JP6909879B2 - Hydrodesulfurization catalyst for hydrocarbon oil, its production method, and hydrodesulfurization method - Google Patents

Description

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

In petroleum refining processes, a wide variety of hydrogenation catalysts are used for the purpose of removing impurities such as sulfur and nitrogen in hydrocarbon oils. However, in recent years when environmental protection is required on a global scale, regulations on the sulfur content of refined hydrocarbon oils are becoming stricter. In particular, reducing the sulfur content of light oil has become a major issue in order to further reduce harmful substances contained in automobile exhaust gas. This is because precious metals and basic oxides used as catalyst materials for exhaust gas treatment equipment are easily poisoned by sulfur. For this reason, in Japan, liquid fuels such as light oil and gasoline have been made sulfur-free by reducing the sulfur content to 10 ppm or less, and along with this, high-performance catalysts with high desulfurization performance have been developed for hydrogenation treatment catalysts. It has been.

Usually, in order to desulfurize a hydrocarbon oil, a treatment of hydrodesulfurizing the hydrocarbon oil under high temperature and high pressure reaction conditions is performed in a hydrogen stream in a fixed bed reaction tower filled with a hydrodesulfurization catalyst. As the hydrodesulfurization catalyst used in this treatment, a catalyst having high desulfurization performance that can comply with environmental regulations is required, and a catalyst in which an active metal such as molybdenum or cobalt is supported on a carrier such as alumina is widely used.

It is known that in order to increase the activity of the hydrogenation catalyst, it is important to satisfactorily control the interaction between the carrier and the active layer precursor during the preparation of the catalyst. According to Non-Patent Document 1, it is reported that the desulfurization activity per unit active point is higher in the carbon carrier than in the alumina carrier and the silica carrier. However, the carbon carrier has many problems in industrial use in terms of low bulk density and physical properties of the carrier such as catalytic activity, and there are few examples of being generally used.

On the other hand, studies on a catalyst using a carrier containing carbon have been widely conducted, and Patent Document 1 states that the carrier contains 0.5 to 2.6% by weight of carbon ^{when the specific surface area of the carrier is less than 150 m 2 / g.} It is described that it shows higher desulfurization activity. However, when the above method is ^{applied to a carrier having a high specific surface area of 150 m 2} / g or more, no improvement in desulfurization activity is observed due to an increase in carbon content. Therefore, this catalyst has a smaller specific surface area than a general industrial catalyst, and there is room for improvement in terms of performance.

Japanese Patent No. 4547922

S.M.A.M. Bouwens et al., Journal of Catalysis, 146, 375-393, (1994).

An object of the present invention is to provide a hydrodesulfurization catalyst for a hydrocarbon oil having excellent desulfurization activity and a method for producing the same. Another object of the present invention is to provide a method for hydrodesulfurizing a hydrocarbon oil, which can remove sulfur and nitrogen in the hydrocarbon oil with a high removal rate.

The hydrodesulfurization catalyst for the hydrocarbon oil of the present invention comprises at least one of molybdenum and tungsten, a first metal component, and at least one second metal component selected from Group VIII of the Periodic Table. The ratio of the content [MO] of the second metal component in terms of oxide (MO) to the content [MOx] of the first metal component in terms of oxide (MOx) ([MO] / [MOx] ) is the impregnating solution is 0.13 or more, is obtained by contacting an inorganic oxide carrier containing aluminum carbide containing a first metal component, and the second metal component, and carbon component, the It is a hydrodesulfurization catalyst for hydrogen oil.
(A) The specific surface area of the inorganic oxide carrier is in the range of ^{200 to 400 m 2 / g.}
(B) The ratio ([C] / [MOx]) of the content [C] of the carbon component to the oxide (MOx) -equivalent content [MOx] of the first metal component is 0.10 to 0. In the range of .40,
(C) The ratio (A / B) of the absorbance A of the spectral peak in the range of ^{1400 to 1800 cm -1} and the absorbance B of the spectral peak in the range ^{of 850 to 850 cm -1 was} determined by Raman analysis using a 532 nm wavelength laser. 1.0 or higher
(D) The source of the carbon component is two or more kinds of organic acids, or a group of organic compounds composed of an organic acid and an organic additive.
The inorganic oxide carrier does not contain boria as an active ingredient.
It is characterized by that.

Specific examples of the present invention are listed below, but the scope of the present invention is not limited.
The inorganic oxide carrier is an aluminum oxide or an inorganic composite oxide composed of aluminum and at least one element selected from titanium, silicon, phosphorus, zirconium and magnesium.
The metal component selected from Group VIII of the Periodic Table is selected from cobalt and nickel.
The metal component is in the range of 5 to 40 parts by mass with respect to 100 parts by mass of the hydrodesulfurization carrier. The form of the oxide of Group VIII of the periodic table is, for example, NiO or CoO .

The method for producing a hydrodesulfurization catalyst for a hydrocarbon oil of the present invention comprises an inorganic oxide carrier containing aluminum, a first metal component which is at least one of molybdenum and tungsten, and at least one selected from Group VIII of the Periodic Table. It consists of a second metal component of the seed and a carbon component,
(A) The specific surface area of the inorganic oxide carrier is in the range of ^{200 to 400 m 2 / g.}
(B) The ratio ([C] / [MOx]) of the content [C] of the carbon component to the oxide (MOx) -equivalent content [MOx] of the first metal component is 0.10 to 0. In the range of .40,
(C) The ratio (A / B) of the absorbance A of the spectral peak in the range of ^{1400 to 1800 cm -1} and the absorbance B of the spectral peak in the range ^{of 850 to 850 cm -1 was} determined by Raman analysis using a 532 nm wavelength laser. 1.0 or higher
(D) The inorganic oxide carrier does not contain boria as an active ingredient.
A method for producing a hydrodesulfurization catalyst for hydrocarbon oil.
(1) Step of preparing an inorganic oxide carrier containing aluminum,
(2) A first metal component that is at least one of molybdenum and tungsten, at least one second metal component selected from Group VIII of the Periodic Table, and two or more organic acids or organic acids. The second metal component selected from Group VIII of the Periodic Table with respect to the content [MOx] of the first metal component in terms of oxide (MOx) , which includes an organic compound group consisting of and an organic additive. The step of contacting the impregnated liquid having a ratio ([MO] / [MOx]) of the content [MO] in terms of oxide (MO) of 0.13 or more to the inorganic oxide carrier.
(3) A step of heat-treating the carrier obtained in the step (2) above to obtain a hydrodesulfurization catalyst.
It is characterized by having.

