JP2000079343A - Catalyst for hydrogenating light oil and hydrogenation of light oil - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a low-price hydrogenation catalyst which can reduce sulfur components in light oil remarkably and to provide a method of hydrogenation by the use of the catalyst. SOLUTION: In a catalyst obtained by impregnating an alumina carrier with an aqueous solution containing cobalt, molybdenum, and phosphorus, the specific surface area measured by a nitrogen adsorption method is 170-300 m/g, the pore volume measured by a mercury press fitting method is 0.5-0.7 ml/g, the average pore diameter in pore distribution measured by a mercury press fitting method is 70-120 Å, the pore volume in the range of the average pore diameter ±15 Å is at least 70% of the total pore volume, and the coordination number of sulfur to the molybdenum metal in the sulfurized catalyst by XAFS measurement is 5-6. The catalytic reaction of light oil is carried out in the presence of the catalyst, under hydrogen partial pressure of 3-8 MPa, at a temperature of 300-420 deg.C, and at a liquid space velocity of 0.3-5 hr-1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst for hydrotreating gas oil and a method for hydrotreating gas oil using the catalyst. More specifically, the present invention relates to a method for hydrotreating gas oil. The present invention relates to a catalyst having an excellent activity capable of greatly reducing the above-mentioned value in the case of using a conventional catalyst of this type and capable of being provided at a low cost, and a method using the catalyst.

[0002]

BACKGROUND ART Each oil fraction obtained by distillation or cracking of crude oil generally contains sulfur compounds, and when these oils are used as fuel, air pollution such as sulfur oxides caused by the sulfur compounds. The substance is released into the atmosphere. In particular,
Air pollution due to exhaust gas from diesel engines has become serious, and as a countermeasure from the viewpoint of fuel, there is a strong demand for reduction of the sulfur content in light oil. In fact, in response to the emission regulations of NOx and particulate matter in diesel vehicle exhaust gas, in Japan, the regulation value of sulfur in diesel was revised to 0.05% from October 1997, and in Europe, It has been proposed that the sulfur content in light oil be 350 ppm by 2000 and 50 ppm by 2005.

[0003] Under such circumstances, the development of an ultra-deep desulfurization technique for greatly removing the sulfur content in light oil has been gaining importance. As a technique for reducing the sulfur content in gas oil, usually, operating conditions for hydrodesulfurization, for example, reaction temperature, liquid space velocity, and the like are made severe. However, when the reaction temperature is increased, carbonaceous material is precipitated on the catalyst, and the activity of the catalyst is rapidly reduced.When the liquid hourly space velocity is reduced, the desulfurization ability is improved, but the purification treatment capacity is reduced, so that the equipment capacity is reduced. There is a need to scale up. Moreover, such severe operating conditions also have adverse effects on properties such as hue and storage stability. Therefore, the best way to achieve ultra-deep desulfurization of gas oil without severe operating conditions is to develop a catalyst having a remarkably excellent desulfurization activity.

[0004] Conventional desulfurization level (sulfur content of produced oil 0.2 to
(0.05% by mass) can be easily achieved by the current desulfurization technology, but the ultra-deep desulfurization region (sulfur content of the generated oil is 0.04% by mass or less) rapidly becomes difficult. This is because sulfur compounds such as 4-methyldibenzothiophene and 4,6-dimethyldibenzothiophene having steric hindrance to the desulfurization active site make desulfurization extremely difficult.

[0005] Therefore, in order to efficiently perform a desulfurization reaction in the deep desulfurization region, the number of active points of the catalyst must be increased so that the desulfurization reaction of a substance having steric hindrance to these desulfurization active points proceeds efficiently. Also, a technique for preparing a fine chemical catalyst capable of increasing the desulfurization activity per active metal amount is required.

Further, there is a strong correlation between the amount of active metal on the catalyst carrier and the desulfurization activity. It is said that as the amount of active metal increases, the active point of the catalyst increases and the desulfurization activity also improves. Many studies have been conducted to increase the amount of active metals supported. For example, Japanese Patent Application Laid-Open No. 4-26515
No. 8 discloses Co as a catalyst for increasing the amount of active metal supported,
(4.5 to 7.0% by mass in terms of oxide) and the content of VIA group metal (19.0 to 25.0% by mass in terms of oxide) are increased, and phosphorus (0.3% in terms of oxide) is increased. (3.0 mass%) is disclosed, and according to this catalyst, the hydrodesulfurization ability of the sulfur-containing hydrocarbon oil is improved. However, the price of cobalt is high, and when a large amount of cobalt is supported, the cost of the catalyst is significantly increased.

[0007]

The object of the present invention is, firstly, to provide an inexpensive gas oil hydrotreating catalyst capable of greatly increasing the hydrodesulfurization active points and consequently enhancing the desulfurization activity. The second is to provide a method for hydrotreating light oil using this catalyst.

[0008]

SUMMARY OF THE INVENTION The present inventors relate to a catalyst of the above object,
The number of catalytic active sites (Co-Mo-S phase) and M
We have attempted to develop a high-performance desulfurization catalyst that precisely controls the degree of sulfidation of o, enables efficient desulfurization reactions, and does not require severe reaction conditions even in the ultra-deep desulfurization region. Specifically, the active metal is highly dispersed and the desulfurization active site (Co-Mo)
-S phase) was examined. As a result, Co, M
When preparing an aqueous solution containing each component of o and phosphorus and loading this aqueous solution on alumina used as a normal catalyst carrier, it is usually considered to increase the amount of active metal to increase the desulfurization active point. However, conversely, when the amount of Co was reduced, it was found that the catalyst became highly active and its hydrodesulfurization activity was significantly improved, and the present invention was proposed.

[0009] The catalyst of the present invention is based on the above-mentioned findings. Among the active metals (Co and Mo), each of Co, Mo, and phosphorus is adjusted so that the specific amount and ratio of the supported metal are reduced. A catalyst obtained by impregnating an aqueous solution containing the components with an alumina carrier, the catalyst basis, in terms of oxide, 2 to 2
4 wt% Co, 16-22 wt% Mo, and 0.8
リ ン 4.5% by mass of phosphorus, and the mass ratio of Co and Mo is
The value of [CoO] / [CoO + MoO ₃ ] is 0.12 to
0.2, the mass ratio of Mo to phosphorus is [P ₂ O ₅ ] / [Mo
O ₃ ], the specific surface area measured by the nitrogen adsorption method is from 170 to 300 m ² / g, and the pore volume measured by the mercury intrusion method is from 0.5 to 0.7 ml / g. The average pore diameter in the pore distribution measured by the mercury intrusion method is 70 to 120.
{, The pore volume in the range of the average pore diameter ± 15} is at least 70% of the total pore volume, and the coordination number of sulfur to Mo metal in the catalyst after sulfidation is 5 to 6 as measured by XAFS. It is characterized by. At this time, CoO, MoO ₃ , P ₂ O ₅ ,
Metal content other than alumina is 1% by mass or less,
The purity of alumina is preferably 98% by mass or more.

[0010] The hydrotreating method of the present invention is characterized in that a hydrogen partial pressure of 3 to 8 MPa, 300 to 420 in the presence of the above-mentioned catalyst.
It is characterized by performing a contact reaction of a gas oil fraction containing a sulfur content at a temperature of 0.3 ° C. and a liquid hourly space velocity of 0.3 to 5 hr ⁻¹ .

As the target oil of the present invention, for example, gas oil fractions such as straight-run gas oil, catalytic cracked gas oil, pyrolyzed gas oil, hydrogenated gas oil, desulfurized gas oil, and vacuum distilled gas oil (VGO) are suitable. Typical properties of these feedstocks include those having a boiling range of 150 to 450 ° C. and a sulfur content of 5% by mass or less.

Alumina, which is a carrier of the catalyst of the present invention, has α
Various aluminas such as -alumina, β-alumina, γ-alumina and δ-alumina can be used, but porous alumina having a high specific surface area is preferable, and γ-
Alumina is suitable. The purity of alumina is 98% by mass
Above, preferably 99% by mass or more is suitable.
As impurities in alumina, SO ₄ ²⁻ , Cl, Fe
₂ O _3, Na ₂ but O, etc., these impurities is desirably as small as possible, 2 wt% of an impurity total amount or less, preferably less than 1 wt%, SO ₄ in each component
^2- <1.5% by mass, Cl, Fe ₂ O ₃ , Na ₂ O <
It is preferably 0.1% by mass.

