JPS63310641A - Catalyst for hydrogenation of hydrocarbon and method for activating same - Google Patents

Abstract

PURPOSE:To improve the activity of a catalyst by impregnating a thio acid into the catalyst composing specified metallic components supported on an inorg. acid as a carrier. CONSTITUTION:Oxides of active metals such as Mo, W, Co and Ni are supported on an inorg. oxide carrier such as alumina or silica-alumina. A thio acid such as thioacetic acid or thiobenzoic acid is impregnated into the resulting catalyst and the catalyst is activated preferably at 100-300 deg.C. Thus, the hydrogenating capacity can be improved.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a catalyst for hydrotreating hydrocarbon oil that is easy to activate and a method for activating the same.

[Conventional technology]

In so-called hydrogenation treatment, in which hydrocarbon oil is hydrogenated, desulfurized, denitrified, decomposed, etc. in the presence of hydrogen, a group 6 metal of the periodic table is used on an inorganic oxide carrier such as alumina, silica-alumina, or titania. and a catalyst supporting a small amount of metal selected from Group 8 metals as a hydrogenation active component,
Mo and W are Group 6 metals, and G is Group 8 metals.
o and Ni are often used.

These metals are usually supported with oxidation dynamics and are not active as they are, so pre-sulfidation is required to convert the oxidation dynamics into sulfuration dynamics and activate them in order to use them for the hydrogenation reaction.

Conventionally, this pre-sulfurization is generally carried out by filling a catalyst in a reactor for hydrogenating hydrocarbon oil and then passing a sulfurizing agent together with hydrogen through the catalyst bed. The operating conditions for pre-sulfiding vary depending on the hydrotreating process and the sulfurizing agent used, but when hydrogen sulfide is used, it is contained in hydrogen at about 0.5 to 5% by volume, and this is added to catalyst II.
! Convert to standard temperature and pressure "i'1.000~3,
000j! When using carbon disulfide, n-butyl mercaptan, dimethyl sulfide, dimethyl disulfide, etc., these are diluted with light hydrocarbon oil and used at a temperature of 250 °C or higher. ~
350℃, pressure 20-100/-2 liquid space velocity 0.5
~2 hr-', hydrogen/hydraulic pressure 200-100 ONl/I
I'm doing it with t.

After performing such a pre-sulfiding operation, the raw material oil to be actually treated is switched to, and the hydrotreating operation is started.

By the way, since the above-mentioned pre-sulfurization operation influences the success or failure of the subsequent hydrogenation treatment, appropriate selection of the materials used and careful operation are required. For example, when using a diluent, if the diluent contains olefins, the polymerization product will poison the catalyst, so it is necessary to use a hydrocarbon oil that does not contain olefins, and if the diluent has high viscosity, the catalyst surface Since heavy oil is not suitable due to its poor moisturizing effect, light distillates have no choice but to be used. Use of such light oil results in increased costs.

In addition, when the catalyst metal reacts with hydrogen at high temperatures and is reduced, it becomes passivated, so in order to prevent this, it is necessary to use a large amount of sulfurizing agent, and the ratio of sulfurizing agent and hydrogen must be maintained properly. Moreover, such pre-sulfurization is normally carried out over several days, but since this operation is temporary, it is often not automated, and requires unusual and complicated operations. The burden on staff is extremely heavy.

Therefore, it has been a challenge to eliminate presulfurization or at least reduce the complexity of the operation.

[Problem that the invention seeks to solve]

Recently, a method has been proposed that can meet these demands.

The method involves impregnating a catalyst on which an active metal is supported with a polysulfide represented by the general formula % (R' is a hydrogen atom or an organic group having 1 to 150 carbon atoms per back), and hydrogen gas is in the absence of, 65-275°C, 0.5-70
According to this method, the polysulfide impregnated in the catalyst sulfurizes the active metal by heat treatment, so that the catalyst is heat-treated under the pressure of bar. Pre-sulfiding inside the reactor eliminates the need for a sulfurizing agent and diluent, making the operation easier, and pre-sulfurizing outside the reactor is also possible. Hydrotreating operations can be started.

