JPH08224471A - Fire resisting inorganic oxide catalyst carrier and hydrogenation catalyst using the same - Google Patents

Abstract

PURPOSE: To provide a hydrogenation catalyst increased in the solid acidity of a silica-containing aluminum based catalyst carrier, optimized in solid acidity distribution and attained in high dispersion of a hydrogenating metallic activated component on the carrier. CONSTITUTION: The hydrogenation catalyst having suitable solid acidity, acidity distribution and excellent in dispersibility of a hydrogenating activated metal is provided by introducing 0.1-5wt.% lanthanoid-based component expressed in terms of metal content based on total weight of the carrier as a reference into the silica-containing alumina containing 2-35wt.% silica.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel hydrotreating catalyst, and more specifically, it uses silica-containing alumina as a carrier to increase the solid acidity and to disperse a hydrogenation-active metal component. The present invention relates to a hydrotreating catalyst having improved properties. According to the invention, especially as a catalyst used in the hydrotreating process of petroleum hydrocarbon oils,
It is possible to provide a catalyst for highly active hydrotreating in which desulfurization activity and denitrification activity are remarkably improved.

[0002]

2. Description of the Related Art Conventionally, in the hydrotreating of petroleum hydrocarbon oils, a refractory inorganic oxide is generally used as a carrier, on which a group consisting of Group VI metal components and Group VIII metal components of the Periodic Table of the Elements is used. A hydrotreating catalyst prepared by supporting at least one hydrogenation active metal component selected from the above is used. As the refractory inorganic oxide, for example, silica, alumina, silica-alumina, zirconia, titania, boria, hafnia and magnesia are used, as the hydrogenation active metal component, for example, molybdenum, tungsten, nickel, cobalt. In particular, cobalt-molybdenum-based, nickel-molybdenum-based, and cobalt-nickel-molybdenum-based hydrotreating catalysts are widely used due to the combination of these active metal components.

One of the most important matters for such a hydrotreating catalyst is that the solid acidity of the catalyst carrier is sufficiently controlled, and at the same time, the hydrogenation active metal component is uniformly distributed on the carrier. It is to be supported in a large amount with a high composition and in a highly dispersed state. Although a highly active hydrotreating catalyst is realized by this, conventionally, the silica is known to exhibit a function of controlling the solid acidity by imparting a strong acid point to the catalyst, for example, According to Japanese Patent Application Laid-Open No. 61-107946, a silica-containing alumina carrier having a silica content of 2% by weight to 40% by weight is superior in solid acidity to an alumina carrier, and carbon of a raw hydrocarbon oil is It is described to have activity in breaking sulfur bonds and carbon-nitrogen bonds.

However, the silica-alumina carrier as described above has a low solid acidity, the solid acidity distribution is not sufficient for the weak acid point, and the ratio of the strong acid point to the amount of the weak acid point is high, which is not preferable. . Furthermore, the dispersibility of the hydrogenation-active metal component is also insufficient, and there has been a strong demand for measures to improve these components.

[0005]

The present invention is based on the above-mentioned background and uses silica-containing alumina as a carrier to increase the solid acidity and to have an optimized solid acidity distribution. An object is to provide a hydrotreating catalyst having improved dispersibility of an active metal component.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have introduced a lanthanoid-based metal component into silica-containing alumina.
Focusing on the fact that a solid-state acidity is increased, a solid-state acidity distribution is optimized, and a hydrotreating catalyst in which high dispersibility of a hydrogenation active metal component is achieved can be obtained, and the present invention is based on this finding. Was completed.

Thus, according to the present invention, at least one lanthanoid-based metal component is added to the silica-containing alumina having a silica content of 2% by weight to 35% by weight as a metal amount. , 0.1% by weight to 5% of the total weight of the carrier
There is provided a refractory inorganic oxide catalyst carrier, characterized in that the main component is a silica-alumina-lanthanoid-based metal component contained in a weight percentage.

