JPH08176560A - Hydrodesulfurization of light oil - Google Patents

Abstract

PURPOSE: To efficiently carry out the hydrodesulfurization of a light oil, enable sufficient response to desulfurization of a hardly desulfurizing substance and obtain an ultralow sulfur light oil at a low cost by reacting a stock oil such as a catalytically cracked light oil under specific conditions. CONSTITUTION: One or more of a catalytically cracked light oil, a thermally cracked light oil, a straight run light oil, a coker gas oil, a hydrotreated light oil and a desulfurization treated light oil are used as a stock oil and catalytically reacted at 320-380 deg.C temperature under 30-80kg/cm<2> pressure at 1.0-5.0hr<-2> liquid space velocity and 100-400l/l hydrogen/oil ratio in the presence of a catalyst prepared by including a group VI metallic component of the periodic table in an amount of 10-30wt.% expressed in terms of an oxide, a group VIII metal of the periodic table in an amount of 1-10wt.% expressed in terms of an oxide and a phosphorus component in an amount of 1-7wt.% expressed in terms of an oxide in a carrier containing 80-99wt.% inorganic oxide and 1-20wt.% zeolite. Thereby, the hydrodesulfurization of the light oil is carried out. Furthermore, the catalytic reaction is preferably performed so as to provide 0.001-0.10wt.% sulfur content in the produced oil.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for hydrodesulfurizing light oil, and more particularly to a method for deeply desulfurizing light oil under a specific condition using a specific catalyst.

[0002]

The gas oil fraction obtained by distillation or cracking of crude oil generally contains sulfur compounds, and when these oils are used as fuel, they are present in the sulfur compounds. Sulfur is converted into sulfur compounds such as oxides and released into the atmosphere. Further, when used in a diesel engine, there is also an adverse effect on a device for removing NOx and the like, so it is desirable that the above-mentioned fraction has as low a sulfur content as possible. A gas oil fraction having a low sulfur content can be obtained by catalytic hydrodesulfurization of a gas oil fraction.

By the way, catalysts conventionally used for hydrodesulfurization of hydrocarbon oils are usually metals of Group VI of the periodic table (hereinafter, simply referred to as "Group VI metal") and Group VIII of the periodic table. A group metal (hereinafter, simply referred to as "Group VIII metal") is supported as an active metal on an oxide carrier such as alumina, magnesia or silica. At this time, generally, Mo or W is used as the Group VI metal, and Co or Ni is used as the Group VIII metal.

In order to improve the activity of this catalyst, phosphorus,
A technique of adding boron or the like has been reported (Japanese Patent Laid-Open No. Sho 5)
No. 2-1503). Further, a technique of mixing zeolite into an inorganic oxide used as a carrier has also been reported (see JP-A-56-20087). Moreover, techniques using both of them have been reported (Japanese Patent Laid-Open No. 61-126196, Japanese Laid-Open Patent Publication No. 2-21454).
No. 4).

However, these prior proposed techniques are mainly aimed at hydrodesulfurization or hydrocracking of heavy oil fractions of hydrocarbon oils, and mainly focus on deep hydrodesulfurization of light oil fractions. It's not the technology I used.

[0006] Further, in recent years, as the regulation of sulfur content in commercial gas oil has become stricter due to environmental problems (0.5 wt% → 0.05 wt%), further deep desulfurization is required, 4-methyldibenzothiophene (hereinafter referred to as "4M-DBT") and 4,6 dimethyldibenzothiophene (hereinafter referred to as "4,6DM-DBT")
It has become necessary to treat difficult-to-desulfurize substances such as

The present invention has been made in view of such circumstances of the prior art, and uses a catalyst that exhibits excellent desulfurization activity in the deep desulfurization region and can sufficiently cope with difficult desulfurization substances. An object of the present invention is to provide a method for hydrodesulfurizing light oil.

[0008]

Means for Solving the Problems As a result of repeated studies to achieve the above object, the present inventors have found that (1) a zeolite made of an inorganic oxide is contained in a carrier, and
When a catalyst containing phosphorus as an active ingredient consisting of a Group I metal component and a Group VIII metal component was used and a catalytic reaction was carried out under specific conditions, the catalyst contained sulfur contained in gas oil. 0.1 wt% or less, and even 0.05 w
It exhibits excellent performance in a hydrodesulfurization reaction of desulfurizing up to t% or less and can sufficiently cope with a substance which is said to be a difficult desulfurization substance. (2) In particular, the above zeolite is 24.4.
When the catalyst has a lattice constant of 5 to 24.55Å and the catalyst has a specific average pore diameter and specific pore diameter distribution, the sulfur content is 0.03 wt% or less and the desulfurization rate is high,
Moreover, they have found that deep desulfurization can be reliably performed with good reproducibility, and completed the present invention.

