JPH0549340B2 - - Google Patents

Description

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

[Conventional technology]

For so-called hydrogenation treatment, in which hydrocarbon oil is subjected to hydrogenation, desulfurization, denitrification, decomposition, etc. in the presence of hydrogen, inorganic oxide carriers formed into pellets and calcined such as alumina, silica-alumina, and titania are used. A catalyst is used in which at least one metal selected from Group 6 metals and Group 8 metals of the periodic table is supported as a hydrogenation active component, and the Group 6 metals include Mo and W, and the Group 8 metals include Mo and W. Co and Ni are often used.

These metals are usually supported in an oxide form and do not show activity in that state, so in order to use them in the hydrogenation reaction, they must be activated by converting them from an oxide state to a sulfide state. Sulfurization is required.

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 presulfiding vary depending on the hydrotreating process and the sulfiding agent used, but when hydrogen sulfide is used, the
The standard temperature and pressure per catalyst are 1000 to 3000, and the temperature is 180℃.
(usually above 250°C), and when using carbon disulfide, n-butyl mercaptan, dimethyl sulfide, dimethyl disulfide, etc., dilute them with light hydrocarbon oil and serve at a temperature of 250 to 350°C.
℃, pressure 20~100Kg/ ^cm2 , liquid space velocity 0.5~2hr ^-1 ,
It is carried out at a hydrogen/oil ratio of 200 to 100N/.

After performing such a pre-sulfiding operation, the raw material oil to be actually treated is switched to, and the hydrotreating operation is started. The presulfiding operation determines the success or failure of the subsequent hydrotreating process, so appropriate selection of materials 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. 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 such presulfurization is normally carried out over several days, this operation is temporary and is often not automated, requiring unusually complicated operations. , the burden on the operator is extremely large. Therefore, it has been a challenge to eliminate presulfurization or at least reduce the complexity of the operation.

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

In this method, a catalyst with the general formula R-S(n)-R' (n is an integer of 3 to 20, R and R' are hydrogen atoms or 1 to 150 carbon atoms per molecule) is applied to a catalyst on which an active metal is supported. impregnated with a polysulfide represented by an organic group having
The catalyst is heat treated at 65-275° C. and under a pressure of 0.5-70 bar in the absence of hydrogen gas.
(Japanese Unexamined Patent Publication No. 111144/1983).

According to this method, the polysulfide impregnated in the catalyst sulfurizes the active metal through heat treatment, so when presulfiding 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 above is the stoichiometric amount required to later sulfurize all the active metal oxides (e.g. CoO, MoO ₃ ) in the catalyst, which can be diluted in a suitable organic solvent and impregnated. do. However, since the above-mentioned polysulfide has a high viscosity, the viscosity tends to be high even when diluted with an organic solvent, and there is a problem that it becomes difficult to penetrate into the catalyst pores.

In addition, the catalyst used for presulfidation is prepared by molding and drying alumina hydrate made from sodium aluminate as a raw material, baking it to turn aluminum into γ-alumina, and then impregnating it with an aqueous solution of a water-soluble compound of an active metal. Then, after drying, heat treatment is performed to convert the active metal into an oxide state, or alumina hydrate and an aqueous solution of a water-soluble active metal compound are mixed, formed, dried, and fired. It is produced by supporting an active metal in the form of an oxide on a support made of γ-alumina.

[Problem to be solved by the invention]

The present invention provides hydrocarbons that can be produced more easily and inexpensively than the conventional methods described above, can be used for hydrotreating without requiring pre-sulfurization treatment, and can be directly subjected to hydrotreating without heat treatment. An object of the present invention is to provide a catalyst for hydrotreating and a method for producing the same.

[Means to solve the problem]

Means for solving the problems according to the present invention are as follows.

1. One or both of boehmite-type alumina powder and γ-alumina powder, at least one of water-soluble compounds of Group 6 metals and Group 8 metals of the periodic table, and carbon having 1 to 15 carbon atoms and hydrogen. At least one or all of the water-soluble compound and the thioacid are present on the bonding surface of each particle of one or both of the boehmite-type alumina powder and the γ-alumina powder. A catalyst for hydrotreating hydrocarbons, which is made of a mixed unfired molded product of these.

2. One or both of boehmite-type alumina powder and γ-alumina powder, a metal from Group 6 of the periodic table,
Carbonization characterized by kneading a solution of at least one water-soluble compound of Group 8 metal and a thio acid of a hydrocarbon consisting of carbon and hydrogen having 1 to 15 carbon atoms, molding, and then drying. A method for producing a catalyst for hydrotreating hydrogen.

3. One or both of boehmite type alumina powder and γ-alumina powder, a group 6 metal of the periodic table,
An aqueous solution of at least one type of water-soluble compound of a Group 8 metal is kneaded, shaped and once dried, and a solution of a thioacid of a hydrocarbon consisting of carbon having 1 to 15 carbon atoms and hydrogen is added to the dried shaped product. After impregnating with
A method for producing a catalyst for hydrotreating hydrocarbons, which comprises drying again.

