JPH11319567A - Hydrodesulfurization catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hydrodesulfurization catalyst which exhibits high hydrogenation treatment ability to hydrogenation treatment for ordinary pressure residual oil or reduced pressure sesidual oil being heavy hydrocarbon oil with high sulfur content and stably produces fuel oil with low sulfur content for a long period, a pref. method for preparing this hydrodesulfurization catalyst, and a method for performing advantageously hydrodesulfurization treatment of hydrocarbon oil by using this hydrodesulfurization catalyst. SOLUTION: A hydrodesulfurization catalyst which is a catalyst wherein 1-10 wt.% nickel oxide, 5-20 wt.% molydbenum trioxide, 0.5-2.0 wt.% magnesium oxide and 3-5 wt.% phosphorus pentaoxide to the catalyst are carried on a fireproof oxide carrier and relations of 0.1 <= magnesium oxide (wt.%)/ phosphorus pentaoxide (wt.%) <= 0.5 and 0.06 <= magnesium oxide (wt.%)/ molydbenum trioxide (wt.%) <= 0.15 exist among carried ratios of magnesium oxide, phosphorus pentaoxide and molydbenum trioxide and a method for hydrogesulfurization of hydrocarbon oil for performing hydrodenation treatment of the hydrocarbon oil by bringing the hydrocarbon oil into contact with the catalyst in the presence of hydrogen, are provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a hydrodesulfurization catalyst used in the field of petroleum refining, a method for producing the same, and a method for hydrodesulfurizing a hydrocarbon oil using the catalyst.

[0002]

2. Description of the Related Art Hydrocarbon oils, particularly atmospheric residual oils and vacuum residual oils, contain high concentrations of sulfur compounds, and when used as fuel, the sulfur compounds are released into the atmosphere as sulfur oxides. Will be done. Accordingly, hydrodesulfurization catalysts for reducing the sulfur concentration in fuel oil have been developed.

[0003] On the other hand, crude oil, which is a fossil fuel, is in a situation where it is unavoidable that it will become heavier in the future due to limited resources. It is inevitable that the amount of sulfur compounds contained in the atmospheric residue and the vacuum residue will be further increased in the future as the crude oil becomes heavier. Therefore, it is considered that the demand for high desulfurization performance of the hydrodesulfurization catalyst is only increasing due to global environmental problems and the like.

[0004] Further, heavy crude oil increases the content of heavy metals (particularly vanadium and nickel) which are poisons of the hydrodesulfurization catalyst and asphaltene which is a coke precursor. Therefore, it is expected that the performance of the hydrodesulfurization catalyst will be extremely deteriorated, and the desulfurization operation on a commercial basis will be difficult.

At present, various countermeasures for increasing the concentration of the poisoning substance of the catalyst in the hydrodesulfurization apparatus have been studied and taken. As a result, the protection of hydrodesulfurization catalysts against heavy metals in crude oil has made considerable progress (Idemitsu Technical Report, Vol. 40, No. 1, pp. 5-8, 1997),
As for the poisoning of the coke precursor, there is no effective means (catalysis chemical technology report, Vol. 10, No. 1,
82-82, 1993).

[0006] JP-A-6-226108 discloses a hydrotreating catalyst in which a polyhydric alcohol is added to a catalyst in which a metal of Group 6 and Group 8 of the periodic table are supported on a catalyst carrier and dried at 200 ° C or less. Is described. But,
This method is not practical because the production method is complicated and only the drying is performed, so that the active ingredient is not fixed and the active ingredient may elute during the reaction.

Japanese Patent Application Laid-Open No. 7-108173 discloses a method for improving the activity of a catalyst by loading polyethylene glycol into an impregnating liquid to uniformly support the metal when the metal is supported on the catalyst carrier. Are listed. However, the catalyst obtained by this method is not sufficiently satisfactory in terms of catalytic activity.

Further, Japanese Patent Application Laid-Open No. 9-150059 discloses a hydrodesulfurization catalyst which is particularly effective for a gas oil fraction having a low molecular weight by using a phosphorus component, a metal component of Group IIA of the periodic table, a molybdenum component and a cobalt component. However, there is no description about a high-molecular-weight petroleum fraction such as an atmospheric residue, and its effect is unknown.

