JPS6190744A - Method of pressulfurizing hydrogenation catalyst - Google Patents

Abstract

PURPOSE:To presulfurize efficiently by bringing a hydrogenation catalyst for coal pitch, etc. into contact with aromatic distillate oil having <=10.5 UOP-K value and contg. >=0.4wt% sulfur in a hydrogen atmosphere under pressure and heating. CONSTITUTION:A hydrogenation catalyst for coal pitch or heavy oil is brought into contact with aromatic distillate oil having <=10.5 UOP-K value and contg. >=0.4wt% sulfur in a hydrogen atmosphere under pressure and heating, and sulfurized. The hydrogenation catalyst to be used is well known heretofore, and the catalyst obtained by depositing an active hydrogenation metallic component on a porous inorg. oxide is used. Sulfurization is conducted at about 100-380 deg.C and at 10-200kg/cm<2>G pressure. The UOP-K value of the aromatic distillate oil is preferably regulated to about 8.5-10.5, and the sulfur content is preferably controlled to about 0.5-1.0wt%.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a method for presulfiding a hydrotreating catalyst for coal-based pitch or heavy oil.

[Prior art]

It is widely known that coal-based pitch and heavy oil are hydrotreated in the presence of a catalyst in order to improve their quality. In order for the hydrotreating catalyst in such hydrotreating to exhibit high activity, it is advantageous to convert it into a sulfide form in advance before starting operation. Conventionally,
In the hydroprocessing of petroleum, the catalyst is heated under hydrogen pressure and heated, and the lye 1 to 1 containing about 1% by weight of sulfur is heated.
It is known that sulfurization is carried out by contacting light hydrocarbon oil such as gas oil (LPO). However, such a sulfiding method cannot be applied to sulfurizing a catalyst when hydrotreating coal-based feedstock oil. That is, in the hydrotreating of coal-based feedstock oil, if the hydrotreating catalyst is sulfurized by the method described above and then brought into contact with the coal-based feedstock oil, solids will precipitate between the catalyst layers, causing the problem of catalyst bed clogging.

〔the purpose〕

The purpose of the present invention is to provide a method for hydrotreating coal-based feedstock oil.
The purpose is to provide an efficient and effective presulfidation method for hydrotreating catalysts.

〔composition〕

According to the present invention, in the method for presulfurizing a hydrotreating catalyst for coal-based pitch or heavy oil, the hydrotreating catalyst is heated under pressure of hydrogen gas and under heating.
A method for sulfurizing a hydrotreating catalyst for coal-based pitch or heavy oil, characterized by sulfurizing it by contacting it with an aromatic distillate having a value of 10.5 or less and a sulfur content of 0.4% by weight or more. is provided.

The hydrogenation catalyst used in the present invention is a conventionally known catalyst, and for example, one in which a hydrogenation-active metal component is supported on a porous inorganic oxide is used. In this case, as the porous inorganic oxide, various conventionally known synthetic or natural products such as γ-alumina, α-alumina, silica, magnesia, boria, zirconia, phosphine, chromia,
In addition to synthetic products such as titania, silica-alumina, alumina-boria, alumina phosphere, silica-magnesia, synthetic zeolite, and synthetic sepiolite, naturally occurring sepiolite, pumice, zeolite, bauxite, attapulgite, kaolin, montmorillonite, etc. Natural products can be mentioned.

As the hydrogenation active metal component, conventionally known ones are used, for example, at least one selected from group I, group II, group II, and group III metals of the periodic table, and specific examples of such metals include Examples include copper, vanadium, molybdenum, tungsten, cobal-1, nickel, iron, etc.
Especially from the point of view of catalyst activity and life, Co-Mo, N
Preference is given to using combinations of i, -Mo, Ni-Li, or Co-Mo-Ni.

The presulfidation of the catalyst according to the invention is preferably carried out by
Prior to supplying the raw material oil to the reactor filled with the catalyst, an aromatic distillate oil having a UOP-K value of 10.5 or less and a sulfur content of 0.4% by weight or more is supplied in advance to react with the catalyst. Catalytic sulfurization. In this case, the sulfiding conditions include a temperature of 100 to 380°C, preferably 280 to 360°C, and a pressure of 10 to 200 kg/cmG, preferably 30 to 18
0kg/cJG, LH3V0.2-5hr-1, preferably 0.3-3hr-', H2/oil hole 200-20
0ON fl/Q, preferably 500-150ON
Q/Q, time 3-50 hours, preferably 10-3
0 hours is adopted.