That is, the gas oil hydrodesulfurization method of the present invention uses at least one of catalytically cracked gas oil, thermally cracked gas oil, straight-run gas oil, coker gas oil, hydrotreated gas oil, and desulfurized gas oil as a feedstock oil. , 80 to 99% by weight of inorganic oxide
And a zeolite containing 1 to 20 wt% of the periodic table group VI metal component in terms of oxide of 10 to 30 wt% and the periodic table group VIII metal in terms of oxide of 1 to 10 wt%.
And a phosphorus component in an amount of 1 to 7 wt% in terms of oxide are used, the pressure (hydrogen partial pressure) is 30 to 80 kg / cm ² , the temperature is 320 to 380 ° C., and the liquid hourly space velocity is 1.0 to 5 0.0h
It is characterized in that the catalytic reaction is carried out with r ⁻¹ and hydrogen / oil ratio of 100 to 400 liters / liter (hereinafter, liter is referred to as “L”).

Further, the gas oil hydrodesulfurization method of the present invention comprises:
The zeolite contained in the above carrier is 24.45 to 24.
It is also characterized in that it has a lattice constant of 55Å, the catalyst used has an average pore diameter of 70 to 80Å, and the proportion of pores having an average pore diameter of ± 15Å is 70% or more.

Further, the method for hydrodesulfurizing light oil of the present invention is also characterized in that the catalytic reaction is carried out so that the sulfur content of the produced oil becomes 0.001 to 0.10% by weight.

The catalyst carrier used in the present invention is
It contains an inorganic oxide and zeolite. Of these, various types can be used as the inorganic oxide, for example,
Silica, alumina, boria, magnesia, titania, silica-alumina, silica-magnesia, silica-zirconia, silica-tria, silica-berrillia, silica-titania, silica-boria, alumina-zirconia, alumina-titania, alumina-boria, Alumina-chromia, titania-zirconia, silica-alumina-tria, silica-alumina-zirconia, silica-alumina-magnesia, silica-magnesia-zirconia, and the like, among them, alumina, silica-alumina, alumina-boria, alumina. -Titania and alumina-zirconia are preferable, and γ-alumina among alumina is particularly preferable. These inorganic oxides may be used alone or
A combination of two or more species can be used.

On the other hand, various kinds of zeolite can be used, for example, A-type zeolite, X-type zeolite,
Examples thereof include Y-type zeolite, stabilized Y-type zeolite, ultra-stable Y-type zeolite, L-type zeolite, and ZSM-type zeolite, with HY-type zeolite and stabilized Y-type zeolite being preferred. These crystalline zeolites can be used alone or in combination of two or more kinds.

Among the above crystalline zeolites, it is particularly preferable to use one having a lattice constant of 24.45 to 24.55Å. Zeolites having a lattice constant of less than 24.45Å may have a low total acid content, resulting in a decrease in overall desulfurization activity. On the other hand, in the case of zeolite having a content of more than 24.55Å, the total acid amount is large, but the acid strength is weak, so that it may be difficult to remove the hardly desulfurizable substance at the present desulfurization reaction temperature.

The content ratio of the inorganic oxide in the carrier is
It is 80 to 99% by weight, preferably 85 to 98% by weight, and the content ratio of the zeolite is 1 to 20% by weight, preferably 2 to 15% by weight.

When the content of the inorganic oxide is less than 80% by weight, the surface area of the whole catalyst becomes relatively small, which is not preferable as a carrier. When it exceeds 99% by weight, the content of the zeolite is relatively 1% by weight. %, The technical significance of containing zeolite does not appear, and the zeolite content is 20%.
If it exceeds 5% by weight, the dispersibility of the active metal deteriorates.

The carrier containing the above-mentioned inorganic oxide and zeolite includes montmorillonite, kaolin, halosite,
Clay minerals such as bentonite, adaval guide, bauxite, kaolinite, nacrite and anoxite may be contained alone or in combination of two or more.