[0009] Next, as a conventional technique for the catalyst performance degradation due to heavy metal components and coke precursor contained in the feedstock,
JP-A-6-184558 describes that the poisoning of the catalyst is reduced by optimizing the distribution of active metals supported on the catalyst carrier. There is no description about reduction of poisoning and no description of desulfurization reaction rate, so its effectiveness is doubtful.

[0010] Also, Japanese Patent Application Laid-Open No. 2-35938 discloses that
Although a catalyst composition for reducing catalyst poisoning due to poisoning by the coke precursor in the feed oil has been proposed, the existence of a co-catalyst that is considered effective for exhibiting catalytic performance is denied, Further, as is clear from the examples, the desulfurization performance is extremely low.

[0011]

SUMMARY OF THE INVENTION It is a first object of the present invention to provide a high-hydrogenation treatment for a high-sulfur-containing heavy hydrocarbon oil such as an atmospheric residue or a vacuum residue. It is an object of the present invention to provide a hydrodesulfurization catalyst which exhibits a capacity and can stably produce low-sulfur fuel oil for a long period of time.

Another object of the present invention is to provide a method for producing a hydrodesulfurization catalyst which can easily and practically produce the hydrodesulfurization catalyst of the present invention.

The present invention further provides a method for advantageously performing hydrodesulfurization treatment of various hydrocarbon oils, particularly heavy oils, using the highly active hydrodesulfurization catalyst of the present invention. It is also intended to provide.

[0014]

Means for Solving the Problems The present inventors have conducted intensive studies on the above problems, and as a result, a hydrodesulfurization catalyst in which a specific metal is supported on a refractory oxide carrier in a specific ratio has a remarkable catalytic activity. The present inventors have found that the poisoning of asphaltene, which is a coke precursor in a hydrocarbon oil, due to deposition on a catalyst is excellent, and have completed the present invention based on this finding.

That is, according to the present invention, the refractory oxide carrier contains 1 to 10 wt% of nickel oxide, 5 to 20 wt% of molybdenum trioxide, 0.5 to 2.0 wt% of magnesium oxide, and A catalyst in which 3 to 5 wt% of phosphorus pentoxide is supported, and 0.1 ≦ magnesium oxide (wt%) / phosphorus pentoxide (wt%) between the supporting ratios of magnesium oxide, phosphorus pentoxide and molybdenum trioxide. An object of the present invention is to provide a hydrodesulfurization catalyst characterized by satisfying a relationship of 0.5 and 0.06 ≦ magnesium oxide (wt%) / molybdenum trioxide (wt%) ≦ 0.15.

The present invention also relates to a method for impregnating a refractory oxide carrier with an impregnating solution in which a nickel compound, a molybdenum compound, a magnesium compound and a phosphorus compound are dissolved in the coexistence of an organic acid compound. An object of the present invention is to provide a method for producing the above hydrodesulfurization catalyst, which carries out a supporting treatment in the coexistence of glycol and calcinates at a temperature of 400 ° C. or more.

According to the present invention, a refractory oxide carrier is impregnated with an impregnating solution in which a magnesium compound is dissolved in the coexistence of an organic acid compound as a first step to carry out a loading treatment.
Baking at a temperature of at least 00 ° C., as a second step, impregnating with an impregnating solution in which a nickel compound, a molybdenum compound and a phosphorus compound are dissolved, and carrying out a supporting treatment in the coexistence of polyethylene glycol having a molecular weight of 300 or more; Another method for producing the above hydrodesulfurization catalyst, which is calcined at the above temperature, is provided.

The present invention also provides a method for hydrodesulfurizing a hydrocarbon oil, wherein the hydrocarbon oil is brought into contact with the catalyst in the presence of hydrogen to carry out a hydrotreatment.

[0019]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The shape of the hydrodesulfurization catalyst of the present invention is not particularly limited, and a shape suitable for a desired reaction type, such as a cylinder, a sphere, three to six leaves, and a honeycomb, can be freely selected. . In particular, in a fixed-bed direct hydrodesulfurization reactor, a columnar, three-leaf or four-leaf shape is suitably used.

Examples of the refractory oxide carrier constituting the hydrodesulfurization catalyst of the present invention include alumina, silica, titania, zirconia, and composite oxide carriers thereof. Alumina is preferred from the viewpoint of metal dispersibility.