4 One or both of boehmite-type alumina powder and γ-alumina powder are kneaded with a solution of a hydrocarbon thioacid consisting of carbon and hydrogen having 1 to 15 carbon atoms, molded, and once dried to form the dried molded product. is impregnated with an aqueous solution of at least one of water-soluble compounds of Group 6 metals and Group 8 metals of the periodic table,
A method for producing a catalyst for hydrotreating hydrocarbons, which comprises drying again.

5 One or both of boehmite-type alumina powder and γ-alumina powder, at least one water-soluble compound of a Group 6 metal or a Group 8 metal of the periodic table, phosphoric acid, and a carbon atom having 1 to 15 carbon atoms. The water-soluble compound, phosphoric acid, and at least one or all of the thioacids are particles of one or both of boehmite-type alumina powder and γ-alumina powder. A catalyst for hydrogenation of hydrocarbons consisting of a mixed unfired molded product interposed at the joint surface of the catalyst.

6 One or both of boehmite-type alumina powder and γ-alumina powder, a Group 6 metal of the periodic table,
A solution of at least one water-soluble compound of a Group 8 metal, phosphoric acid, and a thioacid of a hydrocarbon having 1 to 15 carbon atoms and hydrogen is kneaded, shaped, and then dried. A method for producing a catalyst for hydrotreating hydrocarbons.

7 One or both of boehmite-type alumina powder and γ-alumina powder, a group 6 metal of the periodic table,
An aqueous solution of at least one water-soluble compound of a Group 8 metal and phosphoric acid is kneaded, molded, and once dried, and the dried molded product contains a hydrocarbon consisting of carbon and hydrogen having 1 to 15 carbon atoms. 1. A method for producing a catalyst for hydrogenation of hydrocarbons, which comprises impregnating a catalyst with a solution of a thioacid and then drying the catalyst again.

8 One or both of boehmite-type alumina powder and γ-alumina powder, a group 6 metal of the periodic table,
An aqueous solution of at least one type of water-soluble compound of a group 8 metal is kneaded, molded and once dried, and the dried molded product is mixed with phosphoric acid and a hydrocarbon consisting of carbon having 1 to 15 carbon atoms and hydrogen. 1. A method for producing a catalyst for hydrogenation of hydrocarbons, which comprises impregnating a catalyst with a solution of thioic acid and then drying the catalyst again.

9 One or both of boehmite type alumina powder and γ-alumina powder, a Group 6 metal of the periodic table,
A solution of at least one water-soluble compound of a Group 8 metal and a hydrocarbon thio acid consisting of carbon and hydrogen having 1 to 15 carbon atoms is kneaded and molded, and once dried, the dried molded product is A method for producing a catalyst for hydrogenation of hydrocarbons, which comprises impregnating with an aqueous solution of phosphoric acid and then drying again.

10 One or both of boehmite type alumina powder and γ-alumina powder is combined with phosphoric acid and
A solution of a hydrocarbon consisting of ~15 carbons and hydrogen with a thioic acid is kneaded, molded and once dried, and the dried molded product is mixed with water-soluble compounds of Group 6 metals and Group 8 metals of the periodic table. 1. A method for producing a catalyst for hydrotreating hydrocarbons, which comprises impregnating with an aqueous solution of at least one type of catalyst and then drying the catalyst again.

11 One or both of boehmite-type alumina powder and γ-alumina powder are kneaded with a solution of a thioacid of a hydrocarbon consisting of carbon and hydrogen having 1 to 15 carbon atoms, molded, and once dried to obtain the dried molded product. for hydrogenation treatment of hydrocarbons, which is characterized in that it is impregnated with an aqueous solution of phosphoric acid and at least one of water-soluble compounds of group 6 metals and group 8 metals of the periodic table, and then dried again. Method for producing catalyst.

12 One or both of boehmite-type alumina powder and γ-alumina powder are kneaded with an aqueous solution of phosphoric acid, molded, and once dried. For hydrogenation treatment of hydrocarbons, characterized in that it is impregnated with a solution of at least one water-soluble compound and a thioacid of a hydrocarbon consisting of carbon and hydrogen having 1 to 15 carbon atoms, and then dried again. Method for producing catalyst.

As the carrier material mainly composed of aluminum oxide used in the present invention, γ-alumina or boehmite obtained by heat treating aluminum hydrate is used. Boehmite is a hydrated oxide of aluminum with the structural formula AlO(OH). Chemically, it is a gel-like substance obtained by hydrolyzing sodium aluminate and dehydrated using a filter press to form dehydrated boehmite gel. Alternatively, a spray-dried product of dehydrated boehmite gel is used. Boehmite is also naturally produced as boehmite, which contains impurities such as SiO ₂ , FeO ₂ , Fe ₂ O ₃ , MgO, and CaO. When boehmite is heated, it dehydrates and changes in the order of γ-alumina → δ-alumina → θ-alumina, and becomes α-alumina (corundum) at temperatures above 1000°C. As described above, since boehmite is an intermediate between aluminum hydroxide and aluminum oxide, it may be used in combination with active γ-alumina, or only γ-alumina may be used as the carrier material. Further, silica or titania may be used in combination with these.

