JP2996435B2 - Hydrodesulfurization of gas oil - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for hydrodesulfurizing gas oil, and more particularly, to a method for deep desulfurizing gas oil under specific conditions using a specific catalyst.

[0002]

2. Description of the Related Art Gas oil fractions obtained by distillation or cracking of crude oil generally contain sulfur compounds, and when these oils are used as fuel, they are present in the sulfur compounds. The resulting sulfur is converted to sulfur compounds such as oxides and released into the atmosphere. In addition, when used in a diesel engine, there is an adverse effect on a device for removing NOx and the like, so that the above-mentioned fraction should desirably have a sulfur content as small as possible. The gas oil fraction having a low sulfur content can be obtained by catalytic hydrodesulfurization of the gas oil fraction.

[0003] The catalysts conventionally used for hydrodesulfurization of hydrocarbon oils usually include a Group VI metal of the Periodic Table (hereinafter simply referred to as a "Group VI metal") and a Group VIII of the Periodic Table. A group metal (hereinafter simply referred to as a "Group VIII metal") is supported as an active metal on an oxide carrier such as alumina, magnesia, and 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 for adding boron or the like has been reported (Japanese Patent Laid-Open No.
See JP-A-2-13503). Furthermore, a technique has been reported in which zeolite is mixed into an inorganic oxide used as a carrier (see JP-A-56-20087). In addition, techniques using both of them have been reported (JP-A-61-126196, JP-A-2-21454).
No. 4).

However, these prior proposals are mainly intended for hydrodesulfurization or hydrocracking of heavy oil fractions of hydrocarbon oils, and mainly focus on the deep hydrodesulfurization of light oil fractions. It is not a technology that has been used.

Further, in recent years, as the regulations on sulfur contained in commercial gas oil have become more stringent due to environmental problems (0.5 wt% → 0.05 wt%), further deep desulfurization has been required. 4-methyldibenzothiophene (hereinafter, referred to as “4M-DBT”) and 4,6 dimethyldibenzothiophene (hereinafter, “4,6DM-DBT”)
It has become necessary to treat hard-to-desulfurize substances.

The present invention has been made in view of such circumstances of the prior art, and uses a catalyst which exhibits excellent desulfurization activity in a deep desulfurization region and which can sufficiently cope with hardly desulfurizable substances. Another object of the present invention is to provide a method for hydrodesulfurizing gas 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 carrier comprising an inorganic oxide contains zeolite and
When a catalyst containing phosphorus as an active component comprising 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 was found to contain sulfur contained in gas oil. 0.1 wt% or less, and 0.05 w
It exhibits excellent performance in hydrodesulfurization reaction to desulfurize to t% or less, and can sufficiently cope with substances which are said to be difficult to desulfurize. (2) Particularly, the above zeolite is 24.4.
In the case where the catalyst has a lattice constant of 5 to 24.55 ° and the catalyst has a specific average pore diameter and a pore diameter distribution, the sulfur content is reduced to 0.03 wt% or less, and the desulfurization rate is high.
Moreover, they have found that depth desulfurization can be reliably performed with good reproducibility, and have completed the present invention.

That is, the method for hydrodesulfurizing gas oil according to the present invention comprises using at least one of a catalytic cracking gas oil, a pyrolysis gas oil, a straight run gas oil, a coker gas oil, a hydrotreated gas oil, and a desulfurized gas oil as a feed oil. 80-99% by weight of inorganic oxide
And a zeolite in an amount of 1 to 20% by weight, a Group VI metal component of the periodic table in an amount of 10 to 30% by weight as an oxide, and a Group VIII metal of the periodic table in an amount of 1 to 10% by weight as an oxide.
And a catalyst containing 1 to 7% by weight of a phosphorus component in terms of oxides, a pressure (hydrogen partial pressure) of 30 to 80 kg / cm ² , a temperature of 320 to 380 ° C., and a liquid hourly space velocity of 1.0 to 3 0.0 h
It is characterized in that the contact reaction is carried out with r ^-1 and a hydrogen / oil ratio of 100 to 400 liter / liter (hereinafter, liter is referred to as “L”).

