JPH01236945A - Catalyst for hydrotreating hydrocarbon and production thereof - Google Patents

Abstract

PURPOSE:To obtain a catalyst for hydrotreating hydrocarbon oil which is easy in activation treatment by carrying the water-soluble compds. of groups VI and VIII metals in the periodic table, phosphoric acid and thio-acid on an inorganic oxide carrier. CONSTITUTION:The water-soluble compds. of both group VI metals such as molybdenum and tungsten in the periodic table and group VIII metals such as cobalt and nickel, phosphoric acid and thio-acid such as thioacetic acid are carried on an inorganic oxide carrier such as alumina and silica. Thereby thio-acid forms a soluble coordination compd. together with metals and metallic sulfide is carried in a high dispersion state on the inorganic carrier. Therefore the catalyst for hydrotreating hydrocarbon oil which has excellent performance is obtained with a simplified operation.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a hydroprocessing catalyst for hydrocarbon oil that can be easily activated.

[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 commonly 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 in the case of using hydrogen sulfide, hydrogen is contained in the hydrogen at a concentration of about 0.5 to 5% by volume, and this is carried out per 2 catalysts at standard temperature and pressure. Convert to 1,000~3,000! ,
It is carried out at a temperature of 180°C or higher (usually 250°C or higher), and when carbon disulfide, n-butyl mercaptan, dimethyl sulfide, dimethyl disulfide, etc. are used, they are diluted with light hydrocarbon oil and used at a temperature of 250°C or higher. 350℃, pressure 20-100kg/cri, liquid space velocity 0, 5-2h
r-', hydrogen/oil stop 200-1000 Nl/! ! I'm doing it.

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 oil has 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. It won't happen. 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 involves impregnating a catalyst on which an active metal is supported with a polysulfide represented by the general formula % (or an organic group having 1 to 150 carbon atoms per molecule), and in the absence of hydrogen gas. Below, the catalyst is heat-treated at 65-275°C and under a pressure of 0.5-70 bar (Japanese Patent Application Laid-Open No.
1-1) 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. Ni1, MOO3) in the catalyst, and it is diluted with an appropriate organic solvent and added to the catalyst. Impregnate. 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 the Problems] As a result of various research into presulfurization methods using sulfurizing agents that are easier to handle than polysulfides, the present inventors found that thioacids were suitable and filed an application earlier. As a result of research, it was found that the impregnation with the sulfurizing agent may be performed after impregnating the active metal, and the same effect can be obtained by using an impregnating liquid containing both the sulfurizing agent and the active metal, and the present invention was achieved.

That is, the present invention provides hydrocarbon hydrogen in which a water-soluble compound of at least one metal selected from Group 6 metals and Group 8 metals of the periodic table and phosphoric acid and thioic acid are supported on an inorganic oxide carrier. A catalyst for chemical treatment, an inorganic oxide carrier impregnated with phosphoric acid and a water-soluble compound of at least one metal selected from Group 6 metals and Group 8 metals of the periodic table, separately or simultaneously as an aqueous solution, and dried. A method for producing a catalyst for hydrotreating hydrocarbon oil characterized in that the dried product is impregnated with a thioacid, and an inorganic oxide carrier containing at least one metal selected from Group 6 and Group 8 metals of the periodic table. This is a method for producing a catalyst for hydrotreating hydrocarbon oil, which is characterized in that it is impregnated with an impregnating liquid containing a water-soluble compound of a metal and phosphoric acid and thioic acid.

As is well known in the art, examples of the inorganic oxide carrier include alumina, silica-alumina, titania, etc., with alumina or silica-alumina being particularly representative.

Furthermore, as is conventionally known, Mo and/or W are preferable as active metals in Group 6 of the periodic table, and raw materials for preparing the impregnating solution include molybdenum dioxide, ammonium baramolybdate, and molybdenum trioxide. Preferred examples include tungsten oxide and ammonium paratungstate.

Similarly, Co and/or Ni are Group 8 metals of the periodic table.
is preferred, and preferred examples of raw materials for preparing the impregnating solution include cobalt nitrate, cobalt carbonate, nickel nitrate, and nickel carbonate. Group 6 metals and Group 8 metals
Group metals may be used alone or in combination.

Phosphorus, also a conventionally known active substance, is also useful in the catalyst of the present invention, and phosphoric acid is suitable as the impregnating form. This phosphoric acid may be impregnated as an aqueous solution separate from the above-mentioned water-soluble compound, or may be impregnated simultaneously using an impregnating solution containing both the above-mentioned water-soluble compound.

In the case of simultaneous impregnation, as the content of phosphoric acid increases, the stiffness increases and impregnation becomes difficult. Therefore, when using this method, the limit is approximately 8% of P2O supported in the catalyst.

Thioacid is represented by the general formula R-COSH (wherein R represents a monovalent hydrocarbon group) and is thioacetic acid (CH3CO3H).
.

Preferred examples include thiobenzoic acid (CJ, C05H).

Generally, a method for producing a catalyst for hydrotreating hydrocarbon oil involves impregnating an inorganic oxide carrier with an aqueous solution of a Group 6 metal component and/or a Group 8 metal component of the periodic table as an active metal, drying, and then calcination. It consists of processes.

In the present invention, after impregnating the active metal water-soluble compound and phosphoric acid in the above step separately or simultaneously, thioic acid is dissolved in an organic solvent such as alcohol and the solution is supported by an impregnation method. Alternatively, a solution containing a water-soluble compound of an active metal and phosphoric acid and thioic acid is supported on an inorganic oxide carrier by an impregnation method. According to such a method, it is not necessary to add a new step to the catalyst manufacturing process, and the conventional calcination step is not required, so it is advantageous in terms of thermal energy.