Further, according to the present invention, at least one lanthanoid metal component is used as a metal amount in silica-containing alumina having a silica content of 2% by weight to 35% by weight, which is composed of silica, alumina and a lanthanoid metal component. , 0.1% by weight to 5% of the total weight of the carrier
The silica-alumina-lanthanoid-based metal component, which is contained in an amount of 1 wt.
There is provided a hydrotreating catalyst which carries at least one hydrogenation-active metal component selected from the group consisting of a Group IB metal component and a Group VIII metal component in the same table.

Furthermore, in a preferred embodiment of the present invention, the lanthanoid metal component is lanthanum (atomic number 57).
To Samarium (atomic number 62), which is at least one member of the cerium group, the refractory inorganic oxide catalyst carrier according to the above item, 70 KJ / m measured by an ammonia adsorption calorimetry
The solid acid amount of ol or more is 0.70 mol / g to 0.95 m
The refractory inorganic oxide catalyst carrier according to the above item which is ol / g, the hydrotreating catalyst obtained by supporting the hydrogenation active metal component on the carrier according to the above item or the above item, and the silica content of 5% by weight to 20% by weight of silica-containing alumina with 0.2% by weight of lanthanum component as metal
~ 3 wt% silica-alumina-lanthanum-based carrier as a hydrogenation active metal component cobalt-molybdenum, nickel-molybdenum or nickel-
There is provided a hydrotreating catalyst supporting cobalt-molybdenum.

One of the greatest features of the present invention is that the silica-containing alumina contains a lanthanoid metal component to increase the solid acidity of the carrier, thereby increasing the carbon-sulfur and carbon-nitrogen contents of the hydrocarbon oil. It is intended to enhance the action of breaking the bond and achieve highly dispersed loading of the hydrogenation active metal component with the increase of the solid acidity.

The present invention will be described in detail below. Carrier The catalyst carrier in the present invention comprises silica, alumina and a lanthanoid-based metal component, and has a silica content of 2% by weight.
It is obtained by adding at least one lanthanoid-based metal component to silica-containing alumina of ˜35 wt%. The silica is suitable for controlling the solid acidity of the carrier, and suppresses an increase in hydrogen consumption due to an excessive dispersion reaction of hydrocarbon oil and the formation of coke in the hydrodesulfurization reaction and the hydrodenitrogenation reaction. In order to do so, the preferred silica content is 5% to 20% by weight, and the more preferred content is in the range of 10% to 16% by weight.

In the present invention, the type of alumina is not particularly limited, and any one of γ-alumina, χ-alumina or η-alumina or a mixture thereof is used.

In addition to silica, other refractory inorganic oxides such as magnesia, calcia,
One or more kinds of zirconia, titania, boria, hafnia, crystalline zeolite and the like can be contained. In this case, since silica has a function of controlling the solid acidity required for the catalyst, its specific addition amount is appropriately determined according to the desired catalyst acid strength. The content of the refractory inorganic oxide such as magnesia, zirconia, titania, boria, hafnia and crystalline zeolite is appropriately in the range of about 1% by weight to about 10% by weight based on the silica-containing alumina.

The above-mentioned lanthanoid-based metal components are lanthanum La to 57 of the 57th element belonging to Group III of the Periodic Table of the Elements.
It includes 15 elements up to element 1 lutetium Lu. That is, the 15 elements are lanthanum La, cerium Ce,
Praseodymium Pr, Neodymium Nd, Promethium Pm,
Samarium Sm, Europium Eu, Gadolinium G
d, terbium Tb, dysprosium Dy, holmium Ho, erbium Er, thulium Tm, ytterbium Yb and lutetium Lu. The lanthanoid-based metal component preferred in the present invention is a cerium-Ce-based metal component from lanthanum La to samarium Sm. More preferable metal components are lanthanum La, cerium Ce, neodymium Nd and the like.

In the present invention, as a method for producing a catalyst carrier comprising a silica-alumina-lanthanoid metal component, a method of cation exchange between a silica-containing alumina prepared beforehand and a lanthanoid metal component, silica-
A method of coprecipitation of an alumina-lanthanoid metal component or a method of depositing a lanthanoid metal component on silica-alumina can be employed.