Water-soluble compounds of group 6 metals in the periodic table include ammonium molybdate and ammonium tungstate of molybdenum and tungsten, which are generally used as active metals in catalysts, and water-soluble compounds of group 8 metals that are generally used as active metals in catalysts. Cobalt, cobalt nitrate, cobalt carbonate, nickel nitrate, and nickel carbonate, which are used as active metals, are used. Molybdenum trioxide and tungsten trioxide can be converted into ammonium molybdate and ammonium tungstate using ammonia gas, and used as an aqueous solution thereof.

The usage amount of thioacids of hydrocarbons consisting of carbon and hydrogen having 1 to 15 carbon atoms is based on metals of group 6 and metals of group 8 of the periodic table.
The amount of sulfur is preferably 1 to 3 times the amount of sulfur required for the group metal to form sulfide forms (eg, MoS ₂ , WS ₂ , CoS, NiS) that exhibit high activity in hydrogenation reactions. If the amount used is less than 1 equivalent, the activity will not be fully utilized, and 3
The amount used in this proportion is sufficient since the activity is no longer improved if the equivalent amount is exceeded.

In the above-mentioned thioacids, the part used as a sulfurizing agent for active metals is the -COSH group in the molecule of the thioacid, so when the number of carbon atoms in the hydrocarbon group increases, the part in the molecule that acts as a sulfurizing agent decreases. Since the amount is relatively small, it is not only uneconomical, but also causes unnecessary carbon and hydrogen to be contained in the catalyst, which is not preferable. Therefore, it is preferable to use thioacids with a small number of carbon atoms such as thioacetic acid (CH ₃ COSH) and thiobenzoic acid (C ₆ H ₅ COSH), and it is preferable to use thio acids with a maximum of 15 carbon atoms. good.

Phosphoric acid is contained in the catalyst at 3% by weight calculated as P ₂ O ₅
It is better to include a certain degree.

The catalyst produced by the production method of the present invention is used for hydrotreating hydrocarbon oil by filling a reaction tower with the dry catalyst as it is. The water used in the process of producing the catalyst may be removed by putting it into the reaction tower and then drying it.

[Effect]

The catalyst according to the invention acts as a sulfiding agent -
Since thioacetic acid and thiobenzoic acid having a COSH group are supported on a carrier material together with a water-soluble active metal compound, the active metal turns into sulfide during the temperature rise process to the hydrodesulfurization reaction temperature of hydrocarbon oil. Converted,
In particular, the hydrocarbon oil can be directly subjected to the hydrodesulfurization reaction without any preliminary sulfurization treatment.
Furthermore, the catalyst of the present invention exhibits excellent activity. The reason for this is not clear, but it is because thioacetic acid and thiobenzoic acid form a soluble coordination compound (metal mercaptide) with the water-soluble active metal compound and are supported on the carrier material in a highly dispersed state. it is conceivable that.

〔Example〕

In all of the following examples, the catalysts were extruded into cylindrical shapes with a diameter of 1.6 mm and a length of 3 to 5 mm.

In addition, activity evaluation was determined by hydrodesulfurization reaction of Kuwait atmospheric gas oil.

The properties of the normal pressure gas oil used in the reaction were as follows.

Specific gravity (15/4℃) 0.844 Sulfur (weight%) 1.13 Nitrogen (weight ppm) 162 Distillation properties (initial boiling point ℃) 203.3 〃 (50 volume % point ℃) 299.0 〃 (end point ℃) 391.8 Reaction is carried out in a flow reactor The reaction was carried out under the following reaction conditions.

Catalyst amount 3 ml Raw oil space velocity 2.0 hr ^-1 Reaction pressure (hydrogen pressure) 30 Kg/cm ² Reaction temperature 330°C Hydrogen/oil ratio 300 N/ Oil passage time 8 hr The treated oil was sampled every 2 hours to determine the sulfur content. The desulfurization rate was determined. The desulfurization rate shown in the following examples is 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.

Example 1 To 300 ml of a solution prepared from 37.0 g of molybdenum trioxide, 15.8 g of cobalt carbonate (Co content 49.1% by weight), ammonia gas and water, 75.2 g of thioacetic acid was added to prepare a solution of metal mercaptide (PH 5.2). ).

272 g of this metal mercaptide solution and spray-dried boehmite-type alumina powder (73.5% by weight Al ₂ O ₃ )
were put into a kneader and kneaded to obtain a mixture of alumina and metal mercaptide, which was then molded.

This molded body was dried at 100°C for 16 hours to obtain catalyst 1.

The breaking strength of Catalyst 1 was 1.5 Kg/mm or more.

The metal content of catalyst 1 is molybdenum is 15% by weight in terms of _MoO3 , cobalt is 4% by weight in terms of CoO, and the amount of thioacetic acid used is as follows:
The amount was 1.5 times the theoretical amount of sulfur required to form MoS ₂ and CoS.