The aromatic distillate oil used in the sulfurization treatment in the present invention is:

The UOP-K value is 10.5 or less, and the sulfur content is 0.
It is 4% by weight or more. UOP as sulfur treatment oil
- If a material with a K value larger than 10.5 is used, solid content will precipitate in the catalyst layer when the raw oil is supplied in place of the pre-sulfiding active oil and the sulfurizing oil and the hydrogenation process is performed. Catalyst clogging will occur. In the case of the present invention, the preferable UOP''-K value of the aromatic distillate is about 8.5 to 10.5.The sulfur content of the aromatic distillate is 0.4.
If the sulfur content is less than 0.4% by weight, the sulfur content becomes too long and the catalyst becomes in an unfavorable reduced state. Undesirable. Furthermore, 1. The oil for sulfurization used in the present invention must be a distillate oil, and its boiling point is generally below 400°C. 6. If the residual oil has a high boiling point, the activity of the resulting sulfurization catalyst will not be sufficiently exerted. So, I don't like it. This is thought to be due to irreversible adsorption of solvent-insoluble components such as toluene-insoluble components (TI) on the catalyst. Such aromatic distillate oils include, for example, various coal tar fractions, such as medium oils, cleaning oils, anthracene oils, and their constituent components such as methylnaphthalene oil and quinoline oil; (or β)-methylnaphthalene, quinoline or isoquinoline itself, etc. can be used. Preferably α-methylnaphthalene,
Examples include β-methylnaphthalene, fractions containing them, or mixtures thereof, anthracene oil and quinoline, or fractions containing them. Furthermore, sulfur-containing compounds such as thiophene and thiophenol can be added to these aromatic distillate oils in order to adjust their sulfur content. Organic solvents with a UOP-K value greater than 10.5, such as petroleum-based kerosene, light oil, light gas oil, etc., are not suitable for the purpose of the present invention.

The LIOP-K value referred to in this specification is commonly used as an index of the aromaticity of crude oil, petroleum fractions, organic solvents, etc., and is expressed by the following formula.

K-47Mo7 TB...Average molar boiling point of solvent (Rankine temperature: 0F+460) S...Specific gravity (60/60°F) Sulfidation treatment of the catalyst filled in the reactor as described above After this is completed, feedstock oil is supplied and hydrotreated. In this case, the feedstock oil is coal-based pitch or heavy oil;
Coal tar, coal tar pitch, coal liquefied oil, etc. are included. Hydrotreating conditions generally include a reaction temperature of 200 to 500°C and a hydrogen pressure of 60 to 300°C.
kg/cJG, liquid hourly velocity (LH3V) 0.1-10H
r-1, hydrogen ZJM feed oil specific oil hole 0-200ON Q/Q
are employed, and preferable conditions are appropriately selected depending on the purpose of the hydrogenation treatment.

〔effect〕

According to the present invention, the catalyst can be sulfurized by a simple method of bringing aromatic distillate oil into contact with the catalyst prior to hydrotreating coal-based pitch or heavy oil, which is extremely effective. be. Furthermore, in the case of the present invention, when the aromatic oil to be supplied is switched to feedstock oil after the sulfurization treatment and the hydrogenation treatment is performed, no precipitation of solids occurs and no clogging of the catalyst layer occurs.

Furthermore, it does not generate sludge in piping, heat exchangers, etc., allowing long-term operation.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 Hydrotreating catalysts having the properties shown in Table 1 were used.

Table-1 Components AQ203: 72.9% by weight MoO3: 20.1% by weight NjO: 3.8% by weight Physical properties Specific surface area = 201 I/g Pore volume 7 0.44 cc/g 500 cc of the catalyst was placed in a fixed bed Fill the hydrotreating equipment,
Prior to the hydrogenation treatment of the feedstock oil, methylnaphthalene oil having the properties shown in Table 2 below was used as the sulfurization treatment oil at a hydrogen pressure of 90 kg/cJG, a temperature of 350°C, and an LH
3V1. Ohr', hydrogen/oil hole 100ON Q
/Q conditions, oil was passed continuously until several hours had passed after the hydrogen sulfide concentration of the device outlet gas reached a certain value, and the catalyst was sulfurized.

Table-2 Boiling point: 230-260°C Specific gravity (1
5°C): 1.016 Sulfur content = 0.9% by weight UOP- value: 9.62 Next, the flow of naphthalene oil was stopped, and instead of this, coal tar pitch [boiling point 300°C, specific gravity (250C)1
18), hydrogen pressure 90 kg/cJG, temperature 360°C, L
H5VO, 5hr-1, hydrogen/oil hole 100ON Q/
Oil was passed under the conditions of Q and hydrogenation treatment was performed.

When hydrotreating coal tar pitch in this way, no increase in the pressure difference in the catalyst layer occurs even after 300 hours have passed;
It was confirmed that the problem of clogging of the catalyst layer did not occur.

Comparative Example In Example 1, petroleum-based light oil with a uop value of 11.9 (sulfur content 1.0% by weight) was used as the oil for sulfurization treatment.
After presulfiding the catalyst, the coal tar pitch was hydrogenated in the same manner except that the catalyst was pre-sulfurized. In this case, the differential pressure in the catalyst layer rose to 0.5 kg/cJG just 20 minutes after the start of the hydrogenation treatment, causing a problem of clogging of the catalyst layer.

Patent applicant: Chiyoda Corporation (1 other person)

Claims (1)

[Claims] (1) In a method of pre-sulfurizing a hydrotreating catalyst for coal-based pitch or heavy oil, the hydrotreating catalyst is heated under pressure of hydrogen gas and has a UOP-K value of 10.5.
The following describes a method for presulfurizing a hydroprocessing catalyst for coal-based pitch or heavy oil, which comprises contacting with an aromatic distillate having a sulfur content of 0.4% by weight or more to sulfurize the catalyst.