JPH01228549A - Catalyst for hydrotreating hydrocarbons and method for activating the same - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

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 on which at least one metal selected from Group 8 metals is supported as a hydrogenation active component,
Group 6 metals include Mo and W; Group 8 metals include C.
o and Ni are often used.

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

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 the catalyst 17.
! Standard temperature and pressure per unit: 1,000 to 3,0
00/, conducted at a temperature of 180°C or higher (usually 250°C or higher), and contains carbon disulfide, n-butyl mercaptan,
When dimethyl sulfide, dimethyl disulfide, etc. are used, dilute them with light hydrocarbon oil and serve at a temperature of 250 to 350.
°C, pressure 20-100 kg/cnf, liquid hourly velocity 0.
5~2 hr-', hydrogen/oil stop 200~1OOONl/
I'm using l.

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-sulfiding 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. 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 to prevent this, it is necessary to use a sulfurizing agent in the column, and the ratio of sulfurizing agent and hydrogen must be maintained appropriately. . Furthermore, although this kind of presulfurization is normally carried out over several days, this operation is temporary and is often not automated, requiring unusual and complicated operations that require operator effort. The burden is extremely heavy.

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

[Problem to be solved by the invention]

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

The method uses a catalyst with the general formula R-5t supported on an active metal.
impregnated with polysulfide represented by n+-R' (n is an integer of 3 to 20, R and R' are hydrogen atoms or organic groups having 1 to 150 carbon atoms per molecule), and The catalyst is heat-treated at 65 to 275°C and under a pressure of 0.5 to 70 bar in the absence of the catalyst (Japanese Patent Application Laid-Open No. 1983-1961).
-1) 1) Publication No. 44). According to this method, the polysulfide impregnated in the catalyst sulfurizes the active metal through heat treatment, so when pre-sulfiding is performed in the reactor, a sulfurizing agent and a diluent are not required, making the operation easier. Pre-sulfurization outside the reactor is also possible, and in that case, the hydrotreating operation can be started immediately by filling the reactor with the pre-sulfurized catalyst.

The amount of polysulfide used is the stoichiometric amount required to later sulfurize the entire active metal oxide (e.g. Nip, Mo(13)) in the catalyst, and diluted with an appropriate organic solvent to prepare 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, it is necessary to use a highly concentrated polysulfide solution. A problem with a solution is that it becomes difficult to penetrate into the catalyst pores.

[Means for Solving the Problems] The present inventors have conducted various studies on presulfurization methods using sulfurizing agents that are easier to handle than polysulfides, and as a result, have found that amino-substituted mercaptans are suitable, and have arrived at the present invention. That is, the present invention provides an amino-substituted mercaptan on a catalyst in which an oxide of at least one metal selected from Group 6 metals and Group 8 metals of the periodic table and an oxide of phosphorus are supported on an inorganic oxide carrier. A catalyst for hydrotreating hydrocarbon oil, which is characterized in that it is impregnated with the amino-substituted mercaptan, and an active catalyst, which is characterized in that the catalyst is impregnated with this amino-substituted mercaptan and is treated in the presence of hydrogen at a temperature between room temperature and 400°C. It is a method of conversion.

As is well known in the art, alumina or silica-alumina are typical examples of inorganic oxide carriers. Furthermore, as is conventionally known, as the Group 6 metal of the periodic table to be supported as an active metal, MO and/or W oxides are preferable, and as the Group 8 metal, CO and/or
Or Ni oxide is preferable. Group 6 metals and Group 8 metals may be used alone or in combination.

Phosphorus, also a conventionally known active material, is also useful in the catalysts of the present invention. Phosphorus may be supported alone or together with a Group 6 metal or a Group 8 metal. - In the case of using a mixed impregnating liquid, as the phosphorus content increases, the stiffness increases and impregnation becomes difficult. Therefore, according to this method, the maximum amount of PzOs supported in the catalyst is 8% by weight.

Amino-substituted mercaptans have the general formula) IJ-R-3H (
2-aminoethanethiol (H, NCII□CI, SH),
Preferred examples include 4-aminothiophenol (lhNC6H4S1). 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 oxide of a Group 6 metal or a Group 8 metal of the periodic table and an oxide of phosphorus.

The supported amount of the amino-substituted mercaptan is determined by the sulfurized form in which Group 6 metals and Group 8 metals of the periodic table exhibit high activity in hydrogenation reactions (eg, MO52, WS2, CoS).

The amount of sulfur is preferably 1 to 3 times the amount required to form 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 catalyst carrying the amino-substituted mercaptan 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 amino-substituted mercaptan. Removal of the solvent may be performed during activation in the presence of hydrogen, and no particular drying operation is required before activation. In the activation treatment in the presence of hydrogen, metals from group 6 and/or metals from group 8 of the periodic table are activated.
The amino-substituted mercaptan coordinated to the group metal undergoes hydrogenolysis, and the metal component changes into sulfide, which is an active species in the hydrogenation reaction. In the activation treatment in the presence of hydrogen, there is no restriction on the reaction pressure, and hydrocarbons may be mixed.