The desulfurization rate of this catalyst 1 was 82.8%.

Example 2 37.0 g of tungsten trioxide, cobalt carbonate (Co
To 300 ml of a solution prepared from 15.8 g (content 49.1% by weight), ammonia gas and water, 52.3 g of thioacetic acid was added to prepare a solution of metal mercaptide (PH 5.6).

This metal mercaptide solution and 272 g of the boehmite-type alumina powder used in Example 1 were placed in a kneader and kneaded to obtain a mixture of alumina and metal mercaptide, which was then molded.

This molded body was dried at 100°C for 16 hours to obtain catalyst 2.

The breaking strength of Catalyst 2 was 1.5 Kg/mm or more.

The metal content of catalyst 2 is 15% by weight of tungsten in terms of WO ₃ and 4% of cobalt in terms of CoO.
The amount of thioacetic acid used was 1.5 times the theoretical amount of sulfur required to convert W and Co into WS ₂ and CoS, respectively.

The desulfurization rate of this catalyst 2 was 82.0%.

Example 3 400 ml of an aqueous solution was prepared from 37.0 g of molybdenum trioxide, 15.8 g of cobalt carbonate (Co content 49.1% by weight), ammonia gas and water (PH7.0).

This solution and 272 g of the boehmite-type alumina powder used in Example 1 were placed in a kneader and kneaded to obtain a mixture of alumina and metal aqueous solution, which was then molded.

This molded body was dried at 100°C for 16 hours.

Next, add an aqueous solution containing 75.2 g of thioacetic acid to the dried product.
After impregnating the entire 120ml, it was dried at 100°C for 16 hours to obtain catalyst 3.

The breaking strength of Catalyst 3 was 1.5 Kg/mm or more.

The metal content of catalyst 3 is molybdenum is 15% by weight in terms of MoO ₃ , cobalt is 4% by weight in terms of CoO, and the amount of thioacetic acid used is such that Mo and Co become MoS ₂ and CoS, respectively. It was 1.5 times the theoretical amount of sulfur required for this purpose.

The desulfurization rate of this catalyst 3 was 82.3%.

Example 4 Aqueous solution containing 272 g of the boehmite-type alumina powder used in Example 1 and 133.6 g of thiobenzoic acid
After putting 300 ml into a kneader and performing kneading to obtain a mixture, it was molded.

This molded body was dried at 100°C for 16 hours.

The total amount of this dry molded product contains 37.0 molybdenum trioxide.
g, cobalt carbonate (Co content 49.1% by weight) 15.8
solution prepared from g, ammonia gas and water 150
ml (PH7.5) and drying at 100°C for 16 hours was repeated twice to obtain catalyst 4.

The breaking strength of Catalyst 4 was 1.5 Kg/mm or more.

The metal content of catalyst 4 is molybdenum is 15% by weight in terms of MoO ₃ , cobalt is 4% by weight in terms of CoO, and the amount of thiobenzoic acid used is as follows:
The amount was 1.5 times the theoretical amount of sulfur required to form MoS ₂ and CoS.

The desulfurization rate of this catalyst 4 was 81.9%.

Example 5 38.5 g of molybdenum trioxide, 16.4 g of cobalt carbonate (Co content 49.1% by weight), 12.5 g of 85% by weight phosphoric acid
Add thioacetic acid to 300 ml of a solution prepared from g and water.
78.2 g was added to form a solution of metal mercaptide containing phosphoric acid (PH 0.8).

This metal mercaptide solution and 673 g of dehydrated boehmite-type alumina gel (Al ₂ O ₃ 29.7% by weight) were placed in a heated kneader and heat kneaded at 95°C to evaporate excess water to mix the alumina and metal mercaptide. After obtaining the product, it was molded.
This molded body was dried at 100°C for 16 hours to obtain catalyst 5.

The breaking strength of Catalyst 5 was 1.5 Kg/mm or more.

The metal content of catalyst 5 is molybdenum is 15% by weight in terms of MoO ₃ , cobalt is 4% by weight in terms of CoO, phosphorus is 3% by weight in terms of P ₂ O ₅ ,
The amount of thioacetic acid used is MoS ₂ and Co for Mo and Co, respectively.
In terms of the theoretical amount of sulfur required to form CoS,
It was 1.5 times bigger.

The desulfurization rate of this catalyst 5 was 83.0%.

Example 6 38.5 g of molybdenum trioxide, 16.4 g of cobalt carbonate (Co content 49.1% by weight), 12.5 g of 85% by weight phosphoric acid
Add thioacetic acid to 300 ml of a solution prepared from g and water.
78.2 g was added to form a solution of metal mercaptide containing phosphoric acid (PH 0.8).

This metal mercaptide solution and 272 g of the boehmite-type alumina powder used in Example 1 were placed in a kneader and kneaded to obtain a mixture of alumina and metal mercaptide, which was then molded.

This molded body was dried at 100° C. for 16 hours to obtain catalyst 6.

The breaking strength of Catalyst 6 was 1.5 Kg/mm or more.