The refractory oxide carrier usually has a specific surface area of 5 to 5.
500m ² / g, preferably it is used as a 50 to 300 m ² / g. If the specific surface area is less than 5 m ² / g, the dispersibility of the supported metal may decrease, and if it exceeds 500 m ² / g, the diffusion of the reactants may be hindered. The pore volume is from 0.2 to 1.5 cm ³ / g, preferably from 0.3 to
1.2 cm ³ / g is used. The pore volume is 0.
If it is less than 2 cm ³ / g, the catalyst pores tend to be immediately filled by the precipitation of metal and coke in the feedstock oil. On the other hand, if it exceeds 1.5 cm ³ / g, the strength of the catalyst is remarkably reduced, and it tends to be unsuitable for practical use. The pore diameter is preferably such that the 50% point of the pore volume is in the range of 100 to 300 °. This is a size suitable for the molecular size of the petroleum fraction as a reactant, and is a size that can be sufficiently diffused to the reaction active site inside the catalyst pores. Regarding these physical property values, the pore volume and the pore distribution were measured by the adsorption / desorption method using nitrogen, and the BJH method [E. P. Barref. L.
G. FIG. Joyner and P.M. P. Halnda,
J. Amer. Chem. Soc. , 73, 373 (1
951)]. The specific surface area is determined by B.I.
E. FIG. T. Method is used.

Preferred metal compounds used in the impregnation solution for the supporting treatment include oxides, sulfates, nitrates, carbonates, and the like.
Basic carbonates, oxalates, acetates, ammonium salts and the like are used as aqueous solutions. Specific examples include paramolybdate, metamolybdate, molybdenum trioxide, nickel nitrate, basic nickel carbonate, magnesium nitrate, magnesium sulfate, magnesium carbonate, and basic magnesium carbonate, which are used as an aqueous solution.

The addition of the phosphorus compound has the effect of increasing the stability of the aqueous solution of the metal compound supported on the catalyst and at the same time improving the catalytic activity as a catalyst component. Preferred phosphorous compounds include phosphoric acid.

As the polyethylene glycol used for the supporting treatment, those having a molecular weight of 300 or more are used.
Preferably, those having a molecular weight of 300 to 10,000, more preferably 350 to 6,000 are used. 3
If it is less than 00, the catalytic activity is inferior, and if it exceeds 10,000, it takes time for the dissolution or loading step, and handling may be difficult.

The amount of polyethylene glycol added is preferably 0.5 to 100 parts by weight of the refractory oxide carrier.
-30 parts by weight, more preferably 1-15 parts by weight.
If the amount is less than 0.5 part by weight, the effect of addition may not be exhibited. If the amount exceeds 30 parts by weight, loading may be difficult.

The loading method is not particularly limited, but known loading operations such as a normal pressure impregnation method, a vacuum impregnation method, a coating method, and a combination thereof are used.

It is known that nickel, one of the supported metals, forms a spinel with alumina as a carrier component and inactivates it. The phosphorus compound has an effect of suppressing the spinelization of nickel and improves the catalytic activity.However, if a large amount of the phosphorus compound is used without using the polyethylene glycol, a nickel-molybdenum-phosphorus composite oxide is generated. On the contrary, the catalytic activity decreases. When the metal compound aqueous solution to which the polyethylene glycol is added is used as in the present invention, the amount of the phosphorus compound added can be increased to 3 to 5% by weight, and the catalytic activity can be dramatically improved. .

In addition, various organic acid compounds are added to the impregnating liquid for supporting the metal compound in order to enhance the stability of the solution and the catalytic activity. As such an organic acid compound, oxalic acid, tartaric acid, succinic acid, malonic acid, malic acid, citric acid, formic acid, acetic acid, propionic acid and the like are used. Malic acid is preferred, and the amount of the acid is usually 0.1 to 100 parts by weight of the refractory oxide carrier.
-30 parts by weight, preferably 5-15 parts by weight. 0.
If the amount is less than 1 part by weight, the effect of addition is not exhibited, and if it exceeds 30 parts by weight, the dissolution of the metal compound may be deteriorated.

The calcination in the present invention is preferably 400
C. to 700.degree. C. in an air or oxygen atmosphere. Preferably, the reaction is performed under such conditions that the residual carbon content in the catalyst by the above-mentioned polyethylene glycol is 1.0% by weight or less.