Therefore, the activation treatment can be performed in a treatment equipment separate from the reactor for hydrotreating hydrocarbons in which the catalyst is used, or can be performed after being loaded into the reactor for hydrotreating. be.

Activation is at a temperature between room temperature and 400°C, preferably at 100°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.

[For production]

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 amino-substituted mercaptan forms a coordination compound with a metal from Group 6 and/or a metal from Group 8 of the periodic table and is supported upon subsequent activation in the presence of hydrogen. This is believed to be because it works effectively to form favorable metal sulfide objects during processing.

〔Example〕

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

Example specific surface area 280n? /g, pore volume 0.75 ml
/g of γ-alumina carrier, 29.0 g of molybdenum trioxide, nickel carbonate (Ni content 43.3%)
), 16.5 g of 85% phosphoric acid, and 80 nl of an impregnating solution prepared from water were impregnated with 1) 1) dried at 0°C for 16 hours and then calcined at 500°C for 2 hours to obtain Mo0.20% by weight.
A catalyst containing 4% by weight of Ni, 57% by weight of P2O was obtained. Add 2-aminoethanethiol 1) to 30 g of the catalyst. 5
18,6 g of 4-aminothiophenol was made into an aqueous solution of 301) 1) with water, and the operation of impregnating the entire amount was repeated twice with 16 hours of drying at 100°C in the middle, and then soaked at 100°C. After drying for 16 hours, catalysts A and B were obtained.

The amount of amino-substituted mercaptan supported on catalysts A and B is Mo
, is 1.5 times the theoretical amount of sulfur required for Ni to become Mo5z, NiS.

The catalysts A and B were loaded into a stainless steel fixed bed flow reaction tube, and 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): 21)'C'' (50vo1.χ): 340℃〃 (end point) :406°C The reaction was carried out under the following conditions.

Catalyst amount: 3ml Raw oil liquid space velocity: 2.0hr-'Reaction pressure (hydrogen pressure): 30kg/cn (reaction temperature: 33
0℃ Hydrogen/oil conversion: 30ONl/1 oil passage time:
The treated oil for 8 hours 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 MOO3/Nip/PzOs system (hereinafter referred to as Mo/Ni) before supporting the amino-substituted mercaptan used in the example
A catalyst (abbreviated as /P system) is loaded into a flow reactor,
After the sulfurization treatment under the following conditions, Kuwait atmospheric gas oil was subjected to a hydrodesulfurization reaction in the same manner as in the example.

Sulfurized oil: 3% by weight n-butyl mercaptan/Kuwaite normal pressure gas oil Catalyst amount: 3ml! Raw material oil liquid space velocity: 2.0hr-'reaction pressure
: 30kg/cJ Reaction temperature : 3
30°C Hydrogen/oil ratio Oil stop: 30ONl/1 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/Ni/P-based catalyst supporting 2-aminoethanethiol and 4-aminothiophenol has a higher molecular weight than a catalyst sulfurized using Kuwait atmospheric gas oil mixed with 3% by weight of n-butyl mercaptan. It is found that it shows activity.

Table 1 (n) Sulfurization method using 3% by weight n-butyl mercaptan atmospheric gas oil.

〔Effect of the invention〕

The present invention provides a catalyst for the hydrogenation of any hydrocarbon, which contains at least one oxide of a Group 6 metal or a Group 8 metal of the periodic table and an oxide of phosphorus, and whose active species is a sulfide of the above-mentioned metal. Applicable to

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.

Claims (6)

[Claims] (1) A catalyst comprising an inorganic oxide as a carrier and an oxide of at least one of a group 6 metal or a group 8 metal of the periodic table and an oxide of phosphorus is impregnated with an amino-substituted mercaptan. Catalyst for hydrotreating hydrocarbons. (2) The catalyst for hydrotreating hydrocarbons according to item (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. (3) The catalyst for hydrogenation of hydrocarbons according to item (1) or item (2), wherein the amino-substituted mercaptan is 2-aminoethanethiol and/or 4-aminothiophenol. (4) Hydrocarbon hydrogen prepared by using an inorganic oxide as a carrier and impregnating an amino-substituted mercaptan into a catalyst containing at least one oxide of a Group 6 metal or a Group 8 metal of the periodic table and an oxide of phosphorus. The catalyst for chemical treatment is heated at room temperature to 4 ℃ in the presence of hydrogen.
1. A method for activating a catalyst for hydrotreating hydrocarbons, the method comprising processing at a temperature of 0.000C. (5) The catalyst for hydrotreating hydrocarbons according to item (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. Activation method. (6) The method for activating a catalyst for hydrogenation of hydrocarbons according to item (4) or item (5), wherein the amino-substituted mercaptan is 2-aminoethanethiol and/or 4-aminothiophenol.