Inorganic oxides other than alumina which are usually used as carriers include, for example, silica, boria, titania, zirconia, magnesia, hafnia, ceria, yttria, niobia, chromia, thoria, etc. There are oxides, crystalline inorganic oxides such as zeolites and molecular sieves, and clay minerals such as montmorillonite, kaolin, bentonite and saponite. These inorganic oxides are not particularly required in the catalyst of the present invention. When these oxides are present in a carrier in a certain amount or more, they may be the main cause of a decrease in desulfurization activity. That is, in the above-mentioned amorphous oxide, the amount of hydroxyl groups required for supporting Mo on the active metal is extremely smaller than that of alumina, so that Mo cannot be highly dispersed and the desulfurization activity decreases. On the other hand, the above-mentioned crystalline inorganic oxides and clay minerals have a surface area higher than that of alumina, but have extremely small pore diameters, so that Mo compounds in an impregnating solution having a molecular diameter larger than the pore diameters are used. ,
In addition to being unable to be supported in the pores, the above-mentioned crystalline inorganic oxide is more expensive than alumina, and if these are contained in the carrier, the cost of the catalyst will be high.

The specific surface area, pore volume, and average pore diameter of the alumina carrier are not particularly limited. However, in order to obtain a catalyst having a high hydrodesulfurization activity with respect to light oil, the specific surface area is preferably 2%.
40 to 400 m ² / g, preferably 300 to 350 m ²
/ G, a pore volume of 0.55 to 0.9 ml / g, preferably 0.65 to 0.8 ml / g, and an average pore diameter of 60 to 12
0 °, preferably 65-90 °, is suitable.

If the specific surface area is less than 240 m ² / g, the dispersibility of the active metal becomes poor, so that the catalyst has a low desulfurization activity. When the specific surface area is larger than 400 m ² / g, the pore diameter becomes extremely small, so that the pore diameter of the catalyst also becomes small. When the pore diameter of the catalyst is small, the diffusion of the sulfur compound into the pores of the catalyst becomes insufficient, and the desulfurization activity decreases.

When the pore volume is less than 0.55 ml / g, a small amount of solvent enters the pore volume when preparing a catalyst by a usual impregnation method. When the amount of the solvent is small, the solubility of the active metal compound is deteriorated, the dispersibility of the metal is reduced, and the catalyst has low activity. In order to increase the solubility of the active metal compound, there is a method of adding a large amount of an acid such as nitric acid. However, if it is added too much, the surface area of the carrier is reduced, which is a main cause of a decrease in desulfurization performance. If the pore volume is larger than 0.9 ml / g, the specific surface area becomes extremely small, the dispersibility of the active metal becomes poor, and the catalyst has a low desulfurization activity.

When the pore diameter is less than 60 °, the pore diameter of the catalyst supporting the active metal also becomes small. When the pore diameter of the catalyst is small, the diffusion of the sulfur compound into the pores of the catalyst becomes insufficient, and the desulfurization activity decreases. When the pore diameter is larger than 120 °, the specific surface area becomes small. If the specific surface area is small,
The dispersibility of the active metal becomes poor, resulting in a catalyst having low desulfurization activity.

The amount of acid of the alumina carrier measured by the ammonia-TPD method is preferably from 0.3 to 1 mmol / g.
If it is less than 0.3 mmol / g, the amount of hydroxyl groups is too small,
Mo may not be highly dispersed and may become a catalyst having a low desulfurization activity. If it is more than 1 mmol / g, the gas oil fraction rapidly over-decomposes on acid sites, and carbon deposition which is a main cause of activity deterioration is caused. Will be invited.

Co, M supported on the above alumina carrier
Of the o and phosphorus components, examples of the Co compound include carbonate, acetate, nitrate, sulfate, and chloride, and are preferably carbonate, acetate, and more preferably carbonate. Examples of the Mo compound include molybdenum trioxide, molybdophosphoric acid, ammonium molybdate, molybdic acid, and the like.
Molybdophosphoric acid and molybdenum trioxide are preferred.
Phosphorus may be derived from these compounds when a compound containing phosphorus such as molybdophosphoric acid is used as the compound of the active ingredient, or when a compound other than the phosphorus compound is used. When phosphorus derived from a phosphorus compound alone is insufficient, another phosphorus source is used together with this compound. Examples of other phosphorus sources include various phosphoric acids, and specific examples include orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid, and polyphosphoric acid. Orthophosphoric acid is particularly preferable.

Among these active components, the content of Co is 2 to 4% by mass, preferably 2.5 to 3.8% by mass in terms of oxide on a catalyst basis. If the content of Co is less than 2% by mass, the active sites attributed to Co cannot be sufficiently obtained, and 4% by mass
Is exceeded, the dispersibility of the active metal deteriorates due to the aggregation of the Co compound, and the inactive precursor Co ₃ O
_{Since four} species (existing as Co ₉ S ₈ after catalytic sulfurization and during hydrogenation treatment) and Co spinel species incorporated in the lattice of the carrier, no improvement in catalytic activity is observed.
Conversely, the catalytic activity decreases.

The content of Mo is 16 to 22% by mass, preferably 16 to 18% by mass in terms of an oxide as a catalyst. If the Mo content is less than 16% by mass, it is not sufficient to exhibit the effect due to Mo. If the Mo content exceeds 22% by mass, the dispersibility of the active metal is deteriorated due to the aggregation of Mo, and the active metal is efficiently dispersed. There is no improvement in catalytic activity because the active metal content exceeds the limit or the catalyst surface area is significantly reduced.

The content of phosphorus is from 0.8 to 4.5% by mass, preferably from 1.0 to 4% by mass in terms of oxide on a catalyst basis. Phosphorus acts to improve the acid properties of the catalyst. When the catalyst exhibits a suitable acidity value, the dispersibility of the active ingredient is improved, the amount of acid sites on the carrier shows an optimal value, the adsorption of sulfur compounds is promoted, and the hydrogenation of sulfur compounds is promoted. Improve desulfurization activity. If the amount of phosphorus is too large, the surface area and pore volume of the catalyst decrease, and the desulfurization activity decreases. If the content of phosphorus is less than 0.8% by mass, the technical significance of including a phosphorus component is not exhibited, and the sulfur content in the gas oil fraction cannot be efficiently removed. , This effect becomes saturated and uneconomical.

With the above contents of the Co, Mo and phosphorus components, the optimum mass ratio of the active metals Co and Mo is:
The value of [CoO] / [CoO + MoO ₃ ] is 0.12 to
The optimum mass ratio of Mo, which is an active metal, to phosphorus, which is a component for improving the acidity of the catalyst, is [P ₂ O ₅ ] / [Mo
O ₃ ] in the range of 0.05 to 0.25. Co and Mo
If the mass ratio is less than 0.12 in the above value, a Co-Mo-S phase, which is considered to be an active point of desulfurization, cannot be sufficiently generated, and the desulfurization activity does not improve. If it is larger than 0.2, useless Co species ( ₈ Co ₉ S or Co spinel species incorporated in the lattice of the carrier) which are not involved in the activity are generated, and the catalytic activity is reduced. If the mass ratio of Mo and phosphorus is less than 0.05 in the above value, Co and Mo cannot be completely integrated, and a Co-Mo-S phase, which is the active point of desulfurization, is hardly obtained finally, and the activity of Low catalyst. When it is larger than 0.25, the surface area and pore volume of the catalyst are reduced, and not only the activity of the catalyst is reduced, but also the acid amount is increased, and carbon precipitation is caused to easily cause deterioration of the activity.

In the catalyst of the present invention, the coordination number of sulfur to Mo metal after the sulfurization treatment is XAFS (X-ra
y Absorption Fine Structu
re << X-ray absorption fine structure >>) is 5 to 6. Coordination number of sulfur is less than 5 (that is, catalyst having low sulfuration degree of Mo)
Does not provide sufficient desulfurization activity. The theoretical upper limit of the coordination number of sulfur to Mo is 6.