[0010] Further, the method for hydrodesulfurizing gas oil of the present invention comprises:
24.45 to 24. zeolite contained in the above carrier.
It is also characterized in that the catalyst used has a lattice constant of 55 °, the used catalyst has an average pore diameter of 70 to 80 °, and the ratio of pores having an average pore diameter of ± 15 ° is 70% or more.

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

The carrier of the catalyst used in the present invention is:
It contains an inorganic oxide and zeolite. Among them, various inorganic oxides can be used, for example,
Silica, alumina, boria, magnesia, titania, silica-alumina, silica-magnesia, silica-zirconia, silica-tria, silica-berylia, 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, etc., among which alumina, silica-alumina, alumina-boria, alumina -Titania and alumina-zirconia are preferred, and among aluminas, γ-alumina is particularly preferred. These inorganic oxides can be used alone or
More than one species can be used in combination.

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

[0014] The above-mentioned crystalline zeolite, lattice constant is 2
Ru used as the 4.45~24.55Å. Lattice constant is 2
With a zeolite of less than 4.45 °, the total acid content is small and the overall desulfurization activity may be reduced. Conversely, 24.5
In the case of zeolite exceeding 5%, although the total amount of acid is large, the acid strength is weak, so that it may be difficult to remove the hardly desulfurizable substance at the current desulfurization reaction temperature.

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

If the amount of the inorganic oxide is less than 80% by weight, the surface area of the entire catalyst is relatively small, for example, which is not preferable. If it exceeds 99% by weight, the zeolite content is relatively 1% by weight. %, The technical significance of containing zeolite is not expressed, and
If the content is more than 10% by weight, the dispersibility of the active metal becomes poor.

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 can be included 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. 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
0-130 ° is preferred.

As the Group VI metal component to be contained in the above-mentioned carrier, various compounds can be used, but a compound of chromium, molybdenum and tungsten is preferable, and a compound of molybdenum and tungsten is particularly preferable. Specific examples of these _{compounds, (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.

As the Group VIII metal component to be contained together with the Group VI metal component, various ones can be used, and compounds such as iron, cobalt, nickel, rhodium, palladium, osmium, iridium and platinum are preferable. In particular, cobalt, nickel carbonate, acetate and phosphate are preferred. These compounds can be used alone or
More than one species can be used in combination.

Further, the above-mentioned Group VI metal and VI
Examples of the phosphorus component to be contained together with the Group II metal include various phosphoric acids, and specifically, orthophosphoric acid, metaphosphoric acid,
Pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid, polyphosphoric acid, and the like,
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, based on the weight of the catalyst, in terms of oxide. % By weight, the Group VIII metal component is 1 to 10% by weight, preferably 3 to 7% by weight, and the phosphorus component is 1 to 7% by weight, preferably 2 to 5% by weight.
It is.

If the Group VI metal component is less than 10% by weight, it is not possible to efficiently remove even the non-desulfurizable substances, and if it exceeds 30% by weight, the dispersibility of the active metal becomes poor. Instead, this effect is saturated and uneconomical. If the content of the Group VIII metal component is less than 1% by weight, the technical significance of including the Group VIII metal component will not be exhibited, and therefore, even difficult-to-desulfurize substances cannot be efficiently removed. %, This effect is saturated and uneconomical. 1% by weight of phosphorus component
If it is less than 7, the technical significance of including the phosphorus component is not exhibited, and therefore it is not possible to efficiently remove even the hardly desulfurizable substances. Even if it exceeds 7% by weight, this effect is saturated. It is uneconomical.

On the above carrier, the above VI, VIII
The method for incorporating the group metal component and the phosphorus component, that is, the method for preparing the catalyst used in the present invention, can be carried out using several known techniques. One way is to
Impregnation in which a solution obtained by dissolving the above Group VI or VIII metal compound and phosphoric acid in a solvent such as water, alcohols, ethers or ketones is supported on the carrier by one or more stages of impregnation. Law. In this impregnation method, when the number of times of the impregnation process is plural, drying and baking may be performed between each impregnation process.