The hydrodesulfurization catalyst of the hydrocarbon oil of the present invention supports an active metal and carbon on an inorganic oxide carrier containing aluminum, and controls the mass ratio and morphology of the active metal and carbon. It is considered that a network structure made of carbon is formed by this control, and the active metal is highly dispersed in this network structure. As demonstrated in the examples described later, the hydrodesulfurization catalyst exhibits high desulfurization activity. be able to. Further, the hydrodesulfurization catalyst of the hydrocarbon oil of the present invention can stably obtain a long service life.
Further, according to the method for producing a hydrodesulfurization catalyst for a hydrocarbon oil of the present invention, an impregnating solution having an appropriate mass ratio of active metal and carbon is brought into contact with the carrier, so that hydrodesulfurization having excellent desulfurization activity is achieved. Can produce catalysts.
Further, by using the hydrodesulfurization catalyst of the hydrocarbon oil of the present invention, it is possible to provide a method for hydrodesulfurizing a hydrocarbon oil having high desulfurization activity.

It is a graph which shows an example of the Raman analysis result of the catalyst prepared in an Example. It is a graph which shows an example of the Raman analysis result of the catalyst prepared in the comparative example.

Hereinafter, preferred embodiments of the present invention will be described in detail.
[About hydrodesulfurization catalyst of hydrocarbon oil]
The hydrodesulfurization catalyst of the hydrocarbon oil of the present invention comprises an inorganic oxide carrier containing aluminum, at least one of molybdenum and tungsten, at least one metal component selected from Group VIII of the Periodic Table, and a carbon component. Consists of.

<Inorganic oxide carrier>
Examples of the aluminum-containing inorganic oxide carrier constituting the hydrodesulfurization catalyst include known carriers used in this type of catalyst, which are made of various inorganic substances. Examples of the carrier composed of this inorganic substance or the inorganic substance component constituting the carrier include various composite oxides composed of alumina or a composite oxide of alumina and at least one selected from silica, phosphorus, titania , zirconia, magnesia and the like. be able to. In other words, the composite oxide comprises aluminum and at least one or more elements selected from titanium, silicon, phosphorus, zirconium and magnesium.

Specific examples of the composite oxide include, but are not limited to, silica-alumina, zeolite, alumina titania, alumina phosphorus , alumina magnesia , alumina zirconia, and alumina titania silica. 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 on a carrier in a highly dispersed state and sufficiently secure catalytic activity, it usually has a porous carrier, particularly a relatively small pore having a pore diameter of 500 Å or less. Those are preferably used. Further, in order to control physical properties such as mechanical strength and heat resistance of the carrier or catalyst, an appropriate binder component or additive may be contained in the formation of the carrier or catalyst.

As the inorganic oxide carrier (hereinafter, also simply referred to as “carrier”) used in the hydrodesulfurization catalyst of the hydrocarbon oil according to the present invention, for example, an aluminum single oxide or a composite oxide composed of aluminum, silicon and titanium. The content of aluminum, etc. when using is described. The content of aluminum in the carrier is preferably 75% by mass or more, more preferably 80% by mass or more in terms of _{aluminum oxide (Al 2} O _3). When the content of aluminum in terms of oxide is less than 75% by mass, the deterioration of the catalyst tends to be accelerated.

The content of silicon in the carrier is preferably 1.0 to 12.0% by mass, more preferably 2.0 to 10.0% by mass in terms of _{silicon oxide (SiO 2).} If it is excessively larger than 12.0% by mass, silica tends to aggregate and the carrier pore distribution becomes broad, so that desulfurization activity and denitrification activity tend to decrease.

The content of titanium in the carrier is preferably 1.0 to 10.0% by mass, more preferably 2.0 to 8.0% by mass in terms of _{titanium oxide (TiO 2).} If the titanium content in terms of oxide is excessively larger than 10.0% by mass, the carrier pore distribution tends to be broad and the desulfurization activity tends to decrease.

The content of phosphorus in the carrier is preferably 0.5 to 8.0% by mass, more preferably 1.0 to 3.0% by mass in terms of _{phosphorus oxide (P 2} O _5). If the phosphorus content in terms of oxide is excessively larger than 8.0% by mass, the maximum carrier distribution tends to be broad and the desulfurization performance tends to deteriorate.

The inorganic oxide carrier of the present invention has the following properties (a) to (d). Each of them will be described in detail below. The pore diameter and pore distribution of the inorganic oxide carrier are values measured by the mercury intrusion method. The pore diameter is a value calculated using a surface tension of mercury of 480 din / cm and a contact angle of 150 °. The pore volume (PV) is a value measured by the water pore filling method.

(A) The pore volume (PV) measured by the pore filling method of water is 0.60 to 1.0 ml / g.
The pore volume (PV) measured by the water pore filling method is preferably in the range of 0.60 to 1.0 ml / g, more preferably 0.75 to 0.95 ml / g. If the pore volume (PV) is excessively smaller than 0.60 ml / g, the desulfurization activity is lowered and the desulfurization performance may be lowered, which is not preferable. On the other hand, if it is excessively larger than 1.0 ml / g, the catalyst strength may decrease, the packing density may decrease, and the desulfurization activity may decrease, which is not preferable.

(B) The specific surface area (SA) measured by the BET method is 200 to 400 m ² / g.
The ratio was measured by the BET method surface area (SA) is, it must be in the range of 200 to 400 m ² / g, preferably from 220~380m ² / g. If the specific surface area (SA) is ^{smaller than 200 m 2} / g, the metal components tend to aggregate and the desulfurization performance may deteriorate, which is not preferable. On the other hand, if it is ^{larger than 400 m 2} / g, the average pore diameter and the pore volume tend to be small, and the desulfurization activity tends to decrease, which is not preferable.

<Metal component>
It is known that the metal component supported on the inorganic oxide carrier for hydrocarbon oil is selected from Group VIA (Group 6 of IUPAC) and Group VIII (Groups 8 to 10 of IUPAC) of the Periodic Table. ing.
As the metal component of Group VIA of the periodic table (first metal component), tungsten can be preferably used in addition to molybdenum, but both molybdenum and tungsten may be used.
Cobalt and nickel are preferably used as the metal component (second metal component) of Group VIII of the periodic table.

The total content of the metal components (first metal component and second metal component) selected from Group VIA and Group VIII of the Periodic Table is as an oxide of the metal component with respect to 100 parts by mass of the inorganic oxide carrier. , 5 to 40% by mass (parts by mass) is preferable, and 10 to 35% by mass is more preferable. If the total content of the first metal component and the second metal component is excessively smaller than 5% by mass, the desulfurization activity required for the reaction may not be secured, and if it is excessively larger than 40% by mass, the metal component is contained. aggregated easily, undesirable since possibility is to inhibit dispersibility.
As a raw material for the metal component, nickel nitrate, nickel carbonate, cobalt nitrate, cobalt carbonate, molybdenum trioxide, ammonium molybdate and the like are preferably used.

<Carbon component>
The source of the carbon component supported on the inorganic oxide carrier for hydrocarbon oil is two or more kinds of organic acids, or a group of organic compounds composed of organic acids and organic additives, but further inorganic. Acids can also be used at the same time. The organic compound group also includes a mixture of one kind of organic acid and one kind of organic additive.
As the organic acid, for example, citric acid, malic acid, gluconic acid, tartaric acid, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminetetraacetic acid (DTPA) are used, and more preferably citric acid, malic acid, tartaric acid, gluconic acid. Can be used.