Further, the catalyst of the present invention is characterized in that after sulfuration treatment,
When O was adsorbed and observed by diffuse reflection FT-IR,
The intensity of the NO spectrum (1860 cm ⁻¹ ) adsorbed on Co was determined by comparing the intensity of the NO spectrum adsorbed on ICo and Mo (169 cm ⁻¹ ).
When the intensity of 0 cm ⁻¹ ) is defined as IMo, ICo / (I
The value of (Co + IMo) is preferably in the range of 0.3 to 0.55. If it is less than 0.3, the Co-Mo-S phase, which is considered to be the active point of desulfurization, is not sufficiently generated, and the desulfurization activity is not improved. If it is larger than 0.55, useless Co species ( ₈ Co ₉ S or Co spinel species incorporated in the lattice of the carrier) which are not involved in the activity are generated, and the catalytic activity is reduced.

[0026] In addition, the catalyst of the present invention comprises CoO, MoO
Preferably, the content of metals other than ₃ , P ₂ O ₅ and alumina is 1% by mass or less. 1% by mass of metals other than these
If it is contained in a larger amount, the active sites are destroyed, resulting in a catalyst having low desulfurization activity.

The catalyst of the present invention is prepared by an impregnation method in which the carrier is impregnated with a solution prepared by dissolving the compound of each of the above components in a solvent such as water or an acid, and the components are supported. In addition, as a method of impregnating each component of Co, Mo, and phosphorus into the carrier, a one-stage impregnation method of simultaneously impregnating these components is preferable. This is because the one-stage impregnation method is considered to be advantageous from the viewpoint of catalyst properties such as desulfurization active points, acid properties, pores, etc., or operability. That is, according to the one-stage impregnation method, Co and Mo are completely integrated and taken into the carrier, so that the active point of desulfurization, Co-
Mo-S phase can be greatly increased. At this time, if the phosphorus component is present in the impregnating solution, Co and Mo
Is promoted.

On the other hand, in the method in which Co and Mo are impregnated in two steps, Co and Mo are not sufficiently integrated, and it is difficult to finally form a Co—Mo—S phase, which is an active site of desulfurization. It is considered to be. For example, Co may be Co ₃ O ₄ species, which is the inactive precursor described above, or Co spinel species, which is not involved in the activity incorporated in the lattice of the carrier.

A specific method for supporting Co and Mo on a carrier is as follows. Co, Mo and phosphorus compounds (M
o When the compound contains phosphorus, the phosphorus compound is not added or an appropriate amount of the phosphorus compound is added). During preparation, heating (30 to 100 ° C.) or addition of an acid (nitric acid, organic acid << citric acid, acetic acid, malic acid, tartaric acid, etc. &quot;) may be performed to promote the dissolution of these compounds. . The prepared solution is gradually added to the carrier so as to be uniform and impregnated. The impregnation time is 1 minute to 5 hours, preferably 5 minutes to 3 hours, the temperature is 5 to 100 ° C, preferably 10 to 80 ° C, and the atmosphere is not particularly limited.
Suitable in nitrogen and vacuum.

After the impregnation and loading, at room temperature to 80 ° C. in a nitrogen stream,
In a stream of air or vacuum, a certain amount of water (LO
I << Loss on ignition >> so as to be 50% or less), and dry in a drying oven in an air stream at 80 to 15%.
Dry at 0 ° C. for 10 minutes to 10 hours. Next, a firing furnace,
The baking is performed in an air stream at 300 to 700 ° C. for 10 minutes to 10 hours.

The catalyst of the present invention prepared as described above has its specific surface area, pore volume and average pore diameter restricted to the following values in order to enhance the hydrogenation activity and desulfurization activity for the gas oil fraction. Is done. The specific surface area (BET method) is 170
３００300 m ² / g, preferably 180-280 m ² / g
And If it is less than 170 m ² / g, the dispersibility of the active metal becomes poor and the catalyst has low desulfurization activity. If it is more than 300 m ² / g, the pore diameter becomes extremely small, so that the catalyst pore diameter also becomes small. During the hydrogenation, the diffusion of the sulfur compound into the pores of the catalyst becomes insufficient, and the desulfurization activity decreases.

The pore volume (mercury intrusion method) is 0.5 to 0.5.
7 ml / g, preferably 0.51 to 0.6 ml / g. If it is less than 0.5 ml / g, during the hydrogenation treatment, the diffusion of sulfur compounds in the pores of the catalyst becomes insufficient, resulting in insufficient desulfurization activity. Becomes extremely small, the dispersibility of the active metal decreases, and the catalyst has a low desulfurization activity.

The average pore diameter is 70-120 °, preferably 75-110 °. If the temperature is less than 70 °, the reactant is less likely to diffuse into the pores, and the desulfurization reaction does not proceed efficiently. If the temperature is more than 120 °, the diffusivity in the pores is good, but the surface area in the pores is reduced. In addition, the effective specific surface area of the catalyst decreases, and the activity decreases.

In order to increase the effective number of pores satisfying the above pore conditions, the pore size distribution of the catalyst, that is, the proportion of pores having a pore diameter of average pore diameter ± 15 ° is 70% or more. Preferably, it is 80% or more. Moreover, the pore distribution is preferably monomodal. If the pore size distribution of the catalyst is not sharp, the pores not involved in the activity increase, and the desulfurization activity decreases.

The shape of the catalyst is not particularly limited, and various shapes usually used for this type of catalyst, for example, a columnar shape or a four-leaf type, can be adopted. It is a leaf type. Usually, the catalyst preferably has a diameter of 1 to 2 mm and a length of 2 to 5 mm. The mechanical strength of the catalyst is determined by the lateral fracture strength (SCS << Side cruise
h strength >>) is preferably 2 lbs / mm or more. If the SCS is less than 2 lbs / mm, the catalyst charged in the reactor is destroyed, and a differential pressure is generated in the reactor,
The continuation of the hydrotreating operation becomes impossible. The closest packed bulk density (CBD) of the catalyst
(energy) is preferably from 0.6 to 0.9.

The distribution of the active metal in the catalyst is preferably a uniform type in which the active metal is uniformly distributed in the catalyst.

The hydrotreating method of the present invention has a hydrogen partial pressure of 3 to 3.
8MPa, 300-420 ° C, liquid space velocity 0.3-
This is a method in which the above catalyst is brought into contact with a gas oil fraction containing a sulfur compound under the condition of 5 hr ^-1 to carry out desulfurization, thereby reducing the non-desulfurizable sulfur compound content in the gas oil fraction.

In order to carry out the hydrotreating method of the present invention on a commercial scale, a fixed bed, a moving bed or a fluidized bed type catalyst layer of the catalyst of the present invention is formed in a reactor, and the raw material is placed in the reactor. Oil may be introduced and the hydrogenation reaction may be performed under the above conditions. Most commonly, a fixed bed catalyst layer is formed in the reactor, the feedstock is introduced into the upper part of the reactor, the fixed bed is passed from top to bottom, and the product flows out from the lower part of the reactor. Alternatively, the feedstock is introduced into the lower part of the reactor, passes through the fixed bed from bottom to top, and the product flows out of the upper part of the reactor.

The hydrotreating method of the present invention may be a single-stage hydrotreating method in which the catalyst of the present invention is charged into a single reactor, or may be charged into several reactors. A multi-stage continuous hydrotreating method may be used.

Before use, the catalyst of the present invention (ie,
Prior to carrying out the hydrotreating method of the present invention), it is activated by sulfidation in a reactor. This sulfurization treatment is performed for 20
Under a hydrogen atmosphere at 0 to 400 ° C., preferably 250 to 350 ° C., and a hydrogen partial pressure of normal pressure or higher, a sulfur distillate containing a sulfur compound and a sulfurizing agent such as dimethyl disulfide or carbon disulfide are added thereto. Or using hydrogen sulfide.