In order to produce the preferred catalyst carrier of the present invention by the lanthanoid-based metal ion exchange method, first, silica-containing alumina is produced, and then the cation of the lanthanoid-based metal is introduced into the silica-containing alumina by ion exchange. To be done. The method for producing silica-containing alumina is not particularly limited, but a water-soluble compound as a raw material, for example,
Water-soluble acidic aluminum compound or water-soluble alkaline aluminum compound, specifically, aluminum sulfate,
Chlorides, nitrates, alkali metal aluminates, aluminum alkoxides and other inorganic or organic salts can be used.

As the water-soluble silicon compound, a silicon-containing compound such as an alkali metal silicate (Na ₂ O: SiO ₂ = 1: 2 to 1: 4 is preferable), tetraalkoxysilane, orthosilicate ester is used. . A gel mixing method in which an alumina hydrate precipitate (alumina hydrogel) is obtained from an aqueous solution of these aluminum compounds and silicon compounds and then mixed with a silica hydrate precipitate (silica hydrogel), alumina hydrate and silica A coprecipitation method of simultaneously precipitating a hydrate or a method of depositing a silica hydrate precipitate on an alumina hydrate precipitate is arbitrarily adopted.

In order to produce the silica-containing alumina preferable as the catalyst carrier of the present invention, for example, the following method is adopted. That is, an acidic aluminum compound is reacted with ammonia in an aqueous solution to form a precipitate of alumina hydrate (alumina hydrogel). As the acidic aluminum compound, aluminum sulfate, chloride, nitrate or the like is used as described above, but sulfate is preferably used. The temperature at which the precipitate is formed is in the range of 30 ° C to 80 ° C, preferably 60 ° C to 75 ° C. When the acidic aluminum compound and ammonia are reacted, the concentration of the resulting alumina hydrate in the aqueous solution is converted to the concentration in terms of alumina,
It is preferable to keep the content in the range of 2% by weight to 10% by weight. For this purpose, the concentration of the acidic aluminum compound used in the reaction in the aqueous solution may be adjusted. When the concentration of the alumina hydrate in the aqueous solution is higher than the above range, the total pore volume decreases when silica gel is deposited on the alumina hydrate. On the other hand, when the concentration of the alumina hydrate produced becomes low, its value as a practical production method decreases.

In the present invention, when the acidic aluminum compound and ammonia are reacted in an aqueous solution, the pH of the aqueous solution is changed.
Is maintained in the range of 7 to 11, preferably 8 to 10, to generate a precipitate. The holding time is at most 2 hours, preferably 0.2 hours to 1.5 hours.

After the retention time has elapsed, the aqueous solution of the water-soluble silicon compound is additionally mixed with the aqueous solution containing the precipitate of alumina hydrate. The concentration of silicon compound in the aqueous solution is 1% by weight
The range is from 10 to 10% by weight, preferably from 2 to 8% by weight. The amount of the silicon compound added to the aqueous solution containing the precipitate of alumina hydrate is an amount corresponding to the composition of the silica-containing alumina of the final product, and the silica content in the silica-containing alumina is 2% by weight to 35% by weight. It is such an amount. The mixed solution of the aqueous solution containing the precipitate of alumina hydrate and the aqueous solution of the water-soluble silicon compound is maintained at a pH of 7 to 11, preferably 8 to 10. In this case, if necessary, adjust the pH of the aqueous solution of mineral acid or the aqueous solution of sodium hydroxide.
A regulator is added to maintain the pH of the mixed aqueous solution within the above range. This mixed aqueous solution is stirred at a temperature of 30 ° C to 80 ° C.
C., preferably in the range of 60.degree. C. to 75.degree. The holding time is at most 2 hours, preferably 0.2 hours-
1.5 hours. By this operation, a precipitate (silica-alumina cake) in which silica hydrate is deposited on alumina hydrate is obtained. This silica-alumina cake is separated from the liquid and then subjected to a conventional washing treatment, for example, a washing treatment using an aqueous solution of ammonium carbonate and water to remove impurity ions and dry until a water content for molding is obtained. The silica-containing alumina is obtained by kneading and extruding.