The metal content of the catalyst 6 is molybdenum is 15% by weight in terms of _MoO3 , cobalt is 4% by weight in terms of CoO, phosphorus is ₃ % by weight in terms of _P2O5 ,
The amount of thioacetic acid used is MoS ₂ and Co for Mo and Co, respectively.
In terms of the theoretical amount of sulfur required to form CoS,
It was 1.5 times as hot.

The desulfurization rate of this catalyst 6 was 83.6%.

Example 7 38.5 g of molybdenum trioxide, 16.4 g of cobalt carbonate (Co content 49.1% by weight), 12.5 g of 85% by weight phosphoric acid
139.0 g of thiobenzoic acid was added to 300 ml of a solution prepared from g and water to obtain a solution of metal mercaptide containing phosphoric acid (PH 1.0).

This metal mercaptide solution and 200 g of γ-alumina powder were placed in a kneader and kneaded to obtain a mixture of alumina and metal mercaptide, which was then molded.

This molded body was dried at 100°C for 16 hours to obtain catalyst 7.

The breaking strength of Catalyst 7 was 1.5 Kg/mm or more.

The metal content of the catalyst 7 is molybdenum is 15% by weight in terms of _MoO3 , cobalt is 4% by weight in terms of CoO, and phosphorus is ₃ % by weight in terms of _P2O5 .
The amount of thiobenzoic acid used is Mo and Co, respectively.
The amount was 1.5 times the theoretical amount of sulfur required to form MoS ₂ and CoS.

The desulfurization rate of this catalyst 7 was 85.8%.

Example 8 38.5 g of molybdenum trioxide, 16.4 g of cobalt carbonate (Co content 49.1% by weight), 12.5 g of 85% by weight phosphoric acid
139.0 g of thiobenzoic acid was added to 300 ml of a solution prepared from g and water to obtain a solution of metal mercaptide containing phosphoric acid (PH 1.0).

This metal mercaptide solution and 673 g of the boehmite-type alumina gel used in Example 5 were placed in a heated kneader to evaporate excess water.
After heat kneading was performed at 95°C to obtain a mixture of alumina and metal mercaptide, it was molded. This molded body was dried at 100°C for 16 hours to obtain catalyst 8.

The breaking strength of Catalyst 8 was 1.5 Kg/mm or more.

The metal content of catalyst 8 is molybdenum is 15% by weight in terms of _MoO3 , cobalt is 4% by weight in terms of CoO, phosphorus is ₃ % by weight in terms of _P2O5 ,
The amount of thiobenzoic acid used is Mo and Co, respectively.
The amount was 1.5 times the theoretical amount of sulfur required to form MoS ₂ and CoS.

The desulfurization rate of this catalyst 8 was 83.8%.

Example 9 38.5 g of molybdenum trioxide, 16.4 g of cobalt carbonate (Co content 49.1% by weight), 12.5 g of 85% by weight phosphoric acid
139.0 g of thiobenzoic acid was added to 300 ml of a solution prepared from g and water to obtain a solution of metal mercaptide containing phosphoric acid (PH 1.0).

This metal mercaptide solution and 272 g of the boehmite-type alumina powder used in Example 1 were placed in a kneader and kneaded to obtain a mixture of alumina and metal mercaptide, which was then molded. This molded body was dried at 100° C. for 16 hours to obtain catalyst 9.

The breaking strength of Catalyst 9 was 1.5 Kg/mm or more.

The metal content of catalyst 9 is molybdenum is 15% by weight in terms of _MoO3 , cobalt is 4% by weight in terms of CoO, phosphorus is ₃ % by weight in terms of _P2O5 ,
The amount of thiobenzoic acid used is Mo and Co, respectively.
The amount was 1.5 times the theoretical amount of sulfur required to form MoS ₂ and CoS.

The desulfurization rate of this catalyst 9 was 84.2%.

Example 10 57.6 g of molybdenum trioxide, 20.9 g of nickel carbonate (Ni content 43.3% by weight), 30.4 g of 85% by weight phosphoric acid
Add thioacetic acid to 300 ml of a solution prepared from g and water.
110.9 g was added to form a solution of metal mercaptide containing phosphoric acid (PH 0.6).

This metal mercaptide solution and 272 g of the boehmite-type alumina powder used in Example 1 were placed in a kneader and kneaded to obtain a mixture of alumina, phosphoric acid, and metal mercaptide, which was then molded.

This molded body was dried at 100°C for 16 hours to obtain catalyst 10.

The breaking strength of Catalyst 10 was 1.5 Kg/mm or more.

The metal content of catalyst 10 is molybdenum is 20% by weight in terms of _MoO3 , nickel is 4% by weight in terms of NiO, phosphorus is _6.5 % by weight in terms of _P2O5 ,
The amount of thioacetic acid used is MoS ₂ and Ni for Mo and Ni, respectively.
In terms of the theoretical amount of sulfur required to form NiS,
It was 1.5 times bigger.

The desulfurization rate of this catalyst 10 was 80.5%.

