JPH0549341B2 - - 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]

In so-called hydrogenation treatment, in which hydrocarbon oil is subjected to hydrogenation, desulfurization, denitrification, decomposition, etc. in the presence of hydrogen, it is formed into a pallet shape of alumina, silica-alumina, titania, etc. and then baked on an inorganic oxide carrier. 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 commonly 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 using hydrogen sulfide, 0.5
~5% by volume, converted into standard temperature and pressure per catalyst of 1000~3000, temperature 180
℃ (usually above 250℃), 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℃.
℃, pressure 20~100Kg/ ^cm2 , liquid space velocity 0.5~2hr ^-1 ,
It is carried out at a hydrogen/oil ratio of 200 to 1000N/.

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 omit presulfurization or at least reduce the complexity of the operation.

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

The method involves applying the general formula R-S(n)-R' (n is an integer from 3 to 20, R,
R′ is a hydrogen atom or an organic group having 1 to 150 carbon atoms per molecule) is impregnated with a polysulfide in the absence of hydrogen gas at a temperature of 65 to 275 °C and a pressure of 0.5 to 70 bar. In this method, the catalyst is heat-treated (Japanese Patent Application Laid-Open 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. , a method in which the active metal is made into an oxide form by drying and heat treatment, or by mixing alumina hydrate and an aqueous solution of a water-soluble compound of the active metal, molding, drying, and baking. - It is made by supporting an active metal in the form of an oxide on a support made of alumina.

[Problem to be solved by the invention]

The present invention is simpler than the above conventional method,
It can be produced at low cost, can be used for hydrogenation treatment without requiring pre-sulfurization treatment, and can be directly subjected to hydrogenation treatment without heat treatment.
An object of the present invention is to provide a catalyst for hydrotreating hydrocarbons 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. consisting of a hydrocarbon amino-substituted mercaptan,
At least one or all of the water-soluble compound and the amino-substituted mercaptan 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.

2. One or both of the boehmite-type alumina powder and the γ-alumina powder contains at least one of the water-soluble compounds of Group 6 metals and Group 8 metals of the periodic table, carbon having 1 to 15 carbon atoms, and hydrogen. 1. A method for producing a catalyst for hydrotreating hydrocarbons, which comprises kneading a solution of a hydrocarbon with an amino-substituted mercaptan, shaping the solution, and then drying the solution.

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

4 A solution of an amino-substituted mercaptan, a hydrocarbon consisting of carbon and hydrogen having 1 to 15 carbon atoms, is kneaded with one or both of boehmite-type alumina powder and γ-alumina powder, molded, and once dried to form the dried molded product. 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 6 metals and group 8 metals of the periodic table, and then drying the catalyst 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 above-mentioned water-soluble compound, phosphoric acid, and at least one or all of the above-mentioned amino-substituted mercaptans are contained in 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 of these particles interposed at the bonding surface of each particle.

6 One or both of the boehmite-type alumina powder and the γ-alumina powder are mixed with 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 number of 1 to 15. 1. A method for producing a catalyst for hydrotreating hydrocarbons, which comprises kneading a solution of a hydrocarbon amino-substituted mercaptan consisting of carbon and hydrogen, shaping the solution, and then drying it.

7 One or both of boehmite-type alumina powder and γ-alumina powder is kneaded with an aqueous solution of at least one of the water-soluble compounds of Group 6 metals and Group 8 metals of the periodic table and phosphoric acid, and then molded. For hydrogenation treatment of hydrocarbons, characterized by drying once, impregnating the dried molded product with a solution of an amino-substituted mercaptan of a hydrocarbon consisting of carbon having 1 to 15 carbon atoms and hydrogen, and drying again. Method for producing catalyst.

8 One or both of boehmite-type alumina powder and γ-alumina powder is kneaded with an aqueous solution of at least one of water-soluble compounds of Group 6 metals and Group 8 metals of the periodic table, molded, and once dried. For hydrogenation treatment of hydrocarbons, which comprises impregnating a dry molded product with a solution of phosphoric acid and an amino-substituted mercaptan of a hydrocarbon consisting of carbon and hydrogen having 1 to 15 carbon atoms, and then drying it again. Method for producing catalyst.

