the NO (nitrogen monoxide) adsorption amount of the sulfurized catalyst is 8.0 ml / g or more. The adsorption amount is more preferably 8.3 ml / g or more, and still more preferably 9.0 ml / g or more. The reaction active point of the catalyst can be measured based on the NO molecule adsorption amount.

  The amount of NO adsorbed after the catalyst is sulfurized varies depending on the carrier composition, active metal composition, and the like, as does the peak temperature of desorbed water. In order to perform NO adsorption, a sulfidation treatment is required, so that it is necessary to lower the reduction temperature of the active metal to a certain temperature or lower. According to the knowledge of the present inventor, in order to make the adsorption amount of NO equal to or more than 8.0 ml / g, at least one of molybdenum and tungsten as an active metal component is converted into oxide on an inorganic oxide carrier. It is important that 15 to 30% by mass, at least one of cobalt and nickel is 3 to 7% by mass in terms of oxide, and the desorption peak temperature of water is 415 ° C. or lower.

[About the hydrotreating method of hydrocarbon oil]
The hydrocarbon oil to be desulfurized by the hydrotreating catalyst of the present invention is, for example, straight-run kerosene or straight-run gas oil obtained from a normal-pressure distillation unit for crude oil, and straight-run heavy oil obtained from a normal-pressure distillation unit. Hydrogenation of reduced-pressure gas oil or reduced-pressure heavy gas oil obtained by treating oil or residual oil with a reduced-pressure distillation device, catalytic cracking kerosene or catalytic cracked gas oil obtained by catalytic cracking of desulfurized heavy oil, reduced-pressure heavy gas oil or desulfurized heavy oil. Hydrocracked kerosene or hydrocracked gas oil obtained by cracking, pyrolyzed kerosene or pyrolyzed gas oil obtained from a pyrolysis apparatus such as a coker, etc., and a fraction having a boiling point of 180 to 390 ° C is 80% by volume or more. The distillate included. The hydrogenation treatment using the catalyst is performed under a high-temperature and high-pressure condition under a hydrogen atmosphere by filling a fixed-bed reactor with the catalyst.

[Production method of hydrotreating catalyst for hydrocarbon oil]
Next, a method for producing the hydrocarbon oil hydrotreating catalyst of the present invention will be described.

The method for producing a catalyst for hydrotreating hydrocarbon oil according to the present invention comprises:
A first step of preparing an inorganic oxide support containing aluminum;
Preparing an impregnation liquid containing a first metal component that is at least one of molybdenum and tungsten, a second metal component that is at least one of cobalt and nickel, and an organic acid; And a second step of supporting a second metal component on the inorganic oxide carrier,
Heat-treating the inorganic oxide carrier carrying the first metal component and the second metal component obtained at the second step at a temperature of 100 to 600 ° C. to obtain a hydrotreating catalyst; Have.
Hereinafter, each step will be described.

<First step>
First, an aqueous solution of a basic aluminum salt and an aqueous solution of an acidic aluminum salt are mixed so that the pH becomes 6.5 to 9.5, preferably 6.5 to 8.5, and more preferably 6.8 to 8.0. To obtain a hydrate of an inorganic oxide. After aging the slurry of the hydrate of the inorganic oxide by a desired method, it is washed to remove by-product salts, and contains hydrates containing alumina or other elements such as silicon other than alumina or alumina. Obtain a slurry. After the slurry of this hydrate is further heated and aged, for example, it is heated and kneaded by a conventional means to form a kneadable material, which is then molded into a desired shape by extrusion molding and the like. C., preferably 90-130.degree. C., and further preferably calcined at 400-800.degree. C., preferably 450-600.degree. C., for example 0.5-10 hours, preferably 2-5 hours to obtain an inorganic oxide. Obtain a carrier.

  When obtaining a hydrate of an inorganic composite oxide containing an element other than aluminum, depending on the pH of the metal salt to be used, after preliminarily mixing with an aqueous solution of an aluminum salt of an acidic aqueous solution or a basic aqueous solution, the pH is adjusted to the above-mentioned range. To obtain a hydrate of the inorganic composite oxide.

  As the basic aluminum salt, sodium aluminate, potassium aluminate and the like are 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. Particularly, titanium sulfate and titanyl sulfate are preferably used because they are inexpensive. Phosphate ions are also used as the phosphate source, and phosphate compounds that generate phosphate ions in water such as ammonium phosphate, potassium phosphate, sodium phosphate, phosphoric acid, and phosphorous acid are used. It is possible.

  When mixing the two kinds of aluminum salt aqueous solutions, the mixture is usually heated to 40 to 90 ° C., preferably 50 to 70 ° C., and kept at that temperature, and the temperature of this solution is ± 5 ° C., preferably ± 2 ° C., more preferably The mixed aqueous solution heated to ± 1 ° C. is added to a mixture of usually 5 to 20 so that the pH becomes 6.5 to 9.5, preferably 6.5 to 8.5, more preferably 6.5 to 8.0. Minutes, preferably between 7 and 15 minutes, to form a precipitate and obtain a hydrate slurry.

  Here, the time required for the addition of the mixed aqueous solution to the basic aluminum salt aqueous solution is not longer than 15 minutes because undesired crystals such as bayerite and gibbsite may be generated in addition to pseudo-boehmite when the time is long. 13 minutes or less is more desirable. Bayerite and gibbsite are not preferred because the specific surface area decreases when heat-treated.