Example 11 38.5 g of molybdenum trioxide, 16.4 g of cobalt carbonate (Co content 49.1% by weight), 12.5 g of 85% by weight phosphoric acid
300 ml of an aqueous solution was prepared from g and water (PH2.0).

This solution and 272 g of the boehmite-type alumina powder used in Example 1 were placed in a kneader and kneaded to obtain a mixture of alumina, metal aqueous solution and phosphoric acid, which was then molded.

This molded body was dried at 100°C for 16 hours.

Next, add an aqueous solution containing 78.2 g of thioacetic acid to the dried product.
After impregnating the entire 115ml, dry at 100℃ for 16 hours to remove the catalyst.
Got 11.

The breaking strength of Catalyst 11 was 1.5 Kg/mm or more.

The metal content of catalyst 11 is molybdenum is 15% by weight in terms of _MoO3 , cobalt is 4% by weight in terms of CoO, phosphorus is ₃ % by weight in terms of _P2O5 ,
The amount of thioacetic acid used is MoS ₂ and Co for Mo and Co, respectively.
In terms of the theoretical amount of sulfur required to form CoS,
It was 1.5 times bigger.

The desulfurization rate of this catalyst 11 was 81.5%.

Example 12 300 ml of a solution prepared from 38.5 g of molybdenum trioxide, 16.4 g of cobalt carbonate (Co content 49.1% by weight), ammonia gas and water (PH 7.0) and Example 1
272 g of the boehmite-type alumina powder used in step 1 was put into a kneader and kneaded to obtain a mixture, which was then molded.

This molded body was dried at 100°C for 16 hours.

Next, 12.5 g of 85% by weight phosphoric acid was added to the dried material,
After impregnating a total amount of 120 ml of an ethanol solution containing 78.2 g of thioacetic acid, the catalyst was dried at 100° C. for 16 hours to obtain catalyst 12.

The breaking strength of Catalyst 12 was 1.5 Kg/mm or more.

The metal content of catalyst 12 is molybdenum is 15% by weight in terms of _MoO3 , cobalt is 4% by weight in terms of CoO, phosphorus is ₃ % by weight in terms of _P2O5 ,
The amount of thioacetic acid used is MoS ₂ and Co for Mo and Co, respectively.
In terms of the theoretical amount of sulfur required to form CoS,
It was 1.5 times bigger.

The desulfurization rate of this catalyst 12 was 82.5%.

Example 13 139.0 g of thiobenzoic acid was added to 300 ml of a solution prepared from 38.5 g of molybdenum trioxide, 16.4 g of cobalt carbonate (Co content 49.1% by weight), ammonia gas and water.
was added to make a solution of metal mercaptide (PH
5.5).

This metal mercaptide solution and 272 g of the boehmite-type alumina powder used in Example 1 were placed in a kneader and kneaded to obtain a mixture, which was then molded.

This molded body was dried at 100°C for 16 hours. Next, add an aqueous solution containing 12.5 g of 85% by weight phosphoric acid to the dried product.
After impregnating the entire 50ml, dry at 100℃ for 16 hours to remove the catalyst.
Got 13.

The breaking strength of Catalyst 13 was 1.5 Kg/mm or more.

The metal content of catalyst 13 is as follows: molybdenum is 15% by weight in terms of MoO ₃ and cobalt is 4% by weight in terms of CoO.
% by weight, phosphorus is 3% by weight converted to P ₂ O ₅ ,
The amount of thiobenzoic acid used is Mo and Co, respectively.
The amount was 1.5 times the theoretical amount of sulfur required to form MoS ₂ and CoS.

The desulfurization rate of this catalyst 13 was 83.1%.

Example 14 272 g of the boehmite-type alumina powder used in Example 1, 78.2 g of thioacetic acid and 85% by weight phosphoric acid
300 ml of an aqueous solution containing 12.5 g was placed in a kneader and kneaded to form a shape.

This molded body was dried at 100°C for 16 hours.

The total amount of this dry molded body contains 38.5 molybdenum trioxide.
g, cobalt carbonate (Co content 49.1% by weight) 16.4
g, a solution prepared from ammonia gas and water
After impregnating the entire amount of 150 ml (PH7.5), catalyst 14 was obtained by drying at 100° C. for 16 hours.

The breaking strength of catalyst 14 was 1.5 Kg/mm or more.

The metal content of catalyst 14 is 15% by weight of molybdenum calculated as MoO ₃ and 4% of cobalt calculated as CoO.
% by weight, phosphorus is 3% by weight converted to P ₂ O ₅ ,
The amount of thioacetic acid used is MoS ₂ and Co for Mo and Co, respectively.
In terms of the theoretical amount of sulfur required to form CoS,
It was 1.5 times bigger.

The desulfurization rate of this catalyst 14 was 82.5%.

Example 15 272 g of the boehmite-type alumina powder used in Example 1 and 300 ml of an aqueous solution containing 78.2 g of thioacetic acid were placed in a kneader and kneaded to form a product. This molded body was dried at 100°C for 16 hours.