In the hydrodesulfurization catalyst of the present invention, nickel oxide is 1 to 10% by weight, and molybdenum trioxide is 5 to 2%.
0 wt%, 0.5 to 2.0 wt% of magnesium oxide and 3 to 5 wt% of phosphorus pentoxide are supported. If the content of nickel oxide is less than 1 wt%, sufficient activity cannot be exhibited, and
If the content is more than 5% by weight, the activity becomes low due to aggregation of the metal. If the content of molybdenum trioxide is less than 5% by weight, sufficient activity cannot be exhibited. Cannot control the poisoning of the coke precursor. If the content exceeds 2.0 wt%, magnesium oxide forms a composite oxide with molybdenum, nickel, etc., resulting in low activity, and phosphorus pentoxide becomes 3 wt%.
If it is less than 5 wt.
%, A complex oxide is formed with molybdenum, nickel, etc., and the activity becomes low.

When the ratio of magnesium oxide (wt%) / phosphorus pentoxide (wt%) is less than 0.1, the improvement in acidity by phosphorus is superior to the effect of adding magnesium, and it becomes impossible to suppress poisoning. When the catalyst is prepared, stable dissolution of the impregnating solution cannot be obtained, and the catalyst cannot be adjusted, and the effect of promoting the reaction of phosphorus tends to be suppressed by excessive magnesium. When the ratio of magnesium oxide (wt%) / molybdenum trioxide (wt%) is less than 0.06, protection of the active metal molybdenum, which is an active metal, from poisoning by the coke precursor does not work sufficiently, and exceeds 0.15. And molybdenum / magnesium aggregates to form low activity.

The hydrodesulfurization catalyst obtained by the present invention is brought into contact with a hydrocarbon oil to carry out hydrodesulfurization treatment. Examples of the hydrocarbon oil used in the hydrodesulfurization treatment include a normal pressure residual oil and a reduced pressure residual oil. In particular, it can be suitably applied to heavy sulfur-containing hydrocarbon oils.

When performing the hydrotreating using the hydrodesulfurization catalyst of the present invention, it is preferable to perform a preliminary sulfidation treatment as an activation or stabilization treatment before performing the hydrotreating reaction. This pre-sulfurization treatment is performed in a temperature range of 200 to 400 ° C. using hydrogen sulfide, carbon disulfide, thiophene, dimethyl disulfide, or the like as a pre-sulfurizing agent.

The reaction conditions for the hydrodesulfurization treatment vary depending on the type of the target oil, but the reaction temperature is preferably 20.
Select in the range of 0 to 500 ° C. Reaction pressure is 15-2
It is preferable to select the range of 50 kg / cm ² .

The reaction system is not particularly limited, but usually employs various processes such as a fixed bed, a moving bed, a boiling bed, a suspension bed, and the like. Adopted to. In the case of such a circulation system, the LHSV (liquid hourly space velocity) is 0.1 to 45 (1 / h).
It is better to select within the range of r).

The supply ratio of hydrogen gas and hydrocarbon oil (hydrogen /
Hydrocarbon oil ratio) is usually 50 to 2,000 Nm ³ / kl
It is preferable to select within the range.

As described above, various hydrocarbon oils including heavy oils using the hydrodesulfurization catalyst of the present invention are described below.
The hydrodesulfurization treatment can be performed efficiently, and a useful hydrocarbon fraction with sufficiently reduced sulfur content can be obtained with a high yield.

[0038]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples of the present invention and Comparative Examples thereof, but the present invention is not limited to these Examples. The amount of the metal compound supported in the catalyst composition was determined for molybdenum and magnesium by "inductively coupled plasma emission spectroscopy (IC
P) "and nickel and phosphorus were quantified by" X-ray fluorescence analysis ".

Example 1 165.0 parts by weight of molybdenum trioxide and 39.3 parts by weight of basic nickel carbonate in an amount equivalent to NiO were replaced with ion-exchanged water 5
It was dissolved in 00 parts by weight. 80-90 ° C for dissolution
And stirred for 1 hour. Next, 50.8 parts by weight of phosphoric acid was added in an amount equivalent to phosphorus pentoxide, and after confirming dissolution, 14.0 parts by weight of basic magnesium carbonate was added in an amount equivalent to magnesium oxide. (PH is adjusted to 1.0 <pH ≦ 2.0), malic acid was added. At this time, the temperature of the aqueous solution was kept at about 40 ° C. Next, 60 parts by weight of polyethylene glycol (molecular weight 400) was added. Next, this impregnating liquid was adjusted to an amount corresponding to the absorption rate of the carrier, and supported on 1,000 parts by weight of a four-leaf type alumina carrier having the above-mentioned physical properties by normal pressure impregnation. The support was dried at 120 ° C. for 3 hours, and then dried at 550 ° C. in air.
After calcining for 5 hours, catalyst A was obtained.