Further, as the organic additive, saccharides (monosaccharides, disaccharides, polysaccharides, etc.) are used, and for example, glucose (glucose; C ₆ H ₁₂ O ₆ ), fructose (fructose; C ₆ H ₁₂ O ₆ ), and so on. Preferable sugars include 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. Each of these sugars may be used alone, or these substances may be mixed. More preferably, glucose and sucrose can be used.

Further, the inorganic acid may be used at the same time as the organic acid. As the inorganic acid, a phosphorus compound is preferable, and as the phosphorus compound used, orthophosphoric acid (hereinafter, also simply referred to as “phosphoric acid”), ammonium dihydrogen phosphate, diammonium hydrogen phosphate, trimetaphosphoric acid, Pyrophosphoric acid and tripolyphosphoric acid are used, and more preferably, orthophosphoric acid can be used.

Assuming that the content of the carbon component is [C] with respect to the content [MOx] of the first metal component in terms of oxide (MOx), the mass ratio [C] / [is the ratio of [C] to [MOx]. MOx] is preferably in the range of 0.10 to 0.40, more preferably in the range of 0.10 to 0.30. If the mass ratio [C] / [MOx] is smaller than 0.10, the amount of carbon is too small with respect to the active metal in the catalyst, so that a carbon network structure is difficult to form, and sintering of the active metal occurs. The activity of the catalyst may decrease. If the mass ratio [C] / [MOx] exceeds 0.40, a large amount of the organic acid used in the preparation of the catalyst or the organic compound group consisting of the organic acid and the organic additive must be used. The viscosity of the liquid increases, which may make it difficult for the metal to be supported in the carrier pores.

The general, the carbon bearing flatness thereof as a structural factor, absorption in the vicinity of 1200～1550Cm ^-1 and near 1550～1650Cm ^-1 of the Raman spectra are known to be detected (carbon material Gakkai: " Latest Carbon Material Experimental Technology (Analysis / Analysis) ”, Cybeck, (2001) 89-99). In the hydrodesulfurization catalyst according to the present invention, in Raman analysis using a laser having a wavelength of 532 nm,
There is scope to spectral peaks of 1400~1800cm ^-1 (peak absorbance), a part of the spectrum, may have an inflection point in the range of 1200~1500cm ^-1.
Since the hydrodesulfurization catalyst according to the present invention has such a characteristic absorption, it is suggested that a network structure is formed by carbon when a metal component is supported. Although the formation mechanism of this structure is not clear, the carbon component dissolves an organic acid and an organic additive that serve as a carbon source (supply source of the carbon component) in the impregnating solution and forms a complex with the ions of the metal component. .. It is considered that the metal complex differs depending on the organic additive to be introduced and the acid type, and partially decomposes and reacts during the heat treatment to form a hard carbon network. In order to construct a more complicated carbon network, it is desirable to introduce two or more kinds of organic acids and organic additives. When such heat treatment is performed under appropriate conditions, the network structure due to carbon is not destroyed, and the metal component retains the active metal in a highly dispersed structure in the network structure due to carbon, and therefore exhibits high desulfurization activity. it is conceivable that.

The hydrodesulfurization catalyst according to the present invention has a peak intensity [A] in the range of ^{1200 to 1800 cm -1} derived from amorphous carbon and 850 to 850 derived from an oxide of molybdenum or tungsten by Raman analysis using a laser having a wavelength of 532 nm. The ratio of peak intensities [B] in the range of 1050 cm ^-1 ([A] / [B]) is preferably 1.0 or more, and more preferably 1.1 or more. The results of Raman analysis and peak intensities [A] and [B are shown in FIGS. 1 and 2 for the hydrodesulfurization catalysts used in Examples and Comparative Examples described later. When the above ratio ([A] / [B]) is 1.0 or more, the active metal is incorporated into the carbon network structure, and when it is less than 1.0, the carbon network structure is difficult to be formed. Further, even if the network structure is formed, it is considered that the active metal is exposed on the surface of the network structure, which makes it difficult to obtain the effect of the present invention.

[About hydrodesulfurization method of hydrocarbon oil]
The hydrocarbon oil to be desulfided by the hydrodesulfurization catalyst of the present invention is, for example, straight kerosene or diesel fuel obtained from an atmospheric distillation apparatus for crude oil, or direct distillation weight obtained from an atmospheric distillation apparatus. Hydrogen depressurized gas oil or decompressed gas oil obtained by treating quality oil or residual fuel oil with a vacuum distillation apparatus, catalytically decomposed kerosene or catalytically decomposed gas oil obtained by catalytically decomposing desulfurized gas oil, decompressed heavy oil or desulfurized heavy oil. Examples thereof include hydrocarbon cracked kerosene or hydrocracked gas oil obtained by chemical decomposition, thermal cracked kerosene or gas cracked gas oil obtained from a thermal cracking device such as a coker, and 80% by volume of a distillate having a boiling point of 180 to 390 ° C. It is a distillate including the above. The hydrodesulfurization treatment using the catalyst is carried out under high temperature and high pressure conditions in a hydrogen atmosphere by filling the fixed bed reactor with the catalyst.

Since the catalyst of the present invention can obtain high desulfurization activity, the amount of hydrodesulfurization refining treatment of hydrocarbon oil can be improved. Moreover, since it has a high denitrifying activity, it can be applied to hydrocarbon oils having a high nitrogen content, and can process a wide variety of raw materials.

<Manufacturing method of hydrodesulfurization catalyst for hydrocarbon oil>
Next, a method for producing a hydrodesulfurization catalyst for the hydrocarbon oil of the present invention will be described.
The method for producing a hydrodesulfurization catalyst for hydrocarbon oil according to the present invention is a first step of preparing an inorganic oxide carrier containing aluminum, and at least one of molybdenum and tungsten on the inorganic oxide carrier containing aluminum. The second step of contacting the impregnating solution containing the metal component of No. 1 with the carbon component of at least one second metal component selected from Group VIII of the periodic table, and the carrier contacted with the impregnating solution in the second step. It has a third step of heat-treating at 100-500 ° C. to obtain a hydrodesulfurization catalyst. Hereinafter, each step will be described.

<First step>
In the first step, the pH of the aqueous solution of the basic aluminum salt and the aqueous solution of the acidic aluminum salt is 6.5 to 9.5, preferably 6.5 to 8.5, and more preferably 6.8 to 8.0. This is a step of obtaining a hydrate of an inorganic oxide by mixing as described above.
When obtaining a hydrate of an inorganic composite oxide containing an element other than aluminum, the pH of the metal salt to be used is adjusted to the above pH range after being mixed in advance with an aqueous solution of an acidic aqueous solution or a basic aqueous solution of an aluminum salt. To obtain a hydrate of an inorganic composite oxide.