The total amount of this dry molded body contains 38.5 molybdenum trioxide.
g, cobalt carbonate (Co content 49.1% by weight) 16.4
After impregnating the entire amount of 100ml (PH2.0) in a solution prepared from g, 12.5g of 85% by weight phosphoric acid, and water,
Catalyst 15 was obtained by drying at 100°C for 16 hours.

The breaking strength of Catalyst 15 was 1.5 Kg/mm or more.

The metal content of catalyst 15 is 15% by weight of molybdenum calculated as MoO ₃ and 4% of cobalt calculated as CoO.
% by weight, phosphorus is 3% by weight converted to P ₂ O ₅ ,
The amount of thioacetic acid used is MoS ₂ and Co for Mo and Co, respectively.
In terms of the theoretical amount of sulfur required to form CoS,
It was 1.5 times bigger.

The desulfurization rate of this catalyst 15 was 82.8%.

Example 16 272 g of the boehmite-type alumina powder used in Example 1 and 300 ml of an aqueous solution containing 12.5 g of 85% by weight phosphoric acid were placed in a kneader and kneaded to form a product.

This molded body was dried at 100°C for 16 hours.

The total amount of this dry molded body contains 38.5 molybdenum trioxide.
g, cobalt carbonate (Co content 49.1% by weight) 16.4
g, a solution prepared from ammonia gas and water
After impregnating the entire amount with 250 ml of a metal mercaptide solution (PH 5.0) obtained by adding 78.2 g of thioacetic acid to 300 ml, the catalyst was dried at 100° C. for 16 hours to obtain catalyst 16.

The breaking strength of Catalyst 16 was 1.5 Kg/mm or more.

The metal content of catalyst 16 is 15% by weight of molybdenum calculated as MoO ₃ and 4% of cobalt calculated as CoO.
% by weight, phosphorus is 3% by weight converted to P ₂ O ₅ ,
The amount of thioacetic acid used is MoS ₂ and Co for Mo and Co, respectively.
In terms of the theoretical amount of sulfur required to form CoS,
It was 1.5 times bigger.

The desulfurization rate of this catalyst 16 was 82.3%.

Conventional example (1) MoO ₃ using γ-alumina as a carrier formed into pellets with a diameter of 1.5 mm and a length of 5 to 10 mm and fired.
A commercially available catalyst (KF-742, manufactured by Nippon Ketsuen Co., Ltd.) containing 15% by weight of CoO and 4% by weight of CoO was subjected to the following presulfurization treatment.

Sulfurized oil 3% by weight n-butyl mercaptan/Kuate atmospheric gas oil Catalyst amount 3 ml Raw oil liquid space velocity 2.0 hr ^-1 Reaction pressure (hydrogen pressure) 30 Kg/cm ² Reaction temperature 316°C Hydrogen/oil ratio 300 N/ Oil passage time 8 hr The activity of this presulfurized catalyst was evaluated in the same manner as in the example, and the desulfurization rate was 82.4%.
It was hot.

(2) Molded into a pellet with a diameter of 1.5 mm and a length of 5 to 10 mm and fired, specific surface area 280 m ² /g, pore area
100 g of a 0.75 ml/g γ-alumina molded carrier was impregnated with 80 ml of an impregnating solution prepared from 19.2 g of molybdenum trioxide, 8.2 g of cobalt carbonate with a Co content of 49.1% by weight, 6.2 g of 85% by weight phosphoric acid, and water, 110℃,
After drying for 16 hours, bake at 500℃ for 2 hours.
MoO ₃ 15% by weight, CoO 4% by weight, P ₂ O ₅ 3% by weight
A containing catalyst was obtained.

This catalyst was pre-sulfurized in the same manner as in (1) above, and its activity was evaluated in the same manner as in the examples. As a result, the desulfurization rate was 80.4%.

〔Effect of the invention〕

The above-mentioned conventional catalyst requires calcination treatment and pre-sulfurization treatment for 8 hours.
The catalyst described in Publication No. 111144 also requires calcination treatment for at least 1 hour after being impregnated with a sulfiding agent, but the catalyst of the present invention and the catalyst produced by the method for producing the same do not require presulfidation and require calcination. It can be used as is for hydrogenation treatment without any
A more economical catalyst than conventional ones can be provided.

Claims (1)