The catalyst A thus obtained is obtained by
2.9 wt% as NiO, MoO _Three13.4w
t%, 1.1 wt% as MgO, P_TwoO_FiveAs 3.6
wt%, average pore diameter is 134 °, pore volume is
0.54ml / g, specific surface area is 183m^Two/ G
Was.

Example 2 Basic magnesium carbonate was converted to magnesium oxide in an amount of 1
4.0 parts by weight was added to an appropriate amount of ion-exchanged water at 40 ° C. Further, malic acid was added so that the pH of the aqueous solution was 1.0 <pH ≦ 2.0. Next, this impregnating liquid was adjusted to an amount corresponding to the absorption rate of the carrier, and supported on 1,000 parts by weight of a four-leaf type alumina carrier having the above-mentioned physical properties by normal pressure impregnation. The support was dried at 120 ° C. for 3 hours, and then dried at 550 ° C. in air.
It was calcined for 5 hours to prepare a magnesium-supported carrier.

164.2 parts by weight of molybdenum trioxide and 38.8 parts by weight of nickel carbonate equivalent to NiO were dissolved in 500 parts by weight of ion-exchanged water. Upon dissolution, the mixture was heated to 80 to 90 ° C. and stirred for 1 hour. Next, 50 parts by weight of phosphoric acid was added in an amount equivalent to phosphorus pentoxide, and an appropriate amount of malic acid was added to adjust the pH of the aqueous solution to 1.0 <pH ≦ 2.0. At this time, the temperature of the aqueous solution was kept at about 40 ° C. Next, 60 parts by weight of polyethylene glycol (molecular weight 400) was added. Next, this impregnating liquid was adjusted to an amount corresponding to the absorption rate of the carrier, and supported by the normal pressure impregnation method using the magnesium-carrying carrier obtained above (corresponding to 1,000 parts by weight of the alumina carrier). The support was dried at 120 ° C. for 3 hours, and calcined in air at 550 ° C. for 5 hours to obtain a catalyst B.

The catalyst B thus obtained was obtained by
3.1 wt% as NiO, MoO _Three13.6w
t%, 1.1 wt% as MgO, P_TwoO_FiveAs 3.5
wt%, the average pore diameter is 127 °, and the pore volume is
0.580ml / g, specific surface area is 183m^Two/ G
Was.

Example 3 169.2 parts by weight of molybdenum trioxide and 40.7 parts by weight of basic nickel carbonate in an amount equivalent to NiO were replaced with ion-exchanged water 5
It was dissolved in 00 parts by weight. 80-90 ° C for dissolution
And stirred for 1 hour. Next, 48.3 parts by weight of phosphoric acid was added in an amount equivalent to phosphorus pentoxide, and after confirming dissolution, 14.0 parts by weight of basic magnesium carbonate was added in an amount equivalent to magnesium oxide. (PH is adjusted to 1.0 <pH ≦ 2.0), malic acid was added. At this time, the temperature of the aqueous solution was kept at about 40 ° C. Next, 60 parts by weight of polyethylene glycol (molecular weight 400) was added. Next, this impregnating liquid was adjusted to an amount corresponding to the absorption rate of the carrier, and supported on 1,000 parts by weight of a four-leaf type alumina carrier having the above-mentioned physical properties by normal pressure impregnation. The support was dried at 120 ° C. for 3 hours, and then dried at 550 ° C. in air.
After calcining for 5 hours, catalyst C was obtained.

The catalyst C thus obtained was obtained by
3.2 wt% as NiO, MoO _Three13.8w
t%, 1.2 wt% as MgO, P_TwoO_Five4.3
wt%, average pore diameter is 134 °, pore volume is
0.482 ml / g, specific surface area is 144 m^Two/ G
Was.