In order to prepare a carrier having a high silicon oxide content in the carrier, when silicate ions are mixed in an aluminum salt, the solubility of the silicate ions decreases and the silicate ions tend to aggregate. It may be difficult to obtain a carrier in which silicon is uniformly dispersed. Therefore, by adding other metal ions and / or metal salts, aggregation of silicate ions can be suppressed, a uniformly dispersed state can be maintained, and a carrier having a high silicon oxide content can be prepared. Become.

Further, 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 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, as the phosphate source, a phosphoric acid compound that includes phosphite ion and generates phosphoric acid ion in water such as ammonia phosphate, potassium phosphate, sodium phosphate, phosphoric acid, and phosphite is used. It is possible.

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

Here, the time required for adding the mixed aqueous solution to the basic aluminum salt aqueous solution is preferably 15 minutes or less because if it becomes long, unfavorable crystals such as bayarite and gibbsite may be formed in addition to pseudoboehmite. 13 minutes or less is more desirable. Bayerite and gibbsite are not preferable because they reduce the specific surface area when heat-treated.

An example of a specific process for producing an inorganic oxide carrier will be given. The above-mentioned inorganic oxide hydrate slurry is aged by a desired method and then washed to remove by-products, and hydrated with alumina or containing other elements such as alumina and silicon other than alumina. Get a slurry of things. After the slurry of this hydrate is further heat-aged, for example, it is heat-kneaded by conventional means to obtain a moldable kneaded product, and then molded into a desired shape by extrusion molding or the like, and then, for example, 70 to 150. It is heat-dried at ° C., preferably 90 to 130 ° C., and further calcined at, for example, 400 to 800 ° C., preferably 450 to 600 ° C., for example, 0.5 to 10 hours, preferably 2 to 5 hours to obtain an inorganic oxide. Obtain a carrier.

<Second step>
The inorganic oxide carrier is brought into contact with an impregnating solution containing at least one of molybdenum and tungsten, a first metal component, at least one second metal component selected from Group VIII of the Periodic Table, and a carbon component.
As the raw material of 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.
The impregnating liquid preferably has a pH of 4 or less using an acid to dissolve the metal component. When the pH exceeds 4, the stability of the dissolved metal component decreases and it tends to precipitate.

As the phosphorus compound, orthophosphoric acid (hereinafter, also simply referred to as “phosphoric acid”), ammonium dihydrogen phosphate, diammonium hydrogen phosphate, trimetaphosphoric acid, pyrophosphoric acid, and tripolyphosphoric acid are preferably used, and more preferably. Orthophosphoric acid can be used.

In the hydrodesulfurization catalyst, the phosphorus compound is preferably contained in an oxide content of 3 to 25% by mass, more preferably 5 to 15% by mass, based on molybdenum oxide. If the content of the phosphorus compound exceeds 25% by mass with respect to molybdenum oxide, the performance of the pre-sulfated hydrodesulfurization catalyst tends to deteriorate, and if it is excessively less than 3% by mass, the stability of the impregnating solution becomes stable. Is not preferable because it becomes worse.

Examples of the carbon component include organic acids and organic additives. As the organic acid, for example, citric acid, malic acid, tartaric acid, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminetetraacetic acid (DTPA) can be used, and citric acid and malic acid are particularly preferably used. The organic additives, saccharides (monosaccharides, disaccharides, polysaccharides, etc.) is used, for example, dextrose _{(glucose; C 6 H 12 O 6)} , fruit sugar _{(fructose; C 6 H 12 O 6)} , malt sugar ( 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 are mentioned as preferable sugars. Each of these sugars may be used alone, or these substances may be mixed. More preferably, glucose and sucrose can be used.

The carbon component has a mass ratio ([C] / [MOx]) of carbon to 0.10 as described above with respect to the content [MOx] of the first metal component in terms of oxide (MOx). It is preferably in the range of ~ 0.40.
The method for incorporating the metal component and the carbon component in the carrier is not particularly limited, and known methods such as an impregnation method (equilibrium adsorption method, pore filling method, initial wetting method, etc.), an ion exchange method, etc. are used. be able to. Here, the impregnation method is a method in which a carrier is impregnated with an impregnating solution containing an active metal and then heat-treated. In the impregnation method, it is preferable to support the metal component at the same time. If the metals are supported separately, the desulfurization activity may be insufficient.

<Third step>
The carrier carrying the metal component obtained by contacting with the impregnating solution in the second step is placed at 100 to 500 ° C., preferably 105 to 480 ° C., more preferably 110 to 470 ° C., for 0.5 to 10 hours, preferably. After heat treatment for 1 to 8 hours, the hydrodesulfurization catalyst of the present invention is produced. Here, if the firing temperature is excessively lower than 100 ° C., the operability due to the residual moisture may be deteriorated, and the metal-supported state may be difficult to be uniform. If the firing temperature is excessively higher than 500 ° C., the amount of the residual carbon component decreases. However, it is not preferable because the carbon network structure is difficult to form and the effect may not be expected.

[Measurement method]
As will be described later, the hydrodesulfurization catalysts in the Examples and Comparative Examples of the present invention are measured with respect to the content, specific surface area and properties of the components. back.
<Method of measuring the content of carrier components (alumina, silica, phosphorus oxide) and metal components (molybdenum, cobalt, nickel)>
3 g of the measurement sample is collected in a zirconia ball with a lid having a capacity of 30 ml, heat-treated (200 ° C., 20 minutes), calcined (700 ° C., 5 minutes), and then _{2 2} g of Na 2 O and 1 g of NaOH are added for 15 minutes. It melted. _Furthermore, after dissolved by adding H ₂ SO 4 25 ml of water 200 ml, and a sample was diluted to 500ml with purified water. _{For the obtained sample, the content of each component was determined by the oxide conversion standard (Al 2} O ₃ , SiO ₂ , P) using an ICP device (ICPS-8100 manufactured by Shimadzu Corporation, analysis software ICPS-8000). ₂ O ₅ , MoO ₃ , NiO, CoO).

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

<Measurement method of pore volume>
The pore volume was measured by the water pore filling method.

<Measurement method for X-ray analysis> (Method for determining crystal shape)
Approximately 30 ml of the measurement sample was collected in a magnetic crucible (B-2 type), heated at 110 ° C. for 12 hours for heat treatment, and then placed in a desiccator and cooled to room temperature. Next, the cooled product was pulverized in a mortar for 15 minutes, and then the crystal morphology was measured using an X-ray diffractometer (RINT1400, manufactured by Rigaku Denki Co., Ltd.). The crystal morphology referred to in the present invention indicates a morphology determined from this measurement result (for example, γ-alumina).