Next, introduction of the lanthanoid metal component into silica-containing alumina by ion exchange will be described. First, the lanthanoid-based metal component can be introduced into the silica-containing alumina by preparing an exchange liquid containing the lanthanoid-based metal component and immersing the exchange liquid in the silica-containing alumina. As the lanthanoid metal component used in the exchange liquid, inorganic salts such as nitrates, sulfates and chlorides, and organic salts such as acetates can be used. A particularly preferred compound is nitrate. The above exchange liquid dissolves these compounds in pure water and an aqueous ammonia solution, and the pH of the obtained aqueous ammonia solution is 6 to 11, preferably 7.0.
Adjusted to 9.5.

The concentration of the lanthanoid metal component in the exchange liquid is 0.001 mol / l to 0.1 mol / l, and the preferable concentration is 0.01 mol / l to 0.05 mol / l.
It is l.

Ion exchange of the lanthanoid metal component is
The temperature of the exchange liquid is 30 ° C to 80 ° C, preferably 50 ° C to 7
It can be carried out by setting the temperature to 5 ° C. and adjusting the immersion time until the desired loading amount is obtained. Generally five
Immersion for 10 to 10 hours is suitable, and the desired loading amount of the lanthanoid metal component is obtained.

The catalyst carrier composed of the silica-alumina-lanthanoid metal component obtained here has a calcination temperature of 400.
The cation exchange catalyst carrier is obtained by calcining at ℃ to 700 ℃, preferably 500 ℃ to 600 ℃.

In addition to the above, as a method for producing silica-containing alumina having a lanthanoid-based metal component introduced therein, a water-soluble lanthanoid-based solution is added to a mixed solution of the above-described aqueous solution containing a precipitate of alumina hydrate and an aqueous solution of a water-soluble silicon compound. Add the metal component solution to the specified weight and add p
By adjusting H so as to be maintained in the range of 7 to 11, preferably 8 to 10, a precipitate in which silica and a lanthanoid metal component hydrate are deposited on an alumina hydrate is obtained, and the precipitate is washed, A method of manufacturing by drying and extrusion molding can also be adopted. The solid acid amount of the catalyst carrier comprising the silica-alumina-lanthanoid metal component obtained as described above can be determined as an effective acid amount of 70 KJ / mol or more by the ammonia adsorption calorimetry method.

According to the present invention, the catalyst carrier comprising the silica-alumina-lanthanoid metal component has a high solid acidity, the acidity distribution has many weak acid points, and the proportion of strong acid points is low as compared with weak acid points. Is obtained.

The shape of the catalyst carrier is determined depending on the reaction to be used and the reaction type of the catalyst.
It may be in any shape such as a bead shape, a pellet shape, a plate shape, a film shape, or a monolith shape. Hydrotreating catalyst In the present invention, the hydrotreating catalyst comprises a silica-containing alumina having a silica content of 2% by weight to 35% by weight and a lanthanoid metal component as a metal of 0.1% by weight based on the total weight of the carrier. It can be obtained by supporting an effective amount of a hydrogenation-active metal component on a catalyst carrier containing a silica-alumina-lanthanoid-based metal component as a main component, the content of which is about 5% by weight.

The hydrogenation-active metal component is represented by V of the Periodic Table of the Elements.
It is one or more metal components selected from the group consisting of Group IB metal components and Group VIII metal components in the same table. That is,
One or more selected from the group consisting of Group VIB chromium, molybdenum and tungsten, Group VIII iron, cobalt, nickel, palladium, platinum, osmium, iridium, ruthenium and rhodium are used. For the hydrodesulfurization and hydrodenitrogenation of sulfur-containing and nitrogen-containing hydrocarbon oils, in particular a combination of a VIB metal component and a Group VIII metal component, for example molybdenum-cobalt,
Combinations of molybdenum-nickel, tungsten-nickel, molybdenum-cobalt-nickel, tungsten-cobalt-nickel and the like can be preferably used. These active metal components are listed in Table VII of the Periodic Table of the Elements.
Group metals such as manganese, and Group IV metals such as
It is also possible to add tin, germanium or the like for use.
These hydrogenation active metal components are preferably supported as oxides and / or sulfides. In addition, the carrier,
In order to increase the catalyst strength, titania or the like can be loaded at the same time.