COMPARATIVE EXAMPLE 1 Molybdenum trioxide (164.2 parts by weight) and basic nickel carbonate (38.8 parts by weight, equivalent to NiO) were converted to ion-exchanged water (5).
It was dissolved in 00 parts by weight. 80-90 ° C for dissolution
And stirred for 1 hour. Next, 50.1 parts by weight of phosphoric acid in an amount equivalent to phosphorus pentoxide was added and dissolved. Further, malic acid was added as needed to adjust the pH of the aqueous solution to about 2.0 (the adjustment range was 1.0 <pH ≦ 2.0). At this time, the temperature of the aqueous solution was kept at about 40 ° C. Next, 60 parts by weight of polyethylene glycol (molecular weight 400) was added. Next, this impregnating liquid was adjusted to an amount commensurate with the absorptivity of the carrier, and a four-leaf type alumina carrier having the above-mentioned physical properties was used.
It was supported by weight under normal pressure impregnation. This carrier is transferred to 120
C. for 3 hours, and calcined in air at 550.degree. C. for 5 hours to obtain a catalyst D.

The catalyst D thus obtained was obtained by
3.2 wt% as NiO, MoO _Three13.3w
t%, P_TwoO_Five3.8% by weight as average pore diameter
Is 124 °, the pore volume is 0.56 ml / g, and the specific surface area is
184m^Two/ G.

Comparative Example 2 173.2 parts by weight of molybdenum trioxide and 41.6 parts by weight of basic nickel carbonate in an amount equivalent to NiO were replaced with ion-exchanged water 5
It was dissolved in 00 parts by weight. 80-90 ° C for dissolution
And stirred for 1 hour. Then, 49.5 parts by weight of phosphoric acid was added in an amount equivalent to phosphorus pentoxide, and after confirming dissolution, basic magnesium carbonate was added in an amount equivalent to 3 in magnesium oxide.
8.1 parts by weight were added, and malic acid was further added to adjust the pH of the aqueous solution to about 2.0 (the adjustment range was 1.0 <pH ≦ 2.0). At this time, the temperature of the aqueous solution was kept at about 40 ° C. Next, polyethylene glycol (molecular weight 400) was added to 6
0 parts by weight were added. Next, this impregnating liquid was adjusted to an amount corresponding to the absorption rate of the carrier, and supported on 1,000 parts by weight of a four-leaf type alumina carrier having the above-mentioned physical properties by normal pressure impregnation. The support is dried at 120 ° C. for 3 hours, and then dried at 550 ° C. and 5 ° C. in air.
After calcining for an hour, catalyst E was obtained.

The catalyst E thus obtained is based on dry weight
3.1 wt% as NiO, MoO _Three13.7w
t%, 2.9 wt% as MgO, P_TwoO_FiveAs 4.1
wt%, average pore diameter is 132mm, pore volume is
0.48 ml / g, specific surface area is 141 m^Two/ G
Was.

Table 1 shows the amounts of active metals and their ratios in the catalyst obtained above.

[0051]

[Table 1] Hydrodesulfurization Treatment Performance Evaluation Experiment 1 First, for the catalysts A, B, and D, using a high-pressure fixed-bed flow-type reactor with a catalyst loading of 30 cc, an atmospheric residual oil obtained from the Middle Eastern heavy crude shown in Table 2 Was evaluated for the initial desulfurization performance using the raw material as a raw material, and the effect of adding Mg was compared and evaluated with a non-added product. Since the catalyst of the present invention is a desulfurization catalyst, it was evaluated in combination with a commercially available demetalization catalyst.

[0052]

[Table 2] Prior to the reaction, as a pretreatment, a feedstock obtained by adding DMDS to LGO (light oil) to the catalyst (the sulfur concentration in the feedstock was adjusted to 2.5 wt%) was added together with hydrogen gas to 25%.
The mixture was circulated at 0 ° C. for 24 hours to be presulfurized. Thereafter, the feedstock oil shown in Table 2 was passed through the catalyst together with hydrogen gas, and subjected to hydrodesulfurization treatment under the following conditions. Reaction conditions Hydrogen partial pressure: 135 kg / cm ² Liquid space velocity: 0.2 (1 / hr) Hydrogen / oil ratio: 700 Nm ³ / kl The evaluation results are shown in Table 3. It turns out that high desulfurization performance can be obtained by using the hydrodesulfurization catalyst of the present invention.