As another method, a spraying method of spraying a solution in which the above-mentioned Group VI, VIII metal compound and phosphoric acid are dissolved on the above-mentioned carrier, or a method of spraying the Group VI, Group VIII metal component with the phosphorus component And a chemical vapor deposition method of chemically vapor depositing them.

As still another method, a kneading method and a coprecipitation method in which the carrier component before molding contains part or all of the above-mentioned Group VI and VIII metal components and a phosphorus component, and is molded. Alkoxide method.

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 hardly desulfurizable substances, 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 diameter of the catalyst is 60 to 120.
よ い, but in particular, 70-80７０, preferably 73
It is suitable to be ~ 77 °. If the average pore diameter is too large, the diffusibility of the reactants into the pores is good, but the effective surface area of the catalyst is small, so that it is difficult to remove the difficult-to-desulfurize substances. In the case of 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 light oil, and therefore, the operation is often performed at a low liquid hourly space velocity. In this case, the contact time becomes longer, so that it is not necessary to use a catalyst having a large average pore diameter to improve the diffusibility of the reactants, and conversely, if a catalyst having a large average pore diameter is used, the result is that No improvement in activity is observed. On the other hand, if the average pore diameter is too small, difficulties in production such as insufficient mechanical strength occur when trying to obtain physical properties (specific surface area, pore volume) required to function as a catalyst.

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

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

When the above-mentioned catalyst is used in an 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. The catalyst includes montmorillonite, kaolin, halloysite, bentonite, Adaval guide, bauxite, kaolinite, nacrite,
Clay minerals such as anoxite, alone or
More than one species may be included in combination.

In the present invention using the above-mentioned catalyst, the raw material oil includes catalytic cracking gas oil, pyrolysis gas oil, straight-run gas oil,
Coker gas oil, hydrotreated gas oil, and desulfurized gas oil can be used, and these can be used alone or in combination of two or more. In addition, these stock 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, more preferably 2.0% by weight or less.

In the present invention, the conditions for the hydrodesulfurization of the feedstock oil are as follows: a pressure (hydrogen partial pressure) of 30 to 8;
0 kg / cm ² , preferably 50-60 kg / cm ² ,
The temperature is from 320 to 380 ° C, preferably from 320 to 360
° C, more preferably 330 to 360 ° C, and the liquid hourly space velocity is 1.0 to 3.0 hr ^-1 , more preferably 1.0 to 3.0 hr ^-1 .
2.0 hr ^-1 , hydrogen / oil ratio of 100 to 400 L /
L, preferably 200 to 300 L / L.

[0034] When the pressure (hydrogen partial pressure) is less than 30kg / cm ^2, can not also be removed until the flame desulphurization substances, even beyond 80 kg / cm ^2, the removal efficiency of the hardly desulfurized substance Not only does it saturate, but it requires expensive equipment that can withstand such high pressures, which is uneconomical. Temperature is 320 ° C
If it is less than that, even the hardly desulfurizable substance cannot be removed, and even if it exceeds 380 ° C., the efficiency of removing the hardly desulfurizable substance is saturated, which is uneconomical. When the liquid hourly space velocity exceeds 5.0 hr ⁻¹ , the contact time between the catalyst and the feed oil becomes too short, so that it is not possible to remove even the hardly desulfurizable substances,
When it is less than r- ¹ , the contact time becomes too long more than necessary, and the processing efficiency is reduced.

The reaction conditions are such that the sulfur content in the product oil is
0 . 001 to 0.05% by weight, more preferably 0.00
5 to 0.04% by weight, more preferably 0.01 to 0.
It is preferable to select a condition that will be 03% by weight. Under such conditions, the life of the above catalyst is equal to or longer than the life of a conventional typical catalyst,
The above-mentioned catalyst can be used for one year or more in an actual device.