The specific surface area, pore volume, and average pore diameter of the carrier used in the present invention are not particularly limited, but in order to make it a catalyst for removing even difficult-to-desulfurize substances, the specific surface area is not limited. Is preferably 250 m ² / g or more, the pore volume is preferably 0.3 to 1.2 cc / g, and the average pore diameter is 5
0 to 130Å is preferable.

As the Group VI metal component contained in the above carrier, various compounds can be used, but compounds of chromium, molybdenum and tungsten are preferable, and compounds of molybdenum and tungsten are particularly preferable. Specific examples of these compounds include (NH ₄ ) ₆ Mo ₇ O ₂₄ · 4H ₂
Ammonium molybdate represented by O, _(NH 4)
₁₀ W ammonium tungstate represented by ₁₂ O ₄₁ · 5H ₂ O, molybdenum oxide represented by MoO _3, H
_{3 (PMo 12 O 40) ·} 30H molybdophosphoric acid represented by _{2 O,} etc. tungstophosphoric acid represented by _{H 3 (PW 12 O 40)} · 30H 2 O and the like. These compounds can be used alone or in combination of two or more kinds.

As the Group VIII metal component to be contained together with the Group VI metal component, various compounds can be used, but compounds such as iron, cobalt, nickel, rhodium, palladium, osmium, iridium and platinum are preferable, Particularly, carbonates, acetates and phosphates of cobalt and nickel are preferable. These compounds may be used alone or
Combinations of more than one species can be used.

Further, the above Group VI metal and Group VI
Examples of the phosphorus component contained together with the Group II metal include various phosphoric acids, and specifically, orthophosphoric acid, metaphosphoric acid,
Examples include pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid, polyphosphoric acid,
In particular, orthophosphoric acid can be preferably used.

The content ratio of the Group VI, Group VIII metal component and phosphorus component is 10 to 30% by weight, preferably 15 to 23% by weight of the Group VI metal component in terms of oxide, based on the weight of the catalyst. % By weight, the Group VIII metal component is 1-10% by weight, preferably 3-7% by weight, and the phosphorus component is 1-7% by weight, preferably 2-5% by weight.
Is.

When the content of the Group VI metal component is less than 10% by weight, even the hardly desulfurizable substance cannot be efficiently removed, and when it exceeds 30% by weight, the dispersibility of the active metal is deteriorated. However, this effect is saturated and uneconomical. When the content of the Group VIII metal component is less than 1% by weight, the technical significance of containing the Group VIII metal component does not appear, and thus even the hardly desulfurizable substance cannot be efficiently removed. Even if it exceeds%, this effect is saturated and becomes uneconomical. Phosphorus component is 1% by weight
When the amount is less than the above, the technical significance of containing the phosphorus component is not expressed, and thus even the hardly desulfurizable substance cannot be efficiently removed. Even when it exceeds 7% by weight, this effect is saturated. It becomes uneconomical.

On the above carrier, the above-mentioned VI, VIII
The method of incorporating the group metal component and the phosphorus component, that is, the method of preparing the catalyst used in the present invention can be carried out by using several known techniques. One way is
Impregnation in which the above-mentioned carrier is dissolved in a solvent such as water, alcohols, ethers, ketones, etc., the group VI or VIII metal compound and phosphoric acid by one or more impregnation treatments There is a law. In this impregnation method, when the number of impregnation treatments is plural, drying / firing may be performed between each impregnation treatment.

As another method, a spraying method in which a solution in which the above-mentioned Group VI or Group VIII metal compound and phosphoric acid are dissolved is sprayed on the above carrier, or a Group VI or Group VIII metal component and phosphorus component is sprayed. There may be mentioned a chemical vapor deposition method in which and are chemically vapor-deposited.

As still another method, a kneading method or a coprecipitation method in which the above-mentioned carrier component before molding is made to contain a part or all of the above-mentioned Group VI or VIII metal component and phosphorus component, and molding is carried out. The alkoxide method can be mentioned.

The specific surface area and pore volume of the catalyst of the present invention prepared by the above various production methods are not particularly limited as long as they can function as a catalyst.
As in the case of the above-mentioned carrier, in order to efficiently remove even the hardly desulfurizable substance, the specific surface area is preferably 200 m ² / g or more and the pore volume is preferably 0.3 to 1.2 cc / g.