<Second step>
The impregnating liquid containing the above-described first metal component, second metal component, and carbon component is brought into contact with the inorganic oxide carrier.
As a raw material of the first metal component, for example, molybdenum trioxide, ammonium molybdate, ammonium metatungstate, ammonium paratungstate, tungsten trioxide and the like are suitably used. As the raw material of the second metal component, nickel nitrate, nickel carbonate, cobalt nitrate, cobalt carbonate and the like are preferably used.
Further, when copper, magnesium or zinc is supported on an inorganic oxide carrier, for example, copper carbonate, magnesium carbonate, zinc carbonate or the like is used.
When phosphorus is supported on an inorganic oxide carrier, orthophosphoric acid (hereinafter, also simply referred to as “phosphoric acid”), ammonium dihydrogen phosphate, diammonium hydrogen phosphate, trimetaphosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, etc. Used.

The impregnating liquid is preferably adjusted to a pH of 4 or less using an organic acid to dissolve the metal component. If the pH exceeds 4, the stability of the dissolved metal component tends to decrease and precipitate. As the organic acid, for example, citric acid, malic acid, tartaric acid, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA) can be used, and citric acid and malic acid are particularly preferably used. Sugars (monosaccharides, disaccharides, polysaccharides, etc.) are used as organic additives. Organic additives such as glucose (glucose; C ₆ H ₁₂ O ₆ ), fructose (fructose; C ₆ H ₁₂ O ₆ ), maltose (maltose; C ₁₂ H ₂₂ O ₁₁ ), lactose (lactose; C ₁₂ H ₂₂ O ₁₁ ), sucrose (sucrose; C ₁₂ H ₂₂ O ₁₁ ) and the like may be added.

<Third step>
The carrier supporting the metal component obtained by being brought into contact with the impregnating liquid in the second step is heated at 100 to 600 ° C., preferably 105 to 550 ° C., more preferably 110 to 500 ° C., for 0.5 to 10 hours, preferably After the heat treatment for 1 to 8 hours, the hydrotreating catalyst of the present invention is produced. Here, if the firing temperature is excessively lower than 100 ° C., the operability due to residual moisture is deteriorated, and the metal carrying state may not be uniform. If the firing temperature is excessively higher than 600 ° C., the metal may aggregate and disperse. It is not preferable because the maintenance effect may not be expected.

[About measurement method]
As described below, for the hydrotreating catalysts in each of the examples and comparative examples of the present invention, the content of the components, the specific surface area and the numerical values relating to the properties are measured, and a method for performing these measurements is described. deep.
<Method for measuring the contents of carrier components (alumina, silica, phosphorus oxide, titania) and metal components (molybdenum, cobalt, nickel, copper, magnesium, phosphorus)>
3 g of a measurement sample is collected in a zirconia ball with a cap having a capacity of 30 ml, heated (200 ° C., 20 minutes), calcined (700 ° C., 5 minutes), and ₂ g of Na ₂ O ₂ and 1 g of NaOH are added thereto 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 obtain a sample. Using an ICP device (ICPS-8100, analysis software ICPS-8000, manufactured by Shimadzu Corporation), the content of each component of the obtained sample was converted into oxide conversion standard (Al ₂ O ₃ , SiO ₂ , P ₂₎ . ₂ O ₅ , TiO ₂ , MoO ₃ , NiO, CoO, MgO, CuO).

<Method for measuring specific surface area>
About 30 ml of the measurement sample was collected in a porcelain crucible (type B-2), heated at a temperature of 300 ° C. for 2 hours, cooled in a desiccator to room temperature, and a measurement sample was obtained. Next, 1 g of this sample was taken, and the specific surface area (m ² / g) of the sample was measured by a BET method using a fully automatic surface area measuring device (manufactured by Yuasa Ionics, Multisorb 12).

<Method for measuring ignition loss>
The catalyst, which is a measurement sample, is calcined at 570 ° C. for 2 hours, and calculated from the amount of mass loss due to the calcining.

<Method of measuring peak temperature of desorbed water by temperature-reduction method>
In the temperature-reduction method, 0.05 g of a catalyst sized to 250 to 710 μm was subjected to a pretreatment at 120 ° C. for 1 hour under a flow of helium gas using a catalyst analyzer (BEL CAT-A) manufactured by Nippon Bell. After the application, the gas was switched to hydrogen gas (99.99%), and the temperature was increased from 50 ° C. to 900 ° C. at a rate of 10 ° C./min. The desorption spectrum of water at the time of temperature rise was measured by a quadrupole mass spectrometer (m / z: 18.34) manufactured by Pfeiffer Vacuum Co., and the desorption peak temperature of water was read from the obtained desorption spectrum. Was.

  FIG. 1 shows a graph as an example of the analysis result of the peak temperature of the desorbed water by the temperature-reduction reduction method. In FIG. 1, the horizontal axis represents temperature, and the vertical axis represents detection current of the quadrupole mass spectrometer. The solid line (1) and the dashed line (2) in FIG. 1A correspond to Examples 6 and 8 described later, respectively, and the solid line (3) and the dashed line (4) in FIG. 1B correspond to Comparative Example 1 described later, respectively. And 5.

<Method of measuring NO adsorption amount>
The measurement of the NO adsorption amount is carried out by using a fully automatic catalytic gas adsorption amount measuring device (manufactured by Okura Riken), and applying a pulse of a mixed gas of helium gas and NO gas (NO concentration 10% by volume) to the sulfurized hydrogenation catalyst. Then, the amount of adsorbed NO molecules per 1 g of the hydrotreating catalyst was measured. Specifically, about 0.02 g of a catalyst pulverized to 60 mesh or less was weighed and charged in a quartz cell, and the catalyst was heated to 360 ° C. to obtain 5% by volume of hydrogen sulfide / 95% by volume of hydrogen. Was passed through at a flow rate of 0.2 liter / min to perform sulfuration treatment for 1 hour, and then kept at 340 ° C. for 1 hour to discharge physically adsorbed hydrogen sulfide out of the system. Thereafter, NO molecules were adsorbed at 50 ° C. with a mixed gas of helium gas and NO gas, and the NO molecule adsorption amount was measured.