When the present invention for hydrodesulfurizing the above feedstock under the above conditions is carried out on a commercial scale, the above catalyst is used as a fixed bed, a moving bed or a fluidized bed in a suitable reactor. What is necessary is just to introduce | transduce the said raw material oil into this reactor, and to process on predetermined conditions.

Most commonly, the catalyst is maintained as a fixed bed such that the feedstock passes down through the fixed bed. The catalyst can be used in a single reactor or in several reactors in series.

[0038]

【Example】

Example 1 As a carrier, the specific surface area was 372 m ² / g, and the pore volume was 0.6.
HY-type zeolite [SiO ₂ / Al ₂ O ₃ molar ratio is 6 and Na ₂ O
The content is 0.3% by weight or less, and the 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 μm.
m] using γ-alumina containing 5% by weight, 20% by weight of Mo as a Group VI metal (oxide), 5% by weight of Co as Group VIII metal (oxide), and 3% by weight of phosphorus (oxidation) The desulfurization reaction was carried out under the conditions shown in Table 1 using the catalyst contained in the product. Table 4 shows the results.

[0039]

[Table 1]

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

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

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

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

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

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

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

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

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

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

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

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

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

Comparative Example 7 A 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 shown in Table 5.

Comparative Example 8 HY zeolite (same HY zeolite as in Example 1)
8% by weight of Mo using γ-alumina containing 10% by weight
A desulfurization reaction was carried out in the same manner as in Example 1 except for the following. The results are shown in Table 5.

Comparative Example 9 HY-type zeolite (the same HY-type zeolite as in Example 1)
A desulfurization reaction was performed in the same manner as in Example 1 except that γ-alumina containing 10% by weight was used and Mo was changed to 35% by weight. The results are 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]

Further, the product oils obtained in the above Examples 1 to 10 and Comparative Examples 1 to 9 were analyzed by GC-AED analyzer for residual sulfur content. Table 6 shows the results.

[0064]

[Table 6]

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

[0066]

[Table 7]

Example 12 Except that the supporting ratio of phosphorus was 7% by weight and a catalyst having an average pore diameter and a pore diameter distribution shown in Table 9 (a ratio of pores having an average pore diameter of ± 15 °) was used. A desulfurization reaction was performed in the same manner as in Example 11. The results are shown in Table 10.

Example 13 A carrier was used, 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 diameter and a pore diameter distribution shown in Table 9 (a ratio of pores having an average pore diameter of ± 15 °). A desulfurization reaction was performed in the same manner as in Example 11. The results are shown in Table 10.

Example 14 A carrier was prepared by using 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 shown in Table 9 (ratio of pores having a pore diameter of ± 15 ° in average pore diameter). A desulfurization reaction was performed in the same manner as in Example 11. The results are shown in Table 10.

Example 15 A carrier was prepared using a specific surface area of 386 m ² / g and a pore volume of 0.67 c.
In c / g, the zeolite used is SiO ₂ / Al ₂ O ₃
5.5, a Na ₂ O content of 0.3% by weight or less, a specific surface area of 730 (Langmuir, m ² / g) and 5
^{30 (BET, m 2 / g} ), crystal size 0.6 to 0.9
μm, a lattice constant of 24.55 °, and the same as Example 11 except that a catalyst having an average pore diameter and a pore diameter distribution shown in Table 9 (proportion of pores having an average pore diameter of ± 15 °) was used. The desulfurization reaction was performed by the following method. The results are shown in Table 10.

COMPARATIVE EXAMPLE 10 A carrier was prepared by using a specific surface area of 336 m ² / g and a pore volume of 0.71 c.
A catalyst comprising only c / g gamma-alumina, not supporting phosphorus as an active ingredient, and having an average pore diameter and a pore diameter distribution shown in Table 9 (ratio of pores having an average pore diameter of ± 15 °). A desulfurization reaction was carried out in the same manner as in Example 11 except for using. Table 10 shows the results.