[0041]

EXAMPLES [Preparation of Catalyst] The procedure for measuring the carrier used in the following Examples and Comparative Examples by the ammonia-TPD method was as follows. Ammonia manufactured by Nippon Bell Co., Ltd.
Using a TPD device, 0.1 g of a sample (carrier) was filled into an adsorption tube, and as a pretreatment, 50 ° C. to 500 ° C. in a He gas stream.
The temperature was raised over a minute, and the temperature was kept at 500 ° C. for 1 hour in the same air flow.
The temperature was lowered to room temperature in 11 minutes and 30 seconds, and ammonia was adsorbed at room temperature and normal pressure for 15 minutes.
Degassing was performed at 100 ° C. for 12 minutes and 30 seconds under a reduced pressure of Torr. For the degassed sample, the temperature was raised at a rate of 10 ° C.
/ Min, in a He gas flow, the ammonia desorption spectrum was observed, and the total ammonia desorption amount was determined and defined as the acid amount.

Example 1 An alumina (γ) having a pore volume of 0.70 ml / g, a surface area of 334 m ² / g, and an average pore diameter of 69 ° was placed in an eggplant type flask.
-Al ₂ O ₃ , 1/16 inch diameter columnar molded product, acid amount 0.52 mmol / g, impurities: Na ₂ O 0.08 mass%, SO ₄ ² -0.53 mass%, SiO ₂ 0.04 mass %) Of 50.00 g and ion-exchanged water there.
3.021 g of cobalt carbonate and molybdophosphoric acid 1 in 5 g
A solution in which 5.1161 g and orthophosphoric acid 1.9532 g were dissolved was added with a pipette, immersed at about 25 ° C. for 1 hour, air-dried in a nitrogen stream, and dried in a muffle furnace at 120 ° C. for about 1 hour.
For 4 hours, and then calcined at 500 ° C. for 4 hours.
I got

Example 2 Into an eggplant type flask, 30.00 g of the same alumina as that used in Example 1 was charged, and ion-exchanged water was added thereto.
A solution prepared by dissolving 1.8315 g of cobalt carbonate, 8.9534 g of molybdophosphoric acid and 0.6258 g of orthophosphoric acid in 1 g was added, dipped, air-dried, dried and calcined under the same conditions as in Example 1 to obtain Catalyst B.

Example 3 Into an eggplant type flask, 30.00 g of the same alumina as that used in Example 1 was charged, and ion-exchanged water was added thereto.
A solution prepared by dissolving 1.8083 g of cobalt carbonate, 8.8401 g of molybdophosphoric acid, and 0.0935 g of orthophosphoric acid in 1 g was added, dipped, air-dried, dried and calcined under the same conditions as in Example 1 to obtain Catalyst C.

Example 4 Into an eggplant type flask, 30.00 g of the same alumina as that used in Example 1 was charged, and ion-exchanged water was added to the flask.
A solution prepared by dissolving 1.8797 g of cobalt carbonate, 9.1890 g of molybdophosphoric acid and 1.7324 g of orthophosphoric acid in 1 g was added, dipped, air-dried, dried and calcined under the same conditions as in Example 1 to obtain Catalyst D.

Example 5 Into an eggplant type flask, 30.00 g of the same alumina as used in Example 1 was charged, and ion-exchanged water was added thereto.
A solution prepared by dissolving 1.5461 g of cobalt carbonate, 9.3364 g of molybdophosphoric acid and 1.1589 g of orthophosphoric acid in 1 g was added, dipped, air-dried, dried and calcined under the same conditions as in Example 1 to obtain Catalyst E.

Example 6 Into an eggplant type flask, 30.00 g of the same alumina as used in Example 1 was charged, and ion-exchanged water was added to the flask.
A solution prepared by dissolving 2.1645 g of cobalt carbonate, 8.8029 g of molybdophosphoric acid, and 1.1849 g of orthophosphoric acid in 1 g was added, dipped, air-dried, dried and calcined under the same conditions as in Example 1 to obtain Catalyst F.

Example 7 In an eggplant type flask, alumina (γ) having a pore volume of 0.71 ml / g, a surface area of 329 m ² / g, and an average pore diameter of 74 ° was used.
-Al ₂ O ₃ , four-leaf molded product having a diameter of 1.27 mm × 1.07 mm, an acid amount of 0.49 mmol / g, impurity: Na
₂ O 0.07% by mass, SO ₄ ²⁻ 0.48% by mass, Si
(O ₂ 0.05% by mass) 50.00 g was added thereto, and 3.021 g of cobalt carbonate, 15.1161 g of molybdophosphoric acid and 1.9 g of orthophosphoric acid were added to 40.5 g of ion-exchanged water.
The solution in which 532 g was dissolved was added and dipped, air-dried, dried and calcined under the same conditions as in Example 1 to obtain Catalyst G.

Example 8 50.00 g of the same alumina as used in Example 1 was charged into an eggplant type flask, and ion-exchanged water was added to the flask.
6.4754 g of cobalt acetate and 1 molybdophosphoric acid in 5 g
A solution prepared by dissolving 5.1161 g of orthophosphoric acid and 1.9532 g of orthophosphoric acid was added, dipped, air-dried, dried and calcined under the same conditions as in Example 1 to obtain Catalyst H.

Example 9 In an eggplant type flask, alumina (γ) having a pore volume of 0.75 ml / g, a surface area of 254 m ² / g and an average pore diameter of 85 ° was used.
-Al ₂ O ₃ , four-leaf molded product having a diameter of 1.27 mm × 1.07 mm, an acid amount of 0.40 mmol / g, and an impurity of Na
₂ O 0.07% by mass, SO ₄ ²⁻ 0.48% by mass, Si
50.0 g of O _{2 (} 0.04% by mass) was added thereto, and 3.021 g of cobalt carbonate, 15.1161 g of molybdophosphoric acid, and 1.9 orthophosphoric acid were added to 40.5 g of ion-exchanged water.
The solution in which 532 g was dissolved was added with a pipette, and about 25
After immersion at 1 ° C. for 1 hour, air-dried in a stream of nitrogen, dried in a muffle furnace at 120 ° C. for about 1 hour, and then calcined at 500 ° C. for 4 hours to obtain Catalyst I.

Comparative Example 1 Into an eggplant type flask, 30.00 g of the same alumina as used in Example 1 was charged, and ion-exchanged water was added to the flask.
A solution in which 1.9047 g of cobalt carbonate, 9.3115 g of molybdophosphoric acid, and 2.3079 g of orthophosphoric acid were dissolved in 1 g was added, dipped, air-dried, dried and calcined under the same conditions as in Example 1 to obtain Catalyst a.

Comparative Example 2 240.00 g of the same alumina as used in Example 1 was charged into an eggplant-shaped flask, and ion-exchanged water 18 was added thereto.
To 4.8 g of ammonium paramolybdate 55.195
A solution in which 3 g is dissolved is added using a pipette, and about 2 g is added.
After immersion at 5 ° C for 1 hour, air-dry in a stream of nitrogen
It was dried at 20 ° C. for about 1 hour, and then baked at 500 ° C. for 4 hours to carry Mo. Thereafter, an aqueous solution in which 58.2580 g of cobalt nitrate hexahydrate was dissolved in 184.8 g of ion-exchanged water was added using a pipette, immersed at about 25 ° C. for 1 hour, air-dried in a nitrogen stream, and dried in a muffle furnace at 120 ° C. C. for about 1 hour and then calcined at 500.degree.
o was carried out to obtain a catalyst b.

Comparative Example 3 240.00 g of the same alumina as used in Example 1 was charged into an eggplant type flask, and ion-exchanged water 18 was added thereto.
Ammonium paramolybdate 62.554 in 4.8 g
The solution in which 7 g was dissolved was added and immersed, air-dried, dried and fired under the same conditions as in the case of supporting Mo in Comparative Example 2 to carry out the supporting of Mo. After this, cobalt nitrate hexahydrate 34.954
An aqueous solution obtained by dissolving 8 g in ion-exchanged water 184.8 g
Under the same conditions as in the case of supporting Co of Comparative Example 2, addition and immersion, air drying, drying, and calcination were performed to carry Co, thereby obtaining a catalyst c.