The amount of the metal component supported is about 0.5 in the catalyst as an oxide.
In the range of about 5% to about 20% by weight, the Group VIB metal is about 5%.
It may range from wt% to about 30 wt%. When the supported metal is supported on the catalyst carrier by the impregnation method, either one-component impregnation method or two-component impregnation method may be adopted depending on the type of the metal to be supported. That is, in order to support two or more metal components, two or more metal components are mixed and impregnated simultaneously from the mixed solution (one-liquid impregnation method), or two or more metal component solutions are separately prepared. It is also possible to prepare and successively impregnate (two-liquid impregnation method), and the metal supporting method is not particularly limited in the present invention.

In order to preferably produce the catalyst of the present invention, a carrier composed of the above-mentioned silica-alumina-lanthanoid metal component is used, on which carrier is selected from the group of the Group VIB metals of the Periodic Table of the Elements. One or more metals to be supported (first step), and then one or more metal components selected from the group of Group VIII metals of the Periodic Table of the Elements (second step). More specifically, according to this two-step method, a second layer is formed on the carrier.
The hydrogenation active metal component supported in the step is one or more metals selected from Group VIII metals of the Periodic Table of the Elements. That is, one or more selected from Group VIII iron, cobalt, nickel, palladium, platinum, osmium, iridium, ruthenium and rhodium are used. Preferably, cobalt and nickel are used alone or in combination of both.

The hydrogenation active metal component supported on the carrier in the first step is one or more metals selected from the group of Group VIB metals of the Periodic Table of the Elements. That is, VI
One or more selected from the chromium, molybdenum, and tungsten of B are used. Preferably molybdenum and tungsten are used alone or in combination.

It is preferable that the hydrogenation-active metal component of Group VIII and Group VIB is supported as an oxide and / or a sulfide, and in the two-step supporting method according to the first and second steps, The loading amount of the metal component is 0.1 wt% of the Group VIII metal in the catalyst, based on the oxide.
-20% by weight, preferably 1% -8% by weight, more preferably 2-5% by weight. The amount of the Group VIB metal is 3% by weight to 30% by weight, preferably 5% by weight to 25% by weight, more preferably 8% by weight to 20% by weight. If less than 0.1% by weight of the Group VIII metal is supported, a catalyst having sufficient activity cannot be obtained, and if it exceeds 20% by weight, the amount of free metal components not bound to the carrier increases. If the free components of the Group VIII metal increase, then the V
When a Group IB metal is supported, an inactive composite oxide is generated, which lowers the dispersibility of the VIB metal and lowers the catalytic activity. On the other hand, when the content of the Group VIB metal is less than 3% by weight, the activity cannot be obtained, and when it exceeds 10% by weight, the dispersibility is lowered and at the same time, the cocatalyst effect of the Group VIII metal is not exhibited.

In the above method of supporting the catalytic metal, the method of supporting the active metal component on the carrier in the first and second steps is as follows: the carrier is immersed in an aqueous solution of a soluble salt of the metal, and the metal component is introduced into the carrier. An impregnation method or a coprecipitation method in which a hydrogenation active metal component is simultaneously precipitated during the production of a carrier can be adopted, and any other method may be adopted, but the operation is simple and the catalyst In order to guarantee the physical properties of, the impregnation method is preferable. As the impregnation operation, the carrier is immersed in the impregnating solution at room temperature or above room temperature to maintain the condition that the desired component is sufficiently impregnated into the carrier. The amount and temperature of the impregnating solution can be appropriately adjusted so that a desired amount of metal is supported. The amount of carrier to be dipped in the impregnation solution is determined according to the supported amount.

The carrier impregnated with the hydrogenation active metal component is washed with water, dried and calcined after separating the impregnating solution. In hydrodesulfurization of heavy hydrocarbon oils, the catalyst may be presulfidized prior to use. The method will be described later.