The amount of the polysulfide used is the stoichiometric amount required to later sulfurize the entire active metal oxide (e.g. NtO+Mo5s) in the catalyst, which is diluted in a suitable organic solvent and impregnated into the catalyst. . Therefore, when impregnating a catalyst with a large amount of active metal supported, it is necessary to use a highly concentrated polysulfide solution. However, since the polysulfide has a high viscosity, there is a problem that it becomes difficult to penetrate into the catalyst pores in a highly concentrated solution.

[Means for solving problems]

The present inventors conducted various studies on presulfurization methods using sulfurizing agents that are easier to handle than polysulfides, and as a result, they discovered that thioacids were suitable and arrived at the present invention.

That is, the present invention is characterized in that a catalyst comprising an oxide of at least one metal selected from Group 6 metals and Group 8 metals of the periodic table supported on an inorganic oxide carrier is impregnated with thioic acid. This activation method is characterized in that a catalyst for hydrotreating hydrocarbon oil, which is characterized by the above, and a catalyst impregnated with this thioic acid are treated in the presence of hydrogen at a temperature of room temperature to 400°C.

As is well known in the art, alumina or silica-alumina is typical as the inorganic oxide carrier. Further, as is conventionally known, the Group 6 metal component of the periodic table supported as an active metal is preferably an oxide of Mo and/or W, and the Group 8 metal component is C.
Oxides of o and/or Ni are preferred. The Group 6 metal component and the Group 8 metal component may be used alone or in combination.

Thioacid is represented by the general formula R-CO3II (wherein R represents a monovalent hydrocarbon group) and is thioacetic acid (CHaC
(OSH), thiobenzoic acid (C,H5COSH), and the like can be mentioned as preferred examples.

These are dissolved in an organic solvent such as alcohol and supported on an inorganic oxide carrier by an impregnation method on a catalyst containing at least one of a group 6 metal component and a group 8 metal component of the periodic table as an oxide.

The supported amount of thioacid is determined by the sulfurized form of group 6 metals and group 8 metals of the periodic table that exhibit high activity in hydrogenation reactions (for example, M
The amount of sulfur is preferably 1 to 3 times the amount of sulfur required to form O5z, WSzt CoS, N15). If the amount supported is less than this, the activity will decrease, and if more than this amount is used, no significant improvement in activity can be expected, so it is uneconomical.

The thioacid-supported catalyst is activated by treatment in the presence of hydrogen at temperatures from room temperature to 400° C., optionally after drying off the solvent used to dissolve the thioacid. Removal of the solvent may occur during activation in the presence of hydrogen, and no specific drying operation is required prior to activation. In the activation treatment in the presence of hydrogen, the thioacid coordinated to the Group 6 metal and/or Group 8 metal of the periodic table undergoes hydrogenolysis, and the above metal components are the active species in the hydrogenation reaction. Changes to sulfide. In the activation treatment in the presence of hydrogen, there is no restriction on the reaction pressure, and hydrocarbons may be mixed. It can also be done with a separate processing device,
It is also possible to carry out the treatment after loading it into a reactor for hydrotreating.

Activation is at a temperature between room temperature and 400°C, preferably between 100°C and 400°C.
It is carried out at a temperature of 300°C. Temperatures higher than 400°C are not preferred because the hydrogenation activity of the treated catalyst decreases.

[Function] The catalyst prepared according to the present invention exhibits an activity equal to or higher than that of a catalyst sulfurized by the prior art in the hydrodesulfurization reaction of hydrocarbon oil. Although the reason is not clear, the thioic acid forms a coordination compound with a metal from Group 6 and/or a metal from Group 8 of the periodic table and is supported during the subsequent activation treatment in the presence of hydrogen. This is thought to be because it works effectively to form metal sulfide objects, which are sometimes desirable.

〔Example〕

Examples and comparative examples of the present invention will be shown below.

Example γ-alumina was used as a carrier, Mo5s was 17% by weight, Co
12.7 g of thioacetic acid or 23.7 g of thiobenzoic acid was added to 30 g of a commercially available catalyst (KF-707, manufactured by Nippon Ketchen ■) containing 4% by weight of O. 15ml of ethanol solution containing Og
After impregnating the entire amount of catalysts, catalysts A and B were dried at 80°C for 16 hours.
I got it.

The amount of thio acid supported on catalysts A and B is Mo, Co is Mo
5t, which is 1.8 times the theoretical amount of sulfur required to form CoS.