[0053]

[Table 3] Performance Evaluation Experiment 2 Next, in order to consider the relationship between the amount of Mg added and the initial desulfurization activity, a small catalyst evaluation device (catalyst amount 3 cc) was used, and LGO (sulfur concentration 1.03 wt%, specific gravity 0.840) was used as a raw material.
Comparative evaluation was performed using 9). This evaluation evaluates how the interaction between Mo, which is an active metal, and phosphorus, which is a component effective for catalytic activity, and Mg component affects the catalytic surface activity.

The reaction conditions were as follows: LHSV = 7.0 (1 / h)
r), a hydrogen pressure of 50 kg / cm ² . Table 4 shows the evaluation results.

[0055]

[Table 4] Performance Evaluation Experiment 3 Further, the deterioration behavior of the catalyst activity with time was evaluated, and the effectiveness of magnesium addition was evaluated. The evaluation catalyst was prepared by combining Catalyst A and Catalyst D with the same amount of a demetalization catalyst, respectively.
0 cc high-pressure fixed-bed flow reactor, and using the above-mentioned normal pressure residual oil as a feed oil, a hydrogen partial pressure of 135 kg / c
m ³ , liquid space velocity 0.2 (1 / hr), hydrogen / oil ratio 70
The test was performed at 0 Nm ³ / kl. The oil was passed while adjusting the reaction temperature so as to keep the sulfur concentration in the produced oil constant at 0.2 wt%.

FIG. 1 shows the results. The degree of catalyst activity deterioration (° C.) in FIG.
The required reaction temperature at which the sulfur concentration in the produced oil at the time is 0.2 wt% is set as a reference value, and the amount of increase in the required reaction temperature at each oil passing time is calculated with respect to the reference value. It is plotted against oil time. That is, the higher the value on the vertical axis, the more the catalytic activity is degraded. It can be seen that Catalyst A has a lower rate of increase in the required reaction temperature per oil passing time than Catalyst D (20 times less than Catalyst D).
%). It has been found that a catalyst having a specific composition obtained by a specific catalyst manufacturing method using magnesium is a high-performance desulfurization catalyst.

[0057]

According to the hydrotreating of hydrocarbon oil using the catalyst composition of the present invention, hydrotreating such as desulfurization can be performed more efficiently than conventional hydrotreating catalysts. A useful hydrocarbon fraction in which the sulfur content and the like are significantly reduced can be obtained in good yield.

[Brief description of the drawings]

FIG. 1 is a graph showing a time-dependent degradation behavior of a catalyst activity.

Claims (4)

[Claims] 1. A refractory oxide carrier containing 1 to 10% by weight of nickel oxide and 5 to 5% by weight of molybdenum trioxide based on a catalyst.
20wt%, magnesium oxide 0.5 ~ 2.0wt%
And a catalyst in which phosphorus pentoxide is supported by 3 to 5 wt%, and 0.1 ≦ magnesium oxide (wt%) / phosphorus pentoxide (wt%) between the supporting ratios of magnesium oxide, phosphorus pentoxide and molybdenum trioxide. ≦ 0.5 and 0.06 ≦ magnesium oxide (wt%) / molybdenum trioxide (wt%) ≦
A hydrodesulfurization catalyst, wherein the relationship of 0.15 is satisfied. 2. A nickel compound, on a refractory oxide carrier.
A molybdenum compound, a magnesium compound, and a phosphorus compound are impregnated with an impregnating solution in which an organic acid compound is dissolved, and a supporting treatment is performed in the presence of polyethylene glycol having a molecular weight of 300 or more, followed by baking at a temperature of 400 ° C or more. A method for producing the hydrodesulfurization catalyst according to claim 1. 3. A refractory oxide carrier, as a first step, impregnated with an impregnating solution in which a magnesium compound is dissolved in the presence of an organic acid compound to carry out a supporting treatment, and calcination at a temperature of 400 ° C. or more; As a second step, a nickel compound, a molybdenum compound and a phosphorus compound are impregnated with an impregnating solution in which an organic acid compound is dissolved in the presence of an organic acid compound, and a supporting treatment is carried out in the presence of a polyethylene glycol having a molecular weight of 300 or more.
The method for producing a hydrodesulfurization catalyst according to claim 1, wherein the catalyst is calcined at a temperature of 0 ° C or higher. 4. A method for hydrodesulfurizing a hydrocarbon oil, comprising subjecting the hydrocarbon oil to contact with the catalyst according to claim 1 in the presence of hydrogen to carry out hydrotreatment.