9 One or both of the boehmite-type alumina powder and the γ-alumina powder, at least one of the water-soluble compounds of Group 6 metals and Group 8 metals of the periodic table, carbon having 1 to 15 carbon atoms, and hydrogen. For hydrogenation treatment of hydrocarbons, the method comprises kneading a solution of a hydrocarbon with an amino-substituted mercaptan, molding the product, drying it once, impregnating the dried molded product with an aqueous solution of phosphoric acid, and drying it again. Method for producing catalyst.

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

11 One or both of boehmite-type alumina powder and γ-alumina powder is kneaded with a solution of amino-substituted mercaptan, 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 is kneaded with an aqueous solution of phosphoric acid, molded, and once dried. For hydrogenation treatment of hydrocarbons, which is characterized by impregnating with a solution of at least one type of chemical compound and an amino-substituted mercaptan of a hydrocarbon consisting of carbon and hydrogen having 1 to 15 carbon atoms, and then drying 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 AO(OH).Chemically speaking, boehmite gel is obtained by dehydrating a gel-like substance obtained by hydrolyzing sodium aluminate using a filter press. , spray-dried dehydrated boehmite gel is used. Boehmite also occurs naturally as boehmite, which includes:
It contains SiO ₂ , FiO ₂ , Fe ₂ O ₃ , MgO, CaO, etc. as impurities. 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 the amino-substituted mercaptan, which is a hydrocarbon consisting of carbon and hydrogen having 1 to 15 carbon atoms, is determined by the use of sulfide forms (e.g., MoS ₂ , WS ₂ ,
The amount of sulfur required to form CoS, NiS)
3 equivalents is better. If the amount used is less than 1 equivalent, the activity will not be fully utilized, and if it exceeds 3 equivalents, the activity will no longer be improved, so the amount used in this ratio is sufficient.

In the above amino-substituted mercaptan, the moiety that acts as a sulfiding agent for the active metal is the -SH group in the molecule of the amino-substituted mercaptan, so when the number of carbon atoms in the hydrocarbon group increases, it acts as a sulfiding agent in the molecule. Since the portion becomes relatively small, this is not only uneconomical, but also causes unnecessary carbon and hydrogen to be contained in the catalyst, which is not preferable. Therefore, 2-aminoethanethiol (H ₂ NCH ₂ CH ₂
SH) and 4-aminothiophenol (H ₂ NC ₆ H ₄
It is preferable to use an amino-substituted mercaptan having a small number of carbon atoms, such as SH), and it is preferable to use a mercaptan having at most 15 carbon atoms.

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 dried catalyst as it is. The water used in the process of producing the catalyst may be removed by entering the reaction tower and then drying it.

[Effect]

The catalyst according to the invention acts as a sulfiding agent -
2-aminoethanethiol and 4-
Since the aminothiophenol is supported on the carrier material together with the water-soluble compound of the active metal, the active metal converts into sulfide during the temperature increase process to the hydrodesulfurization reaction temperature of the hydrocarbon oil, and especially during pre-sulfurization treatment. Even if this is not carried out, the hydrocarbon oil can be directly subjected to the hydrodesulfurization reaction. Furthermore, the catalyst of the present invention exhibits excellent activity. The reason is not clear, but 2
This is thought to be due to the fact that -aminoethanethiol and 4-aminothiophenol 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.

〔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 in circulation The reaction was carried out using a type reactor under the following reaction conditions.

Catalyst amount 3ml Raw oil space velocity 2.0hr ^-1 Reaction pressure (hydrogen pressure) 30Kg/ ^cm2 Reaction temperature 330℃ Hydrogen/oil ratio 300N/ Oil passage time 8hr The treated oil was sampled every 2 hours and the sulfur content was determined. The desulfurization rate was determined. The desulfurization rates shown in the examples below are average values of the desulfurization rates determined from the sulfur content of treated oil sampled at the 4th, 6th, and 8th hours.