<Measurement method of Raman spectrum>
Raman spectrum measurement by laser excitation with a laser wavelength of 532 nm was performed at room temperature. After crushing, the measurement sample was measured from 200 to 2000 cm ^{-1 using a LabRAM manufactured by HORIBA, Ltd.}

[Example]
Preparation example of inorganic oxide carrier, preparation example of impregnating liquid, preparation example of hydrodesulfurization catalyst which is an example of the present invention using each inorganic oxide carrier and impregnating liquid, each inorganic oxide carrier and impregnation An example of preparation of a hydrodesulfurization catalyst, which is a comparative example using a liquid, is described below.
First, an example of preparing an inorganic oxide carrier will be described.

<Preparation of Inorganic Oxide Carrier A>
Tank steam jacketed capacity 100L, _Al 2 _{O 3} concentration in terms of 22% by weight aqueous sodium aluminate solution (manufactured by JGC Catalysts and Chemicals (Ltd.)) 9.09kg were charged, and diluted with ion-exchanged water 40. After making it 00 kg, add 60.0 g of sodium gluconate (manufactured by Fuso Chemical Industry Co., Ltd.) having a concentration of 99% by mass, heat to 60 ° C. with stirring, and aluminic acid containing sodium gluconate having a concentration of 5% by mass. An aqueous sodium solution (L1) was prepared.
Further, aluminum sulfate aqueous solution obtained by diluting 14.29 kg of an aqueous aluminum sulfate solution (manufactured by Nikki Catalyst Kasei Co., Ltd.) having a concentration _{of 7% by mass in terms of Al 2} O _{3 with 25.71 kg of ion-exchanged water was heated to 60 ° C.} An aqueous aluminum solution (L2) was prepared.
Next, while stirring the sodium aluminate aqueous solution (L1), the aluminum sulfate aqueous solution (L2) was added thereto in 10 minutes, and 3.8% by mass of alumina oxide in terms of _{Al 2} O _{3 concentration was added.} A hydrate slurry was prepared. At this time, the pH of the alumina oxide hydrate slurry was 7.2.

The obtained alumina oxide hydrate slurry was aged at 60 ° C. for 60 minutes with stirring, and then the alumina oxide hydrate slurry was dehydrated using a flat plate filter, and then ammonia having a concentration of 0.3% by mass was used. It was washed with 1.5 L of aqueous solution. The 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 to form a slurry, and then ammonia water having a concentration of 15% by mass was added to adjust the pH to 10.5. .. 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, heated while kneading with a double-armed kneader with a steam jacket, and concentrated and kneaded to a predetermined water content. The obtained kneaded product was molded into a cylinder having a diameter of 1.8 mm and a length of 3 mm using a screw-type extrusion molding machine, heat-treated at 110 ° C. for 12 hours, and then fired at 550 ° C. for 3 hours in an electric furnace. An inorganic oxide carrier (A) (hereinafter, also simply referred to as “carrier A”; the same applies to the following preparation examples, examples and comparative examples) was prepared.
Table 1 shows the measurement results of the crystal morphology and specific surface area of the inorganic oxide carrier A by X-ray analysis.

<Preparation of inorganic oxide carrier B>
In the preparation of the carrier A, after heat treatment at 110 ° C. for 12 hours, the same preparation as that of the carrier A was performed except that the firing temperature in the electric furnace was set to 800 ° C. to obtain the carrier B.
Table 1 shows the measurement results of the crystal morphology and specific surface area of the inorganic oxide carrier B by X-ray analysis.

<Preparation of inorganic oxide carrier C>
In the preparation of carrier A, a tank with a steam jacket having a capacity of 100 L was diluted with 8.91 kg of a 22 mass% sodium aluminate aqueous solution and 39.20 kg of ion-exchanged water in terms of _{Al 2} O _{3 concentration, and then converted to SiO 2} concentration. Add 1.20 kg of a 5 mass% sodium aluminate solution (manufactured by AGC SITEC Co., _{Ltd .; SiO 2} concentration 24 mass%) with stirring and heat to 60 ° C. to prepare a basic aluminum salt aqueous solution. did. Further, the same preparation as that of the carrier A was carried out except that 14.00 kg of the aluminum sulfate aqueous solution and 25.2 kg of the ion-exchanged water for diluting the aluminum sulfate were used to obtain the carrier C.
Table 1 shows the measurement results of the crystal morphology and specific surface area of the inorganic oxide carrier C by X-ray analysis.

<Preparation of Inorganic Oxide Carrier D>
In the preparation of carrier A, a tank with a steam jacket having a capacity of 100 L was diluted with 8.45 kg of an aqueous sodium aluminate solution and 28.8 kg of ion-exchanged water, and then 4.20 kg of a sodium silicate solution was added with stirring to 60. Aqueous solution of basic aluminum salt was prepared by heating to ° C. Further, the same preparation as that of the carrier A was carried out except that 13.29 kg of the aluminum sulfate aqueous solution and 23.91 kg of the ion-exchanged water for diluting the aluminum sulfate were used to obtain the carrier D.
Table 1 shows the measurement results of the crystal morphology and specific surface area of the inorganic oxide carrier D by X-ray analysis.

<Preparation of inorganic oxide carrier E>
Tank steam jacketed capacity 100L, _Al 2 _{O 3} at a concentration in terms of putting 22 wt% aqueous sodium 8.64kg aluminate, diluted with deionized water 29.4Kg, sodium gluconate at a concentration 100 wt% 57.0 g was added and heated to 60 ° C. with stirring to prepare an aqueous sodium aluminate solution (L3) containing sodium aluminate having a concentration of 5% by mass. Further, 2.54 kg of an acidic aluminum salt aqueous solution obtained by diluting 13.57 kg of an aqueous aluminum sulfate solution with 24.4 kg of ion-exchanged water and 0.46 kg of titanyl sulfate (manufactured by Teika Co., Ltd.) _{having a TiO 2 concentration of 33% by mass.} The aqueous solution of titanium mineral salt dissolved in the ion-exchanged water of No. 1 was mixed and heated to 60 ° C. to prepare an aqueous solution of aluminum sulfate (L4).
Next, while stirring the sodium aluminate aqueous solution (L3), the aluminum sulfate aqueous solution (L4) was added thereto in 10 minutes, and 3.8% by mass of alumina titania oxidation in terms of _{Al 2} O _{3 concentration was obtained.} The same preparation as that for carrier A was carried out except that a hydrated slurry was prepared, and carrier E was obtained.
Table 1 shows the measurement results of the crystal morphology and specific surface area of the inorganic oxide carrier E by X-ray analysis.