Comparative Example 4 Into an eggplant type flask, 30.00 g of the same alumina as that used in Example 1 was charged, and ion-exchanged water was added thereto.
A solution in which 1.9569 g of cobalt carbonate, 9.5666 g of molybdophosphoric acid and 3.5060 g of orthophosphoric acid were dissolved in 1 g was added, dipped, air-dried, dried and calcined under the same conditions as in Example 1 to obtain a catalyst d.

Comparative Example 5 Into an eggplant-shaped flask, 30.00 g of the same alumina as that used in Example 1 was charged, and ion-exchanged water was added thereto.
A solution prepared by dissolving 1.2368 g of cobalt carbonate, 9.6032 g of molybdophosphoric acid, and 1.159 g of orthophosphoric acid in 1 g was added, dipped, air-dried, dried and calcined under the same conditions as in Example 1 to obtain a catalyst e.

Comparative Example 6 Into an eggplant type flask, 150.00 g of the same alumina as used in Example 1 was charged, and ion-exchanged water 2 was added thereto.
A solution in which 12.2728 g of cobalt carbonate, 42.3508 g of molybdophosphoric acid and 4.3417 g of orthophosphoric acid were dissolved in 3.1 g was added, dipped, air-dried, dried and calcined under the same conditions as in Example 1 to obtain catalyst f. Was.

Comparative Example 7 Into an eggplant-shaped flask, 50.00 g of the same alumina as used in Example 1 was charged, and ion-exchanged water was added thereto.
A solution obtained by dissolving 10.7923 g of cobalt acetate, 13.3378 g of molybdophosphoric acid and 4.3417 g of orthophosphoric acid in 8 g was added and immersed under the same conditions as in Example 1;
Drying and baking were performed to obtain a catalyst g.

Comparative Example 8 Into an eggplant-shaped flask, 50.00 g of the same alumina as that used in Example 1 was charged, and ion-exchanged water was added thereto.
A solution prepared by dissolving 12.9508 g of cobalt acetate, 12.4486 g of molybdophosphoric acid and 2.0832 g of orthophosphoric acid in 8 g was added and immersed in the same conditions as in Example 1;
Drying and calcination were performed to obtain a catalyst h.

Comparative Example 9 Into an eggplant-shaped flask, 50.00 g of the same alumina as used in Example 1 was charged, and ion-exchanged water was added thereto.
A solution obtained by dissolving 15.1093 g of cobalt acetate, 11.5594 g of molybdophosphoric acid and 2.1266 g of orthophosphoric acid in 8 g was added and immersed under the same conditions as in Example 1;
Drying and calcination were performed to obtain a catalyst i.

Comparative Example 10 Into an eggplant-shaped flask, 50.00 g of the same alumina as used in Example 1 was charged, and ion-exchanged water was added thereto.
6.4904 g of nickel acetate and 1 molybdophosphoric acid in 8 g
A solution prepared by dissolving 5.1161 g of orthophosphoric acid and 1.9532 g of orthophosphoric acid was added, dipped, air-dried, dried and calcined under the same conditions as in Example 1 to obtain a catalyst j.

Comparative Example 11 Into an eggplant type flask, 50.00 g of the same alumina as that used in Example 1 was charged, and ion-exchanged water was added thereto.
4.4423 g of nickel acetate and cobalt acetate 6.
A solution in which 6481, molybdophosphoric acid (15.5192 g) and orthophosphoric acid (2.553 g) were dissolved was added, dipped, air-dried, dried and calcined under the same conditions as in Example 1 to obtain a catalyst k.

Comparative Example 12 An alumina (γ) having a pore volume of 0.54 ml / g, a surface area of 247 m ² / g and an average pore diameter of 74 ° was placed in an eggplant-shaped flask.
-Al ₂ O ₃ , 1/16 inch diameter columnar molded product, acid amount 0.36 mmol / g, impurities: Na ₂ O 0.07 mass%, SO ₄ ² -0.52 mass%, SiO ₂ 0.04 mass %) Of 30.00 g, and ion-exchanged water there.
A solution prepared by dissolving 1.8553 g of cobalt carbonate, 9.0697 g of molybdophosphoric acid and 1.1719 g of orthophosphoric acid in 0 g was added, immersed, air-dried, dried and calcined under the same conditions as in Example 1 to obtain Catalyst 1.

Comparative Example 13 An alumina (γ) having a pore volume of 0.54 ml / g, a surface area of 358 m ² / g and an average pore diameter of 53 ° was placed in an eggplant-shaped flask.
-Al ₂ O ₃ , 1/16 inch diameter columnar molded product, acid amount 0.54 mmol / g, impurities: Na ₂ O 0.08 mass%, SO ₄ ² -0.49 mass%, SiO ₂ 0.04 mass %) Of 50.00 g of ion-exchanged water.
3.021 g of cobalt carbonate and molybdophosphoric acid 1 in 5 g
A solution obtained by dissolving 5.1161 g of orthophosphoric acid and 1.9532 g of orthophosphoric acid was added, dipped, air-dried, dried and calcined under the same conditions as in Example 1 to obtain a catalyst m.

Comparative Example 14 An alumina (γ) having a pore volume of 0.57 ml / g, a surface area of 378 m ² / g, and an average pore diameter of 53 ° was placed in an eggplant-shaped flask.
-Al ₂ O ₃ , four-leaf shaped product having a diameter of 1.27 × 1.07 mm, acid amount 0.66 mmol / g, impurity: Na ₂ O
0.09 mass%, SO ₄ ²⁻ 0.53 mass%, SiO ₂
50.05 g) was added thereto, and 3.021 g of cobalt carbonate, 15.1161 g of molybdophosphoric acid, and 1.953 g of orthophosphoric acid were added to 33.5 g of ion-exchanged water.
The solution in which 2 g was dissolved was added and immersed, air-dried, dried and calcined under the same conditions as in Example 1 to obtain a catalyst n.

Comparative Example 15 An alumina (γ) having a pore volume of 0.71 ml / g, a surface area of 298 m ² / g, and an average pore diameter of 84 ° was placed in an eggplant-shaped flask.
-Al ₂ O ₃ , 1/16 inch diameter columnar molded product, acid amount 0.44 mmol / g, impurities: Na ₂ O 0.08 mass%, SO ₄ ² -0.57 mass%, SiO ₂ 0.04 mass %) Of 30.00 g, and ion-exchanged water was added thereto.
A solution in which 1.8553 g of cobalt carbonate, 9.0697 g of molybdophosphoric acid and 1.1719 g of orthophosphoric acid were dissolved in 5 g was added, dipped, air-dried, dried and calcined under the same conditions as in Example 1 to obtain a catalyst o.

Comparative Example 16 Into an eggplant type flask, 30.00 g of the same alumina as used in Example 1 was charged, and ion-exchanged water was added to the flask.
3.1746 g of cobalt carbonate and 1 molybdophosphoric acid per 1 g
A solution in which 5.2149 g and 1.0995 g of orthophosphoric acid were dissolved was added, dipped, air-dried, dried and calcined under the same conditions as in Example 1 to obtain a catalyst p.

Comparative Example 17 An alumina (γ) having a pore volume of 0.68 ml / g, a surface area of 316 m ² / g and an average pore diameter of 74 ° was placed in an eggplant-shaped flask.
-Al ₂ O ₃ , 1/16 inch diameter columnar molded product, acid amount 0.48 mmol / g, impurities: Na ₂ O 0.09 mass%, SO ₄ ² -0.52 mass%, SiO ₂ 0.04 mass %) Of 30.00 g of ion-exchanged water.
A solution in which 1.8553 g of cobalt carbonate, 9.0697 g of molybdophosphoric acid, and 1.1719 g of orthophosphoric acid were dissolved in 9 g was added, dipped, air-dried, dried and calcined under the same conditions as in Example 1 to obtain a catalyst q.

Comparative Example 18 30.00 g of the same alumina as that used in Example 1 was charged into an eggplant-shaped flask.
A solution in which 9.3115 g of molybdenum phosphoric acid and 2.3079 g of orthophosphoric acid were dissolved in 1 g was added, immersed, air-dried, dried and calcined under the same conditions as in the case of supporting Mo in Comparative Example 2, and Mo was supported. Thereafter, an aqueous solution in which 4.6606 g of cobalt nitrate hexahydrate was dissolved in 23.1 g of ion-exchanged water was added under the same conditions as in the case of supporting Co in Comparative Example 2, immersed, air-dried, dried, and calcined to obtain a Co-supported solution. Was carried out to obtain a catalyst r.