[Example]
Preparation Examples of Inorganic Oxide Carriers, Preparation Examples of Impregnating Liquids, Preparation Examples of Hydrotreating Catalysts that are Examples of the Present Invention Using Each Inorganic Oxide Carrier and Impregnating Liquid, and Each Inorganic Oxide Carrier and Impregnation A preparation example of a hydrotreating catalyst which is a comparative example using a liquid is described below.
First, a preparation example of the inorganic oxide carrier will be described.
<Preparation of inorganic oxide carrier A>
8.95 kg of a 22 mass% aqueous sodium aluminate solution in terms of Al ₂ O ₃ concentration was put into a tank with a steam jacket having a capacity of 100 L (liter), diluted with 33 kg of ion-exchanged water, and then converted into P ₂ O ₅ concentration. 5.40 kg of a 2.5 mass% sodium phosphate solution was added with stirring, and the mixture was heated to 60 ° C. to prepare a basic aluminum salt aqueous solution. Further, an acidic aluminum salt aqueous solution obtained by diluting 12.79 kg of a 7 mass% aqueous aluminum sulfate solution in terms of Al ₂ O ₃ concentration with 23 kg of ion-exchanged water was heated to 60 ° C. The acidic aluminum salt aqueous solution is added to the tank containing the basic aluminum salt aqueous solution at a constant rate using a roller pump until the pH becomes 7.2 (addition time: 10 minutes), and hydration containing phosphorus and alumina is performed. A 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% by mass aqueous ammonia solution. The diluted cake-like slurry after washing was diluted with ion-exchanged water so as to have an Al ₂ O ₃ concentration of 10% by mass, and the pH was adjusted to 10.5 with 15% by mass aqueous ammonia. This was transferred to an aging tank equipped with a reflux machine, and aged at 95 ° C. for 10 hours while stirring. The slurry after aging was dewatered and concentrated and kneaded to a predetermined water content while kneading with a double-arm kneader equipped with a steam jacket. The obtained kneaded product was molded into a columnar shape having a diameter of 1.6 mm by an extrusion molding machine, and dried at 110 ° C. The dried molded product was fired in an electric furnace at a temperature of 500 ° C. for 3 hours to obtain a carrier A.

<Preparation of inorganic oxide carrier B>
In a tank with a capacity of 100 L equipped with a steam jacket, 9.23 kg of a 22 mass% aqueous sodium aluminate solution in terms of Al ₂ O ₃ concentration was put, diluted with 35 kg of ion-exchanged water, and then 2.5 P in terms of P ₂ O ₅ concentration. 1.80 kg of a mass% sodium phosphate solution was added with stirring, and the mixture was heated to 60 ° C. to prepare a basic aluminum salt aqueous solution. An acidic aluminum salt aqueous solution obtained by diluting 13.19 kg of a 7 mass% aluminum sulfate aqueous solution in terms of Al ₂ O ₃ concentration with 24 kg of ion-exchanged water was heated to 60 ° C. The acidic aluminum salt aqueous solution is added to the tank containing the basic aluminum salt aqueous solution at a constant rate using a roller pump until the pH becomes 7.2 (addition time: 10 minutes), and hydration containing phosphorus and alumina is performed. A product slurry B was prepared. The subsequent steps were performed in the same manner as in the case of the carrier A of Example 1 to obtain the carrier B.

<Preparation of inorganic oxide carrier C>
In a tank with a steam jacket having a capacity of 100 L, 9.38 kg of a 22 mass% sodium aluminate aqueous solution in terms of Al ₂ O ₃ concentration was put, diluted with 36 kg of ion-exchanged water, and heated to 60 ° C. An aluminum salt aqueous solution was prepared. In addition, an acidic aluminum salt aqueous solution obtained by diluting 13.39 kg of a 7 mass% aqueous aluminum sulfate solution in terms of Al ₂ O ₃ concentration with 24 kg of ion-exchanged water was heated to 60 ° C. A tank containing the basic aluminum salt solution, added at a constant rate until the pH is 7.2 to acidic aluminum salt aqueous solution by using a roller pump (addition time: 10 minutes), containing Alumina hydrate Slurry C was prepared. The subsequent steps were performed in the same manner as in the case of the carrier A of Example 1 to obtain the carrier C.

<Preparation of inorganic oxide carrier D>
In a tank having a capacity of 100 L and equipped with a steam jacket, 9.23 kg of a 22% by mass aqueous sodium aluminate solution in terms of Al ₂ O ₃ concentration was added, diluted with 36 kg of ion-exchanged water, and heated to 60 ° C. An aluminum salt aqueous solution was prepared. Also, 1 kg of an acidic aluminum salt aqueous solution obtained by diluting 13.19 kg of a 7 mass% aluminum sulfate aqueous solution in terms of Al ₂ O ₃ concentration with 24 kg of ion exchange water, and 0.14 kg of 33 mass% titanium sulfate in terms of TiO ₂ concentration in 1 kg. Was mixed with an aqueous solution of titanium sulfate dissolved in ion-exchanged water and heated to 60 ° C. to prepare a mixed aqueous solution. A hydrate slurry containing titania and alumina was added to the tank containing the basic aluminum salt aqueous solution at a constant rate using a roller pump until the pH reached 7.2 (addition time: 10 minutes). D was prepared. The subsequent steps were performed in the same manner as in the case of the carrier A of Example 1 to obtain the carrier D.