<Preparation of inorganic oxide carrier F>
Put 8.91 kg of sodium aluminate aqueous solution in a tank with a steam jacket with a capacity of 100 L, dilute with 30.3 kg of ion-exchanged water, add 59.0 g of sodium gluconate, and heat to 60 ° C. with stirring. , Sodium gluconate-containing sodium aluminate aqueous solution (L5) having a concentration of 5% by mass was prepared. Further, an acidic aluminum salt aqueous solution obtained by diluting 14.00 kg of an aluminum sulfate aqueous solution with 25.2 kg of ion-exchanged water and a titanium mineral salt aqueous solution obtained by dissolving 0.18 kg of titanium sulfate in 1.02 kg of ion-exchanged water were mixed. , 60 ° C. to prepare an aqueous aluminum sulfate solution (L6).
Then, the stirring of the aqueous sodium aluminate solution (L5), the aqueous aluminum sulfate solution (L6) to this was added over 10 minutes, _Al 2 _{O 3} concentration in terms of 3.8% by weight of alumina titania oxide The same preparation as that for carrier A was carried out except that a hydrated slurry was prepared, to obtain carrier F.
Table 1 shows the measurement results of the crystal morphology and specific surface area of the inorganic oxide carrier F by X-ray analysis.

<Preparation of Inorganic Oxide Carrier G>
In the preparation of the carrier A, after heat treatment at 110 ° C. for 12 hours, the same preparation as that of the carrier A was performed except that the firing temperature in the electric furnace was set to 950 ° C. to obtain the carrier G.

Table 1 shows the measurement results of the crystal morphology and specific surface area of the inorganic oxide carrier G by X-ray analysis.
Although the measurement results of the pore volume of the carrier are not shown in Table 1, the carriers A and D are 0.78 ml / g, the carriers B, C and G are 0.76 ml / g, and the carrier E. Was 0.75 ml / g, and the carrier F was 0.74 ml / g.

<Preparation of impregnating liquid a1>
169.9 g of molybdenum trioxide (manufactured by Climax Co., _{Ltd .; MoO 3} concentration 99.9% by mass) and 70.1 g of cobalt carbonate (manufactured by Tanaka Chemical Laboratory Co., Ltd .; CoO concentration 61% by mass) are added to ion-exchanged water. It was suspended in 400 ml, after 5 hours liquid capacity is heated by applying an appropriate reflux measures to not reduce in the suspension 95 ° C., manufactured by phosphoric acid (Kanto Chemical (Co.); P ₂ O ₅ concentration 62 Add 42.0 g of citric acid (manufactured by Kanto Chemical Co., Ltd .:, purity 99.9 mass%) 64.3 g and gluconic acid (manufactured by Kanto Chemical Co., Ltd., purity 50 mass%) 147.8 g. It was dissolved to prepare an impregnating solution a1.
<Preparation of impregnating liquid a2>
162.0 g of molybdenum trioxide and 34.6 g of cobalt carbonate were suspended in 400 ml of ion-exchanged water, and the suspension was heated at 95 ° C. for 5 hours with appropriate reflux measures so that the liquid volume did not decrease. After that, 34.3 g of phosphoric acid, 31.7 g of citric acid and 140.8 g of gluconic acid were added and dissolved to prepare an impregnating solution a2.
<Preparation of impregnating liquid a3>
166.7 g of molybdenum trioxide and 59.3 g of cobalt carbonate were suspended in 400 ml of ion-exchanged water, and the suspension was heated at 95 ° C. for 5 hours with appropriate reflux measures so that the liquid volume did not decrease. After that, 35.3 g of phosphoric acid, 54.3 g of citric acid and 144.9 g of gluconic acid were added and dissolved to prepare an impregnating solution a3.
<Preparation of impregnating liquid a4>
171.9 g of molybdenum trioxide and 99.1 g of cobalt carbonate were suspended in 400 ml of ion-exchanged water, and the suspension was heated at 95 ° C. for 5 hours with appropriate reflux measures so that the liquid volume did not decrease. After that, 24.3 g of phosphoric acid, 90.8 g of citric acid and 149.5 g of gluconic acid were added and dissolved to prepare an impregnating solution a4.
<Preparation of impregnating liquid a5>
An impregnating solution a5 was prepared in the same manner as the impregnating solution a1 except that the amount of citric acid was changed to 85.7 g and the amount of gluconic acid was changed to 108.2 g.
<Preparation of impregnating liquid a6>
An impregnating solution a6 was prepared in the same manner as the impregnating solution a1 except that the amount of citric acid was changed to 34.3 g and the amount of gluconic acid was changed to 59.0 g.
<Preparation of impregnating liquid a7>
An impregnating solution a7 was prepared in the same manner as the impregnating solution a1 except that the amount of gluconic acid was changed to 29.6 g.
<Preparation of impregnating liquid a8>
An impregnating solution a8 was prepared in the same manner as the impregnating solution a1 except that the amount of citric acid was changed to 107.1 g and the amount of gluconic acid was changed to 147.8 g.
<Preparation of impregnating liquid a9>
159.3 g of molybdenum trioxide and 20.4 g of cobalt carbonate were suspended in 400 ml of ion-exchanged water, and the suspension was heated at 95 ° C. for 5 hours with appropriate reflux measures so that the liquid volume did not decrease. After that, 33.7 g of phosphoric acid, 18.7 g of citric acid and 138.5 g of gluconic acid were added and dissolved to prepare an impregnating solution a9.

<Preparation of impregnating liquid b>
The impregnating liquid b was prepared in the same manner as the impregnating liquid a1 except that the gluconic acid was changed to 73.9 g of tartaric acid (manufactured by Kanto Chemical Co., Inc .; tartaric acid concentration 99% by mass).

<Preparation of impregnating liquid c1>
An impregnating solution c1 was prepared in the same manner as the impregnating solution a1 except that 74.7 g of glucose (manufactured by Kanto Chemical Co., Inc., purity 98% by mass) was used instead of gluconic acid.
<Preparation of impregnating liquid c2>
The impregnating solution c2 was prepared in the same manner as the impregnating solution c1 except that the metal type was changed from cobalt to nickel and 77.9 g of nickel carbonate (manufactured by Shodo Chemical Industry Co., Ltd .; NiO concentration 55% by mass) was changed. did.
<Preparation of impregnating liquid c3>
The impregnating liquid c3 was prepared in the same manner as the impregnating liquid c1 except that the amount of cobalt was changed to 55.6 g of cobalt carbonate and 16.1 g of nickel carbonate was added.

<Preparation of impregnating liquid d>
An impregnating solution d was prepared in the same manner as the impregnating solution a1 except that 73.9 g of sucrose (manufactured by Kanto Chemical Co., Inc., purity 99% by mass) was used instead of gluconic acid.

<Preparation of impregnating liquid e>
An impregnating solution e was prepared in the same manner as the impregnating solution a1 except that 65.0 g of malic acid (manufactured by Kanto Chemical Co., Inc., purity 98% by mass) was used instead of citric acid.

<Preparation of impregnating liquid f>
The impregnating liquid f was prepared in the same manner as the impregnating liquid a1 except that the addition of phosphoric acid was removed.

<Preparation of impregnating solution g>
An impregnating solution g was prepared in the same manner as the impregnating solution a1 except that the amount of citric acid was 107.1 g and the addition of gluconic acid was removed.