Example 1 74.6 g of 2-aminoethanethiol was added 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 to prepare a solution of metal mercaptide.

A solution of this metal mercaptide and a spray-dried boehmite-type alumina powder (A ₂ O ₃ 73.5% by weight) were mixed together.
After putting 272g into a kneader and performing kneading to obtain a mixture of alumina and metal mercaptide,
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 MoO ₃ , cobalt is 4% by weight in terms of CoO, and the amount of ₂ -aminoethanethiol used is as follows: It was 1.5 times the theoretical amount of sulfur required to achieve this.

The desulfurization rate of this catalyst 1 was 81.8%.

Example 2 37.0g 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, 52.1 g of 2-aminoethanethiol was added to prepare a solution of metal mercaptide.

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 2-aminoethanethiol used was 1.5 times the theoretical amount of sulfur required for converting W and Co into WS ₂ and CoS, respectively.

The desulfurization rate of this catalyst 2 was 81.5%.

Example 3 300 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.

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 2-aminoethanethiol to the dried product.
After impregnating a total amount of 120 ml of an ethanol solution containing 74.6 g, the catalyst 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 2-aminoethanethiol used is Mo and Co are MoS ₂ and CoS, respectively. It was 1.5 times the theoretical amount of sulfur required to

The desulfurization rate of this catalyst 3 was 81.5%.

Example 4 272 g of the boehmite-type alumina powder used in Example 1 and 300 ml of an aqueous solution containing 121.1 g of 4-aminothiophenol 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.

37.0g of molybdenum trioxide is added to the total amount of this dry molded product.
150 ml of a solution prepared from 15.8 g of cobalt carbonate (Co content 49.1% by weight), ammonia gas and water (PH
The operation of impregnating the entire amount of 7.5) 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 and cobalt is ₄ % by weight in terms of CoO. It was 1.5 times the theoretical amount of sulfur required to achieve this.

The desulfurization rate of this catalyst 4 was 81.3%.

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
77.6 g of 2-aminoethanethiol was added to 300 ml of a solution prepared from 2-aminoethanethiol and water to obtain a solution of metal mercaptide containing phosphoric acid.

This metal mercaptide solution and 673 g of dehydrated boehmite-type alumina gel (A ₂ O ₃ 29.7% by weight)
The mixture was placed in a heating kneader and heat kneaded at 95°C to evaporate excess moisture 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 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 2-aminoethanethiol used was 1.5 times the theoretical amount of sulfur required to convert Mo and Co into MoS ₂ and CoS, respectively.

The desulfurization rate of this catalyst 5 was 81.8%.

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
77.6 g of 2-aminoethanethiol was added to 300 ml of a solution prepared from 2-aminoethanethiol and water to obtain a solution of metal mercaptide containing phosphoric acid.

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 MoO ₃ , cobalt is 4% by weight in terms of CoO, and phosphorus is 3% by weight in terms of P ₂ O ₅ .
The amount of 2-aminoethanethiol used was 1.5 times the theoretical amount of sulfur required to convert Mo and Co into MoS ₂ and CoS, respectively.

The desulfurization rate of this catalyst 6 was 82.5%.

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
125.9 g of 4-aminothiophenol was added to 300 ml of a solution prepared from 300 ml of 4-aminothiophenol to obtain a solution of metal mercaptide containing phosphoric acid.

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 4-aminothiophenol used was 1.5 times the theoretical amount of sulfur required to convert Mo and Co into MoS ₂ and CoS, respectively.

The desulfurization rate of this catalyst 7 was 83.8%.

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
125.9 g of 4-aminothiophenol was added to 300 ml of a solution prepared from 300 ml of 4-aminothiophenol to obtain a solution of metal mercaptide containing phosphoric acid.

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 4-aminothiophenol used was 1.5 times the theoretical amount of sulfur required to convert Mo and Co into MoS ₂ and CoS, respectively.