The size of the carrier is not particularly limited, but in the case of a carrier for fixed bed catalyst, the size is usually 0.5 mm to.
It is about 4.5 mm. Further, the shape and size of the catalyst of the present invention have a shape and size depending on the carrier used. Next, hydrotreating of hydrocarbon oil by using the hydrotreating catalyst of the present invention will be described. As the hydrocarbon oil, naphtha, atmospheric gas oil, vacuum gas oil, catalytic cracking gas oil, thermal cracking gas oil, vacuum distillation gas oil, heavy cracking oil and the like can be widely used.

Particularly, by using the hydrotreating catalyst of the present invention, vacuum distillation gas oil containing a considerable amount of sulfur, nitrogen and metal, cracked gas oil from a catalytic cracking unit, caulking of residual oil and visbrake. It is possible to easily perform desulfurization and denitrification of light oil and the like obtained from slag and the like. For example,
About 2 wt% to about 4 wt% sulfur content, about 0.03 wt% ~
Middle east crude oil vacuum distillation gas oil containing about 0.2% by weight of nitrogen, and light cycle oil from catalytic cracking equipment, hydrogen of gas desulfurization difficult to desulfurize and hard to denitrogenate obtained from coking and visbreaking of residual oil. The chemical treatment can be effectively performed.

The reaction conditions can be appropriately selected depending on the type of feed oil, desired desulfurization rate or denitrification rate. That is, reaction temperature: about 280 ° C. to about 420 ° C., reaction pressure: about 20 kg / cm ² to about 200 kg / cm ² , ratio of hydrogen-containing gas to feed oil: about 100 liters / liter to about 2
70 liter / liter, and liquid space velocity; about 0.5V
/ H / V to about 4.0 V / H / V is adopted. The hydrogen concentration in the hydrogen containing gas may range from about 60% to about 100%.

In carrying out the hydrodesulfurization, the catalyst may be used in any form of a fixed bed, a fluidized bed or a moving bed, but it is preferable to adopt the fixed bed in terms of equipment or operation. It is also possible to combine two or more reaction towers for hydrodesulfurization to achieve a high desulfurization rate.

The catalyst of the present invention may optionally be presulfidized prior to use. Presulfiding can be carried out in situ in the reaction tower. That is, a sulfur-containing distillate oil is added to the calcined catalyst at a temperature of about 150 ° C to about 400 ° C.
Pressure (total pressure); about 15 kg / cm ² to about 100 kg / c
m ² , liquid hourly space velocity; about 0.3 V / H / V to about 2.0 V /
H / V and hydrogen-containing gas are contacted under the conditions of about 50 liters / liter to about 1500 liters / liter,
After the sulfurization treatment is completed, the sulfur-containing distillate oil is switched to the feedstock oil and the operation is started under the appropriate operating conditions for desulfurization of the feedstock oil. In addition to the above methods, the sulfurization treatment may be carried out by directly contacting the catalyst with hydrogen sulfide or other sulfur compound, or by adding it to a suitable distillate oil and contacting it with the catalyst.

[0040]

INDUSTRIAL APPLICABILITY In the present invention, by introducing a lanthanoid metal component into silica-containing alumina, a catalyst carrier having an increased solid acidity and an optimized solid acidity distribution can be obtained. It was found that the hydrotreating catalyst obtained by supporting the components exhibited remarkably improved desulfurization activity and denitrification activity.

[0041]

EXAMPLES The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention. The methods used to evaluate the physical properties of the catalyst are as follows. 1) Specific surface area After holding 0.3 g of the sample under the conditions of 250 ° C. and 1 × 10 ⁻³ Torr, nitrogen gas was adsorbed at the liquid nitrogen temperature (77 K), and the specific surface area was calculated by the BET method. 2) Pore Volume Nitrogen Adsorption Method Following the above measurement, nitrogen gas was adsorbed to a relative pressure of 1.0 at liquid nitrogen temperature (77K), and BJH method (EP Bar) was used.
reff, L.L. G. Joyner and P.P. P. H
alnda, J Amer. Chem. Soc. , 7
3 , 373 (1951)) and the pore volume was calculated from the adsorption isotherm adsorption data. 3) Solid acidity Ammonia adsorption heat measurement method After holding 1 g of a sample for 4 hours under the condition of 400 ° C. and 1 × 10 ⁻⁴ Torr, ammonia gas is adsorbed, and the heat of adsorption generated at that time is measured. The ammonia adsorption amount was measured from the heat of adsorption, and the total acid amount was calculated from the measurement result.