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 changed to 3% by weight. The results are shown in Table 10.

Comparative Example 12 The average pore diameter and the pore diameter distribution shown in Table 9 without phosphorus being supported (the ratio of the pores having a pore diameter of an average pore diameter ± 15 °)
A desulfurization reaction was performed in the same manner as in Example 11 except that the above catalyst was used. The results are shown in Table 10.

Comparative Example 13 A carrier was used, having a specific surface area of 374 m ² / g and a pore volume of 0.69 c.
In 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 0.6-0.9μ
m, a lattice constant of 24.38 °, and a catalyst having an average pore diameter and a pore diameter distribution shown in Table 9 (the ratio of pores having an average pore diameter of ± 15 °) was used.
A desulfurization reaction was performed in the same manner as in Example 1. Table 1 shows the results.
0 is also shown.

Comparative Example 14 A desulfurization reaction was carried out in the same manner as in Example 11 except that a catalyst differing only in physical properties (average pore diameter) was used. The results are shown in Table 10.

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

Examples 11 to 15 and Comparative Example 10
The compositions of the catalysts used in Tables 1 to 15 are shown in Table 8, and the physical properties are shown in Table 9.
Shown in

[0078]

[Table 8]

[0079]

[Table 9]

[0080]

[Table 10]

Further, GC-AED analysis was performed on the product oils obtained in Example 11 and Comparative Example 10 to analyze residual sulfur content. Table 11 shows the results.

[0082]

[Table 11]

[0083]

As described in detail above, according to the present invention,
Using a catalyst that shows excellent activity in the deep desulfurization area,
In addition, since the catalyst performs the hydrodesulfurization reaction of gas oil under specific reaction conditions under which the catalyst can exhibit its performance in the above range, it is problematic when producing gas oil having a sulfur content of 0.05% by weight or less. 4M-DBT or 4,6DM-DB
It can sufficiently cope with the desulfurization of difficult-to-desulfurize substances such as T, and can provide ultra-low sulfur gas oil at low cost.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Etsuo Suzuki Gunma Pref., Meiwa Village, Gunma Prefecture, Niizato 689-8 Nisato (72) Inventor Katsumi Oki 1368, Shinmei, Satte-shi, Saitama 980, Albany-Cornell Street (72) Inventor, Hatsuro Yamazaki 4-72-8, Nishishinjuku, Hasuda City, Saitama Prefecture (72) Inventor Shunji Kitada 4-20, Hanaguri, Soka City, Saitama Prefecture (56) References JP-A-6-1994 121931 (JP, A) (58) Field surveyed (Int. Cl. ⁶ , DB name) C10G 45/12 C10G 45/08

Claims (2)

(57) [Claims] (1) catalytic cracking gas oil, pyrolysis gas oil, straight-run gas oil,
At least one of coker gas oil, hydrotreated gas oil, and desulfurized gas oil is used as a raw material oil, and 80 to 99% by weight of an inorganic oxide and a lattice constant of 24.45 to 24.45 %.
A support containing 1 to 20% by weight of a zeolite having 24.55 % and a Group VI metal component of the periodic table in an amount of 10 to 3 in terms of oxide.
0 wt% and 1 to 10% by weight of Group VIII metal in terms of oxide and 1-7 wt% of the phosphorus component in terms of oxide
Containing, having an average pore diameter of 70 to 80 °, and an average pore diameter of
The ratio of pores having a pore diameter of ± 15 ° is 70% or more.
That the catalyst used, 30~80kg / cm ² pressure, temperature 320-380
A method for hydrodesulfurizing gas oil, comprising: performing a contact reaction at a temperature of 1.0 ° C., a liquid hourly space velocity of 1.0 to 3.0 hr ⁻¹ , and a hydrogen / oil ratio of 100 to 400 L / L. 2. The product oil has a sulfur content of 0.001 to 0.05.
Hydrodesulfurization method of claim 1 Symbol placement of the gas oil and performing catalytic reaction for a weight%.