<Preparation of impregnating liquid h>
An impregnating solution h was prepared in the same manner as the impregnating solution a1 except that 74.7 g of glucose was used instead of the gluconic acid and the addition of citric acid was removed.

<Preparation of impregnating liquid i>
The impregnating liquid i was prepared in the same manner as the impregnating liquid a1 except that no organic substance was used.
For each of the above-mentioned impregnating liquids, the content of the second metal component selected from Group VIII of the periodic table in terms of oxide (MO) with respect to the content [MOx] of the first metal component in terms of oxide (MOx). The ratio of the amount [MO] ([MO] / [MOx]) is described.
The impregnating liquids a1, b, c1, d, e, f, a5, a6, a7, g, h, i, and a8 ([MO] / [MOx]) are
[MOx] = 169.9 g x 0.999 (purity 99.9%) = 169.7 g
Since [MO] = 70.1 g × 0.61 (purity 61%) = 42.8 g,
42.8 / 169.7 = 0.25.
The ([MO] / [MOx]) of the impregnating liquid a2 is
[MOx] = 162.0 g x 0.999 = 161.8 g
Since [MO] = 34.6 g × 0.61 = 21.1 g,
21.1 / 161.8 = 0.13.
The ([MO] / [MOx]) of the impregnating liquid a3 is
[MOx] = 166.7 g x 0.999 = 166.5 g
Since [MO] = 59.3 g × 0.61 = 36.2 g,
36.2 / 166.5 = 0.22.
The ([MO] / [MOx]) of the impregnating liquid a4 is
[MOx] = 171.9g x 0.999 = 171.7g
Since [MO] = 99.1 g × 0.61 = 60.5 g,
60.5 / 171.9 = 0.35.
The ([MO] / [MOx]) of the impregnating liquid c2 is
[MOx] = 169.9g x 0.999 = 169.7g
Since [MO] = 77.9 g × 0.55 (purity 55%) = 42.8 g,
42.8 / 169.7 = 0.25.
The ([MO] / [MOx]) of the impregnating liquid c3 is
[MOx] = 169.9g x 0.999 = 169.7g
[MO] = (55.6 g x 0.61) + (16.1 g x 0.55)
= 33.9 + 8.9 = 42.8 g, so
42.8 / 169.7 = 0.25.
The ([MO] / [MOx]) of the impregnating liquid a9 is
[MOx] = 159.3 g x 0.999 = 159.1 g
Since [MO] = 20.4 g × 0.61 = 12.4 g,
12.4 / 159.1 = 0.08.

<Example 1: Preparation of hydrodesulfurization catalyst>
The water content of the prepared impregnating liquid a1 was adjusted so as to have a volume corresponding to the volume that completely fills the pore volume of the carrier A. Since the pore volume of the carrier A is 0.78 ml / g as described above, the volume of the impregnating liquid a1 to be adjusted with respect to 500 g of the carrier A is 390 ml (0.78 ml / g × 500 g). .. Next, 500 g of the impregnated solution a1 whose volume has been adjusted is spray-impregnated on the carrier A, and then heat-treated at 120 ° C. for 2 hours to obtain a hydrodesulfurization catalyst (hereinafter, also simply referred to as “catalyst”. The same applies to the above.) The properties of the obtained catalyst are shown in Table 1.

<Examples 2 to 18: Preparation of hydrodesulfurization catalyst>
The type of carrier (preparation example) prepared as described above and the type of impregnating solution (preparation example) are combined as shown in Table 1, and the others are the same as in Example 1 in Examples 2 to 18. The catalyst was prepared. The properties of the obtained catalyst are shown in Table 1.
<Comparative Examples 1 to 8 : Preparation of Hydrodesulfurization Catalyst>
The type of the prepared carrier (preparation example) and the type of the impregnating solution (preparation example) as described above are combined as shown in Table 1, and the others are the same as in Example 1 in Comparative Example 1 and Comparative Example 3. -The catalyst of Comparative Example 8 was prepared. Further, a catalyst of Comparative Example 2 was prepared in the same manner as in Comparative Example 1 except that 500 g of the impregnating solution a1 was spray-impregnated with the carrier A and then heat-treated at 500 ° C. for 2 hours. The properties of the obtained catalyst are shown in Table 1.
As representatives of the above catalyst group, the results of Raman analysis and the peak intensities [A] and peak intensities [B] of the catalyst of Example 3 and the catalyst of Comparative Example 3 are shown in FIGS. 1 and 2.

<Confirmation test>
(Confirmation test method)
The catalyst of Example 1 was filled in a fixed bed reactor and pre-sulfurized in order to desorb and activate the oxygen atoms contained in the catalyst. This pre-sulfurization treatment is carried out by circulating 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. In this confirmation test, petroleum distillate containing a sulfur compound, dimethyl sulfide, dimethyl disulfide, carbon disulfide, or other sulfurizing agent added, or hydrogen sulfide at 200 to 400 ° C. at normal pressure or higher. Pre-sulfurization was performed by creating a pressure hydrogen atmosphere.

Next, straight gas oil (density 0.8468 g / cm ^{3 at} 15 ° C., sulfur content 1.13% by mass, nitrogen content 0.083% by mass) was supplied into the fixed bed flow reactor at a rate of 150 ml / hour. Then, hydrodesulfurization treatment was carried out, and hydrorefining was carried out. The reaction conditions at that time were a hydrogen partial pressure of 4.5 MPa, a liquid space velocity of 1.0 ^h-1 , and a hydrogen-oil ratio of 250 Nm ³ / kl. Then, the reaction temperature is changed in the range of 300 to 360 ° C., sulfur analysis and nitrogen analysis in the refined oil at each temperature are performed, and the temperature at which the sulfur content in the refined oil becomes 8 ppm and the temperature at which the nitrogen content becomes 1 ppm are set respectively. I asked.
Then, the same confirmation test was carried out for each catalyst in Examples 2 to 18 and Comparative Examples 1 to 8. Table 1 shows the temperature at which the sulfur content in the refined oil becomes 8 ppm (reaction temperature) and the temperature at which the nitrogen content becomes 1 ppm in the hydrorefining treatment using each catalyst.

(Evaluation result of confirmation test)
When the catalysts of Examples 1 to 18 were used, the reaction temperature at which the sulfur content in the refined oil became 8 ppm was 340 to 349 ° C., which was lower than 350 ° C. in any of the catalysts.
On the other hand, when the catalysts of Comparative Examples 1 to 8 were used, the reaction temperature was 350 to 360 ° C., and 350 ° C. or higher in any of the catalysts, and Examples 1 to 18 The reaction temperature is clearly higher than when the catalyst of. Therefore, it can be seen that the desulfurization activity of the catalysts of Examples 1 to 18 is higher than that of the catalysts of Comparative Examples 1 to 8.
Further, the reaction temperature at which the nitrogen content in the refined oil becomes 1 ppm is 300 to 319 ° C. when the catalysts of Examples 1 to 18 are used, which is lower than 320 ° C. in any of the catalysts. ..

