JP2921379B2 - 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.

[0006] In recent years, as the regulations on the sulfur content in commercial light oil have become more stringent due to environmental problems (0.5 wt% → 0.05 wt%), further deep desulfurization has been required, and in this region, it is difficult to desulfurize. Substance 4M
-DBT (4 methyl dibenzothiophene), 4,6DM
-It has become necessary to treat difficult-to-desulfurize substances centered on DBT (4,6 dimethyldibenzothiophene).

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 surprisingly found that a carrier containing an inorganic oxide and a HY-type zeolite contains a Group VI metal , Under a specific reaction condition, the catalyst supporting a specific metal of the Group VIII metals can reduce the sulfur content in light oil to 0.10 wt% or less, and further to 0.05 wt% or less. The present inventors have found that they show excellent performance in hydrodesulfurization reaction for desulfurization and can sufficiently cope with substances which are said to be difficult to desulfurize, and have completed the present invention.

That is, the present invention relates to at least one of catalytic cracking gas oil, pyrolysis gas oil, straight run gas oil, coker gas oil, hydrotreated gas oil, and desulfurized gas oil, which has a boiling point range of 150 to 400 ° C. content of which those 3% by weight or less as a feed oil, an inorganic oxide 80-99 wt% and the HY type zeo <br/> write 1 to 20% by weight in a carrier consisting Nde containing, periodic table group VI metal The content of the component is 10 to 30% by weight in terms of oxide, and a small amount of cobalt and nickel as Group VIII metals of the periodic table.
Used was contained 1-10 wt% of one in terms of oxide catalyst even without the pressure (hydrogen partial pressure) 30~80kg / cm
^2. Temperature 320-360 ° C, liquid hourly space velocity 0.5-
5.0 hr ^-1 , a hydrogen / oil ratio of 100 to 400 liter / liter (hereinafter, liter is referred to as “L”), and a sulfur content of the produced oil of 0.01 to 0.08 % by weight.
Thus, a gist of the present invention is a method for hydrodesulfurizing gas oil, which comprises performing a catalytic reaction.

Hereinafter, the present invention will be described in detail. The catalyst support used in the present invention contains an inorganic oxide and zeolite. Of these, as inorganic oxides,
Various types can be used, for example, silica, alumina, boria, magnesia, titania, silica-alumina, silica-magnesia, silica-zirconia, silica-tria, silica-beryllia, 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, among others.
Alumina, silica-alumina, alumina-boria, alumina-titania, and alumina-zirconia are preferred, and γ-alumina is particularly preferred among aluminas. These inorganic oxides can be used alone or in combination of two or more.

[0011] Together with the above inorganic oxide, HY-type
A catalyst carrier used in the method of the present invention by incorporating
(Hereinafter referred to as “zeolite”, “HY type zeolite”
Olite ") .

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 of the catalyst becomes small, meaning that it has no meaning as a carrier. Therefore, the technical significance of containing the zeolite does not appear, and when the zeolite exceeds 20% by weight, the dispersibility of the active metal becomes poor.

The carrier containing the above 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 composed of each of the above components are not particularly limited. However, in order to obtain a catalyst that can remove even difficult-to-desulfurize substances, The specific surface area 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 preferably 50 to 130 °.

As the Group VI metal component to be contained in the above carrier, various ones 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.

[0017] As the Group VIII metal component to be contained together with the Group VI metal component described above, cobalt, nickel
Use of the compound, in particular cobalt, carbonates nickel,
Acetate, phosphate salt rather be used preferably (hereinafter, "second VI
When describing "Group II metal", "cobalt", "nickel"
”) . These compounds can be used alone or in combination of two or more.

The content ratio of these Group VI and VIII metal components is 10 to 30% by weight, preferably 15% by weight, based on the weight of the catalyst in terms of oxide.
-23% by weight, and the Group VIII metal component is
0% by weight, preferably 3 to 7% by weight.

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 is deteriorated. In addition, 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.

The method for incorporating the above-mentioned Group VI metal component and Group VIII metal component into the support, that is, the method for preparing the catalyst used in the present invention, can be carried out using some known techniques. it can. As one method, a solution obtained by dissolving the Group VI metal compound and the Group VIII metal compound in a solvent such as water, alcohols, ethers, and ketones on the carrier is An impregnation method in which the support is carried out by one or more stages of impregnation treatment is given. 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 in which a solution in which the above-mentioned Group VI metal compound and the above-mentioned Group VIII metal compound are dissolved is sprayed onto the above-mentioned carrier, or a Group VI metal component and a Group VIII metal compound are sprayed. A chemical vapor deposition method in which a group metal component is chemically vapor-deposited can be used.

As still another method, a kneading method in which a part or all of the above-mentioned Group VI metal component and Group VIII metal component is added to the above-mentioned carrier component before molding and a co-precipitation method are used. Alkoxide method.

The specific surface area, pore volume and average pore diameter of the catalyst of the present invention prepared by the above-mentioned various production methods are as follows:
Although not particularly limited, as in the case of the above-mentioned carrier, in order to efficiently remove even the non-desulfurizable substance, the specific surface area is 200 m ² / g or more and the pore volume is 0.3
-1.2 cc / g and an average pore diameter of 60-120 ° are preferred.

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 inches in length.