The average pore size of the catalyst is 60 to 120.
It may be about Å, but especially 70 to 80Å, preferably 73
It is suitable to set it to ~ 77Å. If the average pore size is too large, the diffusibility of the reaction material into the pores is good, but the effective surface area of the catalyst becomes small, so that it becomes difficult to remove the hardly desulfurizable material. When performing a deep desulfurization reaction, it is important to reduce the sulfur content to a predetermined level or less without deteriorating the hue of the produced gas oil, and thus operation is often performed at a low liquid hourly space velocity. In this case, since the contact time becomes long, it is not necessary to use a catalyst with a large average pore size to improve the diffusivity of the reactants. As a result, no improvement in activity is observed. On the other hand, if the average pore diameter is too small, problems such as insufficient mechanical strength will occur when trying to obtain the physical properties (specific surface area, pore volume) required to function as a catalyst, such as difficulty in production.

Furthermore, the pore size distribution of the catalyst (that is, the proportion of pores having an average pore size of ± 15Å) is 7
0% or more, preferably 80% or more is desirable. If the value of the pore size distribution is small and the distribution curve is broad, the number of effective pores for the reaction will be relatively small even if the average pore size is ideal, and a highly active catalyst will be obtained. Can not be expected.

The shape of the catalyst is not particularly limited, and various shapes usually used for this type of catalyst,
For example, a columnar shape, a four-leaf type, or the like can be adopted.
As for the size, usually, the diameter is preferably 1/10 to 1/22 inch and the length is preferably 3.2 to 3.6 inch.

When the above catalyst is used in the actual process to which the present invention is applied, it may be used alone, or may be used as a mixture with a known catalyst or a known inorganic oxide carrier. Further, the above catalyst, montmorillonite, kaolin, halosite, bentonite, adaval guide, bauxite, kaolinite, nacrite,
Clay minerals such as anoxite, alone or 2
It is also possible to include a combination of two or more species.

In the present invention using the above-mentioned catalyst, as the feedstock oil, catalytically cracked gas oil, thermally cracked gas oil, straight run gas oil,
Examples thereof include coker gas oil, hydrotreated gas oil, and desulfurized gas oil, which can be used alone or in combination of two or more kinds. In addition, these raw material oils have a boiling point range of 150 to 400 ° C., preferably 200 to 400 ° C.
380 ° C., more preferably 220 to 340 ° C.,
It is suitable that the sulfur content is 3% by weight or less, preferably 2.5% by weight or less, and more preferably 2.0% by weight or less.

Further, in the present invention, the hydrodesulfurization reaction conditions of the above feed oil include a pressure (hydrogen partial pressure) of 30 to 8
0 kg / cm ² , preferably 50-60 kg / cm ² ,
The temperature is 320 to 380 ° C., preferably 320 to 360
C., more preferably 330 to 360.degree. C., liquid hourly space velocity of 1.0 to 5.0 hr.sup.- ¹ , preferably 1.0 to 3.0 h.
r ⁻¹ , more preferably 1.0 to 2.0 hr ⁻¹ , hydrogen / oil ratio 100 to 400 L / L, preferably 20.
0-300 L / L is mentioned.

If the pressure (hydrogen partial pressure) is less than 30 kg / cm ² , even the hardly desulfurizable substance cannot be removed, and even if it exceeds 80 kg / cm ² , the removal efficiency of the hardly desulfurized substance is high. Not only is it saturated, but expensive equipment that can withstand such high pressures is required, which is uneconomical. Temperature is 320 ℃
If it is less than this, even the hardly desulfurizable substance cannot be removed, and even if it exceeds 380 ° C., the removal efficiency of the hardly desulfurizable substance is saturated, which is uneconomical. If the liquid hourly space velocity exceeds 5.0 hr ^-1 , the contact time between the catalyst and the feedstock becomes too short, and even the hardly desulfurizable substance cannot be removed.
When it is less than r ^-1 , the contact time becomes unnecessarily long and the treatment efficiency is lowered.

The reaction conditions are such that the sulfur content in the produced oil is 0.001 to 0.10% by weight, preferably 0.001 to
0.05% by weight, more preferably 0.005-0.04
It is preferable to select the conditions such that the weight%, and more preferably 0.01 to 0.03% by weight. Under such conditions, the life of the above catalyst becomes equal to or longer than the life of a typical conventional catalyst, and it becomes possible to use the above catalyst for one year or more in an actual apparatus.