In this measurement, an "adsorption heat measuring device" manufactured by Tokyo Riko Co., Ltd. was used, and an acid amount having an adsorption heat of 70 kJ / mol or more was defined as the total acid amount. Example 1 (Preparation of carrier) 3 liters of pure water was heated to about 70 ° C., and an aqueous sodium hydride solution was added thereto to prepare alkaline water having a pH of about 12. Next, in this alkaline water, an aluminum sulfate aqueous solution (aluminum sulfate Al ₂ (SO ₄ )
It was prepared by dissolving 518 g of ₃ in 710 g of pure water. ) Is added, the pH is adjusted to 8.4 to 8.8 with a 2N sodium hydroxide aqueous solution or a 2N nitric acid aqueous solution, and the pH is adjusted to about 0.8 at about 70 ° C.
It was heat-aged for 5 hours. This gave a suspension containing a precipitate of hydrated alumina (hydrogel). An aqueous sodium silicate solution (prepared by dissolving 38 g of No. 3 water glass in 210 g of pure water) was added to this suspension, and a 2N nitric acid aqueous solution was added as necessary to set the pH to about 9,
Aging was carried out at a temperature of 0 ° C. for 0.5 hours, whereby a slurry liquid containing a precipitate of alimina hydrate silica hydrate was obtained.

The slurry solution was filtered, washed with an aqueous solution of ammonium carbonate and water, and then kneaded while being dried in a kneader at 80 ° C. until it had a water content capable of molding, and a cylinder having a diameter of 1.5 mm by an extrusion molding machine. Molded into a mold and 16 at 120 ℃
It was dried for an hour and further calcined at 700 ° C. for 3 hours to obtain a silica-alumina carrier. The content of silica in this carrier was 11% by weight. (Ion exchange) of lanthanum nitrate _{(La (NO 3) 3 ·} 6H
₂ O) 43.3 g of an ion exchange solution containing 0.01 mol / l as lanthanum ions was dissolved in pure water and aqueous ammonia for 10 liters of. After adjusting the liquid temperature of the ion exchange liquid to 70 ° C., 100 g of the carrier was immersed for 10 hours while stirring. The lanthanum-impregnated silica alumina obtained by this immersion was dried at 120 ° C. for 16 hours and then calcined at 500 ° C. for 3 hours to obtain an ion-exchanged carrier.

The amount of lanthanum introduced into the silica-alumina carrier obtained here was 1.
It was 5% by weight. (Carrier of hydrogenation active metal component) The silica-alumina-lanthanum carrier obtained by the above production method is impregnated with an aqueous solution of ammonium paramolybdate,
The impregnated carrier was dried at 120 ° C. for 16 hours and calcined at 450 ° C. for 3 hours to carry 20% by weight of molybdenum oxide. Next, a molybdenum oxide-supporting carrier was impregnated with an aqueous cobalt nitrate solution, dried at 120 ° C. for 16 hours, and calcined at 500 ° C. for 3 hours to support 5% by weight of cobalt oxide to obtain a catalyst.
The hydrotreating catalyst thus obtained is referred to as catalyst A, and the physical properties of the catalyst are shown in Table 1. Example 2 lanthanum nitrate _{(La (NO 3) 3 ·} 6H 2 O) 130.
0 g was dissolved in pure water and ammonia water, and an ion exchange solution having a concentration of 0.03 mol / l as lanthanum ions was added to
Example 1 except that a catalyst carrier prepared by the same method as that described in Example 1 was dipped in the liter, and 3% by weight of lanthanum was introduced based on the total weight of the carrier.
A hydrotreating catalyst B was obtained in the same manner as in. The physical properties of this catalyst B are shown in Table 1. Example 3 A catalyst was prepared and obtained in the same manner as in Example 1 except that cerium nitrate (Ce (NO ₃ ) ₃ .6H ₂ O) was used instead of lanthanum nitrate as the lanthanoid metal component. A hydrogenation-active metal component was supported on the carrier to obtain a hydrotreating catalyst C. Example 4 A catalyst D was obtained in the same manner as in Example 1 except that neodymium nitrate (Nd (NO ₃ ) ₃ .6H ₂ O) was used instead of lanthanum nitrate as the lanthanoid-based metal component.