The catalysts A and B were loaded into a stainless steel fixed bed flow reaction tube and activated under the following conditions.

Catalyst amount: 3ml Pressure 2 Atmospheric pressure Temperature: 200°C Hydrogen flow rate: 4BNl/hr Time: 3hr Using the catalyst activated under the above conditions, a hydrodesulfurization reaction of Kuwait atmospheric gas oil was carried out. The properties of the atmospheric gas oil used in the reaction were as follows.

Specific gravity (15/4℃): 0.848 Sulfur: 1.61% by weight Nitrogen: 157ppm by weight Distillation properties (initial boiling point): 211℃ 〃 (50vd%): 340℃ 〃 (End point'): 406℃ Reaction was carried out using a flow reactor under the following reaction conditions.

Catalyst amount: 3aal Raw material oil/liquid space velocity: 2.0hr-'Reaction pressure (hydrogen pressure): 30kg/cj Reaction temperature: 330
°C Hydrogen/oil conversion: 30ONt'/l' Oil passage time: 8 hr The treated oil was sampled every 2 hours, the sulfur content was measured, and the desulfurization rate was determined. Table 1 shows the average value of the desulfurization rate determined from the sulfur content of the treated oil sampled at the 4th hour, 6th hour, and 8th hour.

Comparative Example The MOO, /COO catalyst used in the example was loaded into a flow reactor and subjected to sulfurization under the following conditions, and then the hydrodesulfurization reaction of Kuwait atmospheric gas oil was carried out in the same manner as in the example. .

Sulfurized oil: 3% by weight n-butyl mercaptan/Kuwaite normal pressure gas oil Catalyst amount: 3cal Raw material oil liquid hourly space velocity: 2.0hr-'Reaction pressure
: 30kg/cd Reaction temperature : 3
16℃ Hydrogen/oil conversion: 30ONg71 oil passage time
: 8 hr Table 1 shows the average value of the desulfurization rate determined from the sulfur content of the treated oil sampled at the 4th hour, 6th hour, and 8th hour.

A Mo/Co-based catalyst supporting thioacetic acid and thiobenzoic acid can exhibit activity equal to or higher than a catalyst sulfurized using Kuwait atmospheric gas oil mixed with 3% by weight of n-butyl mercaptan. I understand.

Table 1 A sulfurization method using normal pressure light oil.

〔Effect of the invention〕

The present invention is applicable to any hydrocarbon hydrotreating catalyst that contains at least one of a Group 6 metal component and a Group 8 metal component of the periodic table as an oxide, and whose active species is a sulfide of the above metal. It is.

According to the present invention, a hydrocarbon hydrotreating catalyst having excellent performance can be obtained with a simpler operation than the conventional sulfurization method.

Patent applicant: Sumitomo Metal Mining Co., Ltd. Procedural amendment (voluntary) September 2, 1986

Claims (6)

[Claims] (1) A hydrocarbon characterized by impregnating a catalyst using an inorganic oxide as a carrier and containing at least one of a group 6 metal component and a group 8 metal component of the periodic table as an oxide with thioacid. Hydrotreating catalyst. (2) Hydrogen in the hydrocarbon according to claim (1), wherein the Group 6 metal of the periodic table is at least one of Mo and W, and the Group 8 metal is at least one of Co and Ni. Catalyst for chemical treatment. (3) The catalyst for hydrogenation of hydrocarbons according to claim (1) or (2), wherein the thioacid is thioacetic acid and/or thiobenzoic acid. (4) A catalyst for hydrogenation of hydrocarbons in which a catalyst containing an inorganic oxide as a carrier and containing at least one of a group 6 metal component and a group 8 metal component of the periodic table as an oxide is impregnated with thioacid. 1. A method for activating a catalyst for hydrogenation of hydrocarbons, which comprises treating at a temperature of room temperature to 400°C in the presence of hydrogen. (5) The hydrocarbon according to claim (4), wherein the Group 6 metal of the periodic table is at least one of Mo and W, and the Group 8 metal is at least one of Co and Ni. A method for activating a hydrotreating catalyst. (6) The method for activating a catalyst for hydrogenation of hydrocarbons according to claim (4) or (5), wherein the thioacid is thioacetic acid and/or thiobenzoic acid.