The desulfurization rate of this catalyst 8 was 82.6%.

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
125.9 g of 4-aminothiophenol was added to 300 ml of a solution prepared from 300 ml of solution and water to obtain a solution of metal mercaptide containing phosphoric acid.

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 4-aminothiophenol used was 1.5 times the theoretical amount of sulfur required to convert Mo and Co into MoS ₂ and CoS, respectively.

The desulfurization rate of this catalyst 9 was 83.5%.

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
110.1 g of 2-aminoethanethiol was added to 300 ml of the solution prepared from the above and water to obtain a solution of metal mercaptide containing phosphoric acid.

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 2-aminoethanethiol used was 1.5 times the theoretical amount of sulfur required to convert Mo and Ni to MoS ₂ and NiS, respectively.

The desulfurization rate of this catalyst 10 was 77.8%.

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
and water to prepare 300 ml of aqueous solution.

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 2-aminoethanethiol to the dried product.
After impregnating the catalyst with a total of 115 ml of an ethanol solution containing 77.6 g, it was dried at 100° C. for 16 hours to obtain catalyst 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 2-aminoethanethiol used was 1.5 times the theoretical amount of sulfur required to convert Mo and Co into MoS ₂ and CoS, respectively.

The desulfurization rate of this catalyst 11 was 82.0%.

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, and 272 g of the boehmite-type alumina powder used in Example 1 were placed in a kneader. After performing kneading and obtaining a mixture,
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 77.6 g of 2-aminoethanethiol, 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 2-aminoethanethiol used was 1.5 times the theoretical amount of sulfur required to convert Mo and Co into MoS ₂ and CoS, respectively.

The desulfurization rate of this catalyst 12 was 81.9%.

Example 13 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, 125.9 g of 4-aminothiophenol was added, and a solution of metal mercaptide was added. did.

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 4-aminothiophenol used was 1.5 times the theoretical amount of sulfur required to convert Mo and Co into MoS ₂ and CoS, respectively.

The desulfurization rate of this catalyst 13 was 83.2%.

Example 14 272 g of the boehmite-type alumina powder used in Example 1, 77.6 g of 2-aminoethanethiol, and 85
300 ml of an aqueous solution containing 12.5 g of phosphoric acid (wt%) was placed in a kneader and kneaded to form a mold.

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

Molybdenum trioxide is added to the entire dry molded body.
38.5g, cobalt carbonate (Co content 49.1% by weight)
Catalyst 14 was obtained by repeating twice the operation of impregnating the entire amount with 150 ml of a solution prepared from 16.4 g, ammonia gas and water and 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 2-aminoethanethiol used was 1.5 times the theoretical amount of sulfur required to convert Mo and Co into MoS ₂ and CoS, respectively.

The desulfurization rate of this catalyst 14 was 81.8%.

Example 15 272 g of the boehmite-type alumina powder used in Example 1 and 115 ml of an aqueous solution containing 77.6 g of 2-aminoethanethiol were placed in a kneader and kneaded to form a product. This molded body was dried at 100°C for 16 hours.

Molybdenum trioxide is added to the entire dry molded body.
38.5g, cobalt carbonate (Co content 49.1% by weight)
After impregnating the entire amount with 100 ml of a solution prepared from 16.4 g, 12.5 g 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 2-aminoethanethiol used was 1.5 times the theoretical amount of sulfur required to convert Mo and Co into MoS ₂ and CoS, respectively.

The desulfurization rate of this catalyst 15 was 81.6%.

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

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

Molybdenum trioxide is added to the entire dry molded body.
38.5g, cobalt carbonate (Co content 49.1% by weight)
After impregnating the entire amount with 250 ml of a metal mercaptide solution obtained by adding 77.6 g of 2-aminoethanethiol to a solution prepared from 16.4 g, ammonia gas and water, 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 2-aminoethanethiol used was 1.5 times the theoretical amount of sulfur required to convert Mo and Co into MoS ₂ and CoS, respectively.