Comparative Example 19 Into an eggplant-shaped flask, 30.00 g of the same alumina as used in Example 1 was charged, and ion-exchanged water was added thereto.
A solution obtained by dissolving 8.5093 g of ammonium paramolybdate in 1 g was added to a pipette under the same conditions as in the case of supporting Mo in Comparative Example 2, and then immersed, air-dried, dried, and calcined to obtain Mo.
Loading was performed. After this, cobalt nitrate hexahydrate 2.18
An aqueous solution obtained by dissolving 47 g in 23.1 g of ion-exchanged water,
Under the same conditions as in the case of supporting Co in Comparative Example 2, addition and immersion, air drying, drying and calcination were carried out to carry Co, thereby obtaining a catalyst s.

Comparative Example 20 Into an eggplant type flask, 30.00 g of the same alumina as that used in Example 1 was charged, and ion-exchanged water was added thereto.
A solution in which 7.1294 g of ammonium paramolybdate was dissolved in 1 g was added, immersed, air-dried, dried, and calcined under the same conditions as in the case of supporting Mo in Comparative Example 2, thereby performing Mo supporting. Thereafter, an aqueous solution in which 6.5540 g of cobalt nitrate hexahydrate was dissolved in 23.1 g of ion-exchanged water was added, dipped, air-dried, dried and calcined under the same conditions as in the case of supporting Co in Comparative Example 2 to obtain a Co-supported solution. Was performed to obtain a catalyst t.

Comparative Example 21 Into an eggplant-shaped flask, 30.00 g of the same alumina as that used in Example 1 was charged.
A solution in which 6.2094 g of ammonium paramolybdate was dissolved in 1 g was added and immersed, air-dried, dried, and calcined under the same conditions as in the case of supporting Mo in Comparative Example 2, thereby carrying out Mo supporting. Thereafter, an aqueous solution obtained by dissolving 9.4669 g of cobalt nitrate hexahydrate in 23.1 g of ion-exchanged water was added under the same conditions as in the case of supporting Co in Comparative Example 2, immersed, air-dried, dried and calcined to obtain a Co-supported solution. Was carried out to obtain a catalyst u.

Comparative Example 22 Into an eggplant-shaped flask, 30.00 g of the same alumina as that used in Example 1 was charged, and ion-exchanged water was added thereto.
A solution in which 5.2896 g of ammonium paramolybdate was dissolved in 1 g was added, immersed, air-dried, dried, and calcined under the same conditions as in the case of supporting Mo in Comparative Example 2 to carry out the supporting of Mo. Thereafter, an aqueous solution obtained by dissolving 12.3798 g of cobalt nitrate hexahydrate in 23.1 g of ion-exchanged water was added to Comparative Example 2
Dipping, air drying, drying,
It was calcined to carry Co, and a catalyst v was obtained.

Comparative Example 23 Into an eggplant-shaped flask, 30.00 g of the same alumina as that used in Example 1 was charged, and ion-exchanged water was added thereto.
A solution in which 3.6797 g of ammonium paramolybdate was dissolved in 1 g was added and immersed, air-dried, dried, and calcined under the same conditions as in the case of supporting Mo in Comparative Example 2, thereby carrying out Mo supporting. Thereafter, an aqueous solution obtained by dissolving 17.4774 g of cobalt nitrate hexahydrate in 23.1 g of ion-exchanged water was added to Comparative Example 2
Dipping, air drying, drying,
It was calcined to carry Co, and a catalyst w was obtained.

Comparative Example 24 Zeolite (5 mass%)-alumina having a pore volume of 0.65 ml / g, a surface area of 382 m ² / g, and an average pore diameter of 62 ° (a lattice constant of 24.39 °, S
A powder of USY zeolite having an iO ₂ / Al ₂ O ₃ molar ratio of 6 was kneaded with alumina hydrate, extruded, and calcined. The alumina was substantially γ-Al ₂ O ₃ and had a diameter of 1 / 16 inch columnar molded product, acid amount 0.77 mmol /
g, impurity in zeolite-alumina: Na ₂ O 0.1
2% by mass, SO ₄ ²⁻ 0.45% by mass, SiO ₂ 3.6
8% by mass << Including SiO ₂ originating from zeolite >>) 5
0.00g was charged, and 3.0921 g of cobalt carbonate and 15.1 g of molybdophosphoric acid were added to 36.5 g of ion-exchanged water.
A solution in which 161 g of orthophosphoric acid and 1.9532 g of orthophosphoric acid were dissolved was added, dipped, air-dried, dried and calcined under the same conditions as in Example 1 to obtain a catalyst x.

Comparative Example 25 An alumina (γ) having a pore volume of 0.68 ml / g, a surface area of 312 m ² / g, and an average pore diameter of 73 ° was placed in an eggplant-shaped flask.
-Al ₂ O ₃ , columnar molded product having a diameter of 1/16 inch, acid amount 0.32 mmol / g, impurities: 1.21% by mass of Na ₂ O, 0.28% by mass of SO ₄ ²⁻ , 0.07% by mass of SiO ₂ %) Of 50.00 g of ion-exchanged water.
3.021 g of cobalt carbonate and molybdophosphoric acid 1 in 5 g
A solution in which 5.1161 g of orthophosphoric acid was dissolved and 1.9532 g of orthophosphoric acid were added to a pipette under the same conditions as in Example 1 and immersed, air-dried, dried and calcined to obtain a catalyst y.

Table 1 shows the elemental analysis values and physical properties of the catalysts of the above Examples and Comparative Examples. The impurities in Table 1 are metals other than CoO, MoO ₃ , P ₂ O ₅ , and alumina, and are shown in terms of oxide. The method and analytical equipment used for the analysis of the catalyst are shown below. [1] Analysis of physical properties a) Measurement method and equipment used:-The specific surface area was measured by the BET method using nitrogen adsorption. As the nitrogen adsorption device, a surface area measuring device (Bellsoap 28) manufactured by Nippon Bell Co., Ltd. was used. -The pore volume, average pore diameter, and pore distribution were measured by a mercury intrusion method. The mercury intrusion device is a porosimeter (MICROMERITICS AUTO-PORE)
9200: manufactured by Shimadzu Corporation).

B) Principle of measurement: The mercury intrusion method is based on the capillary phenomenon law. For mercury and cylindrical pores, this law is: D = − (1 / P) 4γ cos θ where D is the pore diameter, P is the applied pressure, γ is the surface tension,
θ is the contact angle. The volume of mercury entering the pores as a function of the applied pressure P is measured. The surface tension of the pore mercury of the catalyst was 484 dyne / cm, and the contact angle was 130 degrees. Pore volume is the total volume of mercury per gram of catalyst that has entered the pores. The average pore diameter is the average value of D calculated as a function of P. -The pore distribution is the distribution of D calculated as a function of P.

C) Measuring procedure: Turn on the power of the vacuum heating degassing apparatus,
Degree 5 × 10^-2Confirm that it is less than Torr. Leave the sample burette empty on the vacuum heating deaerator
I can. The degree of vacuum is 5 × 10^-2If the pressure falls below Torr,
Close the cock of the sample burette and heat it with vacuum
Remove from the device, cool down and weigh. Put the sample (catalyst) in the sample buret. Hang the sample burette with sample in the vacuum heating deaerator.
The degree of vacuum is 5 × 10 ^-21 after Torr
Hold for more than an hour. Sample burette with sample from vacuum heating deaerator
After removal and cooling, the weight is measured to determine the sample weight. Put the sample in the cell for AUTO-PORE 9200
You. It is measured according to AUTO-PORE 9200.

[2] Analysis of chemical composition a) Analysis method and equipment used: Metal analysis in the catalyst was performed by inductively coupled plasma emission analysis (I
CPS-2000: manufactured by Shimadzu Corporation).・ Quantification of metals was performed by the absolute calibration curve method.