<Preparation of inorganic oxide carrier E>
A tank with a capacity of 100 L equipped with a steam jacket was charged with 8.44 kg of a 22 mass% sodium aluminate aqueous solution in terms of Al ₂ O ₃ concentration, diluted with 35 kg of ion-exchanged water, and heated to 60 ° C. An aluminum salt aqueous solution was prepared. Further, 6 kg of an acidic aluminum salt aqueous solution obtained by diluting 12.05 kg of a 7 mass% aqueous aluminum sulfate solution in terms of Al ₂ O ₃ concentration with 22 kg of ion-exchanged water, and 0.91 kg of 33 mass% titanium sulfate in terms of TiO ₂ concentration as 6 kg Was mixed with an aqueous solution of titanium sulfate dissolved in ion-exchanged water and heated to 60 ° C. to prepare a mixed aqueous solution. A hydrate slurry containing titania and alumina was added to the tank containing the basic aluminum salt aqueous solution at a constant rate using a roller pump until the pH reached 7.2 (addition time: 10 minutes). E was prepared. The subsequent steps were performed in the same manner as in the case of the carrier A of Example 1 to obtain the carrier E.

<Preparation of inorganic oxide carrier F>
A tank with a capacity of 100 L equipped with a steam jacket was charged with 7.50 kg of a 22 mass% sodium aluminate aqueous solution in terms of Al ₂ O ₃ concentration, diluted with 34 kg of ion-exchanged water, and then heated to 60 ° C. An aluminum salt aqueous solution was prepared. Further, 12 kg of an acidic aluminum salt aqueous solution obtained by diluting 10.71 kg of a 7 mass% aqueous aluminum sulfate solution in terms of Al ₂ O ₃ concentration with 19 kg of ion exchange water, and 1.82 kg of 33 mass% titanium sulfate in terms of TiO ₂ concentration as 12 kg Was mixed with an aqueous solution of titanium sulfate dissolved in ion-exchanged water and heated to 60 ° C. to prepare a mixed aqueous solution. A hydrate slurry containing titania and alumina was added to the tank containing the basic aluminum salt aqueous solution at a constant rate using a roller pump until the pH reached 7.2 (addition time: 10 minutes). F was prepared. The subsequent steps were performed in the same manner as in the case of the carrier A of Example 1 to obtain the carrier F.

<Preparation of inorganic oxide carrier G>
Into a tank having a capacity of 100 L equipped with a steam jacket, 9.09 kg of a 22 mass% aqueous sodium aluminate solution in terms of Al ₂ O ₃ concentration was added, diluted with 35 kg of ion-exchanged water, and then 2.5 P in terms of P ₂ O ₅ concentration. 1.80 kg of a mass% sodium phosphate solution was added with stirring, and the mixture was heated to 60 ° C. to prepare a basic aluminum salt aqueous solution. Further, an acidic aluminum salt aqueous solution obtained by diluting 12.99 kg of a 7 mass% aluminum sulfate aqueous solution in terms of Al ₂ O ₃ concentration with 23 kg of ion-exchanged water and 0.14 kg of 33 mass% titanium sulfate in terms of TiO ₂ concentration as 0.1%. An aqueous solution of titanium sulfate dissolved in 9.9 kg of ion-exchanged water was mixed and heated to 60 ° C. to prepare a mixed aqueous solution. The mixed aqueous solution was added to the tank containing the basic aluminum salt aqueous solution at a constant rate using a roller pump until the pH reached 7.2 (addition time: 10 minutes), and hydration containing phosphorus, titania, and alumina was performed. A product slurry G was prepared. The subsequent steps were performed in the same manner as in the case of the carrier A of Example 1 to obtain the carrier G.

<Preparation of inorganic oxide carrier H>
Into a tank with a capacity of 100 L equipped with a steam jacket, 9.09 kg of a 22 mass% aqueous sodium aluminate solution in terms of Al ₂ O ₃ concentration was put, diluted with 35 kg of ion-exchanged water, and 5 mass% of silicic acid in terms of SiO ₂ concentration was diluted. 0.90 kg of the sodium solution and 1.80 kg of a sodium phosphate solution of 2.5% by mass in terms of P ₂ O ₅ concentration were added with stirring, and the mixture was heated to 60 ° C. to prepare a basic aluminum salt aqueous solution. Further, an aqueous solution of acidic aluminum salt obtained by diluting 12.99 kg of an aluminum sulfate aqueous solution of 7 mass% in terms of Al ₂ O ₃ concentration with 23 kg of ion-exchanged water was heated to 60 ° C. to prepare a mixed aqueous solution. The mixed aqueous solution was added to the tank containing the basic aluminum salt aqueous solution at a constant rate using a roller pump until the pH reached 7.2 (addition time: 10 minutes), and hydration containing phosphorus, silica, and alumina was performed. A product slurry H was prepared. The subsequent steps were performed in the same manner as in the case of the carrier A of Example 1 to obtain the carrier H.