The amount of thioacid used is determined based on the sulfide form B (e.g. M
O3! The amount of sulfur is preferably 1 to 3 times the amount of sulfur required to form 1 WSt+ Cod, N15). If the amount used is less than this, the activity will decrease, and if more than this amount is used, no improvement in activity can be expected, so it is uneconomical.

After drying and removing the solvent used, the catalyst prepared according to the present invention is packed into a reaction tower and subjected to hydrotreating of hydrocarbon oil.

In the present invention, it is not necessary to subject the dried catalyst to any special treatment, and the dried catalyst can be immediately filled into a reactor for hydrotreating hydrocarbon oil and used.

[For production]

Catalysts prepared by the method of the present invention exhibit superior activity in hydrodesulfurization reactions of hydrocarbon oils than catalysts sulfurized by prior art techniques. The reason is not clear, but the thioic acid forms a soluble coordination compound with the metal of Group 6 and/or Group 8 of the periodic table, and the metal sulfide is supported in a highly dispersed state on the inorganic oxide support. This is thought to be due to the fact that the

〔Example〕

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

Example 1 Specific surface area 280/g, pore volume 0.75 ta l
/ g of γ-alumina support 16.5 g of molybdenum dioxide, nickel carbonate (Ni content 143.3%)
80 mj of impregnating solution prepared from 10.5 g, 16.5 g of 85% phosphoric acid and water! 1) Dry at 0°C for 16 hours. Next, 40 g of the dried material was impregnated with 22 tons of an alcohol solution containing 16.9 g of thioacetic acid, and then 1)
Catalyst A was obtained by drying at ℃ for 16 hours.

The metal content of catalyst A is 20-t% molybdenum converted to Moo, 4 wt% nickel converted to NiO, 7 wt% phosphorus converted to P2O, and the amount of thioacetic acid used is Mo. , Ni′lJ<Mo51. The amount was 1.5 times the theoretical amount of sulfur required to form NiS.

Example 2 To 50 g of alumina carrier similar to that used in Example 1, 14.5 g of molybdenum trioxide, 5.3 g of di-nokel carbonate,
The entire amount was impregnated with 47 ml of an impregnating solution (pH = 5) prepared from 8.2 g of phosphoric acid, 23.6 g of thioacetic acid, and water, and
Catalyst B was obtained by drying at 0°C for 16 hours.

The metal content of catalyst B is molybdenum is 20-t% converted to Moo, nickel is 4wt% converted to NiO, and phosphorus is P! 0. The amount of thioacetic acid used was 1.1 times the theoretical amount of sulfur required to convert Mo and Ni to 5 g of Mo+NiS.

Example 3 [Activity Evaluation] Using catalysts A and B prepared in Examples 1 and 2, 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% nitrogen by weight
157 Weight - Distillation properties (initial boiling point) 21) °C (50 vol, χ) 340 °C (end point) 406 °C The reaction was carried out using a flow reactor under the following reaction conditions.

Catalyst amount 3III! ! Raw material oil liquid space velocity 2. Ohr day reaction pressure (hydrogen pressure) 3
0kg/cot Reaction temperature 330℃ Hydrogen/oil ratio Oil stop 30ONj! /I! Oil passing time: 8 hours 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 catalyst of Example 1 before being supported with thioacetic acid was heated at 500°C for 2 hours.
After being fired for an hour, it was sulfurized (or pre-sulfurized) using Kuwait atmospheric gas oil mixed with n-butyl mercaptan and subjected to a reaction.

[Sulfurization treatment]

Catalyst amount: 3 tons! Raw material oil liquid space velocity 2.0hr-' Reaction pressure 30kg/ad Reaction temperature 316℃ Hydrogen/oil stop 300 Nβ/β Oiling time: 8 hours [Activity evaluation] The conditions for activity evaluation are exactly the same as in Example 3.

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.

Both catalysts A and B impregnated with thioacetic acid exhibit higher activity than catalysts sulfurized using Kuwait atmospheric gas oil mixed with 3% by weight of n-butyl mercaptan.

Table 1 (N) Sulfurization method using 3-t% n-butyl mercaptan atmospheric gas oil [Effects of the invention] According to the present invention, the operation is simplified and superior to the conventional sulfurization method. A catalyst for hydrotreating hydrocarbon oil having excellent performance can be obtained.

Patent applicant: Sumitomo Metal Mining Co., Ltd.

Claims (9)

[Claims] (1) A water-soluble compound of at least one metal selected from Group 6 metals and Group 8 metals of the periodic table, and phosphoric acid and thioic acid are supported on an inorganic oxide carrier. Catalyst for hydroprocessing of 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 thioacid is thioacetic acid and/or thiobenzoic acid. (4) Impregnating an inorganic oxide carrier with a water-soluble compound of at least one metal of Group 6 metal or Group 8 metal of the periodic table and phosphoric acid as an aqueous solution, separately or simultaneously, and drying the resulting dried product. 1. A method for producing a catalyst for hydrotreating hydrocarbons, which comprises impregnating a catalyst with a thioic acid. (5) Production of a 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. Method. (6) The method for producing a catalyst for hydrogenation of hydrocarbons according to item (4) or item (5), wherein the thioacid is thioacetic acid and/or thiobenzoic acid. (7) Hydrocarbon hydrogenation characterized by impregnating an inorganic oxide carrier with an impregnating liquid containing at least one of a group 6 metal or a group 8 metal of the periodic table, phosphoric acid, and thioic acid. Method for producing treatment catalyst. (8) Production of a catalyst for hydrotreating hydrocarbons according to item (7), 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. Method. (9) The method for producing a catalyst for hydrogenation of hydrocarbons according to item (7) or item (8), wherein the thioacid is thioacetic acid and/or thiobenzoic acid.