In carrying out the present invention in which the above feed oil is hydrodesulfurized under the above conditions on a commercial scale, the above catalyst is used in a suitable reactor as a fixed bed, moving bed or fluidized bed, The feedstock oil may be introduced into the reactor and treated under predetermined conditions.

Most commonly, the catalyst described above is maintained as a fixed bed, with the feedstock passing downwardly through the fixed bed. The catalyst can be used in a single reactor or in several reactors in series.

[0038]

【Example】

Example 1 A carrier having a specific surface area of 372 m ² / g and a pore volume of 0.6
5 cc / g, average pore size 62Å, HY-type zeolite [SiO ₂ / Al ₂ O ₃ molar ratio 6 and Na ₂ O
Content is 0.3 wt% or less, specific surface area is 970
(Langmuir, m ² / g) and 620 (BE
T, m ² / g) and the crystal size is 0.7 to 1.0 μ.
m] 5 wt% γ-alumina was used, 20 wt% Mo as a Group VI metal (oxide), 5 wt% Co as a Group VIII metal (oxide), 3 wt% phosphorus (oxidation). The desulfurization reaction was carried out under the conditions shown in Table 1 using the catalyst contained therein. The results are shown in Table 4.

[0039]

[Table 1]

Example 2 As a carrier, a specific surface area of 387 m ² / g and a pore volume of 0.6
5 cc / g, average pore diameter 61Å, 10% by weight of HY-type zeolite (the same HY-type zeolite as in Example 1) γ
-The desulfurization reaction was performed in the same manner as in Example 1 except that alumina was used. The results are also shown in Table 4.

Example 3 A carrier having a specific surface area of 405 m ² / g and a pore volume of 0.6
5 cc / g, average pore diameter 67Å, and 20% by weight of HY-type zeolite (HY-type zeolite same as in Example 1) γ
-The desulfurization reaction was performed in the same manner as in Example 1 except that alumina was used. The results are also shown in Table 4.

Example 4 The desulfurization reaction was carried out in the same manner as in Example 1 except that phosphorus was 1% by weight. The results are also shown in Table 4.

Example 5 A desulfurization reaction was carried out in the same manner as in Example 1 except that phosphorus was 5% by weight. The results are also shown in Table 4.

Example 6 A desulfurization reaction was carried out in the same manner as in Example 2 except that phosphorus was 7% by weight. The results are also shown in Table 4.

Example 7 A desulfurization reaction was carried out in the same manner as in Example 1 except that Mo was 25% by weight and Co was 3% by weight. The results are also shown in Table 4.

Example 8 A desulfurization reaction was carried out in the same manner as in Example 1 except that Mo was 25% by weight and Co was 8% by weight. The results are also shown in Table 4.

Example 9 15 wt% W and 5 wt% Co instead of 20 wt% Mo
The desulfurization reaction was performed in the same manner as in Example 1 except that Ni was changed to 3% by weight. The results are also shown in Table 4.

Example 10 The desulfurization reaction was performed in the same manner as in Example 1 except that Mo was 15% by weight and Co was 8% by weight. The results are also shown in Table 4.

Comparative Example 1 A carrier having a specific surface area of 336 m ² / g and a pore volume of 0.7
The desulfurization reaction was carried out in the same manner as in Example 1 except that γ-alumina having 1 cc / g and an average pore diameter of 68 Å was used and phosphorus was not contained. The results are shown in Table 5.

Comparative Example 2 The desulfurization reaction was carried out in the same manner as in Comparative Example 1 except that phosphorus was 3% by weight. The results are also shown in Table 5.

Comparative Example 3 The desulfurization reaction was carried out in the same manner as in Example 1 except that phosphorus was not added. The results are also shown in Table 5.

Comparative Example 4 The desulfurization reaction was carried out in the same manner as in Example 1 except that phosphorus was changed to 10% by weight. The results are also shown in Table 5.

Comparative Example 5 A carrier having a specific surface area of 412 m ² / g and a pore volume of 0.6
5 cc / g, average pore diameter 70Å, and 30% by weight of HY-type zeolite (the same HY-type zeolite as in Example 1) γ
-The desulfurization reaction was performed in the same manner as in Example 1 except that alumina was used. The results are also shown in Table 5.

Comparative Example 6 Example 1 was repeated except that Co was not supported and phosphorus was 5% by weight.
The desulfurization reaction was carried out in the same manner as in. The results are also shown in Table 5.