The physical properties of each catalyst are shown in Table 1. Comparative Example 1 A catalyst carrier was prepared in the same manner as in Example 1 except that lanthanum ion-exchange was not carried out, and the resulting carrier was loaded with a hydrogenation-active metal component to give a hydrotreating catalyst a. Obtained. The physical properties of catalyst a are also shown in Table 1.

[0046]

Table 1 Examples Comparative Examples Catalyst A Catalyst B Catalyst C Catalyst D Catalyst a MoO ₃ , wt% 19.8 19.4 19.9 19.6 20.0 CoO, wt% 5.1 4.9 5.0 4.9 4.6 La, wt% 1.1 2.3 ────── ─ Ce, Wt% ── ── 0.9 ── ── Nd, Wt% ── ── ── 1.2 ── SiO ₂ , wt% 8.6 8.6 8.6 8.7 8.7 Al ₂ O ₃ , wt% Remainder Remainder Remainder Remainder ratio Surface area, m ² / g 249 245 243 248 260 (BET method) Pore volume, ml / g 0.41 0.41 0.40 0.40 0.42 (N ₂ adsorption method) Solid acidity 0.76 0.83 0.73 0.77 0.67 (Ammonia adsorption heat measurement method) Application example 1 Using the catalysts A, B, C and D of Examples 1 to 4 and the comparative catalyst a, a Middle East crude oil vacuum distillation gas oil having the following properties was subjected to hydrotreating under the hydrotreating conditions shown below. Feedstock properties: Density (15 ° C) g / ml 0.922 Sulfur content wt% 2.00 Nitrogen content wtppm 800 Hydrotreating conditions; Reaction temperature ℃ 370 Reaction pressure kg / cm ² G 60 Hydrogen gas / feedstock oil Ratio 1 / l 210 Table 2 shows the results of the hydrotreatment. The sulfur level of the hydrotreated oil obtained as a result of the hydrotreatment is from 0.05% by weight to
0.1 wt%, nitrogen level 300 ppm-40
It is 0 ppm.

[0047]

Table 2 Table 2 Hydrotreating results Catalyst type Catalyst A Catalyst B Catalyst C Catalyst D Catalyst a Relative desulfurization activity% 109 106 106 106 107 100 Relative denitrification activity% 117 108 116 116 118 100 As described above, The hydrotreating catalyst using the refractory inorganic oxide catalyst carrier according to the present invention from Examples and Comparative Examples is compared with conventionally proposed hydrotreating catalysts,
It has been found that the desulfurization activity and the denitrification activity are remarkably high, and that it can be effectively applied to the hydrotreatment of the feed oil which is said to be difficult to desulfurize and difficult to denitrify.

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Claims (2)

[Claims] 1. A silica-containing alumina comprising silica, alumina and a lanthanoid metal component, wherein the silica content is 2% by weight to 35% by weight, and at least one lanthanoid metal component is used as a metal amount based on the total weight of the carrier. 0.1
A refractory inorganic oxide catalyst carrier comprising a silica-alumina-lanthanoid metal component as a main component, which is contained in an amount of 5% by weight to 5% by weight. 2. A silica-containing alumina comprising silica, alumina and a lanthanoid-based metal component, wherein the silica content is 2% by weight to 35% by weight, and at least one lanthanoid-based metal component as a metal amount, based on the total weight of the carrier. 0.1
At least one selected from the group consisting of Group VIB metal components of the Periodic Table of Elements and Group VIII metal components of the periodic table on a carrier containing a silica-alumina-lanthanoid-based metal component as a main component in an amount of 5% to 5% by weight. A catalyst for hydrotreating, which carries the hydrogenation-active metal component of.