<Preparation of inorganic oxide carrier I>
Into a tank with a steam jacket having a capacity of 100 L, 9.05 kg of a 22 mass% sodium aluminate aqueous solution in terms of Al ₂ O ₃ concentration was put, diluted with 35 kg of ion-exchanged water, and 5 mass% of silicic acid in terms of SiO ₂ concentration was diluted. 0.90 kg of the sodium solution and 1.80 kg of a sodium phosphate solution of 2.5% by mass in terms of P ₂ O ₅ concentration were added with stirring, and the mixture was heated to 60 ° C. to prepare a basic aluminum salt aqueous solution. Further, 0.12 kg of an acidic aluminum salt aqueous solution obtained by diluting 12.92 kg of a 7 mass% aluminum sulfate aqueous solution in terms of Al ₂ O ₃ concentration with 23 kg of ion exchange water, and 0.14 kg of 33 mass% titanium sulfate in terms of TiO ₂ concentration as 0%. An aqueous solution of titanium sulfate dissolved in 9.9 kg of ion-exchanged water was mixed and heated to 60 ° C. to prepare a mixed aqueous solution. The mixed aqueous solution is added to the tank containing the basic aluminum salt aqueous solution at a constant rate using a roller pump until the pH becomes 7.2 (addition time: 10 minutes), and contains silica, phosphorus, titania, and alumina. A hydrate slurry I was prepared. The subsequent steps were performed in the same manner as in the case of the carrier A of Example 1 to obtain the carrier I.

<Preparation of inorganic oxide carrier J>
A tank with a capacity of 100 L equipped with a steam jacket was charged with 7.50 kg of a 22 mass% sodium aluminate aqueous solution in terms of Al ₂ O ₃ concentration, diluted with 34 kg of ion-exchanged water, and then heated to 60 ° C. An aluminum salt aqueous solution was prepared. Further, 12 kg of an acidic aluminum salt aqueous solution obtained by diluting 10.71 kg of a 7 mass% aqueous aluminum sulfate solution in terms of Al ₂ O ₃ concentration with 19 kg of ion-exchanged water and 1.80 kg of 33 mass% titanium sulfate in terms of TiO ₂ concentration as 12 kg Was mixed with an aqueous solution of titanium sulfate dissolved in ion-exchanged water and heated to 60 ° C. to prepare a mixed aqueous solution. A hydrate slurry containing titania and alumina was added to the tank containing the basic aluminum salt aqueous solution at a constant rate using a roller pump until the pH reached 7.2 (addition time: 10 minutes). J was prepared. The subsequent steps were performed in the same manner as in the case of the carrier A of Example 1 to obtain the carrier J.

<Preparation of inorganic oxide carrier K>
A tank with a capacity of 100 L equipped with a steam jacket was charged with 4.09 kg of a 22% aqueous sodium aluminate solution in terms of Al ₂ O ₃ concentration, diluted with 25 kg of ion-exchanged water, and then 5% by weight of silicic acid in terms of SiO ₂ concentration. A sodium solution (30.00 kg) was added with stirring, and the mixture was heated to 60 ° C. to prepare a basic aluminum salt aqueous solution. Also, an acidic aluminum salt aqueous solution obtained by diluting 8.57 kg of a 7 mass% aluminum sulfate aqueous solution in terms of Al ₂ O ₃ concentration with 15 kg of ion-exchanged water was heated to 60 ° C. to prepare a mixed aqueous solution. A hydrate slurry containing silica and alumina was added to the tank containing the basic aluminum salt aqueous solution at a constant rate using a roller pump until the pH reached 7.2 (addition time: 10 minutes). K was prepared. Subsequent steps were performed in the same manner as in the case of the carrier A of Example 1 to obtain the carrier K.

<Preparation of inorganic oxide carrier L>
2.15 kg of a 22 mass% aqueous sodium aluminate solution in terms of Al ₂ O ₃ concentration was put into a tank with a steam jacket having a capacity of 100 L, diluted with 25 kg of ion-exchanged water, and then silicic acid of 5 mass% in terms of SiO ₂ concentration was added. A sodium solution (30.0 kg) was added with stirring, and the mixture was heated to 60 ° C. to prepare a basic aluminum salt aqueous solution. Further, an aqueous solution of an acidic aluminum salt obtained by diluting 3.97 kg of a 7 mass% aqueous aluminum sulfate solution in terms of Al ₂ O ₃ concentration with 7 kg of ion-exchanged water, and 2.27 kg of 33 mass% titanium sulfate in terms of TiO ₂ concentration of 7 wt. An aqueous solution of titanium sulfate dissolved in 0.1 kg of ion-exchanged water was mixed and heated to 60 ° C. to prepare a mixed aqueous solution. The mixed aqueous solution was added to the tank containing the basic aluminum salt aqueous solution at a constant rate using a roller pump until the pH reached 7.2 (addition time: 10 minutes), and the hydration containing silica, titania and alumina was added. A product slurry L was prepared. The subsequent steps were performed in the same manner as in the case of the carrier A of Example 1 to obtain the carrier L.

<Preparation of inorganic oxide carrier M>
The carrier A obtained in the same manner as in Example 1 was dried at 110 ° C., and then calcined in an electric furnace at 800 ° C. and calcined for 3 hours to obtain a carrier M.

Next, an example of adjusting the impregnating liquid will be described.
<Preparation of impregnating liquid a>
282 g of molybdenum trioxide, 56 g of cobalt carbonate and 54 g of nickel carbonate are suspended in 800 ml of ion-exchanged water, and the suspension is heated at 95 ° C. for 5 hours by applying a suitable refluxing device so that the liquid volume does not decrease. And 84 g of citric acid were added and dissolved to prepare impregnation liquid a.

<Preparation of impregnating liquid b>
333 g of molybdenum trioxide, 56 g of cobalt carbonate and 43 g of nickel carbonate are suspended in 800 ml of ion-exchanged water, and this suspension is heated at 95 ° C. for 5 hours by applying a suitable reflux device so that the liquid volume does not decrease. , 23 g of phosphoric acid and 120 g of citric acid were added and dissolved to prepare an impregnating solution b.