When the above 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 starting 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, and the boiling point range is 150 to
The temperature is 400 ° C, preferably 200 to 380 ° C, more preferably 220 to 340 ° C, and 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 reaction of the feedstock 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 320 to 360 ° C, preferably 330 to 360
° C, the liquid hourly space velocity is 0.5-5.0 hr ^-1 , preferably 1.0-2.0 hr ^-1 , and the hydrogen / oil ratio is 100-4.
00 L / L, preferably 200 to 300 L / L.

[0028] 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 1, it is not possible to remove even the hardly desulfurizable substance, and even if it exceeds 360 ° C., the removal efficiency of 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,
If it is less than r- ¹ , not only the contact effect is saturated, but also the processing efficiency is reduced.

The reaction conditions are such that the sulfur content in the product oil is
0 . Conditions are selected so as to be from 0.01 to 0.08 % by weight. Under such conditions, the life of the above catalyst is equal to or longer than the life of a typical conventional 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,
It is also possible to use several reactors in series.

[0032]

【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 of 6, Na ₂ O content of 5 cc / g, average pore diameter of 62 °]
3% by weight or less, surface area 900 to 1100 (Langmu)
ir, m ² / g) and 600-700 (BET, m ²
/ G), crystal size 0.7-1.0 μm] using 5% by weight of γ-alumina, and using Mo as a Group VI metal in 20%
A desulfurization reaction was carried out under the conditions of Table 1 using a catalyst containing 5% by weight (oxide) and 5% by weight (oxide) of Co as a Group VIII metal. Table 4 shows the results.

[0033]

[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 The carrier had a specific surface area of 350 m ² / g and a pore volume of 0.6.
1 cc / g, average pore size 60 °, 1% by weight of HY-type zeolite (HY-type zeolite as in Example 1) 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 5 A desulfurization reaction was carried out in the same manner as in Example 1 except that the content of Mo was 15% by weight and the content of Co was 3% by weight. The results are shown in Table 4.

Example 6 A desulfurization reaction was carried out in the same manner as in Example 1, except that the content of Mo was 15% by weight and the content of Co was 8% 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 the content of Mo was 25% by weight and the content of 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 the content of Mo was 25% by weight and the content of Co was 8% by weight. The results are shown in Table 4.

Example 9 A desulfurization reaction was carried out in the same manner as in Example 1 except that W was used instead of Mo. 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 Ni was used instead of Co. The results are shown in Table 4.

Example 11 A desulfurization reaction was carried out in the same manner as in Example 1 except that W was used instead of Mo and Ni was used instead of Co. 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 performed in the same manner as in Example 1 except that 1 cc / g and γ-alumina having an average pore diameter of 68 ° were used.
Table 5 shows the results.

Comparative Example 2 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 of 60 °, 30% by weight of HY-type zeolite (HY-type zeolite as in Example 1) γ
-A desulfurization reaction was performed in the same manner as in Example 1 except that alumina was used. D 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 no Group VI metal was supported. 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 Mo was changed to 15% by weight (oxide). This result
Also shown in Table 5.

Comparative Example 5 A desulfurization reaction was carried out in the same manner as in Example 1 except that the content of Co was changed to 8% by weight (oxide). The results are shown in Table 5.

Comparative Example 6 A desulfurization reaction was carried out in the same manner as in Example 1 except that the content of Co was changed to 35% by weight (oxide). This result
Also shown in Table 5.

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

[0051]

[Table 2]

[0052]

[Table 3]

[0053]

[Table 4]

[0054]

[Table 5]

Further, the product oils obtained in the above Examples and Comparative Examples were subjected to a GC-AED analyzer to analyze a specific residual sulfur content. The results are shown in Tables 6 and 7. Table 6 shows the results of depth desulfurization at LHSV 1.5, and Table 7 shows the results of depth desulfurization at LHSV 3.0.

[0056]

[Table 6]

[0057]

[Table 7]

[0058]

As described in detail above, according to the present invention,
It is possible to sufficiently cope with desulfurization of 4M-DBT and 4,6DM-DBT which are difficult to desulfurize substances at a sulfur content of 0.05% by weight.
It can be provided at low cost.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kazuo Dei 1134-2 Gondogendo, Satte City, Saitama Prefecture Cosmo Research Institute, Inc. R & D Center (72) Inventor Osamu Chiyoda 1134-2 shares in Gondogendo, Satte City, Saitama Prefecture Cosmo Research Institute R & D Center (72) Inventor Hatsutaro Yamazaki 1134-2 Gongendo, Satte City, Saitama Prefecture Cosmo Research Institute R & D Center (56) References JP-A-7-163884 (JP, A JP-A-3-284355 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C10G 45/12 C10G 45/08

Claims (1)

(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, having a boiling range of 150 to 400;
C. and a sulfur content of 3% by weight or less as a raw material oil, 80-99% by weight of inorganic oxide and HY type zeolite 1-2.
And 0 wt% to a carrier consisting Nde contains, 10 to 30% by weight of the Periodic Table Group VI metal component in terms of oxide, the periodic table V
At least one of cobalt and nickel as Group III metals
One was used to was contained 1-10 wt% in terms of oxide catalysts, 30~80kg / cm ² pressure, the temperature from 320 to 360
C, the liquid hourly space velocity is 0.5-5.0 hr ^-1 , the hydrogen / oil ratio is 100-400 L / L, and the sulfur content of the produced oil is 0.01-0.08 % by weight. A method for hydrodesulfurizing gas oil, comprising performing a catalytic reaction.