Comparative Example 7 The desulfurization reaction was carried out in the same manner as in Example 1 except that Co was changed to 15% by weight. The results are also shown in Table 5.

Comparative Example 8 HY-type zeolite (the same HY-type zeolite as in Example 1)
Using 10% by weight of γ-alumina, 8% by weight of Mo
The desulfurization reaction was performed in the same manner as in Example 1 except that The results are also shown in Table 5.

Comparative Example 9 HY-type zeolite (the same HY-type zeolite as in Example 1)
The desulfurization reaction was performed in the same manner as in Example 1 except that 10 wt% γ-alumina was used and Mo was 35 wt%. The results are also shown in Table 5.

The compositions and physical properties of the catalysts used in the above Examples and Comparative Examples are shown in Tables 2 and 3, respectively.

[0059]

[Table 2]

[0060]

[Table 3]

[0061]

[Table 4]

[0062]

[Table 5]

The produced oils obtained in Examples 1 to 10 and Comparative Examples 1 to 9 were applied to a GC-AED analyzer to analyze the residual sulfur content. Table 6 shows the results.

[0064]

[Table 6]

Example 11 A carrier having a specific surface area of 372 m ² / g and a pore volume of 0.6
HY type zeolite [SiO ₂ / Al ₂ O at 5 cc / g
The molar ratio of ₃ is 6, the Na ₂ O content is 0.3 wt% or less,
Specific surface area of 970 (Langmuir, m ² / g) and 620 (BET, m ² / g), crystal size of 0.7-.
1.0 μm, lattice constant is 24.45Å] 5 wt% γ
-Alumina is used and the active metal loading is Co: Mo: P
= 5: 20: 3 (oxide,% by weight), using a catalyst having an average pore size and a pore size distribution (proportion of pores having an average pore size of ± 15Å) shown in Table 9, Table 7 The desulfurization reaction was performed under the conditions of. The results are shown in Table 10.

[0066]

[Table 7]

Example 12 Except that the loading ratio of phosphorus was set to 7% by weight and the catalyst having the average pore size and the pore size distribution (the ratio of the pores having the average pore size ± 15Å) shown in Table 9 was used. The desulfurization reaction was performed in the same manner as in Example 11. The results are also shown in Table 10.

Example 13 A carrier having a specific surface area of 387 m ² / g and a pore volume of 0.65 c
c / g, gamma-alumina containing 10% by weight of HY-type zeolite, and using a catalyst having an average pore size and a pore size distribution (ratio of pores having an average pore size of ± 15Å) shown in Table 9 A desulfurization reaction was performed in the same manner as in Example 11. The results are also shown in Table 10.

Example 14 A carrier having a specific surface area of 403 m ² / g and a pore volume of 0.65 c
c-g, gamma-alumina containing 20% by weight of HY-type zeolite, and using a catalyst having an average pore diameter and a pore diameter distribution (ratio of pores having an average pore diameter of ± 15Å) shown in Table 9 A desulfurization reaction was performed in the same manner as in Example 11. The results are also shown in Table 10.

Example 15 A carrier having a specific surface area of 386 m ² / g and a pore volume of 0.67 c
c / g, the zeolite used is SiO ₂ / Al ₂ O ₃
Molar ratio of 5.5, Na ₂ O content of 0.3 wt% or less, specific surface area 730 (Langmuir, m ² / g) and 5
30 (BET, m ² / g), crystal size 0.6 to 0.9
The same as Example 11 except that the catalyst having the average pore size and pore size distribution (the ratio of the pores having the average pore size ± 15 Å) shown in Table 9 is used with μm and a lattice constant of 24.55Å. The desulfurization reaction was carried out by the above method. The results are also shown in Table 10.

COMPARATIVE EXAMPLE 10 A carrier having a specific surface area of 336 m ² / g and a pore volume of 0.71 c
A catalyst consisting of only c / g of gamma-alumina, not supporting phosphorus as an active ingredient, and having an average pore diameter and a pore diameter distribution (a proportion of pores having an average pore diameter of ± 15Å) shown in Table 9. The desulfurization reaction was performed in the same manner as in Example 11 except that The results are shown in Table 10.

Comparative Example 11 A desulfurization reaction was carried out in the same manner as in Comparative Example 10 except that the loading ratio of phosphorus was 3% by weight. The results are also shown in Table 10.