<Preparation of impregnation liquid c>
329 g of molybdenum trioxide, 131 g of cobalt carbonate and 13 g of copper carbonate are suspended in 800 ml of ion-exchanged water, and the suspension is heated at 95 ° C. for 5 hours with a suitable refluxing device so that the liquid volume does not decrease. And 23 g of phosphoric acid and 118 g of citric acid were added and dissolved to prepare an impregnation liquid c.

<Preparation of impregnating liquid d>
331 g of molybdenum trioxide, 132 g of cobalt carbonate and 14 g of nickel carbonate are suspended in 800 ml of ion-exchanged water, and this suspension is heated at 95 ° C. for 5 hours by applying a suitable refluxing device so that the liquid volume does not decrease. And 35 g of phosphoric acid and 119 g of citric acid were added and dissolved to prepare an impregnating liquid d.

<Preparation of impregnation liquid e>
331 g of molybdenum trioxide and 132 g of cobalt carbonate are suspended in 800 ml of ion-exchanged water, and this suspension is heated at 95 ° C. for 5 hours with a suitable reflux device so that the liquid volume does not decrease. And 119 g of citric acid were added and dissolved to prepare an impregnation liquid e.

<Preparation of impregnation liquid f>
294 g of molybdenum trioxide, 105 g of cobalt carbonate and 25 g of copper carbonate are suspended in 800 ml of ion-exchanged water, and this suspension is heated at 95 ° C. for 5 hours by applying a suitable reflux device so that the liquid volume does not decrease. And 45 g of phosphoric acid and 94 g of citric acid were added and dissolved to prepare an impregnation liquid f.

<Preparation of impregnating liquid g>
294 g of molybdenum trioxide, 105 g of cobalt carbonate and 33 g of magnesium carbonate are suspended in 800 ml of ion-exchanged water, and the suspension is heated at 95 ° C. for 5 hours with a suitable refluxing device so as not to reduce the liquid volume. , 45 g of phosphoric acid and 94 g of citric acid were added and dissolved to prepare an impregnating solution g.

<Preparation of impregnating liquid h>
454 g of molybdenum trioxide, 170 g of cobalt carbonate and 49 g of nickel carbonate are suspended in 800 ml of ion-exchanged water, and the suspension is heated at 95 ° C. for 5 hours with a suitable refluxing device so that the liquid volume does not decrease. , 65 g of phosphoric acid and 153 g of citric acid were added and dissolved to prepare an impregnating liquid h.

<Preparation of impregnation liquid i>
186 g of molybdenum trioxide and 70 g of cobalt carbonate are suspended in 800 ml of ion-exchanged water, and this suspension is heated at 95 ° C. for 5 hours with a suitable refluxing device so that the liquid volume does not decrease, and then 20 g of phosphoric acid And 63 g of citric acid were added and dissolved to prepare an impregnation liquid i.

<Preparation of impregnation liquid j>
282 g of molybdenum trioxide and 101 g of cobalt carbonate are suspended in 800 ml of ion-exchanged water, and this suspension is heated at 95 ° C. for 5 hours with a suitable refluxing device so that the liquid volume does not decrease. Was added and dissolved to prepare an impregnation liquid j.

<Preparation of impregnation liquid k>
324 g of molybdenum trioxide and 141 g of cobalt carbonate are suspended in 800 ml of ion-exchanged water, and this suspension is heated at 95 ° C. for 5 hours with a suitable reflux device so that the liquid volume does not decrease. Was added and dissolved to prepare an impregnation liquid k.

<Preparation of impregnation liquid 1>
231 g of molybdenum trioxide and 85 g of cobalt carbonate are suspended in 800 ml of ion-exchanged water, and this suspension is heated at 95 ° C. for 5 hours with a suitable reflux device so that the liquid volume does not decrease. Was added and dissolved to prepare an impregnating liquid 1.

<Preparation of impregnation liquid m>
287 g of molybdenum trioxide and 66 g of cobalt carbonate are suspended in 800 ml of ion-exchanged water, and this suspension is heated at 95 ° C. for 5 hours with a suitable reflux device so that the liquid volume does not decrease. And 59 g of citric acid were added and dissolved to prepare an impregnating liquid m.

<Preparation of impregnating liquid n>
238 g of molybdenum trioxide, 66 g of cobalt carbonate and 40 g of nickel carbonate were suspended in 800 ml of ion-exchanged water, and this suspension was heated at 95 ° C. for 5 hours by applying a suitable reflux device so as not to reduce the liquid volume. Thereafter, 43 g of phosphoric acid and 60 g of citric acid were added and dissolved to prepare an impregnating liquid n.

<Preparation of impregnation liquid o>
234 g of molybdenum trioxide, 65 g of cobalt carbonate, and 26 g of nickel carbonate were suspended in 800 ml of ion-exchanged water, and this suspension was heated at 95 ° C. for 5 hours with a suitable reflux device so that the liquid volume did not decrease. Thereafter, 21 g of phosphoric acid and 58 g of citric acid were added and dissolved to prepare an impregnation liquid o.

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples.
<Example 1: Preparation of hydrodesulfurization catalyst>
After impregnating liquid a is spray-impregnated into 1000 g of the support A, the impregnating liquid a is dried at 200 ° C., and further calcined at 450 ° C. for 1 hour in an electric furnace to obtain a hydrotreating catalyst (hereinafter, also simply referred to as “catalyst”. The same applies to the above.)
<Examples 2 to 17: Preparation of hydrodesulfurization catalyst>
The types of carriers (preparation examples) adjusted as described above and the types of impregnating liquids (preparation examples) were combined as shown in Table 1 described below, and the others were the same as in Example 1, and The catalyst of Example 17 was prepared.