On the other hand, when the catalysts of Comparative Examples 1 to 8 were used, the reaction temperature was 320 to 330 ° C., and 320 ° C. or higher in any of the catalysts, and Examples 1 to 18 The reaction temperature is clearly higher than when the catalyst of. Therefore, it can be seen that the denitrification activity of the catalysts of Examples 1 to 18 is higher than that of the catalysts of Comparative Examples 1 to 8.

In this way, the factors that cause the difference in desulfurization activity and denitrification activity between the catalyst of the example and the catalyst of the comparative example will be considered. First, looking at the properties of the catalysts of Comparative Examples 1 to 5 , the absorbance ratio (A / B) of the spectral peaks in the Raman analysis described above is defined as the lower limit of 1.0 of the present invention. Is below. Therefore, it is considered that the carbon network structure is not sufficiently formed in these catalysts, and therefore the desulfurization activity is lower than that of the catalysts of each example. Regarding the catalyst of Comparative Example 2, since the firing temperature of the catalyst in contact with the impregnating solution was as high as 500 ° C., the carbon component was scattered and the ratio of the carbon component content to the oxide-equivalent content of all metal components was It is 0.0.

For the catalyst of Comparative Example 6 , the absorbance ratio (A / B) of the spectral peak in the Raman analysis was larger than 1.0, but the ratio of the carbon component content to the oxide-equivalent content of all metal components was It is larger than 0.4 specified as the upper limit of the present invention. In these catalysts, it is considered that the viscosity of the impregnating solution becomes high and the impregnating solution does not sufficiently reach the pores of the carrier, resulting in a decrease in desulfurization activity.
In the catalyst of Comparative Example 7, [MO] / [MOx] is less than 0.10, and the ratio of the first metal component to the second metal component is not appropriate.
In the catalyst of Comparative Example 8 , the specific surface area of the carrier was as small as 180 m ² / g, which was lower than the lower limit of 200 m ² / g specified in the present invention, and the degree of aggregation of metal components was increased. It is considered that the desulfurization activity is reduced.

On the other hand, in each of the catalysts of Examples 1 to 18, the absorbance ratio (A / B) of the spectral peaks in the Raman analysis was 1.0 or more, and the oxide-equivalent content of all metal components. Since the ratio of the content of the carbon component to the carbon component is in the range of 0.10 to 0.40, it is considered that a network structure made of carbon is formed and the active metal is incorporated in this network structure in a highly dispersed state. Be done. The specific surface area of the carrier is also adjusted in ^{the range of 200 to 400 m 2} / g, and therefore, each catalyst of Examples 1 to 18 exhibits high desulfurization activity.

The hydrodesulfurization catalyst of the present invention is extremely useful in industry because it can highly hydrodesulfurize hydrocarbon oils.

Claims (6)

It contains at least one of molybdenum and tungsten, a first metal component, and at least one second metal component selected from Group VIII of the periodic table, and is converted into an oxide (MOx) of the first metal component. The impregnated solution in which the ratio ([MO] / [MOx]) of the content [MO] of the second metal component in terms of oxide (MO) to the content [MOx] in is 0.13 or more is mixed with aluminum. obtained by contacting an inorganic oxide carrier containing a first metal component, and the second metal component, a hydrodesulfurization catalyst for hydrocarbon oil containing a carbon component, a,
(A) The specific surface area of the inorganic oxide carrier is in the range of ^{200 to 400 m 2 / g.}
(B) The ratio ([C] / [MOx]) of the content [C] of the carbon component to the oxide (MOx) -equivalent content [MOx] of the first metal component is 0.10 to 0. In the range of .40,
(C) The ratio (A / B) of the absorbance A of the spectral peak in the range of ^{1400 to 1800 cm -1} and the absorbance B of the spectral peak in the range ^{of 850 to 850 cm -1 was} determined by Raman analysis using a 532 nm wavelength laser. 1.0 or higher
(D) The source of the carbon component is two or more kinds of organic acids, or a group of organic compounds composed of an organic acid and an organic additive.
The inorganic oxide carrier does not contain boria as an active ingredient.
Hydrodesulfurization catalyst for hydrocarbon oils. The first aspect of claim 1, wherein the inorganic oxide carrier is an aluminum oxide or an inorganic composite oxide composed of aluminum and at least one element selected from titanium, silicon, phosphorus, zirconium and magnesium. Hydrodesulfurization catalyst for hydrocarbon oils. The hydrodesulfurization catalyst for a hydrocarbon oil according to claim 1 or 2, wherein the second metal component selected from Group VIII of the periodic table is selected from cobalt and nickel. Any one of claims 1 to 3, wherein the total content of the first metal component and the second metal component is in the range of 5 to 40 parts by mass with respect to 100 parts by mass of the hydrodesulfurization carrier. Hydrodesulfurization catalyst for hydrocarbon oils according to the above. It consists of an inorganic oxide carrier containing aluminum, a first metal component which is at least one of molybdenum and tungsten, at least one second metal component selected from Group VIII of the Periodic Table, and a carbon component.
(A) The specific surface area of the inorganic oxide carrier is in the range of ^{200 to 400 m 2 / g.}
(B) The ratio ([C] / [MOx]) of the content [C] of the carbon component to the oxide (MOx) -equivalent content [MOx] of the first metal component is 0.10 to 0. In the range of .40,
(C) The ratio (A / B) of the absorbance A of the spectral peak in the range of ^{1400 to 1800 cm -1} and the absorbance B of the spectral peak in the range ^{of 850 to 850 cm -1 was} determined by Raman analysis using a 532 nm wavelength laser. 1.0 or higher
(D) The inorganic oxide carrier does not contain boria as an active ingredient.
A method for producing a hydrodesulfurization catalyst for hydrocarbon oil.
(1) Step of preparing an inorganic oxide carrier containing aluminum,
(2) A first metal component that is at least one of molybdenum and tungsten, at least one second metal component selected from Group VIII of the Periodic Table, and two or more organic acids or organic acids. The second metal component selected from Group VIII of the Periodic Table with respect to the content [MOx] of the first metal component in terms of oxide (MOx), which includes an organic compound group consisting of and an organic additive. The step of contacting the impregnated liquid having a ratio ([MO] / [MOx]) of the content [MO] in terms of oxide (MO) of 0.13 or more to the inorganic oxide carrier.
(3) A step of heat-treating the carrier obtained in the step (2) above to obtain a hydrodesulfurization catalyst.
A method for producing a hydrodesulfurization catalyst for a hydrocarbon oil. A method for hydrodesulfurizing a hydrocarbon oil, which comprises contacting the hydrocarbon oil with the hydrodesulfurization catalyst of the hydrocarbon oil according to any one of claims 1 to 4 in the presence of hydrogen.

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