[Claims] 1. One or both of boehmite-type alumina powder and γ-alumina powder, and a metal of Group 6 of the periodic table, metal of Group 8 of the periodic table.
It consists of at least one water-soluble compound of group metal and a hydrocarbon thioacid having 1 to 15 carbon atoms and hydrogen, and at least one or all of the water-soluble compound and the thioacid are , a boehmite-type alumina powder, a γ-alumina powder, or a γ-alumina powder. A catalyst for hydrogenation of hydrocarbons, comprising an unfired mixed molded product of boehmite-type alumina powder and/or γ-alumina powder. 2 One or both of the boehmite-type alumina powder and γ-alumina powder contains metals from group 6 of the periodic table and metals from group 8 of the periodic table.
A hydrocarbon compound characterized by kneading a solution of at least one water-soluble compound of group metal and a thioacid of a hydrocarbon having 1 to 15 carbon atoms and hydrogen, forming the mixture, and then drying it. A method for producing a catalyst for hydrotreating. 3 One or both of the boehmite-type alumina powder and γ-alumina powder contains metals from group 6 of the periodic table and metals from group 8 of the periodic table.
An aqueous solution of at least one of the water-soluble compounds of group metals is kneaded, shaped and once dried, and the dried shaped product is impregnated with a solution of a thioic acid of a hydrocarbon consisting of carbon having 1 to 15 carbon atoms and hydrogen. 1. A method for producing a catalyst for hydrotreating hydrocarbons, which comprises drying again after drying. 4 One or both of boehmite-type alumina powder and γ-alumina powder are kneaded with a solution of a hydrocarbon thioacid having 1 to 15 carbon atoms and hydrogen, molded, and once dried, and the dried molded product is , periodic table 6th
A method for producing a catalyst for hydrogenation of hydrocarbons, which comprises impregnating the catalyst with an aqueous solution of at least one of water-soluble compounds of group metals and group 8 metals, and then drying the catalyst again. 5 One or both of boehmite-type alumina powder and γ-alumina powder, and a metal of group 6 of the periodic table, metal of group 8 of the periodic table.
It consists of at least one water-soluble compound of group metal, phosphoric acid, and a thio acid of a hydrocarbon having 1 to 15 carbon atoms and hydrogen; A catalyst for hydrogenation of hydrocarbons, comprising an unfired mixture of boehmite-type alumina powder, γ-alumina powder, or both particles, in which at least one or all of the acids are present at the bonding surface of each particle. 6 One or both of the boehmite-type alumina powder and γ-alumina powder contains metals from group 6 of the periodic table and metals from group 8 of the periodic table.
A solution of at least one water-soluble compound of group metal, phosphoric acid, and a thioic acid of a hydrocarbon having 1 to 15 carbon atoms and hydrogen is kneaded, shaped, and then dried. A method for producing a catalyst for hydrotreating hydrocarbons. 7 One or both of the boehmite type alumina powder and γ-alumina powder contains metals from group 6 of the periodic table and metals from group 8 of the periodic table.
An aqueous solution of at least one of the water-soluble compounds of group metals and phosphoric acid is kneaded, molded, and once dried, and the dried molded product is coated with a hydrocarbon thiocarbon having 1 to 15 carbon atoms and hydrogen. A method for producing a catalyst for hydrogenation of hydrocarbons, which comprises impregnating with an acid solution and then drying again. 8 One or both of the boehmite-type alumina powder and γ-alumina powder contains metals from group 6 of the periodic table and metals from group 8 of the periodic table.
An aqueous solution of at least one of the water-soluble compounds of group metals is kneaded, molded and once dried, and the dried molded product is mixed with phosphoric acid and a thio acid of a hydrocarbon having 1 to 15 carbon atoms and hydrogen. After impregnating the solution with
A method for producing a catalyst for hydrotreating hydrocarbons, which comprises drying again. 9 One or both of the boehmite type alumina powder and γ-alumina powder contains metals from group 6 of the periodic table and metals from group 8 of the periodic table.
A solution of at least one water-soluble compound of group metal and a hydrocarbon thioacid consisting of carbon and hydrogen having 1 to 15 carbon atoms is kneaded and molded, and once dried, the dried molded product is coated with phosphorus. A method for producing a catalyst for hydrogenation of hydrocarbons, which comprises impregnating with an aqueous acid solution and then drying again. 10 One or both of boehmite type alumina powder and γ-alumina powder, phosphoric acid and a carbon atom having 1 to 1 carbon atoms.
A solution of a hydrocarbon thioacid consisting of 15 carbons and hydrogen is kneaded, shaped and once dried, and the dried shaped product is injected with one of the water-soluble compounds of group 6 metals and group 8 metals of the periodic table. A method for producing a catalyst for hydrogenation of hydrocarbons, which comprises impregnating with at least one kind of aqueous solution and then drying again. 11 One or both of boehmite-type alumina powder and γ-alumina powder is kneaded with a solution of a thioacid of a hydrocarbon having 1 to 15 carbon atoms and hydrogen, molded, and once dried, and the dried molded product is A catalyst for hydrogenation of hydrocarbons, characterized in that the catalyst is impregnated with an aqueous solution of phosphoric acid and at least one of water-soluble compounds of Group 6 metals and Group 8 metals of the periodic table, and then dried again. manufacturing method. 12 One or both of the boehmite-type alumina powder and the γ-alumina powder are kneaded with an aqueous solution of phosphoric acid, molded, and once dried, and the dried molded product is injected with an aqueous solution of a Group 6 metal or a Group 8 metal of the periodic table. A catalyst for hydrogenation of hydrocarbons, characterized in that the catalyst is impregnated with a solution of at least one type of chemical compound and a thioacid of a hydrocarbon consisting of carbon and hydrogen having 1 to 15 carbon atoms, and then dried again. manufacturing method.