Next, a comparative example will be described.
<Comparative Example 1: Preparation of hydrodesulfurization catalyst>
Using the impregnating liquid e of Example 6 as the impregnating liquid, 1000 g of the carrier C prepared in Example 5 was spray-impregnated, dried at 120 ° C., and then calcined to obtain a hydrotreated catalyst.
<Comparative Example 2: Preparation of hydrodesulfurization catalyst>
Using the impregnating liquid e of Example 6 as the impregnating liquid, 1000 g of the carrier B prepared in Example 3 was spray-impregnated, dried at 120 ° C., and then calcined to obtain a hydrotreated catalyst <Comparative Example 3> Comparative Example 10: Preparation of Hydrodesulfurization Catalyst>
The type of carrier (Preparation Example) adjusted as described above and the type of impregnating solution (Preparation Example) were combined as shown in Table 1 below, and the others were the same as in Example 1, and Comparative Examples 3 to The catalyst of Example 10 was prepared.

  Table 1 shows the properties of each carrier in Examples 1 to 17 and Comparative Examples 1 to 10 obtained as described above, and Table 2 shows the properties of each catalyst. In Table 1, the specific surface area indicates the specific surface area of the catalyst. In Table 2, the supported amounts (% by mass) of each element are catalyst-based values as described above. The supported amounts of the oxides of Ni, Cu, and Mg in Table 2 are shown in the column on the right of the column showing the oxides. The carbon content is also a value based on the catalyst.

＜触媒の評価＞
（評価のための確認試験）
実施例１〜１７及び比較例１〜１０の各触媒について、触媒性能と触媒再生性能とについて評価した。
（１）触媒性能の評価のための確認試験
各触媒を固定床反応装置に充填し、触媒に含まれている酸素原子を脱離させて活性化するために、予備硫化処理した。この処理は、硫黄化合物を含む液体または気体を２００℃〜４００℃の温度、常圧〜１００ＭＰaの水素圧雰囲気下の管理された反応容器中で流通させることによって行われる。

<Evaluation of catalyst>
(Confirmation test for evaluation)
For each of the catalysts of Examples 1 to 17 and Comparative Examples 1 to 10, the catalyst performance and the catalyst regeneration performance were evaluated.
(1) Confirmation test for evaluating catalyst performance
Each catalyst was packed in a fixed-bed reactor and subjected to a pre-sulfurization treatment in order to desorb and activate oxygen atoms contained in the catalyst. This treatment is performed by flowing a liquid or gas containing a sulfur compound in a controlled reaction vessel at a temperature of 200 ° C. to 400 ° C. and a hydrogen pressure atmosphere of normal pressure to 100 MPa.

Then, straight-run gas oil (density 0.8468 g / cm ^{3 at} 15 ° C., sulfur content 1.13% by mass, nitrogen content 0.083% by mass) was fed into the fixed bed flow reactor at a rate of 150 ml / hour. Then, hydrodesulfurization treatment was performed, and hydrorefining was performed. The reaction conditions at that time are a hydrogen partial pressure of 4.5 MPa, a liquid hourly space velocity of 1.0 h ⁻¹ , and a hydrogen oil ratio of 250 Nm ³ / kl. Then, the reaction temperature was changed within the range of 300 to 385 ° C., and the sulfur in the refined oil was analyzed at each temperature to determine the temperature at which the sulfur content in the refined oil was 8 ppm.

(2) Confirmation test for evaluation of catalyst regeneration performance
The regeneration of the catalyst was performed using the following method. 100 g of the used catalyst extracted after the reaction was placed in a nitrogen atmosphere maintained at 200 ° C. to remove oil adhering to the surface. Thereafter, calcination was carried out in an air atmosphere while controlling the temperature of the catalyst at 400 to 450 ° C. until the carbon content became 1% by weight or less. After calcination, the catalyst was cooled and used again for the activity test.

The method of calculating the performance after reproduction is as follows. As for the test results in the activity test, a reaction rate constant was obtained from an Arrhenius plot, and a regeneration rate from a fresh catalyst (unused catalyst) was calculated. Specifically, after the sulfuration treatment was performed by flowing hydrogen sulfide, the hydrodesulfurization treatment was performed under the conditions described in the above (1). From the change in the sulfur concentration in the hydrocarbon oil before and after passing through the reactor, a reaction rate constant was determined based on the following equation 1. Then, on the reaction rate constant of the unused catalyst _{(K n0),} the value of the ratio expressed in percentage of the reaction rate constant (Kn) of the regenerated catalyst _{((K n / K n0)} × 100 [%]) of the relative activity And
K _n = LHSV × 1 / (n−1) × (1 / S ⁿ⁻¹ −1 / S ₀ ⁿ⁻¹ ) Equation 1
here,
K _n: reaction rate constant
n: how many times the desulfurization reaction rate is proportional to the sulfur concentration of the feedstock oil (1.5 for LGO)
S: Sulfur concentration in treated oil (%)
S ₀ : Sulfur concentration in feed oil (%)
LHSV: liquid hourly space velocity (hr ^-1 )
Table 3 shows the results of the above confirmation tests.