B) Measurement procedure: Uniseal was charged with 0.05 g of catalyst and 1 m of hydrochloric acid (50%).
l, one drop of hydrofluoric acid, and 1 cc of pure water, and dissolve by heating. After dissolution, polypropylene volumetric flask (50 ml)
Then, add pure water and weigh to 50 ml. This solution is measured by ICPS-2000.

[3] Measurement of Coordination Number of Sulfur to Molybdenum Metal The coordination number of sulfur to molybdenum metal in the catalyst after the sulfidation treatment was examined by XAFS measurement. a) Pretreatment of catalyst and preparation of measurement disk: For pretreatment of catalyst, the catalyst was packed in a flow-through reaction tube and placed in a nitrogen stream at room temperature.
Minute treatment, the atmosphere gas was switched to H ₂ S (5%) / H ₂ , the temperature was increased at a rate of 5 ° C./min, and reached 400 ° C.
Hold for 4 hours. Thereafter, the temperature was lowered to 200 ° C. in the same atmosphere, the atmosphere gas was switched to nitrogen, and the temperature was lowered to room temperature.
The pretreatment (sulfurization treatment) was completed. After the above-mentioned pretreatment, the measurement disc is discharged while the nitrogen gas is passed through the reaction tube,
The reaction tube in which the valve was closed in the order of the inlets was directly transferred into a glove bag purged with nitrogen, and in the glove bag, the catalyst in the reaction tube was transferred to an agate mortar and crushed to a diameter of 13 m.
m and a pressure of 180 kg / cm ² with an IR disk molding machine. The molded disk was stored in a nitrogen-purged glove box until XAFS measurement was performed.

B) Measurement: High Energy Accelerator Research Organization Synchrotron Radiation Facility (KEK-P) of the Institute of High Energy Physics
Using the hard X-ray beam line F), the above disk was measured using an XAFS measuring apparatus BL-10B.

C) Analysis: XAFS measurement of molybdenum disulfide crystal (MoS ₂ ) was performed as a standard sample, and the peak intensity of Mo—S in the molybdenum sulfide on the catalyst was converted to the number of coordinating atoms of sulfur to molybdenum metal. As the corresponding one, the average number of coordinating atoms of sulfur to molybdenum was calculated from the XAFS radial distribution function of each catalyst.

Specifically, it was calculated by the following equation. First, XAFS measurement was performed on a standard sample (molybdenum disulfide crystal) having a clear crystal structure, and the following formulas (1) and (2) were used.
Find ΔR, K. ΔR = Rr−Robs, r (1) Nr = K · hr · Rr ² (2) where Rr: interatomic distance based on crystallographic data (Å) Robs, r: interatomic distance in the radial distribution function ( Å) Nr: Coordination number based on crystallographic data hr: Peak intensity in radial distribution function K: Constant

Next, ΔR and K are substituted into the equations (3) and (4), the interatomic distance (R) is obtained, and the average number of coordinating atoms (N) of each catalyst is obtained. Rr = Robs, s + ΔR (3) Nr = K · hs · R ² (4) where Robs, s: interatomic distance in the radial distribution function of each catalyst (Å) hs: in the radial distribution function of each catalyst Peak intensity

[4] Measurement of NO Adsorption FT-IR (Fourier Transform Infrared Spectroscopy) In order to examine the amount of NO gas adsorbed on the active metals (Co, Mo) in the catalyst after the pretreatment, the catalyst after the pretreatment was examined. Was adsorbed to the sample, and observed by a diffuse reflection method FTIR (FTIR-8100M, manufactured by Shimadzu Corporation). At this time, a spectrotech company was used as a heating vacuum type diffuse reflection cell (KBr window plate).

A) Pretreatment of catalyst (sulfurization treatment):
After pulverization, the mixture was placed in a diffuse reflection cell and heated in a He gas stream,
After reaching 00 ° C., the temperature was maintained for 30 minutes, and then H ₂ S (5
%) / H ₂ gas and hold for 2 hours, followed by He
After switching to gas and flashing for 30 minutes, the temperature was lowered to room temperature in the same airflow, and the pretreatment was terminated.

B) FT-IR measurement: After holding at room temperature in a NO gas stream for 30 minutes, switching to He gas was performed, and after 30 minutes of exhaust treatment, FT-IR measurement was performed.

C) Analysis of measurement result: NO adsorbed on Co
Spectrum (1860 cm ^-1), and examines the respective intensities of the adsorbed NO spectrum (1690 cm ^-1) to Mo, a value indicated by the following equation, comparing each catalyst. ICoMoS = ICo / (ICo + IMo) where ICo: intensity of NO spectrum adsorbed on cobalt IMo: intensity of NO spectrum adsorbed on molybdenum

As a representative example, N in catalyst G
FIG. 1 shows the O-adsorption FT-IR spectrum.

[0091]

[Table 1-1]

[0092]

[Table 1-2]

The abbreviations in Table 1 mean the following. SA: specific surface area PV: pore volume MPD: average pore diameter PSD: pore distribution CBD: densely packed bulk density MoS coordination number: coordination number of sulfur to Mo measured by XAFS ICoMoS: relative NO by IR measurement Adsorption amount

[Hydrogenation reaction of straight-run gas oil] Examples 1 to 8, Comparative Examples 1 to 25 Catalysts A to H and a to y prepared in the above Examples and Comparative Examples
, A straight-run gas oil having the following properties was hydrotreated in the following manner. First, the catalyst was filled in a high-pressure flow reactor to form a fixed-bed catalyst layer, which was pretreated under the following conditions. Next, a mixed fluid of the feedstock oil and the hydrogen-containing gas heated to the reaction temperature is introduced from the top of the reactor, and the hydrogenation reaction proceeds under the following conditions, and the mixed fluid of the produced oil and the gas is reacted. It was discharged from the lower part of the device, and the generated oil was separated by a gas-liquid separator.

Catalyst pretreatment conditions: pressure; normal pressure atmosphere; hydrogen sulfide (5%) / hydrogen gas flow temperature: maintained at 150 ° C. for 0.5 hr, then 350 ° C.
Step temperature rise for 1 hour at

Hydrogenation reaction conditions: Reaction temperature; 340 ° C. Pressure (hydrogen partial pressure); 4.9 MPa Liquid hourly space velocity; 1.5 hr ^-1 hydrogen / oil ratio; 560 m ³ / m ³

Properties of feed oil: Oil type; Middle eastern straight-run gas oil Specific gravity (15/4 ° C); 0.8567 Distillation properties: Initial boiling point: 203.0 ° C, 50% point: 315.5 ° C, 90% The point is 371.0 ° C and the end point is 38
9.0 ° C. Sulfur component; 1.364% by mass Nitrogen component; 150 ppm Kinematic viscosity (℃ 30 ° C.); 6.608 cSt Pour point; 5.0 ° C. Cloudy point; 6.0 ° C. cetane index; 57.1 Seybolt color -10 ASTM color; 0.5 aniline point; 74.3 ° C

The reaction results were analyzed by the following method. The reactor was operated at 340 ° C., and after 6 days had passed, the product oil was collected and its properties were analyzed. [1] Desulfurization rate (HDS) (%): The ratio of sulfur lost from the feedstock oil by converting the sulfur content in the feedstock to hydrogen sulfide by a desulfurization reaction is defined as the desulfurization rate, and the feedstock oil and product oil Was calculated by the following equation from the sulfur analysis value. [2] Desulfurization reaction rate constant (Ks): sulfur content (S
The constant of the reaction rate equation for obtaining the 1.5-order reaction order with respect to the decrease in p) is defined as the desulfurization reaction rate constant (Ks). The higher the reaction rate constant, the better the catalytic activity. These results were as shown in Table 2.