The desulfurization rate of this catalyst 16 was 81.5%.

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.

This catalyst was subjected to the following pre-sulfurization treatment.

Sulfurized oil 3% by weight n-butyl mercaptan/
Kuwait 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 Examples of this pre-sulfurized catalyst As a result of activity evaluation in the same manner as above, 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 volume
100 g of a 0.75 ml/g γ-alumina molded support 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 subjected to pre-sulfurization 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 conventional catalyst described above requires 8 hours for presulfiding treatment, and the catalyst described in Japanese Patent Publication No. 61-111144 also requires at least one hour after impregnation with the sulfurizing agent.
Although a time-consuming calcination treatment is required, the catalyst of the present invention and the catalyst produced by its manufacturing method do not require presulfidation and can be used as is for hydrogenation treatment without calcination, making it more economical than conventional methods. can provide a useful catalyst.

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.
At least one of the water-soluble compounds of group metals and an amino-substituted mercaptan of a hydrocarbon having 1 to 15 carbon atoms and hydrogen; A catalyst for hydrogenation of hydrocarbons consisting of an unfired mixture of boehmite-type alumina powder, γ-alumina powder, or both particles, which are all interposed at the bonding surface of each particle. 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.
Kneading a solution of at least one water-soluble compound of group metal and an amino-substituted mercaptan of a hydrocarbon consisting of carbon and hydrogen having 1 to 15 carbon atoms,
A method for producing a catalyst for hydrotreating hydrocarbons, which comprises forming and then drying the catalyst. 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 a solution of an amino-substituted mercaptan, a hydrocarbon consisting of carbon and hydrogen having 1 to 15 carbon atoms, is added to the dried shaped product. A method for producing a catalyst for hydrotreating hydrocarbons, which comprises impregnating and then drying again. 4 A solution of an amino-substituted mercaptan, a hydrocarbon consisting of carbon and hydrogen having 1 to 15 carbon atoms, is kneaded with one or both of boehmite-type alumina powder and γ-alumina powder, molded, and once dried to form the dried molded product. 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 6 metals and group 8 metals of the periodic table, 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.
consisting of at least one water-soluble compound of group metal, phosphoric acid, and an amino-substituted mercaptan of a hydrocarbon having 1 to 15 carbon atoms and hydrogen; At least one or all of the amino-substituted mercaptans are
A catalyst for hydrogenation of hydrocarbons comprising an unfired mixture of boehmite-type alumina powder, γ-alumina powder, or both particles interposed 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 an amino-substituted mercaptan 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 amino acid consisting of carbon and hydrogen having 1 to 15 carbon atoms. 1. A method for producing a catalyst for hydrotreating hydrocarbons, which comprises impregnating with a solution of substituted mercaptan 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, shaped and once dried, and the dried shaped product is treated with phosphoric acid and an amino-substituted hydrocarbon having 1 to 15 carbon atoms and hydrogen. A method for producing a catalyst for hydrogenation of hydrocarbons, which comprises impregnating a catalyst with a mercaptan and then drying it 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 an amino-substituted mercaptan of a hydrocarbon 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, phosphoric acid and a carbon atom having 1 to 1 carbon atoms.
A solution of a hydrocarbon amino-substituted mercaptan consisting of 15 carbons and hydrogen is kneaded, molded and once dried, and the dried molded product is injected with metals from group 6 of the periodic table and metals from group 8 of the periodic table.
1. 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 then drying the catalyst again. 11 One or both of boehmite-type alumina powder and γ-alumina powder is kneaded with a solution of an amino-substituted mercaptan, a hydrocarbon consisting of carbon and hydrogen having 1 to 15 carbon atoms, molded, and once dried to form 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 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. For hydrogenation treatment of hydrocarbons, which is characterized by impregnating with a solution of at least one type of chemical compound and an amino-substituted mercaptan of a hydrocarbon consisting of carbon and hydrogen having 1 to 15 carbon atoms, and then drying again. Method for producing catalyst.