（触媒の性状及び確認試験の評価結果）
実施例１〜１７は、触媒の性状に関してすべて適切な値になっている。これに対して、比較例１及び２は、脱離水のピーク温度が適切値の上限である４１５℃を越えており、強熱減量が適切値の上限である５重量％を大幅に大きく越えており、含有している炭素量も適切値の上限である２重量％を越えている。比較例３及び７は、４５０℃以下及び９００℃以下の各々における脱離水のピーク温度が４１５℃を越えており、比較例５は、９００℃以下における脱離水のピーク温度が４１５℃を越えている。また比較例４及び７は、ＮＯ吸着量が適切値の下限である８．０ｍｌ／ｇを下回っており、比較例８及び９は、４５０℃以下及び９００℃以下の各々における脱離水のピーク温度が４１５℃を越えており、更にＮＯ吸着量が８．０ｍｌ／ｇを下回っている。

(Evaluation results of catalyst properties and confirmation tests)
Examples 1 to 17 all have appropriate values with regard to the properties of the catalyst. On the other hand, in Comparative Examples 1 and 2, the peak temperature of the desorbed water exceeded the upper limit of the appropriate value of 415 ° C., and the ignition loss significantly exceeded the upper limit of the appropriate value of 5% by weight. Therefore, the amount of carbon contained exceeds the upper limit of an appropriate value of 2% by weight. In Comparative Examples 3 and 7, the peak temperature of the desorbed water at 450 ° C. or lower and 900 ° C. or lower exceeded 415 ° C., and in Comparative Example 5, the peak temperature of the desorbed water at 900 ° C. or lower exceeded 415 ° C. I have. In Comparative Examples 4 and 7, the NO adsorption amount was lower than the lower limit of the appropriate value of 8.0 ml / g, and in Comparative Examples 8 and 9, the peak temperatures of desorbed water at 450 ° C. or lower and 900 ° C. or lower, respectively. Is higher than 415 ° C., and the NO adsorption amount is lower than 8.0 ml / g.

  In Examples 1 to 17, the temperature at which the sulfur content in the refined oil is 8 ppm, which is an index of the catalyst performance, is 360 ° C. or less, and the relative activity, which is the index of the catalyst regeneration performance, is 80% or more. . On the other hand, Comparative Examples 1 and 2 are inferior in catalyst regeneration performance, Comparative Examples 4 to 10 are inferior in catalyst performance, and Comparative Example 3 is inferior in both catalyst performance and catalyst regeneration performance.

  INDUSTRIAL APPLICABILITY The hydrodesulfurization catalyst of the present invention is extremely useful in industry because it can highly hydrodesulfurize a hydrocarbon oil.

Claims (7)

(1) As an active metal component, a first metal component that is at least one of molybdenum and tungsten and a second metal component that is at least one of cobalt and nickel are provided on the inorganic oxide support. Carried,
(2) The content of the first metal component is 15 to 30 parts by mass in terms of oxide with respect to 100 parts by mass of the catalyst, and the content of the second metal component is 100 parts by mass of the catalyst. And 3 to 7 parts by mass in terms of oxide, and carbon derived from an organic acid is 2.0 parts by mass or less on an element basis with respect to 100 parts by mass of the catalyst.
(3) The specific surface area of the catalyst is 140 to 350 m ² / g, the average pore diameter of the catalyst measured by a mercury intrusion method is 50 to 130 °,
(4) The peak temperature of desorbed water up to 450 ° C. based on the temperature-reduction method of the catalyst is less than 5.0% and the peak temperature of desorbed water is less than 412.0 ° C. The amount of adsorption is 8.0 ml / g or more;
A hydrotreating catalyst for hydrocarbon oils, characterized in that:   2. The catalyst for hydrotreating hydrocarbon oil according to claim 1, wherein the inorganic oxide carrier contains 80 to 100 parts by mass of aluminum in terms of alumina based on 100 parts by mass of the inorganic oxide carrier. 3. 3. The catalyst for hydrotreating hydrocarbon oil according to claim 1, wherein the inorganic oxide carrier corresponds to at least one of the following (1) to (3). 4.
(1) Phosphorus contains 5.0 parts by mass or less of phosphorus in terms of phosphoric acid with respect to 100 parts by mass of the inorganic oxide carrier.
(2) Titanium is contained in an amount of 20.0 parts by mass or less based on 100 parts by mass of the inorganic oxide carrier.
(3) Silicon is contained in an amount of 2.0 parts by mass or less in terms of silica with respect to 100 parts by mass of the inorganic oxide carrier.   The active metal component contains molybdenum and cobalt, and further contains at least one of nickel, copper, magnesium, and zinc in an amount of 0 to 3.0 parts by mass in terms of oxide based on 100 parts by mass of the catalyst. The catalyst for hydrotreating hydrocarbon oil according to any one of claims 1 to 3, wherein   5. The hydrocarbon according to claim 1, wherein the catalyst has a maximum peak temperature of desorbed water in a range up to 900 ° C. of 415 ° C. or lower, based on a temperature-reduction method. 6. Oil hydrotreating catalyst. A method for producing a hydrocarbon oil hydrotreating catalyst according to any one of claims 1 to 5,
(1) a step of preparing an inorganic oxide carrier containing aluminum;
(2) preparing an impregnation liquid containing a first metal component that is at least one of molybdenum and tungsten, a second metal component that is at least one of cobalt and nickel, and an organic acid; Supporting a metal component and a second metal component on the inorganic oxide carrier,
(3) A hydrotreating catalyst obtained by heat-treating the inorganic oxide carrier carrying the first metal component and the second metal component obtained in the step (2) at a temperature of 100 to 600 ° C. Obtaining a
A method for producing a hydrotreating catalyst, comprising: A condition in which a hydrogen partial pressure is 3 to 8 MPa, a temperature is 300 to 420 ° C., and a liquid hourly space velocity is 0.3 to 5 hr ^{−1 in} the presence of the hydrotreating catalyst according to any one of claims 1 to 5. in hydrotreating a hydrocarbon oil which is characterized in that the hydrotreating of a hydrocarbon oil.

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