Comparative Example 12 The average pore diameter and the pore diameter distribution shown in Table 9 (the proportion of pores having an average pore diameter of ± 15Å) without supporting phosphorus.
A desulfurization reaction was carried out in the same manner as in Example 11 except that the catalyst of 1 was used. The results are also shown in Table 10.

COMPARATIVE EXAMPLE 13 A carrier having a specific surface area of 374 m ² / g and a pore volume of 0.69 c
c / g, the zeolite used is SiO ₂ / Al ₂ O ₃
Molar ratio 10, Na ₂ O content 0.3 wt% or less, specific surface area 950 (Langmuir, m ² / g) and 610
(BET, m ² / g), crystal size 0.6 to 0.9 μ
m and a lattice constant of 24.38Å, and using a catalyst having an average pore diameter and a pore diameter distribution (ratio of pores having an average pore diameter of ± 15Å) shown in Table 9, Example 1
The desulfurization reaction was performed in the same manner as in 1. The results are shown in Table 1.
Shown together with 0.

Comparative Example 14 A desulfurization reaction was carried out in the same manner as in Example 11 except that catalysts having different physical properties (average pore diameter) were used. The results are also shown in Table 10.

Comparative Example 15 A desulfurization reaction was carried out in the same manner as in Example 11 except that catalysts differing only in the physical properties (pore size distribution) were used. The results are also shown in Table 10.

The above Examples 11 to 15 and Comparative Example 10
Table 8 shows the compositions of the catalysts used in Examples 15 to 15, and Table 9 shows the physical properties.
Shown in

[0078]

[Table 8]

[0079]

[Table 9]

[0080]

[Table 10]

Further, the produced oils obtained in Example 11 and Comparative Example 10 were subjected to GC-AED analysis to analyze the residual sulfur content. The results are shown in Table 11.

[0082]

[Table 11]

[0083]

As described in detail above, according to the present invention,
Using a catalyst showing excellent activity in the deep desulfurization region,
Moreover, since the catalyst carries out the hydrodesulfurization reaction of light oil under specific reaction conditions capable of maximizing its performance in this region, it becomes a problem when producing light oil having a sulfur content of 0.05% by weight or less. 4M-DBT or 4,6DM-DB
It is possible to sufficiently deal with desulfurization of a hardly desulfurizable substance such as T, and it is possible to provide ultra-low sulfur gas oil at low cost.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazuo Idei 294 Kamitatakashima, Ohira-cho, Shimotsuga-gun, Tochigi Prefecture (72) Inventor Etsuo Suzuki Meiwa-mura, Era-gun, Gunma Prefecture 689-8 (72) Inventor Katsumi Oki Saitama 1368 Shinmeiuchi, Satte-shi, prefecture (72) Inventor Takashi Fujikawa 980, Albany Cornell Street, California, United States (72) Inventor Hattataro Yamazaki 4-72-8 Nishi-Shinjuku, Hasuda-shi, Saitama (72) Inventor Shunji Kitada Saitama 4-20 Hanaguri, Soka City

Claims (3)

[Claims] 1. A catalytically cracked gas oil, a thermally cracked gas oil, a straight-run gas oil,
At least one of coker gas oil, hydrotreated gas oil, and desulfurized gas oil was used as a feed oil, and a carrier containing 80 to 99% by weight of inorganic oxide and 1 to 20% by weight of zeolite was added to a carrier of Group VI of the periodic table. The metal component is 10 to 30 wt% in terms of oxide, the Group VIII metal of the periodic table is 1 to 10 wt% in terms of oxide, and the phosphorus component is 1 in terms of oxide.
With 7 wt% content is allowed catalyst, 30~80kg / cm ² pressure, temperature 320-380
A hydrodesulfurization method of gas oil, which comprises carrying out a catalytic reaction at a temperature of 1.0 ° C., a liquid hourly space velocity of 1.0 to 5.0 hr ⁻¹ and a hydrogen / oil ratio of 100 to 400 liters / liter. 2. The zeolite contained in the carrier is 24.45.
It has a lattice constant of ˜24.55Å, the catalyst used has an average pore diameter of 70-80 Å, and the proportion of pores having an average pore diameter of ± 15 Å is 70% or more. Item 1. A method for hydrodesulfurizing gas oil according to Item 1. 3. The sulfur content of the produced oil is 0.001 to 0.10.
The hydrodesulfurization method of gas oil according to claim 1 or 2, wherein the catalytic reaction is carried out so that the amount of the catalyst is in a weight percentage.