[0099]

## EQU1 ## Desulfurization rate (%) = [(Sf-Sp) / Sf] × 100 Desulfurization reaction rate constant = [1 / ＝ (Sp) −1 / √ (S
f)] × (LHSV) where Sf: sulfur content in feed oil (% by mass) Sp: sulfur content in reaction product oil (% by mass) LHSV: liquid hourly space velocity (hr ⁻¹ ) Specific activity (%) = Each desulfurization reaction rate constant / desulfurization reaction rate constant of comparative catalyst a x 100

[0100]

[1 of Table 2]

[0101]

[Table 2-2]

Conventional desulfurization zone (sulfur content 0.2 to 0.05)
Mass%), the existing catalysts (comparative catalysts a to y) can be easily desulfurized, but in the deep desulfurization region (sulfur content 0.05 mass% or less), 4,6-dimethyldibenzothiophene or Due to the presence of a non-desulfurizable sulfur compound such as 4-methyldibenzothiophene, desulfurization becomes extremely difficult. In contrast, as can be seen from Table 2, the catalyst A of the present invention
It can be seen that when ~ H is used, the depth desulfurization region of 0.05% by mass or less can be easily cleared. This means that the catalyst of the present invention has extremely excellent activity against the desulfurization reaction of light oil in the deep desulfurization region under the same conditions such as hydrogen partial pressure and reaction temperature as in the conventional gas oil hydrotreatment. It shows that it has.

[Hydrogenation Reaction of Vacuum Gas Oil] Examples 7, 9 and Comparative Examples 1 and 14 Using the catalysts G, I, a and n prepared in Examples 7 and 9 and Comparative Examples 1 and 14, Hydrogenation of the vacuum gas oil having the following properties was performed in the following manner. First, the catalyst was filled in a high-pressure flow reactor to form a fixed-bed catalyst layer, which was pretreated under the following conditions. Next, a mixed fluid of the feedstock oil and the hydrogen-containing gas heated to the reaction temperature is introduced from the upper part of the reactor, and the hydrogenation reaction of the desulfurization reaction and the decomposition reaction proceeds under the following conditions (in the desulfurization operation mode). After performing the reaction, mild
(The reaction was performed in a hydrocracking operation mode.) A mixed fluid of produced oil and gas was discharged from the lower part of the reactor, and the produced oil was separated by a gas-liquid separator.

Conditions for pretreatment of catalyst: pressure (hydrogen partial pressure); 4.9 MPa sulphidating agent; feed oil (Middle Eastern straight-run gas oil) in the above [hydrotreating reaction of straight-run gas oil] Temperature: 290 ° C. Maintain 1.5 hr, then 320 ° C
At a step temperature of 15 hours maintained at a rate of 25 ° C. /
hr)

Desulfurization reaction (desulfurization operation mode) conditions: reaction temperature; 360 ° C. pressure (hydrogen partial pressure); 4.9 MPa liquid space velocity; 0.66 hr ^-1 hydrogen / oil ratio; 560 m ³ / m ³ decomposition reaction (mild) hydrocracking operation mode) conditions: reaction temperature; 400 ° C. pressure (hydrogen partial pressure); 4.9 MPa liquid hourly space velocity; 0.66 hr ^-1 hydrogen / oil ratio; 560 m ³ / m ³

Properties of feed oil: Oil type; Arabian light vacuum gas oil Specific gravity (15/4 ° C.); 0.9185 Distillation properties: Initial boiling point: 349.0 ° C., 50% point: 449.0 ° C., 90% point 529.0 ° C., endpoint 56
6.0 ° C Sulfur component; 2.45% by mass Nitrogen component; 0.065% by mass Pour point; 35 ° C Asphaltene; <100 ppm Aniline point; 82 ° C

The desulfurization activity was analyzed by the following method. The reactor was operated at 360 ° C., and after 10 days had passed, the produced oil was collected and its properties (desulfurization rate (HDS)
(%), Desulfurization reaction rate constant (Ks), specific activity (%)) are analyzed in the same manner as in the case of the above [hydrotreating reaction of straight-run gas oil], and the degree of deterioration of catalyst activity (%) is described later. And analyzed.

The decomposition activity was analyzed by the following method. After the evaluation of the desulfurization activity, the reaction temperature was raised to 400 ° C., and the reactor was operated at the same temperature. After 20 days had passed, the produced oil was sampled and its properties were analyzed. [1] Cracking rate (HYC) (%): The hydrocracking rate of the catalyst is represented by a ratio of a fraction of 343 ° C. or less in a total fraction of a product oil obtained by gas chromatography distillation according to ASTM D2887. Was. The higher the decomposition activity of the catalyst, the more
The yield of light fractions of 43 ° C. or less is increased. [2] Decomposition reaction rate constant (Kc): 1
The constant of the reaction rate equation for obtaining the next reaction order is defined as the decomposition reaction rate constant (Kc). The higher the reaction rate constant, the better the catalytic activity. [3] Deterioration degree: Regarding the rate of deterioration of the desulfurization activity, the rate of decrease in the reaction rate in the early stage of the operation (day 10 of the reaction) and the late stage of the operation (day 40 of the reaction) was defined as the degree of deterioration, and was calculated by the following equation. . In addition, the reaction rate in the latter half of the operation was obtained by sampling the oil produced on the 40th day of the reaction and following the same procedure as in the early stage of the operation. These results are shown in Table 3. As is clear from Table 3, the decomposition activity can be improved by setting the average pore diameter of the catalyst to 100 to 120 °.

[0109]

[Number 2] decomposition rate (%) = [the product oil in 343 ° C. ^- the amount / quantity of product oil total distillate] × 100 decomposition reaction rate constant = - (LHSV) · ln (1-decomposition rate / 100) ratio Activity (%) = [decomposition reaction rate constant / decomposition reaction rate constant of comparative catalyst a] × 100 Deterioration degree (%) = [｛(reaction rate on reaction day 10) − (reaction rate on reaction day 40) ｝ / (Reaction rate on the 10th day of reaction)] × 100

[0110]

[Table 3]

[0111]

As described in detail above, according to the present invention,
The following effects can be obtained. (1) Since it has a high desulfurization activity, the sulfur content in light oil can be significantly reduced. (2) A light oil base material having a low sulfur content can be supplied at low cost. (3) Since the reaction conditions can be made substantially the same as the reaction conditions in the conventional hydrotreating, the conventional apparatus can be diverted without significant modification.

[Brief description of the drawings]

FIG. 1 NO adsorption FT-IR for catalyst G of the present invention
It is a spectrum.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Tomoyuki Yogo 1134-2, Gondogendo, Satte City, Saitama Prefecture Inside the R & D Center, Cosmo Research Institute, Inc. (72) Nobumasa Nakajima 1134- 2 Research and Development Center, Cosmo Research Institute, Inc.

Claims (4)

[Claims] 1. A catalyst obtained by impregnating an alumina carrier with an aqueous solution containing cobalt, molybdenum, and phosphorus, comprising 2 to 4% by mass of cobalt, expressed as an oxide, on a catalyst basis.
6 to 22% by mass of molybdenum and 0.8 to 4.5% by mass of phosphorus, wherein the mass ratio of cobalt to molybdenum is [cobalt oxide] /
The value of [cobalt oxide + molybdenum trioxide] is 0.12
The mass ratio of molybdenum to phosphorus is 0.05 to 0.25 in terms of [phosphorus pentoxide] / [molybdenum trioxide], and the specific surface area measured by the nitrogen adsorption method is 170 to 300 m ^2. /
g, the pore volume measured by the mercury intrusion method is 0.5 to 0.7 ml /
g, average pore diameter 70- in pore distribution measured by mercury intrusion method
The pore volume in the range of 120 °, average pore diameter ± 15 ° is at least 70% of the total pore volume, and the coordination number of sulfur to molybdenum metal in the catalyst after the sulfidation treatment is 5 to 6 by XAFS measurement. A catalyst for hydrotreating light oil, which is characterized in that: 2. The catalyst for hydrotreating light oil according to claim 1, wherein the content of metals other than cobalt oxide, molybdenum trioxide, phosphorus pentoxide and alumina is 1% by mass or less. 3. The catalyst for hydrotreating light oil according to claim 1, wherein the purity of the alumina is 98% by mass or more. 4. Gas oil containing sulfur at a hydrogen partial pressure of 3 to 8 MPa, 300 to 420 ° C. and a liquid hourly space velocity of 0.3 to 5 hr ⁻¹ in the presence of the catalyst according to claim 1. A method for hydrotreating light oil, comprising performing a catalytic reaction of a fraction.